JP2006273891A - Ink composition, recording method and recorded material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition capable of obtaining an image having an excellent glossy feeling for various recording media, especially the recording media having gloss, showing less bronze phenomenon and having a good fixing property and abrasion resistance such as a gloss change, etc. <P>SOLUTION: This ink composition at least containing a coloring agent covered by a water insoluble polymer and resin particles is characterized in that the water insoluble polymer is a polymer obtained by polymerization using at least a polymerizable unsaturated monomer and a polymerization initiator by a solution polymerization method, the coloring agent covered with the water insoluble polymer is the coloring agent obtained by a phase inversion emulsification of dissolving the water insoluble polymer with an organic solvent, adding at least the coloring agent and water, mixing and then removing the organic solvent to disperse in an aqueous medium, and the resin particles are made of at least a polymer obtained by a polymerization by emulsion polymerization method using a cross-linking agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink composition. More specifically, the present invention relates to an ink composition suitable for use in an ink jet recording system.

  The ink jet recording method is a printing method in which printing is performed by causing ink droplets to fly and adhere to a recording medium such as paper. Due to recent advances in inkjet recording technology, the inkjet recording method has been used for high-definition image recording (printing), which has been the field of photography and offset printing. High-quality recording has been demanded not only for paper and dedicated paper for ink jet recording (matte and glossy) but also for recording media such as printing paper.

As an ink used for ink jet recording, an ink composition is generally known that includes a coloring material that is a colorant, water, a water-soluble organic solvent, a surfactant, and the like.
As the colorant, dyes or pigments are used. In particular, water-soluble dyes are often used for color inks because of high color saturation, transparency, and high solubility in water. However, such dyes generally have insufficient light resistance and gas resistance, and because they are water-soluble, there are also problems with water resistance. The recorded matter has a drawback that the recorded image has poor storage stability. On the other hand, a colorant insoluble in water is advantageous in terms of water resistance. Among pigments that are insoluble in water, in particular, pigments are color materials excellent in light resistance, gas resistance, and water resistance, and therefore, pigment inks that take advantage of these color material properties have been developed. An aqueous pigment ink in which a pigment is dispersed with a surfactant or a polymer dispersant, an aqueous pigment ink using a self-dispersing pigment with a water-dispersible functional group added to the pigment surface, or a pigment coated with a water-dispersible resin An aqueous pigment ink using colored fine particles has been proposed.

  In such a pigment ink, pigment particles (including pigment-containing colored fine particles) are stably dispersed in the ink liquid. The process of drying the ink after the ink has adhered to a recording medium such as paper. As the moisture and volatile solvents evaporate, the stable dispersion system collapses and the pigments tend to aggregate. When the aggregated pigment is deposited on a recording medium such as paper, the smoothness of the surface is lost, the glossiness is deteriorated, the uniformity of the printed image is deteriorated, and there is a problem that a high-quality image cannot be obtained. Further, the reflected light of the deposited pigment makes it possible to see a color with a hue different from the original hue (bronze phenomenon), and there is a problem that an image with a uniform desired hue cannot be obtained. In addition, the pigment deposited on the surface is peeled off by rubbing, and the pigment on the surface is rubbed or crushed when touched with a finger, etc. There was also a problem.

  Regarding the image quality of the pigment ink, the particle diameter of the pigment dispersed in the ink is limited for the purpose of improving glossiness and dispersibility (see Patent Document 1), and the pigment and the pigment derivative are simultaneously contained. For the purpose of improving bleeding and color developability (see Patent Document 3), containing inorganic fine particles (see Patent Document 4), and plain paper For the purpose of improving the printing density and glossiness of ink jet paper, an ink containing a water-insoluble vinyl polymer dispersion containing a pigment (see Patent Document 5) has been proposed.

  However, even such a pigment ink is insufficient for glossiness and uniformity of a printed image, and in particular, the reflected light of the pigment aggregated on the paper surface appears to have a hue different from the original hue. There is a problem that the quality of the water-soluble dye ink is inferior to the rubbing resistance such as (bronze phenomenon) and ink fixability and gloss change.

JP 2002-356737 A JP 2002-294134 A JP 2001-123098 A JP-A-11-209671 Japanese Patent Laid-Open No. 2005-41994

  The present invention has been made in view of the above problems, and the object of the present invention is to produce images having excellent gloss without bronzing on various recording media, particularly recording media having gloss. It is an ink composition that can be obtained and has an excellent rubbing resistance, and is particularly suitable for use in an ink jet recording system.

As a result of intensive studies, the inventors have determined that, in an ink composition containing at least a colorant and a resin particle coated with a water-insoluble polymer, the water-insoluble polymer uses at least a polymerizable unsaturated monomer and a polymerization initiator. A colorant that is obtained by polymerization by a solution polymerization method and is coated with a water-insoluble polymer. After dissolving the water-insoluble polymer in an organic solvent, add at least the colorant and water, and mix the organic solvent. A colorant obtained by phase inversion emulsification method that is removed and dispersed in an aqueous system, and the resin particle is a polymer obtained by polymerization by emulsion polymerization method using at least a crosslinking agent. The knowledge that the problem could be solved was obtained. The present invention is based on such knowledge, and the configuration of the present invention is as follows.
(1) In an ink composition containing at least a colorant and resin particles coated with a water-insoluble polymer, the water-insoluble polymer is polymerized by a solution polymerization method using at least a polymerizable unsaturated monomer and a polymerization initiator. The obtained colorant, which is coated with a water-insoluble polymer, is dissolved in an organic solvent, and then mixed with at least the colorant and water, and the organic solvent is removed and dispersed in an aqueous system. An ink composition comprising: a colorant obtained by a phase inversion emulsification method, wherein the resin particles are a polymer obtained by polymerization by an emulsion polymerization method using at least a crosslinking agent.
(2) The ink composition according to (1), wherein the colorant is a water-insoluble colorant.
(3) The ink composition according to (1) or (2), wherein the water-insoluble polymer is a branched polymer.
(4) The ink composition according to any one of (1) to (3), wherein the resin particles are made of a polymer that does not form a film at a temperature of 40 ° C. or lower.
(5) The ink composition according to any one of (1) to (4), wherein the resin particles have an average particle diameter of 20 to 80 nm.
(6) The colorant is a pigment, includes at least water and a water-soluble organic compound, and has an average particle diameter in the range of 50 to 150 nm in any one of (1) to (5) An ink composition according to any one of the above.
(7) The ink composition according to (6), wherein at least a polyhydric alcohol, a solid wetting agent, and a butyl ether of glycol are used in combination as the water-soluble organic compound.
(8) The polyhydric alcohol is a combination of two or more selected from glycerin, diethylene glycol, triethylene glycol, 1,5-pentanediol and 1,2-hexanediol, and the solid wetting agent is trimethylolethane or tri The ink composition according to (6) or (7), wherein the ink composition is methylolpropane or urea, and the butyl glycol is diethylene glycol monobutyl ether or triethylene glycol monobutyl ether.
(9) The composition according to any one of (1) to (8), which is used in an ink jet recording system.
(10) A recording method for performing printing by attaching the ink composition according to any one of (1) to (9) to a recording medium.
(11) An ink jet recording method according to any one of (1) to (9), wherein ink droplets are ejected and the droplets are attached to a recording medium for printing. .
(12) A recorded matter recorded by the recording method according to (10) or (11).

Hereinafter, the ink composition of the present invention will be described in detail based on preferred embodiments thereof.
The ink composition of the present invention is an ink composition containing at least a colorant and resin particles coated with a water-insoluble polymer. The water-insoluble polymer is a solution using at least a polymerizable unsaturated monomer and a polymerization initiator. The colorant coated by the water-insoluble polymer is polymerized by the polymerization method. After dissolving the water-insoluble polymer in an organic solvent, add at least the colorant and water and mix to remove the organic solvent. The resin particles are a polymer obtained by polymerization by emulsion polymerization using at least a polymerizable unsaturated monomer and a polymerization initiator. It is characterized by being the ink composition.
Each of these components will be described in detail.

[Colorant]
As the colorant of the present invention, existing dyes and pigments described in “Dye Handbook” (publisher: Maruzen Co., Ltd.) and the like can be used.
The colorant of the present invention is preferably a water-insoluble colorant, and a more preferred colorant is a pigment. As the pigment that can be used in the present invention, any of known inorganic pigments and organic pigments can be used, and pigments such as Pigment Yellow, Pigment Red, Pigment Violet, Pigment Blue, and Pigment Black described in the Color Index. In addition, phthalocyanine-based, azo-based, anthraquinone-based, azomethine-based, condensed ring-based pigments can be exemplified. Further, organic pigments such as yellow No. 4, 5, 205, 401; orange 228, 405; blue No. 1, 404, etc., titanium oxide, zinc oxide, zirconium oxide, iron oxide, ultramarine blue, bitumen, Examples thereof include inorganic pigments such as chrome oxide. For example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42, 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 153, 155, 174, 180, 198, C.I. I. Pigment Red 1,3,5,8,9,16,17,19,22,38,57: 1,90,112,122,123,127,146,184,202,209, C.I. I. Pigment Bio Red 1,3,5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, C.I. I. Pigment Black 1, 7, etc., and an ink composition can also be formed using a plurality of pigments.

  These pigments are preferably contained in the ink of the present invention in the range of 0.5 to 8% by weight. If the content is less than 0.5% by weight, the print density (color developability) may be insufficient. If the content is more than 8% by weight, the gloss on the glossy media will be deteriorated, the nozzles may be clogged, and the ejection will be poor. There may be a problem in reliability such as stability.

[Colorant coated with water-insoluble polymer]
The water-insoluble polymer used for the colorant coated with the water-insoluble polymer of the present invention is a polymer obtained by polymerization by a solution polymerization method using at least a polymerizable unsaturated monomer and a polymerization initiator. The polymer refers to a polymer having a solubility in 100 g of water at 25 ° C. of less than 1 g after neutralization.

  Examples of the polymerizable unsaturated monomer include vinyl aromatic hydrocarbons, methacrylic acid esters, methacrylamide, alkyl-substituted methacrylamide, maleic anhydride, vinyl cyanide compounds, methyl vinyl ketone, and vinyl acetate. Specifically, styrene, α-methylstyrene, vinyl toluene, 4-t-butyl styrene, chlorostyrene, vinyl anisole, vinyl naphthalene, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n- There are amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, etc. Use alone or in combination of two or more It is also possible.

Furthermore, the water-insoluble polymer of the present invention preferably contains a monomer having a hydrophilic group and a monomer having a salt-forming group in order to impart gloss to the printed image.
Examples of the monomer having a hydrophilic group include polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, and ethylene glycol / propylene glycol monomethacrylate. These can be used alone or in admixture of two or more. In particular, polyethylene glycol (2-30) monomethacrylate, polyethylene glycol (1-15) / propylene glycol (1-15) monomethacrylate, polypropylene glycol (2-30) methacrylate, methoxypolyethylene glycol (2-30) methacrylate, methoxy The gloss of printed images is further improved by using monomer components that constitute branched chains such as polytetramethylene glycol (2-30) methacrylate and methoxy (ethylene glycol / propylene glycol copolymer) (1-30) methacrylate. To do.

  Monomers having a salt-forming group include acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid, etc., and each can be used alone or in combination of two or more.

Furthermore, a macromonomer such as a styrene macromonomer or a silicone macromonomer having a polysynthetic functional group at one end, or other monomers can be used in combination.
In the polymerization, a known radical polymerization agent or polymerization chain transfer agent may be added.

  The colorant coated with the water-insoluble polymer of the present invention is obtained by a phase inversion emulsification method. That is, the above water-insoluble polymer is dissolved in an organic solvent such as methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone, dibutyl ether, a colorant is added to the resulting solution, and then a neutralizing agent and water are added. By adding, kneading and dispersing, an oil-in-water type dispersion is prepared, and an organic solvent is removed from the obtained dispersion to obtain an aqueous dispersion. For the kneading and dispersing treatment, for example, a ball mill, a roll mill, a bead mill, a high-pressure homogenizer, a high-speed stirring type disperser, or the like can be used.

  The neutralizing agent is preferably a tertiary amine such as ethylamine or trimethylamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia or the like, and the pH of the resulting aqueous dispersion is preferably 6-10.

  The water-insoluble polymer to be coated is preferably a polymer having a weight average molecular weight of about 10,000 to 150,000 from the viewpoint of stably dispersing a colorant, particularly a pigment. The weight average molecular weight can be measured by a molecular weight analysis method by gel permeation chromatography (GPC).

  Further, from the viewpoint of color development and glossiness on glossy media, the average particle size in the ink composition is preferably in the range of 50 to 150 nm. In addition, these average particle diameters can be obtained by particle size measurement using a Microtrac UPA150 (manufactured by Microtrac) or a particle size distribution analyzer LPA3100 (manufactured by Otsuka Electronics Co., Ltd.).

  The colorant covered with the water-insoluble polymer of the present invention may have a shape in which a part of the colorant is exposed without being completely covered with the water-insoluble polymer.

[Resin particles]
The resin forming the resin particles is preferably one or more selected from the group consisting of acrylic resins, methacrylic resins, styrene resins, urethane resins, acrylamide resins, and epoxy resins. . These resins may be used as homopolymers, or may be used as copolymers, and any of single-phase structure and multi-phase structure (core-shell type) can be used. Resin.

  In general, when a polymer dispersed as a colorant dispersion is used in combination with a polymer as an additive, the polymer as the dispersant and the polymer as the additive are absorbed and desorbed with respect to the colorant, and the dispersion stability is lost and the storage stability is lost. There is a problem of deterioration. However, in the present invention, since the colorant is coated with a water-insoluble polymer by the phase inversion emulsification method, it is stable as dispersed particles, and the resin fine particles are internally cross-linked, so they exist as strong resin particles. In addition, the resin particles produced by the emulsion polymerization method contain a small amount of surfactant that cannot be removed (surfactant used in emulsion polymerization), thereby inhibiting the adsorption / desorption of water-insoluble polymer and resin particles. The dispersion stability is considered to be maintained.

  Furthermore, the resin particles of the present invention are preferably a polymer that does not form a film at a temperature of 40 ° C. or lower. The addition of resin particles in the present invention is not intended to improve fixability and abrasion resistance by forming a resin film, but by leaving fine particles on the surface of the recording medium, the surface slipperiness is improved and coloring due to rubbing. The purpose is to prevent peeling and gloss change of the agent. By using a polymer that does not form a film at 40 ° C. or lower, reliability such as clogging recovery can be obtained compared to the case of using a film-forming polymer. There is an advantage that it is remarkably good.

  The resin particles used in the present invention are preferably blended in the ink composition in the form of an emulsion (for example, so-called “acrylic emulsion”) of resin particles obtained by emulsion polymerization of at least an unsaturated monomer. The reason is that the resin particles may be insufficiently dispersed even if they are added to the ink composition as they are, so that the emulsion form is preferable for the production of the ink.

  An emulsion of resin particles (such as an acrylic emulsion) can be obtained by a known emulsion polymerization method. For example, it can be obtained by emulsion polymerization of an unsaturated monomer (such as an unsaturated vinyl monomer) in water containing a polymerization initiator and a surfactant.

  Examples of unsaturated monomers include acrylic acid ester monomers, methacrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl cyanide compounds generally used in emulsion polymerization. Examples include monomers, halogenated monomers, olefin monomers, and diene monomers. Furthermore, specific examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate. Acrylic acid esters such as dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl Methacrylate, n-hexyl methacrylate, 2-ethyl Hexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, methacrylic esters such as phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and vinyl esters such as vinyl acetate; vinyl such as acrylonitrile and methacrylonitrile Cyanides; halogenated monomers such as vinylidene chloride and vinyl chloride; simple aromatic vinyl such as styrene, α-methylstyrene, vinyltoluene, 4-t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene Olefins such as ethylene and propylene; dienes such as butadiene and chloroprene; vinyl ether, vinyl ketone, vinyl pyrrolide Vinyl monomers such as acrylic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid; acrylamides such as acrylamide, methacrylamide and N, N′-dimethylacrylamide; 2-hydroxy Examples thereof include hydroxyl group-containing monomers such as ethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, and these can be used alone or in combination of two or more.

  Further, as the crosslinking agent, a crosslinkable monomer having two or more polymerizable double bonds can be used. Examples of the crosslinkable monomer having two or more polymerizable double bonds include polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4-acryloxypropyloxyphenyl) propane, 2,2 ' -Diacrylate compounds such as bis (4-acryloxydiethoxyphenyl) propane, triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate , Tetraacrylate compounds such as ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, hexaacrylate compounds such as dipentaerythritol hexaacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol Dimethacrylate, 2 Examples include dimethacrylate compounds such as 2'-bis (4-methacryloxydiethoxyphenyl) propane, trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate, methylenebisacrylamide, and divinylbenzene. It can be used alone or in combination.

  In addition to the polymerization initiator and surfactant used in emulsion polymerization, a chain transfer agent, further a neutralizing agent, and the like may be used according to a conventional method. In particular, ammonia and inorganic alkali hydroxides such as sodium hydroxide and potassium hydroxide are preferred as the neutralizing agent.

In the present invention, the resin particles are used in an amount of 0.1 to 5% by weight from the viewpoint of more effectively obtaining ink jet proper physical property values, reliability (clogging, ejection stability, etc.), fixing properties, and glossiness. It is preferably contained in the ink of the present invention.
On the other hand, the average particle diameter of the resin particles used in the present invention is improved by improving the sliding stability of the surface of the recording medium by the particles without deteriorating the dispersion stability in the ink composition and the gloss of the recorded image. In order to obtain the effect of improving the average particle size, the average particle size is preferably 20 to 80 nm. In addition, these average particle diameters can be obtained by particle size measurement using a Microtrac UPA150 (manufactured by Microtrac) or a particle size distribution analyzer LPA3100 (manufactured by Otsuka Electronics Co., Ltd.).

[Water-soluble organic compounds]
An ink composition suitable for the ink jet recording method of the present invention, which contains water and a water-soluble organic compound. Water is the main solvent, and it is preferable to use pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water. In particular, it is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide in order to prevent the generation of mold and bacteria and enable long-term storage of the ink composition.

