CN102153914A - 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 the Water-borne modification and the photolytic activity of ink vehicle resin.The Water-borne modification approach of resin mainly contains physics dispersion method, chemical dissolution method and physical chemistry composite algorithm, and the physics method is that stirring makes resin dispersion in water medium by brute force in the presence of dispersion agent, 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 forms the aqueous solution of resin salt after salify makes resin have hydrophilic solvability; 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 simple physics of approach effect or the chemistry route of resin Water-borne modification more effective.The UV photolytic activity of resin, mainly be to adopt to issue the unsaturated prepolymer that the third contact of a total solar or lunar eclipse causes radical polymerization in the UV rayed, theoretically, the active prepolymer of every UV-curable all can be used for the preparation of water-based UV printing ink, yet not all UV active prepolymer all is fit to the preparation of water-based UV printing ink in the practical application.
Unsaturated polyester is subjected 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 big, the China ink layer is easy to crack, attachment fastness is low, wear no resistance.Unsaturated polyester resin (UPR) is one of the thermosetting resin comparatively rapidly of development both at home and abroad in recent years.Yet UPR is hard and crisp after solidifying, and impact property is poor, and cure shrinkage height shortcomings such as (general cure shrinkage are 7%～8%) restricts its widespread use.At present, the modification at UPR mainly concentrates on its toughening modifying and low two aspects of modification of shrinking.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 considers, introduces soft segment when synthetic UPR, can effectively improve fragility, but too much adding soft segment, can cause resin solidification after physical strength descend.Is a kind of faster method of modifying of development in recent years based on the second phase material elastomerics to the UPR toughening modifying.What elastic body toughening was commonly used is that fluid rubber is toughness reinforcing.Owing 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 at UPR mainly is 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 fragility of LPA modification can improvement 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 maximize favourable factors and minimize unfavourable ones by bound energy, 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 at 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 is equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is a 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; Start stirring after being heated to the solid dissolving, 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, treat to add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) with the first step synthetic terminal hydroxy group unsaturated polyester oligomer solution, electronic stirring is equipped with in vulcabond and dibutyl tin laurate adding, 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, it is constant to system-NCO% that the adding polyglycol ether carries out block copolymerization, it is constant to system-NCO% that the adding dimethylol propionic acid carries out chain extending reaction, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, adding Monoethanolamine MEA BASF and water compounded solvents are stirred well to system pH and equal 8～8.5, keep 30 minutes no changes, it is qualified to adjust viscosity with water compounded solvents, stop to stir, filter discharging, keep in Dark Place;
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, in container, mix, after stirring, pour into and be dispersed to fineness 15 μ m in the sand mill, adding photosensitizers, defoamer, anti-friction composition, stablizer are uniformly dispersed, and adjust viscosity to qualified filtration discharging with water compounded solvents, promptly get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect the every performance index of China ink layer.
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 are little, China ink layer attachment fastness height, strong, the low VOC discharging of picture and text reproducibility, 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.
Launch the present invention with written language below.
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 is equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is a 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; Start stirring after being heated to the solid dissolving, 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, treat to add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) with the first step synthetic terminal hydroxy group unsaturated polyester oligomer solution, electronic stirring is equipped with in vulcabond and dibutyl tin laurate adding, 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, it is constant to system-NCO% that the adding polyglycol ether carries out block copolymerization, it is constant to system-NCO% that adding dimethylol propionic acid (DMP) carries out chain extending reaction, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, adding Monoethanolamine MEA BASF and water compounded solvents are stirred well to system pH and equal 8～8.5, keep 30 minutes no changes, it is qualified to adjust viscosity with water compounded solvents, stop to stir, filter discharging, keep in Dark Place;
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, in container, mix, after stirring, pour into and be dispersed to fineness 15 μ m in the sand mill, adding photosensitizers, defoamer, anti-friction composition, stablizer are uniformly dispersed, and adjust viscosity to qualified filtration discharging with water compounded solvents, promptly get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect the every performance index of China ink layer.
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 the mol ratio of the two 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 made up of unsaturated polyester ester oligomer, polyoxyethylene glycol and dimethylol propionic acid, and three's mol ratio is 1: 1: 1; The polymerization degree of polyglycol ether 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 a neutralizing agent, and its consumption is a foundation to keep system terminal point pH to equal 8～8.5.
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 65%～80%, 6%～10%, 3%～4% of ink formulations total mass respectively.
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 a paraffin, stablizer is a para benzoquinone, its consumption accounts for 0.6% of ink formulations total mass respectively, 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 made up 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, the 186g ethylene glycol and the 50g dimethylbenzene 2g vitriol oil add successively electronic stirring are housed, water trap, thermometer, in the electric mantle heated reaction vessel, start stirring after being heated to the solid dissolving, 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, be evacuated to hydroxyl value and meet the requirements, steam dimethylbenzene, add benzoquinones and stir, treat to add the 100g reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps 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 electronic stirring is housed, water trap, thermometer, in the electric mantle heated reaction vessel, be warming up to 60 ℃ of insulation reaction, to system-NCO%, it is the isocyanate group content constant, it is constant to system-NCO% that adding 86.2g polyglycol ether carries out block reaction, it is constant to system-NCO% that adding 13.4g dimethylol propionic acid carries out chain extending reaction, 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 ℃, adding Monoethanolamine MEA BASF and water compounded solvents are stirred well to system pH and equal 8～8.5, keep 30 minutes no changes, it is qualified to adjust viscosity with water compounded solvents, stop to stir, filter discharging, keep in Dark Place.
(3) preparation of unsaturated polyester block polymers of polyurethane water-based UV printing ink
Accurately take by weighing 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 the sand mill below the 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, promptly gets unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect the every performance index of China ink layer, 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 (9)
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 is equipped with in electronic stirring, water trap, thermometer, the electric mantle heated reaction vessel, it is saturated acid anhydrides that dibasic acid anhydride adopts phthalic anhydride, MALEIC ANHYDRIDE is a 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; Start stirring after being heated to the solid dissolving, 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, treat to add reactive thinner when resin is cooled to below 50 ℃, stir, discharging is standby, keeps in Dark Place;
(2) with the first step synthetic terminal hydroxy group unsaturated polyester oligomer solution, electronic stirring is equipped with in vulcabond and dibutyl tin laurate adding, 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, it is constant to system-NCO% that the adding polyglycol ether carries out block copolymerization, it is constant to system-NCO% that the adding dimethylol propionic acid carries out chain extending reaction, add methacrylic acid-β hydroxyl ethyl ester carry out end capping to system-NCO% equals at 0 o'clock, adding Monoethanolamine MEA BASF and water compounded solvents are stirred well to system pH and equal 8～8.5, keep 30 minutes no changes, it is qualified to adjust viscosity with water compounded solvents, stop to stir, filter discharging, keep in Dark Place;
(3) accurate weighing unsaturated polyester block polymers of polyurethane water-based low-melting ink vehicle and face, filler, in container, mix, after stirring, pour into and be dispersed to fineness 15 μ m in the sand mill, adding photosensitizers, defoamer, anti-friction composition, stablizer are uniformly dispersed, and adjust viscosity to qualified filtration discharging with water compounded solvents, promptly get unsaturated polyester block polymers of polyurethane water-based UV printing ink, scrape the sample colorimetric, after UV curing machine solidifies drying, detect the every performance index of China ink layer.
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 the mol ratio of the two 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 made up of unsaturated polyester ester oligomer, polyoxyethylene glycol and dimethylol propionic acid, and three's mol ratio is 1: 1: 1; The polymerization degree of polyglycol ether 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, vulcabond is a tolylene diisocyanate, isocyanate group molar excess percentage ratio is 50%～100%, and the segmented copolymer number-average molecular weight is 2500～5000.
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, 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.
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 low-melting ink vehicle of step (2) prepares, Monoethanolamine MEA BASF is a neutralizing agent, and its consumption is a foundation to keep system terminal point pH to equal 8～8.5.
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 prepared, water-based low-melting ink vehicle, pigment and filler accounted for 65%～80%, 6%～10%, 3%～4% of ink formulations total mass respectively.
8. 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 a paraffin, stablizer is a para benzoquinone, and its consumption accounts for 0.6%, 0.2% of ink formulations total mass respectively, 0.1%, 0.1%.
9. 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 made up of Virahol, ethanol, ethylene glycol ethyl ether, distilled water, and mass ratio is 2: 2: 1: 1.
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Cited By (4)
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| CN103665310A (en) * | 2013-12-13 | 2014-03-26 | 湖南邦弗特新材料技术有限公司 | Preparation method of temperature-resistant UV (ultraviolet) curing 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 |
| CN108864807A (en) * | 2013-11-11 | 2018-11-23 | 日立化成株式会社 | Adhesive for printing ink, printing ink and its application and printed article |
| CN117402544A (en) * | 2023-11-17 | 2024-01-16 | 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864807A (en) * | 2013-11-11 | 2018-11-23 | 日立化成株式会社 | Adhesive for printing ink, printing ink and its application and printed article |
| CN108864807B (en) * | 2013-11-11 | 2021-10-01 | 昭和电工材料株式会社 | Binder for printing ink, application thereof, and printed matter |
| CN103665310A (en) * | 2013-12-13 | 2014-03-26 | 湖南邦弗特新材料技术有限公司 | Preparation method of temperature-resistant UV (ultraviolet) curing resin |
| 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 |
| CN117402544A (en) * | 2023-11-17 | 2024-01-16 | 东莞市瑞盟涂料有限公司 | Low-VOC (volatile organic compound) water-based paint 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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