CN101899235B - Water-borne ink composition and preparation method thereof - Google Patents
Water-borne ink composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides a water-borne ink composition and a preparation method thereof. The water-borne ink composition comprises water-borne polyurethane, a pigment, a cross-linking agent, a thickening agent and an ethylene-vinylacetate copolymer. The preparation method of the water-borne ink composition provided by the invention has the following steps: weighting and placing the ethylene-vinylacetate copolymer, the water-borne polyurethane, the pigment, the thickening agent and the cross-linking agent in a reactor based on a weight ratio thereof, adding water in the reactor, and stirring at room temperature to obtain the water-borne ink composition provided by the invention. The water-borne ink composition has good adhesion with a base material and has the characteristic of good spreadability on the surface of the base material; and an ink layer formed on the surface of the base material by the water-borne ink has good wear-resisting property.
Description
Technical field
The present invention relates to a kind of printing ink, relate in particular to a kind of aqueous ink compsn and preparation method thereof.
Background technology
At present, through phone housing, the button of decoration technique inside mold (IML) technology preparation, have the fabrication cycle weak point, can show multi-color, the product appearance is bright and clean attractive in appearance, but also has good wear-resisting, anti-stroke, chemical resistant properties premium properties, is more and more favored.And described film interior trim technology is just with behind the film forming that prints, and is embedded in the injection moulding die cavity mold-closing injection then.Casting resin combines with ink lay at the back side of film, and panel picture and text, sign place the technology between the resin of film and injection moulding, and be recent; In conjunction with the IML characteristics; Film interior trim technology of having arisen and new technologies such as physical vapor deposition combines make the metal effect of shell, button etc. obtain the good protection while and have guaranteed performances such as good wear-resisting, anti-stroke, chemical resistant properties again, still; The problem of following is; After adopting physical vapor deposition to be coated with on the films such as being contained in polycarbonate, polyethylene terephthalate, when the IML processing procedure is hot-forming, come off easily, distortion etc., this just need cover end printing ink as protection in coating application behind.But when using solvent type ink to protect, the easy corroding metal coating of employed solvent has influenced metal effect; Use ultraviolet light polymerization (UV) when printing ink is protected, the UV coating is more crisp, when hot-forming; Receiving under the situation of external force, the easy drawing crack of coating, and make metal level also by drawing crack; Therefore have the people to expect the employing water color ink, be used in the aqueous binder that has only Proll company of film interior trim technology at present, it is too fast to there is curing speed; Printing easy blocking half tone and in the big shortcoming of viscosity, viscosity is too big, causes the generation of glutinous mould phenomenon easily; And then the danger of drawing crack metal plating is arranged, viscosity is too big, can cause well wetting and spreading on metal plating of coating.
CN1676556 discloses a kind of screen printing water printing ink and method of manufacture thereof.Its water color ink is made up of high-performance water-based polyurethane, pigment, auxiliary agent, accomplishes through Synthesis of Waterborne Polyurethane, two steps of ink formulation.Synthetic water based polyurethane at first.Dispersion agent, 0-0.5wt% skimmer, the thickening material of 0.1-1wt%, 0-6wt% mediator agent ratio with 70-87wt% aqueous polyurethane, 12-18wt% pigment, 0-0.8wt% prepares water color ink through thorough mixing then.The water color ink strong adhesion of its invention, bonding dynamics are high, color clear, but when it is applied to the film interior trim because the viscosity of water color ink is too big, therefore caused water color ink can not be on coating fine wetting and spreading.
Summary of the invention
Technical problem to be solved by this invention provides the good aqueous ink compsn of a kind of spreadability,
Said composition comprises aqueous polyurethane, color stuffing, thickening material, linking agent, and this aqueous ink compsn also comprises ethylene-vinyl acetate copolymer.
The present invention also provides a kind of method for preparing above-mentioned ink composite, takes by weighing aqueous polyurethane, ethylene-vinyl acetate copolymer, color stuffing, additive by certain weight ratio and joins in the reaction kettle, stirs under the room temperature, can obtain printing ink.
Prepared water color ink that obtains and base material have sticking power, water color ink has good spreading property simultaneously.
Embodiment
The present invention provides a kind of aqueous ink compsn, and said composition comprises aqueous polyurethane, color stuffing, linking agent, thickening material, and this aqueous ink compsn also comprises ethylene-vinyl acetate copolymer.
Aqueous ink compsn provided by the present invention; Can be widely used on polycarbonate, ABS, polyethylene terephthalate plastic rubber substrate and the various sheet package printing ground; And can apply to the protection of IML process metal coating, make metal level be difficult for burn into and be difficult for drawing crack that bonding force is good between coating and the base material; Spreadability at substrate surface is good, makes metal effect obtain good protection.
The aqueous polyurethane that is adopted in the present invention is preferably through the aqueous polyurethane after the modification of machine silicon.Through organic-silicon-modified waterborne polyurethane resin, can effectively improve thermotolerance, solvent resistance, weathering resistance, chemical-resistant and the sticking power of paint film, make the over-all properties of coating be improved.
Described color stuffing above-mentioned is that pigment dyestuff is through grinding the water-based pigment dyestuff slurry that obtains after the dispersion agent dispersion grinding; Can select different colours according to client's demand, be benchmark with the water-based paint gross weight, and the aqueous color paste consumption is the 0-30wt% of total consumption; According to the effect selection consumption; Said water-based paint is conventionally known to one of skill in the art, can be commercially available, like among Ciba UNISPERSE RED 2030-S2, the Ciba UNISPERSE GREEN G-E one or more.Color stuffing is a particulate state, and wherein the particle diameter of color stuffing is 100-5000nm.
Said ethylene-vinyl acetate copolymer, main effect is the scratch resistance that increases the surface, and the spreadability that increases water color ink provided by the present invention; With the water color ink gross weight is benchmark; The ethylene-vinyl acetate copolymer consumption is the 1-5wt% of gross weight, preferred 2-4wt%, and said ethylene-vinyl acetate copolymer is conventionally known to one of skill in the art; Can be commercially available, like BYK-8421, BYK-526 etc.
In modifying process, also added linking agent; The linking agent that is adopted among the present invention is one or more in trimethylolpropane tris-(3-aziridinyl)-propionic ester, ethyleneimine, propyleneimine, the Soluol XC 100; Mainly be with aqueous polyurethane in carboxyl film forming crosslinking curing, be benchmark with the water color ink gross weight, the consumption of linking agent is total consumption 0.5-10wt%; The preferred 1-4wt% that selects; Said water cross-linking agent is conventionally known to one of skill in the art, can be commercially available, like the DSM CX-100 of DSM company;
In addition, in order further to improve the quality of water color ink, can also comprise in dispersion agent, flow agent, petition of surrender surface tension promoting agent, the skimmer one or more in this printing ink.
As adding dispersion agent, flow agent, petition of surrender surface tension promoting agent, skimmer, then their interpolation total amount accounts for the 0.1-10% of water color ink gross weight in the prescription.
Wherein, Dispersion agent is the polypropylene acid derivative, gather methyl-prop diluted acid verivate, maleic anhydride copolymer is in diisobutylene-cis-butenedioic anhydride, vinylbenzene-cis-butenedioic anhydride, condensation naphthalenesulfonate, the Povidone, USP/EP one or more; With the aqueous ink compsn gross weight is benchmark, and dispersant dosage is the 0.1-5 weight % of total consumption, selects 0.5-2 weight % under the preferable case; Said wandering agent can be commercially available, like TEGO Disper 750W, TEGO Disper 752W etc.
Flow agent is one or more in organic silicon modified by polyether, polyester modification organosilicon, reactive organosilicon, the polysiloxane-polyether copolymer.Among the present invention; With the water color ink gross weight is benchmark, and the flow agent consumption is the 0.01-2 (wt%) of system total amount, selects 0.05-1 (wt%) under the preferable case; Said flow agent can be commercially available, like TGEO Glide 482, TGEO Glide 450, BYK-380, BYK-333 etc.
