JPS61502065A - Method for improving the oxidation method of sulfur dyes - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Kyoto 2 of 2 The present invention relates to an improved method for oxidizing and fixing sulfur dyes or vat dyes. do.

After dyeing with sulfur dyes or vat dyes, oxidation can be carried out using various oxidizing agents. is known. Among the oxidizing agents, the most widely used oxidizing agents are, for example: 2, which are listed below. - alkali metal chromates or dichromates, - bromides, chlorides or iodides halogen-containing compounds of alkali metals, such as Hydrogen monoperoxide.

However, the use of chromates or dichromates means that these salts contaminate wastewater considerably. Additionally, these compounds can significantly alter the brightness of certain colors. It can also reduce the hydrophilicity of fibers.

In particular, the use of halogen-containing derivatives in the presence of alkali metal vanadates is often However, these compounds may be used in certain devices such as jiggers. It is known that it is difficult to use in some cases.

Although the use of hydrogen peroxide is effective in alkaline media, it nevertheless The disadvantage is that many dyes are excessively oxidized.

Not all dyes can be oxidized when using hydrogen peroxide in acid media .

Certain metals can activate the decomposition of dilute aqueous hydrogen peroxide solutions, and acidic pH It is known that hydrogen peroxide can speed up the rate of oxidation in the area 0 For example, using iron, nickel, and copper salts such as copper sulfate can reduce hydrogen peroxide Decomposition can be significantly activated. However, the above performed in the presence of copper salts Such oxidation significantly changes the various colors.

On the other hand, the use of vanadate in hydrogen peroxide is oxidized by hydrogen peroxide oxidizing solution. It doesn't increase the speed enough.

In contrast, the present applicant has oxidized sulfuric acid steel in the presence of metal salts in hydrogen peroxide. The amount is insufficient to increase speed and is insufficient to produce various colors. If a small amount of vanadate is present and at the same time a small amount of vanadate is present in the bath, the brightness will change. It has been experimentally found that all dyes are easily oxidized without oxidation.

Separately the same amount of steel sulfate or vanadate can be used to make all these different dyes. It does not oxidize as quickly as when used simultaneously; , if vanadate and metal salt are used simultaneously in the presence of hydrogen peroxide, All sulfur dyes are rapidly oxidized regardless of the dyeing method or equipment used.

Therefore, the present invention provides an oxidation method for sulfur dyes or vat dyes that overcomes the various drawbacks mentioned above. Regarding the method, the present invention is characterized in that a small amount of alkali metal vanadate and metal salt are present simultaneously. It consists in using a hydrogen peroxide solution.

The oxidation is carried out in a relatively acidic medium in the pH range 3-6 at 20-95°C, preferably at 40°C. It is carried out at a temperature of ~60°C.

Various compounds of copper, iron, nickel, cobalt or manganese are used as metal salts. can be used. However, the present invention does not require the use of copper salts such as copper sulfate. is preferable.

Vanadate consists of alkali metal vanadate and ammonium vanadate You can choose from the family.

The required amount of hydrogen peroxide in the present invention is 0.1 to 30 g per oxidation bath 11, preferably is 1 to 5 g.

The amount of vanadate is 0.05-0.51 per 11 oxidation baths! , preferably 0.1~ It is 0.2g.

The amount of selected metal salt can vary from 0.01 to 1 g per oxidation bath 11. For example, it is preferable to use 0.05 to 0.1 g of sulfuric acid steel per oxidation bath 11. It is.

According to the present invention, all sulfur dyes or vat dyes can be dyed with dyeing methods, equipment for using them and It can be oxidized regardless of the nature of the fiber being dyed.

The examples described below illustrate the advantages offered by the present invention, without including any limitations. can be explained. In the example described below, color index No. , Sulfur Red No. 1 corresponding to 53228 Use 0. This dye is one of the substances that is difficult to oxidize; provide the most difficult obstacles.

泗---”nee Sulfur Red No. 10% bleached cotton woven fabric.

10 (proportions are expressed relative to the weight of the fiber), as described below. Use a dye bath with proportions: dye 10% Sodium sulfide 10% Sodium chloride 10% A bath ratio of weight of fiber/volume of dyeing bath of 1/10 is used.

Dyeing is carried out at a temperature of 95°C for 1 hour; after dyeing, the fabric is soaked in hot and then cold water. Divide the sample into three sections and add the stain on each of these sections. The samples were then oxidized separately by the procedure described below: A. % concentration of hydrogen peroxide with a solution containing 2 g per 11% and ioam acetate. Ta.

Oxidation is carried out at a temperature of 50° C. for 15 seconds.

B. For the second section of the sample, an additional 0.2y/1 sodium vanadate was added to the oxidation bath. The same conditions as in A were used except that In the third section of the C1 sample, according to the present invention, 30% concentration sodium chlorite 2g/l and sodium vanadate 0 ．． The same conditions were used except that 2y/l was added to the oxidation bath.

The results are listed below: Trial A"B: 4 oxidation is very slow and clearly insufficient and the dye is not oxidized.

Trial Lg conversion is rapidly completed.

Medicine---j'' engineering Staining was carried out in the same manner as in Example 1. After staining and rinsing, the sample is divided into four sections viz. Divide into A, B, C, and D, and dye each of these sections in the baths described below. More oxidized: 12 g/l') acetic acid at 30% concentration Hz Oz 10cc/l 111 Color-2y/e (7) 30% Concentration Ht O210ee/1 acetic acid 0.05tt/1 copper sulfate N L distance between two animals -2y/h7>30% concentration H20z10cc/j! of acetic acid 0.1y/1 sodium vanadate Acetic acid at 30% concentration H*0210cc/Il of 12g/1 to glare 0.05971 copper sulfate 0.1y/l sodium vanadate For all of these baths, a temperature of 50°C using the following conditions: -1/20 bath ratio (fiber weight/bath volume ratio) oxidation rate for baths A, B and C. It has been observed that the oxidation of the dye is insufficient, e.g. even after 30 seconds of treatment. cannot be obtained.

In contrast, the oxidation achieved in a bath is very rapid; in fact, in this case Complete oxidation is observed after 10 seconds of treatment; It is observed that it does not undergo any changes.

3: Using the above conditions again. Three separate sections of dyed and rinsed fibers The oxidation is carried out using the baths described below, respectively: A) 30% concentration H2O2 of 2y/1 10ee/j! of acetic acid B) 30% concentration Ht Ot of 2y/l 10ee/1 acetic acid 0.051F/l' copper sulfate C) 30% concentration H20° of 21/1 10cc/f acetic acid 0.2y/N sulfuric acid steel After treatment, the oxidation achieved with baths A and B is clearly insufficient. What is this? In contrast, the oxidation achieved in bath C is clearly faster, but in the latter case the dye In this example, the material peels off and takes on a bluish tinge, which is no longer consistent with the specifications of the dye used. Remember, there is no vanadate in the bath composition.

Example – 4 knees Dyeing is carried out on a jigger using a 10% strength dye.

After dyeing, oxidation is carried out under conditions compared below.

A. Rinse by passing through cold water twice with a jigger.

8.3y/h7) 30% concentration H202 10cc/4! of acetic acid 0.1y/l copper sulfate 0.1y/l sodium vanadate Oxidize on a jigger using.

Pass through the jigger twice at 50°C. Rapid and complete treatment of all dyed materials oxidation is observed.

CO oxidation was carried out in a bath in the absence of hydrogen peroxide, i.e. 30% concentration of sodium chlorite at 3y/l. Sodium vanadate with thorium 0.2y/l 10cc/1 acetic acid Similar conditions are used except that a bath containing .

In this case, oxidation of the dyed material is clearly visible regardless of the number of passes through the oxidation bath. It is incomplete.

The above example shows that hydrogen peroxide, metal salt and alkali metal vanadate are simultaneously oxidized. It explains the effect when it exists.

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Claims (13)

[Claims] 1. In a method for oxidizing sulfur dyes or vat dyes in the presence of hydrogen peroxide solution , hydrogen peroxide solution is activated by the combined action of metal salts and alkali metal vanadates. of sulfur dyes or vat dyes in the presence of a hydrogen peroxide solution characterized by Oxidation method. 2. The metal salt can be selected from various salts of iron, copper, nickel and manganese. 2. The method as claimed in claim 1, wherein it is preferred to use copper salts. 3. Vanadate from alkali metal vanadate and ammonium vanadate 3. The method according to claim 1 or 2, wherein the method is selected from the group consisting of: 4. From claim 1, wherein the amount of metal salt is from 0.01 to 1 g per liter of oxidizing bath. The method described in any one of paragraphs up to paragraph 3. 5. Claim 4, wherein the amount of metal salt is 0.05 to 0.1 g per liter of oxidizing bath. Method described. 6. Claims in which the amount of vanadate is 0.05 to 0.5 g per liter of oxidation bath. The method according to any one of paragraphs 1 to 5. 7. Claim 1, wherein the amount of vanadate is 0.1 to 0.2 g per liter of oxidation bath. The method described in Section 6. 8. Claim 1, wherein the amount of hydrogen peroxide is 0.1 to 30 g per liter of oxidation bath. The method according to any one of paragraphs 7 to 7. 9. Claim 7, wherein the amount of hydrogen peroxide is 1 to 5 g per liter of oxidizing bath. the method of 10. Claims 1 to 9, wherein the oxidation is carried out in an acidic medium with a pH range of 3 to 6. The method described in any one of the preceding paragraphs. 11. Claims 1 to 10, wherein the oxidation is carried out at a temperature of 20 to 95°C. The method described in any one of the above. 12. 12. A process according to claim 11, wherein the oxidation is carried out at a temperature of 40 to 60<0>C. 13. The dye is Sulfur Red No. Claims 1 to 12 which are 10 The method described in any one of the preceding paragraphs.