CN104262526B - Aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate and preparation method thereof - Google Patents
Aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate and preparation method thereof.In terms of mass fraction, this resin is 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 solvent copolymerization form, and being subsequently adding pH adjusting agent regulation pH is 7～8, adds 30～60 parts of water as dispersant.Low temperature (< 50 DEG C) crosslinking curing can be realized as the ink that binder is prepared by this water-dispersible acrylate resin, and the dry solidification time short (surface drying time 25s～50s), low polar material PE, PP film has the adhesive force (0 grade) of excellence, there is good tinting strength, tinting power, anti-caking and water-fast solvent resistance.
Description
Technical field
The present invention relates to a kind of ink acrylate technical field, be specifically related to a kind of aqueous printing ink dispersibility quick-dry type
Low-temperature self-crosslinking acrylate and preparation method thereof.
Background technology
Printing-ink is made up of binder resin, pigment, auxiliary agent and solvent, is widely used on packaging material, its performance
And the solvent used is determined by resin completely.At present printing-ink binder resin mostly be polyamide, chlorinated polypropylene,
Polyurethane resin etc., these traditional solvent type inks have good adhesive force and a water-fast solvent resistance, but all with benzene class,
The organic solvent such as ketone, esters is as diluent, and during production and application, the volatilization due to these organic solvents can cause sternly
The air pollution of weight, is detrimental to health and ecological environment, and therefore various countries all work out and promulgated that corresponding laws and regulations are to limit
Use to such organic solvent；These solvents are all oil products simultaneously, owing to energy shortage causes oil price significantly to carry
Height, these solvent prices also sharp rise, and this has resulted in the raising of production cost.Therefore exploitation environmental protection novel print at a low price
Brush ink has good market prospect.
In packaging material, the plastic basis material such as PE, PP is widely used because of advantages such as light weight good toughness, but owing to its surface can be low resistance to
The characteristics such as hot difference are difficult to reach preferable printing effect.Traditional solvent type ink can reach preferable printing effect, but by
To be phased out in the harm of organic solvent and the restriction that is used for.With water in the environmental protection type resin ink occurred in market
Property resin ink be main, it is using water as solvent, and surface tension is relatively big, and the plastic bottom material surfaces such as PE, PP can be relatively low, should
Water color ink is difficult to its complete wetting is reached preferable adhesive force, easily causes the defects such as film shrinkage cavity；And the steaming of water
Sending out latent heat high, the drying and forming-film time is long, and being especially dried under the conditions of low temperature and high relative humidity affects product use more slowly, it is impossible to meet
Some use requirements in particular cases, although improve temperature and can accelerate the rate of drying of water color ink, but PE, PP etc. mould
Material film at high temperature can be Texturized, should not be with the resin ink needing high temperature drying to solidify, therefore exploitation quick-dry type low-temperature setting
Environment-friendlyink ink significant.
The Chinese patent of Publication No. CN101230125 discloses a kind of alcohol-soluble polyurethane soluble in water and preparation side thereof
Method, but its resistance to water is poor；The Chinese patent of Publication No. 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 No.
