CN101824250B - Fluorocarbon resin coating - Google Patents
Fluorocarbon resin coating Download PDFInfo
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- CN101824250B CN101824250B CN2010101493582A CN201010149358A CN101824250B CN 101824250 B CN101824250 B CN 101824250B CN 2010101493582 A CN2010101493582 A CN 2010101493582A CN 201010149358 A CN201010149358 A CN 201010149358A CN 101824250 B CN101824250 B CN 101824250B
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Abstract
The invention provides a fluorocarbon resin coating, which comprises the following components in percentage by weight: 20 to 70 percent of fluorocarbon resin of which the weight-average molecular weight is between 5,000 and 20,000, 1 to 7 percent of fluorine-containing compound or silicon-containing compound, 1 to 5 percent of inorganic nanometer-powder, 1.1 to 7.2 percent of drier, and the balance of organic solvent, wherein the fluorine-containing compound or the silicon-containing compound comprises one or more radicals of an epoxy group, an amino group, a hydroxyl group, a carboxyl group, a sulfonic acid group and an ester group. The fluorocarbon resin coating cannot generate free low surface energy substances in use; and when the fluorocarbon resin coating is coated on the surface of a coating workpiece to form a coating layer, on the first hand, the coating workpiece is isolated from a painting environment to ensure that the coating workpiece can be cleaned easily and the cleaning cost is reduced, and on the other hand, the painting effect is not influenced to avoid shrinkage cavities on the surface of a paint film.
Description
Technical field
The present invention relates to paint field, particularly a kind of fluorocarbon resin coating.
Background technology
Coating is a kind of Chemicals that contain pigment or do not contain pigment, process with resin and wet goods.Can dry and hard film forming on body surface with applying coating, the surface of coated article and surrounding medium are separated, thereby the coated article body is played a protective role.Contact angle was one type of fast-developing in recent years Surface Engineering coating system greater than the coating of 90 degree when low surface energy coatings was meant after the coating and contacts with matrix.Low surface energy coatings mainly includes machine silicon coating, fluorocarbon resin coating and organosilicon-fluorine coating; Wherein, Coating appellation with the fluorocarbon resin main film forming substance is a fluorocarbon resin coating, and the carbon fluorine chain in the fluorocarbon polymer is short, and chain can be high; Therefore molecular structure stabilized, polarity are low; And fluorine atom arranges and closely in that carbon skeleton is outer, thereby prevented that carbon atom and carbochain from exposing, so type coating has performances such as chemical-resistant and protection against corrosion, wear resistance, insulativity, the contamination resistance of excellence.
Disclose a kind of fluoride resin antifouling paint compositions among the Chinese patent CN1437626A, this kind coating is mainly used in and suppresses the stained of ground in the marime fouling environment.Disclose a kind of low surface energy anti-fouling paint compsn among the Japanese Patent NO.6-506632 (international publication number WO94/06870), this kind coating is mainly used in the external wall soiling protective.Among the Chinese patent CN1427054A, announce a kind of surface hydrophilicity that has, polluted release effects and to the non-staining coating of the good anti fouling performance of greasy dirt, this kind coating is mainly used in the protection buildings.Announced a kind of have good antifouling property, nontoxic fluorine-containing low surface energy for marine anti-fouling ship paint among the Chinese patent CN1388196A, this kind coating is mainly used in and reduces the pollution of sea life to boats and ships.
In automobile production, application is important production process, and in coating process, the workpiece that wall, ground and the various carriage in the spray room, chassis, sled, frock, anchor clamps etc. need recycle is polluted by over-sprayed paint fog through regular meeting.Because these equipment claimed life-time service under the environment that sprays paint, the over-sprayed paint fog that accumulates above it can get more and more, thereby often needs the processing of keeping a public place clean of these workpiece.Conventional cleaning method is for burning, use paint remover, high temperature fluidized bed cleaning or Cleaning by High Pressure Water Jet.But above-mentioned cleaning mode exists all that cleaning cost is high, cleaning performance is not good and problem such as environmental pollution.Therefore the inventor considers, low surface energy coatings is applied in the application workpiece, the application workpiece and the environment that sprays paint is isolated, and then reduce the harm of cleaning cost and environment being caused.But do not find also that at present fluorocarbon resin coating well known in the art is widely used in the application workpiece; This is because in the painting dressing automobiles production process; Spray paint to free low surface energy material and sensitivity thereof, if having the low surface energy material to separate out oozes out and can cause great effect by paint film, free low surface energy material is if cause serious paint film drawback in painting workshop long-term accumulation meeting in the coating; Be that shrinkage cavity appears in coating surface, have a strong impact on the effect of spraying paint.Contain the low surface energy material of free state in the existing fluorocarbon resin coating, like low-molecular-weight fluorocarbon or silicone oil etc., therefore, existing fluorocarbon coating can not be applied to the application workpiece.
