JP2017019252A - Receptive solution for inkjet recording, ink set for inkjet recording including receptive solution, and method for producing printed matter using ink set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a receptive solution for inkjet recording which enhances characteristics required for an inkjet recording method, in particular, prevention of clogging of a nozzle and storage stability, and can improve water resistance and image quality of a printed matter, and to provide an ink set for inkjet recording including the receptive solution.SOLUTION: There is provided a receptive solution for inkjet recording which contains polyvalent metal salt, a water-soluble solvent and a resin, where a resin emulsion is contained as the resin, and the polyvalent metal salt is salt containing polyvalent metal ions and inorganic amphoteric ions.SELECTED DRAWING: None

Description

  The present invention relates to a receiving solution for ink jet recording, an ink set for ink jet recording including the receiving solution, and a method for producing a printed matter using the ink set.

  The ink jet recording method is a recording method in which ink droplets are directly ejected from a very fine nozzle onto a recording medium such as paper and applied to obtain characters and images. This recording method is easy to downsize, speed up, reduce noise, save power, and color, and can perform non-contact printing on recording media. The scope of application has been expanded to commercial printing applications.

  As inks used in ink jet recording systems, water-based dye inks in which various water-soluble dyes are dissolved in water or a mixture of water and a water-soluble organic solvent are widely used. However, when water-based dye ink is ejected onto recording media such as plain paper and recycled paper, which are widely used, the ink is absorbed by the paper fiber and spreads around the landing position, which is called feathering. Can occur. In order to solve this problem, there has been proposed an inkjet dedicated paper in which a receiving layer for absorbing and receiving a water-based dye ink is formed on the surface of a recording medium such as paper (see, for example, Patent Documents 1 to 3). However, in office and commercial printing applications, the cost of the printed material itself must be reduced, and as a recording medium, non-coated paper such as inexpensive copy paper that has not been subjected to special treatment to improve printability Is often used.

  Therefore, paying attention to the fact that the dye is anionic, prior to applying the aqueous dye ink to the recording medium, an ink jet recording receiving solution containing a polyvalent metal salt is applied to the recording medium, and then the ink jet recording receiving is received. It has been proposed to apply an aqueous dye ink on a solution (see, for example, Patent Documents 4 to 7). In recent years, not only water-based dye inks but also water-based pigment inks have been widely used because feathering can be suppressed compared to water-based dye inks. However, water-based pigment inks can also be fixed using the receiving solution. It is known that it can be performed (for example, refer patent documents 8-11).

JP-A-57-069054 Japanese Patent Laid-Open No. 6-143797 JP 2009-178912 A JP 63-299970 A JP-A-5-202328 JP 2001-162920 A JP 2012-111845 A Japanese Patent Laid-Open No. 11-034478 JP-A-9-207424 JP 2011-251436 A JP 2012-136589 A

  In a conventional ink jet recording receiving solution (hereinafter sometimes simply referred to as a reaction solution or a processing solution), the polyvalent metal salt contained in the ink jet recording receiving solution is precipitated, and nozzle clogging or ink jet recording in the ink jet head is performed. Blockage of the reaction liquid flow path in the apparatus may occur. In general, it is said that the receiving solution for ink jet recording deteriorates with the passage of time, and it is required to improve the storage stability and suppress the deterioration of the receiving solution. There is also a need for further improvements in water resistance and image quality of printed matter.

  Until now, in the ink containing the coloring material, in the expectation of the moisturizing effect and the pH adjusting effect, a compound containing an organic zwitterion such as an amino acid may be contained in the ink jet recording receiving solution. It has not been found that the performance and stability of the receiving solution can be improved by containing a polyvalent metal salt of an organic zwitterion.

  The present invention has been made in view of the above circumstances, and an object thereof is to prevent nozzle clogging, which is a characteristic required for an ink jet recording system, and to improve storage stability. And providing an ink-jet recording receiving solution capable of improving the water resistance and image quality of printed matter, and an ink-jet recording ink set including the receiving solution.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that the composition of the polyvalent metal salt contained in the ink-jet recording receiving solution has a specific composition, so that bleeding or unevenness of the printed matter is caused. As a result, the present inventors have found that it is possible to contribute not only to prevention of clogging but also to prevention of clogging of the nozzles of the receiving solution and the ink set and improvement of storage stability.

  (1) A receiving solution for ink jet recording containing a polyvalent metal salt, a water-soluble solvent, and a resin, wherein the resin emulsion is contained as the resin, and the polyvalent metal salt is composed of a polyvalent metal ion and an organic compound. A receiving solution for inkjet recording, which is a salt containing zwitterions.

  (2) The ink jet recording receiving solution according to (1), wherein the polyvalent metal salt is a salt substantially free of an inorganic salt.

  (3) The inkjet recording receiving solution according to (1) or (2), wherein a mass molar concentration of the polyvalent metal salt in the inkjet recording receiving solution is 0.001 mol / kg or more and 1.0 mol / kg or less. .

  (4) The inkjet recording receiving solution according to any one of (1) to (3), wherein the polyvalent metal salt is a salt of a polyvalent metal ion and an amino acid ion.

  (5) The inkjet recording receiving solution according to (4), wherein the amino acid is an α-amino acid.

  (6) The accepting solution for inkjet recording according to (4) or (5), wherein the amino acid is an amino acid containing a nitrogen-containing heterocyclic structure.

  (7) The polyvalent metal ion is one or more polyvalent metal ions selected from the group consisting of calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions, any of (1) to (6) A receiving solution for ink-jet recording according to claim 1.

  (8) An ink set for ink-jet recording comprising the ink-jet recording receiving solution according to any one of (1) to (7) and an ink-jet recording ink containing a coloring material.

  (9) A method for producing a printed matter including a step of applying the ink-jet recording receiving solution according to any one of (1) to (7) on a recording medium or an ink containing a coloring material.

  According to the present invention, a receiving solution for inkjet recording, which can prevent nozzle clogging, which is a characteristic required for an inkjet recording system, can improve storage stability, and can improve the image quality of printed matter, It is possible to provide an ink set including the receiving solution and a method for producing a printed matter using the receiving solution or the ink set.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Accepting solution for inkjet recording>
The ink jet recording receiving solution of the present invention (hereinafter sometimes simply referred to as “receiving solution”) contains at least a polyvalent metal salt, a water-soluble solvent, and a resin. Hereinafter, the polyvalent metal salt, the water-soluble solvent and the resin contained in the receiving solution will be described.

[Multivalent metal salt]
The polyvalent metal salt contained in the receiving solution of the present invention is a salt containing a polyvalent metal ion and an organic amphoteric ion. A polyvalent metal ion refers to a metal ion having a valence of at least two or more. An organic zwitterion is a molecular ion of an organic compound, and refers to a molecular ion containing both basic groups and acidic groups in the same molecular ion. In this specification, the accepting solution containing a polyvalent metal salt is not only an accepting solution obtained by adding a polyvalent metal salt at the time of preparing the accepting solution, but also a compound capable of generating polyvalent metal ions, It is a concept that includes a receiving solution containing a polyvalent metal ion and an organic zwitterion by adding a compound capable of generating an organic zwitterion during the preparation of the receiving solution. For example, a compound capable of generating an organic amphoteric ion (for example, pyrrolidone carboxylic acid) and a compound capable of generating a polyvalent metal ion (for example, hydroxylation) without being added directly as a polyvalent metal salt at the time of preparation of a receiving solution. By adding calcium) to the receiving solution, each compound forms an ion in the receiving solution, and organic amphoteric ions (for example, pyrrolidone carboxylic acid ions) and polyvalent metal ions (for example, calcium ions) are received in the receiving solution. Also within the scope of the present invention is an embodiment that is contained within.

  Among the aspects of the accepting solution containing the above polyvalent metal salt, the accepting solution is produced by adding a polyvalent metal salt containing a polyvalent metal ion and an organic amphoteric ion to a water-soluble solvent. preferable. This is because the receiving solution of the present invention can be easily produced. In addition, since the polyvalent metal salt containing the polyvalent metal ion and the organic amphoteric ion is less likely to reduce the dispersion stability of the resin emulsion in the receiving solution, it can be used as a preferable receiving solution. .

  By containing a polyvalent metal salt in the receiving solution, bleeding and feathering can be effectively suppressed. The molar concentration of the polyvalent metal salt in the ink jet recording receiving solution is preferably 0.001 mol / kg or more and 1.0 mol / kg or less, and preferably 0.01 mol / kg or more and 0.5 mol / kg or less. More preferably, it is most preferably 0.02 mol / kg or more and 0.35 mol / kg or less. Bleeding and feathering can be more effectively suppressed when the molar mass concentration of the polyvalent metal salt is 0.001 mol / kg or more. By setting the mass molar concentration of the polyvalent metal salt to 1.0 mol / kg or less, the precipitation of the polyvalent metal salt can be further suppressed.

  The content of the inorganic salt in the polyvalent metal salt is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably substantially not contained in the total amount of the polyvalent metal salt. By setting the content of the inorganic salt to a predetermined amount or less, ejection stability and storage stability can be improved. In the present specification, the phrase “substantially containing no inorganic salt” means that the inorganic salt is 1% by mass or less based on the total amount of the polyvalent metal salt.

  Examples of inorganic salts include conventionally known inorganic salts. Specific examples include magnesium chloride, calcium chloride, zinc chloride, aluminum chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium nitrate, and calcium nitrate.

[Organic zwitterion]
The organic zwitterion contained in the polyvalent metal salt of the receiving solution of the present invention is a molecular ion of an organic compound, and includes a functional ion of both a basic group and an acidic group in the same molecular ion. Say. By using the molecular ion of the organic compound, the solubility in the receiving solution can be improved. Moreover, the amphoteric ion containing both the basic group and the functional group of the acidic group is contained in the receiving solution, so that the ion state can be stably formed even in the receiving solution (in the water-soluble solvent). . Furthermore, the molecular ion of the organic compound has a higher molecular weight than the inorganic compound, and the charge density can be dispersed within the molecule, so that the solubility in the receiving solution is good. Therefore, it is possible to prevent nozzle clogging of the ink jet head due to the precipitation of the polyvalent metal salt and blockage of the flow path of the reaction liquid in the ink jet recording apparatus. A molecular ion containing both basic and acidic functional groups in the same molecular ion is, for example, an amino acid having an amino group that is a basic group and a carboxyl group that is an acidic group in the same molecular ion. An ion etc. can be mentioned.

(Amino acid ion)
The amino acid ion contained in the polyvalent metal salt of the receiving solution of the present invention is a molecular ion having an amino group and a carboxyl group in the same molecule. Examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, hydroxyproline, serine, threonine, tryptophan, tyrosine, valine, Pantothenic acid, pyrrolidone carboxylic acid, nicotinic acid, 2-pyridinecarboxylic acid, pyrrole-3-carboxylic acid, 3-pyridinecarboxylic acid, pyrrole-2-carboxylic acid, oxalicin, pipecolic acid, morpholine carboxylic acid, N-acetylglycine, N-acetyl-DL-alanine, glycylglycine, glycyl-DL-alanine, N-glycyl-DL-2-aminobutyric acid, DL-leucylglycine, N-acetyl-DL-leucine Benzoylglycine, N- (3-methylbenzoyl) glycine, L-alanyl-L-proline, glycyl-L-proline, N-acetyl-4-hydroxypyrrolidine-2-carboxylic acid, 2-pyrrolidinone-1-methyl acetate, Examples include 2-hydroxyquinoline-4-carboxylic acid, 1-benzyl-4-carboxy-2-pyrrolidinone, 4-carboxy-2-pyrrolidinone, 1-methyl-4-carboxy-2-pyrrolidinone, 1-acetylproline, and the like. .

  Among them, the amino group that is a basic group and the carboxyl group that is an acidic group are present in the vicinity, so that the acid-base balance is improved and the stability of the receiving solution can be further improved. Therefore, among these, an α-amino acid in which an amino group and a carboxyl group are bonded to the same carbon atom is more preferable. Examples of α-amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, hydroxyproline, serine, threonine, tryptophan, tyrosine, Valine, pantothenic acid, pyrrolidone carboxylic acid, 2-pyridinecarboxylic acid, pyrrole-2-carboxylic acid, oxalicin, pipecolic acid, morpholine carboxylic acid, N-acetylglycine, N-acetyl-DL-alanine, glycylglycine, glycyl- DL-alanine, N-glycyl-DL-2-aminobutyric acid, DL-leucylglycine, N-acetyl-DL-leucine, benzoylglycine, N- (3-methylbenzoyl) glycine L- alanyl -L- proline, glycyl -L- proline, etc. N- acetyl-4-hydroxypyrrolidine-2-carboxylic acid.

  Among them, since the hydrophilic-hydrophobic balance is good, it is excellent in compatibility with each component contained in the receiving solution, and the stability of the receiving solution can be kept good. It is more preferable that it is an amino acid. Examples of amino acids having a nitrogen-containing heterocyclic structure include histidine, proline, tryptophan, pyrrolidone carboxylic acid, nicotinic acid, 2-pyridinecarboxylic acid, pyrrole-3-carboxylic acid, 3-pyridinecarboxylic acid, and pyrrole-2-carboxylic acid. Acid, pipecolic acid, morpholine carboxylic acid, L-alanyl-L-proline, glycyl-L-proline, N-acetyl-4-hydroxypyrrolidine-2-carboxylic acid, 2-pyrrolidinone-1-acetic acid, 2-hydroxyquinoline- Examples include 4-carboxylic acid, 1-benzyl-4-carboxy-2-pyrrolidinone, 4-carboxy-2-pyrrolidinone, 1-methyl-4-carboxy-2-pyrrolidinone, 1-acetylproline and the like.

  Among amino acids having a nitrogen-containing heterocyclic structure, it is an amino acid having a lactam structure from the viewpoint of good ion stability, high solubility in a receiving solution, and good accepting solution stability. It is more preferable. Examples of amino acids having a lactam structure include pyrrolidone carboxylic acid.

[Multivalent metal ion]
The polyvalent metal ion contained in the polyvalent metal salt of the receiving solution of the present invention refers to a metal ion having a valence of at least two or more. By using polyvalent metal ions, ink bleeding can be suppressed. Examples of the polyvalent metal ion include calcium ion, magnesium ion, aluminum ion, titanium ion, iron (II) ion, iron (III) ion, cobalt ion, nickel ion, copper ion, zinc ion, barium ion, and strontium ion. Is mentioned. Among them, since the interaction with the color material in the ink is large and the effect of suppressing bleeding and unevenness is enhanced, at least one selected from calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions is used. It is preferable to contain.

  Therefore, the polyvalent metal salt relating to the present invention has one or more polyvalent metal ions selected from calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions as organic amphoteric ions as α-amino acid ions. It is preferable to use a valent metal ion. In addition, an organic amphoteric ion is an amino acid ion having a nitrogen-containing heterocyclic structure, and the polyvalent metal ion is one or more polyvalent metal ions selected from calcium ion, magnesium ion, nickel ion, zinc ion, and aluminum ion It is preferable to do. Further, the organic amphoteric ion may be an amino acid ion having a lactam structure, and the polyvalent metal ion may be one or more polyvalent metal ions selected from calcium ion, magnesium ion, nickel ion, zinc ion, and aluminum ion. preferable.

[Water-soluble solvent]
The solvent used in the receiving solution of the present invention can disperse or dissolve a resin or the like. As such a solvent, a water-soluble solvent having water solubility is used.

  Here, in this specification, the water-soluble solvent means a solvent that can be dissolved in 100 parts by mass of water at 25 ° C. under 5 atm. Specifically, the water-soluble solvent that can be used in the receiving solution of the present invention preferably contains water, a water-soluble organic solvent, or a mixed solvent thereof. It is preferable that water, a water-soluble organic solvent or a mixed solvent thereof is contained in an amount of not less than 50% by mass, particularly preferably not less than 70% by mass, and particularly preferably not less than 80% by mass. preferable. By including water, a water-soluble organic solvent or a mixed solvent thereof in such a range, the dispersion stability of the resin can be further improved. In addition, as water contained in the said water-soluble solvent, it does not contain various ion, It is preferable to use deionized water, such as ion-exchange water, distilled water, and ultrapure water.

  Examples of such water-soluble organic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-pentanol. Alkyl alcohols having 1 to 5 carbon atoms; monovalent such as 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol and 3-methoxy-n-butanol Alcohols: 1-dimethylformamide, dimethylacetamide, 3-methoxypropanamide, 3-butoxypropanamide, N, N-dimethyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropanamide, N, N -Dibutyl-3-butoxyp Amides such as panamide and N, N-dimethyl-3-butoxypropanamide; Ketones or ketoalcohols such as acetone and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Oxyethylene or oxy such as polyethylene glycol and polypropylene glycol Propylene copolymer; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1,3-propanediol, 2-methyl- 1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 2-pentanediol, 1,2-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3- Diols such as methyl-1,5-pentanediol and 2-methyl-2,4-pentanediol; Triols such as glycerin, trimethylolethane, trimethylolpropane and 1,2,6-hexanetriol: mesoerythritol, Tetrahydric alcohols such as pentaerythritol; ethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl) ether, diethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl, n- Hexyl, 2-ethylhexyl Sil) ether, triethylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl) ether, propylene glycol monomethyl (or ethyl, isopropyl, n-butyl, isobutyl) ether, dipropylene glycol monomethyl (or ethyl, isopropyl, n Monoalkyl ethers such as -butyl, isobutyl) ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol die Dialkyl ethers of polyhydric alcohols such as ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, Alkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine and N-butyldiethanolamine; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone And cyclic compounds such as γ-butyrolactone and sulfolane.

  When the water-soluble solvent contains a water-soluble organic solvent, particularly when the receiving solution is ejected by inkjet, the water-soluble organic solvent should contain a solvent having a boiling point higher than that of water, that is, a solvent having a boiling point higher than 100 ° C. Among them, those having a boiling point of 150 ° C. or higher are preferable, and those having a boiling point of 180 ° C. or higher are particularly preferable. In particular, when the receiving solution is ejected by ink jet, it suppresses that the water-soluble organic solvent in the ink volatilizes and the viscosity of the receiving solution increases in the receiving solution adhering to the nozzle or in a fine tube inside the ink jet head. This is because it is possible to prevent the inkjet head from being damaged due to clogging of the nozzles and tubes. Moreover, as a result, it is because it can be set as the receiving solution with favorable fluidity | liquidity and favorable continuous discharge property and discharge property after being left. The water-soluble organic solvent having a boiling point higher than that of water is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more in all the water-soluble organic solvents.

  Further, when the boiling point of the water-soluble organic solvent is too high, much energy is required for drying, and it takes a long time for drying, so that it is difficult to cope with high-speed continuous printing. Therefore, the boiling point of the water-soluble organic solvent is preferably 300 ° C. or less.

  When printing on a low-absorbent substrate and a non-absorbent substrate, it is preferable to suppress the content of the low-volatile solvent because the solvent does not easily penetrate into the substrate, and a water solution having a boiling point of 250 ° C. or higher. The content of the volatile organic solvent is preferably less than 5 parts by mass with respect to 100 parts by mass of the receiving solution. Furthermore, it is more preferable that the water-soluble organic solvent having a boiling point of 280 ° C. or higher is not substantially contained. In the present specification, “substantially not containing a water-soluble organic solvent at 280 ° C. or higher” means less than 1 part by mass with respect to 100 parts by mass of the receiving solution.

  Examples of the water-soluble organic solvent having a boiling point of 280 ° C. or higher include triethylene glycol (boiling point: 285 ° C.), tetraethylene glycol (boiling point: 314 ° C.), glycerin (boiling point: 290 ° C.), 1,2,6-hexane. Examples include triol, trimethylolethane, trimethylolpropane, diglycerin, polyethylene glycol, and polypropylene glycol.

  Examples of water-soluble organic solvents having a boiling point of 250 ° C. or higher and lower than 280 ° C. include tripropylene glycol (boiling point: 268 ° C.), tripropylene glycol monobutyl ether (boiling point: 274 ° C.), triethylene glycol monobutyl ether (boiling point: 271 ° C.), Examples include diethylene glycol mono-2-ethylhexyl ether (boiling point: 272 ° C.), 1,6-hexanediol (boiling point: 250 ° C.), 3-methyl-1,5-pentanediol (boiling point: 250 ° C.), and the like. .

  Examples of water-soluble organic solvents having a boiling point of 200 ° C. or higher and lower than 250 ° C. include dipropylene glycol (boiling point: 232 ° C.), diethylene glycol (boiling point: 244 ° C.), tripropylene glycol monomethyl ether (boiling point: 242 ° C.), diethylene glycol monobutyl ether ( Boiling point: 231 ° C.), triethylene glycol monomethyl ether (boiling point: 249 ° C.), diethylene glycol monoisopropyl ether (boiling point: 207 ° C.), ethylene glycol mono-2-ethylhexyl ether (boiling point: 229 ° C.), ethylene glycol monohexyl ether ( Boiling point: 208 ° C), dipropylene glycol monopropyl ether (boiling point: 212 ° C), dipropylene glycol monobutyl ether (boiling point: 229 ° C), dipropylene glycol monomethyl ether Teracetate (boiling point: 209 ° C), diethylene glycol monobutyl ether acetate (boiling point: 247 ° C), 1,3-propanediol (boiling point: 214 ° C), 1,3-butanediol (boiling point: 208 ° C), 1,4- Butanediol (boiling point: 230 ° C), 1,2-pentanediol (boiling point: 210 ° C), 1,2-hexanediol (boiling point: 223 ° C), 1,5-pentanediol (boiling point: 242 ° C), 1, 6-hexanediol (boiling point: 250 ° C.), 2,2,4-trimethyl-1,3-pentanediol (boiling point: 232 ° C.), 3-methyl-1,3-butanediol (boiling point: 203 ° C.), 2 -Methyl-1,3-pentanediol (boiling point: 214 ° C), 2-ethyl-1,3-hexanediol (boiling point: 244 ° C), and the like.

  Water-soluble organic solvents having a boiling point of 180 ° C. or higher and lower than 200 ° C. include ethylene glycol (boiling point: 197 ° C.), propylene glycol (boiling point: 187 ° C.), 1,2-butanediol (boiling point: 193 ° C.), 2-methyl -2,4-pentanediol (boiling point: 198 ° C.) and the like.

  The water contained in the water-soluble solvent does not contain various ions, and it is preferable to use deionized water. The water content is not particularly limited as long as each component can be dispersed or dissolved, but it is preferably in the range of 10% by mass to 95% by mass in the water-soluble solvent. In particular, it is preferably in the range of 20% by mass to 95% by mass, and more preferably in the range of 30% by mass to 90% by mass.

  The content of the water-soluble organic solvent is preferably in the range of 5% by mass to 90% by mass in the water-soluble solvent, and more preferably in the range of 5% by mass to 80% by mass. In particular, it is preferable to be within the range of 10% by mass or more and 70% by mass or less.

  This is because when the content of water and the water-soluble organic solvent is within the above range, the moisture retention is good and nozzle clogging or the like can be reduced. Further, it can be easily ejected by the ink jet head.

[resin]
The receiving solution of the present invention contains a resin. By containing the resin in the receiving solution, the water resistance of the printed matter printed with the receiving solution and the ink is improved. Further, at least a part of the resin contained in the receiving solution of the present invention is contained as a resin emulsion. In the present invention, the resin emulsion means an aqueous dispersion in which the continuous phase is a water-soluble solvent and the dispersed particles are resin fine particles. By forming the resin emulsion, the resin can be dispersed in the receiving solution as resin fine particles by electrostatic repulsion. The resin emulsion generally has a property of thickening and aggregating when a water-soluble solvent which is a continuous phase is reduced by evaporation, permeation, or the like, and has an effect of promoting fixing of a coloring material to a printing substrate. The resin contained in the receiving solution of the present invention is not particularly limited as long as it can exhibit the desired water resistance. For example, acrylic resin, polystyrene resin, polyester resin, vinyl chloride resin, acetic acid Vinyl resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, urethane resin, silicone (silicon) resin, acrylamide resin, epoxy resin, or a copolymer resin or a mixture thereof can be used. These are preferable in that the solvent resistance can be improved in addition to the water resistance. Especially, since it can be set as the thing excellent in discharge stability, water resistance, and solvent resistance, it is preferable that an acrylic resin is included.

  The acrylic resin is not particularly limited as long as it is contained as a main component of the monomer constituting the (meth) acrylic acid ester monomer. As the (meth) acrylic acid ester monomer, a known compound can be used, and a monofunctional (meth) acrylic acid ester can be preferably used. Examples thereof include (meth) acrylic acid alkyl esters, (meth) acrylic acid aralkyl esters, (meth) acrylic acid alkoxyalkyl esters, and the like. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl , (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-iso-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid Hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid octyl, (meth) acrylic acid-iso-octyl, (meth) acrylic acid nonyl, (meth) acrylic acid-iso-nonyl, (meth) acrylic Dodecyl acid, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, ( T) cyclohexyl acrylate, (meth) acrylate-2-methylcyclohexyl, (meth) acrylate dicyclopentanyl, (meth) acrylate dicyclopentenyl, (meth) acrylate dicyclopentanyloxyethyl, (meth) ) Dicyclopentenyloxyethyl acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate , Naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, (meth) acrylic acid Full frills, (meth) acrylic Tetrahydrofuryl, tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, glycidyl (meth) acrylate, (meth) 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate Perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate , (Meth) acrylic acid-3- (N, N-dimethylamino) Propyl, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as diethylaminoethyl, trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane , Etc. “(Meth) acryl” means both “acryl” and “methacryl”. These monomers can be obtained from Mitsubishi Rayon Co., Ltd., Nippon Oil & Fat Co., Ltd., Mitsubishi Chemical Co., Ltd., Hitachi Chemical Co., Ltd., etc.

  The monomer constituting the acrylic resin may include an acid group-containing monomer having an acid group, a hydroxyl group-containing monomer having a hydroxyl group, and an amino group-containing monomer having an amino group. Examples of the acid group-containing monomer having an acid group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, Ethylenic acid such as italonic acid monomethyl ester, itaconic acid monobutyl ester, vinyl benzoic acid, oxalic acid monohydroxyethyl (meth) acrylate, carboxyl group-containing aliphatic monomers such as carboxyl-terminated caprolactone-modified (meth) acrylate Mention may be made of a carboxyl group-containing monomer having a saturated double bond and a carboxyl group. The hydroxyl group-containing monomer containing a hydroxyl group is not particularly limited as long as it has an unsaturated double bond and a hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta ) Acrylate, 3-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, methyl α- (Hydroxymethyl) (meth) acrylate, ethyl α- (hydroxymethyl) (meth) acrylate, n-butyl α- (hydroxymethyl) (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4- Hydro Butyl (meth) acrylate, and the like. The amino group-containing monomer is not particularly limited as long as it has an unsaturated double bond and an amino group. For example, (meth) acrylamide N-monomethyl (meth) acrylamide, N-monoethyl (meta ) Acrylamide, N, N-dimethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl ( Acrylamide compounds such as (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl acrylamide, diacetone acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acyl Rate, nitrogen-containing (meth) acrylate compounds such as ethylene oxide addition (meth) acrylate of morpholine, N-vinylpyrrolidone, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinyloxazolidone, N-vinyl Succinimide, N-vinylmethylcarbamate, N, N-methylvinylacetamide, (meth) acryloyloxyethyltrimethylammonium chloride, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, (meth) acrylonitrile, etc. Can be mentioned.

