CN103946421A

CN103946421A - Aqueous binder composition for metal surface treatment agents

Info

Publication number: CN103946421A
Application number: CN201280055823.3A
Authority: CN
Inventors: 永井彰典; 木村友哉; 宇留岛秀人
Original assignee: Kansai Paint Co Ltd
Current assignee: Kansai Paint Co Ltd
Priority date: 2011-11-14
Filing date: 2012-11-05
Publication date: 2014-07-23
Also published as: JP6092786B2; JPWO2013073401A1; WO2013073401A1

Abstract

The present invention provides an aqueous binder composition for chromate-free metal surface treatment agents that have excellent coatability and liquid stability and are capable of forming a surface treatment film having excellent corrosion resistance, adhesiveness and electrical conductivity. This aqueous binder composition for metal surface treatment agents contains: a reaction product of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group, or a reaction product of the above-described silane coupling agents and an alkoxysilane compound such as trialkoxysilane wherein a hydrocarbon group such as an alkyl group is directly bonded to a silicon atom; a specific acid compound; and water.

Description

Metal conditioner use binder composition

Technical field

The present invention relates to be applicable to process surperficial, the coating of metal base and the aqueous adhesive composition that the storage stability metal conditioner that can form surface treatment epithelium excellent and erosion resistance, adaptation and excellent electric conductivity is used; The metal conditioner that contains this aqueous adhesive composition; Utilize the surface treatment method of the metallic substance of this metal conditioner; And the manufacture method of above-mentioned aqueous adhesive composition.

Background technology

Conventionally, excellent as adaptation to metal material surface, can give to metal material surface the technology of erosion resistance etc., known following methods: for metal material surface, utilization contains chromic acid, dichromic acid or their salt to be implemented method that chromic salt processes, implements parkerized method, mainly utilize method that not chromate-containing inorganic components implements and process, utilizes silane coupling agent to implement the method processed etc. as the treatment solution of main component, and by these methods for practicality.

As utilizing not chromate-containing inorganic components, implement the technology of processing, in patent documentation 1, a kind of metal conditioner is disclosed for example, it contains: vanadium compound, and the metallic compound that comprises at least one metal in selected among zirconium, titanium, molybdenum, tungsten, manganese and cerium.But this metal conditioner exists processes the erosion resistance of epithelium, the problem of poorly conductive.

As the technology of using silane coupling agent, the surface treatment agent that a kind of organic solvent is has for example been proposed in patent documentation 2, it contains: by making to react with the silane coupling agent containing epoxy group(ing) the oxyalkylsiloxane with a large amount of alkoxysilyls and the polysiloxane obtaining containing amino silane coupling agent, wherein show by using this surface treatment agent, can form the improved siloxane film of the adaptation of base material.But this surface treatment agent is organic solvent system, therefore exist in safety and sanitation and the problem of environment aspect, from the viewpoint of these, make suitable water system and aspect stability of solution, having problems.

In patent documentation 3, disclose a kind of metallic substance surface treating composition, it contains: metal ion, (B) more than the specific divalent of water medium, (A) is selected from sour composition, (C) in specific fluoro-acid, phosphoric acid and acetic acid and has the silane coupling agent of specific functional group and (D) specific water soluble phenol resin based polymer.But there is liquid stabilising in this surface treating composition, coating is insufficient and the problem of the poorly conductive of processing epithelium.

In patent documentation 4, disclose a kind of metal material surface composition for treating, wherein coordinated phosphoric acid based compound (A), fluoro-acid (B) and containing amino silane coupling agent with containing the mixture (C) of the silane coupling agent of epoxy group(ing).But there is still inadequate problem of liquid stabilising and electroconductibility in said composition.

A kind of surface treating agent for metallic materials has been proposed in patent documentation 5, it contains: (a) containing the silane coupling agent of reactive organic group with at least have 2 reaction product with the organic compound of the group of this responding property of reactivity organic group, that is, as functional group, there is the compound of 2 above trialkoxysilyl (silanol group) and (b) be selected from organic acid, phosphoric acid and complex fluoride (Wrong fluorochemical) in compound.But there is still inadequate problem of liquid stabilising and electroconductibility in said composition.

The surface treatment agent of prior art as above, the whole important documents under discontented being enough to: coating and liquid stabilising are excellent, form the epithelium of erosion resistance, adaptation, excellent electric conductivity, not containing chromic salt; Still having problems when practical.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2002-30460 communique

Patent documentation 2: Japanese kokai publication hei 11-43647 communique

Patent documentation 3: Japanese kokai publication hei 11-106945 communique

Patent documentation 4: TOHKEMY 2006-213958 communique

Patent documentation 5: TOHKEMY 2001-49453 communique.

Summary of the invention

The problem that invention will solve

Main purpose of the present invention is to solve the problem described above existing in prior art, provide a kind of not containing chromic salt, coating and liquid stabilising are excellent, and can form the aqueous adhesive composition that the metal conditioner of the surface treatment epithelium of erosion resistance, adaptation and excellent electric conductivity is used.

A further object of the present invention is to provide the metal conditioner that contains above-mentioned aqueous adhesive composition, the surface treatment method of metallic substance that uses this metal conditioner and the manufacture method of above-mentioned aqueous adhesive composition.

Solve the means that problem is used

The inventor etc. conduct in-depth research in order to solve these problems of the prior art, result is this time found, contain reaction product, the binder composition of specific acid compound and water, described reaction product is: have amino silane coupling agent and the silane coupling agent with epoxy group(ing), according to circumstances Direct Bonding has the alkoxysilane compound containing trialkylsilyl group in molecular structure such as trialkoxy silane this or 3 the reaction product of the alkyl such as alkyl further and on Siliciumatom, in this reaction product, do not there is in fact epoxy group(ing), existing hydrolization group is in fact all hydrolyzed and generates silanol group, and suitably control the condensation of silanol group, the particlized that inhibition is caused by the condensation of silanol group, gelation, thereby can obtain the metal conditioner use binder composition of liquid stabilising excellence, the coating of the metal conditioner that contains this binder composition and liquid stabilising are excellent, by the processing for metal material surface, can form erosion resistance, the epithelium of adaptation and excellent electric conductivity, completed thus the present invention.

Therefore, the invention provides metal conditioner use binder composition, it is characterized in that,

This aqueous adhesive composition is the binder composition of pH4.0～10.0, and it contains:

By making (a) there is the silane coupling agent of at least one primary amino or secondary amino group and hydrolization group and (b) there is the silane coupling agent of at least one epoxy group(ing) and hydrolization group, further and (c) formula according to circumstances: (R) _4-n-Si-(X) _nat least one alkoxysilane compound containing trialkylsilyl group in molecular structure reaction that [in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 that reactive substituting group replaces, and X represents alkoxyl group, and n represents 1～3 integer] represents and reaction product (A);

Being selected from phosphoric acid is that acid compound and nitric acid are at least one the sour stablizer (B) in acid compound; And

Water,

Wherein, for silane coupling agent (a), the ratio that reaches 1.0～5.0 equivalents with the amount of epoxy group(ing) 1 equivalent with respect in silane coupling agent (b), amino active hydrogen in silane coupling agent (a) coordinates,

In at least a portion of reaction product (A), above-mentioned amino and epoxy group(ing) chemical bonding,

For reaction product (A), do not there is in fact the unreacted epoxy group(ing) based on silane coupling agent (b), and, hydrolization group and the alkoxysilyl based on alkoxysilane compound containing trialkylsilyl group in molecular structure (c) based on silane coupling agent (a) and silane coupling agent (b) are in fact all hydrolyzed into silanol group, and there is the weight-average molecular weight in 500～20000 scope

The amount reaching with the amino neutralization equivalent in silane coupling agent (a) in 0.1～2.0 scope contains sour stablizer (B).

The invention provides metal conditioner, it is characterized in that, contain above-mentioned metal conditioner use binder composition and rust-preventive agent.

The surface treatment method that the invention provides metallic substance, is characterized in that, above-mentioned metal conditioner is coated to metal material surface, makes it dry, and on this metal material surface, forming dry epithelium weight is 0.05～3.0g/m ²surface treatment epithelium.

The manufacture method that the invention provides above-mentioned aqueous adhesive composition, is characterized in that,

Make (a) there is the silane coupling agent of at least one primary amino or secondary amino group and hydrolization group and (b) there is the silane coupling agent of at least one epoxy group(ing) and hydrolization group, further and (c) formula according to circumstances: (R) _4-n-Si-(X) _n[in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, X represents alkoxyl group, n represents 1～3 integer] at least one alkoxysilane compound containing trialkylsilyl group in molecular structure reaction of representing and generate silane reaction product (A'), then by interpolation in silane reaction product (A'), being selected from phosphoric acid is that acid compound and nitric acid are, after at least one sour stablizer (B) in acid compound is prepared the aqueous liquid of silane reaction product, to carry out desolventizing.

Invention effect

For metal conditioner use binder composition of the present invention, the alkoxyl group of the hydrolization group based on silane coupling agent and the alkoxysilane compound containing trialkylsilyl group in molecular structure that according to circumstances exists be in fact all hydrolyzed into silanol group, and suitably suppress the condensation of silanol group, do not there is in fact unreacted epoxy group(ing) simultaneously, therefore liquid stabilising is excellent, and the tackiness agent of using as metal conditioner is brought into play excellent performance.

For the metal conditioner that contains aqueous adhesive composition of the present invention, coating and liquid stabilising are excellent, can form not chromate-containing metal finishing epithelium erosion resistance, adaptation and excellent electric conductivity, do not control material containing pollutions such as 6 valency chromium in epithelium.

According to the surface treatment method of use surface treatment agent of the present invention, can on the surface of metallic substance, form and be difficult to the erosion resistance taken into account and electroconductibility is all excellent in the past, and also excellent epithelium of adaptation.

Therefore, the present invention also has contribution for recycle of environmental preservation and surface treated metallic substance etc.

Manufacture method for aqueous adhesive composition of the present invention, by thering is desolventizing operation, can remove alcohol being generated by the hydrolysis of silane coupling agent etc., can be using the binder composition of gained as processing without hazardous material, can improve solids component ratio simultaneously, by containing specific acid, can keep the liquid stabilising of the aqueous adhesive composition after desolventizing operation and desolventizing operation.

Below, for metal conditioner use binder composition of the present invention, the metal conditioner that contains this binder composition, use the surface treatment method of metallic substance of this metal conditioner and the manufacture method of above-mentioned aqueous adhesive composition to be described in detail.

Embodiment

First for metal conditioner use binder composition, describe.

metal conditioner use binder composition

Metal material surface of the present invention process with binder composition be contain reaction product (A), be selected from the sour stablizer (B) of specific acid and pH4.0～10.0 of water, preferred 5.0～10.0, more preferably 6.0～10.0 stable binder composition, described reaction product (A) is by making at least two kinds of silane coupling agents, further reacting with alkoxysilane compound containing trialkylsilyl group in molecular structure the reaction product (A) obtaining as required.Binder composition of the present invention can make organic solvent content reach below 3 quality % by desolventizing, consequently, does not have flash-point, can be as processing without hazardous material in fire service law.

reaction product (A)

Reaction product in aqueous adhesive composition of the present invention (A) is the following reaction product obtaining: make to have the silane coupling agent (a) of at least one primary amino or secondary amino group and hydrolization group and have the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group, further and (c) formula according to circumstances: (R) _4-n-Si-(X) _nat least one alkoxysilane compound containing trialkylsilyl group in molecular structure that [in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, and X represents alkoxyl group, and n represents 1～3 integer] represents carries out addition reaction and/or hydrolysis reaction.

