CN101693797B - Environment-friendly water-based polyurethane ink and preparation method thereof - Google Patents
Environment-friendly water-based polyurethane ink and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an environment-friendly water-based polyurethane ink and a preparation method thereof. The preparation method comprises the following steps: preparing polyester polyol with the molecular weight of 1,500-2,500 by adopting a multi-component copolycondensation; preparing a polyurethane polycondensate containing an active end through primary chain extension; preparing the water-based polyurethane containing a hydrophilic functional group through secondary chain extension; neutralizing with alkali, carrying out water-solubility process with deionized water under the action of high-speed shearing; and vaporizing an organic solvent to prepare the water-based polyurethane and the water-based polyurethane ink. The water-based polyurethane ink has strong attaching force, adjustable color and high peel strength, can be applied to the fields of paper, plastic, card making and the like and is innoxious and environment-friendly.
Description
Technical field
The present invention relates to a kind of environment-friendly water-based polyurethane ink and preparation method thereof.
Background technology
The restriction that the harm of toxicity to human body of benzene, ketone and environment is strict Printing ink producing and use taking benzene, ketone as primary solvent, and gradually to without benzene, without the friendly type ink of the environmental protection future development of ketone.Environment-friendly type ink is experiencing without benzene, without the solvent type ink (being mainly alcohol dissolubility and ester soluble ink) of ketone, and progressively moves towards water color ink.In recent years, the market of environment-friendly type ink product shoots up, and is day by day subject to people's attention, and particularly packs ink, has become an important growth field of global ink.
Polyurethane ink rely on its unique performance advantage progressively fast development get up, it has, and easy to use, stable performance, strong adhesion, glossiness are high, good heat resistance, and can be applicable to the advantages such as various mode of printings.From development and the use procedure of ink; polyurethane ink can be divided into three generation products; first-generation product; polyurethane ink taking benzene, ketone (toluene, acetone, butanone etc.) as solvent; in this,, product was along with the raising of people's quality of life and increasingly strictly and just being eliminated gradually of environmental protection requirement in generation, strictly banned use of especially in the printing of food pack.S-generation product, the polyurethane ink taking ester or alcohol as solvent, this ink is not owing to being developed rapidly containing noxious solvents such as benzene and ketone, and increasing in the share in market, its over-all properties is better.Third generation product is at present just at the water-based polyurethane ink of development research.
Water-based polyurethane ink, owing to not containing volatile organic solvent, improve Working environment, eliminate the hazardous and noxious substances in solvent type ink completely, eliminated the pollution of packaged commodity, can meet multiple performance requriements, therefore, more and more be subject to people's attention, water-based polyurethane ink has obtained development faster abroad, and water color ink is also that the unique one of current united states drug and food control office can be printed and unrestricted ink in food, drug packaging.
Summary of the invention
The invention provides a kind of environment-friendly water-based polyurethane ink and preparation method thereof.
In order to complete the preparation of this ink, the present invention adopts the method for segmentation copolycondensation to prepare polyester polyol, has prepared aqueous polyurethane, and prepared water-based polyurethane ink as ink adhesive by substep chain extension, neutralization and Water-borne modification.
A kind of environment-friendly water-based polyurethane ink preparation method, it comprises the steps:
The first step, the preparation of polyester diol or polyester polyol: adopt the method for multicomponent copolycondensation, carry out segmentation polycondensation at three different temperature sections, prepare polyester polyol; Its temperature section is respectively 80-130 DEG C, 150-190 DEG C, 200-240 DEG C; Raw material adopts binary or poly-basic organic acid and binary or polyvalent alcohol, described binary or poly-basic organic acid comprise terephthalic acid, phthalic acid, inclined to one side three phenylformic acid, Pyromellitic Acid, the composition of one or more of succinic acid, sebacic acid, hexanodioic acid, propanedioic acid, described binary or polyvalent alcohol comprise one or more composition of ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), glycerol, glycol ether, Triethylene glycol, glycerol; Catalyzer is strong organic acid, as toluene sulfonic acide, Phenylsulfonic acid, chlorinated carboxylic acid etc.Body material (being binary and binary) proportioning represents with the mol ratio of carboxyl and alcoholic extract hydroxyl group, and it is worth 1: between 1.05-1.8, catalyst levels is (by weight) between 0.1-0.6%; Make the number-average molecular weight of resin between 1000-2500, be preferably between 1200-2200;
Preparation process is as follows: the raw material of proportional quantity is joined in vacuum glass reactor, be heated to 120-130 DEG C, stir; question response mixture limpid transparent after, add the catalyzer of proportional quantity, keep this temperature; react 2 hours, be then warming up to 160-170 DEG C, continue reaction 3-4 hour; be warmed up to 200-230 DEG C and logical protection of ammonia, reaction 2-3 hour, closes down nitrogen; vacuumize; reaction 0.5-1 hour, cooling discharging, and sealing is preserved.
