CN109554019A - A kind of water-borne UV-curing ink of temperature response type polymer modification and its preparation method and application - Google Patents
A kind of water-borne UV-curing ink of temperature response type polymer modification and its preparation method and application Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
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Abstract
The invention discloses a kind of water-borne UV-curing ink of temperature response type polymer modification and its preparation method and application.The application of the temperature response type polymer refers to modified water-soluble UV cured printing ink, is that 15~20% prepolymer with temperature response characteristics for accounting for total mass of raw material is added in the raw material of water-borne UV-curing ink, to promote water-based ink rapid draing.Temperature response type polymer modification is to promote this method of water-borne UV-curing rapid ink drying simple, efficient and environmental-friendly, in the case where keeping existing drying process condition, the quick diffusion discharge that moisture in ink film can be achieved, effectively solves the problems, such as water-based ink slow drying speed.
Description
Technical field
The invention belongs to environment-friendly ink preparation field, in particular to a kind of temperature response type polymer modification is water-borne UV-curing
Ink and its preparation method and application.
Background technique
With the environmental protection policy of ink printing industry to flourish and country's publication is more stringent, many developed countries
Starting legislation control air quality, limits the discharge amount of organic volatile, demand of the market to non-solvent ink is increasing, because
This research and development, which is suitable for the demanding environment-friendly ink that is packed for of the sanitary conditions such as food, beverage, tobacco and wine, drug, becomes off-set oil from now on
The important development direction of ink.Water-based ink gradually replaces discharge organic volatile compound because it has environmental protection and cost advantage
(VOC) solvent-based ink becomes the direction of ink industry development now.But compared with solvent-based ink, water-based ink is because dry
Dry slow and adhesion property is bad, and significantly limits its use scope.Though the environmental protection of UV cured printing ink tool, dry solidification are quick
Etc. advantages, but prepolymer viscosity is larger, need to be added and dilute with the reactive diluent of certain irritation and toxicity.And UV solidified oil
Ink is mostly from import, and at high price, technology is mostly overseas enterprise's monopolization, and the country only has a small amount of enterprise and is able to produce, greatly limits
The popularization and application of environmentally friendly class ink are made.
Existing environment-friendlyink ink is mostly water-based ink, i.e., using water as solvent, so as to avoid generating VOCs, but
Compared to traditional oil-based ink, the rate of drying of water-based ink is slower, influences whether the production efficiency of printed matter, thus limits
The development of water-based ink is made.
Summary of the invention
The present invention is to solve the problems, such as that existing water-based ink rate of drying is too slow, provides a kind of simple, efficient and ring
The water-based ink of border close friend removes water drying means, i.e., the water-borne UV-curing ink of a kind of temperature response type polymer modification and its preparation
Methods and applications.The water-borne UV-curing ink has intelligent temperature response characteristic, can in the case where keeping existing drying process condition
The quick diffusion discharge for realizing moisture in ink film, effectively solves the problems, such as water-based ink slow drying speed.
The present invention provides a kind of application of temperature response type polymer, can be promoted for modified water-soluble UV cured printing ink
Water-borne UV-curing rapid ink drying, the modified water-soluble UV cured printing ink are added in the raw material of the water-borne UV-curing ink
Add 15~20% prepolymer with temperature response characteristics for accounting for total mass of raw material, it is described pre- with temperature response characteristics
Contain hydrophilic radical and hydrophobic group in polymers, while there are reactive epoxy groups.
The hydrophilic radical is polar group, including ehter bond or amide；The hydrophobic group refers to alkyl substituent,
Including methyl, ethyl or isopropyl.
The weight average molecular weight of the prepolymer with temperature response characteristics is 20000-100000, molecular weight distributing index
For 1.9-2.0.
The prepolymer with temperature response characteristics is formed through free-radical polymerized according to parts by weight by following components:
5~10 parts of glycidyl methacrylate,
10~15 parts of monomer,
0.1~0.4 part of potassium peroxydisulfate initiator；
The glycidyl methacrylate provides reactive epoxy groups；The monomer provides hydrophilic radical and dredges
Aqueous group, the monomer be n-isopropyl acrylamide, N- isopropyl acrylamide, N, N- acrylamide,
N- caprolactam, vinyl methyl ether, in polyethylene glycol monomethyl ether methacrylate any one and it is a kind of with
On combined with arbitrary proportion.
The present invention utilizes temperature sensitivity structural unit (the poly-N-isopropyl acryloyl on temperature response type polymer architecture
Amine, LCST=31 DEG C；Poly-N-isopropyl Methacrylamide, LCST=45 DEG C；Poly- N, N- acrylamide, LCST=
25-35℃；Poly-N-vinylcaprolactam, LCST=30-50 DEG C；Polyvinyl methyl ether, LCST=35 DEG C；Polyethylene glycol first
Base ether metacrylic acid ester, LCST=26 DEG C), pass through macromolecular chain fast volume caused by higher drying temperature (> 50 DEG C)
Phase transition, the state that chain conformation is collapsed by the random coil variation being swollen for contraction, macromolecular chain become hydrophobic from hydrophilic, accelerate
Moisture is realized that aqueous UV ink temperature detect switch (TDS) intelligently accelerates drying, is effectively solved aqueous oil by the diffusion of ink film internal layer outer layers
The problem of black slow drying speed.
The prepolymer with temperature response characteristics synthesizes according to the following steps:
(1) in the reaction vessel equipped with blender, condensing unit and temperature regulating device, deionized water is added, methyl is added
Glycidyl acrylate, the mixture of monomer and a part of initiator potassium persulfate after pre-emulsification 10-30min, are warming up to
60-70 DEG C is passed through nitrogen reaction；
(2) after when reaction progress 1-3h is small, residual monomer and initiator is added, the reaction was continued, and 12-16h obtains temperature sound
The pre-polymer solution of characteristic is answered, drying obtains the prepolymer with temperature response characteristics.
The present invention also provides the water-borne UV-curing ink of temperature response type polymer modification, form according to parts by weight,
Include:
Aqueous polyurethane acrylate class binder lotion, 30~60 parts；
Prepolymer with temperature response characteristics, 15~20 parts；
Water-soluble photoinitiator, 1~5 part；
Pigment, 10~15 parts；
Auxiliary agent, 5~10 parts；
Deionized water, 10~20 points
The aqueous polyurethane acrylate class binder lotion is made of following components in parts by weight:
10~20 parts of isophorone diisocyanate；
5~10 parts of hydroxymethyl propionic acid acrylate；
1~5 part of polyethylene glycol；
0.05~0.2 part of dibutyl tin dilaurate；
10~20 parts of hydroxy propyl methacrylate；
0.05~1 part of polymerization inhibitor；
10~20 parts of deionized water.
The auxiliary agent includes crosslinking agent, inorganic filler, levelling agent, defoaming agent and slipping agent.
The crosslinking agent is light resting form crosslinking agent, is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole or phenyl miaow
Azoles.
The inorganic filler, levelling agent, defoaming agent and slipping agent are the usual auxiliaries of ink area, no longer superfluous herein
It states.
The water-soluble photoinitiator is 2,2- dimethyl -2- hydroxy acetophenone, Alpha-hydroxy phenylcyclohexyl ketone, 2- first
At least one of base -1- (4- methyl mercapto phenyl) -2- morpholinyl -1- acetone, 2- isopropyl thioxanthone.
Prepolymer with temperature response characteristics is introduced into ink body as binder with aqueous UV urethane acrylate
Post-crosslinking effect can occur with the crosslinking agent in auxiliary agent-methylimidazole resting form crosslinking agent for system, and generating has heterogeneous knot
The network shaped polymer of structure forms cross-linked network, the water resistance of ink, ink film hardness after solidification with PU body resin
Etc. performances obtained very big improvement.
The water-borne UV-curing ink, it is faster than general traditional water-based ink rate of drying, effectively solve the aqueous oil of tradition
The problem of black slow drying speed.
The aqueous polyurethane acrylate class binder lotion synthesizes according to the following steps:
(1) under nitrogen atmosphere protection, reaction is added in isophorone diisocyanate and hydroxymethyl propionic acid acrylate
In kettle, dibutyl tin dilaurate is then added, under the conditions of 50-60 DEG C of temperature, is stirred to react 1-4h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution is stirred to react 3-6h under the conditions of 60-70 DEG C of temperature, obtains solution B；
(3) addition hydroxy propyl methacrylate carries out sealing end and is cooled to room temperature in above-mentioned solution B, is added in triethanolamine
With at salt.Deionized water is added, stirs 10-30min, finally carries out ultrasonic oscillation 10-30min and obtains aqueous polyurethane propylene
Esters of gallic acid binder lotion.
