CN104861848A - Component-type colored water-based polyurethane copolymer paint for metal - Google Patents
Component-type colored water-based polyurethane copolymer paint for metal Download PDFInfo
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Abstract
The invention relates to component-type colored water-based polyurethane copolymer paint for metal and belongs to the technical field of polyurethane paint and synthetic resin paint. The paint comprises priming paint and finishing paint and is characterized in that the priming paint as well as the finishing paint is prepared by mixing a component A, a component B and component C according to the weight ratio of 3.7:5.8:0.5, wherein the component A and the component C of the priming paint are the same as those of the finishing paint; the component A is a home-made internally-emulsified polyurethane tripolymer; and the components B comprise home-made internally-emulsified epoxy resin and are prepared from polyurethane, epoxy resin and other raw materials in percentage by weight respectively by corresponding production technologies. The paint has the advantages of beautiful color and luster, simple technologies, flexibility and convenience in preparation, high adhesive force, high hardness, long service life, acid/alkali/biochemical substance corrosion resistance and environment friendliness, and solves the problems in the prior art that the volatilization of organic solution steam can easily cause air environment pollution and the requirements for zero pollution, good color and luster and strong anti-corrosion performance are hard to meet.
Description
Technical field
The present invention relates to the coloured aqueous paint of a kind of component-type polyurethane interpolymer metal, belong to urethane synthetic resin paint technical field.
Background technology
Automobile, train, the inside and outside application paint vehicle of the metal product such as boats and ships, steel tower can effectively prevent metal rusting, chemical corrosion, and aesthetic appeal.Traditional water-borne coatings paint generally produces paint by organic solvent, and a large amount of organic solution steam evaporate in air, is the one of the main reasons causing haze to pollute.And no matter traditional water-borne coatings paint is prime paint or surface layer paint is generally do not have coloured, the multiple demand that market is pollution-free to water-miscible paint, color and luster is beautiful, protective is strong cannot be met.
Summary of the invention
The object of the invention is to, there is provided a kind of to be mixed by internal emulsification type Polyurethane tripolymer, internal emulsification type epoxy resin and other raw materials by weight, the used polymer network worn mutually can be formed fast under catalyst action, prime paint snappiness, wear resistance, rust-preventing characteristic are strong, and surface layer paint color and luster is beautiful, and anticorrosion resistance to acids and bases is strong, long service life, strong adhesion, fast drying, the environment friendly and pollution-free coloured aqueous paint of component-type polyurethane interpolymer metal; Solution prior art organic solution steam evaporate in air and easily causes environmental pollution, and is difficult to meet pollution-free, that color and luster is beautiful, protective is strong market requirement problem.
The present invention realizes above-mentioned purpose by the following technical solutions
The coloured aqueous paint of a kind of component-type polyurethane interpolymer metal is made up of prime paint, surface layer paint, prime paint, surface layer paint are made up of first component, component B, the third component respectively, it is characterized in that: all each free first component of prime paint, surface layer paint: component B: the third component is mixed by weight the ratio of 3.7: 5.8: 0.5; First component, third component of the first component of prime paint, the third component and surface layer paint are identical;
First component and the internal emulsification type Polyurethane tripolymer of prime paint, surface layer paint are made up of the raw material of following weight percent:
Tolylene diisocyanate 7.00%
Di-isocyanate 13.00%
(dehydration) dimethylbenzene 10.00%
Toluene 1.40%
Phosphoric acid 0.10%
Carboxylic acid/polyhydric alcohol solutions 20.00%
Tri-n-butyl phosphine 0.03%
Benzoyl chloride 0.06%
Hydrophilic solvent 20.11%
Deionized water 28.30%
Carboxylic acid/polyhydric alcohol solutions is become by the mixed raw material of following weight percent:
Dimethylol propionic acid 35%
TriMethylolPropane(TMP) 5%
Neopentyl glycol 10%
Dimethylbenzene (dehydration) 35%
Toluene 6%
Hydrophilic solvent is become by the mixed raw material of following weight percent:
Ethanol 50%
Cyclohexanone 20%
Butanone 10%
Acetate butyl 20%
The first component of prime paint, surface layer paint and internal emulsification type Polyurethane tripolymer, according to the proportioning raw materials of above-mentioned weight percent, prepared by following production technique:
Dimethylbenzene (dehydration) by 10.00%, the toluene of 6%, 20.00% carboxylic acid/polyhydric alcohol solutions drop into reactor, start stirring, open reflux exchanger, be warming up to 50 DEG C; Then be added dropwise in reactor by the toluene diisocyanate of 7.00%, time for adding is 1 hour; Be warming up to 60 DEG C after being added dropwise to complete, keep reaction, after 2 hours, the phosphoric acid of 0.10% is dropped into reactor;
The diisocyanate resin of 13.00% is added dropwise to reactor, time for adding is 2 hours, after being added dropwise to complete, be warming up to 70 DEG C, keep reaction, after 2 hours, the three normal-butyl phosphorus of 0.03% are dissolved into solution with appropriate toluene and be added dropwise to reactor, time for adding is 30 minutes, after being added dropwise to complete, be warming up to 80 DEG C, keep reaction to be warming up to 90 DEG C again after 2 hours, keep reaction 2 hours, now sampling detects free carbimide ﹤ 0.2%;
Subsequently the Benzoyl chloride q. s. toluene of 0.06% is dissolved into solution, slowly adds in reactor, be warming up to 100 DEG C, keep 20 minutes, to restrain trimerization reaction, be cooled to 80 DEG C, start evacuator, get rid of to deviate from organic solvent;
The hydrophilic solvent of 20.11% is slowly dropped into reactor, is incubated at 80 DEG C, 1 hour time, mix thoroughly, be cooled to 60 DEG C; Get the deionized water of 1.415%, be added dropwise to reactor, observation material reaction situation, is slowly warming up to 80 DEG C, make the carbimide complete reaction of dissociating, observation material does not occur that namely boiling explosion phenomenon reacts normal, is cooled to 60 DEG C, and the deionized water of remaining 26.885% is slowly dropped into reactor, mix thoroughly, be cooled to 30 DEG C of dischargings, i.e. obtained internal emulsification type Polyurethane tripolymer, packaging, for subsequent use;