The Chinese patent of CN102140219 discloses a kind of water-base resin for plastic and its preparation method and application, passes through phase inversion
Being prepared for the water-base resin of a kind of plastics, hardness enhanced water resistance is good, and the adhesive force on PE, PP film is 1 grade, but its
The alcohol ethers of middle addition and benzene class organic solvent cannot meet the requirement of environmental protection；The U.S. of Publication No. US2007059503-A1
Patent provides the multicomponent water-base resin of a kind of consumer electronics market plastic basis material, and VOC content is low, can be formed multiple
The good adhesion of plastic basis material, but for the plastic basis material poor adhesive force of low polarity.In Publication No. CN103396508
State's patent discloses a kind of low-temperature self-crosslinking waterborne acrylic paint and preparation method thereof, as water-based ink resin binder,
There is adhesive force on the plastic sheetings such as PE, PP, PO excellent, water-tolerant glossiness advantages of higher, but prepared at it
Journey is used the organic solvents such as alcohol ether solvent and DMF, is unfavorable for producing environmental protection, simultaneously in course of reaction
In need reduce pressure distillation take organic solvent away, add operating procedure thus add cost；And cannot thoroughly take away organic
Solvent, be mixed in this with the product that water is solvent adds time of dried coating film solidification, and make product in use
There is certain hazardness.The Chinese patent of Publication No. CN103387637 discloses a kind of water solublity self-crosslinking acrylic ester tree
Oil/fat composition and preparation method thereof, level of residual monomers is low, and resin dissolubility again is good, it is adaptable to print compound oil ink in OPP and to multiple
Close the bad PET composite packaging of requirement of strength and paper printing.But during its resin-made is standby, use chain-transferring agent uncle 12
Mercaptan, the most poisonous, and there is foul smell, construction worker and surrounding can be impacted.Prepared by this invention simultaneously
The molecular resin amount gone out is less, and molecular weight distribution is relatively wide, and molecular weight distribution index is relatively big, can cause the mechanicalness of resin coating film
Can be poor with water-fast solvent resistance.
Summary of the invention
Present invention aims to the deficiency that existing aqueous printing ink soluble resin exists, it is provided that a kind of ink low temperature is quick
Dry solidification, there is the environmentally friendly water-dispersible acrylate resin of good adhesive force and water-fast solvent resistance.
Further object is that the preparation method that a kind of low-temperature self-crosslinking water-dispersed resin is provided.
The purpose of the present invention is achieved through the following technical solutions:
A kind of aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate is in terms of mass fraction, hard by 12～20 parts
Monomer, 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 crosslinking
Monomer, 0.3～0.6 part of initiator, 50～70 parts of organic solvent copolymerization；Adding pH adjusting agent regulation pH is 7～8, adds 30～60
Part water is as dispersant；
Described hard monomer is methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, methacrylic acid
One or more in isobornyl thiocyanoacetate；
Described soft monomer is in n-butyl acrylate, ethyl acrylate, acrylic acid 2 ethylhexyl ester, n-octyl
One or more；
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 is N n-methylolacrylamide, N hydroxyethyl acrylamide, N-[2-(2-methyl-4-oxopentyl), ethylene methacrylic
One or more in base ketone, methacrylic acid acetoxyl group ester, acrylic acid acetoxyl group ester；
Described initiator is the one in azodiisobutyronitrile, 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 alkalescence 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 by hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer and initiator mix homogeneously, drip
It is added in reactor；Reaction temperature is kept to continue reaction 3.5～4 hours at 70～78 DEG C after completion of dropwise addition；Then dropping pH adjusts
Joint agent, adds water, discharging after stirring.
For realizing the object of the invention further, it is preferable that a class hydrophilic monomer is the one in acrylic acid, methacrylic acid.
Two class hydrophilic monomers are acrylic acid 2 hydroxypropyl acrylate, acrylic acid 2 hydroxyl ethyl ester, methacrylic acid 2 hydroxyl ethyl ester, metering system
One in acid 2 hydroxypropyl acrylates.
Described organic solvent be mass ratio be that ethanol and the ethyl acetate of 5:1～1:1 forms.
One or more in ethanolamine, triethanolamine and ammonia of described pH adjusting agent.
The preparation method of described aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate, comprises the steps:
(1) adding organic solvent in a kettle., mixing speed is 250～300rpm, and is heated to 70～78 DEG C；
(2) by hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer, initiator mix homogeneously
After be at the uniform velocity added drop-wise in reactor, 2.5～3 hours dropping complete；
(3) after drop to be mixed adds, continuation insulation reaction 3.5～4 hours；
(4) stopped reaction be cooled to 35～45 DEG C after insulation reaction completes, adding pH adjusting agent regulation pH is 7～8,
The water weighing amount of calculation joins in reaction vessel, discharging after stirring, and obtains water dispersible quick-dry type low-temperature self-crosslinking third
Alkene acid ester resin.
Comonomer of the present invention organic solvent ethanol, ethyl acetate mixed solvent in be polymerized complete and after adding pH adjusting agent
It is directly added into dispersant water, and need not distill or other operation removal organic solvents.
The mixed solvent that organic solvent is ethanol and ethyl acetate used in the present invention, wherein ethanol is important organic solvent,
Preparation technology is the most ripe, cheap and easy to get, quick-drying nontoxic, has the title of " green solvent ", can be miscible with arbitrarily ratio with water.
Ethyl acetate is that one has excellent solubility and drip-dry organic solvent, can be miscible with ethanol, has fruit aroma and deposits
It is in the beverage wine placed for a long time, belongs to innoxious solvent.Ethanol evaporation latent heat is little, is dried rapidly, is not affected by humidity.
Dehydrated alcohol surface tension under the conditions of 25 DEG C is 21.82mN m-1, the surface tension of the ethanol water of mass fraction 60%
For 26.23mN m-1, the surface tension of the ethanol water of mass fraction 30% is 32.98mN m-1, ethyl acetate is 25
Surface tension under the conditions of DEG C is 23.39mN m-1, all far below 25 DEG C under the conditions of the surface tension 72.01mN m of water-1,
And the surface tension of PE, PP plastic sheeting is about 31mN m-1, according to Young equation:Can be from table
Surface tension tries to achieve wetting contact angle, and liquid low surface tension force can reduce wetting contact angle, improves wetting efficiency, therefore with ethanol,
The mixed solvent of ethyl acetate and the aqueous solution of the ethanol of certain mass mark, ethyl acetate mixed solvent make the resin energy of solvent
Enough complete wetting PE, PP substrate surface thus for increasing the film adhesive force to material surface.
Chain transfer due to ethanol can reduce the molecular weight of synthetic resin, by adding ethyl acetate as helping in the present invention
Solvent, can reduce the chain transfer of molecular resin, simultaneously by suitably reduce initiator amount, reduce reaction temperature,
Suitably increase the conditions such as monomer dropping speed and obtain the acrylate with desired molecular weight, it is ensured that during film
Film property.Resin number-average molecular weight obtained in the present invention is between 30000～40000.
Meanwhile, the boiling point of ethanol and ethyl acetate is respectively 78.4 DEG C and 77 DEG C, belongs to the quick-drying solvent that low boiling volatilization is fast,
Therefore rate of drying low-temperature self-crosslinking propylene faster can be obtained by regulation organic solvent ethanol, ethyl acetate with the ratio of water
Acid ester resin.
Comonomer employed in the present invention is acrylic ester monomer, and the content of the hydrophilic monomer in comonomer can be protected
The water solublity of the acrylic resin prepared by card；By introducing crosslinkable group in the copolymer, under the conditions of alkalescence ethanol,
Ethyl acetate mixed solvent and ethanol, ethyl acetate mixed solvent aqueous solution in will not crosslink reaction, and can be completely
Being dissolved in the aqueous solution of ethanol, ethyl acetate mixed solvent and ethanol, ethyl acetate mixed solvent, the storage keeping good is steady
Qualitative, molecular resin is in the molecule in unfolding structure simultaneously, can guarantee that the wettability good to ground；And in use
With etoh solvent, ethyl acetate, water and the volatilization of nertralizer ammonia, system is faintly acid thus crosslinks reaction shape
Reticulate Structured cured film forming, thus the thermostability of resin and water-fast solvent resistance are greatly improved, simultaneously because at film-forming
During the generation of cross-linking reaction, the active force between molecular resin and ground is strengthened thus is greatly improved the attachment of ink resin
Power.
The present invention compared with prior art, has the advantage that and beneficial effect:
(1) the water dispersible quick-dry type low-temperature self-crosslinking acrylate organic solvent in preparation process prepared by the present invention
Using the mixed solvent of ethanol and ethyl acetate, evaporation rate is fast, has slight fruit aroma, does not has penetrating odor, will not
Humans and animals is produced illeffects, is a kind of environmentally friendly resin.
(2) there is carboxyl, hydroxyl, amide in the water dispersible quick-dry type low-temperature self-crosslinking acrylate prepared by the present invention
Base isopolarity group, molecular weight is moderate, can mix with the water of arbitrary proportion.
(3) the water dispersible quick-dry type low-temperature self-crosslinking acrylate prepared by the present invention can at low temperatures (< 50 DEG C)
Rapid draing (25s～50s) reaction forms network structure and realizes the dry solidification of ink film, is particularly suited for the end of non-refractory
Material and need the environment that rapid draing solidifies.
(4) the water dispersible low-temperature self-crosslinking acrylate prepared by the present invention has good water-fast solvent resistance, uses
Acetone soak method is tested its degree of cross linking and is reached 89.5%, the ink prepared by this water dispersible low-temperature self-crosslinking acrylate
After film immersion 24h, water is unstained, and wiping is not faded or the most slightly fades.
(5) the water dispersible low-temperature self-crosslinking acrylate prepared by the present invention as ink adhesive and aqueous color paste,
Ink prepared by deionized water, defoamer has good adhesive force on the ground such as PE, PP of low polarity, at PE ground
On adhesive force reach 0 grade, the adhesive force on PP ground reaches 0 grade.
(6) production technology of the present invention is simple, and gained resin price low performance is good, and easy construction can be adjusted according to actual needs
Soft monomer, the ratio of hard monomer in joint resin；One class hydrophilic monomer, the ratio of two class hydrophilic monomers；Etoh solvent, acetic acid
Ethyl ester and the ratio of water, use the products needed for environment and different grounds with prepared difference, have wider adaptability and answer
By value.Obtained water dispersible quick-dry type low-temperature self-crosslinking acrylic resin mix with aqueous color paste, defoamer after
Required water color ink is prepared after stirring 15～30min under the rotating speed of 200～300rpm, simple and convenient easily operated.
Accompanying drawing explanation
Fig. 1 is to crosslink the infared spectrum of water dispersible low-temperature self-crosslinking acrylate before and after reaction, and wherein a represents
Crosslinking the water-dispersible acrylate resin after reaction, b represents the water-dispersible acrylic's ester not crosslinking reaction
Resin.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the scope of protection of present invention is not limited to and embodiment
The scope expressed.
Water dispersible quick-dry type low-temperature self-crosslinking acrylic resin prepared by various embodiments of the present invention and the ink product configured are surveyed
Method for testing is according to following standard testing
Vitrification point: ASTM D6604-2000 (2009) e1
Solid content: GB/T2973-1995
Tinting strength, tinting power: GBT 13217.6-2009
Resistance to blocking: GBT 13217.8-2009
Solvent resistance test: resin coating film regular for size is dried in 80 DEG C of baking ovens constant weight, and weigh after taking-up m0, afterwards will
Film immerses 24h in acetone, then takes out the m that weighs after drying in 80 DEG C of baking ovens1, solvent resistance is with the degree of cross linking
Represent.
Surface drying time: fingers-touch method, touches ink pellet surface with finger, without stickiness, sticks on hand for surface drying without ink
Water resistance test: by ink on ground after film 50 DEG C dry 20min, dried film removes edge thickness not
Equal part, is cut into long 10cm, the testing bar of wide 3cm, is placed in water 25 DEG C and soaks 24h, observes water staining conditions and wiping
Wipe the situation of fading
Adhesive force test: by ink on ground after film 50 DEG C dry 20min, be bonded at ink-printed surface with 3M adhesive tape,
Roll 3 times above with the pressure roller of certain loading, open adhesive tape according to the method for 180 ° of peel strengths of test, test it attached
Put forth effort, it is stipulated that 0 grade is optimal, and 5 grades is worst
Embodiment 1
Taking 50g ethanol, the mixed solvent of 10g ethyl acetate is added to equipped with agitator, the 250mL tetra-mouthfuls burning of reflux condensing tube
In Ping, it is heated to 75 DEG C and maintains the reflux for 10min；By 16g methyl methacrylate, 16g butyl acrylate, 6g propylene
Acid, 2g 2-hydroxypropyl acrylate, 1.2g N-[2-(2-methyl-4-oxopentyl), 0.4g azodiisobutyronitrile mix homogeneously, treat diacetone
Acrylamide and azodiisobutyronitrile are added drop-wise in flask by 60mL constant pressure funnel after dissolving, and dropping in 2.5 hours is complete；
React at such a temperature after completion of dropwise addition 4 hours, then cool to 40 DEG C, in flask, drip 2-3mL ammonia, continue to stir
Mix；Weigh 40g water and join in flask, continue stirring 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate is semi-transparent clear thick liquid, nonirritant gas
Taste, stable storing, vitrification point 15 DEG C, solid content 29%, tinting strength, tinting power 100%, anti-caking 0%, solvent resistance 89.65%.
In drying varniss solidification process volatilization the mixed solvent that solvent is water, ethanol, ethyl acetate, do not result in environmental pollution and
Infringement health.
Take water dispersible low-temperature self-crosslinking acrylate prepared by 70g, 20g aqueous color paste, 0.15g defoamer BYK 016
It is sequentially added in reactor, disperses 30min under the rotating speed of 300rpm, after stirring, i.e. obtain required water color ink.
After testing, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is not faded, 30 DEG C of surface drying time 35s,
Doing solid work 30min hardening time, do solid work 11min hardening time for 50 DEG C, on PE ground, adhesive force is 0 grade, attached on PP ground
Put forth effort to be 0 grade.The preparation of resin select the mixed solvent of ethanol and ethyl acetate as reaction dissolvent, and by suitable work
Skill condition makes resin have suitable molecular weight, add simultaneously water-dispersible after also can realize rapid draing.Introduce room-temperature self crosslinking body
System is capable of the fast setting of paint film and obtains good water-fast solvent resistance and adhesive force good on PE/PP film.
Infrared spectrum comparison diagram under the conditions of Fig. 1 is 30 DEG C, before and after cross-linking reaction generation.After a represents and crosslinks reaction
Water-dispersible acrylate resin, b represents the water-dispersible acrylate resin not crosslinking reaction.Contrast with b, a
At middle 1543cm-1, the N-H bending vibration absworption peak of amide groups disappears, and occurs stretching of hydrazone-N=C-double bond at 1655cm-1
Contracting vibration absorption peak, illustrates to there occurs cross-linking reaction under the conditions of 30 DEG C.
Embodiment 2
The mixed solvent taking 40g ethanol and 10g ethyl acetate is added to equipped with agitator, the 250mL tetra-mouthfuls burning of reflux condensing tube
In Ping, it is heated to 73 DEG C and maintains the reflux for 10min；By 20g ethyl methacrylate, 20g ethyl acrylate, 7.5g first
Base acrylic acid, 2.5g acrylic acid-2-hydroxyl ethyl ester, 1g N-[2-(2-methyl-4-oxopentyl), 0.5g azodiisobutyronitrile mix homogeneously,
It is added drop-wise in flask by 60mL constant pressure funnel after N-[2-(2-methyl-4-oxopentyl) and azodiisobutyronitrile dissolve, within 3 hours, drips
Add complete；React at such a temperature after completion of dropwise addition 4 hours, then cool to 40 DEG C, in flask, drip 4-5mL ammonia,
Continue stirring；Weigh 50g water and join in flask, continue stirring 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate is semi-transparent clear thick liquid, nonirritant gas
Taste, stable storing, vitrification point 16 DEG C, solid content 31%, tinting strength, tinting power 100%, anti-caking 0%, solvent resistance 87.52%.
Take water dispersible low-temperature self-crosslinking acrylate prepared by 70g, 25g aqueous color paste, 0.15g defoamer BYK 016
It is sequentially added in reactor, disperses 30min under the rotating speed of 300rpm, after stirring, i.e. obtain required water color ink.
After testing, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is slightly faded, 30 DEG C of surface drying times
45s, does solid work 34min hardening time, does solid work 13min hardening time for 50 DEG C, and on PE ground, adhesive force is 1 grade, at the bottom of PP
On material, adhesive force is 0 grade.
Embodiment 3
Take 40g ethanol and the mixed solvent of 30g ethyl acetate, be added to equipped with agitator, the 250mL tetra-mouthfuls of reflux condensing tube
In flask, it is heated to 72 DEG C and maintains the reflux for 15min；By 15g ethyl methacrylate, 9g acrylic acid 2 ethylhexyl ester,
4.5g methacrylic acid, 1.5g 2-hydroxypropyl acrylate, 0.6g N n-methylolacrylamide, 0.3g azodiisobutyronitrile
Mix homogeneously, is added drop-wise to flask by 60mL constant pressure funnel after N n-methylolacrylamide and azodiisobutyronitrile are dissolved
In, dropping in 2.5 hours is complete；React at such a temperature after completion of dropwise addition 3.5 hours, then cool to 40 DEG C, in flask
Dropping 2-3mL triethanolamine, continues stirring；Weigh 30g water and join in flask, continue stirring 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate is semi-transparent clear thick liquid, nonirritant gas
Taste, stable storing, vitrification point 29 DEG C, solid content 23%, tinting strength, tinting power 99%, anti-caking 0.5%, solvent resistance 86.24%.
Take water dispersible low-temperature self-crosslinking acrylate prepared by 70g, 30g aqueous color paste, 0.2g defoamer BYK 016
It is sequentially added in reactor, disperses 25min under the rotating speed of 250rpm, after stirring, i.e. obtain required water color ink.
After testing, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is slightly faded, 30 DEG C of surface drying times
25s, does solid work 28min hardening time, does solid work 10min hardening time for 50 degrees Celsius, and on PE ground, adhesive force is 1 grade,
On PP ground, adhesive force is 0 grade.
Embodiment 4
The mixed solvent taking 50g ethanol and 15g ethyl acetate is added to equipped with agitator, the 250mL tetra-mouthfuls burning of reflux condensing tube
In Ping, it is heated to 75 DEG C and maintains the reflux for 10min；By 16g isobutyl methacrylate, 12g ethyl acrylate, 5.5g
The mixing of acrylic acid, 1.5g Hydroxypropyl methacrylate, 1.4g N-[2-(2-methyl-4-oxopentyl), 0.4g azodiisobutyronitrile is all
Even, it is added drop-wise in flask by 60mL constant pressure funnel after N-[2-(2-methyl-4-oxopentyl) and azodiisobutyronitrile dissolve, 3 is little
Time drip complete；React at such a temperature after completion of dropwise addition 4 hours, then cool to 40 DEG C, in flask, drip 3-4mL
Ammonia, continues stirring；Weigh 40g water and join in flask, continue stirring 20min, discharging.
After testing, gained water dispersible low-temperature self-crosslinking acrylate is semi-transparent clear thick liquid, nonirritant gas
Taste, stable storing, vitrification point 30 DEG C, solid content 26%, tinting strength, tinting power 100%, anti-caking 0%, solvent resistance 89.27%.
Take water dispersible low-temperature self-crosslinking acrylate prepared by 70g, 10g aqueous color paste, 0.1g defoamer BYK 016
It is sequentially added in reactor, disperses 25min under the rotating speed of 300rpm, after stirring, i.e. obtain required water color ink.
After testing, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is not faded, 30 DEG C of surface drying time 30s,
Doing solid work 26min hardening time, do solid work 10min hardening time for 50 DEG C, on PE ground, adhesive force is 0 grade, attached on PP ground
Put forth effort to be 0 grade.
Embodiment 5
Taking 35g ethanol, the mixed solvent of 35g ethyl acetate is added to equipped with agitator, the 250mL tetra-mouthfuls burning of reflux condensing tube
In Ping, it is heated to 73 DEG C and maintains the reflux for 10min；By 12g methyl methacrylate, 13g butyl acrylate, 5g methyl
Acrylic acid, 0.9g N hydroxyethyl acrylamide, 0.3g azodiisobutyronitrile mix homogeneously, treat N hydroxyethyl acrylamide and idol
Nitrogen bis-isobutyronitrile is added drop-wise in flask by 60mL constant pressure funnel after dissolving, and dropping in 3 hours is complete；After completion of dropwise addition
React 3.5 hours at a temperature of Gai, then cool to 40 DEG C, in flask, drip 3-4mL ethanolamine, continue stirring；Weigh
30g water joins in flask, continues stirring 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, vitrification point 22 DEG C, solid content 24%, tinting strength, tinting power 98%, anti-caking 1%, solvent resistance 87.42%.
Take water dispersible low-temperature self-crosslinking acrylate prepared by 70g, 30g aqueous color paste, 0.15g defoamer BYK 016
It is sequentially added in reactor, disperses 30min under the rotating speed of 250rpm, after stirring, i.e. obtain required water color ink.
After testing, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is slightly faded, 30 DEG C of surface drying times
34s, does solid work 35min hardening time, does solid work 15min hardening time for 50 DEG C, and on PE ground, adhesive force is 1 grade, at the bottom of PP
On material, adhesive force is 1 grade.
Comparative example: process for preparing resins is selected from the Chinese patent embodiment 1 of Publication No. CN103396508, ink system
Preparation Method and method of testing are by the method for the invention.
A (), by 30g glycol monoethyl ether and 20g N, N dimethylformamide joins in band reflux condenser reactor, stirs
Mix and be warming up to 60 DEG C, after backflow is stable, obtaining mixed solvent；
B () is by 4g styrene, 15g methyl methacrylate, 21g ethyl acrylate, 4g acrylic acid, 2g acrylic acid hydroxyl
Ethyl ester, 1g N n-methylolacrylamide, 1g N-[2-(2-methyl-4-oxopentyl) and 0.6g azodiisobutyronitrile join in stirred tank, stir
Mix 30 minutes and obtain mixing raw material after solid particle is completely dissolved；
C mixing raw material in step a reactor is warming up to 70 DEG C by (), after backflow is stable, by former for the mixing in step b
Gob enters in reactor, and control temperature is at 70～75 DEG C, and time for adding is 3.5 hours；
After (d) dropping, maintain the temperature at 75 DEG C, react 1 hour；
E () insulation terminates after, prepared crude propylene acid ester resin is carried out decompression distillation, extracts unreacted monomer and big portion
Divide solvent；
F () decompression distillation terminates after, it is cooled to 45 DEG C；
G () dropping 4g triethylamine regulation resin pH value, to 7.5～8.0, adds 70g water, maintains the temperature at 45 DEG C, stirring
30 minutes, after resin is the most water-soluble, cool the temperature to 40 DEG C, discharging.
Gained low-temperature self-crosslinking water-borne acrylic resin is the micro-yellow thick liquid of semi-transparent clear, has no irritating odor, and paint film is done
Dry solidification process there is a little alcohol ether solvent volatilize, vitrification point 30 DEG C, solid content 21%, tinting strength, tinting power 100%, anti-
Caking property 0%, ink water-resistance property of coating water after soaking 24 hours is unstained, and wiping is slightly faded, 30 DEG C of surface drying time 134s,
Doing solid work 110min hardening time, do solid work 40min hardening time for 50 DEG C, on PE ground, adhesive force is 1 grade, on PP ground
Adhesive force is 0 grade.
Claims (4)
1. aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate, it is characterised in that in terms of 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 regulation pH is
7～8, add 30～60 parts of water as dispersant；
Described hard monomer is methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, methacrylic acid
One or more in isobornyl thiocyanoacetate；
Described soft monomer is in n-butyl acrylate, ethyl acrylate, acrylic acid 2 ethylhexyl ester, n-octyl
One or more；
A described class hydrophilic monomer is the one in acrylic acid and methacrylic acid；
Two described class hydrophilic monomers are acrylic acid 2 hydroxypropyl acrylate, acrylic acid 2 hydroxyl ethyl ester, methacrylic acid 2 hydroxyl ethyl ester and first
One in base acrylic acid 2 hydroxypropyl acrylate；
Described cross-linking monomer is N n-methylolacrylamide, N hydroxyethyl acrylamide, N-[2-(2-methyl-4-oxopentyl), ethylene methacrylic
One or more in base ketone, methacrylic acid acetoxyl group ester, acrylic acid acetoxyl group ester；
Described initiator is the one in azodiisobutyronitrile, 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 alkalescence 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 by hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer and initiator mix homogeneously, drip
It is added in reactor；Reaction temperature is kept to continue reaction 3.5～4 hours at 70～78 DEG C after completion of dropwise addition；Then dropping pH adjusts
Joint agent, adds water, discharging after stirring.
A kind of aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate, its feature
Be: described organic solvent be mass ratio be that ethanol and the ethyl acetate of 5:1～1:1 forms.
A kind of aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate, its feature
It is: one or more in ethanolamine, triethanolamine and ammonia of described pH adjusting agent.
4. according to the aqueous printing ink dispersibility quick-dry type low-temperature self-crosslinking acrylate described in any one of claim 15
Preparation method, it is characterised in that: comprise the steps:
(1) adding organic solvent in a kettle., mixing speed is 250～300rpm, and is heated to 70～78 DEG C；
(2) by hard monomer, soft monomer, a class hydrophilic monomer, two class hydrophilic monomers, cross-linking monomer, initiator mix homogeneously
After be at the uniform velocity added drop-wise in reactor, 2.5～3 hours dropping complete；
(3) after drop to be mixed adds, continuation insulation reaction 3.5～4 hours；
(4) stopped reaction be cooled to 35～45 DEG C after insulation reaction completes, adding pH adjusting agent regulation pH is 7～8,
In terms of mass fraction, weigh 30～60 parts of water and join in reaction vessel, discharging after stirring, obtain water dispersible quick-drying
Type low-temperature self-crosslinking acrylate.
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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 |
| CN110804864A (en) * | 2019-09-29 | 2020-02-18 | 嘉兴市恒悦纺织有限公司 | Processing technology of flame-retardant antibacterial polyester fabric |
| CN112574617A (en) * | 2020-11-30 | 2021-03-30 | 江苏科技大学 | Quick-drying water-based ink composition and preparation method and application thereof |
| CN112851849B (en) * | 2021-01-12 | 2023-01-31 | 广东彤德新材料有限公司 | Air-drying water-soluble acrylic resin and preparation method thereof |
| CN115304957B (en) * | 2022-07-20 | 2024-03-01 | 成都托展新材料股份有限公司 | Water-based ink dispersoid and preparation method thereof |
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| CN1878835A (en) * | 2005-02-11 | 2006-12-13 | 德古萨公司 | Aqueous compositions |
| CN101696262A (en) * | 2009-10-23 | 2010-04-21 | 华南理工大学 | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents |
| CN102574936A (en) * | 2009-07-23 | 2012-07-11 | 阿克马法国公司 | Aqueous self-crosslinkable polymer dispersion made from hard-core, soft-shell structured polymer particles, and coating or treatment compositions |
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| CN1878835A (en) * | 2005-02-11 | 2006-12-13 | 德古萨公司 | Aqueous compositions |
| CN102574936A (en) * | 2009-07-23 | 2012-07-11 | 阿克马法国公司 | Aqueous self-crosslinkable polymer dispersion made from hard-core, soft-shell structured polymer particles, and coating or treatment compositions |
| CN101696262A (en) * | 2009-10-23 | 2010-04-21 | 华南理工大学 | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents |
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