CN1500841A - New pattern UV light solidifying powdery paints - Google Patents

New pattern UV light solidifying powdery paints Download PDF

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Publication number
CN1500841A
CN1500841A CNA021489424A CN02148942A CN1500841A CN 1500841 A CN1500841 A CN 1500841A CN A021489424 A CNA021489424 A CN A021489424A CN 02148942 A CN02148942 A CN 02148942A CN 1500841 A CN1500841 A CN 1500841A
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China
Prior art keywords
coating
gram
prepolymer resin
powder coating
uvecoat
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CNA021489424A
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CN100374515C (en
Inventor
杰 魏
魏杰
秦长喜
王艳梅
刘瀛
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Beijing University of Chemical Technology
China Lucky Film Group Corp
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Beijing University of Chemical Technology
China Lucky Film Group Corp
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Priority to CNB021489424A priority Critical patent/CN100374515C/en
Publication of CN1500841A publication Critical patent/CN1500841A/en
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Publication of CN100374515C publication Critical patent/CN100374515C/en
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Abstract

The present invention relates to one kind of UV cured paint, and is especially one kind of UV cured powdered paint. The paint includes UV initiator 1-7 wt%, prepolymer resin 70-90 wt%, assistant 1-5 wt% and inorganic nano material 2-15 wt%. The UV cured powdered paint of the present invention has low smelting temperature, fast curing speed and smooth coating, and is safe, economic and suitable for painting various kinds of base material.

