阅读说明：本技术 一种快速固化uv油墨及其制备工艺 (Fast curing UV (ultraviolet) ink and preparation process thereof ) 是由 不公告发明人 于 2021-01-19 设计创作，主要内容包括：本发明公开了一种快速固化UV油墨及其制备工艺,该快速固化UV油墨包括如下重量份原料：改性连接料40-60份、颜色填料10-15份、无水乙醇10-15份、稳定剂1-2份、流平剂1-2份、消泡剂1-2份、分散剂1-2份、光引发剂3-5份以及去离子水60-80份；包括混合、研磨、加入光引发剂等步骤制得,其中制备了一种改性连接料,可以使制备的油墨具有优异的反应活性、抗老化与耐变黄性能,还制备了一种光引发剂,该光引发剂含有长链烷基和氟原子,引入有机氟可以有效减弱氧阻聚对固化反应的阻碍,同时长链烷基可以将光引发剂拖拽至分子表面,进一步提升光引发剂的抗氧阻聚性能,实现快速固化。(The invention discloses a fast curing UV ink and a preparation process thereof, wherein the fast curing UV ink comprises the following raw materials in parts by weight: 40-60 parts of modified connecting material, 10-15 parts of color filler, 10-15 parts of absolute ethyl alcohol, 1-2 parts of stabilizer, 1-2 parts of flatting agent, 1-2 parts of defoaming agent, 1-2 parts of dispersant, 3-5 parts of photoinitiator and 60-80 parts of deionized water; the preparation method comprises the steps of mixing, grinding, adding a photoinitiator and the like, wherein a modified connecting material is prepared, so that the prepared ink has excellent reactivity, ageing resistance and yellowing resistance, and the photoinitiator is also prepared, contains long-chain alkyl and fluorine atoms, and can effectively weaken the obstruction of oxygen inhibition on curing reaction by introducing organic fluorine, and meanwhile, the photoinitiator can be dragged to the surface of a molecule by the long-chain alkyl, so that the anti-oxygen inhibition performance of the photoinitiator is further improved, and the rapid curing is realized.)

1. A fast curing UV ink is characterized in that: the feed comprises the following raw materials in parts by weight: 40-60 parts of modified connecting material, 10-15 parts of color filler, 10-15 parts of absolute ethyl alcohol, 1-2 parts of stabilizer, 1-2 parts of flatting agent, 1-2 parts of defoaming agent, 1-2 parts of dispersant, 3-5 parts of photoinitiator and 60-80 parts of deionized water;

the fast curing UV ink is prepared by the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 30-40min at the temperature of 50-60 ℃ and the rotating speed of 400-600r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2-3h at the rotating speed of 800-;

step S3: adding the mixed material obtained in the step S2 into a stirring kettle, heating to 55-65 ℃, adding a photoinitiator into the stirring kettle, stirring for 20-30min at the temperature of 55-65 ℃ and the rotation speed of 500-;

the modified connecting material is prepared by the following steps:

step A1: adding dichloromethane into a reaction kettle which is cleaned and dried, then sequentially adding glycerol and a complexing agent into the reaction kettle, reacting at 10-15 deg.C and 50-100r/min for 30-40min, maintaining at 5-10 deg.C and 100-200r/min, adding epoxy cyclopentane into the reaction kettle by using dropping funnel, the temperature is maintained at 5-10 ℃, the rotation speed is 100-, then dripping epoxy chloropropane from the dropping funnel into the reaction kettle, continuing to perform heat preservation reaction for 4-5h at the temperature of 5-10 ℃ and the rotating speed of 100-;

step A2: adding the intermediate A1 into a reaction kettle which is cleaned and dried, slowly adding a polymerization inhibitor, a catalyst and acrylic acid into the reaction kettle at the temperature of 50-60 ℃, heating to 110-115 ℃ and reacting for 2-3h to obtain an intermediate A2;

step A3: adding the intermediate A2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol and dibutyltin dilaurate into a reaction kettle, reacting for 1-2h at 60-70 ℃ under the protection of nitrogen, reducing the temperature to 45-50 ℃ after the reaction is finished, then adding 2, 2-dimethylolpropionic acid into the reaction kettle, reacting for 2-3h at 60-70 ℃ after the addition is finished, adding acetone during the reaction to adjust the viscosity, adding hydroxypropyl acrylate to react for 1-2h at 60-65 ℃, and adding absolute ethyl alcohol to react for 0.5-1h after the reaction is finished, thus obtaining the modified connecting material.

2. The fast curing UV ink according to claim 1, wherein: the color filler is any one of titanium dioxide, zinc oxide, carbon black, iron oxide yellow, iron oxide red, lithopone yellow and cobalt blue; the stabilizer is coconut oil fatty acid diethanolamide; the flatting agent is any one of polydimethylsiloxane, polymethyl alkyl siloxane, organic modified polysiloxane and fluorocarbon flatting agent; the defoaming agent is any one of castor oil, linseed kernel, oil animal oil, a polysiloxane defoaming agent, a polyether modified silicone oil defoaming agent and a higher alcohol defoaming agent; the dispersing agent is any one of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide and fatty acid polyglycol ester.

