CN101560351B - Corrosion proof impregnating varnish used for water-based metal components and manufacturing method thereof - Google Patents

Corrosion proof impregnating varnish used for water-based metal components and manufacturing method thereof Download PDF

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CN101560351B
CN101560351B CN2009100092337A CN200910009233A CN101560351B CN 101560351 B CN101560351 B CN 101560351B CN 2009100092337 A CN2009100092337 A CN 2009100092337A CN 200910009233 A CN200910009233 A CN 200910009233A CN 101560351 B CN101560351 B CN 101560351B
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polyaniline
water
described amount
deionized water
aniline
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CN101560351A (en
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刘善江
杨磊
徐小东
肖铭
刘国旭
商艳明
郭晓峰
耿耀宗
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Hebei Chenyang Industry and Trade Group Co Ltd
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Hebei Chenyang Industry and Trade Group Co Ltd
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Abstract

The invention discloses a corrosion proof impregnating varnish used for water-based metal components and a manufacturing method thereof. The corrosion proof impregnating varnish is made of de-ionized water, propanediol, dispersant, antifoaming agent, wetting agent, carbon black, iron oxide black, water borne acroid resin, water borne epoxy resin, dipropylene glycol butyl ether, propylene glycol ether and polyaniline water solution, polyaniline carrier particles or polyaniline emulsion. The manufacturing method comprises: the propanediol and the de-ionized water are mixed and stirred, and then added with the dispersant, the antifoaming agent, the wetting agent and the polyaniline water solution or the water solution of emulsion or carrier particles to be evenly mixed together; the carbon black and the iron oxide black are added in to the mixed solution to form uniform pigment paste which is then put into a blending tank after being ground to be evenly stirred; the obtained mixture is added with the water borne acroid resin, the water borne epoxy resin, the dipropylene glycol butyl ether and the propylene glycol ether to be stirred; finally, the stirred mixture is added with the de-ionized water to be diluted and ground. The invention has the advantages of high coating efficiency, stable coating quality, uniform paint film of dip coating, flat and smooth paint film, good hardness, strong adhesive attraction, good corrosion proof performance, excellent painting performance at edges and corners, no leaking painting, good salt mist resistance, environmental protection, low cost,etc.

Description

A kind of corrosion proof impregnating varnish used for water-based metal components and manufacture method thereof
One, technical field
The present invention relates to a kind of polyaniline-modified aqueous metal member special anti-corrosion impregnating varnish and preparation method thereof.
Two, background technology
Countries such as the hardware main exit America and Europe of domestic production, its application mode is based on dip-coating, showering, lacquer liquid stability requirement height, after the dip-coating, it is thinner to film, be generally 5-15um, antiseptic property is had relatively high expectations, in particular for the hardwares such as sofa extensible member on the indoor sofa, it also has strict requirement with lacquer on the feature of environmental protection, do not contain harmful materials such as phthalate, gylcol ether, halohydrocarbon, benzene,toluene,xylene, ethylbenzene, do not contain poisonous heavy metal lead, cadmium, chromium, mercury.
The application of hardware is monopolized by Shanghai Li Li factory of U.S. The Valspar Corporation with lacquer always, the hardware of its production is made by single water-borne acrylic resin with lacquer, it meets above-mentioned environmental requirement, but because the preservative property of acrylic resin, solvent resistance is relatively poor, in use there are problems, salt fog resistance is relatively poor, paint film thickness is that the salt spray resistance of the paint film of 5-10um has only 8 hours, dip-coating workpiece corner angle are not hung lacquer, be unsuitable for carrying out shower coat, and price is higher, existing market is difficult to accept, our company's disclosure of an invention number be the aqueous metal member of CN 101255303A with lacquer, the problems referred to above have been had tangible improvement, but aspect antiseptic property, have still lacked perfection.
Three, summary of the invention
The present invention solves the above-mentioned problems in the prior art exactly, provides a kind of aqueous, environmental protective, stability is high, rate of drying is fast, hardness is high, strong adhesion, good corrosion resistance, dip-coating workpiece corner angle are hung good corrosion proof impregnating varnish used for water-based metal components of lacquer performance and preparation method thereof.
For addressing the above problem; technical scheme of the present invention is: a kind of corrosion proof impregnating varnish used for water-based metal components; it is made by following proportioning raw materials, counts by weight percentage: the deionized water of 8-15%; the propylene glycol of 1-5%; the dispersion agent of 0.5-1.5%; the defoamer of 0.1-0.5%; the wetting agent of 0.5-1.5%; the carbon black of 2-8%; the iron oxide black of 10-22%; the water-borne acrylic resin of 25-33%; the aqueous epoxy resins of 20-28%; the dipropylene glycol butyl ether of 1-3%; the polyaniline aqueous solution of the propylene glycol of 2-5% and 1-12% or polyaniline carrier particles or polyaniline emulsion.