Should illustrate, in this specification sheets, sometimes these the 2 kinds of compositions of silane coupling agent (b) by making to have the silane coupling agent (a) of at least one primary amino or secondary amino group and hydrolization group and have at least one epoxy group(ing) and hydrolization group are carried out to the reaction product that addition reaction and/or hydrolysis reaction obtain and be called " reaction product (A-1) "; By by make to have at least one primary amino or secondary amino group and hydrolization group silane coupling agent (a), there is the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group and (c) formula: (R) _4-n-Si-(X) _n[in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, X represents alkoxyl group, and n represents 1～3 integer] these 3 kinds of compositions of at least one alkoxysilane compound containing trialkylsilyl group in molecular structure of representing carry out addition reaction and/or hydrolysis reaction and reaction product be called " reaction product (A-2) ".

In at least a portion of above-mentioned reaction product (A), form the chemical bond that the addition reaction due to the amino of silane coupling agent (a) and the epoxy group(ing) of silane coupling agent (b) produces.Epoxy group(ing) is consumed in this addition reaction, it is desirable to, and does not have in fact the unreacted epoxy group(ing) that is derived from silane coupling agent (b) in reaction product (A).

For reaction product (A), the alkoxysilyl of the hydrolization group based on silane coupling agent (a) and silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) based on according to circumstances existing is in fact all hydrolyzed into silanol group, and can have the weight-average molecular weight in 500～20000 scope.Specifically, reaction product (A-1) conventionally preferably has 500～10000, particularly preferably have the weight-average molecular weight in 1000～6000 scope, and reaction product (A-2) preferably has 500～20000 conventionally, particularly preferably have the weight-average molecular weight in 1000～10000 scope.

In this specification sheets, " hydrolization group based on silane coupling agent (a) and silane coupling agent (b) and the according to circumstances alkoxysilyl of the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) of existence are in fact all hydrolyzed into silanol group " refers to, in nmr analysis (NMR), do not find the state at the peak of hydrolization group and alkoxysilyl, normally at least 95% in hydrolization group and alkoxysilyl is hydrolyzed into the state of silanol group.In this specification sheets, " not having in fact unreacted epoxy group(ing) " refers to, in nmr analysis (NMR), do not find the state at the peak of unreacted epoxy group(ing), and normally the ratio of the unreacted epoxy group(ing) in epoxy group(ing) is the state below 5%.In this specification sheets, sometimes comprise " alkoxysilyl " and " hydrolization group " both, be referred to as " water-disintegrable functional group ".

In this specification sheets, the weight-average molecular weight of reaction product (A) is, the retention time (retention volume) of the polystyrene standard that molecular weight by the retention time (retention volume) of using gel permeation chromatography (GPC) to measure based on measuring is under the same conditions known is scaled the molecular weight of polystyrene and the value of trying to achieve.As gel permeation chromatography device, " HLC-8120GPC " (trade(brand)name, the Eastソー society system) of use, as post, use 1 " TSKgel GMHHR-L " (trade(brand)name, Eastソー society system), as detector, use differential refraction rate meter, can be in moving phase: dimethyl formamide (containing trolamine 0.5 quality %), measure temperature: under 25 ℃, the condition of flow velocity: 1mL/min, measure.

Silane coupling agent (a) (being sometimes referred to as below " (a) composition ") so long as in 1 molecule, have at least one, the preferably primary amino of 1 or 2 or the silane coupling agent of secondary amino group and hydrolization group, there is no particular limitation.Said hydrolyzed group, there is no particular limitation, as preferred hydrolization group, can enumerate the alkoxyl group that is bonded directly to element silicon, that is, and alkoxysilyl.

Concrete example as silane coupling agent (a), such as enumerating: N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330, N-(2-amino-ethyl) APTES, 3-TSL 8330, APTES etc., wherein can preferably be used N-(2-amino-ethyl) 3-TSL 8330, N-(2-amino-ethyl) APTES, 3-TSL 8330, APTES.

Silane coupling agent (b) (being sometimes referred to as below " (b) composition ") so long as have the silane coupling agent of at least one epoxy group(ing) and hydrolization group in 1 molecule, and there is no particular limitation.Said hydrolyzed group, there is no particular limitation, as preferred hydrolization group, can enumerate the alkoxyl group that is bonded directly to element silicon, that is, and alkoxysilyl.

Concrete example as silane coupling agent (b), such as enumerating: γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl triethoxyl silane etc., wherein can preferably be used γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxyl silane.

In addition the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) (being sometimes referred to as below " (c) composition ") according to circumstances using, is by formula: (R) _4-n-Si-(X) _nthe alkoxysilane compound containing trialkylsilyl group in molecular structure that [in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, and X represents alkoxyl group, and n represents 1～3 integer] represents.As above-mentioned, do not there is reactive substituting group, such as enumerating: chloro, fluorine-based, methoxyl group, oxyethyl group, propoxy-etc., as alkyl, such as enumerating: alkyl, thiazolinyl base, cycloalkyl, aryl, aralkyl etc.In addition, as alkoxyl group, the alkoxyl group of the carbonatomss 1～6 such as preferred methoxyl group, oxyethyl group, propoxy-.

Alkoxysilane compound containing trialkylsilyl group in molecular structure (c) comprises trialkoxy silane compound, dialkoxy silicane compound and monoalkoxy silane compound, from viewpoints such as the solvabilities water medium, consider, preferably at least contain the alkoxysilane compound containing trialkylsilyl group in molecular structure of 80 quality % trialkoxy silane compounds, wherein preferably only contain the alkoxysilane compound containing trialkylsilyl group in molecular structure of trialkoxy silane compound.

As above-mentioned trialkoxy silane compound, for example, can enumerate: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, amyltrimethoxysilane, hexyl Trimethoxy silane, octyl group Trimethoxy silane, methyl three (methoxy ethoxy) silane, ethyl three (methoxy ethoxy) silane, 3,3,3-trifluoro propyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (methoxy ethoxy) silane, phenyltrimethoxysila,e, phenyl triethoxysilane etc., wherein, methyltrimethoxy silane particularly preferably, Union carbide A-162, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, methyl three (methoxy ethoxy) silane, ethyl three (methoxy ethoxy) silane.

As above-mentioned list-or two-alkoxysilane compound containing trialkylsilyl group in molecular structure, such as enumerating: monoalkoxy silane such as trimethylammonium methoxy silane, trimethylethoxysilane, trimethylammonium propoxy-silane, triethyl methoxy silane, triethyl-ethoxy-silicane alkane; The dialkoxy silicanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl dipropoxy silane, diethyl dimethoxy silane, diethyl diethoxy silane, methylethyl dimethoxy silane, methylethyl diethoxy silane, dipropyl Trimethoxy silane etc.

Reaction product (A), be in reaction product (A-1) and manufacture (A-2), mixing ratio for silane coupling agent (a) and silane coupling agent (b), can be epoxy group(ing) 1 equivalent making with respect in silane coupling agent (b), the amount of the amino active hydrogen in silane coupling agent (a) reaches 1.0～5.0 equivalents, preferably 1.5～4.0 equivalents, the more preferably ratio of 2.0～3.5 equivalents.

For example, for 3-TSL 8330, in 1 molecule, amino has 2 active hydrogens, so 1 mole of 3-TSL 8330 is equivalent to active hydrogen base 2 equivalents.In addition, for N-(2-amino-ethyl) 3-TSL 8330, in 1 molecule, possess the primary amino with 2 active hydrogens and the secondary amino group with 1 active hydrogen, in 1 molecule, amount to and there are 3 active hydrogens, so 1 mole of N-(2-amino-ethyl) 3-TSL 8330 is equivalent to active hydrogen base 3 equivalents.

In the manufacture of reaction product (A-2), the mixing ratio of silane coupling agent (a), silane coupling agent (b) and alkoxysilane compound containing trialkylsilyl group in molecular structure (c) can be, based on above-mentioned (a), (b) and (c) total amount 100 mass parts of composition, (a) and (b) composition add up to 30～95 mass parts, be preferably 50～90 mass parts, 60～90 mass parts more preferably, (c) composition is 5～70 mass parts, is preferably 10～50 mass parts, 10～40 mass parts more preferably then.Should illustrate, for silane coupling agent (a), as mentioned above, can coordinate with following ratio, described ratio is epoxy group(ing) 1 equivalent making with respect in silane coupling agent (b), and the amount of the amino active hydrogen in silane coupling agent (b) reaches 1.0～5.0 equivalents, is preferably 1.5～4.0 equivalents, the ratio of 2.0～3.5 equivalents more preferably.

Reaction product (A-1) can obtain by the aqueous liquid of silane reaction product (A'-1) (aqueous solution) is carried out to desolventizing by method described later, the aqueous liquid of described silane reaction product (A'-1) is, by in containing the water medium of acid neutralizing agent, make silane coupling agent (a) and silane coupling agent (b) carry out addition reaction and hydrolysis reaction and the aqueous liquid that obtains; Or, by organic solvent or under non-solvent condition, make silane coupling agent (a) and silane coupling agent (b) carry out addition reaction, and then the aqueous liquid that makes this addition reaction be hydrolyzed in containing the water medium of acid neutralizing agent and react and obtain.

In this specification sheets, " water medium " refers to, water or at least contain 80 water of quality % water and the mixed liquid of other liquid, refers to the liquid of the reaction product that can dissolve or disperse silane coupling agent (a), silane coupling agent (b) and silane coupling agent (a) and silane coupling agent (b).As other liquid in above-mentioned mixed liquid, such as enumerating: organic solvent, neutralizing agent, tensio-active agent, in them 2 kinds or mixture of more than two kinds etc.

As the organic solvent in above-mentioned mixed liquid, can preferably use water miscible organic solvent, such as enumerating: methyl alcohol, ethanol, Virahol, n-propyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monobutyl ether etc.

As the neutralizing agent in above-mentioned mixed liquid, as acid neutralizing agent, for example can enumerate: formic acid, acetic acid, propionic acid, butyric acid, 2 ethyl hexanoic acid, lactic acid, succsinic acid, pentanedioic acid, citric acid, methacrylic acid, 1-hydroxyl ethane-1, the organic acids such as 1-di 2 ethylhexyl phosphonic acid, the two phosphonic acids of hydroxyl methane, tosic acid; The mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, as alkaline neutraliser, such as enumerating: inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor; MEA, diethylamide, triethylamine, diisopropylamine, triisopropylamine, dibutylamine, monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, N, the amine compound such as N-dimethylaminoethanol.

As the tensio-active agent in above-mentioned mixed liquid, can use itself known tensio-active agent such as anionic surfactant, nonionic surfactant, cationic surfactant, amphoterics, macromolecular tensio-active agent, reactive surfactant.

As the acid neutralizing agent that contains above-mentioned water medium, can be used as the cited acid neutralizing agent of acid neutralizing agent in above-mentioned mixed liquid.

In the manufacture method of the aqueous liquid of silane reaction product (A'-1), first for manufacture the method for the aqueous liquid of silane reaction product (A'-1) via the operation of reacting in water medium, for representational manufacture method, method for making 1 and method for making 2 describe.

