JP2001348519A - Light curable ink - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To eliminate "stickiness" after recording on a recording medium, especially a non-absorbent recording medium, to improve fixability and abrasion resistance of a colorant, and to prevent color mixing and clogging. Provided is a two-part ink that has improved water resistance and enables printing with good image quality. SOLUTION: The ink composition in the two-pack type ink includes:
Reactive monomers, reactive oligomers, reactive polymers,
By including a high-boiling wetting agent composed of at least one of reactive sugars and including a polyvalent metal salt and a photo-curing agent in the aggregating liquid, after printing 3 on the recording medium 2, drying 4,
Upon receiving the ultraviolet irradiation 5, the "stickiness" of the image portion is eliminated, the fixability of the colorant and the abrasion resistance are improved, and the image quality is further improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition, a recording method and a recorded product using the same, and a recording apparatus suitable for performing the recording method. The present invention particularly relates to an ink composition suitable for recording on a non-ink-absorbing material or a low-ink-absorbing material such as a plastic or a metal (that is, a non-ink-absorbing recording medium).
The present invention relates to a recording method and a recorded material using the same, and a recording apparatus suitable for performing the recording method.

[0002]

2. Description of the Related Art Conventionally, an aqueous ink composition generally contains water as a main component and further contains a coloring component and a wetting agent such as glycerin. As the recording medium used for the aqueous ink composition, one that can absorb the ink composition to some extent and allow the colorant to permeate, such as paper, is used. As a recording method for performing printing using an aqueous ink composition, an ink jet recording method has recently attracted attention. The ink jet recording method is a recording method in which small droplets of an ink composition fly and adhere to a recording medium to perform printing.

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 plastic or metal, a solvent-based ink composition using an organic solvent (especially lipophilic) is generally used. Paint is used. When printing on a non-absorbable recording medium, the solvent-based ink composition and paint are excellent in sticking property, abrasion resistance, durability and the like. However, certain organic solvents can be toxic to animals and plants. Therefore, attention must be paid to its use and disposal, and handling is often inconvenient.

[0004] Even when printing and painting on a non-absorbent recording medium, the use of an aqueous ink composition can provide safety, environmental, and environmental benefits.
It can be said that it is preferable in terms of convenience of use. However, in printing on a non-absorbent recording medium, it is required that the colorant component of the aqueous ink composition be firmly fixed to the surface of the recording medium. For that purpose, it is required that the time until fixing, that is, the drying time is short. In order to improve the fixability of the colorant to the recording medium, it has been proposed to add a resin to the aqueous ink composition. It is considered that this resin fixes a colorant on the recording medium as a binder.

As an ink composition containing a resin, for example, JP-B-62-1426 discloses an ink in which a pigment and a resin emulsion are dispersed in water.
JP-A-3-60068 discloses that a pigment is dispersed in a water-insoluble resin emulsion dispersion, and JP-A-1-217088 discloses that an emulsion having a specific film-forming temperature is used. Gazette and Japanese Patent Laid-Open No. 4-1
No. 8462 also proposes an ink using a resin emulsion. Further, Japanese Patent Application Laid-Open No. 56-14785
9 and JP-A-56-147860;
JP-A-5703 proposes an aqueous dispersion-based pigment ink using a polymer dispersant and a water-soluble organic solvent.

[0006] However, when recording is performed on a recording medium by an ink jet recording method using an ink composition containing a resin, the resin, the coloring, and the like are reduced due to the presence of a polyvalent metal added to improve water resistance. The agent and the like agglomerated, causing clogging. Therefore, in order to obtain a water-resistant and stable image without color bleeding, an ink composition containing at least one chemical dye having at least one carboxyl group and a polyvalent metal salt solution are separately used. A so-called two-component ink has been proposed (JP-A-5-202328). In addition, in order to obtain a high-quality color image having a high image density and no color bleed, the color ink containing at least a surfactant or a penetrable solvent for imparting permeability and a salt and the salt are used to increase the color ink. It has also been proposed to use a combination of a viscous or agglomerated black ink, that is, to use a two-part ink composed of a first liquid containing a salt and an ink composition (JP-A-6-106735). No.). In addition, an ink jet recording method for recording using a two-component ink has been proposed (for example, Japanese Patent Application Laid-Open No.
240557, JP-A-3-240558).

[0007]

SUMMARY OF THE INVENTION The present inventor has proposed an ink jet recording method using a two-part ink comprising a coagulating liquid and an ink composition as described above to form a recording medium, particularly a non-absorbent recording medium. When recording was performed, it was observed that "stickiness" occurred because the recording surface was hard to harden. When investigating the cause of the "stickiness," the two-pack ink used a water-soluble organic solvent, glycerin, ethylene glycol, diethylene glycol, etc. as a wetting agent, and sugar to prevent clogging. It has been found that the use of a wetting agent having a high boiling point and a water retention property causes "stickiness".

The present invention has been made on the basis of the above findings, and it is an object of the present invention to provide a recording medium, particularly a non-absorbent recording medium, in which the recording surface is solidified at an early stage to eliminate "stickiness". To provide a two-part ink capable of improving the fixability and abrasion resistance of a colorant, not causing color mixing and clogging, improving water resistance, and obtaining good image quality. The purpose of the present invention is to provide a recording method using

[0009]

SUMMARY OF THE INVENTION The present invention provides a monomer, oligomer, polymer, sugar, or sugar having a photoreactive group which becomes a wetting agent at a high boiling point and is polymerized in the presence of a photocuring agent upon irradiation with light. Monomers, oligomers, polymers, and sugars (hereinafter, referred to as “reactive monomers”, “reactive oligomers”, “reactive polymers”, and “reactive sugars”, respectively) in the ink composition. A photocuring agent may be contained in at least one of the coagulation liquid containing at least one of the ink composition and the polyvalent metal salt, polyamine, or polyamine derivative, and the recording portion may be cured by light irradiation after recording. The above object is achieved by a possible two-part ink.

[0010] That is, the photocurable two-pack ink according to the present invention comprises a "high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, a colorant, and a polymer. Fine particles, water, an ink composition containing at least a water-soluble organic solvent, and an aggregating liquid containing at least an aggregating agent that forms an aggregate when contacted with the ink composition; Accordingly, at least one of the ink composition and the aggregating liquid contains a photo-curing agent ”(claim 1).

[0011] The recording method according to the present invention is characterized in that a high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, a coloring agent,
Polymer fine particles, water, an ink composition containing at least a water-soluble organic solvent, and an aggregating liquid containing at least an aggregating agent that forms an aggregate when contacted with the ink composition, Accordingly, a recording method for performing recording using a photocurable two-component ink, wherein at least one of the ink composition and the aggregation liquid contains a photocuring agent, A step of adhering the aggregating liquid onto the recording medium, a step of adhering the ink composition onto the recording medium to record an image, a step of drying at least a recorded image portion after the previous two steps, and a drying step. Later, a step of irradiating at least the recorded image portion with light and curing,
Has "(claim 10).

Further, the recorded matter according to the present invention is "characterized by the above-mentioned recording method" (claim 16), and preferably, "the ink composition on the recording medium" is provided. The step of adhering an object and / or the step of adhering the aggregation liquid onto a recording medium is an ink jet recording method in which droplets are ejected and adhered to the recording medium to perform recording. "

The recording apparatus according to the present invention further comprises a high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, a coloring agent, polymer fine particles, water, An ink composition containing at least a water-soluble organic solvent; and an aggregating liquid containing at least an aggregating agent that forms an agglomerated substance when contacted with the ink composition. A recording apparatus for performing recording using a photocurable two-component ink, wherein at least one of the liquid and the coagulation liquid contains a photocuring agent, and records the coagulation liquid. Means for performing a step of adhering the ink composition on a medium, means for performing a step of recording an image by adhering the ink composition on a recording medium, means for performing a step of drying at least a recorded image portion, (A means for irradiating the recorded image portion with light and performing a step of curing) ”(claim 17), and preferably,“ the means for adhering the aggregation liquid onto a recording medium and / or the ink. The means for adhering the composition onto the recording medium is an ink jet recording mechanism for ejecting liquid droplets and adhering to the recording medium to perform recording "and / or" where the curing means is an ultraviolet irradiation means. There is ".

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is intended to eliminate the "stickiness" that has occurred during recording using a two-part ink using a conventional ink composition containing fine polymer particles. A high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, in place of at least a part of the glycerin, ethylene glycol, diethylene glycol, and sugar used; Accordingly, a light curing agent is used, and light is irradiated after recording to cure the recorded portion.

The ink composition used in the present invention comprises:
Reactive monomers, reactive oligomers, reactive polymers,
A high-boiling wetting agent consisting of at least one reactive sugar,
It contains at least a colorant, polymer fine particles, water, a water-soluble organic solvent, and, if necessary, a photocuring agent. In the present invention, the “ink composition” means a black ink composition when performing monochrome recording, and a color ink composition when performing color printing, specifically, a yellow ink composition and a magenta ink. Composition, and cyan ink composition, and in some cases, black ink composition. Also,
In the present invention, “light” refers to a light having a wavelength of about 1 nm to about 1 m.
m means electromagnetic waves, i.e., ultraviolet light, visible light and infrared light, and in particular, means ultraviolet light having a wavelength of about 220 to 400 nm.

The high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer and a reactive sugar contained in the ink composition is preferably
Has a boiling point of 180 ° C. or more, acryloyl group, methacryloyl group, acrylic group, acrylamide group, allyl group,
Having at least one of a photoreactive group (photopolymerizable group) consisting of a vinyl ether group, a vinyl thioether group and a vinyl amino group, or being cured by being irradiated with light after recording and in the presence of a photocuring agent Is possible.

The reactive monomer may be any monomer having at least one photoreactive group, or any monomer that is polymerized in the presence of a photocuring agent when irradiated with light. And oil-soluble ones. The water-soluble monomer preferably has an adhesion-imparting group in addition to the photoreactive group. The adhesion-imparting group is a functional group that does not participate in the polymerization reaction by the photoreactive group (photopolymerizable group) and has a function of imparting adhesion to the surface of a recording medium (particularly a recording medium having no ink absorption). And examples thereof include an amino group or an amide group. Examples of the water-soluble monomer include, for example, 2
-Hydroxyl ethyl methacrylate, ethyl diethylene glycol acrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethacrylate, methoxypolyethylene glycol methacrylate, ethoxylated trimethylol Examples thereof include propane triacrylate, (meth) acrylate containing a phosphoric acid group, and N-vinyl-2-pyrrolidone.
Of course, these water-soluble monomers can be used alone or in combination of two or more. The content of the water-soluble monomer is preferably 0.1 to the total weight of the ink composition.
It is 5 to 40% by weight, more preferably 1 to 40% by weight. When the content of the water-soluble monomer exceeds 40% by weight, water resistance and moisture resistance may not be obtained, and when it is less than 0.5% by weight, rub resistance and adhesion may decrease. .

Examples of the crosslinkable monomer having two or more polymerizable double bonds upon irradiation with light 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′-bis (4-acryloxypropyl Diacrylate compounds such as (roxyphenyl) propane and 2,2′-bis (4-acryloxydiethoxyphenyl) propane; trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate Triacrylate compounds such as acrylates; tetraacrylate compounds such as ditrimethylol tetraacrylate, tetramethylol methane tetraacrylate, and pentaerythritol tetraacrylate; hexaacrylate compounds such as dipentaerythritol hexaacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene Glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol Dimethacrylate, polybu Dimethacrylate compounds such as tylene glycol dimethacrylate and 2,2'-bis (4-methacryloxydiethoxyphenyl) propane; trimethacrylate compounds such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; methylene bisacrylamitide And divinylbenzene. When using an oil-soluble monomer, it is used after emulsifying with a surfactant.
As the surfactant, a polymerizable surfactant is preferable. The polymerizable surfactant is preferably an anionic polymerizable surfactant or a nonionic surfactant.

Examples of the anionic polymerizable surfactant include sodium vinyl sulfonate and 2-sulfoethyl methacrylate. Examples of the nonionic polymerizable surfactant include polyoxyethylene alkyl ether. Modified acrylic acid, modified acrylic acid of polyoxyethylene polystyryl phenyl ether, monoacrylate of polyoxyethylene-polyoxypropylene glycol, and the like, and commercially available products include acrylic acid of polyoxyethylene alkyl phenyl ether Modified products such as N177E (manufactured by Daiichi Kogyo Seiyaku) and the like can be mentioned.

As the reactive oligomer, an oligomer having at least one photoreactive group, or an oligomer (prepolymer, low polymer) which is polymerized in the presence of a photocuring agent when irradiated with light is used. Any thing may be used, and any of water-soluble and oil-soluble ones can be used.
Oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, polyol acrylate, acryl alkyd resin, acrylated spirane resin, unsaturated polyester and the like can be mentioned.

The reactive polymer may be any polymer having at least one photoreactive group, or any photoreactive polymer which is polymerized in the presence of a photocuring agent upon irradiation with light. Water-soluble ones can be used, for example, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyamide, polyacrylate,
Water-based polymers such as polymethacrylate, polyacrylic acid, and polymethacrylic acid are included.

The reactive saccharide may be any saccharide having at least one photoreactive group, or any saccharide that is polymerized in the presence of a photocuring agent when irradiated with light. And oil-soluble ones can be used,
For example, those described in the following formulas 1 to 7 are exemplified.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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(In the above formula, R = H, —CH3) The reactive saccharide provides water retention to the ink composition, prevents clogging, and improves the reliability of the ink.

The content of the high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar in the ink composition is from 10 to 80% by weight based on the ink composition. , Preferably 20 to 8
When the content is less than 10% by weight, there is a problem that drying takes a long time. When the content is more than 80% by weight, coagulation due to contact with the coagulation liquid occurs. There is a problem that it is difficult.

The colorant contained in the ink composition may be either a dye or a pigment. Pigments are preferred in terms of light resistance and water resistance. It is also possible to use a pigment and a dye together. The content of the colorant in the ink composition is preferably about 0.5 to 25% by weight, and more preferably about 2 to 15% by weight.

The pigment is not particularly limited, and either an inorganic pigment or an organic pigment can be used. As inorganic pigments, in addition to titanium oxide and iron oxide, contact method,
Carbon black produced by a known method such as a furnace method and a thermal method can be used.
As the organic pigment, azo pigments (azo lake pigments,
Insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc., phthalocyanine pigments (copper phthalocyanine pigments, metal-free phthalocyanine pigments), condensed polycyclic pigments (anthraquinone pigments, perylene pigments, perinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, Isoindolinone pigments, quinoflurone pigments, etc., dye lakes (basic dye lakes, acid dye lakes, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used. The particle size of the pigment is preferably 10 μm or less, more preferably 0.1 μm or less.

Particularly, carbon black used as a black ink includes No. 2300, No. 900, MCF88, N
o.33, No.40, No.45, No.52, MA7, MA8, MA100, No.2200B, etc., manufactured by Columbia Raven5750, Raven5250, Raven5000,
Raven3500, Raven1255, Raven700, etc.
Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch70
0, Monarch 800, Monarch 880, Monarch 900, Monarch
1OOO, Monarch 11OO, Monarch 1300, Monarch 1400, etc. are Color Black FW1, Color Black FW manufactured by Degussa
2, Color Black FW2V, Color Black FW18, Color Black
FW200, Color B1ack S150, Color Black S160, Color
Black S170, Printex 35, Printex U, Printex V, Pri
ntex 140U, Special Black 6, Special Black 5, Speci
al Black4A, Special Black 4, etc. can be used. Pigments used for yellow inks include CI Pigment Yell
ow 1, CI Pigment Yellow 2, CI Pigment Yellow 3,
CI Pigment Yellow 12, CI Pigment Yellow 13, CI
Pigment Yellow 14C, CIPigment Yellow 16, CIPig
ment Yellow 17, CI Pigment Yellow 73, CI Pigment
Yellow 74, CI Pigment Yellow 75, CI Pigment Yell
ow 83, CI Pigment Yellow 93, CI Pigment Yellow 9
5, CI Pigment Yellow 97, CI Pigment Yellow 98, C.
I.Pigment Yellow114 、 CIPigment Yellow128 、 CIPi
gment YelloW129 、 CIPigment Yellow151 、 CIPigmen
t Yellow 154 and the like. Pigments used in magenta ink include CI Pigment Red 5, CI Pigment
ment Red 7, CI Pigment Red 12, CI Pigment Red 48
(Ca), CI Pigment Red 48 (Mn), CI Pigment Red 57 (C
a), CI Pigment Red 57: 1, CI Pigment Red 112, CI
Pigment Red 123, CI Pigment Red 168, CI Pigment
Red 184, CI Pigment Red 202 and the like. Pigments used in cyan ink include CI Pigment Blue
1, CI Pigment Blue 2, CI Pigment Blue 3, CI Pig
ment Blue 15: 3, CIPigment Blue 15:34, CIPigmen
t Blue 16, CI Pigment Blue 22, CI Pigment Blue 6
0, CIVat Blue 4, and CIVat Blue 60.

Pigments that can be dispersed in water without a dispersant (surface-treated pigments) can be used. The surface-treated pigment was allowed to be dispersed in water without a dispersant by a surface treatment such that at least one functional group of a carbonyl group, a carboxyl group, a hydroxyl group or a sulfone group or a salt thereof was bonded to the surface. Things. Specifically, for example, by a physical treatment such as vacuum plasma or a chemical treatment such as an oxidation treatment with hypochlorous acid, sulfonic acid, or the like, a functional group or a molecule containing a functional group is carbon black ink or the like. To the surface of the pigment particles. The functional group introduced into one pigment particle may be a single kind or a plurality of kinds, and the kind and the degree of the introduced functional group depend on dispersion stability in ink, color density and the entire surface of the ink jet head. It may be appropriately determined in consideration of the drying property and the like. In the present invention, a state in which a pigment is stably present in water without a dispersant is also referred to as dispersion. The pigment preferably used in the present invention can be obtained, for example, by the method described in JP-A-8-3498. The carbon black ink treated by the method described in this publication has a high surface active hydrogen content of 1.5 to 2.5 mmol / g. As a result, they disperse very well in water. Also,
Examples of the pigment include MicroJet CW1 or CW2 manufactured by Orient Chemical Industries, Ltd.

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;
Glucosides such as savonin; alginic acid and alginic acid derivatives such as propylene glycol alginate, triethanolamine alginate and ammonium alginate; cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose 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 copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-
Styrene-acrylic resin such as acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylate copolymer; styrene-maleic acid copolymer Styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate- Examples include vinyl acetate-based copolymers such as maleic ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and salts thereof. 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. Pigment dispersion used in the present invention, for example,
Pigment and dispersant and water or water and a water-soluble organic solvent (for example,
A mixture of the low-boiling point organic solvent is mixed, and a disperser (for example, a bead mill, ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, Or a par mill or the like).

Examples of the dyes include direct dyes, acid dyes, food dyes, basic dyes, photoreactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes. Can be used.

The polymer fine particles contained in the ink composition include acrylic resin, vinyl acetate resin, styrene butadiene resin, vinyl chloride resin, acryl-styrene resin, butadiene resin, styrene resin,
Examples include particles formed of a crosslinked acrylic resin, a crosslinked styrene resin, a benzoguanamine resin, a phenol resin, a silicone resin, an epoxy resin, and the like. The polymer fine particles contained in the ink composition promote the adhesion of the colorant to the recording medium surface by interaction with at least one of a polyvalent metal salt, a polyamine, and a polyamine derivative in a coagulation liquid described below. It has.

The polymer fine particles preferably have a glass transition point not higher than the drying temperature in the drying step before light irradiation in the present invention or the temperature in the light irradiation furnace. Such polymer fine particles are preferably used in the form of an aqueous emulsion containing the polymer fine particles as dispersed particles. Here, the form of the aqueous emulsion containing polymer fine particles as dispersed particles means an aqueous dispersion of polymer fine particles using polymer fine particles as a dispersoid and water as a dispersion medium. The aqueous emulsion containing the polymer fine particles as dispersed particles preferably has a drying temperature in a drying step before light irradiation in the present invention or a minimum film forming temperature equal to or lower than a temperature in a light irradiation furnace. The aqueous emulsion in which the polymer fine particles are dispersed particles is used when the ambient environmental temperature is equal to or higher than the minimum film forming temperature, in other words, when the glass transition point of the polymer fine particles is lower than the ambient environmental temperature, As the components are lost due to evaporation or the like, the polymer fine particles come close to each other and approach close-packing, and are fused by the action of the capillary pressure in the interparticle space to form a polymer film. It is preferable that the film formation of the polymer fine particles be performed at a drying temperature of the drying step before light irradiation in the present invention or at a temperature lower than the temperature in the light irradiation furnace, since the coloring agent is more firmly fixed to the recording medium. Here, the "minimum film forming temperature" means that an aqueous emulsion obtained by dispersing polymer fine particles in water is thinly cast on a metal plate such as aluminum, and a transparent continuous film is formed when the temperature is increased. Means the lowest temperature at which In a temperature region lower than the minimum film forming temperature, a white powder is formed.

"Film-forming property" means that when a polymer fine particle is dispersed in water to form an aqueous emulsion, a polymer film is formed as the water component of the aqueous emulsion is evaporated. I do. The ink composition to which the polymer fine particles are added has a property that a polymer film is similarly formed when water and an aqueous organic solvent are evaporated. The polymer film plays a role of firmly fixing the colorant component in the ink composition to the surface of the recording medium. Thus, it is considered that an image having excellent abrasion resistance and water resistance can be realized.

The content of the polymer fine particles is preferably 1 to 30% by weight, more preferably 1 to 30% by weight, based on the ink composition.
-10% by weight. Further, the particle diameter of the polymer fine particles is preferably about 400 nm or less, more preferably 2 nm or less.
It is not more than 00 nm, more preferably about 5 to 80 nm.

The polymer fine particles preferably have a carboxyl group on the surface and have high cohesion with a divalent metal salt. For example, as a polymer fine particle, a structure containing 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having a carboxyl group and crosslinked by a crosslinkable monomer having two or more polymerizable double bonds. And those containing 0.2 to 4% by weight of a structure derived from a crosslinkable monomer. In the polymerization, two or more polymerizable double bonds, more preferably, three-dimensionally cross-linkable polymer obtained by copolymerizing a cross-linkable monomer having three or more, the nozzle plate surface is reduced. The ink composition makes it more difficult to get wet, so that flight bending can be further prevented and ejection stability can be further improved.

As the polymer fine particles, those having a single-particle structure and those having a core-shell structure composed of a core portion and a shell portion surrounding the core portion can also be used. Here, 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 polymer fine particles 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 Examples include cyan compound monomers, halogenated monomers, olefin monomers, and diene monomers.

The polymer fine particles having a core-shell structure are produced by a known method, generally by multi-stage emulsion polymerization or the like. For example, JP-A-4-76004
Can be manufactured by the method disclosed in Japanese Patent Application Publication No. Examples of the unsaturated vinyl monomer used in the polymerization include those described above.

In the ink composition according to the present invention, a low-boiling organic solvent (particularly, a solvent having a low boiling point) is added to the ink composition of the present invention for the purpose of increasing the drying speed in a drying step before light (particularly, ultraviolet light) irradiation. (Low-boiling alcohol). As the low-boiling alcohol, the number of carbon atoms is 1
And aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol. These low-boiling organic solvents can be used alone or in combination of two or more. The content of the low-boiling organic solvent (particularly, low-boiling alcohol) is based on the total weight of the ink composition.
Preferably 1 to 30% by weight, more preferably 10 to 20%
% By weight. If it exceeds 30% by weight, there may be a problem in dischargeability, and if it is less than 1% by weight, the drying rate may decrease in the drying step before light (particularly, ultraviolet light) irradiation.

The ink composition of the present invention may contain other additives, for example, a pH adjuster, a preservative and / or a fungicide. Examples of the pH adjuster include various amines such as diethanolamine and triethanolamine, and hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide.

The ink composition of the present invention contains the above components in an aqueous medium. The aqueous medium is water or a mixture of water and a water-soluble organic solvent (for example, the low-boiling organic solvent).

The ink composition of the present invention comprises, for example, a high-boiling wetting agent comprising the pigment dispersion prepared by the above-mentioned method and the above-mentioned reactive monomer, reactive oligomer, reactive polymer and reactive sugar. At least one of the polymer fine particles;
It can be produced by mixing water, a water-soluble organic solvent and a photocuring agent with a stirrer.

The coagulating liquid used in the present invention contains a coagulant. When the flocculant comes into contact with the ink composition, a flocculant is formed. As the aggregating agent, any compound can be used as long as it is a compound that destroys and aggregates the dispersed and / or dissolved state of the pigment and / or polymer fine particles in the ink composition. Examples of flocculants include:
Mention may be made of polyvalent metal salts, polyamines and polyamine derivatives. As the polyvalent metal salt, for example, divalent to
Trivalent metals, preferably divalent metals such as magnesium, calcium, barium, copper, nickel or zinc, or trivalent metals such as aluminum, iron or chromium, acetic acid, butyric acid, formic acid, propionic acid, isobutyric acid, Water-soluble salts such as carboxylate salts such as valeric acid, isovaleric acid and pivalic acid, and nitrates can be mentioned. Examples of polyamines and polyamine derivatives include cationic polymers that are soluble in water and positively charged in water. Among them, calcium and magnesium salts are preferred in view of the pH of the coagulating liquid and the quality of the obtained printed matter.

The concentration of these polyvalent metal salts in the aggregating solution may be appropriately determined within a range where the effect of preventing printing quality and clogging can be obtained, and is preferably about 10 to 30% by weight, and more preferably about 10 to 30% by weight. Is about 15 to 25% by weight. The content of the polyamine and the polyamine derivative is preferably 0.5 to 10% by weight of the aggregation liquid.

The aggregation liquid may contain a polymerizable surfactant to improve the wettability of the non-ink-absorbing recording medium. In general, the presence of a surfactant causes a decrease in adhesion. However, when a polymerizable surfactant is used, excellent adhesion to a non-ink-absorbing recording medium can be obtained. As the polymerizable surfactant, a chaotic polymerizable surfactant or a nonionic polymerizable surfactant is preferably used from the viewpoint of the stability of the aggregation liquid. Examples of the chaotic polymerizable surfactant include acrylate-modified quaternary ammonium salts, and specific examples thereof include dimethylaminoethyl methyl methacrylate chloride and dimethylaminoethyl benzyl methacrylate. Or N, N'-dimethylaminopropylacrylamidomethyl chloride salt.

The ink composition and / or the coagulating liquid may contain a photo-curing agent, if necessary. The content of the photocuring agent is selected according to the type of the curing agent, the type of the reactive high-boiling wetting agent such as the reactive monomer, the reactive oligomer, the reactive polymer, and the reactive sugar, and the amount used thereof. Is included in the ink composition, the amount necessary for polymerization of a reactive high-boiling wetting agent such as a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, for example, a reactive monomer , Reactive oligomers, reactive polymers, reactive sugars and other reactive high boiling point wetting agents,
The concentration may be 0.1 to 10% by weight, but when it is contained in the aggregating liquid, it must be selected in consideration of the ratio of the portion where the aggregating liquid overlaps the ink composition on the recording medium.

As the photo-curing agent, light (particularly, when the wavelength is
Any substance that generates a radical upon irradiation with ultraviolet light (220 nm to 400 nm) can be used. Specifically, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n- Butyl ether, benzyl methyl ketal,
Thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Examples include methylpropan-1-one, methylbenzophyllformate, 1-hydroxycyclohexylphenyl ketone, azobisisobutylylonitrile, benzoyl peroxide, di-tert-butyl peroxide and the like. These photocuring agents can be used singly or in combination. In particular, a water-soluble photocuring agent, 4- (2-hydroxyethoxy) phenyl-
(2-Hydroxy-2-propyl) ketone [trade name: Darocure 2959 (manufactured by Ciba Specialty)] is preferred.

The purpose of preventing a decrease in the curing rate due to absorption or concealment of light (particularly ultraviolet light) by the pigment in the ink composition of the present invention when light (particularly ultraviolet light) is irradiated. And a sensitizer can be used. Examples of the sensitizer include an aliphatic amine, an amine having an aromatic group, or a cyclic amine compound such as piperidine, a urea compound such as O-tolylthiourea, a soluble salt of sodium siethylthiophosphate or aromatic sulfinic acid. A sulfur compound such as N, N'-disubstituted-p-aminobenzonitrile, a phosphorus compound such as tri-n-butylphosphine or sodium diethyldithiophosphate, a Michler's ketone, an N-nitrosohydroxylamine derivative, an oxazolidine compound ,
Examples include nitrogen compounds such as tetrahydro-1,3-oxazine compounds, formaldehyde or condensates of acetaldehyde and diamine. These sensitizers can be used alone or in combination of two or more.

The recording method according to the present invention is a method for recording an image on a recording medium using a photocurable two-part ink comprising the above ink composition and a coagulating liquid, wherein the coagulating liquid is applied to the recording medium. The method includes a step of adhering the ink composition onto the recording medium, a step of recording an image by adhering the ink composition on a recording medium, a drying step, and a subsequent curing step by light irradiation.

The order in which the coagulating liquid and the ink composition are applied to the recording medium may be any order. That is, the coagulating liquid is applied to the recording medium, and then the ink composition is applied to the recording medium. Any of the following methods can be suitably performed: a method of applying the aggregation liquid after printing the ink composition, and a method of mixing the aggregation liquid and the ink composition immediately before or immediately after the adhesion.

Regarding the adhesion of the coagulating liquid to the recording medium,
Either a method in which the coagulation liquid is selectively applied only to the place where the ink composition is to be applied or a method in which the coagulation liquid is applied to the entire recording medium may be used. The former is economical because it can minimize the consumption of the coagulating liquid, but requires a certain degree of accuracy in the position where both the coagulating 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 aggregation liquid and the ink composition is relaxed compared to the former, but a large amount of the aggregation liquid is attached to the entire recording medium, which is disadvantageous from the viewpoint of drying properties. There may be. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the aggregation liquid.

Means for adhering the coagulating liquid to the recording medium;
Means for adhering the ink composition to the recording medium can be a recording method usually used in the printing industry and the coating industry, for example, direct injection, spraying, coating, transfer and the like, preferably recording droplets An ink jet recording method in which printing is performed by discharging to a medium is preferable.

That is, the photocurable two-pack type ink composed of the ink composition and the coagulation liquid ejects the ink composition droplets and the coagulation liquid droplets, and adheres each droplet to the recording medium. The present invention can be advantageously applied to an ink jet recording method for performing recording. Here, the order of the ejection of the droplets of the aggregation liquid and the ejection of the droplets of the ink composition is not particularly limited, as described above, and the droplets of the aggregation liquid are first discharged, and then, A droplet of the ink composition can be discharged, or a droplet of the ink composition can be discharged first, and then a droplet of the aggregation liquid can be discharged. When the droplets of the ink composition and the aggregating liquid come into contact with each other, the dispersed and / or dissolved state of the pigment and / or polymer particles in the ink composition is destroyed, and aggregates are generated. In general, since ink does not penetrate into a recording medium on an ink non-absorbing recording medium, in multicolor printing such as a color image, color mixing or color mixing due to multicolor overlapping printing occurs in a boundary region of different colors. In addition, edge blurring due to ink flow occurs. On the other hand, when the photocurable two-part ink of the present invention is used, an agglomerate is generated as described above, so that the above-described color mixing and blurring of edges can be prevented. Further, the adhesive component in the above-mentioned aggregation solution can improve the adhesiveness to the ink non-absorbing recording medium.

When applied to an ink-jet recording method, as described above, the droplets of the coagulating liquid and the ink composition are ejected onto the surface of the recording medium by the ink-jet recording method to adhere the image. After that, it is preferable to carry out a recording method including a step of drying the image on the recording medium and a step of curing the dried image. The drying step can be performed, for example, by heating the image forming surface or the back surface of the recording medium carrying the attached image.
The curing step can be performed, for example, by irradiating the dried image forming surface with a curing light beam (particularly, ultraviolet light).

For example, after a droplet of the coagulating liquid is adhered onto the surface of a non-ink-absorbing recording medium such as plastic or metal by the ink jet recording method, a droplet of the ink composition is discharged thereon. The dispersing and / or dissolving state of the pigment and / or polymer fine particles in the ink composition is destroyed by the flocculant, and the flocculant is formed. In general, since ink does not penetrate into a recording medium on an ink non-absorbing recording medium, in multicolor printing such as a color image, color mixing or color mixing due to multicolor overlapping printing occurs in a boundary region of different colors. In contrast, when the photocurable two-part ink of the present invention is used, agglomerates are generated as described above, whereas the edge blurring due to the ink flow occurs. Therefore, the color mixing and the edge blurring are prevented. can do. Further, the adhesive component in the above-mentioned aggregation solution can improve the adhesiveness to the ink non-absorbing recording medium.

After an image is formed on the recording medium, moisture (and an organic solvent or the like present in some cases) is evaporated by using a heating means such as warm air or irradiation with far infrared rays to dry the recording medium. At this time, when the recording medium is made of plastic, the recording medium is dried in a temperature range that does not deform by heating. Next, when light (especially, ultraviolet light) is irradiated, the reactive monomer, the reactive oligomer, the reactive polymer, and the reactive sugar are respectively reacted by the photocuring agent, and the polymer fine particles are brought into close proximity by aggregation. In combination with this, a very strong film containing pigments is formed. In particular, when a water-soluble monomer having an adhesion-imparting group is used, excellent adhesion to a recording medium can be obtained. The light irradiation is not particularly limited as long as it is a method of sufficiently irradiating at least a portion of the recording medium where the image is formed with the ink composition. Of course, the entire recording medium may be irradiated.

As described above, even when printing is performed on a non-ink-absorbing recording medium (for example, a recording medium made of plastic or metal), the ink has excellent fixability to the substrate and abrasion resistance, as well as water resistance and moisture resistance. And a recorded matter having excellent chemical resistance.
Furthermore, when an ink non-absorptive recording medium that has been subjected to a surface treatment such as a hydrophilic treatment is used, the adhesion to the recording medium is further improved, and the fixability is further improved. Such a hydrophilic treatment can be performed by, for example, corona discharge or chemical treatment.

In order to improve the adhesion to the non-ink-absorbing recording material as the adherend, it is necessary to increase the wettability with the non-ink-absorbing recording material, and to increase the intermolecular force (Van der Waals force, It is important to increase the hydrogen bond, etc., and the polymerizable surfactant is effective for the former, and an acrylic monomer having an amino group and / or an amide group (specifically, an amide group or an amino group) is It is considered to be effective for the latter.

One embodiment of the ink jet recording apparatus according to the present invention will be described with reference to the drawings. FIG.
FIG. 1 is a diagram schematically illustrating a configuration of an embodiment of an inkjet recording apparatus according to the present invention. A recording medium 2 is conveyed from a recording medium supply source 1 to a recording mechanism 3, for example, an ink jet recording mechanism, provided with means for adhering a coagulating liquid and means for adhering an ink composition to form an image. In 3, the aggregation liquid and the ink composition are attached to the surface of the recording medium 2 and printing is performed. The printed recording medium 2 is then heated and dried by a drying mechanism 4 having a heater or the like. After drying, the recording medium 2 is conveyed to a curing mechanism 5 provided with an ultraviolet irradiation means and the like, where it undergoes a curing treatment by ultraviolet irradiation. The recording medium 2 that has undergone the curing process is conveyed to and stored in the recording article storage unit 6.

The ink jet recording apparatus according to the present invention comprises:
Means for storing the ink composition and the coagulating liquid in a tank, supplying the ink composition and the coagulating liquid to the recording head via the ink tube, and further comprising a drying means ( For example, a heating unit) or a drying unit (for example, a heating unit) on the paper discharge side from the recording head operating area, and a curing unit (for example, on the paper discharge side of the drying unit (for example, heating unit)) Ultraviolet irradiation means). The drying means is not limited as long as the dissolved components in the ink composition and the coagulating liquid can be dried. The drying means may be a direct heating means for contacting and heating the recording medium, or may be an infrared ray or a microwave. (An electromagnetic wave having a maximum wavelength of about 2,450 MHz) or the like, or an indirect heating means for heating without contacting the recording medium by blowing hot air or the like.
When the heating is performed by the indirect heating means, the heating may be performed from either the image forming surface side of the recording medium or the back surface side of the recording medium. As an ultraviolet irradiation means as one of the curing means, an ultraviolet irradiation lamp represented by a high-pressure mercury lamp and a metal halide lamp can be used. Specifically, a metal halide lamp or a high-pressure mercury lamp can be used. For example, F
Commercially available lamps such as H lamp, D lamp or V lamp manufactured by usionSystem can also be used. The metal halide lamp has a continuous spectrum compared to a high-pressure mercury lamp (having a main wavelength of 365 nm), has a high luminous efficiency in the range of 200 to 450 nm, and has a wide range of long wavelengths. Therefore, when a pigment is used as in the ink composition of the present invention, a metal halide lamp is suitable.

The recording medium used in the present invention may be any of those having an absorbency with respect to an ink composition such as paper and those having a substantially non-absorbent property with respect to an ink composition. "Substantially non-absorbable with respect to the ink composition" means that when the ink composition is applied to the recording medium, the recording medium is such that the ink composition does not penetrate the recording medium at all for a time of several seconds. means. Specific examples of the recording medium to which the inkjet recording method according to the present invention can be applied include polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polysulfone,
Plastic media based on ABS resin, polyvinyl chloride, etc., recording media and paper that have been metal-coated on metal surfaces such as brass, iron, aluminum, SUS, copper, etc. or on non-metallic substrates by vapor deposition, etc. Examples of the recording medium include a recording medium having a water-repellent treatment or the like as a base material, a recording medium having a cloth surface or the like subjected to a water-repellent treatment or the like, and a recording medium made of a so-called ceramic material obtained by firing an inorganic material at a high temperature.

[0069]

Next, examples of the present invention will be described together with comparative examples.
The present invention will be specifically described, but the present invention is not limited by the following examples.

<Preparation of Polymer Fine Particles> [Polymer Fine Particle 1] 900 g of ion-exchanged water and 4 g of sodium lauryl sulfate were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer.
The temperature was raised to 70 ° C. while purging with nitrogen while stirring. The internal temperature was maintained at 70 ° C., and 2 g of potassium persulfate was added as a polymerization initiator. After dissolution, 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 435 g of styrene, 475 g of butyl acrylate, and 30 g of methacrylic acid were stirred in advance. The emulsion produced in addition to the polymerization was continuously dropped into the reaction solution over 3 hours. After dropping,
Aging was performed for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and aqueous ammonia were added to adjust the solid content to 40% by weight and pH 8. The obtained aqueous emulsion had a minimum film formation temperature of 22 ° C.

[Polymer Fine Particle 2] In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer,
900 g ion-exchanged water and sodium lauryl sulfate 4
g, and the temperature was increased to 70 ° C. while stirring and replacing with nitrogen. The internal temperature was maintained at 70 ° C., and 2 g of potassium persulfate was added as a polymerization initiator.
g, acrylamide 20 in 3 g of sodium lauryl sulfate
435 g of styrene, 475 g of butyl acrylate,
An emulsion produced by adding 30 g of methacrylic acid and 2 g of ethylene glycol dimethacrylate under stirring was continuously dropped into the reaction solution over 3 hours. After completion of dropping, aging was performed for 3 hours. After the obtained aqueous emulsion was cooled to room temperature, ion-exchanged water and aqueous ammonia were added to adjust the solid content to 40% by weight and pH 8. The obtained aqueous emulsion had a minimum film formation temperature of 22 ° C.

[Examples 1 to 16, Comparative Examples 1 to 14] <Preparation of Ink Composition> Ink compositions 1 and 2 having the compositions shown in Table 1 and the compositions shown in Table 2, respectively.
To 10 were prepared and used in combination with the ink composition and the coagulating liquid described in Table 3 to perform tests for fixing property, adhesion, and water resistance by the following test methods. Indicated. Further, using the ink compositions 1 to 10 and the aggregation liquids 1 and 2 in combination shown in Table 4, a color mixing test was performed. The results are shown in Table 4. Further, for the ink compositions 1 to 10 used in Examples 1 to 4 and Comparative Examples 1 to 6, a test of the clogging characteristics was performed by the following test method.
The results are also shown in Table 5.

<Recording test> [Recording test method] On a polyethylene terephthalate film and an ABS using an ink jet printer
After printing using the aggregating liquid shown in Table 1 and the ink composition shown in Table 2, a pre-drying means (heater) was used.
And a treatment by an ultraviolet irradiation means (ultraviolet irradiation lamp).

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[Evaluation Method] (Evaluation 1) Drying of Printed Surface The surface of the printed matter printed by the above recording method is touched with a finger to check for stickiness.

(Evaluation 2) Fixing Property The printing portion was pressed with a writing pressure of 5 × 10 5 N using a yellow-water-based fluorescent pen (ZEBRA PEN2 (trade name) manufactured by Zebra Co., Ltd.) on the printed matter printed in accordance with the recording test method.
/ M2, and the presence or absence of peeling of the printed portion from each substrate was visually observed, and evaluated by the following three grades (A, B, NG). A: There is no peeling from the substrate. B: Peeling from the substrate is observed. NG: Peeled completely from the substrate.

(Evaluation 3) Adhesion A scotch clear tape (trade name, manufactured by 3M Company) was attached to the printed portion of the recorded matter printed according to the above recording method.
After loading at 300g / cm2, peel off the tape,
The state of peeling of the printed portion from the substrate was visually checked, and evaluated by the following three steps (A, B, NG). A: There is no peeling from the substrate. B: Peeling from the substrate is observed. NG: Peeled completely from the substrate.

(Evaluation 4) Water Resistance The recorded matter printed in accordance with the above recording method was immersed in water for 10 times.
After being immersed for a minute and taken out of the water, the state of the printed part was visually observed and evaluated according to the following three grades (A, B, NG). A: There is no change in the printing section. B: Ink flow is seen in the printing section. Alternatively, peeling of the printed portion from the substrate is observed. NG: The printed portion was completely separated from the base material, and characters and images could not be distinguished.

(Evaluation 5) Color Mixing The aggregation liquid 1 was placed in the first row of the nozzle row of the ink jet printer head, the ink composition 1 was placed in the second row, the ink composition 2 was placed in the third row, and the ink composition was placed in the fourth row. The ink composition 4 was set on the object 3 and the fifth row, respectively. First, the aggregation liquid was landed on the recording medium, and then printing was performed so that the ink composition was landed on the same position. Printing was performed in the same manner except that the aggregation liquid 2 was used instead of the aggregation liquid 1. Further, the aggregation liquid 1 was set in the first row of the nozzle row of the ink jet printer head, the ink composition 5 was set in the second row, and the ink composition 8 was set in the third row, and printing was performed on the recording medium by the above method. . In the same manner, when the ink composition 6 is set in the second row and the ink composition 8 is set in the third row, when the ink composition 7 is set in the second row and the ink composition 8 is set in the third row,
When the ink composition 10 was set in the second row and the ink composition 8 was set in the third row, printing was similarly performed on a recording medium.
Further, in the same manner, the coagulation liquid 2 is used instead of the coagulation liquid 1.
Printing was performed in the same manner except for using. The recorded matter printed according to the above-mentioned recording method was visually observed for the presence or absence of uneven color mixture at the color boundary, and evaluated according to the following three grades (A, B, NG). A: There is no color mixture and the boundary is clear. B: Color mixture is slightly generated. NG: The colors are so mixed that the color boundaries are not clear, and the image is not clear.

(Evaluation 6) Clogging Characteristics An ink jet printer MJ710V2C is filled with the ink composition, and alphanumeric characters are printed continuously for 10 minutes. Then, without stopping the printer and capping,
It is left for 1 hour in an environment of a temperature of 40 ° C. and a humidity of 25%.
After leaving, alphanumeric characters are printed again, and the number of return operations required until print quality equivalent to that before leaving is obtained is examined. The evaluation is performed according to the following criteria. A: The print quality equivalent to the initial one can be obtained by the return operation of 0 to 2 times. B: Print quality equivalent to the initial one can be obtained with three to five recovery operations. NG: Print quality equivalent to the initial one cannot be obtained after six or more return operations.

From the results of Tables 3 to 5, Examples 1 to 4 using the photocurable ink of the present invention showed that the ink compositions 5 to 10
Compared with Comparative Examples 1 to 6, which are excellent in that both the printing surface drying property and the clogging property are satisfied at the same time, and are excellent in fixing property, adhesion, water resistance, and color mixing. It is clear that an excellent effect is also exhibited in that no effect occurs.

[0086]

As described in detail above, the present invention provides a high-boiling wetting composition comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar in an ink composition of a two-pack ink. Agent, a polyvalent metal salt in the aggregation liquid, a polyamine, at least one of a polyamine derivative, and, if necessary, a light curing agent in one of them, the recording medium, especially Eliminates "stickiness" after recording on a non-absorbent recording medium, improves colorant fixation and abrasion resistance, does not cause color mixing and clogging, improves water resistance, and further improves image quality. This is an excellent effect.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an embodiment of an ink jet recording apparatus according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Recording medium supply source 2 Recording medium 3 Recording mechanism 4 Drying mechanism 5 Curing mechanism 6 Recording article storage part

Claims (19)

[Claims] 1. A high-boiling wetting agent comprising at least one of a reactive monomer, a reactive oligomer, a reactive polymer, and a reactive sugar, a coloring agent, polymer particles, water, and a water-soluble organic solvent. An ink composition, comprising an aggregating liquid containing at least an aggregating agent that forms an aggregate when contacted with the ink composition, and, if necessary, at least one of the ink composition and the aggregating liquid. A photocurable two-part ink, wherein one liquid contains a photocuring agent. 2. The high-boiling wetting agent comprising at least one of the above-mentioned reactive monomer, reactive oligomer, reactive polymer, and reactive sugar is an acryloyl group, a methacryloyl group, an acrylamide group, an allyl group, a vinyl ether group,
The photocurable two-part ink according to claim 1, wherein the photocurable two-part ink has at least one of a photoreactive group consisting of a vinylthioether group and a vinylamino group. 3. A high-boiling wetting agent comprising at least one of the above-mentioned reactive monomer, reactive oligomer, reactive polymer, and reactive sugar, which is polymerized in the presence of a photo-curing agent upon irradiation with light. The photocurable two-part ink according to claim 1. 4. The content of a high-boiling wetting agent comprising at least one of the reactive monomer, reactive oligomer, reactive polymer, and reactive sugar is 20 to 80% by weight based on the ink composition. The photocurable two-pack ink according to claim 1. 5. The high boiling wetting agent comprising at least one of the reactive monomer, the reactive oligomer, the reactive polymer, and the reactive sugar has a boiling point of 180 ° C. or higher. 2. The photocurable two-part ink according to item 1. 6. The composition according to claim 1, wherein the content of the polymer fine particles is 0.1 to 30% by weight based on the ink composition.
6. The photocurable two-pack ink according to any one of 5. 7. The method according to claim 1, wherein the colorant is a pigment.
7. The photocurable two-pack ink according to any one of 6. 8. The photocurable two-part ink according to claim 1, wherein the coagulant is at least one of a polyvalent metal salt, a polyamine, and a polyamine derivative. 9. The polyvalent metal salt comprises at least one of a divalent metal such as calcium, magnesium, barium, copper, zinc and nickel, and a nitrate or carboxylate of a trivalent metal such as aluminum, iron and chromium. The photocurable two-part ink according to claim 8, wherein: 10. A reactive monomer, a reactive oligomer,
When the ink composition contains at least one of a high-boiling wetting agent composed of at least one of a reactive polymer and a reactive sugar, a colorant, polymer particles, water, and a water-soluble organic solvent, and comes into contact with the ink composition An aggregating liquid containing at least an aggregating agent that generates an agglomerate, and if necessary, at least one of the ink composition and the aggregating liquid contains a photocuring agent. What is claimed is: 1. A recording method for performing recording using a photocurable two-component ink, comprising: a step of adhering a coagulating liquid onto a recording medium; and adhering the ink composition onto the recording medium to record an image. A recording method, comprising: a step of drying at least a recorded image portion after the above two steps; and a step of irradiating at least the recorded image portion with light and curing after the drying step. 11. The recording method according to claim 10, wherein the step of depositing the ink composition on the recording medium is after the step of depositing the aggregation liquid on the recording medium. 12. The recording method according to claim 11, wherein the step of adhering the ink composition on the recording medium is before the step of adhering the aggregation liquid on the recording medium. 13. An ink-jet method in which the step of depositing the ink composition on the recording medium and / or the step of depositing the aggregating liquid on the recording medium performs recording by discharging droplets and attaching the droplets to the recording medium. The recording method according to any one of claims 10 to 12, which is a recording method. 14. The recording method according to claim 10, wherein the recording medium is a medium having a surface that does not substantially absorb the photocurable two-component ink. 15. The surface of the recording medium is made of plastic,
The rubber composition is a rubber, a metal, or a ceramic.
3. The recording method according to any one of 3. 16. A recorded matter recorded by the recording method according to claim 10. Description: 17. A reactive monomer, a reactive oligomer,
When the ink composition contains at least one of a high-boiling wetting agent composed of at least one of a reactive polymer and a reactive sugar, a colorant, polymer particles, water, and a water-soluble organic solvent, and comes into contact with the ink composition An aggregating liquid containing at least an aggregating agent that generates an agglomerate, and if necessary, at least one of the ink composition and the aggregating liquid contains a photocuring agent. What is claimed is: 1. A recording apparatus for performing recording using a photocurable two-component ink, comprising: means for adhering an aggregating liquid onto a recording medium; and adhering an ink composition onto the recording medium to record an image. A recording apparatus comprising: means for drying at least a recorded image portion; and means for irradiating at least the recorded image portion with light and curing the portion. 18. Ink jet recording wherein the means for adhering the coagulating liquid on a recording medium and / or the means for adhering the ink composition on a recording medium ejects droplets and adheres to the recording medium to perform recording. 18. A mechanism, which is a mechanism.
The recording device according to claim 1. 19. The recording apparatus according to claim 17, wherein the curing unit is an ultraviolet irradiation unit.