KR20210052793A - An organic fluorescent pigment dispersion and method for preparing an organic fluorescent pigment dispersion - Google Patents

Abstract

The present invention relates to a formaldehyde-free aqueous fluorescent pigment dispersion composition and a method for manufacturing the same, and specifically, to a dispersant composition including: an organic fluorescent pigment in which formaldehyde-free resin fine particles are colored with a dye; (b) pigment dispersants; and (c) water, and to a method for manufacturing an organic fluorescent pigment dispersion composition, including the steps of: mixing (a) an organic fluorescent pigment, pigment dispersants, and water; and manufacturing an organic fluorescent pigment dispersion using a bead mill. The formaldehyde-free organic fluorescent pigment dispersion according to the present invention is particularly useful for inkjet inks.

Description

Manufacturing method of organic fluorescent pigment dispersion and organic fluorescent pigment dispersion {AN ORGANIC FLUORESCENT PIGMENT DISPERSION AND METHOD FOR PREPARING AN ORGANIC FLUORESCENT PIGMENT DISPERSION}

The present invention relates to a method for preparing a dispersion comprising a formaldehyde-free organic fluorescent pigment dispersed in an aqueous liquid medium. Specifically, the present invention (a) formaldehyde-free organic fluorescent pigment; (b) a pigment dispersant; And (c) an organic fluorescent pigment dispersion comprising water, and to the use of the organic fluorescent pigment dispersion in ink, particularly inkjet printing inks.

Conventional ink used in the inkjet recording method has been mainstream in which various water-soluble dyes are dissolved in water alone or in a solvent composed of water and a water-soluble solvent, and various additives are added as necessary. However, in the case of printing using such a dye-based ink, there is a problem in that the water resistance of the recorded image on the recording medium is low, so that dye bleeding occurs, or due to the low light resistance, a change in color tone or a decrease in density occurs due to light.

In order to improve the above problems of dye-based inks, it is known to apply so-called pigment-based inks using carbon black or various organic pigments as a colorant to an inkjet recording method. When printing is performed using a pigment-based ink, the ink dried on the recording medium does not dissolve or bleed in water, so that the water resistance is good. In addition, since the pigment is less reactive to light than the dye, the light resistance of the pigment-based ink is superior to that of the dye-based ink.

Such pigment-based inks are generally prepared by adding various additives to a pigment dispersion prepared by dispersing a mixture consisting of a pigment, a liquid medium, and a dispersing agent with a dispersing machine such as a ball mill or a sand mill. Pigment dispersions used in inkjet recording inks contain pigment particles in pigment dispersions up to a particle diameter level of 200 nm or less in order to prevent clogging of the nozzles of a printing device (inkjet printer), clarity of printed images, secondary color reproduction, and securing transparency. It is necessary to micronize and disperse. In addition, it is known that when fine particles are made to the level of a particle diameter of 50 nm or less, a high chroma and high transparency image close to that of a dye ink can be formed.

Pigment dispersions containing fine particles of pigment particles used in inkjet inks are prepared by various methods using polymer dispersions, self dispersions, encapsulation dispersions, and the like.

In addition to Cyan, Magenta, Yellow, and Black, which are used as the basic four colors of inkjet pigment inks, the color gamut can be widened by using inks such as Orange, Green, Red, Blue, Violet, and Fluorescent as spot color inks.

In particular, fluorescent inks have higher visibility than non-fluorescent inks, because fluorescent dyes change the wavelength of part of the absorbed light energy together with the reflected light from the incident light source to be radiated. Therefore, fluorescent inks are easily recognized by humans due to their high visibility, and are widely used as propaganda advertisements, signs for alerting, and point colors.

Conventionally, organic fluorescent pigments used in aqueous fluorescent paints or aqueous fluorescent inks are amorphous resin particles obtained by dyeing a compound such as formaldehyde and melamine, and a compound such as toluene sulfonamide with a fluorescent dye and performing a cocondensation reaction. It is about 1.5 to 10.0 μm (refer to Patent Documents 1, 2, and 3).

In addition, there are also organic fluorescent pigments having an average particle diameter of about 0.05 to 1.50 μm by emulsion polymerization of acrylonitrile and styrene-based monomers in water (refer to Patent Documents 4 and 5).

