CN1238453C - Organosilicon emulsion composition for water-borne coating cover surface - Google Patents
Organosilicon emulsion composition for water-borne coating cover surface Download PDFInfo
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- CN1238453C CN1238453C CN 02113256 CN02113256A CN1238453C CN 1238453 C CN1238453 C CN 1238453C CN 02113256 CN02113256 CN 02113256 CN 02113256 A CN02113256 A CN 02113256A CN 1238453 C CN1238453 C CN 1238453C
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Abstract
The present invention relates to organic silicone emulsion composition used for a water paint coating cover surface. The composition is mainly used for the water paint coating cover surface for preventing water and dirt, improving the weather resistance of the coating and preventing the corrosion of micro organisms for the coating. The composition is prepared from organic silicone emulsion and crosslinking modifying agents according to a definite proportion, particularly from the following detailed components counted by solid parts by weight: (A) 100 portions of organic silicone emulsion, (B) 15 to 30 portions of alkoxy silane dispersion liquid, (C) 0 to 5 portions of hexafluorosilicic acid ethyl ester dispersion liquid, (D) 0 to 6 portions of fluosilicate, (E) 0 to 5 portions of polyphosphate, and (F) 0 to 3 portions of organotin compound dispersion liquid.
Description
The present invention relates to a kind of organosilicon emulsion composition that is used for the water-borne coating cover surface protection.Said composition can be sprayed or brush on the water-borne coating surface forms the coating that one deck naked eyes are difficult for discovering; this coating has obvious hydrophobic; can improve pollution resistance, weathering resistance, the waterproof tint retention of water-borne coatings significantly; prevent the erosion action of mould simultaneously, the work-ing life of improving protected coating to water-borne coating.
The generally not supporting use protective material of water-borne coatings that uses uses methyl silanol salt or acrylic resin and acrylic copolymeric resin as the cover protective material under a few cases at present.Because water-borne coatings itself is the medium dispersive with water exactly, exist a large amount of hydrophilic materials, the organism that contains simultaneously many easy breed bacteria and mould again, therefore list improves from the prescription of water-borne coatings itself and the material property of use thereof, it is very high to exist performance costs such as weather-proof, the resistant of improving coating significantly, waterproof mildew-resistant, and not thoroughly and reliable.As time goes by, sanitas and mould inhibitor in the coating constantly move, and in the moist out of doors rainy environment, this problem will be outstanding all the more.The present invention attempts to adopt the method for composite Materials Design; allow water-borne coatings only realize that the basic function of coating is promptly opacifying property, ornamental; keep necessary sticking power and the color and luster that needs, and allow the water-borne coatings protective material solve hydrophobic nature and improve weathering resistance and prevent extraneous hazardous substances such as mould from the surface to the erosion of water-borne coating.Reaching these purposes and do not influencing simultaneously the outward appearance and the color and luster of original coating, comparatively thoroughly solving the disadvantage of water-borne coating effectively, making it durable in use, for a long time Chang Xin with lower cost.
If use methyl silanol salt or have following several problem as the composition of main ingredient: at first with it, because methyl silanol salt is low molecular compound, progressively condensation under the necessary aerial carbonic acid gas effect, thereby influenced by carbon dioxide in air concentration and ventilation condition, curing reaction speed is very slow, the time in common needs several days even several weeks, in the meantime, in case the quilt that rains is drenched then is not reached effect fully.In addition, the curing reaction degree is not high, after rainwater repeatedly washes away, will progressively reduce effect.Secondly,, filmogen in the coating such as acrylic resin there are the catalytic hydrolysis effect, the stability of coating is affected because methyl silanol salt generally is strong alkaline substance.
In addition, no matter use the solvent type or acrylic resin of emulsion-type or acrylic copolymer resin all to have the problem of an epithelium ventilation property difference.Even organosilicon-Acrylate copolymer also is difficult to escape by luck, this mainly is because of the general large usage quantity of CALCIUM ACRYLATE in the multipolymer, and the ventilation property difference of acrylic polymer causes.Buildings or water-borne coating all have the requirement of ventilation property, if ventilation property is poor, tend to cause the bubbling phenomenon that can't freely overflow and produce owing to moisture in body of wall or the coating.On the other hand, this acrylic resin or acrylic copolymer resin generally all have enhanced shine as covering material, can not keep the gloss of original coating.
Purpose of the present invention is exactly in order to overcome above-mentioned defective, thereby provide a kind of organosilicon emulsion composition that cover uses on various water-borne coatings surface, single-component uses, quick solidifying and thoroughly, because pure organosilicon material has good ventilation property, therefore, can make water-borne coating keep the ventilation property that needs, coating bubbling problem can not occur.
Another object of the present invention is exactly as the protectant application of water-borne coatings with organosilicon emulsion composition of the present invention.
A further object of the invention has just provided a kind of method for formulating that is used for the organosilicon emulsion composition of water-borne coatings cover protection.Composition of the present invention is by 100 parts of organic silicon emulsions; 10～30 parts of many organoalkoxysilanes dispersion liquids are preferably 15～25 parts, are preferably 18～23 parts especially; At least a silicofluoride, its consumption is 0～6 part, is preferably 1～3 part, is preferably 1～2 part especially; Silicofluoric acid ethyl ester dispersion liquid, its consumption is 0～5 part, is preferably 1～3 part, is preferably 2～3 parts especially; Its consumption of at least a polyphosphoric acid salt is 0～5 part, is preferably 0～3 part, is preferably 0～1 part especially; The organo-tin compound dispersion liquid, its consumption is 0～3 part, is preferably 0～1.5 part, is preferably 0～0.8 part especially; Regulating the said composition solid content with deionized water is 10～40%, is preferably 10～25%, is preferably 10～15% especially.The used umber of above component all calculates by its solid part weight.
Used organic silicon emulsion can be with anion organosilicon emulsion or positively charged ion organic silicon emulsion or nonionic organic silicon emulsion in the organosilicon emulsion composition of the present invention, can be with the pressure dispersion emulsion of polymkeric substance synthesizing organo-silicon emulsion or silicone oil.The organosilicon polymer side group can be C
1～C
4Alkyl or phenyl, benzyl, but two end groups all must have a hydroxyl respectively.Ability and how alkoxy silane cross linked reaction like this.Simultaneously the number-average molecular weight of organosilicon molecule should remain between 100～3000, and molecular weight is too low, and curing speed can slow down; Molecular weight is too high can to influence its cross-linking density again.Preferred number-average molecular weight is 500～2500, and particularly preferred number-average molecular weight is 800～2000.
In addition, for preferred organosilicon negatively charged ion of organic silicon emulsion resin or positively charged ion synthetic emulsion resin, this mainly be because the synthetic resins molecular weight more near ideal range, simultaneously stability is better; On the other hand, under identical emulsifying agent consumption condition, the stability of negatively charged ion or cation emulsion resin is better than non-ionic type.Preferred especially organosilicon cationic synthetic emulsion resin, this mainly is that the quaternary amine that contains in the cation emulsion resin has very strong fungus and mildew resistance function.Most preferably make emulsifying agent with the non-ionic type quaternary amine, make catalyzer synthetic organosilicon cationic emulsion with tetra-alkyl ammonium hydroxide, this also considers from stable aspect.
The many organoalkoxysilanes that use in the silicon composition among the present invention have following structure:
R in the formula
1Be C
1～C
4Alkyl, phenyl, benzyl or OR
2Base, preferred C
1～C
2Alkyl or OR
2Base, preferred especially OR
2Base.This main because phenyl, benzyl are sterically hindered bigger, and preferred OR
2This is to consider from increasing cross-linking set quantity for a base, if polymkeric substance or silicone oil molecular weight hang down then do not have this necessity.R
2, R
3Base respectively is H, C
1～C
4Alkyl or alkali metal, preferred C
1～C
4Alkyl.This is because C
1～C
2The alkyl stability that existing good reactive behavior is necessary again concerning this many organoalkoxysilanes.
Using at least a silicofluoride in the present composition preparation, is best with potassium silicofluoride, and Sodium Silicofluoride takes second place, all at preferred row.The polyphosphoric acid salt of Shi Yonging in addition, its polymerization degree is preferably 2～4, is preferably 3 especially; To use 1～divalent salt best, for example: Potassium tripolyphosphate etc.The organo-tin compound that uses is with dibutyl tin laurate or stannous octoate best results, particularly dibutyl tin laurate best results.
The invention will be further described below by embodiment and comparative example, but the present invention is not limited only to these examples.
The appraisal procedure of water-borne coatings protective material using method and effect is described as follows:
(1) using method:
Sample to be tested is sprayed on drying that water-borne coatings forms coating base plate surface completely by the concentration of 10% solid content with agricultural atomizer, must sprays fully.Treat that first pass did not spray before the complete drying by first pass spraying method spraying second time, in the environment of 25 ℃ of relative humidity 45%～70%, place, treat behind the complete drying.
(2) appraisal procedure:
1. following test condition is 23 ℃ ± 2 ℃ of room temperatures, humidity 45%～70%, and substrate is 107 paint coatings (4%PVA1799: 250 order talcum powder=1: 1).
2. the artificial accelerated aging experiment condition is: three power are the medium pressure mercury lamp of 300W, and envrionment temperature is 85 ℃ ± 5 ℃, and Continuous irradiation was observed after 72 hours.If complete efflorescence of coating or serious discoloration are chosen as the difference level; Slight efflorescence of coating or variable color be chosen as can the level; Slightly variable color and do not have efflorescence and be chosen as good level of coating; The coating no change is chosen as top grade.
3. hydrophobicity is evaluated as through the material upstream face after the surface treatment and takes out (the about 0.1MPa of hydraulic pressure) after 10 minutes at continuous water spray, and moisture infiltrates base material and also causes the swelling of paint coating saboteur to be poor level; Moisture can not infiltrate base material, but can surface spreading be can the level; Moisture goes out to have at material surface slightly to be sprawled or wetting is good level; Moisture is nonwetting fully at material surface, only forms some globule persons not of uniform size and is top grade.
4. reliability evaluation was done a hydrophobicity test every 1 day, and the grading standard class can not reduce.15 tests all degradation do not the take place, and the person is top grade; Continuous reduction person is not taken place for 10 times be good level; Continuous reduction person is not taken place for can level for 5 times; Reduction person promptly occurs less than 5 experiments and be the difference level.
5. midew proof is with reference to the anti-mould assay method of GB/T1741-1979 paint film.
6. the measuring method of dry solidification time is that embodiment or comparative example sample produce stable hydrophobic interaction required time.Specific practice was to do one time the hydrophobicity evaluation experimental every 2 hours, and continuous 5 hydrophobicity no changes are then so that wherein the time is set time for the first time.
7. the mensuration of water-intake rate is with reference to paint film water-intake rate assay method HG.2-1612-85 in the national standard laid down by the ministries or commissions of the Central Government and the specialized standard
Embodiment 1
With number-average molecular weight 100 parts of the non-ionic type emulsions of 250 hydroxymethyl silicone oil, 25 parts of Union carbide A-162 dispersion emulsions, 4 parts of Sodium Silicofluorides, 4 parts of silicofluoric acid ethyl ester dispersion emulsions, 2 parts of trisodium phosphates, 2 parts of stannous octoates, regulating solid content with deionized water is 20%.
Embodiment 2
With number-average molecular weight is 100 parts of 1500 PDMS (polydimethyl silane) anionic polymer emulsions, 20 parts of methyltrimethoxy silane dispersion emulsions, 2 parts of Sodium Silicofluorides, 3 parts of silicofluoric acid ethyl ester dispersion emulsions, 2 parts of tripoly phosphate sodium STPPs, 1 part of dibutyl tin laurate dispersion emulsion, regulating solid content with deionized water is 15%.
Embodiment 3
With number-average molecular weight 1500 100 parts of PDMS cationic polymer emulsions (adopting most preferred method for making), 20 parts of Union carbide A-162 dispersion emulsions, 1.5 parts of potassium silicofluorides, 2.5 parts of silicofluoric acid ethyl ester dispersion emulsions, 1 part of Potassium tripolyphosphate, 0.5 part of dibutyl tin laurate dispersion emulsion, regulating solid content with deionized water is 15%.
Used material umber all calculates by solid part weight among the above embodiment.
Comparative example 1:
Methyl acid alcohol sodium water solution is diluted to 10% solid content.
Comparative example 2:
With proportion of composing is vinylbenzene 30% (weight), Butyl acrylate 40% (weight), and methyl methacrylate 28%, the mixed monomer synthetic polymer emulsion of vinylformic acid 2% is diluted to 10% solid content.
Comparative example 3:
The organosilicon crylic acid latex that adopts nuclear-shell emulsion polymerization to form.Nuclear is for accounting for the PDMS of gross weight 15%, and shell is pressed the monomer composition of comparative example 2, accounts for 85% of gross weight.Specific practice is to drip mixed monomer in as the PDMS anionic emulsion of seed emulsion continuously, and the control dropping time is 2 hours, and temperature of reaction is 80 ℃ ± 1 ℃, is polymerized through 5 hours altogether.And then be cooled to below 40 ℃ with ammoniacal liquor and transfer between PH to 7.0～7.5, obtain solid content and be 50 ± 2% polymer emulsion.It is 10% stand-by that this emulsion is transferred solid content with deionized water.
Comparative result such as following table:
By above embodiment and comparative example as can be seen, composition of the present invention is as the cover protecting materials of water-borne coatings, and hydrophobicity, water-intake rate, polluting proofing property, ageing resistance, the water tolerance of water-borne coatings had outstanding improved action.Especially with the component of positively charged ion silicon breast, have more the unexistent outstanding resistance to fungi of other organic silicon emulsion component as organosilicon emulsion composition.Therefore, clearly this based composition has vast market prospect and huge commercial value.
Although the present invention has been done detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leaving the spirit and scope of the present invention can be obvious as various changes and modifications.
Claims (2)
1, a kind of organosilicon emulsion composition that is used for water-borne coating cover surface protection, it is by multiple emulsion and dispersion liquid is composite forms, and its composition is as follows in solid part weight:
(A) organic silicon emulsion is 100 parts, and this emulsion is anionic organic silicon emulsion, cation type organic silicon emulsion or non-ionic type organic silicon emulsion; This emulsion is the pressure dispersion emulsion of organosilicon polymer synthetic emulsion or silicone oil; This emulsion feature is that the polymer molecular chain two ends must be hydroxyl in the organic silicon emulsion, and number-average molecular weight is 100～2000;
(B) many organoalkoxysilanes dispersion agent is 15～30 parts, and wherein many organoalkoxysilanes have following structure:
R in the formula
1Be C
1～C
4Alkyl, phenyl, benzyl or OR
2Base, R
2, R
3Respectively be H, C
1～C
4Alkyl or alkali metal;
(C) at least a silicofluoride, its consumption are 0～6 part;
(D) silicofluoric acid ethyl ester dispersion liquid, its consumption are 0～5 part;
(E) at least a polyphosphoric acid salt, its consumption are 0～5 part;
(F) organo-tin compound dispersion liquid, its consumption are 0～3 part.
2, the organosilicon emulsion composition of claim 1 qualification is as the protectant application of water-borne coatings cover.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113256 CN1238453C (en) | 2002-01-22 | 2002-01-22 | Organosilicon emulsion composition for water-borne coating cover surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113256 CN1238453C (en) | 2002-01-22 | 2002-01-22 | Organosilicon emulsion composition for water-borne coating cover surface |
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|---|---|
| CN1434090A CN1434090A (en) | 2003-08-06 |
| CN1238453C true CN1238453C (en) | 2006-01-25 |
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| CN 02113256 Expired - Fee Related CN1238453C (en) | 2002-01-22 | 2002-01-22 | Organosilicon emulsion composition for water-borne coating cover surface |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555385B (en) * | 2009-05-07 | 2012-10-24 | 中国科学院广州化学研究所 | Water-reducible silicone coating and preparation method thereof |
| CN102030990B (en) * | 2009-09-28 | 2012-12-12 | 复旦大学 | Silicone oil microcapsule with slow-release characteristics and preparation method thereof |
| CN101818024B (en) * | 2010-04-09 | 2013-06-12 | 中科院广州化学有限公司 | Aqueous emulsion type organic silicon antifouling paint and preparation method and application thereof |
| CN105622878B (en) * | 2016-02-26 | 2018-04-27 | 武汉理工大学 | A kind of preparation method of aqueous waterproofing paint |
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