JP2842564B2 - Antibacterial viscose rayon and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to viscose rayon having antibacterial properties, and more particularly to viscose rayon having excellent antibacterial properties against methicillin-resistant Staphylococcus aureus (abbreviation: MRSA) and a method for producing the same.

[0002]

2. Description of the Related Art Recently, textile products having antibacterial properties have attracted attention from the viewpoints of preventing body odor and preventing bacterial infection, and the emergence of effective products is desired. In particular, MR
Since a textile product having antibacterial properties against SA is expected to prevent the propagation of MRS A and prevent hospital-acquired infection, the emergence of such a textile product is desired. Conventionally, as a means of imparting antibacterial properties to textiles, in particular, to impart antibacterial properties to MRSA, methods such as kneading of chitosan or silver zeolite are known. Further, silver zeolite has a disadvantage that it becomes silver sulfide and blackens the color tone of rayon.

As a method for imparting antibacterial properties to fibers, it has been conventionally known to add a quaternary ammonium salt compound, for example, as described in JP-A-63-2753111.
Japanese Patent Laid-Open Publication No. H10-175686 discloses a paper or a nonwoven fabric impregnated with an alcohol solution of a low molecular weight quaternary ammonium salt compound and an anionic high molecular weight quaternary ammonium salt compound.
Wet tissue) and that the wipe is particularly suitable for toilet seat cleaners.

[0004]

SUMMARY OF THE INVENTION The antibacterial wiping paper technology described in the above publication is simply applied to viscose rayon, that is, an antibacterial material obtained by impregnating viscose rayon with the antibacterial substance. The viscose rayon has a problem that the antibacterial property is not sufficiently maintained. For example, such antibacterial viscose rayon sheets,
When applied to materials that are repeatedly washed and used, such as clothes in hospitals, there is a problem that as the number of washings is increased, the antibacterial property is rapidly reduced, which is not practical.

In order to prevent the quaternary ammonium salt compound from falling off during washing, for example, a method of dispersing in a spinning solution (viscose) using a quaternary ammonium salt compound together with a surfactant has been proposed. Although it can be considered, this method has a problem that the surfactant acts on the quaternary ammonium salt compound to reduce the antibacterial action of the quaternary ammonium salt compound.

In order to prevent such a decrease in antibacterial activity, a quaternary ammonium salt compound must be added in a large amount of 10% or more. As a result, the fiber surface becomes too slippery and When heated during processing, there has been a problem that the quaternary ammonium salt compound is decomposed to cause yellowing and impair the feel of the fiber.

The present invention solves the above-mentioned problems, and can prevent the antibacterial property from being reduced even when the quaternary ammonium salt compound is contained at a content of 10% or less even in repeated washing. And viscose rayon exhibiting excellent antibacterial properties and a method for producing the same.

[0008]

In order to solve the above-mentioned problems, the antibacterial viscose rayon of the present invention has a polymer substance having an anion distributed uniformly in viscose rayon, and A quaternary ammonium salt compound is held on the surface of the viscose rayon.

The method for producing an antibacterial viscose rayon according to the present invention comprises mixing a viscose with a polymer substance having an anion, spinning the obtained viscose, refining it into viscose rayon, Coarse rayon is characterized by being treated with an alcohol solution or a water dispersion of a quaternary ammonium salt compound. As the alcohol, ethanol and isopropyl alcohol are generally used.

[0010] The antibacterial viscose rayon of the present invention exhibits excellent antibacterial properties, especially excellent antibacterial action against MRSA, and can reduce the decrease in antibacterial action even after repeated washing.

In the present invention, the high molecular substance having an anion is carboxymethylcellulose (abbreviation: CMC),
One or more of sodium alginate, sodium polystyrene sulfonate, polysodium methacrylate, sodium polyacrylate or copolymers thereof, oxidized starch, phosphate starch, isobutylene maleate copolymer and the like can be used. Sodium sulfonate is preferred. Among these high molecular substances, CMC has a carboxyl group and thus has an action of strengthening the bond with a quaternary ammonium salt compound.

In particular, it is preferable that these anion-containing polymer substances have a molecular weight of 10,000 to 500,000. If the molecular weight is less than 10,000, it is easy to fall off during spinning, which causes contamination of the spinning bath and high cost, which is not preferable. On the other hand, if the molecular weight exceeds 500,000, depending on the amount added, it may cause the viscosity of the viscose to increase, making uniform dispersion in the viscose difficult. It causes the power to decrease.

The quaternary ammonium salt compound used in the present invention is a compound represented by the following formula (1).

[0014]

Embedded image Particularly preferably, didecyldimethylammonium chloride, stearyltrimethylammonium chloride,
Behenyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, cocoalkyldimethylbenzylammonium chloride, tallowalkyltrimethylammonium chloride, hardened tallowalkyltrimethylammonium chloride, octadecyltrimethylammonium chloride and the like.

The content of the polymer material having an anion in viscose rayon is preferably 0.01 to 30%, particularly preferably 0.5 to 5%. The content is 0.
If the concentration is less than 01%, the adsorption of the cationic antibacterial quaternary ammonium salt compound is weakened, and if it exceeds 30%, the spinning bath is contaminated and the texture of viscose rayon is lowered, which is not preferable.

The content of the quaternary ammonium salt compound in viscose rayon is 0.001 to 1
0%, particularly preferably 0.03 to 5%. If the content is less than 0.001%, the antibacterial property becomes insufficient, and 10%
If the ratio exceeds, the fiber surface becomes too slippery and the texture of the fiber is lowered, and the decomposition of the quaternary ammonium salt compound is accompanied by coloring such as yellowing, which is not preferable.

The antibacterial viscose rayon of the present invention can be produced by the following method. A polymer substance having an anion is added to viscose for producing viscose rayon, mixed and finely dispersed. The method of adding, mixing and finely dispersing the polymer substance having an anion includes a method of adding viscose xanthate when it is dissolved, a method of adding viscose and stirring, and a method of mixing finely using a mixer immediately before spinning the viscose. A method of dispersing can be adopted.

The amount of the high molecular substance having an anion added to viscose should be slightly larger than the target amount in the final viscose rayon in consideration of elution into the spinning bath during spinning. is necessary. The yield at the time of spinning differs depending on the type of molecular weight of the polymer substance, and is determined empirically. Usually, if the molecular weight of the polymer substance is 10,000 or more, the approximately 90% or more with almost no elution it can be kept in the fiber.

Further, when a large amount of the high molecular weight polymer is added to viscose, the viscosity increases and spinning cannot be performed smoothly. Therefore, those having a molecular weight exceeding 500,000 are not preferred. The addition amount is appropriately adjusted depending on the type and properties of the polymer substance so that the viscosity of the viscose is 30 to 80 pois, and it is preferable to add the viscose at a viscosity of about 10 pois.

The viscose in which the polymer material having an anion obtained as described above is finely dispersed can be spun by the same method as the usual spinning method of viscose. That is, in accordance with the viscose rayon production method, discharge spinning is performed in an acidic spinning bath composed of sulfuric acid, sodium sulfate, and zinc sulfate, stretched, scoured, and dried. Viscose to which a polymer substance having an anion is added can be used as viscose for strong rayon, viscose for polynosic, and viscose for rayon paper.

In order to incorporate the quaternary ammonium salt compound into the fiber, the viscose rayon obtained by spinning, drawing and refining the viscose as described above is added to a solution of the quaternary ammonium salt compound or It is performed by applying in the form of a dispersion. Examples of the method of the application include an immersion method,
Spray method and any method can be adopted.

The quaternary ammonium salt compound may be applied to the viscose rayon after the spinning at any stage as long as it is after the scouring. This is advantageous because it penetrates into the water to increase the permeability and eliminates the need for twice drying.

The antibacterial viscose rayon of the present invention obtained as described above can prevent the antibacterial property from being reduced even after repeated washing, and is effective not only for general bacteria but also for MRS.
A has an excellent antibacterial effect on A. In addition, cotton-forming, spinning, and weaving can be performed in the same manner as ordinary fibers, and if necessary, blending with other fibers, blending, mixing and weaving and knitting, futons, sheets, mats, carpets, curtains, and white coats , Shoji, wallpaper, socks, underwear, shirts, etc.

In addition, if the content of each of the polymer material having an anion and the quaternary ammonium salt compound in the present invention in the viscose rayon, the fiber performance is higher than that of the non-added ordinary viscose rayon material. It has good spinnability without any change in texture. In addition, the antibacterial property has sufficient washing resistance, and the antibacterial property is sufficiently maintained even in the dyeing process of cotton and yarn.

[0025]

【Example】

Example 1 An ordinary rayon viscose solution having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight was added to sodium polystyrene sulfonate (PSS-Na: trade name,
(Sulfonation degree 84%, molecular weight 20,000, manufactured by Tokuyama Soda Co., Ltd.)
Was mixed and finely dispersed so as to be 5.0% by weight based on cellulose. Viscose obtained (viscosity: 70 poi
s) was spun into a spinning bath consisting of 98 g / l of sulfuric acid, 360 g / l of sodium sulfate, and 17 g / l of zinc sulfate at 47 ° C., stretched and scoured in accordance with a conventional method to obtain 4.6% of sodium polystyrene sulfonate. A viscose rayon containing kneading was created.

A solution of 3.0% by weight of didecyldimethylammonium chloride (Arcard 210-50, trade name, manufactured by Lion Corporation) per viscose rayon, into which sodium polystyrene sulfonate obtained in the above step was kneaded. Coarse rayon is immersed at 40 ° C for 2 minutes,
After dehydration and drying, the antibacterial viscose rayon of Example 1 to which 2.8% of didecyldimethylammonium chloride had adhered was obtained.

Example 2 In a normal rayon viscose solution having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight, sodium alginate (1-3F, trade name, manufactured by Kimitsu Chemical Industry Co., Ltd., average (Molecular weight: 50,000) was mixed and finely dispersed so as to be 1.0% by weight based on cellulose. The resulting viscose (viscosity: 70 pois) was subjected to a conventional method at 47 ° C. at 98 g / l sulfuric acid and 360 g /
1 and 17 g / l of zinc sulfate were spun, stretched, and scoured to prepare a kneaded viscose rayon containing 0.9% of sodium alginate.

Viscose rayon kneaded with sodium alginate obtained in the above step into a solution of cocoalkyltrimethylammonium chloride (Nissan Cation FB: trade name, manufactured by NOF CORPORATION) of 3.0% by weight per viscose rayon. Was immersed at 40 ° C. for 2 minutes, dehydrated, and dried to obtain an antibacterial viscose rayon of Example 2 to which 2.7% of cocoalkyltrimethylammonium chloride had adhered.

Example 3 In a normal rayon viscose solution having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight, sodium polyacrylate (Aquaric DL) was added.
522: trade name, manufactured by Nippon Shokubai Co., Ltd., average molecular weight 22
Was mixed and finely dispersed so as to be 2.5% by weight based on cellulose. Viscose obtained (viscosity: 70 poi
s) was spun into a spinning bath consisting of 98 g / l of sulfuric acid, 360 g / l of sodium sulfate, and 17 g / l of zinc sulfate at 47 ° C., stretched, and scoured at a temperature of 47 ° C. to reduce sodium polyacrylate to 2.3%. A viscose rayon containing kneading was created.

Viscose kneaded with sodium polyacrylate obtained in the above step in a solution of behenyltrimethylammonium chloride (Nissan Cation VB: trade name, manufactured by Nippon Oil & Fats Co., Ltd.) of 2.0% by weight per viscose rayon. The rayon was immersed at 40 ° C. for 2 minutes, dehydrated, and dried to obtain an antibacterial viscose rayon of Example 3 to which 1.9% of behenyltrimethylammonium chloride was adhered.

Example 4 Carboxymethylcellulose (reagent manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight: 110,000) was added to a normal rayon viscose solution having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight. It was mixed and finely dispersed so as to be 1.0% by weight based on cellulose. The resulting viscose (viscosity: 70 pois) was subjected to a conventional method at 47 ° C. at 98 g / l sulfuric acid and 360 g /
l, 17 g / l of zinc sulfate, spun into a spinning bath, stretched and scoured to reduce carboxymethylcellulose to 0.9 g / l.
% Viscose rayon was prepared.

A solution of 3.0% by weight of stearyl trimethylammonium chloride (Arcard 18-63: trade name, manufactured by Lion Corporation) per viscose rayon was added to
The carboxymethylcellulose-kneaded viscose rayon obtained in the above step is immersed at 40 ° C. for 2 minutes, dehydrated, and dried, and the antibacterial viscose of Example 4 to which 2.8% of stearyltrimethylammonium chloride adheres. I got rayon.

Comparative Example 1 An ordinary rayon viscose solution (viscosity: 70 pois) having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight was subjected to a conventional method at 98.degree. 1 and 17 g / l of zinc sulfate, spun out, stretched, scoured and dried to prepare ordinary viscose rayon.

The ordinary viscose rayon obtained in the above step was added to a solution of 3.0% by weight of didecyldimethylammonium chloride (Arcard 210-50, trade name, manufactured by Lion Corporation) per viscose rayon at 40 ° C. 2
Then, the viscose rayon of Comparative Example 1 to which 2.8% of didecyldimethylammonium chloride adhered was obtained.

COMPARATIVE EXAMPLE 2 A normal rayon viscose solution (viscosity: 70 pois) having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight was subjected to a conventional method at 98.degree. 1 and 17 g / l of zinc sulfate, spun out, stretched, scoured and dried to prepare ordinary viscose rayon.

The ordinary viscose rayon obtained in the above step was added to a 2.0% by weight of coconut alkyldimethylbenzylammonium chloride (Nissan Cation F2 Conc: trade name, manufactured by NOF CORPORATION) per viscose rayon. It was immersed at 40 ° C. for 2 minutes to obtain viscose rayon of Comparative Example 2 to which 1.7% of cocoalkyldimethylbenzylammonium chloride had adhered.

Comparative Example 3 Stearyl trimethylammonium chloride (Arcade 18-63: trade name, manufactured by Lion Corporation) was added to a normal rayon viscose solution having a cellulose concentration of 8.5% by weight and an alkali concentration of 5.7% by weight.
Was mixed and finely dispersed so as to be 3.0% by weight based on cellulose. Viscose obtained (viscosity: 70 poi
s) was spun into a spinning bath consisting of 98 g / l of sulfuric acid, 360 g / l of sodium sulfate, and 17 g / l of zinc sulfate at 47 ° C., stretched and scoured according to a conventional method to obtain stearyltrimethylammonium chloride in an amount of 2.2%. The kneaded viscose rayon of Comparative Example 3 was prepared.

[Comparative Example 4] A normal viscose rayon without any antibacterial treatment was prepared according to a conventional method to obtain a viscose rayon of Comparative Example 4.

Each of the viscose rayons of Examples 1 to 4 and Comparative Examples 1 to 4 was evaluated for antibacterial activity against MRSA. As an evaluation method, antibacterial property was measured and washing was performed under the following conditions.

Measurement of antibacterial activity 1) Bacteria used for the test Methicillin-resistant Staphylococcus aureus 2) Test method As an antibacterial evaluation method, a processing evaluation test method for sanitary products according to the unified standard established by the Textile Products Sanitation Processing Council. The shake flask method (CTM0923 method) was used. The sterilization rate was calculated by the following equation.

[0041]

(Equation 1) 3) Washing method Washing was performed based on the standard of JIS C 9606 (electric washing machine). 4 containing 2 g / l of detergent New Beads (registered trademark: manufactured by Kao Corporation) using a home electric washing machine
After washing in an aqueous solution at 0 ° C. for 5 minutes, washing with water was carried out for 2 minutes and dehydration was carried out, followed by washing with water for 2 minutes, dehydration and drying. Repeated washing was performed by repeating the above operation.

The viscose rayon obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was washed 0, 3,
The test was performed 5, 10, 30, and 50 times, respectively, and the sterilization rate was measured and determined. The values obtained are shown in Table 1 below.

[0043]

[Table 1] According to Table 1, it is found that the samples in which only the antibacterial agent is simply adsorbed as in Comparative Examples 1 and 2 have poor washing resistance, and the antibacterial property is maintained only about five times. On the contrary,
The viscose rayon kneaded with a polymer material having an anion and treated with a solution or dispersion of a quaternary ammonium salt compound as in Examples 1 to 4 has a wash resistance of 5%.
It goes up to 0 times or more, and it is understood that there is an effect of maintaining the antibacterial property. The viscose rayon obtained by kneading and spinning the quaternary ammonium salt compound as in Comparative Example 3 had no antibacterial effect when washed.

Comparative Example 5 An ordinary viscose rayon was prepared according to a conventional method. On the other hand, sodium polystyrene sulfonate (PSS-N
A: Trade name, manufactured by Tokuyama Soda Co., Ltd., sulfonation degree 84
%, Molecular weight of 20,000) and 1.0% by weight of didecylmethylammonium chloride (Arcard 210-50: trade name, manufactured by Lion Corporation) in an amount of 5.0% by weight.
The immersion liquid was prepared by mixing and dispersing in a 0% ethanol solution. Add the ordinary viscose rayon to this immersion liquid for 40 minutes.
C. for 2 minutes, dehydrated, and dried to prepare viscose rayon of Comparative Example 5 to which 0.9% of sodium polystyrenesulfonate and 4.5% of didecyldimethylammonium chloride adhered. The viability of the obtained viscose rayon was measured against the number of washings, and the results are shown in Table 2 below.

[0045]

[Table 2] According to Table 2, it can be seen that the viscose rayon obtained by the immersion treatment of Comparative Example 5 has no washing resistance for keeping the antibacterial property.

Examples 5 to 9 In the same manner as in Examples 1 to 4, except that the type of the polymer material having an anion and the quaternary ammonium salt compound used were changed. Five to nine antibacterial viscose rayons were produced. The anion-containing polymer materials used are the compounds shown in A, B, C and D below, and the quaternary ammonium salt compounds used are the compounds shown in A, A, C and D below. Table 3 below shows combinations of the types of the high molecular substance having an anion and the quaternary ammonium salt compound used in Examples 5 to 9. The antibacterial viscose rayons of Examples 5 to 9 obtained as described above were washed 50 times and the sterilization rate was measured. The values obtained are shown in Table 3 below.

A: sodium polystyrene sulfonate (3.0% fiber weight) B: sodium polyacrylate (5.0% fiber weight) C: sodium alginate (2.0% fiber weight) D: carboxymethyl cellulose (1.5 against fiber weight
%) A: Coconut trimethylammonium chloride (3.0% by weight of fiber) (Nissan Cation FB: trade name, manufactured by NOF Corporation) i: Tallow trimethylammonium chloride (2.0% by weight of fiber) (Nissan cationic ABT ₂ -500: trade name, manufactured by NOF Corporation) c: stearyl trimethyl ammonium chloride (vs. fiber weight 1.0%) e: didecyl dimethyl ammonium chloride (vs. fiber weight 3.0%)

[0048]

[Table 3]

[0049]

The antibacterial viscose rayon obtained by the production method of the present invention can prevent a decrease in antibacterial property even after repeated washing, and is excellent not only for general bacteria but also for MRSA. Viscose rayon exhibiting improved antibacterial properties.

The antibacterial viscose rayon of the present invention can be made into cotton, spun, and woven and knitted in the same manner as ordinary fibers.
Futons, sheets, mats, carpets, curtains, white coats,
Antibacterial properties can be imparted to shoji, wallpaper, socks, underwear, shirts and the like for a long period of time.

The antibacterial viscose rayon of the present invention has a quaternary ammonium compound content of 0.001 to 10%.
As a result, the antibacterial property can be prevented from deteriorating even after repeated washing, so that the content of the quaternary ammonium compound does not need to be as large as 10% or more. Does not hurt.

Further, the antibacterial viscose rayon of the present invention can sufficiently withstand the step of dyeing cotton or yarn and maintain the antibacterial property.

────────────────────────────────────────────────── (5) References JP-A-3-249201 (JP, A) Patent 2665807 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 13/46 D01F 2/00-2/30

Claims (8)

(57) [Claims] 1. An antibacterial agent, wherein a polymer substance having an anion is uniformly distributed in viscose rayon, and a quaternary ammonium salt compound is held on the surface of the viscose rayon. Sex viscose rayon. 2. The high-molecular substance having an anion is carboxymethylcellulose having a molecular weight of 10,000 to 500,000, sodium alginate, sodium polystyrene sulfonate, polysodium methacrylate, sodium polyacrylate or a copolymer thereof, oxidized. Starch, starch phosphate,
2. The antibacterial viscose rayon according to claim 1, wherein the antibacterial viscose rayon is at least one polymer selected from isobutylene maleate copolymer. 3. The antibacterial viscose rayon according to claim 1, wherein the quaternary ammonium salt compound is a compound represented by the following formula. Embedded image 4. The antibacterial viscose rayon according to claim 1, wherein the quaternary ammonium salt compound is selected from a quaternary dimethyl ammonium salt compound and a quaternary trimethyl ammonium salt compound. . 5. The antibacterial viscose rayon according to claim 1, wherein the quaternary ammonium salt compound is didecyldimethylammonium chloride. 6. The viscose rayon has a content of the polymer material having an anion of 0.01 to 30%.
The antibacterial viscose rayon according to claim 1, 2, 3, 4, or 5, which is (weight to fiber). 7. The content of said quaternary ammonium salt compound in viscose rayon is 0.001 to 10%.
(Weight per fiber).
The antibacterial viscose rayon as described. 8. Viscose is mixed with a polymer substance having an anion, (2) The obtained viscose is spun and refined into viscose rayon, and (3) the viscose rayon is mixed with viscose. A method for producing an antibacterial viscose rayon, comprising treating with a solution or dispersion of a quaternary ammonium salt compound.