CN102690385A - Method for polymerizing water-borne acrylate coating - Google Patents
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Abstract
The invention relates to a method for polymerizing a water-borne acrylate coating. Hard monomers, soft monomers and a metallic-ion crosslinking agent are subjected to emulsion polymerization in an initiating system to form the water-borne acrylate coating. By adding the crosslinking agent for crosslinking modification of water-borne acrylate, the water-borne acrylate coating with high water resistance, solvent resistance, acid resistance, compressive property and long storage period is obtained. The water-borne acrylate coating prepared by the method can serve as a priming coat or finishing coat material for coatings or building materials, an adhesive, a pressure-sensitive adhesive, a processing agent for paper or a finishing coat material for textiles, particularly serves as the finishing coat material for the coatings or the building materials.
Description
Technical field
The present invention relates to a kind of polymerization method of water-borne coatings, particularly improve the polymerization method of acrylic ester aquosity coating property.
Background technology
Water soluble acrylic acid lipin polymer emulsion has good weathering resistance, resistance to acids and bases, polluting proofing property, performance such as environmentally friendly, has become a kind of important coating variety.But there are defectives such as film-forming temperature is high, not high, the anti-after tackiness of the physical strength of filming is not good in pure third, phenylpropyl alcohol coating; Only through introducing function monomer, or to carry out modification through means such as core-shell emulsion polymerization and soap-free polymerizations be to satisfy increasingly high application requiring.
Therefore people have carried out a large amount of research to emulsion that can room temperature film-forming, as: US4772680 is through acetoacetyl and the normal temperature crosslinked emulsion of ketoimine reaction acquisition.US 6538062 utilizes the material and the hydrazides that contain active carbonyl to react the room temperature crosslinking curing of realizing coating.The siloxanes of EP 1210834 usefulness special constructions is hydrolyzed into the normal temperature crosslinked coating of silanol condensation prepared.Because the Si-O bond energy is big, to light, thermally-stabilised, be not subject to action of ultraviolet light, therefore with organo-siloxane as cross-linking monomer, make coating in self-vulcanizing, can improve the weathering resistance of coating, high-and low-temperature resistance property, water tolerance, performances such as hardness.Though vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three common unsaturated organosilicon oxygen alkane such as ('beta '-methoxy Ethoxysilanes) can be applied in and improve solution property in the solution polymerization; But because siloxanes facile hydrolysis; Produce a large amount of condensation prods; And making polyreaction can't carry out at aqueous phase, the application that therefore improves emulsion property with the organo-siloxane that contains unsaturated group and other an organosilane monomer direct polymerization is also seldom.JP51-146525, though JP54-3512 with the organo-siloxane that contains unsaturated group and other an organosilane monomer direct polymerization, stability of emulsion is poor, separates, condenses.CN1217360A; CN1217360A is with hydroxyl ZGK 5 protection organo-siloxane, and this method is the synthesis of hydroxy ZGK 5 at first, adds in the polymerization system again; Hydroxyl siloxanes and organo-siloxane carry out graft reaction; Be used for protecting not hydrolysis of organo-siloxane, the siloxanes after the grafting improves the performance of emulsion, complex process as linking agent.In addition, in the present emulsion polymerization technique, linking agent often adds when dripping monomer or preparatory emulsification, and partial cross-linked dose is enclosed in emulsion particle inside, to crosslinked not contribution between particle; So just reduced linking agent and be distributed in the surperficial probability of emulsion particle, not only dosage of crosslinking agent is big, and the degree of crosslinking of the film during the build-up of particles film forming reduces relatively.
CN1297616C discloses a kind of polymerization method of water-borne coatings, particularly improves the polymerization method of esters of acrylic acid water-borne coatings performance.Main technique is: hard monomer, initiator are added in the emulsifier aqueous solution that contains part initiator, hard monomer, pH value buffer reagent, react, be added drop-wise in the emulsifier aqueous solution that contains part initiator, hard monomer, pH value buffer reagent; React; Drip soft monomer and continue insulation reaction, in system, add siloxane crosslinker, remain the pH value in certain limit; So that siloxanes is formed protection; Make organo-siloxane stable existence in the emulsion that with water is medium, and when film forming, mainly be distributed in the emulsion particle surface, improve film forming degree of crosslinking; A kind of technology is simple, film properties good thereby provide, and the direct crosslinking polymerization of organo-siloxane improves the polymerization process of emulsion property.But should invention owing to directly add siloxane crosslinker in the polyreaction, though the organic solvent-resistant of filming that obtains, alkaline-resisting, acidproof, water-fast and compressive property is all fine, the shelf lives is short, has only 1 to 2 day.