The hydroxymethyl propionic acid acrylate, chemical structure are as follows:
The preparation method of the water-borne UV-curing ink of temperature response type polymer modification of the present invention synthesizes aqueous poly- first
Urethane acrylate class binder lotion and the prepolymer with temperature response characteristics, are then prepared institute by diluent of water
State the water-borne UV-curing ink of temperature response type polymer modification.
Beneficial effects of the present invention are higher in addition to drying process efficiency, also reside in:
The present invention is based on Molecular Designs to synthesize aqueous UV cured printing ink polyurethane binder, introduces parent in the molecule
Aqueous glycol unit structure.Isophorone diisocyanate and hydroxymethyl propionic acid acrylate reactions first, after certain phase
Polyethylene glycol is added, is finally blocked with hydroxy propyl methacrylate.Non-ionic hydrophilic segment is introduced using polyethylene glycol；Benefit
Carboxyl is introduced with hydroxymethyl propionic acid acrylate, obtains the double bond containing self-emulsifying resin of ionic；Pass through hydroxyethyl methacrylate second
The hydroxyl of ester reacted with polyurethane terminal isocyanate group introduce optical active group, synthesized can self-emulsifying it is water-borne UV-curing
The polyurethane resin of ink.
The water-borne UV-curing ink of temperature response type polymer modification of the present invention has aqueous, environmental protective, nontoxicity, cost
It is cheap, rate of drying is fast, with the high advantage of substrate adhesive property.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1
A. the synthesis of temperature response characteristics prepolymer:
(1) in the three-neck flask equipped with blender, condenser pipe and temperature regulating device, 10 parts of deionized waters are added, are added one
The mixture and initiator potassium persulfate of part methyl glycidyl acrylate (2 parts), monomer (10 parts of vinyl methyl ether)
It 0.05 part, after pre-emulsification 30min, is warming up to 70 DEG C and is passed through nitrogen reaction.
(2) after when reaction progress 3 is small, remaining glycidyl methacrylate (3 parts), monomer (vinyl first is added
5 parts of base ether) and 0.05 part of initiator, the reaction was continued obtains the pre-polymer solution of temperature response characteristics for 16 hours, and drying obtains pre-
Polymers.It is tested by gel permeation chromatography (GPC), the weight average molecular weight for obtaining prepolymer is 100000, molecular weight distributing index
It is 2.0.
B. the preparation of aqueous polyurethane acrylate class binder lotion:
(1) under nitrogen atmosphere protection, by isophorone diisocyanate (10 parts) and hydroxymethyl propionic acid acrylate (5
Part) be added in reaction kettle, dibutyl tin dilaurate (0.05 part) then is added, under the conditions of 60 DEG C of temperature, 200rpm turns
Speed is stirred to react 4h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution (1 part), under the conditions of 70 DEG C of temperature, 200rpm revolving speed is stirred to react 6h, obtains solution B；
(3) addition hydroxy propyl methacrylate (10 parts) carries out sealing end and is cooled to room temperature in above-mentioned solution B, and three second are added
Hydramine is neutralized into salt.Deionized water is added, 1000rpm stirs 30min, finally carries out ultrasonic oscillation 30min and obtains aqueous gather
Urethane acrylate class binder lotion.
C. the preparation of the water-borne UV-curing ink of temperature response type polymer modification is formulated as follows:
Aqueous polyurethane acrylate class binder lotion, 30 parts；
The prepolymer of temperature response characteristics, 20 parts；
Water-soluble photoinitiator, 1 part；
Pigment, 10 parts；
Auxiliary agent, 5 parts；
Deionized water, 20 parts.
Wherein auxiliary agent includes 1 part of crosslinking agent (imidazoles), 1 part of inorganic filler (silica), 1 part of levelling agent (Bi Ke chemistry
BYK-380N), 1 part of defoaming agent (Bi Ke chemistry BYK022) and 1 part of slipping agent, water-soluble photoinitiator 2,2- dimethyl -2- hydroxyl
Benzoylformaldoxime (1 part).
Comparative example 1
In addition to the synthesis of the prepolymer with temperature response characteristics, temperature response characteristics pre-polymerization is not introduced in ink component
Object, other preparation conditions, formula and operating procedure are same as Example 1.
Embodiment 2
A. the synthesis of temperature response characteristics prepolymer:
(1) in the three-neck flask equipped with blender, condenser pipe and temperature regulating device, 12 parts of deionized waters are added, are added one
The mixture and initiator over cure of part methyl glycidyl acrylate (3 parts), monomer (n-isopropyl acrylamide, 9 parts)
Sour potassium (0.1 part) after pre-emulsification 20min, is warming up to 65 DEG C and is passed through nitrogen reaction.