Method for making 1 > of the aqueous liquid of < silane reaction product (A'-1)

The method for making 1 of the aqueous liquid of silane reaction product (A'-1) is following method: in water medium, the silane coupling agent (a) that makes to have at least one primary amino or secondary amino group and the hydrolization group reaction that is hydrolyzed, then this hydrolysis reactant is mixed in containing the water medium of acid neutralizing agent with the silane coupling agent (b) with at least one epoxy group(ing) and hydrolization group, be hydrolyzed and react and addition reaction, generate silane reaction product (A').Following method specifically: add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group in water medium, make after the hydrolization group hydrolysis based on silane coupling agent (a), complex acid neutralizing agent, then add the silane coupling agent (b) with at least one epoxy group(ing) and hydrolization group, be hydrolyzed and react and addition reaction, obtain the aqueous liquid of silane reaction product (A'-1).

In this method for making 1, therefore silane coupling agent (a) has amino, conventionally has water-solublely, and above-mentioned water medium can be water, but for solvability raising, pH regulator etc., can be also the mixed liquid that contains acid neutralizing agent, organic solvent and/or tensio-active agent etc. as required.

In above-mentioned method for making 1, if add silane coupling agent (a) in water medium, the heat release due to hydrolysis reaction, therefore in order to prevent violent reaction, preferably slowly carries out the interpolation of silane coupling agent (a).If cause violent reaction, can cause tempestuously the condensation reaction of the silanol group being generated by hydrolysis reaction, easily produce particlized, gelation.

Hydrolysis reaction by the hydrolization group based on silane coupling agent (a) in water medium generates silanol group.Then, to complex acid neutralizing agent in the reactant solution generating, then add silane coupling agent (b).To the reaction mixture solution generating carry out in acid and time acid neutralizing agent used amount be, in reaction mixture solution after neutralization, with respect to amino 1.0 equivalents of silane coupling agent (a), conventionally reach 0.1～1.0 equivalent, the preferred amount of 0.1～0.5 equivalent.While being combined with acid neutralizing agent in advance in water medium, the use level of the acid neutralizing agent coordinating in can subtend reactant solution regulates to reach above-mentioned neutralization equivalent scope.By the cooperation of this acid neutralizing agent, can make the pH of aqueous liquid of the silane reaction product (A'-1) of gained be generally 4～10, be preferably 5～10, pH6～10 more preferably.

In reactant solution, add the moment of silane coupling agent (b), whole or most of hydrolysis of the hydrolization group of preferred silane coupling agent (a), but can be also the only part hydrolysis of hydrolization group.

Then, in reactant solution after neutralizing to above-mentioned acid, add silane coupling agent (b), carry out amino and the addition reaction between the epoxy group(ing) based on silane coupling agent (b) and the hydrolysis reaction of hydrolization group based on silane coupling agent (a), can obtain the aqueous liquid of silane reaction product (A'-1).These reactions conventionally at the temperature of 20～100 ℃, carry out approximately 0.5～approximately 20 hour, preferably at the temperature of 40～90 ℃, carry out approximately 1～approximately 10 hour.

In the aqueous liquid of the silane reaction product so obtaining (A'-1), as solids component can be at common 3～30 quality %, preferably the scope of 5～20 quality % contains silane reaction product (A'-1).

Method for making 2 > of the aqueous liquid of < silane reaction product (A'-1)

The method for making 2 of the aqueous liquid of silane reaction product (A'-1) is following method: in water medium, make to have after the hydrolization group hydrolysis of silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group, add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group, in containing the water medium of acid neutralizing agent, be hydrolyzed and react and addition reaction, obtain the aqueous liquid of silane reaction product (A'-1).

In this method for making 2, silane coupling agent (b) is poorly soluble in water conventionally, therefore uses the water medium that contains acid neutralizing agent.Because water medium contains acid neutralizing agent, thereby hydrolysis that can facilitation of hydrolysis group can make the water-soluble of reactant be improved.

In above-mentioned method for making 2, while adding silane coupling agent (b) in water medium, in order to prevent violent reaction, preferably carry out lentamente the interpolation of silane coupling agent (b).If add silane coupling agent (b) in water medium, the hydrolysis of the hydrolization group in silane coupling agent (b) is carried out, and generates silanol group.In the reaction mixture generating, whole or most of hydrolysis of the hydrolization group of preferred silane coupling agent (b), but can be also the only part hydrolysis of hydrolization group.

Then, in above-mentioned reaction mixture solution, add silane coupling agent (a), carry out amino and the addition reaction between the epoxy group(ing) based on silane coupling agent (b) and the hydrolysis reaction of hydrolization group based on silane coupling agent (a), can obtain the aqueous liquid of silane reaction product (A'-1).

Above-mentioned reaction after silane coupling agent (a) adds can at the temperature of common 20～100 ℃, carry out approximately 0.5～approximately 20 hour, preferably at the temperature of 40～90 ℃, carry out approximately 1～approximately 10 hour.In above-mentioned reaction mixture solution, add the moment of silane coupling agent (a), the amount of the acid neutralizing agent coordinating in liquid is preferably the amount that amino 1.0 equivalents with respect to silane coupling agent (a) conventionally reach 0.1～1.0 equivalent, reach especially 0.1～0.5 equivalent.By the cooperation of this acid neutralizing agent, can make the pH of the aqueous liquid of silane reaction product (A'-1) be generally 4～10, be preferably 5～10, pH6～10 more preferably.

In the aqueous liquid of the silane reaction product so obtaining (A'-1), with solid component meter, can be with common 3～30 quality %, preferably the amount in the scope of 5～20 quality % contains silane reaction product (A'-1).

Then, for method for making 3, describe, this method for making 3 is the methods of the aqueous liquid of silane reaction product (A'-1) of manufacturing via the operation that silane coupling agent (a) and silane coupling agent (b) are reacted in non-solvent or organic solvent.

Method for making 3 > of the aqueous liquid of < silane reaction product (A'-1)

The method for making 3 of the aqueous liquid of silane reaction product (A'-1) is following method: in organic solvent or under the condition of non-solvent, make to have at least one primary amino or secondary amino group and hydrolization group silane coupling agent (a), there is the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group, between amino and epoxy group(ing), carry out addition reaction, then make this addition reaction be dissolved or dispersed in the water medium that contains water and acid neutralizing agent, the reaction that is hydrolyzed, obtains the aqueous liquid of silane reaction product (A'-1).

Above-mentioned method for making 3 is, first makes silane coupling agent (a) and silane coupling agent (b), in organic solvent or under the condition of non-solvent, carries out addition reaction between amino and epoxy group(ing).This addition reaction is thermopositive reaction, preferably suppresses violent reaction, for example preferably, both are slowly mixed, and after mixing finishes, for example stir about is 30 minutes～approximately 2 hours, in the stage of tending towards stability in reaction, at the temperature of 60～90 ℃, heat and within approximately 1～approximately 20 hour, carry out addition reaction.While reacting in organic solvent, as organic solvent, preferably water dissolubility and easily carry out the lower boiling water-soluble solvent of the desolventizing in subsequent handling, can enumerate as concrete example: the low-boiling point alcohol solvents such as ethanol, Virahol, n-propyl alcohol.

After above-mentioned addition reaction finishes, addition reaction mixture is dissolved or dispersed in the water medium that contains acid neutralizing agent, the reaction that is hydrolyzed, can obtain the aqueous liquid of silane reaction product (A'-1) thus.Said hydrolyzed reaction can be carried out as follows: addition reaction mixture is dissolved or dispersed in the water medium that contains acid neutralizing agent, conventionally at the temperature of 20～100 ℃, react approximately 0.5～approximately 20 hour, preferably at the temperature of 40～90 ℃, react approximately 1～approximately 10 hour.The amount of the acid neutralizing agent in the water medium coordinating in above-mentioned addition reaction mixture is, makes amino 1.0 equivalents with respect to used silane coupling agent (a), conventionally reaches 0.1～1.0 equivalent, preferably reaches the amount of 0.1～0.5 equivalent.By this acid neutralizing agent, can make the pH of aqueous liquid of the silane reaction product (A'-1) of gained be generally 4～10, be preferably 5～10, pH6～10 more preferably.In the aqueous liquid of the silane reaction product so obtaining (A'-1), with solid component meter, can be with 3～30 quality %, preferably the amount in the scope of 5～20 quality % contains silane reaction product (A'-1).

Reaction product (A-2) can obtain as follows: silane coupling agent (a), silane coupling agent (b) and alkoxysilane compound containing trialkylsilyl group in molecular structure (c), for the addition reaction between hydrolysis reaction and epoxy group(ing) and amino, are carried out to desolventizing by method described later to the aqueous liquid of generated silane reaction product (A'-2).This reaction can be undertaken by following method: the method for reacting in water medium; Or, after making part reaction in alcoholic solvent or under the condition of non-solvent, the method for further reacting in water medium etc.

In the manufacture method of the aqueous liquid of above-mentioned silane reaction product (A'-2), first, for manufacture the method for the aqueous liquid of silane reaction product (A'-2) by the method for reacting in water medium, for the method for making 1 as representative manufacture method and method for making 2, describe.

Method for making 1 > of the aqueous liquid of < silane reaction product (A'-2)

The method for making 1 of the aqueous liquid of silane reaction product (A'-2) is following method: in water medium, the silane coupling agent (a) that makes to have at least one primary amino or secondary amino group and the hydrolization group reaction that is hydrolyzed, then make this hydrolysis reactant react with silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) with at least one epoxy group(ing) and hydrolization group, generate silane reaction product (A'-2).

Representative method for making as the method for making 1 of the aqueous liquid of silane reaction product (A'-2), can be listed below method: in water medium, the silane coupling agent (a) that makes to have at least one primary amino or secondary amino group and the hydrolization group reaction that is hydrolyzed, this hydrolysis reactant is mixed in containing the water medium of acid neutralizing agent with silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) with at least one epoxy group(ing) and hydrolization group, be hydrolyzed and react and addition reaction, generate silane reaction product (A'-2).

In this method for making 1, therefore (a) composition has amino, conventionally has water-solublely, and above-mentioned water medium can be water, but for solvability raising, pH regulator etc., can be also the mixed liquid that contains acid neutralizing agent, organic solvent and/or tensio-active agent etc. as required.

In above-mentioned method for making 1, if add (a) composition in water medium, the heat release due to hydrolysis reaction, therefore in order to prevent violent reaction, preferably slowly carries out the interpolation of (a) composition.If cause violent reaction, can cause tempestuously the condensation reaction of the silanol group being generated by hydrolysis reaction, easily produce particlized, gelation.

Hydrolysis reaction by the hydrolization group based on (a) composition in water medium generates silanol group.From the raising of water-soluble, the viewpoint of the raising of stability consider, preferably, in the reaction mixture solution generating, add acid neutralizing agent, then add (b) composition and (c) composition.At this moment, to the reaction mixture solution generating carry out in acid and time acid neutralizing agent used amount can be, in reaction mixture solution after neutralization, with respect to amino 1 equivalent of (a) composition, conventionally reach 0.1～2.0 equivalent, preferably reach the amount of 0.1～1.0 equivalent.In water medium, in advance during complex acid neutralizing agent, preferably the use level of the acid neutralizing agent coordinating is regulated to reach above-mentioned neutralization equivalent scope in reaction-ure mixture solution.By the cooperation of this acid neutralizing agent, can make the pH of the water medium liquid that contains silane reaction product (A'-2) of gained be generally 4～10, be preferably 5～10, more preferably 6～10.

