WO2019142810A1 - Multifilament and insect repellent woven/knitted fabric - Google Patents

Abstract

The present invention provides a multifilament which exhibits excellent weather resistance and sustainability in terms of insect repellent properties. A multifilament which contains a pyrethroid compound, and wherein the amount of the pyrethroid compound in the surface is 0.1-15 μg/cm².

Description

Multifilament, insect repellent woven fabric

The present invention relates to a multifilament, insect repellent woven fabric.
The present application claims priority based on Japanese Patent Application Nos. 2018-005050 filed in Japan on January 16, 2018 and Japanese Patent Application No. 2018-196665 filed in October 18, 2018, The contents are incorporated herein.

In recent years, damage caused by various pests such as mosquitoes, fleas, lice, mites and flies has increased. One of the methods for avoiding the damage caused by pests is a method in which a liquid containing an insect repellent is directly applied to the exposed area of the skin by spraying or the like. However, in this method, the duration of the insect repellent performance is short, and skin irritation by direct application may be a problem.

Therefore, various insect repellent fibers having insect repellent properties have been proposed. An insect repellent is attached to or contained in the insect repellent fiber. Therefore, insect repellent performance is exhibited when pests come in contact with insect repellent fibers (Patent Documents 1 to 3).
Patent Document 1 describes a polymer composition containing an olefin polymer and an insect repellent agent and a fiber obtained using the polymer composition. In the polymer composition of Patent Document 1, the content of the insect repellent agent is 0.1 to 10 parts by weight per 100 parts by weight of the olefin polymer.
Patent Document 2 describes a pest repellent processing method of polyester fiber. In the pest-repellent processing method of polyester fiber of patent document 2, polyester fiber is heat-processed in the liquid containing a pyrethroid type compound.
Patent Document 3 describes an insect repellent fiber capable of releasing an insect repellent. The insect repellent fiber described in Patent Document 3 contains an insect repellent, and has a core and a sheath.

JP 2008-106232A JP 10-219565 A International Publication No. 2016/143809

However, the insect repellent fiber has a problem that the content of the insect repellent decreases with time due to long-term use, and the insect repellent performance decreases with a decrease in the content of the insect repellent.
The fibers obtained by using the polymer composition described in Patent Document 1 have not been studied at all in terms of enhancing the weather resistance of insecticidal performance when used outdoors.
In the pest repellent processing method described in Patent Document 2, after the polyester fiber is produced, the pyrethroid compound is adhered to the surface of the fiber. Therefore, in the pest repellent processing method described in Patent Document 2, the adhesion amount of the pyrethroid compound may be reduced by washing or the like, and an insect repellent fiber having sufficient durability of insect repellent performance can not be obtained.
The insect-repellent fiber described in the example of Patent Document 3 is a monofilament of core-sheath structure in which the thickness of the sheath is 5 μm or more and the insect-repellent agent is contained in the core. However, since the thickness of the sheath portion is 5 μm or more, the insect-repellent fiber described in the example of Patent Document 3 does not have sufficient insect-repellent performance.

An object of the present invention is to provide a multifilament which is excellent in weather resistance and durability of insect repellent performance; and an insect repellent woven fabric which is excellent in weather resistance and durability of insect repellent performance.

The present invention has been completed as a result of intensive studies by the inventors of the present invention to provide a multifilament capable of exhibiting excellent insect-repellent performance even after long-term use.
The summary of the present invention relates to the following.
[1] A multifilament comprising a pyrethroid compound, wherein the surface amount of the pyrethroid compound is 0.1 to 15 μg / cm ² .
[2] The multifilament of [1], wherein the single fiber fineness of the single fiber constituting the multifilament is 1 to 15 dtex.
[3] The multifilament of [1] or [2], wherein the content of the pyrethroid compound is 0.1 to 3% by mass with respect to 100% by mass of the multifilament.
[4] The multifilament according to any one of [1] to [3], further comprising a high molecular weight hindered amine stabilizer, wherein the content of the high molecular weight hindered amine stabilizer is 0.05 to 1% by mass. .
[5] The multifilament of any one of [1] to [4], wherein the controlled release amount of the pyrethroid compound for 24 hours is 0.05 to 3 μg / cm ² · 24 hr.
[6] The multifilament of any one of [1] to [5], wherein the surface amount of the pyrethroid compound after weathering for 250 hours is 0.1 to 15 μg / cm ² .
[7] The multifilament of any one of [1] to [6], wherein the 24-hour sustained release amount of the pyrethroid compound after the 250-hour weathering test is 0.05 to 3 μg / cm ² · 24 hr.
[8] The single fiber has a core and a sheath formed outside the core, the core contains the pyrethroid compound, and the content of the pyrethroid compound is multifilament 100. The multifilament according to any one of [1] to [7], which is 0.1 to 3% by mass with respect to mass%, and the single fiber fineness of the single fiber is 1 to 7 dtex.
[9] The multifilament of [8], wherein the thickness of the sheath portion is 4 μm or less.
[10] The multifilament of [8] or [9], wherein the ratio (V1 / V2) of the volume V1 of the core to the volume V2 of the sheath is 1/3 to 3/1.
[11] The multifilament of any one of [8] to [10], wherein the resin constituting the core part is a polyolefin resin.
[12] Any one of [8] to [11], wherein the resin constituting the sheath part is at least one selected from the group consisting of polypropylene resins, polyethylene resins, polyester resins, and polyamide resins. Multifilament.
[13] The multifilament according to any one of [1] to [12], wherein the reduction rate of the pyrethroid compound calculated by the following formula (1) is 70% or less.
(Decrease rate of pyrethroid compound) = (W1-W2) / (W1) × 100 (1)
In the formula (1), W1 is the content of the multifilament pyrethroid compound before the 250 hour weathering test, and W2 is the content of the multifilament pyrethroid compound after the 250 hour weathering test.
[14] The multifilament of any one of [1] to [13], wherein the repellent rate of pests after a 250-hour weathering test is 70% or more.
[15] An insect-repellent woven or knitted fabric comprising the multifilament according to any one of [1] to [14].
[16] The insect repellent woven or knitted fabric according to [15], wherein the content of the multifilament is 10% by mass or more.
[17] The insect-repellent woven fabric according to [15] or [16], further comprising a fusion yarn, wherein an intersection of the multifilament and the fusion yarn is thermally bonded by the fusion yarn.

The first aspect of the present invention relates to the following.
<1> A polyolefin multifilament having an insect repellent performance which contains a pyrethroid compound and the surface amount of the pyrethroid compound in the fiber is 3 to 15 μg / cm ² .
<2> The polyolefin multifilament of <1>, wherein the content of the pyrethroid compound is 0.1 to 3% by mass.
<3> A polyolefin multifilament of <1> or <2>, wherein the monofilament fineness of the multifilament is 1 to 15 dtex.
<4> The polyolefin multifilament of any one of <1> to <3>, wherein the controlled release amount of the pyrethroid compound from the fiber is 0.1 to 3 μg / cm ² · 24 hr.
<5> A polyolefin multifilament according to any one of <1> to <4>, containing 0.1 to 1% by mass of a high molecular weight hindered amine stabilizer.
<6> The polyolefin multifilament of any one of <1> to <5>, wherein the surface amount of the pyrethroid compound in the fiber after the weathering test for 250 hours is 3 to 15 μg / cm ² .
<7> The polyolefin multifilament of any one of <1> to <6>, wherein the controlled release amount of the pyrethroid compound from the fiber after the weathering test for 250 hours is 0.1 to 3 μg / cm ² · 24 hr.

The second aspect of the present invention relates to the following.
«1» A core-sheath composite multifilament having a single fiber constituting a multifilament and a sheath formed on the outer side of the core, containing a pyrethroid-based compound in the core, a pyrethroid series A core-sheath composite multifilament having a content of the compound of 0.1 to 3% by mass and a single fiber fineness of 1 to 7 dtex with respect to 100% by mass of the core-sheath composite multifilament.
<< 2 >> core-sheath composite type multifilament of << 1 >> in which the thickness of the sheath portion is 4 μm or less.
<< 3 >> A core-sheath composite multifilament of << 1 >> or << 2 >> in which the ratio (V1 / V2) of the volume V1 of the core to the volume V2 of the sheath is 1/3 to 3/1.
<< 4 >> The core-sheath composite multifilament of any one of << 1 >> to << 3 >>, wherein the resin constituting the core part is a polyolefin resin.
«5» Any one of «1» to «4», wherein the resin constituting the sheath is at least one selected from the group consisting of polypropylene resins, polyethylene resins, polyester resins, and polyamide resins. Core-sheath complex type multifilament.
«6» The sheath of any of «1» to «5», further comprising a high molecular weight hindered amine stabilizer, wherein the content of the high molecular weight hindered amine stabilizer is 0.05 to 1% by mass. Composite type multifilament.
<< 7 >> The core-sheath composite multifilament of any of << 1 >> to << 6 >>, wherein the surface amount of the pyrethroid compound is 0.1 to 4.0 μg / cm ² .
<< 8 >> The core-sheath composite multifilament of any of << 1 >>-<7 >>, wherein the controlled release amount of the pyrethroid compound for 24 hours is 0.05 to 3 μg / cm ² · 24 hr.
«9» Any sheath / sheath composite multifilament of «1» to «8» having a repellent rate of 70% or more after a 250-hour weathering test.
<< 10 >> The core-sheath composite multifilament of any one of <1> to <9>, wherein the surface amount of the pyrethroid compound after the 250-hour weathering test is 0.1 to 4.0 μg / cm ² .
<< 11 >> The core-sheath composite multifilament of any of << 1 >>-<10 >>, wherein the 24-hour sustained release amount of the pyrethroid compound after the 250-hour weathering test is 0.05 to 3 μg / cm ² · 24 hr.
An insect-repellent woven or knitted fabric comprising a core-sheath composite multifilament according to any one of <12><1> to <11>.
<< 13 >> The insect-repellent woven fabric of << 12 >> in which the content of the core-sheath composite multifilament is 10% by mass or more.
<14> An insect-repellent woven fabric according to <12> or <13>, further comprising a fusion yarn, wherein an intersection of the core-sheath composite multifilament and the fusion yarn is thermally bonded by the fusion yarn.

According to the present invention, it is possible to provide a multifilament which is excellent in weather resistance and durability of insect repellent performance; and an insect repellent woven or knitted fabric which is excellent in weather resistance and durability of insect repellent performance.

The meanings of the following terms in the present specification are as follows.
The "surface amount of pyrethroid compound" refers to the mass per unit area of the pyrethroid compound present on the surface of the multifilament. "Surface amount of pyrethroid compound" can be obtained, for example, by taking a knitted fabric containing multifilament as a sample, immersing the sample in 99.7% methanol for 10 minutes at 25.degree. The mass of the pyrethroid compound can be measured, and the mass can be determined by dividing the mass by the surface area of the sample.
The “single fiber fineness” is a value calculated by dividing the total fineness of multifilaments by the number of filaments (that is, the number of single fibers constituting the multifilaments).
“Content of pyrethroid-based compound” refers to the mass of pyrethroid-based compound extracted in 99.7% methanol by immersing the multifilament in 99.7% methanol at 45 ° C. for 48 hours It is a value calculated by doing.
The “24 hour sustained release amount of pyrethroid compound” is the mass of the pyrethroid compound released from the inside of the multifilament to the surface of the multifilament in 24 hours. For the “24 hour sustained release amount of pyrethroid compound”, for example, a knitted fabric containing multifilaments is used as a sample, and after being dipped and washed in 99.7% of methanol, the sample after standing for 24 hours in a 20 ° C. environment It can be determined as the surface amount of the pyrethroid compound to be measured.
"250-hour weathering test" means a carbon arc weathering test performed under the conditions of a temperature of 63 ° C and a testing time of 250 hours.
The "insecting performance" means that the KT 50 value is relatively low, and refers to the performance that exerts a pest repellent effect with a high repellent rate.
The “KT 50 value” means the time when it is expected that 50% of the input pest will tip over when the pest is input into a test container having a sample containing multifilaments.
"Pests" are insects that cause damage to humans, livestock, pets and agricultural products. Pests are classified into hygiene pests, agricultural pests, food pests, etc., depending on the target of the harm. For example, hygiene pests include mosquitoes, flies, cockroaches, fleas, bedbugs, lice, mites and the like. However, pests are not limited to these examples.
“-” Indicating a numerical range means that numerical values described before and after that are included as the lower limit value and the upper limit value.

The multifilament of the present invention contains a pyrethroid compound. In the multifilament of the present invention, the pyrethroid compound functions as a pest repellent component. It can be said that pyrethroid compounds are insect repellents.
The pyrethroid compound is not particularly limited as long as it exhibits insect-repellent performance. However, as the pyrethroid compound, etofenprox is particularly preferable.

Rat oral LD ₅₀ can be used as an indicator of acute toxicity of etofenprox. In addition, the daily intake allowance (hereinafter referred to as "ADI") can be used as an indicator of chronic toxicity of etofenprox.
The rat oral LD ₅₀ and ADI are described as follows in KIX SDS Co., Ltd., Kanagawa Prefecture KISNET, Encyclopedia of Pesticide Toxicity (3rd edition) and the like.
· Etofenprox of rat oral _LD 50: _42880mg / kg body weight.
ADI of etofenprox: 0.03 mg / kg body weight 24 hr.

Further examples of pyrethroid compounds include permethrin and metfluthrin.
Rat Oral _{LD 50} for permethrin is 383 mg / kg body weight, ADI is 0.05 mg / kg body weight · 24 hr or.
Rat Oral _{LD 50} for metofluthrin is 2000 mg / kg body weight, ADI is 0.04 mg / kg body weight · 24 hr or.

Thus, ADI is almost the same level for all of etofenprox, permethrin and metfluthrin. But with respect to the rat oral LD _50, etofenprox, permethrin, the numerical value of etofenprox Among Metofluthrin highest. Therefore, etofenprox is preferable because it is more safe than permethrin, metfluthrin, and the like.

In addition, etofenprox is licensed to the United States Environmental Protection Agency (EPA). And, since etofenprox is classified as Class U (Unlikely to present acute hazard in normal use) in "CLASSIFICATION OF ACTIVE PESTICIDE INGREDIENTS" published by the World Health Organization (WHO), serious danger Not likely to show. Furthermore, etofenprox is also seminegative to the results of the patch test by river method.
From the above, it is considered that etofenprox is a highly safe compound, and thus it is preferable as a pyrethroid compound.

In the multifilament of the present invention, the surface amount of the pyrethroid compound is 0.1 to 15 μg / cm ² . Surface weight of pyrethroid compound is preferably 0.5 ~ 14.8μg / cm ^2, more preferably 2.0 ~ 14.8μg / cm ^2, more preferably ^{3.0 ~ 15.0μg / cm 2, 3} . 5 to 14.8 μg / cm ² is particularly preferred, and 4.5 to 14.5 μg / cm ² is most preferred.
When the surface amount of the pyrethroid compound is 0.1 μg / cm ² or more, the repellent rate of pests is 80% or more, and the multifilament can be provided with insect repellent performance. That is, it can be said that the multifilament has insect-repellent performance when the surface amount of the pyrethroid compound is 0.1 μg / cm ² or more.
If the surface amount of the pyrethroid compound is 3.0 μg / cm ² or more, it is possible to easily obtain a fast-acting insect repellent performance that the KT 50 value is within 30 minutes.
When the surface amount of the pyrethroid compound is 15 μg / cm ² or less, the production cost of the multifilament can be reduced.

In the multifilament of the present invention, the content of the pyrethroid compound is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, and still more preferably 0.4 to 1.5% by mass. preferable.
When the content of the pyrethroid compound is 0.1% by mass or more, excellent repellent performance such as a repellent rate of pest of 80% or more is easily obtained. When the content of the pyrethroid compound is 3% by mass or less, the spinning properties at the time of obtaining a multifilament tend to be stable.

The multifilament of the present invention preferably further contains a high molecular weight hindered amine stabilizer. When the multifilament further contains a high molecular weight type hindered amine stabilizer, the weatherability of the multifilament is further enhanced.
The number average molecular weight of the high molecular weight hindered amine stabilizer is 1000 or more, preferably 2000 or more. When the number average molecular weight of the high molecular weight hindered amine stabilizer is 2000 or more, the elution of the high molecular weight hindered amine stabilizer from the multifilament into water tends to be suppressed.

Examples of high molecular weight hindered amine stabilizers include N, N ′, N ′ ′, N ′ ′ ′-tetrakis- (4,6-bis- (butyl- (N-2,2,6,6-tetra) Methylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1, 3,5-Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) Polymers of dimethyl imino}] succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and the like can be mentioned.

When the multifilament further contains a high molecular weight hindered amine stabilizer, the content of the high molecular weight hindered amine stabilizer is preferably 0.05 to 1% by mass, more preferably 0.075 to 0.9% by mass. 0.1 to 0.9% by mass is more preferable, and 0.1 to 0.7% by mass is particularly preferable.
When the content of the high molecular weight hindered amine stabilizer is 0.05% by mass or more, the weather resistance of the multifilament tends to be sufficiently recognized. When the content of the high molecular weight type hindered amine stabilizer is 1% by mass or less, yarn breakage tends to be reduced during production of the multifilament.

The single fiber fineness of the single fiber constituting the multifilament of the present invention is preferably 1 to 15 dtex, more preferably 1.5 to 13 dtex, and still more preferably 2 to 10 dtex.
The total fineness of the multifilament is not particularly limited. The total fineness of the multifilament may be, for example, 40 to 200 dtex, or 50 to 150 dtex.
When the single fiber fineness is 1 dtex or more, yarn breakage at the time of production of the multifilament is reduced, and the spinning property is improved. When the single fiber fineness is 15 dtex or less, sufficient softness is obtained when the multifilament is made into a fiber product.
Under the condition that the total fineness of the multifilament is constant, the finer the single fiber, the larger the surface area of the multifilament. Therefore, the insect repellent performance is further enhanced.

In the multifilament, the resin constituting the single fiber is not particularly limited. As a specific example of resin which comprises a single fiber, polyolefin resin (a polypropylene resin, polyethylene resin etc.), polyester resin, a polyamide resin is mentioned, for example.
Among these, in consideration of the low heat resistance of the pyrethroid compound, the resin constituting the single fiber is preferably a polyolefin resin, more preferably a polypropylene resin or a polyethylene resin, because the melting point is relatively low.
Thus, the multifilament can be said to be a kind of chemical fiber.

In the case of a multifilament, when the resin constituting the single fiber is a polypropylene resin, the specific gravity of polypropylene is relatively small, so the multifilament becomes light. In this case, the multifilament can be suitably applied to material applications.
In the case of a multifilament, when the resin constituting the single fiber is a polyethylene resin, the polyethylene resin serves as a cooling sensation material, and therefore the multifilament can be suitably applied to applications such as clothing for summer.

The 24-hour sustained release amount of the pyrethroid compound can be said to be a sustained release amount of the pyrethroid compound volatilized from the multifilament fiber.
In the multifilament of the present invention, the sustained release amount of the pyrethroid compound for 24 hours is preferably 0.05 to 3 μg / cm ² · 24 hr, more preferably 0.1 to 3 μg / cm ² · 24 hr, 0.15 to 2 μg / Cm ² · 24 hr is more preferable, and 0.2 to 1.5 μg / cm ² · 24 hr is particularly preferable.
When the 24 hour sustained release amount of the pyrethroid compound is 0.05 μg / cm ² · 24 hr or more, the insect repellent performance is further improved. When referring to the upper limit value of the 24-hour sustained release amount of the pyrethroid compound, durability of the insect repellent performance is sufficiently recognized even at 3 μg / cm ² · 24 h or less.

In the multifilament of the present invention, the surface amount of the pyrethroid compound after the 250 hour weathering test is preferably 3 to 15 μg / cm ² .
When the surface amount of the pyrethroid compound after the 250-hour weathering test is 3 μg / cm ² or more, the repellent rate of pests is 80% or more, and the weather resistance of insect repellent performance and the durability of insect repellent performance are further improved.
The upper limit of the surface amount of the multifilamentary pyrethroid compound after the 250-hour weathering test is not particularly limited. Regarding the upper limit value, insect repellent performance is sufficiently recognized even at 15 μg / cm ² or less.

In the multifilament of the present invention, the amount of sustained release for 24 hours after the 250 hour weathering test is preferably 0.05 to 3 μg / cm ² · 24 hr, more preferably 0.1 to 3 μg / cm ² · 24 hr.
When the 24-hour sustained release amount after the 250-hour weathering test is 0.1 μg / cm ² · 24 hr or more, sufficient insect-repellent performance is observed. When referring to the upper limit value of the 24-hour sustained release after the 250-hour weathering test, the durability of the insect-repellent performance is sufficiently recognized even at 3 μg / cm ² · 24 h or less.

In the multifilament of the present invention, the reduction rate of the pyrethroid compound calculated by the following formula (1) is preferably 70% or less. If the reduction rate is 70% or less, the insect repellent performance is likely to be sustained even when used outdoors for a long time.
(Decrease rate of pyrethroid compound) = (W1-W2) / (W1) × 100 (1)
In the formula (1), W1 is the content of the multifilament pyrethroid compound before the 250 hour weathering test, and W2 is the content of the multifilament pyrethroid compound after the 250 hour weathering test.

In the multifilament of the present invention, the repellent rate of pests after a 250 hour weathering test is preferably 70% or more, more preferably 75% or more, and still more preferably 80% or more.
When the repellent rate of the pests after the 250 hour weathering test is 70% or more, satisfactory insect repellent performance is observed even when used outdoors for about a year, and the weather resistance of the multifilament repellent performance is further excellent.
When the repellent rate of pests after the 250-hour weathering test is 75% or more, the insecticidal performance of the multifilament tends to be sufficiently recognized even after long-term use.
When the repellent rate of pests after the 250-hour weathering test is 80% or more, the durability and the rapid effect of the multifilament filamentous insecticidal performance are further excellent.

The multifilament of the present invention can be produced, for example, by melt spinning. For example, a single fiber can be made to contain a predetermined amount of pyrethroid-based compound by melt-kneading a resin as a raw material of the single fiber and the pyrethroid-based compound in the spinning stage. At the time of melt-kneading, a pyrethroid compound may be kneaded into a resin as a raw material of single fibers.
The production method using kneading is more durable and lasting in insect repellent performance than the production method by post-processing in which the pyrethroid compound is attached to the surface of the fiber after producing the fiber as described in Patent Document 2 Get better.

(Action effect)
In the multifilament described above, since the surface amount of the pyrethroid compound is 0.1 to 15 μg / cm ² , the pyrethroid compound has sufficient insect-repellent performance even with a small content of the pyrethroid compound, which will be described later. As shown in the examples, the weather resistance and durability of the insect repellent performance are excellent.

The multifilament of the present invention is preferably a core-sheath composite multifilament in which single fibers constituting the multifilament have a core and a sheath.
Hereinafter, a core-sheath composite multifilament will be described as a preferred embodiment of the multifilament of the present invention.

In the single fiber constituting the core-sheath composite multifilament, the sheath is formed on the outside of the core.
The core-sheath composite multifilament contains a pyrethroid-based compound in the core portion. Even if the core-sheath composite type multifilament contains the pyrethroid-based compound in the core, the pyrethroid-based compound is gradually released from the core to the surface of the fiber, so that the sustainability of the insecticidal performance is further improved.

In the core-sheath composite multifilament, the thickness of the sheath portion of the single fiber is preferably 4 μm or less, more preferably 3.9 μm or less, and still more preferably 3.8 μm or less. The lower limit of the thickness of the sheath portion of the single fiber is not particularly limited, and may be, for example, 0.7 μm or more.
When the thickness of the sheath portion is 4 μm or less, the surface amount of the pyrethroid compound tends to be a value suitable for exhibiting a sufficient insect repellent performance, and the immediate effect of the insect repellent performance is improved.
When the thickness of the sheath portion is 3.9 μm or less, the core-sheath composite multifilament is more likely to exhibit sufficient insect-repellent performance. Even when the thickness of the sheath portion is 3.8 μm or less, the durability of the insect-repellent performance of the core-sheath composite multifilament is sufficiently recognized.

In the core-sheath composite multifilament, the ratio (V1 / V2) of the volume V1 of the core to the volume V2 of the sheath of a single fiber is preferably 1/3 to 3/1, and 1 / 2.5 to 2.8 / 1 is more preferable, and 1/2 to 2.5 / 1 is more preferable.
When the ratio (V1 / V2) is 1/3 or more, the surface amount of the pyrethroid compound tends to be a value suitable for exhibiting sufficient insect-repellent performance.
When the ratio (V1 / V2) is 3/1 or less, the immediate effect of the insect-repellent performance of the core-sheath composite multifilament is improved.

In the core-sheath composite multifilament, the resin constituting the core of the single fiber is not particularly limited. As a specific example of resin which comprises the core part of a single fiber, polyolefin resin (a polypropylene resin, polyethylene resin etc.), polyester resin, a polyamide resin is mentioned, for example.
Among these, in view of the low heat resistance of the pyrethroid compound, the resin constituting the core of the single fiber is preferably a polyolefin resin because a melting point is relatively low, and a polypropylene resin or a polyethylene resin is preferable. More preferable.

In the core-sheath composite multifilament, when the resin constituting the core of the single fiber is a polypropylene resin, the specific gravity of polypropylene is relatively small, so the core-sheath composite multifilament becomes light. In this case, the core-sheath composite multifilament can be suitably applied to material applications.
In the core-sheath composite type multifilament, when the resin constituting the core portion of the single fiber is polyethylene resin, the polyethylene resin serves as a cooling sensation material, so the core-sheath composite type multifilament is used for applications such as clothing for summer It can apply suitably.

In the core-sheath composite multifilament, the resin constituting the sheath portion of the single fiber is preferably at least one selected from the group consisting of polypropylene resins, polyethylene resins, polyester resins and polyamide resins. Thereby, when producing a core-sheath composite multifilament, it becomes easy to contain the pyrethroid compound in the core by so-called kneading. As a result, the weather resistance and durability of the insect-repellent performance of the core-sheath composite multifilament are further excellent.

In the core-sheath composite multifilament, the single fiber fineness of single fibers constituting the multifilament is preferably 1 to 7 dtex, more preferably 1.5 to 6 dtex, and still more preferably 2 to 4 dtex.
In the core-sheath composite multifilament, when the single fiber fineness of the single fiber constituting the multifilament is 1 dtex or more, yarn breakage at the time of production of the multifilament decreases. In the core-sheath composite multifilament, when the single fiber fineness of the single fiber constituting the multifilament is 7 dtex or less, sufficient softness is obtained when made into a fiber product, and the insect repellent performance is further improved.

In the core-sheath composite multifilament, the content of the pyrethroid compound is preferably 0.1 to 3% by mass, and more preferably 0.2 to 2.5% by mass with respect to 100% by mass of the core-sheath composite multifilament. And 0.3 to 2.0% by mass is more preferable.
When the content of the pyrethroid compound is 0.1% by mass or more based on 100% by mass of the core-sheath complex type multifilament, excellent repellent performance of 80% or more of pest repellant rate is obtained, and the core-sheath complex type multi The weather resistance and durability of the insect repellent performance of the filament are further excellent. When the content of the pyrethroid compound is 3% by mass or less with respect to 100% by mass of the core-sheath composite multifilament, the spinning properties when obtaining the core-sheath composite multifilament tend to be stable.

The core-in-sheath composite multifilament preferably further contains a high molecular weight hindered amine stabilizer. In this case, the core-sheath composite multifilament may contain a high molecular weight hindered amine stabilizer in the core or in the sheath. When the core-in-sheath composite type multifilament contains a high molecular weight type hindered amine stabilizer, the weather resistance and durability of the insect-repellent performance of the core-in-sheath composite type multifilament are further excellent.

When the core-sheath composite multifilament further contains a high molecular weight hindered amine stabilizer, the content of the high molecular weight hindered amine stabilizer is 0.05 to 1% by mass with respect to 100% by mass of the core-sheath composite multifilament. Is preferable, 0.075 to 0.9% by mass is more preferable, and 0.1 to 0.8% by mass is more preferable.
When the content of the high molecular weight hindered amine-based stabilizer is 0.05% by mass or more based on 100% by mass of the core-sheath composite multifilament, the weather resistance and the durability of the insect-repellent performance of the core-sheath composite multifilament are further excellent .
When the content of the high molecular weight type hindered amine stabilizer is 1% by mass or less with respect to 100% by mass of the core-sheath complex type multifilament, the occurrence frequency of the yarn breakage at the time of producing the core-sheath complex type multifilament may be reduced it can.

The surface amount of the core-sheath composite multifilament pyrethroid compound is preferably 0.1 to 5.0 μg / cm ^2, more preferably 0.5 to 4.5 μg / cm ² , and 2.0 to 4.0 μg / cm ^2. cm ² is more preferred.
When the surface amount of the core-sheath composite multifilament pyrethroid compound is 0.1 μg / cm ² or more, the insect-repellent performance of the core-sheath composite multifilament tends to be further excellent. When the surface amount of the core-sheath complex multifilament pyrethroid compound is 2.0 μg / cm ² or more, the rapid action is excellent.
When the surface amount of the pyrethroid compound of the core-sheath complex type multifilament is 5.0 μg / cm ² or less, the durability of the insect-repellent performance of the core-sheath complex type multifilament is further excellent.

0.05 to 3 μg / cm ² · 24 hr is preferable, and 0.07 to 2 μg / cm ² · 24 hr is more preferable, and the controlled release amount of the core-sheath complex type multifilament pyrethroid compound is preferably 0.1 to 1. More preferably, 5 μg / cm ² · 24 hr.
When the 24-hour sustained release amount of the core-sheath complex type multifilament pyrethroid compound is 0.05 μg / cm ² · 24 hr or more, the insect-repellent performance of the core-sheath complex type multifilament tends to be further excellent and the repellent rate of pests increases. There is.
When the 24-hour sustained release amount of the pyrethroid compound of the core-sheath complex type multifilament is 3 μg / cm ² · 24 h or less, the durability of the insect-repellent performance of the core-sheath complex type multifilament is further excellent.

70% or more is preferable, as for the repellent rate of the pest after a 250-hour weathering test, 75% or more is more preferable, and 80% or more is more preferable.
When the repellent rate of pests after weathering for 250 hours is 70% or more, satisfactory insect repellent performance is observed even when used outdoors for about a year, and the weather resistance of the repellent performance of the core-sheath composite type multifilament is It is further excellent.
When the repellent rate of pests after the 250-hour weathering test is 75% or more, the insect-repellent performance of the core-sheath composite multifilament tends to be sufficiently recognized even after long-term use.
When the repellent rate of pests after the 250-hour weathering test is 80% or more, the durability and immediate effect of the insect-repellent performance of the core-sheath composite multifilament are further excellent.

0.1 to 4.0 μg / cm ² is preferable, 0.2 to 3.5 μg / cm ² is more preferable, and the surface amount of the core-sheath complex type multifilament pyrethroid compound after the weathering test for 250 hours is preferably 0. 3 to 3.0 μg / cm ² is more preferable.
If the surface amount of the core-sheath composite multifilament pyrethroid compound after the weathering test for 250 hours is 0.1 μg / cm ² or more, excellent insect-repellent performance tends to be exhibited even after long-term use .
The upper limit of the surface amount of the core-sheath composite multifilamentary pyrethroid compound after the 250-hour weathering test is not particularly limited. When the upper limit value of the surface amount after the 250-hour weathering test is mentioned, the stickiness of the material can be reduced if it is 4.0 μg / cm ² or less. Moreover, the sustainability of the insect repellent performance is further excellent while maintaining the repellent performance.

0.05 to 3 μg / cm ² · 24 hr is preferable, and 0.1 to 2.5 μg / cm ² · 24 hr is more preferable for the 24-hour sustained release amount of the core-sheath complex type multifilament pyrethroid compound after the weathering test for 250 hours 0.2 to 2.0 μg / cm ² · 24 hr is more preferable.
When the 24 hour sustained release amount of the core-sheath complex type multifilament pyrethroid compound after the weathering test for 250 hours is 0.05 μg / cm ² · 24 hr or more, the insect-repellent performance of the core-sheath complex type multifilament is further excellent and the long-term There is a tendency for excellent insect repellent performance to be exhibited even after use.
Although the upper limit value of the 24-hour sustained release amount of the pyrethroid compound of the core-sheath complex type multifilament after the 250 hour weathering test is not particularly limited, the insecticidal performance of the core-sheath complex type multifilament when it is 3 μg / cm ² · 24 h or less The sustainability of the

The total fineness of the core-sheath composite multifilament is not particularly limited. The total fineness of the core-sheath composite multifilament may be, for example, 40 to 200 dtex, or 50 to 150 dtex. The total fineness of the core-in-sheath composite multifilament can be appropriately set according to the application. When the total fineness of the core-in-sheath complex type multifilament is constant, the surface area of the core-in-sheath complex type multifilament is larger as the single fibers constituting the multifilament are relatively fine. Therefore, the insect-repellent performance of the core-sheath composite multifilament is further enhanced.

The core-sheath composite multifilament can be produced, for example, by melt spinning. For example, a predetermined amount of pyrethroid-based compound can be contained in the core by melt-kneading the resin serving as the raw material of the core of the single fiber and the pyrethroid-based compound in the spinning stage. At the time of melt-kneading, the pyrethroid-based compound may be kneaded into the resin as the raw material of the core portion of the single fiber. By kneading the pyrethroid-based compound into the resin, the reduction amount of the pyrethroid-based compound due to washing, use outdoors, and the like is suppressed. As a result, the core-sheath composite multifilament can be provided with durability and durability with excellent insect-repellent performance, as compared with the method of attaching the pyrethroid compound to the surface of the fiber after the production of the fiber.

When a high molecular weight hindered amine stabilizer is contained in the multifilament, the high molecular weight hindered amine stabilizer may be added to the polyolefin resin constituting the multifilament. By containing the high molecular weight type hindered amine stabilizer in the multifilament, it is possible to prevent the reduction of the surface amount of the pyrethroid compound after the 250 hour weathering test and the sustained release amount for 24 hours. As a result, excellent insect repellent performance with a pest repellent rate of 80% or more is maintained for a long period of time, and weatherability and durability are further improved.

(Action effect)
In the core-sheath composite multifilament described above, since the pyrethroid compound is contained in the core portion of the single fiber constituting the multifilament, the elution amount of the pyrethroid compound can be suppressed to a relatively small amount. Better weatherability and durability of performance.
In the core-sheath composite multifilament, when the content of the pyrethroid compound is 0.1% by mass or more and the single fiber fineness is 7 dtex or less, the single fiber is relatively thin as compared with the conventional product, The pyrethroid compound easily moves from the core of the single fiber to the surface of the sheath. As a result, the insecticidal performance of the multifilament is further improved.
In the core-sheath composite multifilament, when the single fiber fineness is 7 dtex or less, the single fiber becomes relatively thinner than the conventional product, and the content of the pyrethroid compound relatively less than the conventional product is efficiently excellent. Insect repellent performance is obtained.

(Use)
The multifilament of the present invention can be used as a material of fiber products. The multifilament of the present invention can be made into various forms of insect repellent fiber products by various processing methods. The insect repellent fiber product may be for materials or clothing.
The multifilaments of the present invention can be applied to applications where persistence or durability of insect repellent performance is required. The multifilament of the present invention can be applied to textile products such as, for example, tents, insect nets, agricultural nets, pet wear, work clothes, hats, outdoor wear and the like.

Insect Repellent Weaving
The insect-repellent woven or knitted fabric of the present invention comprises the multifilament of the present invention described above. The insect-repellent woven or knitted fabric of the present invention may include the core-sheath composite multifilament described above.
The insect-repellent woven or knitted fabric of the present invention may further include a fusible yarn in addition to the multifilament and core-sheath composite multifilament of the present invention.

10 mass% or more is preferable, as for the content rate of the multifilament in a insect-repellent woven fabric, 20 mass% or more is more preferable, and 30 mass% or more is further more preferable.
When the content of the multifilament in the insect-repellent woven or knitted fabric is 10% by mass or more, the weatherability, durability and insect repellent rate of the insect-repellent woven or knitted fabric are further excellent.
The upper limit of the content of multifilaments in the insect-proof woven fabric is not particularly limited.

When the insect-repellent woven or knitted fabric of the present invention further comprises a fusible yarn, it is preferable that the crossing points of the multifilament and the fusible yarn be thermally adhered by the fusible yarn. When the crossing points are heat-bonded by the fusion yarn, the crossing points are fixed, and it is easy to physically prevent the insects from entering the gaps between the fibers in the insect-repellent woven fabric.

The insect-repellent woven fabric of the present invention can be produced, for example, by weaving or knitting multifilaments. In the production of insect-repellent woven or knitted fabric, multifilaments may be twisted or dyed.

(Action effect)
Since the insect repellent woven fabric of the present invention contains the above-described multifilament of the present invention, the weather resistance and durability of the insect repellent performance of the insect repellent woven fabric can be improved.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following description.
The measuring method for the multifilament is shown below.

<Measurement method>
(Single fiber fineness)
The total fineness of the multifilaments was measured and divided by the number of filaments to calculate.

(Content of pyrethroid compound)
Using a 20-gauge tubular knitting machine, a tubular knit fabric of Tengu tissue, which was knitted with multiple filaments, was used as an evaluation sample. 50 mg of the evaluation sample was immersed in 50 mL of 99.7% methanol, allowed to penetrate the fiber for 48 hours at 45 ° C., and the pyrethroid compound in the fiber was extracted into 99.7% methanol. Thereafter, analysis was performed by high performance liquid chromatography to measure the mass A of the pyrethroid compound contained in 99.7% of methanol, and the content of the pyrethroid compound was measured by the following formula (2).
Content of pyrethroid compound in fiber (% by mass) = (A / mass of evaluation sample) × 100 (2)

(Surface amount of pyrethroid compound)
Using a 20-gauge tubular knitting machine, a multi-filament knitted fabric with a base weight of 70 g / m ² was prepared, and a square evaluation sample with a side length of 50 mm was prepared from the knitted fabric. . This evaluation sample was immersed in 50 mL of 99.7% methanol under a 25 ° C. environment for 10 minutes, and the amount of pyrethroid compound contained in 99.7% methanol was measured using high performance liquid chromatography. The measured value was divided by the area of the tubular knitted fabric to calculate the content of the pyrethroid-based compound per unit area of the sample, and the surface amount (μg / cm ² ) of the pyrethroid-based compound was calculated.

(24 hour sustained release of pyrethroid compounds)
Using a 20-gauge tubular knitting machine, a multi-filament knitted fabric with a base weight of 70 g / m ² was prepared, and a square evaluation sample with a side length of 50 mm was prepared from the knitted fabric. . This evaluation sample was immersed and washed in 50 mL of 99.7% methanol. The washed sample is left to stand in a 20 ° C. environment for 24 hours, and then immersed in 50 mL of 99.7% methanol for 10 minutes at 25 ° C. environment, and using high performance liquid chromatography in 99.7% methanol The amount of pyrethroid compound contained was measured. The measured value was divided by the area of the tubular knitted fabric, the content of the pyrethroid compound per unit area of the sample was calculated, and it was defined as the sustained release amount (μg / cm ² · 24 hr) of the pyrethroid compound for 24 hours.

(Pest repellent rate)
Using a 20-gauge tubular knitting machine, a tubular knit fabric of Tengumu, which has a basis weight of 70 g / m ² knitted with multifilaments, was prepared and used as an evaluation sample. Next, two shelters were placed in the test container, and one evaluation sample was placed in one of the shelters. Thus, the place where the shelter in which the evaluation sample was placed was set as the treated area, and the place where the shelter in which the evaluation sample was not placed was set as the untreated area.
Next, the same amount of food and water were placed in each of the two shelters, and 10 German cockroaches (pest) were placed in the test container. Next, after illuminating the light from above the test container for 10 hours, the two shelters were simultaneously removed from each test container, and the numbers of pests in the treated area and the untreated area were respectively measured. Based on the number of pests measured, the repellent rate of pests was calculated by the following equation (3).
Repellency rate of pests (%) = [(number of pests in untreated area)-(number of pests in treated area) / (number of pests in untreated area) x 100 (3)

(KT50 value)
Using a 20-gauge tubular knitting machine, a tubular knit fabric of Tengumu, which has a basis weight of 70 g / m ² knitted with multifilaments, was prepared and used as an evaluation sample. Next, an evaluation sample was placed on the entire surface of the bottom of the test container, and 10 German cockroaches were placed on the evaluation sample. Record the time when the German cockroach turned over one by one, plot the obtained data to create a first-order approximation line, and the time (minutes) when five animals, 50% of the inserted German cockroach, turn over, KT50 It is a value.
The smaller the KT50 value, the higher the immediate effect, and therefore it can be used to evaluate the insecticidal performance.

(250 hours weathering test)
The carbon arc weathering test was conducted under the conditions of a temperature of 63 ° C. and a test time of 250 hours.

(Rinse test)
First, the multifilament was rinsed once under the conditions of a water temperature of about 20 ° C. and a rinse time of 15 minutes.
Next, the elution amount of the pyrethroid compound in water after one rinse was measured. Thereafter, after setting a time interval of 24 hours, the operation of further rinsing the multifilament under the same conditions as the first rinse was repeated four times for a total of five rinses. The concentration of etofenprox eluted in water after the first rinse was taken as the elution volume in the rinse test (1 time), and the concentration of etofenprox eluted in water after the fifth rinse was tested in the rinse (5 times) The elution amount of. The detection limit of the concentration of eluted etofenprox is 0.2 ppm. When the elution amount was less than the detection limit value, the result was described as “ND” in the table.

Example 1A
Masterbatch of etofenprox as pyrethroid-based compound as an insect repellent (manufactured by KNIX, melting point 105 ° C.), polypropylene resin as a polyolefin-based resin (manufactured by Japan Polypropylene Corp., Novatec PPSA 03, high molecular weight hindered amine stabilizer 0.1) The mass%, MFR: 30 g / 10 min (230 ° C.), melting point 155 to 165 ° C., density 0.89 to 0.91 g / cm ³ ) were prepared. Ethofenprox and a polypropylene resin were melt-kneaded at a blending amount of 0.5% by mass of etofenprox.
The melt-kneaded ETO obtained under the conditions of a spinning temperature of 215 ° C. and a discharge amount of 17.9 g / min using a spinneret in which the shape of the nozzle hole is round (diameter 0.8 mm) and the number of holes is 30. The fenprox blended polypropylene resin was spun and wound up at a spinning speed of 550 m / min.
Subsequently, drawing is performed under the conditions of a drawing ratio of 2.98 times, a heat setting temperature of 100 ° C., and a winding speed of 400 m / min to obtain a polypropylene multifilament having a total fineness of 110 dtex and a filament count of 30. The Hereinafter, the configuration of the multifilament will be described using the total fineness (dtex) and the number of filaments (f). For example, the polypropylene multifilament of Example 1A is described as a 110 dtex / 30f multifilament.
The polypropylene multifilament of Example 1A had a single fiber fineness of 3.5 dtex, a tensile strength of 3.53 cN / dtex, and a tensile elongation of 80.3%.

Example 2A
Example 1A is carried out in the same manner as Example 1A, except that the blend ratio of etofenprox is 1.0% by mass and melt blending of etofenprox and polypropylene resin is carried out and the draw ratio is changed to 3.09 times. The melt-kneaded ethofenprox-blended polypropylene resin was spun and drawn to obtain 110 dtex / 30f polypropylene multifilament of Example 2A.
The polypropylene multifilament of Example 2A had a single fiber fineness of 3.5 dtex, a tensile strength of 3.53 cN / dtex, and a tensile elongation of 74.4%.

Example 3A
The ethofenprox and the polypropylene resin were melt-kneaded using the etofenprox and the polypropylene resin used in Example 1A, with the blending amount of the ethofenprox being 1.0% by mass.
Melt-kneaded etofen at a spinning temperature of 200 ° C. and a discharge rate of 40.6 g / min using a spinneret in which the shape of the nozzle hole is round (diameter 0.8 mm) and the number of holes is 30. Prox blended polypropylene resin is spun, stretched at a draw ratio of 2.33 times, heat setting temperature: 138 ° C, winding speed: 2700 m / min to obtain polypropylene multifilament of Example 3A of 135 dtex / 30 f. The
The polypropylene multifilament of Example 3A had a single fiber fineness of 4.5 dtex, a tensile strength of 3.6 cN / dtex, and a tensile elongation of 40%.

Example 4A
The ethofenprox and the polypropylene resin were melt-kneaded using the etofenprox and the polypropylene resin used in Example 1A, with the blending amount of the ethofenprox being 1.0% by mass.
Conducted using spinneret with round nozzle shape (diameter 0.8 mm) and 48 holes, and changing the discharge amount to 13.9 g / min and the draw ratio to 2.51 The melt-kneaded etofenprox-containing polypropylene resin was spun and drawn in the same manner as in Example 1A to obtain the polypropylene multifilament of Example 4A of 96 dtex / 48f.
The polypropylene multifilament of Example 4A had a single fiber fineness of 2 dtex, a tensile strength of 2.72 cN / dtex, and a tensile elongation of 51.9%.

Example 5A
The ethofenprox and the polypropylene resin were melt-kneaded using the etofenprox and the polypropylene resin used in Example 1A, with the blending amount of the ethofenprox being 1.0% by mass.
Conducted using spinneret with round nozzle shape (diameter 0.8 mm) and 32 holes, and changed the discharge amount to 15.1 g / min and the draw ratio to 2.93 times In the same manner as in Example 1A, the melt-kneaded etofenprox blended polypropylene resin was spun and drawn to obtain a polypropylene multifilament of Example 5A of 96 dtex / 32f.
The polypropylene multifilament of Example 5A had a single fiber fineness of 3 dtex, a tensile strength of 2.87 cN / dtex, and a tensile elongation of 48%.

Example 6A
In Example 6A, polyethylene resin (HE 490, MFR = 22.2 g / 10 min (190 ° C.), melting point 125-140 ° C., density 0.94 g / cm ³ ) was used as the polyolefin resin.
Using the ethofenprox used in Example 1A, the blended amount of ethofenprox was 1.0% by mass, and the ethofenprox and the polyethylene resin were melt-kneaded.
The melt-kneaded ETO obtained by using a spinneret having a round nozzle shape (diameter 0.8 mm) and a number of holes of 30 and a spinning temperature of 205 ° C. and a discharge amount of 6.8 g / min. The fenprox blended polyethylene resin was spun and taken up at a spinning speed of 600 m / min.
Subsequently, drawing was performed under the conditions of a drawing ratio of 3.85 times, a heat setting temperature of 80 ° C., and a winding speed of 380 m / min to obtain a polyethylene multifilament of Example 6A of 56 dtex / 30 f.
The polyethylene multifilament of Example 6A had a single fiber fineness of 1.9 dtex, a tensile strength of 1.98 cN / dtex, and a tensile elongation of 75.0%.

Example 7A
The ethofenprox and the polypropylene resin were melt-kneaded using the etofenprox and the polypropylene resin used in Example 1A, with the blending amount of the ethofenprox being 1.0% by mass.
It is carried out except that the discharge amount is changed to 29.2 g / min and the draw ratio is changed to 5.53 times using a spinneret in which the shape of the nozzle hole is round (diameter 1.0 mm) and the number of holes is 10. The melt-kneaded etofenprox blended polypropylene resin was spun and drawn in the same manner as in Example 1A to obtain a polypropylene multifilament of Example 7A at 100 dtex / 10 f.
The polypropylene multifilament of Example 7A had a single fiber fineness of 10 dtex, a tensile strength of 4.55 cN / dtex, and a tensile elongation of 28.8%.

Regarding the multifilaments of Example 1A to Example 7A, the content of etofenprox, the surface amount of etofenprox, the 24-hour sustained release amount of etofenprox, the repellent rate of pests, the KT50 value to the description of the above-mentioned measuring method Therefore, it measured. The results are shown in Tables 1 and 2. In Tables 1 and 2, "PP" is a polypropylene resin, and "PE" is a polyethylene resin.

Example 8A
The 110 dtex / 30 f polypropylene multifilament obtained in Example 2A was weathered for 250 hours.
The multifilament after the 250-hour weathering test had a tensile strength of 2.9 cN / dtex and a tensile elongation of 26.1%.
The polypropylene multifilament after weathering for 250 hours has an etofenprox content of 0.31% by mass, the surface amount of etofenprox in the fiber is 3.1 μg / cm ² , and the etofenprox from the fiber is The controlled release amount for 24 hours was 0.39 μg / cm ² · 24 hr, the repellent rate of pests was 100%, and the KT 50 value was 30 minutes or more.
From the results of Example 8A, it can be confirmed that the 110 dtex / 30f polypropylene multifilament obtained in Example 2A is excellent in weather resistance and durability of insecticidal performance.

Example 1B
A masterbatch resin X (manufactured by Knicks, main component: polyethylene resin) containing etofenprox, which is a pyrethroid compound, as an insect repellent, and a polypropylene resin (Novatec PPSA03, manufactured by Japan Polypropylene Corp.) were prepared.
The masterbatch resin X and the polypropylene resin were blended so that the content of etofenprox as the resin B of the core portion was 1.0% by mass, and the mixture was melt-kneaded. As resin C of a sheath part, it melt-kneaded using 100 mass% of the same polypropylene resin as what was used for the core part.
Next, using a spinneret in which the shape of the nozzle hole is round and the number of holes is 30, the core portion and the resin composed of the resin B at a spinning temperature of 200 ° C. and a spinning speed of 800 m / min. An undrawn yarn of a core-sheath structure having a sheath composed of C was obtained. At this time, the ratio (V1 / V2) of the volume V1 of the core to the volume V2 of the sheath is 1/1.
Next, drawing was performed under the conditions of a drawing ratio of 2.96 times, a drawing speed of 400 m / min, and a heat setting temperature of 100 ° C., to obtain a core-sheath composite multifilament of 135 dtex / 30f of Example 1B.

Example 2B
In Example 1B, melt-kneaded etofenprox was prepared in the same manner as in Example 1B, except that a master batch resin of black pigment (6030, manufactured by Nippon Pigment Co., Ltd.) was prepared and the draw ratio was changed to 3.34. The blended polypropylene resin was spun and stretched to obtain a core-sheath composite multifilament of 135 dtex / 30 f of Example 2B.
In the core-sheath composite multifilament of Example 2B, the content of the black pigment was 1.08% by mass.

Example 3B
In Example 2B, a high molecular weight type hindered amine stabilizer-containing masterbatch resin (manufactured by Nippon Pigment Co., Ltd., MF05) is prepared, and spinning is performed in which the shape of the nozzle hole is round (diameter 0.8 mm) and the number of holes is 60. Melt-kneaded etofen in the same manner as in Example 2B, except that drawing was performed at a spinning speed of 1140 m / min using a die, followed by drawing at a draw ratio of 2.58 and a drawing speed of 2818 m / min. Prox blended polypropylene resin was spun and drawn to obtain a core-sheath composite multifilament of 135 dtex / 30 f of Example 3B.
In the core-sheath composite multifilament of Example 3B, the content of the black pigment was 1.08% by mass.

Example 4B
In Example 1B, an etofenprox blended polypropylene resin melt-kneaded in the same manner as in Example 1B except that a white pigment (manufactured by Nippon Pigment Co., Ltd., 98S3) was prepared and the draw ratio was changed to 3.32 times. The resultant was drawn and stretched to obtain a core-sheath composite multifilament of Example 4B of 135 dtex / 30 f.
In the core-sheath composite multifilament of Example 4B, the content of the white pigment was 0.72% by mass.

Example 5B
In Example 2B, the ratio (V1 / V2) is set to 1 / 1.7, and a masterbatch resin is blended in the core portion so that the etofenprox content is 1.35% by mass, and the stretching ratio is 3.3. The melt-kneaded etofenprox-blended polypropylene resin melt-kneaded in the same manner as in Example 2B except that the ratio was changed to 62 times, and stretched to obtain a core-sheath composite multifilament of Example 5B of 135 dtex / 30f.
The core-sheath composite multifilament of Example 5B had a black pigment content of 1.08% by mass.

Example 6B
In Example 5B, the ratio (V1 / V2) is set to 2/1, and the master batch resin is blended in the core portion so that the etofenprox content is 0.75% by mass, and the draw ratio is 3.55 times The melt-kneaded etofenprox-blended polypropylene resin melt-kneaded in the same manner as in Example 5B except that it was changed to, and stretched to obtain a core-sheath composite multifilament of Example 6B of 135 dtex / 30 f.
The core-sheath composite multifilament of Example 6B had a black pigment content of 1.08% by mass.

Example 7B
In Example 2B, the masterbatch resin is compounded in the core portion so that the etofenprox content is 0.4% by mass, and the drawing ratio is changed to 3.64 times in the same manner as in Example 2B. The melt-kneaded ethofenprox-blended polypropylene resin was spun and drawn to obtain a core-sheath composite multifilament of Example 7B of 135 dtex / 30 f.
The core-sheath composite multifilament of Example 7B had a black pigment content of 1.08% by mass.

Example 8B
In Example 2B, as a solid yarn which does not form a core-sheath structure and does not have a core portion and a sheath portion, the blending amount of etofenprox in the entire yarn is 0.5% by mass, and the draw ratio is 3.%. The melt-kneaded etofenprox-blended polypropylene resin melt-kneaded in the same manner as in Example 2B, except that it was changed to 35 times, and stretched to obtain the multifilament of Example 8B of 135 dtex / 30f.
In the multifilament of Example 8B, the content of the black pigment was 1.08% by mass.

Example 9B
Example 3B The core-sheath complex type multifilament of the example 3B and the polypropylene multifilament not containing the pyrethroid compound were combined at 1: 3 to prepare a tubular knit fabric of the example 9B.
As a result of evaluating the insect repellent performance of the tubular knitted fabric of Example 9B, the repellent rate of pests was 100%.

Example 10B
The core-sheath composite type multifilament of Example 3B and the polypropylene multifilament containing no pyrethroid compound were subjected to a single-twisting process at 1: 1 to produce a tubular knit of Example 10B. As a result of evaluating the insect repellent performance of the tubular knitted fabric of Example 10B, the repellent rate of pests was 100%.

The core-sheath composite multifilament of Example 1B to Example 7B, the multifilament of Example 8B, single fiber fineness, tensile strength, content of etofenprox, content of high molecular weight type hindered amine stabilizer, etofen The surface amount of Prox, the 24-hour sustained release amount of etofenprox, the repellent rate of pests, and the KT 50 value were measured.
Next, a 250 hour weathering test was conducted on the core-sheath composite multifilaments of Examples 1B to 7B. With respect to the core-in-sheath composite multifilaments of each example after the 250-hour weathering test, the surface amount of ethofenprox, the 24-hour sustained release amount of etofenprox, and the repellent rate of pests were measured.
Tables 3 and 4 show the results of rinsing tests of the core-sheath composite multifilament of Example 1B and Example 2B and the multifilament of Example 8B in combination with the above measurement results.

The core-in-sheath composite multifilaments of Examples 1B to 7B and the multifilament of Example 8B exhibited excellent KT 50 values, and were expected to exhibit excellent persistence of insect-repellent performance.
Furthermore, it was confirmed that the core-sheath composite multifilaments of Examples 1B to 7B had a repellent rate of 80% or more after 250 hours of weathering test, and had sufficient durability.
In the core-sheath composite multifilaments of Examples 1B and 2B, the elution amount in the rinse test (one time) was less than the detection limit value. On the other hand, in the multifilament of Example 8B, the elution amount in the rinse test (one time) was 0.5 ppm. Thus, since the core-sheath composite type multifilament of Examples 1B and 2B can suppress the elution amount of the pyrethroid compound to a small amount as compared with the multifilament of Example 8B, the weather resistance and durability of the insect repellent performance are maintained. It was considered to be even better for sex. Thus, it has been confirmed that the weatherability and durability of the insect-repellent performance are further improved in the core-sheath composite multifilament having the core portion and the sheath portion.

The multifilament of the present invention is excellent in weather resistance and durability of insect-repellent performance.
The multifilament of the present invention is useful as a material for insect repellent fiber products. ADVANTAGE OF THE INVENTION According to the multifilament of this invention, the fiber product which is excellent in the sustainability of insect-repellent performance can be provided.

Claims (17)

1. A multifilament comprising a pyrethroid-based compound, wherein a surface amount of the pyrethroid-based compound is 0.1 to 15 μg / cm ² .
2. The multifilament according to claim 1, wherein a single fiber fineness of single fibers constituting the multifilament is 1 to 15 dtex.
3. The multifilament according to claim 1 or 2, wherein the content of the pyrethroid compound is 0.1 to 3% by mass with respect to 100% by mass of the multifilament.
4. The multifilament according to any one of claims 1 to 3, further comprising a high molecular weight hindered amine stabilizer, wherein the content of the high molecular weight hindered amine stabilizer is 0.05 to 1% by mass.
5. The multifilament according to any one of claims 1 to 4, wherein the 24-hour sustained release amount of the pyrethroid compound is 0.05 to 3 μg / cm ² · 24 hr.
6. The multifilament according to any one of claims 1 to 5, wherein a surface amount of the pyrethroid based compound after a weathering test for 250 hours is 0.1 to 15 μg / cm ² .
7. The multifilament according to any one of claims 1 to 6, wherein the 24-hour sustained release amount of the pyrethroid compound after the 250-hour weathering test is 0.05 to 3 μg / cm ² · 24 hr.
8. The single fiber has a core and a sheath formed on the outside of the core,
   The core portion contains the pyrethroid compound, and the content of the pyrethroid compound is 0.1 to 3% by mass with respect to 100% by mass of the multifilament,
   The multifilament according to any one of claims 1 to 7, wherein the single fiber fineness of the single fiber is 1 to 7 dtex.
9. The multifilament according to claim 8, wherein the thickness of the sheath portion is 4 μm or less.
10. The multifilament according to claim 8 or 9, wherein the ratio (V1 / V2) of the volume V1 of the core to the volume V2 of the sheath is 1/3 to 3/1.
11. The multifilament according to any one of claims 8 to 10, wherein the resin constituting the core portion is a polyolefin resin.
12. The mulch according to any one of claims 8 to 11, wherein the resin constituting the sheath portion is at least one selected from the group consisting of polypropylene resins, polyethylene resins, polyester resins, and polyamide resins. filament.
13. The multifilament according to any one of claims 1 to 12, wherein the reduction rate of the pyrethroid compound calculated by the following formula (1) is 70% or less.
    (Decrease rate of pyrethroid compound) = (W1-W2) / (W1) × 100 (1)
    In the formula (1), W1 is the content of the multifilament pyrethroid compound before the 250 hour weathering test, and W2 is the content of the multifilament pyrethroid compound after the 250 hour weathering test.
14. The multifilament according to any one of claims 1 to 13, wherein a repellent rate of pests after a 250 hour weathering test is 70% or more.
15. An insect repellent woven or knitted fabric comprising the multifilament according to any one of claims 1 to 14.
16. The insect-repellent woven or knitted fabric according to claim 15, wherein the multifilament content is 10% by mass or more.
17. The insect-repellent woven or knitted fabric according to claim 15 or 16, further comprising a fusion yarn, wherein an intersection of the multifilament and the fusion yarn is thermally bonded by the fusion yarn.