JP2002052804A - Recording method for printing on recording medium by using two liquids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording method which can realize a fine image excellent in fixing properties and wear and abrasion resistance in regard to a recording medium. SOLUTION: In this recording method, printing is made on a recording medium by adhering thereto an ink composition which contains a coloring agent, a resin emulsion, an acetylene glycol and water at least and a reactive solution which contains a reaction agent bringing about an agglomerate when it comes into contact with the ink composition. The method comprises a process of making the reactive solution adhere onto the recording medium, a process of making the ink composition adhere onto the recording medium to record the image thereon and a process of washing the recording medium printed with the reactive solution and the ink composition made to adhere thereto, with a polar solvent. The purpose of the method can be achieved by making the surface tension of the ink composition 40 nM/m or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

2. Description of the Related Art 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 printing using the aqueous ink composition,
2. Description of the Related Art In recent years, an inkjet recording method has 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 printed on a non-absorbable recording medium, the solvent-based ink composition and paint have excellent fixation, abrasion resistance, durability, and the like. However, certain organic solvents can be toxic to animals and plants. Therefore, care must be taken in use and disposal, and handling is often inconvenient.

[0004] Even when printing and painting on a non-absorbent recording medium, the recording method using the aqueous ink composition is preferable from the viewpoints of safety, environment, convenience of use, and the like. However, in printing on a non-absorbent recording medium, it is required that the coloring 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.
Japanese Patent Application No. -5703 proposes an aqueous dispersion-based pigment ink using a polymer dispersant and a water-soluble organic solvent.

On the other hand, as an ink jet recording method, a color ink containing at least a surfactant or a penetrating solvent for imparting permeability and a salt is used in combination with a black ink which thickens or aggregates by the action of the salt. By doing so, it has been proposed that a high-quality color image having a high image density and no color bleed can be obtained. (JP-A-6-106735). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids of a first liquid containing a salt and an ink composition. In addition, other ink jet recording methods for printing two liquids have been proposed (for example, JP-A-3-240557, JP-A-3-240557).
-240558).

[0007]

SUMMARY OF THE INVENTION The present inventor performed printing on a recording medium, particularly a non-absorbent recording medium, by an ink jet recording method using two liquids consisting of a reaction liquid and an ink composition.
A case where the printed surface was not sufficiently formed into a film was observed. For this reason, the present inventor tried to heat the recording medium after printing in order to advance the film formation of the printing surface. Deterioration and deformation by heat were observed. The present inventor has recently improved the fixation of the colorant on the recording medium by improving the progress of film formation on the printing surface, the abrasion resistance, and the image quality can be improved more than expected. In order to improve the progress of film formation on the surface, it has been found that it is desirable to wash with a polar solvent. The present invention is based on such findings.

Accordingly, an object of the present invention is to provide a recording method which is excellent in the fixability of a coloring agent to a recording medium and can realize a good image.

According to the recording method of the present invention, the recording medium contains at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water, and has a surface tension equal to or less than the surface tension of the recording medium. A recording method for performing printing by adhering an ink composition and a reaction liquid containing a reactant that forms an aggregate when the ink composition comes into contact with the ink composition, wherein the reaction liquid is adhered to a recording medium. A step of recording an image by depositing the ink composition on a recording medium, and a step of washing the recording medium printed by depositing the reaction liquid and the ink composition with a polar solvent. Recording method. Further, according to another aspect of the present invention, the present invention also provides a recording device. The recording apparatus according to the present invention, a recording medium, a colorant, resin emulsion particles, a water-soluble organic solvent, and at least water, and an ink composition having a surface tension equal to or less than the surface tension of the recording medium, What is claimed is: 1. A recording apparatus for performing printing by adhering a reaction liquid containing a reaction agent that generates an agglomerate when contacted with the ink composition, and means for adhering the reaction liquid on a recording medium, and recording Means for adhering the ink composition on a medium to record an image, means for adhering the reaction liquid on a recording medium, and means for adhering the ink composition on a recording medium to record an image. Means for controlling, and means for washing the recording medium printed with the reaction liquid and the ink composition attached thereto with a polar solvent.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Recording method A recording method according to the present invention comprises a step of depositing a reaction solution described below on a recording medium, a step of recording an image by depositing an ink composition described later, and a reaction solution. And washing the recording medium printed by attaching the ink composition with a polar solvent, wherein the ink composition is at least a colorant, resin emulsion particles, a water-soluble organic solvent, , Water, and the surface tension of which is equal to or less than the surface tension of the recording medium.

In the recording method according to the present invention, the colorant is firmly attached to the recording medium by attaching the reaction liquid and the ink composition to the recording medium and washing the printed recording medium with a polar solvent. Sticks and has abrasion resistance, and
A good image can be realized. The reason why such an effect occurs is not clear, but can be inferred as described below. First, when the reaction liquid and the ink composition come into contact, the reaction agent in the reaction liquid destroys the colorant in the ink composition, the dispersed state of the resin emulsion particles,
It is thought to agglomerate it. It is considered that these aggregates fix the colorant on the surface of the recording medium. Further, in the present invention, the ink composition contains resin emulsion particles having specific properties, and it is expected that the presence of the resin emulsion particles promotes the formation of the aggregate. Next, the printing surface formed on the recording medium by contacting the reaction liquid with the ink composition, at the beginning of the contact, an aggregate formed of a colorant and resin emulsion particles near the surface of the recording medium, and the aggregate is Separate water or a water-soluble organic solvent is present. The aggregates are fixed on the recording medium and washed with water or a water-soluble organic solvent with a polar solvent, thereby promoting the formation of the resin emulsion particles into films.In other words, the resin emulsion particles are united with each other. A resin film is formed. It can be expected that this resin film will be more firmly fixed to the recording medium surface due to the presence of the carboxyl group. As a result, it is considered that the colorant was firmly fixed to the surface of the recording medium. Although the above mechanism is considered to be applicable to both absorptive and non-absorptive recording media, in particular, it is thought that the effect is remarkably exerted in a non-absorbent recording medium. Can be Note that the above mechanism is merely an assumption, and the present invention is not construed as being limited to this mechanism.

Regarding the adhesion of the reaction liquid to the recording medium, there are either a method of selectively adhering the reaction liquid only at the place where the ink composition is applied, or a method of adhering the reaction liquid to the entire recording medium. Is also good. The former is economical because it can minimize the consumption of the reaction liquid, but requires a certain degree of accuracy in the position where both the reaction liquid and the ink composition are adhered. On the other hand, the latter requires less precision of the adhesion position of the reaction liquid and the ink composition than the former, but causes a large amount of the reaction liquid to adhere to the entire recording medium, and is disadvantageous from the viewpoint of drying properties. There are cases. Therefore,
Which method is employed may be determined in consideration of the combination of the ink composition and the reaction liquid.

Means for adhering the reaction liquid to the recording medium and means for adhering the ink composition to the recording medium are described in the printing industry,
A recording method generally used in the coating industry can be used, and examples thereof include direct injection, spraying, coating, and transfer. An ink jet recording method for performing printing by discharging a suitable liquid onto a recording medium is preferable.

In the present invention, the method of washing the recording medium after printing with a polar solvent includes, specifically, rinsing, rinsing, dipping, or a mixing means of the recording medium or its surface with a polar solvent. can give. The washing method can be performed continuously or intermittently during printing. As the polar solvent to be used, a solvent which does not exfoliate the coloring component fixed to the recording medium, is water-soluble, and is safe is preferably used. Specific examples of such a polar solvent include:
Water, alcohols having 5 or less carbon atoms, preferably lower alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; sulfoxides represented by the formula R (R ′) S ＝ O, wherein R and R ′ are each a straight-chain Or branched alkyl groups having 5 or less carbon atoms), preferably sulfoxides such as dimethylsulfoxide and diethylsulfoxide;
Amines having 5 or less carbon atoms, preferably lower aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine and hexylamine, preferably dimethylamine, diethylamine, dipropylamine and diisopropylamine Lower aliphatic secondary amines, preferably lower aliphatic tertiary amines such as trimethylamine and triethylamine, and the like, and mixtures thereof are suitably used. Among them, a particularly preferred polar solvent is water. According to the aspect of the present invention, a method of heating and drying the recording medium after cleaning the recording medium with a polar solvent can be used.

In the present invention, a recording medium that is capable of absorbing ink compositions such as paper and one that is substantially non-absorbable with respect to ink compositions is suitably used. "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 in 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,
Recording media and paper that have been coated with a metal sheet by a method such as evaporation on a plastic sheet based on ABS resin, polyvinyl chloride, etc., a metal surface such as brass, iron, aluminum, SUS, or copper, or a non-metallic base material A recording medium that has been subjected to a water-repellent treatment or the like as a base material, a recording medium that has been subjected to a water-repellent treatment or the like on the surface of a fiber such as cloth, and an inorganic material fired at high temperature
Examples include a recording medium made of a so-called ceramic material.

In the case where printing is performed on a non-absorbing recording medium using two liquids, if the surface tension of the non-absorbing recording medium is lower than the surface tension of the ink composition, the colorant after washing with water is used. Is not sufficiently fixed, and the abrasion resistance of the recorded matter may be slightly reduced. In these cases, as shown in the recording method of the present invention, the ink composition contains at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water, and has a non-absorbable surface tension of the ink composition. By making the surface tension of the recording medium or less, the wettability of the ink composition on the surface of the non-absorbing recording medium is improved, and the fixability of the colorant on the surface of the non-absorbing recording medium is improved. In a preferred embodiment of the recording method of the present invention, the surface tension of the ink composition is set to 40 mN / m.
The ink composition preferably contains a surfactant, and more preferably has a surface tension of 40 mN / m or less. Further, in the recording method of the present invention, the fixability of the colorant can be further improved by printing the ink composition on the non-absorbent recording medium in the order of the ink and the reaction liquid.

Ink Composition The ink composition used in the present invention contains at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water, and has a surface tension of 40 mN / m or less. It is preferred that In the present invention, the ink composition means a black ink composition when performing monochrome printing, and a color ink composition when performing color printing, specifically, a yellow ink composition and a magenta ink composition. , And cyan ink composition, and in some cases, black ink composition.

Resin emulsion particles The ink composition of the present invention comprises resin emulsion particles. In the present invention, “resin emulsion particles” refers to fine particles of a polymer component, that is, fine polymer particles. The “resin emulsion particles” are preferably made of a polymer having a film forming ability. "Resin emulsion" refers to an aqueous dispersion in which the continuous phase is water and the dispersed particles are resin emulsion particles. "Resin emulsion" may also be referred to as "polymer emulsion" or "water-based emulsion". In the present invention, specific examples of the polymer component constituting the resin emulsion particles include a styrene- (meth) acrylic acid copolymer, a styrene- (meth) acrylic acid copolymer, and a styrene- (meth) acrylate- ( (Meth) acrylic acid copolymer, poly (meth) acrylate, styrene-
Butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, chloroprene copolymer, polyolefin, polystyrene, polyvinyl acetate, polyamide, ethylene-vinyl acetate copolymer, vinyl acetate-acrylate copolymer, polyurethane, etc. No. In the present invention, the resin emulsion particles promote the fixation of the colorant to the surface of the recording medium by interacting with a reactant in a reaction solution described later, in particular, a polyvalent metal ion or polyallylamine or a derivative of polyallylamine. Having.

According to a preferred embodiment of the present invention, the minimum film forming temperature of the resin emulsion containing the resin emulsion particles is preferably room temperature or lower, more preferably 25 ° C. or lower, and most preferably 20 ° C. or lower. Is preferred. If the film formation of the resin emulsion can be carried out at room temperature or lower, after washing the printed recording medium with a polar solvent, heating and drying means are not required, and at the room temperature or lower, film formation on the printing surface automatically proceeds. It is preferable because the coloring agent firmly adheres to the recording medium. Here, the “minimum film forming temperature” means that the resin emulsion obtained by dispersing the resin emulsion particles in water is thinly cast on a metal plate such as aluminum, and when the temperature is raised, a transparent continuous film is formed. The lowest temperature at which a film is formed. Further, according to a preferred embodiment of the present invention, the glass transition temperature of the resin emulsion particles is preferably 10 ° C. or lower.

The term "film-forming property" means that when a resin emulsion particle is dispersed in water to form a resin emulsion, a water component which is a continuous phase of the resin emulsion is evaporated to form a polymer film. Means that The ink composition to which the resin emulsion particles are added,
When water or the aqueous organic solvent is removed from the periphery of the resin emulsion particles, a resin film (polymer film) is formed. This resin 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 resin emulsion particles is at least 5% by weight, preferably at least 8% by weight, based on the ink composition. The polymer fine particles of the resin emulsion are contained in a weight ratio of 1 to 20, more preferably 2 to 10, with respect to the colorant.

The particle size of the resin emulsion particles is 1
00 nm or less, more preferably 5 to 80 nm
It is about.

According to a preferred embodiment of the present invention,
The particle has a carboxyl group on its surface.
It also reacts with divalent metal salts and has high cohesiveness.
Preferably. Specifically, resin emulsion particles
Are 3 volumes of an aqueous emulsion of 0.1% by weight,
with 1 volume of an aqueous solution of a bivalent metal salt having a concentration of mol / l
The transmittance of the light having a wavelength of 700 nm is 50% of the initial value.
1 × 10 ^FourSeconds or less (preferably 1 × 10^ThreeSecond
Below, more preferably 1 × 10^TwoSeconds)
It has a cohesive property with a divalent metal salt. Resin emul
When John particles come into contact with divalent metal ions, they aggregate and float.
This creates play and reduces the clarity of the solution. The amount of this suspended matter generated
Is measured by light transmittance. Where the divalent metal ion
What is Ca²⁺, Cu²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Ba
²⁺And the anions that form salts with it
Cl^-, NO^3-, I^-, Br^-, ClO^3-And CH_ThreeCO
O ^-Is raised. Such high cohesiveness is
The particles have relatively many carboxyl groups on their surface.
This is considered to be due to having As above
A large amount of carboxyl groups that exhibit
Ink comprising resin emulsion particles on the surface
The composition is a water-repellent treated inkjet recording head.
No affinity for the nozzle plate. Therefore, conventionally,
Problems with ink compositions containing water-soluble resins
The ink composition wets the nozzle plate well,
As a result, ink droplets may be bent and ejection failures may occur.
It has the great advantage that it is effectively prevented. Advantages of the present invention
According to a preferred embodiment, the resin emulsion particles have a concentration of 10%.
Teflon plate of resin emulsion dispersed in water by weight
The above contact angle is preferably 70 ° or more. Further
The resin emulsion particles are dispersed in water at 35% by weight.
The surface tension of the resin emulsion is 40 mN / m (40
dyne / cm, 20 ° C.) or more.
By using resin emulsion particles as described above,
In the inkjet recording method, more flight bend
Can be prevented, and good printing can be performed.

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

According to another preferred embodiment of the present invention, the resin emulsion particles comprise 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having a carboxyl group, and have a polymerizable double bond. It is preferable to have a structure cross-linked by a cross-linkable monomer having two or more and containing 0.2 to 4% by weight of a structure derived from the cross-linkable monomer. By using a cross-linkable polymer obtained by copolymerizing a cross-linkable monomer having two or more, more preferably three or more polymerizable double bonds at the time of polymerization to form a three-dimensional cross-link, the ink composition of the nozzle plate is reduced. It becomes more difficult to get wet by the object, the flight bending can be further prevented, and the ejection stability can be further improved.

In the present invention, a resin emulsion particle having a single particle structure can be used. On the other hand, in the present invention, it is also possible to use resin emulsion particles 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 kinds of 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 shell part partially covers the core part may be used.
Further, a part of the shell polymer may form a domain or the like in the core particle. Further, a layer having a multilayer structure of three or more layers including layers having different compositions may be further provided between the core part and the shell part.

According to a preferred embodiment of the present invention, it is preferable that the core is formed of a polymer having an epoxy group and the shell is formed of a polymer 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 emulsion particles (that is, polymer fine particles) are united and deformed by the pressure accompanying film formation. Thereby, the epoxy group of the core and the carboxyl group of the shell are combined to form a network 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 1 to 10% by weight. Here, the reaction between some epoxy groups and carboxyl groups before film formation is permissible in the present invention as long as the film-forming ability is not lost. In the present invention, the property that a reactive functional group coexists in such a resin emulsion particle 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 resin emulsion used in the present invention is:
It 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.

Examples of the unsaturated vinyl monomer include acrylic ester monomers, methacrylic ester monomers, aromatic vinyl monomers, and vinyl ester monomers generally used in emulsion polymerization. , Vinyl cyanide compound monomers,
Examples include halogenated monomers, 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,
Methacrylates such as n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and the like; and Vinyl esters such as vinyl acetate; acrylonitrile,
Vinylcyan compounds such as methacrylonitrile; halogenated monomers such as vinylidene chloride and vinyl chloride; styrene, 2-methylstyrene, vinyltoluene, tert-butylstyrene, chlorostyrene, vinylanisole and vinylnaphthalene Aromatic vinyl monomers; ethylene,
Olefins such as propylene and isopropylene; dienes such as butadiene and chloroprene; vinyl ethers;
And vinyl monomers such as vinyl ketone and vinyl pyrrolidone. For a monomer having no carboxyl group, the use of an unsaturated vinyl monomer having a carboxyl group is indispensable. Preferred examples thereof include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. And the use of methacrylic acid is preferred. In addition, usable emulsifiers include anionic surfactants, nonionic surfactants, and mixtures thereof.

In the present invention, as described above,
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-
Diacrylate compounds such as butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, and polypropylene glycol diacrylate; trimethylolpropane triacrylate, trimethylolethane triacrylate Acrylates, triacrylate compounds such as tetramethylol methane 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, 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 Dimethacrylate compounds such as methacrylate, polybutylene glycol dimethacrylate, 2,2′-bis (4-methacryloxydiethoxyphenyl) propane; trimethacrylate compounds such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate; methylene bis Acrylamide and divinylbenzene are mentioned.

Further, by adding acrylamides or hydroxyl group-containing monomers in addition to the above monomers, the printing stability can be further improved. Examples of acrylamides include acrylamide and N, N '
-Dimethylacrylamide. 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 do.

The resin emulsion composed of resin emulsion particles having a core-shell structure is prepared by a known method.
Generally, it is produced 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 the unsaturated vinyl monomer used in the polymerization include those described above.

The introduction of an epoxy group into the above-mentioned core may be achieved by co-existing an unsaturated vinyl monomer having an epoxy group, such as glycidyl acrylate, glycidyl methacrylate, or allyl glycidyl ether, with another unsaturated vinyl monomer. Examples of the method include a method of polymerizing, or a method of simultaneously adding an epoxy compound when preparing core particles by polymerizing one or more unsaturated vinyl monomers to form a composite. The former method is preferred from the viewpoint of easiness of polymerization and polymerization stability.

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.

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

According to a preferred embodiment of the present invention, the resin is preferably a polymer having both a hydrophilic part and a hydrophobic part.

Colorant The colorant contained in the ink composition used in the present invention includes:
Any of a dye and a pigment may be used. Pigments are preferred in terms of light resistance and water resistance. It is also possible to use a pigment and a dye together.

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 or a thermal method can be used. Examples of organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc., dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

In particular, carbon black used as black ink includes No. 2300, No. 900, MCF
88, No. 33, No. No. 40, No. 45, No. 52, MA7, MA8, MA10
0, No2200B etc. are Raven 5750, Rave manufactured by Columbia
n 5250, Raven 5000, Raven3500, Raven 1255, Raven 7
00 etc. are Cabot's Regal 400R, Regal 330R, Re
gal 660R, Mogul L, Monarch 700, Monarch 800, Mona
rch 880, Monarch 900, Monarch 1000, Monarch 1100,
Monarch 1300, Monarch 1400, etc. are Colo manufactured by Degussa
r Black FW1, Color Black FW2, Color Black FW2V, Co
lor Black FW18, Color Black FW200, Color Black S15
0, Color Black S160, Color Black S170, Printex35,
Printex U, Printex V, Printex 140U, Special Black
6, Special Black 5, Special Black 4A, Special Bla
ck 4 etc. can be used. Examples of the pigment used in the yellow ink include C.I. I. Pigment Yellow1, C.I. I. Plgment Yel
low2, C. I. Pigment Yellow 3, C.I. I. Pigment Yellow
12, CI Pigment Yellow 13, C.I. I. Pigment Yellow 14,
C. I. Pigment Yellow 16, CI Pigment Yellow 17, C.I.
I. Pigment Yellow 73, CI Pigment Yellow 74, C.I. I. P
igment Yellow75, C.I. I. Pigment Yellow83, C.I. I. Pig
ment Yellow93, C.I. I. Pigment Yellow95, C.I. I. Pigme
nt Yellow97, C.I. I. Pigment Yellow 98, C.I. I. Pigment
Yellowl14, C.I. I. Pigment Yellow128. CI. Pigment
Yellow129, CI. Pigment Yellow151, C.I. I. Pigment Y
ellow154 and the like. Examples of the pigment used in the magenta ink include C.I. I. Pigment Red5, C.I. I. Pigm
ent Red7, CI. Pigment Red 12, C.I. I. Pigment Red4
8, C. I. Pigment Red4, C.I. I. Pigment Red 57, C.I. I. P
igment Red 57: 1, CI. Pigment Red 112, CI Pigment
Red 122, CI Pigment Red 168, CI Pigment Red 184, C.
I. Pigment Red 202 and the like. Pigments used in cyan ink include CI Pigment Blue1, CI Pigme
nt Blue 2, CI Pigment Blue 3, CI Pigment Blue 15:
3, C. I.Pigment Blue15: 4, CIigment Blue 16,
CI Pigment Blue 22, CI Pigment Blue 60, C.I. I. Vat B
lue4, C. I. Vat Blue60 and the like.

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

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

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 glue,
Proteins such as gelatin, casein, albumin;
Natural gums such as gum arabic and tragacanth; glucosides such as saponin; alginic acid derivatives such as alginic acid and propylene glycol alginate, triethanolamine alginate and ammonium alginate; cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose and ethylhydroxycellulose And the like. 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-acryl. Acrylic resins such as acid ester copolymer, acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene -Α-methylstyrene-
Acrylic acid copolymer, styrene-α-methylstyrene-
Styrene-acrylic resin such as acrylic acid-acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-
Acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer Examples include polymers, vinyl acetate-based copolymers such as 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.

The content of the colorant in the ink composition is as follows:
It is preferably about 0.5 to 25% by weight, more preferably 2 to 25% by weight.
About 15% by weight.

A water-soluble organic solvent, acetylene glycol,
According to a preferred embodiment of the present invention, the surface tension of the ink composition is preferably 40 mN / m or less, and the surface tension of the ink composition is reduced to 40 mN / m by containing a surfactant.
/ M or less. According to a more preferred embodiment of the present invention, the surfactant contained in the ink composition is acetylene glycol. As the acetylene glycol that can be used in the ink composition used in the present invention, a compound represented by the following chemical formula (IV) is preferable.

Embedded image (In the formula, 0 ≦ m + n ≦ 50, R1, R2, R3, and R4 are each independently an alkyl group.) As a typical example of the compound represented by the above formula, Olfine Y, Surfy Knoll 82, Surfynol 44
0, Surfynol 465 and Surfynol 485 (all manufactured by Air Products and Chemicals, Inc.). These may be used alone or in combination of two or more.

The ink used in the present invention may further contain a water-soluble organic solvent, and a preferable water-soluble organic solvent is a low-boiling organic solvent.
Methanol, ethanol, n-propyl alcohol, iso
-Propyl alcohol, n-butanol, Sec-butanol, tert-butanol, iso-butanol, n-pentanol and the like. Particularly, a monohydric alcohol is preferable.

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

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 more 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 colorant, and excellent storage stability can be realized. Further, an ink composition that maintains fluidity and redispersibility for a long time even when left in an open state (a state where it is exposed to air at room temperature) can be realized. 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 higher include ethylene glycol (boiling point: 197 ° C .; hereinafter, the boiling point is shown in parentheses) and propylene glycol (187
° C), diethylene glycol (245 ° C), pentamethylene glycol (242 ° C), trimethylene glycol (214 ° C)
° C), 2-butene-1, 4-diol (235 ° C), 2-ethyl-1,3-hexanediol (243 ° C), 2-methyl-
2,4-pentanediol (197 ° C), N-methyl-2-pyrrolidone (202 ° C), 1,3-dimethyl-2-imidazolidinone (257-260 ° C), 2-pyrrolidone (245 ° C), glycerin (290 ° C), tripropylene glycol monomethyl ether (243 ° C), dipropylene glycol monoethyl glycol (198 ° C), dipropylene glycol monomethyl ether (190 ° C), dipropylene glycol (2
32 ° 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), diethylene glycol monomethyl ether (194 ° C.) and a boiling point of 20
Those having a temperature of 0 ° C. or higher are more preferable. 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 about 0.5 to 40% by weight, more preferably 2 to 20% by weight, based on the ink composition.

According to a preferred embodiment of the present invention, the ink composition used in the present invention can comprise a sugar, a tertiary amine, an alkali hydroxide, or an alginic acid derivative. Addition of sugar and tertiary amine results in wetting.
Further, the addition of the tertiary amine and the alkali hydroxide brings about stabilization of the dispersion of the colorant in the ink composition and the polymer fine particles of the resin emulsion in the ink.

Examples of sugars include monosaccharides, disaccharides, oligosaccharides
Sugars (including trisaccharides and tetrasaccharides) and polysaccharides
Preferably glucose, mannose, fructo
, Ribose, xylose, arabinose, galactose
, Aldonic acid, glucitol, sorbitol, maltoux
, Cellobiose, lactose, sucrose, trehalose
And maltotriose. here,
Polysaccharides mean sugars in a broad sense, alginic acid, α-cyclo
Dextrin, cellulose, and other substances that exist widely in nature
It will be used in a meaning that includes quality. Also, these sugars
As the derivative of the reducing sugar of the above-mentioned saccharide [(for example,
Sugar alcohol (general formula HOCH_Two(CHOH) nCH _TwoOH (where n
= Represents an integer of 2 to 5)], an oxidized sugar (for example,
Aldonic acid, uronic acid, etc.), amino acids, thiosugars, etc.
can give. In particular, sugar alcohols are preferred.
And maltitol, sorbitol and the like. this
The amount of sugar added is preferably about 0.1 to 40% by weight,
More preferably, it is about 1 to 30% by weight.

Examples of the tertiary amine include trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, triisopropanolamine, butyldiethanolamine and the like. These may be used alone or in combination. The amount of these tertiary amines added to the ink composition is
Preferably about 0.1 to 10% by weight, more preferably,
0.5 to 5% by weight.

Examples of the alkali hydroxide include potassium hydroxide, sodium hydroxide and lithium hydroxide, and the amount of the alkali hydroxide is preferably about 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. It is about.

Preferred examples of the alginic acid derivative include:
Alginic acid alkali metal salts (eg, sodium salt, potassium salt), alginic acid organic salts (eg, triethanolamine salt), and alginic acid ammonium salts are exemplified. The amount of the alginic acid derivative added to the ink composition is preferably about 0.01 to 1% by weight, and more preferably about 0.05 to 0.5% by weight.

The reason why a good image can be obtained by adding the alginic acid derivative is not clear, but the polyvalent metal salt present in the reaction solution reacts with the alginic acid derivative in the ink composition to change the dispersion state of the colorant. This is considered to be caused by promoting the fixation of the colorant to the recording medium.

The ink composition used in the present invention may further contain a surfactant. As examples of the surfactant, the same surfactant as that used in the preparation of the resin emulsion described above can be suitably used.

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 Solution The reaction solution used in the present invention comprises a reactant. Here, the term "reactant" refers to the state of dispersion and / or dissolution of pigments and / or resin emulsion particles in the ink composition. It can be broken and agglomerated. Examples include polyvalent metal salts, polyamines, and polyamine derivatives.

The polyvalent metal salt that can be used in the reaction solution is composed of polyvalent metal ions having two or more valences and an anion bonded to these polyvalent metal ions, and is soluble in water. Specific examples of polyvalent metal ions include Ca ²⁺ , Cu ²⁺ ,
Divalent metal ions such as Ni ²⁺ , Mg ²⁺ , Zn ²⁺ , Ba ²⁺ , Al ³⁺ ,
^Examples include trivalent metal ions such as Fe ³⁺ and Cr ³⁺ . Anions include Cl ⁻ , NO ₃ ⁻ , I ⁻ , Br ⁻ , ClO ₃ ⁻ , and CH ₃ CO
O- ^and others.

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

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

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

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

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

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

Polyallylamine and polyallylamine derivatives which can be used in the reaction solution are cationic polymers which are soluble in water and are positively charged in water. For example,
Examples include those represented by the following formula (I), formula (II), and formula (III).

[0067]

Embedded image (In the above formula, X- represents a chloride ion, a bromide ion, an iodide ion, a nitrate ion, a phosphate ion, a sulfate ion, an acetate ion, etc.) In addition to the above, a polymer obtained by copolymerizing allylamine and diallylamine or diallylmethylammonium Copolymers of chloride and sulfur dioxide can be used.

The content of these polyallylamine and polyallylamine derivative is 0.5 to 10% by weight of the reaction solution.
It is preferred that

According to a preferred embodiment of the present invention, the reaction solution contains a polyol in addition to the polyvalent metal salt. Here, this polyol has a vapor pressure at 20 ° C. of 0.01.
mmHg or less, and the addition amount thereof is 1 or more, preferably 1.0-5.
It is set to 0. Further, according to a preferred embodiment of the present invention, the amount of the polyol added to the reaction solution is preferably 10% by weight or more, more preferably 10 to 30% by weight.
It is about.

Preferred specific examples of the polyol include polyhydric alcohols such as glycerin, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1,4-butanediol. further,
Preferred specific examples of polyols include sugars such as monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides)
And polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucosyl, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like.

Even if these polyols are added alone,
It may be added as a mixture of two or more. When it is added as a mixture of two or more, the amount added is 1 or more by weight in total with respect to the polyvalent metal salt.

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. Preferred examples of the high-boiling organic solvent, although partially overlap with the polyol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol And 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,
Alkyl ethers of polyhydric alcohols such as triethylene glycol monoethyl ether and triethylene glycol monobutyl ether, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, triethanol Amines and the like. 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 is not particularly limited, but is preferably 0.5 to 40% by weight based on the reaction solution.
And more preferably about 2 to 20% by weight.

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

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

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

[0077]

Embedded image (In the formula, 0 ≦ m + n ≦ 50, R1, R2, R3, and R4 are each independently an alkyl group.) As a typical example of the compound represented by the above formula, Olfine Y, Surfy Knoll 82, Surfynol 44
0, Surfynol 465 and Surfynol 485 (all manufactured by Air Products and Chemicals, Inc.). These may be used alone or in combination of two or more.

According to a preferred embodiment of the present invention, the reaction solution is
It comprises triethanolamine for pH adjustment. When triethanolamine is added, the amount added is 0.
About 2.0% by weight is preferred.

The reaction liquid may be colored by adding the colorant described in the section of the ink composition to have the function of the ink composition.

Recording Apparatus A recording apparatus according to the present invention will be described with reference to the drawings. FIG. 1 shows the configuration of a recording apparatus according to the present invention.
A recording medium is carried from a supply source 1 containing a recording medium to a printing process including an inkjet recording mechanism 2. The reaction liquid and the ink composition are ejected from the recording head provided in the inkjet recording mechanism 2 onto the surface of the recording medium to form the printing surface 3. The recording head includes a nozzle for discharging a reaction liquid and a nozzle for discharging an ink composition, which are not shown in the drawing. The recording medium on which the printing surface 3 is formed is carried into a cleaning step. The recording medium on which the printing surface 3 is formed is washed by a washing mechanism 4 with a polar solvent.
The cleaning mechanism 4 has means for collecting and separating a cleaning liquid not shown in the figure. After the cleaning, the recording medium is carried into a drying step. The recording medium is dried by the drying mechanism 5. The drying mechanism 5 may be a device that contacts and heats the recording medium, or may be a device that heats the recording medium without contacting it, such as irradiating infrared rays or blowing hot air.
After drying, the recording medium is carried into the product storage 6 as a product. Note that this recording apparatus is performed by a roll or a conveyor not shown in the figure as a means for conveying the recording medium.

FIG. 2 shows an embodiment of the recording apparatus according to the present invention. 2, the components having the same configuration as the mechanism in FIG. 1 are denoted by the same reference numerals as those in FIG. From the PET film roll 11, the PET film is carried into a printing process including the inkjet recording mechanism 2. The reaction liquid and the ink composition are ejected from the recording head provided in the inkjet recording mechanism 2 onto the surface of the PET film to form the printing surface 3. The PET film on which the printing surface 3 is formed passes through the support 12 and is carried into the cleaning step. The PET film on which the printing surface 3 is formed is washed with a polar solvent in a washing machine groove 4. After washing, the PET film is carried into the drying process. The PET film is dried by the drying mechanism 5. After drying, the printed PET
It is wound around a roll 13 as a film product.

[0082]

The embodiments of the present invention will be described below, but these examples explain the contents of the present invention and do not limit the scope of the present invention.

Preparation of Resin Emulsion Resin Emulsion 1 A flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged with 100 ml of distilled water and 0.1 g of potassium persulfate. The temperature was heated to 70 ° C. Then, 100 ml of distilled water and sodium dodecylbenzenesulfonate were added to 1. An emulsion was prepared by stirring Og, 30 g of styrene, 55 g of 2-ethylhexyl acrylate, and 5 g of methacrylic acid. This was gradually dropped into the flask using a dropping funnel. The obtained emulsion was cooled to room temperature, filtered through a 0.4 μm filter, and prepared with distilled water so that the concentration of resin emulsion particles became 35%. The particle diameter of the obtained resin emulsion particles is 70 nm, the glass transition point is 5 ° C., the minimum film forming temperature of the obtained resin emulsion is about 20 ° C., and the surface tension is 48 × 10 ⁻³ N / m (20
° C). 3 volumes of the resin emulsion having 0.1% by weight of the resin emulsion particles and 1 volume of a 1 mol / l aqueous solution of magnesium nitrate are brought into contact with each other, and the time (half-life) at which the light transmittance at 700 nm becomes 50% of the initial value (half-life) Was 80 seconds. The contact angle of the resin emulsion prepared so as to contain 10% by weight of the resin emulsion particles on a Teflon plate was 78 °.

Resin Emulsion 2 A flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged with 100 ml of distilled water and 0.1 g of potassium persulfate. Until heated. Then, 100 ml of distilled water and sodium dodecylbenzenesulfonate were added to 1. An emulsion was prepared by stirring Og, 50 g of styrene, 35 g of 2-ethylhexyl acrylate and 5 g of methacrylic acid. This was gradually dropped into the flask using a dropping funnel. The obtained emulsion was cooled to room temperature, and the emulsion was filtered with a 0.4 μm filter, and the emulsion was prepared with distilled water so that the concentration of the resin emulsion particles became 35%. The particle size of the obtained resin emulsion particles is 120 nm,
The glass transition point is 40 ° C., the minimum film forming temperature of the obtained resin emulsion is about 60 ° C., and the surface tension is 42 × 10 ⁻³ N / m (20
° C). 3 volumes of the resin emulsion having 0.1% by weight of the resin emulsion particles and 1 volume of a 1 mol / l aqueous solution of magnesium nitrate are brought into contact with each other, and the time (half-life) at which the light transmittance at 700 nm becomes 50% of the initial value (half-life) Was 800 seconds. The contact angle on the Teflon plate of the resin emulsion prepared so as to contain 10% by weight of the resin emulsion particles was 65 °.

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) the mixture) for 2 hours. Thereafter, the glass beads were removed to prepare a pigment dispersion. Next, the solvent excluding the pigment and the dispersant was mixed, and the resulting ink dispersion was gradually dropped while stirring the pigment dispersion liquid as an ink solvent, followed by stirring at room temperature for 20 minutes. The mixture was filtered through a 5 μm membrane filter to obtain an ink composition for inkjet recording.

Ink composition 1 Carbon black MA7 (manufactured by Mitsubishi Chemical) 5% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 1 (as concentration of polymer fine particles) 10% by weight Surfynol 465 1% % Glycerin 10% by weight Deionized water Remaining Surface tension: 33 (mN / m)

Ink composition 2 Carbon black MA7 (manufactured by Mitsubishi Chemical Corporation) 5% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 2 (as concentration of polymer fine particles) 10% by weight Surfynol 465 5% by weight glycerin 10% by weight Deionized water Remaining Surface tension: 38 (mN / m)

Ink composition 3 Carbon black MA7 (manufactured by Mitsubishi Chemical Corporation) 5% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Glycerin 10% by weight Deionized water Remaining surface tension: 45 (mN / m)

Color Ink Set 1 Cyan Ink 1 C.I. I Pigment Blue 15: 3 2% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 1 (as the concentration of polymer fine particles) 10% by weight Diethylene glycol 15% by weight Surfynol 465 1% by weight Ion-exchanged water residue Amount Surface tension: 33 (mN / m) Magenta ink 1 C.I. Pigment Red 122 3% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 1 (as the concentration of polymer fine particles) 15% by weight Diethylene glycol 10% by weight Surfinol 465 0.6% by weight Surfinol TG 0 0.3% by weight Deionized water Remaining surface tension: 34 (mN / m) Yellow ink 1 I Pigment Yellow 74 3.5% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 1 (as concentration of polymer fine particles) 15% by weight Diethylene glycol 10% by weight Surfynol 465 1% by weight Ion-exchanged water residue Quantity Surface tension: 33 (mN / m)

Color Ink Set 2 Cyan Ink 2 C.I. I Pigment Blue 15: 3 2% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 2 (as concentration of polymer fine particles) 10% by weight Diethylene glycol 15% by weight Surfynol TG 0.3% by weight Ion exchange Water Remaining Surface tension: 37 (mN / m) Magenta ink 2 C.I. I Pigment Red 122 3% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 2 (as the concentration of polymer fine particles) 15% by weight Diethylene glycol 20% by weight Surfynol 465 0.5% by weight Deionized water residue Amount Surface tension: 38 (mN / m) Yellow ink 2 C.I. I Pigment Yellow 74 3.5% by weight Styrene-acrylic acid copolymer (dispersant) 1% by weight Resin emulsion 2 (as the concentration of polymer fine particles) 15% by weight Diethylene glycol 10% by weight Surfynol 465 0.5% by weight ion exchange Water Remaining Surface tension: 38 (mN / m)

Color Ink Set 3 Cyan Ink 3 Pigment KET BLUE EX-1 3% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Glycerin 10% by weight Deionized water residue Amount Surface tension: 50 (mN / m) Magenta Ink 3 Pigment KET Red 309 4% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Glycerin 15% by weight Deionized water Remaining amount Surface tension: 48 (mN / m) Yellow ink 3 Pigment KET Yellow 403 3% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer (dispersant) 1% by weight Glycerin 15% by weight Ion exchange Water Remaining Surface tension: 48 (mN / m)

Preparation of Reaction Solution A reaction solution was prepared according to the following composition. Reaction liquid 1 Magnesium nitrate hexahydrate 25% by weight Triethylene glycol / mono / butyl ether 10% by weight Glycerin 10% by weight Deionized water

Reaction liquid 2 Polyallylamine PAA-HCL-3L 20% by weight (resin component 50%, manufactured by Nitto Boseki) Diethylene glycol 15% by weight Deionized water

Printing Evaluation Test Examples were made by combinations shown in Table 1 below.
The printed material targeted for the following evaluation was prepared by printing the ink composition and the reaction solution of the above example on an aluminum plate at normal temperature and normal humidity using an inkjet printer MJ-930C manufactured by Seiko Epson Corporation. Obtained. Printing was performed simultaneously on the aluminum plate with 100% duty of the reaction liquid, black ink, and color ink, and printing was performed both when printing the reaction liquid first and when printing the ink first. After printing, the printed matter was washed with water and subjected to the following printing evaluation test. The unit “duty” used in the present specification is defined by the following formula (I):
This shows the unit of the calculated value D.

(Equation 1)

[Table 1]

Evaluation 1: Evaluation of ink fixation after washing The printed surface of the printed matter was strongly rubbed with fingers and nails, and the ink fixability was evaluated according to the following criteria. A: There was no peeling of the ink on the aluminum plate. B: The ink was slightly peeled when rubbed with a nail. C: The ink peeled slightly when rubbed with a finger, and peeled when rubbed with a nail. D: The ink completely peeled off even when rubbed with a finger. Evaluation 2: Color Bleed The printed matter was visually evaluated for uneven color mixture at the color boundary according to the following criteria. A: The boundary was clear without color mixing. B: Color mixture slightly occurred. C: Color mixing occurred in a whisker-like manner. D: The colors were mixed so that the color boundaries were not clear.

The results of the above evaluation test were as shown in Table 2 below.

[Table 2]

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a recording apparatus according to the present invention.

FIG. 2 is a view showing one embodiment of a recording apparatus according to the present invention, in which the recording apparatus for printing a PET film is shown.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Supply source 1 Recording head 2 Ink jet recording mechanism 3 Printing surface 4 Cleaning mechanism 5 Drying mechanism 6 Product storage tray 11 PET film roll 12 Support stand 13 Product roll

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41J 3/04 101Z F-term (Reference) 2C056 EA09 EA13 FB01 FB04 FC01 2H086 BA05 BA18 BA19 BA23 BA52 BA59 BA60 4J039 AD01 AD03 AD04 AD08 AD09 AD10 AD11 AD15 AD17 AE04 AE05 AE08 BA04 BA13 BA35 BA37 BC07 BC08 BC09 BC10 BC11 BC13 BC15 BC50 BE01 BE02 BE12 BE22 BE28 CA06 EA15 EA16 EA17 EA19 EA36 EA43 EA48 FA01 FA02 FA06 GA24

Claims (28)

[Claims] An ink composition comprising at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water on a recording medium, and a reaction for forming an aggregate when the ink composition comes into contact with the ink composition. A printing method for printing by adhering a reaction liquid containing an agent, wherein the step of adhering the reaction liquid on a recording medium, and adhering the ink composition on a recording medium to record an image. And a step of washing the recording medium printed by attaching the reaction liquid and the ink composition with a polar solvent, wherein a surface tension of the ink composition is A recording method that has a surface tension or less. 2. The ink composition has a surface tension of 40 mN /
2. The recording method according to claim 1, wherein m is equal to or less than m. 3. The ink composition contains a surfactant,
2. The recording method according to claim 1, wherein the surface tension is 40 mN / m or less. 4. The recording method according to claim 3, wherein said surfactant is acetylene glycol. 5. The recording method according to claim 4, wherein said acetylene glycol is a compound represented by the following chemical formula. Embedded image (Where 0 ≦ m + n ≦ 50, R1, R2, R3, and R4 are each independently an alkyl group) 6. The recording method according to claim 1, wherein said recording medium is substantially non-absorbable with respect to said ink composition. 7. The recording method according to claim 1, wherein the surface of the recording medium is made of plastic, rubber, metal, or ceramic. 8. The recording method according to claim 1, wherein the step of recording an image by discharging droplets of the ink composition onto the recording medium is performed before the step of attaching the reaction liquid to the recording medium. 9. The recording method according to claim 1, wherein said colorant is a pigment. 10. The recording method according to claim 1, wherein a minimum film forming temperature of the resin emulsion containing the resin emulsion particles is 25 ° C. or less. 11. The content of the resin emulsion particles is as follows:
5% by weight or more with respect to the ink composition, and the resin emulsion particles with respect to the colorant in a weight ratio of 1 to 20
The recording method according to any one of claims 1 to 10, wherein the recording method includes the following. 12. The resin emulsion particles having a particle size of 10
The recording method according to claim 1, wherein the recording method is 0 nm or less. 13. The resin emulsion particles have a film-forming property, have a carboxyl group on the surface thereof,
When 3 volumes of an aqueous emulsion of 1% by weight and 1 volume of an aqueous solution of a divalent metal salt having a concentration of 1 mol / l are brought into contact with each other, the time at which the light transmittance at a wavelength of 700 nm becomes 50% of the initial value is 1
The recording method according to any one of claims 1 to 12, wherein the recording method has a reactivity with a divalent metal salt so as to be 10 ⁴ seconds or less. 14. The resin emulsion particles of 10% by weight.
The recording method according to any one of claims 1 to 13, wherein the resin emulsion prepared so as to have a contact angle on a Teflon (registered trademark) plate of 70 ° or more. 15. The resin emulsion particles of 35% by weight
The resin emulsion prepared so as to have a surface tension of 40 mN / m (20 ° C.) or more.
5. The recording method according to claim 4. 16. The resin emulsion particles having a structure derived from an unsaturated vinyl monomer having a carboxyl group.
A structure cross-linked by a cross-linkable monomer having at least 10% by weight and having two or more polymerizable double bonds, wherein a structure derived from the cross-linkable monomer is 0.2 to 4%. weight%
The recording method according to any one of claims 1 to 15, wherein the recording method comprises: 17. The recording method according to claim 1, wherein said resin emulsion particles have a core-shell structure. 18. The recording method according to claim 1, wherein the resin emulsion particles have a self-crosslinking property. 19. A core comprising a resin having an epoxy group, and a shell comprising a resin having a carboxyl group.
The recording method according to claim 1. 20. The recording method according to claim 1, wherein the water-soluble organic solvent has a boiling point of 180 ° C. or higher. 21. The recording method according to claim 1, wherein the reactant is a polyvalent metal salt, polyallylamine, or a derivative of polyallylamine. 22. The recording method according to claim 1, wherein the polyvalent metal salt is a nitrate or a carboxylate. 23. A carboxylic acid ion constituting the carboxylate is a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms (a hydrogen atom on the saturated aliphatic hydrocarbon group of the carboxylic acid is substituted with a hydroxyl group). Or 6-1 carbon atoms
23. The recording method according to claim 22, wherein the recording method is derived from a carbocyclic monocarboxylic acid of 0. 24. The recording method according to claim 1, wherein said reaction solution further comprises triethylene glycol monobutyl ether and glycerin. 25. An ink jet recording method in which 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 the droplet to the recording medium to perform printing. The recording method according to any one of claims 1 to 24. 26. A recorded matter printed by the recording method according to any one of claims 1 to 25. 27. An ink composition comprising a recording medium containing at least a colorant, resin emulsion particles, a water-soluble organic solvent, and water, and having a surface tension equal to or lower than the surface tension of the recording medium; What is claimed is: 1. A recording apparatus for performing printing by adhering a reaction liquid containing a reaction agent that forms an aggregate when brought into contact with a composition, comprising: means for adhering the reaction liquid on a recording medium; and Means for recording an image by adhering the ink composition to a recording medium, means for adhering the reaction liquid onto a recording medium, and means for recording an image by adhering the ink composition onto a recording medium. And a means for washing the recording medium printed with the reaction liquid and the ink composition printed thereon with a polar solvent. 28. The ink jet recording means according to claim 27, wherein the means for controlling the means for adhering the reaction liquid on a recording medium and the means for adhering the ink composition on the recording medium to record an image is an ink jet recording means. The described device.