In above-mentioned reaction mixture solution, add (b) composition and (c) moment of composition, preferably whole or most of hydrolysis of the hydrolization group of (a) composition, but can be also only a part of hydrolysis of hydrolization group.

At above-mentioned (b) composition and (c) composition of adding in the reaction mixture solution of acid neutralization, carry out amino and the addition reaction of epoxy group(ing) and the hydrolysis reaction of water-disintegrable functional group, can obtain thus silane reaction product (A'-2) aqueous liquid.These reactions can be carried out approximately 0.5～approximately 20 hour conventionally at the temperature of 20～100 ℃, preferably at the temperature of 40～90 ℃, carry out approximately 1～approximately 10 hour.

In the silane reaction product obtaining in water medium like this (A'-2) aqueous liquid, with solid component meter, can be with common 3～30 quality %, preferably the amount in the scope of 5～20 quality % contains silane reaction product (A'-2).

Method for making 2 > of the aqueous liquid of < silane reaction product (A'-2)

The method for making 2 of the aqueous liquid of silane reaction product (A'-2) is following method: in water medium, after the silane coupling agent (b) that makes to have at least one epoxy group(ing) and hydrolization group and alkoxysilane compound containing trialkylsilyl group in molecular structure (c) are hydrolyzed and react, add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group, in containing the water medium of acid neutralizing agent, be hydrolyzed and react and addition reaction, generate silane reaction product (A'-2).

In this method for making 2, (b) composition, with (c) the common hydrolysis rate of composition is slower, is therefore preferably used and contains acid as the water medium of catalyzer, that is, and and the water medium that contains acid neutralizing agent.By making water medium contain acid neutralizing agent, thus can facilitation of hydrolysis the hydrolysis of group, can improve the water-soluble of reaction mixture.

In above-mentioned method for making 2, in water medium, add (b) composition and (c) during composition, in order to prevent violent reaction, preferably carry out lentamente (b) composition and (c) interpolation of composition.If add (b) composition and (c) composition in water medium, (b) composition and (c) the water-disintegrable functional group in composition be hydrolyzed, generate silanol group.In the reaction mixture generating, preferably (b) composition and (c) whole or most of hydrolysis of the water-disintegrable functional group of composition, but can be also the only part hydrolysis of hydrolization group.

Then, in above-mentioned reaction mixture solution, add (a) composition, carry out amino and the addition reaction between the epoxy group(ing) based on (b) composition and the hydrolysis reaction of water-disintegrable functional group based on (a) composition, can obtain thus the aqueous liquid of silane reaction product (A'-2).

(a) the above-mentioned reaction of composition after adding can conventionally at the temperature of 20～100 ℃, carry out approximately 0.5～approximately 20 hour, preferably at the temperature of 40～90 ℃, carry out approximately 1～approximately 10 hour.In above-mentioned reaction mixture solution, add the moment of (a) composition, the amount of the acid neutralizing agent coordinating in liquid can be, amino 1 equivalent with respect to (A) composition conventionally reaches 0.1～2.0 equivalent, preferably reaches the amount of 0.1～1.0 equivalent.By the cooperation of this acid neutralizing agent, can make the pH of the aqueous liquid of silane reaction product (A'-2) be generally 4～10, be preferably 5～10, more preferably 6～10.

In the aqueous liquid of the silane reaction product obtaining in water medium like this (A'-2), with solid component meter, can be with common 3～30 quality %, preferably the amount in the scope of 5～20 quality % contains silane reaction product (A'-2).

Then, for method for making 3, describe, this method for making 3 is by alcoholic solvent or under the condition of non-solvent, make (a), (b) and (c) after a part for composition is reacted, the method for further reacting is manufactured the method for the aqueous liquid of silane reaction product (A'-2) in water medium.

Method for making 3 > of the aqueous liquid of < silane reaction product (A'-2)

The method for making 3 of the aqueous liquid of silane reaction product (A'-2) is following method: in organic solvent, particularly in alcoholic solvent or under the condition of non-solvent, make (a), (b) and (c) a kind in composition or 2 kinds of compositions are hydrolyzed after reaction, in water medium, further add remaining one-tenth to assign to be hydrolyzed and react and addition reaction, generate thus silane reaction product (A'-2).

Representative method for making as the method for making 3 of the aqueous liquid of silane reaction product (A'-2), can be listed below method: in alcoholic solvent or under the condition of non-solvent, the silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) that make to have at least one epoxy group(ing) and hydrolization group are hydrolyzed after reaction, this hydrolysis reactant is dissolved or dispersed in the water medium that contains acid neutralizing agent, then add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group, be hydrolyzed and react and addition reaction, generate silane reaction product (A'-2).

In the representative method for making of above-mentioned method for making 3, preferably, first, in alcoholic solvent or under the condition of non-solvent, with respect to (b) composition and (c) the total molar weight 1 of composition, add the water of approximately 1～approximately 5 times of molar weight, make (b) composition and (c) the composition reaction that is hydrolyzed.This hydrolysis reaction is thermopositive reaction, preferably suppresses violent reaction, for example, preferably both are added lentamente.Due to violent reaction, also there is condensation reaction in the silanol group generating when this hydrolysis reaction, if condensation reaction is excessively carried out, easily causes gelation, therefore need to arouse attention.Said hydrolyzed reaction can conventionally at the temperature of 20～80 ℃, carry out approximately 0.5～approximately 10 hour, preferably at the temperature of 30～70 ℃, carry out approximately 1～approximately 5 hour.As above-mentioned alcoholic solvent, preferably water dissolubility and easily carry out the solvent of the desolventizing in subsequent handling, as concrete example, can enumerate: the low-boiling point alcohol solvents such as ethanol, Virahol, n-propyl alcohol.

After this hydrolysis reaction, the reaction mixture of gained is dissolved or dispersed in the water medium that contains acid neutralizing agent.Then, in the water medium of the reaction mixture of gained, add (a) composition, be hydrolyzed reaction and (a) addition reaction between the epoxy group(ing) in the amino in composition and (b) composition, generation silane reaction product (A'-2).The amount of the acid neutralizing agent in above-mentioned water medium can be, amino 1 equivalent in (a) composition coordinating in the water medium with respect to reactant conventionally reaches 0.1～2.0 equivalent, preferably reaches the amount of 0.1～1.0 equivalent.By the cooperation of this acid neutralizing agent, can make the pH of aqueous liquid of the silane reaction product (A'-2) of gained be generally 4～10, be preferably 5～10, more preferably 6～10.

Hydrolysis reaction in above-mentioned water medium and addition reaction can conventionally at the temperature of 20～100 ℃, carry out approximately 0.5～approximately 20 hour, preferably at the temperature of 40～90 ℃, carry out approximately 1～approximately 10 hour.

In addition, as method for making 3, the method that can be listed below: in alcoholic solvent or under the condition of non-solvent, the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group is hydrolyzed after reaction, the reaction mixture of gained is dissolved or dispersed in the water medium that contains acid neutralizing agent, then add silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) with at least one epoxy group(ing) and hydrolization group, be hydrolyzed and react and addition reaction, generate thus silane reaction product (A'-2).

By above-described method for making 1～3, can obtain with the state dissolving or disperse the aqueous liquid of silane reaction product (A'-2) in water medium.

In this specification sheets, silane reaction product (A'-1) and silane reaction product (A'-2) are referred to as to silane reaction product (A') in the lump.

In aqueous liquid by the silane reaction product utilizing above-described method to obtain (A'), add the sour stablizer (B) of the following stated, after preparing thus the aqueous liquid of silane reaction product, carry out the operation of desolventizing, can manufacture the stable aqueous adhesive composition of the reaction product (A) that contains the solids component that becomes binder composition.

acid stablizer (B)

Sour stablizer (B) in the present composition is the composition that contributes to improve the liquid stabilising of aqueous adhesive composition of the present invention, is to suppress aqueous adhesive composition or used the condensation reaction of the silanol group of the reaction product (A) in the metal conditioner of aqueous adhesive composition, the composition that liquid stabilising is improved.In addition, sour stablizer (B) is also improved the effect of the erosion resistance of the surface treatment epithelium being formed by surface treatment agent sometimes.

In the present composition, sour stablizer (B) is that to be selected from phosphoric acid be that acid compound and nitric acid are at least one acid in acid compound.

As above-mentioned phosphoric acid, be acid compound, such as enumerating: the inorganic phosphates such as phosphoric acid (ortho-phosphoric acid), condensed phosphoric acid, phosphorous acid are acid compound; The organic phosphoric acids such as organic phospho acid are acid compound.Condensed phosphoric acid comprises metaphosphoric acid and Tripyrophosphoric acid, and metaphosphoric acid is the phosphoric acid condenses of ring-type, comprises three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid etc., and Tripyrophosphoric acid is the phosphoric acid condenses of chain, comprises tetra-sodium, three Tripyrophosphoric acid, four Tripyrophosphoric acid etc.In addition, as organic phospho acid, for example, can enumerate: Amino Trimethylene Phosphonic Acid, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, the two phosphonic acids of hydroxyl methane, ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) etc.

As above-mentioned nitric acid, be acid compound, such as enumerating nitric acid, nitrous acid etc.

These sour stablizers can use separately respectively or two or more is used in combination.

In acid stablizer (B), wherein preferably phosphoric acid and nitric acid, particularly preferably phosphoric acid.

Based on reaction product (A) 100 mass parts, the use level of sour stablizer (B) is generally 1～10 mass parts, is preferably 2～8 mass parts, 3～7 mass parts more preferably.

the manufacture of metal conditioner use binder composition

Metal conditioner use binder composition of the present invention for example can be manufactured by the following method, the method is characterized in that: make to have the silane coupling agent (a) of at least one primary amino or secondary amino group and hydrolization group and have the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group, according to circumstances further and likes: (R) _4-n-Si-(X) _n[in formula, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, X represents alkoxyl group, n represents 1～3 integer] at least one alkoxysilane compound containing trialkylsilyl group in molecular structure (c) reaction of representing and generate silane reaction product (A'), then by interpolation in silane reaction product (A'), being selected from phosphoric acid is that acid compound and nitric acid are, after at least one sour stablizer (B) in acid compound is prepared the aqueous liquid of silane reaction product, to carry out desolventizing.

Above-mentioned silane reaction product (A') is same with reaction product (A), preferably, the epoxy group(ing) chemical bonding of the amino of silane coupling agent (a) and silane coupling agent (b), do not there is in fact the unreacted epoxy group(ing) based on silane coupling agent (b), and based on silane coupling agent (a), the water-disintegrable functional group of silane coupling agent (b) and alkoxysilane compound containing trialkylsilyl group in molecular structure (c) is in fact all hydrolyzed into silanol group, even if but there is a small amount of unreacted epoxy group(ing), or a part for water-disintegrable functional group is not hydrolyzed into silanol group and is residual, in desolventizing operation, react, the reaction product obtaining after desolventizing operation (A) is not if have in fact unreacted epoxy group(ing), water-disintegrable functional group is in fact all hydrolyzed to the reaction product of silanol group, within being also included within silane reaction product (A').

The aqueous liquid of silane reaction product for example can be prepared as follows: to adding sour stablizer (B) as in the aqueous liquid of silane reaction product obtained above (A'), mix.

The desolventizing of the aqueous liquid of the silane reaction product so obtaining is the operation that easily makes liquid stabilising variation, but according to the present invention, by mixing acid stablizer (B) before desolventizing operation, can keep the stability of liquid.

