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Description  |
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The presnt invention relates to a jet ink use in ink jets and, more
particularly, to an ink for which is suitable for use in printing patterns
on woven or non-woven cloths. The present invention is concerned also with
an ink jet printing method which makes use of the ink.
2. Related Background Art
Hitherto, various methods have been used in printing patterns on woven or
non-woven cloths, such as roller printing method, screen printing method,
transfer printing method, and so forth. It has been proposed also to print
patterns on woven or non-woven cloths by means of an ink jet, as disclosed
in Japanese Patent Laid-Open No. 59108/1975.
The conventional general printing methods require printing plates such as a
plate for printing cylinder and a screen plate, which are generally
expensive. The transfer printing method also requires an expensive plate
for transferring a sheet of transfer paper. Therefore, these conventional
methods are not profitable unless the quantity of the product is
sufficiently large. In addition, since the fashion of the print pattern
changes rapidly, there is a risk in that a large quantity of the printed
products are not sold but kept in stock when production cannot follow the
rapid change in the fashion.
The printing method making use of an ink jet has been proposed to deal with
these problems. This method, however, suffers from the following
disadvantages. Namely, the quality of the print tends to be impaired due
to blotting on the cloth, partly because the ink jet printer does not
allow the use of an ink having high viscosity and partly because cloth
usually has rougher texture than paper, thus making it difficult to print
patterns of minute or delicate design. In addition, the discharge of the
ink tends to be unstable and the response to high frequency is liable to
be impaired depending on the physical property of the ink, owing to the
fact that the ink has to be discharged through minute nozzles at high
velocity and at high frequency.
It is also known that the print formed by using a conventional ink for ink
jet, particularly that printed by use of a reactive dye or reactive
disperse dye, exhibits a slow dye-fixing rate and a minimal washing
fastness.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide an ink for
ink jet printing which is capable of overcoming the problems from the view
point of economy involved by the conventional printing methods, and also
eliminates problems encountered by the known ink jet printing, more
particularly obtaining precise and stable prints, and at the same time,
achieving a high dye-fixing rate and a high degree of washing fastness of
the printed material.
Another object of the present invention is to provide an ink jet printing
method which makes use of such ink.
To these ends, according to the present invention, there is provided an ink
for use in an ink jet comprising as the main components, a reactive dye or
a reactive dispersing dye, and a solvent composed mainly of water and an
organic solvent which is not reactive with the dye.
According to another aspect of the present invention, there is provided an
ink jet printing method in which an ink for printing is applied by an ink
jet system to a cloth having fibers dyeable by a reactive dye, wherein
said ink comprises as the main components a reactive or reactive
dispersing dye, and a solvent composed mainly of water and an organic
solvent which is not reactive with said dye.
According to a further aspect of the present invention, there is provided
an ink jet printing method in which an ink for printing is applied by an
ink jet system to a cloth having fibers dyeable by a reactive dye followed
by a dye-fixing treatment, wherein said ink comprises as the main
components a reactive dye or reactive dispersing dye, and a solvent
composed mainly of water and an organic solvent which is not reactive with
said dye.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The major feature of the ink in accordance with the present invention
resides in that an organic solvent which is not reactive with reactive dye
or reactive disperse dye contained in the ink is used as the solvent which
constitutes the liquid medium of the ink.
Through an intense study on the printing method of the ink jet type, the
inventors have found that superior quality of printing is obtainable when
a reactive dye or a reactive dispersion dye is used as the dye for the
printing ink together with a polyhydric alcohol or a similar organic
solvent which is commonly used as a part of the liquid medium of ink, but
in such a case, another new problem may occur, that is, the dye-fixing
rate is impaired, and the fastness of the printed material to washing is
reduced.
The inferior dye-fixing rate is considered to be attributable to the fact
that a part of the dye reacts with the solvent such as polyhydric alcohol
during the storage of the ink, resulting in a reduced reactivity with the
fibers of the cloth.
Regarding the fastness to washing, it is considered that the water content
of the ink which has attached to the cloth is evaporated rapidly, whereas
the solvent such as polyhydric alcohol remains on the cloth without being
evaporated. The solvent such as polyhydric alcohol then reacts with a part
of the dye, during heating or alkali treatment conducted in the
post-treatment subsequent to the printing, and so reaction products easily
come off when the cloth is washed. The reduce the washing fastness.
In view of the above, the present invention proposes to use, as the organic
solvent which constitutes a liquid medium of an ink, an organic solvent
which is not reactive with the reactive dye or reactive dispersion dye.
The reactive dye which can be used in the ink of the present invention
includes various types of dye which have been used in dyeing fibers or in
the conventional printing method, such as water-soluble azo dyes,
anthraquinone dyes, phthalocyanine dyes, and so forth, most of which are
known.
The reactive dye has a water-soluble radical such as sulfonic acid radical
or carboxylic radical, as well as a radical which forms a covalent bond
with the fibers through reaction with hydroxyl or amino group in the
fiber. Examples of such latter radical are dichlorotriazine,
monochlorotriazine, trichloropyrimidine, monochlorodifluoropyrimidine,
chlorobenzothiazole, dichloropyridazone, dichloropyridazine,
dichloroquinoxaline, epoxy and 3-carboxypyridiniotrazine radicals, and
further
--SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
--SO.sub.2 NHCH.sub.2 CH.sub.2 OSO.sub.3 H,
--NHCOCH.sub.2 CH.sub.2 OSO.sub.3 H,
--NHCOCH.sub.2 CH.sub.2 Cl,
--NHCOCH.dbd.CH.sub.2, --SO.sub.2 CH.dbd.CH.sub.2,
--CH.sub.2 NHCOCCl.dbd.CH.sub.2,
--NHCOCBr.dbd.CH.sub.2,
--NHCOCH.sub.2 Cl, --NHCH.sub.2 OH, and --PO.sub.3 H.
The ink in accordance with the present invention can contain any one of the
reactive dyes mentioned above. Amongst these reactive dyes, the following
dyes are used preferably.
C.I. Reactive Yellow 2, 3, 13, 15, 17, 18, 23, 24, 37, 42, 57, 58, 64, 75,
76, 77, 79, 81, 84, 85, 87, 88, 91, 92, 93, 95, 111, 115, 116, 130, 131,
132, 133, 135, 136, 137, 139, 140, 142, 143, 144, 145, 146, 147, 148, 151,
162, 163,
C.I. Reactive Orange 5, 7, 11, 12, 13, 15, 16, 35, 45, 46, 56, 62, 70, 72,
74, 82, 84, 87, 91, 92, 93, 95, 97, 99,
C.I. Reactive Red 3, 13, 16, 21, 22, 23, 24, 29, 31, 33, 35, 45, 49, 55,
63, 85, 106, 109, 111, 112, 113, 114, 118, 126, 128, 130, 131, 141, 151,
170, 171, 174, 176, 177, 180, 183, 184, 186, 187, 188, 190, 193, 194, 195,
196, 200, 201, 202, 204, 206, 218, 221,
C.I. Reactive Violet 1, 4, 5, 6, 22, 24, 33, 36, 38,
C.I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 18, 19, 21, 25, 27, 28, 38,
39, 40, 41, 49, 52, 63, 71, 72, 74, 75, 77, 78, 79, 89, 100, 101, 104,
105, 119, 122, 147, 158, 160, 162, 166, 169, 170, 171, 172, 173, 174, 176,
179, 184, 190, 191, 194, 195, 198, 204, 211, 216, 217,
C.I. Reactive Green 5, 8, 12, 15, 19, 23,
C.I. Reactive Brown 2, 7, 8, 9, 11, 16, 17, 18, 21, 24, 26, 31, 32, 33,
C.I. Reactive Black 1, 5, 8, 13, 14, 23, 31, 34, 39 and the like.
When the fiber to be subjected to the printing is made of wool or nylon,
C.I. Reactive Yellow 21, 34, 39, 69, 98, 125, 127,
C.I. Reactive Orange 29, 53, 68,
C.I. Reactive Red 28, 65, 66, 78, 83, 84, 100, 116, 136, 147, 154, 172,
C.I. Reactive Violet 34,
C.I. Reactive Blue 50, 69, 94, 177,
C.I. Reactive Brown 12 and the like are preferably used.