Said petition of surrender surface tension promoting agent is one or more in dialkyl sulfosuccinates, sodium alkyl naphthalene sulfonate, Viscotrol C sulphate, alkylphenol polyvinyl ether, polyoxyethylene glycol alkyl ester, poly-phosphate, silicate, polyacrylic acid derivative, the maleic anhydride copolymer; The promoting agent consumption is the 0.01-5 (wt%) of total consumption; Select 0.05-2 (wt%) under the preferable case; Said promoting agent is conventionally known to one of skill in the art; Can be commercially available, like TEGO WET 280, TEGO WET 270, TEGO WET 500 etc.
Said thickening material is mainly one or more in water-based wilkinite, organobentonite, methylcellulose gum, Walocel MT 20.000PV, Natvosol, titanate coupling agent, polypropylene acid, the Povidone, USP/EP; It mainly has been emulsifying effect; Regulating the viscosity of printing ink, is benchmark with the water color ink gross weight, and the thickening material consumption is 0.1-5wt%; Select 0.5-2wt% under the preferable case; Said thickening material is conventionally known to one of skill in the art, can be commercially available, like vapour crust HV30, ROHM AND HAAS TT-615, ASE-60 etc.
Said skimmer is one or more in silicone emulsion, higher alcohols fatty acid ester compound, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene amidogen ether, polyoxypropylene ethylene oxide glyceryl ether, polyoxyethylene polyoxypropylene season penta methanol-ethers; With the water color ink gross weight is benchmark; The consumption of skimmer is 0.05-1wt%; Select 0.1-0.5wt% under the preferable case; Said skimmer is conventionally known to one of skill in the art, can be commercially available, like among TEGO 825, TEGO 902W, BYK-011, the BYK-024 one or more.
The present invention also provides the preparation method of water color ink; This method comprises by certain weight ratio and takes by weighing ethylene-vinyl acetate copolymer, aqueous polyurethane, color stuffing, additive, linking agent; Solvent joins in the reaction kettle, stirs 30-120min under the room temperature, can obtain printing ink.
Wherein, the synthetic of the aqueous polyurethane that the present invention adopted may further comprise the steps:
1, according to following weight percent as follows (wt%) take by weighing synthetic needed each component
Polyvalent alcohol: 30-70, vulcabond: 20-40, catalyzer: 0.1-1, organosilicon: 1-8, wetting ability chainextender: 5-20, neutralizing agent: 2-10;
2, in the dry reaction still of reflux condensing tube, stirring tank is housed, add polyvalent alcohol and a spot of catalyzer (10% solution of dibutyl tin laurate) that step 1 takes by weighing, add the vulcabond that step 1 takes by weighing again, at 60 ℃ of reaction 2h; Add the acetone viscosity reduction then, add the wetting ability chainextender chain extension that step 1 takes by weighing again, react 4h again; Cool to 40 ℃; Add an amount of acetone then and make mixture be easy to stir, then under whipped state, add the neutralizing agent that step 1 takes by weighing and neutralize; Add the organosilicon stirring 1h that step 1 takes by weighing again; 1h is stirred in adding distil water emulsification then, and last underpressure distillation goes out the emulsion that acetone obtains, and promptly gets organic silicon modified aqueous polyurethane.
