JP6441104B2 - Anti-coloring agent for erosion processing of knitted fabrics containing cellulosic fibers, erosion processing agent containing the same and erosion processing method - Google Patents

Description

  The present invention relates to an anti-coloring agent for use in the discharge processing of a knitted fabric containing cellulosic fibers, a discharge processing agent containing the same, and a discharge processing method.

  Conventionally, the discharging process that prints the discharging paste on the knitted fabric made of two or more kinds of fibers having different discharging properties and embrittles and removes the highly discharging fibers is also called opal processing and is widely known. ing. The chemical reaction in the removal process varies depending on the type of fiber. For example, a method for removing polyester fibers is also called alkali weight loss, and is alkali hydrolysis using sodium hydroxide or the like. On the other hand, removal of cellulosic fibers such as cotton and acetate uses acid hydrolysis, carbonization and dissolution with a hot organic solvent.

  It is known to remove only the acetate fiber by performing a patterning process on the knitted fabric made of acetate fiber and polyester fiber as a removal process. As a method for removing a knitted fabric containing diacetate fiber or triacetate fiber, a method of printing and heat-treating a paste liquid containing an organic solvent such as acetone, or a method of printing and heat-treating a paste liquid containing sulfuric acid or aluminum sulfate, etc. However, the former was crying and the mold was unclear, and there was a risk of fire. In the latter case, there is a problem that the discharge is incomplete, and when the temperature is high, yellowing and embrittlement of the partner fiber to be mixed easily occur, and it is difficult to remove the embrittled fiber.

In Patent Document 1, in the removal processing of a knitted fabric containing acetate fibers such as diacetate fibers and triacetate fibers, ethylene carbonate and / or propylene carbonate and a general formula HOOC (CH ₂ ) _n COOH (n = 0 to 8). There has been proposed a discharge processing method for printing a paste liquid containing a dicarboxylic acid represented by the following formula: However, there is a problem that although the discharging effect on the diacetate fiber is sufficient, sufficient discharging property cannot be obtained on the triacetate fiber.

In Patent Document 2, in the process of discharging a knitted fabric containing acetate fibers, alkylene carbonate, dicarboxylic acid represented by the general formula HOOC (CH ₂ ) _n COOH (n = 0 to 8), magnesium, An extraction processing method has been proposed in which a paste liquid containing an inorganic acid salt or organic acid salt of a metal selected from the group consisting of aluminum, iron, cobalt, nickel, zinc, chromium, copper and tin is printed and heat-treated. Yes. The invention of Patent Document 2 is intended to promote removal by carbonate and improve the removal property of triacetate fiber. However, when heat treatment at 150 ° C. or higher is performed, the removal portion is burnt and colored. There was a problem that the coloring due to scoring became deeper as the time became longer. In addition, there is a problem that if it is burnt into a dark color, it cannot be removed by washing.

（式中、Ｘは水酸基、カルボン酸基、アルキルエーテル基、アルキレングリコールエーテル基又はポリアルキレングリコールエーテル基、ｎは１〜５の整数、Ｒはアルキル基又はアリル基をそれぞれ表わす。） In Patent Document 3, one or two kinds selected from sulfates such as aluminum sulfate and compounds represented by the following general formulas (1) and (2) in the discharge processing of knitted fabrics containing acetate fibers. A method for preventing coloring of the mating fiber in the removed portion by printing a paste containing the above is mentioned.

(In the formula, X represents a hydroxyl group, a carboxylic acid group, an alkyl ether group, an alkylene glycol ether group or a polyalkylene glycol ether group, n represents an integer of 1 to 5, and R represents an alkyl group or an allyl group.)

  However, the compounds represented by the general formulas (1) and (2) have a problem that there are many substances that are highly toxic and irritating to humans and have a high influence on the aqueous environment.

Japanese Patent Laid-Open No. 48-68898 JP 49-49000 A JP 58-109694 A

  As described above, in the removal processing of a knitted fabric containing cellulosic fibers such as diacetate fiber and triacetate fiber, the knitted fabric after the treatment has sufficient discharging performance and coloring does not occur, and safety and There has been no known removal processing agent or removal processing method that has no problem of environmental impact. In view of this situation, the present invention provides a discharge processing agent and a discharge processing method that have sufficient discharging performance, do not cause coloring of the knitted fabric after processing, and have low safety and environmental load. This is the issue.

  In the prior art, in order to reduce the occurrence of “burning”, that is, coloring, it has been studied to accelerate the discharge and perform the treatment in a short time. However, the inventors noticed that coloring of the knitted fabric is caused by carbonized fiber residues adhering to the knitted fabric, and the residues cannot be removed even by a washing step after heat treatment. Then, it was found that by adding a coloring inhibitor and hydrolyzing while suppressing carbonization of the fibers, adhesion of the carbonized residue is suppressed and coloring can be prevented and useful. In addition, when a specific polyhydric alcohol compound is added to the removal processing agent in the removal processing of knitted fabrics containing cellulosic fibers such as diacetate fibers or triacetate fibers, carbonization and adhesion of cellulose fibers due to heat treatment is suppressed. Thus, the present invention was completed by finding out that coloring of the extracted portion could be prevented.

  That is, the present invention provides an anti-coloring agent for discharge processing of a knitted fabric containing cellulosic fibers, which contains one or more of a polyhydric alcohol ethylene oxide adduct and / or a polyhydric alcohol fatty acid ester ethylene oxide adduct. About. The number of moles of ethylene oxide added is preferably 1-15. The cellulosic fibers are preferably diacetate fibers or triacetate fibers.

The present invention also provides a paste, a sulfate, a dicarboxylic acid represented by the general formula HOOC (CH ₂ ) _n COOH (n = 0 to 8), a polyhydric alcohol ethylene oxide adduct and / or a polyhydric acid. The present invention relates to a discharge agent for knitted fabrics containing cellulosic fibers, including one or more alcohol fatty acid ester ethylene oxide adducts. The content of the polyhydric alcohol ethylene oxide adduct and / or the polyhydric alcohol fatty acid ester ethylene oxide adduct with respect to the removal processing agent is preferably 5 to 30% by weight. The cellulosic fibers are preferably diacetate fibers or triacetate fibers.

  The present invention also includes a step of printing the above-described discharge processing agent on a knitted fabric containing cellulosic fibers, a step of performing a heat treatment after the printing step, and a fiber embrittled after the heat treatment step. And a step of removing the material. The cellulosic fibers are preferably diacetate fibers or triacetate fibers.

  The heat treatment temperature is preferably 150 to 200 ° C., and the heat treatment time is preferably less than 10 minutes. Moreover, it is preferable that the said removal process is a process of removing the embrittled fiber by performing alkali washing.

  Furthermore, the present invention relates to a discharge processed product obtained by any of the above discharge processing methods.

  According to the present invention, it is possible to effectively prevent coloring in the discharge processing of a knitted fabric containing cellulosic fibers using a compound with high safety and low environmental impact, and good discharge The effect can be obtained. According to the present invention, it is possible to obtain a discharge processed product that is less colored and in which cellulosic fibers have been excellently discharged.

(Anti-coloring agent)
The anti-coloring agent of the present invention contains one or more of a polyhydric alcohol ethylene oxide adduct and / or a polyhydric alcohol fatty acid ester ethylene oxide adduct. Specific examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol and propylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, and sugar alcohols such as xylitol, sorbitol, and erythritol. Among these, glycerin is more preferable in terms of preventing coloring.

  As polyhydric alcohol fatty acid ester, ester of said polyhydric alcohol and fatty acid can be used. As the fatty acid, a saturated or unsaturated fatty acid having 4 to 24 carbon atoms can be used. For example, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, linolenic acid, linoleic acid And unsaturated fatty acids such as palmitoleic acid and oleic acid.

  Examples of the polyhydric alcohol fatty acid ester include glycerin fatty acid ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester, and the like. Specifically, stearic acid monoglyceride, oleic acid monoglyceride, sorbitan monolaurate, sorbitan monostearate, sorbitan Examples thereof include monooleate, sorbitan monopalmitate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol dioleate and the like.

  The addition mole of ethylene oxide to the polyhydric alcohol or polyhydric alcohol fatty acid ester is preferably 1 to 15 moles, and more preferably 3 to 9 moles. When the added mole number of ethylene oxide is 1 to 15 moles, the discharge processing agent that has a good anti-coloring action and performs printing is maintained at an appropriate viscosity. The method for adding ethylene oxide to the polyhydric alcohol or polyhydric alcohol fatty acid ester is not particularly limited, and an ethylene oxide adduct is produced using a known method.

  As the anti-coloring agent of the present invention, one of the above compounds may be used, and it is also preferable to use a mixture of two or more. When using 2 or more types, the blending ratio and blending method are not particularly limited.

  Although not bound by a specific theory, when performing an extraction process using an extraction processing agent containing the anti-coloring agent of the present invention, hydrolysis is performed while suppressing carbonization of cellulosic fibers during processing. As a result, it is considered that the carbonized fibers are less likely to adhere to the surface of the knitted fabric and are easily removed by washing, whereby coloring is suppressed. It is a new concept that does not have a conventional color removal process by adding an anti-coloring agent, and it does not interfere with the performance of the conventional color removal agent and greatly changes the conventional process. It is possible to effectively prevent the coloring without performing.

(Exhaust processing agent containing anti-coloring agent)
The removal processing agent includes the above-described anti-coloring agent, paste, and a component having a removal action. Examples of the component having a removal action include sulfate, a general formula HOOC (CH ₂ ) _n COOH (n = An integer of 0 to 8). Examples of the sulfate include aluminum sulfate, ferrous sulfate, ferric sulfate, copper sulfate, zinc sulfate, stannous sulfate, sodium hydrogen sulfate, and the like, and preferably aluminum sulfate is used. The amount of sulfate used may be adjusted in accordance with the weight of the cellulosic fiber to be removed, but it is generally preferably used in the range of 4 to 30% by weight with respect to the removal processing agent.

Examples of the dicarboxylic acid represented by the general formula HOOC (CH ₂ ) _n COOH (n = 0 to 8) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples thereof include sebacic acid, and oxalic acid is preferably used. What is necessary is just to adjust the usage-amount of dicarboxylic acid according to the weight of the cellulosic fiber to process, and it is preferable to use in the range of 1 to 40 weight% with respect to a removal processing agent.

  As the paste contained in the removal processing agent, any one or two or more of locust bean gum, starch, dextrin, crystal gum, tragacanth, cellulose and the like can be used. The ratio of the paste is not particularly limited as long as it can maintain the proper viscosity for printing and performing heat treatment, but it is preferably contained, for example, in an amount of 1 to 10% by weight with respect to the removal processing agent. .

  The amount of the coloring inhibitor used is preferably in the range of 5 to 30% by weight with respect to the removal processing agent. In particular, the polyhydric alcohol ethylene oxide adduct and / or polyhydric alcohol fatty acid ester ethylene oxide adduct is preferably 5 to 30% by weight, more preferably 10 to 25% by weight with respect to the removal processing agent. preferable. If it is this range, the favorable coloring effect will be acquired and the compounding property to a removal processing agent is also favorable.

  In addition, other compounds such as dyes can be added to the removal processing agent.

(Exhaust processing method)
A discharging process using the above-described discharging agent will be described.
The above removal processing agent is preferably applied to a woven or knitted fabric containing cellulosic fibers. Cellulose fibers include fibers such as acetate fibers (particularly diacetate fibers and triacetate fibers), cotton, cupra, rayon, Tencel (registered trademark), forrese (registered trademark), and particularly diacetate fibers and / or Or the woven / knitted fabric containing a triacetate fiber is preferable.

  The fiber used in combination with the cellulosic fiber is not particularly limited as long as it has a different dischargeability from the cellulosic fiber. For example, polyester fiber, polyamide fiber, polytrimethylene terephthalate fiber, polybutylene terephthalate fiber, polypropylene fiber Polyethylene fiber or the like can be used. A woven fabric or a knitted fabric (collectively referred to as a knitted fabric) composed of yarns, staples, and the like in which cellulosic fibers and these fibers are combined by an arbitrary method such as blending, blending, and twisting is collectively subjected to a discharge process. In addition, these knitted fabrics may include only one type of cellulosic fiber, or may include two or more types.

  The removal process can be performed using the above-described removal process agent in accordance with generally known processes such as printing, heat treatment, and washing. In the printing process, a discharging agent is printed in a shape corresponding to a desired pattern on a knitted fabric containing cellulosic fibers. A printing method, a spray method, or the like is used for the printing of the discharge processing agent. The printing method is not particularly limited, and a form printing method, a flat screen method, a rotary screen method, a roller method and the like are used. The amount of the removal processing agent attached to the knitted fabric can be arbitrarily determined according to the printing method, the woven fabric structure of the fabric, and the desired pattern. For example, in the case of the flat screen method, the texture of the weaving agent, the viscosity of the rubber squeegee, the hardness of the rubber squeegee, and the pressure of the rubber squeegee that prints the agent for removing the surface by the mesh of the formwork that prints the desired pattern. Then, the printing speed of the squeegee is determined, and the discharging agent is uniformly applied to the desired pattern on the fabric. As a confirmation of whether or not the cloth is uniformly attached, the printing part is not visually damaged, there is no difference in the pattern between the left and right rubber squeegees, and the removal processing agent penetrates uniformly into the back of the printing part. . After printing the removal processing agent on the knitted fabric, drying is performed as appropriate, followed by heat treatment.

  Examples of the heat treatment method include a baking method, a steam method, an HT steam method, and the like, and the HT steam method is more preferable.

  It is preferable that the heat processing temperature is 150-200 degreeC. In particular, 150 to 180 ° C. is preferable when the diacetate fiber is discharged, and 170 to 200 ° C. is preferable when the triacetate fiber is discharged. If it is in this range, sufficient discharging can be performed and coloring of the extracted portion can be suppressed. If the temperature is lower than the lower limit of the range, discharging is not sufficient, and if the temperature is higher than the upper limit of the range, coloring of the discharged portion is increased.

  The heat treatment time is preferably less than 10 minutes. If it is less than 10 minutes, coloring of the extracted portion is suppressed, and if longer than that, coloring of the extracted portion increases.

  After the heat treatment step, washing is performed to remove the embrittled cellulosic fibers in the printed part. As a cleaning method, alkali cleaning is preferable, and cleaning is more preferably performed twice. For example, as the first cleaning, soda ash 2 g / L, cleaning at 60 ° C. × 2 minutes is performed. Thereafter, as the second washing, soda ash 2 g / L, surfactant 2 g / L, washing at 80 ° C. for 20 minutes is performed, followed by washing with water, dehydration, and drying. The alkali used in the primary cleaning and the secondary cleaning is not particularly limited, and a surfactant may be used in combination when the alkali cleaning is performed in the primary cleaning.

  Examples of the surfactant used for cleaning include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and these can be used alone or in admixture of two or more.

  Examples of nonionic surfactants include ether type non-alkylating agents such as higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, styrenated alkylphenol alkylene oxide adducts, styrenated phenol alkylene oxide adducts, and higher alkylamine alkylene oxide adducts. Ionic surfactants; Ether ester type nonionic surfactants such as fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and fatty acid alkylene oxide adducts; polypropylene glycol ethylene oxide Polyalkylene glycol type nonionic surfactants such as adducts; fatty acid ester of glycerol, fatty acid ester of pentaerythritol Ester-type nonionic surfactants such as fatty acid esters of terbitol, sorbitol, fatty acid esters of sorbitan, fatty acid esters of sucrose; other nonionic surfactants such as alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines Can be mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The addition form of the alkylene oxide may be random addition of two or more kinds or block addition.

  As anionic surfactants, anionic surfactants of carboxylates such as fatty acid soaps; higher alcohol sulfates, higher alcohol alkylene oxide adduct sulfates, polyoxyalkylene ether sulfates, phenol alkylene oxide adducts sulfuric acid Ester salt, alkylphenol alkylene oxide adduct sulfate ester, styrenated alkylphenol alkylene oxide adduct sulfate ester, styrenated phenol alkylene oxide adduct sulfate ester, polyhydric alcohol alkylene oxide adduct sulfate ester, sulfated oil, sulfuric acid Sulfate salts such as sulfated fatty acid esters, sulfated fatty acids, sulfated olefins; alkylbenzene sulfonates, alkylnaphthalenesulfonates, naphthalene Anionic surfactants of sulfonic acid ester salts such as formalin condensates such as phonic acid, sulfonates such as α-olefin sulfonate, paraffin sulfonate and sulfosuccinic acid diester salt; oleoyl methyl taurine sodium salt, higher alcohol Phosphate ester salt, polyoxyalkylene ether phosphate ester salt, phenol alkylene oxide adduct phosphate ester salt, alkylphenol alkylene oxide adduct phosphate ester salt, styrenated alkylphenol alkylene oxide adduct phosphate ester salt, styrenated phenol alkylene Phosphate ester salts such as oxide adduct phosphate salts and polyhydric alcohol alkylene oxide adduct phosphate esters salts; N-methyl taurine oleate, N-methyl taurine Other anionic surfactants such as theaphosphate may be mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The addition form of the alkylene oxide may be random addition of two or more kinds or block addition. Examples of the salt include alkali metal salts such as lithium, sodium, and potassium; primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, and allylamine; dimethylamine, diethylamine, dipropylamine, dibutylamine, diallylamine, and the like 2 Examples thereof include tertiary amines such as tertiary amine, trimethylamine, triethylamine, tripropylamine, and tributylamine, and amine salts such as alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

  Examples of cationic surfactants include alkyl ether quaternary ammonium salts, alkylamide quaternary ammonium salts, dialkyl ester quaternary ammonium salts, dialkylimidazoline quaternary ammonium salts, alkylamidoamines, alkyl etheramines, alkylamidoguanidines, and arginine derivatives. be able to.

  Examples of amphoteric surfactants include alkyl betaine surfactants, amidopropyl betaine surfactants, imidazolinium betaine surfactants, and the like.

  By the above processing method, it is possible to obtain an extraction processed product in which the cellulose fiber in the portion where the extraction processing agent is printed is dropped. The extracted processed product is subjected to known treatments such as dyeing and finishing as necessary.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples.

[Example 1]
Fabric to be treated:
A satin fabric (diacetate 60) using warps and wefts of twisted diacetate filaments (Mitsubishi Rayon Co., Ltd., 84 dtex) and polyester conjugate filaments (Unitika Trading Co., Ltd., 56 dtex). % / Polyester 40%).
Extracting agent: An extracting agent having the following composition was used.
・ Maypro gum NP (12% aqueous solution) (manufactured by Sanki Co., Ltd.) 50% by weight
Aluminum sulfate (Sumitomo Chemical Co., Ltd., iron-free sulfate band) 10% by weight
・ Oxalic acid (dihydrate) (manufactured by Nacalai Tesque, Inc., (reagent)) 2% by weight
・ Glycerin ethylene oxide 3 mol adduct (Madesei Chemical Co., Ltd.) 20% by weight
・ Water 18% by weight
Removal process:
A square pattern was printed on the fabric to be treated with the above-described discharge processing agent and dried at 110 ° C. for 2 minutes. Subsequently, the superheated steam process was performed for 170 degreeC x 6 minutes using the HT steamer. Thereafter, alkali washing was performed at 2 ° C. with soda ash at 60 ° C. for 2 minutes. Next, it was washed in a soaping bath of 2 g / L of soda ash and 2 g / L of Laccoal ISF (manufactured by Meisei Chemical Industry Co., Ltd., nonionic surfactant) at 80 ° C. for 20 minutes, then washed with water, dehydrated, dried, and subjected to a removal process. A fabric was obtained.
Rating:
The dischargeability and the coloration of the treated fabric were visually evaluated. As an evaluation standard, regarding the pitting property, a fiber in which the printed part was not visually confirmed was determined to be good, and a fiber whose residue was visually confirmed was determined to be not removed. Regarding the coloring, ◎ indicates that there is no difference between the fabric and the printed part, ○ indicates that the color is slightly colored but does not cause a quality problem, and X indicates that the printed part is colored brown. . The results are shown in Table 1.

[Examples 2-7, Comparative Examples 1-4]
Exhaust processing was carried out in the same manner as in Example 1 except that the discharge processing agent and superheated steam treatment temperature and time were set to the respective compositions and conditions shown in Table 1, and the obtained discharge processed fabric was evaluated. The results are shown in Table 1.
Each glycerin ethylene oxide adduct, sorbitan monolaurate ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, and pentaerythritol dioleate ethylene oxide adduct are manufactured by Meisei Chemical Industry Co., Ltd. Nippon Soda Co., Ltd., ferric chloride (hexahydrate) is manufactured by Wako Pure Chemical Industries, Ltd. (special grade reagent), and glycerin is manufactured by Kao Corporation (purified glycerin). It was.

As shown in Table 1, Examples 1-4 and Example 6 containing a polyhydric alcohol ethylene oxide adduct, Examples 5 and 7 containing a polyhydric alcohol fatty acid ester ethylene oxide adduct, In Examples 1 to 3, there was no coloration after the discharge treatment, and Examples 4 to 7 were slightly colored but had no problem in quality.
On the other hand, in Comparative Example 1 containing no anti-coloring agent, the dischargeability was good, but coloring occurred. In Comparative Example 2 containing ethylene carbonate, which is a corrosion accelerator, coloring occurred, and in Comparative Example 3 containing ferric chloride, the pitting property was poor. Comparative Example 4 using glycerin was inferior in both the dischargeability and coloring.

[Example 8]
Fabric to be treated:
A flat slab yarn using polyester long fiber (56 decitex made by Mitsubishi Rayon Co., Ltd.) for the core yarn and triacetate long fiber (61 decitex made by Mitsubishi Rayon Co., Ltd.) as the decorative yarn is used for the warp and weft. A fabric (69% triacetate / 31% polyester) was used.
Extracting agent: An extracting agent having the following composition was used.
・ Maypro gum NP (12% aqueous solution) (manufactured by Sanki Co., Ltd.) 50% by weight
Aluminum sulfate (Sumitomo Chemical Co., Ltd., iron-free sulfate band) 10% by weight
・ Oxalic acid (dihydrate) (manufactured by Nacalai Tesque, Inc., (reagent)) 2% by weight
・ Glycerin ethylene oxide 3 mol adduct (Madesei Chemical Co., Ltd.) 20% by weight
・ Water 18% by weight
Removal process:
A square pattern was printed on the fabric to be treated with the above-described discharge processing agent and dried at 110 ° C. for 2 minutes. Subsequently, the superheated steam process was performed for 175 degreeC x 7 minutes using the HT steamer. Thereafter, alkali washing was performed at 2 ° C. with soda ash at 60 ° C. for 2 minutes. Next, it was washed in a soaping bath of 2 g / L of soda ash and 2 g / L of Laccoal ISF (manufactured by Meisei Chemical Industry Co., Ltd., nonionic surfactant) at 80 ° C. for 20 minutes, then washed with water, dehydrated, dried, and subjected to a removal process. A fabric was obtained.
Rating:
The dischargeability and the coloration of the treated fabric were visually evaluated. Evaluation criteria were evaluated similarly to Examples 1 to 7 and Comparative Examples 1 to 4. The results are shown in Table 2.

[Examples 9 to 13, Comparative Examples 5 to 6]
Exhaust processing was carried out in the same manner as in Example 8 except that the discharge processing agent and the superheated steam treatment temperature and time were set to the respective compositions and conditions shown in Table 2, and the resulting discharged fabric was evaluated. Table 2 shows the results.
Each glycerin ethylene oxide adduct, sorbitan monolaurate ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, and pentaerythritol dioleate ethylene oxide adduct are manufactured by Meisei Chemical Industry Co., Ltd. Nippon Soda Co., Ltd., and ferric chloride (hexahydrate) were manufactured by Wako Pure Chemical Industries, Ltd. (special grade reagent).

As shown in Table 2, Examples 8 to 10 and Example 12 containing polyhydric alcohol ethylene oxide adducts, Example 11 and Example 13 containing polyhydric alcohol fatty acid ester ethylene oxide adducts were pitted. In Examples 8 to 9, there was no coloration after the discharge treatment, and Examples 10 to 13 were slightly colored but had no problem in quality.
On the other hand, Comparative Example 5 containing ethylene carbonate was poor in both the dischargeability and coloring, and Comparative Example 6 containing ferric chloride was poor in coloring.

[Example 14]
Fabric to be treated:
A plain woven fabric using 45th single yarn (manufactured by Shikibo Co., Ltd., 65% polyester / 35% cotton) obtained by blending polyester short fibers and cotton was used.
Extracting agent: An extracting agent having the following composition was used.
・ Maypro gum NP (12% aqueous solution) (manufactured by Sanki Co., Ltd.) 50% by weight
Aluminum sulfate (Sumitomo Chemical Co., Ltd., iron-free sulfate band) 10% by weight
・ Oxalic acid (dihydrate) (manufactured by Nacalai Tesque, Inc., (reagent)) 2% by weight
・ Glycerin ethylene oxide 3 mol adduct (Madesei Chemical Co., Ltd.) 20% by weight
・ Water 18% by weight
Removal process:
A square pattern was printed on the fabric to be treated with the above-described discharge processing agent and dried at 110 ° C. for 2 minutes. Next, a dry heat treatment was performed at 180 ° C. for 1 minute using a pin tenter. Thereafter, alkali washing was performed at 2 ° C. with soda ash at 60 ° C. for 2 minutes. Next, it was washed in a soaping bath of 2 g / L of soda ash and 2 g / L of Laccoal ISF (manufactured by Meisei Chemical Industry Co., Ltd., nonionic surfactant) at 80 ° C. for 20 minutes, then washed with water, dehydrated, dried, and subjected to a removal process. A fabric was obtained.
Rating:
The dischargeability and the coloration of the treated fabric were visually evaluated. Evaluation criteria were evaluated similarly to Examples 1 to 7 and Comparative Examples 1 to 4. The results are shown in Table 3.

[Examples 15 to 20]
Exhaust processing was performed in the same manner as in Example 14 except that the discharge processing agent and the dry heat treatment temperature and time were changed to the respective compositions and conditions shown in Table 3, and the resulting discharged fabric was evaluated. Table 3 shows the results.
Each glycerin ethylene oxide adduct, sorbitan monolaurate ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, and pentaerythritol dioleate ethylene oxide adduct are manufactured by Meisei Chemical Industry Co., Ltd. Nippon Soda Co., Ltd., and ferric chloride (hexahydrate) were manufactured by Wako Pure Chemical Industries, Ltd. (special grade reagent).

  As shown in Table 3, Examples 14 to 17 and Example 19 containing a polyhydric alcohol ethylene oxide adduct and Examples 18 and 20 containing a polyhydric alcohol fatty acid ester ethylene oxide adduct are other than acetate fibers. The same effect was obtained with the cellulosic fibers.

  As described above, the polyhydric alcohol ethylene oxide adducts or polyhydric alcohol fatty acid ester ethylene oxide adducts of Examples 1 to 20 did not inhibit the dischargeability, and good anticoloring properties were obtained. By using the polyhydric alcohol ethylene oxide adduct or the polyhydric alcohol fatty acid ester ethylene oxide adduct as a coloring preventing agent to be blended in the discharge processing agent in the discharge processing of the fabric containing cellulosic fibers according to the present invention, It excels in the pitting property and prevention of coloring, and improves the safety for humans and enables the pitting process considering the environmental load.

Claims (11)

From a knitted fabric containing cellulosic fibers containing one or more of a polyhydric alcohol ethylene oxide adduct and / or a polyhydric alcohol fatty acid ester ethylene oxide adduct having an addition mole number of ethylene oxide of 1 to 15 to cellulose Anti-coloring agent for erosion processing that removes fiber . The anti-coloring agent according to claim 1, wherein the cellulosic fibers are diacetate fibers or triacetate fibers . Sizing agent, sulfate and general formula HOOC (CH ₂ ) _n 1 of polyhydric alcohol ethylene oxide adduct and / or polyhydric alcohol fatty acid ester ethylene oxide adduct having a dicarboxylic acid represented by COOH (n = integer of 0 to 8) and an addition mole number of ethylene oxide of 1 to 15. An extraction processing agent for discharging cellulosic fibers from a knitted fabric containing cellulosic fibers, comprising seeds or two or more species. 4. The extraction according to claim 3, wherein the content of the polyhydric alcohol ethylene oxide adduct and / or the polyhydric alcohol fatty acid ester ethylene oxide adduct is 5 to 30% by weight in the discharge processing agent. Erosion processing agent. The discharge processing agent according to claim 3 or 4, wherein the cellulosic fibers are diacetate fibers or triacetate fibers. A step of printing the extractant according to any one of claims 3 to 5 on a knitted fabric containing cellulosic fibers;
A step of performing a heat treatment after the printing step;
After the heat treatment step, removing the embrittled fibers;
A process for removing a metal, including The discharge processing method according to claim 6, wherein the cellulosic fibers are diacetate fibers or triacetate fibers . The removal processing method according to claim 6 or 7, wherein a temperature of the heat treatment is 150 to 200 ° C. The heat treatment time of the said heat processing is less than 10 minutes, The removal processing method of any one of Claims 6-8. The removal processing method according to any one of claims 6 to 9, wherein the removing step is a step of removing the embrittled fiber by performing alkali cleaning. A method for manufacturing a discharge-processed product including the discharge processing method according to claim 6.