JPS61179273A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent discharge stability and can form clear and fine pattern on woven or nonwoven fabric, consisting of an acid dye and an aq. medium and having a specified polyvalent metal content. CONSTITUTION:0.1-15wt% acid dye (e.g. C.I. Acid Yellow 17) and optionally additives such as dispersant, surfactant, viscosity modifier, resistivity modifier, anti-foaming agent, penetrant, mildewproofing agent, pH adjustor, etc. are dissolved in an aq. medium composed of water alone or water and a hydrophilic high-boiling org. solvent (e.g. ethylene glycol). The soln. is purified by salting out, fractional precipitation or ion exchange to obtain an ink compsn. for ink jet recording, which has a viscosity of 50cP at 25 deg.C and a polyvalent metal content of 100ppm or below (excluding the quantity of a polyvalent metal in a metal-contg. dye).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an ink composition for inkjet recording,
In particular, it is suitable for printing woven or non-woven fabrics made of fibers that can be dyed with acid dyes, such as wool, silk, nylon, acrylic, etc., or blended woven fabrics or blended non-woven fabrics made of these fibers and other natural fibers or composite TO & fibers. The present invention relates to an ink composition suitable for inkjet recording.

(Prior Art) Conventionally, woven or non-woven fabrics made of fibers that can be dyed with acid dyes, such as wool, silk, nylon, acrylic, etc., or blended woven fabrics of these fibers with other natural fibers or synthetic fibers, etc. For printing, printing methods such as roller printing, screen printing, and transfer printing are used, and some printing methods using inkjet recording methods have also been proposed.

(Problem to be solved by the invention) However, in the conventional general textile printing method, it is necessary to create printing plates for printing, and the creation of these plates, such as printing plate cylinders and screen plates, is expensive. Also, in transfer printing, the production of plates for printing transfer paper is expensive, so
The cost is not worth it unless you produce it in large quantities. Ma.

In addition, since the fashion period of printed cloth patterns is generally short, making plates each time increases the cost, and there is a serious problem that it is not possible to respond quickly to trends, and a large amount of inventory may be required. In order to solve these drawbacks, printing using an inkjet method has been proposed, but printing using this inkjet method causes various problems such as clogging of the ink ejection section of the recording device.
Practical implementation was not always easy.

Furthermore, depending on the type and concentration of the acidic dye, even if the dye is completely dissolved when the ink is prepared, a precipitate may form if the ink is left to stand, resulting in problems with the storage stability of the ink.

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

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

(Disclosure of the Invention) That is, the present invention consists of an acidic dye and an aqueous medium, and the polyvalent metal content thereof is 100 ppm or less (however, the polyvalent metal in the metal-containing dye is not considered). This is a characteristic ink composition for inkjet recording.

To explain the present invention in more detail, the first feature of the present invention is that an acid dye is used as a coloring component of the inkjet recording ink composition, and the second feature is that an acid dye is used as a coloring component of the inkjet recording ink composition. The point is that the polyvalent metal content of the ink composition containing the dye is adjusted to 1100 pp or less.

As a result of various studies on textile printing using the Infusiera method, the present inventor has found that various problems with the above-mentioned equipment and problems with the storage stability of the ink are caused by alkaline earth metals and other polyvalent metals present in the ink composition. The object of the present invention was mainly achieved by discovering that this is due to the presence of inorganic salts of metal ions or colloids thereof, and by adjusting the content of these polyvalent metals to below a certain concentration.

The acid dyes that first characterize the present invention and are used in the present invention are materials that are known per se and are water-soluble azo, anthraquinone, and other materials that are widely used in fiber dyeing or conventional textile printing methods. It is a dye. These acidic dyes have water-soluble groups such as sulfonic acid groups and carboxyl groups in their structures, and are capable of ionic adsorption or salt formation with basic moieties such as amino groups, imino groups, and amide groups in fibers. It dyes fibers through natural adsorption, etc.

In the present invention, any of these conventionally known acid dyes can be used, and preferred acid dyes in the present invention include C,1, Acid Yellow 17.19.2
5.39.40.42.44.49.50.61.64
．． 76.79.110.127.135.143.15
1.159.169.174.190.195.196
゜197.199.218.219.222.227,
C, 1, Acid Orange 3.19.24.28: 1
．． 33.43.45.47.51.67.94.116
．． 127.138.145.156, C, 1, Acid Red 35.42.57.62.80.82.111.
114.118.119.127.128.131.1
43.151.154.158.249.257.26
1.263.266.299.301.336.337
．． 361.396.397, C, 1, Acid Violet 5.34.43.47.48.90.103.12
6, C, 1, Acid Blue 25.40.41.62.
72.76.78.80.82.92.106.112
．． 113.120.127: t, 129.138.1
43.175.181.205.207.220.22
1.230.232.247.258.260.264
．． 271.277.278.279.280.288.
290.326, C, 1, Ashi・, De Green 16, ■
7.19.20.25.28.40.41.71, C,
1, Acid Brown 4.248, C, 1, Acid Black 7.24.29.48.52:l, 172, etc.

In the present invention, as a medium for dissolving the acidic dye as described in "2" above, any medium used in conventional general dyeing or a medium used in conventional inkjet recording ink can be used, such as water or water. and a water-soluble organic solvent are preferred, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
C1-C4 alkyl alcohols such as 5eC-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohols such as acetone and diacetone alcohol; tetrahydrofuran, dioxane, etc. ethers; polyalkylene gelylcols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol,
Butylene glycol, triethylene glycol, 1.2
．． Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as 6-hexandriol, thiodiglycol, hexylene glycol, diethylene glycol: glycerin; ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ) Lower alkyl ethers of polyhydric alcohols such as ether, triethylene glycol monomethyl (or ethyl) ether: N-methyl-2-pyrrolidone, 1,
Examples include 3-dimethyl-2-imidazolidinone.

The above-mentioned media can be used alone or as a mixture, but
The most preferred medium composition consists of water and one water-soluble organic solvent, where the water-soluble solvent contains at least one water-soluble high temperature point organic solvent, such as ethylene glycol, propylene glycol, glycerin, etc. It contains alcohol. The amount of these media used is such that when the ink composition is prepared, the content of the acidic dye is about 0.
The amount is 1 to 15% by weight.

The essential components of the ink composition of the present invention are as described in 1. However, various other conventionally known dispersants, surfactants, and viscosity modifiers may be added as necessary.

Dispersants or surfactants that can be added as necessary include fatty acid groups, alkyl sulfate salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate salts, and naphthalene sulfone formalin. Anionic dispersants or surfactants such as condensates, polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block copolymer, and other nonionic dispersants 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 preferred, and using these viscosity modifiers,
Alternatively, the viscosity of the ink composition of the present invention may be reduced to 2.
The temperature is 50 cps or less, preferably 1 to 15 cps at 5°C.

Further, in order to prepare ink used in an inkjet recording method of the type in which the ink is charged, a resistivity adjuster such as inorganic salts such as lithium chloride, ammonium chloride, and sodium chloride is added.

Note that when applied to an ic-jet method in which ink is ejected by the action of thermal energy, thermal physical property values (eg, specific heat, coefficient of thermal expansion, thermal conductivity, etc.) may be adjusted.

In addition, additives other than the above three types may be used as necessary.
For example, antifoaming agents, penetrants, antifungal agents, pH adjusters, etc. can be added as appropriate.

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

The inkjet recording ink composition of the present invention is obtained as described above, but the particularly important points in the present invention are as follows.
When blending the essential components and optional components as described in 1 above, the polyvalent metal content of the obtained ink composition is adjusted to 100 ppm or less, and the ink composition is adjusted to have a polyvalent metal content as described above. The object of the present invention is mainly achieved by having the following. Such adjustment of the polyvalent metal content can be achieved by limiting the material of the device for dissolving the acidic dye used in the present invention, by purifying the acidic dye by any known method, and by distilling the water used as a medium. This is achieved by using water or deionized water.

Purification methods include conventionally known salting-out methods, extraction methods, fractional precipitation methods, methods using ion exchange membranes, ultrafiltration methods,
Suitable methods include a reverse osmosis method, a method using a microfilter, a method using a chelating agent, a recrystallization method, a method using a flocculant, or a combination of these methods.

In the inkjet recording ink composition of the present invention,
When the polyvalent metal content is 100 pp+m or more,
This may cause clogging, etc. In addition, the ejection stability of the ink may be poor, problems may occur with the dissolution stability of the ink itself, and the level dyeing of woven fabrics may also be impaired. resolved rapidly.

The above inkjet recording ink composition of the present invention is
It is useful for printing woven or non-woven fabrics by inkjet recording, and is particularly useful for printing woven or non-woven fabrics made of fibers that can be dyed with acid dyes, such as wool, silk, nylon, acrylic, etc., or these fibers and cotton, linen, and bis. Natural #li like a course etc! It is useful for printing mixed woven fabrics or blended nonwoven fabrics made of a or synthetic fibers such as polyester fibers, acetate fibers, polypropylene fibers, and vinylon fibers. Any conventionally known woven or nonwoven fabric can be used, but in addition, these woven or nonwoven 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 that can quickly absorb and retain the ink composition applied to the surface of the fibers constituting the woven fabric.

The inkjet recording method used to apply the inkjet recording ink composition of the present invention to the above-mentioned woven fabric, nonwoven fabric, or molded article effectively removes the ink composition from a nozzle and Any method may be used as long as it can be applied to cloth or nonwoven fabric, and representative methods include, for example, IEEE Tr
ans action industry
Applications Vol, JA-13, N
o, 1 (February/March 1977 issue) and Nikkei Electronics No. 305 (December 8, 1982 issue). The methods described in these are suitable for use with the inkjet recording ink composition of the present invention.To explain some of them, there is an electrostatic suction method. A strong electric field is applied between the ink composition and an accelerating electrode placed in front of the nozzle, and the ink particles are drawn out one after another from the nozzle. Information signals are given to the deflection electrodes while the drawn ink composition flies between the deflection electrodes. There are two methods: one is a method of recording ink droplets in response to an information signal without deflecting the ink droplets, and both methods are effective in applying the inkjet recording ink of the present invention.

The second method is to forcibly eject minute ink particles by applying high pressure to the ink with a small pump and mechanically vibrating the nozzle with a crystal oscillator. At the same time as the injection, it is charged according to the information signal. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the amount of charge. Another method using this method is called the microdot inkjet method. In this method, ink pressure and excitation conditions are kept within a certain range of values, and two types of ink droplets, large and small, are produced from the nozzle tip. is generated, and only these medium- and small-diameter droplets are used for recording. The feature of this method is that it is possible to obtain a group of minute droplets even with a nozzle diameter that conventionally has a large wave.

A third method is a piezo element method, in which a piezo element is used as a pressure means for applying pressure to the ink, instead of a mechanical means such as a pump as in other methods. This method applies an electric signal to a piezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from a nozzle.

Further, the ink composition of the present invention is disclosed in Japanese Patent Application Laid-open No. 54-5183.
In the method described in Publication No. 7, the ink subjected to the action of thermal energy undergoes a rapid volume change, and the ink is ejected from the nozzle by the action force caused by this state change. suitable,
Shows excellent ejection stability.

Any of the various inkjet recording methods described above can be used, and any of these methods can be used to record woven fabrics,
Patterns such as characters and figures are formed on fabrics such as non-woven fabrics using colored ink compositions, but as described above, the inkjet recording ink composition of the present invention has polyvalent metal content controlled to a certain concentration or less. This makes it possible to print uniformly.

Therefore, a clear and fine pattern can be formed by passing through a dyeing process such as a steaming method, if necessary. On the other hand, when conventional inkjet recording ink compositions are used, they not only cause the above-mentioned equipment problems, but also have poor level dyeing properties, making it difficult to form fine patterns on woven fabrics. Ta.

As described above, the ink composition for inkjet recording of the present invention allows the ink composition to be deposited on a woven fabric or the like in accordance with the image signal, and the acid dye in the ink composition in this state is simply absorbed by the woven fabric. Since there are cases where the dye is merely attached to the cloth, it is preferable to subsequently perform a step of reaction-fixing the dye onto the m-fiber and removing the unfixed dye. Such reactive fixing and removal of unreacted dye can be carried out in accordance with a conventionally known method of washing after treatment such as a steaming method.

According to the present invention as described above, there is no need to create an expensive printing plate as in conventional general textile printing, and the image to be printed can be created and modified extremely easily using a computer. It is possible to respond to changes in fashion from time to time without requiring expensive technology. Therefore, sufficient profits can be secured even with small-scale production without mass production as in the prior art. Furthermore, it has the advantage that it can be applied not only to industrial textile printing methods but also to hobby print printing in ordinary households.

Next, the present invention will be explained in more detail with reference to Examples. Note that the numbers in the middle of the sentence and % are based on weight.

Example 1 Acid dye (C, 1, Ac1d Red 2fi3)
5 parts anionic surfactant (dispersant) Nikkor SLS, manufactured by Nikko Chemicals) 0.1 part ethylene glycol 15 parts diethylene glycol 15 parts water
65 parts All of the above components were mixed, and the mixed solution was adjusted to pH 8.5 with sodium hydroxide, stirred for 4 hours, and then filtered using Fluorobor Filter FP-
The water-based ink (A) of the present invention was obtained by passing through Zoo (manufactured by Sumitomo Electric).

Example 2 Acid dye (C:, r, Ac1d Yellow 25)
3-part acid dye (C, 1, Ac1d Oran
ge 19) 1 part anionic surfactant (Thymol C1 manufactured by Kao Soap) 0.1 part nonionic surfactant (Emulgen 950, manufactured by Kako Soap) 0.2 part 1so
-Propyl alcohol 0.5 parts Propylene glycol 15 parts Polyethylene glycol 400 6 parts Water
75 parts A water-based ink (B) of the present invention was obtained in the same manner as in Example 1 except that all the above components were used.

Example 3 Acid dye (C, 1, Ac1d Blue 40)
7 parts nonionic surfactant (Emulgen 931, manufactured by Kako Soap) 0.1 part nonionic surfactant (Rheodor TW-P120, manufactured by Kako Soap) 0.1 part ethyl calpitol 20 parts water
73 parts A water-based ink (C) of the present invention was obtained in the same manner as in Example 1 except that all the above components were used.

Example 4 Acid dye (C, 1, Ac1d Black 24)
3 parts nonionic surfactant, Tucor NP-15, Nikko Chemical Acid) 0.1 part ethylene glycol 25 parts glycerin
5 parts 1,3-dimethylimidazolidinone 5 parts water
A water-based ink (D) of the present invention was obtained in the same manner as in Example 1 except that all the components described in 1.62 parts were used.

Comparative Example 1 Acid dye (C, T, Ac1d Green 25)
8 parts anionic surfactant 0.
5 parts (manufactured by Kakoru C1 Kao Soap) Ethylene glycol 15 parts Polyethylene glycol 600 10 parts Water
A water-based ink (E) for comparison was obtained in the same manner as in Example 1 except that 60 copies of the above-mentioned sample were used.

Each water-based ink (A to E) of Examples 1 to 4 and Comparative Example 1
The properties are shown in Table 1 below.

Usage Example 1 Each water-based ink of Examples 1 to 4 and Comparative Example 1 (A-E)
(1) An inkjet printer (nozzle size: 40 x 50 Ii) using thermal energy according to the method described in JP-A-54-51837, (2
) Inkjet printer project using piezo elements
-108OA (manufactured by Canon, nozzle size 65JLφ
) and used a 10-piece nozzle to print 10 dots continuously on 100% nylon shirozette fabric.

In addition, 100 cc of each water-based ink (A-E) was placed in a glass bottle and stored at 40°C for one week to evaluate the storage stability of the ink. The results are shown in Table 2 below.

In addition, the water-based inks (A-D) of Examples 1 to 4 were applied to an inkjet printer PJ-108 using a piezo element.
A (manufactured by Canon, nozzle size 65ILφ), (1) prints on 100% nylon georgette fabric, then puts it in a 95℃ oven for 30 minutes to fix it, then washes it with a neutral detergent. To my horror, I got a clear print.

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48 58 80 180
*I Shows the results of analysis using an ICPC inductively coupled plasma emission spectrometer.

-Kakura J) -Ra Ei- Example Comparative example 你) ``Complete, y zpi completef Completef Main 1 once stuckness ノ dan Z evening 2 l) 0 1
0 1 10 printer (2) 0
0 0 0 8 Name - Storage Stability ○ ○ OOX*1 Each type of printer uses 10 nozzles for 10 dos 5. Number of nozzles that were clogged when 1 liter of continuous pudding was produced*2 After storing the ink at 40°C for one week, it was visually determined whether or not foreign matter was generated in the glass bottle.

O: No foreign matter ×: Foreign matter generated Patent applicant Canon Co., Ltd. Procedural amendment (method) % formula % 1. Indication of the incident Japanese Patent Application No. 18738/1982 2. Name of the invention Ink composition for inkjet recording 3. Amendment Patent applicant 146 Address 401, 4th floor, Taiyo Building, 3-27 Kanda Sakuma-cho, Chiyoda-ku, Tokyo (101) 5 Date of amendment order May 8, 1985 ( Shipping date: May 28, 1985)6
, Subject of amendment The detailed description of the invention in Description 7, Contents of the amendment, is amended as follows.

(1) rIEEE Tra on page 13 of the specification, lines 5-6
nsactions on Industry App
lications J is ``IEEE Trans acti on Industry Applications''.
ons on Industry Application
ions sword.

that's all

Claims (1)

[Claims] (1) An inkjet recording ink composition comprising an acidic dye and an aqueous medium and having a polyvalent metal content of 100 ppm or less (however, polyvalent metals in the metal-containing dye are not taken into account). .