JPH0742428B2 - Inkjet printing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an inkjet printing method suitable for printing a fabric (woven fabric or non-woven fabric).

(Prior Art) Conventionally, as a printing method for a fabric (woven cloth or non-woven cloth), a printing method such as roller printing, screen printing or transfer printing has been used, and a printing method using an inkjet method has also been partially proposed. (See Japanese Patent Laid-Open No. 50-59108).

(Problems to be Solved by the Invention) However, in the conventional general printing method, it is necessary to prepare a printing plate for printing, and these printing plates, for example,
It is expensive to make a printing plate cylinder and a screen plate, and also to make a plate for printing transfer paper in transfer printing, so that the cost cannot be adjusted unless a considerable amount is produced. Further, generally, the fashion period of the pattern of the print cloth is short, so that plate making each time further increases the cost, and it is not possible to quickly respond to those fashions, and there is a serious problem that a large amount of inventory may be held.

An ink jet printing method has been proposed to solve these drawbacks, but with this ink jet printing, the viscosity of the ink used cannot be increased too much due to the nature of the printer, and the woven fabric is used for paper and the like. In comparison, since the weave is coarse, there is a problem of bleeding of the inkjet ink adhering to the woven fabric surface, making it difficult to create a fine pattern. Further, since the ink is ejected from the fine nozzles at a high speed and at a high frequency, there are drawbacks such that the ejection is unstable and the response to the frequency is limited depending on the physical property value of the ink.

Further, the printed matter formed by using the conventional ink-jet ink, particularly when the reactive dye is used, has a low dyeing rate of the dye and has low wash fastness.

Therefore, an object of the present invention is to provide an economical problem in the conventional general printing method as described above and various problems in the printing method by the ink jet method, particularly a problem of accurate and stable printing and a dye fixing rate of the printed material. Another object of the present invention is to provide an inkjet printing method capable of simultaneously solving the problems of washing fastness.

Such and other objects of the present invention are achieved by the present invention described below.

DISCLOSURE OF THE INVENTION That is, the present invention provides an inkjet printing method, which is performed by applying a printing ink to a cloth containing fibers dyeable with a reactive dye by an inkjet method, wherein (A) the cloth is not previously alkali-treated. (B) As the printing ink, a main composition component is a reactive dye having a reactive group selected from the following group, and a solvent mainly composed of water and an organic solvent non-reactive with the reactive dye. And (C) applying the ink to the cloth, and then performing a dyeing step including an alkali treatment, the inkjet printing method.

"Dichlorotriazine group, monochlorotriazine group, trichloropyrimidine group, monochlorodifluoropyrimidine group, chlorobenzothiazole group, dichloropyridazone group, dichloropyridazine group, dichloroquinoxaline group,
Epoxy group, 3-carboxypropyl pyridinium niobium triazine _{group, -SO 2 CH 2 CH 2 OSO} 3 H, -SO 2 NHCH 2 CH 2 OSO 3 H, -NHCOCH 2 CH 2 OSO 3 H, -NHCOCH 2 CH 2 Cl, _{-NHCOCH = CH 2, -SO 2 CH} = CH 2, -CH 2 NHCOCCl = CH 2, -NHCOCBr = CH 2, -NHCOCH 2 Cl, -NHCH 2 OH, more detail description of -PO ₃ H "invention Then, the main feature of the ink of the present invention is that an organic solvent which is non-reactive with the reactive dye is selected as the organic solvent constituting the liquid medium of the ink containing the reactive dye.

That is, the present inventor has conducted various researches on ink-jet printing, and as a result, has adopted a reactive dye as a dye of ink-jet printing ink and is widely used as a part of a liquid medium of the ink. Excellent printing can be achieved by using organic solvents such as
A new problem arises in that the dye fixation ratio is low and the wash fastness of the resulting print is also deteriorated for some reason, and such a decrease in the dye fixation ratio means that part of the dye is polyhydric alcohol during storage of the ink. It is presumed that this occurs because it reacts with the like and the reaction with the fiber is hindered.

In addition, the washing fastness is deteriorated because the water in the ink attached to the fabrics evaporates quickly, but the polyhydric alcohol etc. does not evaporate rapidly and the fabrics remain as they are, and the post-printing post-treatment It can be assumed that it reacts with a part of the reactive dye during heating or alkali treatment, and this reaction product is easily removed during washing, resulting in a decrease in washing fastness.

For the above reasons, the present invention solves the above problems by washing and using an organic solvent that does not react with the reactive dye as the organic solvent used in the ink.

The reactive dyes used in the present invention are water-soluble azo dyes, anthraquinone dyes, phthalocyanine dyes and other dyes which are widely used in the dyeing of fibers or the conventional printing methods, and many of them are known.

These reactive dyes have a water-soluble group such as a sulfonic acid group or a carboxyl group in their structure, and can react with a hydroxyl group or an amino group of the fiber to form a covalent bond with the fiber, for example, dichloro. Triazine group, monochlorotriazine group, trichloropyrimidine group, monochlorodifluoropyrimidine group, chlorobenzothiazole group, dichloropyridazone group, dichloropyridazine group, dichloroquinoxaline group, epoxy group, 3-carboxypyridiniotriazine group, -SO ₂ CH ₂ CH ₂ OSO ₃ H, -SO ₂ NHCH ₂ CH ₂ OSO ₃ H, -NHCOCH ₂ CH ₂ OSO ₃ H, -NHCOCH ₂ CH ₂ Cl, -NHCOCH = CH ₂ , -SO ₂ CH = CH _{2, -CH 2 NHCOCCl = CH 2} , -NHCOCBr = CH 2, and has a _{-NHCOCH 2 Cl, -NHCH 2 OH,} -PO 3 group H and the like.

In the present invention, any of these reactive dyes can be used. Among them, preferred reactive dyes in the present invention include CI reactive yellow 2, 3, 13, 15, 17, 18, 2
3, 24, 37, 42, 57, 58, 64, 75, 76, 77, 79, 81, 8
4, 85, 87, 88, 91, 92, 93, 95, 111, 115, 116, 13
0, 131, 132, 133, 135, 136, 137, 139, 140, 142, 14
3,144,145,146,147,148,151,162,163 CI Reactive Orange 5,7,11,12,13,15,1
6, 35, 45, 46, 56, 62, 70, 72, 74, 82, 84, 87, 9
1, 92, 93, 95, 97, 99, CI Reactive Red 3, 13, 16, 21, 22, 23, 24,
29, 31, 33, 35, 45, 49, 55, 63, 85, 106, 109, 11
1, 112, 113, 114, 118, 126, 128, 130, 131, 141, 15
1, 170, 171, 174, 176, 177, 180, 183, 184, 186, 18
7, 188, 190, 193, 194, 195, 196, 200, 201, 202, 20
4, 206, 218, 221, CI Reactive Violet 1, 4, 5, 6, 22, 2
4, 33, 36, 38, CI Reactive Blue 2, 3, 5, 8, 10, 13, 14,
15, 18, 19, 21, 25, 27, 28, 38, 39, 40, 41, 49, 5
2, 63, 71, 72, 74, 75, 77, 78, 79, 89, 100, 101, 1
04, 105, 119, 122, 147, 158, 160, 162, 166, 169, 1
70, 171, 172, 173, 174, 176, 179, 184, 190, 191, 1
94, 195, 198, 204, 211, 216, 217, CI Reactive Green 5, 8, 12, 15, 19, 23, CI Reactive Brown 2, 7, 8, 9, 11, 16, 1
7, 18, 21, 24, 26, 31, 32, 33, CI Reactive Black 1, 5, 8, 13, 14, 23, 3
1, 34, 39 and the like.

If the textile to be printed is wool or nylon, CI Reactive Yellow 21, 34, 39, 69, 98, 125, 1
27, CI Reactive Orange 29, 53, 68, CI Reactive Red 28, 65, 66, 78, 83, 84, 10
0, 116, 136, 147, 154, 172, CI reactive violet 34, CI reactive blue 50, 69, 94, 177, CI reactive brown 12 and the like are suitable.

In the present invention, the liquid medium in which the reactive dye as described above is dissolved or dispersed comprises a liquid medium in a conventional general dyeing, a liquid medium used in a liquid medium of a conventional inkjet ink, particularly water and an organic solvent. However, it is necessary to use an organic solvent that does not have active hydrogen, such as a hydroxyl group or an amino group, that reacts with a reactive dye, as the organic solvent used by mixing with water.

Examples of such an organic solvent include amides such as dimethylformamide and dimethylacetamide; ketones such as acetone and methylethylketone; ethers such as tetrahydrofuran and dioxane; N-methyl-2-pyrrolidone and 1,3-dimethyl- 2-Imidazolidinone and the like can be mentioned, and particularly preferable organic solvents include polyoxyethylene (addition mol number: 1 to 15) dialkyl (C1 to C4) ether, polyoxyethylene / oxypropylene block ( Or a random) copolymer (additional mol number: 1 to 15) dialkyl (C1 to C4) ether, etc. may be mentioned.

Such organic solvents can be used alone or as a mixture, and it is preferable to use such an organic solvent in a proportion of about 1 to 70% by weight in the ink solvent. The amount of the ink solvent used is preferably such that the content of the reactive dye becomes about 0.1 to 15% by weight when the ink is prepared.

The essential components of the ink of the present invention are as described above, but various other dispersants, surfactants, viscosity modifiers, other types of dyes, etc. can be added as necessary. Of course, it is preferable to select and use those additives which do not react with the reactive dye, but if the amount used is very small, even if they are reactive, there will be substantially no problem.

Examples of the dispersant or surfactant that can be added as necessary include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkylsulfosuccinates, alkyl phosphate ester salts, and naphthalene sulfonate formalin. Condensates, anionic dispersants such as polyoxyethylene alkyl sulfate salts or surfactants; polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Nonionic dispersants or surfactants such as polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer are important.

As the viscosity modifier, mainly water-soluble natural or synthetic polymers such as carboxymethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic and starch are preferable, and using these viscosity modifiers,
Alternatively, the viscosity of the ink of the present invention can be adjusted to 50 at 25 ° C. without use.
cps or less, preferably 1 to 15 cps.

Further, in order to prepare an ink used in an ink jet type of charging the ink, a specific resistance adjusting agent such as an inorganic salt of lithium chloride, ammonium chloride or sodium chloride is added.

When applied to an inkjet system of a type that ejects ink by the action of thermal energy, thermal physical property values (for example, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

In addition, if necessary, other than the above three additives,
For example, a defoaming agent, a penetrating agent, an antifungal agent, a pH adjusting agent and the like can be added as appropriate.

The inkjet ink of the present invention can be obtained by adding necessary components to a liquid medium and simply dissolving or dispersing them.

Although the inkjet ink of the present invention is obtained as described above, it is possible to adjust the surface tension of the ink obtained by blending the above-mentioned essential components and optional components to a range of about 30 to 60 dyne / cm. preferable. Such adjustment of the surface tension can be easily achieved by those skilled in the art by selecting reactive dyes and liquid media, and by adding various additives.

In the inkjet ink of the present invention, when the surface tension is 30 dyne / cm or less, the ink adhered to the woven or non-woven fabric made of various fibers causes excessive bleeding on the surface to form a fine pattern. If the surface tension exceeds the upper limit of the above range, it becomes difficult to obtain stable and uniform droplets during ink ejection. The above surface tension values are KYOWACBVP
SURFACETENSIOMETER A-1 (trade name, Kyowa Kagaku Co., Ltd.)
Manufactured by K.K.) under the condition of 25 ° C.

The above ink-jet ink of the present invention is useful for printing a cloth (woven cloth or non-woven cloth) by an ink jet method, and in particular, it can be dyed with a reactive dye such as cotton, hemp, viscose, wool, silk, nylon and the like. It is useful for printing a woven or non-woven fabric made of various fibers, or a mixed woven fabric or non-woven fabric made of these fibers and synthetic fibers such as polyester fibers, acetate fibers, polypropylene fibers and vinylon fibers. These woven or non-woven fabrics may be pretreated for inkjet printing. Such pretreatment can be carried out by applying a water-soluble or water-dispersible polymer or the like capable of quickly absorbing and retaining the ink applied to the surface of the fibers constituting the woven or non-woven fabric.

The inkjet method used to apply the inkjet ink of the present invention to the woven or non-woven fabric as described above is a method in which the ink can be effectively released from the nozzle and applied to the woven or non-woven fabric as a range. Any method may be used as long as it is, and typical ones of those methods are, for example, IEEE Trans Actions on Industry Applications (IEEE Trans
-Actions on Industry Applications) Vol.JA-13, N
o.1 (February and March 1977) and Nikkei Electronics January 29, 1973, April 6, 1974 and December 1982.
It is described in the 6th issue of the month.

These described methods are suitable for use of the inkjet ink of the present invention, and some of them will be described. First, there is an electrostatic suction method. In this method, the nozzle and the nozzle placed several mm ahead of the nozzle are placed. A method of applying a strong electric field between the accelerating electrode and the ink to form ink particles from the nozzle and drawing them one after another, and recording information by giving an information signal to the deflection electrodes while the drawn ink flies between the deflection electrodes. There is a method of ejecting ink particles in response to an information signal without deflecting the ink, and any of them is effective for application of the inkjet ink of the present invention.

The second method is to apply a high pressure to the ink with a small pump, and mechanically vibrate the nozzle with a crystal oscillator or the like to forcibly eject minute ink particles.
The ejected ink particles are charged at the same time as the ejection according to the information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the charge amount.

As another method using this method, there is a method called a micro dot inkjet method. In this method,
Keep the ink pressure and excitation conditions within a certain range,
Two types of ink droplets, large and small, are generated from the tip of the nozzle, and only these medium and small diameter droplets are used for recording. The feature of this method is that a fine droplet group can be obtained even with a nozzle diameter as thick as the conventional one. A third method is a piezo element method. In this method, a piezo element is used as a pressure means applied to ink, instead of a mechanical means such as a pump unlike other methods. In this method, an electric signal is applied to the piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from the nozzle. Further, the ink of the present invention, the method described in JP-A-54-59936, the ink undergoing the action of thermal energy causes a rapid volume change, by the action force due to this state change,
It is suitable for a method of performing ink-jet printing by ejecting ink from a nozzle, and exhibits excellent ejection stability.

Any of the various inkjet methods as described above can be used, and by adopting any of these methods, a pattern such as a character or a figure is formed by ink attached to a cloth such as a woven cloth or a non-woven cloth. The inkjet ink of the invention is
As described above, the surface tension is preferably controlled within a certain range, so that the ejection stability of droplets from the nozzle is extremely excellent. Further, the presence of the texture of the woven cloth or the like allows the ink to properly adhere without excessively bleeding.

Therefore, a clear and fine pattern can be formed by the subsequent dyeing process by treatment with alkali or heat treatment. On the other hand, when the conventional inkjet ink is used, the dots do not adhere to the target position accurately, or the dots of the adhered ink bleed quickly along the texture of the woven fabric and It was difficult to form a fine pattern.

As described above, the ink-jet ink of the present invention allows the ink to adhere to the woven cloth or the like according to the image signal, and the reactive dye in the ink in this state simply adheres to the woven cloth. Therefore, it is preferable to carry out the reaction fixing of the dye on the fiber and the step of removing the unfixed dye.

In such a fixing process, the reactive dye reacts with the fiber, but when a printing ink containing an organic solvent that reacts with a reactive dye such as a polyhydric alcohol as in the conventional case is used,
When the ink is stored, a part of the dye already reacts with the organic solvent, which causes a decrease in the dye fixing rate.

Furthermore, since these polyhydric alcohols and the like are non-volatile, they remain to some extent during this fixing step, and by this fixing step, the reactive dye reacts with the organic solvent such as the polyhydric alcohol and these reaction products become It causes deterioration of washing fastness.

In the present invention, by not using such a reactive organic solvent, it is possible to prevent a decrease in dye dyeing rate and a decrease in washing fastness of the printed product.

These reaction fixing and unreacted dye removal methods may be conventionally known methods, for example, steaming method, HT steaming method, thermofix method, alkali pad steam method, alkali blotch steam method, alkali shock method, alkali After processing by cold fix method etc.,
It can be performed according to a conventionally known method such as washing.

(Operation / Effect) According to the present invention as described above, it is not necessary to make an expensive printing plate when printing, as in the case of conventional general printing, and an image to be printed can be created and modified very easily by a computer. Therefore, it is possible to respond to changes in fashion at any time without the need for expensive editions as in the prior art.

Therefore, it is possible to secure a sufficient profit even in a small-scale production, instead of the large-scale production as in the prior art. Therefore, it has an advantage that it can be applied not only to an industrial printing method but also to a hobby print in a general household, and a printed article having high washing fastness can be provided.

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, "%" and "%" are based on weight.

Example 1 Reactive dye (CIReactive Red 24) 5 parts Tetraethylene glycol dimethyl ether 30 parts Water 65 parts All the above components were mixed and the mixture was adjusted to pH with sodium hydroxide.
After adjusting to 8.3 and stirring for 5 hours, it was filtered with Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain the water-based ink (A) of the present invention.

Example 2 Reactive dye (CIReactive Blue 216) 6 parts Diethylene glycol diethyl ether 6 parts N-methyl-2-pyrrolidone 15 parts Water 73 parts The same procedure as in Example 1 was carried out except that all the above components were used. An aqueous ink (B) was obtained.

Example 3 Reactive dye (CIReactive Orange 16) 4 parts Reactive dye (CIReactive Yellow 37) 4 parts Dipropylene glycol dimethyl ether 10 parts 1,3-Dimethyl-2-imidazolidinone 20 parts Nonionic surfactant (trade name Emulgen PP) −150,
Kao Co., Ltd.) 0.2 parts Water 63 parts Mix all the above components, adjust the mixture to pH 4.7 with acetic acid and stir for 5 hours, then use Fluoropore Filter FP-100
(Product name, manufactured by Sumitomo Electric Co., Ltd.) was filtered to obtain the water-based ink (C) of the present invention.

Example 4 reactive dye (CIReactive Red 180) 7 parts _{H 3 C- (OC 3 H 6} ) - using _{(OC 2 H 4) -OC 2} H 5 20 parts Water 73 parts The above All components, other embodiments In the same way as 1
An aqueous ink (D) of the present invention was obtained.

Comparative Example 1 A comparative ink (E) was obtained in the same manner as in Example 1 except that triethylene glycol was used instead of tetraethylene glycol dimethyl ether in the components of Example 1.

The properties of the inks of the above Examples and Comparative Examples are shown in Table 1 below.

Example 5 Water-based inks (AE) of Examples 1 to 4 and Comparative Example 1
Was mounted on an inkjet printer utilizing heat energy according to the method described in Japanese Patent Laid-Open No. 54-59936, and after printing on a cloth, an alkaline atmosphere 10
After fixing by evaporation for 1 minute at 0 ° C, then
The printed matter was obtained by washing with a neutral detergent for 10 minutes. The types of fabrics and the results are shown in Table 2.

Example 6 An aqueous ink (F) was obtained in the same manner as in Example 2 except that acetone was used instead of diethylene glycol diethyl ether in Example 2. The surface tension of this ink (F) was 46 dyne / cm, and the pH was 8.3.

A printed matter was obtained in the same manner as in Example 5 using the ink (F). The results were almost the same as when using the ink (B).

Example 7 Reactive dye (CIReactive Red 24) 2 parts 1,3-Dimethyl-2-imidazolidinone 50 parts N-methyl-2-pyrrolidone 10 parts Water 38 parts A water-based ink (G) was obtained in the same manner. The surface tension of this ink (G) is 43dy
It was ne / cm and pH was 8.3. A printed matter was obtained in the same manner as in Example 5 using the ink (G). The results were almost the same as when using the ink (A).

Example 8 10 parts of reactive dye (CIReactive Blue 21) ethylene glycol monoethyl ether acetate 20
Part Ion-exchanged water 69.9 parts Citric acid 0.1 part The same procedure as in Example 1 except that the above components were used to obtain an aqueous ink (H). The pH of this ink (H) was 3.2. A printed matter was obtained in the same manner as in Example 5 using the ink (H). At this time, when the time until the printed matter was subjected to the steaming heat treatment was performed immediately after the printing and when it was performed one week after the printing, two kinds of evaluations were performed.
Satisfactory results were obtained in the items (bleeding, variation in dot diameter, dye dyeing ratio, selective fastness), and no difference was observed between the two.

Comparative Example 2 When the same ink (H) as in Example 8 was used to obtain a printed matter similar to that in Example 5, various fabrics were sprayed with 0.1% sodium citrate aqueous solution in advance and then dried. Except for this, the same examination as in Example 8 was performed. As a result, there was no problem when steaming was performed immediately after printing, but when the steaming heat treatment was carried out one week after printing, the dyeing rate was remarkably reduced, and alkali treatment was not performed at the stage of dyeing in terms of stability of color development. The result is that it is desirable to do.

Claims (11)

[Claims] 1. An ink-jet printing method comprising applying a printing ink to a cloth containing fibers dyeable with a reactive dye by an ink-jet method, wherein (A) the cloth is not previously alkali-treated, and (B) the above As the printing ink, use an ink containing a reactive dye having a reactive group selected from the following group and a solvent mainly composed of water and an organic solvent that is non-reactive with the reactive dye as main composition components. And (C) an inkjet printing method, which comprises applying a dyeing process including an alkali treatment after applying the ink to the cloth. "Dichlorotriazine group, monochlorotriazine group, trichloropyrimidine group, monochlorodifluoropyrimidine group, chlorobenzothiazole group, dichloropyritazone group, dichloropyridazine group, dichloroquinoxaline group,
Epoxy group, 3-carboxypropyl pyridinium niobium triazine _{group, -SO 2 CH 2 CH 2 OSO} 3 H, -SO 2 NHCH 2 CH 2 OSO 3 H, -NHCOCH 2 CH 2 OSO 3 H, -NHCOCH 2 CH 2 Cl, _{-NHCOCH = CH 2, -SO 2 CH} = CH 2, -CH 2 NHCOCCl = CH 2, -NHCOCBr = CH 2, -NHCOCH 2 Cl, -NHCH 2 OH, -PO 3 H " 2. The inkjet printing method according to claim 1, wherein the fiber is any one of cotton, hemp, viscose, wool, silk and nylon. 3. The ink jet printing method according to claim 1, wherein the cloth is a mixed woven cloth or a non-woven cloth containing at least fibers dyeable with a reactive dye. 4. The inkjet printing method according to claim 1, wherein the organic solvent is an organic solvent having no active hydrogen. 5. The organic solvent is dimethylformamide,
Dimethylacetamide, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, N-methyl-2
The inkjet printing method according to claim 1, wherein the method is at least one selected from the group consisting of -pyrrolidone and 1,3-dimethyl-2-imidazolidinone. 6. The organic solvent is a dialkyl (1 to 4 carbon atoms) ether of polyoxyethylene (1 to 15 addition moles), a polyoxyethylene / oxypropylene block (or random) copolymer (addition moles). Number 1-15
The inkjet printing method according to claim 1, wherein the inkjet printing method is at least one selected from among (4) dialkyl (1 to 4 carbon atoms) ethers. 7. The ink-jet printing method according to claim 1, wherein the organic solvent is contained in the solvent in an amount of 1 to 70% by weight. 8. The ink-jet printing method according to claim 1, wherein the reactive dye is contained in the ink in an amount of 0.1 to 15% by weight. 9. The ink jet printing method according to claim 1, further comprising any one of a dispersant, a surfactant and a viscosity modifier in the ink. 10. The surface tension of ink is 30 to 60 dyne / cm (2
The inkjet printing method according to claim 1, wherein the temperature is adjusted to 5 ° C.). 11. The inkjet printing method according to claim 1, wherein the viscosity of the ink is adjusted to 50 cps (25 ° C.) or less.