JP2761520B2 - Cationic regenerated cellulose products - Google Patents

Description

The present invention relates to a cationic regenerated cellulose product having excellent reactivity with anionic dyes and various anionic compounds and excellent adsorption performance. More specifically, it relates to a cationic regenerated cellulose product regenerated by mixing a bisquaternary ammonium salt polymer in a viscose stage.

[Related Art] Viscose rayon (regenerated cellulose fiber) is a kind of cellulosic fiber like cotton and hemp, and inherently exhibits weak anionicity. Therefore, dyeing with an anionic dye such as an acid dye or a metal-containing complex dye cannot be performed, and good dyeing cannot be performed unless the presence of alkali and high pH and high temperature are used for the reactive dye. For this reason, the hue and the number of colors are limited, and in the case of a blended or woven product with another kind of fiber, it must be dyed twice. Furthermore, various treatment agents such as softening agents, water repellents, flame retardants, etc. are often anionic, but due to their weak bonding force, their washing resistance is extremely poor and they cannot be practically used. Disadvantages.

Therefore, various treatment methods have been conventionally proposed mainly for dyeing with an anionic dye. Most of them are to cationize cotton, yarn, cloth and the like of viscose rayon with an aqueous solution of a cationic compound that reacts with cellulosic fibers.

As this kind of compound, as a reactive group in the compound,
A fiber-reactive compound containing a halogenated triazine group or a halogenated pyrimidine group (for example, JP-A-52-155286);
Monofunctional fourth having one reactive group capable of reacting with a cellulosic fiber material, such as 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-epoxypropyltrimethylammonium chloride.
Grade compounds (for example, JP-B-39-5985, JP-B-46-40510)
Bifunctional quaternary compounds having two or more quaternary ammonium groups in one molecule and having two or more halohydrin groups and / or epoxy groups as reactive groups (JP-A No. 60-134080).

Among them, the bifunctional quaternary compound has been developed by the present inventors, and has a high molecular weight, a high affinity for a fiber material, is highly reactive, is soluble in water, and further has an alkali catalyst. Reacts efficiently with fiber material underneath. In addition, the treated cellulosic fiber dyed anion dye has high fastness and good dyeability.

[Problems to be Solved by the Invention] However, treating cotton, yarn, and fabric of viscose rayon using these compounds has the advantage of being able to cope with small lots, but increases the number of extra steps, thus increasing the cost. This also reduces efficiency. Moreover, the cost is increased due to the use of many drugs, and in many cases, the reaction efficiency is generally poor and the effect is not sufficient.

Therefore, the present inventors have conducted intensive research focusing on the possibility of efficiently cationizing at low cost without adding an extra step if the above-mentioned cationic compound is mixed at the viscose stage and spun. .

However, among the compounds described above, the effect of cationization is not sufficient even in the case of treatment with an aqueous solution, and due to the low molecular weight, it is eluted in the spinning bath during regeneration and hardly remains in the fiber, and the effect is almost zero. I knew there wasn't. If the compound is made long to increase the molecular weight, air is likely to be mixed into the viscose due to the surface active effect, making uniform and powerful spinning impossible.

The elution of the compound into the spinning solution is somewhat better, but due to bifunctionality, a cross-linking reaction occurs in the viscose, and the viscose thickens or gels, and the spinning conditions become severe and the spinning conditions become severe. Unavailable.

In the case of cellophane, which is the same regenerated cellulose product as rayon, the dyeing is carried out in the film-forming process, so the concentration of the dyeing bath decreases due to the inflow of washing water. Irregularities also tend to occur. Also,
Since it cannot be processed after immersion in a bath, it is also difficult to add functions such as sterilization and deodorization to cellophane. Similarly, it is also difficult to firmly fix various anionic functional chemicals to the viscose regenerated sponge.

[Means for Solving the Problems] Accordingly, the present inventors have further studied and studied a quaternary salt-containing polymer (a quaternary ammonium nitrogen atom to be attached to or coated on a synthetic fiber product and surface-cationized). Polymer containing at least one monomer containing two quaternary ammonium nitrogen atoms (hereinafter referred to as "bis quaternary ammonium salt polymer"). The use has led to solving the above problems.

The bisquaternary ammonium salt polymer has a high residual ratio because it is less dissolved into the spinning bath because of its high molecular weight, and is stable in the spinning bath without causing a crosslinking reaction or the like in the viscose liquid. Moreover, it has a feature that the effect of cationization is greater than that of a monoquaternary ammonium salt polymer having one quaternary ammonium nitrogen atom.

The bis-quaternary ammonium salt polymer used in the present invention is a polymer or copolymer containing as a main component at least one monomer having two quaternary ammonium nitrogen atoms as represented by the general formula [I]. It is.

However, in the formula (I), R ₁ is hydrogen or a methyl group, R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ each represent an alkyl group having 1 to 18 carbon atoms, an oxyalkyl group or an aralkyl group, and A represents —COO— or —CO—NR ₇ — (where R ₇ is hydrogen, methyl or B represents CH _{2 n} (where n represents an integer of 2, 3 or 4) or —CH ₂ CH (OH) CH ₂
And X and Y each represent a halogen or a methosulfate group.

The bisquaternary ammonium salt monomer represented by the formula [I] is obtained, for example, by reacting a tertiary amine monomer with a quaternized compound. In this case, tertiary amine monomers include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, 3- (dimethylamino) propyl acrylate, 4- (dimethylamino) butyl acrylate, and 3- (dimethylamino)- 2-Hydroxypropyl methacrylamide and others are used. Examples of the quaternized compound include (2-hydroxy-3-chloropropyl) trimethylammonium chloride, (2-hydroxy-3-chloropropyl) stearyldimethylammonium chloride, and (2-hydroxy-3-chloropropyl) dimethyloctylammonium. Chloride,
(2-Hydroxy-3-bromopropyltrimethylammonium chloride, (2-hydroxy-3-chloropropyl) triethylammonium chloride, (2-hydroxy-3-bromopropyl) triethylammonium chloride, etc. These bis-quaternaries Examples of the monomer copolymerized with the ammonium salt monomer include methyl acrylate, methyl methacrylate, lauryl methacrylate, diethylaminoethyl methacrylate, N-methylolacrylamide, vinyl acetate, and styrene.

These combinations result in a wide variety of bisquaternary ammonium salt polymers. The polymerization of these monomers may be carried out in a conventional manner, and may be carried out in water or an organic solvent using a radical catalyst. The degree of polymerization is not particularly limited, but if the degree of polymerization is low, it is easily eluted into the spinning bath, and if it is too high, the viscosity of viscose becomes high and spinning becomes difficult. For example, the viscosity (30 ° C) of a 25% (wt%) aqueous solution of a polymer is
About 100 to 20000 cp is preferable.

Cotton and yarn of viscose rayon spun by mixing these bisquaternary ammonium salt polymers into viscose,
The fabric is dyed very well with an anionic dye, similarly to the case where ordinary viscose rayon is treated with the above-mentioned cationic compound, and is clearly dyed with a reactive dye without using alkali or sodium sulfate. The adsorption of other anionic treating agents and other compounds is also very good.

The mixing ratio of the bisquaternary ammonium salt polymer is about 0.5 to 50% by weight, based on the solid content of cellulose (dry weight) in the viscose liquid. If it is less than 0.5%, a sufficient effect of cationization cannot be seen, and if it is more than 50%, the physical properties of the fiber are greatly reduced and the practical value is poor. More preferably, it is about 5 to 20%.

In the present invention, the type of viscose is not particularly limited,
Fibers such as regular type, high-strength rayon, highly wet elastic viscose rayon and the like, or viscose used for producing cellophane and sponge can be used. Further, the mixing of the bisquaternary ammonium salt polymer into the viscose may be mixed with the viscose already prepared, or the viscose may be prepared after mixing with the cellulose xanthate after sulfidation. Good.

The rayon of the present invention thus obtained can be dyed well with an anionic dye, and can be easily treated with various treatment agents such as an anionic softening agent, a water repellent, and a flame retardant. It can be performed reliably. Furthermore, it can be used as it is as an adsorbent for anionic substances, and can be combined with an anionic bactericide, a deodorant, or the like to produce various functional fiber materials. Also, in the case of cellophane or sponge, dyeing with an anionic dye is performed well, and various treating agents and functional substances can be firmly bound.

[Examples] Next, the present invention will be described in more detail with reference to examples.

Example 1 A polymer of a bisquaternary ammonium salt monomer represented by the formula [II] (viscosity at 30 ° C. of a 25% aqueous solution is 4000 c
p) is 0%, 5%, 10%, 20%
% And 30% and mix well.

This polymer-mixed viscose was spun from a nozzle into a spinning bath containing sulfuric acid 120 g /, sodium sulfate 300 g /, and zinc sulfate 15 g /, stretched, scoured, and dried to obtain a 7d-thick cationized rayon.

The degree of cationization of the resulting cationized rayon,
Dyeing was performed with a reactive dye, which is a kind of anionic dye, and the degree of the dyeing was used to judge. Staining conditions and measurement results (L
Values are shown in Table 1. The cationized rayon is 5c long
The sheet was cut into pieces of about m to form a cotton, and subjected to a test.

Staining conditions Remazol Brilliant Red F-3B (reactive dye,
Each of the above cationized rayon cottons is immersed in a dye aqueous solution (manufactured by Hoechst Co.) adjusted to 10% owf (without using an auxiliary such as alkali or sodium sulfate) at a bath ratio of 1:20, and heated to 60 ° C. 60
Stain for minutes. Subsequently, it was sufficiently washed with water and air-dried.

L value The L value of each obtained dyed cotton was measured using a colorimetric color difference meter (Z-1001-DP type manufactured by Nippon Denshoku Industries Co., Ltd.). Note that L
The value represents the brightness, and the larger the value, the brighter, that is, the lower the surface staining density. That is, in the case of 0% (the cationizing agent was not mixed), it was dyed only in a very light red color.
Those mixed with the cationizing agent were dyed vivid red according to the concentration.

Examples 2 to 9 Bis quaternary ammonium salt polymers of the formula [I]
In Example 1, A, B, R _{1 to} R ₆ , X and Y in Table ₁ were each a polymer of a monomer shown in Table 2 (25% aqueous solution, viscosity at 30 ° C. is shown in Table 2). In the same manner as described above, cationized rayon cotton was obtained. Viscose of bisquaternary ammonium salt polymer The mixing ratio with respect to cellulose is 10% by weight based on cellulose.

Each cationized rayon cotton was dyed in the same manner as in Example 1, and the L value was measured. Table 2 also shows the measurement results.

Comparative Examples 1-4 Instead of the cationic compound in Example 1, the following reactive quaternary ammonium (Comparative Examples 1-3), tertiary amine polymer (Comparative Example 4) and monoquaternary ammonium polymer (Comparative) Example 5) was mixed with viscose (solid concentration of cellulose: 10%) and spun in the same manner as in Example 1 to obtain rayon cotton. In addition, staining was performed under the same conditions as in Example 1, and L value was measured. Table 3 shows the results.

Comparative Example 1 was (2-hydroxy-3-chloropropyl) trimethylammonium chloride, Comparative Example 2 was (2-hydroxy-3-chloropropyl) dimethylbutylammonium chloride, and Comparative Example 3 was (2-hydroxy-3-chloropropyl). Chloropropyl) dimethyllauryl ammonium chloride, Comparative Example 4 was polydimethylaminoethyl acrylate (concentration 25%, viscosity 2500 cp at 30 ° C.) Comparative Example 5 was poly [trimethyl (methacryloylethyl) ammonium chloride] (concentration 25%, 30 ° C.) The viscosity was 2000 cp).

The dyed articles of these comparative examples are lighter in color than those of the examples, and particularly those of comparative examples 1 and 2 are hardly stained. The results of Comparative Example 3 are somewhat better, but these are probably due to the fact that most of the cationic compound elutes into the spinning bath during viscose regeneration and hardly remains. In Comparative Examples 4 and 5, it is considered that the elution is small because of the polymer, but the cationic effect is inferior to that of the present invention.

[Effects of the Invention] As described in detail above, the cationic regenerated cellulose product of the present invention is obtained by mixing a bisquaternary ammonium salt polymer in a viscose stage and regenerating the same by a conventional method. And, as is clear from the test results, it shows an extremely excellent ability to adsorb anionic substances such as anionic dyes.
This is presumably due to the fact that the bisquaternary ammonium salt polymer remained in the regenerated cellulose product in an amount sufficient to sufficiently exhibit cationicity, and exhibited excellent cationic performance.

Thus, the viscose rayon, cellophane and sponge of the present invention are extremely easily and reliably dyed with an anionic dye, treated with an anionic treating agent, and adsorbed with various anionic compounds, which were conventionally difficult or extremely unsatisfactory. And greatly improve the application and performance.

Claims (1)

(57) [Claims] 1. A cationic regenerated cellulose product obtained by mixing a bisquaternary ammonium salt polymer in viscose and regenerating it.