(2) after when reaction progress 2 is small, remaining glycidyl methacrylate (3 parts), monomer (N- isopropyl is added
Acrylamide, 5 parts) and initiator potassium persulfate (0.1 part), the reaction was continued obtain within 14 hours temperature response characteristics prepolymer it is molten
Liquid, drying obtain prepolymer.It is tested by gel permeation chromatography (GPC), the weight average molecular weight for obtaining prepolymer is 80000, point
Son amount profile exponent is 2.0.
B. the preparation of aqueous polyurethane acrylate class binder lotion:
(1) under nitrogen atmosphere protection, by isophorone diisocyanate (12 parts) and hydroxymethyl propionic acid acrylate (6
Part) be added in reaction kettle, dibutyl tin dilaurate (0.1 part) then is added, under the conditions of 60 DEG C of temperature, 200rpm revolving speed
It is stirred to react 3h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution (2 parts), under the conditions of 65 DEG C of temperature, 200rpm revolving speed is stirred to react 4h, obtains solution B；
(3) addition hydroxy propyl methacrylate (12 parts) carries out sealing end and is cooled to room temperature in above-mentioned solution B, and three second are added
Hydramine is neutralized into salt.Deionized water is added, 1000rpm stirs 25min, finally carries out ultrasonic oscillation 25min and obtains aqueous gather
Urethane acrylate class binder lotion.
C. the preparation of the water-borne UV-curing ink of temperature response type polymer modification is formulated as follows:
Aqueous polyurethane acrylate class binder lotion, 40 parts；
The prepolymer of temperature response characteristics, 18 parts；
Water-soluble photoinitiator, 2 parts；
Pigment, 11 parts；
Auxiliary agent, 6 parts；
Deionized water, 16 parts.
Wherein auxiliary agent includes 1 part of crosslinking agent (2-ethyl-4-methylimidazole), 2 parts of inorganic fillers (talcum powder), 1 part of levelling
Agent (Bi Ke chemistry BYK-380N), 1 part of defoaming agent (Bi Ke chemistry BYK022) and 1 part of slipping agent, water-soluble photoinitiator 2,2-
Dimethyl -2- hydroxy acetophenone (1 part), Alpha-hydroxy phenylcyclohexyl ketone (1 part) mixture.
Comparative example 2
In addition to the synthesis of the prepolymer with temperature response characteristics, temperature response characteristics pre-polymerization is not introduced in ink component
Object, other preparation conditions, formula and operating procedure are same as Example 2.
Embodiment 3
A. the synthesis of temperature response characteristics prepolymer:
(1) in the three-neck flask equipped with blender, condenser pipe and temperature regulating device, 14 parts of deionized waters are added, are added one
The mixing of part methyl glycidyl acrylate (4 parts), monomer (5 parts of n-isopropyl acrylamide, 2 parts of vinyl methyl ether)
Object and initiator potassium persulfate (0.2 part) after pre-emulsification 15min, are warming up to 65 DEG C and are passed through nitrogen reaction.
(2) after when reaction progress 1.5 is small, remaining glycidyl methacrylate (3 parts), monomer (N- isopropyl is added
3 parts of base acrylamide, 3 parts of vinyl methyl ether) and initiator potassium persulfate (0.1 part), the reaction was continued 14 hours obtains temperature
The pre-polymer solution of response characteristic, drying obtain prepolymer.It is tested by gel permeation chromatography (GPC), obtains the weight of prepolymer
Average molecular weight is 50000, molecular weight distributing index 1.9.
B. the preparation of aqueous polyurethane acrylate class binder lotion:
(1) under nitrogen atmosphere protection, by isophorone diisocyanate (15 parts) and hydroxymethyl propionic acid acrylate
In (7.5 parts) addition reaction kettles, dibutyl tin dilaurate (0.15 part) then is added, under the conditions of 55 DEG C of temperature,
200rpm revolving speed is stirred to react 2h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution (3 parts), under the conditions of 65 DEG C of temperature, 200rpm revolving speed is stirred to react 4h, obtains solution B；
(3) addition hydroxy propyl methacrylate (15 parts) carries out sealing end and is cooled to room temperature in above-mentioned solution B, and three second are added
Hydramine is neutralized into salt.Deionized water is added, 1000rpm stirs 15min, finally carries out ultrasonic oscillation 15min and obtains aqueous gather
Urethane acrylate class binder lotion.
