CN102532997B - Boiling-resistant aqueous composite ink and preparation method thereof - Google Patents
Boiling-resistant aqueous composite ink and preparation method thereof Download PDFInfo
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- CN102532997B CN102532997B CN201110405287.2A CN201110405287A CN102532997B CN 102532997 B CN102532997 B CN 102532997B CN 201110405287 A CN201110405287 A CN 201110405287A CN 102532997 B CN102532997 B CN 102532997B
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Abstract
The invention discloses boiling-resistant aqueous composite ink and a preparation method thereof. The boiling-resistant aqueous composite ink mainly comprises raw materials including aqueous polyurethane resin, a pigment and water, and a surface wetting agent, a wetting dispersing agent and a defoaming agent are additionally added. The preparation method of the boiling-resistant aqueous composite ink comprises the following steps of: firstly, adding partial aqueous polyurethane resin into a stirring reaction kettle; secondly, slowly adding the surface wetting agent, the wetting dispersing agent and partial defoaming agent, and adding the pigment after stirring and dispersing; thirdly, stirring and dispersing at high speed, and grinding after dispersing; fourthly, adding the residual aqueous polyurethane resin and defoaming agent and stirring and dispersing, and adding the water until the required viscosity is obtained through regulation; and at last, stirring, dispersing, filtering and packaging. The boiling-resistant aqueous composite ink, provided by the invention, is prepared by taking the high-performance aqueous polyurethane resin as a connecting material, and has the advantages of good pigment dispersibility, wide use range, lower film forming temperature, better mechanical property of formed film, more uniform particle size distribution and the like, and can be used for soft retort packages.
Description
Technical field
The present invention relates to a kind of food product pack printed matter compound oil ink, particularly relate to a kind of aqueous composite ink of anti-boiling the and preparation method thereof.
Background technology
China's printing ink manufacturing started to produce from the early 1980s take since the benzene dissolubility compound oil ink that chlorinated polypropylene is the main body binder, twenty or thirty develops relatively rapid between year, and the technique of the manufacture production of printing ink and printing use is all ripe.But, trend analysis from gravure composite printing ink, benzene dissolubility compound oil ink has the following shortcoming that is difficult to overcome in producing and using: (1) use in a large number aromatic hydrocarbon solvent: because the main body binder urethane resin of printing ink uses toluene in building-up process, and also need to dissolve with toluene; So the matrix resin of existing benzene dissolubility compound oil ink is all to using toluene as true solvent, inevitably to use a large amount of toluene in the production of printing ink and in the middle of using, because resin is poor to the release property of toluene, the toxicity of toluene is very large, in food flexible packing, very easily cause the residual solvent of printing finished product excessive, thereby contaminated food products, on quality and the safety generation impact greatly of food; (2) range of application is narrower: in the plastic compound flexible packaging industry, the outer printing film the most often used is tri-kinds of BOPP, PET and BOPA, and benzene dissolubility compound oil ink is only applicable to the printing of BOPP and compound, all fail to provide excellent sticking power and combined strength bination to PET and BOPA, more can not for freezing, containing grease, boil, the packing of the food such as boiling; (3) poor heat stability: due to the poor heat stability of chlorinated polypropylene, easily discharge chlorine and form hydrogenchloride in the production of printing ink and storage process, make printing ink become strongly-acid, thereby the package stability and the printing that have influence on printing ink are used.
Owing to there being above-mentioned major defect, benzene dissolubility compound oil ink can not adapt to China's requirement of flourishing Flexible-Packaging Industry day by day gradually.In addition, for the consideration to food safety and sanitation and the day by day strict security legislation of adaptation, people need environment-friendly type printing ink, wish to reduce in printing-ink as far as possible and the use procedure of printing ink in the usage quantity of the aromatic hydrocarbon solvents such as toluene, dimethylbenzene, or need to not use the printing-ink of above-mentioned aromatic hydrocarbon solvent.Therefore, develop the development that compound oil ink that performance is more excellent can better adapt to current printing packaging industry.
Along with the aggravation of global environmental pollution and environmental destruction degree, people more and more pay close attention to life, concern for the environment and development, advocate production, use green product, and particularly wholesomeness, the feature of environmental protection for food product pack proposed stricter requirement.As everyone knows, traditional used for packing foods printing ink is the benzophenone dissolubility, although dissolvent residual has been done to strict demand, also has the injury that health is produced and prints the security problems that rear dissolvent residual affects smell and the food of food.
In order effectively to solve the dissolvent residual problem of used for packing foods printing ink, person skilled starts to be studied to water color ink.That the water color ink of anti-the boiling has is nontoxic, have no irritating odor, non-corrosiveness, do not fire, not quick-fried, safety in utilization good, can environment and the person not existed to harm directly with the tap water dilution, belongs to typical Green Product.The water color ink of anti-the boiling is specially adapted to the package printed matters such as food, beverage, medicine, is universally acknowledged environment-friendly type printing material, is also unique printing ink through the approval of U.S. food medicine association in current all printing-inks.Therefore, active development will become an inexorable trend with green gravure ink and water color ink that application meets environmental requirement.Though the molten printing ink of alcohol can effectively solve the residual injury that health is produced of toluene kind solvent and dissolvent residual affects the problems such as food pack-aging quality, and the gravure industry is widely applied at home, but intaglio plate alcohol dissolubility ink used for plastic or residual solvent odor arranged.Aquosity intaglio printing ink has caused many concerns as the substituted systems of solvent type ink, but the printing ink Water-borne modification in the packaging film printing still can not be used widely even to this day.
At present, the aqueous composite ink that has a small amount of printing ink factory to produce is chalk, be the use ACRYLIC EMULSION as binder, modulation forms, it is poor to pigment-dispersing, gloss is low, adjustment of the printing plate weak effect, the half tone rate of transform are low, and printing ink can not be for boiling.
Summary of the invention
The objective of the invention is the weak point existed for existing aqueous composite ink, a kind of aqueous composite ink of anti-boiling the and preparation method thereof is provided.The present invention's aqueous composite ink of anti-the boiling be take waterborne polyurethane resin and is prepared from as binder, product of the present invention has advantages such as pigment-dispersing are good, of many uses, film-forming temperature is lower, the mechanical property of film forming better, size distribution is more even, and can be for the boiling soft packaging.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides a kind of aqueous composite ink of anti-the boiling, with weight percentage, mean, the described aqueous composite ink of anti-the boiling is mainly by raw material waterborne polyurethane resin 45～55%, pigment 10～20% and water 30～40% form, add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for waterborne polyurethane resin, 0.3～1.0% of pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for waterborne polyurethane resin, 1.0～3.0% of pigment and three kinds of raw material gross weights of water, the add-on of defoamer accounts for waterborne polyurethane resin, 0.5～1.5% of pigment and three kinds of raw material gross weights of water.
According to the above-mentioned aqueous composite ink of anti-the boiling, the solid content of described waterborne polyurethane resin is 30～35%, and number-average molecular weight is 22000～25000.
According to the above-mentioned aqueous composite ink of anti-the boiling, described pigment is Rutile type Titanium Dioxide, benzidine yellow G, permanent bordeaux F5R, 15:4 phthalocyanine blue or carbon black.
According to the above-mentioned aqueous composite ink of anti-the boiling, described surface active agent is U.S. aerochemistry surface active agent 104E; Described wetting dispersing agent is German Bi Ke chemistry wetting dispersing agent BYK-191; Described defoamer is the high auxiliary agent TEGO-1488 of German enlightening.
According to the above-mentioned aqueous composite ink of anti-the boiling, described waterborne polyurethane resin is prepared from by the following method:
The raw material of a, described waterborne polyurethane resin consists of PCDL 48～55%, isophorone diisocyanate 15～20%, dibutyl tin laurate 10～15%, dimethylol propionic acid 5～10% and triethylamine 5～10%;
B, raw material according to the described waterborne polyurethane resin of step a forms the various raw materials of preparation, at first the PCDL of preparation and isophorone diisocyanate are joined in stirred autoclave and heated, and slowly stir, when temperature rises to 55～60 ℃, high-speed stirring is 20～25 minutes, add respectively the raw material dibutyl tin laurate of preparation after high-speed stirring in the mode of titration, dimethylol propionic acid and triethylamine, add water after three kinds of raw material titration are complete, the add-on of water accounts for 5～10% of all raw material gross weights, and rapidly the temperature of reaction soln in reactor is down to 20～30 ℃, test the properties of synthetic waterborne polyurethane resin, after reaching requirement, packed for standby use.
According to the above-mentioned aqueous composite ink of anti-the boiling, the stirring velocity of high-speed stirring described in step b in the time of 20～25 minutes is 1200～1500 rev/mins.
A kind of preparation method of the aqueous composite ink of anti-the boiling, described preparation method comprises the following steps:
A, according to the proportioning ratio of the above-mentioned aqueous composite ink of anti-the boiling, take various raw materials;
B, at first 15～20% of raw water based polyurethane total resin weight is joined in stirred autoclave, then the defoamer that slowly adds surface active agent, wetting dispersing agent and 0.5～1.0%, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 600～800 rev/mins 10～15 minutes;
C, then by required pigment, slowly add in stirred autoclave, with the speed dispersed with stirring of 1200～1500 rev/mins 45～50 minutes, after dispersed with stirring, adopt excellent pin formula shredder to be ground, grind 3～4 times, control temperature in process of lapping between 35～50 ℃, check that material reaches required fineness requirement;
80～85% and remaining 0.3～0.5% defoamer that add remaining waterborne polyurethane resin gross weight after d, grinding, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 1200～1500 rev/mins 25～30 minutes, add the water of preparation to adjust to required viscosity, and, with the speed dispersed with stirring of 1200～1500 rev/mins 5～10 minutes, finally adopt 400 order net filtrations packings.
positive beneficial effect of the present invention:
1, the present invention's aqueous composite ink of anti-the boiling is to take homemade waterborne polyurethane resin to be prepared from as binder, the self-control waterborne polyurethane resin that it adopts has the advantages such as solubility is good, wetting scattered to pigment dyestuff, anti-high shear force, and can participate in grinding, adhesiveproperties is good, and boiling resistance can be good.
2, the present invention take homemade high-performance water-based polyurethane resin to prepare the aqueous composite ink of anti-the boiling as binder, thereby make food product pack break away from the pollution of solvent for printing inks fully, improve the scientific and technological content of product, improve thus domestic compound oil ink water-base resin in shortcomings such as colo(u)rant dispersion are difficult, printability is poor, drying is slow, boiling resistance is poor.Therefore, the product aqueous composite ink of anti-boiling of the present invention has advantages such as pigment-dispersing are good, of many uses, film-forming temperature is lower, the mechanical property of film forming better, size distribution is more even, and can be for the boiling soft packaging.
3, the present invention's aqueous composite ink of anti-the boiling is 60 in print speed
~under the printing condition that 150m/min, printing element are unilateral stretching polypropylene (OPP) film (surface treatment reaches 38 dyne) and polyethylene terephthalate (PET) film (surface treatment reaches 48 dyne), its the key technical indexes can reach the specification of quality of same kind of products at abroad, and its specification of quality is as follows:
Colo(u)rant dispersion and stability: under 50 ℃, standing 15 days, without bad phenomenon such as pigment flocculation, precipitation, gels;
Sticking power: on PET and OPP film, the 3M adhesive tape sticks at the ink film surface, firmly throws off, and 95% does not come off;
Compound soundness: detect by GB GB8808 and carry out, reach solvent product of the same type;
Boiling resistance: 121 ℃/15min, printing ink without oozing out, colour-fast, compound without bad phenomenon such as foamings.
four, embodiment:
Further explain the present invention below in conjunction with embodiment, but do not limit content of the present invention.
Embodiment 1:
The present invention's aqueous composite ink of anti-the boiling, mean with weight percentage, and main raw material consists of waterborne polyurethane resin 50%, Rutile type Titanium Dioxide 15% and water 35%; Add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for 0.6% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for 2.0% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, and the add-on of defoamer accounts for 1.0% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water.
The solid content of described waterborne polyurethane resin is 30～35%, and number-average molecular weight is 22000～25000; Described surface active agent is U.S. aerochemistry surface active agent 104E; Described wetting dispersing agent is German Bi Ke chemistry wetting dispersing agent BYK-191; Described defoamer is the high auxiliary agent TEGO-1488 of German enlightening.
Described waterborne polyurethane resin is to adopt following methods to be prepared from:
The raw material of a, described waterborne polyurethane resin consists of PCDL 54%, isophorone diisocyanate 16%, dibutyl tin laurate 12%, dimethylol propionic acid 9% and triethylamine 9%;
B, raw material according to the described waterborne polyurethane resin of step a forms the various raw materials of preparation, at first the PCDL of preparation and isophorone diisocyanate are joined in stirred autoclave and heated, and slowly stir, high-speed stirring 25 minutes (stirring velocity is 1300 rev/mins) when temperature rises to 55 ℃, add respectively the raw material dibutyl tin laurate of preparation after high-speed stirring in the mode of titration, dimethylol propionic acid and triethylamine, add water after three kinds of raw material titration are complete, the add-on of water accounts for 8% of all raw material gross weights, and rapidly the temperature of reaction soln in reactor is down to 20～30 ℃, test the properties of synthetic waterborne polyurethane resin, after reaching requirement, packed for standby use.
The preparation method of the present invention's aqueous composite ink of anti-the boiling, described preparation method's detailed step is as follows:
A, according to the proportioning ratio of the above-mentioned aqueous composite ink of anti-the boiling, take various raw materials;
B, at first 20% of raw water based polyurethane total resin weight is joined in stirred autoclave, then the defoamer that slowly adds surface active agent, wetting dispersing agent and 0.7%, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 600～800 rev/mins 10～15 minutes;
C, then by required pigment, slowly add in stirred autoclave, with the speed dispersed with stirring of 1200～1500 rev/mins 45～50 minutes, after dispersed with stirring, adopt excellent pin formula shredder to be ground, grind 3～4 times, control temperature in process of lapping between 35～50 ℃, check that material reaches required fineness requirement;
80% and remaining 0.3% defoamer that add remaining waterborne polyurethane resin gross weight after d, grinding, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 1200～1500 rev/mins 25～30 minutes, add the water of preparation to adjust to required viscosity, and, with the speed dispersed with stirring of 1200～1500 rev/mins 5～10 minutes, finally adopt 400 order net filtrations packings.
Embodiment 2: substantially the same manner as Example 1, difference is:
The present invention's aqueous composite ink of anti-the boiling, mean with weight percentage, and main raw material consists of waterborne polyurethane resin 45%, permanent bordeaux F5R 18% and water 37%; Add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for 0.3% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for 2.6% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, and the add-on of defoamer accounts for 1.2% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water.
Described waterborne polyurethane resin is to adopt following methods to be prepared from, difference from Example 1:
In step a: the raw material of described waterborne polyurethane resin consists of PCDL 50%, isophorone diisocyanate 20%, dibutyl tin laurate 15%, dimethylol propionic acid 5% and triethylamine 10%;
In step b: high-speed stirring 22 minutes (stirring velocity is 1400 rev/mins) when temperature rises to 60 ℃, the add-on of water accounts for 5% of all raw material gross weights.
The preparation method of the present invention's aqueous composite ink of anti-the boiling, difference from Example 1:
In step b: at first 15% of raw water based polyurethane total resin weight is joined in stirred autoclave, then slowly add the defoamer of surface active agent, wetting dispersing agent and 0.8%;
Steps d: 85% and remaining 0.4% defoamer that add remaining waterborne polyurethane resin gross weight after grinding.
Embodiment 3: substantially the same manner as Example 1, difference is:
The present invention's aqueous composite ink of anti-the boiling, mean with weight percentage, and main raw material consists of waterborne polyurethane resin 55%, benzidine yellow G 13% and water 32%; Add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for 0.5% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for 1.5% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, and the add-on of defoamer accounts for 1.0% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water.
Described waterborne polyurethane resin is to adopt following methods to be prepared from, difference from Example 1:
In step a: the raw material of described waterborne polyurethane resin consists of PCDL 48%, isophorone diisocyanate 18%, dibutyl tin laurate 14%, dimethylol propionic acid 10% and triethylamine 10%;
In step b: high-speed stirring 20 minutes (stirring velocity is 1500 rev/mins) when temperature rises to 60 ℃, the add-on of water accounts for 10% of all raw material gross weights.
The preparation method of the present invention's aqueous composite ink of anti-the boiling, difference from Example 1:
In step b: at first 20% of raw water based polyurethane total resin weight is joined in stirred autoclave, then slowly add the defoamer of surface active agent, wetting dispersing agent and 0.6%;
Steps d: 80% and remaining 0.4% defoamer that add remaining waterborne polyurethane resin gross weight after grinding.
Embodiment 4: substantially the same manner as Example 1, difference is:
The present invention's aqueous composite ink of anti-the boiling, mean with weight percentage, and main raw material consists of waterborne polyurethane resin 48%, carbon black 20% and water 32%; Add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for 0.8% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for 3.0% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, and the add-on of defoamer accounts for 1.5% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water.
Described waterborne polyurethane resin is to adopt following methods to be prepared from, difference from Example 1:
In step a: the raw material of described waterborne polyurethane resin consists of PCDL 53%, isophorone diisocyanate 17%, dibutyl tin laurate 14%, dimethylol propionic acid 8% and triethylamine 8%;
In step b: high-speed stirring 22 minutes (stirring velocity is 1400 rev/mins) when temperature rises to 60 ℃, the add-on of water accounts for 7% of all raw material gross weights.
The preparation method of the present invention's aqueous composite ink of anti-the boiling, difference from Example 1:
In step b: at first 15% of raw water based polyurethane total resin weight is joined in stirred autoclave, then slowly add the defoamer of surface active agent, wetting dispersing agent and 1.0%;
Steps d: 85% and remaining 0.5% defoamer that add remaining waterborne polyurethane resin gross weight after grinding.
Embodiment 5: substantially the same manner as Example 1, difference is:
The present invention's aqueous composite ink of anti-the boiling, mean with weight percentage, and main raw material consists of waterborne polyurethane resin 52%, 15:4 phthalocyanine blue 12% and water 36%; Add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for 1.0% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for 1.2% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water, and the add-on of defoamer accounts for 0.8% of waterborne polyurethane resin, pigment and three kinds of raw material gross weights of water.
Described waterborne polyurethane resin is to adopt following methods to be prepared from, identical with embodiment 1.
The preparation method of the present invention's aqueous composite ink of anti-the boiling, difference from Example 1:
In step b: at first 20% of raw water based polyurethane total resin weight is joined in stirred autoclave, then slowly add the defoamer of surface active agent, wetting dispersing agent and 0.5%;
Steps d: 80% and remaining 0.3% defoamer that add remaining waterborne polyurethane resin gross weight after grinding.
Claims (1)
1. the aqueous composite ink of anti-the boiling, it is characterized in that: with weight percentage, mean, the described aqueous composite ink of anti-the boiling is mainly by raw material waterborne polyurethane resin 45～55%, pigment 10～20% and water 30～40% form, add in addition surface active agent, wetting dispersing agent and defoamer, the add-on of surface active agent accounts for waterborne polyurethane resin, 0.3～1.0% of pigment and three kinds of raw material gross weights of water, the add-on of wetting dispersing agent accounts for waterborne polyurethane resin, 1.0～3.0% of pigment and three kinds of raw material gross weights of water, the add-on of defoamer accounts for waterborne polyurethane resin, 0.5～1.5% of pigment and three kinds of raw material gross weights of water,
The solid content of described waterborne polyurethane resin is 30～35%, and number-average molecular weight is 22000～25000; Described surface active agent is U.S. aerochemistry surface active agent 104E; Described wetting dispersing agent is German Bi Ke chemistry wetting dispersing agent BYK-191; Described defoamer is the high auxiliary agent TEGO-1488 of German enlightening;
Described waterborne polyurethane resin is to be prepared from by the following method:
The raw material of a, described waterborne polyurethane resin consists of PCDL 48～55%, isophorone diisocyanate 15～20%, dibutyl tin laurate 10～15%, dimethylol propionic acid 5～10% and triethylamine 5～10%;
B, raw material according to the described waterborne polyurethane resin of step a forms the various raw materials of preparation, at first the PCDL of preparation and isophorone diisocyanate are joined in stirred autoclave and heated, and slowly stir, when temperature rises to 55～60 ℃, high-speed stirring is 20～25 minutes, add respectively the raw material dibutyl tin laurate of preparation after high-speed stirring in the mode of titration, dimethylol propionic acid and triethylamine, add water after three kinds of raw material titration are complete, the add-on of water accounts for 5～10% of all raw material gross weights, and rapidly the temperature of reaction soln in reactor is down to 20～30 ℃, test the properties of synthetic waterborne polyurethane resin, after reaching requirement, packed for standby use.
2, the aqueous composite ink of anti-boiling the according to claim 1 is characterized in that: described pigment is Rutile type Titanium Dioxide, benzidine yellow G, permanent bordeaux F5R, 15:4 phthalocyanine blue or carbon black.
3, the aqueous composite ink of anti-boiling the according to claim 1 is characterized in that: the stirring velocity of high-speed stirring described in step b in the time of 20～25 minutes is 1200～1500 rev/mins.
4, a kind of preparation method of the aqueous composite ink of anti-boiling the claimed in claim 1, is characterized in that, described preparation method comprises the following steps:
A, according to the proportioning ratio of the described aqueous composite ink of anti-boiling of claim 1, take various raw materials;
B, at first 15～20% of raw water based polyurethane total resin weight is joined in stirred autoclave, then the defoamer that slowly adds surface active agent, wetting dispersing agent and 0.5～1.0%, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 600～800 rev/mins 10～15 minutes;
C, then by required pigment, slowly add in stirred autoclave, with the speed dispersed with stirring of 1200～1500 rev/mins 45～50 minutes, after dispersed with stirring, adopt excellent pin formula shredder to be ground, grind 3～4 times, control temperature in process of lapping between 35～50 ℃, check that material reaches required fineness requirement;
80～85% and remaining 0.3～0.5% defoamer that add remaining waterborne polyurethane resin gross weight after d, grinding, adopt the frequency conversion dispersion machine with the speed dispersed with stirring of 1200～1500 rev/mins 25～30 minutes, add the water of preparation to adjust to required viscosity, and, with the speed dispersed with stirring of 1200～1500 rev/mins 5～10 minutes, finally adopt 400 order net filtrations packings.
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| CN104774498A (en) * | 2015-04-29 | 2015-07-15 | 林振坤 | Glass printing ink with anti-UV-ageing performance and preparation method thereof |
| CN105860652A (en) * | 2016-04-28 | 2016-08-17 | 佛山市恒学科技服务有限公司 | Environment-friendly water-based ink |
| CN106928423B (en) * | 2017-05-06 | 2020-01-10 | 黄山中泽新材料有限公司 | High-temperature-cooking-resistant polyester polyurethane resin and preparation method thereof |
| CN107502047A (en) * | 2017-09-05 | 2017-12-22 | 浙江华宝油墨有限公司 | Resistance to anti-boiling ink of polyurethane and preparation method thereof |
| CN108384319A (en) * | 2018-04-27 | 2018-08-10 | 福建格林春天新材料股份有限公司 | A kind of nylon printing digestion resistant water-based ink and preparation method thereof |
| CN111393905A (en) * | 2020-05-11 | 2020-07-10 | 浙江锦丰新材料科技有限公司 | Production process and production equipment of PU (polyurethane) ink |
| CN114806263B (en) * | 2022-05-11 | 2022-10-28 | 浙江华宝油墨有限公司 | Gravure boiling-resistant waterborne polyurethane ink and preparation method thereof |
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| CN101693797A (en) * | 2009-10-19 | 2010-04-14 | 湖南工业大学 | Environment-friendly water-based polyurethane ink and preparation method thereof |
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