CN104262526A - Water-dispersible quick-drying low-temperature self-crosslinked acrylate resin for inks and preparation method thereof - Google Patents
Water-dispersible quick-drying low-temperature self-crosslinked acrylate resin for inks and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-dispersible quick-drying low-temperature self-crosslinked acrylate resin for inks and a preparation method thereof. The water-dispersible quick-drying low-temperature self-crosslinked acrylate resin for inks is prepared by copolymerizing the following components in parts by mass: 12-20 parts of hard monomer, 12-20 parts of soft monomer, 4.5-10 parts of first-type hydrophilic monomer, 0.5-2.5 parts of second-type hydrophilic monomer, 0.6-2 parts of crosslinkable monomer, 0.3-0.6 part of initiator and 50-70 parts of solvent. A pH regulator is added to regulate the pH value to 7-8; and 30-60 parts of water is added as a dispersing agent. The ink prepared by using the water-dispersible acrylate resin as the connecting material can implement low-temperature (<50 DEG C) crosslinking curing, and has the advantages of short drying and curing time (the surface drying time is 25-50 seconds), excellent adhesive force (Grade 0) on low-polarity materials (PE (polyethylene) and PP (polypropylene) films), favorable staining power, favorable bonding resistance, favorable water resistance and favorable solvent resistance.
Description
Technical field
The present invention relates to a kind of ink acrylate resin technical field, be specifically related to a kind of aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin and preparation method thereof.
Background technology
Printing-ink, by binder resin, pigment, auxiliary agent and solvent composition, is widely used on wrapping material, and the solvent of its performance and use is determined by resin completely.Current printing-ink binder resin mostly is polyamide resin, Chlorinated Polypropylene III, urethane resin etc., these traditional solvent type inks have good sticking power and water-fast solvent resistance, but all using organic solvents such as benzene class, ketone, ester classes as thinner, because the volatilization of these organic solvents can cause serious atmospheric pollution in production and application process, be detrimental to health and ecotope, therefore various countries all work out and have promulgated that corresponding laws and regulations are with the use of restriction to such organic solvent; These solvents are all petroleum productss simultaneously, and because energy shortage causes oil price significantly to improve, these solvent prices also sharp rise, and this just causes the raising of production cost.Therefore develop environmental protection novel printing ink at a low price and there are good market outlook.
In wrapping material, the plastic basis material such as PE, PP is widely used because of advantages such as light weight good toughness, but is difficult to reach desirable printing effect due to characteristics such as its surface energy low heat resistant differences.Traditional solvent type ink can reach desirable printing effect, but due to organic solvent harm and to its use restriction will progressively be eliminated.Based on water-base resin ink in the environmental protection type resin ink occurred in market, it is using water as solvent, and surface tension is comparatively large, and the plastic bottom material surface energy such as PE, PP are lower, this water color ink is difficult to its complete wetting and reaches desirable sticking power, easily causes the defects such as film shrinkage cavity; And evaporation of water latent heat is high, the drying and forming-film time is long, especially under low temperature and high relative humidity condition, drying affects product use more slowly, can not meet in some service requirementss in particular cases, although improve the rate of drying that temperature can accelerate water color ink, but the plastic films such as PE, PP at high temperature can be Texturized, should not with the resin ink needing high temperature drying to solidify, the environment-friendlyink ink therefore developing quick-dry type low-temperature curing is significant.
Publication number is that the Chinese patent of CN101230125 discloses a kind of alcohol-soluble polyurethane soluble in water and preparation method thereof, but its water tolerance is poor; Publication number is that the Chinese patent of CN102127213 discloses a kind of waterborne acrylic alkyd resin and its preparation method and application, but its dry solidification film formation time is oversize can not meet coating specification; Publication number is that the Chinese patent of CN102140219 discloses a kind of water-base resin for plastic and its preparation method and application, a kind of water-base resin of plastics has been prepared by phase inversion, hardness enhanced water resistance is good, sticking power on PE, PP film is 1 grade, but the alcohol ethers wherein added and benzene class organic solvent cannot meet the requirement of environmental protection; Publication number is the polycomponent water-base resin that the United States Patent (USP) of US2007059503-A1 provides a kind of consumer electronics market plastic basis material, and VOC content is low, can form the good adhesion to multiple plastic basis material, but for the plastic basis material poor adhesive force of low polarity.Publication number is that the Chinese patent of CN103396508 discloses a kind of low-temperature self-crosslinking waterborne acrylic paint and preparation method thereof, as water-based ink resin binder, there is sticking power on the plastics films such as PE, PP, PO excellent, water-tolerant glossiness advantages of higher, but in its preparation process, use alcohol ether solvent and N, the organic solvents such as dinethylformamide, be unfavorable for production environmental protection, in reaction process, need underpressure distillation to take organic solvent away simultaneously, add operation steps thus add cost; And thoroughly cannot take organic solvent away, being mixed in this use water is the time adding dried coating film solidification in the product of solvent, and makes product in use have certain hazardness.Publication number is that the Chinese patent of CN103387637 discloses a kind of water-soluble self-crosslinking acrylic ester resin combination and preparation method thereof, level of residual monomers is low, resin again dissolubility is good, is applicable to print compound oil ink in OPP and require bad PET composite packaging and paper printing to combined strength bination.But in its resin preparation process, use chain-transfer agent tert-dodecyl mercaptan, not only poisonous, and there is foul smell, can impact construction worker and surrounding environment.The molecular resin amount that this invention is simultaneously prepared is less, and molecular weight distribution is comparatively wide, and molecular weight distribution index is comparatively large, can cause the mechanical property of resin coating film and water-fast solvent resistance poor.
Summary of the invention
The object of the invention is to the deficiency existed for existing aqueous printing ink soluble resin, provide a kind of ink low temperature rapid drying to solidify, there is the environmentally friendly water-dispersible acrylate resin of good sticking power and water-fast solvent resistance.
Another object of the present invention is the preparation method providing a kind of low-temperature self-crosslinking water-dispersed resin.
Object of the present invention is achieved through the following technical solutions:
A kind of aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin, in mass fraction, by 12 ~ 20 parts of hard monomers, 12 ~ 20 parts of soft monomers, 4.5 ~ 10 part of one class hydrophilic monomer, 0.5 ~ 2.5 part of two class hydrophilic monomer, 0.6 ~ 2 part of cross-linking monomer, 0.3 ~ 0.6 part of initiator, 50 ~ 70 parts of organic solvent copolymerization; Adding pH adjusting agent regulates pH to be 7 ~ 8, adds 30 ~ 60 parts of water as dispersion agent;
Described hard monomer is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Propenoic acid, 2-methyl, isobutyl ester, isobornyl methacrylate;
Described soft monomer be n-butyl acrylate, ethyl propenoate, Bing Xi Suan ?2 ?ethylhexyl ester, one or more in n-octyl;
A described class hydrophilic monomer is the acrylic monomer containing carboxyl;
Two described class hydrophilic monomers are the acrylic ester monomer containing hydroxyl;
Described cross-linking monomer be N ?n-methylolacrylamide, N ?hydroxyethyl acrylamide, diacetone-acryloamide(DAA), methyl vinyl ketone, methacrylic acid acetoxyl group ester, one or more in vinylformic acid acetoxyl group ester;
Described initiator is the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic solvent is the mixed solvent of ethanol and ethyl acetate;
Described pH adjusting agent is one or more in alkaline amine or Ammonia material;
During preparation, first the mixed solvent of ethanol and ethyl acetate is joined in reactor, stir and be warming up to 70 DEG C ~ 78 DEG C; Then hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer and initiator are mixed, be added drop-wise in reactor; Dropping terminates rear maintenance temperature of reaction and continues reaction 3.5 ~ 4 hours at 70 ~ 78 DEG C; Then drip pH adjusting agent, add water, discharging after stirring.
For realizing the object of the invention further, preferably, a class hydrophilic monomer is the one in vinylformic acid, methacrylic acid.
Two class hydrophilic monomers be Bing Xi Suan ?2 ?hydroxypropyl acrylate, Bing Xi Suan ?2 ?hydroxyl ethyl ester, Jia base Bing Xi Suan ?2 ?hydroxyl ethyl ester, Jia base Bing Xi Suan ?2 ?one in hydroxypropyl acrylate.
Ethanol and the ethyl acetate of described organic solvent to be mass ratio be 5:1 ~ 1:1 form.
Described pH adjusting agent be selected from thanomin, trolamine and ammoniacal liquor one or more.
The preparation method of described aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin, comprises the steps:
(1) add organic solvent in a kettle., stirring velocity is 250 ~ 300rpm, and is heated to 70 ~ 78 DEG C;
(2) hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer, initiator are at the uniform velocity added drop-wise in reactor after mixing, within 2.5 ~ 3 hours, dropwise;
(3), after liquid to be mixed dropwises, insulation reaction is continued 3.5 ~ 4 hours;
(4) stopped reaction be cooled to 35 ~ 45 DEG C after insulation reaction completes, adding pH adjusting agent regulates pH to be 7 ~ 8, the water taking calculated amount joins in reaction vessel, discharging after stirring, and obtains water dispersible quick-dry type low-temperature self-crosslinking acrylate resin.
Comonomer of the present invention is polymerized complete and directly adds dispersion agent water after adding pH adjusting agent in the mixed solvent of organic solvent ethanol, ethyl acetate, and need not distill or other operation removal organic solvents.
Organic solvent used in the present invention is the mixed solvent of ethanol and ethyl acetate, and wherein ethanol is important organic solvent, and preparation technology is simply ripe, cheap and easy to get, and quick-drying is nontoxic, has the title of " green solvent ", can with water with arbitrarily than miscible.Ethyl acetate is that one has excellent solubility and drip-dry organic solvent, can be miscible with ethanol, has fruit aroma and is present in the long-time beverage wine placed, belonging to innoxious solvent.Ethanol evaporation latent heat is little, rapidly dry, not by humidity effect.The surface tension of dehydrated alcohol under 25 DEG C of conditions is 21.82mNm
-1, the surface tension of the aqueous ethanolic solution of massfraction 60% is 26.23mNm
-1, the surface tension of the aqueous ethanolic solution of massfraction 30% is 32.98mNm
-1, the surface tension of ethyl acetate under 25 DEG C of conditions is 23.39mNm
-1, all far below the surface tension 72.01mNm of the water under 25 DEG C of conditions
-1, and the surface tension of PE, PP plastics film is about 31mNm
-1, according to Young equation:
moisten contact angle can be tried to achieve from surface tension, liquid low surface tension force can reduce moisten contact angle, improve wetting efficiency, therefore making the resin of solvent with the mixed solvent of ethanol, ethyl acetate and the ethanol of certain mass mark, the aqueous solution of ethyl acetate mixed solvent can complete wetting PE, PP substrate surface thus for increase film is to the sticking power of material surface.
Chain transfer due to ethanol can reduce the molecular weight of synthetic resins, by adding ethyl acetate as solubility promoter in the present invention, the chain transfer of molecular resin can be reduced, simultaneously by suitably reducing initiator amount, reducing temperature of reaction, suitably increasing the acrylate resin that the condition acquisitions such as monomer dropping speed have desired molecular weight, ensure that and be coated with the film-forming properties in membrane process.The resin number-average molecular weight obtained in the present invention is between 30000 ~ 40000.
Simultaneously, the boiling point of ethanol and ethyl acetate is respectively 78.4 DEG C and 77 DEG C, belong to the quick-drying solvent that lower boiling volatilizees fast, therefore by regulating the ratio of organic solvent ethanol, ethyl acetate and water can obtain rate of drying low-temperature self-crosslinking acrylate resin faster.
The comonomer adopted in the present invention is acrylic ester monomer, and the content of the hydrophilic monomer in comonomer can ensure the water-soluble of prepared acrylic resin; By introducing crosslinkable group in the copolymer, crosslinking reaction can not be there is in the aqueous solution of ethanol, ethyl acetate mixed solvent and ethanol, ethyl acetate mixed solvent under alkaline condition, and can be dissolved in the aqueous solution of ethanol, ethyl acetate mixed solvent and ethanol, ethyl acetate mixed solvent completely, keep good preservation stability, molecular resin is in the molecule in unfolding structure simultaneously, can ensure the wettability good to ground; And in use with the volatilization of etoh solvent, ethyl acetate, water and neutralizing agent ammoniacal liquor, system is slightly acidic thus crosslinking reaction formation reticulated structure film-forming occurs, thus significantly improve the thermotolerance of resin and water-fast solvent resistance, simultaneously due to the generation of crosslinking reaction in film-forming process, the reactive force between molecular resin and ground is strengthened thus is greatly improved the sticking power of ink resin.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
(1) organic solvent in preparation process of the water dispersible quick-dry type low-temperature self-crosslinking acrylate resin prepared by the present invention adopts the mixed solvent of ethanol and ethyl acetate, evaporation rate is fast, there is slight fruit aroma, there is no irritating smell, can not produce deleterious effect to humans and animals, be a kind of environmentally friendly resin.
(2) there is carboxyl, hydroxyl, amide group isopolarity group in the water dispersible quick-dry type low-temperature self-crosslinking acrylate resin prepared by the present invention, molecular weight is moderate, can mix with the water of arbitrary proportion.
(3) the water dispersible quick-dry type low-temperature self-crosslinking acrylate resin prepared by the present invention (<50 DEG C) rapid drying (25s ~ 50s) reaction can form dry solidification, the ground being particularly useful for non-refractory and the environment needing rapid drying to solidify that reticulated structure realizes ink film at low temperatures.
(4) the water dispersible low-temperature self-crosslinking acrylate resin prepared by the present invention has good water-fast solvent resistance, test its degree of crosslinking by acetone infusion method and reach 89.5%, after the ink film immersion 24h prepared by this water dispersible low-temperature self-crosslinking acrylate resin, water is unstained, and wiping is not faded or only slightly faded.
(5) ink prepared as ink adhesive and aqueous color paste, deionized water, defoamer of the water dispersible low-temperature self-crosslinking acrylate resin prepared by the present invention at the ground of low polarity as PE, PP having good sticking power, sticking power on PE ground reaches 0 grade, and the sticking power on PP ground reaches 0 grade.
(6) production technique of the present invention is simple, and gained resin price lower performance is good, easy construction, can regulate the ratio of soft monomer in resin, hard monomer according to actual needs; The ratio of one class hydrophilic monomer, two class hydrophilic monomers; The ratio of etoh solvent, ethyl acetate and water, with the product needed for obtained different environment for use and different ground, has adaptability and using value widely.Obtained required water color ink stir 15 ~ 30min after obtained water dispersible quick-dry type low-temperature self-crosslinking acrylic resin mixes with aqueous color paste, defoamer under the rotating speed of 200 ~ 300rpm after, simple and convenient easy handling.
Accompanying drawing explanation
Fig. 1 is the infared spectrum that water dispersible low-temperature self-crosslinking acrylate resin before and after crosslinking reaction occurs, and wherein a represents the water-dispersible acrylate resin occurred after crosslinking reaction, and b represents the water-dispersible acrylate resin that crosslinking reaction does not occur.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but the scope of protection of present invention does not limit to the scope expressed with embodiment.
Water dispersible quick-dry type low-temperature self-crosslinking acrylic resin prepared by various embodiments of the present invention and the ink product testing method that configures are according to following standard testing
Second-order transition temperature: ASTM D6604-2000 (2009) e1
Solid content: GB/T2973-1995
Tinting strength: GBT 13217.6-2009
Resistance to blocking: GBT 13217.8-2009
Solvent resistance test: by resin coating film regular for size dry constant weight in 80 DEG C of baking ovens, weigh after taking-up m
0, afterwards film is immersed 24h in acetone, then takes out the m that to weigh after drying in 80 DEG C of baking ovens
1, solvent resistance is with degree of crosslinking
represent.
Surface drying time: fingers-touch method, touches ink pellet surface with finger, and without stickiness, sticking without ink is being surface drying on hand
Water resistance test: by ink on ground after film 50 DEG C dry 20min, dried film removes the part of edge thickness inequality, is cut into long 10cm, the testing bar of wide 3cm, is placed in 25 DEG C, water and soaks 24h, observe water staining conditions and wipe out pornographic condition
Sticking power is tested: by ink on ground after film 50 DEG C dry 20min, be bonded at ink-printed surface with 3M adhesive tape, with the pressure roller of certain loading roll extrusion above 3 times, adhesive tape is opened according to the method for test 180 ° of stripping strengths, test its sticking power, specify that 0 grade is best, 5 grades is the poorest
Embodiment 1
Get 50g ethanol, the mixed solvent of 10g ethyl acetate is added in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, and is heated to 75 DEG C and keeps backflow 10min; 16g methyl methacrylate, 16g butyl acrylate, 6g vinylformic acid, 2g 2-hydroxypropyl acrylate, 1.2g diacetone-acryloamide(DAA), 0.4g Diisopropyl azodicarboxylate are mixed, be added drop-wise in flask by 60mL constant pressure funnel after diacetone-acryloamide(DAA) and Diisopropyl azodicarboxylate dissolve, within 2.5 hours, dropwise; React 4 hours at such a temperature after dropping terminates, then cool to 40 DEG C, in flask, drip 2-3mL ammoniacal liquor, continue to stir; Taking 40g water joins in flask, continues to stir 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate resin is semi-transparent clear thick liquid, has no irritating odor, stable storing, second-order transition temperature 15 DEG C, solid content 29%, tinting strength 100%, anti-caking 0%, solvent resistance 89.65%.The solvent volatilized in drying varniss solidification process is the mixed solvent of water, ethanol, ethyl acetate, can not cause environmental pollution and infringement HUMAN HEALTH.
Get water dispersible low-temperature self-crosslinking acrylate resin prepared by 70g, 20g aqueous color paste, 0.15g defoamer BYK ?016 to be added to successively in reactor, disperse 30min under the rotating speed of 300rpm, after stirring, namely obtain required water color ink.
After testing, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is not faded, and 30 DEG C of surface drying time 35s, do solid work 30min set time, does solid work 11min set time for 50 DEG C, and on PE ground, sticking power is 0 grade, and on PP ground, sticking power is 0 grade.The preparation of resin selects the mixed solvent of ethanol and ethyl acetate as reaction solvent, and makes resin have suitable molecular weight by suitable processing condition, also can realize rapid drying after adding water-dispersion simultaneously.Introduce room-temperature self crosslinking system can realize the fast setting of paint film and obtain good water-fast solvent resistance and sticking power good on PE/PP film.
Fig. 1 is under 30 DEG C of conditions, the infrared spectra comparison diagram before and after crosslinking reaction occurs.A represents the water-dispersible acrylate resin occurred after crosslinking reaction, and b represents the water-dispersible acrylate resin that crosslinking reaction does not occur.Contrast with b, in a, the N-H flexural vibration absorption peak of 1543cm-1 place amide group disappears, and occurs the stretching vibration absorption peak of hydrazone-N=C-double bond at 1655cm-1 place, illustrates to there occurs crosslinking reaction under 30 DEG C of conditions.
Embodiment 2
The mixed solvent getting 40g ethanol and 10g ethyl acetate is added in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, and is heated to 73 DEG C and keeps backflow 10min; 20g β-dimethyl-aminoethylmethacrylate, 20g ethyl propenoate, 7.5g methacrylic acid, 2.5g vinylformic acid-2-hydroxyl ethyl ester, 1g diacetone-acryloamide(DAA), 0.5g Diisopropyl azodicarboxylate are mixed, be added drop-wise in flask by 60mL constant pressure funnel after diacetone-acryloamide(DAA) and Diisopropyl azodicarboxylate dissolve, within 3 hours, dropwise; React 4 hours at such a temperature after dropping terminates, then cool to 40 DEG C, in flask, drip 4-5mL ammoniacal liquor, continue to stir; Taking 50g water joins in flask, continues to stir 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate resin is semi-transparent clear thick liquid, has no irritating odor, stable storing, second-order transition temperature 16 DEG C, solid content 31%, tinting strength 100%, anti-caking 0%, solvent resistance 87.52%.
Get water dispersible low-temperature self-crosslinking acrylate resin prepared by 70g, 25g aqueous color paste, 0.15g defoamer BYK ?016 to be added to successively in reactor, disperse 30min under the rotating speed of 300rpm, after stirring, namely obtain required water color ink.
After testing, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is slightly faded, and 30 DEG C of surface drying time 45s, do solid work 34min set time, does solid work 13min set time for 50 DEG C, and on PE ground, sticking power is 1 grade, and on PP ground, sticking power is 0 grade.
Embodiment 3
Get the mixed solvent of 40g ethanol and 30g ethyl acetate, be added in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, be heated to 72 DEG C and keep backflow 15min; By 15g β-dimethyl-aminoethylmethacrylate, 9g Bing Xi Suan ?2 ?ethylhexyl ester, 4.5g methacrylic acid, 1.5g 2-hydroxypropyl acrylate, 0.6g N ?n-methylolacrylamide, 0.3g Diisopropyl azodicarboxylate mix, until N ?n-methylolacrylamide and Diisopropyl azodicarboxylate dissolve after be added drop-wise in flask by 60mL constant pressure funnel, within 2.5 hours, dropwise; React 3.5 hours at such a temperature after dropping terminates, then cool to 40 DEG C, in flask, drip 2-3mL trolamine, continue to stir; Taking 30g water joins in flask, continues to stir 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate resin is semi-transparent clear thick liquid, has no irritating odor, stable storing, second-order transition temperature 29 DEG C, solid content 23%, tinting strength 99%, anti-caking 0.5%, solvent resistance 86.24%.
Get water dispersible low-temperature self-crosslinking acrylate resin prepared by 70g, 30g aqueous color paste, 0.2g defoamer BYK ?016 to be added to successively in reactor, disperse 25min under the rotating speed of 250rpm, after stirring, namely obtain required water color ink.
After testing, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is slightly faded, 30 DEG C of surface drying time 25s, do solid work 28min set time, do solid work 10min set time for 50 degrees Celsius, on PE ground, sticking power is 1 grade, and on PP ground, sticking power is 0 grade.
Embodiment 4
The mixed solvent getting 50g ethanol and 15g ethyl acetate is added in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, and is heated to 75 DEG C and keeps backflow 10min; 16g Propenoic acid, 2-methyl, isobutyl ester, 12g ethyl propenoate, 5.5g vinylformic acid, 1.5g Hydroxypropyl methacrylate, 1.4g diacetone-acryloamide(DAA), 0.4g Diisopropyl azodicarboxylate are mixed, be added drop-wise in flask by 60mL constant pressure funnel after diacetone-acryloamide(DAA) and Diisopropyl azodicarboxylate dissolve, within 3 hours, dropwise; React 4 hours at such a temperature after dropping terminates, then cool to 40 DEG C, in flask, drip 3-4mL ammoniacal liquor, continue to stir; Taking 40g water joins in flask, continues to stir 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate resin is semi-transparent clear thick liquid, has no irritating odor, stable storing, second-order transition temperature 30 DEG C, solid content 26%, tinting strength 100%, anti-caking 0%, solvent resistance 89.27%.
Get water dispersible low-temperature self-crosslinking acrylate resin prepared by 70g, 10g aqueous color paste, 0.1g defoamer BYK ?016 to be added to successively in reactor, disperse 25min under the rotating speed of 300rpm, after stirring, namely obtain required water color ink.
After testing, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is not faded, and 30 DEG C of surface drying time 30s, do solid work 26min set time, does solid work 10min set time for 50 DEG C, and on PE ground, sticking power is 0 grade, and on PP ground, sticking power is 0 grade.
Embodiment 5
Get 35g ethanol, the mixed solvent of 35g ethyl acetate is added in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, and is heated to 73 DEG C and keeps backflow 10min; By 12g methyl methacrylate, 13g butyl acrylate, 5g methacrylic acid, 0.9g N ?hydroxyethyl acrylamide, 0.3g Diisopropyl azodicarboxylate mix, until N ?hydroxyethyl acrylamide and Diisopropyl azodicarboxylate dissolve after be added drop-wise in flask by 60mL constant pressure funnel, within 3 hours, dropwise; React 3.5 hours at such a temperature after dropping terminates, then cool to 40 DEG C, in flask, drip 3-4mL thanomin, continue to stir; Taking 30g water joins in flask, continues to stir 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylic resin is semi-transparent clear thick liquid, has no irritating odor, stable storing, second-order transition temperature 22 DEG C, solid content 24%, tinting strength 98%, anti-caking 1%, solvent resistance 87.42%.
Get water dispersible low-temperature self-crosslinking acrylate resin prepared by 70g, 30g aqueous color paste, 0.15g defoamer BYK ?016 to be added to successively in reactor, disperse 30min under the rotating speed of 250rpm, after stirring, namely obtain required water color ink.
After testing, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is slightly faded, and 30 DEG C of surface drying time 34s, do solid work 35min set time, does solid work 15min set time for 50 DEG C, and on PE ground, sticking power is 1 grade, and on PP ground, sticking power is 1 grade.
Comparative example: process for preparing resins is selected from the Chinese patent embodiment 1 that publication number is CN103396508, ink preparation method and testing method are by the method for the invention.
A 30g ethylene glycol monomethyl ether and 20g N, N ?dimethyl formamide join in band reflux exchanger reactor by (), stir and be warming up to 60 DEG C, obtaining mixed solvent after reflux stabilizes;
(b) by 4g vinylbenzene, 15g methyl methacrylate, 21g ethyl propenoate, 4g vinylformic acid, 2g Hydroxyethyl acrylate, 1g N ?n-methylolacrylamide, 1g diacetone-acryloamide(DAA) and 0.6g Diisopropyl azodicarboxylate join in stirring tank, stir and after solid particulate dissolves completely, obtain mixing raw material in 30 minutes;
C mixing raw material in step a reactor is warming up to 70 DEG C by (), after reflux stabilizes, by the mixing raw material instillation reactor in step b, control temperature is at 70 ~ 75 DEG C, and time for adding is 3.5 hours;
D () dropwises after, maintain the temperature at 75 DEG C, react 1 hour;
E () insulation terminates after, underpressure distillation is carried out to obtained crude propylene acid ester resin, extracts unreacted monomer and most of solvent;
F () underpressure distillation terminates after, be cooled to 45 DEG C;
G () drips 4g triethylamine and regulates resin pH value to 7.5 ~ 8.0, add 70g water, maintain the temperature at 45 DEG C, stir 30 minutes, cool the temperature to 40 DEG C, discharging after resin is completely water-soluble.
Gained low-temperature self-crosslinking water-borne acrylic resin is the micro-yellow thick liquid of semi-transparent clear, have no irritating odor, a little alcohol ether solvent is had to volatilize in drying varniss solidification process, second-order transition temperature 30 DEG C, solid content 21%, tinting strength 100%, anti-caking 0%, ink water-resistance property of coating immersion after 24 hours water be unstained, wiping is slightly faded, 30 DEG C of surface drying time 134s, do solid work 110min set time, do solid work 40min set time for 50 DEG C, on PE ground, sticking power is 1 grade, and on PP ground, sticking power is 0 grade.
Claims (6)
1. aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin, it is characterized in that, in mass fraction, by 12 ~ 20 parts of hard monomers, 12 ~ 20 parts of soft monomers, 4.5 ~ 10 part of one class hydrophilic monomer, 0.5 ~ 2.5 part of two class hydrophilic monomer, 0.6 ~ 2 part of cross-linking monomer, 0.3 ~ 0.6 part of initiator, 50 ~ 70 parts of organic solvent copolymerization; Adding pH adjusting agent regulates pH to be 7 ~ 8, adds 30 ~ 60 parts of water as dispersion agent;
Described hard monomer is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Propenoic acid, 2-methyl, isobutyl ester, isobornyl methacrylate;
Described soft monomer be n-butyl acrylate, ethyl propenoate, Bing Xi Suan ?2 ?ethylhexyl ester, one or more in n-octyl;
A described class hydrophilic monomer is the acrylic monomer containing carboxyl;
Two described class hydrophilic monomers are the acrylic ester monomer containing hydroxyl;
Described cross-linking monomer be N ?n-methylolacrylamide, N ?hydroxyethyl acrylamide, diacetone-acryloamide(DAA), methyl vinyl ketone, methacrylic acid acetoxyl group ester, one or more in vinylformic acid acetoxyl group ester;
Described initiator is the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic solvent is the mixed solvent of ethanol and ethyl acetate;
Described pH adjusting agent is one or more in alkaline amine or Ammonia material;
During preparation, first the mixed solvent of ethanol and ethyl acetate is joined in reactor, stir and be warming up to 70 DEG C ~ 78 DEG C; Then hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer and initiator are mixed, be added drop-wise in reactor; Dropping terminates rear maintenance temperature of reaction and continues reaction 3.5 ~ 4 hours at 70 ~ 78 DEG C; Then drip pH adjusting agent, add water, discharging after stirring.
2. a kind of aqueous printing ink according to claim 1 dispersed quick-dry type low-temperature self-crosslinking acrylate resin, is characterized in that: a class hydrophilic monomer is the one in vinylformic acid, methacrylic acid.
3. a kind of aqueous printing ink according to claim 1 dispersed quick-dry type low-temperature self-crosslinking acrylate resin, is characterized in that: two class hydrophilic monomers be Bing Xi Suan ?2 ?hydroxypropyl acrylate, Bing Xi Suan ?2 ?hydroxyl ethyl ester, Jia base Bing Xi Suan ?2 ?hydroxyl ethyl ester, Jia base Bing Xi Suan ?2 ?one in hydroxypropyl acrylate.
4. a kind of aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin according to claim 1, is characterized in that: ethanol and the ethyl acetate of described organic solvent to be mass ratio be 5:1 ~ 1:1 form.
5. a kind of aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin according to claim 1, is characterized in that: described pH adjusting agent be selected from thanomin, trolamine and ammoniacal liquor one or more.
6. according to claim 1 ?the preparation method of aqueous printing ink dispersed quick-dry type low-temperature self-crosslinking acrylate resin described in 5 any one, it is characterized in that: comprise the steps:
(1) add organic solvent in a kettle., stirring velocity is 250 ~ 300rpm, and is heated to 70 ~ 78 DEG C;
(2) hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer, initiator are at the uniform velocity added drop-wise in reactor after mixing, within 2.5 ~ 3 hours, dropwise;
(3), after liquid to be mixed dropwises, insulation reaction is continued 3.5 ~ 4 hours;
(4) stopped reaction be cooled to 35 ~ 45 DEG C after insulation reaction completes, adding pH adjusting agent regulates pH to be 7 ~ 8, the water taking calculated amount joins in reaction vessel, discharging after stirring, and obtains water dispersible quick-dry type low-temperature self-crosslinking acrylate resin.
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| CN106117407A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Ambient self cross-linkable acrylic emulsion and preparation method thereof |
| CN108148157A (en) * | 2018-01-31 | 2018-06-12 | 南雄市翔远化学科技有限公司 | A kind of water solubility low-temperature self-crosslinking acrylic resin and preparation method thereof |
| CN108752533A (en) * | 2018-06-08 | 2018-11-06 | 常熟国和新材料有限公司 | A kind of preparation method of ink resin |
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| CN106117407A (en) * | 2016-07-28 | 2016-11-16 | 上海维凯光电新材料有限公司 | Ambient self cross-linkable acrylic emulsion and preparation method thereof |
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