JPH1046077A - Ink composition for ink jet printing and printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet printing method affording adequate settability of a colorant on materials to be printed, also affording glossy, favorable prints with high finger touch feeling, scratch resistance, water resistance, light resistance and image denseness, and developing no blurring and color bleeding so as to be compatible with plain paper and reclaimed paper. SOLUTION: This ink composition for ink jet printing comprises a core-shell- type resin emulsion with water as the continuous phase composed of a reaction liquor containing at least polyvalent metal salt(s), at least a colorant, and polymer fine particles each made up of at least three layers laminated, i.e., chore portion, shell portion and a third layer sandwiched between the core and shell portions, a water-soluble organic solvent, a saccharide, and water. This ink composition is put on a material to be printed to afford images.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording method for an ink jet printer, and more particularly to an ink jet recording method capable of performing high-quality printing on plain paper and recycled paper.

[0002] More specifically, the present invention relates to an ink jet recording method in which a reaction solution containing a polyvalent metal salt is attached to a recording medium, and thereafter, an ink composition is printed on the recording medium.

Further, the present invention relates to an ink jet recording method for forming an image by adhering an ink composition to a recording medium having an ink absorbing layer.

Further, an ink jet recording method for forming an image by adhering an ink composition to paper or a recording medium having an ink absorbing layer coated with a water-soluble resin containing a polyvalent metal salt.

[0005] Further, the present invention relates to an ink-jet recorded matter obtained by the above-mentioned ink-jet recording method and an ink-jet recording apparatus using the recording method.

[0006]

2. Description of the Related Art An ink jet recording method is a printing method in which ink droplets are made to fly and adhere to a recording material 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, ink used for ink jet recording mainly contains water, and further contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

However, when printing is performed on plain paper using such an ink, the ink permeates the inside of the recording paper, so that a sufficient image density cannot be obtained, or a problem arises from uneven permeation. There are problems such as "bleeding" and "uneven printing". When color printing is performed,
Since inks of different colors adhere one after another before the previously attached inks are fixed, a phenomenon (hereinafter referred to as “color bleed”) occurs in which colors are mixed unevenly at the boundary between colors, and the image Was not satisfactory.

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 material, and then an ink composition containing a dye material 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.

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.

[0010]

However, the above-mentioned prior art has the following problems.

First, when a pigment is used as a colorant for the ink, the fixability to paper is not sufficient, and when the printed body is rubbed with a finger, the paper becomes dirty, or when the printed body is marked with a marker pen, For example, the printed portion becomes dirty and the coloring agent (pigment) of the ink easily separates from the surface of the printed body, and thus there is a problem in the touch property and abrasion resistance of the printed body. Further, in recent years, in offices and the like, the use of not only high quality paper but also recycled paper has been increasing. However, in many cases, recycled paper is more permeable to ink than high quality paper, and high quality images can be obtained with high quality paper. Even in this case, there is a problem that image bleeding and color bleeding occur on recycled paper.

When a water-soluble dye is used as a coloring agent, the water resistance is generally poor, and the printed body may be illegible due to water droplets.

Further, the disturbance of the color density of the printed matter caused by the bias of the coloring components on the paper is referred to as printing unevenness.
Although this does not cause a serious problem with characters of normal size, it becomes an important problem in applications where graphics, graphs, and the like must be printed.

Accordingly, the present invention has been made to solve these problems, and an object of the present invention is not to cause bleeding, color bleeding and uneven printing when using not only high quality paper but also all plain paper and recycled paper. Another object of the present invention is to provide an ink composition and an ink jet recording method which are excellent in fixability of printed matter, excellent in water resistance and light resistance, and excellent in storage stability of the ink.

[0015]

Means for Solving the Problems The ink composition of the present invention comprises at least a colorant, a core portion in which dispersed particles are the core of a particle, a shell portion as an outer shell of the particle, and further sandwiched between the core portion and the shell portion. A core-shell type resin emulsion having a continuous layer of water composed of polymer fine particles obtained by laminating at least three layers of the separated layers, a water-soluble organic solvent,
Polymer fine particles comprising water and, more specifically, a core-shell type resin emulsion in which at least three or more layers having at least a core part having an epoxy group and a shell part having at least a carboxyl group are laminated. Characterized by the fact that water consisting of Furthermore, an ink jet recording method is characterized in that an image is formed by adhering a reaction liquid containing a polyvalent metal salt to a recording medium and the ink composition described above.