Third component of prime paint, surface layer paint and blended ethamine are become by the mixed raw material of following weight percent:
Triethylene diamine 30%
N-Ethylmorphine quinoline 20%
Triethylamine 20%
Pure water 30%
The component B of prime paint and the coloured paint vehicle of rape oil alkyd epoxy resin, become by the mixed raw material of following weight percent:
Water-based rape oil Synolac 24.00%
Internal emulsification type epoxy resin 12.00%
Red iron oxide 13.00%
Titanium dioxide two chromium 09.00%
Zinc oxide 11.00%
Talcum powder 05.20%
Organobentonite 01.00%
Methyl-silicone oil 0.30%
Sodium hexametaphosphate 99 0.50%
D10 anticorrosion and bactericidal agent 0.20%
Methyl-2-pyrrolidone 0.80%
Deionized water 23.00%
The component B of surface layer paint and the coloured paint vehicle of Viscotrol C alkyd epoxy resin, become by the mixed raw material of following weight percent:
Water-based ricinoleyl alcohol acid resin 30.00%
Internal emulsification type epoxy resin 12.00%
Titanium dioxide 13.00%
Lithopone powder 14.00%
Magnesiumcarbonate powder 12.00%
Ultramarine powder 0.02%
Aerosil 0.60%
Methyl-silicone oil 0.30%
Sodium hexametaphosphate 99 0.60%
Methyl-2-pyrrolidone 0.70%
D10 anticorrosion and bactericidal agent 0.20%
Deionized water 16.58%
Internal emulsification type epoxy resin in the component B of prime paint and the component B of the coloured paint vehicle of rape oil alkyd epoxy resin and surface layer paint and Viscotrol C alkyd epoxy resin coloured enamel material formula, is all made up of the raw material of following weight percent:
Dihydroxyphenyl propane 23.25% ethylene glycol 1.00%
Polyoxyethylene 4.70% butanols 6.15%
Pure softening water 36.60% sodium carbonate 1.00%
Epoxy chloropropane 10.67% sodium hydroxide 1.00%
Catalyzer 1.00% internal emulsifying agent 3.43%
In and chainextender 0.80% solubility promoter 12.40%
This internal emulsification type epoxy resin, according to the proportioning raw materials of above-mentioned weight percent, is made by following production technique:
By the dihydroxyphenyl propane of 23.25%, the ethylene glycol of 1.00%, the polyoxyethylene of 4.70% drops into reactor, knocks down reactor, start stirring by 1/3rd of 3.43% internal emulsifying agent consumption;
By the pure softening water of 36.60%, the sodium carbonate of 1.00%, the sodium hydroxide of 1.00% mixes, get mixing total amount 2/3rds slowly drop into reactor, open reflux exchanger, are warming up to 65 DEG C, reaction maintenance is sample thief inspection after 1 hour, is cooled to 40 DEG C after the transparent shape of solution;
10.67% epoxy chloropropane is slowly dropped into reactor, mixes rear material solution thoroughly and start spontaneous temperature, produce thermopositive reaction to 60 DEG C, reaction maintenance is after 2 hours, and the internal emulsifying agent of 2/3rds of remainder is dropped into reactor, and be warming up to 80 DEG C, now reflux quickening;
The catalyst drops of 1.00% is added reactor, time for adding 1 hour, drip the pH value of rear maintenance solution 8.1, be warming up to 90 DEG C, reaction maintenance 3 hours, sample thief proving ring oxygen molecule amount reaches design requirements, be cooled to 70 DEG C, add the solubility promoter of 12.40%, mix thoroughly, be cooled to 40 DEG C, add in 0.80% and chainextender, regulate pH value 7.2, be warming up to 60 DEG C, reaction maintenance 1 hour, after observation solution is transparent, be cooled to 40 DEG C of dischargings, namely obtained internal emulsification type epoxy resin, for subsequent use.
The internal emulsifying agent of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: dimethylol propionic acid 50%, ethylene glycol monoethyl ether 20%, alkyl diol 30%.
The catalyzer of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: tartrate 33%, hexahydropyridine 17%, pure softening water 50%.
Become with the mixed raw material of chainextender by following weight percent in described preparation internal emulsification type epoxy resin: adipic acid 40%, diisopropanolamine (DIPA) 30%, pure water 30%.
The solubility promoter of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: ethanol 60%, toluene 20%, cyclohexanone 20%.
The present invention's beneficial effect is compared with prior art
This component-type polyurethane interpolymer metal with coloured aqueous paint by self-control internal emulsification type Polyurethane tripolymer, by hydrophilic carboxylic acid, dimethylol propionic acid, the polyreaction of isocyanic ester is introduced with water miscible polyvalent alcohol, neopentyl glycol, butyleneglycol, like this, at the initial stage of polyreaction, just be inlaid into network polymer systems that is blended, that run through mutually, and hydrophilic carboxylic acid molecules and hydrophilic polyol molecule; When isocyanic ester is when reacting generation tripolymer, just become the blended interpolymer of water miscible internal emulsification type isocyanic ester diversification, i.e. aqueous polyurethane paint vehicle.Mutually the used polymer network worn, can realize adding colouring material in prime paint, surface layer paint, enamelled coating color and luster and color beautiful, production technique is simple, and preparation is flexible, and coating operation is easily controlled, enamelled coating is to the strong adhesion of metal, and hardness is high, lacquer painting long service life.By self-control internal emulsification type epoxy resin, hydrophilic group is incorporated on epoxy molecule chain, epoxy resin is made to obtain the character of self-emulsifying, in occurring with hydroxy-acid group and while curing reaction, promote that the group of the urethano in first component reacts with the oh group in component B paint vehicle, make the polynary resin of copolymerization in paint film along with the volatilization rapid reaction crosslinking curing of moisture content, can be attached to metal faced securely, make the over-all properties that paint film layer possesses very strong sea water resistance, resistance to sunlight burns solarization, chemical species corrodes.Effective raising superpolymer raw material is as the water-soluble ability of alkyd, epoxy resin, urethane; Can not to environment.Solve prior art organic solution steam well to evaporate in air and easily cause environmental pollution, and be difficult to meet pollution-free, that color and luster enriches, protective is strong market requirement problem.
Embodiment
Below this component-type polyurethane interpolymer metal embodiment of coloured aqueous paint is described in detail:
The coloured aqueous paint of a kind of component-type polyurethane interpolymer metal is made up of prime paint, surface layer paint, and prime paint, surface layer paint are made up of first component, component B, the third component respectively; The all each free first component of prime paint, surface layer paint: component B: the third component is mixed by weight the ratio of 3.7: 5.8: 0. 5; First component, third component of the first component of prime paint, the third component and surface layer paint are identical;
First component and the internal emulsification type Polyurethane tripolymer of prime paint, surface layer paint are made up of the raw material of following weight percent:
Tolylene diisocyanate 7.00%;
Di-isocyanate 13.00%;
Hydrophobizing agent: dimethylbenzene (dehydration) 10.00%;
Return agents: toluene 1.40%;
Stablizer: phosphoric acid 0.10%
Catalyst for trimerization: tri-n-butyl phosphine 0.03%
Internal emulsifying agent: carboxylic acid/polyhydric alcohol solutions 20.00%;
Trimerization inhibitor; Benzoyl chloride 0.06%;
Hydrophilic solvent 20.11%;
Deionized water 28.30%;
Internal emulsifying agent: carboxylic acid/polyhydric alcohol solutions is become by the mixed raw material of following weight percent:
Dimethylol propionic acid 35%; TriMethylolPropane(TMP) 5%;
Neopentyl glycol 10%; Dimethylbenzene (dehydration) 35%; Toluene 6%;
Hydrophilic solvent is become by the mixed raw material of following weight percent:
Ethanol 50%; Cyclohexanone 20%; Butanone 10%; Acetate butyl 20%;
The first component of prime paint, surface layer paint and internal emulsification type Polyurethane tripolymer, according to the proportioning raw materials of above-mentioned weight percent, prepared by following production technique:
Dimethylbenzene (dehydration) by 10.00%, the toluene of 6%, 20.00% carboxylic acid/polyhydric alcohol solutions drop into reactor, start stirring, open reflux exchanger, be warming up to 50 DEG C; Then be added dropwise in reactor by the toluene diisocyanate of 7.00%, time for adding is 1 hour; Be warming up to 60 DEG C after being added dropwise to complete, keep reaction, after 2 hours, the phosphoric acid of 0.10% is dropped into reactor;
The diisocyanate resin of 13.00% is added dropwise to reactor, time for adding is 2 hours, after being added dropwise to complete, be warming up to 70 DEG C, keep reaction, after 2 hours, the three normal-butyl phosphorus of 0.03% are dissolved into solution with appropriate toluene and be added dropwise to reactor, time for adding is 30 minutes, after being added dropwise to complete, be warming up to 80 DEG C, keep reaction to be warming up to 90 DEG C again after 2 hours, keep reaction 2 hours, now sampling detects free carbimide ﹤ 0.2%;
Subsequently the Benzoyl chloride q. s. toluene of 0.06% is dissolved into solution, slowly adds in reactor, be warming up to 100 DEG C, keep 20 minutes, restrain trimerization reaction, be cooled to 80 DEG C, start evacuator, get rid of to deviate from organic solvent;
The hydrophilic solvent of 20.11% is slowly dropped into reactor, is incubated at 80 DEG C, 1 hour time, mix thoroughly, be cooled to 60 DEG C; Get the deionized water of 1.415%, be added dropwise to reactor, observation material reaction situation, is slowly warming up to 80 DEG C, make the carbimide complete reaction of dissociating, material to be observed does not occur that namely boiling explosion phenomenon reacts normal, is cooled to 60 DEG C, and the deionized water of remaining 26.885% is slowly dropped into reactor, mix thoroughly, be cooled to 30 DEG C of dischargings, i.e. obtained internal emulsification type Polyurethane tripolymer, packaging, for subsequent use;
Third component of prime paint, surface layer paint and blended ethamine become by the mixed raw material of following weight percent:
Triethylene diamine 30%; N-Ethylmorphine quinoline 20%;
Triethylamine 20%; Pure water 30%;
Blended ethamine is as catalyzer;
The component B of prime paint and the coloured paint vehicle of rape oil alkyd epoxy resin, become by the mixed raw material of following weight percent:
Self-control: water-based rape oil Synolac 24.00%
Self-control: internal emulsification type epoxy resin 12.00%
Pigment agent: red iron oxide 13.00%
Rust-preventive agent: titanium dioxide two chromium 9.00%
Filler: zinc oxide 11.00%
Filler: talcum powder 5.20%
Filler: organobentonite 1.00%
Defoamer: methyl-silicone oil 0.30%
Wetting dispersing agent: Sodium hexametaphosphate 99 0.50%
D10 anticorrosion and bactericidal agent 0.20%
Film coalescence aid: methyl-2-pyrrolidone 0.80%
Deionized water 23.00%
The component B of surface layer paint and the coloured paint vehicle of Viscotrol C alkyd epoxy resin, become by the mixed raw material of following weight percent:
Self-control: water-based ricinoleyl alcohol acid resin 30.00%
Self-control: internal emulsification type epoxy resin 12.00%
Pigment agent: titanium dioxide 13.00%
Pigment agent: lithopone powder 14.00%
Pigment agent: magnesiumcarbonate powder 12.00%
Pigment agent: ultramarine powder 0.02%
Thickening material: aerosil 0.60%
Defoamer: methyl-silicone oil 0.30%
Wetting dispersing agent: Sodium hexametaphosphate 99 0.60%
Film coalescence aid: methyl-2-pyrrolidone 0.70%
D10 anticorrosion and bactericidal agent 0.20%
Deionized water 16.58%
Internal emulsification type epoxy resin in the component B of prime paint and the component B of the coloured paint vehicle of rape oil alkyd epoxy resin and surface layer paint and Viscotrol C alkyd epoxy resin coloured enamel material formula is made up of the raw material of following weight percent:
Dihydroxyphenyl propane 23.25% ethylene glycol 1.00%
Polyoxyethylene 4.70% butanols 6.15%
Pure softening water 36.60% sodium carbonate 1.00%
Epoxy chloropropane 10.67% sodium hydroxide 1.00%
Catalyzer 1.00% internal emulsifying agent 3.43%
