CN102260445B - Polyester-modified acrylate resin aqueous paint, and preparation method thereof - Google Patents
Polyester-modified acrylate resin aqueous paint, and preparation method thereof Download PDFInfo
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- CN102260445B CN102260445B CN201110039391.4A CN201110039391A CN102260445B CN 102260445 B CN102260445 B CN 102260445B CN 201110039391 A CN201110039391 A CN 201110039391A CN 102260445 B CN102260445 B CN 102260445B
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Abstract
The invention relates to a polyester-modified acrylate resin aqueous paint. The paint is prepared from components of, by weight: 75 to 95% of an acrylate resin solution, 5 to 15% of a filing material, 0 to 5% of a leveling agent, 0 to 5% of a solvent, 0 to 2% of a dispersant, and 0 to 5% of a thickening agent. The invention provides an aqueous paint with good glossiness, good hardness and good impact strength. The invention also provides a preparation method of the paint. The aqueous paint has advantages of simple preparation method, common raw materials, low cost, and suitability for industrialized productions.
Description
One, technical field
The invention belongs to macromolecular material and preparation field thereof, relate to a kind of polyester-modified acrylate resin aqueous paint and preparation method thereof.
Two, background technology
Along with developing rapidly of coating technology, coating is more and more extensive in the application in the fields such as industry, life, also more and more harsher in the requirement aspect environmental protection to coating.At present, on market, for the coating of metal material surface, there is the features such as strong adhesion, chemical resistance be good, but generally there is the defects such as gloss dimness, hardness and impact strength be poor, thereby greatly affect visual appearance and the image appearance of metallic material components.Therefore, develop that a kind of luster performance is good, hardness and the high coating of impact strength and to form compound be industry active demand.
Three, summary of the invention
Technical problem to be solved by this invention is to provide that a kind of luster performance is good, hardness and the good water-borne coatings of impact strength and preparation method thereof, and this water-borne coatings preparation method is simple, raw material is common, cost is lower, be applicable to large-scale industrial production.
For realizing technical problem to be solved by this invention, the technical scheme of employing is: a kind of polyester-modified acrylate resin aqueous paint, by weight percentage, consists of following component:
Described filler is titanium dioxide, silicon-dioxide, calcium carbonate or talcum powder.Described flow agent can be Madaaflow flow agent.Described solvent can be dimethylbenzene, methylethylketone, butanone or acetone etc.Described dispersion agent can be non-silicone dispersion agent, contains silicone dispersion agent or Emulgen930 dispersion agent.
The present invention is also that described acrylic ester resin solution is for by weight percentage, the solution consisting of following component:
The present invention is also that described polyester liquid is for by weight percentage, the polyester liquid consisting of following component:
The present invention is also that described methacrylic ester is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, the carbonatoms ester class methacrylic compound that is 5-10.The ester class methacrylic compound that wherein carbonatoms is 5-10 is methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic heptyl heptylate, Octyl methacrylate, nonyl methacrylate and decyl-octyl methacrylate.
The present invention is also that described methacrylic acid hydroxyl ester is at least one in hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, the carbonatoms hydroxyl ester class methacrylic compound that is 5-10.The hydroxyl ester class methacrylic compound that wherein carbonatoms is 5-10 is methacrylic acid hydroxy pentane ester, the own ester of hydroxyethyl methacrylate, hydroxyethyl methacrylate heptyl ester, hydroxyethyl methacrylate monooctyl ester, hydroxyethyl methacrylate ester in the ninth of the ten Heavenly Stems and hydroxyethyl methacrylate ester in the last of the ten Heavenly stems.
The present invention be also described dioctyl phthalate compound be m-phthalic acid, phthalic acid, containing at least one in the alkyl-dimethyl acid compound of 5-10 carbon atom.Wherein the alkyl-dimethyl acid compound containing 5-10 carbon atom is pentane dioctyl phthalate compound, hexmae dicarboxylic acid compound, heptane dioctyl phthalate compound, octane dicarboxylic acid compound or nonane dicarboxylic acid compound.
A preparation method for polyester-modified acrylate resin aqueous paint, step is,
A, get 30～70 parts of acrylic ester resin solutions, 5～15 parts of fillers, 0～5 part of flow agent, 0～5 solvent, mix afterwards with ball mill grinding, make particle diameter≤10um;
B, get 20～50 parts of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 parts of water under 10～20 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 80～120um;
C, 80～120 parts of filter cakes, 0.1～1 part of dispersion agent, 0.1～1 part of thickening material are ground with sand milling, make coating.
The present invention is also that the preparation method of described acrylic ester resin solution is, by following per-cent, takes each component,
Mix, under the condition of 60-100 ℃, add appropriate methylethylketone, fully stir, make acrylic ester resin solution.
The present invention is also that the preparation method of described polyester liquid is, by following per-cent, takes each component,
Fully be uniformly mixed, under 150～300 ℃ of conditions, heat 5～12 hours, make polyester liquid.
A using method for polyester-modified acrylate resin aqueous paint, is first coated with surface by paint spay-coating at quilt, films and be dried 15～20 minutes under 70～100 ℃ of environment; Under 150～190 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
The present invention is also that described phosphoric acid ester is that 2-methacryloyl oxyethyl group phosphoric acid ester is or/and epoxy phosphate ester.
The present invention is also that described acrylamide compound is that N-butoxymethyl acrylamide is or/and Methacrylamide.
The present invention is also that described initiator is at least one in Diisopropyl azodicarboxylate, sodium peroxide, Potassium peroxide, ammonium peroxide.
The present invention is also that the hydroxyl value of described acrylic ester resin solution is 30～60, and acid number is 5～12, and weight-average molecular weight is 50000～120000.
