JPH08302255A - Ink composition for ink-jet recording - Google Patents

Abstract

PURPOSE: To obtain an ink composition excellent in delivery stability free from clogging of a nozzle. CONSTITUTION: This ink for ink-jet recording comprises a colorant, a water-soluble organic solvent. water and a water-insoluble disintegrant having swelling properties when brought into contact with water. A physically or chemically cross-linked water-insoluble polyvinylpyrrolidone, water-insoluble cellulose, water-insoluble cellulose derivative, its salt, water-insoluble starch or its water- insoluble derivative is used as the disintegrant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for ink jet recording,
More specifically, it relates to an ink composition for inkjet recording, which is excellent in ejection stability. BACKGROUND ART An inkjet recording method is a recording method in which droplets of an ink composition are ejected from a fine nozzle onto a recording medium to cause the ink droplets to adhere to the recording medium for recording. Therefore, in the ink jet recording method, the ejection stability of the ink, that is, the clogging does not occur in the fine nozzles or the tips thereof is an important characteristic.

In particular, when printing is not performed for a long period of time and the solvent in the ink composition has evaporated, nozzle clogging is likely to occur. Furthermore, it may be observed that ink deposits adhere to the nozzles or the nozzle plate even when the printing pause time is short.

In order to prevent evaporation of the solvent in the ink composition, which is considered to be the cause of deposits, a moisturizer is added to the ink composition. By adding a high boiling point organic solvent such as glycerol as a moisturizing agent, the evaporation of the solvent is suppressed.

Further, JP-A-62-53385 discloses a colorant, especially a water-insoluble colorant such as a disperse dye.
Impurities contained in are the cause of ink deposits and purification of colorants has been proposed. According to the disclosure of this publication, by setting the refining level of the colorant to 90% or more, ink deposits in the nozzles are effectively suppressed.

Regarding the water-soluble colorant, JP-A-61-161
No. 113670 discloses that a metal ion having a valence of 2 or more is a cause of the precipitate, and JP-A-61-113671 discloses that a magnesium ion is a cause of the precipitate. Therefore, these publications propose to remove these metal ions from the ink composition. Also, Japanese Patent Laid-Open No. 61-11
No. 3672 proposes removal of the hydrophobic colloid from the ink composition, assuming that the hydrophobic colloid is the cause of the deposit.

All of these conventional techniques leave room for improvement, and it can be said that there is still a need for an ink composition having excellent ejection stability.

[0007]

SUMMARY OF THE INVENTION The present inventors have now found an ink composition that can easily remove ink deposits even if they occur. The present invention, contrary to the conventional method for suppressing the generation of deposits from an ink composition or the method for removing the cause thereof, can easily remove the deposits even if they occur. In that case, it is based on the idea that good ejection stability is ensured.

Therefore, an object of the present invention is to provide an ink composition having excellent ejection stability.

The ink composition according to the present invention contains at least a colorant, a water-soluble organic solvent, water, and a water-insoluble disintegrating agent having a property of swelling when contacted with water. The one.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The "disintegrant" used in the ink composition of the present invention has a property of swelling due to hydration upon contact with water, and is generally called a disintegrant in the pharmaceutical field. And may have essentially the same function as. However, in the present invention, a disintegrating agent which is itself insoluble in water is used. here,
"Insoluble in water" or "water-insoluble" means water: N-
For a mixed solution of methyl-2-pyrrolidone of 9: 1,
A solubility of about 0.2 g / l or less, more preferably about 0.1 g / l or less, and most preferably about 0.05 g / l or less shall be meant.

According to a preferred embodiment of the present invention, the disintegrating agent preferably has a hydration degree of 2 or more, more preferably 3
That is all. Here, the degree of hydration is defined as the ratio of the weight of the disintegrant in a hydrated state (that is, the state in which the maximum amount of water is contained) to the dry weight of the disintegrant.

Furthermore, according to a preferred embodiment of the present invention, the disintegrant is contained in the ink composition as fine particles, and 9 of the particles are contained.
It is preferable that 0% or more has a particle size of less than 10 μm and 99% or more has a particle size of less than 20 μm. Even more preferably, 90% or more has a particle size of less than 7 μm,
Further, 99% or more has a particle size of less than 14 μm.

The fine particle diameter of such a disintegrant can be realized by dispersing the disintegrant by a conventional dispersion method. Further, it is preferable to control the particle size and distribution of the particles by filtering with a filter having a specific pore size. Generally, particles having a size larger than or close to the nozzle diameter of the recording head cause clogging of the nozzle, so particles of such a size should be filtered out in advance with a filter or the like. It goes without saying that it is preferable to have it.

Although the present invention is not intended to be limited by the following theory, the reason why the presence of the disintegrant improves the ejection stability in the present invention is considered as follows. If the ink composition adheres to the nozzle or nozzle plate of the recording head and the solvent evaporates,
A precipitate is generated. In the ink composition according to the present invention, the precipitate contains a disintegrant. When printing is restarted, a new ink composition is supplied. When the precipitate and the water contained in the ink composition come into contact with each other, the disintegrant in the precipitate expands more, such as by hydration, so that the precipitate is "disintegrated". It is considered that this makes it easier for the deposit adhered to the nozzles or nozzle plate of the recording head to be removed by the cleaning operation.

Specific examples of the disintegrant used in the present invention include the following substances. These may optionally be physically or chemically crosslinked to render them water insoluble or water insoluble. Specific examples of these substances include polyvinylpyrrolidone; cellulose; wood substances;
Water-insoluble cellulose derivatives and salts thereof; water-insoluble starch (eg potato starch, rice starch, wheat starch, corn starch, etc.) and their water-insoluble derivatives and salts thereof; water-insoluble natural rubber (eg gum arabic) , Acacia gum, guar gum, xanthine gum, carrageenan gum, tragacanth gum, karaya gum, veegum etc.) and their derivatives and salts thereof; alginic acid and its derivatives and salts thereof; ion exchange resins (eg divinylbenzene and styrene) Copolymers, copolymers of divinylbenzene and methacrylic acid, etc .; water-insoluble inorganic substances (eg clay, bentonite, surface-treated bentonite, finely divided silica); natural sponges; citrus pulp; water-insoluble cotton derivatives etc. You can

It is also preferred to utilize the substances mentioned above which are commercially available as disintegrants. Specific examples thereof include a water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Kolli.
don CL-M (trade name, manufactured by BASF), a water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion liquid Crospo
vidone M (trade name, manufactured by BASF), a fine particle dispersion of water-insoluble cellulose derivative Croscarmel
lose sodium type A (trade name, FM
C), a water-insoluble cellulose derivative fine particle dispersion C
roscarmellose sodium type
NF (trade name, manufactured by FMC), fine particle dispersion of water-insoluble starch derivative HPS-101 (trade name, manufactured by Nitto Kagaku Co., Ltd.), water-insoluble alginic acid A2,830-8 (product number, Aldrich) , Water-insoluble synthetic ion exchange resin Amberlite IRP-88 (trade name, manufactured by Sigma Chemical Co., Ltd.), water-insoluble organic bentonite-based Sven (trade name, manufactured by Tsuchiya Kaolin Industry Co., Ltd.), purified water-insoluble bentonite Examples include Bengal (trade name, manufactured by Tsuchiya Kaolin Industry Co., Ltd.). Further, the crosslinked carboxymethyl guar gum described in US Pat. No. 4,970,078 is also preferable.

The amount of the disintegrant added to the ink composition according to the present invention is preferably about 2 to 20% by weight, more preferably about 4 to 12% by weight, calculated as the dry weight of the disintegrant.

The water used in the ink composition according to the present invention is preferably deionized water, ultrafiltration, reverse osmosis water, distilled water or the like, which is pure water or ultrapure water. It is also preferable to use water that has been sterilized by ultraviolet irradiation, addition of hydrogen peroxide, etc. in order to prevent the generation of mold and bacteria when the ink is stored for a long period of time.

Preferred water-soluble organic solvents in the present invention are ethylene glycol, propylene glycol,
1,3-butanediol, 1,4-butanediol,
Alcohols such as 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc. Ethers, ketones such as acetonylacetone, γ-butyrolactone, diacetin, ethylene carbonate, esters such as triethyl phosphate, formamide, dimethylformamide, diethylformamide, dimethylacetamide, 2-pyrrolidone, N-methyl-2- Nitrogen compounds such as pyrrolidone, sulfur compounds such as dimethylimidazolidinone, dimethylsulfoxide, sulfolane, and 1,3-propanesultone, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy) Butoxy) 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, diacetone alcohol, monoethanolamine, thiodiglycol, morpholine, N-ethylmorpholine, 2- Examples thereof include polyfunctional compounds such as methoxyethyl acetate, diethylene glycol monoethyl ether acetate, and hexamethylphosphoramide.

The amount of the water-soluble organic solvent added to the ink composition according to the present invention is preferably about 0 to 40% by weight, more preferably about 5 to 30% by weight, based on the ink composition.

There are two kinds of colorants preferably used in the present invention, one is a water-soluble colorant, and the other is a relatively sparingly soluble colorant.

Preferred examples of the water-soluble colorant include acidic
Examples include dyes, direct dyes, and food coloring agents. More concrete
Examples of such dyes include Solar Yellow NY Concentrated (commercial
Product name, Sumitomo Chemical Co., Ltd., C.I. I. Acid yellow
-1), D & C Yellow # 10 (trade name, Tricon, CI
Cid Yellow 3), Solar Pure Yellow 8G (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Acid yellow
7), Sun Fast Yellow GGL (trade name, Sumitomo Mikuni Kagaku)
Business Co., Ltd., C.I. I. Acid Yellow 11), Xylene
Light Yellow 2G 140% (trade name, Mitsubishi Kasei Kogyo Co., Ltd.
Company, C.I. I. Acid Yellow 17), Diacid Levelin
g Yellow NR (trade name, Mitsubishi Kasei Co., Ltd., C.I.
I. Acid Yellow 19), Tartrazine Extra Conce
ntrated (trade name, Sandoz, CI Acid Yellow
23), Diacid Fast Yellow R 140% (trade name, Mitsubishi Kabushiki Kaisha)
Sei Kogyo Co., Ltd., C.I. I. Acid Yellow 25), Su
minol Fast Yellow 2PG (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Acid Yellow 29), Metanil Yellow
YK (trade name, ICI, CI Acid Yellow 3
6), Suminol Milling Yellow O (trade name, Sumitomo Chemical Co., Ltd.
Business Co., Ltd., C.I. I. Acid Yellow 38), Polar
Yellow 5G (trade name, Ciba-Geigy, CI Acid Toy
Yellow 40), Suminol Milling Yellow MR (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Acid yellow 4
2), Suminol Milling Brilliant Yellow 5G (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid yellow
44), Suminol Leveling Yellow GR (trade name, Sumitomo
Gaku Kogyo Co., Ltd., C.I. I. Acid Yellow 49), Or
tolan Yellow G (trade name, BASF, CI Acid Ye
Rho 59), Xylene Fast Yellow P (trade name, Sandoz,
C. I. Acid Yellow 61), Carbolan Yellow 4G
(Product name, ICI, CI Acid Yellow 70), Ca
rbolan Yellow 3GS (trade name, ICI, CI Acid Toy
Yellow 72), Xylene Milling Yellow 3GL (trade name,
Sandoz, C.I. I. Acid Yellow 75), Acid Nylon
Fast Orange RL (trade name, Takaoka Chemical Industry Co., Ltd.,
C. I. Acid Yellow 76), Suminol Milling Ye
llow G (trade name, Sumitomo Chemical Co., Ltd., CI reed
Dod Yellow 78), Irganol Yellow 4GLS (trade name,
Ciba-Geigy, C.I. I. Acid Yellow 79), Aizen
Opal Yellow 3GH (trade name, Hodogaya Chemical Co., Ltd.,
C. I. Acid Yellow 98), Palatine Fast Yell
ow GRN (Brand name, BASF, CI Acid Yellow 9
9), Polar Yellow 5GN (trade name, Ciba-Geigy, C.I.
I. Acid Yellow 110), Lanasyn Yellow 3GL (
Trade name, Sandoz, C.I. I. Acid Yellow 111),
Lanasyn Yellow GLN (trade name, Sandoz, CI Acid
Do Yellow 112), Irgalan Yellow GL (trade name, Ci
ba-Geigy, C.I. I. Acid Yellow 114), Cibala
n Yellow GRL (trade name, Ciba-Geigy, CI Acid
Yellow 116), Vialon Fast Yellow G (trade name, BA
SF, C.I. I. Acid Yellow 118), Vialon Fast
Yellow R (trade name, BASF, CI Acid Yellow 1
19), Lanyl Brilliant Yellow 3G (trade name, Sumitomo
Gaku Kogyo Co., Ltd., C.I. I. Acid Yellow 127),
Cibalan Yellow FGL (trade name, Ciba-Geigy, CI
Sid Yellow 128), Lanyl Brilliant Yellow SG
(Product name, Sumitomo Chemical Co., Ltd., CI Acid Toy
Yellow 131), Nylamine Yellow GS (trade name, ICI,
C. I. Acid Yellow 135), Suminol Milling
Yellow 4G (trade name, Sumitomo Chemical Co., Ltd., CI
Acid Yellow 141), Supranol Fast Yellow 6G
(Product name, Bayer AG, CI Acid Yellow 14
2), Kayakalan Yellow GL (trade name, Nippon Kayaku Co., Ltd.
Company, C.I. I. Acid Yellow 161), Lanafast Yel
low GL (trade name, Mitsui Toatsu Chemicals, Inc., CI reed
Dod Yellow 162), Lanafast Yellow 2RL (Product
Name, Mitsubishi Kasei Co., Ltd., C.I. I. Acid yellow
163), Solar Pure Yellow GOO (trade name, Sumitomo Chemical
Industry Co., Ltd., C.I. I. Acid Yellow 164), Mi
tsui Nylon Fast Yellow 3G (trade name, Mitsubishi Kasei Co., Ltd.
Ceremony company, C.I. I. Acid Yellow 165), Chrysami
ne (trade name, Takaoka Chemical Industry Co., Ltd., CI Dilek
Toe Yellow 1), Nippon Pure Yellow 5G (trade name, housing
Tomo Chemical Co., Ltd., C.I. I. Direct yellow
8), Direct Fast Yellow A (trade name, Kansai Dye Manufacturing Co., Ltd.
Ceremony company, C.I. I. Direct Yellow 11), Chrysoph
enine (trade name, Sumitomo Chemical Co., Ltd., CI Die
Rect Yellow 12), Chrysamine G (trade name, made in Japan
Yakuhin Co., Ltd., C.I. I. Direct Yellow 24), Dire
ct Fast Yellow 5GL (trade name, Hodogaya Chemical Co., Ltd.
Company, C.I. I. Direct Yellow 26), Sirius Super
Yellow 5G (trade name, Bayer AG, CI Direct Key
Yellow 27), Direct Fast Yellow BC (trade name, Kansai
Dye Manufacturing Co., Ltd., C.I. I. Direct yellow 2
8), Benzo Cuprol Yellow GRL (trade name, Bayer AG,
C. I. Direct Yellow 33), Sumilight Supra
Yellow 2GL (trade name, Sumitomo Chemical Co., Ltd., CI
Direct Yellow 39), Aizen Primura Yellow GCL
H (trade name, Hodogaya Chemical Co., Ltd., CI Dire
Yellow 49), Direct Fast Yellow R (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Direct yellow 5
0), Sirius Supra Yellow FGR-LL (trade name, Bayer A
G, C. I. Direct Yellow 58), Direct Fast Y
ellow GN (trade name, Nippon Kayaku Co., Ltd., CI Dai
Recto Yellow 86), Carodirect Yellow RL (Product
Name, Caroline Color and Chemical, C.I. I. Dilek
Toe Yellow 86), Kayarus Light Yellow F8G (Product
Name, Nippon Kayaku Co., Ltd., C.I. I. Direct yellow 8
7), Diacupro Yellow GR (trade name, Mitsubishi Kasei Co., Ltd. stock)
Company, C.I. I. Direct Yellow 88), Kayarus Cu
pro Yellow GG (trade name, Nippon Kayaku Co., C.I.
Dairetoku Yellow 89), Solar Yellow 3GL (Product
First name, Sandoz, C.I. I. Direct Yellow 98), Aize
n Primura Yellow 2RH (trade name, Hodogaya Chemical Co., Ltd.
Company, C.I. I. Direct Yellow 100), Sirius Sup
ra Yellow GD (trade name, Bayer AG, CI Direct
Yellow 110), Sunset Yellow (trade name, Yamato dye)
Manufacturing Co., C.I. I. Food Yellow 3), Tartrazi
ne (brand name, Daiwa Dye Mfg. Co., Ltd., CI Food Toy
Yellow 4), Solar Fast Red 3G (trade name, Sumitomo Chemical Co., Ltd.
Business Co., Ltd., C.I. I. Acid Red 1), Chuganol F
ast Red B (trade name, Chugai Chemical Co., Ltd., CI reed
Dread 6), Sumitomo Fast Scarlet A (trade name,
Sumitomo Mikuni Chemical Co., Ltd., C.I. I. Acid red
8), Silk Scarlet (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Acid Red 9), Solar Red S (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Acid red 1
3), Solar Rubine Extra (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Acid Red 14), Acid Brilliant
Scarlet 3R (trade name, Takaoka Chemical Industry Co., Ltd., C.I.
I. Acid Red 18), Aizen Ponceau RH (Product
Name, Hodogaya Chemical Co., Ltd., C.I. I. Acid red
26), Aizen Amaranth (trade name, Hodogaya Chemical Co., Ltd.
Company, C.I. I. Acid Red 27), Suminol Leveli
ng Red 6BL Extra Concentrated (trade name, Sumitomo Chemical Co., Ltd.
Business Co., Ltd., C.I. I. Acid Red 32), Diacid S
upra Red 3B (trade name, Mitsubishi Kasei Co., Ltd., C.I.
I. Acid Red 35), Azo Rubinol 3GS 250% (quote
Product name, Mitsubishi Kasei Co., Ltd., C.I. I. Acid red
37), Supracene Red B (trade name, Bayer AG, C.I.
I. Acid Red 42), Aizen Erythrosine (Product
Name, Hodogaya Chemical Co., Ltd., C.I. I. Acid red
51), Solar Rhodamine B (trade name, Sumitomo Chemical Co., Ltd.
Ceremony company, C.I. I. Acid Red 52), Suminol Leve
ling Rubiol3GP (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Acid Red 57), Erio Fast Red GB
Product name, Ciba-Geigy, C.I. I. Acid Red 75), Er
io AcidRed XG (trade name, Ciba-Geigy, CI Acid
Dread 77), Alizarine Rubinol R (trade name, Baye
r AG, C.I. I. Acid Red 80), Alizarine Rubi
nol 3G (trade name, Bayer AG, CI Acid Red 8
2), Alizarine Rubinol5G (trade name, Yamada Kabushiki Kaisha)
Institute of Science, C.I. I. Acid Red 83), Suminol Mi
lling Red PG (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Acid Red 85), Aizen Eosine GH Concentr
ated (trade name, Hodogaya Chemical Co., Ltd., CI reed)
Dread 87), Roccelline NS Concentrated 120%
(Product name, Sumitomo Chemical Co., Ltd., CI Acidre
88), Acid Anthracene Red 3BL (trade name, Sumitomo
Mikuni Chemical Industry Co., Ltd., C.I. I. Acid red 8
9), PylamCertified D & C Red # 28 (trade name, Pylam
, C.I. I. Acid Red 92), Aizen Rose Bengal
B (trade name, Hodogaya Chemical Co., Ltd., CI reed
94), Acid Anthracene Red G (trade name,
Chugai Chemical Co., Ltd., C.I. I. Acid Red 97), Be
nzyl Fast Red B (trade name, Ciba-Geigy, CI reed
Dread 106), Sulfonine Scarlet GNL (Product
First name, Sandoz, C.I. I. Acid Red 116), Sulfon
ine Red RS (trade name, Sandoz, CI Acid Red
114), Suminol Milling Scarlet R (trade name, Sumitomo
Chemical Industry Co., Ltd., C.I. I. Acid Red 117),
Suminol Fast Red G (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Acid Red 118), Kayanol Milling Re
d Brown V (trade name, Nippon Kayaku Co., CI reed
Doddred 119), Benzyl Fast Rubine 3BW (Product
First name, Ciba-Geigy, C.I. I. Acid Red 129), Po
lar Brilliant Red BN (trade name, Ciba-Geigy, CI
Acid Red 130), Polar Brilliant Red 3BN
(Brand name, Ciba-Geigy, CI Acid Red 13
1), Supranol Brilliant Red B (trade name, Bayer AG,
C. I. Acid Red 133), Polar Red 3B (Product
First name, Ciba-Geigy, C.I. I. Acid Red 134), Ca
rbolan Crimson BS (trade name, ICI, CI acid
Red 138), Brilliant Alizarin Milling Red FBL
(Trade name, Sandoz, CI Acid Red 143),
Suminol Milling Scarlet G (trade name, Sumitomo Chemical Co., Ltd.
Ceremony company, C.I. I. Acid Red 145), Supranol F
ast Red BB (trade name, Bayer AG, CI Acid Red
154), Supranol Brilliant Red 3B (trade name, Ba
yer AG, C.I. I. Acid Red 155), Suminol Mi
lling Red G (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Acid Red 158), Irganol Red BLS (Product
First name, Ciba-Geigy, C.I. I. Acid Red 168), Pa
latine Fast Red RN (trade name, BASF, CI Acid
Red 180), Neolan Red GRE (trade name, Ciba-Geig
y, C.I. I. Acid Red 183), Sumilan Violet
Brown B (trade name, Sumitomo Chemical Co., Ltd., CI
Sid Red 184), Palatine Fast Pink BN (Product
Name, BASF, C.I. I. Acid Red 186), Neolan B
ordeaux RM (trade name, Ciba-Geigy, CI Acid Re
194), Neolan Red REG (trade name, Ciba-Geigy,
C. I. Acid Red 198), Coranil Red HE 3B
(Brand name, Hoechst AG, CI Acid Red 19
9), Lanyl Scarlet G (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Acid Red 209), Lanyl Red GG
(Product name, Sumitomo Chemical Co., Ltd., CI Acidre
211), Lanyl Red B (trade name, Sumitomo Chemical Co., Ltd.
Ceremony company, C.I. I. Acid Red 215), Lanasyn Re
d 2GL280% (trade name, Mitsubishi Kasei Co., Ltd., CI
Acid Red 216), Lanasyn Bordeaux RL (Product
First name, Sandoz, C.I. I. Acid Red 217), Irgala
n Red 2BL (trade name, Ciba-Geigy, CI Acid Re
219), Polar Brilliant Red B (trade name, Ciba
-Geigy, C.I. I. Acid Red 249), Cibalan Br
illiant Red BL (trade name, Ciba-Geigy, CI Acid
Dread 252), Kayaku Acid Brilliant Red 3BL
(Product name, Nippon Kayaku Co., Ltd., CI Acid Red
254), Kayakalan Bordeaux BL (trade name, Nippon Kayaku
Co., Ltd., C.I. I. Acid Red 256), Mitsui N
ylon Rast Red 3B (trade name, Mitsui Toatsu Chemicals, Inc.
C. I. Acid Red 257), Lanasyn Scarlet GL
250% (trade name, Mitsubishi Kasei Co., Ltd., CI reed
Dread 262), Mitsui Acid Brilliant Milling
Red BL (trade name, Mitsui Toatsu Chemicals, Inc., CI reed
Dodred 265), Mitsui Nylon Fast Red BB (Product
Mitsui Toatsu Chemicals, Inc., C.I. I. Acid red 2
66), Suminol Milling Brilliant Red 4BS (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid red 2
74), Supranol Brilliant Red GW (trade name, Bayer
AG, C.I. I. Acid Red 276), Luganil Red NB
(Brand name, BASF, CI Acid Red 282), Lu
ganil Red NG (trade name, BASF, CI Acid Red
283), Neopolar Brilliant Red B (trade name, Ciba-G
eigy, C.I. I. Acid Red 303), Kayakalan Sc
arlet GL (trade name, Nippon Kayaku Co., Ltd., CI Acid
Dread 317), Kayakalan Red BL (trade name, made in Japan
Yakuhin Co., Ltd., C.I. I. Acid Red 318), Lanafa
stRed 2GL (trade name, Mitsui Toatsu Chemicals, Inc., CI
Acid Red 320), Lanafast Rubine RL (Product
Mitsui Toatsu Chemicals, Inc., C.I. I. Acid red 3
21), Mitsui Nylon Fast Red B (trade name, Mitsui Toatsu)
Chemical Co., C.I. I. Acid Red 322), Japa
nol Fast Red F (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Direct Red 1), Benzopurpurine 4B (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Direct red
2), Aizen Primula Scarlet GSH (trade name, Hodogaya)
Gaku Kogyo Co., Ltd., C.I. I. Direct Red 4), Diph
enyl Brilliant Pink P (trade name, Ciba-Geigy, C.I.
I. Direct Red 9), DirectBrilliant Pink 3B
(Product name, Ciba-Geigy, CI Direct Red 1
1), Diacotton Bordeaux GH (trade name, Mitsubishi Kasei)
Co., Ltd., C.I. I. Direct Red 13), Kayaku D
irect Bordeaux (trade name, Nippon Kayaku Co., C.I.
Direct Red 17), Nippon Brilliant Rose BD C
oncentrated (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Direct Red 20), Direct Fast Scarlet 4B
S (trade name, Sumitomo Chemical Co., Ltd., CI Dilek
Tread 23), Chloramine Fast Scarlet 4BSL (Product
First name, Sandoz, C.I. I. Direct Red 24), Congo
Red (trade name, Mitsubishi Kasei Co., Ltd., CI Dairay
Coctred 28), Diacotton Rhoduline Red B (Product
Name, Mitsubishi Kasei Co., Ltd., C.I. I. Direct red
31), Azine Fast Red DGL (trade name, Sumitomo Chemical Co., Ltd.
Ceremony company, C.I. I. Direct Red 33), Direct Sca
rlet B (trade name, Sumitomo Chemical Co., Ltd., CI die
Rect Red 37), Direct Fast Red 3B (Product name, Medium
Gaika Chemical Co., Ltd., C.I. I. Direct Red 39), Ni
tto Direct Rubinol B (trade name, Nitto Dye Manufacturing Stock Association
Company, C.I. I. Direct Red44), Benzo Brillian
t Red 8BS (trade name, Bayer AG, CI Direct
46), NipponFast Orange F3RS (trade name, Sumitomo
Chemical Industry Co., Ltd., C.I. I. Direct Red 62),
Cuprofix Red C-5BL (trade name, Sandoz, CI Dire
Chord Red 63), Chlorazol Fast Pink BK (trade name,
ICI, C.I. I. Direct Red 76), Sumilight Su
pra Red 4BL Concentrated (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Direct Red 79), Sirius Red F
3B (trade name, Bayer AG, CI Direct Red 8
0), Suprazo Red 4B (trade name, Mitsui Toatsu Chemical Co., Ltd.
Company, C.I. I. Direct Red 81), Kayarus Supra
Rubine BL (trade name, Nippon Kayaku Co., Ltd., CI Dai
Rect Red 83), Sumilight Supra Brown 3RL (quote)
Product name, Sumitomo Chemical Co., Ltd., C.I. I. Directory
84), SumilightSupra Scarlet BNS Concentrated
(Product name, Sumitomo Chemical Co., Ltd., CI Direct
Red 89), Sirius Supra Scarlet BN (trade name, Ba
yer AG, C.I. I. Direct Red 96), Kayarus Su
pra Bordeaux GL (trade name, Nippon Kayaku Co., Ltd., C.I.
I. Direct Red 99), Sirius Scarlet B (Product
Name, Bayer AG, C.I. I. Direct Red 113), Dia
cupor Red SB (trade name, Mitsubishi Kasei Co., Ltd., C.I.
I. Direct Red 197), Direct Scarlet B New
(Product name, Sumitomo Chemical Co., Ltd., CI Direct
Red 201), Sirius Supra Scarlet G-LL (Product
Name, Bayer AG, C.I. I. Direct Red 218), So
lar Rubinol SLR (trade name, Sandoz, CI Dilek
Tread 220), Kayarus Light Scarlet R2G (Product
Name, Nippon Kayaku Co., Ltd., C.I. I. Direct red 22
4), Kayarus Light Red F5G (trade name, Nippon Kayaku Co., Ltd.
Company, C.I. I. Direct Red 225), Kayarus Li
ght Red FSB (trade name, Nippon Kayaku Co., C.I.
Electred 226), Kayarus Light Rose FR (quote)
Product name, Nippon Kayaku Co., Ltd., C.I. I. Direct red 2
27), Kayarus Cupro Red 2B (trade name, Nippon Kayaku Co., Ltd.
Company, C.I. I. Direct Red 228), Nippon Bor
deaux NS Concentrated (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Direct Red 229), Nippon Resin
Fast Scarlet 4BA (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Direct Red 230), Azine Light Bord
eaux FBX (trade name, Sumitomo Chemical Co., Ltd., CI Da
Electred 231), New Coccine (trade name, Yamato
Dye Manufacturing Co., Ltd., C.I. I. Hood Red 4), Amaran
th (trade name, Daiwa Dye Mfg. Co., C.I.
Yellow 9), Erythrosine (trade name, Hodogaya Chemical Co., Ltd.)
Ceremony company, C.I. I. Food Yellow 9), Patent Pure Bl
uu VX (trade name, Sumitomo Mikuni Chemical Co., Ltd., CI
Acid Blue 1), Patent Blue AF (trade name, BASF,
C. I. Acid Blue 2), Rakuto Brilliant Bule
FCF (trade name, Rakuto Chemical Industry Co., Ltd., CI reed
Do Blue 9), Brilliant Acid Blue R (trade name, Ci
ba-Geigy, C.I. I. Acid Blue 15), OrientSolu
ble Blue OBC (trade name, Orient Chemical Industry Co., Ltd.
Company, C.I. I. Acid Blue 22), Suminol Leveling
Blue 4GL (trade name, Sumitomo Chemical Co., Ltd., CI
Acid Blue 23), Nylomine Blue GS (trade name, IC
I, C.I. I. Acid Blue 25), Acilan Astrol B
(Brand name, Bayer AG, CI Acid Blue 27),
Acid Nylon Fast Dark Blue B (trade name, Takaoka Chemical Industry
Co., Ltd., C.I. I. Acid Blue 29), Erio Anthr
acene Brilliant Blue 2GL (trade name, Ciba-Geigy, C.I.
I. Acid Blue 40), Diacid Light Blue BR 200
% (Trade name, Mitsubishi Kasei Co., Ltd., CI Acid
Blue 41), Solway Blue (trade name, ICI, C.I.
Acid Blue 43), Solway Blue BN (trade name, ICI)
, C.I. I. Acid Blue 45), Brilliant Alizari
ne Light Blue 3F (trade name, Sandoz, CI Acid
Deblue 54), Kayanol Blue BL (trade name, Nippon Kayaku)
Co., Ltd., C.I. I. Acid Blue 59), Derma Blue
2B (trade name, Sandoz, CI Acid Blue 6
2), Brilliant Alizarine Light Blue 3FR (trade name,
Sandoz, C.I. I. Acid Blue 62), Alizarine Li
ght Blue FG (trade name, Sandoz, CI Acid Bull
-72), Rakuto Indigo Carmine Blue G (trade name, stock
Rakuto Chemical Industry Co., Ltd., C. I. Acid blue 7
4), Suminol Fast Sky Blue B (trade name, Sumitomo Chemical Co., Ltd.
Business Co., Ltd., C.I. I. Acid Blue 78), Alizarin
e Fast Blue R (trade name, Ciba-Geigy, CI Acid
Deblue 80), Xylene Fast Blue (trade name, Sandoz,
C. I. Acid Blue 82), Coomassie Brilliant
Blue R (trade name, ICI, CI Acid Blue 8
3), Coomassie Brilliant Blue G (trade name, ICI,
C. I. Acid Blue 90), Suminol Fast Navy Bl
ue R (trade name, Sumitomo Chemical Co., Ltd., CI Acid
De Blue 92), Orient Soluble Blue OBB (trade name,
Orient Chemical Industry Co., Ltd., C.I. I. Acid blue
93), Supranol Cyanine 7BF (trade name, Bayer AG,
C. I. Acid Blue 100), Supranol Blue GL
(Brand name, Bayer AG, CI Acid Blue 10
2), Sumitomo Brilliant Blue FG (trade name, Sumitomo Mikuni
Chemical Industry Co., Ltd., C.I. I. Acid Blue 103),
Acilan BrilliantBlue FFR (trade name, Bayer AG, C.I.
I. Acid Blue 104), CoomassieUltra Sky SE
(Product name, ICI, CI Acid Blue 112), Co
omassie Navy Blue 2RN (trade name, ICI, CI reed
Blue 113), Supramine Blue R (trade name, Baye
r AG, C.I. I. Acid Blue 117), Suminol Mill
ingCyanine GR Extra (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Acid Blue 120), Brilliant Aliz
arine Milline Blue 2RL (trade name, Sandoz, CI
Sid Blue 126), Kayanol Milling Blue GW
Product name, Nippon Kayaku Co., Ltd., C.I. I. Acid Blue 12
7), Xylene Fast Blue PR (trade name, Sandoz, C.I.
I. Acid Blue 129), Supranol Brilliant Blu
e FG (trade name, Bayer AG, CI Acid Blue 13
0), Brilliant Alizarine Milling Blue RWL (Product
First name, Sandoz, C.I. I. Acid Blue 131), Mitsui
Acid MillingBlue BS (trade name, Mitsui Toatsu Chemical Co., Ltd.
Company, C.I. I. Acid Blue 138), Carbonan Brill
iant Blue (trade name, ICI, CI Acid Blue 1
40), Xylene Brilliant Blue 5GM (trade name, Sando
z, C.I. I. Acid Blue 142), Brilliant Aliza
rine Milling Blue FGL (trade name, Sandoz, CI
Cid Blue 143), Ortolan Blue G (trade name, BAS
F, C. I. Acid Blue 151), Neolan Blue GG
(Product name, Ciba-Geigy, CI Acid Blue 15
4), Neolan Blue GG (trade name, Ciba-Geigy, C.I.
Acid Blue 158), Aizen Opal Blue BH (Product
Name, Hodogaya Chemical Co., Ltd., C.I. I. Acid blue
161), Irgalan Blue GL (trade name, Ciba-Geigy,
C. I. Acid Blue 166), Lanyl Violet 4B Ex
tra Concentrated (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Acid Blue 167), Cibalan Blue (Product
First name, Ciba-Geigy, C.I. I. Acid Blue 168), La
nyl Blue BR (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Acid Blue 170), Lanyl Blue 3G (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid blue 1
71), Carobolan Brilliant Blue 2GS (trade name, ICI
, C.I. I. Acid Blue 175), Alizarine Light
Blue HRL 180% (trade name, Mitsubishi Kasei Co., Ltd.,
C. I. Acid Blue 182), Cibalan Brilliant
Blue GL (trade name, Ciba-Geigy, CI Acid Bull
183), Cibalan Navy Blue RL (trade name, Ciba-Gei
gy, C.I. I. Acid Blue 184), Irgalan Navy B
lue 2GL (trade name, Ciba-Geigy, CI Acid Bull
-187), Aizen Opal Blue New Concentrated (Product
Name, Hodogaya Chemical Co., Ltd., C.I. I. Acid blue
192), Isolan Blue FBN (trade name, Bayer AG, C.I.
I. Acid Blue 199), Alizarine Brilliant Sk
y Blue BLW (trade name, Bayer AG, CI Acid Bull
-203), Alizarine Brilliant Sky BlueRLW (Product
Name, Bayer AG, C.I. I. Acid Blue 204), Aliz
arine Brilliant Sky Blue RW (trade name, Bayer AG,
C. I. Acid Blue 205), Lanacron Navy Blue
B (trade name, Ciba-Geigy, CI Acid Blue 22
9), Kayakalan Blue Black RL (trade name, Nippon Kayaku Co., Ltd.
Ceremony company, C.I. I. Acid Blue 234), Mitsui Nyl
on Blue BL (trade name, Mitsui Toatsu Chemicals, Inc., CI
Acid Blue 236), Direct Sky Blue GB (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Direct blue
1), Direct Black BH (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Direct Blue 2), Direct Blue 2B
(Product name, Sumitomo Chemical Co., Ltd., CI Direct
Blue 6), Diphenyl Blue BT (trade name, Ciba-Geigy,
C. I. Direct Blue 8), Direct Sky Blue (quote)
Product name, Sumitomo Chemical Co., Ltd., C.I. I. Direct bull
-15), Direct Brilliant Blue RW (trade name, Sumitomo
Gaku Kogyo Co., Ltd., C.I. I. Direct Blue 22), Ni
ppon New Blue 5 BS Concentrated (trade name, Sumitomo Chemical
Industry Co., Ltd., C.I. I. Direct Blue 25), Benz
Brilliant Sky Blue 8GS (trade name, Bayer AG, C.I.
I. Direct Blue 41), Sumilight Supra Blue B
RR Concentrated (trade name, Sumitomo Chemical Co., Ltd.,
C. I. Direct Blue 71), Durazol Blue 2GN
(Product name, ICI, CI Direct Blue 76), So
lar Blue 2GLN (trade name, Sandoz, CI Direct
Blue 77), Sirius Supra Blue G (trade name, Bayer
AG, C.I. I. Direct Blue 78), Chlorantine Fa
st Blue 2RLL (trade name, Ciba-Geigy, CI Dilek
Toe Blue 80), Special Fast Turquosie 8GLLiquid
(Product name, Mobay Chemical, CI Direct Blue
86), SolarBlur FGL (trade name, Sandoz, CI da
Elect Blue 90), Sumilight Supra Blue FBGL
(Product name, Sumitomo Chemical Co., Ltd., CI Direct
Blue 98), Chlorantine Fast Briliant Blue 2GLL
(Product name, Ciba-Geigy, CI Direct Blue 10
6), Kayarus Supra Blue FFRL (trade name, Nippon Kayaku Co., Ltd.
Ceremony company, C.I. I. Direct Blue 107), Benzamin
e Indigo Blue BRLS (trade name, Bayer AG, CI die
Recto Blue 120), Cuprophenyl Brilliant Blue2B
L (trade name, Ciba-Geigy, CI Direct Blue 1
58), CuprophenylNavy Blue 2BL (trade name, Ciba-Ge
igy, C.I. I. Direct Blue 160), Coprantine
Blue 3RLL (trade name, Ciba-Geigy, CI Direct
Blue 163), Kayarus Cupro Blue 4GL (trade name, date
Hon Kayaku Co., Ltd. I. Direct Blue 166),
Direct Copper Blue 2B (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Direct Blue 168), Dialuminous
Blue RF (trade name, Mitsubishi Kasei Co., Ltd., CI da
Elect Blue 192), Dialuminous Blue GF (Product
Name, Mitsubishi Kasei Co., Ltd., C.I. I. Direct blue
193), Diacupro BlueR (trade name, Mitsubishi Kasei Co., Ltd.
Ceremony company, C.I. I. Direct Blue 194), Diacupro
Blue B (trade name, Mitsubishi Kasei Co., Ltd., CI Da
Elect Blue 195), Diacupro Navy Blue BR
Product name, Mitsubishi Kasei Co., Ltd., C.I. I. Direct bull
196), Carodirect Turquoise FBL Supra Concent
rated (trade name, Caroline Color and Chemical, C.I.
I. Direct Blue 199), Aizen Primula Blue B
GLH (trade name, Hodogaya Chemical Co., Ltd., CI Die
Rect Blue 200), Kayarus Supra Blue BRL 200
(Product name, Nippon Kayaku Co., Ltd., CI Direct Bull
-201), Kayarus Supra Blue 4G (trade name, made in Japan
Yakuhin Co., Ltd., C.I. I. Direct Blue 202), Kaya
rus Supra Blue RCL (trade name, Nippon Kayaku Co., Ltd., C.I.
I. Direct Blue 203), Chlorantine FastBlue
2BLL (trade name, Ciba-Geigy, CI Direct Bull
-207), SiriusSupra Blue FGG (trade name, Bayer A
G, C. I. Direct Blue 225), Sirius Supra
Blue 3G (trade name, Bayer AG, CI Direct Bull
-226), Kayarus Supra Blue BCL (trade name, made in Japan
Yakuhin Co., Ltd., C.I. I. Direct Blue 236), Kaya
rus Supra Blue BWL (trade name, Nippon Kayaku Co., Ltd., C.I.
I. Direct Blue 237), Diacupro Navy Blue B
L (trade name, Mitsubishi Kasei Co., Ltd., CI Dilek
Toblue 246), Kayarus Cupro Navy Blue CLW (quote)
Product name, Nippon Kayaku Co., Ltd., C.I. I. Direct blue 2
48), Azine Navy Blue B Concentrated (trade name, housing
Tomo Chemical Co., Ltd., C.I. I. Dairetoku Blue 24
9), Indigo Carmine (trade name, Daiwa Dye Manufacturing Co., Ltd.
Company, C.I. I. Food Blue 1), C.I. I. Hood blue
(Hodogaya Chemical Co., Ltd.), Acid Blue Black 10B
(Product name, Mitsui Toatsu Chemicals, Inc., CI Acid Bud
Rack 1), Orient Nigrosine BR, OZ (trade name, orientation
Ento Chemical Co., Ltd., C.I. I. Acid black
2), Inoe Acid Black M (trade name, Inoue Chemical Co., Ltd.
Industry, C.I. I. Acid Black 7), Suminol Mill
ing Black 8BX (trade name, Sumitomo Chemical Co., Ltd., C.I.
I. Acid Black 24), Suminol Milling Black
VLG (trade name, Sumitomo Chemical Co., Ltd., CI Acid
De Black 26), Suminol Milling Black NB (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid black
29), Suminol Fast Black BR Concentrated (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid black
31), Sulfonine Gray BWL (trade name, Sandoz, C.I.
I. Acid Black 44), Coomassie Fast Gray 3G
S (trade name, ICI, CI Acid Black 48),
Xylene Fast Gray P 200% (trade name, Mitsubishi Kasei Co., Ltd.
Company, C.I. I. Acid Black 50), Neolan Gray
3B (trade name, Ciba-Geigy, CI Acid Black 5
1), Aizen Opal Black WGH (trade name, Hodogaya Chemical Industry)
Co., Ltd., C.I. I. Acid Black 52), Lanasyn
Gray BL (trade name, Sandoz, CI acid black
58), Lanyl Gray B (trade name, Sumitomo Chemical Co., Ltd.
Company, C.I. I. Acid Black 60), Lanyl Gray GG
(Product name, Sumitomo Chemical Co., Ltd., CI Acid Bud
Rack 62), Vialon Fast Black R (trade name, BASF,
C. I. Acid Black 63), Irgalan Olive BGL
(Product name, Ciba-Geigy, CI Acid Black 6
4), Sella Fast Black FF (trade name, Ciba-Geigy,
C. I. Acid Black 67), Coranil Gray HEG
(Product name, Hoechst AG, CI Acid Black 7
2), Derma Gray LL (trade name, Sandoz, CI reed)
Dod Black 76), Derma Carbon GTS (trade name, Sand
oz, C.I. I. Acid Black 77), Nippon Leather
Black B (trade name, Sumitomo Chemical Co., Ltd., CI
Cid black 94), Cibalan Black BGL (trade name, C
iba-Geigy, C.I. I. Acid Black 107), Cibal
an Black 2GL (trade name, Ciba-Geigy, CI Acid
Dblack 108), Kayanol Milling Black TLB (quote)
Product name, Nippon Kayaku Co., Ltd., C.I. I. Acid black 1
09), Kayanol Milling Black TLR (trade name, made in Japan
Yakuhin Co., Ltd., C.I. I. Acid Black 110), Kaya
balan Gray BL (trade name, Nippon Kayaku Co., Ltd., CI
Acid Black 112), Lanyl Gray 3B (trade name,
Sumitomo Chemical Co., Ltd., C.I. I. Acid black 11
5), Aizen Opal Black BNH (trade name, Hodogaya Chemical Industry
Co., Ltd., C.I. I. Acid Black 118), Aizen
Opal Black New Concentrated (trade name, Hodogaya Chemical Industry
Business Co., Ltd., C.I. I. Acid Black 119), Aize
n Floslan Gray BLH (trade name, Hodogaya Chemical Co., Ltd.
Company, 121), Aizen Floslan Gray GLH (brand name, soil preservation
Tani Chemical Co., Ltd., C.I. I. Acid black 12
2), Irgalan Black GBL (trade name, Ciba-Geigy, C.I.
I. Acid Black 131), Lanasyn Black BRL 20
0% (brand name, Mitsubishi Kasei Co., Ltd., CI Acid
Black 132), Isolan Black RL (trade name, Bayer
AG, C.I. I. Acid Black 139), Isolan Gray
BRLS (trade name, Bayer AG, CI Acid Black 1
40), Kayakalan Black 2RL (trade name, Nippon Kayaku Co., Ltd.
Company, C.I. I. Acid Black 155), Kayanol Mi
lling Gray GW (trade name, Nippon Kayaku Co., Ltd., CI
Acid Black 156), Lanafast BlueBlack BL
(Product name, Mitsui Toatsu Chemicals, Inc., CI Acid Bud
Rack 157), Lanafast Black BGL (trade name, Mitsui East)
Pressure Chemical Co., Ltd., C.I. I. Acid Black 158),
Lanafast Black 2BL (trade name, Mitsui Toatsu Chemicals, Inc.
C. I. Acid Black 159), Aizen Opal Navy
Blue RH (trade name, Hodogaya Chemical Co., Ltd., CI
Acid Black 191), Diacotton Fast Black (quote
Product name, Mitsubishi Kasei Co., Ltd., C.I. I. Direct bra
17), Sumilight Black G Concentrated (Product
Name, Sumitomo Chemical Co., Ltd., C.I. I. Acid black
19), Formal Fast Black G (trade name, Ciba-Geigy,
C. I. Acid Black 22), Direct Fast Black
AB (trade name, Sumitomo Chemical Co., Ltd., CI Acid
Black 32), Nippon Leather Black A (trade name, housing
Tomo Chemical Co., Ltd., C.I. I. Acid black 3
8), Sirius Black VE (trade name, Bayer AG, C.I.
Acid Black 51), Chlorantine Fast Gray RLN
(Product name, Ciba-Geigy, CI Acid Black 5
6), Chlorantine Fast Gray 3GLL (trade name, Ciba-Gei
gy, C.I. I. Acid Black 62), Kayarus Supra
Gray VGN (trade name, Nippon Kayaku Co., Ltd., CI Acid
De Black 71), Sumilight Gray G Concentrated
(Product name, Sumitomo Chemical Co., Ltd., CI Acid Bud
Rack 74), Sumilight Supra Gray R Concentrated
(Product name, Sumitomo Chemical Co., Ltd., CI Acid Bud
Rack 76), Sirius Supra Gray GG (trade name, Bayer
AG, C.I. I. Acid Black 77), Cuprofix Gray
2R (trade name, Sandoz, CI Acid Black 9
4), Diacupro Gray 2R (trade name, Mitsubishi Kasei Kogyo Co., Ltd.
Company, C.I. I. Acid Black 105), Diacupro Gre
y B (trade name, Mitsubishi Kasei Co., Ltd., CI Acid
De Black 106), Diacupro Gray B (trade name, Mitsubishi
Kasei Kogyo Co., Ltd., C.I. I. Acid black 10
7), Diacupro Black RY (trade name, Mitsubishi Kasei Co., Ltd. stock)
Company, C.I. I. Acid Black 108), Sirius Sup
ra Gray CG-LL (trade name, Bayer AG, CI Acid
Black 112), Chlorantine Fast Gray NGLL (Product
First name, Ciba-Geigy, C.I. I. Acid Black 113),
Solar Gray 3LR (trade name, Sandoz, CI Acid Bud
Rack 117), Kayarus Supra Gray 3BL (trade name, date
Hon Kayaku Co., Ltd. I. Acid Black 132),
Sirius Supra Gray BLL (trade name, Bayer AG, CI
Acid Black 133), Diacupro Special Black G
U (trade name, Mitsubishi Kasei Co., Ltd., CI Acid
Black 146), Ford Black 2 etc.
It

Preferred examples of the relatively poorly soluble colorant include oil-soluble dyes, disperse dyes, and solvent-soluble pigments. As a more specific example, as a yellow system, 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., C.I. I. Solvent Yellow 29), Oil Yellow 3G (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Yellow 1)
6), Oil Yellow GGS (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Yellow 56),
Varifast Yellow 1101 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Yellow 1105
(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), Oreosol Brilliant Yellow 5G (trade name, Taoka Chemical Industry Co., Ltd.) CI Solvent Yellow 150), Oleosol Fast Yellow 2G (trade name, Taoka Chemical Industry Co., Ltd., CI Solvent Yellow 21), Oleosol Fast Yellow GCN (trade name, Taoka Chemical Industry Co., Ltd.) CI Solvent Yellow 151), Eisenzotte Yellow 1 (trade name, Hodogaya Chemical Co., Ltd., CI Solvent Yellow 56), Eisenzotte Yellow 3 (trade name, Hodogaya Chemical Co., Ltd.) Made by CI Solvent Yellow 16), Aizen Zott Yellow 6 (Product) , Hodogaya Chemical Co., Ltd.,
C. I. Solvent Yellow 33), Aizen spirone yellow GRLH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone yellow 3RH (trade name, Hodogaya Chemical Co., Ltd.), Orazol Yellow 2GLN
(Trade name, manufactured by Ciba Geigy, CI 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,
C. I. Solvent Yellow 25), Olaset Yellow GHS (trade name, manufactured by Ciba Geigy, CI Solvent Yellow 163), Firamid Yellow R (trade name, manufactured by Ciba Geigy, CI Solvent Yellow 2)
1) etc. are mentioned. Oil red 5 for red
B (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI
Solvent Red 27), Oil Red RR (trade name,
Orient Chemical Industry Co., Ltd., C.I. I. Solvent Red 24), Varifast 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 2
303 (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, Orient Chemical Industry Co., Ltd.) Manufactured), 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), 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 red GEH (trade name, Hodogaya Chemical Co., Ltd.), Aizen spirone red CG
H (trade name, Hodogaya Chemical Co., Ltd.), Eisenzod Pink 1 (trade name, Hodogaya Chemical Co., Ltd.,
C. I. Solvent Red 49), Orazol Red 3
GL (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 (trade name, manufactured by Ciba Geigy, C.I.
I. Solvent Red 125), Orazol Red B
(Trade name, manufactured by Ciba Geigy, CI Solvent Red 7), Filamid Red GR (trade name, manufactured by Ciba Geigy, CI Solvent Red 225), Filester Red GA (product name, manufactured by Ciba Geigy, C.I.
Solvent Red 135), Fillester Red RBA
(Trade name, manufactured by Ciba Geigy, CI Solvent Red 230), Orazol Pink 5BLG (trade name, manufactured by Ciba Geigy, CI Solvent Red 127) and the like. Examples of the blue color include oil blue 613 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), oil blue 2N (trade name, manufactured by Orient Chemical Industry Co., Ltd., C.I.
I. Solvent Blue 35), Oil Blue BOS (trade name, manufactured by Orient Chemical Industry 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 3
8), Varifast Blue 1607 (trade name, manufactured by Orient Chemical Industry Co., Ltd.), Varifast Blue 2605
(Trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Blue 70), Varifast Blue 2610
(Trade name, manufactured by Orient Chemical Industry Co., Ltd.), Oleosol Fast Blue ELN (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Blue 70), Oleosol Fast Blue GL (trade name, Taoka Chemical Industry Co., Ltd.) Company made,
C. I. Solvent Blue 70), Oleosol Blue G
(Trade name, manufactured by Taoka Chemical Co., Ltd.), Eisenzod Blue 1 (trade name, manufactured by Hodogaya Chemical Co., Ltd., C.I.
I. Solvent Blue 25), Eisenzotte Blue 2
(Product name, Hodogaya Chemical Co., Ltd., CI Solvent Blue 14), Aizen spirone blue GNH (Product name, Hodogaya Chemical Co., Ltd.), Aizen spirone blue 2BNH (Product name, Hodogaya Chemical Co., Ltd.) Co., Ltd.), Eisenspiron Blue BPNH (trade name, Hodogaya Chemical Co., Ltd.), Orazol Blue GN (trade name, 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 Synthetic Chemical Industry Co., Ltd., Pyramid Blue R (trade name, manufactured by Ciba Geigy, CI Solvent Blue 13)
2), Filer Blue GN (trade name, manufactured by Ciba Geigy, CI Solvent Blue 67) and the like. As a black type, oil black HBB (trade name,
Orient Chemical Industry Co., Ltd., C.I. I. Solvent Black 3), Oil Black 860 (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) Varifast Black 1802 (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., C.I. C. I. 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., C.I. Solvent Black 27), Bali Fast Bu 3830 ((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, Orient Chemical Industry Co., Ltd.) CI Solvent Black 5), Spirit Black AB (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 5),
Nigrosine base (trade name, manufactured by Orient Chemical Industry Co., Ltd., CI Solvent Black 7), oleosol fast black RL (trade name, manufactured by Taoka Chemical Industry Co., Ltd., CI Solvent Black 27), oleosol 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 Chemical Co., Ltd.) Co., Ltd.
C. I. Solvent Book 7), Eisenspiron Black MH (product name, Hodogaya Chemical Co., Ltd.), Eisenspiron Black GMH Special (product name, Hodogaya Chemical Co., Ltd.), Aizenspiron Black R
LH Special (trade name, manufactured by 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.). I.
Solvent Black 29), Oil Black FS Special (trade name, manufactured by Chuo Gosei Kagaku Co., Ltd.) and the like can be mentioned.

As the disperse dye, Oraset Yellow 8
GF (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, Sumitomo Chemical Co., Ltd., CI Disperse Yellow 54), Kayaset Yellow AG (trade name, Nippon Kayaku Co., Ltd., CI Disperse Yellow 54), Sumipura Red B-2 (trade name, manufactured by Sumitomo Chemical Co., Ltd., CI Disperse Red 191), Kayaset Red B (trade name, manufactured by Nippon Kayaku Co., Ltd., CI Disperse Red 60), Fillester Violet BA
(Trade name, manufactured by Ciba Geigy, CI Disperse Violet 57) and the like.

As the solvent-soluble pigment, 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., C.I.
I. Pigment Yellow 3), Fillester Yellow R
NB (trade name, manufactured by Ciba-Geigy, CI Pigment Yellow 147), Kayaset Yellow E-AR (trade name, manufactured by Nippon Kayaku Co., CI Pigment Yellow 147), Kayaset Yellow E-L2R (Trade name, manufactured by Nippon Kayaku Co., Ltd., CI Pigment Yellow 14
2), Permanent Red 4R (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Red 3), Popy Red (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Red 17), Brilliant Fastska Rate (trade name, manufactured by Daido Kasei Co., Ltd., CI Pigment Red 22), 3040 red (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Red 23), fast pink clay 6G (trade name) Manufactured by Noma Chemical Industry Co., Ltd., C.I.
I. Pigment Red 81), Eosin Lake (trade name, manufactured by Arimoto Chemical Industry Co., Ltd., CI Pigment Red 90), 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) and the like.

The amount of the colorant added to the ink composition according to the present invention is preferably about 0.5 to 15% by weight, more preferably about 2 to 10% by weight, based on the ink composition.

[0027]

EXAMPLES The present invention will be explained in more detail by the following examples, but the present invention is not limited to these examples.

The following ink compositions of Examples 1 to 20 and Comparative Examples 1 to 8 were prepared.

Unless otherwise specified, the disintegrant which is the dispersoid of the fine particle dispersion liquid used below has been subjected to the following dispersion process.

Dispersion of disintegrant A mixture of 10 parts of disintegrant and 90 parts of cyclohexane was dispersed for 72 hours in an alumina ball mill using alumina balls. The resulting dispersion was filtered through a 10 μm screen mesh to remove relatively large particles. Cyclohexane was distilled off under reduced pressure, and the disintegrant was dried under vacuum in the presence of phosphoric anhydride.

Example 1 Water-insoluble black colorant Oleosol Black AR (trade name, manufactured by Taoka Chemical Industry Co., Ltd.) (30 g) was added to N-methyl-
2-Pyrrolidone was dissolved in 60 g with stirring and heated to 80 ° C. Fine particle dispersion of water-insoluble cross-linked polyvinylpyrrolidone Kollidon CL-M (trade name, BAS
60 g (manufactured by Company F) was dissolved in 500 g of ion-exchanged water.
To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 2 Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Cr
ospovidone M (trade name, manufactured by BASF) 60
g was dispersed in a solution composed of 350 g of ion-exchanged water and 150 g of ethylene glycol. Add the water-soluble black colorant Aizen Opal B to this solution under stirring.
60 g of rack WGH (trade name, Hodogaya Chemical Co., Ltd.) was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 3 Water-insoluble yellow colorant Kayaset Yellow E-L2R
45 g (trade name, manufactured by Nippon Kayaku Co., Ltd.) is dissolved in 80 g of N, N-dimethylformamide while stirring, and 60
Heated to ° C. Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Crospovidone M 40g
Was dispersed in a solution consisting of 470 g of ion-exchanged water and 50 g of glycerol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 4 Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Cr
50 g of ospovidone M, 45 ion-exchanged water
It was dispersed in a solution consisting of 0 g and 50 g of diethylene glycol. To this solution under stirring, 60 g of a water-soluble yellow colorant, Filerster Yellow RNB (trade name, manufactured by Ciba Geigy), was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 5 Water-insoluble blue colorant Varifast Blue 1607 (trade name, manufactured by Orient Chemical Industry Co., Ltd.) (40 g) was added to N-
Dissolve in 80 g of methyl-2-pyrrolidone with stirring,
Heated to 80 ° C. Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Crospovidone M 60
g was dispersed in a solution composed of 350 g of ion-exchanged water and 150 g of ethylene glycol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 6 Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Ko
llidon CL-M 50 g, ion-exchanged water 42
It was dispersed in a solution consisting of 0 g and 80 g of ethylene glycol. To this solution under stirring, 60 g of a water-soluble blue colorant, Suminol Fast Sky Blue (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 7 Water-insoluble red colorant Varifast Red 1306 (trade name, manufactured by Orient Chemical Industry Co., Ltd.) (30 g) was added to N-
Dissolve in 80 g of methyl-2-pyrrolidone with stirring,
Heated to 60 ° C. Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Crospovidone M 60
g was dispersed in a solution composed of 400 g of ion-exchanged water and 100 g of diethylene glycol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 8 Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Ko
llidon CL-M 60 g, ion-exchanged water 45
It was dispersed in a solution consisting of 0 g and 50 g of glycerol. Add the water-soluble red colorant Be to this solution under stirring.
60 g of nzo Brilliant Red 8BS (trade name, manufactured by Bayer AG) was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 9 35 g of water-insoluble black colorant Spirit Black AB (trade name, manufactured by Orient Chemical Industry Co., Ltd.) was dissolved in 70 g of N-methyl-2-pyrrolidone while stirring, and 8
Heated to 0 ° C. Fine water dispersion of water-insoluble cellulose derivative Croscarmellose sodium
50 g of type A (trade name, manufactured by FMC) was dispersed in a solution composed of 400 g of ion-exchanged water and 100 g of ethylene glycol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 10 Fine Particle Dispersion of Water-Insoluble Cellulose Derivative Crosca
50 g of rmellose sodium type NF (trade name, manufactured by FMC) was dispersed in a solution composed of 400 g of ion-exchanged water and 90 g of diethylene glycol. Add the water-soluble yellow colorant C to this solution under stirring.
arodirect Yellow RL (trade name, C
aroline Color and Chemica
(manufactured by Company I) 60 g was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 11 Water-insoluble red colorant Oleosol Fast Red GL
35 g (trade name, manufactured by Taoka Chemical Industry Co., Ltd.) was dissolved in 70 g of formamide with stirring and heated to 80 ° C. Water-insoluble starch derivative fine particle dispersion HPS-1
70 g of 01 (trade name, manufactured by Nitto Kagaku Co., Ltd.) was dispersed in a solution consisting of 400 g of ion-exchanged water and 90 g of ethylene glycol. To this solution under stirring was added the colorant solution dropwise. After completion of dropping, add 2 more solutions.
After stirring for an hour, an ink composition was obtained.

Example 12 Microparticle dispersion of water-insoluble starch derivative HPS-101
60 g was dispersed in a solution composed of 450 g of ion-exchanged water and 50 g of glycerol. Add the water-soluble blue colorant Kayanol Milli to this solution under stirring.
ng BlueG (trade name, manufactured by Nippon Kayaku Co., Ltd.) 60
g was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 13 Water-insoluble yellow colorant Varifast Yellow 1101
(Trade name, manufactured by Orient Industry Co., Ltd.) 50 g, N-
It was dissolved in 100 g of methyl-2-pyrrolidone with stirring and heated to 80 ° C. Water-insoluble rubber derivative (crosslinked carboxymethyl guar gum, US Pat. No. 4,970,0
40 g (prepared according to No. 78), ion-exchanged water 420
g and 90 g of diethylene glycol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 14 Water-insoluble rubber derivative (crosslinked carboxymethyl guar gum, prepared according to US Pat. No. 4,970,078)
50 g was dispersed in a solution composed of 450 g of ion-exchanged water and 50 g of diethylene glycol. Add the water-soluble red colorant Aizen Ponc to this solution under stirring.
eau RH (trade name, Hodogaya Chemical Co., Ltd.) 5
5 g was added. After the addition is complete, the solution is stirred for a further 2 hours,
An ink composition was obtained.

Example 15 Water-insoluble blue colorant Oraset Blue 2R (trade name,
40 g (manufactured by Ciba Geigy) was dissolved in 90 g of N, N-dimethylformamide with stirring and heated to 60 ° C. Water-insoluble alginic acid A2,830-8 (product number,
50 g of Aldrich) was dispersed in 500 g of ion-exchanged water. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 16 Water-insoluble alginic acid A2,830-8 (product number, Al
50 g of drich) was dispersed in a solution consisting of 450 g of ion-exchanged water and 50 g of diethylene glycol. Add the water-soluble black colorant Su to this solution under stirring.
minol Fast Black BR Conce
imported (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 3
5 g was added. After the addition is complete, the solution is stirred for a further 2 hours,
An ink composition was obtained.

Example 17 Water-insoluble black colorant oil black FS Special A
Dissolve 50 g (trade name, manufactured by Chuo Gosei Co., Ltd.) in 100 g of N-methyl-2-pyrrolidone while stirring,
Heated to ° C. Water-insoluble synthetic ion exchange resin Amberlite IRP-88 (trade name, manufactured by Sigma Chemical Co.) 40 g
400 g of ion-exchanged water and ethylene glycol 1
It was dispersed in a solution consisting of 20 g. To this solution under stirring was added the colorant solution dropwise. After completion of dropping
The solution was further stirred for 2 hours to obtain an ink composition.

Example 18 Water-insoluble synthetic ion exchange resin Amberlite IRP-8
850 g was dispersed in a solution composed of 400 g of ion-exchanged water and 100 g of ethylene glycol. Add the water-soluble red colorant Alizarin to this solution under stirring.
e Rubinol R (trade name, manufactured by Bayer) 60
g was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Example 19 Water-insoluble yellow colorant Oleosol Brilliant Yellow 5G (trade name, manufactured by Taoka Chemical Industry Co., Ltd.) 30 g
-Methyl-2-pyrrolidone was dissolved in 75 g with stirring and heated to 60 ° C. Water-insoluble organic bentonite type S-ben (trade name, manufactured by Tsuchiya Kaolin Industry Co., Ltd.)
30 g was dispersed in a solution composed of 400 g of ion-exchanged water and 100 g of ethylene carbonate. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Example 20 30 g of water-insoluble purified bentonite-based Bengel (trade name, manufactured by Tsuchiya Kaolin Industry Co., Ltd.) was added to ion-exchanged water 4
It was dispersed in a solution consisting of 60 g and 40 g of ethylene glycol. Add the water-soluble blue colorant, Lanyl Violet 4B Extra Co, to this solution under stirring.
35 g of ncentrated (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 1 Water-soluble carboxymethyl cellulose Na salt 36,03
8-4 (product number, Aldrich) 4% aqueous solution 4
50 g of ethylene glycol was added to 50 g, and the mixture was stirred. Add the water-soluble yellow colorant Ca to this solution under stirring.
60 g of roderod Yellow RL was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 2 Water-soluble Na salt of alginic acid 18,094-7 (product number,
20 g of Aldrich) was dissolved in a solution of 450 g of ion-exchanged water and 50 g of diethylene glycol. Add the water-soluble black colorant SuminolFast BR Concentrat to this solution under stirring.
35 g of ed was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 3 Water-insoluble yellow colorant Kayaset Yellow E-L2R
45 g was dissolved in 80 g of N, N-dimethylformamide with stirring and heated to 60 ° C. Water-soluble polyvinylpyrrolidone Kollidon 12PF (trade name, B
15 g of ASF) was dissolved in a solution containing 500 g of ion-exchanged water and 20 g of glycerol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 4 Water-insoluble blue colorant Oraset Blue 2R (trade name,
40 g (manufactured by Ciba Geigy) was dissolved in 90 g of N-methyl-2-pyrrolidone with stirring and heated to 60 ° C. Water-insoluble crystalline cellulose, graded grade Avicel PH-M15 (trade name, manufactured by Asahi Kasei Corporation) 40 g
Was dispersed in 500 g of ion-exchanged water. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 5 Water-insoluble crosslinked polyvinylpyrrolidone fine particle dispersion Ko
Ilidon CL-M (not subjected to the above dispersion step, used as it is on the market) 60 g, ion-exchanged water 450
g and 50 g of glycerol. Add the water-insoluble red colorant B to this solution under stirring.
enzo Brilliant Red 8BS 60g
Was added. After the addition was completed, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 6 Water-insoluble blue colorant, Oraset Blue 2R, 30 g
Was dissolved in 75 g of N-methyl-2-pyrrolidone with stirring and heated to 60 ° C. 30 g of a water-insoluble organic bentonite type esben (not subjected to the above-mentioned dispersion step, used as it is on the market) was dispersed in a solution consisting of 400 g of ion-exchanged water and 100 g of ethylene carbonate. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 7 Xanthine gum 28,602-8 (product number, Aldr
ich) water-insoluble rubber derivative was carboxymethylated by reacting this xanthine gum with monochloroacetic acid under caustic conditions. From the stoichiometric ratio of monochloroacetic acid and xanthine gum, the degree of substitution was about 40%. Crosslinking of carboxymethylated xanthine gum is 56
Concentrated hydrochloric acid in acetone at ° C was added to this xanthine gum in an amount such that the ratio of hydrochloric acid to xanthine gum was 1:10. The product was washed thoroughly with water and dried over anhydrous phosphorus under reduced pressure.

The water-insoluble rubber derivative (that is, crosslinked carboxymethylxanthine gum) thus obtained was dispersed with a ball mill to prepare a fine particle dispersion.

Water-insoluble yellow colorant Varifast Yellow 1101 (50 g) was added to N-methyl-2-pyrrolidone 1
It was dissolved in 100 g with stirring and heated to 80 ° C. 40 g of the fine particle dispersion liquid obtained as described above was dispersed in a solution composed of 420 g of ion-exchanged water and 90 g of diethylene glycol. To this solution under stirring was added the colorant solution dropwise. After the completion of the dropping, the solution was further stirred for 2 hours to obtain an ink composition.

Comparative Example 8 A dispersion ink composition was prepared as follows according to the method described in JP-A-62-53385. The disperse dye Kayaset Red B-2 (trade name, manufactured by Nippon Kayaku Co., Ltd.) was purified to 95%. 25g of this dye
20 g of anionic surfactant Demol-N (trade name, manufactured by Kao Corporation), ethylene glycol 75 g, diethylene glycol 65 g, and ion-exchanged water 325.
It was subjected to a dispersion treatment with an alumina ball mill for about 36 hours. The pH of the dispersion was adjusted to 8.3 with a 0.01 M sodium hydroxide solution, and the dispersion was further treated for 3 hours. The dispersion was passed through a 10 μm screen mesh to remove large particles, and an ink composition was obtained.

Measurement of Solubility of Disintegrant The solubility of the disintegrant added to the ink compositions of the above Examples and Comparative Examples was measured as follows. First, 1 g of the disintegrant was put in a mixed solution of 100 ml of distilled water and N-methyl-2-pyrrolidone at 9: 1 and boiled for 4 hours. The solution was cooled to room temperature and then centrifuged at 10,000 rpm for 2 hours. The supernatant was filtered (Teflon filter, average pore size 1 μm), and 50 ml of the filtrate was placed in a bottle whose weight was previously measured. The solvent was evaporated by standing for 10 days, and the remaining solvent was distilled off under reduced pressure. Then, the bottle was dried under reduced pressure at 120 ° C. for 48 hours. The weight of the bottle was measured again, and from the difference between the weight of the bottle and the weight of the bottle measured earlier, water and N
The solubility (g / l) in a 9: 1 mixed solution with -methyl-2-pyrrolidone was determined. That is, the solubility (g /
l) = [weight difference (g) × (100 ml / 50 ml) /
0.1 (l)]. The results were as shown in Table 1.

Measurement of Particle Size Distribution of Disintegrant The particle size distribution of the disintegrant added to the ink compositions of the above Examples and Comparative Examples was measured by Malvern 3600E Particle Sizer.
(Malvern, Southborough, Massachusetts, USA)
It measured using. This device measures the particle size distribution by scattering laser light, and can measure the average particle size and the particle size distribution in the range of about 0.5 μm to 500 μm. The disintegrant was measured as a dispersion in cyclohexane without water swelling. The results were as shown in Table 1.

Measurement of the degree of hydration of the disintegrant 2 g of the disintegrant added to the ink compositions of the above Examples and Comparative Examples was added to 40 ml of ion-exchanged water in a 100 ml centrifuge tube whose weight was previously measured. The centrifuge tube was capped and shaken vigorously for 10 minutes to obtain a homogeneous dispersion. This dispersion was allowed to stand for 10 minutes and then vigorously shaken again for 10 minutes. The centrifuge tube was centrifuged for 15 minutes at 2000 rpm. The supernatant was decanted, the tube was weighed and the hydrated disintegrant in the centrifuge tube was weighed. The hydration degree was calculated from the following formula. Degree of hydration = (weight of hydrated disintegrant / dry weight of disintegrant) The results were as shown in Table 1.

Evaluation of Continuous Printing Performance of Ink Composition Using the ink compositions of the above-mentioned Examples and Comparative Examples, continuous printing was carried out for 24 hours using an inkjet printer MJ-500 (manufactured by Seiko Epson Corporation). The printing environment was 25 ° C. and the relative humidity was 30%. The weight of the ink printed on one sheet of recording paper was measured 5 times in total after 5 minutes of printing and then every 6 hours. The average value of the five measured values of the measured ink weight per recording paper was determined, and the deviation of each measured value from the average value was determined. And the maximum deviation was evaluated as follows. That is, the maximum deviation is less than 4%: ◎ -The maximum deviation is 4% or more and less than 8%: ○ -The maximum deviation is 8% or more and less than 15%: △ -The maximum deviation is 15% or more: × It was as shown in Table 1.

Evaluation of Clogging Characteristic 1 Using the ink compositions of the above-mentioned Examples and Comparative Examples, printing was carried out for 30 minutes using an inkjet printer MJ-500. The printing environment was 25 ° C. and the relative humidity was 30%. After printing, remove the recording head from the printer, 4
10 in an environment of 0 ° C and relative humidity of 30% without a cap
Left for days. After that, the recording head was mounted on the printer again, and printing was performed after the cleaning operation. The number of cleaning operations and the ink ejection state were evaluated as follows.
In the case of all the ink compositions, the number of cleanings until the ink is ejected from all the nozzles is 1 time: ◎ 2 or 3 times: ○ 3 to 10 times: △ 10 nozzles that do not eject remain: × The results are shown in Table 1.

Evaluation 2 of Clogging Property 2 The same test as the evaluation 1 of the clogging property was conducted except that the recording head was removed from the printer and placed in an environment in which the temperature of 40 ° C. was changed to the temperature of 60 ° C. The result is
It was as shown in Table 1.

[0067]

[Table 1]

[0068]

[Table 2]

Claims (5)

[Claims] 1. An ink composition for ink jet recording comprising at least a colorant, a water-soluble organic solvent, water, and a water-insoluble disintegrating agent having a property of swelling when contacted with water. 2. The hydration degree of the disintegrant (wherein the hydration degree is the ratio of the weight of the hydrated disintegrant to the dry weight of the disintegrant) is 2 or more. Ink composition. 3. The disintegrant has a solubility of 0.2 g / l in a mixed solution of water: N-methyl-2-pyrrolidone 9: 1.
The ink composition according to claim 1, wherein: 4. The ink composition containing the disintegrant as particles, 90% or more of the particles having a particle size of less than 10 μm, and 99% or more of the particles having a particle size of less than 20 μm. Ink composition. 5. A water-insoluble polyvinylpyrrolidone in which the disintegrant is physically or chemically crosslinked; a water-insoluble cellulose; a water-insoluble wood substance; a water-insoluble cellulose derivative and a salt thereof; a water-insoluble starch; Water-insoluble derivatives thereof and salts thereof; water-insoluble natural rubbers and derivatives thereof and salts thereof; alginic acid and derivatives thereof and salts thereof; ion exchange resins; water-insoluble inorganic substances; natural sponges; citrus pulp; The ink composition according to claim 1, which is selected from the group consisting of organic cotton derivatives.