JP2006316372A - Method for carrying out preventive processing of discoloration of cellulosic fiber by washing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for carrying out preventive processing of discoloration of a cellulosic fiber by washing, capable of preventing discoloration by a fluorescent brightener in washing after processing without causing discoloration of dye by heat treatment during processing. <P>SOLUTION: The cellulosic fiber is treated with a treating solution containing one or more kinds of compounds selected from phosphonic acid derivatives of a polycarboxylic acid or phosphinic acid derivatives of the polycarboxylic acid. The phosphonic acid derivative of the polycarboxylic acid may preferably be 2-phosphono-1,2,3,4-butanetetracarboxylic acid and the phosphinic acid derivative of the polycarboxylic acid may preferably be phosphinicobisuccinic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a washing discoloration preventing processing method for cellulosic fibers, which prevents the whiteness and color of a fiber product from being changed by a fluorescent whitening agent in a detergent when washing a fiber product comprising cellulosic fibers. is there.

  In general, fluorescent whitening agents are blended in detergents used when washing textile products such as clothing. This fluorescent whitening agent is blended to remove dullness caused by wearing general clothing such as cotton, improve whiteness, and make it look more clean and clean. The fluorescent whitening agent is a kind of anionic direct dye that absorbs ultraviolet rays and emits fluorescence, and is adsorbed on cellulosic fibers such as cotton during washing.

  Here, depending on the clothing, when the fluorescence is superimposed on the original color due to the action of the fluorescent brightener, the color may appear different from the original color. In particular, colors such as light pink, light yellow, and light blue appear to be greatly different in appearance color before and after washing even when the dye is not removed by washing. Also, in the case of white-colored clothing, it looks different white depending on whether there is fluorescence.

  These phenomena are not favored by consumers who have a strong emphasis on fashionability in recent years and are sensitive to color sensations, and may be subject to product claims as defects in clothing, such as discoloration or discoloration. In addition, in the case of uniforms and yukatas worn by many people at the same time, the color of items that are not washed may appear different, which may impair the unification as a group of corner clothing.

  In addition, in order to prevent the fluorescent whitening agent in the detergent from adhering to the cellulosic fibers due to washing, it has been conventionally cross-linked with a cellulose-reactive methylolated resin to make it difficult for the fluorescent whitening agent to bind directly. Alternatively, a method has been used in which adsorption is prevented by carboxymethylating cellulose to anionize and repelling it with an anionic fluorescent whitening agent in a washing bath.

  However, processing with a methylolated resin has the problem of free formalin and the disadvantage of reducing the strength of the fiber. Further, if the carboxymethylation is carried out so that the fluorescent brightener can be prevented from adhering, there is a drawback in that the fibers become swollen and the texture is roughly cured.

Therefore, a method for preventing fluorescent discoloration of cellulosic fibers disclosed in Patent Document 1 below has been proposed. This processing method is characterized in that a cellulosic fiber is treated with a treatment solution having a pH of 1 to 7 of an alkali metal salt of a water-soluble polycarboxylic acid having at least one free carboxyl group. Particularly, the alkali metal salt of the water-soluble polycarboxylic acid is at least one selected from the group consisting of alkali metal salts of butanetetracarboxylic acid, citric acid, malic acid, succinic acid and tartaric acid.
Japanese Patent No. 3626121

  By the way, according to the processing method disclosed in the above-described method for preventing fluorescent discoloration of cellulosic fibers, there is no concern about harmful chemicals such as formalin remaining, and the fabric texture is not impaired. Discoloration due to the fluorescent whitening agent can be prevented.

  However, in this method, the reactivity of the polycarboxylic acid to the cellulosic fiber is low, and the reaction requires heat treatment at a high temperature for a long time. Further, the pH of this treatment solution is generally acidic, and there is a drawback that yellowing of the fiber occurs by heat treatment for a long time at a high temperature.

  As a result, although discoloration due to the fluorescent whitening agent due to washing after processing can be prevented, discoloration during processing can only produce products with colors that are not the original color of the dyed fiber but also the yellowing due to processing. There wasn't.

  In particular, it is difficult to produce clean non-fluorescent white products and clean light pink or light blue textile products, and prevents discoloration due to fluorescent whitening agents due to washing without changing the original clean color of dyed dyes. I couldn't.

  In view of the above, an object of the present invention is to provide a washing discoloration preventing processing method for cellulosic fibers capable of preventing discoloration due to washing without causing discoloration of dye due to processing. .

In solving the above-mentioned problems, according to the method for preventing discoloration from washing of cellulose fibers according to the present invention, at least selected from phosphonic acid derivatives of polycarboxylic acids or phosphinic acid derivatives of polycarboxylic acids. Cellulosic fibers are treated with a treatment liquid containing one or more compounds.

  According to this, it is possible to prevent discoloration due to the fluorescent brightener due to washing after processing without causing discoloration of the dye due to heat treatment during processing.

  According to the present invention, in the method for preventing washing discoloration of cellulosic fibers according to claim 1, the phosphonic acid derivative of the polycarboxylic acid is represented by the following chemical formula:

Thus, 2-phosphono-1,2,3,4-butanetetracarboxylic acid represented may be used.

  According to the present invention, as described in claim 3, in the method for preventing discoloration of cellulose fiber according to claim 1, the phosphinic acid derivative of the polycarboxylic acid is represented by the following chemical formula:

It may be phosphinicobisuccinic acid expressed as such.

  Hereinafter, an embodiment of a method for preventing washing discoloration of cellulosic fibers according to the present invention will be described.

  In the present embodiment, the cellulosic fibers include natural cellulosic fibers such as cotton and hemp, and regenerated cellulosic fibers such as rayon, cupra, polynosic, and tencel. In addition, the cellulosic fiber may be one of the natural cellulosic fiber or the regenerated cellulosic fiber used alone or mixed with other fibers by blending, weaving or knitting. Furthermore, the cellulosic fiber in the present embodiment may be any form of fiber such as a knitted fabric, a woven fabric, a non-woven fabric, or a thread or cotton made of the above-described fibers.

  Moreover, in this embodiment, polycarboxylic acid should just be a compound which has a 2 or more carboxyl group in 1 molecule. Specifically, as the polycarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, propanedicarboxylic acid, propanetricarboxylic acid, butanedicarboxylic acid Acid, butanetricarboxylic acid, butanetetracarboxylic acid and the like can be mentioned. In general, citric acid or butanetetracarboxylic acid is used for fiber processing.

  In order to react these polycarboxylic acids with cellulosic fibers, heat treatment for a long period of time as described above is required. In the processing of polycarboxylic acid, a catalyst such as sodium phosphinate may be used to increase the reaction efficiency. However, due to the reducibility of this catalyst, the dye may be discolored by processing.

  Therefore, the inventors of the present invention can efficiently react with the cellulosic fiber without yellowing the cellulosic fiber by heat treatment at a lower temperature for a short time, and cause the dye to be discolored due to the reducing property of the catalyst. However, it has been found that a specific polycarboxylic acid derivative is effective as a method for introducing an anionic group into a cellulosic fiber.

  These polycarboxylic acid derivatives include one or more compounds selected from phosphonic acid derivatives of polycarboxylic acids or phosphinic acid derivatives of polycarboxylic acids.

  In this embodiment, examples of the phosphonic acid derivative of polycarboxylic acid include phosphonosuccinic acid, phosphonopropane dicarboxylic acid, phosphonobutane dicarboxylic acid, phosphonobutane tricarboxylic acid, phosphonic acid described in European Patent No. 0484196, for example. Nobutane tetracarboxylic acid and the like. Here, particularly preferably, as the phosphonic acid derivative of the polycarboxylic acid, the following chemical formula 5

There is 2-phosphono-1,2,3,4-butanetetracarboxylic acid represented by:

  In the present embodiment, examples of the phosphinic acid derivative of polycarboxylic acid include phosphinicosuccinic acid and phosphinicobisuccinic acid described in European Patent No. 0564346. Here, particularly preferably, the phosphinic acid derivative of the polycarboxylic acid is represented by the following chemical formula

There is phosphinicobisuccinic acid represented by it.

  Next, actual processing of cellulosic fibers will be described.

  The cellulosic fibers to be processed are scoured by a conventional method in advance. In some cases, the cellulosic fibers are bleached and mercerized. Further, the cellulosic fibers are not bleached when produced, and are bleached when non-fluorescent white. Furthermore, in the case of a beautiful colored product such as light pink, dyeing by a usual method is performed after bleaching.

  Thereafter, the cellulosic fiber is treated with a treatment liquid containing the polycarboxylic acid derivative. Specifically, a cellulose fiber is impregnated with an aqueous solution of the polycarboxylic acid derivative. This impregnation may be performed by any method such as a pad method, a spray method or a coating method.

  Here, the amount of the polycarboxylic acid derivative imparted to the cellulosic fiber is 1% to 10%, preferably 1% to 5%, more preferably 1% to 3% with respect to the fiber weight. If it is less than 1%, it is impossible to prevent the fluorescent whitening agent from adhering to the fibers due to washing. Further, if it exceeds 10%, the texture of the fiber is greatly impaired.

  In addition, when the amount is 5% or more and 10% or less, the effect of so-called fiber anti-molding and shrink-proofing can be obtained, but the strength of the fiber decreases. Therefore, in the case where the strength reduction of the fiber is suppressed as much as possible and the texture is emphasized, there is no effect of fendering or shrinkage, but the range of 1% to 5%, more preferably 1% to 3% is preferable.

  For these phosphonic acid derivatives of polycarboxylic acid or phosphinic acid derivatives of polycarboxylic acid, Arkofix PCM New (55% solid content aqueous solution) marketed by European Clariant can be used as a commercially available chemical. Furthermore, an additional catalyst, a softening agent, a pH adjuster, and various other functional processing agents may be used in combination in the treatment liquid as necessary.

  After the impregnation described above, the cellulosic fibers are dried and then heat treated for reaction. This heat treatment is appropriately selected depending on the relationship between the reactivity and the yellowing of the fiber, but is usually performed in the range of 140 ° C to 190 ° C, preferably in the range of 150 ° C to 180 ° C. The time for the heat treatment is appropriately selected in relation to the temperature, but is usually 10 seconds to 5 minutes, preferably about 30 seconds to 3 minutes.

  As described above, in this embodiment, cellulosic fibers are treated with a treatment liquid containing one or more compounds selected from phosphonic acid derivatives of polycarboxylic acids or phosphinic acid derivatives of polycarboxylic acids. Is. Thereby, the cellulosic fiber processed as described above can prevent discoloration due to the fluorescent whitening agent in washing without causing discoloration of the dye due to processing.

  Hereinafter, in the present embodiment, the following examples and comparative examples were prepared and evaluated.

Preparation of test cloth:
The test cloth used for the evaluation was a 50% broad woven fabric (144 warps / inch, 80 wefts / inch) of 100% cotton subjected to normal desizing, scouring, bleaching and mercerization.

  For dyeing, the following reactive dyes were used to dye three colors of light pink, light yellow, and light blue by a normal continuous dyeing method.

Light pink: C.I. I. Reactive Red 21, 3g / L
Pale yellow: C.I. I. Reactive Yellow 37, 3g / L
Light blue: C.I. I. Reactive Blue 19, 3g / L
Example 1:
In Example 1, Arkofix PCM New (European Clariant, 55% solids aqueous solution) was used as the phosphonic acid derivative of polycarboxylic acid or the phosphinic acid derivative of polycarboxylic acid.

  An aqueous solution containing 5% Arkofix PCM New was prepared as a treatment liquid. The above-mentioned treatment liquid was immersed and squeezed by the pad method for each of the above-mentioned dyed cloths, and applied with a pickup of 80% with respect to the weight of the test cloth.

  After application of the treatment liquid, the test cloth was dried at 100 ° C. for 2 minutes. Subsequently, heat treatment was performed at 180 ° C. for 1 minute to complete the reaction. After the heat treatment, it was washed with water and dried to prepare a work cloth of Example 1.

  The obtained processed fabric maintained a beautiful light pink, beautiful light yellow, and a beautiful light blue color without causing discoloration of the dye due to processing.

Comparative Example 1:
In this Comparative Example 1, 5% citric acid (reagent grade 1) was used instead of 5% Arkofix PCM New in the treatment solution of Example 1 for the same test cloth as in Example 1. In this case, 3% sodium phosphinate dihydrate (reagent grade 1) was used in combination as a reaction catalyst. Other conditions were created in the same manner as in Example 1.

Comparative Example 2:
In this comparative example 2, 5% 1,2,3,4-butanetetracarboxylic was used instead of 5% Arkofix PCM New in the treatment liquid of the example 1 with respect to the same test cloth as in the above example 1. Acid (industrial chemical) was used. In this case, 3% sodium phosphinate dihydrate (reagent grade 1) was used in combination as a reaction catalyst. Other conditions were created in the same manner as in Example 1.

Comparative Example 3:
In Comparative Example 3, 5% Fixaplet ECO (modified glyoxal resin from Mitsui BASF) was used instead of 5% Arkofix PCM New in the treatment solution of Example 1 for the same test cloth as in Example 1 above. )It was used. In this case, 1.5% of Condensol LF (magnesium chloride catalyst) was used in combination as a reaction catalyst. Other conditions were created in the same manner as in Example 1.

  The characteristics of each Example and each Comparative Example produced as described above were evaluated. In this evaluation, changes in hue of the test cloth due to processing, tensile strength and strength reduction rate of the test cloth due to processing, and washing discoloration preventing effect were adopted as evaluation items.

  In addition, these evaluation was performed with the following method. The change in the hue of the test cloth due to processing was visually evaluated. The tensile strength and strength reduction rate of the test cloth due to processing were evaluated by the JIS L 1096 6.12 labeled strip method (test piece width: 1 inch). The washing discoloration prevention effect was evaluated by repeating the home washing in accordance with JIS L 0217 method 103 for the test cloth 5 times. The detergent used was 2% powder attack (detergent with fluorescent whitening agent from Kao Corporation) based on the weight of the laundry cloth.

  According to these evaluations, the evaluation results shown in Table 1 below were obtained.

  According to Table 1, Example 1 described above is the comparative example for any evaluation items of the change in the hue of the test cloth by processing, the tensile strength and strength reduction rate of the test cloth by processing, and the washing discoloration prevention effect. It can be seen that it is superior to 1, 2, and 3.

In carrying out the present invention, not only the above-described embodiment but also the following various modifications can be mentioned.
(1) The object to be subjected to washing discoloration prevention processing does not have to be a dyed cellulosic fiber, and may be produced or a non-fluorescent white product.
(2) The cellulosic fiber to be subjected to washing discoloration prevention processing does not have to be mercerized, and may be non- mercerized or ammonia mercerized.
(3) The object to be processed for preventing discoloration from washing is not limited to woven fabrics, but may be knitted fabrics made of cellulosic fibers, non-woven fabrics, yarns, cotton, etc., and clothing after these have been sewn. Also good.

Claims (3)

A method for preventing discoloration of cellulose fibers by treating the cellulose fibers with a treatment liquid containing at least one compound selected from phosphonic acid derivatives of polycarboxylic acids or phosphinic acid derivatives of polycarboxylic acids. The phosphonic acid derivative of the polycarboxylic acid has the following chemical formula 1

2. The process for preventing discoloration of cellulosic fibers according to claim 1, which is represented by 2-phosphono-1,2,3,4-butanetetracarboxylic acid. The phosphinic acid derivative of the polycarboxylic acid has the following chemical formula

2. A method for preventing washing discoloration of cellulosic fibers according to claim 1, which is phosphinicobisuccinic acid represented by the formula.