Therefore, the inventor considers that providing a kind of does not contain the fluorocarbon coating of free state low surface energy material and be applied to the application workpiece, and then makes the application workpiece avoid the over-sprayed paint fog infringement, does not influence the effect of spraying paint.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of fluorocarbon resin coating, and said fluorocarbon resin coating can be applicable to the application workpiece, and the application workpiece and the environment that sprays paint are isolated, and reduces and cleans cost, and use said fluorocarbon resin coating not influence the effect of spraying paint.
In order to solve above technical problem, the present invention provides a kind of fluorocarbon resin coating, comprising:
The weight-average molecular weight of 20wt%～70wt% is 5000～20000 fluorocarbon resin;
The fluorochemicals of 1wt%～7wt% or silicon-containing compound, said fluorochemicals or silicon-containing compound contain one or more groups in epoxy group(ing), amino, hydroxyl, carboxyl, sulfonic group, the ester group;
The inorganic nanometer-powder of 1wt%～5wt%;
The siccative of 1.1wt%～7.2wt%;
The siccative of surplus.
Preferably, said fluorocarbon resin is fluoroolefins resin, vinylformic acid fluoride resin or fluoro ether resin.
Preferably; Said fluorochemicals is fluorine butyric acid, Perfluorocaprylic Acid, fluorine-containing alkyl sodium sulfonate, fluorine-containing oxa-amide salt, fluorine-containing oxa-quaternary amine, perfluor acid Witepsol W-S 55,2; 2-two (3-amino-4-hydroxy phenyl) HFC-236fa, N-[4-cyanic acid-3-(trifluoromethyl) phenyl]-2-methyl-2, one or more in the 3-epoxy group(ing) propionic acid amide.
Preferably, said silicon-containing compound is carboxylic alkyl modified polyorganosiloxane and/or quaternary ammonium salt modified polysiloxane.
Preferably, said inorganic nanometer-powder is one or more in SiO 2 powder, aluminium sesquioxide powder, the lime carbonate end.
Preferably, the particle diameter of said inorganic nanometer-powder is 50nm～600nm.
Preferably, said siccative is tetrabutyl tin, tetrabutyl cobalt or rare earth drier.
Preferably, said solvent is YLENE, butylacetate, butanols or butanone.
Preferably, also comprise: the softening agent of 0.1wt%～1.2wt%.
Preferably, said softening agent is one or more in acrylics, alkyd based resin, epoxy property phenolic resinoid, the polyester resin.
The invention provides a kind of fluorocarbon resin coating; It is to be that 5000～20000 fluorocarbon resin is a main film forming substance with weight-average molecular weight; The fluorocarbon resin of molecular weight in above-mentioned scope not only had been difficult for forming the compound of free state but also being prone to film forming, and the fluorochemicals in the said fluorocarbon resin coating or silicon-containing compound be tensio-active agent, reduced the surface tension between each component interface in the coating; It can better be dissolved each other, form the stabilizing solution system; It contains one or more groups in epoxy group(ing), amino, hydroxyl, carboxyl, sulfonic group, the ester group simultaneously; In film formation reaction, also play linking agent, therefore said fluorochemicals or silicon-containing compound not only can increase the mutual solubility of each component in the coating but also can not be present in the coating system with free state.In sum; Fluorocarbon resin coating provided by the invention in use can not produce free low surface energy material; This fluorocarbon resin is coated in the coating that the application workpiece surface forms; Can realize the application workpiece and the environment isolation of spraying paint on the one hand, make the application workpiece easy to clean, reduce cleaning cost; Do not influence the effect of spraying paint on the other hand again, avoid coating surface shrinkage cavity to occur.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of fluorocarbon resin coating, comprising:
The weight-average molecular weight molecular weight of 20wt%～70wt% is 5000～20000 fluorocarbon resin;
The fluorochemicals of 1wt%～7wt% or silicon-containing compound, and contain one or more groups in epoxy group(ing), amino, hydroxyl, carboxyl, sulfonic group, the ester group in said fluorochemicals or the silicon-containing compound;
The inorganic nanometer-powder of 1wt%～5wt%;
The siccative of 1.1wt%～72wt%;
The organic solvent of surplus.
According to the present invention, fluorocarbon resin is preferably one or more in the following polymkeric substance: fluoroolefins resin, vinylformic acid fluoride resin, fluoro ether resin are preferably fluoroolefins resin and vinylformic acid fluoride resin.Said fluorocarbon resin weight-average molecular weight is 5000～20000, and if the fluorocarbon resin molecular weight is too small, and then the coating that makes of resin in use is prone to ooze out the free state compound thus, causes the paint film drawback; If molecular weight then is difficult for participating in film formation reaction excessive.The fluorocarbon resin weight-average molecular weight is preferably 8000～16000, and more preferably 10000～15000.The content of fluorocarbon resin is 20wt%～70wt%, is preferably 40wt%～60wt%.
