CN103613993B - Hydroxyl silicone oil modified waterborne UV (Ultraviolet) printing ink and preparation method thereof - Google Patents
Hydroxyl silicone oil modified waterborne UV (Ultraviolet) printing ink and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydroxyl silicone oil modified waterborne UV (Ultraviolet) printing ink and a preparation method thereof, belonging to the technical field of environment friendly printing ink. The waterborne UV printing ink provided by the invention comprises the following components in percentage by mass: 60-85% of hydroxyl silicone oil modified hyperbranched waterborne polyurethane acrylate prepolymers (connecting materials), 1-10% of photoinitiator, 5-15% of pigment, 5-20% of solvent and 0-1% of auxiliaries. The preparation method comprises the steps: respectively and sufficiently grinding the prepolymers, the pigment and the solvent according to the proportion; dispersing at the temperature of 40-50 DEG C and the rotating speed of 400-600rpm for 1-2h; adding the photoinitiator and the auxiliaries, and uniformly mixing; and standing to obtain the waterborne UV printing ink. The printing ink is environment friendly, nontoxic, high in curing speed, good in stability, favorable in ageing resistance and the solvent resistance, excellent in adhesive force and wear resistance and suitable for various printing ways and production requirements and can be widely applied to surfaces of printed materials such as a paper material, wood, plastics, metal, glass and the like.
Description
Technical field
The present invention relates to a kind of hydroxyl silicon oil modified water-based UV ink and preparation method thereof, belong to environment-friendly ink technical field.
Background technology
Ink is mainly made up of pigment, low-melting ink vehicle, organic solvent and auxiliary agent, VOC quantity discharged is large, environmental pollution is serious, water color ink adopts water as solvent, replace organic solvent, obviously having reduced VOC quantity discharged, be applicable to the high package printed matters of health conditions requiring such as food, beverage, medicine, toy for children, there is poor solvent resistance, dry slow, low in glossiness, easily causes the drawbacks such as paper contraction in this class ink.UV ink mainly comprises prepolymer, light trigger, pigment, reactive thinner and auxiliary agent, and because of it, to have solidification rate fast, and environmental pollution is little, and cured product performance is good, is suitable for the advantage of high-speed automated production, range of application expanding day.But have pungency and toxicity in various degree to human body adding of reactive thinner in UV ink, it is not environmentally friendly product completely.
Water-based UV ink combines the advantage of water color ink and UV ink, is developed rapidly in recent years, also will be one of main development direction of the friendly type ink of FUTURE ENVIRONMENT.Its advantage mainly contains following several aspect: (1) needn't regulate viscosity by reactive thinner, can solve VOC and toxicity, irritating problem; (2) water-based system can regulate ink viscosity and rheological more easily; (3) be easy to obtain the inviscid dry film before photocuring, ensure the smooth finish of cured film, simplified dustproof operation, and before solidifying, ink film can refer to touch, stackable and repairing, the mechanical scratch of dry film is also easy to repair; (4) can obtain super book type cured film; (5) being applicable to the general coating method such as spraying, roller coat, brushing and equipment is easy to clean; (6) there is flame retardant resistance, greatly reduce the danger of fire; (7) water-based UV ink is due to the viscosity of its system and the relative molecular mass of prepolymer irrelevant (only relevant with solid content), and needn't add low molecular reactive thinner, can not take into account the two problem of hardness and snappiness thereby solved traditional light-curable ink.The patent of this respect mainly contains CN 101659785 B, CN 101659809 A, CN 102030884 A, CN 102241914 A and CN 102153914 A at present, disclose and utilized hydrophilic monomer in ink vehicle, to introduce a large amount of polar groups and unsaturated double-bond, obtained water-based UV curing system.This system adopts water to replace reactive thinner as solvent, combines the advantage of water color ink and UV ink when solving environmental problem.But still there is following some shortcomings part in water-based UV ink: (1) water-based UV ink good hydrophilic property, water tolerance is relatively poor.(2) low-melting ink vehicle in water-based UV ink, as the polymkeric substance such as urethane acrylate or epoxy acrylate, adopts " single stage method " synthetic conventionally, and microreaction process is wayward, and the ink stability of making is poor.(3) over-all properties such as glossiness, hardness, sticking power, ageing-resistant, wearability also has larger gap compared with solvent type ink.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome shortcoming that existing water-based UV ink exists with not enough, provides that a kind of water resistance is good, good stability, ageing-resistant and solvent resistance is good, the hydroxyl silicon oil modified water-based UV ink of sticking power and abrasion resistance properties excellence.
Another object of the present invention is to provide the preparation method of above-mentioned hydroxyl silicon oil modified water-based UV ink.
For realizing object of the present invention, adopt following technical scheme:
A hydroxyl silicon oil modified water-based UV ink, the component that comprises following quality percentage composition: low-melting ink vehicle 60～85%, light trigger 1～10%, pigment 5～15%, solvent 5～20%, auxiliary agent 0～1%; Described low-melting ink vehicle is hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer.
Described hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer is preferably prepared by a method comprising the following steps:
(1) in nitrogen protection, under the condition that 100～250rpm rotating speed stirs, polyester diol or polyether Glycols, hydroxy silicon oil, vulcabond and catalyzer are joined in reaction vessel, in 40～60 DEG C of temperature ranges, react 1～3h, obtain solution A; Mol ratio hydroxy silicon oil/polyester diol or the polyether Glycols of described hydroxy silicon oil and dibasic alcohol (polyester diol or polyether Glycols) are preferably 1:1～4, mol ratio vulcabond/dibasic alcohol and the hydroxy silicon oil of vulcabond and dibasic alcohol and hydroxy silicon oil are preferably 1:1～3, and in A solution, the quality percentage composition of catalyzer is preferably 0.01～0.1%.
(2) in above-mentioned A solution, add multi-hydroxy carboxy acid, in 70～80 DEG C of temperature ranges, react 1～2h, obtain solution B; In B solution, multi-hydroxy carboxy acid's quality percentage composition is preferably 2～15%.
(3) in above-mentioned B solution, add glycol amine, in-5～0 DEG C of temperature range, react 0.5～1.5h, in 70～80 DEG C of temperature ranges, react 2～4h(to till the quality percentage composition minimum of-NCO group), add acetone to regulate viscosity, obtain solution C; Mol ratio glycol amine/the vulcabond of described glycol amine and vulcabond is preferably 1:0.2～0.5, and in C solution, the quality percentage composition of acetone is preferably 10～35%.
(4) solution C is cooled to below 50 DEG C, adds triethylamine neutralization, under the condition stirring at 950～1100rpm rotating speed, add deionized water, stir 1～1.5h, make hydroxyl silicon oil modified hyperbranched aqueous polyurethane, be designated as solution D; In described triethylamine and step (2), mol ratio triethylamine/multi-hydroxy carboxy acid of multi-hydroxy carboxy acid is preferably 1:1～2, and in D solution, the quality percentage composition of deionized water is preferably 35～60%.
(5) in nitrogen protection, under the condition that 100～250rpm rotating speed stirs, polyfunctionality hydroxy acrylate, vulcabond, catalyzer and Resorcinol are joined in reaction vessel, in 40～60 DEG C of temperature ranges, react 1～3h(constant to the quality percentage composition of-NCO group till), add acetone to regulate viscosity, the vulcabond that obtains polyfunctionality hydroxy acrylate half end-blocking, is designated as solution E; Mol ratio vulcabond/polyfunctionality hydroxy acrylate of described vulcabond and polyfunctionality hydroxy acrylate is preferably 1:0.5～1.5, in E solution, the quality percentage composition of catalyzer is preferably 0.01～0.1%, the quality percentage composition that in E solution, the quality percentage composition of Resorcinol is preferably acetone in 0.01～0.1%, E solution is preferably 10～20%.
(6) in nitrogen protection, under the condition that 100～250rpm rotating speed stirs, the vulcabond of hydroxyl silicon oil modified hyperbranched aqueous polyurethane and polyfunctionality hydroxy acrylate half end-blocking is joined in reaction vessel, in 70～80 DEG C of temperature ranges, react 2～4h(to till the quality percentage composition minimum of-NCO group), add acetone to regulate viscosity, obtain hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer; The hyperbranched aqueous polyurethane of the vulcabond of mol ratio polyfunctionality hydroxy acrylate half end-blocking of the vulcabond of described polyfunctionality hydroxy acrylate half end-blocking and hydroxyl silicon oil modified hyperbranched aqueous polyurethane/hydroxyl silicon oil modified is for being preferably 1:1～6, and in hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer, the mass percent of acetone is preferably 20～40%.
Hydroxy silicon oil described in step (1) is preferably one or more the mixture in methyl hydroxy silicon oil, aminomethyl phenyl hydroxy silicon oil and hydroxy terminated fluorosilicone oil; Described polyester diol or polyether Glycols are preferably one or more the mixture in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG, hydroxy-terminated polybutadienes, polycaprolactone dibasic alcohol, PCDL; Described vulcabond is preferably one or more the mixture in tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and 4,4 – diphenylmethanediisocyanates.
Multi-hydroxy carboxy acid described in step (2) is preferably one or more the mixture in dimethylol propionic acid, dimethylolpropionic acid, tartrate.
Glycol amine described in step (3) is preferably one or more the mixture in diethanolamine, diisopropanolamine (DIPA).
Polyfunctionality hydroxy acrylate described in step (5) is preferably one or more the mixture in the prepolymer of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate monomer or hydroxyl polyfunctional acrylic ester.
Catalyzer described in step (1) and (5) is preferably one or more the mixture in dibutyl tin laurate, triethylene diamine.
Described light trigger is preferably 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-to one or more the mixture in hydroxyl ether phenyl-acetone and 1-hydroxy cyclohexyl phenylketone.
Described pigment optimization is one or more the mixture in water-based red pigment, water soluble green pigment, water-based blue pigments.
Described solvent is preferably one or more the mixture in deionized water, ethanol, acetone.
Described auxiliary agent is preferably one or more the mixture in defoamer, flow agent, strengthening agent, fire retardant, antimildew disinfectant; Described antimildew disinfectant is preferably MIT, and flow agent is preferably polyether-modified polydimethylsiloxane.
The preparation method of above-mentioned hydroxyl silicon oil modified water-based UV ink, comprise following steps: get respectively hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer, pigment and solvent by proportioning and fully grind, in the temperature range of 40～50 DEG C, under 400～600rpm rotating speed, disperse 1～2h, add light trigger and auxiliary agent, stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.
The present invention has the following advantages and effect with respect to prior art tool:
The present invention is taking vulcabond, dibasic alcohol, hydroxy silicon oil, multi-hydroxy carboxy acid, glycol amine as main raw material, with polyfunctionality hydroxy acrylate end-blocking, " two-step approach " synthesis of super branched water-based UV cured resin (hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer); Afterwards, add pigment, solvent fully to grind, add auxiliary agent and light trigger and stir, obtain hydroxyl silicon oil modified water-based UV ink.Dibasic alcohol and hydroxy silicon oil are used for regulating snappiness, and during multi-hydroxy carboxy acid is used for and salify, polyfunctionality hydroxy acrylate is given polymkeric substance photosensitive property.
Hydroxyl silicon oil modified water-based UV ink environment-protecting asepsis of the present invention, solidification rate is fast, good stability, ageing-resistant and solvent resistance is good, sticking power and abrasion resistance properties excellence, be applicable to multiple mode of printing and production requirement, can be widely used in the surface of the stocks such as paper material, timber, plastics, metal, glass.
Embodiment
The present invention is further illustrated by following unrestriced embodiment, but non-in order to limit the scope of the invention.
Embodiment 1
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 5g polyoxyethylene glycol (molecular weight is 400), 7g methyl hydroxy silicon oil (hydroxyl quality percentage composition is 6%), 8.7g Toluene-2,4-diisocyanate, 4-vulcabond and 0.009g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h; Add 1.41g dimethylol propionic acid, react 1.5h at 75 DEG C; Add 1.05g diethanolamine, at 0 DEG C, react 0.5h, at 70 DEG C, react 4h, in reaction process, add 4.26g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 1.22g triethylamine and salify, under the condition stirring, add 18g deionized water at 1000rpm rotating speed, stirring at normal temperature 1h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of methyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 11.6g Hydroxyethyl acrylate, 0.0015g Resorcinol, 8.7g Toluene-2,4-diisocyanate, 4-vulcabond and 0.009g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h, add 2.5g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of Hydroxyethyl acrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by hyperbranched aqueous polyurethane hydroxyl silicon oil modified 4.25g methyl (hydroxyl quality percentage composition is 8%) with 4.5g Hydroxyethyl acrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 12%) joins in four-hole boiling flask; at 70 DEG C, react 4h; add 5.07g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of methyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned methyl of 7g, 1g water-based red pigment (ferric oxide aqueous red pigment) and 0.95g deionized water fully grinds, in 40 DEG C, under the condition that 500rpm rotating speed stirs, disperse 2h, add 1g 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone (light trigger) and 0.05g MIT (antimildew disinfectant), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 1.