Wherein, polyvalent alcohol above-mentioned is polyester polyol or polyether glycol, and relative molecular mass is 500-8000, selects 1000-5000 under the preferable case, and consumption is the 30-70% of organic silicon modified aqueous polyurethane synthetic total mass, is preferably 40-60%;
Said vulcabond is a kind of among TDI (tolylene diisocyanate), MDI (diphenylmethanediisocyanate), IPDI (isophorone diisocyanate), the HDI (hexamethylene diisocyanate); Consumption is the 20-40% of organic silicon modified aqueous polyurethane synthetic total mass, is preferably 25-35%;
Said organosilicon is a kind of in mono amino organosilicon, the two amido organosilicon, and said organosilicon is that consumption is the 1-8% of organic silicon modified aqueous polyurethane synthetic total mass, is preferably 2-6%;
Said wetting ability chainextender is dimethylol propionic acid (DMPA), terepthaloyl moietie, glycol ether, TriMethylolPropane(TMP), hydrazine (NH
2NH
2), in the quadrol one or more, said wetting ability chainextender consumption is the 5-20% of organic silicon modified aqueous polyurethane synthetic total mass, is preferably 8-18%;
Said neutralizing agent is a kind of in the acetic acid in dimethylethanolamine, Monoethanolamine MEA BASF, trolamine, the diethylolamine (HAc), and said neutralizing agent consumption is the 2-10% of organic silicon modified aqueous polyurethane synthetic total mass, is preferably 3-8%;
Said catalyzer is one or more in dibutyl tin laurate, dibutyltin diacetate, the 2-ethylhexyl inferior tin of acid and methylsulphonic acid bismuth, Bismuth Octoate, bismuth citrate, the bismuth oxide; Under the preferable case in selection methylsulphonic acid bismuth, Bismuth Octoate, bismuth citrate, the bismuth oxide one or more; Said catalyst levels is the 0.1-1% of organic silicon modified aqueous polyurethane synthetic total mass; Be preferably 0.2-0.8%, said catalyzer can be commercially available, like TEGO KAT720;
A kind of preferred method of preferred preparation water color ink specifically is provided:
With aqueous polyurethane, ethylene-vinyl acetate copolymer, color stuffing, linking agent, dispersion agent, according to 40-70: 2-4: 0.1-30: 0.5-10: the 0.5-2 proportioning; Join in the reaction kettle; At room temperature use high speed dispersor high-speed stirring 15-30min; And then slowly to drip thickening material to viscosity be 5000-10000CP; (use rotational viscosimeter test Yuyao Yinhuan Flow Instrument Co., Ltd NDJ-79 type rotational viscosimeter), and high-speed stirring 15-30min again; The last linking agent that adds the flow agent, the petition of surrender surface tension promoting agent that accounts for total weight 0.05-2wt% that account for total weight 0.05-2wt% more respectively, accounts for water color ink gross weight 1-4wt% mix stir 30-120min after, can obtain water color ink of the present invention.
Embodiment 1
Present embodiment is explained aqueous ink compsn provided by the invention and preparation method thereof, and this method comprises:
1) organic silicon modified aqueous polyurethane
In reaction kettle, add the PCDL of 5500g and the catalyzer (methylsulphonic acid bismuth 10% solution) of 20g, add 2500g isophorone diisocyanate (IPDI) again, under 60 ℃ of conditions, react 2h; Add 500g acetone viscosity reduction then, add 900g dimethylol propionic acid (DMPA) chain extension again, react 4h again; Cool to 40 ℃; Add the 500g tertiary amine and neutralize, add 600g mono amino organosilicon reaction 1h then, under agitation add 10000g zero(ppm) water emulsion reaction 1h; Underpressure distillation goes out acetone and obtains emulsion, promptly prepares organic silicon modified aqueous polyurethane.
2) preparation of water color ink
Take by weighing organic silicon modified aqueous polyurethane 650g, ethylene-vinyl acetate BYK-526 50g, mill base Ciba UNISPERSE RED 2030-S2 230g, water 50g, dispersion agent TEGO Disper 750W 5g, skimmer TEGO 902W 5g, thickening material HV30 20g, flow agent TGEO Glide 450 5g, petition of surrender surface tension promoting agent TEGO WET 270 5g, water cross-linking agent DSM CX-100 30g by embodiment 1 preparation; The BYK-526 ethylene-vinyl acetate of first organic silicon modified aqueous polyurethane with 650g, 50g, water 50g, the Ciba UNISPERSE RED 2030-S2 mill base of 230g, the TEGO Disper 750W dispersion agent of 5g, the TEGO 902W skimmer of 5g join in the reaction kettle; At room temperature use the speed high-speed stirring 30min of high speed dispersor 2500r/min; And then slowly drip the HV30 thickening material of 20g; To viscosity 8500CP (Yuyao Yinhuan Flow Instrument Co., Ltd NDJ-79 type rotational viscosimeter); And the speed high-speed stirring 30min of 2500r/min again; Last TGEO Glide 450 flow agents of 5g, TEGO WET 270 petition of surrender surface tension promoting agents and the 30g DSM CX-100 water cross-linking agent of 5g of adding respectively again; At room temperature mix 60min under the speed with high speed dispersor 2500r/min, make water color ink sample T1.
Embodiment 2
Present embodiment is used for explaining aqueous ink compsn provided by the invention and preparation method thereof.
Adopt to prepare T2 with embodiment 1 identical method, different is with the weight of water color ink is benchmark, and the content of aqueous polyurethane is 40%; The content of ethylene-vinyl acetate copolymer is 2 weight %; The content of pigment is 2 weight %, and the content of ethyleneimine is 0.5%, and the content of methylcellulose gum is 0.5 weight %; Method through described in the embodiment makes sample T2.
Embodiment 3
Present embodiment is used for explaining water color ink provided by the present invention and preparation method thereof.
This enforcement is adopted and to be prepared sample T3 with embodiment 1 identical preparation method, and different is, is benchmark with the weight of water color ink; The content of aqueous polyurethane is 70%, and the content of ethylene-vinyl acetate copolymer is 4 weight %, and the content of pigment is 5 weight %; The content of propyleneimine is 5%, and the content of Povidone, USP/EP is 2 weight %, and does not adopt in the present embodiment through silane-modified aqueous polyurethane; Method through described in the embodiment makes sample T3.
Comparative Examples 1
This Comparative Examples is used for explaining reference printing ink and preparation method thereof.
Prepare aqueous polyurethane and synthetic water silk screen painting ink according to disclosed a kind of silk screen printing ink of CN1676556 and method of manufacture, as reference printing ink CT1.
Electric mixer is being housed, in the reaction kettle of the prolong that confluxes, TM, nitrogen inlet, is adding polyoxygenated third rare glycol 620g, isophorone diisocyanate 252g, dimethylol propionic acid 70g reacts 2H under 80 ℃ condition, obtain performed polymer.Add 50g acetone then and reduce viscosity, add 55g triethylamine neutralizing agent salify, cooling adds the 1000g emulsifying water then.Add 12g quadrol chainextender, obtain aqueous polyurethane emulsion, underpressure distillation goes out solvent then.
The preparation of reference water color ink:
Take by weighing the aqueous polyurethane that 800g was made by the last step; 190g pigment Ciba UNISPERSERED 2030-S2,3g dispersion agent TEGO Disper 750W, 4g skimmer TEGO 902W drop in the batching still; Surely stirred 1 hour with the speed of high speed dispersor 2500r/min down in advance the chamber; Add 3g thickening material HV30 then, with the speed stirring 30min of high speed dispersor 2500r/min, after discharging both must the reference water color ink behind the shredder thorough mixing.
Embodiment 4-6
Present embodiment is used for detecting the good surface properties of on plastic cement, printing of T1-T3
It is that 145 millimeters, width are that 45 millimeters, thickness are 2 millimeters ABS plastic plate (propylene-butadiene-styrene terpolymer) (Biyadi Co Ltd that the water color ink T1-T3 that embodiment 1-3 is made is printed on length respectively; 757) on; At room temperature dry 24 hours, detect the surface property of printing ink T1-T3 behind the plastic cement surface printing respectively according to following method then:
One, sticking power test
Testing standard: ISO 2409
Testing method: use the knife back of surgical knife on coating, to draw 12 road cuts, wherein at least two cuts and other cut at an angle of 90, to form grid from the teeth outwards, the length of side of grid is 1 millimeter.Guarantee that every cut all is cut to body material.Along the both direction of cut each with brush 5 times.3M adhesive tape (Dongguan Ao Mike company; The adhesive tape model is 3M600) be bonded on the surface; With finger tip that wiping belt is tight, guarantee to contact with the good of coating, in 5 minutes, tear adhesive tape well-regulated open off adhesive tape at 0.5-1 in second with 60 ° angle from the free end of adhesive tape.