Beneficial effect of the present invention is:
1, water-borne coatings of the present invention, its coating gloss is greater than 90%, and pencil hardness is greater than 2H, and impact strength is greater than 50cm, and coating has satisfactory stability with matrix, reaches 10 years steady time.
2, the solvent resistance of water-borne coatings of the present invention is good, and resistance to methylethylketone is greater than 120 times, and 1 grade of water logging in 48 hours test, has good provide protection to metallic surface.
3, the acrylic ester resin solution polymerization technique described in of the present invention is simple, stirring reaction under lesser temps and condition of normal pressure, energy-saving safe.
Four, embodiment
For better understanding the present invention, those skilled in the art can implement technical solution of the present invention, below in conjunction with embodiment, the present invention are done further and are illustrated.
Embodiment 1:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 90 grams of acrylic ester resin solutions, 8.5 grams of titanium dioxide, 0.5 gram of Madaaflow, 0.5 gram of methylethylketone, Emulgen9300.3 gram, 0.2 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 8.5 grams of titanium dioxide, and 0.5 gram of Madaaflow, 0.5 gram of methylethylketone, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 40 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.3Emulgen930,0.2 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 10 grams of methyl methacrylates, 25 grams of β-dimethyl-aminoethylmethacrylates, 10 grams of vinylbenzene, 10 grams of methyl acrylates, 10 grams of ethyl propenoates, 15 grams of propyl acrylates, 2 grams of hydroxy methyl methacrylate, 3 grams of hydroxyethyl methylacrylates, 1 gram, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 1 gram of N-butoxymethyl acrylamide, 10 grams of polyester liquids, 2 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 80 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 40, and acid number is 5.5, and weight-average molecular weight is 65000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 2 grams of oxalic acids, 2 grams of propanedioic acid, 4 grams of hexanodioic acids, 1 gram of FUMARIC ACID TECH GRADE, 1 gram of propylene diacid, 5 grams of neopentyl glycol, 10 grams of butyleneglycols, 5 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 150 ℃ of conditions, heat 12 hours, make polyester liquid.
Embodiment 2:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 90 grams of acrylic ester resin solutions, 8.5 grams of silicon-dioxide, 0.5 gram of Madaaflow flow agent, 0.5 gram of dimethylbenzene, 0.3 gram of non-silicone dispersion agent, 0.2 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 8.5 grams of silicon-dioxide, and 0.5 gram of Madaaflow, 0.5 gram of dimethylbenzene, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 40 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 18 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.3 gram of non-silicone dispersion agent, 0.2 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 35 grams of methyl methacrylates, 10 grams of vinylbenzene, 35 grams of methyl acrylates, 5 grams of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 1 gram of epoxy phosphate ester, 1 gram of Methacrylamide, 10 grams of polyester liquids, 2 grams of ammonium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 75 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 45, and acid number is 6.5, and weight-average molecular weight is 70000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of pentane dioctyl phthalate, 4 grams of succinic acid, 4 grams of pentanedioic acids, 1 gram of maleic acid, 1 gram of propylene diacid, 5 grams of neopentyl glycol, 5 grams of hexylene glycols, 5 grams of propylene glycol, 5 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 180 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 3:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 95 grams of acrylic ester resin solutions, 5 grams of titanium dioxide.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, and 5 grams of titanium dioxide mix the rear ball mill grinding of using, and make particle diameter≤8um; Get 45 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 12 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 95um; 100 grams of filter cakes are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 10 grams of methyl methacrylates, 10 grams of β-dimethyl-aminoethylmethacrylates, 5 grams of propyl methacrylates, 5 grams of butyl methacrylate, 5 grams of methacrylic acid pentyl esters, 10 grams of vinylbenzene, 5 grams of methyl acrylates, 10 grams of ethyl propenoates, 10 grams of vinylformic acid pentyl esters, 10 grams of Octyl acrylates, 2 grams of hydroxy methyl methacrylate, 2 grams of hydroxyethyl methylacrylates, 1 gram of hydroxyethyl methacrylate heptyl ester, 1 gram, (methyl) vinylformic acid, .5 gram of 2-methacryloyl oxyethyl group phosphoesterase 30 or, 0.5 gram of epoxy phosphate ester, 0.2 gram of N-butoxymethyl acrylamide, 0.8 gram of Methacrylamide, 10 grams of polyester liquids, 1 gram of Diisopropyl azodicarboxylate, 1 gram of sodium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 45, and acid number is 8, and weight-average molecular weight is 90000.
Wherein, the component of polyester liquid is: 5 grams of phthalic acids, 5 grams of hexmae dicarboxylic acids, 5 grams of heptane dioctyl phthalate, 5 grams of octane dicarboxylic acids, 2 grams of propanedioic acid, 2 grams of succinic acid, 4 grams of pentanedioic acids, 2 grams of propylene diacid, 5 grams of hexylene glycols, 10 grams of propylene glycol, 5 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 9 hours, make polyester liquid.
Embodiment 4:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 80 grams of acrylic ester resin solutions, 12 grams, calcium carbonate, 3 grams of Madaaflow flow agents, 2 grams of methylethylketones, 1 gram of non-silicone dispersion agent, 2 grams of thickening materials.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 45 grams of acrylic ester resin solutions, 12 grams of calcium carbonate, and 3 grams of Madaaflow flow agents, 2 grams of methylethylketones, mix the rear ball mill grinding of using, and make particle diameter≤10um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 90um; 100 grams of filter cakes, 1 gram of non-silicone dispersion agent, 2 grams of thickening materials are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 20 grams of β-dimethyl-aminoethylmethacrylates, 10 grams of N-Hexyl methacrylates, 5 grams of decyl-octyl methacrylates, 10 grams of vinylbenzene, 15 grams of propyl acrylates, 10 grams of butyl acrylates, 10 grams of vinylformic acid heptyl esters, 1 gram of methacrylic acid hydroxy butyl ester, 4 grams of methacrylic acid hydroxy butyl esters, 1 gram, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 1 gram of N-butoxymethyl acrylamide, 10 grams of polyester liquids, 2 grams of Potassium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 90 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8.5, and weight-average molecular weight is 95000.
