CN104140753B - A kind of not only can ED application but also the water paint that can spray and preparation method thereof - Google Patents
A kind of not only can ED application but also the water paint that can spray and preparation method thereof Download PDFInfo
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- CN104140753B CN104140753B CN201410384586.6A CN201410384586A CN104140753B CN 104140753 B CN104140753 B CN 104140753B CN 201410384586 A CN201410384586 A CN 201410384586A CN 104140753 B CN104140753 B CN 104140753B
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Abstract
The present invention relates to a kind of not only can ED application but also the water paint that can spray and preparation method thereof, described coating is one-component, had thermoplastic elastomer modified anionic acrylic resin by 18-36 weight portion, 4-9 weight portion blocked isocyanate curing agent, 0.2-0.6 weight portion nertralizer, 16-32 weight portion color stuffing, 0.4-0.8 weight portion aqueous levelling agent, 0.2-0.5 weight portion water-based thickener, 21.1-61.2 parts by weight of deionized water form, fineness≤15 μm.The coating of the present invention not only can ED application but also can spray, utilization efficiency of coatings reaches more than 95%, solves utilization rate of spraying paint low and reclaim a complicated difficult problem, two kinds of application modes on film performance without impact, greatly reduce painting cost and energy-saving and emission-reduction, there is extraordinary social benefit.
Description
[technical field]
The invention belongs to water paint and preparation method technical field, relate to a kind of not only can ED application but also the water paint that can spray and preparation method thereof.
[background technology]
Present stage is when progressively replacing organic solvent type coatings with water paint, it is common to adopts the coating process as the contour painting rate of electrophoretic painting and electrostatic spraying, and makes great efforts to develop the recovery and reuse technology of discarded water paint, to reach the fully utilized of coating.Electrophoretic coating utilization rate can reach more than 95%, even when adopting electrostatic spray application ideally, also having the over-sprayed paint fog of more than 10% to disperse, if adopting hand spray to have at least the over-sprayed paint fog of more than 50% to disperse.Therefore, how to reclaim the coating cloud that disperses, utilize so as to recirculate, improve the utilization rate of paint, reduce the discharge of waste water, waste residue, reduce the important topic that cost is coating worker research.But the coating recycling that over-sprayed paint fog retracting device cannot will reclaim on the market now, and reclaimer is complicated and cost is high, solves over-sprayed paint fog but without very effective approach and recycles problem.
[summary of the invention]
The present invention is directed to the deficiencies in the prior art, there is provided a kind of not only can ED application but also the water paint that can spray and preparation method thereof, product of the present invention is one-component coating, utilization efficiency of coatings reaches more than 95%, solve the difficult problem that utilization rate of spraying paint is low and recovery is complicated, performance without impact, is greatly reduced painting cost and energy-saving and emission-reduction, has extraordinary social benefit by two kinds of application modes.This coating both may be used for workpiece weld in electrophoresis process and had been difficult to film on electrophoresis, directly weld is sprayed, it is also possible to be provided purely for the spraying of metalwork, and over-sprayed paint fog is directly used in electrophoresis after water curtain reclaims, and cost recovery is low.This paint coatings hardness reaches 2H, impact strength is 50Kg.cm, adhesive force is 0 grade, has very excellent acidproof, alkaline-resisting, resistance to water, also has good corrosion resistance, salt fog resistance reaches 800 hours, unidirectional Erosion Width≤2mm, and there is very excellent weather resistance, through 1000 hours QUV degradations, gloss loss≤15%, Δ E≤1.5.
The technical scheme is that a kind of not only can ED application but also the single-component water-based coating that can spray, its feature mainly comprises thermoplastic elastomer modified anionic acrylic resin, this thermoplastic elastomer modified anionic acrylic resin is by 11-21 parts by weight of propylene glycol monobutyl ether, 7-19 parts by weight of isobutanol, 8-12 weight portion SBS, 5-9 weight parts of methacrylic acid, 7-12 parts by weight of acrylic acid hydroxyl ethyl ester, 11-15 parts by weight of methylmethacrylate, the different monooctyl ester of 10-16 parts by weight of acrylic acid, 9-13 parts by weight of styrene, 0.8-1.6 weight portion benzoyl peroxide, 0.2-0.4 weight portion azodiisobutyronitrile and 3-9 weight portion methyl iso-butyl ketone (MIBK) composition.
This coating also can include following optimization composition further:
In described single-component water-based coating, in every elastomer-modified anionic acrylic resin of 18-36 parts per weight of thermoplastic, it is also added with 16-32 weight portion color stuffing.
