WO2023206990A1 - 一种传印能力好的荧光油墨及制备方法 - Google Patents

一种传印能力好的荧光油墨及制备方法 Download PDF

Info

Publication number
WO2023206990A1
WO2023206990A1 PCT/CN2022/126749 CN2022126749W WO2023206990A1 WO 2023206990 A1 WO2023206990 A1 WO 2023206990A1 CN 2022126749 W CN2022126749 W CN 2022126749W WO 2023206990 A1 WO2023206990 A1 WO 2023206990A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
fluorescent
microspheres
ink
stirring
Prior art date
Application number
PCT/CN2022/126749
Other languages
English (en)
French (fr)
Inventor
罗伟文
阮玉雅
Original Assignee
中山市富日印刷材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中山市富日印刷材料有限公司 filed Critical 中山市富日印刷材料有限公司
Publication of WO2023206990A1 publication Critical patent/WO2023206990A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to the technical field of fluorescent ink, and in particular to a fluorescent ink with good printing ability and a preparation method.
  • the main component of fluorescent ink is a fluorescent agent, also known as a fluorescent dye, which absorbs a certain form of energy to excite photons and releases the absorbed energy in the form of low visible light, thereby producing fluorescence.
  • a fluorescent agent also known as a fluorescent dye
  • High-quality fluorescent inks generally require 65-75% imported fluorescent ink essence to meet the standards. In addition to reducing the pigment content of low-end and cheap fluorescent inks, they also do not use specially selected binders/auxiliaries, even if the fluorescent ink is increased. The content of ink essence increases the concentration, but it cannot be avoided when printing: 1) When printing 3-5 hundred prints, there will be ink accumulation and excessive emulsification; 2) Because the ink is difficult to disperse, it will cause problems during printing. Ink does not transfer evenly to the substrate.
  • the present invention provides a fluorescent ink with good printing ability and a preparation method.
  • a fluorescent ink with good printing ability is made of the following raw materials in parts by weight: 1-5 parts of P(St-co-AM) microspheres, 0.3-0.5 parts of stabilizer, 1-2 parts of fluorescent agent, carbon 3-5 parts of black, 10-20 parts of connecting material, 0.4-0.6 parts of sodium dodecyl sulfate solution, 0.4-0.6 parts of cobalt isooctanoate, 5-8 parts of polyethylene wax and 80-90 parts of solvent;
  • the P (St-co-AM) microspheres are made of the following raw materials by weight: 10-15 parts of styrene, 10-15 parts of acrylamide, 1-3 parts of ammonium persulfate, 3-5 parts of dibenzoyl peroxide parts and 60-70 parts of deionized water.
  • the preparation method of the P(St-co-AM) microspheres is as follows:
  • the connecting material is one of rosin modified phenolic resin, modified alkyd resin and asphalt resin.
  • the stabilizer is one of hydroxypropyl cellulose and polyethylene glycol.
  • the concentration of the sodium lauryl sulfate solution is 0.08-0.14g/L.
  • the solvent consists of isopropyl alcohol and ethanol in a ratio of 1:1.
  • a method for preparing fluorescent ink as described above including the following steps:
  • Prepolymerization Put the above-mentioned weight parts of P(St-co-AM) microspheres, stabilizer and solvent into a stirring tank, start stirring, and raise the temperature to 60-65°C while stirring.
  • the stirring speed is 50-60r/min, stirring time is 15-20 minutes, to obtain prepolymer solution;
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 80-90°C, stirring speed is 50-60r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • the present invention uses soap-free emulsion polymerization to innovatively prepare P(St-co-AM) microspheres.
  • the microspheres can be effectively combined with fluorescent dyes and have strong coloring power and stable properties.
  • the grafting effect significantly improves the dispersion of the ink, allowing the ink to be better transferred to the substrate during printing.
  • the printing transfer ability is good, the stability is also improved, and the fluorescence effect is good.
  • the preparation method of the present invention includes prepolymerization, microsphere coloring and ultrasonic dispersion.
  • the fluorescent ink toner produced is fine.
  • the cavitation effect of ultrasonic waves not only breaks the dyed microspheres into finer pigment particles, but also The monomer droplets are suspended and dispersed into smaller droplets, thereby reducing the phenomenon of ink stacking failure caused by the accumulation of ink pigment particles.
  • a fluorescent ink with good printing ability is made of the following raw materials in parts by weight: 1-5 parts of P(St-co-AM) microspheres, 0.3-0.5 parts of stabilizer, 1-2 parts of fluorescent agent, carbon 3-5 parts of black (purchased from Dongguan Canyu Chemical Co., Ltd.), 10-20 parts of connecting material, sodium dodecyl sulfate solution (the molecular formula is CH 3 (CH 2 ) 10 CH 2 OSO 3 Na) 0.4-0.6 0.4-0.6 parts of cobalt isooctanoate (chemical formula is C 16 H 30 CoO 4 ), 5-8 parts of polyethylene wax (purchased from Shanghai Kaiyin Chemical Co., Ltd.) and 80-90 parts of solvent.
  • the P(St-co-AM) microspheres are made of the following raw materials in parts by weight: 10-15 parts of styrene (molecular formula C 8 H 8 ), 10-15 parts of acrylamide (chemical formula C 3 H 5 NO) 1-3 parts of ammonium persulfate (chemical formula (NH 4 ) 2 S 2 O 8 ), 3-5 parts of dibenzoyl peroxide (purchased from Jinan Yucai Chemical Co., Ltd.) and 60-70 parts of deionized water It is difficult to polymerize styrene and acrylamide under normal circumstances. In this application, dual initiators are used to prepare P(St-co-AM) microspheres.
  • the present invention uses a soap-free emulsion polymerization method to innovatively prepare P(St-co-AM) microspheres.