Dispersion agent in the above-mentioned described corrosion proof impregnating varnish used for water-based metal components is one or more in ammonium salt, maleic anhydride copolymer and the Viscotrol C sulphate of acrylate copolymer; Defoamer is one or both in polyoxyethylene glycol and the polysiloxane, and when defoamer was two kinds of polyoxyethylene glycol and polysiloxane, its proportioning was 1: 0.5-2; Wetting agent is polyether-modified polydimethylsiloxane or polydimethylsiloxane.
The polyaniline aqueous solution in the above-mentioned described corrosion proof impregnating varnish used for water-based metal components is made by following proportioning raw materials, count by weight percentage: the deionized water of 85-95%, the sodium-based montmorillonite of 2-10%, the aniline of 0.5-1.5%, the organic sulfonic acid of 0.8-3.0% and the Ammonium Persulfate 98.5 of 1-3%; Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
Polyaniline carrier particles in the above-mentioned described corrosion proof impregnating varnish used for water-based metal components is made by following proportioning raw materials, count by weight percentage: the deionized water of 60-80%, the sodium-based montmorillonite of 10-32%, the aniline of 1.5-2.5%, the organic sulfonic acid of 4-6.5% and the Ammonium Persulfate 98.5 of 2-8%; Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
Polyaniline emulsion in the above-mentioned described corrosion proof impregnating varnish used for water-based metal components is made by following proportioning raw materials, counts by weight percentage: the deionized water of 84-92%, the aniline of 0.5-2.5%, the organic sulfonic acid of 5.5-8.5% and the Ammonium Persulfate 98.5 of 1-6%; Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
A kind of making method of corrosion proof impregnating varnish used for water-based metal components, it may further comprise the steps:
1, as using the polyaniline carrier granule, in the deionized water of elder generation with the 1/5-1/4 of the polyaniline carrier granule adding 8-15% of 1-12%, forms the aqueous solution of polyaniline carrier granule;
2, with 2/3 the deionized water of the propylene glycol of 1-5%, 8-15%,,, add in the pot of getting the raw materials ready, with the speed stirring at low speed of 400-600rpm with the deionized water of 1/2-8/15 as using the polyaniline carrier granule;
3, the aqueous solution that adds the polyaniline aqueous solution of the wetting agent of defoamer, 0.5-1.5% of dispersion agent, the 0.1-0.5% of 0.5-1.5% and 1-12% or polyaniline emulsion or the above-mentioned polyaniline carrier granule that mixes successively evenly after, add the carbon black of 2-8% and the iron oxide black of 10-22%, with the speed high speed dispersion of 1200rpm more than 20 minutes, form even mill base, do not have obvious dry mash piece;
4, the mill base that stirs is ground, till fineness≤20um; The qualified mill base of grinding is squeezed into accent to be converted in the jar, start stirring, low speed mixing is even, slowly add the water-borne acrylic resin of 25-33%, the aqueous epoxy resins of 20-28%, the dipropylene glycol butyl ether of 1-3% and the propylene glycol of 2-5% successively, stir more than at least 15 minutes, add 1/3, as using the polyaniline carrier granule, the deionized water that adds 1/4-4/15 is transferred rare to being coated with for 4 viscosity 30-50 seconds.
