CN1304502C - Curing nanometer building paint from fluoride carbon resin at normal temperature and production thereof - Google Patents
Curing nanometer building paint from fluoride carbon resin at normal temperature and production thereof Download PDFInfo
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- CN1304502C CN1304502C CNB2004100499745A CN200410049974A CN1304502C CN 1304502 C CN1304502 C CN 1304502C CN B2004100499745 A CNB2004100499745 A CN B2004100499745A CN 200410049974 A CN200410049974 A CN 200410049974A CN 1304502 C CN1304502 C CN 1304502C
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Abstract
The present invention relates to the field of macromolecule paint, particularly to nano resin fluorinated carbon building paint solidified at normal temperature and a preparing method thereof. For obtaining the nano resin fluorinated carbon building paint solidified at the normal temperature, the present invention adopts a tin catalyst and has good functions so that the present invention can be realized. Meanwhile, between nanotechnology is used, unique performance is provided for the paint. A few auxiliary agents, such as a moist dispersing agent, a defoaming agent, a solidifying agent, an anti-settling agent, an ultraviolet absorbent, etc., are added to the paint of the present invention. Tinting pigment can also be added to the paint so that a coating film has certain covering power and various required colors. The paint of the present invention has the characteristics of long antiageing time, good stain resistance, good water resistance of the coating layer, good chemicals resistance, good salt and fog resistance, high hardness of the coating layer, strong adhesive force, etc.
Description
Technical field
The present invention relates to the high-molecular coating field, particularly about fluorocarbon-containing resin nanometer building coating of ambient cure and preparation method thereof.
Background technology
Fluorine atom diameter minimum, F-C bond distance is very short, bond energy is up to 477 KJ (kilojoule)/moles, thereby fluorine-type resin, has good high thermal resistance, chemical-resistant resistance and organic solvent, rub resistance, hate that oil, hydrophobic nature and surface are sticking, didirtresistance, weathering resistance etc.But its main drawback is to be difficult to processing, is insoluble to most of organic solvents, and temperature during up to 300～400 ℃ flowability still bad, this has just limited the use of fluorocarbon resin greatly.
1938, the U.S. developed the PTFE teflon resin, because antiseptic property is excellent especially, plastics king's title was arranged.The polyvinylidene fluoride resin PVDF that occur the sixties is mainly used in building coating.With KYNAR500 is the PVDF fluorine coating of brand, through the true test in 30 years, can keep original appearance substantially, has embodied the good weather resisteant energy of fluoro-containing coating, abroad mainly as the cover protection of the metal finishing sheet material of landmark building.
Chinese patent application number is 95104359 to disclose a kind of fluorocarbon coating of using about buildings roof and wall, makes it have durable, high temperature resistant, corrosion-resistant, weather, anti-excellent results such as fade.Its deficiency is that must carry out chemically cleaning to material surface handles and prime, and its drying temperature needs more than 230 ℃ simultaneously.Chinese patent application number be 97104244 disclose relevant metallic surface and applied fluorocarbon resin coating after, make its surface have high rigidity, good characteristic such as being stained with property not, but it has certain requirement to workpiece surface, workpiece surface need carry out chemical treatment simultaneously, and it must be dried under 400～420 ℃.
Summary of the invention
One of purpose of the present invention is to improve the performance of existing fluorocarbon coating; provide a kind of cheap and can be at Air drying solidified fluorocarbon-containing resin nanometer building coating; decoration coating especially for skin; this coating also can be coated on surfaces such as aluminium, roof, body of wall, ceramic tile, road sign, billboard, indicator plate, glass reinforced plastic, aluminium section bar, materials for construction, and special recommendation is used for the artifact protection.
Another object of the present invention is to provide the preparation method of the fluorocarbon-containing resin nanometer building coating of ambient cure.
The present invention has used tin class catalyzer in order to obtain the fluorocarbon-containing resin nanometer building coating of ambient cure, and it has good effect, and the present invention is achieved.Simultaneously owing to used nanotechnology also to give the coating particular performances.
Added some auxiliary agents in coating of the present invention, as Ricinate, defoamer, solidifying agent, anti-settling agent, UV light absorber etc., also can add tinting pigment, making films has certain opacifying power and needed various color.
The fluorocarbon-containing resin nanometer building coating of ambient cure of the present invention, but ordinary method construction, roll and method application such as spraying both available brush.
The fluorocarbon-containing resin nanometer building coating of ambient cure of the present invention, component and content by weight percentage are:
Fluorocarbon resin 30～90%
Catalyzer 0.001～1%
Dispersion agent 0.01～1%
Defoamer 0.01～1%
Anti-settling agent 0.01～5%
Nano-grade inorganics 0.5～10%
UV light absorber 0.01～2%
Pigment 0～30%
Pigment extender 0～30%
Solvent 1～20%
During use, can further add solidifying agent in coating, the add-on of solidifying agent is 2～30% of a coating gross weight.
Fluorocarbon resin of the present invention can be commercially available commercial fluorocarbon resin, as the HF001 resin, and ZB-C resin etc.
Catalyzer of the present invention can be a tin compound, comprises tindioxide, stannous oleate, stannous octoate, dibutyltin diacetate, dibutyl tin laurate, 2-2-ethylhexoic-dibutyl tin or dibutyl tin oxide etc.
Pigment extender of the present invention, main effect is at tinting pigment and makes have certain opacifying power and a color back of filming replenish required pigment part, and to filmed " filling effect " to increase coating thickness, improve weather resistance, thermotolerance and the surface hardness of filming, the contraction that reduction is filmed etc.Pigment extender can be light calcium carbonate, talcum powder, mica powder, ground barium sulfate, silica powder or their any mixture etc.; Be preferably talcum powder or mica powder, the levelling property that light calcium carbonate is filmed because of its influence among the present invention, ground barium sulfate and silica powder relative density Da Yi precipitation, thereby consumption is difficult for too high.
Dispersion agent of the present invention can be: the Anti-Terra-P of long-chain polyamino amidophosphoric acid salt such as BYK company (Bayer A.G), the BYK-P104S of undersaturated poly carboxylic acid of polymer such as BYK company, the Texaphor-963 of the salt of the derivative of poly carboxylic acid and amine such as Henkel company (Henkel KGaA company) and the SN-Dispersant-5040 of polycarboxylate sodium's class such as Henkel company etc.
Defoamer of the present invention can be: broken bubble polymkeric substance and the mixture of polysiloxane such as the BYK070 of BYK company, 5400,5600 etc. of modified organic silicon such as the modest trade of Taiwan moral stock company.
Anti-settling agent of the present invention can be: 4604A, 4604B, the 4604C of organobentonite such as Tianjin organic pottery clay factory, 275 or the 902 electric neutrality polymeric amide of the modest trade of Taiwan moral stock company and the mixture of polyester etc. of anion surfactant such as the modest trade of Taiwan moral stock company.
UV light absorber of the present invention can be: the Sanduvor3212 of aniline ethylenediamines and hindered amine mixture such as Clariant company, the Sanduvor3035 of benzophenone class such as Clariant company, the Tinuvin292 of hindered amines such as Ciba etc.
Pigment of the present invention can be coating various pigment commonly used, as high performance exterior coating since directly expose with atmosphere in, and directly be painted on the cement mortar surface that is alkalescence, weathering resistance, alkali resistance mineral dye is preferably selected in recommendation for use; Comprise Rutile type Titanium Dioxide, zinc oxide, medium chrome yellow medium yellow, deep chrome yellow, cadmium red or their any mixture etc.
Solidifying agent of the present invention can be: biuret polyisocyanate, hexamethylene diisocyanate (HDI) tripolymer, any mixed trimer of HDI and tolylene diisocyanate etc.
Solvent of the present invention can be: n-butyl acetate, ethyl acetate, 1-Methoxy-2-propyl acetate, toluene or dimethylbenzene etc.Any mixture
Nano-inorganic substance of the present invention can be: nano titanium oxide, nano silicon, nanometer titanium dioxide zinc, nano hydrotalcite or nano imvite etc.
The preparation method of the fluorocarbon-containing resin nanometer building coating of ambient cure of the present invention:
Under agitation, in container, add 30～90% fluorocarbon resin, 0.01～1% dispersion agent, 0.01～1% defoamer, 0.01～5% anti-settling agent, 0.01～2% UV light absorber, 0.5～10% nano-grade inorganics stirred 0.5～2 hour, 0.001～1% the catalyzer of adding again after evenly to be mixed, reacted 1～3 hour, and in above-mentioned composition, added 0～30% pigment again, high speed dispersion, add 0～30% pigment extender again, grind through sand mill, make fineness below 40 microns, it is even to add 1～20% stirring solvent again.
During use, can further add solidifying agent in coating, the add-on of solidifying agent is 2～30% of a coating gross weight, stirs, and slaking is 10～60 minutes under 15～40 ℃ of conditions, and then constructs.
For further improving the mix effect, can adopt the container that twin shaft double speed stirrer is housed, the twin shaft rotating speed of twin shaft double speed stirrer is one fast one slow, sawtooth disk impeller is equipped with in the end of high speed shaft, and its circumferential speed reaches about 20m/s, mainly plays dissemination, slow-speed shaft drives one three leaf frame type agitating blade, the main mixing effect that rises, its rotating speed is very low, to adapt to the mix of sticky material.The outer rim of frame type agitating blade and stainless cylinder of steel gap are very little, can play the effect of scraping wall.Twin shaft also does pumping doing turning motion simultaneously, further improves the mix effect.
The fluorocarbon-containing resin building coating of Air drying of the present invention has the excellent properties of following uniqueness:
1. the ageing-resistant time is long: it can reach 15～20 years and not come off, not efflorescence.This weathering resistance free from worldly cares comes from the high strength of C-F key, and unreactiveness coating is provided, and with the ultraviolet light degradation property.Artificial accelerated aging in daylight type senile experiment machine experiment showed, fluorocarbon coating after 5000 hours, and its gloss retention is still more than 80%, can keep the bright-coloured of self color and luster throughout the year.
2. contamination resistance can be good: be not afraid of oil, do not have electrostatic adhesion, if body of wall has dust, after rainwater dashes pouring, expose new coating immediately, a kind of feeling of freshness is arranged.
3. water-resistant coating is good especially, the energy waterproof, and water can not enter matrix by coating.
4. chemical-resistant resistance and salt spray resistance are good: its chemical proofing is than several times to tens times of other coating, and fluorocarbon coating also has mildew resistance and flame retardant resistance.
5. coating hardness height, sticking power is good: with the suitable jail of body of wall bonded, collide, beat coating and all do not play sled behind the coating curing, do not come off, the coating rub resistance is difficult for scratching.
Fluorocarbon-containing resin building coating over-all properties ideal, economic benefit and the obvious social benefit of ambient cure of the present invention.Fluorocarbon coating also has characteristics such as the soft elegance of filming, feel is smooth, snappiness is good except that having above performance, be a kind of over-all properties ideal coating products.
Embodiment
Below with reference to embodiment the present invention is described in further detail.
Embodiment 1.
In middle body is equipped with the stainless cylinder of steel of drum type of twin shaft double speed stirrer, add 30% fluorocarbon resin HF001 resin, under the stirring at low speed with 0.02% dispersant A nti-Terra-P, 0.03% defoamer BYK070,0.04% anti-settling agent 275,2% nanometer titanium dioxide zinc, 0.2% UV light absorber Sanduvor3035, join in the stainless cylinder of steel, to be mixed evenly after, add 0.001% the inferior tin of octoate catalyst again, after reaction for some time, add 20% pigment Rutile type Titanium Dioxide again in composition, high speed dispersion adds 30% pigment extender talcum powder again, behind sand mill, check that fineness below 20～40 microns, adds 15% N-BUTYL ACETATE again, stir.
In use, adding in composite paint is the solidifying agent biuret polyisocyanate of its gross weight 8.709%, stirs, and slaking is constructed after 30～50 minutes again under 15～40 ℃ of conditions.
The coating of embodiment 1 is well suited for doing high performance outer wall building coating, and gained coating component is as follows, performance technologies parameter such as table 1.
Fluorocarbon resin HF001 resin 30%
The inferior tin 0.001% of octoate catalyst
Dispersant A nti-Terra-P 0.02%
Defoamer BYK070 0.03%
Anti-settling agent 275 0.04%
Nanometer titanium dioxide zinc 2%
UV light absorber Sanduvor3035 0.2%
Pigment Rutile type Titanium Dioxide 20%
Pigment extender talcum powder 24.709%
Solidifying agent biuret polyisocyanate 8%
Solvent butyl acetate 15%
Embodiment 2
In middle body is equipped with the stainless cylinder of steel of drum type of twin shaft double speed stirrer, add 50% fluorocarbon resin ZB-C resin, under the stirring at low speed with 0.05% dispersion agent Texaphor-963,0.05% defoamer 5400,0.04% anti-settling agent 902,5% nanometer titanium dioxide zinc, 0.06% UV light absorber Sanduvor3212, join in the stainless cylinder of steel, to be mixed evenly after, add 0.002% catalyzer dibutyl tin oxide again, after reaction for some time, in composition, add 8% pigment medium chrome yellow medium yellow again, after the high speed dispersion, add 6.798% pigment extender ground barium sulfate again, through checking behind the sand milling that fineness is below 20 microns, add 5% dimethylbenzene and 5% N-BUTYL ACETATE again, stir.
In use, adding in composite paint is solidifying agent hexamethylene diisocyanate (HDI) tripolymer of its gross weight 20%, stirs, and slaking is constructed after 30～50 minutes again under 15～40 ℃ of conditions.
The coating of embodiment 2 is well suited for doing high performance high light enamel paint, and gained coating component is as follows, performance technologies parameter such as table 1.
Fluorocarbon resin ZB-C resin 50%
Catalyzer dibutyl tin oxide 0.002%
Dispersion agent Texaphor-963 0.05%
Defoamer 5,400 0.05%
Anti-settling agent 902 0.04%
Nanometer titanium dioxide zinc 5%
UV light absorber Sanduvor3212 0.06%
Pigment medium chrome yellow medium yellow 8%
Pigment extender ground barium sulfate 6.798%
Solidifying agent hexamethylene diisocyanate (HDI) tripolymer 20%
Solvent xylene 5%
N-BUTYL ACETATE 5%
Embodiment 3
In middle body is equipped with the stainless cylinder of steel of drum type of twin shaft double speed stirrer, add 65% fluorocarbon resin ZB-C resin, under the stirring at low speed with 0.03% dispersion agent Texaphor-963,0.04% defoamer 5400,0.3% anti-settling agent 902,1.6% nano imvite, 0.029% UV light absorber Tinuvin328, join in the stainless cylinder of steel, to be mixed evenly after, add 0.001% catalyzer dibutyl tin laurate again, after reaction for some time, in composition, add 4% pigment zinc oxide again, after the high speed dispersion, add 5% pigment extender talcum powder again, through checking behind the sand milling that fineness is below 20 microns, add 5% dimethylbenzene and 5% 1-Methoxy-2-propyl acetate again, stir.
In use, adding in composite paint is the solidifying agent biuret polyisocyanate of its gross weight 14%, stirs, and slaking is constructed after 15～30 minutes again under 15～40 ℃ of conditions.
The coating of embodiment 3 is well suited for doing high performance finishing paint, and gained coating component is as follows, performance technologies parameter such as table 1.
Fluorocarbon resin % ZB-C resin 65%
Catalyzer dibutyl tin laurate 0.001%
Dispersion agent Texaphor-963 0.03%
Defoamer 5,400 0.04%
Anti-settling agent 902 0.3%
Nano imvite 1.6%
UV light absorber Tinuvin328 0.029%
Pigment zinc oxide 4%
Pigment extender talcum powder 5%
Solvent 1-Methoxy-2-propyl acetate 5%
Dimethylbenzene 5%
Solidifying agent biuret polyisocyanate 14%
Table 1
| Project | Index | The method of inspection | ||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | ||||
| The shock-resistant kg.cm of gloss sticking power (method of drawing a circle) level hardness (fork method) | 90 1 0.65 50 | 90 1 0.65 50 | 90 1 0.65 50 | GB/T9754 GB/T9286 GB/T6739 GB/T1732 | ||
| The heatproof difference changes and abrasion resistance | Can normally use 12000 paint films not have breakage in-40 ℃～140 ℃ scopes | GB/T1765 | ||||
| Chemical proofing | 10% sulfuric acid, 10% hydrochloric acid, 10% sodium hydroxide, 10% ammoniacal liquor toluene | The unchanged paint film of the unchanged paint film of the unchanged paint film of the unchanged paint film of paint film is unchanged | The unchanged paint film of the unchanged paint film of the unchanged paint film of the unchanged paint film of paint film is unchanged | The unchanged paint film of the unchanged paint film of the unchanged paint film of the unchanged paint film of paint film is unchanged | GB/T1765 | |
| Salt spray resistance experiment 2000 hours | Paint film is non-foaming, do not come off | GB/T1765 | ||||
| The artificial accelerated aging experiment | 2000 hours | Paint film loss of gloss rate 11%, 2 grades of variable colors | GB/T1765 | |||
| 5000 hours | Paint film loss of gloss rate 25%, paint film does not have efflorescence, and variable color is that 2 grades (value of chromatism 3.2) do not have be full of cracks and other catabiosis | GB/T1865 | ||||
Claims (10)
1. the fluorocarbon-containing resin nanometer building coating of an ambient cure is characterized in that: the component of described coating and content by weight percentage are:
Fluorocarbon resin 30～90%
Catalyzer 0.001～1%
Dispersion agent 0.01～1%
Defoamer 0.01～1%
Anti-settling agent 0.01～5%
Nano-grade inorganics 0.5～10%
UV light absorber 0.01～2%
Pigment 0～30%
Pigment extender 0～30%
Solvent 1～20%
Described dispersion agent is selected from long-chain polyamino amidophosphoric acid salt, the undersaturated poly carboxylic acid of polymer, a kind of among the salt of the derivative of poly carboxylic acid and amine and the polycarboxylate sodium;
Described nano-inorganic substance is nano titanium oxide, nano silicon, nanometer titanium dioxide zinc, nano hydrotalcite or nano imvite;
Described catalyzer is tindioxide, stannous oleate, stannous octoate, dibutyltin diacetate, dibutyl tin laurate, 2-2-ethylhexoic-dibutyl tin or dibutyl tin oxide;
The fineness of the solid matter in the above-mentioned coating is below 40 microns.
2. coating according to claim 1 is characterized in that: further be added with solidifying agent in the described coating, the add-on of solidifying agent is 2～30% of a coating gross weight.
3. coating according to claim 1 is characterized in that: described pigment extender is light calcium carbonate, talcum powder, mica powder, ground barium sulfate, silica powder or their any mixture.
4. coating according to claim 1 is characterized in that: described defoamer is selected from brokenly a kind of in the mixture of bubble polymkeric substance and polysiloxane and the modified organic silicon.
5. coating according to claim 1 is characterized in that: described anti-settling agent is selected from organobentonite, anion surfactant, a kind of in the mixture of electric neutrality polymeric amide and polyester.
6. coating according to claim 1 is characterized in that: described UV light absorber is selected from aniline ethylenediamines and hindered amine mixture, benzophenone class, a kind of in the hindered amines.
7. coating according to claim 1 is characterized in that: described pigment is Rutile type Titanium Dioxide, zinc oxide, medium chrome yellow medium yellow, deep chrome yellow, cadmium red or their any mixture.
8. coating according to claim 2 is characterized in that: described solidifying agent is biuret polyisocyanate, hexamethylene diisocyanate tripolymer, any mixed trimer of hexamethylene diisocyanate and tolylene diisocyanate.
9. preparation method according to claim 1,3,4,5,6 or 7 described coating is characterized in that:
Under agitation, the fluorocarbon resin that in container, adds 30～90wt%, 0.01 the dispersion agent of～1wt%, 0.01 the defoamer of～1wt%, 0.01 the anti-settling agent of～5wt%, 0.01 the UV light absorber of～2wt%, the nano-grade inorganics of 0.5～10wt% stirs, the catalyzer that adds 0.001～1wt% after evenly more to be mixed, react, in above-mentioned composition, add the pigment of 0～30wt% again, high speed dispersion, the pigment extender that adds 0～30wt% again, grind through sand mill, make fineness below 40 microns, the stirring solvent that adds 1～20wt% again is even.
10. preparation method according to claim 9 is characterized in that: further be added with solidifying agent in the described coating, the add-on of solidifying agent is 2～30wt% of coating gross weight, stirs.
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| CNB2004100499745A CN1304502C (en) | 2004-06-23 | 2004-06-23 | Curing nanometer building paint from fluoride carbon resin at normal temperature and production thereof |
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| CNB2004100499745A CN1304502C (en) | 2004-06-23 | 2004-06-23 | Curing nanometer building paint from fluoride carbon resin at normal temperature and production thereof |
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| CN1304502C true CN1304502C (en) | 2007-03-14 |
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