As long as the condition of this desolventizing can be removed alcohol equal solvent in the aqueous liquid of silane reaction product, that generate by being hydrolyzed, liquid stabilising is not produced to obstacle, have no particular limits, for example desolventizing can carry out as follows: conventionally 50～90 ℃, underpressure distillation approximately 0.5～approximately 20 hour at the temperature of 60～80 ℃ especially, preferably approximately 0.5～approximately 3 hour.The variation of the liquid pH being caused by desolventizing operation is little, but in the situation that the pH of the binder composition in desolventizing or after desolventizing exceeds outside above-mentioned scope, can regulate pH by adding neutralizing agent.

Desolventizing product can directly be used as metal conditioner use binder composition, or as required, in order to regulate solids component or to regulate pH, after hydrous water, neutralizing agent etc., as metal conditioner use binder composition.

Metal material surface of the present invention is processed has the pH in common 4.0～10.0, preferably 5.0～10.0, more preferably 6.0～10.0 scope with binder composition.In addition, in binder composition of the present invention, solid component concentration can be conventionally at 5～30 quality %, preferably in the scope of 5～20 quality %, and organic solvent amount be 3 quality % following, be below 1 quality % especially, be preferably do not have flash-point without hazardous material.In addition, mobility from the viewpoint of liquid, for metal material surface processing binder composition of the present invention, measuring 20 ℃ of temperature, the liquid viscosity of measuring under the condition of 60rpm with Type B rotational viscosimeter is preferably generally below 2.5cps, especially for below 2.4cps.

metal conditioner

Metal conditioner of the present invention contains binder composition and rust-preventive agent for above-described metal conditioner.

As above-mentioned rust-preventive agent, be at the conventional rust-preventive agent of paint field, such as enumerating: the metallic compound that contains the metals such as manganese, cobalt, zinc, magnesium, nickel, titanium, vanadium, zirconium, tin, calcium, silicon, tungsten, molybdenum, hafnium and aluminium; Inorganic phosphate, organic phosphoric acid etc.As this metallic compound, such as enumerating: the carbonate of this metal, phosphoric acid salt, nitrate, vitriol, acetate, fluoro-acid and salt, oxide compound etc.These metallic compounds can be anhydrides, can be also hydrate while existing.In above-mentioned metallic compound, wherein preferably contain the metallic compound of titanium, vanadium and zirconium.

As the concrete example of above-mentioned metallic compound, can enumerate: alkaline carbonic acid zirconium (ZrCO ₄zrO ₂8H ₂o), zirconium carbonate ammonium, single nickel salt, zirconium nitrate, vanadylic sulfate, zirconium sulfate, aluminum nitrate, nickelous acetate, zirconium acetate, vanadium oxide, ammonium meta-vanadate; Hexafluoro metatitanic acid (H ₂tiF ₆), hexafluoro zirconic acid (H ₂zrF ₆), hexafluoro SiClx acid (H ₂siF ₆), six hafnium fluoride acid (H ₂hfF ₆), hexafluoro aluminic acid (H ₃alF ₆), tetrafluoride boric acid (HBF ₄) etc. the salt (for example, sodium salt, sylvite, lithium salts, ammonium salt, amine salt, zinc salt etc.) etc. of fluoro-acid, these fluoro-acids.

As the concrete example that can be used as the inorganic phosphate of rust-preventive agent, can enumerate: phosphoric acid (ortho-phosphoric acid), three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid, tetra-sodium, three Tripyrophosphoric acid, four Tripyrophosphoric acid etc., concrete example as organic phosphoric acid, can enumerate: Amino Trimethylene Phosphonic Acid, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, 1-hydroxyl methane-1,1-di 2 ethylhexyl phosphonic acid, ethylene diamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) etc.Wherein, preferably phosphoric acid, the two phosphonic acids of hydroxyl methane and 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid.

These can be used as rust-preventive agent above-mentioned metallic compound, inorganic phosphate, organic phosphoric acid can use separately respectively or two or more is used in combination.

The use level of the above-mentioned rust-preventive agent in metal conditioner of the present invention, from the viewpoint of the stability of erosion resistance, electroconductibility and surface treatment agent, solids component 100 mass parts based on reaction product (A), can be generally 0.1～100 mass parts, are preferably 0.3～80 mass parts, 0.5～60 mass parts more preferably.

In metal conditioner of the present invention, except above-mentioned aqueous adhesive composition and above-mentioned rust-preventive agent, further can contain common paint additive as required, such as organic resin composition, wax composition, weighting agent, organic solvent etc.

As above-mentioned organic resin composition, be to improve the composition that the erosion resistance etc. of the epithelium of gained coordinates for object, such as enumerating: the organic resin such as the resol of water-soluble or water dispersible, epoxy resin, urethane resin, acrylic resin.While coordinating organic resinous principle, from viewpoints such as erosion resistance, electroconductibility, consider, all solids composition based on metal conditioner, in solids component amount, its use level can be generally 0.1～30 quality %, is preferably 0.2～25 quality %, 0.3～20 quality % more preferably.

Above-mentioned wax composition is for giving the composition of oilness to formed epithelium surface, such as enumerating: the carboxylate of polyol compound and lipid acid is that fatty acid ester wax, silicon are that wax, fluorine are that the polyolefin-waxes such as wax, polyethylene, lanolin are wax, montanin wax, Microcrystalline Wax, carnauba wax etc.These waxes can be used singly or two or more kinds mixed respectively.While coordinating wax, from the viewpoint of forming process, erosion resistance etc., all solids composition based on metal conditioner, in solids component amount, its use level can be generally 0.1～10 quality %, is preferably 0.2～7.5 quality %, 0.3～5 quality % more preferably.

As the weighting agent that can coordinate as required in metal conditioner, such as enumerating: zirconia sol, alumina sol, silicon dioxide gel (colloided silica aqueous dispersions) etc.

In addition, the water medium of metal conditioner of the present invention can be water conventionally, but for example in order to regulate rate of drying, or the objects such as the coating that makes metal conditioner improves, the organic solvents such as low Grade alcohol that also can contain the methyl alcohol, ethanol, propyl alcohol and so on of a small amount of (for example, the total amount based on water medium is that 5 quality % are following).This organic solvent can be the residual organic solvents such as alcohol in the desolventizing operation of carrying out when obtaining aqueous adhesive composition, can be also the organic solvent adding after when preparing metal conditioner.

Surface treatment agent of the present invention comprise build bath (building bath) with composition (concentrated solution) and operation use composition (diluent) the two.Build bath and can be generally 10～40 quality %, be preferably 15～30 quality % with the total solids constituent concentration in composition, operation can be generally 1～40 quality %, be preferably 5～30 quality % with the total solids constituent concentration in composition.

By surface treatment agent of the present invention with operating while using composition, for this surface treatment agent, coating from the viewpoint of surface treatment agent, preferably, use Type B rotational viscosimeter, the viscosity of measuring under the condition of 20 ℃ of temperature and revolution 60rpm is below 2.5mPa s, especially for below 2.4mPa s.

In addition, surface treatment agent of the present invention preferably have be generally 5.0～10.0, be the pH in 6.0～9.0 scope especially.Now, as pH adjusting agent, the pH adjusting agent of using as raising pH, such as using the alkali metal hydroxides such as ammoniacal liquor, amine compound, sodium hydroxide; The alkaline carbonates such as sodium carbonate etc., in addition, as the pH adjusting agent that reduces pH and use, for example, can be used hereinbefore the acid as acid neutralizing agent example.If the pH of surface treatment agent is too low, become excessively with the reactivity of substrate surface, the tendency that exists film-forming properties, the electroconductibility of formed epithelium to become bad.In addition, if the pH of surface treatment agent is too high, surface treatment reduces by the stability of composition, has the tendency of the erosion resistance reduction of formed epithelium.

The storage stability of metal conditioner of the present invention is excellent.Its reason is not yet clear and definite, but think to be caused by following item: at the composition for binder constituents by the mixture of the silane coupling agent with the reactive base reacting to each other of more than two kinds, in storage, sometimes between reactive base, react and storage stability is reduced, but in surface treatment agent of the present invention, make in advance amino that silane coupling agent has and epoxy reaction, use in fact the not reaction product of the epoxy group(ing) of remained unreacted, therefore the amino thing that storage stability is reduced with epoxy reaction can not occur in storage; Binder constituents is stabilization due to stablizer (B), and the condensation of the silanol group generating by being hydrolyzed is inhibited etc.The inventor etc. think that silanol group is coordinated in stablizer (B) and stabilization, and the reaction between silanol group is inhibited.

the surface treatment method of metallic substance

The surface treatment method of metallic substance is also provided according to the present invention, it is characterized in that, above-mentioned metal conditioner is coated to metal material surface, make it dry, on this metal material surface, form dry epithelium weight and be generally 0.05～3.0g/m ², be preferably 0.1～1.0g/m ², 0.2～0.8g/m more preferably ²surface treatment epithelium.Dried epithelium mass deficiency 0.05g/m ²time, being difficult to coated metal material fully, the erosion resistance of coated metal material becomes insufficient, if dried epithelium quality surpasses 3.0g/m ², the tendency that exists the electroconductibility of surface treatment epithelium to reduce.

The method that is coated with above-mentioned metal conditioner at metal material surface has no particular limits, and can adopt itself known coating process, for example, and pickling process, spraying method, rolling method etc.On metal material surface, formed surface treatment agent layer preferably carries out heat drying, the condition of heat drying at this moment has no particular limits, preferably by approximately 50～approximately 250 ℃ conventionally, especially heat at the temperature of approximately 100～approximately 250 ℃ approximately 1～approximately 60 second, within approximately 2～approximately 30 seconds, be dried especially.

The metallic substance that can be coated with metal conditioner of the present invention has no particular limits, for example can enumerate: iron plate, steel plate galvanized, galvanized alloy are (for example, iron-zinc, aluminium-zinc, nickel-zinc alloy etc.) steel plate, tin plate, stainless steel plate, aluminium sheet, aluminium alloy plate etc., wherein preferably steel plate galvanized and galvanized alloy steel plate.In addition, the size of this metallic substance, shape etc. also have no particular limits.

If heat drying is carried out in the metallic surface that is coated with metal conditioner of the present invention, because the dehydrating condensation between the silanol group of the silane coupling agent in reaction product (A) forms the continuous epithelium with siloxane bond.The compound with siloxane bond generating is the compound of slightly water-soluble, the formation epithelium that contains this compound has been given play to the effect that intercepts water, thinks consequently, improves the erosion resistance of metallic substance, simultaneously, owing to being epithelium based on siloxane bond, therefore can suppress the reduction of electroconductibility.In addition, the silanol group and the metal material surface that by the hydrolysis of silane coupling agent, are produced react and form epoxy bond (オキサン Knot closes), and the adaptation that forms epithelium is improved.And then, in metal conditioner of the present invention, using making in advance amino in silane coupling agent and epoxy reaction reaction product (A) as binder constituents, contribute to the raising of erosion resistance.

[embodiment]

Following example embodiment and comparative example are described more specifically the present invention, but scope of the present invention is not subject to any restriction of these embodiment.In embodiment and comparative example, " part " and " % " is in case of no particular description all in quality criteria.

the manufacture of aqueous adhesive composition

Embodiment 1

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate N-2-(amino-ethyl)-57 parts of 3-TSL 8330, under agitation spend wherein 3 hours and drip 61 parts of γ-glycidoxypropyltrimewasxysilane.Because dropping produces heat release, but remain on below 40 ℃, after dropping finishes, under agitation slaking, naturally cooling 1 hour, then heat and at 80 ℃, react 5 hours.By 1H-NMR measurement result, confirmed not residual epoxy group(ing) in this reacted content.Then, add 1000 parts of 28 parts of acetic acid and deionized waters, stir 30 minutes, make reacted contents melting, obtain the aqueous liquid of silane reaction product (A').Adopting the neutralization equivalent of the silane reaction product (A') of acetic acid is 0.9.

In the aqueous liquid of this silane reaction product (A'), add 6 parts of 89% phosphate aqueous solutions, further stir 30 minutes, after adding 250 parts of deionized waters that it is dissolved, by the underpressure distillation at 60～70 ℃, be concentrated into 1000 parts, the methyl alcohol being produced by hydrolysis is distilled and removed together with moisture, then with 200 object filters, filter, obtain the aqueous adhesive composition A1 as the aqueous solution.In aqueous adhesive composition A1, in total acid, the neutralization equivalent of utilizing phosphoric acid is 0.1.

The solids component of aqueous adhesive composition A1 is that 10%, pH is 6.5.Utilize the methanol concentration less than 1.5% in the aqueous adhesive composition A1 of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A1 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A1 is approximately 4500, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 2

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 1000 parts of deionized waters, while use cooling N-2-(amino-ethyl)-57 parts of the 3-TSL 8330 that drop into lentamente of ice bath, make its dissolving.Then coordinate 12 parts of acetic acid in this content after, drop into 61 parts of γ-glycidoxypropyltrimewasxysilane, stirs and within 30 minutes, make its dissolving, then heat and at 80 ℃, react 5 hours, obtain the aqueous liquid of silane reaction product (A').By 1H-NMR measurement result, confirm not residual epoxy group(ing) in this silane reaction product (A').Utilizing the neutralization equivalent of the silane reaction product (A') of acetic acid is 0.4.

Then, in the aqueous liquid of this silane reaction product (A'), coordinate 6 parts of 89% phosphate aqueous solutions, stir 30 minutes, after adding 250 parts of deionized waters that it is dissolved, by the underpressure distillation at 60～70 ℃, be concentrated into 1000 parts.After the methyl alcohol being produced by hydrolysis is like this distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition A2 as the aqueous solution.In aqueous adhesive composition A2, in total acid, the neutralization equivalent of utilizing phosphoric acid is 0.1.

The solids component of aqueous adhesive composition A2 is that 10%, pH is 7.1.The methanol concentration less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The solids component of aqueous adhesive composition A2 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A2 is approximately 4000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 3

To being equipped with, in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 19 parts of 1000 parts of deionized waters and acetic acid, while stir, drop into lentamente 61 parts of γ-glycidoxypropyltrimewasxysilane, stir and within 10 minutes, make its dissolving.Then, drop into lentamente wherein N-2-(amino-ethyl)-57 parts of 3-TSL 8330, stir and within 30 minutes, make, after its dissolving, to heat and at 80 ℃, react 5 hours, obtain the aqueous liquid of silane reaction product (A').By 1H-NMR measurement result, confirm not residual epoxy group(ing) in this silane reaction product (A').Utilizing the neutralization equivalent of the silane reaction product (A') of acetic acid is 0.6.

In the aqueous liquid of this silane reaction product (A'), coordinate 6 parts of 89% phosphate aqueous solutions, stir 30 minutes, after adding 250 parts of deionized waters that it is dissolved, by the underpressure distillation at 60～70 ℃, be concentrated into 1000 parts.The methyl alcohol being produced by hydrolysis is like this distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition A3 as the aqueous solution.In aqueous adhesive composition A3, in total acid, the neutralization equivalent of utilizing phosphoric acid is 0.1.

The solids component of aqueous adhesive composition A3 is that 10%, pH is 6.7.The methanol concentration less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The solids component of aqueous adhesive composition A3 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A3 is approximately 4000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 4

Except 57 parts of the use levels of N-2-(amino-ethyl)-3-TSL 8330 in embodiment 1 being changed to 62 parts and 61 parts of the use levels of γ-glycidoxypropyltrimewasxysilane are changed to 56 parts, 28 parts of the use levels of acetic acid are changed to 30 parts, other and embodiment 1 carry out same operation, obtain the aqueous adhesive composition A4 of solids component 10%, pH6.5.In aqueous adhesive composition A4, in total acid, utilizing the neutralization equivalent of acetic acid is 0.9, and the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A4, utilize the methanol concentration less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A4 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.5 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A4 is approximately 4000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 5

Except 57 parts of the use levels of N-2-(amino-ethyl)-3-TSL 8330 in embodiment 1 being changed to 45 parts and 61 parts of the use levels of γ-glycidoxypropyltrimewasxysilane are changed to 73 parts, 28 parts of the use levels of acetic acid are changed to 25 parts, other and embodiment 1 carry out same operation, obtain the aqueous adhesive composition A5 of solids component 10%, pH6.5.In aqueous adhesive composition A5, in total acid, utilizing the neutralization equivalent of acetic acid is 0.9, and the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A5, utilize the methanol concentration less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A5 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 2.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A5 is approximately 5300, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 6

Except N-2-(amino-ethyl) in embodiment 2-57 parts of 3-TSL 8330 being changed to 65 parts of APTESs, 12 parts of the use levels of acetic acid being changed to 7 parts, 61 parts of the use levels of γ-glycidoxypropyltrimewasxysilane are changed to 70 parts and 6 parts of the use levels of 89% phosphate aqueous solution are changed to 3 parts, other and embodiment 2 carry out same operation, obtain the aqueous adhesive composition A6 of solids component 10%, pH7.1.In aqueous adhesive composition A6, in total acid, utilizing the neutralization equivalent of acetic acid is 0.4, and the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A6, utilize the determining alcohol less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A6 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of APTES is 2.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A6 is approximately 3000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 7

Except 57 parts of the use levels of N-2-(amino-ethyl)-3-TSL 8330 in embodiment 1 being changed to 61 parts and 61 parts of the use levels of γ-glycidoxypropyltrimewasxysilane are changed to 64 parts, 28 parts of acetic acid are changed to 11 parts of 60% aqueous nitric acid, mismatch 89% phosphate aqueous solution, other and embodiment 1 carry out same operation, obtain the aqueous adhesive composition A7 of solids component 10%, pH9.0.In aqueous adhesive composition A7, the neutralization equivalent of utilizing nitric acid is 0.2.

For aqueous adhesive composition A7, utilize the methanol concentration less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A7 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 2.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A7 is approximately 3000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 8

Except 61 parts of γ-glycidoxypropyltrimewasxysilane in embodiment 3 being changed to 72 parts of γ-glycidoxypropyl triethoxyl silanes, other and embodiment 3 carry out same operation, obtain the aqueous adhesive composition A8 of solids component 10%, pH6.7.In aqueous adhesive composition A6, in total acid, utilizing the neutralization equivalent of acetic acid is 0.6, and the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A7, utilize the determining alcohol less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A8 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 2.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A8 is approximately 4000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 9

Except 28 parts of acetic acid in embodiment 1 being changed to 11 parts of 35% aqueous hydrochloric acids, other and embodiment 1 carry out same operation, obtain the aqueous adhesive composition A9 of solids component 10%, pH8.6.In aqueous adhesive composition A9, in total acid, utilizing the neutralization equivalent of hydrochloric acid is 0.2, and the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A9, utilize the methanol concentration less than 1.5% of gas chromatograph for determination, do not observe flash-point.The solids component of aqueous adhesive composition A9 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A9 is approximately 3000, does not find the change of molecular weight of desolventizing operation front and back.

Embodiment 10

Except 1000 parts of deionized waters in embodiment 2 are changed to 864 parts, other operates similarly to Example 2 and obtains the aqueous liquid of silane reaction thing.The neutralization equivalent of utilizing acetic acid in the aqueous liquid of silane reaction thing is 0.4.Then in the aqueous liquid of the silane reaction thing of gained, add 89% phosphate aqueous solution, after stirring, do not add deionized water, and do not carry out underpressure distillation, in addition carry out same operation with embodiment 2, obtain the aqueous adhesive composition A10 of solids component 10%, pH7.1.In aqueous adhesive composition A10, in total acid, the neutralization equivalent of utilizing phosphoric acid is 0.1.

For aqueous adhesive composition A10, the methanol concentration that utilizes gas chromatograph for determination is 5.0%, and flash-point is 76 ℃.The solids component of aqueous adhesive composition A10 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed, in addition, by 1H-NMR measurement result, confirms not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A10 is approximately 3500.

Comparative example 1

In embodiment 2, do not add 89% phosphate aqueous solution, operate similarly to Example 2 and obtain aqueous adhesive composition AC1.The aqueous liquid of silane reaction product produces gonorrhoea in underpressure distillation, in the aqueous adhesive composition AC1 finally obtaining, generates a large amount of throw outs.Therefore,, for this aqueous adhesive composition AC1, below do not test.

Comparative example 2

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 874 parts of deionized waters, on one side cooling with ice bath, drop into lentamente N-2-(amino-ethyl)-57 parts of 3-TSL 8330 on one side, make its dissolving.Then, coordinate 12 parts of acetic acid in this content after, drop into 61 parts of γ-glycidoxypropyltrimewasxysilane, stir and within 30 minutes, make its dissolving.Be warming up to 80 ℃ of reactions 5 hours, obtain the aqueous liquid of silane reaction product (A').By 1H-NMR measurement result, confirm not residual epoxy group(ing) in this silane reaction product.The neutralization equivalent of utilizing the silane reaction thing of acetic acid is 0.4.The aqueous liquid of the silane reaction product of gained is directly filtered with 200 object filters, obtain aqueous adhesive composition AC2.

The solids component of aqueous adhesive composition AC2 is 10%, pH is 7.4.The methanol concentration that utilizes gas chromatograph for determination is 8%, and flash-point is 65 ℃.In addition, by 1H-NMR measurement result, confirm not residual epoxy group(ing).With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition AC2 is approximately 4000.

Comparative example 3

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 864 parts of deionized waters, on one side cooling with ice bath, drop into lentamente N-2-(amino-ethyl)-57 parts of 3-TSL 8330 on one side, make its dissolving.Then, coordinate 12 parts of acetic acid in this content after, in the temperature of reaction soln, be no more than under the condition of 10 ℃, spend 1 hour and drip 61 parts of γ-glycidoxypropyltrimewasxysilane, further stir and within 30 minutes, make its dissolving.From 1H-NMR measurement result, in this silane reaction product, for epoxy group(ing), 30% unreacted at initial stage and residual.The neutralization equivalent of utilizing acetic acid in the aqueous liquid of silane reaction product is 0.4.Directly with 200 object filters, filter, obtain the aqueous adhesive composition AC3 as the aqueous solution.

The solids component of aqueous adhesive composition AC3 is 10%, pH is 7.4, and in addition, the methanol concentration that utilizes gas chromatograph for determination is 5.0%, and flash-point is 76 ℃.The solids component of aqueous adhesive composition AC3 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyltrimewasxysilane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3 equivalents.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition AC3 is approximately 1500.