  Examples of the water-soluble organic compound include glycerin, 1,2,6-hexanetriol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1, 4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1 Polyhydric alcohols such as 1,2-pentanediol, trimethylolethane, methylolpropane, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, (Sorbit), maltose Sugars such as cellobiose, lactose, sucrose, trehalose, maltotriose, so-called solid wetting agents such as sugar alcohols, hyaluronic acids, ureas, alkyls having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, isopropanol Alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether , Diethylene glycol mono-iso-propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono Glycols such as n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether Ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidino , Formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, sulfolane and the like, and one or more of these can be used. These water-soluble organic compounds are used in the ink composition. From the viewpoint of ensuring appropriate physical property values (such as viscosity), printing quality, and reliability, it is preferably contained in the ink composition in an amount of 10 to 50% by weight.

  Furthermore, in the present invention, as a water-soluble organic compound, at least a polyhydric alcohol, a solid wetting agent, and a butyl ether of glycol are used in combination to improve reliability such as print quality, ejection stability, and clogging recovery. An excellent ink composition can be provided. This is because polyhydric alcohols and solid wetting agents are suitable for controlling water retention (moisturizing properties) and penetrability of the ink composition into recording media such as plain paper, and glycol butyl ethers are suitable for ejection stability and recording. The ink composition is suitable for controlling the penetrability of the ink composition into the medium. By using these in combination, it is possible to provide a highly reliable ink composition such as print quality, ejection stability, and clogging recovery.

  As a particularly preferred water-soluble organic compound, the polyhydric alcohol is a combination of two or more selected from glycerin, diethylene glycol, triethylene glycol, 1,5-pentanediol and 1,2-hexanediol, and the solid wetting agent is Trimethylolethane or trimethylolpropane or urea, and butyl glycols include diethylene glycol monobutyl ether or triethylene glycol monobutyl ether.

[Other additives]
Further, it may contain a surface tension adjusting agent in order to control the wettability of the ink to the recording medium, to impart uniform glossiness, to obtain the penetrability into the recording medium and the printing stability in the ink jet recording method. preferable. As the surface tension adjusting agent, acetylene glycol surfactants and polyether-modified siloxanes are preferable.
Examples of acetylene glycol surfactants include Surfynol 420, 440, 465, 485, 104, STG (product of Air Products), Olphine PD-001, SPC, E1004, E1010 (product of Nissin Chemical Industry Co., Ltd.) ), Acetylenol E00, E40, E100, LH (product of Kawaken Fine Chemical Co., Ltd.) and the like. Examples of the polyether-modified siloxanes include BYK-346, 347, 348, and UV3530 (Bic Chemie product). A plurality of these may be used in the ink composition, and the surface tension is preferably adjusted to 20 to 40 mN / m, and the ink contains 0.1 to 3.0% by weight.

Furthermore, the ink composition of the present invention preferably contains a pH adjuster.
As the pH adjuster, it is possible to use alkali metal hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide, amines such as ammonia, triethanolamine, tripropanolamine, diethanolamine and monoethanolamine. Although it is possible, it preferably contains at least one pH adjusting agent selected from alkali metal hydroxides, ammonia, triethanolamine, and tripropanolamine, and is preferably adjusted to pH 6-10. If the pH is out of this range, the material constituting the ink jet printer will be adversely affected, and the clogging recoverability will deteriorate.

  Further, an antifoaming agent, an antioxidant, an ultraviolet absorber, an antiseptic / antifungal agent and the like can be added as necessary.

  The ink of the invention can be suitably used for writing instruments such as pens, stamps and the like, but can be more suitably used as an ink set for inkjet recording. In the present invention, the ink jet recording system means a system in which ink is ejected as droplets from a fine nozzle and the droplets are attached to a recording medium. This will be specifically described below.

  As a first method, there is an electrostatic suction method, which applies a strong electric field between the nozzle and the acceleration electrode placed in front of the nozzle, and continuously ejects ink from the nozzle in the form of droplets. This is a method in which a print information signal is applied to the deflection electrode while the ink droplet is flying between the deflection electrodes for recording, or a method in which the ink droplet is ejected in response to the print information signal without being deflected.

  The second method is a method in which ink droplets are forcibly ejected by applying pressure to the ink liquid with a small pump and mechanically vibrating the nozzle with a crystal resonator or the like. The ejected ink droplet is charged simultaneously with the ejection, and a printing information signal is given to the deflection electrode and recorded while the ink droplet flies between the deflection electrodes.

  The third method is a method using a piezoelectric element, in which a pressure and a print information signal are simultaneously applied to an ink liquid by a piezoelectric element to eject and record ink droplets.

  The fourth method is a method in which the ink liquid is rapidly expanded in volume by the action of heat energy, and the ink liquid is heated and foamed with a microelectrode in accordance with a print information signal to eject and record ink droplets.

  Any of the above methods can be used in the ink jet recording method using the ink composition of the present invention.

  The recorded matter of the present invention is recorded at least using the above ink composition. By using the ink composition of the present invention, this recorded matter is provided as a recorded matter having excellent color development and glossiness, and further having good abrasion resistance.

<Example>
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples.

[Adjustment of colorant dispersion]
A colorant dispersion having dispersed particles of a colorant coated with a water-insoluble polymer was prepared by the following method.

(Synthesis of water-insoluble polymers 1 to 3)
In a reaction vessel sufficiently substituted with nitrogen gas using 20 parts by weight of an organic solvent (methyl ethyl ketone), 0.03 part by weight of a polymerization chain transfer agent (2-mercaptoethanol), a polymerization initiator, and each monomer shown in Table 1. The mixture was polymerized with stirring at 75 ° C., 0.9 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile dissolved in 40 parts by weight of methyl ethyl ketone was added to 100 parts by weight of the monomer component, and The polymer solution was obtained by aging for 1 hour.

(Colorant dispersion 1)
5 parts obtained by drying the polymer solution obtained as water-insoluble polymer 1 under reduced pressure was dissolved in 15 parts of methyl ethyl ketone, and the polymer was neutralized with an aqueous sodium hydroxide solution. Furthermore, C.I. I. 15 parts of Pigment Yellow 74 was added and kneaded with a disperser while adding water.
After 100 parts of ion-exchanged water was added to the kneaded mixture and stirred, methyl ethyl ketone was removed at 60 ° C. under reduced pressure, and a part of the water was further removed, whereby a yellow pigment having a solid content concentration of 20% by weight was removed. An aqueous dispersion was obtained.

(Colorant dispersion 2)
6 parts obtained by drying the polymer solution obtained as the water-insoluble polymer 2 under reduced pressure were dissolved in 45 parts of methyl ethyl ketone, and the polymer was neutralized with an aqueous sodium hydroxide solution. Furthermore, C.I. I. 18 parts of Pigment Violet 19 was added and kneaded with a disperser while adding water.
After 120 parts of ion-exchanged water was added to the kneaded product and stirred, methyl ethyl ketone was removed at 60 ° C. under reduced pressure, and a part of the water was further removed to obtain a magenta pigment having a solid content concentration of 20% by weight. An aqueous dispersion was obtained.

(Colorant dispersion 3)
The polymer solution obtained as the water-insoluble polymer 3 was dried under reduced pressure, 5 parts obtained was dissolved in 15 parts of methyl ethyl ketone, and the polymer was neutralized with an aqueous sodium hydroxide solution. Furthermore, C.I. I. 15 parts of Pigment Blue 15: 4 was added and kneaded with a disperser while adding water.
After 100 parts of ion-exchanged water was added to the kneaded product and stirred, methyl ethyl ketone was removed at 60 ° C. under reduced pressure, and a part of the water was further removed, whereby a cyan pigment having a solid content concentration of 20% by weight was removed. An aqueous dispersion was obtained.

[Preparation of resin particles]
A resin dispersion (emulsion) having resin particles as dispersed particles was prepared by the following method. The presence or absence of film formation was judged visually by applying the emulsion thinly on an aluminum plate in an environment of room ambient temperature of about 25 ° C. Further, the particle diameter is a value of an average particle diameter measured by a particle size distribution measurement of Microtrac UPA150 (manufactured by Microtrac).

(Method for producing resin particle 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 1000 g of ion-exchanged water and 6.5 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. The internal temperature was kept at 70 ° C., 4 g of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 2 g of sodium lauryl sulfate, 20 g of acrylamide, 550 g of styrene, 200 g of butyl acrylate, and 30 g of methacrylic acid, An emulsion prepared by adding 1 g of ethylene glycol diacrylate to stirring was continuously dropped into the reaction solution over 4 hours. After completion of the dropwise addition, aging was performed for 3 hours.
After cooling the obtained aqueous emulsion to room temperature, ion exchange water and ammonia water were added to adjust the solid content to 37% by weight and pH 8.
The obtained aqueous emulsion was confirmed not to form a film at a temperature of 40 ° C., and the average particle size of the resin particles was 40 nm.

