CN104109443A - Water-based environment-friendly colorful texture coating and preparation method thereof - Google Patents
Water-based environment-friendly colorful texture coating and preparation method thereof Download PDFInfo
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- CN104109443A CN104109443A CN201410322223.XA CN201410322223A CN104109443A CN 104109443 A CN104109443 A CN 104109443A CN 201410322223 A CN201410322223 A CN 201410322223A CN 104109443 A CN104109443 A CN 104109443A
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Abstract
The invention discloses a water-based environment-friendly colorful texture coating and a preparation method thereof to solve the problems that a product is poisonous and inflammable and pollutes the environment as the existing colorful coating contains organic solvent. The water-based environment-friendly colorful texture coating comprises the following components in parts by mass: 30-50 parts of emulsion, 20-40 parts of color particles, 0.5-1.5 parts of thickener, 0.4-0.8 part of dispersant, 0.2-0.4 part of wetting agent, 0.5-2 parts of propylene glycol, 0.2-0.5 part of defoaming agent, 1-3 parts of titanium dioxide, 3-5 parts of talcum powder, 1-5 parts of calcium carbonate, 0.1-0.3 part of neutralizer and 10-40 parts of softened water. Modified starch and pigment are used as raw materials to prepare color particles, the color particles and composite starch emulsion are used as raw materials to prepare the environment-friendly colorful particle coating, and the water-based environment-friendly colorful texture coating is environment-friendly, free of color bleeding, good in compatibility, good in repeatability and the like.
Description
Technical field
The invention belongs to environmental protection coating material field, be specifically related to colorful texture coating of a kind of aqueous, environmental protective and preparation method thereof.
Background technology
Multicolor finish is in coating, to contain particulate material different with the inconsistent color of paint vehicle, that sizes and shape is different, a kind of compound suspended dispersed body coating of composition.It includes two or more colored particle conventionally, and the colour image of formation is various.Once construction can obtain the different multicolour pattern of depth level, after use, can receive significant decorative effect.Multicolor finish can need the surface of multiple color for brushing, utilize multicolor finish can simulate the state of wallpaper.And a lot of application of multicolor finish are all to be replaced by wallpaper.As multicolor finish can be brushed irregular surface easily, can also be for outer wall coating.Have rich color, change in pattern is various; Excellent performance, the feature such as water-fast, oil resistant, washability.
Present most multicolor finish is all prepared based on the water inconsistent characteristic of oil, and this uncompatibility has kept the dispersion of different pigment, thereby produces colorful system in a kind of coating.Such multicolor finish must comprise organic solvent, thereby produces shortcoming poisonous, inflammable, contaminate environment.Along with the increase of now environmental problem being paid close attention to, present stage mostly is water-soluble colorful coating exploitation.Water-soluble colorful coating is different from the coating products of traditional single-phase, monochromatic homogeneity, but polychrome, heterogeneous mix particles coexist, and easily cause the bleeding of color grain and dispersion medium muddy.
Summary of the invention
The object of the present invention is to provide the colorful texture coating of a kind of aqueous, environmental protective, to solve existing multicolor finish, comprise organic solvent, make product have problem poisonous, inflammable, contaminate environment.
Another object of the present invention is to provide the preparation method of the colorful texture coating of a kind of aqueous, environmental protective.
Technical solution of the present invention is as follows: the colorful texture coating of a kind of aqueous, environmental protective, the raw material that comprises following mass parts: emulsion 30-50 part, color grains 20-40 part, thickening material 0.5-1.5 part, dispersion agent 0.4-0.8 part, wetting agent 0.2-0.4 part, propylene glycol 0.5-2 part, defoamer 0.2-0.5 part, titanium dioxide 1-3 part, talcum powder 3-5 part, calcium carbonate 1-5 part, 0.1～0.3 part of neutralizing agent, softening water 10-40 part.
Preferably, described thickening material is a kind of in Natvosol, carboxymethyl cellulose, carboxymethyl starch, hydroxypropylated starch, alkali swelling ACRYLIC EMULSION or polyurethane associative thickener.
Preferably, described dispersion agent is a kind of in polycarboxylate sodium, polyacrylic acid sodium salt, poly carboxylic acid or amine salt derivative.
Preferably, described wetting agent is a kind of in aliphatic acid polyethenoxy ether, sorbitan stearate, alkylbenzene sulfonate or alkylsulfonate.
Preferably, described defoamer is a kind of in fatty acid metal soap, organophosphate, water drain silica or fatty acid ester.
