CN102702933B - Ultraviolet curing woodware colored paint coating and preparation method thereof - Google Patents
Ultraviolet curing woodware colored paint coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ultraviolet curing woodware colored paint coating and a preparation method thereof. The coating contains the following ingredients in part by weight: 40 to 60 parts of ultraviolet curing resin, 25 to 40 parts of reaction type monomer and 3 to 6 parts of photoinitiator. The ultraviolet curing woodware colored paint has the advantages that the problems of poor covering power, adhesive power and the like in the conventional furniture coating photocuring colored paint technology are solved by selecting a technology of a formula for synthesizing different active monomers and the photoinitiator. After the UV colored paint is used, the adhesive power of construction can reach the standard of primary adhesive power of GB\T9286-1979, and the functional coating represents an advanced technology in the industry.
Description
Technical field
The present invention relates to ultraviolet-curing paint, be specifically related to a kind of ultraviolet cured woodware color paint coating and preparation method thereof.
Background technology
Repainting hours is short, production efficiency advantages of higher because having for ultraviolet-curing paint, increasingly extensive in the application of field of furniture in recent years.And along with the official applying, more and more higher to the requirement of ultraviolet-curing paint, as the ultraviolet-curing paint from transparent makes the transition as real look ultraviolet-curing paint.By selecting the technology of different reactive monomers and light trigger synthesizing formula, overcome the problem such as opacifying power, sticking power that existing furniture application light-curing colored paint technology exists.Can be used for the techniques such as roller coat, showering, spraying.Using after the construction of UV colored paint sticking power can get at GB T9286-1979 one-level sticking power standard functionality coating is also leading technology in industry the inside.
But UV cure wood coatings will use UV-light that it is solidified in coating process, the principle of solidification is that UV-light is excited the light trigger in coating, produce a large amount of free radical or ion, two keys in these radicals or ion and performed polymer or unsaturated monomer play crosslinking reaction, form monomer gene, thereby initiated polymerization, crosslinked and graft reaction are converted into coating solid-state within the several seconds by liquid state.If but opacifying power is very good or the too thick ultraviolet cured woodware color paint coating of glue spread absorbs less than UV-light, cannot complete film-forming, film adhesive is poor.
In order to overcome the problem of poor adhesive force of existing coating, ultraviolet-curing paint is done in many ways and has been improved:
Chinese patent application CN03114651.1 (publication number is CN1537907A) relates to a kind of ultraviolet light polymerization white traffic marking coating, it is characterized in that: it comprises photosensitive prepolymer, photosensitive dilution reactive monomer, light trigger, light sensitizer, white pigment, filler and flow agent, anti-settling agent composition; Wherein photosensitive prepolymer is containing 5 parts-120 parts; 5 parts-100 parts of photosensitive dilution reactive monomers; 1 part-5 parts of light triggers; 0 part-5 parts of light sensitizers; 5 parts-20 parts of white pigments; 5 parts-70 parts of fillers; 0 part-1 part of flow agent; 0 part-1 part of anti-settling agent.This ultraviolet light fast solidification white traffic marking coating, " moment " fast setting has high gloss, high adhesive force, high-wearing feature and enhanced water resistance simultaneously at normal temperatures, and its cost is low, pollution-free, is green environmental friendly coatings.But this patent is mainly in the research and development for UV white traffic marking coating system
Chinese patent application 201010591897.1 (publication number is CN102070982A) discloses a kind of ultraviolet light polymerization based white primer and utilizes the construction technology of this based white primer in medium density fiberboard, and the composition of raw materials of this ultraviolet light polymerization based white primer forms 20-35 part urethane acrylate, 20-30 part modified poly ester acrylate, 15-20 part monomer, 10-20 part weighting agent, 3-5 part light trigger, 0.5-1 part anti-settling agent and 0.2-0.3 part defoamer by each component of following parts by weight.But this patent is mainly in the research and development for UV White system.