In and chainextender 0.80% solubility promoter 12.40%
Internal emulsification type epoxy resin, according to the proportioning raw materials of above-mentioned weight percent, is prepared by following production technique:
By the dihydroxyphenyl propane of 23.25%, the ethylene glycol of 1.00%, the polyoxyethylene of 4.70% drops into reactor, knocks down reactor, start stirring by 1/3rd of 3.43% internal emulsifying agent consumption;
By the pure softening water of 36.60%, the sodium carbonate of 1.00%, the sodium hydroxide of 1.00% mixes, get mixing total amount 2/3rds slowly drop into reactor, open reflux exchanger, are warming up to 65 DEG C, reaction maintenance is sample thief inspection after 1 hour, is cooled to 40 DEG C after the transparent shape of solution;
10.67% epoxy chloropropane is slowly dropped into reactor, mixes rear material solution thoroughly and start spontaneous temperature, produce thermopositive reaction to 60 DEG C, reaction maintenance is after 2 hours, and the internal emulsifying agent of 2/3rds of remainder is dropped into reactor, and be warming up to 80 DEG C, now reflux quickening;
Dropped into by the catalyzer of 1.00% and drip still, start to drip, time for adding 1 hour, drips off the pH value of rear maintenance solution 8.1, be warming up to 90 DEG C, reaction maintenance 3 hours, sample thief proving ring oxygen molecule amount reaches design requirements, be cooled to 70 DEG C, add the solubility promoter of 12.40%, mix thoroughly, be cooled to 40 DEG C, add in 0.80% and chainextender, regulate pH value 7.2, be warming up to 60 DEG C, reaction maintenance 1 hour, after observation solution is transparent, be cooled to 40 DEG C of dischargings, namely obtained internal emulsification type epoxy resin, for subsequent use.
The internal emulsifying agent of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: dimethylol propionic acid 50%, ethylene glycol monoethyl ether 20%, alkyl diol 30%.
The catalyzer of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: tartrate 33%, hexahydropyridine 17%, pure softening water 50%.
Become with the mixed raw material of chainextender by following weight percent in described preparation internal emulsification type epoxy resin: adipic acid 40%, diisopropanolamine (DIPA) 30%, pure water 30%.
The solubility promoter of described preparation internal emulsification type epoxy resin is become by the mixed raw material of following weight percent: ethanol 60%, toluene 20%, cyclohexanone 20%.
This component-type polyurethane interpolymer metal with prime paint, the first component of surface layer paint of coloured aqueous paint, the third component is raw materials used and production technique is all identical; Internal emulsification type epoxy resin in the component B of prime paint, surface layer paint is raw materials used and production technique is all identical; First component: the internal emulsification type epoxy resin in internal emulsification type Polyurethane tripolymer and component B is the key point making the coloured aqueous paint of this component-type polyurethane interpolymer metal.
Below the specific embodiment of the coloured aqueous paint of this component-type polyurethane interpolymer metal:
To produce 1000 kilograms of first component internal emulsification type Polyurethane tripolymers:
1), first component: internal emulsification type Polyurethane tripolymer, is prepared as follows by the raw material of above-mentioned weight percent and production technique:
Get toluene diisocyanate 70 kilograms, diisocyanate resin 130 kilograms, dehydration dimethylbenzene 100 kilograms, toluene 14 kilograms, phosphatase 11 kilogram, internal emulsifying agent carboxylic acid/polyhydric alcohol solutions 200 kilograms, tri-n-butyl phosphine 0.3 kilogram, Benzoyl chloride 0.6 kilogram, hydrophilic solvent 201.1 kilograms, deionized water 283 kilograms;
To be dewatered dimethylbenzene 100 kilograms, toluene 14 kilograms, internal emulsifying agent carboxylic acid/polyhydric alcohol solutions 200 kilograms, drop into reactor, start stirring, open reflux exchanger, be warming up to 50 DEG C; By paint toluene diisocyanate 70 kilograms, be added dropwise to reactor, time for adding is 1 hour, after being added dropwise to complete, and is warming up to 60 DEG C, keeps reaction after 2 hours by phosphatase 11 kilogram input reactor; Paint is added dropwise to reactor with diisocyanate resin 130 kilograms, and start to drip, time for adding is 2 hours; After completing, be warming up to 70 DEG C.Keep reaction 2 hours;
By 300 grams, catalyst for trimerization three normal-butyl phosphorus, be dissolved into solution, be added dropwise to reactor with appropriate toluene, start to drip, time for adding is 30 minutes; After completing, be warming up to 80 DEG C, keep reaction 2 hours, be warming up to 90 DEG C, keep reaction 2 hours; After the carbimide that sampling detection dissociates is less than 0.2%, by trimerization inhibitor Benzoyl chloride 600 grams, after being dissolved into solution with q. s. toluene, slowly drops into reactor, be warming up to 100 DEG C, keep 20 minutes, trimerization reaction is restrained; Be cooled to 80 DEG C, start evacuator, deviate from organic solvent; (referring to dimethylbenzene, toluene, a small amount of carbimide etc. of not participating in reaction)
By hydrophilic solvent 211 kilograms, slowly drop into reactor, be incubated at 80 DEG C, 1 hour time, mix thoroughly, be cooled to 60 DEG C; Remove ionized water 1 kilogram, be added dropwise to reactor, start to drip, observation material reaction situation, is slowly warming up to 80 DEG C, is reacted completely by free carbimide, observation material does not occur that namely boiling explosion phenomenon reacts normal, is cooled to 60 DEG C, by deionized water 282 kilograms, slow input reactor, mixes thoroughly, is cooled to 30 DEG C, discharging, i.e. obtained internal emulsification type Polyurethane tripolymer, packaging, first component is for subsequent use.
