KR20170029779A - Ink composition comprising intelligent microemulsion ink vehicle resin and manufacturing method of the same - Google Patents

Abstract

The present invention relates to an ink-jet printer, which is capable of printing on all digital, analog, and digital-analog type printing objects using an electronic control device and is capable of recycling resources, ≪ / RTI > In addition, ink droplets having intelligent self-assembly, self-assembly, self-dispersing, self-cleaning, and magnetic restoration ability for all coloring matter expressing color and ink vehicle as a main object of the present invention have monodispersed distribution, The present invention relates to the preparation of an ink vehicle in which an ink vehicle can be cured in a suspended state and in an emulsified state which can be cured by low energy depending on pH, temperature and humidity. More specifically, the present invention relates to an ink- An ink composition and a coating method which require a high conversion ratio such as environment-friendly printing and dyeing of fibers and nanoimprinting of printed electronic molecules through high polymerization conversion rate, and a manufacturing method in which the final curing process is simplified.

Description

FIELD OF THE INVENTION [0001] The present invention relates to an ink composition comprising an intelligent microemulsion ink vehicle and a method of manufacturing the ink composition. [0002]

The present invention relates to an ink-jet printer, which is capable of printing on all digital, analog, and digital-analog type printing objects using an electronic control device and is capable of recycling resources, The present invention relates to an ink vehicle having a monodispersed distribution with an ink moving body having intelligent self-assembly, self-structuring, self-dispersion, self-cleaning, The present invention relates to ink manufacture of an ink vehicle which has a maleic micelle and is switchable in a suspended state and an emulsified state in which the low energy curing can be carried out according to pH, temperature and humidity.

More specifically, the present invention relates to an ink composition which requires a high conversion rate, such as technology for eliminating the additional non-water-soluble, non-degradable material generated in the production of an ink vehicle, environmentally friendly and dyeing of fibers and dyeing by high polymerization conversion, And a manufacturing method in which the coating method and the final curing process are simplified.

The present invention relates to a process for the surface treatment of a target substrate to be printed by dissolving or dispersing an excess or a small amount of surfactant, acid or alkali when dispersed in a coloring material used in screen lithography, photolithography, digital inkjet ink, To reduce the interfacial tension between the ink and the target substrate, so that functional elements such as ink adhesion and color development are based on physicochemical processing.

In order to compensate for this problem, various types of surfactants can be added to the ink composition system because the characteristics of the ink composition system vary greatly depending on the solvent used.

However, the amount of surfactant added increases the COD and BOD levels in wastewater treatment and causes water pollution due to eutrophication. This problem can be minimized by using benign starch in aqueous or vegetable oil based inks, but the fundamental problem is difficult to solve.

In addition, organic solvent-based, non-aqueous mainstream vehicles, or petroleum-based oil bases, can cause problems in the ink production process as well as discarded ink problems.

To solve this problem, Hewlett Packard has proposed a solution for latex ink composition and photocurable ink production of a non-aqueous system with patents (US4978969A, US6057384, US6248805, US6866438, US7030175, US7119133, WO2007040745, WO2005097924) It is only possible to use materials that have not been universally applicable and can be applied to special treatments.

In addition, in the case of Canon's patent (JP2007193253, JP2006055781), a water-based emulsion type ink which is thermodynamically stable but has poor chemical stability is introduced. In the case of Seiko Epson, the patent (EP1914279A2, US2007213438A1, JP2007092071, EP1754759) Although various attempts have been made by suggesting a photo-curing by ultraviolet rays or a petroleum-based oil-based ink, it is not a fundamental solution.

In addition, patent applications filed, disclosed and registered by the company (KR / 2004/26504, KR / 2006/92861, PCT / KR2010 / 6401, PCT / KR2010 / 7024, PCT / KR2010 / 7192, PCT / KR2010 / In addition to the above problems of ink production, there is a problem in that the magnetic properties of the magnetic recording medium, which affects the stability of the head, Iron, phosphate, and phosphate are mainly used for surfactants. Suggested solutions as a complementary solution in this section are based on water and vegetable oil based solvents that can be presented or utilized in academic circles. Based on the polymerization of microemulsion and subnano suspension, supercritical fluid of high molecular weight organic / inorganic hybrid polymer particles with subnano size and three-dimensional switching micelle form capable of suspension and emulsification of advanced ink can be used Ink It proposed a method of manufacturing a fluid (PCT / KR2013 / 001622).

And the problem of discoloration such as photo deterioration is difficult to solve, it is possible to supplement the technical defects with the method of manufacturing the new ink vehicle fluid of the present invention, thereby making it easier to use and more powerful In addition to durability printing and printing, we propose an ink manufacturing method that can be used in the dyeing sector.

The object of the present invention is to provide a method for producing an ink for use in a printing and dyeing method, which is a means for mankind to express color, and an ink vehicle for stable binding of the ink to the printing body in a smooth physical- (PCT / KR2013 / 001622) through a light source using low energy as a simple curing system in a short period of time and in a short period of time. And to provide an environmentally friendly and durable ink composition using a simpler, lower energy and more stable energy.

In order to solve the above problems, the present invention provides a method of manufacturing a coloring material, comprising: selecting a coloring material and a polymerizing material; Purifying the dye material and the polymer material; Oil-inorganic synthesizing the purified pigment material, and polymerizing the purified polymer material into an ink vehicle; Adjusting the physical properties of the ink vehicle; Mixing the compounded pigment with a physically controlled ink vehicle; Dispersing the mixed ink vehicle and the synthesized pigment in a homogenized dispersion at normal temperature and pressure; And mixing the dispersed substance with zirconium-silica-hafnium alloy beads to rearrange the molecules of the dispersed substance to prepare a master stock solution.

Here, the method for producing the ink composition may include a letdown step of diluting the master stock solution with a diluting solvent; Adjusting the viscosity and the surface tension according to the amount of the additive to prepare an ink composition; And filtering the ink composition with a membrane filter.

Further, it is preferable that the polymer material includes the following chemical formula (1) and chemical formula (2).

[Chemical Formula 1]

(2)

(Wherein R ₁ , R ₂ and R ₃ are acrylic or methacrylic functional groups).

Also, the average particle size of the dispersed material contained in the master stock solution is preferably 0.7 to 1 nm.

In addition, the present invention provides an ink composition which is produced by the above-described production method and does not produce a chemical harmful to the environment.

 The method of manufacturing an ink composition according to the present invention enables printing and dyeing by adding chemicals to a minimum.

In addition, the produced material enhances photodegradation and biodegradation ability of an intelligent ink vehicle in an ink composition to decompose non-water-soluble and poorly soluble materials or to capture and decompose environmental pollutants in the air even when harmful chemicals are generated, And can be cured at low energy by pH, temperature, and humidity, which is a method of curing using minimum amount of light energy.

1 schematically shows a process for producing an ink composition according to the present invention.

