JP2003335987A - Ink for ink jet recording, ink set, ink cartridge, recording apparatus and recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for ink jet recording giving good color tone when printed on a plain paper. <P>SOLUTION: The ink set for ink jet recording is composed of a black ink and a color ink. The color ink is an aqueous dispersion of fine polymer particles containing a colorant. Pigments are used as the colorants for the color ink and the black ink. A specific moistening agent, an 8-11C polyol or glycol ether, a water-soluble organic solvent and water are included in the ink in combination with a specific surfactant and a fluorine-based surfactant having a specific structure to improve the color developing property, especially remarkably improve the chroma of magenta color, remarkably improve the chroma of secondary colors comprising green, blue and red, especially green color and improve the color-developing property of a pigment-based ink. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink, an ink set, an ink cartridge, a recording apparatus, and a recording method using a pigment as a coloring material for a black ink and a color ink of an ink set for ink jet recording, and more particularly,
The present invention relates to an ink jet recording ink set which, when a perfluoroalkyl sulfonate having a specific structure is used among surfactants, can produce good color when printed on plain paper.

[0002]

2. Description of the Related Art Conventionally, water-based inks using a water-soluble dye as a colorant have been mainly used in ink jet printers. However, the above-mentioned dye inks have the drawback of being poor in weather resistance and water resistance, and in recent years, pigment inks that use pigments instead of water-soluble dyes have been remarkably researched and have recently been put on the market. However, pigment inks still have many problems in color development and stability as compared with dye inks. Especially, with improvement in image quality improvement technology of OA printers, pigment inks have the same print quality as dye inks. , Hue, saturation, luster, storability, etc. have come to be required.

However, magenta color ink and cyan color ink, which are particularly used as pigment inks, are C.I.
I. Pigment Red 122, C.I. I. Pigment Blue 15: 3 is generally used, and the color reproduction range is different from that of dye ink. Further, toning is performed to reduce the hue error, but in this case, the deterioration of saturation is unavoidable, which causes a problem in print quality.

On the other hand, the pigment itself is being improved in order to change the hue regardless of the above-mentioned toning.
In 000-17207, a cyan pigment having a hue in the same color gamut as a cyan dye is proposed by using a phthalocyanine pigment having a specific crystal structure, but it has not been possible to satisfy all the characteristics such as a cost problem. Absent.

Further, by using a pigment as a coloring material for black ink,
Use as an ink set by using a dye as a coloring material for yellow, magenta, and cyan color inks.
Although there are many proposals such as Japanese Patent No. 590, etc., it is the current situation that satisfactory plain paper characteristics when printed on plain paper have not been obtained yet.

In addition, as an ink set consisting of black ink and color ink, a black ink having self-dispersion type carbon black and a color ink containing a coloring material having a polarity opposite to that of the coloring material of the black ink are used. Such an ink set is disclosed in JP-A-10-140064. Also, Japanese Patent Laid-Open No. 2000-191972
Japanese Patent Publication discloses an ink set in which the colorant-containing resin-dispersed ink has different ionic properties. However, prints using these ink sets have improved color boundary bleeding, but other plain paper properties are still unsatisfactory.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks, and an ink and an ink set using a pigment as a coloring material in a water-based ink for ink jet recording, and a preferred use of this ink and the ink set. PROBLEM TO BE SOLVED: To provide an ink jet recording method, an ink cartridge containing this ink set, and a recording device provided with this ink cartridge, and particularly to obtain an ink jet recording ink and ink set capable of producing good color when printed on plain paper, ink jet An object of the present invention is to provide a recording method, an ink cartridge, and a recording device.

[0008]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that an aqueous dispersion (hereinafter referred to as an emulsion) in which a coloring material is contained in fine polymer particles.
Ink using a specific wetting agent, penetrating agent, water-soluble organic solvent, and surfactant, especially a fluorine-based surfactant having a specific structure, has a higher viscosity than conventional ink In addition to the characteristics of conventional inks with high penetrability, such as low tension and quick penetration of the vehicle during printing on plain paper, leaving the coloring material component on the surface, a fluorosurfactant is used. By further, not only the coloring material component is likely to remain on the paper surface, there is no uneven distribution of the coloring material, the coloring material is evenly present on the paper surface, and the leveling property with respect to the paper is remarkably improved. The present invention has been completed by finding that an image with high saturation and high color density and with less strike-through can be obtained.

Further, in an ink set composed of a black ink and a color ink, a color ink in which a pigment ink is used as a color material and an ink of self-dispersion type is used as a color material in the ink having the above-mentioned composition containing fine colored polymer particles. When a black ink having a high viscosity and a low surface tension is combined like the color ink, the black image density is high in the printing on the plain paper, the color boundary bleeding between the black and the color is extremely small, and it has a specific structure. It has been found that the use of a fluorine-based surfactant makes it possible to obtain a markedly improved color saturation, and it is possible to obtain a recorded image having excellent color-developing properties of color and double-sided printability with less strike-through.

The invention completed by the present inventors based on the above findings has the following constitution. (1) In an inkjet recording ink set comprising a black ink and a color ink, the color ink is an aqueous dispersion of polymer fine particles containing a coloring material, and the black ink and the color ink are glycerin or Glycerin and 1,3-butanediol,
Triethylene glycol, 1,6-hexanediol,
Propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, and at least one kind of wetting agent selected from trimethylolethane (hydroxy compound of the first kind), and 8 or more carbon atoms At least one selected from anions, nonions and amphoteric surfactants, containing at least 11 or less polyol (second type hydroxy compound) or glycol ether, water-soluble organic solvent and water, and fluorine-based At least one kind of surfactant is contained (the fluorochemical surfactant may not be contained in the case of black ink), and the fluorochemical surfactant is a perfluoroalkyl sulfone represented by the following structural formula. It is an acid salt and uses a pigment as a coloring material. Jet recording ink set according to claim.

[0011]

[Chemical 9] (R ₁ , R ₂ and R ₃ represent either a perfluoroalkyl group or a fluorine atom, and M ₁ represents any of Li, Na and K.)

(2) In the above (1), the anion, nonion and amphoteric surfactant are at least one selected from the surfactants represented by the following general formulas (I) to (IX). The inkjet recording ink set described above.

R ₄ —O— (CH ₂ CH ₂ O) _m CH ₂ COOM ... (I) (wherein R ₄ is an alkyl group having 6 to 14 carbon atoms and may be branched, and m is 3 To an integer of 12 and M represents any one of alkali metal ion, quaternary ammonium, quaternary phosphonium, and alkanolamine.)

[0014]

[Chemical 10] (In the formula (II), R ₅ represents a branched alkyl group having a prime number of ₅ to 16, and M represents an alkali metal ion, quaternary ammonium, quaternary phosphonium, or alkanolamine.)

[0015]

[Chemical 11] (In the formula (III), R represents a carbon chain having 6 to 14 carbon atoms which may be branched, and k represents an integer of 5 to 20.)

R- (OCH ₂ CH ₂ ) _n OH ... (IV) (In the formula (IV), R represents a carbon chain having 6 to 14 carbon atoms which may be branched, and n represents an integer of 5 to 20. )

[0017]

[Chemical 12] (In the formula (V), R represents a carbon chain having 6 to 14 carbon atoms which may be branched, and j, k, m and n each represent an integer of 1 to 20.)

[0018]

[Chemical 13] (In the formula (VI), R'is a carbon chain having 6 to 14 carbon atoms, j,
k, m, and n represent the integer of 1-20. )

[0019]

[Chemical 14] (In the formula (VII), p and q represent an integer of 0 to 40.)

[0020]

[Chemical 15] (In the formula (VIII), R ₆ and R ₇ are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms, and R ₈ is 10 to 2 carbon atoms.
0 represents an alkyl group or an alkenyl group. )

[0021]

[Chemical 16] (In the formula (IX), R ₉ and R ₁₀ are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ₁₁ is an alkyl group having 10 to 16 carbon atoms which may contain an amide group or an alkyl group derived from coconut oil. Represents.)

(3) The ink set for ink jet recording according to (1) or (2) above, wherein the polymer forming the polymer fine particles is a vinyl polymer or a polyester polymer.

(4) The above-mentioned (1), wherein the polyol having a carbon number of 8 or more and 11 or less (a second type of hydroxy compound) or glycol ether is 2-ethyl-1,3-hexanediol. The ink set for inkjet recording according to any one of to (3).