  • the soap-free emulsion refers to a polymerization method that does not contain an emulsifier. This method effectively avoids the reaction of the emulsifier during the emulsion polymerization process. Under the influence of the system, the prepared polymer microspheres are clean and free of impurities.
  • the present invention introduces hydrophilic groups by adding functional monomer acrylamide (AM) to enhance the interaction between the microsphere surface and the water phase interface, reduce the surface energy of the microsphere surface, and improve the stability of the microsphere. At the same time, it can also greatly increase the polymerization reaction rate.
  • AM functional monomer acrylamide
  • the soap-free emulsion polymerization method also has obvious shortcomings.
  • the particle size of the microspheres produced is relatively large, generally several hundred nanometers. Therefore, an ultrasonic dispersion step must be added during the ink preparation process. Ultrasonic waves enhance the cavitation of the liquid medium, causing the bubbles to expand and compress more intensely, thus making the pigment-coated microspheres smaller.
  • the particle size of dyed microspheres dispersed by ultrasonic was reduced to one-third. This is because the cavitation effect of ultrasonic waves not only breaks the dyed microspheres into finer pigment particles, but also makes the monomer beads The droplets are suspended and dispersed into smaller droplets. In this way, ultrasonic dispersion can make up for the shortcomings of the large particle size of the microspheres produced by soap-free emulsion polymerization, making the final dyed microspheres smaller in size.
  • the preparation process of the P(St-co-AM) microspheres is affected by the stirring speed.
  • Microspheres produced by soap-free emulsion polymerization have poor monodispersity. The faster the stirring speed, the worse the monodispersity.
  • the stirring speed is 80-90r/min, the shear speed in the system is relatively moderate. , the obtained microspheres have relatively uniform particle sizes.
  • the stabilizers are hydroxypropyl cellulose (the molecular formula is C 36 H 70 O 19 ), polyvinylpyrrolidone (the chemical formula is (C 6 H 9 NO) n ) and polyethylene glycol (the chemical formula is HO(CH 2 CH One of 2 O) n H).
  • Stabilizers play a vital role in the preparation of fluorescent ink.
  • the stabilizers used are all amphiphilic compounds that can be grafted onto the molecular chain of microspheres and positioned on the surface of the microspheres, thereby providing steric stabilization. , so that the microspheres will not agglomerate together and have good dispersion.
  • the fluorescent agent is preferably a fluorescent whitening agent produced by Jinan Huijinchuan Trading Co., Ltd., with model number CBS-127.
  • the main component of the carbon black is carbon. It is a black powder obtained by partial combustion or thermal cracking decomposition of hydrocarbons. It is cheap, has strong coloring ability and good stability, and can be combined with the P(St-co-AM) Microspheres bind effectively.
  • the connecting material is one of rosin modified phenolic resin, modified alkyd resin and asphalt resin. Rosin-modified phenolic resin is preferred. Rosin-modified phenolic resin can better effectively combine with the colored microspheres, so that the colored microspheres can be well dispersed and transferred to the surface of the substrate through the printing machine.
  • the sodium lauryl sulfate solution is used as an emulsifier in the system, and the concentration of the sodium lauryl sulfate solution is 0.08-0.14g/L.
  • the concentration of the sodium lauryl sulfate solution used in the present invention is far Far smaller than its critical micelle concentration (about 2.3g/L), there are no micelles formed by the emulsifier during the polymerization process, and the oligomers with hydrophilic groups at the chain ends are close to each other when they reach the critical micelle concentration. Form oligomer micelles, solubilize monomers, and form reaction nuclei, so colored microspheres with good monodispersity can be obtained.
  • the cobalt isooctanoate is an oxidizing desiccant with extremely strong drying ability, especially to promote surface drying.
  • the cobalt isooctanoate used in the present invention plays a role in accelerating the drying of the oxidized conjunctiva of the ink. It is also called a drier and is one of the most important additives.
  • Common desiccants include manganese desiccant and other metal desiccants, but the drying effects of these desiccants are not ideal and are generally not used for inks.
  • the polyethylene wax is used as a friction-resistant additive. When added to the ink, it can float on the ink film after being printed on the substrate to increase friction resistance.
  • the amount of polyethylene wax used is very critical to the performance of the ink, directly affecting the fluidity, transferability and gloss of the ink.
  • the present invention uses a heated copolymerization method to color P(St-co-AM) microspheres.
  • the principle is to embed the fluorescent agent on the expanded microspheres through heating.
  • the microspheres expand when heated, and the carbon black diffuses into the interior of the microspheres. , and then color the microspheres.
  • a method for preparing fluorescent ink as described above including the following steps:
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 80-90°C, stirring speed is 50-60r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • a fluorescent ink made of the following raw materials by weight: 3 parts of P(St-co-AM) microspheres, 0.4 parts of stabilizer, 1.5 parts of fluorescent agent, 4 parts of carbon black, 15 parts of connecting material, 12 parts 0.5 parts of sodium alkyl sulfate solution, 0.5 parts of cobalt isooctanoate, 6 parts of polyethylene wax and 85 parts of solvent.