Second step, a chain extending reaction: the polyester diol making taking the first step or polyester polyol are body material, coordinates an appropriate chainextender and wetting ability component, taking acetone as solvent, by dripping the method for multicomponent isocyanate, preparation is containing polymkeric substance or the polycondensate of hydrophilic radical.Wherein: multicomponent isocyanate can be Toluene-2,4-diisocyanate, 4-vulcabond, isophorone diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate etc.; Chainextender is a kind of molecular weight 400-800, the polycondensate of the hydroxyl between 400-600 preferably; Wetting ability component adopts dimethylol propionic acid (DMP).Body material (being polyester diol and polyisocyanates) proportioning represents with the mol ratio of alcoholic extract hydroxyl group and isocyanate group, and it is worth 1: between 1.05-1.5; Between chainextender weight percentage 20%-30% in whole solid constituent; Wetting ability component adopts dimethylol propionic acid (DMP), and the weight percentage in whole solid constituent is between 3.5-15.5%, and the content of acetone is (by the emphasis of whole system) between 50-65%; Catalyzer can be dibutyl tin dilaurate, a kind of or its composition of triethylenediamine, and consumption is between the 0.1-1.0% of solid constituent total amount
Preparation process is as follows: by proportioning raw materials, polyester diol or polyester polyol, chainextender, wetting ability component and an acetone are joined in reactor successively, and the catalyzer of add-on, drip multicomponent isocyanate in 45-50 DEG C, after dripping completely, reaction 1-2 hour, is then warming up to 55 DEG C, reaction 3-5 hour, wetting ability component is consumed while appearance without muddiness, by system be chilled to 30-50 DEG C stand-by.
The 3rd step, secondary chain extension reaction: after a described chain extending reaction completes, be between 30-50 DEG C time in temperature, drip gradually secondary chain extension agent in above-mentioned (after one time chain extension completes) system, after dripping, continue reaction 1-1.5 hour, then keep 35 DEG C of temperature stand-by.Secondary chain extension agent adopts more active small molecule chain extender, comprise isophorone diamine, quadrol, diethyl triamine etc., it is a kind of micromolecular compound containing active hydroxyl that the present invention adopts homemade secondary chain extension agent, and its active hydroxy radical content is between 1.0-4.0mmol/g.Proportioning raw materials is 1 by the mole ratio of the mole number of residual isocyanate base after chain extension for the first time and active hydroxyl: between 1-2.0.
The 4th step, the Water-borne modification of urethane: by the 3rd step gained secondary chain extension reactant, under constantly stirring, be neutralized between pH8-10 with organic amine, then under high speed shear effect, with deionized water Water-borne modification, and distillating recovering solvent, the solid content of the polyurethane aqueous dispersions obtaining is between 30_60%.Organic amine can triethylamine, the composition of one or more of di-n-butyl amine, trolamine, and the pH value after add-on is completed by reaction determines, its pH is between 8-10.
The 5th step, the preparation of ink: aqueous polyurethane, pigment, dispersion agent, defoamer, weighting agent, water, Virahol etc. are mixed in proportion, disperseing grinding distribution in sand mill, when meeting the requirements of after fineness, take out and Lou obtain polyurethane aqueous ink.Its proportioning raw materials is as follows: aqueous polyurethane accounts between the 20-45% of solid amount, and weighting agent accounts for the 15-20% of solid amount, and pigment accounts between the 20-35% of solid amount.
The prepared polyester diol of above-mentioned steps 1 is white or the liquid of light solid or thickness, and number-average molecular weight (changes according to proportioning raw materials and level of response) between 1000-2500, and hydroxy radical content is between 1.1-1.5mmol/g.Its molecular weight is determined by the forming of raw material, proportioning and level of response, can be carried out Theoretical Calculation by following formula:
Wherein, X
nrepresent the polymerization degree, q represents the molar excess point rate of raw material, and p represents level of response.Proportioning raw materials of the present invention is between 1: 1.05 ~ 1.8 by the mol ratio of carboxyl and hydroxyl.
The polycondensate that above-mentioned steps 2 obtains through chain extension is the colourless solution taking acetone as solvent, contains active isocyanate group, and wherein the content of hydrophilic component (is pressed solid content) between 3.5-15.5%.