The reactive dispersion dye which can be used for the ink of the present
invention may be azo dyes or anthraquinone dyes which exhibit slight
solubility in water and which have been used in printing of
polyester/cotton mix-spun cloth.
The reactive dispersion dye generally has a molecular structure similar to
that of the disperse dye, and has a radical which forms a covalent bond
with fiber through reaction with hydroxyl or amino group in the fiber.
Examples of such a radical are ethyleneimine, azide, sulfonethyleneimide,
dichlorotriazine, monochlorotriazine, trichloropyrimidine, monochloro
difluoropyrimidine, chlorobenzothiazole, dichloropyridazone,
dichloropyridazine, dichloroquinoxaline, epoxide and
3-carboxypyridiniotriazine radicals, and further
--SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
--SO.sub.2 NHCH.sub.2 CH.sub.2 OSO.sub.3 H,
--NHCOCH.sub.2 CH.sub.2 OSO.sub.3 H,
--NHCOCH.sub.2 CH.sub.2 Cl,
--NHCOCH.dbd.CH.sub.2,
--SOCH.dbd.CH.sub.2,
--CH.sub.2 NHCOCCl.dbd.CH.sub.2,
--NHCOCBr.dbd.CH.sub.2,
--NHCOCH.sub.2 Cl,
--NHCH.sub.2 OH, --PO.sub.3 H,
--SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3,
--SO.sub.2 CH.sub.2 CH.sub.2 OCOOC.sub.4 H.sub.9, and the like.
The ink in accordance with the present invention can contain any one of
these reactive dispersion dyes, among which the dyes expressed by the
following formulae and their derivatives are used preferably.
##STR1##
In the ink in accordance with the present invention, the reactive dye or
the reactive dispersion dye of the type mentioned above may be dissolved
or dispersed in a liquid medium conventionally used in general dyeing or a
solvent used for a liquid medium for inks in ink jets, particularly in a
medium containing water and an organic solvent. It is necessary that, when
the organic solvent is used in a mixture with water, the solvent does not
have active hydrogen such as of hydroxyl or amino group which would react
with the reactive dye or reactive dispersion dye.
Preferable examples of such an organic solvent are amides such as
dimethylformamide and dimethylacetoamide, ketones such as acetone and
methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and other
solvents such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
and so forth. Among these solvents, the following solvents are used most
preferably: dialkyl (carbon number 1 to 4) ether of polyoxyethylene (added
mol number 1 to 15); dialkyl (carbon number 1 to 4) ether of
polyoxyethylene.oxypropylene block (or random) polymer (added mol number 1
to 15), and the like.
The organic solvent may be used solely, although alternatively, a mixture
of two or more of such solvents may be used. Preferably, the organic
solvent occupies about 1 to 70 wt % of the ink solvent. The amount of the
ink solvent is preferably selected such that the content of the dye
explained about ranges between about 0.1 to 15 wt % of the ink.
In addition to the essential components mentioned above, the ink in
accordance with the present invention can contain, as required, various
additives such as a dispersing agent, surfactant, viscosity adjusting
agent, another dye, and so forth. It is also preferred that the additive
used in the ink of the present invention is not reactive with the dye
mentioned above. This, however, is not essential and the additive may be
reactive with the dye, if such an additive is used only in a trace amount.
Important examples of the dispersing agent or surfactant which may be used
as required are: anionic dispersing agents or surfactants such as fatty
acid salt, alkylsulfate, alkylbenzene sulfonate, alkylnaphthalene
sulfonate, dialkylsulfosuccinate, alkylphosphate, naphthalene
sulfonate-formalin condensation product, and polyoxyethylene
alkylsulfonate; and nonionic dispersing agents or surfactants such as
polyoxyethylene alkylether, polyoxyethylene alkylphenylether,
polyoxyethylene fatty acid ester, sorbitan fatty acid ester,
polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine,
glycerine fatty acid ester, and oxyethylene oxypropylene block polymer.
