CN101153196B - Aqueous composition for single rust-proof treatment of metal panel and single rust-proof treatment metal panel - Google Patents

Abstract

The present invention provides anaqueous composition for one time process of metal plate which has excellent close property, anti-rusting and processability for the metal plates such as steel plate and aluminum, even not processed by the chrome treatment, oxidation treatment, metallic compound treatment, coarse graining treatment, etc. The anaqueous composition includes the anaqueous compound of composite resin (ABC) formed by dissolving or dispersing the composite resin (ABC) to anaqueous agent and the solidifying agent (D) of the composite resin (ABC). The polysiloxane chain segment (B) of the composite resin (AB) of the composite resin (ABC) is combined with the polysiloxane chain segment (C) of the condensate (c) of alkyl group Trialkoxysilane with one to three alkyl group carbon atoms through the silicon-oxygen key. The polymer segment (A) and polysiloxane chain segment (B) having the neutralized acid radical in the composite resin (AB) are combined through chemical bond. The present invention also provides a one time rust prevention treatment metal plate for one time rust prevention treatment by using the aqueous composition.

Description

The once antirust processing use of metal sheet compsn and once antirust processing metal sheet

Technical field

The present invention relates to be used for the waterborne compositions of the once antirust processing of metal sheets such as steel plate, aluminium sheet.Particularly, the present invention relates to excellent with the adaptation of metal sheet, can give the metal sheet once antirust processing use compsn of excellent rust-preventing characteristic, processibility etc. and use the once antirust processing use of this metal sheet compsn to carry out the once antirust processing metal sheet of once antirust processing metal sheet surface.

Background technology

Be to adopt to carry out plating or molten zinc plating and further carry out the once antirust processing that chromium handles above that and handle steel plate for metal machining object such as building materials, automobile, household electrical appliances, X-former, phonomoter with chromium in the past.Carrying out that this chromium handles is in order to improve the rust-preventing characteristic of steel plate, but quilt such as chromic salt that use point out influence environment, health risk etc., so require to develop the non-chromium processing steel plate that does not carry out this chromium processing.

On the other hand, from improving considerations such as processibility, punching property, rust-preventing characteristic, adopted various organic resins for example the surface treatment agent of acrylic resin, urethane resin, olefin resin, epoxy resin etc. also using.But, only contain the surface treatment agent of these organic resins because rust-preventing characteristic is not enough, use with above-mentioned chromium treatment agent combination usually, thereby still require to shift to non-chromium.

To these requirements, for example reported about by organic resin and flakey silicon dioxide granule, also have non-chromium steel plate that non-chromium rust-preventive agent constitutes technology (reference example such as patent documentation 1) with surface treatment agent.

But the surface treatment agent of record in the above-mentioned patent documentation 1 is owing to contain flakey silicon-dioxide, so as the stability existing problems of compsn, and rust-preventing characteristic is also insufficient.

In addition, aluminium is used to multiple article such as building materials, automobile component, household electrical appliances, daily necessities owing to have excellent processibility, light weight.The aluminium sheet that is used for above-mentioned article is implemented surface treatment usually,, surface-functional antirust to give and keep outward appearance etc.This surface treatment generally is to carry out through forming organic coating film in surface of aluminum plate.But it is difficult directly forming organic coating film in surface of aluminum plate, and what adopt so far is surface of aluminum plate to be carried out once oxidation handle, and perhaps carries out metallic compound and handles, and perhaps carries out roughened with sandblasting etc., forms the method for organic coating film subsequently.And these methods must be carried out repeatedly surface treatment according to purpose, and not only technology is numerous and diverse, but also have the high such problem of manufacturing cost.

Particularly require the situation of the purposes of surface hydrophilicity as aluminium fin of the important use of aluminium sheet etc.; Must carry out hydrophilic treatment, thereby requiring to develop to carry out these surface-treated surface treatment agents together as the antirust processing of the aluminium sheet of base material and final film coated surface.

To these requirements; For example reported that it is the technology of resin as the compound coating of organic-inorganic of principal constituent that use contains acid-organosilicon crylic acid, said silicone acrylic resin obtains (reference example such as patent documentation 2) through acrylic resin and organopolysiloxane reaction.

But rust-preventing characteristic, the wetting ability of the surface treatment agent of record are all insufficient in the above-mentioned patent documentation 2, are difficult to use during actual the use.

Patent documentation 1: the spy opens the 2003-253462 communique

Patent documentation 2: the spy opens the 2004-291445 communique

Summary of the invention

The technical problem that invention will solve

The problem that the present invention will solve is to provide a kind of chromium processing, oxide treatment, metallic compound processing, roughened etc. of not needing; Metal sheets such as steel plate, aluminium sheet are demonstrated excellent adaptation, and the metal sheet once antirust processing use compsn of excellences such as rust-preventing characteristic, processibility and use the once antirust processing use of this metal sheet compsn to carry out the once antirust processing metal sheet of once antirust processing.

The technical scheme of dealing with problems

The inventor furthers investigate in order to solve above-mentioned problem repeatedly; The Water-borne modification thing that the result finds to contain compound resin (ABC) with can with the surface treatment use compsn of the solidifying agent (D) of this compound resin (ABC) reaction; Even do not carry out chromium processing, oxide treatment, metallic compound processing, roughened etc.; Also can give excellent rust-preventing characteristic, processibility etc. to various metal sheets; And the especially suitable once antirust processing use compsn of the once antirust processing use of this metal sheet compsn as steel plate, aluminium sheet; When being used for the once antirust processing of steel plate; Obtain all excellent once antirust processing steel plate of adaptation, rust-preventing characteristic, processibility, scratch resistance easily; When being used for the once antirust processing of the metal sheet of aluminium sheet; Obtain all excellent once antirust processing aluminium sheet of adaptation, rust-preventing characteristic, processibility, wetting ability easily, the Water-borne modification thing of said compound resin (ABC) is to dissolve or be dispersed in the aqueous medium and form through silicon-oxygen key bonded compound resin (ABC) by the ZGK 5 segment (B) of the compound resin (AB) of chemical bond combination and from the ZGK 5 segment (C) of the condenses (c) of the alkyltrialkoxysilaneand of alkyl carbon atoms several 1～3 through the polymer segment (A) with the acidic group that neutralize and ZGK 5 segment (B).Thus, accomplished the present invention.

Promptly; The present invention relates to the once antirust processing use of a kind of metal sheet compsn; It is characterized in that; Contain the Water-borne modification thing of compound resin (ABC) and the solidifying agent (D) of said compound resin (ABC), the ZGK 5 segment (B) of the compound resin (AB) that polymer segment (A) and the ZGK 5 segment (B) of the Water-borne modification thing of said compound resin (ABC) through having the acidic group that neutralized combined by chemical bond dissolves or is dispersed in the aqueous medium and form through silicon-oxygen key bonded compound resin (ABC) with ZGK 5 segment (C) from the condenses (c) of the alkyltrialkoxysilaneand of alkyl carbon atoms several 1～3.

In addition, the present invention relates to the once antirust processing use of a kind of steel plate compsn, it is characterized in that, comprise the once antirust processing use of above-mentioned metal sheet compsn.The invention still further relates to the once antirust processing use of a kind of aluminium sheet compsn, it is characterized in that, comprise the once antirust processing use of above-mentioned metal sheet compsn.

In addition, the present invention relates to a kind of once antirust processing metal sheet, it is characterized in that, its metal sheet for using the once antirust processing use of above-mentioned metal sheet compsn to carry out once antirust processing.The invention still further relates to a kind of once antirust processing steel plate, it is characterized in that, its steel plate for using the once antirust processing use of above-mentioned steel plate compsn to carry out once antirust processing.The invention still further relates to a kind of once antirust processing aluminium sheet, it is characterized in that, its aluminium sheet for using the once antirust processing use of above-mentioned aluminium sheet compsn to carry out once antirust processing.

The beneficial effect of the invention

Even the once antirust processing use of metal sheet of the present invention compsn does not carry out chromium processing, oxide treatment, metallic compound processing, roughened etc., also can give excellent rust-preventing characteristic, processibility etc. to various metal sheets.The especially suitable once antirust processing use compsn of the once antirust processing use of this metal sheet compsn as steel plate, aluminium sheet; When being used for the steel plate purposes; Obtain all excellent once antirust processing steel plate of adaptation, rust-preventing characteristic, processibility, scratch resistance easily; When being used for the aluminium sheet purposes, obtain all excellent once antirust processing aluminium sheet of adaptation, rust-preventing characteristic, processibility, wetting ability easily.

Embodiment

The metal sheet once antirust processing use compsn that the present invention relates to below is described particularly and is used the once antirust processing use of this metal sheet compsn to carry out the once antirust processing metal sheet of once antirust processing.

The ZGK 5 segment (B) of the compound resin that uses among the present invention (ABC) compound resin (AB) that can be polymer segment (A) with the acidic group that neutralized and ZGK 5 segment (B) be combined by chemical bond with from the ZGK 5 segment (C) of the condenses (c) of the alkyltrialkoxysilaneand of alkyl carbon atoms several 1～3 through silicon-oxygen key bonded compound resin (ABC), can enumerate the compound resin that for example has following structure: ZGK 5 segment (B) is chemically combined compound resin with Grafting Structure on the side chain of the polymer segment with the acidic group that neutralized (A); ZGK 5 segment (B) have in above-mentioned polymer segment (A) terminal chemically combined block structure compound resin ZGK 5 segment (B) with from the ZGK 5 segment (C) of the condenses (c) of the alkyltrialkoxysilaneand of alkyl carbon atoms several 1～3 compound resin through silicon-this structure of oxygen key Chemical bond.

The not special restriction of the above-mentioned polymer segment (A) that is had as for above-mentioned compound resin (ABC) and the Chemical bond of above-mentioned ZGK 5 segment (B); Can enumerate combination of following structural formula (S-1) for example or following structural formula (S-2) etc.; Wherein consider the especially preferred compound resin that uses combination with structural formula (S-1) from the angle of filming that can form rust-preventing characteristic, have excellent weather resistance.

[Chemical formula 1]

Here, the carbon atom in the structural formula (S-1) constitutes the part of above-mentioned polymer segment (A), and Siliciumatom and Sauerstoffatom constitute the part of above-mentioned ZGK 5 segment (B).

[Chemical formula 2]

Here, the carbon atom in the structural formula (S-2) constitutes the part of above-mentioned polymer segment (A), and Siliciumatom constitutes the part of above-mentioned ZGK 5 segment (B).

For above-mentioned compound resin (ABC) is dispersed or dissolved in the aqueous medium; The polymer segment (A) that constitutes above-mentioned compound resin (ABC) is necessary for the polymer segment with the acidic group that neutralized; Wherein has acidic group and with Siliciumatom bonded hydroxyl and/or with the polymkeric substance of Siliciumatom bonded hydrolization group (being designated hereinafter simply as Siliciumatom bonded hydroxyl and/or hydrolization group) (a ') or as the polymer segment of the polymkeric substance (a) of its corrective from easily carrying out chemically combined angle consideration with Siliciumatom bonded hydroxyl or with Siliciumatom bonded hydrolization group hydrolytic condensation with the combination of above-mentioned structural formula (S-1), especially be preferably coming from ZGK 5 segment (B) or its synthesis material have.Above-mentioned polymkeric substance (a ') and polymkeric substance (a) are so long as have acidic group or the polymkeric substance beyond the ZGK 5 of the acidic group that neutralized gets final product; Can enumerate for example vinyl based polymers such as acrylic acid polymer, fluoroolefin polymkeric substance, vinyl ester polymer, aromatic vinyl polymer, polyolefin polymer as its kind; Polyether polyols with reduced unsaturation, polyester polymers, polyether polymer etc.; Wherein especially preferred vinyl based polymer and polyether polyols with reduced unsaturation, more preferably acrylic acid polymer.

Acidic group as in the above-mentioned polymkeric substance (a ') can be enumerated for example carboxyl, phosphate, phosphate ester acid base, phosphorous acid base, sulfonic group, sulfino etc., considers from the skeleton that imports to compound resin (ABC) easily, especially preferred carboxyl.

As the basic cpd that uses during above-mentioned acidic group in neutralization for example can use methylamine, n n dimetylaniline, Trimethylamine 99, ethamine, diethylamine, triethylamine, 2-monoethanolamine, organic amine such as 2-dimethylaminoethanol; Inorganic alkaline compounds such as ammonia, sodium hydroxide, Pottasium Hydroxide; Quaternary ammonium hydroxides such as TMAH, 4-n-butyl ammonium hydroxide, trimethyl benzyl volatile caustic etc. especially preferably use organic amine and ammonia (can be ammoniacal liquor).

Being dispersed or dissolved in the angle that the aqueous dispersion that forms the aqueous medium or the aqueous solution keeps good storage stability from above-mentioned compound resin (ABC) considers; The above-mentioned compound resin (ABC) of the preferred relative 100 weight % of the acidic group of the neutralization in the above-mentioned polymkeric substance (a) exists with the ratio of 0.1～20 weight %, and more preferably the ratio with 0.2～10 weight % exists.

In addition; As in the above-mentioned polymkeric substance (a ') with Siliciumatom bonded hydrolization group so long as the functional group that can generate with Siliciumatom bonded hydroxyl (silanol group) through hydrolysis get final product; For example can enumerate with Siliciumatom bonded halogen atom, with Siliciumatom bonded alkoxyl group, with Siliciumatom bonded acyloxy, with Siliciumatom bonded phenoxy, with Siliciumatom bonded sulfydryl, amino with the Siliciumatom bonded, with Siliciumatom bonded carboxamido-group, with Siliciumatom bonded amino oxygen base, with Siliciumatom bonded imino-oxygen base, with Siliciumatom bonded thiazolinyl oxygen base etc.; Wherein from the reaction that can easily be hydrolyzed; And the angle that can easily remove reacted by product is considered, especially preferred and Siliciumatom bonded alkoxyl group.

Above-mentioned polymer segment (A) in the scope of the effect of not damaging the present invention performance, can have except the acidic group that neutralize, and Siliciumatom bonded hydroxyl and with other functional groups the Siliciumatom bonded hydrolization group.As other such functional groups can enumerate the carboxyl that for example is not neutralized, by end capped carboxyl, acid anhydride, hydroxyl, by end capped hydroxyl, cyclocarbonate radical, epoxy group(ing), carbonyl, primary amide base, secondary amide base, carbamate groups, polyethylene glycol groups, W 166 base and by the group of following structures formula (S-3) expression etc.

[chemical formula 3]

ZGK 5 segment (B) as constituting above-mentioned compound resin (ABC) can be enumerated the segment that for example comes from the ZGK 5 with Siliciumatom bonded hydroxyl and/or hydrolization group.Here, above-mentioned and Siliciumatom bonded hydrolization group can enumerate with in above-mentioned polymer segment (A), put down in writing with the identical group of Siliciumatom bonded hydrolization group, preferred group is also identical.

Especially preferably have by the formula (S-4) and (S-5) segment of structure of expression as above-mentioned ZGK 5 segment (B).Have by formula (S-4) and (S-5) the above-mentioned ZGK 5 segment of the structure of expression owing to have excellences such as three-dimensional netted polysiloxane structure, the solvent resistance of filming that obtains, weathering resistance.

[chemical formula 4]

[chemical formula 5]

General formula (S-4) and (S-5) in, R ¹For with the organic group of Siliciumatom bonded carbonatoms 4～12, R ²And R ³Respectively be independently with Siliciumatom bonded methyl or with Siliciumatom bonded ethyl.Here, R ¹Especially be preferably the alkyl with Siliciumatom bonded carbonatoms 4～12, more preferably the alkyl of phenyl or carbonatoms 4.R ²And R ³Preferably be with Siliciumatom bonded methyl or with Siliciumatom bonded ethyl, more preferably be and Siliciumatom bonded methyl.

As have by above-mentioned general formula (S-4) and (S-5) the ZGK 5 segment of structure of expression can enumerate segment from the ZGK 5 that obtains through the hydrolytic condensation hydrocarbyl alkoxy silanes, said hydrocarbyl alkoxy silanes be preferably have with single alkyl trialkoxy silane of the organic group (being designated hereinafter simply as " organic group of Siliciumatom bonded carbonatoms 4～12 ") of Siliciumatom bonded carbonatoms 4～12 and/or have 2 with Siliciumatom bonded methyl and/or with the dialkyl dialkoxy silicane of Siliciumatom bonded ethyl (being designated hereinafter simply as " Siliciumatom bonded methyl and/or ethyl ").These ZGK 5 segments have organic group and the Siliciumatom bonded hydroxyl and/or the hydrolization group of Siliciumatom bonded carbonatoms 4～12; And/or; 2 with Siliciumatom bonded methyl and/or ethyl and with Siliciumatom bonded hydroxyl and/or hydrolization group, can have any one structure in wire, branch-like, the ring-type.

As the organic group of above-mentioned Siliciumatom bonded carbonatoms 4～12 for example can enumerate all with Siliciumatom bonded carbonatoms be 4～12 alkyl, naphthenic base, aryl, aralkyl etc.Here, these groups also can have substituting group.

Organic group as this Siliciumatom bonded carbonatoms 4～12; Preferably with Siliciumatom bonded alkyl; For example can enumerate all and alkyl such as Siliciumatom bonded normal-butyl, isobutyl-, n-hexyl, n-octyl, dodecyl, cyclohexyl methyl; Naphthenic base such as cyclohexyl, 4-methylcyclohexyl, aryl such as phenyl, 4-aminomethyl phenyl, aralkyl such as benzyl etc.More preferably with Siliciumatom bonded phenyl or with Siliciumatom bonded carbonatoms be 4 alkyl.

The ZGK 5 segment (C) that constitutes above-mentioned compound resin (ABC) is the segment of the condenses (c) of the alkyltrialkoxysilaneand that comes from alkyl carbon atoms several 1～3, the condenses (c) of the alkyltrialkoxysilaneand of the alkyl carbon atoms of this use several 1～3 have with Siliciumatom bonded hydroxyl and/or with Siliciumatom bonded alkoxyl group.

Condenses (c) as the abovementioned alkyl trialkoxy silane preferably has the structure by formula (S-6) expression.From ZGK 5 segment with condenses of the alkyltrialkoxysilaneand of structure shown in the formula (S-6) owing to have three-dimensional netted polysiloxane structure, so excellences such as the solvent resistance of filming that obtains, weathering resistancies.

[chemical formula 6]

Here, the R in the general formula (S-6) ⁴Alkyl for carbonatoms 1～3.

Above-mentioned compound resin (ABC) is considered from obtaining the excellent especially angle of filming of adaptation, rust-preventing characteristic, resistance to cracking; Preferred relative 100 weight part compound resins (ABC); ZGK 5 segment (B) and be 25～85 weight parts, more preferably 45～85 weight parts from the total amount (B+C) of the ZGK 5 segment (C) of the condenses (c) of alkyltrialkoxysilaneand.

In addition; Above-mentioned compound resin (ABC) is considered from obtaining the excellent especially angle of filming of weather resistance, resistance to cracking; Preferred relative 100 weight part compound resins (ABC); Amount from the ZGK 5 segment (C) of the condenses (c) of abovementioned alkyl trialkoxy silane is 15～60 weight parts, more preferably 30～60 weight parts.

Above-mentioned compound resin (ABC) can in all sorts of ways and make, and is especially preferably made by the technology that comprises following manufacturing process (I)～(II).

(I) to the condensation that is hydrolyzed of the polymkeric substance that has acidic group and Siliciumatom bonded hydroxyl and/or hydrolization group simultaneously (a ') and hydrocarbyl alkoxy silanes (b) and/or its hydrolytic condensate (b-1), the operation of the polymer segment (A ') that obtains origin autohemagglutination compound (a ') and the compound resin that forms chemical bond from the ZGK 5 segment (B) of hydrocarbyl alkoxy silanes (b) (A ' B);

(II) then; To the condensation that is hydrolyzed of the condenses (c) of the alkyltrialkoxysilaneand of the carbonatoms 1～3 of the compound resin that obtains (A ' B) and alkyl; Process by the ZGK 5 segment (B) of compound resin (A ' B) with from the ZGK 5 segment (C) of the condenses (c) of the alkyltrialkoxysilaneand of the carbonatoms 1～3 of alkyl behind silicon-oxygen key bonded compound resin (A ' BC), obtain the operation of compound resin (ABC) with the acidic group in this compound resin of basic cpd neutralization (A ' BC); Perhaps; With in the basic cpd with the compound resin of gained (A ' B) in acidic group and after processing compound resin (AB); The condenses (c) of the alkyltrialkoxysilaneand of the carbonatoms 1～3 of hydrolytic condensation alkyl, obtain by the ZGK 5 segment (B) of compound resin (AB) with from the ZGK 5 segment (C) of the condenses (c) of the alkyltrialkoxysilaneand of the carbonatoms 1～3 of alkyl operation through silicon-oxygen key bonded compound resin (ABC).

Hydrolysis-condensation reaction can in all sorts of ways and react in the above-mentioned ME, but it is easier with the method that catalyzer reacts in the way of ME, to supply with water, therefore preferably.

Here, the said hydrolyzed condensation reaction be meant said hydrolyzed property group a part since water etc. influence the generation hydrolysis, form hydroxyl, the condensation reaction of then between this hydroxyl, hydrolization group, carrying out.

Above-mentioned polymkeric substance (a ') be the polymkeric substance that has acidic group and Siliciumatom bonded hydroxyl and/or hydrolization group simultaneously; Except acidic group was not neutralized, the polymkeric substance (a) that has the acidic group that neutralized and Siliciumatom bonded hydroxyl and/or hydrolization group with above-mentioned the time was identical.

When using the vinyl based polymer as above-mentioned polymkeric substance (a '), this vinyl polymer can be through for example making the vinyl monomer that contains acidic group and containing the vinyl monomer of Siliciumatom bonded hydroxyl and/or contain the vinyl monomer of Siliciumatom bonded hydrolization group and other vinyl monomers of adding as required carry out polymerization and make.

Can enumerate the various vinyl monomers of acidic groups such as for example containing carboxyl, phosphate, phosphate ester acid base, phosphorous acid base, sulfonic group, sulfino as the above-mentioned vinyl monomer that contains acidic group, especially preferably contain the vinyl monomer of carboxyl (can be the acid anhydride).

For example can enumerate unsaturated carboxylic acid classes such as (methyl) vinylformic acid, 2-carboxy ethyl (methyl) propenoate, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid as the above-mentioned carboxylic acid group's of containing vinyl monomer; The anhydrides of unsaturated polycarboxylic acid such as maleic anhydride, itaconic anhydride; The anhydrides of unsaturated monocarboxylic acid such as acrylic anhydride, methylacrylic acid; The mixed acid anhydride of saturated carboxylic acids such as unsaturated carboxylic acid such as vinylformic acid, methylacrylic acid and acetic acid, propionic acid, phenylformic acid; The various monoesters classes (half ester class) of saturated dicarboxylic acid classes such as monomethyl itaconate, the positive butyl ester of methylene-succinic acid list, monomethyl maleate, the positive butyl ester of toxilic acid list, monomethyl fumarate, the positive butyl ester of fumaric acid list and saturated monohydroxy alcohol class; Single vinyl esters of saturated dicarboxylic acid such as hexanodioic acid list vinyl acetate, mono succinate vinyl acetate; The anhydrides of saturated polycarboxylic acids such as succinyl oxide, Pyroglutaric acid, anhydride phthalic acid, trimellitic acid 1,2-anhydride and contain the addition reaction resultant with the ethene base system monomer class of carbon atom bonded hydroxyl, above-mentioned monomer class that contains carboxyl and lactone addition reaction and the various monomer classes that obtain.Consider from the angle that imports to vinyl polymer easily, especially unsaturated carboxylic acid class such as preferred (methyl) vinylformic acid.

In addition; Above-mentioned carboxylic acid group can be by end-blocking; Can enumerate the ethene base system monomer class that for example trimethyl silyl (methyl) propenoate, dimethyl-tertiary butyl silyl (methyl) propenoate, trimethyl silyl crotonate etc. contain the silyl ester group as having this ethene base system monomer by end capped carboxyl; 1-ethoxyethyl group (methyl) propenoate, 2-methoxyl group-2-(methyl) acryloxy propane, 2-(methyl) acryloxy THF etc. contain the monomer class of semi-acetal ester group or hemiketal ester group, and (methyl) tert-butyl acrylate, the Ba Dousuan tert-butyl ester etc. contain the monomer class of tert-butyl ester base.

Can enumerate for example trihydroxy-vinyl silanes, oxyethyl group dihydroxy ethylene base silane, diethoxy hydroxyl vinyl silanes, dichloro hydroxyl vinyl silanes, 3-(methyl) acryloxy propyl group ortho-siliformic acid, 3-(methyl) acryloxy propyl group methyl dihydroxyl silane etc. as above-mentioned containing with the vinyl monomer of Siliciumatom bonded hydroxyl.

Can use the vinyl monomer that for example has by the hydrolization group of formula (S-7) expression as the above-mentioned vinyl monomer that contains with Siliciumatom bonded hydrolization group.

[chemical formula 7]

Here, the R in the general formula (S-7) ⁵Be 1 valency organic groups such as alkyl, aryl, aralkyl, R ⁶Be halogen atom, alkoxyl group, acyloxy, phenoxy, aryloxy, sulfydryl, amino, carboxamido-group, amino oxygen base, imino-oxygen base or thiazolinyl oxygen base, b is 0～2 integer.

Vinyl monomer as having the hydrolization group of being represented by above-mentioned general formula (S-7) can be enumerated for example vinyltrimethoxy silane; Vinyltriethoxysilane; The vinyl methyl dimethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Vinyltriacetoxy silane; Vinyl trichloro silane; 2-trimethoxysilylethylgroup group vinyl ether; 3-(methyl) acryloxy propyl trimethoxy silicane; 3-(methyl) acryloxy propyl-triethoxysilicane; 3-(methyl) acryloxy propyl group methyl dimethoxysilane; 3-(methyl) acryloxy propyltrichlorosilan etc.From the reaction that can easily be hydrolyzed, and the angle consideration that can easily remove reacted by product, especially preferred vinyl Trimethoxy silane, 3-(methyl) acryloxy propyl trimethoxy silicane.

In addition; For example can enumerate (methyl) alkyl-acrylates that (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate etc. have the alkyl of carbonatoms 1～22 as other above-mentioned vinyl monomers; (methyl) vinylformic acid aralkyl ester classes such as (methyl) benzyl acrylate, (methyl) vinylformic acid 2-phenyl chlorocarbonate; (methyl) vinylformic acid cycloalkyl ester classes such as (methyl) cyclohexyl acrylate, (methyl) IBOA; (methyl) vinylformic acid ω-alkoxy alkyl classes such as (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 4-methoxyl group butyl ester; Vinylbenzene, to aromatic vinyl base system monomer classes such as t-butyl styrene, alpha-methyl styrene, Vinyl toluenes; Vinyl carboxylates classes such as vinyl acetate, propionate, new vinyl acetate acid, vinyl benzoate; The alkyl esters of Ba Dousuan such as methyl crotonate, ethyl crotonate; The dialkyl esters of unsaturated dibasic acids such as dimethyl maleate, n-butyl maleate, dimethyl fumarate, dimethyl itaconate, alpha-olefines such as ethene, propylene, fluoroolefin classes such as vinylidene, tetrafluoroethylene, R 1216, chlorotrifluoroethylene; Alkyl vinyl such as ethyl vinyl ether, n-butyl vinyl ether ethers; Naphthenic base vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, N, N-dimethyl-(methyl) acrylic amide, N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine, N-vinyl pyrrolidone etc. contain the monomer class of teritary amide base;

(methyl) vinylformic acid hydroxyalkyl acrylate classes such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester; 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether etc. contain the vinyl ethers of hydroxyl; 2-hydroxyethyl allyl ethers, 2-hydroxybutyl allyl ethers etc. contain the allyl ether series of hydroxyl, and these contain the addition reaction with lactone such as the ethene base system monomer class of carbon atom bonded hydroxyl and ε-GBL;

2-dimethyl aminoethyl (methyl) propenoate, 2-diethylamino ethyl (methyl) propenoate, 2-di amino-ethyl (methyl) propenoate, 3-dimethylaminopropyl (methyl) propenoate, 4-dimethylamino butyl (methyl) propenoate, N-[2-(methyl) acryloxy] ethyl morpholine etc. contain amino (methyl) esters of acrylic acid of uncle; Vinyl pyridine, N-VCz, N-vinylquinoline etc. contain the amino aromatic vinyl base system monomer class of uncle; N-(2-dimethylamino) ethyl (methyl) acrylic amide, N-(2-diethylamino) ethyl (methyl) acrylic amide, N-(the 2-di is amino) ethyl (methyl) acrylic amide etc. contain amino (methyl) acrylic amide of uncle; N-(2-dimethylamino) ethyl crotonic acid acid amides, N-(4-dimethylamino) butyl Ba Dousuan acid amides etc. contain the amino Ba Dousuan amides of uncle, and 2-dimethyl aminoethyl vinyl ether, 2-diethylamino ethyl vinyl ether, 4-dimethylamino butyl vinyl ether etc. contain the amino vinyl ethers of uncle etc.

Above-mentioned other vinyl monomers can be selected its kind and amount aptly according to surface of steel plate of the present invention is handled the characteristic that the use compsn is given in the scope of the effect of not damaging the present invention's performance.

In addition; In order to improve solvability or the dispersiveness of above-mentioned compound resin (ABC) to aqueous medium, above-mentioned polymkeric substance (a ') can use has the polymkeric substance that is selected from least a hydrophilic radical in the group that is formed by anionic property group, cationic group and nonionic group.

The vinyl monomer that the vinyl based polymer that can be used as above-mentioned polymkeric substance (a ') for example can contain acidic group through polymerization method polymerizations such as ontological idea of freedom base polymerization, solution free radical polymerization method, non-water-dispersion radical polymerizations is made with containing with the vinyl monomer of Siliciumatom bonded hydroxyl and/or contain with the vinyl monomer of Siliciumatom bonded hydrolization group and other vinyl monomers of adding as required.Consider the especially preferred so-called solution free radical polymerization method of making the vinyl based polymer through the above-mentioned vinyl monomer of radical polymerization in organic solvent that is suitable for from easy manufacturing.

During with the above-mentioned vinyl monomer of above-mentioned radical polymerization polymerization, can use polymerization starter as required.For example can enumerate 2 as this polymerization starter; 2 '-Diisopropyl azodicarboxylate, 2; 2 '-azo two (2; The 4-methyl pentane nitrile), 2,2 '-azo two azo cpd classes such as (2-methylbutyronitriles), peroxides such as t-butylperoxy pivarate, tert butyl peroxy benzoate, tert-butyl hydroperoxide 2-ethylhexanoate, ditertiary butyl peroxide, cumene hydroperoxide, di-isopropyl peroxycarbonates etc.

Can enumerate for example fatty family or alicyclic ring family hydro carbons such as normal hexane, normal heptane, octane, hexanaphthene, pentamethylene as above-mentioned organic solvent; Toluene, YLENE, ethylbenzene etc. are aromatic hydrocarbon based; Alcohols such as methyl alcohol, ethanol, propyl carbinol, glycol monomethyl methyl ether, propylene glycol monomethyl ether; Ester classes such as vinyl acetic monomer, n-butyl acetate, n-Amyl acetate, terepthaloyl moietie monomethyl ether acetate, propylene glycol monomethyl ether acetate; Ketones such as acetone, methylethylketone, MIBK, methyl-n-amyl ketone, pimelinketone; Diethylene glycol dimethyl ether, Diethylene Glycol dibutyl ether etc. gather alkane glycol dialkyl ether, and 1, ethers such as 2-glycol dimethyl ether, THF 、 diox; N-Methyl pyrrolidone, N, N,N-DIMETHYLACETAMIDE, ethylene carbonate etc., these solvents can be separately separately or make up more than 2 kinds and use.

Above-mentioned polymkeric substance (a ') preferably has the number-average molecular weight of 500～200,000 scope, more preferably has 700～100,000 scope, especially preferably has 1,000～50,000 scope.Polymkeric substance (a ') through use has the number-average molecular weight in such scope can prevent tackify and gelation, and can form filming of excellent in te pins of durability when making above-mentioned compound resin (ABC).

Then, describe to the hydrocarbyl alkoxy silanes (b) that in above-mentioned manufacturing process (I), is used to constitute ZGK 5 segment (B) and/or its hydrolytic condensate (b-1).

The not special restriction of above-mentioned hydrocarbyl alkoxy silanes (b); From making the excellent compound resin (ABC) of dispersion stabilization; And the angle of filming that can form excellent in te pins of durability considers, especially preferably have the organic group of carbonatoms 4～12 single alkyl trialkoxy silane, have the dialkyl dialkoxy silicane of 2 methyl and/or ethyl.

The hydrolytic condensate (b-1) of above-mentioned hydrocarbyl alkoxy silanes (b) so long as the condenses that obtains through hydrolytic condensation hydrocarbyl alkoxy silanes (b) get final product; Not special restriction, have through hydrolytic condensation the organic group of Siliciumatom bonded carbonatoms 4～12 single alkyl trialkoxy silane, have the condenses that the dialkyl dialkoxy silicane of 2 Siliciumatom bonded methyl and/or ethyl obtains and be preferably.

Can enumerate for example isobutyl-Trimethoxy silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane etc. as above-mentioned single alkyl trialkoxy silane with organic group of Siliciumatom bonded carbonatoms 4～12.

Can enumerate for example dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl-two n-butoxy silane, dimethyl-diacetoxy silane, diethylammonium dimethoxy silane, diethylammonium diacetoxy silane etc. as dialkyl dialkoxy silicane with 2 Siliciumatom bonded methyl and/or ethyl.

In these hydrocarbyl alkoxy silanes (b), from the reaction that can easily be hydrolyzed, and the angle consideration that can easily remove reacted by product, preferred isobutyl-Trimethoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne.And these hydrocarbyl alkoxy silanes (b) can be used separately, also can be also with more than 2 kinds.

In above-mentioned manufacturing process (I); Can use the hydrolytic condensate (b-1) of hydrocarbyl alkoxy silanes (b) fully separately; But consider from the angle of easily making compound resin (A ' B) through hydrolytic condensation; Preferably use hydrocarbyl alkoxy silanes (b) separately or, especially preferably use hydrocarbyl alkoxy silanes (b) separately also with hydrocarbyl alkoxy silanes (b) and its hydrolytic condensate (b-1).At this, use hydrocarbyl alkoxy silanes (b) to be meant separately and only use hydrocarbyl alkoxy silanes (b), also comprise and with the situation of the hydrocarbyl alkoxy silanes more than 2 kinds (b).

Hydrolysis-condensation reaction can in all sorts of ways and react in the above-mentioned manufacturing process (I), but the method for reacting through supply water and catalyzer in the way of above-mentioned manufacturing process (I) is easy, and is therefore preferred.

As catalyzer for example can use separately or and with the following catalyzer more than 2 kinds: inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid; Organic acids such as tosic acid, mono phosphoric acid ester isopropyl ester, acetic acid; Inorganic base such as sodium hydroxide, Pottasium Hydroxide; Titanate esters such as tetra isopropyl titanate, tetrabutyl titanate ester; 1; 8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), 1,5-diazabicyclo [4.3.0] carbon in the ninth of the ten Heavenly Stems-5-alkene (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butyl amine, dimethyl benzyl amine, monoethanolamine, imidazoles, 1-Methylimidazole etc. contain the compounds of basic nitrogen atom; Tetramethyl ammonium, 4-butyl ammonium, dilauryl dimethyl ammonium etc. have muriate, bromide, carboxylate salt, oxyhydroxide etc. as the anionic quaternary ammonium salts of pairing, tin carboxylate salts such as dibutyl tin diacetate, dibutyl tin diocatanoate, dibutyl tin two LAURIC ACID 99 MIN salt, dibutyl tin diacetyl acetone hydrochlorate, stannous octoate, Triple Pressed Stearic Acid tin etc.

With respect to the above-mentioned hydrocarbyl alkoxy silanes of 100 weight parts (b) and/or its hydrolytic condensate (b-1); Above-mentioned catalyzer preferably uses in the scope of 0.0001～10 weight part; More preferably use, use particularly preferably in the scope of 0.001～1 weight part in the scope of 0.0005～3 weight part.

In addition; 1 mole of hydrolization group that is had with respect to above-mentioned hydrocarbyl alkoxy silanes (b) and/or its hydrolytic condensate (b-1) and hydroxyl; The water that when carrying out the said hydrolyzed condensation reaction, uses is suiting more than 0.05 mole; Be preferably more than 0.1 mole, be preferably 0.5～3.0 mole especially.

Above-mentioned catalyzer and water can be supplied with together, also can supply with one by one, also can supply with the prior mixture that has mixed catalyzer and water.

The temperature of reaction of said hydrolyzed condensation reaction suits in 0～150 ℃ scope, preferably in 20～100 ℃ scope.In addition, the pressure as reaction can carry out under any one condition in normal pressure, pressurization or the decompression.

The by product that generates in the said hydrolyzed condensation reaction is an alcohol and water, if can reduce stability of the water-based curable coating compositions that obtains etc., also can remove through methods such as distillations.

Then, the condenses (c) to the alkyltrialkoxysilaneand of the carbonatoms 1～3 of the alkyl that in above-mentioned manufacturing process (II), is used to constitute ZGK 5 segment (C) carries out detailed explanation.

Alkyltrialkoxysilaneand as the carbonatoms 1～3 of abovementioned alkyl can be enumerated for example methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, sec.-propyl Trimethoxy silane etc.; From the reaction that can easily be hydrolyzed; And easily remove the angle consideration of reacted by product, especially preferable methyl Trimethoxy silane, ethyl trimethoxy silane.These alkyltrialkoxysilaneand can be used separately, also can be also with more than 2 kinds.

As the not special restriction of the method that obtains its condenses (c) by the abovementioned alkyl trialkoxy silane, can enumerate the whole bag of tricks, but easy through supplying with the be hydrolyzed method of condensation reaction of water and catalyzer, therefore preferably.

Water and catalyzer about use this moment can use under the condition identical with the hydrolysis-condensation reaction of above-mentioned manufacturing process (I).

In addition, in above-mentioned manufacturing process (II), except the condenses (c) of the alkyltrialkoxysilaneand of the carbonatoms 1～3 of alkyl, can and with other silane compounds and its hydrolytic condensate.

Can enumerate for example 4 functional alkoxysilanes compounds such as tetramethoxy-silicane, tetraethoxysilane or four positive propoxy silane, the hydrolytic condensate of this 4 functional alkoxysilanes compound etc. as other silane compounds.These compounds can and be used in the scope of the effect of not damaging the present invention's performance.

Also with above-mentioned 4 functional alkoxysilanes compounds and its hydrolytic condensate the time; Preferably with respect to the 100 moles of % of whole Siliciumatoms that constitute above-mentioned ZGK 5 segment (B) and ZGK 5 segment (C), in the Siliciumatom that this 4 functional alkoxysilanes compound and its hydrolytic condensate are had is no more than the scope of 20 moles of % and usefulness.

The once antirust processing use of metal sheet of the present invention compsn contains the Water-borne modification thing of the compound resin (ABC) that in aqueous medium, disperses or dissolves above-mentioned compound resin (ABC) and form, the aqueous dispersion of preferred compound resin (ABC) and the solidifying agent (D) of compound resin (ABC); Its method of manufacture is restriction not; Manufacturing can in all sorts of ways; Especially preferred make compound resin (ABC) through above-mentioned manufacturing process (I)～(II) after, make with the manufacturing process of following (III).

(III) compound resin (ABC) that obtains in the above-mentioned manufacturing process (II) is mixed with aqueous medium, disperse or dissolve compound resin (ABC) after, Water-borne modification thing and the operation of solidifying agent (D) of mixing the compound resin (ABC) of gained.

As the above-mentioned aqueous medium that uses in the present invention can enumerate water, can with water blended organic solvent and their mixture.As can enumerating for example alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol with water blended organic solvent; Ketone such as acetone, methylethylketone; Terepthaloyl moietie, Diethylene Glycol, Ucar 35 etc. gather the alkane glycols, gather the alkyl ether of alkane glycol, lactams such as N-N-methyl-2-2-pyrrolidone N-etc.In the present invention, can only make water, also can make water with can with the mixture of water blended organic solvent, can also only use can with water blended organic solvent.From security, the angle of the load of environment is considered, preferably only make water or water and can with the mixture of water blended organic solvent, especially preferably only make water.

Then, the acidic group that the solidifying agent (D) of the compound resin that uses among the present invention (ABC) so long as have can be had with compound resin (ABC) and/or get final product with the compound of the functional group of Siliciumatom bonded hydroxyl reaction can suitably be selected to use.As above-mentioned can with acidic group and/or with the functional group of Siliciumatom bonded hydroxyl reaction for example can enumerate NCO, blocked isocyanate base etc. can with carboxyl reaction and also can with the functional group of Siliciumatom bonded hydroxyl reaction; Epoxy group(ing), cyclocarbonate radical, carboxamido-group, hydroxyl 、 oxazolinyl, carbodiimide, diazanyl etc. can with the functional group of carboxyl reaction; N-hydroxymethyl amino, N-alkoxy methyl amino etc. can with Siliciumatom bonded hydroxyl reaction and also can with the functional group of carboxyl reaction, Siliciumatom bonded hydroxyl, Siliciumatom bonded hydrolization group, carboxyl etc. can with functional group of Siliciumatom bonded hydroxyl reaction etc.

Can enumerate the compound with Siliciumatom bonded hydroxyl and/or hydrolization group, the compound with NCO and Siliciumatom bonded hydroxyl and/or hydrolization group, the compound with epoxy group(ing) and Siliciumatom bonded hydroxyl and/or hydrolization group, polyisocyanate compound, blocked polyisocyanates compound, polyepoxides, gather cyclic carbonate compound, aminoresin, contain uncle or compound, multi-carboxy compound, the polyol 、 Ju oxazoline compound of secondary amide base, gather carbodiimide compound, polyhydrazide compound etc. as the concrete example of above-mentioned solidifying agent (D), especially preferably have the compound of Siliciumatom bonded hydroxyl and/or hydrolization group, compound, polyisocyanate compound, blocked polyisocyanates compound, polyepoxides 、 Ju oxazoline compound with epoxy group(ing) and Siliciumatom bonded hydroxyl and/or hydrolization group.These solidifying agent can be distinguished independent use perhaps also with more than 2 kinds.When using above-mentioned preferred solidifying agent, preferably with these preferred solidifying agent whiles and with polyhydrazide compound, aminoresin as above-mentioned solidifying agent (D).

In addition; Above-mentioned compound resin (ABC) has carboxyl or during the carboxyl that was neutralized, is preferably to use as above-mentioned solidifying agent (D) to have compound, the polyepoxides 、 Ju oxazoline combination of compounds of epoxy group(ing) and Siliciumatom bonded hydroxyl and/or hydrolization group.

For example can enumerate same compound of when making above-mentioned compound resin (ABC) illustrative spendable compound or their hydrolytic condensate etc. as above-mentioned compound with Siliciumatom bonded hydroxyl and/or hydrolization group with Siliciumatom bonded hydroxyl and/or hydrolization group.

Can enumerate for example 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, β-(3 as above-mentioned compound with epoxy group(ing) and Siliciumatom bonded hydroxyl and/or hydrolization group; The 4-epoxycyclohexyl) ethyl trimethoxy silane etc.; Their hydrolytic condensate has the vinyl based copolymer class of epoxy group(ing) and water-disintegrable silyl etc.

Can enumerate for example tolylene diisocyanate, ditan-4 as above-mentioned polyisocyanate compound; Aromatic diisocyanate classes such as 4 '-vulcabond, m xylene diisocyanate, α, α; α '; α '-aralkyl diisocyanates such as tetramethyl-m xylene diisocyanate, hexamethylene diisocyanate, LDI, 1, the diisocyanate based methylcyclohexane of 3-, 2-methyl isophthalic acid; The diisocyanate based hexanaphthene of 3-, 2-methyl isophthalic acid, aliphatics or ester ring type diisocyanates such as the diisocyanate based hexanaphthene of 5-, isophorone diisocyanate;

Above-mentioned polyisocyanate compound and polyalcohols carry out the various prepolymer classes with NCO that addition reaction obtains; Above-mentioned polyisocyanate compound carries out the prepolymer class with chlorinated isocyanurates ring that cyclic trimerizationization obtains; Above-mentioned polyisocyanate compound and water react the polyisocyanates with biuret structure that obtains; By 2-NCO ethyl (methyl) propenoate, 3-pseudoallyl-α, what α-Er Jiajibianji isocyanic ester, (methyl) acryl isocyanic ester etc. had a NCO contains vinyl based copolymer class that contains NCO that vinyl monomer obtains as the ethene base system monomer class of neccessary composition etc.

Can enumerate with various end-capping reagents as above-mentioned blocked polyisocyanates compound above-mentioned polyisocyanate compound is carried out the compound that end-blocking obtains.Can enumerate for example alcohols such as methyl alcohol, ethanol, lactate as above-mentioned end-capping reagent; Phenol, salicylate etc. contain the compounds of phenol property hydroxyl; Amides such as ε-Ji Neixianan, 2-Pyrrolidone; Oximes such as acetoxime, methyl ethyl ketoxime, methyl acetoacetate, ethyl 3-oxobutanoate, Acetyl Acetone isoreactivity methylene compound class etc.

Can enumerate the poly epihydric alcohol ethers of aliphatics such as terepthaloyl moietie, pinakon, NSC 6366, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, hydrogenation dihydroxyphenyl propane for example or ester ring type polyvalent alcohol as above-mentioned polyepoxides; The poly epihydric alcohol ethers of fragrant family glycol such as dihydroxyphenyl propane, bisphenol S, Bisphenol F; The poly epihydric alcohol ethers of polyether glycols such as polyoxyethylene glycol, W 166, polytetramethylene glycol; The poly epihydric alcohol ethers of three (2-hydroxyethyl) chlorinated isocyanurates; The poly glycidyl ester class of aliphatics such as hexanodioic acid, BTCA, phthalic acid, terephthalic acid or aromatic series polycarboxylic acid, the diepoxide class of hydrocarbon system dienes such as cyclooctadiene, VCH, two (3; 4-epoxycyclohexyl methyl) adipic acid ester, 3; 4-epoxycyclohexyl methyl-3, ester ring type polyepoxidess such as 4-epoxycyclohexyl carboxylicesters contain the vinyl based copolymer class of 2 above epoxy group(ing) etc.

As above-mentioned Ju oxazoline compound for example can enumerate 2,2 '-to phenylene two (1, the 3-oxazoline), 2; 2 '-tetramethylene two (1, the 3-oxazoline), 2,2 '-eight methylene radical two low-molecular-weight gathering (1 such as (2-oxazolines); The 3-oxazoline) compound, 2-pseudoallyl-1,3-oxazoline etc. contains 1; The monomeric homopolymer of ethene base system of 3-oxazolinyl or with can obtain with the ethene base system monomer copolymerization of its copolymerization contain 1, the vinyl based polymer of 3-oxazolinyl etc.

Can enumerate for example organic acid dihydrazide compounds such as oxalic acid two hydrazides, propanedioic acid two hydrazides, amber acid dihydrazide etc. as above-mentioned polyhydrazide compound.

Can enumerate that for example trimeric cyanamide, benzoguanamine, acetylguanamine, urea, glycoluril etc. contain aldehyde cpd (or aldehyde supply material) reaction such as amino compound and formaldehyde, acetaldehyde and the various aminoresin with hydroxyalkyl that obtain as above-mentioned aminoresin, lower alcohols such as above-mentioned aminoresin with hydroxyalkyl and methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol react the aminoresin that contains alkoxyalkyl that obtains etc.

Usage quantity as above-mentioned solidifying agent (D); For example when solidifying agent (D) during for compound, blocked polyisocyanates compound with Siliciumatom bonded hydroxyl and/or hydrolization group, aminoresin, multi-carboxy compound; The solids component amount of solidifying agent (D) is in the scope of 0.1～200 weight part with respect to the above-mentioned compound resin of 100 weight parts (ABC) preferably; More preferably in the scope of 0.5～150 weight part, be preferably especially in the scope of 1～100 weight part.

In addition; For example when solidifying agent (D) for compound, polyepoxides with epoxy group(ing) and Siliciumatom bonded hydroxyl and/or hydrolization group, gather cyclic carbonate compound, contain primary or compound, the polyol 、 Ju oxazoline compound of secondary amide base, gather carbodiimide compound, polyhydrazide compound etc. have can with the compound of the group of carboxyl reaction; And above-mentioned compound resin (ABC) is when containing the compound resin of carboxyl; With respect to 1 equivalent carboxyl in the above-mentioned compound resin (ABC); Can be preferably in 0.2～5.0 normal scope in the solidifying agent (D) with the amount of the group (epoxy group(ing), cyclocarbonate radical, carboxamido-group, hydroxyl 、 oxazolinyl, carbodiimide, hydrazide group etc.) of carboxyl reaction; More preferably in 0.5～3.0 normal scope, be preferably especially in 0.7～2.0 normal scope.

And then; For example work as solidifying agent (D) for having compound, the polyisocyanate compound of NCO and Siliciumatom bonded hydroxyl and/or hydrolization group; And above-mentioned compound resin (ABC) is when having the compound resin of Siliciumatom bonded hydroxyl and/or hydrolization group; With respect to 1 equivalent Siliciumatom bonded hydroxyl and/or hydrolization group in the above-mentioned compound resin (ABC); The amount of the NCO in the solidifying agent (D) is preferably in 0.1～10 normal scope, more preferably in 0.3～5.0 normal scope, is preferably especially in 0.5～2.0 normal scope.

In addition; Above-mentioned solidifying agent (D) be preferably when with above-mentioned compound resin (ABC) dissolving or the aqueous dispersion after disperseing be not easy isolating solidifying agent when mixing, can enumerate and for example have the wetting ability that can be dispersed or dissolved in above-mentioned aqueous medium degree, be dispersed or dissolved in the solidifying agent in the above-mentioned aqueous dispersion equably; Though can not be dispersed or dissolved in separately in the above-mentioned aqueous medium, when mixing, can invade, merge, absorption etc., with incorporate solidifying agent of particulate forms etc. to compound resin (ABC) particle with aqueous dispersion.Make " BURNOCK DNW-5000 " (content of NCO is the aqueous dispersion of the polyisocyanate compound of 13.5 weight % as being dispersed or dissolved in the big Japanese ink chemical industry (strain) that uses among the embodiment 5,6,7 that states after solidifying agent in the above-mentioned aqueous dispersion for example can be enumerated equably; Nonvolatile component 80 weight %), " ELASTRON BN-77 " (aqueous self-emulsifying body of blocked polyisocyanates compound is made in the first industrial pharmacy (strain); Solids component 31 weight %), Japanese catalyst (strain) is made " EPOCROS WS-500 "! the equivalent of oxazolinyl be 220g/eq contain 1; The aqueous solution of the water soluble resin of 3-oxazolinyl, content 40 weight %) etc.In addition, as when mixing with above-mentioned aqueous dispersion and the incorporate solidifying agent of compound resin (ABC) particle for example can enumerate after the 3-glycidoxypropyltrime,hoxysilane (3GPTMS), the Mitsubishi Chemical's (strain) that use among the embodiment 1～4,8,9 that states make " MKC SILICATE MS-51 " (polymethoxy siloxanes of condensation degree 2～9), NAGASE (strain) makes " DENACOL EX-614B " (epoxy equivalent (weight) is the epoxy compounds of 173g/eq) etc.

Also can contain thermosetting resin as required in the once antirust processing use of the metal sheet of the present invention compsn.Can enumerate vinyl resin, vibrin, urethane resin, epoxy resin, epoxy ester resin, acrylic resin, phenol resins, petroleum resin, ketone resin, silicone resin or their modified resin etc. as this thermosetting resin.

Can use various inorganic particulates such as clay mineral, metal, MOX or glass as required in the once antirust processing use of the metal sheet of the present invention compsn, but preferably not use usually.Kind as metal can be used gold and silver, copper, platinum, titanium, zinc, nickel, aluminium, iron, silicon, germanium, antimony etc., and also can use their MOX.

Can use known additive commonly used such as mineral dye, pigment dyestuff, filler pigment, dyestuff, wax, tensio-active agent, stablizer, flowing regulator, skimmer, flow agent, rheology control agent, UV light absorber, inhibitor or softening agent etc. as required in the once antirust processing use of the metal sheet of the present invention compsn.

The once antirust processing use of this metal sheet of the present invention compsn can especially be preferably used as the once antirust processing use compsn of steel plate, aluminium sheet aptly as the once antirust processing use compsn of various metal sheets.For example, directly be coated on surface of steel plate as the once antirust processing of steel plate and make its curing and when using, obtain all excellent once antirust processing steel plate of adaptation, rust-preventing characteristic, processibility, scratch resistance easily; Once antirust processing directly is coated on the aluminium sheet and makes its curing and when using, obtain all excellent once antirust processing aluminium sheet of adaptation, rust-preventing characteristic, processibility, wetting ability easily as the metal sheet of aluminium sheet.

The not special restriction of the thickness that the once antirust processing of using the once antirust processing use of metal sheet of the present invention compsn to form is filmed is preferably 0.1～10 micron, more preferably 0.3～7 micron.Thickness can be suppressed at and generate crackle on the cured coating film in above-mentioned scope the time, can form the cured coating film with excellent rust-preventing characteristic.

For example can be suitable for manually various coating processes such as rolling method, spraying method, dip coating, flow coat method, mechanical rolling method, spread coating, electropaining method as be coated with surface of steel plate processing use method for compositions of the present invention to metal sheet.

Through above-mentioned coating process after metal sheet surface is coated with the once antirust processing use of metal sheet of the present invention compsn; Through placing at normal temperatures about 1～10 day; Perhaps about 60～600 ℃ TR heats 10 second～2 hour, preferably heat 20 second～10 minute, the surface-treated metal plate of filming that can obtain having excellences such as adaptation, rust-preventing characteristic, processibility 150～400 ℃ TR.

[embodiment]

Then, through embodiment and comparative example the present invention is described more specifically.Here, part and the % in the example is weight basis.

Synthetic example 1 [the modulation example of the condenses of methyltrimethoxy silane (c-1)]

In reaction vessel, add 1,421 part of methyltrimethoxy silane (MTMS), be warming up to 60 ℃ with stirrer, TM, tap funnel, cooling tube and nitrogen inlet.Then, with the mixture that dripped 0.17 part " A-3 " (sec.-propyl acid SULPHOSUCCINIC ACID ESTER that Sakai chemistry (strain) is made) and 207 parts of deionized waters in 5 minutes.After dripping end, being warming up in the reaction vessel is 80 ℃, stirs 4 hours and the condensation reaction that is hydrolyzed.Then; Under the decompression of 300～10mmHg, (be meant that reduced pressure when heating up in a steamer of methyl alcohol begins is 300mmHg, finally is decompressed to the condition of 10mmHg; Below same), in 40～60 ℃ the TR to the condenses distillation that obtains 2 hours, remove the first alcohol and water of generation, obtain 1; The condenses (c-1) that 000 umber average molecular weight is 1,000, the effective constituent in the reaction solution is 70.0% methyltrimethoxy silane.Theoretical yield (weight part) when here, the effective constituent in the above-mentioned reaction solution is the whole condensation reaction of methoxyl group by MTMS, ethyl trimethoxy silane silane monomers such as (ETMS) calculates (following same) divided by the value of the actual receipts amount (weight part) after the condensation reaction [the actual receipts amount (weight part) after theoretical yield (the weight part)/condensation reaction during the whole condensation reaction of methoxyl group of silane monomer].

Synthetic example 2 [the modulation example of the condenses of ethyl trimethoxy silane (c-2)]

To with the same reaction vessel of synthetic example 1 in add 1,296 part of ETMS, be warming up to 60 ℃.Then, with the mixture that dripped 0.14 part " A-3 " and 171 parts of deionized waters in 5 minutes.After dripping end, being warming up in the reaction vessel is 80 ℃, stirs 4 hours and the condensation reaction that is hydrolyzed.Then; Under the decompression of 300～10mmHg, in 40～60 ℃ the TR to the condenses distillation that obtains 2 hours; Remove the first alcohol and water of generation; The condenses (c-2) that obtain 1,000 umber average molecular weight and be 1,100, the effective constituent in the reaction solution is 70.0% ethyl trimethoxy silane.

Synthetic example 3 [the modulation example of the aqueous dispersion of compound resin (ABC-1)]

To with the same reaction vessel of synthetic example 1 in add 126 parts of Ucar 35 list propyl ethers (PnP), 59 parts of phenyltrimethoxysila,e (PTMS) and 62 parts of dimethyldimethoxysil,ne (DMDMS), be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 21 parts of TEB 3Ks (MMA), 20 parts of NSC 20956s (BMA), 14 parts of Bing Xisuandingzhis (BA), 13 parts of vinylformic acid (AA), 2 parts of 3-methyl allyl acyloxypropyl trimethoxysilanes (MPTS), 3.5 parts of PnP and 3.5 parts of tert-butyl hydroperoxide 2-ethylhexanoate (TBPEH) in 4 hours; After dripping end; Further under uniform temp, reacted 2 hours; Had simultaneously carboxyl and with the number-average molecular weight 14 of Siliciumatom bonded hydrolization group; 000 polymkeric substance (a '-1) then with the mixture that dripped 0.016 part " A-3 " and 45 parts of deionized waters in 5 minutes, and then stirred 1 hour under uniform temp; The condensation reaction that is hydrolyzed obtains comprising to have carboxyl simultaneously and with the polymer segment of Siliciumatom bonded hydrolization group and from the compound resin of the ZGK 5 segment of PTMS and DMDMS (A ' B-1).Then; Add the condenses (c-1) of 290 parts of methyltrimethoxy silanes; And then add 59 parts of deionized waters; Under uniform temp, stirred 16 hours, the condensation reaction that is hydrolyzed obtains containing the reaction solution that above-mentioned compound resin (A ' B-1) and ZGK 5 segment (C-1) from the condenses (c-1) of methyltrimethoxy silane carry out bonded compound resin (A ' BC-1).

Then, under the decompression of 300～10mmHg, under 40～60 ℃ the condition to the reaction solution distillation that obtains 2 hours, remove the first alcohol and water of generation; Add 15 parts of triethylamines (TEA) then; In and the carboxyl in the compound resin (A ' BC-1) and process compound resin (ABC-1), then, carry out the dispersion in hydrotropisms's medium through adding 497 parts of deionized waters; Obtain 1,000 part of nonvolatile component and be the aqueous dispersion of 35.1% compound resin (ABC-1).

Synthetic example 4 [the modulation example of the aqueous dispersion of compound resin (ABC-2)]

To with the same reaction vessel of synthetic example 1 in add 36 parts of PnP, 80 parts of Virahols (IPA), 32 parts of PTM and 19 parts of DMDMS, be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 99 parts of MMA, 86 parts of BMA, 67 parts of BA, 16 parts of AA, 5 parts of MPTS, 14 parts of PnP and 14 parts of TBPEH in 4 hours; After dripping end; Further reaction 2 hours under uniform temp, had simultaneously carboxyl and with the polymkeric substance (a '-2) of the number-average molecular weight 18,000 of Siliciumatom bonded hydrolization group; Then with the mixture that dripped 0.9 part " A-3 " and 24 parts of deionized waters in 5 minutes; And then under uniform temp, stirred 10 hours, the condensation reaction that is hydrolyzed obtains comprising to have carboxyl simultaneously and with the polymer segment of Siliciumatom bonded hydrolization group and from the compound resin of the ZGK 5 segment of PTMS and DMDMS (A ' B-2).Then; Add 18 parts of TEA; In and the carboxyl in the compound resin (A ' B-2) and after processing compound resin (AB-2); Add the condenses (c-1) of 124 parts of methyltrimethoxy silanes, and then add 550 parts of deionized waters, generate above-mentioned compound resin (AB-2) through hydrolytic condensation and carry out bonded compound resin (ABC-2) with ZGK 5 segment (C-1) from the condenses (c-1) of methyltrimethoxy silane; And make the dispersion in compound resin (ABC-2) the hydrotropisms medium, obtain the dispersion-s of compound resin (ABC-2).

Then, under the decompression of 300～10mmHg, under 40～60 ℃ the condition to the dispersion-s distillation that obtains 2 hours, remove the first alcohol and water of IPA, generation, obtain 1,000 part of nonvolatile component and be the aqueous dispersion of 40.0% compound resin (ABC-2).

Synthetic example 5 [the modulation example of the aqueous dispersion of compound resin (ABC-3)]

To with the same reaction vessel of synthetic example 1 in add 60 parts of PnP, 50 parts of IPA, 54 parts of PTMS and 32 parts of DMDMS, be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 40 parts of MMA, 84 parts of BMA, 51 parts of methylacrylic acid 2-ethylhexyls (2-EHMA), 19 parts of AA, 6 parts of MPTS, 10 parts of PnP and 10 parts of TBPEH in 4 hours; After dripping end; Further reaction 2 hours under uniform temp, had simultaneously carboxyl and with the polymkeric substance (a '-3) of the number-average molecular weight 17,000 of Siliciumatom bonded hydrolization group; Then with the mixture that dripped 0.9 part " A-3 " and 24 parts of deionized waters in 5 minutes; And then under uniform temp, stirred 10 hours, the condensation reaction that is hydrolyzed obtains comprising to have carboxyl simultaneously and with the polymer segment of Siliciumatom bonded hydrolization group and from the compound resin of the ZGK 5 segment of PTMS and DMDMS (A ' B-3).Then; Add 21 parts of TEA; In and the carboxyl in the compound resin (A ' B-3) and after forming compound resin (AB-3); Add the condenses (c-1) of 207 parts of methyltrimethoxy silanes, and then add 570 parts of deionized waters, generate above-mentioned compound resin (AB-3) through hydrolytic condensation and be able to bonded compound resin (ABC-3) with ZGK 5 segment (C-1) from the condenses (c-1) of methyltrimethoxy silane; And make in compound resin (ABC-3) the hydrotropisms medium and disperse, obtain the dispersion-s of compound resin (ABC-3).

Then, under the decompression of 300～10mmHg, under 40～60 ℃ the condition to the dispersion-s distillation that obtains 2 hours, remove the first alcohol and water of IPA, generation, obtain nonvolatile component and be 1,000 part of the aqueous dispersion of 40.3% compound resin (ABC-3).

Synthetic example 6 [the modulation example of the aqueous dispersion of compound resin (ABC-4)]

Use the condenses (c-2) of 207 parts of ethyl trimethoxy silanes except the condenses (c-1) that substitutes 207 parts of methyltrimethoxy silanes; Substitute 51 parts of 2-EHMA and use 31 parts of 2-EHMA and 20 parts of 2-hydroxyethyl methacrylates (2-HEMA) in addition; Likewise operate with synthetic example 5 and obtain the aqueous dispersion that 1,000 part of nonvolatile component is 40.0% compound resin (ABC-4).

Relatively more synthetic example 1 [relatively using the modulation example of the aqueous dispersion of compound resin (RAB-1)]

To with the same reaction vessel of synthetic example 1 in add 60 parts of PnP, 365 parts of MTMS and 32 parts of DMDMS, be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 93 parts of MMA, 53 parts of BA, 27 parts of MPTS, 7 parts of AA, 20 parts of 2-HEMA, 10 parts of PnP and 10 parts of TBPEH in 4 hours; After dripping end; Further reaction 2 hours under uniform temp, had simultaneously carboxyl and with the polymkeric substance (Ra '-1) of the number-average molecular weight 16,000 of Siliciumatom bonded hydrolization group; Then with the mixture that dripped 4.6 parts " A-3 " and 154 parts of deionized waters in 5 minutes; And then under uniform temp, stirred 10 hours, the condensation reaction that is hydrolyzed obtains comprising to have carboxyl simultaneously and with the polymer segment of Siliciumatom bonded hydrolization group and from the compound resin of the ZGK 5 segment of MTMS and DMDMS (RA ' B-1).Then, add 21 parts of TEA, in and the carboxyl in the compound resin (RA ' B-1) and after forming compound resin (RAB-1), add 530 parts of deionized waters, carry out the dispersion in above-mentioned compound resin (RAB-1) the hydrotropisms medium, obtain the dispersion-s of compound resin (RAB-1).

Then, under the decompression of 300～10mmHg, under 40～60 ℃ the condition to the dispersion-s distillation that obtains 2 hours, remove the first alcohol and water of generation, obtain 1,000 part of nonvolatile component and be the aqueous dispersion of 40.3% compound resin (RAB-1).

The aqueous dispersion of the compound resin that obtains (RAB-1) is placed after 30 days gelation is taken place.

Relatively more synthetic example 2 [relatively using the modulation example of the aqueous dispersion of resin (RA-2)]

To with the same reaction vessel of synthetic example 1 in add 36 parts of PnP and 80 parts of IPA, be warming up to 80 ℃.Then, under uniform temp, in above-mentioned reaction vessel, dripped the mixture that contains 99 parts of MMA, 86 parts of BMA, 67 parts of BA, 16 parts of AA, 5 parts of MPTS, 14 parts of PnP and 14 parts of TBPEH, after dropping finishes with 4 hours; Further under uniform temp, reacted 2 hours; Obtain having the polymkeric substance (Ra '-2) of the number-average molecular weight 20,000 of carboxyl, add 18 parts of TEA then; In with polymkeric substance in carboxyl; And then add 400 parts of deionized waters, and carry out the dispersion in hydrotropisms's medium, relatively used the dispersion-s of resin (RA-2).

Then, under the decompression of 300～10mmHg, under 40～60 ℃ the condition to the dispersion-s distillation that obtains 2 hours, remove IPA and water, obtain 710 parts of nonvolatile component and be 40.0% the aqueous dispersion of relatively using resin (RA-2).

Above-mentioned synthetic routine 1～6 and the content of relatively synthetic example 1～2 be summarized in the below table 1～table 3.

Table 1

Table 2

Table 3

Abbreviation in above-mentioned table 1～table 3:

PTMS: phenyltrimethoxysila,e

MTMS: methyltrimethoxy silane

DMDMS: dimethyldimethoxysil,ne

MMA: TEB 3K

BMA: NSC 20956

2-EHMA: methylacrylic acid 2-ethylhexyl

BA: Bing Xisuandingzhi

AA: vinylformic acid

The MPTS:3-methacryloxypropyl trimethoxy silane

2-HEMA: 2-hydroxyethyl methacrylate

TBPEH: tert-butyl hydroperoxide-2-ethylhexanoate

Embodiment 1

Mix aqueous dispersion, 5 parts of 3-glycidoxypropyltrime,hoxysilane (3GPTMS) and 5 parts of PnP of the compound resin (ABC-1) that obtains in 100 parts of synthetic examples 3, obtain the once antirust processing use of steel plate of the present invention compsn as solidifying agent (D).Then, go up the once antirust processing use of the steel plate compsn that coating obtains at Zn-Fe fusion steel plate (being untreated in the surface), make that dry film thickness is 2 microns, drying is 5 minutes under 150 ℃, obtains once antirust processing steel plate (P-1).

Then, following adaptation and the rust-preventing characteristic of estimating the once antirust processing film of the once antirust processing steel plate (P-1) that obtains.Evaluation result is shown in Table 4.

Adaptation: measure according to JIS K-5400 8.5.2 grid adhesive tape method.On the once antirust processing film of above-mentioned once antirust processing steel plate,, forms 100 grids, paste the cellulose film adhesive tape, adhere to remaining number of grid and estimate through peeling off fast and counting with the covering total-grid with the wide rag of cutter incision 1mm.Metewand is described below.

Metewand

Zero: do not peel off (remaining grid number is 100).

△: remaining grid number is 60～99.

*: remaining grid number is below 59.

Rust-preventing characteristic: estimate according to JIS K-5400 9.1 salt water resistance sprayability tests.Metewand is described below.

Zero: do not get rusty.

△: the rag being produced by cutter partly gets rusty.

*: whole face all gets rusty.

Embodiment 2～4

Use except the aqueous dispersion of alternative composite resin (ABC-1) the aqueous dispersion of the aqueous dispersion of the compound resin (ABC-2) that obtains in the synthetic example 4～6～(ABC-4), likewise operate with the foregoing description 1 and obtain once antirust processing steel plate (P-2)～(P-4).

Then, likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing steel plate (P-2)～(P-4) that obtains with embodiment 1.Evaluation result is shown in Table 4.

Embodiment 5～9

The aqueous dispersion that mixes the compound resin (ABC-4) that obtains in the synthetic example 6 according to the composition shown in the below table 4 and big Japanese ink chemical industry (strain) are made " BURNOCK DNW-5000 ", and (content of NCO is the aqueous dispersion of 13.5% polyisocyanate compound; Nonvolatile component 80%), " ELASTRON BN-77 " (aqueous self-emulsifying body of blocked polyisocyanates compound is made in the first industrial pharmacy (strain); Solids component 31%), Japanese catalyst (strain) is made " EPOCROS WS-500 "! the equivalent of oxazolinyl be 220g/eq contain 1; The aqueous solution of the water soluble resin of 3-oxazolinyl; Content 40%), Mitsubishi Chemical's (strain) makes " MKC SILICATE MS-51 " (polymethoxy siloxanes of condensation degree 2～9) or NAGASE (strain) makes " DENACOL EX-614B " (epoxy equivalent (weight) is the epoxy compounds of 173g/eq) and PnP, obtains the once antirust processing use of steel plate of the present invention compsn respectively.Then; Except the once antirust processing use of each steel plate compsn that use obtains; Likewise operate with embodiment 1 and obtain once antirust processing steel plate (P-5)～(P-9), likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing steel plate (P-5)～(P-9) that obtains then with embodiment 1.Evaluation result is shown in Table 5.

Comparative example 1

Except not using 3-glycidoxypropyltrime,hoxysilane (3GPTMS) fully, likewise operate with embodiment 1 and obtain the relatively once antirust processing steel plate (R-1) of usefulness as solidifying agent (D).

Then, likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing steel plate (R-1) that obtains with embodiment 1.Evaluation result is shown in Table 6.

Comparative example 2

Mix aqueous dispersion, 20 parts of hole sea chemical industry (strain) of the compound resin (RA-2) that obtains in 100 parts of relatively more synthetic examples 2 and make " LFSHN-050 " (flakey silicon dioxide gel; 0.01～0.5 micron of thickness, 0.6 micron of face diameter, solids component 15%) and 5 parts of PnP, the relatively once antirust processing use of the steel plate compsn of usefulness obtained.Then, except the once antirust processing use of the steel plate compsn that use obtains, likewise operate with embodiment 1 and obtain the relatively once antirust processing steel plate (R-2) of usefulness.

Then, likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing steel plate (R-2) that obtains with embodiment 1.Evaluation result is shown in Table 6.

Comparative example 3

Further mix 5 parts of tripolyphosphates in the once antirust processing use of the steel plate compsn that in above-mentioned comparative example 2, obtains, obtain the relatively once antirust processing use of the steel plate compsn of usefulness.Then, except the once antirust processing use of the steel plate compsn that use obtains, likewise operate with embodiment 1 and obtain the relatively once antirust processing steel plate (R-3) of usefulness.

Then, likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing steel plate (R-3) that obtains with embodiment 1.Evaluation result is shown in Table 6.

Table 4

Table 5

Table 6

Synthetic example 7 [the modulation example of the condenses of dimethyldimethoxysil,ne (c-3)]

To with the same reaction vessel of synthetic example 1 in add 1,200 part of dimethyldimethoxysil,ne (DMDMS), be warming up to 60 ℃.Then, with the mixture that dripped 0.1 part " A-3 " and 200 parts of deionized waters in 5 minutes.After drip finishing, be warming up to and reach 80 ℃ in the reaction vessel, stirred 4 hours, condensation reaction is hydrolyzed.Then; Under the decompression of 300～10mmHg, in 40～60 ℃ the TR to the condenses distillation that obtains 2 hours; Remove the first alcohol and water of generation; The condenses (c-3) that obtain 990 umber average molecular weights and be 1,000, the effective constituent in the reaction solution is 75.0% dimethyldimethoxysil,ne.

Relatively more synthetic example 3 [relatively using the modulation example of the aqueous dispersion of resin (RAC-3)]

To with the same reaction vessel of synthetic example 1 in add 60 parts of PnP, 130 parts of IPA, be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 40 parts of MMA, 84 parts of BMA, 31 parts of 2-EHMA, 20 parts of 2-HEMA, 19 parts of AA, 6 parts of MPTS, 10 parts of PnP and 10 parts of TBPEH in 4 hours; After dripping end; Further reaction 2 hours under uniform temp, had simultaneously carboxyl and with the polymkeric substance (Ra '-3) of the number-average molecular weight 17,000 of Siliciumatom bonded hydrolization group.Then; Add 21 parts of TEA; In and the carboxyl in the compound resin (Ra '-3) and after forming compound resin (RA-3); Add the condenses (c-3) of 270 parts of dimethyldimethoxysil,ne, and then add the mixture of 0.5 part " A-3 " and 700 parts of deionized waters, generate above-mentioned resin (RA-3) and be able to bonded compound resin (RAC-3) from the ZGK 5 segment (C-3) of the condenses (c-3) of dimethyldimethoxysil,ne; And carry out the dispersion in compound resin (RAC-3) the hydrotropisms medium, obtain the dispersion-s of compound resin (RAC-3).

Then, under the decompression of 300～10mmHg, in 40～60 ℃ the TR,, remove the first alcohol and water of IPA, generation, obtain nonvolatile component and be 1,000 part of the aqueous dispersion of 40.1% compound resin (RAC-3) the dispersion-s distillation that obtains 2 hours.

Relatively more synthetic example 4 [relatively using the modulation example of the solvent solution of resin (RAC-4)]

To with the same reaction vessel of synthetic example 1 in add 60 parts of PnP, 130 parts of IPA, be warming up to 80 ℃.Then; Under uniform temp in above-mentioned reaction vessel with dripping the mixture contain 40 parts of MMA, 84 parts of BMA, 31 parts of 2-EHMA, 20 parts of 2-HEMA, 19 parts of AA, 6 parts of MPTS, 10 parts of PnP and 10 parts of TBPEH in 4 hours; After dripping end; Further reaction 2 hours under uniform temp, had simultaneously carboxyl and with the polymkeric substance (Ra '-4) of the number-average molecular weight 17,000 of Siliciumatom bonded hydrolization group.Then; Add the condenses (c-3) of 200 parts of IPA, 270 parts of dimethyldimethoxysil,ne; And then add the mixture of 0.5 part " A-3 " and 10 parts of deionized waters, obtaining above-mentioned resin (Ra '-4) and ZGK 5 segment (C-3) from the condenses (c-3) of dimethyldimethoxysil,ne, to be able to the bonded nonvolatile component be 45.0% compound resin (RAC-4) solvent solution.

With above-mentioned synthetic routine 3 and the content of relatively synthetic example 3～4 be summarized in the below table 7～table 8.

Table 7

Table 8

In above-mentioned table 7～table 8:

MTMS: methyltrimethoxy silane

ETMS: ethyl trimethoxy silane

DMDMS: dimethyldimethoxysil,ne

PTMS: phenyltrimethoxysila,e

MMA: TEB 3K

BMA: NSC 20956

2-EHMA: methylacrylic acid 2-ethylhexyl

BA: Bing Xisuandingzhi

AA: vinylformic acid

The MPTS:3-methacryloxypropyl trimethoxy silane

2-HEMA: 2-hydroxyethyl methacrylate

TBPEH: tert-butyl hydroperoxide-2-ethylhexanoate

Embodiment 10

Mix aqueous dispersion, 5 parts of 3-glycidoxypropyltrime,hoxysilane (3GPTMS) and 5 parts of PnP of the compound resin (ABC-1) that obtains in 100 parts of synthetic examples 3, obtain the once antirust processing use of aluminium sheet of the present invention compsn as solidifying agent (D).Then; [(strain) エ Application ジ ニ ア リ Application グ テ ス ト サ one PVC ス (engineering test Service Co., Ltd) makes at aluminium sheet; JISH4000, A1050P] go up the once antirust processing use of the aluminium sheet compsn that coating obtains, make that dry film thickness is 1 micron; Drying is 10 minutes under 150 ℃, obtains once antirust processing aluminium sheet (P-10).

Then, likewise estimate the adaptation and the rust-preventing characteristic of the once antirust processing film of the once antirust processing aluminium sheet (P-10) that obtains with embodiment 1, and estimate surface hydrophilicity as follows.Evaluation result is shown in Table 9.

Surface hydrophilicity: use consonance interface chemistry (strain) to make full-automatic contact angle appearance DropMaster700, measure the water contact angle of treat surface.

Embodiment 11～13

Use except the aqueous dispersion of alternative composite resin (ABC-1) the aqueous dispersion of the aqueous dispersion of the compound resin (ABC-2) that obtains in the synthetic example 4～6～(ABC-4); Likewise operate with the foregoing description 10 and obtain the once antirust processing use of aluminium sheet compsn; And then except the once antirust processing use of the aluminium sheet compsn that use obtains, likewise operate with embodiment 10 and obtain once antirust processing aluminium sheet (P-11)～(P-13).

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (P-11)～(P-13) that obtains with embodiment 10.Evaluation result is shown in Table 9.

Embodiment 14～18

" ELASTRON BN-77 " made in aqueous dispersion and big Japanese ink chemical industry (strain) manufacturing " BURNOCK DNW-5000 ", the first industrial pharmacy (strain) according to the compound resin (ABC-4) that obtains in the synthetic example 6 of the mixing of the composition shown in the below table 10, Japanese catalyst (strain) is made " EPOCROSWS-500 ", Mitsubishi Chemical's (strain) manufacturing " MKC SILICATE MS-51 " or NAGASE (strain) and made " DENACOL EX-614B " and PnP, obtains the once antirust processing use of aluminium sheet of the present invention compsn respectively.Then; Except the once antirust processing use of each aluminium sheet compsn that use obtains; Likewise operate with embodiment 10 and obtain once antirust processing aluminium sheet (P-14)～(P-18), likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (P-14)～(P-18) that obtains then with embodiment 10.Evaluation result is shown in Table 10.

Comparative example 4

Except not using 3-glycidoxypropyltrime,hoxysilane (3GPTMS) fully, likewise operate with embodiment 10 and obtain the relatively once antirust processing aluminium sheet (RP-4) of usefulness as solidifying agent (D).

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (RP-4) that obtains with embodiment 10.Evaluation result is shown in Table 11.

Comparative example 5

Mix aqueous dispersion, 5 parts of 3GPTMS and 5 parts of PnP of the compound resin (RA-2) that obtains in 100 parts of relatively more synthetic examples 2, obtain the relatively once antirust processing use of the aluminium sheet compsn of usefulness.Then, except the once antirust processing use of the aluminium sheet compsn that use obtains, likewise operate with embodiment 10 and obtain the relatively once antirust processing aluminium sheet (RP-5) of usefulness.

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (RP-5) that obtains with embodiment 10.Evaluation result is shown in Table 11.

Comparative example 6

Mix aqueous dispersion, 5 parts of 3GPTMS and 5 parts of PnP of the compound resin (RAC-3) that obtains in 100 parts of relatively more synthetic examples 3, obtain the relatively once antirust processing use of the aluminium sheet compsn of usefulness.Then, except the once antirust processing use of the aluminium sheet compsn that use obtains, likewise operate with embodiment 10 and obtain the relatively once antirust processing aluminium sheet (RP-6) of usefulness.

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (RP-6) that obtains with embodiment 10.Evaluation result is shown in Table 11.

Comparative example 7

With the solvent solution of the compound resin (RAC-4) that obtains in 100 parts of relatively synthetic examples 4 as the once antirust processing use of the aluminium sheet compsn of usefulness relatively; And use the once antirust processing use of this aluminium sheet compsn, likewise operate with embodiment 10 in addition and obtain the relatively once antirust processing aluminium sheet (RP-7) of usefulness.

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (RP-7) that obtains with embodiment 10.Evaluation result is shown in Table 11.

Comparative example 8

Mix the solvent solution of the compound resin (RAC-4) that obtains in 100 parts of relatively more synthetic examples 4 and " CYMEL 300 " (methyl type melamine resin that Mitsui CYTEC Co., Ltd. makes; Nonvolatile component 100%), obtain the relatively once antirust processing use of the aluminium sheet compsn of usefulness.Then, except the once antirust processing use of the aluminium sheet compsn that use obtains, likewise operate with embodiment 10 and obtain the relatively once antirust processing aluminium sheet (RP-8) of usefulness.

Then, likewise estimate adaptation, rust-preventing characteristic and the surface hydrophilicity of the once antirust processing film of the once antirust processing aluminium sheet (RP-8) that obtains with embodiment 10.Evaluation result is shown in Table 11.

Table 9

Table 10

Table 11

Claims (16)

1. the application of waterborne compositions in the once antirust processing of metal sheet; It is characterized in that; Said waterborne compositions contains compound resin (ABC) and dissolves or be dispersed in the aqueous medium and the Water-borne modification thing of the compound resin (ABC) that forms and the solidifying agent (D) of said compound resin (ABC); The ZGK 5 segment (B) of compound resin (AB) is through silicon-oxygen key to combine with the ZGK 5 segment (C) that is the condenses (c) of 1～3 alkyltrialkoxysilaneand from the alkyl carbon atoms number in the said compound resin (ABC), and the polymer segment (A) and the ZGK 5 segment (B) that have the acidic group that neutralized in the said compound resin (AB) are combined by chemical bond.

2. the application of waterborne compositions according to claim 1 in the once antirust processing of metal sheet; It is characterized in that said compound resin (ABC) is for contain the said ZGK 5 segment (B) of 25～85 weight % and the compound resin of said ZGK 5 segment (C) altogether.

3. the application of waterborne compositions according to claim 2 in the once antirust processing of metal sheet is characterized in that, said compound resin (ABC) is the compound resin that contains the said ZGK 5 segment (C) of 15～60 weight %.

4. according to claim 1, the application of 2 or 3 described waterborne compositions in the once antirust processing of metal sheet; It is characterized in that; Said compound resin (ABC) is that said polymer segment (A) and said ZGK 5 segment (B) carry out the bonded compound resin through the combination of being represented by following structural formula (S-1), and said structural formula (S-1) is:

[Chemical formula 1]

Here, the carbon atom in the structural formula (S-1) constitutes the part of said polymer segment (A), and Siliciumatom and Sauerstoffatom constitute the part of said ZGK 5 segment (B).

5. the application of waterborne compositions according to claim 4 in the once antirust processing of metal sheet is characterized in that said polymer segment (A) is the segment from the vinyl based polymer.

6. according to claim 1, the application of 2 or 3 described waterborne compositions in the once antirust processing of metal sheet; It is characterized in that the condenses that the condenses of said alkyltrialkoxysilaneand (c) obtains for hydrolytic condensation methyltrimethoxy silane and/or Union carbide A-162.

7. according to claim 1, the application of 2 or 3 described waterborne compositions in the once antirust processing of metal sheet; It is characterized in that, said solidifying agent (D) for be selected from by have with Siliciumatom bonded hydroxyl and/or with the compound of Siliciumatom bonded hydrolization group, in a molecule, have NCO and with the compound of Siliciumatom bonded hydrolization group, in a molecule, have epoxy group(ing) and with compound, polyisocyanate compound, blocked polyisocyanates compound, the polyepoxides of Siliciumatom bonded hydrolization group, gather cyclic carbonate compound, aminoresin, contain at least a compound in the group that compound, multi-carboxy compound and the polyol of primary amide base or secondary amide base form.

8. according to claim 1, the application of 2 or 3 described waterborne compositions in the once antirust processing of metal sheet, it is characterized in that, obtain said waterborne compositions through the method for manufacture that comprises following operation (I)～(III),

(I) to have simultaneously acidic group and with Siliciumatom bonded hydroxyl and/or with the condensation that is hydrolyzed of the polymkeric substance of Siliciumatom bonded hydrolization group (a ') and hydrocarbyl alkoxy silanes (b) and/or its hydrolytic condensate (b-1), obtain the operation of the compound resin that polymer segment (A ') and ZGK 5 segment (B) from hydrocarbyl alkoxy silanes (b) from polymkeric substance (a ') combine by chemical bond (A ' B);

(II) then; It to the carbonatoms of compound resin of gained (A ' B) and alkyl the condensation that is hydrolyzed of the condenses (c) of 1～3 alkyltrialkoxysilaneand; Obtain the ZGK 5 segment (B) of compound resin (A ' B) with from the alkyl carbon atoms number be the ZGK 5 segment (C) of condenses (c) of 1～3 alkyltrialkoxysilaneand behind silicon-oxygen key bonded compound resin (A ' BC), obtain the operation of compound resin (ABC) with the acidic group in this compound resin of basic cpd neutralization (A ' BC); Perhaps; With in the basic cpd with the compound resin of gained (A ' B) in acidic group and after processing compound resin (AB); The carbonatoms of hydrolytic condensation alkyl is the condenses (c) of 1～3 alkyltrialkoxysilaneand, obtains the ZGK 5 segment (B) of compound resin (AB) and is that the ZGK 5 segment (C) of condenses (c) of 1～3 alkyltrialkoxysilaneand is through the operation of silicon-oxygen key bonded compound resin (ABC) from the alkyl carbon atoms number;

(III) then, the compound resin (ABC) of gained is mixed with aqueous medium, disperse or dissolve compound resin (ABC) and after obtaining the Water-borne modification thing of compound resin (ABC), mix the operation of the solidifying agent (D) of said compound resin (ABC).

9. the application of waterborne compositions according to claim 8 in the once antirust processing of metal sheet; It is characterized in that, said hydrocarbyl alkoxy silanes (b) for have with single alkyl trialkoxy silane of the organic group of Siliciumatom bonded carbonatoms 4～12 and/or have 2 with Siliciumatom bonded methyl and/or with the dialkyl dialkoxy silicane of Siliciumatom bonded ethyl.

10. the application of waterborne compositions according to claim 9 in the once antirust processing of metal sheet is characterized in that the organic group of said carbonatoms 4～12 is alkyl, naphthenic base, aryl or aralkyl.

11. the application of waterborne compositions according to claim 8 in the once antirust processing of metal sheet is characterized in that, and said polymkeric substance (a ') be the vinyl based polymer.

12. the application of waterborne compositions in the once antirust processing of steel plate is characterized in that said waterborne compositions comprises the waterborne compositions of any record in the claim 1～11.

13. the application of waterborne compositions in the once antirust processing of aluminium sheet is characterized in that said waterborne compositions comprises the waterborne compositions of any record in the claim 1～11.

14. an once antirust processing metal sheet is characterized in that, the metal sheet that said metal sheet carries out once antirust processing for the waterborne compositions that uses any record in the claim 1～11.

15. an once antirust processing steel plate is characterized in that, the steel plate that said steel plate carries out once antirust processing for the waterborne compositions that uses claim 12 record.

16. an once antirust processing aluminium sheet is characterized in that, the aluminium sheet that said aluminium sheet carries out once antirust processing for the waterborne compositions that uses claim 13 record.