CN1923927A - Nano composite normal temperature type gage mark coating and preparation method thereof - Google Patents
Nano composite normal temperature type gage mark coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses nanometer composite normal-temperature reticle paint and preparing method, which comprises the following parts: 15-30% polymer resin, 25-35% toluene and or xylene, 1-5% acetone and or carbinol, 0.5-2.5% plasticizer, 5-18% white dye or yellow dye, 20-42% filler and 0.2-4% nanometer oxide or nanometer oxide condensate. The preparing method comprises the following steps: stirring prepared nanometer oxide slurry or nanometer oxide material together according to certain proportion; adding in the slurry with blended slurry; grinding to certain fineness; packing.
Description
Technical field
The present invention relates to coating technology and fine chemical technology, be specially a kind of nano composite normal temperature type gage mark coating and preparation method thereof.
Background technology
21 century is the rapid development period of Chinese Economy Development, and communications and transportation is the basis and the lifeblood of national economy, and " want richness, repair the roads earlier " is the known by everybody absolute principle that China's Economic development particularly draws in the practice of southeastern coastal areas Economic development.Over past ten years, especially in the big city, along with the raising of people's living standard, the individual purchases car quantity and sharply rises, road traffic pressure with day increase severely, add the progressively enforcement of urbanization and urbanization strategy, thus to the traffic safety excellent service standard and have a good transport and communication network and proposed very high requirement.In order to dwindle the gap with developed country as early as possible, change China's traffic facilities deficiency, technical equipment falls behind, the situation of transportcapacity and traffic requirements contradiction, just begin one's study from the eighties in 20th century development strategy of highway in China net of the Ministry of Communications, country drops into huge fund and is used for the modern transportation Facilities Construction, from 1998, the annual fund of road construction that drops into of China is up to more than 2,000 hundred million yuan, finished 3,150 hundred million yuan of traffic fixed investments in 2002, the demand of road markings lacquer in all parts of the country is increasing, the requirement of road markings lacquer is also more and more higher, and traffic paint will guarantee road traffic, equipment, play tangible effect in the personnel safety.This shows: road markings engineering application of paints scope is very wide, and market forecast is considerable.
The normal temperature type marking paint is the traditional product of China's marking paint, and marking paint the earliest is exactly this kind, with its easy construction, the few advantage of one-time investment and be subjected to user's favor.The normal temperature type marking paint mainly is made up of white or yellow ultramarine, pigment extender and synthetic resins.Each component is fully mixed liquid lacquer, during use, with the appointment thinner dilution of factory, normal temperature construction down.The time of drying of normal temperature type traffic paint is longer, is mainly used in traffic flow is little, life requirement is not high road and place, as narrow road, pavement patching, parking lot etc.At present, people attempt by utilizing novel process, new prescription to optimize normal temperature type marking paint performance, to shorten time of drying, to improve weathering resistance and wear resistance etc.
Summary of the invention
The purpose of this invention is to provide a kind of nano composite normal temperature type gage mark coating and preparation method thereof with excellent abrasive resistance and weathering resistance.
Technical program of the present invention lies in:
A kind of nano composite normal temperature type gage mark coating, by weight percentage, this coating is by 15～30% fluoropolymer resins, 25%～35% toluene and/or dimethylbenzene, 1～5% acetone and/or methyl alcohol, 0.5～2.5% softening agent, 5～18% white pigments or yellow ultramarine, 20～42% fillers, 0.1～0.9% wetting dispersing agent, 0.1～2% thickening material, 0.2～4% nano-oxide or nano-oxide thickened pulp are formed.
Nano-oxide of the present invention refers to nano silicon oxide and/or nano-calcium carbonate or the nano-titanium oxide of mean particle size below 100nm of primary particle.
The weight of nano-oxide thickened pulp of the present invention consists of: nano-oxide 10～60%, and macromolecule dispersing agent 0.5～10.5%, surplus is a solvent.Described macromolecule dispersing agent is selected from Disperbyk 103, Disperbyk 106, Disperbyk 107, Disperbyk 110, Disperbyk 111, Disperbyk 164, Disperbyk 180, Disperbyk 182, Disperbyk 184, Disperbyk 190, Disperbyk 191, Disperbyk 192, Disperbyk 2000, Anti-Terra-P, the Anti-Terra-202 of German Bi Ke chemical company; Solsperse 3000, the Solsperse13940 of Avecia company, Solsperse17000, Solsperse20000, Solsperse32000, Solsperse34750; The TEXAPHOR of Henkel Corp.
963, TEXAPHOR
963S, TEXAPHOR
3061, TEXAPHOR
3073, TEXAPHOR
3112, TEXAPHOR
3241, TEXAPHOR
3250, TEXAPHOR
3287; Deuchem Co., Ltd. 902,904,904S, 923,923S, DP-981, DP-S81; The EFKA-44 of Holland EFKA auxiliary agent company, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-54, EFKA-63, EFKA-64, EFKA-65, EFKA-66, EFKA-71, EFKA-701, EFKA-745, EFKA-764, EFKA-766, EFKA-4008, EFKA-4009, EFKA-4540, EFKA-4550, EFKA-4524, EFKA-POLYMER 400, EFKA-POLYMER 401, EFKA-POLYMER 402, EFKA-POLYMER 403, EFKA-POLYMER 450, EFKA-POLYMER 451, EFKA-POLYMER 452, EFKA-POLYMER 453, EFKA-POLYMER 4010; The DISPERS610 of Di Gao chemical company, DISPERS610S, DISPERS630S, DISPERS700, DISPERS710; HypersolL4707, the HypersolL4708 of Denmark KVK company, HypersolL4742, HypersolL4744, HypersolL4963, Aquasol 4604, Aquasol 4602, Aquasol 5601; AB1010, AB1015, AB1020, AB1030 in the Elvacite of the E.I.Du Pont Company dispersion agent; The IncrosperseM of Croda resin company, Incrosperse I..Described solvent can adopt toluene, dimethylbenzene, trimethylbenzene, Solvesso100, Solvesso150, Solvesso200, solvent naphtha, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, ethylene glycol, propylene glycol, methylethylketone, mibk, pimelinketone, isophorone, ethyl acetate, the positive fourth fat of acetic acid, butyl acetate, methoxyacetic acid third fat, ethylene glycol ethyl ether, butyl glycol ether, the ethylene glycol ethyl ether amyl acetate, the butyl glycol ether amyl acetate, propylene-glycol ethyl ether, the propylene glycol butyl ether, the propylene glycol monomethyl ether amyl acetate, the propylene-glycol ethyl ether amyl acetate, propylene glycol butyl ether amyl acetate, dipropylene glycol methyl ether, the dipropylene glycol ether, trichloroethane.
Fluoropolymer resin of the present invention is one or more of the lower thermoplastic acrylic resin of acid number, chlorinated rubber, Resins, epoxy.
Softening agent of the present invention is a dioctyl sebacate, Octyl adipate, Dinonylphthalate, dioctyl terephthalate, dioctyl phthalate (DOP), trioctyl trimellitate, one or more of epoxy soybean oil; White pigment of the present invention preferably adopts titanium dioxide; Yellow ultramarine of the present invention preferably adopts the sun-proof medium chrome yellow medium yellow; Filler of the present invention is one or more of wollastonite, ground barium sulfate, lime carbonate, talcum powder, calcined kaolin, process white.The granularity of filler is respectively 200～400 orders.
Among the present invention, preferably add auxiliary agents such as some wetting dispersing agents and thickening material again, by weight percentage, wetting dispersing agent 0.1～0.9%, thickening material 0.1～2%.Described wetting dispersing agent can adopt the Yelkin TTS in the natural polymer subclass, acid or many ammonia salt of the long-chain polyester of synthetic macromolecule class, trade names can be selected for use: EFKAPolymer 400, EFKA Polymer 401, EFKA Polymer 402, EFKA Polymer 403; Also can select polycarboxylic acid or its amine salt for use, trade names can be selected EFKA 66 for use, TROYSOL 98C, F108; Described thickening material can adopt gaseous oxidation silicon, organobentonite class, castor oil derivative or Ployethylene Wax.
The present invention also provides the preparation method of above-mentioned nano composite normal temperature type gage mark coating, comprises the steps:
1) at first prepares the nanometer thickened pulp.Earlier macromolecule dispersing agent is added in the solvent, add nano-oxide then, 400-2000rpm high speed dispersion 2～60 minutes, the slurry of gained ground in ball mill or ball mill 20 minutes～24 hours, made nano-oxide and starched; Its weight consists of: nano-oxide is 10～60%, macromolecule dispersing agent 0.5～10.5%, and surplus is a solvent.
