CN103193924A - Phase-control film-formation styrene-acrylate painting emulsion and preparation method thereof - Google Patents

Abstract

The invention relates to a preparation method of styrene-acrylate copolymer painting emulsion for elastic painting of inner and outer walls of a building. The preparation of styrene-acrylate copolymer painting emulsion comprises the preparation method of styrene-acrylate seed emulsion and the preparation method of painting emulsion and the styrene-acrylate copolymer painting emulsion mainly comprises styrene, acrylate, silane coupling agent, emulgator, initiator, defoamer, pH adjusting agent, molecular weight regulator and water. By utilizing the strong surface effect of organic nano particles and designability of the distribution of inner and outer polymers of emulsion particles and combining the seed emulsion aggregation method and the phase-control dispersion film formation technology, the painting emulsion with high performance is produced by utilizing conventional raw materials; and the compactness, mechanical property and the outdoor aging resistance problems of a paint film can be successfully solved. The painting emulsion can be used as a film formation substance for the inner-outer wall emulsion paint of different buildings and also can be used for preparing anticorrosion metal anti-corrosive primer and varnish of wooden doors and windows.

Description

Phased film forming styrene-acrylic coating emulsion and preparation method

Technical field

The present invention relates to a kind of building inside and outside wall elastic coating is the preparation method of coating emulsion with copolymer in cinnamic acrylic ester, be specifically related to a kind of cinnamic acrylic ester type coating emulsion of phased film forming, by the coating of emulsion preparation and their preparation method, belong to the building coating field.

Background technology

Copolymer in cinnamic acrylic ester is that (be called for short: the styrene-acrylic coating emulsion) in occupation of the principal market of all kinds of building coating emulsions, 2009, all kinds of styrene-acrylic coating emulsions of China consumed nearly 700,000 tons to coating emulsion.The performance of styrene-acrylic coating emulsion and cost determination the main body of domestic construction coating quality.Nineteen ninety-five, German BASF AG has taken the lead in since the high-performance styrene-acrylic coating 296DS introducing Chinese market, and numerous domestic manufacturer begins competitively to research and develop high-performance styrene-acrylic coating emulsion.Regrettably, the styrene-acrylic coating emulsion of domestic production at present, exist always and can't solve water tolerance and color developing, equilibrium problem between pigment supporting capacity and the paint film mechanical property, the more important thing is that the weathering resistance of the styrene-acrylic coating emulsion of domestic production is poor, improve weathering resistance often with the MMA copolymerization, cause cost to increase substantially, the user is difficult to accept.Along with China's rapid development of economy, the building coating consumption is annual all to be increased progressively with 15% rate of increase, 2009, the China's Mainland consumes 3,600,000 tons of building coatings altogether, wherein consume nearly 900,000 tons of all kinds of coating emulsions, wherein high-performance styrene-acrylic coating emulsion consumes nearly 300,000 tons, and by 2011, Architectural Paint in China has broken through 4,500,000 tons, and actual building coating consumption was 4,600,000 tons in 2011.Along with the standardization of China's architectural finish, high-performance styrene-acrylic coating emulsion has begun to be widely used in the application of external wall of high-rise building, and the weathering resistance that how to improve styrene-acrylic just becomes the technical bottleneck that can restriction be used at external wall of high-rise building.Therefore develop high-end building coating emulsion and be always the eternal problem of domestic coating emulsion factory.

Chinese patent CN102372960A discloses a kind of high resistant styrene-acrylic latex coating, and it mainly is to be stirred according to weight proportion by following raw materials according to make: 157 parts of benzene emulsions, 13 parts of dispersion agents, 80 parts of deionized waters, 15 parts of adipic dihydrazide, 2 parts of dispersion agents, 4 parts of defoamers, 11 parts of mould inhibitors, 23 parts of kaolin, 15 parts of titanium dioxides, 15 parts of dicalcium powders, 15 parts of film coalescence aid, 12 parts of polyethers thickening materials.

Chinese patent CN1872888A discloses the synthetic method of the cruel emulsion of a kind of vinylbenzene for building one vinylformic acid; this copolymer emulsion is to be medium with water; be comonomer with vinylbenzene, (methyl) acrylate and (methyl) vinylformic acid; and adding emulsifying agent and initiator, to carry out emulsion polymerization synthetic; the weight percent of each moiety is: water 40～55%; vinylbenzene 18～30%; (methyl) acrylate 18～30; (methyl) vinylformic acid 0.5～3%; emulsifying agent 0.5～4%; initiator 0.1～0.5%, protection glue 0.1～0.5%.

Chinese patent CN1249111C discloses a kind of preparation method of modifying cinepazid emulsion, be to be polymerization single polymerization monomer with vinylbenzene, butyl acrylate, vinylformic acid, be modified monomer with the organic fluorine, be the emulsifying agent of system with the compound emulsifying agent, the employing thermal decomposition initiating is initiator, after with silane coupling agent organic fluorine being carried out pre-treatment, make catalyzer with the undecyl Phenylsulfonic acid, adopt the polymerization of nucleocapsid technology to obtain modifying cinepazid emulsion.

In the prior art styrene-acrylic coating emulsion is carried out many improvement, but still existed pigment volume concentration (PVC) little, poor to the pigment supporting capacity, problems such as color developing difference and anti-rainprint ability, weathering resistance is not significantly improved.

Summary of the invention

The present invention exists weather resistance poor to solve present building inside and outside wall coating with the styrene-acrylic coating emulsion always, pigment volume concentration (PVC) is little, poor to the pigment supporting capacity, problems such as color developing difference and anti-rainprint ability are purpose, tackle the styrene-acrylic coating emulsion mutually and carry out brand-new design and systematic study.Utilize the controlled emulsion polymerization technology of seed to combine with phased film technique, styrene-acrylic coating of a kind of high-performance (weather-proof, super water-fast, resistant and high color development) and preparation method thereof is provided.

Mostly conventional seeded emulsion polymerization is at strictness control emulsifying agent consumption below CMC, and need multistep monomer swell-polymerization just can finish, and initial seed is positioned at the innermost layer of emulsion particle, the emulsification dosage of adding because of per step polymerization is all below CMC, therefore size distribution is very narrow, but the particle diameter of final latex grain is all very big, general all more than 160nm, this is advantage for synthetic PVC plasticized modifier, but for the preparation coating emulsion be exactly shortcoming because the building coating particle size of emulsion is more thin, it is to the supporting capacity of pigment, adhesive property to pigment and base material is just more good, and this is because the super surface effects of the same existence of nano level organic polymer.

The present invention utilizes the particle form design of emulsion particle that seeded emulsion polymerization is combined with phased film forming mechanism, solving resistance to soiling and low temperature flexibility and be difficult to balanced problem, specifically is composition and the hydrophilic size thereof that adopts the shell polymkeric substance of the strict final particle size of emulsion of control of the seed law and final emulsion emulsion particle.The related seed emulsion particle diameter of the present invention is little, narrow distribution, and moderate wetting ability is arranged, the monomer that can guarantee follow-up dropping polymerization all carries out polymerization in the inside of each emulsion particle of seed emulsion, the very big absorption merit of bringing because of the super surface effects of these superfine particles, all follow-up monomers are carried out increase-volume with the function in black hole, polymerization, therefore the shell polymkeric substance is not the polymkeric substance that forms of follow-up monomer but seed polymer, and when emulsion solid content is higher, the shell polymkeric substance begins to break, flexible polymer, and then improves the color developing of coating and reduces the film-forming temperature of coating on the top layer of final latex grain with fragment or size distribution.

For realizing purpose of the present invention, according to a first aspect of the invention, provide seed emulsion of a kind of cinnamic acrylic ester type coating and preparation method thereof.According to a second aspect of the invention, provide cinnamic acrylic ester type emulsion and preparation method thereof.

Technical scheme of the present invention is summarized as follows:

1. cinnamic acrylic ester type seed emulsion, this emulsion is by the vinylbenzene as monomer component, butyl acrylate, methyl methacrylate and ethyl propenoate, in the presence of the reactive emulsifier that contains olefinic double bond (or containing carbon-to-carbon double bond) and anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate and water, undertaken by adding water-soluble radical initiator that emulsion polymerization prepares, wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), the ratio (by weight) of butyl acrylate (BA) is St:MMA:EA:BA=(7～25): (15～40): (10～30): (20～70 or 20～60), preferably (8～20): (25～35): (12～27): (30～40) are more preferably (8～20): (25～30): (15～25): (30～35).

Preferably, the consumption of anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate is 2～12wt% of monomer total amount, preferred 3～9wt%, more preferably 3.2～8wt%, further preferred 3.5～7wt%, more preferably 4～6wt%, for example 5wt%.Preferably, the consumption of reactive emulsifier is the 2-～2wt% of monomer total amount, preferred 3～9wt%, more preferably 3.2～8wt%, further preferred 3.5～7wt%, more preferably 4～6wt%, for example 5wt%.

Preferably, the consumption of radical initiator is 0.4～2.0wt% of monomer total amount, preferred 0.45～1.5wt%, preferred 0.45～1.0wt%, more preferably 0.5-0.9wt%, further preferred 0.55-0.85wt%, more preferably 0.6-0.8wt%, for example 0.7wt%.

Preferably, all monomers are 28～50:50～72 with the ratio (by wt) of the relative consumption of deionized water (DW), preferred 30～40:60～70, and more preferably 32～37:63～68, wherein the weight sum of whole monomers and deionized water (DW) is 100 weight parts.

2. according to above 1 seed emulsion, wherein the Hunk constant (Hansch) of the polymkeric substance in the seed emulsion is 2.25～3.10, is preferably 2.30～3.00; Preferred 2.35～2.90, be preferably 2.35～2.55 or 2.55～2.8; And/or this polymkeric substance has 5.0～10.0 ℃, preferred 5.5～9.5 ℃ or 6.0～9.0 ℃, and the second-order transition temperature (Tg) of 6.5～8.5 ℃ or 7.0～8.0 ℃ more preferably.Wherein Hunk (Hansch) constant has reflected the amphipathic property size according to me that forms behind the monomer polymerization.

3. according to above 1 or 2 described seed emulsion, it is characterized in that the solid content of described seed emulsion at 20-60wt%, preferably between 25-58wt%, more preferably between the 30-56wt%, more preferably between the 35-45wt%, preferably between 40-53wt%, more preferably between 48～51wt%.More preferably, solid content also can be at 30-40wt%, preferably between 33-37wt%, and for example 35wt% or 36wt%.

4. according to any one seed emulsion in above 1～3, it is characterized in that: reactive emulsifier (or being called response type surfactant active) be selected from following in these one or both or multiple: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy polyethylene glycol methacrylate-styrene polymer (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

The above initiator is for example inorganic peracid salt initiators or organic peroxide evocating agent of radical initiator, oxidation-reduction trigger system.Preferably the inorganic peracid salt initiators is more preferably persulphate, in initiator system of ammonium persulfate, Potassium Persulphate, the Sodium Persulfate any one or two or more.

5. according to any one seed emulsion in above 1～4, it is characterized in that: also comprise neutralizing agent in the described seed emulsion.Described neutralizing agent is a kind of in ammoniacal liquor or the alkyl alcohol ammonia; Preferably ammoniacal liquor, for example ammoniacal liquor of 25-28wt% concentration.

Further preferably, in seed emulsion, contain based on total reaction mixture weight 0.5～4%, preferred 1～3%, the neutralizing agent of 1.5-2wt% (as the ammoniacal liquor of 25-28wt% concentration).

6. according to any one seed emulsion among the above 1-5, it is characterized in that: also comprise sanitas and/or defoamer in the described seed emulsion.

Described sanitas is one or more in Sodium Benzoate, daconil M, the aminopropanol compound, preferably BIT-20 (1,2-benzisothiazole-3-ketone, U.S. Sol company); Further preferably, in seed emulsion, contain based on total reaction mixture weight 0～0.2% preferred 0.05～0.1% sanitas;

Described defoamer is silicone antifoam agent or fluorine modified siloxane defoamer, preferably one or more in water-based silicone oil, the silicone emulsion; Further WBA defoamer (U.S. Kening Co.,Ltd) preferably; Further preferably, in seed emulsion, contain based on total reaction mixture weight 0～0.2% preferred 0.05～0.1% defoamer.

7. according to any one seed emulsion in above 1～6, it is characterized in that: the number average bead diameter of described seed emulsion is 25～40nm, preferred 27～38nm, or 30～35nm, further preferred 31～34nm, or 32～33nm, and/or, the size distribution index is more preferably less than 0.10 less than 0.12

8. according to any one seed emulsion in above 1～7, it is characterized in that: the minimum film-forming temperature of described seed emulsion (MFT) is 4～12 ℃, preferred 5～10 ℃, and for example 6,7,8,9 ℃.

9. prepare the method for the seed emulsion of any one in above 1～8, this method may further comprise the steps:

(1) pre-emulsification: with 25～37 weight parts (preferred 27-35, more preferably 28-32) deionized water, 2～10 weight parts (preferred 3-8, preferred 4～6 or 4.5～5.0) anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), 2～10 weight parts (preferred 3-8, preferred 4～6 or 5.0～-5.5 weight parts) after the reactive emulsifier that contains olefinic double bond (or containing carbon-to-carbon double bond) stirs for some time (for example 10～20 minutes), drip 90-110 weight part (preferred 95～105 weight parts) by vinylbenzene, methyl methacrylate, the monomer mixture that ethyl propenoate and butyl acrylate are formed, continue high-speed stirring emulsification (for example 0.5-1.5 hour), obtain pre-emulsion; The ratio (by weight) of wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), butyl acrylate (BA) is St:MMA:EA:BA=(7～25): (15～40): (10～30): (20～70 or 20～60), preferably (8～20): (25～35): (12～27): (30～40) are more preferably (8～20): (25～30): (15～25): (30～35);

(2) polymerization: with 70～95 weight parts (preferred 75～90 weight parts, for example 80,85 weight parts) deionized water, 0.7～3 weight parts (preferred 0.8-2 weight part, 1.5 weight parts for example) rebasing anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), under agitation condition, be warming up to 70～95 ℃ (preferred 80～88 ℃, preferred 82～86 ℃, or 84～85 ℃), (for example keep 1-10 minute, treat that temperature dashes to the highest and stable several minutes, for example 1～4 minute, or after 2～3 minutes), drip pre-emulsion and the initiator solution (deionized water of the initiator of 0.20-0.50 weight part+2-5 weight part) of step (1) gained, temperature of reaction control is at 80～92 ℃ (preferred 83～90 ℃, preferred 86～88 ℃) during dropping, total dropping time control was 60～130 minutes (preferred 80～110 minutes, preferred 90～100 minutes); Drip and finish 40～80 minutes (preferred 50～70 minutes, for example 60 minutes) of insulation, back;

(3) step 2 gained emulsion is cooled to 15-40 ℃ (preferred 20～35 ℃), add 1-6 weight part (preferred 2-5, more preferably 3-4) anionic emulsifier sodium lauryl sulphate (SDS) or Sodium dodecylbenzene sulfonate (SDBS), randomly add the sanitas of 0 weight part or 0.01-0.3 weight part (for example 0.1-0.2 weight part) and/or the defoamer of 0 weight part or 0.01-0.3 weight part (for example 0.1-0.2 weight part), neutralizing agent (for example ammoniacal liquor) neutralization (for example to pH value 8.0～8.50) of final reaction mixture, filter then, obtain seed emulsion.

In addition, according to above the 9th method, the preferred embodiment of this method is identical with the defined condition of above preferred embodiment for seed emulsion.

10. by any one the prepared seed emulsion of method among the above 1-10, wherein the Hunk constant (Hansch) of the polymkeric substance in the seed emulsion is 2.25-3.10, is preferably 2.30-3.00; Preferred 2.35-2.90 is preferably 2.35-2.55 or 2.55-2.8; And/or this polymkeric substance has 5.0～10.0 ℃, preferred 5.5～9.5 ℃ or 6.0～9.0 ℃, and the second-order transition temperature (Tg) of 6.5～8.5 ℃ or 7.0～8.0 ℃ more preferably.

Preferably, more than the number average bead diameter of 10 described seed emulsion be 28～40nm, preferred 29～38nm, or 30～36nm, further preferred 31～34nm, or 32～33nm, and/or size distribution index (PDI) is more preferably less than 0.10 less than 0.12,

11. the method for preparation (phased film forming) copolymer in cinnamic acrylic ester type coating emulsion (being called for short the styrene-acrylic coating emulsion), this method may further comprise the steps:

(1) pre-emulsification: add 14～37 weight parts (preferred 15～34 weight parts, preferred 16～32 weight parts, more preferably 18～28 weight parts in the pre-emulsification still, 24,26 weight parts for example) deionized water is under whipped state, add 0.2～1.5 weight part (preferred 0.3～1.2 weight part, more preferably 0.4～1.1 weight part, for example 0.5,0.6,0.7,0.8,0.9,1.0 weight part) the non-reactive emulsifier [C of the terminal hydroxy group sulfonation of 0.1～0.8 weight part (preferred 0.2～0.6 weight part) for example ₅-C ₁₀Alkyl alcohol Soxylat A 25-7 type emulsifying agent, as the alkyl alcohol Soxylat A 25-7 (EO:15～20) of terminal hydroxy group sulfonation (hereinafter to be referred as emulsifying agent B or mixed emulsifier B, Shanghai official loyal to his sovereign Fine Chemical Co., Ltd), and/or the siliceous emulsifying agent of 0.1～0.6 weight part (preferred 0.2～0.5 weight part) is (as S-240, Germany's Degussa)] with 0.2～1.2 weight part (preferred 0.4～1.0 weight part) contain the olefinic double bond reactive emulsifier of (or containing carbon-to-carbon double bond), through after a while after (for example 10～30 minutes), drip 100 weight parts by vinylbenzene (St), butyl acrylate (BA), vinylformic acid (AA), acrylamide (AM), the monomer mixture that 2-EHA (EHA) and cross-linking monomer are formed, high-speed stirring emulsification for some time (for example 45～75 minutes, as 1 hour);

Wherein the relative consumption (based on total monomer weight) of various monomers is:

Vinylbenzene (St) 52～72%, preferred 54～68%, more preferably 55～66%;

Butyl acrylate (BA) 10～24%, preferred 11～20%, more preferably 11.4～18%;

Vinylformic acid (AA) 1.2～5%, preferred 1.5～4.5%, 2.5～4%;

Acrylamide (AM) 1.2～5%, preferred 1.5～4.5%, preferred 2.5～4%;

2-EHA (EHA) 12～22%, preferred 13～18%, more preferably 14～17%;

Cross-linking monomer 0.5～1.2%, preferred 0.6～1.0%, more preferably 0.7～0.9%;

Perhaps, the relative consumption of various monomers (wherein the consumption sum of various monomers is 100 weight parts) is:

Vinylbenzene (St) 52～72 weight parts, preferred 54～68 weight parts, more preferably 55～66 weight parts;

Butyl acrylate (BA) 10～24 weight parts, preferred 11～20 weight parts, more preferably 11.4～18 weight parts;

Vinylformic acid (AA) 1.2～5 weight parts, preferred 1.5～4.5 weight parts, 2.5～4 weight parts;

Acrylamide (AM) 1.2～5 weight parts, preferred 1.5～4.5 weight parts, preferred 2.5～4 weight parts;

2-EHA (EHA) 12～22 weight parts, preferred 13～18 weight parts, more preferably 14～17 weight parts;

Cross-linking monomer 0.5～1.5 weight part, preferred 0.6～1.2 weight part, more preferably 0.7～1.0 weight part;

(2) polymerization: the deionized water that adds 20～35 weight parts (preferred 25～30 weight parts) in the polymerization reactor, buffer reagent (as the hydrophosphate buffer reagent) with interpolation 0 or 0.1-0.3 weight part, stir, be warming up to 70-93 ℃ (preferred 84～92 ℃, preferred 86～90 ℃), add 5～32 weight parts (preferred 7-28 weight part, preferred 10-25 weight part, preferred 12-22 weight part, as 13,14,15,16,18,20 weight parts) any one described seed emulsion or above 10 seed emulsion in above 1～8, under the temperature of 85-90 ℃ (87～89 ℃), add rebasing initiator solution (for example persulphate such as the APS of the deionized water of 2-5 weight part+0.1-0.5 weight part) then, after for some time (for example 3～8 minutes), begin to drip step (1) gained pre-emulsion and initiator solution (for example persulphate such as the APS of the deionized water of 5-6 weight part+0.3-0.8 weight part), the dropping time, control was 150～300 minutes (preferred 180～250 minutes), dropping temperature control is at 76～89 ℃ (preferred 80～88 ℃), drip and finish 45～75 minutes (preferred 50～70 minutes) of insulation, back, cool to 62～72 ℃ (preferred 66～70 ℃) again, add neutralizing agent (for example ammoniacal liquor);

(3) eliminate the back: under 60-70 ℃ (preferred 65～67 ℃), initiator A is eliminated in a kind of back that adds the 0.2-0.5 weight part in step (2) the gained emulsion, 5～15 minutes (for example 10 minutes) back drips a kind of back of 0.2-0.5 weight part and eliminates initiator B, the dropping time was controlled at 15～45 minutes, and preferred 20～40 minutes, for example 30 minutes, carry out the insulation second time after dropwising, soaking time is 30 minutes-3 hours (preferred 45～75 minutes, preferred 50～70 minutes, for example 60 minutes);

Wherein, the back elimination initiator A of described 0.2～0.5 weight part organic hydroperoxide (as the tertbutyl peroxide) aqueous solution that is 0.2～0.5 weight part (as the organic hydroperoxide (as tertbutyl peroxide) of deionized water+0.1～0.2 weight part of 0.1～0.3 weight part); The back elimination initiator B of described 0.2～0.5 weight part is the aqueous solution (as the reductive agent (as sodium formaldehyde sulphoxylate and/or sodium bisulfite) of the deionized water+0.1-0.3 weight part of 0.1～0.2 weight part) of reductive agent (as sodium formaldehyde sulphoxylate and/or sodium bisulfite);

(4) be cooled to 15～40 ℃ (preferred 20～35 ℃) after insulation finishes for the second time, emulsifying agent (the QM-1580 for example that adds 0.2～0.5 weight part, the loyal Fine Chemical Co., Ltd in Shanghai, LCN407, Germany gram Lay benefactor department), add optional (0 or 0.2～0.4 weight part) neutralizing agent (for example ammoniacal liquor), (0 or 0.2～0.4 weight part) defoamer, (0 or 0.2～0.4 weight part) sanitas (as BIT-20) after stirring for some time (for example 15～30 minutes), continue to stir 45～75 minutes (preferred 50～70 minutes, for example 60 minutes) again;

(5) filter (for example using 500 mesh filter screens) at last, making phased film forming copolymer in cinnamic acrylic ester is coating emulsion.

Above-described " non-reactive emulsifier " generally is the emulsifying agent that contains sodium group such as the emulsifying agent B that contains polyoxyethylene segment (PEO), and/or the emulsifying agent (being called for short siliceous emulsifying agent) that contains the polysiloxane segment is as siliceous emulsifying agent S-240 (Dow corning company).The surface tension of siliceous emulsifying agent generally is between 2～20 dyne, preferably between 5～18 dyne.

12. be the method for coating emulsion (be called for short styrene-acrylic coating emulsion) according to the phased film forming copolymer in cinnamic acrylic ester of above 11 described preparations, wherein said cross-linking monomer is vinyl three (C ₁-C ₃Alkoxyl group) silane, preferably A151 (being vinyltriethoxysilane).

13. according to above 11 or 12 described methods, wherein in the pre-emulsion that in step (1), forms or in step (2) in the dropping pre-emulsion or afterwards, also drip the molecular weight regulator of 0.5～8 weight part (preferred 1～7, more preferably 2～6).This conditioning agent is TEXNOL (containing ester group and two secondary hydroxyls, Yi Shi Man) and/or vinylchlorid (VC) preferably.The vinylchlorid of the TEXNOL of 1～2 weight part and/or 1.5～2.5 weight parts for example.Because the saturation vapour pressure of vinylchlorid is higher, is generally 6kg/cm ², if consumption, can directly be absorbed in the styrene monomer after a little while.If consumption is big, then use the polymerization reactor of pressurization, for example autoclave.

14. according to any one described method in above 11～13, wherein reactive emulsifier (or being called response type surfactant active) be selected from following in these one or both or multiple: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

15, according to any one described method among the above 11-14, wherein reactive emulsifier (or being called response type surfactant active) is to be selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or a kind of and a kind of binding substances that is selected among NRS-10 or the SE-10N in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Be more preferably a kind of and a kind of binding substances that is selected among NRS-10 or the SE-10N that is selected from 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

16. according to any one described method for preparing cinnamic acrylic ester type coating emulsion in above 11～15, wherein the reactive emulsifier that contains olefinic double bond (or containing carbon-to-carbon double bond) of 0.2～1.2 weight part (preferred 0.4～1.0) comprises for example NRS-10 or the SE-10N of 0.1～0.6 weight part (preferred 0.2～0.5), with 0.1～0.6 weight part (preferred 0.2～0.5) be selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or a kind of in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS)].

More preferably, the reactive emulsifier that contains olefinic double bond (or containing carbon-to-carbon double bond) of 0.2～1.2 weight part (preferred 0.4～1.0) comprises a kind of among NRS-10 or the SE-10N of being selected from who is selected from a kind of and 0.1～0.6 weight part (preferred 0.2～0.5) in 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3) of 0.1～0.6 weight part (preferred 0.2～0.5) for example.

In the above method for preparing cinnamic acrylic ester type coating emulsion, sanitas is Alex251 or BIT-20 preferably; Further preferably, in the styrene-acrylic coating emulsion, contain (or interpolation) based on total reaction mixture weight 0～0.2%, preferred 0.01～0.1% sanitas.Described defoamer is silicone antifoam agent or fluorine modified siloxane defoamer, preferably one or more in water-based silicone oil, the silicone emulsion; Further one or more in DF60 defoamer, Tego902W defoamer, the WBA defoamer (U.S. Kening Co.,Ltd) preferably; Further preferably, in cinnamic acrylic ester type coating emulsion, contain (or interpolation) based on total reaction mixture weight 0～5 ‰, preferred 1～4 ‰ defoamer.

17. the phased film forming copolymer in cinnamic acrylic ester by any described method preparation in above 11～16 is coating emulsion (being called for short the styrene-acrylic coating emulsion), the solid content of wherein said cinnamic acrylic ester type coating emulsion is between 35-60wt%, preferably between 40-55wt%, more preferably between 42～51wt%.

18. according to above 17 described coating emulsions, the number average particle size of particle is between 70～90nm in the wherein said cinnamic acrylic ester type coating emulsion, preferred 75～88nm, or between 80～86nm.The second-order transition temperature (Tg) of the polymkeric substance of this cinnamic acrylic ester type coating emulsion is 25～30 ℃, preferred 26～28 ℃.

19, cinnamic acrylic ester type coating is characterized in that: described cinnamic acrylic ester type coating comprises following component:

More than 17 or 18 described cinnamic acrylic ester type coating emulsion 100-400 weight parts, preferred 150-350, more preferably 200-300 weight part;

Filler 250-600 weight part, preferred 300-550 weight part, preferred 330-500 weight part, 350-450 weight part;

Pigment 0 or 0.5-150 weight part, preferred 10-130 weight part, more preferably 30-110 weight part, more preferably 50-100 weight;

Pigment dispersing agent 0 or 0.1-8 weight part, preferred 1-6 weight part;

Pigment wetting agent 0 or 0.05-2 weight part, preferred 0.1-1.5 weight part;

Defoamer 0 or 0.02-0.50 weight part, the 0.05-0.30 weight part;

Thickening material 0 or 1-5 weight part, preferred 1.5-4 weight part;

PH regulator agent 0 or 1-10 weight part, preferred 2-8 weight part, preferred 3-7 weight part;

Film coalescence aid 0 or 1-10 weight part, preferred 2-8 weight part, preferred 3-7 weight part;

Sanitas 0 or 0.1-3 weight part, preferred 0.5-2 weight part, preferred 0.8-1.5 weight part;

Mould inhibitor 0 or 0.1-3 weight part, preferred 0.5-2 weight part, preferred 0.8-1.5 weight part;

Water 160-400 weight part, preferred 200-350 weight part, more preferably 250-300 weight part.

20. according to above 19 coating, wherein said pigment be in titanium dioxide, ferric oxide, carbon black, toner pigment slurry or the organic synthesis pigment one or both or multiple; Filler be in calcium carbonate, talcum powder, kaolin, the wollastonite powder one or both or multiple.

Described pigment dispersing agent is preferably polycarboxylate sodium's type dispersion agent, preferred SN-5040 (Japanese Nuo Puke chemical industry company limited);

Described pigment wetting agent is preferably PE-100 (Shenzhen Hai Chuan chemical industry company limited), and/or AF-10 (Dow Chemical);

Described defoamer be in liquid metal soap defoamer, silica anhydride defoamer, the non-silicon defoaming agent any one or two or more, preferably among the defoamer NXZ (Japanese Nuo Puke chemical industry company limited), SN-DEFOAMER345, DH-X2205 (Foshan Supreme Being converge company) any one or two or more;

Described thickening material is preferably thickening material TT935 (U.S. Rhom and Hass) and/or ASE-60 (U.S. Rhom and Hass);

Described pH regulator agent is preferably AMP-95 (2-amino-2-methyl-1-propanol, Dow Chemical).

Film coalescence aid is preferably TEXNOL.

21. the method for above 19 or 20 the described cinnamic acrylic ester type coating of preparation, this method comprises the steps:

(1) in having the dispersing apparatus of whipping device (as disperseing cylinder), add water, open and stir, add wetting agent, dispersion agent, pH regulator agent, after the stirring and dissolving, rotating speed (for example carrying to 1500～1800 rev/mins) back of improving whipping device adds filler and disperses (jitter time is 30～50 minutes) with optional pigment;

(2) slurry after will disperseing grinds, and fineness (mean particle size) reaches below 20 microns or 20 microns;

(3) under low speed (for example 500～800 rev/mins) agitation condition, above 17 or 18 described cinnamic acrylic ester type coating emulsions, defoamer, thickening material, pH regulator agent, optional film coalescence aid, sanitas, mould inhibitor are dropped in the dispersing apparatus, mixing and stirring is filtered and is made described cinnamic acrylic ester type coating.

22. above 19 or 20 described cinnamic acrylic ester type coating are used for all kinds of building inside and outside wall emulsion paints of preparation, anti-corrosion of metal priming paint, the purposes of the varnish of woodenware door and window.

" choosing " expression in this application wantonly is with or without.

The wetting ability size of the particle diameter of seed emulsion and distribution thereof, seed polymer and soft or hard final decision:

(1) determine the polymerization place of follow-up monomer and have follow-up monomer to form the position of polymkeric substance, the particle diameter of seed emulsion is more little, and lipophilicity is more strong, and the polymerization probability of follow-up monomer in each emulsion particle of seed emulsion increases; Seeding polymerization is more soft, and final emulsion is more good to the compactness of the cohesive force of ground and film, and film-forming temperature is more low, and the film coalescence aid add-on is more little, and VOC content is more low;

(2) lipophilicity of seeded emulsion polymerization thing is too strong, causes final latex grain outermost layer polymkeric substance wetting ability to descend, and causes the decline to pigment and base material wetting ability, thereby causes emulsion to the supporting capacity decline of pigment and the decline of color developing;

(3) lipophilicity of seeded emulsion polymerization thing is too strong, also can cause back thickening phenomenon occurring after adding associative thickener, causes the rheology index of coating to improve, and levelling property descends;

(4) lipophilicity of seeded emulsion polymerization thing is too strong, also can cause the rate of drying heterogeneity of paint film, finally causes the compactness of paint film to descend, and causes water resistance to descend.Thereby the water pollution capacity that bears dirty descends.

Hansch (Hunk) constant value of monomer commonly used is as shown in table 1 below:

The Hunk constant (Hansch) of table 1 monomer commonly used

Therefore, consider from Hunk constant value and the second-order transition temperature value of polymkeric substance that the present invention adopts vinylbenzene (St), butyl acrylate (BA), methyl methacrylate (MMA), ethyl propenoate (EA) as the comonomer component for preparing seed emulsion.

For coating emulsion, select the rule of emulsifying agent to be, guaranteeing polymerization stability, stability in storage, under the prerequisite of salt stability, the emulsifying agent consumption is as far as possible little, therefore selects compatibilization effect good as far as possible, the emulsifying agent that micelle-forming concentration (CMC) value is little.The superfine particle diameter of seed emulsion has determined all emulsifying agents that maximum compatibilization effect must be arranged, and has only sodium lauryl sulphate (SDS) and Sodium dodecylbenzene sulfonate (SDBS) to have this feature at present.Because the water tolerance of SDBS is better, therefore preferred SDBS and reactive emulsifier are composite as polymeric emulsifiers.

In the emulsion film forming process, the hydrophilic small molecules material all can to the coating surface diffusion, be enriched in together under effect capillaceous with final minor amount of water then in the later stage of drying process.Therefore the consumption of emulsifying agent is very important to the water tolerance of paint film.Along with the increase of emulsifying agent consumption, the polymerization stability of the monomer compatibility that wetting ability is big decreases.This is that hydrophilic monomer increases to micella internal divergence resistance because emulsification dosage increases, and the outer field hydration layer of emulsion particle thickens, due to water nucleation probability increases; And along with the SDBS consumption increases, micellar concentration increases, and increases but increase to the free emulsification dosage in a certain amount of back, the chance that causes new emulsion particle to generate increases, along with the increase of reactive emulsifier consumption, the homogeneous nucleation probability increases, and the probability that generates new emulsion particle is also increasing.

Described initiator can be inorganic radical initiator (for example Potassium Persulphate, Sodium Persulfate or ammonium persulphate) or organic oxidation-reduction initiator (for example organo-peroxide (as tert-butyl peroxide)-organic reducing agent (as vitamins C)) or inorganic oxide-reduction initiator.Also can be the combination of dissimilar two kinds of initiators, for example combination of inorganic radical initiator and organic oxidation-reduction initiator.The preferred inorganic radical initiator of the present invention, further preferred persulphate, more preferably one or more in ammonium persulphate (APS), Potassium Persulphate, the Sodium Persulfate.

Preferably, described cross-linking monomer is vinylsiloxane, and with the increase of its consumption, the breaking tenacity of paint film increases, and extension at break reduces, and the contamination resistance of paint film all is trend of rising always.Described vinylsiloxane can be one or more among A151, A171, the A-174, preferably A151.

The polymerization stability of emulsion, mechanical stability and salt stability reduce gradually with the increase of amount ofthe cross-linking monomer, and the scrubbing resistance ability of paint film, anti-contamination ability increase with its increase.The consumption of cross-linking monomer has a significant impact the color developing that improves coating.This be because, before film forming, the siloxane bond of A151 is not opened, the molecular weight of basic polymkeric substance and gel content are irrelevant with amount ofthe cross-linking monomer, but begin crosslinking curing after the film forming, the high silicon hydroxyl of activity can with base material, pigment particles, react between the polymkeric substance, not only increased the sticking power to base material, the water tolerance of gaseous state paint film, contamination resistance, and improved the color developing of paint film.

Described reactive emulsifier, can further improve emulsion polymer itself to the wettability of pigment and the water tolerance of paint film, the present invention is any one among any one in allyloxy hydroxypropyl sodium sulfonate (COPS-1), the allyloxy hydroxypropyl sodium phosphate salt (COPS-3) and NRS-10 or the SE-10N most preferably.

Reactive emulsifier NRS-10 chemical constitution is for containing allylic extraordinary ether alcohol sulfate, and soap-free polymerization and the consumption of the control emulsion preferably of its polymerization activity seldom just play water-fast effect.The NRS-10 that the loyal Fine Chemical Co., Ltd in preferred Shanghai produces, more environmental protection of the NRS-10 of its more Japanese ADK chemical production.

The emulsifying agent of described styrene-acrylic emulsion is emulsifying agent B and reactive emulsifier compound preferably.When the emulsifying agent total amount is identical, improve with the salt stability of the increase emulsion of emulsifying agent B ratio, it is big that particle diameter becomes.This is because emulsifying agent B has than NRS-10 or the longer Soxylat A 25-7 segment of SE-10N; It is big that particle diameter becomes, and is that the hydration bed thickness of formation is due to the particle diameter that light scattering method is measured is higher because of Soxylat A 25-7 chain segment length.And, the scrub resistance of paint film, the color developing of coating all can improve along with the raising of reactive emulsifier consumption, this be because reactive emulsifier finally on main polymer chain, reduced the interfacial effect of emulsifying agent and base material, reduced the phenomenon that is rushed to of emulsifying agent simultaneously, so far the initial whiting time of paint film postpones, and the wet sticking power of paint film improves; But the polymerization activity base of reactive emulsifier is allylic structure, exist active low always, be not suitable for the copolymerization of high-content, active high styrene monomer especially, therefore after the reactive emulsifier amount is increased to a certain degree, because activity is low, the chance of homopolymerization increases, and not only polymerization stability descends, and the water-fast whiting of paint film, water-proof all can descend.Therefore reactive emulsifier should be noted the control of consumption in styrene-acrylic coating emulsion prescription.

SIPPMER COPS-1 is present the most classical non-oil-in-water type reactive emulsifier in the world, the letex polymerization that is used for acrylate can improve the mechanical stability of emulsion greatly, emulsion is to supporting capacity and the color developing of paint film and the water tolerance of paint film of pigment, but the price of Yin Qigao, it is its bottleneck that uses at coating emulsion of restriction always, at present this product domesticizes, and quality reaches the level of Luo Diya substantially, and price is half of imported product.COPS-3 also is the another kind of non-oil-in-water type reactive emulsifier of at first being developed by Rhodia, its chemical name is for being allyloxy hydroxyl sodium phosphate, the difference of the two is the difference of phosphorus and sulphur, but the coordination ability of phosphorus atom is stronger, easier and pigment particles forms chelate bond, and linkage force is bigger, should be stronger to the sticking power aspect that improves with base material.When utilizing described styrene-acrylic emulsion preparation coating, along with the increase of non-oil-in-water type reactive emulsifier consumption, the saturated water absorption of paint film increases, and the initial whiting time is normal distribution trend, and wet sticking power increases, and the scrubbing resistance ability increases; This is because along with the increase of non-oil-in-water type reactive emulsifier consumption, drying varniss speed reaches unanimity, due to the compactness of paint film increases.Wet sticking power increase is because the powerful sequestering action of sulfonic group or phosphate has improved the dispersing of pigments wetting ability, has improved due to the binding ability of base material.Be that the non-oil-in-water type reactive emulsifier of hydrophilic group is to improving paint film adhesion with the sodium phosphate group, water tolerance is better than the non-oil-in-water type reactive emulsifier with sodium sulfonate group, and the two is suitable to the color developing of coating, but to the supporting capacity (CPVC represents with critical pigment volume concentration) of the pigment that improves emulsion, the reactive emulsifier of sodium sulfonate group is better.

Therefore, preferably, the emulsifying agent consumption is the 4.00～21.00wt ‰ of total monomer weight, preferred 6.00～20wt ‰ or 8～18wt ‰, more preferably 10～16wt ‰ or 12～14wt ‰, wherein emulsifying agent B consumption is the 1.00～6.00wt ‰ of total monomer weight, preferred 2.00～3.00wt ‰, NRS-10 or SE-10N consumption are the 1.00～6.00wt ‰ of total monomer weight, preferred 2.00～5.00wt ‰, more preferably 3.00～4.00wt ‰, the polymerization stability of this moment, final particle size of emulsion size and size distribution, viscosity and salt stability all meet the requirement of coating emulsion.The consumption of non-oil-in-water type reactive emulsifier COPS-1 or COPS-3 is at the 1.00～5.00wt ‰ of monomer total amount, preferred 2.00～3.00wt ‰.

Preferably, also comprise non ionic polymer type emulsifying agent in the described emulsifying agent, preferred siliceous emulsifying agent.The segmented copolymer of the preferred polysiloxane of described siliceous emulsifying agent and polyethers totally is nonionic, and is very little to grain diameter influence, but because its surface tension is extremely low, influences the polymerization behavior.Further preferably, the surface tension of selected siliceous emulsifying agent is between 2～20 dyne, preferably between 5～18 dyne.Particularly preferably be S-240 emulsifying agent (German Degussa company).The consumption of siliceous emulsifying agent is influential to polymerization stability, and with the increase of siliceous emulsifying agent consumption, polymerization stability descends, and color developing strengthens, the performance of comprehensive polymerization stability and paint film, and the suitable consumption of siliceous emulsifying agent is 1～4 ‰, and preferred 2 ‰～3.00 ‰.

Further preferably, the emulsifying agent that the preparation of styrene-acrylic coating emulsion is selected is the composite use of emulsifying agent B, NRS-10, COPS-3 and S-240, and consumption is respectively with respect to the monomer total amount: 1.00～6.00wt ‰, 1.00～5.00wt ‰, 1.00～4.00wt ‰.Be preferably 2.00～3.00wt ‰, 3.00～4.00wt ‰.

Described initiator, can be inorganic radical initiator (for example Potassium Persulphate, Sodium Persulfate or ammonium persulphate), organic oxidation initiator (one or more in for example organo-peroxide (as tert-butyl peroxide), or organic reducing initiator (as sodium formaldehyde sulphoxylate, sodium bisulfite).

Any one seed emulsion that described seed emulsion is the invention described above.Particle size of emulsion is more little, and its weathering resistance improves, and the character of seed emulsion itself has a strong impact on styrene-acrylic particle size of emulsion and size distribution and final emulsion polymer in the distribution of emulsion particle, and these all influence the weather resistance of paint film.Among the present invention, along with the seed emulsion consumption increases, the seed polymer content of coating surface increases, and the styrene content of seed polymer is very little, so weather resistance increases.And the particle of styrene-acrylic coating emulsion inside is the glassy phase of superfine particle diameter, when paint film is passed in the ultraviolet ray in the atmosphere, a part is passed the space of particle, and then the be excited molecular orbital(MO) of attitude of another part absorbs, and then improves the ultraviolet aging resistance performance of paint film.This is that the tunnel effect of nanoparticle provides.But, the consumption of seed emulsion can not be too high, this is because the seed emulsion consumption increases, particle diameter sharply diminishes, and causes the viscosity of emulsion sharply to increase, and not only gives packing, the taking-up of emulsion, transfer causes difficulty, and the rheology index increase of finally preparing the coating of high emulsion content, the levelling property of coating descends, and also can cause the degradation of part paint film.

For improving the performance of described styrene-acrylic coating emulsion, can also add emulsion preparation auxiliary agent commonly used.

Preferably, also comprise neutralizing agent in the described styrene-acrylic coating emulsion, ammoniacal liquor for example, methylol ammonia, preferred ammoniacal liquor.Ammoniacal liquor is usually with 20-40wt%, more general 22-35wt% among the present invention, and especially the concentration of 25wt% is used.

Preferably, can also add sanitas in the described styrene-acrylic coating emulsion, for example Sodium Benzoate, daconil M, aminopropanol compound, preferably one or more among Alex251, the BIT-20 (U.S. Sol company).Further preferably, in the styrene-acrylic coating emulsion, contain based on total reaction mixture weight 0～0.2% preferred 0～0.1% sanitas.

Preferably, can also add defoamer in the described styrene-acrylic coating emulsion, described defoamer is silicone antifoam agent or fluorine modified siloxane defoamer, one or more in preferred water-based silicone oil, the silicone emulsion; In further preferred DF60 defoamer, Tego902W defoamer, the WBA defoamer (U.S. Kening Co.,Ltd) one or more.Further preferably, in the styrene-acrylic coating emulsion, contain based on total reaction mixture weight 0～5 ‰ preferred 1～4 ‰ defoamer.

Color stuffing described in the present invention specifically refers to pigment and filler.Wherein, the performance of pigment has substantial connection with the opacifying power of filming, uniform coloring, tint retention and chalking resistance, can be this area one or more pigment commonly used, include but not limited to, titanium dioxide, ferric oxide, carbon black and various toner pigment slurry (for example phthalocyanine blue), more than fineness requirement 1200 orders, the Rutile type Titanium Dioxide (R902) that preferably adopts du pont company to produce.

Filler is a kind of non-coloring power or the pigment extender that extremely less colored power is only arranged, mainly play coating performance adjustment, film performance change and further reduce the effect of filler cost, can be this area one or more fillers commonly used, include but not limited to be calcium carbonate, talcum powder, kaolin, wollastonite powder, more than fineness requirement 1200 orders, preferably adopt in ultra-fine talcum powder (1200 order), heavy calcium carbonate (1200 order) or the wollastonite powder (1200 order) any one or a few.The preferred Beijing Mei Yahua of the embodiment of the invention becomes coarse whiting (1200 order), talcum powder (1200 order), the wollastonite powder (1200 order) of trade Co., Ltd.

Described dispersion agent is polycarboxylate sodium's type dispersion agent, the SN-5040 of preferred Japanese Nuo Puke chemical industry company limited.

Described wetting agent comprises pigment wetting agent and base material wetting agent.Pigment wetting be pigment by the prerequisite of stable dispersion, the pigment wetting process is actually the process that the gas of surface of pigments is replaced by base-material solution, emulsion itself is very poor to the wetting ability of pigment, so must use wetting agent.According to the color stuffing of determining, select corresponding wetting dispersing agent, the multi-usage tensio-active agent PE-100 of the preferred Shenzhen of the present invention Hai Chuan chemical industry company limited.

The present invention also comprises auxiliary film forming matter, auxiliary film forming matter is film forming separately, just form to be coated with at coating and play auxiliary effect in the membrane process, as various auxiliary agents such as film coalescence aid, defoamer, frostproofer, neutralizing agent, sanitas, thickening materials, though their consumptions in coating are little, physicalies such as the storage of coating, the water tolerance of constructing and filming, ageing resistance, abrasion resistance all there is obvious effect.

Described molecular weight regulator is any one or a few among uncle's lauryl mercaptan (t-DM), n-dodecyl mercaptan (n-DM), thiohydracrylic acid butyl ester, thiohydracrylic acid monooctyl ester, secondary alcohol, vinylchlorid, the TEXNOL.When using t-DM and n-DM, because its polarity and acrylate copolymer differ bigger, though the molecular-weight adjusting effect is pretty good, the reduction of the gloss of the emulsion coatings formulated that makes, the molecular weight regulator of the high optical coating emulsion of uncomfortable cooperation; And consumption can not be too big, otherwise residual smell is very heavy, and this is still worthless for the clean flavor of preparation coating.Use the thiohydracrylic acid butyl ester, during the thiohydracrylic acid monooctyl ester, the effect of adjusting molecular weight and t-DM and n-DM are suitable, also not delustring, but not only expensive, and still have bad smell residual, can there be the problem of using t-DM and n-DM to occur equally.The molecular weight effect of regulating letex polymerization with secondary alcohol is all good not as other molecular weight regulators, can supply the selectable Virahol that has at present, isopropylcarbinol, but taste is very big, still is not suitable as the molecular weight regulator of clean flavor coating emulsion.Vinylchlorid is that a lipophilicity is fine, and the polymerisable unsaturated vinyl monomer of chain transfer constant maximum is behind monomer such as vinylbenzene, acrylate and the chloroethylene copolymer, not only can improve the water tolerance of multipolymer, the compactness of paint film, sticking power etc., and the molecular weight that reduces multipolymer can be arranged.But make the saturated vapor pressure that the molecular-weight adjusting monomer notes vinylchlorid with vinylchlorid, the saturated vapor pressure of vinylchlorid is very high, generally at 6kg/cm ², when consumption after a little while, vinyl chloride monomer can be absorbed in styrene monomer earlier and cross in the butyl acrylate, its absorption liquid is together entered in the pre-emulsification still get final product then, polymerization process afterwards just can carry out under normal pressure.Therefore, preferred TEXNOL.TEXNOL is the high boiling point organic compound that had not only contained ester group in a part structure but also contained two secondary hydroxyls, and is not only good with the multipolymer consistency, and smell is very little and have certain molecular-weight adjusting effect.Further preferably, the composite use of TEXNOL and vinyl chloride monomer.

Along with the increase of molecular weight regulator consumption, the molecular weight of polymkeric substance reduces, and the structural gel content of polymkeric substance reduces, the minimum film-forming temperature of emulsion, and the scrub performance of paint film and wet sticking power will improve; And the molecular weight of polymkeric substance reduces, and the color developing of coating increases.Therefore, preferably, the TEXNOL consumption is 1～4% of monomer total amount, and is preferred 2～3%, and the VC consumption is 1.00～4.50% of monomer total amount, preferred 1.50～4.00%, further preferred 2.50～3.50%.

Described defoamer can be liquid metal soap defoamer, as the Japanese Nuo Puke chemical industry defoamer NXZ of company limited; Can be for the silica anhydride defoamer, as SN-DEFOAMER345; Can be non-silicon defoaming agent, for example Foshan Supreme Being converges the DH-X2205 of company.

Described neutralizing agent can be ammoniacal liquor or methylol ammonia, preferred ammoniacal liquor.

The associative thickener (TT935) of the preferred U.S. of described thickening material Rhom and Hass, thickening material (ASE-60).

Interpolation sanitas, the mould inhibitor that can also choose wantonly in the described coating.Described sanitas can be in Sodium Benzoate, daconil M, the aminopropanol compound any one or a few.

The AMP-95 of the preferred Dow Chemical of described pH regulator agent.

The invention still further relates to a kind of method for preparing above-mentioned styrene-acrylic coating, this method comprises the steps:

(1) in disperseing cylinder, add water to open and stir, add wetting agent, dispersion agent, pH regulator agent, after the stirring and dissolving, raising rotating speed (for example carrying to 1500～1800 rev/mins) adds color stuffing and disperses, and disperses 30～50 minutes;

(2) slurry after will disperseing grinds, and fineness reaches below 30 microns;

(3) under low speed (for example 500～800 rev/mins) agitation condition, described any one styrene-acrylic emulsion of second aspect present invention, defoamer, thickening material, pH regulator agent, molecular weight regulator, sanitas, mould inhibitor are dropped in the dispersion cylinder, mixing and stirring is filtered and is made styrene-acrylic coating.

Coating of the present invention can be used for the filmogen of all kinds of building inside and outside wall emulsion paints, also can be used for anti-corrosion of metal priming paint, the preparation of the varnish of woodenware door and window etc.

" choose " expression in this application wantonly and be with or without, for example " randomly add " expression and add or do not add.

Described " water " is preferably " deionized water " in this application.

The present invention utilizes the controlled emulsion polymerization technology of seed to combine with phased film technique, has solved the technical bottleneck of preparation high-performance building exterior wall with the styrene-acrylic coating emulsion.The present invention has the following advantages:

(1) the seed emulsion controllable polymerization is combined with phased film technique, realized final particle size of emulsion, size distribution control, realized distribution control and the polymkeric substance amphipathic property distribution control of polymkeric substance inside and outside emulsion particle.Used seed emulsion belongs to international initiative in design concepts such as quoting of the wetting ability of seed polymer and lipophilicity, particle diameter and distribution thereof and siliceous emulsifying agent; Finally reach seed emulsion and have best amphipathic property, the most rational super surface effects.

(2) the controlled letex polymerization of seed is combined with phased film technique, realized just can making the target emulsion that over-all properties is reached advanced world standards with conventional raw material.

(3) utilize the tunnel effect of organic nano particle, successfully improved the ageing-resistant performance of styrene-acrylic coating emulsion;

(4) utilize the seeded emulsion polymerization technology, solved successfully that the production process emulsion particle diameter is difficult to control and the quality fluctuation problem that causes;

(5) utilize the seeded emulsion polymerization technology, reduced the emulsifying agent consumption of preparation fine grain size emulsion significantly, thereby improved the water tolerance of paint film, contamination resistance;

(6) utilize the designability of the inside and outside distribution of polymer of the powerful surface effects of organic nano particle and latex particle, seed emulsion polymerization is combined with the phased membrane technique that diffuses into, realized with the most conventional raw material (monomer, linking agent, emulsifying agent, auxiliary agent) makes the coating emulsion of high-performance (weather-proof, super water-fast, resistant and high color development);

(7) this seeded emulsion polymerization technology is different from the prior seed letex polymerization, and the outside of seed polymer distribution objectives emulsion emulsion particle has successfully solved the low surface energy emulsifying agent fast to the diffusion problem of coating surface;

(8) problems such as paint film compactness, mechanical property and anti-outdoor aging have successfully been solved by particle diameter and the control that distributes.

(9) the designed intermediate raw material seed emulsion of the present invention and the production process of final styrene-acrylic coating emulsion and raw materials used production method just reach discharging standards through simple improvement, are the methods that an environment-protecting clean is produced.

In this application, described " styrene-acrylic " emulsion, coating refer to cinnamic acrylic ester emulsion, coating, are to introduce the cinnamic acrylic emulsion system of hard monomer.

In this application, the monomer with lower glass transition temperatures (being lower than 30 ℃) is known as " soft monomer ", and the monomer with high glass-transition temperature (being higher than 32 ℃) is known as " hard monomer ".

In this application, the multipolymer with lower glass transition temperatures is known as " flexible polymer ", and the multipolymer with high glass-transition temperature is known as " hard polymer ".

Description of drawings

Fig. 1 is the transmission electron microscope sectional view of the coating emulsion of the prepared embodiment 10 of the seed emulsion of employing embodiment 5.

Wherein the seeded emulsion polymerization thing is distributed in the outside of the particle of coating emulsion.

Embodiment

Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.

Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not a corresponding national standard, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.

The embodiment explanation:

1. the source of embodiment raw material and specification

(1) embodiment seed emulsion, styrene-acrylic emulsion preparation raw material sources and specification

(2) styrene-acrylic coating prepares used additives and color stuffing source and specification

2. performance test standard

3. main analytical instrument, equipment

Embodiment

The preparation of I seed emulsion

(1) pre-emulsification adds the deionized water that measures in the 5000ml there-necked flask, opens and stirs, and adds the emulsifying agent of metering, begins to drip the monomer that measures behind the 15min, the about 1h of continuation high-speed stirring emulsification;

(2) polymerization adds deionized water in the 1000ml four-hole boiling flask that has stirring, reflux exchanger, thermometer and constant pressure funnel, open and stir, the rebasing emulsifying agent that adds metering, when being warming up to 85 ℃, the initiator solution that adds metering, treat temperature dash to the highest and stablize 2 minutes after, begin to drip pre-emulsion and drip initiator solution, temperature control is at 86～88 ℃ during dropping, and the time of dropping was always controlled at 90～100 minutes; Drip and finish back insulation 1h;

(3) cool to emulsifying agent and sanitas and the defoamer that adds metering below 40 ℃, be neutralized to pH value to 8.0～8.50 with ammoniacal liquor at last, filter then, measure the every index of seed emulsion, comprise transformation efficiency, slag yield, particle diameter and size distribution, emulsion particle form.

The component prescription of embodiment seed emulsion (outside the demonomerization ratio, other consumption is in weight part)

The polymerization result of table 2 different monomers mix proportion scheme gained seed emulsion

Remarks: * monomer ratio: ST:MMA:EA:BA; * does not reach 100% because of the glass effect transformation efficiency

1. polymerization temperature is 88 ℃, and 2. the SDBS amount is 5% of amount of monomer, and the COPS-1 consumption is 5.00% of amount of monomer; 3. the APS consumption is 7.00 ‰ of amount of monomer

The data declaration of table 2: along with the Hunk constant reduction of mix monomer and the reduction of design Tg, monomer conversion improves, and throw out reduces particle diameter and diminishes.

The preparation of II styrene-acrylic coating emulsion

(1) pre-emulsification: in the 5000ml there-necked flask, add the deionized water (DW) that measures, open and stir, add the emulsification emulsifying agent of metering, begin to drip the monomer that measures behind the 15min, the about 1h of continuation high-speed stirring emulsification;

(2) polymerization: in the 5000ml there-necked flask that has stirring, reflux exchanger, thermometer and constant pressure funnel, add deionized water, open and stir, when being warming up to 86～90 ℃, add the above-mentioned seed emulsion that measures, in the time of 88 ℃, add metering component three, begin to drip component one and component two after about 5 minutes, the dropping time was controlled at 180～250 minutes, dropping temperature control is at 80～88 ℃, drip and finish back insulation 1h, cool to 66～70 ℃ and add neutralizing agent A, carry out the back then and eliminate;

(3) eliminate the back: under 65～67 ℃, add component and drip component six after five, 10 minutes, 30 minutes dropping time, carry out the insulation second time after dropwising;

(4) be cooled to below 40 ℃ after for the second time insulation finishes, add component eight, stirs and add component nine after 20 minutes, component ten, and component 11 continue stirring 60 minutes then;

(5) filter packing, every performance of mensuration emulsion at last with 500 mesh filter screens; Comprise transformation efficiency, slag yield, particle diameter and size distribution, emulsion particle form.

The component prescription of styrene-acrylic coating emulsion (weight part, g)

The Hunk constant of the polymkeric substance of seed emulsion is equal to or less than 2.98pKa, much smaller than the Hunk constant (generally between 3.8～4.25pKa) of the polymerization mix monomer that drips during coating emulsion in preparation subsequently, so seed polymer is finally at the skin of final styrene-acrylic emulsion emulsion particle.Fig. 1 is the Electronic Speculum figure that adopts the styrene-acrylic emulsion that the seed emulsion of embodiment 5 makes, to prove the exactness of above-mentioned deduction.

As seen from Figure 1, compare with the follow-up monomer of styrene-acrylic emulsion, the vinylbenzene consumption of seed emulsion is few, seed polymer (20wt% following) is white in color, and follow-up dropping polymerization single polymerization monomer styrene content is up to 52%, and the color of follow-up dropping polymkeric substance is black, therefore the ball center of Fig. 1 partly is that follow-up monomer polymerization forms, and the shell polymkeric substance is to be formed by seed polymer, that is to say, seed polymer finally is distributed in the outside of emulsion particle.

The preparation of III styrene-acrylic coating

(1) in the special-purpose dispersion of coating preparation cylinder, add deionized water and open stirring, add pigment wetting agent (PE-100) successively, pigment dispersing agent (SN5040), and multifunctional assistant AMP-95, after stirring and dissolving finishes, rotating speed is carried to 1500～1800 rev/mins, added color stuffing and disperse, under this speed, disperseed 40 minutes;

(2) slurry after will disperseing grinds, and allows fineness reach below the 40 μ m;

(3) under low speed (for example 500～800 rev/mins) agitation condition, the styrene-acrylic emulsion that the embodiment II is made adds in the dispersion cylinder, simultaneously appropriate amount of defoamer, thickening material, AMP-95, TEXNOL is dropped into mixing and stirring, filters and makes styrene-acrylic coating.

Styrene-acrylic coating composition prescription

Embodiment 1～3 and Comparative Examples 1 are used for measuring traditional performance and the mechanical property of coating; Embodiment 4 and Comparative Examples 2 are used for measuring color developing.

The paint film property of phenylpropyl alcohol plough coating is:

Remarks: 1-(5%CaCl ₂: 1:4,48h); 2-divides 5 grades, and 5 ★ are best.

Claims (22)

1. copolymer in cinnamic acrylic ester type seed emulsion, this emulsion is by the vinylbenzene as monomer component, butyl acrylate, methyl methacrylate and ethyl propenoate, in the presence of the reactive emulsifier that contains olefinic double bond (or containing carbon-to-carbon double bond) and anionic emulsifier sodium lauryl sulphate or Sodium dodecylbenzene sulfonate and water, undertaken by adding radical initiator that emulsion polymerization prepares, wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), the ratio (by weight) of butyl acrylate (BA) is St:MMA:EA:BA=(7～25): (15～40): (10～30): (20～70 or 20～60), preferably (8～20): (25～35): (12～27): (30～40).

2. according to the seed emulsion of claim 1, wherein the Hunk constant (Hansch) of the polymkeric substance in the seed emulsion is 2.25～3.10, is preferably 2.30～3.00; And/or this polymkeric substance has 5.0～10.0 ℃, the second-order transition temperature (Tg) of preferred 5.5～9.5 ℃ or 6.0～9.0 ℃.

3. seed emulsion according to claim 1 and 2 is characterized in that the solid content of described seed emulsion at 20-60wt%, preferably between 30～50wt%.

4. according to any one seed emulsion in the claim 1～3, it is characterized in that: reactive emulsifier be selected from following in these one or both or multiple: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

5. according to any one seed emulsion in the claim 1～4, it is characterized in that: also comprise neutralizing agent in the described seed emulsion.

6. according to any one seed emulsion in the claim 1～5, it is characterized in that: also comprise sanitas and/or defoamer in the described seed emulsion.

7. according to any one seed emulsion in the claim 1～6, it is characterized in that: the number average bead diameter of described seed emulsion is 25～40nm, preferred 27～38nm, and/or size distribution index (PDI) is more preferably less than 0.10 less than 0.12.

8. according to any one seed emulsion in the claim 1～7, it is characterized in that: the minimum film-forming temperature of described seed emulsion (MFT) is 4～12 ℃.

9. prepare the method for the seed emulsion of any one in the claim 1～8, this method may further comprise the steps:

(1) pre-emulsification: with the deionized water of 25～37 weight parts, the anionic emulsifier sodium lauryl sulphate (SDS) of 2～10 weight parts or Sodium dodecylbenzene sulfonate (SDBS), after reactive emulsifier stirring and dissolving for some time of containing olefinic double bond of 2～10 weight parts, drip the monomer mixture of being formed by vinylbenzene, methyl methacrylate, ethyl propenoate and butyl acrylate of 90-110 weight part, continue high-speed stirring emulsification, obtain pre-emulsion; The ratio (by weight) of wherein said monomer component vinylbenzene (St), methyl methacrylate (MMA), ethyl propenoate (EA), butyl acrylate (BA) is St:MMA:EA:BA=(7～25): (15～40): (10～30): (20～70 or 20～60), preferably (8～20): (25～35): (12～27): (30～40);

(2) polymerization: with the deionized water of 70～95 weight parts (preferred 75～90 weight parts), rebasing anionic emulsifier sodium lauryl sulphate (SDS) or the Sodium dodecylbenzene sulfonate (SDBS) of 0.7～3 weight part, under agitation condition, be warming up to 70～95 ℃, kept 1～20 minute, drip pre-emulsion and the initiator solution of step (1) gained, temperature of reaction control is at 80～92 ℃ during dropping, and the time of dropping was always controlled at 60～130 minutes; Drip and finish back insulation 40～80 minutes;

(3) step 2 gained emulsion is cooled to 15～40 ℃, the anionic emulsifier sodium lauryl sulphate (SDS) or the Sodium dodecylbenzene sulfonate (SDBS) that add 1～6 weight part, randomly add the sanitas of 0 weight part or 0.01-0.3 weight part and/or the defoamer of 0 weight part or 0.01-0.3 weight part, the final reaction mixture neutralizes with neutralizing agent, filter then, obtain seed emulsion.

10. by the prepared seed emulsion of the method for any one in the claim 1～10, wherein the Hunk constant (Hansch) of the polymkeric substance in the seed emulsion is 2.25～3.10, be preferably 2.30～3.00, and/or this polymkeric substance has 5.0～10.0 ℃, the second-order transition temperature (Tg) of preferred 5.5～9.5 ℃ or 6.0～9.0 ℃.

11. prepare the method for copolymer in cinnamic acrylic ester type coating emulsion, this method may further comprise the steps:

(1) pre-emulsification: the deionized water that adds 14～37 weight parts in the pre-emulsification still, under whipped state, add the non-reactive emulsifier of 0.2～1.5 weight part and the reactive emulsifier that contains olefinic double bond of 0.2～1.2 weight part, after after a while, drip the monomer mixture of being formed by vinylbenzene (St), butyl acrylate (BA), vinylformic acid (AA), acrylamide (AM), 2-EHA (EHA) and cross-linking monomer of 100 weight parts, high-speed stirring emulsification for some time;

Wherein the relative consumption (based on total monomer weight) of various monomers is:

Vinylbenzene (St) 52～72%;

Butyl acrylate (BA) 10～24%;

Vinylformic acid (AA) 1.2～5%;

Acrylamide (AM) 1.2～5%;

2-EHA (EHA) 12～22%;

Cross-linking monomer 0.5～1.2%;

(2) polymerization: the water that adds 20～35 weight parts in the polymerization reactor, with the buffer reagent that adds 0 or 0.1～0.3 weight part, stir, be warming up to 70-93 ℃, the seed emulsion of any one described seed emulsion or claim 10 in the claim 1～8 of interpolation 5～32 weight parts, add rebasing initiator solution down at 85-90 ℃ then, after for some time, begin to drip step (1) gained pre-emulsion and initiator solution, the control of dropping time was at 150～300 minutes, and dropping temperature is controlled at 76～89 ℃, dripped to finish back insulation for some time, cool to 62～72 ℃ again, add neutralizing agent;

(3) eliminate the back: under 60～70 ℃, initiator A is eliminated in a kind of back that adds 0.2～0.5 weight part in step (2) the gained emulsion, eliminate initiator B through a kind of back that drips 0.2～0.5 weight part after 5～15 minutes, the dropping time, control was at 15～45 minutes, carry out the insulation second time after dropwising, soaking time is 30 minutes-3 hours;

(4) be cooled to 15～40 ℃ after insulation finishes for the second time, add the emulsifying agent of 0.2～0.5 weight part, add optional neutralizing agent, optional defoamer, optional sanitas after stirring for some time, continue again to stir;

(5) filter at last, the copolymer in cinnamic acrylic ester that makes phased film forming is coating emulsion.

12. the copolymer in cinnamic acrylic ester of the phased film forming of preparation according to claim 11 is the coating emulsion method of (being called for short the empty film forming styrene-acrylic of Xiang coating emulsion), wherein said cross-linking monomer is vinyl three (C1-C3 alkoxyl group) silane.

13. according to claim 11 or 12 described methods, wherein in step (1)) in the pre-emulsion that forms or in step (2) in the dropping pre-emulsion or afterwards, also drip the molecular weight regulator of 0.5-8 weight part.

14. according to any one described method in the claim 11～13, wherein reactive emulsifier be selected from following in these one or both or multiple: allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Preferably, reactive emulsifier is selected from one or both in 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

15. according to any one described method in the claim 11～14, wherein reactive emulsifier is to be selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12), nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or a kind of and a kind of binding substances that is selected among NRS-10 or the SE-10N in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS); Be more preferably a kind of and a kind of binding substances that is selected among NRS-10 or the SE-10N that is selected from 3-allyloxy-2-hydroxyl-propyl sulfonic acid sodium (COPS-1) or the 3-allyloxy-2-hydroxyl-propyl group sodium phosphate salt (COPS-3).

16. according to the method that is coating emulsion of the phased film forming copolymer in cinnamic acrylic ester of any one described preparation in the claim 11～15, wherein the reactive emulsifier that contains olefinic double bond of 0.2～1.2 weight part comprises NRS-10 or the SE-10N of 0.1～0.6 weight part, with 0.1～0.6 weight part be selected from allyl group hydroxyalkylated sulfonic acid sodium (SAHS), allyl group oxygen ethyl polyethylene-oxide (6,8,10 or 12) nonylplenyl ether ammonium sulfate (DNS-86), maleic anhydride derivative sodium sulfonate (M12), 2-acrylate amide group-2-methyl-propyl sulfonate (AMPS), 3-allyl group oxygen base-2-hydroxyl-propyl sulfonic acid sodium (COPS-1), 3-allyl group oxygen base-2-hydroxyl-propyl group sodium phosphate (COPS-3), methoxy poly (ethylene glycol) methacrylate (MPEGMA), sodium vinyl sulfonate (SVS), 2-methyl-2-propylene-1-sodium sulfonate (SMS), 2-acrylamide-2-methyl isophthalic acid-propane sulfonic acid sodium (AMPSA), or a kind of in 2-acrylamido-2-methylbutane sodium sulfonate (SAMBS).

17. the phased film forming copolymer in cinnamic acrylic ester by any described method preparation in the claim 11～16 is coating emulsion, the solid content that wherein said phased film forming copolymer in cinnamic acrylic ester is coating emulsion is between 35-60wt%.

18. according to claim 17 a described coating emulsion, wherein said phased film forming copolymer in cinnamic acrylic ester is that the number average particle size of particle is between 70～90nm in the coating emulsion.

19. phased film forming copolymer in cinnamic acrylic ester is latex coating, it is characterized in that: described coating comprises following component:

More than 17 or 18 described copolymer in cinnamic acrylic ester be coating emulsion 100-400 weight part;

Filler 250-600 weight part;

Pigment 0 or 0.5-150 weight part;

Pigment dispersing agent 0 or 0.1-8 weight part;

Pigment wetting agent 0 or 0.05-2 weight part;

Defoamer 0 or 0.02-0.50 weight part;

Thickening material 0 or 1-5 weight part;

PH regulator agent 0 or 1-10 weight part;

Film coalescence aid or 1-10 weight part;

Sanitas 0 or 0.1-3 weight part;

Mould inhibitor 0 or 0.1-3 weight part;

Water 160-400 weight part.

20. according to above 19 coating, wherein said pigment be in titanium dioxide, ferric oxide, carbon black, toner pigment slurry or the organic synthesis pigment one or both or multiple; Filler be in calcium carbonate, talcum powder, kaolin, the wollastonite powder one or both or multiple.

21. above 19 or 20 methods that described phased film forming copolymer in cinnamic acrylic ester is latex coating of preparation, this method comprises the steps:

(1) in having the dispersing apparatus of whipping device (as disperseing cylinder), add water, unlatching is stirred, and adds wetting agent, dispersion agent, pH regulator agent, after the stirring and dissolving, adds filler behind the rotating speed of raising whipping device and disperses with optional pigment;

(2) slurry after will disperseing grinds, and fineness (mean particle size) reaches below 40 microns or 40 microns;

(3) under the stirring at low speed condition, claim 17 or 18 described cinnamic acrylic ester type coating emulsions, defoamer, thickening material, pH regulator agent, optional film coalescence aid, sanitas, mould inhibitor are dropped in the dispersing apparatus, mixing and stirring is filtered and is made described cinnamic acrylic ester type coating.

22. be that latex coating is used to prepare all kinds of building inside and outside wall emulsion paints, anti-corrosion of metal priming paint, the purposes of the varnish of woodenware door and window according to claim 19 or 20 described phased film forming copolymer in cinnamic acrylic ester.

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