Fluorochemicals in the fluorocarbon resin coating that the embodiment of the invention provides or silicon-containing compound are on the one hand as tensio-active agent; Reduce the surface tension between each component interface in the coating; It can better be dissolved each other; Form the stabilizing solution system,, therefore also in film formation reaction, play linking agent simultaneously because it contains one or more groups in epoxy group(ing), amino, hydroxyl, carboxyl, sulfonic group, the ester group.Said fluorochemicals or silicon-containing compound not only can strengthen the mutual solubility of each component in the coating but also can not be present in the coating system with free state.According to the present invention; Said fluorochemicals is preferably one or more in the following compound: fluorine butyric acid, Perfluorocaprylic Acid, fluorine-containing alkyl sodium sulfonate, fluorine-containing oxa-amide salt, fluorine-containing oxa-quaternary amine, perfluor acid Witepsol W-S 55,2; 2-two (3-amino-4-hydroxy phenyl) HFC-236fa, N-[4-cyanic acid-3-(trifluoromethyl) phenyl]-2-methyl-2,3-epoxy group(ing) propionic acid amide.Said silicon-containing compound is preferably selected from one or more in carboxylic alkyl modified polyorganosiloxane and the quaternary ammonium salt modified polysiloxane.The content of said fluorochemicals or silicon-containing compound is 1wt%～7wt%, is preferably 3wt%～5wt%.
Inorganic nanometer-powder plays enhancement in coating system, in order to heat-resistance type, chemicals-resistant and the ageing-resistant performance after the raising coating film forming, make low surface energy coat be difficult for decomposing, and can the quality of spraying paint of painting hall not impacted.According to the present invention, the content of inorganic nanometer-powder is 1wt%～5wt%, is preferably 2wt%～4wt%, and inorganic nanometer-powder preferably selects for use particle diameter to be preferably in the SiO 2 powder, aluminium sesquioxide powder, lime carbonate end of 50nm～600nm one or more.
Siccative can quicken the curing speed of coating, is preferably tetrabutyl tin, tetrabutyl cobalt or rare earth drier according to siccative of the present invention, and content is 1.1wt%～72wt%, and preferred content is 2.5wt%～6.5wt%.Organic solvent is preferably YLENE, butylacetate, butanols or butanone, more preferably butylacetate.
According to the present invention, said fluorocarbon resin coating also preferably includes: the softening agent of 0.1wt%～1.2wt%, and in order to the sticking power of the film forming properties that improves fluorocarbon resin and itself and coating ground.Softening agent is preferably selected from one or more in acrylics, alkyd based resin, epoxy property phenolic resinoid, the polyester resin.
Can preparing of said fluorocarbon resin coating according to method well known to those skilled in the art; Specifically can for: be dissolved in the solvent after fluorocarbon resin, fluorochemicals or silicon-containing compound, inorganic nanometer-powder, softening agent mixed, stirring solvent evenly added siccative and continues to stir and obtain the emulsion form fluorocarbon resin coating in the back.
In order further to understand the present invention, fluorocarbon resin provided by the invention is described below in conjunction with embodiment.PVDF in following examples is provided by Guangzhou Li Chang Fluroplast-4 ltd, and weight-average molecular weight is 12000; Fluoro ether resin is provided by Italian Solvy SolexisS.P.A (Italy) company, and trade names are Hylar; The bisphenol-A liquid novolac epoxy 128 of epoxy phenolics for providing for Wuxi impregnating material of a specified duration ltd; The vinylformic acid fluoride resin is provided by Shandong Zhongfu Chemical Technology Co., Ltd., and weight-average molecular weight is 15000; Carboxylic alkyl modified polyorganosiloxane is provided by Shin-Etsu Chemial Co., Ltd, and model is KF-9701; Quaternary ammonium salt modified polysiloxane is provided by Daukangnin GmbH, and model is OP-8800.
Embodiment 1
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 2
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 3
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 4
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 5
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 6
The composition of the fluorocarbon resin coating that present embodiment provides is:
Among the embodiment 7
The composition of the fluorocarbon resin coating that present embodiment provides is:
Among the embodiment 8
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 9
The composition of the fluorocarbon resin coating that present embodiment provides is:
Embodiment 10
The composition of the fluorocarbon resin coating that present embodiment provides is:
The fluorocarbon resin coating that embodiment 1 to 10 is provided is sprayed on the application bracket surface, and coat-thickness is 120 microns, measures coating performance and lists in table 1.
The water contact angle test
Testing tool: the G-1 type ε rma angle gauge formula contact angle instrument that Japanese Kyowa company produces.
Testing method: the deionized water water droplet dripped behind coatingsurface 1min test, each sample is got 3 points of mutually huge spacing 5mm and is measured, and totally 6 readings are got arithmetical av.
Pencil hardness test
Testing tool: the fertile and husband * prestige of Sheen 720N and Bonn pencil test appearance
Testing method: with the pencil of various different hardness, become miter angle with coatingsurface, draw on coatingsurface with 765 gram forces, the hardness of just in time scratching the pencil of coating is the pencil hardness of this paint film.
Table 1 coating performance test result
The present invention provides a kind of fluorocarbon resin coating; This coating and application workpiece had bonding force preferably; The coating that forms at the application workpiece surface has higher hardness and antifouling property preferably, has reduced the cleaning cost, does not therefore contain the low surface energy compounds of free state simultaneously in the said fluorocarbon resin coating; Therefore use fluorocarbon resin coating can not influence the effect of spraying paint, avoid coating surface the generation of shrinkage cavity situation to occur.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (6)
1. a fluorocarbon resin coating that is used for the painting dressing automobiles workpiece is characterized in that, comprising:
The weight-average molecular weight of 20wt%～70wt% is 5000～20000 fluorocarbon resin, and said fluorocarbon resin is fluoroolefins resin, vinylformic acid fluoride resin or fluoro ether resin;
The fluorochemicals of 1wt%～7wt% or silicon-containing compound; Said fluorochemicals is fluorine butyric acid, Perfluorocaprylic Acid, fluorine-containing alkyl sodium sulfonate, fluorine-containing oxa-amide salt, fluorine-containing oxa-quaternary amine, perfluor acid Witepsol W-S 55,2; 2-two (3-amino-4-hydroxy phenyl) HFC-236fa, N-[4-cyanic acid-3-(trifluoromethyl) phenyl]-2-methyl-2, one or more in the 3-epoxy group(ing) propionic acid amide; Silicon-containing compound is carboxylic alkyl modified polyorganosiloxane and/or quaternary ammonium salt modified polysiloxane;
The inorganic nanometer-powder of 1wt%～5wt%;
The siccative of 2.5wt%～6.5wt%, said siccative are tetrabutyl tin or rare earth drier;
The organic solvent of surplus.
2. fluorocarbon resin coating according to claim 1 is characterized in that, said inorganic nanometer-powder is one or more in SiO 2 powder, aluminium sesquioxide powder, the lime carbonate end.
3. fluorocarbon resin coating according to claim 2 is characterized in that, the particle diameter of said inorganic nanometer-powder is 50nm～600nm.
4. fluorocarbon resin coating according to claim 1 is characterized in that, said solvent is YLENE, butylacetate, butanols or butanone.
5. fluorocarbon resin coating according to claim 1 is characterized in that, also comprises: the softening agent of 0.1wt%～1.2wt%.
6. fluorocarbon resin coating according to claim 5 is characterized in that, said softening agent is one or more in acrylics, alkyd based resin, epoxy property phenolic resinoid, the polyester resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101493582A CN101824250B (en) | 2010-04-19 | 2010-04-19 | Fluorocarbon resin coating |
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| CN2010101493582A CN101824250B (en) | 2010-04-19 | 2010-04-19 | Fluorocarbon resin coating |
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| CN101824250B true CN101824250B (en) | 2012-01-25 |
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| CN105505028B (en) * | 2015-11-23 | 2018-07-20 | 许晓丽 | A kind of one-pack-type fluorocarbon coating and preparation method thereof |
| CN105462481B (en) * | 2015-12-23 | 2017-10-03 | 怀化学院 | A kind of compositions of ultraviolet curing type |
| CN108610780A (en) * | 2016-12-02 | 2018-10-02 | 洛阳尖端技术研究院 | A kind of fluorocarbon resin coating and preparation method thereof |
| CN111187557A (en) * | 2020-03-18 | 2020-05-22 | 哈尔滨市雪鹰工程材料有限公司 | Cold zone temperature difference resistant epoxy resin protective paint coating |
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| CN101230224A (en) * | 2008-02-27 | 2008-07-30 | 孟中 | Fluorosilicone rubber nano composite alloy three-proof paint and production method thereof |
| CN101275056A (en) * | 2008-05-16 | 2008-10-01 | 哈尔滨金士源科技有限公司 | Anti-sticking anti-scribbling paint composition |
| CN101514270A (en) * | 2009-02-27 | 2009-08-26 | 哈尔滨金士源科技有限公司 | Ice coating resistance paint composition |
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