CN109554019B - Temperature response type polymer modified water-based UV (ultraviolet) curing ink and preparation method and application thereof - Google Patents
Temperature response type polymer modified water-based UV (ultraviolet) curing ink and preparation method and application thereof 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
- 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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/67—Unsaturated compounds having active hydrogen
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- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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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
- 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
Abstract
The invention discloses temperature response type polymer modified water-based UV curing ink and a preparation method and application thereof. The application of the temperature response type polymer refers to modified water-based UV curing ink, and is characterized in that a prepolymer with temperature response characteristics accounting for 15-20% of the total mass of raw materials is added into the raw materials of the water-based UV curing ink so as to promote the rapid drying of the water-based ink. The method for promoting the rapid drying of the water-based UV curing ink by modifying the temperature response type polymer is simple, efficient and environment-friendly, can realize the rapid diffusion and discharge of water in an ink film under the condition of keeping the existing drying process, and effectively solves the problem of low drying speed of the water-based ink.
Description
Technical Field
The invention belongs to the field of preparation of environment-friendly ink, and particularly relates to temperature-responsive polymer modified water-based UV (ultraviolet) curing ink as well as a preparation method and application thereof.
Background
With the vigorous development of the ink printing industry and the release of stricter environmental protection policies by countries, many developed countries begin to legislate the control of air quality, limit the discharge amount of organic volatile matters, and the market demand for non-solvent type inks is increasing, so that the development of environment-friendly inks for packaging which are suitable for food, beverage, cigarette and wine, medicines and the like with high requirements on sanitary conditions becomes an important development direction of printing inks in the future. The water-based ink has the advantages of environmental protection and cost, and gradually replaces solvent-based ink which discharges organic volatile compounds (VOC), so that the water-based ink becomes the development direction of the ink industry at present. However, compared with solvent-based inks, water-based inks have a slow drying rate and poor adhesion, and thus the application range of the water-based inks is greatly limited. Although the UV curing ink has the advantages of environmental protection, rapid drying and curing and the like, the prepolymer has high viscosity and needs to be diluted by adding an active diluent with certain irritation and toxicity. And the UV curing ink comes from import mostly, the price is high, the technology is mostly monopolized by foreign enterprises, only a small number of enterprises can produce at home, and the popularization and the application of the environment-friendly ink are greatly limited.
Most of the existing environment-friendly ink is water-based ink, namely water is used as a solvent, so that VOCs can be prevented from being generated, but compared with the traditional oil-based ink, the water-based ink is low in drying speed, the production efficiency of printed products can be influenced, and the development of the water-based ink is limited.
Disclosure of Invention
The invention provides a simple, efficient and environment-friendly water-based ink dewatering and drying method for solving the problem that the existing water-based ink is too slow in drying speed, namely a temperature response type polymer modified water-based UV (ultraviolet) curing ink and a preparation method and application thereof. The water-based UV curing ink has an intelligent temperature response characteristic, can realize rapid diffusion and discharge of water in an ink film under the condition of keeping the existing drying process, and effectively solves the problem of low drying speed of the water-based ink.
The invention provides an application of a temperature response type polymer, which is used for modifying water-based UV curing ink and can promote the rapid drying of the water-based UV curing ink, wherein the modified water-based UV curing ink is prepared by adding a prepolymer with a temperature response characteristic, which accounts for 15-20% of the total mass of raw materials, into the raw materials of the water-based UV curing ink, and the prepolymer with the temperature response characteristic contains a hydrophilic group, a hydrophobic group and a reactive epoxy group.
The hydrophilic group is a polar group including an ether bond or an amide; the hydrophobic group refers to an alkyl substituent including methyl, ethyl or isopropyl.
The weight average molecular weight of the prepolymer with the temperature response characteristic is 20000-100000, and the molecular weight distribution index is 1.9-2.0.
The prepolymer with the temperature response characteristic is prepared by the following components in parts by weight through free radical copolymerization:
5-10 parts of glycidyl methacrylate,
10-15 parts of a monomer,
0.1-0.4 part of potassium persulfate initiator;
the glycidyl methacrylate provides a reactive epoxy group; the monomer provides a hydrophilic group and a hydrophobic group, and is any one or more of N-isopropyl acrylamide, N-isopropyl methacrylamide, N-diethyl acrylamide, N-vinyl caprolactam, vinyl methyl ether and polyethylene glycol methyl ether methacrylate in any proportion.
The invention utilizes temperature sensitive structural units (poly-N-isopropyl acrylamide, LCST is 31 ℃; poly-N-isopropyl methacrylamide, LCST is 45 ℃; poly-N, N-diethyl acrylamide, LCST is 25-35 ℃; poly-N-vinyl caprolactam, LCST is 30-50 ℃; polyvinyl methyl ether, LCST is 35 ℃; polyethylene glycol methyl ether methacrylate, LCST is 26 ℃) on the temperature responsive polymer structure, through the rapid volume phase transformation of a high-molecular chain caused by a higher drying temperature (>50 ℃), the chain conformation is changed from a swelled random coil to a contracted and collapsed state, the high-molecular chain is changed from hydrophilic to hydrophobic, the diffusion of water from the inner layer to the outer layer of the ink film is accelerated, the intelligent accelerated drying of the temperature control switch of the water-based UV ink is realized, and the problem of low drying speed of the water-based ink is effectively solved.
The prepolymer with the temperature response characteristic is synthesized according to the following steps:
(1) adding deionized water into a reaction vessel provided with a stirrer, a condensing device and a temperature control device, adding a mixture of glycidyl methacrylate and a monomer and a part of initiator potassium persulfate, pre-emulsifying for 10-30min, heating to 60-70 ℃, and introducing nitrogen for reaction;
(2) and after the reaction is carried out for 1-3h, adding the residual monomers and the initiator, continuously reacting for 12-16h to obtain a prepolymer solution with the temperature response characteristic, and drying to obtain the prepolymer with the temperature response characteristic.
The invention also provides temperature response type polymer modified water-based UV curing printing ink which comprises the following components in parts by weight:
30-60 parts of aqueous polyurethane acrylate binder emulsion;
15-20 parts of prepolymer with temperature response characteristic;
1-5 parts of a water-based photoinitiator;
10-15 parts of pigment;
5-10 parts of an auxiliary agent;
10 to 20 minutes of deionized water
The aqueous polyurethane acrylate binder emulsion comprises the following components in parts by weight:
10-20 parts of isophorone diisocyanate;
5-10 parts of hydroxymethyl propionic acid acrylate;
1-5 parts of polyethylene glycol;
0.05-0.2 part of dibutyltin dilaurate;
10-20 parts of hydroxypropyl methacrylate;
0.05-1 part of polymerization inhibitor;
10-20 parts of deionized water.
The auxiliary agent comprises a cross-linking agent, an inorganic filler, a flatting agent, a defoaming agent and a slipping agent.
The cross-linking agent is a light latent cross-linking agent and is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole or phenylimidazole.
The inorganic filler, the leveling agent, the defoaming agent and the slipping agent are common auxiliary agents in the field of printing ink, and are not described again here.
The aqueous photoinitiator is at least one of 2, 2-dimethyl-2-hydroxyacetophenone, alpha-hydroxycyclohexyl benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and 2-isopropyl thioxanthone.
The prepolymer with the temperature response characteristic and the water-based UV polyurethane acrylate are introduced into an ink system as connecting materials, and can generate post-crosslinking action with a crosslinking agent-methylimidazole latent crosslinking agent in an auxiliary agent to generate a network polymer with a heterogeneous structure, and the network polymer and polyurethane main body resin form a network crosslinking structure, so that the water resistance, ink film hardness and other properties of the cured ink are greatly improved.
The water-based UV curing ink has a higher drying speed than the common traditional water-based ink, and effectively solves the problem of low drying speed of the traditional water-based ink.
The aqueous polyurethane acrylate binder emulsion is synthesized by the following steps:
(1) under the protection of nitrogen atmosphere, adding isophorone diisocyanate and hydroxymethyl propionic acid acrylate into a reaction kettle, then adding dibutyltin dilaurate, and stirring and reacting for 1-4h at the temperature of 50-60 ℃ to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding a polyethylene glycol solution into the solution A, and stirring and reacting for 3-6h at the temperature of 60-70 ℃ to obtain a solution B;
(3) adding hydroxypropyl methacrylate into the solution B, sealing, cooling to normal temperature, adding triethanolamine, and neutralizing to form salt. Adding deionized water, stirring for 10-30min, and finally performing ultrasonic oscillation for 10-30min to obtain the waterborne polyurethane acrylate binder emulsion.
The chemical structure of the hydroxymethyl propionic acid acrylate is as follows:
the preparation method of the temperature response type polymer modified water-based UV curing ink comprises the steps of firstly synthesizing water-based polyurethane acrylate connecting material emulsion and prepolymer with temperature response characteristic, and then preparing the temperature response type polymer modified water-based UV curing ink by taking water as a diluent.
The invention has the advantages of higher efficiency in the drying process, as follows:
the polyurethane binder for the water-based UV curing ink is designed and synthesized based on a molecular structure, and a hydrophilic dihydric alcohol unit structure is introduced into molecules. Firstly, reacting isophorone diisocyanate with hydroxymethyl acrylic acid ester, adding polyethylene glycol after certain stages, and finally, blocking with hydroxypropyl methacrylate. Introducing a non-ionic hydrophilic chain segment by using polyethylene glycol; introducing carboxyl by utilizing hydroxymethyl propionic acid acrylate to obtain ionic self-emulsifying resin containing double bonds; the hydroxyl of hydroxyethyl methacrylate reacts with the terminal isocyanate group of polyurethane to introduce a photoactive group, so that the self-emulsifiable polyurethane resin for the water-based UV curing ink is synthesized.
The temperature response type polymer modified water-based UV curing ink has the advantages of water-based environmental protection, no toxicity, low cost, high drying speed and high bonding performance with a base material.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
A. Temperature response characteristic prepolymer synthesis:
(1) in a three-necked flask equipped with a stirrer, a condenser tube and a temperature control device, 10 parts of deionized water was added, a part of a mixture of glycidyl methacrylate (2 parts), a monomer (10 parts of vinyl methyl ether) and 0.05 part of potassium persulfate as an initiator were added, pre-emulsification was carried out for 30min, and then the temperature was raised to 70 ℃ and nitrogen gas was introduced for reaction.
(2) And when the reaction is carried out for 3 hours, adding the rest of glycidyl methacrylate (3 parts), a monomer (5 parts of vinyl methyl ether) and 0.05 part of an initiator, continuously reacting for 16 hours to obtain a prepolymer solution with temperature response characteristics, and drying to obtain a prepolymer. The weight average molecular weight of the prepolymer was 100000 and the molecular weight distribution index was 2.0 as measured by Gel Permeation Chromatography (GPC).
B. Preparing aqueous polyurethane acrylate binder emulsion:
(1) under the protection of nitrogen atmosphere, adding 10 parts of isophorone diisocyanate (isophorone diisocyanate) and 5 parts of hydroxymethyl propionic acid acrylate (hydroxymethyl propionic acid acrylate) into a reaction kettle, then adding 0.05 part of dibutyltin dilaurate, and stirring and reacting at the temperature of 60 ℃ and the rotating speed of 200rpm for 4 hours to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding polyethylene glycol solution (1 part) into the solution A, and stirring and reacting for 6 hours at the temperature of 70 ℃ and the rotating speed of 200rpm to obtain solution B;
(3) adding hydroxypropyl methacrylate (10 parts) into the solution B, sealing, cooling to normal temperature, and adding triethanolamine to neutralize and form salt. Adding deionized water, stirring at 1000rpm for 30min, and finally performing ultrasonic oscillation for 30min to obtain the aqueous polyurethane acrylate binder emulsion.
C. The temperature response type polymer modified water-based UV curing ink is prepared by the following formula:
30 parts of waterborne polyurethane acrylate binder emulsion;
20 parts of prepolymer with temperature response characteristic;
1 part of water-based photoinitiator;
10 parts of pigment;
5 parts of an auxiliary agent;
deionized water, 20 parts.
The auxiliary agent comprises 1 part of cross-linking agent (imidazole), 1 part of inorganic filler (silicon dioxide), 1 part of flatting agent (BYK-380N), 1 part of defoaming agent (BYK 022) and 1 part of slipping agent, and the water-based photoinitiator is 2, 2-dimethyl-2-hydroxyacetophenone (1 part).
Comparative example 1
The preparation conditions, formulation and operation steps were the same as in example 1 except that the prepolymer having temperature response characteristics was synthesized without introducing the prepolymer having temperature response characteristics into the ink components.
Example 2
A. Temperature response characteristic prepolymer synthesis:
(1) 12 parts of deionized water are added into a three-neck flask provided with a stirrer, a condenser tube and a temperature control device, a part of the mixture of glycidyl methacrylate (3 parts), a monomer (N-isopropylacrylamide, 9 parts) and an initiator potassium persulfate (0.1 part) are added, pre-emulsification is carried out for 20min, and then the temperature is raised to 65 ℃ and nitrogen is introduced for reaction.
(2) And when the reaction is carried out for 2 hours, adding the rest of glycidyl methacrylate (3 parts), a monomer (N-isopropylacrylamide, 5 parts) and an initiator potassium persulfate (0.1 part), continuously reacting for 14 hours to obtain a prepolymer solution with temperature response characteristics, and drying to obtain a prepolymer. The prepolymer was found to have a weight average molecular weight of 80000 and a molecular weight distribution index of 2.0 by Gel Permeation Chromatography (GPC) test.
B. Preparing aqueous polyurethane acrylate binder emulsion:
(1) under the protection of nitrogen atmosphere, adding isophorone diisocyanate (12 parts) and hydroxymethyl propionic acid acrylate (6 parts) into a reaction kettle, then adding dibutyltin dilaurate (0.1 part), and stirring at the rotating speed of 200rpm at the temperature of 60 ℃ for reaction for 3 hours to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding polyethylene glycol solution (2 parts) into the solution A, and stirring and reacting for 4 hours at the temperature of 65 ℃ and the rotating speed of 200rpm to obtain solution B;
(3) adding hydroxypropyl methacrylate (12 parts) into the solution B, sealing, cooling to normal temperature, and adding triethanolamine to neutralize and form salt. Adding deionized water, stirring at 1000rpm for 25min, and finally performing ultrasonic oscillation for 25min to obtain the aqueous polyurethane acrylate binder emulsion.
C. The temperature response type polymer modified water-based UV curing ink is prepared by the following formula:
40 parts of waterborne polyurethane acrylate binder emulsion;
18 parts of prepolymer with temperature response characteristic;
2 parts of a water-based photoinitiator;
11 parts of pigment;
6 parts of an auxiliary agent;
deionized water, 16 parts.
The auxiliary agent comprises 1 part of a cross-linking agent (2-ethyl-4-methylimidazole), 2 parts of an inorganic filler (talcum powder), 1 part of a flatting agent (BYK-380N), 1 part of a defoaming agent (BYK 022) and 1 part of a slipping agent, and the water-based photoinitiator is a mixture of 2, 2-dimethyl-2-hydroxyacetophenone (1 part) and alpha-hydroxycyclohexyl benzophenone (1 part).
Comparative example 2
The preparation conditions, formulation and operation steps were the same as in example 2 except that the prepolymer having temperature response characteristics was synthesized without introducing the prepolymer having temperature response characteristics into the ink components.
Example 3
A. Temperature response characteristic prepolymer synthesis:
(1) adding 14 parts of deionized water into a three-neck flask provided with a stirrer, a condenser pipe and a temperature control device, adding a part of glycidyl methacrylate (4 parts), a mixture of monomers (5 parts of N-isopropylacrylamide and 2 parts of vinyl methyl ether) and an initiator potassium persulfate (0.2 part), pre-emulsifying for 15min, heating to 65 ℃, and introducing nitrogen for reaction.
(2) After the reaction is carried out for 1.5 hours, the rest of glycidyl methacrylate (3 parts), monomer (3 parts of N-isopropylacrylamide, 3 parts of vinyl methyl ether) and initiator potassium persulfate (0.1 part) are added, the reaction is continued for 14 hours to obtain a prepolymer solution with temperature response characteristics, and the prepolymer solution is dried to obtain the prepolymer. The prepolymer was found to have a weight average molecular weight of 50000 and a molecular weight distribution index of 1.9 by Gel Permeation Chromatography (GPC).
B. Preparing aqueous polyurethane acrylate binder emulsion:
(1) under the protection of nitrogen atmosphere, adding 15 parts of isophorone diisocyanate (isophorone diisocyanate) and 7.5 parts of hydroxymethyl propionic acid acrylate (hydroxymethyl propionic acid acrylate) into a reaction kettle, then adding 0.15 part of dibutyltin dilaurate, and stirring and reacting for 2 hours at the temperature of 55 ℃ and the rotating speed of 200rpm to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding a polyethylene glycol solution (3 parts) into the solution A, and stirring and reacting for 4 hours at the temperature of 65 ℃ and the rotating speed of 200rpm to obtain a solution B;
(3) adding hydroxypropyl methacrylate (15 parts) into the solution B, sealing, cooling to normal temperature, and adding triethanolamine to neutralize and form salt. Adding deionized water, stirring at 1000rpm for 15min, and finally performing ultrasonic oscillation for 15min to obtain the aqueous polyurethane acrylate binder emulsion.
C. The temperature response type polymer modified water-based UV curing ink is prepared by the following formula:
45 parts of aqueous polyurethane acrylate binder emulsion;
17 parts of prepolymer with temperature response characteristic;
3 parts of a water-based photoinitiator;
12 parts of pigment;
7 parts of an auxiliary agent;
deionized water, 14 parts.
The auxiliary agent comprises 2 parts of a cross-linking agent (1 part of 2-methylimidazole and 1 part of 2-ethyl-4-methylimidazole), 2 parts of an inorganic filler (talcum powder), 1 part of a flatting agent (BYK-380N), 1 part of a defoaming agent (BYK 022) and 1 part of a slipping agent, and the water-based photoinitiator is a mixture of 2, 2-dimethyl-2-hydroxyacetophenone (1 part), alpha-hydroxycyclohexyl benzophenone (1 part) and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (1 part).
Comparative example 3
The preparation conditions, formulation and operation steps were the same as in example 3 except that the prepolymer having temperature response characteristics was synthesized without introducing the prepolymer having temperature response characteristics into the ink components.
Example 4
A. Temperature response characteristic prepolymer synthesis:
(1) adding 18 parts of deionized water into a three-neck flask provided with a stirrer, a condenser pipe and a temperature control device, adding a part of mixture of glycidyl methacrylate (5 parts), a monomer (N-isopropylacrylamide, 6 parts) and an initiator potassium persulfate (0.2 part), pre-emulsifying for 10min, heating to 60 ℃, and introducing nitrogen for reaction.
(2) And when the reaction is carried out for 3 hours, adding the rest of glycidyl methacrylate (4 parts), a monomer (N-isopropylacrylamide, 6 parts) and an initiator potassium persulfate (0.2 part), continuously reacting for 15 hours to obtain a prepolymer solution with temperature response characteristics, and drying to obtain a prepolymer. The weight average molecular weight of the prepolymer was 40000 and the molecular weight distribution index was 1.9 as measured by Gel Permeation Chromatography (GPC).
B. Preparing aqueous polyurethane acrylate binder emulsion:
(1) under the protection of nitrogen atmosphere, adding 18 parts of isophorone diisocyanate and 9 parts of hydroxymethyl propionic acid acrylate into a reaction kettle, then adding 0.18 part of dibutyltin dilaurate, and stirring at the rotating speed of 200rpm for reaction for 2 hours at the temperature of 55 ℃ to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding a polyethylene glycol solution (4 parts) into the solution A, and stirring and reacting for 4 hours at the temperature of 65 ℃ and the rotating speed of 200rpm to obtain a solution B;
(3) adding hydroxypropyl methacrylate (18 parts) into the solution B, sealing, cooling to normal temperature, and adding triethanolamine to neutralize and form salt. Adding deionized water, stirring at 1000rpm for 10min, and finally performing ultrasonic oscillation for 10min to obtain the aqueous polyurethane acrylate binder emulsion.
C. The temperature response type polymer modified water-based UV curing ink is prepared by the following formula:
50 parts of aqueous polyurethane acrylate binder emulsion;
16 parts of prepolymer with temperature response characteristic;
4 parts of a water-based photoinitiator;
13 parts of pigment;
8 parts of an auxiliary agent;
deionized water, 12 parts.
The auxiliary agent comprises 2 parts of a cross-linking agent (1 part of 2-methylimidazole and 1 part of 2-ethyl-4-methylimidazole), 2 parts of an inorganic filler (talcum powder), 2 parts of a flatting agent (BYK-380N), 1 part of an antifoaming agent (BYK 022) and 1 part of a slipping agent, and the water-based photoinitiator is a mixture of 2, 2-dimethyl-2-hydroxyacetophenone (1 part), alpha-hydroxycyclohexyl benzophenone (1 part), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (1 part) and 2-isopropyl thioxanthone (1 part).
Comparative example 4
The preparation conditions, formulation and operation steps were the same as in example 4 except that the prepolymer having temperature response characteristics was synthesized without introducing the prepolymer having temperature response characteristics into the ink composition.
Example 5
A. Temperature response characteristic prepolymer synthesis:
(1) 20 parts of deionized water are added into a three-neck flask provided with a stirrer, a condenser pipe and a temperature control device, a part of the mixture of glycidyl methacrylate (5 parts), a monomer (5 parts of vinyl methyl ether) and an initiator potassium persulfate (0.1 part) are added, pre-emulsification is carried out for 10min, and then the temperature is raised to 60 ℃ and nitrogen is introduced for reaction.
(2) After the reaction is carried out for 1 hour, adding the rest of glycidyl methacrylate (5 parts), monomer (N-isopropylacrylamide, 5 parts) and initiator potassium persulfate (0.1 part), continuing the reaction for 12 hours to obtain a prepolymer solution with temperature response characteristics, and drying to obtain a prepolymer. The weight average molecular weight of the prepolymer was 20000 and the molecular weight distribution index was 1.9 as measured by Gel Permeation Chromatography (GPC).
B. Preparing aqueous polyurethane acrylate binder emulsion:
(1) under the protection of nitrogen atmosphere, adding 20 parts of isophorone diisocyanate and 10 parts of hydroxymethyl propionic acid acrylate into a reaction kettle, then adding 0.2 part of dibutyltin dilaurate, and stirring at the rotating speed of 200rpm at the temperature of 50 ℃ for reaction for 1 hour to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding a polyethylene glycol solution (5 parts) into the solution A, and stirring and reacting for 3 hours at the temperature of 60 ℃ and the rotating speed of 200rpm to obtain a solution B;
(3) adding hydroxypropyl methacrylate (20 parts) into the solution B, sealing, cooling to normal temperature, and adding triethanolamine to neutralize and form salt. Adding deionized water, stirring at 1000rpm for 10min, and finally performing ultrasonic oscillation for 10min to obtain the aqueous polyurethane acrylate binder emulsion.
C. The temperature response type polymer modified water-based UV curing ink is prepared by the following formula:
60 parts of waterborne polyurethane acrylate binder emulsion;
15 parts of prepolymer with temperature response characteristic;
5 parts of a water-based photoinitiator;
15 parts of pigment;
10 parts of auxiliary agent;
deionized water, 10 parts.
The auxiliary agent comprises 3 parts of a cross-linking agent (1 part of 2-methylimidazole, 1 part of 2-ethyl-4-methylimidazole and 1 part of 2-phenylimidazole), 2 parts of an inorganic filler (talcum powder), 2 parts of a flatting agent (BYK-380N), 2 parts of a defoaming agent (BYK 022) and 1 part of a slipping agent, and the water-based photoinitiator is 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (5 parts).
Comparative example 5
The preparation conditions, formulation and operation steps were the same as in example 5 except that the prepolymer having temperature response characteristics was synthesized without introducing the prepolymer having temperature response characteristics into the ink components.
Comparative example 6
The ratio of the monomer to the initiator was controlled to 20:0.4, and a temperature response characteristic prepolymer having a weight average molecular weight of 10000 and a molecular weight distribution index of 2.0 was prepared, and other preparation conditions and operation steps were the same as those of example 5.
Comparative example 7
The ratio of the monomer to the initiator was controlled to 20:0.02, and a temperature response characteristic prepolymer having a weight average molecular weight of 200000 and a molecular weight distribution index of 1.9 was prepared, and other preparation conditions and operation steps were the same as those of example 5.
Example 6
The monomer in the step of synthesizing the prepolymer having temperature response characteristics was replaced with N-isopropyl methacrylamide in an amount of 15 parts, and the other components were added in the same amounts and in the same steps as in example 1, and the obtained prepolymer having temperature response characteristics had a molecular weight of 90000 and a distribution index of 1.9.
Example 7
The monomer in the step of synthesizing the prepolymer having temperature response characteristics was replaced with N, N-diethylacrylamide in an amount of 16 parts, and the other components were added in the same amounts and in the same manner as in example 1, and the obtained prepolymer having temperature response characteristics had a molecular weight of 95000 and a distribution index of 2.0.
Example 8
The monomer in the step of synthesizing the prepolymer having temperature response characteristics was replaced with N-vinylcaprolactam in an amount of 17 parts, and the other components were added in the same amounts and in the same steps as in example 1, and the resulting prepolymer having temperature response characteristics had a molecular weight of 85000 and a distribution index of 1.9.
Example 9
The monomer in the step of synthesizing the prepolymer having temperature response characteristics was replaced with ethylene glycol methyl ether methacrylate in an amount of 15 parts, the other components were added in the same amounts and in the same steps as in example 1, and the obtained prepolymer having temperature response characteristics had a molecular weight of 70000 and a distribution index of 1.9.
Mixing the components in proportion, putting the mixture into a special barrel, stirring the mixture by a stirrer to preliminarily mix the pigment and the connecting material to form paste, grinding the stirred material, checking whether the properties such as hue, fineness, fluidity, viscosity, dryness and the like meet the design requirements, and filling the ink into a barrel for later use after adjustment and finished product inspection.
Ink Performance testing
Testing the drying speed: a sample is prepared by a blade coating mode, the sample is dried at the temperature of 60 ℃, the printing thickness of the ink is 5 mu m, and the time when the moisture is reduced to trace amount (completely dry) is tested.
And (3) testing adhesion fastness: reference GB/T13217.7-2009
In order to verify the comprehensive performance of the environmentally friendly UV curable ink of the present invention, the drying performance and the adhesion fastness of the environmentally friendly UV curable inks of the above 5 examples and 5 comparative examples were tested.
The test results are shown in the following table:
as can be seen from the above table, when the weight average molecular weight is 10000-100000 and the molecular weight distribution index is 1.9-2.0, the drying time of the temperature-responsive polymer modified aqueous UV-curable ink obtained in examples 1-5 according to the present invention is between 2-3 s, and the drying time is significantly shortened compared to the comparative examples 1-5; meanwhile, the adhesion fastness of the environment-friendly water-based UV curing ink is kept between 97 and 98 percent; when the weight average molecular weight is out of the above range, compared with example 5, when comparative example 6 adopts a molecular weight of 10000 and a molecular weight distribution index of 2.0, the drying speed and the adhesion performance are reduced, which indicates that the lower the molecular weight of the prepolymer with the temperature response characteristic is, the shorter the molecular chain is, so that the prepolymer with the temperature response characteristic is difficult to perform the crosslinking reaction caused by the ring opening of the epoxy group in the ink system, a crosslinked network system cannot be formed, and the effect of improving the drying speed of the ink cannot be achieved; when the weight average molecular weight is out of the above range, as compared with example 5, in comparative example 7 using the molecular weight of 200000 and the molecular weight distribution index of 1.9, the drying speed and the adhesion property are also decreased, indicating that when the molecular weight of the prepolymer having the temperature response characteristic is too high, the longer the molecular chain, the more the chain entanglement is, so that the diffusion of the prepolymer having the temperature response characteristic in the ink system is affected, and the failure to form an effective crosslinked network system also results in no effect of increasing the drying speed of the ink. Examples 6-9 were prepared using prepolymers from different monomers (poly-N-isopropylmethacryl, poly-N, N-diethylacryloyl, poly-N-vinylcaprolactam, polyethylene glycol methyl ether methacrylate) to prepare aqueous UV inks, and it can be seen that all aqueous UV inks show faster drying speed and good adhesion.
The invention prepares the environment-friendly temperature response type polymer modified water-based UV curing ink which intelligently responds to temperature and has high drying speed. The temperature response type polymer modified water-based UV curing ink takes water as a solvent, can effectively reduce the volatilization of organic volatile matters, and meets the development requirement of green environmental protection; the temperature response type polymer modified water-based UV curing ink has an intelligent temperature response characteristic, can realize rapid diffusion and discharge of water in an ink film under the condition of keeping the existing drying process, and effectively solves the problem of low drying speed of the water-based ink. Can be used for printing medicines and cigarette packet packaging products, meets the strict requirement of sanitary conditions, and also meets the requirement of low carbon and environmental protection.
Claims (6)
1. The temperature response type polymer modified water-based UV curing ink is characterized by being capable of being dried quickly, wherein a prepolymer with temperature response characteristics is added into the raw materials of the water-based UV curing ink, wherein the prepolymer accounts for 15-20% of the total mass of the raw materials, contains hydrophilic groups and hydrophobic groups, and simultaneously contains reactive epoxy groups;
the prepolymer with the temperature response characteristic is prepared by the following components in parts by weight through free radical copolymerization:
5-10 parts of glycidyl methacrylate,
10-15 parts of a monomer,
0.1-0.4 part of potassium persulfate initiator;
the glycidyl methacrylate provides a reactive epoxy group; the monomer provides a hydrophilic group and a hydrophobic group, and is any one or more of N-isopropyl acrylamide, N-isopropyl methacrylamide, N-diethyl acrylamide, N-vinyl caprolactam, vinyl methyl ether and polyethylene glycol methyl ether methacrylate in any proportion;
the water-based UV curing printing ink is water-based polyurethane acrylate connecting material emulsion; the paint consists of the following components in parts by weight:
10-20 parts of isophorone diisocyanate;
5-10 parts of hydroxymethyl propionic acid acrylate;
1-5 parts of polyethylene glycol;
0.05-0.2 part of dibutyltin dilaurate;
10-20 parts of hydroxypropyl methacrylate;
0.05-1 part of polymerization inhibitor;
10-20 parts of deionized water.
2. The temperature-responsive polymer-modified aqueous UV-curable ink according to claim 1, wherein the weight-average molecular weight of the prepolymer having temperature-responsive property is 20000-100000 and the molecular weight distribution index is 1.9-2.0.
3. The temperature-responsive polymer-modified aqueous UV-curable ink according to claim 1, wherein said prepolymer having temperature-responsive characteristics is synthesized by the following steps:
(1) adding deionized water, glycidyl methacrylate, a monomer mixture and a part of initiator potassium persulfate into a reaction vessel provided with a stirrer, a condensing device and a temperature control device, pre-emulsifying for 10-30min, heating to 60-70 ℃, and introducing nitrogen for reaction;
(2) and after the reaction is carried out for 1-3h, adding the residual monomer and the initiator, continuously reacting for 12-16h to obtain a prepolymer solution with a temperature response characteristic, and drying to obtain the prepolymer with the temperature response characteristic.
4. The temperature-responsive polymer-modified aqueous UV-curable ink according to claim 1, characterized in that it comprises, in parts by weight:
30-60 parts of aqueous polyurethane acrylate binder emulsion;
15-20 parts of prepolymer with temperature response characteristic;
1-5 parts of a water-based photoinitiator;
10-15 parts of pigment;
5-10 parts of an auxiliary agent;
10-20 parts of deionized water;
the auxiliary agent comprises a cross-linking agent, an inorganic filler, a flatting agent, a defoaming agent and a slipping agent;
the cross-linking agent is a light latent cross-linking agent and is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole or phenylimidazole;
the aqueous photoinitiator is at least one of 2, 2-dimethyl-2-hydroxyacetophenone, alpha-hydroxycyclohexyl benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and 2-isopropyl thioxanthone.
5. The temperature-responsive polymer-modified aqueous UV-curable ink according to claim 4, wherein the aqueous urethane acrylate binder emulsion is synthesized by the following steps:
(1) under the protection of nitrogen atmosphere, adding isophorone diisocyanate and hydroxymethyl propionic acid acrylate into a reaction kettle, then adding dibutyltin dilaurate, and stirring and reacting for 1-4h at the temperature of 50-60 ℃ to obtain a solution A;
(2) when the isocyanate value in the reactant is not changed any more by measuring with a di-n-butylamine method, adding a polyethylene glycol solution into the solution A, and stirring and reacting for 3-6h at the temperature of 60-70 ℃ to obtain a solution B;
(3) adding hydroxypropyl methacrylate into the solution B, sealing, cooling to normal temperature, adding triethanolamine, and neutralizing to form salt; adding deionized water, stirring for 10-30min, and finally performing ultrasonic oscillation for 10-30min to obtain the waterborne polyurethane acrylate binder emulsion.
6. The preparation method of the temperature response type polymer modified water-based UV curing ink as claimed in claim 4 or 5, characterized in that the temperature response type polymer modified water-based UV curing ink is prepared by firstly synthesizing the water-based polyurethane acrylate binder emulsion and the prepolymer with the temperature response characteristic, and then adding the water-based photoinitiator, the pigment and the auxiliary agent by taking water as the diluent.
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