JPS63303182A - Improved method for producing recycled 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] <Industrial Application Field> The present invention relates to an improved method for producing regenerated cellulose fibers, and more particularly to improving the dyeability and economic efficiency in dyeing processing of regenerated cellulose fibers. .

<Prior Art> Conventionally, cellulose fibers can be dyed with anionic dyes such as mono-reactive dyes and direct dyes, but these bonds are not due to covalent bonds or physicochemical adsorption;
The affinity between dye and fiber is not very high. Therefore, when dyeing cellulose fibers, it is necessary to add a large amount of salt or alkali to increase the affinity between the dye and the fiber, increase the concentration of the dye in the dye bath, or dye it at high temperature for a long time. This poses a major operational and economical problem. Furthermore, cellulose fibers have the problem that even with the same anionic dyes, it is impossible to dye them with acid dyes, which are excellent for dyeing animal hair fibers and polyamide fibers, and as a result, they are less versatile in dyeing. ◎ As a solution to the above-mentioned problems, a cationic compound is added to cellulose fibers to cationically charge the fiber surface, increasing its affinity for anionic dyes.
Up to now, methods have been proposed to improve stainability. For example, there is a method in which monocationic compounds, such as fixing agents, are applied to fibers in advance and dyed with anionic dyes, but these compounds have a weak bond with the fibers, resulting in poor durability and As a result, there are problems such as poor dyeing consistency. Furthermore, special public service 61-601
Regarding the dyeing method disclosed in Japanese Patent No. 94, in which the dyeability of cyanionic dyes is improved by polymerizing a monomer containing a quaternary nitrogen atom within cellulose fibers, Since the polymerization reaction takes place in the amorphous region of the fibers, the fibers harden and the moisture content decreases, resulting in the loss of the excellent texture and characteristics of cellulose-based FF1M. Furthermore, in order to overcome the drawbacks of these fiber adsorption type or intrafiber polymerization type compounds, compounds containing quaternary ammonium salts that react with fibers through chemical bonding have been proposed.

(Special Publication No. 39-5985, Publication No. 46-4051
No. 0, JP-A-60-9980). For example, Japanese Patent Publication No. 39-5985, Japanese Patent Publication No. 46-405
There is 3-c10-2-hydroxyglobil trimethylammonium chloride described in Publication No. 10, but since this is a -functional group type compound, its bonding force with fibers is weak, and its stability and durability after treatment are poor. The problem is that there is a lack of Furthermore, trimethylamine is generated during or after the treatment, causing foul odor and pollution, which poses a problem in practical use.

On the other hand, as a polyfunctional compound disclosed in JP-A-60-9980, for example, trimethylene-bis(3
- Kuro C! -2-Hydroxyglobildimethylammonium chloride), which has cross-linked cellulose and cellulose through multiple reactive groups, resulting in a dense fiber structure and, as a result, increased processing capacity of the fibers. As the strength decreases, the degree of swelling decreases, leading to nine problems.

Further, a common problem with the above-mentioned compounds is the fact that the affinity between the obtained cationized cellulose and the anionic dye is too strong, making it impossible to obtain level dyeing properties. From the above points, it has been found that although the conventional cationized cellulose m and m improve dyeing properties, they have problems in level dyeing properties, stability, workability, etc., and are far from practical use. .

<Problems to be Solved by the Invention> In view of the above-mentioned drawbacks, the present inventors have conducted extensive research and have found that there is a close relationship between the structure of cationic compounds and these problems. In other words, there are problems with conventional cationized cellulose (stability, level dyeing,
Strength,! #Moisture) can be solved by examining the molecular structure of cationic compounds. For example, in order to improve stability and durability, it is necessary to increase the number of functional groups in the compound in order to increase the number of reaction points between the compound and the fiber. In addition, to solve problems such as a decrease in strength and swelling degree and an inability to obtain level dyeing, the length of the compound molecule, more specifically, the distance between multiple ionically charged nitrogen atoms, should be adjusted to a certain value. It turns out that the problem can be solved by This is considered to be because the nitrogen-to-nitrogen distance has a great influence on the charge distribution of ions and the structure of cellulose. On the other hand, when the compounds obtained from these research results were applied to natural cellulose tits, almost no effect was observed, whereas regenerated cellulose fibers showed excellent stability, level dyeing, etc. It was found that it showed a positive effect.

Based on the above results, the inventors have discovered that all of the above-mentioned problems can be solved by treating regenerated cellulose fibers with a certain specific compound, and have completed the present invention. That is, an object of the present invention is to provide a method for producing a regenerated cellulose image line that is excellent in dyeability, economical efficiency, and safety.

Means for Solving the Problems〉 That is, the present invention provides regenerated cellulose fibers having the general formula (I).
This is an improved method for producing regenerated cellulose tRm in which the regenerated cellulose tRm is treated with a cationic compound (hereinafter referred to as a cationizing agent) shown in t-%.

General formula (I) [In formula (I), A, , A2. A3 and A4 are each hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group.

Must be an aryl group or an aralkyl group with carbon atoms Aa of 7 to 18, X is an integer of 1 or more, B1 and B2 are each hydrogen except when both are hydrogen, and if the number of carbon atoms exceeds 18, there will be problems with liquid stability. It is not preferred in the treatment of abrasive fibers. X
Practically speaking, it is preferably 3 or less. When X becomes large, there is a problem with liquid stability.

In the present invention, treatment is performed with an aqueous solution containing a cationizing agent or an aqueous solution containing a cationizing agent and an alkali.

Examples of alkalis include NaOH, xou, Na2Co,
, K2CO,.

(Nus)2cos, (NH4), Co or other alkaline substances and mixtures thereof can be used.

Specific treatment methods include dipping method, banding method,
Examples include a printing method and a spray method, and the treatment temperature may be 0 to 150° C. for the dipping method, and 0 to 200° C. for other methods, either dry heat or moist heat. The treatment time is appropriately selected depending on the treatment temperature and treatment method. The amount of cationizing agent (I) to be used in the present invention can be arbitrarily changed depending on the type of fiber material, processing method, etc., but is preferably 1 to 2.
A treatment solution of 001/no is suitable. After the reaction is carried out by the above-mentioned treatment, unreacted cationizing agent and alkali are removed by washing with water. (9) If necessary, an acid may be added for neutralization. In addition, the regenerated cellulose fiber ta in the present invention
It refers to Toha, viscose process rayon, copper ammonia process rayon, and polynosic rayon, and these processing conditions can be in any form such as cotton, yarn, woven fabric, knitted fabric, blended with other materials, blended fiber, mixed twist. There is no problem even if it is a mixed knit or mixed weave.

The cationized regenerated cellulose fiber of the present invention exhibits dyeability that is superior to direct dyes, reactive dyes, and vat dyes used in conventional dyeing of cellulose fibers, and is indispensable for conventional dyeing. There is no need for the addition of salt or alkali, or post-treatment with a fixing agent, and it is also possible to dye at low temperatures, and furthermore, there is no need for a wastewater treatment process after dyeing, which is economical. We can provide fibers with excellent workability and safety.

Furthermore, it can be said that the present invention greatly contributes to the rationalization of the dyeing process in order to save energy and reduce costs.

On the other hand, it has the advantage of being able to be dyed with acid dyes and metal-containing dyes, which were currently impossible to dye.

Acid dyes are typical dyes for animal hair fibers and polyamide fibers, but once it becomes possible to dye with these dyes, it becomes possible to dye composite materials in the same color or dye single materials in different colors using a bath. , the versatility in dyeing is increased.

Furthermore, compared to conventional regenerated cellulose fibers, the cationized regenerated cellulose fibers of the present invention have almost no change in fiber strength or degree of swelling, but tend to increase in flexibility and hygroscopicity. That is, it can be said that the cationized regenerated cellulose fiber of the present invention exhibits characteristics that are superior to conventional regenerated cellulose fibers not only in improved dyeability but also in feel and properties.

A further noteworthy fact is that the cationized regenerated cellulose fibers of the present invention have significantly improved wet fastness compared to conventional regenerated cellulose fibers. This is thought to be due to the fact that the binding force between the dye and the fibers has become stronger than that of conventional ones, but this treatment also covers the shortcomings of conventional regenerated cellulose fibers. This can be said to be an extremely noteworthy invention as an unprecedented method for improving the dyeability of sludge fibers.

Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A scoured white rayon cloth was immersed in an aqueous solution containing a cationizing agent (90g/) listed in Appendix IK at a bath ratio of 1:50,
The temperature was raised to 60°C, and caustic soda was added to the tube for 60 minutes.
3! do. Thereafter, it was washed with water, neutralized with an aqueous acetic acid solution, washed with water, dehydrated, and dried to obtain cationized rayon cloth 1. Incidentally, caustic soda is a cationizing agent (12 parts per 100 parts by weight) in terms of solid content.

The cationized cloth t Diacid Alizoline Light Blue 4GL (Diacid Allza
linellght Bl Tsuru/4GL) Section 200 (acid dye manufactured by Mitsubishi Chemical Industries, Ltd.) 14ovf, p
Dyeing was carried out at 90° C. for 30 minutes in H3.5 and bath ratio 1:50. Thereafter, it was washed with water, soaped, dehydrated, and dried to obtain a blue cationized cloth.

Comparative example 1 Different! ! The same treatment as in Example 1 was carried out, except that a trimethylene gas (3C:12 hydroxyglobil dimethylammonium chloride) compound was used in place of the cationizing agent (4) described in Section 1.

Table 1 shows the dyeing characteristics of the dyed fabrics of Example 1 and Comparative Example 1 obtained by the above method.

Table 1 ") K/a value: Kub@lka Munk It is calculated by the formula of 2 numbers and has a proportional relationship with the density of the dyed product. Here, it was measured with a Macbeth S-2020 side color device.

As is clear from the results in Table 1, the products of the present invention have excellent level dyeing properties and considerably improved dyeing properties compared to the comparative examples.

Example 2 Refined white rayon cloth was treated with a cationizing agent (
B) Immerse in a mixed aqueous solution of 90 g # and 101//l of caustic soda, squeeze to 804 with a mangle, wind up on a roll, seal with a polyethylene sheet, leave at 20°C for 20 hours, and then wash with water. Thereafter, the same processing as in Example 1 was performed.

Sumifix Brilliant Blue R (Suml
flxBrllll Blu@R) (manufactured by Sumitomo Chemical, reactive dye) Staining was performed under the conditions of 1011/l, 20° C., and 16 hours. At this time, salt and alkali necessary for conventional reactive dye dyeing were not added.

Comparative Example 2 The same treatment as in Example 2 was carried out, except that 3chloro2hydroxypropyltrimethylammonium chloride gold was used instead of the cationizing agent (B) listed in Attached Table 1.

The OK/S value of the dyed products of Example 2 and Comparative Example 2 obtained by the above O method was measured, and the change in dyeing amount (K/8 value) when the samples were washed several times was measured, The results are shown in Table 2.

Shallow 2 According to the above results, the product of the present invention has better dyeing properties and better dyeability than the comparative example.
Excellent stability and durability.

Further, in the comparative example, a bad odor was generated during drying after washing, and it was confirmed that the product was far from being suitable for practical use.

Example 3 Refined Pempelg (Asahi Kasei Co., Ltd. Copper-ammonia process rayon) white cloth was cationized using the same treatment method as Example 1, and then Kayaras Fugura Red EWS (Kay
arus 5upra Red EWS) (Direct dye manufactured by Nippon Kayaku Co., Ltd.) Soaked in a dye solution with a concentration of 2011/l,
After squeezing to 80% using a mangle, it was dried using a tenter at 100°C for 1 minute, followed by washing, soaping, dehydration, and drying. At this time, no salts such as mirabilite were added.

Comparative Example 3 Same as Example 3 except that cotton cloth was used instead of Penvelve white cloth.
Cationization and staining were performed under the same conditions. The results of dyeability (K/S value) and color fastness (water, washing, light fastness) of the dyed fabrics of Example 3 and Comparative Example 3 are shown in Tables 3-1 and 3-11.

Table 3-1 Table 3'''' ■ (Grade) As mentioned above, the product of the present invention has excellent dyeing properties and level fastness, while the comparative example has excellent stability and durability after dyeing. It was inferior in sex.

Furthermore, in the Examples, although a very rational dyeing process called dry drying was employed, the products of the present invention had sufficient dyeability and fastness.

Example 4 A refined white rayon cloth was cationized in the same manner as in Example 2, and then Kayanol Milling Blue GW (K
ayanol Mill, Blue GW) (manufactured by Nippon Kayaku Co., Ltd., acid dye), Kayarasugelable Blue-4
G (Kayarua 5upra Blue 4G)
(manufactured by Nippon Kayaku Co., Ltd., direct dye), Sumifix Supura Blue BRF (SumlfLx 5upra Blu
e BRF) (manufactured by Sumitomo Chemical Co., Ltd.).

Each sample was dyed with each dye (reactive dye) at a concentration of 14 owf at 60° C. for 30 minutes.

Comparative Example 4 Example 1 for rayon that has not been cationized
The same staining was performed.

The dyeability of the dyed fabrics of Example 4 and Comparative Example 4 obtained by the above method is shown in Figure 4.

4 Comparative Example 5 Using the same reactive dye and direct dye as in Example 4, a refined white rayon cloth was dyed under the following conditions. For reactive dyes, add 301/ml of Glauber's salt to the dye liquor in advance, and after raising the temperature (60°C), add 101/ml of Na 2 COa.
/j and stain for 60 minutes. For direct dyes, after heating (to 90°C), add Glauber's Salt 2011/j and dye for 60 minutes. Table 5 shows data comparing the K/S value and wet fastness of the rayon-dyed fabric obtained by such a conventional dyeing method and the cationized rayon-dyed fabric obtained in Example 4.

Table 5 Korean λ1″”sa620nm ””λ0″”-640
From the results above, it was confirmed that the cationized regenerated cellulose fibers of the present invention have significantly improved wet durability compared to conventional regenerated cellulose fibers.

Example 5 A plain woven fabric made of 50 d of rayon and 100 d of silk twisted and twisted.The fabric was cationized and printed using the same treatment method as in Example 2. Gluing conditions are shown below.

Reactive dye ``20 Gluing agent Nisnor Algin M (4th section) Dye used 709 Sumifix Sugera Yellow 3RF (Sumitomo Chemical (
Co., Ltd.) (8umlfix 8upra Yella
gf3RF) Sumificuki Puriri'an' Tread C
F ()〆(Sumiflx 5upra Br1ll Red
GF) Sumifix Spra-Plue BRF (#
)(Sumifix 8upra Blu@
BRF) After printing, it was dried at 100°C for 1 minute, and then subjected to moist heat treatment at 105°C for 15 minutes using an HT steamer. Subsequently, desizing, washing with water, soaping, dehydration, and drying were performed. As a soaping agent, 2 cc/l of Bisnor RK (manufactured by Ippo Sha Yushi Kogyo Co., Ltd., an anionic activator) was used.

The cationized rayon silk twisted fabric obtained through the above process was very bright and dyed in the same color.

Example 6 A cotton jersey fabric tube made of 70% rayon and 30 width wool blended yarn (40 cotton count) It was cationized under the same conditions as in Example 1 and dyed under the following conditions.

Dye: Kayano Milling Blue GW (Kayano
lMllll, Blue GW) (Nippon Kayaku Co., Ltd.)
Made.

Acidic dye) 2% owf Bath ratio: 1:50 Warming: 90°C The cationized rayon cool blend fabric obtained through a process of time = 30 minutes or more was dyed in a deep color and the same color.

Example 7 A refined white rayon cloth was immersed in a cationizing agent (CI9011/11. caustic soda 1011/1 bath) listed in Attached Table 1 and squeezed to a size of 80 with a mangle.
5upra Br111. Red GF) (9 reactive dye manufactured by Sumitomo Chemical Co., Ltd.) Immerse in a 1011/l bath, squeeze with a mangle, and dry at 100°C for 1 minute. Subsequently, the cloth is washed with water, soaped, dehydrated, and dried.

The cationized rayon cloth obtained through the above process was dyed in a very bright, dark, and even color.

Example 8 Refined Pempelg white cloth was mixed with cationized 41(c) 1001/l listed in Attached Table 1 and Kayarasugerai IC!
-RL (Kayarus 5upra Yellow
w RL) (Nippon Kayaku Co., Ltd., direct dye) 10.9
After immersing it in a mixed aqueous solution containing J/J, it was squeezed with a mangle to a ratio of 80°C at 100°C.

Dry for 1 minute. The steps after washing with water are the same as in Example 7.

The cationized Bemperg dyed fabric obtained by the above-mentioned process had a considerably deep color and was evenly dyed.

Example 9 The refined Penpelg knitted fabric was cationized in the same manner as in Example 1.

Comparative Example 6 The refined Bemperg knitted fabric was treated with a resin finishing agent Sumitex Resin MS-18 (Sumit@x Realm NS-
18) (Manufactured by Sumitomo Chemical Co., Ltd. - Brioquibul-based resin processing agent) Section 15 and Sumitex Accelerator X-8X
-80 (Su@x Ace X-80) (Sumitomo Chemical (
Co., Ltd., composite metal salt catalyst) 4.54, squeezed with a mangle to a ratio of 80, dried at 100°C for 1 minute, and further heat-treated at 165°C for 2 minutes.

Table 9 shows the measurement results of the saturated moisture content and swelling degree strength of the Bempergue knitted fabrics of Example 9 and Comparative Example 6 obtained as described above, and the Pempergue knitted fabrics with a refining level of 9. Note that the strength was measured by de-knitting the knitted fabric and using yarn.

In addition, water absorption was measured by the Pisic method.

Table 9 According to the above results, the products of the present invention retain the excellent properties of regenerated cellulose fibers compared to resin-processed products, and also have improved water absorption compared to conventional regenerated cellulose fffa.

Table 1 in the margin below: 1 Cationizing agent (A)
1. □ □Cationizing agent (uniform □Cationizing agent (C) Effect of the present invention>) As is clear from the above results, the cationized regenerated cellulose fiber of the present invention is superior to the previously proposed cationized cellulose fiber. It has excellent properties such as flexibility, swelling degree, and hygroscopicity, and overcomes the drawbacks of conventional cationized cellulose fibers (
It overcomes the problems of poor durability and level dyeing properties, and also significantly improves wet fastness compared to conventional regenerated cellulose fibers.

Claims (1)

[Claims] A method for producing regenerated cellulose fibers, characterized by treatment with a compound represented by formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In formula (I), A_1, A_2, A_3 and A_4 are hydrogen, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, An aryl group or an aralkyl group having 7 to 18 carbon atoms, x is an integer of 1 or more, B_1 and B_2 are
Each is hydrogen, except when both are hydrogen, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (X is a halogen atom), ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ , Y is an acid residue. ]