JP3346755B2 - Color ink composition, ink composition excellent in color reproducibility and light fastness, and recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition used for color ink jet recording, and more particularly, to a yellow ink composition, a magenta ink composition and a cyan ink composition, and a solvent system suitable for the color ink composition. And a color inkjet recording method using the ink composition.

[0002]

2. Description of the Related Art In a so-called color ink jet recording method for forming a color image using an ink jet recording method, at least a yellow ink, a magenta ink and a cyan ink are generally used. In the color ink jet recording method, it is first important that the ink composition of each color has good color reproducibility. In particular, it is preferable that good colors can be reproduced even on plain paper, and it is particularly preferable that good colors can be reproduced even on acidic paper.

Further, among the color ink jet recording methods, in addition to three colors of yellow, magenta and cyan,
There is a method in which yellow, magenta, and cyan inks are layered to form red, green, and blue, and even black, and color printing is performed with a total of seven colors (for black, yellow, magenta, and cyan are superimposed). There is also a method of preparing a black ink and using it, other than the method of obtaining by striking).

In such a color ink jet recording method, in addition to the color reproducibility of the ink alone, good reproducibility of red, green, and blue tones when printed in an overlapping manner is important. Even if an ink composition having good color reproducibility by itself is used, good color reproducibility may not be expected even after color mixing by overstrike, and as a result of color mixing, good color is obtained on coated paper. Even if reproducibility can be realized, it is often observed that recording paper having high acidity still has poor color reproducibility. Therefore, it can be said that there is a need for an ink composition and a combination thereof that can obtain good color reproduction without being affected by the paper quality of the recording paper even after color mixing.

The color ink composition used for ink-jet recording also has the performance generally required of ink-jet recording ink compositions, such as not causing clogging of nozzles and changing the composition and physical properties during storage. It is necessary to meet. In particular, it is desired that after the printing is stopped for a certain period of time and the printing is restarted thereafter, the flying of the ink droplets and the missing dots do not occur. That is, it is desirable that the “pause time” until the disturbance of the ink droplet flight or missing dots is observed is long. Such an ink composition having a long pause time may be hereinafter referred to as an ink having excellent intermittent ejection stability.

[Summary of the Invention] The present inventors have recently obtained some knowledge on an ink composition which satisfies various characteristics required for an ink composition for color inkjet recording. The present invention is based on these findings.

That is, in the first aspect of the present invention, an object of the present invention is to provide a yellow ink composition having excellent color reproducibility.

[0008] The present invention also provides, in a second aspect thereof,
An object of the present invention is to provide a magenta ink composition having excellent color reproducibility. In the third aspect of the present invention, an object of the present invention is to provide a shear ink composition having excellent color reproducibility. Further, in the fourth aspect of the present invention, an object of the present invention is to provide a solvent system suitable for a color ink composition. Still another object of the present invention, in the fifth aspect, is to provide a color ink jet recording method for realizing a good color printed image using the ink composition.

Therefore, the yellow ink composition according to the first aspect of the present invention has a C.I. I. Direct Yellow 86 and C.I. I. Direct Yellow 132 and 1: 3-3:
At a weight ratio of 1 and 0.3% based on the ink composition.
〜3.0% by weight.

The magenta ink composition according to the second aspect of the present invention comprises C.I. I. Acid Red 52 and C.I.
I. Acid Red 289 at a weight ratio of 1: 2 to 2: 1 and each of 0.3 to 2.5 based on the ink composition.
% By weight.

The shear ink composition according to the third aspect of the present invention comprises C.I. I. Direct Bull 199, C.I. I.
Direct Blue 86, and C.I. I. One or more dyes selected from the group consisting of Acid Blue 9
-4% by weight.

Further, the color ink composition according to the fourth aspect of the present invention is represented by at least water, a dye, a hydrophilic high-boiling low-volatile solvent, a polyhydric alcohol lower alkyl ether, and the following formula (I). 7 to 12% by weight, preferably 7 to 10% by weight of a lower alkyl ether of a polyhydric alcohol, and 0.5 to 1.2% by weight of an acetylene glycol of the following formula (I). Is 0.5 to 1% by weight.

[0013]

Embedded image (Where R ¹ , R ² , R ³ , and R ⁴ each independently represent a C _1-6 alkyl group, and n + m represents 0 to 30). Further, the color according to the fifth aspect of the present invention. The ink jet recording method is a color ink jet recording method using a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the yellow ink composition of the first embodiment is used as a yellow ink composition, and a magenta ink composition. A method comprising using each of the magenta ink compositions of the second embodiment as an ink composition.

DETAILED DESCRIPTION OF THE INVENTION The yellow ink composition according to the first embodiment of the present invention comprises C.I. I. Direct Yellow 86 and C.I. I. Direct Yellow 1
32 and 1: 3 to 3: 1, preferably 1: 2 to 2: 1,
Weight ratio, and each is 0.3 to 0.3 based on the ink composition.
3.0% by weight, preferably 0.5 to 2.0. According to the yellow ink composition of the present invention, it is possible to reproduce an ideal yellow color tone.
In particular, an ideal color tone can be obtained on plain paper, especially on plain acidic paper. However, if the addition amount of the two dyes is out of the above range, the color becomes yellowish or reddish yellow by itself, and the reproduction of the ideal yellow color tone cannot be obtained. And green color reproduction cannot be obtained. Further, there is a possibility that a large difference occurs in color reproducibility between ordinary neutral paper and ordinary acidic paper. Further, clogging may easily occur in the ink ejection port of the recording head.

The magenta ink composition according to the second aspect of the present invention comprises C.I. I. Acid Red 52 and C.I. I. Acid Red 289 at a weight ratio of 1: 2 to 2: 1, preferably 2: 3 to 3: 2, and 0.3 to 3.5% by weight, preferably 0%, based on the ink composition. 0.5 to 2.5 is used. According to the magenta ink composition according to the present invention, it is possible to reproduce an ideal magenta color tone. In particular, an ideal color tone can be obtained on plain paper, especially on plain acidic paper. However, when the addition amount of the two dyes is out of the above range, the magenta becomes bluish or reddish alone, and the reproduction of an ideal magenta color tone cannot be obtained. Blue color reproduction cannot be obtained. Further, there is a possibility that a large difference occurs in color reproducibility between ordinary neutral paper and ordinary acidic paper. Further, clogging may easily occur in the ink ejection port of the recording head.

Further, the cyan ink composition according to the third aspect of the present invention comprises C.I. I. Direct Blue 199, C.I.
I. Direct Blue 86, and C.I. I. It contains one or more dyes selected from the group consisting of Acid Blue 9 in an amount of 1 to 4% by weight, preferably 1.5 to 3.5% by weight. According to the cyan ink composition of the present invention, an ideal color tone can be obtained even on plain paper, especially plain acidic paper.

The solvent system of the yellow ink composition, magenta ink composition and cyan ink composition according to the present invention is not particularly limited, but preferably contains an organic solvent capable of dissolving the above-mentioned dye and water.

Specific examples of preferable organic solvents include, for example, amides such as dimethylformamide and dimethylacetamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; ethylene glycol and propylene glycol Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as triethylene glycol and diethylene glycol; glycerin; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl Polyhydric alcohol lower monoalkyl ether such as (or ethyl) ether and triethylene glycol monomethyl (or ethyl) ether Lower polyalkyl alcohols such as triethylene glycol dimethyl (or ethyl) ether; alkyl alcohols having 1 to 5 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and n-butyl alcohol; sulfolane , Pyrrolidone, N-methyl-2-pyrrolidone, 1,
3-dimethyl-2-imidazolidinone, 1,5-pentanediol and the like. These organic solvents can be used alone or as a mixture.

Further, the ink composition may further contain various additives as a third component in order to improve various characteristics. For example, for the purpose of preparing various physical properties such as viscosity, surface tension, pH, specific resistance, etc., and preserving and preventing mold, anionic diameter interface of fatty acid salt, alkyl sulfate ester salt, alkyl benzene sulfonic acid, alkyl naphthalene sulfonate, etc. Activator; acetylene glycols, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester,
Nonionic surfactants such as sorbitan fatty acid esters;
Water-soluble natural or synthetic polymers such as celluloses, polyvinylpyrrolidone, polyvinyl alcohol, and water-soluble resins; diethanolamine, triethanolamines;
Inorganic salts of lithium chloride, ammonium chloride, sodium chloride and the like can be added.

Further, according to a fourth aspect of the present invention, there is provided an ink composition comprising a solvent system suitable for a color ink composition. According to a preferred embodiment of the present invention, a more excellent ink composition can be obtained by combining the solvent system of the fourth embodiment with the yellow, magenta, and cyan ink compositions according to the first to third embodiments. it can.

By combining the solvent system of this embodiment with the colorant system used in the first to third embodiments, an ink composition having excellent intermittent ejection stability can be obtained. Specifically, such a combination can provide an excellent ink composition having a “pause time” of more than 20 seconds. When an ink composition having excellent intermittent ejection stability is used, a so-called flushing operation (an operation in which ink is ejected from a nozzle at regular intervals, which is performed to maintain the physical properties of the ink composition near the nozzle constant) This is extremely advantageous because the number of times of performing can be reduced.

However, the colorant of the ink composition according to the fourth embodiment is not limited to the systems used in the first to third embodiments, and may be used in combination with a wide range of coloring systems. It is possible.

First, the ink composition according to the fourth aspect of the present invention first comprises a polyhydric alcohol lower alkyl ether. Preferred specific examples of the polyhydric alcohol lower alkyl ether include mono, di and triethylene glycol C _1-6 alkyl ether, mono, di and tripropylene glycol C _1-6 alkyl ether, more preferably triethylene glycol monobutyl ether,
Examples thereof include diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and propylene glycol monobutyl ether. Most preferred is triethylene glycol monobutyl ether.

This amount is preferably 7 to 12% by weight, more preferably 7 to 10% by weight.

Further, the ink composition according to the fourth aspect of the present invention comprises the acetylene glycol represented by the above formula (I). Preferred specific examples of acetylene glycol are shown in the following table.

R ¹ R ² R ³ R ⁴ n + m No. 1 iso-butyl methyl methyl iso-butyl 10 No. 2 iso-butyl methyl methyl iso-butyl 3.5 No. No. 3 ethyl methyl methyl ethyl 10 No. No. 4 methyl methyl methyl methyl 0 No. No. 5 ethyl methyl methyl ethyl 0 No. 6 iso-butyl methyl methyl iso-butyl One acetylene glycol is most preferred.

As these acetylene glycols, commercially available ones can be used. For example, Surfynol 440, 465, 82, and TG (manufacturer:
AirProduct and Chemicals, Inc., sales agency: Shin-Etsu Chemical Co., Ltd.) can be used.

The amount of acetylene glycol added is 0.5 to
It is preferably 1.2% by weight, more preferably 0.1% by weight.
5 to 1% by weight.

By using the lower alkyl ether of polyhydric alcohol and acetylene glycol in combination in the above-mentioned amounts, the quick drying property of the ink composition can be improved, and the deterioration of print quality due to bleeding or color mixing can be prevented. Further, when a polyhydric alcohol lower alkyl ether is used alone, a phenomenon that the resin constituting the recording head and the ink flow path is eroded is often observed, but in combination with acetylene glycol, such a phenomenon is observed. The erosion phenomenon can also be prevented. Further, by adding 50% by weight or more of a hydrophilic high-boiling point low-volatile solvent described below to the polyhydric alcohol lower alkyl ether,
The effect can be further improved.

Further, in the case of color printing, if dots begin to flow and color mixing or the like occurs between adjacent dots, the quality of a color image will be degraded. According to the combination of polyhydric alcohol lower alkyl ether and acetylene glycol, such color mixing can be prevented, and a high-quality color image can be realized.

The coloring components of the ink used in the present invention include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, and oil dyes. And any of them can be used. Among them, a water-soluble dye is preferably used from the viewpoint of the performance of the recording liquid. I. Direct Red 2, 4, 9, 23, 26, 3
1, 39, 62, 63, 72, 75, 76, 79, 8
0, 81, 83, 84, 89, 92, 95, 111, 1
73, 184, 207, 211, 212, 214, 21
8, 221, 223, 224, 225, 226, 22
7,232,233,240,241,242,24
3, 247, C.I. I. Direct violet 7, 9, 47, 48,
51, 66, 90, 93, 94, 95, 98, 100,
101, C.I. I. Direct Yellow 8, 9, 11, 12, 2
7, 28, 29, 33, 35, 39, 41, 44, 5
0, 53, 58, 59, 68, 86, 87, 93, 9
5, 96, 98, 100, 106, 108, 109, 1
10, 130, 132, 142, 144, 161, 16
3, C.I. I. Direct Blue 1, 10, 15, 22, 2
5, 55, 67, 68, 71, 76, 77, 78, 8
0, 84, 86, 87, 90, 98, 106, 108,
109, 151, 156, 158, 159, 160, 1
68, 189, 192, 193, 194, 199, 20
0, 201, 202, 203, 207, 211, 21
3, 214, 218, 225, 229, 236, 23
7, 244, 248, 249, 251, 252, 26
4, 270, 280, 288, 289, 291, C.I. I. Direct Black 9, 17, 19, 22, 3
2, 51, 56, 62, 69, 77, 80, 91, 9
4, 97, 108, 112, 113, 114, 117,
118, 121, 122, 125, 132, 146, 1
54, 166, 168, 173, 199, C.I. I. Acid Red 35, 42, 52, 57, 6
2, 80, 82, 111, 114, 118, 119, 1,
27, 128, 131, 143, 151, 154, 15
8, 249, 254, 257, 261, 263, 26
6,289,299,301,305,336,33
7, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47,
48, 90, 103, 126, C.I. I. Acid Yellow 17, 19, 23, 25, 3
9, 40, 42, 44, 49, 50, 61, 64, 7
6, 79, 110, 127, 135, 143, 151,
159, 169, 174, 190, 195, 196, 1
97, 199, 218, 219, 222, 227; I. Acid Blue 9, 25, 40, 41, 62,
72, 76, 78, 80, 82, 92, 106, 11
2,113,120,127: 1,129,138,1,
43, 175, 181, 205, 207, 220, 22
1, 230, 232, 247, 258, 260, 26
4, 271, 277, 278, 279, 280, 28
8, 290, 326; I. Acid Black 7, 24, 29, 48, 5
2: 1, 172, C.I. I. Reactive Red 3, 13, 17, 19, 2
1, 22, 23, 24, 29, 35, 37, 40, 4
1, 43, 45, 49, 55, C.I. I. Reactive Violet 1, 3, 4, 5,
6, 7, 8, 9, 16, 17, 22, 23, 24, 2,
6, 27, 33, 34, C.I. I. Reactive Yellow 2, 3, 13, 14, 1
5, 17, 18, 23, 24, 25, 26, 27, 2,
9, 35, 37, 41, 42, C.I. I. Reactive Blue 2, 3, 5, 8, 10, 1
3, 14, 15, 17, 18, 19, 21, 25, 2
6, 27, 28, 29, 38, C.I. I. Reactive Black 4, 5, 8, 14, 2
1, 23, 26, 31, 32, 34, C.I. I. Basic Red 12, 13, 14, 15, 1
8, 22, 23, 24, 25, 27, 29, 35, 3,
6, 38, 39, 45, 46, C.I. I. Basic violet 1, 2, 3, 7, 1
0, 15, 16, 20, 21, 25, 27, 28, 3
5, 37, 39, 40, 48, C.I. I. Basic Yellow 1, 2, 4, 11, 13,
14, 15, 19, 21, 23, 24, 25, 28, 2
9, 32, 36, 39, 40, C.I. I. Basic Blue 1, 3, 5, 7, 9, 22,
26, 41, 45, 46, 47, 54, 57, 60, 6
2, 65, 66, 69, 71, C.I. I. Basic Black 8 and the like.

The amount of the dye is determined depending on the type of the dye, the type of the solvent component, the characteristics required for the ink, and the like.
The range is preferably from 15 to 15 wt%, more preferably from 0.5 to 10 wt%. Examples of the hydrophilic high-boiling low-volatile solvent used in the present invention include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol, and high-boiling volatile solvents such as polypropylene glycol. N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, Nn Water-soluble organic solvents such as nitrogen-containing organic solvents such as -butyldiethanolamine, triisopropanolamine, and triethanolamine can be added within a range that does not cause printing bleeding. Particularly, diethylene glycol, glycerin and the like are preferable. It is well known that these hydrophilic high-boiling low-volatile solvents are added as humectants to prevent clogging and the like, but the greatest effect as an essential component of the present invention is to reduce the erosion of members. is there. In particular, when a volatile component such as water evaporates in the head or in the ink supply path due to occurrence of an abnormal situation due to a failure of the printing apparatus or the like, the member erosion of the polyhydric alcohol lower alkyl ether is reduced. Further, according to a preferred embodiment of the present invention, the ink composition preferably further contains benzotriazole. The addition of this benzotriazole is a type of printer in which the ink composition is supplied from the ink container to the recording head, where the ink absorber is placed in the ink container, and the ink composition is absorbed and impregnated into the ink absorber. This is extremely advantageous for a printer that is held and held. Generally, a porous foam such as urethane foam is used as the ink absorber in the ink container. However, the catalyst, the foaming agent, and the regulator used in the production process are often used from these absorbers. A phenomenon in which the foaming agent and other additives were dissolved in the ink composition was observed. These dissolved components change the physical properties of the ink (for example,
Or the contact angle changes). Furthermore, these components change the physical properties of the ink flow path and the nozzle surface, and may impair the ejection stability of the ink droplets. These phenomena can be effectively prevented by adding benzotriazole to the ink composition.

As the recording head, a recording head whose nozzle surface has been subjected to a water-repellent treatment for stable ejection of ink droplets is used. For this water-repellent treatment, eutectoid plating using, for example, a nickel-fluorine-based polymer is generally used (for example, a treatment described in European Patent Publication 0506128A1 is preferable. That is, an ink discharge nozzle is formed). (A water-repellent treatment obtained by electroplating a nickel electroformed plate in a nickel plating solution in which polytetrafluoroethylene (PTFE) is dispersed at a concentration of about 20% is preferable.) In this water-repellent treatment, a phenomenon that deterioration of the water-repellent treatment is accelerated by polyhydric alcohol lower alkyl ether, acetylene glycol or the like may be observed. The addition of benzotriazole is also advantageous in that the water repellent treatment of the nozzle surface can be effectively prevented from deteriorating.

An ink jet recording method according to a fifth aspect of the present invention comprises:
The color inkjet recording is performed by a combination of the magenta ink according to the second aspect and a specific cyan ink. In the present invention, the color inkjet recording method is not particularly limited, especially yellow,
In addition to the three colors magenta and cyan, printing any two of the three colors overlaid to form red, green, and blue, and then overlapping three colors or using black ink to reproduce black The printing method using a total of seven colors is preferably adopted as the ink jet recording method according to the present invention. The yellow ink according to the first and second embodiments, the magenta ink, and the cyan ink according to the third embodiment, in addition to being excellent in color reproducibility in each case, also include any two of the ink compositions. This is because, by overprinting, red, green, and blue close to the ideal color tone can be obtained without being affected by the quality of the recording paper. That is,
Red obtained by superposing yellow ink and magenta ink, green obtained by superposing yellow ink and cyan ink, and blue obtained by superposing magenta ink and cyan ink are of paper quality (for example, This is because each color is reproduced as very close to the ideal color tone on various types of recording paper without being affected by ordinary recording paper having high acidity. That is, good color reproducibility can be obtained regardless of the recording material.

Further, according to a preferred embodiment of the present invention, the ejection amounts of the yellow ink, magenta ink and cyan ink may be the same in forming red, green or blue. Normally, in the overprinting of the ink compositions as described above, the red, green, and blue colors are adjusted by adjusting the ejection amounts of the yellow, magenta, and cyan ink compositions from the nozzles for each color tone. Although this is theoretically possible, it is complicated and impractical. That is, it is not practical to make the ejection amount of yellow ink different between red and green. Therefore, the ejection amounts of the yellow, magenta, and cyan inks are kept constant, and red,
The present invention that can reproduce green and blue can be said to be very advantageous.

The physical properties of the above ink composition, particularly the ink composition according to the fourth aspect of the present invention, are determined by the composition and can be appropriately determined in consideration of some requirements. Surface tension is 29mN / m
It is preferable that this is the case.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following,% represents% by weight.

Example A The following yellow ink composition was prepared.

Example A1 C.I. I. Direct Yellow 86 0.3% C.I. I. Direct Yellow 132 0.9% (weight ratio 1: 3) Glycerin 5% Water Remaining

Example A2 C.I. I. Direct Yellow 86 1% C.I. I. Direct Yellow 132 2% (addition weight ratio 1: 2) Ethylene glycol 10% Surfynol 465 1% Water remaining amount

Example A3 C.I. I. Direct Yellow 86 1% C.I. I. Direct Yellow 132 1% (addition weight ratio 1: 1) Glycerin 5% Ethylene glycol 5% Water Remaining

Example A4 C.I. I. Direct Yellow 86 2% C.I. I. Direct Yellow 132 3% (additional weight ratio 2: 3) Glycerin 5% Diethylene glycol 10% Surfynol 465 1% Water remaining amount

Example A5 C.I. I. Direct Yellow 86 3% C.I. I. Direct Yellow 132 1% (addition weight ratio 3: 1) Glycerin 5% Polyethylene glycol # 200 5% Water Remaining

Comparative Example A1 C.I. I. Direct Yellow 86 2% Glycerin 5% Water Remaining

Comparative Example A2 C.I. I. Direct Yellow 132 2% Diethylene glycol 10% Water Remaining

Comparative Example A3 C.I. I. Direct Yellow 86 0.2% C.I. I. Direct Yellow 132 0.2% Glycerin 5% Diethylene glycol 5% Surfynol 465 1% Water remaining

Comparative Example A4 C.I. I. Direct Yellow 86 4% C.I. I. Direct Yellow 132 1% Polyethylene glycol # 200 10% Water Remaining

Comparative Example A5 C.I. I. Direct Yellow 86 4% C.I. I. Direct Yellow 132 4% Glycerin 5% Ethylene glycol 5% Surfynol 465 1% Water Remaining The ink composition was mixed with the above components, stirred at 60 ° C. for 2 hours to dissolve, and then a 0.8 μm diameter membrane was used. It was prepared by filtration under pressure of ² kg / cm ² using a filter.

Evaluation Test A The yellow ink compositions obtained in Examples A1-5 and Comparative Examples A1-5 were evaluated as follows. The printing was performed with a discharge nozzle diameter of 30 μm, a piezoelectric element driving voltage of 80 V,
The test was performed using a prototype 48 nozzle inkjet printer adjusted to a driving frequency of 3 kHz, a resolution of 360 dots / inch, and an ink ejection amount of 0.08 μg / dot.

Evaluation A1 : Color Reproducibility (Coated Paper) A solid (100% duty) printed image (3 × 3 cm) was formed on each of the yellow inks on an inkjet paper IJ mat coat NM (manufactured by Mitsubishi Paper Mills) having a coat layer. Formed. The color reproducibility of yellow is determined by the CIE (Commision Internationale de I'Ecl)
the color difference indication method specified in airage) L ^* a ^* b ^* color system of Macbeth CE-7000 spectrophotometer (Ma
cbeth), the measured value and ISO 2
845-1975 yellow color tone reference value (L ^* = 9
0.7, a ^* =-18.8, b ^* = 91.1) were obtained from the following equation (I). ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δ
b ^* ) ² ] ^1/2 (I) The obtained color differences are as described in Table 1 below. In the table, the color difference ΔE ^* ab was determined based on the following criteria. Color difference ΔE ^* ab is less than 5-good (○) 5 or more-bad (x)

Evaluation A2 : Color Reproducibility (Plain Paper, Neutral Paper, Acidic Paper) In the same manner as in Evaluation A1, a solid print image was formed on the next plain paper (neutral and acidic paper). Recording paper used for evaluation Xerox-R (Fuji Xerox Co., Ltd., neutral paper) Neenah bond (25% cotton fiber,
Neneah bond, acid paper) Canon Dry (Canon Sales, acid paper) EPP (Epson Sales, acid paper) Xerox 4024 3R721 (Xerox, acid paper) Conqueror (100 g / m ² ) (ArjoWi)
gging company, neutral paper) The color reproducibility of this solid printing was evaluated in the same manner as in Evaluation A1, except that the color difference was determined based on the printing on Xerox-P paper. The color difference and its determination are as described in Table 1.

Evaluation A3 : Discharge stability (clogging of nozzles) A printing operation was performed using each yellow ink composition, and it was confirmed that ink droplets were discharged from all nozzles. afterwards,
The printer was left in a temperature environment of 40 ° C. without capping the recording head. One month later, the printing state when the printing operation was performed was evaluated as follows. -Normal printing was performed immediately or within 3 times of the recovery operation (cleaning operation by absorbing about 1 cc by the pump)-good (○)-Normal printing was performed after 4 to 10 recovery operations-somewhat poor (△)-Normal printing was performed after 11 or more recovery operations, or normal printing was not restored-defective (x)

[Table 1]

Example B Next, the following magenta ink composition was prepared.

Example B1 C.I. I. Acid Red 52 0.3% C.I. I. Acid Red 289 0.6% Diethylene glycol 20% Proxel XL2 0.5% (Preservative: manufactured by ZENECA) Water

Example B2 C.I. I. Acid Red 52 1% C.I. I. Acid Red 289 2% Diethylene glycol 10% Glycerin 13% Proxel XL2 0.5% Water Remaining

Example B3 C.I. I. Acid Red 52 1% C.I. I. Acid Red 289 1% Diethylene glycol 15% Surfynol 465 1% Proxel XL2 0.5% Water Remaining

Example B4 C.I. I. Acid Red 52 2.5% C.I. I. Acid Red 289 1.3% Glycerin 15% Polyethylene glycol (# 200) 10% Proxel XL2 0.5% Water Remaining

Example B5 C.I. I. Acid Red 52 0.9% C.I. I. Acid Red 289 0.6% Diethylene glycol 15% Triethylene glycol monobutyl ether 10% Proxel XL2 0.3% Water Remaining

Example B6 C.I. I. Acid Red 52 0.9% C.I. I. Acid Red 289 0.7% Glycerin 10% Triethylene glycol 10% Surfynol 465 1.5% Proxel XL2 0.3% Water Remaining

Example B7 C.I. I. Acid Red 52 1.2% C.I. I. Acid Red 289 0.8% Glycerin 10% Diethylene glycol 5% Triethylene glycol monobutyl ether 10% Proxel XL2 0.5% Water Remaining

Example B8 C.I. I. Acid Red 52 0.7% C.I. I. Acid Red 289 0.7% Glycerin 15% Polyethylene glycol (# 200) 10% Proxel XL2 0.3% Water Remaining

Comparative Example B1 C.I. I. Acid Red 52 2% Glycerin 15% Proxel XL2 0.5% Water Remaining

Comparative Example B2 C.I. I. Acid Red 289 2% Diethylene glycol 20% Proxel XL2 0.3% Water Remaining

Comparative Example B3 C.I. I. Acid Red 52 0.2% C.I. I. Acid Red 289 0.2% Glycerin 10% Diethylene glycol 15% Proxel XL2 0.5% Water Remaining

Comparative Example B4 C.I. I. Acid Red 52 0.5% C.I. I. Acid Red 289 2% Glycerin 10% Polytriethylene glycol (# 200) 15% Proxel XL2 0.5% Water Remaining

Comparative Example B5 C.I. I. Acid Red 52 3% C.I. I. Acid Red 289 3% Glycerin 10% Triethylene glycol 15% Proxel XL2 0.3% Water Remaining The ink composition was mixed with the above components, stirred at 70 ° C. for 2 hours and dissolved to obtain 0.8 μm. It was prepared by filtration under pressure at a pressure of ² kg / cm ² using a membrane filter having a diameter.

Evaluation Test B The magenta ink compositions obtained in Examples B1 to B5 and Comparative Examples B1 to B5 were evaluated as follows. The printing was performed with a discharge nozzle diameter of 30 μm, a piezoelectric element drive voltage of 25 V,
The test was performed using a prototype 48 nozzle inkjet printer adjusted to a driving frequency of 5 kHz, a resolution of 360 dots / inch, and an ink ejection amount of 0.05 μg / dot.

Evaluation B1 : Color Reproducibility (1) A solid printed image (3 × 3 cm) was formed on the following plain paper using each of the magenta ink compositions. Recording paper used for evaluation: Neenah Bond (Kimberly-Clar)
Xerox-P (manufactured by Fuji Xerox Co., neutral paper) Canon Dry (manufactured by Canon Sales Co., acid paper) Yamayuri (Honshu Paper Co., Ltd., acid paper) Ricopy 6200 (manufactured by Ricoh Company) , Acid paper) EPP (acid paper made by Seiko Epson) Xerox R (acid paper made by Fuji Xerox) Xerox4024 3R721 (Xerox Co., Ltd.)
Conqueror (100 g / m ² ) (ArjoWi)
gging, neutral paper) Rapid Copy (neutral paper, manufactured by Igepa Plus) Mode White Copy 80 (neutral paper, manufactured by Modo) The color reproducibility of the solid printing is determined by ISO 284-197.
5, the magenta color tone reference value (L ^* = 48.4, a ^* = 7)
8.1, b ^* = − 7.1) and evaluated in the same manner as in evaluation A1.

The obtained color differences are as shown in Table 2 below. In the table, the color difference ΔE ^* ab was determined based on the following criteria. ΔE ^* ab is less than 2−excellent (◎) for all the recording papers. At least one recording paper having ΔE ^* ab of 2 or more and less than 3 exists, or the average ΔE ^* ab of all recording papers is 2 or more and less than 3 There is at least one recording paper having ΔE ^* ab of 3 or more, or the average ΔE ^* ab of all recording papers is 3 or more.

Evaluation B2 : Color Reproducibility (2) For some of the solid prints created in Evaluation B1, Xe
The color difference was determined based on the printing on the rox-P paper, and evaluated.
The judgment was made in the same manner as 1. The color differences for each type of paper and the determination results are as shown in Table 2.

Evaluation B3 : Ejection stability (clogging of nozzles) The ejection stability of each magenta ink composition was evaluated in the same manner as in Evaluation A3. The results are as shown in Table 2.

Evaluation B4 : Ejection stability (continuous recording for a long time) Using each magenta ink composition, printing was performed at 5 ° C. and 20 ° C.
Continuous printing was performed for 48 hours under each temperature environment of 40 ° C. and 40 ° C. The printing state was evaluated as follows. There was no dot missing at all temperatures, and stable printing was possible-good (o) dot missing occurred over time at any temperature-somewhat poor (△) at any temperature Missing dots occurred from the beginning of printing-defective (x)

[Table 2]

Example C Next, a combination of a color ink composition comprising a black ink, a yellow ink, a magenta ink and a cyan ink having the compositions shown in Table 3 was prepared. Examples C1 to C1
Comparative Examples C1 to C8, and combinations of the color ink compositions having compositions shown in Table 2 and Table 4 were prepared.

In the table, B, Y, M, and C respectively represent black, yellow, magenta, and cyan inks, TEG-mBE represents triethylene glycol monobutyl ether, and DEG-mBE represents diethylene glycol monobutyl ether. . Further, the surface tension of the obtained ink composition was measured. The values were as described in the table.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

Evaluation C The ink composition was evaluated as follows. The printing was performed with a discharge nozzle diameter of 30 μm, a piezoelectric element drive voltage of 20 V,
The test was performed using a prototype 48 nozzle inkjet printer adjusted to a driving frequency of 5.5 kHz, a resolution of 360 dots / inch, and an ink ejection amount of 0.05 μg / dot.

Printing is performed using PPC paper (Xerox Corporation, PPC Paper, Ricoh Company, RICOPY62) as recording paper.
00), recycled paper (Honshu Paper Co., Ltd., Yamayuri), bond paper (Mead Co., Gilbert Bond 25% cotton paper), and high quality paper (Oji Paper, OK fine paper L).

Evaluation C1 : Quick-drying Solid printing was performed by using the ink composition of each color and printing by combining and printing two colors in combination. After a lapse of a predetermined time from the printing, a recording paper of the same type as the recording paper on which the printing was performed was brought into close contact with a pressure of 200 g / cm ² , and it was observed whether or not ink transfer occurred between the two sheets.
The results were evaluated as follows. These evaluation results
The results were as shown in Table 5. In all prints, no ink transfer was observed even in less than 1 second from printing-excellent (◎) In all prints, no ink transfer was observed 1-2 seconds after printing-good (○) In printing, no ink transfer was observed 2 to 5 seconds after printing-slightly defective (不良) In either printing, ink transfer was recognized even after 5 seconds or more after printing-defective (x)

Evaluation C2 : Single-color print quality Alphabets were printed using the ink compositions of each color.
The bleeding of the print and the occurrence of whiskers were visually observed. The results were evaluated as follows. Evaluation result is 5th
As shown in the table. -Bleeding and whiskers were hardly observed-excellent (◎)-Bleeding and whiskers were slightly recognized depending on paper-
Good (O)-Bleeding and whiskers were recognized on some papers-Somewhat poor (B)-Bleeding and whiskers were observed on all papers-Bad (X)

Evaluation C3 : Mixed-color printing quality One of the four ink compositions was solid-printed, and then the other color ink composition was solid-printed so as to be in contact with the solid printing. The boundary was visually observed, and the results were evaluated as follows. The evaluation results were as shown in Table 5. -In any combination, bleeding due to color mixing and whiskers were hardly observed-excellent (◎)-There was a combination in which bleeding due to color mixing and slight whiskers were observed-good (○)-bleeding due to color mixing depending on paper There was a combination where whiskers were observed-Somewhat poor (△)-In all papers, bleeding due to color mixing and whiskers were observed-Poor (X)

Evaluation C4 : Ejection stability Printing was continuously performed at room temperature using the ink compositions of each color. The time until dot missing and ink scattering were observed a total of ten times was measured. The results were evaluated as follows. The evaluation results were as described in Table 5. -48 hours or more for all ink compositions-excellent
(A)-24 to 48 hours for any color ink composition-good (O)-1 to 24 hours for any color ink composition-
Slightly poor (△)-Within 1 hour for any color ink composition-poor (×)

Evaluation C5 : High-speed response performance The ejection stability at the time of high-speed response was evaluated in the same manner as in Evaluation C3 except that the driving frequency of the recording head was set to 10 kHz. The results were as shown in Table 5.

Evaluation C6 : Intermittent Ejection Stability After printing one line using the ink composition of each color under an environment of 15 ° C. and a humidity of 20%, printing was stopped for a certain period of time, and then printing was restarted. The first dot at the time of resuming printing was checked for dot missing or flight bending. The rest time until missing dots or flight bending was observed was evaluated as follows. The evaluation results were as described in Table 5.

Evaluation C7 : Member Erosion of Ink Composition Head member and supply / supply that ink may come into contact with
Waste liquid members (specifically, ABS, AS, PS, PP, P
SF, PC, PE, PET, PBT, nylon, AC
S, POM, butyl rubber, silicone rubber, fluoro rubber,
(EPDM rubber) was immersed in each color ink and allowed to stand at 25 ° C. for 3 months, after which changes in weight and changes in appearance were observed. The results were evaluated as follows. The evaluation results were as described in Table 5. -Weight change of each member is within ± 5% and there is almost no change in appearance-excellent (◎)-Weight change of each member is within ± 10% and there is almost no change in appearance-good (○)-Weight change of each member Is more than ± 10%, but there is almost no change in appearance-slightly poor (・)-The weight change of each member is more than ± 10%, causing swelling and dissolution-poor (x)

[Table 11]

Example D A dye having the composition shown in Table 6 below and other components were mixed to form an ink composition having the following composition, a combination of Examples D1 to D4 and Comparative Examples D1 to D5. Obtained.

Examples D1-4 and Comparative Examples D1-5 Dyes Amounts given in Table 6 Glycerin 5% by weight Diethylene glycol 10% by weight Surfynol 465 1% by weight Pure water Balance

Examples D5-6 Dyes Amounts shown in Table 6 Triethylene glycol monobutyl ether 17% by weight Diethylene glycol 10% by weight Surfynol 465 0.8% by weight Pure water Balance

[Table 12]

Evaluation D These ink compositions were evaluated as follows. Evaluator: Printing is possible under the conditions of a discharge nozzle diameter of 30 μm, a piezoelectric element drive voltage of 25 V, a drive frequency of 5 kHz, a resolution of 360 dots / inch, and an ink discharge amount of 0.05 μg / dot.
An inkjet recording printer with a nozzle inkjet recording head. Recording paper Xerox-R (Fuji Xerox Co., Ltd.) Neenah bond (25% cotton fiber,
Neneah bond) Canon Dyr (Canon Sales Co., Ltd.) EPP (Epson Sales Co., Ltd.) Xerox 4024 3R721 (Xerox) Evaluation method Using the combination of the ink compositions of the above Examples and Comparative Examples, red, green and blue were used. Solid printing
(Solid printing). That is, red was overprinted with yellow and magenta inks, green was overprinted with yellow and cyan inks, and blue was overprinted with magenta and cyan inks.

The color reproducibility of the solid printed image (3 × 3 cm) is determined by CIE (Commision Inte- gration).
rnationale de I'Eclairage), the L ^* a ^* b ^* color system of the color difference display method is Macbeth CE-7.
000 spectrophotometer (manufactured by Macbeth), and the measured values were compared with ISO 2845-19 shown in Table 7 below.
The color difference from the 75 tone reference values was determined from the following equation (I).

Table 7 L * a * b * Red 47.4 70.3 47.5 Green 47.6-74.1 23.2 Blue 19.2 35.5-53.0 ΔE ^* ab = [( ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 (I) The obtained color differences are as described in Table 8 below. In the table, ΔE ^* ab of the average value of the five color difference recording papers was determined based on the following criteria. When the color differences ΔE ^* ab of the three colors are all 20 or less: ◎ When there is more than 20 even for one color and 30 or less… ○ When there is more than 30 even for one color… × Table 8 ΔE * ab red green blue D1 21.0 17.5 26.5 ２ 2 23.2 19.1 18.6 3 18.8 19.7 19.3 ４ 4 24.7 25.8 28.7 ０ 5 18.0 16. 2 13.0 ◎ 6 15.2 17.6 12.4 ◎ 7 19.4 14.4 16.7 ◎ 8 18.1 19.2 17.1 ◎ 9 17.7 19.8 11.1 ◎ Comparison Example D1 18.8 45.0 33.8 × 2 41.2 19.7 39.3 × 3 42.3 19.7 38.8 × 4 45.1 32.5 19.3 × 5 40.9 36 0.3 19.3 ×

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 5-317068 (32) Priority date December 16, 1993 (December 16, 1993) (33) Priority claim country Japan (JP) (72) Inventor Yoshiyuki Koike 3-5-5 Yamato, Suwa City, Nagano Prefecture Inside Seiko Epson Corporation (72) Inventor Etsuko Yoshiike 3-5-5 Yamato Suwa City, Nagano Prefecture Seiko Epson Shares In-company (72) Inventor Yoshiharu Yoshida 3-5-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (72) Inventor Hiroko Hayashi 3-5-3 Yamato, Suwa-shi, Nagano Seiko Epson (72) Inventor Kazuhide Kubota 3-5-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (56) References JP-A-59-59757 (JP, A) JP-A-61- 183370 (JP, A) JP-A-61-272276 (JP, A) JP-A-1-1588083 (JP, A) JP-A-6-191143 (JP, A) JP-A-6-228482 (JP, A) JP-A-58 -222166 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (15)

(57) [Claims] Claims: 1. I. Direct Yellow 86 and C.I.
I. Direct Yellow 132 in a weight ratio of 1: 3 to 3: 1 and each of 0.3 to 0.3 based on the ink composition.
A yellow ink composition comprising 3.0% by weight. 2. C. I. Acid Red 52 and C.I. I. Acid Red 289, in a weight ratio of 1: 2 to 2: 1,
And 0.3 to 2.5% by weight based on the ink composition.
A magenta ink composition comprising: 3. A combination of a yellow ink composition and a magenta ink composition, wherein the yellow ink composition is the ink composition according to claim 1, and the magenta ink composition is the ink according to claim 2. A combination, which is a composition. 4. A combination of a yellow ink composition and a cyan ink composition, wherein the yellow ink composition is the ink composition according to claim 1, and the cyan ink composition is C.I. I. Direct blue 19
9, C.I. I. Direct Blue 86, and C.I. I. A combination, which is an ink composition containing 1 to 4% by weight of one or more dyes selected from the group consisting of Acid Blue 9. 5. A combination of a magenta ink composition and a cyan ink composition, wherein the magenta ink composition is the ink composition according to claim 2, and the cyan ink composition is the ink according to claim 4. A combination, which is a composition. 6. A magenta ink composition comprising a combination of a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the yellow ink composition is the ink composition according to claim 1. Is the ink composition according to claim 2, wherein the cyan ink composition is the ink composition according to claim 4. 7. An ink cartridge containing a yellow ink composition, a magenta ink composition, and, if necessary, a cyan ink composition in a partitioned fraction, wherein the yellow ink composition An ink cartridge according to claim 1, wherein the magenta ink composition is the ink composition according to claim 2, and the cyan ink composition is the ink composition according to claim 4. 8. A color ink jet recording method using a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the ink composition according to claim 1 is used as a yellow ink composition. A method comprising using the ink composition according to claim 2 as a magenta ink composition. 9. The method according to claim 8, wherein the ink composition according to claim 4 is used as a cyan ink composition. 10. The method according to claim 8, wherein any two of a yellow ink composition, a magenta ink composition, and a cyan ink composition are superposed and printed to form red, green, and blue, and color printing is performed. 10. The method according to 9. 11. The method according to claim 8, wherein acidic paper is used as the recording paper. 12. The ink jet recording method according to claim 1, wherein the ink composition is supplied from an ink container to a recording head, an ink absorber is placed in the ink container, and the ink composition is supplied to the recording head in the ink container. The method according to any one of claims 8 to 11, wherein the recording head is impregnated and held in an absorber, and the nozzle of the recording head is subjected to an ink jet recording apparatus configured to be subjected to a water scraping treatment. . 13. The method according to claim 12, wherein said ink absorber is urethane foam. 14. The method according to claim 12, wherein the water-repellent treatment is a eutectoid plating treatment using a nickel-fluorine-based polymer. 15. A recorded matter recorded by the method according to claim 8. Description: