JPH02274738A - Cationic regenerated cellulose product - Google Patents

Abstract

PURPOSE:To obtain a cationic regenerated cellulose product excellent in reactivi ty with an anionic dye or an anionic compound and adsorptivity for them by mixing a viscose with a bis(quat. ammonium salt) polymer. CONSTITUTION:A viscose is mixed with a polymer based on a monomer having two quat. ammonium groups (e.g. an acrylic monomer of the formula), desirably a bis(quat. ammonium salt) polymer of a viscosity of about 100 to 20000cP when determined in a 25wt.% aqueous solution at 30 deg.C, and the mixture is formed into a cationic regenerated cellulose product such as a cotton, yarn, cloth or the like of viscose rayon. The amount (in terms of the solid matter) of the bis(quat. ammonium salt) polymer mixed is 0.5 to 50wt.%, desirably 5 to 20wt.% based on the dry weight of the cellulose in the viscose solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a cationic regenerated cellulose product that has excellent reactivity and adsorption performance with anionic dyes and various anionic compounds. More specifically, the present invention relates to a cationic regenerated cellulose product that is regenerated by mixing a bis-quaternary ammonium salt polymer at the viscose stage.

[Prior Art] Viscose rayon (regenerated cellulose fiber) is a type of cellulose fiber like cotton and linen, and inherently exhibits weak anionic properties. Therefore, dyeing with anionic dyes such as acidic dyes and metal-containing complex dyes is not possible, and good dyeing with reactive dyes requires the presence of alkali, high pl+, and high temperature. Therefore, the hue and number of colors are limited, and products mixed with other types of tFh fibers or interwoven products must be dyed twice. Furthermore, many of the various processing agents such as fabric softeners, water repellents, and flame retardants are anionic, but because the bonding strength with these agents is weak, their washing resistance is extremely poor, making them impossible to put into practical use. It has some drawbacks.

Therefore, various treatment methods have been proposed in the past, mainly regarding dyeing with anionic dyes.

In most cases, viscose rayon cotton, thread, fabric, etc. are cationized using an aqueous solution of a cationic compound that reacts with cellulose fibers.

Examples of this type of compound include (1) fiber-reactive compounds containing a halogenated triazine group or a halogenated pyrimidine group as a reactive group in the compound (for example, JP-A No. 52-15528;
6), (3-Chloro-2hydroxypropyl l-rimedylammonium chloride and 2,3-epoxypropyltrimethylammonium chloride), which have one reactive group that can react with cellulose fiber materials; Functional type quaternary compounds (e.g., Japanese Patent Publication No. 39-5985, Japanese Patent Publication No. 4.6-40510, etc.), - Has two or more quaternary ammonium groups in the molecule, and has a halohydrin group and an epoxy group as reactive groups. Trifunctional quaternary compounds having two or more of one or both groups (Japanese Patent Application Laid-Open No. 6O-13408)
0) etc.

Among these, the trifunctional quaternary compound (3) was developed by the present inventors, and has a large molecular weight and a high affinity for fiber materials, is highly reactive, is soluble in water, and has an alkaline catalyst. reacts efficiently with fiber materials in the presence of In addition, the treated cellulose fibers dyed with anion dyes have high fastness and good dyeability.

[Problems to be Solved by the Invention] However, while treating viscose rayon cotton, thread, and fabric with these compounds has the advantage of being able to handle small rosés, it requires an additional process. It is costly and inefficient. Furthermore, the cost is high because many drugs are used, and the reaction efficiency is generally poor (many of them are not sufficiently effective).

Therefore, the present inventors conducted intensive research focusing on the possibility that by mixing the above-mentioned cationic compound at the viscose stage and spinning it, cationization could be achieved efficiently at low cost without requiring any extra steps. .

However, among the above compounds, those shown in (1) and (2) do not have sufficient cationization effects even when treated with an aqueous solution, and because of their low molecular weight, they melt into the spinning bath during regeneration and hardly remain in the fibers. It turned out that there was almost no effect. Also, ■
When a long chain is used to increase the molecular weight of a compound, air tends to be mixed into the viscose due to the surfactant effect, making uniform and strong spinning impossible.

In addition, the compound (■) is somewhat better eluted into the spinning solution, but because it is bifunctional, it causes a crosslinking reaction in the viscose, which thickens the viscose and turns it into a gel, making the spinning conditions harsher. is unusable.

In addition, in the case of cellophane, which is a regenerated cellulose product like rayon, dyeing is done in the film forming process, so the dyeing bath loses its concentration due to the inflow of washing water, so there is a lot of waste, such as constantly replenishing high-concentration liquid. It also tends to cause unevenness. Furthermore, since it is not possible to process the cellophane after immersing it in a bath, it is difficult to add functions such as sterilization and deodorizing properties to cellophane. Similarly, it is difficult to firmly adhere various anionic functional chemicals to viscose recycled sponge.

[Means for Solving the Problems] Therefore, the present inventors continued their research and developed a quaternary salt-containing polymer (quaternary ammonium nitrogen atom) that can be attached or coated onto synthetic fiber products to give them a cationic surface treatment. (hereinafter, such polymers are referred to as r-bis quaternary ammonium salt polymers). By using this method, we have been able to solve the above problems.

Since the bisquaternary ammonium salt polymer is a polymer, there is little elution into the spinning bath, so the residual rate is large, and it does not cause a crosslinking reaction in the viscose liquid and is stable even in the spinning bath. Moreover, it has a feature that the cationization effect is greater than that of a mono-quaternary 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 whose main component is at least one monomer containing two quaternary ammonium nitrogen atoms as shown in formula (1).

However, R1 is hydrogen or a methyl group, R2, R3,
R4, R5 and R6 each represent an alkyl group, oxyalkyl group or aralkyl group having 1 to 18 carbon atoms, and A is -C
Any of OO- or -Co-NRv (wherein R7 represents either hydrogen, methyl group or ethyl group),
B is +CHZ (however, n indicates an integer of 2.3 or 4)
or CH2CH(OH) C)+ 2-,
X and Y each represent either a halogen or a methosulfate group.

The bisquaternary ammonium salt monomer represented by formula [I] can be obtained, for example, by reacting a tertiary amine monomer with a quaternized compound. In this case, the tertiary amine monomers include dimethylamine ethyl methacrylate-1.
, 3(dimethylamino)-2-hydroxypropylmethacrylamide and others are used. The quaternized compounds include (2-hydroxy-3-chloropropyl)trimethylammonium chloride, (2-hydroxy-3-chloropropyl)stearyldimethylammonium chloride, and (2hydroxy-3-chloropropyl)dimethyloctylammonium chloride. , (2-
Examples include hydroxy-3-bromopropyltrimethylammonium chloride, (2-hydroxy-3-chloropropyl)triethylammonium chloride, (2hydroxy-3=bromopropyl)triethylammonium chloride, and the like. Examples of monomers to be copolymerized with these bis-quaternary ammonium salt monomers include methyl acrylate, methyl methacrylate, lauryl methacrylate, diethylaminoethyl methacrylate, N-methylolacrylamide, vinyl acetate, and styrene.

These combinations yield a wide variety of bis-quaternary ammonium salt polymers. Incidentally, these monomers may be polymerized by a conventional method, and may be polymerized using a radical catalyst in water or an organic solvent. The degree of polymerization is not particularly limited, but if the degree of polymerization is low, it will easily dissolve into the spinning bath, and if it is too high, the viscosity of the viscose will become high and it will be spun into shoes. For example, the viscosity of a 25% (wt%) aqueous solution of a polymer (30°C
) is preferably about 100 to 20,000 cp.

Viscose rayon cotton fabric made by mixing these bis-quaternary ammonium salt polymers into hiscose and spinning is produced by treating the fabric with an anionic dye, similar to ordinary viscose rayon treated with the above-mentioned cationic compound (2). It dyes well and is vividly dyed with reactive dyes without using alkali or Glauber's salt. In addition, adsorption of other anionic processing agents and other compounds is also extremely good.

The mixing ratio of the bisquaternary ammonium salt polymer is 0.5 to 50% by weight based on the solid content of cellulose (dry type M) in the viscose liquid. If it is less than 0.5%, no sufficient cationization effect will be observed, and if it is more than 50%, the physical properties of the fiber will be greatly reduced and the practical value will be poor. More preferably, it is about 5 to 20%.

In the present invention, the type of viscose is not particularly limited, and any fiber such as regular type, strong rayon, high wet elasticity viscose rayon, or viscose used for manufacturing cellophane or sponge can be used. . In addition, the bisquaternary ammonium salt polymer may be mixed into viscose by mixing it into already prepared viscose, or by mixing it with cellulose xanthate after sulfurization and then preparing viscose. good.

The rayon of the present invention thus obtained can be dyed well with anionic dyes, and can also be easily treated with various treatment agents such as anionic softeners, water repellents, and flame retardants to make it water resistant. It can be done reliably. Furthermore, it can be used as it is as an adsorbent for anionic substances, and can be made into various functional fiber materials by combining anionic disinfectants, deodorants, etc. Furthermore, in the case of cellophane and sponge, dyeing with anionic dyes is performed well, and various processing agents and functional substances can be firmly bound.

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

Example 1 For viscose with a cellulose concentration of 6% and an alkali concentration of G, a polymer of a bisquaternary ammonium salt monomer represented by the formula CI
000cp), solid content based on cellulose O%, 5%, 1
Add at a ratio of 0%, 20%, and 30% and mix well.

H3 This polymer mixed viscose was mixed with sulfur M l 20 g/
β, sodium sulfate 300 g/#, zinc sulfate 15 g'
/j! Spinning from a nozzle into a spinning bath containing
Dried 7 d thick cationized rayon (M).

The degree of cationization of the obtained cationized rayon was determined by dyeing with a reactive dye, which is a type of anionic dye. The staining conditions and measurement results (I-value) are shown in Table-1. In addition, the length of cationized rayon is 5c.
The fibers were cut into cotton-like pieces and used for testing.

Dyeing conditions Remazol Brilliant Trend F to 3B (reactive dye, manufactured by Hoechst) Each of the above cationized rayons was added to a dye aqueous solution adjusted to 10% O, W, F (no auxiliary agents such as alkali or Glauber's salt were used). Cotton is immersed in a bath ratio of 1:20, heated and dyed at 60°C for 60 minutes. Subsequently, it was thoroughly washed with water and air-dried.

L value The L value of each dyed cotton obtained was measured using a colorimetric color difference needle (Z-1001-DP type manufactured by Nippon Denshoku Kogyo @ Candle). still,
The L value represents brightness, and the larger the value, the lighter the surface staining density. That is, in the case of 0% (no other cationic agent mixed), only a very light red color was dyed, but in the case of cationizing agent mixed, the dyed color was bright red depending on the concentration.

Table-1 Examples 2 to 9 As a bis-quaternary ammonium salt polymer, A, +3. Cationized rayon was prepared in the same manner as in Example 1 using a polymer of monomers in which R, -R6, X and Y are shown in Table 2 (25% aqueous solution, viscosity at 30°C is shown in Table 2). I made cotton.

The mixing ratio of the bisquaternary ammonium salt polymer to the viscose is 10% by weight based on the cellulose.

Each cationized cotton was dyed in the same manner as in Example 1, and its L value was measured. The measurement results are also shown in the table.
Shown in 2.

Comparative Examples 1 to 4 Instead of the cationic compound in Example 1, the following reactive quaternary ammonium (Comparative Examples 1 to 3), tertiary amine polymer (Comparative Example 4), and monoquaternary ammonium polymer (Comparative Example 5) were mixed with viscose (10% solid content of cellulose) and spun in the same manner as in Example 1 to obtain rayon cotton. In addition, it was dyed under the same conditions as in Example 1, and the scale value was measured. The results are shown in Table-3.

In addition, Comparative Example 1 is (2-hydroxydi-3-chloropropyl)trimethylammonium chloride, Comparative Example 2 is (
2-Hydroxy-3-chloropropyl)dimethylbutylammonium chloride, Comparative Example 3 Ha(2-hydroxy-3-chloropropyl)dimethyllauryl ammonium chloride, Comparative Example 4 was polydimethylaminoethyl acrylate (concentration 25%, 30°C Viscosity 2500cp)
Comparative Example 5 used poly[i.dimethyl(methacryloylethyl)ammonium chloride] (concentration 25%, viscosity at 30° C. 2000 cp).

The dyed products of these comparative examples are lighter in color than those of the examples,
In particular, those of Comparative Examples 1 and 2 were hardly dyed. Comparative Example 3 was somewhat better, but this is probably because most of the cationic compounds were eluted into the spinning bath during viscose regeneration, and very little remained. Further, it is thought that the samples of Comparative Examples 4 and 5 have less elution due to the polymer, but this is probably due to the fact that the cationic effect is inferior to that of the samples of the present invention.

[Effects of the Invention] As detailed above, the cationic regenerated cellulose product J of the present invention is obtained by mixing a bisquaternary ammonium salt polymer at the viscose stage and regenerating this by a conventional method. . As is clear from the test results, it exhibits an extremely excellent ability to adsorb anionic substances such as anionic dyes.

This is believed to be because the bis-quaternary ammonium salt polymer remains in the regenerated cellulose product in an amount sufficient to fully exhibit cationic properties, and also exhibits excellent cationic performance.

Therefore, the viscose rayon, cellophane, and sponge of the present invention can be easily and reliably dyed with anionic dyes, treated with anionic treatment agents, and adsorbed with various anionic compounds, which were previously difficult or extremely unsatisfactory. This greatly improves the application and performance.

Claims (1)

[Claims] 1. A cationic regenerated cellulose product characterized by mixing bisquaternary ammonium salt polymer into viscose and regenerating the mixture.