  • the preparation steps of the fluorescent ink of Example 1 are as follows:
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 90°C, stirring speed is 50r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • a fluorescent ink made of the following raw materials by weight: 3 parts of polystyrene microspheres (purchased from Dongguan Kemai New Materials Co., Ltd.), 0.4 parts of stabilizer, 1.5 parts of fluorescent agent, 4 parts of carbon black, 15 parts of connecting material, 0.5 parts of sodium dodecyl sulfate solution, 0.5 parts of cobalt isooctanoate, 6 parts of polyethylene wax and 85 parts of solvent.
  • the preparation steps of the fluorescent ink of Example 2 are as follows:
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 90°C, stirring speed is 50r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • a fluorescent ink made of the following raw materials in parts by weight: 3 parts of P(St-co-AM) microspheres, 1.5 parts of fluorescent agent, 4 parts of carbon black, 15 parts of connecting material, and sodium dodecyl sulfate solution 0.5 parts, 0.5 parts of cobalt isooctanoate, 6 parts of polyethylene wax and 85 parts of solvent.
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 90°C, stirring speed is 50r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • a fluorescent ink made of the following raw materials by weight: 3 parts of P(St-co-AM) microspheres, 0.4 parts of stabilizer, 1.5 parts of fluorescent agent, 4 parts of carbon black, 15 parts of connecting material, 12 parts 0.5 parts of sodium alkyl sulfate solution, 0.5 parts of cobalt isooctanoate, 6 parts of polyethylene wax and 85 parts of solvent.
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 90° C., the stirring speed is 50 r/min, stir until the solution is uniform, and the fluorescent ink of Example 4 is obtained.
  • a fluorescent ink made of the following raw materials by weight: 3 parts of P(St-co-AM) microspheres, 0.4 parts of stabilizer, 1.5 parts of fluorescent agent, 4 parts of carbon black, 15 parts of connecting material, 12 parts 0.5 parts of sodium alkyl sulfate solution, 0.5 parts of cobalt isooctanoate, 6 parts of polyethylene wax and 85 parts of solvent.
  • Microsphere coloring Add the above-mentioned weight parts of fluorescent agent, carbon black, connecting material, sodium dodecyl sulfate solution, cobalt isooctanoate and polyethylene wax to the above prepolymer solution, and stir while raising the temperature to 80C, stirring speed is 50r/min, stir until the solution is uniform, and obtain a fluorescent solution;
  • Example 1 The printing lines of Example 1 are smooth, the dots are full, there is no flying ink, paste and ink accumulation during printing, and the imprint adheres well.
  • Example 2 The printing lines of Example 2 are smooth and the dots are full. Ink flying phenomenon occurs in the later stage of printing, and the overall imprint adhesion is good.
  • the printed product of Example 3 has smooth lines and full dots. There is no ink flying, smearing or ink accumulation during printing, and the imprint adheres well.
  • the printed product of Example 4 has smooth lines and full dots. Ink flying, smearing and ink accumulation occur during printing, and the imprint adhesion effect is average.
  • the printed product of Example 5 has smooth lines and full dots. There is no ink flying, smearing or ink accumulation during printing, and the imprints are generally adhered.
  • the applicant measured the fineness, viscosity, initial drying property, tinting strength, adhesion fastness and dye uptake rate of Examples 1-5, among which:
  • the fineness is tested in accordance with the standard of GB/T13217.1-91, and the unit is ⁇ m;
  • the viscosity is tested in accordance with the standard of GB/T13217.1-91, and the unit is (25°C ⁇ 1)S;
  • the tinting strength is tested in accordance with the standard of GB/T13217.1-91, and the unit is (%);
  • the adhesion fastness is tested according to the standard of GB/T13217.1-91, and the unit is (%);
  • the dye uptake rate is based on Beer-Lambert's law, which essentially means that when other conditions are constant, the absorbance of a dilute solution is directly proportional to its concentration.
  • the dye uptake rate can be obtained based on the ratio of the absorbance of P(St-co-AM) microspheres at ⁇ max in a tetrahydrofuran solution to the absorbance of an undyed mixture of the same concentration at ⁇ max in a tetrahydrofuran solution.
  • P(St-co-AM) microspheres have stronger coating and are more stable than existing polystyrene microspheres; they are dispersed through ultrasonic The resulting P(St-co-AM) microspheres are smaller, with better coloring ability and adhesion fastness; excellent synergy can be produced between P(St-co-AM) microspheres and stabilizers, making the microspheres The dye uptake rate is increased and the luminous intensity is good.
  • the applicant has also studied the impact of the type and ratio of solvents on microspheres, but has not yet formed detailed and complete experimental data. Based on the existing experimental data and combined with preliminary analysis, the type and ratio of solvents have an impact on the dyeing of microspheres. The rate has a great influence, which directly affects the fluorescence effect of the ink. From a theoretical perspective, the solvent used in the present invention is composed of isopropyl alcohol and ethanol, and the ratio of 1:1 is not an optimal combination.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

