CN104893429A - Prepolymer method used for preparing modified nano carbon black water-based color paste - Google Patents
Prepolymer method used for preparing modified nano carbon black water-based color paste Download PDFInfo
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Abstract
The invention relates to a prepolymer method used for preparing modified nano carbon black water-based color paste. Carbon black possesses excellent stainability and stability, and is widely applied to the industrial fields such as rubber, paint, and plastic. Particle size of carbon black is small; specific surface area is large; surface function group content is low; particle clustering is easily caused, and is difficult to eliminate; so that further application of carbon black is limited to a great extent. The prepolymer method comprises following steps: (1) a polyurethane prepolymer is synthesized from polyethylene glycol and diisocyanate; (2) a carbon black aqueous dispersion is prepared with a hyperdispersant; (3) the polyurethane prepolymer is subjected to chain extension and dispersion in the carbon black aqueous dispersion so that the surfaces of carbon black particles are coated with polyurethane layers, and the steadily dispersed modified nano carbon black water-based color paste is obtained. The odified nano carbon black water-based color paste can be used for coloring of coating of leather, plastic, and woodenware, and especially can be used for leather coating as a novel black pigment paste; obtained coating layers are high in black brightness, and possesses dry and wet rubbing resistance, wear resistance, excellent flexicity, and high warping strength.
Description
Technical field
The present invention relates to a kind of method that prepolymer method prepares modified Nano aqueous carbon black mill base, particularly a kind of preparation method that can be used for the modified Nano aqueous carbon black mill base of hide finishes toning.
Background technology
Along with growth in the living standard, the demand of people to high-grade leather goods such as removal vehicle seat cover leather, upholstery leathers is also increasing, and these leather goods need to have highly water-fast, wear resistance, wet-rub resistance and the contour physical property of high black luminance usually.
The black pigment cream used in current leather finish, mainly comprise with casein be adhesive components containing casein pigment and with polymer hyper-dispersant dispersion without casein pigment, the requirement of conventional Spraying technique can be met, but be difficult to the high physical property demand meeting some high-grade leather goods.Therefore, prepare a kind of novel black pigment cream with high abrasion, high resistance to wet rubbing, high black luminance, in order to improve leather goods quality and to increase leather goods added value.
Carbon black, as a kind of important industrial raw material, has good tinting strength, light screening properties and chemical stability, nontoxic, is widely used in the industry such as rubber, coating and plastics, as weighting agent, tinting material and strengthening agent etc.Because nano carbon black particle diameter is little, specific surface area is large and surface functional group content is low, very easily reunites, is not easily dispersed in polymeric matrix, limit it and further apply between particle.Therefore, to carbon black carry out modification to improve its dispersiveness be always carbon black research focus (Li Xianhui, Wu Chifei. the sign of nano carbon black and the optimization [J] of preparation condition thereof. nanosecond science and technology, 2006,2 (5): 46-49.).
In recent years, the method for modified carbon black mainly contains Direct dispersion method, oxidation modification method, graft modification method and coating modification method.Wherein, utilize polymkeric substance to carry out coating modification to nano carbon black particle and become one of the preferred method improving carbon black dispersiveness in water-based system (Zhou Yanyang, Zhang Qiuyu, Liu Yali, et al. Encapsulation and dispersion of carbon black by an in situ controlling radical polymerization of AA/BA/St with DPE as a control agent [J]. Colloid And Polymer Science, 2013,291 (10): 2399-2408.).The research of existing coating modification carbon black method mainly based on emulsion polymerization and interfacial polymerization, and about the research also rare report of prepolymer method coating modification carbon black.Emulsion polymerization is under inorganic particulate exists, the avidity between monomer and inorganic particulate is improved by means of tensio-active agent, monomer is assembled at particle surface, polymerization under initiator causes, prepare modified Nano aqueous carbon black mill base (Tiarks Franca, Landfester Katharina, Antonietti Markus. Encapsulation of carbon black by miniemulsion polymerization [J]. Macromolecular Chemistry And Physics, 2001,202 (1): 51-60.; Landfester Katharina. The generation of nanoparticles in miniemulsions [J]. Advanced Materials, 2001,13 (10): 765-768.).The limitation of the method is type and the consumption that strictly must control monomer, initiator and emulsifying agent, to avoid the formation of the not exclusively coated and straight polymer particle of polymkeric substance.And interfacial polymerization utilizes organic polymer to form polymer layer at surface of inorganic particles, prepare modified Nano aqueous carbon black mill base (Wang Jian, Li Zhengjun, Fan Wuhou, Deng. the performance study [J] of modified Nano aqueous carbon black mill base/urethane composite membrane. leather science and engineering, 2012,22 (2): 20-25.).The limitation of the method is that carbon black particle Surface coating is complete not, and the parent/hydrophobicity of coating layer is difficult to regulate.Comparatively speaking, prepolymer method first synthesizes organic prepolymer, and then chain extension and dispersion in inorganic particulate dispersion liquid, and prepolymer is wrapped in particle surface, prepares stable modified Nano aqueous carbon black mill base.The method utilizes the hydrophilic and hydrophobic of prepolymer to control the parent/hydrophobicity of coated rear whole particle, and the controllability of coating layer is stronger, more easily meets specific performance requriements.
Summary of the invention
The object of the present invention is to provide a kind of method adopting prepolymer method to prepare modified Nano aqueous carbon black mill base, the modified Nano aqueous carbon black mill base that it prepares can improve the wear resistance of leather coating, wet-rub resistance and black luminance, and has good suppleness and flexible resistance.
Realizing technical scheme of the present invention is:
The present invention adopts prepolymer method to utilize polyoxyethylene glycol (400 ~ 4000) and vulcabond synthesis of polyurethane prepolymer, chain extension, dispersion in carbon black dispersion liquid, layer of polyurethane is made to be coated on carbon black particle surface, improve carbon black dispersiveness in an aqueous medium, prepare stable modified Nano aqueous carbon black mill base.
Adopt prepolymer method to prepare a method for modified Nano aqueous carbon black mill base, it is characterized in that the method comprises the following steps:
(1) preparation of prepolymer
Polyoxyethylene glycol is placed in the there-necked flask being furnished with agitator, thermometer and condensing works, vacuum hydro-extraction 2 ~ 4 h under 110 ~ 130 ° of C, then be cooled to 45 ~ 55 ° of C, add vulcabond, be warming up to 60 ~ 70 ° of C and react 0.5 ~ 1.0 h, add catalyzer again, reaction 1 ~ 2 h, then adds chainextender, then continues reaction 2 ~ 4 h, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
(2) preparation of carbon black dispersion liquid
Hyper-dispersant is dissolved in the water, then under the stirring velocity of 6000 ~ 18000 r/min, adds carbon black, high speed dispersion 1 ~ 3 h, obtain stable sooty water dispersion liquid.
(3) preparation of modified Nano aqueous carbon black mill base
Sooty water dispersion liquid prepared by above-mentioned steps (2) is mixed with quadrol and deionized water, under 35 ° of C water-baths and rapid stirring, then add the prepolymer prepared by above-mentioned steps (1), carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
The present invention's molecular weight polyethylene glycol used is 400 ~ 4000, and its consumption is 30 ~ 120 g.
The present invention's vulcabond used is the one in aliphatics or aromatic diisocyanate, and its consumption is 10 ~ 40 g.
The present invention's catalyzer used is the one in organic tin catalyzer, and its consumption is 0.05 ~ 1.05 g.
The present invention's chainextender used is dimethylol propionic acid, and its consumption is 1 ~ 5% of polyoxyethylene glycol and vulcabond total amount.
The present invention's hyper-dispersant used is the one in non-ionic polymers hyper-dispersant, and its consumption is 10 ~ 30 g.
The mass ratio of the prepolymer that the present invention is used and carbon black controls between 1:0.5 to 1:5.0.
Compared with convention pigment cream, the invention has the advantages that:
Cost is low, preparation technology is simple, and the nano carbon black aqueous color paste obtained, not containing casein, can meet the requirement of the aspects such as high-grade leather goods high abrasion, high resistance to wet rubbing, particularly wet-rub resistance can and black luminance particularly outstanding.
Embodiment
Embodiment 1:
The preparation of prepolymer
30 ~ 120 g polyoxyethylene glycol (400) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 50 ° of C, add 10 ~ 40 g aromatic series tolylene diisocyanates, be warming up to 60 ° of C and react 0.5 ~ 1 h, add 0.05 ~ 1.05 g dibutyltin dilaurate catalyst again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of sooty water dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 10 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 2:
The preparation of prepolymer
30 ~ 120 g polyoxyethylene glycol (4000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 50 ° of C, add 10 ~ 40 g aromatic series tolylene diisocyanates, be warming up to 60 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 10 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 3:
The preparation of prepolymer
30 ~ 120 g polyoxyethylene glycol (400) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aliphatic diisocyanates, be warming up to 70 ° of C and react 0.5 ~ 1 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add prepared 5g prepolymer, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 4:
The preparation of prepolymer
30 ~ 120 g polyoxyethylene glycol (4000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aliphatic diisocyanates, be warming up to 70 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 5 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 5:
30 ~ 120 g polyoxyethylene glycol (1000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aromatic series tolylene diisocyanates, be warming up to 60 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 10 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 6:
30 ~ 120 g polyoxyethylene glycol (1000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aromatic series tolylene diisocyanates, be warming up to 60 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 20 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 7:
30 ~ 120 g polyoxyethylene glycol (2000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aliphatics tolylene diisocyanates, be warming up to 70 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 10 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
Embodiment 6:
30 ~ 120 g polyoxyethylene glycol (2000) are placed in the there-necked flask being furnished with agitator, thermometer and condensing works, after 120 ° of C vacuum hydro-extraction 2 ~ 4 h, be cooled to 55 ° of C, add 10 ~ 40 g aliphatics tolylene diisocyanates, be warming up to 70 ° of C and react 0.5 ~ 1.0 h, add 0.05 ~ 1.05 g organic tin catalyzer again, reaction 1 ~ 2 h, then add 1 ~ 5% dimethylol propionic acid and carry out chain extension, continue reaction 2 ~ 4 h again, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer.
The preparation of carbon black dispersion liquid
15 g hyper-dispersants are dissolved in 50 g deionized waters, then under the stirring velocity of 6000 r/min, add 10 g carbon blacks, high speed dispersion 1 h, obtain stable sooty water dispersion liquid.
The preparation of modified Nano aqueous carbon black mill base
60 prepared g sooty water dispersion liquids are mixed with 0.2 ~ 1.0 g quadrol and 10 ~ 40 g deionized waters, under 35 ° of C water-baths and rapid stirring, then add 20 prepared g prepolymers, carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
The modified Nano aqueous carbon black mill base excellent property prepared according to preparation method of the present invention, after leather finish, coating is Bearable dry and wet wipe not only, and suppleness and flexible resistance good, black luminance is high, can meet the requirement of the aspects such as high-grade leather goods high abrasion, high resistance to wet rubbing.In addition, preparation method of the present invention also has reference and reference for the development & application of the application such as plastics, woodenware tinting material.
Claims (7)
1. a preparation method for modified Nano aqueous carbon black mill base, is characterized in that the method comprises the following steps:
(1) preparation of prepolymer: polyoxyethylene glycol is placed in the there-necked flask being furnished with agitator, thermometer and condensing works, vacuum hydro-extraction 2 ~ 4 h under 110 ~ 130 ° of C, then be cooled to 45 ~ 55 ° of C, add vulcabond, be warming up to 60 ~ 70 ° of C and react 0.5 ~ 1.0 h, add catalyzer again, reaction 1 ~ 2 h, then adds chainextender, then continues reaction 2 ~ 4 h, until isocyano-content reaches theoretical value (judging by Di-n-Butyl Amine volumetry), obtain prepolymer; (2) preparation of carbon black dispersion liquid: hyper-dispersant is dissolved in the water, then adds carbon black, high speed dispersor stirs 0.5 ~ 3.0 h, obtains stable sooty water dispersion liquid; (3) preparation of modified Nano aqueous carbon black mill base: the sooty water dispersion liquid prepared by above-mentioned steps (2) is mixed with quadrol and deionized water, under 35 ° of C water-baths and rapid stirring, add the prepolymer prepared by above-mentioned steps (1), carry out chain extension, dispersion and coated, maintain 10 ~ 40 min, obtain modified Nano aqueous carbon black mill base.
2. method according to claim 1, it is characterized in that the molecular weight of the polyoxyethylene glycol in described step (1) is 400 ~ 4000, its consumption is 30 ~ 120 g.
3. method according to claim 1, the vulcabond that it is characterized in that in described step (1) is the one in aliphatics or aromatic diisocyanate, and its consumption is 10 ~ 40 g.
4. method according to claim 1, the catalyzer that it is characterized in that in described step (1) is the one in organic tin catalyzer, and its consumption is 0.05 ~ 1.05 g.
5. method according to claim 1, it is characterized in that the chainextender in described step (1) is dimethylol propionic acid, its consumption is 1 ~ 5% of polyoxyethylene glycol and vulcabond total amount.
6. method according to claim 1, it is characterized in that in described step (2), hyper-dispersant is the one in non-ionic polymers hyper-dispersant, its consumption is 10 ~ 30 g.
7. method according to claim 1, is characterized in that the mass ratio of prepolymer in described step (3) and carbon black controls between 1:0.5 to 1:5.0.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107603342A (en) * | 2017-06-10 | 2018-01-19 | 合肥聚合辐化技术有限公司 | A kind of ink-jet printed white coating ink of fabric |
| CN108102335A (en) * | 2017-11-27 | 2018-06-01 | 广德粤华塑业制品有限公司 | A kind of PU environmental protection color |
| JP2018154829A (en) * | 2017-03-17 | 2018-10-04 | 三洋化成工業株式会社 | Polyurethane resin-coated pigment water dispersion |
| CN109627897A (en) * | 2018-12-14 | 2019-04-16 | 合众（佛山）化工有限公司 | A kind of modified premix emulsion of graphene and its black conductive coating |
| CN111423748A (en) * | 2019-12-24 | 2020-07-17 | 江苏海阳锦纶新材料有限公司 | Production process of high-temperature-resistant dispersing agent for dispersing carbon black color paste to nanoscale |
| CN111499824A (en) * | 2020-04-17 | 2020-08-07 | 珠海中墨科技有限公司 | Structured dispersing agent for UV ink-jet and color paste and preparation method thereof |
| CN113088133A (en) * | 2021-02-07 | 2021-07-09 | 纳琳威纳米科技南通有限公司 | High-blackness UV nano high-speed code spraying color paste and preparation method thereof |
| TWI739455B (en) * | 2020-06-02 | 2021-09-11 | 普羅森科技股份有限公司 | Low-shrinkage photocurable material and manufacturing method thereof |
| CN114574006A (en) * | 2022-01-22 | 2022-06-03 | 德欣精细化工(深圳)有限公司 | Preparation method of superfine special carbon black |
| CN115558091A (en) * | 2022-09-20 | 2023-01-03 | 中国纺织科学研究院有限公司 | Black hydrophilic polyester and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018154829A (en) * | 2017-03-17 | 2018-10-04 | 三洋化成工業株式会社 | Polyurethane resin-coated pigment water dispersion |
| CN107603342A (en) * | 2017-06-10 | 2018-01-19 | 合肥聚合辐化技术有限公司 | A kind of ink-jet printed white coating ink of fabric |
| CN108102335A (en) * | 2017-11-27 | 2018-06-01 | 广德粤华塑业制品有限公司 | A kind of PU environmental protection color |
| CN109627897A (en) * | 2018-12-14 | 2019-04-16 | 合众（佛山）化工有限公司 | A kind of modified premix emulsion of graphene and its black conductive coating |
| CN111423748A (en) * | 2019-12-24 | 2020-07-17 | 江苏海阳锦纶新材料有限公司 | Production process of high-temperature-resistant dispersing agent for dispersing carbon black color paste to nanoscale |
| CN111499824A (en) * | 2020-04-17 | 2020-08-07 | 珠海中墨科技有限公司 | Structured dispersing agent for UV ink-jet and color paste and preparation method thereof |
| TWI739455B (en) * | 2020-06-02 | 2021-09-11 | 普羅森科技股份有限公司 | Low-shrinkage photocurable material and manufacturing method thereof |
| CN113088133A (en) * | 2021-02-07 | 2021-07-09 | 纳琳威纳米科技南通有限公司 | High-blackness UV nano high-speed code spraying color paste and preparation method thereof |
| CN114574006A (en) * | 2022-01-22 | 2022-06-03 | 德欣精细化工(深圳)有限公司 | Preparation method of superfine special carbon black |
| CN115558091A (en) * | 2022-09-20 | 2023-01-03 | 中国纺织科学研究院有限公司 | Black hydrophilic polyester and preparation method thereof |
| CN115558091B (en) * | 2022-09-20 | 2024-02-06 | 中国纺织科学研究院有限公司 | Black hydrophilic polyester and preparation method thereof |
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Application publication date: 20150909 |