Description

A kind of novel UV photocuring powder coating
Technical field
The present invention relates to a kind of UV photo-cured coating, particularly a kind of UV photocuring powder coating.
Background technology
Ultraviolet-curing paint is a kind of new coating that grows up 1960's, and to the formulation of rules such as the energy, ecology and environmental protection, further promoted the development of this class coating along with in the world the seventies.This coating be with high-octane UV-light as solidifying the energy, absorb ultraviolet luminous energy by the light trigger in the coating and form free radical, cause photosensitive resin and reactive thinner molecule, and then the generation chain polymerization, making films reaches curing.This curing mode gives photo-cured coating many advantages: coating can 100% film-forming, solvent-free volatilization pollution problem, capacity usage ratio are high, and therefore development is rapidly in recent ten years.
Powder coating is a kind of and the diverse solventless coatings of traditional liquid coating, is by various polymkeric substance, pigment, and mixing such as auxiliary agent back grinding and processing forms, and its equipment and device of plastic processing are close.Powder coating has simplifies working process, save energy and resource, non-environmental-pollution, characteristics such as production efficiency height.Being mainly used in the metal device application, now being widely used in all respects such as household electrical appliance, instrument, trolley part, oil pipeline, also is to develop one of very fast coating variety.
Compare many advantages with traditional coating though powder coating and UV be coating material solidified, on using, still had many limitation.Heat curable powder coating processing temperature height, set time are long, can not use on heat-sensitive substrate materials such as plastics, timber, paper, also are not suitable for the application of thermo-labile article such as scolding tin spare, electronic component; In addition, because the gentle curing of its melt-flow is carried out synchronously, flow time is short, is prone to phenomenons such as orange peel, shrinkage cavity, influences surface quality.Liquid UV is coating material solidified owing to still contain reactive thinner, and Diazolidinyl Urea and eyes in the use, and the uncured component of liquid material infiltration ground can constantly be dispersed in the air and go, and cause atmospheric pollution.
The UV cured powder paint is the new coating technology that the powder coating processing technology is combined with the UV curing technology, and it combines the advantage of traditional powder coating and liquid UV curing technology, has overcome the two defective.Compare with powder coating, UV powder melts temperature is 100~140 ℃, melt temperature (177~200 ℃) than heat curable powder coating is low, curing speed is in second, (10~30min) is faster, thereby the metal device of general thermo-sensitive material such as MDF plate (medium density fibre board (MDF)), timber, plastics, paper and the baking of some non-refractories can be used the application of UV cured powder paint than the speed of heat curable powder coating.The powder of UV powder coating is heat-staple, makes its processing easier, can adopt common forcing machine processing, and can not occur crosslinked phenomenon because of processing temperature is high; The fusion of UV powder coating and curing are divided into two tangible stages, have solved the thermosetting powder coating(s) levelling and have solidified the eclipsed problem.Its fusion, flow and before UV solidifies, to reach best melt-flow level state, guarantee paint film ideal planeness.Compare with UV solidified liquid coating, the raw material of UV powder coating is the high-molecular weight resin, avoided the harm of reactive thinner in the liquid UV coating, and shrinking percentage is low, with base material sticking power height; An application of UV powder coating can form superior in quality paste paint film (75~125um), reduced numerous and diverse technology that the UV liquid coating repeatedly applies; The powder that the spraying of UV powder coating is splashed down is convenient to reclaim and is used, and is more economical than liquid UV coating.It is the patented technology that adds the powder coating component as a kind of filler that Korean Patent KR9505345 discloses with lime carbonate and silicon-dioxide.It is the liquid UV radiation curable coating that adds as a kind of filler that the patent WO0241078 of UCB. S.A. (BE) Bruxelles Belgium has introduced with silicon-dioxide and lime carbonate, adds the performance that filler can improve coating.Another of the said firm piece patent US6017640 discloses with a kind of UV curable of response type inorganic nanoparticles or powder coating component of thermofixation of containing, and can obviously promote performances such as the hardness of coating, anti-organic solvent and raising glossiness.Therefore, be that the UV powder coating of solvent-free environment-protection coating has higher technical superiority, economic advantages and ecological dominance than thermosetting powder coating and UV solidified liquid coating equally.
