JPH1110856A - Ink for ink jet recording and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize the acquisition of a favorable printed image having no printing unevenness and developing a small blur on a regenerated paper by a method wherein a solution containing a multivalent metal salt or the like and its derivative is employed as a reactive solution adhering to a recording medium and a composition containing a colorant and the like and an aqueous solvent and having a specified pH value is employed as an ink composition. SOLUTION: A chamber for an ink composition and a chamber for a reactive solution are provided in an ink tank 2, which communicates through an ink tube 3 with a recording head 1. The reactive solution is discharged from a nozzle surface during the movement of the recording head 1 so as to form a band-like reactive solution adherent region on a recording medium 7. Next, the recording medium 7 is moved by the predetermined amount towards its paper feeding direction. During the movement of the recording medium 7, the recording head 1 is moved to the direction opposite to the above-mentioned paper feeding direction so as to return to the left end position of the recording medium 7 in order to print the ink composition to the reactive solution adherent region. This reactive solution contains a multivalent metal salt or a polyallyl amine or its derivative. The ink composition contains at least a colorant, an inorganic oxide colloid and an aqueous solvent and has the pH of 9 or higher.

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, and more particularly, to an ink jet recording method for printing by attaching a reaction liquid and an ink composition to a recording medium.

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,
It is stated that an insoluble complex is formed from the polyvalent metal ion and the dye, and the presence of this complex makes it possible to obtain a high-quality image having water resistance and 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] In the ink jet recording method for printing two liquids, the point that further improvement in performance is desired is as follows.

The first is to improve the fixing ability of the coloring component. In recent years, recycled paper is increasingly used in place of high quality paper. In many cases, recycled paper is more permeable to ink than high-quality paper. For this reason, even if a high-quality image can be obtained on high-quality paper, image bleeding or color bleeding may occur on recycled paper, and improvement is required.

[0008] The second problem is uneven printing. What is printing unevenness?
This is a disturbance in the color density of the printed matter caused by the bias of the coloring components on the paper. Printing unevenness is not a major problem for characters of normal size, but it is an important problem in applications where graphics, graphs, and the like must be printed.

The third is to expand the coloring components that can be used. Many ink jet recording methods for printing two liquids utilize a salting-out phenomenon of a metal ion and a carboxyl ion contained in a coloring component. Therefore, it is a precondition that the coloring component has a carboxyl group. However, some dyes are solubilized by the action of a group other than a carboxyl group, for example, a sulfone group, and it can be said that a recording method that enables the use of such a dye is required.

[0010]

SUMMARY OF THE INVENTION The present inventors have now realized that a good image can be obtained by using an ink composition containing an inorganic oxide colloid and having a pH of 9 or more in an ink jet recording method for printing two liquids. I got the knowledge that I can do it. The present invention is based on this finding.

Accordingly, an object of the present invention is to provide a method capable of realizing a good image in an ink jet recording method for printing two liquids.

More specifically, an object of the present invention is to provide an ink jet recording method for printing two liquids capable of realizing a good image even on recycled paper.

Still another object of the present invention is to provide an ink jet recording method for printing two liquids capable of realizing an image having no printing unevenness.

Still another object of the present invention is to provide an ink jet recording method for printing two liquids which can use a wide range of coloring components.

The ink jet recording method according to the present invention is an ink jet recording method for performing printing by adhering a reaction liquid and an ink composition to a recording medium, wherein the reaction liquid is a polyvalent metal salt or polyallylamine or polyallylamine. An ink composition containing at least a colorant, an inorganic oxide colloid, and an aqueous solvent and having a warp pH of 9 or more is used.

[0016]

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.

In the ink jet recording method according to the present invention, good printing can be realized by contact between the reaction liquid and the ink composition. The following is a hypothesis, and the reason is as follows, provided that the present invention is not interpreted in a limited manner. When the reaction liquid and the ink composition come in contact, the polyvalent metal ion or polyallylamine or a derivative thereof in the reaction liquid destroys the colorant in the ink composition, the inorganic oxide colloid, and the dispersed state of other components,
It is thought to agglomerate it. In particular, it is considered that a polyvalent metal ion or polyallylamine or a derivative thereof in the reaction liquid reacts with the inorganic oxide colloid in the ink composition to form an aggregate. It is considered that these aggregates suppress the penetration of the coloring agent into the recording medium. Further, the colloid particles remaining on the recording medium adhere to the recording medium, and further bind together to form a film,
It is considered that the colorant has an effect of promoting fixation to the recording medium. These are considered to realize an image with high color density, less blur, and less print unevenness. Also,
In a color image, there is also an advantage that uneven color mixing in a boundary region of different colors, that is, color bleed can be effectively prevented. The above mechanism is only an assumption, and the present invention is not construed as being limited to this mechanism.

In the present invention, as described above, it is considered that the inorganic oxide colloid reacts with the polyvalent metal ion or polyallylamine or a derivative thereof in the reaction solution to form an aggregate efficiently. Can be Therefore, even if the coloring agent is less likely to form an aggregate with a polyvalent metal ion or polyallylamine or a derivative thereof,
A good print image can be realized. This means that the method according to the invention allows the use of a wide variety of colorants, regardless of the type of colorant. This is a great advantage of the present invention.

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.

Further, as described later, the reaction liquid may contain a coloring agent and function as an ink composition.

Ink Composition The ink composition used in the present invention contains at least a colorant, an inorganic oxide colloid, and an aqueous solvent.

Inorganic Oxide Colloid The inorganic oxide colloid (also referred to as inorganic oxide sol) used in the present invention is composed of water or an organic solvent which mixes well with water, and the dispersoid is an inorganic oxide colloid. It means a colloid solution composed of fine particles. Examples of the inorganic oxide include high molecular weight silicic anhydride (SiO ₂ ) and alumina (Al ₂
O ₃ ) and the like, but are not limited thereto. The particle diameter of the inorganic oxide ultrafine particles is generally about 1 to 100 nm, preferably in the range of 1 to 20 nm, and more preferably in the range of 1 to 10 nm. Also,
The dispersion medium of the inorganic oxide colloid is water or an organic solvent having good compatibility with water, such as methanol, ethanol,
A mixed solvent with isopropyl alcohol, n-propanol or the like is generally used. The inorganic oxide colloid is obtained by dispersing the ultrafine particles of the above inorganic oxide in water or the above organic solvent. A dispersion in which the above-mentioned inorganic oxide ultrafine particles are dispersed in water is called an aqueous sol, and a dispersion in an organic solvent is called an organosol.

The inorganic oxide colloid used in the present invention needs to have the property of interacting with the polyvalent metal salt or polyallylamine or a derivative thereof and aggregating as described above.

As such an inorganic oxide colloid,
It is also possible to use a commercially available product. Specific examples thereof include Snowtex S, Snowtex N, Snowtex C, Snowtex SS, Snowtex XS, Snowtex 20, Snowtex 3 in which ultrafine particles of high molecular weight silicic anhydride are dispersed in water.
0, Snowtex 40 (manufactured by Nissan Chemical), Ca
taloid SI-350, Cataloid SI
-500, Cataloid SI-30, Catal
oid S-20L, Cataloid S-20H,
Cataloid S-30L, Cataloid S-
30H, Cataloid SI-40 (all manufactured by DuPont) and the like. In addition, alumina sol is used as a colloid in which ultrafine particles of alumina are dispersed in water.
0, alumina sol 200, and alumina sol 520 (all manufactured by Nissan Chemical Industries, Ltd.). OSCAL-14 in which ultrafine particles of high molecular weight silicic anhydride are dispersed in an organic solvent
32 (isopropyl alcohol sol; manufactured by Catalyst Chemical Industry)
Is also available. The pH of the above-mentioned commercially available inorganic oxide colloid solutions is often adjusted 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 a commercially available inorganic oxide colloid solution is added to the ink, the pH and the pH of the stable dispersion region of the inorganic oxide colloid are increased. Ink p
It is necessary to add H in consideration of H.

The addition amount of the inorganic oxide colloid may be appropriately determined in consideration of the type and the aggregate thereof, but is preferably, for example, about 0.1 to 15% by weight of the ink composition, and more preferably 0.1 to 15% by weight. It is in the range of about 5 to 5.0% by weight. Further, a plurality of inorganic oxide colloids may be added.

PH of Ink Composition The ink composition according to the present invention has a pH of 9 or more, more preferably a lower limit of 10 or more, and an upper limit of 11.5 or less. By setting the pH of the ink composition to the above value, a good image can be obtained.
Adjustment of the pH of the ink composition may be performed with either an organic base or an inorganic base. Preferred examples of the organic base include triethanolamine, diethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, and morpholine. Preferred examples of the inorganic base include lithium, sodium, potassium, which are alkali metal hydroxides.
A hydroxide of rubidium, cesium, or francium is mentioned, and potassium hydroxide is particularly preferable. The addition of the alkali metal hydroxide is preferable from the viewpoint of better image formation as compared with the case of using another organic base or inorganic base. Although the reason is not clear, it is considered that the reactivity between the polyvalent metal salt or polyallylamine or a derivative thereof and the inorganic oxide colloid is improved, and as a result, a good image can be realized. The amount of alkali metal hydroxide added is
The pH may be appropriately determined as long as the pH can be realized, but from the viewpoint of good image formation, for example, 0.0% of the ink composition may be used.
It is preferably about 1 to 1% by weight, more preferably 0.01% by weight.
０．２0.2% by weight. Further, a plurality of alkali metal hydroxides may be added.

