CN105111881B - A kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate - Google Patents
A kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate Download PDFInfo
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- CN105111881B CN105111881B CN201510552781.XA CN201510552781A CN105111881B CN 105111881 B CN105111881 B CN 105111881B CN 201510552781 A CN201510552781 A CN 201510552781A CN 105111881 B CN105111881 B CN 105111881B
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Abstract
The present invention provides a kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate, the coating uses polyurethane modified acrylic resin, so that the coating has excellent fire-retardant and wear-resisting property, and curing rate is fast, also there is preferable mechanical property, ageing-resistant performance and resistance to chemical corrosion, strong adhesive force, ductility are good, high temperature resistant, service life length, change processing technology, concentrated on antitheft door door-plate slab and complete roller coat processing, simplify machining clearance, without being separately provided painting workshop.
Description
Technical field
The present invention relates to a kind of antitheft door door-plate with acrylic resin modified energy-saving and environment-friendly paint.
Background technology
Acrylic resin is the resin made of acrylate and methacrylate and other olefinic type monomers are copolymerized, with
Other synthetic macromolecule resins are compared, and acrylic resin has the advantages that many prominent, such as excellent fast light, weatherability, outdoor
The durability that is exposed to the sun is strong, and ultraviolet resistance irradiation is not easily decomposed and turns yellow, and can keep original gloss and color and luster for a long time, heat-resist,
There are the contamination of the chemicals such as preferable acid and alkali resistance, salt, grease and detergent and corrosive nature, fabulous pliability and minimum pigment
Reactivity.Therefore, automobile, household electrical appliances, metal furniture, coiled material industry, instrument and meter, building, textile, woodwork, papermaking and
Plastic products etc. industrially have a wide range of applications.
However, heat caused by the linear structure of acrylic resin sticks the shortcomings of cold short, anti-after-tackiness and heat resistance are bad pair
Its application range has certain limitations.The equal phase structure of acrylic resin causes its cold tolerance and heat resistance to be difficult to take into account,
Such as to increase resistance to low temperature, then can lose resistance to elevated temperatures, vice versa, thus common acrylic compounds coating material is just not
Can avoid there are disadvantages mentioned above.
The shortcomings that overcoming acrylic resin " hot sticky cold crisp ", widens its weather resistance, and optimal method is to change material
Aggregated structure, the glass transition temperature and flow temperature for making material no longer interrelate.Wherein use polyurethane-modified propylene
Acid resin is a kind of method preferably, and studies both at home and abroad more at present, more deep method.
Polyurethane is high by the block formed made from stepwise polymerization reaction, by polyester soft segment and carbamate hard section
Molecular material, its unique aggregated structure impart the excellent weather resistance of polyurethane.The two phase structure of polyurethane carries for it
Splendid weather resistance is supplied.Purpose using polyurethane modified acrylic resin is by corresponding modification technology, will be gathered
Urethane strand is introduced into acrylic resin, and it is in two-phase or multiphase structure to make modified material, so that the vitrifying of material
Temperature and flow temperature are determined by different phase regions, to widen the weather resistance of material.
At present, there are following polyurethane modified acrylic resin coating for the country：
Chinese patent CN201010269992.X, discloses a kind of acrylic resin-polyurethane resin heat preservation coating, it leads
If it is made of following raw materials according according to weight proportion stirring：60 parts of acrylic resins, 30 parts of closed perlites, 25 parts of aphthenic acids
Cobalt, 10 parts of methylcellulose, 75 parts of polyurethane resins, 12 parts of powdered whitings, 10 parts of diatomite, 6 parts of mortar kings, 10 portions of bananas
Water, 65 parts of water, 2 parts of defoamers, 8 parts of thickeners, 6 parts of coalescents.However, it only enumerates acrylic resin and polyurethane
Resin, but the two does not organically combine to form polyurethane modified acrylic resin, still can not realize polyurethane-modified acrylic acid
The performance of resin.
In addition, the application mode of existing acrylic resin paint uses spray-coating, such as Chinese patent mostly
CN201310607469.7, discloses a kind of powdery paints thermosetting acrylic resin, which is equipped with unclassified stores system
Into thermosetting powder coating, the film formed after spraying, has excellent weatherability, good flow leveling, excellent
Case hardness and high-luster, durability and decoration performance；Available for indoor or outdoors mental section or construction material.Can be
TGIC is substituted to a certain extent, avoids the use of toxic substance.
However, wherein, spraying be by spray gun or dish-style atomizer, by means of pressure or centrifugal force, be dispersed into uniformly and
Fine droplet, is applied over the coating process on coated article surface.Main problem in spraying is coating cloud and the volatilization of high degree of dispersion
Solvent (i.e. volatile organic contaminant, VOCs) out, both pollutes environment, is unfavorable for health, and wastes coating, causes
Economic loss.The coating for volatilizing, being diffused into air, then form volatile organic contaminant, is detrimental to health.In spraying car
Between, main source of the coating as volatile organic contaminant, volatile organic compounds concentration mistake in air in painting workshop
It is easy to cause acute poisoning when high, headache, dizziness, cough, Nausea and vomiting or in dead drunk liquor-saturated shape occurs in the lighter；Severe one can go out
Existing hepatotoxicity is even gone into a coma quickly, and some can also can be in peril of one's life.The long-term spraying for staying in volatile organic compounds pollution
In workshop, slow poisoning can be caused, infringement liver and nervous system, cause general weakness, drowsiness, pruitus etc..Some is also
Endocrine disorder may be caused, influence sexual function；Benzene and dimethylbenzene can also damage system, so that trigger leukaemia.
The content of the invention
It is an object of the invention to provide a kind of antitheft door door-plate acrylic resin modified energy-saving and environment-friendly paint, the painting
Material uses polyurethane modified acrylic resin so that the coating has excellent fire-retardant and wear-resisting property, and curing rate
Hurry up, also with preferable mechanical property, ageing-resistant performance and resistance to chemical corrosion, strong adhesive force, ductility are good, high temperature resistant,
Service life is grown, and changes processing technology, is concentrated on antitheft door door-plate slab and is completed roller coat processing, simplifies machining clearance, without
It is separately provided painting workshop.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate, each composition quality fraction is such as in the coating
Under：Polyurethane modified acrylic resin：70~80 parts, hydroxypropyl methyl cellulose：3~5 parts, amino resins：It is 5~10 parts, different
Isophoronediamine：10~15 parts, diphenylmethanediamiand：3~8 parts, cetyl benzenesulfonic acid sodium：5~15 parts, octadecyl three
Methyl bromide ammonium：1~5 part, alumina silicate：10~20 parts, fluorin modified crylic acid ester：2~6 parts, organosiloxane defoamer：2~5
Part, aluminium triphosphate：5~8 parts, polyamide wax pulp：5~10 parts, propylene glycol methyl ether acetate：30~40 parts, water：90~100
Part.
Further, each composition quality fraction is as follows in the coating：Polyurethane modified acrylic resin：70~76 parts, hydroxyl
Propyl methocel：3~5 parts, amino resins：5~7 parts, isophorone diamine：10~13 parts, diphenylmethanediamiand：3
~4 parts, cetyl benzenesulfonic acid sodium：5~7 parts, Cetyltrimethylammonium bromide：1~4 part, alumina silicate：10~14 parts, fluorine
Modification acrylate：2~4 parts, organosiloxane defoamer：2~3 parts, aluminium triphosphate：5~6 parts, polyamide wax pulp：5~7
Part, propylene glycol methyl ether acetate：30~34 parts, water：90~93 parts.
Preferably, each composition quality fraction is as follows in the coating：Polyurethane modified acrylic resin：73 parts, hydroxypropyl
Methylcellulose：4 parts, amino resins：6 parts, isophorone diamine：12 parts, diphenylmethanediamiand：6 parts, cetyl benzene sulphur
Sour sodium：6 parts, Cetyltrimethylammonium bromide：3 parts, alumina silicate：12 parts, fluorin modified crylic acid ester：3 parts, organosiloxane disappears
Infusion：2 parts, aluminium triphosphate：6 parts, polyamide wax pulp：5 parts, propylene glycol methyl ether acetate：30 parts, water：90 parts.
In addition, the preparation of the polyurethane modified acrylic resin, includes the following steps：
1) nucleus emulsion is prepared
The end NCO base polyurethane prepolymer for use as of 30~40 mass point is taken, is added in the water of 60~80 mass point, stirs and evenly mixs,
Obtain nucleus emulsion；
2) shell emulsion is prepared
By the methyl methacrylate of 50~60 mass point, the ethyl methacrylate of 5~10 mass point, 5~10 mass
The water mixing of the styrene divided, the emulsifying agent of 1~3 mass point and 40~50 mass point, stirs, emulsifies, obtain shell emulsion；
3) polyurethane modified acrylic resin is prepared
Reaction bulb is taken, the water of 30~40 mass point, the initiator of 1~5 mass point, the breast of 1~3 mass point are added into bottle
Agent, the buffer of 0.5~2 mass point, stirs and evenly mixs, and then adds the nucleus emulsion, after addition is warming up to 70~80 DEG C,
40~60min is kept the temperature, shell emulsion is then added dropwise into the reaction bulb, is at the uniform velocity added dropwise, is added dropwise in 1.5~2h, wherein,
When shell emulsion surplus is 1/5~1/3, the reducing agent of 0.5~2 mass point is added, after shell emulsion is added dropwise, 75~
At 80 DEG C, 1~1.5h is kept the temperature, is cooled to room temperature, filters to obtain the polyurethane modified acrylic resin.
Separately have, the emulsifying agent in the step 2) and step 3) is selected from ethyoxyl phenolic ether ammonium sulfate, Nonyl pheno
One kind in ether, allyl ether hydroxypropyl azochlorosulfonate acid sodium.
Again, initiator described in step 3) is one kind in azodiisobutyronitrile, peroxidating two acyl, persulfate.
Further more, the one kind of buffer described in step 3) in dibastic sodium phosphate, disodium hydrogen phosphate and sodium acid carbonate.
And reducing agent described in step 3) is sodium sulfate salt or sodium hypophosphite.
In addition, the coating is coated to antitheft door door-plate steel slab surface, 230~240 DEG C of roller coat temperature, roller by roll coating model
It is 1~2 time to apply number.
The beneficial effects of the present invention are：
The coating uses polyurethane modified acrylic resin, has excellent fire-retardant and wear-resisting property, and cure speed
Degree is fast, and also with preferable mechanical property, ageing-resistant performance and resistance to chemical corrosion, strong adhesive force, ductility is good, resistance to height
Temperature, service life length, change processing technology, are concentrated on antitheft door door-plate slab and complete roller coat processing, simplify machining clearance, nothing
Painting workshop need to be separately provided.
The antitheft door door-plate slab stage can by roller coat by paint spraying provided by the present invention in antitheft door door-plate
Steel slab surface, forms coating, can directly carry out following process, obtain moulding anti-theft door board, even if baroque security door
Harden structure, also completes paint spraying in the slab stage, without follow-up application, instead of in existing process " needed for being first processed into
Shape, then sprays to obtain shaped article again " technique, coating and antitheft door door-plate slab strong adhesive force will not be because processing work
Skill and crack or come off.Roller coating technology due to being roller coat shaping quick-drying replaces spraying coating process, the utilization of coating during application
Degree can reach more than 90%, reduce volatilization and waste in air, effectively reduce because spraying causes coating to volatilize what is formed
VOCs, VOCs discharge capacitys≤420ppm in roller coat workshop, coating environment protecting are good.The antitheft door door-plate system completed to roller coat application
Product are processed, the curved performances of antitheft door door-plate T up to 0T (it is completely seamless to close up after 180 ° of the finished product slab bending after roller coat,
Coating, which does not burst, to come off) or 1T (twice after 180 ° of bendings, outermost coated surface is not fallen off slab, is not burst), ensure anti-
Steal door board quality.
The polyurethane modified acrylic resin is prepared by way of core-shell emulsion polymerization, obtains heterogeneous latex
Particle, after tack is shouldered when can effectively lift film formation at low temp performance, the high temperature of coating, and make it that coating is steady with excellent storage
It is qualitative, after forming film coated in steel slab surface, higher hardness can be kept at high temperature, the wear-resisting property of coating obtains very big
Lifting.
Embodiment
Below by specific embodiment, the present invention is described further, but embodiment is not intended to limit the protection of the present invention
Scope.
Table 1 is for a kind of antitheft door door-plate described in the embodiment of the present invention with acrylic resin modified energy-saving and environment-friendly paint into sub-prime
Measure fraction list.Table 2 is preparation polyurethane modified acrylic resin ingredient lists described in the embodiment of the present invention.Table 3 is the present invention
A kind of acrylic resin modified energy-saving and environment-friendly paint performance parameter list of antitheft door door-plate described in embodiment.Table 4 is the present invention
A kind of antitheft door door-plate described in embodiment is with acrylic resin modified energy-saving and environment-friendly paint roller coat in antitheft door door-plate steel slab surface
Coating performance parameter list afterwards.
The antitheft door door-plate is as follows with acrylic resin modified energy-saving and environment-friendly paint preparation method：
The acrylic resin modified energy-saving and environment-friendly paint each component of the antitheft door door-plate is added in high speed dispersor, is stirred
After mixing uniformly, 30~60min of high speed dispersion, stirring, discharging, filtering, packaging, storage.
The polyurethane modified acrylic resin process for preparation is as follows：
Reaction bulb is taken, the water of 30~40 mass point, the initiator of 1~5 mass point, the breast of 1~3 mass point are added into bottle
Agent, the buffer of 0.5~2 mass point, stirs and evenly mixs, and then adds the nucleus emulsion, after addition is warming up to 70~80 DEG C,
40~60min is kept the temperature, shell emulsion is then added dropwise into the reaction bulb, is at the uniform velocity added dropwise, is added dropwise in 1.5~2h, wherein,
When shell emulsion surplus is 1/5~1/3, the reducing agent of 0.5~2 mass point is added, after shell emulsion is added dropwise, 75~
At 80 DEG C, 1~1.5h is kept the temperature, is cooled to room temperature, filters to obtain the polyurethane modified acrylic resin.
Wherein, the emulsifying agent is selected from ethyoxyl phenolic ether ammonium sulfate, nonylphenol polyoxyethylene ether, allyl ether hydroxypropyl sulphur
One kind in sour sodium.The initiator is azodiisobutyronitrile, one kind in peroxidating two acyl, persulfate.The buffer
One kind in dibastic sodium phosphate, disodium hydrogen phosphate and sodium acid carbonate.The reducing agent is sodium sulfate salt or sodium hypophosphite.
1 (unit of table：Part)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Polyurethane modified acrylic resin | 73 | 80 | 70 | 75 | 78 |
| Hydroxypropyl methyl cellulose | 4 | 5 | 3 | 4 | 5 |
| Amino resins | 6 | 8 | 10 | 9 | 7 |
| Isophorone diamine | 12 | 10 | 13 | 15 | 14 |
| Diphenylmethanediamiand | 6 | 8 | 4 | 3 | 7 |
| Cetyl benzenesulfonic acid sodium | 6 | 10 | 5 | 15 | 12 |
| Cetyltrimethylammonium bromide | 3 | 1 | 4 | 5 | 2 |
| Alumina silicate | 12 | 15 | 10 | 20 | 18 |
| Fluorin modified crylic acid ester | 3 | 2 | 6 | 5 | 4 |
| Organosiloxane defoamer | 2 | 2 | 5 | 4 | 3 |
| Aluminium triphosphate | 6 | 8 | 6 | 5 | 7 |
| Polyamide wax pulp | 5 | 8 | 9 | 10 | 7 |
| Propylene glycol methyl ether acetate | 30 | 35 | 40 | 38 | 32 |
| Water | 90 | 95 | 92 | 100 | 98 |
2 (unit of table：Quality point)
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Tensile strength (MPa) | 35 | 33 | 25 | 28 | 30 |
| Elongation at break (%) | 9.0 | 8.5 | 8.8 | 8.0 | 8.3 |
| Shore hardness | 65 | 63 | 55 | 60 | 58 |
A kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate described in the embodiment of the present invention is passed through into roller coat
Mode is coated in antitheft door door-plate steel slab surface, after curing at 200 DEG C, is cooled to room temperature, and when placement 48 is small, measures slab table
Finishing coat performance is as shown in table 4.Wherein, impact resistance test method measure with reference to as defined in standard GB/T/T1732-93
The method of paint film impact resistance, is fallen within test plate (panel) without causing the maximum that paint film destroys high with the weight of fixed mass (1kg)
Spend (cm) and represent paint film impact resistance.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Impact resistance (cm) | 120 | 110 | 118 | 116 | 114 |
| Salt spray resistance duration (h) | 3150 | 3100 | 2900 | 2950 | 3130 |
| Artificial accelerated aging duration (h) | 3200 | 3250 | 3280 | 3100 | 3190 |
| Heat resistance | 780 | 740 | 750 | 700 | 760 |
It is antitheft with acrylic resin modified energy-saving and environment-friendly paint application using a kind of antitheft door door-plate provided by the present invention
Obtained antitheft door door-plate after door board slab, the curved performances of T are up to 0T or 1T.Utilization efficiency of coatings is high, and every 30 kilograms of coating can
1 ton of slab of application.Do not crack under 230 DEG C of high temperature, is non-discolouring, ageing resistance is strong, places consecutive sunlight 10~15 outdoors
It is year not yellowing, non-discolouring.Acidproof corrosion resistance is strong, the good product of roller coat is put into 85 DEG C of water boil 2H life be progressively heated at again
100 DEG C, product without change colour, fall paint, blistering.At normal temperatures with after 5% Nad solution immersion 24H, product surface non-corroding, become
Color and coating come off.Pure cotton cloth is dipped in full 95% alcohol bag on 500g counterweights, it is left with speed (20mm) 40-60 times per minute
Right stroke wipes 50 circulations in product surface, without de-oiling of fading.This hair is coated with according to the X methods detection of drawing in U.S. ASTM
The moulding anti-theft door board product of bright provided coating, can reach the 0=ASTM grades of ISO grades, and notching edge is completely smooth,
The peeling that edge has not a particle of.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, can be to the technology of invention
Scheme technical scheme is modified or replaced equivalently, without departing from the scope of technical solution of the present invention, it should all cover the power in the present invention
In sharp claimed range.
Claims (3)
- A kind of 1. acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate, it is characterised in that each component in the coating Mass fraction is as follows：Polyurethane modified acrylic resin：70 ~ 80 parts, hydroxypropyl methyl cellulose：3 ~ 5 parts, amino resins：5 ~ 10 parts, different Buddhist That ketone diamines：10 ~ 15 parts, diphenylmethanediamiand：3 ~ 8 parts, cetyl benzenesulfonic acid sodium：5 ~ 15 parts, octadecyl trimethyl Ammonium bromide：1 ~ 5 part, alumina silicate：10 ~ 20 parts, fluorin modified crylic acid ester：2 ~ 6 parts, organosiloxane defoamer：2 ~ 5 parts, trimerization Aluminum phosphate：5 ~ 8 parts, polyamide wax pulp：5 ~ 10 parts, propylene glycol methyl ether acetate：30 ~ 40 parts, water：90 ~ 100 parts；The preparation of the polyurethane modified acrylic resin, includes the following steps：1) nucleus emulsion is preparedThe end NCO base polyurethane prepolymer for use as of 30 ~ 40 mass parts is taken, is added in the water of 60 ~ 80 mass parts, stirs and evenly mixs, obtains core breast Change liquid；2) shell emulsion is preparedBy the methyl methacrylate of 50 ~ 60 mass parts, the ethyl methacrylate of 5 ~ 10 mass parts, the benzene second of 5 ~ 10 mass parts The water mixing of alkene, the emulsifying agent of 1 ~ 3 mass parts and 40 ~ 50 mass parts, is stirred, emulsification, obtains shell emulsion；3) polyurethane modified acrylic resin is preparedReaction bulb is taken, the water of 30 ~ 40 mass parts of addition into bottle, the initiator of 1 ~ 5 mass parts, the emulsifying agent of 1 ~ 3 mass parts, The buffer of 0.5 ~ 2 mass parts, stirs and evenly mixs, and then adds the nucleus emulsion, after addition is warming up to 70 ~ 80 DEG C, insulation 40 ~ 60min, shell emulsion is then added dropwise into the reaction bulb, is at the uniform velocity added dropwise, is added dropwise in 1.5 ~ 2h, wherein, emulsified in shell When liquid surplus is 1/5 ~ 1/3, the reducing agent of 0.5 ~ 2 mass parts is added, after shell emulsion is added dropwise, at 75 ~ 80 DEG C, is protected 1 ~ 1.5h of temperature, is cooled to room temperature, and filters to obtain the polyurethane modified acrylic resin；Emulsifying agent in the step 2) and step 3) is selected from ethyoxyl phenolic ether ammonium sulfate, nonylphenol polyoxyethylene ether, pi-allyl One kind in ether hydroxypropyl azochlorosulfonate acid sodium；Initiator described in step 3) is azodiisobutyronitrile, one kind in peroxidating two acyl, persulfate；The one kind of buffer described in step 3) in dibastic sodium phosphate, disodium hydrogen phosphate and sodium acid carbonate；Reducing agent described in step 3) is sodium sulfate salt or sodium hypophosphite；The coating is coated to antitheft door door-plate steel slab surface, 230 ~ 240 DEG C of roller coat temperature by roll coating model, and roller coat number is 1 ~ 2 time.
- 2. a kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate according to claim 1, its feature exist In each composition quality number is as follows in the coating：Polyurethane modified acrylic resin：70 ~ 76 parts, hydroxypropyl methyl fiber Element：3 ~ 5 parts, amino resins：5 ~ 7 parts, isophorone diamine：10 ~ 13 parts, diphenylmethanediamiand：3 ~ 4 parts, cetyl benzene Sodium sulfonate：5 ~ 7 parts, Cetyltrimethylammonium bromide：1 ~ 4 part, alumina silicate：10 ~ 14 parts, fluorin modified crylic acid ester：2 ~ 4 parts, Organosiloxane defoamer：2 ~ 3 parts, aluminium triphosphate：5 ~ 6 parts, polyamide wax pulp：5 ~ 7 parts, propylene glycol methyl ether acetate：30~ 34 parts, water：90 ~ 93 parts.
- 3. a kind of acrylic resin modified energy-saving and environment-friendly paint of antitheft door door-plate according to claim 1, its feature exist In each composition quality number is as follows in the coating：Polyurethane modified acrylic resin：73 parts, hydroxypropyl methyl cellulose：4 Part, amino resins：6 parts, isophorone diamine：12 parts, diphenylmethanediamiand：6 parts, cetyl benzenesulfonic acid sodium：6 parts, ten Eight alkyl trimethyl ammonium bromides：3 parts, alumina silicate：12 parts, fluorin modified crylic acid ester：3 parts, organosiloxane defoamer：2 parts, three Poly aluminium phosphate：6 parts, polyamide wax pulp：5 parts, propylene glycol methyl ether acetate：30 parts, water：90 parts.
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| CN104419273B (en) * | 2013-09-04 | 2017-03-01 | 陶氏环球技术有限公司 | Prepare the method for colored dispersion and the colored dispersion being obtained by it |
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| CN101967329A (en) * | 2009-07-28 | 2011-02-09 | 上海汇丽涂料有限公司 | Water-based colorful imitation marble paint |
| CN102796429A (en) * | 2012-09-05 | 2012-11-28 | 珠海市美筑化工有限公司 | Water-soluble paint, preparation method and spraying technique thereof |
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