As the viscosity adjusting agent, a water-soluble natural or synthetic high
molecular material such as carboxymethyl cellulose, sodium polyacrylate,
polyvinyl pyrrolidone, arabic gum, starch and so forth are preferably
used. With or without such viscosity adjusting agent, the viscosity of the
ink is adjusted to be 50 cps or less, preferably 1 to 15 cps, at
25.degree. C.
For preparing an ink for use in ink jet system which employs electrostatic
charging of the ink, a specific-resistance adjusting agent such as an
inorganic salt, e.g., lithium chloride, ammonium chloride and sodium
chloride may be added.
When the ink jet is of the type in which the ink is discharged by the
action of heat energy, the ink may require adjustment of thermal physical
properties such as specific heat, thermal expansion coefficinet, heat
conductivity, and so forth.
The ink in accordance with the present invention can contain other types of
additive such as an antifoamer, a penetrating agent, an antimold agent and
a pH adjuster.
The ink in accordance with the present invention for use in ink jet is
generally prepared by mixing or dissolving the essential components as
mentioned above with or without addition of the above-mentioned optional
component, and then grinding the mixture by a suitable known grinding
means such as a ball mill, a sand mill or a speed-line mill. When a
reactive dispersion dye is used, the particle size of the dye is selected
to be 30 .mu.m or less, preferably 20 .mu.m or less. Too large a particle
size of the reactive dispersion dye will cause problems such as blocking
of an ink jet nozzle upon recording, non-level dyeing property of the dye
in the subsequent dyeing process, and so forth. When a medium capable of
dissolving a reactive dispersion dye is used in combination with such a
type of dye, the ink composition in accordance with the present invention
can be obtained simply by a dissolving operation such as, for example, by
heating.
It is also preferred that, during the preparation of the ink of the present
invention from the above-mentioned essential components and optional
component, the surface tension of the ink is adjusted to range between 30
and 60 dyne/cm. Such an adjustment of the surface tension can be effected
without substantial difficulty by those skilled in the art, through
suitable selection of the dye and the combination between the dye and the
solvent and through addition of a suitable additive.
When the surface tension is below 30 dyne/cm, the ink attaching to a cloth
woven from various fibers or a non-woven cloth undesirably blots to make
it difficult to print a minute or delicate pattern on the cloth. On the
other hand, any level of surface tension exceeding above-mentioned range
makes it difficult to form ink droplets of a uniform size at the time of
ink discharging. The above-mentioned values of the surface tension are the
values as measured at 25.degree. C. by a surface tension meter which is
produced by TOA DENPA KOGYO K.K. under the commercial name of KYOWA CBVP
SURFACETENSIOMETER A-1.
The ink of the present invention for ink jet is suitable for use in
printing of patterns on a woven or non-woven cloth by ink jet printing.
More particularly, the ink of the invention is suited to printing on woven
or non-woven cloths formed of fibers which are dyeable with the reactive
dye, such as cotton, hemp, viscose, wool, silk and nylon, as well as
mix-spun woven or non-woven cloths formed of mix-spun yarns of the
above-mentioned fibers and synthetic fibers such as polyester fibers,
acetate fibers, polypropylene fibers, vinylon fibers and so forth. If
necessary, these woven or non-woven cloths may be subjected to a
pre-treatment for facilitating printing by ink jet. Such a pretreatment
may be effected by applying a water-soluble polymer or a water-dispersible
polymer to the surface of the fibers so as to enable the cloth to quickly
absorb and hold the ink.
Any type of ink jet system can be used for printing patterns on a woven or
non-woven cloth by means of ink jet, provided that it enables the ink to
be released from nozzles to reach the woven or non-woven cloth as a
target. Typical examples of such ink jet systems are disclosed in, for
instance, "IEEE Transactions on Industry Applications" Vol. JA-13, No. 1
(Feb. and Mar., 1977) and also in Nikkei Electronics No. 305 (Dec. 6,
1982).
The ink in accordance with the present invention can conveniently be used
in these known ink jet systems. Some of these ink jet systems will be
explained hereinafter.
In a first system known as electrostatic attraction type ink jet system, a
strong electric field is developed between a nozzle and an accelerating
electrode which is disposed several millimeters ahead of the nozzle. Under
the influence of the electric field, the ink is successively extracted in
the form of particles or droplets from the nozzle and, while the ink
droplets fly in the gap between deflecting electrodes, the signal is
applied to the deflecting electrodes, so that a desired pattern is
printed. Alternatively, the ink droplets are jetted in accordance with the
information signal, without being deflected. Either of these methods can
be carried out successfully with the ink of the present invention.
In a second system, the ink is pressurized to a high pressure by means of a
small-capacity pump, while the nozzle is vibrated by, for example, a
quartz oscillator, whereby minute ink droplets are jetted forcibly.
Simultaneously with the jetting, the ink droplets are electrostatically
charged in accordance with the information signal. The ink droplets thus
charged are deflected by amount corresponding to the quantity of the
charges, when they pass through a gap between deflecting electrode plates.
In a modification which is usually referred to as "microdot ink jet
system", the ink pressure and the exciting condition are maintained within
given optimum ranges so as to generate two kinds of ink droplets from the
tip of nozzle, one being large while the other is small, and only the
small droplets are used in the printing. This modification makes it
possible to form minute ink droplets by means of nozzles with
comparatively large nozzle port diameters as those in ordinary ink jet
systems.
A third system employs, for the purpose of pressurizing the ink,
piezoelectric elements in place of mechanical ink pressurizing eans such
as a pump. The ink is pressurized and jetted from a nozzle by a mechanical
displacement of the piezoelectric element energized by an electric signal.
The ink in accordance with the present invention can be used preferably
also in an ink jet system disclosed in Japanese Patent Laid-Open No.
59936/1979 in which a drastic change in the volume of the ink is generated
by heat energy and a resultant force acts to discharge the ink from a
nozzle thereby effecting printing. In this system, a high degree of
stability of the ink jet is achieved.
The ink in accordance with the present invention can be used in any one of
these known ink jet systems, for the purpose of printing characters and
patterns on a woven or non-woven cloth. In a preferred form of the ink in
accordance with the present invention, since the surface tension is
controlled to fall within a predetermined range, the jetting of the ink
droplets from the nozzle is performed in a very stable manner. In
addition, the jetted ink attaches appropriately to the cloth without
excessive blotting despite the presence of texture in the cloth.
Therefore, a clear and minute pattern can be formed through a subsequent
dyeing step by an alkali treatment or heat treatment. In contrast, the
conventional inks often fail to form fine or delicate pattern sometimes as
a result of mis-attaching of the ink dots to the predetermined positions
and sometimes as a result of rapid spreading of the ink dots along the
texture which permits the ink to blot.
According to the invention, the ink can attach to the cloth precisely in
conformity with picture signals. The ink jet, however, merely causes the
ink to attach to the cloth. It is, therefore, preferred that a suitable
post-treatment be conducted to cause the dye to react with and be fixed to
the fibers of the cloth and to remove the dye which has not been fixed.
The dye reacts with the fibers during the fixing treatment. In the case of
conventional printing inks containing organic solvents such as a
polyhydric alcohol reactive with the dye, a part of the dye undesirably
reacts with the organic solvent while the ink is stored, resulting in a
lowered dye-fixing rate. In addition, the organic solvent such as
polyhydric alcohol, which is non-volatile, remains on the cloth to some
extent so that it reacts with the dye during the fixing treatment to form
a reaction product, resulting in deterioration in the washing fastness.
Unlike these conventional inks, the ink in accordance with the present
invention can effectively prevent the dye-fixing rate and the washing
fastness of the printed cloth from being lowered, by virtue of the fact
that an organic solvent which is not reactive with the dye is used.
The reaction fixing of the dye and the removal of the unreacted dye can be
effected by known methods such as steaming method, HT steaming method,
thermo-fix method, alkali-pad steam method, alkali-blotch steam method,
alkali-shock method, alkali cold-fix method, and so forth, followed by
washing.
According to the invention, the necessity for the production of an
expensive printing plate, which is essential in the ordinary printing
methods, is eliminated and the image to be printed can easily be formed
and modified by means of a computer. It is therefore possible to cope with
a rapid change in the fashion, while dispensing with the conventional
expensive plate. This makes it possible to obtain a sufficient profit even
by small-quantity production, unlike the conventional printing method
which is not paying unless a large quantity of products is produced. The
printing by the use of the ink and the printing method in accordance with
the present invention can be carried out not only in an industrial scale
but also in a house-hold scale for enabling individual to produce a
printed cloth having a high washing fastness according to her or his taste
.
The invention will become more apparent from the following description of
examples and comparison examples in which the contents are expressed
either in terms of weight parts (parts) or weight percents (%).
Example 1
______________________________________
Reactive dye (C.I. reactive red 24)
5 parts
Tetraethyleneglycol dimethylether
30 parts
Water 65 parts
______________________________________
A mixture solution of these materials was adjusted to pH 8.3 using sodium
hydroxide and was stirred for 5 hours, followed by filtration by a
Fluoropore Filter FP-100 (commercial name, produced by SUMITOMO ELECTRIC
IND., LTD), thus obtaining a water-based ink (1A) in accordance with the
present invention.
Example 2
______________________________________
Reactive dye (C.I. reactive blue 216)
6 parts
Diethyleneglycol diethylether
6 parts
N--methyl-2-pyrrolidone
15 parts
Water 73 parts
______________________________________
Using these materials, a water-based ink (1B) of the invention was formed
by the same process as that in Example 1.
Example 3
______________________________________
Reactive dye (C.I. reactive orange 16)
4 parts
Reactive dye (C.I. reactive yellow 37)
3 parts
Dipropyleneglycol dimethylether
10 parts
1,3-dimethyl-2-imidazolidinone
20 parts
Nonionic surfactant (commercial name EMULGEN
0.2 parts
PP-150, produced by KAO CORP.)
Water 63 parts
______________________________________
The mixture solution was adjusted to pH 4.7 by means of acetic acid and
stirred for 5 hours, followed by filtration by means of Fluoropore Filter
FP-100 (produced by SUMITOMO ELECTRIC IND., LTD), thus forming a
water-based ink (1C) in accordance with the invention.
Example 4
______________________________________
Reactive dye (C.I. reactive red 180)
7 parts
H.sub.3 C--(OC.sub.3 H.sub.6)--(OC.sub.2 H.sub.4)--OC.sub.2 H.sub.5
20 parts
Water 73 parts
______________________________________
Using these materials, a water-based ink (1D) in accordance with the
invention was formed in the same process as Example 1.
Comparison Example 1
A comparison example (1E) of ink was prepared by the same process as
Example 1, except that triethylene-glycol was used instead of
tetraethyleneglycol dimethylether.
The properties of the inks of Examples 1 to 4 and the Comparison Example 1
are shown in Table 1.
Example 5
Printing was conducted on different types of cloth by means of an ink jet
printer utilizing heat energy as disclosed in Japanese Patent Laid-Open
No. 59936/1979, using the water-based inks of Examples 1 to 4 and the
Comparison Example 1. After the printing, the cloth was subjected to a
fixing treatment by steaming which was conducted in an alkali atmosphere
for 1 minute at 100.degree. C., followed by 10-minute washing by a neutral
detergent. The kinds of the cloth and the properties of the print on these
cloths are shown in Table 2.
TABLE 1
______________________________________
Comp.
Examples 1-4 Example 1
Ink 1A Ink 1B Ink 1C Ink 1D
Ink 1E
______________________________________
Surface 53 52 48 46 59
tension
(dyne/cm)
pH 8.3 8.3 4.7 4.7 8.3
______________________________________
TABLE 2
__________________________________________________________________________
Ink 1B Ink 1C
Ink 1A Polyester 65%
Polyester 50%
Ink 1D
Ink 1E
Cotton 100%
Cotton 35%
Cotton 50%
Wool 100%
Cotton 100%
Cloths
(Georgette)
(Broad) (Broad) (Taffeta)
(Georgette)
__________________________________________________________________________
Blot *1
o o o o o
Fluctuation
o o o o o
in dot dia.
*2
Dye-fixing
o o o o x
rate *3
Washing
o o o o x
fastness *4
__________________________________________________________________________
Example 6
______________________________________
Dye of formula (2) 5 parts
Anionic surfactant (dispersing agent)
30 parts
(Commercial name DEMOL N produced by
KAO CORP. Tetraethyleneglycol dimethylether
Water 61 parts
______________________________________
The above-mentioned materials were subjected to dispersing treatment which
was conducted for about 36 hours in a alumina ball mill, and the mixture
was adjusted to pH 8.3 by sodium hydroxide. The mixture was then subjected
again to dispersing treatment which was conducted for 3 hours by means of
an alumina ball mill, followed by filtration conducted with Fluoropore
Filter FP-1000 (produced by SUMITOMO ELECTRIC IND., LTD.) so as to remove
coarse particles exceeding 10 .mu.m, whereby a water-based ink (2A) of the
invention was obtained.
Example 7
______________________________________
Dye of formula (7) 4 parts
Anionic surfactant (Commercial name NIKKOL
0.05 parts
OTP-100S, produced by NIKKON CHEMICALS
LTD.)
Anionic surfactant (Commercial name
1.5 parts
DEMOL C, produced by KAO CORP.)
Nonionic surfactant (commercial name EMULGEN
0.2 parts
981, produced by KAO CORP.)
Diethyleneglycol diethylether
6.5 parts
N--methyl-2-pyrrolidone 15 parts
Water 73 parts
______________________________________
Using these materials, a water-based ink (2B) of the invention was prepared
in the same process as Example 6.
Example 8
______________________________________
Dye of formula (14) 7 parts
Dye of formula (15) 2 parts
Nonionic surfactant (Commercial name
1.5 parts
EMULGEN 707, produced by KAO CORP)
Nonionic surfactant (Commercial name
0.2 parts
RHEODOL TW-P120, produced by KAO COPR)
Dipropyleneglycol dimethylether
10 parts
1,3-dimethyl-2-imidazolidinone
20 parts
Water 57.5 parts
______________________________________
These materials as a mixture were subjected to dispersing treatment which
was conducted in an alumina ball mill for about 40 hours, and the mixture
was adjusted to pH 5.6 by acetic acid. The mixture was then subjected
again to dispersing treatment which was conducted for 2 hours, followed by
filtration by Fluoropore Filter FP-500 (produced by SUMITOMO ELECTRIC
IND., LTD. so as to remove coarse particles exceeding 5 .mu.m, whereby a
water-based ink (2C) of the present invention was prepared.
Example 9
______________________________________
Dye of formula (9) 6 parts
Anionic surfactant (Commercial name
5.5 parts
IONET D-2, produced by SANYO CEMICAL
INDUSTRIES)
H.sub.3 C--(OC.sub.3 H.sub.6)--(OC.sub.2 H.sub.4).sub.2 --OC.sub.2
H.sub.5 20 parts
Water 68.5 parts
______________________________________
Using these materials, a water-based ink (2D) of the invention was prepared
by the same process as Example 8.
Comparison Example 2
An ink (2E) as a comparison example was formed by the same materials and
the same process as Example 6, except that triethyleneglycol was used in
place of tetraethyleneglycol dimethylether in Example 6.
Comparison Example 3
An ink (2F) as a comparison example was formed by the same materials and
the same process as Example 8, except that dipropyleneglycol was used in
place of dipropyleneglycol dimethylether in Example 8.
The properties of the inks of Examples 6 to 9 and Comparison Examples 2
and 3 are shown in Table 3.
Example 10
Printing was conducted on different types of mix-spun woven cloth by means
of an ink jet printer employing heat energy as disclosed in Japanese
Patent Laid-Open No. 59936/1979, using the water-based inks 2A-2F) of
Examples 6 to 9 and the Comparison Examples 2 and 3. After the printing,
each cloth was subjected to a heat-treatment which was conducted for 90
seconds at 180.degree. C., followed by dyeing treatment conducted for 20
seconds at 90.degree. C. in an alkali bath adjusted by sodium carbonate.
The cloth was then washed by a neutral detergent, whereby printed cloths
were obtained. The results are shown in Table 4.
TABLE 3
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Ink 2A Ink 2B Ink 2C Ink 2D
Ink 2E
Ink 2F
______________________________________
Surface 44 50 38 42 55 41
tension
(dyne/cm)
pH 8.3 8.3 5.6 5.6 8.3 5.6
______________________________________
TABLE 4
__________________________________________________________________________
Ink 2A
Ink 2B
Ink 2C
Ink 2D
Ink 2E
Ink 2F
Polyester
Polyester
Polyester
Polyester
Polyester
Polyester
65% 65% 50% 50% 65% 65%
Cotton
Cotton
Cotton
Cotton
Cotton
Cotton
35% 35% 50% 50% 35% 35%
Cloths (Satin)
(Broad)
(Broad)
(Knit)
(Satin)
(Broad)
__________________________________________________________________________
Blot *1
o o o o o o
Fluctuation
o o o o o o
in dot dia. *2
Dye-fixing
o o o o x x
rate *3
Washing
o o o o x x
fastness *4
__________________________________________________________________________
*1 Sharpness of fine line (about 1 mm wide) of the printed pattern was
examined by visual check. Mark o represents "good", while x represents
"poor".
*2 Dots were printed in a line of 30 cm long at a pitch of 1 mm and the
fluctuation of the dot diameter was visually checked. Mark o represents
"good", while x represents "poor".
*3 The print immediately after the streaming treatment and the print afte
10minute washing were compared visually. Mark o represents that there was
no difference, while x represents that reduction in the color thickness
was observed after washing.
*4 The print after additional 1hour washing by a neutral detergent was
visually compared with the print after 10minute washing.
Mark o represents that there was no difference, while x represents that a
reduction in the color thickness was observed when the washing time became
longer.
Example 11
A water-based ink (3A) in accordance with the present invention was
prepared by the same process as Example 2, except that acetone was used in
place of the diethyleneglycol diethylether in Example 2. The ink 3A showed
a surface tension of 46 dyne/cm and a pH value of 8.3.
Printing was carried out using the ink 3A on various cloths substantially
under the same conditions as Example 5. The results were substantially the
same as those obtained with the ink 1B.
Example 12
______________________________________
Reactive dye (C.I. reactive red 24)
2 parts
1,3-dimethyl-2-imidazolidinone
50 parts
N--methyl-2-pyrrolidone 10 parts
Water 38 parts
______________________________________
Using these materials, a water-based ink (3B) of the invention was prepared
by the same process as Example 1. The ink 3B showed a surface tension of
43 dyne/cm and a pH value of 8.3.
Printing was carried out using the ink 3B on various cloths substantially
under the same conditions as Example 5. The results were substantially the
same as those obtained with the ink 1A.
Example 13
______________________________________
Dye of formula (7) 10 parts
Anionic surfactant (dispersing agent,
5 parts
Commercial name DEMOL N, produced
by KAO COPR.)
1,3-dimethyl-2-imidazolidinone
70 parts
Water 15 parts
______________________________________
Using these materials, a water-based ink (3C) of the invention was prepared
by the same process as Example 6. The ink 3C showed a surface tension of
39 dyne/cm and a pH value of 8.3.
Printing was carried out using the ink 3C on various cloths substantially
under the same conditions as Example 10. The results were substantially
the same as those obtained with the ink 2A.
Example 14
Five types of water-based ink (3D), (3E), (3F), (3G) and (3H) were prepared
by the same process as Example 13, substituting the dyes of formulae (1),
(5), (12), (16) and (18) for the dye used in Example 13. These inks showed
surface tension and pH value of the samelevels as those shown by the ink
3C.
Printing was carried out using individually these five types of ink 3D to
3H on various cloths substantially under the same conditions as Example
10. The results were substantially the same as those obtained with the ink
3C.
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