CN102516859B - Anti-doodling and anti-affixing paint and its preparation method - Google Patents
Anti-doodling and anti-affixing paint and its preparation method Download PDFInfo
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- CN102516859B CN102516859B CN201110401629.3A CN201110401629A CN102516859B CN 102516859 B CN102516859 B CN 102516859B CN 201110401629 A CN201110401629 A CN 201110401629A CN 102516859 B CN102516859 B CN 102516859B
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Abstract
The invention discloses an anti-doodling and anti-affixing paint and its preparation method. the paint is composed of two components A and B, wherein the component A contains, by weight, 4-20 parts of pseudo-perfluoroalkyl modified polysiloxane, 20-42 parts of hydroxy acrylic resin, 10-35 parts of pigments and fillers, 1-8 parts of an auxiliary agent, 10-36 parts of an organic solvent; and the component B contains, by weight, 12-30 parts of polyisocyanate prepolymer. The mass ratio of the component A to the component B is 2-8:1. The component A is prepared by the following steps of: adding hydroxy acrylic resin, pigments and fillers, the auxiliary agent and the organic solvent into a grinder, uniformly grinding to prepare slurry, pouring the ground slurry and pseudo-perfluoroalkyl modified polysiloxane together into a high-speed dispenser, dispersing at 800-1500 r/min for 0.5-2 hours, filtering and packaging to obtain the required component A. When in use, the anti-doodling and anti-affixing paint is obtained by uniformly mixing the components A and B at the mass ratio of 2-8:1. A paint film formed by the paint has the following advantages of low surface energy, small friction coefficient, excellent anti-doodling and anti-affixing performance and superstrong scrub resistance.
Description
Technical field
The present invention relates to coating and preparation method thereof, be specifically related to a kind of anti-doodling and anti-affixing coating and preparation method thereof.
Background technology
In city, no matter be communal facility, on public transport stop board, waiting booth, electric pole, wall, or public transport, on subway, train, light rail train, bus, the scribble of various coating and drawing at random and the small advertisement of arbitrarily putting up all are seen everywhere, be commonly called as " city psoriasis ", not only have a strong impact on city look and feel, and will expend a large amount of manpower and materials for removing these scribbles, there is the coating of anti-doodling and anti-affixing performance in the urgent need to exploitation.Existing research shows, the surface of low surface energy can effectively prevent that scribble from adhering to and polluting, and can easily remove by simply wiping.Polysiloxane has excellent hydrophobic and lyophobic property and oilness, is applied in coating, and can significantly reduce the surface of filming can; By modification, grafting fluoroalkyl side chain on polysiloxane backbone, when film forming, fluoro-containing group strictly is orientated film coated surface due to its great surfactivity, and making films obtains better low surface energy effect.
The scientific research personnel has also done a few thing in the research and development of anti-doodling and anti-affixing coating, and patent CN101585995B has reported take oil-based anti-graffiti adhesion resistant paint prepared as main raw material by Hydroxylated acrylic resin, fluorocarbon resin, hydroxyl polydimethylsiloxaneresins resins, hexamethyl vulcabond biuret; Patent CN 101565579B discloses take the anti-doodling and anti-affixing coating that fluorocarbon resin and aliphatic polymeric isocyanate solidifying agent be composition; Patent US 5387434 has reported take the type of the damage certainly anti-doodling paint that water soluble wax, water glass, rosin and tackiness agent be composition, uses high-pressure water heating to remove scribble, after cleaning, need apply a coating again.Although the above-mentioned report about anti-doodling and anti-affixing coating and preparation method thereof is arranged, but, from disclosed paper and patent, there is not yet the report that the fluoroalkyl modified polyorganosiloxane is applied to prepare in the dual-component polyurethane system anti-doodling and anti-affixing coating at present both at home and abroad.
Summary of the invention
Technical problem: the purpose of this invention is to provide that a kind of and existing composition is different has excellent anti-doodling and anti-affixing, superpower scrub resistance, an anti-liquid medium, coating surface can be low, frictional coefficient is little, easy to clean, anti-doodling and anti-affixing coating of long service life and preparation method thereof.
Technical scheme: anti-doodling and anti-affixing coating of the present invention is comprised of A, B two components, by weight,
The A component is:
4～20 parts of fluoroalkyl modified polyorganosiloxanes,
20～42 parts of Hydroxylated acrylic resins,
10～35 parts of color stuffings,
1～8 part of auxiliary agent,
10～36 parts of organic solvents,
The B component is 12～30 parts of polyisocyanate prepolymers;
The weight ratio of A component and B component is 2～8: 1.
The hydroxyl value of described Hydroxylated acrylic resin is 5～200mg KOH/g, and number-average molecular weight is 4000～50000.
Described color stuffing is one or more in aerosil, Rutile type Titanium Dioxide, anatase thpe white powder, ptfe micropowder, talcum powder, barium sulfate, calcium carbonate, mica powder, aluminium powder or hollow glass micropearl.
Described auxiliary agent is one or more in wetting dispersing agent, flow agent, defoamer, siccative, anti-wear agent, scratching resistant or adhesion promoter.
