JPWO2018117128A1 - Insect-proof multifilament and knitted fabric - Google Patents

Abstract

An object of the present invention is to provide an insect repellent multifilament and a woven or knitted fabric that can exhibit the insect repellent to the maximum for a long period of time and further maintain a good quality by avoiding yarn breakage and the like. . According to the present invention, when the multifilament in which etofenprox is contained in a polybutylene terephthalate resin having a melting point of 150 to 190 ° C. is dyed, the etofenprox is added to 0.18 to 1. A multifilament characterized by containing 97% by mass and containing ethofenprox by 0.25 to 3.00% by mass when undyed is provided.

Description

  The present invention relates to an insect-proof multifilament and a woven / knitted fabric, and more particularly to an insect-proof multifilament containing etofenprox in a low-melting point polybutylene terephthalate resin and a woven / knitted fabric using the multifilament.

  In recent years, attempts have been made to impart insect repellent properties to insect repellent nets such as various fabric products and screen doors by using an insect repellent.

  For example, Patent Document 1 discloses an insect repellent net in which an insect repellent is contained in a multifilament yarn race. The insect net of Patent Document 1 is manufactured by impregnating a multifilament yarn lace with an aqueous liquid containing an insect repellent and an adhesive and then drying. The insect net of Patent Document 1 not only physically prevents insects from entering the room, but also exhibits a chemical insect repellent property by an insect repellent. Furthermore, since the insect repellent is fixed to the gaps of many filaments and the knots of the lace, the amount of the insect repellent is large and the insect repellent is difficult to fall off. However, even with the insect net of Patent Document 1, the insect repellent falls off when a strong stress such as friction is applied. Furthermore, even if the insect repellent can be held on the race surface for a long time without dropping off, the insect repellent gradually loses its effect over time. Thus, the insect net of Patent Document 1 still has room for improvement in terms of sustaining insect repellent properties.

  Patent Document 2 discloses an insect repellent monofilament comprising a resin composition containing 1 to 15 parts by weight of a pest repellent with respect to 100 parts by weight of a thermoplastic resin, and a fabric using such an insect repellent monofilament. Yes.

JP 2001-220970 A JP 2008-169141 A

  However, as a result of intensive studies by the inventor, even though etofenprox, which is an insect repellent, can be used without any problem as long as it is a monofilament that is a single thick thread as in Patent Document 2, a multi-layer composed of a plurality of thin filaments is used. It was found that when used as a filament, the insect repellent could not be fully exhibited. Alternatively, it is conceivable to use a large amount of etofenprox to provide sufficient insect repellent properties, but if the amount of etofenprox used is excessive, yarn breakage or yarn fluffing tends to occur, and spinning operability It was also found that was damaged.

  Accordingly, an object of the present invention is to provide an insect repellent multifilament capable of maximizing insect repellent over a long period of time and maintaining good quality by avoiding yarn breakage and the like, and a method for producing the same. It is to be.

  Another object of the present invention is to provide an insect-proof woven fabric or knitted fabric that can exhibit insect-proofing properties to the maximum and for a long time.

  According to the present invention, in the insecticidal dyeing multifilament in which etofenprox is contained in a polybutylene terephthalate resin having a melting point of 150 to 190 ° C. and dyed, the etofenprox is 0.18 to 1 Insect-proof dyeing multifilament characterized by containing .97% by mass, and an insect-proofing fabric or knitted fabric using the insect-proof dyeing multifilament are provided. In such an insect-proof fabric or knitted fabric, it is preferable that the fineness of the insect-proof dyeing multifilament is 30 to 2000 dtex and the number of single yarns is 10 to 300.

  Further, according to the present invention, in the polybutylene terephthalate resin having a melting point of 150 to 190 ° C., etofenprox is contained in an unstained insect-proof unstained multifilament, and the etofenprox is reduced to 0.00. An insect-proof undyed multifilament characterized by containing 25 to 3.00% by mass, and an insect-proof fabric or knitted fabric using the insect-proof undyed multi-filament are provided. In such an insect-proof fabric or knitted fabric, it is preferable that the fineness of the insect-proof undyed multifilament is 30 to 2000 dtex and the number of single yarns is 10 to 300.

