CN104130630A - Biomass environment-friendly water-based color paste and preparation method thereof - Google Patents
Biomass environment-friendly water-based color paste and preparation method thereof Download PDFInfo
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Abstract
The invention discloses biomass environment-friendly water-based color paste and a preparation method thereof, and aims to solve the problems of single function, poor storage stability and low color keeping degree in the conventional water-based color paste. The preparation method of the biomass environment-friendly water-based color paste comprises the following steps: dispersing an inorganic or metal pigment, a composite modified starch emulsion, a dispersing agent, a biomass stabilizer, a moistening agent, aluminum starch dodecenyl succinate and a pH adjusting agent for a certain period of time, and grinding the mixture; and adding an antifoaming agent, stirring the mixture uniformly at a low speed, filtering the mixture, and packaging the filtered mixture to obtain a biomass water-based color paste product. The product prepared by using the preparation method can be applied to coating, printing and advertising ink jet, and has the characteristics of environmental friendliness, stability, high color retention and the like.
Description
Technical field
The invention belongs to emulsion paint mill base preparation field, be specifically related to a kind of biomass environment-friendly aqueous color paste and preparation method thereof.
Background technology
Aqueous color paste refers to that by organic or inorganic pigment the homogeneous of formation, stable, has certain mobility or thixotropic fluidity, the concentrated pigment slurry of stronger tinctorial strength under wetting, the dissemination of tensio-active agent.Aqueous color paste is for painted, and Application Areas comprises the industries such as coating, printing, papermaking, weaving.Be mainly used at present coating industry, pigment exists with liquid state, makes coating material production become simple and easy to operate.
Existing aqueous color paste ubiquity function singleness: can only, for water-borne coatings, be mainly used in factory's toning of emulsion paint; Package stability is poor; Add in exterior wall paint, protect the degree of look without shortcomings such as assurances.
Summary of the invention
The object of the present invention is to provide a kind of biomass environment-friendly aqueous color paste, to solve the not high problem of degree that function singleness, package stability that existing aqueous color paste exists are poor, protect look.
Another object of the present invention is a kind of preparation method that a kind of biomass environment-friendly aqueous color paste is provided.
To achieve the above object of the invention, technical scheme of the present invention is, a biomass environment-friendly aqueous color paste, is prepared from by appended mass percent by following ingredients: pigment 40-60 part, biomass stablizer 1-5 part, composite modified starch emulsion 15-25 part, laurylene base succinic acid starch aluminium 1-5 part, dispersion agent 5-15 part, defoamer 0.2-0.6 part, pH adjusting agent 0.1-0.5 part, wetting agent 1-4 and softening water 5-15 part.Laurylene base succinic acid starch aluminium substitution value is more than 0.05.
Preferably, described pigment is a kind of in titanium dioxide, zinc oxide, carbon black, iron oxide black, red iron oxide, iron oxide yellow, iron oxide green, ultramarine, cobalt blue, aluminium powder, copper powder.
Preferably, described biomass stablizer is a kind of in carboxymethyl starch, hydroxypropylated starch, starch octenyl succinate anhydride, carboxymethyl cellulose or Natvosol.
Preferably, described dispersion agent is a kind of in polycarboxylate, polyacrylate, long-chain polyamino amidophosphoric acid salt, phosphate ester salt, aliphatic acid polyethenoxy ether, sorbitan stearate, alkylbenzene sulfonate, alkylsulfonate, polycarboxylate is OROTAN731A polycarboxylate sodium or dispersant with high efficiency SN-5040 polycarboxylate sodium, and polyacrylate is SN-5000 polyacrylic acid sodium salt or ROHM AND HAAS polyacrylic acid sodium salt 9400.
Preferably, described defoamer is any one in fatty acid metal soap, organophosphate, water drain silica, fatty acid ester; Described pH adjusting agent is a kind of in sodium hydroxide, sodium bicarbonate, 2-amino-2-methyl-1-propanol, ammoniacal liquor; Described wetting agent is a kind of in polyoxyethylene glycol, polypropylene glycol, glycerine, propylene glycol, BT, polyethyleneglycol derivative, polypropylene glycol derivative.
Preferably, the raw material that described 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.