C. the preparation of the water-borne UV-curing ink of temperature response type polymer modification is formulated as follows:
Aqueous polyurethane acrylate class binder lotion, 45 parts；
The prepolymer of temperature response characteristics, 17 parts；
Water-soluble photoinitiator, 3 parts；
Pigment, 12 parts；
Auxiliary agent, 7 parts；
Deionized water, 14 parts.
Wherein auxiliary agent includes 2 parts of crosslinking agents (1 part of 2-methylimidazole, 1 part of 2-ethyl-4-methylimidazole), 2 parts of inorganic fillers
(talcum powder), 1 part of levelling agent (Bi Ke chemistry BYK-380N), 1 part of defoaming agent (Bi Ke chemistry BYK022) and 1 part of slipping agent, water
Property photoinitiator be 2,2- dimethyl-2- hydroxy acetophenone (1 part), Alpha-hydroxy phenylcyclohexyl ketone (1 part), 2- methyl-1-(4-
Methyl mercapto phenyl) -2- morpholinyl -1- acetone (1 part) mixture.
Comparative example 3
In addition to the synthesis of the prepolymer with temperature response characteristics, temperature response characteristics pre-polymerization is not introduced in ink component
Object, other preparation conditions, formula and operating procedure are same as Example 3.
Embodiment 4
A. the synthesis of temperature response characteristics prepolymer:
(1) in the three-neck flask equipped with blender, condenser pipe and temperature regulating device, 18 parts of deionized waters are added, are added one
The mixture and initiator over cure of part methyl glycidyl acrylate (5 parts), monomer (n-isopropyl acrylamide, 6 parts)
Sour potassium (0.2 part) after pre-emulsification 10min, is warming up to 60 DEG C and is passed through nitrogen reaction.
(2) after when reaction progress 3 is small, remaining glycidyl methacrylate (4 parts), monomer (N- isopropyl is added
Acrylamide, 6 parts) and initiator potassium persulfate (0.2 part), the reaction was continued obtain within 15 hours temperature response characteristics prepolymer it is molten
Liquid, drying obtain prepolymer.It is tested by gel permeation chromatography (GPC), the weight average molecular weight for obtaining prepolymer is 40000, point
Son amount profile exponent is 1.9.
B. the preparation of aqueous polyurethane acrylate class binder lotion:
(1) under nitrogen atmosphere protection, by isophorone diisocyanate (18 parts) and hydroxymethyl propionic acid acrylate (9
Part) be added in reaction kettle, dibutyl tin dilaurate (0.18 part) then is added, under the conditions of 55 DEG C of temperature, 200rpm turns
Speed is stirred to react 2h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution (4 parts), under the conditions of 65 DEG C of temperature, 200rpm revolving speed is stirred to react 4h, obtains solution B；
(3) addition hydroxy propyl methacrylate (18 parts) carries out sealing end and is cooled to room temperature in above-mentioned solution B, and three second are added
Hydramine is neutralized into salt.Deionized water is added, 1000rpm stirs 10min, finally carries out ultrasonic oscillation 10min and obtains aqueous gather
Urethane acrylate class binder lotion.
C. the preparation of the water-borne UV-curing ink of temperature response type polymer modification is formulated as follows:
Aqueous polyurethane acrylate class binder lotion, 50 parts；
The prepolymer of temperature response characteristics, 16 parts；
Water-soluble photoinitiator, 4 parts；
Pigment, 13 parts；
Auxiliary agent, 8 parts；
Deionized water, 12 parts.
Wherein auxiliary agent includes 2 parts of crosslinking agents (1 part of 2-methylimidazole, 1 part of 2-ethyl-4-methylimidazole), 2 parts of inorganic fillers
(talcum powder), 2 parts of levelling agents (Bi Ke chemistry BYK-380N), 1 part of defoaming agent (Bi Ke chemistry BYK022) and 1 part of slipping agent, water
Property photoinitiator be 2,2- dimethyl-2- hydroxy acetophenone (1 part), Alpha-hydroxy phenylcyclohexyl ketone (1 part), 2- methyl-1-(4-
Methyl mercapto phenyl) -2- morpholinyl -1- acetone (1 part), 2- isopropyl thioxanthone (1 part) mixture.
Comparative example 4
In addition to the synthesis of the prepolymer with temperature response characteristics, temperature response characteristics pre-polymerization is not introduced in ink component
Object, other preparation conditions, formula and operating procedure are same as Example 4.
Embodiment 5
A. the synthesis of temperature response characteristics prepolymer:
(1) in the three-neck flask equipped with blender, condenser pipe and temperature regulating device, 20 parts of deionized waters are added, are added one
The mixture and initiator potassium persulfate of part methyl glycidyl acrylate (5 parts), monomer (5 parts of vinyl methyl ether)
(0.1 part) after pre-emulsification 10min, is warming up to 60 DEG C and is passed through nitrogen reaction.
(2) after when reaction progress 1 is small, remaining glycidyl methacrylate (5 parts), monomer (N- isopropyl is added
Acrylamide, 5 parts) and initiator potassium persulfate (0.1 part), the reaction was continued obtain within 12 hours temperature response characteristics prepolymer it is molten
Liquid, drying obtain prepolymer.It is tested by gel permeation chromatography (GPC), the weight average molecular weight for obtaining prepolymer is 20000, point
Son amount profile exponent is 1.9.
B. the preparation of aqueous polyurethane acrylate class binder lotion:
(1) under nitrogen atmosphere protection, by isophorone diisocyanate (20 parts) and hydroxymethyl propionic acid acrylate (10
Part) be added in reaction kettle, dibutyl tin dilaurate (0.2 part) then is added, under the conditions of 50 DEG C of temperature, 200rpm revolving speed
It is stirred to react 1h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A
Polyglycol solution (5 parts), under the conditions of 60 DEG C of temperature, 200rpm revolving speed is stirred to react 3h, obtains solution B；
(3) addition hydroxy propyl methacrylate (20 parts) carries out sealing end and is cooled to room temperature in above-mentioned solution B, and three second are added
Hydramine is neutralized into salt.Deionized water is added, 1000rpm stirs 10min, finally carries out ultrasonic oscillation 10min and obtains aqueous gather
Urethane acrylate class binder lotion.
C. the preparation of the water-borne UV-curing ink of temperature response type polymer modification is formulated as follows:
Aqueous polyurethane acrylate class binder lotion, 60 parts；
The prepolymer of temperature response characteristics, 15 parts；
Water-soluble photoinitiator, 5 parts；
Pigment, 15 parts；
Auxiliary agent, 10 parts；
Deionized water, 10 parts.
Wherein auxiliary agent includes 3 parts of crosslinking agents (1 part of 2-methylimidazoles, 1 part of 2-ethyl-4-methylimidazole, 2- phenylimidazole 1
Part), 2 parts of inorganic fillers (talcum powder), 2 parts of levelling agents (Bi Ke chemistry BYK-380N), 2 parts of defoaming agents (Bi Ke chemistry BYK022)
And 1 part of slipping agent, water-soluble photoinitiator are 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone (5 parts).
Comparative example 5
In addition to the synthesis of the prepolymer with temperature response characteristics, temperature response characteristics pre-polymerization is not introduced in ink component
Object, other preparation conditions, formula and operating procedure are same as Example 5.
Comparative example 6
The ratio for controlling monomer and initiator is 20:0.4, and preparation weight average molecular weight is 10000, and molecular weight distributing index is
2.0 temperature response characteristics prepolymer, other preparation conditions and operating procedure are same as Example 5.
Comparative example 7
The ratio for controlling monomer and initiator is 20:0.02, and preparation weight average molecular weight is 200000, molecular weight distributing index
For 1.9 temperature response characteristics prepolymer, other preparation conditions and operating procedure are same as Example 5.
Embodiment 6
Monomer in the synthesis step of prepolymer with temperature response characteristics replaces with N- isopropyl acrylamide,
Dosage is 15 parts, and the additive amount and step of other components are same as Example 1, and gained has the prepolymer of temperature response characteristics
Molecular weight is 90000, profile exponent 1.9.
Embodiment 7
Monomer in the synthesis step of prepolymer with temperature response characteristics replaces with N, and N- acrylamide is used
Amount is 16 parts, and the additive amount and step of other components are same as Example 1, and gained has point of the prepolymer of temperature response characteristics
Son amount is 95000, profile exponent 2.0.
Embodiment 8
Monomer in the synthesis step of prepolymer with temperature response characteristics replaces with N- caprolactam, dosage
It is 17 parts, the additive amount and step of other components are same as Example 1, and gained has the molecule of the prepolymer of temperature response characteristics
Amount is 85000, profile exponent 1.9.
Embodiment 9
Monomer in the synthesis step of prepolymer with temperature response characteristics replaces with Ethylene Glycol Methyl ether methyl
Acid esters, dosage are 15 parts, and the additive amount and step of other components are same as Example 1, and gained has the pre- of temperature response characteristics
The molecular weight of polymers is 70000, profile exponent 1.9.
Each component is mixed in proportion, is put into special bucket, is stirred with blender, keeps pigment and binder preliminary
Mixing forms paste, and the material after stirring will be ground, and checks form and aspect, fineness, mobility, viscosity and drying property etc.
Whether property meets design requirement, and ink barrelling is spare after adjusted and finished product inspection.
Ink performance test
Rate of drying test: sample is made with blade coating mode, is dried under the conditions of 60 DEG C of temperature, ink print thickness exists
5um, test moisture drop to time when trace (absolutely dry).
Attachment fastness test: referring to GB/T 13217.7-2009
In order to verify the comprehensive performance of environment-friendly type UV cured printing ink of the present invention, above-mentioned 5 embodiments and 5 are compared
The drying property and attachment fastness of environment-friendly type UV cured printing ink in example are tested.
Test result is as follows shown in table:
As seen from the above table, when weight average molecular weight is between 10000-100000, when molecular weight distributing index 1.9-2.0,
Compared to comparative example 1-5, the obtained water-borne UV-curing ink of temperature response type polymer modification of 1-5 according to embodiments of the present invention
Drying time between 2~3s, drying time is obviously shortened；Meanwhile the attachment of the environment-friendly type aqueous UV cured printing ink of the present invention
Fastness is maintained at 97-98%；When weight average molecular weight exceeds range above, compared with Example 5 compared with comparative example 6 uses molecular weight
It is 10000, when molecular weight distributing index is 2.0, rate of drying and adhesion property decline show there is the pre- of temperature response characteristics
Polymers molecular weight is lower, and strand is shorter, so that the prepolymer with temperature response characteristics is difficult to carry out ring in ink system
Cross-linking reaction caused by oxygen groups open loop can not form cross-linked network system, not have the effect for improving ink setting speed；When
Weight average molecular weight exceeds range above, and using molecular weight compared with, comparative example 7 compared with Example 5, molecular weight distribution refers to for 200000
When number is 1.9, rate of drying and adhesion property also decline, when showing to have the prepolymer molecular weight of temperature response characteristics too high,
Strand is longer, and chain entanglement is more serious, so that diffusion of the prepolymer with temperature response characteristics in ink system is impacted,
Also lead to not to form effective cross-linked network system, also do not have the effect for improving ink setting speed.Embodiment 6-9 is to adopt
(poly-N-isopropyl methacryl, poly- N, N- diethyl acryloyl, poly N-vinyl are in oneself for the prepolymer obtained with different monomers
Amide, polyethylene glycol monomethyl ether methacrylate) prepare aqueous UV ink, it can be seen that all aqueous UV ink show compared with
Fast rate of drying and good attachment fastness.
The present invention is prepared for a kind of pair of fast environment-friendly type temperature response type polymer modification of temperature intelligent response, rate of drying
Water-borne UV-curing ink.The water-borne UV-curing ink of temperature response type polymer modification takes water as a solvent, and can be effectively reduced
The volatilization of organic volatile meets environmentally protective demand for development；The water-borne UV-curing oil of temperature response type polymer modification
Ink has intelligent temperature response characteristic, in the case where keeping existing drying process condition, it can be achieved that in ink film the quick diffusion of moisture arrange
Out, water-based ink slow drying speed is effectively solved the problems, such as.It can be used for medicine to print with cigarette packet package, meet stringent health
Condition requirement, while meeting the requirement of low-carbon environment-friendly.
Claims (8)
1. a kind of application of temperature response type polymer, which is characterized in that be that can promote water for modified water-soluble UV cured printing ink
Property UV cured printing ink rapid draing, the modified water-soluble UV cured printing ink is added in the raw material of the water-borne UV-curing ink
Account for 15~20% prepolymer with temperature response characteristics of total mass of raw material, the pre-polymerization with temperature response characteristics
Contain hydrophilic radical and hydrophobic group in object, while there are reactive epoxy groups.
2. application according to claim 1, which is characterized in that the hydrophilic radical is polar group, including ehter bond or
Amide；The hydrophobic group refers to alkyl substituent, including methyl, ethyl or isopropyl.
3. application according to claim 1 again, which is characterized in that the prepolymer with temperature response characteristics is divided equally
Son amount is 20000-100000, molecular weight distributing index 1.9-2.0.
4. application according to claim 1,2 or 3, which is characterized in that the prepolymer with temperature response characteristics by
Following components are formed through free-radical polymerized according to parts by weight:
5~10 parts of glycidyl methacrylate,
10~15 parts of monomer,
0.1~0.4 part of potassium peroxydisulfate initiator；
The glycidyl methacrylate provides reactive epoxy groups；The monomer provides hydrophilic radical and hydrophobicity
Group, the monomer are n-isopropyl acrylamide, N- isopropyl acrylamide, N, N- acrylamide, N- second
Alkenyl caprolactam, vinyl methyl ether, any one and more than one in polyethylene glycol monomethyl ether methacrylate with
Arbitrary proportion combination.
5. application according to claim 4, which is characterized in that the prepolymer with temperature response characteristics according to
Lower step synthesis:
(1) in the reaction vessel equipped with blender, condensing unit and temperature regulating device, deionized water, methacrylic acid contracting is added
Water glyceride, the mixture of monomer and a part of initiator potassium persulfate after pre-emulsification 10-30min, are warming up to 60-70 DEG C
It is passed through nitrogen reaction；
(2) after when reaction progress 1-3h is small, residual monomer and initiator is added, the reaction was continued, and 12-16h is obtained with temperature
The pre-polymer solution of response characteristic, drying obtain the prepolymer with temperature response characteristics.
6. the resulting water-borne UV-curing ink of temperature response type polymer modification of application described in claim 1, which is characterized in that
It is formed according to parts by weight, comprising:
Aqueous polyurethane acrylate class binder lotion, 30~60 parts；
Prepolymer with temperature response characteristics, 15~20 parts；
Water-soluble photoinitiator, 1~5 part；
Pigment, 10~15 parts；
Auxiliary agent, 5~10 parts；
Deionized water, 10~20 parts；
The aqueous polyurethane acrylate class binder lotion is made of following components in parts by weight:
10~20 parts of isophorone diisocyanate；
5~10 parts of hydroxymethyl propionic acid acrylate；
1~5 part of polyethylene glycol；
0.05~0.2 part of dibutyl tin dilaurate；
10~20 parts of hydroxy propyl methacrylate；
0.05~1 part of polymerization inhibitor；
10~20 parts of deionized water；
The auxiliary agent includes crosslinking agent, inorganic filler, levelling agent, defoaming agent and slipping agent；
The crosslinking agent is light resting form crosslinking agent, is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole or phenylimidazole；
The water-soluble photoinitiator is 2,2- dimethyl-2- hydroxy acetophenone, Alpha-hydroxy phenylcyclohexyl ketone, 2- methyl-1-
At least one of (4- methyl mercapto phenyl) -2- morpholinyl -1- acetone, 2- isopropyl thioxanthone.
7. the water-borne UV-curing ink of temperature response type polymer modification according to claim 6, which is characterized in that the water
Property polyurethane acrylates binder lotion synthesizes according to the following steps:
(1) under nitrogen atmosphere protection, isophorone diisocyanate and hydroxymethyl propionic acid acrylate are added in reaction kettle,
Then dibutyl tin dilaurate is added, under the conditions of 50-60 DEG C of temperature, is stirred to react 1-4h, obtains solution A；
(2) it when no longer being changed with the value that di-n-butylamine method measures into reactant isocyano, is added in above-mentioned solution A poly-
Ethylene glycol solution is stirred to react 3-6h under the conditions of 60-70 DEG C of temperature, obtains solution B；
(3) addition hydroxy propyl methacrylate carries out sealing end and is cooled to room temperature in above-mentioned solution B, and triethanolamine is added and neutralizes
At salt；Deionized water is added, stirs 10-30min, finally carries out ultrasonic oscillation 10-30min and obtains watersoluble polyurethane acrylic acid
Esters binder lotion.
8. the preparation method of the water-borne UV-curing ink of temperature response type polymer modification, feature described in claim 6 or 7 exist
In aqueous polyurethane acrylates binder lotion and the prepolymer with temperature response characteristics being synthesized first, then with water
For diluent, water-soluble photoinitiator, pigment and auxiliary agent is added, it is solid that the aqueous UV of temperature response type polymer modification is prepared
Carburetion ink.
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