Preferably, described neutralizing agent is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium bicarbonate or 2-amino-2 methyl isophthalic acids-propyl alcohol.
Preferably, emulsion is composite modified starch emulsion, the raw material that composite modified starch emulsion comprises following mass parts: 60-80 parts of Sumstar 190s, 20-40 parts of acidolysis etherification starchs, 0.5-2 parts, expansion inhibitor, 0.01-0.03 part of linking agent, 2-6 parts of emulsifying agents, 1-5 parts of initiators, 200-400 parts of deionized waters, 1-2 parts of NaOH and mix monomer, mix monomer comprises 65-150 parts of 35-160 parts of hard monomers and soft monomers.
Preferably, described mix monomer also comprises 1-2.5 parts of function monomers.
Preferably, described expansion inhibitor is sodium-chlor; Described linking agent is a kind of in epoxy chloropropane, phosphorus oxychloride or Trisodium trimetaphosphate; Described hard monomer is a kind of in methyl methacrylate, methyl-prop diluted acid ethyl ester or vinyl acetate, and described soft monomer is a kind of in ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; Described function monomer be vinylformic acid, methyl-prop diluted acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid-
-hydroxypropyl acrylate or methacrylic acid-
a kind of in the different monooctyl ester of-hydroxypropyl acrylate; Described emulsifying agent is anionic emulsifier sodium lauryl sulphate and the nonionic emulsifying agent BD-109 mixture of 1:1.5-2 ratio in mass ratio; Described initiator is a kind of in Potassium Persulfate or ammonium peroxydisulfate.
The preparation method of the colorful texture coating of above-mentioned aqueous, environmental protective, is characterized in that it comprises the steps:
The preparation of A, color grains: take raw material by following mass fraction, modified starch 75-90 part, softening agent 10-25 part, pigment dyestuff 30-40 part, join and in high-speed mixer, mix 5-10min, temperature 100-160 ℃, rotating speed is that under 50-100rpm condition, plasticizing is extruded, extrude rear cooling crush granulation, prepare the particle of particle diameter 0.1-2mm;
The preparation of B, colorful texture coating:
Getting softening water, thickening material, dispersion agent, wetting agent, titanium dioxide, talcum powder, calcium carbonate adds in dispersion machine, with 1000～1500r/min dispersed with stirring 10-20min, then add successively emulsion, color grains, propylene glycol, defoamer, neutralizing agent, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective;
Described modified starch is the single or composite modified starch of hydrophobicity, selects a kind of in esterification starch, etherification starch, hydroxyalkylation starch, cross-linking starch or graft starch, and moisture content is controlled at 12-17%;
Described softening agent is a kind of in glycerine, ethylene glycol, propylene glycol, Xylitol, polyoxyethylene glycol, sorbyl alcohol, triglyceride level, methane amide or urea;
Described pigment is pigment dyestuff-commercially available pigment dyestuff that is easy to get, and is selected from that the Chinese is husky yellow, a kind of in solid orange, toluidine red, permanent bordeaux, permanent yellow, phthalocyanine blue or phthalocyanine green forever.
The preparation of color grains of the present invention is based on following principle: starch, after hydrophobic modified, has improved mechanical property, water resistance and the thermoplastic property of starch.Can improve the consistency with other insoluble polymer.Under the effect of thermal field, external force field and interpolation small molecules softening agent, starch granules is destroyed, softening agent small molecules penetrates between starch molecule, form hydrogen bond with starch molecule, replaced the hydrogen bond between partial starch-starch, thereby the reactive force between starch molecule is reduced, be transformed into thermoplastic starch, be easy to processing.Add pigment dyestuff and plasticity-starch jointly to extrude, make the certain polymerization of pigment and plasticity-Starch formation, make starch play the provide protection to pigment.
Beneficial effect of the present invention
1. color grains of the present invention is that plasticity-starch is combined gained with pigment dyestuff, has the feature of nontoxic, environmental protection, safety, and is hard particles, has hydrophobicity, for coating, can not produce bleeding phenomenon.
2. to select emulsion be the consistency of utilizing composite modified starch emulsion that modified starch obtains through graft reaction for skeleton, acrylate monomer and Vinyl Acetate Monomer and color grains to have in the present invention, easily dispersion.
3. the present invention adopts and manually prepares hard color grains and prepare multicolor finish, and the composite mode of color grains, addition are controlled, and coating repeatability better.
4. product of the present invention is used for wall decoration, the coating color desktop obtaining, and gloss is graceful, is better than wallpaper.Can clean, be suitable for the decorating inner and external walls in hotel, restaurant, commercial building, building for working and general room.
5. product has the features such as environmental protection, nonbleeding, consistency be good, reproducible.
Embodiment
With regard to specific embodiment, the present invention is further described below, in embodiment, not marked raw material is and is purchased.
The Sumstar 190 of mentioning in composite modified starch emulsion in following embodiment and acidolysis etherification starch are that one or both mixtures of take in yam starch, waxy corn starch, tapioca (flour), sticky rice flour, W-Gum make as raw material adopts following methods.
Wherein in embodiment 1-5, the preparation method used of Sumstar 190 and acidolysis etherification starch is as follows:
1. Sumstar 190 preparation method is: starch adds deionized water water, and to be mixed with concentration be 38% starch milk, is heated to 55 ℃, and adding concentration is 30% H
2o
2solution is as oxygenant, and oxygenant consumption is 6% of starch butt amount, the CuSO that the concentration of take is 0.5%
4solution is catalyzer, 0.02% of catalyst levels starch butt amount, and take mass percent concentration 3% NaOH solution and mass percent concentration 5% HCl is pH adjusting agent, regulating pH is 7.3, oxidizing reaction 3-4h, washing, dry, pulverize and obtain Sumstar 190 product.
2. acidolysis etherification starch is that acidolysis sodium starch glycolate and acidolysis hydroxypropylated starch mix, the preparation process of wherein acidolysis carboxymethyl starch is: in acidified starch, add 80% ethanol, be mixed with the starch milk of concentration 35%, under whipped state, the NaOH ethanol that dropping mass percent concentration is 40%, NaOH ethanol is formulated by NaOH and 95% ethanol, at the temperature of 30 ℃, stir alkalization 30min, be warming up to 45 ℃, slowly add sodium chloroacetate ethanol, sodium chloroacetate ethanol be take by sodium chloroacetate and sodium hydroxide and 95% ethanol ratio that mass ratio is 3:1:4 and is mixed and obtain, reaction 3h, with 5% hydrochloride ethanol liquid, regulate pH value to 7, filter, by 80% washing with alcohol 3 times, dry, pulverize whitely or pale yellow powder shape product, be acidolysis carboxymethyl starch.
3. the preparation process of acidolysis hydroxypropylated starch is: in deionized water water, add with respect to starch quality than 13% expansion inhibitor, add the sodium hydroxide that accounts for starch quality 1.0%%, mix to dissolving, the starch milk that adds acidified starch furnishing 35% prepared by step (1), stir alkalization 40min, be warming up to 42 ℃, add the propylene oxide that accounts for starch quality 5%, etherification reaction 14h, add 10% salt acid for adjusting pH to 7.0, centrifuge dehydration, obtain acidolysis hydroxypropylated starch after being dried, sieving;
4. the preparation process of the acidified starch that acidolysis carboxymethyl starch and acidolysis hydroxypropylated starch preparation process are used is: in starch, adding mass percent concentration is in 0.6% HCl solution, be mixed with the starch milk of concentration 38%, be heated to 50 ℃ of temperature, acidolysis reaction 2h; After acidolysis finishes, add the NaOH solution of mass percent concentration 5% to regulate pH to 7, filtration, washing, the dry acidified starch that to obtain.
Wherein in embodiment 6-10, the preparation method used of Sumstar 190 and acidolysis etherification starch is as follows:
1. Sumstar 190 preparation method is: starch adds the starch milk that deionized water water is mixed with concentration 40%, is heated to 55 ℃, and adding concentration is 30% H
2o
2solution is as oxygenant, and oxygenant consumption is 6% of starch butt amount, the CuSO that the concentration of take is 0.5%
4solution is catalyzer, 0.02% of catalyst levels starch butt amount, and take mass percent concentration 3% NaOH solution and mass percent concentration 5% HCl is pH adjusting agent, regulating pH is 7.3, oxidizing reaction 3h, washing, dry, pulverize and obtain Sumstar 190 product.
2. acidolysis etherification starch is that acidolysis sodium starch glycolate and acidolysis hydroxypropylated starch mix, the preparation process of wherein acidolysis carboxymethyl starch is: in acidified starch, add 90% ethanol, be mixed with the starch milk of concentration 38%, under whipped state, the NaOH ethanol that dropping mass percent concentration is 40%, NaOH ethanol is formulated by NaOH and 95% ethanol, at the temperature of 30 ℃, stir alkalization 40min, be warming up to 45 ℃, slowly add sodium chloroacetate ethanol, sodium chloroacetate ethanol be take by sodium chloroacetate and sodium hydroxide and 95% ethanol ratio that mass ratio is 3:1:6 and is mixed and obtain, reaction 4h, with 5% hydrochloride ethanol liquid, regulate pH value to 7.5, filter, by 80% washing with alcohol 3 times, dry, pulverize whitely or pale yellow powder shape product, be acidolysis carboxymethyl starch.
