JPS648755B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for printing cellulose fibers, protein fibers, and synthetic polyamide fibers using reactive dyes, and its purpose is to improve dyeing density (dye utilization rate) of printed products. In addition to dramatically improving the quality of printing, it also greatly simplifies the cleaning process for dyed objects after printing.

A reactive dye is a dye that has a reactive group that can covalently bond to a hydroxyl group or an amino group of fibers, and by using this dye, products with excellent color fastness based on the above bond can be obtained. There are advantages. However, when printing fibers using the above dyes, approximately 50 to 70% of the commonly used dyes bind firmly to the fibers, but the remaining approximately 30 to 50% remain unreacted or in a hydrolyzed state. It only adheres to the fibers and is easily removed from the fibers. Therefore, when printing using reactive dyes, in order to obtain products with practical color fastness, it is necessary to remove the unreacted dyes and their hydrolyzates that adhere to the fibers after printing. For example, after washing with water or hot water, it is essential to thoroughly wash the dyed object using a detergent such as a surfactant at a high temperature of around 100°C (high-temperature washing process).
However, this washing process removes approximately 30 to 50% of the dye used.
% of the dye is washed away, and the loss of the dye itself is extremely serious, and the reduction in dye utilization rate (dyeing density) caused by this process is also a serious problem. Moreover, the dye that falls off from the dyed object during the above process has a great risk of contaminating the white area of the printed object, and there is also the problem of disposing of the dye waste liquid.Furthermore, the above washing process itself requires high temperatures, making it energy-efficient. It is also uneconomical.

In addition, when printing fibers using reactive dyes, it is generally necessary to use alkaline agents such as heavy dyes, soda ash, and caustic soda. If stored, the dye may undergo hydrolysis and change over time, and the paste itself may not have a uniform alkaline concentration, and its use may cause uneven color. Furthermore, in recent years, a so-called wet transfer printing method has been developed that uses a printing ink containing a dye and a transfer paper made of a transfer resin to dye the printing ink onto the dyed object by heating, steaming, etc. after transferring the printing ink to the dyed object. This method is attracting attention because of its ability to dye minute patterns, but when this method is used, the ink layer itself is thin, so there is a serious drawback, especially when the dye comes off during the washing process after printing. In any case, printing using reactive dyes requires complicated cleaning processes such as washing with water, hot water, and high-temperature washing after printing, and the current situation is that nearly 50% of the dye used is removed to obtain a practical product. It is in.

In view of the above-mentioned current situation, the present inventors have provided a method for dramatically increasing the dye utilization rate, requiring only a slight washing with water in the subsequent washing step, and obtaining printed products with clear, deep colors and good color fastness. As a result of various studies aimed at achieving this goal, the present inventors have discovered that all of the above objects can be achieved by pretreatment using the specific water-soluble polymer described below, and have now completed the present invention.

That is, in printing cellulose fibers, protein fibers, and synthetic polyamide fibers using reactive dyes, the present invention provides (a) prior to printing the general formula [In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. HX represents an organic or inorganic acid. ] A polymer consisting of repeating monomer units represented by the above general formula [ ] and (b) copolymerized with the repeating monomer units represented by the above general formula [] and the monomer blended in an amount up to 1/2 mole with respect to the monomer forming the unit. A printing method characterized in that the fibers are pretreated with an aqueous solution containing a water-soluble polymer selected from copolymers consisting of units of possible other monomers and having a molecular weight of 10,000 or less.

According to the method of the present invention, by pre-treating fibers using the above-mentioned specific water-soluble polymer, the reaction used can be carried out under neutral conditions without adding any alkaline agent to the printing paste during subsequent printing. Substantially all of the dyes can be firmly attached to the fibers, producing very deep colors.
A printed product can be obtained that is clear and has good color fastness. Furthermore, as a result, the washing process after printing is sufficient with a very simple water washing process that simply removes the glue adhering to the fibers, which is very favorable in terms of energy and dyeing waste. Furthermore, the method of the present invention can be carried out according to a wet transfer printing method, and there is no need to add an alkaline agent to the ink, and therefore, the stability of the ink is also extremely good. The reason why the pretreatment of the present invention exhibits such excellent effects is still not clear, but the specific water-soluble polymer described above has a large number of aliphatic secondary amino groups in the polymer. Since this group reacts extremely well with the reactive group of the reactive dye molecule even under neutral conditions, a polymeric dye apparently bound by covalent bonds is formed.
It is believed that this constitutes a reactive dye layer firmly fixed on the fibers, and thus it is possible to obtain dyed articles with extremely deep and vivid colors and excellent color fastness.

In the present invention, first, cellulose fibers, protein fibers, and synthetic polyamide fibers are
Pretreatment with an aqueous solution containing a water-soluble polymer selected from the following and having a molecular weight of 10,000 or less. The molecular weight of each water-soluble polymer used here was determined by a gel filtration method using Cephadex G-100 (manufactured by Pharmacia Fine Chemicals, Sweden) as a filler, and was approximately 10,000 or less. This is important, and if this value exceeds about 10,000, it will be difficult to achieve the desired effect of the present invention. The particularly preferred molecular weight of the polymer is about 500 to 5,000.

The polymer shown in (a) in the above water-soluble polymer is
For example, general formula It can be produced by cyclization polymerizing a compound represented by the formula [wherein R ₁ , R ₂ and HX are the same as above] using a radical polymerization catalyst. The polymerization method at this time may be according to a known method. Examples of the radical polymerization catalyst include ammonium persulfate, hydrogen peroxide, benzoyl peroxide, tertiary butyl hydroperoxide, azobisisobutyronitrile, and cumene hydroperoxide. Examples of the solvent include water and polar solvents such as methanol, ethanol, isopropanol, n-propanol, formamide, dimethylformamide, dioxane, acetonitrile, and dimethylsulfoxide. In addition, the polymerization reaction can be carried out using the general formula []
Dissolve 100 parts by weight of the compound in 20 to 100 parts by weight of a solvent, add 0.05 to 10 parts by weight of a radical polymerization catalyst, and add 0.01 to 5 parts by weight of a reducing agent such as acidic sodium sulfite, ferrous sulfate, or copper sulfate as necessary. Can be used in combination.
Polymerization temperature is usually 70~110℃, polymerization time is usually 10~
The time period is preferably about 50 hours, and the polymerization reaction is advantageously carried out while blowing nitrogen gas.

Other copolymerizable monomer units in the copolymer shown in (b) in the above water-soluble polymer include:
Typically, the unit represented by the formula −SO ₂ − [], the general formula [In the formula, R ₁ and R ₂ are the same as above. Y represents a halogen atom] and acrylic monomer units can be exemplified. When introducing the unit represented by the above formula [] into a copolymer, for example, the reaction may be carried out while blowing sulfur dioxide gas into the cyclization polymerization reaction system of the compound represented by the above general formula []. When introducing the unit represented by the above general formula [], the following general formula is often introduced into the cyclization polymerization reaction system of the compound represented by the above general formula []. [In the formula, R ₁ , R ₂ and Y are the same as above] may be present as a comonomer. Similarly, when introducing an acrylic monomer unit, acrylic acid, methacrylic acid, acrylamide, etc. may be used as a comonomer. , methacrylamide, alkali metal or ammonium salts of acrylic or methacrylic acid, lower alkyl esters of acrylic or methacrylic acid, tertiary or quaternary amino substituted lower alkyl esters, tertiary or quaternary amino and hydroxy substituted A lower alkyl ester or the like may be present. Among the units introduced using the above acrylic monomer, particularly preferred units are represented by the following formula [].

[In the formula, R ₃ is H or CH ₃ , Y is NH ₂ , OH,
ONa, OK, ONH ₄ , OCH ₃ , OC ₂ H ₅ , OC ₂ H ₄ N
(CH ₃ ) ₂ , OC ₂ H ₄ N (C ₂ H ₅ ) ₂ , OC ₂ H ₄ N (CH ₃ ) ₃・
_Cl , _OC2H4N ( _CH3 )( _C2H5 ) ₂・Cl _,
OCH ₂ CH (OH) CH ₂ N (CH ₃ ) ₂ or OCH ₂ CH
(OH)CH ₂ N(CH ₃ ) ₃・Cl] The production conditions for the homopolymer may be similar to those for the homopolymer shown in (a) above, and the monomers that can be copolymerized are: It can be blended in an amount up to 1/2 mole with respect to the compound represented by the above general formula [], and the copolymer thus obtained can exhibit approximately the same effect as the homopolymer shown in (a) above. .

Pretreatment with a water-soluble polymer selected from (a) and (b) above and having a molecular weight of 10,000 or less according to the present invention can be carried out according to a conventional pad treatment method or coating treatment method. For example, typically, the fibers to be treated are padded in an aqueous solution in which approximately 0.1 to 2.0% by weight of the above water-soluble polymer is dissolved, and the fibers to be treated are padded at a reduction rate of 50 to 50%.
This can be done by squeezing at 200%, or by coating the fibers with a paste or the like containing the polymer so that the same amount of polymer as described above adheres to the fibers. The above aqueous solution, paste, etc. may further contain ordinary surfactants, urea, sizing agents, fiber processing resins, etc., as necessary.
In this case, the pH of the liquid is about 6 to 10, preferably 6 to 8.
It is desirable to adjust the amount to a certain degree. It is preferable to dry appropriately after the above-mentioned pad treatment or coating treatment.

In the present invention, after the above pretreatment, the treated fabric is then printed using a reactive dye. This printing is carried out using a conventional printing paste containing a reactive dye.
This can be carried out by screen printing, roller printing, wet transfer printing, etc. In particular, in the present invention, there is no need to add and blend an alkaline agent into the printing paste. To explain the above wet transfer printing in more detail, first, a release layer made of a resin or adhesive that softens and melts under heat and pressure is formed on the base sheet, and then a desired pattern is formed on this with printing ink containing a reactive dye. A method can be applied in which a transfer paper is prepared by printing the above, and then the transfer paper and the object to be dyed which have been pretreated as described above are brought into close contact with each other, and the printing ink layer is transferred onto the object by heating and pressing.

In the above printing process, the reactive dyes include:
Any of a variety of known materials can be used. The dye typically includes, for example, a dichlorotriazinyl group, a dichloroquinoxaline group, a trichloropyrimidine group, a monochlorodifluoropyrimidine group, a vinylsulfonyl group, a monochlorotriazinyl group, a chloroacetyl group, as a reactive group. Examples include dyes having vinylsulfonyl/N-methyltaurine, an α-bromoacrylamino group, an acryloylamino group, a monofluorotriazinyl group, a difluorotriazinyl group, and the like. These dyes are usually water-soluble, but need not be particularly water-soluble, and may be water-insoluble, that is, dispersed.

After the above printing process is finished, in the present invention, approximately
Steam treatment with saturated steam or high-temperature steam at 100-150℃ for about 5-60 minutes, followed by low-temperature washing.
Unnecessary paste, ink material, resin, etc. are removed to obtain the desired printed material with clear, deep color and good color fastness.

In order to explain the present invention in more detail below, synthesis examples of water-soluble polymers used in the present invention are listed as reference examples, and then examples are listed. In addition, each example central part and %
The figures are based on weight.

Reference Example 1 100 g of diallylamine hydrochloride and 40 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a gas inlet tube, and a thermometer, and the mixture is stirred to dissolve uniformly. While blowing nitrogen gas through the gas inlet tube, the internal temperature was raised to 80°C, and while stirring, 2 g of an 80% butanol solution of tertiary butyl hydroperoxide was added dropwise over 1 hour. The reaction is exothermic and the internal temperature rises to 90℃. After the addition is complete, stirring is continued at 90°C to obtain a light brown viscous liquid. The polymerization rate measured by colloid titration method was 90%. The intrinsic viscosity of the above polymer determined in a 0.1N potassium chloride solution was 0.13 at 30°C. When the molecular weight distribution of this polymer was measured by gel filtration using Cephadex G-50 (manufactured by Pharmacia Fine Chemicals, Sweden) as a filler, most of the molecular weights were in the range of 1,000 to 4,000.

Reference Example 2 135 g of diallylamine hydrochloride and 250 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a gas introduction tube, and a thermometer, and the mixture is stirred to dissolve uniformly. Raise the internal temperature to 50℃ and release sulfur dioxide gas to approx.
After blowing for 15 minutes, add a 10% aqueous solution of ammonium persulfate.
Drop 50g over 1 hour. During this time, continue to blow sulfur dioxide gas. After blowing in 64 g of sulfur dioxide gas for about 2 hours, the stirring reaction was continued at 50°C for 10 hours, and then nitrogen gas was blown in to remove free sulfur dioxide gas. A pale yellow, slightly viscous, transparent liquid is thus obtained. The polymerization yield measured by colloid titration was 92%. The intrinsic viscosity of the obtained polymer determined in a 0.1N potassium chloride solution is:
It was 0.15 at 30℃. In addition, when the molecular weight distribution of this polymer was determined by gel filtration method, most of the molecular weight distribution was 1500~
It was in the 5000 range.

Reference Example 3 135 g of diallylamine hydrochloride and 100 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a metering pump, a gas inlet tube, and a thermometer, and the mixture is stirred to dissolve uniformly. Next, increase the internal temperature to 50℃ while blowing in nitrogen gas.
20ml of ammonium persulfate 20% aqueous solution per minute.
Add at a rate of 0.2 ml. Five minutes after the start of addition, 180 g of a 20% acrylamide aqueous solution was gradually added dropwise over 3 hours. The reaction is exothermic, and the temperature of the reaction solution is raised to 55°C, and the same temperature is maintained until the dropwise addition of acrylamide is completed. If the stirring reaction is continued for 10 hours, a yellow transparent viscous liquid is obtained. The polymerization yield determined by colloid titration was 75%. The intrinsic viscosity of the resulting polymer determined in a 0.1N aqueous potassium chloride solution was 0.09 at 30°C. When the molecular weight distribution of this polymer was measured by gel filtration, most of the molecular weight distribution was in the range of 500 to 2,500.

Reference Example 4 135 g of diallylamine hydrochloride, 80 g of diallyldimethylammonium chloride, and 100 g of water are placed in a reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, a thermometer, and a gas inlet tube, and are stirred to uniformly dissolve them. The internal temperature was raised to 60°C, and 40 g of a 20% aqueous solution of ammonium persulfate was gradually added dropwise over 2 hours from the dropping funnel while stirring and blowing nitrogen gas through the gas inlet tube. When the polymerization is continued at 60°C for 24 hours after the dropwise addition, a viscous light brown liquid is formed. The polymerization yield of this product was 85% by colloid titration.
The intrinsic viscosity of this polymer determined in a 0.1N potassium chloride solution was 0.11. Furthermore, when the molecular weight distribution of this polymer was determined by gel filtration, it was mostly in the range of 1000 to 3500.

Example 1 50 g of cotton satin was mixed with 1.0 g of the polymer obtained in Reference Example 1.
% and polyoxyethylene nonylphenol ether (average number of added moles of ethylene oxide 15)
Squeezing ratio 100 after padding with aqueous solution containing 0.5%
% and dry at 100℃ for 2 minutes for pretreatment.

Next, a pattern was printed on the pretreated cotton sateen using a printing paste having the following composition, and its weight was 85 g.

<Printing paste prescription>"Mikasion Brilliant Red 8BS" (manufactured by Nippon Kayaku Co., Ltd.) 30 parts urea 50 parts 10% - "Snow Algin TSSL" (manufactured by Fuji Chemical Co., Ltd.)
400 parts turpentine emulsion (emulsified by adding 5 parts of nonionic emulsifier and 25 parts of water to 70 parts of mineral turpentine) 200 parts of sodium metanitrobenzelsulfonate 10 parts of water 310 parts in total 1000 parts Next, 100 parts of the above printed fabric was added. After drying at ℃, steam treatment with saturated steam at 100℃ for 10 minutes, and wash with water to wash away unnecessary glue. In this way, a printed cloth with a clear red pattern is obtained.

The washing liquid during the water washing was not colored at all, and no dye was observed to come off as a result of this water washing. In addition, the printed fabric obtained above was treated with a surfactant “Senkanol”.
When washed at 100°C for 20 minutes at a dyeing ratio of 1:50 using an aqueous solution containing 2 g of ``CW'' (manufactured by Nippon Someka Co., Ltd.), there was no coloration of the washing liquid and no shedding of the dye was observed.

Comparative Example 1 A pattern was printed on 50 g of cotton satin using a printing paste having the following composition, and the weight was measured to be 85 g.

<Printing paste prescription>"Mikasion Brilliant Red 8BS" 30 parts urea 50 parts 10% - "Snow Algin TSSL" 400 parts turpentine emulsion (same as Example 1)
200 parts Sodium metanitrobenzenesulfonate 10 parts Sodium bicarbonate 15 parts Water 295 parts Total 1000 parts Next, the above printed fabric was dried at 100°C and then steamed with saturated steam at 100°C for 10 minutes, and the washing liquid turned dark red. Coloring was observed and considerable dye loss was observed. The amount of dye removed from the washing solution was measured by spectrophotometry and was approximately 0.38 g. When this was further washed at 100° C. for 20 minutes in the same manner as in Example 1, the washing liquid was colored red, and the amount of dye removed by this treatment was measured in the same manner as about 0.20 g. From this, the dye utilization rate was calculated to be 55% using the following formula.

(0.38+0.20)/(85-50)×30/1000×100≈55.2 The thus obtained printed fabric had a much lower dye density than that obtained in Example 1.

Example 2 Cotton knit was padded with an aqueous solution containing 1.0% of the polymer obtained in Reference Example 2, 0.5% of polyoxyethylene nonylphenol ether (added moles of ethylene oxide: 20), and 0.5% of "Snow Algin TSSL", and then the squeezing rate was The pretreatment of the present invention is performed by squeezing at 100% and drying at 100°C for 2 minutes.

Next, a pattern is printed on the pretreated cotton knit with a printing paste having the following composition, and then dried at 100°C.

<Printing paste prescription>"Mikasion Blue 2R" (manufactured by Nippon Kayaku Co., Ltd.) 40 parts urea 50 parts 10% - "Snow Algin TSSL" 400 parts turpentine emulsion (same as Example 1)
200 parts Sodium metanitrobenzenesulfonate 10 parts Water 300 parts Total 1000 parts The printed fabric thus obtained was steam-treated with saturated steam at 100°C for 10 minutes, and washed with water to remove unnecessary sizing agent, resulting in a clear dark blue color. A printed cloth with a pattern is obtained.

No shedding of the dye was observed during the water washing. In addition, the obtained printed cloth is called “Senkanol CW”.
The dye was washed for 2 minutes at 100° C. with a 2 g/water solution at a bath ratio of 1:50, but the dye did not come off.

Example 3 After padding #40 cotton broadcloth (without mercerization) with an aqueous solution containing 1.0% of the water-soluble polymer obtained in Reference Example 3 and 0.5% of polyoxyethylene nonylphenol ether (number of moles of ethylene oxide added: 15). Pre-dry treatment for 2 minutes at 100% squeezing rate.

Next, the above pretreated fabric was printed with a printing paste having the following composition in the same manner as in Example 1, and then printed with saturated steam at 100°C.
After steaming for 30 minutes, it is washed with water to obtain a printed cloth with a clear bright blue pattern.

<Printing paste formulation>"Procion Turquoise Blue H-A" (manufactured by ICI) 30 parts Urea 50 parts 10% - "Snow Algin TSSL" 400 parts Turpene emulsion (same as Example 1) 200 parts Metanitrobenzenesulfonic acid Soda: 10 parts Water: 310 parts Total: 1000 parts The resulting printed fabric did not show any loss of dye during the above-mentioned washing with water, and also showed no loss of dye when washed with the same "Senkanol CW" as in Example 1. was not seen.

Example 4 Silk habutae was padded in the same padding bath as in Example 1, dried and pre-treated, then printed with a pattern using the same printing paste as in Example 1, dried, steamed and washed with water. Then, a printed cloth with a clear red pattern is obtained.

No dye was observed to come off during the above-mentioned water washing, and no dye was observed to come off even after the high temperature washing treatment using "Senkanol CW" as in Example 1.

Example 5 When the same operation as in Example 2 was carried out on silk habutae, a printed cloth with a clear blue pattern was obtained without any dye coming off during washing. This is Example 1
The dye did not come off even when subjected to high-temperature cleaning treatment using the same ``Senkanol CW''.

Example 6 The same operation as in Example 2 was carried out using nylon jersey as the material to be dyed. Substantially no dye was observed to come off during washing with water or high-temperature washing.

Example 7 Water-soluble polymer obtained from wool muslin in Reference Example 4
After padding with an aqueous solution containing 1.0%, 0.5% of "Snow Algin TSSL" and 0.5% of polyoxyethylene nonylphenol ether (20 moles of added ethylene oxide), pre-drying treatment was performed for 2 minutes at a squeezing rate of 100%.

Next, the pretreated fabric was printed in the same manner as in Example 1 using a printing paste with the following composition, dried at 100°C, steamed with saturated steam at 100°C for 30 minutes, washed with water, and printed with a clear blue pattern. Get the cloth.

<Printing paste prescription> “Verofix Blue GGL”
GGL, manufactured by Bayer) 30 parts Urea 50 parts Glycerin 50 parts "Senka Salt SP" (manufactured by Nippon Someka Co., Ltd.) 30 parts Locust bean gum glue (12%) 350 parts Sodium metanitrobenzenesulfonate 10 parts Water 480 parts Total 1000 In the obtained printed fabric, no dye was observed to come off at all during the above-mentioned water washing, and no dye was also observed to come off even after the same high-temperature washing treatment with "Senkanol CW" as in Example 1.

Example 8 A varnish consisting of 50 parts of rosin ester ("Ester Gum A", manufactured by Arakawa Chemical Industry Co., Ltd.) and 50 parts of toluene was applied to unbleached tissue paper (basis weight 30 g/m ² ) by gravure coating at 5 g/m ² Apply and dry. On top of that, a printing ink consisting of 10 parts of "Mikasion Brilliant Red 5BS" (manufactured by Nippon Kayaku Co., Ltd.), 25 parts of rosin-modified maleic acid resin, 40 parts of isopropyl alcohol, 23 parts of toluene, and 2 parts of surfactant was used. Print the picture pattern using the gravure method and create transfer paper.

Next, the printed surface of the transfer paper obtained above was superimposed on cotton knit that had been padded and dried in the same padding bath as used in Example 2 and pretreated.
10 kg/
cm ² and 5 m/min to transfer the printing ink from the transfer paper support onto the cotton knit to obtain a transfer cloth. The transfer cloth is steam-treated with 100° C. saturated steam for 20 minutes, and washed with 40-50° C. hot water containing 2 g of “Senkanol CW” for 10 minutes. Even after this washing, no dye was observed to come off at all.

In this way, a printed cloth with a bright red picture pattern transferred thereto which is deep in color and has good color fastness is obtained. Even when this product was further washed with water containing 2 g of "Senkanol CW" at 100°C for 20 minutes, no loss of dye was observed.

Example 9 A varnish consisting of 50 parts of rosin ester ("Ester Gum AAL", manufactured by Arakawa Chemical Industry Co., Ltd.) and 50 parts of toluene was applied at 5 g/m ² on a thin paper with a basis weight of 30 g/m ² by gravure coating. After drying, a picture pattern is printed thereon by a gravure method using the printing ink prepared in Example 8 to prepare transfer paper.

Next, 1.0% of the water-soluble polymer obtained in Reference Example 1,
Padded in a padding bath containing 2.0% polyethylene glycol (``PEG6000'', manufactured by Sanyo Chemical Co., Ltd.), 2.0% dextrin, and 0.5% polyoxyethylene nonylphenol ether (number of moles of ethylene oxide added: 20), and with a squeezing rate of 100%. A transfer cloth is obtained by transferring to cotton sateen that has been squeeze-dried and pretreated in the same manner as in Example 8 using the transfer paper prepared above. This was steamed for 20 minutes with saturated steam at 100℃, and 40~
Wash with hot water at 50℃ for 5 minutes. No loss of dye was observed during this washing.

In this way, a printed cloth with a red picture pattern transferred thereto which is clear, deep, and has good color fastness is obtained. Even when this product was subjected to the same high-temperature washing treatment as in Example 8, no dye was observed to come off.

Example 10 Pre-process silk habutae in the same manner using the transfer paper and pad bath used in Example 9, transfer the pattern onto it, and wash it with hot water after steaming to check for the dye to come off. To obtain a printed cloth with a red picture pattern transferred thereto, which is clear, deep in color and has good color fastness without any color. This product is made with water containing 2g of "Senkanol CW" at 100℃20
Even after washing for several minutes, no dye was observed to come off.

Example 11 The procedure of Example 9 was repeated except that nylon jersey was used as the transfer cloth.

The obtained transfer cloth was steam-treated with saturated steam at 100℃ for 20 minutes, and then washed for 5 minutes with hot water at 40-50℃ containing 2 g of "Senkanol CW". The amount of shedding was practically negligible.

In this way, a transferred nylon cloth with a red picture pattern which was brightly colored and had good color fastness was obtained. This product is made with water containing 2g of "Senkanol CW" at 100℃20
After washing for several minutes, no dye was observed to come off.

Example 12 A red pattern with good color fastness was produced in the same manner as in Example 9, except that wool muslin was used as the transfer cloth and the same bath as used in Example 3 was used as the pad bath. to obtain a wool muslin cloth with a transfer of . This one is "Senkanor CW"
The dye did not come off even after washing with water containing 2 g/ml at 100°C for 20 minutes.

Example 13 Transfer printing was carried out on cotton sateen in the same manner as in Example 9, except that each of the polymers obtained in Reference Examples 3 and 4 was used as the water-soluble polymer used in the pad bath. A printed fabric with a clear deep color and good color fastness similar to that of Example 9 was obtained. No loss of dye was observed in each fabric during the same low-temperature and high-temperature washing steps as in Example 9.

Example 14 Acrylic ^acid-
Acrylic ester copolymer (“Aron B-300”,
(manufactured by Toagosei Kagaku Co., Ltd.) was coated at 3 g/m ² using the gravure coating method and then dried. A glue consisting of 40 parts of white dextrin and 60 parts of water was applied thereon at 5 g/m ² and dried. Next, a picture pattern is printed thereon by a gravure method using the printing ink prepared in Example 8 to prepare a transfer paper.

Next, a silk habutae was padded in the same padding bath as used in Example 9, and the printed surface of the transfer paper was superimposed on the pretreated silk cloth without squeezing drying at a squeezing rate of 100%. The image is transferred by passing between heated rolls heated to 10° C. at a rate of 10 kg/cm ² and 5 m/min.
The resulting transfer cloth was steam-treated with 100°C saturated steam for 20 minutes, and washed with 30°C water containing 2 g of "Senkanol CW" for 5 minutes. No loss of dye was observed during this washing.

In this way, a printed fabric with a clear deep color and good color fastness is obtained. This one is "Senkanor CW" 2
Even after high-temperature washing treatment at 100° C. for 20 minutes with water containing 100 g/g/g, no loss of the dye was observed.

Example 15 Using cotton knit as the fabric to be dyed, the same operation as in Example 14 was carried out to obtain a printed fabric with clear density and good color fastness without any dye coming off when washed with water at 20°C for 5 minutes. obtain. Even when this product was subjected to the same high-temperature washing treatment as in Example 14, no loss of dye was observed.

Claims (1)

[Claims] 1. When printing cellulose fibers, protein fibers, and synthetic polyamide fibers using reactive dyes,
Prior to printing (a) General ceremony [In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. HX represents an organic or inorganic acid. ] A polymer consisting of repeating monomer units represented by the above general formula [ ] and (b) copolymerized with the repeating monomer units represented by the above general formula [] and the monomer blended in an amount up to 1/2 mole with respect to the monomer forming the unit. Copolymers consisting of units of possible other monomers. 2 Units of other copolymerizable monomers represented by the formula -SO ₂ - [], general formula [In the formula, R ₁ and R ₂ are the same as above. Y represents a halogen atom. ] The method according to claim 1, wherein the acrylic monomer unit is at least one selected from the group consisting of the following units and acrylic monomer units. 3. The method according to claim 1, wherein the pretreatment is performed by a padding method or a coating method. 4 Claim 1 in which the printing is performed by screen printing, roller printing, or wet transfer printing
The method described in section.