JPH0784713B2 - Soaping agent and method for improving fastness of dyed product using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a soaping agent for polyester fiber / cellulosic fiber mixed-woven mixed-spinning cloth and a method for improving the fastness of a dyed product using the same.

[Prior Art / Problems] Conventionally, the polyester fiber side is dyed with a disperse dye in the dyeing process of a polyester fiber / cellulose fiber mixed woven mixed fabric, such as a tetron / cotton mixed woven mixed fabric and a tetron / rayon mixed woven mixed fabric. After that, reduction washing is performed, then the cellulose fiber side is dyed with a reactive dye, a direct dye, a slene dye, and the like, and finally soaping (two-bath two-stage method) is used. However, in this method, the unfixed dye is removed after each dyeing step, in order to prevent dye cross-contamination and to obtain a clear and robust dyed product, a washing operation must be carried out, which makes the process complicated. It took a long time.

Therefore, from the viewpoints of productivity improvement, energy saving, etc., after dyeing the polyester fiber side, dyeing the cellulose fiber side without reducing and washing, and finally performing soaping treatment (so-called bath treatment), it is clear and robust. A soaping agent that can obtain a dyed product is desired.

In addition, a one-bath dyeing method using a mixed dye of a disperse dye and a reactive dye has been attempted, but in the case of this dyeing method, an unfixed disperse dye is used because the reactive dye is reduced by a reducing substance and discolors. A soaping agent that cannot be reduced and washed and that can be treated in the same bath was required.

Conventionally, after dyeing a mixed woven mixed fabric of polyester fiber / cellulose fiber, a mixture of urea peroxide and an organic solvent, an ester compound having a polyoxyalkylene chain and an aromatic nucleus, polyoxyethylene alkyl ester, etc. are used for the same bath treatment. Attempts have been made to use it as a soaping agent, but the effect is not always sufficient, and the present situation is that a drastic solution has not been reached.

Therefore, an object of the present invention is to produce a clear and fast dyed product without reducing and washing polyester fiber /
It is another object of the present invention to provide a soaping agent for cellulose fiber mixed and woven mixed-spun cloth and a method for improving the fastness of dyed products using the soaping agent.

[Means for Solving Problems] Therefore, the present inventors have proposed a soaping agent and a soaping agent for performing soaping treatment in the same bath without performing reduction washing after dyeing a polyester fiber / cellulosic fiber mixed woven mixed spun cloth. As a result of diligent studies on a method for improving fastness using this, a disperse dye, a reactive dye, which is used for dyeing a polyester fiber / cellulose fiber interwoven and mixed spun cloth, by performing a soaping treatment using the following soaping agent, Unfixed dyes such as slene dyes can be removed without recontamination in a white place, and a dyeing product can be obtained which has comparable fastness and color tone as compared with the two-bath two-step method of reducing and washing. The inventors have found that it is useful for simplifying the dyeing process, improving productivity, reducing costs, etc., and have completed the present invention.

That is, the present invention relates to (a) a water-soluble polymer having one or more kinds selected from unsaturated carboxylic acids and derivatives thereof as essential constituent monomers; and (b) an aromatic compound having active hydrogen. Another object of the present invention is to provide a soaping agent for a polyester fiber / cellulose fiber mixed spun cloth, which is composed of an alkylene oxide adduct.

Further, according to the present invention, a water-soluble polymer containing (a) one or more kinds selected from unsaturated carboxylic acids and derivatives thereof as an essential constituent monomer after dyeing a polyester fiber / cellulose fiber mixed spinning cloth; And (b) a method for improving the fastness of a dyed product, which comprises treating with a soaping agent comprising an alkylene oxide adduct of an aromatic compound having active hydrogen.

Examples of the monomer used for obtaining the above-mentioned component (a) that can be used in the present invention include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and derivatives thereof. . The derivative is not particularly limited as long as it is a water-soluble derivative, and examples thereof include alkylene oxide adducts of the above-mentioned acids (ethylene oxide, propylene oxide adduct, etc.), alkyl esters (methyl ester, ethyl ester) of the alkylene oxide adducts. Ester, etc.), salts of the above acids and mixtures thereof. In addition to these monomers, pentene, isobutylene, diisobutylene, allyl alcohol, allyl alcohol ethylene oxide adducts, alkyl esters of unsaturated carboxylic acids (methyl ester, ethyl ester, etc.), and the above unsaturated carboxylic acids such as styrene. A monomer copolymerizable with the acid and / or its derivative can be added, but the monomer to be copolymerized is
When it is 90 mol% or more, the polymer tends to be insoluble in water, which is not preferable. The method for polymerizing these monomers is a conventionally known method.

Examples of the synthetic method include radical polymerization of a monomer such as maleic anhydride with an organic peroxide such as benzoyl peroxide or cumene hydroperoxide, or an azo compound such as α, α′-azobisisobutyronitrile. Polymerization under a catalyst in a solvent that does not inhibit radical polymerization such as acetone, methyl ethyl ketone, and toluene, followed by hydrolysis to form a salt, after neutralizing a monomer compound with an alkali metal hydroxide, and then using a solution such as ammonium persulfate. A method of polymerizing under a radical polymerization catalyst and the like can be mentioned. The temperature at the time of polymerization varies depending on the kind of the catalyst used and the like, but is preferably in the range of 20 to 120 ° C. However, the present invention is not limited to these methods.

Regarding the average molecular weight of the polymer, the optimum value varies depending on the component of the monomer and the ratio thereof, but it is preferably about 1,000 to 10,000. If the component ratio is outside the above range, the soaping effect tends to be insufficient. Further, the water-soluble polymer is preferably used so as to have a pH of approximately 5 to 12, but when the content of the unsaturated carboxylic acid is high, the pH tends to be low. Therefore, it is preferable to use the acid as a salt as appropriate.

The reaction of adding alkylene oxide to unsaturated carboxylic acid can be easily carried out by a conventionally known method such as addition at 60 to 140 ° C. under an alkali catalyst. Examples of the alkylene oxide to be added include ethylene oxide and propylene oxide, and the average number of moles added is 1 to 50 mol, preferably 3 to 20 mol, per 1 mol of the carboxyl group of the unsaturated carboxylic acid. Is good.

If the average number of added moles is outside the above range, the cleaning property during soaping tends to be insufficient.

Examples of the type of water-soluble polymer salt include alkali metal salts, ammonium salts, and organic amine salts such as diethanolamine and triethanolamine.

Specific examples of the component (a) include polyacrylic acid salts,
Acrylic acid-maleic acid copolymer salt, maleic acid polymer salt, maleic acid-pentene copolymer, maleic acid ethylene oxide adduct-diisobutylene copolymer, maleic acid propylene oxide adduct methyl ester-allyl alcohol copolymer And a methacrylic acid-allyl alcohol ethylene oxide adduct copolymer.

Examples of the aromatic compound having active hydrogen of the component (b) that can be used in the present invention include (polyvalent)
Examples thereof include phenols, aromatic amines, and alkylphenols (cresol, butylphenol, octylphenol, nonylphenol, etc.), but preferably polynuclear phenols such as phenylphenol, cumylphenol, naphthol, etc. ) In addition to the reaction product of phenols with benzyl chloride or styrene monomer, and further with their formaldehyde or acetaldehyde condensate, polynuclear aromatic amines can be mentioned as preferable ones. The reaction of adding an alkylene oxide to these aromatic compounds having active hydrogen is carried out, for example, under an alkali catalyst at 60 to 140
It can be easily performed by a conventionally known method such as adding at 0 ° C. Examples of the alkylene oxide to be added include ethylene oxide and propylene oxide, and the average number of moles added is 1 to 50 mol, preferably 3 to 20 mol, per 1 mol of the functional group having active hydrogen in the aromatic compound. Good to have. If the average number of added moles is outside the above range, the cleaning property during soaping tends to be insufficient.

In the soaping agent of the present invention, the weight mixing ratio of the above-mentioned components (a) and (b) is (a) :( b) = 1 to 99:99 to 1, preferably (a) :( b) = 20. ~ 80: It is good to use in the range of 80 ~ 20.

Further, the amount of the soaping agent used in the method for improving the fastness of a dyed product using the soaping agent of the present invention varies depending on the method of soaping, etc., but is generally 0 in the soaping bath.
It is preferable to add it in an amount of 01 g (solid content conversion) / l or more, preferably 0.1 to 10 g (solid content conversion) / l, and it is desirable that the soaping temperature is 50 to 100 ° C. for 5 to 30 minutes.

EXAMPLES Next, the present invention will be described in more detail by way of examples, but it should be understood that the present invention is not necessarily limited to the following examples.

Examples Blending Examples of Soaping Agents Table 1 shows blending examples of the soaping agents of the present invention.

Soaping treatment example Polyester / cotton (35/65) blended yarn is used with Dye A
After dyeing at ℃ for 1 hour, wash with water and use Dye B to make Glauber's salt 80
g / l and 20 g / l of soda ash were added, and the mixture was dyed at 60 ° C. for 1 hour and washed with water. 1.0g / l of the soaping agent listed in Table 1
In a soaping bath (bath ratio 1:15) added so that
It was washed with water for 10 minutes, and washed with hot water.

White spot pollution resistance and various fastnesses were measured. The results obtained are shown in Table 3. The results are shown in Lab-based whiteness (W) using Digital Color Studio CS-101D manufactured by Nippon Denshoku Industries Co., Ltd. The larger the value, the higher the whiteness.

Dye A (Disperse Dye) Nippon Kayaku Kayaron Polyester Navy Blue R-SF2.5owf Sumitomo Chemical Sumikaron Turquoise Blue S-GL 1.0owf Sumitomo Chemical Sumikaron Yellow 6G-SL 0.5owf Dye B (Reactive Dye) Hoechst Remazol Yellow GR 1.0owf Hoechst Remazol Black B 0.5owf Bayer Levafix Turquoise Blue E-BA 1.0owf (where owf represents the weight% relative to the cloth) <Evaluation method> White field contamination prevention-in each formulation of the example, When performing soaping, the stain cloth is measured by simultaneously adding the dyed cloth and the attached white cloth to the soaping bath.

Washing test-JIS L-0844 (Method A-4) Organic solvent test-JIS L-0861 (Perchlorethylene) Water test-JIS L-0846 (Method A) Hot pressing test-JIS L-0850 [Wet (strong)] A
Method] Friction test-JIS L-0849 (Gakushin type 200 g x 100 times, wet) Comparative Example 1 A polyester / cotton ( 35/65 ) blended yarn was used with Dye A.
After dyeing for 1 hour at ℃, after washing with water, hydrosulfite 2g / l, caustic soda 2g / l, amylazine D (Daiichi Kogyo Seiyaku: reducing detergent) 1.0g / l reducing bath (bath ratio 1:15 ) At 80 ° C. for 15 minutes, and then washed with hot water. Dye B 60
Dye at ℃ for 1 hour, rinse with hot water, and then wash at 85 ℃ for 10 minutes in a soaping bath (bath ratio 1:15) to which 2g / l of Granup NC (Sanyo Kasei: Soaping agent) was added. It was washed with water.
White spot contamination prevention and various fastnesses were measured in the same manner as in the examples. The results obtained are also shown in Table 3.

Comparative Example 2 A dyed product was obtained in the same manner as in Example except that the soaping agent shown in Table 2 was used. White spot contamination prevention and various fastnesses were also measured in the same manner as in the examples. The results obtained are also shown in Table 3.

Comparative Example 3: Use Example of Component (a) Only Implemented except that only the sodium salt (average molecular weight 6,000) of the maleic acid-pentene (molar ratio 50/50) copolymer shown in Table 1 was used as the soaping agent. A dyed product was obtained in the same manner as in the example. White spot contamination prevention and various fastnesses were also measured in the same manner as in the examples. The results obtained are also shown in Table 3.

Comparative Example 4: Use Example of Component (b) Only A dyed product was obtained in the same manner as in Example except that only 12 mol of the styrenated phenol-ethylene oxide 12 mol adduct shown in Table 1 was used as the soaping agent. . White spot contamination prevention and various fastnesses were also measured in the same manner as in the examples. The results obtained are also shown in Table 3.

As is clear from the results in Table 3, the dyed product obtained by dyeing the polyester fiber side, then dyeing the cotton side without reduction washing and soaping with the soaping agent of the present invention The fastness is equal to or higher than that, and the soaping agent of the present invention is also excellent in white spot contamination prevention. Further, it can be seen that the white field contamination prevention property and the fastness are excellent as compared with those using the method of the present invention.

[Effects of the Invention] The effects obtained by the present invention are as follows.
It is an object of the present invention to provide a soaping agent for polyester fiber / cellulosic fiber interwoven yarn cloth, which can obtain a clear and fast dyed product, and a method for improving the fastness of the dyed product using the soaping agent.

Claims (6)

[Claims] 1. A water-soluble polymer having (a) one or more kinds selected from unsaturated carboxylic acids and their derivatives as essential constituent monomers; and (b) an aromatic compound having active hydrogen. A soaping agent for polyester fiber / cellulose fiber mixed-spun cloth, which is composed of an alkylene oxide adduct. 2. The unsaturated carboxylic acid is acrylic acid, methacrylic acid and / or maleic acid.
The soaping agent according to the item. 3. The weight mixing ratio of (a) and (b) is (a):
The soaping agent according to claim 1 or 2, wherein (b) = 1 to 99:99 to 1. 4. A polyester fiber / cellulosic fiber-spun fabric is dyed, and then (a) 1 selected from unsaturated carboxylic acids and derivatives thereof.
A water-soluble polymer having one or more kinds as essential constituent monomers; and (b) a dyeing product characterized by being treated with a soaping agent comprising an alkylene oxide adduct of an aromatic compound having active hydrogen Robustness improvement method. 5. The unsaturated carboxylic acid is acrylic acid, methacrylic acid and / or maleic acid.
A method for improving the fastness of the dyed product according to the item. 6. A weight mixing ratio of (a) and (b) is (a):
(B) = 1 to 99:99 to 1, wherein the fastness method for improving the fastness of the dyed product according to claim 4 or 5.