JPH10114140A - Reactive liquid used for two-pack ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the shelf life and print stability of a reactive liquid by using the reactive liquid which contains at least, components selected from a polyvalent metal salt, a compound containing nitrogen or sulfur, an amine and a cationic surfactant. SOLUTION: This ink jet recording method comprises a step to print a reactive liquid and an ink composition on a recording medium. The reactive agent contains at least, components selected from a polyvalent metal salt, a compound containing nitrogen or sulfur, an amine and a cationic surfactant. The compound containing nitrogen comprises a 5- or 6-membered saturated or unsaturated cyclic compound which contains, at least, one nitrogen atom and an optionally alkyl-substituted amide derivative. It is possible to inhibit the generation of a deposit by allowing the presence of the compound containing nitrogen or sulfur in the reactive liquid and simultaneously improve the print quality and the print stability by adding an amine. Further, it is possible to promote the generation of a flocculate by adding the cationic surfactant, and consequently, fix a coloring component rapidly and positively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording method for printing by depositing a reaction liquid and an ink composition on a recording medium and a reaction liquid used for the method.

2. Description of the Related Art An ink jet recording method is a printing method in which small droplets of an ink composition fly and adhere to a recording medium such as paper to perform printing. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. In general, an ink composition used for ink jet recording contains water as a main component, and further contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

On the other hand, as an ink jet recording method, a method has recently been proposed in which a polyvalent metal salt solution is applied to a recording medium and then an ink composition containing a dye having at least one carboxyl group is applied ( For example, JP-A-5-202328). In this method,
An insoluble complex is formed from the polyvalent metal ion and the dye,
It is said that the presence of this composite makes it possible to obtain a high-quality image that is water-resistant and has no color bleed.

[0004] Further, by using a color ink containing at least a surfactant or a penetrating solvent for imparting permeability and a salt, and a black ink which thickens or aggregates by the action of the salt, an image is formed. It has been proposed that a high-quality color image having a high density and no color bleed can be obtained (Japanese Patent Laid-Open No. 6-10673).
No. 5). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids of a first liquid containing a salt and an ink composition.

In addition, an ink jet recording method for printing two liquids has been proposed (for example, see Japanese Patent Application Laid-Open No.
240557, JP-A-3-240558).

[0006]

SUMMARY OF THE INVENTION The present inventors have recently used such an ink jet recording method for printing two liquids.
The knowledge that the presence of a specific compound in a reaction solution containing a polyvalent metal salt can improve the storage stability and printing stability of the reaction solution and further improve the quality of a printed image obtained. Obtained. The present invention is based on this finding.

Accordingly, an object of the present invention is to provide a good reaction liquid used in an ink jet recording method for printing two liquids.

Another object of the present invention is to provide an ink jet recording method for printing two liquids which realizes a good printed image without clogging.

The reaction liquid according to the present invention is used in an ink jet recording method for printing by attaching the reaction liquid and an ink composition to a recording medium, and comprises a polyvalent metal salt, a nitrogen-containing compound or It contains at least a component selected from the group consisting of a sulfur-containing compound, an amine, and a cationic surfactant.

The ink jet recording method according to the present invention utilizes the above-mentioned reaction solution.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Ink jet recording method The ink jet recording method according to the present invention comprises a step of printing a reaction liquid and an ink composition on a recording medium.

The order in which the reaction liquid and the ink composition are applied to the recording medium may be any order, that is, a method in which the reaction liquid is applied to the recording medium, and then the ink composition is applied to the recording medium. A method of adhering the reaction liquid after printing the ink composition and a method of mixing the reaction liquid and the ink composition immediately before or immediately after the ejection can be suitably performed.

According to the ink jet recording method of the present invention, good printing can be realized. The following is a hypothetical theory, and it is not intended that the present invention be interpreted in a limited manner. The reason why good printing can be realized is considered as follows. When the reaction liquid comes into contact with the ink composition, the polyvalent metal salt in the reaction liquid destroys the dispersion state of the colorant and the like in the ink composition and causes the colorant components and the like to aggregate. The aggregates adhere to the recording medium,
It is considered that printing with high color density, less bleeding, and less unevenness is realized. Further, in a color image, there is an advantage that uneven color mixing in a boundary region of different colors, that is, color bleed can be effectively prevented.

Regarding the adhesion of the reaction liquid to the recording medium, there are either a method in which the reaction liquid is selectively applied only to the place where the ink composition is to be applied, or a method in which the reaction liquid is applied to the entire surface of the paper. You may. The former is economical because it can minimize the consumption of the reaction solution,
A certain degree of accuracy is required for the position where both the reaction liquid and the ink composition are attached. On the other hand, in the latter, the requirement for the accuracy of the adhesion position of the reaction liquid and the ink composition is relaxed as compared with the former, but a large amount of the reaction liquid adheres to the entire surface of the paper, and the paper is easily curled during drying. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid. When the former method is adopted, the reaction liquid can be attached by an ink jet recording method.

Reaction Solution The reaction solution used in the present invention basically comprises at least a polyvalent metal salt and a component selected from the group consisting of a nitrogen-containing compound or a sulfur-containing compound, an amine, and a cationic surfactant. Comprising.

The polyvalent metal salt that can be used in the polyvalent metal salt reaction solution is composed of a divalent or higher polyvalent metal ion and an anion bonded to these polyvalent metal ions, and is soluble in water. Things. Specific examples of polyvalent metal ions include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ ,
Divalent metal ions Al ³⁺ such as Mg ²⁺ , Zn ²⁺ , Ba ²⁺ ,
Trivalent metal ions such as Fe ³⁺ and Cr ³⁺ can be mentioned. Examples of anions include Cl ⁻ , NO ₃ ⁻ , I ⁻ , Br ⁻ , C
10 ₃ ^- and CH ₃ COO- ^{and the} like.

In particular, a metal salt composed of Ca ²⁺ or Mg ²⁺ gives favorable results from two viewpoints, that is, the pH of the reaction solution and the quality of the printed matter obtained.

The concentration of these polyvalent metal salts in the reaction solution may be appropriately determined within the range where the printing quality and the effect of preventing clogging can be obtained, but it is preferably about 0.1 to 40% by weight, more preferably. Is about 5 to 25% by weight.

In a preferred embodiment of the present invention, the polyvalent metal salt contained in the reaction solution is composed of divalent or higher polyvalent metal ions and nitrate ions or carboxylate ions bound to these polyvalent metal ions. It is soluble in water.

Here, the carboxylate ion is preferably derived from a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms or a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid,
Isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid and the like. Particularly, formic acid and acetic acid are preferable.

The hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid may be substituted with a hydroxyl group, and a preferred example of such a carboxylic acid is lactic acid.

Further, preferred examples of the carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid, and more preferably benzoic acid.

Containing nitrogen-containing compounds or sulfur-containing compounds
Reaction Solution According to the first aspect of the present invention, a reaction solution containing a nitrogen-containing compound or a sulfur-containing compound is provided. In the present specification, a nitrogen-containing compound is a 5- or 6-membered saturated or unsaturated heterocyclic compound containing at least one nitrogen,
And amide derivatives which may be alkyl-substituted.

The reaction solution containing a nitrogen-containing compound according to the present invention is one in which the generation of precipitates during storage is small. It is believed that the presence of a nitrogen-containing compound or a sulfur-containing compound suppresses generation of precipitates. When a nitrogen-containing compound or a sulfur-containing compound is not present, precipitates having a size of about 10 μm to 50 μm often occur in a reaction solution during storage, particularly in a reaction solution once exposed to a high temperature (for example, a temperature exceeding 60 ° C.). To be observed. Such deposits are not preferable because they cause clogging of nozzles of the ink jet recording head. By causing the nitrogen-containing compound or the sulfur-containing compound to be present in the reaction solution containing the polyvalent metal salt, the generation of precipitates even in the reaction solution during storage, especially in the reaction solution exposed to the high temperature as described above. Is not substantially observed. Thereby, the reliability of the ink jet recording method is improved.

The reason why the generation of precipitates is suppressed by the presence of these nitrogen-containing compounds or sulfur-containing compounds in the reaction solution is not clear, but the unpaired electrons of the nitrogen or sulfur atoms cause the formation of the precipitates. It is conceivable that the ion species or the like causing the stabilization are stabilized. However, these are hypotheses, and the present invention is not limited to this hypothesis.

As the 5- or 6-membered saturated or unsaturated heterocyclic compound containing at least one nitrogen, pyrrolidine and piperidine are preferably 5- or 6-membered saturated compounds.
Or as a 6-membered unsaturated compound, pyrrole, imidazole, pyrazole, pyridine, pyridazine, pyrimidine,
Pyrazine and (alkyl-substituted) amide derivatives include pyrrolidone, N-substituted pyrrolidone, imidazolidinone, N-substituted imidazolidinone and the like. More preferred specific examples include 2-pyrrolidone, N-lower alkyl (preferably methyl) -substituted pyrrolidone, 1,3-lower alkyl-substituted (preferably methyl) -2-imidazolidinone, and the like. Further, the sulfur-containing compound is preferably thiodiglycol.

The concentration of these nitrogen-containing compounds or sulfur-containing compounds in the reaction solution may be appropriately determined within a range where the effect of preventing printing quality and preventing clogging can be obtained, but is preferably about 0.5 to 20% by weight. , More preferably 2-1
It is about 0% by weight.

Reaction Solution Containing Amine According to a second aspect of the present invention, there is provided a reaction solution containing an amine. By adding an amine, printing quality and printing stability can be simultaneously improved. In this embodiment, the amine contained in the reaction solution means ammonia or ammonia in which 1 to 3 hydrogen atoms have been substituted with a hydrophobic hydrocarbon group, that is, primary, secondary and tertiary amines.

According to a preferred embodiment of the present invention, the reaction solution according to the present invention comprises ammonia as an amine. Ammonia has a small increase in viscosity when added to a reaction solution and has a high solubility in water as compared with an amine having a normal hydrocarbon group. Therefore, an amount sufficient to satisfy both the print quality and the print stability can be added. Further, addition of ammonia hardly affects the surface tension of the reaction solution, and does not unnecessarily reduce the wettability of the reaction solution. Therefore, the obtained printed matter has a sharp edge and its OD value is high. Further, since ammonia has volatility, the drying speed of the ink is reduced, and after drying, the effect of having a strong abrasion resistance is also obtained.

The amount of ammonia added may be appropriately determined in consideration of the pH of the reaction solution, but is generally 0.5% by weight or less, preferably 0.1% by weight or less in the reaction solution. I do.

The hydrocarbon group of the primary, secondary and tertiary amines may be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group, and may be any of a straight or branched chain. Good.

According to a preferred embodiment of the present invention, the primary amine having a hydrocarbon group bonded to an amino group (—NH ₂ ) is an amine having a linear hydrocarbon group having about 6 to 18 carbon atoms. Preferably, more preferably, the carbon number is 12 to 1.
About 8 linear hydrocarbon groups. Specific examples of these include laurylamine, cetylamine, and stearylamine. With these additions, both print quality and print stability can be compatible at a high level.

The amount of the amine to be added may be appropriately determined depending on the kind of the amine, and specifically, can be individually determined for each amine in consideration of print quality, print stability, and amine solubility. . Generally, it is added in an amount of about 0.01% to 1% by weight in the reaction solution. Amines having a small number of carbon atoms in the hydrocarbon group can be added to the reaction solution in a relatively large amount, but amines having a large number of carbon atoms in the hydrocarbon group have low solubility and increase the viscosity of the reaction solution. Generally, the amount that can be added is limited.

Secondary and tertiary amines can also be used in the present invention, as well as the primary amines described above. Examples of secondary and tertiary amines are di-n-propylamine, di-n-butylamine,
Di-n-amylamine, di-n-octylamine, distearylamine (secondary amine), trimethylamine, propyldimethylamine, butyldimethylamine, octyldimethylamine, stearyldimethylamine (third amine) Is mentioned.

It is also possible to use an amine whose hydrocarbon group has a cyclic structure. Examples include cyclohexylamine, dicyclohexylamine, benzylamine, N-cyclohexyl-n-dodecylamine, N
-Benzyl-n-dodecylamine, No-tolyl-n
-Dodecylamine, Np-tolyl-n-dodecylamine and the like.

Further, in the present invention, the term amine is used to include a cyclic imine. Examples of cyclic imines include pyrrolidine, piperidine, hexamethylene imine, octamethylene imine, and decamethylene imine, all of which can provide stable printing characteristics.
Particularly, octamethyleneimine having a methylene chain of 8 to 10 gives a good effect, and the printing stability is remarkably improved as compared with octylamine or dibutylamine having the same total number of carbon atoms.

In the present invention, the amine is preferably added in the form of an inorganic acid salt or amide. Examples of the inorganic acids include various inorganic acids such as nitric acid, nitrous acid, hydrochloric acid, bromic acid, and chromic acid. By adding the amine to the reaction solution in the form of an inorganic acid salt, the solubility of the amine is improved, and the storage stability and printing stability can be improved. Further, by appropriately selecting the kind of the inorganic acid, it is possible to prevent the pH from being biased toward the alkali side.

Examples of the amide include those obtained by heat-treating a mixture of an amine and a fatty acid, and include C _n H _{2n + 1} NH ₂
And C _n-1 mixture of H _2n-1 COOH (n is an integer, the same applies hereinafter), a mixture of _{(C n H 2n + 1)} 2 NH with _{C n-1 H 2n-1} COOH, (C n H _{2n + 1} ) ₃ N and C _n-1 H _2n-1 COOH
The mixture obtained by heat-treating the mixture has the same effect as when the amine is added to the reaction solution.

A part of the amine in which the hydrocarbon group has a cyclic structure, the cyclic imine, and the amide also have a function as the nitrogen-containing compound of the reaction solution according to the first embodiment.

Further, according to a preferred embodiment of the present invention, the amine preferably has an appropriate volatility.
The ink composition containing the amine having volatility is quickly dried after adhering to paper, and after drying, a printed matter having robust abrasion resistance is obtained.

According to a preferred embodiment of the present invention, the amine has a vapor pressure of at least 0.01 Pa at 25 ° C. Specifically, in addition to the above-mentioned ammonia, dicyclohexylamine nitrite and the like are applicable.

[0042] According to a third aspect of the cationic surfactants present invention, the reaction solution comprising a cationic surfactant. As described above, in the inkjet recording method according to the present invention, the polyvalent metal salt in the reaction liquid destroys the dispersion state of the colorant and the like in the ink composition, aggregates the colorant components and the like, and the aggregated matter is recorded. It is considered that the toner adheres to the medium and realizes printing with high color density, less bleeding, and less unevenness. It is believed that the addition of a cationic surfactant further promotes the formation of the above-mentioned aggregates. As a result, the colorant component can be quickly and reliably fixed on the recording medium, and good printing can be performed. here,
Since the cationic surfactant has high solubility in an aqueous solvent, it is advantageous in that the concentration of the cationic surfactant contained in the reaction solution can be increased. In addition, cationic surfactants also act as penetrants. Therefore, there is an advantage that the drying property of the printed matter can be improved at the same time. Further, in a color image, there is an advantage that uneven color mixing in a boundary region of different colors, that is, color bleed can be effectively prevented.

The cationic surfactant used in the present invention includes primary, secondary, tertiary and quaternary ammonium salts and those derived therefrom,
And a sulfuric acid-based cationic surfactant.
In particular, a cationic surfactant containing one quaternary nitrogen atom is preferable. Further, those in which at least two or more of the substituents bonded to the quaternary nitrogen atom each contain six or more carbon atoms are preferable from the viewpoint of high cohesion.

Specific examples of the cationic surfactant include:
A quaternary ammonium salt represented by the following formula (I) is exemplified.

[0045] ^{R 1 R 2 R 3 R 4} N + X - (I) ( wherein, R ¹ and R ² are independently C ₈ -C ₂₀ alkyl group, a benzyl group or a phenyl group,, R ³ and R ⁴ represents a C ₁ -C ₄ alkyl group independently, X ^-
Represents a counter ion)

Specific examples of the cationic surfactant represented by the formula (I) include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride, octadecyl Amine acetates.

The amount of the cationic surfactant to be added to the reaction solution is not particularly limited, but is preferably 0.1 to 20% by weight.
And more preferably about 5 to 10% by weight.

Other components of the reaction liquid The reaction liquid according to the present invention is colored by adding the colorant described in the section of the ink composition described below, and has the function of the ink composition. Is also good. In this case, when the coloring agent is a dye, the reaction solution preferably further contains glycerin. By the presence of glycerin, it is possible to further suppress the generation of a precipitate which is considered to be caused by the precipitation of the dye.

The concentration of glycerin in the reaction solution may be appropriately determined within the range where the effect of preventing clogging can be obtained, but is preferably 0.5 based on the reaction solution (or dye).
About 40% by weight, more preferably about 2 to 20% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain a wetting agent comprising a high-boiling organic solvent. The high boiling point organic solvent prevents clogging of the head by preventing the reaction solution from drying. Preferred examples of the high-boiling organic solvent include ethylene glycol, diethylene glycol,
Polyhydric alcohols such as triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; ethylene glycol Alkyl ethers of polyhydric alcohols such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether , Urea, triethanolamine, etc. It is.

The amount of the high-boiling organic solvent is not particularly limited, but is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain a low-boiling organic solvent. Preferred examples of the low boiling organic solvent include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol and n-
Butanol, sec-butanol, tert-butanol, iso-butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable. Low-boiling organic solvents have the effect of shortening the drying time of the ink. The addition amount of the low boiling organic solvent is preferably 0.5 to 10% by weight, and more preferably 1.5 to 6% by weight.

According to a preferred embodiment of the present invention, the reaction solution may contain a penetrant. Examples of the penetrant include various surfactants such as anionic surfactants and amphoteric surfactants, alcohols such as methanol, ethanol and isopropyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether. Examples include lower alkyl ethers of polyhydric alcohols such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether.

The penetrant which can be used in the present invention is more preferably a compound represented by the following formula (I) and / or a lower alcohol ether of a polyhydric alcohol.

[0055]

Embedded image (Where 0 ≦ m + n ≦ 50, and R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group) Specific examples of the compound represented by the above formula (I) Are Orfin Y, Surfinol 82, Surfinol 440, Surfinol 465, Surfinol 485 (all manufactured by Air Products a
nd Chemicals. Inc. ). These may be used alone or in combination of two or more.

According to a preferred embodiment of the present invention, the reaction solution contains triethanolamine for pH adjustment.
When triethanolamine is added, its amount is preferably about 0 to 2.0% by weight.

Ink Composition In the present invention, the ink composition means a black ink composition when performing monochrome printing, and a color ink composition when performing color printing, specifically, a yellow ink composition. , Magenta ink composition, and cyan ink composition, and in some cases, black ink composition.

The ink composition used in the present invention contains at least a colorant and water.

The colorant contained in the ink composition used in the present invention may be either a dye or a pigment. However, the colorant in the ink is inactivated by the action of insolubilizing or thickening the ink composition. For suppressing penetration, dispersed pigments are more advantageous than dyes dissolved in aqueous media.

Dyes include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes,
Various dyes usually used for ink jet recording, such as a soluble vat dye and a reactive disperse dye, can be used.

As pigments, inorganic pigments and organic pigments can be used without any particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. Examples of organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc., dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

According to a preferred embodiment of the present invention, these pigments are preferably added to the ink as a pigment dispersion obtained by dispersing in an aqueous medium with a dispersant or a surfactant. As a preferred dispersant, a dispersant commonly used for preparing a pigment dispersion, for example, a polymer dispersant can be used.

Preferred examples of the dispersant or surfactant include polyacrylic acid, polymethacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, and acrylic acid-alkyl acrylate copolymer. Styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid-
Acrylic acid alkyl ester copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer Copolymer, styrene-maleic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate- Crotonic acid copolymer and vinyl acetate-acrylic acid copolymer.

According to a preferred embodiment of the present invention, these copolymers have a weight average molecular weight of 3,000 to 50,000.
Degree, more preferably 5,000 to
About 30,000, most preferably 7,000 to 15,
It is about 000.

The amount of the dispersing agent added may be appropriately within a range that stably disperses the pigment and does not lose other effects of the present invention. According to a preferred embodiment of the present invention, the amount of the pigment: dispersant is preferably in the range of about 1: 0.06 to 1: 3, more preferably in the range of about 1: 0.125 to 1: 3. .

The amount of the pigment added to the ink is 0.5 to 25.
% By weight, more preferably 2 to 15% by weight.
It is about.

According to a preferred embodiment of the present invention, the ink composition preferably comprises a resin emulsion. Here, the resin emulsion means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. As the resin component of the dispersed phase, acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acryl-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, Benzoguanamine resin, phenol resin, silicone resin, epoxy resin and the like can be mentioned.

According to a preferred embodiment of the present invention, the resin is preferably a polymer having both a hydrophilic part and a hydrophobic part. Further, the particle size of these resin components is not particularly limited as long as an emulsion is formed.
Or less, more preferably about 5 to 100 nm.

These resin emulsions can be obtained by dispersion polymerization of a resin monomer in water together with a surfactant, if necessary. For example, an emulsion of an acrylic resin or a styrene-acrylic resin can be obtained by dispersing and polymerizing a (meth) acrylate or a (meth) acrylate and styrene together with a surfactant in water.
The mixing ratio of the resin component and the surfactant is usually 10: 1.
It is preferable to set it to about 5: 1. When the amount of the surfactant used is in the above range, better water resistance and permeability of the ink can be obtained. Although the surfactant is not particularly limited, preferred examples thereof include anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfate, and the like), nonionic surfactants ( For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, etc.) can be used alone or in combination. A mixture of more than one species can be used. Also, acetylene glycol (Olefin Y and Surfynol 82, 104, 440, 465, and 485 (all of which are Air Products and Chemicals In
c.)) can also be used.

The proportion of the resin and water as the disperse phase component is suitably in the range of 60 to 400 parts by weight of water, preferably 100 to 200 parts by weight with respect to 100 parts by weight of the resin.

It is also possible to use a commercially available resin emulsion, for example, Microgel E-100.
2, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001
(Acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.) Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, Zeon Corporation) Made), Cybinol S
K-200 (acrylic resin emulsion, manufactured by Seiden Chemical Co., Ltd.).

The ink used in the present invention preferably contains a resin emulsion such that the resin component is 0.1 to 40% by weight of the ink, more preferably 1 to 2%.
It is in the range of 5% by weight.

The resin emulsion has an effect of suppressing the penetration of the coloring component and promoting the fixation to the recording medium by the interaction with the polyvalent metal ion. Also, depending on the type of resin emulsion, a film is formed on the recording medium,
It also has the effect of improving the abrasion resistance of the printed matter.

According to a preferred embodiment of the present invention, the ink composition may contain a thermoplastic resin in the form of a resin emulsion. Here, the thermoplastic resin is a resin having a softening temperature of 50.
C. to 250C, preferably 60C to 200C. Here, the term "softening temperature" refers to the glass transition point, melting point, and temperature at which the viscosity of the thermoplastic resin becomes 10 ¹¹ to 10 ¹² poise, the pour point, and the minimum film formation temperature (MFT) when in the form of a resin emulsion. Means the lowest temperature. When an ink composition containing such a resin emulsion is used, it is preferable to perform a heating step of heating the recording medium after recording at a temperature equal to or higher than the softening temperature of the thermoplastic resin.

These resins have strong water resistance when heated and cooled to a temperature higher than the softening or melting temperature.
It is preferable to select one that forms a film having abrasion resistance.

Specific examples of the water-insoluble thermoplastic resin include polyacrylic acid, polymethacrylic acid, polymethacrylic acid ester, polyethylacrylic acid, styrene-
Butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, fluororesin, vinylidene fluoride, polyolefin resin, cellulose, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, polystyrene, Styrene-acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyamide, rosin resin, polyethylene, polycarbonate, vinylidene chloride resin, cellulose resin, vinyl acetate resin, ethylene-vinyl acetate copolymer ,
Examples include, but are not limited to, vinyl acetate-acrylic copolymers, vinyl chloride resins, polyurethanes, rosin esters, and the like.

Specific examples of the low molecular weight thermoplastic resin include animal and plant waxes such as polyethylene wax, montan wax, alcohol wax, synthetic oxidized wax, α-olefin-maleic anhydride copolymer, carnauba wax, lanolin, paraffin wax. And microcrystalline wax.

As such a resin emulsion, known resin emulsions can be used. For example, JP-B-62-1426, JP-A-3-56573, JP-A-3-79678, and JP-A-3-160068. The resin emulsion described in JP-A-4-18462 can be used as it is.

According to a preferred embodiment of the present invention, the ink composition may contain an alginic acid derivative. Preferred examples of the alginic acid derivative include alkali metal alginates (eg, sodium salts and potassium salts), organic alginates (eg, triethanolamine salts), and ammonium alginates.

The amount of the alginic acid derivative added to the ink composition is preferably about 0.01 to 1% by weight.
More preferably, it is about 0.05 to 0.5% by weight.

Although the reason why a good image can be obtained by adding the alginic acid derivative cannot be determined, the polyvalent metal salt present in the reaction solution reacts with the alginic acid derivative in the ink composition to change the dispersion state of the colorant. It is considered that this is because the fixation of the colorant to the recording medium is promoted.

The ink composition used in the present invention may contain an inorganic oxide colloid. Preferred examples of the inorganic oxide colloid include colloidal silica,
Alumina colloid is mentioned. These are generally colloidal solutions in which ultrafine particles such as SiO ₂ and Al ₂ O ₃ are dispersed in water or an organic solvent. The inorganic oxide colloid which is commercially available, the dispersion medium is water, methanol, 2-propanol, and the n- propanol, xylene and the like, SiO _2, Al ₂ 0 particle size of ₃ such particles 5
Those having a thickness of 100 nm are generally used. In addition, the pH of the inorganic oxide colloid solution is often adjusted not to a neutral region but to acidic or alkaline. This is because the stable dispersion region of the inorganic oxide colloid exists on the acidic side or the alkaline side, and when added to the ink composition, the pH of the stable dispersion region of the inorganic oxide colloid and the pH of the ink are adjusted. It is necessary to add in consideration.

The amount of the inorganic oxide colloid added to the ink composition is preferably 0.1 to 15% by weight, and two or more kinds can be added.

According to a preferred embodiment of the present invention, the ink composition preferably contains an organic solvent. This organic solvent is preferably a low-boiling organic solvent, and preferred examples thereof include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, is
o-butanol, n-pentanol and the like.
Particularly, a monohydric alcohol is preferable. Low-boiling organic solvents have the effect of shortening the drying time of the ink.

According to a preferred embodiment of the present invention, the ink composition used in the present invention preferably further comprises a wetting agent comprising a high-boiling organic solvent. Preferred examples of the high-boiling organic solvent include ethylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-
Polyhydric alcohols such as hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, trimethylolpropane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinone, triethanolamine and the like.

The wetting agent was added in an amount of 0.5
Preferably, it is in the range of 2 to 20% by weight. Further, the amount of the low-boiling organic solvent to be added is preferably 0.5 to 10% by weight of the ink, more preferably 1.5 to 6% by weight.

According to a preferred embodiment of the present invention, the ink composition preferably contains a saccharide. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosyl , (Sorbit), maltose, cellobiose,
Lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a sugar in a broad sense, and is used to include a substance widely existing in nature such as alginic acid, α-cyclodextrin, and cellulose.

Further, derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols (general formula H
OCH ₂ (CHOH) n CH ₂ OH (where n = 2
Represented by an integer of 5), oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thiosugars and the like. In particular, sugar alcohols are preferred, and specific examples include maltitol and sorbitol.

The content of these saccharides is 0.1 to 0.1% of the ink.
A suitable range is 40% by weight, preferably 0.5 to 30% by weight.

In addition, if necessary, a pH adjuster, a preservative, a fungicide and the like may be added.

Ink Jet Recording Apparatus An ink jet recording apparatus for carrying out the ink jet recording method according to the present invention will be described below with reference to the drawings.

The ink jet recording apparatus shown in FIG. 1 is an embodiment in which an ink composition and a reaction liquid are stored in a tank, and the ink composition and the reaction liquid are supplied to a recording head via an ink tube. That is, the recording head 1 and the ink tank 2 are connected by the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and the ink composition,
In some cases, a room for a plurality of color ink compositions and a room for a reaction liquid are provided.

The recording head 1 moves along the carriage 4
It is moved by a timing belt 6 driven by a motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by the platen 8 and the guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is supplied to the waste ink tank 13 via the tube 12.
Is stored.

FIG. 2 is an enlarged view of the nozzle surface of the recording head 1. The portion indicated by 1b is the nozzle surface of the reaction liquid, and the nozzle 21 for discharging the reaction liquid is provided in the vertical direction. On the other hand, the portion indicated by 1c is the nozzle surface of the ink composition, and from the nozzles 22, 23, 24, and 25, the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are respectively provided. Discharged.

Further, an ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG. The recording head 1 moves in the direction of arrow A. During that move,
The reaction liquid is discharged from the nozzle surface 1b to form a band-like reaction liquid attachment region 31 on the recording medium 7. Next, the recording medium 7 is transported by a predetermined amount in the paper feed direction arrow B. During that time, the recording head 1 moves in the direction opposite to the arrow A in the figure, and returns to the position on the left end of the recording medium 7. Then, the ink composition is printed on the reaction liquid adhering area where the reaction liquid has already adhered, and a printing area 32 is formed.

Further, as shown in FIG. 4, in the recording head 1, all the nozzles can be arranged in the horizontal direction. In the figure, 41a and 41b are discharge nozzles of a reaction liquid, respectively, from the nozzles 42, 43, 44 and 45, a yellow ink composition, a magenta ink composition,
A cyan ink composition and a black ink composition are ejected. In the recording head of such an aspect, the recording head 1 can perform printing both in the forward path and the return path in which the recording head 1 reciprocates on the carriage, so that the recording head 1 has a higher speed than the case of using the recording head shown in FIG. Printing can be expected.

Further, by adjusting the surface tensions of the reaction liquid and the ink composition, regardless of the order of their attachment,
High quality printing is obtained more consistently. In this case, the number of the reaction solution discharge nozzles may be one (for example, 4 in the figure).
1b can be omitted), and further downsizing of the head and speeding up of printing can be achieved.

Further, in some ink jet recording apparatuses, replenishment of the ink composition is performed by replacing a cartridge which is an ink tank. This ink tank may be integrated with the recording head.

FIG. 5 shows a preferred example of an ink jet recording apparatus using such an ink tank. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 5, the recording heads 1a and 1b
Are integrated with the ink tanks 2a and 2b.
The recording head 1a or 1b discharges the ink composition and the reaction liquid, respectively. The printing method may be basically the same as that of the apparatus shown in FIG. In this embodiment, the recording head 1a and the ink tank 2a and the recording head 1a and the ink tank 2b move on the carriage 4.

FIG. 6 shows a preferred example of an ink jet recording apparatus provided with a heater for heating a printed recording medium. FIG. 6 is similar to that shown in FIG. 1 except that a heater 14 is provided. The heater 14 may be a heater that contacts a recording medium and heats the recording medium, or may be a heater that irradiates infrared rays or the like or blows hot air without contacting the recording medium.

According to a preferred embodiment of the present invention, the ink jet recording apparatus further contains a reaction liquid and an ink composition, and the amounts of the ink composition and the reaction liquid are such that the ink composition is consumed first. Those that are exhausted are preferred.

According to another preferred embodiment, there is provided an ink tank used in an ink jet recording apparatus. This ink tank may preferably be a replaceable cartridge type, and more preferably may be integrated with the recording head. In any of the embodiments, it is preferable that the reaction liquid and the ink composition are contained, and the amounts of the ink composition and the reaction liquid are such that the ink composition is consumed first.

Contrary to this embodiment, if the reaction liquid is consumed before the ink composition, the reaction liquid is generally transparent. It will be difficult to know when you are exhausted. In other words, the fact that the reaction solution has been consumed can be known for the first time by observing the print and the fact that the print quality has deteriorated, and the user is always required to observe the print quality.

On the other hand, in the ink jet recording apparatus according to this embodiment, since the ink composition itself is colored, it is possible to easily know the consumption thereof. further,
Since the reaction liquid does not run out before the ink composition is completely consumed, it is possible to perform an ink jet recording method for printing two liquids stably. On the other hand, it is conceivable to provide a sensor means or the like in a tank portion for storing the ink composition and the reaction liquid and observe the consumption, but in this embodiment, such a complicated mechanism can be replaced by a very simple mechanism. It is also valuable in that respect.

In this embodiment, when a plurality of ink compositions are used, “the ink composition is consumed earlier than the reaction liquid” means that any one of the ink compositions is consumed. As long as the reaction liquid still remains at the time of exhaustion, it does not necessarily mean that the reaction liquid must remain even when all of the plurality of ink compositions are consumed, It is preferable that the reaction liquid remains even when all of the ink composition is completely consumed.

[0106]

The present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

Example A Preparation of Reaction Solutions Reaction solutions A1 to 10 were prepared by mixing the following components.

Reaction solution A1 Magnesium nitrate hexahydrate 5% by weight Glycerin 20% by weight Triethylene glycol monobutyl ether 10% by weight 2-pyrrolidone 5% by weight Triethanolamine 0.2% by weight Pure water balance

Reaction solution A2 Magnesium nitrate hexahydrate 5% by weight Glycerin 20% by weight Triethylene glycol monobutyl ether 10% by weight 2-pyrrolidone 10% by weight 0.2% by weight of triethanolamine Remaining pure water

Reaction solution A3 Magnesium nitrate hexahydrate 5% by weight Glycerin 20% by weight Diethylene glycol monobutyl ether 10% by weight 1,3-dimethyl-2-imidazolidinone 10% by weight Triethanolamine 0.2% by weight Pure water Remaining amount

Reaction liquid A4 Magnesium nitrate hexahydrate 5% by weight Glycerin 20% by weight Surfinol 465 0.7% by weight Thiodiglycol 5% by weight Triethanolamine 0.2% by weight Pure water

Reaction solution A5 Calcium nitrate tetrahydrate 5% by weight Glycerin 20% by weight Triethylene glycol monobutyl ether 10% by weight 2-pyrrolidone 5% by weight Triethanolamine 0.2% by weight Pure water balance

Reaction liquid A6 Acid Yellow 23 3.2% by weight Magnesium nitrate hexahydrate 5% by weight Glycerin 12% by weight Diethylene glycol monobutyl ether 3% by weight Surfynol 465 0.7% by weight Siethylene glycol 4% by weight 2 -Pyrrolidone 5% by weight Triethanolamine 0.1% by weight Pure water balance

Reaction liquid A7 Reactive Red 180 4.2% by weight Magnesium nitrate hexahydrate 5% by weight Glycerin 17% by weight Siethylene glycol monobutyl ether 3% by weight Surfynol 465 0.7% by weight Diethylene glycol 4% by weight 2-Pyrrolidone 5% by weight Triethanolamine 0.9% by weight Pure water

Reaction liquid A8 Acid Blue 9 1.5% by weight Direct Blue 199 3.5% by weight Magnesium nitrate hexahydrate 5% by weight Glycerin 12% by weight Siethylene glycol monobutyl ether 3% by weight Surfynol 465 0 0.7 wt% diethylene glycol 4 wt% 2-pyrrolidone 5 wt% triethanolamine 0.1 wt% pure water

Reaction solution A9 Magnesium nitrate hexahydrate 5% by weight Glycerin 20% by weight Triethylene glycol monobutyl ether 10% by weight Triethanolamine 0.2% by weight Pure water

Reaction liquid A10 Calcium nitrate tetrahydrate 5% by weight Glycerin 20% by weight Triethylene glycol monobutyl ether 10% by weight Triethanolamine 0.2% by weight Pure water

Preparation of ink composition Black ink A1 Carbon black MA7 5% by weight (manufactured by Mitsubishi Kasei Corporation) Styrene-acrylic acid copolymer 1% by weight (dispersant) Sucrose 0.7% by weight Maltitol 6.3% by weight % Glycerin 10% by weight 2-pyrrolidone 2% by weight ethanol 4% by weight Pure water

[0119] Carpon black and a dispersant are mixed, and the mixture is mixed with a glass peas (with a diameter of 1.
7 mm, 1.5 times (weight) of the mixture) for 2 hours. Thereafter, the glass peas were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. The mixture was filtered through a 5 μm membrane filter to obtain a black ink for inkjet recording.

Evaluation A1 of Reaction Solution A : Amount of Foreign Substances Generated The reaction solution was sealed in Teflon bin and left at 70 ° C. for 1 week. After standing, 10 ml of the reaction solution was passed through a 10 μm mesh filter to collect foreign substances. The result is the first
As shown in the table. In the table, the number of filtered foreign substances is less than 20 -A The number of filtered foreign substances is 20 or more and less than 100 -B The number of filtered foreign substances is 100 or more -C.

Evaluation A2 : Printing stability The reaction solution was filled in an ink cartridge of MJ-500C (manufactured by Seiko Epson Corporation) and mounted on a printer. Print 10,000 patterns of mixed characters and graphics on A4 paper.
It was observed whether or not "missing" occurred.

Since the reaction solutions 1 to 5 were transparent, acid blue 9 (dye) was added in an amount of 0.5% by weight and colored so that bending and detachment could be easily confirmed.

The results were as shown in Table 1. In the table, the number of occurrences of bends and omissions is less than 20 times -A The number of occurrences of bends and omissions is 20 times or more and less than 50 times -B The number of times of occurrence of bends and omissions is 50 times or more -C.

Evaluation A3 : Print quality (bleeding) Printing was performed on each of the following papers using an ink jet printer MJ-500C. For printing, 100% dut the reaction solution
After printing with y, characters were printed with black ink A1. After drying, the characters were examined for bleeding.

Xerox P paper (manufactured by Xerox Co., Ltd.) Riccopy 6200 paper (manufactured by Ricoh Co., Ltd.) Xerox 4024 paper (manufactured by Xerox Co., Ltd.) Neenah Bond paper (manufactured by Kimberly-Clark Co., Ltd.) Xerox R paper (manufactured by Xerox Co., recycled paper) Yamayuri paper (Recycled paper manufactured by Honshu Paper Co., Ltd.)

The results were as shown in Table 1. In the table, the results are shown as -A for clear printing without bleeding, -B for whisker-like bleeding, and -C for bleeding that does not clearly show the outline of characters.

Table 1 Reaction solution Evaluation A1 Evaluation A2 Evaluation A3 Example A1 A1 ABA AA2 A2 A A A A A3 A3 B B A A4 A4 A B A A A5 A5 A B A A6 A6 B B B A B A A A B A8 A8 B BB Comparative Example A1 A9 CCA A2 A10 CCA

Example B Preparation of Reaction Solutions Reaction solutions B1 to B10 were prepared by mixing the following components. The above components were mixed and stirred at room temperature for 1 hour, and then the composition was subjected to suction filtration with a 5 μm membrane filter,
A reaction solution was obtained.

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

Preparation of Ink Composition Black ink B1 Carbon black MA7 5% by weight (manufactured by Mitsubishi Kasei Corporation) Styrene acrylic acid copolymer 1% by weight (dispersant) Bon coat 4001 3% by weight (acrylic resin emulsion, resin component 50%, MF
T5 ° C, manufactured by Dainippon Ink Co., Ltd.) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight 2-Pyrrolidone 2% by weight Ethanol 4% by weight Pure water

[0139] Carbon black and a dispersant are mixed, and the mixture is mixed with glass beads (diameter of 1. 1) in a sand mill (Yaskawa Seisakusho).
7 mm, 1.5 times (weight) of the mixture) for 2 hours. Thereafter, the glass beads were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. The mixture was filtered through a 5 μm membrane filter to obtain an ink for inkjet recording.

Evaluation of reaction solution B1 : Print quality (bleeding) Printing was performed on each of the following papers using an ink jet printer MJ-500C (manufactured by Seiko Epson Corporation).
First, after printing the reaction solution at 100% duty,
Characters were printed with black ink B1. After drying, the characters were examined for bleeding.

Xerox P paper (manufactured by Xerox Co., Ltd.) Riccopy 6200 paper (manufactured by Ricoh Co., Ltd.) Xerox 4024 paper (manufactured by Xerox Co., Ltd.) Neenah Bond paper (manufactured by Kimberly-Clark Co.) Xerox R paper (manufactured by Xerox Co., Ltd., recycled paper ) Yamayuri paper (recycled paper manufactured by Honshu Paper Co., Ltd.)

The results were as shown in Table 2. In the table, clear printing without bleeding-A: whisker-like bleeding-B: bleeding so that the outline of characters is not clear-C.

Evaluation B2 : Clogging Characteristics The head of an ink jet printer MJ-500C was filled with the reaction solution, and alphanumeric characters were printed continuously for 10 minutes. After that, stop the printer.
Left for 1 month in Rh environment. After the standing, alphanumeric characters were printed again, and the number of clogging recovery operations required until printing equivalent to that before the standing was obtained was examined. The results were as shown in Table 2. In the table, the same printing as the initial is possible with 0 to 2 return operations-A The same printing as the initial is possible with 3 to 5 returning operations-B The same printing as the initial is possible even with 6 or more returning operations Impossible-
C.

Evaluation B3 : Discharge stability The head of an ink jet printer MJ-500C was filled with the reaction solution, and alphanumeric characters were printed continuously on A4 size paper. If a flight deflection (meaning that the ink droplet does not fly straight) occurs during printing, a return operation is performed. If the flight turns are not corrected even after performing the return operation,
The number of printed sheets up to that point was used as a parameter indicating ejection stability.

The results are shown in Table 2.

The number of prints until the flight bend does not recover is 10,000 or more. -A The number of prints until the flight bend no longer recovers is 1000.
0 or less -B The number of prints until the flight bend cannot be restored is 5000
Sheets or less -C

Table 2 Reaction Solution Evaluation B1 Evaluation B2 Evaluation B3 Example B1 B1 AA AAB2 B2 A A A AB3 B3 A A A B B4 B4 A A A B B5 B5 A A A B6 B6 A A A A B A B A B B B8 B8 A A A Comparative Example B1 B9 A A C B2 B10 A B C

Example C Preparation of Reaction Solutions Reaction solutions C1 to C5 were prepared by mixing the following components.

Reaction solution C1 Swanol CA-2150 10% by weight (lauryltrimethylammonium chloride, solid content 50%,
Nikko Chemicals Co., Ltd.) Magnesium nitrate hexahydrate 5% by weight Glycerin 10% by weight Triethanolamine 0.2% by weight Pure water

Reaction solution C2 Swanol CA-2350 10% by weight (cetyltrimethylammonium chloride, solid content 50%, manufactured by Nikko Chemicals Co., Ltd.) Calcium nitrate tetrahydrate 5% by weight Glycerin 10% by weight Triethanolamine 0. 2% by weight pure water

Reaction solution C3 Swanol CA-3080 3% by weight (dioctyldimethylammonium chloride, solid content 80%,
Nikko Chemicals Co., Ltd.) Magnesium acetate tetrahydrate 5% by weight Glycerin 10% by weight Triethanolamine 0.2% by weight Pure water

Reaction solution C4 cation M2-100 5% by weight (octadecyldimethylbenzylammonium chloride, manufactured by NOF Corporation) Calcium acetate monohydrate 5% by weight Glycerin 10% by weight Triethanolamine 0.2% by weight Pure Water remaining

Reaction liquid C5 Cation SA 5% by weight (octadecylamine acetate, manufactured by NOF Corporation) Calcium formate (anhydrous) 5% by weight Glycerin 10% by weight Triethanolamine 0.2% by weight Pure water

Preparation of ink composition Black ink C1 Carbon black Raven 1080 5% by weight (manufactured by Colombian Carbon) Styrene-acrylic acid copolymer 1% by weight (dispersant) Boncoat 4001 5% by weight (acrylic resin emulsion, resin component 50%, manufactured by Dainippon Ink and Chemicals, Inc.) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight 2-pyrrolidone 2% by weight Ethanol 4% by weight Pure water

A mixture of carbon black and a dispersant was mixed in a sand mill (manufactured by Yaskawa Seisakusho) to form glass beads (diameter 1.7).
mm, 1.5 times the weight (weight) of the mixture). Thereafter, the glass beads were removed, other components were added, and the mixture was stirred at room temperature for 20 minutes. The mixture was filtered through a 5 μm membrane filter to obtain an ink composition for inkjet recording.

The following color ink set C1 comprising the black ink C2 and each of the yellow, cyan, and magenta ink compositions was prepared according to the method for the black ink C1.

Black ink C2 carbon black MA7 5% by weight (manufactured by Mitsubishi Chemical Corporation) Styrene-acrylic acid copolymer 1% by weight (dispersant) Boncoat 5454 5% by weight (styrene-acrylic resin emulsion, resin component 45
%, Manufactured by Dainippon Ink and Chemicals, Inc.) Sucrose 0.7 wt% Maltitol 6.3 wt% Glycerin 10 wt% 2-Pyrrolidone 2 wt% Ethanol 4 wt% Pure water

Color Ink Set C1 Yellow ink, magenta ink and cyan ink were prepared from the following colorants (pigments) and liquid media, respectively.

<Pigment> Yellow ink Pigment KETYELLOW403 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Magenta ink Pigment KETRED309 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Cyan ink Pigment KETBLUEEX-1 2% by weight ( <Liquid medium> Styrene-acrylic acid copolymer 0.4% by weight (dispersant) Boncoat 4001 2% by weight Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight % 2-pyrrolidone 2% by weight Ethanol 4% by weight Pure water (remaining amount)

Printing Evaluation Test The ink compositions and reaction liquids shown above were combined as shown in Table 3 below, and printing was actually performed by an ink jet printer to evaluate printing quality and the like.

Evaluation C1 : Print quality (bleeding) Evaluation was performed in accordance with the evaluation A3. The results were as shown in Table 3 below.

Evaluation C2 : Print quality (OD value) The reaction liquid was printed at 100% duty on the paper used in Evaluation C1 above using an ink jet printer MJ-700V2C, and then characters were printed with black ink. After drying, the reflection OD value of the printed matter was determined using Macbeth PCMI.
I (Macbeth).

The results were as shown in Table 3 below.

Evaluation C3 : Printing unevenness The following papers were printed at 100% duty using an inkjet printer MJ-700V2C.

Ricopy 6200 paper (manufactured by Ricoh Co., Ltd.) Canon PB PAPER paper (Canon Co., Ltd.)
The OD values at any five points of the obtained printed matter were measured using Machbet.
h The measurement was performed using PCMII, and the average value was determined.
This procedure was repeated five times, and the maximum value and the minimum value of the five average values were determined. When this difference is less than 0.5, there is no practical problem, and more preferably, it is less than 0.4.

The results were as shown in Table 3 below. In the table, A: OD value difference is less than 0.2 B: OD value difference is 0.2 or more and less than 0.4 C: OD value difference is 0.4 or more.

Evaluation C4 : A 100% duty reaction liquid was printed on the paper used in Evaluation A3 above using a color bleed ink jet printer MJ-700V2C, and then a 100% duty printing was performed with each color ink composition of the color ink set C1. At the same time, characters were printed with black ink C1 or C2. The printed material obtained was examined for the presence of non-uniform color mixing at the boundary between characters. The print was visually observed.

The results were as shown in Table 3 below. In the table, A: no color mixture and sharp boundaries B: whisker-like color mixture occurs C: The colors are mixed so that the characters and outlines are not clear.

Table 3 Reaction liquid Black ink Evaluation C1 Evaluation C2 Evaluation C3 Evaluation C4 Example C1 C1 A 1.41 A-C2 C1 2 A 1.43 A-C3 C2 2 A 1.43 A-C4 C3 2 A 1.45 A-C5 C4 1 A 1.45 A-C6 C42 A1.48 AAC7 C52 A1.46 A A Comparative example C1-2 B1.33 BC

[Brief description of the drawings]

FIG. 1 is a view showing an ink jet recording apparatus for carrying out a method according to the present invention. In this embodiment, a recording head and an ink tank are independent of each other, and an ink composition and a first liquid are recorded by an ink tube. Supplied to

FIG. 2 is an enlarged view of a nozzle surface of a recording head,
Is the nozzle surface of the first liquid, and 1c is the nozzle surface of the ink composition.

FIG. 3 is a diagram illustrating inkjet recording using the recording head of FIG. 2; In the figure, reference numeral 31 denotes a first liquid adhering area, and reference numeral 32 denotes a printing area where the ink composition is printed on the first liquid adhering.

FIG. 4 is a diagram showing another aspect of the recording head, in which all the ejection nozzles are arranged in the horizontal direction.

FIG. 5 is a view showing an ink jet recording apparatus for carrying out the method according to the present invention. In this embodiment, the recording head and the ink tank are integrated.

FIG. 6 is a view showing an ink jet recording apparatus for performing the method according to the present invention, in which a heating means 14 for heating a recording medium after an image is recorded in this embodiment is provided.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording head 2 Ink tank 3 Ink tube 21 First liquid discharge nozzle 22, 23, 24, 25 Ink composition discharge nozzle 31 First liquid adhesion area 32 Printing area

Claims (20)

[Claims] 1. A reaction liquid used in an ink jet recording method for printing by adhering a reaction liquid and an ink composition to a recording medium, comprising at least one of a polyvalent metal salt and nitrogen. A reaction comprising at least a component selected from the group consisting of a 5- or 6-membered saturated or unsaturated heterocyclic compound, an amide derivative which may be alkyl-substituted, a sulfur-containing compound, an amine, and a cationic surfactant. liquid. 2. A 5- or 6-membered saturated or unsaturated heterocyclic compound containing at least one nitrogen atom, an amide derivative which may be alkyl-substituted, or a sulfur-containing compound is pyridine, 2-pyrrolidone, 1,3 or The reaction solution according to claim 1, which is selected from -dimethyl-2-imidazolidinone and thiodiglycol. 3. The reaction solution according to claim 1, wherein the amine is ammonia. 4. The reaction solution according to claim 3, wherein the concentration of the ammonia is 0.5% by weight or less. 5. The method according to claim 1, wherein the amine is a saturated compound having 12 to 18 carbon atoms,
The reaction solution according to claim 1, which is a primary, secondary, or tertiary amine having an unsaturated hydrocarbon group. 6. The reaction solution according to claim 1, wherein the amine contained in the reaction solution is a cyclic imine. 7. The method according to claim 5, wherein the amine contained in the reaction solution is an inorganic acid salt or an amide derivative.
Or the reaction solution according to 6. 8. The reaction solution according to claim 1, wherein the amine has a vapor pressure of more than 0.01 Pa at 25 ° C. 9. The reaction solution according to claim 1, wherein the cationic surfactant comprises one quaternary nitrogen atom in its molecular structure. 10. The cationic surfactant, wherein at least two or more of the substituents bonded to a quaternary nitrogen atom in the molecular structure contain at least six carbon atoms, respectively.
The reaction solution according to claim 9. 11. The reaction solution according to claim 10, wherein the cationic surfactant is represented by the following formula (I). ^{R 1 R 2 R 3 R 4} N + X - (I) ( wherein, R ¹ and R ² are independently C ₈ -C ₂₀ alkyl group, a benzyl group or a phenyl group,, R ³ and R ⁴ independently represents a C ₁ -C ₄ alkyl group, X ^-
Represents a counter ion) 12. The reaction solution according to claim 1, further comprising a colorant and glycerin. 13. The reaction solution according to claim 1, wherein the polyvalent metal salt is a nitrate or a carboxylate. 14. A reaction medium according to claim 1 and an ink composition adhered to a recording medium,
An inkjet recording method for printing. 15. The ink jet recording method according to claim 14, wherein said ink composition comprises a colorant and a resin emulsion. 16. The ink jet recording method according to claim 15, wherein the colorant of the ink composition is a pigment. 17. The method according to claim 14, wherein the reaction liquid is adhered to a recording medium, and thereafter, the ink composition is printed on the recording medium.
The inkjet recording method according to any one of the above. 18. The method according to claim 14, wherein the ink composition is printed on a recording medium, and thereafter, a reaction liquid is applied to the recording medium.
The inkjet recording method according to any one of the above. 19. The ink jet recording method according to claim 14, wherein the reaction liquid and the ink composition are mixed immediately before or immediately after ejection from an ink jet recording apparatus and printed on a recording medium. . 20. Recorded matter printed by the method according to claim 14. Description: