CN100389158C - Room temperature crosslinked aqueous coating and preparation method thereof - Google Patents
Room temperature crosslinked aqueous coating and preparation method thereof Download PDFInfo
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- CN100389158C CN100389158C CNB2005100752555A CN200510075255A CN100389158C CN 100389158 C CN100389158 C CN 100389158C CN B2005100752555 A CNB2005100752555 A CN B2005100752555A CN 200510075255 A CN200510075255 A CN 200510075255A CN 100389158 C CN100389158 C CN 100389158C
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Abstract
The present invention relates to room temperature crosslinked water paint which comprises A copolymer emulsion and B copolymer emulsion with different functional group shell structures, and also relates to a synthesis method of the A polymer emulsion and the B polymer emulsion and a preparation method of the water paint. The present invention provides a room temperature curing crosslinked water paint in a friendly environment and a preparation method thereof. The present invention has the advantages that the cost of raw materials is low, the preparation technology and the construction technology are simple, and the heat resistance, the indentation performance, the water resistance, the hardness, etc. of a paint film of the water paint are improved.
Description
Technical field:
The present invention relates to a kind of room temperature crosslinked aqueous coating and preparation method thereof.
Background technology:
Performances such as esters of acrylic acid coating is with good film-forming properties, and is fast light, weather-proof are widely used in paint field, but it has shortcomings such as poor water resistance, difference of hardness.In order to improve the physical strength of filming, performances such as water tolerance will make macromolecular chain be cross-linked with each other when filming usually.Therefore people generate ketimine structure as US4772680 by acetoacetyl and hydrazine reaction and obtain normal temperature crosslinked emulsion can normal temperature crosslinked film forming emulsion having carried out a large amount of research; EP567128, CN1144242 can at room temperature carry out stable reaction by having the polymkeric substance of holding carboxyl and the polymkeric substance of nitrogen heterocyclic ring alkene class group, the mixed in molar ratio that CN1537895 presses primary amine group/epoxide group=1: 1 with two kinds of components realizes crosslinking reaction.The emulsion coatings resin of mentioning among the CN1554721 is the internal layer that the compound that will have primary amine group is fixed on latex particle, coat with methacrylic ester and acrylate then, obtaining copolymer emulsion, is to mix composition at 1: 1 with the emulsion of this copolymer emulsion and end ring oxycompound and with primary amine group/epoxide group more in molar ratio.And during the two-pack construction, mix the back and solidify easily in the construction time, the system viscosity is increased, unfavorable to constructing, human factor is bigger to the influence of filming, and above-mentioned normal temperature crosslinked system is insufficient to be that material toxicity is big, costs an arm and a leg.
Summary of the invention:
In order to solve the problems of the prior art, it is filmogen that the present invention attempts with A, two kinds of nucleocapsid structure latex particles of B composition polymer emulsion, a kind of room temperature crosslinked aqueous coating and preparation method thereof is provided, make cost of material cheap, preparation and construction technology are simple, and improve stability, the increase degree of crosslinking of emulsion.
A kind of room temperature crosslinked aqueous coating, formulated by two kinds of polymer emulsions of A, B and other auxiliary agents, it is characterized in that two kinds of polymer emulsions of A, B are the emulsion of nucleocapsid structure latex particle, wherein the nucleocapsid structure latex particle stratum nucleare of polymer emulsion A is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, and shell is alkene class hard monomer, alkene class soft monomer and the multipolymer that contains the vinyl monomer of epoxide group, anhydride group or reactive halogen group;
The nucleocapsid structure latex particle stratum nucleare of polymer emulsion B is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, shell be alkene class hard monomer, alkene class soft monomer and can with the multipolymer of the vinyl monomer of epoxide group, anhydride group, reactive halogen radical reaction;
The solid content of A, two kinds of polymer emulsions of B is 25～55%, and latex A and the mass ratio of emulsion B in water-borne coatings are 1: 3～3: 1.
Nucleocapsid structure latex particle stratum nucleare accounts for 25～75% of total polymer mass among latex A and the emulsion B, and shell accounts for 75～25% of total polymer mass.