2), to produce the internal emulsification type epoxy resin in 1000 kilograms of component B formulas:
Internal emulsification type epoxy resin in the component B formula of prime paint, surface layer paint, raw material and production technique preparation by above-mentioned weight percent:
By dihydroxyphenyl propane 232.5 kilograms, ethylene glycol 10 kilograms, polyoxyethylene 47 kilograms of reactors that put into production; By 1/3rd of internal emulsifying agent consumption, namely 11.4 kilograms, knock down into reactor, start stirring; After pure softening water 360 kilograms, 10 kilograms, sodium carbonate, 10 kilograms, sodium hydroxide are first mixed, get 2/3rds of total amount, namely slowly knock down into reactor for 235 kilograms; Open reflux exchanger, be warming up to 65 DEG C, reaction maintenance is sample thief test after 1 hour, is cooled to 40 DEG C after solution is transparent; By epoxy chloropropane 106.7 kilograms, slowly knock down into reactor, mix rear material solution thoroughly and start spontaneous temperature, produce thermopositive reaction to 60 DEG C, the internal emulsifying agent 22.8 kilograms of remainder, after 2 hours, is knocked down into reactor, is warming up to 80 DEG C by reaction maintenance, and backflow is accelerated; By catalyzer 10 kilograms, knock down into dropping still, start to drip, 1 hour time, after dripping off, keep the pH value of solution 8.1.Be warming up to 90 DEG C, reaction maintenance is after 3 hours, and sample thief test epoxy molecule amount reaches design requirements, is cooled to 70 DEG C; Add solubility promoter 110 kilograms, mix thoroughly, be cooled to 40 DEG C; With chainextender 8 kilograms in adding, regulate pH value 7.2, be warming up to 60 DEG C, reaction maintenance 1 hour, after observation solution is transparent, is cooled to 40 DEG C, discharging, and namely obtained internal emulsification type epoxy resin, for subsequent use.
Water-based ricinoleyl alcohol acid resin in water-based rape oil Synolac in the component B of prime paint and rape oil alkyd epoxy resin coloured enamel material formula, the component B of surface layer paint and alkyd epoxy resin coloured enamel material formula, see present inventor's article that [Chinese coating] periodical o. 11th, the 12nd phase in 2004 publishes.
Water-based rape oil Synolac is made up of the raw material of following weight percent:
Rape salad oil 21.52%; Castor Oil Fatty Acid 5.75%;
TriMethylolPropane(TMP) 6.97%; Neopentyl glycol 5.85%;
Isopropylcarbinol 1.59%; Naphthenic acid lithium 0.01%;
The inclined front three acid anhydrides 6.00% of benzene; Deionization 48.84%;
Hydrophilic solvent 1.57%; Triethylamine 0.70%;
Internal emulsifying agent: dimethylol propionic acid 1.20%;
To produce 1000 kilograms; Production technique is as follows:
Get rape salad oil 215.20 kilograms, Castor Oil Fatty Acid 57.50 kilograms, TriMethylolPropane(TMP) 69.70 kilograms, neopentyl glycol 58.50 kilograms, isopropylcarbinol 15.90 kilograms, naphthenic acid lithium 0.01 kilogram, 60.00 kilograms, the inclined front three acid anhydrides of benzene, internal emulsifying agent dimethylol propionic acid 12.00 kilograms, commixed type hydrophilic solvent 15.70 kilograms, triethylamine 7.00 kilograms, deionized water 488.40 kilograms;
By rape salad oil 215.20 kilograms, Castor Oil Fatty Acid 57.5 kilograms, TriMethylolPropane(TMP) 50 kilograms, neopentyl glycol 45.8 kilograms, isopropylcarbinol 15.9 kilograms, drop into reactor, pass into carbon dioxide gas, start stirring, open reflux exchanger, be warming up to 120 DEG C, add naphthenic acid lithium 100 grams, be warming up to 230 DEG C, react after 3 hours, inspection by sampling, after alcoholysis is transparent, be cooled to 180 DEG C, add 60 kilograms, the inclined front three acid anhydrides of benzene, internal emulsifying agent dimethylol propionic acid 12 kilograms, insulation is at 180 DEG C, react after 2 hours, every 30 minutes, sampling and testing acid number pH value reaches 70 milligrams of KOH/ gram, be cooled to 90 DEG C, add commixed type hydrophilic solvent 75.7 kilograms, after stirring, by triethylamine 3 kilograms, slowly add, adjust pH value to 7.2, be cooled to 60 DEG C, add deionized water 488.4 kilograms, mix thoroughly, be cooled to 30 DEG C, discharging, i.e. obtained water-based rape oil Synolac, for subsequent use.