3. The fast curing UV ink according to claim 1, wherein: the photoinitiator is prepared by the following steps:

step B1: adding ethylene oxide and 25-30% by mass of monomethylamine aqueous solution into a reaction kettle, then adding a catalyst, stirring and mixing for 5-10min under the condition of the rotation speed of 100-;

step B2: adding octadecanol and hydrogen bromide into a reaction kettle, then adding a sulfuric acid solution with the mass fraction of 98%, reacting for 4-5h at the temperature of 120-; adding the intermediate B2 and the intermediate B1 obtained in the step B1 into a reaction kettle, reacting for 2-3h at the temperature of 100-;

step B3: adding methanol into a reaction kettle, adding an intermediate B4 and thioxanthone acetic acid into the reaction kettle, stirring and reacting at the rotation speed of 300-400r/min and the temperature of 20-25 ℃ for 2-3h, filtering and collecting filtrate after the reaction is finished, adding deionized water into the filtrate, removing water by using a rotary evaporator, adding chloroform for removing impurities, performing rotary evaporation again after the impurities are removed, placing the filtrate in a vacuum drying box after the rotary evaporation is finished, and drying at 60 ℃ for 12h to obtain an intermediate B5;

step B4: adding isophorone diisocyanate and dibutyltin dilaurate into a reaction kettle, adding an intermediate B5 obtained in the step B3 into the reaction kettle at the temperature of 40-50 ℃ and the rotation speed of 200-400r/min, adding acetone at the same time, reacting for 2-3h, adding a reaction solution into deionized water for hydrolysis after the reaction is finished, extracting by using ethyl acetate, removing the ethyl acetate by using a rotary evaporator after the extraction is finished, placing a product in a vacuum drying box, drying for 10-12h at the temperature of 50-60 ℃ to obtain an intermediate B6, adding an intermediate B6, perfluoroalkylethyl acrylate, LiOH and absolute ethyl alcohol into the reaction kettle, reacting for 5-6h at the temperature of 30-35 ℃, and removing the LiOH and the ethyl alcohol after the reaction is finished to obtain the photoinitiator.

4. The fast curing UV ink according to claim 3, wherein: the dosage ratio of the ethylene oxide, the monomethylamine aqueous solution and the catalyst in the step B1 is 3 mol: 1 mol: 0.2g, wherein the catalyst is an ethylene oxide catalyst with the mass fraction of 3%, and the dosage ratio of the octadecanol, the hydrogen bromide and the sulfuric acid solution in the step B2 is 0.05 mol: 20 g: 4g of the total weight of the mixture; the dosage ratio of the intermediate B2 to the intermediate B1 is 1 mol: 0.5-1mol, wherein the mixing ratio of the ethyl acetate to the absolute ethyl alcohol is 1mL to 1-5 mL; the dosage ratio of the methanol, the intermediate B4 and the thioxanthone acetic acid in the step B3 is 0.3g-0.4 g: 1 mmol: 5 mL; the using ratio of the isophorone diisocyanate, the dibutyltin dilaurate, the intermediate B5 and the acetone in the step B4 is 2 g: 0.02 g: 10 mmol: 8-10mL, wherein the dosage ratio of the intermediate B6, the perfluoroalkyl ethyl acrylate, the LiOH and the absolute ethyl alcohol is 1 mmol: 1 mmol: 0.02 g: 10 mL.

5. The fast curing UV ink according to claim 1, wherein: in the step A1, the dosage ratio of dichloromethane, glycerol, complexing agent, cyclopentane epoxide, epichlorohydrin and deionized water is 5-10 mL: 2mL of: 2 g: 1 mol: 1 mol: 10mL, wherein the complexing agent is boron trifluoride diethyl ether.

6. The fast curing UV ink according to claim 1, wherein: the using amount ratio of the intermediate A1, the polymerization inhibitor, the catalyst and the acrylic acid in the step A2 is 1-2 g: 0.2 g: 0.3 g: 1g, the polymerization inhibitor is hydroxyanisole, and the catalyst is N, N-dimethylbenzylamine.

7. The fast curing UV ink according to claim 1, wherein: the dosage ratio of the intermediate 2, the hexamethylene diisocyanate, the triethanolamine, the polyoxyethylene glycol, the dibutyltin dilaurate, the 2, 2-dimethylolpropionic acid and the hydroxypropyl acrylate in the step A3 is 1-1.5 mol: 1 mol: 0.5 mol: 1 mol: 0.1 g: 0.5 mol: 2 mol.

8. The process for preparing a fast curing UV ink according to claim 1, wherein: the method specifically comprises the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 30-40min at the temperature of 50-60 ℃ and the rotating speed of 400-600r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2-3h at the rotating speed of 800-;

step S3: and (4) adding the mixed material obtained in the step S2 into a stirring kettle, heating to 55-65 ℃, adding a photoinitiator into the stirring kettle, stirring for 20-30min at the temperature of 55-65 ℃ and the rotating speed of 500-.

Technical Field

The invention relates to the technical field of UV (ultraviolet) printing ink, in particular to rapid curing UV printing ink and a preparation process thereof.

Background

UV refers to ultraviolet light, and UV ink refers to ink which forms a film and dries ink by polymerizing monomers in an ink vehicle into polymers by using ultraviolet light of different wavelengths and energies under the irradiation of ultraviolet light. The UV ink also belongs to ink, and is ink which does not use a solvent, has high drying speed, good luster, bright color, water resistance, solvent resistance and good wear resistance. UV inks have become a relatively mature ink technology with almost zero pollutant emissions. UV inks have the property of selective absorption of UV light. Drying is affected by the total energy of the light radiated by the UV light source and the energy distribution of the light of different wavelengths. Under the irradiation of UV light, the UV ink photopolymerization initiator absorbs photons with a certain wavelength, is excited to an excited state to form free radicals or ions, then through intermolecular energy transfer, the polymerized prepolymer, the photosensitive monomer and the photosensitive polymer become excited states to generate a charge transfer complex, and the complex particles are continuously crosslinked and polymerized to be cured into a film. Meanwhile, the UV ink is economical and efficient, covers all printing fields, and is generally more used on high-grade printing pieces due to higher price than solvent-based ink. The UV printing ink comprises UV grinding, UV freezing, UV foaming, UV wrinkling, UV raised characters, UV refraction, UV decoration, UV light fixation and UV oil-polishing special package printing ink. On the printing surface with metal mirror surface gloss, drying equipment printed by UV ink is processed by UV light by adopting a silk-screen printing process means, so that a unique visual effect is produced, the printing machine is elegant, solemn and luxurious, and is mainly used for packaging and printing of medium-high grade elegant and unique cigarettes, wine, cosmetics, health care products, foods and medicines.