Comparative example 4

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 61 parts of γ-glycidoxypropyltrimewasxysilane, add 15 parts of 28 parts of acetic acid and deionized waters, after stirring and being hydrolyzed for 30 minutes, while remove cut, be warming up to 100 ℃.And then at 100 ℃, maintain 1 hour, and promote condensation, obtain the aqueous solution of water white thickness.Under agitation, in the aqueous solution of this thickness, spend 1 hour dropping N-2-(amino-ethyl)-57 parts of 3-TSL 8330.After dropping finishes, stir 1 hour, then heat and at 80 ℃, react 5 hours.By 1H-NMR measurement result, confirmed not residual epoxy group(ing) in this reacted content.Then, coordinate 833 parts of deionized waters, stir 30 minutes, make reacted contents melting, but liquid is gonorrhoea, can not dissolve completely.

The weight-average molecular weight of the resin solid composition of resulting aqueous adhesive composition AC4 surpasses 10000.For aqueous adhesive composition AC4, below do not test.

The cooperation of the aqueous adhesive composition in embodiment 1～10 shown in following table 1 and comparative example 1～4, proterties etc.In table 1, omit the use level of water.

[table 1]

the storage test of aqueous adhesive composition

The aqueous adhesive composition of making in embodiment 1～10 and comparative example 2 and 3, the storage at each temperature of 20 ℃, 30 ℃, 40 ℃ and 50 ℃ 30 days, is evaluated to the storage stability of liquid based on liquid appearance and liquid viscosity with following benchmark.The results are shown in following table 2.The liquid state at initial stage is also recorded in the lump.Liquid viscosity adopts Type B rotational viscosimeter, under the condition of measuring 20 ℃ of temperature and revolution 60rpm, measures.　

Zero: liquid appearance is colourless～mono-yellow transparent, and viscosity is below 2.5mPa s.　

△: liquid appearance is for muddy a little, visible precipitate thing or seston, viscosity surpasses 2.5mPa s, but does not observe remarkable thickening or gelation.　

*: liquid appearance is for quite muddy, and visible precipitate thing or seston, observe remarkable thickening or gelation.

[table 2]

the preparation of metal conditioner

Embodiment 11～22 and comparative example 5 and 6

The composition of metal conditioner and mixing ratio thereof and liquid stabilising are shown in following table 3.Each composition is mixed, to reach the mixing ratio shown in following table 3, use acetic acid or ammoniacal liquor to be adjusted to pH7.0, obtain each metal conditioner.Storage stability with the metal conditioner of following method evaluation gained.It the results are shown in following table 3.

storage stability

Liquid appearance and liquid viscosity based on preserving under institute's fixed temperature after 1 week are evaluated with following benchmark.Liquid viscosity is used Type B rotational viscosimeter, under the condition of measuring 20 ℃ of temperature and revolution 60rpm, measures.　

Zero: liquid appearance is transparent, viscosity is below 2.5mPa s.　

[table 3]

the manufacture of surface treatment plate

Embodiment 23～40 and comparative example 7 and 8

For thickness of slab 0.6mm two sides electrogalvanizing steel plate (the weight per unit area 20g/m of EG material, one side ²) surface, the aqueous solution of the concentration 2% of alkali cleaner (Japanese シービーケミカル society system, trade(brand)name " ケミ Network リー Na ー 561B ") has been dissolved in use, under the condition of temperature 60 C, carry out 2 minutes spray treatment, carry out thus degreasing, remove the dust or the oil that on surface, adhere to, after washing, be dried.According to the indication shown in following table 4, utilize rolling method, gained on the steel plate galvanized of skimming treatment, be coated with above-described embodiment and comparative example in each metal conditioner of obtaining, carry out baking in 20 seconds so that starting material arrive temperature is 100 ℃, obtain surface treatment plate.For metal conditioner, use the metal conditioner at initial stage after manufacturing, and at 20 ℃, preserve the metal conditioner after 7 days.

Each surface treatment plate of the making for using the metal conditioner of preparing in each embodiment and comparative example, the test method based on following, carries out the test of erosion resistance and electroconductibility.Its test-results is shown in following table 4.In addition, for each surface treatment plate, the result of carrying out aftermentioned fitness test is, each surface treatment plate is not all found peeling off of surface treatment epithelium, and adaptation is good.

[table 4]

test method:

Erosion resistance:

By the end face portion of each surface treatment plate of gained and back part sealing, carry out the salt spray testing (SST) based on JIS Z 2371.According to following benchmark, carry out the rusting rate after 120 hours and 240 hours evaluation test time.　

A: do not observe and get rusty.　

B: 5% of the not enough entire area of getting rusty.　

C: get rusty account for entire area more than 5% and less than 10%.　

D: get rusty account for entire area more than 10% and less than 50%.　

E: get rusty and account for the more than 50% of entire area.

Electroconductibility:

Use the ア of Mitsubishi Chemical Na リテッ Network (strain) ロレ processed スタ GP, ASP terminal, measure the sheet resistance value at any 10 places of surface treatment plate, to be shown as 10 ^-4number of times below Ω is evaluated.　

A: whole 10 times

B:6～9 time

C:1～5 time

D:0 time.

Fitness test:

On the surface treatment epithelium face of each surface treatment plate, with cutting knife, to arrive the mode of matrix, in 10mm four directions, make checker so that form the square of 100 1mm * 1mm.To push the mode of this checker portion from outside, carry out cupping (Erichsen) test (7mm extruding) afterwards, closely sealed glassine paper adhesive tape in the processing department through extruding, while peeling off in moment, evaluates the extent of exfoliation of surface treatment epithelium.

the manufacture of aqueous adhesive composition

Embodiment 41

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 850 parts of deionized waters, while use cooling N-2-(amino-ethyl)-53 parts of the 3-TSL 8330 that drop into lentamente of ice bath, make its dissolving.Then, in this content, coordinate after 23 parts of acetic acid neutralize, drop into the mixture of 16 parts of 66 parts of γ-glycidoxypropyl triethoxyl silanes and methyltrimethoxy silanes, stir and within 30 minutes, make after its dissolving, at 80 ℃, react 5 hours, obtain the aqueous liquid of silane reaction product (A').By 1H-NMR measurement result, confirm not residual epoxy group(ing) in this silane reaction product (A').

Then,, to adding 300 parts of 10 parts of 89% phosphate aqueous solutions and deionized waters in the aqueous liquid of this silane reaction product (A'), after it is dissolved, at 60～70 ℃, by underpressure distillation, be concentrated into 1000 parts.After the alcohol being generated by hydrolysis is like this distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition A11 as the aqueous solution.The solids component of aqueous adhesive composition A11 is 10%, pH is 6.1.The determining alcohol less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The resin solid composition of aqueous adhesive composition A11 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.Epoxy group(ing) 1 equivalent with respect to used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents, with respect to the sour neutralization equivalent of this amino, is 1.0.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A11 (utilizing GPC to measure) is for approximately 7.0 * 10 ³.

Embodiment 42～49 and comparative example 11

Except changing in embodiment 41 mix proportion as shown in table 5, other and embodiment 41 similarly operate, and prepare aqueous adhesive composition A12～A19 and AC6.For aqueous adhesive composition A12～A19 and AC6, utilize the equal less than 1.5% of determining alcohol of gas chromatograph for determination, do not observe flash-point.The intrinsic numerics such as acid neutralization equivalent, the equivalent with respect to the amino active hydrogen of epoxy group(ing) 1 equivalent, solids component, pH, weight-average molecular weight are as shown in table 5.

Embodiment 50

To being equipped with, in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 21 parts of 850 parts of deionized waters and acetic acid, stir on one side, drop into lentamente 30 parts of 61 parts of γ-glycidoxypropyl triethoxyl silanes and methyltrimethoxy silanes on one side, stir and within 10 minutes, make its dissolving.Then, in this content, drop into lentamente N-2-(amino-ethyl)-49 parts of 3-TSL 8330, stir and within 30 minutes, make, after its dissolving, at 80 ℃, to react 5 hours, obtain the water medium of silane reaction thing.By 1H-NMR measurement result, confirmed not residual epoxy group(ing) in this silane reaction thing.

Then,, to adding 300 parts of 10 parts of 89% phosphate aqueous solutions and deionized waters in the water medium of this silane reaction thing, after it is dissolved, at 60～70 ℃, by underpressure distillation, be concentrated into 1000 parts.The alcohol being generated by hydrolysis is like this distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition A20 as the aqueous solution.The solids component of aqueous adhesive composition A20 is 10%, pH is 6.1.The determining alcohol less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The resin solid composition of aqueous adhesive composition A20 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.Sour neutralization equivalent with respect to this amino is 1.0.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A20 (utilizing GPC to measure) is 7.2 * 10 ³.

Embodiment 51

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate N-2-(amino-ethyl)-61 parts of 3-TSL 8330, spend and within 3 hours, drip wherein 49 parts of γ-glycidoxypropyltrimewasxysilane, after dropping finishes, stir 1 hour, then at 80 ℃, react 5 hours.By 1H-NMR measurement result, confirmed not residual epoxy group(ing) in this content.In this content, coordinate after 21 parts of acetic acid neutralize, coordinate 850 parts of deionized waters, it is dissolved, then drop into 30 parts of methyltrimethoxy silanes, at 60 ℃, stir 30 minutes, make its hydrolysis, obtain the aqueous liquid of silane reaction product (A').

Then, to adding 300 parts of 10 parts of 89% phosphate aqueous solutions and deionized waters in the aqueous liquid of this silane reaction product (A'), at 60～70 ℃, by underpressure distillation, be concentrated into 1000 parts, the alcohol being generated by hydrolysis is distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition A21 as the aqueous solution.The solids component of aqueous adhesive composition A21 is 10%, pH is 6.1.The determining alcohol less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The resin solid composition of aqueous adhesive composition A21 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.Sour neutralization equivalent with respect to this amino is 1.0.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A21 (utilizing GPC to measure) is 7.0 * 10 ³.

Embodiment 52

The use level of γ-glycidoxypropyl triethoxyl silane, N-2-(amino-ethyl)-3-TSL 8330, acetic acid, methyltrimethoxy silane in embodiment 41 is changed to amount as shown in table 5, and then add 9 parts of 60% aqueous nitric acid when dropping into acetic acid, in addition operate equally with embodiment 41, obtain aqueous adhesive composition A22.The solids component of aqueous adhesive composition A22 is 10%, pH is 8.0.The determining alcohol less than 1.5% of utilizing gas chromatograph for determination, does not observe flash-point.The resin solid composition of aqueous adhesive composition A22 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.Sour neutralization equivalent with respect to this amino is 0.4.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition A22 (utilizing GPC to measure) is 3.0 * 10 ³.

Comparative example 9

To being equipped with in the separable flask of reflux exchanger, thermometer and stirrer, coordinate 826 parts of deionized waters, on one side cooling with ice bath, drop into lentamente N-2-(amino-ethyl)-62 parts of 3-TSL 8330 on one side, make its dissolving.Then, in this content, coordinate after 33 parts of acetic acid neutralize, drop into 78 parts of γ-glycidoxypropyl triethoxyl silanes, stirs 30 minutes, make, after its dissolving, at 80 ℃, to react 5 hours, obtain the aqueous liquid of silane reaction product (A').By 1H-NMR measurement result, confirm not residual epoxy group(ing) in this silane reaction thing.

Then, in the aqueous liquid of this silane reaction product (A'), add 300 parts of deionized waters, after it is dissolved, at 60～70 ℃, by underpressure distillation, be concentrated into 1000 parts.After the alcohol being generated by hydrolysis is like this distilled and removed together with moisture, with 200 object filters, filter, obtain the aqueous adhesive composition AC4 as the aqueous solution.Aqueous adhesive composition AC4 produces throw out in enrichment process, after filtering, still has gonorrhoea with 200 object filters.Cannot be used as binder aqueous solution, the evaluation after therefore not carrying out.

Comparative example 10

In the aqueous liquid of the silane reaction product (A') obtaining except make N-2-(amino-ethyl)-3-TSL 8330 and the reaction of γ-glycidoxypropyl triethoxyl silane in comparative example 9, do not add deionized water, and do not carry out outside underpressure distillation, other and comparative example 9 operate equally, obtain aqueous adhesive composition AC5.The solids component of aqueous adhesive composition AC5 is 10%, pH is 6.1.The determining alcohol that utilizes gas chromatograph for determination is 5.2%, and flash-point is 76 ℃.The resin solid composition of aqueous adhesive composition AC5 does not have alkoxysilyl, and alkoxysilyl is hydrolyzed.With respect to epoxy group(ing) 1 equivalent of used γ-glycidoxypropyl triethoxyl silane, the amount of the amino active hydrogen of N-2-(amino-ethyl)-3-TSL 8330 is 3.0 equivalents.Sour neutralization equivalent with respect to this amino is 1.0.The weight-average molecular weight of the resin solid composition of aqueous adhesive composition AC5 (utilizing GPC to measure) is 4.0 * 10 ³.

[table 5]

the storage test of aqueous adhesive composition

The liquid of making in embodiment 41～52 and comparative example 10 and 11, the storage at each temperature of 20 ℃, 30 ℃, 40 ℃ and 50 ℃ 30 days, is evaluated to the storage stability of liquid based on liquid appearance and liquid viscosity with following benchmark.The results are shown in following table 6.The liquid state at initial stage is also recorded in the lump.In comparative example 1, only record the liquid state at initial stage.Liquid viscosity, measuring 20 ℃ of temperature, adopts Type B rotational viscosimeter, under the condition of revolution 60rpm, measures.　

Zero: liquid appearance is colourless～faint yellow transparent, and liquid viscosity is below 2.5mPa s.　

[table 6]

the preparation of metal conditioner

Embodiment 53～66 and comparative example 12 and 13

The cooperation of metal conditioner and liquid stabilising are shown in following table 7.Coordinate each composition, to reach the Pei He Group shown in following table 7, become, use acetic acid or ammoniacal liquor to be adjusted to pH7.0, obtain each metal conditioner.

[table 7]

Storage stability in above-mentioned table 7, liquid appearance and liquid viscosity based on preserving under institute's fixed temperature after 1 week are evaluated with following benchmark.Liquid viscosity, measuring 20 ℃ of temperature, is used Type B rotational viscosimeter, under the condition of revolution 60rpm, measures.　

Zero: liquid appearance is transparent, viscosity is below 2.5mPa s.　

the manufacture of surface treatment plate (surface treatment method)

Embodiment 67～86 and comparative example 14 and 15

For thickness of slab 0.6mm two sides electrogalvanizing steel plate (the weight per unit area 20g/m of EG material, one side ²) surface, the aqueous solution of the concentration 2% of alkali cleaner (Japanese シービーケミカル society system, trade(brand)name " ケミ Network リー Na ー 561B ") has been dissolved in use, under the condition of temperature 60 C, carry out 2 minutes spray treatment, carry out thus degreasing, remove the dust or the oil that on surface, adhere to, after washing, be dried.As described in Table 8, utilize rolling method, gained on the steel plate galvanized of skimming treatment, be coated with above-described embodiment and comparative example in each metal conditioner of obtaining, carry out baking in 20 seconds so that starting material arrive temperature is 100 ℃, obtain surface treatment plate.For metal conditioner, use the metal conditioner at initial stage after manufacturing, and at 20 ℃, preserve the metal conditioner after 7 days.

Each surface treatment plate of the making for using the metal conditioner of preparing in each embodiment and comparative example, the test method based on following, carries out the test of erosion resistance and electroconductibility after erosion resistance, degreasing.Its test-results is shown in following table 8.In addition, for each surface treatment plate, the result of carrying out aftermentioned fitness test is, each surface treatment plate is not all found peeling off of surface treatment epithelium, and adaptation is good.

[table 8]

test method:

Erosion resistance:

For each surface treatment plate of gained, by the end face portion of each surface treatment plate and back part sealing, carry out the salt spray testing (SST) based on JIS Z 2371.According to following benchmark, carry out the rusting rate after 120 hours and 240 hours evaluation test time.　

A: do not observe and get rusty.　

B: 5% of the not enough entire area of getting rusty.　

C: get rusty account for entire area more than 5% and less than 10%.　

D: get rusty account for entire area more than 10% and less than 50%.　

E: get rusty and account for the more than 50% of entire area.

Erosion resistance after degreasing:

Each surface treatment plate for gained, the aqueous solution of the concentration 2% of alkali cleaner (Japanese パーカライ Application ジ Application グ (strain) makes " FC-4460 ") has been dissolved in use, under the condition of 60 ℃, 2 minutes spray treatment, carry out degreasing, then wash, be dried, obtain degreasing rear surface disposable plates.By the end face portion of this degreasing rear surface disposable plates and back part sealing, carry out the salt spray testing (SST) based on JIS Z 2371.According to the benchmark with identical in above-mentioned erosion resistance, the rusting rate of 120 hours evaluation test time.

Electroconductibility:

A: whole 10 times

B:6～9 time

C:1～5 time

D:0 time.

Fitness test:

On the surface treatment epithelium face of each surface treatment plate, with cutting knife, to arrive the mode of matrix, in 10mm four directions, make checker so that form the square of 100 1mm * 1mm.To push the mode of this checker portion from outside, carry out drawing test (7mm extruding) afterwards, closely sealed glassine paper adhesive tape in the processing department through extruding, while peeling off in moment, evaluates the extent of exfoliation of surface treatment epithelium.

Claims

1. metal conditioner use binder composition, is characterized in that,

By making (a) there is the silane coupling agent of at least one primary amino or secondary amino group and hydrolization group and (b) there is the silane coupling agent of at least one epoxy group(ing) and hydrolization group, further and (c) formula according to circumstances: (R) _4-n-Si-(X) _nat least one alkoxysilane compound containing trialkylsilyl group in molecular structure reaction representing and reaction product (A);

Water,

Above-mentioned formula: (R) _4-n-Si-(X) _nin, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, and X represents alkoxyl group, and n represents 1～3 integer,

2. aqueous adhesive composition claimed in claim 1, wherein,

Silane coupling agent (a) is at least one compound being selected from N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330, N-(2-amino-ethyl) APTES, 3-TSL 8330, APTES

Silane coupling agent (b) is at least one compound being selected from γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl triethoxyl silane.

3. aqueous adhesive composition claimed in claim 1, wherein, based on above-mentioned (a), (b) and (c) total amount 100 mass parts of composition, is combined with alkoxysilane compound containing trialkylsilyl group in molecular structure (c) with the ratio of 5～70 mass parts.

4. aqueous adhesive composition claimed in claim 1, wherein, organoalkoxysilane (c) is selected from methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, amyltrimethoxysilane, hexyl Trimethoxy silane, octyl group Trimethoxy silane, methyl three (methoxy ethoxy) silane, ethyl three (methoxy ethoxy) silane, 3, 3, 3-trifluoro propyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (methoxy ethoxy) silane, at least one trialkoxy silane in phenyltrimethoxysila,e and phenyl triethoxysilane.

5. aqueous adhesive composition claimed in claim 1, wherein, sour stablizer (B) is phosphoric acid or nitric acid.

6. aqueous adhesive composition claimed in claim 1, wherein, based on reaction product (A) 100 mass parts, contains sour stablizer (B) 1～10 mass parts.

7. aqueous adhesive composition claimed in claim 1, wherein, solids component ratio is 5～30 quality %, and organic solvent amount is below 3 quality %,

This aqueous adhesive composition be do not have flash-point without hazardous material.

8. metal conditioner, it contains metal conditioner use binder composition and the rust-preventive agent described in any one in claim 1～7.

9. metal conditioner claimed in claim 8, wherein, solids component 100 mass parts based on reaction product (A), contain rust-preventive agent 0.1～100 mass parts.

10. water-based metal surface treatment agent claimed in claim 8, it further contains organic resin and/or the wax of water-soluble or water dispersible.

The surface treatment method of 11. metallic substance, is characterized in that, the metal conditioner described in any one in claim 8～10 is coated to metal material surface, makes it dry, and at this metal material surface, forming dry epithelium weight is 0.05～3.0g/m ²surface treatment epithelium.

The manufacture method of the aqueous adhesive composition in 12. claims 1～7 described in any one, is characterized in that,

Make (a) there is the silane coupling agent of at least one primary amino or secondary amino group and hydrolization group and (b) there is the silane coupling agent of at least one epoxy group(ing) and hydrolization group, further and (c) formula according to circumstances: (R) _4-n-Si-(X) _nat least one alkoxysilane compound containing trialkylsilyl group in molecular structure representing reacts and generation silane reaction product (A'), then by interpolation in silane reaction product (A'), being selected from phosphoric acid is that acid compound and nitric acid are after at least one sour stablizer (B) in acid compound is prepared the aqueous liquid of silane reaction product, carry out desolventizing

Above-mentioned formula: (R) _4-n-Si-(X) _nin, R represents according to circumstances optionally not had the alkyl of the carbonatoms 1～18 of reactive substituting group replacement, and X represents alkoxyl group, and n represents 1～3 integer.

The manufacture method of the aqueous adhesive composition described in 13. claims 12, wherein,

In water medium, the silane coupling agent (a) that makes to have at least one primary amino or secondary amino group and the hydrolization group reaction that is hydrolyzed, then by this hydrolysis reactant and there is the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group and according to circumstances further and alkoxysilane compound containing trialkylsilyl group in molecular structure (c) in containing the water medium of acid neutralizing agent, mix, be hydrolyzed and react and addition reaction, generate silane reaction product (A').

The manufacture method of the aqueous adhesive composition described in 14. claims 12, wherein,

In water medium, make to have the silane coupling agent (b) of at least one epoxy group(ing) and hydrolization group and according to circumstances further make alkoxysilane compound containing trialkylsilyl group in molecular structure (c) be hydrolyzed after reaction, add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group, in containing the water medium of acid neutralizing agent, be hydrolyzed and react and addition reaction, generate silane reaction product (A').

The manufacture method of the aqueous adhesive composition described in 15. claims 12, wherein,

In organic solvent or under the condition of non-solvent, make the silane coupling agent (b) that there is the silane coupling agent (a) of at least one primary amino or secondary amino group and hydrolization group and there is at least one epoxy group(ing) and hydrolization group carry out addition reaction, then this addition reaction is dissolved or dispersed in the water medium that contains acid neutralizing agent, the reaction that is hydrolyzed, generates silane reaction product (A').

The manufacture method of the aqueous adhesive composition described in 16. claims 12, wherein,

Under alcoholic solvent or the condition at non-solvent, the silane coupling agent (b) and the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) that make to have at least one epoxy group(ing) and hydrolization group are hydrolyzed after reaction, this hydrolysis reactant is dissolved or dispersed in the water medium that contains acid neutralizing agent, then add the silane coupling agent (a) with at least one primary amino or secondary amino group and hydrolization group, be hydrolyzed and react and addition reaction, generate silane reaction product (A').