JPH09169160A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate the generation of feathering, blur or color bleeding in an image by using a disperse ink containing a water-soluble org. solvent, which has water and a hydrophobic coloring agent dissolved therein and has vapor pressure less than that of water, and having a hydrophobic coloring agent dispersed therein and a water-soluble dye ink containing water and a water-soluble dye. SOLUTION: A disperse ink containing a water-soluble org. solvent having at least water and a hydrophobic coloring agent dissolved therein and having vapor pressure less than that of water and having a hydrophobic coloring agent dispersed therein and a water-soluble dye ink containing at least water and a water-soluble dye are used in combination to form an image. The disperse ink generates no feathering or blur and color bleeding on recording paper and water-soluble dye ink and forms a sharp full-color image. The hydrophobic coloring agent particles in the disperse ink are stably dispersed because electrostatic repulsive force acts between the coloring agent particles by charging the coloring agent particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to an image forming method using an ink jet method and an ink used therefor.

[0002]

2. Description of the Related Art The conventional ink jet method is an electrostatic suction method, an air pressure feeding method, a method that uses pressure during heating and foaming
An ink droplet is generated by a method of ejecting ink, such as a method utilizing electric deformation of a piezoelectric element, and the ink droplet is attached to a recording paper to form an image.
The characteristics required for the ink used in this method are irregular ink flow along the paper fibers (hereinafter referred to as feathering) and ink droplets adhering to the recording paper regardless of the recording paper type. There is no greater penetration of ink (hereinafter referred to as bleeding), especially when forming a full-color image, the image is disturbed due to the mixture of ink in the area where the black and color inks overlap regardless of the recording paper type. (There is no color bleed below),
Also, the water resistance of the image is good.

In order to obtain a good image without color bleeding, a method of forming a full-color image with four color inks in which water-soluble dyes deposited by a chemical reaction are combined is disclosed in JP-A-5-208548, page 2. Item 10 to page 2, item 23, JP-A-6-57192, page 3, item 10 to page 4, item 23, JP-A-6-100811, item 3, page 6 to item 7, item 22, JP-A-6- It is proposed in the specification of page 106841, page 4, item 13 to page 13, item 64. A method of forming an image by combining a black pigment ink that precipitates in a specific pH region and a water-soluble dye ink of a color in a specific pH region is disclosed in JP-A No. 7-1837, page 3, item 9 to page 5, item 31. Has been proposed to. Further, a method of forming an image by improving the permeation speed of ink into a recording paper is disclosed in JP-A-5-132643, page 3, page 1.
Paragraphs 2 to 13, page 75, JP-A-6-287494, page 2, paragraphs 13, 3 to 24, JP-A 7-3196
It is proposed in Japanese Patent Publication No. Gazette specification, page 2, item 7 to page 4, item 12.

[0004]

However, Japanese Patent Laid-Open Publication No.
The inks proposed in JP-A-08548, JP-A-6-57192, JP-A-6-100811, and JP-A-6-106841 are water-soluble dyes only as colorants. Therefore, there is a problem that the image has no water resistance. In addition, the ink proposed in the specification of JP-A-7-1837 is
Since the black pigment ink contains a large amount of the dispersant, there is a problem that the image has no water resistance. Also, Japanese Unexamined Patent Publication No.
-132643 gazette specification, Unexamined-Japanese-Patent No. 6-287494
The inks proposed in Japanese Patent Application Laid-Open No. 7-3196 and Japanese Patent Application Laid-Open No. 7-3196 have a problem that feathering, bleeding, and color bleeding are not completely solved.

Therefore, an object of the present invention is to realize an image forming method and an ink used therefor which solve the above-mentioned problems of the prior art.

[0006]

The image forming method of the present invention comprises a water-soluble solvent which dissolves at least water, a sparingly water-soluble or water-insoluble hydrophobic coloring agent and a hydrophobic coloring agent and has a vapor pressure smaller than that of water. A dispersion ink containing an organic solvent and in which the hydrophobic colorant is dispersed, and a water-soluble dye ink containing at least water and a water-soluble dye are used.

The image forming method of the present invention is characterized in that the color tone of the dispersion ink is black and the color tone of the water-soluble dye ink is selected from yellow, magenta and cyan. .

Further, the image forming method of the present invention is characterized in that after the image is formed with the water-soluble dye ink, the image is formed with the dispersed ink.

Further, the image forming method of the present invention is characterized in that the dispersion ink and / or the water-soluble dye ink contains a water-soluble polymer.

The image forming method of the present invention is characterized in that the disperse ink and / or the water-soluble dye ink contains a surfactant.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The image forming method of the present invention comprises a hydrophobic colorant containing at least water, a hydrophobic colorant, and a water-soluble organic solvent having a vapor pressure smaller than that of water. And a water-soluble dye ink containing at least water and a water-soluble dye are used in combination. The dispersion ink of the present invention forms a clear full-color image without causing feathering, bleeding, and color bleeding regardless of whether it is on a recording paper or a water-soluble dye ink. The reason for this is not clear, but it is presumed as described below.

In the dispersion ink used in the present invention, the electrostatic repulsive force acts between the colorant particles due to the charge of the hydrophobic colorant particles, and the particles are stably dispersed. When this ink is attached to the recording paper, the inorganic salts in the paper are ionized and dissolved in the ink. Then, the electrostatic repulsion state between the colorant particles changes and the dispersion state becomes unstable, the particles agglomerate and settle on the paper, and other ink liquid components permeate and evaporate into the paper to form an image. To do. Therefore, no feathering or blurring occurs in the image. Further, the water-soluble dye is ionized and dissolved in the water-soluble dye ink. Therefore, when the disperse ink and the water-soluble dye ink come into contact with each other, the colorant particles agglomerate and settle by the same action as the inorganic salts in the paper, so that the inks do not mix with each other and color bleeding does not occur. This means that the pH of the water-soluble dye ink is 8 or above or 6 or above.
It can be inferred from the fact that the color bleed is substantially eliminated in the following cases and when the image is previously formed with the water-soluble dye ink and the image is formed with the dispersion ink.

Further, a sparingly water-soluble or water-insoluble hydrophobic coloring agent is used in the dispersion ink. Therefore, even if water adheres to the image, the coloring component does not dissolve out, and the water resistance is good.

A water-soluble organic solvent which dissolves a hydrophobic colorant and has a vapor pressure smaller than that of water is added to the dispersed ink. Therefore, when fixing ink on paper,
First, the water in the ink evaporates first and the water-soluble organic solvent concentration rises. Then, the vicinity of the surface of the hydrophobic colorant particles existing on the paper is dissolved and the colorant particles are bonded to each other and the colorant particles and the paper fiber are bonded to each other. Therefore, the abrasion resistance of the image is good.

The individual components used in the ink of the present invention will be described in detail below.

The sparingly water-soluble or water-insoluble hydrophobic colorant used in the dispersion ink of the present invention is preferably an oil-soluble dye, a disperse dye or a solvent-soluble pigment. The oil-soluble dyes include yellow oil yellow 105 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), oil yellow 107 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), oil yellow 129 (trade name, Orient Chemical Industry Co., Ltd.). Manufactured by CI Solvent Yellow 29), oil yellow 3G (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI solvent yellow 16), oil yellow GGS (trade name manufactured by Orient Chemical Industry Co., Ltd., C.I. I. Solvent Yellow 5
6), Varifast Yellow 1101 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Yellow 11
05 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Yellow 4120 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Yellow 82), Oplas Yellow 130 (trade name, Orient Chemical Industry Co., Ltd.) Manufactured by CI Solvent Yellow 77), Oplas Yellow 136 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Yellow 33), Oplas Yellow 140 (trade name manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Yellow 93), Oleosol Brilliant Yellow 5G (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Yellow 150), Oleosol Fast Yellow 2G (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Yellow 21), Oleosol Fast Yellow G N (trade name, manufactured by Taoka Chemical Co., Ltd., CI Solvent Yellow 151), Aizen Zott Yellow 1 (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Solvent Yellow 56), Aizen Zott Yellow 3 (Product name, Hodogaya Chemical Co., Ltd.
C. I. Solvent Yellow 16), Aizen Zott Yellow 6 (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I.
I. Solvent Yellow 33), Eisenspiron Yellow GRLH (trade name, Hodogaya Chemical Co., Ltd.),
Aizen spirone yellow 3RH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone yellow C-2G
H (trade name, Hodogaya Chemical Co., Ltd.), Eisenspiron Yellow C-GNH (trade name, Hodogaya Chemical Co., Ltd.), Orazole Yellow 2GLN (trade name, Ciba Geigy Co., C.I. Solvent Yellow 88),
Orazol Yellow 2RLN (trade name, manufactured by Ciba Geigy, CI Solvent Yellow 89), Orazole Yellow 3R (trade name, manufactured by Ciba Geigy, CI Solvent Yellow 25), Oraset Yellow GHS (trade name, Ciba Geigy, CI Solvent Yellow 163), Filamid Yellow R (trade name, Ciba Geigy, CI Solvent Yellow 21), Oil Yellow 185 (trade name, Chuo Gosei Kagaku Co., Ltd.,
C. I. Similar to Solvent Red 18), Alcohol Yellow Y-10 (trade name, manufactured by Chuo Gosei Kagaku Co., Ltd.),
Dialesin Yellow L3G (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Yellow 93), Dialesin Yellow 3G (brand name, manufactured by Mitsubishi Kasei Co., Ltd., C.I.
I. Solvent Yellow 98), Diaresin Yellow F (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Yellow 104), Diaresin Yellow HG (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Yellow 114) , Dialesin Yellow HC (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Yellow 112),
Dialesin Yellow HL (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Yellow 105), Dialesin Yellow GR (trade name, manufactured by Mitsubishi Kasei Co., Ltd., C.I.
I. Oil Red 5B (trade name, CI Solvent Red 27, manufactured by Orient Chemical Industry Co., Ltd.), oil red R as a red type such as Solvent Yellow 113)
R (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI
Solvent Red 24), Bali Fast Red 1306
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Red 109), Varifast Red 1355
(Trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Red 2303 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Red 3304 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Red 8) ), Varifast Red 3306 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Red 3320
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Red 132), oil pink 312 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Pink 2310N (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Red 218), Oprah Red 330 (trade name, manufactured by Orient Chemical Industry Co., Ltd.,
C. I. Solvent Red 179), Oprah Red 3
39 (trade name, manufactured by Orient Chemical Industry Co., Ltd., C.I.
I. Solvent Red 135), Oprah Red 338
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Red 111), Oleosol Fast Red B
L (trade name, manufactured by Taoka Chemical Co., Ltd., CI Solvent Red 132), Oleosol Fast Red RL
(Trade name, manufactured by Taoka Chemical Co., Ltd., CI Solvent Red 122), oleosol fast red GL (trade name, manufactured by Taoka Chemical Co., Ltd., CI Solvent Red 132), oleosol red 2G ( (Product name, made by Taoka Chemical Co., Ltd.), Oleosol Fast Pink FB
(Trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Red 218), Aizen Zott Red 1 (trade name,
Hodogaya Chemical Co., Ltd., C.I. I. Solvent Red 24), Aizen Zott Red 2 (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Solvent Red 27), Aizen Zott Red 3 (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I. Solvent Red 18), Aizen spirone red BEH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone fiery red BH (trade name, Hodogaya Chemical Co., Ltd., CI Solvent Red 81) , Eisenspiron Red GEH (trade name,
Hodogaya Chemical Co., Ltd.), Eisenspiron Red C-GH (trade name, Hodogaya Chemical Co., Ltd.), Eisenspiron Red C-BH (trade name, Hodogaya Chemical Co., Ltd.), Eisen Zot Pink 1 (trade name, Hodogaya Chemical Co., Ltd., CI Solvent Red 4
9), Orazole Red 3GL (trade name, manufactured by Ciba Geigy, CI Solvent Red 130), Orazole Red 2BL (trade name, manufactured by Ciba Geigy, CI Solvent Red 132), Orazole Red G ( Product name, Ciba Geigy, CI Solvent Red 12
5), Orazol Red B (trade name, manufactured by Ciba Geigy, CI Solvent Red 7), Pyramid Red GR (trade name, manufactured by Ciba Geigy, CI Solvent Red 225), Fillester Red GA ( Product name,
Ciba Geigy, C.I. I. Solvent Red 13
5), Fillester Red RBA (trade name, manufactured by Ciba Geigy, CI Solvent Red 230), Orazol Pink 5BLG (trade name, manufactured by Ciba Geigy, C.I.
I. Solvent Red 127), Oil Pink 330
(Trade name, manufactured by Chuo Gosei Kagaku Co., Ltd., CI Solvent Red 49), alcohol pink P-30 (trade name,
Chuo Gosei Kagaku Co., Ltd., Dialesin Red K (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Red 155), Dialesin Red H5B (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent) Red 52), etc.
Oil blue 613 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), oil blue 2N (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Blue 35), oil blue BOS (trade name, Orient Chemical Industry) Industrial Co., Ltd.), Varifast Blue 1603 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Blue 1605 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Blue 38), Varifast Blue 1607. (Brand name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Blue 2606 (Brand name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Blue 7)
0), Varifast Blue 2610 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Oleosol Fast Blue E
LN (trade name, manufactured by Taoka Chemical Co., Ltd., CI Solvent Blue 70), Oleosol Fast Blue GL
(Brand name, Taoka Chemical Industry Co., Ltd., CI Solvent Blue 70), Oreosol Blue G (Brand name, Taoka Chemical Industry Co., Ltd.), Eisenzod Blue 1 (Brand name, Hodogaya Chemical Co., Ltd.) CI Solvent Blue 25), Eisenzod Blue 2 (trade name, Hodogaya Chemical Co., Ltd., CI Solvent Blue 1)
4), Aizen spirone blue GNH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue 2BN
H (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue BPNH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue C-RH (product name, Hodogaya Chemical Co., Ltd.), Eisenspiron Blue E
2BH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI
Solvent Blue 73), Orazol Blue GN (trade name, manufactured by Ciba Geigy, CI Solvent Blue 6)
7), Orazol Blue 2GLN (trade name, manufactured by Ciba Geigy, CI Solvent Blue 48), Oraset Blue 2R (trade name, manufactured by Ciba Geigy, CI Solvent Blue 68), Oil Blue BO (product) Name, manufactured by Chuo Gosei Kagaku Co., Ltd., CI Solvent Blue 2
5), Pyramid Blue R (trade name, manufactured by Ciba Geigy, CI Solvent Blue 132), Filester Blue GN (trade name, manufactured by Ciba Geigy, CI Solvent Blue 67), Kayaset Blue K- FL (trade name, manufactured by Nippon Kayaku Co., Ltd.), Alcohol Blue B-10
(Trade name, manufactured by Chuo Gosei Kagaku Co., Ltd.), Dialesin Blue N (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Blue 94), Dialesin Blue K (trade name, manufactured by Mitsubishi Kasei Co., Ltd., C I. Solvent Blue 78),
DIARESIN BLUE P (trade name, manufactured by Mitsubishi Kasei,
C. I. Solvent Blue 95), Dialesin Blue LR (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Solvent Blue 35), Dialesin Blue H3G (trade name,
Oil black HBB (trade name, manufactured by Orient Chemical Industry Co., Ltd., such as Mitsubishi Kasei Co., Ltd.)
C. I. Solvent Black 3), Oil Black 86
0 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI
Solvent Black 3), Oil Black BS (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 7), Oil Black BY (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Black 18
02 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Black 1807 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Black 3804 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black) 34), Varifast Black 3810 (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 29), Varifast Black 3820.
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 27), Varifast Black 383
0 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Spirit Black SB (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 5), Spirit Black SSBB (trade name, manufactured by Orient Chemical Industry Co., Ltd.) CI Solvent Black 5), Spirit Black AB (trade name, manufactured by Orient Chemical Industry Co., Ltd.,
C. I. Solvent Black 5), Nigrosine Base (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 7), Oplus Black 836 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Oplus Black 838 (trade name) Manufactured by Orient Chemical Industry Co., Ltd.),
Oplus Black HZ (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 3), Oleosol Fast Black RL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Black 27), Oreo Sol Black AR (trade name, manufactured by Taoka Chemical Co., Ltd.), Aizen Zot Black 6 (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Solvent Black 3), Aizen Zot Black 8 (trade name, Hodogaya) Made by Chemical Industry Co., Ltd.
C. I. Solvent Black 7), Eisenspiron Black MH (product name, Hodogaya Chemical Co., Ltd.), Eisenspiron Black GMH Special (product name, Hodogaya Chemical Co., Ltd.), Aizenspiron Black RLH Special (product) Name, Hodogaya Chemical Co., Ltd.), Orazole Black CN (trade name, manufactured by Ciba Geigy, CI Solvent Black 28), Orazole Black RLI (trade name, manufactured by Ciba Geigy, C.I.
Solvent Black 29), Oil Black FS Special A (trade name, manufactured by Chuo Gosei Kagaku KK, CI Solvent Black 7) and the like. The disperse dyes are Oraset Yellow 8GF (trade name, manufactured by Ciba Geigy, CI Disperse Yellow 82), Aizen Zott Yellow 5 (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Disperse). Yellow 3), Sumiplus Yellow HLR (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
I. Disperse Yellow 54), Kayaset Yellow AG (trade name, manufactured by Nippon Kayaku Co., C.I. Disperse Yellow 54), Dialesin Yellow H2G
(Trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Disperse Yellow 160), oil yellow 54 (trade name, manufactured by Chuo Gosei Kagaku Co., Ltd., CI Disperse Yellow 5)
4), Dialesin Red H (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Disperse Red 5), Sumipura red B-2 (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
I. Disperse Red 191), Kayaset Red B
(Trade name, manufactured by Nippon Kayaku Co., Ltd., CI Disperse Red 60), Filester Violet BA (trade name, manufactured by Ciba Geigy, CI Disperse Violet 57), Plast Tread 8335 (trade name, provided) CI Chemicals Co., Ltd., CI Disperse Violet 17), Plast Tread 8375 (trade name, Arimoto Chemical Co., Ltd., CI Disperse Red 60), Plast Blue 8516 (trade name, Arimoto) CI Disperse Blue 14) manufactured by Kagaku Kogyo Co., Ltd. and the like. The solvent-soluble pigments are Hansa Yellow G (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Yellow 1), Hansa Yellow GR (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Yellow 2). , Hansa Yellow 10G (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Yellow 3), Filester Yellow RNB (trade name, manufactured by Ciba Geigy, CI Pigment Yellow 1)
47), Kayaset Yellow E-AR (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Pigment Yellow 147),
Kayaset Yellow E-L2R (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Pigment Yellow 142), Permanent Red 4R (trade name, manufactured by Daido Kasei Co., Ltd., C.I.
I. Pigment Red 3), Poppy Red (trade name, manufactured by Dainichiseika Kogyo Co., Ltd., CI Pigment Red 1)
7), Brilliant Fast Scallet (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Red 22),
3040 Red (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.,
C. I. Pigment Red 23), Fast Pink Lake 6G (trade name, Noma Chemical Industry Co., Ltd., CI Pigment Red 81), Eosin Lake (trade name, Arimoto Chemical Industry Co., Ltd., CI Pigment Red 90), Fernal Rose Toner 170 (trade name, Arimoto Chemical Co., Ltd.), Kayaset Red E-CG (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Pigment Red 250),
Kayaset Red E-BG (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Pigment Red 249), Carmin BS
(Trade name, manufactured by Dainippon Ink and Chemicals, Inc., CI
Pigment Red 114), Oraset Pink RF (trade name, manufactured by Ciba Geigy, CI Pigment Red 1)
81).

These hydrophobic colorants can be used alone or in admixture of two or more. Further, these hydrophobic colorants are preferably added in the range of 0.5 to 20 wt% with respect to the total amount of the ink. If the added amount is 0.5 wt% or more, a sufficient image density can be obtained. 20w
When it is t% or less, it is easy to set the ink viscosity to a range in which the ink can be ejected in the inkjet method.

The water-soluble dye used in the water-soluble dye ink is
Direct dyes, acid dyes and basic dyes are preferred. Direct dye is yellow, yellow
G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Yellow 8), chrysophenine (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Yellow 12),
Chrysamine G (trade name, manufactured by Nippon Kayaku Co., Ltd., CI
Direct Yellow 24), Direct Fast Yellow 5LG (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I.
I. Direct Yellow 26), Sumilite Supra Yellow BC Conc. (Sumitomo Chemical Co., Ltd., C.I.
I. Direct Yellow 28), Kayals Supra Yellow 2LG (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Yellow 39), Direct Fast Yellow GC (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Direct Yellow 39). Direct Yellow 44), Direct Fast Yellow GN (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Yellow 85), Direct Fast Yellow R Special (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Yellow) Yellow 86), Kayals Light Yellow F8
G (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Yellow 87), Kayaru Scupro Yellow GR (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Yellow 88), Kayaru Scupro Yellow EG (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Yellow 89) and the like, magenta, Eisen Direct Fast Red FH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Direct Red 1), Nippon Fast Scarlet G
SX (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Red 4), Nippon Brilliant Pink B Conc. (Product name, Sumitomo Chemical Co., Ltd., CI Direct Red 9), Direct Brilliant Pink 3B
(Trade name, CI Direct Red 11 manufactured by Ciba-Geigy), Eisen Direct Vodax GH (trade name, CI Direct Red 13 manufactured by Hodogaya Chemical Co., Ltd.), Kayak Direct Vodax BK (product) Name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Red 1
7), Nippon Brilliant Rose BD Conc. (Product name, Sumitomo Chemical Co., Ltd., CI Direct Red 20), Direct Fast Scarlet 4BS (Product name, Hodogaya Chemical Co., Ltd., CI Direct Red 23), Congo Red (Product name) , Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Red 28), Direct Scarlet B (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Direct Red 37), Kayak Direct Scarlet 3B (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Direct Red 39), Kayals Supra Red 6BL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Red 79), Sumilite Red F3B (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Direct red 8
0), Sumilite Red 4B (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Red 81), Kayals Supra Scarlet BNL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Red 89) ), Direct Scarlet B New (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Direct Red 201), Kyalus Light Scarlet F2G (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Direct Red 224), Kayals Light Red F5G (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Red 225), Kayals Light Red F5B (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I. Direct Red 226), Kayals Light Rose FR (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Red 227), Nippon Resin Fast Scarlet 4BA (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I. Direct Red 23
0) etc. as direct sky blue 6B as cyan
(Brand name, Taoka Chemical Co., Ltd., CI Direct Blue 1), Direct Blue 2B (Brand name, Mitsubishi Kasei Co., Ltd., CI Direct Blue 6), Direct Sky Blue 5B (Brand name) CI Direct Blue 15) manufactured by Hodogaya Chemical Co., Ltd., Direct Brilliant Blue RW (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Blue 22), Kayals Blue G Conc. (Trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Direct Blue 78), Eisen Primula Turquoise Blue GLH (trade name, Hodogaya Chemical Co., Ltd., CI Direct Blue 86), Sumilite Supra Blue FGL (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Direct Blue 90), Sumilite Supra Blue FBGL (trade name, manufactured by Sumitomo Chemical Co., Ltd.,
C. I. Direct Blue 98), Kayals Supra Blue FF2GL (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Direct Blue 106), Kayals Supra Blue FFRL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Blue 108), Kayals Supra Blue BR
L200 (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Blue 201), Sumilite Supra Blue 3G
S (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Blue 202), Kayals Supra Blue RCL
(Trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Blue 203), Kayarusu Supra Blue BCL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Blue 2)
36), Kayals Supra Blue BWL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Blue 237), and the like, Direct Fast Black D (trade name,
Manufactured by Nippon Kayaku Co., Ltd., C.I. I. Direct Black 1
7), Kayals Black G Conc. (Trade name, manufactured by Nippon Kayaku Co., Ltd., CI direct black 19), direct fast black B (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI direct black 22), direct fast black AB ( Trade name, Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Black 32), Direct Deep Black EX (trade name, Sumitomo Chemical Co., Ltd., CI Direct Black 38), Direct Fast Black Conc. (Brand name, CI Direct Black 51 manufactured by Hodogaya Chemical Co., Ltd.), Kayals Supra Gray VGN (Brand name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Black 71), Sumilite Gray G Conc. (Product name, Sumitomo Chemical Co., Ltd.,
C. I. Direct Black 74), Sumilite Supra Gray R Conc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Direct Black 75), Diacupuro Gray 2R (trade name, manufactured by Mitsubishi Kasei Co., Ltd., C.I.
I. Direct Black 105), Diacupuro Gray R (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Black 106), Diacupuro Gray B (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Black) 107), Diacupro Black RY (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Black 108), Kayals Supra Gray CGL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Black 112) ), Sumilite Supra Gray NGL Conc.
(Product name, Sumitomo Chemical Co., Ltd., CI Direct Black 113), Kayals Supra Gray 3BL
(Trade name, manufactured by Nippon Kayaku Co., Ltd., CI Direct Black 132), Diacupuro Special Black G
U (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Direct Black 146) and the like. Acid dyes
Solar Yellow NY Conc. As yellow. (Brand name, Sumitomo Chemical Co., Ltd., CI Assid Yellow 1), Solar Pure Yellow 8G (Brand name, Sumitomo Chemical Co., Ltd., CI Assid Yellow 7), Diaside Leveling Yellow NR (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Assid Yellow 19), Eisenter Tradine Conc. (Trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Yellow 23), Suminol Fast Yellow R Conc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Yellow 25), diacidite yellow 2GP (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Assid Yellow 29), Kayanol milling Yellow O (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Assid Yellow 38), Suminol Milling Yellow MR (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
I. Assid Yellow 42), Diaside Milling Yellow H5G (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., C.I.
I. Assid Yellow 44), Kayanor Yellow NF
G (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Yellow 49), Suminol Fast Yellow G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Yellow 61), Kayanol Milling Yellow 4 GW (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Yellow 7
0), Kayanol Milling Yellow 3GW (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Yellow 72),
Suminol Milling Yellow G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Yellow 78), Eisen Opal Yellow 3GH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Yellow 98) ), Kayanol Yellow N5G (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Assid Yellow 110), Kayanol Milling Yellow 5GW (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
Assid Yellow 127), Cibaran Yellow FGL
(Trade name, manufactured by Ciba-Geigy, CI Assid Yellow 128), Kayanol Fast Yellow NG (trade name, manufactured by Nippon Kayaku Co., CI Assid Yellow 1)
35), Suminol Milling Yellow 4G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Yellow 14)
1), Kayakaran Yellow GL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Yellow 161), Solar Pure Yellow GOO (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Yellow) 164) such as Solar Fast Red 3G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 1) as magenta, and Suminol Fast Red B Conc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 6), kayak silk scarlet (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Acid Red 9), Solar Red S (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Assid red 1
3), Eisen Brilliant Scarlet 3RH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Red 18), Suminol Leveling Red 6BL Extra Conc. (Product name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
I. Ascid Red 32), Suminol Leveling Brilliant Red S3B (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 35), Suminol Leveling Rubinol 3GS (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I. I. acid red 37), Eisen acid rhodamine BH (trade name, manufactured by Hodogaya Chemical Co., Ltd.,
C. I. Assidred 52), Suminol leveling rubinol 3GP (trade name, manufactured by Sumitomo Chemical Co., Ltd.,
C. I. Assid red 57), Kayanol milling red PG (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid red 85), Eisen Eosin GH Conc. (Brand name, Hodogaya Chemical Co., Ltd., CI Assid Red 87), Eisen Assid Phloxine PB (Brand name, Hodogaya Chemical Co., Ltd., CI Assid Red 92), Eisen Rose Bengal B (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Red 94),
Lacto acid red anthracene red G (trade name, manufactured by Rakuto Chemical Co., Ltd., CI acid red 9
7), benzyl fast red B (trade name, manufactured by Ciba-Geigy, CI Assid red 106), Kayanor milling scarlet FGW (trade name, manufactured by Nippon Kayaku Co., CI Assid red 111), Kaya Noll Milling Red RS (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Acid Red 114), Suminol Milling Scarlet R (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
I. Acid Red 117), Suminol Fast Red G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 118), Kayanol Milling Red Brown V (trade name, manufactured by Nippon Kayaku Co., CI Acid Red 119), Suminol Milling Brilliant Red 3BW (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI.
Acid Red 129), Suminol Milling Brilliant Red 3BN Conc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 131), Kayak Assid Red 3B (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. ASCID RED 134), SUMINOL MILLING BRILLIANT RED BS (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI ASSID RED 138), Suminol milling scarlet G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Ascid Red 145), Diacid Fast Red 3BL (trade name, manufactured by Mitsubishi Kasei Co., Ltd.,
C. I. Acid Red 158), Eisen Opal Pink BH (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I.
I. Assid Red 186), Suminol Milling Brilliant Red B Conc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Red 249), Cibaran Brilliant Red BL (trade name, manufactured by Ciba Geigy,
C. I. Acid Red 252), Kayak Acid Red Brilliant Red 3BL (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Acid Red 254), Kayak Acid Red Brilliant Red BL (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Acid red 265), diacid red N
2B (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Assid Red 266), Kayanor Milling Red 3BW
(Trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Red 274), Kayaka Lance Scarlet GL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Red 317),
Kayakalance Scarlet BL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Red 318) and the like, Patent Blue AF (trade name, manufactured by BASF, C.I.) as cyan.
I. Acid Blue 7), Lactor Brilliant Blue FCF (trade name, manufactured by Rakuto Chemical Co., Ltd., C.I.
Assid Blue 9), Orient Soluble Blue O
BC (trade name, manufactured by Orient Chemical Industry Co., Ltd., C.I.
I. ASSID BLUE 22), SUMINOL LEVELING BLUE 4GL (trade name, manufactured by Sumitomo Chemical Co., Ltd., C.I.
Ascid Blue 23), Kayanol Blue N2G (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Acid Blue 4)
0), Kayanol Blue BL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Asid Blue 59), Suminol Leveling Sky Blue R Extraconc. (Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Blue 6
2), Lacto Indigo Carmine Blue G (trade name, manufactured by Rakuto Chemical Co., Ltd., CI Assid Blue 7
4), Diacide Alizarin Sky Blue B (trade name,
Mitsubishi Kasei Kogyo Co., Ltd., C.I. I. Assid blue 7
8), Alizarin Fast Blue R (trade name, manufactured by Ciba Geigy, CI Acid Blue 80), Suminol Fast Blue G (trade name, manufactured by Sumitomo Chemical Co., Ltd.,
C. I. ASSID BLUE 82), ORIENT SOLUBLE BLUE OBB (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI ASSID BLUE 93), Kayanor Milling Ultra Sky SE (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. ASSID BLUE 112), Kyanol Milling Blue GW (trade name, manufactured by Nippon Kayaku Co., C.I.
27), Alizarin Fast Blue BE (trade name, manufactured by Ciba Geigy, CI Assid Blue 129), Kayanor Milling Blue BW (trade name, manufactured by Nippon Kayaku Co., CI Assid Blue 138), Kayanor Milling Blue 2RW (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. Acid Blue 140), Neolan Blue 2R (trade name, manufactured by Ciba Geigy, CI Acid Blue 15)
4), Aizen Opal Blue 2GLH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Blue 15)
8), Aizen Opal Blue BH (trade name, Hodogaya Chemical Co., Ltd., CI Asid Blue 161),
Kayakaran Blue BL (trade name, manufactured by Nippon Kayaku Co., Ltd.,
C. I. Assid blue 168), Kayakaran blue 3
GL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Blue 171), Kayanol Milling Blue 2GW (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Blue 1)
75), Suminol Milling Brilliant Blue GG
(Trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Assid Blue 183), Eisen Opal Blue New Conc. (Trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Asid Blue 192) and the like, assid blue black 10B (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., C.I.
I. Assid Black 1), Orient Nigrosine BR
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Asid Black 2), Suminol Milling Black 8B
X (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Black 24), Kayanor Milling Black VLG
(Brand name, manufactured by Nippon Kayaku Co., Ltd., CI Asid Black 26), Suminol Milling Black NB (Brand name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Black 31), Suminol Fast Gray 3G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Black 4
8), Kayanol Gray P (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Black 50), Neo Langley 3B (trade name, manufactured by Ciba Geigy, CI Assid Black 51), Eisen Opal Black WGH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Asid Black 52), Lana Fast Gray BGL Extra Conc. (Trade name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Assid Black 58), Lana Fast Gray BL (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Asid Black 60), Lana Fast Gray 2GL Extra Conc. (Brand name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Assid Black 62), Dia Leather Black G (Brand name, manufactured by Mitsubishi Kasei Co., Ltd., CI Assid Black 77), Dia Leather Black B (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Assid Black 94), Cibaran Black 2GL (trade name, manufactured by Ciba Geigy, Inc.
C. I. Assid Black 108), Kyanol Milling Black TLB (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
I. ASSID BLACK 109), Kyanol Milling Black TLR (trade name, manufactured by Nippon Kayaku Co., Ltd., C.I.
Acid black 110), Kayanol gray BL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI acid black 112), Eisen Opal Black BNH (trade name,
Hodogaya Chemical Co., Ltd., C.I. I. Assid Black 118), Eisen Opal Black New Conc.
(Trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Black 119), Kayakaran Black 2RL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Black 1)
55), Kayanol Milling Gray GW (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Acid Black 156),
Lana Fast Blue Black BL (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Assid Black 157), Lana Fast Black BGL (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Assid Black) 158), Lana Fast Black 2BL (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., CI Asid Black 159) and the like. The basic dye is, as yellow, Aizen Catylon Yellow 3GLH (trade name, manufactured by Hodogaya Chemical Co., Ltd.,
C. I. Basic Yellow 11), Eisencatilon Brilliant Yellow 5GLH (product name, Hodogaya Chemical Co., Ltd., CI Basic Yellow 13), Eisencatilone Yellow GLH (product name, Hodogaya Chemical Co., Ltd., C I. Basic Yellow 14), Sumiacrylic Yellow 3R (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Yellow 32), Die Acrylic Supra Brilliant Yellow 2GL (trade name, manufactured by Mitsubishi Kasei Co., Ltd., C I. Basic Yellow 3
3), Daiacrylic Supra Yellow 5RL (trade name,
Mitsubishi Kasei Kogyo Co., Ltd., C.I. I. Basic Yellow 34), Aizen Catillon Yellow 3RLH (trade name,
Hodogaya Chemical Co., Ltd., C.I. I. Rhodamine 6GCP (trade name, manufactured by BASF, CI Basic Red 1) as magenta, such as Basic Yellow 36),
Paramagenta base (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Basic Red 9), Eisencatillon pink FGH (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd., CI Basic Red 13), Sumi Acrylic Brilliant Red 4G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Red 14), Sumi Acrylic Brilliant Red BB (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Red 15), Aizen Catillon Red GTLH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Red 18), Sumiacrylic Red G (trade name, Sumitomo Chemical Co., Ltd., CI Basic Red 18), die Acrylic Supra Red R
(Product name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Basic Red 32), Die Acrylic Supra Red 2BL
(Brand name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Basic Red 34), Daiacrylic Supra Brilliant Pink R (brand name, manufactured by Mitsubishi Kasei Co., Ltd., CI Basic Red 35), Aizen Catillon brilliant Pink BH (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I.
I. Basic Red 36), Aizen Catilene Brilliant Scarlet RH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Red 37), Aizen Catilen Red GLH (trade name, Hodogaya Chemical Co., Ltd., C I. Basic Red 38), Aizen Catillon Red BLH (trade name, manufactured by Hodogaya Chemical Co., Ltd.,
C. I. Eisen Basic Pure Blue 5GH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 3) as cyan, such as Basic Red 39), Eisen Victoria Pure Blue BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd.) , CI Basic Blue 7), Eisen Methylene Blue FZ (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 9), Eisen Methylene Blue BH Conc. (Product name,
Hodogaya Chemical Co., Ltd., C.I. I. Basic Blue 9), Sumi Acrylic Blue R (trade name, Sumitomo Chemical Co., Ltd., CI Basic Blue 21), Sumi Acrylic Blue GG (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Basic Blue 22), New Methylene Blue NS Conc. (Product name, Sumitomo Chemical Co., Ltd.,
C. I. Basic Blue 24), Basic Blue G
O (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Blue 25), Eisen Victoria Blue BH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 26), Eisen Marine Blue BNX (Product name,
Hodogaya Chemical Co., Ltd., C.I. I. Basic Blue 28), Eisen Marine Blue RNX (trade name, Hodogaya Chemical Co., Ltd., CI Basic Blue 2)
9), Aizen Catillon Blue 5GLH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Blue 4
5), Eisencatillon Blue 3RLH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Blue 4
7), Daiacrylic Supra Blue 5RL (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Basic Blue 5
8), Daiacrylic Supra Blue 2RL (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Basic Blue 5
9), Daiacrylic Supra Blue FGL (trade name, manufactured by Mitsubishi Kasei Co., Ltd., CI Basic Blue 6
0), Aizen Catillon Blue GLH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 6)
5), Eisencatillon Blue NBLH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Blue 6
6), Aizen Catillon Blue NRLH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 6
7), Aizen Catillon Blue 2RLH (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Basic Blue 6
8) etc. as black as Eisenkachi Long Ray BLH (trade name, Hodogaya Chemical Co., Ltd., CI Basic Black 2), Daiacrylic Supra Black BSL
(Trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Basic Black 8) and the like.

These water-soluble dyes are preferably added in the range of 0.5 to 20 wt% with respect to the total amount of ink.
If the added amount is 0.5 wt% or more, a sufficient image density can be obtained. When the content is 20 wt% or less, it is easy to set the ink viscosity to a range in which ink can be ejected in the inkjet method.

As water, deionized water, ultrafiltered water, reverse osmosis water, distilled water, or other pure water or ultrapure water is used. When the ink is stored for a long period of time, water sterilized by ultraviolet irradiation treatment, hydrogen peroxide treatment, etc. can be used for the purpose of preventing the generation of mold and bacteria.

The water-soluble organic solvent used in the dispersion ink is preferably one that is compatible with water to dissolve the hydrophobic colorant and has a vapor pressure smaller than that of water. Specifically, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
2-butene-1,4-diol, 2-methyl-2,4-
Alcohols such as pentanediol, glycerin, 1,2,6-hexanetriol, ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, acetonyl acetone, methyl ethyl ketone Such as ketones, γ-butyrolactone, diacetin, ethylene carbonate, esters such as triethyl phosphate, formamide, dimethylformamide, diethylformamide, dimethylacetamide, 2-pyrrolidone,
Nitrogen compounds such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, sulfur compounds such as 1,3-propane sultone, lactic acid amide, acetamide,
Carboxylic acid amides such as N-methylacetamide, methyl carbamate, ethyl carbamate, ε-caprolactam, γ-valerolactam, α-pyridone and isatin, carboxylic acid derivatives of lactones such as gluconolactone, 2-amino- 2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, bis (hydroxyethyl) terephthalate, N,
N'-dimethyl-1,3-propanediamine, 2,2-
Dimethyl-1,3-propanediol, ethyl gallate, 2-ethyl-2- (hydroxymethyl) -1,3-
Propanediol, glutaric anhydride, glycolamide, 2-hydroxymethyl-2-methyl-1,3-propanediol, imidazole, 2-imidazolidinone,
Nicotinamide, 1,1 ′, 1 ″ -nitrotri-2-
Propanol, succinimide, 1,2,3,6-tetrahydrophthalimide, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N,
N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, thiourea, 2,2,4-trimethyl-1,3-pentanediol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ) Ethanol, 2-isopropoxyethanol, 2-
Butoxyethanol, 2-isopentyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether Examples thereof include polyfunctional compounds such as ether, diacetone alcohol, monoethanolamine, thiodiglycol, morpholine, N-ethylmorpholine, 2-methoxyethyl acetate, diethylene glycol monoethyl ether acetate, and hexamethylphosphoramide. These water-soluble organic solvents may be used alone or in combination of two or more. The mixing ratio of water and the water-soluble organic solvent is not particularly limited as long as it is equal to or lower than the saturated solubility of the water-soluble organic solvent in water. Further, these water-soluble organic solvents can be added to the water-soluble dye ink.

The essential components of the dispersion ink of the present invention are water, a hydrophobic colorant and a water-soluble organic solvent, and the water-soluble dye ink is water and a water-soluble dye. A water-soluble polymer for further improvement, a surfactant for further improving the image forming speed, and a penetration accelerator, a surface tension adjusting agent, a hydrotropic agent, a moisturizing agent which are generally used in inkjet inks. If necessary, an auxiliary agent for inkjet ink such as a pH adjusting agent, an antifungal agent, a chelating agent, an antiseptic agent, a rust preventive agent, an antioxidant and an ultraviolet absorber can be added.

The water-soluble polymer is a nonionic polymer whose functional group imparting water solubility is a hydroxyl group, a carbonyl group, a polyethyleneoxyl group, an alkoxy group, a lactam, an ester group, an amino group, an imino group, or the like. Inorganic acid salts, organic acid salts and other cationic polymers, sulfonic acid groups, carboxylic acid groups, phosphoric acid groups and other alkali metal salts, ammonium salts and other anionic polymers, cationic functional groups And an anionic polymer having both anionic functional groups are preferable. Specifically as the nonionic polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formal. Polymers, polyvinyl alcohol-partial butyral compounds, synthetic polymers such as vinylpyrrolidone-vinyl acetate copolymer, cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyalkyl starch. , Starch acetate, cross-linked starch, dextri , And the like starch derivatives such as dextran. Specific examples of the cationic polymer include starch derivatives such as cationic starch, synthetic polymers such as poly (4-vinylpyridine) salt, polyamide, polyallylamine salt and polyethyleneimine salt. Further, as the anionic polymer, for example, carboxymethyl cellulose salt, cellulose derivative such as viscose, alginate, gum arabic, tongant gum, natural polymer such as lignin sulfonate, starch phosphate, carboxymethyl starch salt, etc. Starch derivative, polyacrylate, polymethacrylate, polyvinylsulfate, polyvinylsulfonate, condensed naphthalenesulfonate, poly (ethylene-acrylic acid) salt, styrene-acrylate copolymer, styrene-
Methacrylate Copolymer, Acrylate Ester-Acrylate Copolymer, Acrylate Ester-Methacrylate Copolymer, Methacrylate-Acrylate Copolymer, Methacrylate-Methacrylate Copolymer ,
Styrene-itaconate copolymer, itaconic acid ester-itaconate copolymer, vinyl naphthalene-acrylate copolymer, vinyl naphthalene-methacrylate copolymer, vinyl naphthalene-itaconate copolymer, etc. And synthetic polymers of Further, as amphoteric polymers, specifically, natural polymers such as gelatin, albumin and casein can be mentioned.

These water-soluble polymers can be used for the purpose of further improving the abrasion resistance of images. further,
The water-soluble polymer has a weight average molecular weight of 2,000 to 1, from the viewpoint of improving the abrasion resistance of the image and ensuring the viscosity of the ink that can be ejected.
It is in the range of, 000,000, and when a nonionic polymer is used, it is 0.01 to 20 w with respect to the total amount of ink.
When a cationic, anionic, or amphoteric polymer is used in the range of t%, 0.01 to 1 with respect to the total amount of ink.
It is preferable to add it in the range of 0 wt%. In addition, it is possible to use one kind or a mixture of two or more kinds of the same ionic polymers, or to mix and use a nonionic polymer and a cationic, anionic or amphoteric polymer.

Surfactants include cationic, anionic,
Both amphoteric and nonionic can be used. As the cationic surfactant, aliphatic amine salt, aliphatic 4
Examples thereof include primary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-
N-methyl-β-alanine salt, N-acylglutamate, alkyl ether carboxylate, acylated peptide, alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, naphthalenesulfonate formalin polycondensate, Dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acyl methyl taurine, sulfated oil, higher alcohol sulfate, secondary higher alcohol sulfate, alkyl ether sulfate, second Higher alcohol ethoxy sulphate, polyoxyethylene alkylphenyl ether sulphate, monoglycer sulphate, fatty acid alkylolamide sulphate ester salt, alkyl ether phosphate ester salt, alkyl phosphate ester salt, etc. . Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, aminocarboxylic acid salts, imidazolinium betaine and the like.
As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin condensate ethylene oxide derivative, Polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene Glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan Fatty acid esters, propylene glycol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides,
Examples thereof include polyoxyethylene alkylamine, alkylamine oxide, acetylene glycol, and acetylene alcohol.

These surfactants are used as a surface tension adjusting agent for ink. The surface tension of the ink of the present invention is
It is preferably in the range of 25 to 70 dyn / cm at 20 ° C., and the surfactant is added so as to be in this range. Other surface tension adjusting agents having such an effect include alcohols such as diethanolamine, triethanolamine, glycerin and diethylene glycol. If the surface tension is less than 25 dyn / cm, feathering or bleeding occurs on the recording paper. 70 dy
If n / cm is exceeded, ink droplets are segregated along the ruled line when the ruled line image is formed, resulting in large image density unevenness.

The surfactant is also used as an ink penetration accelerator. Other penetration enhancers having similar effects include alcohols such as ethanol, isopropanol, butanol, pentanol, 2-pyrrolidone, N-
Lactams such as methyl-2-pyrrolidone and ethers such as diethylene glycol mono-n-butyl ether and triethylene glycol mono-n-butyl ether are also preferable.

When a surfactant is used, it may be used alone or as a mixture of two or more of the same ionic surfactants, or a nonionic surfactant and a cationic or anionic surfactant may be used.
Alternatively, it is possible to mix an amphoteric surfactant.
Further, when a large amount of a surfactant is added to the dispersed ink, the hydrophobic colorant is solubilized in the ink. Then, feathering and bleeding occur in the image, and the water resistance also deteriorates. Therefore, the minimum necessary amount is added.

When a hydrotropic agent is added, urea,
Alkyl urea, ethylene urea, propylene urea, and thiourea are preferable, and it is preferable to add them in the range of 0.5 to 20 wt% with respect to the ink.

When a moisturizer is added, polyols such as glycerin, diethylene glycol, maltitol, and sorbitol are preferable, and 1 to 25 wt% of the ink is used.
% Is preferably added.

The method for producing the dispersed ink of the present invention comprises the steps described below.

The first step is a step of preparing a colorant solution in which at least a hydrophobic colorant is dissolved in a water-soluble organic solvent. This step is not particularly limited as long as the hydrophobic colorant can be dissolved in the water-soluble organic solvent. For example, there is a method in which a water-soluble organic solvent is added to the hydrophobic colorant and stirred, or the hydrophobic colorant is added to the water-soluble organic solvent while stirring. At this time, if it is difficult to dissolve, heating may be performed. If the colorant solution thus prepared contains impurities or insolubles, it can be removed by filtration or centrifugation. further,
In this step, it is also possible to add an auxiliary for inkjet ink, a water-soluble polymer, and a surfactant.

The second step is a step of preparing a solution containing at least water. In this step, an aqueous solution of an inkjet ink aid, a water-soluble polymer, and a surfactant can be prepared. If it is not necessary to prepare such an aqueous solution, this step can be omitted.

The third step is a step of mixing the colorant solution obtained in the first step with the aqueous solution or water obtained in the second step. In this step, a method is used in which a colorant solution is added little by little to a certain amount of water or an aqueous solution, or conversely, water or an aqueous solution is little by little added to a certain amount of colorant solution. Further, it can be produced by a method of continuously mixing a fixed amount of a colorant solution and water or an aqueous solution. Further, in this step, it is possible to add a water-soluble polymer, an inkjet aid, and a surfactant.

Here, when the ink is prepared by a method that does not take the first, second and third steps or the first and third steps into consideration, for example, a hydrophobic colorant is added to an aqueous solution containing a water-soluble organic solvent. When mixed with, most of the hydrophobic coloring agent is separated by sedimentation and does not become an ink.

The method for producing the water-soluble dye ink of the present invention is not particularly limited as long as it is a method of mixing at least water and the water-soluble dye to dissolve the water-soluble dye. If necessary, an auxiliary agent for inkjet ink, a water-soluble polymer, a surfactant, and a water-soluble organic solvent may be added.

[0037]

The present invention will be described in more detail with reference to the following examples. Furthermore, the inks obtained in the individual examples and comparative examples described below were evaluated by the methods described below.

<1. Image quality evaluation> MJ-700V2C (trade name, manufactured by Seiko Epson Corporation) was filled with the obtained ink, and XER which is recycled paper as recording paper
Using OX-R (trade name, manufactured by Fuji Xerox Co., Ltd.), an image was formed with the dispersed ink so that the dots would overlap immediately after the image was formed with the water-soluble dye ink. Then, the color bleed state of the obtained image was confirmed by observing with a microscope of 100 times. The evaluation criteria are ⊚ when the difference in dot diameter between the recording paper and the portion where the inks overlap each other is less than 2%, ∘ when the difference is less than 5%, and also less than 10%. And Δ when the content was 10% or more.

<2. Evaluation of water resistance of image> 0.3 ml of pure water was adhered to the image obtained in the quality evaluation of the image, and the image was distorted after it was naturally dried.
The evaluation criteria were ⊚ when the image formed with the dispersed ink was not disturbed, and x when the image was disturbed regardless of the image.

<3. Evaluation of abrasion resistance of image> The obtained ink was filled in MJ-700V2C, and an image was formed on XEROX-P (trade name, manufactured by Fuji Xerox Co., Ltd.) which is a high quality paper as a recording paper. Then, the obtained image was rubbed while applying a load of 600 g and 300 g to the long end of the paper clip, and the disorder of the image after rubbing was visually confirmed.
The evaluation criteria were ⊚ when no image distortion was observed under a load of 600 g, ◯ when no image distortion was observed under a load of 300 g, and × when no image distortion was observed under a load of 300 g. And

<4. Dispersion ink particle size and ζ-potential measurement> Particle size and ζ- of hydrophobic colorant particles of the obtained dispersion ink
The potential was measured with an electrophoretic light scattering photometer ELS-800 (trade name, manufactured by Otsuka Electronics Co., Ltd.).

Example 1 <Dispersion Ink 1> [Hydrophobic Colorant] Oil Black FS Special A (trade name, C.I. Solvent Black 7 manufactured by Chuo Gosei Kagaku Co., Ltd.)
5.0 g [Water-soluble organic solvent] N-methyl-2-pyrrolidone ... 5.0 g Ethylene carbonate ... 10.0 g [Water] Pure water ... 80.0 g First, N-methyl-2-pyrrolidone And ethylene carbonate were mixed with stirring, and Oil Black FS Special A was added thereto and dissolved by stirring while heating at 50 ° C. to prepare a colorant solution. Then, the obtained colorant solution is diluted with pure water to 50
The whole amount of the colorant solution was gradually added dropwise over 1 hour while heating at 0 ° C., and the mixture was further stirred and mixed for 2 hours. This is 20
After cooling to 0 ° C., pressure filtration was performed using a filter having a pore size of 0.45 μm to prepare black dispersion ink 1.

In Dispersion Ink 1, since N-methyl-2-pyrrolidone, which is also used as a penetration enhancer in the water-soluble organic solvent, is used, the ink penetration rate is within 10 seconds, and the image forming rate is improved. It showed various characteristics.

<Water-soluble dye ink 1Y> [Water-soluble dye] Direct Fast Yellow 5LG (trade name, CI Direct Yellow 26 manufactured by Hodogaya Chemical Co., Ltd.)
・ ・ ・ 4.0 g [Water] Pure water ・ ・ ・ 96.0 g <Water-soluble dye ink 1M> [Water-soluble dye] Congo Red (trade name, manufactured by Mitsubishi Kasei Co., Ltd.,
C. I. Direct Red 28) ... 4.0 g [water] Pure water ... 96.0 g <Water-soluble dye ink 1B> [Water-soluble dye] Kayals Supra Blue BRL200 (trade name, manufactured by Nippon Kayaku Co., Ltd., C I. Direct Blue 201) ...
-4.0 g [water] Pure water ... 96.0 g A water-soluble dye was added to pure water heated to 50 ° C, and the mixture was stirred and dissolved while heating for 1 hour. After cooling this to 20 ° C., it is filtered under pressure using a filter having a pore size of 0.45 μm to obtain water-soluble dye inks 1Y, 1
M, 1B were prepared.

(Example 2) <Dispersion ink 2> [Hydrophobic colorant] Oil black HBB (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 3) ... 2
0.0 g [water-soluble organic solvent] furfuryl alcohol ... 10.0 g ethylene glycol ... 9.0 g [water-soluble polymer] polyvinylpyrrolidone (weight average molecular weight 10,000,
(Product name: PVP K-15, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ ・ ・ 2.5 g [Surfactant] Polyoxyethylene (20) cetyl ether (trade name:
Bridge 58, manufactured by Imperial Chemical Industries) ... 0.5 g [Hydrotropic agent] Urea ... 10.0 g <Water> Pure water ... 48.0 g First, pure water heated to 70 ° C. with urea Polyoxyethylene (20) cetyl ether was added and dissolved by stirring to prepare an aqueous solution. Next, Olaset Yellow 8GF and Filester Violet BA were added to furfuryl alcohol heated to 70 ° C., and the mixture was stirred and heated while heating to 70 ° C.,
Ethylene glycol was added thereto and further mixed with stirring to prepare a colorant solution. While adding the colorant solution to the obtained aqueous solution at 70 ° C., the total amount of the colorant solution is 1
Gradually add dropwise over 1 hour, keeping at 70 ℃
Stirred for hours. Polyvinylpyrrolidone was gradually added thereto, and the mixture was stirred and mixed as it was, and then gradually cooled to 20 ° C. with stirring for 1 hour. And pore size 0.4
Black dispersion ink 2 was prepared by pressure filtration using a 5 μm filter.

Dispersion Ink 2 exhibited a more preferable characteristic that a clear image with high density was obtained because a hydrotropic agent was used. Similar results were obtained when ethylene urea, propylene urea, or thiourea was used instead of urea. Further, since the water-soluble polymer was used, the image showed more preferable characteristics that it was not disturbed at all even when the image was rubbed with a load of 600 g. Further, the use of the penetration accelerator and the surface tension adjusting agent as the surfactant resulted in the ink permeation rate of 5 seconds or less, and thus the image forming rate was improved, which is more preferable property.

<Water-soluble dye ink 2Y> [Water-soluble dye] Aizen Opal Yellow 3GH (trade name, CI Assid Yellow 98 manufactured by Hodogaya Chemical Co., Ltd.)
・ 10.0 g [water-soluble organic solvent] diethylene glycol mono-n-butyl ether ...
10.0 g [Surfactant] Acetylene glycol (trade name: Surfynol 46
(5, made by Air Products and Chemicals) ...
0.1 g [Water] Pure water ... 79.9 g <Water-soluble ink 2M> [Water-soluble dye] Sumiacrylic red G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Red 18) ... -8.0 g [water-soluble organic solvent] diethylene glycol mono-n-butyl ether ...
10.0 g [Surfactant] Acetylene glycol (trade name: Surfynol 46
(5, made by Air Products and Chemicals) ...
0.1 g [Water] Pure water ... 81.9 g <Water-soluble dye ink 2B> [Water-soluble dye] Basic Blue GO (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Basic Blue 25) ... -8.0 g [water-soluble organic solvent] diethylene glycol mono-n-butyl ether ...
10.0 g [Surfactant] Acetylene glycol (trade name: Surfynol 46
(5, made by Air Products and Chemicals) ...
0.1 g [Water] Pure water ... 81.9 g First, a water-soluble dye was added to pure water heated to 50 ° C., and dissolved by stirring while heating for 1 hour. Next, diethylene glycol mono-n-butyl ether and acetylene glycol were added thereto, and the mixture was further stirred and mixed for 1 hour. After stirring and mixing, the mixture was cooled to 20 ° C. and pressure-filtered using a filter having a pore size of 0.45 μm to prepare water-soluble dye inks 2Y, 2M and 2B.

In the water-soluble dye inks 2Y, 2M and 2B, diethylene glycol mono-n-butyl ether, which is also used as a penetration enhancer in the water-soluble organic solvent, and a surfactant which is a penetration enhancer and a surface tension adjusting agent, are used. Since it was used, the ink permeation speed was within 5 seconds, and the more preferable characteristic was that the image forming speed was improved.

(Example 3) <Dispersion ink 3> [Hydrophobic colorant] Fillester Violet BA (trade name, CI Disperse Violet 57 manufactured by Ciba-Gaiki)
9.0g Aizen Zott Yellow 5 (trade name, Hodogaya Chemical Co., Ltd., CI Disperse Yellow 3) ...
1.0 g <water-soluble organic solvent> 2-methyl-2,4-pentanediol ... 20.0
g <Water> Pure water: 70.0 g First, add Filester Violet BA and Aizen Zott Yellow 5 to 2-methyl-2,4-pentanediol heated to 50 ° C and stir while heating to 50 ° C. A colorant solution was prepared by dissolving. The resulting colorant solution and pure water were gradually added dropwise while being heated to 50 ° C. and mixed, and this was stirred for 1 hour while being heated to 50 ° C.
After cooling this to 20 ℃, pore size 0.4
Black dispersion ink 3 was prepared by pressure filtration using a 5 μm filter.

<Water-soluble dye ink 3Y> [Water-soluble dye] Daiacrylic Supra Yellow 5RL (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., CI Basic Yellow 34)
... 10.0 g [Water-soluble polymer] Poly (4-vinylpyridine) ethyl bromide salt (weight average molecular weight 70,000, trade name: P4VP, manufactured by Koei Chemical Industry Co., Ltd.) ... 1.0 g [ Water] Pure water ... 89.0 g <Water-soluble dye ink 3M> [Water-soluble dye] Nippon Brilliant Pink B Conc. (Product name, Sumitomo Chemical Co., Ltd., CI Direct Red 9)
..4.0 g [water-soluble polymer] Methyl cellulose (weight average molecular weight 2,300, trade name: Metroze SM, manufactured by Shin-Etsu Chemical Co., Ltd.) ...
0.2 g [Water] Pure water ... 95.8 g <Water-soluble dye ink 3B> [Water-soluble dye] Alizarin Fast Blue BE (trade name, manufactured by Ciba-Geigy, CI Acid Blue 129) ... 4. 0 g [Water-soluble polymer] Sodium alginate (weight average molecular weight 2,500, manufactured by Kanto Kagaku Co., Ltd.) ... 1.5 g [Water] Pure water ... 94.5 g Pure water heated to 50 ° C., respectively A water-soluble dye was added and dissolved by stirring while heating for 1 hour. A water-soluble polymer was further added thereto, and the mixture was stirred and dissolved while heating for 1 hour. After cooling this to 20 ° C., it was filtered under pressure using a filter having a pore size of 0.45 μm to prepare water-soluble dye inks 3Y, 3M, and 3B.

(Example 4) <Dispersion ink 4> [Hydrophobic colorant] Oleosol Black AR (trade name, manufactured by Taoka Chemical Industry Co., Ltd.) ... 4.5 g Hansa Yellow G (trade name, Daido Kasei) C.I. Pigment Yellow 1)
..1.5 g [water-soluble organic solvent] Glycerin ... 2.5 g Diethylformamide ... 12.5 g <Surfactant> Sodium octylphenoxyethoxyethyl sulfonate (trade name: Newcol 861SE, Nippon Emulsifier Co., Ltd.) ) ... 0.25 g Sodium bisnaphthalene sulfonate (trade name: Disrol SH, manufactured by Nippon Emulsifier Co., Ltd.) ... 0.25 g <Water> Pure water ... 78.5 g First, glycerin and diethylformamide Mix 5
Oleosol Black AR and Hansar Yellow G were added to what was heated at 0 ° C., and dissolved by stirring for 1 hour while heating at 50 ° C. to prepare a colorant solution. Next, the prepared colorant solution was heated to 50 ° C., and pure water heated to 50 ° C. was gradually added dropwise thereto and stirred and mixed for 1 hour. Furthermore, sodium octylphenoxyethoxyethyl sulfonate and sodium bisnaphthalene sulfonate are added here,
The mixture was stirred and mixed for 2 hours while heating at 50 ° C. This is 20
After cooling to 0 ° C., pressure filtration was performed using a filter having a pore size of 0.45 μm to prepare black dispersion ink 4.

In Dispersion Ink 4, since a yellow colorant was used as a complementary color, more preferable characteristics that a more realistic black color could be expressed were exhibited. further,
Since glycerin, which is also used as a moisturizer as a water-soluble organic solvent, was used, the head was filled with ink at 60 ° C.
-30% RH-Ink was ejected from all the nozzles even after the condition without cap for 7 days, which is a more preferable characteristic.

<Water-soluble dye ink 4Y> [Water-soluble dye] Suminol Milling Yellow G (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Asid Yellow 78) ... 2
0.0g [Water-soluble organic solvent] Triethylene glycol mono-n-butyl ether ...
・ 10.0 g [water-soluble polymer] vinyl alcohol-vinyl acetate copolymer (weight average molecular weight 137,700, trade name: Denkapoval B-1
7, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 g [surfactant] sodium oleate (manufactured by Wako Pure Chemical Industries, Ltd.)
-0.1 g [water] pure water ... 68.9 g <water-soluble dye ink 4M> [water-soluble dye] Benzyl Fast Red B (trade name, manufactured by Ciba-Geigy, CI Acid Red 106) ... 15.0 g [Water-soluble organic solvent] Triethylene glycol mono-n-butyl ether ...
・ 10.0 g [water-soluble polymer] vinyl alcohol-vinyl acetate copolymer (weight average molecular weight 137,700, trade name: Denkapoval B-1
7, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 g [surfactant] sodium oleate (manufactured by Wako Pure Chemical Industries, Ltd.)
-0.1 g [Water] Pure water ... 73.9 g <Water-soluble dye ink 4B> [Water-soluble dye] Patent Blue AF (trade name, manufactured by BASF Corporation, CI.
Assidblue 7) ... 15.0 g [water-soluble organic solvent] triethylene glycol mono-n-butyl ether ...
・ 10.0 g [water-soluble polymer] vinyl alcohol-vinyl acetate copolymer (weight average molecular weight 137,700, trade name: Denkapoval B-1
7, manufactured by Denki Kagaku Kogyo Co., Ltd.) 1.0 g [surfactant] sodium oleate (manufactured by Wako Pure Chemical Industries, Ltd.)
-0.1 g [water] Pure water ... 73.9 g To pure water heated to 50 ° C, triethylene glycol mono-n-butyl ether, vinyl alcohol-vinyl acetate copolymer and sodium oleate were added, respectively. It was stirred and dissolved while heating for 1 hour. A water-soluble dye was further added thereto, and the mixture was stirred and dissolved while heating for 1 hour. After cooling this to 20 ° C., it was filtered under pressure using a filter having a pore size of 0.45 μm to prepare water-soluble dye inks 4Y, 4M, and 4B.

(Example 5) <Dispersion ink 5> [Hydrophobic colorant] Hansa Yellow GR (trade name, manufactured by Daido Kasei Co., Ltd.,
C. I. Pigment Yellow 2) ... 1.0 g Aizen spirone red BEH (trade name, Hodogaya Chemical Co., Ltd.) ... 4.0 g Varifast Blue 2610 (trade name, Orient Chemical Co., Ltd.)・ 4.0 g [water-soluble organic solvent] tetrahydrofurfuryl alcohol ... 30.0 g [water-soluble polymer] dextrin (weight average molecular weight 3,000, trade name: Amycor No. 1B, manufactured by Nitto Kagaku Co., Ltd.) ... 3.
5 g <Water> Pure water ... 57.5 g First, Hansa Yellow GR, Eisenspirone Red BEH and Varifast Blue 2610 were added to tetrahydrofurfuryl alcohol and dissolved by stirring for 1 hour to prepare a colorant solution. Next, dextrin was gradually added to pure water with stirring and dissolved by stirring for 1 hour to obtain an aqueous solution.
An aqueous solution was gradually added dropwise to the obtained colorant solution, and the mixture was stirred and mixed for 1 hour. After stirring, pore size 0.45
Black dispersion ink 5 was prepared by pressure filtration using a μm filter.

<Water-Soluble Dye Ink 5Y> [Water-Soluble Dye] Daiacrylic Supra Brilliant Yellow 2GL (trade name, CI Basic Yellow 33 manufactured by Mitsubishi Kasei Co., Ltd.) ... 3.0 g [surfactant ] Dodecyltrimethylammonium chloride (trade name:
0.2 g of distearyl dimethyl ammonium chloride (trade name: Kotamine D86P, manufactured by Kao Corporation) ...
5 g [Water] Pure water ... 96.3 g <Water-soluble dye ink 5M> [Water-soluble dye] Paramagenta base (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Basic Red 9) ... 3 0.0 g [Surfactant] Dodecyl trimethyl ammonium chloride (trade name:
0.2 g of distearyl dimethyl ammonium chloride (trade name: Kotamine D86P, manufactured by Kao Corporation) ...
5 g [Water] Pure water ... 96.3 g <Water-soluble dye ink 5B> [Water-soluble dye] Eisen Marine Blue BNX (trade name, CI Basic Blue 28 manufactured by Hodogaya Chemical Co., Ltd.) ...・
3.0 g [Surfactant] Dodecyl trimethyl ammonium chloride (trade name:
0.2 g of distearyl dimethyl ammonium chloride (trade name: Kotamine D86P, manufactured by Kao Corporation) ...
5 g [Water] Pure water ... 96.3 g A water-soluble dye was added to pure water heated to 50 ° C., and the mixture was stirred and dissolved while heating for 1 hour. To this, dodecyltrimethylammonium chloride and distearyldimethylammonium chloride were added, and the mixture was further stirred and dissolved for 1 hour. After cooling this to 20 ° C., it was filtered under pressure using a filter having a pore size of 0.45 μm to prepare water-soluble dye inks 5Y, 5M and 5B.

(Example 6) Dispersion ink 1 prepared in Example 1 and water-soluble dye inks 2Y, 2Y prepared in Example 2
The evaluations described above were performed by combining M and 2B.

Example 7 Dispersion ink 1 prepared in Example 1, water-soluble dye ink 3Y prepared in Example 3, water-soluble dye ink 4M prepared in Example 4, water-soluble dye ink prepared in Example 5 The evaluation described above was performed in combination with the functional dye ink 5B.

(Example 8) <Water-soluble dye ink 8Y> [Water-soluble dye] Diaside Milling Yellow H5G (trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd. CI Acid Yellow 44)
-4.0 g [alkali] triethanolamine ... 2.0 g [water] pure water ... 94.0 g <water-soluble dye ink 8M> [water-soluble dye] Eisenrose Bengal B (trade name, Hodogaya Chemical Co., Ltd. CI ASSID RED 94) ... 4.0, manufactured by Kogyo Co., Ltd.
g [Alkali] Triethanolamine ... 2.0 g [Water] Pure water ... 94.0 g <Water-soluble dye ink 8B> [Water-soluble dye] Aizen Opal Blue BH (trade name, Hodogaya Chemical Co., Ltd. Manufactured by CI ASSID BLUE 161) ...
4.0 g [alkali] triethanolamine ... 2.0 g [water] pure water ... 94.0 g Water-soluble dye and triethanolamine are added to pure water heated to 50 ° C. and heated for 1 hour While stirring, it was dissolved. After cooling this to 20 ° C., it is filtered under pressure using a filter with a pore size of 0.45 μm,
Is 8.3 water-soluble dye ink 8Y, the same 8.1 water-soluble dye ink 8M, and the same 8.4 water-soluble dye ink 8
B was prepared. Then, when the above-described evaluation was performed in combination with the dispersion ink 1 prepared in Example 1, color bleeding did not occur at all. Upon further detailed observation, no difference was found in the dot diameter on the recording paper and on the water-soluble dye ink in the portion where the dispersion ink 1 was printed. Similar results were also obtained with the image formed with the water-soluble dye inks 8Y, 8M, and 8B immediately after the image was formed with the dispersion ink 1 on the recording paper.

(Example 9) <Water-soluble dye ink 9Y> [Water-soluble dye] Aizen Catilone Yellow GLH (trade name, CI Basic Yellow 14 manufactured by Hodogaya Chemical Co., Ltd.)
・ ・ 4.0g [Acid] Lactic acid ・ ・ ・ 1.0g [Water] Pure water ・ ・ ・ 95.0g <Water-soluble dye ink 9M> [Water-soluble dye] Sumiacrylic Brilliant Red 4G (trade name, Sumitomo Chemical Co., Ltd. C.I. Basic Red 14) ・
..4.0 g [acid] lactic acid ... 1.0 g [water] pure water ... 95.0 g <water-soluble dye ink 9B> [water-soluble dye] Aizen Marine Blue RNX (trade name, Hodogaya Chemical Industry Co., Ltd. C.I. Basic Blue 29) ...
4.0 g [acid] Lactic acid ... 1.0 g [water] Pure water ... 95.0 g Water-soluble dye and lactic acid were added to pure water heated at 50 ° C., and dissolved by stirring while heating for 1 hour. Let This is 2
After cooling to 0 ° C., pressure filtration is performed using a filter having a pore size of 0.45 μm to obtain a water-soluble dye ink 9Y having a pH of 5.8 and a water-soluble dye ink 9 having a pH of 5.9.
A water-soluble dye ink 9B of M and 5.6 was prepared.
Then, when the above-described evaluation was performed in combination with the dispersion ink 1 prepared in Example 1, color bleeding did not occur at all. Upon further detailed observation, no difference was found in the dot diameter on the recording paper and on the water-soluble dye ink in the portion where the dispersion ink 1 was printed. Similar results were also obtained with the image formed with the water-soluble dye inks 9Y, 9M, and 9B immediately after the image was formed with the dispersion ink 1 on the recording paper.

(Example 10) <Dispersion ink 10Y> [Hydrophobic colorant] Oleosol Brilliant Yellow 5G (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Yellow 15)
0) ... 5.0 g [Water-soluble organic solvent] N-methyl-2-pyrrolidone ... 10.0 g Glycerin ... 5.0 g <Water> Pure water ... 80.0 g First, N-methyl 2-Olisol brilliant yellow 5G was added to 2-pyrrolidone and dissolved by stirring for 1 hour to prepare a colorant solution. Next, glycerin was gradually added to pure water with stirring and dissolved by stirring for 1 hour to obtain an aqueous solution. Add the resulting colorant solution slowly to the aqueous solution,
Stir and mix for 1 hour. After stirring, pore size 0.45 μm
The yellow dispersion ink 10Y was prepared by pressure filtration using the above filter.

<Water-soluble dye ink 10Bk> [Water-soluble dye] Direct Fast Black B (trade name, CI Direct Black 22 manufactured by Hodogaya Chemical Co., Ltd.) ...
・ 3.0g [Water] Pure water ・ ・ ・ 97.0g Direct Fast Black B to pure water heated to 50 ℃
Was added and dissolved by stirring while heating for 2 hours. After cooling this to 20 ℃, pore size 0.45μ
A black water-soluble dye ink 10Bk was prepared by pressure filtration using a filter of m.

The dispersion ink 10Y and the water-soluble dye ink 10Bk described above and the water-soluble dye inks 1M and 1B prepared in Example 1 were used for the evaluation described above. Then, the dispersion ink 10Y and the water-soluble dye ink 10
Although a slight color bleeding occurred in the black portion in the image in which the Bk dots overlapped, it was at a level where there was no practical problem. Further, the dispersion ink 10Y was aggregated on the water-soluble dye ink, and the difference in dot diameter between the recording paper and the water-soluble dye ink was less than 3%.

(Comparative Example 1) In this comparative example, in Japanese Patent Laid-Open No. 6-1
Water-soluble dye inks 11Bk, 11Y, 11M and 11B were prepared using the materials and methods described in the specification of Japanese Patent Publication No. 00811.

<Water-Soluble Dye Ink 11Bk> [Water-Soluble Dye] Aizen Catilone Black BXH (trade name, manufactured by Hodogaya Chemical Co., Ltd.) ... 3.0 g [Water-soluble organic solvent] Ethanol ... 0g Ethylene glycol ... 15.0g [Water] Pure water ... 77.0g <Water-soluble dye ink 11Y> [Water-soluble dye] Eisentertrazin conc. (Product name, Hodogaya Chemical Co., Ltd., CI Asid Yellow 23) ...
3.0 g [water-soluble organic solvent] ethanol ... 5.0 g ethylene glycol ... 15.0 g [surfactant] Emulgen 909 (trade name, manufactured by Kao Corporation) ...
1.0 g [Water] Pure water ... 76.0 g <Water-soluble dye ink 11M> [Water-soluble dye] Aizen assid phloxine PB (trade name, manufactured by Hodogaya Chemical Co., Ltd., CI Assid Red 92) ) ...
3.0 g [water-soluble organic solvent] ethanol ... 5.0 g ethylene glycol ... 15.0 g [surfactant] Emulgen 909 (trade name, manufactured by Kao Corporation) ...
1.0 g [Water] Pure water ... 76.0 g <Water-soluble dye ink 11B> [Water-soluble dye] Aizen Primula Turquoise Blue GLH (trade name,
Hodogaya Chemical Co., Ltd., C.I. I. Direct Blue 86) ... 3.0 g [Water-soluble organic solvent] Ethanol ... 5.0 g Ethylene glycol ... 15.0 g [Surfactant] Emulgen 909 (trade name, manufactured by Kao Corporation) ...
1.0 g [water] Pure water ... 76.0 g Each of the compositions shown above is mixed and dissolved, and pressure-filtered using a filter having a pore size of 0.45 μm to perform water-soluble dye inks 11Bk, 11Y, 11M and 11M was prepared. Then, when the evaluation described above was performed, only the water-soluble dye was used as the colorant of the ink,
The image was not water resistant.

(Comparative Example 2) In this comparative example, in Japanese Patent Laid-Open No. 7-1
Black pigmented ink 12 was prepared using the materials and methods described in the 837 publication.

<Pigment ink 12> [Coloring agent] Carbon black FW-18 ... 3.5 g [Water-soluble organic solvent] Hydroxypivalyl / hydroxypivalate ...
0 g Ethoxylated glycerin ... 5.0 g [Dispersant] DAXAD 30-30 (trade name, manufactured by WR Grace and Corporation) ... 1.75 g [Water] Pure water ... 84.75 g First, Carbon black FW-18 and DAXAD 30
-30 was mixed on a roll mill for 24 hours. Next, hydroxypivalyl hydroxypivalate, ethoxylated glycerin and pure water were added thereto, and further mixed by a roll mill for 24 hours. Then, pressure filtration was performed using a filter having a pore size of 0.45 μm to prepare a pigment ink 12 that precipitates at a pH of less than 7.0.

The pigment ink 12 prepared and the water-soluble dye inks 1Y, 1M and 1B of Example 1 were combined and evaluated as described above. By the way, pigment ink 12,
The pHs of the water-soluble dye inks 1Y, 1M and 1B were 8.7, 7.7, 7.5 and 7.8 at 25 ° C, respectively. Then, the portion where the pigment ink 12 is printed is
Feathering, bleeding, and color bleed occurred regardless of the water-soluble dye ink. Furthermore, the pigment ink 12
Used a large amount of dispersant, so the image was not waterfast. Further, since carbon black was used as the colorant of the pigment ink 12, the abrasion resistance of the image was low.

(Comparative Example 3) In this comparative example, JP-A-6-2 is used.
Water-soluble dye inks 13Bk, 13Y, 13M and 13B were prepared using the materials and methods described in the 87494 publication.

<Water-soluble dye ink 13Bk> [Water-soluble dye] C.I. I. Direct Black 168 ... 3.0 g [water-soluble organic solvent] 3-methylpentane-1,5-diol ... 10.0
g [Water] Pure water ... 87.0 g <Water-soluble dye ink 13Y> [Water-soluble dye] Eisentertrazin Conc. (Product name, Hodogaya Chemical Co., Ltd., CI Asid Yellow 23) ...
2.0 g [water-soluble organic solvent] 3-methylpentane-1,5-diol ... 10.0
g [Water] Pure water ... 88.0 g <Water-soluble dye ink 13M> [Water-soluble dye] Kayak Assid Brilliant Red 3BL (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Assid Red 254)
..1.25 g [water-soluble organic solvent] 3-methylpentane-1,5-diol ... 10.0
g [water] pure water ... 88.75 g <water-soluble dye ink 13B> [water-soluble dye] C.I. I. Acid blue 249 ... 1.5 g [water-soluble organic solvent] 3-methylpentane-1,5-diol ... 10.0
g [water] Pure water ... 88.5 g Each of the compositions shown above is mixed and dissolved, and pressure-filtered using a filter having a pore size of 0.45 μm to obtain water-soluble dye inks 13Bk, 13Y, 13M and 13B. Prepared. Then, when the evaluation described above was performed, only the water-soluble dye was used as the colorant of the ink,
The image was not water resistant. Further, feathering, bleeding and color bleeding occurred.

(Comparative Example 4) As a water-soluble organic solvent, 15.0 g of ethanol having a vapor pressure higher than that of water was used.
A black dispersion ink 14 was prepared with the same composition and method as in Example 1 except that methyl-2-pyrrolidone and ethylene carbonate were not used. When the above-mentioned evaluation was performed, the abrasion resistance of the image was low because the vapor pressure of the water-soluble organic solvent was higher than that of water.

Table 1 shows the evaluation results of the inks prepared in the above Examples and Comparative Examples.

[0072]

[Table 1]

In Examples 1 to 10, the water-soluble organic solvent in which the hydrophobic colorant was dispersed in the dispersed ink, the hydrophobic colorant was dissolved, and the vapor pressure was smaller than that of water was used. Further, regarding the water-soluble dye ink, a water-soluble dye that has been ionized in the ink was used. Therefore, when the above-mentioned evaluation was performed, feathering, bleeding and color bleeding did not occur in the image, and the abrasion resistance was also good. Also,
Similar results were obtained when images were formed so that the dots of the dispersed ink and the water-soluble dye ink did not overlap each other. Further, as compared with the case where the image is formed with the water-soluble dye ink so that the dots are overlapped immediately after the image is formed with the dispersion ink, it is slightly smaller when the image is formed with the water-soluble dye ink and then the dispersion ink. It is more preferable because the drying speed of the ink becomes faster and it is more suitable for high speed printing. Furthermore, since a poorly water-soluble or water-insoluble hydrophobic coloring agent was used for the dispersed ink, the water resistance of the image was good.

[0074]

As described above, the image forming method of the present invention dissolves at least water, a sparingly water-soluble or water-insoluble hydrophobic coloring agent and a hydrophobic coloring agent, and has a vapor pressure smaller than that of water. A dispersion ink containing a water-soluble organic solvent and having a hydrophobic colorant dispersed therein and a water-soluble ink containing at least water and a water-soluble dye are used in combination. When an image is formed by this method, the hydrophobic colorant particles in the dispersed ink are aggregated by the inorganic salts in the recording paper and the water-soluble dye in the water-soluble dye ink, and are separated from the liquid component in the ink and remain on the recording paper. To do. Therefore, it is possible to obtain an effect that feathering, bleeding, and color bleeding do not occur in an image. Further, when the color tone of the dispersion ink is black and the color tone of the water-soluble dye ink is selected from 1 to 3 types from yellow, magenta, and cyan to form an image, the quality of a black image, which is a problem particularly in a full-color image, can be obtained. It has become possible to have the effect of further improvement. Furthermore, when the image is formed with the water-soluble dye ink and then the image is formed with the dispersion ink, the hydrophobic colorant particles in the dispersion ink are aggregated with the ionized water-soluble dye in the water-soluble dye ink. It has become possible to have the effect that does not occur. Furthermore, because of the action of the water-soluble organic solvent, the hydrophobic colorant particles on the paper are bonded to each other and the hydrophobic colorant particles and the paper fiber are bonded to each other, which makes it possible to have an effect that the abrasion resistance of the image is good. . In addition, the effect can be further improved by using a water-soluble polymer. Further, by using the surfactant as the surface tension adjusting agent and the penetration accelerator, it becomes possible to improve the penetration speed of the ink into the recording paper and further improve the image forming speed. Furthermore, since the poorly water-soluble or water-insoluble hydrophobic coloring agent is used in the dispersion ink, the coloring component is not solubilized in water, and it is possible to obtain the effect of good water resistance.

Claims (5)

[Claims] 1. A water-soluble organic solvent which dissolves at least water, a sparingly water-soluble or water-insoluble hydrophobic coloring agent and a hydrophobic coloring agent and has a vapor pressure smaller than that of water, and the hydrophobic coloring agent is dispersed. And a water-soluble dye ink containing at least water and a water-soluble dye are used. 2. The image formation according to claim 1, wherein the color tone of the dispersion ink is black, and the color tone of the water-soluble dye ink is selected from yellow, magenta, and cyan. Method. 3. After image formation with a water-soluble dye ink,
The image forming method according to claim 1, wherein an image is formed with the dispersed ink. 4. The image forming method according to claim 1, wherein the dispersion ink and / or the water-soluble dye ink contains a water-soluble polymer. 5. The dispersion ink and / or the water-soluble dye ink contains a surfactant.
The image forming method as described in the above.