These fluorescent pigments are used alone or in combination as an aqueous fluorescent composition composed of a binder, water, and other additives. However, the former has high color concentration and fluorescence intensity, but contains formaldehyde, which has a strong odor, which has problems in terms of environment and safety, has a specific gravity of about 1.30 to 1.45, and has a problem in dispersion stability when using an aqueous fluorescent composition. In addition, the latter fluorescent pigments emulsion-polymerized with acrylonitrile and styrene-based monomers have a small particle diameter range of 0.05 to 1.50 μm and a low specific gravity of around 1.2, but the concentration is low, and there is a slight residual styrene monomer, and there is also an odor. Like the former, there were also problems in terms of environment and safety. In addition, these aqueous fluorescent compositions are typically emulsion-type, but the composition considerably contained a VOC film-forming aid and an anti-freezing agent.

There are also water-based fluorescent paints or water-based fluorescent inks in which two fluorescent pigments are mixed, but they have the above disadvantages as they are, which is a problem.

In addition, since the inkjet head diameter is as small as several microns, it is required that the particle size of the organic fluorescent pigment be very small in the case of inkjet recording ink.

In addition, since it is difficult to prepare aqueous fluorescent pigment dispersions suitable for inkjet fluorescent inks, conventional inkjet fluorescent inks include solvent-based fluorescent inks using fluorescent dyes as colorants or dissolving fluorescent pigments in organic solvents. There is a problem that it is harmful to the body and the human body (see Patent Document 6).

In particular, DayGlo SPL-N series, which are commercially available as formaldehyde-free fluorescent pigment dispersions for fibers, stationery and cosmetics among aqueous organic fluorescent pigment dispersions, Panax NFC series, SINOIHI SW-100 series, SF-8000 series, SF There is a -3000N series, but it is particularly unsuitable for manufacturing inkjet ink due to its large particles, high viscosity, and low filterability, and the manufactured ink has a problem that stability and output stability are not maintained for a long time.

Accordingly, the present inventors have a formaldehyde-free aqueous fluorescent pigment dispersion that has suitable physical properties (small particle size, low viscosity, excellent filterability, etc.) that can solve the above-described problems, and has excellent dispersion stability and stability for mixing with ink composition materials. By inventing the invention, it is intended to provide an aqueous fluorescent pigment dispersion that is particularly useful for inkjet inks.

In addition, it is intended to provide a formaldehyde-free aqueous fluorescent pigment dispersion according to the present invention as a useful colorant for eco-friendly inks, paints, textiles, and stationery.

USP 2938873 publication USP 3116256 publication JP 51-5678 publication JP 52-29336 publication JP 2001-181544 publication JP 6058955 publication

An object of the present invention is (a) formaldehyde-free organic fluorescent pigment; (b) a pigment dispersant;

And (c) to provide a water-based fluorescent pigment dispersion containing water.

Another object of the present invention is to provide a method for preparing a dispersion of an aqueous fluorescent pigment useful in ink, in particular, inkjet inks, by dispersing (a) a formaldehyde-free organic fluorescent pigment with a pigment dispersant.

In order to achieve the above object, the present invention (a) formaldehyde-free organic fluorescent pigment; (b) a pigment dispersant; And (c) it provides an aqueous fluorescent pigment dispersion containing water.

The present invention also provides a method of dispersing (a) a formaldehyde-free organic fluorescent pigment with a pigment dispersant to prepare a water-based fluorescent pigment dispersion useful in ink, particularly inkjet inks.

The aqueous fluorescent pigment dispersion according to the present invention has high saturation and excellent storage stability, after mixing a formaldehyde-free fluorescent pigment, a pigment dispersant, and water, and dispersing it with a bead mill. By providing a pigment dispersion, it can be used as a colorant in inks, especially inkjet inks.

In addition, the formaldehyde-free aqueous fluorescent pigment dispersion according to the present invention can be used in eco-friendly paints, textiles, stationery, etc. that are harmless to the human body and the environment.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.

In one aspect of the present invention, (a) formaldehyde-free organic fluorescent pigment; (b) a pigment dispersant; And (c) water-based organic fluorescent pigment dispersion.

In another aspect, the present invention is to provide a method for preparing an aqueous organic fluorescent pigment dispersion by dispersing (a) a formaldehyde-free organic fluorescent pigment with a pigment dispersant.

In the present invention, the aqueous organic fluorescent pigment dispersion may be prepared by dispersing a formaldehyde-free organic fluorescent pigment with a pigment dispersant.

In the present invention, the organic fluorescent pigment is prepared by dyeing one or two or more synthetic resins of a polyamide resin, a ketone resin, and a vinyl copolymer, and an oil dye or a basic dye as a colorant.

The fluorescent dye used for the resin fine particles dyed with the fluorescent dye is not particularly limited, and can be appropriately adjusted for each target color tone and maximum absorption wavelength. For example, it can be used by selecting from basic dyes, direct dyes, fluorescent brightening dyes, and the like, and among them, one kind or a combination of two or more daylight fluorescent dyes is preferred.