3. the preparation process of acidolysis hydroxypropylated starch is: in deionized water water, add with respect to starch quality than 15% expansion inhibitor, add the sodium hydroxide that accounts for starch quality 1.2%, mix to dissolving, the starch milk that adds acidified starch furnishing 38% prepared by step (1), stir alkalization 60min, be warming up to 42 ℃, add the propylene oxide that accounts for starch quality 10%, etherification reaction 18h, add 10% salt acid for adjusting pH to 7.0, centrifuge dehydration, obtain acidolysis hydroxypropylated starch after being dried, sieving;
4. the preparation process of the acidified starch that acidolysis carboxymethyl starch and acidolysis hydroxypropylated starch preparation process are used is: in starch, adding mass percent concentration is in 0.8% HCl solution, be mixed with the starch milk of concentration 40%, be heated to 55 ℃ of temperature, acidolysis reaction 3h; After acidolysis finishes, adding mass percent concentration is that 5% NaOH solution regulates pH to 7, filters, washing, the dry acidified starch that to obtain.
Embodiment 1
1. the preparation of color grains
Take the husky yellow 300g of esterification starch 750g, softening agent glycerine 100g, the pigment dyestuff Chinese, join and in high-speed mixer, mix 5min, 100 ℃ of temperature, rotating speed is under 50 rpm conditions, in single screw extrusion machine plasticizing, extrude, extrude rear cooling crush granulation, prepare the particle of particle diameter 0.1mm.
2. the preparation of colorful texture coating
Get softening water 300g, thickening material Natvosol 10g, dispersion agent polycarboxylate sodium 8g, wetting agent aliphatic acid polyethenoxy ether AEO-9 4g, titanium dioxide 30g, talcum powder 50g, calcium carbonate 50g adds in dispersion machine, with 1000r/min dispersed with stirring 10min, add successively composite modified starch emulsion 300g, color grains 200g, propylene glycol 20g, defoamer fatty acid metal soap 5g, neutralizing agent sodium hydroxide 3g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 60kg, acidolysis etherification starch 40 kg, expansion inhibitor 2 kg, linking agent 0.03 kg, hard monomer 35 kg, soft monomer 65 kg, function monomer 1 kg, emulsifying agent 2 kg, initiator 1 kg, deionized water 200 kg, NaOH are 1.2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.4 by substitution value mixes with the ratio of 1:2 with the acidolysis hydroxypropylated starch of substitution value 0.1), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 10.5;
(3) the linking agent phosphorus oxychloride of mass fraction under step (2) gained starch milk adds, reaction 1h, adding volumetric concentration is 10% salt acid for adjusting pH to 8.5;
(4) at step (3) gained starch milk, be warming up to 80 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (Potassium Persulfate), adding deionized water, to be mixed with mass concentration be that 5% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the BD-109 emulsifying agent that the ratio of 1:2 is mixed in mass ratio, then 1/4 amount that adds step (5) initiator solution, 1/10 amount of mix monomer (methyl methacrylate, butyl acrylate, vinylformic acid mix), reacts 20 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 80 ℃, reaction 2h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 6, obtains coating emulsion.
Embodiment 2
1. the preparation of color grains
Take etherification starch 780g, softening agent ethylene glycol 140g, pigment dyestuff solid orange 320g forever, join and in high-speed mixer, mix 6min, 110 ℃ of temperature, rotating speed is under 60rpm condition, in twin screw extruder plasticizing, extrude, extrude rear cooling crush granulation, prepare the particle of particle diameter 0.5mm.
2. the preparation of colorful texture coating
Get softening water 250g, thickening material carboxymethyl cellulose 10g, dispersion agent polycarboxylate sodium 4g, wetting agent 3g, titanium dioxide 10g, talcum powder 50g, calcium carbonate 50g add in dispersion machine, with 1100r/min dispersed with stirring 15min, add successively emulsion 360g, color grains 250g, propylene glycol 10g, defoamer organophosphate 2g, neutralizing agent potassium hydroxide 1g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Embodiment 3
1. the preparation of color grains
Take hydroxyalkylation starch 800g, softening agent propylene glycol 160g, pigment dyestuff toluidine red 340g, join and in high-speed mixer, mix 10min, 150 ℃ of temperature, rotating speed is under 80rpm condition, in single screw extrusion machine plasticizing, extrude, extrude rear cooling crush granulation, prepare the particle of particle diameter 1mm.