Colorant The colorant contained in the ink composition used in the present invention may be a dye or a pigment. In the present invention, an extremely wide range of colorants can be used as described above.

The 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. As a preferred dispersant, a dispersant commonly used for preparing a pigment dispersion, for example, a polymer dispersant or a surfactant can be used.

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

Aqueous solvent The aqueous solvent which is the basic solvent of the ink composition according to the present invention comprises an aqueous organic solvent and water.

The aqueous 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 and te.
rt-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.

According to a preferred embodiment of the present invention, the aqueous solvent preferably further contains a wetting agent comprising a high-boiling organic solvent. 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, 2-pyrrolidone, N-methyl-2 Pyrrolidone, 1,3-dimethyl -
2-imidazolidinone, triethanolamine and the like.

The amount of the wetting agent added is 0.5% of the ink.
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.

Further, the ink composition used in the present invention may contain a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, various surfactants such as amphoteric surfactants, methanol, ethanol, alcohols such as iso-propyl alcohol,
Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether,
And lower alkyl ethers of polyhydric alcohols such as dipropylene glycol monobutyl ether.

The ink composition used in the present invention may further contain, if necessary, a pH adjuster, a preservative, a fungicide and the like. For example, examples of the pH adjuster include potassium hydroxide, sodium hydroxide, and triethanolamine.

Sugar According to a preferred embodiment of the present invention, the ink composition used in the present invention preferably contains a sugar.
By adding the sugar, the color density can be further improved, and bleeding and printing unevenness can be extremely reduced.
Further, in a color image, color bleeding can be prevented at a higher level. Specific examples of saccharides include monosaccharides,
Examples include disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, gluciseal, sorbitol, 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.

The derivatives of these saccharides include reducing sugars of the aforementioned saccharides (for example, sugar alcohols (formula H
OCH2 (CHOH) n CH2 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 suitably in the range of 0.1 to 40% by weight, preferably 0.5 to 30% by weight of the ink composition.

Epoxy group-containing compound and epoxy curing
According to a preferred embodiment of the agent present invention, the ink composition used in the present invention, the comprises an epoxy group-containing compounds are preferred. In the present invention, the epoxy group-containing compound is a compound having at least two or more epoxy groups in a molecular structure, which means that a cross-linking reaction involving an epoxy group is caused to be a resin (that is, a high molecular weight). It shall be. By adding the epoxy group-containing compound, it is possible to impart good rub resistance and water resistance to a printed image.

The epoxy group-containing compound used in the present invention includes a compound having an epoxy group and further having a functional group capable of reacting with the epoxy group, and a compound having an epoxy group but capable of reacting with the epoxy group. And a compound having no such compound.

Here, the functional group capable of reacting with the epoxy group means a group which reacts with the epoxy group to cause a cross-linking reaction, and includes, for example, a hydroxyl group, a carboxyl group, and a sulfonic acid group. In the present invention, when an epoxy group-containing compound having a functional group capable of reacting with an epoxy group is further used, the addition of an epoxy curing agent to a reaction solution as described later can be omitted. On the other hand, when an epoxy curing agent is further added to the reaction solution while using an epoxy group-containing compound having a functional group capable of reacting with an epoxy group, the fixing speed of printing can be further improved. Which advantage is obtained can be appropriately selected.

In the present invention, the mechanism by which good printing can be obtained by adding an epoxy group-containing compound to the ink composition is considered as follows. However, this mechanism is only an assumption, and the present invention is not construed as being limited to this mechanism.

In the method according to the present invention, the reaction solution
The ink composition is adhered to a recording medium. When the ink composition adheres to the recording medium, coagulation occurs due to the interaction between the polyvalent metal ion or polyallylamine or its derivative due to the polyvalent metal salt in the reaction liquid and the inorganic oxide colloid in the ink composition. As described above. Here, when the reaction solution contains an epoxy curing agent, a crosslinking reaction of the epoxy group of the epoxy group-containing compound occurs, and resinification proceeds. Further, when a compound having a functional group capable of reacting with an epoxy group is used as the epoxy group-containing compound, it is considered that the resination proceeds by the following mechanism despite the absence of an epoxy curing agent. That is, when the distance between the epoxy group-containing compounds becomes extremely small due to the aggregation of the polyvalent metal salt or polyallylamine or a derivative thereof and the inorganic oxide colloid in the reaction solution, the epoxy group between adjacent epoxy group-containing compounds becomes It is expected that a phenomenon occurs in which a reactive group reacts therewith. It is considered that a cross-linking reaction occurs between the epoxy group-containing compounds due to this reaction, and the compound turns into a resin. By the above resinification, the print is firmly attached to the recording medium, and a resin film is formed on the print surface. Such printing is good rub resistance, water resistance,
It is considered that light resistance will be obtained.

It is apparent that it is not preferable that the epoxy group-containing compounds having a functional group capable of reacting with the epoxy group in the ink composition react with each other. Use is preferably avoided.

The epoxy group-containing compound preferably used in the present invention includes an epoxy group-containing resin emulsion and a water-soluble epoxy compound.

According to a preferred embodiment of the present invention, as the epoxy group-containing resin emulsion, the continuous phase is water and the dispersed phase is the following formula (I) and (II):

[0050]

Embedded image (Wherein R ¹ and R ³ independently represent H or CH ₃ , and R ² represents an alkyl group (preferably C ₁ -C ₁ )
₂₁ alkyl), hydroxyl group, comprising a copolymer comprising a repeating unit represented by a carboxyl group and comprising one or more groups selected from sulfonic acid group), an epoxy group-containing acrylic resin Emulsions. The resin is not limited by the mode of copolymerization, and may be, for example, a block copolymer, a random copolymer, or the like.

The terminal of such a copolymer does not substantially affect the properties of the copolymer because the copolymer is a polymer, but generally the terminus of the fragment of the polymerization initiator is attached. Let's be. Examples of such a section of the polymerization initiator include a section of a polymerization initiator such as ammonium persulfate and potassium persulfate, specifically, -OSO3H.

Preferred examples of R ² include —OH, —C
OOH, -COO-R (where R represents a linear or branched alkyl group, preferably a C _1-12 alkyl group, and one or more hydrogen atoms on the alkyl group are a hydroxyl group, a phosphono group Or an aryl group (for example, a phenyl group or a tolyl group) substituted with a sulfonic acid group. Specific examples of the group represented as R ² is, -OH, -COOH,
_{-COOCH 2 CH 2 OH, -COOCH 2} CH (CH 3)
_{OH, -COOCH 2 CH 2 PO (} OH) 2, -C 6 H 5 S
O ₃ H, —COOCH ₂ CH ₂ SO ₃ H, —COOCH ₃ ,
—COOC ₂ H ₅ , —COOC ₄ H ₉ , —COOC ₆ H ₁₃ ,
—COO (CH ₂ ) ₁₁ CH, —COOCH ₂ CH (C
H ₃ ) CH ₂ C (CH ₃ ) _{3 and the} like. Where R
^The hydroxyl group, carboxyl group, or sulfonic acid group that may be included in ² is a functional group that can react with an epoxy group. Therefore, when R ² contains only an alkyl group and when R ² contains a hydroxyl group, a carboxyl group, or a sulfonic acid group but does not substantially react with an epoxy group, the resin emulsion reacts with the epoxy group. It has no possible functional groups. When R ² contains a hydroxyl group, a carboxyl group, or a sulfonic group in addition to the alkyl group, the resin emulsion has a functional group capable of reacting with the epoxy group.

It is also possible to use a commercially available resin emulsion, examples of which are Armatex Z116 (manufactured by Mitsui Toatsu Chemicals, Inc.), Newcoat S-2170 and S-1080 (Shin Nakamura Chemical Co., Ltd.). Industrial Co., Ltd.), Banatex # 952 and HG-9
(Manufactured by Shin-Nakamura Chemical Co., Ltd.), Piestex B-
3 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The water-soluble epoxy compound preferably contains two or more epoxy groups reactive with an epoxy curing agent described below in one molecule, and is typically a water-soluble diepoxide. . Examples of the water-soluble epoxy compound preferably used in the present invention include those represented by the following formula.

[0055]

Embedded image (In the formula, n represents a natural number of 4 to 9.) Preferred examples of the water-soluble epoxy compound include polyethylene glycol glycidyl ether. Commercially available products include Epolite 400E (polyethylene glycol # 400 glycidyl ether, manufactured by Kyoeisha Chemical),
Epolite 200E (polyethylene glycol # 200
Glycidyl ether, manufactured by Kyoeisha Chemical), Epolite 80
MF (glycerin diglycidyl ether, manufactured by Kyoeisha Chemical), Epiol G-100 (glycerin diglycidyl ether, manufactured by NOF CORPORATION), and denacol (manufactured by Nagase Kasei Co., Ltd.).

The epoxy group-containing compound having a functional group reactive with an epoxy group preferably used in the present invention includes, for example, at least a part of R ^{2 in} the epoxy group-containing resin emulsion capable of reacting with an epoxy group. Functional groups, that is, those containing a functional group selected from a hydroxyl group, a carboxyl group, and a sulfonic acid group. Part of R ² is an alkyl group (preferably C ₁ to
₂₁ alkyl) and may not contain a functional group capable of reacting with an epoxy group. As a commercially available product, Almatex Z116 (manufactured by Mitsui Toatsu Chemicals, Inc.) can be mentioned.

The content of the epoxy group-containing compound in the ink composition according to the present invention is preferably about 1 to 10% by weight of the ink composition, more preferably 1 to 5% by weight.

The ink composition used in the present invention contains a resin emulsion as described later. When the epoxy group-containing compound is an epoxy group-containing resin emulsion, the epoxy group-containing compound is It also functions as a resin emulsion,
It is not necessary to include a resin emulsion of another component.
However, according to a preferred embodiment of the present invention, it is preferable that a resin emulsion is further added in addition to the epoxy group-containing resin emulsion.

In the present invention, an epoxy curing agent may preferably be included in the reaction solution. This epoxy curing agent
Together with the epoxy group-containing compound contained in the above-mentioned ink composition, it means a compound that promotes resinification (higher molecular weight) of the epoxy group-containing compound by a crosslinking reaction. In the present invention, any epoxy curing agent that gives a print having good abrasion resistance and water resistance in an ink jet recording method as described below can be used without any particular limitation.

The epoxy curing agent preferably used in the present invention is typically water-soluble. As such a curing agent, an amine compound, for example, ethylenediamine,
Diethylaminopropylamine, N-aminoethylpiperazine, trimethylhexamethylenediamine, modified aliphatic amine, water-soluble polyamine, water-soluble room temperature curing catalyst other than amine, for example, aromatic sulfonic acid such as P-phenolsulfonic acid, for epoxy emulsion Curing agents. It is also possible to use a commercially available curing agent, for example, Armatex H700
(Manufactured by Mitsui Toatsu Chemicals, Inc.) and Epoki-H (manufactured by Mitsui Toatsu Chemicals, Inc.).

The concentration of such an epoxy curing agent in the reaction solution is preferably about 0.1 to 40% by weight, more preferably about 1 to 20% by weight.

In the present invention, when the ink composition is printed on the recording medium to which the reaction liquid has adhered, the epoxy curing agent contained in the reaction liquid and the epoxy group-containing compound contained in the ink composition React, and a crosslinking reaction of the epoxy group-containing compound proceeds. The reaction is represented, for example, as follows.

[0063]

Embedded image As a result, the conversion of the epoxy group-containing compound into a resin (in the case of a resin emulsion, a higher molecular weight) is promoted. Due to such resinification during printing formed on the recording medium, the printing is firmly adhered to the recording medium, and a resin film is formed on the printing surface. Such printing has good abrasion resistance,
It has water resistance and light resistance.

Resin Emulsion According to a preferred embodiment of the present invention, the ink composition used in the present invention preferably comprises a resin emulsion. The resin emulsion preferably used is one in which the continuous phase is water and the resin component of the dispersed phase does not contain an epoxy group. As described above, when the epoxy group-containing compound is an epoxy group-containing resin emulsion, the addition of this resin emulsion is not essential.
Examples of such a resin component include an acrylic resin, a vinyl acetate resin, a styrene-butadiene resin, a vinyl chloride resin, an acryl-styrene resin, a butadiene resin, and a styrene resin.

Further, commercially available resin emulsions include:
For example, Microgel E-1002, 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,
Dainippon Ink and Chemicals, Inc.), SAE-1014
(Styrene-acrylic resin emulsion, manufactured by Zeon Corporation), Sibinol SK-200 (acrylic resin emulsion, manufactured by Siden Chemical Co., Ltd.), and the like.

According to a preferred embodiment of the present invention, these resins are preferably polymers having both a hydrophilic part and a hydrophobic part. The particle size of these resin components is not particularly limited as long as an emulsion is formed.
nm or less, more preferably 5 to 100 n
m.

These resin emulsions can be obtained by emulsifying a polymer obtained by a polymerization reaction by adding a surfactant and water, or by emulsion-polymerizing a monomer in water in the presence of a surfactant. it can. For example,
An acrylic resin emulsion or an emulsion of styrene-acrylic resin can be obtained by emulsion polymerization of (meth) acrylate or styrene and (meth) acrylate in the presence of an emulsifier such as a surfactant. . The mixing ratio of the resin component and the surfactant is usually preferably about 10: 1 to 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. The surfactant is not particularly limited, but preferred examples thereof include anionic surfactants (eg, alkyl sulfate, alkyl allyl sulfonate, dialkyl succinate, alkyl naphthalene sulfonate, etc.), and nonionic surfactants having an HLB of 10 or more (eg, polyoxygenated surfactants). Ethylene alkyl ether, polyoxyethylene alkyl allyl ether, etc.), and these can be used alone or as a mixture of two or more.

The ratio of the resin as the disperse phase component to water is preferably from 60 to 400 parts by weight, more preferably from 100 to 200 parts by weight, based on 100 parts by weight of the resin.

The ink composition used in the present invention comprises a resin emulsion, the resin component of which is 0.1 to 0.1% of the ink composition.
The content is preferably 40% by weight, more preferably 1 to 25% by weight.

Both the resin emulsion containing an epoxy group and the resin emulsion not containing an epoxy group suppress the penetration of coloring components by interaction with a polyvalent metal ion or polyallylamine or a derivative thereof. Further, it is considered to have an effect of promoting fixing to a recording medium.

Reaction Solution The reaction solution used in the present invention basically comprises a polyvalent metal salt or polyallylamine or a derivative thereof, and water. Further, when the ink composition contains an epoxy group-containing compound, it preferably contains the above-mentioned epoxy curing agent.

In the present invention, the polyvalent metal salt contained in the reaction solution is composed of a polyvalent metal ion having two or more valences, and preferably a nitrate ion or a carboxylate ion bound to these polyvalent metal ions. It is soluble in water.

Here, the carboxylate ion is preferably derived from a carboxylic acid selected from the group consisting of a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms and a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. Things. Carbon number 1
Preferred examples of the saturated aliphatic monocarboxylic acids of Nos. To 6 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.

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

On the other hand, specific examples of polyvalent metal ions include:
Examples thereof include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ and Ba ^2+, and trivalent metal ions such as Al ³⁺ , Fe ³⁺ and Cr ³⁺ . The anion, Cl ^-, N
O ₃ ⁻ , I ⁻ , Br ⁻ , ClO ₃ ⁻ , and CH ₃ COO ⁻ .

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

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

Polyallylamine and its derivatives that can be used in the reaction solution are cationic polymers that are soluble in water and positively charged in water. For example, Expression (a), Expression (b), and Expression (c) are given.

[0080]

Embedded image (Wherein, X ^- represents chloride ion, bromide ion, iodide ion, nitrate ion, phosphate ion, sulfate ion, acetate ion, etc.)

Further, a polymer obtained by copolymerizing allylamine and diallylamine or a copolymer of diallylmethylammonium chloride and sulfur dioxide can be used.

The content of the polyallylamine or a derivative thereof is preferably 0.5 to 10% by weight of the reaction solution.

In the present invention, the reaction solution preferably contains a wetting agent such as a high-boiling organic solvent. Preferred examples of the high boiling point organic solvent include those described in the section of the ink composition. The high boiling point organic solvent prevents clogging of the head by preventing the reaction solution from drying.

The amount of the high-boiling organic solvent to be added 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, it is preferable to add triethylene glycol monobutyl ether and glycerin as the high boiling organic solvent. When these are added in combination, the addition amounts of triethylene glycol monobutyl ether and glycerin are 10
About 20% by weight and about 1-15% by weight are preferred.

The reaction liquid may be colored by adding a colorant, and may have the function of the ink composition.

In addition, a pH adjuster, a preservative, a fungicide and the like may be added to the reaction solution as needed to improve the storage stability.

Among them, the pH adjuster includes triethanolamine. When triethanolamine is added, its amount is preferably about 0 to 2.0% by weight. . The alkali metal hydroxide that can be added in the ink composition according to the present invention is basic, and thus can also serve as a pH adjuster.

Ink Jet Recording Method and Recording Apparatus An ink jet recording method according to the present invention and an ink jet recording apparatus for carrying out the method 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 is mounted on a carriage 4 and moves while being guided by a guide 9 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. In this embodiment, the cap 1
0 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is stored in a waste ink tank 13 via a tube 12.

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, 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 1b and the ink tank 2b move on the carriage 4.

[0097]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation of Ink Composition and Reaction Solution The following ink compositions were prepared.

Black ink 1 Carbon black MA7 5% by weight (manufactured by Mitsubishi Chemical Corporation) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex Z116 3% by weight (epoxy group-containing acrylic resin emulsion, resin component 50 %, manufactured by Mitsui Toatsu chemicals, Inc.) Snowtex S 2 wt% (colloidal silica, SiO ₂ content 30%, manufactured by Nissan chemical Industries, Ltd.) sucrose 0.7 wt% maltitol 6.3 wt% glycerin 10 wt% KOH 0. 1% by weight Deionized water Remaining pH = 10.0

The carbon black and the dispersant were mixed together and mixed with glass beads (1.7 mm in diameter, 1.5 times the weight (weight) of the mixture) in a sand mill (manufactured by Yasukawa Seisakusho).
Time dispersed. Thereafter, the glass beads were removed, the 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 inkjet recording ink.

According to the method for producing the black ink 1,
The following ink composition was prepared. Black ink 2 Carbon black Raven1080 5% by weight (manufactured by Colombia Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex Z116 3% by weight (epoxy group-containing acrylic resin emulsion, resin component 50%, Mitsui Toatsu Chemical Co., Ltd.) Snowtex C 2% by weight (colloidal silica, SiO ₂ content 20%, manufactured by Nissan Chemical) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight Triethanolamine 0 9.9% by weight Deionized water Remaining pH = 9.8

Black ink 3 Carbon black Raven1080 5% by weight (manufactured by Colombia Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Maltitol 5% by weight glycerin 10% by weight Deionized water remaining amount pH = 7.7

Color ink set 1 Cyan ink 1 Pigment KETBLUEEX-1 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex Z116 3% by weight (epoxy group Containing acrylic resin emulsion, resin component 50%, Mitsui Toatsu Chemicals, Inc.) Snowtex S 2% by weight (colloidal silica, SiO ₂ content 30%, Nissan Chemical) Sucrose 0.7% by weight Maltitol 6.3 % By weight Glycerin 10% by weight KOH 0.1% by weight Deionized water Remaining pH = 10.3

Magenta ink 1 pigment KETRED309 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex Z116 3% by weight (epoxy group-containing acrylic resin emulsion, resin Ingredient 50%, Mitsui Toatsu Chemicals Co., Ltd.) Snowtex S 2% by weight (colloidal silica, SiO ₂ content 30%, Nissan Chemical) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight KOH 0.1% by weight Deionized water Remaining pH = 10.3

Yellow ink 1 pigment KETYELLOW403 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex Z116 3% by weight (epoxy group-containing acrylic resin emulsion, resin Ingredient 50%, Mitsui Toatsu Chemicals Co., Ltd.) Snowtex S (colloidal silica, SiO ₂ content 30%, Nissan Chemical) Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 10% by weight KOH 0. 1% by weight Ion exchange water Remaining pH = 10.3 Color ink 2 Cyan ink 2 Pigment KETBLUEEX-1 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) 1% by weight of styrene-acrylic acid copolymer (dispersant) glycerin 10 wt% ion-exchanged water Balance pH = 7.8 magenta ink 2 Fee KETRED309 2 wt% (Dainippon Ink and Chemicals, Inc.) Styrene - acrylic acid copolymer (dispersant) 1 wt% sucrose 1% Glycerin 10 wt% Ion-exchanged water Balance pH = 7.5 Yellow Ink 3 Pigment KETYELLOW403 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Maltitol 5% by weight glycerin 10% by weight Deionized water Remaining pH = 7.6

A reaction solution was prepared by mixing the following components.

Reaction liquid 1 Magnesium nitrate hexahydrate 25% by weight Triethylene glycol monobutyl ether 10% by weight Glycerin 10% by weight Deionized water

Reaction liquid 2 calcium acetate tetrahydrate 10% by weight Almatex H700 3% by weight (water-soluble polyamine, manufactured by Mitsui Toatsu Chemicals, Inc.) Triethylene glycol monobutyl ether 10% by weight Glycerin 10% by weight Ion Exchange water level

Printing Evaluation Test The following evaluation tests were performed using the following papers. In the following, the ink compositions and the reaction liquids were used in combinations shown in the table below. The printing was performed using an inkjet printer MJ-700V2C (manufactured by Seiko Epson Corporation).

Xerox P paper (manufactured by Xerox Co., Ltd.) Ricopy 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., Ltd.)・ Recycled paper) Yamayuri paper (Honshu Paper Co., Ltd. ・ Recycled paper)

Evaluation 1: Printing Quality (Single Color Bleeding) After the reaction liquid was adhered to recording paper at 100% duty, characters were printed with the ink composition. The presence or absence of bleeding in the obtained printed matter was evaluated according to the following criteria. A: No bleeding occurs on all papers B: Slight bleeding occurs only on some paper (recycled paper) C: Whisker-like bleeding occurs on all papers NG: Blurring occurs so that the outline of characters is not clear Do

Evaluation 2: After the print quality (color bleed) reaction solution was adhered to the recording paper at 100% duty, 1
Color inks (cyan, magenta, yellow) were simultaneously printed at a duty of 00%, and uneven color mixture at color boundaries was visually evaluated. The results were evaluated according to the following criteria. A: When there is no color mixing on all papers and the boundaries are clear B: When color mixing slightly occurs on some papers (recycled paper) C: When color mixing occurs in a mustache on all evaluation papers NG: When the colors are mixed so that the color boundaries are not clear on all the evaluation sheets

Evaluation 3: After the ink fixing reaction liquid was adhered to the recording paper at a duty of 100%, it was printed on a glossy film (manufactured by Seiko Epson Corporation) for an inkjet printer MJ-700V2C.
The printed matter was air-dried for 24 hours. After drying, an adhesive tape (cellophane tape: Sekisui tape (manufactured by Sekisui Chemical)) was applied to the printed portion of the printed matter, rubbed with a finger two or three times, and then the adhesive tape was peeled off. The state of the printed matter in the spots was visually observed and evaluated according to the following criteria: A: no peeling of the ink (colorant) at all B: slight peeling of the ink (colorant) NG: ink (coloring) Agent) completely peels off

