CN103319665B - Single-component room-temperature multiple-self-crosslinking aqueous epoxy acrylate resin emulsion and preparation method thereof - Google Patents
Single-component room-temperature multiple-self-crosslinking aqueous epoxy acrylate resin emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a single-component room-temperature multiple-self-crosslinking aqueous epoxy acrylate resin emulsion and a preparation method thereof. The method comprises the steps of: firstly, in parts by mass, preparing 40-50 parts of bisphenol A type epoxy resin and 50-60 parts of unsaturated fatty acid, introducing nitrogen gas to protect under the action of a catalyst, and carrying out esterification reaction so as to synthesize unsaturated fatty acid-modified epoxy ester resin; then, adding a cosolvent to room-temperature self-crosslinking epoxy ester resin, dropwise adding an initiator, monomers with hydrophilic groups, self-crosslinking functional monomers and a chain transfer agent to the room-temperature self-crosslinking epoxy ester resin in 1-3 h at the temperature of 100-110 DEG C, and then, carrying out free radical grafting and copolymerizing reaction so as to obtain single-component room-temperature multiple-self-crosslinking aqueous epoxy acrylate resin; and adding an amine neutralizer to neutralize, and then, adding deionized water to disperse, thereby obtaining a single-component dual-self-crosslinking aqueous epoxy acrylate resin emulsion. The emulsion has the advantages of fast paint film drying, strong adhesive power, high mechanical strength and excellent corrosion resistance.
Description
Technical field
The invention belongs to coating class technical field, be specifically related to a kind of matrix resin being mainly used in the protective system of steel product, be particularly useful for the protection of vehicular traffic, engineering machinery, steel furniture production etc. and the self-crosslinking aqueous protective system of one component room temperature of coating application.
Technical background
Epoxy resin, as one of three large interchangeable heat thermosetting resins, has fabulous tack, stability, wear resistance, erosion resistance, insulativity and physical strength, is widely used in coatings industry.But traditional epoxy resin will use a large amount of organic solvents in the application, this adds cost on the one hand, and the shortcomings such as another aspect organic solvent is inflammable, explosive, poisonous, contaminate environment bring a lot of inconvenience to storage and construction.This shortcoming limits the extensive use of epoxy resin in coatings industry.Along with day by day improving and the continuous enhancing of people's environmental consciousness of various countries' environmental regulation, be that the water-borne coatings of solvent and dispersion agent obtains as the coating variety of environmental protection and develops rapidly with water, exploitation water-borne coatings has become the development trend of following coating industry.
In order to improve the paint film property of water-borne coatings, can reach the excellent properties of solvent based coating paint film, after dried coating film, formation is crosslinked becomes common demands.By crosslinked, the three-dimensional net structure of emulsion film height of formation, thus the water tolerance of film, erosion resistance and physical strength are improved significantly than non-crosslinked type emulsion.According to crosslinking method, crosslinked high-temperature cross-linking, UV curing cross-linked and normal temperature crosslinked can be divided into.High-temperature cross-linking needs to heat and lot of energy, and the range of application of UV curing cross-linked is restricted, as not being applied in building coating.And the normal temperature crosslinked energy of can not only saving, but also be applicable to any application and execution conditions.According to packaging means, the crosslinked crosslinked and two component of single-component that can be divided into again is cross-linked.Two component refers to coating products and solidifying agent two components, and during packaging, two kinds of components must packing storage, now with the current, and two components are general very short for mixed duration of service, must disposablely be finished.The two component of the many employings of existing water-based anticorrosive paint, application cost is high, and constructing operation is loaded down with trivial details, and single-component packaging can avoid these defects.Therefore, develop the self-crosslinking aqueous coating of one component room temperature and have more wide market outlook and using value.