2. the preparation of colorful texture coating
Get softening water 400g, thickening material carboxymethyl starch 15g, dispersion agent, poly carboxylic acid 4g, wetting agent alkylbenzene sulfonate 2g, titanium dioxide 30g, talcum powder 30g, calcium carbonate 30g add in dispersion machine, with 1500r/min dispersed with stirring 18min, add successively composite modified starch emulsion 380g, color grains 280g, propylene glycol 5g, water drain silica 3g, neutralizing agent ammoniacal liquor 1g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, expansion inhibitor 1.5 kg, linking agent 0.02 kg, hard monomer 80 kg, soft monomer 120 kg, emulsifying agent 4 kg, initiator 2.5 kg, deionized water 300 kg, NaOH are 1.5 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.8 by substitution value mixes with the ratio of 1:4 with the acidolysis hydroxypropylated starch of substitution value 0.08), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 11;
(3) the linking agent Trisodium trimetaphosphate of mass fraction under step (2) gained starch milk adds, reaction 2h, adding volumetric concentration is 10% salt acid for adjusting pH to 9;
(4) at step (3) gained starch milk, be warming up to 85 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (ammonium peroxydisulfate), adding deionized water, to be mixed with mass concentration be that 8% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.5 is mixed in mass ratio, then add 1/10 amount 1/4 amount and mix monomer (methyl-prop diluted acid ethyl ester mixes with ethyl propenoate) of step (5) initiator solution, react 30 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 85 ℃, reaction 2.5h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 7, obtains coating emulsion.
Embodiment 4
1. the preparation of color grains
Take cross-linking starch 830g, softening agent Xylitol 180g, pigment dyestuff permanent bordeaux 350g, join and in high-speed mixer, mix 10min, 120 ℃ of temperature, rotating speed is under 90rpm condition, twin screw extruder plasticizing is extruded, and extrudes rear cooling crush granulation, prepares the particle of particle diameter 1.5mm.
2. the preparation of colorful texture coating
Get softening water 200g, thickening material hydroxypropylated starch 5g, dispersion agent amine salt derivative 5g, wetting agent alkylsulfonate 3g, titanium dioxide 20g, talcum powder 40g, calcium carbonate 40g add in dispersion machine, with 1200r/min dispersed with stirring 20min, add successively composite modified starch emulsion 400g, color grains 270g, propylene glycol 10g, fatty acid ester 4g, neutralizing agent sodium bicarbonate 3g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 80 kg, acidolysis etherification starch 20 kg, expansion inhibitor 1 kg, linking agent 0.01 kg, hard monomer 160 kg, soft monomer 100 kg, emulsifying agent 6 kg, initiator 5 kg, deionized water 350 kg, NaOH1.8 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.1 by substitution value mixes with the ratio of 1:3 with the acidolysis hydroxypropylated starch of substitution value 0.12), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 11;
(3) the linking agent epoxy chloropropane of mass fraction under step (2) gained starch milk adds, reaction 3h, adding volumetric concentration is 10% salt acid for adjusting pH to 9;
(4) at step (3) gained starch milk, be warming up to 90 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (Potassium Persulfate), adding deionized water, to be mixed with mass concentration be that 6% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the BD-109 emulsifying agent that the ratio of 1:1.6 is mixed in mass ratio, then add 1/10 amount 1/4 amount and mix monomer (vinyl acetate, butyl acrylate mix) of step (5) initiator solution, react 25 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 80 ℃, reaction 3h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 6, obtains coating emulsion.
Embodiment 5
1. the preparation of color grains
Take graft starch 880g, softening agent polyoxyethylene glycol 220g, pigment dyestuff permanent yellow 380g, join and in high-speed mixer, mix 8min, 150 ℃ of temperature, rotating speed is under 100rpm condition, in single screw extrusion machine plasticizing, extrude, extrude rear cooling crush granulation, prepare the particle of particle diameter 1.8mm.