With the rapid development speed of modern times, all aspects need to finish the work more rapidly, and the same is true for ink curing, so that the common UV ink often cannot be completely cured and surface cured after being printed at a certain speed at a high speed, but ink deep layer is not completely cured, so that the quality problems of adhesion, scratching and the like in printing are caused.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides the rapid curing UV ink and the preparation process thereof, which are used for solving the quality problems of adhesion, scratching and the like caused by incomplete curing of the surface and incomplete curing of the deep layer of the ink after the common UV ink is printed at a certain speed at a high speed.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme: the fast curing UV printing ink comprises the following raw materials in parts by weight: 40-60 parts of modified connecting material, 10-15 parts of color filler, 10-15 parts of absolute ethyl alcohol, 1-2 parts of stabilizer, 1-2 parts of flatting agent, 1-2 parts of defoaming agent, 1-2 parts of dispersant, 3-5 parts of photoinitiator and 60-80 parts of deionized water;

the fast curing UV ink is prepared by the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 30-40min at the temperature of 50-60 ℃ and the rotating speed of 400-600r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2-3h at the rotating speed of 800-;

step S3: adding the mixed material obtained in the step S2 into a stirring kettle, heating to 55-65 ℃, adding a photoinitiator into the stirring kettle, stirring for 20-30min at the temperature of 55-65 ℃ and the rotation speed of 500-;

the modified connecting material is prepared by the following steps:

step A1: adding dichloromethane into a reaction kettle which is cleaned and dried, then sequentially adding glycerol and a complexing agent into the reaction kettle, reacting at 10-15 deg.C and 50-100r/min for 30-40min, maintaining at 5-10 deg.C and 100-200r/min, adding epoxy cyclopentane into the reaction kettle by using dropping funnel, the temperature is maintained at 5-10 ℃, the rotation speed is 100-, then dripping epoxy chloropropane from the dropping funnel into the reaction kettle, continuing to perform heat preservation reaction for 4-5h at the temperature of 5-10 ℃ and the rotating speed of 100-;

step A2: adding the intermediate A1 into a reaction kettle which is cleaned and dried, slowly adding a polymerization inhibitor, a catalyst and acrylic acid into the reaction kettle at the temperature of 50-60 ℃, heating to 110-115 ℃ and reacting for 2-3h to obtain an intermediate A2;

step A3: adding the intermediate A2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol and dibutyltin dilaurate into a reaction kettle, reacting for 1-2h at 60-70 ℃ under the protection of nitrogen, reducing the temperature to 45-50 ℃ after the reaction is finished, then adding 2, 2-dimethylolpropionic acid into the reaction kettle, reacting for 2-3h at 60-70 ℃ after the addition is finished, adding acetone during the reaction to adjust the viscosity, adding hydroxypropyl acrylate to react for 1-2h at 60-65 ℃, and adding absolute ethyl alcohol to react for 0.5-1h after the reaction is finished, thus obtaining the modified connecting material.

Further, the color filler is any one of titanium dioxide, zinc oxide, carbon black, iron oxide yellow, iron oxide red, lithopone yellow and cobalt blue; the stabilizer is coconut oil fatty acid diethanolamide; the flatting agent is any one of polydimethylsiloxane, polymethyl alkyl siloxane, organic modified polysiloxane and fluorocarbon flatting agent; the defoaming agent is any one of castor oil, linseed kernel, oil animal oil, a polysiloxane defoaming agent, a polyether modified silicone oil defoaming agent and a higher alcohol defoaming agent; the dispersing agent is any one of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide and fatty acid polyglycol ester.

Further, the photoinitiator is prepared by the following steps:

step B1: adding ethylene oxide and 25-30% by mass of monomethylamine aqueous solution into a reaction kettle, then adding a catalyst, stirring and mixing for 5-10min under the condition of the rotation speed of 100-;

step B2: adding octadecanol and hydrogen bromide into a reaction kettle, then adding a sulfuric acid solution with the mass fraction of 98%, reacting for 4-5h at the temperature of 120-; adding the intermediate B2 and the intermediate B1 obtained in the step B1 into a reaction kettle, reacting for 2-3h at the temperature of 100-;

step B3: adding methanol into a reaction kettle, adding an intermediate B4 and thioxanthone acetic acid into the reaction kettle, stirring and reacting at the rotation speed of 300-400r/min and the temperature of 20-25 ℃ for 2-3h, filtering and collecting filtrate after the reaction is finished, adding deionized water into the filtrate, removing water by using a rotary evaporator, adding chloroform for removing impurities, performing rotary evaporation again after the impurities are removed, placing the filtrate in a vacuum drying box after the rotary evaporation is finished, and drying at 60 ℃ for 12h to obtain an intermediate B5;

step B4: adding isophorone diisocyanate and dibutyltin dilaurate into a reaction kettle, adding an intermediate B5 obtained in the step B3 into the reaction kettle at the temperature of 40-50 ℃ and the rotation speed of 200-400r/min, adding acetone at the same time, reacting for 2-3h, adding a reaction solution into deionized water for hydrolysis after the reaction is finished, extracting by using ethyl acetate, removing the ethyl acetate by using a rotary evaporator after the extraction is finished, placing a product in a vacuum drying box, drying for 10-12h at the temperature of 50-60 ℃ to obtain an intermediate B6, adding an intermediate B6, perfluoroalkylethyl acrylate, LiOH and absolute ethyl alcohol into the reaction kettle, reacting for 5-6h at the temperature of 30-35 ℃, and removing the LiOH and the ethyl alcohol after the reaction is finished to obtain the photoinitiator.