Described organic solvent is the combination more than three kinds or three kinds in ritalin, vinyl acetic monomer, N-BUTYL ACETATE, toluene, p-Xylol, o-Xylol, m-xylene, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate, methylcarbonate, acetone, pimelinketone.
Described polyisocyanate prepolymers is a kind of in HDI tripolymer, MDI tripolymer, IPDI tripolymer or TDI tripolymer.
The preparation method of anti-doodling and anti-affixing coating is characterized in that:
The preparation of described A component:
Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, after grinding evenly, make slurry; Ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperse 0.5～2 hour under 800～1500 rev/mins after, filtered and packaged, obtain required A component;
During use, by A, B two components by 2～8: 1 weight proportion mixes and gets final product.
Described fluoroalkyl modified polyorganosiloxane is synthetic obtaining under catalyst action by fluorinated acrylate monomer and polymethyl hydrogen siloxane; its synthetic method is: under room temperature, fluorinated acrylate monomer, solvent, catalyzer are joined in reactor; stir and under protection of inert gas; be warming up to more than 80 ℃; drip polymethyl hydrogen siloxane, react 2～30 hours, then be cooled to room temperature; except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation.
Described fluorinated acrylate monomer is a kind of in trifluoroethyl methacrylate, vinylformic acid tetrafluoro propyl ester, tetrafluoropropyl propyl ester, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters.
The structural formula of described polymethyl hydrogen siloxane is:
10≤n in formula≤200.
Beneficial effect: the Hydroxylated acrylic resin in A component of the present invention can with the B component in the polyisocyanate prepolymers crosslinking curing, generation has the cancellated paint film of 3 D stereo, and this double-component polyurethane paint film cross-linking density is high, compact structure, hardness are high, scrub resistance and anti-liquid medium excellence; Added the very competent fluoroalkyl modified polyorganosiloxane of hydrophobic and oil repellent in system, surface energy and the frictional coefficient of paint film have been reduced significantly, give paint film with excellent anti-doodling and anti-affixing, can effectively prevent scribble on paint film adhere to and to the infiltration in paint film, scribble can be removed through simple scouring, various non-setting adhesives, glue also are difficult to stick to coating surface, and non-setting adhesive is pasted 500 times repeatedly without any glue residue.
Embodiment
Below by specific embodiment; the present invention will be further described, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in scope disclosed by the invention; the variation that can expect easily or replacement, all should be encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the scope of claim protection.
Embodiment 1:
The anti-doodling and anti-affixing coating that the present embodiment provides is comprised of A, B two components, comprises by weight following raw material:
The A component:
The B component:
18 parts of HDI tripolymers
Wherein, the synthetic method of fluoroalkyl modified polyorganosiloxane is: under room temperature, 60g vinylformic acid hexafluoro butyl ester, solvent, catalyzer are joined in reactor, stir and under the high pure nitrogen protection, be warming up to 90 ℃, then drip the 16.8g polymethyl hydrogen siloxane, react 28 hours, then be cooled to room temperature, except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation; Wherein the structural formula of polymethyl hydrogen siloxane is:
n=28 in formula;
The method for preparing anti-doodling and anti-affixing coating is: Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, grind 3 hours under the rotating speed of 2500 rev/mins, grind and evenly make slurry; Then ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperseed, after 1 hour, to filter and package under the rotating speed of 1000 rev/mins, obtain required A component;
During use, A, B two components are mixed, adjust to suitable viscosity and can construct.
Embodiment 2:
The anti-doodling and anti-affixing coating that the present embodiment provides is comprised of A, B two components, comprises by weight following raw material:
The A component:
The B component:
16 parts of MDI tripolymers
Wherein, the synthetic method of fluoroalkyl modified polyorganosiloxane is: under room temperature, 80g dodecafluoroheptyl methacrylate, solvent, catalyzer are joined in reactor, stir and under the high pure nitrogen protection, be warming up to 110 ℃, then drip the 13.2g polymethyl hydrogen siloxane, react 16 hours, then be cooled to room temperature, except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation; Wherein the structural formula of polymethyl hydrogen siloxane is:
The method for preparing anti-doodling and anti-affixing coating is: Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, under the rotating speed of 2500 rev/mins, grind 3h, grind and evenly make slurry; Then ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperseed, after 1.5 hours, to filter and package under the rotating speed of 1000 rev/mins, obtain required A component;
During use, A, B two components are mixed, adjust to suitable viscosity and can construct.
Embodiment 3:
The anti-doodling and anti-affixing coating that the present embodiment provides is comprised of A, B two components, comprises by weight following raw material:
The A component:
The B component:
18 parts of TDI tripolymers
Wherein, the synthetic method of fluoroalkyl modified polyorganosiloxane is: under room temperature, 100g vinylformic acid ten trifluoro monooctyl esters, solvent, catalyzer are joined in reactor, stir and under the high pure nitrogen protection, be warming up to 135 ℃, then drip the 15.6g polymethyl hydrogen siloxane, react 8 hours, then be cooled to room temperature, except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation; Wherein the structural formula of polymethyl hydrogen siloxane is:
The method for preparing anti-doodling and anti-affixing coating is: Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, under the rotating speed of 2500 rev/mins, grind 4h, grind and evenly make slurry; Then ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperseed, after 1.5 hours, to filter and package under the rotating speed of 1000 rev/mins, obtain required A component;
During use, A, B two components are mixed, adjust to suitable viscosity and can construct.