Preferably, 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 above-mentioned a kind of biomass environment-friendly aqueous color paste, is characterized in that figure comprises the steps:
A, pigment is added to dispersion machine, regulate dispersing speed 500-800r/min, in described ratio, successively softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent are added to dispersion cylinder, regulate dispersing speed 500-800r/min, middle dispersion 20-30min, obtain homogeneous slurry, heighten and disperse rotating speed to 1000-1500r/min, disperse 20-40min;
B, above-mentioned steps a gained mixture is proceeded to horizontal sand mill or three-roll grinder be ground to fineness and be not more than 5 μ m;
C, in described ratio, add defoamer, 500-800r/min rotating speed stirs, and filters and packages, and obtains biomass water-based mill base.
Beneficial effect of the present invention: the 1. composite modified starch emulsion that the present invention adopts is prepared after being cross-linked rear and acrylate monomer grafting with Sumstar 190, the mixing of acidolysis etherification starch.As high molecular polymer, have the advantage of acrylate and starch emulsion concurrently, and there is certain wettability, can increase mill base product film-forming properties, stability, dispersiveness and wettability, both can be applicable to water-borne coatings, also can be used for printing and advertising painting, the feature such as there is stability, protect that look is acted charitably.
2. the present invention has added laurylene base succinic acid starch aluminium, has hydrophilic and hydrophobic two kinds of character, due to the introducing of hydrophobic grouping, makes the activated surface of starch tool.Add in mill base system, can prevent the agglomeration of granules of pigments, reduce the surface tension of water, can play obvious stable dispersion effect.
3. the present invention selects modified starch or modified fibre degree as biomass stablizer, has solved the difficult points such as flocculation in aqueous color paste storage process, precipitation, minute water, and the quality guaranteed period can reach more than 2 years.
4. gained mill base of the present invention be take biomass base material as main auxiliary agent, has the feature of environmental protection, health, belongs to environmentally friendly product.
Embodiment
With regard to specific embodiment, the present invention is further described below.
In following 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 1-3, 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 4-11, 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: biomass environment-friendly aqueous color paste (white)
Titanium dioxide 40kg, biomass stablizer carboxymethyl starch 5 kg, composite modified starch emulsion 22kg, laurylene base succinic acid starch aluminium 1kg, dispersion agent OROTAN731A polycarboxylate sodium 15 kg, defoamer fatty acid metal soap 0.4 kg, pH adjusting agent sodium hydroxide 0.2 kg, wetting agent polyoxyethylene glycol 3 kg, softening water 13.4 kg.
2. the preparation of aqueous color paste
A) in described ratio, titanium dioxide is added to dispersion machine, regulate dispersing speed 600r/min, in described ratio successively by softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent, add dispersion cylinder, disperse 25min, obtain homogeneous slurry, heighten and disperse rotating speed to 1500r/min, disperse 20min.
B) above-mentioned steps a gained mixture being proceeded to horizontal sand mill or three-roll grinder is ground to fineness and is not more than 5 μ m.
C) in described ratio, add defoamer, 600r/min stirring at low speed is even, filters and packages, and obtains biomass water-based mill base (white).
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. biomass environment-friendly aqueous color pastes (black)
Carbon black 40 kg, biomass stablizer hydroxypropylated starch 3 kg, composite modified starch emulsion 25 kg, laurylene base succinic acid starch aluminium 2 kg, dispersion agent dispersant with high efficiency SN-5040 polycarboxylate sodium 10 kg, defoamer organophosphate 0.2 kg, pH adjusting agent sodium bicarbonate 0.3 kg, wetting agent polypropylene glycol 2 kg, softening water 5kg.
2. the preparation of aqueous color paste
A) in described ratio, carbon black is added to dispersion machine, regulate dispersing speed 500r/min, in described ratio successively by softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent, add and disperse to disperse 30min in cylinder, obtain homogeneous slurry, heighten and disperse rotating speed to 1500r/min, disperse 30min.
B) above-mentioned steps a gained mixture being proceeded to horizontal sand mill or three-roll grinder is ground to fineness and is not more than 5 μ m.
C) in described ratio, add defoamer, 500r/min stirring at low speed is even, filters and packages, and obtains biomass water-based mill base (black).
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 3. biomass environment-friendly aqueous color pastes (blueness)
Ultramarine 50 kg, biomass stablizer starch octenyl succinate anhydride 1 kg, composite modified starch emulsion 20 kg, laurylene base succinic acid starch aluminium 3 kg, dispersion agent SN-5000 polyacrylic acid sodium salt 5 kg, defoamer fatty acid ester 0.3 kg, pH adjusting agent 2-amino-2-methyl-1-propanol 0.5 kg, wetting agent glycerine 3 kg, softening water 7.2 kg.