  Furthermore, according to the present invention, a polybutylene terephthalate resin having a melting point of 150 to 190 ° C. is mixed with 0.4 to 5.0% by mass of etofenprox to obtain a mixture, and the mixture is obtained from the polybutylene terephthalate resin. And melt-kneading at a temperature of +10 to 30 ° C., spinning and dyeing the resulting melt-kneaded product to obtain an insecticidal dyeing multifilament containing 0.18 to 1.97% by mass of etofenprox This invention provides a method for producing an insect-repellent dyed multifilament.

  Furthermore, according to the present invention, a polybutylene terephthalate resin having a melting point of 150 to 190 ° C. is mixed with 0.4 to 5.0% by mass of etofenprox to obtain a mixture, and the mixture is converted into the polybutylene terephthalate. Melting and kneading at a temperature of the melting point of the resin +10 to 30 ° C., and spinning the obtained melt-kneaded product to obtain an insect-proof undyed multifilament containing 0.25 to 3.00% by mass of etofenprox A method for producing an insect-repellent undyed multifilament is provided.

  In the present specification, the insect-proof dyed multifilament and the insect-proof unstained multifilament are sometimes collectively referred to as insect-proof multifilament. Similarly, woven fabrics or knitted fabrics using insect-proof dyed multifilaments and woven fabrics or knitted fabrics using insect-proof undyed multifilaments may be collectively referred to as insect-proof woven or knitted fabrics. In addition, the woven fabric and the knitted fabric may be collectively referred to as a woven or knitted fabric.

  In the insect-proof multifilament and insect-proof woven or knitted fabric of the present invention, etofenprox is kneaded into the multifilament, and when insects such as mosquitoes touch the etofenprox on the surface of the multifilament, they hate it and leave. Insect protection is demonstrated by the principle. In the present invention, etofenprox gradually exudes from the inside of the multifilament over time, so that the insect repellent can be exhibited over a long period of time.

  A technique for kneading etofenprox into a filament has existed for a while (for example, Patent Document 2). However, this technique only relates to a monofilament and could not provide sufficient insecticidal properties to a multifilament. However, the present invention succeeds in making the used etofenprox exhibit maximum insect repellent properties in a multifilament. The reason is not clear, but the present inventor thinks as follows.

  That is, the insect repellent filament can be obtained by blending materials such as a matrix resin and an insect repellent, and heating the blend to a temperature higher than the melting point of the resin for melt spinning. When etofenprox is used as an insect repellent, etofenprox has a low melting point and tends to sublimate, so that when exposed to an excessively high temperature, it often volatilizes out of the filament.

  In particular, the present invention relates to a multifilament composed of a plurality of thin threads, not a monofilament that is a single thick thread. Multifilaments have a larger surface area than monofilaments and are therefore particularly prone to volatilization due to the excessively high temperatures described above.

  However, in the present invention, by using a polybutylene terephthalate resin (hereinafter sometimes abbreviated as PBT resin) having a low melting point (150 to 190 ° C.) as the matrix resin, the melting temperature during spinning is lowered, It effectively suppresses the evaporation of etofenprox. As a result, in the present invention, a sufficient amount of etofenprox can be present in the multifilament without using a large amount of etofenprox as a material. It is considered that the insect repellent can be exhibited to the maximum and for a long time.

  Furthermore, in this invention, volatilization of etofenprox in a dyeing | staining process is also suppressed by employ | adopting the above-mentioned low melting-point PBT resin as a matrix resin. In detail, for example, after processing a multifilament after spinning into a woven or knitted fabric, a dyeing bath in which a dye or the like is dissolved is heated to a predetermined temperature, and dyeing is performed by immersing the woven or knitted fabric in the dyeing bath for several hours. There is. So far, it has not been thought that a large amount of etofenprox is lost in the dyeing process, but the present inventors have found that the loss of etofenprox occurs more in the dyeing process than in the melt spinning process. . This is a surprising fact considering that the dyeing temperature is lower than the melting temperature at the time of spinning. The inventor presumes that in the dyeing process, the amount of loss increases as a result of the multifilament being heated for a long time. However, in the present invention, since the low melting point PBT resin is employed as the matrix resin as described above, the dyeing temperature can be suppressed, and even if the immersion time is long, etofenprox is hardly lost.

  Thus, in the present invention, by a very simple means of adopting a low melting point PBT resin as a matrix resin, it is possible to suppress the loss of etofenprox in the spinning process, which is essential for producing a multifilament, Even in the dyeing process where a large amount of etofenprox is lost, the amount of etofenprox can be maintained. Therefore, since it is not necessary to mix | blend excess etofenprox, it has succeeded in the implementation | achievement of the multifilament which exhibits high insect-proofing property, avoiding thread breakage etc. and maintaining favorable quality.

  Moreover, since the PBT resin has an excellent texture and is suitable for various uses, the present invention can be widely applied to living materials and industrial materials.

  The present invention relates to an insect-proof multifilament and an insect-proof woven or knitted fabric using the multi-filament.

<Insect repellent multifilament>
In the insect repellent multifilament of the present invention, etofenprox which is an insect repellent is kneaded into polybutylene terephthalate resin (PBT resin).

  The PBT resin is a polyester resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded, and may be polybutylene terephthalate (homopolymer), and may be a terephthalic acid unit and 1,4-butane. It may be a polybutylene terephthalate copolymer containing other copolymer components other than the diol unit, or may be a mixture of a homopolymer and the copolymer.

  Examples of dicarboxylic acids other than terephthalic acid that may be contained in the PBT resin include, for example, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl. -2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis (4,4'-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid; Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid; and adipic acid, sebacic acid, azelaic acid, dimer acid, etc. Aliphatic dicarboxylic acids; and the like.

  Examples of diols other than 1,4-butanediol that may be contained in the PBT resin include aliphatic or alicyclic diols having 2 to 20 carbon atoms, and bisphenol derivatives. Specifically, ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4′-dicyclohexylhydroxymethane, 4 4,4'-dicyclohexylhydroxypropane, ethylene oxide addition diol of bisphenol A, and the like.

  When the PBT resin is a copolymer, the copolymer contains one or more dicarboxylic acids other than terephthalic acid and / or one or more diols other than 1,4-butanediol as diol units. Yes.

  In the PBT resin, from the viewpoint of spinning operability, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably 50 mol% or more, more preferably 70 mol% or more. Similarly, the proportion of 1,4-butanediol in the diol unit is preferably 50 mol% or more, more preferably 70 mol% or more.

  In addition to the above bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and triol (for example, glycerin and trimethylolpropane) are introduced to introduce a branched structure, and fatty acids are used for molecular weight adjustment. A small amount of monofunctional compounds such as these can also be used.

  When the PBT resin is a copolymer, preferred copolymers include polyalkylene glycols, particularly polyester ether resins copolymerized with polytetramethylene glycol, dimer acid copolymerized polybutylene terephthalate resins, and isophthalic acid copolymerized polymers. Examples include butylene terephthalate resin. In addition, a copolymer means the thing whose copolymerization amount is 1 mol% or more and less than 50 mol% in a PBT resin all segment, Preferably it is 1 mol% or more and less than 30 mol%.

  The intrinsic viscosity (IV) of the PBT resin used in the present invention is preferably 0.6 to 1.0 dl / g. The intrinsic viscosity can be measured at 25 ° C. in a 1: 1 [mass ratio] mixed solvent of tetrachloroethane and phenol.

  The present invention has an important feature in that the melting point of the PBT resin is as low as 150 to 190 ° C., preferably 160 to 180 ° C. If the melting point is too high, the melting temperature in the spinning process and the dyeing temperature in the dyeing process must be increased, and a lot of etofenprox will be volatilized in these processes. When the melting point is too low, heat resistance and the like are insufficient. The melting point can be confirmed, for example, by differential scanning calorimetry. In order to obtain a PBT resin having such a melting point, a known means may be adopted as necessary. For example, an appropriate kind and an appropriate amount of a copolymer component may be blended to adjust the melting point.

Etofenprox is represented by the following chemical formula, the chemical name is 2- (4-ethoxyphenyl) -2-methylpropyl = 3-phenoxybenzyl = ether, and exhibits insect repellent by the same mechanism of action as pyrethroid. However, it has the advantages of low toxicity to warm-blooded animals, weak irritation to skin and mucous membranes, and low fish toxicity.

  In the insect-proof multifilament of the present invention, when not dyed, ethofenprox is contained in an amount of 0.25 to 3.00% by mass, preferably 0.28 to 2.75% by mass. include. That is, in the present invention, since the low melting point PBT resin is used as the matrix resin, the heating temperature at the time of spinning can be lowered. Therefore, it effectively suppresses the evaporation of etofenprox during spinning, is susceptible to temperature, and contains a sufficient amount of etofenprox even though it is a multifilament that requires delicate spinning conditions. And exhibits good insect repellent properties. If the content ratio of etofenprox exceeds the above numerical range, the spinning operability, stretching operability, and weaving / knitting processability may be impaired. Further, the texture may be impaired.

  The insect-repellent dyed multifilament obtained by dyeing the above-mentioned insect-repellent unstained multifilament contains 0.18 to 1.97% by mass of etofenprox, and preferably 0.24 to 1.97. Mass% is included. By using the low-melting point PBT resin as the matrix resin, not only the heating temperature at the time of spinning described above, but also when dyeing, the dyeing temperature can be lowered. The filament contains a sufficient amount of etofenprox even after dyeing.

  In addition, when the multifilament has not been dyed, it means that the multifilament has not been dyed. As long as the multifilament has not been dyed, it includes a multifilament that is originally deposited with a pigment such as an inorganic pigment or an organic pigment. On the other hand, when the multifilament is dyed, it includes those dyed after processing into woven and knitted fabrics, and those dyed before processing, and also dyes multifilaments deposited with pigments. Also included.

  In the present invention, a known insect repellent may be used in combination with etofenprox as long as the effect is not impaired. Examples of known insect repellents other than etofenprox include pyrethroid insecticides such as pyrethrin, cinerine, jasmolin, allethrin, resmethrin, and fenvalerate; cyclic diene insect repellents such as toxaphene and benzoepin; And phosphorus insect repellents; carbamate insect repellents such as carbaryl, mesomil and promecarb;

The multifilament of the present invention may further contain a known additive. Known additives include, for example, sustained release aids such as benzenesulfonic acid amide; dissimilar thermoplastic resins used as dispersion aid resins, affinity resins (eg, ethylene-ethyl acrylate); weathering agents; Flame retardants; antioxidants; inorganic pigments such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, silicon carbide, barium sulfate, and carbon black; organic pigments such as phthalocyanine metal-based and cobalt blue; metal stearates; ethylene bis Stearylamide; calcium metasilicate; hydrous magnesium silicate; aminosilane; melamine cyanurate; ionomers; sequestering agent; clathrate compound; Epoxy compound; Oxazoline compound; Clay, Talc Kaolin, particles such as inorganic particles or crosslinked polymer particles such as zirconium acid; antioxidants; ion exchanger; and the like.
An embodiment in which a pigment such as an inorganic pigment or an organic pigment is used as an additive and the dyeing step is omitted is preferable in that a multifilament exhibiting a desired color can be obtained while suppressing the volatilization of etofenprox. .

  The fineness of the multifilament of the present invention may be appropriately determined according to the use, but generally 30 to 2000 dtex is preferable, and 30 to 300 dtex is more preferable. If the multifilament is too thin, thread breakage or single thread breakage (yarn fluff) may occur easily. If the multifilament is too thick, desired quality (flexibility, texture) may not be obtained.

  The number of single filaments of the multifilament of the present invention may be appropriately determined according to the use, but from the viewpoint of ease of spinning and cost, 10 to 300 are preferable, 10 to 50 are more preferable, and 12 to 36 are preferable. Particularly preferred.

  The multifilament of the present invention can be produced by a known method. For example, a desired material is prepared, and the material is melt-kneaded at a temperature as low as possible by a conventional melt spinning apparatus, preferably at a melting point of PBT resin as a matrix resin +10 to 30 ° C.

  Each material may be mixed directly, or may be mixed after making it into a masterbatch if necessary. A known thermoplastic resin may be used for the master batch.

  The PBT resin is used for spinning, and it is necessary to dry the material after mixing and before melting to remove moisture. Drying conditions are preferably 80 to 130 ° C. and 3 to 5 hours.

  What is necessary is just to determine the compounding quantity of a material suitably so that each component quantity in the multifilament finally obtained may become in the above-mentioned numerical range. For example, it is preferable to use a low melting point PBT resin which is a matrix resin in an amount of 90.0% by mass or more, preferably 95.0 to 99.6% by mass with respect to the entire material. Moreover, it is preferable to use 0.4-5.0 mass% of etofenprox (pure part) with respect to the whole material, it is more preferable to use 0.5-3.5 mass%, It is particularly preferable to use ~ 3.0% by mass.

  Next, the melt-kneaded product is extruded. When extruding, it is important to shorten the residence time to avoid excessive heat history. Although depending on the scale of the apparatus and the like, the residence time is usually preferably 2 to 10 minutes, and particularly preferably 4 to 8 minutes. If the residence time is too short, melt and kneading may be insufficient, resulting in yarn, and yarn breakage may occur easily. If the residence time is too long, it causes an increase in the amount of etofenprox volatilized during spinning, which is not preferable. Moreover, there is a possibility that inconveniences such as a decrease in viscosity, yellowing, and insufficient strength elongation may occur.

  Next, the extruded melt-kneaded material is discharged from the die, and air is blown to solidify by cooling. Thereby, an undrawn yarn is obtained.

  Next, the obtained undrawn yarn is drawn. The stretching temperature is preferably 30 to 70 ° C. The draw ratio is preferably 3.0 to 5.5 times.

  Next, if necessary, the multifilament before being used for weaving or knitting may be dyed. That is, usually, dyeing is often performed after weaving or knitting, but depending on the application or the like, it may be performed before weaving or the like. Dyeing is performed, for example, by preparing a dyeing bath in which a known dye and an auxiliary agent are dissolved, adjusting the temperature to 80 to 120 ° C., and immersing the undyed multifilament in the bath like the woven or knitted fabric described later.

  The multifilament of the present invention thus obtained contains a sufficient amount of etofenprox not only before dyeing but also after dyeing, and exhibits excellent insecticidal properties. In addition, etofenprox is not applied to the surface, but is kneaded inside the multifilament and oozes out on the multifilament surface little by little, so that the insect repellent is maintained over a long period of time. . Moreover, the present invention is a multifilament composed of a plurality of thin threads. Multifilaments are generally more susceptible to yarn breakage and yarn fluff than monofilaments. In particular, when a foreign substance such as etofenprox is kneaded into the resin, the problems of spinning operability such as yarn breakage and yarn fluff are very remarkable. However, in the present invention, by using a low melting point PBT, avoiding the use of a large amount of etofenprox, and preferably by finely adjusting the spinning conditions, the occurrence of yarn breakage and yarn fluff can be effectively suppressed. Yes.

The insect-proof multifilament of the present invention may be used as it is in the state of a long fiber, but may be cut into an appropriate length and used in the state of a short fiber.
As a case where it is used in the state of short fibers, it can be considered that it is used for, for example, a woven fabric, a knitted fabric, a nonwoven fabric, and various auxiliary materials. In use, short fibers may be twisted and used as a spun yarn.
Examples of the use as long fibers include use as yarns and use in woven or knitted fabrics.
From the viewpoint that the effects of the present invention can be maximized, it is preferable to use the insect-proof multifilament of the present invention in a woven fabric or a knitted fabric while maintaining the long fibers.

<Weaving and knitting>
In the present invention, the insect-proof multifilament of the present invention as a long fiber is used as at least part of warp or weft, preferably as all warp or all weft, particularly preferably all warp and all warp. It can be used as a weft to obtain a woven fabric. Hereinafter, such a woven fabric may be referred to as the woven fabric of the present invention.

  A known fabric structure can be applied to the fabric of the present invention. Examples of the woven fabric structure include, for example, a Mihara organization (plain weave, oblique weave, satin weaving, etc.), change organization (variation plain weave, satin weaving, change oblique weaving, steep oblique, Yamagata oblique, altered satin weaving, etc.) Single organization such as special organization (Hachisu or pear fabric), mixed tissue, etc .; double weaving (such as ball rasha), vertical double weaving (double-sided satin, etc.), double organization (such as Futsuori, bag weaving), etc. Examples include a pile structure (vertical velvet, etc.), a pile structure (bendaku, corduroy, etc.) and a pile structure such as a towel structure; In addition to the specific examples described above, there is a fabric structure described in JIS L 0206: 1999.

  Weaving may be performed according to a known method, that is, a known method may be selected according to the selected fabric structure or the like.

  Further, in the present invention, the insect-proof multifilament of the present invention as a long fiber is used as at least a part of the knitting yarn, preferably as all the knitting yarns, and warp knitting or weft knitting to obtain a knitted fabric You can also. Hereinafter, such a knitted fabric may be referred to as a knitted fabric of the present invention, and may be collectively referred to as a woven or knitted fabric of the present invention together with the above-described woven fabric of the present invention.

  A known knitting structure can be applied to the knitted fabric of the present invention. Examples of the knitting structure include weft knitting structures such as flat knitting, rib knitting, pearl knitting, and double-side knitting; warp knitting structures such as single denby knitting, single cord knitting, single atlas knitting, and half tricot knitting. Depending on the knitting structure, pattern yarn may be used in addition to the knitting yarn (ground yarn). As the handle yarn, the multifilament of the present invention may be used, or a known yarn may be used.

  The knitting may be performed according to a known method, that is, an appropriate known method may be selected according to the selected knitting structure or the like.

  Before weaving the woven fabric of the present invention or knitting the knitted fabric of the present invention, the multifilament of the present invention described above may be wound up, and preparations such as warping and gluing may be made.

  After weaving or knitting, the knitted or knitted fabric obtained may be dyed depending on the application. Dyeing may be performed by a known dip dyeing or printing method. Due to the fact that the multifilament matrix resin is a low-melting point PBT resin, the present invention can reduce the heating temperature of each process including the dyeing temperature, thereby effectively removing the etofenprox. It has an important feature in terms of restraining. For example, in the case of dip dyeing, a knitted or knitted fabric is heated as a preset at 90 to 130 ° C. at a speed of 15 to 30 m / min as necessary. Next, a dyeing bath in which a known dye and an auxiliary agent are dissolved is prepared, and the temperature is adjusted to 80 to 120 ° C. The woven or knitted fabric is soaked in this bathtub and dyed. During the immersion, the inside of the bathtub is preferably stirred. After dyeing, if necessary, the knitted or knitted fabric may be heated at a speed of 15 to 25 m / min at 100 to 140 ° C. as a final set. If the woven or knitted fabric is exposed to an excessively high temperature in this dyeing process or is heated for an excessively long time, etofenprox present in a sufficient amount in the multifilament may be volatilized in the dyeing process. Therefore, it is preferable to set the heating temperature and heating time in each heating operation in the dyeing process within the above-described numerical ranges to avoid a decrease in etofenprox in the dyeing process.

  After weaving and knitting, or after dyeing as necessary, the woven or knitted fabric is subjected to finish processing such as texture adjustment using a softener or glue, and correction of fabric distortion by heating at a temperature of 100 to 140 ° C. It's okay.

In the woven or knitted fabric of the present invention thus obtained, when not dyed, ethofenprox is contained in 0.25 to 3.00% by mass, preferably 0.28 to 2.75% by mass in the insect-proof undyed multifilament. It is.
On the other hand, when dyed, the woven or knitted fabric of the present invention contains 0.18 to 1.97% by mass, preferably 0.24 to 1.97% by mass of etofenprox in the insect-proof dyeing multifilament. .
That is, when the multifilament of the present invention after spinning is used for a woven or knitted fabric, etofenprox may be slightly volatilized by heating in processes such as weaving, knitting, and dyeing. It is preferable that Prox is contained in the multifilament in the woven or knitted fabric in the above-described numerical range.
Further, regardless of the presence of absence or other filaments used in dyeing, the entire woven or knitted fabric of the present invention, etofenprox is 0.11~2.40g / ^{m 2,} in particular 0.15~2.40g / ^{m 2} Preferably it is present. In the woven or knitted fabric of the present invention, when the amount of etofenprox satisfies these numerical ranges, a woven or knitted fabric with high product value that has excellent insect repellent properties and that suppresses the occurrence of filament cracking, fluff, etc. can get.

  In the woven or knitted fabric of the present invention, it is preferable to use a multifilament having a fineness of 30 to 2000 dtex and a single yarn number of 10 to 300. When the texture is important, it is more preferable to use a multifilament having a fineness of 30 to 300 dtex and a single yarn number of 10 to 50. When importance is attached to high strength and high durability, it is more preferable to use a multifilament having a fineness of 300 to 2000 dtex and a single yarn number of 50 to 300. In order to maximize the effects of the present invention, it is particularly preferable to use a multifilament having a fineness of 30 to 300 dtex and a single yarn number of 10 to 50.

  The woven or knitted fabric of the present invention can be widely applied to various uses, that is, not only living materials but also industrial materials. Living materials include, for example, health equipment (trampolines, etc.), bedding, interior (curtains, etc.), clothing, decorative items (hats, scarves, gloves, etc.), strollers, insect nets, air conditioner filters, screen door nets, outdoor equipment (tents) , Eaves, etc.). Industrial materials mean, for example, materials for civil engineering, automobiles, housing, electronics, and aircraft industries.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these Examples. In each example and comparative example, various characteristics were determined according to the following methods.

<Measurement of the amount of etofenprox in multifilament>
The content of etofenprox in multifilaments in undyed and dyed knitted fabrics was measured by liquid chromatography.

<Thread breakage, yarn fluff>
The frequency of yarn breakage during spinning and drawing was counted by the number of times per unit time and evaluated according to the following criteria.
Very good; 0 times / 2hr
Good; 1 time / 2hr
Poor; more than 2 times / 2hr

<Tensile strength, tensile elongation>
According to JIS L-1013: 1999-8.5, the tensile strength and tensile elongation of the multifilament obtained in each of the examples and comparative examples were measured. Specifically, the sample (40 cm) was attached to a tensile tester (AGSJ-1KN manufactured by Shimadzu Corp.) at a holding interval of 200 mm in a strongly pulled state, and the test was performed at a constant speed extension of a pulling speed of 200 mm / min. . Read the elongation when the initial load is applied as looseness (mm), pull the sample further, measure the load and elongation (mm) when the sample is cut, and use the following formula to determine the tensile strength (tensile strength) and elongation The rate (tensile elongation) was calculated. The number of tests was 10, and the average value was calculated.
T _b = SD / F ₀
T _b represents a tensile strength, SD represents the strength at break, F ₀ represents a positive amount fineness of the sample.
Elongation rate (%) = [(E ₂ −E ₁ ) / (L + E ₁ )] × 100
E ₁ represents a loose (mm), _{E 2} represents an elongation (mm) at break, L is expressed gripping interval (mm).

<Insect repellent>
A selective evasion test was conducted in a shelter test using the habit of preferring a dark space where German cockroaches are dark. Details of the test method are shown below.
First, a sample {undyed knitted fabric or dyed knitted fabric obtained in each example and comparative example (5 cm × 5 cm)}, food, and water were placed in a test container. Next, a nesting shelter was installed on each sample. Next, 10 German cockroaches were placed in a test container. The light was then illuminated from above the test container. After leaving it to stand for 10 hours or more, the shelter was removed while taking a video of the entire test container. From the captured video, the number of German cockroaches in each shelter was counted, and the repelling rate was calculated from the following equation.
Repelling rate (%) = {(C ₀ −C) / C ₀ } × 100
C represents the number of insects of the treated area, C ₀ represents the number of the non-treated group insect.

<Knitting operability>
The number of yarn breaks during knitting was counted and evaluated according to the following criteria.
Very good; 0 times / 2hr
Good; 1 time / 2hr
Poor; more than 2 times / 2hr

<Texture>
The undyed knitted fabric (20 cm × 20 cm) obtained in each Example and Comparative Example was gently grasped with the palm of the dominant hand, and the softness and repulsive force were recognized from the touch and feel, and evaluated according to the following criteria.
Very good; soft and repulsive (sharp feeling)
Good; somewhat hard bad; hard or too soft

<Dyed color>
The color tone of the dyed knitted fabric obtained in each Example and Comparative Example was evaluated according to the following criteria.
Very good; dark dyeing good; slightly light dyeing bad; light dyeing (lighter color)

<Example 1>
Master batch of titanium oxide (concentration 40 wt%) (RX-4214 manufactured by Nippon Pigment), master batch of etofenprox (etofenprox manufactured by Mitsui Agro) and matrix resin (isophthalic acid copolymer PBT manufactured by Polyplastics) Resin Duranex 500LP, melting point 170 ° C., IV = 0.875) was prepared. To 100 parts by mass of the matrix resin, 1 part by mass of a titanium oxide master batch and 3 parts by mass of etofenprox master batch were added and dry blended. At this time, the pure mass of etofenprox was 0.58 mass% with respect to the entire material. The blend was then dried at 90 ° C. for 5 hours. The dried dry blend was put into a melt spinning apparatus, and the melt-kneaded product was extruded from the die at a temperature of 190 ° C., a residence time of 8 minutes, and an extrusion rate of 0.5 kg / hr · sp to obtain an undrawn yarn. The obtained undrawn yarn was drawn at a draw ratio of 3.6 times and a drawing temperature of 50 ° C. to obtain an insect-proof multifilament having a fineness of 83 dtex and 12 single yarns.

  The obtained undyed multifilament was used as a front heel, a middle heel, and a back heel, and an undyed knitted fabric was obtained using a warp knitting machine (manufactured by KARL MAYER).

The obtained undyed knitted fabric was dyed. Specifically, after performing presetting under conditions of 110 ° C. and 18 m / min, a dyeing bath having the conditions shown in Table 1 below was prepared, and the undyed knitted fabric after presetting was immersed in this bath at 100 ° C. for 4 hours. . Then, final setting was performed under conditions of 125 ° C. and 18 m / min to obtain a dyed knitted fabric.

<Example 2>
Example 1 except that 1 part by weight of titanium oxide masterbatch and 5 parts by weight of etofenprox masterbatch were blended per 100 parts by weight of PBT resin, and the pure content of etofenprox was 0.94% by weight. Insect repellent unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 3>
The same procedure as in Example 1 except that 1 part by mass of titanium oxide masterbatch and 7 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 1.30% by mass. Insect repellent unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 4>
The same procedure as in Example 1 except that 1 part by mass of titanium oxide masterbatch and 10 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 1.80% by mass. Insect repellent unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative Example 1>
The same procedure as in Example 1 was performed except that 1 part by mass of titanium oxide masterbatch and 20 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 3.30% by mass. Insect repellent unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative example 2>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 0.3 part by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 0.06% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative Example 3>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 1 part by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 0.20% by mass. Insect repellent unstained multifilaments were obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Comparative example 4>
Example 1 except that 1 part by mass of titanium oxide masterbatch and 1.5 parts by mass of etofenprox masterbatch were blended per 100 parts by mass of PBT resin, and the pure content of etofenprox was 0.29% by mass. Similarly, an insect-proof unstained multifilament was obtained. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

Various measurements were performed on the undyed multifilament, the undyed knitted fabric, and the dyed knitted fabric obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results are shown in Table 2 and Table 3.

<Example 5>
An insect-proof unstained multifilament was obtained in the same manner as in Example 1 except that the number of single yarns was 24. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 1. Next, in the same manner as in Example 1, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

<Example 6>
An insect-proof unstained multifilament was obtained in the same manner as in Example 2 except that the number of single yarns was 24. Next, an undyed knitted fabric was obtained from the obtained undyed multifilament in the same manner as in Example 2. Next, in the same manner as in Example 2, the obtained undyed knitted fabric was dyed to obtain a dyed knitted fabric.

Various measurements were performed on the undyed multifilament, undyed knitted fabric and dyed knitted fabric obtained in Examples 5 and 6. The results are shown in Tables 4 and 5.

Claims (8)

In the insect-repellent dyeing multifilament in which etofenprox is contained and dyed in a polybutylene terephthalate resin having a melting point of 150 to 190 ° C.,
An insect-repellent dyeing multifilament characterized by containing 0.18 to 1.97% by mass of etofenprox. In a polybutylene terephthalate resin having a melting point of 150 to 190 ° C., etofenprox is contained, and is not dyed, in an insect-proof unstained multifilament,
An insect-repellent undyed multifilament characterized by containing 0.25 to 3.00% by mass of etofenprox.   An insect repellent woven or knitted fabric using the insect repellent dyed multifilament according to claim 1.   The insect-proof fabric or knitted fabric according to claim 3, wherein the fineness of the insect-proof dyeing multifilament is 30 to 2000 dtex, and the number of single yarns is 10 to 300.   An insect-repellent woven or knitted fabric using the insect-repellent undyed multifilament according to claim 2.   The insect-proof fabric or knitted fabric according to claim 5, wherein the fineness of the insect-proof undyed multifilament is 30 to 2000 dtex and the number of single yarns is 10 to 300. A polybutylene terephthalate resin having a melting point of 150 to 190 ° C. is mixed with 0.4 to 5.0% by mass of etofenprox to obtain a mixture,
The mixture is melt-kneaded at a temperature of the melting point of the polybutylene terephthalate resin + 10 to 30 ° C., and the resulting melt-kneaded product is spun.
Dye
A method for producing an insect-repellent dyeing multifilament comprising obtaining an insect-repellent dyeing multifilament containing 0.18 to 1.97% by mass of etofenprox. A polybutylene terephthalate resin having a melting point of 150 to 190 ° C. is mixed with 0.4 to 5.0% by mass of etofenprox to obtain a mixture,
The mixture is melt-kneaded at a temperature of the melting point of the polybutylene terephthalate resin + 10-30 ° C., and the obtained melt-kneaded product is spun.
A method for producing an insect-repellent undyed multifilament, which comprises obtaining an insect-repellent undyed multifilament containing 0.25 to 3.00% by mass of etofenprox.