JPS6035472B2 - Discharge printing paste composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel discharge printing paste composition that uses a combination of a plurality of specific reducing metal salts as a discharge printing agent, the main purpose of which is to provide an outstandingly stable discharge printing paste composition in any discharge printing method. The object of the present invention is to create a discharge printing paste that exhibits a discharge printing effect, a significantly strong discharge printing effect, and has excellent economic efficiency.

Conventionally, in the dyeing industry, discharge printing agents have been used to chemically decompose and decolorize many types of dyes, such as manganese dioxide, dichromate, cupric salt, molybdate, lead peroxide, Oxidizing agents such as ferric salts, ozone, persulfates, nitrates, chlorates, iodine, nitro compounds, anthraquinos, nitrites, etc., and stannous salts, hydrosulfite salts, rongalite, noipo Reducing agents such as , sulfur, acid sulfites, phosphites, hydrazine compounds, hydroquinone, thiourea dioxide, aldehydes, etc. are used.

However, oxidizing agents generally tend to make the cloth vertical, making them almost unsuitable for use as discharge printing agents, and are only used for fixing some reduction dyeing dyes. Therefore, reducing agents are often used as discharge printing agents, but among them, only a few are used in practice, such as sulfoxylic acid derivatives, stannous salts, and zinc powder.

These have good decolorizing properties after dye decomposition, and are particularly excellent in restoring the white color to cloth. In particular, it has an intermediate property between stannous salt, a sulfoxylic acid derivative that exhibits the strongest reducing power, and zinc powder, which has low reducing power but is economical, and the outline of the discharge printing pattern is generally sharp. Due to its unique characteristics, it has become the most commonly used textile printing process in recent years. There are many types of stannous salts, such as stannous chloride, stannous sulfate, stannous phosphate, and stannous organic acids, and these are mixed into the base paste to prepare discharge printing paste. However, no matter which stannous salt is used, the basic factor that exhibits the discharge effect is only the chemical content of stannous, and the binding group is only a regulating factor for the stannous ion concentration. Therefore, in order to increase the reducing power, it is necessary to incorporate a large amount of the stannous salt into the discharge printing paste. However, there are other problems such as the fact that stannous salts are extremely expensive.

Incidentally, trivalent titanium salts and divalent chromium salts are conceivable compounds that exhibit properties comparable to stannous salts as reducing agents, but these are extremely unstable in the air and are extremely expensive. It has little practical value. ．． In order to solve this problem, the present inventor has conducted various studies and found that any one of the salts of a specific metal with a low valence and which has high reducibility under all discharge printing conditions. A material that can coexist with one or more salts of a specific metal group with low valence and low reducing properties is extremely suitable as a discharge printing agent. The present invention was thus completed.

Next, the configuration of the present invention will be explained in detail.

The present invention provides a group consisting of a divalent chromium salt, a divalent tin salt, and a trivalent titanium salt (hereinafter referred to as the first group) in the base paste.

), and a group consisting of monovalent copper salts, divalent iron salts, divalent manganese salts, and trivalent antimony salts (hereinafter referred to as the 2nd group). 1 selected from
This is a discharge printing paste composition characterized by containing one or more salts as a reducing agent. The salts constituting the first group in the present invention are salts of a specific group of low-valent metals having high reducing properties, and among them, divalent chromium salts include monochromic chloride, monooxalic acid Examples of divalent tin salts include chromium, chromium trioxide, and chromium sulfate.
stannous chloride, stannous phosphate, stannous citrate, stannous Rodan,
Examples of the trivalent titanium salt include stannous tartrate, stannous aluminate, stannous hydroxide, stannous sulfite, stannous benzoate, sodium stannate, and tin monoxide. Examples include titanium oxide, titanium oxalate, potassium titanium oxalate, titanous titanium fluoride, potassium titanate oxalate, and the like.

In the present invention, the above substances are blended into the base glue in an aqueous solution or a dispersed state, but two or more types may be mixed.
They are selected depending on the discharge printing effect.

In addition, since these are generally unstable in air, for example, in the case of potassium titanite, the calculated amount of potassium titanate is mixed in the base paste in advance, and the calculator is heated and heated. The preferred method is to gradually introduce zinc powder into the base paste and convert it into titanite; in the case of stannous chloride, a method in which a small amount of metallic tin powder is mixed in; In the case of chromium salts, a method of producing them in an electrolytic state in a sealed container is preferred. Next, the second group of salts are salts of a specific metal group at a low valence and have low reducing properties, and specifically include monovalent copper salts, divalent iron salts, divalent iron salts, and divalent iron salts.
Firstly, monovalent copper salts include cuprous chloride, cuprous oxide, cuprous bromide, etc., and divalent iron salts include cuprous chloride, cuprous oxide, cuprous bromide, etc. , ferrous chloride,
Examples include potassium ferrocyanide, ferrous oxalate, ferrous ammonium sulfate, ferrous hydroxide, ferrous carbonate, ferrous ferrous oxide, etc., and divalent manganese salts include manganous chloride, sulfuric acid, etc. Manganous manganese, highly acidic manganese, etc. are mentioned, and 3
Examples of antimony salts include antimony trichloride and antimony sesquioxide.

All of these are produced when a salt of a specific metal group at a higher valence is reduced by the salts of the first group, and is changed to a lower valence that exhibits reducing properties, such as chloride. Ferrous iron has the property of being easily generated from ferric chloride and has reducing properties. However, the reducing action of the second group salts is slow, and when used alone, the discharge printing effect is extremely poor and does not lead to decolorization. One or more of these salts are mixed into the base paste in an aqueous solution or dispersed form, but like the first group of salts, some of them undergo some oxidation in the air, such as ferrous salts. In such cases, it is desirable to add a small amount of iron powder, aluminum powder, etc.

Alternatively, a ferrous salt may be blended into the base paste and converted to a ferrous salt in the base paste using a reducing agent such as sulfur dioxide gas while heating. In the present invention, the discharge printing paste is formed by mixing the salts of the first group and the second group, and the effects thereof are basically as follows.

{1' The stability of the first group in air is significantly increased by the combined use of the second group.

■ The reducing effects of both groups mutually exhibit their characteristics, eliminating waste in the decolorizing effect.

For example, the reducing action in a moated system of stannous chloride and ferrous chloride is shown by the following chemical formula.

SnC12...SnH→SnH+++2HoFeC
12. ...FeH→Fe+++Toka 0 Ho in the above formula contributes to reduction, while the reduction formula for the azo group and nitro group in the dye structure is shown below. The final product amine in the above formula is considered a colorless compound.

However, stannous salts make A, A' and B, 8, C completely possible, but in ferrous salts A is difficult and A' and below are easy. That is, if a small amount of stannous salt is present at the initial stage of reduction, ferrous salt is sufficient for the subsequent reduction, and has a characteristically strong effect on nitro groups. Therefore, as shown in the above chemical formula, the reduction reaction is quantitative, and there is no need to use large quantities of only high-molecular-weight and expensive ferrous salts, and ferrous salts can perform the reducing action extremely effectively. .

Moreover, as a result of the mixture of the two being simultaneously oxidized in the air, the loss of stannous salt is reduced and the efficacy is maintained for a long time. In the present invention, the salts of the first group and the second group are added to the base paste in this way, but the base paste includes starches, locust bean gums, and guar gum as thickeners used in ordinary dyeing. Examples include synthetic thickeners such as silica gums, cellulose derivatives, and polyvinyl methyl ether.

These are used alone or in a mixture in the form of an aqueous solution to prepare the discharge printing paste of the present invention. In addition to the above-mentioned reducing agent, the discharge printing paste of the present invention contains other reducing agents, metal salts, white pigments, extender pigments, pigments, photobrighteners, pH control agents, oil and fat surfactants, preservatives, It does not depart from the gist of the present invention even if ordinary dyeing agents such as resin agents, organic solvents, porous substances, etc. are blended.

As the discharge printing paste of the present invention, a mixture of stannous salt and ferrous salt is considered to be most advantageous because of its ease of availability.

In this case, the mixing ratio of both is arbitrary; if the pigment is light colored, the total amount may be small, and if the pigment is dark colored, the total amount may be increased, and the ferrous salt is increased compared to the stannous salt. It is sufficient to use a large amount of ferrous salt, which is used in large quantities and is extremely inexpensive.
In any case, the amount of expensive stannous salt can be significantly reduced. In order to perform discharge printing using the discharge printing paste of the present invention, the discharge printing paste of the present invention is applied to the ground cloth to be discharged by a known method in the following steps: printing, drying, heating or dry heat, washing, and then drying. A white or colored discharge print is obtained. In addition, when padding the cloth with the ground dyeing dye in an incompletely dyed state and printing the discharge printing paste of the present invention on the dried cloth to be discharge printed, or when applying the known ground dyeing dye to the cloth on which the discharge printing paste of the present invention is printed in advance, It can also be applied to the padding or overprinting method, and also to the sublimation transfer printing method, and the effect is the same as in the above case.
The target dischargeable dyes in the present invention are direct dyes,
Among acid dyes, metal-containing dyes, naphthol dyes, disperse dyes, organic pigments, etc., those with a so-called azo dye structure are particularly suitable and can be easily discharged. Can be used as any color.

Discharge-printed fabrics targeted by the present invention include woven and knitted fabrics of cotton, hemp, wool, rayon, acetate, nylon, polyacrylic, and polyester, mixed weaves, mixed knits, and blends thereof, as well as leather, synthetic leather, etc. Can be mentioned. Next, the effects of the present invention will be listed.

[11] The discharge printing agent in the discharge printing paste of the present invention significantly stabilizes the reducing action by using the second group salts which have the function of preventing oxidation of the first group salts in the air.

Therefore, the reducing power of divalent chromium salts and trivalent titanium salts, which were difficult to use alone, can be effectively utilized, and the effectiveness of divalent tin salts can be further enhanced. ■ Group 2 salts, which are one of the discharge printing agents in the discharge printing paste of the present invention, have a slow reducing action and a slow reduction rate, but in addition to the reducing action of Group 1 salts, their synergistic effect allows them to develop other colors. As a result of characteristically decomposing the base and adjusting the reduction effect, unlike the conventional discharge printing effect made only of Group 1 salts, there is no problem such as the tatami phenomenon on the base dye and "burning" of the discharge print area. Suppresses reducibility and eliminates waste in reducing action.

Legs The first group salts in the discharge printing paste of the present invention are useful only in the initial stage of reduction, and the amount of salts added can be significantly reduced.In fact, the discharge printing effect becomes even stronger when a large amount of second group salts are added. There is no negative effect on the area around the discharge printing pattern.

[4} A divalent iron salt as a discharge printing agent in the discharge printing paste of the present invention; 2.
The valent manganese salt and the trivalent antimony salt are very economically advantageous, and the monovalent steel salt can particularly greatly utilize the chelating action of the divalent steel salt after the reducing action has been exerted.

Legs The discharge printing paste of the present invention can further effectively control the reducing action by adding an acid, an acid generator, an alkali, or an alkali generator to the paste. It is also possible to use a staining agent in combination.

Finally, the performance of the discharge printing paste of the present invention and the conventional discharge printing paste is compared as follows.

Table 1 Discharge dyeing paste of the present invention 〇 〇 〇 〇 Sulfoxylate ◎ × × △ Discharge dyeing paste made of tin salt discharge dyeing fabric 〇 〇 △ × Zinc powder discharge dyeing paste × 〇 〇 〇Gonou, The evaluation indicates superiority or inferiority in the order of ◎, ○, △, and ×.

Example 1 Yuzen paste 65 parts by weight (hereinafter, parts by weight are abbreviated as parts).

), 2 parts of stannous chloride and 7 parts of ferrous oxalate, 26 parts of water
A white discharge printing paste was obtained. Next, the dispersion beam material Dianics Fast Orange B Conc (trade name) 1% (
The above discharge printing paste is printed in a striped pattern on a ground-dyed acetate satin fabric (based on the weight of the fabric) using the screen printing method, dried,
Next, a steam treatment was performed at 100 to 105 qo for 20 minutes, followed by water washing, acid washing, reduction washing, and drying. In this way, an acetate satin woven cloth was obtained which exhibited a clear white discharge-printed cotton pattern on the clear-colored base beam.

For comparison, 2 parts of stannous chloride and 7 parts of ferrous oxalate blended in the above discharge printing paste were mixed with 9 parts of stannous chloride,'
. ) 2 parts of stannous chloride, 7 parts of water, 2 parts of stannous chloride,
Prepare a discharge printing paste that can be replaced with 2 parts of oxalic acid, 5 parts of water, and 9 parts of ferrous ironate, perform discharge printing in the same manner, and compare the results with the results of the discharge printing paste of this example. For example, Table 2
It is as follows. Table 2 Word King, the evaluations in the table are Excellent, Good, Fair,
Indicate superiority or inferiority by rank of not acceptable.

(The same applies hereinafter.) Example 2 1 part of ammonium sulfate was added to 87 parts of Mapro Gum NP (trade name) 6% base glue, followed by 3 parts of stannous chloride, 2 parts of titanium chloride, and 5 parts of ferrous chloride. 1 part and 2 parts of diethylene glycol were mixed to obtain a white discharge printing paste.

This is printed on a polyester knitted fabric using roller printing in a polka dot pattern, dried, and then the cloth is coated with an overprint base paste consisting of 5% of the disperse dye Miketone Polyester Discharge Plue R (trade name). The print was printed so as to cover the surface, and after drying, high-pressure steaming was performed at 130 qo for 20 minutes, followed by washing with water, reduction cleaning, and drying. In this way, a polyester knitted fabric was obtained which exhibited a clear white discharge-printed polka dot pattern on a dark tone background. For comparison, discharge printing pastes were prepared by changing the amount of the discharge printing agent 1 in the above-mentioned discharge printing paste as follows.

...5 parts of stannous chloride and 5 parts of stannous titanium chloride.

{o- 3 parts of stannous chloride and 2 parts of titanium chloride, and ferrous chloride in the examples was replaced with water.

1.1 Ferrous Chloride will be anchored.

Perform discharge printing in the same manner as in the example using the above discharge printing paste,
Comparing these results with the results of the discharge printing of this example,
It is as shown in Table 3.

Table 3 Example 3 The discharge printing agent in the discharge printing paste of Example 2 was changed as follows, and the same discharge printing process as in Example 2 was eliminated. As a result, as shown in Table 4,
Satisfactory results were obtained in all cases except for 'IJ).

(I) 3 parts of stannous chloride, 2 parts of chromous chloride, and 5 parts of ferrous oxalate.

(〇｝2 parts of stannous chloride, 1 part of titanium chloride, and 7 parts of manganese oxalate.

5 parts of titanium oxalate, 5 parts of ferrous chloride.

(2) 6 parts ferrous phosphate, 4 parts antimony trichloride.
6 parts of stannous chloride, 4 parts of ferrocyanide. N
5 parts stannous sulfite, 5 parts ferrous hydroxide.

{t} 4 parts of sodium stannite, 2 parts of cuprous oxide, 4 parts of manganese carbonate. Mix 6 parts of ferrous chloride with 6 parts of ferric chloride and 2 parts of zinc powder, and 4 parts of stannous sulfate.

t'J} 5 parts of stannous chloride, 5 parts of ferric chloride.

In addition, as a comparison ratio, the case where only 10 parts of (l) stannous chloride was added is added. Table 4 Example 4 10% hydroxyethyl cellulose base glue 38 parts, 20%
3 parts of stannous chloride and 4 parts of zinc chloride are uniformly mixed with 38 parts of lame crystal gum base paste, and 6 parts of acidic sodium oxalate is added while reducing the loss to add stannous oxalate to the paste. generated-
Further, 2 parts of urea, 3 parts of acid clay, 2 parts of activated carbon, and 4 parts of ferrous oxalate were mixed to obtain a discharge printing paste.

Next is Exlanmos fabric (product name), which is a complete acrylic weave.
A small flower pattern is printed using a rotary screen, followed by Eisencatelon Marine Flu GRL, a cationic dye.
A color paste containing 5% H (trade name) was printed so as to cover the entire surface of the discharge printing lake, and after drying, it was steamed at 10500℃ for 20 minutes.
Washed with water, acid washed, and dried. In this way, an acrylic printing method was obtained that successfully produced a clear and sharp white discharge dyed floret pattern on a dark-tone ground.

For comparison, a white discharge-printed cloth could not be obtained using the same discharge-printing paste in which ferrous oxalate was replaced with water.

Example 5 In the printing process of Example 4, if the base dye base dye paste is padded onto the cloth in advance and dried, the same discharge paste is applied in the same manner, and the same operation is carried out, almost the same advantages are obtained. The discharge printing results were obtained.

Example 6 The same process as in Example 2 was applied in a colored discharge dyeing lake consisting of 98 parts of the discharge paste of Example 2, 1 part of Karon Polyester Yellow 6GSF (trade name), and 1 part of water. A colored discharge-printed polyester cloth with a sharp yellow polka dot pattern on the ground was obtained.

Example 7 Polyacrylic acid ester emulsion (solid content 38%) 2$, 5% hydroxyethyl cellulose 5
part, Mineral Turben 35 parts, Vissurf #1400 (
(Product name, emulsifier) 2 parts, ammonium sulfite 2 parts, stearic acid powder 5 parts, water 14 parts, and Neo Color Yellow M3
Sufficiently emulsify 5 parts of 0 (trade name, pigment), and further,
5 parts of Shushun stannous powder, 5 parts of sodium meta-anathimonite powder, and 2 parts of formalin were added to obtain a colored discharge printing paste.

The discharge printing paste was dyed with Dianic Thread R-S, which is a disperse dye.
E (product name) and Procion Brilliant Red Day 7B
Printed on a polyester/cotton blend broadcloth (65:35 efficiency) ground-dyed red with (reactive dye, trade name) using a rat autoscreen printing machine with a screen plate with a random lattice pattern, and dried. , 6000, 10 in a high temperature steamer
It was treated for 1 minute, then washed with water, washed with alkali, soaped, and dried.

In this way, an excellent colored discharge-printed blended fabric with a clear yellow irregular lattice pattern on a red background was obtained. As a comparative example, the sodium metaantimonite blended in the discharge printing paste of this example was replaced with sodium aluminate powder and stannous phosphate powder and the same treatment was carried out, but in the former case, the discharge printing was insufficient and the light color was A colored discharge printing pattern was obtained, but in the latter case, a sharp colored discharge printing pattern was obtained.

Reference Example In addition to the metal salts in the discharge printing paste of the present invention, examples of other metal salts include molybdenum, tungsten, vanadine,
Similar effects were observed when testing low-valent salts such as thallium, cerium, and cobalt, but the materials are expensive and it is generally considered unnecessary to coexist in small amounts in the discharge dyeing lake of the present invention. Considering the economic efficiency, it was unsatisfactory.

Claims (1)

[Claims] 1. In the base paste, one or more salts selected from the group consisting of divalent chromium salts, divalent tin salts, and trivalent titanium salts, and monovalent copper One or two selected from the group consisting of salt, divalent iron salt, divalent manganese salt, and trivalent antimony salt
A discharge printing paste composition comprising at least one type of salt as a reducing agent. 2. The discharge printing paste composition according to claim 1, which contains a stannous salt and a ferrous salt as reducing agents in the base paste.