CN110128875A - A kind of novel flexographic printing water-based ink binder self-crossing emulsion and preparation method thereof - Google Patents
A kind of novel flexographic printing water-based ink binder self-crossing emulsion and preparation method thereof Download PDFInfo
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- CN110128875A CN110128875A CN201910422326.6A CN201910422326A CN110128875A CN 110128875 A CN110128875 A CN 110128875A CN 201910422326 A CN201910422326 A CN 201910422326A CN 110128875 A CN110128875 A CN 110128875A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
The invention discloses a kind of novel flexographic printing water-based ink binder self-crossing emulsions and preparation method thereof, wherein, the novel flexographic printing is the copolymer emulsion being prepared by following components through emulsion copolymerization with water-based ink binder self-crossing emulsion: 30~70 parts by weight of deionized water, 5~35 parts by weight water-base resins, the alkyl acrylate monomer that the total carbon number of 2~40 parts by weight is 4~12, the methacrylate-based monomer that the total carbon number of 0~25 parts by weight is 5~20, 0~25 weight parts of styrene monomer, 0.2~5 parts by weight (methyl) dihydroxypropyl ester monomer, the cross-linking monomer of 0.5~5 parts by weight, the metallic-ion crosslinking agent of 0.01~0.5 parts by weight, 0.01~0.1 parts by weight initiator and 0~10 parts by weight pH adjusting agent.Self-crosslinking reaction can occur at room temperature for the novel flexographic printing water-based ink binder self-crossing emulsion in the present invention, have excellent solubility, water resistance, printing transferability.
Description
Technical field
The present invention relates to water-base resin and its synthesis technical field, in particular to a kind of novel flexographic printing water-based ink
Binder self-crossing emulsion and preparation method thereof.
Background technique
In recent years, as atmosphere pollution and environmental protection are more and more paid attention to, the high Traditional Packing of VOC emission amount
Printing industry is faced with huge transition pressure, therefore the status of flexible printing and water-based ink is gradually increased.As aqueous oil
Ink connecting material, acrylic emulsion due to the advantages that its synthesis is simple, and molecular weight is high, weatherability, oil resistivity and high gloss and by
To the favor on printing circle.However, using small-molecular emulsifier prepare traditional acrylic emulsions there are some disadvantages, such as
Printing metastatic is poor, insufficient to the adhesive force of non-absorbability base material, solubility is poor, slow drying speed, and small-molecular emulsifier is easy
Ink pellet surface is moved to, poor water resistance etc. is caused, is not able to satisfy the requirement of flexo technology.Water-base resin is usually hydrophobic monomer
(such as methyl methacrylate, butyl acrylate, styrene etc.) and monomer (such as acrylic acid, methyl containing carboxylic acid group
Acrylic acid etc.) random copolymer.A series of small-molecular emulsifiers can be overcome to exist by macromole emulsifying agent of water-base resin
The problem of.It is had many advantages using the acrylic emulsion that water-base resin is emulsifier preparation, such as newton rheological behaviour, excellent
Freeze-thawing Characteristics and stability, good wetability, are easy to printing machine cleaning, good solubility etc. at good pigment-dispersing.
In the development process of flexographic printing water-based ink binder at this stage, there is also many insufficient.Patent is public
Patent disclosed in 102911559 A of the number of opening CN " a kind of water-based ink is anti-to after-tack pure-acrylic emulsion ", is to protect using self-control water-base resin
It protects colloid and prepares pure-acrylic emulsion using different acrylate class monomer as comonomer.But this method makes when preparing water-base resin
Small-molecular emulsifier, during being brought into synthetic emulsion, so that still containing more small point in the lotion of preparation
Sub- emulsifier, will cause the poor water resistance of lotion, and influence the surface nature of lotion.In addition acrylic acid is prepared using water-base resin
When lotion, the parameters such as the molecular size range and molecular weight distribution of water-base resin, acid value, glass transition temperature have the performance of lotion
Very big influence, therefore have very strict requirement to these parameters, especially require its molecular weight distribution will be as far as possible
It is narrow.It is obvious that the water-base resin of conventional method preparation does not have these characteristics, therefore can not really be answered by extensive industrialization
With.In addition this method does not use any cross-linking monomer, and there are the hydrophilic radicals such as a large amount of carboxyl in emulsion system, therefore its glue
The mechanical mechanics property of film is poor, water-fast, medium-resistance is bad, is unable to satisfy the performance requirement of high-quality ink.
Patent disclosed in 101717463 A of patent publication No. CN " a kind of water-soluble ink connecting material resin for plastic and
Preparation method " using styrene and different acrylate class monomer as comonomer prepare it is a kind of can infinitely be dissolved in water, it is stingless
Swash the styrene-acrylic emulsion of property smell.But many alcoholic solvents are added in its issued patents, VOC emission amount is high, and does not also refer to lotion
Solubility.
Patent disclosed in 104789041 A of patent publication No. CN " the modified compound alkali soluble emulsion of zirconium chelate and its system
Standby high solubility water-based ink and method " discloses a kind of compound alkali soluble emulsion that zirconium chelate is modified, and is based on the cream
The high solubility water-based ink of liquid preparation.But this method belongs to the traditional acrylic emulsion prepared using small-molecular emulsifier,
There is the deficiency of printing transferability difference in its corresponding ink, be unable to satisfy the requirement of high speed flexo technology, and use ethyl alcohol, different
Propyl alcohol equal solvent.
Summary of the invention
The purpose of the present invention, it is desirable to provide a kind of with excellent solubility, water resistance, the novel soft version print for printing transferability
Brush water-based ink binder self-crossing emulsion and preparation method thereof.
The technical scheme is that
Novel flexographic printing water-based ink binder self-crossing emulsion, to be prepared by following components through emulsion copolymerization
The copolymer emulsion arrived: 30~70 parts by weight of deionized water, 5~35 parts by weight water-base resins, the total carbon number of 2~40 parts by weight are 4
~12 alkyl acrylate monomer, the methacrylate-based monomer that the total carbon number of 0~40 parts by weight is 5~20,0~20 weight
Part styrene monomer, 0.2~5 parts by weight (methyl) dihydroxypropyl ester monomer, 0.5~5 part of cross-linking monomer, 0.01~0.5
The metallic-ion crosslinking agent of parts by weight, 0.1~2 parts by weight initiator and 0~10 parts by weight pH adjusting agent.
The water-base resin be the hydrophobic monomer containing carbon-carbon double bond and containing carbon-carbon double bond containing carboxylic group
It is methyl methacrylate, ethyl acrylate, butyl acrylate and benzene that the random copolymer of monomer, which is by the hydrophobic monomer,
One of ethylene is a variety of, and the monomer containing carboxylic acid group is that acrylic acid, methacrylic acid and maleic acid are a kind of or more
Kind, it is obtained through ontology or polymerisation in solution, the water-base resin number-average molecular weight is 2000~15000, and acid value is 50~300, glass
Glass temperature is 20 DEG C~150 DEG C.
The alkyl acrylate monomer that total carbon number is 4~12 is methyl acrylate, ethyl acrylate, acrylic acid fourth
One of ester, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, isobornyl acrylate are a variety of.Wherein preferably go out butyl acrylate,
One of Isooctyl acrylate monomer, isobornyl acrylate are a variety of.
The methacrylate-based monomer that total carbon number is 5~20 be methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, isobornyl methacrylate, lauryl methacrylate, in octadecyl methacrylate
It is one or more.
(methyl) crylic acid hydroxy ester be hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate,
Hydroxy propyl methacrylate.
The cross-linking monomer is glycidyl methacrylate, (methyl) acrylamide, hydroxymethyl acrylamide, hydroxyl
Ethyl acrylamide and DAAM/ADH's is one or more.
The metallic-ion crosslinking agent is zinc ion complex compound, zirconium ion complex compound, calcium ion complex compound, magnesium ion complexing
One of object and chromium ion complex compound are a variety of.
The initiator is one of potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate or a variety of.
The pH adjusting agent is potassium hydroxide, in sodium hydroxide, ammonium hydroxide, AMP-95, triethylamine, ethylenediamine, triethanolamine
It is one or more.Wherein preferably go out sodium hydroxide, ammonium hydroxide, tri- kinds of AMP-95 of composition.
The novel flexographic printing preparation method of water-based ink binder self-crossing emulsion, includes the following steps:
(1) it stocks up: according to preparing raw material: 30~70 parts by weight of deionized water, the aqueous tree of 5~35 parts by weight as following formula
The methyl that alkyl acrylate monomer that rouge, the total carbon number of 2~40 parts by weight are 4~12, the total carbon number of 0~40 parts by weight are 5~20
Acrylic ester monomer, 0~20 weight parts of styrene monomer, 0.2~5 parts by weight (methyl) dihydroxypropyl ester monomer, 0.5~
5 parts of cross-linking monomer, 0.1~2 parts by weight initiator and 0~10 parts by weight pH adjusting agent；
(2) water-base resin is dissolved: in the reactor equipped with reflux condensing tube, thermometer, agitating paddle and nitrogen inlet duct
Water-base resin and portions of de-ionized water weighted in step (1) is added, and middle addition pH adjusting agent under mechanical stirring, 70
DEG C~100 DEG C at persistently stir 30~90 minutes and obtain aqueous resin solution；
(3) seed emulsion is prepared: the alkyl acrylate monomer, total for being 4~12 by total carbon number weighted in step (1)
Methyl acrylic ester unsaturated monomer, styrene monomer, (methyl) dihydroxypropyl ester monomer and the crosslinking that carbon number is 4~20
Monomer respectively takes 4wt% and remaining deionized water to be added in the aqueous resin solution prepared in step (2), persistently stirs 20~40
The initiator of 50wt% is added after minute, keeps the temperature 20~40 minutes at a temperature of 80~85 DEG C in the case where lasting stirring and is planted
Sub- lotion；
(4) prepare lotion: by remaining total carbon number be 4~12 alkyl acrylate monomer, total carbon number be 5~20 first
Base esters of acrylic acid unsaturated monomer, styrene monomer, (methyl) dihydroxypropyl ester monomer, cross-linking monomer and initiator are 60
It being added drop-wise in~180 minutes in step (3) in seed emulsion obtained, reaction temperature is controlled at 70 DEG C~90 DEG C, heat preservation 90~
180 minutes.
(5) addition of crosslinking agent: being down to 65~75 degrees Celsius for reaction temperature, with pH adjusting agent by reacting solution pH value tune
It is whole that metal crosslinking agent is added to 7~9,20~40 minutes are kept the temperature, room temperature is down to adipic dihydrazide is added and persistently stir 30~40
Minute, the lotion being then obtained by filtration is novel flexographic printing water-based ink binder self-crossing emulsion.
The advantages and beneficial effects of the present invention are:
1. assigning the excellent solubility of ink and printing transferability by the present invention in that using water-base resin as emulsifier；
The monomer of reaction can be crosslinked without using any small-molecular emulsifier, and introducing room temperature, improves the water resistance of ink；It will be newborn
Liquid size controlling is in 100nm hereinafter, to guarantee it with ideal rate of drying and excellent filming performance；By using big point
The compounded technology of son amount and the water-base resin of small-molecular-weight assigns the high glossiness of ink and the dispersibility to mill base.By making
It assigns ink excellent mechanical mechanics property and resistance to medium with MULTIPLE COMPOSITE cross-linking system, while utilizing different cross-linking systems
The difference of cross-linking reaction speed, the solubility for solving water-based ink are asked with what mechanical performance, resistance to medium can balance very well
Topic.Water-based ink resin binder simple process prepared by the present invention, it is low in cost, have excellent performance, have very high using valence
Value.
2. a kind of simple production process of the present invention, safety and environmental protection, self-crosslinking acrylic ester emulsion at low cost, will be obtained
Acrylic acid ester emulsion be applied to a kind of available stability of flexographic printing industry is good, glossiness is high, water resistance is strong, have it is excellent
Different solubility and the water-based ink for printing transferability.There is excellent adhesive force on black, PE film and pure white PE film applied to PP.?
High-end product packaging aspect has a wide range of applications.
Specific embodiment
[embodiment 1]
The dissolution of water-base resin: temperature is under 80 DEG C, revolving speed 300r/min, nitrogen atmosphere, in 2L reaction kettle successively
It is the ammonium hydroxide 43.7g that 7000 water-base resin 140g, deionized water 656.3g and mass concentration are 25% that molecular weight, which is added, is passed through
Pure transparent aqueous resin solution is obtained after the stirring of 30-40min.
It prepares monomer mixed solution: taking styrene 112.4g, methyl methacrylate 112.4g, butyl acrylate 87.6g, third
The different monooctyl ester 87.6g of olefin(e) acid, isobornyl acrylate 8g, hydroxy-ethyl acrylate 8g, Diacetone Acrylamide 12g and methacrylic acid
Ethylene oxidic ester 2g is uniformly mixed, obtains yellow transparent solution.
For temperature under 86~88 DEG C, revolving speed 300r/min, nitrogen atmosphere, the yellow for taking the above-mentioned preparation of 4wt% to complete is saturating
Bright solution is added in the water-base resin dissolved, while sodium peroxydisulfate 2g is added and obtains blue seed emulsion.
Residual monomer solution is added dropwise into system, control time for adding is a hour, while 1.2g sodium peroxydisulfate is added dropwise
Aqueous solution, time for adding are slightly longer than the monomer dropping time.After being added dropwise, keep the temperature in 88 DEG C of 2 hours of curing.
Reaction temperature is down to 70 degrees Celsius, AMP-95 aqueous solution 60g is added into system, 25% mass concentration is added
Zinc acetate solution 8g, heat preservation cure 30 minutes at 70 DEG C, are down to room temperature addition adipic dihydrazide 6g and persistently stir 30 minutes, use
200 mesh filter screen filtering and dischargings obtain milky emulsion, flexographic printing water-based ink binder lotion as of the present invention.
[embodiment 2]
The dissolution of water-base resin: temperature is under 80 DEG C, revolving speed 300r/min, nitrogen atmosphere, in 2L reaction kettle successively
It is the ammonium hydroxide 43.7g that 7000 water-base resin 140g, deionized water 356.3g and mass concentration are 25% that molecular weight, which is added, is passed through
Pure transparent aqueous resin solution is obtained after the stirring of 30-40min.
It prepares monomer mixed solution: taking styrene 112.4g, methyl methacrylate 112.4g, butyl acrylate 87.6g, third
The different monooctyl ester 87.6g of olefin(e) acid, isobornyl acrylate 8g, hydroxy-ethyl acrylate 8g and Diacetone Acrylamide 12g and metering system
Acid glycidyl ester 2g is uniformly mixed, obtains yellow transparent solution.
It prepares pre-emulsion: deionized water 303.7g, aqueous resin solution 100g being added in monomer mixed solution, magnetic force stirs
It mixes 30 minutes, obtains white pre-emulsion.
Remaining 440g aqueous resin solution is added in a kettle, and sodium peroxydisulfate 1.5g is added, reaction temperature is 88
DEG C, pre-emulsion and sodium persulfate aqueous solution 1.2g are added dropwise into reaction kettle, time for adding is a hour.After being added dropwise to complete,
Heat preservation is in 88 DEG C of 2 hours of curing.
Reaction temperature is down to 70 degrees Celsius, AMP-95 aqueous solution 60g is added into system, 25% mass concentration is added
Zinc acetate solution 8g, heat preservation cure 30 minutes at 70 DEG C, are down to room temperature addition adipic dihydrazide 6g and persistently stir 30 minutes, use
200 mesh filter screen filtering and dischargings obtain milky emulsion, flexographic printing water-based ink binder lotion as of the present invention.
[embodiment 3]
The dissolution of water-base resin: temperature is under 80 DEG C, revolving speed 300r/min, nitrogen atmosphere, in 2L reaction kettle successively
It is the ammonium hydroxide 43.7g that 7000 water-base resin 140g, deionized water 356.3g and mass concentration are 25% that molecular weight, which is added, is passed through
Pure transparent aqueous resin solution is obtained after the stirring of 30-40min.
It prepares monomer mixed solution: taking styrene 112.4g, methyl methacrylate 112.4g, butyl acrylate 87.6g, third
The different monooctyl ester 87.6g of olefin(e) acid, isobornyl acrylate 8g, hydroxy-ethyl acrylate 8g and Diacetone Acrylamide 12g and metering system
Acid glycidyl ester 2g is uniformly mixed, obtains yellow transparent solution
It prepares fine crankshaft liquid: deionized water 303.7g, aqueous resin solution 100g being added in monomer mixed solution, and is added
Octadecyl acrylate 2g obtains white fine crankshaft liquid using biomixer dispersion 10min.
Remaining 440g aqueous resin solution is added in a kettle, and sodium peroxydisulfate 1.5g is added, reaction temperature is 88
DEG C, fine crankshaft liquid and 1.2g sodium persulfate aqueous solution are added dropwise into reaction kettle, time for adding is a hour, after being added dropwise to complete.
Heat preservation 2 hours of curing at 88 DEG C.
Reaction temperature is down to 70 degrees Celsius, AMP-95 aqueous solution 60g is added into system, 25% mass concentration is added
Zinc acetate solution 8g, heat preservation cure 30 minutes at 70 DEG C, are down to room temperature addition adipic dihydrazide 6g and persistently stir 30 minutes, use
200 mesh filter screen filtering and dischargings obtain milky emulsion, flexographic printing water-based ink binder lotion as of the present invention.
[embodiment 4]
Molecular weight is 7000 water-base resin 140g, deionization in the preparation of water-based ink binder lotion by present implementation
It is 7000 water-base resin 70g, deionized water 616.2g that the ammonium hydroxide 43.7g that water 656.3g and mass concentration are 25%, which is changed to molecular weight,
The ammonium hydroxide 21.8g for being 25% with mass concentration.Other are same as Example 1
[embodiment 5]
Molecular weight is 7000 water-base resin 140g, deionization in the preparation of water-based ink binder lotion by present implementation
It is 7000 water-base resin 280g, deionized water that the ammonium hydroxide 43.7g that water 656.3g and mass concentration are 25%, which is changed to molecular weight,
The ammonium hydroxide 87.4g that 726.6g and mass concentration are 25%.Other are same as Example 1
[embodiment 6]
The water-base resin 140g that molecular weight is 7000 is changed to by present implementation in the preparation of water-based ink binder lotion
The water-base resin 140g that molecular weight is 8600.Other are same as Example 1.
[embodiment 7]
The water-base resin 140g that molecular weight is 7000 is changed to by present implementation in the preparation of water-based ink binder lotion
The water-base resin 140g that molecular weight is 12000.Other are same as Example 1.
[embodiment 8]
The water-base resin 140g that molecular weight is 7000 is changed to by present implementation in the preparation of water-based ink binder lotion
The water-base resin 80g that the water-base resin 60g and molecular weight that molecular weight is 2000 are 12000.Other are same as Example 1.
[embodiment 9]
The ammonium hydroxide 43.7g that mass concentration is 25% is changed to by present implementation in the preparation of water-based ink binder lotion
31.67g AMP-95.Other are same as Example 1.
[embodiment 10]
The ammonium hydroxide 43.7g that mass concentration is 25% is changed to by present implementation in the preparation of water-based ink binder lotion
The ammonium hydroxide 21.85g that the AMP-95 and mass concentration of 15.83g is 25%.Other are same as Example 1.
[embodiment 11]
The ammonium hydroxide 43.7g that mass concentration is 25% is changed to by present implementation in the preparation of water-based ink binder lotion
The AMP-95 of 6.33g, the ammonium hydroxide 17.48g and 10.31gNaOH that mass concentration is 25%.Other are same as Example 1.
[embodiment 12]
Glycidyl methacrylate 2g is changed to 4g in the preparation of water-based ink binder lotion and handed over by present implementation
Join monomeric acrylamide.Other are same as Example 1.
[embodiment 13]
Glycidyl methacrylate 2g is changed to 4g hydroxyl in the preparation of water-based ink binder lotion by present implementation
Methacrylamide.Other are same as Example 1.
[embodiment 14]
Hydroxy-ethyl acrylate 8g is changed to hydroxypropyl acrylate in the preparation of water-based ink binder lotion by present implementation
8g.Other are same as Example 1.
[embodiment 15]
Sodium peroxydisulfate is replaced with ammonium persulfate in the preparation of water-based ink binder lotion by present implementation entirely.Other with
Embodiment 1 is identical.
[embodiment 16]
Sodium peroxydisulfate is replaced with potassium peroxydisulfate in the preparation of water-based ink binder lotion by present implementation entirely.Other with
Embodiment 1 is identical.
[embodiment 17]
The zinc acetate solution 8g of 25% mass concentration is changed to by present implementation in the preparation of water-based ink binder lotion
4g zirconium ion complex compound Tyzor212.Other are same as Example 1
[comparative example]
The dissolution of water-base resin: temperature is under 80 DEG C, revolving speed 300r/min, nitrogen atmosphere, in 2L reaction kettle successively
It is the ammonium hydroxide 43.7g that 7000 water-base resin 140g, deionized water 656.3g and mass concentration are 25% that molecular weight, which is added, is passed through
Pure transparent aqueous resin solution is obtained after the stirring of 30-40min.
It prepares monomer mixed solution: taking styrene 112.4g, methyl methacrylate 112.4g, butyl acrylate 87.6g, third
The different monooctyl ester 87.6g of olefin(e) acid, isobornyl acrylate 8g, hydroxy-ethyl acrylate 8g are uniformly mixed, obtain yellow transparent solution.
For temperature under 86~88 DEG C, revolving speed 300r/min, nitrogen atmosphere, the yellow for taking the above-mentioned preparation of 4wt% to complete is saturating
Bright solution is added in the water-base resin dissolved, while sodium peroxydisulfate 2g is added and obtains blue seed emulsion.
Residual monomer solution is added dropwise into system, control time for adding is a hour, while 1.2g sodium peroxydisulfate is added dropwise
Aqueous solution, time for adding are slightly longer than the monomer dropping time.After being added dropwise, keeps the temperature in 88 DEG C of 2 hours of curing, is down to room temperature,
AMP-95 aqueous solution 60g is added into system, obtains milky emulsion with 200 mesh filter screen filtering and dischargings, it is as of the present invention
Flexographic printing water-based ink binder lotion.
Table one, the comparison of lotion stoste of the embodiment of the present invention
Particle size determination is measured using NanoZS nano particle size analyzer in table, and test temperature is 25 DEG C, and measurement is made even three times
Mean value to get the latex particle into lotion partial size and particle diameter distribution.
The measurement of the degree of cross linking is measured using acetone soak method in table, is impregnated 24 hours in acetone, and front and back quality is calculated
Change to get the degree of cross linking of latex film is arrived.
The measurement use of table medium viscosity examines grace cup viscosmeter and glue is filled viscosmeter, then flows out glue, starts simultaneously
Stopwatch to glue stream silk interrupts, and stops stopwatch, which is the condition viscosity of glue, and replication is primary, and error is not more than
The 3% of average value.
The present invention applies on flexographic printing water-based ink, the experimental data comparison of each case study on implementation performance:
Table two, simple water-soluble printing ink formula
| Resin binder | Mill base | Moistening flatting agent | Defoaming agent | Antiwear assistant |
| 50% | 40% | 1% | 1% | 8% |
Table three, the performance comparison being film-made on BOPP/PE film substrate using proof press
The mensuration mode of adhesive force is to take one section of ink batten (long 10cm or so) in upper table, takes one with 3M600 adhesive tape is viscous
Determine the ink film of area, flattens, take adhesive tape off rapidly, in triplicate, observation ink film the case where being sticked out by adhesive tape, according to sticking out from few
To mostly use it is excellent, good, in, difference determine grade.
Water resistance mensuration mode is that ink batten obtained is cut lower sub-fraction into the water and soaked in upper table
Not yet.After for 24 hours, be drawn off whether observation deionized water changes colour and whether film has and fall off, according to change colour and fall off from
It is few to mostly use it is excellent, good, in, difference determine grade.
Resisting the mensuration mode being adhered in upper table is that a doubling contacts in 30 minutes by ink batten obtained, at 50 DEG C
In baking oven, be pressed under 2KG counterweight, place 2 hours, depending on its trace adhesion situation, according to trace adhesion use from less to more it is excellent,
It is good, in, difference determine grade.
The mensuration mode of solubility is to coat one layer of ink on the glass substrate in upper table, after just doing, drips water, is seen
Examine ink dissolution situation, according to dissolution from more to less using it is excellent, good, in, difference determine grade.
Being confirmed by result above, the styrene-acrylic emulsion designed by using the present invention is available, and partial size is small, stability is high,
Adhesive force it is good it is a kind of with excellent solubility, water resistance, print transferability novel flexographic printing water-based ink binder
Self-crossing emulsion.
Industrial applicability
By the invention it is possible to a kind of simple production process, safety and environmental protection, acrylic acid ester emulsion at low cost is made, it will
Obtained acrylic acid ester emulsion be applied to a kind of available stability of flexographic printing industry is good, glossiness is high, water resistance is strong,
Water-based ink with excellent solubility and printing transferability.It is excellent attached applied to having on PP ink, PE film and pure white PE film
Put forth effort.It has a wide range of applications in terms of high-end.
Place, those skilled in the art can not select from the prior art to the greatest extent in the embodiment of the present invention.
Disclosed above is only a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, is appointed
What those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, answer
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with above-mentioned scope of protection of the claims
It is quasi-.
Claims (11)
1. a kind of novel flexographic printing water-based ink binder self-crossing emulsion, which is characterized in that be by following components through cream
The copolymer emulsion that liquid combined polymerization is prepared: 30~70 parts by weight of deionized water, 5~35 parts by weight water-base resins, 2~40 weights
Measure the alkyl acrylate monomer that the total carbon number of part is 4~12, the methyl acrylic ester that the total carbon number of 0~25 parts by weight is 5~20
Monomer, 0~25 weight parts of styrene monomer, 0.2~5 parts by weight (methyl) dihydroxypropyl ester monomer, 0.5~5 parts by weight
Cross-linking monomer, the metallic-ion crosslinking agent of 0.01~0.5 parts by weight, 0.01~0.1 parts by weight initiator and 0~10 parts by weight pH
Regulator.
2. novel flexographic printing according to claim 1 water-based ink binder self-crossing emulsion, which is characterized in that institute
Stating water-base resin is the random of the hydrophobic monomer containing carbon-carbon double bond and the monomer containing carbon-carbon double bond and containing carboxylic group
Copolymer, the water-base resin number-average molecular weight be 2000~15000, acid value be 50~300, glass transition temperature be 20 DEG C~
150℃。
3. novel flexographic printing according to claim 2 water-based ink binder self-crossing emulsion, which is characterized in that institute
Stating hydrophobic monomer is one of methyl methacrylate, ethyl acrylate, butyl acrylate and styrene or a variety of, described
Monomer containing carboxylic acid group is one of acrylic acid, methacrylic acid and maleic acid or a variety of.
4. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, the alkyl acrylate monomer that total carbon number is 4~12 is methyl acrylate, ethyl acrylate, butyl acrylate, third
One of olefin(e) acid monooctyl ester, Isooctyl acrylate monomer and isobornyl acrylate are a variety of.
5. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, the methacrylate-based monomer that total carbon number is 5~20 is methyl methacrylate, ethyl methacrylate, first
In base butyl acrylate, isobornyl methacrylate, lauryl methacrylate and octadecyl methacrylate
It is one or more.
6. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, (methyl) crylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and first
One of base hydroxypropyl acrylate is a variety of.
7. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, the cross-linking monomer is glycidyl methacrylate, (methyl) acrylamide, hydroxymethyl acrylamide, hydroxyl second
Base acrylamide and DAAM/ADH's is one or more.
8. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, the metallic-ion crosslinking agent is zinc ion complex compound, zirconium ion complex compound, calcium ion complex compound, magnesium ion complex compound
With one of chromium ion complex compound or a variety of.
9. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, feature
It is, the initiator is one of potassium peroxydisulfate, ammonium persulfate and sodium peroxydisulfate or a variety of.
10. any novel flexographic printing water-based ink binder self-crossing emulsion according to claim 1~3, special
Sign is that the pH adjusting agent is in potassium hydroxide, sodium hydroxide, ammonium hydroxide, AMP-95, triethylamine, ethylenediamine and triethanolamine
It is one or more.
11. the preparation side of any novel flexographic printing water-based ink binder self-crossing emulsion of claim 1~9
Method, which comprises the steps of:
(1) stock up: according to preparing raw material as following formula: 30~70 parts by weight of deionized water, 5~35 parts by weight water-base resins, 2~
The methacrylic acid that alkyl acrylate monomer that the total carbon number of 40 parts by weight is 4~12, the total carbon number of 0~25 parts by weight are 5~20
Esters monomer, 0~25 weight parts of styrene monomer, 0.2~5 parts by weight (methyl) dihydroxypropyl ester monomer, 0.5~5 part
Cross-linking monomer, the metallic-ion crosslinking agent of 0.01~0.5 parts by weight, 0.01~0.1 parts by weight initiator and 0~10 parts by weight pH
Regulator；
(2) it dissolves water-base resin: being added in the reactor equipped with reflux condensing tube, thermometer, agitating paddle and nitrogen inlet duct
Weighted water-base resin and portions of de-ionized water in step (1), and under mechanical stirring in be added pH adjusting agent, 70 DEG C~
It is persistently stirred at 100 DEG C 30~90 minutes and obtains aqueous resin solution；
(3) seed emulsion is prepared: alkyl acrylate monomer, total carbon number by total carbon number weighted in step (1) for 4~12
For 5~20 methyl acrylic ester unsaturated monomer, styrene monomer, (methyl) dihydroxypropyl ester monomer and cross-linking monomer
It respectively takes 4wt% and remaining deionized water to be added in the aqueous resin solution prepared in step (2), persistently stirs 20~40 minutes
The initiator of 50wt% is added afterwards, keeps the temperature 20~40 minutes at a temperature of 80~85 DEG C in the case where lasting stirring and obtains seed cream
Liquid；
(4) prepare lotion: by remaining total carbon number be 4~12 alkyl acrylate monomer, total carbon number be 5~20 methyl-prop
Olefin(e) acid esters unsaturated monomer, styrene monomer, (methyl) dihydroxypropyl ester monomer, cross-linking monomer and initiator 60~
It is added drop-wise in 180 minutes in step (3) in seed emulsion obtained, reaction temperature controls the heat preservation 90~180 at 70 DEG C~90 DEG C
Minute.
(5) addition of crosslinking agent: being down to 65~75 degrees Celsius for reaction temperature, with pH adjusting agent by reacting solution pH value adjust to
7~9, metal crosslinking agent is added, keeps the temperature 20~40 minutes, is down to room temperature addition adipic dihydrazide and persistently stirs 30~40 points
Clock, the lotion being then obtained by filtration are novel flexographic printing water-based ink binder self-crossing emulsion.
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| CN114456666A (en) * | 2022-03-30 | 2022-05-10 | 北京化工大学 | High-temperature-resistant water-based gloss oil, and preparation method and application thereof |
| CN114752016A (en) * | 2022-05-12 | 2022-07-15 | 北京化工大学 | Ethanol dilution resistant core-shell type self-crosslinking polyacrylate emulsion and preparation method thereof |
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