JP2777191B2 - Fiber with insect repellent and repellent effect - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a fiber having an insect repellent and repellent effect. More specifically, the present invention relates to a method for converting a human body, a house, or a specific place from insect pests or insects that cause discomfort. Textile products used for the purpose of protection, for example clothing such as janbar, trousers, socks, gloves, mufflers, hats, handkerchiefs, towels, patches, etc., or daily necessities such as insect repellent nets, screen doors, mosquito nets, ropes, strings, tapes, mats, etc. And a fiber having an insect repellent and repellent effect.

[Prior Art] As a method for protecting a human body from pests, a method using an insect repellent or a repellent is known. Currently, N, N-diethyl-m-toluamide (deet) is mainly used for this purpose, and is a method of mixing with a spray or cream and spraying or applying directly to the skin. However, in this method, there is a great possibility that the insect repellent substance will migrate or fall off due to sweating or contact with clothes, and a stable effect cannot be expected.

These forms are also considered harmless to the human body, but if used by irritable people or people with weak skin,
Redness, rash, swelling, itching, etc. appear and are difficult to apply. In addition, there are many problems such as the fact that even ordinary people must use it so as not to touch the mucous membranes such as eyes and nose, wounds and the like. Recently, there has been proposed a method called an insect repellent jumper, in which an insect repellent drug is absorbed by a jumper or the like before outdoor activities and then used. However, fiber materials (polyester, nylon, cotton, etc.) usually used for clothes, etc., basically do not have the property of absorbing and retaining drugs, etc., and in this method, they are simply stained to the weave. There are problems such as dropout from the product and poor effect persistence.

[Problems to be Solved by the Invention] The present invention provides a fiber material for insect repellent and repellent products that can safely protect a human body from pests for a long time without fear of causing troubles on the skin.

[Means for Solving the Problem] The present inventors consider that by providing a fiber material having a pest and repellent effect, it is possible to impart an insect repellent and repellent effect to various fiber products constituted by the material. As a result of intensive studies, they have found a fiber having excellent insect repellency and sustained-release property and a repellent and repellent effect.

Attention has been paid to an ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVAc) in order to impart exhaustion of the insect repellent.
That is, EVAc has a strong affinity for fats and oils, especially vegetable oils, and has the property of swelling by absorbing a large amount of the oils,
Insect repellents and repellents are dissolved in vegetable oil, and fibrous EV
By immersing Ac, it was expected that the insect repellent could be exhausted into the fiber.

However, EVAc is inferior in spinnability, and melt spinnability alone is poor, and physical properties such as strength and elongation are not sufficient as a fiber material. Therefore, EVAc is melt-spun together with another resin with excellent spinnability to form a fiber, thereby exhausting the insect repellent solution.
A fiber material that can be held and has sufficient physical properties was successfully obtained.

Among the substances having an insect repellent and repellent effect used in the present invention, the most suitable are those having a property of being directly exhausted to the EVAc part of the fiber. However, those that can be dissolved in vegetable oils without being directly exhausted by EVAc, after dissolving in vegetable oil,
It can be exhausted into EVAc with vegetable oil. Although diethylamide, which is the most common insect repellent and repellent, is not directly exhausted by EVAc, it can be exhausted into EVAc together with these solvents by dissolving it in oat oil, olive oil, castor oil and the like. Even if the substance is solid at normal temperature, it can be exhausted by the same method as long as it is soluble in vegetable oils. Insect repellent that can be exhausted into EVAc by this method,
As repellents, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diethyl fumarate, N, N-diethyl-m-toluamide, ethyl benzoate, safrole,
Isosafrole, eugenol, citronellol, anethole, 1-carvone, cinnamaldehyde, benzaldehyde, O-methyl-N-phenylthiocarbamate,
O- ethyl -N- phenylene thioether carbamates, O- propyl -N- phenylene thioether carbamate, 2,3,4,5-bis (delta ₂ - butylene) - tetrahydrofurfuryl, di -
Normal-propyl isosine comeronate, di-normal-butyl succinate, 2-hydroxyethyl octyl sulfide, paradichlorobenzene, naphthalene, camphor, N-butyl acetanilide, N, N-diethyl succinamate, dimethyl phthalate, 2, 3,4,5
-Bis- (Δ ₂ -butylene) -tetrahydrofuran,
2,3,4,5-bis - (delta ₂ - butylene) - tetrahydrofurfuryl alcohol, diethylamide caprylate, second
Grade butyl styryl ketone, nonyl styryl ketone, N-
Propyl acetanilide, 2-ethyl-1,3-hexanediol, dibutyl di-n-butyl succinate, methoxymethyl, 2-butoxyethyl-2-furfuriden acetate, dibutyl phthalate, tetrahydrothiophene, β-naphthol, diallyl Disulphide,
Bis (dimethylthiocarbamoyl) disulphide, 2-
Butyl-2-ethyl-1,3-propanediol, m-tolyl-N-methylcarbamate, 5-chloro-4-amino-2,6-dimethylpyrimidine, 1-hexanoyl-piperidine, 1-pentanoyl-2,6 -Dimethyl-piperidine, O-ethyl-S-tertiarybutyl-sulfenylxanthate, 1-pentanoylhexahydro- ^1H -azepine, 1-hexanoyl3-pipecholine, 1
-Hexanoyl 2-pipecholine, 4-hexanoyl-2,
Examples thereof include 6-dimethylmorpholin, 1-octanoylpyrrolidine, naphthoquinone, and benzoquinone. These materials can be exhausted into EVAc either by themselves being exhausted by EVAc or by being dissolved in vegetable oil to be exhausted by EVAc.

When using vegetable oils, the compatibility with the substance to be dissolved must be carefully considered. Many vegetable oils or the main components of vegetable oils have a repellent effect by themselves. For example, housefly and mosquito rose geranium oil, sandalwood oil, menthol, citral, etc.,
Benzaldehyde for bees, neryl formate for mites, cockroach for cockroaches, cinnamic alcohol, methyl eugenol, geraniol, linalool,
Phenylacetaldehyde and the like are effective against menthol and cotton beetle. By using these vegetable oils and repellents, a greater repellent effect can be expected. In addition, the vegetable oils used in the present invention are specifically Avies oil, Amyris oil, Angelica oil, Ambrett seed oil, Ylang ylang oil, Elemin oil, Oak moss oil, Oyutiya oil, Origanum oil, Oris oil, Cassie oil, Kananga oil Oil, chamomile oil, kyapute oil, karamus oil, galvanum oil, guaiatu oil, grapefruit oil, Costas oil, syrup oil,
Citronella oil, jasmine oil, grape brain oil, sweet orange oil, stylax oil, spearmint oil, sedarwood oil, geranium oil, dabana oil, tansy oil, turpentine oil, chiy bellows flower essential oil, neroli oil, pine oil, pachiyuri 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,
Natural vegetable oils such as pore de rose oil, aromatic oil, mandarin oil, eucalyptus oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, rose oil, rosemary oil, and the main types of these natural vegetable oils Synthetic compounds that mimic the components: α-pinene, β-pinene, camphene, limonene,
Myrcene, tenpen-based hydrocarbons such as β-caryooffylene, linalool, geraniol, nerol, citronellol, lavandulol, myrcenol, α-terpineol, 2-menthol, borneol, noball, isobornylcyclohexanol, funarillel, nerolidol, santalol, Cedrol, terpene alcohols such as pakiuri alcohol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamon alcohol, anth alcohol, d, α-dimethylphenylethyl alcohol, α-phenylethanol, β
Alcohols such as phenylethyl dimethylcarbinol, phenoxyethanol, and patch, diphenylether isosafluoroeugenol, p-methylanthole,
Anethole, eugenol, isoeugenol, methyl eugenol, methyl isoeugenol, benzylisoeugenol, safrole, isosafrole, methyl-
phenols such as β-naphthyl ether and ethyl-β-naphthyl ether and derivatives thereof, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, 2-methylundecanal, tridecanal, tetradecanal, hexadecanal, trans-
Aliphatic aldehydes such as 2-hexenal and 2,6-nonanedienal, citral, citronellal, hydroxycitronellal, perilaldehyde, citronellyloxyacetaldehyde, laral, sinensal and other terpene aldehydes, benzaldehyde, phenylacetaldehyde, 3-phenyl Enylpropionaldehyde, cinnamaldehyde, α-amyl cinnamaldehyde, α-
Hexylcinnamaldehyde, anisaldehyde, cuminaldehyde, piperonal, cyclamenaldehyde,
Acetals such as pt-butyl-α-methyldihydrocinnamaldehyde, aromatic aldehydes such as vanillin and boubonal, citral dimethyl acetal, citral diethyl acetal, hydroxycitronellal dimethyl acetal, phenylacetaldehyde dimethyl acetal, 2-heptanone, Aliphatic ketones such as 3-octanone, 2-octanone, 2-undecanone, carboxylic acids, mentones, terpene ketones such as pulegone, p-methylacetophenone, p-methoxyacetophenone, benzophenone, benzylideneacetone, anisylacetone, p Aromatic ketones such as -hydroxybenzylacetone, 2-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 Alicyclic ketones such as maltol, cyclothene, and furaneol, alicyclic ethers, alicyclic lactones, muscone, dibetone, cyclopentadecanone, cyclopentadecanolide, umbretride,
Cyclohexadecanolide, ethylene brasilate, 12-
Macrocyclic ketones such as oxahexadecanolide, 11-oxahexadecanolide, and 10-oxahexadecanolide, lactones, musk xylene, musk ketone, musk ambretto, mosquen, celestride, fantrid, tonalide, boraxolide, and synthetic musks , Rose oxide, oxide ketone, linalool oxide, cyclic ethers such as 1,8-cineole, bicyclodihydrohomophanenesyl oxide, indole, skatole, 6-methylquinoline, 7-methylquinoline, 6-isopropylquinoline, 2-methyl Tetrahydroquinoline, 6-methyltetrahydroquinoline, 2-isobutylthiazole, 2-
Furylmethanethiol, 2-methylpyrazine, 2,5-dimethylvirazine, 2,3,5-trimethylpyrazine, etc., a heterocyclic compound, geranyl formate, benzyl formate, ethyl acetate,
Esters of aliphatic acids such as geranyl acetate, methyl benzoate,
It is a synthetic vegetable oil comprising a mixture of isoamyl benzoate, ethyl anisate, methyl salicylate, esters of aromatic acids such as methyl cinnamate and the like.

The EVAc used in the present invention has a vinyl acetate content of 10 to
Either 40% by weight ethylene-vinyl acetate copolymer or a partially saponified EVAc with 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 10-40% by weight
It is. 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, and at first glance it seems to be compatible with the present invention. However, the swelling accompanying the exhaustion is extremely large, and the physical properties (strength, hardness, etc.) after the exhaustion. ) Has many problems such as a large decrease, and is not suitable for the present invention. Also, the ratio of vinyl acetate
If it is less than 1.0%, the exhaustion amount and the exhaustion rate are both small and not practical. The proportion of vinyl acetate in the partially saponified EVAc is also 10 to 40% for the same reason as that of ordinary EVAc.

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. Polyester containing polyethylene terephthalate or polybutylene terephthalate as a main component, nylon 6, nylon 6,6, and polyamide containing meta-xylene diamine nylon as a main component are considered to be suitable as the resin.

Next, a method for producing a fiber having an insect repellent and repellent effect according to the present invention will be described. FIG. 1 shows an outline of the spinning apparatus of the present invention.

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 types of polymer streams are combined by a packing metal attached to the head, and then discharged from a spinneret to be converted into fibers.

The composite form of the resin (A) and the resin (B) is determined in consideration of the exhaustion performance of the vegetable oil solution of the repellent, the repellency, the expression of insect repellent effect, the durability and the like, and the processability such as spinnability and stretchability. It is sufficient if A contains 10 to 90%, preferably 20 to 80% of the yarn surface area. 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 also be performed without problems. Depending on the resin to be compounded and the form of the compound, the two resins may peel off during stretching, and in that case, high-speed spinning would be effective. Otherwise, it is also possible to obtain a high-strength yarn by spinning at a normal spinning speed and performing reliable drawing.

In order to exhaust the repellent and the vegetable oil solution of the repellent into the fiber or woven or knitted 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 repellent of EVAc and the repellent of the vegetable oil solution are remarkably fast. However, when the exhaustion rate is faster than in the process and the exhaustion rate is required, the method of pressurization is preferable.

Also, the rate of exhaustion 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] The fiber having an insect repellent and repellent effect and the method for producing the same according to the present invention can be used for a long period of time by exhausting and retaining a substance having an insect repellent and repellent effect by post-processing.
The present invention enables various textile products having a repellent effect, and relieves the user of the trouble caused by skin troubles, instability of the effect, etc., as in conventional spray products.

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 added was extruded with a 40φ extruder, while 20 wt% of vinyl acetate was extruded from a 40φ extruder, and each was weighed in a predetermined amount. The mixture was swept down into a spinning pack, discharged from a round hole nozzle, and a composite spinning was performed 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.
% N, N-diethyl-m-toluamide (deet) -olive oil solution at 40 ° C. for 30 minutes. After immersion, the knitted fabric was washed in a neutral detergent warm solution (about 30 ° C.) to completely remove the solution adhering to the knitted fabric and between the stitches. Thereafter, it was washed with water, dehydrated and air-dried. After standing overnight and air-drying, the weight increase was measured and found to be 190%.

The repellent effect of this deet-olive solution exhausted knitted fabric on Drosophila melanogaster was examined by the following method.

As shown in FIG. 4, one partition is placed in the center of a cubic container made of a transparent acrylic plate of 1 mx 1 mx 1 m. This partition has a 5 cm × 10 cm passage in the center. The volumes of the two rooms are the same, and one room (A) has
8 g of the tube knitted with the deet-olive oil solution exhausted, and 8 g of the tube knitted with the olive oil only exhausted in the other room (B).

30 Drosophila were released almost at the center of the partition, and 2 hours later, the percentage of Drosophila in the room (B) was expressed as a percentage, which was defined as the repellent rate. After measurement of the repellency, both knitted fabrics were taken out of the container and air-dried until the next measurement day.
Table 1 shows the test results. As is clear from Table 1,
The fiber of the present invention has a long-lasting repellent effect on Drosophila.

On the other hand, the safety of the knitted fabric on the skin was examined as follows. Subject 10 men and women between the ages of 20 and 45,
et The exhaust cylinder knitted fabric was attached to the arm. 9:00 am to 5 pm wearing time
Until the hour, the same tubular knitted fabric was used for 5 days. Five days later, the condition of the skin at the wearing site was observed, and there was no particular problem.

[Example 2] When a similar experiment was performed on house mosquitoes using the same tubular knitted fabric and apparatus as in Example 1, as shown in Table 2, a repellent effect similar to that of Drosophila was confirmed. .

[Example 3] Polybutylene terephthalate having [η] = 0.68 was extruded into 40φ, while EVAc having a vinyl acetate content of 25wt% was extruded from a 40φ extruder, each of which was weighed in a predetermined amount, and was then washed down into a spinning pack and discharged from a round hole nozzle. Then, high-speed composite spinning was performed at a spinning speed of 3500 m / min to obtain a multifilament of 90 denier 24 filaments. The cross section of the composite yarn was as shown in FIG. 5, 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 a 5 wt% deet-hatsuka oil solution 40
It was immersed in C for 40 minutes. After immersion, the skein was washed with a detergent (about 30 ° C.) and then washed with water. After rinsing and left to air dry for one day, the skein was wound back on a bobbin. In the yarn thus obtained, 35 mg of deet was exhausted per 1 g of the yarn before exhaustion.

About 3 g of the deet exhaust yarn was sewn into a hiking hat as shown in FIG. The repellent rate of this hat was determined in the same manner as in Example 1 by using a hat of the same type and nothing sewn as a control. The repellent rate did not fall below 90% even after 2 weeks.

Example 4 Using the same deet exhaustion yarn as in Example 3, the yarn was sewn into the sleeve of a cotton jumper. By the same method as in Example 1,
When the repellency of the jumper was measured, even after 2 weeks
93%.

Comparative Example 1 The composite weight ratio of EVAc and polyethylene terephthalate was 9
At 0:10, the ratio of EVAc to the fiber surface was 95%, and composite spinning was attempted. 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. . Also, the drawability was extremely poor, such as breakage of single yarn and fluff 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 diagram showing an example of the 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, FIG. FIG. 6 is a simulated cross-sectional photograph of the fiber of the present invention according to Example 3, and FIG. 6 shows a hat sewn with the fiber of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-1379 (JP, A) JP-A-60-119910 (JP, A) JP-A-60-71736 (JP, A) (58) Investigation Field (Int.Cl. ⁶ , DB name) D01F 8/00-8/18 D06M 13/00-15/715

Claims (2)

(57) [Claims] 1. A resin (A) containing an ethylene-vinyl acetate copolymer having a weight ratio of vinyl acetate of 10 to 40% by weight and a melt index of 2 to 200 as a main component, and the resin (A) A composite fiber comprising a thermoplastic resin (B) having a higher melting point, wherein the resin (A) occupies 10 to 90% of the fiber surface area. And a substance having an insect repellent and repellent effect dispersed therein. 2. The substance having an insect repellent and repellent effect is N, N-
Diethyl-m-toluamide, pyrimidine derivative, piperidine derivative, xanthogen derivative, azepine derivative, pipecoline derivative, morpholine derivative, pyrrolidine derivative, quinones, dihydric alcohols, phthalate esters, 2,3,4,5-bis _2. The fiber according to claim 1, wherein the fiber is at least one selected from the group consisting of (Δ ₂ -butylene) -tetrahydrofurfural, dinormal propyl isosine comeronate, dinormal butyl succinate, and 2-hydroxyethyloctyl sulfide. .