2. the preparation of colorful texture coating
Getting softening water 400g, thickening material alkali swelling ACRYLIC EMULSION 5g, dispersion agent polycarboxylate sodium 4g, wetting agent aliphatic acid polyethenoxy ether AEO-9 2g, titanium dioxide 10g, talcum powder 30g, calcium carbonate 30g adds in dispersion machine, with 1500r/min dispersed with stirring 10min, add successively composite modified starch emulsion 450g, color grains 300g, propylene glycol 5g, water drain silica 2g, neutralizing agent 2-amino-2 methyl isophthalic acids-propyl alcohol 2g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 60 kg, acidolysis etherification starch 40 kg, expansion inhibitor 2 kg, linking agent 0.03 kg, hard monomer 148 kg, soft monomer 150 kg, function monomer 2 kg, emulsifying agent 5 kg, initiator 4 kg, deionized water 400 kg, NaOH2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.2 by substitution value mixes with the ratio of 1:4 with the acidolysis hydroxypropylated starch of substitution value 0.15), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 10.5;
(3) the linking agent Trisodium trimetaphosphate of mass fraction under step (2) gained starch milk adds, reaction 2h, adding volumetric concentration is 10% salt acid for adjusting pH to 8.5;
(4) at step (3) gained starch milk, be warming up to 85 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (Potassium Persulfate), adding deionized water, to be mixed with mass concentration be that 7% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.7 is mixed in mass ratio, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (methyl methacrylate, ethyl propenoate, Hydroxyethyl acrylate mix), react 20 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 90 ℃, reaction 3h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 7, obtains coating emulsion.
Embodiment 6
1. the preparation of color grains
Take the blue 400g of graft starch 900g, softening agent sorbyl alcohol 250g, organic pigment phthalocyanine, join and in high-speed mixer, mix 10min, 160 ℃ of temperature, rotating speed is under 50 rpm conditions, twin screw extruder plasticizing is extruded, and extrudes rear cooling crush granulation, prepares the particle of particle diameter 2mm.
2. the preparation of colorful texture coating
Get softening water 100g, polyurethane associative thickener 5g, dispersion agent polyacrylic acid sodium salt 7g, wetting agent 4g, titanium dioxide 10g, talcum powder 30g, calcium carbonate 10g add in dispersion machine, with 1500r/min dispersed with stirring 15min, add successively composite modified starch emulsion 500g, color grains 400g, propylene glycol 8g, fatty acid ester 4g, sodium hydroxide 2g, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, expansion inhibitor 1 kg, linking agent 0.02 kg, hard monomer 80 kg, soft monomer 120 kg, function monomer 2.5 kg, emulsifying agent 4 kg, initiator 3 kg, deionized water 300 kg, NaOH1 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.6 by substitution value mixes with the ratio of 1:3.5 with the acidolysis hydroxypropylated starch of substitution value 0.08), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 11.5;
(3) the linking agent epoxy chloropropane of mass fraction under step (2) gained starch milk adds, reaction 3h, adding volumetric concentration is 10% salt acid for adjusting pH to 9.5;
(4) at step (3) gained starch milk, be warming up to 80 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (Potassium Persulfate), adding deionized water, to be mixed with mass concentration be that 8% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.8 is mixed in mass ratio, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (methyl methacrylate, Isooctyl acrylate monomer, Rocryl 410 mix), react 20-30 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 85 ℃, reaction 2.5h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 6, obtains coating emulsion.
Embodiment 7. difference from Example 1 are that the softening agent in the preparation of color grains is sorbyl alcohol, and pigment dyestuff is phthalocyanine green.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 80 kg, acidolysis etherification starch 20 kg, expansion inhibitor 0.5 kg, linking agent 0.01 kg, hard monomer 35 kg, soft monomer 65 kg, function monomer 1 kg, emulsifying agent 3 kg, initiator 2 kg, deionized water 200 kg, NaOH1.2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.3 by substitution value mixes with the ratio of 1:2 with the acidolysis hydroxypropylated starch of substitution value 0.05), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 11.5;
(3) the linking agent phosphorus oxychloride of mass fraction under step (2) gained starch milk adds, reaction 1h, adding volumetric concentration is 10% salt acid for adjusting pH to 9.5;
(4) at step (3) gained starch milk, be warming up to 90 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (ammonium peroxydisulfate), adding deionized water, to be mixed with mass concentration be that 5% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.9 is mixed in mass ratio, then add 1/4 amount of step (5) initiator solution and mix monomer (methyl methacrylate, butyl acrylate, vinylformic acid-
the mixing of-hydroxypropyl acrylate) 1/10 amount, reacts 30 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 80 ℃, reaction 2h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 7, obtains coating emulsion.