Alkene class hard monomer is a kind of in the following material or their combination: vinylbenzene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, uncle's nine NSC 11801, uncle's ten NSC 11801, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer.
Alkene class soft monomer is a kind of in the following material or their combination: ethyl propenoate, butyl acrylate, vinylformic acid isopentyl ester, 2-EHA.
Polyenoid class cross-linking monomer is a kind of in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate.
The vinyl monomer that contains epoxide group, anhydride group or reactive halogen group is a kind of in the following material or their combination: glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, maleic anhydride, vinylchlorid vinyl ether, vinyl chloroacetate, p-chloromethyl styrene.
Can be a kind of in the following material or their combination with the vinyl monomer of epoxide group, anhydride group, reactive halogen radical reaction: vinylformic acid, methacrylic acid, acrylamide, n-methylolacrylamide, acrylic amine ethyl ester, methacrylic acid N, silomate base ethyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
The nuclear shell structure rubber particle latex of polymer emulsion A adopts following method preparation:
In the reactor of protection of inert gas, under the agitation condition, add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification, be heated to 40～80 ℃, the aqueous solution initiated polymerization that adds initiator, react and finished stratum nucleare particle building-up reactions in 1～2 hour, wherein used alkene class hard monomer, alkene class soft monomer and the monomeric mass ratio of polyenoid class: 40～80: 20～60: 0.01～1.0;
Then the shell olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～3 hour, finish the synthetic of shell particle, wherein used alkene class hard monomer, alkene class soft monomer and contain the mass ratio of the vinyl monomer of epoxide group, anhydride group or reactive halogen group: 20～50: 20～90: 5～40;
In reactor, add the back afterwards and eliminate initiator solution, be incubated 1～2 hour,, filter discharging, obtain the nuclear shell structure rubber particle latex of polymer emulsion A through cooling.
The nuclear shell structure rubber particle latex of polymer emulsion B adopts following method preparation:
In the reactor of protection of inert gas, under the agitation condition, add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification, be heated to 40～80 ℃, the aqueous solution initiated polymerization that adds initiator, react and finished stratum nucleare particle building-up reactions in 1～2 hour, wherein used alkene class hard monomer, alkene class soft monomer and the monomeric mass ratio of polyenoid class are 40～80: 20～60: 0.01～1.0;
Then the shell olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～3 hour, finish the synthetic of shell particle, wherein used alkene class hard monomer, alkene class soft monomer and can be 20～50: 20～90: 5～40 with the mass ratio of the vinyl monomer of the reaction of epoxide group, anhydride group or reactive halogen group;
In reactor, add the back afterwards and eliminate initiator solution, be incubated 1～2 hour,, filter discharging, obtain the nuclear shell structure rubber particle latex of polymer emulsion B through cooling.
Preparation latex A and the used initiator of emulsion B are Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or ammonium persulfate-sodium bisulfite.
The present invention also provides a kind of preparation method of above-mentioned room temperature crosslinked aqueous coating, by A, two kinds of polymer emulsions of B and other auxiliary agents are formulated, concrete compound method is: earlier with A, two kinds of polymer emulsions of B are mixed and made into to behind the filmogen, composite again with film coalescence aid, flow agent, defoamer, thickening material, rheology modifier, mould inhibitor, sanitas, wetting agent, anti-zoned colored agent, matting agent and color stuffing are made water-borne coatings, A wherein, two kinds of emulsions of B account for 70～95% of coating gross weight altogether, other auxiliary agents are 30～5%, and the total resultant of each component is 100% in the described room temperature crosslinked aqueous coating.
The present invention proposes to be synthesized by seeded emulsion polymerization respectively the A emulsion and the B emulsion of different functional groups, and the structure of latex particle is nucleocapsid structure, and wherein the shell of the latex particle of A emulsion is uniform-distribution with epoxy-functional, anhydride group, reactive halogen group; The shell of B component latex particle is uniform-distribution with carboxyl, amido, hydroxyl.Then A emulsion and B emulsion are mixed according to a certain percentage, and with composite formation water-borne coatingss such as auxiliary agent.When emulsion or water-borne coatings state, because the existence of the formed electrostatic double layer of emulsifying agent, be subjected to the charge repulsion effect of electrostatic double layer at the aqueous phase latex particle, coalescence does not take place in latex particle, so the functional group separately of A emulsion and B emulsion does not react.But when water-borne coatings is filmed, because the volatilization gradually of moisture, under certain temperature and film coalescence aid assistance, between latex particle gradually near and merge, polymer molecular chain holds mutually and closes, A emulsion and B emulsion particle shell functional group meet, and the crosslinking reaction of covalency takes place, and make performances such as paint film water tolerance, thermotolerance and hardness all be improved.
Embodiment:
Embodiment 1;
(1) the A emulsion is synthetic
Having water of condensation, stir, thermometer, add 35.7 kilograms of deionized waters in 100 liters of enamel reaction stills of Dropping feeder, 0.15 kilogram alkyl diphenyl disodium sulfonate, 0.30 the reactive emulsifier allyl group polyethoxye sulfonate (SEN-10) of kilogram, 9.1 kilogram vinylbenzene, 2.8 kilograms of butyl acrylates, 0.1 kilogram of Vinylstyrene, stirring and emulsifying, logical nitrogen 20min is warming up to 40 ℃ of initiated polymerizations, adds 0.012 kilogram of Potassium Persulphate and 0.012 kilogram of sodium bisulfite water liquid (water yield is 0.4 kilogram), after the initiation reaction 1 hour, the temperature of reaction of system remains on 60 ± 2 ℃ gradually.
The preparation of shell polymkeric substance:
With 5.8 kilograms of methyl methacrylates that mix, 10.0 the kilogram butyl acrylate, 3.0 kilograms of glycidyl methacrylate drip (water yield is 1.8 kilograms) simultaneously with 0.018 kilogram of Potassium Persulphate and 0.018 kilogram of aqueous solution of sodium bisulfite, be added dropwise to complete afterreaction 1 hour in 2 hours.
Be warming up to 72 ± 2 ℃.Add the rongalite of 0.015 kilogram of back elimination initiator and 0.015 kilogram tertbutyl peroxide and (be made into the aqueous solution, the water yield is 0.4 kilogram), reacted 1～2 hour, be cooled to below 40 ℃ and filter discharging, get the emulsion of two-layer core shell structure, solid content 45%, reacting balance in the polymerization process is not found gel.
(2) the B emulsion is synthetic:
The synthetic of B emulsion is that other condition is identical with technology with the methacrylic acid of weight such as the glycidyl methacrylate in the A emulsion synthetic component replaces with.
(3) preparation of varnish type coating (following said umber is mass parts)
A emulsion and B emulsion mixed in 1: 3 ratio of mass ratio make the A/B mixed emulsion.
100 parts of A/B mixed emulsions of the present invention are added in the stirring tank, open and stir, drip 0.2 part pH value conditioning agent AMP95 gradually, 795,2 parts of furtherance films of film coalescence aid auxiliary agent (propylene glycol) of 5 parts, 0.5 part of wetting agent, 0.8 part flow agent 2020,0.2 part defoamer 681F, 5230,0.01 parts of mould inhibitors 1138 of 0.1 part of thickening material, 0.01 part sanitas MV, 5 parts of anti-zoned colored agent (anti-scraping 810) are fully stirred, and make varnish type water-borne coatings.
(4) performance measurement and measuring method thereof: (concrete data see Table 2)
The mensuration of degree of crosslinking: take by weighing a certain amount of film that in baking oven, dries to constant weight, pack in the load weighted in advance filter paper, in apparatus,Soxhlet's, use acetone extracting 48 hours, film after the extracting is dried to constant weight in baking oven, calculate the degree of crosslinking of film according to following formula: the quality (g) * 100% of weight (the g)/extracting cephacoria of film degree of crosslinking=extracting caudacoria.
Cup impression performance measurement that coating is water-fast:
In beaker, irritate 400ml water, boil.On tested base material, fall some boiling water, on will also having the beaker of boiling water to be positioned over then to film.Beaker is placed 15min on tested base material.After the 15min, take beaker away, grade to filming immediately; Wait to film and recover to grade after 6 hours.Nothing is turned white, and no impression is a top grade, and no impression has little turning white, but reverts to good level after doing, impression is arranged or turn white after can not revert to failure.
The water resistance test of film: GB/T1733-93 tests according to GB.
The test of film hardness: use paint film pencil scratch hardness instrument according to GB GB/T6739-1966.
The synthetic used monomer and the consumption of embodiment 2-12:A emulsion see Table 1, and the synthetic used monomer and the consumption of B emulsion see Table 2, and the blending ratio of A emulsion and B emulsion sees Table 3, and other preparation condition is with embodiment 1.
The synthetic used monomer and the consumption of table 1:A emulsion
Unit: kilogram
The synthetic used monomer and the consumption of table 2:B emulsion
Unit: kilogram
St is a vinylbenzene in the table, MMA is a methyl methacrylate, and BA is a butyl acrylate, and DVB is a Vinylstyrene, GMA is a glycidyl methacrylate, AN is a vinyl cyanide, and AA is a vinylformic acid, and MAA is a methacrylic acid, TEGDA triethylene Glycol dimethacrylate, the MAL maleic anhydride, IBOMA isobornyl methacrylate, AM are acrylamide; IPA vinylformic acid isopentyl ester, IBOA is an isobornyl acrylate, HEA Hydroxyethyl acrylate, MAL2 are MALEIC ANHYDRIDE, TPGDA tripropylene glycol dimethacrylate, the EA ethyl propenoate, the VCA vinyl chloroacetate, uncle's VeoVa-10 ten NSC 11801, DMEA methacrylic acid N, silomate base ethyl ester, the NAM n-methylolacrylamide.
20 ℃ of degree of crosslinking of room temperature, The performance test results such as water-fast cup indentation test, resistance to boiling water, room temperature water tolerance, film hardness see Table 3.
Table 3: the every testing performance index result of embodiment 1-12A, B emulsion proportion and water-borne coatings
Embodiment 13-18: the preparation of colored paint type coating
In the dispersion cylinder of high speed dispersor, add 100 parts of deionized waters, 5 parts of dispersion agent DP-270 consumptions, 1.5 parts of defoamer 681F, 1200 rev/mins were stirred 10 minutes, slowly add 50 parts of commercially available rutile titanium dioxides successively, 10 parts of kaolin, 5 parts of talcum powder continued dispersed with stirring 20 minutes, ground twice with sand mill, fineness reaches below 30 microns and forms pigment slurry, and is stand-by.
In the paint still, under the 100-300 rev/min of stirring velocity, adding will be pressed mass ratio listed in the table 4 by the embodiment of the invention 2,4,6,8,10 or two kinds of emulsions of 12 synthetic A, B and be mixed stirring, be mixed with 100 parts of A/B mixed emulsions, drip 0.2 part pH value conditioning agent AMP95 then gradually, 795,2 parts of furtherance films of film coalescence aid auxiliary agent (propylene glycol) of 5 parts, 0.5 part wetting agent, 0.2 part of defoamer 681F.
Ground pigment slurry is slowly added in the emulsion in the paint still, slowly add 2020,0.5 parts of thickening materials 5230 of 2.0 parts of flow agents then successively, 0.02 part 1138,0.02 parts of sanitas MV of mould inhibitor look color and require to add various color paste tonings, fully stir, make colored paint type water-borne coatings.
Table 4: the every testing performance index result of colored paint type water-borne coatings of embodiment 13-18 prescription
Claims (4)
1. room temperature crosslinked aqueous coating, formulated by two kinds of polymer emulsions of A, B and other auxiliary agents, it is characterized in that two kinds of polymer emulsions of A, B are the emulsion of nucleocapsid structure latex particle, wherein the nucleocapsid structure latex particle stratum nucleare of polymer emulsion A is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, and shell is alkene class hard monomer, alkene class soft monomer and the multipolymer that contains the vinyl monomer of epoxide group, anhydride group or reactive halogen group;
The nucleocapsid structure latex particle stratum nucleare of polymer emulsion B is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, shell be alkene class hard monomer, alkene class soft monomer and can with the multipolymer of the vinyl monomer of epoxide group, anhydride group or reactive halogen radical reaction;
The stratum nucleare of nucleocapsid structure latex particle accounts for the 25-75% of total polymer mass among latex A and the emulsion B, shell accounts for the 75-25% of total polymer mass, the solid content of A, two kinds of polymer emulsions of B is 25～55%, and latex A and the mass ratio of emulsion B in water-borne coatings are 1: 3～3: 1;
Described alkene class hard monomer is a kind of in the following material or their combination: vinylbenzene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, uncle's nine NSC 11801, uncle's ten NSC 11801, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer;
Alkene class soft monomer is a kind of in the following material or their combination: ethyl propenoate, butyl acrylate, vinylformic acid isopentyl ester, 2-EHA;
Polyenoid class cross-linking monomer is a kind of in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate;
The vinyl monomer that contains epoxide group, anhydride group or reactive halogen group is a kind of in the following material or their combination: glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, maleic anhydride, vinylchlorid vinyl ether, vinyl chloroacetate, p-chloromethyl styrene;
Can be a kind of in the following material or their combination with the vinyl monomer of epoxide group, anhydride group or reactive halogen radical reaction: vinylformic acid, methacrylic acid, acrylamide, n-methylolacrylamide, acrylic amine ethyl ester, methacrylic acid N, silomate base ethyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
2. according to the room temperature crosslinked aqueous coating of claim 1, it is characterized in that the nuclear shell structure rubber particle latex of polymer emulsion A adopts following method preparation:
In the reactor of protection of inert gas, under the agitation condition, add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification, be heated to 40～80 ℃, the aqueous solution initiated polymerization that adds initiator, react and finished stratum nucleare particle building-up reactions in 1～2 hour, wherein used alkene class hard monomer, alkene class soft monomer and the monomeric mass ratio of polyenoid class: 40～80: 20～60: 0.01～1.0;
Then the shell olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～3 hour, finish the synthetic of shell particle, wherein used alkene class hard monomer, alkene class soft monomer and contain the mass ratio of the vinyl monomer of epoxide group, anhydride group or reactive halogen group: 20～50: 20～90: 5～40;
In reactor, add the back afterwards and eliminate initiator solution, be incubated 1～2 hour,, filter discharging, obtain the nuclear shell structure rubber particle latex of polymer emulsion A through cooling;
The nuclear shell structure rubber particle latex of polymer emulsion B adopts following method preparation:
In the reactor of protection of inert gas, under the agitation condition, add deionized water, emulsifying agent, nuclear layer monomer successively and carry out emulsification, be heated to 40～80 ℃, the aqueous solution initiated polymerization that adds initiator, react and finished stratum nucleare particle building-up reactions in 1～2 hour, wherein used alkene class hard monomer, alkene class soft monomer and the monomeric mass ratio of polyenoid class are 40～80: 20～60: 0.01～1.0;
Then the shell olefinic monomer is mixed, be added dropwise in the reactor simultaneously with initiator solution, after dropwising, reacted 0.5～3 hour, finish the synthetic of shell particle, wherein used alkene class hard monomer, alkene class soft monomer and can be 20～50: 20～90: 5～40 with the mass ratio of the vinyl monomer of the reaction of epoxide group, anhydride group or reactive halogen group;
In reactor, add the back afterwards and eliminate initiator solution, be incubated 1～2 hour,, filter discharging, obtain the nuclear shell structure rubber particle latex of polymer emulsion B through cooling.
3. according to the water-borne coatings of claim 2, it is characterized in that: preparation latex A and the used initiator of emulsion B are Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or ammonium persulphate one sodium bisulfite.
