JPH11335982A - Printing liquid and dyeing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing liquid capable of simultaneously providing both a multicolored splashed pattern and resist dyeing by mixing a specific heat sensitive polyacrylamide and a fluorine-based water- and oil-repellent agent. SOLUTION: This printing liquid is obtained by blending 4-8 pts.wt. heat- sensitive polyacrylamide derivative capable of performing phase-transition to a hydrophobic state at a high temperature higher than the transition temperature and to a hydrophilic state at a low temperature lower than the transition temperature in the coexistent state with water, e.g. poly-N-isopropylacrylamide, with 15-25 pts.wt. fluorine-based water- and oil-repellent agent, 0.5-2 pts.wt. dye, 0.5-2 pts.wt. crosslinking agent, 0.5-2 pts.wt. reagent and 61-79.5 pts.wt. water. A silk yarn such as a hand-spun yarn is partially printed by using the printing liquid and dried by heating. The dried silk yarn is subjected to ground yarn dyeing of the whole yarns, and the dyed product is further subjected to steaming treatment and washing treatment to dye the yarn in the dyeing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water- and oil-repellent solution for a solution of a heat-sensitive polyacrylamide derivative which undergoes a reversible hydrophilic (low temperature) -hydrophobic (high temperature) phase transition depending on temperature in the presence of water. In addition, a printing solution in which dyes and auxiliaries are dispersed, and a method for dyeing silk yarn such as hand-spun and hand-pulled yarn in a Kasuri form using this printing solution, particularly require the squeezing work conventionally required. The present invention relates to a printing liquid capable of performing Kasuri-like dyeing by one-time partial printing and ground color dyeing, and a dyeing method using the same.

[0002]

2. Description of the Related Art Dyeing and printing are known as dyeing methods for yarn and yarn bundles. In addition, there is a so-called tataki-dyeing and rub-in printing, which is contrasted with a plain dyeing, a method using both of them, or a patterning method, which is a so-called kasuri-dyeing in a so-called kakujaku production area. While solid color dyeing is a single color,
Kasuri dyeing is most practically used in the production area of Kijyaku as a method of dyeing in multiple colors.

[0003] In the bat dyeing, a yarn bundle is tightly tied to a pattern pattern portion with cotton yarn or rubber, and a yarn bundle is tied to the tip of a rod to dye other portions called ground, and dye is contained. Beat on a plate and dye. For example, an example of the process is shown in FIG. First, the yarn bundle is dyed with a yellow dye, and the portion of the yarn bundle where the yellow color is to be left is tightly wrapped with cotton yarn or rubber. Next, the yarn bundle is decolorized. Next, the yarn bundle is dyed with a red dye, and the portion of the yarn bundle where the red color is to be left is tightly wrapped with cotton yarn or rubber. Next, the yarn bundle is decolorized. In the same manner, the color-dyeing-closing-decoloring is sequentially repeated for the color to be partially dyed such as blue, green, and brown. Finally, the yarn bundle is soaked and dyed in a dark blue dye, which is the ground color, washed with water and dried to complete the Kasuri dyeing.

[0004]

As described above, in the Kasuri dyeing, if the number of partial colors of the Kasuri which becomes a design pattern increases, the work process of dyeing, bundling, and decoloring is repeated by the number of colors, and finally the tataki dyeing is performed. The part other than the part enclosed by is stained. Since this work is a division of labor between a machine shop and a dyeing shop, it naturally goes back and forth between them each time, and the labor and time required other than the working time are large. Furthermore, since dyeing-closing-decoloring is repeated, even if the work is carried out with great care and care, the Kasuri thread is easily damaged by fluffing and splitting.

[0005] The strength of the yarn bundle varies from person to person, and even the same person has different stiffness due to health conditions during work, expansion and contraction of the yarn due to temperature and humidity, and the like. If the squeezing strength is different, the dyeing cannot be performed uniformly. Therefore, it is necessary to perform the dyeing while adjusting the number of times of tapping the yarn bundle according to the individual squeezing condition. Therefore, dyeing of the kasuri was extremely troublesome and difficult.

[0006] The tying work requires experience, intuition and knack, and a technician who can tie in about 2,000 places a day takes one month to tie a piece of kasuri, and three to six months to become a luxury product. Cost. In addition, even if it is an expert, it is extremely difficult to wrap it evenly. Since the inside of the constricted portion is not visible, it is necessary to untie and loosen the constricting thread in the course of dyeing while dyeing. Even with such careful work,
There are many cases of failure, and the person who dyes and dyes ends up in vain, troubles the responsibility and reimbursement problems, and the economic loss is large.

[0007] In addition, dyes to be applied to bat dyeing,
The selection of auxiliaries is also an important factor, and is selected according to the hue and fineness of the kasuri from among those that are limited in consideration of the affinity and penetrability to the yarn, dyeing speed, leveling properties, and fastness. And use. Therefore, it cannot be said that all the desired hues of the kasuri and the ground color are satisfied, and it is often impossible to realize a well-designed design.

[0008] The rub-in printing is a method of applying a dye solution to a stainless steel spatula, dyeing a thread-bundle-shaped pattern pattern in multiple colors, and then printing a large-area ground portion in a single color. In general, a method is used in which a portion to be ground is previously dyed in a solid color, and a portion to be a kasuri is colored with a spatula by applying a dye solution to a multicolor. It is difficult to uniformly dye a wide area by rub printing, and the border between the ground and the kasuri, which is said to be a painting, tends to blur and the pattern tends to be unclear. Therefore, the selection of a dye and an auxiliary agent to be applied is also an important factor as in the case of the bamboo dyeing. In addition, the suitability of pre-gluing the yarn greatly affects work efficiency and workmanship.

[0009] In some cases, a method for producing a kasuri using both rub-in printing and tataki-dyeing has been performed. However, it is natural to take into account the current status and issues of the above-mentioned rub-in printing and tataki-dyeing, so the difficulty in terms of technology and time is doubled. Are rare.

[0010] In the pattern printing, the yarn is glued in advance,
Spread the yarn to the specified length and width on the printing stand, print the printing paste with a squeegee on the pattern paper with the pattern cut out, changing the pattern for each hue, drying, steaming, and soaping And wash with water and dry. As described above, the pattern paper is produced for each hue, and since each pattern paper is not allowed to deviate in size, specialized technology is required, and the cost and labor required for the production are large.

In addition, since the production of a pattern requires considerable equipment and cost, the cost of the pattern production is not paid unless a large number of lots are processed in one pattern. It is becoming a trend. Of course, in the printing process, the selection of dyes and auxiliaries to be applied is also an important factor, and skilled skills and techniques are required, and a large workplace is required. Due to the various problems described above, there is a strong demand for solving these problems in the Kasuri production area.

The present invention has been made in view of the above-mentioned problems of the conventional kasuri dyeing, and has as its object to enable coloring and anti-dyeing to be simultaneously applied to silk threads of various shapes. This allows
Instead of the so-called tataki-dyeing method, stencil printing method, or a combination of the two methods, the work labor in the Kasuri manufacturing process is reduced, and both coloring and anti-dyeing are performed simultaneously. Can be checked at any time.

[0013]

Means for Solving the Problems The present inventors utilize the characteristics of a heat-sensitive polyacrylamide derivative in combination with the characteristics of a water- and oil-repellent agent, and use a viscous aqueous solution containing this as a main component. Then, various yarns and yarn bundles were dyed with kasuri as a design pattern, and at the same time, a means for preventing dyeing from being contaminated by others was examined. In particular, a study was made of a means that does not require the consolidation work conventionally required, and that can perform Kasuri-like dyeing by one-time partial printing and ground color printing. The present invention has been made as a result of this study.

The printing liquid according to the present invention is a solution containing a heat-sensitive polyacrylamide derivative which undergoes a phase transition to be hydrophobic at a high temperature above the transition temperature in a state coexisting with water and hydrophilic at a low temperature below the transition temperature. And a water- and oil-repellent agent, which becomes water-repellent when diluted and dispersed in water and subjected to a heat treatment, and a dye and an auxiliary agent. A preferred composition of the printing liquid is 4 to 8 parts by weight of a phase-transferring heat-sensitive polyacrylamide derivative, 15 to 25 parts by weight of a water / oil repellent, 0.5 to 2 parts by weight of a dye, and a crosslinking agent. Is 0.5 ~
2 parts by weight and 0.5 to 2 parts by weight of a reagent, which are dissolved or dispersed in 61 to 79.5 parts by weight of water.

Further, the dyeing method according to the present invention comprises the steps of using the above-described printing solution, printing the printing solution on a yarn, heating and drying the printed printing solution, and drying the printing solution on the yarn. The method is characterized in that the yarn is dyed through a process of dip-dyeing the ground color in a state where the yarn is adhered, and a process of subsequently heating the yarn in a wet manner and washing with water.

As described above, a heat-sensitive polyacrylamide derivative which undergoes a reversible phase transition to hydrophobic at a high temperature and hydrophilic at a low temperature in the presence of water, a water / oil repellent, a dye,
When a yarn or a yarn bundle is partially printed using a printing liquid containing an auxiliary agent as a component, the colored portion of the kasuri that becomes a pattern is colored by the dye contained in the printing liquid. Further, when the yarn or yarn bundle to which the printing liquid is adhered is heated and dried, the heat-sensitive polyacrylamide-based derivative and the water- and oil-repellent agent settle on the colored portion of the yarn or yarn bundle, and prevent the dyeing of the background color later. It will exhibit the action of dyeing. Therefore, when the dye which becomes the ground color is subsequently dyed on the yarn or yarn bundle, this dye does not adhere to the previously colored portion. Thereafter, the yarn or yarn bundle is heated in a wet manner and washed with water to remove the heat-sensitive polyacrylamide-based derivative and the water / oil repellent, and the yarn or yarn bundle contains only a partially colored dye and a ground color dye. Remains. This makes it possible to perform a Kasuri-shaped dyeing.

[0017] The partially colored portion can be dyed at a plurality of portions by using a printing liquid containing a dye of a different color, and subsequent drying alone does not require a consolidation step. For this reason, it is possible to easily perform the Kasuri-shaped dyeing only by performing the partial coloring using the printing liquid according to the present invention and the ground color using the dye for the ground color, and the accompanying steps.

[0018]

Next, embodiments of the present invention will be described specifically and in detail. The heat-sensitive polyacrylamide-based derivative, which is one component of the dye solution according to the present invention, is colorless and transparent, and the water and oil repellent is milky white. For this reason, by adding a dye together with these, a printing solution adjusted to an arbitrary hue is obtained, and the appearance when printing a yarn or a bundle of yarns with this printing solution and the printed Kasuri portion do not change color. , Can be confirmed by visual feeling as it is. The water- and oil-repellent is preferably a fluorine-based one using an organic fluorine compound such as perfluoroalkyl ester of polyacrylic acid or chromium fluorocarboxylate.

A dye is dissolved in water or hot water in a solution of the heat-sensitive polyacrylamide-based derivative having hydrophilicity at low temperature and the fluorine-based water- and oil-repellent solution which is diluted and dispersed with water before heating, and cooled. After that, when the viscous printing liquid dispersed and dissolved together with the auxiliary agent is printed on the yarn or the yarn bundle, the auxiliary agent necessary for coloring and fixing the fiber and the dye is adsorbed on the fiber of the yarn. At the same time, when the viscous solution comprising the heat-sensitive polyacrylamide-based derivative and the fluorine-based water- and oil-repellent is dried, the heat-sensitive polyacrylamide-based derivative is solidified, the printed portion is formed into a film, and a thin layer is formed. In addition, since the aqueous solution of the heat-sensitive polyacrylamide derivative is a viscous liquid, it also acts as an adhesive for water and oil repellents, dyes, and other auxiliaries. Hold on. For this reason, the edge of the pattern is sharp and migration is prevented. Further, such properties of the printing liquid have an effective function of preventing the printed portion from falling off against friction and breakage during each operation after printing the yarn.

On the other hand, acetic acid added as an auxiliary promotes coloring and fixation of the dye on the yarn, and changes the transition temperature of a heat-sensitive polyacrylamide derivative such as poly-N-isopropylacrylamide from 31 ° C. to 26 ° C. Lower to 5 ° C. For this reason, when dyeing other than the partially printed part,
When dyeing a so-called ground color, dyeing can be performed from a low temperature. Therefore, when dyeing a large area portion, it effectively works in the subsequent background color dyeing step as a measure for preventing spotting. After drying the yarn or yarn bundle printed as a pattern in this way, when a heat treatment is performed for several minutes in a dryer, the fluorine-based water- and oil-repellent contained in the printed portion is converted into a heat-sensitive polyacrylamide-based derivative. , Or singly renders it hydrophobic and exhibits water repellency.

Here, when only the water and oil repellent is added to the printing liquid without adding the heat-sensitive polyacrylamide-based derivative,
It reduces the coloring and fixation of the dye, and is more water-repellent than necessary, so that it cannot be completely removed by soaping or washing with water for a short time. For this reason, after the ground color dyeing is performed, the water / oil repellent remains during the gluing operation in the weaving preparation process, which hinders the adhesion of the glue and hinders the subsequent work in the preparation process.

When only a heat-sensitive polyacrylamide-based derivative is added to a printing liquid without adding a water- and oil-repellent agent, the water-repellency is poor and dye and moisture can be prevented from penetrating from the surface of the printing portion. This makes it impossible to completely prevent intrusion of dye or moisture from the side parallel to the yarn bundle. For this reason,
At the time of ground color dyeing, the ground color dye becomes blurred in the partially dyed portion of the kasuri, and a clear picture is not obtained.

For these reasons, the use of a fluorine-based water- and oil-repellent together with a heat-sensitive polyacrylamide-based derivative provides hydrophobicity and water repellency for thermal stimulation, and hydrophobicity and water repellency in a low-temperature bath. May not be shown very much. In addition, after finishing various processes such as printing, heat treatment, dip dyeing, and steaming, the threads and yarn bundles are washed with water to remove the heat-sensitive polyacrylamide-based derivative and the fluorine-based water- and oil-repellent, which exhibited anti-dyeing action. can do.

More specifically, when a fluorine-based water- and oil-repellent, a dye, and an auxiliary agent are mixed and adjusted in the viscous liquid of the heat-sensitive polyacrylamide derivative, the fluorine-containing water-repellent oil-repellent agent is mixed in the viscous liquid of the heat-sensitive polyacrylamide derivative. Water and oil repellents, dyes and auxiliaries are dispersed. When the printing liquid thus obtained is printed on a yarn bundle, moisture, dye, and water / oil repellent diffuse and permeate into the fiber of the yarn. Of course, the dye and the water / oil repellent are also dispersed in the thermosensitive polyacrylamide-based viscous liquid attached to the yarn bundle, but the dye and the water / oil repellent have more particles than the viscous liquid. Due to its small size and low viscosity, it diffuses and penetrates inside the yarn bundle. On the other hand, the heat-sensitive polyacrylamide-based derivative having a high viscosity aggregates near the surface of the yarn bundle. Since the heat-sensitive polyacrylamide-based derivative is a pasty polymer, it forms a film when dried. Next, by heat-treating this film, the fluorine-based water / oil repellent develops water repellency inside and outside of the yarn bundle, and in the next ground color dyeing process, the dyeing liquid penetrates into the fibers of the printed portion. To prevent.
In short, in the ground color dyeing process, the heat-sensitive polyacrylamide-based derivative near the surface of the yarn bundle and the water / oil repellent inside the yarn bundle prevent the intrusion of the dyeing liquor.

Immediately after the background color is dyed, the yarn bundle is steamed. However, since the heat-sensitive polyacrylamide-based derivative has a hygroscopic property, it takes in moisture in steam and softens into a rubbery form.
It plays an important role in supplying water to the fibers of the yarn bundle. At this time, temperature and moisture are indispensable for the color development and fixation of the dye. If either one of them is insufficient, the dyeing cannot be performed. The water- and oil-repellent agent can prevent the intrusion and contamination of the dye from the outside, but does not supply the water necessary for coloring and fixing the dye in the printed portion as described above. Therefore,
The water- and oil-repellent agent alone sufficiently exerts the effect of dyeing prevention, but hinders coloring. Thus, the heat-sensitive polyacrylamide-based derivative and the water- and oil-repellent agent complement each other's functions, and can simultaneously perform coloring and anti-dyeing actions.

After the dyeing of the kasuri and the ground color portion is completed, the dyes and auxiliaries, heat-sensitive polyacrylamide-based derivatives and water- and oil-repellents, which are excessively adhered in the soaping and washing steps, are removed. When pinging, the water- and oil-repellent agent can be removed in a hot water bath with a surfactant added as a soaping agent, and when washing with water, the heat-sensitive polyacrylamide-based derivative can be removed. For this reason, there is no hindrance to gluing after dyeing and subsequent steps.

The preferred composition of the printing liquid is 4 to 8 parts by weight of a phase-transferring heat-sensitive polyacrylamide derivative, 15 to 25 parts by weight of a fluorine-based water / oil repellent, and 0.5 to 5 parts by weight of a dye.
2 parts by weight, 0.5 to 2 parts by weight of a crosslinking agent, and 0.1% of a reagent.
5 to 2 parts by weight, water is 61 to 79.5 parts by weight. Here, the thermosensitive polyacrylamide-based derivative is 20% by weight.
It is added before and after the aqueous solution.

If the amount of the heat-sensitive polyacrylamide derivative is less than 4 parts by weight, coloring with the dye and fixing of the dye are deteriorated. On the other hand, when the heat-sensitive polyacrylamide-based derivative exceeds 8 parts by weight, the ground color dye becomes blurred on the partially dyed portion of the kasuri when the ground color is dyed, and it is difficult to obtain a clear picture. If the fluorine-based water- and oil-repellent is less than 15 parts by weight, sufficient water repellency cannot be obtained, and when the ground color is dyed, the ground color dye bleeds into the partially dyed portion of the kasuri,
A clear picture cannot be obtained. On the other hand, if the fluorine-based water- and oil-repellent exceeds 25 parts by weight, it will be unnecessarily water-repellent and cannot be completely removed by short-time soaping or washing with water, resulting in poor workability.

[0029]

Next, embodiments of the present invention will be described specifically and in detail. (Example 1) 1 part of Kayano Lumiring Yellow MR (Nippon Kayaku) as a dye was added to 47 parts of water, and dissolved by heating.
After cooling, 30 parts by weight of a 19.3% aqueous solution of poly NIPAM (Kokijin) as a heat-sensitive polyacrylamide-based derivative was added. Then, Asahi Guard A was used as a water and oil repellent.
20 parts by weight of G710 (Meisei Kagaku), 1 part by weight of Emafix SSS (Dainichi Saccharification) as a cross-linking agent, and 1 part by weight of acetic acid as a reagent were added sequentially to make a total of 100 parts. This was sufficiently stirred to produce a printing liquid.

Next, 200 g of silk denim yarn with 200 denier was added.
After bundling 00 pieces, the above-mentioned printing solution was printed to a width of 1 cm with a stainless spatula and air-dried indoors. The printed part does not bleed, and the inner and outer layers of the yarn bundle are even and transparent.
It was observed that it was printed in vivid yellow. Next, after heat-treating for 3 minutes at a temperature of 150 ° C. in a drier, 2 g / l of Irgalane Black BGL (Ciba Geigy) and 2 ml / l of acetic acid as a ground color dye were added to a yarn weight of 1%.
Dyeing was carried out at a temperature of 50 ° C. for 2 minutes in a 00-fold diluted dye solution. Thereafter, the yarn bundle was immediately dehydrated with a centrifugal dehydrator. At this time, it was observed that the portion printed in yellow remained clear and uncontaminated even in the black dyeing bath.

Next, in a stainless steel steaming box at 100 ° C.
After steaming for 45 minutes, the mixture was treated at a temperature of 50 ° C. with a soaping agent, 3 ml / l of P-clean A (Morin Chemical), and then washed with water and dried. At this time, the paste printed on the printed portion was good. After drying, the yellow-printed Kasuri portion remained sharp, and the black-soaked portion was observed as pure black, and the most conspicuous yellow was observed without contamination as a good Kasuri. In addition, the dyed yarn did not show occurrence of fluff or fiber separation.

Comparative Example 1 In Example 1, the heat-sensitive polyacrylamide derivative was replaced with Asahigard AG71.
The printing liquid was printed on a hand-pulled yarn in the same manner as in Example 1 except that the amount was changed to 10 parts by weight of 0, heat-treated, steamed, soaped, and washed with water. At the time of preparation of the printing liquid, the viscosity was low and mixing was easy, but at the time of rubbing printing, it easily bleed, but after drying it was 1.2 cm after drying and the picture was unclear. Was observed. In addition, when the ground color was dyed with Irgaran Black BGL, it was observed that the portion printed in yellow was contaminated with black. After each of the steps of steaming, soaping, washing and drying, it was observed that a slightly printed portion of yellow remained. In other words, the printed portion that is to be Kasuri was almost black, did not have a pattern, and could not be used.

(Comparative Example 2) In Example 1, the heat-sensitive polyacrylamide derivative of the printing liquid was replaced with polyNIPAM.
50 parts by weight of Asahi Guard AG710
The printing liquid was printed on a hand-pulled yarn in the same manner as in Example 1 except that the amount was changed to 30 parts by weight, heat-treated, steamed, soaped, and washed with water. At the time of preparation of the printing liquid, the viscosity was high and mixing was difficult, and at the time of rubbing printing, it was difficult to rub and the printing liquid did not penetrate into the yarn bundle. For this reason,
The surface of the yarn bundle had a large printing area, and the inside could not be dyed.
Further, when the ground color was dyed with Irgaran Black BGL, it was observed that the yellow printed portion of the surface of the yarn bundle remained sharply, but the inside was stained with black. After the steps of steaming, soaping, washing and drying, it was observed that a slightly printed portion of yellow remained.
In other words, a very small part of the printed portion to be Kasuri was yellow and almost black, and did not have a pattern, indicating that it could not be used.

Comparative Example 3 In Example 1, Marpolose EM was used as the heat-sensitive polyacrylamide derivative.
Example 1 except that 30 parts by weight of a 5% aqueous solution of -400 (Matsumoto Yushi Seiyaku Co., Ltd.) was used and 20 parts by weight of Duck 204 (colored dye repellent, Tanaka Naoki Dye Shop) was used as a water and oil repellent.
In the same manner as described above, the printing liquid was printed on hand-pulp yarn, heat-treated, steamed, soaped, and washed with water. It was observed that the viscosity was high when the printing liquid was adjusted, it was difficult to mix, and during the rubbing printing, the printing liquid did not penetrate into the inside of the yarn bundle, so the inside and outside rubbing widths were different, and the picture was blurred. . The printed part had an opaque, whitish, pale yellow color.
When the ground color was dyed with Irgaran Black BGL, it was observed that the portion printed in yellow was contaminated with black. After the steps of steaming, soaping, washing and drying, it was observed that a slightly printed yellow portion remained. In other words, the printed portion that is to be Kasuri was almost black, did not have a pattern, and could not be used.

(Example 2) PolyNIPAM, Asahigard AG710 and a cross-linking agent were used in the same manner as in Example 1 except that Ranyl Red B (Sumitomo Chemical Industries) was used as the dye. In addition, a printing solution was prepared. This printing liquid could be mixed uniformly, and the liquid was also stable.

Thereafter, in Example 1, printing was carried out in the same manner as in Example 1 except that 200 yarns / bundle of glued silk (120 denier) were used instead of the glued silk yarn as the yarn bundle to be dyed. The liquid is printed on the yarn bundle, dried, heat treated,
Steamed, soaped, washed with water and dried. At the time of printing, the dye liquor penetrated well, and it was possible to print the inside and outside of the yarn bundle evenly, and the picture was sharp. At the time of dyeing with the black dye, even if the yarn bundle was immersed in the dyeing bath, it was confirmed that the color of the kasuri was red as it was, and the state of the non-polluted kasuri could be visually confirmed. Even after the steps of steaming, soaping, washing and drying, it was confirmed that the printed portion of the kasuri was dyed vivid red and the ground color was dyed black, and that the printed portion had good desizing.

Comparative Example 4 In Example 2, Caesar gum (2) was used as the heat-sensitive polyacrylamide derivative.
% Aqueous solution) and 30 parts by weight of the dyeing paste G-3 (Tanaka Naoki Dye Shop) as a water / oil repellent, to prepare a printing liquid in the same manner as in Example 2. did. This printed paste had a high viscosity and was difficult to mix with stirring.

Next, in the same manner as in Example 2, the printing liquid was printed on a glued silk thread and air-dried indoors. The printing paste has high viscosity, so it is difficult to print, the outside of the yarn bundle is wide, the inside is narrow, the picture is unclear, and the printed part is opaque and white pink with a pale pink color Was observed.
Then, in the same manner as in Example 2, the yarn bundle was heat-treated, dyed, steamed, soaped, washed with water and dried. At the time of dyeing, it was observed that the printed portion was stained black immediately after the start of the dyeing, and that the portion of the Kasuri that had been stained black did not restore to red even after the soaping.

(Example 3) In the same manner as in Example 1 above, as a dye, Kayanol Milling Blue 2RW (Nippon Kayaku)
In the same manner as in Example 1 except that 1 part by weight of was used, poly NIPAM, Asahigard AG710 and a crosslinking agent were added to prepare a printing agent. This printing liquid could be mixed uniformly, and the liquid was also stable.

Thereafter, a printing solution was printed on the glued hand-made pongee yarn in the same manner as in Example 1 and dried. It was observed that the printed portion did not bleed, and that the inner and outer layers of the yarn bundle were uniformly and transparent, and that the printed portion was printed in a clear blue color. The time required for printing was 5 minutes. Next, heat treatment, dyeing, steaming, and soaping were performed in the same manner as in Example 1 above.
Washed with water and dried. The blue-printed kasuri portion remained sharp, and the black-colored portion was observed as pure black. In addition, the dyed yarn did not show fluff or fiber separation, and it was observed that the yarn was not rough as in the case of the glued hand-pulp yarn before dyeing.

Comparative Example 5 In Example 3, 0.5 parts by weight of Caesar gum was used as the heat-sensitive polyacrylamide derivative, and Asahigard AG7 was used as the water and oil repellent.
A printing liquid was prepared in the same manner as in Example 3 except that water and 97.5 parts by weight were used without adding No. 10 or a crosslinking agent. The composition of this printing liquid is a standard one commonly used in the Yuki region of Ibaraki prefecture.

Next, the printing liquid was printed on the glued hand-made pongee yarn in the same manner as in Example 3 and air-dried, followed by steaming in a stainless steel steaming box for 45 minutes. The printed portion was not bleeding, and the printed portion was observed as clear blue. Next, the printed portion was wrapped with a traditional method using a catan thread (cotton, 20th twin yarn) to prevent the printed portion from being dyed. The time required for this closing was 50 minutes. Next, dyeing was carried out in a black dyeing bath having the same dyeing bath composition and dyeing temperature as in the above-mentioned example, while seeing the yarn bundle, so that the dye solution penetrated between the confined portions. The part previously printed in blue was not visible at the time of dyeing because it was confined with cotton thread. Next, the yarn bundle was pulled up from the dye solution, dehydrated and dried indoors. Next, the portion enclosed by the cotton thread was loosened. In the part previously printed in blue, a clearly remaining part and a part contaminated with black by the invasion of dye from between the yarns confined by the katan yarn were observed.

Example 4 In Example 1, 1 part by weight of each of the following dyes 1 to 11 was used as the dye, and the yarn bundle to be dyed was hand-spun (silk, 160 denier) 100 yarns / bundle. Other than that, dyeing of Kasuri was performed in the same manner as in Example 1. 1: Polar brilliant blue RAW 2: Spranol cyanine 7BF 3: Kayanol milling red GRA 4: Irgaran yellow-GL 5: PM green GL 6: Irgaran violet RL 7: Direct scarlet B 8: Sumilite violet BB 9 : Irganol Yellow 3GL 10: Kayanol milling grease 5 GW 11: Kayanol milling violet FBW

In each of the steps of preparing a printing liquid, printing on a yarn bundle, heat treatment, dyeing, steaming, soaping, washing and drying,
As in Example 1, it was observed that each of the clear hues could be dyed as a kasuri and was stained without contamination by a black dye. Incidentally, the dyeing of each of the dyes 1 to 11 by the rub-in printing method usually performed in the production area and the dyeing by the method of Example 4 were performed in the light fastness test JISL0843, xenon. Arc light tester 2.5KW, friction test JISL0
849, friction tester 2 type, hot water test JISL0845,
Each test was carried out for Beaker Method No. 2. At this time, there was almost no difference in deterioration and contamination between the two, and they had almost the same grade. This indicates that the dyeing method of the present invention has the same fastness as the ordinary dyeing method.

(Example 5) Using a printing solution prepared in the same manner as in Example 1 above, using a spatula with a stainless steel spatula, 100 pieces of glued hand pongee (silk, 200 denier) per bundle were 1 m thick.
m, the printing part with a spacing of 2 mm is printed at 5 places with a width of 3 cm,
Naturally dried. Next, the yarn bundle is placed in a stainless steel steaming box.
After steaming at a temperature of 00 ° C. for 45 minutes, printing was performed in yellow with a width of 3 cm, and then a printing liquid prepared in the same manner as in Example 1 except that no dye was added was further printed.
It was observed that the printed yellow portion did not bleed, and that the inner and outer layers of the yarn bundle were uniformly and transparent, and that the printed portion was printed in clear yellow.

Next, after a heat treatment in a dryer at a temperature of 150 ° C. for 3 minutes, Irgaran Black BGL was added to 2%.
g / l and 2 ml of acetic acid in a 100-fold volume
It was dyed at a temperature of 2 ° C. for 2 minutes and immediately dehydrated with a centrifugal dehydrator. It was observed that the yellow-printed portion and the white residue portion to which no dye was added remained clear and uncontaminated even in the black bath.

Next, at 100 ° C. in a stainless steel steaming box,
After steaming for 45 minutes, P-clean A was used as a soaping agent.
Was washed in a 3 ml / l bath at a temperature of 50 ° C. for 10 minutes, then washed with water and dried. The yellow-printed part and the white part without dye addition remained sharp and the black-dyeed part was observed as pure black, and the most conspicuous yellow and white were not contaminated and observed as good Kasuri .
In addition, the dyed yarn did not show occurrence of fluff or fiber separation.

[0048]

As described above, according to the present invention, it is possible to simultaneously perform dyeing and dyeing of a Kasuri pattern requiring multicolored hues in one step, and furthermore, there is no damage to the yarn and decolorization. Because it is possible to use dyes that cannot be used, there are many applicable dyes,
Existing equipment can be used as it is, easily and quickly,
It can be dyed safely. In addition, since it is not necessary to perform the closing operation and unraveling of the kasuri, the process can be shortened, labor can be saved, and the cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing an example of a dyeing method according to the present invention.

FIG. 2 is a flow sheet showing an example of a dyeing method to which a conventional consolidation step is applied.

[Procedure amendment]

[Submission date] April 5, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

1. A heat-sensitive polyacrylamide derivative which undergoes a phase transition to be hydrophobic at a high temperature above the transition temperature and hydrophilic at a low temperature below the transition temperature in the coexistence with water, and 4 to 8 parts by weight of a fluorine-based derivative. 61 to 79 parts by weight of 15 to 25 parts by weight of the water and oil repellent, 0.5 to 2 parts by weight of the dye, 0.5 to 2 parts by weight of the crosslinking agent, and 0.5 to 2 parts by weight of the reagent. 5. A printing liquid characterized by being dissolved or dispersed in water of 5.

2. A printing solution according to claim 1, wherein
A step of partially printing the yarn, a step of heating and drying the printed printing liquid, a step of drying the printing liquid on the yarn and dyeing the entire yarn with a ground color in a state where the yarn is adhered, and thereafter, the yarn is dyed. Steaming and washing with water.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

The printing liquid according to the present invention is a solution containing a heat-sensitive polyacrylamide derivative which undergoes a phase transition to be hydrophobic at a high temperature above the transition temperature in a state coexisting with water and hydrophilic at a low temperature below the transition temperature. And a water- and oil-repellent agent, which becomes water-repellent when diluted and dispersed in water and subjected to a heat treatment, and a dye and an auxiliary agent. Of this printing liquid
The composition is such that the heat-sensitive polyacrylamide derivative undergoing a phase transition is 4 to 8 parts by weight, the water / oil repellent is 15 to 25 parts by weight,
The dye is 0.5 to 2 parts by weight, the crosslinking agent is 0.5 to 2 parts by weight, and the reagent is 0.5 to 2 parts by weight.
It is melted or dispersed in 79.5 parts by weight of water.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

[0032] (Comparative Example 1) Example 1, water repellent
The printing liquid was printed on hand-pulled yarn in the same manner as in Example 1 except that the oil repellent was 10 parts by weight of Asahigard AG710, heat-treated, steamed, soaped, and washed with water. When adjusting the printing liquid, the viscosity was low and mixing was easy,
At the time of rub printing, it is easy to bleed, but it is 1.2 cm after drying, despite rubbing in 1 cm width,
It was observed that the picture was blurred. In addition, when the ground color was dyed with Irgaran Black BGL, it was observed that the portion printed in yellow was contaminated with black.
After each of the steps of steaming, soaping, washing and drying, it was observed that a slightly printed portion of yellow remained. In other words, the printed portion that is to be Kasuri was almost black, did not have a pattern, and could not be used.

Claims (3)

[Claims] 1. A water- and oil-repellent agent, a dye and a solution of a heat-sensitive polyacrylamide derivative which undergoes a phase transition to become hydrophobic at a high temperature above the transition temperature and become hydrophilic at a low temperature below the transition temperature in the presence of water. A printing liquid comprising an auxiliary agent dispersed therein. 2. A heat-sensitive polyacrylamide derivative which undergoes a phase transition to be hydrophobic at a high temperature above the transition temperature and hydrophilic at a low temperature below the transition temperature in the presence of water, and 4 to 8 parts by weight of a fluorine-based derivative. 61 to 79 parts by weight of 15 to 25 parts by weight of the water and oil repellent, 0.5 to 2 parts by weight of the dye, 0.5 to 2 parts by weight of the crosslinking agent, and 0.5 to 2 parts by weight of the reagent. 5. A printing liquid characterized by being dissolved or dispersed in water of 5. 3. A step of partially printing a yarn using the printing liquid according to claim 1 or 2, a step of heating and drying the printed printing liquid, and a step of drying the printing liquid on the yarn. And a step of dyeing the entire yarn with a ground color in a state where the yarn is adhered, and thereafter, a process of steaming and washing the yarn with water.