According to a preferred embodiment of the present invention, there is provided an ink jet recording method comprising: a material selection step (S11) for using various inks; A step of purifying the material (S12); Organic-inorganic synthesis step (S13) of the dye material; Polymerizing the ink vehicle (S13); Adjusting the properties of the synthesized polymerized material (S14); Blending the synthesized pigment with the polymerized ink vehicle (S15); A blended normal temperature-atmospheric pressure homogenization dispersion step (S16); (S17) of preparing a master stock solution by rearranging molecules having an average particle size of 0.7 to 1 nm by putting zirconium / silica / hafnium alloy beads of 0.03 mm to 0.3 mm in the milling machine; A descdown step (S18) of diluting the master stock solution with a diluting solvent; A pre-imaging step (S19) for diluting by adding an ink additive; A step (S20) of diluting by adding an ink functional additive; Adjusting the viscosity and the surface tension to prepare an ink composition (S21); And filtering the prepared ink composition with an inline member lane using a fine filter paper (S22); (S23) or dyeing step (S24), and the produced ink does not produce and discharge toxic chemicals in the process and the final product.

According to another preferred embodiment of the present invention, it is preferable that the pigment is selected from the group consisting of Sunhoon: quinacridone, cyan: phthalocyanine, yellow: benzimidazoline, and black: carbon black. As dye dyes, it is preferable to select dyes: quinine dyes, cyan dyes: anthraquinone dyes, yellow: imine dyes dyes, and black: white carbon dyes.

The pigments and dyes may be prepared by selectively mixing the dyes and pigment ratios for each color, and thereafter, in a nitrogen atmosphere under standard conditions, N-methylpyrrolidone as an aqueous solvent, dimethylsulfoxide as a co-solvent and tetrabutyl alcohol as a non- It is preferable to add it to the mixed solution.

The organophosphorus is added to the blend liquid in which the pigment and the dye are regularly mixed with each other by sequential addition to the copper catalyst, and is polymerized into a salt-pigment copolymerized pigment by the Ziegler-Natta reaction.

The copolymerizable colorant thus synthesized is crystallized by using hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide or the like to synthesize a chromophore.

Other synthetic methods of this synthesis include the use of Char coal, Ethylenedioctyl thiophene, pyrrole, and aniline under a nitrogen atmosphere in the presence of 2-pyrrolidone (dimethyl sulfoxide) as a water-based quantum solvent, 2-pyrrolidone, After the addition of methyl alcohol, an Au catalyst and benzyl peroxide (BPO) as a photoinitiator (2,2-Azobis (2methylpropion) dihydrodicholoride: V-50), which is a free radical initiator, Followed by stirring at 600 rpm for 6 hours. And photopolymerized at an ultraviolet wavelength of 253 nm for 24 hours to form nano spherical particles having electric conductivity.

According to another suitable embodiment of the present invention, the step of polymerizing and preparing the ink vehicle fluid may comprise the step of preparing a polymer dispersed surfactant in ultrapure water or vegetable oil.

According to the detailed embodiment of the present invention, the oil in water (O / W), the water in oil (W / O), the oil in water in oil Acrylate, methacrylate, unsaturated polyester, silane, amide, and the like to polymerize and prepare an ink vehicle fluid having a multi phase in the form of water in oil in water (W / O / W) (Meth) acrylate, acrylic acid, methacrylic acid, urea, and the like are added to monomers having a mixing weight ratio (wt%) of 10 to 20, Polyethylene Oxide_block_ Polypropylene Oxide having a blend weight ratio (wt%) of less than 1, such as vegetable oil base (soybean oil, sesame oil, perilla oil, flaxseed oil, rosin oil) or animal oil (pig oil, PEO / PPO / PEO, PPO / PEO / PPO) blocking reaction type polymer surfactant and Hexadecyltrimethylammonium bromide (DTAB), Dodecyl benzoic acid (DBA), and Tetradecyltrimethylammonium bromide (DBA), which are reactive anionic surfactants such as sodium lauryl sulfate, sodium bis (2-ethylhexyl) (di, mono) sulfosuccinate, (TTAB), reactive amphoteric surfactants such as Lecitin and sodium chloride, and mixtures thereof selected from the group consisting of glycerin and diol as a emulsifier having a mixing weight ratio (wt%) of less than 1 to 10 (2-azobis (2methylpropion) dihydrodicholoride: V-50), 2,2-azobis (2methylpropion acid: V-501), Amino persulfate APS), Potassium persulfate (KPS), etc., and 2- (Dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2-Cyano-2-propyl dodecyl trithiocarbonate, Cyanomethyl methyl (phenyl) carbamodithioate and 4-Cyano-4- (phenylcarbonothioylthio) pentanoic acid Reversib Special Additions of Atom Transfer Radicals (RAFT) and Atom Transfer Radicals (RAFT) with special monomer having a weight ratio (wt%) of less than 1 such as vinyl acetate (VAc), N-vinylpyrrolidone (NVP), and N-vinylcarbazole 2,2'-Azobis (2-methylpropionitrile), a thermal radical initiator with a blend weight ratio (wt%) of less than 1 for polymerization (ATRP): AIBN, Benzoyl peroxide (BPO) Photoinitiators having a weight ratio (wt%) of less than 1 of Acetophenones such as 4,6-trimethylbenzoyldiphenylphosphine oxide, Benzoins, Benzophenones, p-toluenesulfonates, phosphates, triflates, hydrates, thioxanthones, Alcohol with a weight ratio, dimethyl sulfoxide. It does not generate and discharge harmful substances during the polymerization process and post-processing process.

According to another preferred embodiment of the present invention, the polymerization preparation of a high molecular weight organic / inorganic hybrid polymer supercritical fluid having a Multi phase phase in the form of oil in water is carried out by using styrene, acrylate, methacrylate, unsaturated polyester Wherein the monomer selected from the group consisting of silane, amide, imine, acrylic acid, methacrylic acid and urea is used as a continuous system having 10 to 20 weight ratio (wt%) and 30 to 80 weight ratio (wt% 2 ~ 3 Blocking Reaction Type Polymer Surfactant composed of Polyethylene Oxide_block_ Polypropylene Oxide (PEO / PPO) with a Pure Water and a Mixture Weight Ratio (wt%) of less than 1, and Sodium Lauryl Sulfate, sodium bis (2-ethylhexyl) mono) sulfosuccinate, betine, etc., and an emulsifier having a weight ratio (wt.%) of less than 1 to less than 10, selected from the group consisting of glycerin and diol (2-azobis (2methylpropion) dihydrodicholoride: V-50), (2,2-Azobis (2methylpropion acid: V-501), Amino persulfate APS), Potassium persulfate (KPS), etc., and 2- (Dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2-Cyano-2-propyl dodecyl trithiocarbonate, Cyanomethyl methyl (phenyl) carbamodithioate and 4-Cyano-4- (phenylcarbonothioylthio) pentanoic acid Reversible Addition Fragmentation Chain transfer (RAFT) A special monomer having a weight ratio (wt%) of less than 1 such as vinyl acetate (VAc), N-vinylpyrrolidone (NVP), and N-vinylcarbazole 2,2'-Azobis (2-methylpropionitrile), a thermal radical initiator with a blend weight ratio (wt%) of less than 1 for polymerization (ATRP): AIBN, Benzoyl peroxide (BPO) , 4,6-trimethylbenzoyldiphenylphosphine oxide and the like, Acetophenones, Benzil, Benzoin, B photoinitiators having a weight ratio (wt.%) of less than 1 of benzophenones, p-toluenesulfonates, phosphates, triflates, hydrates and thioxanthones and dimethy sulfoxide having a blend weight ratio (wt.%) of less than 1 as co-solvent.

According to another preferred embodiment of the present invention, the polymerization preparation of a high molecular weight organic / inorganic hybrid polymer supercritical fluid having a Multi phase phase in the form of Water in Oil is carried out in the presence of styrene, acrylate, methacrylate, unsaturated polyester (Wt.%) Of a monomer selected from the group consisting of silane, amide, imine, acrylic acid, methacrylic acid, urea and the like in a weight ratio of 10 to 20 (2-ethylhexyl) (di, mono) sulfosuccinate, betine, and polyoxyethylene polyoxypropylene oxide (PEO / PPO) , And a mixture thereof selected from the group consisting of glycerin and diol as an emulsifier having a mixing weight ratio (wt%) of less than 1 to 10 (2-azobis (2methylpropion) dihydrodicholoride: V-5), 2,2-azobis (2methylpropion acid: V-501), Amino persulfate (APS), Potassium persulfate KPS) and Reversible Addition Fragmentation Chain Transfer (RAFT) such as 2- (Dodecylthiocarbonothioylthio) -2-methylpropionic acid, 2-Cyano-2-propyl dodecyl trithiocarbonate, Cyanomethyl methyl (phenyl) carbamodithioate and 4-Cyano- ) Special monomers with a weight ratio (wt%) of less than 1 such as vinyl acetate (VAc), N-vinylpyrrolidone (NVP), and N-vinylcarbazole (NVC), and atom transfer radical polymerization 2,2'-Azobis (2-methylpropionitrile), a thermal radical initiator having a blend weight ratio (wt%) of less than 1, AIBN, Benzoyl peroxide (BPO), and a representative photoinitiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc., Acetophenones, Benzil, Benzoin, Benzophenone a photoinitiator having a weight ratio (wt%) of less than 1 of p-toluenesulfonates, phosphates, triflates, hydrates, thioxanthones and an alcohol having a blend weight ratio of less than 1 as co-solvent.

In the case of vegetable oils described above, Palm, Soybean, Rapeseed, Sunflower seed, Peanut, Cottonseed, Palm kernel, Coconut, Olive, Corn oil, Grape seed oil, Hazelnut and other nut oils, Linseed oil, oil, Safflower oil, Sesame oil, and the like.

In case of animal oil, it includes pig oil, iron oil and the like. Ingredients include linoleic acid, alpha-linolenic acid, and oleic acid.

 In the case of diols, the linear structure of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,6-hexanediol, 1,3-butanediol, 1,2-pentanediol, Etohexadiol, p-Menthane-3,8-diol, and 1,2-decanediol. diol, 2-Methyl-2,4-pentanediol, and the like. Alcohols to be polymerized include primary alcohols such as ethyl (propyl, utyl) alcohol, secondary alcohols such as isopropyl alcohol, tertiary alcohols such as tetrabutyl alcohol, and polyhydric alcohols, unsaturated aliphatic alcohols, and alicyclic alcohols.

As a substitute for glycerin and diol used as emulsifiers, Mowiol, a polyvinyl alcohol precursor having a saponification value of 80 to 100%, may be used, or polyol oxide, propylene oxide, glycerol (ethoxy) propoxylate, polyamide-graft- cellulose such as sorbitol and mannitol, Pectin, Arabic Gum, Guar Gum, sodium alginate, etc., such as cellulose, Soluble strach (Methyl, Ethyl, Propyl) cellulose, CMC-Ca, CMC-Na, Dextrin and Cyclodextrin Chitin, glucosamine, hyruronic acid, polylactic acid, polyglutamic acid and other nonionic surfactants such as Span 20, 40, 60, 80, Tween 20, 40, 60, 80, 85 and X Serion from Xtrion , Micellman's 39235, 64840, 93320, D310 and Pluronic Serise from BASF or Aerosol Serise from Cytec.

Examples of the polymerization terminator include sodium hydroxymethanesulfinate hydrate (SFS), tert-butyl hydroperoxide (TBHP), hydrogen peroxide (HPO), DL-ascorbic acid (Vitamin C), and Benzonic acid. Examples of the pH regulator include citric acid, boric acid, Soda, potassium phosphate, sodium bicarbonate, sodium carbonate, sulphide, manganese, and lithium carbonate.

In order to stabilize the finished polymer in a water-based or vegetable oil-based solvent, special inorganic compounds, organic monomers, oligomers, prepolymers and polymers may be used as stabilizers. The inorganic compounds added to the polymerization process include lithium, sodium, potassium, boric, Iodine, Silver, Gold, Strontium, Aluminum, Copper, Iron, Magnesium, Tungsten, Cobalt, Zinc, Titanium, Silica, Antimony, Indium, Iridium, Hafnium, Zirconium, Barium and Beryllium, and organic monomers such as toluenesulfonate and maleate. Examples of the oligomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, (di (tri) ethylene (meth) Diol, polycarbonate urethane diol, and in the case of the polymer, polystyrene sulfonic acid, polystyrene maleic acid, polysiloxane and the like are used. And cinnamic acid and polycinnamic acid, which are used as photosensitive polymer polymerization initiators. Oxidation (deterioration) inhibitors include tocopherol and polymeric plasticizers such as polyethylene glycol, vinylpyrrolidone, vinyl alcohol, vinyl acetate, succinic acid, citric acid, and malic acid, which are used in foods and pharmaceuticals. Hydrophobic hydrocarbons fluorine, hydrated porous silica, hydrated porous alumina are included as surface tension modifiers. In addition, vinyl butyral and vinyl foam were used for glossiness and transparency of the processing elements of the polymer. The combined weight of the polymeric binder, the antioxidant, the stabilizer, the photosensitive polymer polymerization initiator, the pH adjuster, the surface tension adjuster, and the gloss transparency adjusting agent is 100 ppb to 1 mg / Kg. According to an embodiment of the present invention, the finished polymeric fluid surface tension is 10 to 40 dyne / cm; A viscosity of 3,000 to 15,000 cPs; And the pH is 7 to 11.

The polymerization preparation of the ink composition according to the present invention includes a high purity purification process which uses chemicals which are harmless to the human body and the environment and which enhances the purity of raw materials which are biodegradable to heat or light. The ink composition according to the present invention, which is manufactured using a chemical substance, discharges substances which are not harmful to the human body and the environment during the process, thereby protecting the operator and protecting the environment.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in detail below with reference to the embodiments shown in the accompanying drawings. The presented embodiments are illustrative and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 schematically illustrates an ink manufacturing process using an ink vehicle fluid according to the present invention.

Referring to FIG. 1, the method for producing an ink composition of the present invention comprises the steps of: (S11) selecting a dye material and a polymer material; A step of purifying the coloring material and the polymerizing material (S12); Organic-inorganic synthesis step (S13) of the dye material; Polymerizing the ink vehicle (S13); Adjusting the physical properties of the polymerized ink vehicle (S14); Blending the synthesized pigment with the polymerized ink vehicle (S15); A blended normal temperature-atmospheric pressure homogenization dispersion step (S16); (S17) of preparing a master stock solution by rearranging molecules having an average particle size of 0.7 to 1 nm by putting zirconium / silica / hafnium alloy beads of 0.03 mm to 0.3 mm in the milling machine; A descdown step (S18) of diluting the master stock solution with a diluting solvent; A step (S20) of diluting by adding an ink function 0 additive; Adjusting the viscosity, the surface tension and the viscosity to prepare an ink composition (S21); And filtering the prepared ink composition with an inline member lane using a fine filter paper (S22); Printing step S23; Dyeing step S24).