The present inventor has conducted intensive studies to solve the above technical problems, and as a result, has found the following findings. That is, in the ink jet recording method for forming an image by adhering a reaction liquid containing a polyvalent metal salt to a recording medium and the ink composition described above, by using the core-shell type resin emulsion described above, high quality paper Not only on the recording medium such as plain paper and recycled paper, but also on the recording medium such as described above, the ink composition is aggregated by the interaction with the polyvalent metal ion, and suppresses the penetration of the coloring agent, so that bleeding and color bleed do not occur. The core-shell type resin emulsion in the ink composition is united and further fused at that time, and the epoxy group and the shell of the core portion of the dispersed particles of the core-shell type resin emulsion are fused. To form a tough crosslinkable film because the carboxyl group and epoxy group of the part react with and crosslink with the functional group. By increasing the adhesion to paper due to the carboxyl group of the shell portion of the dispersed particles of the shell-type resin emulsion, the printed matter has excellent fixability, excellent touch and abrasion resistance, and also has water resistance and light resistance. I found that it was also excellent. Furthermore, although the core-shell type resin emulsion used in the present invention has a polymer having a functional group that reacts with each other in the same particle, each reactive group is present separately in the core part and the shell part. Therefore, it was found that the ink state was stable.

The present inventor has completed the present invention by finding the new facts described above.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The core-shell type resin emulsion used in the present invention includes a core portion in which dispersed particles are the core of a particle, a shell portion as an outer shell of the particle, and a layer sandwiched between the core portion and the shell portion. Is a resin emulsion having water as a continuous layer composed of polymer fine particles obtained by laminating at least three or more layers. More specifically, a layer containing at least three layers of dispersed particles, each containing a polymer having a functional group that reacts with each other, and a layer containing a polymer inert to any of these functional groups. Is a resin emulsion having water as a continuous layer comprising polymer fine particles obtained by laminating the above.

Hereinafter, the core-shell type resin emulsion used in the present invention will be described in more detail.

The structure of the core-shell type resin emulsion used in the present invention has a core portion made of an epoxy group-containing compound and a shell portion made of a copolymer having at least a carboxyl group. The group-containing compound is a copolymer containing an ethylenically unsaturated compound having an epoxy group as an essential component,
The shell part is a copolymer containing an ethylenically unsaturated compound having a carboxyl group as an essential component. More specifically, the epoxy group-containing ethylenically unsaturated compound which is an essential component of the copolymer forming the core is glycidyl methacrylate or / and glycidyl acrylate, and the essential component of the copolymer forming the shell is The ethylenically unsaturated compound having a carboxyl group is methacrylic acid and / or acrylic acid.

Further, the structure of the core-shell type resin emulsion used in the present invention includes a core portion composed of an epoxy group-containing compound and a shell portion composed of a copolymer having at least a carboxyl group and a functional group which reacts with an epoxy group. And those having the following. More specifically, the copolymer having an epoxy group forming the core portion is a copolymer containing glycidyl methacrylate or / and glycidyl acrylate as an essential component, and the shell portion contains methacrylic acid or / and / or acrylic acid as an essential component. age,
Further, it is a copolymer comprising an unsaturated compound having a functional group which reacts with an epoxy group.

The core-shell type resin emulsion preferably used in the present invention is disclosed in JP-A-7600.
4, wherein the continuous phase is water, and the first layer is a core part of particles made of a copolymer having an epoxy group, comprising three layers in which the dispersed particles are laminated, A second layer composed of an epoxy group and a copolymer inert to any of the functional groups capable of reacting with the epoxy group, and
A third layer that is an outer shell of particles made of a copolymer having a functional group capable of reacting with an epoxy group is laminated, and a second layer is laminated between the first layer and the third layer. Is a resin emulsion having a core-shell structure. In the above dispersed particles, more specifically, the first layer containing at least a copolymer having an epoxy group is a copolymer containing an epoxy derivative such as glycidyl methacrylate, glycidyl acrylate, or allyl glycidyl ether as an essential component. There is a third layer containing a copolymer having a functional group capable of reacting with an epoxy group, acrylic acid containing a carboxyl group, methacrylic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester , An ethylenically unsaturated carboxylic acid such as fumaric acid or its monoalkyl ester, N-methylaminoethyl methacrylate containing an amino group, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylethyl acrylate, etc. Are alkylamino esters of methacrylic acid,
Monovinyl pyridines such as vinyl pyridine, vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether, and alkylamino groups such as N- (2-dimethylaminoethyl) acrylamide and N- (2-dimethylaminoethyl) methacrylamide. It is a copolymer using unsaturated amides or the like alone or in combination of two or more as essential constituents. Further, the second layer containing a copolymer inert to both the epoxy group and the functional group capable of reacting with the epoxy group may be a methyl-, ethyl-, isopropyl-, n-butyl-, isobutyl-, n- -Amyl-, isoamyl-, n-hexyl-, 2-ethylhexyl-, octyl-, decyl-, dodecyl-, octadecyl-, cyclohexyl-, phenyl-, benzyl-,
Acrylic esters such as 2-hydroxyethyl, hydroxypropyl-acrylate or methacrylate or vinyl esters such as methacrylic ester and vinyl acetate, acrylonitrile, methacrylonitrile and the like, styrene, 2-methylstyrene, vinyltoluene, t-butyl Aromatic vinyls such as styrene, chlorostyrene, vinylanisole, vinylnaphthalene and divinylbenzene; amides such as acrylamide, methacrylamide, maleic amide, N-methylolacrylamide, N-methylolmethacrylamide, and diacetoneacrylamide; Vinylidene halides such as vinylidene, vinylidene fluoride, etc., ethylene, propylene, isopropylene butadiene, vinylpyrrolidone, vinyl chloride, vinyl ether, vinylidene Ketones, vinyl amides, chloroprene, a copolymer was used alone or in combination of two or more like. The monomers used for these second layers include a first layer containing a copolymer having an epoxy group and a third layer containing a copolymer having a functional group capable of reacting with an epoxy group. It is also used as a comonomer to form. Dispersed particles of the above resin emulsion,
It is obtained by laminating copolymers produced by successively copolymerizing by an emulsion polymerization method using monomers necessary for sequentially producing a desired copolymer.

