JPS61194282A - Treatment of cationic cellulose fiber - 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 The present invention relates to a method for treating dyed products made from cationized cellulose fiber crystals. More specifically, after dyeing (including printing) cellulose fibers that have been cationized to make them easier to dye with anionic dyes, they are treated with a certain type of fixation treatment agent to significantly improve their stain resistance. The present invention also relates to a method for treating dyed cellulose fibers to improve various fastnesses such as sunlight fastness. In addition, the anti-fouling property in this case is
This refers to resisting staining (so-called color transfer) caused by dyes that have fallen off from other dyed items during soaping baths and home washing.

Originally, anionic dyes are internally reactive dyes and acidic dyes.

Metal-containing complex dyes have low affinity for cellulose fibers, resulting in poor dyeability and low fastness.However,
It is desirable to be able to dye blends and woven products of cellulose fibers and other types of fibers in one bath, to dye conjugate fibers that combine different types of fibers, and to have a large number of colors from the viewpoint of fatuillin. From various aspects, there are many demands for good dyeing of cellulose fibers alone or blended or interwoven products with other fibers using reactive dyes or acid dyes.

From this point of view, there are two methods: (1) pre-treating fibers prior to dyeing using a treatment agent such as a polyamine-based fixing agent or a dicyanamine-based fixing agent, and (2) cationizing cellulose fibers with a cationizing agent containing a quaternary ammonium group. A method of dyeing after chemical treatment has been proposed.

However, although the dye absorption efficiency is improved somewhat in case (2), it is still insufficient, and the quality of the product is not particularly improved.In fact, the texture is deteriorated due to the polymer coating of the fixing agent formed on the fiber surface. This results in rough cutting, which makes subsequent texture adjustment difficult. Furthermore, there was a drawback that the hue of the dyed product was different from that of the dye, making it extremely difficult to obtain clear dyeing. Furthermore, even if clear dyeing is obtained, there is a problem in that dyes that have fallen off from other dyed products in soaping baths or home washing are adsorbed, resulting in significant staining.

In addition, ■ was proposed to improve the drawbacks of ■, and it shows extremely good dyeing properties depending on the type of cationizing agent used. This has become a big problem. Therefore, methods have been proposed, such as post-treatment using a 7-ion activator such as castor oil sulfate after dyeing, or treatment with a compound containing an aromatic sulfonate (Japanese Patent Publication No. 40957/1983). At present, none of them are satisfactory, such as insufficient stain resistance or reduced sunlight fastness.

As a result of extensive research to overcome the drawbacks of the conventional methods described above, the present inventors dyed the entire or partial fiber (product) by dipping or printing cationized cellulose fiber with an anionic dye. By treating the resulting dyed cellulose fibers with a special fixing treatment agent, it is possible to obtain deep-colored dyed products without impairing the texture of the cellulose fibers themselves. It was discovered that it has extremely excellent stain resistance against dyes, and also has improved dyeing fastness, which led to the completion of the present invention.

In the present invention, suitable polymers used as a post-treatment agent for cellulosic fibers or dyed products thereof include 50G-1,
Goo, 000, preferably 1.000-500.00
It is a polymer containing carboxyl groups with a molecular weight of 0. These may be linear and/or crosslinked and may contain, in addition to carboxyl groups, other functional groups, preferably those derived from carboxyl groups.
Further, a completely or partially neutralized salt may be formed.

The carboxyl group-containing polymer used in the present invention is
Examples of suitable carboxylic acids obtained by polymerizing a polymerizable unsaturated carboxylic acid by a conventional method include acrylic acid, methacrylic acid, α-hydroxyacrylic acid, crotonic acid,
Examples include isocrotonic acid, itaconic acid, and maleic anhydride, and homopolymers and copolymers thereof are preferably used.

Further, in the present invention, copolymers of these unsaturated carboxylic acids and various ethylenically unsaturated compounds are also used. Examples of these ethylenically unsaturated monomers include ethylene, propylene, isobutylene, butadiene, alkyl (C+ to C4) or hydroxyalkyl (C, to
C4) acrylate, alkyl (C+~C4) or hydroxyalkyl (C+~Ca>methacrylate,
alkyl (C1-C4) α-hydroxy acrylate,
Acrylamide, methacrylamide, acrylonitrile, methacrylaterile, divinyldioxane, divinylbenzene, vinyl ether, or vinyl ester of (C, to Cs) carboxylic acid, vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc. There is. Preferred copolymers are those obtained by copolymerization of acrylic acid or methacrylic acid with one of the above-mentioned olefinic heptamers.

In the case of maleic anhydride, alkyl (C
+ to C4) Copolymers with ethylenically unsaturated monomers such as vinyl ethers or styrene are used.

The most preferred polymers according to the present invention are polyacrylic acid, polymethacrylic acid, poly-alpha-hydroxyacrylic acid, ethylene and maleic anhydride copolymers, and methyl vinyl ether and maleic anhydride copolymers. Of course, the maleic anhydride copolymer must be at least partially hydrolyzed.

The cellulose fibers used as the raw material to be dyed in the present invention may have various shapes, such as thread-like shapes.

Examples of cellulose materials include fabrics, mats, paper, cotton, etc., and cellulose raw materials include cotton, hemp, pulp, and the like. In addition to cellulose fibers alone, the cellulose fibers used in the present invention include various natural fibers,
Also included are those containing appropriate amounts of different types of fibers, such as chemical 9 synthetic fibers. Furthermore, among cellulose fibers, cationized and non-cationized products are naturally included.

In order to dye the cellulose fibers described above according to the present invention, first, a cationization treatment is performed as a pretreatment. , 2,3-epoxypropyltrimethylammonium chloride, trimethylene-bis(3-chloro-
A compound containing a cationic group in its molecule, such as 2-hydroxypropyl-dimethylammonium chloride, and a group reactive with the hydroxyl group in the cellulose molecule is used to form cellulose fibers in an aqueous or organic medium. react with.

Next, the thus pretreated cationized cellulose fibers are dyed. In this case, any anionic dye can be used, such as reactive dyes, acid dyes, Direct dyes, sulfur dyes, etc. are commonly used. This dyeing process can be carried out using a dye alone, but it can also be carried out using an electrolyte,
Naturally, it is also possible to dye by adding a leveling agent, an alkaline agent, a sizing agent, etc.

In the present invention, one or more of the above-mentioned fixing agents are applied to the dyed cellulose fiber obtained by carrying out the cationization treatment and the dyeing treatment on the entire fiber or partially. The treatment in this case is usually carried out by a dipping method, but depending on the case, it can also be carried out by a puffing method, a spraying method, or a printing method. When the dipping method is used, the fixing agent is dissolved in an aqueous medium or a suitable organic solvent, and the dyed cellulose fiber is dipped into this medium. In this case, the concentration of the processing agent in the medium is 0.01 to 50% by weight.
, preferably from 0.02 to 30% by weight, and the treatment temperature is from 0 to 130°C, preferably from 20 to 80°C.

The processing time varies depending on the processing agent concentration and processing temperature, but generally a few seconds to about 30 minutes is sufficient. The amount of treatment agent attached to the dyed cellulose fiber is 0.01 to 30% by weight, preferably 0.02 to 20% by weight, based on the dyed product.
It is.

According to the method of the present invention, it is possible to perform deep color dyeing without impairing the texture of cellulose fiber itself, and the dyed product obtained has improved fastness compared to conventional methods. It is especially advantageous that the adsorption of other dyes is significantly inhibited, so that there is no contamination by other anionic dyes in soaping baths or in domestic laundry.

Next, the present invention will be explained in more detail with reference to synthesis examples and examples.The present invention is not necessarily limited to the following examples. Note that % is % by weight.

[Synthesis example]

Synthesis example l.

17 with a stirring bar, cooling tube, temperature needle, N2 gas introduction tube and 9 dropping funnels! - 5 ion-exchanged water in 4 flasks
00g was charged and the temperature was raised to 100°C. Inside the system is 100℃
When it reaches 400g of 50% acrylic acid aqueous solution,
100 g of a 0.1% ammonium persulfate aqueous solution was simultaneously added dropwise over 3 hours. After the addition was completed, the mixture was aged at 100° C. to obtain a fixing agent made of polyacrylic acid. In addition,
The molecular weight was about soo, ooo when measured by GPC (gel permeation chromatography).

Synthesis Example 2 Using the apparatus used in Synthesis Example 1, 500 g of ion-exchanged water was charged into a flask and the temperature was raised to 100°C. When the temperature inside the system reached 100°C, add 400 g of 50% methacrylic acid aqueous solution and 100 g of 0.1% ammonium persulfate aqueous solution.
were added simultaneously over a period of 3 hours. 100 after addition
The mixture was aged at ℃ for 1 hour to obtain a fixing treatment agent made of polymethacrylic acid.

The molecular weight was approximately 300,000 when measured by GPC.

Synthesis Example 3 Using the apparatus used in Synthesis Example 1, 490 g of ion-exchanged water was charged into a flask, and the temperature was raised to 100°C. When the temperature inside the system reached 100°C, 50% acrylic 3. 400 g of aqueous solution, 10 g of thioglycol, and 100 g of 10% ammonium persulfate aqueous solution were each simultaneously added dropwise over 5 hours. After the addition was completed, the mixture was aged at 100° C. for 1 hour to obtain a fixing agent made of polyacrylic acid. In addition, the molecular weight was about 1000 when measured by GPC.

Synthesis Example 4 Using the apparatus used in Synthesis Example 1, 560 g of ion-exchanged water was charged into a flask, and the temperature was raised to 60°C. 6 in the system
When the temperature reached 0℃, add 350g of 50% acrylic acid aqueous solution.
, 50 g of 50% crotonic acid, and 40 g of a 0.1% ammonium persulfate aqueous solution were each simultaneously added dropwise over 2 hours.

After the addition was completed, the mixture was aged at 60° C. for 2 hours to obtain a fixation treatment agent. In addition, the molecular weight was approximately so, ooo when measured by GPC.

Synthesis Example 5 Using the apparatus used in Synthesis Example 1, 500 g of ion-exchanged water was charged into a flask and the temperature was raised to 70°C. When the temperature in the system reached 70°C, add 300 g of 50% aqueous acrylic acid solution, 50 g of 50% isopropyl I solution of methyl methacrylate, and 50% 2-acrylamide-2-methylpropanesulfonate (manufactured by Nitto Kaisha: trade name). TBA
S) 50g of aqueous solution, 10% ammonium persulfate aqueous solution
00g were added dropwise at the same time over 2 hours. After the addition was completed, the mixture was aged at 70° C. for 2 hours to obtain a fixing agent consisting of acrylic acid, methyl methacrylate, and TBAS. The molecular weight was about aooo when measured by GPC.

Synthesis Example 6 Using the apparatus used in Synthesis Example 1, 795 g of ion-exchanged water + 100 g of acrylamide and 100 g of itaconic acid were charged into a flask, and the temperature was raised to 50°C. 5 within the system
When the temperature reached 0°C, 75 g of persulfuric acid was added.

After the addition was completed, polymerization was carried out for 24 hours to obtain a fixation treatment agent consisting of acrylamide and itaconic acid fixation treatment agents. The molecular weight was about 3000 when measured by GPC.

Synthesis Example 7 A solution of 267 g of maleic anhydride dissolved in 2089 mJ of benzene and 95% benzoyl peroxide were placed in a No. 31 autoclave, and oxygen in the system was removed using high-purity ethylene. Next, increase the system pressure to approximately 250 ps using high-purity ethylene.
ig, stirring was started, and the temperature was raised to 70°C. When the temperature inside the system reaches 70℃, increase the pressure to 300 ps i
The pressure was adjusted to 1.5 g, and ethylene was supplied to maintain this pressure, and polymerization was carried out for 16 hours. Add 1716g of water to this,
Benzene was removed to obtain a fixing agent consisting of a copolymer of hydrolyzed maleic anhydride and ethylene in a molar ratio of 50:50. The molecular weight was about 5000 when measured by GPC.

〔Example〕

Example 1゜ Cotton broadcloth (#40) was treated with 3-chloro-2-hydroxy-propyltrimethylammonium chloride (r
cTAJ), washed with water, dyed with a reactive dye, and then post-treated with a fixation treatment agent. The specific conditions in this case are as follows.

A: Cationization treatment conditions CTA concentration; 10% by weight bath ratio, 1:20 temperature, 80°C time; 6G minutes B: Dyeing conditions Dyeing bath i Procion 8rl11. Red
5% by weight aqueous solution bath ratio of H-38 to cotton broadcloth: 1:30 Temperature: 60°C Time: 30 minutes -2: Fixation treatment agent C-3 obtained in Synthesis Example 2 - Fixation treatment agent C-4 obtained in Synthesis Example 3; Fixation treatment agent C-5 obtained in Synthesis Example 4; Fixation treatment obtained in Synthesis Example 5 Agent C-6; Fixation treatment agent C-7 obtained in Synthesis Example 6; Fixation treatment agent C-8 obtained in Synthesis Example 7; Maleic acid and butadiene copolymer (manufactured by Nippon Petrochemical Co., Ltd.) in a 20% aqueous solution. C-9; Jerimer AC-1038 (manufactured by Nippon Pure Chemical Industries, Ltd.: 10% polyacrylic acid aqueous solution, viscosity 12000 cP/25°C) was neutralized with ammonia and diluted to make a 20% aqueous solution C-10 ; Adjust the pH of Jerimer AC-103 (manufactured by Nippon Pure Chemical Industries, Ltd.; sodium polyacrylate 40% aqueous solution, viscosity 400 cP/25°C) with hydrochloric acid.
Adjusted to H5 and made into a 20% aqueous solution C-ratio 1; No fixation treatment agent C-ratio 2: β-naphthalenesulfonate sodium aldehyde condensate C-ratio 3; Castor oil sulfate (ratio is a comparative example) Fixation Treatment method The dyed product obtained by sequentially performing the treatments A and B above was fixed under the following conditions.

Fixation treatment agent concentration: Solid content 5il volume% solution bath
Ratio: 1:20 Temperature: 80°C Processing time i: 20 minutes Next, the dyed product thus obtained was subjected to the following test and the results are shown in Table 1. The evaluation of the test results was as follows: It is divided into 5 stages from 5 to 5, and the larger the value, the better the result.

+1) Conditions for using Kayarus 5upra VGN as stain resistance test dye: Dye concentration 0.01% by weight, bath ratio 1; 50 = immersion temperature and time 60°C XIO minutes (2) Massat fastness JIS-LO849 method Type (3) Washing fastness JIS-LO844 method A-2 method Table 1 (4) Sunlight fastness JIS-LO841 method Example 2゜Using the same fabric obtained by cationization treatment in Example 1, l for the fabric weight of acid dye Diacid Red 3BL! Amount of water in aqueous solution i! i- After crushing and dyeing, fixation treatment was carried out in the same manner as in Example 1. The obtained dyed product was tested in the same manner. The results are shown in Table 2.

Example 3゜Use the cationized cloth shown in Example 1 and apply it to l1a
Yaras Light 5carlet F2O was dyed by dipping it in an aqueous solution of 1% by weight based on the weight of the fabric, followed by fixation treatment in the same manner, and the obtained dyed product was tested in the same manner. The results are shown in Table 3.

Example 4゜ Sodium alginate Table 2 Table 3 Table 4 1%, Diamira Br1ll Red F-3
Next, apply 1 part of the same fixing agent as in Example 1 to hot water (the area where the pattern is not printed) with a color paste containing 81%.
0%.

Colorless paste containing 1% sodium alginate is printed.

This printed fabric was dried at 120°C for 3 minutes, treated with 100°C steam for 1 minute, washed with water, and then heated with 2 g/l soap water for 10 minutes at 90°C.
Soap for a minute and rinse again.

Table 4 shows the results of similarly examining the stain resistance and sunlight fastness of the hot water portion of this printed fabric.

From this table, it can be seen that contamination of hot water is well prevented.

Claims (1)

[Claims] 1. A cationized cellulose fiber or a dyed product thereof,
1. A method for treating cationized cellulose fibers, the method comprising treating cationized cellulose fibers using a fixing agent whose main component is a polymer containing a carboxyl group or a carboxyl group neutralized in the form of a salt. 2. The polymer containing a carboxyl group is a homopolymer or copolymer of a polymerizable unsaturated carboxylic acid, or a copolymer of an ethylenically unsaturated monomer that can be polymerized with these, and these polymers have a molecular weight of 500 to 1.000.000. and the polymerizable unsaturated carboxylic acid is 20
The method for treating cationized cellulose fibers according to claim 1, wherein the cationized cellulose fibers are contained in an amount of at least % by weight.