CN1398931A - Water-thinned latex paint containing nano calcium carbonate for cuter wall and its prepn process - Google Patents
Water-thinned latex paint containing nano calcium carbonate for cuter wall and its prepn process Download PDFInfo
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Abstract
The present invention is a water-thinned latex paint containing nanometer calcium carbonate for outer wall and its preparation process. The paint consists of nanometer calcium carbonate, modified polymer emulsion, other pigment and filler, assistant A, assistant B, assistant C and calcium carbonate slurry. The modified polymer emulsion consists of soft monomer and hard monomer in the mass ratio of 54/46 to 56/44, the soft monomer is methyl acrylate, ethyl acrylate or capryl acrylate; and the hard monomer is methyl methacrylate or styrene. The nanometer calcium carbonate as the paint solid component can disperse homogeneously in the latex paint without needing surface modification and the paint has raised performance.
Description
Technical field
The present invention relates to a kind of water based emulsion exterior coating and preparation method thereof, particularly relate to a kind of water emulsion coating that contains nano-calcium carbonate, all acrylic ester copolymer emulsion or latex of copolymer in cinnamic acrylic ester and preparation method thereof.
Technical background
Traditional building coating is divided into solvent reducible coatings and water-borne coatings two big classes usually.Because containing a large amount of volatile organic solvents in the solvent reducible coatings pollutes environment and is day by day replaced by environment-friendly type aqueous coating.Water emulsion coating is to be the coating of main film forming substance and color stuffing, auxiliary agent and water composition with the synthetic resins water miscible liquid.The major function of exterior coating is to decorate and protect the outer wall of buildings.As exterior coating should have tint retention well outside, also should have good water tolerance, resistance to soiling and weathering resistance, simultaneously, also should easy construction, reasonable price.Polyacrylate dispersion is the emulsion that has multiple performance and have many uses, and wherein, all acrylic ester copolymer emulsion, latex of copolymer in cinnamic acrylic ester successfully are used for building coating, and the performance that improves coating is played an important role.Typical all acrylic ester copolymer emulsion prescription is monomer butyl acrylate 28.46, methyl methacrylate 14.45, methacrylic acid 0.876, emulsifying agent alkylbenzene polyethers sodium sulfonate 1.31, initiator ammonium persulfate 0.175, WATER AS FLOW MEDIUM 54.72.The formulation monomer butyl acrylate 22.7 of typical latex of copolymer in cinnamic acrylic ester; vinylbenzene 21.9; methyl methacrylate 1.9; methacrylic acid 1.0; emulsifying agent MS-1 2.4, protective colloid sodium polymethacrylate 1.4, initiator ammonium persulfate 0.24; buffer reagent sodium bicarbonate 0.22, WATER AS FLOW MEDIUM 48.3.(drawing) from " polymer emulsion composition principle performance and application " Chemical Industry Press.
Nano-calcium carbonate extensively receives publicity as a kind of new type functional packing material.Reported the application of nano-calcium carbonate in the amino varnish of polyester in " nano-calcium carbonate surface modification and in coating applied research " (1999 the 2nd phases of Beijing University of Chemical Technology's journal) to surface modification.Nanometer grade calcium carbonate is compared with common micron order lime carbonate, directly applies in the organic medium to have two shortcomings: the one, the particle surface energy height is in the thermodynamics unsteady state, very easily assemble agglomerating, thereby influenced the effect of nano-calcium carbonate; Lime carbonate surface hydrophilic oleophobic is difficult to disperse in organic medium, and does not have bonding force between the base-material, easily causes boundary defect, causes material property to descend.So, must carry out surface modification to nano-calcium carbonate.Disclosing its weight of a kind of exterior coating in " emulsion exterior coating and preparation method thereof " (Chinese patent application number 01107541.4) forms: color stuffing 25～35%, nanoparticle 2.5～4%, auxiliary agent A 1.6～1.9%, auxiliary agent B 0.6～1.0%, polymer emulsion 35～55%, auxiliary agent C 3～6%, all the other are water.The amount that nanoparticle adds in this coating is less, and need carry out pre-treatment to nanoparticle could be dispersed in nanoparticle between the binder resin.The preparation of coating need be passed through process of lapping.
Summary of the invention
The objective of the invention is to propose a kind of water based emulsion exterior coating and preparation method who contains nano-calcium carbonate, this coating contains nano-calcium carbonate, all acrylic ester copolymer emulsion or latex of copolymer in cinnamic acrylic ester, nano-calcium carbonate can be dispersed in the water emulsion coating, can improve the performance of coating comprehensively.In the coating preparation process, do not need Nano particles of calcium carbonate is carried out surface modification treatment, do not need to carry out milled processed yet, simplified production technique, saved production cost.
The water based emulsion exterior coating is to be the coating that main film forming substance and color stuffing, auxiliary agent and water are formed with the water-based emulsion.Contain nano-calcium carbonate in the color stuffing of the water based emulsion exterior coating that the present invention proposes, filmogen is polymer-modified emulsion, (A) system component (mass fraction): (1) nano-calcium carbonate: 4～10; (2) polymer-modified emulsion: 35～50; (3) other color stuffings: 17～29; (4) auxiliary agent A: 0.40～0.56; (5) auxiliary agent B: 0.5～1.1; (6) auxiliary agent C:0.74～1.2; (7) calcium carbonate serosity water: 12～30.(B) prescription of polymer-modified emulsion: (1) monomer: form by soft monomer and hard monomer, soft monomer is ethyl propenoate, butyl acrylate or Octyl acrylate, hard monomer is methyl methacrylate or vinylbenzene, soft monomer: hard monomer (mass ratio)=54: 46～56: 44; (2) emulsifying agent is 2%～3% of a monomer total amount; (3) initiator is an ammonium persulphate, is 0.1%～0.3% of monomer total amount; (4) the 3rd component methacrylic acids (MAA) are 1% of monomer total amounts; (5) deionized water is 128%～147% of a monomer total amount; (6) emulsion solid content is 40%～44%.
The particle diameter of nano-calcium carbonate is preferably in below the 50nm in the coating of the present invention.
Other color stuffings are at least a in titanium dioxide, kaolin, zinc sulfide white, talcum powder, the barite in the coating of the present invention.
Auxiliary agent A is dispersion agent or dispersion agent and wetting agent in the coating of the present invention.
Auxiliary agent B is at least a in film coalescence aid, multifunctional assistant, mould inhibitor, the sterilant in the coating of the present invention.
Auxiliary agent C is at least a in frostproofer, defoamer, pH regulator agent, the thickening material in the coating of the present invention.
The emulsifying agent of polymer-modified emulsion is at least a in sodium lauryl sulphate (SDS), alkylphenol polyoxyethylene (OP-10), polyoxyethylene octylphenol ether (10) the sulfocarboxylic acid esters (MS-1) in the coating of the present invention.
The preparation method of coating of the present invention is prepared into the polymer-modified emulsion of membrane substance earlier, be mixed with coating with color stuffing, auxiliary agent and water again, working method is as follows, (A) preparation of polymer-modified emulsion: (1) joins in the stirred reactor with whole emulsifying agents (making solvent with 50% of the total consumption of deionized water) earlier; (2) soft monomer and hard monomer are divided into two portions use separately, the consumption of the consumption of first part's soft monomer and first part's hard monomer is respectively 8%～20% of total consumption of soft monomer and the total consumption of hard monomer; (3) add first part's soft monomer and first part's hard monomer in the reactor; When (4) the question response system reaches kick off temperature, add half (making solvent) of the total consumption of initiator, when reacting to " turning blue " state, keep constant temperature under polymerization temperature etc. system with 1/4 of the total consumption of deionized water; (5) again methacrylic acid is divided into two, is blended in respectively in second section soft monomer and the second section hard monomer, splash in the lump in the stirred reactor with remaining initiator (making solvent) again with 1/4 of the total consumption of deionized water; (6) continue reaction again and finish, obtain polymer-modified emulsion until polyreaction.(B) preparation process of coating is as follows: (1) raw material solid content is 23%～26% nano-calcium carbonate slurries, adds the in addition 150 rev/mins of stirrings of nano-calcium carbonate slurries in container, adds auxiliary agent A and with 700 rev/mins of high-speed stirring; (2) add other color stuffings, continue with 700 rev/mins of stirrings, with 800 order net filtrations; (3) in another container, add polymer-modified emulsion, auxiliary agent B, with 150 rev/mins of stirring at low speed 5 minutes; Stirring velocity is brought up to 250 rev/mins again, the color stuffing after add filtering reduces stirring velocity to 150 rev/min; (4) add auxiliary agent C, regulate viscosity, regulate the pH value between 8～9, froth breaking, discharging obtains coating.
Lime carbonate used in the present invention is the nano-calcium carbonate of particle diameter below 100nm, and particle diameter preferably is no more than 50nm.The present invention can give coating with the peculiar series of effects of nano-calcium carbonate calcium material, comprehensively improves every performance of coating.
Coating raw material of the present invention adopts the nano-calcium carbonate slurries.Because calcium carbonate particles is present among the water with nano level state, its surperficial possess hydrophilic property, and particle diameter is minimum has an extremely strong adsorptive power, can adsorb the periphery that one deck water molecules is enclosed in Nano particles of calcium carbonate, and the nano-calcium carbonate filler does not need to carry out surface treatment procedure.Owing to the usage ratio height of nano-calcium carbonate in color stuffing, greatly reduce the average fineness of color stuffing in the formulation for coating material of the present invention, therefore in the process of preparation coating, need not grind.The solid content of nano-calcium carbonate slurries used in the present invention contains enough slurry water owing in the raw material nano calcium carbonate serosity, so coating can additionally not add water in process for preparation 23%～26%.The nano-calcium carbonate slurry solid content is low excessively, can make the solid content of whole coating finished product low excessively; The nano-calcium carbonate slurry solid content is too high, and the nano-calcium carbonate of aqueous phase is easy to generate the phenomenon of " reunion ", can not bring into play the performance advantage of nanometer particle and will influence coating property.
Why the present invention can use the nanometer grade calcium carbonate filler of large portion to improve the performance of coating, make calcium carbonate particles not reunite not carrying out reaching nano level dispersion under the surface-treated situation in coating, this is that the prescription of emulsion is relevant with the polymeric working method with the coating filmogen.Though the same the 3rd component of using methacrylic acid (MAA) as emulsion of preparation method that the present invention is traditional with emulsion, its consumption only is 1% of a monomer total amount, wants much less than traditional method consumption.Acid can damage the stability of emulsion to a certain extent, method of the present invention is to add acid after polymerization system is initiated again, its working method is that monomer is divided into two portions, first part is 8%～20% of a monomer total amount, 50% of first part's monomer and initiator total amount carried out initiation reaction earlier, is blended in respectively in remaining second section hard monomer and the second section soft monomer after methacrylic acid (MAA) is divided into two slowly to be added drop-wise among the reaction system in the lump again.The addition manner of this methacrylic acid can improve the combined state of emulsion and nano-calcium carbonate under the less prerequisite of emulsifying agent consumption, help improving the performance of coating.The present invention proposes soft or hard than within 54: 46～56: 44 scope.The monomeric soft or hard ratio of emulsion can influence the compound degree with nano-calcium carbonate, and will have influence on every performance of paint film.The solid content of the emulsion that the present invention proposes is between 40%～44%.The combined state of too high emulsion of the solid content of emulsion and nano-calcium carbonate can worsen, even can cause the obvious reunion of filler in recombination process; The solid content of emulsion is low excessively, can make the solid content of coating low excessively on the one hand, also can have a strong impact on the film forming properties of coating on the other hand.
The order of coating preparation of the present invention and the manner of formulation of process and traditional water emulsion coating are basic identical.When color stuffing suspension joins in the emulsion, add slowly, the stirring velocity of emulsion is wanted suitably simultaneously.The stirring velocity of this moment is crossed and low can be unfavorable for the color stuffing dispersion in coating, especially nano-calcium carbonate, reunites easily and loses nano level small-size effect and surface effects; The too high stability that can destroy emulsion of stirring velocity causes simultaneously to splash and is unfavorable for production operation.It is a surname for about 250 rev/mins that the present invention adopts so that the highest stirring velocity that splashing of liquid exceed not to take place.
The consumption of the non-nano level color stuffing that coating of the present invention is used is between 17～29.The color stuffing of other non-nano levels used in the present invention is normally used titanium dioxide, kaolin, talcum powder, barite, zinc sulfide white etc.The use of filler can reduce production costs, and gives the performance of some particular requirement of coating.
The used auxiliary agent A of coating of the present invention is general dispersion agent, wetting agent.For example: Disperbyk161 (polymer that contains close pigment group), the Disperbyk171 (the segmented copolymer emulsion that has acid close pigment group) of the Atsurf3222 of the TENL070 of dispersion agent Henkel company (complicated sulfonamide derivatives), Britain ICI company (a kind of alkylation nonionogenic tenside), BYK Chemie company, RHODOLINEDP-270 (a kind of low molecular weight sodium polyacrylate) etc., wetting agent: alkylphenol polyoxyethylene (OP-10) etc.
The used auxiliary agent B of coating of the present invention is general film coalescence aid, multifunctional assistant, mould inhibitor, sterilant etc.For example: film coalescence aid NEXTCOAT795 (2,2,4-trimethylammonium-1,3-pentanediol-mono isobutyrate), multifunctional regulator AMP-95 (2-amino-2-methyl-1-propanol) is a kind of lower molecular weight organic amino lactone value conditioning agent, effect with dispersion color stuffing reduces the smell of coating simultaneously effectively, the KathonLXE of rohmhaas company and Rozone2000, the PreventolA4 of German Baye company has the mouldy effect that prevents coating.
The used auxiliary agent C of coating of the present invention is general frostproofer, defoamer, pH regulator agent, thickening material etc.For example: antifreeze glycol or propylene glycol, defoamer 681F (a kind of mineral oil antifoam agent), pH regulator agent available adjustment agent AMP-95, rheology thickening material RHEOLATE 430.
Coating provided by the invention is the very little coating of a kind of average fineness, can make coatingsurface very flat, the glossiness height.From microtexture, the surface of coating is very flat, and projection is higher than that the macrobead of coating surface is few, and when running into external friction, suffered resistance reduces greatly, shows performances such as the scrubbing resistance that can improve coating, scrape resistant, wear-resisting, anti-pickup on macro property.Appearance of coat is full, and opacifying power is good, and the time of doing solid work is short.The resistance to settling of color stuffing, the thixotropy of coating have clear improvement.Need not add any flow agent in the formulation for coating material, the levelling effect is just fine.
Coating and traditional calcium carbonate coating with the embodiment of the invention 1 preparation are done contrast, for more convenient, traditional lime carbonate is with 1～2 μ m light calcium carbonate, and other are identical with embodiment 1, coating property is tested according to the relevant regulations of GB, and its test result is seen attached list.
From subordinate list as can be seen, exterior coating of the present invention obviously is better than traditional coating at multinomial performances such as fineness, glossiness, paint film appearance, hardness, snappiness, wear resistance, abrasion resistance, polluting proofing property, opacifying power, sticking power, resistance to settlings.
With the sample of atomic force microscope observation coating, the dispersion of the Nano particles of calcium carbonate of coating of the present invention in coating do not have agglomeration in order as can be seen.And be higher than nano-calcium carbonate calcium paint of the present invention far away as the surface degree that is uneven of the micro-calcium carbonate coating of reference.
Specific embodiment
The preparation of the polymer-modified emulsion of embodiment 1A. (usage quantity is a mass fraction):
Adopt all acrylic ester polymerization: use sodium lauryl sulphate (SDS) and alkylphenol polyoxyethylene (OP-10) as compound emulsifying agent, wherein the consumption of sodium lauryl sulphate (SDS) is 0.25 part, alkylphenol polyoxyethylene (OP-10) consumption is 0.55 part, with these two kinds of emulsifier mix heating for dissolving in 25 parts of deionized waters.The emulsifier solution that dissolving is finished joins in the reactor, stirs, heats up.Add 2.2 parts of 1.8 parts of methyl methacrylates (total consumption 10%) and butyl acrylates (total consumption 10%) in the reactor, be warming up to 75 ℃ and add and use 0.02 part of 13.8 parts of dissolved ammonium persulphate of deionized water.Waiting temperature rise to 80 ℃ of monomers begin to be initiated, keep 80 ℃ of temperature of reaction when " turning blue " phenomenon obviously occurring etc. system, beginning drips 19.8 parts of 16.2 parts of methyl methacrylates (total consumption 90%) and butyl acrylates (always 90% of consumption) simultaneously, in this methyl methacrylate and butyl acrylate, respectively mixed 0.2 part of methacrylic acid, also drip in reactor simultaneously with 0.02 part of 20 parts of dissolved ammonium persulphate of deionized water, the control rate of addition makes all drip thing and dropwises about 1 hour evenly.Continue reaction about 3.5 hours afterwards, cooling discharging obtains polymer-modified emulsion.Polymer-modified emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 1.8+16.2=18,
Butyl acrylate (soft monomer) 2.2+19.8=22,
Total amount is 40; Soft monomer: hard monomer=22: 18=55: 45,
Methacrylic acid: 0.2+0.2=0.4 accounts for 1% of the total consumption of total monomer,
Emulsifying agent: account for the total consumption 2% of monomer,
Initiator: account for the total consumption 0.1% of monomer,
Deionized water: 58.8, account for the total consumption 147% of monomer,
Recording the actual solid content of emulsion is 42%.Because the evaporation of moisture and monomer volatilization in polymerization process, to the solid content that makes emulsion and design solid content error to some extent.B. prepare latex coating: (usage quantity is a mass fraction)
In container, add commercially available solid content and be 32 parts in 25% nano-calcium carbonate slurries (specification is 50nm, below identical) (wherein: 8 parts in lime carbonate, 24 parts of slurry water), 150 rev/mins of stirrings of start low speed.Add auxiliary agent A: 0.43 part of dispersion agent DP-270,700 rev/mins of stirrings slowly add other color stuffings successively after 10 minutes: 13 parts in rutile titanium white powder, 5 parts of kaolin, 2 parts in zinc sulfide white, continued dispersed with stirring 20 minutes, and stop to stir.Filter one time with 800 purpose stainless (steel) wires, stand-by.In another container, add 46 parts of polymer-modified emulsions, 0.3 part of auxiliary agent B: AMP-95,795 0.1 parts of film coalescence aid, 0.2 part of Rozone2000, use big stirring rake to stir 5 minutes for 150 rev/mins.The stirring velocity accent soon to not causing about 250 rev/mins of the top speed of splashing, is added the color stuffing slurries that dispersing and filtering is good then lentamente, keep this stirring velocity and continue slowly to reduce after 10 minutes stirring velocity to 150 commentaries on classics branch, continuation was stirred 2 hours.Add auxiliary agent C: 0.44 part of antifreeze glycol, 0.02 part of defoamer 681F, pH regulator agent: AMP-95 0.07 part of (the pH value of regulating coating is between 8～9), 430 0.44 parts of thickening materials (adjusting viscosity).Discharging obtains coating.Formulation for coating material:
8 parts of nano-calcium carbonates, 20 parts of other pigment, 46 parts of emulsions, 0.43 part of auxiliary agent A, 0.6 part of auxiliary agent B, 0.97 part of auxiliary agent C, 24 parts in calcium carbonate serosity water, coating solid content are 47.3%.
This coating property test result is seen attached list.This coating has splendid thixotropy, is easy to construction, and paint film appearance is plentiful bright and clean, and the good springiness of paint film, strong adhesion (top grade), washability are more than 20,000 times, and polluting proofing property can excellence (≤18%).Brushing went through for two years at exterior wall, and wall paint light as new is without any peeling off cracking phenomena.Coating canning and storage 1 year does not have layering, caking, has good preservation stability.
The preparation of the polymer-modified emulsion of embodiment 2A. (usage quantity is a mass fraction):
Adopt the cinnamic acrylic ester polymerization: emulsifying agent is selected 1.2 parts of MS-1 for use, with joining in the reactor after 20 parts of heating for dissolving of deionized water dissolving, stir, heat up, add 4.32 parts of 3.68 parts of vinylbenzene (total consumption 20%) and butyl acrylates (always 20% of consumption) in the reactor, be warming up to 72 ℃, and add with 0.06 part of 20 parts of dissolvings of deionized water ammonium persulphate, monomer begins to be initiated, when " turning blue " phenomenon obviously occurring etc. system, temperature recovery to 75 ℃, it is constant that controlled temperature keeps, drip 17.28 parts of 14.72 parts of vinylbenzene respectively having mixed 0.2 part of methacrylic acid respectively and butyl acrylates simultaneously, also in reactor, drip simultaneously with 0.06 part of 18.3 parts of dissolved ammonium persulphate of deionized water.Be warming up to 95 ℃ after dropwising, be incubated 30 minutes.Cooling discharging obtains polymer-modified emulsion.Polymer-modified emulsion formulations:
Monomer: vinylbenzene (hard monomer) 3.68+14.72=18.4,
Butyl acrylate (soft monomer) 4.32+17.28=21.6,
Total amount is 40; Soft monomer: hard monomer=21.6: 18.4=54: 46,
Methacrylic acid: 0.2+0.2=0.4 accounts for the total consumption 1% of monomer,
Emulsifying agent: account for the total consumption 3% of monomer,
Initiator: account for the total consumption 0.3% of monomer,
Deionized water: 58.3, account for the total consumption 145.7% of monomer,
Recording the actual solid content of emulsion is 40%.B. prepare latex coating (usage quantity is a mass fraction):
Working method is with embodiment 1, with commercially available solid content 25% 40 parts in nano-calcium carbonate slurries (wherein: 10 parts in lime carbonate, 30 parts of slurry water), auxiliary agent A: 0.56 part of dispersant A tsurf3222, other color stuffings: 12 parts in rutile titanium white powder, 8 parts of kaolin, 2.5 parts of talcum powder, 35 parts of polymer-modified emulsions, 0.47 part of auxiliary agent B: AMP-95,795 0.2 parts of film coalescence aid, 0.3 part of PreventolA4, auxiliary agent C: 0.57 part of frostproofer propylene glycol, defoamer 681F0.03 part, 0.01 part of pH regulator agent: AMP-95,430 0.39 parts of thickening materials.Formulation for coating material:
10 parts of nano-calcium carbonates, 22.5 parts of other pigment, 35 parts of emulsions, 0.56 part of auxiliary agent A, 0.97 part of auxiliary agent B, 1.0 parts of auxiliary agent C, 30 parts in calcium carbonate serosity water, coating solid content 46.5%.
The coating surface drying time is no more than 1 hour, and the time of doing solid work is no more than 2 hours, and second painting does not have difficulty, good leveling property (≤5 minutes), sagging not, easy construction; Paint film appearance is plentiful, smooth bright and clean, the snappiness of paint film good (20 ℃, 0.5mm did not split in 20 hours), strong adhesion (top grade), hardness height (3H), alkaline-resisting water-based (48 hours are no abnormal), washability excellence (20,000 times are not show-through), minimum film-forming temperature is-1.6 ℃, can construct under the zero degree environment, barreled stores any sedimentation phenomenon half a year.
The preparation of the polymer-modified emulsion of embodiment 3A. (usage quantity is a mass fraction)
Adopt the cinnamic acrylic ester polymerization: join with 1.2 parts of MS-1 in 20 parts the deionized water, stir, heat up, add 2.2 parts of 1.8 parts of vinylbenzene and butyl acrylates, be warming up to 72 ℃ and 0.06 part of 18.3 parts of dissolved ammonium persulphate of deionized water of adding, monomer causes when system begins " turning blue ", temperature keeps about 75 ℃, drip 20.2 parts of each 15.8 parts of vinylbenzene that mixed 0.2 part of methacrylic acid respectively and butyl acrylates, drip with 0.06 part of 20 parts of dissolved ammonium persulphate of deionized water simultaneously, be warming up to 95 ℃ after dropwising, continue reaction 0.5 hour, cooling, discharging when being stirred to cool to room temperature.Polymer-modified emulsion formulations:
Monomer: vinylbenzene (firmly) 1.8+15.8=17.6,
Butyl acrylate (soft) 2.2+20.2=22.4,
Total amount is 40; Soft monomer: hard monomer=22.4: 17.6=56: 44,
Methacrylic acid: 0.2+0.2=0.4 accounts for 1% of the total consumption of monomer,
Emulsifying agent: account for the total consumption 3% of monomer,
Initiator: account for the total consumption 0.3% of monomer
Deionized water: 58.3, account for 145.7% of the total consumption of monomer,
Recording the actual solid content of emulsion is: 42%.B. prepare latex coating (usage quantity is a mass parts):
Working method is with embodiment 1, with solid content 24% 35 parts in nano-calcium carbonate slurries (wherein: 8.4 parts in lime carbonate, 26.6 parts of slurry water), auxiliary agent A: 0.5 part of dispersion agent DP-270, other color stuffings: 13 parts in rutile titanium white powder, 5 parts of kaolin, 2.6 parts of talcum powder, 42 parts of polymer-modified emulsions, 0.49 part of auxiliary agent B: AMP-95,795 0.08 parts of film coalescence aid, 0.3 part of Rozone2000, auxiliary agent C: 0.54 part of ethylene glycol, 0.02 part of 0.02 part of defoamer 681F, pH regulator agent: AMP-95,430 0.45 parts of thickening materials.Formulation for coating material:
8.4 parts of nano-calcium carbonates, 20.6 parts of other pigment, 42 parts of emulsions, 0.5 part of auxiliary agent A, 0.87 part of auxiliary agent B, 1.03 parts of auxiliary agent C, 26.6 parts in calcium carbonate serosity water, coating solid content are 46.65%.
This coating has splendid thixotropy, pigment suspension.Brushing is at exterior wall, and wall surface levelling light after a year is without any peeling off cracking phenomena.Wash-resistant property (2.5 ten thousand times are not show-through) and polluting proofing property energy (≤17%) excellence, whiteness reaches 93.96.
The preparation of the polymer-modified emulsion of embodiment 4A. (usage quantity is a mass parts):
Adopt all acrylic ester hot polymerization legal: with 0.84 part of 0.42 part of SDS and OP-10 as compound emulsifying agent, with these two kinds of emulsifier mix heating for dissolving in 11.2 parts of deionized waters.The emulsifier solution that dissolving is finished joins in the reactor, stirs, heats up.Add 2.3 parts of 1.8 parts of methyl methacrylates (total consumption 9.5%) and Octyl acrylates (total consumption 10%) in the reactor, be warming up to 75 ℃ and add and use 0.063 part of 25 parts of dissolved ammonium persulphate of deionized water.Waiting temperature gos up to 80 ℃, monomer begins to be initiated, keep 80 ℃ of temperature of reaction when " turning blue " phenomenon obviously occurring etc. system, begin to drip 20.8 parts of 17.1 parts of methyl methacrylates (total consumption 90.5%) and Octyl acrylates (always 90% of consumption), in this methyl methacrylate and butyl acrylate, respectively mixed 0.21 part of methacrylic acid, also drip in reactor with 0.063 part of 20 parts of dissolved ammonium persulphate of deionized water simultaneously, the control rate of addition dropwises about 1 hour evenly.Continue reaction about 3.5 hours, cooling discharging obtains polymer-modified emulsion.Polymer-modified emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 1.8+17.1=18.9,
Octyl acrylate (soft monomer) 2.3+20.8=23.1,
Total amount is 42; Soft monomer: hard monomer=23.1: 18.9=55: 45,
Methacrylic acid: 0.21+0.21=0.42, account for the total consumption of monomer 1%,
Compound emulsifying agent: account for 3% of the total consumption of monomer,
Initiator: account for 0.3% of the total consumption of monomer,
Deionized water: 56.2, account for 134% of the total consumption of monomer,
Recording the actual solid content of emulsion is 44%.B. prepare latex coating (usage quantity is a mass parts):
Working method is with embodiment 1, with solid content 26% 35 parts in nano-calcium carbonate slurries (wherein: 9.1 parts in lime carbonate, 25.9 parts of slurry water), auxiliary agent A: 0.5 part of dispersion agent TENLO70, other color stuffings: 15 parts in rutile titanium white powder, 7 parts of kaolin, 3 parts of talcum powder, 37.2 parts of polymer-modified emulsions, 0.53 part of auxiliary agent B: AMP-95,795 0.26 parts of film coalescence aid, PreventolA
40.31 part, auxiliary agent C: 0.6 part of propylene glycol, 0.02 part of 0.06 part of defoamer 681F, pH regulator agent: AMP-95,430 0.52 parts of thickening materials.Formulation for coating material:
9.1 parts of nano-calcium carbonates, 25 parts of other pigment, 37.2 parts of emulsions, 0.5 part of auxiliary agent A, 1.1 parts of auxiliary agent B, 1.2 parts of auxiliary agent C, 25.9 parts in calcium carbonate serosity water, the solid content of coating are 50.5%.
This coating is tested through GB, every excellent performance.Glossiness: 22.6, the wear resisting property excellence, snappiness (20 ℃, 0.5mm did not split in 20 hours), sticking power top grade (400 grams do not scratch), hardness 3H, washability 2.5 ten thousand times is stored not sedimentation half a year, does not lump.Paint film appearance is full bright and clean.Sagging not, thixotropy is strong, and workability is good.
The polymer-modified emulsion preparation of embodiment 5A. (usage quantity is a mass parts):
Adopt all acrylic ester polymerization: initiator is an ammonium persulphate, successively drop into half, 0.28 part of OP-100.58 part and SDS are as compound emulsifying agent, be dissolved in 20 parts the deionized water, stir, heat up, add 2.3 parts of 1.9 parts of methyl methacrylates and ethyl propenoates, after rising to 75 ℃, equitemperature adds with 0.0215 part of 15.67 parts of dissolved ammonium persulphate of deionized water, when " turning blue " phenomenon occurring etc. system, be warmed up to 80 ℃ and keep this temperature, drip 21.35 parts of 17.45 parts of methyl methacrylates all respectively having mixed 0.215 part of methacrylic acid and ethyl propenoates simultaneously, drip with 0.0215 part of 20 parts of dissolved ammonium persulphate of deionized water simultaneously, after dropwising about one hour, be incubated 3.5 hours.Cooling discharging obtains polymer-modified emulsion.Emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 1.9+17.45=19.35,
Ethyl propenoate (soft monomer) 2.3+21.35=23.65,
Total amount is 43; Soft monomer: hard monomer=23.65: 19.35=55: 45,
Methacrylic acid: 0.215+0.215=0.43 accounts for the total consumption 1% of monomer,
Emulsifying agent: account for the total consumption 2% of monomer,
Initiator: account for the total consumption 0.1% of monomer,
Deionized water: 55.67, account for the total consumption 129% of monomer,
Recording the actual solid content of emulsion is 44%.B. prepare latex coating: (usage quantity is a mass parts)
Working method is with embodiment 1,31.1 parts in nano-calcium carbonate slurries (wherein: 8.09 parts in lime carbonate, 23.01 parts of slurry water) with solid content 26%, auxiliary agent A: 0.46 part of dispersion agent DP-270, other color stuffings: 14 parts in rutile titanium white powder, 3 parts of kaolin, 50 parts of polymer-modified emulsions, 0.2 part of auxiliary agent B: AMP-95,795 0.1 parts of film coalescence aid, 0.2 part of Rozone2000, auxiliary agent C: 0.46 part of antifreeze glycol, 0.02 part of 0.02 part of defoamer 681F, pH regulator agent: AMP-95,430 0.44 parts of thickening materials.Formulation for coating material:
8.09 parts of nano-calcium carbonates, 17 parts of other pigment, 50 parts of emulsions, 0.46 part of auxiliary agent A, 0.5 part of auxiliary agent B, 0.94 part of auxiliary agent C, 23.01 parts in calcium carbonate serosity water, coating solid content are 47.1%
This paint thixotropy is good, and elasticity (20 ℃, 0.5mm, do not ftracture in 20 hours), strong adhesion, washability (2.5 ten thousand times are not show-through), polluting proofing property energy (≤14%), levelling property (≤3 minutes), resistance to settling (not sedimentation in a year is not lumpd), glossiness (25.37), wear resisting property good (top grade), whiteness (93.26).
The preparation of the polymer-modified emulsion of embodiment 6A. (usage quantity is a mass parts):
Adopt all acrylic ester polymerization: 0.49 part of 0.35 part of SDS and OP-10 is added in 20 parts of the deionized waters, stir, heat up, add 2.5 parts of 2 parts of methyl methacrylates and butyl acrylates, when rising to 75 ℃, equitemperature also adds with 0.021 part of 17 parts of dissolved ammonium persulphate of deionized water, temperature recovery to 80 ℃, monomer causes when system begins " turning blue ", keep 80 ℃ of temperature of reaction, drip 20.6 parts of 16.9 parts of methyl methacrylates respectively having mixed 0.21 part of methacrylic acid respectively and butyl acrylates, drip with 0.021 part of 20 parts of dissolved ammonium persulphate of deionized water simultaneously, about 1 hour, dropwise evenly.Continue reaction 3.5 hours afterwards, cooling, discharging when being stirred to cool to room temperature obtains polymer-modified emulsion.Emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 2+16.9=18.9,
Butyl acrylate (soft monomer) 2.5+20.6=23.1,
Total amount is 42; Soft monomer: hard monomer=23.1: 18.9=55: 45,
Methacrylic acid: 0.21+0.21=0.42 accounts for 1% of the total consumption of monomer,
Emulsifying agent: account for 2% of the total consumption of monomer,
Initiator: account for 0.1% of the total consumption of monomer,
Deionized water: 56.7, account for 135% of the total consumption of monomer.
Recording the actual solid content of emulsion is 43%.B. prepare latex coating (usage quantity is a mass fraction):
Working method is with embodiment 1,38.96 parts in nano-calcium carbonate slurries (wherein: 8.96 parts in lime carbonate, 30 parts of slurry water) with solid content 23%, auxiliary agent A: 0.51 part of dispersion agent DP-270, other color stuffings: 14.3 parts in rutile titanium white powder, 2.5 parts of kaolin, 2 parts of talcum powder, 40 parts of polymer-modified emulsions, 0.5 part of auxiliary agent B: AMP-95,795 0.11 parts of film coalescence aid, PreventolA
40.22 part, auxiliary agent C: 0.43 part of propylene glycol, 0.02 part of 0.02 part of defoamer 681F, pH regulator agent: AMP-95,430 0.43 parts of thickening materials.Formulation for coating material:
8.96 parts of nano-calcium carbonates, 18.8 parts of other pigment, 40 parts of emulsions, 0.51 part of auxiliary agent A, 0.83 part of auxiliary agent B, 0.9 part of auxiliary agent C, 30 parts in calcium carbonate serosity water, coating solid content are 45%.
This paint flow levelling (≤4 minutes), whiteness (90.32), glossiness (19.88), snappiness (20 ℃, 0.5mm radius-of-curvature, 20 hours leakless), sticking power (top grade), surface drying time (≤1 hour) is done solid work the time (≤2 hours) hardness (2H), washability (20,000 times are not show-through), wear resisting property excellence (750g, 300 go round and round a millstone damage quality≤0.0022g), polluting proofing property (≤20%), thixotropy is good, is easy to construction, sagging is not stored no sedimentation in a year.
The preparation of the polymer-modified emulsion of embodiment 7A. (usage quantity is a mass fraction):
Adopt the method for embodiment 1, different is, and first part's methyl methacrylate is 1.44 parts (total consumptions 8%), first part's butyl acrylate is 1.76 parts (total consumptions 8%), and the second section methyl methacrylate is that 16.56 parts (total consumptions 92%), second section butyl acrylate are 20.24 parts (total consumptions 92%).Polymer-modified emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 1.44+16.56=18,
Butyl acrylate (soft monomer) 1.76+20.24=22,
Total amount is 40; Soft monomer: hard monomer=22: 18=55: 45,
Methacrylic acid: 0.2+0.2=0.4 accounts for 1% of the total consumption of total monomer,
Emulsifying agent: account for the total consumption 2% of monomer,
Initiator: account for the total consumption 0.1% of monomer,
Deionized water: 58.8, account for the total consumption 147% of monomer.
Recording the actual solid content of emulsion is 40%.B. prepare latex coating: (usage quantity is a mass parts)
Working method is with embodiment 1,26 parts in nano-calcium carbonate slurries (wherein: 6 parts in lime carbonate, 20 parts of slurry water) with solid content 23%, auxiliary agent A: 0.4 part of dispersion agent DP-270, other color stuffings: 12 parts in rutile titanium white powder, 9 parts of kaolin, 5 parts of talcum powder, 2 parts in zinc sulfide white, 44 parts of polymer-modified emulsions, 0.4 part of auxiliary agent B: AMP-95,795 0.08 parts of film coalescence aid, 0.22 part of Rozone2000, auxiliary agent C: 0.45 part of antifreeze glycol, defoamer 681F0.016 part, 0.02 part of pH regulator agent: AMP-95,430 0.4 parts of thickening materials.Formulation for coating material:
6 parts of nano-calcium carbonates, 28 parts of other pigment, 44 parts of emulsions, 0.4 part of auxiliary agent A, 0.7 part of auxiliary agent B, 0.886 part of auxiliary agent C, 20 parts in calcium carbonate serosity water, coating solid content are 51.6%.
This coating whiteness 95.27, glossiness 24.4, opacifying power 142g/m
2, washability is more than 2.5 ten thousand times, not sedimentation in a year, and minimum film-forming temperature-2 ℃, second painting is accessible.
The preparation of the polymer-modified emulsion of embodiment 8A. (usage quantity is a mass fraction):
Adopt the method for embodiment 7, different is that butyl acrylate is changed to ethyl propenoate, and all the other are all identical.Polymer-modified emulsion formulations:
Monomer: methyl methacrylate (hard monomer) 1.44+16.56=18,
Ethyl propenoate (soft monomer) 1.76+20.24=22,
Total amount is 40; Soft monomer: hard monomer=22: 18=55: 45,
Methacrylic acid: 0.2+0.2=0.4 accounts for 1% of the total consumption of total monomer,
Emulsifying agent: account for the total consumption 2% of monomer,
Initiator: account for the total consumption 0.1% of monomer,
Deionized water: 58.8, account for the total consumption 147% of monomer.
Recording the actual solid content of emulsion is 40%.B. prepare latex coating: (usage quantity is a mass parts)
Working method is with embodiment 1,16 parts in nano-calcium carbonate slurries (wherein: 4 parts in lime carbonate, 12 parts of slurry water) with solid content 25%, auxiliary agent A: 0.4 part of dispersion agent DP-270,0.1 part of wetting agent OP-10, other color stuffings: 14 parts in rutile titanium white powder, 7 parts of kaolin, 4 parts of talcum powder, 4 parts in zinc sulfide white, 44 parts of polymer-modified emulsions, 0.41 part of auxiliary agent B: AMP-95,795 0.08 parts of film coalescence aid, 0.2 part of Rozone2000, PreventolA
40.1 part, auxiliary agent C: 0.38 part of antifreeze glycol, 0.01 part of 0.023 part of defoamer 681F, pH regulator agent: AMP-95,430 0.33 parts of thickening materials.Formulation for coating material:
4 parts of nano-calcium carbonates, 29 parts of other pigment, 44 parts of emulsions, 0.5 part of auxiliary agent A, 0.79 part of auxiliary agent B, 0.743 part of auxiliary agent C, 12 parts in calcium carbonate serosity water, coating solid content are 55.6%.
This coating fineness 55, whiteness 93.38, glossiness 24.5, washability is more than 2.5 ten thousand times, not sedimentation in a year, skinning not, minimum film-forming temperature-2 ℃, second painting is accessible.
Subordinate list
| Performance | The present invention (embodiment 1) | Traditional coating |
| Fineness (μ m) | ????25 | ????70 |
| Glossiness | ????23.6 | ????8.4 |
| Paint film appearance | Paint film is full, and is smooth bright and clean | Smooth, normal |
| Whiteness | ????94.92 | ????92.63 |
| Time of drying (surface drying) | ????55min | ????1h |
| Time of drying (doing solid work) | ????1h30min | ????3h45min |
| Hardness | ????3H | ????B |
| Snappiness (20 ℃, 0.5 millimeter radius, 20 hours) | Do not ftracture | Tiny slight crack is arranged |
| Wear resistance (g/750g, 300 change) | ????0.0008 | ????0.0255 |
| Abrasion resistance | 20,000 times are not show-through | 10,000 times show-through |
| Opacifying power (g/m 2) | ????113 | ????136 |
| Sticking power (400g) | Excellent | Difference |
| Polluting proofing property (whiteness loss %) | ????18 | ????36 |
| Alkaline-resisting water-based (48 hours) | No abnormal | No abnormal |
| Levelling property | Excellent | Excellent |
| Thixotropy | Excellent | Generally |
| 2 years settleabilities | Not sedimentation | Sedimentation |
| Minimum film-forming temperature (℃) | ????-1 | ????0 |
| Second painting | Normally | Normally |
Claims (8)
1, a kind of water based emulsion exterior coating that contains nano-calcium carbonate is to be the coating that main film forming substance and color stuffing, auxiliary agent and water are formed with the water-based emulsion, it is characterized in that: contain nano-calcium carbonate in the color stuffing, filmogen is polymer-modified emulsion, (A) system component (mass fraction):
(1) nano-calcium carbonate: 4～10;
(2) polymer-modified emulsion: 35～50;
(3) other color stuffings: 17～29;
(4) auxiliary agent A: 0.4～0.56;
(5) auxiliary agent B: 0.5～1.1;
(6) auxiliary agent C:0.74～1.2;
(7) calcium carbonate serosity water: 12～30, (B) prescription of polymer-modified emulsion:
(1) monomer: be made up of soft monomer and hard monomer, soft monomer is ethyl propenoate, vinylformic acid
Butyl ester or Octyl acrylate, hard monomer are methyl methacrylate or vinylbenzene, soft list
Body: hard monomer (mass ratio)=54: 46～56: 44;
(2) emulsifying agent is 2%～3% of a monomer total amount;
(3) initiator is an ammonium persulphate, is 0.1%～0.3% of monomer total amount;
(4) the 3rd component methacrylic acids (MAA) are 1% of monomer total amounts;
(5) deionized water is 128%～147% of a monomer total amount;
(6) emulsion solid content is 40%～44%.
2, coating according to claim 1 is characterized in that: the particle diameter of nano-calcium carbonate is below 50nm.
3, coating according to claim 1 is characterized in that: other color stuffings are at least a in titanium dioxide, kaolin, zinc sulfide white, talcum powder, the barite.
4, coating according to claim 1 is characterized in that: auxiliary agent A is dispersion agent or dispersion agent and wetting agent.
5, coating according to claim 1 is characterized in that: auxiliary agent B is at least a in film coalescence aid, multifunctional assistant, mould inhibitor, the sterilant.
6, coating according to claim 1 is characterized in that: auxiliary agent C is at least a in frostproofer, pH regulator agent, defoamer, the thickening material.
7, coating according to claim 1 is characterized in that: the emulsifying agent of polymer-modified emulsion is at least a in sodium lauryl sulphate (SDS), alkylphenol polyoxyethylene (OP-10), polyoxyethylene octylphenol ether (10) the sulfocarboxylic acid esters (MS-1).
8, the preparation method of coating according to claim 1 is prepared into the polymer-modified emulsion of membrane substance earlier, is mixed with coating with color stuffing, auxiliary agent and water again, and working method is as follows: (A) preparation of polymer-modified emulsion
(1) joins and stir with whole emulsifying agents (making solvent) earlier with 50% of the total consumption of deionized water
Mix in the reactor;
(2) soft monomer and hard monomer are divided into two portions use, the usefulness of first part's soft monomer separately
The consumption of amount and first part's hard monomer is respectively that total consumption of soft monomer and hard monomer are total
8%～20% of consumption.
(3) add first part's soft monomer and first part's hard monomer in the reactor;
When (4) the question response system reached kick off temperature, half of the total consumption of adding initiator (spent
1/4 of the total consumption of ionized water is made solvent), when reacting to " turning blue " state etc. system,
Keep constant temperature under polymerization temperature;
(5) again methacrylic acid is divided into two, is blended in second section soft monomer and second respectively
In the part hard monomer, again with remaining initiator (with 1/4 of the total consumption of deionized water
Make solvent) splash in the lump in the stirred reactor;
(6) continue to react to the polyreaction end again, obtain polymer-modified emulsion, (B) preparation process of coating is as follows:
(1) the raw material solid content is 23%～26% nano-calcium carbonate aqueous slurry, adds in container
Go into the in addition 150 rev/mins of stirrings of nano-calcium carbonate slurries, add auxiliary agent A and with 700
Rev/min high-speed stirring;
(2) add other color stuffings, continue with 700 rev/mins of stirrings, with 800 order net filtrations;
(3) in another container, add polymer-modified emulsion, auxiliary agent B, with 150 rev/mins of low speed
Stir; Stirring velocity is brought up to 250 rev/mins again, is added the color stuffing after filtering,
Reducing stirring velocity to 150 a rev/min continuation stirs;
(4) add auxiliary agent C, regulate viscosity, regulate the pH value between 8～9, froth breaking, discharging
Obtain coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021179824A CN1169893C (en) | 2002-05-28 | 2002-05-28 | Water-thinned latex paint containing nano calcium carbonate for cuter wall and its prepn process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021179824A CN1169893C (en) | 2002-05-28 | 2002-05-28 | Water-thinned latex paint containing nano calcium carbonate for cuter wall and its prepn process |
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| Publication Number | Publication Date |
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| CN1169893C CN1169893C (en) | 2004-10-06 |
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|---|---|---|---|
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