The making method of the polyaniline aqueous solution in the making method of above-mentioned described corrosion proof impregnating varnish used for water-based metal components, it may further comprise the steps: (1) places ultrasonic generator or beaker with the sodium-based montmorillonite of 2-10%, 9/10 the deionized water that adds 85-95%, ultrasonic dispersing or dispersed with stirring are more than 1 hour, make sodium-based montmorillonite homodisperse and abundant swelling in deionized water, stirring, heat temperature raising are to 78-82 ℃; (2) with the aniline of 0.5-1.5% and the organic sulfonic acid wiring solution-forming of 0.8-3.0%, and the formation aniline solution that stirs; (3) Ammonium Persulfate 98.5 that takes by weighing 1-3% is dissolved in 1/10 the deionized water of 85-95% and forms ammonium persulfate aqueous solution; (4) in nitrogen N 2Protection under, aniline solution is splashed in the described sodium-based montmorillonite aqueous dispersions, keep 78-82 ℃, stir and to disperse intercalation compound more than 3 hours down, form mixing solutions; Cooling subsequently, to the described Ammonium Persulfate 98.5 aqueous solution of mixed solution and dripping, the mixing solutions color is deepened gradually, after blackish green, continues reaction again more than 24 hours; Promptly get the polyaniline aqueous solution.Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
The making method of polyaniline carrier particles in the making method of above-mentioned described corrosion proof impregnating varnish used for water-based metal components, it may further comprise the steps: it may further comprise the steps (1): (1) at room temperature, the deionized water of 60-80% is inserted in the beaker, the sodium-based montmorillonite that takes by weighing 10-32% adds beaker, beaker is put into ultrasonic generator carry out ultrasonic dispersing, make it to be uniformly dispersed, be warming up to 78-82 ℃; (2) with the aniline of 1.5-2.5% and the organic sulfonic acid wiring solution-forming of 4-6.5%, and the formation aniline solution that stirs; (3) aniline solution is joined in the beaker lentamente, continue ultrasonic dispersing more than 5 hours in ultrasonic generator, reduce to the Ammonium Persulfate 98.5 that room temperature slowly adds 2-8%, reaction was continued more than 24 hours in the back that stirs; (4) then with its suction filtration, colourless to filtrate with washed with de-ionized water, 58-62 ℃ of oven dry promptly gets the polyaniline carrier granule after the grinding.Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
The making method of polyaniline emulsion in the making method of above-mentioned described corrosion proof impregnating varnish used for water-based metal components, it may further comprise the steps: (1) at room temperature, 9/10 the deionized water of 84-92% is placed there-necked flask, the organic sulfonic acid that adds 5.5-8.5%, brute force stirs, (2) aniline that then slowly drips 0.5-2.5% forms emulsion, the Ammonium Persulfate 98.5 that takes by weighing 1-6% is dissolved in 1/10 the deionized water of 84-92% and forms ammonium persulfate aqueous solution, stir and slowly be added to ammonium persulfate aqueous solution in the emulsion down, dropwise the back and continue reaction 5~8 hours, promptly get the polyaniline emulsion.Described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
Water-borne acrylic resin is the water-repellent preservation resin that U.S. ROHM AND HAAS is produced, and for aquosity metallic protective paint has been set up new standard of performance, and provides reference formulation for water-based metal priming paint and finish paint.Paint film property, corrosion-resistant as high gloss, hardness, levelling and solvent resistance are good.Comprise that at various metal substrates good sticking power etc. is all arranged on the galvanized sheet.The aqueous metallic paint that uses the watersoluble modified acrylic acid resin to make; reduced the maintenance cost of metal building, reduced the number of times of recoat, the good protection to metal substrate is provided; has excellent gloss retention; corrosion-resistant, anti-solvent, the lasting anti-marquis of color; dryness speed is fast; hardness is good, and is good to the wettability of pigment, coating surface color even unanimity.Aqueous epoxy resins and their derivative have excellent sticking power usually on steel, water tolerance, the erosion resistance of the aqueous metallic paint paint film of its making are stronger, and the while has also increased the sticking power with ground, have improved the hardness of paint film.
Because the present invention has adopted water-borne acrylic resin and aqueous epoxy resins composite, realize the mutual supplement with each other's advantages of two kinds of resins, the gloss retention of water-based protection usefulness resin excellence, corrosion-resistant, anti-solvent, the lasting anti-marquis of color, fast drying, hardness is good, and is good to the wettability of pigment; The aqueous epoxy resins water tolerance, erosion resistance is strong, has excellent sticking power on steel, the hardness height.Two kinds of composite resins are good stability also, does not fire, not quick-fried, nuisanceless, low tempertaure storage never degenerates.Efficient auxiliary agent enhancements such as employing dispersion agent, defoamer and wetting agent are wetting to ground, prevented shrinkage cavity.In addition, also promote surperficial smooth and gloss, made paint film uniform distribution on the metallic surface, and strengthened the extension lacquer performance of workpiece corner angle.
In a word, the present invention has easy construction, quick, adopts the production technique of spraying or dip-coating, the coating efficiency height, and coating quality is stable, the paint film of dip-coating is even, and paint film is smooth, smooth, and hardness is good, strong adhesion, antiseptic property is good, and corner angle extension lacquer property is good, no holiday phenomenon, and salt spray resistance can reach 96 hours.In the scope of application of more extensively drawing together, the application property that can obtain to suit.This product does not contain harmful materials such as phthalate, glycol ester class, halohydrocarbon, benzene,toluene,xylene, ethylbenzene, not leaded Ge, Cadmium, mercury or the like heavy metal.Meet the requirement of international up-to-date environmental regulation, characteristics such as the cost of material is low are suitable for the use of domestic export hardware fully.