  Moreover, as a monomer which comprises an acrylic resin, you may have another monomer as needed other than the said (meth) acrylic acid ester monomer. Such other monomers are not particularly limited as long as they can be copolymerized with the above (meth) acrylic acid ester monomer and can have desired water resistance and solvent resistance. Instead, it may be a monofunctional monomer having one ethylenically unsaturated double bond or a polyfunctional monomer having 2 or more. For example, vinyl monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, N-vinyl carbazole, vinyl imidazole, vinyl ether, vinyl ketone, vinyl pyrrolidone; styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives, aromatic vinyl monomers such as vinyltoluene, chlorostyrene; olefin monomers such as ethylene, propylene, isopropylene; butadiene, chloroprene, etc. Diene monomers; vinylcyan compound monomers such as acrylonitrile and methacrylonitrile can be used. In addition, diacrylate compounds such as polyethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate; triacrylate compounds such as trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate Dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; divinylbenzene and the like can be used. The acrylic resin can be formed using these monomers, but the copolymerization form of the monomers is not particularly limited, and for example, block copolymers, random copolymers, graft copolymers, etc. Can do. The resin emulsion can be produced by, for example, emulsion polymerization reaction and neutralization after the reaction. As the emulsifier, a normal polymer surfactant may be used, or a reactive surfactant having an unsaturated bond may be used. The synthesis method is not particularly limited. For example, in the presence of a reactive surfactant, a non-reactive surfactant, polyvinyl alcohol, a cellulose derivative, water, a monomer, an emulsifier, and a polymerization start Emulsion polymerization can be performed by mixing with an agent. The resin emulsion can also be obtained by mixing resin fine particles with water together with a surfactant without causing an emulsion polymerization reaction. For example, it can be obtained by adding resin fine particles comprising a (meth) acrylic acid ester or styrene and a (meth) acrylic acid ester and a surfactant and mixing them in water.

  Commercially available resin emulsions include, for example, Acryt WEM-031U, WEM-200U, WEM-321, WEM-3000, WEM-202U, WEM-3008 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic-urethane resin emulsion), Acryt UW-550CS, UW-223SX, AKW107, RKW-500 (manufactured by Taisei Fine Chemical Co., Ltd., acrylic resin emulsion), LUBRIJET N240 (manufactured by Lubrizol, acrylic resin emulsion), Superflex 150, 210, 470, 500M, 620, 650, E2000, E4800, R5002 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), Vinibrand 701FE35, 701FE50, 701FE65, 700, 701, 71 , 737, 747 (manufactured by Nissin Chemical Co., Ltd., vinyl chloride-acrylic resin emulsion), vinylim 2706, 2585 (manufactured by Nissin Chemical Co., Ltd., acrylic resin emulsion), Movinyl 743N, 6600, 7470, 7720 (Nippon Gosei Co., Ltd.) Examples thereof include, but are not limited to, chemical product (acrylic resin emulsion).

  The average particle size of the resin emulsion is preferably from 30 to 300 nm, more preferably from 50 to 250 nm, from the viewpoints of dispersion stability in the receiving solution and inkjet discharge properties. In the present invention, the number average particle size of the pigment can be measured using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000) at a measurement temperature of 25 ° C.

  The mass average molecular weight of the resin emulsion is preferably 10,000 to 1,000,000, more preferably 100,000 to 500,000 from the viewpoints of the stability of the receiving solution and the water resistance of the coating film. In the present invention, the molecular weight of the resin indicates the mass average molecular weight Mw, and is a value measured by GPC (gel permeation chromatography). In “HLC-8120GPC” manufactured by Tosoh Corporation, It can be measured using polystyrene standard for calibration curve as standard.

  The glass transition point of the resin emulsion can form a printed matter having water resistance, solvent resistance and scratch resistance even when printed on a low-absorbent substrate or a non-absorbent substrate. It is possible to avoid applying a high temperature to form, making a lot of energy unnecessary, and making the printing substrate less susceptible to damage by heat. 90 degreeC is more preferable and 20-80 degreeC is more preferable. The glass transition temperature (Tg) can be measured by, for example, a differential scanning calorimeter “DSC-50” manufactured by Shimadzu Corporation.

  The resin emulsion is not limited to any one of cationic, nonionic, and anionic, but the acid value of the resin emulsion is 25 mgKOH / g or less from the viewpoint of water resistance of the printed matter, storage stability of the receiving solution, etc. It is preferable that

[Other ingredients]
The receiving solution may further contain a conventionally known additive as required. Examples of the additive include a viscosity adjuster, a surfactant, a pH adjuster, a surface tension adjuster, an antioxidant, an antiseptic and an antifungal agent.

  The surfactant is not particularly limited. For example, polysiloxane compounds, anionic surfactants, nonionic surfactants, fluorine surfactants, alkylene oxide modified acetylene glycol surfactants, alkylene An oxide non-modified acetylene glycol surfactant may be used.

  In the present invention, the ink recording medium may include any one of an alkylene oxide non-modified acetylene glycol surfactant, an alkylene oxide modified acetylene glycol surfactant, and a polysiloxane compound as a surface tension adjuster. This is preferable because the wettability with respect to the film can be further improved.

  Specific examples of the alkylene oxide non-modified acetylene glycol surfactant include 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl Examples include -1-pentyn-3-ol, 3-hexyne-2,5-diol, and 2-butyne-1,4-diol. Moreover, as a commercial item, Surfynol 61,82,104 (all are the air products company make) etc. can be used.

  Specific examples of the alkylene oxide-modified acetylene glycol surfactant include Surfynol 420, 440, 465, 485, TG, 2502, Dinol 604, 607 (all manufactured by Air Products), Surfynol SE, MD -20, Olfine E1004, E1010, PD-004, EXP4300, PD-501, PD-502, SPC (all manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol EH, E40, E60, E81, E100, E200 ( All include Kawaken Fine Chemical Co., Ltd.).

  Examples of commercially available polysiloxane compounds include FZ-2122, FZ-2110, FZ-7006, FZ-2166, FZ-2164, FZ-7001, FZ-2120, SH 8400, FZ-7002, and FZ-2104. 8029 ADDITIVE, 8032 ADDITIVE, 57 ADDITIVE, 67 ADDITIVE, 8616 ADDITIVE (all manufactured by Toray Dow Corning), KF-6012, KF-6015, KF-6004, KF-6013, KF-6011, KF-6043 , KP-104, 110, 112, 323, 341 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-300 / 302, BYK-301, BYK-306, BYK-307, BYK-320, BYK-325 BYK-330 BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-310, BYK-315, BYK-370, BYK-UV3570, BYK-322, BYK-323, BYK-3455, BYK-Silclean3700 (all manufactured by BYK Chemie) ), Silface SAG503A, Silface SJM-002, Silface SJM-003 (all manufactured by Nissin Chemical Industry Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Wet 240, TEGO Wet 25 , TEGO Wet 240, (both, Evonik Co., Ltd.) and the like can be given. In the present invention, among them, a polyether group-modified polysiloxane compound having a polyether group can be preferably used, and a water-soluble polyether group-modified polysiloxane compound can be particularly preferably used.

  Specific examples of anionic surfactants, nonionic surfactants, fluorosurfactants, and alkylene oxide-modified acetylene glycol surfactants include emal, latemul, neopelex, demole (all of which are anions Surfactants; manufactured by Kao Corporation, Sannor, Lipolane, Lipon, Lipar (all are anionic surfactants; manufactured by Lion Corporation), Neugen, Epan, Sorgen (all are nonionic surfactants; Ichi Kogyo Seiyaku Co., Ltd.) Emulgen, Amito, Emazole (Non-ionic surfactants; Kao Co., Ltd.), Naroacty, Emalmin, Sannonic (Non-ionic surfactants; Sanyo Kasei Kogyo Co., Ltd.) ), MegaFuck (Fluorosurfactant; manufactured by DIC Corporation), Surf (Fluorosurfactant; manufactured by AGC Seimi Chemical Co., Ltd.), Nippon Cytec Industries Co., Ltd., AEROSOL TR-70, TR-70HG, OT-75, OT-N, MA-80, IB-45, EF- 800, A-102, PEX OT-P, PELEX CS, PELEX TR, Plex TA, Nippon Emulsifier Co., Ltd. New Coal 290-A, New Coal 290-KS, New Coal 291-M, New Cole 291-PG, New Coal 291-GL, New Coal 292-PG, New Coal 293, New Coal 297 (all are anionic surfactants), Emulgen 320P, Emulgen 350, Emulgen 430, Emulgen 130K manufactured by Kao Corporation , Emulgen 150 Daiichi Kogyo Seiyaku Co., Ltd. Igen TDS-120, Neugen TDS-200D, Neugen TDS-500F, Aoki Yushi Kogyo Co., Ltd. BROWNON SR-715, BROWNON SR-720, BROWNON SR-730, BROWNON SR-750, BROWNON EN-1520A, BROWNON EN-1530 BROWNON EN-1540, Nippon Emulsifier Co., Ltd. New Coal 2310, New Coal 2320, New Coal 2327, New Coal 1545, New Coal 1820, Nikko Chemicals Co., Ltd. NIKKOL BPS20, NIKKOL BPS30 (both nonionic surfactants) Agent) and the like. The content of these surfactants is appropriately adjusted according to the content of the solvent, resin, pigment and other surfactants. These surfactants may be used alone or in combination of two or more. The content of the surfactant is appropriately adjusted according to the ink miscibility and detergency, the wettability to the inner wall of the flow path, and the inkjet discharge property, and in 100 parts by mass of the receiving solution, preferably 0.05 to 5 parts by mass, More preferably 0.5 to 3 parts by mass are contained.

[Surface tension of receiving solution]
The surface tension of the receiving solution is preferably 35 mN / m or less, more preferably 32 mN / m or less, even more preferably 30 mN / m or less, particularly from the viewpoint of wettability to the surface of the recording medium and miscibility with ink. When applying to an absorptive base material, 26 mN / m or less is more preferable. When the receiving solution is ejected by the ink jet method, the surface tension of the receiving solution is preferably 20 mN / m or more from the viewpoint of improving the ejection stability of the receiving solution from the ejection head. The surface tension of the receiving solution can be adjusted by appropriately selecting the water-soluble solvent and the surfactant. The surface tension in the present invention is a value measured by the Wilhelmy method (Kyowa Interface Science model: CBVP-Z) at a measurement temperature of 25 ° C.

<Ink set for inkjet recording>
In the ink jet recording method of the present invention, an ink set for ink jet recording in which the receiving solution of the present invention and the ink for ink jet recording are combined can be used.

<Ink for inkjet recording>
In the present invention, the inkjet recording ink includes a color material, a resin, a solvent, and, if necessary, a surfactant. The inkjet ink includes at least a water-soluble solvent. As long as the effect is not impaired, another component may be further contained as necessary.

[Color material]
In the present invention, the color material of the ink for ink jet recording is not particularly limited, and may be dye-based or pigment-based, but resistance such as water resistance and light resistance of the printed matter. It is preferable to use a pigment-based ink that has good quality. In the present invention, the pigment that can be used in the ink for ink jet recording is not particularly limited, and examples thereof include organic pigments and inorganic pigments that are conventionally used in ink for ink jet recording. These may be used alone or in combination of two or more. Specific organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine organic pigments, quinacridone organic pigments, perylene organic pigments, dioxazine organic pigments, nickel azo pigments, isoindolinones. Organic pigments, pyranthrone organic pigments, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, etc. Examples of solid solution pigments and other pigments include carbon black.

  When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, 213, 214, C.I. I. Pigment Red 5, 7, 9, 12, 48, 49, 52, 53, 57, 97, 112, 122, 123, 149, 168, 177, 180, 184, 192, 202, 206, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, 64, 71, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment brown 23, 25, 26, C.I. I. Pigment black 7 and the like.

  Specific examples of pigments that can be used in ink jet recording inks in the present invention include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, zinc white, sulfuric acid. Lead, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, inorganic solid solution pigment, etc. .

  In the present invention, the average dispersed particle diameter of the inorganic pigment that can be used in the ink for inkjet recording is not particularly limited as long as it can produce a desired color. The number average particle diameter is preferably in the range of 5 to 300 nm from the viewpoint of good dispersibility and dispersion stability of the pigment and obtaining sufficient coloring power, although it varies depending on the type of pigment used. It is more preferable that the thickness is 30 to 150 nm. If the number average particle size is not more than the above upper limit value, nozzle clogging of the inkjet head is unlikely to occur, a homogeneous image with high reproducibility can be obtained, and the resulting printed matter can be of high quality. . When the number average particle diameter is not more than the above lower limit, the light resistance may be lowered. In the present invention, the number average particle size of the pigment is measured using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000) at a measurement temperature of 25 ° C.

  In the present invention, the content of the pigment that can be used in the ink for ink jet recording is not particularly limited as long as a desired image can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of pigment, it is preferably in the range of 0.05% by mass or more and 20% by mass or less, and 0.1% by mass or more and 10% by mass or less with respect to the entire ink composition. It is more preferable to be within the range. When the pigment content is in the range of 0.05% by mass or more and 20% by mass or less, the pigment can have excellent balance between dispersion stability and coloring power.

  In the present invention, the pigment that can be used in the ink for inkjet recording is a pigment dispersion in which the pigment is dispersed in a water-soluble solvent by a pigment dispersant, but the hydrophilic group is directly modified on the surface of the pigment. The pigment dispersion may be a self-dispersed pigment. Here, the pigment dispersant is a water-soluble resin and refers to a resin having a function of improving the dispersibility of the pigment in the ink by adhering to a part of the pigment surface. The water-soluble resin is one that dissolves 1 part by mass or more at 1 atm in 100 parts by mass of water at 25 ° C. By making the pigment dispersant, which is a water-soluble resin, adhere to a part of the pigment surface, the dispersibility of the pigment in the ink is improved, and a high gloss image can be obtained. In the present invention, the pigment that can be used in the ink for inkjet recording may be a combination of a plurality of organic pigments and inorganic pigments. A pigment dispersion dispersed in a water-soluble solvent with a pigment dispersant and a self-dispersing pigment May be used in combination.

  In the present invention, examples of the self-dispersing pigment that can be used in the ink for inkjet recording include, for example, a carbonyl group, a carboxyl group, a hydroxyl group, and a sulfonic acid group described in JP 2012-51357 A as hydrophilic groups. And those modified with a phosphorus-containing group having at least one P—O or P═O bond. Examples of commercially available products include “CAB-O-JET 200, CAB-O-JET 250C, CAB-O-JET 260M, CAB-O-JET 270Y, CAB-O-JET 740Y, CAB-” manufactured by Cabot. O-JET 300, CAB-O-JET 400, CAB-O-JET 450C, CAB-O-JET 465M, CAB-O-JET 470Y, CAB-O-JET 480V, CAB-O-JET 352K, CAB-O -JET 554B, CAB-O-JET 1027R "," Microjet black 162, Aqua-Black 001, BONJET BLACK CW-1, BONJET BLACK CW-2, BONJET BLACK CW-3 "manufactured by Orient Chemical Industries, Tokai Mosquito Examples include “Aqua-Black 162, Aqua-Black 001” manufactured by Bonn Co., Ltd., and LIOJET WD BLACK 002C manufactured by Toyo Ink Manufacturing Co., Ltd. Etc.

  In the present invention, the pigment dispersant for the pigment that can be used in the ink for inkjet recording is not particularly limited. For example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone (silicon), and fluorine can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  As the pigment dispersant, a water-soluble polymer dispersant can be preferably used. Examples of water-soluble polymer dispersants include polyester-based, polyacryl-based, polyurethane-based, polyamine-based, and polycaptolactone-based main chains, and amino groups, carboxy groups, sulfo groups, and hydroxy groups in the side chains. And dispersants having a polar group such as For example, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene and unsaturated carboxylic acid esters such as acrylic acid esters; (Partial) amine salts, (partial) ammonium salts and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters (Co) polymers and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethylenimine derivatives (poly (lower alkylene imines) and free carboxyl group-containing polyesters Amides and their bases obtained by the reaction); polyallylamine derivatives (polyallyl) (Reaction product obtained by reacting min and one or more compounds selected from polyesters, polyamides having a free carboxyl group, or co-condensates of esters and amides (polyesteramides)) Etc. Among these, a water-soluble polymer dispersant containing a (meth) acrylic resin is preferable from the viewpoints of ink dispersion stability and image sharpness of printed matter. In addition, it is preferable that the functional group of the water-soluble polymer dispersant has an acidic group from the viewpoint of dispersion stability and compatibility.

  Specific examples of the water-soluble polymer dispersant include SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000, JONCRYL67, JONCRYL586, JONCRYL6LCR, JONCRYL6L, JONCRYL6LJL6LCR, JONCRYL618L -JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA5220, EFKA6230, SOLPERSE20000, SOLPERSE27000, SOLPERSE41000, SOLPERSE41090, SOLPERSE43000, SOLSPE manufactured by Lubrizol SE44000, SOLSPERSE 46000, SOLSPERSE 47000, SOLSPERSE 54000, BYKJET-9150, BYKJET-9151, BYKJET-9170, DISPERBYK-168, DISPERBYK-190, DISPERBYK-198, DISPERBY20-S It is done.

[resin]
In the present invention, the resin used in the ink for ink jet recording promotes the fixing of the pigment to the surface of the recording medium. The resin is preferably a resin emulsion in terms of excellent fixability and excellent water resistance of printed matter, and can be the same as the receiving solution.

[Water-soluble solvent]
In the present invention, examples of the water-soluble solvent used in the ink for inkjet recording include water and water-soluble organic solvents. The water-soluble organic solvent can be the same as the water-soluble organic solvent exemplified in the receiving solution. Water and water-soluble organic solvents can be used alone or as a mixture.

[Surfactant]
In the present invention, the surfactant used in the ink for ink jet recording can be the same as the surfactant exemplified in the receiving solution. Surfactants can be used alone or as a mixture.

[Wax emulsion]
In the present invention, the ink for ink jet recording may contain a wax emulsion having a pigment content or less as required. By containing a wax emulsion having a pigment content or less, an ink composition having excellent storage stability and ejection stability can be obtained, and ink having excellent abrasion resistance and capable of producing glossy printed matter. It can be a composition. The polyolefin wax generally refers to a relatively low molecular weight soft polyolefin having a molecular weight of less than 10,000, and is different from a hard polyolefin resin having a molecular weight of 10,000 or more used for a film forming material or the like. For example, a normal temperature solid wax melted by heating, hot water and an emulsifier can be mixed to form a wax emulsion. The wax emulsion that can be used in the present invention preferably contains a polyolefin wax having a melting point of 85 ° C. or more and 140 ° C. or less, and the wax emulsion preferably has an average particle size of 140 nm or less.

  Examples of wax emulsions include AQUACER-507, AQUACER-513, AQUACER-515, AQUACER-526, AQUACER-531, AQUACER-533, AQUACER-535, AQUACER-537, AQUACER-539, AQUACER-552, AQUACER-402, , AQUACER-1547 (manufactured by Big Chemie), Nopcoat PEM-17 (manufactured by Sannopco), JONCRYLWAX4, JONCRYLWAX26, JONCRYLWAX28, JONCRYLWAX120 (manufactured by BASF).

[Other ingredients]
In the present invention, the ink for ink jet recording may further contain a conventionally known additive as necessary, as in the case of the receiving solution. Examples of the additive include a viscosity adjusting agent, a pH adjusting agent, a surface tension adjusting agent, an antioxidant, an antiseptic, and an antifungal agent.

[Ink preparation method]
The method for preparing the ink that can be used in the ink set of the present invention is not particularly limited. For example, a method of preparing a self-dispersing pigment, resin, surfactant and other components as necessary in a water-soluble solvent, a method of adding a pigment and a dispersant to a water-soluble solvent, and then dispersing the resin. , A method of preparing by adding a surfactant and other components as needed, and adding a pigment, a resin, a surfactant and other components as necessary to a water-soluble solvent, and then dispersing the pigment to prepare And the like.

<Inkjet recording method>
An ink jet recording method using the receiving solution or ink set of the present invention (hereinafter sometimes simply referred to as an ink jet recording method) is not particularly limited. For example, ink is applied onto a recording medium. An ink jet recording method including a step of applying the receiving solution of the present invention before or after can be mentioned. In the case of an absorptive base material, it is easy to suppress feathering and back-through due to ink being absorbed by paper fibers. It is preferable to apply the ink after applying the receiving solution to the surface of the recording medium because the spreadability can be improved and the effect of suppressing bleeding is more easily exhibited. More preferably, after the receiving solution is applied to the surface of the recording medium by the ink jet method, the ink of the ink set is applied by the ink jet method.

[recoding media]
In the ink jet recording method, the recording medium is not particularly limited, and any of an absorbent substrate, a low absorbent substrate, and a non-absorbent substrate can be suitably used. As an absorptive base material, uncoated paper, such as a re-paper, medium quality paper, quality paper, and copy paper (PCC); Fabrics, such as cotton, a synthetic fabric, silk, hemp, a nonwoven fabric, etc. are mentioned, for example. In particular, the ink jet recording method is preferably applied to non-coated paper because it is easy to suppress feathering and back-through. The absorbency of the recording medium is, for example, JAPAN TAPPI Paper Pulp Test Method No. The test can be performed with 51-87 or the like. Non-coated paper has high absorbency because it is not coated with a coating agent that reduces ink penetration and absorption.

Here, “low-absorbent substrate” or “non-absorbent substrate” in the present specification is a record in which the water absorption amount from the start of contact to 30 msec in the Bristow method is 10 mL / m ² or less. Say medium. This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Examples of the low-absorbency substrate include coated paper such as finely coated paper, lightweight coated paper, coated paper, art paper, cast paper, and the like. Coated paper is a paper coated with a coating agent made by adding a white pigment or a binder component to improve surface smoothness, and it is difficult for ink to be absorbed and penetrated. Examples of the non-absorbable substrate include plastic films such as polyester resins, polypropylene resins, vinyl chloride resins, polyimide resins; metals, metal-deposited paper, glass, synthetic rubber, natural rubber, leather, etc. Yes, but not limited to these. The ink jet recording method that can be used for the ink set of the present invention can be suitably used even when a low-absorbing substrate or a non-absorbing substrate having low ink permeability is used. A clear image in which bleeding is suppressed can be obtained.

[Printer]
The method for applying the receiving solution to the recording medium of the present invention is not particularly limited as long as it is a method that can apply the receiving solution only to the printing portion or the entire printing surface, and a conventionally known method can be used. For example, a method of applying the receiving solution by a spray method, a coater method, an ink jet method, a gravure method, or a flexo method can be used, and among these, application by a coater method or an ink jet method is preferable. According to the coater method, the receiving solution can be uniformly applied in a short time. In addition, according to the ink jet system, it is easy to apply to any place or to the entire printing surface. By applying the ink to the recording medium to which the receiving solution is applied, there is no color unevenness or white spot, and feathering and color bleeding can be suppressed.

  The receiving solution and ink set of the present invention can be applied to any ink jet recording apparatus such as a piezo system, a thermal system, and an electrostatic system, and among them, it is preferably used for a piezo ink jet recording apparatus. A piezo-type recording head uses a piezoelectric vibrator as a pressure generating element, and discharges ink droplets by pressurizing and depressurizing a pressure chamber by deformation of the piezoelectric vibrator. In such a recording head, as an attempt to further improve the image quality and the recording speed, an attempt is made to further increase the image quality by increasing the types of colors that can be recorded by increasing the number of nozzle rows, Attempts have been made to improve the recording speed by increasing the number of nozzle openings constituting one nozzle row. Furthermore, in order to increase the number of nozzles provided in one head, attempts have been made to miniaturize the nozzles.

  However, when the head nozzles are miniaturized, flying bends and nozzle clogging are likely to occur due to the adhered and residual ink. In addition, when aggregates are generated in the ink components over a long period of use, it becomes an obstacle to the flying of ink droplets, and troubles such as flight bending and nozzle clogging occur. For this reason, there is an urgent need to develop an inkjet ink that can be stably discharged without causing clogging in the inkjet head. Therefore, the ink of the ink set of the present invention, which can suppress the generation of aggregates and is excellent in stability, is suitable for a piezo type ink jet recording apparatus, and can be used for both a serial head type and a line head type recording apparatus. Can do.

  According to the ink jet recording method of the present invention, it is possible to obtain a clear image with suppressed bleeding and white spots, and to suppress deterioration of the apparatus and to have excellent ejection stability.

  The ink jet recording method can suppress feathering and back-through which are particularly problematic when an absorbent substrate is used as a recording medium, and a low-absorbent substrate or a non-absorbent substrate can be used as a recording medium. Since white spots and color bleeding that are particularly problematic when used can be suppressed, bleeding and white spots are suppressed regardless of the recording medium.

  When an absorbent substrate such as non-coated paper is used as a recording medium, the ink easily penetrates into the recording medium, so that the pigment does not stay on the surface of the recording medium but the ink reaches the back side of the substrate. Or the density of the color material on the surface of the recording medium is low, and there is a problem that feathering tends to occur along the fiber of the paper and a clear image cannot be obtained. When a low-absorbing substrate or a non-absorbing substrate is used as the recording medium, the ink hardly penetrates and is repelled on the surface of the recording medium. For this reason, there is a problem that the dots are not sufficiently spread, the printing surface is not sufficiently filled with ink, and printing unevenness and white spots are likely to occur. Further, when a non-absorbent substrate is used as a recording medium, there is a problem that the time required for drying becomes long and the ink droplets that are repelled are irregularly connected, so that bleeding and unevenness are likely to occur. .

  As a result of intensive studies, the inventors of the present invention applied the ink for inkjet after applying the receiving solution of the present invention to the printing surface and drying the receiving solution before drying the substrate. It was found that printing unevenness and white spots in the material can be suppressed. The application timing of the receiving solution to the recording medium is not particularly limited as long as the ink and the receiving solution are in contact with each other on the recording medium, but the ink is used in order to more effectively suppress feathering and bleeding. It is preferable to apply just before discharging. By applying ink before the receiving solution dries, the ink on the surface of the recording medium tends to get wet and the dot diameter of the ink increases, so printing irregularities and white spots are eliminated, and the receiving solution and the ink are mixed immediately. It is presumed that the dispersion state of the pigment changes rapidly and the ink is fixed without causing color bleeding.

  In the present invention, it is preferable that ink is ejected and applied to the recording medium while the surface of the recording medium is heated to 30 ° C. or higher and 60 ° C. or lower. By setting the surface temperature of the ink application portion of the recording medium at the time of ink application to 30 ° C. or more, the ink spreads well even in the case of a low or non-absorbent substrate, and a clear printed matter is manufactured. Is possible. In addition, by setting the surface temperature of the ink application portion of the recording medium at the time of ink application to 60 ° C. or less, distortion of the recording medium due to heat can be suppressed, and a good image can be printed. Ink sticking on the nozzle surface of the head is suppressed, and ejection stability can be maintained.

<Method for producing printed matter>
A printed matter can also be produced using the inkjet recording method. For example, the manufacturing method of the printed matter including the process of apply | coating the receiving solution of this invention on the recording medium or the ink containing a coloring material can be mentioned. By including the step of applying the receiving solution of the present invention, it is possible to suppress bleeding and white spots of the printed matter and obtain a clear image. The application of the receiving solution of the present invention on the recording medium or the ink containing the coloring material means that the receiving solution of the present invention is applied on the recording medium and the ink containing the coloring material is applied on the recording medium. This is a concept that includes both the application of the receiving solution of the present invention. In particular, it is preferable to apply the ink to the surface of the recording medium after the receiving solution is applied to the surface of the recording medium. If it is ejected by the ink jet method, it is easy to apply the receiving solution or ink to an arbitrary place, or it can be applied to the entire surface of the recording medium. It is preferable to apply the receiving solution and ink of the present invention to the surface of a recording medium.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Preparation of receiving solution>
Examples and Comparative Examples as shown in Tables 1 to 3 below using polyvalent metal salts, resins (resin emulsions), water-soluble solvents (water-soluble organic solvents, water (ion-exchanged water)), and surfactants. The receiving solution was prepared. In the table, the numerical values of A-1 to D-3 and R-1 to R-4 represent values as solid contents. Table 4 shows the molar molar concentration of the metal salt in the ink jet recording receiving solutions of Examples and Comparative Examples.

The symbols in the table indicate the following.
A-1: Calcium pyrrolidonecarboxylate (molecular weight 296)
A-2: Magnesium pyrrolidonecarboxylate (molecular weight 281)
A-3: Zinc pyrrolidone carboxylate (molecular weight 322)
A-4: Calcium pantothenate (molecular weight 477)
A-5: Calcium glutamate (molecular weight 332)
A-6: Calcium pipecolate (molecular weight 296)
A-7: Proline magnesium (molecular weight 252)
A-8: Hydroxyproline calcium (molecular weight 328)
B-1: Magnesium nitrate (molecular weight 148)
B-2: Zinc acetate (molecular weight 182)
C-1: Sodium pyrrolidonecarboxylate (molecular weight 151)
D-1: Pyrrolidone carboxylic acid (molecular weight 129)
D-2: Proline (molecular weight 115)
D-3: Pantothenic acid (molecular weight 219)
S-1: Propylene glycol (boiling point 188 ° C.)
S-2: 1,3-propanediol (boiling point 224 ° C.)
S-3: 1,2-pentanediol (boiling point 210 ° C.)
S-4: Dipropylene glycol monomethyl ether (boiling point 187 ° C.)
S-5: Diethylene glycol diethyl ether (boiling point 255 ° C.)
S-6: Glycerin (boiling point 290 ° C.)
R-1: Mobile 7720 (Nippon Synthetic Chemical Acrylic Resin)
R-2: ACRYT UW-550CS (acrylic resin manufactured by Taisei Fine Chemical Co., Ltd.)
R-3: Vinibrand 701FE65 (vinyl chloride resin manufactured by Nissin Chemical Industry Co., Ltd.)
R-4: PRINTRITE DP676 (urethane resin manufactured by Lubrizol)
P-1: BYK-349 (polysiloxane surfactant manufactured by Big Chemie)
P-2: TEGO Twin 4000 (polysiloxane surfactant manufactured by Evonik)
W-1: The unit of numerical values in the ion-exchange water table is parts by mass.

<Preparation of ink>
The inks of Examples and Comparative Examples were prepared as follows using a pigment dispersion, resin (resin emulsion), water-soluble solvent (water-soluble organic solvent, water (ion-exchanged water)), surfactant, and wax emulsion. . The adjustment method of a pigment dispersion and resin (resin emulsion) is shown below.

1. Preparation of pigment dispersion A pigment dispersant was prepared by the following method.

  In 200 g of toluene kept at 100 ° C., 63 g of methyl methacrylate, 27 g of butyl acrylate, 30 g of butyl methacrylate, 15 g of acrylic acid, 15 g of methacrylic acid, and 3.6 g of tert-butylperoxy-2-ethylhexanoate Was added dropwise over 1.5 hours. After the completion of the dropping, the mixture was reacted at 100 ° C. for 2 hours and then cooled to obtain a resin solution. The resin was purified from the resin solution with hexane to obtain a pigment dispersant having a molecular weight of 20000 and an acid value of 143 mgKOH / g.

(1) Preparation of Pigment Dispersion PD-1 (Red) In 80 g of ion-exchanged water, 2.5 g of the pigment dispersant obtained above and 0.6 g of N, N-dimethylaminoethanol were dissolved. I. 15 g of Pigment Red 122 and 0.05 g of an antifoaming agent (“Surfinol 104PG” manufactured by Air Products) were added and dispersed in a paint shaker using zirconia beads to obtain pigment dispersion PD-1 (red) It was.

(2) Preparation of pigment dispersion PD-2 (blue), pigment dispersion PD-3 (yellow), pigment dispersion PD-4 (black) C.I. I. Instead of CI Pigment Red 122, C.I. I. Pigment blue 15: 4 (PB15: 4), C.I. I. Pigment Dispersion PD-2 (Blue), Pigment Dispersion PD-3 (Yellow), in the same manner as Pigment Dispersion PD-1 (Red), except that Pigment Yellow 155 (PY155) and Carbon Black were used. Pigment dispersion PD-4 (black) was obtained.

(3) Preparation of Pigment Dispersion PD-5 (Black) In 80 g of ion-exchanged water, 15 g of carbon black and 2 g of pigment dispersant SOLSPERSE 47000 (solid content acid value 20 mgKOH / g, polymer dispersant) as solid content 0.05 g of a foaming agent (“Surfinol 104PG” manufactured by Air Products) was added and dispersed with a paint shaker using zirconia beads to obtain pigment dispersion PD-5 (black).

(4) Preparation of Pigment Dispersion PD-6 (Red), Pigment Dispersion PD-7 (Blue), Pigment Dispersion PD-8 (Yellow) Instead of carbon black, C.I. I. Pigment red 122 (PR122), C.I. I. Pigment blue 15: 4 (PB15: 4), C.I. I. Pigment Dispersion PD-6 (Red), Pigment Dispersion PD-7 (Blue), Pigment Dispersion are the same as Pigment Dispersion PD-5 (Black) except that Pigment Yellow 74 (PY74) is used. Body PD-8 (yellow) was obtained.

2. Preparation of Resin Emulsion A resin emulsion was prepared by the following method. The average particle size of the obtained resin emulsion was measured at 25 ° C. using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000).

(1) Preparation of Resin Emulsion RE-1 After the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube and dropping funnel was sufficiently substituted with nitrogen gas, a reactive surfactant (Kao ( 0.75 g, potassium persulfate 0.04 g, 0.3 g of methacrylic acid and 150 g of pure water were added and stirred at 25 ° C. and mixed. A pre-emulsion was prepared by dropwise adding a mixture of 112 g of methyl methacrylate, 22.5 g of 2-ethylhexyl acrylate, and 15 g of butyl acrylate. In addition, after sufficiently replacing the inside of the flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube and dropping funnel with nitrogen gas, a reactive surfactant (trade name: Latemul, manufactured by Kao Corporation) PD-104) 3 g, potassium persulfate 0.01 g and pure water 200 g were stirred and mixed at 70 ° C. Thereafter, the prepared pre-emulsion was dropped into the flask over 3 hours. After further aging at 70 ° C. for 3 hours, the mixture was cooled, adjusted to pH 8 with N, N-dimethylethanolamine, filtered through # 150 mesh (manufactured by Nippon Textile), and 500 g of resin emulsion RE-1 (Solid content 30% by mass, glass transition temperature 36 ° C., acid value 1 mgKOH / g, hydroxyl value 0 mgKOH / g, average particle diameter 90 nm, conductivity 80 μS / cm).

(2) Preparation of Resin Emulsion RE-2 Synthesis was performed by adjusting the monomer composition by the same synthesis method as that for resin emulsion RE-1. Using 1.5 g of methacrylic acid, 115.5 g of methyl methacrylate, 18 g of 2-ethylhexyl acrylate and 15 g of butyl acrylate, glass transition temperature of 64 ° C., acid value of 7 mgKOH / g, hydroxyl value of 0 mgKOH / g, average particle diameter A resin emulsion RE-2 having 90 nm and conductivity of 110 μS / cm was obtained.

3. Ink preparation The following inks were prepared using a pigment dispersion, a resin emulsion, a water-soluble solvent, a surfactant, and ion-exchanged water.

Ink A (Mg)
Pigment dispersion PD-1 (red) 20 parts by mass Resin emulsion RE-1 20 parts by mass Propylene glycol 40 parts by mass Nopcoat PEM-17 1 part by mass TegoTwin4200 1 part by mass Ion-exchanged water 18 parts by mass

  Pigment dispersion PD-1 (red) is replaced with pigment dispersion PD-2 (blue), pigment dispersion PD-3 (yellow), and pigment dispersion PD-4 (black), respectively, and ink A (Cy) Ink A (Ye) and Ink A (Bk) were respectively adjusted. A combination of ink A (Mg), ink A (Cy), ink A (Ye), and ink A (Bk) was used as ink A.

Ink B (Bk)
Pigment dispersion PD-5 (black) 20 parts by mass Resin emulsion RE-2 20 parts by mass 1,3-propanediol 10 parts by mass Propylene glycol 35 parts by mass AQUACER 515 1 part by mass Silface SAG503A 1 part by mass Dinol 604 0.5 mass Ion-exchanged water 12.5 parts by mass

Pigment dispersion PD-5 (black) is replaced with pigment dispersion PD-6 (red), pigment dispersion PD-7 (blue), and pigment dispersion PD-8 (yellow), respectively, and ink B (Mg) Ink B (Cy) and Ink B (Ye) were respectively adjusted. A combination of ink B (Bk), ink B (Mg), ink B (Cy), and ink B (Ye) was used as ink B.

Ink C (Bk)
CAB-O-JET 400 30 parts by mass Resin Emulsion RE-1 20 parts by mass Propylene glycol 30 parts by mass PEM-17 1 part by mass Silface SAG503A 1 part by mass Ion-exchanged water 18 parts by mass

CAB-O-JET 400 is replaced with CAB-O-JET 470Y, CAB-O-JET 465M, and CAB-O-JET 450C, respectively, and ink C (Ye), ink C (Mg), and ink C (Cy) Was adjusted respectively. A combination of ink C (Bk), ink C (Ye), ink C (Mg), and ink C (Cy) was used as ink C.

[Evaluation]
(Evaluation 1-3)
Evaluation 1: Storage stability of received solution As an accelerated test of storage stability, the received solution was sealed in a glass container and stored at 60 ° C. for 2 weeks. evaluated. The results are shown in Tables 1 and 2. A and B are actual use ranges.

A: No precipitate is generated.
B: A slight precipitate is formed.
C: Many precipitates are generated.

Evaluation 2: Discharge stability of receiving solution The receiving solution was filled in a 600 dpi inkjet head, and printing was continuously performed for 3 hours, and the number of nozzles that were bent or not ejected was confirmed. The results are shown in Tables 1 and 2. A and B are actual use ranges.
A: The number of bent or non-ejection nozzles is less than 1% of all nozzles.
B: The number of bent or non-ejection nozzles is 1% or more and less than 3% of all nozzles.
C: The number of bent or non-ejection nozzles is 3% or more of all nozzles.

Evaluation 3: Intermittent discharge of receiving solution The receiving solution was filled in an ink jet head of 600 dpi, and the receiving solution was discharged from all nozzles at a discharge speed of 10 m / sec, and then left for 1 hour. Thereafter, the receiving solution was again discharged from all the nozzles at the same discharge speed. Then, the presence or absence of the non-ejection nozzle was visually observed and evaluated according to the following criteria. The results are shown in Tables 1 and 2. A and B are actual use ranges.

A: There is no non-ejection nozzle.
B: There are non-ejection nozzles, but all nozzles are immediately ejected by cleaning.
C: There are non-ejection nozzles, and there are nozzles that do not recover even after cleaning.

(Evaluation 4-8)
In order to evaluate the image quality improvement performance of the receiving solution, printing was performed with an ink set of the receiving solution and ink at a resolution of 720 × 720 dpi, and evaluations 4 to 8 were performed. The receiving solutions of Examples and Comparative Examples were used as the receiving solutions. The inks used were ink A and ink C (hereinafter, the ink set including the receiving solution and the ink of the example is an ink set according to the example, and the ink set including the receiving solution and the ink of the comparative example is according to a comparative example) Sometimes referred to as ink set.) Printing is performed by ejecting the receiving solution onto a recording medium (OK top coat + (Oji Paper Coated Paper)), which is a low-absorbing substrate, and then ejecting the ink to produce high-definition color digital standard image data (ISO / JIS). -SCID) and solid images of each color were printed and evaluated, and the results are shown in Tables 1 to 3.

  Furthermore, the ink sets containing the receiving solutions of Examples and Comparative Examples and inks A to C were evaluated using a non-absorbent substrate as a recording medium. Specifically, the surface temperature of the recording medium when the receiving solutions and inks A to C of Examples and Comparative Examples are applied to the surface of the substrate on a polyvinyl chloride film (IMAMAGin JT5829R manufactured by MACtac) without a receiving layer. The temperature was set to 40 ° C., the receiving solution and ink were ejected to print the same image as described above, and then the surface temperature of the printed material was set to 80 ° C. and dried. And evaluation 4-8 was implemented about this printed matter. The results are shown in Table 5.

Evaluation 4: Bleeding evaluation from the printed part to the non-printed part A: No blur was observed and the image was clear.
B: Slight bleeding was observed, but the image was clear.
C: Bleeding was observed and the image was unclear.
A and B are actual use ranges.

Evaluation 5: Color boundary bleeding (Bleeding in which inks of different colors adjoining irregularly)
A: No blur was observed and the image was clear.
B: Slight bleeding was observed, but the image was clear.
C: Bleeding was observed and the color boundary was unclear.
A and B are actual use ranges.

Evaluation 6: Solid filling (filling of solid printed portions (white spots))
A: Printing unevenness and white spots were not observed, and the solid portion was sufficiently filled with ink (the dot diameter was sufficiently widened).
B: Although there was slight unevenness, the solid part was buried.
C: The solid portion was not sufficiently filled and unevenness was observed.
A and B are actual use ranges.

Evaluation 7: Dryability test The dryness test was done about the printed matter printed with the ink set which concerns on an Example and a comparative example. Specifically, as described above, solid printing was performed by inkjet using an ink set of the receiving solution and ink, and the time until the solid printing portion was dried at 80 ° C. was confirmed. The results are shown in Tables 1 and 2.
A: Dried in less than 3 minutes.
B: It dried in 3 minutes or more and less than 10 minutes.
C: Dried in 10 minutes or more.
A and B are actual use ranges.

Evaluation 8: Water resistance evaluation Water resistance evaluation was performed on the printed matter printed by the ink sets according to Examples and Comparative Examples. Specifically, as described above, solid printing was performed with an ink set of a receiving solution and ink, and a test piece obtained by drying the solid printing portion at 100 ° C. for 3 minutes was wiped with ion-exchanged water, and the printed matter was visually confirmed. The results are shown in Tables 1 and 2.
A: No change was observed in the printed matter.
B: The color of the printed material was slightly light.
C: The color of the printed material was clearly light.
A and B are actual use ranges.

[Evaluation results]
From Tables 1 and 2, it is a receiving solution containing a polyvalent metal salt, a water-soluble solvent, and a resin, which are calcium ions, magnesium ions, zinc ions and organic amphoteric ions that are polyvalent metal ions. The accepting solutions of the examples containing polyvalent metal salts containing amino acid ions had excellent evaluation results in Evaluations 1 to 3, and thus were excellent in storage stability, continuous ejection properties, and intermittent ejection properties. It turns out to be a receiving solution.

  On the other hand, from Table 3, the receiving solutions of Comparative Examples 1 to 6 containing a salt that does not contain an organic amphoteric ion as a polyvalent metal salt are receiving solutions inferior in storage stability, continuous dischargeability, and intermittent dischargeability. I understand that. This is because the use of an inorganic salt that does not contain organic amphoteric ions as the polyvalent metal salt results in poor compatibility with each component contained in the receiving solution, generation of precipitates, and gelation of the receiving solution. It is thought that it was difficult to maintain the stability of the receiving solution because of the occurrence of thickening and thickening.

  Further, from Tables 1 and 2, the receiving solutions of the examples show that the printed matter printed on the low-absorbent substrate has an excellent evaluation result in Evaluations 4 to 7, and therefore, from the printing part to the non-printing part. It turns out that it is a receiving solution which can be made into the printed matter excellent in the blur suppression effect, the blur suppression effect of a color boundary, solid filling property, and drying property.

  On the other hand, from Table 3, a compound containing no polyvalent metal ion as a polyvalent metal salt (pyrrolidone carboxylic acid only (Comparative Example 7), proline only (Comparative Example 8), pantothenic acid only (Comparative Example 9), and pyrrolidone carboxylic acid In the receiving solutions of Comparative Examples 7 to 10 containing a polyvalent metal salt containing sodium ions that are not polyvalent metal ions as acids and metal ions (Comparative Example 10), the printed matter printed on the low-absorbent substrate bleeds. It can be seen that this is a receiving solution that is solid and becomes a printed matter with poor drying properties.

  Furthermore, from Tables 1 and 2, the receiving solutions of the examples were printed on a low-absorbency substrate, and the printed material with excellent water resistance was obtained because the printed material printed on the low-absorbent substrate had an excellent evaluation result in Evaluation 8. It turns out that it is a receiving solution that can be made.

  On the other hand, it can be seen from Table 3 that the receiving solution of Comparative Example 11 containing no resin is a receiving solution in which the printed matter printed on the low-absorbent substrate becomes a printed matter with poor water resistance.

  Moreover, even when it prints on the polyvinyl chloride film which is a non-absorbent base material from Table 5, the printed matter manufactured by the ink set which concerns on an Example has the evaluation result excellent in evaluation 4-8. On the other hand, the ink set according to the comparative example is inferior in comparison with the ink set according to the example. Therefore, it can be seen that the ink set of the present invention is an ink set capable of obtaining a printed matter with good image quality and water resistance even when a non-absorbent substrate is used as a recording medium.

Claims (9)

An ink jet recording receiving solution containing a polyvalent metal salt, a water-soluble solvent, and a resin,
Containing a resin emulsion as the resin,
The accepting solution for inkjet recording, wherein the polyvalent metal salt is a salt containing a polyvalent metal ion and an organic amphoteric ion.   The receiving solution for inkjet recording according to claim 1, wherein the polyvalent metal salt is a salt that does not substantially contain an inorganic salt.   The receiving solution for inkjet recording according to claim 1 or 2, wherein the molar concentration of the polyvalent metal salt in the receiving solution for inkjet recording is 0.001 mol / kg or more and 1.0 mol / kg or less.   4. The ink jet recording receiving solution according to claim 1, wherein the polyvalent metal salt is a salt of a polyvalent metal ion and an amino acid ion. 5.   The receiving solution for inkjet recording according to claim 4, wherein the amino acid is an α-amino acid.   The receiving solution for inkjet recording according to claim 4 or 5, wherein the amino acid is an amino acid containing a nitrogen-containing heterocyclic structure.   The inkjet according to any one of claims 1 to 6, wherein the polyvalent metal ion is one or more polyvalent metal ions selected from the group consisting of calcium ions, magnesium ions, nickel ions, zinc ions, and aluminum ions. Receiving solution for recording. A receiving solution for inkjet recording according to any one of claims 1 to 7;
An inkjet recording ink containing a colorant;
An ink set for ink-jet recording, comprising:   A method for producing a printed matter comprising a step of applying the receiving solution for inkjet recording according to any one of claims 1 to 7 onto a recording medium or an ink containing a color material.