JP2778984B2 - Antimicrobial fiber and method for producing the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a fiber having an excellent antibacterial activity and a method for producing the same.

[Prior Art] Polyester-based and polyamide-based fibers are widely used not only in clothing but also in daily life products such as bedding products, carpets, sofas, and other interior and living products.

On the other hand, various bacteria and fungi inhabit our living environment, and they breed when they find suitable places. The human body surface is no exception, and bacteria live in humid areas. Many of the diseases currently referred to as skin disorders are thought to be caused by the abnormal growth of bacteria on the skin surface. In addition, these bacteria also propagate in clothes and the like moistened with sweat and cause a property deterioration phenomenon of fibers, or give off odor and give discomfort. In particular, since synthetic fibers lack the property of absorbing sweat, when the fibers are worn, microorganisms propagate on the skin, clothing, and the like to which sweat is attached, causing rot and causing a sweaty smell. Accordingly, there has been a demand for the development of a clean, comfortable and safe polyester fiber product that does not give off odor by suppressing the growth of microorganisms on the fiber.

There was a time when organotin and organomercury compounds were used to impart antibacterial properties to fibers, but the toxicity of these compounds was regarded as a problem, and most of them are currently banned.

As a post-processing method for imparting antibacterial properties to fibers,
Conventionally, silicone quaternary ammonium salts and the like have been used as particularly safe antibacterial and antifungal agents. For example, JP-A-57-51874 discloses a carpet having an organosilicone quaternary ammonium salt adsorbed thereon and a method for producing the same. However, silicone-based quaternary ammonium salts have strong binding power to cellulosic fibers and exhibit antibacterial properties that are durable for washing, but do not form strong bonds to synthetic fibers; Only those that show

It has long been known that metal compounds such as silver, copper, and zinc that elute silver ions, copper ions, and zinc ions exhibit antibacterial properties. For example, aqueous solutions of silver nitrate and copper sulfate have been widely used as disinfectants and disinfectants. However, the liquid form is inconvenient in terms of handling, and its use is limited.

Thus, fibers in which metal ions such as silver, copper, and zinc are held in a polymer have been devised. For example, JP-A-54-147220 proposes a method in which a metal compound such as silver, copper, zinc or the like is dispersed and mixed in a polymer to form fibers. Also silver ion,
A method of adding and mixing copper ion-exchanged zeolite-based solid particles with an organic polymer has been proposed in JP-A-59-133235. In these methods, the effect of the metal compound on the polymer is considered to be considerably large, so that the usable range is significantly limited, and the processability in the fiberization step, particularly, the breakage of single yarn during spinning and the packing due to packing filter packing. Problems such as shortening of service life and frequent occurrence of feathers in drawn yarns are problems. Also, looking at the manifestation of antibacterial performance apart from these process problems, the mere inclusion of metal ions in the polymer material is not sufficient for metal ions that are effective for antibacterial action on the fiber surface. Since the sustained release is insufficient, the absolute level of the antibacterial effect is low, and a sufficient effect cannot be expected.

JP-A-56-12347 proposes a method of adhering a complex of a compound of copper, silver or zinc and casein to the fiber surface in a water-insoluble state. This fiber can prevent the composite from falling off by washing with water or the like by insolubilizing the composite with water.However, insolubilization with casein requires the use of formalin. It is feared that it will occur.

In addition, there is a problem that the metal compound-containing fiber cannot be separated, and has an adverse effect on the skin. Numerous bacteria called resident bacteria exist on the skin, and it is said that by keeping the ecosystem of these bacteria in a well-balanced state, the skin can be protected from other harmful bacteria. Because metal compounds have a strong bactericidal action, these indigenous bacteria that are harmless to the human body will be indiscriminately killed, and the ecosystem of the indigenous bacteria will be destroyed and harmful bacteria from the outside world will be propagated on the skin. Inflammation on the skin is feared.

[Problems to be solved by the present invention] An object of the present invention is to provide a fiber having an antibacterial deodorizing effect without impairing the safety of skin.