The core-shell type resin emulsion used in the present invention is very stable in ordinary storage owing to the structure described above, even though a polymer having a mutually reactive functional group is present in the same particle. .

Since the ink composition for ink-jet recording of the present invention is used at room temperature, in order to obtain a quick drying property, a touch property, an abrasion resistance and a water resistance of a printed body at room temperature,
It is necessary that the core-shell type resin emulsion used in the present invention be formed into a film at room temperature. Therefore, the glass transition point of the dispersed particles (polymer fine particles) is preferably 20 ° C. or lower. The glass transition point of the dispersed particles is 20 ° C
Under the following conditions, the core-shell type resin emulsion used in the present invention forms a film at room temperature, and at that time, a sufficient crosslinking reaction occurs.

The particle diameter of the core-shell type resin emulsion is preferably about 150 nm or less.

As the core-shell type resin emulsion, a commercially available core-shell type resin emulsion can be used, and examples thereof include EPG1001 (manufactured by Mitsui Toatsu Chemicals, Inc.). EPG1001 has a three-layer core-shell structure in which the structure of the dispersed particles is a three-layer structure in which a core portion composed of a copolymer containing glycidyl methacrylate as an essential component and a copolymer containing an outermost shell containing methacrylic acid as an essential component. It is a resin emulsion.

The content of the core-shell type resin emulsion in the ink composition for ink jet recording of the present invention is as follows:
The solid content (resin concentration) is preferably about 1 to 10% by weight of the ink composition, more preferably 1 to 5% by weight.

The core-shell type resin emulsion used in the present invention suppresses the penetration of the colorant by interaction with polyvalent metal ions, and further promotes fixing to recording media such as high quality paper, plain paper, and recycled paper. It has the effect of doing. That is, in the present invention, in the ink jet recording method of forming an image by adhering a reaction liquid containing a polyvalent metal salt to the recording medium and the ink composition of the present invention using the core-shell type resin emulsion described above. First, on the recording medium, since the resin emulsion in the ink composition and the polyvalent metal ion in the reaction liquid cohere with each other, the penetration of the colorant into the recording medium is suppressed. Further, the -COOH group of the shell portion of the resin emulsion and the OH group of the cellulose constituting the paper fiber are firmly attached by hydrogen bonding, and at the same time, the resin emulsion is further fused and fused to form a film. . At that time (during fusion), the epoxy group in the core portion of the resin emulsion and the functional group reacting with -COOH and / or the epoxy group in the shell portion react and crosslink to form a tough crosslinkable film. it can. Therefore, the obtained prints have good finger touch, abrasion resistance, water resistance, light resistance, high OD value and good gloss.
However, the description of this mechanism has been described in order to explain the effect when the above resin emulsion is used,
It is not binding on the invention.

Preferred embodiments of the ink composition of the present invention include:
A glass transition obtained by laminating at least three layers of a colorant, a core portion where the dispersed particles are the core of the particle, a shell portion which is the outer shell of the particle, and at least three layers sandwiched between the core portion and the shell portion. Containing a core-shell type resin emulsion having a continuous layer of water consisting of polymer fine particles having a temperature of 20 ° C. or less, a water-soluble organic solvent having a boiling point of 180 ° C. or more, water, sugar, a tertiary amine and an alkali hydroxide. I do.
The use of a water-soluble organic solvent having a boiling point of 180 ° C. or more results in water retention and wettability of the ink composition, and the addition of sugar and tertiary amine also brings wettability. The addition of the tertiary amine and the alkali hydroxide results in the colorant in the ink composition as well as the stabilization of the dispersion of the core-shell emulsion. Therefore, the ink composition of the present invention has a glass transition point of 20 ° C.
Despite the use of a core-shell type resin emulsion with a continuous layer of water consisting of the following polymer fine particles, it has excellent storage stability without colorant aggregation or viscosity increase even after long-term storage. In addition, the fluidity and re-dispersibility are maintained for a long time even when left open (at room temperature and in contact with air), and nozzle clogging during printing or restarting after printing is interrupted. No ejection occurs and the ejection stability is high.

