JP2006282811A - Ink set and recorded matter obtained using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set that can realize printing qualities excellent in color developability, gloss property, fixing property and metamerism (dependence on a light source) regardless of the kind of recording media. <P>SOLUTION: The ink set comprises at least a yellow ink composition, a magenta ink composition and a cyan ink composition, where each ink composition comprises at least a polymer particle comprised of the same or similar water-insoluble vinyl polymer containing a pigment and a trialkanolamine. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink set capable of realizing print quality excellent in color developability, glossiness, fixability, and metamerism (light source dependency) regardless of the type of recording medium, and a recorded matter using the ink set. Is.

  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, since pigments are color materials excellent in water resistance, light resistance, gas resistance and water resistance, development of pigment inks utilizing these color material characteristics has been promoted. Water-based pigment ink dispersed with a surfactant or polymer dispersant, water-based pigment ink using a self-dispersed pigment with a water-dispersible functional group on the pigment surface, and pigment coated with a water-dispersible resin An aqueous pigment ink using fine particles has been proposed.

  Since such pigment ink deposits and colors pigment fine particles on the surface of the recording medium, the pigment ink is particularly excellent in color development on plain paper as compared with the case where the color penetrates into the recording medium and dyes like the dye ink. On the other hand, pigment particles (including pigment-containing colored fine particles) are stably dispersed in the ink liquid, but in the process of drying the ink after the ink has adhered to a recording medium such as paper, As the 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 printed image is deteriorated, and a high-quality image cannot be obtained.

  Further, if the aggregation properties of the ink compositions constituting the ink set are different, there is a problem that the uniformity of glossiness is lost and an unnatural print image is formed. Also, depending on the combination of pigment types selected as an ink set, metamerism (a phenomenon in which the color of a printed material observed using a certain light source does not match the color of the same printed material observed using another light source; ) May occur.

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 In order to improve the color developability and glossiness of inkjet paper, ink containing a water-insoluble vinyl polymer dispersion containing a pigment (see Patent Document 5), or a combination of specific pigment types for the purpose of suppressing metamerism Ink sets (see Patent Document 6) are proposed.
JP 2002-356737 A JP 2002-294134 A JP 2001-123098 A JP-A-11-209671 Japanese Patent Laid-Open No. 2005-41994 JP 2003-192967 A

  However, when an ink set is formed using a plurality of such water-based pigment inks, depending on the type of recording medium to be recorded, good print quality can be obtained with respect to color development, glossiness, fixability, and metamerism (light source dependency). There were cases where it was not possible.

The problem to be solved by the present invention is the above-mentioned problem.
Accordingly, an object of the present invention is to provide an ink set that can realize print quality excellent in color development, glossiness, fixability, and metamerism (light source dependency) regardless of the type of recording medium. .

The present invention relates to the following 1. The object is achieved by providing the invention.
1. An ink set comprising at least a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein each ink composition is composed of a polymer particle and a triglyceride containing a pigment in the same or similar water-insoluble vinyl polymer. An ink set comprising at least alkanolamine.

The present invention also provides the following 2. -15. Each invention is provided.
2. 2. The ink set according to 1, wherein a content of the trialkanolamine is 10 to 50% by weight with respect to 100% by weight of the pigment.

  3. 3. The ink set according to 1 or 2, wherein the content of the trialkanolamine is 1% by weight or more based on the total amount of the ink composition.

  4). 4. The ink set according to any one of 1 to 3, wherein the trialkanolamine is triethanolamine and / or tripropanolamine.

  5. The water-soluble vinyl polymer comprises (1) one or more monomers A selected from the group consisting of monomers represented by the following formula 1, formula 2, formula 3 and formula 4, and (2) a salt-forming group 5. The ink set according to any one of 1 to 4, wherein a monomer and (3) a monomer copolymerizable with the monomer A and the salt-forming group-containing monomer are polymerized.

  6). 6. The ink according to 5 above, wherein the copolymerizable monomer (3) is at least one selected from the group consisting of (meth) acrylic acid esters, aromatic ring-containing monomers and macromers. set.

  7). 7. The ink set as described in 6 above, wherein the aromatic ring-containing monomer is at least one selected from the group consisting of styrene, α-methylstyrene, vinyl toluene and vinyl naphthalene.

  8). 8. The ink set as described in 6 or 7 above, wherein the macromer is a styrenic macromer having a polymerizable functional group at one end.

  9. The ink set according to any one of 1 to 8, wherein the water-insoluble vinyl polymer has a weight average molecular weight of 3000 to 300,000.

  10. 10. The ink set according to any one of 1 to 9, wherein the additive amount of the pigment is 0.5 to 15% by weight with respect to each ink composition.

  11. The yellow ink composition contains C.I. I. Pigment Yellow 74, and the magenta ink composition contains C.I. I. Pigment Violet 19, and the cyan ink composition contains C.I. I. The ink set according to any one of 1 to 10 above, which comprises CI Pigment Blue 15: 4.

  12 Furthermore, each said ink composition is an ink set of any one of said 1-11 which comprises at least the compound represented by following formula 5 and formula 6.

  13. Furthermore, each said ink composition is an ink set of any one of said 1-12 which comprises glycol butyl ether.

  14 14. The ink set according to any one of 1 to 13, which is used in a recording method in which printing is performed by attaching ink to a recording medium.

  15. The ink set according to any one of 1 to 14, which is used in an inkjet recording method.

  16. The recorded matter recorded by the inkjet recording method using the ink set of any one of said 1-15.

According to the present invention, there is provided an ink set capable of realizing print quality excellent in color developability, glossiness, fixability, and metamerism (light source dependency) regardless of the type of recording medium.
In addition, according to the present invention, a recorded matter having print quality excellent in color development, glossiness, fixability, and metamerism (light source dependency) is provided.

In the present specification, “(meth) acryl” means “methacryl” or “acryl”.
The “same water-insoluble vinyl polymer” means that the monomer (for example, the type of monomer described later) and the composition ratio (content ratio) of the monomers are exactly the same. ,
(I) The types of monomers are exactly the same, but the composition ratio (content ratio) of each monomer is different,
(Ii) Monomer serving as a main component of the polymer [meaning a monomer that is a constituent unit of a water-insoluble vinyl polymer and whose content (raw material basis) is 10% by weight or more. ] Is essentially the same (substantially the same as the difference in the type of salt, the number of repeating oxyalkylene units, the chain length of the alkyl group, the difference between the acryloyl group and the toacryloyl group, etc. Meaning that the composition ratio (content ratio) of the main component monomer is exactly the same,
(Iii) Monomer that is a main component of a polymer [meaning a monomer that is a constituent unit of a water-insoluble vinyl polymer, and whose content (raw material basis) is 10% by weight or more. ] Is essentially the same (substantially the same as the difference in the type of salt, the number of repeating oxyalkylene units, the chain length of the alkyl group, the difference between the acryloyl group and the toacryloyl group, etc. Meaning that the composition ratio (content ratio) of the main component monomer is different,
Means.

The ink set according to the present invention will be described below based on preferred embodiments thereof.
As described above, the ink set of the present invention is an ink set comprising at least a yellow ink composition, a magenta ink composition, and a cyan ink composition, and each ink composition is the same or similar water-insoluble. It is characterized by comprising at least polymer particles in which a pigment is contained in a vinyl polymer and trialkanolamine.

  Since the ink set of the present invention has such a configuration, it is possible to realize print quality excellent in color development, glossiness, fixability, and metamerism (light source dependency) regardless of the type of recording medium. In particular, it is possible to obtain an image in which uniform glossiness is formed on a glossy recording medium.

  Examples of the water-insoluble vinyl polymer used in the present invention include (1) one or more monomers A selected from the group consisting of monomers represented by the following formula 1, formula 2, formula 3, and formula 4, (2) A product obtained by polymerizing a monomer composition containing a monomer that contains a salt-forming group and (3) the monomer A and a monomer that can be copolymerized with the salt-forming group-containing monomer has color development properties, glossiness, and fixing properties. It is preferable in that it can be improved.

  The proportion of the content in the monomer composition is as follows: (1) monomer A is 5 to 45% by weight, (2) salt-forming group-containing monomer is 3 to 40% by weight, and (3) copolymerizable monomer is 0 to 87%. It is preferable that it is weight%.

  The weight average molecular weight of the water-insoluble vinyl polymer is preferably 3000 to 300000, and more preferably 5000 to 200000, from the viewpoint of excellent printing density and printing stability.

  When the monomer of the formula 1 is used for the water-soluble vinyl polymer, there is an advantage that an ink excellent in gloss of a printed image can be obtained. Moreover, when the monomer of Formula 2 is used for the water-soluble vinyl polymer, an ink excellent in ejection property can be obtained. Moreover, when the monomer of Formula 2, Formula 3 or Formula 4 is used for the water-soluble vinyl polymer, excellent dispersion stability can be imparted to the colorant.

In formulas 1 to 4, R ¹ is a hydrogen atom or a methyl group. R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkylphenyl group having 1 to 9 carbon atoms. Among these, an octyl group and a nonylphenyl group are preferable from the viewpoints of water resistance and scratch resistance.

  m is a number from 1 to 30. From the viewpoint of ejection properties and print density, m is preferably a number from 2 to 25. n is a number from 1 to 30. From the viewpoint of ejection properties and print density, n is preferably a number from 2 to 25. In the monomer of Formula 3, the oxyethylene group and the oxypropylene group are block-added or randomly added. In the monomer of Formula 4, the oxypropylene group and the oxytetramethylene group are block-added or randomly added.

Representative examples of the monomer of formula 1 include polyethylene glycol mono (meth) acrylate and the like.
Specific examples of the monomer of Formula 2 include polypropylene glycol mono (meth) acrylate and the like.

  Specific examples of the monomer of Formula 3 include ethylene glycol / propylene glycol (meth) acrylate, poly (ethylene glycol / propylene glycol) mono (meth) acrylate, octoxypolyethylene glycol / polypropylene glycol mono (meth) acrylate, octoxypoly ( (Ethylene glycol / propylene glycol) mono (meth) acrylate, stearoxy polyethylene glycol / polypropylene glycol mono (meth) acrylate, stearoxy poly (ethylene glycol / propylene glycol) mono (meth) acrylate, nonylphenoxy polyethylene glycol / polypropylene glycol mono ( (Meth) acrylate, nonylphenoxypoly (ethylene glycol / propylene glycol) (Meth) acrylate. These can be used alone or in admixture of two or more.

  Specific examples of the monomer of formula 4 include propylene glycol / tetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate, propylene glycol / polybutylene glycol mono (meth) acrylate, poly (Propylene glycol / butylene glycol) mono (meth) acrylate and the like. These can be used alone or in admixture of two or more.

  Among the monomers A, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, ethylene glycol / propylene glycol (meth) acrylate and poly (ethylene glycol / propylene glycol) mono (meth) acrylate It is preferable from the viewpoint of dischargeability.

  Specific examples of commercially available monomer A include NK ester M-20G, 40G, 90G, 230G manufactured by Shin-Nakamura Chemical Co., Ltd., Bremer PE series of Nippon Oil & Fats Co., PME-100, 200, 400, 1000, PP-1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 30PPT-800, 50PPT-800 , 70PPT-800, APT series, 10PPB-500B, 10APB-500B, 50POEP-800B, 50AOEP-800B, ASEP series, PNEP series, PNPE series, 43ANEP-500, 70ANEP-550 and the like.

  The salt-forming group-containing monomer (2) is preferably an anionic monomer or a cationic monomer. Anionic monomers and cationic monomers can be used alone or in admixture of two or more.

  Examples of the anionic monomer include one or more selected from the group consisting of an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.

  Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid. These can be used alone or in admixture of two or more.

  Examples of unsaturated sulfonic acid monomers include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylic acid ester, bis- (3-sulfopropyl) -itaconic acid ester, and the like. Can be mentioned. These can be used alone or in admixture of two or more.

  Examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acrylic acid. And leuoxyethyl phosphate. These can be used alone or in admixture of two or more.

  Among the anionic monomers, unsaturated carboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoints of ink viscosity and dischargeability.

  Examples of the cationic monomer include one or more selected from the group consisting of an unsaturated tertiary amine-containing vinyl monomer and an unsaturated ammonium salt-containing vinyl monomer.

  Examples of the unsaturated tertiary amine-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N. -Dimethylaminopropyl (meth) acrylamide, N, N-dimethylarylamine, vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-6-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. It is done. These can be used alone or in admixture of two or more.

  Examples of unsaturated ammonium salt-containing monomers include N, N-dimethylaminoethyl (meth) acrylate quaternized product, N, N-diethylaminoethyl (meth) acrylate quaternized product, N, N-dimethylaminopropyl (meth). Examples include acrylate quaternized products. These can be used alone or in admixture of two or more.

  Among the cationic monomers, N, N-dimethylaminoethyl (meth) acrylate, NN-dimethylaminopropyl (meth) acrylamide and vinyl pyrrolidone are preferable.

  The copolymerizable monomer (3) is preferably at least one selected from the group consisting of (meth) acrylic acid esters, aromatic ring-containing monomers and macromers from the viewpoint of water resistance and scratch resistance. .

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate (Meth) acrylic acid esters in which the ester moiety such as (iso) stearyl (meth) acrylate is an alkyl group having 1 to 18 carbon atoms are used, and these are used alone or in combination of two or more. be able to.

  In addition, said (iso or tertiary) and (iso) mean both the case where these groups exist, and the case where it is not so, and when these groups do not exist, it shows normal.

  From the viewpoint of water resistance, the aromatic ring-containing monomer may be styrene, vinylnaphthalene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, 4-vinylbiphenyl, 1,1-diphenylethylene, benzyl (meth) acrylate, phenoxyethyl ( Selected from the group consisting of (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, 2-acryloyloxyethyl phthalate and neopentyl glycol acrylate benzoate 1 or more types are preferable. Among these, at least one selected from the group consisting of styrene, α-methylstyrene, vinyl toluene, and vinyl naphthalene is more preferable from the viewpoint of water resistance and scratch resistance.

  As a typical example of the macromer, there is a macromer having a polymerizable functional group at one end and preferably having a number average molecular weight of 500 to 500,000, more preferably 1000 to 10,000.

  Specific examples of the macromer include a styrenic macromer having a polymerizable functional group at one end, a silicone macromer having a polymerizable functional group at one end, a methyl methacrylate macromer having a polymerizable functional group at one end, Examples thereof include a styrene / acrylonitrile macromer having a polymerizable functional group at one end, a butyl acrylate macromer having a polymerizable functional group at one end, and an isobutyl methacrylate macromer having a polymerizable functional group at one end. Among these, a styrenic macromer having a polymerizable functional group at one end is preferable from the viewpoint of sufficiently containing a colorant in the water-insoluble vinyl polymer.

  The styrenic macromer having a polymerizable functional group at one end includes a styrene homopolymer having a polymerizable functional group at one end and a copolymer of styrene and another monomer having a polymerizable functional group at one end. A polymer is mentioned.

  In the copolymer of styrene and another monomer having a polymerizable functional group at one end, examples of the other monomer include acrylonitrile. Further, the content of styrene is preferably 60% by weight or more, and more preferably 70% by weight or more from the viewpoint of sufficiently containing the pigment in the vinyl polymer.

  Among the styrenic macromers having a polymerizable functional group at one end, a styrenic macromer having an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group at one end is preferable.

  Examples of commercially available styrenic macromers include AS-6, AS-6S, AN-6, AN-6S, HS-6S, and HS-6 manufactured by Toagosei Co., Ltd.

  The number average molecular weight of the macromer is measured by gel chromatography using 1 mmol / L 2 dodecyldimethylamine-containing chloroform as a solvent using polystyrene as a standard substance.

  The content of the aromatic ring-containing monomer in the water-insoluble vinyl polymer is preferably 0.1 to 70% by weight, more preferably 1 to 50% by weight from the viewpoints of water resistance, scratch resistance, ink viscosity and ejection stability. %.

  The content of the macromer in the water-insoluble vinyl polymer is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight from the viewpoint of water resistance and scratch resistance.

  The pigment used in each ink composition included in the ink set of the present invention may be any of organic pigments and inorganic pigments conventionally used in ink compositions for inkjet. If necessary, extender pigments can be used in combination. Specific examples include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, nitro pigments, and nitroso pigments.

  In the yellow ink composition, a yellow pigment is used as a colorant. I. Pigment yellow 74, 93, 109, 110, 128, 138, 150, 151, 154, 155, 180, 185 and the like. Among them, C.I. I. Pigment Yellow 74 and 110 are preferable.

  In the magenta ink composition, a magenta pigment is used as the colorant, and examples of the magenta pigment include C.I. I. Pigment red 122, 202, 209 and C.I. I. Pigment Violet 19 or the like is preferably used. I. Pigment red 122, C.I. I. Pigment Violet 19 is preferable.

  In the cyan ink composition, a cyan pigment is used as the colorant. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 16 and 60 are preferably used. I. Pigment Blue 15: 3 and 15: 4 are preferred.

  These cyan pigments, magenta pigments, and yellow pigments may be used alone or in combination of two or more.

  In a particularly preferred embodiment, the yellow ink composition is a C.I. I. Pigment Yellow 74, and the magenta ink composition contains C.I. I. Pigment Violet 19, and the cyan ink composition contains C.I. I. It is preferable to include CI Pigment Blue 15: 4 from the viewpoint that color development and metamerism of a color image can be suppressed.

Preparation of Polymer Particle Dispersion Including Pigment Polymer particles containing the pigment in the same or similar water-insoluble vinyl polymer used in the present invention may be blended in the ink composition as a dispersion of the polymer particles. preferable. Specifically, the polymer particle dispersion containing the pigment can be prepared by the method described in JP-A No. 2001-247810. For example, it can be preferably prepared by the following steps. That is,
(1) Step of preparing a solvent dispersion by mixing a polymer solution dissolved in a water-soluble organic solvent, a pigment, and, if necessary, a neutralizing agent. (2) Developing this dispersion into an aqueous phase to develop an aqueous solution. Transfer emulsification step for preparing a suspension (3) The step comprises a step of distilling off the water-soluble organic solvent added at the time of preparing the solvent dispersion and including the pigment in polymer particles.

  The neutralizing agent may be appropriately determined. Examples of the alkali include tertiary amines such as trimethylamine and triethylamine, ammonia, sodium hydroxide, potassium hydroxide and the like. As the acid, an inorganic base such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid, propionic acid, lactic acid, succinic acid, glycolic acid, gluconic acid or glyceric acid can be used.

  As the organic solvent, water-soluble organic solvents are preferable, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone, and ethers such as dibutyl ether, tetrahydrofuran, and dioxane. It is done.

  Dispersers can be used for the process of including the pigment in the polymer. Dispersers such as ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, jet mill, ang mill, etc. To do. More preferably, a high-pressure homogenizer that is less likely to be mixed with crushed pieces of the dispersion medium is used.

  The particle size of the polymer particles thus obtained is preferably about 25 to 250 nm, more preferably the lower limit is about 30 nm and the upper limit is about 175 nm.

  The weight ratio of these pigments to the polymer containing them is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10. The addition amount of the pigment is in the form of being included in the polymer and is preferably 0.5% by weight or more and 15% by weight or less based on the weight of the pigment alone, and more preferably the upper limit value. Is 10% by weight, and a more preferred lower limit is 1% by weight.

  According to a preferred aspect of the present invention, an ink set comprising a yellow ink composition, two kinds of magenta ink compositions having different color densities, and two kinds of cyan ink compositions having different color densities may be used. Here, the two types of magenta ink compositions having different color densities are a magenta ink composition having a higher density and a magenta ink composition having a lower density (hereinafter referred to as “light magenta ink composition”). There is). The two cyan ink compositions having different color densities are a cyan ink composition having a higher density and a cyan ink composition having a lower density (hereinafter sometimes referred to as “light cyan ink composition”). It consists of. The light magenta ink composition and the light cyan ink composition can be prepared by appropriately selecting pigments and other components and appropriately changing the blending amounts thereof to reduce the color density.

  The trialkanolamine used in the present invention is preferably used not as a neutralizing agent for a pigment-containing water-insoluble vinyl polymer but as a gloss-imparting agent for an ink composition, and has a uniform gloss on a glossy recording medium. It is contained in yellow, magenta and cyan ink compositions in order to form a retained image.

  In addition, the content of the trialkanolamine is preferably 10 to 50% by weight with respect to 100% by weight of the pigment, from the viewpoint of erosion to members used in the printer, ink viscosity, and gloss, More preferably, it is 1% by weight, more preferably 1% by weight or more based on the total amount of the ink composition, and more preferably, the upper limit is 3% by weight and the lower limit is 1% by weight.

  The trialkanolamine used in the present invention is not particularly limited, but triethanolamine and / or tripropanolamine are preferable from the viewpoint of improving printing stability and glossiness.

  Each ink composition in the ink set of the present invention preferably contains at least a compound represented by the following formulas 5 and 6 from the viewpoint of color developability and printing stability.

  As the compound of Formula 5, commercially available products such as Olphine STG (trade name, manufactured by Nissin Chemical Co., Ltd.) and Surfynol 104 (trade name, manufactured by Air Products and Chemicals Inc.) can be used. Commercially available products such as Surfynol 400 series (trade name, manufactured by Air Products and Chemicals Inc.) and Olphine E1010 (trade name, manufactured by Nissin Chemical Co., Ltd.) can be used as the compound of formula 6. The total content of the compounds of formulas 5 and 6 is preferably 0.03 to 5% by weight, more preferably 0.5 to 3% by weight, based on the ink composition.

  Moreover, it is preferable that each ink composition contains glycol butyl ether from the viewpoint that excellent print quality can be formed. As the glycol butyl ether, for example, glycol mono-n-butyl ether is particularly preferable. Examples of such glycol mono-n-butyl ether include ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, or dipropylene. A thing chosen from glycol mono-n-butyl ether is mentioned as a preferable thing. Two or more of these may be used in combination. The glycol butyl ether is preferably 0.05 to 15% by weight, more preferably 0.5 to 10% by weight, based on the ink composition.

  Each ink composition in the ink set of the present invention comprises water as a main solvent. As the water, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold or bacteria can be prevented when the ink composition is stored for a long period of time.

  Each ink composition in the ink set of the present invention preferably further comprises 1,2-alkanediol. Such 1,2-alkanediol is preferably selected from the group consisting of 1,2-alkanediols having 4 to 10 carbon atoms. In this case, 1,2-alkanediol may be mixed and added.

  In a preferred embodiment of the invention, the 1,2-alkanediol is a group consisting of 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and mixtures thereof. More selected. These are more preferable from the viewpoint of excellent permeability to a recording medium.

  In a more preferred embodiment of the present invention, the 1,2-alkanediol is preferably 1,2-hexanediol or 1,2-pentanediol, more preferably 1,2-hexanediol. .

  The addition amount of 1,2-alkanediol is preferably 0.25 wt% or more and 15 wt% or less with respect to the total amount of the ink composition, and a more preferable upper limit value is 10 wt%, and a more preferable lower limit value. The value is 0.5% by weight.

  According to a preferred aspect of the present invention, each ink composition preferably comprises a polyol in order to prevent clogging of the nozzles of the ink jet recording head. Such polyols are preferably water-soluble polyols, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, 1, 3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, mesoerythritol, pentaerythritol, thiodi Glycol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol And the like.

  Further, lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and ε-caprolactam, and ureas such as urea, thiourea, ethylene urea, and 1,3-dimethylimidazolidinone can also be used. Furthermore, as monosaccharides, disaccharides, oligosaccharides and polysaccharides, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, maltotri Aose can also be added. Furthermore, derivatives of these saccharides can also be used, and examples thereof include the reducing sugars, oxidized sugars, amino acids, and thio sugars of the aforementioned sugars. Of these, sugar alcohols are particularly preferred, and specific examples include maltitol and sorbit. Moreover, you may obtain and use commercially available products, such as HS-500 and HS-300 (made by Hayashibara Biochemical Research Institute). You may use these in mixture of 2 or more types.

  The addition amount of these clogging prevention components is preferably 5% by weight or more and 40% by weight or less with respect to the total amount of the ink composition, a more preferable upper limit value is 30% by weight, and a more preferable lower limit value is 10% by weight.

  These components are preferably added together with other ink additives in such an amount that the ink viscosity becomes 5 cPs or less at 25 ° C.

  Each ink composition in the ink set of the present invention has other optional components such as a preservative, a fungicide, and a pH adjuster other than trialkanolamine (preferably an ink composition) in order to improve various properties. In such an amount that the pH is adjusted to 8 to 11), an antioxidant, a conductivity adjusting agent, a surface tension adjusting agent, or an oxygen absorbent.

  Each ink composition in the ink set of the present invention may be prepared by supplying and dispersing the above-described components to a dispersing / mixing machine (for example, a ball mill, a sand mill, an attritor, a basket mill, a roll mill, etc.). . According to a preferred embodiment of the present invention, it is preferable to filter the ink stock solution obtained by the above-described dispersing / mixing device using a filter such as a membrane filter or a mesh filter to remove coarse particles.

  The ink set according to the present invention is used in a recording method using an ink composition. Examples of the recording method using the ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, and other various printing methods. The ink set according to the present invention is used in a recording method in which an ink composition is attached to a recording medium for printing, and is preferably used in an ink jet recording method.

  According to another aspect of the present invention, there is provided an ink jet recording method for performing printing by ejecting droplets of an ink composition and attaching the droplets to a recording medium. At least yellow, magenta and cyan ink compositions are used. According to a preferred aspect of the present invention, the ink set according to the present invention described above is used as such an ink set. By such an ink jet recording method, it is possible to prevent the occurrence of uneven gloss (uneven gloss) and metamerism that may occur when printing on glossy paper.

  Further, according to the present invention, it is possible to provide a recorded matter recorded by the ink jet recording method using the ink set described above. Such recorded matter has a print quality excellent in color development, glossiness, fixability, and metamerism (light source dependency).

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this Example.

Preparation of Yellow Ink Composition (Y1 to Y6), Magenta Ink Composition (M1 to M6), and Cyan Ink Composition (C1 to C6) First, polymers used for each ink composition were obtained as follows.
In a reaction vessel, 20% by weight of methyl ethyl ketone, 0.03 part by weight of a polymerization chain transfer agent (2-mercaptoethanol), and 10% by weight of each monomer amount (parts by weight) shown in Table 1 are added. Mixing was performed and nitrogen gas substitution was sufficiently performed to obtain a mixed solution.

  On the other hand, the remaining 90% by weight of the amount (parts by weight) of each monomer shown in Table 1 was charged into the dropping funnel, and then 0.27 parts by weight of a polymerization chain transfer agent (2-mercaptoethanol), methyl ethyl ketone 60 Part by weight and 1.2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and mixed, and the gas was sufficiently replaced with nitrogen gas to obtain a mixed solution.

  Under a nitrogen atmosphere, the temperature of the mixed solution in the reaction vessel was increased to 65 ° C. while stirring, and the mixed solution in the dropping funnel was gradually dropped into the reaction vessel over 3 hours. After completion of the dropwise addition, the liquid temperature of the mixed solution was maintained at 65 ° C. for 2 hours, and then a solution in which 0.3 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 5 parts by weight of methyl ethyl ketone was prepared. In addition to the mixed solution, the mixture was further aged at 65 ° C. for 2 hours and 70 ° C. for 2 hours to obtain a polymer solution of polymer A or polymer B. The weight average molecular weights of polymer A and polymer B were 70000, respectively.

The details of each compound shown in Table 1 are as follows.
Polyethylene glycol monomethacrylate (m = 23): manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester M230G, wherein in Formula 1, m is 23, and R ¹ and R ² are methyl groups.

Polypropylene glycol monomethacrylate (n = 9): manufactured by Nippon Oil & Fats Co., Ltd., trade name: BLEMMER PP-500, in formula 2, R ¹ is a methyl group and R ² is a hydrogen atom.

Poly (ethylene glycol / propylene glycol) monomethacrylate: manufactured by Nippon Oil & Fats Co., Ltd., trade name: BLEMMER 50PEP-300, in the above formula 3, m is 3.5, n is 2.5, R ¹ is a methyl group, Monomer in which R ² is a hydrogen atom and an oxypropylene group and an oxyethylene group are randomly added

Styrene macromer: manufactured by Toagosei Co., Ltd., trade name: AS-6S (styrene macromer), number average molecular weight: 6000, polymerizable functional group: methacryloyloxy group

(Preparation of pigment dispersion Y (1))
5 parts by weight of the polymer obtained by drying the polymer solution of polymer A obtained above under reduced pressure was dissolved in 45 parts by weight of methyl ethyl ketone, and a predetermined amount of neutralizing agent (20% aqueous sodium hydroxide solution) was added thereto. Neutralize the salt-forming groups, and I. 20 parts by weight of Pigment Yellow 74 was added and kneaded in a bead mill for 2 hours. To the obtained kneaded product, 120 parts by weight of ion-exchanged water was added and stirred. Then, methyl ethyl ketone was removed at 60 ° C. under reduced pressure, and a part of the water was further removed, so that the solid content concentration was 20% by weight. An aqueous dispersion of pigment-containing vinyl polymer particles (pigment dispersion Y (1)) was obtained.

(Preparation of pigment dispersion Y (2))
In the preparation of the pigment dispersion Y (1), an aqueous dispersion of pigment-containing vinyl polymer particles having a solid content concentration of 20% by weight (pigment dispersion) was prepared except that the polymer A was changed to the polymer B. Y (2)) was obtained.

(Preparation of pigment dispersion Y (3))
In the preparation of the pigment dispersion Y (2), C.I. I. Pigment Yellow 74 is C.I. I. Except having changed to pigment yellow 110, it adjusted by the same method and obtained the water dispersion (pigment dispersion Y (3)) of the pigment containing vinyl polymer particle | grains whose solid content concentration is 20 weight%.

(Preparation of pigment dispersion M (1))
In the preparation of the pigment dispersion Y (1), C.I. I. Pigment Yellow 74 is C.I. I. Except having changed to pigment violet 19, it adjusted by the same method and obtained the water dispersion (pigment dispersion liquid M (1)) of the pigment containing vinyl polymer particle | grains whose solid content concentration is 20 weight%.

(Preparation of pigment dispersion M (2))
In the preparation of the pigment dispersion M (1), an aqueous dispersion of pigment-containing vinyl polymer particles having a solid content concentration of 20% by weight (pigment dispersion) was prepared except that the polymer A was changed to the polymer B. M (2)) was obtained.

(Preparation of pigment dispersion M (3))
In the preparation of the pigment dispersion M (2), C.I. I. Pigment Violet 19 is C.I. I. Except having changed to pigment red 122, it adjusted by the same method and obtained the water dispersion (pigment dispersion liquid M (3)) of the pigment containing vinyl polymer particle | grains whose solid content concentration is 20 weight%.

(Preparation of pigment dispersion C (1))
In the preparation of the pigment dispersion Y (1), C.I. I. Pigment Yellow 74 is C.I. I. Except having changed to pigment blue 15: 4, it adjusted by the same method and obtained the water dispersion (pigment dispersion C (1)) of the pigment containing vinyl polymer particle | grains whose solid content concentration is 20 weight%.

(Preparation of pigment dispersion C (2))
In the preparation of the pigment dispersion C (1), an aqueous dispersion of pigment-containing vinyl polymer particles having a solid content concentration of 20% by weight (pigment dispersion) was prepared except that the polymer A was changed to the polymer B. C (2)) was obtained.

(Preparation of pigment dispersion C (3))
In the preparation of the pigment dispersion C (2), C.I. I. Pigment Blue 15: 4 to C.I. I. Except having changed to pigment blue 15: 3, it adjusted by the same method and obtained the water dispersion (pigment dispersion C (3)) of the pigment containing vinyl polymer particle | grains whose solid content concentration is 20 weight%.

  According to the composition shown in Table 2 below, the pigment dispersion of yellow ink, magenta ink or cyan ink described above, solvents and ultrapure water were mixed and stirred for 2 hours. Then, it filtered using the membrane filter (brand name) (made by Nippon Millipore Limited) with a hole diameter of about 1.2 micrometers, and prepared the ink composition. In Table 2, the amount of each composition added is% by weight.

Preparation of Ink Set The yellow, magenta, and cyan ink compositions obtained above were combined as shown in Table 3 below to obtain an ink set.

  For each of the ink sets 1 to 9 shown in Table 3, the following color developability, glossiness, scratch resistance, metamerism, and print stability were evaluated. For the evaluation, PX-A550 (manufactured by Seiko Epson) was used as a printer, and the ink set shown in Table 3 was used for yellow ink, magenta ink, and cyan ink. The evaluation results are shown in Table 4.

Evaluation 1: Color development For each ink set shown in Table 3, a color chart composed of color 384 patches is printed on Xerox4024 (manufactured by Xerox), and using Spectrolino (manufactured by Gretag Macbeth), L *, a * of the printed matter , B * was measured. For the color reproduction range, the color space is divided into 10 by L * values, and the a * b * space area (a * and b * values) of each L * value is obtained, and then a * b of all L * values. * Calculated by calculating the spatial region and calculating the L * a * b * color space volume (gamut value). The obtained results were evaluated according to the following criteria.
Evaluation A: The size of the color reproduction range is 200000 or more.
Evaluation B: The color reproduction range is 150,000 or more and less than 200000.
Evaluation C: The color reproduction range is less than 150,000.

Evaluation 2: Glossiness For each ink set shown in Table 3, a solid color pattern composed of cyan, magenta, yellow, red, green, and blue was printed on photographic paper <glossy> (manufactured by Seiko Epson), and GM-268 ( Using a Konica Minolta Co., Ltd., the 20 ° glossiness of the printed matter was measured. The obtained results were evaluated according to the following criteria.
Evaluation A: The average value of 20 ° glossiness is 30 or more.
Evaluation B: The average value of 20 ° glossiness is 15 or more and less than 30.
Evaluation C: The average value of 20 ° glossiness is less than 15.

Evaluation 3: Scratch resistance For each ink set shown in Table 3, a color chart composed of color 384 patches was printed on Xerox 4024 (manufactured by Xerox Co., Ltd.), and when 48 hours had passed after printing, a Southerland Lab Tester was used. The scratch resistance was evaluated according to JIS K 5701. The evaluation criteria are as follows.
Evaluation A: There is no peeling of the colorant.
Evaluation B: Slight peeling of colorant (less than 20% of the whole colorant)
Evaluation C: There is peeling of the colorant (20% or more and less than 80% of the whole colorant)
Evaluation D: Colorant is almost peeled off (80% or more of the whole colorant is peeled off)

Evaluation 4: Metamerism For each ink set shown in Table 3, a composite gray formed only with color inks is printed on photographic paper <glossy> (manufactured by Seiko Epson), and the gray color when using a D50 light source and an A light source The color change amount ΔE was measured, and the absolute value | ΔE | of the maximum value was obtained. The obtained results were evaluated according to the following criteria.
Evaluation A: | ΔE | is less than 5.
Evaluation B: | ΔE | is 5 or more and less than 10.
Evaluation C: | ΔE | is 10 or more.

Evaluation 5: Printing stability Using an ink jet printer PX-A550 (trade name, manufactured by Seiko Epson Corporation), the obtained ink composition was filled in an ink cartridge, mounted on the printer, and continuously for 10 minutes. After printing and confirming that all nozzles discharged normally, continuous printing was performed on photographic paper <gloss> (trade name, manufactured by Seiko Epson Corporation) for a long time in an environment of a temperature of 40 ° C. About each ink composition, the dot missing at the time of printing and the presence or absence of ink scattering were observed, and the ejection stability was evaluated according to the following criteria.
Evaluation A: No dot dropout or ink scattering occurs even after 4 hours.
Evaluation B: After 3 hours, occurrence of missing dots or ink scattering could be confirmed.
Evaluation C: After 2 hours, dot missing or ink splattering was confirmed.
Evaluation D: Occurrence of missing dots or ink scattering occurred within 1 hour.

  The present invention is an ink set capable of realizing printing quality excellent in color development, glossiness, fixing property and metamerism (light source dependency) regardless of the type of the recording medium, and excellent recorded by the ink set. It has industrial applicability as a recorded matter with high print quality.

Claims (16)

  An ink set comprising at least a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein each ink composition includes a polymer particle and a tribite containing a pigment in the same or similar water-insoluble vinyl polymer. An ink set comprising at least alkanolamine.   The ink set according to claim 1, wherein the content of the trialkanolamine is 10 to 50% by weight with respect to 100% by weight of the pigment.   The ink set according to claim 1 or 2, wherein the content of the trialkanolamine is 1% by weight or more based on the total amount of the ink composition.   The ink set according to claim 1, wherein the trialkanolamine is triethanolamine and / or tripropanolamine. The water-soluble vinyl polymer comprises (1) one or more monomers A selected from the group consisting of monomers represented by the following formula 1, formula 2, formula 3 and formula 4, and (2) a salt-forming group The ink set according to any one of claims 1 to 4, wherein a monomer and (3) a monomer copolymerizable with the monomer A and the salt-forming group-containing monomer are polymerized.

  The copolymerizable monomer (3) is at least one selected from the group consisting of (meth) acrylic acid esters, aromatic ring-containing monomers and macromers. Ink set.   The ink set according to claim 6, wherein the aromatic ring-containing monomer is at least one selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, and vinylnaphthalene.   The ink set according to claim 6 or 7, wherein the macromer is a styrenic macromer having a polymerizable functional group at one end.   The ink set according to any one of claims 1 to 8, wherein the water-insoluble vinyl polymer has a weight average molecular weight of 3000 to 300,000.   The ink set according to any one of claims 1 to 9, wherein the amount of the pigment added is 0.5 to 15% by weight with respect to each ink composition.   The yellow ink composition contains C.I. I. Pigment Yellow 74, and the magenta ink composition contains C.I. I. Pigment Violet 19, and the cyan ink composition contains C.I. I. The ink set according to any one of claims 1 to 10, comprising CI Pigment Blue 15: 4. The ink set according to any one of Claims 1 to 11, wherein each of the ink compositions comprises at least a compound represented by Formula 5 and Formula 6 below.

  The ink set according to any one of claims 1 to 12, wherein each of the ink compositions comprises glycol butyl ether.   The ink set according to any one of claims 1 to 13, which is used in a recording method in which printing is performed by attaching ink to a recording medium.   The ink set according to any one of claims 1 to 14, which is used in an ink jet recording method.   A recorded matter recorded by the ink jet recording method using the ink set according to claim 1.