Four, embodiment
The invention will be further described below in conjunction with specific examples, and following content all calculates according to weight ratio.
Embodiment 1, present embodiment is made by following proportioning raw materials:8% deionized water, 1% propylene glycol, 0.5% dispersion agent:acrylate copolymer De salt, defoamer:0.05% polyoxyethylene glycol and 0.05% polysiloxane, 0.5% wetting agent:polyether-modified polydimethylsiloxane, 4% carbon black, 11.9% iron oxide black, 33% water-borne acrylic resin, 28% aqueous epoxy resins, 3% dipropylene glycol butyl ether, 5% propylene glycol:propylene glycol butyl ether and, 5.0% polyaniline solutions.The polyaniline aqueous solution is by, 85% deionized water, 10% sodium-based montmorillonite, and 1.5% aniline, 2% organic sulfonic acid:tosic acid and, 1.5% Ammonium Persulfate, 98.5 are made.
Its making method may further comprise the steps:
1, the making of the polyaniline aqueous solution: (1) places ultrasonic wave to send out the sodium-based montmorillonite of above-mentioned described amount and answers device, adds 9/10 deionized water of above-mentioned described amount, and ultrasonic dispersing is more than 1 hour, and stir the back, heat temperature raising is to 78-82 ℃; (2) with the aniline and the organic sulfonic acid wiring solution-forming of described amount, and the formation aniline solution that stirs; (3) Ammonium Persulfate 98.5 that takes by weighing described amount is dissolved in 1/10 the deionized water and forms ammonium persulfate aqueous solution; (4) in nitrogen N 2Protection under, aniline solution is splashed in the described sodium-based montmorillonite aqueous dispersions, keep 78-82 ℃, stir and to disperse intercalation compound more than 3 hours down, form mixing solutions; Cooling subsequently, to the Ammonium Persulfate 98.5 aqueous solution initiated polymerization of the described amount of mixed solution and dripping, the mixing solutions color become blackish green after, continue reaction more than 24 hours, promptly get the polyaniline aqueous solution.
2, with 2/3 deionized water, propylene glycol, the polyaniline aqueous solution, add in the pot of getting the raw materials ready according to formula ratio, stir with the 400-600rpm rotating speed.
3, according to formula ratio, add successively after dispersion agent, defoamer and wetting agent mix, add color stuffing: carbon black and iron oxide black, more than 20 minutes, form even mill base with the speed high speed dispersion of 1200rpm, there is not obvious dry mash piece.
4, the mill base that stirs is ground, fineness≤20um; The qualified mill base of grinding is squeezed into accent to be converted in the jar, start stirring, low speed mixing is even, the water-borne acrylic resin and aqueous epoxy resins and the solubility promoter that slowly add formula ratio successively: dipropylene glycol butyl ether and propylene glycol, stir more than at least 15 minutes, survey initial viscosity, according to initial viscosity, the deionized water that adds 1/4-4/15 is transferred rare to being coated with for 4 viscosity 30-50 seconds.
5, check its viscosity to meet the requirements, soak plate checking dryness, hardness, surface effect, meet the requirements, surfacing, no significant defect is packed.
Embodiment 2, present embodiment are made by following proportioning raw materials: 15% deionized water, 2.5% propylene glycol, 1% dispersion agent: maleic anhydride copolymer, 0.5% defoamer: polyoxyethylene glycol, 1% wetting agent: polydimethylsiloxane, 7% carbon black, 14% iron oxide black, 25% water-borne acrylic resin, 24% aqueous epoxy resins, 1.5% dipropylene glycol, 2.5% propylene glycol: the propylene glycol monomethyl ether and 6% the polyaniline aqueous solution.The polyaniline aqueous solution is by 90% deionized water, 5% sodium-based montmorillonite, and 0.5% aniline, 1.5% organic sulfonic acid: Witco 1298 Soft Acid and 3% Ammonium Persulfate 98.5 are made.Its making method is with example 1.
