JPH1112519A - Ink composition giving highly light-resistant image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition excellent in abrasion resistance and water resistance as well as light resistance, and useful in color ink jet printers, etc., by including a coloring material, polymeric microparticles having ultraviolet light absorbing ability and light stability, and others. SOLUTION: This ink composition is obtained by including (A) 2-15 wt.% of a coloring material consisting of a pigment <=0.1 μm in particle size, (B) water, (C) 5-10 wt.% of a water-soluble organic solvent consisting of a low- boiling organic solvent such as a monohydric alcohol, and (D) 1-5 wt.% of polymeric microparticles <=30 deg.C in glass transition temperature, 5-100 nm or so in size with simple particle or core-shell structure made from a polymer emulsion prepared, for example, by adding an ultraviolet light absorber such as 2(2'-hydroxy-5'-methylphenyl)benzotriazole to a monomer component such as butyl acrylate or styrene followed by emulsion polymerization, and also 1-10 wt.% of a high-boiling organic solvent such as glycerol as a wetting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition, and more particularly, to an ink composition preferably used in an ink jet recording method.

[0002] In the recording method using the background art ink composition, a solvent component dissolving or dispersing the coloring material is essential. As the solvent component, a mixed solvent of water and a water-soluble organic solvent is widely used from the viewpoint of safety. When the ink composition is applied on a recording medium, the solvent component soaks or evaporates into the recording medium, thereby fixing the color material component on the recording medium and recording characters or images. Various performances are required for the obtained images.

[0003] Among the required performance, light resistance is as follows.
Various proposals have been made to improve the performance.
Water-soluble dyes are widely used as coloring materials for aqueous ink compositions due to their good water solubility, but it is generally pointed out that they have poor light fastness. Therefore, an ink composition in which a water-insoluble coloring material such as a pigment having excellent light resistance is dispersed has been proposed.

However, it has been pointed out that inorganic pigments such as carbon black and metal-containing organic pigments such as copper phthalocyanine pigment are excellent in light resistance, but many other organic pigments do not have sufficient light resistance. Was. Therefore,
It can be said that there is a need for a method for improving the light fastness of an ink composition using such an organic pigment as a coloring material. In addition, dyes are attractive because of the variety of available types, and a method that can improve the light fastness of an image even in an ink composition containing the dye as a coloring material has been desired.

[0005] More recently, color images have been formed with a plurality of ink compositions. In the case of a color image using such a plurality of ink compositions, if even one color has poor light resistance, the hue of the image changes and the quality of the color image is extremely deteriorated. Therefore, the color ink composition is required to have more controlled light fastness.

In recent years, ink jet recording printers have begun to spread widely. This ink jet recording method is a printing method in which small droplets of an ink composition are made to fly and adhere to a recording medium such as paper to perform printing. This method
The feature is that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. In particular, color ink jet recording apparatuses have been improved in image quality and have been used as photo output machines, and have also been used as digital printing machines, plotters, CAD output devices, and the like. Images printed by such widely used ink jet recording printers can be used in various forms, especially printed materials of photographic specifications are exposed to fluorescent light or direct sunlight such as outdoors for a long time as a display. It is conceivable to be in a place where it is done. Therefore, light resistance is an extremely important required property in the ink composition used in the ink jet recording method.

As a means for improving the light resistance of the ink composition, addition of an ultraviolet absorber or a light stabilizer to the ink composition can be considered. However, since most ultraviolet absorbers and light stabilizers are oil-soluble, it is difficult to make a sufficient amount of the water-soluble ink composition.

On the other hand, as an ink jet recording method, a method has recently been proposed in which a polyvalent metal salt solution is applied to a recording medium and then an ink composition containing a dye having at least one carboxyl group is applied ( For example, JP-A-5-202328). In this method,
An insoluble complex is formed from the polyvalent metal ion and the dye,
It is said that the presence of this composite makes it possible to obtain a high-quality image that is water-resistant and has no color bleed.

Further, by using a color ink containing at least a surfactant or a penetrating solvent for imparting permeability and a salt, and a black ink which thickens or aggregates by the action of the salt, an image is formed. It has been proposed that a high-quality color image having a high density and no color bleed can be obtained (Japanese Patent Laid-Open No. 6-10673).
No. 5). That is, an ink jet recording method has been proposed in which a good image can be obtained by printing two liquids of a first liquid containing a salt and an ink composition.

In addition, other ink jet recording methods for printing two liquids have been proposed (for example, see Japanese Patent Application Laid-Open No.
240557, JP-A-3-240558).

[0011]

SUMMARY OF THE INVENTION The present inventors have recently developed an ink composition by adding, as fine particles, a polymer having an ultraviolet absorbing ability and / or a light stabilizing ability and a film forming ability to the ink composition. We propose a method to improve light fastness.

That is, an object of the present invention is to provide an ink composition which realizes a printed image having excellent light fastness.

More specifically, the present invention relates to an ink composition which can provide not only light fastness, but also scratch resistance, water resistance, and an image having excellent print quality without bleeding or color bleed. Its purpose is to provide.

Another object of the present invention is to provide an ink composition which is excellent in ejection stability and storage stability when used in an ink jet recording method.

Still another object of the present invention is to provide an ink composition capable of obtaining an image of good quality, particularly an image free from bleeding and color bleed in a so-called two-liquid recording method.

The ink composition according to the present invention is an ink composition comprising a coloring material, water, a water-soluble organic solvent, and polymer fine particles, wherein the polymer fine particles are
It is composed of a polymer having a film forming ability and an ultraviolet absorbing ability and / or a light stabilizing ability.

[0017]

DETAILED DESCRIPTION OF THE INVENTION

1. Ink Composition The ink composition according to the present invention is used in a recording method using the ink composition. Examples of the recording method using the ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, and various other printing methods. In particular, the ink composition according to the present invention is preferably used for an ink jet recording method.

The ink composition according to the present invention basically comprises
It comprises a coloring material, water, a water-soluble organic solvent, and polymer fine particles. The polymer fine particles are made of a polymer having a film forming ability and an ultraviolet absorbing ability and / or a light stabilizing ability.

2. Polymer fine particles The polymer fine particles used in the ink composition according to the present invention have a film-forming ability.

In the present invention, the polymer fine particles having a film-forming ability mean those which form a uniform film when the ink composition containing the same is dried. The following theory is merely an assumption, and the reason why the ink composition according to the present invention realizes an image having excellent light fastness, provided that the present invention is not limited to the following theory, is as follows. When the ink composition according to the present invention adheres to the recording medium, the solvent component permeates or evaporates into the recording medium,
The color material is fixed on the recording medium. At that time, since the polymer fine particles contained in the ink composition have a film forming ability, a film covering the coloring material component is formed. Since this film is made of a polymer having an ultraviolet absorbing ability and / or a light stabilizing ability, it has an ultraviolet absorbing ability and / or a light stabilizing ability. More specifically, when the coloring material is a pigment, a film in which the pigment is dispersed is formed. The ultraviolet light is blocked by this film and does not reach the pigment therein, so that the image has light resistance.
When the coloring material is a dye, it is considered that a film in which the dye is incorporated therein is formed on the surface of the recording medium, and a part of the dye dyes the recording medium and is fixed therein. The ultraviolet light is blocked by this film and does not reach the layer of the recording medium on which the dye in or under the film is fixed, so that the image is considered to have light resistance.

According to a preferred embodiment of the present invention, the particle size of the polymer fine particles is preferably about 5 nm to 200 nm, more preferably about 5 nm to 100 nm.

The content of the fine polymer particles in the ink composition according to the present invention is preferably about 1 to 10% by weight, more preferably 1 to 5% by weight of the ink composition. According to a preferred embodiment of the present invention, the polymer fine particles preferably have a single particle structure. According to still another preferred embodiment, the polymer fine particles preferably have a core-shell structure composed of a core portion and a shell layer surrounding the core portion.

According to a preferred embodiment of the present invention, the polymer fine particles are preferably dispersed in the ink composition as dispersed particles of a polymer emulsion. That is,
In preparing the ink composition according to the present invention, the polymer fine particles are preferably mixed in a form of a polymer emulsion with the components constituting the ink composition. According to a preferred embodiment of the present invention, the particle size of the polymer fine particles in the polymer emulsion is preferably about 200 nm or less, more preferably about 5 to 100 nm. According to a preferred embodiment of the present invention, the polymer constituting the polymer fine particles preferably has a glass transition point of 30 ° C. or lower. By using such a polymer, the ink composition according to the present invention more reliably forms a film at normal temperature.

Further, according to a preferred embodiment of the present invention, when the polymer fine particles are dispersed in the ink composition as dispersed particles of the polymer emulsion, the minimum film forming temperature of the polymer emulsion is preferably 30 ° C. or lower. Here, the minimum film forming temperature refers to a temperature at which a transparent continuous film is formed when a polymer emulsion is thinly cast on a metal plate such as aluminum and the temperature is increased. According to this aspect, it is possible to improve the quick drying property, finger touch property, abrasion resistance, and water resistance of the printed matter.

Further, according to a preferred embodiment of the present invention, the polymer fine particles preferably contain a thermoplastic polymer as a component. Also, the polymer may be cross-linked. Examples of thermoplastic polymers include ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyethylene, polypropylene, polystyrene, poly (meth) acrylate, (meth) acrylic acid-
Styrene copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-maleic acid copolymer, styrene-itaconic acid ester copolymer, polyvinyl acetate, polyester, polyurethane, and polyamide However, the present invention is not limited to these.

According to the first preferred embodiment of the present invention, the polymer fine particles are composed of a polymer containing an ultraviolet absorber and / or a light stabilizer.

According to a second preferred embodiment of the present invention, the polymer fine particles are composed of a polymer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability in its structure. As described above, most of the ultraviolet absorbers and the light stabilizers are oil-soluble, so that it is difficult to make a sufficient amount of them exist in the water-soluble ink composition. However, according to the present invention, it is possible to obtain a water-soluble ink composition that can impart sufficient light fastness to an image printed thereby. Further, in any of the first and second embodiments, the abundance of the site having the ultraviolet absorbing ability and / or the light stabilizing ability in the polymer fine particles and the presence of the ultraviolet absorbing agent and / or the light stabilizer. Since the amount can be basically set arbitrarily, it is possible to obtain an advantage that its ultraviolet absorbing ability and / or light stabilizing ability can be set arbitrarily.

In the present invention, the ultraviolet absorbing ability and the ultraviolet absorbing agent and the light stabilizing ability and the light stabilizer follow the definitions understood in the art. In other words, from its mechanism of action, UV-absorbing ability and UV-absorbing agent generally means a strong energy possessed by UV-
It means that it is gradually converted to thermal energy and released by keto-enol type tautomerism, and is stabilized.On the other hand, the light stabilizing ability and the light stabilizing agent are radical scavenging, hydroperoxide decomposition, heavy metal , Which is stabilized by the quenching of singlet oxygen. In the present invention,
Either one may be present, but according to a preferred embodiment of the present invention, both are preferably present together.

2-1. Polymer Fine Particles of First Embodiment The polymer fine particles according to the first embodiment of the present invention are obtained by physically mixing an ultraviolet absorber and / or a light stabilizer with a polymer component described below.

The ultraviolet absorber and light stabilizer usable in the present invention include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a hindered phenol ultraviolet absorber, a salicylate ultraviolet absorber, and a cyanoacrylate ultraviolet absorber. Examples thereof include those selected from the group consisting of ultraviolet absorbers, nickel complex-based ultraviolet absorbers, and hindered amine-based light stabilizers.

More specifically, as the benzophenone-based ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone is exemplified.

As the benzotriazole-based ultraviolet absorber, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole and 2 (2'-hydroxy-4 '
-Octoxyphenyl) benzotriazole, 2 (2 ′
-Hydroxy-3'-tert-butyl-5'-methylphenyl) 5-chlorobenzotriazole.

Further, examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

Examples of the cyanoacrylate-based ultraviolet absorber include ethyl-2-cyano-3,3'-diphenylacrylate and methyl-2-cyano-3-methyl-3-methyl-3-cyano-3-methyl-3-methyl-3-acrylate.
(P-methoxyphenyl) acrylate, butyl-2-
And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Further, nickel complex salt ultraviolet absorbers include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2-2 ′
-Thiobis (4-tert-octylferrate) -2
-Ethylhexylamine nickel (II), 2-2'-thiobis (4-tert-octylferrate) triethanolamine nickel (II).

As the hindered amine light stabilizer, those having a 2,2,6,6-tetramethylpiperidine skeleton and 2,2,6,6-tetramethylpiperidine-1-oxyl (tri Acetone-amine-N-oxyl).

It is also possible to use commercially available UV absorbers or light stabilizers. The following are specific examples thereof.

First, 2,4-dihydroxybenzophenone (SEES) was used as a benzophenone-based ultraviolet absorber.
ORB 100 (Sibro Chemical), Biosorb 100
(Kyoto), KEMISORB 10 (Chempro Chemical),
ASL 23 (Shonan Chemical Industry), UVINUL 400
(BASF), Inhibitor DHBP (Eas
tman Kodak), 2-hydroxy-4-methoxybenzophenone (Sumisorb 110 (Sumitomo), SEESORB 101 (Shibro Kasei), Biosorb 110 (Kyoto), KEMISORB 11 (Chemipro Kasei), ASL 24 (Shonan Chemical Industry), UVI
NUL M-40 (BASF), Siasorb UV
9 (ACC), Tomisorb 300 (Yoshitomi)), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (SEESORB 101 S (Sibro Chemical), KE
MISORB 11 S (Chempro Chemical), ASL 2
4 S, 24 ST (Shonan Chemical Industry), UVINUL
MS-40 (BASF), Siasorb UV 284
(ACC), Harisorb 101S (Yoshitomi)), 2-hydroxy-4-n-octoxybenzophenone (Adecastab 1413 (Asahi Denka), Sumisorb 13)
0 (Sumitomo), SEESORB 102 (Sibro Chemical),
KEMISORB 12 (Chemipro Kasei), Biosorb 530 (joint), Siasorb UV 531 (A
CC), Tomisorb 800 (Yoshitomi), Harisorb 1
08 (Harima)), 2-hydroxy-4-n-dodecyloxybenzophenone (Inhibitor DHBP (Ea
stman Kodak), SEESORB 103
(Sibro Chemical), KEMISORB 13 (Chempro Chemical), UV-ehek Ald-320 (Fer
o)), bis (5-benzoyl-4-hydroxy-2-)
Methoxyphenyl) methane (ADK STAB LA-51)
(Asahi Denka)), 2,2'-dihydroxy-4-methoxy benzophenone (KEMISORB111 (Chemipro Kasei), Siasorb UV 24 (ACC)), 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone (UVINUL D-49 (BASF)).

As a benzotriazole-based ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (ADEKA STAB LA-32) is used.
(Asahi Denka), Sumisorb 200 (Sumitomo), SE
ESORB 701 (Sibro Chemical), TINUVIN
P (Ciba Geigy), KEMISORB 71 (Chempro Chemical), Biosorb 520 (Kyoto), JF-7
7 (Johoku)), 2- [2'-hydroxy-3 ', 5'-
Bis (α, α-dimethylbenzyl) phenyl] benzotriazole (TINUVIN 234 (Chiba Geigy)), 2- (2′-hydroxy-3 ′, 5′-di-t
-Butyl-phenyl) benzotriazole (ADK STAB LA-38 (Asahi Denka), Sumisorb 320
(Sumitomo), SEESORB 705 (Sibro Chemical), T
INUVIN 320 (Ciba Geigy), Biosorb 582 (Kyoto)), 2- (2'-hydroxy-3-)
t-butyl-5'-methylphenyl) -5-chlorobenzotrizole (ADEKA STAB LA-36 (Asahi Denka);
Sumisorb 300 (Sumitomo), SEESORB
703 (Sibro Chemical), TINUVIN 326 (Ciba
Geigy), Biosorb (joint), Tomissorb (Yoshitomi), JF-600 (Johoku)), 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole (adecastab) LA-34 (Asahi Denka), SEESORB 702 (Sibro Chemical), TIN
UVIN 327 (Chiba Geigy), KEMISOR
B 72 (Chempro Kasei), Biosorb 580 (Kyodo)), 2- (2'-hydroxy-3 ', 5'-di-t)
-Amyl) -benzotriazole (Sumisorb)
350 (Sumitomo), SEESORB 704 (Sibro Chemical), TINUVIN 328 (Ciba Geigy), Biosorb 591 (Kyoto)), 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole (Sumisorb 340 (Sumitomo) ), SEESORB
709 (Sibro Chemical), Biosorb 583 (joint), JF-83 (Johoku), Cyasorb UV54
11 (ACC)), 2,2'-methylene bis [4-
(1,1,3,3-tetramethylbutyl) -6- (2N
-Benzotriazol-2-yl) phenol] (ADK STAB LA-31 (Asahi Denka)).

As salicylate-based ultraviolet absorbers, phenyl salicylate (SEESORB 201 (Sibro Chemical), Salol P (Iwaki), KEMISORB 21
(Chemipro Kasei)), 4-t-butylphenyl salicylate (SEESORB 202 (Sibro Kasei), Butisalol (Iwaki), KEMISORB 28 (Chemipro Kasei) DICTBS (Japan)).

Ethyl-2-cyano-3,3'-diphenyl acrylate (SEESORB501 (Shibro Kasei), Biosorb 910 (Kyoto), Uhisolator 300 (Daiichi Kasei Kogyo), UVINUL N-589 as cyanoacrylate-based ultraviolet absorbers (BAS
F)), 2-Ethylhexyl-2-cyano-3,3'-
Diphenyl acrylate (UVINUL N-589
(BASF)).

As the ultraviolet absorber, those having a high molecular weight are commercially available, for example, MARK LA manufactured by Asahi Denka.
-51, MARK LA-31, SEE manufactured by Cipro Kasei
SORB 706, UVA 101 made by Takemoto Yushi or the like can be used.

Further, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate (Sanol LS-770 (Sankyo), Adecastab LA-77 (Asahi Denka)) is used as a hindered amine light stabilizer. , Screw-
[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl] sebacate (Tinuvin 765 (Ciba-Geigy), SANOL LS 765 (Sankyo)), bis- (1,2,2,6,6) -Pentamethyl-
4-piperidinyl) -2- (3,5-di-tetra-butyl-4-hydroxybenzyl) -2-n-butylmalonate (TINUVIN 144 (Ciba Geigy)),
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (ADEKA STAB LA-57 (Asahi Denka)),
Tetrakis (1,2,2,6,6-pentamethyl-4-
Piperidyl) -1,2,3,4-butane tetracarboxylate (ADEKA STAB LA-52 (Asahi Denka)), 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,3 4-butane tetra
Carboxylate (ADEKA STAB LA-67 (Asahi Denka) 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetra
Carboxylates (ADK STAB LA-62 (Asahi Denka)) can be mentioned.

According to a preferred embodiment of the present invention, it is preferable to further add a phosphorus-based antioxidant in addition to the ultraviolet absorber and / or the light stabilizer. The discoloration of the polymer and the additive is suppressed by the addition of the phosphorus-based antioxidant, so that the advantage of suppressing the change in the color tone of the ink composition and the image is obtained.

The production of the polymer fine particles according to the first aspect of the present invention can be preferably carried out as follows.
That is, (1) a polymerization reaction is carried out by adding an ultraviolet absorber and / or a light stabilizer to a system comprising a monomer which is a reactive species and a polymerization catalyst, and the obtained polymer is dissolved in an organic solvent and stirred. (2) A solution emulsification method in which water is added to the polymer solution to form an emulsion, and (2) water is poured into a polymer and an emulsifier obtained in the same manner as above without melting or kneading with a kneading mixer. It can be obtained by a method of adding little by little, or (3) a direct emulsification method in which a molten polymer is gradually added to a heated emulsifier aqueous solution while stirring to emulsify. According to another embodiment, (4) the polymer fine particles are reacted with a polyol and a diisocyanate or a polyisocyanate in the presence of an ultraviolet absorber and / or a light stabilizer and a catalyst to emulsify the obtained polyurethane. It is also possible to get it.

According to another embodiment, the fine polymer particles used in the present invention can be obtained by known emulsion polymerization. Specifically, an ultraviolet absorber and / or
Alternatively, it can be obtained by dissolving a light stabilizer in a monomer and subjecting this monomer component to emulsion polymerization in water in the presence of a polymerization catalyst and an emulsifier with another monomer component. Here, usable emulsifiers include anionic surfactants, nonionic surfactants, and mixtures thereof. Examples of anionic surfactants include alkyl sulfonates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, dialkyl sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether sulfates, and polyoxyethylene sulfonates. Ethylene phenyl ether sulfate and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, and polyoxyethylene fatty acid. Esters and polyglycerin fatty acid esters. This emulsion polymerization is a preferred method for producing polymer fine particles in the form of a polymer emulsion. According to a preferred embodiment of the present invention, from the viewpoint of obtaining a stable polymer emulsion, the HLB thereof is 15 to 20.
The use of a surfactant is preferred.

The monomer component used in the above-mentioned production method is not particularly limited as long as it gives the polymer component of the polymer fine particles described above.
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl
(Meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate ) Acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylates such as acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl methacrylate, and glycidyl acrylate; and vinyl esters such as vinyl acetate; acrylonitrile, methacrylonitrile, and other styrene; 2-methylstyrene,
Aromatic vinyls such as vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene and divinylbenzene; vinylidene halides such as vinylidene chloride and vinylidene fluoride; ethylene, propylene, isopropylene butadiene, vinylpyrrolidone; Vinyl chloride, vinyl ether, vinyl ketone, chloroprene, etc., and ethylenic esters such as acrylic acid, methacrylic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester containing a carboxyl group. Saturated carboxylic acid; acrylamide having an amide group,
N-containing amino groups such as N, N-dimethylacrylamide
Alkylamino esters of acrylic acid or methacrylic acid such as -methylaminoethyl methacrylate, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate; N- (2-dimethylamino Unsaturated amides having an alkylamino group such as ethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, etc .; monovinylpyridines such as vinylpyridine; dimethylaminoethyl Vinyl ethers having an alkylamino group such as vinyl ether; vinyl sulfonic acid, styrene sulfonic acid and salts thereof, such as vinyl imidazole; Roiruamino 2-methylpropanesulfonic acid, and those having a sulfonic group of the salts. These monomers can be used alone or in combination of two or more.

As described above, the polymer fine particles can have a single particle structure or a core-shell structure, and any structure can be adopted for the polymer fine particles of the first embodiment.

Here, the polymer fine particles having a core-shell structure are not particularly limited, but can be produced by a known method, generally by multi-stage emulsion polymerization or the like.

When the polymer fine particles have a core-shell structure, the ultraviolet absorber and / or the light stabilizer may be present in either the core portion or the shell layer, or may be present in both.

Further, according to a preferred embodiment of the present invention, the polymer fine particles of the first embodiment have either a carboxyl group or a sulfonic acid functional group in both the single particle structure and the core-shell structure. Those having an amide group, a hydroxyl group, or an amino group are more preferable. In the case of a core-shell structure, these functional groups are preferably present in the shell layer. These groups may be present in the structure of the monomer in the above-mentioned production method, or may be added to the surface of the polymer fine particles by graft polymerization or the like after obtaining them. Although the presence of such a group seems to be preferable based on the following possible mechanism, the following theory is merely an assumption and the present invention is not limited thereto. Hydrophilic groups such as carboxyl groups, sulfonic acid groups, amide groups, amino groups, and hydroxyl groups on the surface of such polymer particles are hydrogen-bonded to the hydroxyl groups (OH groups) of cellulose constituting paper fibers, and the polymer fine particles and paper The fibers are firmly adsorbed. as a result,
Penetration of a coloring material such as a pigment into the paper is suppressed. In particular, the polymer fine particle structure is a core-shell structure, and the shell layer has a carboxyl group, a sulfonic acid group, an amide group, an amino group,
When a hydrophilic group such as a hydroxyl group is contained, the proportion of these hydrophilic groups on the surface of the fine particle particles increases,
Further effects can be obtained. The water and water-soluble organic solvent in the vicinity of the polymer particles adsorbed on the paper fibers penetrate into the paper and decrease, so that the polymer particles coalesce and further fuse together to take in a color material such as a pigment to form a film. Is formed. Further, the ink composition containing the polymer fine particles having these groups does not wet the surface of the nozzle plate of the recording head of the ink jet printer which has been subjected to the water repellent treatment. As a result, ejection failure due to wetting of the surface of the nozzle plate of the ink and occurrence of flight bending are not caused, and the ejection stability is excellent. Furthermore, the ink composition containing the polymer fine particles having these groups has excellent storage stability.

2-2. Polymer fine particles of the second embodiment The polymer fine particles according to the second embodiment of the present invention comprise a polymer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability in the structure of the polymer described below. Examples of the site having an ultraviolet absorbing ability that can be used in this embodiment include a benzophenone skeleton, a benzotriazole skeleton, a hindered phenol skeleton, a salicylate skeleton, and a cyanoacrylate skeleton. Is mentioned.

The specific structure of these skeletons is as follows:

[0054]

Embedded image Benzotriazole skeleton:

[0055]

Embedded image Hindered phenol skeleton:

[0056]

Embedded image Salicylate skeleton:

[0057]

Embedded image Cyanoacrylate skeleton:

[0058]

Embedded image And a hindered amine skeleton:

[0059]

Embedded image It is.

The introduction of a site having an ultraviolet absorbing ability and / or a light stabilizing ability into the polymer structure is carried out by copolymerizing a copolymerizable monomer having the above skeleton in the molecular structure with another monomer. can do.

In the present invention, specific examples of the monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability include the above-mentioned moiety having an ultraviolet absorbing ability and / or a light stabilizing ability, a methacryl group and an acroyl group. And an ethylenically unsaturated group such as a vinyl group and an allyl group.

The following are specific examples of such a monomer. First, as a specific example of a monomer having an ultraviolet absorption site having a benzophenone skeleton,
These include:

[0063]

Embedded image

[0064]

Embedded image Further, specific examples of the monomer having an ultraviolet absorbing portion having a benzotriazole skeleton include the following.

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image Further, specific examples of the monomer having a UV absorbing site having a hindered phenol skeleton include the following.

[0068]

Embedded image Further, specific examples of the monomer having a light stable site having a hindered amine skeleton include the following.

[0069]

Embedded image

[0070]

Embedded image As a monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability, a commercially available monomer can be used. Examples of commercially available products include a monomer having an ultraviolet absorbing portion having a benzotriazole skeleton As RUVA-93 available from Otsuka Chemical Co., Ltd.
(2- (2′-hydroxy-5-methylacryloxyethylphenyl) -2H-benzotriazole). As a monomer having a light stabilizing site having a hindered amine skeleton, ADK STAB LA-82 (1, 2, 2, 6, available from Asahi Denka Kogyo KK)
6-pentamethyl-4-piperidyl methacrylate),
LA-87 (2,2,6,6-tetramethyl-4-piperidyl methacrylate).

The polymer fine particles according to the second embodiment are:
It can be produced by polymerizing a monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability and a polymerization method appropriately selected in consideration of the types of other monomers.

According to a preferred embodiment of the present invention, the polymer fine particles of the second embodiment used in the present invention can be obtained by known emulsion polymerization. Specifically, it is obtained by emulsion-polymerizing a monomer component constituting a polymer and a monomer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability in water in the presence of a polymerization catalyst and an emulsifier. Can be.

Specific examples of the monomer component constituting the polymer which can be used in the second embodiment include:
The same as the monomer component constituting the polymer fine particles of the first embodiment can be used. Further, specific examples of the emulsifier used in the above emulsion polymerization include those similar to those described in the first embodiment.

The polymer fine particles of the second embodiment may be in the form of a polymer emulsion, and can be preferably produced by the above-mentioned emulsion polymerization. Also,
As the polymer fine particles of the second embodiment in the form of a polymer emulsion, it is also possible to use a commercially available product, such as UVA-383MA manufactured by BASF.
And UVA-383MG.

As described above, the polymer fine particles can have a single particle structure or a core-shell structure, and any structure can be adopted for the polymer fine particles of the second embodiment.

Here, the polymer fine particles of the second embodiment having a core-shell structure can be similarly produced by the method described in the first embodiment.

When the polymer particles have a core-shell structure, the polymer having an ultraviolet absorbing ability and / or a light stabilizing ability may constitute either the core part or the shell layer, or may constitute both. May be.

Also, like the polymer fine particles according to the first embodiment, the polymer fine particles according to the second embodiment preferably have a functional group of either a carboxyl group or a sulfonic acid group. Further, those having an amide group, a hydroxyl group or an amino group are preferred. When the polymer fine particles according to the second aspect have a core-shell structure, it is preferable that these functional groups are present in the shell layer.

3. Coloring Material The coloring material contained in the ink composition according to the present invention may be either a dye or a pigment, but is preferably a pigment.

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

As the pigment, inorganic pigments and organic pigments can be used. As inorganic pigments, in addition to titanium oxide and iron oxide, contact method, furnace method,
Carbon black produced by a known method such as 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 (for example,
Basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used. In particular, as carbon black used as black ink, Mitsubishi Chemical No.2300, No.900, MCF88, No.3
3, No.40, No.45, No.52, MA7, MA8, MA100, No2200B etc.
Columbia Raven5750, Raven5250, Raven5000, Rav
en3500, Raven1255, Raven700, etc.
gal 400R, Regal 330R, Rega l660R, Mogul L, Monarch700,
Monarch 800, Monarch 880, Monarch 900, Monarch 10
00, Monarch 1100, Monarch 1300, Monarch 1400 etc.
Degussa Color Black FW1, ColorBlack FW2, Co
lor Black FW2V, Color Black FW18, Color Black FW20
0, ColorBlack S150, Color Black S160, Color Black
S170, Printex 35, Printex U, Printex V, Printex 140
U, Special Black 6, Special Black 5, Special Black
4A, Special Black 4 etc. can be used. Pigment used for yellow ink is CIPigment Yellow
1, CIPigment Yellow 2, CIPigment Yellow3, CI
Pigment Yellow 12, CIPigment Yellow 13, CIPigm
ent Yellow 14C, CIPigment Yellow 16, CIPigment
Yellow 17, CIPigment Yellow 73, CIPigment Yell
ow 74, CIPigment Yellow 75, CIPigment Yellow 8
3, CIPigment Yellow 93, CIPigment Yellow95, C.
I. Pigment Yellow97, CIPigment Yellow 98, CIPig
ment Yellow114, CIPigment Yellow128, CIPigment
Yellow129, CIPigment Yellow151, CIPigment Yel
low154 and the like. Pigments used in magenta ink include CI Pigment Red 5, CI Pigment
Red 7, CIPigment Red 12, CIPigment Red 48 (C
a), CIPigment Red48 (Mn), CIPigment Red 57 (Ca),
CIPigment Red 57: 1, CIPigment Red 112, CIPi
gment Red 123, CIPigment Red 168, CIPigment Re
d 184, CIPigment Red 202 and the like. Pigments used in cyan ink include CI Pigment Blue
1, CIPigment Blue 2, CIPigment Blue 3, CIPi
gment Blue 15: 3, CIPigment Blue 15:34, CIPigme
nt Blue 16, CIPigment Blue 22, CIPigment Blue
60, CIVat Blue 4 and CIVat Blue 60. However, it is not limited to these.

The particle size of these pigments is preferably 10 μm or less, more preferably 0.1 μm or less.

According to a preferred embodiment of the present invention, these pigments are preferably added to the ink as a pigment dispersion obtained by dispersing in an aqueous medium with a dispersant or a surfactant. As a preferred dispersant, a dispersant commonly used for preparing a pigment dispersion, for example, a polymer dispersant can be used. It will be apparent to those skilled in the art that the dispersant and surfactant contained in this pigment dispersion will also function as the dispersant and surfactant of the ink composition. Preferred examples of the polymer dispersant include natural polymers, specific examples of which include glue, gelatin, casein, proteins such as albumin, gum arabic, natural gums such as tragacanth gum, glucosides such as savonin, Alginic acid and propylene glycol alginate triethanolamine alginate, alginic acid derivatives such as ammonium alginate, methylcellulose, carboxymethylcellulose,
Examples include cellulose derivatives such as hydroxyethyl cellulose and ethyl hydroxy cellulose. 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 acid ester copolymers, acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers Styrene-acrylic resin such as styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride Copolymer, vinyl naphthalene-acrylic acid copolymer , Vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinylethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, acetic acid Examples include vinyl acetate copolymers such as vinyl-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 pigment in the ink composition of the present invention is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight.

4. Water-Soluble Organic Solvent Also, the ink composition according to the present invention comprises a water-soluble organic solvent. The water-soluble organic solvent is preferably a low-boiling organic solvent, and examples thereof include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, sec-butanol and 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 amount of the low boiling organic solvent added is preferably 0.1 to 30% by weight of the ink, more preferably 5 to 10% by weight.

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-
Polyhydric alcohols such as hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, trimethylolpropane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinones and the like.

The wetting agent was added in an amount of 0.1% of the ink.
-30% by weight is preferred, and more preferably 1-10% by weight.

According to a preferred embodiment of the present invention, when the glass transition point of the polymer fine particles is 30 ° C. or less or the minimum film forming temperature of the polymer emulsion is 30 ° C. or less, the use of a water-soluble organic solvent having a boiling point of 180 ° C. or more is preferred. preferable. Preferred examples of the water-soluble organic solvent include ethylene glycol (boiling point: 197 ° C .; hereinafter, the parentheses indicate the boiling point), propylene glycol (187 ° C.), diethylene glycol (245 ° C.), pentamethylene glycol (242
° C), trimethylene glycol (214 ° C), 2-butene-1,4-diol (235 ° C), 2-ethyl-1,
3-hexanediol (243 ° C), 2-methyl-2,
4-pentanediol (197 ° C), N-methyl-2-
Pyrrolidone (202 ° C), 1,3-dimethyl-2-imidazolidinone (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 (232 ° C), triethylene glycol monomethyl ether (249 ° C), tetraethylene glycol (327 ° C), triethylene glycol (288 ° C), diethylene glycol monobutyl ether (230 ° C), diethylene glycol monoethyl ether (202 ° C.), diethylene glycol monomethyl ether (194 ° C.) and the like. According to a preferred embodiment of the present invention, as a high boiling water-soluble solvent, for example,
Ethylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, glycerin, dipropylene glycol , Tetraethylene glycol, triethylene glycol, N-methyl-2-
It is preferred to use one selected from pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 2-pyrrolidone.

Further, according to a preferred embodiment of the present invention, the ink composition according to the present invention preferably contains a sugar, a tertiary amine, an alkali hydroxide, or ammonia.
Due to these additions, the colorant does not agglomerate or increase in viscosity even during long-term storage, and has excellent storage stability. An ink composition which maintains the dispersibility for a long time and has high ejection stability without clogging of the nozzle at the time of restarting during printing or after printing is interrupted can be obtained.

The sugars that can be added to the ink composition according to the present invention include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, and the like. Ribose,
Xylose, arabinose, galactose, aldonic acid, glucitol, (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a sugar in a broad sense, and is used to include a substance widely existing in nature such as alginic acid, α-cyclodextrin, and cellulose. Derivatives of these saccharides are represented by reducing sugars of the above-mentioned saccharides (for example, sugar alcohols (general formula HOCH ₂ (CHOH) nCH ₂ OH, where n is an integer of 2 to 5). ), Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thiosugars, etc. Particularly preferred are sugar alcohols.
Specific examples include maltitol and sorbitol.

The content of these saccharides is from 0.1 to 0.1% of the ink.
It is in the range of 40% by weight, more preferably 1 to 30% by weight.

The tertiary amine which can be added to the ink composition according to the present invention includes trimethylamine, triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, triisopropenolamine, butyldiethanolamine and the like. These may be used alone or in combination.
The addition amount of these tertiary amines to the ink composition of the present invention is 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
% By weight.

The alkali hydroxides that can be added to the ink composition according to the present invention are potassium hydroxide, sodium hydroxide and lithium hydroxide, and the amount added to the ink composition of the present invention is from 0.01 to 0.01. It is 5% by weight, preferably 0.05-3% by weight.

The ink composition of the present invention may further contain a surfactant. Examples of surfactants include:
Anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurate, ammonium salts of polyoxyethylene alkyl ether sulfate, etc.), nonionic surfactants (for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester) , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamides, etc.) and acetylene glycols (olefin Y, and Surfynol 82, 104,
440, 465, and 485 (all Air Products
and Chemicals Inc.). These can be used alone or in combination of two or more.

The ink composition of the present invention may contain general-purpose polymer fine particles in addition to the above-mentioned polymer fine particles. The general-purpose polymer fine particles are preferably used in the form of a polymer emulsion. Examples of the polymer fine particles include an acrylic polymer, a vinyl acetate polymer, a styrene-butadiene copolymer, a vinyl chloride polymer, an acryl-styrene copolymer, a butadiene polymer, and a styrene polymer. Further, the particle diameter of these polymer fine particles is preferably about 200 nm or less, more preferably 5 to 2 nm.
It is about 00 nm. As these polymer fine particles, those commercially available in the form of a polymer emulsion can also be used. For example, Microgel E-10 can be used.
02, E-5002 (styrene-acrylic polymer emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4
001 (acrylic polymer emulsion, manufactured by Dainippon Ink and Chemicals, Inc.) Boncoat 5454 (styrene-acrylic polymer emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic polymer emulsion, ZEON Corporation) Corporation), Sibinol SK-200 (acrylic polymer emulsion, manufactured by Siden Chemical Co., Ltd.), and the like.

In addition, if necessary, a pH adjuster, a preservative, a fungicide, a phosphorus-based antioxidant, and the like may be added.

The ink composition according to the present invention can be produced by dispersing and mixing the above components by a suitable method. Preferably, first, the pigment, the polymer dispersant, and water are mixed with an appropriate dispersing machine (for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a jet mill, an ang mill). Then, a uniform pigment dispersion is prepared, and then, in water, a water-soluble organic solvent having a boiling point of 180 ° C. or higher, sugar, a pH adjuster, a preservative, a fungicide, etc. are added and sufficiently dissolved. A polymer emulsion containing the polymer fine particles as dispersed particles is added, and the mixture is sufficiently stirred at room temperature with an appropriate disperser to prepare an ink solvent. While stirring the pigment dispersion with an appropriate dispersing machine, the ink solvent is gradually dropped, and further stirred sufficiently. After sufficient stirring, filtration is performed to remove coarse particles and foreign substances that cause clogging, thereby obtaining a target ink composition.

5. Inkjet recording method The ink composition according to the present invention is preferably used in an inkjet recording method as described above. Further, the ink composition according to the present invention is preferably used in a color inkjet recording method using a plurality of color ink compositions. This color inkjet recording method will be described with reference to the drawings.

The ink jet recording apparatus shown in FIG. 1 is an embodiment in which an ink composition is stored in a tank, and the ink composition is supplied to a recording head via an ink tube. That is, the recording head 1 and the ink tank 2 are connected by the ink tube 3. Here, the inside of the ink tank 2 is partitioned, and a room for the ink composition, and in some cases, a plurality of color ink compositions is provided.

The recording head 1 moves along the carriage 4
It is moved by a timing belt 6 driven by a motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 1 by the platen 8 and the guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is supplied to the waste ink tank 13 via the tube 12.
Is stored.

FIG. 2 is an enlarged view of the nozzle surface of the recording head 1. The portion indicated by 1c is the nozzle surface of the ink composition, and the nozzles 22, 23, 24, and 25 eject the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition, respectively. You.

Further, an ink jet recording method using the recording head shown in FIG. 2 will be described with reference to FIG.
The recording head 1 moves in the direction of arrow A. During the movement, the ink composition is printed to form a print area 31.

Further, in some ink jet recording apparatuses, replenishment of the ink composition is performed by replacing a cartridge which is an ink tank. This ink tank may be integrated with the recording head.

FIG. 4 shows a preferred example of an ink jet recording apparatus using such an ink tank. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 4, the recording head 1 is integrated with the ink tank 2. The printing method may be basically the same as that of the apparatus shown in FIG. And in this aspect,
The recording head 1 and the ink tank 2 move on the carriage 4 together.

6. Recording method using two liquids Furthermore, according to a preferred embodiment of the present invention, the ink composition according to the present invention comprises an ink composition and a reactant that contacts the ink composition to form an aggregate. It is preferably used in a recording method using two liquids including a reaction liquid. According to this method, excellent fixability, finger touch and abrasion resistance,
An image having excellent water resistance and good OD value and gloss can be obtained. The reason is that the dispersing state of the coloring material and the polymer emulsion causes the reaction agent to disintegrate, causing agglomerates, and has excellent fixability to a recording medium such as paper, high OD value and glossiness, It is believed that high-quality images without feathering, bleeding, or bleeding are realized.

Examples of the reactant which forms an aggregate upon contact with the ink composition according to the present invention include polyvalent metal salts and / or
Or polyallylamine and / or its derivative.

As the polyvalent metal salt, those which are composed of polyvalent metal ions having a valence of 2 or more and anions bonded to these polyvalent metal ions and which are soluble in water are used. Specific examples of the polyvalent metal ion include Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg
Divalent metal ions such as ²⁺ , Zn ²⁺ , Ba ²⁺ , Al ³⁺ ,
Examples include trivalent metal ions such as Fe ³⁺ and Cr ³⁺ . Specific examples of the anion include Cl ⁻ , NO ₃ ⁻ , I ⁻ , Br ⁻ ,
ClO ₃ ^- and CH ₃ COO ^- and the like, preferably, nitrate ions or carboxylate ions. Here, the carboxylate ion is preferably derived from a carboxylic acid selected from the group consisting of a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms and a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms. is there. Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and hexanoic acid. Particularly, formic acid and acetic acid are preferable. A hydrogen atom on the saturated aliphatic hydrocarbon group of the monocarboxylic acid may be substituted with a hydroxyl group. Preferred examples of such a carboxylic acid include benzoic acid and naphthoic acid, and more preferably benzoic acid. Is an acid.

Further, polyallylamine and polyallylamine derivatives are cationic polymers which are soluble in water and positively charged in water. For example, Expression (a), Expression (b), and Expression (c) are given.

[0109]

Embedded image (In the formula, X ^- represents a chloride ion, a bromide ion, an iodide ion, a nitrate ion, a phosphate ion, a sulfate ion, an acetate ion, and the like.) Further, a polymer obtained by copolymerizing allylamine and diallylamine, and diallylmethylammonium chloride Copolymers with sulfur dioxide can be used.

The reaction solution used in the present invention basically comprises a polyvalent metal salt and / or polyallylamine and / or a polyallylamine derivative, and water.

The concentration of the polyvalent metal salt in the reaction solution may be appropriately determined within the range where the printing quality and the effect of preventing clogging can be obtained. Preferably, the concentration is about 0.1 to 40% by weight of the reaction solution. And more preferably about 5 to 25% by weight. The concentration of the polyallylamine and / or polyallylamine derivative in the reaction solution is preferably 0.5 to 10% by weight of the reaction solution. .

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

The amount of the high-boiling organic solvent is not particularly limited, but is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.

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

Further, the reaction liquid may be colored by adding a color material, and may have the function of the ink composition.

Regarding the adhesion of the reaction liquid to the recording medium, either of the method of selectively applying the reaction liquid only at the place where the ink composition is applied and the method of adhering the reaction liquid to the entire paper can be used. 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, in the latter, the demand for the accuracy of the adhesion position of the reaction liquid and the ink composition is eased compared to the former, but a large amount of the reaction liquid is attached to the whole paper,
Paper is easy to curl. Therefore, which method is adopted may be determined in consideration of the combination of the ink composition and the reaction liquid.

According to a preferred embodiment of the present invention, the ink composition and the reaction liquid are preferably applied to a recording medium by a so-called ink jet recording method. That is, a recording method in which droplets are ejected from ink ejection holes of an ink jet recording head and adhered to a recording medium to form an image is preferable.

The ink jet recording method using the ink composition and the reaction liquid according to the present invention will be further described with reference to the drawings.

The ink jet recording apparatus shown in FIG. 5 is an embodiment in which the ink composition and the reaction liquid are stored in a tank, and the ink composition and the reaction liquid are supplied to the recording head via an ink tube. That is, the recording head 51 and the ink tank 52 are communicated by the ink tube 3. Here, the inside of the ink tank 52 is partitioned, and a room for an ink composition, and in some cases, a plurality of color ink compositions and a room for a reaction liquid are provided.

The recording head 51 is moved along the carriage 4 by the timing belt 6 driven by the motor 5. On the other hand, the paper 7 as a recording medium is placed at a position facing the recording head 51 by the platen 8 and the guide 9. In this embodiment, a cap 10 is provided. A suction pump 11 is connected to the cap 10 to perform a so-called cleaning operation. The sucked ink composition is stored in a waste ink tank 13 via a tube 12.

FIG. 6 is an enlarged view of the nozzle surface of the recording head 51.
Shown in The portion indicated by 51b is the nozzle surface of the reaction liquid, and the nozzle 21 for discharging the reaction liquid is provided in the vertical direction. On the other hand, the portion indicated by 51c is the nozzle surface of the ink composition, and from the nozzles 22, 23, 24, and 25, the yellow ink composition, the magenta ink composition, the cyan ink composition, and the black ink composition are respectively provided. Discharged.

Further, an ink jet recording method using the recording head shown in FIG. 6 will be described with reference to FIG.
The recording head 51 moves in the direction of arrow A. During the movement, the reaction liquid is discharged from the nozzle surface 51b, and the recording medium 7
A belt-like reaction liquid attachment region 61 is formed on the upper surface. Next, the recording medium 7 is transported by a predetermined amount in the paper feed direction arrow B. During that time, the recording head 51 moves in the direction opposite to the arrow A in the figure, and returns to the position on the left end of the recording medium 7. Then, the ink composition is printed on the reaction liquid adhering area where the reaction liquid has already adhered, and a printing area 62 is formed.

Further, as shown in FIG.
In the above, all the nozzles can be arranged in the horizontal direction. In the figure, 41a and 41b are discharge nozzles of the reaction liquid, and the nozzles 42, 43, 44, and 45 discharge yellow ink composition, magenta ink composition, cyan ink composition, and black ink composition, respectively. You. In the print head of such an aspect, the print head 51 can perform printing both in the forward path and the return path in which the print head 51 reciprocates on the carriage, so that the print head 51 operates at a higher speed than in the case of using the print head shown in FIG. Printing can be expected.

Further, in some ink jet recording apparatuses, replenishment of the ink composition is performed by replacing a cartridge which is an ink tank. This ink tank may be integrated with the recording head.

FIG. 9 shows a preferred example of an ink jet recording apparatus using such an ink tank. In the figure, the same members as those of the apparatus of FIG. 1 are denoted by the same reference numerals. In the embodiment of FIG. 9, the recording heads 51a and 51
b is integrated with the ink tanks 52a and 52b. The recording head 51a or 51b discharges the ink composition and the reaction liquid, respectively. The printing method may be basically the same as that of the apparatus shown in FIG. In this embodiment, the recording head 51a and the ink tank 52
a, recording head 51a, and ink tank 52b
Move together on the carriage 4.

[0126]

EXAMPLE 1 200 ml of distilled water and 0.6 g of sodium dodecylbenzenesulfonate were charged into a reaction vessel equipped with a polymer emulsion 1 stirrer, a reflux condenser, a dropping device, a thermometer and a nitrogen inlet tube, and then charged in a nitrogen atmosphere. The mixture is heated to 70 ° C. with stirring, and 2 g of potassium persulfate is further added. On the other hand, 40 g of butyl acrylate, 50 g of styrene, 5 g of acrylamide, 5 g of acrylic acid, 0.15 g of t-dodecyl mercaptan, and ultraviolet absorber 2 (2′-hydroxy-5′-methylphenyl) benzotriazole (SEES manufactured by Cipro Kasei)
1 g of ORB709) was mixed and dissolved, and this was dropped into the reaction vessel. Furthermore, after reacting at 70 ° C. for 6 hours, the mixture was cooled to room temperature, ammonia water was added as a neutralizing agent to prepare PH, and the mixture was filtered through a 10 μm filter.
A polymer emulsion containing dispersed polymer fine particles containing an ultraviolet absorber is obtained. The glass transition point of this polymer emulsion is 20 ° C. and the minimum film forming temperature is 25 ° C.

Polymer Emulsion 2 Distilled water (200 ml) and sodium dodecylbenzenesulfonate (0.6 g) were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, a thermometer and a nitrogen inlet tube, and stirred in a nitrogen atmosphere. While heating to 70 ° C., 2 g of potassium persulfate is further added. On the other hand, 40 g of butyl acrylate, 50 g of styrene, 5 g of acrylamide, 5 g of acrylic acid, 0.1 g of t-dodecyl mercaptan, and a monomer 2 (2'-hydroxy-5'-methacryloxyethylphenyl)-having a skeleton having an ultraviolet absorbing ability 2H-
5 g of benzotriazole (RUVA-93 manufactured by Otsuka Chemical) and monomers 1,2,2 having a skeleton having light stabilizing ability
1 g of 2,6,6-pentamethyl-4-piperidyl methacrylate (ADEKA STAB LA-82 manufactured by Asahi Denka) is mixed and dissolved, and the mixture is dropped into the reaction vessel. Further 70
After reacting at 6 ° C. for 6 hours, the mixture was cooled to room temperature, ammonia water was added as a neutralizing agent to adjust the pH, and the mixture was filtered through a 10 μm filter. To obtain a polymer emulsion using the polymer fine particles having the above as dispersed particles. The glass transition point of this polymer emulsion is 20 ° C and the minimum film formation temperature is 25 ° C.
Met.

Measurement of Glass Transition Point A film obtained by drying the water content of the polymer emulsion is measured by a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min.

Measurement of minimum film forming temperature A minimum film forming temperature measuring device is set, and when the temperature gradient on the aluminum sample plate reaches equilibrium, the polymer emulsion of the sample is spread thinly and dried. Observation on the sample plate after drying is completed, a transparent continuous film is formed in a temperature region higher than the minimum film formation temperature, but becomes a white powder in a temperature region lower than the minimum film formation temperature. The temperature at this boundary is measured as the minimum film forming temperature.

[0130]

[0131]

[0132]

The above ink is prepared as follows. First, a pigment, a dispersant, and water are mixed and dispersed in a sand mill (manufactured by Yasukawa Seisakusho) for 2 hours together with glass beads (diameter 1.7 mm, 1.5 times the weight (weight) of the mixture). Is removed to prepare a pigment dispersion. Then
To the water are added the polymer emulsion 1, glycerin, maltitol, 2-pyrrolidone, triethanolamine, and potassium hydroxide, and the mixture is stirred at room temperature for 20 minutes. Then, the pigment dispersion is gradually added dropwise with stirring. 2
Stir for 0 minutes. This is filtered through a 5 μm membrane filter to obtain an ink for inkjet recording.

[0134]

[0135]

[0136] The above ink was prepared in the same manner as for the color ink 1.

Color Ink 3 This ink used was UVA-383MA, a commercially available polymer emulsion manufactured by BASF, in which fine particles of a polymer having the above-described portion having the ability to absorb ultraviolet light in its structure were dispersed. Such polymer fine particles use 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone as a copolymer component as a monomer having a site capable of absorbing ultraviolet light, and have a glass transition point of about 27 ° C. and a minimum composition of the polymer emulsion. The film temperature is below 0 ° C.

(Cyan Ink 3) C.I. I. Pigment Blue 15: 3 2% by weight Styrene-acrylic acid copolymer ammonium salt (molecular weight 7000, polymer component 38%: dispersant) 1% by weight UVA-383MA manufactured by BASF 5% by weight Glycerin 10% by weight Maltitol 7% by weight 2-pyrrolidone 2 wt% triethanolamine 1.0 wt% KOH 0.1 wt% pure water

[0139]

[0140] The above ink was prepared in the same manner as for the color ink 1.

[0141]

[0142]

[0143] The above ink is prepared in the same manner as for the color ink 1.

[0144]

[0145]

[0146]

The above ink is prepared in the same manner as for the color ink 1.

[0148]

[0149]

Evaluation Test Evaluation 1: Light fastness (printing method) Using the ink jet recording apparatus shown in FIG.
The yellow, magenta, and cyan inks of the color inks 1 to 5 were converted to plain paper Xerox 4024 and Xerox P, respectively.
And inkjet paper (Seiko Epson Corporation)
) At 100% duty to obtain a solid image of 3 cm × 3 cm. Example 1: Recorded matter obtained by using the color ink 1 by the above printing method. Example 2: Recorded matter obtained by using the color ink 2 by the above printing method. Example 3: Recorded matter obtained by using the color ink 3 by the above printing method. Comparative Example 1: Recorded matter obtained by using the color ink 4 by the above printing method. Comparative Example 2: Recorded matter obtained using color ink 5 by the above printing method. Using the inkjet recording apparatus shown in FIG. 5, the reaction liquid 1 and each of the yellow, magenta, and cyan inks of the color inks 1 to 5 were mixed with plain paper Xerox 4024, Xerox P, and inkjet paper (Seiko Epson Corporation).
) At 100% duty to obtain a solid image of 3 cm × 3 cm. Example 4: Reaction liquid 1 and color ink 1 by the above printing method
Recorded matter obtained by using Example 5: Reaction liquid 1 and color ink 2 by the above printing method
Recorded matter obtained by using Example 6: Reaction liquid 1 and color ink 3 in the above printing method
Recorded matter obtained by using Comparative Example 3: Reaction liquid 1 and color ink 4 by the above printing method
Recorded matter obtained by using Comparative Example 4: Reaction liquid 1 and color ink 5 by the above printing method
Recorded matter obtained by using

Evaluation Method The solid image recorded matter obtained by the above method is subjected to an exposure test for 600 hours using a xenon fade meter. The color before and after exposure of the solid image portion was determined by Macbeth.
It is measured by a CE-7000 spectrophotometer (manufactured by Macbeth), and is represented by an L * a * b * color difference display method specified by CIE, and a color change before and after exposure of a solid image portion is represented by a color difference obtained by the following equation. Color difference: ΔE * ab = [(ΔL *) ² + (Δa *) ² + (Δ
b *) ² ] ^1/2 The value is evaluated according to the following criteria. The color density of the solid image portion before and after the exposure was measured using a Macbeth densitometer TR927 (Macbeth).
And the change in color density before and after exposure of the solid image portion is evaluated according to the following criteria. The evaluation results are as shown in the following table.

[Table 1]

[Table 2]

Evaluation 2: Print Quality (Bleeding) Using the ink jet recording apparatus shown in FIG. 5, printing was performed on the following papers using the reaction liquid 1 or the reaction liquid 2 and the yellow, magenta and cyan inks of the color inks 1 to 5 respectively. Do. The combinations are as follows. Example 7: Reaction liquid 1 and color ink 1 by the above printing method
Recorded matter obtained by using Example 8: Reaction liquid 1 and color ink 2 by the above printing method
Recorded matter obtained by using Example 9: Reaction liquid 2 and color ink 1 by the above printing method
Recorded matter obtained by using Example 10: Recorded matter obtained by using the reaction liquid 2 and the color ink 2 by the printing method described above. Comparative Example 5: Recorded matter obtained using color ink 4 by the above printing method. Comparative Example 6: Reaction liquid 1 and color ink 5 by the above printing method
Recorded matter obtained by using First, after printing the reaction solution at 100% duty,
Print 24 letters of the alphabet with each color ink. Discharge rate of both reaction liquid and ink is 0.07μg / do
t and the density are 360 dpi. The recording paper used for the evaluation is as follows. Xerox P paper (manufactured by Xerox Co., Ltd.) Riccopy 6200 paper (manufactured by Ricoh Co., Ltd.) Xerox 4024 paper (manufactured by Xerox Co., Ltd.) Neenah Bond paper (manufactured by Kimberly-Clark Co., Ltd.) Xerox R paper (manufactured by Xerox Co., Ltd., recycled paper) Yamayuri Paper (Recycled paper manufactured by Honshu Paper Co., Ltd.) The presence or absence of bleeding in the characters of the obtained recorded matter is visually observed and evaluated as follows. A: Vivid characters were obtained on all papers without bleeding. ：: Some paper has whisker-like bleeding. Δ: All paper has whisker-like bleeding. ×: Blurring has occurred so that the outline of the character is not clear. The evaluation results are as shown in the following table.

[Table 3]

Evaluation 3: Abrasion Resistance Test (Line Marker Resistance)
Properties) After the printed matter printed in Evaluation 2 was dried at room temperature for 24 hours, the printed characters of the recorded matter were written with a water pressure of 4.9 × using a water-based fluorescent pen ZEBRA PEN2 (trademark) of Zebra Corporation.
Rubbing is performed at 10 ⁵ N / m ² , and the presence or absence of dirt is visually observed and evaluated as follows. ：: No stain is generated even after rubbing twice. ×: Staining occurs with one rub. The evaluation results were as shown in the following table.

[Table 4]

Evaluation 4: Color Bleed Using the ink jet recording apparatus shown in FIG. 5, printing is performed on the following papers using the reaction liquid 1 and the yellow, magenta, and cyan inks of the color inks 1 to 5. The combinations are as follows. Example 11: Recorded matter obtained by using the reaction liquid 1 and the color ink 1 by the above printing method. Example 12: A recorded matter obtained by using the reaction liquid 1 and the color ink 2 by the above printing method. Example 13: Recorded matter obtained by using the reaction liquid 2 and the color ink 1 by the above printing method. Comparative Example 7: A recorded matter obtained by using only the color ink 4 without using the reaction liquid in the above printing method. Comparative Example 8: Reaction liquid 1 and color ink 5 by the above printing method
Recorded matter obtained by using The recording paper used for the evaluation is shown below. Xerox P paper (manufactured by Xerox Co., Ltd.) Riccopy 6200 paper (manufactured by Ricoh Co., Ltd.) Xerox 4024 paper (manufactured by Xerox Co., Ltd.) Neenah Bond paper (manufactured by Kimberly-Clark Co., Ltd.) Xerox R paper (manufactured by Xerox Co., Ltd., recycled paper) Yamayuri Paper (Recycled paper manufactured by Honshu Paper Co., Ltd.) Printing is performed by first printing the reaction solution at 100% duty.
Prints each color of the color ink (cyan, magenta, yellow). The presence or absence of uneven color mixture at the boundary between the colors is visually observed and evaluated according to the following criteria. The ejection amount of both the reaction liquid and the ink is 0.07 μg / dot, and the density is 360 dpi. ：: When there is no color mixing and the boundary is clear Δ: When color mixing occurs like a whisker ×: When the color is mixed so that the boundary is not clear The evaluation results are as shown in the following table.

[Table 5]

Evaluation 5: Storage stability The following ink composition (50 cc) was placed in a glass sample bottle, left at 60 ° C. for 2 weeks, and examined for viscosity, sedimentation and the occurrence of foreign matter. Example 15: Color ink 1 was subjected to this test. Example 16: Color ink 2 was subjected to this test. Example 17: Color ink 3 was subjected to this test. Comparative Example 9: Color ink 4 was subjected to this test. Comparative Example 10: Color ink 5 was subjected to this test. The evaluation is performed as follows. ：: No sediment or foreign matter was generated, and there was no change in viscosity. Δ: No sediment or foreign matter was generated, but there was a change in viscosity. ×: There is generation of sediment or foreign matter. The evaluation results were as shown in Table 7.

Evaluation 6: Clogging reliability The heads of the ink jet recording apparatus shown in FIG. 1 were filled with the yellow, magenta, and cyan inks of the color inks 1 to 5, and alphanumeric characters were printed continuously for 10 minutes. .
After that, the printer is stopped and left for one week in an environment of a temperature of 40 ° C. and a humidity of 25% without capping. 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. In addition,
The ink compositions used for the test are as follows. Example 15: Color ink 1 was subjected to this test. Example 16: Color ink 2 was subjected to this test. Example 17: Color ink 3 was subjected to this test. Comparative Example 9: Color ink 4 was subjected to this test. Comparative Example 10: Color ink 5 was subjected to this test. Evaluation is performed according to the following criteria. Print quality equivalent to the initial one was obtained by the return operation of 0 to 2 times. : Good print quality equivalent to the initial one was obtained with 3 to 5 recovery operations. : 印字 Print quality equivalent to the initial one could not be obtained after 6 or more return operations. : × This evaluation result is as shown in Table 7.

Evaluation 7: Discharge stability An ink jet printer MJ-700V2C (manufactured by Seiko Epson Corporation) was filled with the ink composition, the discharge amount was 0.7 μg / dot, the density was 360 dpi, and alphabetic characters were continuously printed at room temperature. I do. Observation of missing dots and scattering of ink is performed, and the time required for occurrence of 10 or more times is examined. In addition, the ink composition used for a test is as follows. Example 15: Color ink 1 was subjected to this test. Example 16: Color ink 2 was subjected to this test. Example 17: Color ink 3 was subjected to this test. Comparative Example 9: Color Ink 4 was subjected to this test. Comparative Example 10: Color ink 5 was subjected to this test. The evaluation is performed as follows. Missing dots or ink splatter for more than 48 hours
Does not occur 0 times. : ド ッ ト Missing dots or ink scattering occurred 10 times within 24 to 48 hours. : O Missing dots or ink scattering occurred 10 times within 1 to 24 hours. : △ 1 missing dot or ink splatter within 1 hour
Occurs zero or more times. : × The evaluation results are as shown in the following table.

[Table 6]

[Brief description of the drawings]

FIG. 1 shows an ink jet recording apparatus for carrying out a method according to the present invention, in which a recording head and an ink tank are independent, and an ink composition is supplied to the recording head by an ink tube. .

FIG. 2 is an enlarged view of a nozzle surface of a recording head, and 1c
Is a nozzle surface in which a plurality of nozzles from which the ink composition is discharged are provided in a line in the vertical direction.

FIG. 3 is a diagram illustrating inkjet recording using the recording head of FIG. 2; In the figure, reference numeral 31 denotes a print of the ink composition.

FIG. 4 is a view showing an ink jet recording apparatus for carrying out the method according to the present invention, in which a recording head and an ink tank are integrated.

FIG. 5 is a view showing an ink jet recording apparatus for carrying out the method according to the present invention, in which a recording head and an ink tank are independent, and an ink composition and a reaction liquid are supplied to the recording head by an ink tube. Supplied.

FIG. 6 is an enlarged view of a nozzle surface of a recording head,
b is the nozzle surface of the reaction liquid, and 51c is the nozzle surface of the ink composition.

FIG. 7 is a diagram illustrating ink jet recording using the recording head of FIG. In the figure, reference numeral 61 denotes a reaction liquid adhering area, and reference numeral 62 denotes a printing area where the ink is printed on the reaction liquid adhering thereto.

FIG. 8 is a diagram showing another aspect of the recording head, in which all the ejection nozzles are arranged in the horizontal direction.

FIG. 9 is a view showing an ink jet recording apparatus for carrying out the method according to the present invention. In this embodiment, the recording head and the ink tank are integrated.

[Explanation of symbols]

 1,51 Recording head 2,52 Ink tank 3 Ink tube 22,23,24,25 Ink ejection nozzle 31 Printing area 21 Reaction liquid ejection nozzle 61 Reaction liquid adhesion area 62 Printing area

Claims (25)

[Claims] 1. An ink composition comprising a coloring material, water, a water-soluble organic solvent, and polymer fine particles, wherein the polymer fine particles have a film-forming ability and an ultraviolet absorbing ability. Alternatively, an ink composition comprising a polymer having a light stabilizing ability. 2. The ink composition according to claim 1, wherein said polymer fine particles are made of a polymer containing an ultraviolet absorber and / or a light stabilizer. 3. The ultraviolet absorber or light stabilizer is a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a hindered phenol ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, The ink composition according to claim 2, wherein the ink composition is selected from the group consisting of a nickel complex salt-based UV absorber and a hindered amine-based light stabilizer. 4. The ink composition according to claim 1, wherein the polymer fine particles comprise a polymer having a site having an ultraviolet absorbing ability and / or a light stabilizing ability in a structure. 5. The method according to claim 1, wherein the site having an ultraviolet absorbing ability or a light stabilizing ability is selected from the group consisting of a benzophenone skeleton, a benzotriazole skeleton, a hindered phenol skeleton, a salicylate skeleton, a cyanoacrylate skeleton, and a hindered amine skeleton. The ink composition according to claim 4, wherein 6. The ink composition according to claim 1, wherein the polymer fine particles have a glass transition point of 30 ° C. or lower. 7. The ink composition according to claim 6, wherein said water-soluble organic solvent has a boiling point of 180 ° C. or higher. 8. The method according to claim 1, wherein the polymer fine particles are made of a polymer containing a thermoplastic polymer as a main component.
8. The ink composition according to any one of claims 1 to 7. 9. The thermoplastic polymer is ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyethylene, polypropylene, polystyrene, poly (meth) acrylate, (meth) acrylic acid
Consists of styrene copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-maleic acid copolymer, styrene-itaconic acid ester copolymer, polyvinyl acetate, polyester, polyurethane, and polyamide The ink composition according to claim 8, which is selected from a group. 10. The ink composition according to claim 1, wherein the polymer fine particles have a single particle structure. 11. The ink composition according to claim 10, wherein said polymer fine particles have a functional group of either a carboxyl group or a sulfonic acid group. 12. The ink composition according to claim 1, wherein the polymer fine particles have a core-shell structure composed of a core portion and a shell layer surrounding the core portion. 13. The ink composition according to claim 12, wherein the shell layer has a functional group of either a carboxyl group or a sulfonic acid group. 14. The polymer fine particles having a particle size of 5 nm to 2 nm.
The ink composition according to any one of claims 1 to 13, which has a thickness of 00 nm. 15. The ink composition according to claim 1, wherein the polymer fine particles are dispersed in the ink composition as dispersed particles of a polymer emulsion. 16. The ink composition according to claim 15, wherein said polymer emulsion has a minimum film formation temperature of 30 ° C. or less. 17. The ink composition according to claim 16, wherein said water-soluble organic solvent has a boiling point of 180 ° C. or higher. 18. The ink composition according to claim 1, wherein the coloring material is a dye or a pigment. 19. An ink jet recording method comprising:
The ink composition according to claim 1. 20. A recording method for printing on a recording medium by adhering an ink composition, wherein the ink composition according to claim 1 is used as the ink composition. 21. An ink jet recording method in which droplets of an ink composition are ejected, and the droplets are attached to a recording medium to perform printing, wherein the ink composition is any one of claims 1 to 19. An ink jet recording method using the ink composition described in the above. 22. A recording medium comprising the ink composition according to any one of claims 1 to 19 and a reaction liquid comprising a reactant which forms an aggregate when contacted with the ink composition. A recording method, comprising a step of forming an image by causing the image to be formed. 23. The recording method according to claim 22, wherein said ink composition and / or said reaction liquid is attached to a recording medium by an ink jet recording method. 24. The recording method according to claim 23, wherein the reaction solution contains at least a reactant, a water-soluble organic solvent, and water. 25. The recording method according to claim 24, wherein the reactant is a polyvalent metal salt or polyallylamine or a derivative thereof.