Wherein, the component of polyester liquid is: 20 grams of phthalic acids, 8 gram 8 of propanedioic acid, 2 grams of propylene diacid, 15 grams of hexylene glycols, 5 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 250 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 5:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 80 grams of acrylic ester resin solutions, 12 grams of talcum powder, 3 grams of flow agents, 2 grams of dimethylbenzene, 1 gram of Emulgen930 dispersion agent, 2 grams of thickening materials.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 45 grams of acrylic ester resin solutions, 12 grams of talcum powder, and 3 grams of flow agents, 2 grams of dimethylbenzene, mix the rear ball mill grinding of using, and make particle diameter≤9um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 18 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 1 gram of Emulgen930,2 grams of thickening materials are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 25 grams of β-dimethyl-aminoethylmethacrylates, 12 grams of vinylbenzene, 25 grams of methyl acrylates, 15 grams of ethyl propenoates, 5 grams of butyl acrylates, 3 grams of hydroxyethyl methylacrylates, 2 grams of Rocryl 410s, 2 grams, (methyl) vinylformic acid, 1 gram of epoxy phosphate ester, 5 grams of N-butoxymethyl acrylamides, 5 grams of polyester liquids.
Above-mentioned each component by taking, mixes, and under the condition of 100 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 60, and acid number is 10, and weight-average molecular weight is 105000.
Wherein, the component of polyester liquid is: 5 grams of m-phthalic acids, 5 grams of phthalic acids, 5 grams of oxalic acids, 5 grams of propanedioic acid, 2 grams of hexanodioic acids, 2 grams of FUMARIC ACID TECH GRADE, 1 gram of propylene diacid, 5 grams of neopentyl glycol, 5 grams of hexylene glycols, 15 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 150 ℃ of conditions, heat 12 hours, make polyester liquid.
Embodiment 6:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 85 grams of acrylic ester resin solutions, 10 grams of titanium dioxide, 2 grams of Madaaflow, 1 gram of butanone, containing 1.5 grams of silicone dispersion agents, 0.5 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 10 grams of titanium dioxide, and 2 grams of Madaaflow, 1 gram of butanone, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 95um; 100 grams of filter cakes, 1.5 grams are ground with sand milling containing silicone dispersion agent, 0.5 gram of thickening material, make coating.
Wherein, the component of acrylic ester resin solution is: 5 grams of methyl methacrylates, 10 grams of propyl methacrylates, 10 grams of methacrylic heptyl heptylates, 12 grams of vinylbenzene, 10 grams of methyl acrylates, 10 grams of ethyl propenoates, 10 grams of propyl acrylates, 10 grams of butyl acrylates, 5 grams of vinylformic acid pentyl esters, 5 grams of hydroxyethyl methylacrylates, 2 grams, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 5 grams of N-butoxymethyl acrylamides, 5 grams of polyester liquids.
Above-mentioned each component by taking, mixes, and under the condition of 90 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 9, and weight-average molecular weight is 110000.
Wherein, the component of polyester liquid is: 10 grams of phthalic acids, 4 grams of oxalic acids, 4 grams of propanedioic acid, 4 grams of succinic acid, 1 gram of maleic acid, 2 grams of propylene diacid, 5 grams of neopentyl glycol, 5 grams of propylene glycol, 15 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 170 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 7:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 85 grams of acrylic ester resin solutions, 10 grams, calcium carbonate, 2 grams of flow agents, 1 gram, acetone, 1.5 grams of non-silicone dispersion agents, 0.5 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 10 gram of two calcium carbonate, and 2 grams of Madaaflow, 1 gram of acetone, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 1.5 grams of non-silicone dispersion agents, 0.5 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 15 grams of butyl methacrylate, 10 grams of methacrylic heptyl heptylates, 12 grams of vinylbenzene, 30 grams of methyl acrylates, 15 grams of ethyl propenoates, 5 grams of hydroxy methyl methacrylate, 2 grams, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 3 grams of N-butoxymethyl acrylamides, 2 grams of Methacrylamides, 5 grams of polyester liquids.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 11, and weight-average molecular weight is 95000.
Wherein, the component of polyester liquid is: 5 grams of heptane dioctyl phthalate, 5 grams of nonane dicarboxylic acids, 4 grams of pentanedioic acids, 8 grams of hexanodioic acids, 3 grams of FUMARIC ACID TECH GRADE, 5 grams of neopentyl glycol, 5 grams of butyleneglycols, 15 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 180 ℃ of conditions, heat 9 hours, make polyester liquid.
Embodiment 8:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 75 grams of acrylic ester resin solutions, 15 grams of talcum powder, 5 grams of flow agents, 3 grams of dimethylbenzene, containing 1 gram of silicone dispersion agent, 1 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 40 grams of acrylic ester resin solutions, 15 grams of talcum powder, and 5 grams of flow agents, 3 grams of dimethylbenzene, mix the rear ball mill grinding of using, and make particle diameter≤9.5um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 20 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 1 gram are ground with sand milling containing silicone dispersion agent, 1 gram of thickening material, make coating.
Wherein, the component of acrylic ester resin solution is: 10 grams of methyl methacrylates, 10 grams of β-dimethyl-aminoethylmethacrylates, 10 grams of propyl methacrylates, 10 grams of methacrylic acid pentyl esters, 10 grams of base Octyl acrylates, 10 grams of vinylbenzene, 17 grams of ethyl propenoates, 10 grams of propyl acrylates, 1 gram of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 3 grams of N-butoxymethyl acrylamides, 4 grams of Methacrylamides, 1 gram of polyester liquid, 3 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 78 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8, and weight-average molecular weight is 120000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 5 grams of oxalic acids, 5 grams of propanedioic acid, 5 grams of succinic acid, 2 grams of FUMARIC ACID TECH GRADE, 2 grams of maleic acids, 1 gram of propylene diacid, 10 grams of neopentyl glycol, 5 grams of hexylene glycols, 5 grams of propylene glycol, 5 grams of butyleneglycols, 15 grams of TriMethylolPropane(TMP)s, 30 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 180 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 9:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 75 grams of acrylic ester resin solutions, 5 grams of silica 1s, 5 grams of Madaaflow flow agents, 3 grams of methylethylketones, 1 gram of Emulgen930 dispersion agent, 1 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 40 grams of acrylic ester resin solutions, 15 grams of silicon-dioxide, and 5 grams of Madaaflow flow agents, 3 grams of methylethylketones, mix the rear ball mill grinding of using, and make particle diameter≤12um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 1 gram of Emulgen930 dispersion agent, 1 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 30 grams of methyl methacrylates, 20 grams of propyl methacrylates, 10 grams of vinylbenzene, 12 grams of methyl acrylates, 15 grams of vinylformic acid heptyl esters, 1 gram of Rocryl 410,1 gram, (methyl) vinylformic acid, 7 grams of N-butoxymethyl acrylamides, 1 gram of polyester liquid, 3 grams of sodium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 90 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 52, and acid number is 8.5, and weight-average molecular weight is 92000.
Wherein, the component of polyester liquid is: 10 grams of phthalic acids, 10 grams of propanedioic acid, 5 grams of succinic acid, 5 grams of maleic acids, 15 grams of neopentyl glycol, 5 grams of hexylene glycols, 15 grams of TriMethylolPropane(TMP)s, 30 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 9 hours, make polyester liquid.
Embodiment 10:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 80 grams of acrylic ester resin solutions, 5 grams of titanium dioxide, 4 grams, calcium carbonate, 3 grams of Madaaflow flow agents, 2 grams of dimethylbenzene, 3 grams of methylethylketones, 3 grams of Emulgen930 dispersion agents, 1 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 5 grams of titanium dioxide, 4 grams of calcium carbonate, 3 grams of Madaaflow flow agents, 2 grams of dimethylbenzene, 3 grams of methylethylketones, mix the rear ball mill grinding of using, and makes particle diameter≤9um; Get 30 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 2 grams of Emulgen930 dispersion agents, 1 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 40 grams of propyl methacrylates, 10 grams of butyl methacrylate, 10 grams of vinylbenzene, 27 grams of butyl acrylates, 1 gram of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 7 grams of N-butoxymethyl acrylamides, 1 gram of polyester liquid, 1 gram of Potassium peroxide, 2 grams of ammonium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 88 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 55, and acid number is 8, and weight-average molecular weight is 87000.
Wherein, the component of polyester liquid is: 10 grams of hexmae dicarboxylic acids, 5 grams of oxalic acids, 5 grams of neopentyl glycol, 5 grams of butyleneglycols, 5 grams of TriMethylolPropane(TMP)s, 70 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 150 ℃ of conditions, heat 12 hours, make polyester liquid.
Embodiment 11:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 80 grams of acrylic ester resin solutions, 9 grams of titanium dioxide, 3 grams of Madaaflow flow agents, 5 grams of methylethylketones, 2 grams of non-silicone dispersion agents, 1 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 9,3 grams of Madaaflow flow agents of 9 grams of titanium dioxide, and 5 grams of methylethylketones, mix the rear ball mill grinding of using, and make particle diameter≤10um; Get 30 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 2 grams of non-silicone dispersion agents, 1 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 30 grams of methyl methacrylates, 10 grams of propyl methacrylates, 8 grams of vinylbenzene, 20 grams of ethyl propenoates, 12 grams of butyl acrylates, 5 grams of hydroxy methyl methacrylate, 2 grams, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 5 grams of N-butoxymethyl acrylamides, 5 grams of polyester liquids, 2 grams of ammonium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 55, and acid number is 6.8, and weight-average molecular weight is 85000.
Wherein, the component of polyester liquid is: 5 grams of heptane dioctyl phthalate, 5 grams of nonane dicarboxylic acids, 5 grams of oxalic acids, 5 grams of hexylene glycols, 5 grams of propylene glycol, 5 grams of TriMethylolPropane(TMP)s, 70 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 250 ℃ of conditions, heat 6 hours, make polyester liquid.
Embodiment 12:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 81 grams of acrylic ester resin solutions, 10.5 grams of titanium dioxide, 2 grams of Madaaflow flow agents, 1 gram of methylethylketone, 0.5 gram of Emulgen930 dispersion agent, 5 grams of thickening materials.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 46 grams of acrylic ester resin solutions, 10.5 grams of titanium dioxide, and 2 grams of Madaaflow flow agents, 1 gram of methylethylketone, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.5 gram of Emulgen930 dispersion agent, 5 grams of thickening materials are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 40 grams of β-dimethyl-aminoethylmethacrylates, 8 grams of vinylbenzene, 32 grams of methyl acrylates, 5 grams of hydroxy methyl methacrylate, 2 grams, (methyl) vinylformic acid, 1 gram of epoxy phosphate ester, 5 grams of N-butoxymethyl acrylamides, 5 grams of polyester liquids, 2 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 100 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 60, and acid number is 11.5, and weight-average molecular weight is 95000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 5 grams of pentane dioctyl phthalate, 5 grams of oxalic acids, 5 grams of hexanodioic acids, 1 gram of FUMARIC ACID TECH GRADE, 2 grams of propylene diacid, 5 grams of neopentyl glycol, 5 grams of hexylene glycols, 2 grams of propylene glycol, 10 grams of TriMethylolPropane(TMP)s, 40 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 220 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 13:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 81 grams of acrylic ester resin solutions, 0.5 gram of silica 1,2 grams of flow agents, 1 gram of dimethylbenzene, 0.5 gram of non-silicone dispersion agent, 5 grams of thickening materials.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 46 grams of acrylic ester resin solutions, 10.5 grams of silicon-dioxide, and 2 grams of flow agents, 1 gram of dimethylbenzene, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 35 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.5 gram of non-silicone dispersion agent, 5 grams of thickening materials are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 35 grams of methyl methacrylates, 5 grams of vinylbenzene, 10 grams of methyl acrylates, 10 grams of ethyl propenoates, 18 grams of vinylformic acid pentyl esters, 7 grams of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 1 gram of 2-methacryloyl oxyethyl group phosphoric acid ester, 4 grams of N-butoxymethyl acrylamides, 8 grams of polyester liquids, 1 gram of Diisopropyl azodicarboxylate.
Above-mentioned each component by taking, mixes, and under the condition of 60 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 30, and acid number is 5, and weight-average molecular weight is 55000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 5 grams of heptane dioctyl phthalate, 5 grams of octane dicarboxylic acids, 5 grams of nonane dicarboxylic acids, 5 grams of propanedioic acid, 5 grams of succinic acid, 3 grams of FUMARIC ACID TECH GRADE, 10 grams of propylene glycol, 2 grams of butyleneglycols, 10 grams of TriMethylolPropane(TMP)s, 40 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 14:
A polyester-modified acrylate resin aqueous paint, its formula consists of: 90 grams of acrylic ester resin solutions, 9 grams of titanium dioxide, 0.5 gram of Madaaflow flow agent, 0.5 gram of methylethylketone, 0.9 gram of Emulgen930 dispersion agent, 0.6 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 9,0.5 grams of Madaaflow flow agents of 9 grams of titanium dioxide, and 0.5 gram of methylethylketone, mixes the rear ball mill grinding of using, and makes particle diameter≤10um; Get 40 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.9 gram of Emulgen930 dispersion agent, 0.6 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 25 grams of propyl methacrylates, 10 grams of butyl methacrylate, 5 grams of vinylbenzene, 38 grams of methyl acrylates, 5 grams of hydroxy methyl methacrylate, 2 grams of hydroxyethyl methylacrylates, 1 gram, (methyl) vinylformic acid, 1 gram of epoxy phosphate ester, 2 grams of N-butoxymethyl acrylamides, 2 grams of Methacrylamides, 8 grams of polyester liquids, 1 gram of sodium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 70 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 40, and acid number is 6.5, and weight-average molecular weight is 58000.
Wherein, the component of polyester liquid is: 17 grams of m-phthalic acids, 10 grams of oxalic acids, 2 grams of FUMARIC ACID TECH GRADE, 10 grams of propylene glycol, 5 grams of butyleneglycols, 9 grams of TriMethylolPropane(TMP)s, 47 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 230 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 15:
A kind of polyester-modified acrylate resin aqueous paint, its formula consists of: 90 grams of acrylic ester resin solutions, 5 grams of titanium dioxide, 4 grams of silicon-dioxide, 0.5 gram of Madaaflow flow agent, 0.2 gram of dimethylbenzene, 0.3 gram of methylethylketone, 0.5 gram of non-silicone dispersion agent, 0.4 gram of Emulgen930 dispersion agent, 0.6 gram of thickening material.
The preparation method of this polyester-modified acrylate resin aqueous paint, gets 50 grams of acrylic ester resin solutions, 5 grams of titanium dioxide, 4 grams of silicon-dioxide, 0.5 gram of Madaaflow flow agent, 0.2 gram of dimethylbenzene, 0.3 gram of methylethylketone, mix the rear ball mill grinding of using, and makes particle diameter≤10um; Get 40 grams of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 grams of water under 15 ℃ of conditions, after filtration, after washing, obtain solid and be divided into 50% filter cake, median size is 100um; 100 grams of filter cakes, 0.5 gram of non-silicone dispersion agent, 0.4 gram of Emulgen930 dispersion agent, 0.6 gram of thickening material are ground with sand milling, make coating.
Wherein, the component of acrylic ester resin solution is: 40 grams of methyl methacrylates, 10 grams of vinylbenzene, 34 grams of methyl acrylates, 3 grams of hydroxy methyl methacrylate, 5 grams of N-butoxymethyl acrylamides, 3 grams of Methacrylamides, 3 grams of polyester liquids, 2 grams of Potassium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 65 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8, and weight-average molecular weight is 75000.
Wherein, the component of polyester liquid is: 17 grams of phthalic acids, 5 grams of propanedioic acid, 5 grams of succinic acid, 2 grams of maleic acids, 10 grams of neopentyl glycol, 5 grams of hexylene glycols, 9 grams of TriMethylolPropane(TMP)s, 47 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 250 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 16:
A kind of acrylic ester resin solution, its recipe ingredient is: 10 grams of methyl methacrylates, 20 grams of β-dimethyl-aminoethylmethacrylates, 10 grams of nonyl methacrylates, 10 grams of vinylbenzene, 20 grams of methyl acrylates, 5 grams of ethyl propenoates, 9 grams of decyl acrylates, 3 grams of hydroxyethyl methylacrylates, 2 grams of N-butoxymethyl acrylamides, 6 grams of Methacrylamides, 3 grams of polyester liquids, 2 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 70 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 44, and acid number is 8.5, and weight-average molecular weight is 88000.
Wherein, the component of polyester liquid is: 18.5 grams of m-phthalic acids, 8 grams of oxalic acids, 1.5 grams of FUMARIC ACID TECH GRADE, 12 grams of neopentyl glycol, 10 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 225 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 17:
A kind of acrylic ester resin solution, its recipe ingredient is: 30 grams of propyl methacrylates, 10 grams of butyl methacrylate, 10 grams of vinylbenzene, 25 grams of ethyl propenoates, 9 grams of propyl acrylates, 3 grams of methacrylic acid hydroxy butyl esters, 8 grams of N-butoxymethyl acrylamides, 3 grams of polyester liquids, 2 grams of sodium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 55, and acid number is 9, and weight-average molecular weight is 102000.
Wherein, the component of polyester liquid is: 15 grams of phthalic acids, 3.5 grams of heptane dioctyl phthalate, 4 grams of oxalic acids, 4 grams of propanedioic acid, 1.5 grams of maleic acids, 6 grams of neopentyl glycol, 6 grams of hexylene glycols, 10 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 18:
A kind of acrylic ester resin solution, its recipe ingredient is: 39.2 grams of methyl methacrylates, 9 grams of vinylbenzene, 34.5 grams of ethyl propenoates, 4 grams of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .1 gram, 5 grams of N-butoxymethyl acrylamides, 6 grams of polyester liquids, 1.2 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 82 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 45, and acid number is 8, and weight-average molecular weight is 95000.
Wherein, the component of polyester liquid is: 5 grams of m-phthalic acids, 5 grams of phthalic acids, 8.5 grams of hexmae dicarboxylic acids, 8 grams of succinic acid, 1.5 grams of propylene diacid, 5 grams of hexylene glycols, 7 grams of propylene glycol, 10 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 250 ℃ of conditions, heat 6 hours, make polyester liquid.
Embodiment 19:
A kind of acrylic ester resin solution, its recipe ingredient is: 25 grams of β-dimethyl-aminoethylmethacrylates, 14.2 grams of propyl methacrylates, 9 grams of vinylbenzene, 30 grams of methyl acrylates, 4.5 grams of ethyl propenoates, 4 grams of hydroxy methyl methacrylate, 1 gram, (methyl) vinylformic acid, 0.1 gram of epoxy phosphate ester, 5 grams of N-butoxymethyl acrylamides, 6 grams of polyester liquids, 1.2 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8.5, and weight-average molecular weight is 96000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 10 grams of pentane dioctyl phthalate, 10 grams of oxalic acids, 7 grams of succinic acid, 2 grams of FUMARIC ACID TECH GRADE, 10 grams of neopentyl glycol, 5 grams of hexylene glycols, 5 grams of propylene glycol, 5 grams of butyleneglycols, 15 grams of TriMethylolPropane(TMP)s, 85 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 300 ℃ of conditions, heat 5 hours, make polyester liquid.
Embodiment 20:
A kind of acrylic ester resin solution, its recipe ingredient is: 20 grams of methyl methacrylates, 170 grams of β-dimethyl-aminoethylmethacrylates, 40 grams of vinylbenzene, 150 grams of methyl acrylates, 18 grams of butyl acrylates, 10 grams of hydroxy methyl methacrylate, 9 grams of hydroxyethyl methylacrylates, 4.5 grams, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .2 gram, 10 grams of N-butoxymethyl acrylamides, 12 grams of Methacrylamides, 28 grams of polyester liquids, 5 grams of Diisopropyl azodicarboxylates, 1.5 grams of sodium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 87 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 45, and acid number is 7.2, and weight-average molecular weight is 96500.
Wherein, the component of polyester liquid is: 20 grams of m-phthalic acids, 10 grams of phthalic acids, 7 grams of oxalic acids, 5 grams of propanedioic acid, 5 grams of succinic acid, 2 grams of maleic acids, 5 grams of hexylene glycols, 10 grams of propylene glycol, 10 grams of butyleneglycols, 15 grams of TriMethylolPropane(TMP)s, 85 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 270 ℃ of conditions, heat 6 hours, make polyester liquid.
Embodiment 21:
A kind of acrylic ester resin solution, its recipe ingredient is: 50 grams of methyl methacrylates, 70 grams of β-dimethyl-aminoethylmethacrylates, 30 grams of methacrylic heptyl heptylates, 40 grams of nonyl methacrylates, 40 grams of vinylbenzene, 30 grams of methyl acrylates, 50 grams of ethyl propenoates, 40 grams of vinylformic acid pentyl esters, 48 grams of Ethyl acrylate, 19 grams of hydroxy methyl methacrylate, 4.5 grams, (methyl) vinylformic acid, 0.2 gram of epoxy phosphate ester, 22 grams of N-butoxymethyl acrylamides, 28 grams of polyester liquids, 6.5 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 80 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8.5, and weight-average molecular weight is 85000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 10 grams of heptane dioctyl phthalate, 5 grams of nonane dicarboxylic acids, 10 grams of oxalic acids, 10 grams of propanedioic acid, 3 grams of FUMARIC ACID TECH GRADE, 2 grams of propylene diacid, 10 grams of neopentyl glycol, 5 grams of hexylene glycols, 5 grams of propylene glycol, 10 grams of butyleneglycols, 18 grams of TriMethylolPropane(TMP)s, 95 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 250 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 22:
A kind of acrylic ester resin solution, its recipe ingredient is: 220 grams of methyl methacrylates, 50 grams of vinylbenzene, 120 grams of methyl acrylates, 60 grams of ethyl propenoates, 23 grams of hydroxy methyl methacrylate, 6 grams, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .3 gram, 18 grams of N-butoxymethyl acrylamides, 10 grams of Methacrylamides, 32 grams of polyester liquids, 9 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 87 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 46, and acid number is 9, and weight-average molecular weight is 105000.
Wherein, the component of polyester liquid is: 20 grams of m-phthalic acids, 15 grams of phthalic acids, 10 grams of oxalic acids, 10 grams of hexanodioic acids, 5 grams of FUMARIC ACID TECH GRADE, 20 grams of neopentyl glycol, 10 grams of propylene glycol, 18 grams of TriMethylolPropane(TMP)s, 95 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 210 ℃ of conditions, heat 9 hours, make polyester liquid.
Embodiment 23:
A kind of acrylic ester resin solution, its recipe ingredient is: 110 grams of β-dimethyl-aminoethylmethacrylates, 110 grams of propyl methacrylates, 50 grams of vinylbenzene, 70 grams of methyl acrylates, 50 grams of ethyl propenoates, 60 grams of propyl acrylates, 13 grams of hydroxy methyl methacrylate, 10 grams of hydroxyethyl methylacrylates, 6 grams, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .3 gram, 28 grams of N-butoxymethyl acrylamides, 32 grams of polyester liquids, 5 grams of Diisopropyl azodicarboxylates, 4 grams of sodium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 78 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 50, and acid number is 8.6, and weight-average molecular weight is 96000.
Wherein, the component of polyester liquid is: 35 grams of phthalic acids, 10 grams of propanedioic acid, 10 grams of succinic acid, 5 grams of maleic acids, 10 grams of hexylene glycols, 10 grams of propylene glycol, 10 grams of butyleneglycols, 18 grams of TriMethylolPropane(TMP)s, 95 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 24:
A kind of acrylic ester resin solution, its recipe ingredient is: methyl methacrylate 102, gram, 21 grams of vinylbenzene, 85 grams of methyl acrylates, 10 grams of hydroxy methyl methacrylate, 2 grams, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .1 gram, 13 grams of N-butoxymethyl acrylamides, 16 grams of polyester liquids, 4 grams of sodium peroxides.
Above-mentioned each component by taking, mixes, and under the condition of 75 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 52, and acid number is 7.8, and weight-average molecular weight is 87000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 10 grams of succinic acid, 2 grams of FUMARIC ACID TECH GRADE, 15 grams of neopentyl glycol, 5 grams of hexylene glycols, 12 grams of TriMethylolPropane(TMP)s, 130 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 280 ℃ of conditions, heat 7 hours, make polyester liquid.
Embodiment 25:
A kind of acrylic ester resin solution, its recipe ingredient is: 30 grams of methyl methacrylates, 20 grams of β-dimethyl-aminoethylmethacrylates, 35 grams of propyl methacrylates, 17 grams of butyl methacrylate, 21 grams of vinylbenzene, 15 grams of methyl acrylates, 30 grams of ethyl propenoates, 20 grams of propyl acrylates, 20 grams of vinylformic acid heptyl esters, 5 grams of hydroxy methyl methacrylate, 5 grams of hydroxyethyl methylacrylates, 2 grams, (methyl) vinylformic acid, 2-methacryloyl oxyethyl group phosphoesterase 30 .1 gram, 13 grams of N-butoxymethyl acrylamides, 16 grams of polyester liquids, 4 grams of Diisopropyl azodicarboxylates.
Above-mentioned each component by taking, mixes, and under the condition of 80 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 55, and acid number is 8.7, and weight-average molecular weight is 96500.
Wherein, the component of polyester liquid is: 20 grams of m-phthalic acids, 25 grams of phthalic acids, 10 grams of oxalic acids, 10 grams of propanedioic acid, 10 grams of succinic acid, 5 grams of FUMARIC ACID TECH GRADE, 5 grams of propylene diacid, 10 grams of neopentyl glycol, 10 grams of hexylene glycols, 10 grams of propylene glycol, 10 grams of butyleneglycols, 25 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 270 ℃ of conditions, heat 8 hours, make polyester liquid.
Embodiment 26:
A kind of acrylic ester resin solution, its recipe ingredient is: 50 grams of methyl methacrylates, 20 grams of β-dimethyl-aminoethylmethacrylates, 32 grams of butyl methacrylate, 21 grams of vinylbenzene, 85 grams of methyl acrylates, 10 grams of hydroxy methyl methacrylate, 2 grams, (methyl) vinylformic acid, 0.1 gram of epoxy phosphate ester, 10 grams of N-butoxymethyl acrylamides, 3 grams of Methacrylamides, 16 grams of polyester liquids, 2 grams of Diisopropyl azodicarboxylates, 2 grams of ammonium peroxide.
Above-mentioned each component by taking, mixes, and under the condition of 85 ℃, adds appropriate methylethylketone, fully stirs, and makes acrylic ester resin solution.The hydroxyl value of this acrylic ester resin solution is 45, and acid number is 8, and weight-average molecular weight is 95000.
Wherein, the component of polyester liquid is: 10 grams of m-phthalic acids, 10 grams of phthalic acids, 5 grams of pentane dioctyl phthalate, 5 grams of hexmae dicarboxylic acids, 5 grams of heptane dioctyl phthalate, 10 grams of nonane dicarboxylic acids, 10 grams of propanedioic acid, 10 grams of succinic acid, 10 grams of pentanedioic acids, 10 grams of FUMARIC ACID TECH GRADE, 20 grams of hexylene glycols, 10 grams of propylene glycol, 10 grams of butyleneglycols, 25 grams of TriMethylolPropane(TMP)s, 50 grams of vinylbenzene.
The preparation method of above-mentioned polyester liquid is: above-mentioned each component taking is fully stirred, mix, under 200 ℃ of conditions, heat 10 hours, make polyester liquid.
Embodiment 27:
A using method for polyester-modified acrylate resin aqueous paint, is first coated with surface by paint spay-coating at quilt, films and be dried 15 minutes under 70 ℃ of environment; Under 150 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
Embodiment 28:
A using method for polyester-modified acrylate resin aqueous paint, is first coated with surface by paint spay-coating at quilt, films and be dried 18 minutes under 80 ℃ of environment; Under 160 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
Embodiment 29:
A using method for polyester-modified acrylate resin aqueous paint, is first coated with surface by paint spay-coating at quilt, films and be dried 20 minutes under 90 ℃ of environment; Under 170 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
Embodiment 30:
A using method for polyester-modified acrylate resin aqueous paint, is first coated with surface by paint spay-coating at quilt, films and be dried 20 minutes under 100 ℃ of environment; Under 190 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
Claims (6)
1. a polyester-modified acrylate resin aqueous paint, is characterized in that, by weight percentage, following component, consists of:
The raw materials by weight meter of acrylic ester resin solution, the solution being formed by following component:
The raw materials by weight meter of polyester liquid, the polyester liquid being formed by following component:
2. a kind of polyester-modified acrylate resin aqueous paint according to claim 1, it is characterized in that, described methacrylic ester is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, the carbonatoms ester class methacrylic compound that is 5-10.
3. a kind of polyester-modified acrylate resin aqueous paint according to claim 1, it is characterized in that, described methacrylic acid hydroxyl ester is at least one in hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, the carbonatoms hydroxyl ester class methacrylic compound that is 5-10.
4. a kind of polyester-modified acrylate resin aqueous paint according to claim 1, is characterized in that, described dioctyl phthalate compound is m-phthalic acid, phthalic acid, containing at least one in the alkyl-dimethyl acid compound of 5-10 carbon atom.
5. a preparation method for polyester-modified acrylate resin aqueous paint, is characterized in that,
A, get 30～70 parts of acrylic ester resin solutions, 5～15 parts of fillers, 0～5 part of flow agent, 0～5 solvent, mix afterwards with ball mill grinding, make particle diameter≤10 μ m;
B, get 20～50 parts of acrylic ester resin solutions and join in the mixture after grinding, be scattered in 2000 parts of water under 10～20 ℃ of conditions, after filtration, after washing, obtain solid part and be 50% filter cake, median size is 80～120 μ m;
C, 80～120 parts of filter cakes, 0.1～1 part of dispersion agent, 0.1～1 part of thickening material are ground with sand milling, make coating;
The preparation method of described acrylic ester resin solution is, by following weight percent, takes each component,
Mix, under the condition of 60-100 ℃, add appropriate methylethylketone, fully stir, make acrylic ester resin solution;
The preparation method of described polyester liquid is, by following weight percent, takes each component,
Fully be uniformly mixed, under 150～300 ℃ of conditions, heat 5～12 hours, make polyester liquid.
6. according to the using method of a kind of polyester-modified acrylate resin aqueous paint described in any one in claim 1 to 4, it is characterized in that, first paint spay-coating is coated with to surface at quilt, film and be dried 15～20 minutes under 70～100 ℃ of environment; Under 150～190 ℃ of conditions, toast 20 minutes again, solidify, obtain required coating.
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| CN103387643B (en) * | 2012-05-08 | 2015-11-25 | 长春市三化实业有限责任公司 | Polyester modification water-and acrylate and automobile water-miscible paint composition |
| CN103819984B (en) * | 2013-01-09 | 2018-05-11 | 苏州Ppg包装涂料有限公司 | Package coating compositions |
| CN104693373A (en) * | 2015-03-27 | 2015-06-10 | 广州慧谷化学有限公司 | Polyester modified water-based phosphorus-contained acrylic resin and preparation method and application thereof |
| CN104987468B (en) * | 2015-07-01 | 2017-11-24 | 湖南晟通纳米新材料有限公司 | Waterborne acrylic modified alkyd resins emulsion and preparation method thereof |
| CN105111382A (en) * | 2015-08-20 | 2015-12-02 | 顾彩霞 | Polyester-modified waterborne phosphate-contained acrylic resin |
| CN106749945B (en) * | 2016-11-29 | 2020-02-28 | 广州慧谷化学有限公司 | Polyester modified water-based acrylic resin, preparation and application in varnish |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012351A (en) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | Weather-resistant rust-proof water paint and preparing method thereof |
| CN101942064A (en) * | 2010-10-13 | 2011-01-12 | 中国科学院长春应用化学研究所 | Modified polyester and water-borne middle coating composition |
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2011
- 2011-02-17 CN CN201110039391.4A patent/CN102260445B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012351A (en) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | Weather-resistant rust-proof water paint and preparing method thereof |
| CN101942064A (en) * | 2010-10-13 | 2011-01-12 | 中国科学院长春应用化学研究所 | Modified polyester and water-borne middle coating composition |
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