Water-based ricinoleyl alcohol acid resin is made up of the raw material of following weight percents:
Viscotrol C 25.90% TriMethylolPropane(TMP) 3.30%;
Neopentyl glycol 3.10% isopropylcarbinol 1.70%;
Yellow lead oxide 0.01%; Benzene inclined front three acid anhydrides 8.86% rosin dibasic alcohol 2.50%; Commixed type hydrophilic solvent 1.93%; Triethylamine 0.80%; Deionized water 51.00%;
Internal emulsifying agent: dimethylol propionic acid 0.90%;
To produce 1000 kilograms of water-based ricinoleyl alcohol acid resins, production technique is as follows:
Get Viscotrol C 259 kilograms, TriMethylolPropane(TMP) 33 kilograms, neopentyl glycol 31 kilograms, isopropylcarbinol 17 kilograms, yellow lead oxide 0.01 kilogram, 88.60 kilograms, the inclined front three acid anhydrides of benzene, internal emulsifying agent dimethylol propionic acid 0.9 kilogram, rosin dibasic alcohol 25 kilograms, commixed type hydrophilic solvent 19.3 kilograms, triethylamine 8 kilograms;
By Viscotrol C 259 kilograms, TriMethylolPropane(TMP) 33.0 kilograms, neopentyl glycol 31 kilograms, isopropylcarbinol 17 kilograms of input reactors, start stirring, open reflux exchanger, pass into carbon dioxide gas, be warming up to 120 DEG C, add yellow lead oxide 0.01 kilogram, be warming up to 230 DEG C, react 3 hours, sampling test, after alcoholysis is transparent, be cooled to 180 DEG C, add 88.6 kilograms, the inclined front three acid anhydrides of benzene, internal emulsifying agent dimethylol propionic acid 0.9 kilogram, rosin dibasic alcohol 25 kilograms, temperature is at 180 DEG C, react after 2 hours, every inspection by sampling in 30 minutes, till acid number reaches 80 milligrams of KOH/ gram, be cooled to 90 DEG C, enter hydrophilic solvent 19.30 kilograms, after mixing thoroughly, be cooled to 50 DEG C, triethylamine 0.80 kilogram is slowly added, pH value is regulated to be 7.5, be warming up to 60 DEG C, mix thoroughly, solution is transparent, be cooled to 30 DEG C, discharging, and obtained water-based ricinoleyl alcohol acid resin, for subsequent use.
This component-type polyurethane interpolymer metal making processes of coloured aqueous paint, adopts the raw material of above-mentioned weight percent, to produce 1000 kilograms;
The component B of priming paint is colored paint product: rape oil alkyd epoxy colored paint material, it is be made up of the starting material of following weight percents: water-based rape oil Synolac 24.00%, internal emulsification type epoxy resin 12.00%, tinting material: red iron oxide 13.00%, rust-preventive agent: titanium dioxide two chromium 9.00%, filler: zinc oxide 11.00%, talcum powder 5.20%, organobentonite 1.00%, defoamer: methyl-silicone oil 0.30%, wetting dispersing agent: Sodium hexametaphosphate 99 0.50%, D10 anticorrosion and bactericidal agent 0.20%, film coalescence aid: N-Methyl pyrrolidone 0.80%(also can adopt N-ethyl pyrrolidone 0.80%), deionized water 23.00%.
The making processes of the component B of prime paint: by water-based rape oil Synolac 240 kilograms, internal emulsification type epoxy resin 120 kg, red iron oxide 130 kilogram, titanium dioxide two chromium 90 kilograms, 110 kilograms, zinc oxide, talcum powder 52 kilograms, organobentonite 10 kilograms, methyl-silicone oil 3 kilograms, Sodium hexametaphosphate 99 5 kilograms, D10 anticorrosion and bactericidal agent 2 kilograms, N-Methyl pyrrolidone 8 kilograms, deionized water 230 kilograms, drop into stirring tank successively, after mixing thoroughly, enter shredder, be ground to 16 microns of fineness to sieve, package spare.
The component B of surface layer paint is colored paint product: the coloured paint vehicle of Viscotrol C alkyd epoxy, is made up of the starting material of following weight percent; Water-based ricinoleyl alcohol acid resin 30.00%, internal emulsification type epoxy resin 12.00%, tinting material: titanium dioxide 13.00%, lithopone powder 14.00%, magnesiumcarbonate powder 12.00%, ultramarine 0.02%, thickening material: aerosil 0.60%, defoamer: methyl-silicone oil 0.30%, wetting dispersing agent: Sodium hexametaphosphate 99 0.60%, D10 anticorrosion and bactericidal agent 0.20%, film coalescence aid: methyl-2-pyrrolidone 0.70%, deionized water 16.58%.
The making processes of the component B of surface layer paint: by water-based ricinoleyl alcohol acid resin 300.0 kilograms, internal emulsification type epoxy resin 120.0 kilograms, titanium dioxide 130.0 kilograms, 140.0 kilograms, lithopone powder, 120.0 kilograms, magnesiumcarbonate powder, 0.02 kilogram, ultramarine, aerosil 6.0 kilograms, methyl-silicone oil 3.0 kilograms, Sodium hexametaphosphate 99 6.0 kilograms, D10 anticorrosion and bactericidal agent 6.0 kilograms, methyl-2-pyrrolidone 7.0 kilograms, deionized water 165.8 kilograms, drops into stirring tank successively, starts stirring, after mixing thoroughly, enter shredder, be ground to 14 microns of fineness, package spare.
The first component of prime paint: component B: the third component, by weight the ratio of 3.7: 5.8: 0.5, to pack greatly 10 kilograms; First component internal emulsification type Polyurethane tripolymer 3.7 kilograms, 5.7 kilograms, component B rape oil alkyd epoxy colored paint material.Third component use, 0.5 kilogram, blended ethamine.Respectively with 3.7 kilograms of buckets, 5.7 kilograms of buckets, 0.5 kilogram of bucket, packs.
The first component of surface layer paint: component B: the third component, finishes the ratio of 3.7: 5.8: 0.5, by weight to pack greatly 10 kilograms; First component internal emulsification type Polyurethane tripolymer 3.7 kilograms; 5.7 kilograms, component B Viscotrol C alkyd epoxy colored paint material; Third 0.5 kilogram, component blend ethamine; Respectively with 3.7 kilograms of buckets, 5.7 kilograms of buckets, 0.5 kilogram of bucket, packs.
Due to the first component of prime paint and surface layer paint, the third component adopt raw material and production technique identical, therefore only need distinguish the component B of prime paint and surface layer paint during packaging.
This component-type polyurethane interpolymer metal application of coloured aqueous paint: during use, first by prime paint first component, component B mixing and stirring, then add the third component, stir, can carry out smearing operation.Prime paint carry out according to the method described above again after having smeared surface layer paint stirring, smear operation.After the first component of prime paint and surface layer paint, component B, the third component mix, all must be finished in 8 hours, need not solidify more than 8 hours after mixing
The prime paint of this component-type polyurethane interpolymer metal with coloured aqueous paint and the first component of surface layer paint, by hydrophilic carboxylic acid, dimethylol propionic acid, with water miscible many Qi alcohol, neopentyl glycol, butyleneglycol introduces the polyreaction of isocyanic ester, make it at the initial stage of polyreaction, be just inlaid into the hydrophilic carboxylic acid molecules of blended, interpenetrating polymer networks system and hydrophilic polyol molecule.Like this, isocyanic ester, when being reacted into tripolymer, just becomes water miscible internal emulsification type isocyanic ester, the aqueous polyurethane paint vehicle of the blended interpolymer of diversification.
The prime paint of this component-type polyurethane interpolymer metal with coloured aqueous paint and the component B of surface layer paint, pass through water soluble alkyd resin, with internal emulsification type epoxy resin, pigment, filler, after auxiliary agent mixing, along with the third component catalyst, adding of solidifying agent, in occurring with first component hydroxy-acid group and curing reaction, promote that the group of the urethano in first component reacts with the oh group in component B paint vehicle, make the volatilization of polynary resin along with moisture of copolymerization in paint film, rapid reaction crosslinking curing, metal level can be attached to securely, paint film layer is made to possess very strong sea water resistance, the resistance to sun shines, the over-all properties of chemical species corrosion.
Compared with traditional paint, this component-type polyurethane interpolymer metal high polymer material of coloured aqueous paint: the good water solubility of alkyd, epoxy resin, urethane, snappiness, the wear resistance of prime paint are strong; The surface layer paint color of smearing is beautiful, and meanwhile, preservative property, resistance to acids and bases, scratch resistance, environment friendly and pollution-free property are strong.The coloured aqueous paint of this component-type polyurethane interpolymer metal shows through repeatedly using, and preparation, applying flexible are conveniently, strong to metal adhesion, lastingly beautiful in colour, seawater corrosion resistance, long service life.Be applicable to all metal objects such as naval vessel, steel tower, automobile, the inside and outside coating of train to use, result of use is good.
The above is the embodiment of this invention, above-mentioned illustrating is not construed as limiting flesh and blood of the present invention, person of an ordinary skill in the technical field can make an amendment above-mentioned embodiment or be out of shape after having read this specification sheets, and does not deviate from the spirit and scope of the invention.
Claims (5)
1. the coloured aqueous paint of component-type polyurethane interpolymer metal, it is made up of prime paint, surface layer paint, prime paint, surface layer paint are made up of first component, component B, the third component respectively, it is characterized in that: all each free first component of prime paint, surface layer paint: component B: the third component is mixed by weight the ratio of 3.7: 5.8: 0.5; First component, third component of the first component of prime paint, the third component and surface layer paint are identical;
First component and the internal emulsification type Polyurethane tripolymer of prime paint, surface layer paint are made up of the raw material of following weight percent:
Tolylene diisocyanate 7.00%
Di-isocyanate 13.00%
Dimethylbenzene (dehydration) 10.00%
Toluene 1.40%
Phosphoric acid 0.10%
Carboxylic acid/polyhydric alcohol solutions 20.00%
Tri-n-butyl phosphine 0.03%
Benzoyl chloride 0.06%
Hydrophilic solvent 20.11%
Deionized water 28.30%
Carboxylic acid/polyhydric alcohol solutions is become by the mixed raw material of following weight percent:
Dimethylol propionic acid 35%
TriMethylolPropane(TMP) 5%
Neopentyl glycol 10%
Dimethylbenzene (dehydration) 35%
Toluene 6%
Hydrophilic solvent is become by the mixed raw material of following weight percent:
Ethanol 50%
Cyclohexanone 20%
Butanone 10%
Acetate butyl 20%
The first component of prime paint, surface layer paint and internal emulsification type Polyurethane tripolymer, according to the proportioning raw materials of above-mentioned weight percent, prepared by following production technique:
Dimethylbenzene (dehydration) by 10.00%, the toluene of 6%, 20.00% carboxylic acid/polyhydric alcohol solutions drop into reactor, start stirring, open reflux exchanger, be warming up to 50 DEG C; Then be added dropwise in reactor by the toluene diisocyanate of 7.00%, time for adding is 1 hour; Be warming up to 60 DEG C after being added dropwise to complete, keep reaction, after 2 hours, the phosphoric acid of 0.10% is dropped into reactor;
The diisocyanate resin of 13.00% is added dropwise to reactor, time for adding is 2 hours, after being added dropwise to complete, be warming up to 70 DEG C, keep reaction, after 2 hours, the three normal-butyl phosphorus of 0.03% are dissolved into solution with appropriate toluene and be added dropwise to reactor, time for adding is 30 minutes, after being added dropwise to complete, be warming up to 80 DEG C, keep reaction to be warming up to 90 DEG C again after 2 hours, keep reaction 2 hours, now sampling detects free carbimide ﹤ 0.2%;
Subsequently the Benzoyl chloride q. s. toluene of 0.06% is dissolved into solution, slowly adds in reactor, be warming up to 100 DEG C, keep 20 minutes, to restrain trimerization reaction, be cooled to 80 DEG C, start evacuator, get rid of to deviate from organic solvent;
The hydrophilic solvent of 20.11% is slowly dropped into reactor, is incubated at 80 DEG C, 1 hour time, mix thoroughly, be cooled to 60 DEG C; Get the deionized water of 1.415%, be added dropwise to reactor, observation material reaction situation, is slowly warming up to 80 DEG C, make the carbimide complete reaction of dissociating, observation material does not occur that namely boiling explosion phenomenon reacts normal, is cooled to 60 DEG C, and the deionized water of remaining 26.885% is slowly dropped into reactor, mix thoroughly, be cooled to 30 DEG C of dischargings, i.e. obtained internal emulsification type Polyurethane tripolymer, packaging, for subsequent use;
Third component of prime paint, surface layer paint and blended ethamine are become by the mixed raw material of following weight percent:
Triethylene diamine 30%
N-Ethylmorphine quinoline 20%
Triethylamine 20%
Pure water 30%
The component B of prime paint and the coloured paint vehicle of rape oil alkyd epoxy resin, become by the mixed raw material of following weight percent:
Water-based rape oil Synolac 24.00%
Internal emulsification type epoxy resin 12.00%
Red iron oxide 13.00%
Titanium dioxide two chromium 09.00%
Zinc oxide 11.00%
Talcum powder 05.20%
Organobentonite 01.00%
Methyl-silicone oil 0.30%
Sodium hexametaphosphate 99 0.50%
D10 anticorrosion and bactericidal agent 0.20%
Methyl-2-pyrrolidone 0.80%
Deionized water 23.00%
The component B of surface layer paint and the coloured paint vehicle of Viscotrol C alkyd epoxy resin, become by the mixed raw material of following weight percent:
Water-based ricinoleyl alcohol acid resin 30.00%
Internal emulsification type epoxy resin 12.00%
Titanium dioxide 13.00%
Lithopone powder 14.00%
Magnesiumcarbonate powder 12.00%
Ultramarine powder 0.02%
Aerosil 0.60%
Methyl-silicone oil 0.30%
Sodium hexametaphosphate 99 0.60%
Methyl-2-pyrrolidone 0.70%
D10 anticorrosion and bactericidal agent 0.20%
Deionized water 16.58%
Internal emulsification type epoxy resin in the component B of prime paint and the component B of the coloured paint vehicle of rape oil alkyd epoxy resin and surface layer paint and Viscotrol C alkyd epoxy resin coloured enamel material formula, is all made up of the raw material of following weight percent:
Dihydroxyphenyl propane 23.25% ethylene glycol 1.00%
Polyoxyethylene 4.70% butanols 6.15%
Pure softening water 36.60% sodium carbonate 1.00%
Epoxy chloropropane 10.67% sodium hydroxide 1.00%
Catalyzer 1.00% internal emulsifying agent 3.43%
In and chainextender 0.80% solubility promoter 12.40%
This internal emulsification type epoxy resin, according to the proportioning raw materials of above-mentioned weight percent, is made by following production technique:
By the dihydroxyphenyl propane of 23.25%, the ethylene glycol of 1.00%, the polyoxyethylene of 4.70% drops into reactor, knocks down reactor, start stirring by 1/3rd of 3.43% internal emulsifying agent consumption;
By the pure softening water of 36.60%, the sodium carbonate of 1.00%, the sodium hydroxide of 1.00% mixes, get mixing total amount 2/3rds slowly drop into reactor, open reflux exchanger, are warming up to 65 DEG C, reaction maintenance is sample thief inspection after 1 hour, is cooled to 40 DEG C after the transparent shape of solution;
10.67% epoxy chloropropane is slowly dropped into reactor, mixes rear material solution thoroughly and start spontaneous temperature, produce thermopositive reaction to 60 DEG C, reaction maintenance is after 2 hours, and the internal emulsifying agent of 2/3rds of remainder is dropped into reactor, and be warming up to 80 DEG C, now reflux quickening;
The catalyst drops of 1.00% is added reactor, time for adding 1 hour, drip the pH value of rear maintenance solution 8.1, be warming up to 90 DEG C, reaction maintenance 3 hours, sample thief proving ring oxygen molecule amount reaches design requirements, be cooled to 70 DEG C, add the solubility promoter of 12.40%, mix thoroughly, be cooled to 40 DEG C, add in 0.80% and chainextender, regulate pH value 7.2, be warming up to 60 DEG C, reaction maintenance 1 hour, after observation solution is transparent, be cooled to 40 DEG C of dischargings, namely obtained internal emulsification type epoxy resin, for subsequent use.
2. the coloured aqueous paint of a kind of component-type polyurethane interpolymer metal according to claim 1, it is characterized in that: the internal emulsifying agent preparing internal emulsification type epoxy resin in described component B is become by the mixed raw material of following weight percent: dimethylol propionic acid 50%, ethylene glycol monoethyl ether 20%, alkyl diol 30%.
3. the coloured aqueous paint of a kind of component-type polyurethane interpolymer metal according to claim 1,2, it is characterized in that: the catalyzer preparing internal emulsification type epoxy resin in described component B is become by the mixed raw material of following weight percent: tartrate 33%, hexahydropyridine 17%, pure softening water 50%.
4. the coloured aqueous paint of a kind of component-type polyurethane interpolymer metal according to claim 1,2,3, it is characterized in that: prepare in described component B in internal emulsification type epoxy resin to become with the mixed raw material of chainextender by following weight percent: adipic acid 40%, diisopropanolamine (DIPA) 30%, pure water 30%.
5. the coloured aqueous paint of a kind of component-type polyurethane interpolymer metal according to claims 1 to 4, it is characterized in that: the solubility promoter preparing internal emulsification type epoxy resin in described component B is become by the mixed raw material of following weight percent: ethanol 60%, toluene 20%, cyclohexanone 20%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213228A (en) * | 2005-07-01 | 2008-07-02 | 晓温-威廉姆斯公司 | Multi-layer coating system including a hydroxyl modified polyurethane dispersion binder |
| CN101243114A (en) * | 2005-08-17 | 2008-08-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a polyisocyanate and a polyol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101213228A (en) * | 2005-07-01 | 2008-07-02 | 晓温-威廉姆斯公司 | Multi-layer coating system including a hydroxyl modified polyurethane dispersion binder |
| CN101243114A (en) * | 2005-08-17 | 2008-08-13 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition comprising a polyisocyanate and a polyol |
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| 龚有林: "水性聚氨酯材料配方设计技巧", 《中国胶黏剂》 * |
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Application publication date: 20150826 |