JPS61118474A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:The titled ink composition, consisting of a disperse dye and medium having a multivalent metal ion concentration thereof below a specific value, and suitable for printing (non)woven fabrics consisting of polyester fibers without requiring the preparation of expensive printing plates in printing. CONSTITUTION:An ink composition, consisting of a disperse dye, preferably C.I. Disperse Yellow 3, 4 or 5, C.I. Disperse Orange 1, 3 or 5, C.I. Disperse Red 1, 4 or 5, C.I. Disperse Violet 1, 4 or 8, C.I. Disperse Green 9, C.I. Disperse Brown 1, 2, 4 or 9, C.I. Disperse Blue 1, 3 or 7, C.I. Disperse Black 1, 3 or 10, etc., and a medium, and having <=100ppm multivalent metal ion concentration thereof.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an ink composition for inkjet recording,
In particular, the present invention relates to an inkjet recording ink composition suitable for printing recording materials made of synthetic resins such as polyester and acetate, and more preferably woven or nonwoven fabrics made of fibers of these synthetic resins.

(Prior art) Traditionally, printing methods such as roller printing, screen printing, and transfer printing have been used to print woven fabrics and nonwoven fabrics made of synthetic fibers such as polyester and acetate, or blended woven fabrics of these fibers and other fibers. In some cases, a printing method using an inkjet recording method has also been proposed.

(The problem that the invention is trying to solve) However,
In conventional general textile printing methods, it is necessary to create printing plates for printing, and these plates 1, such as printing plate cylinders and screen plates, are expensive, and transfer paper is also required for printing in transfer printing. The production of plates for this is expensive, so it is not cost-effective unless a large quantity is produced, and
In general, the fashion period for printed cloth patterns is short, so making plates each time increases the cost, and there is a serious problem in 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, inkjet printing has been proposed, but this inkjet printing causes various problems such as clogging of the ink ejection section of the recording device, and it is not necessarily easy to put it into practical use. There wasn't. Furthermore, since a disperse dye is used as the dye, it is difficult to maintain the dispersion stability 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 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.

Another object of the present invention is to print an inkjet recorder capable of printing not only woven fabrics but also various synthetic resin molded products such as polyester sheets and films with excellent durability and patterns. An object of the present invention is to provide an ink composition for use in the present invention.

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 is an ink composition for inkjet recording comprising a disperse dye and a medium, and characterized in that the concentration of polyvalent metal ions is 100 pp layer or less.

To explain the present invention in more detail, the first feature of the present invention is that a disperse dye is used as a coloring component of an inkjet recording ink composition, and the second feature is that a disperse dye is used as a coloring component of an inkjet recording ink composition. The polyvalent metal ion concentration of the ink composition was adjusted to 100 ppm or less.

As a result of various studies on textile printing using the inkjet method, the present inventor has found that various troubles with the above-mentioned equipment and problems with ink dispersion stability are caused by alkaline earth metal and other polyvalent metal ions 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 or colloids thereof, and adjusting the concentration of these polyvalent metal ions to below a certain level.

The disperse dye used in the present invention, which first characterizes the present invention, is a material known per se, and is a water-insoluble azo-based, anthraquinone-based, or other material that is widely used in fiber dyeing or sublimation transfer technology. It is a dye. These disperse dyes do not have water-soluble groups such as sulfonic acid groups or carboxyl groups in their structure, and have molecular weights within a certain range, and can be used after or after being applied to fibers or woven fabrics as an aqueous dispersion. In the present invention, any of these conventionally known disperse dyes can be used, and is preferred in the present invention. Disperse dyes include c, r, deathbirds yellow 3゜4.5.7.9.13, 24, 30.33
．． 34.42, 44.49.50.51.54.56.
58.60.63.64.66.68.71.74.7
6.79.82.83.85.86.88.90.91
．． 93.98.99.100.104.114.116
, 118.119.122.124, 126.135.
140,141.149.180.162.163.1
64°165.179, tao, 182.183.18
6.192.198.199.202.204.210
．． 211.215.216.218.224;C,Z,
Deathbirds Orange 1.3.5.7.11.13.17
．． 20.21.25.29.30.31.32.33.
37.38, 42.43.44.45.47, 48.4
9,50.53.54.55.58.57.58.59
．． 61.66.71.73.76.78.80.89.
90.91.93.96.97.119.127,13
0,139,142. c.Z.

