JPS6024866B2 - Transfer printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer printing method, and particularly to a transfer printing method using a discharge printing agent.

The dyeing technique conventionally called discharge printing generally refers to removable dyes (dyes that are discharged using a discharge printing agent).

On the other hand, dyes that cannot be discharged with a discharge dye are called non-discharge dyes), and after drying, a glue paste containing a discharge dye is printed, steamed, washed with water, and soaped to create the pattern. A method of discharging only a portion is known. Alternatively, the ground color is pre-dyed with a removable dye, and after drying, a glue paste containing a discharge dye and a non-removable dye that is not discharged with the discharge dye and has a different hue from the releasable dye is used. There is also a known method of printing, steaming, washing, and soaping, then coloring and discharge printing in which only the patterned areas have different hues. Although the method differs slightly depending on the dye type, a few specific examples will be described below. '1' Discharge printing of acrylonitrile fibers Discharge printing is carried out using a cationic dye discharge agent, such as removable dyes or non-removable dyes, and can be roughly divided into reduction discharge printing methods and oxidation discharge printing methods.

The reduction discharge printing method uses dechlorin or stannous chloride as a reducing agent, and the oxidation discharge printing method uses sodium chlorite or sodium hypochlorite as an oxidizing agent.

Dyes for background dyeing include Zebronje O-Iso L (Dupont dye), Astrazon Orange Wave L (Bayer dye), Astrazon Red Wave L, and Maxilon Red BL.
(dye manufactured by Ciba-Geigy), Eisenkatilon Blue GLH (dye manufactured by Hodogaya Chemical Co., Ltd.), Maxilon Blue GR
Typical dyes include Diacrylic Blable and Ball L (manufactured by Mitsubishi Kasei), which can be easily discharged with stannous chloride.

Next, the typical non-dischargeable dyes that can be used in the colored discharge printing method are Eisenkatilon Brilliant Yellow 30LH, Eisenkatilon Yellow 50LH, Eisenkatilon Buri IJ Entretsudo Z4GH, Eisenkatilon Brilliant Pink FGH, and Eisenkachiron Brilliant Pink FGH. Lone brilliant tread string day, crampon kachiro sobrilliant blue 3RLH, crampon kachiron turkis blue 1 LH
(All of the above are dyes manufactured by Hodogaya Chemical Co., Ltd.), Diacrylic Z Lubrilliant Pink R, Diacrylic Brilliant Violet FRL, Diacrylic Brilliant Violet RH
L (dye manufactured by Mitsubishi Kasei Co., Ltd.), Anthrazone Red Violet FaR, Anthrazone Blue F2R, Suminol Blue 3R, Suminol Blue 2-Mosquito (dye manufactured by Sumitomo Chemical Co., Ltd.)
etc. can be given.

[2] Discharge printing of polyester fibers Polyester fibers have a delicate fiber structure and are hydrophobic, making it extremely difficult for discharge printing agents to penetrate and diffuse into the fibers. Therefore, a discharge printing reinforcing agent (carrier 1) must be used in combination. better results can be obtained.

Generally, the following two or three methods are known.

A coverable disperse dye (removable dye) is padded onto a polyester fiber cloth, dried, and then a glue paste containing a discharge agent is printed.
After drying, it is steamed under normal pressure to decompose the dye in the printed area, and then
A method in which the thermosol is heated under high pressure to dye the dye in the non-printed areas. Alternatively, pad a removable dye (removable dye), dry it, then print a glue paste containing a discharge agent, dry it, and then apply thermosol or high-pressure steaming to remove the imprinted area at the same time as the discharge printing process. How to dye the parts as well. Alternatively, there is a method in which a glue paste containing a discharge printing agent is printed on a ground-dyed cloth, and after drying, discharge printing is carried out by thermosol or high-pressure steaming. Discharging agents that can be used include Decro IJ and stannous chloride.
Removable dyes include Resolin Yellow SOS, Resolin Yellow NL, Resolin Yellow Brown GLS, Resolin Orange 30L, Resolin Scarlet 30L,
Resolin Red RL, Resolin Red BRL, Resolin Rubin BL, Resolin Blue BBLS, Resolin Navy Full-GLS, Resolin Brilliant Scarlet P
There are dyes such as GG (all dyes manufactured by Bayer), and non-dischargeable dyes used for coloring and discharge printing include Resolin Brilliant Yellow 70L Paste and Resolin Brilliant Red BS.
Paste, Resolin Violet RL, Resolin Flu RRL, Resolin Flu FBL Paste 50%, Resolin Brilliant Yellow PGG, Resolin Brilliant Violet PRL (all dyes manufactured by Bayer), etc. are used.

{3l Other methods include white discharge printing with dechlorin for polyamide fibers, white discharge printing with dechlorin for acetate fibers, colored discharge printing with stannous chloride, and Rongarit C (manufactured by Hoechst) for regenerated cellulose fibers. Hydrosulfite R Conc (manufactured by Ciba-Geigy), Alvarite CP (Daiichi Pharmaceutical Co., Ltd.), and the like are known.

As mentioned above, white discharge printing and colored discharge printing methods are known and put into practical use for many types of dyes.

However, all of these methods use discharge printing paste to print directly onto yarn-dyed cloth, and their ability to express patterns is limited, making it extremely difficult to express elaborate patterns.
In order to solve the above-mentioned problems, the present invention makes use of the advantages of the conventional white discharge printing and colored discharge printing methods, and further takes advantage of the advantages of the transfer lacquer zero dyeing method, making it possible to express extremely elaborate patterns. This will be explained in detail according to the drawings.

As shown in Figure 1, art paper, coated paper, printing base paper,
A hydrophobic resin layer 2 is provided on a transfer sheet base 1 such as printing paper such as pure white paper, cellophane, acetate film, aluminum foil, or a film laminated with these, and a discharge printing agent is contained on this hydrophobic resin layer 2. A transfer sheet 4 is prepared by forming a pattern layer 3 by an appropriate printing method, such as a gravure method or a screen 0 printing method, using the ink.

Next, as shown in FIG. 2, the transfer sheet 4 is placed in a steam atmosphere, for example under normal pressure, on a dyed cloth 5 that has been pre-dyed with a dye (removable dye) that can be discharged with a discharge agent contained in the ink. Alternatively, by closely contacting and heating in a pressurized saturated or superheated steam atmosphere, the discharge printing agent on the transfer sheet 4 discharges the dischargeable dye in the steam atmosphere without transferring the hydrophobic resin layer 2 and ink 3. . Next, finishing is performed by a conventional method to obtain a discharge printed cloth. The greatest feature of the present invention is that the discharge printing action occurs at the same time as the discharge printing agent is transferred to the cloth to be discharged in a steam atmosphere. Transfer printing is performed in one step.

Colored discharge printing is also possible by simultaneously containing a non-dischargeable dye that is not discharged in the discharge printing agent in the above-mentioned ink. Specifically, the resins suitable for forming the hydrophobic resin layer described in the present invention include acetyl cellulose, caprylic cellulose, nitrocenolose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cellulose acetate butyrate, and cellulose propionate. ,
Polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, modified polyvinyl chloride, polyvinyl formal, polyvinyl butyral, polyvinyl alkyl ether, vinyl acetate/ethylene copolymer, polyacrylate, polyacrylate, polyacrylic Examples include acid ester, methyl methacrylate, cyanoacrylate, acrylate/vinyl acetate copolymer, polystyrene, polyamide, polyurethane, chain polyester, polyhydroxy ether, maleic acid resin, cyclized rubber, chlorinated rubber, etc. As the thermal transfer conditions, the steaming condition can be saturated or superheated steam at normal pressure of 100 pm to 22,000 pm, and the high temperature and high pressure saturated steam, and the heating condition is 50 pm.
~220° C., and the pressure conditions should be sufficient to bring the transfer sheet and the transfer cloth into close contact, and it goes without saying that the above conditions and time will vary depending on the target material and dye type.
Further, as an alternative method of the present invention, there is also the following method.

That is, as shown in FIG. 3, a hydrophobic resin layer 7 is applied on a transfer sheet base 6, and a removable layer 8 is formed on the resin layer 7 with an endless plate or a desired pattern using ink containing a removable dye. Further, a transfer sheet 10 is prepared on which a pattern layer 9 is appropriately formed by overprinting with an ink containing a discharge printing agent and containing or not containing a non-dischargeable dye that cannot be discharged by the discharge printing agent. Next, as shown in FIG. 4, the transfer sheet 10 is brought into close contact with the cloth 11 to be dyed in a steam atmosphere, heated and pressurized, and then washed with water or soaped as necessary to remove the releasable dye and discharge the dye. In this method, a removable dye is discharged using a discharging agent in the area where the ink containing the agent overlaps, and the discharged area is dyed with a non-removable dye, or colored discharge printing or white discharge printing is performed. The dyed fabrics that can be used in the present invention include synthetic fibers such as acrylic, polyester, and polyamide, natural fibers such as natural cellulose and proteinaceous, and mixed structures of synthetic fibers and natural fibers. It can be applied to fibers.

Further, the dye can be selected from the above-mentioned dyes depending on the fiber to which it is applied.

Because the present invention has the above-described configuration, unlike conventional discharge printing methods, it is possible to reproduce very elaborate patterns by combining tweezers, and problems such as pattern joining, which are extremely difficult from a plate-making perspective, can be solved by the present invention. The problem has been resolved and the practical effect is tremendous. The effects will become clearer from the following examples.
Example 1 {1) Gravure ink was prepared using the following formulation.

■ A transfer sheet base was created using the following method.
The paper is 30 evenings/elbow print base paper (manufactured by Daisanko Paper)
Versamite 725/Thyroid #244/IPA/Toluol: 15/3/4 using 35-mount gravure endless edition
It was uniformly coated with a varnish of 0/42 (weight ratio) to form a transfer sheet base. (3' Yarn-dyed cloth was obtained by the method shown below.

Astrazon Blue GL (manufactured by Bayer)...1 Speed rate character plan Z Blocking mourning★shiku dragon straw stage 100℃ x 3
After steaming under normal pressure, the cloth was washed with water and dried to obtain a yarn-dyed cloth. Next, a transfer sheet was obtained in which a pattern was formed on the transfer sheet base of [2' with the gravure ink of '1' and a gravure plate having a plate depth of 35 mm. Next, apply this transfer sheet to {3} yarn-dyed cloth.
Steaming was performed at the same time as the transfer under the conditions of transfer cylinder temperature of 15℃, pressure of 500mm/skin, transfer time of 8 minutes of rat sand in normal pressure saturated steam at 00℃, and more perfect dye fixation. In order to achieve this, the fabric was allowed to stay in atmospheric pressure saturated steam at 100 pm for 18 minutes, and an extremely good colored discharge printed fabric was obtained. Example 2 '1.1 Gravure ink was prepared using the following formulation.

/Isamitsudo725...15
．． 0 Thyroid #244...
2.0 triol...39
-0 inpropyl alcohol...30
．． 0 Nonionic surfactant...1.0
Eisenkatilon Brilliant Yellow 30LH
...3.0Stannic chloride
...10.01〇〇-〇'21 An ink having the following formulation was prepared, and solid printing was performed on the transfer sheet base shown in Example 1 using a 35-gravure endless plate.

Versamite 725...15
．． 0 Erosil #200 (Silica fine particle powder manufactured by Nippon Erosil Co., Ltd.) ...2.0 Toluol
...39.0 Inpropyl alcohol ...40.0 Nonionic surfactant ...1.0 Astrazone Red
Group L (manufactured by Bayer)
...3.0100-〇 After forming a pattern on the transfer sheet obtained in {21] with the ink obtained in [1} using a 35r gravure plate, a plain weave of cashmilon was applied under the same transfer conditions as in Example 1. After transferring to cloth (manufactured by Asahi Kasei Co., Ltd.), steaming was carried out at normal pressure for 20 minutes at 100°C to strengthen the bond between the dye and the fibers, and after applying a sawpisog finish, an extremely good dyed product was obtained. .

Example 3 ○) Polyester silk twill #465 (manufactured by Toray Industries) was padded with the following dyeing formulation solution and dried.

Resolin NaWBlueGLS 3 Taaboran IS (surfactant manufactured by Bayer) 1 Tarebegal PT (carrier 1 manufactured by Bayer) 4 Sodium dihydrogen phosphate (pH stabilizer) 1 night 9 days / 21 Example 1
A pattern was formed on a transfer sheet base shown in '211 using a gravure plate using the following ink.

Tamanol 10 eaves (phenol resin manufactured by Arakawa Forest Products)
15.0 Erogil #200
2.0 toluol
...33.0 inpropyl alcohol
...35.0 Dianics Brilliant Red B-SE.・・5.0Stannic chloride
...10.0 [31 The transfer sheet obtained in {21] was applied to a polyester cloth of '1} for 13 times at the same time as steaming in a high pressure steamer for 20 minutes at a heating cylinder temperature of 150°C and a pressure of 100 minutes/immediately. When adhesion was carried out under these conditions and a subsequent soaping finish was applied, an extremely good dyed product was obtained.

Example 4 [1' Printing was carried out using a gravure endless plate with a plate depth of 35 mm on a high-quality paper with a basis weight of 60 cm and a plate depth of 35 mm with the ink of the following formulation,
A dry transfer printing sheet was obtained.

Echi'Rece'Relose (Etocel N-7, manufactured by Hercules). ...7.0 Ethyl alcohol ...40.0 Impropyl alcohol ...33.0 Sumikalon Change B Conc (sublimable dye manufactured by Sumitomo Chemical Co., Ltd.) ...15.0100-〇 [21 Using a transfer sheet named '11' Dry transfer printing was carried out on polyester silk quill #465 (manufactured by Toray Industries, Ltd.) under the following conditions: 20,000, 4 inkstone sand, 400 m/base to obtain a yarn-dyed cloth.

A pattern was formed on the transfer sheet base shown in '31 Example 1■ using a No. 35 French gravure plate using the ink shown below.

/A Summit 725...1
5.0 Thyroid #244...
・2.0 toluol. ．．
．． 39.0 Inpropyl alcohol...
・30.0 nonionic surfactant...
1.0 Resolin Blue-FBL...
3.0Stannic chloride...10.
0100-〇■ Using the transfer sheet obtained in '3},
The yarn-dyed fabric obtained by the dry transfer printing shown in (3) was steamed at the same time as the transfer in a high-pressure steamer for 20 minutes at 130°C under the conditions described above, and was then finished by soaping. Very good coloring was obtained. A discharge dyed product was obtained.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, and FIGS.
The figure shows a cross-sectional view of a transfer sheet used in the present invention, and FIGS. 2 and 4 show cross-sectional views when a transfer resin layer and the like are transferred to a cloth to be dyed using the transfer sheet. 1, 6...Transfer paper base, 2,7...
Hydrophobic resin layer, 3, 9...Picture layer, 4, 10...
...Transfer sheet, 5, 1 1 Dyeing cloth, 8...
...Removable dye layer. Figure 1 Figure 2 Figure 3 Figure 4

Claims (1)

[Scope of Claims] 1 A hydrophobic resin layer is provided on a base sheet, and an ink containing a discharging agent on the resin layer or an ink containing a discharging agent and a non-discharging dye that is not discharged by the discharging agent. A transfer sheet is created by forming an appropriate pattern with the dye, and then the transfer sheet is brought into close contact with the fabric to be dyed, which has been pre-dyed with a removable dye that is discharged with the above-mentioned discharging agent, in a steam atmosphere and heated. , a transfer printing method characterized by white discharge printing or colored discharge printing, and further soaping treatment and appropriate post-treatment. 2. A hydrophobic resin layer is provided on the base sheet, and a removable dye layer is formed on the resin layer on the entire surface or in an appropriate pattern using an ink containing a removable dye that can be discharged with a discharging agent, and then A transfer sheet is created by appropriately forming a pattern with an ink containing a discharge printing agent or an ink containing a discharge printing agent and a non-dischargeable dye that is not discharged by the discharge printing agent, and then the transfer is performed in a steam atmosphere. A transfer printing method characterized in that a sheet is brought into close contact with a cloth to be dyed and heated to perform white discharge printing or colored discharge printing, and further performing soaping treatment and appropriate post-treatment.