Embodiment 4:
The anti-doodling and anti-affixing coating that the present embodiment provides is comprised of A, B two components, comprises by weight following raw material:
The A component:
The B component:
19 parts of IPDI tripolymers
Wherein, the synthetic method of fluoroalkyl modified polyorganosiloxane is: under room temperature, 85g trifluoroethyl methacrylate, solvent, catalyzer are joined in reactor, stir and under the high pure nitrogen protection, be warming up to 160 ℃, then drip the 30.8g polymethyl hydrogen siloxane, react 4 hours, then be cooled to room temperature, except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation; Wherein the structural formula of polymethyl hydrogen siloxane is:
n=155 in formula;
The method for preparing anti-doodling and anti-affixing coating is: Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, under the rotating speed of 3000 rev/mins, grind 4h, grind and evenly make slurry; Then ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperseed, after 2 hours, to filter and package under the rotating speed of 1000 rev/mins, obtain required A component;
During use, A, B two components are mixed, adjust to suitable viscosity and can construct.
By the paint spay-coating of above-described embodiment 1～embodiment 4 the regulation base material on, after film-forming, formed paint film is carried out to following technical feature test: outward appearance, hardness, sticking power, wear resistance, anti-neutral salt spray, artificial ageing resistance, anti-liquid medium, anti-solvent wiping, anti-graffiti property, anti-adhibit quality.The properties test result sees the following form:
Claims (2)
1. an anti-doodling and anti-affixing coating, it is characterized in that being: described coating is comprised of A, B two components, by weight,
The A component is:
Described fluoroalkyl modified polyorganosiloxane is synthetic obtaining under catalyst action by fluorinated acrylate monomer and polymethyl hydrogen siloxane, its synthetic method is: under room temperature, fluorinated acrylate monomer, solvent, catalyzer are joined in reactor, stir and under protection of inert gas, be warming up to more than 80 ℃, drip polymethyl hydrogen siloxane, react 2～30 hours, then be cooled to room temperature, except desolventizing, obtain fluoroalkyl modified polyorganosiloxane transparent, thickness through rotary evaporation;
Described fluorinated acrylate monomer is a kind of in trifluoroethyl methacrylate, vinylformic acid tetrafluoro propyl ester, tetrafluoropropyl propyl ester, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, vinylformic acid octafluoro pentyl ester, methacrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, vinylformic acid ten trifluoro monooctyl esters or methacrylic acid ten trifluoro monooctyl esters;
The structural formula of described polymethyl hydrogen siloxane is:
10≤n in formula≤200;
The B component is 12～30 parts of polyisocyanate prepolymers;
The weight ratio of A component and B component is 2～8:1;
The hydroxyl value of described Hydroxylated acrylic resin is 5～200mgKOH/g, and number-average molecular weight is 4000～50000;
Described color stuffing is one or more in aerosil, Rutile type Titanium Dioxide, anatase thpe white powder, ptfe micropowder, talcum powder, barium sulfate, calcium carbonate, mica powder, aluminium powder or hollow glass micropearl;
Described auxiliary agent is one or more in wetting dispersing agent, flow agent, defoamer, siccative, anti-wear agent, scratching resistant or adhesion promoter;
Described organic solvent is the combination more than three kinds or three kinds in ritalin, vinyl acetic monomer, N-BUTYL ACETATE, toluene, p-Xylol, o-Xylol, m-xylene, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate, methylcarbonate, acetone, pimelinketone;
Described polyisocyanate prepolymers is a kind of in HDI tripolymer, MDI tripolymer, IPDI tripolymer or TDI tripolymer.
2. the preparation method of an anti-doodling and anti-affixing coating as claimed in claim 1 is characterized in that:
The preparation of described A component:
Hydroxylated acrylic resin and color stuffing, auxiliary agent, organic solvent are joined in shredder, after grinding evenly, make slurry; Ground slurry is put in high speed dispersor together with the fluoroalkyl modified polyorganosiloxane, disperse 0.5～2 hour under 800～1500 rev/mins after, filtered and packaged, obtain required A component;
During use, A, B two components are mixed and get final product by 2～8:1 weight proportion.
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| CN201110401629.3A CN102516859B (en) | 2011-12-07 | 2011-12-07 | Anti-doodling and anti-affixing paint and its preparation method |
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| CN201110401629.3A CN102516859B (en) | 2011-12-07 | 2011-12-07 | Anti-doodling and anti-affixing paint and its preparation method |
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| CN102516859B true CN102516859B (en) | 2014-01-01 |
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| CN105176357A (en) * | 2015-10-21 | 2015-12-23 | 中航百慕新材料技术工程股份有限公司 | Water-based double-component anti-doodling paint |
| US10259971B2 (en) * | 2015-12-18 | 2019-04-16 | Hrl Laboratories, Llc | Anti-fouling coatings fabricated from polymers containing ionic species |
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