Summary of the invention
Deficiency to prior art; The object of the present invention is to provide a kind of polymerization method; Said method is carried out cross-linking modified through adding linking agent to water-and acrylate; Obtain a kind of water tolerance, anti-solvent, acidproof, water-fast and compressive property is all fine, and long water soluble acrylic acid ester paint of shelf lives.
The present invention is through making metallic-ion crosslinking agent stable existence in the emulsion that with water is medium; And when film forming, mainly be distributed in the emulsion particle surface; Improve film forming degree of crosslinking; A kind of technology is simple, film properties good thereby provide, and the direct crosslinking polymerization of metallic-ion crosslinking agent improves the polymerization process of emulsion property.
Making metallic-ion crosslinking agent through the control pH value of reaction system is stable existence in the emulsion of medium at water, and in emulsion drying and forming-film process again hydrolytic condensation make film crosslinked; To the characteristics of metallic-ion crosslinking agent cross-linking system, the adding process sequence of adjustment hard monomer, soft monomer and linking agent, the film forming properties of raising coating.
In order to achieve the above object, the present invention has adopted following technical scheme:
The polymerization method of said water soluble acrylic acid ester paint through carrying out letex polymerization in the initiator system of hard monomer, soft monomer, metallic-ion crosslinking agent, obtains the water soluble acrylic acid ester paint.
Those skilled in the art can select required soft monomer and hard monomer in the acrylate paint polymerization process voluntarily according to the experience of oneself; As optimal technical scheme, hard monomer according to the invention is selected from the mixture of a kind of in TEB 3K, isobornyl methacrylate, vinylbenzene, vinyl cyanide, the SY-Monomer G or at least two kinds.Said mixture is the mixture of TEB 3K and isobornyl methacrylate for example; The mixture of vinylbenzene and vinyl cyanide; The mixture of vinyl cyanide and SY-Monomer G; The mixture of TEB 3K, vinylbenzene, vinyl cyanide, the mixture of vinylbenzene, vinyl cyanide and SY-Monomer G.
Soft monomer according to the invention is selected from the mixture of a kind of in methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, the Isooctyl acrylate monomer or at least two kinds.Said mixture is the mixture of methyl acrylate, ethyl propenoate for example; The mixture of Bing Xisuandingzhi, Isooctyl acrylate monomer; The mixture of methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, the mixture of ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer.
The emulsifying agent of said letex polymerization is that anionic emulsifier is or/and nonionic emulsifier.Mentioned emulsifier can be anionic or non-ionic type, also can be the compound use of anionic/non-ionic type, strengthens the consumption of emulsifying agent; Can make emulsion more stable; And can reduce the particle diameter of particle, but the introducing of emulsifying agent makes the wetting ability of film strengthen, water tolerance significantly descends; The consumption of said emulsifying agent accounts for 0.1 ~ 4wt% of hard monomer and soft monomer quality summation; For example 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.20wt%, 0.22wt%, 0.24wt%, 0.26wt%, 0.28wt%, 3.8wt%, 3.6wt%, 3.4wt%, 3.2wt%, 3.0wt%, 2.8wt%, preferred 0.5 ~ 3.5wt%, further preferred 1 ~ 3wt%.
Said anionic emulsifier is selected from the mixture of a kind of in sodium lauryl sulphate, X 2073, ethoxylated alkylphenol sulfuric acid amine, alkyl oxy DAADBSA disodium, the dioctyl disodium sulfosuccinate or at least two kinds.Said mixture is the mixture of sodium lauryl sulphate and sodium laurylsulfonate for example; The mixture of ethoxylated alkylphenol sulfuric acid amine and alkyl oxy DAADBSA disodium; The mixture of alkyl oxy DAADBSA disodium, dioctyl disodium sulfosuccinate; The mixture of sodium lauryl sulphate, X 2073, ethoxylated alkylphenol sulfuric acid amine, the mixture of ethoxylated alkylphenol sulfuric acid amine, alkyl oxy DAADBSA disodium, dioctyl disodium sulfosuccinate.
Said nonionic emulsifier is selected from: octylphenol ethoxylate, appoint the mixture of a kind of in basic phenol ethoxylate, the polyoxyethylene sorbitan carboxylic ester or at least two kinds.Said mixture is the mixture of octylphenol ethoxylate, a basic phenol ethoxylate for example; The mixture of appointing basic phenol ethoxylate, polyoxyethylene sorbitan carboxylic ester, the mixture of octylphenol ethoxylate, a basic phenol ethoxylate, polyoxyethylene sorbitan carboxylic ester.
Said metallic-ion crosslinking agent is selected from and contains Zn
2+, Mg
2+, Ca
2+, Al
3+In a kind of material of or at least two kinds of combinations.Said combination is Zn for example
2+, Mg
2+Combination, Ca
2+, Al
3Combination, Zn
2+, Mg
2+, Ca
2+Combination, Mg
2+, Ca
2+, Al
3+Combination.The said material that contains these metals ions can be selected wherein a kind of as linking agent, also can select at least two kinds mixture.Contain Zn in for example a kind of material
2+And Mg
2+, a kind of in addition material contains Al
3+, this kind linking agent just can be the combination of these two kinds of materials so.Those skilled in the art can select to contain the metallic-ion crosslinking agent kind of above-mentioned metals ion voluntarily, and the present invention does not limit this.The present invention is typical but unrestriced for example metal acetate for example has zinc acetate, magnesium acetate, lime acetate, aluminum acetate etc., also can select metal-complexing salt, for example NH
3With above-mentioned configuration metal ions Zn
2+, Mg
2+, Ca
2+, Al
3+Coordination salt.
The quality of said metallic-ion crosslinking agent accounts for 0.20 ~ 1wt% of hard monomer and soft monomer quality summation; For example 0.30wt%, 0.35wt%, 0.40wt%, 0.45wt%, 0.50wt%, 0.55wt%, 0.60wt%, 0.65wt%, 0.70wt%, 0.75wt%, 0.80wt%, 0.85wt%, 0.90wt%, 0.95wt%; Preferred 0.20 ~ 0.5wt%, further preferred 0.2 ~ 0.3wt%.
The initiator of said letex polymerization is selected from the mixture of a kind of of Potassium Persulphate, ammonium persulphate, sodium sulfite anhy 96, ammonium bisulfite or at least two kinds.Said mixture is the mixture of Potassium Persulphate, ammonium persulphate for example, the mixture of sodium sulfite anhy 96 and ammonium bisulfite, the mixture of ammonium persulphate and sodium sulfite anhy 96, the mixture of ammonium persulphate, sodium sulfite anhy 96, ammonium bisulfite.
Preferably, the quality of said initiator accounts for 0.1 ~ 5wt% of hard monomer and soft monomer quality, and for example 0.5,, t%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, preferred 0.5 ~ 4wt%, further preferred 1 ~ 3wt%.
As preferred version, said method comprising the steps of:
(1) hard monomer is added in the emulsifier aqueous solution that contains initiator, under 50 ~ 90 ℃, polymerization reaction time is more than the 35min, carries out letex polymerization;
(2) add soft monomer and continue insulation reaction, in system, add metallic-ion crosslinking agent, react 2h after-filtration discharging at least, obtain the water soluble acrylic acid ester paint.
Preferably, polymerization reaction time is more than the 50min described in the step (1), for example 55min, 60min, 65min, 70min, 75min, 80min, 90min, 100min, 110min, preferred 60 ~ 100min, further preferred 80min;
Preferably, need pH value to 6 ~ 8 of control reaction system in step (1) and the step (2), for example 6.2,6.4,6.6,6.8,7.0,7.2,7.4,7.6,7.8,8.0.
Preferably, through adding pH regulator agent control pH value of reaction system.
Preferably, said pH regulator agent is selected from: the mixture of a kind of in sodium hydrogencarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC or at least two kinds.Said mixture is the mixture of sodium hydrogencarbonate and disodium-hydrogen for example, the mixture of disodium-hydrogen and dihydrogen sulfate sodium, the mixture of sodium hydrogencarbonate and SODIUM PHOSPHATE, MONOBASIC, the mixture of sodium hydrogencarbonate, disodium-hydrogen, SODIUM PHOSPHATE, MONOBASIC.
Effect of the present invention: present method is directly participated in reaction as linking agent with metallic-ion crosslinking agent, and with the method that the pH value is regulated, it is stable to make that metallic-ion crosslinking agent remains, and simplifies polymerization technique, reduces cost.The reaction later stage adds the metallic-ion crosslinking agent linking agent; Linking agent has the surface of bigger Probability Distribution at emulsion particle; Make the more metals ion can hydrolytic condensation when film forming; The reticulated structure that forms has improved the degree of crosslinking of film, thereby has improved the performance and the storage periods such as water tolerance, hardness of film.Add hard monomer during reaction earlier and can guarantee that film has certain rigidity; The back adds soft monomer, can be when suitably reducing the soft monomer consumption, guarantee that emulsion can film forming in lower temperature; And make film that certain snappiness arranged; Make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
A) hard monomer is added drop-wise in the emulsifier aqueous solution that contains initiator, under 50-90 ℃, reacts; Wherein hard monomer is selected from: one or more in TEB 3K, isobornyl methacrylate, vinylbenzene, vinyl cyanide, the SY-Monomer G; Emulsifying agent can be anionic, non-ionic type, also can be the compound use of anionic/non-ionic type, and consumption is 0.1 ~ 4wt% of monomer total mass, preferred 0.5 ~ 3.5wt%, further preferred 1 ~ 3wt%.Wherein anionic emulsifier is selected from: one or more in sodium lauryl sulphate, X 2073, ethoxylated alkylphenol sulfuric acid amine, alkyl oxy DAADBSA disodium, the dioctyl disodium sulfosuccinate; Nonionic emulsifier is selected from: one or more in octylphenol ethoxylate, a basic phenol ethoxylate, the polyoxyethylene sorbitan carboxylic ester.Increase the consumption of emulsifying agent; Can make emulsion more stable, and can reduce the particle diameter of particle, but the introducing of emulsifying agent makes the wetting ability of film strengthen; Water tolerance significantly descends; The consumption of said emulsifying agent accounts for 0.1 ~ 4wt% of hard monomer and soft monomer quality summation, preferred 0.5 ~ 3.5wt%, further preferred 1 ~ 3wt%.
B) hard monomer dropwises, and reacts after at least 35 minutes, drips soft monomer and continues insulation reaction at least 1 hour; Soft monomer is selected from: one or more in methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, the Isooctyl acrylate monomer; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming.
C) in system, add metallic-ion crosslinking agent; React after 2 hours discharging at least.In the reaction, whenever surveyed a pH value, keep the pH value in 6～8 scope at a distance from 30 minutes.Wherein, said metallic-ion crosslinking agent is selected from and contains Zn
2+, Mg
2+, Ca
2+, Al
3+In a kind of compound of or at least two kinds combination; The quality of said metallic-ion crosslinking agent accounts for 0.20 ~ 1wt% of hard monomer and soft monomer quality summation, preferred 0.20 ~ 0.5wt%, further preferred 0.2 ~ 0.3wt%.
Initiator is selected from the mixture of a kind of of Potassium Persulphate, ammonium persulphate, sodium sulfite anhy 96, ammonium bisulfite or at least two kinds; The quality of said initiator accounts for 0.1 ~ 5wt% of hard monomer and soft monomer quality, preferred 0.5 ~ 4wt%, further preferred 1 ~ 3wt%.
The pH regulator agent is selected from a kind of in sodium hydrogencarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC.
Embodiment 1
A) hard monomer is added drop-wise in the emulsifier aqueous solution that contains initiator, under 50-90 ℃, reacts; Wherein hard monomer is a TEB 3K, and emulsifying agent is a sodium lauryl sulphate, and consumption is the 0.1wt% of monomer total mass;
B) hard monomer dropwises, and reacts after at least 35 minutes, drips soft monomer and continues insulation reaction at least 1 hour; Soft monomer is a methyl acrylate; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming;
C) in system, add metallic-ion crosslinking agent; React after 2 hours discharging at least.In the reaction, whenever surveyed a pH value, keep the pH value in 6～8 scope at a distance from 30 minutes.Wherein, said metallic-ion crosslinking agent is a magnesium acetate, and its quality accounts for the 0.20wt% of hard monomer and soft monomer quality summation.Initiator is a Potassium Persulphate, and its quality accounts for the 0.1wt% of hard monomer and soft monomer quality.The pH regulator agent is a sodium hydrogencarbonate.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 2
A) hard monomer is added drop-wise in the emulsifier aqueous solution that contains initiator, under 50-90 ℃, reacts; Wherein hard monomer is a vinyl cyanide, and emulsifying agent is an X 2073, and consumption is the 4wt% of monomer total mass;
B) hard monomer dropwises, and reacts after at least 35 minutes, drips soft monomer and continues insulation reaction at least 1 hour; Soft monomer is an ethyl propenoate; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming;
C) in system, add metallic-ion crosslinking agent; React after 2 hours discharging at least.In the reaction, whenever surveyed a pH value, keep the pH value in 6～8 scope at a distance from 30 minutes.Wherein, said metal ion crosslinked is a zinc acetate, and its quality accounts for the 1wt% of hard monomer and soft monomer quality summation.Initiator is an ammonium persulphate, and its quality accounts for the 5wt% of hard monomer and soft monomer quality.The pH regulator agent is a sodium hydrogencarbonate.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Embodiment 3
A) hard monomer is added drop-wise in the emulsifier aqueous solution that contains initiator, under 50-90 ℃, reacts; Wherein hard monomer is a vinyl cyanide, and emulsifying agent is an X 2073, and consumption is the 2wt% of monomer total mass;
B) hard monomer dropwises, and reacts after at least 35 minutes, drips soft monomer and continues insulation reaction at least 1 hour; Soft monomer is an ethyl propenoate; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming;
C) in system, add metallic-ion crosslinking agent; React after 2 hours discharging at least.In the reaction, whenever surveyed a pH value, keep the pH value in 6～8 scope at a distance from 30 minutes.Wherein, said metallic-ion crosslinking agent is a zinc acetate, and its quality accounts for the 0.5wt% of hard monomer and soft monomer quality summation.Initiator is an ammonium persulphate, and its quality accounts for the 3wt% of hard monomer and soft monomer quality.The pH regulator agent is a sodium hydrogencarbonate.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Comparative Examples
A) hard monomer is added drop-wise in the emulsifier aqueous solution that contains initiator, under 50-90 ℃, reacts; Wherein hard monomer is a vinyl cyanide, and emulsifying agent is an X 2073, and consumption is the 2wt% of monomer total mass;
B) hard monomer dropwises, and reacts after at least 35 minutes, drips soft monomer and continues insulation reaction at least 1 hour; Soft monomer is an ethyl propenoate; Add hard monomer during monomer dropping earlier, after add soft monomer, make in the emulsion particle hard outer soft, thereby when can guarantee to have certain degree of hardness, again can be in lower temperature film forming;
C) in system, add vinyltriethoxysilane; React after 2 hours discharging at least.In the reaction, whenever surveyed a pH value, keep the pH value in 6～8 scope at a distance from 30 minutes.Wherein, said vinyltriethoxysilane linking agent is a zinc acetate, and its quality accounts for the 0.5wt% of hard monomer and soft monomer quality summation.Initiator is an ammonium persulphate, and its quality accounts for the 3wt% of hard monomer and soft monomer quality.The pH regulator agent is a sodium hydrogencarbonate.Test this polymerization system stability, degree of crosslinking and film forming water tolerance, its result such as table 1.
Table 1 embodiment 1-3 and Comparative Examples polymerization system stability, degree of crosslinking and film forming water tolerance
Coating to obtaining in the foregoing description and the Comparative Examples has carried out the shelf lives test; The experiment proof; Relatively and siloxanes as the crosslinked water soluble acrylic acid ester paint that obtains of linking agent, the shelf lives of the crosslinked water soluble acrylic acid ester paint that obtains of metallic-ion crosslinking agent rises appreciably.
Applicant's statement, the present invention explains detailed method of the present invention through the foregoing description, but the present invention is not limited to above-mentioned detailed method, does not mean that promptly the present invention must rely on above-mentioned detailed method and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the polymerization method of a water soluble acrylic acid ester paint is characterized in that, said method obtains the water soluble acrylic acid ester paint through carrying out letex polymerization in the initiator system of hard monomer, soft monomer, metallic-ion crosslinking agent.
2. the method for claim 1 is characterized in that, said hard monomer is selected from the mixture of a kind of in TEB 3K, isobornyl methacrylate, vinylbenzene, vinyl cyanide, the SY-Monomer G or at least two kinds.
3. according to claim 1 or claim 2 method is characterized in that, said soft monomer is selected from the mixture of a kind of in methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, the Isooctyl acrylate monomer or at least two kinds.
4. like the described method of one of claim 1-3, it is characterized in that the emulsifying agent of said letex polymerization is that anionic emulsifier is or/and nonionic emulsifier.
5. like the described method of one of claim 1-4; It is characterized in that said anionic emulsifier is selected from the mixture of a kind of in sodium lauryl sulphate, X 2073, ethoxylated alkylphenol sulfuric acid amine, alkyl oxy DAADBSA disodium, the dioctyl disodium sulfosuccinate or at least two kinds.
6. like the described method of one of claim 1-5, it is characterized in that said nonionic emulsifier is selected from: octylphenol ethoxylate, appoint the mixture of a kind of in basic phenol ethoxylate, the polyoxyethylene sorbitan carboxylic ester or at least two kinds.
7. like the described method of one of claim 1-6, it is characterized in that the consumption of said emulsifying agent accounts for 0.1 ~ 4wt% of hard monomer and soft monomer quality summation, preferred 0.5 ~ 3.5wt%, further preferred 1 ~ 3wt%.
8. like the described method of one of claim 1-7, it is characterized in that said metallic-ion crosslinking agent is selected from and contains Zn
2+, Mg
2+, Ca
2+, Al
3+In a kind of compound of or at least two kinds combination;
The quality of said metallic-ion crosslinking agent accounts for 0.20 ~ 1wt% of hard monomer and soft monomer quality summation, preferred 0.20 ~ 0.5wt%, further preferred 0.2 ~ 0.3wt%.
9. like the described method of one of claim 1-8, it is characterized in that the initiator of said letex polymerization is selected from the mixture of a kind of of Potassium Persulphate, ammonium persulphate, sodium sulfite anhy 96, ammonium bisulfite or at least two kinds;
The quality of said initiator accounts for 0.1 ~ 5wt% of hard monomer and soft monomer quality, preferred 0.5 ~ 4wt%, further preferred 1 ~ 3wt%.
10. like the described method of one of claim 1-9, it is characterized in that, said method comprising the steps of:
(1) hard monomer is added in the emulsifier aqueous solution that contains initiator, under 50 ~ 90 ℃, polymerization reaction time is more than the 35min, carries out letex polymerization;
(2) add soft monomer and continue insulation reaction, in system, add metallic-ion crosslinking agent, react 2h after-filtration discharging at least, obtain the water soluble acrylic acid ester paint.
Polymerization reaction time is more than the 50min described in the step (1), preferred 60 ~ 100min, further preferred 80min;
Need pH value to 6 ~ 8 of control reaction system in step (1) and the step (2);
Through adding pH regulator agent control pH value of reaction system;
Said pH regulator agent is selected from the mixture of a kind of in sodium hydrogencarbonate, disodium-hydrogen, the SODIUM PHOSPHATE, MONOBASIC or at least two kinds.
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