Embodiment 3, present embodiment is made by following proportioning raw materials: 10.8% deionized water, 5% propylene glycol, 1.5% dispersion agent: Viscotrol C sulphate, 0.2% defoamer: polysiloxane, 1.5% wetting agent: polyether-modified polydimethylsiloxane, 8% import carbon black, 22% iron oxide black, 27% water-borne acrylic resin, 20% aqueous epoxy resins, 1% dipropylene glycol butyl ether, 2% propylene glycol: the propylene-glycol ethyl ether and 1% the polyaniline aqueous solution.The polyaniline aqueous solution is by 95% deionized water, 2% sodium-based montmorillonite, and 1.2% aniline, 0.8% organic sulfonic acid: camphorsulfonic acid and 1% Ammonium Persulfate 98.5 are made.Its making method is with example 1.
Embodiment 4, present embodiment is made by following proportioning raw materials: 12% deionized water, 3% propylene glycol, dispersion agent: the ammonium salt of 0.4% acrylate copolymer, 0.4% maleic anhydride copolymer and 0.45% Viscotrol C sulphate, defoamer: 0.2% polyoxyethylene glycol and 0.1% polysiloxane, 1.25% wetting agent: polydimethylsiloxane, 2% import carbon black, 10% iron oxide black, 30.2% watersoluble modified acrylic acid resin, 22% aqueous epoxy resins, 2% dipropylene glycol butyl ether, 4% propylene glycol: propylene glycol butyl ether and 12% polyaniline solutions.The polyaniline aqueous solution is by 91.2% deionized water, 3% sodium-based montmorillonite, and 0.8% aniline, 3% organic sulfonic acid: polystyrolsulfon acid and 2% Ammonium Persulfate 98.5 are made.Its making method is with example 1.
Embodiment 5, present embodiment is made by following proportioning raw materials: 15% deionized water, 3% propylene glycol, dispersion agent: the ammonium salt of 0.3% acrylate copolymer and 0.3% maleic anhydride copolymer, defoamer: 0.1% polyoxyethylene glycol and 0.2% polysiloxane, 0.5% wetting agent: polyether-modified polydimethylsiloxane, 4% carbon black, 12.8% iron oxide black, 29% water-borne acrylic resin, 27% aqueous epoxy resins, 2.6% dipropylene glycol, 4.2% propylene glycol: propylene glycol monomethyl ether, 1% polyaniline carrier particles.The polyaniline carrier particles is by 60% deionized water, 32% sodium-based montmorillonite, and 2% aniline, 4% organic sulfonic acid: tosic acid and 2% Ammonium Persulfate 98.5 are made.
Its making method may further comprise the steps:
1, the making of polyaniline carrier granule: (1) at room temperature, the deionized water of above-mentioned described amount is inserted in the beaker, and the sodium-based montmorillonite that takes by weighing described amount adds beaker, beaker is put into ultrasonic generator carry out ultrasonic dispersing, make it to be uniformly dispersed, be warming up to 78-82 ℃; (2) aniline of described amount and organic sulfonic acid are made into the aqueous solution formation aniline solution that stirs; (3) aniline solution is joined lentamente in the beaker continue ultrasonic dispersing more than 5 hours after, reduce to the Ammonium Persulfate 98.5 that room temperature slowly adds described amount, reaction was continued more than 24 hours in the back that stirs; (4) then with its suction filtration, colourless to filtrate with washed with de-ionized water, 58-62 ℃ of oven dry promptly gets the polyaniline carrier granule after the grinding.
2, the polyaniline carrier of described amount is added in the deionized water of 1/5-1/4, form the aqueous solution of polyaniline carrier granule;
3, add in the pot of getting the raw materials ready according to the aqueous solution of formula ratio, stir with the 400-600rpm rotating speed with deionized water, propylene glycol and the polyaniline carrier granule of 1/2-8/15;
4, according to formula ratio, add successively after dispersion agent, defoamer and wetting agent mix, add color stuffing: import carbon black and iron black, high speed dispersion (1200rpm) formed even mill base more than 20 minutes, did not have obvious dry mash piece;
5, the mill base that stirs is ground, fineness≤20um; The qualified mill base of grinding is squeezed into accent to be converted in the jar, start stirring, low speed mixing is even, the water-borne acrylic resin and aqueous epoxy resins and the solubility promoter that slowly add formula ratio successively: dipropylene glycol butyl ether and propylene glycol, stir more than at least 15 minutes, survey initial viscosity, according to initial viscosity, the deionized water that adds 1/4-4/15 is transferred rare to being coated with for 4 viscosity 30-50 seconds.
6, check its viscosity to meet the requirements, soak plate checking dryness, hardness, surface effect, meet the requirements, surfacing, no significant defect is packed.
Embodiment 6, present embodiment is made by following proportioning raw materials: 13% deionized water, 4% propylene glycol, dispersion agent: 0.45% maleic anhydride copolymer and 0.3% Viscotrol C sulphate, 0.3% defoamer: polyoxyethylene glycol, 0.75% wetting agent: polyether-modified polydimethylsiloxane, 5% carbon black, 16% iron oxide black, 26% water-borne acrylic resin, 25% aqueous epoxy resins, 2.5% dipropylene glycol, 3% propylene glycol: propylene glycol butyl ether and 3.7% polyaniline carrier particles.The polyaniline carrier particles is by 80% deionized water, 10% sodium-based montmorillonite, and 1.5% aniline, 5% organic sulfonic acid: Witco 1298 Soft Acid and 3.5% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 5.
Embodiment 7, present embodiment is made by following proportioning raw materials: 14.1% deionized water, 3.5% propylene glycol, 0.8% dispersion agent: maleic anhydride copolymer, 0.5% defoamer: polyoxyethylene glycol, 0.6% wetting agent: polyether-modified polydimethylsiloxane, 6% carbon black, 13% iron oxide black, 26% water-borne acrylic resin, 24% aqueous epoxy resins, 2.5% dipropylene glycol, 4% propylene glycol: propylene glycol propyl ether, 5% polyaniline carrier particles.The polyaniline carrier particles is by 63% deionized water, 20% sodium-based montmorillonite, and 2.5% aniline, 6.5% organic sulfonic acid: camphorsulfonic acid and 8% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 5.
Embodiment 8, present embodiment is made by following proportioning raw materials: 10% deionized water, 4% propylene glycol, 0.9% dispersion agent: the ammonium salt of acrylate copolymer, 0.2% defoamer: polysiloxane, 0.9% wetting agent: polyether-modified polydimethylsiloxane, 5% carbon black, 15% iron oxide black, 31% water-borne acrylic resin, 21% aqueous epoxy resins, 1% dipropylene glycol, 3% propylene glycol: propylene glycol butyl ether and 8% polyaniline carrier particles.The polyaniline carrier particles is by 72% deionized water, 15% sodium-based montmorillonite, and 1% aniline, 6% organic sulfonic acid: polystyrolsulfon acid and 6% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 5.
Embodiment 9, present embodiment are made by following proportioning raw materials, 9% deionized water, 2% propylene glycol, 1.5% dispersion agent: the ammonium salt of acrylate copolymer, 0.5% defoamer: polyoxyethylene glycol, 1.5% wetting agent: polyether-modified polydimethylsiloxane, 3% carbon black, 18% iron oxide black, 28% water-borne acrylic resin, 26% aqueous epoxy resins, 1% dipropylene glycol, 3.5% propylene glycol: propylene-glycol ethyl ether, 6% polyaniline milk sap.The polyaniline emulsion is by 84% deionized water, 2.5% aniline, and 8.5% organic sulfonic acid: tosic acid and 5% Ammonium Persulfate 98.5 are made.
Its making method may further comprise the steps:
1, the making of polyaniline emulsion: (1) at room temperature, with 9/10 deionized water of above-mentioned described amount in there-necked flask, the Witco 1298 Soft Acid that adds described amount, brute force stirs, (2) aniline that then slowly drips described amount forms emulsion, and the Ammonium Persulfate 98.5 that takes by weighing described amount is dissolved in 1/10 the deionized water and forms ammonium persulfate solution, stirs slowly to be added to ammonium persulfate solution in the emulsion down, dropwise the back and continue reaction 5~8 hours, promptly get the polyaniline emulsion.
2, with 2/3 deionized water, propylene glycol, polyaniline emulsion, add in the pot of getting the raw materials ready according to formula ratio, stir with the 400-600rpm rotating speed;
2, with 2/3 deionized water, propylene glycol, the polyaniline aqueous solution, add in the pot of getting the raw materials ready according to formula ratio, stir with the 400-600rpm rotating speed.
3, according to formula ratio, add successively after dispersion agent, defoamer and wetting agent mix, add color stuffing: carbon black and iron oxide black, more than 20 minutes, form even mill base with the speed high speed dispersion of 1200rpm, there is not obvious dry mash piece.
4, the mill base that stirs is ground, fineness≤20um; The qualified mill base of grinding is squeezed into accent to be converted in the jar, start stirring, low speed mixing is even, the water-borne acrylic resin and aqueous epoxy resins and the solubility promoter that slowly add formula ratio successively: dipropylene glycol butyl ether and propylene glycol, stir more than at least 15 minutes, survey initial viscosity, according to initial viscosity, the deionized water that adds 1/4-4/15 is transferred rare to being coated with for 4 viscosity 30-50 seconds.
5, check its viscosity to meet the requirements, soak plate checking dryness, hardness, surface effect, meet the requirements, surfacing, no significant defect is packed.
Embodiment 10, present embodiment are made by following proportioning raw materials, 15% deionized water, 2.5% propylene glycol, 1% dispersion agent: maleic anhydride copolymer, 0.5% defoamer: polyoxyethylene glycol, 1% wetting agent: polydimethylsiloxane, 7% carbon black, 14% iron oxide black, 25% water-borne acrylic resin, 24% aqueous epoxy resins, 1.5% dipropylene glycol, 2.5% propylene glycol: propylene glycol monomethyl ether and 6% polyaniline milk sap.The polyaniline emulsion is by 92% deionized water, 0.5% aniline, and 5.5% organic sulfonic acid: Witco 1298 Soft Acid and 2% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 9.
Embodiment 11, present embodiment are made by following proportioning raw materials, 10.8% deionized water, 5% propylene glycol, 1.5% dispersion agent: Viscotrol C sulphate, 0.2% defoamer: polysiloxane, 1.5% wetting agent: polyether-modified polydimethylsiloxane, 8% import carbon black, 22% iron oxide black, 27% water-borne acrylic resin, 20% aqueous epoxy resins, 1% dipropylene glycol butyl ether, 2% propylene glycol: propylene-glycol ethyl ether and 1% polyaniline milk sap.The polyaniline emulsion is by 90% deionized water, 2% aniline, and 7% organic sulfonic acid: camphorsulfonic acid and 1% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 9.
Embodiment 12, present embodiment is made by following proportioning raw materials, 12% deionized water, 3% propylene glycol, dispersion agent: the ammonium salt of 0.4% acrylate copolymer, 0.4% maleic anhydride copolymer and 0.45% Viscotrol C sulphate, defoamer: 0.2% polyoxyethylene glycol and 0.1% polysiloxane, 1.25% wetting agent: polydimethylsiloxane, 2% import carbon black, 10% iron oxide black, 30.2% watersoluble modified acrylic acid resin, 22% aqueous epoxy resins, 2% dipropylene glycol butyl ether, 4% propylene glycol: propylene glycol butyl ether and 12% polyaniline milk sap.The polyaniline emulsion is by 87% deionized water, 1% aniline, and 6% organic sulfonic acid: polystyrolsulfon acid and 6% Ammonium Persulfate 98.5 are made.Its making method is with embodiment 9.

Claims (4)

1. corrosion proof impregnating varnish used for water-based metal components, it is characterized in that: it is made by following proportioning raw materials, counts by weight percentage: the aqueous epoxy resins of the iron oxide black of the wetting agent of the dispersion agent of the deionized water of 8-15%, the propylene glycol of 1-5%, 0.5-1.5%, the defoamer of 0.1-0.5%, 0.5-1.5%, the carbon black of 2-8%, 10-22%, the water-borne acrylic resin of 25-33%, 20-28%, the dipropylene glycol butyl ether of 1-3%, the propylene glycol of 2-5% and the polyaniline aqueous solution or polyaniline carrier particles or the polyaniline emulsion of 1-12%; The described polyaniline aqueous solution is made by following proportioning raw materials, counts by weight percentage: the deionized water of 85-95%, the sodium-based montmorillonite of 2-10%, the aniline of 0.5-1.5%, the organic sulfonic acid of 0.8-3.0% and the Ammonium Persulfate 98.5 of 1-3%; Described polyaniline carrier particles is made by following proportioning raw materials, counts by weight percentage: the deionized water of 60-80%, the sodium-based montmorillonite of 10-32%, the aniline of 1.5-2.5%, the organic sulfonic acid of 4-6.5% and the Ammonium Persulfate 98.5 of 2-8%; Described polyaniline emulsion is made by following proportioning raw materials, counts by weight percentage: the deionized water of 84-92%, the aniline of 0.5-2.5%, the organic sulfonic acid of 5.5-8.5% and the Ammonium Persulfate 98.5 of 1-6%.
2. corrosion proof impregnating varnish used for water-based metal components according to claim 1 is characterized in that: described dispersion agent is one or more in ammonium salt, maleic anhydride copolymer and the Viscotrol C sulphate of acrylate copolymer; Defoamer is one or both in polyoxyethylene glycol and the polysiloxane, and when defoamer was two kinds of polyoxyethylene glycol and polysiloxane, its proportioning was 1: 0.5-2; Wetting agent is polyether-modified polydimethylsiloxane or polydimethylsiloxane.
