JPH0340870A - Treating of various fiber - Google Patents

Abstract

PURPOSE:To uniformly and efficiently treat various fibers by continuously decreasing pH of treating solution treating (e.g. dyeing) said fibers with adding sulfonate derived from vicinal diol compound, etc., to said solution. CONSTITUTION:For instance, a sulfonate derived from a vicinal diol compound expressed by the formula (R1 is alkyl or phenyl, etc.; R2 is alkyl derivative, etc.) or polyol compound is added to treating solution for treatment such as general dyeing of various fibers, or one-bath dyeing or one-bath scouring of mixed woven fabric or combined woven fabric in an amount of 0.5-50g/l to gradually and continuously decreasing pH of said treating bath from 5-13 at initial to 3-8 at finishing of treating process in a treating process of various fibers such as dyeing, or one-bath dyeing of various mixed spinning, combined weaving or combined woven fabric making possible to dye various fibers more uniformly and more efficiently than conventional method.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Fields The present invention provides a method for treating various types of fibers by lowering or maintaining the pH using acids liberated under the treatment conditions. It relates to a method for efficiently performing processing.

(b) Prior Art In the conventional method, when a certain wt fiber is subjected to several treatments, it is usual to treat each treatment in a different treatment bath and in a different p I-1 region. In other words, scouring agents, leveling agents, various dyes, etc. commonly used in treatments such as scouring and dyeing have a unique p I-1 region where they can most efficiently demonstrate their original performance. If you try to perform many treatments in the same bath at the same time, the performance of each treatment agent will not be fully demonstrated, resulting in uneven and insufficient effects.
However, with the recent trend towards rationalization and energy saving,
There is a strong demand for a method that can perform these treatments simultaneously in the same bath, sufficiently uniformly, and efficiently.

(C) Problems to be solved by the invention Recently, a method using a pH-maintaining compound in a one-bath dyeing method has been developed.
JP-A-62-69889) has been attempted, but these compounds are an addition reaction of sulfonate salts to shrimp halohydrin, and this adduct does not eliminate the sulfone group even when hydrolyzed, and p I-(Since dehydrohalogenation is used as a retention effect, corrosion of equipment etc. becomes a problem, so it cannot be said to be a preferable compound.

(d) Means for Solving the Problems The present invention, as a result of repeated research in consideration of the shortcomings of the prior art, has been developed to improve the dyeing of various fibers, bath scouring dyeing, and blending, interweaving, or interlacing of fabrics. It is an object of the present invention to provide a method in which the functions of processing agents used in these treatments can be fully and efficiently exerted when performing various treatments such as dyeing, and uniform treatments can be performed.

The method of the present invention allows allylsulfonic acid and alkylsulfonic acid or their derivatives to be extracted from a vicinal diol compound, a polyol compound, or an epoxy compound when treating various fibers with a treatment liquid containing one or more types of treatment agents. This is a method for treating each of the fibers of the present invention, which is characterized in that a derived sulfonic acid ester, that is, a compound represented by the following structural formula (1), is added to the treatment solution as an esterifying agent.

RISO20-CH2Cl-1-R2(I)
○■4 (However, (I>R2 in the formula represents an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, and (I>R2 in the formula represents various alkyl derivatives or various alkyl-substituted phenyl derivatives. , ) That is, in the present invention, the above (
I) Utilizing the fact that an ester compound having the basic skeleton represented by the formula releases acids represented by R, So, and H by hydrolysis, and by adding at least one of these compounds to the treatment liquid. The pH of the treatment liquid is lowered or kept constant, and one or more treatments can be carried out simultaneously and uniformly and efficiently in the same bath.

A method for treating each fffl fiber using the method of the present invention will be specifically described below.

<1>゛The method of gradually lowering the pH of the treatment solution is to use synthetic polyamide 41! It is effective when dyeing fibers and natural polyamide fibers with acid dyes. Dyeing with acidic dyes largely depends on the p I-1 of the dyeing bath, and the lower the p I-1, the better the dyeing. Therefore, the method of adding acid in advance at the beginning of dyeing, or adding acid during or at the end of dyeing,
There is a high possibility that the dye stains rapidly from the beginning of dyeing or from the time when acid is added, resulting in staining spots.Therefore, the above ester compound is added to the dyeing bath at the beginning or during the dyeing process. By gradually lowering the p I-1 from weakly alkaline to acidic, it becomes possible to rationally control the rate of dyeing of synthetic and natural polyamide fibers with acidic dyes.

(2) The method of gradually lowering the pH of the treatment solution is effective for one-bath dyeing of blended, interwoven, or interwoven fabrics. For example, for blended, interwoven, or interwoven fabrics of synthetic or natural polyamide fiber and cellulose fiber. When acid dyes and direct dyes or reactive dyes are treated in the same bath, by adding the above ester compound to the dyeing bath, p I-1 of the treatment bath can be
Direct dyes or reactive dyes dye cellulose fibers while the temperature ranges from alkaline to neutral, and as the temperature rises and the temperature drops from neutral to acidic, acidic dyes dye the polyamide fibers. Therefore, the staining of polyamide fibers by direct dyes or reactive dyes and the staining of cellulose fibers by acid dyes are reduced, so this is a very effective method especially when dyeing different colors.

<3> The method of gradually lowering the pH of the treatment liquid is effective, for example, for one-bath scouring dyeing of various fibers.

Generally, the scouring effect is exhibited under alkaline conditions, but if the dye is treated under alkaline conditions until the end of the dyeing process, it may adversely affect the dyeability, such as hydrolysis of the dye or a decrease in the dye exhaustion rate. However, by adding the above-mentioned ester compound to the treatment solution, a scouring effect is exerted between room temperature and about 90°C, when the pH of the treatment solution ranges from alkaline to neutral, and at higher temperatures, the pH increases. Since it is reduced from neutral to acidic, hydrolysis of the dye is also suppressed, and together with the scouring effect, good dyeability can be obtained without reducing the exhaust rate.

In the case of examples (1> to (3)), the rate of decrease in the pH of the treatment bath,
The accuracy of maintaining pH is determined by the type of compound added and its amount used, the type of fiber to be treated, the treatment method, the type and amount of treatment agent, and the temperature and temperature increase rate of the treatment bath. It is.

Typical examples of vicinal diol compounds used in the present invention include ethylene glycol, propylene glycol, or derivatives thereof; typical examples of polyol compounds include glycerin, $i compounds, or derivatives thereof; and epoxy compounds. Typical examples include glycidol, ethylene oxide, propylene oxide, and bunacols (Nagase Chemical Industries, Ltd.).

Furthermore, representative examples of the esterifying agent include para-toluenesulfonic acid, para-toluenesulfonyl chloride, methanesulfonyl chloride, and the like.

Among these esters obtained by the reaction of alcohols and acids, compounds obtained by the reaction of glycols and allylsulfonyl halide or alkylsulfonyl halide are obtained by the reaction of epoxy compounds with allylsulfonic acid or alkylsulfonic acid. These are the compounds corresponding to the obtained compounds. Among these ester compounds, it is particularly preferable to use ethylene glycol, or a compound obtained from glycerin or glycidol and para-toluenesulfonic acid, and these compounds do not contain halogen elements or metals.

The method of the present invention can be applied to treatments such as general dyeing, blending, interweaving, or interweaving, such as single-bath dyeing and -bath scouring dyeing. It can be used even if it contains one or more dyes, scouring agents, etc. In other words, general dyes such as disperse dyes, basic dyes, reactive dyes, direct dyes, and fluorescent dyes can be used. In addition, in order to adjust the initial pH of the treatment solution, alkaline agents, acidic agents, and their buffers may be used. Examples of alkaline agents used include sodium hydroxide, sodium carbonate, and tertiary sodium phosphate. For example, alkali metal acid salts such as alkali metal salts, or alkali metal lower carboxylate salts such as sodium acetate can be used. Further, as the acidic agent, inorganic acids such as sulfuric acid, organic carboxylic acids such as formic acid, acetic acid, oxalic acid, etc. can be used. Ammonium sulfate, ammonium acetate, etc. can be used as a buffering agent together with these.

The amount of the ester compound used in the present invention is determined by the treatment method, the type of fiber to be treated, the alkaline agent, acidic agent, WL street agent, etc. used in combination, and therefore depends on the desired pH condition. Although it has to be determined empirically, it can be used in the shell in an amount of about 0.05 to 50 g/l, preferably about 0.1 to 20 g/l.

In the method of the present invention, the treatment conditions are set so that the pH of the treatment solution changes from 5 to 13 at the beginning of the treatment process to 3 to 8 at the end or during the treatment process due to the addition of the ester compound. preferable.

The above-mentioned ester compound in the present invention may be added in batches, divided into portions, or continuously, and the timing of addition is not particularly limited, and may be added from the start of the treatment process. Any time before the end is fine.

The treatment temperature and treatment time in the method of the present invention are from 20 DEG C. to 140 DEG C. for 30 minutes to 2 hours.

The fibers to which the method of the present invention can be applied are synthetic fibers or natural fibers, and may also be blended, interwoven, or interwoven fabrics thereof, and may be in any form such as yarn, woven fabric, knitted fabric, nonwoven fabric, etc. .

Next, a synthesis example of the above ester compound will be shown below.

(Synthesis Example 1) 200 parts of isopropyl alcohol and 172 parts of para-toluenesulfonic acid were charged in a reaction vessel, and 111 parts of glycidol was added dropwise at about 50°C and reacted for 2 hours. After completion of the reaction, the target product was obtained by distillation under reduced pressure. Ta. This product (A) was clearly dissolved in water.

(Synthesis Example 2) 186 parts of ethylene glycol and 190 parts of para-toluenesulfonyl chloride were charged into a reaction vessel, and the system was heated to 40°C.
124 parts of a 50% caustic potassium aqueous solution was added dropwise while maintaining the temperature. After the reaction was completed for 3 hours, the reaction product was filtered, and the solution was distilled under reduced pressure to obtain the desired product. This product (B) is clearly soluble in water.

(Synthesis Example 3) 152 parts of propylene glycol and 114 parts of methanesulfonyl chloride were placed in a reaction vessel, and while the system was maintained at 40°C, 79 parts of pyridine was added dropwise, and the mixture was reacted for 3 hours.
After the reaction was completed, the reaction product was filtered, and the soybean liquor was distilled under reduced pressure to obtain the desired product. This product (C) is clearly soluble in water.

(e) Examples Next, examples of the method of the present invention are shown below. However, the method of the present invention is not limited to those shown below, and the above ester compound ( The compounds used in the following examples are as follows.

Decomposition acid A Para-toluenesulfonic acid ester of glycidol B Para-toluenesulfonic acid ester of ethylene glycol C Methanesulfonic acid ester of propylene glycol The dyeing property of the dyed product obtained in the following example is a slow dyeing with no dyeing spots. In the following examples, if there is no stain and the dyed product has a high final dyeing density, it is marked as ○, and in other cases, it is marked as ×.

Example (1) Dyeing of synthetic polyamide fiber A pre-scoured synthetic polyamide cloth was dyed under the following conditions.

Dye CI Ac1d Yellow 127CI A
c1d Red 299 CI ACid blue 280 Ammonium sulfate 1.0 Decomposition acid 1.0 Temperature/time 100°C 0.5'g o, w, f' 0.5% o, w, r O,5% o, wJ g/1 g/l × 30 minutes decomposition acid decomposition acid heating rate 2℃/separate bath ratio 1:20 Test machine Minicolor-12 dyeing tester (manufactured by Chixam Giken Co., Ltd.) Ammonium sulfate, dye, decomposition acid at room temperature were added in this order and the temperature was started to rise.The results are shown in the table below.

Initial pH Final pH Staining decomposition acid None 7.19 6.66 X
Decomposition acid A 7.04 4.79 0
Decomposition acid B 7.21 5.02 0
Decomposition acid C7,244,64Q Very good dyed products can be obtained with the addition of decomposition acid.
There was almost no dye residue.

Example 2) Dyeing of wool A previously refined wool fabric was dyed under the following conditions.

Dye CI Ac1d Yellow 121 0.
3% o, w rCI Ac1d Orange 1
22 0.3% o, w, rCI Ac1d Bl
ack 712 (), 3% o, vt, f leveling agent Newbon WS (leveling agent manufactured by NICCA Chemical Co., Ltd.) 1.0% o-w-f sodium sulfate 5.0% o-w, f decomposition acid
1.0g/l or 90% acetic acid temperature/time 100℃ x 30 minute temperature rate
2°C/separate bath ratio 1:20 Test machine Minicolor-12 dyeing test machine (manufactured by Chixam Giken Co., Ltd.) At room temperature, ammonium sulfate, leveling agent, dye, and acid were added in this order, and the temperature was started to rise. The results are shown in the table below.

Initial pH #LipH stainability 90% acetic acid 3,93 5.00
x Decomposition acid A 7.75 6.24
0 decomposition acid B 8,37 6.56
0 decomposition acid C7,546,340 The product to which the decomposition acid was added gave a much more evenly dyed product than the one to which acetic acid was added.

Example (3) Synthetic polyamide/cellulose (50150
) Dyeing of mixed fabrics.

A pre-scoured synthetic polyamide/cellulose interwoven fabric was dyed under the following conditions.

Dye ■ CI Direct Blue 237 2.
0% o, w, rCI Ac1d Yellow 1
29 2.0% o, w, f dye ■ CI Direct
Yellow 86 2.0% o, W, rCI
Ac1d Blue 229 2.0% o, w,
r Sodium sulfate 1o-og/1 Decomposition acid o, 2 g/l or 90% acetic acid Temperature/time 100°C x 30 minutes Cutoff temperature rate
1°C/bath ratio 1:20 Test @ Machine Minicolor-12 dyeing tester (manufactured by Chixam Giken Co., Ltd.) At room temperature, add sodium sulfate, dye, and acid in this order.
The temperature started to increase. The results are shown in the table below.

<Dye■> Initial DHiP: pu contamination 90%
Acetic acid 5,78 6.15 Strong decomposing acid A 8.24 6.66 Less decomposing acid B 8,11 6.79 Less decomposing acid C8,316,52 less <Dye ■> Initial pH Final pal Contamination '10
% Acetic acid 4.87 5.95 Strong decomposition acid A
γO56,45 less decomposition acid B 7.
56 6.79 Low decomposition acid C7,326
, 32 When a small amount of decomposing acid is added, there is very little contamination of synthetic polyamide fibers by direct dyes and contamination of cellulose fibers by acid dyes, resulting in good dyed products, compared to when acetic acid is added. Obtained.

Example (4) Dyeing of wool/cellulose (50150) mixed fabric.

A wool/cellulose interwoven fabric that had been vt kneaded in advance was dyed under the following conditions.

Dye ■ CI Direct Blue 237 2.
OX o, w, rCI Ac1d Yellow 1
29 2.05! a, w, f dye ■ CI Dir
ect Yellow 86 2.0% o, w, rCI
Ac1d Blue 229 2.0% o,
wr Sodium sulfate 10-0g/1 Decomposition acid (L2g/l or 90% acetic acid Temperature/time 100℃ x 30 minutes Acceleration rate
1℃/separate bath ratio 1:20 Test machine Minicolor-12 dye test machine (manufactured by Chixam Giken Co., Ltd.) At room temperature, add sodium sulfate, dye, and acid in this order.
The temperature started to increase. The results are shown in the table below.

Dye ■〉 Initial pH Final pH Contamination 90% acetic acid
5,80 6.91 Strong decomposition acid A
8.13 7.35. less decomposition acid
B 8.56 7.52 Less decomposition acid CL45 7.34 Less <dye■>
Initial 3U1pH Final pH contamination 90% acetic acid 5
,23 6.11 Strong decomposition acid A
7.21 6.57 Less decomposition acid B
7.61 6.78 Less decomposition acid C7
, 286, 42 When a small amount of decomposing acid is added, there is very little contamination of wool by direct dyes and contamination of cellulose fiber by acid dyes, resulting in good dyed products compared to when acetic acid is added. Obtained.

Example (5) Synthetic polyamide/cellulose (50150
〉Dyeing of mixed fabrics.

A pre-scoured synthetic polyamide/cellulose interwoven fabric was dyed under the following conditions.

Dye ■ CI ReaCt Blue 27 2. O
X o, w, fCI Ac1d Yellow 129
2.0 No, w, f dye ■ CI React
Yellow 57 2.0% o, w, fCI A
c1d Blue 229 2.0% o, w, f
Sodium sulfate 20.0 g/l Sodium carbonate 5-0 g/1 Decomposition acid 15-Og/l Temperature/time 50°C x 30 minutes further 100@C
X 30 minutes heating rate 1°C/bath ratio 1:20 Test machine Minicolor-12 dyeing tester (manufactured by Chixam Giken Co., Ltd.) Sodium sulfate, sodium carbonate, dye, and decomposition acid were added in this order at room temperature. , the temperature started to increase.

The results are shown in the table below.

Dye ■〉 Initial MpH Final pH Contamination Decomposition acid None
11,24 9.65 Strong decomposition acid A
10.86 5.82 Less decomposition acid B
11.10 5.99 Less decomposition acid - 010,975,59 less dye■> Initial pl+ Final pH contamination No decomposition acid 11,31 9.87 Strong decomposition acid A 10.98 6.53 Less decomposition acid B 11. 11 6.87 Less decomposing acid C11,236,51 If less decomposing acid is added, the reactive dye will strongly stain the synthetic polyamide fibers, and the exhaustion rate of acidic dye will also be greatly reduced. When a decomposing acid is added, there is less contamination of synthetic polyamide fibers by reactive dyes and less contamination of cellulose fibers by acid dyes, and both fibers have a sufficient dye exhaustion rate, resulting in good dyed products. It was done.

Example (6> One-bath scouring and dyeing of polyester fibers) Unscoured polyester palace was treated under the following conditions, and the scouring property (
The adhesive properties (removability) were evaluated.

Dispersant Nikka Sunsalt 5D-07 (manufactured by Nicca Chemical) 0.5g/1 1.0g/l Sodium bicarbonate Sodium carbonate decomposition acid Temperature/time heating rate Bath ratio 2-0g/1 10, Og/1 130 °C x 30 minutes 2 °C/min 1:20 Test machine Minicolor-12 dyeing test machine (manufactured by Chixam Giken Co., Ltd.) At room temperature, an alkali agent, a dispersant, and a decomposing acid were added in this order, and the temperature was started to rise. After the treatment was completed, it was cooled, washed with water, and dried, and its scouring properties were evaluated. The evaluation method is the cationic dye qualitative method (
Maxilon Blue 5G was used (a method in which treated cloth was placed in a 12 g/l aqueous solution, dyed at pH 4° and 5.50° C. for 5 minutes, and evaluated based on the degree of adsorption of the cationic dye to the glue).

As a result, instead of alkaline agents and decomposing acids, acetic acid LOg
In the cases treated with /l, almost no sizing agent fell off, but in the cases treated with the above method, there was no adsorption of cationic dye at all, and most of the sizing agents fell off. It was confirmed that it was emulsified in the treated cloth without re-adhering to the cloth.

2) Unscoured polyester pallet was scoured and dyed in one bath under the following conditions.

Dye CI Disperse Yellow 160
1.0% o, w, fCI Disperse fl
ed 153 0.5% o, w, fCI Di
sparse blue 56 1.0%
o, w, 1 dispersant Nikka Sunsalt 5D-
07 (manufactured by NICCA CHEMICAL) 0.5g/l Hydrogen carbonate 1-0g/l Sodium carbonate 2-0g/1 Decomposition acid 10, Og/l Temperature/time 130°C x 30 minutes Heating rate
2°C/split bath ratio 1:20 Test @ Machine Minicolor-12 dyeing tester (manufactured by Chixam Giken Co., Ltd.) At room temperature, the alkali agent, dispersant, dye, and decomposition acid were added in this order and the temperature was started to rise. The results are shown in the table below.

Initial pH Final pH Staining decomposition acid None 10,40 9.97 x
Decomposition acid A Io, 03 6.21 0
Decomposition'@B 9.89 6.67 0
Decomposition acid C10,366,110 When decomposition acid is not added, the exhaustion rate of the dye is greatly reduced and the dyed material is discolored, whereas when decomposition acid is added, general dyeing of polyester fibers A good dyed product was obtained, with almost the same exhaustion rate as that obtained by dyeing by the dyeing method (method of dyeing in an acidic region).

4. Effects of the Invention The method of the present invention allows the pH of the fiber treatment solution to be lowered gradually and continuously, making it possible to dye fibers more uniformly and efficiently than with conventional methods. It becomes possible. Furthermore, even when dyeing blended, interwoven, or interwoven fabrics, it is possible to dye them more uniformly and efficiently in one bath. Furthermore, it is now possible to efficiently perform one-bath scouring dyeing of various fibers, which has been extremely difficult in the past.

Claims (6)

[Claims] (1) When treating various fibers with a treatment liquid containing one or more types of treatment agents, a sulfonic acid ester derived from a vicinal diol compound, a polyol compound, or an epoxy compound is added to the treatment liquid. This is a method for processing various types of fibers. (2) Allylsulfonic acid, alkylsulfonic acid, or their derivatives are used as esterifying agents, particularly para-toluenesulfonic acid, para-toluenesulfonyl chloride, methanesulfonyl chloride, according to claim 1. It's a method. (3) The method according to claim 1, which is a method for dyeing various fibers. (4) The method according to claim 1, which is a method for one-bath dyeing of various blended, interwoven, or interwoven fabrics. (5) The method according to claim 1, which is a method for single-bath scouring and dyeing of various fibers. (6) By adding the above compound to the treatment liquid, the pH of the treatment liquid whose pH is 5 to 13 at the beginning of the treatment process is reduced or maintained to 3 to 7 at the end of the treatment process or during the treatment process. This is the method according to claims 1 to 5.