JPH05302269A - Mothproofing fiber - Google Patents

Abstract

PURPOSE:To obtain mothproofing fiber, having high safety without malodor, excellent in durability and having rust preventing properties by applying a composition prepared by blending a pyrethroid-based compound with a specific aminosilicone and a rust preventing agent in a specific weight ratio to a textile material. CONSTITUTION:The objective mothproofing fiber is obtained by applying an aqueous emulsion composition prepared by blending (A) a pyrethroid-based compound (e.g. phenothrin) with (B) an aminosilicone having 4.5X10<-2> to 6.5X10<3>g equiv./mol amino equiv. and (C) a rust preventing agent at (1:1) to (1:20) weight ratio of the components (A)/(B) and (1:0.5) to (1:10) weight ratio of the components (A)/(C) to natural fiber, synthetic fiber, etc., by spraying so as to provide 0.01-1wt.% amount of the applied component (A). This fiber has high safety and high persistence of mite repellent effects and is excellent in dry-cleaning resistance with no volatility. A compound of the formula [R is 2-4C alkyl; Y1 is 8-18C alkyl, etc.; Y2 to Y4 are (CH2)nCOOO (n is 1-3); X1 is H, Na, etc.; X2 to X4 are H, Na, etc.], e.g. an ethylenediaminetetraacetate is used as the rust preventing agent. This fiber is suitable as wadding, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to insect repellent fibers. More specifically, the present invention relates to an insect-repellent fiber that has excellent dry cleaning resistance and that repels harmful insects such as mites or suppresses the growth of harmful insects.

[0002]

2. Description of the Related Art In the past, insecticides such as DDT and BHC have been used for the control of house hygiene pests such as mites.
Due to its carcinogenicity, its use was banned in 1971, and in recent years, low toxicity pyrethroid drugs and organophosphorus fenitrothion and fenthion have been used as insect repellents. Regarding the use of a pyrethroid drug as an insect repellent, JP-A-55-149202 and JP-A-55-149203 disclose inclusions with cyclodextrin. In addition, Japanese Patent Publication 2-555
No. 51 discloses a pyrethroid insecticide and a synergist,
During the production of acrylic synthetic fibers, wet spinning and drawing,
It is disclosed that the gel is swollen after washing with water. Further, JP-A-59-203505 discloses a pyrethroid insecticide held in a bedding filler or the like.

However, all of them have problems such as poor washing resistance (particularly dry cleaning resistance), a small mite-preventing effect, and a rough texture.

[0004]

Under the above circumstances, the present invention is an insect-repellent fiber having higher safety, less volatility, soft texture, and a long-lasting effect of repelling mites and suppressing the growth of mites. The challenge is to provide.

[0005]

In order to solve the above problems, the present invention has the following constitution. That is, a pyrethroid-based compound having an amino equivalent of 4.5 × 10 ^{2 to} 6.5 ×
An insect-repellent fiber comprising 10 ³ gram equivalents / mole of an aminosilicone and a rust preventive agent, wherein the weight ratio of aminosilicone to pyrethroid compound is 1: 1 to 1: 1.
20, the weight ratio of the rust preventive agent to the pyrethroid compound is 1: 0.5 to 1:10, and the amount of the pyrethroid compound attached to the fiber is 0.01 to 1.0% by weight. An insect-repellent fiber characterized in that the rusting agent is a compound represented by the following general formula (I).

[0006]

[Chemical 2] In the formula, R: C _{2 to} C ₄ alkyl group, Y ₁ : C _{8 to} C ₁₈
Alkyl or - (CH ₂₎ n -COO group (n:. 1 to
_{3), Y 2, Y 3} , Y 4 :-( CH 2) n -COO group _{(n: 1~3), X 1} : No, H, Na or K, X _2, X
₃ , X ₄ : represents H, Na or K.

The present invention will be described in detail below. In the present invention, the pyrethroid compound means phenothrin (3-phenoxybenzyl ester of d-cis chrysanthemic acid and d
-2: 8 mixture of trans-chrysanthemic acid with 3-phenoxybenzyl ester), synthetic pyrethrins, alectrins, furatolines, bartholins, dimethrins and natural pyrethrins. Among these pyrethroid compounds, even when subjected to a high temperature treatment of 150 ° C. or higher, the volatility is low, and the compatibility with aminosilicone described later is good, and the mite repellent effect and the mite growth inhibitory effect are less likely to decrease due to washing. From the viewpoint of excellent safety, phenothrin represented by the following chemical formula is preferable.

[0008]

[Chemical 3] Incidentally, in the present invention, as a synergist of a pyrethroid compound, generally known piperonyl butoxide,
Piperonyl cyclone, propyl isome, sulfoxide (octyl sulfoxide of isosaflor),
The combined use of safroxan, tropical, sezoxane, cinepyrines and the like is preferable because it is possible to further enhance the effect of preventing mites.

The amount of the pyrethroid compound attached to the insect repellent fiber of the present invention is 0.01% by weight or more and 1.0% by weight or less,
It is preferably 0.02 to 0.5% by weight.
If the adhered amount in the fiber is less than 0.01% by weight, good mite repellent effect and mite growth suppression effect cannot be obtained. On the other hand, when the amount of adhesion exceeds 1.0% by weight, pyrethroid compounds are generally less toxic than organophosphorus insecticides, but toxicity to the human body may become a problem depending on the intended use. It is not preferable.

The aminosilicone used in the present invention has an amino group in the molecule of the silicone polymer, and may have other substituents such as an epoxy group in addition to the amino group.

The amino equivalent of the aminosilicone is 4.5 × 10 ^{2 to} 6.5 × 10 ³ gram equivalent / mol. When the amino equivalent is less than 4.5 × 10 ² gram equivalent / mol, the compatibility with the pyrethroid compound and the rust preventive agent is good and the washing durability is good,
There is a problem that the tick repellent effect is small. It is considered that this is because the pyrethroid compound is strongly coated with the silicone polymer. On the other hand, the amino equivalent is 6.
When it exceeds 5 × 10 ³ gram equivalent / mole, the initial mites-repelling effect is excellent, but there is a problem that the repelling performance is lowered by washing such as dry cleaning.

When the insect-repellent fiber of the present invention is used for stuffed cotton such as futon cotton or for woven yarn such as tatami mat, the card machine or the loom is rusted in the process of spinning and weaving the insect-repellent fiber. A rust preventive agent is attached to the fiber in order to prevent a problem of the passability. In the present invention, as the rust preventive agent, an amino compound represented by the general formula (I) is used. Antirust agents other than amino compounds having such a structure have a problem that the pyrethroid compound used in the present invention inhibits the tick repellent effect and tick growth inhibitory effect. Specific examples of such amino compounds include the following compounds.

[0013]

[Chemical 4] Here, X means an alkali metal such as Na or K.

[0014]

[Chemical 5] Here, R ₁ is a C _4-18 alkyl group, and R ₂ is C _2-4.
In the formula, X means an alkali metal such as Na or K.

When the rust preventive represented by the general formula (I) is further used in combination with an alkyl phosphate compound such as octyl phosphate potassium salt, sodium sulfite or the like, the compound represented by the general formula (I) can be obtained. The rust preventive effect is further improved, which is preferable.

In the present invention, the weight ratio of aminosilicone to pyrethroid compound is from 1: 1 to 1:20. If the weight ratio of the aminosilicone to the pyrethroid compound is less than 1: 1, the mite-proof property of the washing durability is significantly reduced. On the other hand, the weight ratio is 1: 2
When it exceeds 0, the insect repellent performance becomes difficult to be manifested, and the object of the present invention cannot be essentially achieved. It is considered that this is because the pyrethroid compound is covered with the aminosilicone film, and the pyrethroid compound is less likely to appear on the surface.

In the present invention, the weight ratio of the rust preventive agent to the pyrethroid compound is 1: 0.5 to 1:10. If the weight ratio of the rust preventive agent to the pyrethroid compound is less than 1: 0.5, the rust preventive effect is small. On the other hand, if the weight ratio exceeds 1:10, the mite preventing property is deteriorated and the mite preventing performance is reduced. Washing resistance decreases. It is considered that this is because the rust preventive agent generally has a strong inorganic property, which adversely affects the film-forming performance of the aminosilicone and lowers the affinity for the fibers, particularly synthetic fibers such as polyester.

As the fiber material of the insect-proof fiber of the present invention, synthetic fibers such as polyester, polyamide and acrylic, semi-synthetic fibers such as rayon, and natural fibers such as cotton and wool can be used, and these are used alone. However, they may be mixed and used, or may be mixed with ordinary fibers having no insect repellent performance. The most preferable fiber material is polyester-based synthetic fiber. That is, the pyrethroid compound and aminosilicone used in the present invention have the highest affinity with the polyester synthetic fiber among various synthetic fibers and natural fibers, and have the best results for the mite-proofing and washing resistance. is there. To exemplify the method for producing insect-repellent fiber of the present invention, a water emulsion obtained by emulsifying and dispersing the above-mentioned pyrethroid compound, aminosilicone and rust preventive agent with a nonionic surfactant or anionic surfactant or a combination thereof. After applying a composition, which is mixed to the target amount of fibers to the target amount, by a padding method, a spray method, a dipping / centrifugal dehydration method, a coating method, and the like, after preliminary drying at 80 to 120 ° C, if necessary. 1
It can be manufactured by heat treatment at 50 to 200 ° C.

The insect-repellent fiber of the present invention can be used as futon cotton, cushions, stuffed cotton for chairs, core yarns for tatami edges and tatami mats, ground yarns and pile yarns for carpets, futon side fabrics, and sheets. It is widely applicable to fabrics such as knitted fabrics and non-woven fabrics.

The method of evaluating the insect repellent effect of the insect repellent processing agent of the present invention was the feed attraction method. That is, a powder feed (CLEA, Japan CF-2) during mite breeding was spread as evenly as possible on a petri dish with a height of 30 mm and a diameter of 200 mm, and 1 g of untreated cotton and cotton treated with insect repellent were added to each of them. 8 cm x
I spread it out to a size of 8 cm and placed it symmetrically one by one.

At the center height of 1.4 cm on this cotton, a powdered feed containing no ticks (water content: 15%)
Place a container with a diameter of 2.8 cm containing 1.0 g at room temperature 25
After placing in an incubator adjusted to a temperature of ± 2 ° C and humidity of 70 to 80% for 40 hours, the number of mites crawling in the feed in the container is counted by the saline floating method to determine the repellent rate, The insect repellent effect was evaluated. The repellent rate was calculated by the following formula. Repelling rate (%) = {(A−B) / A} × 100 Here, A represents the number of mites of untreated cotton, and B represents the number of mites of insect-repellent treated cotton.

The larger the number is, the more effective the repellency is. The repellency is preferably 40% or more in terms of practicality. Hereinafter, the present invention will be specifically described with reference to examples.

[0023]

【Example】

(Examples 1 to 4 and Comparative Examples 1 to 3) Single fiber fineness was emulsified with a 9-mole adduct of nonylphenol ethylene oxide to a tow of 500,000 denier consisting of polyester synthetic fiber having a denier of 6 denier, An amino silicone (TK silicone AS6) having a pyrethroid-based compound content of 0.1% by weight and a binder having an amino equivalent of 3.5 × 10 ³ gram equivalent / mol.
5. Takamatsu Yushi Co., Ltd.) to 0.5% by weight in terms of solid content, and further disodium ethylenediaminetetraacetic acid disodium salt as a rust inhibitor to 0.15% by weight in terms of solid content. After applying the prepared water emulsion composition by spraying, staple cutting to 51 mm, and then 175
Heat treatment was carried out at ℃ for 3 minutes to obtain a mite-proof fluffy cotton. The weight ratio of aminosilicone to the pyrethroid compound was 1: 5, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 1.5. As the pyrethroid compounds, phenothrin (Example 1), pyrethrin (Example 2), alectrin (Example 3), and furatulin (Example 4) were used. The compounding ratios were all the same as in Example 1. When the mites repellency of these four types of cotton wool was measured by the above method, all showed good repellency effects (Examples 1 to 4). The results are shown in Table 1.

[0024]

[0025]

[Table 1]

Next, as comparative examples, those in which phenothrin was not used in the above-mentioned Example 1 (Comparative Example 1), those in which aminosilicone was not used in the above-mentioned Example 1 (Comparative Example 2), and the rust preventive agent in the above-mentioned Example 1 were used. An ethylenediaminetetraacetic acid disodium salt (Comparative Example 3) was prepared in the same manner as in Example 1, but as shown in Table 1, all the characteristics as in Examples 1 to 4 were obtained. Those satisfying the above conditions were not obtained (Comparative Examples 1 to 3). The results are also shown in Table 1.

(Examples 5, Comparative Examples 4 and 5) 0.15% by weight of phenothrin as a pyrethroid compound with respect to 500,000 denier tow made of polyester synthetic fiber having a single fiber fineness of 11 denier (Example 5) ), 0.005
A staple was manufactured under exactly the same conditions as in Example 1 except that the content was set to be 2.0% by weight (Comparative Example 4) and 2.0% by weight (Comparative Example 5). In Example 5, the weight ratio of the aminosilicone to the pyrethroid compound is 1: 3.33, and the weight ratio of the rust preventive agent to the pyrethroid compound is 1: 1, which is highly safe and has a good anti-drying property. A tick effect was obtained. In Comparative Example 4, the weight ratio of the aminosilicone to the pyrethroid compound was 1: 100, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1:30, and the effect of preventing mites was poor. In Comparative Example 5, the weight ratio of the aminosilicone to the pyrethroid compound was 1: 0.25, the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 0.075, and there was a slight odor. It was difficult to apply as. The results are shown in Table 2.

[0028]

[0029]

[Table 2]

(Example 6, Comparative Examples 6 to 9) 0.4% by weight (Example 6) and 0.1% by weight of aminosilicone having an amino equivalent of 3.5 × 10 ³ gram equivalents / mole in Example 1 were used. % (Comparative Example 6) and 3.5% by weight (Comparative Example 7), staples were manufactured under the same conditions as in Example 1.
The weight ratio of aminosilicone to the pyrethroid compound is 1: 4 (Example 6), 1: 1 (Comparative Example 6), 1: 3.
5 (Comparative Example 7), and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 1.5 in all cases. Also,
Instead of the aminosilicone of Example 1, one having an amino equivalent of 1.0 × 10 gram equivalent / mol (Comparative Example 8) and one having an amino equivalent of 1.5 × 10 ⁴ gram equivalent / mol / mol (Comparative Example) A staple was manufactured under the same conditions as in Example 1 except that 9) was used. The weight ratio of the aminosilicone to the pyrethroid compound was 1: 4, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 1.5. The results are shown in Table 3.

[0031]

[0032]

[Table 3]

(Comparative Examples 10 to 16) In Example 1,
A trial production of staples was performed under the same conditions as in Example 1 except that the disodium salt of ethylenediaminetetraacetic acid, which is an anticorrosive agent, was changed to 0.03% by weight (Comparative Example 10) and 2.0% by weight (Comparative Example 11). did. The weight ratio of aminosilicone to the pyrethroid compound was 1: 4, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 0.3 (Comparative Example 10) and 1: 200 (Comparative Example 11). It was The former was inferior in rust resistance, and the latter had a problem in mites repellency. Further, instead of the rust preventive agent of Example 1, octylpyrudinium chloride (Comparative Example 12), 20 moles of ethylene oxide and 20 moles of propylene oxide were added, and a tetronic nonionic surfactant ( A staple made of polyester-based synthetic fiber was manufactured under the same conditions as in Example 1 except that Comparative Example 13) was used. The weight ratio of the aminosilicone to the pyrethroid compound was 1: 4, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 1.5. The anticorrosion property was not good in either case.

Further, in place of the aminosilicone of Example 1, an acrylic ester resin (Primal HA-1
0, manufactured by Nippon Reichhold Co., Ltd. (Comparative Example 14), urethane resin (Elastron 3000 Super, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (Comparative Example 15), dimethylsiloxane type silicone resin (Toray Silicone SH87).
00, manufactured by Toray Dow Corning Silicone Co., Ltd.
A staple was experimentally manufactured under the same conditions as in Example 1 except that (Comparative Example 16) was used. The weight ratio of the binder to the pyrethroid compound was 1: 4, and the weight ratio of the rust preventive agent to the pyrethroid compound was 1: 1.5.
Met. No good tick repellent effect was obtained. The results are shown in Table 4.

[0035]

[0036]

[Table 4]

[0037]

The present invention has high safety for the human body,
It provides fibers with little odor and high durability against dry cleaning, and has a tick-proof effect. It is widely used for stuffed cotton such as futon cotton and cushions, futon side cloth, sheets, blankets and carpets. Applicable.

Further, even in the stage of producing the mite-proof fiber, the iron parts of the card machine, the loom, etc. are not rusted, and there are few problems in industrialization, and the productivity is extremely high.

Claims (2)

[Claims] 1. A pyrethroid compound having an amino equivalent of 4.
An insect-controlling fiber comprising 5 × 10 ^{2 to} 6.5 × 10 ³ gram equivalents / mole of aminosilicone and a rust preventive, wherein the weight ratio of aminosilicone to pyrethroid compound is 1: 1 to 1:20. The weight ratio of the rust preventive agent to the pyrethroid compound is 1: 0.5 to 1:10, and the amount of the pyrethroid compound attached to the fiber is 0.01.
% To 1.0% by weight, and the rust preventive agent is a compound represented by the following general formula (I). [Chemical 1] In the formula, R: C _{2 to} C ₄ alkyl group, Y ₁ : C _{8 to} C ₁₈
Alkyl or - (CH ₂₎ n -COO group (n:. 1 to
_{3), Y 2, Y 3} , Y 4 :-( CH 2) n -COO group _{(n: 1~3), X 1} : No, H, Na or K, X _2, X
₃ , X ₄ : represents H, Na or K. 2. The insect repellent fiber according to claim 1, wherein the pyrethroid compound is phenothrin.