Usually containing bringing out crosslinked functional group by self chemical reaction or additional crosslink agent in the polymer molecular chain of ambient crosslinking water-borne coatings film-forming resin.Self-crosslinking realizes being cross-linked from condensation or autooxidation from the function monomer of condensation or autoxidation performance in room temperature film-forming process by being incorporated into having on polymer molecular chain.Room-temperature self crosslinking system mainly contains following four kinds: in the By Hydrolysis At Room Temperature polycondensation self-crosslinking based on the room-temperature self crosslinking of N hydroxymethyl acrylamide and derivative thereof, siloxanes, the room-temperature self crosslinking based on epoxide group and unsaturated fatty acids, the room temperature autoxidation of double bond is cross-linked.The room-temperature self crosslinking coating of current exploitation is adopt single crosslinking method mostly, along with people require more and more higher to the film performance of coating, the performance of single crosslinked water-borne coatings often can not meet the requirement of application, and the multiple cross-linked cross-linking density that effectively can improve paint film, and then improve the performances such as the water tolerance of paint film, wear resistance, erosion resistance and physical strength, represent the development trend of water-based anticorrosive paint self-crosslinking technology in the future.
Summary of the invention
The object of the invention is to the weak point overcoming existing aqueous epoxy resins etching ground, multiple self-crosslinking aqueous epoxy acrylic resin emulsion of a kind of one component room temperature and preparation method thereof is provided, its product advantage be using water as solvent, nontoxic pollution-free, emulsion particle diameter are little, stability in storage good, brushing performance is good, paint film flat smooth, glossiness are high, keep again the strong adhesion of solvent epoxy varnish etching ground, water-tolerant, the excellent properties such as corrosion-resistant and wear-resisting simultaneously.
Of the present invention and the Water-borne modification of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature be adopt free radical grafting modification method, under the effect of initiator, the methylene radical on epoxy molecule chain is caused and form free radical, with the acrylic monomer graft copolymerization with carboxyl, carboxyl introduced by epoxy molecule chain, then in and salify after in water dispersion and obtain self-emulsified aqueous epoxy emulsion.Emulsion particle obtained by chemic modified method is little, is generally nm level, good stability.
Of the present invention and the multiple self-crosslinking of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature be realized by two kinds of approach: one is by epoxy resin and unsaturated fatty acids, esterification occurs under the effect of catalyzer to produce self-drying type epoxy ester, utilizes the autoxidation of the carbon-carbon double bond on unsaturated fatty acids be cross-linked and realize the room-temperature self crosslinking of coating, two is when water-borne modification of epoxy resin, two kinds had the acrylic acid or the like function monomer (N ?n-methylolacrylamide and methyl propenoic acid glycidyl ether) of self-crosslinking performance, by free yl graft polymerization reaction and other acrylic monomer copolymerization, be incorporated on epoxy molecule chain in the lump, utilize N ?the polycondensation of n-methylolacrylamide activity itself group or the crosslinking reaction with carboxylic acrylic monomer in system, and these two kinds of self-crosslinking modes of condensation dehydration reaction between the hydroxyl produced after the epoxide group open loop of methyl propenoic acid glycidyl ether and realize the multiple self-crosslinking of room temperature of water-based epoxy acrylic resin emulsion.
In order to reach above object, this technology adopts following technical scheme:
The synthesis of the first step unsaturated fatty acids modified epoxy ester resin
In mass fraction, be raw material by 40 ~ 50 parts of bisphenol A type epoxy resins and 50 ~ 60 parts of unsaturated fatty acidss, pass into nitrogen protection under the effect of 0.5 ~ 2 part of catalyzer, esterification is carried out when 120 ~ 150 DEG C, after the massfraction being reacted to unsaturated fatty acids drops to 60 ~ 70%, be warming up to 190 ~ 210 DEG C again, reacting to system acid number lower than 5mgKOH/100g is terminal, obtained room-temperature self crosslinking epoxy ester resin;
In such scheme, described epoxy resin be bisphenol A type epoxy resin E ?20, E ?12 or its mixture; Described unsaturated fatty acids is dehydrated castor oleic acid, linolenic acid, eleostearic acid, or its mixture.Described catalyzer is one or more in tetrabutyl titanate, Mono-n-butyltin, triphenylphosphine and Tetrabutyl amonium bromide;
The synthesis of the multiple self-crosslinking aqueous epoxy acrylic resin of second step one component room temperature
Added by solubility promoter in room-temperature self crosslinking epoxy ester resin, by percentage to the quality, controlling room temperature self-cross-linking epoxy ester resin solid content is 45 ~ 60%; Under passing into nitrogen protection condition, in mass fraction, by 1 ~ 3 part of initiator, 22 ~ 45 parts there is hydrophilic radical monomer, 8 ~ 15 parts of self-crosslinking function monomers and 0.21 ~ 0.56 part of chain-transfer agent, at 100 ~ 110 DEG C, be added drop-wise in 1 ~ 3h in room-temperature self crosslinking epoxy ester resin and carry out free radical grafting copolymerization reaction, after insulation 0.5 ~ 1.5h, to add after 0.5 ~ 1 initiator insulation reaction 2 ~ 4h again, finally insulation reaction 1 ~ 3h after being warming up to 115 ~ 125 DEG C, namely obtains the multiple self-crosslinking aqueous epoxy acrylic resin of one component room temperature;
In such scheme, described in have hydrophilic radical monomer be vinylformic acid, methacrylic acid, n-butyl acrylate, vinylbenzene or methyl methacrylate; Described self-crosslinking function monomer be methyl propenoic acid glycidyl ether and N ?n-methylolacrylamide, mass ratio shared by two kinds is 1:10 ~ 1:20; Described initiator is benzoyl peroxide; Described chain-transfer agent is n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, n-dodecyl mereaptan, chooses wherein one or more; Described solubility promoter is propyl carbinol, Virahol, butyl glycol ether, propylene glycol monomethyl ether, chooses wherein one or more.
The configuration of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the 3rd step one component room temperature
In mass fraction, by 45 ~ 60 parts of multiple self-crosslinking aqueous epoxy acrylic resins of one component room temperature, to add 40 ~ 60 DEG C time in the amine neutralizing agent of resinous acid value equivalent 70 ~ 100% and after, add 40 ~ 55 parts of deionized water dispersions again, namely obtain the dual self-crosslinking aqueous epoxy acrylic resin emulsion of single-component.
In such scheme, the described neutralizing agent described in the 3rd step configuration is triethylamine, N, N ?dimethylethanolamine, trolamine, 2 ?An Ji ?1 ?propyl alcohol, N ?ethyl beautiful jade, choose wherein one or more, consumption is 70 ~ 100% of resin emulsion acid number equivalent.
Two-step reaction of the present invention and the configuration of final step emulsion can be carried out in same reactor, therefore easy to operate, save energy.Gained water-based epoxy acrylic resin emulsion smell is little, and outward appearance is pale yellow transparent shape, and the emulsion particle diameter of size distribution result display is evenly distributed, and particle diameter is at below 100nm.
The multiple self-crosslinking aqueous epoxy acrylic resin emulsion of this one component room temperature through spraying, brush or dip-coating behind iron and steel material quality surface, seasoning gets final product film forming in five days at ambient temperature, paint film glossy clear after film forming, there is excellent glossiness, in 40 DEG C of boiling water, soak seven days without any whiting, salt spray resistance can reach more than 200h.
Relative to prior art, beneficial effect of the present invention is as follows:
(1) by the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature prepared by the present invention, combine the tack of epoxy resin excellence, wear resistance, erosion resistance, insulativity and physical strength, the advantages such as the glossiness excellent with acrylic resin and resistance to outdoor aging performance, pass through self-emulsification in the epoxy simultaneously, introduce the hydrophilic radicals such as (methyl) acrylic acid carboxyl, make its Water-borne modification, not only product nontoxic pollution-free, meet environment protection requirement, obtained emulsion particle is little, and storage stability is good.
(2) this product emulsion adopts single-component packaging, and can at room temperature condition self-crosslinking film-forming, in use without the need to adding solidifying agent, film process is also without the need to heating or radiation, therefore not only reduce energy loss and save cost, and avoid the defect of two component packaging constructing operation complexity, use convenient.
(3) in film performance, the single self-crosslinking of the different single-component coating in the past of this emulsion, but adopt multiple self-crosslinking structure, the cross-linking density of further raising film, the rate of drying of paint film becomes faster, thus make the sticking power of film, water tolerance, corrosion-resistant and wear resisting property obtains and improves greatly.
Embodiment
For understanding the present invention better, below in conjunction with embodiment, the present invention is further illustrated, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
The preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature, comprises the following steps:
A. in the reactor being connected with nitrogen protection, after adding 30gE-12 type epoxy resin and 20gE-20 type epoxy resin, be warming up to 100 DEG C, after insulation 0.5h makes the complete melting of E-12 type epoxy resin of solid state, open and stir, add the mixture of 38g linolenic acid and 15g eleostearic acid again, and add 0.5g catalyzer Mono-n-butyltin, insulation reaction 3h after being warming up to 140 DEG C, now in system, the mass concentration of unsaturated fatty acids drops to 60%, and then after being warming up to 195 DEG C after insulation reaction 6h system acid number be 2.8mgKOH/g, be reaction end, obtain the room-temperature self crosslinking epoxy ester resin of unsaturated fatty acids modification.
B. be equipped with in the reactor of the 40g room-temperature self crosslinking epoxy ester resin synthesized above-mentioned, add 60g propyl carbinol to dilute and stir and be warming up to 105 DEG C, at 1.68g initiator benzoyl peroxide and 0.36g chain-transfer agent n-dodecyl mereaptan, drip 4g methacrylic acid, 30g vinylbenzene, 6.7g n-butyl acrylate, 6.3g methyl methacrylate and 1g methyl propenoic acid glycidyl ether and 12gN-n-methylolacrylamide (dissolving with 40g butyl glycol ether), 110 DEG C of insulation 1h are being warming up to again after dripping in 2h, add residue 0.42g initiator (dissolving with 20g propylene glycol monomethyl ether) again, continue insulation 2h, finally be warming up to 120 DEG C of insulation reaction 1h again, the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature that solid content is 45% can be obtained.
C. be in the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature of 45% at 50g solid content, add 1.5g neutralizing agent triethylamine and 4g deionized water, 500r/min dispersed with stirring 30min, can obtain the multiple self-cross-linking epoxy acrylic acid resin emulsion of one component room temperature that solid content is 26%.
This emulsion is light yellow transparent liquid, and smell is little, and emulsion particle diameter is 92nm, and viscosity is 300mPa.s, and acid number is 22.5mgKOH/g.After spraying to steel surface, room temperature condition lower five days drying and forming-films, film is smooth, has excellent glossiness, and in 40 DEG C of boiling water, soak seven days without any whiting, salt spray resistance can reach more than 200h.
Embodiment 2
The preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature, comprises the following steps:
A. in the reactor being connected with nitrogen protection, after adding 40gE-12 type epoxy resin, be warming up to 110 DEG C, after insulation 0.5h makes the complete melting of E-12 type epoxy resin of solid state, open and stir, add the mixture of 30g dehydrated castor oleic acid and 20g eleostearic acid again, and add 2g catalyzer triphenylphosphine, insulation reaction 3h after being warming up to 150 DEG C, now in system, the mass concentration of unsaturated fatty acids drops to 70%, and then after being warming up to 200 DEG C after insulation reaction 5h system acid number be 3.1mgKOH/g, be reaction end, obtain the room-temperature self crosslinking epoxy ester resin of unsaturated fatty acids modification.
B. in the reactor of the above-mentioned 55g room-temperature self crosslinking epoxy ester resin being equipped with to synthesize, add 50g propyl carbinol to dilute and stir and be warming up to 110 DEG C, under the effect of 2.4g initiator benzoyl peroxide and 0.27g chain-transfer agent octyl mercaptan, drip 4g methacrylic acid, 13g vinylbenzene, 4.7g n-butyl acrylate, 2.3g methyl methacrylate and 1g methyl propenoic acid glycidyl ether and 20gN-n-methylolacrylamide (dissolving with 30g butyl glycol ether), 115 DEG C of insulation 1h are being warming up to again after dripping in 2h, add residue 0.55g initiator (dissolving with 40g propylene glycol monomethyl ether) again, continue insulation 2h, finally be warming up to 120 DEG C of insulation reaction 1h again, the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature that solid content is 50% can be obtained.
C. be in the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature of 50% at 55g solid content, add 1.7g neutralizing agent N ' N ?dimethylethanolamine and 4g deionized water, 500r/min dispersed with stirring 30min, can obtain the multiple self-cross-linking epoxy acrylic acid resin emulsion of one component room temperature that solid content is 28%.
This emulsion is light yellow transparent liquid, and smell is little, and emulsion particle diameter is 89nm, and viscosity is 275mPa.s, and acid number is 21mgKOH/g.After spraying to steel surface, room temperature condition lower five days drying and forming-films, film is smooth, has excellent glossiness, and in 40 DEG C of boiling water, soak seven days without any whiting, salt spray resistance can reach more than 200h.
Embodiment 3:
The preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature, comprises the following steps:
A. in the reactor being connected with nitrogen protection, after adding 30gE-12 type epoxy resin and 10gE-20 type epoxy resin, be warming up to 100 DEG C, after insulation 0.5h makes the complete melting of E-12 type epoxy resin of solid state, open and stir, add 37g linolenic acid again, and add 1g catalyzer Tetrabutyl amonium bromide, insulation reaction 2h after being warming up to 160 DEG C, now in system, the mass concentration of unsaturated fatty acids drops to 65%, and then after being warming up to 210 DEG C after insulation reaction 6h system acid number be 2.8mgKOH/g, be reaction end, obtain the room-temperature self crosslinking epoxy ester resin of unsaturated fatty acids modification.
B. in the reactor of the above-mentioned 70g room-temperature self crosslinking epoxy ester resin being equipped with to synthesize, add 40g propyl carbinol dilution epoxy ester and stir and be warming up to 105 DEG C, under the effect of 1.7g initiator benzoyl peroxide and 0.24g chain-transfer agent n-butyl mercaptan, drip 4g methacrylic acid, 6.7g vinylbenzene, 2.3g methyl methacrylate and 1.5g methyl propenoic acid glycidyl ether and 15.5gN-n-methylolacrylamide (dissolving with 30g butyl glycol ether), 115 DEG C of insulation 1h are being warming up to again after dripping in 2h, add residue 0.86g initiator (dissolving with 10g propylene glycol monomethyl ether) again, continue insulation 2h, finally be warming up to 125 DEG C of insulation reaction 1h again, the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature that solid content is 55% can be obtained.
C. be in the multiple self-cross-linking epoxy acrylic acid resin of one component room temperature of 55% at 60g solid content, add 1.9g neutralizing agent 2 ?An Ji ?1 ?propyl alcohol and 4g deionized water, 500r/min dispersed with stirring 30min, can obtain the multiple self-cross-linking epoxy acrylic acid resin emulsion of one component room temperature that solid content is 30%.
This emulsion is light yellow transparent liquid, and smell is little, and emulsion particle diameter is 80nm, and viscosity is 290mPa.s, and acid number is 22.5mgKOH/g.After spraying to steel surface, room temperature condition lower five days drying and forming-films, film is smooth, has excellent glossiness, and in 40 DEG C of boiling water, soak seven days without any whiting, salt spray resistance can reach more than 200h.
For above-described embodiment, detect according to coating industry national standard each embodiment products obtained therefrom, detected result is as shown in table 1.The detected result of table 1 and the basic test data of product, compare with water-borne coatings existing on market, describe product nontoxic pollution-free of the present invention, emulsion particle diameter is little, stability in storage good, brushing performance is good, paint film flat smooth, glossiness are high, keep again the strong adhesion of solvent epoxy varnish etching ground, water-tolerant, the excellent properties such as corrosion-resistant and wear-resisting simultaneously.
The multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature that table 1 three kinds of embodiments obtain and coating property thereof
Claims (7)
1. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature, is characterized in that comprising the following steps:
The synthesis of the first step unsaturated fatty acids modified epoxy ester resin
In mass fraction, be raw material by 40 ~ 50 parts of bisphenol A type epoxy resins and 50 ~ 60 parts of unsaturated fatty acidss, pass into nitrogen protection under the effect of 0.5 ~ 2 part of catalyzer, esterification is carried out when 120 ~ 150 DEG C, after the massfraction being reacted to unsaturated fatty acids drops to 60 ~ 70%, be warming up to 190 ~ 210 DEG C again, reacting to system acid number lower than 5mgKOH/100g is terminal, obtained room-temperature self crosslinking epoxy ester resin; Described catalyzer is one or more in tetrabutyl titanate, Mono-n-butyltin, triphenylphosphine and Tetrabutyl amonium bromide;
The synthesis of the multiple self-crosslinking aqueous epoxy acrylic resin of second step one component room temperature
Added by solubility promoter in room-temperature self crosslinking epoxy ester resin, by percentage to the quality, controlling room temperature self-cross-linking epoxy ester resin solid content is 45 ~ 60%; Under passing into nitrogen protection condition, in mass fraction, by 1 ~ 3 part of initiator, 22 ~ 45 parts there is hydrophilic radical monomer, 8 ~ 15 parts of self-crosslinking function monomers and 0.21 ~ 0.56 part of chain-transfer agent, at 100 ~ 110 DEG C, be added drop-wise in 1 ~ 3h in room-temperature self crosslinking epoxy ester resin and carry out free radical grafting copolymerization reaction, after insulation 0.5 ~ 1.5h, to add after 0.5 ~ 1 part of initiator insulation reaction 2 ~ 4h again, finally insulation reaction 1 ~ 3h after being warming up to 115 ~ 125 DEG C, namely obtains the multiple self-crosslinking aqueous epoxy acrylic resin of one component room temperature;
Described have hydrophilic radical monomer be acrylic or methacrylic acid;
Described self-crosslinking function monomer be the methyl propenoic acid glycidyl ether of mass ratio 1:10 ~ 1:20 and N ?n-methylolacrylamide;
Described initiator is benzoyl peroxide;
The configuration of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the 3rd step one component room temperature
In mass fraction, by 45 ~ 60 parts of multiple self-crosslinking aqueous epoxy acrylic resins of one component room temperature, to add 40 ~ 60 DEG C time in the amine neutralizing agent of resinous acid value equivalent 70 ~ 100% and after, add 40 ~ 55 parts of deionized water dispersions again, namely obtain the dual self-crosslinking aqueous epoxy acrylic resin emulsion of single-component.
2. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature according to right 1, is characterized in that: described bisphenol A type epoxy resin be bisphenol A type epoxy resin E ?20, E ?12 or its mixture.
3. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature according to right 1, is characterized in that: described unsaturated fatty acids is one or more in dehydrated castor oleic acid, linolenic acid and eleostearic acid.
4. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature according to right 1, is characterized in that: described chain-transfer agent is the different monooctyl ester of n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, n-dodecyl mereaptan or thiohydracrylic acid.
5. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature according to right 1, is characterized in that: described solubility promoter includes but not limited to propyl carbinol, Virahol, butyl glycol ether or propylene glycol monomethyl ether.
6. the preparation method of the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of the one component room temperature according to right 1, it is characterized in that: described amine neutralizing agent include but not limited to triethylamine, N, N ?dimethylethanolamine, trolamine or 2 ?An Ji ?1 ?propyl alcohol or N ?ethyl morpholine.
7. the multiple self-crosslinking aqueous epoxy acrylic resin emulsion of one component room temperature, is characterized in that it is by preparation method described in claim 1 ?6, any one obtains.
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| CN103319665A (en) | 2013-09-25 |
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