Summary of the invention
The object of the present invention is to provide a kind of novel UV photocuring powder coating.
Technical scheme of the present invention is, a kind of UV photocuring powder coating, and it comprises: (1) light trigger, (2) prepolymer resin, (3) auxiliary agent, (4) inorganic nano material, its each component concentration is: light trigger 1~7%; Prepolymer resin 70~90%; Auxiliary agent 1~5%; Inorganic nano material 2~15%.
A kind of preferred version, each component concentration of wherein said UV photocuring powder coating is: light trigger 2~5%; Prepolymer resin 80~90%; Auxiliary agent 3~4%; Inorganic nano material 5~10%.
A kind of preferred version, wherein said inorganic nano material are the lime carbonate of nanometer grade calcium carbonate or silicon-dioxide parcel.
The composition of UV photocuring powder coating of the present invention is made up of prepolymer resin, light trigger, auxiliary agent and inorganic nano material, the overall performance behind the main body prepolymer resin decision paint solidification wherein, comprise the viscosity in the solidification process and solidify after hardness, snappiness, weathering resistance and the chemical-resistant etc. of filming, therefore, resin choice is the key of decision performance powder coating.UV cured powder paint common resins has: epoxy acrylate, acrylic resin, unsaturated polyester, polyester acrylate, polyether acrylate.The Uvecoat TM series that the prepolymer resin that uses in the embodiment of the invention provides as UCB. S.A. (BE) Bruxelles Belgium, Uvecoat 3000, Uvecoat 3001, Uvecoat 9010, but be not limited in these.Light trigger is determining the speed of coating photocuring reaction, the selection of light trigger is unusual important problem in the UV cured powder paint, at first, used light trigger must be solid at normal temperatures, will consider in addition after the initiator fusion and the consistency of resin and the deep layer problem of solidification of initiator.Can obtain the coating of good decorative effect and excellent weather resistance behind the free radical photo-initiation initiated polymerization, the initiator that the present invention selects is a radical photoinitiator, comprise: the st-yrax derivative, as Benzoin ethyl ether, benzoin dimethylether (Irgacure 651); The acetophenones derivative that replaces, as 1-hydroxy-cyclohexyl methyl phenyl ketone (Irgacure 184), right-hydroxyethyl ether-α, alpha-alpha-dimethyl methyl phenyl ketone (Darocur 2959) and their composition I rgacure 651/Darocur 2959, Irgacure 184/Darocur 2959.For coating performance and the use properties that improves UV photocuring powder coating also needs to add some auxiliary agents, comprise stopper, defoamer, flow agent etc., wherein stopper is Resorcinol and p methoxy phenol, and defoamer is BYK088, and flow agent is BYK373.By adding different nano materials coating is carried out modification among the present invention, by adding different types of nano material such as CaCO 3, SiO 2The CaCO of parcel 3Nanoparticle can fine raising hardness of film and resistance to acids and bases.
The preparation and the using method of UV photocuring powder coating of the present invention are, behind the first premix by a certain percentage of the light trigger, prepolymer resin, auxiliary agent and the inorganic nano material that propose among the present invention, adopt common forcing machine hot melt batch mixing, through compressing tablet cooling, broken, be ground into fine powder (180 order) again.With pressurized air with dry powder through lance ejection to ground to be painted, earlier make powder melts and keep molten state through infrared radiation, be light-cured into part crosslinked coating film forming that makes through uv-radiation again.
Embodiment
The present invention will be further described below by concrete comparative example and embodiment
Comparative example 1
With 83.7g prepolymer resin Uvecoat 3000 and 9.3g prepolymer resin Uvecoat 9001,4g light trigger Irgacure 651,3g auxiliary agent (stopper p methoxy phenol wherein: 0.5 gram, flow agent BYK373:1.5 gram, defoamer: BYK088:1.0 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified, and measuring film coated surface hardness is that 2H, sticking power are 99%, and shock resistance is 50.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Comparative example 2
With 68.3g prepolymer resin Uvecoat 3000 and 22.7g prepolymer resin Uvecoat 9001,5g light trigger Irgacure184,4g auxiliary agent (stopper p methoxy phenol wherein: 0.5 gram, flow agent BYK373:2.0 gram, defoamer: BYK088:1.5 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Comparative example 3
With 79.9g prepolymer resin Uvecoat 3001 and 14.1g prepolymer resin Uvecoat 9001,1g light trigger Darocure2959,5g auxiliary agent (stopper p methoxy phenol wherein: 1.0 grams, flow agent BYK373:2.0 gram, defoamer: BYK088:2.0 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Comparative example 4
With 85.5g prepolymer resin Uvecoat 3000 and 4.5g prepolymer resin Uvecoat 9001,7g light trigger Darocure2959,3g auxiliary agent (stopper p methoxy phenol wherein: 0.5 gram, flow agent BYK373:1.5 gram, defoamer: BYK088:1.0 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Comparative example 5
With 76.8g prepolymer resin Uvecoat 3000 and 19.2g prepolymer resin Uvecoat 9001,3g light trigger Irgacure651/Darocure2959 (1: 1), 1g auxiliary agent (stopper p methoxy phenol wherein: 0.1 gram, flow agent BYK373:0.4 gram, defoamer: BYK088:0.5 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified second, measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Comparative example 6
With 82.7g prepolymer resin Uvecoat 3001 and 11.3g prepolymer resin Uvecoat 9001,4g light trigger Irgacure184/Darocure2959 (3: 1), 2g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:1.0 gram, defoamer: BYK088:0.8 gram), after melting mixing is even, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays at 120 ℃ of following abundant fusion levellings, use the 1kw high voltage mercury lamp again, with 80W.cm -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Embodiment 1
With 84g prepolymer resin Uvecoat 3001 and 6g prepolymer resin Uvecoat 9001,2g light trigger Irgacure184/Darocure2959 (1: 3), 3g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:2.0 gram, defoamer: BYK088:0.8 gram), nanometer CaCO 35g, melting mixing evenly after, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays,, use the 1kw high voltage mercury lamp again, with 80W.cm at 120 ℃ of abundant fusion levellings down -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Embodiment 2
With 79g prepolymer resin Uvecoat 3001 and 2g prepolymer resin Uvecoat 9001,5g light trigger Irgacure184/Darocure2959 (1: 3), 4g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:3.0 gram, defoamer: BYK088:0.8 gram), nanometer CaCO 310g, melting mixing evenly after, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays,, use the 1kw high voltage mercury lamp again, with 80W.cm at 120 ℃ of abundant fusion levellings down -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Embodiment 3
With 70g prepolymer resin Uvecoat 3000 and 12g prepolymer resin Uvecoat 9001,5g light trigger Irgacure651/Darocure2959 (1: 3), 3g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:2.0 gram, defoamer: BYK088:0.8 gram), SiO 2The nanometer CaCO of parcel 310g, melting mixing evenly after, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays,, use the 1kw high voltage mercury lamp again, with 80W.cm at 120 ℃ of abundant fusion levellings down -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Embodiment 4
With 77.5g prepolymer resin Uvecoat 3000 and 8.5g prepolymer resin Uvecoat 9001,4g light trigger Irgacure651/Darocure2959 (1: 3), 4g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:3.0 gram, defoamer: BYK088:0.8 gram), SiO 2The nanometer CaCO of parcel 36g, melting mixing evenly after, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays,, use the 1kw high voltage mercury lamp again, with 80W.cm at 120 ℃ of abundant fusion levellings down -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Embodiment 5
With 80g prepolymer resin Uvecoat 3000 and 6g prepolymer resin Uvecoat 9001,3g light trigger Darocure2959,3g auxiliary agent (stopper p methoxy phenol wherein: 0.2 gram, flow agent BYK373:2.0 gram, defoamer: BYK088:0.8 gram), SiO 2The nanometer CaCO of parcel 38g, melting mixing evenly after, cooling is ground into fine powder (180 order), be sprayed at base material after, under infrared rays,, use the 1kw high voltage mercury lamp again, with 80W.cm at 120 ℃ of abundant fusion levellings down -1The UV-irradiation of illumination is solidified, and measures film performance.(hardness is pressed GB6739-86 method test, sticking power and press that the GB9286-88 method is tested, shock resistance is pressed the GB1732-88 method and tested.)
Test-results
Example Curing speed (s) Pencil hardness Sticking power Resistance to impact shock
Comparative example 1 20 ????2H ????99/100 ????42
Comparative example 2 35 ????1H ????96/100 ????35
Comparative example 3 20 ????1H ????100/100 ????37
Comparative example 4 7 ????2H ????100/100 ????45
Comparative example 5 9 ????1H ????100/100 ????35
Comparative example 6 30 ????1H ????100/100 ????40
Embodiment 1 15 ????3H ????100/100 ????46
Embodiment 2 20 ????3H ????100/100 ????48
Embodiment 3 10 ????3H ????100/100 ????50
Embodiment 4 9 ????5H ????100/100 ????50
Embodiment 5 12 ????4H ????100/100 ????49
Condition of cure: 1KW high voltage mercury lamp, illumination 80W/cm
Hardness test: press the test of GB6739-86 method
The sticking power test: cross-hatching is pressed the test of GB9286-88 method
Resistance to impact shock: press the test of GB1732-88 method
Can illustrate by data in the table, the lime carbonate that adds inorganic nano level lime carbonate and silicon-dioxide parcel in photocuring powder coating of the present invention has carried out modification to coating, make that this coating has that melt temperature is low, curing speed is fast, cured paint film sticking power is good, hardness is high and profile pattern reaches the characteristics of no tangerine peel phenomenon well, over-all properties is better than the thermofixation powder coating of use at present, especially can be used for temperature-sensitive material such as medium-density plate etc.

Claims (3)

1. UV photocuring powder coating, it comprises: (1) light trigger, (2) prepolymer resin, (3) auxiliary agent, (4) inorganic nano material, its each component concentration is: light trigger 1~7%; Prepolymer resin 70~90%; Auxiliary agent 1~5%; Inorganic nano material 2~15%.
2. UV photocuring powder coating according to claim 1 is characterized in that described each component concentration is: light trigger 2~5%; Prepolymer resin 80~90%; Auxiliary agent 3~4%; Inorganic nano material 5~10%.
3. UV photocuring powder coating according to claim 1 is characterized in that, described inorganic nano material is the lime carbonate of nanometer grade calcium carbonate or silicon-dioxide parcel.
CNB021489424A 2002-11-14 2002-11-14 New pattern UV light solidifying powdery paints Expired - Fee Related CN100374515C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311697A (en) * 2010-07-05 2012-01-11 湖南松井化学技术有限公司 Ultraviolet light or electron beam radiation curing powder coating
CN102744897A (en) * 2012-07-05 2012-10-24 张家港市民扬塑胶科技有限公司 Production process for nanometer reinforced PET slabs with high transparency and high weatherability
CN102775901A (en) * 2012-07-20 2012-11-14 江苏科技大学 Light-cured plasticized coating composition and preparation method thereof
WO2012159583A1 (en) * 2011-05-25 2012-11-29 Superl Technology Limited Methods of powder coating and items to be powder coated
CN107964336A (en) * 2017-08-16 2018-04-27 广东美的环境电器制造有限公司 UV cures anion powder coating and its preparation method and application and anion release product
CN108384411A (en) * 2018-02-09 2018-08-10 杭州五源科技实业有限公司 A kind of woodwork light curable conductive powdery paints and preparation method thereof
CN108659684A (en) * 2018-04-28 2018-10-16 佛山市莱威化工科技有限公司 A kind of UV radiation curable powder coatings and preparation method thereof and construction technology
CN110158741A (en) * 2019-05-27 2019-08-23 合肥淼通市政工程有限公司 Urban Underground pipeline non-excavation rehabilitation dredging method
CN110283486A (en) * 2019-07-12 2019-09-27 顺德职业技术学院 Novel UV curing powder anti-flaming dope and preparation method thereof
CN111378352A (en) * 2020-04-24 2020-07-07 容七英 Anticorrosive powder coating for steel box girder and preparation method thereof
WO2022048148A1 (en) * 2020-09-07 2022-03-10 佛山宜可居新材料有限公司 Uv-curable powder coating resin having multiphase structure and preparation method therefor

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* Cited by examiner, † Cited by third party
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US5922473A (en) * 1996-12-26 1999-07-13 Morton International, Inc. Dual thermal and ultraviolet curable powder coatings
CN1058038C (en) * 1996-12-31 2000-11-01 中国科学院感光化学研究所 Low contract photo-solidification cladding material, its prepn. method and use
CN1091456C (en) * 2000-06-07 2002-09-25 湖南亚大化工建材有限公司 Ultravoilet cured paint without irritation
CN1208399C (en) * 2001-02-27 2005-06-29 清华大学 Method for covering nano calcium carbonate on heavy mass calcium carbonate surface
CN1263808C (en) * 2001-02-27 2006-07-12 清华大学 Surface nano modifying method for micrometer granule

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311697A (en) * 2010-07-05 2012-01-11 湖南松井化学技术有限公司 Ultraviolet light or electron beam radiation curing powder coating
WO2012159583A1 (en) * 2011-05-25 2012-11-29 Superl Technology Limited Methods of powder coating and items to be powder coated
CN102744897A (en) * 2012-07-05 2012-10-24 张家港市民扬塑胶科技有限公司 Production process for nanometer reinforced PET slabs with high transparency and high weatherability
CN102775901A (en) * 2012-07-20 2012-11-14 江苏科技大学 Light-cured plasticized coating composition and preparation method thereof
CN102775901B (en) * 2012-07-20 2015-08-05 江苏科技大学 A kind of composition and method of making the same of photocuring plasticising coating
CN107964336A (en) * 2017-08-16 2018-04-27 广东美的环境电器制造有限公司 UV cures anion powder coating and its preparation method and application and anion release product
CN108384411A (en) * 2018-02-09 2018-08-10 杭州五源科技实业有限公司 A kind of woodwork light curable conductive powdery paints and preparation method thereof
CN108384411B (en) * 2018-02-09 2020-04-24 杭州五源科技实业有限公司 Woodwork photocuring conductive powder coating and preparation method thereof
CN108659684A (en) * 2018-04-28 2018-10-16 佛山市莱威化工科技有限公司 A kind of UV radiation curable powder coatings and preparation method thereof and construction technology
CN110158741A (en) * 2019-05-27 2019-08-23 合肥淼通市政工程有限公司 Urban Underground pipeline non-excavation rehabilitation dredging method
CN110283486A (en) * 2019-07-12 2019-09-27 顺德职业技术学院 Novel UV curing powder anti-flaming dope and preparation method thereof
CN111378352A (en) * 2020-04-24 2020-07-07 容七英 Anticorrosive powder coating for steel box girder and preparation method thereof
WO2022048148A1 (en) * 2020-09-07 2022-03-10 佛山宜可居新材料有限公司 Uv-curable powder coating resin having multiphase structure and preparation method therefor

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