CN105038429A - Inner wall latex paint with excellent freeze thawing stability and preparation method of inner wall latex paint - Google Patents
Inner wall latex paint with excellent freeze thawing stability and preparation method of inner wall latex paint Download PDFInfo
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Abstract
The invention belongs to the field of paint, and discloses inner wall latex paint with excellent freeze thawing stability and a preparation method of the inner wall latex paint. The latex paint comprises the following raw material components: water, an anion-nonionic composite dispersion wetting agent, nano dispersion colloid, a film-forming additive, a defoaming agent, a thickening agent, pigment filler, an anticorrosion agent and styrene-acrylate emulsion, wherein the anion-nonionic dispersion wetting agent is a mixture of an anion dispersion agent and a nonionic wetting agent, biologically degradable, green and environment-friendly, and the synergistic effect of the anion dispersion agent and the nonionic wetting agent facilitates the improvement of storage stability and freeze thawing stability of the paint; the nano dispersion colloid reduces the specific surface area of the pigment filler and synergistically improves the effect of the anion-ionic composite dispersion wetting agent; the styrene-acrylate emulsion has excellent freeze thawing stability. In general, the inner wall latex paint has no need of anti-freezing assistant solvent and has excellent freeze thawing stability.
Description
Technical field
The invention belongs to paint field, be specifically related to a kind of internal wall emulsion coating with excellent freeze-thaw stability and preparation method thereof.
Background technology
Latex coating is moderate, easy construction environmental protection, is widely used in interior decoration and covers with paint, lacquer, colour wash, etc.But there is the shortcoming of freeze-thaw stability difference because being dispersion medium with water in latex coating.Freeze thawing, refers to water to be the coating thermal exchange at low ambient temperatures of dispersion medium.Freeze-thaw stability be coating experience freeze with thaw cycle after recover the stability of flowable state.Latex coating is made up of synthetic resin emulsion, pigment and filler, auxiliary agent, water, and synthetic resin emulsion belongs to colloidal dispersion system, and latex coating belongs to coarse dispersion system on the whole, is a kind of heterogeneous dispersion system of thermodynamic instability.Therefore thermal exchange very easily destroys the stability of latex coating, gently then causes that the outward appearance of coating changes, viscosity rises, heavy then cause coating condense into block, cannot flowable state be recovered and lose use value.During the coating of application freeze-thaw stability difference, exist region and season limitation, this hinders the application & development of product largely.
For solving the problem, Chinese scholars has carried out many-sided research.
Patent application CN103205172A, patent CN1890334A and CN102272214A all by adding antifreezing agent in latex coating, and the freezing point reducing latex coating dispersion medium improves the freeze-thaw stability of latex coating.But the antifreezing agent added is generally VOC solvent, this causes again VOC content in product to raise.In today that environmental regulation is day by day harsh, there is limitation in this method.
Document (AliceP.King, HaroldNaidus.Therelationshipbetweenemulsionfreeze-thawst abilityandpolymerglasstransitiontemperature.I.Astudyofth epolymersandcopolymersofmethylmethacrylateandethylacryla te [J] .JournalofPolymerScience.PartC:PolymerSymposia, 1969,27 (1): 311-319) have studied the glass transition temperature Tg of synthetic polymer resin and the relation of freeze-thaw stability.Result shows: in the letex polymerization of methyl methacrylate (MMA)/ethyl propenoate (EA), with methacrylic acid (MAA) for function monomer, the Tg of synthetic polymer resin is higher, reaches the identical MAA consumption needed for freeze-thaw stability cycle index fewer.At present, by everybody generally accepted viewpoint be: the polymer emulsion with high Tg, emulsion more easily recovers flowable state after freezing; And there is the polymer emulsion of relatively low Tg, emulsion is freezed rear latex particle and irreversible condensation is more easily occurred and cannot recover flowable state.Therefore, adopt the synthetic polymer resin of high Tg in theory, the excellent latex coating of freeze-thaw stability can be prepared.But this achieves the goal premised on the film forming properties of sacrificial coatings paint film.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is to provide a kind of internal wall emulsion coating with excellent freeze-thaw stability.The present invention starts with from the factor affecting latex coating dispersion stability, solves the problem of latex coating freeze-thaw stability difference from root, has prepared a kind of latex coating namely without the need to adding any antifreeze auxiliary agent with excellent freeze-thaw stability.
Another object of the present invention is to the preparation method that above-mentioned latex coating is provided.
Object of the present invention is achieved through the following technical solutions:
Have an internal wall emulsion coating for excellent freeze-thaw stability, described latex coating feed composition comprises water, anion-nonionic composite diffusion wetting agent, nano-dispersed colloid, film coalescence aid, defoamer, thickening material, color stuffing, sanitas and styrene-acrylate emulsion.
Described anion-nonionic composite diffusion wetting agent is the mixture of anionic dispersing agents and non-ionic wetting agent; Described anionic dispersing agents is polyphosphoric acid salt dispersion agent or polyacrylic salt dispersant; Described non-ionic wetting agent is alkyl polyoxyethylene ether class wetting agent.
Described polyphosphoric acid salt dispersion agent is the lucky Buddhist nun POLYRONNC in German Bake; Described polyacrylic salt dispersant is that Tao Shi spy is good loose
tM1124 or special good loose
tM731A;
Described polyethenoxy ether class wetting agent is alkyl polyoxyethylene ether; Polyethenoxy ether class wetting agent is Clariant EmulsogenLCN407 or EMULGEN709.
In described anion-nonionic composite diffusion wetting agent, the mass ratio of anionic dispersing agents and non-ionic wetting agent is (1:1) ~ (1:2).
Described anionic dispersing agents makes color stuffing surface there is electrostatic double layer protective layer, and the hydrophobic group of non-ionic wetting agent makes color stuffing surface Existential Space steric hindrance, and the synergy of both is conducive to the stability in storage and the freeze-thaw stability that improve coating.
Described nano-dispersed colloid is SS-I water nano hydrophobizing agent or SS-II water nano hydrophobizing agent, and Beijing is initiated nanosecond science and technology company and produced; The particle diameter of described nano-dispersed colloid is 20 ~ 500nm, and active constituent content is between 30 ~ 50%.The small-size effect of described nano-dispersed colloid can improve the volume filling density of color stuffing in coating greatly, reduce capillary action, reduce the specific surface area of color stuffing, the collaborative anion-nonionic composite diffusion wetting agent that strengthens, to the dispersion moistening effect of color stuffing, promotes the raising of the freeze-thaw stability of coating.
Described styrene-acrylate emulsion adopts core-shell emulsion polymerization legal system standby, and shell second-order transition temperature is 18 ~ 40 DEG C, comprises the anionic and nonionic compound emulsifying agent of particular type and content and functional polymerization single polymerization monomer, has excellent freeze-thaw stability.
Described styrene-acrylate emulsion prepares by the following method:
A pH buffer reagent, anionic-nonionic compound emulsifier, first part's initiator and first part's water add in reactor by (), mixing post-heating; Question response actuator temperature is heated to 78 ~ 82 DEG C, drips first part's polymerization main monomer, dropwises in 5 ~ 10min, insulation 20 ~ 30min;
B () drips the solution that second section polymerization main monomer, second section water and second section initiator are prepared in reactor simultaneously, start to drip functional polymerization single polymerization monomer when second section polymerization main monomer residue 1/2 ~ 1/3, the all materials of this step dropwise in 3 ~ 4h, are then warming up to 85 ~ 90 DEG C of insulation reaction 0.5 ~ 1h;
C () insulation terminates after, be cooled to 50 ~ 60 DEG C, with ammoniacal liquor adjust ph to 7 ~ 9, after cooling, obtain styrene-acrylate emulsion.
Described initiator is divided into first part's initiator and second section initiator, and the consumption of described first part initiator is 20 ~ 40% of initiator gross weight.Described moisture is first part's water and second section water, and the consumption of first part's water is 60 ~ 80% of water gross weight.Described polymerization main monomer is divided into first part to be polymerized main monomer and second section polymerization main monomer, and described first part polymerization main monomer is 8 ~ 15% of polymerization main monomer gross weight.The consumption of described water is 100% ~ 150% of polymerization main monomer total mass, and when described functional polymerization single polymerization monomer comprises methacrylic acid, methacrylic acid adds along with being polymerized main monomer in batches.
Described pH buffer reagent is NaHCO
3or NaHPO
4in one, the consumption of pH buffer reagent is 0.3% ~ 0.6% of polymerization main monomer total mass;
Described anionic-nonionic compound emulsifier is have the one in the compound of formula I ~ formula III general structure:
In formula I ~ formula III, R
1, R
2, R
3and R
4independently be selected from C
1~ C
13straight-chain paraffin base, C
1~ C
13containing the alkyl of branched structure or C
2~ C
15hydroxyalkyl; M is the integer of 3 to 50; N is the integer of 3 to 50; X is sulfonate groups (-SO
3 -m
+), sulfate group (-SO
4 -m
+), carboxylate groups (-COO
-m
+) in one; M
+for Na
+, K
+or NH
4 +.M herein
+both the M in formula I had been referred to
+, also refer to the M of X group in formula II and formula III
+.
The consumption of described anionic-nonionic compound emulsifier is 0.5% ~ 1% of polymerization main monomer total mass.
Described initiator is the one in Sodium Persulfate, ammonium persulphate or Potassium Persulphate, and the consumption of initiator is 0.4% ~ 0.6% of polymerization main monomer total mass.
Described polymerization main monomer is that alkyl acrylate mixes with cinnamic, and described alkyl acrylate is butyl acrylate or Isooctyl acrylate monomer; In described polymerization main monomer, alkyl acrylate and cinnamic mass ratio are (48 ~ 35): (52 ~ 65).
Described functional polymerization single polymerization monomer is have the one in the compound of formula IV ~ formula V general structure: or described functional polymerization single polymerization monomer is methacrylic acid and has mixture a kind of in the compound of formula IV ~ formula V general structure.
In formula IV ~ formula V, R
5be selected from C
1~ C
13straight-chain paraffin base, C
1~ C
13containing the alkyl of branched structure or C
2~ C
15hydroxyalkyl; O is the integer of 3 to 50; X is sulfonate groups (-SO
3 -m
+), sulfate group (-SO
4 -m
+), carboxylate groups (-COO
-m
+) in one; M
+for Na
+, K
+or NH
4 +.
The described consumption with the compound of formula IV ~ formula V general structure is 0.2 ~ 0.6% of polymerization main monomer quality.
The consumption of described methacrylic acid is 1 ~ 2% of polymerization main monomer quality.
Described anion-nonionic composite diffusion wetting agent is non-APEO class Environmentally-friesurface surface surface-active agent, and its consumption is 0.6 ~ 1% of latex coating total mass.
The consumption of described nano-dispersed colloid is 1 ~ 3% of latex coating total mass.
The consumption of described styrene-acrylate emulsion is 9 ~ 15% of latex coating total mass.
Described film coalescence aid is non-VOC high boiling point clean taste ester class organic compound, and consumption is 8 ~ 10% of emulsion consumption in latex coating; The clean taste film coalescence aid of GVE that film coalescence aid selects Shanghai Ji Wei Industrial Co., Ltd. to produce or GV100 film coalescence aid.
Described defoamer is Blackburn CF439 or RHODOLINE681F, and consumption is 0.2 ~ 0.4% of latex coating total mass;
Described thickening material is Natvosol class thickening material, Clariant Natvosol HS30000YP2 or Aksu Natvosol BermocollEBS451FQ, and consumption is 0.4 ~ 0.6% of latex coating total mass;
Described color stuffing is pigment and filler; Described pigment is Rutile type Titanium Dioxide, and consumption is 3 ~ 10% of latex coating total mass;
Described filler is the mixture of kaolin, talcum powder and water-ground limestone, and respective consumption is respectively 10 ~ 15%, 5 ~ 9%, 20 ~ 30% of latex coating total mass.
Described sanitas is water mildow-proof antiseptic-germicide
nB203 (Guangdong Tianchen Biotechnology Co., Ltd.) or Tao Shi ROCIMA
tM631; Its consumption is 0.2 ~ 0.35% of latex coating total mass.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability, specifically comprises the following steps:
(1) defoamer is divided into first part's defoamer and second section defoamer, its mass ratio is (0.1 ~ 0.2): (0.1 ~ 0.2); Thickening material is divided into first part's thickening material and second section thickening material, its mass ratio is (0.2 ~ 0.3): (0.2 ~ 0.3); Described moisture is first part's water, second section water, Part III water, the consumption of the consumption > second section water of first part's water, the consumption of the consumption > Part III water of first part's water; Preferably, first part's water: second section water: the mass ratio of Part III water is (20 ~ 30): (3 ~ 5): (2 ~ 5);
In first part's water, add anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer, first part's thickening material respectively, be uniformly dispersed, obtain mixture;
(2) in mixture, add nano-dispersed colloid, pigment and filler, high speed dispersion, making beating is ground to fineness≤60 μm; Reduce rotating speed, in slurry, add sanitas, second section water and second section thickening material mixed solution successively, then add Part III water flushing pipe again, middling speed is uniformly dispersed, and obtains dispersed paste;
(3) paint: add styrene-acrylate emulsion and second section defoamer in the dispersed paste of step (2), middling speed mixes, and obtains internal wall emulsion coating.
Described in step (1), the rotating speed of dispersion is 400 ~ 450rpm, and the time of dispersion is 10 ~ 15min.
Described in step (2), the rotating speed of high speed dispersion is 1400 ~ 1500rpm; Described reduction rotating speed refers to that rotating speed reduces to 1000 ~ 1200rpm; The rotating speed of described middling speed dispersion is 1000 ~ 1200rpm, and the time of described middling speed dispersion is 10 ~ 15min.
The rotating speed of the dispersion of middling speed described in step (3) is 1000 ~ 1200rpm, and the time of described dispersion is 20 ~ 25min.
General latex coating is made up of synthetic resin emulsion, pigment and filler, auxiliary agent and water, and synthetic resin emulsion belongs to colloidal dispersion system, and latex coating belongs to coarse dispersion system on the whole, is a kind of heterogeneous dispersion system of thermodynamic instability.For latex coating dispersion, the stable main of it realizes jointly by the electrical charge rejection effect between disperse phase viscosity, color stuffing particle, between synthetic emulsion polymkeric substance or spatial separation effect.Latex coating freeze-thaw stability is poor, illustrates that low temperature environment destroys latex coating dispersion stability.This is because under low temperature environment, latex coating dispersion medium water freezes to form ice crystal, cause volumetric expansion extrusion synthetic resin emulsion particle and color stuffing particle, cause emulsion particle breakdown of emulsion, color stuffing is condensed into block, latex dispersions stability is destroyed, finally cause product to go bad, cause huge financial loss.
