JP3214903B2 - Fiber bleach dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for bleaching and dyeing fibers.

[0002]

2. Description of the Related Art Cellulose fibers such as cotton, hemp, rayon, etc. are dyed using a chlorine-based or oxygen-based bleach such as sodium hypochlorite or hydrogen peroxide, after scouring to obtain sharpness. It is a common practice to remove the bleaching agent by reducing, neutralizing, or washing with water after exposing underneath, followed by dyeing. In this method, a great deal of time and energy is required for removing the bleaching agent and the bleaching agent and for the soaping step after dyeing with the reactive dye.

[0003]

Prior to dyeing with a dye, the fibers are scoured and bleached to obtain a bleaching effect, and the dyeing is performed in the same bath to simplify the process.
In order to shorten the process, a new method and a bleaching dye for fibers are required to make this possible.

[0004]

Means for Solving the Problems The present inventors have already found a bleaching agent capable of bleaching only the color consisting of impurities in fibers without destroying the dye, and have applied for a patent as a dye bleaching agent and a dye bleaching method. Furthermore, after bleaching, a method was found in which excess bleaching agent could be completely decomposed, and the dyes that could be used without the steps of withdrawing the bleaching solution and washing the bleaching agent were limited. No method was completed, and a method for dyeing in the same bath was completed and a patent application was filed (Japanese Patent Application No. 3-250).
218). However, in this method, it was found that there was a dye which had difficulty in color matching by one-bath dyeing from a greige machine. In other words, what is extracted from the fibers in the scouring process affects the dyeing, and depending on the dye, it is necessary to take a scouring solution to accurately match the color, and use this scouring solution to perform color matching. there were.

If the effects of the scouring solution can be eliminated without removing the heated scouring solution, bleaching and dyeing can be carried out in the same bath without limitation on the dyes that can be used, and as a result of intensive research, The present inventors have found that the objective can be achieved by washing the fiber once or several times with water before entering the process, and arrived at the present invention.

That is, the present invention comprises the following (1), (2) and (3). (1) When dyeing a natural fiber, the natural fiber is firstly washed one or more times with water, drained from the bath, scoured under heating, and without draining the bath, an organic compound represented by the following general formula (1). Bleaching with a bleach containing peracid or a salt or complex thereof or a mixture thereof as a main component, subsequently decomposing the bleach using a salt represented by the following general formula (2), and discharging the bath after bleaching A bleach dyeing method for fibers, characterized in that dyeing is performed successively without dyeing.

General formula (1)

Embedded image

(Where R is a substituted or unsubstituted alkyl group, allyl group or aralkyl group, and n is a natural number of 1 to 6.) General formula (2) R ¹ X (where R ¹ is a metal ion or X represents a substituted or unsubstituted quaternary ammonium group, and X represents a halogen ion.)

(2) The method for bleaching and dyeing fibers according to (1), wherein an acid or an acid anhydride is added during bleaching.

(3) The method for bleach-dyeing fibers according to (1) or (2), wherein the natural fibers are cellulose fibers alone or mixed with other fibers (blended, woven or knitted product).

The water washing in the present invention is carried out in the first time by adding an appropriate amount of a surfactant as necessary and usually without heating, and then adding water washing as necessary. The surfactant is used to increase the wettability of the fiber, and any of anionic, nonionic or mixed surfactants and amphoteric surfactants can be used. Washing may be performed under heating.

Specific examples of the organic peracid or its salt (metal salt or ammonium salt) represented by the general formula (1), which is a dye bleaching agent for fibers of the present invention, include formic acid, peracetic acid, perpropionic acid, Chloroacetic acid, pertrifluoroacetic acid, perbutyric acid, percaprylic acid, perlauric acid, disuccinic acid, diperglutaric acid, diperadipic acid, monopernonanedioic acid, dipernonanedioic acid, monoperdecane Diacid, diperdecandioic acid, monoperdodecandioic acid, diperdodecandioic acid, monoperoundecanoic acid, diperoundecanoic acid, diperphthalic acid, diperterephthalic acid, perbenzoic acid, m-chloro Perbenzoic acid,
2,4-dichloroperbenzoic acid, monoperphthalic acid, magnesium monoperphthalate, monopersuccinic acid, magnesium monopersuccinate, monopermaleic acid, calcium monopermaleate, monoperglutaric acid, monoperglutarate Magnesium acid, pertrimellitic acid, perpyromellitic acid and the like. Particularly preferred are magnesium monoperphthalate and diperdodecandioic acid.

The concentration of the bleaching agent in the bleaching bath is preferably 0.05 to 10% owf, particularly preferably 0.3 to 5% owf in terms of active oxygen content.

[0014] The pH in the bleaching step needs to be adjusted to an acidic side in order to make the bleach used effectively act on bleaching. The pH is preferably 1-7, particularly preferably 2-5.
It is. To adjust the pH, an acid or acid anhydride is used, but any water-soluble acid or acid anhydride can be used. For example, inorganic materials include sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. For organic, formic acid, acetic acid, acetic anhydride, propionic acid, butyric acid,
Isobutyric acid, oxalic acid, succinic acid, tartaric acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, adipic acid, citric acid, malic acid and the like are preferable, and acetic acid, maleic anhydride, malic acid and the like are preferable. The temperature of the bleaching bath is preferably from 20 to 110 ° C, particularly preferably from 40 to 95 ° C.
The bath ratio of the bleaching bath is 1: 5 to 1:50, preferably 1:10.
１ ： 1: 25.

The metal which becomes the metal ion of the salt of the formula (2) for decomposing the bleach is sodium, potassium, lithium, copper, aluminum, magnesium, calcium, zinc, barium, tin, iron, cobalt, nickel, etc. And
The substituted or unsubstituted quaternary ammonium group of the salt that decomposes the bleaching agent includes an ammonium group, a monomethyl ammonium group, a dimethyl ammonium group, a trimethyl ammonium group, a tetramethyl ammonium group, a monoethyl ammonium group, a diethyl ammonium group, and a triethyl ammonium group. And an ammonium group such as a monomethyltriethylammonium group and a tetraethylammonium group, and an ammonium group which may be substituted with a higher alkyl group, an allyl group or an aralkyl group. The halogen ion of the salt that decomposes the bleach is a fluorine ion, a chloride ion, a bromine ion or an iodine ion. The salt of a quaternary ammonium group and a halogen ion may be formed from a substituted or unsubstituted amine and a halogen acid. Particularly preferred salts are sodium chloride, potassium bromide, ammonium chloride and the like.

After bleaching, when the bleaching agent is decomposed in the bath,
The concentration of the salt used is usually from 0.05 to 10% by weight, preferably from 0.3 to 5% by weight.

In decomposing the bleaching agent, the temperature used is usually from 20 to 110 ° C, preferably from 40 to 95 ° C.

The natural fibers used in the present invention include cellulose fibers such as cotton and hemp, wool and silk, and cellulose fibers are preferred. Dyes applicable to the present invention include various commercially available dyes, and particularly preferred are reactive dyes. The amount used and the dyeing method are determined in accordance with the summary standards for those commercially available products. Examples of typical reactive dyes include:
Kayashion (Nippon Kayaku), Remazol (Hoechst), Procion (ICI), Daimira (Mitsubishi Kasei), Sermazol (Mitsui Toatsu Chemicals), Sumifix (Sumitomo Chemical), Cibacron (CIBA), Levafix (Bayer), Fixazole (Daito Chemical) and the like.

A metal ion sealant such as Kayachelator C-1000 (Nippon Kayaku Co., Ltd.) for suppressing the catalytic decomposition of the active ingredient of the bleaching agent by metal ions in the bleaching bath.
Manufactured), ethylenediaminetetraacetic acid or Diquest 201
0 (manufactured by Mitsubishi Monsanto Kasei Co., Ltd.) is usually 0 to 10 parts with respect to 1 part of the bleaching agent, and a diluent for improving handling, stability and safety, for example, water, organic solvent, celite or ultrafine particles Anhydrous silica is preferably used in an amount of 0 to 1 part of bleach.
100 parts can be included.

The bleaching agent and the salt for decomposing the bleaching agent of the present invention can be in any form such as a solution, a suspension, a paste or a powder depending on the dyeing method.

[0021]

According to the present invention, the bleaching agent disclosed in the present invention is used in the scouring / bleaching / dyeing process of natural fibers, especially cellulose fibers alone or mixed fibers with other fiber materials (synthetic fibers, etc.). If a salt for decomposing the acid anhydride and the bleaching agent is used, in the bleaching and dyeing of the fiber, first, scouring and bleaching in the same bath are performed first, followed by bleaching after bleaching to discharge or rinse by decomposing the bleaching agent. Dyeing can be carried out without the washing operation, and it is possible to obtain a dye bleaching effect equivalent to or higher than that of the usual method of dyeing after scouring and exposing underneath.

[0022]

The present invention will now be described in more detail with reference to the following Examples, which are for illustrative purposes only and do not limit the present invention.

First, in Example 1, the bleaching agent of the present invention was compared with hydrogen peroxide (Comparative Example 1-1) and sodium hypochlorite (Comparative Example 1-2), which are the most common bleaching agents. Was evaluated for its bleaching ability and its effect on dyeing.

In Example 2, an example using another kind of dye was shown. Examples of blending are shown in Examples 3 and 4.

Embodiment 1 The greige was first washed with an aqueous solution of 1 g / l Sunmol BH-21K (manufactured by Nichika Chemical Co., Ltd.), and then heated at 80 ° C. in a bath having the composition shown in Examples 1-1 to 4 shown below. Treated at the temperature for 20 minutes and scoured and bleached. Subsequently, without discharging the bath, 10 g / l of sodium chloride and 0.4 g / l of sodium carbonate were added, and the mixture was heated to 90 ° C. and treated for 20 minutes. Further, the temperature was lowered to 80 ° C. without draining the bath, and a dye and anhydrous sodium sulfate were added among the following dyeing agents, followed by treatment at the same temperature for 10 minutes. Subsequently, sodium carbonate was added and staining was performed at the same temperature for 1 hour. After dyeing, it was rinsed and then washed with 98 ° C soapy water for 15 minutes. The ratio of the fibers in the bath to the bleaching and dyeing baths is 1:15.

Kayashion Blue E-CM 2% o. w. f. Anhydrous sodium sulfate 100 g / l sodium carbonate 20 g / l

Example 1-1 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l (Metal ion sealant manufactured by Nippon Kayaku Co., Ltd.) 40 % Peracetic acid 2 g / l (commercial product: available oxygen 8.4%)

Example 1-2 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 27% diperdodecane diacid 2.3 g / l (Akzo Co., Ltd .: available oxygen 3.3%)

Embodiment 1-3

Example 1-4 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l Perbenzoic acid 1 g / l (commercial product: available oxygen 10. 5%)

Comparative Example 1 An undyed cotton cloth (hereinafter referred to as an undyed cloth) that has not been bleached after scouring is used in a bleach bath having the composition shown in Comparative Examples 1-1 and 1-2 under the same conditions as in Example 1. Bleached. Subsequently, the dyeing treatment was performed under the same conditions as in Example 1 using the same dyeing agent as in Example 1 without draining the bath.

Comparative Example 1-1 Sodium metasilicate 4 g / l Sodium carbonate 20 g / l Kayachelator C-1000 2 g / l 30% Hydrogen peroxide 2.7 g / l (commercial product: available oxygen 10.2% )

Comparative Example 1-2 12% sodium hypochlorite 0.9 g / l (commercial product: available chlorine 5.7%)

Comparative Example 2 The undyed cloth is bleached under the same conditions as in Example 1-2, and subsequently dyed under the same conditions as in Example 1 using the same dyeing agent as in Example 1 without performing salt treatment at 90 ° C. Processing was performed. (Japanese Patent Laid-Open No. 3-2
27451. )

Comparative Example 3 1g / l sun molding B
The scouring and bleaching were carried out under the same conditions as in Example 1-2 without washing with an H-21K aqueous solution. Subsequently, without discharging the bath, 10 g / l of sodium chloride and 0.4 g / l of sodium carbonate were added, and the mixture was heated to 90 ° C. and treated for 20 minutes. Further, the dyeing treatment was performed under the same conditions as in Example 1 using the same dyeing agent as in Example 1 without discharging the bath. (Japanese Patent Application 3-250
218. ) Clarity of dyed cloth against greige fabric or undyed cloth Bleachability Example 1-1 ○ ○ Example 1-2 ○ ○ Example 1-3 ○ ○ Example 1-4 ○ ○ Comparative Example 1-1 ○ × × Comparative Example 1-2 ○ × × Comparative Example 2 ○ ×× Comparative Example 3 ○ × Bleaching ability ○: Sufficient bleaching ability △: Insufficient bleaching ability ×: Almost no bleaching ability ××: No bleaching ability at all ：: practically usable △: slight discoloration ×: considerable discoloration XX: significant discoloration

Comparative Example 4 The undyed fabric was first treated and bleached in a bath having the following composition at a temperature of 80 ° C. for 20 minutes. Sodium metasilicate 4 g / l Sodium carbonate 20 g / l Kayachelator C-1000 2 g / l 30% hydrogen peroxide 2.7 g / l After bleaching, drain the bath and carefully rinse the bleaching cloth with cold water, Thereafter, treatment was carried out at a temperature of 80 ° C. for 10 minutes in a bath containing the dye and anhydrous sodium sulfate in the following dyeing chemical composition. Subsequently, sodium carbonate was added, and staining was performed at the same temperature for 1 hour.

Kayashion Blue E-CM 2% o. w. f. After dyeing, anhydrous sodium sulfate 100 g / l sodium carbonate 20 g / l was rinsed, and then washed with 98 ° C. soapy water for 15 minutes. The ratio of fiber to bleaching bath and dyeing bath was 1:15. The usual excellent dyeings are obtained.

Embodiment 2 FIG. First, the greige was washed with a 1 g / l aqueous solution of Sunmol BH-21K (manufactured by Nika Chemical Co., Ltd.), and then washed again with water.
-1 at a temperature of 80 ° C. in a bath having the composition shown in 1-3.
Minutes and bleached. Subsequently, 10 g / l of potassium bromide (KBr) was added without discharging the bath, the temperature was raised to 90 ° C., and the mixture was treated for 20 minutes. Subsequently, the temperature was raised to 60 ° C. without draining the bath, and the dyeing agent and anhydrous sodium sulfate were added to the next dyeing agent, followed by treatment at the same temperature for 10 minutes. Subsequently, crystalline trisodium phosphate was added and staining was performed at the same temperature for 1 hour.
After dyeing, it was carefully washed with water, dried in the shade and dried. The ratio of the fibers in the bath to the bleaching and dyeing baths is 1:15. Diamond Mira Turkey Blue G 2% o. w. f. Anhydrous sodium sulfate 50 g / l crystalline trisodium phosphate 20 g / l

Example 2-1 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 40% peracetic acid 2 g / l

Example 2-2 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 27% diperdodecane diacid 2.3 g / l

Example 2-3 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l H-48 15.6 g / l

Comparative Example 5 The undyed cloth was bleached in a bleach bath having the composition shown in Comparative Examples 5-1 and 5-2 under the same conditions as in Example 2. Subsequently, the dyeing treatment was performed under the same conditions as in Example 2 using the same dyeing agent as in Example 2 without draining the bath.

Comparative Example 5-1 Sodium metasilicate 4 g / l Sodium carbonate 20 g / l Kayachelator C-1000 2 g / l 30% hydrogen peroxide 2.7 g / l

Comparative Example 5-2 12% sodium hypochlorite 0.9 g / l Sharpness of dyed cloth against greige fabric or undyed cloth Bleachability Example 2-1 ○ ○ Example 2-2 ○ ○ Example 2-3 ○ ○ Comparative example 5-1 ○ ×× Comparative example 5-2 ○ ×× Bleaching ability ○: Sufficient bleaching ability △: Insufficient bleaching ability ×: Almost no bleaching ability ××: No bleaching ability at all Vivid Degree ○: Endurable for practical use △: Slight discoloration ×: considerable discoloration XX: significant discoloration

Example 3 A 50:50 blend of cotton and acrylic (hereinafter referred to as an acrylic blend) was first prepared with 1 g / l of Sunmole BH.
After washing with a -21K aqueous solution, only the acrylic portion was dyed in a bath having the following dyeing chemical composition at 98 ° C for 1 hour. Kayacryl Light Blue 4GSL-ED 1% o. w. f. Acetic acid 0.5 g / l

Next, the temperature was lowered to 80 ° C. without discharging the bath, and the mixture was treated in a bath having the composition shown in Examples 3-1 to 3 below at a temperature of 80 ° C. for 20 minutes to bleach. Subsequently, 10 g / l of sodium chloride was added without draining the bath, and 90 ° C.
And heated for 20 minutes. Subsequently, the temperature was lowered to 80 ° C. without draining the bath, and a dye and anhydrous sodium sulfate were added to the next dyeing agent, followed by treatment at the same temperature for 10 minutes. Subsequently, sodium carbonate was added and staining was performed at the same temperature for 1 hour. Kayashi On Turkey EA 1% o. w. f. Anhydrous sodium sulfate 100 g / l Sodium carbonate 20 g / l After dyeing, washing with water and then 80 g of Demol N 2 g / l
(A product of Kao Corporation) for 15 minutes. The ratio of the fibers in the bath to the bleaching and dyeing baths is 1:15.

Example 3-1 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 40% peracetic acid 2 g / l

Example 3-2 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 27% diperdodecane diacid 2.3 g / l

Example 3-3 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l H-48 15.6 g / l

Comparative Example 6 After scouring the acrylic mixed fabric, dyed with Kayacryl Light Blue 4GSL-ED in the same manner as in Example 3, and in a bleach bath having the composition shown in Comparative Examples 5-1 and 5-2, under the same conditions as in Example 3. Bleached. Subsequently, the dyeing treatment was performed under the same conditions as in Example 3 using the same dyeing agent as in Example 3 without draining the bath.

Comparative Example 6-1 Sodium metasilicate 4 g / l Sodium carbonate 20 g / l Kayachelator C-1000 2 g / l 30% hydrogen peroxide 2.7 g / l

Comparative Example 6-2 Sharpness of dyed cloth against 12% sodium hypochlorite 0.9 g / l blended cloth Bleaching ability Example 3-1 ○○ Example 3-2 ○ ○ Example 3-3 ○ ○ Comparative Example 6-1 ○ ×× Comparative Example 6-2 ○ ×× Bleaching ability ○: Sufficient bleaching ability △: Insufficient bleaching ability ×: Almost no bleaching ability ××: No bleaching ability at all Clarity ○: Durable for practical use △: Slight discoloration ×: considerable discoloration XX: significant discoloration

Embodiment 4 FIG. 50: 5 of cotton and polyester
No. 0 blended cloth (hereinafter referred to as polyester blended cloth) was washed with 1 g / l of an aqueous solution of Sunmol BH-21K, and then washed in a pressure-resistant container in a bath having the following dyeing agent composition.
Only the polyester part was dyed at 0 ° C. for 1 hour. Kayaceron Turkish E-GL 1% o. w. f. Acetic acid 0.45 g / l Sodium acetate (trihydrate) 0.55 g / l

Next, the temperature was lowered to 80 ° C. without discharging the bath, and the mixture was treated in a bath having the composition shown in Examples 4-1 to 3 below at a temperature of 80 ° C. for 20 minutes to bleach. Subsequently, 10 g / l of sodium chloride was added without draining the bath, and 90 ° C.
And heated for 20 minutes. Subsequently, the temperature was lowered to 80 ° C. without draining the bath, and a dye and anhydrous sodium sulfate were added to the next dyeing agent, followed by treatment at the same temperature for 10 minutes. Subsequently, sodium carbonate was added and staining was performed at the same temperature for 1 hour. Kayashi On Turkey EA 1% o. w. f. After dyeing with anhydrous sodium sulfate 100 g / l sodium carbonate 20 g / l, it was washed with water, and then washed with soap water at 98 ° C. for 15 minutes. The ratio of the fibers in the bath to the bleaching and dyeing baths was 1:
Fifteen.

Example 4-1 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 40% peracetic acid 2 g / l

Example 4-2 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l 27% diperdodecandioic acid 2.3 g / l

Example 4-3 Sunmol BH-21K 2 g / l Maleic anhydride 0.3 g / l Kayachelator C-1000 2 g / l H-48 15.6 g / l

Comparative Example 7 After scouring the polyester blended cloth, first in a pressure-resistant container, and in a bath having the following dyeing chemical composition:
Stained for 1 hour at 0 ° C. Kayaceron Turkish E-GL 1% o. w. f. Acetic acid 0.45 g / l Sodium acetate (trihydrate) 0.55 g / l Then, the temperature was lowered to 80 ° C. without discharging the bath, and the bleaching was carried out with the composition shown in Comparative Examples 6-1 and 6-2. Bleaching was performed in the bath under the same conditions as in Example 4. Using the same staining agent as in Example 4 without subsequently draining the bath,
Staining was performed under the same conditions as described above.

Comparative Example 7-1 Sodium metasilicate 4 g / l Sodium carbonate 20 g / l Kayachelator C-1000 2 g / l 30% hydrogen peroxide 2.7 g / l

Comparative Example 7-2 Sharpness of dyed cloth against 12% sodium hypochlorite 0.9 g / l blended cloth Bleaching ability Example 4-1 ○ ○ Example 4-2 ○ ○ Example 4-3 ○ ○ Comparative Example 7-1 ○ ×× Comparative Example 7-2 ○ ×× Bleaching ability ○: Sufficient bleaching ability △: Insufficient bleaching ability ×: Almost no bleaching ability ××: No bleaching ability at all Clarity ○: Durable for practical use △: Slight discoloration ×: considerable discoloration XX: significant discoloration

[0061]

The dye bleaching agent of the present invention is used, and the washing operation is performed only at the beginning to eliminate the discharging operation and / or washing conventionally required between the fiber scouring step and the bleaching step and the dyeing step. Can save water and heat for heating,
Time savings in cleaning and / or draining, improvements in water treatment, etc. can be obtained.

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06P 5/00

Claims (3)

(57) [Claims] When dyeing a natural fiber, the natural fiber is firstly washed one or more times with water, drained from the bath, scoured with heating, and expressed by the following general formula (1) without draining the bath. The bleaching agent is bleached with a bleach containing an organic peracid or a salt or complex thereof or a mixture thereof as a main component, and then the bleach is decomposed using a salt represented by the following general formula (2). A method for bleaching and dyeing fibers, wherein dyeing is performed successively without discharging. General formula (1) (However, R represents a substituted or unsubstituted alkyl group, allyl group or aralkyl group, and n represents a natural number of 1 to 6.) General formula (2) R ¹ X (where R ¹ is a metal ion or substituted or unsubstituted) X represents a substituted quaternary ammonium group, and X represents a halogen ion.) 2. The method according to claim 1, wherein an acid or an acid anhydride is added during bleaching. 3. The method according to claim 1, wherein the natural fiber is a cellulose fiber alone or a cellulose fiber mixed with other fibers.