The boiling point used in the present invention is 180 ° C.
The above water-soluble organic solvent is not particularly limited as long as it satisfies the above conditions.
More than one species can be used in combination. Preferred examples of the water-soluble organic solvent include ethylene glycol (boiling point: 19
7 ° C .; the parentheses below indicate the boiling point), propylene glycol (187 ° C.), diethylene glycol (245 ° C.),
Pentamethylene glycol (242 ° C.), trimethylene glycol (214 ° C.), 2-butene-1,4-diol (235 ° C.) 2-ethyl-1,3-hexanediol (243 ° C.), 2-methyl-2, 4-pentanediol (197 ° C.), N-methyl-2-pyrrolidone (202
C), 1,3-dimethyl-2-imidazolidinone (25
7-260 ° C), 2-pyrrolidone (245 ° C), glycerin (290 ° C), tripropylene glycol monomethyl ether (243 ° C), dipropylene glycol monoethyl glycol (198 ° C), dipropylene glycol monomethyl ether (190 ° C) , Dipropylene glycol (232 ° C), triethylene glycol monomethyl ether (249 ° C), tetraethylene glycol (327 ° C), triethylene glycol (288 ° C),
Diethylene glycol monobutyl ether (230
C), diethylene glycol monoethyl ether (20
2 ° C), diethylene glycol monomethyl ether (1
94 ° C.). More preferably, the boiling point is 200
A temperature of at least ℃ is good.

The content of these water-soluble organic solvents in the ink composition of the present invention is in the range of 10 to 40% by weight, more preferably 10 to 30% by weight of the ink composition.

The saccharide used in the present invention is a monosaccharide,
Examples include disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, (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 (general formula H
OCH ₂ (CHOH) _n CH ₂ OH (where n = 2 to 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.
It is in the range of 40% by weight, more preferably 1 to 30% by weight.

The tertiary amine used in the present invention is
Examples include trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, triisopropenolamine, butyldiethanolamine and the like. These may be used alone or in combination. These serve as catalysts for a crosslinking reaction during the formation of a film.

The amount of these tertiary amines added to the ink composition of the present invention is 0.1 to 10% by weight, more preferably
0.5 to 5% by weight.

The alkali hydroxide used in the present invention is potassium hydroxide or sodium hydroxide, and the amount added to the ink composition of the present invention is 0.01 to 5% by weight.
And preferably 0.05 to 3% by weight.

The colorant contained in the ink composition of the present invention may be a dye or a pigment, but is preferably a pigment in terms of light resistance and water resistance.

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 the pigment, 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 dyes (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.

In the present invention, the pigment is preferably added to the ink as a pigment dispersion liquid dispersed in an aqueous medium with a dispersant. As a dispersant used for preparing a pigment dispersion, a dispersant generally used for preparing a pigment dispersion, for example, a polymer dispersant or a surfactant can be used. It will be apparent to those skilled in the art that the surfactant contained in the pigment dispersion will also function as the surfactant of the ink composition described below.

The content of the pigment in the ink composition of the present invention is preferably about 0.5 to 25% by weight, and more preferably about 2 to 15% by weight.

The ink composition of the present invention may further contain a surfactant. Examples of surfactants include:
Anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfate, etc.), nonionic surfactants (for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester) Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, etc.) and acetylene glycol (olefin Y, and Surfynol 82, 104, 44).
0, 465, and 485 (all Air Products and C
chemicals Inc.). These can be used alone or in combination of two or more.

The ink composition of the present invention may contain a general-purpose resin emulsion in addition to the core-shell type resin emulsion. As the resin emulsion, the continuous phase is water, and the dispersed particles are acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acryl-styrene resin, butadiene resin, styrene resin, etc. There are some. The particle size of these resin components is preferably about 150 nm or less, more preferably about 5 to 100 nm.
These resin emulsions can be obtained by emulsion polymerization of monomers in the presence of a polymerization catalyst (also referred to as a polymerization initiator) and an emulsifier (generally a surfactant is used). 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.).

Further, in order to shorten the drying time of the ink, a low boiling organic solvent may be further added in addition to the above high boiling organic solvent. Preferred examples of the low boiling organic solvent used include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butanol, tert-butanol, iso-butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable.

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

<Reaction Solution> The reaction solution used in the present invention will be described below.

The reaction solution used in the present invention basically contains a polyvalent metal salt and water. The polyvalent metal salt contained in the reaction solution used in the present invention,
It is composed of a polyvalent metal ion having a valence of 2 or more and an anion bonded to the polyvalent metal ion, and can be used as long as it is soluble in water. Specific examples of the polyvalent metal ion include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ , and Ba ²⁺
And divalent metal ions such as Al ³⁺ , Fe ³⁺ and Cr ³⁺ . Specific examples of the anion include Cl ⁻ , NO ₃ ⁻ , I ⁻ , Br ⁻ , ClO ₃ ⁻ and C.
H ₃ COO ^{− and the} like, and preferably a nitrate ion or a carboxylate ion. 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. is there. Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and hexanoic acid. Particularly, formic acid and acetic acid are preferable. A hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid may be substituted with a hydroxyl group. Preferred examples of such a carboxylic acid include benzoic acid and naphthoic acid, and more preferably benzoic acid. Is an acid.