2. the preparation of aqueous color paste
A) in described ratio, ultramarine is added to dispersion machine, regulate dispersing speed 800r/min, in described ratio successively by softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent, add and disperse to disperse 25min in cylinder, obtain homogeneous slurry, heighten and disperse rotating speed to 1000r/min, disperse 40min.
B) above-mentioned steps a gained mixture being proceeded to horizontal sand mill or three-roll grinder is ground to fineness and is not more than 5 μ m.
C) in described ratio, add defoamer, 700r/min stirring at low speed is even, filters and packages, and obtains biomass water-based mill base (blueness).
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 4. biomass environment-friendly aqueous color pastes (green)
Iron oxide green 60 kg, biomass stablizer carboxymethyl cellulose 4 kg, composite modified starch emulsion 15 kg, laurylene base succinic acid starch aluminium 5 kg, dispersion agent ROHM AND HAAS polyacrylic acid sodium salt 9400 are 7 kg, defoamer water drain silica 0.5 kg, pH adjusting agent ammoniacal liquor 0.1 kg, wetting agent propylene glycol 4 kg, softening water 15 kg.
2. the preparation of aqueous color paste
A) in described ratio, red iron oxide is added to dispersion machine, regulate dispersing speed 700r/min, in described ratio successively by softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent, add and disperse to disperse 30min in cylinder, obtain homogeneous slurry, heighten and disperse rotating speed to 1000r/min, disperse 30min.
B) above-mentioned steps a gained mixture being proceeded to horizontal sand mill or three-roll grinder is ground to fineness and is not more than 5 μ m.
C) in described ratio, add defoamer, 800r/min stirring at low speed is even, filters and packages, and obtains biomass water-based mill base (green).
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 5. biomass environment-friendly aqueous color pastes (gold)
Copper powder 50 kg, biomass stablizer Natvosol 2 kg, composite modified starch emulsion 15 kg, laurylene base succinic acid starch aluminium 5 kg, dispersion agent aliphatic acid polyethenoxy ether AEO-9 are 5 kg, defoamer 0.6 kg, pH adjusting agent 0.4 kg, wetting agent 1,2,4-trihydroxybutane, 1 kg, softening water 11 kg.
2. the preparation of aqueous color paste
A) in described ratio, copper powder is added to dispersion machine, regulate dispersing speed 800r/min, in described ratio successively by softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent, add and disperse to disperse 20min in cylinder, obtain homogeneous slurry, heighten and disperse rotating speed to 1500r/min, disperse 20min.
B) above-mentioned steps a gained mixture being proceeded to horizontal sand mill or three-roll grinder is ground to fineness and is not more than 5 μ m.
C) in described ratio, add defoamer, 800r/min stirring at low speed is even, filters and packages, and obtains biomass water-based mill base (gold).
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 1-5 presses building coating use mill base chemical industry standard (HG/T 3951-2007), and performance index are detected, and result is as table 1.
As can be seen from Table 1, aqueous color paste of the present invention can reach coating mill base index request completely, and aspect harmful substance contents far below index request, especially formaldehyde content does not detect, and has the good feature of environmental protection.
Embodiment 6, biomass environment-friendly aqueous color paste (white): difference from Example 1 is that pigment is zinc oxide, and dispersion agent is, wetting agent polyethyleneglycol derivative;
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 7, biomass environment-friendly aqueous color paste (black): difference from Example 1 is that pigment is iron oxide black, and dispersion agent is sulfonic acid LAS linear alkyl benzene sulphonic acid, wetting agent polypropylene glycol derivative;
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 8, biomass environment-friendly aqueous color paste (redness): difference from Example 1 is that pigment is red iron oxide, and dispersion agent is-SAS isomery alkylsulfonate;
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 9, biomass environment-friendly aqueous color paste (yellow): difference from Example 1 is that pigment is iron oxide yellow, dispersion agent is long-chain polyamino amidophosphoric acid salt.
Embodiment 10, biomass environment-friendly aqueous color paste (blueness): difference from Example 1 is that pigment is cobalt blue, and dispersion agent is phosphate ester salt.
Embodiment 11, biomass environment-friendly aqueous color paste (silver color): difference from Example 1 is that pigment is aluminium powder.
Claims (10)
1. a biomass environment-friendly aqueous color paste, is prepared from by appended mass percent by following ingredients: pigment 40-60 part, biomass stablizer 1-5 part, composite modified starch emulsion 15-25 part, laurylene base succinic acid starch aluminium 1-5 part, dispersion agent 5-15 part, defoamer 0.2-0.6 part, pH adjusting agent 0.1-0.5 part, wetting agent 1-4 and softening water 5-15 part.
