JPH05186727A - Ink for ink jet printing, ink jet printing method, and machinery using the ink - Google Patents

Abstract

PURPOSE:To provide an ink and a printing method which satisfy the requirements for conventional printing ink and ink jet printing generally used, i.e. simultaneously satisfy the requirements on dyeing for obtaining a vividly and densely dyed material and the requirements on delivery performance for obtaining stable delivery for a short or long period of time to realize highly reliable printing. CONSTITUTION:An ink for ink jet printing containing a reactive dye and an aqueous liquid medium, which contains chloride and/or sulfate ions in an amount of 10-20,000ppm based on the reactive dye; and an ink jet printing method comprising applying a printing ink by an ink jet system to a cloth containing cellulose fibers and then subjecting the cloth to exhaustion, wherein the printing ink is the above-mentioned ink.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-jet printing ink, an ink-jet printing method and a device using such an ink, and in particular, a woven or non-woven fabric such as cotton which is mainly composed of cellulose fibers and which can be dyed with a reactive dye. Alternatively, the present invention relates to an ink-jet printing ink suitable for printing a mixed-spun woven fabric or a mixed-spun nonwoven fabric composed of these fibers and other synthetic fibers, an inkjet-printing method using the same, and a device using such an ink.

[0002]

2. Description of the Related Art The mainstream of printing at present is screen printing or roller printing. These methods are not suitable for high-mix low-volume production, and it is difficult to quickly respond to a fashion. Therefore, a plateless electronic printing system has recently been demanded. In response to this demand, many printing methods using ink jet recording have been proposed, and expectations from various fields are increasing. As an ink jet printing ink, (1) color is developed to a sufficient density, (2) the nozzle of the head is not clogged, (3) the ink is quickly dried on the cloth, (4) on the cloth Less irregular bleeding, (5) No change in physical properties or precipitation of solids during storage, (6) No change in ejection characteristics during long-term durability, especially due to the method using heat energy In this case, performances such as disconnection and deposition of foreign matter on the heat generating head and (7) good dyeing rate are required.

In order to satisfy these required performances, the following means have been conventionally proposed. First, as for the problem mentioned in (1) above, it is a general means to increase the concentration of the dye to give a sufficient concentration, and in particular, to use a small droplet of 200 pl or less, It was an indispensable technique for strong fabrics. However, in such an ink, the water in the ink evaporates from the tip of the nozzle, so that the viscosity is increased and the dye that is a solid content is deposited to cause the problem (2). Therefore, in order to solve the problem described in (2) above, measures such as adding a polyhydric alcohol such as glycerin have been adopted.
If the dye concentration exceeds 5%, no particular solution is obtained, and satisfactory results cannot be obtained except for a very specific combination of dye and solvent. Regarding the problem mentioned in (3) above, the water repellency of the fabric has a large influence, but for example,
There is no particular problem when the water-based ink is used for the cloth mainly composed of cellulose fibers. With respect to the problem (4), many proposals have already been made. For example, the addition of tannin in JP-A-61-231289 and the carboxylic acid group-containing polymer in JP-A-62-283174 have been proposed. Although addition to ink is mentioned, the problem (2) is unavoidable in all cases. Above (5)
The problems listed in (6) and (6) may be due to the structure of the dye, but detailed studies have not been made and the problems have not been sufficiently solved. With regard to (7) above, in the case of inkjet printing, the absolute amount of the dye adhering to the fabric is much smaller than that of the type using conventional printing paste, and therefore an improvement in the excellent reactivity of the dye itself is expected. Has been done. As described above, in the prior art, even if a means for individually satisfying each performance can be found, a printing ink and an inkjet printing method which satisfy these performances at the same time and solve the series of problems described above are known. The current situation is that it has not been done.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problems of the conventional general printing ink and ink jet printing as described above, that is, high dyeing rate.
An ink, a printing method, and an ink which simultaneously satisfy both a dyeing problem of obtaining a clear and highly concentrated dyed product and a discharge performance problem of enabling stable and reliable printing for a short or long period of time. An object is to provide a device using such ink.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention provides an inkjet printing ink containing a reactive dye and an aqueous liquid medium, wherein the reactive dye contains 10 to 20,000 ppm of chlorine ions and / or sulfate ions. Ink, a method for applying a printing ink to a cloth containing a cellulose fiber by an inkjet method, and then performing a dyeing treatment, wherein the printing ink is the above-mentioned ink, and such A device that uses ink.

[0006]

The present inventors have improved the ink for ink-jet printing ink so as to simultaneously satisfy the various required performances as described above, and as a result, as a result, a specific amount of chlorine is added to the reactive dye contained in the ink. By containing ions and / or sulfate ions, even in a printing method that uses small droplets and a small amount of ink is applied, as in inkjet printing, color development characteristics such as level dyeing and dyeing rate are significantly improved. I found that. This phenomenon is considered to be due to the existence of some effect in these ionic substances that can maximize the reaction characteristics of the dye at the molecular level. Further, in a preferred embodiment of the present invention, by further containing at least one substance selected from the group consisting of silicon, iron, nickel and zinc in the ink in a specific ratio, the leveling property,
It is possible to further improve the coloring property such as dyeing property.
Moreover, limiting the content ratios of silicon, iron, nickel and zinc in the ink within the above specific range is particularly effective when an inkjet head utilizing thermal energy is used.
It is also extremely effective in obtaining stable ejection characteristics of ink for a long period of time. The reason for this is that an excessive content of these substances causes a decrease in the foaming power due to deposits on the head, but the formation of deposits by moderate addition causes
It is possible to alleviate the cavitation at the time of defoaming without causing a decrease in the foaming power and prevent the disconnection.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The ink-jet printing ink of the present invention is characterized by containing a reactive dye and an aqueous liquid medium and, in addition, containing a specific amount of a specific substance. The substances used in the present invention and mainly characterizing the present invention are chloride ions and / or sulfate ions, and the amount added to the ink is 0.1 to 20 relative to the reactive dye contained in the ink. 1,000 ppm, preferably 10-1
5,000 ppm, more preferably 10 to 10,000
It is in the ppm range. Within this range, not only the above-mentioned color-developing characteristics are improved, but also the problem of clogging which is usually concerned can be dealt with in the use in the printing field. On the other hand, when the content of chlorine ion and / or sulfate ion is out of the range of 10 to 20,000 ppm with respect to the reactive dye, the effect of improving the color forming property is insufficient.

In a preferred embodiment of the present invention, the above ink further contains at least one substance selected from the group consisting of silicon, iron, nickel and zinc in a total amount of 0.1. ~ 30 ppm, preferably 0.2-20
It is preferable that the content is in the range of ppm, more preferably 0.3 to 10 ppm. Furthermore, the ink of the present invention is
The total amount of calcium and / or magnesium in the ink in combination with the above metals is 0.1 to 30 ppm, preferably 0.2 to 20 ppm, more preferably 0.3 to 10 ppm.
It is preferably contained in the range of ppm, and the dyeing rate can be further improved.

Preferred one of the dyes used in the present invention
Examples are reactive dyes having vinyl sulfone groups or monochlorotriazine groups. Specific examples of these dyes include C.I. I. Reactive Yellow 2, 15, 37, 4
2, 76, 95; C.I. I. Reactive Red 21, 2
2, 24, 33, 45, 111, 112, 114, 18
0, 218, 226; C.I. I. Reactive blue 1
5, 19, 21, 38, 49, 72, 77, 176, 2
03, 220; C.I. I. Reactive orange 5, 1
2, 13, 35; C.I. I. Reactive brown 7, 1
1, 33, 46; C.I. I. Reactive green 8, 1
9; C.I. I. Reactive Violet 2, 6, 22;
C. I. Examples thereof include those typified by Reactive Black 5, 8, 31, 39 and the like. Another preferred dye is a reactive dye having at least two reactive groups. Specific examples of these dyes include C.I. I. Reactive Yellow 168, 175; C.I. I. Reactive red
228, 235; C.I. I. Reactive Blue 230,
235; C.I. I. Reactive Orange 95; C.I. I.
Examples of the dye include one having two or more reactive groups in one molecule represented by Reactive Brown 37, but the present invention is not limited to the above dyes. However, the use of the dyes exemplified in any of the above aspects is a preferable aspect in that more efficient dyeing property to a fabric can be obtained. These dyes can be used alone, as a mixture, or as a mixture having different hues, and can also be used in combination with other dyes. However, the above C. I. When using a commercially available dye with a number, all of them contain impurities,
It is preferably purified before use. One or more of these dyes are contained in the ink, and the amount used is preferably 5 to 25% by weight, more preferably 5 to 20% by weight, and particularly preferably 5 to 15% by weight based on the total amount of the ink. It is in the range of% by weight. That is, particularly in the case of inkjet printing, since small droplets are used, it is difficult to obtain a desired coloring density when the dye concentration in the ink is too low, and when the density is too high, the ink ejection suitability is insufficient. Disappear. In the present invention, it is a particularly preferable embodiment that the amount of the dye used is set within the above range in order to obtain a desired color density with good reproducibility.

Water, which is an essential component of the liquid medium of the ink of the present invention, is 30 to 90% by weight, preferably 40 to 90% by weight, and more preferably 50 to 85% by weight based on the total amount of the ink.
It is in the range of% by weight. Although the above are the essential components of the ink of the present invention, a general organic solvent can be used together as a liquid medium of the ink. For example, ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; oxyethylene such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol Or an oxypropylene addition polymer; alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol and hexylene glycol; 1,2,6-hexane Triols such as triol; thiodiglycol; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyi Lower alkyl ethers of polyhydric alcohols such as (or ethyl) ether and triethylene glycol monomethyl (or ethyl) ether; polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether Lower dialkyl ethers; sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

The content of the water-soluble organic solvent as described above is generally in the range of 3 to 60% by weight, preferably 5 to 50%, based on the total weight of the ink. When the liquid medium as described above is used in combination, it can be used alone or as a mixture,
The most preferred liquid medium composition is one in which the solvent contains at least one polyhydric alcohol. Among them, thiodiglycol alone or a mixed system of diethylene glycol and thiodiglycol is particularly preferable in further improving various inkjet recording characteristics (ejection stability, ejection response, ink storage stability, etc.) described above. It is something.
The main components of the ink of the present invention are as described above, but other various dispersants, surfactants, viscosity modifiers, surface tension modifiers, optical brighteners and the like can be added as necessary. For example, viscosity adjusting agents such as polyvinyl alcohol, celluloses and water-soluble resins; various cationic or nonionic surfactants; surface tension adjusting agents such as diethanolamine and triethanolamine; pH adjusting agents with buffer solutions, antifungal agents Etc. can be mentioned.

The cloth used in the present invention is preferably composed mainly of cellulose fibers containing at least an alkaline substance. There is no particular limitation on the method for producing the cloth, but the cloths described in JP-A-63-168382 and JP-B-3-46589 can be used. As described above, the printing ink of the present invention is applied onto the cloth, but in this state it is merely attached, so that the reaction fixing of the dye to the fiber and the removal step of the unfixed dye are continued. Is preferably applied. Such reaction fixing and removal of the unreacted dye may be a conventionally known method, for example, a steaming method, an HT steaming method, a thermofix method, or an alkali treatment if a cloth which has been previously alkali-treated is not used. It can be carried out according to a conventionally known method of washing after treatment by a pad steam method, an alkali blotch steam method, an alkali shock method, an alkali cold fix method, or the like.

The ink jet printing method of the present invention is a method of using the above ink of the present invention, and the ink jet recording method used may be any conventionally known ink jet recording method. 599
In the method described in Japanese Patent No. 36, the method in which the ink subjected to the action of thermal energy causes a rapid volume change and the action force resulting from this state change ejects the ink from the nozzle is most effective. By using the ink of the present invention in such a system, stable printing is possible. As an example of an apparatus suitable for performing printing using the ink of the present invention, there is an apparatus that applies thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generates a droplet by the thermal energy. An example of the head configuration, which is the main part of the apparatus, is shown in FIGS. 1, 2 and 3. The head 13 is made by bonding glass, ceramics or a plastic plate having a groove 14 through which ink is passed, and a heating head 15 (a head is shown in the drawing, but not limited to this) used for thermal recording. Obtained. The heating head 15 has a protective film 16 formed of silicon oxide or the like,
It is composed of aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 formed of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina. The ink 21 reaches the ejection orifice (fine hole) 22 and forms a meniscus 23 by the pressure P.

Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith,
The pressure causes the meniscus 23 to project, the ink 21 to be ejected, and the recording droplet 24 to be discharged from the orifice 22 to fly toward the cloth 25 containing the cellulose fiber. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head comprises a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that described in FIG.
It is manufactured closely. 1 is a cross-sectional view of the head 13 taken along the ink flow path, and FIG. 2 is a cross section of FIG.
It is a cutting plane along a line.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, it is held in a protruding form in the moving path of the recording head. Reference numeral 62 denotes a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration that moves in a direction perpendicular to the moving direction of the recording head and abuts the ejection port surface to perform capping. Further, 63 is an absorber provided adjacent to the blade 61, and like the blade 61, is held in a protruding form in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head which has a discharge energy generating means and discharges ink to a cloth containing cellulose fibers which faces the discharge port surface on which the discharge ports are arranged for recording.
Reference numeral 6 denotes a carriage for mounting the recording head 65 and moving the recording head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown).
is doing. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area. 51 is a paper feeding section for inserting a cloth containing cellulose fibers, 5
A paper feed roller 2 is driven by a motor (not shown). With these configurations, the cloth containing the cellulose fibers is fed to the position facing the ejection opening surface of the recording head,
As the recording progresses, the paper is ejected to the paper ejecting section provided with the paper ejecting roller 53.

In the above structure, when the recording head 65 returns to the home position after recording is completed, the cap 62 of the head recovery section 64 is retracted from the movement path of the recording head 65, but the blade 61 projects into the movement path. There is. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to project into the movement path of the recording head. Recording head 6
When 5 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the above-described position at the time of wiping. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. To move the recording head to the home position,
Not only at the end of recording or at the time of ejection recovery, the recording head moves to the home position adjacent to the recording area at a predetermined interval while moving in the recording area for recording, and the wiping is performed with this movement. .

FIG. 5 is a diagram showing an example of an ink cartridge in which ink is supplied to the head via an ink supply member, for example, a tube. Here, 40 is an ink containing portion containing the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42, the ink in the ink bag 40 can be supplied to the head. 44
Is an absorber that receives waste ink. It is preferable for the present invention that the surface of the ink containing portion which is in contact with the ink is formed of polyolefin, particularly polyethylene. The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separately provided as described above, but is also preferably used in the one in which they are integrated as shown in FIG.

In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a plurality of orifices. Head portion 71
It is configured to be ejected as an ink droplet from. For the present invention, it is preferable to use polyurethane as the material of the ink absorber. Reference numeral 72 is an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66. In particular, when the ink of the present invention is used and a particularly effective printing method is obtained, the ejection droplets are 20 to 200.
It is preferable that the conditions are pl, the amount of ejected ink is 4 to 40 nl / mm ² , the driving frequency is 1.5 KHz or more, and the head temperature is 35 to 60 ° C.

[0020]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, "%" and "%" are based on weight unless otherwise specified. Example 1 Reactive dye (CI Reactive Yellow 95) 10 parts Thiodiglycol 24 parts Diethylene glycol 11 parts Potassium chloride 0.004 parts Sodium sulfate 0.002 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Water 55 parts Above Mix all components and pour the mixture with sodium hydroxide.
The mixture was adjusted to H8.4, stirred for 2 hours, and then filtered with a Fluoropore filter FP-100 (trade name, manufactured by Sumitomo Electric Co., Ltd.) to obtain an ink-jet printing ink (A) of the present invention.

Example 2 Reactive dye (CI Reactive Red 24) 10 parts Thiodiglycol 15 parts Diethylene glycol 10 parts Tetraethylene glycol dimethyl ether 5 parts Potassium chloride 0.04 parts Sodium sulfate 0.01 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Nickel chloride 0.0002 parts Water 60 parts All the above components are mixed, and the mixture solution is mixed with sodium hydroxide.
The mixture was adjusted to H7.9, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Co., Ltd.) to obtain an ink-jet printing ink (B) of the present invention.

Example 3 Reactive dye (CIReactive Blue 72) 13 parts Thiodiglycol 23 parts Triethylene glycol monomethyl ether 6 parts Potassium chloride 0.05 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Zinc chloride 0. 0003 parts Water 58 parts All of the above ingredients are mixed and the mixture is hydrated with sodium hydroxide.
The mixture was adjusted to H8.3, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the ink-jet printing ink (C) of the present invention.

Example 4 Reactive dye (CIReactive Brown 11) 2 parts Reactive dye (CIReactive Orange 12) 1.5 parts Reactive dye (CIReactive Black 39) 6.5 parts Thiodiglycol 23 parts Diethylene glycol 5 parts Isopropyl alcohol 3 parts Sulfuric acid Potassium 0.01 part Sodium metasilicate 0.001 part Iron sulphate 0.0005 part Nickel sulphate 0.0003 part Zinc sulphate 0.0003 parts Water 59 parts All the above components are mixed and the mixture is p-hydrated with sodium hydroxide.
The mixture was adjusted to H8.2, stirred for 2 hours, and then filtered through Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Co., Ltd.) to obtain the ink-jet printing ink (D) of the present invention.

Example 5 Reactive dye (CI Reactive Blue 49) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.08 parts Potassium sulfate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulfate 0.001 parts Nickel chloride 0.0003 parts Zinc sulphate 0.0003 parts Water 51.9 parts All the above ingredients are mixed and the mixture is hydrated with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered with a Fluoropore filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain an ink-jet printing ink (E) of the present invention.

Example 6 Reactive Dye (CI Reactive Blue 49) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.08 parts Potassium sulphate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulphate 0.001 parts Nickel chloride 0.0003 parts Zinc sulphate 0.0003 parts Calcium chloride 0.006 parts Water 51.9 parts All the above ingredients are mixed and the mixture is p-hydrated with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered through Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the ink-jet printing ink (F) of the present invention.

Example 7 Reactive dye (CI Reactive Blue 49) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.08 parts Potassium sulfate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulfate 0.001 parts Nickel chloride 0.0003 parts Zinc sulphate 0.0003 parts Magnesium chloride 0.01 parts Water 51.9 parts All the above components are mixed, and the mixed solution is mixed with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Co., Ltd.) to obtain the ink-jet printing ink (G) of the present invention.

Comparative Example 1 Reactive dye (CI Reactive Yellow 95) 10 parts Thiodiglycol 24 parts Diethylene glycol 11 parts Potassium chloride 0.3 parts Sodium sulfate 0.1 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Water 54 Inkjet printing ink (H) was obtained in the same manner as in Example 1 except that all the above components were used.

Comparative Example 2 Reactive dye (CI Reactive Yellow 95) 10 parts Thiodiglycol 24 parts Diethylene glycol 11 parts Potassium chloride 0.3 parts Sodium sulfate 0.1 parts Sodium metasilicate 0.000005 parts Iron chloride 0.000005 parts Nickel chloride 0.000003 parts Zinc chloride 0.000002 parts Water 54.6 parts Ink (I) for inkjet printing was obtained in the same manner as in Example 1 except that all the above components were used.

Comparative Example 3 Reactive dye (CI Reactive Red 24) 10 parts Thiodiglycol 15 parts Diethylene glycol 10 parts Tetraethylene glycol dimethyl ether 5 parts Potassium chloride 0.00006 parts Sodium sulfate 0.00002 parts Sodium metasilicate 0.0001 parts Iron chloride 0.00005 parts Nickel chloride 0.00002 parts Water 60 parts An ink for inkjet printing (J) was obtained in the same manner as in Example 1 except that all the components described above were used.

Comparative Example 4 Reactive dye (CI Reactive Blue 49) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.0001 parts Potassium sulfate 0.0001 parts Sodium metasilicate 0.000005 parts Iron chloride 0.000005 parts Nickel chloride 0.000003 parts Zinc chloride 0.000002 parts Water 52 parts An ink for inkjet printing (K) was obtained in the same manner as in Example 1 except that all the above components were used.

USE EXAMPLE 1 Each ink jet printing ink of Examples 1 to 7 (A to
G) the color bubble jet copier PIXEL PR
O (trade name, manufactured by Canon) head (nozzle number 256,
Check for clogging of nozzles, decrease in discharge droplet volume and discharge speed, etc. when continuous printing of 1 × 10 ⁸ pulses is performed with 10 nozzles using flying droplets 20-40 pl). It was Also, after printing the alphanumeric characters continuously for 3 minutes with the same head, stop the printing, leave it for 3 minutes without the cap, and then print the alphanumeric characters again to check whether the characters are blurred or missing. Examined. Further, the same head was used to continuously print alphanumeric characters for 3 minutes, then the printing was stopped, the printing was left uncapped for 3 days, and clogging due to the adhesion of solid matter near the tip of the nozzle was examined ( 45-60 heads
The temperature was raised to the range of ° C and used. ). Moreover, 100 cc of each ink-jet printing ink (A to G) was placed in a glass bottle and stored at 40 ° C. for 3 days, and the storage stability of the ink was examined. The properties of the ink and the evaluation results are shown in Tables 1 and 3.

USE EXAMPLE 2 Ink jet textile printing inks (AK) of Examples 1 to 7 and Comparative Examples 1 to 4 were color bubble jet copier PIX.
It is mounted on EL PRO (product name Canon), printed on a 100% cotton georgette fabric that has been alkali-treated in advance, fixed by steam heat treatment at 100 ° C for 2 minutes, and then washed with a neutral detergent, The sharpness and bleeding property of the dyed product were evaluated. The results are shown in Tables 1 to 4 (a solid sample of 2 × 10 cm was used as the print and the ink injection amount was 1).
Created under the condition of 6 nl / mm ² . In addition, when the inks of Examples 1 to 7 were used, they had a sufficient superiority in terms of dyeing rate as compared with the case of using the inks of Comparative Examples 1 to 4.

[0033]

[Table 1]

[Table 2]

[0034]

[Table 3]

[Table 4]

Example 8 Reactive dye (CI Reactive Yellow 168) 10 parts Thiodiglycol 23 parts Diethylene glycol 12 parts Potassium chloride 0.004 parts Sodium sulfate 0.002 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Water 55 Part All the above ingredients are mixed and the mixture is mixed with sodium hydroxide.
The mixture was adjusted to H8.4, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain an ink-jet printing ink (L) of the present invention.

Example 9 Reactive dye (CI Reactive Red 235) 10 parts Thiodiglycol 13 parts Diethylene glycol 11 parts Tetraethylene glycol dimethyl ether 6 parts Potassium chloride 0.04 parts Sodium sulfate 0.01 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Nickel chloride 0.0002 parts Water 60 parts All the above components are mixed, and the mixture solution is mixed with sodium hydroxide.
The mixture was adjusted to H7.9, stirred for 2 hours, and then filtered using Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the ink-jet printing ink (M) of the present invention.

Example 10 Reactive dye (CI Reactive Blue 235) 13 parts Thiodiglycol 25 parts Triethylene glycol monomethyl ether 6 parts Potassium chloride 0.05 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Zinc chloride 0. 0003 parts Water 56 parts All the above ingredients are mixed and the mixture is hydrated with sodium hydroxide.
The mixture was adjusted to H8.3, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain an ink-jet printing ink (JN) of the present invention.

Example 11 Reactive dye (CI Reactive Brue 230) 6.5 parts Reactive dye (CI Reactive Brown 11) 2 parts Reactive dye (CI Reactive Orange 12) 1.5 parts Thiodiglycol 24 parts Diethylene glycol 5 parts Isopropyl alcohol 2 parts Sulfuric acid Potassium 0.01 part Sodium metasilicate 0.001 part Iron sulphate 0.0005 part Nickel sulphate 0.0003 part Zinc sulphate 0.0003 parts Water 59 parts All the above components are mixed and the mixture is p
The mixture was adjusted to H8.2, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Co., Ltd.) to obtain the ink-jet printing ink (O) of the present invention.

Example 12 Reactive dye (CI Reactive Brown 37) 15 parts Thiodiglycol 18 parts Diethylene glycol 15 parts Sodium chloride 0.08 parts Potassium sulfate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulfate 0.001 parts Nickel chloride 0.0003 parts Zinc sulphate 0.0003 parts Water 51.9 parts All the above ingredients are mixed and the mixture is hydrated with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the ink-jet printing ink (P) of the present invention.

Example 13 Reactive dye (CI Reactive Brown 37) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.08 parts Potassium sulfate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulfate 0.001 parts Nickel chloride 0.0003 parts Zinc sulphate 0.0003 parts Calcium chloride 0.006 parts Water 51.9 parts All the above ingredients are mixed and the mixture is p-hydrated with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered through Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the ink-jet printing ink (Q) of the present invention.

Example 14 Reactive dye (CI Reactive Brown 37) 15 parts Thiodiglycol 16 parts Diethylene glycol 17 parts Sodium chloride 0.08 parts Potassium sulfate 0.01 parts Sodium metasilicate 0.0005 parts Iron sulfate 0.001 parts Nickel chloride 0.0003 parts Zinc sulfate 0.0003 parts Magnesium chloride. 0.01 parts Water 51.9 parts All of the above ingredients are mixed and the mixture is hydrated with sodium hydroxide.
The mixture was adjusted to H7.7, stirred for 2 hours, and then filtered using Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain an ink-jet printing ink (R) of the present invention.

Comparative Example 5 Reactive dye (CI Reactive Yellow 168) 10 parts Thiodiglycol 23 parts Diethylene glycol 12 parts Potassium chloride 0.3 parts Sodium sulfate 0.1 parts Sodium metasilicate 0.001 parts Iron chloride 0.0005 parts Water 54 Inkjet printing ink (S) was obtained in the same manner as in Example 1 except that the above components were used.

Comparative Example 6 Reactive dye (CI Reactive Yellow 168) 10 parts Thiodiglycol 23 parts Diethylene glycol 12 parts Potassium chloride 0.3 parts Sodium sulfate 0.1 parts Sodium metasilicate 0.000005 parts Iron chloride 0.000005 parts Nickel chloride 0.000003 parts Zinc chloride 0.000002 parts Water 54.6 parts An ink for inkjet printing (T) was obtained in the same manner as in Example 1 except that all the above components were used.

Comparative Example 7 Reactive dye (CI Reactive Red 235) 10 parts Thiodiglycol 13 parts Diethylene glycol 11 parts Tetraethylene glycol dimethyl ether 6 parts Potassium chloride 0.00006 parts Sodium sulfate 0.00002 parts Sodium metasilicate 0.0001 parts Iron chloride 0.00005 parts Nickel chloride 0.00002 parts Water 60 parts An ink for inkjet printing (U) was obtained in the same manner as in Example 1 except that all the above components were used.

Comparative Example 8 Reactive dye (CI Reactive Brown 37) 15 parts Thiodiglycol 18 parts Diethylene glycol 15 parts Sodium chloride 0.0001 parts Potassium sulfate 0.0001 parts Sodium metasilicate 0.000005 parts Iron chloride 0.000005 parts Nickel chloride 0.000003 parts Zinc chloride 0.000002 parts Water 52 parts Ink (V) for inkjet printing was obtained in the same manner as in Example 1 except that the above components were used.

Use Example 3 Instead of the inks (A to G) in Use Example 1, Examples 8 to were used.
Each of the inkjet printing inks (L to R) of No. 14 was used, and the same evaluations as in Use Example 1 were carried out except that Table 5
And the results of Table 8 were obtained. Use Example 4 In place of the inks (A to K) in Use Example 2, Examples 8 to
The same evaluations were performed as in Use Example 2 except that the ink jet printing inks (LV) of Example 14 and Comparative Examples 5 to 8 were used, and the results of Table 6 and Table 8 were obtained. Example 8
When the inks of Nos. 14 to 14 were used, the dyeing ratio was sufficiently superior to that of the inks of Comparative Examples 5 to 8. Furthermore, when the amount of undyed dye that had eluted into the cleaning liquid was observed, the amount of the ink using Examples 8 to 14 was clearly smaller than that of the reactive dye having one reactive group. ..

[Table 5]

[0047]

[Table 6]

* 1 Measured by ion chromatography (values for reactive dyes are shown). * 2 ICP (Inductively Coupled Plasma Atomic Emission Spectroscopy) was used for analysis. Si, Fe, Ni and Zn, and Ca, M
Content of g (ppm) * 3 The number of nozzles that did not cause nozzle clogging, decrease in discharge droplet amount or discharge speed, etc. when continuous printing of 1 × 10 ⁸ pulses was performed with 10 nozzles. Measured and evaluated according to the following criteria. ◯: 10 lines Δ: 6 to 9 lines x: 5 lines or less * 4 After continuous printing for 3 minutes, leave without a cap for 3 minutes to reprint, and evaluate according to the following criteria. ◯: No defects from the first letter. Δ: A part of the first character is scratched or chipped. X: No printing is possible from the first character. * 5 After continuous printing for 3 minutes, when left for 3 days without a cap, the state of clogging due to the adhesion of solid matter near the tip of the nozzle is evaluated according to the following criteria. ◯: No clogging. Δ: Clogging occurred but recovered by suction. X: The clogging does not recover even when sucked. * 6 After storing the ink at 40 ° C. for 3 days, it was visually determined whether or not foreign matter was generated in the glass bottle. ◯: No foreign material △: Small foreign material generated ×: Large foreign material generated

[0049]

[Table 7]

[Table 8] * 7 Judged by the sharpness of the pattern when observed with the naked eye. ◯: Good Δ: Slightly inferior ×: Inferior * 8 Observed and judged by the naked eye. ◯: Good Δ: Slightly inferior X: Inferior

[0050]

As described above, according to the ink of the present invention, a dyed product having a high density without bleeding can be obtained especially for a fabric to be dyed which is mainly composed of cellulose fibers. It becomes possible. Further, according to the ink of the present invention, in inkjet printing, it is possible to perform printing with high reliability of ejection performance without causing clogging or the like in the head nozzle for a long period of time. In particular, it is remarkably good in recording of a type in which ink is ejected due to the bubbling phenomenon of ink due to thermal energy.

[0051]

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of a head portion of an inkjet recording apparatus.

FIG. 2 is a cross-sectional view of a head portion of an inkjet recording device.

3 is an external perspective view of a head in which the head shown in FIG.

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

FIG. 5 is a vertical sectional view of an ink cartridge.

FIG. 6 is a perspective view of a recording unit.

[Explanation of symbols]

 61: Wiping member 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage

Claims (14)

[Claims] 1. An inkjet printing ink containing a reactive dye and an aqueous liquid medium, wherein the reactive dye contains 10 to 20,000 ppm of chlorine ions and / or sulfate ions. ink. 2. The ink for ink-jet printing according to claim 1, wherein the ink contains 0.1 to 30 ppm of at least one substance selected from the group consisting of silicon, iron, nickel and zinc. 3. The ink according to claim 1, wherein the reactive dye is contained in an amount of 5 to 25% by weight. 4. The reactive dye having a vinyl sulfone group or a monochlorotriazine group.
The ink for inkjet printing according to item 4. 5. The ink for ink-jet printing according to claim 1, wherein the reactive dye is a reactive dye having at least two reactive groups. 6. A fabric containing cellulose fibers,
An inkjet printing method in which a printing ink is applied by an inkjet method, and then a dyeing treatment is performed, wherein the printing ink is the ink according to claim 1. 7. The inkjet printing method according to claim 6, wherein the inkjet method is an inkjet method using heat energy. 8. A recording unit comprising an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets, wherein the ink is the ink according to claim 1. unit. 9. The recording unit according to claim 8, wherein the head portion includes a head that applies thermal energy to the ink to eject ink droplets. 10. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is
An ink cartridge, which is the ink described in 1. 11. An ink according to claim 1, wherein the ink is an ink jet recording apparatus including a recording unit having an ink containing portion containing ink and a head portion for ejecting the ink as ink droplets. An ink jet recording apparatus characterized by the above. 12. The head unit includes a head which causes thermal energy to act on ink to eject ink droplets.
1. The inkjet recording device according to 1. 13. A recording head for ejecting ink droplets,
The ink according to claim 1, wherein the ink is an ink cartridge having an ink containing portion containing ink, and an ink supply device for supplying the ink from the ink cartridge to a recording head. Characteristic inkjet recording device. 14. The ink jet recording apparatus according to claim 13, wherein the recording head is a head which applies thermal energy to ink to eject ink droplets.