JP2003020560A - Method for processing regenerated cellulose fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method, not impairing the appearance even when washing is repeated without impairing the strength and the touch feeling by controlling fibrillation which is a defect of a polynosic fiber or a regenerated cellulose fiber produced by a solvent-spinning method. SOLUTION: A regenerated cellulose fiber is treated with an aqueous solution containing three components composed of an acid, hydrogen peroxide and a metal compound having decomposition activity to hydrogen peroxide and then heat-treated to suppress fibrillation of the polynosic fiber or the regenerated cellulose fiber produced by the solvent-spinning method.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to regenerated cellulose fibers, especially polynosic fibers produced by viscose spinning or solvent-spun regenerated cellulose fibers produced by solvent spinning. The present invention relates to a processing method for suppressing fibrillation. [0002] Regenerated cellulose fibers are produced from ordinary rayon produced by the viscose method, polynosic fibers having high crystallinity and orientation using pulp having a high degree of polymerization, and copper produced by the copper ammonia method. Ammonia rayon is known. [0003] In recent years, solvent-spun regenerated cellulose fibers produced using an amine oxide-based solvent as a cellulose solvent have been developed and used. However, among the regenerated cellulose fibers, solvent-spun regenerated cellulose fibers and polynosic fibers, in particular, have a feature of being easily fibrillated by physical factors such as friction due to high crystallinity and high orientation. Utilizing this easy-to-fibrillate characteristic, for example, after kneading a knitted fabric made of these fibers and applying a physical force such as tapping to generate significant fibrils, most of the fibrils generated using the cellulolytic enzyme So-called peach-skin-like products have been developed in which only fine fibrils are left behind. However, this method requires a long processing time, has a problem in the reproducibility of the hue of the object,
There is a problem that the strength is lowered and it is difficult to adapt to thin objects, and fibrils are generated again due to repeated washing and the quality is remarkably impaired. The applications and usage methods are limited. Also, recently, the needs for textile products have diversified, and there is a growing demand for clear and flexible products that do not generate fibrils even after repeated washing. [0005] From such a viewpoint, many methods for preventing fibrillation of polynosic fiber and solvent-spun regenerated cellulose fiber have been proposed. For example, JP-A-7-7
No. 0930 discloses a method using a formalin-based treating agent, and JP-A-9-302584 and
195765 discloses a method using an epoxy-based treating agent. However, all of these methods use a polyfunctional reagent to cause a cross-linking reaction between celluloses to prevent fibrillation, and thus have a drawback of impairing the flexibility of fibers. On the other hand,
No. 1-61642 discloses a method of dissolving and removing generated fibrils using an amine oxide and a surfactant which are solvents used when obtaining regenerated cellulose fibers. Due to the use, the fiber has a drawback that the fiber becomes coarse and hard and the soft feel is impaired. SUMMARY OF THE INVENTION The present invention suppresses fibrillation, which is a drawback of polynosic fiber and solvent-spun regenerated cellulose fiber, without impairing the strength of the fiber product and the soft feel of the fiber. It is another object of the present invention to provide a method for processing regenerated cellulose fibers which does not impair the appearance even after repeated washing. Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned disadvantages, and as a result, have found that regenerated cellulose fibers can be treated with acid, hydrogen peroxide, and hydrogen peroxide. After treatment with an aqueous solution containing three components consisting of a metal compound having decomposition activity, by heat treatment, the fibrillation of polynosic fibers and solvent-spun regenerated cellulose fibers can be significantly suppressed, and the fiber strength and soft texture are improved. The inventors have found that the appearance is not impaired even after repeated washing without impairment, and the present invention has been completed. That is, the present invention provides a method for producing polynosic fibers or solvent-spun regenerated cellulose by strongly oxidizing only the vicinity of the fiber surface to cause cleavage of glycosidic bonds and reducing only the degree of polymerization of cellulose molecules near the fiber surface. This is a processing method for suppressing the fibrillation phenomenon caused by the high degree of polymerization, high crystallinity, and high orientation of the fiber. [0010] Therefore, in the object to be treated which has been processed according to the present invention, since the degree of polymerization is reduced only in the vicinity of the fiber surface, the strength is slightly reduced and the washing is repeated without impairing the soft texture. However, fibrils hardly occur and the appearance is not impaired. DETAILED DESCRIPTION OF THE INVENTION The regenerated cellulose fibers used in the present invention are polynosic fibers and solvent-spun regenerated cellulose fibers. Examples of the form include cotton, thread, knit, woven and non-woven fabric. The present invention relates to a process for processing a regenerated cellulose fiber comprising a polynosic fiber and a solvent-spun regenerated cellulose fiber, wherein water containing three components of acid, hydrogen peroxide, and a metal compound having a decomposition activity for hydrogen peroxide is used. It is characterized by using a processing liquid. When the concentration of a metal compound having a large effect on the oxidation reaction and having a decomposition activity for hydrogen peroxide is converted into a metal element, and the value obtained by multiplying the value by 100 is used, the total concentration of the three components in the water treatment solution is calculated. Is preferably used in the range of 2 to 5%. The sum of the concentrations of the three components is 2
%, The effect of suppressing fibrillation is insufficient, which is not preferable. If the total concentration of the three components exceeds 5%, the fiber strength is undesirably reduced. Next, the components constituting the three components will be described. As the acid, a mineral acid or an organic acid having a function as a stabilizer for hydrogen peroxide and an auxiliary function for cleaving a glucoside bond is used. However, mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are not preferred because they corrode metals used in the treatment apparatus, and the use of organic acids is preferred. Examples of such organic acids include formic acid, acetic acid, propionic acid, tartaric acid, malic acid, citric acid, and the like, and non-volatile acids such as tartaric acid, malic acid, and citric acid are particularly preferable. It is preferable to use these organic acids singly or as a mixture of two or more, and add them so that the concentration becomes 0.5% or more. If the amount added is less than 0.5%, the stability of hydrogen peroxide will decrease. [0014] Hydrogen peroxide is a central treating agent in the present processing, and it is preferable to use it by adding 1% or more. If the addition amount is less than 1%, the effect of suppressing fibrils becomes insufficient, which is not preferable. The metal compound having decomposition activity for hydrogen peroxide is selected from heavy metals such as titanium, chromium, manganese, iron, cobalt, nickel and copper which have decomposition activity for hydrogen peroxide in a water treatment bath. Hydrochloride, nitrate,
Sulfates, acetates, double salts thereof, and complex compounds such as ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) and diethylenetriaminepentaacetic acid (hereinafter abbreviated as DTPA) are preferably used. However, the toxicity of metals,
Considering the effect of release into the environment, iron hydrochloride, nitrate, sulfate or complex compounds of iron such as EDTA and DTPA are particularly preferable. In the present invention, these metal compounds may be used alone or in combination of two or more, and the concentration calculated as the metal element is 0.005% (100 times the value of 0.1%).
5%) or more. If the addition amount is less than 0.005%, the effect of suppressing fibrils becomes insufficient, which is not preferable. In the present invention, each of the components is added in the above-mentioned range, and the total of the concentrations of the three components is calculated by converting the concentration of the metal compound having decomposition activity to hydrogen peroxide into a metal element. When a value multiplied by 100 is used, the polynosic fiber or the solvent-spun regenerated cellulose fiber is treated in a water treatment bath such that the total concentration of the three components is in the range of 2 to 5%. After applying the three components to the polynosic fiber or the solvent-spun regenerated cellulose fiber, heat treatment is performed. As a method for applying the three components, a commonly used method is used, and a padding method is preferably used. That is,
A water treatment bath containing the above three components is prepared, immersed in this solution at room temperature for 1 to 10 seconds, and then squeezed to apply the three components to the object. The aperture ratio at this time may be within a normal range, and is selected within a range of 60 to 100%. The heat treatment may be performed by a commonly used method, particularly preferably steaming. The steaming may be performed at 95 to 105 ° C. for 1 to 5 minutes. Further, a surfactant or the like may be added to the water treatment liquid bath for the purpose of improving the permeability of the unrefined fibers and the like. [0017] Even if the dyeing treatment is carried out after the main processing, the fibril is suppressed, so that the finished quality of the fiber product can be improved. In order to pursue a more advanced texture,
After performing the processing according to the present invention, for example, a method of treating with a cellulolytic enzyme as a known method may be performed. The present invention relates to polynosic fibers or solvent-spun regenerated cellulose fibers and other fibers, for example, natural fibers such as cotton, hemp, wool and silk, ordinary rayon,
Cotton-like, thread-like, woven, etc. mixed with regenerated cellulose fibers such as copper ammonia rayon and high wet modulus rayon, and synthetic fibers such as nylon, acrylic and polyester
It can also be applied to knits, non-woven fabrics and the like. According to the present invention, a processing method is provided for these fiber products, in which the generation of fibrils is suppressed without impairing the soft texture and the appearance is not impaired even after repeated washing without generating fibrils. You can do it. The present invention will now be described in detail with reference to examples, but the present invention is not limited to these ranges. The appearance, texture, tear strength, burst strength, and stability of hydrogen peroxide were measured by the following methods. <Appearance> In order to confirm the state of the fibrils, they were stained and inspected as an appearance inspection. The method uses a 3.0% (owf) black dye (Sumifix Black B150).
%, Manufactured by Sumitomo Chemical Co., Ltd.) in a 50 L dye bath containing 5% sodium sulfate and 2% sodium carbonate at 70 ° C. for 60 hours.
After staining for minutes, it was washed. Furthermore, in a treatment bath containing 0.2% of a silicone finishing oil (Silicoran AN-1700, manufactured by YAS & Co., Ltd.), the oil is treated at 40 ° C. for 20 minutes, dehydrated, dried, and then JIS L-02171.
Samples washed 30 times by the 03 method (home washing) were visually judged by five inspectors, and judged according to the following criteria. ：: Fibrils were not generated and the appearance was remarkably excellent. ：: No fibrils were generated and the appearance was excellent. Δ: Fibril generation is small, but appearance is slightly inferior. ×: Fibrils are frequently generated and the appearance is poor. <Hand feeling> JIS L-0127 103
The sample after 30 washings by the method (home washing) was examined by a sensory test by five inspectors, and the flexibility was determined according to the following criteria. All five good: ◎ Three or four good: ○ One or two good:
△ All five bad: × [Tear strength (N kgf｝)] JIS L
It was measured according to -10968-8-15D (Benduram method). <Burst strength kPa> JIS L-101
It measured according to the 8A method (Mullen method). <Stability of Hydrogen Peroxide (%)> With respect to the treatment liquid obtained by mixing the acid, the metal compound and the hydrogen peroxide, the concentrations of the hydrogen peroxide immediately after preparation and after 2 hours at 25 ° C. were determined. The value obtained by dividing the concentration of hydrogen peroxide by the concentration of hydrogen peroxide immediately after preparation was multiplied by 100, and the decomposition rate was determined as a measure of stability. The concentration of hydrogen peroxide was measured by accurately weighing about 5 g of the treatment solution in a 100 ml conical beaker,
After adding 2 ml of a 2% aqueous sulfuric acid solution, titration was performed with an N / 2-potassium permanganate solution, and the point at which the faint red color of potassium permanganate did not disappear was determined by the following equation. (Equation 1) Where a is the amount of the processing solution collected (g) b is the titer of N / 2-potassium permanganate (cm ³ ) f is the factor of N / 2-potassium permanganate [Example 1] A plain woven fabric using a treated polynosic fiber (manufactured by Fujibo Ehime Co., Ltd.) using a 50th single yarn and having a continuous density of 132 yarns / inch and a horizontal density of 80 yarns / inch is subjected to ordinary continuous desizing and scouring. (1) was obtained. Hydrogen peroxide, iron (III) (EDTA is 100
Multiplied value), 10% of the concentration shown in Table 1 containing malic acid.
50 L of each kind of water treatment liquid was prepared, and the stability of hydrogen peroxide of each water treatment liquid was measured. 115c for each water treatment solution
Each piece of the plain woven fabric (1) having a size of mx 10 m was immersed for 2 seconds, squeezed at a squeezing ratio of 85%, immediately subjected to a steaming treatment at 102 ° C for 1.5 minutes, washed with water and dried. Sample N
o. 1 to No. 10 was obtained. The appearance, hand, and tear strength of the obtained sample were measured. The results are shown in Table 1. [Table 1] As is clear from Table 1, even when the total concentration of the three components is within the preferred range of 2 to 5%, when one component is less than the preferred concentration, Sample No. As shown in 1 and 2, the effect of suppressing fibrils is insufficient from the appearance,
Sample No. Although the effect of suppressing fibrils is sufficient as in No. 3, the stability of hydrogen peroxide is extremely poor, which is not preferable. Sample No. 1 in which the concentration of each component is equal to or higher than the preferred concentration and the sum of the concentrations of the three components is within the preferred range 4
Nos. 9 to 9 show that the generation of fibrils is suppressed and the appearance and texture are both excellent. Sample No. In Nos. 7 to 9, a decrease in tear strength is observed, but such a decrease does not pose a practical problem. By the way, about tear strength, 7.8N
{Kgf} or more is a standard value in the industry in general.
Sample No. 7 to 9 show clearly higher numerical values, and are not problematic. Sample No. In No. 10, fibrils are suppressed and the appearance and texture are excellent, but since the concentrations of the three components are beyond the preferred ranges, the tear strength is undesirably reduced. [Example 2] A plain woven fabric with a yarn count of 50 (single density 132) using lentining lyocell (trade name, manufactured by Lentining Co., Ltd.) which is a solvent-spun regenerated cellulose fiber.
This fabric was subjected to ordinary continuous desizing and scouring to obtain a plain fabric (2). 2% hydrogen peroxide, 0.015% ferric chloride converted to iron, 1.5% citric acid
Two 50 L each of a water treatment liquid having a total concentration of the three components contained of 5% (the value of iron was multiplied by 100) was prepared, and the stability of hydrogen peroxide in the water treatment liquid was measured. Next, in the same manner as in Example 1, the plain fabric (2) having a size of 115 cm × 10 m and the plain fabric (1) obtained in Example 1 were treated with a water treatment solution. 11 and sample no. 12 was obtained. In addition, unprocessed plain fabrics (1) and (2) were prepared as Comparative Samples 1 and 2. The obtained sample No. Appearance, texture, and tear strength of 11, 12 and Comparative Samples 1 and 2 were measured.
Table 2 shows the results. [Table 2] [0030] As is clear from Table 2, the same as in Example 1 regardless of whether the acid was changed to citric acid, the iron compound was changed to ferric chloride, or the sample was changed to solvent-spun regenerated cellulose fiber. In addition, the concentration of each component is a preferable concentration,
If the total concentration of the components is within the preferred range, Comparative Sample 1
Alternatively, it is apparent that there is no generation of fibrils as compared with Comparative Sample 2, and the appearance and texture are remarkably excellent. Example 3 A 60-count double yarn using bleached polynosic fiber (manufactured by Fujibo Ehime Co., Ltd.) was wound around a small beam and warped. Hydrogen peroxide 2%, ferric chloride converted to iron element 0.01%, malic acid 0.5%
Fifty liters of a water treatment liquid having a total concentration of the three components contained of 3.5% (the value of iron was multiplied by 100) was prepared, and the stability of hydrogen peroxide in the treatment liquid was measured. 40 m / min in the water treatment liquid
The yarn wound on the beam was passed while unwinding at a speed of 絞 り, squeezed at a squeezing ratio of 85%, and immediately subjected to a steaming treatment at 102 ° C. for 1.5 minutes, followed by washing and drying. Using the double yarn processed and processed at the 60th count, a sheet knitting machine (18 inches × 24G × 1392N) was used to obtain a sheet knitting machine. 13. In addition, a sheet laying machine was knitted using a polynosic fiber 60th twin yarn to obtain Comparative Sample 3. The obtained sample No. 13 and Comparative Sample 3 were measured for appearance, texture, and burst strength. Table 3 shows the results. [Table 3] As is clear from Table 3, even when the yarn is treated by the method of the present invention and knitted using the treated yarn, the concentration of each component of the treatment liquid is a preferable concentration, and the concentration of the three components is When the total is in the preferable range, it is apparent that there is no generation of fibrils as compared with Comparative Sample 3, and the appearance and texture are remarkably excellent. Example 4 Using the 30th single yarn made of unbleached polynosic fiber (manufactured by Fujibo Ehime Co., Ltd.), a knitted fabric was knitted in the same manner as in Example 3, and then scoured by a usual method. The bleached sheet was obtained. 2% hydrogen peroxide,
Iron (III) (EDTA converted to iron element) 0.01
%, Malic acid 0.5%, citric acid 0.5%, the total concentration of the three components is 4% (iron value is 100 times). The properties were measured. Subsequently, a sheet laying machine having a size of 1 mx 10 m was immersed in the treatment solution for 2 seconds, squeezed at a squeezing ratio of 85%, and immediately heated to 102 ° C.
, Steaming for 1.5 minutes, washing and drying
o. 14 was obtained. In addition, a sheet laying machine not treated with the water treatment liquid was used as Comparative Sample 4. The obtained sample No. 14 and Comparative Sample 4 were measured for appearance, texture, and tear strength. Table 4 shows the results. [Table 4] As is clear from Table 4, even if two types of acids were used in the method of the present invention, not fibrils, there was no generation of fibrils, and the appearance and the appearance were remarkably improved.
It is clear that the texture is excellent. Although a slight decrease in the stability of hydrogen peroxide is observed, this does not pose a practical problem. Example 5 Plain fabric similar to that of Example 1 using a spun yarn of No. 50 single yarn consisting of 70% bleached polynosic fiber (Fujibo Ehime Co., Ltd.) and 30% cotton fiber To obtain a normal continuous desizing scouring bleached plain fabric. The total concentration of the three components containing 2% hydrogen peroxide, 0.015% ferric chloride in terms of iron, and 1.5% malic acid is 5% (iron value multiplied by 100). 50 L of a certain water treatment solution was prepared, and the stability of hydrogen peroxide was measured. Example 1
A plain fabric having a size of 115 cm × 10 m was treated with the above-mentioned water treatment liquid in the same manner as in 15 was obtained. Also,
The plain fabric not treated with the water treatment liquid was used as Comparative Sample 5. The obtained sample No. 15 and Comparative Sample 5,
The hand and the tear strength were measured. Table 5 shows the results. [Table 5] As is evident from Table 5, the woven fabric obtained by blending the polynosic fiber with other fibers has no fibrils and has a remarkably excellent appearance and texture as compared with Comparative Sample 5. Although the tear strength is slightly lower than that of the comparative sample 5, it does not actually cause a problem. According to the method for processing regenerated cellulose fibers of the present invention, the generation of fibrils due to repeated processing or washing, which is a drawback of polynosic fibers or solvent-spun cellulose fibers, is suppressed, and flexible fibers are obtained. It has the effect of significantly improving the quality without impairing the texture, and has a small decrease in strength.It can be used to control fibrillation in a wide range of fields, including thin materials that were previously unsuitable for fibrillation suppression processing. is there.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Koji Ando             5-3-16 Viewer, Koshigaya, Koshigaya City, Saitama Prefecture             203 Koshigaya F term (reference) 4L031 AA02 AB01 AB32 BA33 CA02                 4L033 AA02 AB01 AB05 AC08 AC15                       BA17 BA18

Claims (1)

Claims 1. A regenerated cellulose fiber is treated with an aqueous solution containing three components consisting of an acid, hydrogen peroxide, and a metal compound having a decomposition activity for hydrogen peroxide, followed by heat treatment. A method for processing a regenerated cellulose fiber.