Grade classification:
0 grade: the edge of otch is level and smooth fully, and the square of grid does not all peel off;
1 grade: the area that peels off part is not more than and 5% of the surperficial adhesive tape area that contacts;
2 grades: peel off area partly greater than 5% of the adhesive tape area that contacts with the surface, and be no more than 15%;
3 grades: peel off area partly greater than 15% of the adhesive tape area that contacts with the surface, and be no more than 35%;
4 grades: peel off area partly greater than 35% of the adhesive tape area that contacts with the surface, and be no more than 65%.Test result is seen table 1
Two, wear-resisting test
The 7-IBB type RCA abrasion appearance that uses U.S. Nuo Man Instrument and Equipment Company to produce, under the effect of 175 gram forces, mill is coated with the coating that installs, the number of times that rubber wheel rotates during the show-through material of record coating.Test result is seen table 1
Three, wetting and spreading property testing
Adopt the DCAT21 surface interface tensiometer of Beijing Orient De Fei Instr Ltd. to test.Operate ink sample according to testing method the test result that gets final product.The big wetting and spreading property of surface tension is poor, and the little wetting and spreading property of surface tension is good.Test result is as shown in table 1
Comparative Examples 2
Present embodiment is used for detecting the good surface properties after printing on the plastic cement of CT1, and each item test event that is adopted among each item performance project of test and the embodiment 4-6 is identical.Test result is as shown in table 1:
Table 1
| Sequence number | T1 | T2 | T3 | CT1 |
| The sticking power test | 0 grade | 0 grade | 0 grade | 0 grade |
| Wear-resisting test | 519 circles | 486 circles | 464 circles | 150 circles |
| The wetting and spreading property testing | 3.465×10 -2 (N/m) | 3.288×10 -2 (N/m) | 3.673×10 -2 (N/m) | 4.468×10 -2 (N/m) |
Can find out that from table 1 surface tension that water color ink coating provided by the invention has a sample T2 of good spreading property such as embodiment 2 preparations is 3.288 * 10
-2And the surface tension of Comparative Examples 1 preparation sample CT1 is 4.468 * 10 (N/m),
-2(N/m); The big wetting and spreading property of surface tension is poor; The little wetting and spreading property of surface tension is good; Therefore the water color ink that is provided in visible aqueous ink compsn provided by the present invention and the ratio is compared, and water color ink wetting and spreading performance provided by the present invention is good, and the abrasion property of being made up of water color ink can be better.
Claims (9)
1. an aqueous ink compsn comprises aqueous polyurethane, color stuffing, linking agent, thickening material, it is characterized in that, this aqueous ink compsn also comprises ethylene-vinyl acetate copolymer; Wherein said linking agent is selected from one or more in trimethylolpropane tris-(3-ethyleneimine base)-propionic ester, ethyleneimine, propyleneimine, the Soluol XC 100; Gross weight with printing ink is a benchmark; The content of ethylene-vinyl acetate copolymer is that the content of 1-5 weight %, aqueous polyurethane is that the content of 30-80 weight %, color stuffing is that the content of 0.1-30 weight %, linking agent is 0.5-10 weight %; The content of thickening material is 0.1-5 weight %, and surplus is a water.
2. aqueous ink compsn according to claim 1 can also comprise: one or more in dispersion agent, flow agent, petition of surrender surface tension promoting agent, the skimmer.
3. aqueous ink compsn according to claim 2, wherein, the addition of one or more in dispersion agent, flow agent, petition of surrender surface tension promoting agent, the skimmer accounts for the 0.1-10% of water color ink gross weight.
4. aqueous ink compsn according to claim 2, wherein, the weight ratio 0.1-5 of dispersion agent, flow agent, petition of surrender surface tension promoting agent, skimmer addition: 0.01-2: 0.01-5: 0.05-1.
5. aqueous ink compsn according to claim 1, the particle diameter of wherein said color stuffing are 100-5000nm.
6. the preparation method of the described water color ink of claim 1; It is characterized in that by weight taking by weighing ethylene-vinyl acetate copolymer, aqueous polyurethane, color stuffing, thickening material, linking agent, water joins in the reaction kettle; Stir under the room temperature, can obtain aqueous ink compsn.
7. the preparation method of water color ink according to claim 6; Gross weight with printing ink is a benchmark; The content of ethylene-vinyl acetate copolymer is that the content of 1-5 weight %, aqueous polyurethane is that the content of 30-80 weight %, color stuffing is that the content of 0.1-30 weight %, linking agent is 0.5-10 weight %; The content of thickening material is 0.1-5 weight %, and surplus is a water.
8. the preparation method of water color ink according to claim 6, wherein thickening material is one or more in water-based wilkinite, organobentonite, methylcellulose gum, Walocel MT 20.000PV, Natvosol, titanate coupling agent, polypropylene acid, the Povidone, USP/EP.
9. the preparation method of water color ink according to claim 6, wherein waterborne polyurethane resin is an organosilicon modified aqueous polyurethane resin.
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| CN102382515B (en) * | 2011-11-08 | 2014-03-26 | 北京印刷学院 | Environment-friendly, strong acid-resistant, strong base-resistant and steaming-resistant ink and preparation method |
| CN102555317B (en) * | 2012-01-05 | 2016-02-24 | 深圳市宜丽环保科技有限公司 | A kind of magnetic anti-counterfeiting health-care material and production method thereof |
| CN103045012B (en) * | 2013-01-18 | 2014-09-10 | 广东佳景科技有限公司 | Anti-static water-based ink and preparation method thereof |
| CN103555054B (en) * | 2013-11-05 | 2015-01-21 | 英科﹒卡乐油墨（苏州）有限公司 | Non-corona waterborne ink for flexible packaging |
| CN105297447A (en) * | 2015-12-14 | 2016-02-03 | 苏州伊甸园苹果服饰有限公司 | Finishing process of shirt fabric |
| CN106280694A (en) * | 2016-08-31 | 2017-01-04 | 昆山大世界油墨涂料有限公司 | A kind of half tone environmental protection ink being applied to leather substance |
| CN106567521B (en) * | 2016-11-14 | 2019-02-05 | 广东天元汇邦新材料股份有限公司 | A kind of preparation method of the environmentally friendly facing film of high metal luster |
| US10184063B2 (en) * | 2016-12-22 | 2019-01-22 | Upm Raflatac Oy | Top coating for label face stock, method for providing the top coating and top coated label face stock |
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| CN1676556A (en) * | 2004-03-30 | 2005-10-05 | 天津科技大学 | Screen printing water-soluble ink |
| US7008994B1 (en) * | 1998-04-15 | 2006-03-07 | Mikuni Shikiso Kabushiki Kaisha | Aqueous pigment dispersion, process for producing the same, and water-based ink comprising the same |
| CN101429362A (en) * | 2008-12-09 | 2009-05-13 | 天津环球磁卡股份有限公司 | Watersoluble silk screen printing ink and method of producing the same |
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|---|---|---|---|---|
| US7008994B1 (en) * | 1998-04-15 | 2006-03-07 | Mikuni Shikiso Kabushiki Kaisha | Aqueous pigment dispersion, process for producing the same, and water-based ink comprising the same |
| CN1676556A (en) * | 2004-03-30 | 2005-10-05 | 天津科技大学 | Screen printing water-soluble ink |
| CN101429362A (en) * | 2008-12-09 | 2009-05-13 | 天津环球磁卡股份有限公司 | Watersoluble silk screen printing ink and method of producing the same |
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Effective date of registration: 20190703 Address after: No. 395 Shenyu Road, Jiading District, Shanghai 201800 Patentee after: Shanghai Tonghui Ink Paint Co., Ltd. Address before: 518118 3001 Ping Ping Road, Pingshan Town, Longgang District, Shenzhen, Guangdong Patentee before: Biyadi Co., Ltd. |