2. a kind of biomass environment-friendly aqueous color paste according to claim 1, is characterized in that: described pigment is a kind of in titanium dioxide, zinc oxide, carbon black, iron oxide black, red iron oxide, iron oxide yellow, iron oxide green, ultramarine, cobalt blue, aluminium powder, copper powder.
3. a kind of biomass environment-friendly aqueous color paste according to claim 1, is characterized in that: described biomass stablizer is a kind of in carboxymethyl starch, hydroxypropylated starch, starch octenyl succinate anhydride, carboxymethyl cellulose or Natvosol.
4. a kind of biomass environment-friendly aqueous color paste according to claim 1, it is characterized in that: described dispersion agent is a kind of in polycarboxylate, polyacrylate, long-chain polyamino amidophosphoric acid salt, phosphate ester salt, aliphatic acid polyethenoxy ether, sorbitan stearate, alkylbenzene sulfonate, alkylsulfonate, polycarboxylate is OROTAN731A polycarboxylate sodium or dispersant with high efficiency SN-5040 polycarboxylate sodium, and polyacrylate is SN-5000 polyacrylic acid sodium salt or ROHM AND HAAS polyacrylic acid sodium salt 9400.
5. a kind of biomass environment-friendly aqueous color paste according to claim 1, is characterized in that: described defoamer is any one in fatty acid metal soap, organophosphate, water drain silica, fatty acid ester; Described pH adjusting agent is a kind of in sodium hydroxide, sodium bicarbonate, 2-amino-2-methyl-1-propanol, ammoniacal liquor; Described wetting agent is a kind of in polyoxyethylene glycol, polypropylene glycol, glycerine, propylene glycol, BT, polyethyleneglycol derivative, polypropylene glycol derivative.
6. a kind of biomass environment-friendly aqueous color paste according to claim 1, it is characterized in that: the raw material that described 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.
7. a kind of biomass environment-friendly aqueous color paste according to claim 6, is characterized in that: described mix monomer also comprises 1-2.5 parts of function monomers.
8. a kind of biomass environment-friendly aqueous color paste according to claim 6, 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.
9. a kind of biomass environment-friendly aqueous color paste according to claim 6, 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 a kind of biomass environment-friendly aqueous color paste claimed in claim 1, is characterized in that figure comprises the steps:
A, pigment is added to dispersion machine, regulate dispersing speed 500-800r/min, in described ratio, successively softening water, composite modified starch emulsion, dispersion agent, biomass stablizer, wetting agent, laurylene base succinic acid starch aluminium, pH adjusting agent are added to dispersion cylinder, regulate dispersing speed 500-800r/min, middle dispersion 20-30min, obtain homogeneous slurry, heighten and disperse rotating speed to 1000-1500r/min, disperse 20-40min;
B, above-mentioned steps a gained mixture is proceeded to horizontal sand mill or three-roll grinder be ground to fineness and be not more than 5 μ m;
C, in described ratio, add defoamer, 500-800r/min rotating speed stirs, and filters and packages, and obtains biomass water-based mill base.
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| US20160221874A1 (en) * | 2015-02-03 | 2016-08-04 | Construction Research & Technology, Gmbh | Liquid coloring suspension and colored cementitious composition |
| CN107129711A (en) * | 2017-07-03 | 2017-09-05 | 四川马可视觉网络科技有限公司 | Anti- tarnishing poster paint |
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| CN108976915A (en) * | 2018-06-11 | 2018-12-11 | 安徽四季能源科技有限公司 | A kind of preparation method of water nano metal mill base |
| CN112898831A (en) * | 2021-02-07 | 2021-06-04 | 山东华诚高科胶粘剂有限公司 | Resin-free color paste and preparation method and application thereof |
| CN114395294A (en) * | 2021-12-02 | 2022-04-26 | 明光科迪新材料有限公司 | Color paste for intelligent color mixing system and preparation method thereof |
| EP4303279A4 (en) * | 2021-03-02 | 2024-06-26 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous pigment dispersion liquid, aqueous ink-jet ink, and dry coating |
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| EP4303279A4 (en) * | 2021-03-02 | 2024-06-26 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous pigment dispersion liquid, aqueous ink-jet ink, and dry coating |
| CN114395294A (en) * | 2021-12-02 | 2022-04-26 | 明光科迪新材料有限公司 | Color paste for intelligent color mixing system and preparation method thereof |
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