In described single-component water-based coating, in every elastomer-modified anionic acrylic resin of 18-36 parts per weight of thermoplastic, it is also added with 0.4-0.8 weight portion aqueous levelling agent, 0.2-0.5 weight portion water-based thickener, 21.1-61.2 parts by weight of deionized water.
In described single-component water-based coating, in every elastomer-modified anionic acrylic resin of 18-36 parts per weight of thermoplastic, it is also added with 4-9 weight portion blocked isocyanate curing agent.
Described blocked isocyanate curing agent is by 12-29 weight portion methyl iso-butyl ketone (MIBK), 37-43 weight portion isophorone diisocyanate, 24-27 weight portion methyl ethyl ketoxime, 6-10 parts by weight of isopropyl alcohol and 4-8 weight portion ethylene glycol monobutyl ether composition.
In described single-component water-based coating, in every elastomer-modified anionic acrylic resin of 18-36 parts per weight of thermoplastic, it is also added with 0.2-0.6 weight portion nertralizer.
Described nertralizer is any one in dibutyl amine or diethanolamine.
Described color stuffing is a kind of or any several mixture in titanium dioxide, white carbon black, Kaolin or barium sulfate.
Described aqueous levelling agent is selected from any one in FLWB-127 or FLWK-134 of commercially available German Silcona.
Described water-based thickener is selected from any one in commercially available BYK-420, BYK-425 or BYK-428.
Present invention additionally comprises a kind of not only can ED application but also the preparation method of water paint that can spray:
By 5-9 weight parts of methacrylic acid, 7-12 parts by weight of acrylic acid hydroxyl ethyl ester, 11-15 parts by weight of methylmethacrylate; the different monooctyl ester of 10-16 parts by weight of acrylic acid; 9-13 parts by weight of styrene, 0.8-1.6 weight portion benzoyl peroxide mix homogeneously obtains mixed liquor a, stand-by；
The azodiisobutyronitrile of 0.2-0.4 weight portion and 3-9 weight portion methyl iso-butyl ketone (MIBK) mix homogeneously are obtained mixed liquor b, stand-by；
By 11-21 parts by weight of propylene glycol monobutyl ether, 7-19 parts by weight of isobutanol and 8-12 weight portion SBS add in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 100 DEG C, start to drip mixed liquor a, being incubated 1 hour after within 3 hours, dripping off, then dropping mixed liquor b, half an hour drips off, then it is warmed up to 110 DEG C and is incubated 2 hours, then cool to less than 45 DEG C and prepare thermoplastic elastomer modified anionic acrylic resin.
Above-mentioned process also may include steps of further:
Elastomer-modified for 18-36 parts per weight of thermoplastic anionic acrylic resin and 4-9 weight portion blocked isocyanate curing agent are added 30 minutes mix homogeneously of stirring in grinding pot, it is subsequently adding 0.2-0.6 weight portion nertralizer to stir 30 minutes, disposable for 21.1-61.2 parts by weight of deionized water addition grinding pot will be stirred 30 minutes again, add 16-32 weight portion color stuffing high speed sand milling 2 hours, to fineness≤15 μm, it is subsequently adding 0.4-0.8 weight portion levelling agent, 0.2-0.5 parts by weight of thickening agent, stir 1 hour, in whole preparation process grinding pot, temperature of charge controls at 15-30 DEG C.Adopt filter screen filtration discharging, it is thus achieved that described not only can ED application but also the water paint that can spray
Described blocked isocyanate curing agent is prepared by following steps: add in the reaction vessel with agitator and condensing tube by 12-29 weight portion methyl iso-butyl ketone (MIBK) and 37-43 weight portion isophorone diisocyanate, lead to nitrogen, be warmed up to 80 DEG C, the blended liquid of dropping 24-27 weight portion methyl ethyl ketoxime and 6-10 parts by weight of isopropyl alcohol, within 2 hours, drip off, after being incubated 2 hours, add 4-8 weight portion ethylene glycol monobutyl ether, continue insulation 1 hour, cool to 45 DEG C with bottom discharge, it is thus achieved that described blocked isocyanate curing agent.
The a kind of of the present invention not only can ED application but also the water paint that can spray provide the benefit that: product of the present invention is one-component coating, utilization efficiency of coatings reaches more than 95%, solve the difficult problem that utilization rate of spraying paint is low and recovery is complicated, two kinds of application modes on performance without impact, greatly reduce painting cost and energy-saving and emission-reduction, having extraordinary social benefit, this paint spraying is convenient, uses environmental protection, safety.This coating adopts thermoplastic elastomer modified anionic acrylic resin, improve thermoplastic elastomer (TPE) by the change of feed way and introduce the efficiency of molecular backbone, the resin of this synthesis is matrix resin and grind resin, color stuffing can well be wrapped up so that not only ED application but also the coating that can spray can become reality.This coating both may be used for workpiece weld in electrophoresis process and had been difficult to film on electrophoresis, directly weld is sprayed, it is also possible to be provided purely for the spraying of metalwork, and over-sprayed paint fog is directly used in electrophoresis after water curtain reclaims.This paint coatings hardness reaches 2H, impact strength is 50Kg.cm, adhesive force is 0 grade, has very excellent acidproof, alkaline-resisting, resistance to water, also has good corrosion resistance, salt fog resistance reaches 800 hours, unidirectional Erosion Width≤2mm, and there is very excellent weather resistance, through 1000 hours QUV degradations, gloss loss≤15%, Δ E≤1.5.
[detailed description of the invention]
Hereinafter principles of the invention and feature being described, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Embodiment 1
1) described thermoplastic elastomer modified anionic acrylic resin formula:
By formula ratio by methacrylic acid, 2-(Acryloyloxy)ethanol, methyl methacrylate, Isooctyl acrylate monomer, styrene, benzoyl peroxide mix homogeneously obtains mixed liquor a, stand-by；
By formula ratio, azodiisobutyronitrile and methyl iso-butyl ketone (MIBK) mix homogeneously are obtained mixed liquor b, stand-by；
By formula ratio by propylene glycol monobutyl ether, isobutanol and SBS (block copolymer of styrene and butadiene) add in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 100 DEG C, start to drip mixed liquor a, after within 3 hours, dripping off, be incubated 1 hour, then dropping mixed liquor b, half an hour drips off, then it is warmed up to 110 DEG C and is incubated 2 hours, then cool to 45 DEG C with bottom discharge, it is thus achieved that described thermoplastic elastomer modified anionic acrylic resin；
2) described blocked isocyanate curing agent formula
By formula ratio, methyl iso-butyl ketone (MIBK) and isophorone diisocyanate are added in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 80 DEG C, the blended liquid of dropping methyl ethyl ketoxime and isopropanol, within 2 hours, drip off, after being incubated 2 hours, add ethylene glycol monobutyl ether, continue insulation 1 hour, cool to 45 DEG C with bottom discharge, it is thus achieved that described blocked isocyanate curing agent.
3) described a kind of not only can ED application but also the aqueous coating formulation that can spray
By formula ratio, thermoplastic elastomer modified anionic acrylic resin and blocked isocyanate curing agent are added 30 minutes mix homogeneously of stirring in grinding pot, it is subsequently adding nertralizer dibutyl amine to stir 30 minutes, disposable for deionized water addition grinding pot will be stirred 30 minutes again, add color stuffing titanium dioxide, Kaolin and barium sulfate high speed sand milling 2 hours, to fineness≤15 μm, it is subsequently adding levelling agent FLWB-127, thickening agent BYK-425, stirring 1 hour, in whole preparation process grinding pot, temperature of charge controls at 15-30 DEG C.Adopt filter screen filtration discharging, it is thus achieved that described not only can ED application but also the water paint that can spray.
Embodiment 2
1) described thermoplastic elastomer modified anionic acrylic resin formula:
By formula ratio by methacrylic acid, 2-(Acryloyloxy)ethanol, methyl methacrylate, Isooctyl acrylate monomer, styrene, benzoyl peroxide mix homogeneously obtains mixed liquor a, stand-by；
By formula ratio, azodiisobutyronitrile and methyl iso-butyl ketone (MIBK) mix homogeneously are obtained mixed liquor b, stand-by；
By formula ratio by propylene glycol monobutyl ether, isobutanol and SBS (block copolymer of styrene and butadiene) add in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 100 DEG C, start to drip mixed liquor a, after within 3 hours, dripping off, be incubated 1 hour, then dropping mixed liquor b, half an hour drips off, then it is warmed up to 110 DEG C and is incubated 2 hours, then cool to 45 DEG C with bottom discharge, it is thus achieved that described thermoplastic elastomer modified anionic acrylic resin；
2) described blocked isocyanate curing agent formula
By formula ratio, methyl iso-butyl ketone (MIBK) and isophorone diisocyanate are added in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 80 DEG C, the blended liquid of dropping methyl ethyl ketoxime and isopropanol, within 2 hours, drip off, after being incubated 2 hours, add ethylene glycol monobutyl ether, continue insulation 1 hour, cool to 45 DEG C with bottom discharge, it is thus achieved that described blocked isocyanate curing agent.