Further, the dosage ratio of the ethylene oxide, the aqueous solution of monomethylamine and the catalyst in the step B1 is 3 mol: 1 mol: 0.2g, wherein the catalyst is an ethylene oxide catalyst with the mass fraction of 3%, and the dosage ratio of the octadecanol, the hydrogen bromide and the sulfuric acid solution in the step B2 is 0.05 mol: 20 g: 4g of the total weight of the mixture; the dosage ratio of the intermediate B2 to the intermediate B1 is 1 mol: 0.5-1mol, wherein the mixing ratio of the ethyl acetate to the absolute ethyl alcohol is 1mL to 1-5 mL; the dosage ratio of the methanol, the intermediate B4 and the thioxanthone acetic acid in the step B3 is 0.3g-0.4 g: 1 mmol: 5 mL; the using ratio of the isophorone diisocyanate, the dibutyltin dilaurate, the intermediate B5 and the acetone in the step B4 is 2 g: 0.02 g: 10 mmol: 8-10mL, wherein the dosage ratio of the intermediate B6, the perfluoroalkyl ethyl acrylate, the LiOH and the absolute ethyl alcohol is 1 mmol: 1 mmol: 0.02 g: 10 mL.

Further, in the step A1, the using ratio of the dichloromethane, the glycerol, the complexing agent, the cyclopentane epoxide, the chloropropylene oxide and the deionized water is 5-10 mL: 2mL of: 2 g: 1 mol: 1 mol: 10mL, wherein the complexing agent is boron trifluoride diethyl ether.

Further, the using ratio of the intermediate A1, the polymerization inhibitor, the catalyst and the acrylic acid in the step A2 is 1-2 g: 0.2 g: 0.3 g: 1g, the polymerization inhibitor is hydroxyanisole, and the catalyst is N, N-dimethylbenzylamine.

Further, the intermediate 2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol, dibutyltin dilaurate, 2-dimethylolpropionic acid and hydroxypropyl acrylate in the step A3 are used in a ratio of 1-1.5 mol: 1 mol: 0.5 mol: 1 mol: 0.1 g: 0.5 mol: 2 mol.

A preparation process of fast curing UV ink specifically comprises the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 30-40min at the temperature of 50-60 ℃ and the rotating speed of 400-600r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2-3h at the rotating speed of 800-;

step S3: and (4) adding the mixed material obtained in the step S2 into a stirring kettle, heating to 55-65 ℃, adding a photoinitiator into the stirring kettle, stirring for 20-30min at the temperature of 55-65 ℃ and the rotating speed of 500-.

(III) advantageous effects

The invention provides a fast curing UV ink and a preparation process thereof. Compared with the prior art, the method has the following beneficial effects: the modified connecting material is prepared by the ring-opening polymerization reaction of the cyclopentane epoxide and epichlorohydrin under the condition that dichloromethane is used as solvent and the complexation of glycerol and complexing agent is used for catalyzing the reaction, so as to generate polyether glycol with large steric hindrance, the polyether polyol is taken as a raw material to synthesize a polyurethane material with polyisocyanate, so that the polyurethane material has good ageing resistance and yellowing resistance, the polyether polyol is fixed on the basis of synthesizing the polyether polyol, the polyether polyol and acrylic acid are synthesized into polyether modified epoxy acrylate under the action of a catalyst and a polymerization inhibitor, and then-NCO of hexamethylene diisocyanate reacts with hydroxyl under the action of a chain extender to obtain a polyurethane prepolymer, so that the polyether epoxy modified polyurethane prepolymer is finally obtained, and the prepared ink has excellent reaction activity, ageing resistance and yellowing resistance; the photoinitiator is prepared by firstly preparing N-methyldiethanolamine from ethylene oxide and monomethylamine, then preparing bromooctadecane from octadecanol and hydrogen bromide through reaction, preparing octadecyl-methyldiethanolamine from bromooctadecane and N-methyldiethanolamine, quaternizing octadecyl-methyldiethanolamine and thioxanthone acetic acid to prepare the thioxanthone light derivative initiator with quaternary ammonium alkyl and hydroxyl, wherein the thioxanthone derivative is one of the photoinitiators widely applied in photocuring materials, has lower triplet energy and higher quantum yield, has stronger absorption at the wavelength of 360-420nm, is easily matched with the emission spectrum of a light source through the regulation and control of an absorption spectrum, and can promote the thioxanthone derivative to carry out a photo-decarboxylation reaction to generate active free radicals through the quaternization of quaternary ammonium cations, The compatibility and the initiation efficiency of a system are improved, the-OH of the photoinitiator reacts with the-NCO of isophorone diisocyanate under the catalysis of dibutyltin dilaurate, and then an organic fluorine compound is introduced, so that the photoinitiator containing long-chain alkyl and fluorine atoms is finally prepared, on one hand, the polarity of the F atom is low, the electronegativity is strong, and the bond energy of a C-F bond is very strong, compared with other materials, the organic fluorine material has excellent performances of hydrophobicity and oleophobicity, low friction coefficient, low surface tension, chemical corrosion resistance and the like, the inhibition of oxygen inhibition polymerization on a curing reaction can be effectively weakened by adding the photoinitiator, on the other hand, a non-polar long chain segment has certain surface migration capacity in a polar material, the photoinitiator can be dragged to the surface of a molecule, the anti-oxygen inhibition performance of the photoinitiator is further improved, and rapid curing is realized.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The fast curing UV printing ink comprises the following raw materials in parts by weight: 40 parts of modified connecting material, 10 parts of titanium dioxide, 10 parts of absolute ethyl alcohol, 1 part of coconut oil fatty acid diethanolamide, 1 part of fluorocarbon, 1 part of linseed oil, 1 part of sodium dodecyl sulfate, 3 parts of photoinitiator and 60 parts of deionized water;

the fast curing UV ink is prepared by the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 30min at the temperature of 50 ℃ and the rotating speed of 400r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2 hours at the rotating speed of 800r/min, and obtaining a mixed material II after grinding is finished;

