JPS62156374A - Method for enhancing dyeing fastness - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for improving the color fastness of dyed products. More specifically, the present invention provides cellulosic fibers or cells [''-
Reactive dye or direct dye of fiber material 4'31 consisting of stainless steel fiber and other fibers. Post-processing of dyed products using random dyes improves color fastness such as wet fastness, light fastness, and chlorine fastness.
Regarding how to make it.

Prior art and its problems Reactive dyes have made remarkable progress in recent years because of their vivid colors and excellent wet fastness.

However, reactive dyes form covalent bonds with fibers and are strongly bonded, but even then, the wash fastness and chlorine fastness are still insufficient, and the dye remaining in the dye bath has a negative impact on the dyed material. Due to contamination, inadequate soaping, or over time, these bonds can be hydrolyzed and cleaved.
Problems often arise as the dye comes off and contaminates other clothing.

As a countermeasure to this problem, dyed products are treated with a dilute aqueous solution of a cationic polymer called a dye fixing agent. In this case, when treated with a condensate of dicyandiamide and a polyethylene polyamine such as ethylenediamine, diethylenetriamine, or triethylenetriamine, washing fastness and acid hydrolysis resistance can be sufficiently achieved, but dyed products treated with a dye fixing agent The disadvantage is that the hue changes and the light fastness and chlorine fastness decrease. In addition, condensates of dimethylamine and epichlorohydrin and quaternary ammonium salt type polycation fixing agents have good color change due to processing and light fastness, or weak wet fastness (especially Newbead dye transfer test), and poor chlorine resistance. The fastness is also insufficient.

Means for Solving the Problems In view of the above-mentioned problems, the inventor has conducted extensive research and has found that:
The present invention has been completed by discovering a method for improving color fastness, which shows remarkable effects in improving color fastness such as wet fastness, light fastness, and chlorine fastness.

That is, the present invention provides a dyed product of cellulose fiber or a fiber material composed of cellulose fiber and other fibers by reactive dyeing 1'
] and [1] at a molar ratio of 1:9 to 9:1 and post-treatment with a 1-wat copolymer. Relates to a method for improving the color fastness of objects.

[I] Formula % Formula % [In the formula, R1 and R2 are the same or different and represent a hydrogen atom or a methyl atom. (IX+) indicates Shodenjo or (1) No acid. ] Allylamine derivative 7 [II] formula % formula % [wherein A represents -C0Q- or -CON 1-1-,
R1 represents a hydrogen atom or a methyl group. R3, R4 and R5 are the same or different and represent a methyl group or an ethyl group, x2 is a halogen atom, Cll3 SO, L or C2R
Indicates 5SO4. n represents an integer of 1 to 5. ] An acrylate derivative represented by.

CI[] Non-acid salt or acid salt of a vinyl group-containing polycyclic amine, or a quaternary ammonium salt obtained by quaternizing the salt with a quaternizing agent.

In the present invention, the seven members of [T] and [II] and/or [I]
It is essential to use a copolymer with a monomer of ], and the wet fastness, light fastness and chlorine fastness of the dyed product can be simultaneously satisfied at a high level.

On the other hand, even when dyed products are treated with monopolymers of the monomers [I], [II], and [1], which have been developed as fixing agents superior to the known dye fixing agents mentioned above, sufficient color fastness cannot be obtained. I can't. That is, when compared with untreated dyed material, [I]
In the case of the 7-mer monopolymer, the degree of improvement in light fastness is low, and depending on the type of dye, a decrease in light fastness is observed. Cu L and [■]'s seven horses! ! Even with the hand aggregate, the chlorine fastness did not improve compared to the untreated dyed material, and the result was unsatisfactory.

In the present invention, the compound represented by formula [I] is a salt of a tertiary amino group-containing di(meth)allylamine and an acid, and the cyanonoramine derivative is diallylamine,
Methyl diallylamine, ethyl diallylamine, propyl diallylamine, butyl diallylamine, amyl diallylamine, hydroxy diallylamine, etc. are commercially available. In addition, inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid and phosphoric acid. Preferred organic acids include saturated fatty acids having 1 to 4 carbon atoms such as acetic acid and propionic acid, maleic acid, Examples include dicarboxylic acids such as phthalic acid and malic acid.

Examples of the compound having formula [II] include tertiary amino group-containing (meth)acrylate derivatives obtained by quaternizing a tertiary amino group-containing (meth)acrylamide derivative using a quaternizing agent.

Examples of tertiary amino group-containing (meth)acrylate derivatives include dimethylamine ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate-1 to dibutylaminoethyl (meth)acrylate. Examples of (meth)acrylamide derivatives containing tertiary amino groups include dimethylaminomethyl (meth)acrylamide, diethylaminomethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethyl Examples include aminohydroxybropyl (meth)acrylamide and diethylaminohydroxybropyl (meth)acrylamide.

Examples of quaternizing agents include alkyl halides such as methyl chloride, methyl bromide, ethyl bromide, and ethyl bromide; aralkyl halides such as benzyl chloride and benzyl bromide; and dialkyl sulfates such as dimethyl@acid and diethyl sulfate.

Compounds belonging to [I11] above include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, behinylpyrowatone, 2'-1LL nylimidacilline,
Examples include 1-vinylimixole, vinyl-2-methylimidazole, 1-vinyl-2-phenylimidazole, morpholinoethyl (meth)acrylate, and morpholinopropyl (meth)acrylamide. Further, examples of the sulfuric acid, sulfuric acid, and quaternizing agent include those mentioned above.

The copolymer used in the method of the present invention comprises the hexamer of [C] and at least one type of hexamer selected from [I] and [1] in a molar ratio of 1:9 to 9. :Used at a ratio of 1,
It is synthesized according to a known radical copolymerization method. Examples of the radical type cocatalyst that can be used include ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoyl peroxide, tertiary butyl hydroperoxide, azobisisobutyronitrile, and cumene oxite.

In addition, water, methanol, ethanol,
Examples include polar solvents such as isopropanol, n-propanol, formamide dimethylformamide, dioxane, acetonitrile, and dimethyl sulfoxide.

The number average degree of polymerization of the copolymer thus obtained is about 10 to 50, preferably 10 to 30, as measured by gel filtration using Sephadex G-25 and Sephadex G-50 (manufactured by Fine Chemicals, Sweden) as fillers.
That's about it.

As the method for treating the dyed material of the present invention, conventional methods can be used as appropriate. For example, a method in which the dyed material is immersed in an aqueous solution in which 1 to 5% of the above copolymer is dissolved in the dyed material and then dried, or a pad is coated with an aqueous solution containing about 1 to 5% by weight of the above copolymer. Examples of processing methods, etc. can be given. In the case of immersion treatment, the bath ratio is usually about 1:10 to 1:30, the treatment temperature is about 20 to 70'C, and the treatment time is 10 to 2
The cropping rate is 0 minutes.

Effects of the Invention The dyed products processed by the method of the present invention have significantly improved wet fastness compared to dyed products processed by the conventional method, and there is almost no discoloration due to the treatment, and no decrease in light fastness is observed. . Furthermore, the fastness to chlorine is also significantly improved.

EXAMPLES In order to make the present invention even clearer, reference examples, comparative examples, and examples are given below.

Reference Examples 1 to 3 The seven polymers shown in Table 1 were polymerized in the proportions shown in Table 2 to obtain copolymers used in the method of the present invention.

Table 1 Table 2 Reference Example 1 In a reaction vessel, diallylamine hydrochloride 2019 (1 mol
66.4%) and 2-(methacryloyloxy)ethyltrimethylammonium me]-sulfate 188.8y
(2 mol 30.0%) was added and stirred to thoroughly mix and dissolve. Next, 40 d of a 20% normal ammonium persulfate aqueous solution was added, and the mixture was stirred at 70 to 75°C for 8 hours while passing nitrogen gas.The reaction rate was measured by the bromination method and found to be 98.5%. Subsequently, the contents were cooled to the lowest temperature, and the resulting yellow transparent viscous liquid was dissolved in a large amount of acetone for 7 hours.
After 70 years, a compound was precipitated. The precipitate was collected by filtration, washed several times with acetone, and dried under reduced pressure to obtain 680 g of copolymer.
(97.2%) was obtained.

Reference Example 2 In a reaction counter, diallylamine salt 2013 (1 mol 66.4%) and 1-vinylimidazole-3-methylammonium methosulfate 1467y (2 mol
30.0%) and stirred to thoroughly mix and dissolve. Next, 40ml of 20% ammonium persulfate aqueous solution was added and stirred at 70-75°C for 8 hours while passing nitrogen gas.The reaction rate was measured by the bromination method and was found to be 98.0.
% was rare. Subsequently, the contents were cooled to air temperature, and the resulting yellow transparent sticky liquid was added to a large amount of acetone to precipitate small compounds. ) After filtering off the impurities, washing with acetone several times and drying under reduced pressure to obtain copolymer 5559 (96
, 7%).

Reference Example 3 In a reaction vessel, 20'l of diallylamine hydrochloride 9 (1 mol 66.4%) and 2-(methacryloyloxy)ethyl 1-rimedylammonium methosulfate 944I
3 (1 mol 30.0%) and 1-pinylimidazole-
3-Methylammonium methlylphate 734 and (
1 mole (30.0%) was added and stirred to thoroughly mix and dissolve. Next, 40+ml of a 20% ammonium persulfate aqueous solution was added and stirred at 70 to 75°C for 8 hours while passing nitrogen gas.The reaction rate was measured by the bromination method and found to be 98.5%. Subsequently, the contents were cooled to room temperature, and the resulting yellow transparent viscous liquid was added to a large amount of acetone to precipitate a polymer. The precipitate was collected by filtration, washed several times with acetone, and dried under reduced pressure to yield 605 g (90 g) of copolymer.
5.0%) was obtained.

Comparative Reference Examples 1 to 3 Monomers 1 to 2 shown in Table 1 were monopolymerized to obtain monopolymers conventionally used for post-treatment of dyed products.

Comparative Reference Example 1 After adding agricultural hydrochloric acid (1 mol) into the reaction vessel,
Stirring was started, and diallylamine 977 was added dropwise from the dropping funnel while the external temperature was being cooled, taking care not to exceed the internal temperature of 35°C. Next, 20r of 20% potassium persulfate aqueous solution
After adding nR and stirring at 70 to 75°C for 8 hours while passing nitrogen gas, the reaction rate was measured by the bromination method and found to be 95.2%. Subsequently, the mixture was cooled to room temperature and 1 q of the yellow transparent viscous liquid was added to a large amount of acetone to precipitate a polymer. The precipitate was filtered and further washed several times with acetone to obtain a single phase compound.

Comparative Reference Example 2 1 to 2-(methacryloyloxy)ethyl in the reaction vessel
Limedylammonium methosulfate-1-9447 ('
After adding 30.0% of I7L), start stirring, add 30d of 20% potassium perMt acid aqueous solution, and stir at 60 to 65°C for 8 hours while passing nitrogen gas through the nitrogen gas introduction tube. , when the reaction rate was measured by the bromination method, 9
It was 8.2%. Subsequently, the mixture was cooled to room temperature, and 1 q of the yellow transparent viscous liquid was added to a large amount of acetone to precipitate the polymer. The precipitate was collected by filtration and further washed several times with acetone to obtain a homopolymer.

Comparative Reference Example 3 1-vinylimidazole-3-methylammonium methosulfate 73=H? (1 mole 30
．． 0%), start stirring, add 30 rBl of 20% potassium persulfate aqueous solution, stir at 60-65°C for 8 hours while passing nitrogen gas through the nitrogen inlet tube, and then check the reaction rate using the bromination method. When measured, it was 98.5%. Subsequently, the yellow transparent viscous liquid obtained by cooling to room temperature was added to a large amount of acetone to avoid precipitation of the polymer. The precipitate was collected by filtration and further washed several times with acetone to obtain a single-use compound.

EXAMPLE A 0.2% by weight aqueous solution of each copolymer and monopolymer prepared in Reference Examples 1 to 3 and Comparative Reference Examples 1 to 3 was prepared. A dyed fabric dyed using the following reactive dye at a concentration of 4% (based on fiber weight) by dipping according to a conventional method was added to an aqueous copolymer solution and an aqueous monopolymer solution in a bath ratio of 1:20. temperature 60
Shun was soaked in 'C for 20 minutes, then washed with water and allowed to cool down.

Reactive dyes used in Test O', 31 a) Procion Br111. Blue H
-Ab) Procion Br111. Red
H-3Bc) Remazol Turq, 31
ue13d) Sumirix 5upra R
Using the ed 3 B F treated cloth, various fastnesses were evaluated according to the following methods. Results in section 3.4.5.6
Shown in the table.

a) Compare with the naked eye the color fastness improver treatment A1 and the stain agent A.
Series judgment using gray scale for discoloration and fading.

b) Washing fastness test No. J 15-L-0844A-IV, using a cotton rag and a double box as an attached vehicle, the degree of contamination was judged by a series using a contamination gray scale.

C) New Beads dye transfer test Prepare a commercially available detergent New Beads 29/Lt water soluble) and soak it in a bath ratio of 1:50 for 30 minutes with the attached cotton gold (1°) and a different weight of the silk box, and put it in a sweat tester. The contamination level was evaluated using the contamination gray scale.

d) Chlorine fastness d-1) 80 as available chlorine according to J l5-L-0821
The test cloth was immersed in a m% solution with a pH of 8±0.2 containing ppm, and was incubated at 25°C for 2 hours. Put it in the test machine. After that, the test cloth was washed under running water for 5 minutes, dehydrated and dried, and its color change and fading was evaluated using a gray scale for color change and fading.

d-2) Washing was carried out continuously for 60 minutes in a domestic washing machine with an inflow of tap water of 6 liters/minute. The discoloration and fading of the test fabric was evaluated using a gray scale for discoloration and fading.

e) Light fastness J 15-L-0842, Fade meter After 20 hours of irradiation, measure the discoloration and fading of the test fabric using the gray scale for fading.
Number judgment.

Table 3 Procion Br111. Blue H-
A Table 4 Procion Br1ll. Red H-3
B Table 5 Remazol Turq, Blue B Table 6 3umifix 5upra Red 3BF 3rd
As is clear from Table 6 (and the wet fastness and knee bead dye transfer tests), the dyed fabric treated by the method of the present invention satisfies the chlorine fastness and light fastness at a high level at the same time. On the other hand, with conventional methods, it has not been possible to obtain a dyed fabric that satisfies the above three fastnesses at the same time.

(that's all)

Claims (1)

[Claims] (1) Dyed products using reactive dyes of cellulose fibers or fiber materials consisting of cellulose fibers and other fibers as shown below [
I] and at least one monomer selected from the following [II] and [III] in a molar ratio of 1:9.
A method for improving the color fastness of a dyed article, which comprises post-treating with a copolymer obtained by copolymerizing at a ratio of ~9:1. [I] Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are the same or different and represent a hydrogen atom or a methyl group. HX_1 represents an inorganic acid or an organic acid. ] Allylamine derivative represented by. [II] Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A represents -COO- or -CONH-, R_1
represents a hydrogen atom or a methyl group. R_3, R_4 and R
_5 are the same or different and represent a methyl group or an ethyl group, X_2 is a halogen atom, CH_3SO_4 or C_2
Indicates H_5SO_4. n represents an integer of 1 to 5. ] An acrylate derivative represented by. [III] An inorganic or organic acid salt of a vinyl group-containing heterocyclic amine, or a quaternary ammonium salt obtained by quaternizing the salt with a quaternizing agent.