In Chinese patent application 201110117999.4 (publication number is CN102212311A), a kind of colored UV photo-cured coating and preparation method thereof is disclosed, this coating lacquer is grouped into by the one-tenth of following weight percent: polyurethane acroleic acid performed polymer 25-55%, acrylic ester monomer 10-60%, solvent 5-50%, light trigger 1-10%, pigment 1-15%, dispersion agent 0.5-10%, auxiliary agent 0.1-2%.This coating has overcome the problems such as volatility, construction that UV photo-cured coating exists be difficult, has low VOC, and good decorating effect, curing speed are fast, easily construction, is applicable to streamline production feature.But its sticking power still do not reach GB T9286-1998 one-level sticking power standard.
And the present invention is preparing colored paint, after the construction of use colored paint, sticking power can get at GB T9286-1998 one-level sticking power standard functionality coating.Constructing operation can adopt the construction technologies such as roller coat, showering, spraying to complete customer requirement simultaneously.
Summary of the invention
The object of this invention is to provide a kind of ultraviolet cured woodware color paint coating and production method thereof, by selecting the technology of different reactive monomers and light trigger synthesizing formula, overcome the problem such as opacifying power, sticking power that existing furniture application light-curing colored paint technology exists.
A kind of ultraviolet cured woodware color paint coating provided by the invention, the composition that contains following weight part: UV-cured resin 40-60 part, response type monomer 25-40 part, light trigger 3-6 part.
Preferably, described ultraviolet cured woodware color paint coating, the composition that contains following weight part: UV-cured resin 45-55 part, response type monomer 30-40 part, light trigger 4-6 part.
Further preferably, described ultraviolet cured woodware color paint coating, the composition that contains following weight part: 53.8 parts of UV-cured resin, 32 parts of response type monomers, 5 parts of light triggers.
Wherein:
Described UV-cured resin is that solid content is one or more in the bisphenol A epoxy acrylate of 95-100%, aromatic polyether type polyurethane diacrylate that solid content is 95-100% or the solid content two functionality polyester acrylates that are 95-100%;
Described response type monomer is the mixture of ethoxylation 1.6-hexanediyl ester, neopentylglycol diacrylate, ethoxylated trimethylolpropane triacrylate and 2-Hydroxy ethyl acrylate, the weight ratio of above-mentioned four kinds of compositions is 5-12: 5-15: 2-10: 5-12, weight ratio is preferably 6-10: 8-12: 4-8: 6-10, weight ratio more preferably 8: 10: 6: 8;
Described light trigger is 2,4,6, the mixture of-trimethylbenzoyl-diphenyl phosphate oxidation, 1-hydroxyl-cyclohexyl-phenyl ketone and isopropyl thioxanthone, and weight ratio is 1-5: 1-5: 0.5-2, preferably according to 2: 2: 1 compositions of weight ratio.
Ultraviolet cured woodware color paint coating provided by the invention, also contains the composition of following weight part: anti-settling agent 0.2-0.8 part, wetting dispersing agent are that 0.1-0.8 part, defoamer are that 0.1-0.5 part, base material flow agent are 0.1-0.2 part, stopper 0.05-0.3 part, pigment 4-12 part.
Preferably, ultraviolet cured woodware color paint coating provided by the invention, also contains the composition of following weight part: anti-settling agent 0.3-0.6 part, wetting dispersing agent 0.3-0.5 part, defoamer 0.1-0.3 part, base material flow agent 0.1-0.2 part, stopper 0.1-0.3 part, pigment 6-10 part.
Further preferably, ultraviolet cured woodware color paint coating provided by the invention, also contains the composition of following weight part: 0.5 part of anti-settling agent, 0.5 part of wetting dispersing agent, 0.2 part of defoamer, 0.1 part of base material flow agent, 0.2 part of stopper, 8 parts of pigment.
Described anti-settling agent is aerosil;
Described defoamer is polysiloxane-polyether copolymer;
Described base material flow agent is polyether-modified polydimethylsiloxane;
Described stopper is MEHQ.
Described wetting dispersing agent is solvent based coating high molecular wetting dispersing agent;
Described pigment is the pigment dyestuff that contains azo-group (N=N-) in chemical structure.
The present invention also provides the preparation method of above-mentioned coating, and the method comprises the steps:
1) take respectively each composition according to proportioning, by UV-cured resin and response type monomer high speed dispersion 10-20 minute, then under agitation add anti-settling agent, stopper, high speed dispersion 10-15 minute, obtains mixture 1;
2) will in mixture 1, add light trigger, defoamer, high speed dispersion 5-10 minute, then adds wetting dispersing agent, base material flow agent, high speed dispersion 10-15 minute; Add again pigment high speed dispersion 20 minutes; Obtain.
Preferably, preparation method provided by the invention comprises the following steps:
1) take respectively each composition according to proportioning, UV-cured resin and response type monomer are disperseed 20 minutes according to 1500 revs/min, then under agitation add anti-settling agent, stopper, 1500 revs/min are disperseed 10-15 minute, obtain mixture 1;
2) in mixture 1, add light trigger, defoamer, 1200 revs/min are disperseed 5-10 minute; Then add wetting dispersing agent, base material flow agent, 1200 revs/min are disperseed 10-15 minute, then add 1500 revs/min of lower high speed dispersion of pigment 20 minutes; Adjust viscosity to 60-100KU/25 DEG C, obtain product.
The using method of ultraviolet cured woodware color paint coating provided by the invention is roller coat, showering, spraying.
Ultraviolet cured woodware color paint coating provided by the invention has the following advantages:
1, ultraviolet cured colored paint paint spraying technique is different from the color paint coating of conventional P U, PE, NC: once single painting opacifying power can be not very good.This be mainly due to photo-cured coating need to absorb UV-light after light trigger be excited, produce a large amount of free radical groups, two keys in these radicals or ion and performed polymer or unsaturated monomer play crosslinking reaction, form monomer gene, thereby initiated polymerization, crosslinked and graft reaction are converted into coating solid-state within the several seconds by liquid state.
Development research by UV colored paint, has drawn following result: response type monomer reasonably combined, disperses and sticking power, the opacifying power result of solidification process have vital role for pigment wetting
2, coating provided by the invention has that solid content is high, sticking power (reaching 1 grade, country), opacifying power is good; Environmental protection, almost tasteless; Ultraviolet light polymerization, the not equal feature of short construction period, construction technology.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
In ultraviolet cured woodware color paint coating provided by the invention, described UV-cured resin is one or more in bisphenol A epoxy acrylate, aromatic polyether type polyurethane diacrylate or two functionality polyester acrylates, can adopt Guangdong Zhong Shan Chiba chemical industry 401 products (two functionality polyester acrylates, 95% solid content) or the JD6080 (bisphenol A epoxy acrylate of Zhan Chen coating group company, 100% solid content), the product such as JD6090 (aromatic polyether type polyurethane diacrylate, 100% solid content);
Described light trigger is 2,4,6, the mixture of-trimethylbenzoyl-diphenyl phosphate oxidation, 1-hydroxyl-cyclohexyl-phenyl ketone and isopropyl thioxanthone.As Beijing, Changzhou English power TPO (2,4,6 ,-trimethylbenzoyl-diphenyl phosphate oxidation), 184 (1-hydroxyl-cyclohexyl-phenyl ketones), the light trigger ITX of the companies such as Changsha Sunyu chemical industry (sec.-propyl sulphur mix anthrone);
Described response type monomer is the mixture of ethoxylation 1.6-hexanediyl ester, neopentylglycol diacrylate, ethoxylated trimethylolpropane triacrylate and 2-Hydroxy ethyl acrylate, as the NPGDA of Nantong Li Tian Chemical Co., Ltd. (neopentylglycol diacrylate), EO-TMPTA (ethoxylated trimethylolpropane triacrylate) and the HEA of Changxing Chemical Co., Ltd. (2-Hydroxy ethyl acrylate), EO-HDDA (ethoxylation 1.6-hexanediyl ester).
Described anti-settling agent is aerosil, selects Degussa A-200;
The preferred polysiloxane-polyether copolymer of described defoamer, the product that the trade mark that can adopt Bi Ke company is BYK-8800;
Described base material flow agent preferred, polyethers modified dimethyl polysiloxane, the product that the trade mark that can adopt Bi Ke company is BYK-333;
Described stopper is preferably MEHQ, can adopt the product of Rui Kai Chemical Co., Ltd.;
Described wetting dispersing agent is solvent based coating high molecular wetting dispersing agent, the product that the trade mark that can adopt Bi Ke company is BYK-164;
Described pigment is the pigment dyestuff that contains azo-group (N=N-) in chemical structure, for Degussa company production code member is P-01X series product.
Embodiment 1: ultraviolet cured woodware color paint coating
1, starting material composition:
2, preparation method
1) take respectively each composition according to proportioning, by JD6080 resin and monomer EO-HDDA, monomer NPGDA, monomer EO-TMPTA, monomer HEA, 1500 revs/min are disperseed 20 minutes, then under agitation add anti-settling agent A-200, stopper, 1500 revs/min are disperseed 10 minutes, obtain mixture 1;
2) will in mixture 1, add light trigger 184, TPO, ITX and defoamer BYK-8800,1200 revs/min are disperseed 5-10 minute; Then add wetting dispersing agent BYK-164, base material flow agent BYK-333,1200 revs/min are disperseed 10-15 minute, then add 1500 revs/min of lower high speed dispersion of pigment P-01X 20 minutes, obtain product.
3, coating process: colored paint is covered with paint, lacquer, colour wash, etc. on base material (construction technology: wood substrates → UV clear bottom → absolutely dry sanding → UV colored paint).At 320mj/cm
2under the light intensity of (appointed condition: 2 mercury lamps of 1 gal lamp), be that 24m/min is cured film forming by conveyer line speed, then the paint after film forming tested.Glue spread is at (15 ± 5) g/m
22 times, last time absolutely dry curing sand milling of middle half-dried curing roller coat.
4, detected result is as follows:
Result shows: embodiment provided by the invention, by selecting different reactive monomers and the technology of light trigger synthesizing formula, has overcome the problem such as opacifying power, sticking power that existing furniture application light-curing colored paint technology exists.Sticking power reaches 1 grade of sticking power standard according to standard GB/T/T9286-1979.
Embodiment 2: ultraviolet cured woodware color paint coating
1, starting material composition:
2, preparation method
1) take respectively each composition according to proportioning, 1500 revs/min of 401 resins and response type monomer EO-HDDA, NPGDA, EO-TMPTA, HEA are disperseed 20 minutes, then under agitation add anti-settling agent A-200, stopper, according to 1500 revs/min of dispersions 15 minutes, obtain mixture 1;
2) will in mixture 1, add light trigger 184, TPO, ITX, defoamer BYK-8800,1200 revs/min are disperseed 5-10 minute; Then add wetting dispersing agent BYK-164, base material flow agent BYK-333,1200 revs/min are disperseed 10-15 minute, then add 1500 revs/min of lower high speed dispersion of pigment P-01X 20 minutes, obtain product.
3, using method:
Colored paint is covered with paint, lacquer, colour wash, etc. on base material (construction technology: wood substrates → UV clear bottom → absolutely dry sanding → UV colored paint).At 320mj/cm
2under the light intensity of (appointed condition: 2 mercury lamps of 1 gal lamp), be that 24m/min is cured film forming by conveyer line speed, then the paint after film forming tested.Glue spread is at 15 ± 5g/m
22 times, last time absolutely dry curing sand milling of middle half-dried curing roller coat.
3, detected result is as follows:
Result shows: embodiment provided by the invention, by selecting different reactive monomers and the technology of light trigger synthesizing formula, has overcome the problem such as opacifying power, sticking power that existing furniture application light-curing colored paint technology exists.Sticking power reaches 1 grade of sticking power standard according to standard GB/T/T9286-1979.
Embodiment 3: ultraviolet cured woodware color paint coating
1, starting material composition:
2, preparation method
1) take respectively each composition according to proportioning, 1500 revs/min of JD6090 resin and monomer EO-HDDA, NPGDA, EO-TMPTA, HEA are disperseed 20 minutes, then under agitation add anti-settling agent A-200, stopper, according to 1500 revs/min of dispersion 10-15 minute, obtain mixture 1;
2) will in mixture 1, add light trigger 184, TPO, ITX, defoamer BYK-8800,1200 revs/min are disperseed 5-10 minute; Then add wetting dispersing agent BYK-164, base material flow agent BYK-333,1200 revs/min are disperseed 10-15 minute, then add 1500 revs/min of lower high speed dispersion of pigment P-01X 20 minutes, obtain product.
3, using method: colored paint is covered with paint, lacquer, colour wash, etc. on base material (construction technology: wood substrates → UV clear bottom → absolutely dry sanding → UV colored paint).At 320mj/cm
2under the light intensity of (2 mercury lamps of 1 gal lamp), be that 24m/min is cured film forming by conveyer line speed, then the paint after film forming tested.Glue spread is at 15 ± 5g/m
22 times, last time absolutely dry curing sand milling of middle half-dried curing roller coat.
4, detected result is as follows:
Result shows: embodiment provided by the invention, by selecting different reactive monomers and the technology of light trigger synthesizing formula, has overcome the problem such as opacifying power, sticking power that existing furniture application light-curing colored paint technology exists.Sticking power reaches 1 grade of sticking power standard according to standard GB/T/T9286-1979.
Comparative example 1:
1, starting material composition:
2, preparation method
1) take respectively each composition according to proportioning, by 401 resins and monomer EO-HDDA, monomer EO-TMPTA, monomer HEA, 1500 revs/min are disperseed 20 minutes, then under agitation add anti-settling agent A-200, stopper, 1500 revs/min are disperseed 10 minutes, obtain mixture 1;
2) will in mixture 1, add light trigger 184, TPO, ITX and defoamer BYK-8800,1200 revs/min are disperseed 5-10 minute; Then add wetting dispersing agent BYK-164, base material flow agent BYK-333,1200 revs/min are disperseed 10-15 minute, then add 1500 revs/min of lower high speed dispersion of pigment P-01X 20 minutes, obtain product.
3, colored paint is covered with paint, lacquer, colour wash, etc. on base material (construction technology: density board/composition board/lagging plate/sticky paperboard → UV clear bottom → absolutely dry sanding → UV colored paint).At 320mj/cm
2under the light intensity of (2 mercury lamps of 1 gal lamp), be that 24m/min is cured film forming by conveyer line speed, then the paint after film forming tested.Glue spread is at 15 ± 5g/m
22 times, last time absolutely dry curing sand milling of middle half-dried curing roller coat.
4, detected result is as follows:
Result shows: embodiment provided by the invention is by selecting the technology of different two kinds of reactive monomers and light trigger synthesizing formula, is coated with to load onto to use light-curing colored paint coating technology to have the problem such as opacifying power, sticking power at existing furniture.Sticking power does not reach 1 grade of sticking power standard according to standard GB/T/T9286-1979.
Comparative example 2: the coating of Chinese patent application 201110117999.4 contrasts
As Chinese patent application 201110117999.4 discloses " a kind of colored UV photo-cured coating ", overcome the problem such as volatility, construction difficulty that existing colored UV photo-cured coating exists, have low VOC, good decorating effect, curing speed are fast, easily construction, are applicable to streamline production feature.But the coating that this patent provides, aspect sticking power, is not particularly still reaching 1 grade of sticking power standard of coating GB T9286-1998 standard aspect the sticking power of furniture wood lacquer.
In fact verified the performance that monomer and pigment wetting disperse, can find out that four kinds of response type monomers provided by the invention share, and make sticking power, the opacifying power better effects if of ultraviolet cured woodware color paint coating.
Although, above use general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some amendments or improvement to it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (7)
1. a ultraviolet cured woodware color paint coating, is characterized in that, this coating is grouped into by the one-tenth of following weight part: UV-cured resin 40-60 part, response type monomer 25-40 part, light trigger 3-6 part, anti-settling agent 0.2-0.8 part, wetting dispersing agent is 0.1-0.8 part, defoamer is 0.1-0.5 part, base material flow agent is 0.1-0.2 part, stopper 0.05-0.3 part, pigment 4-12 part, described UV-cured resin is that solid content is the bisphenol A epoxy acrylate of 95-100%, solid content is one or more in the aromatic polyether type polyurethane diacrylate of 95-100% or two functionality polyester acrylates that solid content is 95-100%, and described response type monomer is ethoxylation 1.6-hexanediyl ester, neopentylglycol diacrylate, the mixture of ethoxylated trimethylolpropane triacrylate and 2-Hydroxy ethyl acrylate, the weight ratio of above-mentioned four kinds of compositions is 5-12:5-15:2-10:5-12, described light trigger is 2,4,6 ,-trimethylbenzoyl-diphenyl phosphate oxidation, the mixture of 1-hydroxyl-cyclohexyl-phenyl ketone and isopropyl thioxanthone, the weight ratio of above-mentioned three kinds of compositions is 1-5:1-5:0.5-2.
2. coating according to claim 1, it is characterized in that, this coating is grouped into by the one-tenth of following weight part: UV-cured resin 45-55 part, response type monomer 30-40 part, light trigger 4-6 part, anti-settling agent 0.3-0.6 part, wetting dispersing agent 0.3-0.5 part, defoamer 0.1-0.3 part, base material flow agent 0.1-0.2 part, stopper 0.1-0.3 part, pigment 6-10 part.
3. coating according to claim 1, it is characterized in that the composition that this coating contains following weight part: 53.8 parts of UV-cured resin, 32 parts of response type monomers, 5 parts of light triggers, 0.5 part of anti-settling agent, 0.5 part of wetting dispersing agent, 0.2 part of defoamer, 0.1 part of base material flow agent, 0.2 part of stopper, 8 parts of pigment.
4. according to the coating described in claim 1-3 any one, described response type monomer is the mixture of ethoxylation 1.6-hexanediyl ester, neopentylglycol diacrylate, ethoxylated trimethylolpropane triacrylate and 2-Hydroxy ethyl acrylate, and the weight ratio of above-mentioned four kinds of compositions is 6-10:8-12:4-8:6-10.
5. coating according to claim 4, it is characterized in that, described response type monomer is the mixture of ethoxylation 1.6-hexanediyl ester, neopentylglycol diacrylate, ethoxylated trimethylolpropane triacrylate and 2-Hydroxy ethyl acrylate, and the weight ratio of above-mentioned four kinds of compositions is 8:10:6:8.
6. according to the coating described in claim 1-3 any one, it is characterized in that, described light trigger is 2; 4; 6, the mixture of-trimethylbenzoyl-diphenyl phosphate oxidation, 1-hydroxyl-cyclohexyl-phenyl ketone and isopropyl thioxanthone, the weight ratio of above-mentioned three kinds of compositions is 2:2:1.
7. a method of preparing the coating described in claim 1-6 any one, is characterized in that, the method comprises the following steps:
1) take respectively each composition according to proportioning, UV-cured resin and response type monomer are disperseed to 10-20 minute, then under agitation add anti-settling agent, stopper, disperse 10-15 minute, obtain mixture 1;
2) in mixture 1, add light trigger, defoamer, disperse 5-10 minute; Then add wetting dispersing agent, base material flow agent, disperse 10-15 minute, then add colo(u)rant dispersion 20 minutes; Adjust viscosity to 60-100KU/25 DEG C, obtain product.
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| CN113755094A (en) * | 2019-03-12 | 2021-12-07 | 浙江纳美新材料股份有限公司 | Special UV color paste for woodware |
| CN110054972A (en) * | 2019-05-10 | 2019-07-26 | 福州展辰新材料有限公司 | A kind of roller coating colored UV curable solid coatings |
| CN111154382A (en) * | 2019-12-31 | 2020-05-15 | 广东立邦长润发科技材料有限公司 | Ultraviolet-curing woodware coating using sanding powder |
| CN112778881A (en) * | 2021-01-06 | 2021-05-11 | 阜阳师范大学 | Epoxy acrylate ultraviolet curing material and preparation method thereof |
| CN115820016A (en) * | 2022-12-12 | 2023-03-21 | 徐猛 | Water-based UV gray wood board paint and preparation method thereof |
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| CN102702933A (en) | 2012-10-03 |
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Address after: 101105 Beijing Tongzhou District Yongle Economic Development Zone Patentee after: Beijing Zhan Chen novel material company limited Patentee after: CHINA ZHANCHEN PAINTS GROUP LTD. Patentee after: Shanghai Zhanchen Paint Co., Ltd. Patentee after: Chengdu Zhan Chen coating company limited Patentee after: Qingdao Zhan Chen novel material company limited Address before: 101105 Beijing Tongzhou District Yongle Economic Development Zone Patentee before: Beijing Zhanchen Chemical Industry Co., Ltd. Patentee before: Zhanchen Coatings Group Co., Ltd. Patentee before: Shanghai Fuchen Chemical Co., Ltd. Patentee before: Chengdu Zhanchen Chemical Co., Ltd. Patentee before: Qingdao Fuchen Chemical Co., Ltd. |
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