JP2002302627A - Two-component reactive recording liquid and recording process and recorded matter using this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording liquid which can print fine images on both absorbable and non-absorbable recording media without any color blur, feathering nor bleeding. SOLUTION: The two-component reactive recording liquid is equipped with at least an aqueous ink composition containing a coloring material and a cationic resin emulsion and a reaction liquid containing an anionic reactive agent and an anionic resin emulsion which generates aggregates when coming into contact with the ink composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part reaction type recording liquid for printing by depositing an ink composition and a reaction liquid on a recording medium, and a recording method and a recording using the same. Regardless of whether the recording medium is made of a substance that absorbs the ink composition or is made of a substance that does not absorb the ink composition, color bleeding is performed without performing a special surface treatment on the recording medium. The present invention relates to a two-component reaction type recording liquid capable of printing an image without color or color bleed, a recording method and a recorded matter using the same.

[0002]

2. Description of the Related Art An aqueous ink composition contains water as a main component, and further contains a coloring component, a wetting agent such as glycerin, a penetrant, a surfactant, a bactericidal / antifungal agent, and the like. Is generally contained. As the recording medium used for the aqueous ink composition, one that can absorb the ink composition to some extent and allow the coloring material to permeate, such as paper and cloth, is used.

On the other hand, when printing or coating is performed on a recording medium which does not basically absorb an aqueous ink composition such as a synthetic resin or metal, a solvent-based ink using an organic solvent (particularly lipophilic) is generally used. Compositions and paints have been used. The reason is that solvent-based inks and coating compositions are composed of raw materials having the property of not dissolving in water, so images printed using these materials have fixing properties, abrasion resistance, and water resistance. And the productivity is excellent because the time required for drying and fixing to a recording medium is short.

[0004] However, organic solvents often show toxicity to animals and plants and have a large environmental load. Therefore, attention must be paid to its use and disposal, and there are many inconveniences in handling. In addition, when used in large quantities, it is necessary to install exhaust treatment equipment and the like.

Therefore, even when printing and painting on a non-absorbable recording medium, the recording method using the aqueous ink composition is considered to be preferable in terms of safety, environment, convenience of use, and the like. Can be

However, when printing is performed on a non-absorbing recording medium using an aqueous ink, the affinity of the ink with the recording medium, that is, the so-called "wettability" becomes a serious problem.
If the wettability of the ink on the recording medium is low, the ink does not spread and becomes water-drop-like (repulsion occurs), so printing cannot be performed. Are mixed with each other (the occurrence of color bleed), and the ink spreads around the printing area (the occurrence of bleeding), which causes a problem in image formation.

In printing on a recording medium, it is also required that the coloring material component of the aqueous ink composition be firmly fixed on the recording medium.

Further, even when printing is performed on a recording medium that absorbs ink, fixing properties, abrasion resistance, and durability are required to some extent. In particular, in order to obtain high-quality images using water-based inks, color bleeding and color bleeding must not occur during printing, and printing on recording media such as ordinary paper such as plain paper. In this case, it is necessary to prevent the phenomenon (feathering) in which the ink extends like a beard only along the paper fibers. Further, depending on the storage environment, water resistance may be required.

The causes of image degradation described above will be described below. (1) Phenomenon that ink spreads around (color bleeding) (2) Phenomenon that ink spreads like a beard only along the fiber of paper (feathering) (3) Boundary of color because each color mixes with each other In order to prevent the occurrence of these image deterioration factors, solvent-based ink compositions and paints are generally used for non-absorptive recording media. However, in many cases, printing is performed using a solvent-based ink composition or a paint in order to avoid the occurrence of the above-described image deterioration factors.

When printing is performed using an aqueous ink for applications requiring fixing properties, abrasion resistance and water resistance, a special surface treatment or a post-printing surface treatment may be applied to the recording medium in advance. Generally done. That is, in the former, an ink receiving layer is formed on the printing surface of the recording medium, and in the latter, a protective layer is formed, such as hot and cold laminating.
There are many known methods for forming an overcoat layer.

However, these special surface treatments and printing surface protection treatments have the drawback that they inevitably complicate the printing apparatus and the printing process, increase the cost, and lower the productivity.

Accordingly, an object of the present invention is to provide a recording liquid capable of printing a good image without color blur, feathering, or color bleed on both absorptive and non-absorbable recording media. .

[0013]

Means for Solving the Problems As a result of intensive studies, the present inventors have conducted printing on an absorptive recording medium by an ink jet recording method using two liquids consisting of a specific ink composition and a specific reaction liquid. As a result, a good image without color bleeding or color bleed was obtained.In addition, even when printing was performed using the same ink on a non-absorbing recording medium, color bleeding, feathering, and color It has been found that good images without bleed can be obtained. Furthermore, the present inventors have also found that these images have excellent fixing properties, abrasion resistance, and water resistance despite being formed using aqueous inks.

The present invention has been made on the basis of the above findings, and has an aqueous ink composition containing a coloring material and a cationic resin emulsion; an anionic reactant which forms an aggregate when contacted with the ink composition; and And a reaction liquid containing an anionic resin emulsion.

Further, the present invention provides a recording method for forming an image on a recording medium using the two-part reaction type recording liquid,
It is another object of the present invention to provide a recording method, which comprises a step of adhering the reaction liquid on a recording medium and a step of adhering the ink composition on a recording medium to form an image.

Further, the present invention provides a recorded matter wherein an image is formed on a recording medium by using the two-part reaction type recording liquid or by using the recording method. It is.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on preferred embodiments. (Two-component reaction type recording solution) The two-component reaction type recording solution of the present invention comprises an aqueous ink composition containing a colorant and a cationic resin emulsion, and an anionic ink which forms an aggregate when contacted with the ink composition. And a reaction solution containing a reaction agent and an anionic resin emulsion. The two-part reaction type recording liquid of the present invention has a good coloring material that is firmly fixed to the recording medium by adhering the ink composition and the reaction liquid to the recording medium, and has no color bleed or color bleed. It is possible to achieve high image quality. The reason why such an effect occurs is not clear, but can be inferred as described below.

First, when the ink composition and the reaction liquid come into contact with each other on the recording medium, the anionic reactant and the anionic resin emulsion in the reaction liquid are converted into the coloring material and the cationic resin emulsion in the ink composition. It is considered that the dispersion state of the particles is destroyed and the particles are aggregated. It is considered that the coloring material is fixed when these aggregates adhere to the surface of the recording medium.

Further, in the present invention, the ink composition contains a cationic resin emulsion, and the reaction liquid contains an anionic resin emulsion. It is expected that this is accelerating retention.

Next, the reaction liquid and the ink composition are brought into contact with each other, and the printed surface of the image formed on the absorbent recording medium is
At the beginning of the contact, agglomeration composed of a coloring material and a resin emulsion and water or a water-soluble organic solvent separated from the agglomerate exist near the surface of the recording medium. Then, water or a water-soluble organic solvent that is unnecessary for fixing the aggregates penetrates into the recording medium or evaporates and is removed from the surface,
The aggregate is fixed only on the recording medium, and the aggregation of the resin emulsion is promoted. The resin emulsion is united to form a resin film. This resin film is
The surface functional groups of the cationic resin emulsion and the surface functional groups of the anionic resin emulsion are electrostatically bonded, and in addition, the surface functional groups are further strengthened by hydrogen bonds formed with the hydrophilic groups present on the recording medium surface. It is presumed that the toner is fixed on the surface of the recording medium and the image is fixed on the surface of the recording medium. Since this agglutination reaction is a quick reaction that occurs instantaneously, it is considered that the occurrence of color bleeding and color bleeding can be suppressed. In addition,
The above mechanism is only an assumption, and the present invention is not construed as being limited to this mechanism.

When an image is formed on the surface of a non-absorbing recording medium by the two-part reaction type recording liquid of the present invention, the separated water or water-soluble organic solvent is removed by a method such as washing to remove the resin. It is preferable to promote the formation of a film.
This resin film does not redissolve in water after the aggregate is dried, and has water resistance, so that color bleeding and color bleeding do not occur even after the recording medium absorbs water.

As described above, the two-part reaction type recording liquid of the present invention includes at least two parts of a specific aqueous ink composition and a specific reaction liquid. Therefore, each of the aqueous ink composition and the reaction liquid included in the recording liquid of the present invention will be described in detail.

(Aqueous ink composition) The aqueous ink composition provided in the two-pack reaction recording liquid of the present invention contains a coloring material and a cationic resin emulsion. The aqueous ink composition usually contains a water-soluble organic solvent and water. In the present invention, the ink composition refers to a black ink composition when performing monochrome printing, and a color ink composition set including at least four colors when performing color printing, specifically, a yellow ink composition. It is also possible to use ink compositions, magenta ink compositions, cyan ink compositions, and even red, green, blue, orange, and violet ink compositions used for the purpose of expanding the color reproduction range. In addition, a black ink composition is included.

(Cationic Resin Emulsion) The cationic resin emulsion contained in the ink composition is a resin dispersion composition (resin emulsion) in which the continuous phase is water and the dispersed phase is a resin component. Some polymer particles have functional groups such as quaternary ammonium, pyridinium, and quaternary phosphonium on the surface, dissociate in water, show a positive zeta potential, and do not aggregate due to their electrostatic repulsion. Refers to a dispersion of polymer fine particles that is stably maintained in a dispersed state.

As the resin component of the dispersed phase, acrylic resin, vinyl acetate resin, styrene-butadiene resin,
Examples include vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenol resin, silicone resin, epoxy resin, and the like.

According to a preferred embodiment of the present invention, the cationic resin emulsion preferably has a minimum film-forming temperature of room temperature or lower, and in fact, has a minimum film-forming temperature of 20 ° C. or lower. Is preferred. If the film formation of the cationic resin emulsion can be carried out at room temperature or lower, the printed recording medium does not require any special heating means. It is preferable because it firmly adheres to the surface.

Here, the "minimum film forming temperature" means that a water-dispersible resin emulsion obtained by dispersing a resin emulsion in water is thinly cast on a metal plate such as aluminum and the temperature is raised. The minimum temperature at which a transparent continuous film is formed when heated. In a temperature range lower than the minimum film forming temperature, a white powder is formed. Further, according to a preferred embodiment of the present invention, the glass transition point of the resin emulsion particles is more preferably 10 ° C. or lower.

"Film-forming property" means that when a resin emulsion is dispersed in water to form a water-dispersible emulsion, a resin film is formed as the water component evaporates. The ink composition to which the resin emulsion has been added has a property that a resin film is similarly formed when water or an aqueous organic solvent is evaporated. The resin film plays a role of firmly fixing the color material component in the ink composition to the surface of the recording medium. by this,
It is considered that an image having excellent durability and water resistance can be realized.

The amount of the cationic resin emulsion (solid content) is preferably 1 to 2 with respect to the ink composition.
It is 5% by weight, more preferably 5 to 15% by weight. Further, the cationic resin emulsion is preferably contained in a weight ratio of 1 to 20, more preferably 2 to 10, with respect to the colorant.

The particle size of the cationic resin emulsion is preferably 100 nm or less, more preferably 5 to 8 nm.
0 nm.

In the present invention, those having a single particle structure can be used as the cationic resin emulsion. On the other hand, in the present invention, it is also possible to use a resin emulsion having a core-shell structure composed of a core portion and a shell portion surrounding the core portion. In the present invention, the “core-shell structure” means “a form in which two or more polymers having different compositions exist in a phase-separated state in a particle”. Therefore, not only a form in which the shell part completely covers the core part but also a part in which the core part is partially covered may be used. Further, a part of the shell polymer may form a domain or the like in the core particle. In addition, in the middle of the core and shell, even more,
It may have a multilayer structure of three or more layers including layers having different compositions.

The cationic resin emulsion can be obtained by known emulsion polymerization. That is, it can be obtained by emulsion polymerization of an unsaturated vinyl monomer in water in the presence of a polymerization catalyst and an emulsifier. Similarly, examples of the unsaturated vinyl monomer include acrylic acid ester monomers, methacrylic acid ester monomers, aromatic vinyl monomers, vinyl ester monomers, olefin monomers, and diene monomers commonly used in emulsion polymerization. Can be In addition, monomers used to introduce a cationic functional group on the surface include, for example, dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, and the like. Examples include quaternary ammonium salts and pyridinium salts. Examples of usable emulsifiers include cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof.

As described above, in the present invention,
It is preferable to have a structure in which a molecule derived from the above monomer is crosslinked by a crosslinking monomer having two or more polymerizable double bonds. Examples of crosslinkable monomers having two or more polymerizable double bonds include diacrylate compounds, triacrylate compounds, tetraacrylate compounds, hexaacrylate compounds, dimethacrylate compounds, trimethacrylate compounds, methylenebisacrylamide, and divinylbenzene. No.

The resin emulsion having a core-shell structure is produced by a known method, generally by multi-stage emulsion polymerization or the like. For example, it can be manufactured by the method disclosed in JP-A-4-76004.
Examples of unsaturated vinyl monomers used for polymerization include:
Those mentioned above are also mentioned. In addition, an initiator, a surfactant, a molecular weight modifier, a neutralizing agent, and the like used in the emulsion polymerization may be used according to a conventional method.

In the present invention, the cationic resin emulsion may be mixed with other components of the ink composition. However, preferably, the cationic resin emulsion is dispersed in water and then mixed with other components of the ink composition. Preferably. In addition, the cationic resin emulsion is preferably used as the last added component in the step of producing the ink composition.

According to a preferred embodiment of the present invention, a surfactant is added together with the cationic resin emulsion, and the mixing ratio of the resin component and the surfactant is adjusted to 1: 1 to 25: 1.
It is preferred that When the amount of the surfactant is within the above range, good water resistance and permeability of the ink can be obtained. The surfactant is not particularly limited, but preferred examples thereof include nonionic (nonionic) surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkyl. Phenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and acetylene glycol derivatives (Olefin Y and Surfynol 8
2, 104, 440, 465, and 485 (all Air Products
and Chemicals Inc.)). These can be used alone or in combination of two or more. In particular, as a surfactant to be mixed with the cationic resin emulsion, it is preferable to add an acetylene glycol derivative such as Surfynol 465 from the viewpoint of improving dispersion stability and color development.

Examples of the surfactant include anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium salt of polyoxyethylene alkyl ether sulfate), and cationic surfactants (for example, dodecyltrimethyl). Ammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium bromide, etc.), amphoteric surfactants (for example, betaine,
Lauryl sulfobetaine, octyl sulfobetaine, 1
-(3-sulfopropyl) pyridinium betaine, etc.),
These may be used alone or in combination of two or more.

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

In the present invention, as the cationic resin emulsion satisfying the above conditions, a known resin emulsion can be used.

(Coloring Material) The coloring material contained in the ink composition provided in the two-pack reaction recording liquid of the present invention may be either a dye or a pigment. It is preferred that It is also possible to use a pigment and a dye together. The pigment is not particularly limited, and any of an inorganic pigment and an organic pigment can be used. 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. As the organic pigment, azo dyes (Azo Lake,
Including insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc., polycyclic pigments (for example, phthalocyanine pigments,
Perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinoflurone pigments),
Dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like can be used.

Particularly, carbon black used as black ink includes Mitsubishi Chemical No. 2300, No. 900, MCF
88, No.33, No.40, No.45, No.52, MA7, MA8, MA100,
No.2200B etc. are Raven 5750, Raven 52 manufactured by Columbia
50, Raven 5000, Raven 3500, Raven 1255, Raven 700
Etc. are Cabot's Regal 400R, Regal 330R, Rega
l 660R, Mogul L, Monarch 700, Monarch 800, Monarc
h 880, Monarch 900, Monarch 1000, Monarch 1100, Mo
narch 1300, Monarch 1400 etc. are Degussa Color
Black FW1, Color Black FW2, Color Black FW2V, Colo
r Black FW18, Color Black FW200, Color Black S15
0, Color Black S160, Color Black S170, Printex 3
5, Printex U, Printex V, Printex 140U, Special Bl
ack 6, Special Black 5, Special Black 4A, Special
Black 4 etc. can be used. Pigments used in the yellow ink include CI Pigment Yellow 1, CI Pigment Ye
llow 2, CI Pigment Yellow 3, ClPigment Yellow 1
2, CI Pigment Yellow 13, CI Pigment Yellow 14C,
CI Pigment Yellow 16, CI Pigment Yellow 17, CI
Pigment Yellow 73, CI Pigment Yellow 74, CI Pigm
ent Yellow 75, CI Pigment Yellow 83, CI Pigment
Yellow 93, CI Pigment Yellow 95, CI Pigment Yell
ow 97, CI Pigment Yellow 98, CI Pigment Yellow 1
14, CI PigmentYellow 128, CI Pigment Yellow 12
9, CI Pigment Yellow 151, CI Pigment Yellow 154 and the like. The pigments used in magenta ink include CI Pigment Red 5, CI Pigment Red 7,
CIigment Red 12, CIigment Red 48 (Ca), CI
Pigment Red 4 (Mn), CI Pigment Red 57 (Ca), C.
I.Pigment Red 57: 1, CI Pigment Red 112, CI Pigm
ent Red 122, CI Pigment Red123, CI Pigment Red 1
68, CI Pigment Red 184, CI Pigment Red 202 and the like. As the pigment used for cyan ink, C.I.
I. Pigment Blue 1, CI Pigment Blue 2, CI Pigment
Blue 3, CI Pigment Blue 15: 3, CI Pigment Blue 1
5:34, CI Pigment Blue 16, CI Pigment Blue 2
2, CI Pigment Blue 60, CIVat Blue 4, CIVat Bl
ue 60.

The particle size of the pigment is preferably 10 μm or less, more preferably 0.1 μm or less.

The pigment is preferably added to the ink as a pigment dispersion 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 this pigment dispersion will also function as the surfactant of the ink composition.

Preferred examples of the polymer dispersant include natural polymers, and specific examples thereof include proteins such as glue, gelatin, casein and albumin; natural rubbers such as gum arabic and tragacanth; saponin and the like. Glucosides; alginic acid derivatives such as alginic acid and propylene glycol alginate, triethanolamine alginate and ammonium alginate; and cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and ethylhydroxycellulose. Further, preferred examples of the polymer dispersant include synthetic polymers, such as polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, and vinyl acetate-
Acrylic resins such as acrylic ester copolymers and acrylic acid-acrylic ester copolymers; styrene-
Acrylic acid copolymer, styrene-methacrylic acid copolymer, sterene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylsterene-acrylic acid copolymer, sterene-α-methylstyrene-acrylic acid-acrylic acid Styrene-acrylic resin such as ester copolymer; styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, and vinyl acetate- Vinyl acetate copolymers such as ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer And their salts. Among them, a copolymer of a monomer having a hydrophobic group and a monomer having a hydrophilic group, and a polymer composed of a monomer having both a hydrophobic group and a hydrophilic group in a molecular structure are preferable.

In the present invention, it is preferable to use a cationic dispersant among the above-mentioned dispersants, since dispersion stability and printing characteristics can be improved. Specific examples of the cationic dispersant include dimethylaminoethyl acrylate, dialkylaminoacrylates such as diethylaminoethylacrylate, dialkylaminomethacrylates such as dimethylaminoethyl methacrylate, dimethylaminostyrene, diethylaminostyrene, methylethylamino Dialkylaminostyrene such as styrene and its quaternary ammonium derivative, methacryloxyethyltrimethylammonium chloride,
Monomers such as methacrylamidopropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, and vinylbenzyltrimethylammonium chloride, and the above-mentioned unsaturated vinyl monomers (the ones used for obtaining a cationic resin emulsion by emulsion polymerization) As the example)
And copolymers thereof. Here, the number of carbon atoms constituting the alkyl group or the alkylene group of these compounds is preferably 1 to 3.

The content of the coloring material in the ink composition is as follows:
It is preferably from 0.5 to 25% by weight, more preferably from 2 to 1% by weight.
5% by weight.

(Other Components in Ink Composition) As a solvent of the ink composition provided in the two-pack reaction type recording liquid of the present invention, water and a water-soluble organic solvent are usually used as main components.

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

Among them, it is preferable to use a water-soluble organic solvent having a boiling point of 180 ° C. or higher. Use of a water-soluble organic solvent having a boiling point of 180 ° C. or higher results in water retention and wettability of the ink composition. As a result, even if the ink composition is stored for a long period of time, there is no aggregation or increase in viscosity of the coloring material, and excellent storage stability can be realized. In addition, open state (state in contact with air at room temperature)
Ink composition that can maintain fluidity and redispersibility for a long time even if left as is. Further, in the ink jet recording method, nozzle clogging does not occur at the time of restarting during printing or after printing is interrupted, and high ejection stability can be obtained.

Examples of the water-soluble organic solvent having a boiling point of 180 ° C. or more include ethylene glycol (boiling point: 197 ° C .; hereinafter, the boiling point is shown in parentheses), 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-1,2
3-hexanediol (243 ° C), 2-methyl-2,4-pentanediol (197 ° C), N-methyl-2-pyrrolidone (202 ° C), 1,3-dimethyl-2-imitazolidinone (25 ° C)
7-260 ° C), 2-pyrrolidone (245 ° C), glycerin (29
0 ° 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 (202 ° C), and diethylene glycol monomethyl ether (194 ° C). Those having a boiling point of 200 ° C. or higher are preferred. These water-soluble organic solvents can be used alone or in combination of two or more.

The content of these water-soluble organic solvents is preferably 0.5 to 40% by weight with respect to the ink composition.
More preferably, it is 2 to 30% by weight.

Further, according to a preferred embodiment of the present invention, the ink composition provided in the two-part reaction type recording liquid of the present invention has various surface active properties in order to improve the affinity (“wetability”) for the recording medium. Agents can be included. As examples of the surfactant, the same surfactant as that used in the preparation of the above-described cationic resin emulsion can be suitably used. Examples of such surfactants include nonionic (nonionic) surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene Ethylenealkylamine, polyoxyethylenealkylamide, and acetylene glycol derivatives (Olefin Y and Surfynol 82, 104, 440, 465,
And 485 (both Air Products and Chemicals In
c.). These can be used alone or in combination of two or more. In particular, as a surfactant to be added to the ink composition, an acetylene glycol derivative such as Surfynol 465 is preferable because dispersion stability and color development can be improved.

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

(Reaction liquid) The reaction liquid included in the two-part reaction type recording liquid of the present invention contains an anionic reactant and an anionic resin emulsion.

(Anionic Resin Emulsion) In the present invention, the anionic resin emulsion comprises an anionic reactant described later in the reaction solution, in particular, a polyacrylic acid-based copolymer such as a polystyrene-acrylic acid copolymer; Interaction with methylcellulose or a salt thereof, for example, has the effect of promoting the fixation of the coloring material to the surface of the recording medium.

The anionic resin emulsion is a resin dispersion composition (resin emulsion) in which the continuous phase is water and the dispersed phase is a resin component. Having a functional group showing charge, carboxyl group, sulfone group, etc., it has a negative zeta potential in water, and keeps a relatively stable dispersed state without aggregation due to its electrostatic repulsion. , A dispersion of fine polymer particles. Here, the resin component of the dispersed phase is the same as that in the cationic resin emulsion in the ink composition described above. Further, the anionic resin emulsion also has a property of reacting with and coagulating with the cationic resin emulsion by electrostatic interaction similarly to the anionic reactant.

According to a preferred embodiment of the present invention, the anionic resin emulsion preferably has a minimum film-forming temperature of room temperature or lower for the same reason as the cationic resin emulsion described above. It is preferable that the film has a minimum film forming temperature of not more than ° C.

The amount (solid content) of the anionic resin emulsion is preferably 1 to 25% by weight, more preferably 5 to 15% by weight, based on the reaction solution.

The particle size of the anionic resin emulsion is, like the particle size of the cationic resin emulsion, preferably 100 nm or less, more preferably 5 to 80 nm.
nm.

According to a preferred embodiment of the present invention, it is preferable that the anionic resin emulsion has a carboxyl group or a sulfone group on its surface and has high reactivity with a cationic functional group. Such high reactivity is considered to be due to the fact that the anionic resin emulsion has relatively many carboxyl groups or sulfone groups on its surface.

An ink composition comprising an anionic resin emulsion having a large amount of a carboxyl group or a sulfone group on its surface so as to exhibit high reactivity as described above,
Low affinity for nozzle plate of water-repellent ink jet recording head. Therefore, the phenomenon that the ink composition wets the nozzle plate nonuniformly, which has conventionally been a problem in the ink composition containing the anionic resin emulsion, and the phenomenon that the ink droplet flies and the ejection failure occurs can be effectively prevented. Therefore, it has a great advantage. According to a preferred embodiment of the present invention, the contact angle of an aqueous emulsion obtained by dispersing an anionic resin emulsion in water at a concentration of 10% by weight on a Teflon (registered trademark) plate is preferably 70 ° or more. Further, the surface tension of the water-dispersible emulsion obtained by dispersing the resin emulsion in water at a concentration of 35% by weight is preferably 40 × 10 ⁻³ N / m (20 ° C.) or more. By using the anionic resin emulsion as described above, the ink jet recording method can further prevent flight bending and achieve good printing.

Further, the ink composition has an advantage that excellent storage stability can be obtained due to dispersion stability caused by the high hydrophilicity of the surface of the anionic resin emulsion.

According to another preferred embodiment of the present invention, the anionic resin emulsion comprises 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having a carboxyl group, and has a polymerizable double bond. Preferably, it has a structure crosslinked by two or more crosslinkable monomers, and contains 0.2 to 4% by weight of a structure derived from the crosslinkable monomer. Due to the use of a cross-linkable polymer obtained by copolymerizing cross-linkable monomers having two or more polymerizable double bonds, more preferably three or more at the time of polymerization and three-dimensionally cross-linking, the nozzle plate surface may be changed depending on the ink composition. Further, it becomes difficult to get wet, the bending of the flight can be further prevented, and the ejection stability can be further improved.

In the present invention, these anionic resin emulsions may have a single-particle structure as in the case of the cationic resin emulsion, or may be composed of a core and a shell surrounding the core. It is also possible to use a resin emulsion having the following core-shell structure.

According to a preferred embodiment of the present invention, the anionic resin emulsion is preferably one in which the core is made of a resin having an epoxy group and the shell is made of a resin having a carboxyl group. The epoxy group and the carboxyl group have the property of reacting with each other, but these two groups are present separately in the core and the shell. Due to the decrease in water or the water-soluble organic solvent, the resin emulsions unite and deform due to the pressure accompanying film formation.
As a result, the epoxy group of the core and the carboxyl group of the shell are combined to form a horizontal mesh structure. Thereby, there is obtained an advantage that a film having higher strength can be formed. The amount of the unsaturated vinyl monomer having an epoxy group is preferably from 1 to 10% by weight. In addition,
Here, the reaction between some epoxy groups and carboxyl groups before film formation is permissible in the present invention unless the film-forming ability is lost. In the present invention, the property that a reactive functional group coexists in such a resin emulsion and that the group reacts during film formation without adding a curing agent to form a network structure is referred to as "self-crosslinking property". Call.

The anionic resin emulsion having a core-shell structure is produced by a known method, generally by multi-stage emulsion polymerization, similarly to the above-described cationic resin emulsion having a core-shell structure. Examples of the unsaturated vinyl monomer used for the polymerization include those described below.

The introduction of an epoxy group into the above-mentioned core portion is achieved by converting an unsaturated vinyl monomer having an epoxy group into
Glycidyl acrylate, glycidyl methacrylate,
Examples include a method of copolymerizing allyl glycidyl ether or the like with another unsaturated vinyl monomer, or a method of simultaneously adding an epoxy compound to prepare core particles by polymerizing one or more unsaturated vinyl monomers to form a composite. Can be. The former method is preferred from the viewpoint of easiness of polymerization and polymerization stability.

The anionic resin emulsion used in the present invention can be obtained by known emulsion polymerization.
That is, it can be obtained by emulsion polymerization of an unsaturated vinyl monomer (unsaturated vinyl monomer) in water in the presence of a polymerization catalyst and an emulsifier. As unsaturated vinyl monomers, acrylate monomers, methacrylate monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl cyanide compound monomers, halogenated monomers, which are generally used in emulsion polymerization, Examples include olefin monomers and diene monomers. Further, as specific examples, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate , Octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate,
Acrylates such as methyl methacrylate;
Ethyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, pendyl methacrylate, glycidyl methacrylate And vinyl esters such as vinyl acetate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; halogenated monomers such as vinylidene chloride and vinyl chloride;
Styrene, 2-methylstyrene, vinyl toluene, tert
-Aromatic vinyl monomers such as butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene;
Olefins such as ethylene, propylene, and isopropylene; dienes such as butadiene and chloroprene; and vinyl monomers such as vinyl ether, vinyl ketone, and vinylpyrrolidone. For monomers having no carboxyl group, it is essential to use an unsaturated vinyl monomer having a carboxyl group.
Acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid are listed, and among them, use of methacrylic acid is preferred. Further, usable emulsifiers include anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof.

As described above, in the present invention,
It is preferable to have a structure in which a molecule derived from the above monomer is crosslinked by a crosslinking monomer having two or more polymerizable double bonds. Examples of crosslinkable monomers having two or more polymerizable double bonds include polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate,
1,6-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2 ′
Diacrylate compounds such as -bis (4-acryloxypropoxyoxyphenyl) propane and 2,2'-bis (4-acryloxydiethoxyphenyl) propane; trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane Triacrylate compounds such as triacrylate; tetraacrylate compounds such as ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate and pentaerythritol tetraacrylate; hexaacrylate compounds such as dipentaerythritol hexaacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triacrylate Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene Recall dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6
-Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate,
2,2'-bis (4-methacryloxydiethoxyphenyl)
Dimethacrylate compounds such as propane; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethanetrimethacrylate;
Examples include methylenebisacrylamide and divinylbenzene.

Further, by adding acrylamides or hydroxyl group-containing monomers in addition to the above-mentioned monomers, the printing stability can be further improved. Examples of acrylamides include acrylamide and N,
N'-dimethylacrylamide is exemplified. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and these may be used alone or in combination of two or more. Can be.

Further, an initiator used in the emulsion polymerization,
Surfactants, molecular weight regulators, and neutralizing agents may also be used in accordance with a conventional method.

In the present invention, the anionic resin emulsion may be mixed with other components of the reaction solution. However, it is preferable that the emulsion is dispersed in water and then mixed with other components of the reaction solution. In addition, the anionic resin emulsion is preferably used as the last added component in the step of producing a reaction solution.

In the present invention, a known anionic resin emulsion can be used as the anionic resin emulsion satisfying the above conditions.

(Anionic Reactant) In the present invention, the “anionic reactant” is a substance capable of destroying the state of dispersion of the coloring material and the cationic resin emulsion in the ink composition and causing them to aggregate. Examples thereof include polyacrylic acid-based copolymers such as polystyrene-acrylic acid copolymer, polystyrene-methacrylic acid copolymer, polyacrylic acid-acrylic acid ester copolymer, and polymethacrylic acid-acrylic acid ester copolymer. Coalescence, carboxymethylcellulose,
And salts thereof.

The concentration of the anionic reactant in the reaction solution is preferably 1 to 5% by weight from the viewpoint of improving the water resistance, storage stability and recording stability of a recorded image such as a printed matter. Preferably it is 2-3% by weight.

According to a preferred embodiment of the present invention, a triethanolamine salt, an ammonium salt, and a sodium carboxymethylcellulose of a polystyrene-acrylic acid copolymer are provided as an anionic reactant.

(Other Components in Reaction Solution) The solvent of the reaction solution used in the present invention usually contains water and a water-soluble organic solvent as main components.

According to a preferred embodiment of the present invention, the reaction solution contains a wetting agent comprising a high-boiling organic solvent. The high-boiling organic solvent prevents the reaction solution from drying. Preferable examples of the high boiling point organic solvent partially overlap with the above-mentioned polyols, but include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, and thioglycol. Polyhydric alcohols such as hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene Examples include alkyl ethers of polyhydric alcohols such as glycol monobutyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and triethanolamine. According to a preferred embodiment of the present invention, the reaction solution preferably contains a combination of triethylene glycol monobutyl ether and glycerin.

The amount of the high boiling organic solvent to be added is not particularly limited, but is preferably 0.5 to 40% by weight based on the reaction solution.
And more preferably 2 to 20% by weight.

The reaction solution may contain a low-boiling organic solvent. Preferred examples of the low boiling organic solvent include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, 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. The addition amount of the low boiling organic solvent is preferably 0.5 to 10% by weight, and more preferably 1.5 to 6% by weight.

The reaction solution may contain a substance having a surface active effect. Examples of these compounds include various surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, alcohols such as methanol, ethanol, and iso-propyl alcohol, and ethylene glycol. And lower alkyl ethers of polyhydric alcohols such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether. By adding these to the reaction solution, it becomes possible to improve the permeability and affinity (“wetability”) of the reaction solution to the recording medium. Specific examples of the above compounds include Orfin Y, Surfynol 82, Surfynol 440, Surfynol 465, Surfynol 48
5 (All manufactured: Air Products and Chemicals In
c. ). These may be used alone or in combination of two or more.

The reaction solution may contain triethanolamine for pH adjustment. When triethanolamine is added, the addition amount is preferably 0.1 to 2.0% by weight.

Further, the reaction liquid may be colored by adding the coloring material described in the above-mentioned ink composition, the extender pigment and other coloring materials, and may have the function of the ink composition. .

(Recording Method) The present invention further relates to a recording method for forming an image on a recording medium by using the above-described two-part reaction type recording liquid, comprising the steps of: adhering the reaction liquid onto the recording medium; The present invention also provides a recording method including a step of forming an image by adhering the ink composition on a recording medium.

In the recording method of the present invention, in the printing step, the ink composition and the reaction liquid are adhered to a recording medium, so that the color It is feasible that the material is firmly fixed to the recording medium and good image quality without color bleed or color bleed is obtained.

The order in which the reaction liquid and the ink composition are adhered to the recording medium is, unless there is any inconvenience in the process, a method of adhering the reaction liquid to the recording medium and then adhering the ink composition to the recording medium, Any of the methods for simultaneously attaching the liquid and the ink composition can be selected.

According to a preferred embodiment of the present invention, the step of depositing the ink composition droplets on the recording medium is performed simultaneously with the step of depositing the reaction liquid on the recording medium, because it is advantageous in terms of productivity. A method is provided.

Regarding the adhesion of the reaction liquid to the recording medium, either the method of selectively depositing the reaction liquid only at the place where the ink composition is applied or the method of attaching the reaction liquid to the entire recording medium is used. There may be. The former is economical because the consumption of the reaction liquid can be suppressed to the minimum necessary amount, 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, the latter requires less precision of the position where the reaction liquid and the ink composition are adhered than the former, but causes a large amount of the reaction liquid to adhere to the entire recording medium, which is disadvantageous in terms of cost. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid.

The means for attaching the reaction liquid to the recording medium and the means for attaching the ink composition to the recording medium are described in the printing industry,
Recording methods commonly used in the coatings industry are possible and include, for example, direct injection, spraying, coating, transfer and the like. Among them, the step of attaching droplets of the ink composition on a recording medium, or the step of attaching a reaction liquid to the recording medium, in terms of good productivity, low facility load, and cost advantages, An ink jet recording method in which droplets are ejected and adhered to a recording medium to perform printing, particularly an on-demand ink jet recording method in which droplets are ejected to a recording medium to perform printing only in printing, is most preferable.

In the present invention, examples of the recording medium include those having water absorbency with respect to the ink composition, such as paper, cloth, nonwoven fabric, porous film, and polymer absorber. Specific examples of the absorptive recording medium to which the recording method of the present invention can be applied include media based on paper, natural fibers and / or synthetic fibers such as cloth and nonwoven fabric, media processed with synthetic resin, and inorganic and organic media. Media composed of a porous film made of a material, media processed with a water-absorbing polymer, recording media in which these are laminated, and recording media in which two or more of these media are combined and combined, and the like. . In particular,
"Xerox" manufactured by Xerox Co., Ltd.
"P", "Xerox 4024" (all trade names), so-called plain paper such as "High-quality plain paper" manufactured by Seiko Epson Corporation, and paper of a type having an ink absorbing layer made of an inorganic / organic material on the surface. Examples include “MC mat paper” and “Photo print paper 2” manufactured by Seiko Epson Corporation.

The base material that does not substantially absorb ink in the present invention, that is, the non-absorptive recording medium includes synthetic resin, rubber, metal, glass, ceramics, and the like. In order to add, a base material obtained by combining and combining a plurality of these materials can also be used. Specific examples include a PET film, an aluminum plate, and a polyolefin sheet.

In addition, in order to further increase the strength and durability of the recording medium and to add functionality, an absorbent base material and a non-water-absorbent base material are combined by means such as lamination or compounding. It is possible to use a recording medium.

Further, it is preferable that the recording medium has a laminated structure composed of a single component such as paper, cloth, nonwoven fabric, porous film, polymer absorber, metal, ceramics, rubber, and synthetic resin. This is preferable from the viewpoint of imparting high functionality to the obtained recorded matter and improving the mechanical strength of the recorded matter. Specific examples include a paper napkin.

The recording medium may be paper, cloth, non-woven fabric,
Porous membrane, polymer absorber, metal, ceramics, rubber,
It is preferable to have a laminated structure in which two or more materials such as synthetic resins are combined in order to impart high functionality to the obtained recorded matter. For example, RC paper (both sides of paper are coated with resin such as polyethylene film,
(A recording medium with an ink absorbing layer on the recording surface)
And an aluminum-deposited PET film.
Among them, a specific example of RC paper is PM photo paper <gloss> manufactured by Seiko Epson Corporation Model number: KA42
0PSK, MC photo paper <semi-gloss> Model number: KA420M
SH and the like.

(Recorded matter) The present invention further provides a recorded matter obtained by forming an image on a recording medium by using the two-part reaction type recording liquid described above or by using the recording method described above. Things. The recorded matter of the present invention has a good image without color blur, feathering, and color bleed.

[0096]

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.

Example 1 Preparation of Cationic Resin Emulsion Dispersion 100 ml of distilled water and 0.1 g of potassium persulfate were added to a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While replacing, the internal temperature was heated to 75 ° C. Next, 260 ml of distilled water, 2.0 g of nonionic surfactant Surfynol-465, 100 g of methacryloxyethyltrimethylammonium chloride, 30 g of 2-hydroxyethyl acrylate, 100 g of acrylonitrile, and 70 g of butyl acrylate were stirred to prepare a mixture. This was gradually dropped into the flask over 3 hours using a dropping funnel. After the obtained emulsion was cooled to room temperature and neutralized with potassium hydroxide, this emulsion was filtered with a 0.4 μm filter, and prepared with distilled water so that the concentration of the resin emulsion became 30%. .

Preparation of Anionic Resin Emulsion Dispersion 100 ml of distilled water and 0.1 g of potassium persulfate were added to a flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel. The temperature was heated to 70 ° C. Next, 100 ml of distilled water, 1.0 g of sodium dodecylbenzenesulfonate, 30 g of styrene, 55 g of 2-ethylhexyl acrylate, and 5 g of methacrylic acid were stirred to prepare an emulsion. This was gradually dropped into the flask using a dropping funnel. The obtained emulsion was cooled to room temperature, and this emulsion was filtered with a 0.4 μm filter, and prepared with distilled water so that the concentration of the resin emulsion became 30%. The obtained emulsion showed a property of aggregating when mixed with a reaction solution described later.

Preparation of Ink Composition An ink composition having the following composition was prepared. Preparation was performed in the following manner. A pigment, a dispersant, and water are mixed and mixed in a sand mill (manufactured by Yasukawa Seisakusho).
1.7 mm, 1.5 times (weight) of the mixture) for 2 hours. Thereafter, the glass beads were removed to prepare a pigment dispersion. Next, a solvent excluding the pigment and the dispersant was mixed and used as an ink solvent. The ink solvent was gradually dropped while stirring the above-described pigment dispersion, followed by stirring at room temperature for 20 minutes. Thereafter, the cationic resin emulsion dispersion was gradually added dropwise, and the mixture was stirred and mixed at room temperature for 10 minutes, and then filtered through a 5 μm membrane filter to obtain an ink composition for inkjet recording.

Black pigment ink composition Carbon black MA-7 (color material, manufactured by Mitsubishi Chemical Corporation) 3% by weight (hereinafter abbreviated as wt)% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate Combined (weight ratio 100: 30: 70) (cationic dispersant) 1 wt% cationic resin emulsion (as solid content) 10 wt% glycerin 10 wt% Surfynol 465 (surfactant, Air Product and Chemicals, Inc) 1 wt% % Remaining ion exchange water

Color Ink Set Cyan Pigment Ink CI Pigment Blue 15: 3 (Coloring Material) 2 wt% Methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butylacrylate copolymer (weight ratio 100: 30: 70) (Cationic dispersant) 1wt% cationic resin emulsion (as solid content) 10wt% diethylene glycol 10wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1wt% ion exchange water

Magenta pigment ink CI Pigment Red 122 (coloring material) 3 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butylacrylate copolymer (weight ratio 100: 30: 70) (cationic dispersant) 1 wt% cationic resin emulsion (as solid content) 10 wt% glycerin 5 wt% diethylene glycol 5 wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1 wt% ion exchanged water

Yellow pigment ink CI Pigment Yellow 74 (coloring material) 3.5 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer (weight ratio 100: 30: 70) (cationic dispersion) 1 wt% cationic resin emulsion (as solid content) 10 wt% glycerin 8 wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1 wt% ion exchange water

Preparation of Reaction Solution A reaction solution was prepared according to the following composition. Preparation was performed in the following manner. While stirring the ion-exchanged water with a magnetic stirrer, carboxymethylcellulose sodium salt is added and mixed and dissolved. After confirming complete dissolution, glycerin and triethylene glycol monobutyl ether are added in this order, and this is also mixed and dissolved. Next, the anionic resin emulsion dispersion was gradually added dropwise, and the mixture was stirred and mixed at room temperature for 10 minutes, and then filtered through a 5 μm membrane filter to obtain a reaction liquid 1.

Reaction Solution 1 Carboxymethylcellulose sodium salt (anionic reactant) 3 wt% (manufactured by Aldrich chemical Inc., ultra-low molecular weight grade) Anionic resin emulsion (as solid content concentration) 10 wt% triethylene glycol monobutyl ether 5 wt% glycerin 10wt% ion exchange water

Recording medium 1: plain paper Xerox P (manufactured by Xerox Corporation) Recording medium 2: plain paper Xerox 4024 (manufactured by Xerox Corporation) Recording medium 3: PET film Xerox Film <No frame> A4 (Fuji Xerox Recording medium 4: Aluminum plate Thickness 0.3 (mm) Recording medium 5: Vinyl chloride sheet Viewcal 900 (manufactured by Lintec Co., Ltd.) Recording medium 6: Polyolefin sheet YUPO FPG 110 (Oji Oil Chemicals, Ltd. )

Example 2 Black Pigment Ink Composition Carbon Black MA-7 (Coloring Material, manufactured by Mitsubishi Chemical Corporation) 5 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer ( (Weight ratio 100: 30: 70) (cationic dispersant) 1 wt% cationic resin emulsion (as solid content) 15 wt% glycerin 10 wt% Surfynol 465 (surfactant) 1 wt% lauryl sulfobetaine (amphoteric surfactant) 0.5wt% ion exchange water

Color pigment ink set Cyan pigment ink CI Pigment Blue 15: 3 (coloring material) 2 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer (weight ratio 100: 30: 70) ) (Cationic dispersant) 1 wt% cationic resin emulsion (as solid content) 15 wt% diethylene glycol 10 wt% Surfynol 465 (surfactant) 1 wt% ion exchange water

Magenta pigment ink CI Pigment Red 122 (coloring material) 3 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butylacrylate copolymer (weight ratio 100: 30: 70) (cationic dispersant) 1 wt% cationic resin emulsion (as solid content) 15 wt% glycerin 5 wt% diethylene glycol 5 wt% Surfynol 465 (surfactant) 1 wt% ion exchange water

Yellow pigment ink CI Pigment Yellow 74 (coloring material) 3.5 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer (weight ratio 100: 30: 70) (cationic dispersion) 1wt% cationic resin emulsion (as solid content) 15wt% glycerin 8wt% Surfynol 465 (surfactant) 1wt% ion exchange water

The ink composition was changed to the above composition, and the other parts were printed on the recording media 1 to 6 in the same manner as in Example 1, and the same evaluation was performed.

Example 3 Reaction Solution 2 Styrene-acrylic acid copolymer ammonium salt (anionic reactant, molecular weight 10,000) 2 wt% anionic resin emulsion (as solid content concentration) 15 wt% triethanolamine (anion 1 wt% triethylene glycol monobutyl ether 5 wt% glycerin 10 wt% ion-exchanged water Remaining Reaction solution 2 having the above composition was prepared in the same manner as in the preparation method of Example 1. Printing was performed on recording media 1 to 6 in the same manner as in Example 1 except that was used, and the same evaluation was performed.

[Comparative Example 1] Black dye ink composition Project Fast Black 2 (coloring material, manufactured by AVECIA) 3.5 wt% glycerin 10 wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1 wt% bird Ethylene glycol monobutyl ether 7wt% ion exchange water

The above dye was added to the ink solvent and dissolved by stirring at room temperature for 20 minutes. Then, the mixture was filtered through a 5 μm membrane filter to obtain an ink composition for inkjet recording. Example 1 except that only the black ink composition was changed to the above composition, and the other color ink compositions did not use a cationic emulsion and did not use a reaction liquid.
Printing was performed on the recording media 1 to 6 in the same manner as described above, and evaluation was performed in the same manner.

Comparative Example 2 Black Pigment Ink Composition Carbon Black MA-7 (Coloring Material, manufactured by Mitsubishi Chemical Corporation) 5 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer ( (Weight ratio 100: 30: 70) (cationic dispersant) 1 wt% glycerin 10 wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1 wt% ion-exchanged water

Color ink set Cyan pigment ink CI Pigment Blue 15: 3 (coloring material) 2 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer (weight ratio 100: 30: 70) (Cationic dispersant) 1wt% diethylene glycol 10wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1wt% ion exchange water

Magenta pigment ink CI Pigment Red 122 (coloring material) 3 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butylacrylate copolymer (weight ratio 100: 30: 70) (cationic dispersant) 1 wt% glycerin 5 wt% diethylene glycol 5 wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1 wt% ion exchange water

Yellow pigment ink CI Pigment Yellow 74 (coloring material) 3.5 wt% methacryloxyethyltrimethylammonium chloride- (2-hydroxyethyl) acrylate-butyl acrylate copolymer (weight ratio 100: 30: 70) (cationic dispersion) 1wt% glycerin 8wt% Surfynol 465 (surfactant, manufactured by Air Product and Chemicals, Inc) 1wt% ion exchange water

The composition of the ink set was changed as described above, and the recording media 1 to 3 were prepared in the same manner as in Example 1 without using the reaction liquid.
And the same evaluation was performed.

Comparative Example 3 Printing was performed on recording media 1 to 3 in the same manner as in Example 1 except that no reaction solution was used, and the same evaluation was performed.

Comparative Example 4 Using the same ink set as in Comparative Example 2, and using the same reaction liquid as in Example 1, printing was performed on recording media 1, 2, and 3 in the same manner as in Example 1. The same evaluation was performed.

Evaluation Test Examples were made by combinations shown in Table 1 below. The printed matter targeted for the following evaluation was prepared by printing the ink composition and the reaction liquid of the above example on a recording medium at normal temperature and normal pressure using an inkjet printer EM-900C manufactured by Seiko Epson Corporation. I got it. Printing was performed by simultaneously discharging the reaction liquid, the black ink, and the color ink onto the recording medium. Thereafter, the recording medium was air-dried, and the following evaluation was performed.

Evaluation item 1: Evaluation of color bleeding after printing The printed material was visually evaluated for bleeding immediately after printing according to the following criteria. A: A good image without bleeding was obtained. B: Slight bleeding occurred. C: Mustache-like bleeding occurred. D: Bleeding occurred so that the color boundary was not clear.

Evaluation item 2: Evaluation of color bleed after printing The printed matter was visually evaluated for uneven color mixture at the color boundary according to the following criteria. A: A good image without color mixture was obtained. B: Color mixture slightly occurred. C: Color mixing was observed. D: Color mixing occurred so that the boundaries of the colors were not clear.

Evaluation item 3: Evaluation of feathering after printing The printed matter was visually evaluated for the presence of mustache-like bleeding according to the following criteria. A: A good image without whisker-like bleeding was obtained. B: Whisker-like oozing slightly occurred. C: A whisker-like bleeding was observed. -: Could not be evaluated due to the effects of bleeding and color bleeding.

Evaluation item 4: Comprehensive evaluation The printed matter was sufficiently dried naturally. The recording media 3 to 6 were sufficiently washed with ion-exchanged water and then air-dried sufficiently, and then visually evaluated.

The results were as shown in Table 1 below.

[0128]

[Table 1]

[0129]

As described above, an aqueous ink composition containing a coloring material and a cationic resin emulsion, an anionic reactant and an anionic resin emulsion which form aggregates when contacted with the aqueous ink composition are used. According to the two-part reaction type recording liquid of the present invention in combination with the reaction liquid containing,
Regardless of whether the recording medium is a material that absorbs the ink composition and the reaction liquid, or a material that does not substantially absorb the ink composition, it is possible to print an image without color bleeding or color bleed on the recording medium.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA05 FC01 FD06 2H086 BA02 BA05 BA11 BA18 BA19 BA21 BA22 BA23 BA53 BA55 BA59 BA62 4J039 AB02 AD09 BC09 BE01 BE22 CA06 EA47 EA48 FA01 FA02 FA03 FA06 GA24

Claims (16)

[Claims] 1. An aqueous ink composition containing a colorant and a cationic resin emulsion, and a reaction liquid containing an anionic reactant and an anionic resin emulsion that form an aggregate when contacted with the ink composition. A two-component reaction type recording liquid characterized by comprising at least: 2. The two-liquid reaction type recording liquid according to claim 1, wherein the coloring material is a pigment. 3. The two-part reactive recording liquid according to claim 1, wherein the amount of the cationic resin emulsion added is 1 to 25% by weight (solid content) based on the ink composition. 4. The two-part reaction type recording liquid according to claim 1, wherein the ink composition further contains a cationic dispersant. 5. The two-part reactive recording liquid according to claim 1, wherein the ink composition further contains a nonionic surfactant. 6. The two-part reaction type recording liquid according to claim 5, wherein the nonionic surfactant is an acetylene glycol derivative. 7. The two-part reaction type according to claim 1, wherein the amount of the anionic resin emulsion added is 1 to 25% by weight (solid content) based on the reaction liquid. Recording liquid. 8. The method according to claim 1, wherein the anionic reactant is at least one selected from the group consisting of polyacrylic acid-based copolymers, carboxymethylcellulose, and salts thereof. Two-component reaction type recording liquid. 9. A recording method for forming an image on a recording medium using the two-part reaction type recording liquid according to claim 1, wherein the reaction liquid is attached to the recording medium. And a step of forming an image by attaching the ink composition onto a recording medium. 10. The recording method according to claim 9, wherein the recording medium is a medium that absorbs an aqueous ink composition such as paper, cloth, nonwoven fabric, a porous film, a polymer absorber, and a reaction liquid. 11. The recording method according to claim 9, wherein the recording medium is a medium that does not substantially absorb an aqueous ink composition such as metal, ceramics, rubber, and synthetic resin and a reaction liquid. 12. The recording medium according to claim 1, wherein the recording medium has a laminated structure composed of a single component such as paper, cloth, nonwoven fabric, porous film, polymer absorber, metal, ceramics, rubber, and synthetic resin. 9. The recording method according to item 9. 13. The recording medium has a laminated structure in which two or more materials such as paper, cloth, nonwoven fabric, porous film, polymer absorber, metal, ceramics, rubber, and synthetic resin are combined. The recording method according to claim 9. 14. The recording according to claim 9, wherein the step of depositing ink composition droplets on the recording medium is performed simultaneously with the step of depositing the reaction liquid on the recording medium. Method. 15. The ink-jet method according to claim 15, wherein the step of depositing a droplet of the ink composition on the recording medium or the step of depositing the reaction liquid on the recording medium is performed by ejecting the droplet and attaching it to the recording medium to perform printing. It is a recording method, Claims 9-
15. The recording method according to any one of 14. 16. The use of the two-part reaction type recording liquid according to any one of claims 1 to 8 or the use of the recording method according to any one of claims 9 to 15, A recorded material comprising an image formed on a recording medium.