In above-mentioned steps 3, the polycondensate obtaining through secondary chain extension is the colourless viscous liquid taking acetone as solvent, secondary chain extension agent is not only conducive to improve molecular weight, reduce molecular weight distribution width, active group (isocyanate groups) is played to the effect of end-blocking, can also improve sticking power and drying rate simultaneously.
In above-mentioned steps 4, through in amine and after salify Water-borne modification, obtain white emulsion, its solid content between 30_60%,
In above-mentioned steps 5, disperseing grinding distribution in sand mill, when meeting the requirements of after fineness, take out and Lou obtain polyurethane aqueous ink.
The present invention passes through the method synthesizing polyester polyvalent alcohol of point one-step polycondensation, and as body material, by the method for secondary chain extension, prepares aqueous polyurethane; Taking this aqueous polyurethane as ink adhesive, be equipped with pigment, weighting agent, dispersion agent etc., adopt sand milling technique, prepare water-based polyurethane ink, this ink adhesion is strong, color is adjustable, stripping strength is high, can be applicable to the requirement of the aspects such as paper, plastics and fabrication, nontoxic, environmental protection.
Brief description of the drawings
Fig. 1 is the infrared spectra of polyester polyol;
Fig. 2 is the infrared spectra of aqueous polyurethane.
Embodiment
Can further be expressly understood the present invention and superiority thereof by specific embodiments of the invention given below, but following embodiment is not limitation of the invention.
The preparation of polyester polyol
Proportioning raw materials (unit: gram)
Hexanodioic acid 292.28
Ethylene glycol 94.7
Neopentyl glycol 68
Toluene sulfonic acide 0.30
Preparation process is as follows: the raw material of proportional quantity is joined in vacuum glass reactor, be heated to 120-130 DEG C, stir; question response mixture limpid transparent after, add toluene sulfonic acide, keep this temperature; react 2 hours, be then warming up to 160-170 DEG C, continue reaction 3-4 hour; be warmed up to 200-230 DEG C and logical protection of ammonia, reaction 2-3 hour, closes down nitrogen; vacuumize; reaction 0.5-1 hour, cooling discharging, and sealing is preserved.Products therefrom is white or light solid, and hydroxy radical content is between 1.0 ~ 1.4mmol/g.
Fig. 1 is the infrared spectra of polyester polyol, and in figure, the strong absorption peak that 3433.23cm-1 occurs is the moving absorption peak ν-OH of the flexible Chun of association hydroxyl, broad peak; Can belong to the moving absorption peak of flexible Chun of ν C-O at the absorption peak at 1132.5cm-1 and 1178.82cm-1 place; Between 3300-2500cm-1, without absorption peak, show the existence without association carboxylic hydroxyl; It is the moving absorption peak of flexible Chun of ν C=O at the absorption peak of 1735.50cm-1.The charateristic avsorption band of infrared spectra shows, utilizes above-mentioned raw material composition and proportioning, has prepared polyester polyol by above-mentioned technique.
Chain extending reaction and Water-borne modification:
Chain extending reaction proportioning raw materials (unit: gram)
Polyester diol 160
Small molecule chain extender 40
Secondary chain extension agent 30
Dimethylol propionic acid (DMP) 15
Toluene-2,4-diisocyanate, 4-vulcabond (TDI) 64.8
Dibutyl tin dilaurate 0.3
Press proportioning raw materials by polyester diol, small molecule chain extender, dimethylol propionic acid, the acetone of dibutyl tin dilaurate and appropriate amount joins in reactor successively, drip TDI in 45-50 DEG C, after dripping completely, reaction 1-2 hour, then be warming up to 55 DEG C, react 3-5 hour (along with the carrying out of reaction, DMP is consumed, occur without muddy), system is chilled to 40-45 DEG C, drip gradually secondary chain extension agent, after dripping, continue reaction 1-2 hour, then be chilled to 35 DEG C (if solubility property declines, can add acetone), drip the acetone soln of triethylamine between pH=8-10, after reacting completely, under high speed shear, drip out ionized water and carry out Water-borne modification, distillating recovering solvent acetone subsequently, after distillation completely, coupling solvent the high-speed stirring of adding appropriate amount are even, discharging sealing is preserved.
Fig. 2 is the infrared spectra of aqueous polyurethane, in figure, at 3366.19cm
-1, occurring that strong flexible Chun moves absorption peak, this peak can belong to the moving absorption peak of flexible Chun of N-H and carboxylic hydroxyl, shows, and isocyanic ester has occurred to react with hydroxyl, at 1735.59cm
-1for ν
c-Othe moving absorption peak of flexible Chun, derive from the absorption of ester bond and the amino-formate bond of polyester diol; 2273.42, without absorption peak, show-N=C=O reacts completely.Infrared result shows, has obtained aqueous polyurethane after secondary chain extension.