本发明公开了一种传印能力好的荧光油墨及制备方法，由以下原料制成：P(St-co-AM)微球、稳定剂、荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴、聚乙烯蜡和溶剂；P(St-co-AM)微球能与荧光染料有效地结合在一起，具有较强的着色力，稳定剂的枝接作用显著提高了油墨的分散性，使油墨在印刷时能更好地转移到承印物上，传印转移能力好，稳定性也得到了改善，荧光效果佳；制备方法包括预聚合、微球着色和超声分散，制得的荧光油墨色粉细幼，超声波的空化作用不仅使染色微球破碎成了更为细小的颜料颗粒，而且使单体珠滴悬浮分散成更小的液滴，从而减少了由于油墨颜料颗粒的堆积造成的堆墨故障的现象。

Description

一种传印能力好的荧光油墨及制备方法 技术领域
本发明涉及荧光墨水技术领域，特别涉及一种传印能力好的荧光油墨及制备方法。
背景技术
荧光墨的主要成分是荧光剂，荧光剂又称荧光染料，吸收一定形态的能量而激发光子，以低可见光形式将吸收的能量释放出来，从而产生荧光现象。如何使荧光剂有效与打印墨水结合成为目前研究荧光墨水的专题。
优质荧光墨一般需要用65-75％的进口荧光墨精才能达标，而低档价廉的荧光油墨除了减其颜料的含量之外，又因没采用特选的连结料/助剂，就算增加荧光墨精的含量令浓度变高，但也没法避免在印刷时会发生：1)印刷3-5百张印件，便有堆墨和过度乳化的状况；2)因油墨难于分散，印刷时油墨不能均匀地转移到承印物。
发明内容
为了克服现有技术的不足，本发明提供一种传印能力好的荧光油墨及制备方法。
本发明解决其技术问题所采用的技术方案是：
一种传印能力好的荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球1-5份、稳定剂0.3-0.5份、荧光剂1-2份、炭黑3-5份、连接料10-20份、十二烷基硫酸钠溶液0.4-0.6份、异辛酸钴0.4-0.6份、聚乙烯蜡5-8份和溶剂80-90份；所述P(St-co-AM)微球由以下重量份数的原料制成：苯乙烯10-15份、丙烯酰胺10-15份、过硫酸铵1-3份、过氧化二苯甲酰3-5份和去离子水60-70份。
所述P(St-co-AM)微球的制备方法如下：
(1)、在通有氮气的高温反应釜中加入上述重量份数的过氧化二苯甲酰、过硫酸铵和去离子水，并开启搅拌，搅拌速度为40-50r/min，搅拌时间为30min，得混合液A；
(2)、边搅拌边通过流量注液器向混合液A中滴入上述重量份数的丙烯酰胺，搅拌速度为80-90r/min，搅拌时间和滴入时间均为2-3min，得混合液B；
(3)、将混合液B转移至水浴锅中水浴加热，升温至90-95℃，然后通过流量注液器滴入上述重量份数的苯乙烯，滴入时间为2-3min，滴完后保温反应2-3小时，保温后开启搅拌并冷却至室温，搅拌速度为50-60r/min，得混合液C；
(4)、利用过滤器将混合液C中大颗粒聚合物过滤出来并去除，得滤液，即为P(St-co-AM)微球。
所述连接料为松香改性酚醛树脂、改性醇酸树脂和沥青树脂中的一种。
所述稳定剂为羟丙基纤维素和聚乙二醇中的一种。
所述十二烷基硫酸钠溶液的浓度为0.08-0.14g/L。
所述溶剂由异丙醇和乙醇组成，比例为1:1。
一种制备如上所述荧光油墨的方法，包括如下步骤：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球、稳定剂和溶剂放入搅拌釜中，开启搅拌，边搅拌边升温至60-65℃，搅拌速度为50-60r/min，搅拌时间为15-20分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至80-90℃，搅拌速度为50-60r/min，搅拌至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10-15min，得荧光油墨。
本发明的有益效果是：
(1)、本发明利用无皂乳液聚合法创新性制得P(St-co-AM)微球，该微球能与荧光染料有效地结合在一起，具有较强的着色力，稳定剂的枝接作用显著提高了油墨的分散性，使油墨在印刷时能更好地转移到承印物上，传印转移能力好，稳定性也得到了改善，荧光效果佳。
(2)、本发明制备方法包括预聚合、微球着色和超声分散，制得的荧光油墨色粉细幼，超声波的空化作用不仅使染色微球破碎成了更为细小的颜料颗粒，而且使单体珠滴悬浮分散成更小的液滴，从而减少了由于油墨颜料颗粒的堆积造成的堆墨故障的现象。
具体实施方式
在本发明所有实施例中，关于温度和压力没有特别强调的，均为常温常压，关于设备使用没有特别说明的，均按常规设置来使用即可。
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。需要说明的是，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。
一种传印能力好的荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球1-5份、稳定剂0.3-0.5份、荧光剂1-2份、炭黑(购自东莞市灿煜化工有限公司)3-5份、连接料10-20份、十二烷基硫酸钠溶液(分子式是CH 3(CH 2) 10CH 2OSO 3Na)0.4-0.6份、异辛酸钴(化学式是C 16H 30CoO 4)0.4-0.6、聚乙烯蜡(购自上海凯茵化工有限公司)5-8份和 溶剂80-90份。
所述P(St-co-AM)微球由以下重量份数的原料制成：苯乙烯(分子式C 8H 8)10-15份、丙烯酰胺(化学式为C 3H 5NO)10-15份、过硫酸铵(化学式为(NH 4) 2S 2O 8)1-3份、过氧化二苯甲酰(购自济南裕才化工有限公司)3-5份和去离子水60-70份，苯乙烯与丙烯酰胺在一般情况下难以聚合，本申请利用双引发剂制备P(St-co-AM)微球。
所述P(St-co-AM)微球的制备工艺如下：
(1)、在通有氮气的高温反应釜中加入上述重量份数的过氧化二苯甲酰、过硫酸铵和去离子水，并开启搅拌，搅拌速度为80-85r/min，搅拌时间为30min，得混合液A；
(2)、边搅拌边通过流量注液器向混合液A中滴入上述重量份数的丙烯酰胺，搅拌速度为80-90r/min，搅拌时间和滴入时间均为2-3min，得混合液B；
(3)、将混合液B转移至水浴锅中水浴加热，升温至90-95℃，然后通过流量注液器滴入上述重量份数的苯乙烯，滴入时间为2-3min，滴完后保温反应2-3小时，保温后开启搅拌并冷却至室温，搅拌速度为85-90r/min，得混合液C；
(4)、利用过滤器将混合液C中大颗粒聚合物过滤出来并去除，得滤液，即含P(St-co-AM)微球的滤液。
反应方程式如下：
Figure PCTCN2022126749-appb-000001
本发明采用了无皂乳液聚合法创新性制得P(St-co-AM)微球，无皂乳液指不含乳化剂的聚合方式，这种方法有效避免了乳液聚合过程中乳化剂对反应体系的影响，制得的聚合物微球干净无杂质。而本发明通过加入功能性单体丙烯酰胺(AM)，引入亲水基团，以此增强微球表面与水相界面的相互作用，降低微球表面的表面能，提升微球的稳定性，同时还能极大提升聚合反应速率。
但无皂乳液聚合法也存在明显缺点，其制得的微球粒径较大，一般在几百纳米，因此在油墨制备过程中必须添加超声分散步骤。超声波使液体介质的空化作用增强，使得气泡膨胀和压缩更为剧烈，进而使包覆颜料的微球变得更为细小。通过研究发现，通过超声分散后的染色微球的粒径减少至三分之一，这是因为超声波的空化作用不仅使染色微球破碎成了更为细小的颜料颗粒，而且使单体珠滴悬浮分散成更小的液滴，如此，通过超声波分散可以弥补由无皂乳液聚合法制得微球的粒径大的缺点，使最终的染色微球粒径变小。
所述P(St-co-AM)微球制备过程受搅拌速度影响。无皂乳液聚合法制得的微球单分散性较差，搅拌速度越快，单分散性越差，通过分析和研究，当搅拌速度为80-90r/min时，体系中的剪切速度相对适中，制得的微球粒径较为均一。
所述稳定剂为羟丙基纤维素(分子式为C 36H 70O 19)、聚乙烯基吡咯烷酮(化学式为(C 6H 9NO) n)和聚乙二醇(化学式为HO(CH 2CH 2O) nH)中的一种。稳定剂在荧光墨水的制备中起到至关重要的作用，所用稳定剂均为双亲性化合物，能枝接到微球分子链上，并定位在微球的表面，从而起到位阻稳定的作用，使微球之间不会团聚在一起，分散性好。
所述荧光剂优选济南汇锦川商贸有限公司生产的荧光增白剂，型号为CBS-127。
所述炭黑主要成分是碳元素，由碳氢化合物的部分燃烧或热裂化分解后所得的黑色粉末，价格低廉，着色能力强，稳定性好，能与所述P(St-co-AM)微球有效结合。
所述连接料为松香改性酚醛树脂、改性醇酸树脂和沥青树脂中的一种。优选松香改性酚醛树脂，松香改性酚醛树脂能更好地与着色微球有效结合，使着色微球得以良好分散，使其通过印刷机转移至承印物表面。
所述十二烷基硫酸钠溶液在体系中用作乳化剂，所述十二烷基硫酸钠溶液的浓度为0.08-0.14g/L，本发明使用的十二烷基硫酸钠溶液的浓度远远小于它的临界胶束浓度(约为2.3g/L)，聚合过程中没有乳化剂形成的胶束，而链端带亲水基团的齐聚物达到临界胶束浓度时，彼此紧靠形成低聚物胶束，增溶单体，形成反应核，因此能得到单分散性好的着色微球。
所述异辛酸钴为氧化型干燥剂，催干能力极强，特别是促进表面干燥。本发明采用的异辛酸钴，起到加速油墨氧化结膜干燥的作用，又称为催干剂，是最重要的助剂之一。常见的干燥剂还有锰干燥剂等金属干燥剂，但这些干燥剂的催干效果都不太理想，一般都不用于油墨。
所述聚乙烯蜡用作耐摩擦助剂，加入到油墨中可以使印在承印物上后能浮在墨膜上以增加耐摩擦性。聚乙烯蜡的用量对油墨的性能影响非常关键，直接影响了油墨流动性、转移性和光泽。
申请人还研究了温度对微球染色情况的影响。研究表明，在80-90℃范围内，温度越高，染料分子越容易进入微球内部，而温度越低，染料分子扩散就较为困难，染料多聚集在微球的表面或者较浅层的内部，制得的荧光墨的显色效果较差。
本发明利用加热共聚法使P(St-co-AM)微球着色，其原理是通过加热的方式使荧光剂镶嵌在膨胀后的微球上，微球受热膨胀，炭黑扩散进入微球内部，进而得到使微球着色。
一种制备如上所述荧光油墨的方法，包括如下步骤：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球、稳定剂和溶剂于搅拌釜中， 开启搅拌，边搅拌边升温至60-65℃，搅拌速度为50-60r/min，搅拌时间为15-20分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至80-90℃，搅拌速度为50-60r/min，搅拌至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10-15min，得荧光油墨。
实施例1：
一种荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球3份、稳定剂0.4份、荧光剂1.5份、炭黑4份、连接料15份、十二烷基硫酸钠溶液0.5份、异辛酸钴0.5份、聚乙烯蜡6份和溶剂85份。
实施例1的荧光油墨的制备步骤如下：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球、稳定剂和溶剂于搅拌釜中，开启搅拌，边搅拌边升温至60℃，搅拌速度为50r/min，搅拌时间为15分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至90℃，搅拌速度为50r/min，搅拌至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10min，得实施例1的荧光油墨。
实施例2：
一种荧光油墨，由以下重量份数的原料制成：聚苯乙烯微球(购自东莞市科迈新材料有限公司)3份、稳定剂0.4份、荧光剂1.5份、炭黑4份、连接料15份、十二烷基硫酸钠溶液0.5份、异辛酸钴0.5份、聚乙烯蜡6份和溶剂85份。
实施例2的荧光油墨的制备步骤如下：
(1)、预聚合：取上述重量份数的聚苯乙烯微球、稳定剂和溶剂于搅拌釜中，开启搅拌，边搅拌边升温至60℃，搅拌速度为50r/min，搅拌时间为15分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至90℃，搅拌速度为50r/min，搅拌至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10min，得实施例2的荧光油墨。
实施例3：
一种荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球3份、荧光剂1.5份、炭黑4份、连接料15份、十二烷基硫酸钠溶液0.5份、异辛酸钴0.5份、聚乙烯蜡6份和溶剂85份。
实施例3的荧光油墨的制备步骤如下：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球和溶剂于搅拌釜中，开启搅拌，边搅拌边升温至60℃，搅拌速度为50r/min，搅拌时间为15分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至90℃，搅拌速度为50r/min，搅拌至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10min，得实施例3的荧光油墨。
实施例4：
一种荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球3份、稳定剂0.4份、荧光剂1.5份、炭黑4份、连接料15份、十二烷基硫酸钠溶液0.5份、异辛酸钴0.5份、聚乙烯蜡6份和溶剂85份。
实施例4的荧光油墨的制备步骤如下：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球和溶剂于搅拌釜中，开启搅拌，边搅拌边升温至60℃，搅拌速度为50r/min，搅拌时间为15分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至90℃，搅拌速度为50r/min，搅拌至溶液均匀，得实施例4的荧光油墨。
实施例5：
一种荧光油墨，由以下重量份数的原料制成：P(St-co-AM)微球3份、稳定剂0.4份、荧光剂1.5份、炭黑4份、连接料15份、十二烷基硫酸钠溶液0.5份、异辛酸钴0.5份、聚乙烯蜡6份和溶剂85份。
实施例5的荧光油墨的制备步骤如下：
(1)、预聚合：取上述重量份数的P(St-co-AM)微球、稳定剂和溶剂于搅拌釜中，开启搅拌，边搅拌边升温至60C，搅拌速度为50r/min，搅拌时间为15分钟，得预聚液；
(2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至80C，搅拌速度为50r/min，搅拌 至溶液均匀，得荧光溶液；
(3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10min，得实施例5的荧光油墨。
申请人对实施例1-5的荧光油墨的印刷效果进行了测试，其中，印刷速率为6000～10000张/小时，测试结果表明：
实施例1印品线条光滑，网点饱满，印刷中没有飞墨、糊版和堆墨现象，印迹附着良好。
实施例2印品线条光滑，网点饱满，印刷后期出现飞墨现象，总体印迹附着良好。
实施例3印品线条光滑，网点饱满，印刷中没有飞墨、糊版和堆墨现象，印迹附着良好。
实施例4印品线条光滑，网点饱满，印刷中出现飞墨、糊版和堆墨现象，印迹附着效果一般。
实施例5印品线条光滑，网点饱满，印刷中没有飞墨、糊版和堆墨现象，印迹附着一般。
申请人对实施例1-5的细度、粘度、初干性、着色力、附着牢度以及上染率进行了测算，其中：
细度按照GB/T13217.1-91的标准进行检测，单位为μm；
粘度按照GB/T13217.1-91的标准进行检测，单位为(25℃±1)S；
着色力按照GB/T13217.1-91的标准进行检测，单位为(％)；
附着牢度按照GB/T13217.1-91的标准进行检测，单位为(％)；
上染率依据Beer-Lambert定律，其实质是当其他条件一定时，稀溶液的吸光度与其浓度是成正比的。根据P(St-co-AM)微球在四氢呋喃溶液中λmax处吸光度与相同浓度未染色的混合液在四氢呋喃溶液中λmax处吸光度的比值，即可得到上染率。
测算结果如下：
材料 细度 粘度 着色力 附着牢度 上染率/％ 发光强度/cd
实施例1 6 43 102 99 94.5 2.97
实施例2 8 41 97 99 79.3 2.1
实施例3 6 40 100 95 85.6 1.73
实施例4 20 41 101 98 91.2 2.43
实施例5 7 42 99 98 89.1 2.68
由以上数据表面，P(St-co-AM)微球与现有的聚苯乙烯微球相比，P(St-co-AM)微球的包覆性更强，更加稳定；通过超声分散后的P(St-co-AM)微球更为细小，着色能力 和附着牢度更佳；P(St-co-AM)微球与稳定剂之间能产生优异的协同作用，使得微球的上染率升高，发光强度好。
申请人还研究了溶剂的种类与配比对微球的影响，但还未形成详细完整的实验数据，根据现有的实验数据，结合初步分析，溶剂的种类与配比对微球的上染率是有较大影响的，其直接影响油墨的荧光效果。而从理论层面上看，本发明采用的溶剂，由异丙醇和乙醇组成，比例为1:1并非是最佳组合。
尽管已经示出和描述了本发明的实施例，本领域的普通技术人员可以理解，在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由权利要求及其等同物限定。

Claims (7)

  1. 一种传印能力好的荧光油墨，其特征在于，由以下重量份数的原料制成：P(St-co-AM)微球1-5份、稳定剂0.3-0.5份、荧光剂1-2份、炭黑3-5份、连接料10-20份、十二烷基硫酸钠溶液0.4-0.6份、异辛酸钴0.4-0.6份、聚乙烯蜡5-8份和溶剂80-90份；所述P(St-co-AM)微球由以下重量份数的原料制成：苯乙烯10-15份、丙烯酰胺10-15份、过硫酸铵1-3份、过氧化二苯甲酰3-5份和去离子水60-70份。
  2. 根据权利要求1所述的荧光油墨，其特征在于，所述P(St-co-AM)微球的制备方法如下：
    (1)、在通有氮气的高温反应釜中加入上述重量份数的过氧化二苯甲酰、过硫酸铵和去离子水，并开启搅拌，搅拌速度为40-50r/min，搅拌时间为30min，得混合液A；
    (2)、边搅拌边通过流量注液器向混合液A中滴入上述重量份数的丙烯酰胺，搅拌速度为80-90r/min，搅拌时间和滴入时间均为2-3min，得混合液B；
    (3)、将混合液B转移至水浴锅中水浴加热，升温至90-95℃，然后通过流量注液器滴入上述重量份数的苯乙烯，滴入时间为2-3min，滴完后保温反应2-3小时，保温后开启搅拌并冷却至室温，搅拌速度为50-60r/min，得混合液C；
    (4)、利用过滤器将混合液C中大颗粒聚合物过滤出来并去除，得滤液，即为P(St-co-AM)微球。
  3. 根据权利要求1所述的荧光油墨，其特征在于，所述连接料为松香改性酚醛树脂、改性醇酸树脂和沥青树脂中的一种。
  4. 根据权利要求1所述的荧光油墨，其特征在于，所述稳定剂为羟丙基纤维素和聚乙二醇中的一种。
  5. 根据权利要求1所述的荧光油墨，其特征在于，所述十二烷基硫酸钠溶液的浓度为0.08-0.14g/L。
  6. 根据权利要求1所述的荧光油墨，其特征在于，所述溶剂由异丙醇和乙醇组成，比例为1:1。
  7. 一种制备如权利要求1-6中任一项所述的荧光油墨的方法，其特征在于，包括如下步骤：
    (1)、预聚合：取上述重量份数的P(St-co-AM)微球、稳定剂和溶剂放入搅拌釜中，开启搅拌，边搅拌边升温至60-65℃，搅拌速度为50-60r/min，搅拌时间为15-20分钟，得预聚液；
    (2)、微球着色：向上述预聚液中添加上述重量份数的荧光剂、炭黑、连接料、十二 烷基硫酸钠溶液、异辛酸钴和聚乙烯蜡，边搅拌边升温至80-90℃，搅拌速度为50-60r/min，搅拌至溶液均匀，得荧光溶液；
    (3)、超声分散：将所述步骤(2)得到的荧光溶液转移至超声波分散仪中，超声分散10-15min，得荧光油墨。
PCT/CN2022/126749 2022-04-26 2022-10-21 一种传印能力好的荧光油墨及制备方法 WO2023206990A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210450507.1A CN114702859B (zh) 2022-04-26 2022-04-26 一种传印能力好的荧光油墨及制备方法
CN202210450507.1 2022-04-26

Publications (1)

Publication Number Publication Date
WO2023206990A1 true WO2023206990A1 (zh) 2023-11-02

Family

ID=82176073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/126749 WO2023206990A1 (zh) 2022-04-26 2022-10-21 一种传印能力好的荧光油墨及制备方法

Country Status (2)

Country Link
CN (1) CN114702859B (zh)
WO (1) WO2023206990A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702859B (zh) * 2022-04-26 2023-06-27 中山市富日印刷材料有限公司 一种传印能力好的荧光油墨及制备方法
CN116482084A (zh) * 2023-02-13 2023-07-25 上海索昕生物科技有限公司 用于光激化学发光检测的感光微球

