JPH09157942A - Regenerated cellulose fiber excellent in dyeing property and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a regenerated cellulosic fiber excellent in dyeing property to acidic dye and light resistance by adding a polyallylamine (derivative) to viscose and spinning the mixture and coagulation-regenerating, refining and drying the spun yarn. SOLUTION: A polyallylamine and/or polyallylamine derivative such as cyanoethylated polyallylamine having 1-100mol% cyanoethylation ratio, preferably in an amount of 0.1-20.0wt.% (based on cellulose) is added to viscose and the mixture is spun and the spun yarn is coagulation-regenerated, refined and dried to provide the objective regenerated cellulose fiber. Furthermore, the degree of polymerization of the polyallylamine (derivative) is preferably >=10000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a regenerated cellulose fiber having excellent dyeing properties for anionic dyes, particularly metal-containing dyes or acid dyes, and excellent light resistance of the dyed product, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Viscose rayon is used in many applications as a fiber having extremely excellent hygroscopicity and as a fiber which is easily dyed. However, since it has no direct affinity for acid dyes, dyeing with acid dyes was extremely difficult. Therefore, for example, when mixed spinning with acid dye and high affinity wool, or mixed knitting, and then dyed, the rayon side and the wool side are individually bathed with a suitable dye, or dyed by a dyeing operation of the bath, Color matching is required, which is complicated and at the same time requires a great deal of expense and processing time.

Therefore, it is of great significance to impart an affinity for ray dyes to rayon, and as a method therefor, a high-molecular polymer having an amino group and an imino group such as polyethyleneimine is used for modification. The method of doing is proposed. For example, JP-B-48-23834 discloses a method of immersing rayon in a polyethyleneimine aqueous solution, and JP-A-64-20313 and JP-A-52-9.
A method of mixing an oligomer or a polymer containing a quaternary ammonium salt with viscose and spinning the mixture in a conventional manner is reported in Japanese Patent No. 1913 and the like.

[0004]

However, in the former case, the modification is carried out by post-treatment, and the operation is complicated, and there is concern about the strength of the bond between polyethyleneimine and rayon, which are modifiers, due to the post-treatment. . On the other hand, in the latter case, the method for making rayon dull yarn is applied as is,
Although it is not complicated and is a very advantageous method for production, when the modified rayon is produced, the compatibility with viscose is very poor when a polymer is used, and the viscosity of viscose increases abnormally. In addition, in the case of oligomers, the outflow to the spinning bath is unavoidable during spinning, and not only the yield is very poor, but also the viscous (fibrous agglomerates) that is thought to be caused by poor coagulation and regeneration in the spinning process. However, there is a drawback that it is difficult to stably produce the modified rayon. In addition, 1-5
Japanese Patent No. 9361 also proposes a method in which polyethyleneimine is used as an additive to solve the above-mentioned problems in the production process, but it has a problem that its use is limited due to poor light resistance. .

[0005]

[Means for Solving the Problems] As a result of intensive studies for solving the above problems, the present inventors have found that polyallylamine and / or polyallylamine derivatives are added to viscose, mixed and spun to produce an acid dye. It was found that not only the dyeing property with respect to [1] but also the fastness to light was improved, and the present invention was completed. That is, the present invention provides a regenerated cellulose fiber containing polyallylamine and / or a polyallylamine derivative and having excellent dyeability, and a method for producing the same.

Hereinafter, the present invention will be described in detail. In the present invention, polyallylamine or a polyallylamine derivative is used. The polyallylamine derivative as referred to in the present invention is derived from polyallylamine and is, for example, N-obtained by reacting with an alkyl halide or the like.
N-cyanoethylated polyallylamine obtained by reacting with alkylated polyallylamine, N, N-dialkylated polyallylamine, acrylonitrile, etc.
N-γ-glutamylated polyallylamine obtained by reacting with activated glutamic acid, ND-obtained by reacting with D-gluconolactone, etc.
Examples thereof include gluconylated polyallylamine, and among them, cyanoethylated polyallylamine is preferable. It is preferable that 1 mol% or more of the amine in the polyallylamine is substituted in these derivatives.

The regenerated cellulose fiber of the present invention contains a polyallylamine or a polyallylamine derivative (hereinafter, both are simply referred to as polyallylamines), the content of which is 0.1 to 0.1% by weight of cellulose.
20.0% is preferable and 0.5 to 10.0% is particularly preferable. If the content is less than 0.1%, the absolute amount of basic nitrogen atoms that are affinity groups for the dye is small, the effect of improving the dyeing property of the target acid dye is not sufficient, and the content is If it exceeds 20.0%, the physical properties of the yarn such as spinnability and strength and elongation are deteriorated, which is not preferable. The degree of polymerization of polyallylamine is preferably 10,000 or more. When the degree of polymerization is less than 10,000, not only the entanglement with the cellulose is bad and the yield in the fiber is deteriorated,
The washing fastness of the product is also reduced.

The regenerated cellulose fiber of the present invention is produced by a continuous spinning method in which polyallylamines are added to and mixed with viscose, discharged from a spinning nozzle, coagulated and regenerated, and then refined and dried. To add and mix polyallylamine to viscose, various methods such as adding and mixing as a solution of water, alkali, alcohol, etc. can be carried out.However, since it can be easily dispersed in viscose, water or alkali can be used. The most preferred method is to add and mix the solution with viscose. The polyallylamines thus added and mixed are extremely uniformly dispersed in viscose, have good viscosity and fluidity, and are spun under the same conditions as normal viscose when spinning. It is obtained by refining and drying. That is, a viscose rayon filament, a viscose rayon filament, and a viscose containing a modifier that does not cause a chemical reaction or physical change that causes troubles when coexisting with polyallylamine. It can be applied to course fibers.

Since the polyallylamine used in the present invention has a great effect of modifying the polyallylamine, a practically small amount of addition is sufficient. Therefore, spinnability and physical properties are substantially the same as those of ordinary viscose rayon. Also,
The regenerated cellulose fiber obtained by the present invention hardly causes stains and physical properties that are likely to occur in the fiber obtained by adding a modifier to viscose. The reason for this is that when a compound containing a basic nitrogen atom is added to viscose, it has the function of solidifying viscose, but polyallylamines have a dispersibility in viscose despite containing a basic nitrogen atom. The present inventors presume that it is very good, and that it is coagulated and regenerated while being extremely uniformly dispersed in viscose. Another feature of the present invention is that nitrogen in polyallylamine exists as an amino group. Therefore, most of the bonds between the polyallylamine and the acid dye are not only electrostatic bonds, but also because the polyallylamine itself has an aggregating effect, dyeing occurs in the state where the acid dye is agglomerated and the light fastness of the dyed product is high. Will be good.

[0010]

The present invention will be described in detail below with reference to examples. The evaluation method in the present example is as follows. 1. Dry strength, dry elongation: JIS L-1069 (fiber tensile test method)
According to. 3. Residual rate of polyallylamines in the fiber: Calculated from the theoretical nitrogen amount in 1 g of rayon obtained from the addition amount of polyallylamine to cellulose (viscose) and the existing nitrogen amount by the Kjeldahl method. The theoretical amount of nitrogen is, for example, the amount of polyallylamine added is 1% / Cell
In the case of, (1 g × 1/100/57 (molecular weight)) mol (a) Measured value is an analytical value by the Kjeldahl method (b) Remaining rate in fiber = (b) / (a) × 100 4. Acid dye absorption rate: Indicates the dye exhaustion amount of a sample piece. It is calculated from the change rate of the dye concentration (measured from the light transmittance of the dyeing solution) before and after dyeing in the dye bath prepared in advance. 5. Lightfastness: In accordance with JIS L-0841 (Dyeing fastness test method against sunlight).

Example 1 Viscose (cellulose 8.5 obtained by a conventional method)
%, Total alkali 6.0%, total sulfur 2.0%) with commercially available polyallylamine (PAA-10C, manufactured by Nitto Boseki Co., Ltd.) at a polyallylamine amount of 0.5% based on the weight of cellulose, 2
%, 5%, 10%, 20%. The method of adding and mixing the polyallylamine aqueous solution to viscose is
A vacuum-closed stirrer was installed in the viscose pipe immediately before spinning, and the mixture was quantitatively and continuously added and mixed by a pump. The polymer-containing viscose thus obtained had a viscosity of 65
After spinning in a usual Mueller bath (sulfuric acid 120 g / L, sodium sulfate 350 g / L, zinc sulfate 15 g / L, spinning bath temperature 45 ° C.) using a spinner of μm × 8000 H, the normal refining process is performed. Then dried at 90 ° C for 24 hours,
3d of fiber was obtained. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained. (Note that as a reference example, the polyallylamine addition rate of 0% is also shown.)

Example 2 In Example 1, the cyanoethylated polyallylamine (1
A 0% aqueous solution (manufactured by Nitto Boseki Co., Ltd.) was added in the same manner as in Example 1 except that the amount of polyallylamine was 1.0%, 5.0% and 10.0% based on the weight of cellulose. I got it. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained.

Example 3 In Example 1, the cyanoethylated polyallylamine (1
A fiber was obtained in the same manner as in Example 1 except that 0% aqueous solution (manufactured by Nitto Boseki) was added so that the amount of polyallylamine was 1.0% based on the weight of cellulose. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained.

Comparative Example 1 Viscose (cellulose 8.5 obtained by a conventional method
%, Total alkali 6.0%, total sulfur 2.0%), an aqueous polyethyleneimine solution (10%) was added so that the amount of polyethyleneimine per cellulose was 2%. The method of addition and mixing to viscose was the same as in Example 1, and the same treatment as in Example 1 was performed thereafter to obtain a regenerated cellulose fiber. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained.

Comparative Example 2 Viscose (cellulose 8.5 obtained by a conventional method
%, Total alkali 6.0%, total sulfur 2.0%), an aqueous polyvinylpyrrolidone solution (10%) was added so that the amount of polyvinylpyrrolidone per cellulose was 5%. The method of addition and mixing to viscose was the same as in Example 1, and the same treatment as in Example 1 was performed thereafter to obtain a regenerated cellulose fiber. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained.

Comparative Example 3 Viscose (cellulose 8.5 obtained by a conventional method)
%, Total alkali 6.0%, total sulfur 2.0%), a polydiethylacrylamide aqueous solution (10%) was added so that the amount of polydiethylacrylamide per cellulose was 10%. The method of addition and mixing to viscose was the same as in Example 1, and the same treatment as in Example 1 was performed thereafter to obtain a regenerated cellulose fiber. Table 1 shows the physical properties, dyeing properties and light fastness of the dyed product obtained.

[0017]

[Table 1]

As is clear from Table 1, the regenerated cellulose fiber of the present invention has no change in not only physical properties such as strength and elongation but also the whiteness of the fiber as compared with ordinary viscose rayon, and the acid dye. The dyeing property with respect to is improved. Further, the regenerated cellulose fiber of the present invention, not only the fiber residual rate of the modifier is very high as compared with Comparative Example,
The improvement in light fastness is remarkable.

[0019]

As described above in detail, the regenerated cellulose fiber of the present invention has the same spinnability and physical properties as those of the viscose fiber, while being dyeable to an anionic dye, particularly to a metal-containing dye or an acid dye. In addition, the dyed product has been improved into a fiber having good light fastness, and its industrial effect is extremely large.

Claims (6)

[Claims] 1. A regenerated cellulose fiber containing polyallylamine and / or a polyallylamine derivative and having excellent dyeability. 2. The content of polyallylamine and / or polyallylamine derivative is 0.1 to 2 relative to cellulose.
The regenerated cellulose fiber having excellent dyeability according to claim 1, which is 0.0% by weight. 3. A regenerated cellulose fiber having excellent dyeability according to claim 1, wherein the polyallylamine and / or polyallylamine derivative has a degree of polymerization of 10,000 or more. 4. The regenerated cellulose fiber having excellent dyeability according to claim 1, wherein the polyallylamine derivative is cyanoethylated polyallylamine. 5. The cyanoethylation ratio of the cyanoethylated polyallylamine is from 1 mol% to 100 mol%.
Regenerated cellulose fiber with excellent dyeability. 6. A viscose rayon production process by a continuous spinning method in which viscose is discharged from a spinning nozzle, coagulated and regenerated, and then refined and dried.
Alternatively, a method for producing a regenerated cellulose fiber having excellent dyeability, which comprises spinning a mixture of a polyallylamine derivative and viscose.