JPS61118473A - Ink composition for ink jet recording - Google Patents

Abstract

PURPOSE:The titled ink composition, consisting of a disperse dye and medium, having a surface tension within a specific range, and suitable for printing (non) woven fabrics consisting of polyester, acetate fibers, etc. without requiring the preparation of expensive printing plates in printing. CONSTITUTION:An ink composition for ink jet recording, consisting of a disperse dye, preferably C.I. Disperse Yellow 3, 4 or 5, C.I. Disperse Violet 1, 4 or 8, C.I. Disperse Blue 1, 3. or 7, C.I. Disperse Black 1, 3 or 10, etc. and a medium, e.g. water or a water-soluble organic solvent, and having a surface tension thereof within 35-50dyne/cm range.

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 materials made of synthetic resins such as polyester and acetate, and more preferably 512V or Al'a textiles made of these synthetic resin uli fibers.

(Conventional technique #i) Conventionally, roller printing, screen printing,
A printing method such as transfer printing is used, and some printing methods using an inkjet recording method have 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, printing using inkjet printing has been proposed, but in printing using inkjet printing, the viscosity of the ink used cannot be made very high due to the nature of the printer, and the viscosity of woven fabric is lower than that of paper. Since the weave is coarse, there is a problem in that the inkjet recording ink composition adhering to the Ia fabric surface smudges on the fabric surface, making it difficult to create fine patterns. Furthermore, because the ink is ejected from fine nozzles at high speed and at a high frequency, there are drawbacks such as unstable ejection and limited response to one frequency depending on the physical properties of the ink.

Therefore, one object of the present invention is to provide an inkjet recording ink composition that can simultaneously solve the economical problems of conventional general textile printing methods as described above and the problems of accurate and stable printing in textile printing methods using inkjet recording. The goal is to provide the following.

Another object of the present invention is to print an inkjet recorder capable of printing characters and other patterns with excellent durability on not only woven fabrics but also various synthetic resin molded products such as polyester sheets and films. 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 consists of (1) a disperse dye and a medium;
This is an ink composition for inkjet recording, characterized in that its surface tension is in the aid of 35 to 60 dBe/c layer.

To explain the present invention in more detail, the configuration that first characterizes the present invention is the inkjet z? ) Using a disperse dye as a coloring component of the recording ink composition. The fifth and second characteristic feature is that the surface tension of the ink composition containing monodisperse dye is adjusted within a certain range.

In other words, as a result of various studies on textile printing using the inkjet method, the inventor of the present invention found that the quality of the above-mentioned printed image is affected by the surface tension of the ink composition, and set these surface tensions to a constant value! 1m! By doing so, the object of the present invention is mainly achieved.

First Characteristics of the Present Invention The disperse dye used in the present invention is a material known per se.

These are water-insoluble azo, anthraquinone, and other dyes that are widely used in textile dyeing or sublimation transfer technology. 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. 80-2 inside
In the present invention, which dyes mainly synthetic fibers such as polyester and acetate at a temperature of 50°C, any of these conventionally known disperse dyes can be used. Preferred disperse dyes in the present invention include: C
, 1, Disbirds Yellow 3゜4.5, 7.9.13
．． 24, 30.33, 34.42.44.49.50.
51.54.56.5B, 60, 83.64.6B, 6
8, 71.74.76.79, 82, 83.85.86
．． 88.90.91.93.98,99,100.10
4. ．． 114,116,118.119゜122.12
4,126,135.140,141.149.160
．． 162.163.164.165.179.180.
182.183.186, 192. 198. 19
9. 202. 204°210, 21.1. 21
5. 216. 218. 224; C, 1, Disbirds Orange 1.3, 5°7, l'1.13, 17, 2
0.21.25.29.30.31, 32, 33, 37
．． 38.42.43.44.45.47% 48.49
, 50.53.54.55.56, 57.5B, 59.
61.66.71,73,76.78.80.89,9
0.91, 93, 96, 97. l19.127,130
, 139, 142. C.I.

Disverse Left l, 4.5, 7, 11.12.13
．． 15.17, 27.43.44.50.52.53.
54.55% 56.58.59.60.65.72,
73, 74.75.76.78.81.82.86.8
8.90, 91.92.93.98, 103, 105,
106.107,108,110. Ill, 113.1
17.118.121, 122, 126, 127.12
B, 131,132,134,135°137.143
, 145, 146, 151.152.153.154.
157. 159. 164°167, 169.
177, 179. 181.183, 184, 1J3
5, 188. 189. 190°191, 192.
200.201.202.2゜3, 205, 206,
207, 210. 221.224, 225. 227
, 229, 239.240.257. 258.277
．． 278. 279°281.28g, 296.303
．． 310.311, 312.320. 324, 328
:C,I.

Disbirds Violet l, 4.8.23, 26.2
7.28.31.33.35.36, 38.40.43
, 48.48.50.51, 52.58.57.59.
61.63.69.77, C,1, Disbirds Green 9; C-I.

Disperse Brown 1.2.4.9.13.19,:
C, 1, Disperse free release l, 3.7.9, 14.
16.19.20.26.27.35.43.44,5
4.55.56.58.60.62.64.70,72
．． 73.75.79.81.82.83.87.91.
93.94, 95. 9&, 102. 106.
108. 112, 113. 115. 118. 1
20. 122.125, 128. 130. 13
9. 141. 142, 143. 146. 148
．． 149. 153°154, 158.165. 1
67, 171. 173.174.176, 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°291, 293. 29
5, 29'7. 301, 315.330, 33320, 1. Disperse Black 1.3.10.24; Power 't't! Iff Nre, Do E-GL, Kayaseron Blue E-TB, Kayaseron Navy Blue-E-EX, Kayaseron Black E-EX, etc. It will be done.

In the present invention, as a medium for dispersing or dissolving the disperse dye as described above, any of the media used in conventional general dyeing and the medium used in conventional inkjet recording inks can be used. For example, water and/or or water-soluble organic solvents are preferred; examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Carbon 11-4 alkyl alcohols such as 5ec-butyl alcohol, tert-butyl alcohol, and isobutyl alcohol; Amides such as dimethylformamide and dimethylacetamide; Ketones or keto alcohols such as 7-setone and diacetone alcohol; tetrahydrofuran, dioxane, etc. Ethers: polyalkylene glycols such as polyethylene glycol and polypropylene glycol: ethylene glycol, propylene glycol, butylene gelylcol, triethylene glycol,
1.2.6-hexandriol, thiodiglycol,
Alkylene glycols in which the fullkylene group contains 2 to 6 carbon atoms, such as 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, 1,3-dimethyl-2-imidazolidinone, and the like.

The above-mentioned media can be used alone or as a mixture, but
The most preferred medium composition is 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.
The amount is -15%.

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

Dispersants or surfactants that may be added as necessary include fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, sialyl sulfosuccinates, furkyl phosphate ester salts, 7-ionic dispersant or surfactant such as naphthalene sulfonic acid formalin condensate, polyoxyethylene furkyl sulfate salt: polyoxyethylene alkyl ether, polyoxyethylene furkylphenyl ether, polyoxyethylene fatty acid ester.

Nonionic dispersants or surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and diethylene oxypropylene 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 preferred, and using these viscosity modifiers,
Alternatively, the word spacing of the ink composition of the present invention may be reduced to 2 without using it.
The temperature is 50 cps or less, preferably 1 to 10 cps at 5°C.

In addition, in order to formulate ink used in inkjet recording methods that charge the ink, lithium chloride, to! A resistivity adjuster such as ammonium tetrachloride or inorganic salts of 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, penetrating agents, antifungal agents, pHTA regulators, etc. can be added as appropriate.

The ink composition for inkjet recording of the present invention is prepared by mixing the above-mentioned essential components and optional components, and grinding the composition by conventionally known grinding means 1, such as a ball mill.

It is generally obtained by mixing and grinding using a sand mill, speed line mill, etc. 1 The particle size of the disperse dye is usually 30 pm or less, preferably 204 m or less. 0 If the particle size is too large, the nozzle during inkjet recording Problems such as clogging may occur, and problems may occur with level dyeing properties in the subsequent dyeing process. Furthermore, when a medium that dissolves the disperse dye is selected as the medium, the ink composition of the present invention can be obtained by mere dissolving action such as heating.

As described above, the inkjet recording ink composition of the present invention can be obtained.9 What is particularly important in the present invention is that the ink composition for inkjet recording of the present invention is obtained by blending the above-mentioned essential components and optional components during or after the grinding treatment. The surface tension of the ink composition is approximately 35
It is to adjust to a range of ~60 dynelcm,
Ink composition as above! ! The objects of the present invention are primarily achieved by having a surface tension within this range. m of such surface tension! 1 can be easily achieved by those skilled in the art by selecting a disperse dye, selecting and combining a medium, and adding various additives.

In the inkjet recording ink composition of the present invention,
If the surface tension is less than 35 dyne/cm,
When applied to a recording material, for example, a woven fabric mainly made of polyester, using the inkjet recording device 2, the adhered ink composition causes excessive bleeding with the surface, making it difficult to form fine patterns, and the surface tension increases. It has been found that if the upper limit of the above range is exceeded, problems such as difficulty in obtaining a stable and uniform drop left during ejection occur. In addition, the above surface tension values are VISCONICEL
D (manufactured by Tokyo Keiki Co., Ltd.) at 25°C.

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 for polyester fibers, 7) II
! ! It is useful for printing polypropylene fibers, vinyl woven fabrics or non-woven fabrics, or blended woven fabrics or blended non-woven fabrics made of these synthetic gA fibers and other m-fibers such as cotton am. Any conventionally known woven fabric or non-Ia fabric can be used, but in addition, these Ja'Ia or non-woven fabrics may be pretreated for inkjet printing. Such pretreatment can be carried out by applying a water-soluble or water-dispersible polyester 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 synthetic fibers 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 representative methods include 1, for example, IE
EE Tramsactions and Indus
stry Applications Vol, J
A-13, No. 1 (February/March 1977 issue) and Nikkei Electronics No. 305 (December B, 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, which uses several layers of nozzles and nozzles. - A strong electric field is applied between the accelerating electrode placed in front of the nozzle, the ink is turned into particles 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. There are two methods: a recording method and a method that ejects ink particles in response to information signals without deflecting the ink particles.
All of these 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 nozzle diameter that is larger than conventional methods.

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, rather than a mechanical means such as a pump as in other methods. 2
This method applies an electrical signal to the Ezo element to cause mechanical displacement, thereby applying pressure to the ink and ejecting it from the nozzle.

Furthermore, 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.

Any of the various inkjet/ink recording methods described above can be used, and by adopting any of these methods, a
A pattern such as a letter or figure is formed on the surface of a non-woven fabric or a molded product using a colored ink composition, but the ink composition for inkjet recording of the present invention has a surface tension within a certain range as described above. Since it is controlled, the ejection stability of droplets from the nozzle is extremely excellent. Further, due to the presence of the texture of the woven fabric, etc., the ink composition does not bleed excessively and adheres appropriately.

Therefore, a clear and fine pattern can be formed through a subsequent dyeing process using heat treatment. On the other hand, when conventional ink compositions for inkjet recording are used, the dots may not adhere to the desired positions accurately, or the dots of the adhered ink composition may quickly move along the weave of the fabric. It was difficult to form fine patterns on the woven fabric due to bleeding.

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, the 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 la, etc., such as by heating to a temperature of 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 images 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 plates as in the prior art. 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 such as polyester films and sheets. Inkjet recording uses ink made from 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,!, Disperse Blue 187) 5 parts Anionic surfactant (dispersant) 4 parts (Demol N manufactured by Kao Soap ■) Ethylene glycol 15 parts Diethylene glycol 13 parts Water
65 parts After dispersing all of the above components in an alumina ball mill for about 36 hours, the pH was adjusted to 8.3 with sodium hydroxide, and further dispersion was carried out for 3 hours in an alumina ball mill. Coarse particles with a particle size of 10 gm or more were removed using a filter FF-1000 (manufactured by Sumitomo Electric Co., Ltd.) to obtain an aqueous ink (A) of the present invention.

Example 2 Disperse dye (C, L Disbirds Orange 55) 3 parts Acidic dye (C, 1, Disbirds Yellow 43) 1 part Anionic surfactant 0.5 part C Nitsukol 0TP-Zoos, Nikko Chemicals M) Anionic surfactant 1.5 parts (Thymol C1 manufactured by Kao Soap) Nonionic surfactant 0.2 parts (Emuldan 911 manufactured by Kao Soap ■) ISO-propyl alcohol 0.5 parts Propylene glycol 15 parts Polyethylene glycol 5 parts water
75 parts After dispersing all of the above ingredients in an alumina ball mill for about 40 hours, the pH 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 Jumiya Electric Co., Ltd. product.

Aqueous ink CB) of the present invention was obtained.

Example 3 Disperse dye (C, 1, Disbird's Red Ill) 7 parts Reactive dye (C, 1, Disbird's Red 80) 2 parts Nonionic surfactant 1.5 parts (Emulgen 707, manufactured by Kao Soapball Co., Ltd.) Nonion System surfactant 2.0 parts (Rheodor TW-P12G, manufactured by Kao Soap ■) Ethyl calpitol 20 parts water
7 Part o From all the above components, Example 2 and rF! Example 5 A water-based ink (C) of the present invention was obtained by the same method as Example 1.

Example 4 3 parts of disperse dye (C, 1, Disperse Blue 214) Fractional dye CC, 1, Disperse Blue 137) 3
Part anionic surfactant 5.5 parts (Ionet D-2. manufactured by Sanyo Chemical Industries, Ltd.) Ethylene glycol
25 parts glycerin
5 parts 1,3-dimethylimidazolidinone 5 parts water

One aqueous ink (D) of the present invention was obtained from 60 parts of each of the above components in the same manner as in the example.

Comparative Example 1 Disperse dye (C, 1, Disbird's Red 55) 5 parts Anionic distributing agent 2 parts (Demol N, manufactured by Kao Soap ■) Fluorine surfactant 0.01 part (Florado FC-431, Jujutsu 3M) ) Ethylene glycol 15 parts Diethylene golicol 13 parts Water
65 parts A comparative aqueous ink (E) was obtained from all the above components in the same manner as in Example 1.

Comparative Example 2 Disperse dye (C, 1, Disbirds Red 239) 0.4
Partially dispersed dye (C, r, Disbirds Red 24o) 0.2
Part anionic surfactant (dispersion #) 0.05 parts (Calibon B, manufactured by Sanyo Chemical Co., Ltd. vIJ) Tetraethylene glycol 1 part N-methyl-2-pyrrolidone
10 parts water
75 parts A comparative aqueous ink (F) was obtained in the same manner as in Example 1.

Each water-based ink (A
-F) properties are shown in Table 81 below.

Usage Examples Each water-based ink (A-
The ink of F) was prepared by the method described in Japanese Patent Application Laid-Open No. 54-51837. After printing on cloth using an inkjet printer that uses thermal energy,
The print was placed in an oven at 215° C. for 3 minutes for fixing, and then washed with a neutral detergent to obtain a print. Second result
Shown in the table.

Usage example 2 Inks of Examples 1-48 and Comparative Example 1.2.

Polyester film (manufactured by Toshi@, Lumirror Q-80)
Table 3 shows the results of evaluating the printed matter after leaving it in an oven at 130° C. for 1 hour to fix it.

Illusion 1j doctor - IJLJI Arashi''shi 1 4, zf! , Hf complete (4,6f gf 4(6f
-d cs 411
55 42 ko8 3
1 G2J 8
．． 3 7.5 5.1 $1.2
11.2 '4.0*-book t 81
45 83 711 85 381 gtt
6 413 12 11 books I I
The results of analysis using CPα limited coupled plasma emission spectroscopy 1 & button are shown.

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

W Koko 3 More per bottle 2 IL potato heather -1 --- Mami M M U ligament and Mayuzumi ink (A) Polyester 100k
(Georgette) OO ink (B) Polyester 611 ms! (Broad Tsu o.

Ink (C) Polyester 65 Elephant & 83R (Broad Tsu o O Ink (D) Polyester + OOX (Tack) 00JLLJ Ink (E), t?Reester room (Di, -
Zewoto) × × Ink (F) Polyester Lo Kui (Ji, -Z) 0 × Book! Visually judge the sharpness of the fine lines (width) on the print. LO: Good ×: Bad book 2 Print 30 cm of dots in a row at approximately 1-interval intervals, and visually judge the dispersion of the dots. 90: Good man ×: Bad 1 vertical ≦ L leak - ILJ! tJLJ ink (A)
Ink CD) Ink (E) Ink CF) Production-1111--mi o o
x.

LzlJ jig 2 pieces soil Q Q
X XO: Good ×: Bad Patent applicant Gyu Yanon Aji Shiki Company 1? /y8. :

Claims (1)

[Claims] (1) Consisting of a disperse dye and a medium, the surface tension of which is 3
An inkjet recording ink composition characterized in that the ink composition has an inkjet recording density of 5 to 60 dyne/cm.