3. according to claim 1 or 2 described corrosion proof impregnating varnish used for water-based metal components, it is characterized in that: described organic sulfonic acid is a kind of in tosic acid, Witco 1298 Soft Acid, camphorsulfonic acid and the polystyrolsulfon acid.
4. the making method of a corrosion proof impregnating varnish used for water-based metal components is characterized in that: described raw material and proportioning are according to the raw material and the proportioning of each described corrosion proof impregnating varnish used for water-based metal components among the claim 1-3:
It may further comprise the steps:
(1) as using the polyaniline carrier particles, earlier the polyaniline carrier particles of described amount is added in the deionized water of 1/5-1/4 of described amount, form the aqueous solution of polyaniline carrier particles;
(2) with 2/3 deionized water of the propylene glycol of described amount, described amount, as using the polyaniline carrier particles, with the deionized water of the 1/2-8/15 of described amount, adding is got the raw materials ready in the pot, with the speed stirring at low speed of 400-600rpm;
(3) aqueous solution that adds dispersion agent, defoamer, wetting agent and the polyaniline aqueous solution of described amount or polyaniline emulsion or the above-mentioned polyaniline carrier particles that mixes successively evenly after, the carbon black and the iron oxide black that add described amount, with the speed high speed dispersion of 1200rpm more than 20 minutes, form even mill base, do not have obvious dry mash piece;
(4) mill base that stirs is ground, till fineness≤20 μ m; The qualified mill base of grinding is squeezed into accent to be converted in the jar, start stirring, low speed mixing is even, the water-borne acrylic resin, the aqueous epoxy resins of described amount, the dipropylene glycol butyl ether of described amount and the propylene glycol of described amount that slowly add described amount successively, stir more than at least 15 minutes, add 1/3 of described amount, as using the polyaniline carrier particles, the deionized water that adds the 1/4-4/15 of described amount is transferred rare to being coated with for 4 viscosity 30-50 seconds;
The making method of the described polyaniline aqueous solution is, it may further comprise the steps: (1) places ultrasonic generator or beaker with the sodium-based montmorillonite of described amount, 9/10 the deionized water that adds described amount, ultrasonic dispersing or dispersed with stirring are more than 1 hour, make sodium-based montmorillonite homodisperse and abundant swelling in deionized water, stirring, heat temperature raising are to 78-82 ℃; (2) with the aniline of described amount and the organic sulfonic acid wiring solution-forming of described amount, and the formation aniline solution that stirs; (3) Ammonium Persulfate 98.5 that takes by weighing described amount is dissolved in 1/10 the deionized water of described amount and forms ammonium persulfate aqueous solution; (4) in nitrogen N 2Protection under, aniline solution is splashed in the described sodium-based montmorillonite aqueous dispersions, keep 78-82 ℃, stir and to disperse intercalation compound more than 3 hours down, form mixing solutions; Cooling subsequently, to the described Ammonium Persulfate 98.5 aqueous solution of mixed solution and dripping, the mixing solutions color is deepened gradually, after blackish green, continues reaction again more than 24 hours;
The making method of described polyaniline carrier particles, it may further comprise the steps: (1) at room temperature, the deionized water of described amount is inserted in the beaker, the sodium-based montmorillonite that takes by weighing described amount adds beaker, beaker is put into ultrasonic generator carry out ultrasonic dispersing, make it to be uniformly dispersed, be warming up to 78-82 ℃; (2) with the aniline and the organic sulfonic acid wiring solution-forming of described amount, and the formation aniline solution that stirs; (3) aniline solution is joined in the beaker lentamente, continue ultrasonic dispersing more than 5 hours in ultrasonic generator, reduce to the Ammonium Persulfate 98.5 that room temperature slowly adds described amount, reaction was continued more than 24 hours in the back that stirs; (4) then with its suction filtration, colourless to filtrate with washed with de-ionized water, 58-62 ℃ of oven dry promptly gets the polyaniline carrier particles after the grinding;
The making method of described polyaniline emulsion, it may further comprise the steps: (1) at room temperature, 9/10 deionized water of described amount is placed there-necked flask, the organic sulfonic acid that adds described amount, brute force stirs, and aniline that (2) then slowly drip described amount forms emulsion, and the Ammonium Persulfate 98.5 that takes by weighing described amount is dissolved in 1/10 the deionized water of described amount and forms ammonium persulfate aqueous solution, under stirring ammonium persulfate aqueous solution slowly is added in the emulsion, dropwises the back and continue reaction 5~8 hours.
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