step S3: adding the mixed material obtained in the step S2 into a stirring kettle, heating to 55 ℃, adding a photoinitiator into the stirring kettle, stirring for 20min at the temperature of 55 ℃ and the rotating speed of 500r/min, and obtaining the fast curing UV ink after stirring;

the modified connecting material is prepared by the following steps:

step A1: adding dichloromethane into a cleaned and dried reaction kettle, sequentially adding glycerol and a complexing agent into the reaction kettle, carrying out heat preservation reaction for 30min at the temperature of 10 ℃ and the rotating speed of 50r/min, keeping the temperature at 5 ℃ and the rotating speed of 100r/min, adding epoxy cyclopentane into the reaction kettle by using a dropping funnel, keeping the temperature at 5 ℃ and the rotating speed of 100r/min, carrying out reaction for 30min, dropwise adding epoxy chloropropane into the reaction kettle from the dropping funnel, continuously carrying out heat preservation reaction for 4h at the temperature of 5 ℃ and the rotating speed of 100r/min, adjusting the pH to 7.3 by using a sodium hydroxide aqueous solution with the mass fraction of 10% after the reaction is finished, washing with deionized water, and carrying out reduced pressure distillation to obtain an intermediate A1;

step A2: adding the intermediate A1 into a clean and dry reaction kettle, slowly adding a polymerization inhibitor, a catalyst and acrylic acid into the reaction kettle at the temperature of 50 ℃, heating to 110 ℃, and reacting for 2 hours to obtain an intermediate A2;

step A3: adding the intermediate A2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol and dibutyltin dilaurate into a reaction kettle, reacting for 1h at 60 ℃ under the protection of nitrogen, reducing the temperature to 45 ℃ after the reaction is finished, then adding 2, 2-dimethylolpropionic acid into the reaction kettle, reacting for 2h at 60 ℃ after the addition is finished, adding acetone during the reaction to adjust the viscosity, adding hydroxypropyl acrylate after the reaction is finished, reacting for 1h at 60 ℃, and adding absolute ethyl alcohol after the reaction is finished, and reacting for 0.5h to obtain the modified connecting material.

Wherein the dosage ratio of the dichloromethane, the glycerol, the complexing agent, the cyclopentane epoxide, the chloropropylene oxide and the deionized water in the step A1 is 5 mL: 2mL of: 2 g: 1 mol: 1 mol: 10mL, wherein the complexing agent is boron trifluoride diethyl ether, and the using ratio of the intermediate A1, the polymerization inhibitor, the catalyst and the acrylic acid in the step A2 is 1 g: 0.2 g: 0.3 g: 1g, the polymerization inhibitor is hydroxyanisole, the catalyst is N, N-dimethylbenzylamine, the intermediate 2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol, dibutyltin dilaurate, 2-dimethylolpropionic acid and hydroxypropyl acrylate in the step A3 are used in a dosage ratio of 1 mol: 1 mol: 0.5 mol: 1 mol: 0.1 g: 0.5 mol: 2 mol.

Wherein the photoinitiator is prepared by the following steps:

step B1: adding ethylene oxide and 25% by mass of monomethylamine aqueous solution into a reaction kettle, then adding a catalyst, stirring and mixing for 5min under the condition of the rotating speed of 100r/min, after the mixing is finished, adjusting the pressure of the reaction kettle to 3.5MPa, adjusting the temperature to 160 ℃, adjusting the rotating speed to 200r/min, reacting for 4h under the condition, taking out reaction liquid after the reaction is finished, and removing methylamine and water through a rotary evaporator to obtain an intermediate B1;

step B2: adding octadecanol and hydrogen bromide into a reaction kettle, then adding a sulfuric acid solution with the mass fraction of 98%, reacting for 4 hours at the temperature of 120 ℃ and the rotation speed of 200r/min after the dropwise addition is finished, keeping the rotation speed of 200r/min after the reaction is finished, cooling to room temperature, standing for 12 hours, and then carrying out suction filtration and washing for 3 times to obtain an intermediate B2; adding the intermediate B2 and the intermediate B1 obtained in the step B1 into a reaction kettle, reacting for 2 hours at the temperature of 100 ℃ and the rotating speed of 300r/min, combining the reactions to obtain an intermediate B3, recrystallizing the intermediate B3 for 3 times by using a mixed solution of ethyl acetate and absolute ethyl alcohol, and performing suction filtration to obtain an intermediate B4;

step B3: adding methanol into a reaction kettle, adding an intermediate B4 and thioxanthone acetic acid into the reaction kettle, stirring and reacting for 2 hours at the rotation speed of 300r/min and the temperature of 20 ℃, filtering and collecting filtrate after the reaction is finished, adding deionized water into the filtrate, removing water by using a rotary evaporator, adding chloroform for impurity removal, performing rotary evaporation again after the impurity removal is finished, placing the rotary evaporation into a vacuum drying oven after the rotary evaporation is finished, and drying for 12 hours at the temperature of 60 ℃ to obtain an intermediate B5;

step B4: adding isophorone diisocyanate and dibutyltin dilaurate into a reaction kettle, adding an intermediate B5 obtained in the step B3 into the reaction kettle at the temperature of 40 ℃ and the rotating speed of 200r/min, adding acetone, reacting for 2h, adding reaction liquid into deionized water for hydrolysis after the reaction is finished, extracting by using ethyl acetate, removing the ethyl acetate by using a rotary evaporator after the extraction is finished, placing a product in a vacuum drying box, drying for 10h at 50 ℃ to obtain an intermediate B6, adding the intermediate B6, perfluoroalkyl ethyl acrylate, LiOH and absolute ethyl alcohol into the reaction kettle, reacting for 5h at the temperature of 30 ℃, and removing LiOH and absolute ethyl alcohol after the reaction is finished to obtain the photoinitiator.

Wherein the dosage ratio of the ethylene oxide, the monomethylamine aqueous solution and the catalyst in the step B1 is 3 mol: 1 mol: 0.2g, wherein the catalyst is an ethylene oxide catalyst with the mass fraction of 3%, and the dosage ratio of the octadecanol, the hydrogen bromide and the sulfuric acid solution in the step B2 is 0.05 mol: 20 g: 4g of the total weight of the mixture; the dosage ratio of the intermediate B2 to the intermediate B1 is 1 mol: 0.5mol, wherein the mixing ratio of the ethyl acetate to the absolute ethyl alcohol is 1mL to 1 mL; the dosage ratio of the methanol, the intermediate B4 and the thioxanthone acetic acid in the step B3 is 0.3 g: 1 mmol: 5 mL; the using ratio of the isophorone diisocyanate, the dibutyltin dilaurate, the intermediate B5 and the acetone in the step B4 is 2 g: 0.02 g: 10 mmol: 8mL, wherein the dosage ratio of the intermediate B6, the perfluoroalkyl ethyl acrylate, the LiOH and the absolute ethyl alcohol is 1 mmol: 1 mmol: 0.02 g: 10 mL.

Example 2

The fast curing UV printing ink comprises the following raw materials in parts by weight: 50 parts of modified connecting material, 12.5 parts of titanium dioxide, 12.5 parts of absolute ethyl alcohol, 1.5 parts of coconut oil fatty acid diethanolamide, 1.5 parts of fluorocarbon, 1.5 parts of linseed oil, 1.5 parts of sodium dodecyl sulfate, 4 parts of photoinitiator and 70 parts of deionized water;

the fast curing UV ink is prepared by the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 35min at the temperature of 55 ℃ and the rotating speed of 500r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 2.5h at the rotating speed of 900r/min, and obtaining a mixed material II after grinding is finished;

step S3: adding the mixed material obtained in the step S2 into a stirring kettle, heating to 60 ℃, adding a photoinitiator into the stirring kettle, stirring for 25min at the temperature of 60 ℃ and the rotating speed of 600r/min, and obtaining the fast curing UV ink after stirring;

the modified connecting material is prepared by the following steps:

step A1: adding dichloromethane into a reaction kettle which is cleaned and dried, then sequentially adding glycerol and a complexing agent into the reaction kettle, carrying out heat preservation reaction for 35min under the conditions that the temperature is 12.5 ℃ and the rotating speed is 75r/min, keeping the temperature at 7.5 ℃ and the rotating speed at 150r/min, adding epoxy cyclopentane into the reaction kettle by using a dropping funnel, keeping the temperature at 7.5 ℃ and the rotating speed at 150r/min for reaction for 35min, then dropwise adding epoxy chloropropane into the reaction kettle from the dropping funnel, continuing carrying out heat preservation reaction for 4.5h under the conditions that the temperature is 7.5 ℃ and the rotating speed is 150r/min, adjusting the pH to 7.4 by using a sodium hydroxide aqueous solution with the mass fraction of 10% after the reaction is finished, then washing by using deionized water, and carrying out reduced pressure distillation to obtain an intermediate;

step A2: adding the intermediate A1 into a clean and dry reaction kettle, slowly adding a polymerization inhibitor, a catalyst and acrylic acid into the reaction kettle at the temperature of 55 ℃, heating to 112.5 ℃, and reacting for 2.5 hours to obtain an intermediate A2;

step A3: adding the intermediate A2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol and dibutyltin dilaurate into a reaction kettle, reacting for 1.5h at 65 ℃ under the protection of nitrogen, reducing the temperature to 47.5 ℃ after the reaction is finished, then adding 2, 2-dimethylolpropionic acid into the reaction kettle, reacting for 2.5h at 65 ℃ after the addition is finished, adding acetone during the reaction to adjust the viscosity, adding hydroxypropyl acrylate to react for 1.5h at 62.5 ℃ after the reaction is finished, and adding absolute ethyl alcohol to react for 0.75h after the reaction is finished, thus obtaining the modified connecting material.

Wherein the dosage ratio of the dichloromethane, the glycerol, the complexing agent, the cyclopentane epoxide, the chloropropylene oxide and the deionized water in the step A1 is 7.5 mL: 2mL of: 2 g: 1 mol: 1 mol: 10mL, wherein the complexing agent is boron trifluoride diethyl ether, and the using ratio of the intermediate A1, the polymerization inhibitor, the catalyst and the acrylic acid in the step A2 is 1.5 g: 0.2 g: 0.3 g: 1g, the polymerization inhibitor is hydroxyanisole, the catalyst is N, N-dimethylbenzylamine, the intermediate 2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol, dibutyltin dilaurate, 2-dimethylolpropionic acid and hydroxypropyl acrylate in the step A3 are used in a dosage ratio of 1.25 mol: 1 mol: 0.5 mol: 1 mol: 0.1 g: 0.5 mol: 2 mol.

Wherein the photoinitiator is prepared by the following steps:

step B1: adding ethylene oxide and 27.5 mass percent of monomethylamine aqueous solution into a reaction kettle, then adding a catalyst, stirring and mixing for 7.5min under the condition of the rotating speed of 150r/min, after the mixing is finished, adjusting the pressure of the reaction kettle to 3.8MPa, the temperature to 180 ℃, the rotating speed to 300r/min, reacting for 4.5h under the conditions, taking out reaction liquid after the reaction is finished, and removing methylamine and water through a rotary evaporator to obtain an intermediate B1;

step B2: adding octadecanol and hydrogen bromide into a reaction kettle, then adding a sulfuric acid solution with the mass fraction of 98%, reacting for 4.5 hours at the temperature of 122.5 ℃ and the rotation speed of 250r/min after the dropwise addition is finished, keeping the rotation speed of 250r/min after the reaction is finished, cooling to room temperature, standing for 12 hours, and then carrying out suction filtration and washing for 3 times to obtain an intermediate B2; adding the intermediate B2 and the intermediate B1 obtained in the step B1 into a reaction kettle, reacting for 2.5 hours at the temperature of 110 ℃ and the rotating speed of 350r/min, obtaining an intermediate B3 after reaction combination, recrystallizing the intermediate B3 for 4 times by using a mixed solution of ethyl acetate and absolute ethyl alcohol, and then performing suction filtration to obtain an intermediate B4;

step B3: adding methanol into a reaction kettle, adding an intermediate B4 and thioxanthone acetic acid into the reaction kettle, stirring and reacting for 2.5 hours at the rotation speed of 350r/min and the temperature of 22.5 ℃, filtering and collecting filtrate after the reaction is finished, adding deionized water into the filtrate, removing water by using a rotary evaporator, adding chloroform for impurity removal, performing rotary evaporation again after the impurity removal is finished, placing the rotary evaporation into a vacuum drying oven after the rotary evaporation is finished, and drying for 12 hours at the temperature of 60 ℃ to obtain an intermediate B5;

step B4: adding isophorone diisocyanate and dibutyltin dilaurate into a reaction kettle, adding an intermediate B5 obtained in the step B3 into the reaction kettle at the temperature of 45 ℃ and the rotating speed of 300r/min, adding acetone at the same time, reacting for 2.5h, adding reaction liquid into deionized water for hydrolysis after the reaction is finished, extracting by using ethyl acetate, removing the ethyl acetate by using a rotary evaporator after the extraction is finished, placing a product in a vacuum drying box, drying for 11h at 55 ℃ to obtain an intermediate B6, adding the intermediate B6, perfluoroalkyl ethyl acrylate, LiOH and absolute ethyl alcohol into the reaction kettle, reacting for 5.5h at the temperature of 32.5 ℃, and removing the LiOH and the absolute ethyl alcohol after the reaction is finished to obtain the photoinitiator.

Wherein the dosage ratio of the ethylene oxide, the monomethylamine aqueous solution and the catalyst in the step B1 is 3 mol: 1 mol: 0.2g, wherein the catalyst is an ethylene oxide catalyst with the mass fraction of 3%, and the dosage ratio of the octadecanol, the hydrogen bromide and the sulfuric acid solution in the step B2 is 0.05 mol: 20 g: 4g of the total weight of the mixture; the dosage ratio of the intermediate B2 to the intermediate B1 is 1 mol: 0.75mol, wherein the mixing ratio of the ethyl acetate to the absolute ethyl alcohol is 1mL to 3 mL; the dosage ratio of the methanol, the intermediate B4 and the thioxanthone acetic acid in the step B3 is 0.35 g: 1 mmol: 5 mL; the using ratio of the isophorone diisocyanate, the dibutyltin dilaurate, the intermediate B5 and the acetone in the step B4 is 2 g: 0.02 g: 10 mmol: 9mL, wherein the dosage ratio of the intermediate B6, the perfluoroalkyl ethyl acrylate, the LiOH and the absolute ethyl alcohol is 1 mmol: 1 mmol: 0.02 g: 10 mL.

Example 3

The fast curing UV printing ink comprises the following raw materials in parts by weight: 60 parts of modified connecting material, 15 parts of titanium dioxide, 15 parts of absolute ethyl alcohol, 2 parts of coconut oil fatty acid diethanolamide, 2 parts of fluorocarbon, 2 parts of linseed oil, 2 parts of sodium dodecyl sulfate, 5 parts of photoinitiator and 80 parts of deionized water;

the fast curing UV ink is prepared by the following steps:

step S1: sequentially adding the modified connecting material, the color filler, the absolute ethyl alcohol, the stabilizer, the flatting agent, the defoaming agent, the dispersing agent and the deionized water into a reaction kettle which is cleaned and dried, stirring and mixing for 40min at the temperature of 60 ℃ and the rotating speed of 600r/min, and obtaining a mixed material I after stirring;

step S2: adding the mixed material I obtained in the step S1 into a ball mill, grinding for 3 hours at the rotating speed of 1000r/min, and obtaining a mixed material II after grinding is finished;

step S3: adding the mixed material obtained in the step S2 into a stirring kettle, heating to 65 ℃, adding a photoinitiator into the stirring kettle, stirring for 30min at the temperature of 65 ℃ and the rotating speed of 700r/min, and obtaining the fast curing UV ink after stirring;

the modified connecting material is prepared by the following steps:

step A1: adding dichloromethane into a cleaned and dried reaction kettle, sequentially adding glycerol and a complexing agent into the reaction kettle, carrying out heat preservation reaction for 40min at the temperature of 15 ℃ and the rotating speed of 100r/min, keeping the temperature at 10 ℃ and the rotating speed of 200r/min, adding epoxy cyclopentane into the reaction kettle by using a dropping funnel, keeping the temperature at 10 ℃ and the rotating speed of 200r/min, carrying out reaction for 40min, dropwise adding epoxy chloropropane into the reaction kettle from the dropping funnel, continuously carrying out heat preservation reaction for 5h at the temperature of 10 ℃ and the rotating speed of 200r/min, adjusting the pH to 7.5 by using a sodium hydroxide aqueous solution with the mass fraction of 10% after the reaction is finished, washing with deionized water, and carrying out reduced pressure distillation to obtain an intermediate A1;

step A2: adding the intermediate A1 into a clean and dry reaction kettle, slowly adding a polymerization inhibitor, a catalyst and acrylic acid into the reaction kettle at the temperature of 60 ℃, heating to 115 ℃, and reacting for 3 hours to obtain an intermediate A2;

step A3: adding the intermediate A2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol and dibutyltin dilaurate into a reaction kettle, reacting for 2 hours at 70 ℃ under the protection of nitrogen, reducing the temperature to 50 ℃ after the reaction is finished, then adding 2, 2-dimethylolpropionic acid into the reaction kettle, reacting for 3 hours at 70 ℃ after the addition is finished, adding acetone during the reaction to adjust the viscosity, adding hydroxypropyl acrylate after the reaction is finished, reacting for 2 hours at 65 ℃, and adding absolute ethyl alcohol to react for 1 hour after the reaction is finished, thus obtaining the modified connecting material.

Wherein the dosage ratio of the dichloromethane, the glycerol, the complexing agent, the cyclopentane epoxide, the chloropropylene oxide and the deionized water in the step A1 is 10 mL: 2mL of: 2 g: 1 mol: 1 mol: 10mL, wherein the complexing agent is boron trifluoride diethyl ether, and the using ratio of the intermediate A1, the polymerization inhibitor, the catalyst and the acrylic acid in the step A2 is 2 g: 0.2 g: 0.3 g: 1g, the polymerization inhibitor is hydroxyanisole, the catalyst is N, N-dimethylbenzylamine, the intermediate 2, hexamethylene diisocyanate, triethanolamine, polyoxyethylene glycol, dibutyltin dilaurate, 2-dimethylolpropionic acid and hydroxypropyl acrylate in the step A3 are used in a dosage ratio of 1.5 mol: 1 mol: 0.5 mol: 1 mol: 0.1 g: 0.5 mol: 2 mol.

Wherein the photoinitiator is prepared by the following steps:

step B1: adding ethylene oxide and a monomethylamine aqueous solution with the mass fraction of 30% into a reaction kettle, then adding a catalyst, stirring and mixing for 10min under the condition of the rotating speed of 200r/min, after the mixing is finished, adjusting the pressure of the reaction kettle to 4MPa, adjusting the temperature to 200 ℃, adjusting the rotating speed to 400r/min, reacting for 5h under the condition, taking out a reaction solution after the reaction is finished, and removing methylamine and water through a rotary evaporator to obtain an intermediate B1;

step B2: adding octadecanol and hydrogen bromide into a reaction kettle, then adding a sulfuric acid solution with the mass fraction of 98%, reacting for 5 hours at the temperature of 125 ℃ and the rotating speed of 300r/min after the dropwise addition is finished, keeping the rotating speed of 300r/min after the reaction is finished, cooling to room temperature, standing for 12 hours, and then carrying out suction filtration and washing for 3 times to obtain an intermediate B2; adding the intermediate B2 and the intermediate B1 obtained in the step B1 into a reaction kettle, reacting for 3 hours at the temperature of 120 ℃ and the rotating speed of 400r/min, combining the reactions to obtain an intermediate B3, recrystallizing the intermediate B3 for 5 times by using a mixed solution of ethyl acetate and absolute ethyl alcohol, and performing suction filtration to obtain an intermediate B4;

step B3: adding methanol into a reaction kettle, adding an intermediate B4 and thioxanthone acetic acid into the reaction kettle, stirring and reacting for 3 hours at the rotation speed of 400r/min and the temperature of 25 ℃, filtering and collecting filtrate after the reaction is finished, adding deionized water into the filtrate, removing water by using a rotary evaporator, adding chloroform for impurity removal, performing rotary evaporation again after the impurity removal is finished, placing the rotary evaporation into a vacuum drying oven after the rotary evaporation is finished, and drying for 12 hours at the temperature of 60 ℃ to obtain an intermediate B5;

step B4: adding isophorone diisocyanate and dibutyltin dilaurate into a reaction kettle, adding an intermediate B5 obtained in the step B3 into the reaction kettle at the temperature of 50 ℃ and the rotating speed of 400r/min, adding acetone simultaneously, reacting for 3h, adding reaction liquid into deionized water for hydrolysis after the reaction is finished, extracting by using ethyl acetate, removing the ethyl acetate by using a rotary evaporator after the extraction is finished, placing a product in a vacuum drying box, drying for 12h at the temperature of 60 ℃ to obtain an intermediate B6, adding the intermediate B6, perfluoroalkyl ethyl acrylate, LiOH and absolute ethyl alcohol into the reaction kettle, reacting for 6h at the temperature of 35 ℃, and removing LiOH and absolute ethyl alcohol after the reaction is finished to obtain the photoinitiator.

Wherein the dosage ratio of the ethylene oxide, the monomethylamine aqueous solution and the catalyst in the step B1 is 3 mol: 1 mol: 0.2g, wherein the catalyst is an ethylene oxide catalyst with the mass fraction of 3%, and the dosage ratio of the octadecanol, the hydrogen bromide and the sulfuric acid solution in the step B2 is 0.05 mol: 20 g: 4g of the total weight of the mixture; the dosage ratio of the intermediate B2 to the intermediate B1 is 1 mol: 1mol, wherein the mixing ratio of the ethyl acetate to the absolute ethyl alcohol is 1mL to 5 mL; the dosage ratio of the methanol, the intermediate B4 and the thioxanthone acetic acid in the step B3 is 0.4 g: 1 mmol: 5 mL; the using ratio of the isophorone diisocyanate, the dibutyltin dilaurate, the intermediate B5 and the acetone in the step B4 is 2 g: 0.02 g: 10 mmol: 8mL, wherein the dosage ratio of the intermediate B6, the perfluoroalkyl ethyl acrylate, the LiOH and the absolute ethyl alcohol is 1 mmol: 1 mmol: 0.02 g: 10 mL.

Comparative example: selecting one UV ink commonly available on the market;

the examples 1-3 and comparative examples were tested for cure time: the inks of examples 1 to 3 and comparative examples were applied to the surface of a test panel of the same area, irradiated with mixed ultraviolet light, the time of ultraviolet irradiation was fixed, after photocuring, whether the test pattern layer reached the curing standard or not was checked, and the photocuring time was obtained by a number of tests, and the results are shown in the following table

Sample (I)	Example 1	Example 2	Example 3	Comparative example
					Speed of light curing(s)	5.1	5.1	4.9	8

It can be seen from the table that the photocuring speeds of the inks of examples 1 to 3 were significantly improved compared to that of the ink of comparative example.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.