Deathbirds Red 1.4.5.7.11,12゜13.
15.17.27.43.44.50, 52.53.5
4.55.56.5B, 59.60.65.72.73
．． 74.75.76.78.81.82.86.88.
90.91.92.93.96, 103.105, 10
6,107.108.110.111.113,117
゜118.121.122.126.127,128.
131.132.134.135.137.143.1
45.146.151.152.153.154,15
7,159,164.167.169.177.179
．． 181.183J184, 185, 188, 189,
190. 191.

192. ZOOl 201. 202. 203.
205, 206, 207. 210. 221, 22
4.225, 227, 229, 239.240. 25
7, 258, 277, 278, 279, 281.288
, 296, 303, 310. 311. 312.3
20.324,328. (,1, Deathbirds Violet 1.4.8.23.26.27.28, 31, 3
3. 35, 36. 3g, 40, 43, 46,
48, 50, 51, 52. 56. 57.59.6
1.63.69.77, C, 1, Deathbirds Green 9
．． C, 1, Deathbirds Brown l, 2.4, 9.13.
191. C, 1, Deathbirds Blue 1.3.7.9.1
4, 16.19.20.26.27.35.43.44
．． 54.55.56.58.60.62.64.70.
72, 73.75.79.81.82.83.87.9
1.93.94.95.96.102.106.108
．． 112.113.115.118.120,122,
125, 128.130, 139.141. 142.
143, 146.148, 149. 153.
154.158, 165, 167, 171. 17
3. 174. 176.181, 183, 185
, 186, 187, 189, 197, 198, 200.
201. 205°207, 211, 214.224
．． 225. 257, 259, 267, 268.
270. 284°285, 287.288. 29
1, 293. 295, 297.301, 315.
330. 333°C, 1, Deathbirds Black 1, 3
．． 10.24; Kayaseron Red E-GL, Kayaseron Blue ~ E-TB, Kayaseron Navy Blue E-E
X, Kayaseron Black E-EX, and the like.

In the present invention, as the medium for dispersing or dissolving the above-described disperse dye, any medium used in conventional general dyeing and the medium used in conventional inkjet recording ink can be used. For example, water and/or Or a water-soluble organic solvent is preferable, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Alkyl alcohols with 1 to 4 carbon atoms such as 5ea-butyl alcohol, tart-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 glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol,
Butylene gelicol, triethylene glycol, 1,2
．． Alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms, such as 6-hexane tensuol, thiodiglycol, hexylene glycol, diethylene glycol; glycerin; ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or Lower alkyl ethers of polyhydric alcohols such as ethyl) ether and 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 or more water-soluble organic solvents, where the water-soluble solvent contains at least one water-soluble high-boiling organic solvent, such as a polyhydric alcohol such as ethylene glycol, propylene glycol, or glycerin. It contains. The amount of these media used is such that when the ink composition is prepared, the content of the disperse dye is approximately 0°1.
-15% by weight.

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

Examples of dispersants or surfactants that can be added as necessary include fatty acid salts, alkyl acid ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, and naphthalene sulfonic acid. Anionic dispersants or surfactants such as formalin condensates, polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acids Nonionic dispersants or surfactants such as esters, polyoxyethylene alkyl amines, glycerin fatty acid esters, oxyethylene oxypropylene block copolymers, etc. 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 can be reduced by 1 to 2 without using it.
It is 50 cps or less, preferably 1 to 1 Ocps 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 inkjet system 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 ink composition for inkjet recording of the present invention can be obtained by mixing the above-mentioned essential components and optional components and subjecting the mixture to a grinding process using conventionally known grinding means such as a ball mill, sand mill, speed line mill, etc. Generally, the particle size of the disperse dye is usually 30JLm or less, preferably 204m or less.If the particle size is too large, problems such as nozzle clogging may occur during inkjet recording, or problems may occur during the subsequent dyeing process. Problems arise with level dyeing, etc. Furthermore, when a medium that dissolves the disperse dye is selected as the medium, the ink composition of the present invention can be obtained only by the dissolving action of heating.

The inkjet recording ink composition of the present invention is obtained as described above, but what is particularly important in the present invention is that when the above-mentioned essential components and optional components are blended, the ink composition obtained during or after the grinding treatment is The purpose is to adjust the polyvalent metal ion concentration of the ink composition to 100 ppm or less,
The object of the present invention is mainly achieved by making the ink composition have the above-mentioned polyvalent metal ion concentration. Such adjustment of the polyvalent metal ion concentration can be achieved by limiting the material of the device for grinding the disperse dye used in the present invention, by refining the disperse dye by any known method, and by adjusting the water used as a medium. This is achieved by using distilled or deionized water. The material of the grinding device is preferably alumina, and the refining method is as follows:
Suitable methods include extracting the disperse dye with an organic solvent or suspending washing with a solvent in which polyvalent metal ions are soluble.

In the inkjet recording ink composition of the present invention,
When the polyvalent metal ion concentration is over toopp■,
This may cause clogging, etc. In addition, the ejection stability of the ink may be poor, problems may occur with the dispersion stability of the ink itself, and the level dyeing of woven fabrics may not be sufficient, but when the concentration is below the above level, these various problems suddenly occur. It will be resolved.

The above inkjet recording ink composition of the present invention is
It is useful for printing woven or non-woven fabrics by inkjet recording, especially polyester Iam, acetate fiber, polypropylene fiber, vinylon fiber, polyamide F.
It is useful for printing woven fabrics or nonwoven fabrics made of synthetic fibers such as am, or mixed woven fabrics or nonwoven fabrics made of these synthetic fibers and other #Jta fibers, such as cotton 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. This can be done 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. Furthermore, the inkjet recording ink composition of the present invention can be applied not only to woven or nonwoven fabrics made of one synthetic fiber as described above, but also to sheets, films, and other molded products made of synthetic resins such as polyester, acetate, polypropylene, and nylon. It also has an excellent effect in adding patterns and patterns.

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, non-woven fabric, or molded articles, and typical examples of these methods include II'
EE Transactions on In
industry Applications Vo
lJA-13, No. 1 (February and March 1977 issues),
Nikkei Electronics No. 305 (December 8, 1982)
day number). The methods described above 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. 111
11 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 jumps between the deflection electrodes. There are two methods: a method for recording, and a method for ejecting ink droplets in response to an information signal without deflecting the ink droplets, both of which are effective in applying the present invention to inkjet recording.

The second method is to apply high pressure to the ink with a small pump and mechanically vibrate the nozzle with a crystal oscillator, etc. to forcibly eject minute ink particles, and the ejected ink particles 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 conventionally large nozzle diameter.

A third method is a piezo element method, in which a piezo element is used as a pressure means to apply pressure to the ink, rather than a mechanical means similar to 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.
Suitable for the method described in Publication No. 7, in which 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. , and exhibits 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 the surface of nonwoven fabric or molded products using colored ink compositions, but as described above, the inkjet recording ink composition of the present invention has a polyvalent metal ion concentration below a certain concentration. Since it is controlled, clogging does not occur and the ejection stability is extremely good. Furthermore, the dye has excellent dispersion stability, and uniform printing is possible.

Therefore, a clear and fine pattern can be formed through the subsequent dyeing process using heat treatment. 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, with the ink composition for inkjet recording of the present invention, the ink composition can be deposited on a woven fabric etc. according to the image signal, and the disperse dye in the ink composition in this state is simply woven into the woven fabric. Since it is simply attached to the cloth, further heat treatment is required. Such heat treatment may be a conventionally known heat treatment. For example, a printed woven fabric or the like is passed between heated rollers and heated at 120 to 250 degrees for several seconds to several tens of seconds.
Heat treatment is carried out at a temperature and time necessary for the disperse dye in the ink composition to dye the resin such as polyester constituting the woven fabric etc., such as by heating to a temperature of °C or passing it through a superheated steam chamber. Just add it.

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. Furthermore, the ink composition of the present invention is useful not only for recording on woven fabrics and non-woven fabrics, but also on hydrophobic synthetic resins 1, such as polyester films and sheets. Conventionally, inkjet recording on transparent recording materials such as polyester sheets has used ink containing water-soluble dyes.

It is necessary to form a hydrophilic ink receiving layer on the recording surface of the polyester sheet, and this receiving layer absorbs and retains ink. Therefore, there was a problem with the abrasion resistance of the recording surface.
According to the ink composition of the present invention, since the dye in the ink is dyed into the polyester film, these problems do not occur, and there is an advantage that the clarity and transparency are further improved. be.

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 Disperse dye (C:, 1. Disperse Blue 187) 5 parts Anionic surfactant (dispersant) 4 parts (Demol N, manufactured by Kao Ishichichi ■) Ethylene glycol 15 parts Diethylene glycol 13 parts Water
After dispersing 65 parts and all components of 2 in an alumina ball mill for about 36 hours, the pH was adjusted to 8.3 with sodium hydroxide.
Further, dispersion was carried out for 3 hours using an alumina ball mill, and then Fluoropore filter FP-1000 (Judendenko ■
Coarse particles with a particle size of 10 gm or more were removed using a water-based ink (A) of the present invention.

Example 2 Disperse dye (C, 1, Disperse Orange 55) 3 parts Acid dye CG, 1. Acid Yellow 49) 1 part anionic surfactant ゛ 0.5 part Kukkor 0TP
-100s, manufactured by Nikko Chemicals) Anionic surfactant 1.5 parts (Demo C1 manufactured by Kao Soap ■) Nonionic surfactant 0.2 parts (Emulgen 911, manufactured by Kao Soap ■) ISO-propyl alcohol 0 .5 parts propylene glycol 15 parts polyethylene glycol 400 5 parts water
75 parts After dispersing all the above components in an alumina ball mill for about 40 hours, the p)I was adjusted to 7.4 with potassium hydroxide, further dispersing for 2 hours, and then using a Fluoropore filter FF-500. (
Coarse particles with a particle size of 54 m or more were removed using a water-based ink (B) of the present invention.

Example 3 Disperse dye (C:, 1. Disbird's Red 111) 7 parts Reactive dye (C, 1, Disbird's Red 8o) 2 parts Nonionic surfactant 1.5 parts (Emulgen 707. Made by Kao Stone Ni ) Nonionic surfactant
2.0 parts (Rheodor TW-P 120, manufactured by Kao Seki m'lJA) Ethyl calpitol 20 parts Water
A water-based ink (C) of the present invention was obtained from 70 copies of the above assembly in the same manner as in Example 2.

Example 4 Disperse dye (C, R, Disperse Blue 214) 3 parts Disperse dye (C, 1, Disperse Blue 197) 3 parts Anionic surfactant 5.5 parts (Ionet) D-・2. Sanyo Chemical Industrial ■) Ethylene Glycol
25 parts glycerin
5 parts 1,3-dimethylimidazolidinone 5 parts water
From the above plenary session of 60 copies, in the same manner as in Example 1,
Aqueous ink (D) of the present invention was obtained.

Comparative Example 1 Disperse dye (C, 1, Disperse Blue 56) 8 parts Anionic surfactant 5 parts (Thymol C1 manufactured by Kao Soap ■) Ethylene glycol 15 parts Polyethylene glycol 600 10 parts Water
After dispersing the above 60 copies using a sand grinder for about 5 hours, adjust the pi (pi) to 8.0 with potassium hydroxide, further dispersing using a sand grinder for 30 minutes, and then dispersing with a fluoropore filter FF. -1000 (manufactured by Sumima Denko) to remove coarse particles with a particle size of 10 m or more to obtain an aqueous ink (E) of the present invention.

Each water-based ink (A-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 IL) using thermal energy according to the method described in JP-A-54-51837, (2)
Inkjet printer PJ- that uses piezo elements
108OA (manufactured by Canon ■, nozzle size 65 φ)
LO' dots were continuously printed on 100% polyester georgette fabric using 10 nozzles. Further, 100 cc of each water-based ink (ANE) 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-1080 using a piezo element.
A (manufactured by Canon ■, nozzle size 65kLφ), (1) print on 100% polyester georgette fabric, then put it in a 215℃ oven for 3 minutes to fix it, and then use a neutral detergent. After washing, clear prints were obtained.

(Left below) n11"Ijigoku)'j'6)!'4C',, f 4,6,9 j6
fdMIC14855423843 1 8.3 7.5 5.1
11.2 8.1 on book L 81
45 83 78 350-Thu 2 11
B 4 +3 11 pieces t t
The results of analysis using a cpas conductive coupled plasma emission spectrometer are shown.

Book 2 Shows the results of analysis using the Coulter Counter.

c)'1f complete f complete)"<'d Main 1 亘闭子性 Gudan74)-Uni)000110zudanz
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.

0: No foreign matter ×: Foreign matter occurred Patent applicant: Canon Co., Ltd. Agent: Patent Attorney Ao 1) Hiroshi Katsu Procedural amendment (voluntary) January 9, 1985

Claims (1)

[Claims] (1) An ink composition for inkjet recording comprising a disperse dye and a medium and having a polyvalent metal ion concentration of 100 ppm or less.