Evaluation 4: Evaluation of discharge stability Using an inkjet printer MJ-700V2C,
Continuous printing was performed at normal temperature, and the presence or absence of missing dots and ink scattering was observed. The results were evaluated according to the following criteria. AA: After 72 hours, the number of missing dots or ink scattering is 10 or less. A: Missing dots or ink scattering occurred 10 times within 48 to 72 hours. B: Missing dots or ink scattering occurred 10 times within 24 to 48 hours. C: Missing dots or ink scattering occurred 10 times within 1 to 24 hours. NG: Missing dots or ink scattering occurred 10 times within one hour.

The evaluation results are as shown in the following table. Reaction liquid Black ink Evaluation 1 Evaluation 3 Evaluation 4 Example 1 1 1 1 A AA A Example 2 2 2 A A A Comparative Example 1 1 3 C NG NG

Reaction liquid Color ink set Evaluation 2 Example 3 1 1 A Comparative example 2 1 2 C Comparative example 3 None 2 NG

[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, and an ink composition and a reaction liquid are supplied to the recording head by an ink tube. Supplied.

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

FIG. 3 is a diagram illustrating an ink jet recording head using the recording head of FIG. 2; In the drawing, reference numeral 31 denotes a reaction liquid adhering area, and reference numeral 32 denotes a printing area where the ink composition is printed on the reaction liquid adhering thereto.

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.

[Explanation of symbols]

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

Claims (19)

[Claims] 1. An ink jet recording method for printing by attaching a reaction liquid and an ink composition to a recording medium, wherein the reaction liquid contains a polyvalent metal salt or polyallylamine or a derivative thereof. Wherein the ink composition contains at least a colorant, an inorganic oxide colloid, and an aqueous solvent, and has a pH of 9
The above is an ink jet recording method. 2. The ink jet recording method according to claim 1, wherein the pH of the ink composition is adjusted by an alkali metal hydroxide. 3. The ink jet recording method according to claim 1, wherein the ink composition further comprises a sugar. 4. The ink jet recording method according to claim 1, wherein said ink composition contains a pigment as a colorant. 5. The ink jet recording method according to claim 1, wherein the ink composition contains colloidal silica as an inorganic oxide colloid. 6. The ink composition according to claim 1, further comprising an epoxy group-containing compound having a functional group capable of reacting with an epoxy group and / or an epoxy group-containing compound having no functional group capable of reacting with an epoxy group. There is Claim 1
6. The ink jet recording method according to any one of 5. 7. The ink jet recording method according to claim 6, wherein the epoxy group-containing compound is an epoxy group-containing resin emulsion and / or a water-soluble epoxy compound. 8. The epoxy group-containing resin emulsion according to claim 1,
8. The ink jet recording method according to claim 7, comprising a copolymer comprising a repeating unit represented by the following formulas (I) and (II). Embedded image (Wherein, R ¹ and R ³ independently represent H or CH ₃ , and R ² comprises, in its structure, one or more groups selected from an alkyl group, a hydroxyl group, a carboxyl group, and a sulfonic acid group) Represents a group). 9. The ink jet recording method according to claim 7, wherein said water-soluble epoxy compound is represented by the following formula. Embedded image (Where n represents a natural number of 4 to 9) 10. The ink jet recording method according to claim 1, wherein the ink composition further comprises a resin emulsion. 11. The reaction solution according to claim 1, wherein the reaction solution contains a nitrate or a carboxylate as a polyvalent metal salt.
The ink jet recording method according to any one of items 10 to 10. 12. A carboxylic acid ion constituting the carboxylate is a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms (a hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid is substituted by a hydroxyl group). Or 6 carbon atoms
The inkjet recording method according to claim 11, which is derived from 10 to 10 carbocyclic monocarboxylic acids. 13. The ink jet recording method according to claim 1, wherein said reaction liquid further comprises an epoxy curing agent. 14. The ink jet recording method according to claim 13, wherein said epoxy curing agent is a water-soluble polyamine. 15. The ink jet recording method according to claim 1, wherein the reaction liquid is attached to a recording medium, and thereafter, the ink composition is printed on the recording medium. 16. The ink jet recording method according to claim 1, wherein the ink composition is printed on a recording medium, and thereafter, a reaction liquid is applied to the recording medium. 17. The ink jet recording method according to claim 1, 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. . 18. A reaction solution comprising a yellow dye, a cyan dye,
Or a color ink comprising a magenta dye,
The ink jet recording method according to claim 1. 19. A recorded matter printed by the method according to claim 1. Description: