Aqueous ink composition and method of recording using the same

A cyan ink comprising a phthalocyanine derivative represented by the following formula (I), excellent in color reproducibility, suitable for use in the ink jet recording method is disclosed. The combination use of this cyan ink comprising the phthalocyanine derivative with yellow and magenta inks, each comprising a specific dye, gives excellent color printing. ##STR1## wherein X represents an ion of a metal selected from Cu, Fe, Co and Ni, R.sup.1 represents H or an alyl group, Z represents --O, --COOH or NR.sup.2 R.sup.3 (where R.sup.2 represents H or an alkyl group, and R.sup.3 represents an alkyl group or phenyl group), n represents an integer of 1 to 15, k and l represent 0 or 1, and m represents an integer of 1 to 4, provided that k, l and m fulfill the inequality 2.ltoreq.k+1+m.ltoreq.4.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to an ink composition for recording, and to a 
method of recording, in particular, an ink jet recording method, using the 
same. More particularly, the present invention relates to an ink 
composition comprising as a colorant a phthalocyanine derivative, to a 
method of recording, in particular, an ink jet recording method, using the 
same, and to a method for forming color images. 
2. Background Art 
Ink compositions are required to have various excellent properties. 
Specifically, they are not only required to have excellent color 
reproducibility, but also required to produce images which are excellent 
in water resistance and light resistance. 
Further, in the ink jet recording method in which droplets of an ink 
composition are ejected on a recording medium to form thereon an image, 
the ink composition is required to have much more excellent properties 
than those required for ordinary writing utensils such as fountain pens 
and ball-point pens. For instance, the ink composition is required to have 
a proper viscosity and a suitable surface tension, to be excellent in 
preservation stability, and not to cause clogging in a nozzle. 
In general, many of these properties required for the ink composition for 
use in the ink jet recording method can be fulfilled by an aqueous ink 
composition comprising a water-soluble dye water and a water-soluble 
organic solvent. The properties of printed images, such as color tone, 
water resistance and light resistance, are highly dependent on the dye 
used. It has been tried to utilize various dyes. 
Ink compositions containing a phthalocyanine derivative as a cyan or blue 
dye have been proposed. For instance, the use of C. I. Direct Blue 86, 87 
or 199 has been proposed. Further, the use of a phthalocyanine derivative 
is also disclosed, for example, in Japanese Laid-Open Patent Publications 
Nos. 2772/1986, 149758/1987, 190273/1987 and 200883/1991. 
However, there is yet room for improvement in these ink compositions 
containing a phthalocyanine derivative. 
On the other hand, such a printer that produces color images by means of 
the ink jet printing method is also popular. Color images are formed by 
using, in general, yellow, magenta and cyan ink compositions, and 
optionally a black ink composition. By superposing these ink compositions, 
red, green, and blue, and optionally black colors are developed. In such 
color printing, each ink composition is required to be highly reproducible 
in its own color. In addition to this, these ink compositions are required 
to be excellent in reproducibility in red, green, and blue, and optionally 
black colors which are developed by superposing ink compositions one over 
another. 
SUMMARY OF THE INVENTION 
We have now found that an ink composition comprising as a colorant a 
specific phthalocyanine derivative has extremely excellent properties. 
Furthermore, we have also found that excellent color printing can be 
obtained by the use of the combination of this cyan ink composition with 
yellow and magenta ink compositions, each comprising a specific dye. 
Accordingly, an object of the present invention is to provide an ink 
composition having various properties which are required for ink 
compositions. 
Another object of the present invention is to provide an ink composition 
having various properties which are required for ink compositions useful 
for ink jet recording. 
A further object of the present invention is to provide a method of 
printing, in particular, an ink jet recording method, by which excellent 
color images can be obtained. 
According to the present invention, there provides a cyan ink composition 
comprising as a colorant a phthalocyanine derivative represented by the 
following formula (I): 
##STR2## 
wherein 
X represents an ion of a metal selected from Cu, Fe, Co and Ni, 
M represents hydrogen atom, an alkali metal, ammonium or an organic amine, 
R.sup.1 represents hydrogen atom or an alkyl group which may be 
substituted, 
Z represents --OH, --COOH or NR.sup.2 R.sup.3 ( where R.sup.2 represents 
hydrogen atom or an alkyl group which may be substituted, and R.sup.3 
represents an alkyl group which may be substituted, or phenyl group which 
may be substituted), 
n represents an integer of 1 to 15, 
k and l each independently represent 0 or 1, and 
m represents an integer of 1 to 4, 
provided that k, l and m fulfill the inequality 2.ltoreq.k+l+m.ltoreq.4. 
According to the present invention, there provides a method in which 
yellow, magenta and cyan ink compositions are used, wherein 
the cyan ink composition comprises as a colorant the compound represented 
by the above formula (I), 
the yellow ink composition comprises as a colorant a compound represented 
by the following formula (II): 
##STR3## 
wherein 
R.sup.4 and R.sup.5 each independently represent --OH; --SO.sub.3 M; or 
phenyl or naphthyl group substituted with --COOM, 
R.sup.6 and R.sup.7 each independently represent hydrogen atom, an alkyl 
group or an alkoxy group, 
R.sup.8 represents hydrogen atom, an alkyl group or a hydroxyalkyl group, 
R.sup.9 represents hydrogen atom, --OH or a hydroxyalkyl group, and 
M is as defined in the above formula (I), or a compound represented by the 
following formula (III): 
##STR4## 
wherein 
R.sup.10 and R.sup.11 each independently represent hydrogen atom, --OH or 
an alkoxy group, 
R.sup.12 and R.sup.13 each independently represent hydrogen atom or an 
alkyl group, and 
M is as defined in the above formula (I), and 
the magenta ink composition comprises as a colorant a compound represented 
by the following formula (IV): 
##STR5## 
wherein 
R.sup.14 represents hydrogen atom or an alkyl group, 
R.sup.15 represents hydrogen atom, a halogen atom or an alkyl group, 
R.sup.16 represents --COOH or --SO.sub.3.sup.-, 
R.sup.17 and R.sup.18 each independently represent hydrogen atom, a halogen 
atom, an alkyl group or --SO.sub.3 M, and 
M is as defined in the above formula (I).

DETAILED DESCRIPTION OF THE INVENTION 
Phthalocyanine Derivatives 
The phthalocyanine derivative for use in the cyan ink composition according 
to the present invention is a compound represented by the above formula 
(I). 
In the formula (I), hydrogen atoms on four benzene rings in the 
phthalocyanine skeleton are substituted with the groups --(SO.sub.3 M)k, 
--(SO.sub.2 NH.sub.2)l and --(SO.sub.2 --NR.sup.1 --(CH.sub.2)N--Z)m. 
While the position of the substitution is not particularly limited, among 
the above three groups, the group --(SO.sub.2 --NR.sup.1 
--(CH.sub.2)N--Z)m should exist in a number of at least one. The above 
groups can exist in a number of four or less in total. In other words, it 
is necessary that k and l represent an integer of 0 or 1, that m be an 
integer of 1 to 4, and that k, l and m be in the relationship which 
fulfills the inequality 2.ltoreq.k+l+m.ltoreq.4. 
In the formula (I), X represents an ion of a metal selected from Cu, Fe, Co 
and Ni. 
Specific examples of the alkali metal and the organic amine represented by 
M in the formula (I) include lithium, sodium, potassium, ammonium, 
dimethylammonium, morpholium and piperidinium. 
The alkyl group represented by R.sup.1 in the formula (I) is preferably a 
linear or branched C.sub.1-4 alkyl group. One or more hydrogen atoms in 
this alkyl group may be substituted, and preferable examples of the 
substituent include hydroxyl group and amino group. 
In NR.sup.2 R.sup.3 represented by Z in the formula (I), R.sup.2 represents 
hydrogen atom or an alkyl group. This alkyl group is preferably a linear 
or branched C.sub.1-4 alkyl group. One or more hydrogen atoms in this 
alkyl group may be substituted, and preferable examples of the substituent 
include hydroxyl group and amino group. Further, R.sup.3 represents an 
alkyl group or phenyl group. This alkyl group is preferably a linear or 
branched C.sub.1-4 alkyl group. One or more hydrogen atoms in this alkyl 
group may be substituted, and preferable examples of the substituent 
include hydroxyl group and amino group. Furthermore, one or more hydrogen 
atoms on the phenyl group may be substituted, and examples of the 
substituent include hydroxyl group and amino group. 
In the formula (I), n represents an integer of 1 to 15. However, when Z is 
--COOH, n is preferably an integer of 2 to 12; and when Z is --OH, n is 
preferably an integer of 5 to 15. 
Specific preferable examples of the phthalocyanine derivative represented 
by the formula (I) include the following compounds (I-1) to (I-16): 
##STR6## 
The compound having the formula (I) can be produced in accordance with a 
known method for preparing a phthalocyanine derivative. For example the 
compound (I) can be obtained in accordance with the method described in 
Japanese Laid-Open Patent Publication No. 22967/1984 or Japanese Laid-Open 
Patent Publication No. 30874/1984. 
The compound having the formula (I) can be produced by the following 
method. The compound (I) can be prepared by reacting a compound 
represented by the following formula (Va): 
##STR7## 
wherein A represents the group --(SO.sub.3 M)k, --(SO.sub.2 NH.sub.2)l or 
--(SO.sub.2 --NR.sup.1 --(CH.sub.2)N--Z)m (where M, R.sup.1, z, k, l and m 
are as defined in the formula (I)), and i represents an integer of 1 to 4, 
or 
a mixture of the compound (Va) and a compound represented by the following 
formula (Vb): 
##STR8## 
wherein B represents the group --(SO.sub.3 M)k, --(SO.sub.2 NH.sub.2)l or 
--(SO.sub.2 --NR.sup.1 --(CH.sub.2)N--Z)m (where M, R.sup.1, Z, k, l and m 
are as defined in the formula (I)), and j represents an integer of 1 to 4, 
with urea and a metal chloride represented by the formula XCln (where n 
agrees with the valency of X). In this reaction excessive urea dissolved 
may also play a role of a reaction solvent, and the reaction can be 
carried out at a temperature of preferably about 190.degree. to 
200.degree. C. 
The values of k, l and m in the compound having the formula (I) can be 
controlled by properly selecting the type and the mixing ratio of the 
compounds (Va) and (Vb). 
Further the compound (I) can be prepared from a compound of the formula 
(VIa): 
##STR9## 
wherein A and i are as defined above, or the compound (VIa), and a 
compound of the formula (VIb): 
##STR10## 
wherein B and j are as defined above, with a metal chloride represented by 
the formula XCln (where n agrees with the valency of X). The reaction is 
carried out by: 
(a) mixing these compounds and heating the mixture, for example, at a 
temperature of approximately 150.degree. to 200.degree. C., or 
(b) heating the mixture at a temperature of approximately 190.degree. to 
200.degree. C. in an inert solvent in the presence or absence of urea. 
Also in this method, the values of k, l and m in the compound (I) can be 
controlled by properly selecting the type and the mixing ratio of the 
compounds (VIa) and (VIb). 
The amount of the compound (I) to be incorporated into the ink composition 
can be properly determined depending upon the type of the solvent 
component used, the properties required for the ink. However, in the case 
where the ink composition will be used in the ink jet recording method, 
the incorporation amount of the compound (I) is preferably from 1.5 to 
8.0% by weight, more preferably from 2.5 to 6.5% by weight of the ink 
composition from the viewpoint of color tone. 
Further, a mixture of water and a water-soluble organic solvent is 
preferred as the solvent for use in ink composition of the present 
invention. Examples of this water-soluble organic solvent include 
polyhydric alcohols such as ethylene glycol, diethylene glycol, 
triethylene glycol, polyethlene glycol, propylene glycol, 1,3-propane 
diol, 1,5-pentane diol, 1,2,6-hexane triol and glycerol; ethers of 
polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene 
glycol monobutyl ether, triethylene glycol monobutyl ether and dipropylene 
glycol monomethyl ether; nitrogen-containing solvents such as formamides, 
dimethylformamide, diethanolamine, triethanolamine, 
1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone and N-methyl-2-pyrrolidone; 
and sulfur-containing solvents such as thiodiglycol and dimethyl 
sulfoxide. 
These solvents can be used either singly or as a mixture of two or more. 
The amount of the solvent is in the range of 3 to 40% by weight, 
preferably in the range of 3 to 30% by weight of ink composition from the 
view point of the prevention of clogging in a nozzle and the quality of 
images printed. 
Further, in order to enhance the drying characteristics of the ink after 
the formation of an image, it is preferable that the ink composition of 
the present invention further comprise a lower alcohol such as ethanol, 
1-propanol or 2-propanol; an anionic surface active agent such as a fatty 
acid salt or an alkylsulfate ester; or a nonionic surface active agent 
such as acetylene glycol, a polyoxyethylene alkyl ether or a 
polyoxyethylene fatty ester. From the viewpoint of the quality of images 
printed, the amount of the lower alcohol to be incorporated is preferably 
in the range of 2 to 10% by weight, more preferably in the range of 2 to 
6% by weight of the ink composition. The amount of the surface active 
agent to be incorporated is preferably in the range of 0.01 to 2% by 
weight of the ink composition. 
The ink composition according to the present invention may further comprise 
a water-soluble polymer or resin, an anti-foaming agent, a pH modifier, a 
mildew-proofing agent and the like, if necessary. 
The ink composition of the invention can be produced in a conventional 
manner. For instance, the ink can be obtained by the following method: all 
of the components are thoroughly mixed and dissolved, and the mixture is 
filtered under pressure through a membrane filter having a hole diameter 
of 0.8 micrometers, and then degased by using a vacuum pump. 
The ink composition according to the present invention is particularly 
suitable for use in the ink jet recording method in which an ink is 
ejected through a fine pore as droplets to conduct recording. The ink 
composition of the invention can also be used for ordinary writing 
utensils, recorders, pen plotters and the like. 
In the case of the ink jet recording method, it is possible to achieve 
excellent image recording by adopting, in particular, a means in which 
droplets are ejected by utilizing the vibration of a piezoelectric device, 
or a means in which thermal energy is utilized. 
Formation of Color Images 
According to another preferred embodiment of the present invention, there 
is provided a method for producing color images, in which the ink 
composition comprising the compound (I) above described, and specific 
yellow and magenta ink compositions are used. 
The yellow ink composition for use in this embodiment comprises as a 
colorant a compound represented by the above formula (II) or (III). 
Further, the magenta ink composition for use in this embodiment comprises 
as a colorant a compound represented by the above formula (IV). 
By using these ink compositions in combination, color images whose colors 
are well reproduced can be formed. These ink compositions are highly 
reproducible in their own colors, and, in addition to this, they are 
excellent in reproducibility in red, green, blue and black colors which 
are obtained by superposing two of or all of the ink compositions one over 
another. 
In the formula (II), one or more hydrogen atoms in the phenyl or naphthyl 
group represented by R.sup.4 or R.sup.5 may be substituted. Specific 
examples of the substituent include hydroxyl group, --SO.sub.3 M, --COOM, 
--PO.sub.3 M.sub.2 (where M is as defined above), an alkyl group 
(preferably a C.sub.1-4 alkyl group), and an alkoxy group (preferably a 
C.sub.1-4 alkoxy group). 
In the formula (II), the alkyl group represented by R.sup.6 or R.sup.7 is 
preferably a linear or branched C.sub.1-3 alkyl group. The alkoxy group 
represented by R.sup.6 or R.sup.7 is preferably a linear or branched 
C.sub.1-4 (preferably C.sub.1-2) alkoxy group. 
The alkyl group represented by R.sup.8 is preferably a linear or branched 
C.sub.1-3 alkyl group. The alkyl moiety of the hydroxyalkyl group 
represented by R.sup.8 is a linear or branched C.sub.1-4 (preferably 
C.sub.1-2) alkyl group. 
Further, the alkyl moiety of the hydroxyalkyl group represented by R.sup.9 
is a linear or branched C.sub.1-4 (preferably C.sub.1-2 ) alkyl group. 
Specific preferable examples of the compound represented by the formula 
(II) include the following compounds (II-1) to (II-10): 
##STR11## 
The alkoxy group represented by R.sup.10 or R.sup.11 in the formula (III) 
is a linear or branched C.sub.1-4 (preferably C.sub.1-2) alkoxy group. 
Further, the alkyl group represented by R.sup.12 or R.sup.13 is preferably 
a linear or branched C.sub.1-4 alkyl group. 
Specific preferable examples of the compound represented by the formula 
(III) include the following compounds (III-1) to (III-10): 
##STR12## 
The alkyl group represented by R.sup.14 in the formula (IV) is preferably a 
linear or branched C.sub.1-4 alkoxy group. 
Further, the halogen atom represented by R.sup.15 is preferably fluorine, 
chlorine, bromine or iodine. Furthermore, the alkyl group represented by 
R.sup.15 is preferably a linear or branched C.sub.1-4 alkyl group. 
The halogen atom represented by R.sup.17 or R.sup.18 is preferably 
fluorine, chlorine, bromine or iodine. Further, the alkyl group 
represented by R.sup.17 or R.sup.18 is preferably a linear or branched 
C.sub.1-4 alkyl group. 
Specific preferable examples of the compound represented by the formula 
(IV) include the following compounds (IV-1) to (IV-10): 
##STR13## 
The ink composition comprising the compound (II), (III) or (IV) can be 
formulated and prepared in the same manner as in the case of the ink 
composition comprising the compound (I). According to the preferred 
embodiment of the present invention, in the case where an image will be 
formed by the ink jet printing method, the amount of the compound (II) or 
(III) to be incorporated into the ink composition is preferably about 0.5 
to 3.0% by weight, more preferably about 1.0 to 2.0% by weight of the ink 
composition. Further, in the case of the compound (IV), the amount thereof 
is preferably about 0.5 to 4.0% by weight, more preferably about 1.0 to 
3.0% by weight of the ink composition. 
EXAMPLES 
The present invention will now be explained more specifically by referring 
to the following Examples. However, the present invention is not limited 
to these examples. 
Example A 
Inks, each having the composition shown in Table 1 were prepared in a 
conventional manner. In the table, figures are in "% by weight" of the ink 
composition and the balances are water. 
TABLE 1 
__________________________________________________________________________ 
Example A Comparative Example A 
Formulation of Ink 
1 2 3 4 5 6 7 8 9 10 
1 2 3 
__________________________________________________________________________ 
Dye 
(I-1) 8 
6 
4 2 1 
(I-5) 1.5 1 
(I-7) 2.5 
2 
(I-8) 3.5 
(I-9) 6.5 
(I-11) 3 
(I-14) 1 
C.I. Acid Blue 9 3 
C.I. Direct Blue 86 4 3 
Ethylene glycol 10 
Diethylene glycol 
40 
30 
10 15 
17 15 10 10 
Glycerol 5 3 4 8 5 5 5 5 
Diethylene glycol monobutyl ether 
10 
Triethylene glycol monobutyl ether 
12 10 
Triethanolamine 1 1 
2-Pyrrolidone 3 
Thiodiglycol 8 8 
Ethanol 4 
1-Propanol 6 3 3 
Surfynol 465* 1 0.8 1.5 1 1 
Mildew-proofing agent 
0.3 
0.3 
0.3 
0.3 0.3 0.3 
__________________________________________________________________________ 
*: Surfynol 465 (manufactured by Nisshin Kagaku Kabushiki Kaisha, 
acetylene glycol surface active agent) 
Evaluation Test A 
The ink compositions of Examples A1 to A10 and of Comparative Examples A1 
to A3 were evaluated in terms of the following Tests A1 to A4, by using 
the following printer and recording papers. 
Printer 
Printer (1): An ink jet printer having an on-demand-type ink jet head 
(diameter of nozzle: 35 micrometers, 48 nozzles) made on an experimental 
basis, which produces droplets by utilizing the vibration of a 
piezoelectric device to conduct recording; the printer can print an image 
under such conditions that the driving frequency is 5 kHz, that the 
voltage for driving the piezoelectric device is 25 V and that the 
resolution is 360 dots/inch. 
Printer (2): Desk Writer 550C (manufactured by Hewlett Packard Corp.) 
Recording Papers 
(1) Coated paper NM for ink jet printing (manufactured by Mitsubishi Paper 
Mills) 
(2) Canon Dry (manufactured by Canon Hanbi) 
(3) Xerox 4024 (manufactured by Xerox) 
(4) Xerox P (manufactured by Fuji Xerox) 
(5) Ricopy 6200 (manufactured by Ricoh) 
Test A1: Color Reproducibility 
A solid image (100% duty) was printed by the printer (1) on each of the 
recording papers (1) to (5) by using each of the inks of Examples and 
Comparative Examples. 
With respect to the solid image (3.times.3 cm) of each color, the 
color-scale values L*, a* and b* according to the color- difference 
indicating system defined by CIE (Commision International de l'Eclairage) 
were measured by Macbeth CE-7000 spectrophotometer (manufactured by 
Macbeth Corp.). The difference between the color-scale values measured and 
the color reference values of cyan according to ISO 2845-1975, shown below 
were obtained, and the color difference was calculated by the following 
equation (i). 
TABLE 2 
______________________________________ 
L* a* b* 
______________________________________ 
Color reference 
53.9 -19.1 -54.2 
values of cyan 
______________________________________ 
##EQU1## 
The average value of the color differences .DELTA.E*ab's which were 
obtained in terms of the images printed on the five recording papers is as 
shown in Table 3, and the color differences were evaluated in accordance 
with the following standard. The color differences shown in Table 3 are 
those values which were obtained in terms of the images printed by using 
the printer (1). Almost the same values were obtained even in the case 
where images were printed by using the printer (2). 
In the table: 
All of the color differences .DELTA.E*ab's of the images printed on the 
five recording papers are 20 or less: O 
At least one of the color differences is more than 20 and 30 or less: 
.largecircle. 
Only one of the color differences is in excess of 30: .DELTA. 
Two or more of the color differences are in excess of 30: X 
Test A2: Quality of Image 
Alphabets and graphic images were printed by the printer (1) and (2) on 
each of the recording papers (1) to (5) with the inks of Examples and 
Comparative Examples. These images were visually observed, and evaluated 
according to the following standard: 
Non-blurred, sharp images having excellent quality: O 
Scarcely-blurred, sharp images having good quality: .largecircle. 
Scarcely-blurred, but slightly lacked in sharpness: .DELTA. 
Remarkably-blurred or lacked in sharpness: X 
Test A3: Water Resistance 
The samples of the solid image printed on the recording paper (3) with the 
printer (1), obtained in the Test A1 were dipped in tap water for one 
hour, pulled out, and dried spontaneously. With respect to these samples, 
the .DELTA.E*ab's were obtained before and after the test in the same 
manner as in Test A1, and the results were evaluated in accordance with 
the following standard: 
The remaining rate obtainable by the following equation (ii) is: 
100-90%: O 
90-75%: .largecircle. 
75-60%: .DELTA. 
60% or lower: X 
##EQU2## 
Test A4: Light Resistance 
The samples of the solid image printed on the recording paper (3) with the 
printer (1), obtained in the Test A1 were placed in a transparent plastic 
cello case, and allowed to stand under the sunlight for 30 days. With 
respect to these samples, the .DELTA.E*ab was obtained before and after 
the test in the same manner as in Test 1, and evaluation was carried out 
in accordance with the following standard: 
The remaining rate obtainable by the above equation (ii) is: 
100-90%: O 
90-75%: .largecircle. 
75% or lower: X 
The results of the Tests 1 to 4 were as shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Ink 
Comparative 
Example A Example A 
Test Item 1 2 3 4 5 6 7 8 9 10 1 2 3 
__________________________________________________________________________ 
Test 1** .DELTA.E*.sub.ab 
28.7 
19.8 
17.6 
12.4 
13.0 
18.1 
17.5 
22.1 
14.8 
16.3 
15.2 
18.3 
16.7 
Color Reproducibility 
Average Value* 
Judgement 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
Test 2** (1) .circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Quality of Image 
(2) .DELTA. 
.largecircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.DELTA. 
.DELTA. 
(3) .largecircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.largecircle. 
(4) .largecircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.largecircle. 
(5) .largecircle. 
.circleincircle. 
.circleincircle. 
.DELTA. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.largecircle. 
Test 3 Water Resistance 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.largecircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
X .DELTA. 
.DELTA. 
Test 4 Light Resistance 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
X .largecircle. 
.largecircle. 
__________________________________________________________________________ 
*: The color differences in Test 1 are those values which were obtained i 
terms of the images printed with the printer (1); almost the same values 
can be obtained even in the case where images are printed with the printe 
(2). 
**: In Tests 1 and 2, the judgments on the images printed with the printe 
(1) were equal to those on the images printed with the printer (2). 
Example B 
Yellow, magenta and cyan inks, each having the composition shown in the 
following Table 4 were prepared in a conventional manner. 
In the table, figures are in "% by weight" of the ink composition and the 
balances are water. 
TABLE 4 
__________________________________________________________________________ 
Formulation of Ink Example B1 
Example B2 
Example B3 
Comparative Example 
__________________________________________________________________________ 
B1 
Yellow Dye 
II-3 1.5 
III-5 2 
III-10 0.5 
C.I. Acid Yellow 23 1.8 
Magenta Dye 
IV-5 
IV-6 
IV-9 
C.I. Acid Red 52 
Cyan Dye 
I-4 
I-3 
I-13 
C.I. Acid Blue 9 
Diethylene glycol 40 37 30 
Glycerol 6 5 3.5 
12 10 8 6 6 5 
2-Pyrrolidone 5 5 5 5 5 5 
Thiodiglycol 10 10 10 
Ethanol 4 4 4 
2-Propanol 6 6 6 
Mildew-Proofing agent 
0.3 
0.3 0.3 
__________________________________________________________________________ 
Formulation of Ink Example B4 
Example B5 
Example B6 
Comparative Example 
__________________________________________________________________________ 
B2 
Yellow Dye 
II-2 1.5 
II-10 0.9 
III-3 1.2 
C.I. Direct Yellow 86 1 
Magenta Dye 
IV-1 2 
IV-4 0.9 
IV-10 1.5 
C.I. Direct Red 9 3 
Cyan Dye 
I-4 1 1 
I-11 3 3 
I-3 2 
I-15 3 
Ethylene glycol 12 12 7 12 8 7 
Polyethylene glycol #200 13 10 8 
Glycerol 3 3 2 10 10 10 
Triethanolamine 1 1 
N-Methyl-2-pyrrolidone 3 2.5 2 3 2.5 2 
1,3-Dimethyl-imidazolidinone 
1 1 1 5 5 5 
Ethanol 8 8 8 
1-Propanol 
Mildew-Proofing agent 0.3 
0.3 0.3 
0.3 
0.3 0.3 
0.3 0.3 0.3 
__________________________________________________________________________ 
Formulation of Ink Example B7 
Example B8 
Example B9 
Comparative Example 
__________________________________________________________________________ 
B3 
Yellow Dye 
II-8 1.4 
III-5 1 
III-7 1.6 
C.I. Acid Yellow 23 1.2 
Magenta Dye 
IV-1 1.7 
IV-8 2 
IV-9 2 
C.I. Acid Red 249 1.4 
Cyan Dye 
I-1 4.5 
I-3 3.5 
I-16 4 
C.I. Direct Blue 86 2.5 
Diethylene glycol 15 13 10 18 15 12 18 16 12 
Glycerol 10 10 8 
Diethylene glycol monobutyl ether 
15 15 15 
Triethylene glycol monobutyl etyher 
8 8 8 8 8 8 
Dipropylene glycol monomethyl ether 5 5 5 
Surfynol 465 1 1 1 0.1 
0.1 0.1 
1 1 1 
Mildew-Proofing agent 
0.3 
0.3 0.3 
0.3 
0.3 0.3 
0.3 
0.3 0.3 
0.3 0.3 0.3 
__________________________________________________________________________ 
Formulation of Ink Example B10 
Example B11 
Example B12 
Comparative Example 
__________________________________________________________________________ 
B4 
Yellow Dye 
II-3 0.5 
III-8 0.5 3 
III-10 1.8 1.8 
Magenta Dye 
IV-5 2.2 4 
IV-9 2.5 
C.I. Acid Red 289 1.5 
Cyan Dye 
I-4 5 8 
I-13 4 
C.I. Direct Blue 199 3 
Diethylene glycol 20 17 12 10 10 10 10 10 10 
1,5-Pentane diol 8 8 8 
1,2,6-Hexane triol 3 3 3 
Glycerol 2 2 
2-Pyrrolidone 6 5 2.5 6 6 3 
Triethanolamine 1 1 1 
2-Propanol 3.5 
3.5 3.5 
Surfynol 465 1.5 
1.5 1.5 
2 2 2 1.5 1.5 1.5 
Duck Algin NSPL (Kibun Pood Chemifa K.K.)** 
0.005 
0.005 
0.005 
Mildew-Proofing agent 
0.3 
0.3 0.3 
0.3 
0.3 0.3 
0.3 
0.3 0.3 
0.3 0.3 0.3 
__________________________________________________________________________ 
*: Acetylene glycol surface active agent 
**: Sodium alginate (watersoluble polymer) 
Evaluation Test B 
The inks of Examples B1 to B12 and of Comparative Examples B1 to B4 were 
evaluated in terms of the following Tests B1 to B3, with the above printer 
and recording papers. 
Test B1: Color Reproducibility 
Solid images (100% duty) of yellow, magenta, cyan, red, green, blue and 
black were printed with the above printer (1) on each of the recording 
papers (1) to (5) with the inks of Examples and Comparative Examples. The 
image of red was obtained by superposing the yellow and magenta inks one 
over the other; the image of green was obtained by superposing the yellow 
and cyan inks one over the other; the image of blue was obtained by 
superposing the magenta and cyan inks one over the other; and the image of 
black was obtained by superposing the yellow, magenta and cyan inks one 
over another. 
With respect to the solid image (3.times.3 cm) of each color, the 
color-scale values L*, a* and b* according to the color- difference 
indicating system defined by CIE (Commision International de l'Eclairage) 
were measured by a Macbeth CE-7000 spectrophotometer (manufactured by 
Macbeth Corp.). The differences between the color-scale values measured 
and the color reference values according to ISO 2845-1975, shown in Table 
5 were obtained, and the color difference was calculated by the above 
equation (i). 
TABLE 5 
______________________________________ 
Color reference values of each color (ISO 2845-1975) 
yellow magenta cyan red green blue black 
______________________________________ 
L* 90.7 48.4 53.9 47.4 47.6 19.2 28.6 
a* -18.4 78.1 -19.1 70.3 -74.1 35.5 0.1 
b* 91.1 -7.1 -54.2 47.5 23.2 -53.0 
-2.5 
______________________________________ 
The average value of the color differences .DELTA.E*ab's which were 
obtained in terms of the images printed on the papers (1) to (5) was as 
shown in Table 6. The color reproducibility was evaluated in accordance 
with the following standard. 
All of the color differences .DELTA.E*ab's obtained in terms of the images 
of red, green, cyan and black are 20 or less: O 
At least one of the color differences is more than 20 and 30 or less: 
.largecircle. 
At least one of the color differences is in excess of 30:X 
The results were as shown in Table 6. 
Further, the same test was carried out with the printer (2), and almost the 
same results as the above were obtained. 
Test B2: Water Resistance 
The samples of the solid image printed on the recording paper (3), obtained 
in the Test B1 were dipped in tap water for one hour, pulled out, and 
dried spontaneously. With respect to these samples, the .DELTA.E*ab was 
obtained before and after the test in the same manner as in Test B1, and 
evaluation was carried out in accordance with the following standard: 
The remaining rate obtainable by the above equation (ii) is: 
100-80% in all of the samples of seven colors: O 
80-60% in all of the samples of seven colors: .largecircle. 
60% or lower in at least one of the samples of seven colors: X 
Test B3: Light Resistance 
The samples of the solid image printed on the recording paper (3), obtained 
in the Test B1 were place in a transparent plastic cello case, and allowed 
to stand under the sunlight for 30 days. With respect to the samples, the 
.DELTA.E*ab was obtained before and after the test in the same manner as 
in Test B1, and evaluation was carried out in accordance with the 
following standard: 
The remaining rate obtainable by the above equation (ii) is: 
100-90% in all of the samples of seven colors: O 
90-75% in all of the samples of seven colors: .largecircle. 
75% or lower in at least one of the samples of seven colors: X 
TABLE 6 
__________________________________________________________________________ 
Test 
Test B1 Color Reproducibility Test 2B 
Test 3B 
.DELTA.E*.sub.ab (Average value in 5 types of recording 
papers) Water 
Light 
Formulation of Ink 
Yellow 
Magenta 
Cyan 
Red 
Green 
Blue 
Black 
Judgement 
Resistance 
Resistance 
__________________________________________________________________________ 
Example 1 17.5 
16.7 24.6 
13.6 
17.5 
26.8 
4.9 
.largecircle. 
.circleincircle. 
.circleincircle. 
Example 2 19.8 
17.2 19.4 
18.2 
19.1 
18.6 
8.0 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 3 3.2 14.5 13.1 
14.8 
19.3 
22.7 
22.4 
.largecircle. 
.circleincircle. 
.circleincircle. 
Example 4 15.3 
18.0 17.7 
19.6 
18.8 
19.3 
19.7 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 5 8.5 12.2 18.1 
18.0 
16.2 
13.0 
17.3 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 6 5.7 11.8 12.8 
20.9 
14.4 
12.4 
20.8 
.largecircle. 
.circleincircle. 
.circleincircle. 
Example 7 11.7 
19.2 16.5 
15.2 
17.6 
17.2 
10.2 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 8 10.0 
17.0 15.6 
19.4 
14.6 
16.7 
7.3 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 9 16.9 
16.4 18.0 
18.1 
19.2 
17.1 
3.8 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 10 7.4 16.7 18.3 
15.3 
8.0 
11.6 
10.4 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 11 12.0 
18.3 16.9 
19.3 
15.0 
14.2 
4.8 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 12 23.2 
20.4 28.8 
15.6 
17.8 
26.3 
3.3 
.largecircle. 
.circleincircle. 
.circleincircle. 
Comparative Example 1 
7.4 21.3 15.7 
32.1 
36.3 
41.2 
30.4 
X X X 
Comparative Example 2 
19.8 
15.3 18.4 
30.6 
18.8 
39.3 
28.7 
X X X 
Comparative Example 3 
7.0 13.9 15.2 
28.4 
19.7 
40.9 
35.0 
X X X 
Comparative Example 4 
12.1 
24.8 16.7 
33.8 
27.9 
45.1 
42.6 
X X X 
__________________________________________________________________________ 
*: The values shown in the table are those obtained in terms of the image 
printed with printer (1). However, almost the same values were obtained 
even in the case where images were printed with the printer (2).