JP3004791B2 - Inkjet printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing and printing a fabric by an ink jet method.

[0002]

2. Description of the Related Art At present, the mainstream of printing is screen printing,
Roller printing. These methods are unsuitable for high-mix low-volume production, and it is difficult to respond quickly to fashion trends. Recently, it has been demanded to establish a plateless electronic printing system.

[0003] In response to this demand, many printing methods using ink jet recording have been proposed, and expectations from various fields have been increasing.

[0004] The problems of ink-jet printing include:
(1) giving a sufficient density for color development; (2) high dyeing rate of the dye on the fabric; easy wastewater treatment after the washing step; (3) irregularity due to color mixing between different colors on the fabric. (4) The range of color reproduction is wide, (5) The process is simpler, and the like.

In order to satisfy these problems, conventionally, various additives have been mainly added to inks,
Various measures have been taken, such as controlling the amount of ink to be applied or applying a treatment to the fabric in advance. However, these methods alone could not solve the problems (3) and (4).

Although it is not an example of a cloth, as a method for solving the problem (3), there is a method of operating the ink ejection order in a specific lightness order as disclosed in Japanese Patent Application Laid-Open No. 62-161541. cases, it in the method of operating a <br/> group Dzu Ku driving sequence in the initial brightness with the ink to solve for the change in brightness after the difference and dyeing of color yield of the dye (3) is not It is.

[0007] In textile printing, there is a washing step as a final step for removing dyes that have not been dyed on the cloth, and handling is performed differently from the case of recording on ordinary paper or the like without performing the conventional washing step. There is a need.

As described above, in the prior art, means for satisfying individual performances to some extent can be found, but it is possible to simultaneously satisfy these performances and obtain the highest quality image that solves a series of such problems. At present, the ink jet printing method has not been known so far.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a conventional ink jet printing as described above, that is, a printing which satisfies the problem of obtaining a clear, high-density, high-definition dyed product. It is to provide a method.

Further, in the conventional method using a paste such as screen printing or roller printing, a large amount of dye is used because the dyeing rate of the dye is low. An object of the present invention is to provide a printing method having a high dyeing rate in order to solve the problem of causing contamination.

The above objects of the present invention are attained by the following present invention.

[0012]

Means for Solving the Problems In the ink jet printing method, the present inventors have studied to simultaneously satisfy the various required performances as described above, and as a result, have controlled the amount of the dye applied to a unit area of the fabric. In addition, the order of the inks is set such that the brightness of the image after the dyeing and washing steps when the same amount of each ink is applied alone is set in the lower order, so that the thickness of the fabric and the structure of the fiber constituting the fabric are reduced. Regardless of slight differences (fiber length, thickness, number from average, etc.), it was found that leveling property and dyeing rate can be improved, and that color development characteristics such as bleeding in a mixed color area between different colors can be remarkably improved. did. This means that the image composed of dots or dots provided on the fabric has a low brightness, that is, a high contrast with the fabric, such as black, and a color having a high human visual sensitivity, and a high brightness, That is, since a structure having a low contrast with a fabric, such as yellow, is framed with a color having a low visual sensitivity, even if a color having a high brightness becomes thick, it is hardly perceived by human eyes. In ink-jet printing, unlike the case of printing on paper, it is necessary to perform dyeing of the applied dye, and in this dyeing process, a difference in coloring due to a difference in dye dyeing rate occurs. Must be in the order of lightness after coloring. In addition, image deterioration may be caused by occurrence of bleeding or the like in the dyeing process. However, by controlling the amount of dye applied as described above, deterioration of an image such as bleeding can be hardly felt. .

Accordingly, the present invention for achieving the above object provides a yellow, magenta, cyan and black color filter.
Ink-jet printing method using only color dye ink
There are at least two colors selected from (a) above four color inks
A step of forming a mixed color portion of at least two colors of ink on the fabric by sequentially depositing small ink droplets on the fabric; and (b) dyeing the fabric by heat-treating the fabric formed with the mixed color portion. step, and (c) removing the dye non-dyed by washing the dyeing is allowed fabric from the fabric, have, 0.025~1mg / cm a total adhesion amount of each dye color mixing unit ^{In addition} to setting the ink droplets in the mixed color portion to ² , the same order of the single color ink droplets is used to carry out each of the above-described steps (a) to (c). It is characterized in that the order of the brightness of the wearing parts is low .

Hereinafter, the present invention will be described in detail.

[0015]

Preferred examples of the material constituting the fabric used in the present invention include natural fibers such as cotton, silk, nylon, and polyester, and synthetic fibers.
Natural fibers such as silk are preferred. The fibers can be used in any form such as a woven fabric, a knitted fabric, and a nonwoven fabric. In general, the physical properties of the fibers are preferably such that the yarns and fibers constituting the fabric have a longer length, a smaller thickness, and a larger number.

For example, in the case of a fabric mainly composed of cellulose fibers, the average fiber length is 25 to 50 mm, the average fiber thickness is 0.6 to 2.2 d, and the number is 70 to 150 / cm.
In the case where the cloth composed of the above fibers is a cloth mainly containing silk fibers, a cloth having an average yarn thickness of 14 to 147d and an average fiber thickness of 2.5 to 3.5d is preferable.

The moisture content of the fabric is preferably slightly higher than the official moisture content of the fibers constituting the fabric. The water content is preferably 5 to 100% higher than the official water content.

The printing ink used in the present invention comprises a dye, water, an organic solvent, an additive and the like, and these inks having different lightness after coloring are appropriately used in the present invention.

The dye is preferably a dye, and any dye may be used as long as it can be dyed on a fabric. Acid dyes, direct dyes, cationic dyes, reactive dyes, disperse dyes, vat dyes and the like can be used. One or more of these dyes are contained in the ink and can be used in combination with dyes having different hues. The amount of the dye is generally 2 to 30% by weight based on the total amount of the ink. , Preferably 3 to 25% by weight,
More preferably, it is in the range of 4 to 20% by weight.

The preferred content of water as the main component of the ink is 10 to 93% by weight, preferably 25 to 87% by weight, more preferably 30 to 80% by weight based on the total amount of the ink.
% By weight.

As for the organic solvent, for example, acetone,
Ketone or keto alcohols such as diacetone alcohol; ethers such as tetrahydrofuran and dioxane;
Oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, hexylene glycol Alkylene glycols wherein the alkylene group contains 2 to 6 carbon atoms;
Triols such as 2,6-hexanetriol; thiodiglycol; glycerin; lower polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether Alkyl ethers; lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone and the like.

The content of the above-mentioned organic solvent is generally from 3 to 60% by weight, preferably from 5 to 60% by weight based on the total weight of the ink.
It is in the range of 50%.

When the above-mentioned media are used in combination, they can be used alone or as a mixture. The most preferred liquid medium composition is one in which the solvent contains at least one polyhydric alcohol. Among them, thiodiglycol alone or a mixture of diethylene glycol and thiodiglycol is particularly preferable.

The content of other substances is 0.001.
By containing 0.15% by weight of chloride ion and / or sulfate ion, the coloring properties such as leveling property and dyeing rate can be further improved, which is preferable.

The main components of the ink of the present invention are as described above, and other various dispersants, surfactants, viscosity modifiers, surface tension modifiers, fluorescent brighteners, etc. may be added as necessary. Can be.

For example, viscosity modifiers such as polyvinyl alcohol, celluloses and water-soluble resins; various surfactants of cationic or nonionic type; surface tension modifiers such as diethanolamine and triethanolamine;
H regulators, fungicides and the like can be mentioned.

As the ink jet recording system for applying the above ink on the fabric, a known system such as a bubble jet can be used.

In the present invention, a plurality of printing ink droplets are sequentially deposited on the cloth by an ink-jet method to form a color mixture portion of at least two colors of ink. In this case, the sum of the adhesion amounts of the respective dyes in the mixed color portion is
0.025 to 1 mg / cm ² , preferably 0.04 to 1 mg / cm ²
0.7 mg / cm ² , more preferably 0.05 to 0.5
mg / cm ² . This value can be obtained by actually measuring the ink ejection amount and the dye concentration in the ink. The amount of dye attached is 0.025 mg / cm ²
If it is less than 10, it is difficult to form a high-density color and bleeding or the like is not conspicuous, so that the effect of the present invention is not clear. 1mg / cm
^When it exceeds ² , no remarkable effect of improving the dyeing rate is observed.

It is necessary to set the printing ink deposition order as follows. In other words, an ink droplet of the same amount of a single color is deposited on the cloth, and after performing a heat treatment and a washing step, the order of the inks having a low lightness at the dyed portion of each ink droplet is set to be clear and sharp. Irregular bleeding in the mixed color area is not conspicuous, and good ink jet printing with a wide color reproduction range can be performed.

The method of measuring the lightness may be performed by a general colorimeter, but the present inventors have used a high-speed spectrophotometer CA-3.
5 (manufactured by Murakami Color Research Laboratory), and the L ^* value when the image of the final dyed part is represented by the perceived chromaticity index defined in the CIE1976 (L ^* , a ^* , b ^* ) space. The brightness value was used.

The fabric having the mixed color portion formed as described above is then subjected to a heat treatment to dye a dye on the fabric. As the heat treatment method, a conventionally known method may be used, for example, a steaming method, an HT steaming method, a thermofix method, or when not using an alkali-treated cloth when an alkali agent is required for fixing, Examples thereof include an alkali pad steam method, an alkali blotch steam method, and an alkali shock method.

Further, in the present invention, the cloth subjected to the above treatment is washed, and undyed dye is removed by a conventionally known method.

[0033]

The following Examples and Comparative Examples the elevation Gaité, the present invention will be described more specifically. In the description, parts and% are based on weight. I. Ink preparation Reactive dye inks and acid dye inks of four colors each were prepared. 1. Reactive dye ink Reactive dye 4-20 parts Thiodiglycol 24 parts Diethylene glycol 11 parts Potassium chloride 0.004 parts Sodium sulfate 0.002 parts Sodium metasilicate 0.001 part Iron chloride 0.0005 parts Water 45-61 parts Reaction used The dyes are as follows. -Yellow ink C.I. I. Reactive Yellow 95 ・ Magenta Ink C.I. I. Reactive Red 226 Cyan Ink C.I. I. Reactive Blue 15 Black ink C.I. I. Reactive Black 39 Each of the above components was mixed, the mixture was adjusted to pH 8.4 with sodium hydroxide, stirred for 2 hours, and then filtered through a Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.). An aqueous ink was obtained. 2. Acid dye ink Acid dye 4-20 parts Thiodiglycol 23 parts Triethylene glycol monomethyl ether 6 parts Potassium chloride 0.05 parts Sodium metasilicate 0.001 part Iron chloride 0.0005 parts Zinc chloride 0.0003 parts Water 51-67 The dyes used are as follows. -Yellow ink C.I. I. Acid Yellow 110-Magenta Ink C.I. I. Acid Red 266 Cyan Ink C.I. I. Acid Blue 90-Black Ink C.I. I. Acid Black 26 Each of the above components is mixed, and the mixed solution is adjusted to pH 4.
After stirring for 2 hours, the mixture was filtered through a Fluoropore Filter FP-100 (trade name, manufactured by Sumitomo Electric Industries, Ltd.) to obtain an aqueous ink. II. Ink jet dyeing apparatus Color bubble jet copier PIXEL PRO (trade name, manufactured by Canon Inc.) was modified so as to be able to increase and decrease the appropriate amount of the discharged liquid, and used.

1. 1. Ink jet method: On-demand type 2. Head voltage: 20 to 40V 3. Head temperature: 20-60 ° C 4. Drive pulse width: 3 to 20 μs 5. Driving frequency: 0.5 to 5 kHz 6. Distance between nozzle and fabric: 1 mm Recording density: 16 dots / mm x 16 dots / mm
(400 dots / inch x 400 dots / inch) III. Fabric The following two fabrics were used, and the water content was adjusted by changing the drawing ratio after adding water.

A: Plain ground cloth (100% Egyptian cotton) b: With 8 hame double coats (100% silk) Using the above four reactive dye inks and cloth a, the amount of dye attached as shown in Table 1. The printing was performed by the above-described ink jet apparatus while changing the moisture content of the cloth and the order of ink ejection. The amount of dye attached can be changed by changing the dye concentration in each ink within the range of 4 to 20% by weight, and further by controlling the driving conditions (head voltage, temperature, driving pulse width, frequency) of the ink jet apparatus to reduce the amount of ejected droplets. It was changed within 20 to 50 pl, and adjusted by performing multiple punching as needed. The water content of the fabric was adjusted by changing the drawing ratio after adding water to the fabric. The printed matter is then 100
Steaming was performed at 5 ° C. for 5 minutes in an alkaline atmosphere, followed by washing and drying. The resulting printed matter was evaluated for clarity and bleeding property, and the average value of the optical density (OD) of the solid color solid portion was measured to be used as a criterion for the dyeing rate. As a result, when the total amount of dye adhered was 0.025 to 1 mg / cm ² and the moisture percentage of the fabric was 5 to 100% higher than the official moisture percentage, clearness and bleeding were good. When the dyeing rate was determined by relative evaluation of the OD value, it was found that when the official moisture regain of the fabric was increased by 5 to 100%, the dyeing rate was lowered when the amount of dye attached was more than 1 mg / cm ^2. . Furthermore, when the ink was ejected in the order of lightness after dyeing, the bleeding property of the mixed color portion was extremely good, and a very clear image was obtained.

[0036]

[Table 1] * 1 The amount of dye attached was determined as follows.

The amount of ejected droplets × the number of dots of 1 cm ² × the concentration of the dye in the ink × the number of multiple ejections × 2 The water content was calculated by the following equation: water content (%) = (W−W ′) / W ′ × 100 W = weight of wet fabric, W ′ = weight of absolutely dry fabric * 3 The order of lightness after dyeing when each of the used inks is applied singly to an equal weight area is black <magenta <
Cyan <yellow.

Driving order A = 1 black, 2 magenta, 3 cyan, 4 yellow B = 1 black, 2 yellow, 3 cyan, 4 magenta C = 1 yellow, 2 cyan, 3 magenta, 4 black * 4 Observed with the naked eye Judgment was made based on the sharpness of the pattern at the time.

：: good Δ: slightly poor X: poor * 5 Observed with the naked eye.

：: good Δ: slightly poor X: poor Using the above-described four colors of acid dye ink and fabric b, the amount of dye attached, moisture content of fabric and ink were used as described in Table 2 in the same manner as in Experimental Example 1. Were printed by the above-mentioned ink jet apparatus by changing the order of the driving. Thereafter, steaming was performed at 100 ° C. for 30 minutes, followed by washing and drying. The resulting printed matter was evaluated for clarity and bleeding property, and the average value of the optical density (OD) was measured and used as a criterion for the dyeing rate. As a result, almost the same results as in Experimental Example 1 were obtained.

[0041]

[Table 2] * 1 The amount of dye attached was determined as follows.

The amount of ejected droplets × the number of dots of 1 cm ² × the concentration of the dye in the ink × the number of multiple shots * 2 The water content was calculated by the following equation: water content (%) = (W−W ′) / W ′ × 100 W = Weight of wet fabric, W '= Weight of absolutely dry fabric * 3 The order of lightness after dyeing when each of the used inks is attached to an equal weight and an equal area is black <magenta <cyan <Yellow.

Driving order A = 1 black, 2 magenta, 3 cyan, 4 yellow B = 1 black, 2 yellow, 3 cyan, 4 magenta C = 1 yellow, 2 cyan, 3 magenta, 4 black * 4 Observed with the naked eye Judgment was made based on the sharpness of the pattern at the time.

：: good Δ: slightly poor X: poor * 5 Observed with the naked eye.

：: good Δ: slightly poor X: poor

[0046]

As described above, according to the ink jet printing method of the present invention, it is possible to obtain a clear, high-density, high-definition dyeing product without bleeding.

Further, according to the present invention, in ink-jet printing, the dyeing rate can be remarkably improved, and the problem of environmental pollution due to wastewater can be dealt with.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) D06P 5/00 111

Claims (1)

(57) [Claims] 1. The method of claim 1 wherein the color is yellow, magenta, cyan and black.
Ink-jet printing using only four color dye inks
A dyeing method, at least two colors selected from (a) above four color inks
A step of forming a mixed color portion of at least two colors of ink on the fabric by sequentially depositing small ink droplets on the fabric; and (b) dyeing the fabric by heat-treating the fabric formed with the mixed color portion. step, and (c) removing the dye non-dyed by washing the dyeing is allowed fabric from the fabric, have, 0.025～1Mg the total adhesion amount of each dye color mixing unit /
cm ^2, and the order of dropping of the ink droplets in the mixed color portion is determined by using the same amount of a single color ink droplet as in the above (a).
An ink-jet printing method, characterized in that the order of the lightness of the dyed portion in a single color of the fabric after performing each of the steps (c) to (c) is low.