CN1488684A - Nano composite latex paint and preparing method thereof - Google Patents
Nano composite latex paint and preparing method thereof Download PDFInfo
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- CN1488684A CN1488684A CNA021331634A CN02133163A CN1488684A CN 1488684 A CN1488684 A CN 1488684A CN A021331634 A CNA021331634 A CN A021331634A CN 02133163 A CN02133163 A CN 02133163A CN 1488684 A CN1488684 A CN 1488684A
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Abstract
The composition of the invented nano composite latex paint comprises (wt%) 0.3-1% of moistening dipersant, 2-70% of nano pulp, 1-4% of film-forming adjuvant, 0.5-2% of anti-sedimentation agent, 0.8-15% of antifreeze agent, 0.5-3% of defoaming agent, 5-30% of pigment, 0-30% of filling material, 10-45% of emulsion, 0.2-2% of thickening agent, 0.2-2% of leveling agent, 0-2% of pH regulating agent, 0-2% of microbiocide and 2-35% of water. Its preparation method includes two steps: firstly, preparing dispersion stable nano material pulp, then adding said nano material pulp into the latex component according to a certain process so as to obtain the invented high-performance product.
Description
Technical field
The present invention relates to coating technology, be specially a kind of nano composite latex paint and preparation method thereof.
Background technology
Emulsion paint is a kind of water-borne coatings, and contained organic volatile is very low, meets environmental protection requirement, belongs to " green coating ".Obtained very great development after emulsion paint produces, people constantly improve every performance of emulsion paint by every means from different aspects.The raising that appears as the emulsion paint performance of nano material has brought opportunity.A kind of building coating of the 0.5-1.5% of containing silicon-base oxide is disclosed as Chinese invention patent CN1277234A.Suspension, cohesive strength, ageing resistance and the stain resistance of coating have been improved.Chinese invention patent CN1287145A has reported a kind of nanometer paint for external wall with preparations such as nano silicon-based oxide, nano-titanium oxide, titanium dioxide, filler and emulsions, has good resistance to soiling, mildew-resistant, anti-algae and long acting antibiotic effect.But the abrasion resistance of these two kinds of coating, package stability are not very good.
Summary of the invention
The purpose of this invention is to provide a kind of nano composite latex paint and preparation method thereof, it has performances such as good storage stability, resistance to deterioration, abrasion resistance.
Technical scheme of the present invention is:
A kind of nano composite latex paint, by weight percentage, be made of following component: 0.3～1% wetting dispersing agent, 2～70% nanometers slurry, 1～4% film coalescence aid, 0.5～2% anti-settling agent, 0.8～15% frostproofer, 0.5～3% defoamer, 5～30% pigment, 0～30% filler, 10～45% emulsions, 0.2～2% thickening material, 0.2～2% flow agent, 0～2%pH adjust agent, 0～2% microbicide, 2～35% water.
Described nanometer slurry is made up of 0.2～80% nano silicon-based oxide, 0.2～80% nano-titanium oxide, 0.2～80% nano zircite, 15～90% water, 0.5～10% wetting dispersing agent; Nanometer slurry content is 5～60% preferably.
Described wetting dispersing agent is that one or more of natural polymer subclass, synthetic macromolecule class, polyvalent carboxylic acid's class, block macromolecular copolymer analog, special polyvinyls is mixed.
Wherein, the TROYSOLLWD, (Langer﹠amp of Ling Gao company of natural polymer subclass such as Troy Chemical Corp (Te Luoyi chemical company); Co) Soya-lecithin-Concentrate W-250; The SN-Dispersant 5027 of polyvalent carboxylic acid's class such as Henkel Corp. (Henkel), SN-Dispersant 5034, SN-Dispersant5040, BEVALOID111, the BEVALOID211 of rhone-poulenc (RH NE-POULENC), the SER-AD FX504 of Sheng Wo company (SERVO), Demol EP, the Demol P of Japanese Kao company, Demol ST, Poise 521, Poise 530, Poise 532A; The PA-01 of synthetic macromolecule class such as Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing, AGS-01, AGS-02 water-borne coatings dispersion agent (esters of acrylic acid), Changzhou radiance is made the F-4 of lacquer factory, F-5, SG-8001 water-borne coatings dispersion agent, the P-19 water-borne coatings dispersion agent of Shanghai coating institute, the PA-100 of last Haikang skill industrial corporation, the PA-101 dispersion agent, the KG-503 of Linan, Hangzhou coatings additive(s) factory, HG-504, the HG-505 dispersion agent, the DP-512 of the Taiwan modest Trading Co., Ltd of moral, DP-518 aqueous dispersant DP-18, the Borchigen NA 20 of Bayer AG, Borchigen NA 40, Borchigen PP 100 water-based wetting dispersing agents, the DISPONL of Henkel Corp.
05 non-ionic type wetting dispersing agent, Hydropalat
759, Hydropalat
875, Hydropalat
3043, Hydropalat
3051, Colorsperse 188 A, Disponil SMO, Hydropalat
3204, the BYK-345 of Germany Bi Ke chemical company, BYK-346, BYK-348, the COATEX DN 440C of brother Supreme Being scholar company (COATEX S.A.), COATEX A 122, COATEX BR 3, the H-30A of associating carbonization company limited (UNION CARBIDE), TRITONX-100, TRITON X-102, TRTON X-405, TRITON CF-10, TRITON GR-5M, TRITONGR-7M GR-9M, TRITON QS-44, TRITON XQS-20, TRITON XZ-301, TERGITOLNP-9, TERGITOL NP-10, TERGITOL NP-11, TERGTOL NP-30, TERGITOLNP-40, TERGITOL NP-70, TERGITOL 15-S-7, TERGITOL 15-S-9, TERGITOL15-S-12, TERGITOL XJ, TERGUTOL XD, TERGITOL XH, the DemolN of Japanese Kao company, Demol NL, Demol RN, Demol RN-L, Demol SN-B; The Hydropalat of Solsperse12000, the Solsperse20000 of BYK-151, the BYK154 of block macromolecular copolymer analog such as German Bi Ke chemical company, Dispebyk180, Disperbyk181, Disperby182, Disperbyk184, Disperby190, Dispebyk191, Avecia company, Solsperse27000, Henkel Corp.
3275, Hydropalat
1080; Special polyvinyls such as Hyonic PE-40, Hyonic PE-60 HyonicPE-90, Hyonic PE-100, Hyonic PE-120, Emulgen A-60, the EmulgenA-90 of Japanese Kao company, Emulgen B-66, Emulgen L-40, Emulgen 900, Emulgen 909, Emulgen 910, Emulgen 911, Emulgen 913, Emulgen 920.
Other auxiliary agent such as film coalescence aid, anti-settling agent, frostproofer, defoamer, pigment, filler, thickening material, flow agent, pH adjust agent, microbicide is an auxiliary agent commonly used during emulsion paint is produced.
Described emulsion can be mixed along one or more of (vinyl acetate between to for plastic-MALEIC ANHYDRIDE) emulsion, propylene ester emulsion, second third (vinyl acetate between to for plastic-acrylate) copolymer emulsion, phenylpropyl alcohol (cinnamic acrylic ester) copolymer emulsion, vinyl acetate between to for plastic-tertiary carbon acid esters copolymer emulsion, vinegar chlorine third (vinyl acetate between to for plastic-vinylchlorid-propylene vinegar) copolymer emulsion, organosilicon crylic acid latex for butylbenzene (butadiene-styrene) emulsion, polyvinyl acetate emulsion, vinegar.
Described pigment can be mixed for one or more of titanium dioxide, zinc oxide, stibium trioxide, white lead, lithopone, white dyes, chrome yellow, zinc-chrome yellow, iron oxide yellow, cadmium yellow, organic yellow, red iron oxide, toluidine red, red, iron oxide black, carbon black, barba hispanica, ultramarine, phthalocyanine blue, chromoxide green, lead chrome green, phthalocyanine green, phthalocyanine chrome green, red lead, calcium plumbite, iron mica, barium metaborate, strontium chromate, strontium yellow, four alkali zinc yellows, zinc chromate, zinc phosphate.
Described filler can be mixed for one or more of water-ground limestone, light calcium carbonate, talcum powder, ground barium sulfate, process white, mica powder, asbestos powder, silica powder, white carbon black, wollastonite powder, wilkinite, grey calcium powder.
The preparation method of nano composite latex paint of the present invention is by its weight percent with described component, the preparation of employing two-step approach, be the nano material slurry that the first step prepares stably dispersing, second step joined the nano material slurry in the component of emulsion paint by certain processing method, and concrete steps are as follows:
1) water is put into the container of homogenizer earlier, (add microbicide, film coalescence aid, wetting dispersing agent, defoamer, anti-settling agent, frostproofer under 100～400rpm) successively at low speed, the nanometer slurry after mixing, adds pigment and filler and slowly adds in the vortex of high speed dispersor; After adding material, improve wheel speed, make its rotating speed 1200～1800rpm, after fineness qualified (20～60 μ m), promptly disperse to finish;
2) after dispersion finishes, adjust the rotating speed of high speed dispersor, make that it adds emulsion gradually at 100～400rpm, pH adjusts agent, adjustment emulsion paint pH value is in 8～9 scopes, stormer viscosity to 70～120KU with thickening material and flow agent adjustment emulsion paint makes nano composite latex paint after sieving.
Nano composite latex paint mixing of the present invention and grinding dispersing apparatus are the common equipments in the coating preparation process, comprise high speed dispersor, sand mill, ball mill and ball mill.
Advantage of the present invention is as follows:
(1) nano material used in the present invention slurry mainly is made up of the nano powder that the particle diameter of stable dispersion is generally less than 100nm, this method makes nano material easier dispersion in coating, solved the compatibility issue of nano material and emulsion, color stuffing, auxiliary agent well, it is more stable that nano composite latex paint is stored.
(2) the homodisperse nanoparticle of the present invention easily is filled in the hole or the pore of coating; improve the permeability resistance of coating, and improved water tolerance, alkali resistance, the polluting proofing property of coating, prevented carbonization of concrete effectively; improving the ornamental while, also protected building masonry wall.
(3) the present invention is because the specific surface area of nanoparticle is big, and surfactivity is big, be very easy to coating in other component produce chemical bonding, make that sticking power is greatly improved, scrub performance significantly improves.
(4) the present invention utilizes nanoparticle to ultraviolet scattering of light and sorption, has improved the guarantor's look and the gloss retention of emulsion paint, has strengthened the ageing resistance of filming.
Embodiment
Unless outside specializing among the present invention, related ratio all is weight percentage.
The evaluation method of nano composite latex paint: test according to GB GB/T 9755-2001 " exterior wall coating material of synthetic resin emulsion ".
Embodiment 1
17.5% water is put into the container of homogenizer earlier, under low speed (300rpm), add 0.5% microbicide Npcocide N-96 (Henkel Corp.) successively, 3% alcohol ester-12 film coalescence aid (Jilin Chemical Industry Company design and research institute), 0.5% wetting dispersing agent Demol EP (Japanese Kao company), 2% defoamer BYK-011 (German Bi Ke chemical company), 1% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 8% ethylene glycol antifreeze, 10% nanometer slurry (contains 3% nano silicon-based oxide, 2% nano-titanium oxide, 5% nano zircite, 85% water, 5%SN-Dispersant 5034), after mixing, with 20% titanium dioxide, 10% water-ground limestone and 5% talcum powder slowly add in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1300rpm of its rotating speed, after fineness reaches 40 μ m, under 300rpm, add 20% propylene ester emulsion, 1% ammoniacal liquor (pH adjusts agent) gradually, adjusting the pH value is 8.5, adds 1% thickening material SO-Thick 30 (Industrial Co., Ltd. is changed in Taiwan three) and 0.5% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjusts viscosity to 90KU, makes nano composite latex paint after sieving.
Embodiment 2
5% water is put into the container of homogenizer earlier, under low speed (200rpm), add 1.5% microbicide BIT (Britain ICI company) successively, 1%Texanol ester alcohol film coalescence aid (U.S. Eastman company), 1% wetting dispersing agent DP-512 (the modest Trading Co., Ltd of Taiwan moral), 0.5% defoamer SN-154 (Henkel KGaA company), 2% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 4% ethylene glycol antifreeze, 30% nanometer slurry (contains 1% nano silicon-based oxide, 1% nano-titanium oxide, 80% nano zircite, 15% water, 3%Disperbyk181), after mixing, with 5% titanium dioxide, 5% red iron oxide, 5.3% lithopone, 2% light calcium carbonate and 5% wollastonite powder slowly add in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1500rpm of its rotating speed, after fineness reaches 40 μ m, under 300rpm, add 30% organosilicon crylic acid latex, 0.5% ammoniacal liquor (pH adjusts agent) gradually, adjusting the pH value is 8.5, adds 0.2% thickening material ModicolVD-S (Henkel KGaA company) and 2% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjusts viscosity to 75KU, makes nano composite latex paint after sieving.
Embodiment 3
2% water is put into the container of homogenizer earlier, under low speed (200rpm), add 2% microbicide TPN (Lanzhou chemical industrial company) successively, 2%Loxasnol 842 DP/3 film coalescence aid (Henkel KGaA company), 1% wetting dispersing agent TD-01 (Tianjin chemical research institute), 1% defoamer BYK-074 (German Bi Ke chemical company), 0.5% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 0.8% propylene glycol frostproofer, 50% nanometer slurry (contains 70% nano silicon-based oxide, 2% nano-titanium oxide, 5% nano zircite, 15% water, 8%BEVALOID 211), after mixing, 5% zinc oxide is slowly added in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1400rpm of its rotating speed, after fineness reaches 40 μ m, under 400rpm, add 32.7% polyvinyl acetate emulsion gradually, add 2% thickening material NATROSOL HH (U.S. AQUALON company) and 1% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjust viscosity, make nano composite latex paint after sieving to 120KU.
Comparative example 1
27.5% water is put into the container of homogenizer earlier, under low speed (300rpm), add 0.5% microbicide Nopcocide N-96 mould inhibitor (Henkel Corp.) successively, 3% alcohol ester-12 film coalescence aid (Jilin Chemical Industry Company design and research institute), 0.5% wetting dispersing agent Demol EP (Japanese Kao company), 2% defoamer BYK-011 (German Bi Ke chemical company), 1% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 8% ethylene glycol antifreeze, after mixing, with 20% titanium dioxide, 10% water-ground limestone and 5% talcum powder slowly add in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1300rpm of its rotating speed, after fineness reaches 40 μ m, under 300rpm, add 20% vinyl acetate emulsion, 1% ammoniacal liquor (pH adjusts agent) gradually, adjusting the ph value is 8.5, adds 1% thickening material SO-Thick30 (Industrial Co., Ltd. is changed in Taiwan three) and 0.5% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjusts viscosity to 90KU, makes composite latex paint after sieving.
Comparative example 2
17.5% water is put into the container of homogenizer earlier, under low speed (300rpm), add 0.5% microbicide Nopcocide N-96 (Henkel Corp.) successively, 3% alcohol ester-12 film coalescence aid (Jilin Chemical Industry Company design and research institute), 0.5% wetting dispersing agent Demol EP (Japanese Kao company), 2% defoamer BYK-011 (German Bi Ke chemical company), 1% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 8% ethylene glycol antifreeze, 10% nanometer slurry (contains 10% nano silicon-based oxide, 85% water, 5%SN-Dispersant 5034), after mixing, with 20% titanium dioxide, 10% water-ground limestone and 5% talcum powder slowly add in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1300rpm of its rotating speed, after fineness reaches 40 μ m, under 300rpm, add 20% propylene ester emulsion, 1% ammoniacal liquor (pH adjusts agent) gradually, adjusting the pH value is 8.5, adds 1% thickening material SO-Thick 30 (Industrial Co., Ltd. is changed in Taiwan three) and 0.5% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjusts viscosity to 90KU, makes nano composite latex paint after sieving.
Comparative example 3
17.5% water is put into the container of homogenizer earlier, under low speed (300rpm), add 0.5% microbicide Nopcocide N-96 (Henkel Corp.) successively, 3% alcohol ester-12 film coalescence aid (Jilin Chemical Industry Company design and research institute), 0.5% wetting dispersing agent Demol EP (Japanese Kao company), 2% defoamer BYK-011 (German Bi Ke chemical company), 1% anti-settling agent SER-AD BEZ 75 (Sheng Wo company), 8% ethylene glycol antifreeze, 10% nanometer slurry (contains 5% nano silicon-based oxide, 5% nano-titanium oxide, 85% water, 5%SN-Dispersant 5034), after mixing, with 20% titanium dioxide, 10% water-ground limestone and 5% talcum powder slowly add in the vortex of high speed dispersor.After adding material, improve wheel speed, make the about 1300rpm of its rotating speed, after fineness reaches 40 μ m, under 300rpm, add 20% propylene ester emulsion, 1% ammoniacal liquor (pH adjusts agent) gradually, adjusting the pH value is 8.5, adds 1% thickening material SO-Thick 30 (Industrial Co., Ltd. is changed in Taiwan three) and 0.5% flow agent ACRYSOL RM-4 (Rhom and Hass) and adjusts viscosity to 90KU, makes nano composite latex paint after sieving.
The emulsion paint The performance test results of the foregoing description 1～3 and comparative example 1～3 is as shown in table 1, as shown in Table 1, contain the performance of nano composite latex paint of nano silicon-based oxide, nano-titanium oxide, nano zircite significantly better than not containing nano-oxide or only containing nano silicon-based oxide or contain the emulsion paint of nano silicon-based oxide, nano-titanium oxide.
Table 1 emulsion paint The performance test results
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Low-temperature stability | Never degenerate | Never degenerate | Never degenerate | Never degenerate | Never degenerate | Never degenerate |
| Contrast ratio, 〉= | 0.90?? | 0.93 | 0.93 | 0.96 | 0.95 | 0.94 |
| Water tolerance (96 hours) | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal |
| Alkali resistance (48 hours) | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal |
| Abrasion resistance/time, 〉= | 1000 | 5000 | 6000 | 12000 | 10000 | 14000 |
| Temperature-change resistance (5 circulations) | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal | No abnormal |
| Polluting proofing property/% ,≤ | 15????? | 12 | 12 | 10 | 8 | 7 |
| Artificial weathering ageing resistance's efflorescence/level ,≤variable color/level ,≤ | 3 3 | 2 2 | 2 2 | 1 1 | 1 1 | 1 1 |
Claims (9)
1, a kind of nano composite latex paint, it is characterized in that by weight percentage, be made of following component: 0.3～1% wetting dispersing agent, 2～70% nanometers slurry, 1～4% film coalescence aid, 0.5～2% anti-settling agent, 0.8～15% frostproofer, 0.5～3% defoamer, 5～3% pigment, 0～30% filler, 10～45% emulsions, 0.2～2% thickening material, 0.2～2% flow agent, 0～2%pH adjust agent, 0～2% microbicide, 2～35% water.
2, according to the described nano composite latex paint of claim 1, it is characterized in that: described nanometer slurry content is 5～60%.
3, according to the described nano composite latex paint of claim 1, it is characterized in that: described nanometer slurry is made up of 0.2～80% nano silicon-based oxide, 0.2～80% nano-titanium oxide, 0.2～80% nano zircite, 15～90% water, 0.5～10% wetting dispersing agent.
4, according to claim 1,2 or 3 described nano composite latex paints, it is characterized in that: described wetting dispersing agent is that one or more of natural polymer subclass, synthetic macromolecule class, polyvalent carboxylic acid's class, block macromolecular copolymer analog, special polyvinyls is mixed.
5, according to claim 1,2 or 3 described nano composite latex paints, it is characterized in that: described emulsion is that one or more of butadiene-styrene emulsion, polyvinyl acetate emulsion, vinyl acetate between to for plastic-MALEIC ANHYDRIDE emulsion, propylene ester emulsion, vinyl acetate between to for plastic-acrylate copolymer emulsion, interpolymer latex of polystyrene and acrylic ester, vinyl acetate between to for plastic-tertiary carbon acid esters copolymer emulsion, vinyl acetate between to for plastic-vinylchlorid-propylene vinegar copolymer emulsion, organosilicon crylic acid latex is mixed.
6, according to claim 1,2 or 3 described nano composite latex paints, it is characterized in that: described pigment is that one or more of titanium dioxide, zinc oxide, stibium trioxide, white lead, lithopone, white dyes, chrome yellow, zinc-chrome yellow, iron oxide yellow, cadmium yellow, organic yellow, red iron oxide, toluidine red, red, iron oxide black, carbon black, barba hispanica, ultramarine, phthalocyanine blue, chromoxide green, lead chrome green, phthalocyanine green, phthalocyanine chrome green, red lead, calcium plumbite, iron mica, barium metaborate, strontium chromate, strontium yellow, four alkali zinc yellows, zinc chromate, zinc phosphate is mixed.
7, according to claim 1,2 or 3 described nano composite latex paints, it is characterized in that: described filler is that one or more of water-ground limestone, light calcium carbonate, talcum powder, ground barium sulfate, process white, mica powder, asbestos powder, silica powder, white carbon black, wollastonite powder, wilkinite, grey calcium powder is mixed.
8, a kind of preparation method according to the described nano composite latex paint of claim 1, it is characterized in that: described component is pressed its weight percent, the preparation of employing two-step approach, it is the nano material slurry that the first step prepares stably dispersing, second step joined the nano material slurry in the component of emulsion paint, and concrete steps are as follows:
1) water is put into the container of homogenizer earlier, under 100～400rpm, add microbicide, film coalescence aid, wetting dispersing agent, defoamer, anti-settling agent, frostproofer successively, the nanometer slurry after mixing, adds pigment and filler and adds in the vortex of high speed dispersor; After adding material, improve wheel speed, make its rotating speed 1200～1800rpm, after fineness reaches 20～60 μ m, promptly disperse to finish;
2) after dispersion finishes, adjust the rotating speed of high speed dispersor, make it adjust agent, adjust emulsion paint pH value in 8～9 scopes at 100～400rpm adding emulsion, pH, stormer viscosity to 70～120KU with thickening material and flow agent adjustment emulsion paint makes nano composite latex paint after sieving.
9, according to the preparation method of the described nano composite latex paint of claim 8, it is characterized in that: described nano composite latex paint mixes and grinds dispersing apparatus is high speed dispersor, sand mill, ball mill or ball mill.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133163 CN1195024C (en) | 2002-10-11 | 2002-10-11 | Nano composite latex paint and preparing method thereof |
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|---|---|---|---|
| CN 02133163 CN1195024C (en) | 2002-10-11 | 2002-10-11 | Nano composite latex paint and preparing method thereof |
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| CN1488684A true CN1488684A (en) | 2004-04-14 |
| CN1195024C CN1195024C (en) | 2005-03-30 |
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| CN 02133163 Expired - Fee Related CN1195024C (en) | 2002-10-11 | 2002-10-11 | Nano composite latex paint and preparing method thereof |
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Owner name: ZHONGKE NANO PAINT TECHNOLOGY (SUZHOU) CO., LTD. Free format text: FORMER OWNER: METAL INST., CHINESE ACADEMY OF SCIENCES Effective date: 20060127 |
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