Embodiment 8. difference from Example 1 are that the softening agent in the preparation of color grains is triglyceride level.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, expansion inhibitor 1.5 kg, linking agent 0.02 kg, hard monomer 70 kg, soft monomer 130 kg, function monomer 1 kg, emulsifying agent 4 kg, initiator 2.5 kg, deionized water 300 kg, NaOH1.5 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.8 by substitution value mixes with the ratio of 1:4 with the acidolysis hydroxypropylated starch of substitution value 0.08), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 11;
(3) the linking agent Trisodium trimetaphosphate of mass fraction under step (2) gained starch milk adds, reaction 2h, adding volumetric concentration is 10% salt acid for adjusting pH to 9;
(4) at step (3) gained starch milk, be warming up to 85 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (ammonium peroxydisulfate), adding deionized water, to be mixed with mass concentration be that 6% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.5 is mixed in mass ratio, then add step (5) initiator solution 1/4 amount and mix monomer (methyl methacrylate, ethyl propenoate, methacrylic acid-
the different monooctyl ester mixing of-hydroxypropyl acrylate) 1/10 amount, reacts 30 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 85 ℃, reaction 2.5h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 7, obtains coating emulsion.
Embodiment 9. difference from Example 1 are that the softening agent in the preparation of color grains is methane amide.
Composite modified starch emulsion materials consumption is as follows: Sumstar 190 60 kg, acidolysis etherification starch 40 kg, expansion inhibitor 2 kg, linking agent 0.03 kg, hard monomer 130 kg, soft monomer 140 kg, function monomer 2 kg, emulsifying agent 5 kg, initiator 4 kg, deionized water 400 kg, NaOH are 2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, in mass fraction, in deionized water, add Sumstar 190 and acidolysis etherification starch (the acidolysis sodium starch glycolate that is 0.2 by substitution value mixes with the ratio of 1:4 with the acidolysis hydroxypropylated starch of substitution value 0.15), form certain density starch milk;
(2) at the expansion inhibitor sodium-chlor of step (1) gained starch milk additional proportion, the sodium hydroxide solution that is 5% by volumetric concentration is adjusted starch milk pH to 10.5;
(3) the linking agent Trisodium trimetaphosphate of mass fraction under step (2) gained starch milk adds, reaction 2h, adding volumetric concentration is 10% salt acid for adjusting pH to 8.5;
(4) at step (3) gained starch milk, be warming up to 85 ℃ of abundant gelatinizations 30 minutes;
(5) take initiator (Potassium Persulfate), adding deionized water, to be mixed with mass concentration be that 8% solution is initiator solution;
(6) in step (4) gained starch milk additional proportion by sodium lauryl sulphate and the OP-10 emulsifying agent that the ratio of 1:1.7 is mixed in mass ratio, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (β-dimethyl-aminoethylmethacrylate, ethyl propenoate, methyl-prop diluted acid mix), react 20 minutes; With constant pressure funnel, at the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer again, after adding, be warming up to 90 ℃, reaction 3h;
(7) reaction system is down to room temperature, and the NaOH aqueous solution that volumetric concentration is 20% regulates pH to 7, obtains coating emulsion.
Embodiment 10. difference from Example 1 are that the softening agent in the preparation of color grains is urea.
Claims (10)
1. the colorful texture coating of aqueous, environmental protective, is characterized in that the raw material that it comprises following mass parts: emulsion 30-50 part, color grains 20-40 part, thickening material 0.5-1.5 part, dispersion agent 0.4-0.8 part, wetting agent 0.2-0.4 part, propylene glycol 0.5-2 part, defoamer 0.2-0.5 part, titanium dioxide 1-3 part, talcum powder 3-5 part, calcium carbonate 1-5 part, 0.1～0.3 part of neutralizing agent, softening water 10-40 part.
2. the colorful texture coating of aqueous, environmental protective according to claim 1, is characterized in that: described thickening material is a kind of in Natvosol, carboxymethyl cellulose, carboxymethyl starch, hydroxypropylated starch, alkali swelling ACRYLIC EMULSION or polyurethane associative thickener.
3. the colorful texture coating of aqueous, environmental protective according to claim 1, is characterized in that: a kind of in polycarboxylate sodium, polyacrylic acid sodium salt, poly carboxylic acid or amine salt derivative of described dispersion agent.
4. the colorful texture coating of aqueous, environmental protective according to claim 1, is characterized in that: described wetting agent is a kind of in aliphatic acid polyethenoxy ether, sorbitan stearate, alkylbenzene sulfonate or alkylsulfonate.
5. the colorful texture coating of aqueous, environmental protective according to claim 1, is characterized in that: described defoamer is a kind of in fatty acid metal soap, organophosphate, water drain silica or fatty acid ester.
6. the colorful texture coating of aqueous, environmental protective according to claim 1, is characterized in that: described neutralizing agent is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium bicarbonate or 2-amino-2 methyl isophthalic acids-propyl alcohol.
7. the colorful texture coating of aqueous, environmental protective according to claim 1, it is characterized in that: described emulsion is composite modified starch emulsion, the raw material that composite modified starch emulsion comprises following mass parts: 60-80 parts of Sumstar 190s, 20-40 parts of acidolysis etherification starchs, 0.5-2 parts, expansion inhibitor, 0.01-0.03 part of linking agent, 2-6 parts of emulsifying agents, 1-5 parts of initiators, 200-400 parts of deionized waters, 1-2 parts of NaOH and mix monomer, mix monomer comprises 65-150 parts of 35-160 parts of hard monomers and soft monomers.
8. the colorful texture coating of aqueous, environmental protective according to claim 7, is characterized in that: described mix monomer also comprises 1-2.5 parts of function monomers.
9. the colorful texture coating of aqueous, environmental protective according to claim 7, is characterized in that: described expansion inhibitor is sodium-chlor; Described linking agent is a kind of in epoxy chloropropane, phosphorus oxychloride or Trisodium trimetaphosphate; Described hard monomer is a kind of in methyl methacrylate, methyl-prop diluted acid ethyl ester or vinyl acetate, and described soft monomer is a kind of in ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; Described function monomer be vinylformic acid, methyl-prop diluted acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid-
-hydroxypropyl acrylate or methacrylic acid-
a kind of in the different monooctyl ester of-hydroxypropyl acrylate; Described emulsifying agent is anionic emulsifier sodium lauryl sulphate and the nonionic emulsifying agent BD-109 mixture of 1:1.5-2 ratio in mass ratio; Described initiator is a kind of in Potassium Persulfate or ammonium peroxydisulfate.
10. the preparation method of the colorful texture coating of claim 1 aqueous, environmental protective, is characterized in that it comprises the steps:
The preparation of A, color grains: take raw material by following mass fraction, modified starch 75-90 part, softening agent 10-25 part, pigment dyestuff 30-40 part, join and in high-speed mixer, mix 5-10min, temperature 100-160 ℃, rotating speed is that under 50-100rpm condition, plasticizing is extruded, extrude rear cooling crush granulation, prepare the particle of particle diameter 0.1-2mm;
The preparation of B, colorful texture coating:
Getting softening water, thickening material, dispersion agent, wetting agent, titanium dioxide, talcum powder, calcium carbonate adds in dispersion machine, with 1000～1500r/min dispersed with stirring 10-20min, then add successively emulsion, color grains, propylene glycol, defoamer, neutralizing agent, after dispersed with stirring is even, obtain the colorful texture coating of aqueous, environmental protective;
Described modified starch is selected a kind of in esterification starch, etherification starch, hydroxyalkylation starch, cross-linking starch or graft starch, and moisture content is controlled at 12-17%;
Described softening agent is a kind of in glycerine, ethylene glycol, propylene glycol, Xylitol, polyoxyethylene glycol, sorbyl alcohol, triglyceride level, methane amide or urea;
Described pigment is selected from that the Chinese is husky yellow, a kind of in solid orange, toluidine red, permanent bordeaux, permanent yellow, phthalocyanine blue or phthalocyanine green forever.
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| CN105295557A (en) * | 2015-11-27 | 2016-02-03 | 广州傲胜人造草有限公司 | Starch-based paint and preparation method thereof |
| CN106497283A (en) * | 2016-10-31 | 2017-03-15 | 富思特新材料科技发展股份有限公司 | A kind of hydrogen bond crosslinks type water-in-water multicolor coating and preparation method thereof |
| CN110157253A (en) * | 2019-04-21 | 2019-08-23 | 嘉宝莉化工集团股份有限公司 | A kind of aqueous, environmental protective texture woodwork coating and preparation method thereof |
| CN111169187A (en) * | 2020-01-16 | 2020-05-19 | 上海准典印务科技有限公司 | Printing method of stain-resistant paper |
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| CN111169187B (en) * | 2020-01-16 | 2021-08-10 | 上海准典印务科技有限公司 | Printing method of stain-resistant paper |
| CN114011217A (en) * | 2021-11-10 | 2022-02-08 | 山东鲁碧建材有限公司 | Wet flue gas desulfurization method |
| CN114011217B (en) * | 2021-11-10 | 2024-04-23 | 山东鲁碧建材有限公司 | Wet flue gas desulfurization method |
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