One. In step S11,

Examples of the selected material of the ink coloring matter (functional material) and the vehicle fluid are as follows, but are not limited thereto.

blue

Pigment phosphorescent (fluorescent) material: C.I. Pigment Blue 15; C.I. Pigment Blue 15: 1; C.I. Pigment Blue 15: 2; C.I. Pigment Blue 15: 3; C.I. Pigment Blue 15: 4

Dye phosphorescent (fluorescent) material: C.I. Direct Blue 190; C.I. Direct Blue 191; C.I. Direct Blue 192

Natural phosphorescent material: Anthocyanin, Fe-Phthalocyanine, Luminol

Red

Pigment phosphorescent (fluorescent) material: C.I. Pigment Red 48; C.I. Pigment Red 48: 1; C.I. Pigment Red 48: 2; C.I. Pigment Red 122; C.I. Pigment Violet19

Dye phosphorescent (fluorescent) material: C.I. Acid Red 84; C.I. Acid Red 87; C.I. Reactive Red 23

Natural phosphorescent material: Carmine A; Carmine B

green

Pigment phosphorescent (fluorescent) material: C.I. Pigment Green 7, C.I. Pigment Green 36, Cu-Phthalocyanine,

Natural phosphorescent material: Luciferin

black

Pigment: C.I. Pigment Black 7, direct dye: Poly azo; Poly Phenol, Natural Dyes: Sepia color, Polypyrrole, Graphene, Fullerene, Graphite, Tannonanotube

White

C.I. Pigment White 6 (Rutile Titanium Dioxide, CI Pigment White 7 (Anatase-type Titanium Dioxide, CI Pigment White 31

etc

Pigment: CI Pigment Violet 23, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Green 7, CI Pigment Green 36, Phthalocyanine, Basic Nile 4, Basic Violet 3, 10b, Disperse Red 1, Disperse Orange 3, 7, Qinacrydione, NLO and Intermediates, Zinc, Sulfide, Fluoresein, polymers and Intermediates, Indole polymers and Intermediates, White Carbon, Lithopone, Fe, Cu, Ag, Au, ZnPhtalocyanine, Luminol , Carmine A, Carmine B, Luciferin, Polyazo Poly Phenol, Titanium dioxide (Rutile, Anatage), Zinc Oxide, Indium Tin Oxide, Tin Oxide, Antimony, Germanium, Carbon, Lithopone, Aluminum Oxide, Gold, Silver, Chopper, Fe _{2 O 3, Lithium, Magnesium, Barium} sulfide, CNT (Carbon Nano Tube, DWCNT, SWCNT, MWCNT), Nanowire, Dendrimer, Graphene, FullereneC60, 61, 70, 74, 84, 90, Poly Thiphene Group (PEDOT, PEDOTPOSS / PSS , PADOT, PT, P3HT, F8T2), Poly Acetylene, Poly Pyrrole, Poly Phenylene Vinylene Group, Poly Vinylene Carbazole, Poly Sprayole, Poly acene, Poly a nylon, Polyglutamate, Iridium, Hafnium, Polyimide, Polyphenyl Sulfide, Fluorescein, TCNQ (Tetracyanoquinodimethane), TCNQTTF (Tetrathiafulvalene), Transfer Metal Group, Alkali Metallic Salt, Cumarin, Cinnamate, NonLinear Polymer, Photo Chromic, Electro Chromic, Chemical Chromic, Poly Imine, Poly N-iso amide (Nylon), Poly Sulfone, Poly Sulfide, Pentacene, Germanium, Gallium

 The fluid was also designed to obtain a dynamically stable polymer of the ink vehicle polymerization fluid.

First, a pressure sensitive adhesive element, such as the following Molecular formula-1, was constructed for adhesion of the platelets in the fluid polymer of the ink vehicle fluid.

 <Molecular formula-1>

Examples of the monomer that can be used as the monomer include Ethylacrylate, Ethylhexylacrylate, Butylacrylate, Propylacrylate, Acrylic acid, Methacrylic acid Hydroxyethylacrylate, Hydroxypropylacrylate, Hydroxybutylacrylate, Ethylene glycol acrylate, Diethylene glycol acrylate, triethylene glycol acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol acrylate, pentaethylene glycol acrylate, ethylene glycol triacrylate, triethylene glycol triacrylate, tetraethylene glycol triacrylate, propylene glycol acrylate, dipropylene glycol acrylate , Tripropylene glycol acrylate, Tetrapropylene glycol acrylate, Propylene glycol diacrylate, Dipropylene glycol diacrylate, Tripropylene glycol diacrylate, Tetrapropylene glycol diacrylate, Propylene glycol triacrylate, Dipropylene glycol triacrylate, Tripropylene gly col triacrylate, and tetrapropylene glycol triacrylate. However, the present invention is not limited thereto.

Examples of the monomer used in the polymerization include methylmethacrylate, styrene, hydroxyethylmethacrylate, hydroxypropylmethacrylate, hydroxybutylmethacrylate, isobutylmethacrylate, N-methyl-iso-acryloamide, N- -butoxymethyl) Acrylamide, Butylmethacrylate, Glycidylmethylmethacrylate, Ethylacrylate, Ethylhexylacrylate, Butylacrylate, Propylacrylate, Hydroxyethylacrylate, Hydroxypropylacrylate, Hydroxybutylacrylate, Ethylene glycol acrylate, Ethylene glycol acrylate, Ethylene glycol diacrylate, Triethylene glycol diacrylate, Tetraethylene glycol acrylate , Pentaethylene glycol acrylate, Ethylene glycol triacrylate, Diethylene glycol triacrylate, Triethylene glycol triacrylate, Tetraethylene glycol triacrylate, Propylene glycol acrylate, Dipropylene glycol acrylate, Tripropylene glycol acrylate, Tetrapropylene glycol a polytrimethylene terephthalate, polytrimethylene terephthalate, polytrimethylene terephthalate, polytrimethylene terephthalate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, But are not limited to, polypyrometallic amic acid, N-methylolacrylamide, polyimine, polyethylene imine, imidazole, Urea, Uracil, melamine, polyethylene glycol-graft-epoxy, polyimide, polyphenyl sulfide and N-isopropylacrylamide.

Examples of the monomer which can be used in the case of the functional groups R2 and R3 include methylmethacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, hydroxybutylmethacrylate, isobutylmethacrylate, N-methyl-iso-acrylamide, N- iso-butoxymethyl acrylamide, butylmethacrylate, glycidymethylmethacrylate, glycol, methyl ether methacrylate and the like, but are not limited thereto.

In addition, a high temperature curing adhesive material, such as the following Molecular formula-2, was constructed on the fluid polymer of the ink vehicle fluid.

 <Molecular formula-2>

The oligomers used in the functional groups of R1 were mainly used as polyacrylate and polyacrylic acid, and silica of PSS and TEOS was used for polymerization. Examples of the monomer that can be used as the monomer include a monomer selected from the group consisting of ethylene phenyl acrylate, polyethylene acrylate, polydiethylene acrylate, polystyrene acrylate, polyethylene diacrylate, polydiethylene diacrylate, polydipropylene diacrylate, polydipropylene diacrylate, polydipropylene diacrylate, polydipropylene acrylate, (D, L-Lactide), Hyaluronic acid, and the like. However, it is not limited to these materials, and examples thereof include polyacrylic acid, polymethyl methacrylic acid, polymethyl acrylic acid, polymethyl methacrylic acid, polysilsesquioxane, tetraethyl orthosilicate, zirconium acrylate, hafnium acrylate, polypropylacrylic acid, bisphenol A acrylate, It is not.

Poly methacrylate and hydrocarbon fluoride are used as the functional groups of R2. Examples of the monomer that can be used as a monomer include polyethylene glycol methacrylate, polyethylene glycol methacrylate, polydiethylene glycol amethacrylate, polytriethylene glycol methacrylate, polyethylene glycol dimethacrylate, polydiethylene glycol dimethacrylate, , Polypropylene glycol methacrylate, Polydipropylene glycol acrylate, Polytripropylene glycol methacrylate, Polypropylene glycol dimethacrylate, Polydipropylene glycol dimethacrylate, Polytripropylene glycol dimethacrylate, Polyethyl acrylamide, Polyethyl methacrylamide Polyglycolide, Acrylic acid, Polymethyl methacrylic acid, Bisphenol A dimethacrylate, Methacrylate, indium tin methacrylate, Iridium methacrylate, Cyclopenta methacrylate, Polypropylene carbonate, Polystyrene-graft-methacrylate, Polybutylic acid, Polyisopyrene, Polyisobutylene, Poly isocyanate , Polyhexadicyanate, benzyl methacrylate, and the like, but are not limited thereto.

2. Material purification step (S12)

In order to precisely polymerize the synthesis and the polymer, the purity of the material to be added should be maintained. Since the monomers used must maintain extremely extreme purity, they are passed through a Sea sand column (diameter: 15 mm, length: 300 mm) and transferred to a cotton column (diameter: 15 mm, length: 300 mm) before fractional distillation Afterwards, polymerization inhibitors were removed from the Inhibite remover column (306312, 306320, Sigma-aldrich) to remove the polymerization inhibitor and the polymerization was stopped by using a light-shielded triple fractionation distillation apparatus (Z748293, Z748307, Z748135 from Sigma-aldrich) The purity is 99.999999999%, and extracted for extraction (64824, 64825, 64826, Sigma-aldrich).

The extracted high purity monomers were stored in a glass container shielded from direct sunlight using Molecular Sieves (334448, Sigma-aldrich) and refrigerated. The procedure for purification of the oligomer is as follows. Excessive purification causes a change in the properties of the oligomer itself. Therefore, a sea column (diameter: 15 mm, length: 300 mm) , The polymerization inhibitor was removed using an Inhibite remover column (Sigma-aldrich Corp. 306312, 306320) and stored in a light-shielded container together with molecular sieves and refrigerated.

  The pre-oligomer was stored in a refrigerator with Molecular Sieves using a sea sand column (diameter: 15 mm, length: 300 mm) and a cotton column (diameter: 15 mm, length: 300 mm).

  The polymer was filtered using an in-line polypropylene membrane filter (GE Polycap HD) and stored at room temperature with the light shielded with molecular sieves.

In the case of the initiator dissolved in water, the initiator was dissolved in methanol and recrystallized using an extraction device (64824, 64825, 64826, Sigma-aldrich) and refrigerated.

In the case of the initiator not soluble in water, it was dissolved in n-hexane and recrystallized using an extraction device (64824, 64825, 64826, Sigma-aldrich)

In the case of an initiator dissolved in a water system, a coloring agent was dissolved in a solvent having a pharmacological property and recrystallized using an extraction device (Sigma-aldrich 64824, 64825, 64826) and stored at room temperature.

In the case of the chromophore not soluble in water, it was dissolved in fuming sulfuric acid and recrystallized using an extraction device (64824, 64825, 64826, Sigma-aldrich) and stored at room temperature.

The remaining synthetic-polymerization additives were high purity reagents from Sigma-aldrich.

3. Synthesis - The polymerization step (S13)

The synthesis-polymerization process was carried out by computer using an automated high-speed reactor (IKA PREMIX Reactor) set to disperse directly into the medium without recycling or washing of the polymer in the water, non-water (vegetable oil) system.

The synthesis-polymerization process involves the precise synthesis-polymerization reaction of transition metal (metallocene) substitution and living ion polymerization (ATRP), inverse irregular segment addition polymerization (RAFT), metal nitrogen oxide polymerization (NMO) , Group transfer polymerization (GTP)) were simultaneously used in the synthesis-polymerization process.

 In the present invention, the pigment is preferably selected from the group consisting of Sunhoon: quinacridone, cyan: phthalocyanine, yellow: benzoimidazoline, and black: carbon black. As dye dyes, it is preferable to select dyes: quinine dyes, cyan dyes: anthraquinone dyes, yellow: imine dyes dyes, and black: white carbon dyes.

Synthesis Example 1

The pigments and dyes were mixed in a ratio of 50 wt% of pigment (CI Pigment Blue 15: 3) and 50 wt% of dye (CI Disperse Blue 60) in 30 wt% color (blue) 40 wt% of methylpyrrolidone, 20 wt% of a copolymerized dimethylsulfoxide, and 5 wt% of tetrabutyl alcohol as an nonsolvent.

To the mixed solution containing the pigment and the dye, 2 wt% of silver and 3 wt% of copper are added to the continuous catalyst, and a salt-pigment copolymerized pigment is synthesized in a reactor heated to 100 ° C in a Ziegler-Natta reaction.

 In the next step, 100 ml of a solution prepared by mixing 0.1 N hydrochloric acid solution and 0.5 N sulfuric acid solution (V / V%) in a ratio of 1: 1 was added dropwise at a rate of 2 ml per minute to the synthetic pigment cooled at 60 ° C. N NaOH solution is added dropwise at a rate of 1 ml per minute. The dye-pigment colorant blended by the ligand reaction is converted to quasicrystallization (blocky). To neutralize the semi-crystallized synthetic colorant, 1 ml of 1N lithium hydroxide is added dropwise at 1 ml per minute, and 25 ml of an aqueous 0.1 N biscarbonate or disodium sulfonate aqueous solution as an oxidation-reduction agent is added dropwise at 1 ml per minute to synthesize a salt-pigment copolymerized colorant. Liquid-liquid separation, washing with water, and drying by precipitation using titanium, silicon, aluminum, zinc or the like whose terminal is substituted with halogen.

Synthesis Example 2

In another synthesis method of the present invention, 10 wt% of Char coal, 5 wt% of Ethylenedioctyl thiopene, 5 wt% of pyrrole and 5 wt% of aniline were mixed with 40 wt% of dimethylsulfoxide as a water-based quantum solvent under a nitrogen atmosphere, After adding 5 wt% of 2-pyrrolidone and 5 wt% of non-covalent methyl alcohol, 1 wt% of Au catalyst and benzyl peroxide (UV) initiator peroxide (BPO) and 0.1 wt% of free radical initiator (2,2-Azobis (2methylpropion) dihydrodicholoride: V-50) were added and stirred at 600 rpm for 6 hours. And photopolymerized at an ultraviolet wavelength of 253 nm for 24 hours to form nano spherical particles having electric conductivity.

Polymerization Example 1

(2.5 wt%), acrylonitrile (0.5 wt%), which is a monomer, for polymerizing and preparing an ink vehicle fluid having various phases in the form of water-in-oil type (O / W) , Monomers composed of methyl methacrylate (1 wt%), TEOS (100 ppb), hydro-ethyl methacrylate (8 wt%) and acrylic acid (4 wt%) were mixed in advance, (80wt%) polymerization mixture as a continuous and discontinuous solvent in the degassing of argon was added to the reactor, and a mixture of Pluornic L-60 (PEO / PPO) -based polymeric surfactant (0.65wt%) and sodium lauryl Sulfate (0.35wt%) reactive anionic surfactant is added to the reactor, and 1,2-propylene glycol (10wt%), which is an emulsifier, is added while degassing for 30 minutes. After the emulsifier was added, the temperature of the reactor was raised to 65 ° C for 30 minutes, and then the temperature of the reactor was stabilized at 65 ° C with the previously mixed monomers (2,2-Azobis (2methylpropion) dihydrodicholoride: V- ), vinyl acetate (0.1 wt%), benzoyl peroxide (0.025 wt%), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (0.025 wt%) and dimethyl sulfoxide (2.7249999 wt% The impeller speed is maintained at 8000 rpm. The emulsion of the polymerized fluid is gradually cooled for 150 minutes to terminate the polymerization.

Polymerization Example 2

According to another embodiment of the present invention, there is provided a process for the polymerization of styrene monomer (2.5 wt%), acrylonitrile (0.5 wt%), , Dimethyl methacrylate (1 wt%), PDMS (100 ppb), hydro-ethyl methacrylate (8 wt%) and methacrylic acid (4 wt%) were mixed and prepared. (80% by weight) of soybean oil (80 wt%) as a continuous and discontinuous solvent in the degassing of argon was added to the reactor, and a mixture of Pluornic F127 (PEO / PPO) reactive type polymer surfactant (0.65 wt%) and sodium bis -ethylhexyl) (di, mono) sulfosuccinate (0.35wt%) The reaction type anionic surfactant is added to the reactor, and glycerol (10wt%), which is an emulsifier, is added while maintaining degassing for 30 minutes. After the emulsifier was added, the temperature of the reactor was raised to 65 ° C for 30 minutes, and then the temperature of the reactor was stabilized at 65 ° C together with the previously mixed monomers (2,2-Azobis (2methylpropion) dihydrodicholoride: V- ), 2,6-trimethylbenzoyldiphenylphosphine oxide (0.025 wt%) such as vinyl acetate (0.1 wt%) 2,2 and -Azobisbutylnitrile (0.025 wt%) and n-propane alcohol (2.7499999 wt% Min and the impeller speed of the reactor is maintained at 8000 rpm. The emulsion of the polymerized fluid is gradually cooled for 150 minutes to terminate the polymerization.

Polymerization Example 3

According to another suitable embodiment, a high molecular weight organic / inorganic hybrid polymer supercritical fluid in the form of a subnano-suspension in the form of water can be prepared by polymerizing monomers such as styrene (2.5 wt%), acrylonitrile (0.5 wt% (1 wt%), TEOS (100 ppb), hydro-ethyl methacrylate (8 wt%), acrylic acid (2 wt%) and methacrylic acid In the degassing of nitrogen, dimethyl ether sulfone (2.6749999 wt%) and co-solvent TBA (0.025 wt%) as a solvent were added to the reactor and degassing was carried out for 30 min. (2methylpropion) dihydrodicholoride: V-50 (0.05wt%) and vinyl acetate (0.1wt%) at 65 ° C together with the mixed monomer in the process of rising to 65 ° C for 30min. wt%) Benzoyl peroxide (0.025 wt%) The polymerization was terminated by gradually cooling the suspension of the polymerized fluid for 120 minutes. The polymerization was terminated by slowly cooling the polymerized suspension for 120 minutes.

When each of the five different types of polymerization is cooled to room temperature, the polymerization is terminated by using a combination of SFS: TBHP as a polymerization terminator or using a combination of HPO: Ascorbic acid. The combination ratio of SFS: TBHP, HPO: Ascorbic acid is 1: 1, and the polymerization reaction is terminated by adding 0.05 to 0.1 (wt%) to the total polymerization ratio of the polymerization mixture.

High molecular weight organic / inorganic hybrid polymer of the final reaction solution The particles of the supercritical fluid have a uniform size of 1 to 2 nm on average and a very monodispersed three-dimensional particle shape with a dispersion index of 1.00 to 1.01. The average It has a weight-average molecular weight of 150,000 and a molecular weight range of 120,000 to 200,000.

4. Physical property adjustment step (S14)

This is the third important step of the final physical property effect in the present invention. Since the polymerization solution polymerized in the polymerization step is a very strong acidic solution in the final pH range of 1.0 to 3.0, adjust the pH to adjust the static viscosity and dynamic viscoelastic complexity so that hydrogen bonding or acidic atmosphere Sodium phosphate or potassium phosphate may be dissolved in 0.1 to 1 N of ultrapure water alone, or both of them may be mixed and dissolved in ultrapure water in an amount of 0.1 to 1 N in order to remove the factor of self-agglomeration.

Fine adjustment of the pH is carried out using boric acid and citric acid and is mainly used as anhydrous. The acid anhydrides used for the fine tuning of the pH can be mixed with the pH adjusting solution. However, the pH range is adjusted from 8.2 to 10.2 and the range used for the pH adjuster of acid anhydrides is 5 ~ 10 (v / v%) compared to sodium phosphate or potassium phosphate.

5. Platelets (or synthetic Functional material ) And ink Vehicle  Fluid Blend  In step S15,

The mixing step of the selective material is the same as the method of manufacturing the dispersed undiluted solution of the patent registered and disclosed in the patent application due to the invention of the present invention.

Examples include the preparation of optional ingredients and mixed solutions of 1 kg each in order to see the characteristics of polymerized fluids prepared in the synthesis-polymerization step and polymerized fluids of the following composition ratios.

Production Example 1

The dye of Synthesis Example 1: 250 g

Fluid of Polymerization Example 1: 125 g

Fluid of Polymerization Example 2: 125 g

Fluid of Polymerization Example 3: 125 g

Ultrapure water: balanced.

Production Example 2

The dye of Synthesis Example 1: 250 g

Fluid of Polymerization Example 1: 125 g

Fluid of Polymerization Example 3: 125 g

Ultrapure water: balanced.

Production Example 4

The dye of Synthesis Example 1: 250 g

Fluid of Polymerization Example 2: 150 g

Fluid of Polymerization Example 3: 125 g

Ultrapure water: balanced.

Production Example 5

Functional material of Synthesis Example 2: 250 g

Fluid of Polymerization Example 1: 125 g

Fluid of Polymerization Example 2: 125 g

Fluid of Polymerization Example 3: 125 g

Ultrapure water: balanced.

Production Example 6

Of Synthesis Example 2: 250 g

Fluid of Polymerization Example 1: 150 g

Fluid of Polymerization Example 2: 125 g

Fluid of Polymerization Example 3: 125 g

Ultrapure water: balanced.

The blend phase is prepared with Air 99.99% nitrogen-lowered Degassing from Airproducts at room temperature 10 ° C for 14-24 hours.

6. At room temperature Atmospheric pressure  Ha Homogenization  In the dispersing step (S16)

Using a homogenizer IKA UD-200, the five blends in the mixing stage were each agitated at a high speed of 26,000 rpm with 99.99% argon-deagassing by Airproducts.

7. milling Rearrangement  In the dispersing step (S17)

The step of dispersing the milling rearrangement of the selective material is the same as the method of manufacturing the dispersion master stock solution of the patent application registered, filed and published in addition to the invention application.

 A zirconium-silicon carbide-hafnium bead of 0.03 to 0.1 mm is placed in the milling machine and rotated at a speed of 2000 to 16000 RPM to uniformly disperse the coloring matter and the polymer (milling time 90 min / 1 Kg). Through such a milling process, a dispersion master stock solution having a monodisperse distribution is produced. In this process, it is preferable that the beads are injected at 60 to 90% of the total volume of the chamber of the milling machine. For the milling work, we can use a machine that has super high-speed milling by using zirconium-silicon carbide-hafnium beads on a commercial wet milling equipment such as Super Nano mill of Nano in-Tech which is commercially available.

The finely finished particles of each master stock have an average size of 0.7 to 1 nm and an average dispersion index of 1.00 to 1.03. The average molecular weight by GPC measurement is 200,000 and the molecular weight range is 180,000 ~ 220,000.

8. Letdown  In step S18,

The master dispersion stock prepared in the previous step was prepared by mixing in IKA Inline T-65. And diluted with the following composition ratio.

The following optional ingredients and 1.2 to 1.5 kg of letdown solution are included.

Production Example 7

Production Example 1 Raw liquid: 1000 g

Ultrapure water: 500 g

Production Example 8

Production Example 2 Liquid: 1000 g

Ultrapure water: 250 g

Production Example 9

Production Example 3 Raw liquid: 1000 g

Ultrapure water: 250 g

Production Example 10

Production Example 4 Raw liquid: 1000 g

Ultrapure water: 200 g

Production Example 11

Production Example 5 Raw liquid: 1000 g

Ultrapure water: 500 g

Production Example 12

Production Example 6 Raw liquid: 1000 g

Ultrapure water: 500 g

It has a uniform size of 1 ~ 2nm on average of the particles in each final solution. The dispersion index is in the form of a very monodisperse three-dimensional ellipsoidal particle of 1.00 ~ 1.01, a viscosity of 150 ~ 250 cPs, and a pH of 8.6 ~ 9.6.

9. Ink Formula  step

The letdown solution prepared in the previous step was made into ink using an IKA Eurostar mechanical stirrer. The composition was prepared as follows.

Includes examples of the following optional element materials and inks.

Production Example 13

Manufacturing 7 liquid: 250g

Diethylene glycol: 50 g

Glycerin: 80g

Ultrapure water: 620 g

Production Example 14

Manufacturing 8 liquid: 250g

Triethylene glycol: 50 g

Glycerin: 80g

2-Pyrrolidone: 20 g

Ultra pure water: 600g

Production Example 15

Manufacturing 9 liquid: 300g

Diethylene glycol methacrylate: 100 g

Poly (ethylene glycol) methyl ether methacrylate solution: 80 g

Hydroxyethyl methacrylate: 320 g

Ultrapure water: 300 g

Production Example 16

Manufacturing 10 liquid: 250g

Poly (ethylene glycol) methyl ether methacrylate solution: 100 g

Hydroxyethyl methacrylate: 320 g

Ultrapure water: 330 g

Production Example 17

Manufacturing 11 liquid: 200g

Polyethylene oxide 1wt% in Water solution: 400g

Poly (ethylene glycol) methyl ether methacrylate solution: 60 g

Hydroxyethyl methacrylate: 240 g

Ultrapure water: 100 g

Production Example 18

Manufacturing 12 liquid: 200g

Polyethylene oxide 1wt% in Water solution: 400g

Poly (ethylene glycol) methyl ether methacrylate solution: 60 g

Hydroxyethyl methacrylate: 240 g

Ultrapure water: 100 g

Production Example 19

Manufacturing 7 liquid: 100g

Manufacturing 8 liquid: 100g

Diethylene glycol: 50 g

Glycerin: 80g

Hosta copy Chage N4P M101 (Clariant GmBH): 30g

Ultrapure water: 740 g

Production example 20

Manufacturing 7 liquid: 50g

Manufacturing 8 liquid: 50g

Polyethylene oxide 1wt% in Water solution: 400g

Poly (ethylene glycol) methyl ether methacrylate solution: 60 g

Hydroxyethyl methacrylate: 240 g

Hosta copy Chage N4P (Clariant GmBH): 30g

Ultrapure water: 270 g

10. Ink filtration step (S22)

The ink composition produced by the present invention filters out impurities generated in the manufacturing process or mixed impurities by a filtration process, and filters particles having a certain size or more. The filtration process is performed by ultrafiltration (3 μm or less), microfiltration (500 nm or less), selective ultra-fine filtration (100 nm or less) using Millpore or General Electric products, filtration by vacuum do. Through the filtration process, the ink composition is uniform in its entirety and has a stable particle size.

11. Printing step (S23)

The printing method can be used with all existing printing methods such as screen printing, flexo printing, nanoimprinting, LIFT, LCVD, CVD, PECVD, TFT-CVD, DOD inkjetting, continuous inkjetting, spin coating, .

12. Staining step (S24)

Existing high-pressure infrared dyeing machine or low-pressure medium infrared dyeing machine can be applied to dyeing.

Embodiments which do not limit the scope of the present invention are presented below.

Example 1

Production Example 13 has a surface tension of 35 dyne / cm; Viscosity 3.2 cPs; And pH 8.4. Epson's Stylus Pro 9400, Hewlett Packard Designer jet z2100, and Canon's Canon IPF 700.

Example 2

Production Example 14 has a surface tension of 35 dyne / cm; Viscosity 2.8 cPs; And a pH of 8.3. Epson's Stylus Pro 9400, Hewlett Packard Designer jet z2100, and Canon's Canon IPF 700.

Example 3

Production Example 15 has a surface tension of 30 dyne / cm; Viscosity 2.9 cPs; And pH 8.2. Epson's Stylus Pro 9400, Hewlett Packard's Designer jet z2100, and Canon's Canon IPF 700.

Example 4

Production Example 16 has a surface tension of 30 dyne / cm; Viscosity 2.8 cPs; And pH 8.5. Epson's Stylus Pro 9400, Hewlett Packard's Designer jet z2100, and Canon's Canon IPF 700.

Example 5

Production Example 17 has a surface tension of 28 dyne / cm; Viscosity 3.5 cPs; And pH 8.2. Epson's Stylus Pro 9400, Hewlett Packard's Designer jet z2100, and Canon's Canon IPF 700.

Example 6

Production Example 18 has a surface tension of 26 dyne / cm; Viscosity 2.9 cPs; And pH 8.4. Epson's Stylus Pro 9400, Hewlett Packard's Designer jet z2100, and Canon's Canon IPF 700.