Table 1
| Performance | Test result |
| Solid content | 70% |
| Stability in storage (normal temperature)/sky | 180 |
| Set time/s | 3 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 6H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 102 |
| VOC discharge | Nothing |
Embodiment 2
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 3.33g polyoxyethylene glycol (molecular weight is 400), 9.44g methyl hydroxy silicon oil (hydroxyl quality percentage composition is 6%), 4.35g Toluene-2,4-diisocyanate, 4-vulcabond and 0.001g dibutyl tin laurate join in four-hole boiling flask, at 50 DEG C, react 2h; Add 0.44g dimethylol propionic acid, react 2h at 70 DEG C; Add 0.53g diethanolamine, at-2 DEG C, react 1h, at 75 DEG C, react 3h, in reaction process, add 3.06g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 0.3g triethylamine and salify, under the condition stirring, add 15g deionized water at 1000rpm rotating speed, stirring at normal temperature 1h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of methyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 2.90g hydroxyethyl methylacrylate, 0.0001g Resorcinol, 3.89g Toluene-2,4-diisocyanate, 4-vulcabond and 0.001g dibutyl tin laurate join in four-hole boiling flask, at 50 DEG C, react 2h, add 1.5g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of hydroxyethyl methylacrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by hyperbranched aqueous polyurethane hydroxyl silicon oil modified 6.8g methyl (hydroxyl quality percentage composition is 10%) with 10.5g hydroxyethyl methylacrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 12%) joins in four-hole boiling flask; at 75 DEG C, react 3h; add 6.37g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of methyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned methyl of 6g, 1.5g water soluble green pigment and 2g deionized water fully grinds, in 50 DEG C, under the condition that 400rpm rotating speed stirs, disperse 1h, add 0.4g 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone (light trigger) and 0.1g MIT (antimildew disinfectant), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 2.
Table 2
| Performance | Test result |
| Solid content | 60% |
| Stability in storage (normal temperature)/sky | 150 |
| Set time/s | 5 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 3H |
| Wear resistance (750g, 500r) | 0.02 |
| Draw lattice sticking power | 1 grade |
| Glossiness/degree | 98 |
| VOC discharge | Nothing |
Embodiment 3
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 5g polycaprolactone dibasic alcohol (molecular weight is 1000), 8.5g aminomethyl phenyl hydroxy silicon oil (hydroxyl quality percentage composition is 8%), 13.05g Toluene-2,4-diisocyanate, 4-vulcabond and 0.018g dibutyl tin laurate join in four-hole boiling flask, at 60 DEG C, react 1h; Add 2g dimethylol propionic acid, react 1h at 80 DEG C; Add 3.94g diethanolamine, at-5 DEG C, react 1.5h, at 80 DEG C, react 2h, in reaction process, add 9.47g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 1.52g triethylamine and salify, under the condition stirring, add 30g deionized water at 1000rpm rotating speed, stirring at normal temperature 1.5h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of aminomethyl phenyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 3.25g hydroxyethyl methylacrylate, 2.9g Hydroxyethyl acrylate, 0.0018g Resorcinol, 13.06g Toluene-2,4-diisocyanate, 4-vulcabond and 0.002g dibutyl tin laurate join in four-hole boiling flask, at 60 DEG C, react 1h, add 4.2g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of hydroxyethyl methylacrylate/Hydroxyethyl acrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by hyperbranched aqueous polyurethane hydroxyl silicon oil modified 10.2g aminomethyl phenyl (hydroxyl quality percentage composition is 10%) with 18.66g hydroxyethyl methylacrylate/Hydroxyethyl acrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 13.5%) joins in four-hole boiling flask; at 80 DEG C, react 2h; add 13.4g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of aminomethyl phenyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned aminomethyl phenyl of 8.5g, 0.5g water-based blue pigments and 0.5g deionized water fully grinds, in 50 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.5g 2-hydroxy-2-methyl-1-phenyl-acetone (light trigger), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 3.
Table 3
| Performance | Test result |
| Solid content | 85% |
| Stability in storage (normal temperature)/sky | 160 |
| Set time/s | 1 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 5H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 101 |
| VOC discharge | Nothing |
Embodiment 4
In nitrogen protection, under the condition that 150rpm rotating speed stirs, 2.5g polyoxyethylene glycol (molecular weight is 400), 3.75g polyoxyethylene glycol (molecular weight is 600), 5.31g aminomethyl phenyl hydroxy silicon oil (hydroxyl quality percentage composition is 8%), 11.11g isophorone diisocyanate and 0.009g dibutyl tin laurate are joined in four-hole boiling flask, at 60 DEG C, react 1h; Add 1.41g dimethylol propionic acid, react 1h at 80 DEG C; Add 2.6g diethanolamine, at-5 DEG C, react 1.5h, at 80 DEG C, react 2h, in reaction process, add 10.5g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 1.22g triethylamine and salify, under the condition stirring, add 32g deionized water at 1000rpm rotating speed, stirring at normal temperature 1.5h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of aminomethyl phenyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, 3.48g Hydroxyethyl acrylate, 0.002g Resorcinol, 9.99g isophorone diisocyanate and 0.001g dibutyl tin laurate are joined in four-hole boiling flask, at 60 DEG C, react 1h, add 3g acetone to regulate viscosity, obtain the isophorone diisocyanate of Hydroxyethyl acrylate half end-blocking;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; hyperbranched aqueous polyurethane hydroxyl silicon oil modified 3.4g aminomethyl phenyl (hydroxyl quality percentage composition is 12%) and the isophorone diisocyanate (NCO quality percentage composition is 15%) of 8.8g Hydroxyethyl acrylate half end-blocking are joined in four-hole boiling flask; at 80 DEG C, react 2h; add 3.4g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of aminomethyl phenyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned aminomethyl phenyl of 8g, 0.6g water-based blue pigments, 0.6 water soluble green pigment and 0.6g deionized water fully grinds, in 50 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.1g 2-hydroxy-2-methyl-1-to hydroxyl ether phenyl-acetone (light trigger) and the polyether-modified polydimethylsiloxane of 0.1g (flow agent), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 4.
Table 4
| Performance | Test result |
| Solid content | 80% |
| Stability in storage (normal temperature)/sky | 180 |
| Set time/s | 3 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 5H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 102 |
| VOC discharge | Nothing |
Embodiment 5
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 3.75g polyoxyethylene glycol (molecular weight is 600), 10.63g hydroxy terminated fluorosilicone oil (hydroxyl quality percentage composition is 6%), 12.51g 4,4-diphenylmethanediisocyanate and 0.011g triethylene diamine join in four-hole boiling flask, at 50 DEG C, react 2h; Add 1.78g tartrate, react 1h at 80 DEG C; Add 1.99g diisopropanolamine (DIPA), at-2 DEG C, react 1h, at 70 DEG C, react 4h, in reaction process, add 10g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 2.42g triethylamine and salify, under the condition stirring, add 40g deionized water at 1000rpm rotating speed, stirring at normal temperature 1h, makes the hyperbranched aqueous polyurethane of hydroxy terminated fluorosilicone oil modification;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 5.8g Hydroxyethyl acrylate, 0.0015g Resorcinol, 6.25g 4,4-diphenylmethanediisocyanate and 0.009g triethylene diamine join in four-hole boiling flask, at 50 DEG C, react 2h, add 3g acetone to regulate viscosity, obtain 4 of Hydroxyethyl acrylate half end-blocking, 4-diphenylmethanediisocyanate;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; by the hyperbranched aqueous polyurethane of 5.1g hydroxy terminated fluorosilicone oil modification (hydroxyl quality percentage composition is 10%) and 4 of 5.25g Hydroxyethyl acrylate half end-blocking; 4-diphenylmethanediisocyanate (NCO quality percentage composition is 2%) joins in four-hole boiling flask; at 75 DEG C, react 3h; add 4.1g acetone to regulate viscosity, obtain the hyperbranched aqueous polyurethane acrylic ester prepolymer of hydroxy terminated fluorosilicone oil modification.
Hyperbranched aqueous polyurethane acrylic ester prepolymer, 0.6g water-based red pigment, 0.6 water soluble green pigment and the 0.6g ethanol of getting the above-mentioned hydroxy terminated fluorosilicone oil modification of 8g fully grind, in 40 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.1g 1-hydroxy cyclohexyl phenylketone (light trigger) and the polyether-modified polydimethylsiloxane of 0.1g (flow agent), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 5.
Table 5
| Performance | Test result |
| Solid content | 80% |
| Stability in storage (normal temperature)/sky | 180 |
| Set time/s | 1 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 6H |
| Wear resistance (750g, 500r) | 0.02 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 101 |
| VOC discharge | Nothing |
Embodiment 6
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 16.67g hydroxy-terminated polybutadienes (molecular weight is 2000), 9.45g hydroxy terminated fluorosilicone oil (hydroxyl quality percentage composition is 6%), 8.7g Toluene-2,4-diisocyanate, 4-vulcabond and 0.018g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h; Add 2.3g tartrate and 2.12g dimethylolpropionic acid, react 2h at 70 DEG C; Add 2.66g diisopropanolamine (DIPA), at 0 DEG C, react 0.5h, at 80 DEG C, react 2h, in reaction process, add 19g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 3.66g triethylamine and salify, under the condition stirring, add 55g deionized water at 1000rpm rotating speed, stirring at normal temperature 1.5h, makes the hyperbranched aqueous polyurethane of hydroxy terminated fluorosilicone oil modification;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 2.91g hydroxyethyl methylacrylate, 0.0002g Resorcinol, 3.89g Toluene-2,4-diisocyanate, 4-vulcabond and 0.001g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h, add 1.5g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of hydroxyethyl methylacrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by the hyperbranched aqueous polyurethane of 8.5g hydroxy terminated fluorosilicone oil modification (hydroxyl quality percentage composition is 8%) with 10.5g hydroxyethyl methylacrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 12%) joins in four-hole boiling flask; at 80 DEG C, react 2h; add 6g acetone to regulate viscosity, obtain the hyperbranched aqueous polyurethane acrylic ester prepolymer of hydroxy terminated fluorosilicone oil modification.
Hyperbranched aqueous polyurethane acrylic ester prepolymer, 1.2g water-based blue pigments, 0.2g acetone and the 0.4g deionized water of getting the above-mentioned hydroxy terminated fluorosilicone oil modification of 8g fully grind, in 40 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.1g 2-hydroxy-2-methyl-1-phenyl-acetone (light trigger), 0.05g MIT (antimildew disinfectant) and the polyether-modified polydimethylsiloxane of 0.05g (flow agent), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 6.
Table 6
| Performance | Test result |
| Solid content | 80% |
| Stability in storage (normal temperature)/sky | 180 |
| Set time/s | 3 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 5H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 100 |
| VOC discharge | Nothing |
Embodiment 7
In nitrogen protection, under the condition that 150rpm rotating speed stirs, 1.25g PTMG (molecular weight is 250), 11.33g methyl hydroxy silicon oil (hydroxyl quality percentage composition is 6%), 8.41g hexamethylene diisocyanate and 0.009g dibutyl tin laurate are joined in four-hole boiling flask, at 60 DEG C, react 1h; Add 1.41g dimethylol propionic acid, react 1h at 80 DEG C; Add 1.05g diethanolamine, at-5 DEG C, react 1.5h, at 75 DEG C, react 3h, in reaction process, add 6.02g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 1.22g triethylamine and salify, under the condition stirring, add 30g deionized water at 1000rpm rotating speed, stirring at normal temperature 1h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of methyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 2.89g hydroxyethyl methylacrylate, 0.0006g Resorcinol, 3.9g Toluene-2,4-diisocyanate, 4-vulcabond and 0.002g dibutyl tin laurate join in four-hole boiling flask, at 50 DEG C, react 2h, add 1.7g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of hydroxyethyl methylacrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by hyperbranched aqueous polyurethane hydroxyl silicon oil modified 6.81g methyl (hydroxyl quality percentage composition is 10%) with 10.52g hydroxyethyl methylacrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 12%) joins in four-hole boiling flask; at 75 DEG C, react 3h; add 7.07g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of methyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned methyl of 8g, 1.2g water-based blue pigments and 0.6g deionized water fully grinds, in 50 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.1g 2-hydroxy-2-methyl-1-phenyl-acetone (light trigger) and the polyether-modified polydimethylsiloxane of 0.1g (flow agent), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 7.
Table 7
| Performance | Test result |
| Solid content | 80% |
| Stability in storage (normal temperature)/sky | 160 |
| Set time/s | 5 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 6H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 102 |
| VOC discharge | Nothing |
Embodiment 8
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 2.55 PCDL (molecular weight is 300), 4.82g methyl hydroxy silicon oil (hydroxyl quality percentage composition is 6%), 8.7g Toluene-2,4-diisocyanate, 4-vulcabond and 0.013g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h; Add 1.41g dimethylol propionic acid, at 75 DEG C, react 1.5h; Add 1.05g diethanolamine, at 0 DEG C, react 0.5h, at 70 DEG C, react 4h, in reaction process, add 5.16g acetone to regulate viscosity; Be cooled to 50 DEG C, add in 1.22g triethylamine and salify, under the condition stirring, add 37.45g deionized water at 1000rpm rotating speed, stirring at normal temperature 1h, makes the hydroxyl silicon oil modified hyperbranched aqueous polyurethane of methyl;
In nitrogen protection, under the condition that 150rpm rotating speed stirs, by 9.93g pentaerythritol triacrylate, 0.0036g Resorcinol, 8.7g Toluene-2,4-diisocyanate, 4-vulcabond and 0.009g dibutyl tin laurate join in four-hole boiling flask, at 40 DEG C, react 3h, add 3.5g acetone to regulate viscosity, obtain the Toluene-2,4-diisocyanate of pentaerythritol triacrylate half end-blocking, 4-vulcabond;
In nitrogen protection; under the condition that 150rpm rotating speed stirs; Toluene-2,4-diisocyanate by hyperbranched aqueous polyurethane hydroxyl silicon oil modified 8.5g methyl (hydroxyl quality percentage composition is 8%) with 12.6g Hydroxyethyl acrylate half end-blocking; 4-vulcabond (NCO quality percentage composition is 10%) joins in four-hole boiling flask; at 70 DEG C, react 4h; add 9.07g acetone to regulate viscosity, obtain the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of methyl.
Getting the hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer of the above-mentioned methyl of 8g, 1.2g water-based blue pigments and 0.6g deionized water fully grinds, in 50 DEG C, under the condition that 600rpm rotating speed stirs, disperse 1h, add 0.1g 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone and 0.05g 2-hydroxy-2-methyl-1-phenyl-acetone (light trigger) and the polyether-modified polydimethylsiloxane of 0.05g (flow agent), stir, leave standstill and obtain hydroxyl silicon oil modified water-based UV ink.The performance of gained ink is as shown in table 8.
Table 8
| Performance | Test result |
| Solid content | 80% |
| Stability in storage (normal temperature)/sky | 180 |
| Set time/s | 5 |
| Water tolerance | Excellent |
| Ageing resistance | Excellent |
| Hardness | 6H |
| Wear resistance (750g, 500r) | 0.01 |
| Draw lattice sticking power | 0 grade |
| Glossiness/degree | 102 |
| VOC discharge | Nothing |
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. a hydroxyl silicon oil modified water-based UV ink, is characterized in that the component that comprises following quality percentage composition: low-melting ink vehicle 60～85%, light trigger 1～10%, pigment 5～15%, solvent 5～20%, auxiliary agent 0～1%; Described low-melting ink vehicle is hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer;
Described hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer is prepared by a method comprising the following steps:
(1) in nitrogen protection, under the condition that 100～250rpm rotating speed stirs, polyester diol or polyether Glycols, hydroxy silicon oil, vulcabond and catalyzer are joined in reaction vessel, in 40～60 DEG C of temperature ranges, react 1～3h, obtain solution A;
(2) in above-mentioned A solution, add multi-hydroxy carboxy acid, in 70～80 DEG C of temperature ranges, react 1～2h, obtain solution B;
(3) in above-mentioned B solution, add glycol amine, in-5～0 DEG C of temperature range, react 0.5～1.5h, in 70～80 DEG C of temperature ranges, react 2～4h, add acetone to regulate viscosity, obtain solution C;
(4) solution C is cooled to below 50 DEG C, adds triethylamine neutralization, under the condition stirring at 950～1100rpm rotating speed, add deionized water, stir 1～1.5h, make hydroxyl silicon oil modified hyperbranched aqueous polyurethane, be designated as solution D;
(5) in nitrogen protection, under the condition that 100～250rpm rotating speed stirs, polyfunctionality hydroxy acrylate, vulcabond, catalyzer and Resorcinol are joined in reaction vessel, in 40～60 DEG C of temperature ranges, react 1～3h, add acetone to regulate viscosity, the vulcabond that obtains polyfunctionality hydroxy acrylate half end-blocking, is designated as solution E;
(6) in nitrogen protection; under the condition that 100～250rpm rotating speed stirs; the vulcabond of hydroxyl silicon oil modified hyperbranched aqueous polyurethane and polyfunctionality hydroxy acrylate half end-blocking is joined in reaction vessel; in 70～80 DEG C of temperature ranges, react 2～4h; add acetone to regulate viscosity, obtain hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer.
2. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that:
The mol ratio of the hydroxy silicon oil described in step (1) and dibasic alcohol is 1:1～4, and the mol ratio of vulcabond and dibasic alcohol and hydroxy silicon oil is 1:1～3, and in A solution, the quality percentage composition of catalyzer is 0.01～0.1%;
In B solution described in step (2), multi-hydroxy carboxy acid's quality percentage composition is 2～15%;
The mol ratio of the glycol amine described in step (3) and vulcabond is 1:0.2～0.5, and in C solution, the quality percentage composition of acetone is 10～35%;
In triethylamine described in step (4) and step (2), multi-hydroxy carboxy acid's mol ratio is 1:1～2, and in D solution, the quality percentage composition of deionized water is 35～60%;
The mol ratio of the vulcabond described in step (5) and polyfunctionality hydroxy acrylate is 1:0.5～1.5, in E solution, the quality percentage composition of catalyzer is 0.01～0.1%, in E solution, the quality percentage composition of Resorcinol is that the quality percentage composition of acetone in 0.01～0.1%, E solution is 10～20%;
The mol ratio of the vulcabond of polyfunctionality hydroxy acrylate half end-blocking described in step (6) and hydroxyl silicon oil modified hyperbranched aqueous polyurethane is 1:1～6, and in hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer, the mass percent of acetone is 20～40%.
3. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that:
Hydroxy silicon oil described in step (1) is one or more the mixture in methyl hydroxy silicon oil, aminomethyl phenyl hydroxy silicon oil and hydroxy terminated fluorosilicone oil; Described polyester diol or polyether Glycols are one or more the mixture in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG, hydroxy-terminated polybutadienes, polycaprolactone dibasic alcohol, PCDL; Described vulcabond is one or more the mixture in tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and 4,4 – diphenylmethanediisocyanates;
Multi-hydroxy carboxy acid described in step (2) is one or more the mixture in dimethylol propionic acid, dimethylolpropionic acid, tartrate;
Glycol amine described in step (3) is one or more the mixture in diethanolamine, diisopropanolamine (DIPA);
Polyfunctionality hydroxy acrylate described in step (5) is one or more the mixture in the prepolymer of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate monomer or hydroxyl polyfunctional acrylic ester;
Catalyzer described in step (1) and (5) is one or more the mixture in dibutyl tin laurate, triethylene diamine.
4. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that: described light trigger is 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone, 2-hydroxy-2-methyl-1-to one or more the mixture in hydroxyl ether phenyl-acetone and 1-hydroxy cyclohexyl phenylketone.
5. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that: described pigment is one or more the mixture in water-based red pigment, water soluble green pigment, water-based blue pigments.
6. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that: described solvent is one or more the mixture in deionized water, ethanol, acetone.
7. hydroxyl silicon oil modified water-based UV ink according to claim 1, is characterized in that: described auxiliary agent is one or more the mixture in defoamer, flow agent, strengthening agent, fire retardant, antimildew disinfectant.
8. hydroxyl silicon oil modified water-based UV ink according to claim 7, is characterized in that: described antimildew disinfectant is that MIT, flow agent are polyether-modified polydimethylsiloxane.
9. the preparation method of the hydroxyl silicon oil modified water-based UV ink described in claim 1-8 any one, it is characterized in that comprising the steps: that getting respectively hydroxyl silicon oil modified hyperbranched aqueous polyurethane acrylic ester prepolymer, pigment and solvent by proportioning fully grinds, in the temperature range of 40～50 DEG C, under 400～600rpm rotating speed, disperse 1～2h, add light trigger and auxiliary agent, stir, obtain hydroxyl silicon oil modified water-based UV ink.
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