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. Preferably, it is about 5 to 25% by weight.

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

The amount of the high-boiling water-soluble 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, it is preferable to add triethylene glycol monobutyl ether and glycerin as the high boiling water-soluble organic solvent. When these are added in combination, the addition amounts of triethylene glycol monobutyl ether and glycerin are preferably about 10 to 20% by weight and about 1 to 15% by weight, respectively. Further, the above-mentioned surfactant may be added to the reaction solution. In addition, a pH adjuster, a preservative, a fungicide, and the like may be added to the reaction solution as needed to improve storage stability.

Further, an epoxy curing agent may be added to the reaction solution. In the inkjet recording method of the present invention for forming an image by adhering a reaction liquid containing a polyvalent metal salt to a recording medium and the ink composition described above, the addition of the epoxy curing agent to the reaction liquid is as described above. When the core-shell type emulsion contained in the ink composition is coalesced and further fused, the epoxy group of the core reacts with the epoxy curing agent, and the formed film is further promoted in cross-linking. Gives a print having rub resistance, water resistance and light resistance.

The epoxy curing agent preferably used in the present invention is typically water-soluble. Further, the (cross-linking) reaction preferably proceeds at room temperature. Examples of such curing agents include amine compounds such as ethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, trimethylhexamethylenediamine, modified aliphatic amines, water-soluble polyamines, and water-soluble room-temperature curing catalysts other than amines, for example, Aromatic sulfonic acids such as P-phenolsulfonic acid, and curing agents for epoxy emulsions. It is also possible to use a commercially available curing agent, examples of which include Armatex H700 (manufactured by Mitsui Toatsu Chemicals, Inc.) and Epoki H
(Made 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.

<Ink Jet Recording Method and 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 a mode 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 the movement, the reaction liquid is ejected 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, reference numerals 41a and 41b denote reaction liquid ejection nozzles, and nozzles 42, 43, 44, and 45 respectively emit 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 1a and the ink tank 2b move on the carriage 4. Regarding the adhesion of the reaction liquid to the recording medium, any of a method of selectively applying the reaction liquid only at a place where the ink composition is applied and a method of attaching the reaction liquid to the entire paper may be used. The former is economical because it can minimize the consumption of the reaction liquid, but requires a certain degree of accuracy in the position where both the reaction liquid and the ink composition are adhered. 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 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.

Further, when printing on an ink jet recording medium having an ink absorbing layer, a printing method using a reaction liquid and an ink composition, and a method using only the ink composition on a special recording medium without using a reaction liquid. There are printing methods, and these may be selected in a timely manner in consideration of print quality.

In the ink jet recording medium having the ink absorbing layer, the ink absorbing layer is made of a water-soluble resin and / or
Or, it is composed of alumina sol and / or silica sol, and has excellent adhesion to the ink composition of the present invention.

A method for forming an image by attaching the ink composition according to any one of claims 1 to 2 to a paper coated with a water-soluble resin containing a polyvalent metal atom or a recording medium having an ink absorbing layer, By coating a paper or a recording medium having an ink-absorbing layer with a water-soluble resin containing a polyvalent metal salt in advance, there is no bleeding or color bleed, no finger touch, no abrasion, without applying a reaction solution during printing. An image having excellent properties can be obtained.

[0068]

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

The amount of the resin emulsion added in the examples is the solid content concentration (resin concentration).

(Black Ink 1) As the core-shell type emulsion in the present invention, the above-mentioned JP-A-4-760 is used.
Almatex EPG1001 manufactured by Mitsui Toatsu Chemicals disclosed in Japanese Patent Publication No. 04-2004 is used.

Carbon black MA7 5% by weight (manufactured by Mitsubishi Kasei Corporation) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex EPG1001 3% by weight (core-shell type acrylic resin emulsion, resin component 50%, Higashi Mitsui Sucrose 0.7% by weight Maltitol 6.3% by weight Glycerin 15% by weight 2-pyrrolidone 2% by weight Triethanolamine 1.0% by weight NaOH 0.1% by weight Pure water Remaining amount (black ink 2) Carbon black Raven1080 5% by weight (Columbia Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Alumatex EPG1001 3% by weight (core-shell type acrylic resin emulsion, resin component 50%, Mitsui Higashi) Sucrose 0. % By weight Maltitol 6.3% by weight Triethylene glycol 15% by weight 2-Pyrrolidone 2% by weight Triethanolamine 1.0% by weight KOH 0.1% by weight Pure water Remaining amount (black ink 3) Carbon black MA7 5% by weight (Mitsubishi Kasei Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex EPG1001 3% by weight (Core-shell type acrylic resin emulsion, resin component 50%, manufactured by Mitsui Toatsu Chemicals, Inc.) Sucrose 0. 7 wt% maltitol 6.3 wt% glycerin 10 wt% triethylene glycol monomethyl ether 5 wt% 2-pyrrolidone 2 wt% triethanolamine 1.0 wt% NaOH 0.1 wt% pure water remaining (black ink 4 ) The core of the dispersed particles (polymer particles) is glycidyl meta A copolymer composed of acrylate and styrene and 2-ethylhexyl acrylate, a shell composed of methacrylic acid, styrene, 2-ethylhexyl acrylate and a copolymer composed of N-methylamino methacrylate, and an intermediate layer of the core and the shell composed of styrene. 2-
A core-shell type resin emulsion, which is a copolymer of ethylhexyl acrylate, was produced and used according to JP-A-4-76004.

