CN101781519A - Transparent anti-graffiti dirt-resistant anti-weathering coating - Google Patents
Transparent anti-graffiti dirt-resistant anti-weathering coating Download PDFInfo
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- CN101781519A CN101781519A CN200910259434A CN200910259434A CN101781519A CN 101781519 A CN101781519 A CN 101781519A CN 200910259434 A CN200910259434 A CN 200910259434A CN 200910259434 A CN200910259434 A CN 200910259434A CN 101781519 A CN101781519 A CN 101781519A
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Abstract
The invention discloses a solvent type double-component transparent anti-graffiti dirt-resistant anti-weathering coating and a preparation method thereof. The coating can be used for surfaces of decorative bricks, ceramic surfaces, mosaic layers, metals and color paint coatings of structures such as bus stops, sidewalks and public facilities for protecting long-life surfaces, prevents graffiti and dirt, and is easy to remove painted ink of marking pens, sprayed paints, crayon marks, pasted adlets, chewing gum, dust and scale, and the like.
Description
Technical field
The present invention relates to the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of a kind of solvent-borne type, this coating can be used for public transport stop board, walkway, the isostructural facing tile layer of public transport facility, pottery magnetic surface, mosaic layer, metal, colored paint coatingsurface as the long lifetime surfacecti proteon, prevent scribble and pickup, make to be coated with all removings easily such as the marking pen printing ink (or ink) that draws, the coating in the spraying, wax crayon mark, paster small advertisement, chewing gum, dust incrustation.
Background technology
Coating and drawing at random, the chewing gum of putting up everywhere, abandoning are the problems that various countries municipal sector is perplexed very much, developed country such as the West Europe and the U.S. is in order to remove the dirt that these hinder the city appearance of the city, all will drop into a large amount of man power and materials every year, expended many economy spendings.In China, along with expanding economy, people go deep into advertisement understanding, have caused a large amount of small advertisements to produce, and for example many bus stop boards have been sticked advertisement and scribbled a large amount of telephone numbers, and this phenomenon is very general in many cities.It is a large amount of artificial that municipal sector has also employed, adopt root out by hand, wiping, and remove, but effect is not ideal with methods such as high pressure water wash away, be not to remove not thoroughly, original sign also is damaged.This phenomenon is referred to as " Graffiti " (scribble) abroad, and it not only diminishes the appearance of the city, makes troubles to people's life, also can spend a large amount of money and clean.
In order to overcome this social phenomenon, external many companies have developed anti-graffiti anti-stick dirty coating for this reason, also have more relevant patent to deliver simultaneously.Domesticly start late relatively, the research degree of depth all can't be compared with developed countries with the input dynamics.Domestic also have some producers to carry out correlative study, its main design thought all is to come the composition material system at some specific resins and corresponding adjuvants, behind this material filming, rete has lower surface tension, and water is difficult for wetting coating surface and produces the dewdrop effect.Paint, mark pen ink, wax crayon etc. are not easy at the coating surface mark, even after on the mark, also can remove than being easier to, and not leave a trace, and also can not damage paint film simultaneously.Even the anti-scribble performance through paint film after repeatedly scribble is removed is unaffected.The scribble cleaning way of this system has water, hot water, detergent liquid and special-purpose scavenging solution.For the small advertisement of pasting, be not easy to paste the jail on this surface, can tear easily or remove, do not stay any vestige fully.
The implementation of anti-doodling paint mainly shows resin and two aspects of special assistant.Mostly special assistant is the material that some can provide low surface energy for paint film, for example fluorine carbon auxiliary agent, organosilicon auxiliary agent, polyethylene or propylene wax.From the angle of resin, except the product employing modified epoxy of fewer companies, generally adopt urethane resin, organic and inorganic silicon compound resin, but the ratio maximum that urethane resin adopts.Wherein adopt the less relatively of aqueous polyurethane, the overwhelming majority has adopted the solvent-type double-component polyurethane system.
Above-mentioned these anti-doodling paints antigraffiti effect at short notice is all very good, but it has a common shortcoming, is exactly that its surface energy can raise after repeatedly scribble removing and physical abrasion, and polluting proofing property can descend; Particularly outdoor through after several years sunlight is exposed to the sun for a long time, along with aging, efflorescence, the cracking of coating resin, the antigraffiti effect of whole coating reduces significantly, has almost completely lost the characteristic of anti-pickup.
Summary of the invention
For overcoming above-mentioned coating owing to the not enough inferior position that causes antigraffiti effect to lose efficacy of long lifetime weathering resistance, the present invention intends developing the two transparent anti-graffiti anti-stick dirty coatings with high weatherability of component of a kind of solvent-borne type, this coating has superpower weathering resistance and excellent abrasive energy, has the strong characteristics of low, the anti-stick dirty ability of surface energy simultaneously.
The present invention realizes by following embodiment:
The two transparent anti-graffiti anti-stick dirty coatings with high weatherability of component of a kind of solvent-borne type is characterized in that described coating is made up of by following weight ratio two kinds of components of A, B,
A component: Hydroxylated acrylic resin 10%～25%; Fluorine modified hydroxyl acrylic resin 10%～25%; Organic-silicon-modified Hydroxylated acrylic resin 10%～25%; Defoamer 0.1%～0.5%; Leveling auxiliary agent 0.2～2%; Protective agent 0.5%～2%; Matting agent 1%～3%; Wetting dispersing agent 0.3-1%; Solvent 5%～40%; Total amount meter based on the A component;
B component: solidifying agent 65%～85%; Solvent 15%～35% is based on the total amount meter of B component;
Wherein, the ratio of the weight of A, B component is 5～10: 1～4, preferred 6～10: 1～2, more preferably 6～7: 1, and most preferably 100: 15.
Wherein in the A component, preferred Hydroxylated acrylic resin 15%～20%; Fluorine modified hydroxyl acrylic resin 15%～20%; Organic-silicon-modified Hydroxylated acrylic resin 15%～20%; Defoamer 0.2%～0.4%; Leveling auxiliary agent 0.3～1.5%, more preferably 0.5-0.8%; Protective agent 0.5%～1.5%, more preferably 0.8-1.2%; Matting agent 1%～3%, preferred 1.5-2%; Wetting dispersing agent 0.5-3%, more preferably 1-2%; Solvent 10-30%, preferred 15-20%.
Wherein Hydroxylated acrylic resin, fluorine modified hydroxyl acrylic resin, organic-silicon-modified Hydroxylated acrylic resin are as base resin, this three kinds of resins mixed abandon can with the crosslinked acquisition low surface tension of polyisocyanate curing agent, give long-acting hydrophobic function of paint film and anti-stick dirty characteristic, improve the ageing-resistant performance of paint film simultaneously.
The present invention also comprises following embodiment, the preparation method of the two transparent anti-graffiti anti-stick dirty coatings with high weatherability of component of a kind of above-mentioned solvent-borne type, and it comprises the steps:
The preparation of A component: in proportion wetting dispersing agent, defoamer, leveling auxiliary agent, protective agent and delustring auxiliary agent are joined in Hydroxylated acrylic resin, fluorine modified hydroxyl acrylic resin, organic-silicon-modified Hydroxylated acrylic resin and the organic solvent of sufficient quantity and stir, stir;
The preparation of B component: in proportion solidifying agent is dissolved in the high boiling organic solvent, stirs.
During use, with two kinds of components of A, B by 5～10: 1～4, preferred 6～10: 1～2, more preferably 6～7: 1, most preferably the ratio thorough mixing of 100: 15 weight and stirring promptly gets transparent anti-graffiti anti-stick dirty coatings with high weatherability of the present invention.
In preferred embodiments, Hydroxylated acrylic resin in the A component and aliphatic polyisocyante are crosslinked as main film forming material.
Fluorine modified hydroxyl acrylic resin can with the crosslinked acquisition low surface tension of polyisocyanate curing agent, give long-acting hydrophobic function of paint film and anti-stick dirty characteristic, improve the ageing-resistant performance of paint film simultaneously.
Organic-silicon-modified Hydroxylated acrylic resin can obtain low surface tension with multi isocyanate crosslinking, gives long-acting hydrophobic function of paint film and anti-stick dirty characteristic, further improves the ageing-resistant performance of paint film.
Protective agent is formed by UV light absorber, quencher and radical scavenger are compound.Described UV light absorber (UVA) is preferably selected from the salicylate class, as salol, and BAD, TBS, OPS etc.Described quencher is preferably selected from metal complexs such as ferrous iron, cobalt, copper, nickel, and organic moiety is substituted phenol or thiobisphenol etc., dithiocar-bamate, phosphonate monoester nickel type, thiobisphenol type etc., more preferably second, n-butyl dithiocarbamate nickel.
Preferred described radical scavenger is selected from hindered amine light stabilizer (HALS) compound, mainly is that piperazine system, piperidines are that derivative and imidazolidone are derivative etc., and two (1,2,2,6, the 6-pentamethyl--4-piperidyl) sebates of choosing are more arranged.
Preferred protective agent middle-ultraviolet lamp absorption agent: quencher: the molar ratio of radical scavenger is 0.8～1.5: 0.4～1.2: 0.4～1.3, more preferably 0.9～1.4: 0.5～1.1: 0.5～1.2, most preferably 1.0～1.3: 0.6～0.9: 0.6～0.9.
In preferred embodiments, wetting dispersing agent in the A component is the auxiliary agent of this area routine, as contain polyamine block copolymer solution, contain the polyamine amide solution of the interpolymer solution of acidic-group, unsaturated polyprotonic acid etc., the block copolymer solution of preferred polyamine, contain the interpolymer solution of acidic-group, more preferably contain the interpolymer solution of acidic-group.
Matting agent as aluminum foil stearate, the Zinc Stearate of metallic soap class, also has the modified oil matting agent, macromolecule wax etc. for to be the conventional auxiliary agent of this area.
Leveling auxiliary agent also is the auxiliary agent of this area routine, as modified polyorganosiloxane type flow agent, the restricted long-chain resin type of consistency flow agent, as Voncoat R 3310 and multipolymer; With the high boiling solvent is the flow agent of main component, preferred modified polyorganosiloxane type flow agent, polyimide, polycarbonate, polyacrylic acid, more preferably modified polyorganosiloxane type flow agent.
Defoamer is the conventional auxiliary agent of this area.The purpose of using defoamer is to prevent that protective membrane from producing pore, and the defoamer of use can be the derivative, acrylic copolymer, modified organic silicone resin of higher fatty acid glyceryl ester, polyethylene polyamine etc.
Solvent is preferably high boiling organic solvent, ester class and ketone, without toluene, dimethylbenzene.More preferably ester class and ketone, also most preferably 1-Methoxy-2-propyl acetate and N-BUTYL ACETATE.
The solidifying agent preferred aliphat isocyanic ester of B component, the more preferably biuret and the tripolymer of hexamethylene diisocyanate (HDI).HDI tripolymer most preferably.
The B component solvent, preferred high boiling organic solvent, as high boiling point aromatic hydrocarbons, ester class and ketone, but without toluene and dimethylbenzene, more preferably ester class, most preferably N-BUTYL ACETATE.
Select for use suitable anti-aging ultraviolet radiation absorption auxiliary agent to reduce the destruction of UV ultraviolet ray in the coating of the present invention, improve the weathering resistance of paint coatings paint coatings.
The present invention selects well behaved and eco-friendly special solvent system; this solvent substituted benzene solvent; make in the coating addition of material that environment and human body are damaged be reduced, compared with traditional solvent-borne type product obvious improvement has been arranged for the protection of environment and human body.
The present invention is by selecting and composite (modification) suitable resin-based materials, in conjunction with the curing system that has excellent weather resistance, curing cross-linked is respond well, add and examine the auxiliary agent combined system of coupling, it is suitable to the effective solvent system of environmental improvement to select, and develops a kind of have anti-pickup function, high weather resisteant, long-effective corrosion, the two transparent anti-graffiti anti-stick dirty coating of component of eco-friendly solvent-borne type.
The transparent anti-graffiti anti-stick dirty coating of final development reaches the requirement of table 1 technical indicator
Table 1
According to a preferred embodiment of the invention, surface property according to base material, earlier with surface to be coated such as facing tile layer, pottery magnetic surface, mosaic layer, metal, colored paint coatingsurface, after will waiting to be coated with the surface and remove clean and dry with means such as high pressure water, pressurized air, the mode that adopts spraying or brush is constructed, and coating dry film thickness is 60～80 μ m.
Embodiment
The present invention is described in detail by the following examples, and described embodiment is convenient to understand the present invention, but not limitation of the present invention, those skilled in the art, on the basis of reading specification sheets of the present invention, any modification or the change made can not deviate from the spirit and scope of the present invention.
Behind the prepared model 5000h of anti-artificial accelerated aging of following embodiment, 0 grade of efflorescence, 1 grade of loss of gloss, 1 grade of variable color; After coatingsurface adopts water-based or permanent pen mark, can remove pickup surface fully with low-pressure water or band water rag; Coatingsurface can be opened this advertisement easily with the papery advertisement of cohesiveness glue under the situation of not destroying the papery advertisement, and coatingsurface not have glue remaining.
Embodiment 1
A component preparation: the wetting dispersing agent that with 1.5 gram molecular weights is 20000 polyamine block copolymer solution, 2 gram protective agents (UV light absorber salol wherein: quencher second, n-butyl dithiocarbamate nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.0: 0.6: 0.6), 2 gram modified polyorganosiloxane type flow agents, 0.4 the aluminum foil stearate of the higher fatty acid glyceryl ester defoamer of gram and 2.1 grams, join 20 gram Hydroxylated acrylic resins, in 20 gram fluorine modified hydroxyl acrylic resins and the organic-silicon-modified Hydroxylated acrylic resin of 22 grams, join again in the 30 gram N-BUTYL ACETATE solvents and stirred 1 hour, make both thorough mixing even.
The preparation of B component: 65 gram HDI tripolymers are dissolved in to stir thorough mixing in the N-BUTYL ACETATEs of 35 grams even.
Before the coating,, after stirring, obtain transparent anti-graffiti anti-stick dirty coating with the mixed of two kinds of components of A, B by 5: 2.
Embodiment 2
A component preparation: the interpolymer solution that 4 grams is contained acidic-group, 1.5 gram protective agent (UV light absorber benzotriazole ester wherein: quencher phosphonate monoester nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.5: 0.8: 0.6), 0.8 gram modified polyorganosiloxane type flow agent, 0.4 the aluminum foil stearate of the modified organic silicone resin defoamer of gram and 2.1 grams, join 20 gram Hydroxylated acrylic resins, in 25 gram fluorine modified hydroxyl acrylic resins and the organic-silicon-modified Hydroxylated acrylic resin of 20 grams, join again in the 25 gram 1-Methoxy-2-propyl acetate solvents and stirred 1 hour, make both thorough mixing even.
The preparation of B component: 70 gram HDI tripolymers are dissolved in to stir thorough mixing in the 1-Methoxy-2-propyl acetates of 30 grams even.
Before the coating,, after stirring, obtain transparent anti-graffiti anti-stick dirty coating with the mixed of two kinds of components of A, B by 6: 1.
Embodiment 3
A component preparation: the wetting dispersing agent that with 0.5 gram molecular weight is 20000 polyamine block copolymer solution, 1.5 gram protective agent (UV light absorber benzophenone wherein: quencher thiobisphenol nickel: radical scavenger two (1,2,2,6,6-pentamethyl--4-piperidyl) molar ratio of sebate is 1.0: 0.9: 0.8), 0.6 gram modified polyorganosiloxane type flow agent, 0.5 the aluminum foil stearate of gram higher fatty acid glyceryl ester defoamer and 1.9 grams, join 15 gram Hydroxylated acrylic resins, in 15 gram fluorine modified hydroxyl acrylic resins and the organic-silicon-modified Hydroxylated acrylic resin of 25 grams, join again in the 40 gram N-BUTYL ACETATE solvents and stirred 1 hour, make both thorough mixing even.
The preparation of B component: 80 gram HDI tripolymers are dissolved in to stir thorough mixing in the N-BUTYL ACETATEs of 20 grams even.
Before the coating,, after stirring, obtain transparent anti-graffiti anti-stick dirty coating with the mixed of two kinds of components of A, B by 7: 1.
Claims (6)
1. the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of solvent-borne type is characterized in that described coating is made up of by following weight ratio two kinds of components of A, B,
A component: Hydroxylated acrylic resin 10%～25%; Fluorine modified hydroxyl acrylic resin 10%～25%; Organic-silicon-modified Hydroxylated acrylic resin 10%～25%; Defoamer 0.1%～0.5%; Leveling auxiliary agent 0.2～2%; Protective agent 0.5%～2%; Matting agent 1%～3%; Wetting dispersing agent 0.3-4%; Solvent 5%～40%; Total amount meter based on the A component;
B component: solidifying agent 65%～85%; Solvent 15%～35% is based on the total amount meter of B component;
Wherein, the ratio of the weight of A, B component is 5～10: 1～4, preferred 6～10: 1～2, more preferably 6～7: 1, and most preferably 100: 15.
2. the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of solvent-borne type according to claim 1, described antiaging agent by UV light absorber, quencher, radical scavenger is compound forms.
3. the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of solvent-borne type according to claim 1 and 2, wherein said UV light absorber is selected from the salicylate class, as salol, benzophenone or benzotriazole compound, described quencher is selected from metal complexs such as ferrous iron, cobalt, copper, nickel, preferred dithiocar-bamate, phosphonate monoester nickel type, thiobisphenol type; Described radical scavenger is selected from hindered amine compound, as two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate.
4. according to the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of each described solvent-borne type of claim 1-3, wherein said solvent is high boiling point aromatic hydrocarbons, ester class and ketone, but does not comprise toluene and dimethylbenzene.
5. the preparation method of the two transparent anti-graffiti anti-stick dirty high weatherability coatings of component of each described solvent-borne type of claim 1-4, it comprises the steps:
The preparation of A component: in proportion fluorine modified hydroxyl acrylic resin, organic-silicon-modified Hydroxylated acrylic resin, Hydroxylated acrylic resin are joined in resin and the solvent, add defoamer, leveling auxiliary agent, protective agent and delustring auxiliary agent, stir;
The preparation of B component: in proportion solidifying agent is dissolved in the high boiling organic solvent, stirs;
During use, with A, B component by 5～10: 1～4, preferred 6～10: 1～2, more preferably 6～7: 1, most preferably the ratio thorough mixing of 100: 15 weight stirs and makes.
6. method according to claim 5, wherein said organic solvent are high boiling organic solvent, as high boiling point aromatic hydrocarbons, ester class and ketone, but do not comprise toluene and dimethylbenzene.
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