CN102153914B - Preparation method of water-based UV ink (ultraviolet) of unsaturated polyester polyurethane segmented copolymer - Google Patents
Preparation method of water-based UV ink (ultraviolet) of unsaturated polyester polyurethane segmented copolymer Download PDFInfo
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Abstract
The invention relates to a preparation method of water-based UV ink (ultraviolet) of unsaturated polyester polyurethane segmented copolymer. The preparation method includes the steps as follows; dihydric alcohol, maleic anhydride and phthalic anhydride are adopted to generate unsaturated polyester oligomer of hydroxyl end group by progressive polycondensation; after progressive addition polymerization with reactive diluent as the solvent, the unsaturated oligomer, polyethylene glycol ether and diisocyanate are subjected to chain extension with water functional monomer to generate unsaturated polyester polyurethane segmented prepolymer solution of isocyanate end group and with hydrophilic function; and after the prepolymer is end-sealed with methacrylic acid-beta hydroxyethyl, monoethanolamine is taken as neutralizer that is dispersed in water while stirred to obtain water-based joining material of unsaturated polyester polyurethane segmented prepolymer. The water-based joining material and the pigment filler, the photosensitizer and the assistant are formulated to prepare water-based UV ink of unsaturated polyester polyurethane segmented prepolymer.
Description
Technical field
The present invention relates to a kind of preparation method of printing ink.
Background technology
At present, the research focus of water-based UV printing ink is Water-borne modification and the photolytic activity of ink vehicle resin.The Water-borne modification approach of resin mainly contains physical dispersion method, chemical dissolution method and physical chemistry composite algorithm, and Physical is to make resin dispersion in water medium by strong stirring under dispersion agent exists, and forms the method for aqueous dispersion type resin emulsion; Chemical dissolution method is to introduce polymerisable aqueous functional monomer in the synthetic design of resin, and polymerization makes resin have hydrophilic solvability by salify, forms the aqueous solution of resin salt; The physical chemistry composite algorithm takes into account physics and chemical process makes resin realize Water-borne modification, considers from the over-all properties of Water-borne modification resin printing ink, adopts the physical chemistry composite algorithm to make the more simple physics of approach effect or the chemistry route of resin Water-borne modification more effective.The UV photolytic activity of resin, mainly to adopt to issue in the UV rayed the unsaturated prepolymer that the third contact of a total solar or lunar eclipse causes radical polymerization, theoretically, the active prepolymer of every UV-curable all can be used for the preparation of water-based UV printing ink, yet in practical application, not all UV active prepolymer all is fit to the preparation of water-based UV printing ink.
Unsaturated polyester is subject to showing great attention to of printing ink circle for a long time as the low-melting ink vehicle resin of water-based UV printing ink, but its widespread use of restriction such as its cure shrinkage is large, the China ink layer is easy to crack, attachment fastness is low, wear no resistance.Unsaturated polyester resin (UPR) is recent domestic development one of thermosetting resin comparatively rapidly.Yet UPR is hard and crisp after solidifying, and impact property is poor, and the shortcomings such as cure shrinkage high (general cure shrinkage is 7%～8%) restrict its widespread use.At present, the modification for UPR mainly concentrates on two aspects of its toughening modifying and low contraction modification.In order to improve the shock resistance of UPR goods, often need UPR to carry out the toughness modification.From introducing the macromole flexible chain, the mobility that increases crosslinked network chain is considered, introduces soft segment when synthetic UPR, can effectively improve fragility, but the too much soft segment that adds, can cause resin solidification after physical strength descend.Development in recent years a kind of method of modifying faster based on second-phase elastic properties of materials body to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing.Due to the high-flexibility of rubber phase, significantly improved the toughness of UP, though rubber elastomer can increase substantially shock strength, stretching, flexural strength, resistance toheat descend to some extent.At present, the low contraction modification for UPR is mainly to reduce its cure shrinkage by adding thermoplasticity shrinking agent (LPA).Shrinking agent commonly used has polystyrene, polymethylmethacrylate and dially phthalate etc., has also developed polycaprolactone, modified polyurethane and cellulose acetate butyl ester etc.Adopt the LPA modification can improve the fragility of UPR, reduce cure shrinkage, improve shock strength, but can reduce the tensile strength of UPR.Urethane has high-flexibility as the extraordinary elastomerics of a kind of property reconciled, and both are in conjunction with maximizing favourable factors and minimizing unfavourable ones, and performance advantage has separately not only reduced cure shrinkage, has also increased toughness.All the time, people concentrate on by adding polyurethane elastomer and UPR physical blending reaching the purpose of modification for the modification of UPR, but have often also reduced other mechanical property when improving its impelling strength, reduction cure shrinkage.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of unsaturated polyester block polymers of polyurethane water-based UV printing ink.
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink, the steps include:
(1) MALEIC ANHYDRIDE, phthalic anhydride, ethylene glycol, dimethylbenzene, the catalyzer that measures added successively in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2: 1～3: 1, hydroxyl molar excess percentage ratio is 50%～100%, and the oligopolymer number-average molecular weight is 500～1000; Be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, and be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) the terminal hydroxy group unsaturated polyester oligomer solution that the first step is synthetic, vulcabond and dibutyl tin laurate add electric stirring are housed, water trap, thermometer, in the there-necked flask of electric mantle heating, be warming up to 60 ℃ of insulations, react to system-NCO%, it is the isocyanate group content constant, add polyoxyethylene glycol to carry out block copolymerization constant to system-NCO%, add dimethylol propionic acid to carry out chain extending reaction constant to system-NCO%, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, add Monoethanolamine MEA BASF and water compounded solvents to be stirred well to system pH and equal 8～8.5, keep 30 minutes unchanged, adjust viscosity with water compounded solvents qualified, stop stirring, filter discharging, keep in Dark Place,
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, mix in container, after stirring, pour into and be dispersed to fineness 15 μ m in sand mill, add photosensitizers, defoamer, anti-friction composition, stablizer to be uniformly dispersed, adjust viscosity to qualified filtration discharging with water compounded solvents, namely get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect China ink layer property indices.
Adopt the UV printing ink of the present invention's preparation, be suitable for intaglio plate and flexographic printing, both can be used for the printing of perviousness matrix (as paper, fabric), also can be used for the printing of impermeability matrix (as plastics, metal), have that printability is good, UV-curable, cure shrinkage is little, China ink layer attachment fastness is high, the picture and text reproducibility strong, low VOC discharging, environmental friendliness.
Embodiment
The present invention is the preparation of unsaturated polyester block polymers of polyurethane water-based UV printing ink, with the chemical equation statement, the steps include:
The first step: terminal hydroxy group unsaturated polyester ester oligomer synthetic;
Second step: the preparation of unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle;
The 3rd step: the preparation of unsaturated polyester block polymers of polyurethane water-based UV printing ink.
The below launches the present invention with written language.
The present invention is the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink, the steps include:
(1) MALEIC ANHYDRIDE, phthalic anhydride, ethylene glycol, dimethylbenzene, the catalyzer that measures added successively in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2: 1～3: 1, hydroxyl molar excess percentage ratio is 50%～100%, and the oligopolymer number-average molecular weight is 500～1000; Be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, and be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) the terminal hydroxy group unsaturated polyester oligomer solution that the first step is synthetic, vulcabond and dibutyl tin laurate add electric stirring are housed, water trap, thermometer, in the there-necked flask of electric mantle heating, be warming up to 60 ℃ of insulations, react to system-NCO%, it is the isocyanate group content constant, add polyoxyethylene glycol to carry out block copolymerization constant to system-NCO%, add dimethylol propionic acid (DMP) to carry out chain extending reaction constant to system-NCO%, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, add Monoethanolamine MEA BASF and water compounded solvents to be stirred well to system pH and equal 8～8.5, keep 30 minutes unchanged, adjust viscosity with water compounded solvents qualified, stop stirring, filter discharging, keep in Dark Place,
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, mix in container, after stirring, pour into and be dispersed to fineness 15 μ m in sand mill, add photosensitizers, defoamer, anti-friction composition, stablizer to be uniformly dispersed, adjust viscosity to qualified filtration discharging with water compounded solvents, namely get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect China ink layer property indices.
When the terminal hydroxy group unsaturated polyester ester oligomer of above-described step (1) was synthetic, reactive thinner was butyl methacrylate and vinylformic acid second diester, and mol ratio both is 1: 1.
When the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of above-described step (2) prepared, hydroxy component was comprised of unsaturated polyester ester oligomer, polyoxyethylene glycol and dimethylol propionic acid, and three's mol ratio is 1: 1: 1; The polymerization degree of polyoxyethylene glycol is 5～10.
When the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of above-described step (2) prepares, vulcabond is tolylene diisocyanate (TDI), isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
When the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of above-described step (2) prepared, adopting methacrylic acid-β hydroxyl ethyl ester was end-capping reagent, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
When the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of above-described step (2) prepared, Monoethanolamine MEA BASF was neutralizing agent, and its consumption is to keep system terminal point pH to equal 8～8.5 as foundation.
When the unsaturated polyester block polymers of polyurethane water-based UV of above-described step (3) printing ink prepared, water-based low-melting ink vehicle, pigment and filler accounted for respectively 65%～80%, 6%～10%, 3%～4% of ink formulations total mass.
When the unsaturated polyester block polymers of polyurethane water-based UV of above-described step (3) printing ink prepares, photosensitizers is that benzophenone, defoamer are organic silicon acrylic ester, anti-friction composition is paraffin, stablizer is para benzoquinone, its consumption accounts for respectively 0.6% of ink formulations total mass, 0.2%, 0.1%, 0.1%.
When the unsaturated polyester block polymers of polyurethane water-based UV of above-described step (3) printing ink prepared, water compounded solvents was comprised of Virahol, ethanol, ethylene glycol ethyl ether, distilled water, and mass ratio is 2: 2: 1: 1.
Further launch the present invention below by embodiment more specifically.
(1) the unsaturated polyester ester oligomer is synthetic
with the 31g MALEIC ANHYDRIDE, the 148g Tetra hydro Phthalic anhydride, 186g ethylene glycol and the 50g dimethylbenzene 2g vitriol oil add successively electric stirring are housed, water trap, thermometer, in the reaction vessel of electric mantle heating, be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add 25g ethylene glycol, being evacuated to hydroxyl value meets the requirements, steam dimethylbenzene, add benzoquinones to stir, when being cooled to below 50 ℃, resin adds the 100g reactive thinner, stir, discharging is standby, keep in Dark Place.
(2) unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle is synthetic
with 74g terminal hydroxy group unsaturated polyester oligomer solution, 97.4g tolylene diisocyanate and 4g dibutyl tin laurate add, electric stirring is housed, water trap, thermometer, in the reaction vessel of electric mantle heating, be warming up to 60 ℃ of insulation reaction, to system-NCO%, it is the isocyanate group content constant, add the 86.2g polyoxyethylene glycol to carry out block reaction constant to system-NCO%, add the 13.4g dimethylol propionic acid to carry out chain extending reaction constant to system-NCO%, add 50g methacrylic acid-β hydroxyl ethyl ester, to system-NCO% equals at 0 o'clock, add water compounded solvents and be cooled to 50 ℃, add Monoethanolamine MEA BASF and water compounded solvents to be stirred well to system pH and equal 8～8.5, keep 30 minutes unchanged, adjust viscosity with water compounded solvents qualified, stop stirring, filter discharging, keep in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane water-based UV printing ink
Accurately take the water-based low-melting ink vehicle by unsaturated polyester block polymers of polyurethane water-based UV ink formulations table 1, pigment, calcene mixes in container, after stirring, pours into and is dispersed in sand mill below fineness 15 μ m; Add benzophenone, organic silicon acrylic ester, paraffin, para benzoquinone is uniformly dispersed, and adjusts viscosity to qualified filtration discharging with water compounded solvents, namely gets unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect China ink layer property indices, test item and result are as shown in table 2.
Table 1 unsaturated polyester block polymers of polyurethane water-based UV ink formulations table
Table 2 unsaturated polyester block polymers of polyurethane water-based UV printing ink detects table
Claims (7)
1. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink, the steps include:
(1) MALEIC ANHYDRIDE, phthalic anhydride, ethylene glycol, dimethylbenzene, the catalyzer that measures added successively in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is unsaturated acid anhydride, the mol ratio of phthalic anhydride and cis-butenedioic anhydride is 2: 1～3: 1, hydroxyl molar excess percentage ratio is 50%～100%, and the oligopolymer number-average molecular weight is 500～1000; Be heated to start stirring after dissolution of solid, and be warming up to 150 ℃, reacted 2 hours, and be warming up to 190 ± 2 ℃ of reactions 1 hour, be cooled to 150 ℃ and add the dibasic alcohol that measures, being evacuated to hydroxyl value meets the requirements, steam solvent, add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) the terminal hydroxy group unsaturated polyester oligomer solution that the first step is synthetic, vulcabond and dibutyl tin laurate add electric stirring are housed, water trap, thermometer, in the there-necked flask of electric mantle heating, be warming up to 60 ℃ of insulations, react to system-NCO%, it is the isocyanate group content constant, add polyoxyethylene glycol to carry out block copolymerization constant to system-NCO%, add dimethylol propionic acid to carry out chain extending reaction constant to system-NCO%, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, add Monoethanolamine MEA BASF and water compounded solvents to be stirred well to system pH and equal 8～8.5, keep 30 minutes unchanged, adjust viscosity with water compounded solvents qualified, stop stirring, filter discharging, keep in Dark Place, when unsaturated polyester block polymers of polyurethane waterborne binder prepared, vulcabond was tolylene diisocyanate, and isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000,
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, mix in container, after stirring, pour into and be dispersed to fineness 15 μ m in sand mill, add photosensitizers, defoamer, anti-friction composition, stablizer to be uniformly dispersed, adjust viscosity to qualified filtration discharging with water compounded solvents, namely get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect China ink layer property indices; When unsaturated polyester block polymers of polyurethane water-based UV printing ink prepared, water-based low-melting ink vehicle, pigment and filler accounted for respectively 65%～80%, 6%～10%, 3%～4% of ink formulations total mass.
2. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the terminal hydroxy group unsaturated polyester ester oligomer of step (1) is synthetic, reactive thinner is butyl methacrylate and vinylformic acid second diester, and mol ratio both is 1: 1.
3. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of step (2) prepares, hydroxy component is comprised of unsaturated polyester ester oligomer, polyoxyethylene glycol and dimethylol propionic acid, and three's mol ratio is 1: 1: 1; The polymerization degree of polyoxyethylene glycol is 5～10.
4. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of step (2) prepares, adopting methacrylic acid-β hydroxyl ethyl ester is end-capping reagent, and its consumption is 1.2～1.5 times of diisocyanate based molar excess number.
5. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle of step (2) prepares, Monoethanolamine MEA BASF is neutralizing agent, and its consumption is to keep system terminal point pH to equal 8～8.5 as foundation.
6. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane water-based UV of step (3) printing ink prepares, photosensitizers is that benzophenone, defoamer are organic silicon acrylic ester, anti-friction composition is paraffin, stablizer is para benzoquinone, and its consumption accounts for respectively 0.6%, 0.2% of ink formulations total mass, 0.1%, 0.1%.
7. the preparation method of unsaturated polyester block polymers of polyurethane water-based UV printing ink according to claim 1, it is characterized in that: when the unsaturated polyester block polymers of polyurethane water-based UV of step (3) printing ink prepares, water compounded solvents is comprised of Virahol, ethanol, ethylene glycol ethyl ether, distilled water, and mass ratio is 2: 2: 1: 1.
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| JP6299765B2 (en) * | 2013-11-11 | 2018-03-28 | 日立化成株式会社 | Binder for printing ink, laminate ink composition for soft packaging, and printed matter |
| CN103665310B (en) * | 2013-12-13 | 2015-09-09 | 湖南邦弗特新材料技术有限公司 | A kind of preparation method of heat-resistance type UV cured resin |
| CN106317360A (en) * | 2016-08-17 | 2017-01-11 | 江阴市虹达化工涂料有限公司 | Polyurethane resin and preparation method thereof |
| CN117402544B (en) * | 2023-11-17 | 2024-04-12 | 东莞市瑞盟涂料有限公司 | Low-VOC (volatile organic compound) water-based paint and preparation method thereof |
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| JP特开2011-57771A 2011.03.24 |
| 崔锦峰等.无溶剂常温固化不饱和聚酯聚氨酯涂料的研究.《中国建材科技》.2011,(第01期),第38-42页. * |
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