Carbon black MA7 5% by weight (manufactured by Mitsubishi Chemical Corporation) Styrene-acrylic acid copolymer (dispersant) 1% by weight Core-shell resin emulsion 3% by weight Sucrose 0.7% by weight Maltitol 6.3 Weight% glycerin 10 weight% triethylene glycol monomethyl ether 5 weight% 2-pyrrolidone 2 weight% triethanolamine 1.0 weight% NaOH 0.1 weight% pure water remaining amount (black ink 5; comparative example) carbon black Raven1080 5 % By weight (manufactured by Colombia Carbon Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% 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 (black ink 6; comparison 5% by weight of carbon black MA7 (manufactured by Mitsubishi Chemical Corporation) 1% by weight of styrene-acrylic acid copolymer (dispersant) 3% by weight of microgel E-5002 (29.2% of styrene-acrylic resin emulsion, resin component 29.2%, MFT about
80 ° C, manufactured by Nippon Paint Co., Ltd.) Sucrose 0.7 wt% Maltitol 6.3 wt% Glycerin 5 wt% 2-Pyrrolidone 2 wt% Triethanolamine 1.0 wt% KOH 0.1 wt% Pure water Remaining amount Preparation of each of the above inks was performed as follows.

First, carbon black, a dispersant and water were mixed and dispersed in a sand mill (manufactured by Yasukawa Seisakusho) with glass beads (1.7 mm in diameter, 1.5 times the weight (weight) of the mixture) for 2 hours. Thereafter, the glass beads were removed to prepare a carbon black dispersion. Then, the resin emulsion, sucrose, maltitol, glycerin, 2
-Pyrrolidone, triethanolamine, and alkali hydroxide were added, and the mixture was stirred at room temperature for 20 minutes. Then, the carbon black dispersant was gradually added dropwise while stirring the ink solvent, and further stirred for 20 minutes. This was filtered through a 5 μm membrane filter to obtain an inkjet recording ink.

Next, examples of the color ink of the present invention will be described.

(Color Ink 1) <Cyan Ink> Pigment KETBLUEEX-1 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex EPG1001 3% by weight ( Core-shell type acrylic resin emulsion, resin component 50%, manufactured by Mitsui Toatsu Chemicals 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 remaining amount <Magenta Ink> Pigment KETRED309 2% by weight (Dai Nippon Ink Chemical Industry Co., Ltd.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Armatex EPG1001 3% by weight (Core-shell type acrylic resin emulsion, resin component 50% , Made by Mitsui Toatsu 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 Remaining amount <Yellow ink> Pigment KETYELLOW403 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Armatex EPG1001 3% by weight (core-shell type acrylic resin emulsion, resin component 50%, manufactured by Mitsui Toatsu 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 Remaining amount (color ink 2; comparative example) <Cyan ink> Pigment KETBLUEEX-1 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Sucrose 0. 7% by weight Maltitol 6.3% by weight Glycerin 10% % 2-pyrrolidone 2% by weight Ethanol 4% by weight Pure water Remaining amount <Magenta ink> Pigment KETRED309 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Sucrose 0 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 <Yellow ink> Pigment KETYELLOW403 2% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Sucrose 0 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 The above ink was prepared as follows.

First, a pigment, a dispersant and water are mixed, and the mixture is mixed with glass beads (diameter 1.7) in a sand mill (manufactured by Yasukawa Seisakusho).
mm, 1.5 times the amount (weight) of the mixture), and the glass beads were removed to prepare a pigment dispersion. Next, a resin emulsion, sucrose, maltitol, glycerin, 2-pyrrolidone, triethanolamine, and alkali hydroxide are added to water, and the mixture is stirred at room temperature for 20 minutes. Then, the carbon black dispersant is gradually added while stirring the ink solvent. And the mixture was further stirred for 20 minutes. This is filtered through a 5 μm membrane filter,
An ink for inkjet recording was obtained.

Hereinafter, an example of preparing a reaction solution according to the present invention will be described.