2) preparation of coating.Earlier with solvent toluene or dimethylbenzene, acetone or methyl alcohol, add in the container, under stirring condition, add fluoropolymer resin then, add softening agent, thickening material, wetting dispersing agent then, with high speed dispersor after 400～1000rpm disperseed 5～30 minutes, under agitation condition, add pigment, filler and nano-oxide or nano-oxide thickened pulp, in the 400-2000rpm high speed dispersion after 5～30 minutes, the gained slurry changes in sand mill or the ball mill and grinds 1～2h, to fineness be below the 60 μ m, discharging, packing gets final product.
The invention has the beneficial effects as follows:
The method that the present invention has proposed prefabricated nano-oxide thickened pulp first prepares the nano composite normal temperature gage mark coating, makes nano-oxide easier dispersion in coating, has well solved the compatibility issue of nano-oxide and components such as resin, solvent.Nano composite normal temperature gage mark coating stability in storage with this method preparation is good, cohesive strength is high, anti-aging, wear-resisting.
Embodiment
Except that specializing, the ratio that relates to is weight ratio among the present invention.
Embodiment 1
Take by weighing 16.5 kilograms of acrylic resins, 4 kilograms of chlorinated rubbers, 9 kilograms of titanium dioxides, 7.2 kilograms of water-ground limestones, 31.5 kilograms of process whites, 28.4 kilograms of dimethylbenzene, 1.6 kilograms of methyl alcohol, 1.8 kilograms of o-phthalic acid dibutyl esters, 2 kilograms of nano-oxide thickened pulp also can be allocated 1.0 kilograms of 0.5 kilogram of wetting dispersing agent F108 and organobentonites into, during making, earlier with dimethylbenzene, methyl alcohol, o-phthalic acid dibutyl ester adds in the container, add acrylic resin and chlorinated rubber under agitation condition, homodisperse added titanium dioxide after 15 minutes under agitation condition, water-ground limestone, process white, nano-oxide thickened pulp etc., in the 1000rpm high speed dispersion after 15 minutes, the gained slurry changes over to and grinds 1h in the sand mill, after fineness reaches 60 μ m, adjusts viscosity, filter and package, promptly get the nano composite normal temperature gage mark coating of the present invention of about double centner.
Wherein, the preparation process of nano-oxide thickened pulp is as follows:
Take by weighing 80 kilograms of ethyl acetates, 45 kilograms of methylethylketones, add 3.25 kilograms of macromolecule dispersing agent Dispersebyk 107, add 65.1 kilograms of rutile type nano titanium oxide again, disperseed 40 minutes with high speed dispersor 1200rpm, then ball mill grinding 12h.The weight ratio of macromolecule dispersing agent Dispersebyk 107 in this nano-titanium oxide slurry is 1.7%.Make the nano-titanium oxide weight ratio and be 33.7% nano-titanium oxide thickened pulp.
Embodiment 2
Take by weighing 20.5 kilograms of acrylic resins, 10 kilograms of medium chrome yellow medium yellows, 20.2 kilograms of water-ground limestones, 2.5 kilograms of process whites, 10 kilograms of talcum powder, 32 kilograms of dimethylbenzene, 2 kilograms of methyl alcohol, 1.6 kilograms of epoxy soybean oils, 1 kilogram of nano-oxide thickened pulp also can be allocated 0.6 kilogram of 66 0.3 kilograms of wetting dispersing agent EFKA and thickening material gaseous oxidation silicon etc. into, during making, earlier with dimethylbenzene, methyl alcohol, epoxy soybean oil adds in the container, adds acrylic resin under agitation condition, and homodisperse is after 15 minutes, under agitation condition, add medium chrome yellow medium yellow, water-ground limestone, talcum powder, process white, nano-oxide thickened pulp etc., after 12 minutes, the gained slurry changes over to and grinds 2h in the sand mill in the 1200rpm high speed dispersion, sends into sand mill then and grinds, fineness less than 60 μ m after, adjust viscosity, filter and package, promptly get the nano composite normal temperature gage mark coating of the present invention of about double centner.
Wherein, the preparation process of nano-oxide thickened pulp is as follows:
Take by weighing double centner methoxyacetic acid third fat, add 11.1 kilograms of macromolecule dispersing agent AB1010, add 47.6 kilograms of nano zine oxides again, disperseed 15 minutes with high speed dispersor 800rpm, the weight ratio of the macromolecule dispersing agent AB1010 in this nano zine oxide slurry of ball mill grinding 6h. is 7% then.Make the nano zine oxide weight ratio and be 30% nanometer zinc oxide concentrated slurry.
Embodiment 3
Take by weighing 15.5 kilograms of acrylic resins, 11 kilograms of titanium dioxides, 21.2 kilograms of water-ground limestones, 17.5 kilograms of process whites, 2.7 kilograms of calcined kaolins, 27.2 kilograms of dimethylbenzene, 1.5 kilograms of methyl alcohol, 1.3 kilograms of dioctyl sebacates, 1.5 kilograms of nano-titanium oxide thickened pulp also can be allocated 0.5 kilogram of wetting dispersing agent TROYSOL 98C0.9 kilogram and organobentonite into, during making, earlier with dimethylbenzene, methyl alcohol, dioctyl sebacate adds in the container, add acrylic resin under agitation condition, homodisperse added titanium dioxide after 15 minutes under agitation condition, water-ground limestone, calcined kaolin, process white, nano-oxide thickened pulp etc., in the 800rpm high speed dispersion after 30 minutes, the gained slurry changes over to and grinds 1.5h in the sand mill, after fineness reaches 60 μ m, adjusts viscosity, filter and package, promptly get the nano composite normal temperature gage mark coating of the present invention of about double centner.Wherein, the nano-titanium oxide thickened pulp is with embodiment 1.
Embodiment 4
Take by weighing 18.5 kilograms of acrylic resins, 10 kilograms of medium chrome yellow medium yellows, water-ground limestone kilogram 7.5,15.2 kilograms of process whites, 8.1 kilograms of talcum powder, 33 kilograms of dimethylbenzene, 3.1 kilograms of methyl alcohol, 1.6 kilograms of phthalic acid dibutyl esters, 1 kilogram of nanometer zinc oxide concentrated slurry also can be allocated 0.6 kilogram of 66 0.3 kilograms of wetting dispersing agent EFKA and thickening material gaseous oxidation silicon etc. into, during making, earlier with dimethylbenzene, methyl alcohol, the phthalic acid dibutyl ester adds in the container, adds acrylic resin under agitation condition, and homodisperse is after 15 minutes, under agitation condition, add medium chrome yellow medium yellow, water-ground limestone, talcum powder, process white, nano-oxide thickened pulp etc., after 10 minutes, the gained slurry changes over to and grinds 2h in the sand mill in the 1500rpm high speed dispersion, sends into sand mill then and grinds, fineness less than 60 μ m after, adjust viscosity, filter and package, promptly get the nano composite normal temperature gage mark coating of the present invention of about double centner.Wherein, nanometer zinc oxide concentrated slurry is with embodiment 2.
Comparative example 1
Take by weighing 16.5 kilograms of acrylic resins, 4 kilograms of chlorinated rubbers, 9 kilograms of titanium dioxides, 7.2 kilograms of water-ground limestones, 31.5 kilograms of process whites, 28.4 kilograms of dimethylbenzene, 1.6 kilograms of methyl alcohol, 1.8 kilograms of o-phthalic acid dibutyl esters, allocate 1.0 kilograms of 0.5 kilogram of wetting dispersing agent F108 and organobentonites into, during making, earlier with dimethylbenzene, methyl alcohol, o-phthalic acid dibutyl ester adds in the container, adds acrylic resin and chlorinated rubber under agitation condition, behind the homodisperse 15 minutes, under agitation condition, add titanium dioxide, water-ground limestone, process white etc., after 15 minutes, the gained slurry changes over to and grinds 1h in the sand mill in the 1000rpm high speed dispersion, after fineness reaches 60 μ m, adjust viscosity, filter and package, promptly get the normal temperature gage mark coating that does not contain nano-oxide of about double centner.
Comparative example 2
Take by weighing 20.5 kilograms of acrylic resins, 10 kilograms of medium chrome yellow medium yellows, 20.2 kilograms of water-ground limestones, 2.5 kilograms of process whites, 10 kilograms of talcum powder, 32 kilograms of dimethylbenzene, 2 kilograms of methyl alcohol, 1.6 kilograms of epoxy soybean oils, allocate 0.6 kilogram of 66 0.3 kilograms of wetting dispersing agent EFKA and thickening material gaseous oxidation silicon etc. into, during making, earlier with dimethylbenzene, methyl alcohol, epoxy soybean oil adds in the container, under agitation condition, add acrylic resin, behind the homodisperse 15 minutes, under agitation condition, add medium chrome yellow medium yellow, water-ground limestone, talcum powder, process whites etc. are in the 1200rpm high speed dispersion after 12 minutes, the gained slurry changes over to and grinds 2h in the sand mill, send into sand mill then and grind, fineness less than 60 μ m after, adjust viscosity, filter and package, promptly get the normal temperature gage mark coating that does not contain nano-oxide of about double centner.
Table 1
| Sticking power/level | Snappiness/mm | Cohesive strength/MPa | Wear resistance mg (200 commentaries on classics/1000kg) | Resistance to deterioration/level | |
| Embodiment 1 | 0 | 2 | 3.2 | 28.2 | 0 |
| Comparative example 1 | 1 | 3 | 3.0 | 35.0 | 1 |
| Embodiment 2 | 0 | 1 | 3.8 | 26.3 | 0 |
| Comparative example 2 | 2 | 3 | 2.7 | 42.1 | 1 |
| Embodiment 3 | 0 | 2 | 3.3 | 30.2 | 0 |
| Embodiment 4 | 1 | 2 | 3.0 | 33.0 | 0 |
Claims (10)
1, a kind of nano composite normal temperature type gage mark coating, it is characterized in that by weight percentage, it basic composition is: fluoropolymer resin 15～30%, toluene and/or dimethylbenzene 25%～35%, acetone and/or methyl alcohol 1～5%, softening agent 0.5～2.5%, white pigment or yellow ultramarine 5～18%, filler 20～42%, nano-oxide or nano-oxide thickened pulp 0.2～4%.
2, nano composite normal temperature type gage mark coating according to claim 1 is characterized in that: one or more of the nano silicon oxide of the median size that nano-oxide refers to primary particle below 100nm, nano-calcium carbonate, nano-titanium oxide, nano zine oxide.
3, nano composite normal temperature type gage mark coating according to claim 1 and 2 is characterized in that the weight of nano-oxide thickened pulp consists of: nano-oxide 10～60%, and macromolecule dispersing agent 0.5～10.5%, surplus is a solvent.
4, nano composite normal temperature type gage mark coating according to claim 1 is characterized in that: fluoropolymer resin is one or more of the lower thermoplasticity acrylic acid resin of acid number, chlorinated rubber, Resins, epoxy.
5, nano composite normal temperature type gage mark coating according to claim 1, it is characterized in that: described softening agent is a dioctyl sebacate, Octyl adipate, Dinonylphthalate, dioctyl terephthalate, dioctyl phthalate (DOP), trioctyl trimellitate, one or more of epoxy soybean oil.
6, nano composite normal temperature gage mark coating according to claim 1 is characterized in that: white pigment adopts titanium dioxide.
7, nano composite normal temperature gage mark coating according to claim 1 is characterized in that: yellow ultramarine adopts the sun-proof medium chrome yellow medium yellow.
8, nano composite normal temperature gage mark coating according to claim 1 is characterized in that: filler is one or more of wollastonite, ground barium sulfate, lime carbonate, talcum powder, calcined kaolin, process white.
9, nano composite normal temperature gage mark coating according to claim 1 is characterized in that also comprising in the coating auxiliary agent: wetting dispersing agent and thickening material, by weight percentage, wetting dispersing agent 0.1～0.9%, thickening material 0.1～2%.
10, the preparation method of the described nano composite normal temperature type gage mark coating of one of a kind of claim 1～9 is characterized in that preparation process is as follows:
1) at first prepares the nanometer thickened pulp: earlier macromolecule dispersing agent is added in the solvent, add nano-oxide then, 400-2000rpm high speed dispersion 2～60 minutes, the slurry of gained ground in ball mill or ball mill 20 minutes～24 hours, made the nano-oxide slurry;
2) preparation of coating: earlier with solvent toluene or dimethylbenzene, acetone or methyl alcohol, add in the container, under stirring condition, add fluoropolymer resin then, add softening agent, thickening material, wetting dispersing agent then, after being uniformly dispersed, under agitation condition, add pigment, filler and nano-oxide or nano-oxide thickened pulp, in the 400-2000rpm high speed dispersion after 5～30 minutes, the gained slurry changes in sand mill or the ball mill and grinds 1～2h, discharging, and packing gets final product.
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| CN101974272A (en) * | 2010-11-15 | 2011-02-16 | 田维兴 | Oily exterior wall paint |
| CN102516862A (en) * | 2011-12-15 | 2012-06-27 | 吴江明峰聚氨酯制品有限公司 | Preparation method of polyurethane marking paint |
| CN102511503A (en) * | 2011-12-06 | 2012-06-27 | 海南大学 | Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method |
| CN102690569A (en) * | 2011-03-23 | 2012-09-26 | 成都澳贝龙科技发展有限公司 | Water-soluble nanometer quick-drying road marking paint |
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| CN100475922C (en) | 2009-04-08 |
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