As a fluorescent dye used for the resin fine particles dyed with the fluorescent dye, specifically, CI Basic Red 1, CI Basic Red 13, CI Basic Red 1:1, CI Basic Violet 7, CI Basic Violet 10, CI Basic Violet 11, CI Basic Orange 22, CI Direct Orange 8, CI Direct Red 9, CI Direct Green 6, CI Fluorescent Whitening Agent 55, CI Fluorescent Brightening White WS 52, CI Fluorescent 162, Fluorescent 112, and the like. Among these, C.I. basic red 1, C.I. basic violet 10, C.I. basic violet 11, C.I. basic red 1:1, and C.I. fluorescent brightening white WS 52 are particularly preferred.

Fluorescent dyes such as Rhodamin and Fluorescein are dissolved in an organic solvent and mixed with a synthetic resin to cure/crush the synthetic resin, thereby confining the fluorescent dye in the resin powder to prepare an organic fluorescent pigment. As a specific product name, SINLOIHI's FM-11, FM-12, FM-13, FM-14, FM-15, FM-16, FM-17, FM-27, FM-34 N, FM-35 N, FM- There are 47, FM-103, FM-105, FM-107, and FM-109.

Further, examples of the resin particles dyed with a basic dye include fluorescent pigments obtained by dyeing the resin particles of an acrylonitrile-based copolymer with a basic fluorescent dye. Specific brand names include SINLOIHI Color SF series (SINLOIHI), NKW and NKP series (Japan Fluorescent Chemical Co., Ltd.).

In addition, since the inkjet head diameter is as small as several microns, in particular, in the case of inkjet fluorescent ink, it is required that the particle size of the organic fluorescent pigment be very small.

The average particle diameter of the resin fine particles dyed with the fluorescent dye is preferably 50 nm to 200 nm, and more preferably 70 nm to 150 nm. If the average particle diameter is less than 50 nm, since the fluorescence intensity is lowered, the saturation of the image is lowered, and if it exceeds 200 nm, the ejection stability of the ink may deteriorate. Therefore, by setting the average particle diameter of the fluorescent pigment to 70 nm to 150 nm, it is possible to prevent diffuse reflection of the pigment particles and provide a printed image having a uniform concentration.

In the present invention, the pigment dispersant is styrene, chloro styrene, vinyl toluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl ( Meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,, 2-phenoxyethyl (meth)acrylic Rate, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3- Chloropropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylamino (meth)acrylate, ethylhexyl acrylate, 2-methoxyethyl ( Meth)acrylate, 3-methoxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene Glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth) )Acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxy Consisting of oxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, meta acrylic acid, maleic acid, and itaconic acid It may be characterized in that it is prepared by polymerizing at least one selected from the group.

In the present invention, the organic fluorescent pigment dispersion contains 10 to 50 mass% of formaldehyde-free organic fluorescent pigment, 5 to 25 mass% of pigment dispersant, and 25 to 75 mass% of water based on 100 mass% of the total dispersion composition. It can be characterized.

In the present invention, the organic fluorescent pigment dispersion is useful for ink, particularly inkjet ink, and may be a paint, coating, fiber, or stationery colorant.

In the present invention, the organic fluorescent pigment dispersion may be characterized by having a viscosity of 2 to 10 cps, 3 to 9 cps, or 4 to 8 cps.

In the present invention, the organic fluorescent pigment dispersion is 40 to 500 g, 45 to 450 g, 100 to 500 g, 100 to 450 g, or It may be characterized by having a filterability of 100 to 400g.

In the present invention, the method for preparing the organic fluorescent pigment dispersion is dispersed at a temperature of 15 to 40°C or 20 to 40°C with a bead mill after adding an organic fluorescent pigment, a pigment dispersant, and water in the step (a). To prepare an organic fluorescent pigment dispersion.

If the temperature in the dispersing step is lower than 15℃, the solubility of the dispersant adsorbed on the surface of the fluorescent pigment may decrease or the viscosity may increase. If the temperature is higher than 40℃, the dispersant adsorbed to the fluorescent pigment Desorption of the dispersant may occur, resulting in a decrease in dispersibility, and a problem of inferior stability of the organic fluorescent pigment dispersion may occur.

As used herein, the term "composition" is considered to include not only products containing specific ingredients, but also any products made directly or indirectly by the combination of specific ingredients.

Hereinafter, the components and preparation method of the organic fluorescent pigment dispersion of the present invention will be described in detail.