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6126731A (en) * 1998-08-21 2000-10-03 Idea Development Company Polymerizable ink composition
JP2007238949A (ja) * 1994-10-31 2007-09-20 Dainippon Ink & Chem Inc インクジェット記録用水性インク及びその製造方法
JP2009067858A (ja) * 2007-09-12 2009-04-02 Ricoh Co Ltd インクジェット用インク及び画像形成方法
CN104212087A (zh) * 2014-09-19 2014-12-17 哈尔滨工业大学 一种单分散荧光微球的制备方法
CN107216421A (zh) * 2017-06-27 2017-09-29 上海交通大学 一种单分散聚苯乙烯微球及其制备方法与应用
CN107793828A (zh) * 2017-11-22 2018-03-13 成都新柯力化工科技有限公司 一种纳米可调色环保油墨及制备方法
CN111088033A (zh) * 2019-12-25 2020-05-01 苏州为度生物技术有限公司 一种单分散高性能量子点荧光微球的制备方法
CN112210248A (zh) * 2020-10-27 2021-01-12 哈尔滨工业大学（深圳） 一种水性荧光墨水及其制备方法和应用
CN112574615A (zh) * 2021-01-19 2021-03-30 江苏硕茂苏彩新材料有限公司 一种快速固化uv油墨及其制备工艺
CN112851846A (zh) * 2021-01-28 2021-05-28 浙江大学 一种无皂乳液聚合制备表面羧基化纳米荧光微球的方法
CN113683717A (zh) * 2021-10-13 2021-11-23 广东省大湾区华南理工大学聚集诱导发光高等研究院 一种微米级聚集诱导发光聚合物微球及其制备方法与应用
CN114702859A (zh) * 2022-04-26 2022-07-05 中山市富日印刷材料有限公司 一种传印能力好的荧光油墨及制备方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007238949A (ja) * 1994-10-31 2007-09-20 Dainippon Ink & Chem Inc インクジェット記録用水性インク及びその製造方法
US6126731A (en) * 1998-08-21 2000-10-03 Idea Development Company Polymerizable ink composition
JP2009067858A (ja) * 2007-09-12 2009-04-02 Ricoh Co Ltd インクジェット用インク及び画像形成方法
CN104212087A (zh) * 2014-09-19 2014-12-17 哈尔滨工业大学 一种单分散荧光微球的制备方法
CN107216421A (zh) * 2017-06-27 2017-09-29 上海交通大学 一种单分散聚苯乙烯微球及其制备方法与应用
CN107793828A (zh) * 2017-11-22 2018-03-13 成都新柯力化工科技有限公司 一种纳米可调色环保油墨及制备方法
CN111088033A (zh) * 2019-12-25 2020-05-01 苏州为度生物技术有限公司 一种单分散高性能量子点荧光微球的制备方法
CN112210248A (zh) * 2020-10-27 2021-01-12 哈尔滨工业大学（深圳） 一种水性荧光墨水及其制备方法和应用
CN112574615A (zh) * 2021-01-19 2021-03-30 江苏硕茂苏彩新材料有限公司 一种快速固化uv油墨及其制备工艺
CN112851846A (zh) * 2021-01-28 2021-05-28 浙江大学 一种无皂乳液聚合制备表面羧基化纳米荧光微球的方法
CN113683717A (zh) * 2021-10-13 2021-11-23 广东省大湾区华南理工大学聚集诱导发光高等研究院 一种微米级聚集诱导发光聚合物微球及其制备方法与应用
CN114702859A (zh) * 2022-04-26 2022-07-05 中山市富日印刷材料有限公司 一种传印能力好的荧光油墨及制备方法

Also Published As

Publication number Publication date
CN114702859B (zh) 2023-06-27
CN114702859A (zh) 2022-07-05

Similar Documents

Publication Publication Date Title
WO2023206990A1 (zh) 一种传印能力好的荧光油墨及制备方法
US6110266A (en) Ink-jet inks containing nanometer-size inorganic pigments
CN104530892B (zh) 一种复合金卡纸用环保型水性清漆及其制备方法
EP1270681A2 (en) Colored fine resin particles and inks containing these for ink-jet recording
CN112126280B (zh) 一种钙钛矿量子点隐形喷墨打印墨水
CN101486845A (zh) 一种纳米色料水性分散体的制备方法
CN101798477B (zh) 一种热转印喷墨墨水纳米胶囊及其制备方法
CN105255261B (zh) 一种水性色浆及其制备方法
AU2020100263A4 (en) Method for preparing hybrid organic pigment powder with light resistance and high dispersion stability
JPH10219160A (ja) 長鎖アルコールを含有するインクジェットインク
CN114133792A (zh) 一种水性纳米颜料分散体
US2776267A (en) Spherical pigments and method of preparing same
JP3387610B2 (ja) インクおよびその製造方法
JP3839894B2 (ja) インクジェット用記録液
CN110591413B (zh) 耐光降解、不扬尘、易分散的有机颜料固体色浆的制备方法
KR101738509B1 (ko) 유무기 하이브리드 안료 입자 및 이를 포함하는 안료-염료 복합체 및 이들의 제조방법
JP4196415B2 (ja) インクジェット記録用マイクロカプセルインク組成物及びその製造方法
WO2014208703A1 (ja) インクジェット印刷用インク、インクジェット印刷用インクの製造方法、及びインクジェット印刷方法
CN115124720B (zh) 一种用于涂料印染粘合剂的改性明胶及其制备方法与应用
JP5318447B2 (ja) 水不溶性色材分散体及びこの製造方法、これを用いた記録液、インクセット、印画物、画像形成方法、並びに画像形成装置
CN113185867A (zh) 一种接枝分散剂及其制备方法和在水性喷墨色浆中的应用
CN113698540A (zh) 一种核壳结构高性能粘合剂的合成方法
CN113047061B (zh) 一种超低粘度彩色颜料及其制备方法与应用
JP2001139607A (ja) 着色樹脂エマルジョン、その製造方法、着色樹脂エマルジョンインク、及び、カラーフィルターの製造方法
JP3386910B2 (ja) 着色電着塗装用顔料分散体組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22939810

Country of ref document: EP

Kind code of ref document: A1