[Means for Solving the Problem] The present invention relates to an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVAc) having a weight ratio of vinyl acetate of 10 to 50% by weight and a melt index of 2 to 200. Consisting of a resin (A) as a main component and a thermoplastic resin (B) having a higher melting point than the resin (A), and 10 to 90% of the fiber surface area
Is a composite fiber occupied by the resin (A), wherein the resin (A)
An antibacterial fiber characterized by hinokitiol being dispersed therein, and a weight ratio of vinyl acetate of 10 to 50.
% By weight, and a resin (A) containing an ethylene-vinyl acetate copolymer having a melt index of 2 to 200 as a main component
And a thermoplastic resin (B) having a higher melting point than the resin (A), and the resin (A) accounts for 10 to 90% of the fiber surface area.
Is immersed in a solution in which hinokitiol is dissolved, and the solution is exhausted by the resin (A).

Hinokitiol is the same substance as 4-isopropyltropone, and is mainly contained as iron (III) complex salt in Taiwan hinoki wood.

Hinokitiol has long been an insect repellent from natural timber,
Known as a fungicide, it is a natural substance and therefore harmless to the human body, and has been widely used in various fields. Focusing on the properties of hinokitiol as shown on the right, the inventors have selected hinokitiol as the antibacterial substance of the antibacterial fiber, and obtained a fiber having an antibacterial effect by incorporating the substance into the fiber.

As a result of diligent and intensive studies to include hinokitiol in the fiber, a composite yarn composed of EVAc and another fiber-forming resin has been obtained. In other words, EVAc is focused on the property that EVAc exhausts a large amount of fats and oils (fatty oils), especially vegetable oils, and the property that hinokitiol dissolves to some extent in vegetable oils.
Then, a composite yarn made of a resin having excellent spinnability is prepared, and the composite yarn is immersed in vegetable oil in which hinokitiol is dissolved, so that the hinokitiol is exhausted and held together with the vegetable oil in EVAc.

In the conventional post-processing method, since the target material is simply coated on the fiber surface, a sufficient amount cannot be added depending on the conditions, or the fibers may fall off due to friction. In recent years, a spinning method by kneading, in which a target substance is added to a polymer melted during fiber formation, has been developed.However, in the case of melt spinning, considerable heat is applied, so that a substance such as hinokitiol used in the present invention is used. In this case, it is not suitable because it may be denatured.

The method according to the present invention is a kind of post-processing method for imparting performance to fibers or woven fabrics, and fabrics.However, since the EVAc portion of the fibers spontaneously exhausts the chemical solution, the performance can be imparted reliably and easily. It has features that can be performed. In addition, since it can basically be exhausted by immersion under normal pressure, there are many advantages such as no need for special equipment such as high temperature and high pressure kettle.

The EVAc used in the present invention has a vinyl acetate content of 10 to
Either a 50% by weight ethylene-vinyl acetate copolymer or a partially saponified EVAc having a similar vinyl acetate content. The melt index is desirably 2 to 200 for both resins. When the melt index is out of the range, the spinnability becomes poor, and the composite spinning becomes difficult. The ratio of vinyl acetate to EVAc is suitably 10 to 50% by weight, preferably 10 to 40%. When the proportion of vinyl acetate exceeds 40%, EVAc becomes completely amorphous. This is a direction in which the rate of exhaustion of the vegetable oil and the amount of exhaustion increase. At first glance, it seems to be compatible with the present invention, but the swelling accompanying the exhaustion is extremely large, and the physical properties (strength, hardness, etc.) after the exhaustion. However, there are many problems such as a large decrease in the ratio, and this is not suitable for the present invention. Also, the ratio of vinyl acetate
If it is less than 10%, both the amount of exhaustion and the exhaustion rate are small and not practical. The proportion of vinyl acetate in the partially saponified EVAc is also from 10 to 50% by weight, preferably from 10 to 50% by weight, for the same reason as ordinary EVAc.
40% by weight is appropriate.

The other thermoplastic resin forming a composite yarn with EVAc preferably has a higher melting point than that of the resin containing EVAc as a main component, preferably 200 ° C. or more, and has excellent spinnability. EVA
Since c has poor spinnability, it can be fiberized by being combined with a resin having excellent spinnability. Further, if the melting point is 200 ° C. or less, it is not preferable because the application thereof is somewhat limited such that it is difficult to develop it for clothing or the like due to insufficient heat resistance. It is considered that polyesters containing polyethylene terephthalate and polybutylene terephthalate as main components, polyamides containing nylon 6, nylon 6,6 and metaxylene diamine nylon as main components, and the like are suitable as the resin.