Organic fluorescent pigment

The organic fluorescent pigment used in the present invention is obtained by coloring resin particles (resin fine particles) with a fluorescent dye. The resin particles include a copolymer of styrene and acrylonitrile, a copolymer of acrylic acid, and the like. The particle diameter is preferably 50 to 200 nm.

The dyes for coloring the resin particles are, for example, direct dyes such as CI Direct Red 2 and CI Direct Yellow 27, CI Acid Red 87, CI Acid Blue 9, CI Acid Yellow 23, CI Acid Red 92, CI Acid Black 2, etc. Acid dye, CI basic blue 3, CI basic blue 45, CI basic red 1, CI basic red 1:1, CI basic violet 1, CI basic violet 7, CI basic violet 11, CI basic yellow 40, CI basic green 1 And other basic dyes, disperse dyes such as CI dispulse yellow 82, and oil-soluble dyes such as CI solvent yellow 44.

The resin particles colored with the dye can be obtained by mixing a dye with a monomer as a preliminary step for synthesizing the resin particles, or by mixing a dye during or after polymerization.

Examples of commercially available products include Lumikol NKW-3002 (green pigment, styrene-acrylonitrile copolymer colored in CI basic yellow 40 and CI basic blue 45), Lumikol NKW-3004 (light orange pigment, styrene-acrylo The nitrile copolymer was colored with CI Basic Yellow 40, CI Basic Violet 11 and CI Basic Red 1:1), Lumikol NKW-3005 (yellow pigment, styrene-acrylonitrile copolymer colored in CI Basic Yellow 40) ), Lumikol NKW-3007 (peach color pigment, styrene-acrylonitrile copolymer colored with CI basic violet 11 and CI basic red 1:1), Lumikol NKW-3008 (light color pigment, styrene-acrylonitrile copolymerization Water colored in CI Basic Blue 45), Lumikol NKW-3077 (purple pigment, styrene-acrylonitrile copolymer colored in CI basic violet 7), Lumicol NKW-3602 (green pigment, styrene-acrylo The nitrile copolymer was colored in CI Basic Yellow 40 and CI Basic Blue 45), Lumikol NKW-3604 (A light orange pigment, styrene-acrylonitrile copolymer was used in CI Basic Yellow 40, CI Basic Violet 11 and CI Basic Red 1 : 1 colored), Lumikol NKW-3605 (yellow pigment, styrene-acrylonitrile copolymer colored in CI basic yellow 40), Lumikol NKW-3607 (peach-colored pigment, styrene-acrylonitrile copolymer) Colored with CI Basic Violet 11 and CI Basic Red 1:1), Lumikol NKW-3608 (light color pigment, styrene-acrylonitrile copolymer colored in CI Basic Blue 45), Lumikol NKW-3677 (purple Pigment, styrene-acrylonitrile copolymer colored with CI Basic Violet 7) (above, manufactured by Japan Fluorescent Chemical Co., Ltd.), Victoria Orange G-21A (light orange pigment, acrylic The acid copolymer was colored in CI Basic Yellow 40, CI Basic Red 1 and CI Basic Violet 11), Victoria Yellow-G-20 (yellow pigment, the copolymer of acrylic acid was used as CI Basic Yellow 40 and CI Despiero. 82), Victoria Green G-24C (yellow-green pigment, a copolymer of acrylic acid colored in CI Basic Yellow 40, CI Despiero 82, and CI Basic Green 1), Victoria Pink G-23 ( Peach pigment, acrylic acid copolymer colored in CI Basic Red 1 and CI Basic Violet 11), Victoria Blue G-25 (a water color pigment, a copolymer of acrylic acid colored in CI Basic Blue 3), Victoria Red G-22 (a red pigment, a copolymer of acrylic acid colored with CI Basic Yellow 40, CI Despiero 42, CI Basic Red 1, CI Basic Violet 11, and CI Basic Blue 3) (above, Mikuni Pigment (Note ), and Cosmokara S-1000 F series (manufactured by Dongyang Soda Co., Ltd.).

In addition, commercially available formaldehyde-free fluorescent pigments include DayGlo's ECO series, Wooksung Chemical's Panax Color FC series, and SINOIHI SX-100 series.

When the organic fluorescent pigment dispersion according to the present invention is used as an inkjet ink colorant, it is generally sprayed through a nozzle having a diameter of 10 to 50 μm, so the average particle size of the pigment must be sufficiently small. In addition, the average particle size of the pigment greatly affects the stability and color development of the ink. The average particle size range of pigments that do not deteriorate the mentioned properties is usually about 0.005 to 15 μm. It should preferably have a particle size of 0.05 to 5 μm, more preferably an average particle size range of 50 to 200 nm as an inkjet pigment.

Dispersant

The pigment dispersant used in the present invention refers to a polymer dispersant that imparts water dispersibility to a fluorescent pigment. The polymeric dispersant generally has a weight average molecular weight in the range of 50,000 to 200,000 as measured by gel permeation chromatography, and more generally refers to a molecular weight of 10,000 to 40,000.

As the polymer dispersant used in the pigment dispersion, a (meth)acrylate and (meth)acrylic acid copolymer or a styrene-acrylic acid copolymer is preferable, and depending on the ratio of the monomer used during polymerization (i.e., hydrophobicity such as unsaturated acrylate) Hydrophilic monomers such as monomer, acrylic acid, or hydroxyacryl) By adjusting the ratio of hydrophilic-hydrophobic properties, the adsorption power with the pigment and the dispersing power in an aqueous or oily medium can be controlled. It can also increase the fixing properties and glossiness of the ink composition.

Monomers that can be used in the copolymerization for preparing the dispersant include, for example, styrene, chlorostyrene, vinyltoluene, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl ( Meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,, 2- Phenoxyethyl (meth)acrylate, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylamino (meth)acrylate, ethylhexyl acrylate , 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth) Acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonyl Phenoxypolypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, methyl α-hydroxymethyl Acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, meta acrylic acid, Maleic acid or itaconic acid, and the like, but is not limited thereto.

Further, the dispersant is at least one or more dispersants selected from polyacrylate polymers, polystyrene-acrylate polymers, styrene maleic anhydride copolymers, and the like.

The pigment dispersant may be characterized in that it has an acid value of 100mgKOH/g or more and 300mgKOH/g or less. When the acid value of the pigment dispersant is less than 100mgKOH/g, the solubility in water is low, making it unsuitable when applying aqueous pigment dispersion. On the other hand, when the acid value exceeds 300mgKOH/g, the dispersant is not adsorbed on the pigment surface due to high solubility in water. There is a problem that it is difficult to function as a dispersant because it exists in a dissolved state.

Volatile organic base compounds used to neutralize the polymer dispersant include, for example, mono (methyl, ethyl, propyl) amines, di (methyl, ethyl, propyl) amines of primary, secondary, and tertiary amines, and tri (Methyl, ethyl, propyl) amine, N,N-dimethylcyclohexyl amine, N,N-dimethylstearyl amine, N,N-dimethylaniline, N-methylpiperazine, N,N-dimethylethanol amine, N, N-diethylethanol amine, triethanolamine, N-methyldiethanolamine, dimethylaminopropanol, 2-methoxyethyldimethylamine, N-hydroxyethylpiperazine, 2-(2-dimethylaminoethoxy)-ethanol and 5-diethylamino-2-pentanone, 3-amino-1-propanol, N-ethylethanolamine, ammonia, and the like, but are not limited thereto. In addition, the nonvolatile base compound includes, for example, an alkoxide, hydroxide, carbonate, or bicarbonate compound among lithium, sodium, and potassium monovalent alkali metals, but is not limited thereto.

Dispersants used for dispersing fluorescent pigments may be commercially available dispersants, for example, Joncyl 693 or Joncryl 67 from BASF, Zetasperse 2500 from Air Product, Zetasperse 3100, Zetasperse 3400, Zetasperse 3600, or Zetasperse 3700, DISPERBYK from BYK 194, DISPERBYK 2012, DISPER 2014, or BYKJET 9170, Lubrizol's Solsperse WV400, Huntsman's JEFFSPERSE X3204 or JEFFSPERSE X3503, but are not limited thereto.

Dispersion process

As a method used for the milling and dispersion treatment of the fluorescent pigment dispersion, for example, a ball mill, a roll mill, a bead mill, a high pressure homogenizer, or a high speed stirrer may be used.

Formaldehyde-free fluorescent pigment, neutralized polymer dispersant, and water are added and stirred, and then dispersed using a bead mill. The beads of the bead mill are suitable for zirconium 0.1~0.5mm and filling rate 50~85%. The temperature at the time of dispersion is preferably 15°C or more and 40°C or less, or 20°C or more and 40°C or less. In order to suppress the generation of bubbles during dispersion, an antifoaming agent or the like may be used together.

[Example]

Hereinafter, the present invention will be described in more detail through examples. These examples are for illustrative purposes only, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not construed as being limited by these examples. Therefore, it will be said that the practical scope of the present invention is defined by the appended claims and their equivalents.

Example 1: Preparation of fluorescent pigment dispersion

1-1: Preparation of fluorescent pigment dispersion

Pink fluorescent pigment (product name ECO Aurora Pink, manufactured by DayGlo) 30% by mass, styrene-acrylic polymer dispersant neutralized with triethanol amine (Joncryl 693, Basf) 25% It was mixed with 60 mass% of a solution and 10 mass% of water. The mixture was dispersed in a bead mill (dyno-mill, KD-Lab.) for 11 hours. The prepared dispersion was let-down to 15% by mass of solid based on a colorant, and then filtered to obtain a fluorescent pigment dispersion (1) having a pH of 7.3 and an average particle size of 86.26 nm.

Using the same method as the preparation of the pigment dispersion, as shown in Table 1 below, fluorescent pigments (ECO Aurora Pink, ECO Saturn Yellow, AX-13-5 red, DayGlo, FZ-6031 Pink, SINOIHI), By varying the dispersant, content ratio, etc., fluorescent pigment dispersions (2) to (11) were prepared. In Table 1, the dispersant SA is a styrene-acrylic polymer dispersant (BASF), and SMA is a styrene maleic anhydride polymer dispersant (Air Product).

Fluorescent pigment dispersion Fluorescent pigment Dispersant Pigment/dispersant content ratio
(Based on solid content) Dispersion time
(hr) Dispersion pH Average particle size of dispersion (nm) One ECO Aurora Pink SA1 2/1 11 7.3 86.26 2 ECO Aurora Pink SA1 5/2 12 7.2 95.0 3 ECO Aurora Pink SA1 3/1 15 7.1 145 4 ECO Aurora Pink SA1 4/1 20 7.0 180 5 ECO Aurora Pink SA2 2/1 11 7.15 87.6 6 ECO Aurora Pink SMA1 2/1 20 6.56 319.0 7 ECO Aurora Pink SMA2 2/1 15 7.04 174.0 8 ECO Saturn Yellow SA1 2/1 13 7.2 94.8 9 ECO Saturn Yellow SA2 2/1 12 7.15 95.0 10 AX-13-5 red SA1 2/1 6 8.1 171.8 11 FZ-6031 Pink SA1 2/1 4 7.87 100.6

* Fluorescent pigment ECO series (ECO Aurora Pink, ECO Saturn Yellow): formaldehyde free

As a result of measuring the average particle size of each of the fluorescent pigment dispersions, it was confirmed that the dispersibility of the fluorescent pigment was better when the SA-based dispersant was applied than the SMA-based dispersant.

Example 2: Fluorescent pigment dispersion property evaluation

2-1: Evaluation of physical properties

Each of the prepared fluorescent pigment dispersions was put in a plastic container of about 300 ml and 500 ml, sealed, and placed in a constant temperature water bath at 25° C. to stabilize the temperature of the dispersion, and then the average particle size, viscosity, pH, and filterability were measured under room temperature conditions.

The average particle size was measured three times using the dynamic light scattering method of Microtrac's NanotracTM 250 equipment (1 minute per measurement), and the viscosity was measured by BROOKFEILD's LVDV-II B-type viscometer (CPE- 40 spindle standard). The pH was measured using TOA's portable HM-20P pH METER, and the filterability was measured using ADVANTEC's 0.8㎛ Syringe filter (CS080AN), and is shown in Table 2 below.

Fluorescent pigment dispersion pH Average particle size
(nm) Viscosity
(cps) Filterability
(g) One 7.3 86.26 7.94 400 2 7.2 95.0 6.49 49.25 3 7.1 145 6.1 5.0 4 7.0 180 5.9 1.5 5 7.15 87.6 7.4 400 6 6.56 319.0 4.92 0 7 7.04 174.0 4.44 2.0 8 7.2 94.8 7.34 400 9 7.15 95.0 6.9 300 10 8.1 171.8 6.27 22.5 11 7.87 100.6 6.5 300 12* 7.78 498.0 40.5 0 13* 6.75 126.7 2.21 0 14* 2.66 671 65.4 0

Commercially available aqueous fluorescent pigment dispersions, fluorescent pigment dispersion 12* (SPL-11N-Pink, DayGlo), 13* (PANAX NFC-Pink, Ukseong Chemical Co., Ltd.), and 14* (SW-117 Pink, SINOIHI) have average particle size. , Viscosity and filterability were unsuitable for manufacturing inkjet inks, and the fluorescent pigment dispersion (11) using FZ-6031 Pink was excellent in dispersibility and physical properties, but it contained formaldehyde, so it was unsuitable for manufacturing eco-friendly ink. .

On the other hand, it was confirmed that the aqueous fluorescent pigment dispersions (1), (2), (5), (8), and (9) prepared according to the present invention had low average particle size and viscosity, and excellent filterability. It was confirmed that it can be usefully used as a colorant.

2-2: Evaluation of stability over time

Each of the prepared fluorescent pigment dispersions was put in about 15 ml, 20 ml glass vial, sealed, and stored at room temperature, 60°C and 80°C. In order to measure the change in stability over time according to temperature, samples were collected by day, and changes in average particle size, viscosity, and pH were measured at room temperature conditions.

The average particle size was ^{measured three times (1 minute per measurement) using the dynamic light scattering method of Microtrac's Nanotrac TM} 250 equipment, and the viscosity was measured by BROOKFEILD's LVDV-II B-type viscometer (CPE). -40 spindle standard), and the pH was measured using TOA's portable HM-20P pH METER, and are shown in Tables 3 and 4 below.

Temperature and
Elapsed time Evaluation item Fluorescent pigment
Dispersion(1) Fluorescent pigment
Dispersion(2) Fluorescent pigment
Dispersion(5) Fluorescent pigment
Dispersion (8) Early Average particle size (nm) 86.26 95.0 87.6 94.8 Viscosity (cps) 7.97 6.49 7.4 7.34 pH 7.3 7.2 7.15 7.2 60℃, 2 weeks Average particle size (nm) 86.6 95.1 77.5 98.2 Viscosity (cps) 5.95 4.6 2.98 6.8 pH 7.13 7.09 6.94 7.1 80℃, 2 weeks Average particle size (nm) 113.4 91.3 123.7 135.0 Viscosity (cps) 5.66 3.0 2.6 8.2 pH 6.97 6.93 6.71 6.81

Temperature and
Elapsed time Evaluation item Fluorescent pigment
Dispersion (9) Fluorescent pigment
Dispersion (12*) Fluorescent pigment
Dispersion (13*) Fluorescent pigment
Dispersion (14*) Early Average particle size (nm) 95.0 498.0 126.7 671.0 Viscosity (cps) 6.9 40.5 2.21 65.4 pH 7.15 7.78 6.75 2.66 60℃, 2 weeks Average particle size (nm) 103.5 gelation 128.0 549.0 Viscosity (cps) 5.58 4.31 2.8 pH 7.08 6.88 2.69 80℃, 2 weeks Average particle size (nm) 176.1 gelation gelation gelation Viscosity (cps) 7.07 pH 6.94

Commercially available fluorescent pigment dispersions (12*) (SPL-11N-Pink, DayGlo), (13*) (PANAX NFC-Pink, Ukseong Chemical Co., Ltd.), and (14*) (SW-117 Pink, SINOIHI) are under high temperature The gelation proceeds over time and the stability over time is inadequate.

The aqueous fluorescent pigment dispersions (1), (2), (5), (8), and (9) prepared by the present invention maintain a stable range of average particle size, viscosity, and pH even over time under high temperature conditions , It was confirmed that the stability over time was also very excellent.

Example 3: Fluorescent Pigment Dispersion Ink Application Check

Using the fluorescent pigment dispersions (1), (5) and commercially available fluorescent pigment dispersions (12*, 13*, 14*) prepared in the present invention, the ink composition for digital textile printing in the composition shown in Table 5 below ( 1) to (5) were prepared. That is, the fluorescent pigment dispersion was mixed with a binder resin, a water-soluble organic solvent, and the like to prepare respective ink compositions. In addition, the physical properties of the prepared ink compositions (1) to (5) are shown in Table 5 below [UCOAT UWS-145 (polyester-based polyurethane, Sanyo Chemical); 1,2-hexanediol (camtrose); Glycerin (LG Household & Health Care); BYK-348 (polyether modified siloxane, BYK); BT550 (1,2-benzisothiazolin-3-one, CDI)].

ink
Composition (1) ink
Composition (2) ink
Composition (3) ink
Composition (4) ink
Composition (5) Fluorescent pigment dispersion Fluorescent Pigment Dispersion (1) Fluorescent pigment
Dispersion(5) Fluorescent pigment
Dispersion (12*) Fluorescent pigment
Dispersion (13*) Fluorescent pigment
Dispersion (14*) Composition in ink composition (% by mass) Fluorescent pigment 5.0 5.0 5.0 5.0 5.0 Binder resin UCOAT
UWS-145 5.0 5.0 5.0 5.0 5.0 Water soluble organic solvent 1,2-hexanediol 2.0 2.0 2.0 2.0 2.0 Moisturizer glycerin 25 25 25 25 25 Surfactants BYK-348 0.1 0.1 0.1 0.1 0.1 antiseptic BT550 0.1 0.1 0.1 0.1 0.1 water Balance Balance Balance Balance Balance Total weight (% by mass) 100 100 100 100 100 Properties of the ink composition Average particle size (nm) 86.7 66.3 531.0 133.5 675.5 Viscosity (cps) 5.95 5.62 10.2 3.9 24.8 pH 7.26 7.17 7.84 7.55 7.22

The ink compositions (1) and (2) for digital textile printing prepared using the fluorescent pigment dispersions (1) and (5) prepared in the present invention have excellent average particle size and viscosity as shown in Table 5, and are used as inkjet printing. Possible physical properties can be secured.

As described above, specific parts of the present invention have been described in detail, and it is obvious that these specific techniques are only preferred embodiments for those of ordinary skill in the art, and the scope of the present invention is not limited thereby. something to do. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (16)

Organic fluorescent pigment dispersion comprising:
(a) formaldehyde-free organic fluorescent pigment;
(b) a pigment dispersant; And
(c) water.
The method of claim 1,
The organic fluorescent pigment dispersion liquid, characterized in that the formaldehyde-free resin fine particles having an average particle size of 50 ~ 200nm dyed with a fluorescent dye.
The method of claim 2, wherein the resin fine particles include at least one of a polyamide resin, a ketone resin, a vinyl copolymer, a copolymer of styrene and acrylonitrile, and a copolymer of acrylic acid. An organic fluorescent pigment dispersion comprising one of dyes.
The method of claim 1,
The pigment dispersant is styrene, chloro styrene, vinyl toluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, Glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,, 2-phenoxyethyl (meth) acrylate, tetrahydrofur Pryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth) Acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylamino (meth)acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylic Rate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tetra Fluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, At least one selected from the group consisting of propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, meta acrylic acid, maleic acid, and itaconic acid An organic fluorescent pigment dispersion, characterized in that prepared by polymerization.
The method of claim 1,
The pigment dispersant comprises at least one selected from the group consisting of a polyacrylate polymer and a polystyrene-acrylate polymer.
The method of claim 1,
An organic fluorescent pigment dispersion, characterized in that the pigment dispersant has an acid value of 100 mgKOH/g or more and 300 mgKOH/g or less.
The method of claim 1,
The pigment dispersion is characterized in that it contains 10 to 50% by mass of formaldehyde-free organic fluorescent pigment, 5 to 25% by mass of a pigment dispersant, and 25 to 75% by mass of water, based on 100% by mass of the total organic fluorescent pigment dispersion. Fluorescent pigment dispersion.
The method of claim 1,
The organic fluorescent pigment dispersion is used in ink, paint, coating, fiber, or stationery colorant, or inkjet ink, organic fluorescent pigment dispersion.
The method of claim 1,
The organic fluorescent pigment dispersion liquid, characterized in that it has a viscosity of 4 to 8 cps, organic fluorescent pigment dispersion. The method of claim 1,
The organic fluorescent pigment dispersion liquid, characterized in that it has a filterability of 40 to 500 g, based on a 0.8㎛ syringe filter (Syringe filter), organic fluorescent pigment dispersion.
Organic fluorescent pigment dispersion preparation method comprising the following steps:
(a) adding and mixing a formaldehyde-free organic fluorescent pigment, a pigment dispersant, and water; And
(b) preparing an organic fluorescent pigment dispersion with a bead mill.
The method of claim 11,
The organic fluorescent pigment is a method for producing an organic fluorescent pigment dispersion, characterized in that the formaldehyde-free resin fine particles having an average particle size of 50 ~ 200nm dyed with a fluorescent dye.
The method of claim 12, wherein the resin fine particles include at least one of a polyamide resin, a ketone resin, a vinyl copolymer, a copolymer of styrene and acrylonitrile, and a copolymer of acrylic acid. A method for producing an organic fluorescent pigment dispersion, characterized in that it contains one of the dyes.
The method of claim 11,
The pigment dispersant is styrene, chloro styrene, vinyl toluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, Glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,, 2-phenoxyethyl (meth) acrylate, tetrahydrofur Pryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth) Acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylamino (meth)acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylic Rate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tetra Fluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, At least one selected from the group consisting of propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, meta acrylic acid, maleic acid, and itaconic acid A method for producing an organic fluorescent pigment dispersion, characterized in that produced by polymerization.
The method of claim 11,
The pigment dispersant comprises at least one selected from the group consisting of a polyacrylate polymer and a polystyrene-acrylate polymer.
The method of claim 11,
In the step (b), a method for preparing an organic fluorescent pigment dispersion, characterized in that to prepare a formaldehyde-free organic fluorescent pigment dispersion by dispersing at a temperature of 15 to 40 °C using a bead mill.