The present invention, by adopting the benzene emulsion of self-control freeze-thaw stability excellence, adds anion-nonionic composite diffusion wetting agent and the nano-dispersed colloid of certain content in latex paint formulations, reaches the object improving latex coating freeze-thaw stability.Described anion-nonionic composite diffusion wetting agent and nano-dispersed colloid can be worked in coordination with and be strengthened electrical charge rejection effect between color stuffing particle, between synthetic emulsion polymkeric substance or spatial separation effect.
Hinge structure of the present invention has following advantage and effect:
(1) anion-nonionic composite diffusion wetting agent of the present invention is non-APEO class tensio-active agent, biodegradable, environmental protection.
(2) the present invention adopts anion-nonionic composite diffusion wetting agent; anionic dispersing agents makes color stuffing surface there is electrostatic double layer protective layer; the hydrophobic group of non-ionic wetting agent makes color stuffing surface Existential Space steric hindrance, and the synergy of both is conducive to the stability in storage and the freeze-thaw stability that improve coating.
(3) small-size effect of nano-dispersed colloid of the present invention can improve the volume filling density of color stuffing in coating greatly, reduce capillary action, reduce the specific surface area of color stuffing, the collaborative effect strengthening anion-nonionic composite diffusion wetting agent, promotes the raising of the freeze-thaw stability of coating.
(4) described styrene-acrylate emulsion adopts core-shell emulsion polymerization legal system standby, comprises the anionic and nonionic compound emulsifying agent of particular type and content and functional polymerization single polymerization monomer, has excellent freeze-thaw stability.
(5) internal wall emulsion coating of the present invention, does not need to add any antifreeze solubility promoter, just has excellent freeze-thaw stability.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Described benzene emulsion (i.e. styrene-acrylate emulsion) adopts core-shell emulsion polymerization legal system standby and obtains, raw materials used component and consumption as follows:
Polymerization main monomer: 60g vinylbenzene (St), 40g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization single polymerization monomer of 0.2g (COPS-2), 0.75g anionic-nonionic compound emulsifier (KL-70), 0.5g ammonium persulphate (APS), 0.4g sodium bicarbonate, 100g deionized water;
Wherein, the concrete structure formula of functional polymerization single polymerization monomer (COPS-2) is:
The concrete structure formula of anionic-nonionic compound emulsifier (KL-70) is:
The described preparation method with the benzene emulsion of excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), first part's ammonium persulphate (25% of initiator gross weight) and first part's deionized water (80% of water gross weight) are added in reactor, mixing post-heating;
(2) main monomer and methacrylic acid mixing will be polymerized, main monomer mixture must be polymerized; Question response actuator temperature is heated to 78 DEG C, drips first part's polymerization main monomer mixture (consumption is polymerization main monomer mixture total weight amount 10%), dropwise, insulation 30min in 10min in reactor;
(3) in reactor, then drip the solution that second section polymerization main monomer mixture, second section deionized water and second section ammonium persulphate are prepared simultaneously, start to drip functional polymerization single polymerization monomer (COPS-2) when second section polymerization main monomer mixture remains 1/2, the all materials of this step dropwise in 3.5h, are then warming up to 90 DEG C of insulation reaction 1h;
(4) after step (3) reaction terminates, be cooled to 50 DEG C, by ammoniacal liquor adjust ph to 8, there is described in obtaining after cooling the benzene emulsion of excellent freeze-thaw stability, be designated as benzene emulsion 1.In described benzene emulsion, the second-order transition temperature (Tg) of emulsion particle polymeric shell layer is 23 DEG C.
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
40.7% water, 0.3% spy fall apart well
tM1124 dispersion agents (Tao Shi), 0.3%EmulsogenLCN407 (Clariant), 1%SS-I nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), 0.9%GV100 film coalescence aid, 0.2%RHODOLINE681F defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.2% sanitas
nB203 and 9% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.1% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 30% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 6% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 4.7% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.1% of latex coating total mass) is added in the mixture after dispersion, be that under the condition of 1000rpm, middling speed mixes 25 minutes, loading barrel packaging at rotating speed, obtain latex coating, be designated as sample 1.
Embodiment 2
Described benzene emulsion (i.e. styrene-acrylate emulsion) adopts core-shell emulsion polymerization legal system standby and obtains, raw materials used component and consumption as follows:
Polymerization main monomer: 52.5g vinylbenzene (St), 47.5g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization single polymerization monomer of 0.6g (COPS-2), 0.5g anionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulphate (APS), 0.6g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization single polymerization monomer (COPS-2) is identical with the functional polymerization single polymerization monomer described in embodiment 1; Anionic-nonionic compound emulsifier (KL-70) is identical with the anionic-nonionic compound emulsifier described in embodiment 1;
In described benzene emulsion, the second-order transition temperature (Tg) of emulsion particle polymeric shell layer is 18 DEG C.
The described preparation method with the benzene emulsion of excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), first part's ammonium persulphate (25% of initiator gross weight) and first part's deionized water (70% of water gross weight) are added in reactor, mixing post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get polymerization main monomer mixture, question response actuator temperature is heated to 80 DEG C, first part's polymerization main monomer mixture (10% of polymerization main monomer mixture total weight amount) is dripped in reactor, dropwise in 10min, insulation 20min;
(3) in reactor, then drip the solution that the polymerization main monomer mixture of surplus, the deionized water of surplus and surplus ammonium persulphate are prepared simultaneously, start to drip functional polymerization single polymerization monomer (COPS-2) when the polymerization main monomer mixture of surplus remains 1/2, the all materials of this step dropwise in 3.5h, are then warming up to 90 DEG C of insulation reaction 1h;
(4) after step (3) reaction terminates, be cooled to 50 DEG C, by ammoniacal liquor adjust ph to 8, there is described in obtaining after cooling the benzene emulsion of excellent freeze-thaw stability, be designated as benzene emulsion 2;
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
38.2% water, 0.3% Tao Shi spy fall apart well
tM731A, 0.6%EMULGEN709 wetting agent, 2%SS-I nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), the clean taste film coalescence aid of 1%GVE, 0.3% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.2% sanitas Tao Shi ROCIMA
tM631 and 10% benzene emulsion 2.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.1% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 28% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 6% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 4.2% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 2 and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as sample 2.
Embodiment 3
Described benzene emulsion (i.e. styrene-acrylate emulsion) adopts core-shell emulsion polymerization legal system standby and obtains, raw materials used component and consumption as follows:
Polymerization main monomer: 65g vinylbenzene (St), 35g butyl acrylate (BA);
Other material: 2g methacrylic acid (MAA), the functional polymerization single polymerization monomer of 0.6g (COPS-2), 0.5g anionic-nonionic compound emulsifier (KL-70), 0.6g ammonium persulphate (APS), 0.6g sodium bicarbonate, 100g deionized water;
Wherein, functional polymerization single polymerization monomer (COPS-2) is identical with functional polymerization single polymerization monomer described in embodiment 1; Anionic-nonionic compound emulsifier (KL-70) is identical with anionic-nonionic compound emulsifier described in embodiment 1;
The second-order transition temperature (Tg) of described benzene emulsion is 40 DEG C.
The described preparation method with the benzene emulsion of excellent freeze-thaw stability is as follows:
(1) sodium bicarbonate, anionic-nonionic compound emulsifier (KL-70), first part's ammonium persulphate (25% of initiator gross weight) and first part's deionized water (70% of water gross weight) are added in reactor, mixing post-heating;
(2) polymerization main monomer and methacrylic acid are mixed to get polymerization main monomer mixture, question response actuator temperature is heated to 80 DEG C, in reactor, drip polymerization main monomer mixture (10% of polymerization main monomer mixture total weight amount), dropwise in 10min, insulation 20min;
(3) in reactor, then drip the solution that the polymerization main monomer mixture of surplus, the deionized water of surplus and surplus ammonium persulphate are prepared simultaneously, start to drip functional polymerization single polymerization monomer (COPS-2) when the polymerization main monomer mixture of surplus remains 1/2, the all materials of this step dropwise in 3.5h, are then warming up to 90 DEG C of insulation reaction 1h;
(4) after step (3) reaction terminates, be cooled to 50 DEG C, by ammoniacal liquor adjust ph to 8, there is described in obtaining after cooling the benzene emulsion of excellent freeze-thaw stability, be designated as benzene emulsion 3.
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
35% water, 0.3% Tao Shi spy fall apart well
tM731A, 0.6%EMULGEN709 wetting agent, 3%SS-II nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), the clean taste film coalescence aid of 1%GVE, 0.4% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.3% sanitas Tao Shi ROCIMA
tM631 and 12% benzene emulsion 3.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.2% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 28% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 5% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 2% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 3 and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be that under the condition of 1000rpm, middling speed mixes 25 minutes, loading barrel packaging at rotating speed, obtain latex coating, be designated as sample 3.
Embodiment 4
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
33.65% water, 0.4% Tao Shi spy fall apart well
tM731A, 0.6%EmulsogenLCN407 (Clariant), 1%SS-II nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), the clean taste film coalescence aid of 1.2%GVE, 0.4% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.35% sanitas Tao Shi ROCIMA
tM631 and 15% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.2% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 25% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 5% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 3.65% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as sample 4.
Comparative example 1
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
41% water, 0.3% Clariant EmulsogenLCN407,1%SS-I nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), 0.9%GV100 film coalescence aid, 0.2%RHODOLINE681F defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.2% sanitas sky occasion
nB203 and 9% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, non-ionic wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.1% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 30% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 6% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 5% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.1% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, comparative sample 1.
Comparative example 2
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
41% water, 0.3% Tao Shi spy fall apart well
tM1124 dispersion agents, 1%SS-I nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), 0.9%GV100 film coalescence aid, 0.2%RHODOLINE681F defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.2% sanitas sky occasion
nB203 (buying ground is Guangzhou Guangdong) and 9% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anionic dispersing agents, film coalescence aid, first part's defoamer (its consumption is 0.1% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 30% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 6% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 5% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.1% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as comparative sample 2.
Comparative example 3
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
34.25% water, 0.2% Tao Shi spy fall apart well
tM731A, 0.2% Clariant EmulsogenLCN407,1%SS-II nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), the clean taste film coalescence aid of 1.2%GVE, 0.4% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.35% sanitas Tao Shi ROCIMA
tM631 and 15% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.2% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 25% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 5% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 4.25% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as comparative sample 3.
Comparative example 4
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
38% water, 0.3% Tao Shi spy fall apart well
tMthe clean taste film coalescence aid of 731A, 0.6%EMULGEN709 wetting agent, 1%GVE, 0.4% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.3% sanitas Tao Shi ROCIMA
tM631 and 12% benzene emulsion 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.2% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 28% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 5% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 5% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Benzene emulsion 1 and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as comparative sample 4.
Comparative example 5
Have an internal wall emulsion coating for excellent freeze-thaw stability, the main ingredient of described internal wall emulsion coating and mass percent are:
38.2% water, 0.3% Tao Shi spy fall apart well
tM731A, 0.6%EMULGEN709 wetting agent, 2%SS-I nano-dispersed colloid (nanosecond science and technology company is initiated in Beijing), the clean taste film coalescence aid of 1%GVE, 0.3% Blackburn CF439 defoamer, 0.4% hydroxyethylcellulose thickener (HS30000YP2 thickening material), 5% rutile titanium white powder, 12% kaolin, 5% talcum powder, 25% water-ground limestone, 0.2% sanitas Tao Shi ROCIMA
tM631 and 10% outsourcing benzene emulsion.
Outsourcing benzene emulsion is produced by the good Chemical Co., Ltd. of Shanghai Poly, and the trade mark is the styrene-acrylate emulsion of BLJ-816, and second-order transition temperature is 23 DEG C.Test its freeze-thaw stability according to GB/T20623-2006, freeze-thaw cycle index is 1.
The described preparation method with the internal wall emulsion coating of excellent freeze-thaw stability is as follows:
By mass percentage, anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer (its consumption is 0.1% of latex coating total mass), first part's thickening material (its consumption is 0.2% of latex coating total mass) is added respectively in first part's water (its consumption is 28% of latex coating total mass), under the condition of rotating speed 400rpm, low speed is uniformly dispersed 10 minutes, obtains slurry; Adding nano-dispersed colloid, pigment, filler more in the slurry, is under the condition of 1400rpm at rotating speed, high speed dispersion, and making beating is ground to fineness≤60 μm; Reduce rotating speed to 1000rpm, sanitas, second section water (its consumption is 6% of latex coating total mass) and second section thickening material (its consumption is 0.2% of latex coating total mass) mixed solution is added successively in slurry, then add Part III water (its consumption is 4.2% of latex coating total mass) flushing pipe again, be that under the condition of 1000rpm, middling speed disperses 10 minutes at rotating speed; Outsourcing benzene emulsion and second section defoamer (its consumption is 0.2% of latex coating total mass) is added in the mixture after dispersion, be under the condition of 1000rpm at rotating speed, after middling speed mixes 25 minutes, loading barrel packaging, obtain latex coating, be designated as comparative sample 5.
Performance test:
1, freeze-thaw stability test:
The freeze-thaw stability of gained sample 1 ~ 4 and comparative sample 1 ~ 5 is tested with reference to GB/T20623-2006.Take out after refrigerated tank test sample being placed in (-10 ± 2) DEG C freezes 18h, then under (23 ± 2) DEG C condition, placing 6h, is once complete freeze-thaw cycle.Open container, fully stir test sample, if there is no lump, cohesion and separation phenomenon, then repeat freeze-thaw cycle.Often by 1 time, freeze thawing index increases by 1, result numeral, and the freeze-thaw stability of the larger expression emulsion of numeral is better.
2, latex coating viscosity test:
Adopt STM-III stormer viscosity meter, probe temperature: (23 ± 1) DEG C.
Test the viscosity after the initial viscosity of gained sample 1 ~ 4 and comparative sample 1 ~ 5, several times freeze-thaw cycle as stated above, it is as shown in the table for result:
Table 1 sample freeze-thaw stability detected result
As can be seen from table 1 test result, only containing anionic dispersing agents and wherein a kind of comparative sample of non-ionic wetting agent 1 and comparative sample 2, the comparative sample 3 that anion-nonionic composite diffusion wetting agent content is less, the freeze-thaw stability of comparative sample 4 containing nano-dispersed colloid is all very poor, and after freeze-thaw cycle 1 to 2 times, viscosity changes greatly; Sample 1 ~ 4 freeze-thaw stability implemented according to invention formula is all better.This illustrates, when preparing latex coating, interpolation anion-nonionic composite diffusion wetting agent and nano-dispersed colloid are conducive to the freeze-thaw stability improving product, and the addition of anion-nonionic composite diffusion wetting agent must not be very few.
As can be seen from table 1 test result, comparative sample 5 freeze-thaw stability adopting outsourcing benzene emulsion to prepare is very poor, and after freeze-thaw cycle 1 time, viscosity changes greatly.Visible when only having styrene-acrylate emulsion to have excellent freeze-thaw stability, the anion-nonionic composite diffusion wetting agent of described certain content, nano-dispersed colloid competence exertion synergy, the common freeze-thaw stability promoting latex coating; Otherwise this synergy will be suppressed, the freeze-thaw stability of latex coating is poor.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. there is an internal wall emulsion coating for excellent freeze-thaw stability, it is characterized in that: described latex coating feed composition comprises water, anion-nonionic composite diffusion wetting agent, nano-dispersed colloid, film coalescence aid, defoamer, thickening material, color stuffing, sanitas and styrene-acrylate emulsion.
2. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 1, it is characterized in that: described anion-nonionic composite diffusion wetting agent is the mixture of anionic dispersing agents and non-ionic wetting agent; Described anionic dispersing agents is polyphosphoric acid salt dispersion agent or polyacrylic salt dispersant; Described non-ionic wetting agent is alkyl polyoxyethylene ether class wetting agent; In described anion-nonionic composite diffusion wetting agent, the mass ratio of anionic dispersing agents and non-ionic wetting agent is (1:1) ~ (1:2);
Described thickening material is Natvosol class thickening material; Described color stuffing is pigment and filler.
3. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 2, it is characterized in that: polyphosphoric acid salt dispersion agent is the lucky Buddhist nun POLYRONNC in German Bake; Polyacrylic salt dispersant is that Tao Shi spy is good loose
tM1124 or special good loose
tM731A; Polyethenoxy ether class wetting agent is alkyl polyoxyethylene ether; Polyethenoxy ether class wetting agent is Clariant EmulsogenLCN407 or EMULGEN709;
Described thickening material is Clariant Natvosol HS30000YP2 or Aksu Natvosol BermocollEBS451FQ; Described pigment is Rutile type Titanium Dioxide;
Described filler is the mixture of kaolin, talcum powder and water-ground limestone.
4. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 1, it is characterized in that: described nano-dispersed colloid is SS-I water nano hydrophobizing agent or the SS-II water nano hydrophobizing agent that the production of nanosecond science and technology company is initiated in Beijing;
Described film coalescence aid is the clean taste film coalescence aid of GVE or the GV100 film coalescence aid of the production of Shanghai Ji Wei Industrial Co., Ltd.;
Described defoamer is Blackburn CF439 or RHODOLINE681F;
Described sanitas is water mildow-proof antiseptic-germicide
or Tao Shi ROCIMA
tM631.
5. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 1, it is characterized in that: described styrene-acrylate emulsion prepares by the following method:
A pH buffer reagent, anionic-nonionic compound emulsifier, first part's initiator and first part's water add in reactor by (), mixing post-heating; Question response actuator temperature is heated to 78 ~ 82 DEG C, drips first part's polymerization main monomer, dropwises in 5 ~ 10min, insulation 20 ~ 30min;
B () drips the solution that second section polymerization main monomer, second section water and second section initiator are prepared in reactor simultaneously, start to drip functional polymerization single polymerization monomer when second section polymerization main monomer residue 1/2 ~ 1/3, the all materials of this step dropwise in 3 ~ 4h, are then warming up to 85 ~ 90 DEG C of insulation reaction 0.5 ~ 1h;
C () insulation terminates after, be cooled to 50 ~ 60 DEG C, with ammoniacal liquor adjust ph to 7 ~ 9, after cooling, obtain styrene-acrylate emulsion;
Described initiator is divided into first part's initiator and second section initiator, and the consumption of described first part initiator is 20 ~ 40% of initiator gross weight; Described moisture is first part's water and second section water, and the consumption of first part's water is 60 ~ 80% of water gross weight; Described polymerization main monomer is divided into first part to be polymerized main monomer and second section polymerization main monomer, and described first part polymerization main monomer is 8 ~ 15% of polymerization main monomer gross weight; In described styrene-acrylate emulsion, shell second-order transition temperature is 18 ~ 40 DEG C.
6. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 5, it is characterized in that:
Described anionic-nonionic compound emulsifier is have the one in the compound of formula I ~ formula III general structure:
In formula I ~ formula III, R
1, R
2, R
3and R
4independently be selected from C
1~ C
13straight-chain paraffin base, C
1~ C
13containing the alkyl of branched structure or C
2~ C
15hydroxyalkyl; M is the integer of 3 to 50; N is the integer of 3 to 50; X is-SO
3 -m
+,-SO
4 -m
+,-COO
-m
+in one; M
+for Na
+, K
+or NH
4 +;
Described functional polymerization single polymerization monomer to be a kind of or described functional monomer had in the compound of formula IV ~ formula V general structure be methacrylic acid with there is mixture a kind of in the compound of formula IV ~ formula V general structure:
In formula IV ~ formula V, R
5be selected from C
1~ C
13straight-chain paraffin base, C
1~ C
13containing the alkyl of branched structure or C
2~ C
15hydroxyalkyl; O is the integer of 3 to 50; X is-SO
3 -m
+,-SO
4 -m
+,-COO
-m
+in one; M
+for Na
+, K
+or NH
4 +;
The consumption with the compound of formula IV or formula V general structure of described functional polymerization single polymerization monomer is 0.2 ~ 0.6% of polymerization main monomer quality; The consumption of the methacrylic acid of described functional polymerization single polymerization monomer is 1 ~ 2% of polymerization main monomer quality; Described methacrylic acid adds along with being polymerized main monomer substep;
Described polymerization main monomer is that alkyl acrylate mixes with cinnamic, and described alkyl acrylate is butyl acrylate or Isooctyl acrylate monomer; In described polymerization main monomer, alkyl acrylate and cinnamic mass ratio are (48 ~ 35): (52 ~ 65);
Described initiator is the one in Sodium Persulfate, ammonium persulphate or Potassium Persulphate;
Described pH buffer reagent is NaHCO
3or NaHPO
4in one.
7. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 5, it is characterized in that: the consumption of described anionic-nonionic compound emulsifier is 0.5% ~ 1% of polymerization main monomer total mass;
The consumption of described initiator is 0.4% ~ 0.6% of polymerization main monomer total mass;
The consumption of described pH buffer reagent is 0.3% ~ 0.6% of polymerization main monomer total mass;
The consumption of described water is 100% ~ 150% of polymerization main monomer total mass.
8. there is the internal wall emulsion coating of excellent freeze-thaw stability according to claim 1, it is characterized in that: the consumption of described anion-nonionic composite diffusion wetting agent is 0.6 ~ 1% of latex coating total mass;
The consumption of described nano-dispersed colloid is 1 ~ 3% of latex coating total mass;
The consumption of described styrene-acrylate emulsion is 9 ~ 15% of latex coating total mass;
The consumption of described film coalescence aid is 8 ~ 10% of styrene-acrylate emulsion weight in latex coating; The consumption of described defoamer is 0.2 ~ 0.4% of latex coating total mass;
The consumption of described thickening material is 0.4 ~ 0.6% of latex coating total mass;
The consumption of described color stuffing is 3 ~ 10% of latex coating total mass;
In described filler kaolinic consumption be latex coating total mass 10 ~ 15%, talcous consumption be the consumption of 5 ~ 9% and dicalcium powder of latex coating total mass is 20 ~ 30% of latex coating total mass;
The consumption of described sanitas is 0.2 ~ 0.35% of latex coating total mass.
9., by the preparation method described in any one of claim 1 ~ 8 with the internal wall emulsion coating of excellent freeze-thaw stability, it is characterized in that: specifically comprise the following steps:
(1) defoamer is divided into first part's defoamer and second section defoamer, its mass ratio is (0.1 ~ 0.2): (0.1 ~ 0.2); Thickening material is divided into first part's thickening material and second section thickening material, its mass ratio is (0.2 ~ 0.3): (0.2 ~ 0.3); Described moisture is first part's water, second section water, Part III water, the consumption of the consumption > second section water of first part's water, the consumption of the consumption > Part III water of first part's water;
In first part's water, add anion-nonionic composite diffusion wetting agent, film coalescence aid, first part's defoamer, first part's thickening material respectively, be uniformly dispersed, obtain mixture;
(2) in mixture, add nano-dispersed colloid, pigment and filler, high speed dispersion, making beating is ground to fineness≤60 μm; Reduce rotating speed, in slurry, add sanitas, second section water and second section thickening material mixed solution successively, then add Part III water flushing pipe again, middling speed is uniformly dispersed, and obtains dispersed paste;
(3) paint: add styrene-acrylate emulsion and second section defoamer in the dispersed paste of step (2), middling speed mixes, and obtains internal wall emulsion coating.
10. there is described in claim 9 preparation method of the internal wall emulsion coating of excellent freeze-thaw stability, it is characterized in that: described in step (1), the rotating speed of dispersion is 400 ~ 450rpm, and the time of dispersion is 10 ~ 15min;
Described in step (2), the rotating speed of high speed dispersion is 1400 ~ 1500rpm; Described reduction rotating speed refers to that rotating speed reduces to 1000 ~ 1200rpm; The rotating speed of described middling speed dispersion is 1000 ~ 1200rpm, and the time of described middling speed dispersion is 10 ~ 15min;
The rotating speed of the dispersion of middling speed described in step (3) is 1000 ~ 1200rpm, and the time of described dispersion is 20 ~ 25min.
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