3) described a kind of not only can ED application but also the aqueous coating formulation that can spray
By formula ratio, thermoplastic elastomer modified anionic acrylic resin and blocked isocyanate curing agent are added 30 minutes mix homogeneously of stirring in grinding pot, it is subsequently adding nertralizer diethanolamine to stir 30 minutes, disposable for deionized water addition grinding pot will be stirred 30 minutes again, add color stuffing white carbon black and Kaolin high speed sand milling 2 hours, to fineness≤15 μm, it is subsequently adding levelling agent FLWK-134, thickening agent BYK-420, stirring 1 hour, in whole preparation process grinding pot, temperature of charge controls at 15-30 DEG C.Adopt filter screen filtration discharging, it is thus achieved that described not only can ED application but also the water paint that can spray.
Embodiment 3
1) described thermoplastic elastomer modified anionic acrylic resin formula:
By formula ratio by methacrylic acid, 2-(Acryloyloxy)ethanol, methyl methacrylate, Isooctyl acrylate monomer, styrene, benzoyl peroxide mix homogeneously obtains mixed liquor a, stand-by；
By formula ratio, azodiisobutyronitrile and methyl iso-butyl ketone (MIBK) mix homogeneously are obtained mixed liquor b, stand-by；
By formula ratio by propylene glycol monobutyl ether, isobutanol and SBS (block copolymer of styrene and butadiene) add in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 100 DEG C, start to drip mixed liquor a, after within 3 hours, dripping off, be incubated 1 hour, then dropping mixed liquor b, half an hour drips off, then it is warmed up to 110 DEG C and is incubated 2 hours, then cool to 45 DEG C with bottom discharge, it is thus achieved that described thermoplastic elastomer modified anionic acrylic resin；
2) described blocked isocyanate curing agent formula
By formula ratio, methyl iso-butyl ketone (MIBK) and isophorone diisocyanate are added in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 80 DEG C, the blended liquid of dropping methyl ethyl ketoxime and isopropanol, within 2 hours, drip off, after being incubated 2 hours, add ethylene glycol monobutyl ether, continue insulation 1 hour, cool to 45 DEG C with bottom discharge, it is thus achieved that described blocked isocyanate curing agent.
3) described a kind of not only can ED application but also the aqueous coating formulation that can spray
By formula ratio, thermoplastic elastomer modified anionic acrylic resin and blocked isocyanate curing agent are added 30 minutes mix homogeneously of stirring in grinding pot, it is subsequently adding nertralizer dibutyl amine to stir 30 minutes, disposable for deionized water addition grinding pot will be stirred 30 minutes again, add color stuffing titanium dioxide, white carbon black and barium sulfate high speed sand milling 2 hours, to fineness≤15 μm, it is subsequently adding levelling agent FLWK-134, thickening agent BYK-428, stirring 1 hour, in whole preparation process grinding pot, temperature of charge controls at 15-30 DEG C.Adopt filter screen filtration discharging, it is thus achieved that described not only can ED application but also the water paint that can spray.
Above-described embodiment 1-3 is prepared not only can ED application but also the water paint that can spray, adopt ED application and two kinds of application modes of spraying to carry out making sheet test, thickness be all 20-30um, and condition of cure is 140 DEG C and toasts 20min.
The key technical indexes of model such as following table:
Thus the present invention prepare not only can ED application but also the water paint that can spray, utilization efficiency of coatings reaches more than 95%, solve the difficult problem that utilization rate of spraying paint is low and recovery is complicated, two kinds of application modes on performance without impact, greatly reduce painting cost and energy-saving and emission-reduction, there is extraordinary social benefit, save the energy and Environmental Safety, the excellent performances such as final coating hardness, impact strength adhesive force, also have good corrosion resistance and very excellent weather resistance simultaneously.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (3)
1. one kind not only can ED application but also the preparation method of water paint that can spray, it is characterised in that:
By 5-9 weight parts of methacrylic acid, 7-12 parts by weight of acrylic acid hydroxyl ethyl ester, 11-15 parts by weight of methylmethacrylate; the different monooctyl ester of 10-16 parts by weight of acrylic acid; 9-13 parts by weight of styrene, 0.8-1.6 weight portion benzoyl peroxide mix homogeneously obtains mixed liquor a, stand-by；
The azodiisobutyronitrile of 0.2-0.4 weight portion and 3-9 weight portion methyl iso-butyl ketone (MIBK) mix homogeneously are obtained mixed liquor b, stand-by；
By 11-21 parts by weight of propylene glycol monobutyl ether, 7-19 parts by weight of isobutanol and 8-12 weight portion SBS add in the reaction vessel with agitator and condensing tube, lead to nitrogen, be warmed up to 100 DEG C, start to drip mixed liquor a, being incubated 1 hour after within 3 hours, dripping off, then dropping mixed liquor b, half an hour drips off, then it is warmed up to 110 DEG C and is incubated 2 hours, then cool to less than 45 DEG C and prepare thermoplastic elastomer modified anionic acrylic resin.
2. as claimed in claim 1 not only can ED application but also the preparation method of water paint that can spray, characterized by further comprising: elastomer-modified for 18-36 parts per weight of thermoplastic anionic acrylic resin and 4-9 weight portion blocked isocyanate curing agent are added 30 minutes mix homogeneously of stirring in grinding pot, it is subsequently adding 0.2-0.6 weight portion nertralizer to stir 30 minutes, disposable for 21.1-61.2 parts by weight of deionized water addition grinding pot will be stirred 30 minutes again, add 16-32 weight portion color stuffing high speed sand milling 2 hours, to fineness≤15 μm, it is subsequently adding 0.4-0.8 weight portion levelling agent, 0.2-0.5 parts by weight of thickening agent, stir 1 hour, in whole preparation process grinding pot, temperature of charge controls at 15-30 DEG C, adopt filter screen filtration discharging, obtain described not only can ED application but also the water paint that can spray.
3. as claimed in claim 2 not only can ED application but also the preparation method of water paint that can spray, it is characterized in that described blocked isocyanate curing agent is prepared by following steps: add in the reaction vessel with agitator and condensing tube by 12-29 weight portion methyl iso-butyl ketone (MIBK) and 37-43 weight portion isophorone diisocyanate, logical nitrogen, it is warmed up to 80 DEG C, the blended liquid of dropping 24-27 weight portion methyl ethyl ketoxime and 6-10 parts by weight of isopropyl alcohol, within 2 hours, drip off, after being incubated 2 hours, add 4-8 weight portion ethylene glycol monobutyl ether, continue insulation 1 hour, cool to 45 DEG C with bottom discharge, obtain described blocked isocyanate curing agent.
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| CN110790886A (en) * | 2019-11-13 | 2020-02-14 | 浩力森涂料（上海）有限公司 | Single-component coating, film-forming resin thereof and preparation method |
| CN116144238A (en) * | 2021-11-23 | 2023-05-23 | 浩力森涂料（上海）有限公司 | Water-based reflective heat-insulating paint for cab coating and preparation method thereof |
| CN114316207B (en) * | 2021-12-22 | 2024-04-16 | 南雄市佳明化工有限公司 | Polyurethane drier, preparation method thereof and curing material |
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| DE1903703C3 (en) * | 1969-01-25 | 1971-12-02 | Basf Ag | Coating agent for the production of electrically depositable coatings |
| JP2001234116A (en) * | 2000-02-23 | 2001-08-28 | Nippon Paint Co Ltd | High weatherability cationic electrodeposition coating material composition |
| CN1807528A (en) * | 2006-02-10 | 2006-07-26 | 冯国贤 | Acroleic acid/polyurethane transparent anode electrophoresis coating and its preparation method |
| CN101081957B (en) * | 2007-06-26 | 2010-12-01 | 广东雅图化工有限公司 | Automobile finishing varnish containing water dispersible acrylic ester and preparation method thereof |
| CN102993795A (en) * | 2011-09-16 | 2013-03-27 | 郑旷宇 | Solvent-free waterproof paint containing segmented copolymer |
| CN103289553B (en) * | 2013-06-24 | 2015-04-29 | 浩力森涂料（上海）有限公司 | Transparent high wear-resistant acrylic acid cathode electrophoretic paint and preparation method thereof |
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Address after: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee after: HLS COATING (SHANGHAI) Co.,Ltd. Patentee after: Hollyson Chemical Technology (Jiangsu) Co., Ltd Address before: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee before: HLS COATING (SHANGHAI) Co.,Ltd. Patentee before: Hollyson Chemical Technology Jiangsu Co., Ltd |