The vegetable oil used in the present invention dissolves hinokitiol, EV
A medium to be introduced into Ac, specifically, Avies oil, Amiris oil, Angelica oil, Ambrett seed oil, Ylang-ylang oil, Elemi oil, Oak moss oil, Oyutia oil, Origanum oil, Oris oil, Cassie oil, Kananga oil, camomill oil, kayapte oil, karamus oil, galvanum oil, guaiatu oil, grapefruit oil, Costas oil, bitter oil, citronella oil, diasmin oil, ginger brain oil, sweet orange oil, stylax oil, spearmint oil , Sedarwood oil, geranium oil, dabana oil, tansy oil, turpentine oil, chiybellose flower essential oil, neroli oil,
Pine oil, patili oil, hatsuka oil, vanilla oil, balsam copaiba oil, balsam true oil, balsam peru oil, palmarosa oil, hillip oil, bitter almond oil, bitter orange oil, hiba oil, vetiver oil, peppermint oil, Penny royal oil, perilla oil, bergamot oil, benzoin oil, boa de rose oil, fragrance oil, mandarin oil, eucalyptus oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, rose oil, rosemary oil, etc. Natural vegetable oils and synthetic compounds that mimic the main components of these natural vegetable oils, i.e., alpha-pinene, beta-pinene, camphene, limonene, myrcene, tempen-based hydrocarbons such as beta-calyophylene, linalool, geraniol, nerol, Citronellol, Ravensroll, Myrsenol,
α-terpineol, 2-menthol, borneol,
Nobor, isobornylcyclohexanol, fuarnesol, nerolidol, terpene alcohols such as santalol, cedrol, pakiuri alcohol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamon alcohol, anth alcohol,
d, α-dimethylphenylethyl alcohol, α-phenylethanol, β-phenylethyldimethylcarbinol,
Alcohols such as phenoxyethanol and patch, diphenyl ether isosafluoroeugenol, p-methylanthole, anethole, eugenol, isoeugenol, methyl eugenol, methylisoeugenol,
Benzylisoeugenol, safrole, isosafrole, phenols such as methyl-β-naphthyl ether, ethyl-β-naphthyl ether and derivatives thereof, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, 2-methylundecanal,
Aliphatic aldehydes such as tridecanal, tetradecanal, hexadecanal, trans-2-hexenal, 2,6-nonanedienal, citral, citronellal, hydroxycitronellal, perilaldehyde, citronellyloxyacetaldehyde, liral, sinensal, etc. Terpene aldehyde, benzaldehyde,
Phenylacetaldehyde, 3-phenylpropionaldehyde, cinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, anisaldehyde, cuminaldehyde, piperonal, cyclamenaldehyde, pt-butyl-α-methyldihydrocinnamaldehyde, Acetals such as aromatic aldehydes such as vanillin and vourbonal, citral dimethyl acetal, citral diethyl acetal, hydroxycitronellal dimethyl acetal, phenylacetaldehyde dimethyl acetal, and fats such as 2-heptanone, 3-octanone, 2-octanone, 2-undecanone Aromatic ketones, carvone, mentone, terpene ketones such as pulegone, p-methylacetophenone, p-methoxyacetophenone, benzopheno , Benzylidene acetone, anisyl acetone, p- hydroxybenzyl acetone, 2-
Aromatic ketones such as acetonaphthone, α-, β-, γ-ionone, α-n, β-n, γ-n methylionone, α-, β
-, Γ-isomethylionone, α-, β-, γ-iron, α-, β-damasenone, α-, β-, γ-damascon, theaspirane, theaspiron, ezran, rosefuran, nootkatone, α-vetibon , Cis-diasmon, dihydrodiasmon, methyl diasmonate, methyl dihydrodiasmonate, diasmin lactone, maltol, cycloten, alicyclic ketones such as furaneol, alicyclic ethers, alicyclic lactones, muscone, cibetone, cyclo Macrocyclic ketones such as pentadecanone, cyclopentadecanolide, ambrettolide, cyclohexadecanolide, ethylene brassate, 12-oxahexadecanolide, 11-oxahexadecanolide, and 10-oxahexadecanolide; Lactones, musk xylene, musk ketone, musk umbret, Sutorido, Fuantorido, tonalid, Borakisorido like synthetic musk, rose oxide, oxide ketone, linalool oxide, 1,
8-Cineol, cyclic ethers such as bicyclodihydrohomofarnesyl oxide, indole, skatole,
6-methylquinoline, 7-methylquinoline, 6-isopropylquinoline, 2-methyltetrahydroquinoline, 6
-Heterocyclic compounds such as -methyltetrahydroquinoline, 2-isobutylthiazole, 2-furylmethanethiol, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, geranyl formate, benzyl formate, ethyl acetate A synthetic vegetable oil comprising a mixture of esters of aliphatic acids such as geranyl acetate, methyl benzoate, isoamyl benzoate, ethyl anisate, methyl salicylate, and esters of aromatic acids such as methyl cinnamate.

Next, the method for producing the fiber of the present invention will be described. First
The figure shows an outline of the spinning device.

One (1) of the two melt extruders has a resin (A) containing EVAc as a main component, and the other (2) has a resin (B) having a higher melting point and superior spinnability than (A). Is filled. The polymer streams melted and extruded by the extruder are each accurately measured by a gear pump and sent to a spinning head. The two polymer streams are combined by a packing metal attached to a head, and thereafter discharged from a spinneret to be converted into fibers.

In the composite form of the resins (A) and (B), the resin A has a small yarn surface area in consideration of performance such as exhaustion performance of hinokitiol solution, development of antibacterial performance, durability, and processability such as spinnability and stretchability. Ten
Any form may be used so as to include 〜90%, preferably 20-80%. FIG. 2 shows an example of a complex form of EVAc according to the present invention with another polymer. When kneading the resins (A) and (B) as in (6) in FIG. 2, a static mixer is used.

Spinning speed is 1000m / min ~ 1,000sm as same as general fiber
/ min, or high-speed spinning at 3000 to 5000 m / min. EVAc alone lacks spinnability, but by combining it with PET, PBT or nylon,
Significant high-speed spinning can be performed. Depending on the composite resin and composite form, two resins may be separated during stretching, and in that case, high-speed spinning will be effective. or,
Otherwise, it is possible to obtain a high-strength yarn by spinning at a normal spinning speed and performing stretching without fail.

In order to exhaust the hinokitiol vegetable oil solution into the fiber, woven fabric or fabric after spinning or drawing, the yarn or fabric is immersed in the solution under normal pressure or under pressure. Even at normal pressure, the exhaustion rate of EVAc is very fast, but when a faster exhaustion rate is required in the process, a method by pressurization is preferable. Also, the exhaustion rate can be increased by heating. When heating, it is necessary to carry out the heating within a range that does not cause volatilization and denaturation of the vegetable oil, elution of EVAc, and the like.

[Effect of the Invention] Since the EVAc component in the fiber spontaneously exhausts the antibacterial substance, the synthetic fiber of the present invention can reliably impart antibacterial performance while being a post-processing method, and also has durability. Excellent antibacterial and insect repellent fiber enabled.

(Examples) Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 Polyethylene terephthalate to which [η] = 0.65 and 0.5 wt% of TiO ₂ was added was extruded by a 40φ extruder, while 20 wt% of vinyl acetate was extruded from a 40φ extruder, and each was weighed in a predetermined amount. , And discharged from a round hole noise to perform composite spinning at a spinning speed of 1000 m / min. The cross section of the composite yarn is as shown in Fig. 3 and 20% of the total fiber surface area is EV
Ac is compounded to include. The spun yarn was drawn on a roller plate to obtain a multifilament of 75 denier 24 filaments.

The drawn yarn was knitted with a tube knitting machine to obtain a tube knitted fabric having a diameter of 7.5 cm. After completely removing the oil component of the knitted fabric with a detergent, 5 wt.
% Hinokitiol / olive oil solution at 40 ° C. for 30 minutes. After immersion, the knitted fabric is heated with a neutral detergent solution (about 30 ° C).
The solution adhering to the inside of the knitted fabric and between the stitches was completely removed. Thereafter, it was washed with water, dehydrated and air-dried. Left overnight,
The weight gain after air drying was measured and found to be 200%. The amount of hinokitiol contained in 1 g of the knitted tubular fabric before exhaustion was 40 mg. When the antibacterial property of the tubular knitted fabric was measured by a halo method using Staphylococcus aureus, a halo having a width of about 5 to 8 mm was formed around the knitted fabric, and it was confirmed that the knitted fabric had antibacterial properties. .

Example 2 Polybutylene terephthalate having [η] = 0.65 was extruded with a 40φ extruder, while EVAc having a vinyl acetate content of 25 wt% was extruded from 40.
After extruding from a φ extruder and measuring a predetermined amount each, it is washed down into a spinning pack, discharged from a round hole nozzle, and spinning speed is 3500
High-speed composite spinning was performed at m / min to obtain a multifilament of 90 denier 24 filaments. The cross section of the composite yarn was as shown in FIG. 4, and the composite was formed so that EVAc contained 30% of the total fiber surface area. The composite yarn was false twisted under normal conditions.

The false twisted yarn is shaped into a skein by a skein raising machine, and 5 wt%
The hinokitiol-hatsuka oil solution was immersed in 40 ° C for 40 minutes. After immersion, the skein was washed with a detergent (about 30 ° C.) and then washed with water. After washing with water and leaving to air-dry for one day, the skein was rolled back to a bobbin. In the yarn thus obtained, 30 mg of hinokitiol was exhausted with respect to 1 g of the yarn before exhaustion.

The hinokitiol exhausted yarn was knitted in the lower part of a commercially available sock and subjected to a wearing test. The socks not knitted with the exhaust yarn and the knitted socks were each worn for one day, and the subject himself evaluated the strength of body odor attached to the socks. As a result, 9 out of 10 subjects judged that the sock knitted with exhaustion yarn had a weaker body odor, and the deodorant effect of the exhaustion was recognized.

Comparative Example 1 The composite weight ratio of EVAc and polyethylene terephthalate was 9
A composite spinning was attempted in which the ratio of EVAc to the fiber surface was 95% at 0:10. However, the warping of the yarn on the nozzle surface was not suppressed and the spinning condition was poor.

Comparative Example 2 An attempt was made to obtain a composite yarn using EVAc having a melt index (MI) of 300 by the same method as in Example 1, but single yarn breakage during spinning frequently occurred and winding was difficult. . In addition, drawability was extremely poor, such as breakage of single yarns and feathers during drawing.

[Brief description of the drawings]

FIG. 1 is a schematic view of a spinning apparatus for obtaining the fiber of the present invention,
FIG. 2 is a view showing an example of a composite form of the fiber of the present invention, FIG. 3 is a simulated cross-sectional photograph of the fiber of the present invention according to Example 1, and FIG. FIG.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-53-61720 (JP, A) JP-A-64-37987 (JP, A) JP-B-46-11591 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) D01F 8/00-8/18

Claims (2)

(57) [Claims] 1. A resin (A) comprising an ethylene-vinyl acetate copolymer having a weight ratio of vinyl acetate of 10 to 50% by weight and a melt index of 2 to 200, and said resin (A) A composite fiber comprising a thermoplastic resin (B) having a melting point higher than that of the thermoplastic resin (B), wherein the resin (A) occupies 10 to 90% of the fiber surface area, and hinokitiol is dispersed in the resin (A). Antibacterial fiber characterized by the following. 2. A resin (A) containing an ethylene-vinyl acetate copolymer having a weight ratio of vinyl acetate of 10 to 50% by weight and a melt index of 2 to 200 as a main component, and the resin (A) A conjugate fiber composed of a thermoplastic resin (B) having a higher melting point and occupying 10 to 90% of the fiber surface area by the resin (A) is immersed in a solution of hinokitiol,
A method for producing antibacterial fibers, wherein the solution is exhausted by the resin (A).