4. the preparation method of a room temperature crosslinked aqueous coating, by A, two kinds of polymer emulsions of B, multiple auxiliary agent, color stuffing is formulated, concrete compound method is: earlier with A, obtain mixed emulsion behind two kinds of polymer emulsion thorough mixing of B, composite again with film coalescence aid, flow agent, defoamer, thickening material, rheology modifier, mould inhibitor, sanitas, wetting agent, anti-zoned colored agent, matting agent and color stuffing are made water-borne coatings, A wherein, two kinds of emulsions of B account for 70～95% of coating gross weight altogether, other auxiliary agents are 30～5%, and the total resultant of each component is 100% in the described room temperature crosslinked aqueous coating;
Two kinds of polymer emulsions of described A, B are the emulsion of nucleocapsid structure latex particle, wherein the nucleocapsid structure latex particle stratum nucleare of polymer emulsion A is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, and shell is alkene class hard monomer, alkene class soft monomer and the multipolymer that contains the vinyl monomer of epoxide group, anhydride group or reactive halogen group;
The nucleocapsid structure latex particle stratum nucleare of polymer emulsion B is the multipolymer of alkene class hard monomer, alkene class soft monomer and polyenoid class cross-linking monomer, shell be alkene class hard monomer, alkene class soft monomer and can with the multipolymer of the vinyl monomer of epoxide group, anhydride group or reactive halogen radical reaction;
The stratum nucleare of nucleocapsid structure latex particle accounts for the 25-75% of total polymer mass among latex A and the emulsion B, shell accounts for the 75-25% of total polymer mass, the solid content of A, two kinds of polymer emulsions of B is 25～55%, and latex A and the mass ratio of emulsion B in water-borne coatings are 1: 3～3: 1;
Described alkene class hard monomer is a kind of in the following material or their combination: vinylbenzene, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, uncle's nine NSC 11801, uncle's ten NSC 11801, uncle's hendecoic acid vinyl acetate, acrylonitrile monemer;
Alkene class soft monomer is a kind of in the following material or their combination: ethyl propenoate, butyl acrylate, vinylformic acid isopentyl ester, 2-EHA;
Polyenoid class cross-linking monomer is a kind of in the following material or their combination: Vinylstyrene, bisacrylamide, ethylene glycol dimethacrylate, tirethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethyl-acrylate;
The vinyl monomer that contains epoxide group, anhydride group or reactive halogen group is a kind of in the following material or their combination: glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, maleic anhydride, vinylchlorid vinyl ether, vinyl chloroacetate, p-chloromethyl styrene;
Can be a kind of in the following material or their combination with the vinyl monomer of epoxide group, anhydride group or reactive halogen radical reaction: vinylformic acid, methacrylic acid, acrylamide, n-methylolacrylamide, acrylic amine ethyl ester, methacrylic acid N, silomate base ethyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200606B (en) * | 2007-10-31 | 2010-09-08 | 傅校坤 | Room temperature cross-linking latex paint |
| JP2009256476A (en) * | 2008-04-17 | 2009-11-05 | Dic Corp | Resin composition for plastic coating and plastic coating |
| CN101864040A (en) * | 2010-05-28 | 2010-10-20 | 青岛科技大学 | Preparation method of butyl acrylate-styrene-acrylonitrile graft copolymer |
| CN102070738B (en) * | 2010-11-30 | 2012-05-23 | 山东电力研究院 | Preparation method of hydroxyl group-containing functional monomer modified acrylate copolymer emulsion |
| CN102558427B (en) * | 2011-12-20 | 2013-09-25 | 四川大学 | Polymer emulsion for water-based printing ink and preparation method thereof |
| CN103525231B (en) * | 2012-07-04 | 2016-12-21 | 长春市三化实业有限责任公司 | Cold curing automobile waterborne clear finish |
| CN109266251A (en) * | 2018-09-06 | 2019-01-25 | 深圳市德顺通科技有限公司 | A kind of low-temperature setting method of high-performance environment protection type adhesive |
| CN111138587B (en) * | 2019-12-25 | 2022-05-31 | 广东银洋环保新材料有限公司 | Environment-friendly water-based printing acrylic emulsion, preparation method thereof and water-based printing paint |
| CN112851885B (en) * | 2021-01-12 | 2022-12-13 | 安徽本雅明涂料有限公司 | Single-component self-crosslinking emulsion with hard barrier layer, preparation method and application |
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