JPH0621246B2 - INKJET PRINTING INK AND INKJET PRINTING METHOD USING THE INK - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ink-jet printing ink and an ink-jet printing method using the same, and in particular cotton, hemp,
Inkjet printing ink suitable for printing mixed woven fabrics or non-woven fabrics made of easily dyeable fibers such as viscose, wool, silk, and narilone, and synthetic dyes that are difficult to dye such as polyester and acetate The present invention relates to an inkjet printing method.

(Prior Art) Conventionally, for printing textiles such as a mixed woven fabric of easily dyeable fibers such as cotton, hemp, viscose, wool, silk and nylon, and synthetic fibers such as polyester and acetate which are difficult to dye. Printing methods such as roller printing, screen printing and transfer printing using a mixed dye of a reactive dye (or a slene dye) and a disperse dye are used, and a printing method by an inkjet recording method is also proposed in part. There is.

(Problems to be solved by the invention) However, in the conventional general printing method, it is necessary to create a printing plate for printing, and it is expensive to create these plates, for example, a printing cylinder or a screen plate. Also, in transfer printing, it is expensive to make a plate for printing a transfer paper, and therefore the cost does not match 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. Ink jet printing has been proposed to solve these drawbacks, but this ink jet printing causes various troubles such as clogging of the ink ejection portion of the recording apparatus and is not always easy to put into practical use. It was Furthermore,
When a dispersion type dye is used, it is difficult to maintain a stable dispersed state of the dye in the ink for a long period of time.

Therefore, an object of the present invention is to simultaneously solve the economical problems in the conventional general printing method as described above, the problems of various troubles and the accurate and stable printing problems in the printing method by ink jet recording. An object is to provide an ink composition for inkjet recording.

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 is an ink for inkjet printing, which comprises a reaction dispersion type dye and a medium, and has a polyvalent metal content of 100 ppm or less. or,
The present invention includes a reactive dispersion dye and a medium, and an ink having a polyvalent metal content of 100 ppm or less, which is formed of a mixed woven fabric or a mixed nonwoven fabric of a reactive dye dyeable fiber and a disperse dye dyeable fiber. Is applied by an inkjet method, followed by a dyeing treatment, and then a washing treatment, which is an inkjet printing method.

The present invention will be described in more detail. The first feature of the present invention is that a reaction dispersion type dye is used as a coloring component of an ink composition for inkjet recording, and the second feature is. This is because the polyvalent metal content of the ink composition containing the reaction-dispersion dye was adjusted to 100 ppm or less.

As a result of various researches on ink-jet printing, the present inventor has found that various problems of the above-mentioned apparatus and problems of dispersion stability of the ink include the alkaline earth metal present in the ink composition and many of them. Inorganic salts of valent metal ions or their colloidal substances, for example, sulfates of calcium, magnesium, iron, zinc, copper, silicon, chromium and the like,
The object of the present invention was mainly achieved by finding out that it was due to the presence of a colloidal substance such as hydrochloride and silicon oxide, iron oxide, etc., and adjusting the content of these polyvalent metals to a certain concentration or less. .

The first feature of the present invention and the reaction-dispersible dye used in the present invention is a material known per se, which is poorly water-soluble, which is partially used in the conventional method for printing polyester / cotton blended woven fabrics. Azo, anthraquinone and other dyes. These reaction-dispersible dyes do not have a water-soluble group such as a sulfonic acid group or a carboxyl group in the 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, , Ethyleneimine group, azido group, sulfoneethyleneimide group, dichlorotriazine group, monochlorotriazine group, trichloropyrimidine group, monochlorodifluoropyrimidine group, chlorobenzothiazole group, dichloropyridazone group, dichloropyridazine group, dichloro group Quinonexane group, epoxy group, 3
- carboxypyridinyl triazine _{group, -SO 2 CH 2 CH 2 OS} 3 H, -SO 2 NHCH 2 CH 2 OS 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, -SO 2 CH 2 CH 2 COCCH 3, - It has a group such as SO ₂ CH ₂ OCOC ₄ H ₉ .

In the present invention, any of these conventionally known reaction-dispersion dyes can be used, and preferable reaction-dispersion dyes in the present invention include: Dyes and derivatives thereof having structures such as are preferred.

In the present invention, as a medium for dispersing the reaction-dispersion dye as described above, any of conventional mediums for general dyeing and mediums used for conventional ink jet recording inks can be used, for example, water or water. And a water-soluble organic solvent are preferable, for example, carbon such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol. Alkyl alcohols of 1 to 4; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol, polypropylene glycol Polyalkylene glycols such as coal; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as hexylene glycol and diethylene glycol; glycerin; ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ethers; N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone and the like can be mentioned.

The above media can be used alone or as a mixture, but the most preferred medium composition is composed of water and at least one water-soluble organic solvent, and the water-soluble solvent is at least one water-soluble high-boiling organic solvent, for example, And polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin. The amount of these media used is such that when the ink composition is prepared, the content of the reaction dispersion type dye is about 0.1 to 15% by weight.

The essential components of the ink composition of the present invention are as described above, but various conventionally known dispersants, surfactants, and viscosity modifiers can be added as necessary.

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. Anionic dispersants such as condensates and polyoxyethylene alkyl sulfates, or surfactants; polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acids Nonionic dispersants such as esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethyleneoxypropylene block copolymers or surfactants 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, without using it, the viscosity of the ink composition of the present invention can be adjusted to 2
It is 50 cps or less at 5 ° C., preferably 1 to 10 cps.

Further, in order to prepare an ink used in an ink jet recording method 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 appropriately added.

The ink composition for ink-jet recording of the present invention is obtained by mixing the above-mentioned essential components and optional components and mixing and milling them with a conventionally known milling means, for example, a ball mill, a sand mill, a speed line mill or the like. Generally, the particle diameter of the disperse dye is usually 30 μm or less, preferably 20 μm or less. If the particle size is too large, problems such as nozzle clogging during inkjet recording may occur,
Problems occur in the level dyeing property in the subsequent dyeing process. When a medium that dissolves the disperse dye is selected as the medium,
The ink composition of the present invention can be obtained by a simple dissolving action such as heating.

As described above, the ink composition for ink jet recording of the present invention can be obtained. A particularly important point in the present invention is to obtain an essential component or an optional component as described above, during the polishing treatment, or after the treatment. The purpose of the present invention is mainly achieved by adjusting the content of the other-valent metal in the ink composition thus obtained to 100 ppm or less, and by making the ink composition have the content of the polyvalent metal as described above. is there. Such adjustment of the content of the other-valent metal is performed by limiting the material of the apparatus for grinding the reaction-dispersion dye used in the present invention or as a method and medium for purifying the reaction-dispersion dye by any known method. This is achieved by using distilled water or deionized water as the water used.

Alumina is preferable as the material of the grinding device, and as the purification method, a method of extracting the dispersion-reactive dye with an organic solvent or suspending with a solvent in which the polyvalent metal is soluble is preferable. .

In the ink composition for inkjet recording of the present invention,
If the polyvalent metal content is 100 ppm or more, it may cause clogging. Further, the ejection stability of the ink is inferior, a problem occurs in the dispersion stability of the dye, and further, the leveling property to the woven fabric is not sufficient, whereas when the concentration is less than the above,
These various problems are rapidly solved.

The inkjet recording ink composition of the present invention described above,
It is useful for textile printing or non-woven textile printing by ink jet recording, and particularly, fibers such as cotton, hemp, viscose, wool, silk, nylon, etc. which can be dyed with a reactive dye and polyester fiber, acetate fiber, polypropylene fiber, vinylon It is useful for one-stage printing of a mixed-spun woven fabric or a mixed-spun nonwoven fabric made of synthetic fibers that can be dyed with a disperse dye such as fibers. Any conventionally known woven or non-woven fabric can be used, and in addition, these woven or non-woven fabrics may be pretreated for inkjet recording printing. Such a pretreatment can be carried out by adding a water-soluble or water-dispersible polymer or the like which can quickly absorb and retain the ink composition applied to the surface of the fibers constituting the woven fabric.

The ink jet recording method used for applying the ink composition for ink jet recording of the present invention to the above-mentioned woven fabric, non-woven fabric or molded product is a woven fabric which is a range by effectively separating the ink composition from the nozzle. Any method may be used as long as it can be applied to a cloth or a non-woven fabric, and typical methods thereof are, for example, IEEE Trans actio
ns on Industry Applications Vol.JA-13, No.1 (1977
February and March), Nikkei Electronics No. 305 (19
December 6, 1982 issue). The methods described in these are suitable for use of the ink composition for ink jet recording of the present invention, and some of them will be described first by the electrostatic suction method. In this method, a nozzle and a few mm of the nozzle are used. A strong electric field is applied between the accelerating electrode placed in front and the ink is atomized from the nozzle and drawn out one after another, and an information signal is given to the deflection electrode while the drawn ink composition flies between the deflection electrodes for recording. Method and a method of ejecting ink particles in response to an information signal without deflecting the ink particles, both of which are effective for application of the one inkjet recording ink of the present invention.

The second method is to apply high pressure to the ink with a small pump,
This is a method in which minute ink particles are forcibly ejected by mechanically vibrating the nozzle with a crystal oscillator or the like, and the ejected ink particles are charged at the same time as ejection in accordance with an information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the charge amount. Another method using this method is called a micro dot ink jet method. In this method, ink pressure and excitation conditions are kept within a certain range of appropriate values, and two types of ink droplets, large and small, are ejected from the nozzle tip. Is generated, and only the medium and small diameter droplets are used for recording. The feature of this method is that a minute droplet group can be obtained even with a nozzle diameter as thick as the conventional one.

A third method is a piezo element method, and in this method, a piezo element is used as a pressure means to be 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 composition of the present invention is disclosed in JP-A-54-5993.
In the method described in Japanese Patent Publication No. 6, a method in which ink subjected to the action of thermal energy undergoes a rapid volume change, and printing is performed by an ink jet method in which ink is ejected from a nozzle by an action force due to this state change Suitable,
Shows excellent ejection stability.

Any of the various inkjet recording 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 on a cloth such as a woven cloth or a non-woven cloth by the colored ink composition. Since the polyvalent metal content of the ink composition for inkjet recording of the present invention is controlled to a certain concentration or less as described above, uniform printing is possible.

Therefore, it is possible to form a clear and fine pattern by a dyeing process such as a subsequent heat treatment or alkali treatment. On the other hand, when the conventional ink composition for inkjet recording is used, the above-mentioned problems in the apparatus occur, and the leveling property is poor and it is difficult to form a fine pattern on the woven fabric. It was

As described above, the ink composition for ink jet recording of the present invention enables the ink composition to adhere to a woven fabric or the like according to an image signal. The reaction dispersion type dye in the ink composition in this state is simply a woven fabric. It is preferred that subsequent steps of fixing the dye to the fiber and removing the unfixed dye are performed as they are only attached to the fabric. The method for removing the fixed and unfixed dyes may be a conventionally known method, for example, a steaming method, an HT steaming method, a thermofix, an alkali pad steam method, an alkali blotch steam method, an alkali shock method, an alkali. After the treatment by the cold fix method or the like, it can be carried out according to a conventionally known method of washing.

According to the present invention as described above, it is not necessary to prepare an expensive printing plate as in the case of conventional general printing in printing, and the image to be printed can be created and modified very easily by a computer. You can adapt to changing trends at any time without the need for expensive editions such as technology. Therefore, it is possible to secure a sufficient profit even in a small amount of production, instead of the mass 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 printing in a general household.

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

Example 1 Dye of the structural formula (2) 5 parts Anionic surfactant (dispersant) (Demol N, manufactured by Kaoishi Sapon Co., Ltd.) 4 parts Ethylene glycol 15 parts Diethylene glycol 13 parts Water 65 parts All the above components After dispersing with an alumina ball mill for about 36 hours, the pH was adjusted to 4.7 with acetic acid, further dispersing with an alumina ball mill for 3 hours, and then Fluoropore Filter FP-1000 (Sumitomo Electric ( Co., Ltd.) was used to remove coarse particles having a particle size of 10 μm or more to obtain an aqueous ink (A) of the present invention.

Example 2 Dye of the structural formula (7) 4 parts Anion size surfactant (Nikkor OTP-100s, Nikko Chemicals Co., Ltd.) 0.05 part Anion size surfactant (Demol C, Kao Soap Co., Ltd.) ) 1.5 parts Nonionic surfactant (Emulgen 981, manufactured by Kao Soap Co., Ltd.) 0.2 parts iso-propyl alcohol 0.5 parts Propylene glycol 15 parts Polyethylene glycol 400 5 parts Water 75 parts All the above components are alumina After dispersing with a ball mill for about 40 hours, the pH was adjusted to 5.6 with acetic acid and further dispersing for 2 hours, then Fluoropore Filter FP-500.
Coarse particles having a particle size of 5 μm or more were removed (by Sumitomo Electric Co., Ltd.) to obtain the aqueous ink (B) of the present invention.

Example 3 Dye of the structural formula (14) 7 parts Dye of the structural formula (15) 2 parts Nonionic surfactant (Emulgen 707, manufactured by Kao Soap Co., Ltd.) 1.5 parts Nonionic surfactant (Leodol) TW-P120, manufactured by Kao Soap Co., Ltd.) 2.0 parts Ethyl carbitol 20 parts Water 70 parts By the same method as in Example 2 above, an aqueous ink (C) of the present invention was obtained.

Example 4 Dye of the structural formula (9) 6 parts Anionic surfactant (Ionette D-2, manufactured by Sanyo Kasei Co., Ltd.) 5.5 parts Ethylene glycol 25 parts Glycerin 5 parts 1,3-Dimethylimidazo Lidinone 5 parts Water 60 parts By the same method as in Example 1 from the above all components, the aqueous ink (D) of the present invention was obtained.

Comparative Example 1 The ink composition of Example 1 was further dispersed in a stainless ball mill for 36 hours to obtain Comparative Ink (E).

Water-based inks (AE) of Examples 1 to 4 and Comparative Example 1
The properties are shown in Table 1 below.

Use Example 1 Each of the aqueous inks of Examples 1 to 4 and Comparative Example 1 (AE)
(1) Inkjet printer using heat energy (nozzle size 40 × 50 μm) according to the method described in JP-A-54-59936, (2) Inkjet printer using piezo element-PJ- 1
080A (Canon Co., Ltd., nozzle size 65μφ)
Mounted on 10 nozzles 65% polyester, 3 cotton
Continuous printing of 10 dots was performed on 5% broad cloth. In addition, 100 cc of each water-based ink (AE) was put in a glass bottle and stored at 40 ° C. for 1 week to evaluate the storage stability of the ink. The results are shown in Table 2 below.

Furthermore, the ink jet printer PJ-1080A (Canon Co., Ltd.) in which the water-based inks of Examples 1 to 4 (A to D) and the water-based ink of Comparative Example 1 (E) were used as piezo elements was used.
The product is mounted on a nozzle with a nozzle size of 65 μφ, printed on 65% polyester and 35% cotton broad cloth, then heat treated at 180 ° C for 90 seconds, and further treated at 90 ° C for 20 seconds in an alkaline bath adjusted with sodium carbonate. And fixed. Then, after washing with a neutral detergent, it was dried and the level dyeing property was evaluated. The results are shown in Table 2 below.

Claims (3)

[Claims] 1. An ink-jet printing ink comprising a reaction-dispersible dye and a medium, the polyvalent metal content of which is 100 ppm or less. 2. An ink containing a reaction-dispersible dye and a medium, the polyvalent metal content of which is 100 ppm or less, is prepared from a mixed woven fabric of reactive dye dyeable fibers and disperse dye dyeable fibers, or a mixed nonwoven fabric. An ink-jet printing method, wherein the cloth is applied by an ink-jet method, dyeing-treated, and then washed. 3. The method according to claim 2, wherein the cloth is pretreated with a water-soluble or water-dispersible polymer.