CN103614042A - Antifouling nano exterior wall coating and preparation method thereof - Google Patents
Antifouling nano exterior wall coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antifouling nano exterior wall coating and a preparation method thereof. The antifouling nano exterior wall coating is composed of the following components: 10-20% of water, 15-30% of rutile titanium dioxide, 0-15% of wollastonite powder, 0-5% of calcined kaolin, 30-60% of nano core-shell composite emulsion, 1-5% of coalescing agent, 0.5-2% of anti-freezing agent and 2.2-5.8% of small-dosage additive. The antifouling nano exterior wall coating and the preparation method thereof disclosed by the invention have the advantages that: 1. inorganic nano particles in the coating disclosed by the invention replace a part of polymers, thereby greatly reducing the use of organic oil resources, lowering the cost and improving the comprehensive performance of the coating; and 2. various performance indexes of the coating disclosed by the invention can meet the requirements of national standard GB/T9755-2001 superior products, the coating especially has excellent water resistance, alkali resistance, stain resistance and artificial aging resistance, and the wash resistance frequency of the coating is more than 10000.
Description
Technical field
The present invention relates to water-based exterior wall paint field, specifically by a kind of silicon sol/acrylate nano core-shell composite emulsion as main film forming substance, formulated a kind of antifouling nanometer exterior wall coating and preparation method thereof.
Background technology
Silicon sol claims again silicic acid water glass, is a kind of poly-metasilicic acid colloidal solution of inorganic polymer that water is disperse phase of take, and colloidal particle is mainly with spherical single or multiple coalescent, and mean particle dia, generally at 5-30nm, is applied in precision casting industry more.Owing to forming the porous skeleton structure of rigidity after silicon sol dehydration between micelle by hydroxyl dehydrating condensation, also can be separately as the filmogen of inorganic paint, film there is densification, hard, acid and alkali-resistance, heat-resisting, ageing resistance good, the advantage such as nontoxic, but also there are a lot of defects, as filmed, be rigidity, flexibility is poor, gloss is not high, easily there are crack, efflorescence etc., limited its application.
At present, coating for internal and external wall mainly with water-based organic polymer emulsion (phenylpropyl alcohol, pure third, silicon third, uncle third, fluorine carbon etc.) as main film forming substance, organic polymer emulsion has the advantages such as good film-forming property, water-tolerant, but also have the deficiencies such as high temperature after tack, resistance to soiling is poor, hardness is low, ultraviolet ageing is poor, various countries investigator is just being devoted to its study on the modification.In coating, use silicon sol and organic polymer emulsion blending, can increase substantially coating hardness and perviousness, strengthen resistance to acids and bases, ageing resistance, abrasion resistance, pollution resistance, overcome the anti-after tackiness of traditional polymer emulsion high temperature etc., caused people's extensive concern and fallen over each other research.Patent No. CN101381541B discloses " a kind of nano organosilicon exterior wall paint ", this emulsion is by silicon third, phenylpropyl alcohol, silicon sol three blending, coordinate suitable water, color stuffing and auxiliary agent formulated, in coating, silicon sol weight percentage is 5-15%, the features such as having pollution resistance is good, hydrophobic, alkali resistance is good, strong adhesion of filming.Patent No. CN102268208A discloses " a kind of nanometer silica sol modified exterior wall emulsion paint and preparation method thereof ", this emulsion paint main raw material is to be formed by polymer emulsion and Nano silica sol blending, the environmental protection of gained exterior wall latex paint, strong adhesion, have good abrasion resistance, polluting proofing property and weathering resistance.
Because nano-silicon dioxide particle surface in silicon sol exists great amount of hydroxy group and in conjunction with water, thereby in coating, hydrophilic increasing of inorganic component must cause water-resistance property of coating sharply to decline, the bad phenomenon such as occurring whiting, foaming after immersion of filming.Add hydrophobizing agent or use high hydrophobicity polymer emulsion can slow down this defect, but the addition of silicon sol is also unsuitable too high, addition generally can only reach 5-15%, and the attenuating of the improvement of performance and cost is had to certain limit.And due to SiO in silicon sol
2there is great amount of hydroxy group in particle surface, when standing, hydroxyl forms hydrogen bond action, System forming stereoscopic three-dimensional reticulated structure, system viscosity sharply rises, thereby such coating easily occurs automatic thickening, returns thick, flocculation, the bad phenomenon such as even scraps in storage process.In addition, due to silicon sol and polymer emulsion performance difference larger, store and film process in all easily there is coalescence or be separated, greatly affected the performance of its performance.
A kind of nano core-shell composite emulsion provided by the invention, for homemade high silicon content silicon sol/acrylate nano core-shell composite emulsion, with SiO
2meter, silicone content accounts for the 40-50% of emulsion total solids part weight percent, and composite polymer particle particle diameter is 60-80nm.This emulsion excellent combination property, and cost is extremely low, is a kind of filmogen of Novel water-based paint, in patent, there is not yet the report that adopts this emulsion to be developed into exterior coating at home.
Summary of the invention
In order to overcome the deficiencies in the prior art, object of the present invention provides a kind of antifouling nanometer exterior wall coating and preparation method thereof, and by the research of formula and the Optimization of technique are gone out, good stability, cost are low, the exterior coating of superior performance.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
1. an antifouling nanometer exterior wall coating, is characterized in that, by following component by weight percentage ratio form: 10～20% pure water; 15～30% Rutile type Titanium Dioxides; 0～15% wollastonite powder; 0～5% calcined kaolin; 30～60% nano core-shell composite emulsion; 1～5% film coalescence aid-ol ester-12; 0.5～2% frostproofer-propylene glycol; 2.2～5.8% low dose of auxiliary agents, it comprises: 0.1～0.2% wetting agent, 0.2～1% dispersion agent, 0.1～0.5% defoamer, 0.1～0.3% multifunctional assistant, 1～2% uv-absorbing agent, 0.5～1% photostabilizer, 0.1～0.3% mould inhibitor, 0.1～0.2% sterilant and 0.1～0.5% thickening material, thickening material be hydrophobically-modified alkali swelling association type, the thickening of acrylic acid class alkali form with type, polyurethanes association type in one or both;
Described nano core-shell composite emulsion is a kind of homemade high silicon content silicon sol/acrylate nano core-shell composite emulsion, with SiO
2meter, silicone content accounts for 40～50% of emulsion total solids part weight percent, and composite polymer particle particle diameter is 60～80nm.
2. a kind of preparation method of antifouling nanometer exterior wall coating as claimed in claim 1, is characterized in that comprising following operation steps:
Step 1: slurry preparation
The pure water, wetting agent, dispersion agent, frostproofer, multifunctional assistant, the defoamer that in Scattered Kettle, add successively formula ratio, under 300～500rpm low speed, dispersed with stirring is even; Add color stuffing, speed governing to 1000～1800rpm, high-speed stirring 30min left and right, fineness <60 μ m.
Step 2: pre-composition preparation, is pre-mixed even one-tenth pre-composition by film coalescence aid, uv-absorbing agent, photostabilizer.
Step 3: paint
Nano-composite emulsion is added in paint mixing kettle, speed governing to 600～900rpm, under middling speed, add step 1 material with slurry, add successively again frostproofer, pre-composition, sterilant, mould inhibitor, dropwise add thickening material diluent, adjust viscosity to appropriate value, finally add the defoamer with step 1 slurry preparation moderate, continue to stir 10min, filter discharging, obtain finished product.
Beneficial effect of the present invention: first, the present invention with nano core-shell composite emulsion for the main film forming substance of filming, this emulsion is to take nano silicon as core, acrylic ester polymer is the clad structure of shell, composite polymer particle particle diameter is little, nanometer titanium dioxide silicone content accounts for 40～50% of total solids part weight ratio, nano silicon dioxide particles can be brought into play the effect of partial polymer, not only can greatly reduce organopolysiloxane oil resource uses, meet environmental requirement, and can reduce costs, in performance, compared with Mixed Pinyin coating, there is great raising.Secondly, this coating has excellent anti-pollution function, major cause is that nano core-shell composite emulsion latex particle size is minimum, after dry film, arrange regular, film forming is fine and close, and hardness is higher, so in the dirts such as dust, greasy dirt are difficult for infiltrating into and film, so that rainwater can wash away removes surface contaminants, thereby coating is kept clean.Again, because nanoemulsions characteristic and a small amount of hydroxyl of silica sphere form slight hydrogen bond action, in coating process without using Natvosol, only adding a small amount of associative thickener just can make system viscosity reach appropriate value, possess good in, low-shear viscosity, viscosity stable storing is good, can also play and reduce costs, do not reduce glossiness, improve the water tolerance of finished product and the effect of levelling property.
Properties of the present invention all can reach the requirement of GB GB/T9755-2001 premium grads, and especially water-fast, alkali resistance, resistance to soiling, artificial ageing resistance are excellent, and washability number of times is more than 10000 times.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment 1
In Scattered Kettle, add successively 110g pure water, 1g wetting agent PE-100,5g dispersion agent 5027,15g propylene glycol, 1g multifunctional assistant AMP-95,1g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 250g titanium dioxide (the former industry CR-95 of Japanese stone), speed governing is to 1500rpm, high-speed stirring 30min left and right, and fineness <60 μ m, standby.
Claim 550g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,48g pre-composition (claims 30g film coalescence aid cs-12,12g ultraviolet absorbers
1130,6g photostabilizer
292, mix); Speed governing, to 800rpm, dropwise adds thickening material diluent I(SN636: water=1: 5) 12g, and thickening material diluent II(SN612: water=1: 3) 4g, finally add 1g BYK-024, and stir 10min, filter discharging, obtain finished product.(viscosity KU=90, contrast ratio=0.96)
Embodiment 2
In Scattered Kettle, add successively 110g pure water, 1.2g wetting agent PE-100,6g dispersion agent 5027,12g propylene glycol, 1g multifunctional assistant AMP-95,1.2g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 170g titanium dioxide (the former industry CR-95 of Japanese stone), 100g wollastonite powder, 30g calcined kaolin, speed governing is to 1500rpm, high-speed stirring 30min left and right, fineness <60 μ m.
Claim 500g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,48g pre-composition (claims 30g film coalescence aid cs-12,12g ultraviolet absorbers
1130,6g photostabilizer
292, mix); Speed governing, to 800rpm, dropwise adds thickening material diluent I(SN636: water=1: 5) 12g, and thickening material diluent II(SN612: water=1: 3) 4g, finally add 1.2g BYK-024, and stir 10min, filter discharging, obtain finished product.(viscosity KU=91, contrast ratio=0.97)
Embodiment 3
In Scattered Kettle, add successively 110g pure water, 1g wetting agent PE-100,5g dispersion agent 5027,15g propylene glycol, 1g multifunctional assistant AMP-95,1g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 250g titanium dioxide (Dupont R902), speed governing is to 1500rpm, high-speed stirring 30min left and right, and fineness <60 μ m, standby.
Claim 550g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,48g pre-composition (claims 30g film coalescence aid cs-12,12g ultraviolet absorbers
1130,6g photostabilizer
292, mix); Speed governing, to 800rpm, dropwise adds thickening material diluent I(Acrysol TT-935: water=1: 1) 4g, and thickening material diluent II(SN612: water=1: 3) 4g, finally add 1g BYK-024, and stir 10min, filter discharging, obtain finished product.(viscosity KU=90, contrast ratio=0.98)
Embodiment 4
In Scattered Kettle, add successively 110g pure water, 1.2g wetting agent PE-100,6g dispersion agent 5027,15g propylene glycol, 1g multifunctional assistant AMP-95,1.2g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 170g titanium dioxide (Dupont R706), 100g wollastonite powder, 30g calcined kaolin, speed governing is to 1500rpm, high-speed stirring 30min left and right, fineness <60 μ m, standby.
Claim 500g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,48g pre-composition (claims 30g film coalescence aid cs-12,12g ultraviolet absorbers
1130,6g photostabilizer
292, mix); Speed governing, to 800rpm, dropwise adds thickening material diluent I(SN636: water=1: 5) 12g, and thickening material diluent II(SN612: water=1: 3) 4g, finally add 1.2g BYK-024, and stir 10min, filter discharging, obtain finished product.(viscosity KU=91, contrast ratio=0.97)
Embodiment 5
In Scattered Kettle, add successively 110g pure water, 1g wetting agent PE-100,2g dispersion agent 5027,4g dispersion agent 5040,15g propylene glycol, 1g multifunctional assistant AMP-95,1.2g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 170g titanium dioxide (the former industry CR-95 of Japanese stone), 120g wollastonite powder, 30g calcined kaolin, speed governing is to 1500rpm, high-speed stirring 30min left and right, fineness <60 μ m, standby.
Claim 500g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,48g pre-composition (claims 30g film coalescence aid cs-12,12g ultraviolet absorbers
1130,6g photostabilizer
292, mix); Speed governing, to 800rpm, dropwise adds thickening material diluent I(SN636: water=1: 5) 12g, and thickening material diluent II(SN612: water=1: 3) 4g, finally add 1.2g BYK-024, and stir 10min, filter discharging, obtain finished product.(viscosity KU=90, contrast ratio=0.95)
Embodiment 6
In Scattered Kettle, add successively 110g pure water, 1.2g wetting agent PE-100,2g dispersion agent 5027,4g dispersion agent 5040,15g propylene glycol, 1g multifunctional assistant AMP-95,1.2g defoamer BYK-024, under the low speed of 400rpm, dispersed with stirring is even; Add 220g titanium dioxide (Dupont R706), 100g wollastonite powder, 30g calcined kaolin, speed governing is to 1500rpm, high-speed stirring 30min left and right, fineness <60 μ m, standby.
Claim 450g nano-composite emulsion to add in paint mixing kettle, under the middling speed of 600rpm, add step 1 material with slurry, stir 10min; Add successively 1g sterilant LX-150,1g mould inhibitor SKANE M-8,40g pre-composition (claims 25g film coalescence aid cs-12,10g ultraviolet absorbers
1130,5g photostabilizer
292, mix); Speed governing is to 800rpm, dropwise add thickening material diluent (Acrysol TT-935: water=1: 1) 6g, finally add 1.2g BYK-024, stir 10min, filter discharging, obtain finished product.(viscosity KU=91, contrast ratio=0.96)
Detection is carried out according to GB/T9755-2001 < < exterior wall coating material of synthetic resin emulsion > >, and embodiment 1 end properties detected result is as shown in table 1 below.
Table 1. embodiment 1 coating finished product detection result
Claims (2)
1. an antifouling nanometer exterior wall coating, is characterized in that, by following component by weight percentage ratio form: 10～20% pure water; 15～30% Rutile type Titanium Dioxides; 0～15% wollastonite powder; 0～5% calcined kaolin; 30～60% nano core-shell composite emulsion; 1～5% film coalescence aid-ol ester-12; 0.5～2% frostproofer-propylene glycol; 2.2～5.8% low dose of auxiliary agents, it comprises: 0.1～0.2% wetting agent, 0.2～1% dispersion agent, 0.1～0.5% defoamer, 0.1～0.3% multifunctional assistant, 1～2% uv-absorbing agent, 0.5～1% photostabilizer, 0.1～0.3% mould inhibitor, 0.1～0.2% sterilant and 0.1～0.5% thickening material, thickening material be hydrophobically-modified alkali swelling association type, the thickening of acrylic acid class alkali form with type, polyurethanes association type in one or both;
Described nano core-shell composite emulsion is a kind of homemade high silicon content silicon sol/acrylate nano core-shell composite emulsion, with SiO
2meter, silicone content accounts for 40～50% of emulsion total solids part weight percent, and composite polymer particle particle diameter is 60～80nm.
2. a kind of preparation method of antifouling nanometer exterior wall coating as claimed in claim 1, is characterized in that comprising following operation steps:
Step 1: slurry preparation
The pure water, wetting agent, dispersion agent, frostproofer, multifunctional assistant, the defoamer that in Scattered Kettle, add successively formula ratio, under 300～500rpm low speed, dispersed with stirring is even; Add color stuffing, speed governing to 1000～1800rpm, high-speed stirring 30min left and right, fineness <60 μ m;
Step 2: pre-composition preparation, is pre-mixed even one-tenth pre-composition by film coalescence aid, uv-absorbing agent, photostabilizer;
Step 3: paint
Nano-composite emulsion is added in paint mixing kettle, speed governing to 600～900rpm, under middling speed, add step 1 material with slurry, add successively again frostproofer, pre-composition, sterilant, mould inhibitor, dropwise add thickening material diluent, adjust viscosity to appropriate value, finally add the defoamer with step 1 slurry preparation moderate, continue to stir 10min, filter discharging, obtain finished product.
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| CN104059529A (en) * | 2014-06-03 | 2014-09-24 | 安徽奥邦新材料有限公司 | Antifouling paint formula |
| CN104559791A (en) * | 2015-02-06 | 2015-04-29 | 广东顺德嘉乐士涂料有限公司 | Nano-modified super fouling-resistant emulsion paint and preparation method thereof |
| CN105255265A (en) * | 2014-07-14 | 2016-01-20 | 开平市开物化工建材有限公司 | High PVC external wall plane latex paint based on HUER thickening agents, and production process thereof |
| CN115449296A (en) * | 2022-08-22 | 2022-12-09 | 德爱威（中国）有限公司 | Anti-tearing solid color primer for outer wall and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104059529A (en) * | 2014-06-03 | 2014-09-24 | 安徽奥邦新材料有限公司 | Antifouling paint formula |
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| CN104559791A (en) * | 2015-02-06 | 2015-04-29 | 广东顺德嘉乐士涂料有限公司 | Nano-modified super fouling-resistant emulsion paint and preparation method thereof |
| CN115449296A (en) * | 2022-08-22 | 2022-12-09 | 德爱威（中国）有限公司 | Anti-tearing solid color primer for outer wall and preparation method thereof |
| CN115449296B (en) * | 2022-08-22 | 2023-12-05 | 德爱威（中国）有限公司 | Tear-off resistant solid color primer for outer wall and preparation method thereof |
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