(Method for producing resin particle 2)
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 800 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 75 ° C. while purging with nitrogen under stirring. The internal temperature was kept at 75 ° C., 6 g of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 2 g of sodium lauryl sulfate, 20 g of acrylamide, 600 g of methyl methacrylate, 215 g of butyl acrylate, 30 g of methacrylic acid, tri An emulsion prepared by adding 5 g of ethylene glycol diacrylate to stirring was continuously dropped into the reaction solution over 5 hours. After completion of the dropwise addition, aging was performed for 3 hours. The obtained aqueous emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by weight and pH 8.
The obtained aqueous emulsion was confirmed not to form a film at a temperature of 40 ° C., and the average particle size of the resin particles was 60 nm.

(Method for producing resin particle 3)
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion exchange water and 3 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. The internal temperature was kept at 70 ° C., 4 g of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 300 g of styrene, 640 g of butyl acrylate, 30 g of methacrylic acid, and tri An emulsion prepared by adding 5 g of ethylene glycol diacrylate to stirring was continuously dropped into the reaction solution over 4 hours. After completion of the dropwise addition, aging was performed for 3 hours. The resulting aqueous emulsion was cooled to room temperature, and then ion-exchanged water and 5% aqueous sodium hydroxide solution were added to adjust the solid content to 40% by weight and pH 8.
The obtained aqueous emulsion was confirmed not to form a film at an ambient temperature of 40 ° C., and the average particle size of the resin particles was 90 nm.

(Method for producing resin particle 4)
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 800 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 75 ° C. while purging with nitrogen under stirring. The internal temperature was kept at 75 ° C., 6 g of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 2 g of sodium lauryl sulfate, 20 g of acrylamide, 600 g of methyl methacrylate, 215 g of butyl acrylate, and 30 g of methacrylic acid were added. The emulsion prepared in addition to stirring was continuously dropped into the reaction solution over 5 hours. After completion of the dropwise addition, aging was performed for 3 hours. The obtained aqueous emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by weight and pH 8.
The obtained aqueous emulsion was confirmed not to form a film at a temperature of 40 ° C., and the average particle size of the resin particles was 70 nm.

[Preparation of ink]
Each component was mixed in the ratio shown in Table 2, stirred at room temperature for 2 hours, and then filtered through a membrane filter having a pore size of 5 μm to prepare each ink. However, the addition amounts shown in Table 2 are all expressed as weight percent concentrations, and the numbers in parentheses in the colorant dispersion represent the solid content concentration of the colorant. The “remaining amount” of ion-exchanged water means adding ion-exchanged water so that the total amount of ink becomes 100 parts.

(Test 1) Average particle size Using a particle size distribution meter (UPA-150 manufactured by Microtrack), the ink composition was diluted 1000 times with pure water, the particle size distribution of the diluted solution was measured, and the volume average particle size was determined. It was.

(Test 2) Bronze For each ink composition, patch patterns of 100% and 50% Duty were created using an ink jet printer PX-V600, and EPSON photo paper <glossy> (trade name: manufactured by Seiko Epson Corporation) In addition, printing was performed at a resolution of 1440 dpi, visually observed under a fluorescent lamp (F11 light source) while changing the angle of the printed matter, and the hue change of reflected light was determined based on the following criteria.
A: The reflected light is white in all patches, and a hue without any uncomfortable feeling can be observed. B: The color can be confirmed in the reflected light with some of the patches, but the hue without any uncomfortable feeling can be observed. C: The color in the reflected light of the printed matter Can be confirmed, and there is a sense of incongruity.

(Test 3) Glossiness About the printed matter of Test 2, 20 ° gloss (G ₂₀ ) was measured using a gloss meter GM-268 (manufactured by Konica Minolta Co., Ltd.), and based on the following criteria from the result of the average glossiness Was judged.
In addition, it can be seen that the glossiness does not match the apparent glossiness even when the 60 ° glossiness, which is generally used as an index of specular glossiness of the printed material, shows a high value, and as a result of sharp studies, the glossiness at a viewing angle of 20 ° is apparent. Accordingly, in the present invention, gloss with a viewing angle of 20 ° was used as an index value.
A; 60 ≦ G ₂₀
B; 45 ≦ G ₂₀ <60
C; G ₂₀ <45

(Test 4) Fixability For the printed matter of Test 2, after printing, the recorded matter was naturally dried for 24 hours, and then a yellow aqueous fluorescent pen ZEBRA PEN2 (registered trademark) manufactured by Zebra Co., Ltd. was used to print characters with a writing pressure of 300 g. / 15mm, and the presence or absence of dirt was visually observed. The result was determined based on the following criteria.
A: Even if the same part is rubbed twice, no stain is produced.
B: Dirt does not occur until one rubbing, but dirt occurs after two rubbing.
C: Dirt is generated by one rubbing.

(Test 5) Gloss Change Regarding the printed matter of Test 2, after printing, the recorded matter was naturally dried for about 2 hours, and then lightly rubbed with a finger, and the presence or absence of gloss change on the printed surface was visually observed. The result was determined based on the following criteria.
A: Trace of rubbing with a finger cannot be discriminated and there is no change in gloss B: Trace of rubbing with a finger can be discerned somewhat, but there is almost no gloss change C: Trace of rubbing with a finger can be discriminated

(Test 6) Storage stability The ink was left in a 70 ° C. environment for 1 week with 50 g of ink in an aluminum pack. After standing, whether or not foreign matters (precipitates) were generated, and for those where no foreign matters were generated, changes in physical properties (viscosity, surface tension, pH, particle diameter) were further determined based on the following criteria.
A: There is no generation of foreign matter and no change in physical properties.
B: Foreign matter is not generated, but the physical properties slightly change.
C: Foreign matter is generated or the physical properties are remarkably changed.

(Test 7) Ejection stability In the case of printing in Test 2, whether or not ink dot dropout or flight bending occurs from the start of printing to the ink end, and if it occurs, printer cleaning is performed as a return operation to normal printing. The number of times it was necessary was evaluated and judged based on the following criteria.
A: No occurrence or cleaning once.
B: Cleaning 2 or 4 times.
C: Cleaning 5 times or more.

(Test 8) Clogging recovery property Using an ink jet printer PX-V600, each ink was filled into the head, and it was confirmed that ink was ejected from all nozzles. The sample was left in an environment of 40 ° C. for one week at an outside position (the head was displaced from the position of the cap provided on the printer and the head was not capped). After being allowed to stand, the number of cleanings required until the ink composition was discharged again from all nozzles was examined, and a determination was made based on the following criteria.
A: One cleaning.
B: 2 to 5 cleanings.
C: Cleaning 6 times or more The above evaluation results are summarized in Table 2.

  As is apparent from Table 3, the ink composition of the present invention is an ink composition capable of obtaining an image having an excellent gloss feeling on various recording media, particularly recording media having gloss. Therefore, there are few bronzing phenomena, and the fixing property and the abrasion resistance such as gloss change are also good. In addition, the ink set is excellent in storage stability, has excellent ejection stability and clogging recovery, is highly reliable, and is suitable for use in an ink jet recording system.

The present invention is not limited to the above-described embodiment, but can be applied to uses such as ink for writing instruments and ink for offset printing.

Claims (12)

  In an ink composition containing at least a colorant and resin particles coated with a water-insoluble polymer, the water-insoluble polymer is a polymer obtained by polymerization by a solution polymerization method using at least a polymerizable unsaturated monomer and a polymerization initiator. The colorant coated with the water-insoluble polymer is a phase inversion in which the water-insoluble polymer is dissolved in an organic solvent, and then at least the colorant and water are added and mixed, and the organic solvent is removed and dispersed in an aqueous system. An ink composition, which is a colorant obtained by an emulsification method, and the resin particles are a polymer obtained by polymerization by an emulsion polymerization method using at least a crosslinking agent.   The ink composition according to claim 1, wherein the colorant is a colorant insoluble in water.   The ink composition according to claim 1, wherein the water-insoluble polymer is a branched polymer.   The ink composition according to claim 1, wherein the resin particles are made of a polymer that does not form a film at a temperature of 40 ° C. or less.   The ink composition according to claim 1, wherein the resin particles have an average particle diameter of 20 to 80 nm.   The colorant is a pigment, contains at least water and a water-soluble organic compound, and has an average particle diameter of pigment particles in the ink composition in the range of 50 to 150 nm. Item 4. The ink composition according to item.   The ink composition according to claim 6, wherein at least a polyhydric alcohol, a solid wetting agent, and a butyl ether of glycol are used in combination as the water-soluble organic compound.   The polyhydric alcohol is a combination of two or more selected from glycerin, diethylene glycol, triethylene glycol, 1,5-pentanediol and 1,2-hexanediol, and the solid wetting agent is trimethylolethane or trimethylolpropane or 8. The ink composition according to claim 6, wherein the ink composition is urea and the butyl glycol is diethylene glycol monobutyl ether or triethylene glycol monobutyl ether.   It is used for an inkjet recording system, The composition as described in any one of Claims 1-8 characterized by the above-mentioned.   A recording method for performing printing by attaching the ink composition according to claim 1 to a recording medium.   10. An ink jet recording method according to claim 1, wherein printing is performed by ejecting ink droplets and attaching the droplets to a recording medium. A recorded matter recorded by the recording method according to claim 10.