Example 7

Production Example 19 has a surface tension of 27 dyne / cm; Viscosity 3.8 cPs; And pH 8.8. Epson's SureLab D3000, and Hewlett Packard's Indigo Digitalpress 3550 output device were able to print 1000 A4 pages at a glance.

Example 8

Production Example 20 has a surface tension of 27 dyne / cm; Viscosity 4.0 cPs; And a pH of 8.9. Epson's SureLab D3000, and Hewlett Packard's Indigo Digitalpress 3550 output device were able to print 1000 A4 pages at a glance.

Example 9

Example 1 was directly printed on the untreated cotton fabric and pretreated cotton fabric, then heated to 60 ° C for 30 minutes with a high-pressure IR dyeing machine and stained at 100 ° C for 10 minutes.

Comparative Example  One

To 750 g of distilled water was added 50 g of styrene / acrylate polymer, Direct Blue 190, and 250 g were put into a bead mill and milled for about 8 hours to prepare a reactive dye-dispersing stock solution having an average particle size of about 70 nm. The following reactive chemicals were added to the obtained blue dispersion stock solution to prepare an ink composition.

 16 wt% to 20 wt% of a reactive dye-containing undiluted solution;

16 wt% to 20 wt% ethylene glycol;

DMSO 2 wt%; and

Distilled water 46 wt% to 54 wt%;

 The produced reactive dye inks were tested for output from Epson's Stylus Pro 7900, Hewlett Packard Designer jet z3200, and Canon's Canon IPF 8000. In the course of the test, some nozzles were removed, and after the curing process, the color reproduction (according to CIE Lab 1976 of the International Lighting Society) was less than that of Examples 1, 7 and 8 in the washing process.

Comparative Example  2

To 750 g of distilled water was added 50 g of a naphthalene copolymer, And Disperse Blue 60, each of which was sufficiently stirred. The dispersion solution thus prepared was put into a bead mill and milled for about 8 hours to prepare a blue dispersion stock solution having an average particle size of about 100 nm. The following reactive chemicals were added to the obtained dispersion liquid of the CDP-type dispersed sublimation dye to prepare an ink composition.

 CDP type dispersion sublimable dye dispersion stock solution 18 wt% to 20 wt%;

18 wt% to 20 wt% diethylene glycol;

DMSO 2wt%;

NaOH 4 wt%; And

Distilled water 50 wt%

 Output test was performed on output ink of Epson's Stylus Pro 7900, Hewlett Packard Designer jet z3200 and Canon IPF 8000 for the transferred ink. During the test process, a small amount of nozzles did not come off. During the curing process, the harmful substances were not discharged, but a small amount of methane gas generated increased the yellowing of the printed matter and the air pollution in the indoor space. Later, the color reproduction was similar to that of Examples 1, 7 and 8 in the washing process, but it was lower than the standard in the durability test.

Comparative Example  3

Styrene / acrylate / methyl methacrylate polymer and Airproduct surfynol-CT 171, BYK disper-180, Degussa tego-750, 760 were added to 600 g of distilled water. Pigment Blue 15: 3 (250 g) was added and stirred sufficiently. The dispersion solution thus prepared was put into a bead mill and milled for about 8 hours to prepare a pigment dispersion stock having an average particle size of about 50 nm. The following reactive chemicals were added to the obtained pigment dispersion stock solution to prepare an ink composition.

 24 wt% pigment stock solution;

10 wt% diethylene glycol;

20 wt% dipropylene glycol;

6 wt% glycerol; and

Distilled water 50 wt%

 The produced ink was subjected to an output test on output devices such as Stylus Pro 7900 from Epson, Hewlett Packard Designer jet z3200 and Canon IPF 8000 from Canon. During the test process, a small amount of nozzles did not come off. During the curing process, the harmful substances were not discharged but a small amount of methane gas was generated, which increased the yellowing of the printed matter and the air pollution in the indoor space. The color reproducibility and abrasion resistance were lower than those of Example 2 in the washing process.

Comparative Example  4

C.I. Pigment Blue 15: 3 (250 g) was added and stirred sufficiently. A dispersion stock solution having an average particle size of about 50 nm was prepared. The petroleum diluted ultraviolet ray curable ink composition was prepared by adding the following reaction chemicals to the resulting pigment dispersion stock solution.

 Pigment dispersion stock solution 12 wt%;

50% by weight of aryl glycol;

Dendrimer 7 5 wt%;

Irgacure 819 5 wt%; and

N-vinylfluorene 28 wt%

 The produced petroleum diluted ultraviolet curing ink was subjected to output tests on output devices such as Stylus Pro 7900, Hewlett Packard Designer jet z3200 and Canon IPF 8000 from Epson. During the test process, there was no dropout of the nozzle and the air pollution in the indoor space was increased due to the generation of a small amount of methane and carbon dioxide gas, though not the emission of harmful substances during the curing process. In comparison with Example 3, the washability and the light resistance test were very good in the washing process, but the color reproduction and the frictional resistance were not good.

Comparative Example  5

In order to compare dyeing of Comparative Example 1 ink with Example No. 9, a cotton fabric pretreatment solution was prepared through a recommended guide of Mimaki Co., LTD (Japan).

Sodium alginate 2wt%;

Urea 7wt%;

Baking soda 3wt%;

Sunflowren SN (fluorescent whitening agent) 1wt%;

6 Sodium Phosphate: 1 wt%;

Fluorescent disperse dye: 1 wt%;

Ultra pure water: 85 wt%

And stained with a high-pressure IR dyeing machine in the same manner as in Example 9. The color density of the non-preprocessed cotton fabric was excellent in Example 9, and was equivalent in terms of washing and rubbing fastness.

Example 9 was superior in light fastness to light. In the pretreated cotton fabric, the color density was the same and the washing and rubbing fastnesses were the same, but the light fastness was lower than in Example 9.

The present invention has been described in detail by showing embodiments. The embodiments presented are illustrative and those skilled in the art will be able to make various modifications and alterations to the disclosed embodiments without departing from the spirit of the invention. The present invention is not limited by these variations and modifications, but is limited only by the claims appended hereto.

Claims (5)

Selecting a dye material and a polymer material;
Purifying the dye material and the polymer material;
Oil-inorganic synthesizing the purified pigment material, and polymerizing the purified polymer material into an ink vehicle;
Adjusting the physical properties of the ink vehicle;
Mixing the compounded pigment with a physically controlled ink vehicle;
Dispersing the mixed ink vehicle and the synthesized pigment in a homogenized dispersion at normal temperature and pressure; And
And mixing the dispersed substance with zirconium-silica-hafnium alloy beads to rearrange the molecules of the dispersed substance to prepare a master stock solution. The method according to claim 1,
A letdown step of diluting the master stock solution with a diluting solvent;
Adjusting the viscosity and the surface tension according to the amount of the additive to prepare an ink composition; And
Further comprising the step of filtering the ink composition with a membrane filter. The method according to claim 1,
Wherein the polymeric material comprises the following formula (1) and formula (2).
[Chemical Formula 1]

(2)

(Wherein R ₁ , R ₂ and R ₃ are acrylic or methacrylic functional groups). The method according to claim 1,
Wherein the dispersed material contained in the master stock solution has an average particle size of 0.7 to 1 nm. An ink composition which is produced by the production method according to any one of claims 1 to 4 and does not produce a chemical harmful to the environment.

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