(Reaction solution 1) Magnesium nitrate hexahydrate 25% by weight Triethylene glycol mono-butyl ether 10% by weight Glycerin 20% by weight Pure water Remaining amount (Reaction solution 2) Magnesium nitrate hexahydrate 25% by weight % Water-soluble polyamine; Armatex H700 3% by weight (manufactured by Mitsui Toatsu Chemicals, Inc.) Triethylene glycol mono-butyl ether 10% by weight Glycerin 20% by weight Pure water Remaining amount The following printing evaluation tests were performed for each of the above inks. Was.
The printing evaluation test is shown below.

Inkjet printer MJ-700V2
C (manufactured by Seiko Epson Corporation) was used to print on each of the following papers. In printing, first, the reaction liquid was printed at 100% duty, and then characters were printed with black ink. The discharge amount of both the reaction liquid and the ink was 0.07 μg / dot, and the density was 360 dpi. The printing test paper used is shown below.

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., Ltd., recycled paper) ) Yamayuri paper (recycled paper manufactured by Honshu Paper Co., Ltd.) <Evaluation 1: Abrasion resistance test (line marker resistance)> After the printed matter printed by the above method was air-dried for 24 hours, yellow aqueous fluorescence manufactured by Zebra Corporation was used. Pen ZEBRA PEN2
(Trademark) and print pressure 4.9 × 10 ⁵ N
/ M ² , and the presence or absence of stains on the yellow portion was visually observed, and evaluated as follows.

◎: No stain is generated even if rubbed twice immediately after printing. ： １: No stain is generated even if rubbed twice after one day. Δ: Stain is not generated until one rub after one day. Some papers stained twice or more. ×: Some papers stained even after one day. The results are shown in Tables 1 and 2.

<Evaluation 2: Print Quality (Bleeding)> The printed matter printed by the above method was examined for the occurrence of bleeding in characters after drying, and evaluated as follows.

◎: Clear printing without bleeding on all papers ：: Whisker-like bleeding on some paper (recycled paper) △: Whisker-like bleeding on all papers X: Character Table 1 and Table 2 show the results.

<Evaluation 3: OD value> The reflection OD value of the printed matter printed by the above method was measured by Macbeth PCMII (manufactured by Macbeth). Table 1 shows the results.

<Evaluation 4: Color Bleed> 100 inks were applied to each of the following papers using an ink jet printer MJ-700V2C.
After adhering the reaction solution to each paper at 100% duty, 100% d
color ink (cyan, magenta, yellow)
And black ink (character) were printed at the same time, and uneven color mixture at the boundary between the characters was visually evaluated as follows.

：: When there is no color mixture and the boundary is clear. Δ: When color mixture occurs like a whisker. ×: When the color is mixed so that the outline of the character is not clear. Show.

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., Ltd., recycled paper) ) Yamayuri paper (recycled paper manufactured by Honshu Paper Co., Ltd.) The results are shown in Table 3.

The results of the above printing evaluation are shown below.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

A glossy film for exclusive use for an ink jet printer MJ-700V2C (manufactured by Seiko Epson Corporation) in which the ink absorbing layer is composed of a water-soluble resin and / or alumina sol and / or silica sol;
The ink was printed on paper coated with a water-soluble resin containing a polyvalent metal salt using an inkjet printer MJ-700V2C (manufactured by Seiko Epson Corporation), and the fixability of the ink was examined.

The paper coated with a water-soluble resin containing a polyvalent metal salt was prepared as follows.

Magnesium nitrate hexahydrate 25% by weight, triethylene glycol monobutyl ether
5% by weight, ethanol 20% by weight, degree of polymerization about 1500
10% by weight of polyvinyl alcohol, 40% by weight of pure water
Was mixed well at room temperature to prepare a coating solution. This was uniformly applied to Xerox 4024 paper (manufactured by Xerox Corporation) using a simple rod coater and air-dried for 24 hours.

The fixing property of the ink was evaluated as follows.
The printed matter was air-dried for 24 hours and tested.

(1) The printed matter was examined in the same manner as in Evaluation 1 (line marker test). ： １: No stain is generated by one rub. Δ: Stain is slightly generated by one rub. ×: Stain is generated by one rub. (2) Adhesive tape (cellophane tape: Sekisui tape (Sekisui Water) ))) 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 portion was visually observed and evaluated (adhesive tape test). ：: There is no peeling of the ink (colorant) from the special glossy paper surface. Δ: The ink (colorant) is on both the special glossy paper surface and the adhesive surface of the adhesive tape. X: The ink (colorant) is the special glossy paper surface. The results are shown in Table 4.

[0097]

[Table 4]

[0098]

As described above, according to the present invention, a reaction solution containing at least a polyvalent metal salt on a recording material, at least a colorant, and a core portion in which dispersed particles are the core of the particles and the outer portion of the particles. A core-shell type resin emulsion in which water is a continuous layer composed of polymer fine particles obtained by laminating at least three layers of a shell portion serving as a shell, and further a layer sandwiched between the core portion and the shell portion; By forming an image by adhering an ink composition for inkjet recording characterized by containing a sugar and water, sufficient fixability of the colorant to the recording medium is obtained, sex,
It is possible to obtain a printed body with excellent abrasion resistance, water resistance and light resistance, and when using not only high quality paper but also all plain paper and recycled paper, the image density is high, and bleeding, color bleeding, printing unevenness The present invention can provide an ink jet recording method for plain paper and recycled paper which does not cause the problem.

[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 inkjet recording using the recording head of FIG. 2; In the figure, reference numeral 31 denotes a reaction liquid adhering area, and reference numeral 32 denotes a region where the reaction liquid is adhering and the ink composition is printed.

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

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication // C08F 265/06 MQM C08F 265/06 MQM

Claims (17)

[Claims] 1. At least a colorant, a core portion in which dispersed particles are the core of a particle, a shell portion as an outer shell of the particle, and at least three layers of a layer sandwiched between the core portion and the shell portion.
An ink composition for inkjet recording, comprising: a core-shell type resin emulsion having a continuous layer of water composed of polymer fine particles obtained by laminating two or more layers; a water-soluble organic solvent; a saccharide; and water. . 2. At least a colorant, a core portion in which the dispersed particles are the core of the particle, a shell portion as the outer shell of the particle, and at least three of the layer sandwiched between the core portion and the shell portion.
A core-shell type resin emulsion having a continuous layer of water composed of polymer fine particles having a glass transition point of 20 ° C. or lower formed by laminating two or more layers; a water-soluble organic solvent having a boiling point of 180 ° C. or higher; water; And a tertiary amine and an alkali hydroxide. 3. The core-shell resin emulsion according to claim 1, wherein the core-shell type resin emulsion comprises a core portion made of an epoxy group-containing compound and a shell portion made of a copolymer having at least a carboxyl group. Ink composition for ink jet recording. 4. The core-shell type resin emulsion according to claim 3, wherein the epoxy group-containing compound in the core portion is a copolymer containing an ethylenically unsaturated compound having an epoxy group as an essential component, and the shell portion has a carboxyl group. 3. The ink composition for ink jet recording according to claim 1, which is a copolymer containing an ethylenically unsaturated compound having the following formula as an essential component. 5. The core-shell type resin emulsion according to claim 4, wherein the copolymer having an epoxy group forming the core is a copolymer containing glycidyl (meth) acrylate as an essential component, and the shell is ( 3. The ink composition for inkjet recording according to claim 1, which is a copolymer containing (meth) acrylic acid as an essential component. 6. A core-shell type resin emulsion comprising a core portion comprising an epoxy group-containing compound and a shell portion comprising a copolymer having at least a functional group which reacts with a carboxyl group and an epoxy group. 3. The ink composition for ink jet recording according to claim 1 or 2, wherein 7. The core-shell type resin emulsion according to claim 6, wherein the copolymer having an epoxy group forming the core is a copolymer containing glycidyl (meth) acrylate as an essential component, and the shell has ( 3. The ink jet recording ink according to claim 1, wherein the copolymer is a copolymer comprising (meth) acrylic acid as an essential component and an ethylenically unsaturated compound having a functional group which reacts with an epoxy group. Composition. 8. A first layer made of a copolymer having at least an epoxy group, a second layer made of a copolymer inert to any of an epoxy group and a functional group capable of reacting with the epoxy group, and Core-shell type resin emulsion in which a third layer made of a copolymer having a functional group capable of reacting with an epoxy group is laminated, and a second layer is laminated between the first layer and the third layer The ink composition for inkjet recording according to claim 1, wherein: 9. The ink composition for inkjet recording according to claim 1, wherein the colorant contained in the ink composition is a pigment. 10. An ink-jet recording method comprising: attaching a reaction liquid containing a polyvalent metal salt to a recording medium to the ink composition according to claim 1 to form an image. 11. The ink jet recording method according to claim 10, wherein the reaction solution further contains an epoxy curing agent. 12. The ink jet recording method according to claim 11, wherein the epoxy curing agent is a water-soluble polyamine. 13. An ink jet recording method comprising forming an image by attaching the ink composition according to claim 1 to a recording medium having an ink absorbing layer. 14. An ink-absorbing layer comprising a water-soluble resin and / or
14. The ink jet recording method according to claim 13, wherein the ink jet recording method comprises an alumina sol and / or a silica sol. 15. An image is formed by attaching the ink composition according to claim 1 to a recording medium having paper or an ink absorbing layer coated with a water-soluble resin containing a polyvalent metal salt. An inkjet recording method characterized by the above-mentioned. 16. An ink jet recording ink composition according to claim 1, wherein the ink composition is an ink jet recording ink composition.
An inkjet recorded matter recorded using the recording method according to any one of the above. 17. An ink jet recording apparatus using the recording method according to claim 10. Description: