JP2005105495A - Antimicrobial fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antimicrobial fiber excellent in duration of washing resistance and antimicrobial effect and a method for producing the same. <P>SOLUTION: The antimicrobial fiber contains rosemary oil at least inside the fiber. The method for producing the antimicrobial fiber is to spin the fiber from a polymer solution by wet spinning and subsequently bring the fiber into contact with rosemary oil in a swollen state. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antibacterial fiber comprising a natural antibacterial agent having excellent washing durability and having an antibacterial activity and a method for producing the antibacterial fiber.

  Conventionally, quaternary ammonium salts such as benzalkonium chloride and benzenetonium chloride, chlorhexidine salts, and the like have been used as antibacterial agents for fibers that impart antibacterial activity to fibers and fiber products. However, these antibacterial agents for fibers have a problem that the antibacterial activity is difficult to sustain, or the antibacterial agents attached to the fibers are easily removed by washing, and the antibacterial effect is lost after several washings. Further, the quaternary ammonium salt of benzalkonium chloride has a drawback of corroding the fiber processing apparatus.

As a countermeasure for solving such a problem, a polymer sheet material (see Patent Document 1) immersed in an aqueous solution of chlorohexidine having a stronger antibacterial activity than the above-mentioned salts is proposed to improve the durability of the antibacterial activity. Moreover, using the quaternary ammonium phosphate as an antibacterial substance is proposed (refer patent document 2, 3), and the problem of the corrosion of the fiber processing apparatus by an antibacterial agent is solved. However, the actual situation is that an antibacterial fiber having a sufficiently long antibacterial effect has not yet been provided. Moreover, these antibacterial agents are synthesized antibacterial agents, and natural and human-friendly antibacterial agents have not yet been provided.
Japanese Patent Publication No. 56-34203 JP-A 64-79102 Japanese Patent Laid-Open No. 1-11302

  In view of the background of such prior art, the present invention provides an antibacterial fiber excellent in both washing durability and durability of an antibacterial effect, and a method for producing the same.

  The present invention employs the following means in order to solve the above problems. That is, the antibacterial fiber of the present invention is characterized by containing rosemary oil at least inside the fiber. Such a method for producing antibacterial fibers is characterized in that after the polymer is wet-spun from a polymer solution, the swollen fibers are brought into contact with rosemary oil.

  ADVANTAGE OF THE INVENTION According to this invention, the fiber can be manufactured and provided with the antibacterial effect excellent in washing durability and sustainability, without corroding a fiber processing apparatus. Moreover, the antibacterial acrylic fiber obtained by the present invention has an effect of holding rosemary oil at least inside the fiber and exhibiting an antibacterial effect excellent in washing durability and durability.

  The present invention has been intensively studied on the above-mentioned problems, that is, antibacterial fibers excellent in washing durability and durability of antibacterial effects, and when a specific natural antibacterial agent is applied to a swollen fiber formed by wet spinning, the fibers They have sought to solve such a problem at once without corroding the processing equipment.

  As the fiber constituting the antibacterial fiber of the present invention, a fiber produced by a wet spinning method is used. That is, according to the wet spinning method, a swollen fiber is produced by a method of densifying the fiber, and the swollen fiber is a porous fiber. During this stage, rosemary oil is used. Are adhered and adsorbed and adhered in the pores, and then densified to be fixed in the fiber. That is, the fiber referred to in the present invention includes all fibers produced by such wet spinning method. Among these, acrylic or acrylic fibers are particularly preferably employed from the viewpoint of fiber strength and the like.

  In this way, the rosemary oil is brought into contact with the swollen fiber after wet spinning, that is, in any step until the swollen fiber is finally densified. It is possible to provide a product having excellent washing durability and durability.

  In other words, internal voids and surface irregularities generated by, for example, desolvation remain in the swollen fiber spun by the wet spinning method, that is, the fiber at the stage where densification is not completed after spinning. The rosemary oil used in the present invention has such characteristics that it penetrates into the voids inside the fibers and the irregularities on the surface, and is easily fixed and held on the fibers by densification of the fibers. The final densification step means a final step that substantially increases the polymer density by, for example, a stretching step, and is not limited by the name of the step. Since the antibacterial fiber produced by contacting the antibacterial agent after the final densification step is fixed only to the fiber surface, the washing durability of the antibacterial effect is poor and the object of the present invention cannot be achieved. Therefore, the antibacterial fiber manufacturing method according to the present invention is a method in which the fiber has many internal voids and surface irregularities immediately after spinning, and finally the internal voids disappear due to densification. It is suitable for fibers manufactured through the process, that is, fibers manufactured by a wet spinning method. In particular, acrylic fibers, rayon, vinylon fibers, and the like are suitable fibers for the present invention, and acrylic fibers such as acrylonitrile fibers are particularly suitable fibers.

  Such an acrylic fiber preferably contains 2 to 8 mol% of at least 92 mol% of acrylonitrile, an ethylenic vinyl monomer copolymerizable with the acrylonitrile, and a sulfonic acid-containing monomer. When the content of acrylonitrile is less than 92 mol%, normal physical properties cannot be obtained, which is not preferable. Examples of the ethylenic vinyl monomer copolymerizable with the acrylonitrile include acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, maleic acid, fumaric acid, Itaconic acid, styrene, vinylidene halide, vinyl ether and the like. Examples of the sulfonic acid-containing monomer include sodium allyl sulfonate, sodium methallyl sulfonate, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methyl Examples include sodium propanesulfonate. The sulfonic acid-containing monomer is preferably copolymerized in an amount of 0.2 to 2.0 mol%. The solvent of the acrylic polymer solution is not particularly limited as long as it dissolves the above acrylic polymer. Organic solvents such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), dimethylformamide, dimethylacetamide, and acetone, rhodan salt aqueous solution, zinc chloride An aqueous solution, an aqueous nitric acid solution or the like is used. The proportion of the acrylic polymer in the acrylic polymer solution is preferably 19 to 25% by weight.

  The acrylic polymer solution as described above is wet-spun and extruded into a bath having a coagulant bath concentration of 50 to 70% by weight and a coagulant concentration of water or alcohol such as 30 to 50% by weight. After drawing at 0.3-2.0, after stretching at a draw ratio of 3.5-7.0 times, washing with water, giving rosemary oil to dry densification, giving after oil, It can be obtained by heat treatment at 100 ° C. to 170 ° C. after crimping by a crimper.

  The rosemary oil referred to in the present invention is an oil extracted from rosemary (Rosmarinus officinalis), which is a typical western herb belonging to Lamiaceae plants, and this oil is safe for humans, particularly skin functionalities. From the point of view, it has excellent safety.

  That is, the rosemary is extracted with a lower alcohol having a water content of 10 to 60% by volume, and water is added to the resulting extract to precipitate a water-insoluble component, which is obtained by filtration. Is. In this case, when the water content of the extraction solvent (lower alcohol) exceeds 60% by volume, unnecessary extraction of water-soluble components increases, which is not preferable. The part of rosemary used for such extraction treatment is preferably the above-ground part, particularly the leaf stalk part of rosemary. This extract may be used as it is, or may be used after drying such as sun drying.

  Such an extraction operation may be performed at room temperature, but the extraction can be performed more efficiently by preferably employing a means for heating under reflux cooling. If this extraction operation is repeated further for the residue after extraction, the yield can be increased.

  After the extraction treatment, when the obtained extract is concentrated under reduced pressure, water-insoluble components begin to precipitate as the alcohol content decreases. After removing the alcohol, water is added to this and suspended with stirring, and then the precipitated component is collected by filtration or the like to obtain a water-insoluble component. Preferably, an impure component such as a coloring component is removed by subjecting the obtained extract or an obtained precipitate component redissolved in alcohol to activated carbon treatment.

  As an example of a specific production method, 500 ml of 90 volume% ethanol (water content 10 volume%) was added to 100 g of dried rosemary stems of rosemary, and the mixture was heated at an external temperature of 110 ° C. for 9 hours under reflux cooling. After soaking for 16 hours while allowing to cool naturally, the mixture is filtered to separate the filtrate (A) and the insoluble residue, and the insoluble residue is rinsed with 300 ml of 90% by volume ethanol to obtain a rinse liquid (B). These filtrate (A) and rinse solution (B) were combined to obtain 700 ml of an extract (primary extract). Next, 300 ml of the 90% by volume ethanol (water content 10% by volume) is further added to the filtered insoluble residue, followed by heating and extraction for 9 hours under reflux cooling, and the residue is filtered to obtain a filtrate (C). The filtrate (C) and the primary extract were combined to obtain 950 ml of extract (D).

  After adding 0.75% by weight of activated carbon to this extract (D) and stirring for 1 hour, the activated carbon was removed by filtration, the extract was concentrated under reduced pressure to distill off the ethanol component, and 210 ml of water was added. In addition, after the water-insoluble component that had been precipitated by stirring was suspended, the precipitated component was collected by filtration and dried at 45 ° C. under reduced pressure to obtain 13.4 g of a solid content. The solid content from this rosemary is the rosemary oil used in the present invention. As such a rosemary extract, Mamorec RUH-21 (R) manufactured by Teikoku Chemical Industry Co., Ltd. can be used as a commercial product.

  There is no particular limitation on the means for bringing the fibers into contact with the antibacterial agent, and for example, means used for applying an oil such as dipping or spraying are preferably used. In the present invention, since the antibacterial agent is fixed and held on the fiber, an antibacterial fiber having an antibacterial effect excellent in washing durability and durability can be obtained.

  The content of such rosemary oil is preferably 0.1% by weight or more and 20% by weight or less, more preferably 0.5% by weight or more and 10% by weight or less of the fiber weight. If it is less than 0.1% by weight, there is no antibacterial performance, and if it exceeds 20% by weight, troubles due to dropping off of the oil agent occur in the subsequent spinning step, which is not preferable.

Next, the effects of the present invention will be described more specifically with reference to examples. The antibacterial effect evaluation method and the washing method used are as follows.
(1) Antibacterial evaluation method A method for measuring the number of bacteria was adopted, and Staphylococcus aureus ATTC6538p was used as a test bacterium. A bouillon suspension of test bacteria was poured onto a sample cloth sterilized by a conventional method, and cultured at 37 ° C. for 18 hours in a sealed container. The number of viable bacteria was measured, and the difference in the number of bacteria increased or decreased represented by the following formula was determined.

(Bacterial count increase / decrease value difference) = log (B1 / C1)
However, log (B1 / A1)> 2
In the formula, A1: Number of bacteria collected and recovered immediately after inoculation on unprocessed cloth
B1: Number of bacteria recovered after dispersion of untreated cloth after culturing at 37 ° C for 18 hours
C1: Number of bacteria collected and dispersed after incubation for 18 hours at 37 ° C of the processed product (3) Washing method In a household washing machine (VH-3410: manufactured by Toshiba Corporation), neutral detergent (Zab: Kao Corporation) Made by washing) 0.2% wash liquid, wash at a temperature of 40 ± 2 ℃, processed product: wash liquid bath ratio 1:50 for 5 minutes with strong inversion, and then rinse with draining and overflowing 2 operations for 2 minutes
Repeated once, this was one wash.

Examples 1-4
A dimethyl sulfoxide (DMSO) solution of an acrylic copolymer consisting of acrylonitrile (AN) / methyl acrylate (MA) / methacryl sulfonic acid soda (SMAS) = 93.5 / 6.0 / 0.5 (weight ratio), Wet spinning was performed in a 30% 60% DMSO aqueous solution. The obtained unstretched solidified fiber was stretched and washed with water, and then commercially available Mamorek RUH-21 (R) (manufactured by Teikoku Kagaku) as a rosemary oil was prepared in a 5 wt% aqueous solution to give 0.4% owf, 0.8 After antibacterial treatment so as to be% owf, 1% owf, and 3% owf, drying and densification was performed at 130 ° C. to obtain an antibacterial acrylic fiber according to the present invention. The obtained fiber was dyed maxi blue and was washed 10 times by the above washing method.

  Table 1 shows the results of calculating the number of bacteria increase / decrease values before and after washing. The acrylic antibacterial fiber according to the present invention had a stable antibacterial effect both before and after washing.

Comparative Examples 1-4
a. Production of antibacterial fiber Acrylic copolymer dimethyl sulfoxide (acrylic acid (AN) / methyl acrylate (MA) / sodium methacryl sulfonate (SMAS) = 93.5 / 6.0 / 0.5 (weight ratio)) DMSO) solution was wet spun into 30 ° C., 60% DMSO aqueous solution. The obtained unstretched solidified fiber was stretched, washed with water, dried and densified at 130 ° C., and then methoxypolyethylene glycol methacrylate, which is an oil for fibers, was formulated into a 5% by weight aqueous solution to give 0.4% owf and 0.8% owf. Acrylic fibers were obtained by treatment with 1% owf and 3% owf oil. The obtained fiber was dyed maxi blue and was washed 10 times by the above washing method.

  Table 1 shows the increase / decrease values of the number of bacteria before and after washing. Antibacterial evaluation by Staphylococcus aureus showed a marked decrease in antibacterial activity after washing.

表１から明らかなように、実施例１〜４のローズマリー油を含有させた繊維は、洗濯耐久性に優れた抗菌性能を有することがわかる。

As is clear from Table 1, it can be seen that the fibers containing the rosemary oils of Examples 1 to 4 have antibacterial performance excellent in washing durability.

Claims (6)

An antibacterial fiber characterized by containing rosemary oil at least inside the fiber. The antibacterial fiber according to claim 1, wherein the fiber is an acrylic fiber. The antibacterial fiber according to claim 1 or 2, wherein the rosemary oil is adhered to 0.1 to 20% by weight of the fiber weight. A method for producing an antibacterial fiber, comprising wet spinning a polymer from a polymer solution and then contacting the swollen fiber with rosemary oil. The method for producing antibacterial fibers according to claim 4, wherein the wet-spun fibers are acrylic fibers. The method for producing an antibacterial fiber according to claim 5, wherein rosemary oil is brought into contact with the swollen fiber in any of the steps until the swollen swollen fiber is finally densified.