(5) The polyol having a carbon number of 8 or more and 11 or less (a second type of hydroxy compound) or glycol ether is 2,2,4-trimethyl-1,3-pentanediol. (1)-
The ink set for inkjet recording according to any one of (3).

(6) The ink set for ink jet recording according to any one of (1) to (5) above, wherein the black ink is a self-dispersion pigment.

(7) The surface tension of the ink is 40 mN / m or less, and the ink viscosity at 25 ° C. is 5 mPas.
The ink set for inkjet recording according to any one of (1) to (6) above, which is an ink of sec or more.

(8) The inkjet according to any one of the above (1) to (7), wherein the aqueous dispersion of fine polymer particles containing the coloring material contains 8 to 20 wt% of solid content. Recording ink set.

(9) An ink jet recording method characterized in that energy is applied to the ink set for ink jet recording according to any one of (1) to (8) to eject the ink.

(10) The ink jet recording method as described in (9) above, wherein the ink is ejected by applying thermal energy to the ink.

(11) The above-mentioned (9) is characterized in that the mechanical energy is applied to the ink to eject the ink.
Inkjet recording method described.

(12) Mj is 5 to 35 pl and Vj is 6 to
20 m, a frequency of 1 kHz or more, a resolution of 300 dpi or more, and one-pass printing conditions, and the ink set for ink jet recording according to any one of (1) to (8) is used, (9) to (11) The inkjet recording method according to any one of 1.

(13) An ink cartridge comprising an ink containing portion containing the ink set for ink jet recording according to any one of (1) to (8).

(14) An ink containing section or an ink cartridge containing the ink set for ink jet recording according to any one of (1) to (8), and a head section for dropping the ink into drops by the action of energy. Alternatively, an inkjet recording apparatus comprising a recording unit.

(15) The ink jet recording apparatus according to (14), wherein an ink repellent film layer is formed on the surface of the nozzle plate of the ink jet recording head by eutectoid plating.

(16) The ink jet recording apparatus according to the above (14) or (15), wherein the nozzle diameter of the ink jet recording head is 30 μm or less.

(17) An ink constituting the ink set described in any one of (1) to (8) above.

The components of each ink will be described below. As the color ink, a polymer emulsion in which polymer fine particles contain a coloring material is used. In the present specification, “containing a coloring material” means either or both of a state in which the coloring material is encapsulated in the polymer particles and a state in which the coloring material is adsorbed on the surface of the polymer particles. In this case, it is not necessary that all the coloring materials mixed in the ink of the present invention are encapsulated or adsorbed in the polymer fine particles, and the coloring materials are dispersed in the emulsion as long as the effects of the present invention are not impaired. Good.

Examples of the coloring material include coloring materials that are water-insoluble or sparingly water-soluble and can be adsorbed by the polymer. In the present specification, the term "water-insoluble or sparingly water-soluble" means that the coloring material is not dissolved in 0.1 part by weight or more with respect to 100 parts by weight of water at 20 ° C, and "dissolved" is visually observed in the aqueous solution surface layer or lower layer. It means that separation or sedimentation of the coloring material is not observed.

Examples of the coloring material of the ink include dyes such as oil-soluble dyes and disperse dyes, and pigments. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorption / encapsulation properties, but pigments are used in the present invention because of the light resistance of the image obtained.

The pigment used in the present invention includes carbon black as the black pigment, and the color pigments include anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone,
Includes perylene, heterocyclic yellow, quinacridone and (thio) indigoid. Representative examples of phthalocyanine blue include copper phthalocyanine blue and its derivative (Pigment Blue 15). Typical examples of quinacridone are Pigment Orange 48, Pigment Orange 49,
Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42.
including. Typical examples of anthraquinone are Pigment Red 43, Pigment Red 194 (Perinone Red),
Pigment Red 216 (Brominated Pyrantron Red)
And Pigment Red 226 (Pyrantron Red). A typical example of pyrelin is Pigment Red 123.
(Bellmillion), Pigment Red 149 (Scarlet), Pigment Red 179 (Maroon), Pigment Red 190 (Red), Pigment Violet, Pigment Red 189 (Yellow Shade Red) and Pigment Red 224. Representative examples of thioindigoides include Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36 and Pigment Violet 38. A typical example of the heterocyclic yellow is Pigment Yellow 117.
And Pigment Yellow 138. Examples of other suitable colored pigments are found in The Color Index, Third Edition (The Society o
f Dyers and Colorists, 1982). When the pigment is used as a colorant, the above dye may be used together for complementary color matching, toning and the like. The blending amount of the above-mentioned coloring material is, in relation to the blending amount of the polymer, about 10 to 200 wt%, particularly about 25 to 1 wt% relative to the weight of the polymer.
It is preferably 50 wt%.

As the polymer forming the above polymer emulsion, for example, a vinyl polymer, a polyester polymer, a polyurethane polymer or the like can be used. Polymers particularly preferably used are vinyl-based polymers and polyester-based polymers.
The polymers disclosed in 000-53897 and 2001-139849 are cited.

According to a preferred embodiment of the present invention, the average particle diameter of the polymer fine particles containing these coloring materials is most preferably 0.16 μm or less in the ink. The content of polymer particles in the ink is 8 to 20 wt% in terms of solid content.
% Is preferable, and more preferably about 8 to 12 wt%.

25 as the ink of the ink set of the present invention
It is preferable to use an aqueous ink having a low surface tension of 40 mN / m or less, more preferably 35 mN / m or less, at a surface tension at 0 ° C. The inventors of the present invention have studied various means for improving the drying property of a recorded image, and as a result, if the surface tension of the ink is adjusted to 40 mN / m or less, most recording materials can be obtained. On the other hand, it is based on the finding that quick permeation drying is possible.

Further, by setting the surface tension of the ink to 40 mN / m or less, the wetting of the ink to the head member is improved, and the frequency response is improved even with high viscosity ink of 8 mPa · sec (25 ° C.) or more, and the ejection is improved. This is because the stability has been remarkably improved. This low surface tension ink can be achieved by using a polyol or glycol ether and a fluorosurfactant in a specific ink composition.

As the ink of the ink set of the present invention, 5
mPa · sec (= 5 cps) or more, preferably 8 mP
Printing quality is remarkably improved by using a high-viscosity ink of a.sec (25 ° C.) or more. 3 mPa · sec (25
℃) low viscosity ink has about 70% water content
However, with high-viscosity ink of about 8 mPa · sec (25 ° C.), it is about 50% or less, and the water evaporation rate when ink droplets land on the paper surface is 2.0 to 3.0 times higher.
Therefore, the high-concentration pigment aggregates on the paper surface at a high speed, and bleeding (feathering) is almost eliminated.

Further, by increasing the polymer emulsion concentration or the pigment concentration, the viscosity of the ink is increased, and the pigment easily aggregates and stays on the paper surface to improve the coloring density and color tone, and almost no feathering is caused. The concentration of the polymer emulsion containing the coloring material in the ink is 8 wt% or more, preferably 10 wt% in terms of solid content.
% Or more. When the ink set is formed by using the self-dispersion type carbon black as the coloring material, the pigment concentration of the black ink is 6 wt% or more, preferably 8 wt% or more.

Further, the ink of the ink set of the present invention has 1,3-butanediol, triethylene glycol, 1,3-butanediol, 1,3-butanediol 6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, and at least one or more high-viscosity wetting agents selected from glycerin and a high-viscosity mixture Wetting agents are used. High viscosity wetting agents can be combined with high pigment concentrations to achieve high viscosity inks.

The ink composition of the present invention is a recording ink having the following constitution, preferably having an ink viscosity of 5 mPa · sec or more, more preferably 8 mPa · sec (25 ° C.) or more. A coloring material for printing, water for dispersing it as an essential component, a wetting agent, a water-soluble organic solvent, a surfactant, an emulsion, which is added as necessary,
It is composed of preservatives and pH adjusters. The reason why the wetting agents 1 and 2 are mixed is to utilize the characteristics of each wetting agent and to adjust the viscosity. Wetting agent 1 is indispensable, but wetting agents 1 and 2 are not necessarily included together.

Colorant Wetting Agent 1 (Glycerin) Wetting Agent 2 (1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, tri At least one or more kinds selected from methylolpropane and trimethylolethane: first type hydroxy compound) Water-soluble organic solvent surfactant Polyol having 8 or more and 11 or less carbon atoms (second type hydroxy compound) or Glycol ether preservative pH adjuster Pure water

The other wetting agent preferably contains sugar. Examples of sugars include monosaccharides, disaccharides,
Examples include oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like. To be Here, the polysaccharide means a sugar in a broad sense, and is meant to include substances widely existing in the natural world such as α-cyclodextrin and cellulose.

The derivatives of these sugars include reducing sugars of the above-mentioned sugars {for example, sugar alcohols (general formula H
It is represented by OCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5). )}, Oxidized sugar (eg,
Aldonic acid, uronic acid, etc.), amino acids, thio acids, etc. Sugar alcohol is particularly preferable, and specific examples thereof include maltitol, sorbitol and the like. The content of these sugars is 0.1 to 40 wt% of the ink composition.
%, Preferably 0.5 to 30 wt% is suitable.

Further, the ratio of the fine polymer particles containing the coloring material and the wetting agent has a great influence on the stability of ink ejection from the head. If the solid content of the pigment is high but the amount of the wetting agent is small, the evaporation of water in the vicinity of the ink meniscus of the nozzle will occur, resulting in ejection failure. The wetting agent content is 10 to 50 wt%
On the other hand, the amount of the polymer particles containing the coloring material is 8 wt% or more, and preferably 8 to 20 wt%.
The ratio of both the wetting agent and the solid content of the polymer fine particles is 0.5 to
Although it is 6.25, it is more preferably 2.0 to 6.0, and most preferably 3.0 to 5.0. Inks in this range are very good in drying property, storage test and reliability test.

Regarding the wetting agent and the water-soluble organic solvent, the ink of the present invention uses water as the liquid medium, but in order to make the ink have desired physical properties, prevent the ink from drying, and disperse the ink. For the purpose of improving stability,
For example, the following water-soluble organic solvents are used. A plurality of these water-soluble organic solvents may be mixed and used.

Specific examples of the wetting agent and the water-soluble organic solvent include the following. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, Polypropylene glycol, 1,2,6
-Hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, thiodiglycol, pentaerythritol, and other polyhydric alcohols other than the first and second types of hydroxy compounds (third Types of hydroxy compounds); ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Polyhydric alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryls such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Ethers; 2-pyrrolidone, N-methyl-2-pyrrolidone,
Nitrogen-containing heterocyclic compounds (lactams) such as N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidinazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide; amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine; sulfur-containing dimethyl sulfoxide, sulfolane, thiodiethanol, etc. Compounds: propylene carbonate, ethylene carbonate and the like.

Among these organic solvents, thiodiethanol, polyethylene glycol 200 to 600, 1,
2,6-hexanetriol, 1,2,4-butanetriol, 2-pyrrolidone and N-methyl-2-pyrrolidone are preferred. These have excellent effects on solubility and prevention of defective ejection characteristics due to water evaporation.

Further, in the present invention, ureas and alkylglycine can be contained as desired. Examples of such ureas include urea, thiourea, ethylene urea, 1,3-dimethyl-2-imidazolidinone, and the like, and alkyl glycines include N-methylglycine and N, N-dimethylglycine. , N-ethylglycine and the like.

Basically, both of these ureas and alkylglycines maintain excellent moisturizing properties (leading to improved storage stability) in water-based inks, and ejection stability and clogging resistance of a recording head of an ink jet printer. Exhibits an excellent effect. Further, since it is widely applicable to adjustment of ink viscosity and surface tension and has excellent resistance to clogging, it is possible to prevent clogging of the head and prevent ejection defects such as flight deflection of ink droplets during ink ejection.

The amount added to the ink is generally 0.
5 to 50% by weight, more preferably 1 to 20% by weight, and if less than 0.5% by weight, the desired properties required for the inkjet printer recording head cannot be satisfied, and 50 w
Addition in excess of t% causes thickening, which adversely affects the storage stability of the ink and leads to defective ejection of the ink.

As the surface active agent used in the present invention, at least one kind of anionic surface active agent, nonionic surface active agent and amphoteric surface active agent is used, and at least one kind of fluorine type surface active agent is used. that time,
A surfactant that does not impair the dispersion stability is selected depending on the combination of the coloring material, the wetting agent, and the water-soluble organic solvent. Further, in the present invention, the wettability to the recording paper can be improved by using the surfactant.

Among the above-mentioned surfactants, particularly preferable surfactants are polyoxyethylene alkyl ether acetate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxypropylene polyoxyethylene alkyl ether, alkylcarbonyl. Examples thereof include oxypolyoxyethylene, alkylcarbonyloxypolyoxyethylene polyoxypropylene, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene block copolymer, and acetylene glycol-based surfactant.

As the anionic surfactant, a polyoxyethylene alkyl ether acetate represented by the following formula (I) and / or a following formula (II) having a branched alkyl chain having 5 to 16 carbon atoms is shown. By using dialkylsulfosuccinic acid, the properties of plain paper are improved, and the stability of the colorant is improved. Further, the use of lithium ion, quaternary ammonium or quaternary phosphonium as the counterion of the above-mentioned surfactant of the present invention makes the surfactant exhibit excellent solubility stability.

R ₄ —O— (CH ₂ CH ₂ O) _m CH ₂ COOM − − − (I) R ₄ : an alkyl group having 6 to 14 carbon atoms which may be branched m: an integer M from 3 to 12: Alkali metal ion, quaternary ammonium, quaternary
Grade phosphonium or alkanolamine

[0063]

[Chemical 17] R ₅ : C ₅ -C 16 branched alkyl group M: Alkali metal ion, quaternary ammonium, quaternary
Grade phosphonium or alkanolamine

Specific examples of the surfactants represented by the above formulas (I) and (II) used in the present invention are shown below in free acid form.

[Chemical 18]

[0065]

[Chemical 19]

Examples of the nonionic surfactant include, for example,
Polyoxyethylene alkyl ether, polyoxypropylene polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxy Examples thereof include ethylene alkylamide.

The acetylene glycol-based surfactant is
2,4,7,9-Tetramethyl-5-decyne-4,7-
Diol, 3,6-dimethyl-4-octyne-3,6-
Acetylene glycols such as diol and 3,5-dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 46 manufactured by Air Products (USA)).
5, 485 or TG) can be used, but Surfynol 465, 104 and TG show particularly good print quality.

Preferred surfactants are those of the general formula (II
I) polyoxyethylene alkylphenyl ethers,
A polyoxyethylene alkyl ether of the general formula (IV),
Examples include nonionic surfactants such as polyoxypropylene polyoxyethylene alkyl ether of general formula (V), polyoxyethylene polyoxypropylene of general formula (VI), and acetylene glycol-based surfactants of general formula (VII). be able to. When these are used in combination, the synergistic effect is further enhanced in penetrability, whereby an ink with less color boundary bleeding and less character bleeding can be obtained.

Specific examples of the above-mentioned surfactant used in the present invention are shown below by the general formulas (III), (IV), (V), (VI) and (VI).
I).

[Chemical 20] R: carbon chain having 6 to 14 carbon atoms which may be branched k: integer of 5 to 20

R- (OCH ₂ CH ₂ ) _n OH --- (IV) R: a carbon chain having 6 to 14 carbon atoms which may be branched n: an integer of 5 to 20

[0071]

[Chemical 21] R: an optionally branched carbon chain having 6 to 14 carbon atoms j, k, m, n: 1 to 20

[0072]

[Chemical formula 22] R ′: carbon chain having 6 to 14 carbon atoms j, k, m, n: integer of 1 to 20

[0073]

[Chemical formula 23] p, q: integer from 0 to 40

Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine and lauryl dihydroxyethyl betaine.

The following specific examples are preferably used, but not limited to these. Lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, stearyl dimethyl amine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, dimethyl lauryl betaine, etc.

The above surfactant (VIII) used in the present invention,
(IX) is specifically shown below.

[Chemical formula 24] (In the formula (VIII), R ₆ and R ₇ are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms, and R ₈ is 10 to 20 carbon atoms.
Represents an alkyl group or an alkenyl group. )

[0077]

[Chemical 25] (In the formula (IX), R ₉ and R ₁₀ are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ₁₁ is an alkyl group having 10 to 16 carbon atoms which may contain an amide group or an alkyl group derived from coconut oil. Represents.)

In particular, in the present invention, by using a perfluoroalkyl sulfonate represented by the following structural formula as the fluorine-containing surfactant, good printing quality, especially color development and even dyeing property on paper are remarkably improved. . As the perfluoroalkyl sulfonate represented by the following structural formula, for example, a combination of R ₁ , R ₂ and R ₃ is C ₃ F ₇ −,
CF ₃ −, F, or C ₄ F ₉ −, F, F, and M ₁ is Na
And FT-110 manufactured by Neos Co., Ltd. is favorably used.

[0079]

[Chemical formula 26] (R ₁ , R ₂ and R ₃ represent either a perfluoroalkyl group or a fluorine atom, and M ₁ represents any of Li, Na and K.)

Further, by using the above-mentioned fluorine-containing surfactant in combination with the polyoxyethylene alkyl ether of the general formula (IV) and the polyoxypropylene polyoxyethylene alkyl ether of the general formula (V), a remarkable improvement in permeability can be achieved. As a result, bleeding at the color boundaries is reduced, the color developability is improved, and ink with less bleeding of characters is selected. The surfactants may be used alone or in combination of two or more.

By setting the pH of the ink to 6 or more, the storage stability of the ink can be obtained, and most of the copy papers, sticky notes and the like used in the office have a pH of 5 to 6, Ink is ejected onto these recording papers from a fine ejection port of 9 to 60 μm and is ejected as droplets having a weight of 3 ng to 50 ng at 5 to 20 m / s, and the adhesion amount in a single color is 1.5 g / m ^{2 to} 30 g. / M ² as JIS P-812
It is possible to provide a recording system for forming a recorded image of high image quality and high resolution by recording on so-called plain paper having a Steckigt sizing degree of 3 seconds or more by the 2 test method. However, p
When H is 9 or more, the physical properties of the surfactant represented by the formula (II) are likely to change due to decomposition during storage, so the formula (II)
When the surfactant represented by is used, the pH is preferably 6-9.

(I) and (I which can be used in the present invention
I), (III), (IV), (V), (VI), (VII), (V
Addition amounts of III) and (IX) can give desired penetrability to the ink characteristics required by the printer system in the range of 0.05 to 10 wt%. Where 0.0
If it is less than 5 wt%, bleeding occurs at the boundary of the two-color overlapping portion in any case, and if it is added in excess of 10 wt%, the compound itself tends to precipitate at a low temperature, resulting in poor reliability.

Further, the addition amount of the above-mentioned fluorine-based surfactant can be reduced by using it in combination with the above-mentioned surfactants (I) to (IX). It is possible to give the desired permeability to the ink properties required by the system. Where 0.0
The combined use of less than 5 wt% has no remarkable effect on the improvement of permeability in any case, and the addition of more than 5 wt% deteriorates reliability such as viscosity increase and aggregation during high temperature storage. The addition amount of 0.1 to 2 wt% can be preferably used from the viewpoint of storability.

The surface tension in the present invention is an index showing the penetrability into paper, and in particular, it shows the dynamic surface tension in a short time of 1 second or less after the surface is formed, and the static surface tension measured at the saturation time. Is different from. As a measuring method, JP-A-63-31
Although any method can be used as long as it can measure the dynamic surface tension of 1 second or less by the conventionally known method described in Japanese Patent No. 237, etc., in the present invention, it was measured using a Wilhelmy type hanging plate type surface tension meter. . The value of surface tension is 40mN / m
The following is preferable, and more preferable is 35 mN / m or less to obtain excellent fixability and dryness.

The polyol or glycol ether having 8 or more and 11 or less carbon atoms used in the present invention is a partially water-soluble polyol having a solubility of 0.1 to less than 4.5 wt% in water at 25 ° C. Alternatively, glycol ether is used in an amount of 0.1 to 10.0 w based on the total weight of the recording ink.
It was found that the addition of t% improves the wettability of the ink to the thermal element, and discharge stability and frequency stability can be obtained even with a small addition amount.

Specific examples of preferable polyols having 8 to 11 carbon atoms include the following. 2-Ethyl-1,3-hexanediol Solubility:
4.2 wt% (20 ° C) 2,2,4-trimethyl-1,3-pentanediol Solubility: 2.0 wt% (25 ° C)

0.1-4.5 wt in water at 25 ° C.
Penetrants having a solubility between less than% have the advantage of very high permeability at the expense of low solubility. Therefore, 2
To produce a very highly penetrative ink by combining a penetrant having a solubility of less than 0.1 to 4.5 wt% in water at 5 ° C. with another solvent or another surfactant. Is possible.

In addition to the above colorant, solvent and surfactant, the following conventionally known additives can be added to the ink of the present invention. <Antiseptic / Antifungal Agent> As an antiseptic / antifungal agent, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like can be used in the present invention.

<PH Adjusting Agent> As the pH adjusting agent, any substance can be used as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared. Examples thereof include amines such as diethanolamine and triethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide and quaternary phosphonium water. Examples thereof include oxides, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate.

Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate and sodium uramildiacetate.

<Rust Inhibitor> Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

<Other Additives> In addition, water-soluble ultraviolet absorbers, water-soluble infrared absorbers and the like can be added depending on the purpose.

Next, the ink set of the present invention will be described. The ink set consists of black ink and color ink. As the color ink, a color ink containing a polymer emulsion containing the above coloring material is applied. The black ink corresponds to a structure in which the polymer emulsion forming the color ink is replaced with a self-dispersion type carbon black.

That is, the ink set of the present invention is an ink jet recording ink set comprising a black ink and at least one kind of color ink, and the black ink preferably contains a self-dispersion pigment, and glycerin or glycerin and 1, At least one or more wetting agents selected from 3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane and trimethylolethane. Containing a (first type of hydroxy compound), at least 8 or more and 11 or less carbon atoms of a polyol (a second type of hydroxy compound) or glycol ether, a water-soluble organic solvent, water, and further,
It may contain at least one or more kinds of surfactants selected from anions, nonions and amphoteric surfactants, and may also contain a fluorine-containing surfactant having a specific structure.
An ink having an ink viscosity at 5 ° C. of 5 mPa · sec or more, in which a color ink contains a polymer emulsion in which polymer fine particles contain a pigment, glycerin or glycerin and 1,3-butanediol, triethylene glycol, 1 , 6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, and at least one or more kinds of wetting agents selected from trimethylolethane (hydroxy compound of the first kind). Contains at least a polyol having a carbon number of 8 or more and 11 or less (a second type of hydroxy compound) or a glycol ether, a water-soluble organic solvent, and water, and
An ink having an ink viscosity at 25 ° C. of 5 mPa · sec or more containing at least one kind of surfactant selected from anions, nonionics and amphoteric surfactants, and containing at least one kind of fluorine-containing surfactant. The inkjet recording ink set is characterized by being present.

The color ink has the following constitution. Polymer emulsion wetting agent 1 (glycerin) containing color coloring agent Wetting agent 2 (1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene) At least one or more kinds selected from glycol, trimethylolpropane, and trimethylolethane: first-type hydroxy compound) Water-soluble organic solvent surfactant Polyol having 8 or more and 11 or less carbon atoms (second-type hydroxy) Compound) or glycol ether antiseptic pH adjuster Pure water

The black ink preferably has the following constitution. (I) Self-dispersible carbon black (ii) Wetting agent 1 (glycerin) (iii) Wetting agent 2 (1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentane (At least one or more kinds selected from diol, diethylene glycol, dipropylene glycol, trimethylolpropane and trimethylolethane) (iv) Water-soluble organic solvent (v) Surfactant (vi) Polyol having 8 or more and 11 or less carbon atoms or Glycol ether (vii) Resin emulsion (viii) Preservative (ix) pH adjuster (x) Pure water

As the coloring material of the black ink, self-dispersion which can be stably dispersed without using a dispersant in which at least one hydrophilic group is bonded to the surface of carbon black directly or through another atomic group. It is preferable to use mold color pigments. As a result, a dispersant for dispersing carbon black is not required unlike the conventional ink. As the self-dispersion carbon black used in the present invention, those having ionicity are preferable, and those charged anionically and those charged cationically are preferable.

As the anionic hydrophilic group, for example,-
COOM ₂ , -SO ₃ M ₂ , -PO ₃ HM ₂ , -PO
_{3 (M 2) 2, -SO} 2 NH 2, -SO 2 NHCOR 12 ( however,
In the formula, M ₂ represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium, and R ₁₂ has 1 to 1 carbon atoms.
2 represents an alkyl group, a phenyl group which may have a substituent or a naphthyl group which may have a substituent. ) And the like. In the present invention, among these, in particular, -C
It is preferable to use one in which OOM ₂ or —SO ₃ M ₂ is bonded to the surface of the color pigment.

Further, "M ₂ " in the hydrophilic group may be, for example, an alkali metal such as lithium, sodium or potassium, and an organic ammonium such as mono-to-trimethylammonium, mono-to-triethylammonium or mono-ammonium. To trimethanol ammonium. As a method for obtaining an anionically charged color pigment, as a method for introducing -COONa on the surface of the color pigment, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, or a reaction of a diazonium salt is performed. However, the present invention is not limited to these.

The cationic hydrophilic group is preferably, for example, a quaternary ammonium group, more preferably a quaternary ammonium group shown below. In the present invention, any one of these is used on the carbon black surface. What is combined with is preferably used as a coloring material.

[0101]

[Chemical 27] (In the above formula, R represents either a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)

As a method for producing the above-mentioned cationic self-dispersion type carbon black having a hydrophilic group bonded thereto, for example, there is a method of bonding an N-ethylpyridyl group having the structure shown below. Include a method of treating carbon black with 3-amino-N-ethylpyridinium bromide, but of course, the present invention is not limited thereto.

[0103]

[Chemical 28]

Further, in the present invention, the hydrophilic group as mentioned above may be bonded to the surface of carbon black through another atomic group. Examples of the other atomic group include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Specific examples of the hydrophilic group described above is bonded to the surface of carbon black via other atomic group, for _{example, -C 2 H 4 COOM 2,} -PhSO 3 M 2, -
C ₅ H ₁₀ NH ₃ ⁺ (However, M _{2 in} the formula represents a hydrogen atom, an alkali metal, ammonium or organic ammonium.)
However, the present invention is not limited to these.

The self-dispersion type carbon black used in the black ink of the ink set of the present invention is cationically or anionically charged by the hydrophilic group on the surface of carbon black, and has water dispersibility by the repulsion of the ions. Moreover, the hydrophilic group also improves the hydrophilicity. Therefore, an aqueous pigment ink stably dispersed in an aqueous medium can be obtained without increasing the particle diameter and viscosity of the pigment even if left for a long time. When the polarity of the black ink is opposite to that of the color inks constituting the ink set, an image with the least color boundary bleeding can be obtained, but in the ink set of the present invention, high viscosity and low surface tension permeability Since it is possible to form an excellent ink, even if the color ink and the black ink have the same polarity, there is very little color boundary bleeding, and even when the ink is mixed on the nozzle maintenance mechanism or nozzle plate, it is extremely An ink set having excellent handleability can be obtained without causing aggregation thickening.

As the other constituent materials used for the black ink of the ink set, the materials described for the ink containing polymer particles containing a coloring material can be applied as they are.
In addition, a resin emulsion is mentioned as a suitable thing only using for black ink. What is a resin emulsion?
It means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. Examples of the resin component of the dispersed phase include acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, styrene resin and the like.

According to a preferred embodiment of the present invention, this resin is preferably a polymer having both a hydrophilic portion and a hydrophobic portion. The particle size of these resin components is not particularly limited as long as it forms an emulsion,
It is preferably not more than about 5 nm, more preferably about 5 to 100 nm.

These resin emulsions can be obtained by mixing resin particles with water, optionally together with a surfactant. For example, an acrylic resin or styrene-acrylic resin emulsion is prepared by adding (meth) acrylic acid ester or styrene, (meth) acrylic acid ester, and optionally (meth) acrylic acid ester, and a surfactant to water. It can be obtained by mixing. The mixing ratio of the resin component and the surfactant is usually preferably about 10: 1 to 5: 1. If the amount of the surfactant used is less than the above range, it becomes difficult to form an emulsion, and if it exceeds the above range, the water resistance of the ink tends to decrease and the penetrability tends to deteriorate, such being undesirable. The ratio of the resin as the dispersed phase component of the emulsion to water is 6 parts by weight of water to 100 parts by weight of the resin.
A range of 0 to 400 parts by weight, preferably 100 to 200 parts by weight is suitable.

Commercially available resin emulsions include Microgel E-1002 and E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.).
Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), Boncoat 5454
(Styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Zeon Corporation), Cybinol SK-200 (acrylic resin emulsion, Saiden Chemical Co., Ltd.) Manufactured) and the like.

The ink used in the present invention preferably contains a resin emulsion such that the resin component is 0.1 to 40 wt% of the ink, more preferably 1 to 2
It is in the range of 5 wt%.

The resin emulsion has the property of thickening and aggregating, has the effect of suppressing the permeation of the coloring component, and further promoting the fixing to the recording material. Further, depending on the type of resin emulsion, a film is formed on the recording material, which has the effect of improving the abrasion resistance of the printed matter.

An ink cartridge containing the ink of the present invention and an ink jet recording apparatus equipped with the ink cartridge will be described with reference to the accompanying drawings. However, the following is only one of the constitutional examples, and the present invention is not limited thereto. Not a thing.

FIG. 1 is a schematic front view of a mechanical portion of a serial type ink jet recording apparatus equipped with an ink cartridge having an ink containing portion containing the ink of the present invention.
The mechanism portion of this ink jet recording apparatus has a main support guide rod 3 and a sub-support guide rod 4 which are laterally bridged between the side plates 1 and 2 on both sides in a substantially horizontal positional relationship. The rod 4 supports the carriage unit 5 slidably in the main scanning direction. The carriage unit 5 has yellow (Y) ink,
Four heads 6 for ejecting magenta (M) ink, cyan (C) ink, and black (Bk) ink,
The ejection surface (nozzle surface) 6a (the nozzle surface on which the ink-repellent coating layer is eutectoid plated) is mounted downward, and four heads 6 are provided above the head 6 of the carriage unit 5. Four ink cartridges 7Y, 7M, 7C, which are ink supply members of respective colors for supplying ink,
It is equipped with 7Bk that can be exchanged.

The carriage unit 5 is connected to a timing belt 11 stretched between a driving pulley (driving timing pulley) 9 rotated by a main scanning motor 8 and a driven pulley (idler pulley) 10 for main scanning. By controlling the drive of the motor 8, the carriage unit 5,
That is, the four heads 6 are moved in the main scanning direction. Further, subframes 13 and 14 are erected on a bottom plate 12 that connects the side plates 1 and 2, and the subframes 13 and 14 are
In between, a conveyance roller 15 for feeding the paper 16 in the sub-scanning direction orthogonal to the main scanning direction is rotatably held. Then, a sub-scanning motor 17 is arranged on the side of the sub-frame 14, and in order to transmit the rotation of the sub-scanning motor 17 to the conveying roller 15, the gear 18 fixed to the rotating shaft of the sub-scanning motor 17 and the conveying roller 15 are provided. And a gear 19 fixed to the shaft.

Further, a reliability maintaining / restoring mechanism (hereinafter referred to as “subsystem”) 21 of the head 6 is arranged between the side plate 1 and the subframe 13. The subsystem 21 holds four cap means 22 for capping the ejection surface of each head 6 with a holder 23.
3 is swingably held by the link member 24, and the carriage unit 5 comes into contact with the engaging portion 25 provided on the holder 23 by the movement of the carriage unit 5 in the main scanning direction. 23 is lifted up and the ink jet head 6 is moved by the cap means 22.
The ejection surface 6a of the carriage unit 5 is capped.
Is moved to the printing area side, the carriage unit 5
The holder 23 is lifted down in accordance with the movement of, and the cap means 22 is separated from the ejection surface 6a of the inkjet head 6.

The cap means 22 is connected to the suction pump 27 via the suction tube 26, forms an atmosphere opening port, and communicates with the atmosphere via the atmosphere opening tube and the atmosphere opening valve. The suction pump 27 discharges the sucked waste liquid to a waste liquid storage tank (not shown) via a drain tube or the like.

Further, on the side of the holder 23, a wiper blade 28, which is a wiping means made of a fibrous member for wiping the ejection surface 6a of the ink jet head 6, a foamed member, or an elastic member such as rubber, is provided as a blade arm 29.
The blade arm 29 is pivotally supported so that it can be pivoted by the rotation of a cam which is pivoted by a driving means (not shown).

Next, the ink cartridge 7 will be described with reference to FIGS. Here, FIG. 2 is an external perspective view of the ink cartridge before being loaded in the recording apparatus, and FIG.
FIG. 3 is a front sectional view of an ink cartridge. The ink cartridge 7 has a cartridge body 41 as shown in FIG.
An ink absorber 42, which absorbs ink of a desired color, is housed therein. The cartridge body 41 is formed by adhering or welding an upper lid member 44 to the upper opening of a case 43 having a wide opening at the top, and is made of, for example, a resin molded product. The ink absorber 42 is made of a porous material such as a urethane foam body and absorbs ink after being compressed and inserted into the cartridge body 41.

An ink supply port 45 for supplying ink to the recording head 6 is formed at the bottom of the case 43 of the cartridge body 41, and a seal ring 46 is fitted on the inner peripheral surface of the ink supply port 45. Further, the upper lid member 44 is formed with an atmosphere opening port 47. In the cartridge main body 41, before the loading, the ink supply port 45 is closed and at the time of handling the cartridge such as loading or transportation,
Alternatively, the pressure applied to the wide side wall during vacuum packaging causes the case 4
A cap member 50 is attached in order to prevent the ink inside from leaking due to the compression deformation of 3.

Further, as shown in FIG. 2, the atmosphere opening port 47 seals by attaching a film-like sealing member 55 having an oxygen permeability of 100 ml / m ² or more to the upper lid member 44. The sealing member 55 is sized to seal not only the atmosphere opening port 47 but also a plurality of grooves 48 formed around it. In this way, the atmosphere opening 47 has an oxygen permeability of 10
By sealing with a sealing member 55 of 0 ml / m ² or more, the ink cartridge 7 is packaged in a reduced pressure state using a packaging member such as an aluminum laminated film that does not have air permeability. Even when a gas is dissolved in the ink due to the atmosphere in the space A (see FIG. 3) generated between the ink and the cartridge body 41, the air in the ink is high outside the cartridge body 41 via the seal member 55. The ink is discharged into the space between it and the packaging member, and the degree of deaeration of the ink is improved.

Further, FIG. 4 shows an example of the construction of a recording cartridge provided with an ink containing section for containing the ink of the present invention and a head section for ejecting ink droplets. That is, the recording unit 30 is of a serial type, and is composed of an inkjet head 6, an ink tank 41 that stores ink supplied to the inkjet head 6, and a lid member that seals the inside of the ink tank 41. Is configured. A large number of nozzles 32 for ejecting ink are formed in the inkjet head 6. Ink is guided from the ink tank 41 to a common liquid chamber (not shown) through an ink supply pipe (not shown), and is ejected from the nozzle 32 in response to an electric signal from the recording apparatus main body input from the electrode 31. .

The recording unit of this type has a structure suitable for a type of head that can be manufactured at low cost, that is, a so-called thermal type or bubble type head that uses thermal energy as a driving power source. In the ink of the present invention, in a recording method such as a bubble method or a thermal method, by adding the above components, the wettability to a thermal element is improved, so that ejection stability and frequency stability can be obtained even with a small addition amount. It is highly suitable because it is safe and secure. Further, the ink of the present invention is suitable not only for a recording method for ejecting ink by applying thermal energy, but also for a recording method for ejecting ink by applying mechanical energy.

Here, the serial type ink jet recording apparatus as described above has been described. However, the ink of the present invention has nozzles in an arbitrary arrangement such as a staggered pattern and has a resolution equal to or a fraction of a target image. It is also possible to apply the present invention to a recording apparatus having a so-called line head, which is densely integrated and arranged in a width larger than the width of the recording medium.

The recording device mentioned here may be not only an output printer for a PC or a digital camera, but also a device having a complex function in combination with a fax, a scanner, a telephone or the like.

[0125]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Preparation Examples, Production Examples and Examples, but the present invention is not limited to the following Preparation Examples, Production Examples and Examples. The amounts (%) of the respective components described in Preparation Examples, Production Examples, and Examples are based on weight.

<Preparation Example 1> (Preparation of Copper Phthalocyanine Pigment-Containing Polymer Fine Particle Dispersion) With reference to Preparation Example 3 of JP 2001-139849 A, that is, an additional sample preparation was performed as described below. First of all, as the preparation of the polymer solution, a mechanical stirrer,
After thoroughly replacing the inside of a 1 L flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux tube and a dropping funnel with nitrogen gas, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, and 4 of polyethylene glycol methacrylate. 0.0 g, styrene macromer (Toagosei Co., Ltd.)
Product name: AS-6) (4.0 g) and mercaptoethanol (0.4 g) were charged, and the temperature was raised to 65 ° C. Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxyethyl methacrylate 60.0 g, styrene macromer (Toagosei Co., Ltd.)
Made, brand name: AS-6) 36.0 g, mercaptoethanol 3.6 g, azobis dimethyl valeronitrile 2.4
A mixed solution of g and 18 g of methyl ethyl ketone was dropped into the flask over 2.5 hours.

After the completion of dropping, a mixed solution of 0.8 g of azobisdimethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. 1 at 65 ° C
After aging for a time, azobis dimethyl valeronitrile 0.
8 g was added and the mixture was aged for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of a polymer solution having a concentration of 50%. Next, a part of the polymer solution was dried and measured by gel permeation chromatography (standard: polystyrene, solvent: tetrahydrofuran). The weight average molecular weight was 15,000.
Met.

28 g of the polymer solution obtained above, 26 g of copper phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone and 30 g of ion-exchanged water were sufficiently stirred. After that, 3 roll mill (manufactured by Noritake Company, Ltd., trade name: NR-8)
4A) was kneaded 20 times. The obtained paste was put into 200 g of ion-exchanged water and sufficiently stirred, and then methyl ethyl ketone and water were distilled off using an evaporator to obtain 160 g of a blue polymer fine particle dispersion having a solid content of 20.0 wt%. The average particle size (D50%) of the polymer particles measured by Microtrac UPA is 93n.
It was m.

<Preparation Example 2> (Preparation of dimethylquinacridone pigment-containing polymer fine particle dispersion) A red-purple polymer fine particle dispersion was prepared in the same manner as in Preparation Example 1 except that the pigment phthalocyanine pigment of Preparation Example 1 was changed to Pigment Pigment Red 122. Got the body Average particle size of polymer particles measured by Microtrac UPA (D50%)
Was 127 nm.

<Preparation Example 3> (Preparation of monoazo yellow pigment-containing polymer particle dispersion) A yellow polymer particle dispersion was prepared in the same manner as in Preparation Example 1 except that the copper phthalocyanine pigment of Preparation Example 1 was changed to Pigment Pigment Yellow 74. Got The average particle diameter (D50%) of the polymer particles measured by Microtrac UPA was 76 nm.

Preparation Example 4 (Preparation of Carbon Black Dispersion) 300 g of commercially available acidic carbon black having a pH of 2.5 (manufactured by Cabot Co., trade name: Monarch 1300) was added to 100 parts of water.
After thoroughly mixing with 0 ml, 450 g of sodium hypochlorite (effective chlorine concentration: 12%) was added dropwise to 100-
The mixture was stirred at 105 ° C for 8 hours. To this liquid was further added 100 g of sodium hypochlorite (effective chlorine concentration: 12%), and the mixture was dispersed for 3 hours with a horizontal disperser. The obtained slurry was diluted 10 times with water, the pH was adjusted with lithium hydroxide, and the conductivity was adjusted to 0.
Pigment concentration 1 after desalting and concentration with ultrafiltration membrane up to 2 mS / cm
A 5% carbon black dispersion was prepared. Coarse particles were removed by centrifugation and filtered through a 1-micron nylon filter to obtain a carbon black dispersion. The average particle size (D50%) measured by Microtrac UPA is 95.
was nm.

<Preparation Example 5> (Preparation of polymer fine particle dispersion of carbon black) Black polymer fine particles were prepared in the same manner as in Preparation Example 1 except that the copper phthalocyanine pigment of Preparation Example 1 was changed to carbon black (FW100 manufactured by Degussa). A dispersion was obtained. The average particle diameter (D50%) of the polymer particles measured by Microtrac UPA was 104 nm.

In the following, ink compositions were prepared using the polymer fine particle dispersions and carbon black dispersions obtained in Preparation Examples 1 to 5 above. The viscosity and surface tension values of the ink compositions obtained in the following production examples are shown in Table 1 below.
<Production Example 1> An ink composition having the following formulation was prepared and adjusted to a pH of 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore diameter of 0.8 μm to obtain an ink composition. Copper phthalocyanine pigment-containing polymer fine particle dispersion of Preparation Example 1 20.0 wt% 1,3-butanediol 23.0 wt% glycerin 8.6 wt% 2-ethyl-1,3-hexanediol 2.0 wt% FT-110 (( Neos Co., Ltd. 0.5 wt% Proxel LV (Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 2> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Dimethylquinacridone pigment-containing polymer fine particle dispersion of Preparation Example 2 20.0 wt% 1,3-butanediol 24.5 wt% glycerin 9.0 wt% 2-ethyl-1,3-hexanediol 2.0 wt% FT-110 (( Neos Co., Ltd.) 0.5 wt% Proxel LV (Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 3> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particle dispersion of Preparation Example 3 20.0 wt% 1,3-butanediol 24.5 wt% glycerin 9.0 wt% 2-ethyl-1,3-hexanediol 2.0 wt% FT-110 (( Neos Co., Ltd.) 0.5 wt% Proxel LV (Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 4> Black pigment ink An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Carbon black dispersion of Preparation Example 4 20.0 wt% 1,3-butanediol 22.5 wt% Glycerin 7.5 wt% 2-Pyrrolidone 2.0 wt% R: C12 of the general formula (IV), n = 9 2.0 wt % 2-Ethyl-1,3-hexanediol 2.0 wt% FT-110 (manufactured by Neos Co., Ltd.) 0.15 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water is added to 100% did.

<Production Example 5> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Copper phthalocyanine pigment-containing polymer fine particle dispersion of Preparation Example 1 20.0 wt% 1,3-butanediol 22.5 wt% glycerin 7.5 wt% 2-ethyl-1,3-hexanediol 2.0 wt% General formula (IV) R: C12, n = 9 2.0 wt% FT-110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 6> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Polymer fine particle dispersion containing dimethylquinacridone pigment in Preparation Example 2 20.0 wt% 1,3-butanediol 22.5 wt% glycerin 7.5 wt% 2-ethyl-1,3-hexanediol 2.0 wt% General formula (IV) R: C12, n = 9 2.0 wt% FT-110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 7> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particle dispersion of Preparation Example 3 20.0 wt% 1,3-butanediol 24.0 wt% glycerin 8.2 wt% 2-ethyl-1,3-hexanediol 2.0 wt% General formula (IV) R: C12, n = 9 2.0 wt% FT-110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 8> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Carbon black-containing polymer fine particle dispersion of Preparation Example 5 5.0 wt% 1,6-hexanediol 22.5 wt% Glycerin 7.5 wt% 2-Pyrrolidone 2.0 wt% Unisafe A-LY (Nippon Yushi Co., Ltd. amphoteric activator) 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% FT-110 (manufactured by Neos Co., Ltd.) 0.15 wt% Proxel LV (manufactured by Avecia) 0.2 wt% ion exchange Water was added to 100%.

<Production Example 9> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Phthalocyanine pigment-containing polymer fine particle dispersion of Preparation Example 1 20.0 wt% 1,6-hexanediol 22.5 wt% Glycerin 10.0 wt% 2,2,4-Trimethyl-1,3-pentanediol 2.0 wt% FT- 110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 10> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Dimethylquinacridone pigment-containing polymer fine particle dispersion of Preparation Example 2 20.0 wt% 1,6-hexanediol 22.5 wt% glycerin 10.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% FT -110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 11> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particle dispersion of Preparation Example 3 20.0 wt% 1,6-hexanediol 22.5 wt% glycerin 10.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% FT -110 (manufactured by Neos Co., Ltd.) 0.5 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 12> An ink composition having the following formulation was prepared and adjusted to a pH of 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore diameter of 0.8 μm to obtain an ink composition. Phthalocyanine pigment-containing polymer particle dispersion of Preparation Example 1 20.0 wt% 1,3-butanediol 24.5 wt% Glycerin 8.2 wt% R of the general formula (IV): C12, n = 9 2.0 wt% 2-ethyl -1,3-Hexanediol 2.0 wt% Proxel LV (Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 13> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Polymer fine particle dispersion containing dimethylquinacridone pigment in Preparation Example 2 20.0 wt% 1,3-butanediol 22.5 wt% glycerin 7.5 wt% 2-ethyl-1,3-hexanediol 2.0 wt% General formula (IV) R: C12, n = 9 2.0 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

<Production Example 14> An ink composition was prepared in the same manner as in Production Example 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particle dispersion of Preparation Example 3 20.0 wt% 1,3-butanediol 23.0 wt% Glycerin 7.8 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% General formula (IV) R: C12, n = 9 2.0 wt% Proxel LV (manufactured by Avecia) 0.2 wt% Ion-exchanged water was added to make 100%.

[0147]

[Table 1]

<Examples 1 to 3> Cyan, magenta, yellow, and black inks produced in the above production examples were used as an ink set of combinations shown in Table 2 below.
An image evaluation test was performed on this. The evaluation method is as follows.

[Image sharpness] (Printer for printing) (1) Print on each of the following papers with an inkjet printer EM-900 (manufactured by Seiko Epson Corporation) while changing the head drive voltage, frequency and pulse width. went. As for the print pattern, the yellow, magenta, and cyan color inks of the present invention were printed at 100% duty, and the black ink filled with the black ink of the present invention printed characters at the same time. The printing conditions are 35 pl for Mj and 20 m / se for Vj.
c, frequency 1 kHz, resolution 360 dpi, one-pass printing. (2) Ink is filled in a BK cartridge of a bubble jet (registered trademark) type inkjet printer BJC430 manufactured by Canon Inc. and a bubble jet (registered trademark) type inkjet printer hp diskjet 815 manufactured by HP, and printing conditions, Mj is 35 pl, and Vj is 20m
/ Sec, frequency is 1 kHz, resolution is 360 dpi,
Solid and characters were printed by one-pass printing. (3) Ricoh inkjet printer IPSiO
The drive voltage, frequency, and pulse width of the Jet 300 head were changed, and solid and characters were printed by one-pass printing under the conditions (1) and (2) above.

(Paper used for printing) The printing test paper used is shown below. My paper (manufactured by NBS Ricoh Co., Ltd.) Paper source S / recycled paper (manufactured by NBS Ricoh Co., Ltd.) PB paper (manufactured by Canon Inc.) Multi-ace (manufactured by Fuji Xerox Office Supply Co., Ltd.) Yamayuri paper (manufactured by Honshu Paper Co., Ltd.) Recycled paper) LH paper (manufactured by Fuji Xerox Office Supply Co., Ltd.) Xerox 4024 paper (manufactured by Fuji Xerox Office Supply Co., Ltd.) Neenah Bond paper (manufactured by Kimberly Clark Co., Ltd.)

(Evaluation Criteria) After the print was dried, the bleeding at the boundary between the two-color overlapping portions and the image bleeding were comprehensively examined visually, and the judgment was made according to the following evaluation criteria. ⊚: Clear printing without blurring on all paper. B: Some paper (recycled paper) has whisker-like bleeding. Δ: Whisker-like bleeding occurs on all paper. X: Blurring occurs so that the outline of the character is not clear.

[0152]

[Table 2]

The results shown in Table 3 below were obtained on any printing test paper, even when printing was performed by any of the printers described in the above (1) to (3).

[0154]

[Table 3]

[Color image evaluation-Color reproducibility evaluation (hue,
Saturation)] Ricoh inkjet printer IPSiO
Using Jet300, My Paper (NBS Co., Ltd.
(Manufactured by Ricoh Co., Ltd.), and the printing pattern is 100% of each of the yellow, magenta, and cyan color inks of the present invention.
% Duty, the black ink filled with the black ink of the present invention printed characters at the same time. Printing conditions are Mj
Is 35 pl, Vj is 20 m / sec, and frequency is 1 kHz.
z, resolution was 360 dpi, and one-pass printing was performed.

After printing and drying, in the above ink set,
Reflective color spectrophotometric densitometer (manufactured by X-Rite Co.) in solid image areas of blue, green, and red areas due to mixed colors of yellow, magenta, and cyan single colors.
Measured by CIE (Commision International de l '
(Eclairage), the coordinates of the L * a * b * color system of the color difference notation method were determined, and the saturation C * was determined for each color. It can be said that the higher the saturation C * value, the better the color development. The saturation C * is defined by the following formula. C * = [(a *) ² + (b *) ² ] ^1/2

[0157]

[Table 4]

[0158]

INDUSTRIAL APPLICABILITY In the present invention, an ink set using a pigment as a color material of a color ink, and by using a fluorine-containing surfactant having a specific structure, an ink of another color particularly in magenta color ink A remarkable effect is recognized, the saturation is remarkably improved, and the coloring property is improved. Further, regarding the printed image on the plain paper, the saturation of the secondary colors green, blue, and red, especially the saturation of the green color, is remarkably improved, and the ink is evenly distributed on the plain paper in the solid image portion. The dyeability was improved, whereby the saturation of all colors was remarkably improved, and in particular, the colorability, which was a problem of pigment-based inks, could be improved.

[Brief description of drawings]

FIG. 1 is a schematic front view showing a configuration example of a serial type ink jet recording apparatus equipped with an ink cartridge containing an ink to which the present invention is applied.

FIG. 2 is an external perspective view of the ink cartridge before being loaded in the recording apparatus.

FIG. 3 is a front sectional view of an ink cartridge.

FIG. 4 is an external perspective view of an ink cartridge integrated with a recording head.

[Explanation of symbols]

1 and 2 side plates 3 Main support guide rod 4 Secondary support guide rod 5 Carriage unit 6 heads 6a Discharge surface (nozzle surface) 7, 7Y, 7M, 7C, 7Bk ink cartridge 8 Main scanning motor 9 Drive pulley (drive timing pulley) 10 Driven pulley (idler pulley) 11 Timing belt 12 Bottom plate 13, 14 subframe 15 Conveyor roller 16 sheets 17 Sub-scanning motor 18, 19 gears 21 subsystem 22 Cap means 23 Holder 24 Link member 25 Engagement part 26 Suction tube 27 Suction pump 28 Wiper blade 29 blade arm 30 recording units 31 electrodes 32 nozzles 41 Cartridge body (ink tank) 42 ink absorber 43 cases 44 Upper lid member 45 ink supply port 46 seal ring 47 Open to the atmosphere 50 Cap member 55 Film seal member A space

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nobuyo Nagai             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2C056 FC02 HA20 HA24                 2C057 AP13 AP55 AP60                 2H086 BA02 BA53 BA55 BA59 BA60                       BA61 BA62                 4J039 AD00 AE06 AE07 BA12 BA29                       BC05 BC06 BC07 BC09 BC10                       BC11 BC13 BC19 BC29 BC33                       BC35 BC47 BC54 BC56 BE12                       BE22 BE28 CA06 EA19 EA48                       GA24

Claims (17)

[Claims] 1. An inkjet recording ink set comprising a black ink and a color ink, wherein the color ink is an aqueous dispersion of fine polymer particles containing a coloring material, and the black ink and the color ink are: At least one selected from glycerin or glycerin and 1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane and trimethylolethane. Contain at least one wetting agent (first type of hydroxy compound), polyol having 8 or more carbon atoms and 11 or less (second type of hydroxy compound) or glycol ether, water-soluble organic solvent and water As well as Contains at least one or more selected from nonions, nonionics and amphoteric surfactants and at least one or more fluorine-containing surfactants (fluorine-containing surfactants may not be contained in the case of black ink) The inkjet recording ink set, wherein the fluorine-based surfactant is a perfluoroalkyl sulfonate represented by the following structural formula, and a pigment is used as a coloring material. [Chemical 1] (R ₁ , R ₂ and R ₃ represent either a perfluoroalkyl group or a fluorine atom, and M ₁ represents any of Li, Na and K.) 2. The anion, nonion and amphoteric surfactant are at least one selected from the surfactants represented by the following general formulas (I) to (IX).
The ink set for ink jet recording according to. _{R 4 -O- (CH 2 CH 2} O) m CH 2 COOM ... (I) ((I) wherein, R ₄ is an alkyl group which may be branched having 6 to 14 carbon atoms, m is 3 to 12 The integer M represents any one of alkali metal ion, quaternary ammonium, quaternary phosphonium, and alkanolamine.) (In the formula (II), R ₅ is a branched alkyl group having ₅ to 16 carbon atoms, M is an alkali metal ion, quaternary ammonium,
Represents either quaternary phosphonium or alkanolamine. ) [Chemical 3] ((III) wherein, R represents optionally branched carbon chain having 6 to 14 carbon atoms which can, k represents an integer of _{5~20.) R- (OCH 2 CH} 2) n OH ... (IV) (( In the formula IV), R represents a carbon chain having 6 to 14 carbon atoms which may be branched, and n represents an integer of 5 to 20). (In the formula (V), R represents a carbon chain having 6 to 14 carbon atoms which may be branched, and j, k, m and n each represent an integer of 1 to 20.) (In the formula (VI), R'is a carbon chain having 6 to 14 carbon atoms, j,
k, m, and n represent the integer of 1-20. ) [Chemical 6] (In the formula (VII), p and q represent an integer of 0 to 40.) (In the formula (VIII), R ₆ and R ₇ are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms, and R ₈ is 10 to 2 carbon atoms.
0 represents an alkyl group or an alkenyl group. ) [Chemical 8] (In the formula (IX), R ₉ and R ₁₀ are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ₁₁ is an alkyl group having 10 to 16 carbon atoms which may contain an amide group or an alkyl group derived from coconut oil. Represents.) 3. The ink set for ink jet recording according to claim 1, wherein the polymer forming the polymer fine particles is a vinyl polymer or a polyester polymer. 4. The polyol having a carbon number of 8 or more and 11 or less (a second type of hydroxy compound) or glycol ether is 2-ethyl-1,3-hexanediol. The ink set for inkjet recording according to any one of 1. 5. The polyol (second type hydroxy compound) or glycol ether having 8 or more and 11 or less carbon atoms is composed of 2,2,4-trimethyl-1,3-pentanediol. Item 4. The ink set for inkjet recording according to any one of Items 1 to 3. 6. The ink set for ink jet recording according to claim 1, wherein the coloring material of the black ink is a self-dispersion pigment. 7. The surface tension of the ink is 40 mN / m or less, and the ink viscosity at 25 ° C. is 5 mPa · s.
7. The ink of ec or more is characterized in that
The ink set for inkjet recording according to any one of 1. 8. The ink set for ink jet recording according to claim 1, wherein the aqueous dispersion of fine polymer particles containing the coloring material contains a solid content of 8 to 20 wt%. . 9. An ink jet recording method, wherein energy is applied to the ink set for ink jet recording according to claim 1 to eject the ink. 10. The ink jet recording method according to claim 9, wherein thermal energy is applied to the ink to eject the ink. 11. The ink jet recording method according to claim 9, wherein the ink is ejected by applying mechanical energy to the ink. 12. Mj is 5 to 35 pl and Vj is 6 to 20.
m, frequency 1 kHz or more, resolution 300 dpi or more,
The ink jet recording method according to any one of claims 9 to 11, wherein the ink set for ink jet recording according to any one of claims 1 to 8 is used under a one-pass printing condition. 13. An ink cartridge comprising an ink containing portion containing the ink set for ink jet recording according to claim 1. 14. An ink containing section or an ink cartridge containing the ink set for ink jet recording according to claim 1, a head section or a recording unit for dripping and ejecting the ink by the action of energy. An ink jet recording apparatus characterized by being provided. 15. The ink jet recording apparatus according to claim 14, wherein an ink repellent film layer is formed on the surface of the nozzle plate of the ink jet recording head by eutectoid plating. 16. The nozzle diameter of the ink jet recording head is 30 μm or less.
Or the inkjet recording device according to item 15. 17. An ink constituting the ink set according to claim 1.