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CN100395295C - Water printing ink using synthetic water solid acrylate resin as base material and its preparation method - Google Patents

Water printing ink using synthetic water solid acrylate resin as base material and its preparation method Download PDF

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Publication number
CN100395295C
CN100395295C CNB2005100109128A CN200510010912A CN100395295C CN 100395295 C CN100395295 C CN 100395295C CN B2005100109128 A CNB2005100109128 A CN B2005100109128A CN 200510010912 A CN200510010912 A CN 200510010912A CN 100395295 C CN100395295 C CN 100395295C
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Prior art keywords
water
color ink
solid
resin
acrylate resin
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Expired - Fee Related
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CNB2005100109128A
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CN1718646A (en
Inventor
张爱国
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KUNMING YUEDUN INK SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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KUNMING YUEDUN INK SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

The present invention relates to water printing ink using synthetic water solid acroid resin as base material and the preparation method of the water printing ink. The present invention belongs to printing ink and a production process thereof, particularly to water printing ink and a production process thereof. The present invention regards an acrylic acid series mixed monomer as a comonomer, ammonium persulphate as an initiator and water as a reaction medium. Water phase suspension copolymerization reaction is implemented when the acrylic acid series mixed monomer, the ammonium persulphate and the water are stirred to obtain the water solid acroid resin. The water solid acroid resin is dissolved by using water, a cosolvent and an amine substance and is matched with pigment, water and an auxiliary agent. Then, the mixture is ground by a sand mill to make up the water printing ink. The product of the present invention has no poison, no pollution, no combustion, no burst and no decolorizing or decoloring and has the characteristics of high use safety, high concentration, less dosage, stable performance, high printing adaptability, strong adhesion, rapid dryness, good water resistance and friction resistance, low manufacturing cost, etc. Printed products have no harmful residual substances after dryness.

Description

It with the synthetic water solid acrylate resin water color ink of base-material and preparation method thereof
Technical field
The invention belongs to printing ink and production technique thereof, particularly water-based printing printing ink and production technique thereof.
Background technology
The liquid ink that extensively adopts at present in the packages printing industry is a solvent with venomous injurants such as aromatic hydrocarbon, ester, ketone, and the content of organic solvent is generally 50%~70% in the printing ink.This kind solvent is most of can the volatilization in printing process, an ink usage reaches 30 tons/year machine room, the annual organic solvent that discharges in atmospheric environment is up to more than 20 tons, severe contamination workshop and atmospheric environment, the health of operator and surrounding resident has been constituted serious threat.In addition, the printing ink that leaves in the workshop belongs to flammable and explosive substance, also is a hidden danger to the safety of factory.Residual solvent in the printing ink has certain influence to the quality of packing content thing.
Water color ink be aqueous high molecular resin, pigment and relevant auxiliary agent through the water-based print ink that chemical process makes with physical mixed, be applicable to gentle edition and intaglio printing.Do not contain volatile organic solvent in the ink, in printing process, workers ' health is had no adverse effects, pollution-free to atmospheric environment.The distinct advantages of ink meets the legislations of environmental protection of increasingly stringent, is subjected to the favor of packages printing circle in the world day by day.With the U.S. is example, the ink consumption of national packages printing industry in 1998 is above 230,000 tons, 95% is the flexographic printing product, 80% intaglio printing product, 20% plastic printing product all adopt ink, now, the flexographic printing annual increasing rate of U.S. newpapers and periodicals industry is 87%, adds, developed country printing houses such as English, meaning all announce to use instead flexible printing press.
At present, the printing-ink that adopts of China's flexographic plate and intaglio printing is traditional water color ink and alcohol-soluble printing ink two big classes: shortcoming such as wash, fade easily that traditional water color ink ubiquity rate of drying is slow, glossiness is low, cause easily that paper shrinks, printed patterns is not water-fast; Alcohol-soluble printing ink is to be primary solvent with the alcohols thereby to cost an arm and a leg, and has toxic.
In the printing ink manufacturing processed, its core is selecting for use of matrix resin.In the manufacturing processed of in the past water color ink, most of producers are that to select the ACRYLIC EMULSION and the solid resin of external import be that matrix is made ink, and this method is based on emulsion.From technical standpoint, not so good based on the ink flow sex change of emulsion, film forming gloss is bad, and dissolubility is bad again, and is bad to the wettability of pigment, wetting bad to forme and printing element particularly, and cause printing adaptability poor, printing effect is bad; From economic angle, the ACRYLIC EMULSION cost of import is higher.
Summary of the invention
It is the water color ink and preparation method thereof of base-material with the synthetic water solid acrylate resin that technical problem to be solved by this invention provides a kind of, it have nontoxic, pollution-free, do not fire, not quick-fried, safety in utilization good, concentration is high, consumption is few, stable performance, printing adaptability is good, attachment fastness is strong, fast drying, printed matter are done the no hazard residue material in back, water-fast and abrasion resistance is good, nondiscoloration, fade, characteristics such as cheap for manufacturing cost.
Solving the scheme that technical problem of the present invention adopts is:
Each weight percentages of components is in the prescription of water color ink, aqueous solid acrylic resin 5%~20%, solubility promoter 5%~20%, pigment 10%~30%, auxiliary agent 0.5%~3%, amine substance 0.5%~10%, surplus is a water, and aqueous solid acrylic resin wherein is that 10%~50% acrylic acid series mix monomer, 0.1%~1.5% ammonium persulphate and surplus are the product of each component copolyreaction of water.
The preparation method of water color ink is, (1) be comonomer with the acrylic acid series mix monomer, with the ammonium persulphate is initiator, with water is reaction medium, according to the above ratio, carries out the aqueous-phase suspending copolyreaction under whipped state, cold filtration again, washing, oven dry obtains white granular aqueous solid acrylic resin; (2) according to the above ratio, go up the aqueous solid acrylic resin of gained earlier with water, solubility promoter and amine dissolving, be equipped with pigment, water and auxiliary agent again, grind through sand mill and form water color ink.
Acrylic acid series mix monomer in the water-soluble printing ink formula of the present invention be selected from vinylformic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, the acrylamide more than two kinds, wherein also can sneak into vinylbenzene; State amine substance in filling a prescription and can be single thing or mixture in ammoniacal liquor, thanomin, triethylamine, the 2-amino-2-methyl propyl alcohol; Solubility promoter can be single thing or the mixture in ethanol, Virahol, ethylene glycol mono-ether, the propylene glycol monomethyl ether; Selection of auxiliary be printing ink with organosilicon ketone and alkynol class mixed aid; Reaction medium when preparation aqueous solid acrylic resin also comprises alcohols.
When preparation aqueous solid acrylic resin, at first in reactor, add reaction medium by formula ratio, stirring is warming up to 60 ℃~90 ℃, stirring velocity is 50 rev/mins~80 rev/mins, adds 1/3 initiator, and beginning slow dropwise addition of acrylic acid again is mix monomer, be controlled in 1 hour~2 hours and dropwise, in the dropping process, regularly add initiator, also added remaining initiator when mix monomer drips, and insulation reaction 1 hour~2 hours.
In preparation water color ink operation, by formula ratio water, solubility promoter, amine substance are dropped in another reactor earlier, again above-mentioned aqueous solid acrylic resin is dropped in the reactor by formula ratio and dissolve, behind molten the finishing, drop into pigment, water, auxiliary agent, with 900 rev/mins~1400 rev/mins stirring velocity high speed dispersion, the process sand mill is ground to the finished product water color ink less than 10 μ m at last.
Embodiment
Embodiment 1
Add in the reactor accounting for the water of weight percent 55% and 4.0% ethanol, be warming up to 60 ℃, stir with 80 rev/mins, add 1/3 of ammonium persulphate total amount, slowly dropwise addition of acrylic acid is a mix monomer, be controlled in 1 hour~2 hours and dropwise, the acrylic acid series mix monomer is for accounting for weight percent 16% butyl acrylate, 12% methyl methacrylate, 12% vinylformic acid.Regularly add ammonium persulphate in the dropping process, also added remaining ammonium persulphate when mix monomer drips, its whole total amounts account for 1.0%, and insulation reaction 1 hour~2 hours.After the reaction, cold filtration, washing, oven dry obtain the solid resin powder again, and its leading indicator is, outward appearance is white in color Powdered, amount of solid>98%, and second-order transition temperature is 20 ℃, acid number is 233mgKOH/g.In proportion in another reactor, earlier to account for 45% water, ethanol 10%, thanomin 5%, the NH4OH 1.0% of concentration 28%, dissolving accounts for the aqueous solid acrylic resin of weight percent 20%, behind molten the finishing, the pigment of input 15% and 4.0% auxiliary agent, stirring velocity high speed dispersion with 900 rev/mins~1400 rev/mins, grind to form particle diameter at last less than 10 μ m water color inks, pigment adopts the WF483 of Switzerland Clariant company, and auxiliary agent is 1.0% the surfyno 1440 of accounting for of U.S. gas chemical company, account for 3.0% surfynolCT-131 and the surfynol DF-66 that accounts for whole total amounts 0.5%.Through filtering, mix colours, packing, can use for color printing factory.The leading indicator of producing good water color ink is as follows:
Color: in tinctorial pattern deviation 5%
Fineness:<10 μ m
Tinting strength: 90~100
Viscosity: (be coated with-4 glasss, second/25 ℃) 60 ± 10 seconds
PH value: 8.5~9.5
Rate of drying: 100~200m/min.
Embodiment 2
Add in the reactor accounting for the water of weight percent 55% and 4.2% ethanol, be warming up to 80 ℃, stir with 70 rev/mins, add 1/3 of ammonium persulphate total amount, slow drip styrene, acrylic acid series mix monomer, be controlled in 1 hour~2 hours and dropwise, vinylbenzene, acrylic acid series mix monomer are the vinylbenzene that accounts for weight percent 24%, 8% butyl acrylate and 8% vinylformic acid.Regularly add ammonium persulphate in the dropping process, also added remaining ammonium persulphate when mix monomer drips, its whole total amounts account for 0.8%, and insulation reaction 1 hour~2 hours.After the reaction, cold filtration, washing, oven dry obtain the solid resin powder again, and its leading indicator is, outward appearance is white in color Powdered, amount of solid>98%, and second-order transition temperature is 55 ℃, acid number is 155mgKOH/g.In proportion in another reactor, earlier to account for 42% water, ethanol 15%, thanomin 3%, NH4OH 1.0% dissolving of concentration 28% accounts for the aqueous solid acrylic resin of weight percent 20%, behind molten the finishing, the pigment of input 15% and 4.5% auxiliary agent, stirring velocity high speed dispersion with 900 rev/mins~1400 rev/mins, grind to form particle diameter at last less than 10 μ m water color inks, pigment adopts the WF13 of Switzerland Clariant company, and auxiliary agent is 1.0% the surfyno 1440 of accounting for of U.S. gas chemical company, account for 3.0% surfynol CT-131 and the surfynol DF-66 that accounts for whole total amounts 0.5%.Through filtering, mix colours, packing, can use for color printing factory.The leading indicator of producing good water color ink is as follows:
Color: in tinctorial pattern deviation 5%
Fineness:<10 μ m
Tinting strength: 90~100
Viscosity: (be coated with-4 glasss, second/25 ℃) 60 ± 10 seconds
PH value: 8.5~9.5
Rate of drying: 100~200m/min.
Embodiment 3
The water that accounts for weight percent 58.5% is added in the reactor, be warming up to 90 ℃, stir with 50 rev/mins, add 1/3 of ammonium persulphate total amount, slowly dropwise addition of acrylic acid is a mix monomer, be controlled in 1 hour~2 hours and dropwise, the acrylic acid series mix monomer is the butyl methacrylate that accounts for weight percent 8%, 20% methyl methacrylate and 12% methacrylic acid.Regularly add ammonium persulphate in the dropping process, also added remaining ammonium persulphate when mix monomer drips, its whole total amounts account for 1.5%, and insulation reaction 1 hour~2 hours.After the reaction, cold filtration, washing, oven dry obtain the solid resin powder again, and its leading indicator is, outward appearance is white in color Powdered, amount of solid>98%, and second-order transition temperature is 95 ℃, acid number is 195mgKOH/g.In proportion in another reactor, earlier to account for 36% water, ethanol 20%, thanomin 4%, NH4OH 1.0% dissolving of concentration 28% accounts for the aqueous solid acrylic resin of weight percent 20%, behind molten the finishing, the pigment of input 15% and 4.5% auxiliary agent, stirring velocity high speed dispersion with 900 rev/mins~1400 rev/mins, grind to form particle diameter at last less than 10 μ m water color inks, pigment adopts the WF153 of Switzerland Clariant company, and auxiliary agent is 1.0% the surfyno440 of accounting for of U.S. gas chemical company, account for 3.0% surfynol CT-131 and the surfynol DF-66 that accounts for whole total amounts 0.5%.Through filtering, mix colours, packing, can use for color printing factory.The leading indicator of producing good water color ink is as follows:
Color: in tinctorial pattern deviation 5%
Fineness:<10 μ m
Tinting strength: 90-100
Viscosity: (be coated with-4 glasss, second/25 ℃) 60 ± 10 seconds
PH value: 8.5~9.5
Rate of drying: 100~200m/min.

Claims (9)

1. one kind is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: the weight percent of each component is,
Aqueous solid acrylic resin 5%~20%, solubility promoter 5%~20%, pigment 10%~30%, auxiliary agent 0.5%~5%, amine substance 0.5%~10%, surplus is a water, and aqueous solid acrylic resin wherein is that 10%~50% acrylic acid series mix monomer, 0.1%~1.5% ammonium persulphate and surplus are the product of each component copolyreaction of water.
2. described by claim 1 is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: the acrylic acid series mix monomer be selected from vinylformic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, the acrylamide more than two kinds.
3. described by claim 1 is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: described amine substance is single thing or the mixture in ammoniacal liquor, thanomin, triethylamine, the 2-amino-2-methyl propyl alcohol.
4. described by claim 1 is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: solubility promoter is single thing or the mixture in ethanol, Virahol, ethylene glycol mono-ether, the propylene glycol monomethyl ether.
5. described by claim 1 is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: described auxiliary agent is printing ink organosilicon ketone and an alkynol class mixed aid.
6. described by claim 2 is the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that: also sneaked into vinylbenzene in the acrylic acid series mix monomer.
7. described by claim 1 is the water color ink of base-material with the synthetic water solid acrylate resin, and it is characterized in that: the reaction medium of aqueous solid acrylic resin also comprises alcohols.
8. one kind is the preparation method of the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that:
(1) be comonomer with 10%~50% acrylic acid series mix monomer, the ammonium persulphate with 0.1%~1.5% is an initiator, is reaction medium with the water of residuals weight per-cent, under agitation carry out the aqueous-phase suspending copolyreaction, cold filtration washs again, oven dry obtains the white granular resin;
(2) with water, solubility promoter and the last operation gained aqueous solid acrylic resin of amine dissolving, be equipped with pigment, water and auxiliary agent again, form water color ink through the sand mill grinding, and the weight percent of each component is, aqueous solid acrylic resin 5%~20%, solubility promoter 5%~20%, pigment 10%~30%, auxiliary agent 0.5%~5%, amine substance 0.5%~10%, surplus are water.
9. described by claim 8 is the preparation method of the water color ink of base-material with the synthetic water solid acrylate resin, it is characterized in that:
(1) when preparation aqueous solid acrylic resin, at first in reactor, add reaction medium by formula ratio, stirring is warming up to 60 ℃~90 ℃, stirring velocity is 50 rev/mins~80 rev/mins, adds 1/3 initiator, and beginning slow dropwise addition of acrylic acid again is mix monomer, be controlled in 1 hour~2 hours and dropwise, in the dropping process, regularly add initiator, also added remaining initiator when mix monomer drips, and insulation reaction 1 hour~2 hours;
(2) in preparation water color ink operation, by formula ratio water, solubility promoter, amine substance are dropped in another reactor earlier, again above-mentioned aqueous solid acrylic resin is dropped in the reactor by formula ratio and dissolve, behind molten the finishing, drop into pigment, water, auxiliary agent, with 900 rev/mins~1400 rev/mins stirring velocity high speed dispersion, the process sand mill is ground to the finished product water color ink less than 10 μ m at last.
CNB2005100109128A 2005-07-14 2005-07-14 Water printing ink using synthetic water solid acrylate resin as base material and its preparation method Expired - Fee Related CN100395295C (en)

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CN101284965B (en) * 2007-04-10 2011-09-07 樊官保 Water-based intaglio ink equal to plate engraving ink and uses thereof
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CN102220048A (en) * 2011-05-28 2011-10-19 谢亚军 Formula of environment friendly water-based ink for transfer printing and preparation method thereof
CN103396508B (en) * 2013-07-29 2016-01-13 华南理工大学 A kind of low-temperature self-crosslinking waterborne acrylic paint and preparation method thereof and application
CN103936910B (en) * 2013-12-03 2016-09-07 义乌市伟航水性油墨有限公司 The method of One-step production quick-dry type plastics water color ink acrylic resin binder
CN108530986A (en) * 2018-05-03 2018-09-14 清远市承明新材料科技有限公司 A kind of preparation method of food packaging water-based ink
CN109467975A (en) * 2018-10-12 2019-03-15 安徽徽合台智能科技有限公司 A kind of high temperature-resistant printing ink and preparation method thereof
CN111363405A (en) * 2018-12-25 2020-07-03 陈丽娟 Environment-friendly water-based printing ink and preparation method thereof
CN110358005B (en) * 2019-08-02 2021-09-10 山西省应用化学研究所(有限公司) Acrylic emulsion and preparation method thereof
CN111690293A (en) * 2020-05-27 2020-09-22 鹤山市科鼎功能材料有限公司 Resin for washable glass temporary protection ink and preparation method thereof
CN112194754B (en) * 2020-09-17 2022-06-24 广东德康化工实业有限公司 Water-based acrylic emulsion, water-based halftone printing ink and preparation method thereof
CN112280373A (en) * 2020-09-28 2021-01-29 江苏悦达印刷有限公司 Anti-oxidation fading printing ink and preparation method thereof
CN115819657A (en) * 2021-11-09 2023-03-21 湖南省硕泰高分子新材料有限公司 Synthesis process of water-based acrylic emulsion
CN114214004B (en) * 2021-12-23 2022-11-18 河南省科学院高新技术研究中心 Composite acrylic resin hot melt adhesive and preparation method thereof

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JP2002327137A (en) * 2001-04-27 2002-11-15 Dainippon Ink & Chem Inc Water-based ink composition
CN1447823A (en) * 2000-08-17 2003-10-08 巴斯福股份公司 Surface active random radical (CO) polymer and dispersion method for using same

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CN1447823A (en) * 2000-08-17 2003-10-08 巴斯福股份公司 Surface active random radical (CO) polymer and dispersion method for using same
JP2002327137A (en) * 2001-04-27 2002-11-15 Dainippon Ink & Chem Inc Water-based ink composition

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