Ink preparation material proportioning: (unit: gram)
Aqueous polyurethane 40
Pigment 35
Weighting agent 25
Coupling solvent 15
Dispersion agent 2
Defoamer 0.5
Water is appropriate
Preparation process is as follows: in order and raw material consumption ink component is joined and is disperseed in sand mill, and add zirconium white/yttrium oxide microballon, and pass into water coolant simultaneously, open motor, sand milling 2-3 hour, measure its fineness with grindometer and reach 3 μ left and right, and add the mixed solvent of water/coupling agent according to viscosity size, reach after requirement, take out leakage, remove zirconium white/yttrium oxide microballon, ink is transferred in container, sealing is preserved.
Claims (5)
1. an environment-friendly water-based polyurethane ink preparation method, is characterized in that it comprises the steps:
The first step, the preparation of polyester diol or polyester polyol: adopt the method for multicomponent copolycondensation, carry out segmentation polycondensation at three different temperature sections, prepare polyester polyol; Its temperature section is respectively 80-130 DEG C, 150-190 DEG C, 200-240 DEG C; Raw material adopts binary or poly-basic organic acid and binary or polyvalent alcohol; Make the number-average molecular weight of resin between 1000-2500; Binary or poly-basic organic acid, binary or polyvalent alcohol proportioning represent with the mol ratio of carboxyl and alcoholic extract hydroxyl group, and it is worth between 1:1.05-1.8, and catalyst levels is between 0.1-0.6% by weight;
Preparation process is as follows: the raw material of proportional quantity is joined in vacuum glass reactor, be heated to 120-130 DEG C, stir, question response mixture limpid transparent after, add the catalyzer of proportional quantity, keep this temperature, react 2 hours, be then warming up to 160-170 DEG C, continue reaction 3-4 hour, be warmed up to 200-230 DEG C and logical protection of ammonia, reaction 2-3 hour, closes down nitrogen, vacuumize, reaction 0.5-1 hour, cooling discharging, and sealing is preserved;
Second step, a chain extending reaction: the polyester diol making taking the first step or polyester polyol are body material, coordinates an appropriate chainextender and wetting ability component, taking acetone as solvent, by dripping the method for multicomponent isocyanate, preparation is containing polymkeric substance or the polycondensate of hydrophilic radical; In body material, polyester diol or polyester polyol and polyisocyanates proportioning represent with the mol ratio of alcoholic extract hydroxyl group and isocyanate group, and it is worth between 1:1.05-1.5; Between chainextender weight percentage 20%-30% in whole solid constituent; Wetting ability component adopts dimethylol propionic acid, and the weight percentage in whole solid constituent is between 3.5-15.5%, and the content of acetone is pressed the weighing scale of whole system between 50-65%; Catalyst levels is between the 0.1-1.0% of solid constituent total amount;
Preparation process is as follows: by proportioning raw materials, polyester diol or polyester polyol, chainextender, wetting ability component and an acetone are joined in reactor successively, and add catalyzer, drip multicomponent isocyanate in 45-50 DEG C, after dripping completely, reaction 1-2 hour, is then warming up to 55 DEG C, reaction 3-5 hour, wetting ability component is consumed while appearance without muddiness, by system be chilled to 30-50 DEG C stand-by;
The 3rd step, secondary chain extension reaction: after a described chain extending reaction completes, be between 30-50 DEG C time in temperature, drip gradually in the system of secondary chain extension agent after an above-mentioned chain extension completes, after dripping, continue reaction 1-1.5 hour, then keep 35 DEG C of temperature stand-by; Secondary chain extension agent adopts the micromolecular compound containing active hydroxyl, and its active hydroxy radical content is between 1.0-4.0mmol/g; Proportioning raw materials is between 1:1-2.0 by the mole ratio of the mole number of residual isocyanate base after chain extension for the first time and active hydroxyl;
The 4th step, the Water-borne modification of urethane: by the 3rd step gained secondary chain extension reactant, under constantly stirring, be neutralized between pH8-10 with organic amine, then under high speed shear effect, with deionized water Water-borne modification, and distillating recovering solvent, the solid content of the polyurethane aqueous dispersions obtaining is between 30-60%;
The 5th step, the preparation of ink: aqueous polyurethane, pigment, dispersion agent, defoamer, weighting agent, water, Virahol are mixed in proportion, disperseing grinding distribution in sand mill, when meeting the requirements of after fineness, take out and Lou obtain polyurethane aqueous ink; Its proportioning raw materials is as follows: aqueous polyurethane accounts between the 20-45% of solid amount, and weighting agent accounts for the 15-20% of solid amount, and pigment accounts between the 20-35% of solid amount;
In the preparation of described ink in order and raw material consumption ink component is joined and is disperseed in sand mill, and add zirconium white/yttrium oxide microballon, and pass into water coolant simultaneously, open motor, sand milling 2-3 hour, measure its fineness with grindometer and reach 3 μ, and add the mixed solvent of water/coupling agent according to viscosity size, reach after requirement, take out leakage, remove zirconium white/yttrium oxide microballon, ink is transferred in container, sealing is preserved.
2. a kind of environment-friendly water-based polyurethane ink preparation method as claimed in claim 1, it is characterized in that binary or the poly-basic organic acid described in the preparation of described polyester diol or polyester polyol comprises terephthalic acid, phthalic acid, inclined to one side three phenylformic acid, Pyromellitic Acid, succinic acid, sebacic acid, hexanodioic acid, the composition of one or more of propanedioic acid, described binary or polyvalent alcohol comprise ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), glycerol, glycol ether, Triethylene glycol, the composition of one or more of glycerol, described catalyzer comprises toluene sulfonic acide, Phenylsulfonic acid and chlorinated carboxylic acid.
3. a kind of environment-friendly water-based polyurethane ink preparation method as claimed in claim 1, the multicomponent isocyanate that it is characterized in that a described chain extending reaction adopts Toluene-2,4-diisocyanate, 4-vulcabond, isophorone diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate etc.; A chainextender is the polycondensate of the hydroxyl between a kind of molecular weight 400-800; Wetting ability component adopts dimethylol propionic acid; Catalyzer adopts dibutyl tin dilaurate, a kind of or its composition of triethylenediamine.
4. a kind of environment-friendly water-based polyurethane ink preparation method as claimed in claim 1, is characterized in that the secondary chain extension agent of described secondary chain extension reaction comprises isophorone diamine, quadrol and the small molecule chain extender containing active hydroxyl.
5. a kind of environment-friendly water-based polyurethane ink preparation method as claimed in claim 1, it is characterized in that in the Water-borne modification of described urethane, organic amine adopts triethylamine, the composition of one or more of di-n-butyl amine, trolamine, pH value after add-on is completed by reaction is definite, and its pH is between 8-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096467A (en) * | 2018-08-24 | 2018-12-28 | 黄山中泽新材料有限公司 | A kind of solvent-free composite high-strength high temperature resistance polyester type polyurethane resin |
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| CN102532997B (en) * | 2011-12-08 | 2014-01-01 | 郑州乐通新材料科技有限公司 | Boiling-resistant aqueous composite ink and preparation method thereof |
| CN103641995A (en) * | 2013-11-19 | 2014-03-19 | 张家港市威迪森油墨有限公司 | Preparation method of thermoplastic polyurethane for printing ink |
| CN104910356A (en) * | 2015-07-07 | 2015-09-16 | 北京市建筑工程研究院有限责任公司 | Preparation method of pyromellitic acid polyester polyol |
| WO2017015789A1 (en) * | 2015-07-24 | 2017-02-02 | 新明（芦台）科技有限公司 | Environmentally-friendly light polypropylene composite floorboard and manufacturing method therefor |
| CN106084988B (en) * | 2016-06-17 | 2019-03-19 | 苍南县宝丰印业有限公司 | A kind of multifunctional water-based ink |
| CN106349808A (en) * | 2016-08-30 | 2017-01-25 | 雷春生 | Method for preparing BOPP base material printing ink binder with high adhesive force |
| CN109111789B (en) * | 2018-09-03 | 2021-08-17 | 厦门欧化实业有限公司 | Benzene-free treatment-free matte gravure ink and preparation method thereof |
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| WO2006027544A1 (en) * | 2004-09-10 | 2006-03-16 | Fujifilm Imaging Colorants Limited | Polyurethanes |
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| CN1676556A (en) * | 2004-03-30 | 2005-10-05 | 天津科技大学 | Screen printing water-soluble ink |
| WO2006027544A1 (en) * | 2004-09-10 | 2006-03-16 | Fujifilm Imaging Colorants Limited | Polyurethanes |
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| CN109096467A (en) * | 2018-08-24 | 2018-12-28 | 黄山中泽新材料有限公司 | A kind of solvent-free composite high-strength high temperature resistance polyester type polyurethane resin |
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