JPH04263617A - Production of insect-proofing acrylic fiber - Google Patents

Abstract

PURPOSE:To provide the title acrylic fiber imparted with durable insect-proofing performance having sustainable activity against sanitary insect pests. CONSTITUTION:Acrylic fiber in primary swollen state and having 50-500% swell, having been put to wet spinning, drawing and washing processes, is imparted with (A) an organic pest controlling agent, (B) an organic pest controlling agent included in a monomer to trimer-type cyclodextrin <=3000 in average molecular weight, (C) an epoxy-modified siloxane and (D) an amino-modified siloxane, followed by drying, crimping, and thermal relaxation treatment, thus obtaining the objective acrylic fiber.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing insect repellent acrylic fibers which have excellent insect repellent effects against sanitary pests and are durable.

0002

[Prior Art] Conventionally, it has been known to impart insect repellent effects to clothing, bedding, etc. by applying insect repellents to fibers or textile products. Many of them tend to fall off, lose their insect repellent effect after a few washes, and have long-lasting problems.

[0003] As a means to prevent the insect repellent from falling off, Japanese Patent Application Laid-Open Nos. 59-163426 and 60-57117 disclose methods for wet spinning, stretching and gel swelling in the acrylic fiber manufacturing process after washing with water. A method has been proposed in which an insect repellent such as an insect repellent or an organic phosphorus insecticide is applied in the form of an emulsion to fibers, and the emulsion is treated with dry heat to incorporate the insect repellent into the fiber.

0004

[Problems to be Solved by the Invention] However, the insect repellent performance obtained by simply incorporating an emulsified insect repellent inside the fiber has a certain degree of durability against relatively mild treatment conditions such as washing. However, it is not possible to sufficiently prevent the insect repellent from falling off during the product processing process, especially in hot water and steaming conditions at high temperatures that use various surfactants, acids, and alkaline processing agents, such as in dyeing finishing. Therefore, it is difficult to maintain the insect repellent effect. The present invention further improves the insect repellent effect and proposes a method for rationally obtaining such insect repellent fibers in the manufacturing process of acrylic fibers.

[0005]

[Means for Solving the Problems] The present invention provides an organic pest control method for producing acrylic fibers by wet spinning, drawing and washing steps, and applying organic pest control to the fibers in a primary swollen state with a degree of swelling of 50 to 500%. an organic pest control agent clathrated with a mono- to trimeric cyclodextrin having an average molecular weight of 3000 or less;
A method for producing insect-repellent acrylic fibers, which comprises applying an epoxy-modified siloxane and an amino-modified siloxane, followed by drying, crimping, and heat relaxation treatment.

[0006] The organic pest control agent (hereinafter referred to as insect repellent) used in the present invention refers to insecticides, insect repellents, repellents, synergists, etc. that are effective against sanitary pests such as fleas, lice, and mites. , for example, organophosphorus insecticides such as fenitrothion, diazinon, acephate, propios, carbaryl,
Carbamate insecticides such as isoprocarbo, pyrethroid insecticides such as phenothrin, vermethrin, cyperamethrin, insect repellents such as camphor, naphthalene, paracyclobenzene, propyl-N,N-diethylsuccicinnamate, propyl mandelate, N , N-diethyl-m-toluamide, N-butylacetanilide, 2-ethyl-
1,3-hexanediol, 2-butyl-2-ethyl-
Repellents such as 1,3-propanediol and diethyl phthalate, synergists such as octachlorodipropyl ether, isobornylthiocyanoacetate, and piperonyl butoxide are used.

The reason why the insect repellent in the present invention is limited to an organic type is (1). Organic insect repellents vaporize even at room temperature and enter the bodies of sanitary pests through the respiratory organs, increasing their insect repellent effects; (2). The emulsion stability of the siloxane emulsion dispersion is superior to that of inorganic insect repellents, and a uniform insect repellent effect can be obtained; (3). It is easier to include it in cyclodextrin than inorganic insect repellents.

In the present invention, the clathrate has an average molecular weight of 3.
It is necessary to use mono- to trimeric cyclodextrin having a molecular weight of 000 or less. This effectively clathrates the insect repellent and forms a film in which the siloxane and organic insect repellent clathrate gradually permeate and adhere from the fiber surface to the inner layer.
This is because it is necessary that the inclusions do not fall off during the dyeing and finishing process, and that they do not substantially dissolve in water or hot water in order to obtain washing resistance. The film that has penetrated and adhered to the surface can be confirmed using the following method. That is, the particle size of cyclodextrin is about 5-1
Although it is 8 angstroms, it is possible to treat the fiber in the same manner using a pigment corresponding to this, and observe its cross section with an optical microscope.

Cyclodextrin has α, β, γ, and δ homologues, which have glucose numbers of 6, 7, 8, and 9.
The molecular weights are 972, 1135, 1297, and 1459, and mono- to trimeric cyclodextrins having an average molecular weight of 3000 or less can be produced by polymerizing with a crosslinking agent such as epichlorohydrin. The inclusion functions of these mono- to trimeric cyclodextrins are similar to each other, and each homologue may be used alone or two or more types of homologues may be used in combination.

[0010] In the present invention, the average molecular weight is 1 to 3000 or less.
In addition to the organic insect repellent clathrated with trimeric cyclodextrin, it contains an unclathrated organic insect repellent. Although clathrate insect repellents have excellent long-lasting effects with little loss of insect repellent effect due to washing, the present invention aims to further improve the durability of this insect repellent by penetrating not only the surface of the fibers but also the inner layer of the fibers. Therefore, it is not preferable to increase the average molecular weight of the clathrate insect repellent to 3000 or more. Therefore, cyclodextrin with an average molecular weight of 3000 or less is used in order to penetrate into the inner layer of the fiber.
A molecular or solution state is preferable, and in the case of a solid dispersion, fine particles are preferable. Limited.

Next, the solubility of cyclodextrin in water at 25°C is 13% for α type, 1.9% for β type, and 3% for γ type.
The solubility varies depending on the type at 0%, and when the temperature increases, the solubility increases, and when polymerized, the solubility decreases at a certain temperature. The cyclodextrin required in the present invention has an average molecular weight of 3000 or less for types 1 to 3, and can be maintained by controlling the temperature to an appropriate emulsified dispersion state to penetrate into the inner fiber layer, but cyclodextrin for types 4 to 5 When the average molecular weight exceeds about 4,000, the solubility is significantly reduced and the desired effect cannot be obtained.

[0012] In the present invention, siloxane firmly fixes the insect repellent to the fibers, prevents the insect repellent from falling off, and improves washing resistance and sustainability of the insect repellent effect. Another purpose is to allow the product to pass smoothly through product manufacturing processes, such as spinning, knitting and weaving processes, and to impart a soft texture and touch to the product.

More importantly, siloxane prevents the insect repellent that has penetrated into the fibers from falling off during the dyeing process of acrylic fibers. That is, by creating a siloxane film on the surface of the fiber containing the insect repellent that has penetrated into the fiber in the primary swollen state, and then heat-treating it, this film becomes strong and the insect repellent-containing fiber becomes more durable. Prevents the clathrated insect repellent contained inside from falling off even if the fiber structure becomes loose due to high heat treatment above the secondary transition point during the commercialization process, such as dyeing process (dyeing or printing). It is something.

[0014] If there is no siloxane coating on the fiber surface, a large amount of the insect repellent inside the fiber will fall off during dipping baths or steaming treatments at temperatures above the secondary transition point, which are assumed to be the dyeing process of the fibers, and also when exposed to high temperatures. The volatilization of the insect repellent underneath is also accelerated, and the insect repellent effect is significantly reduced. In addition, the siloxane coating on the fiber surface has a great effect on insect repellent effects during use and washing of products manufactured using this fiber.

The present invention is characterized in that epoxy-modified siloxane and amino-modified siloxane are not used alone, but both are used as the siloxane.

The epoxy-modified siloxane has the following formula (1
) is used.

embedded image Dimethylsiloxane is particularly preferably used as the basic skeleton. As the amino-modified siloxane, a compound represented by the following formula (2) is used.

embedded image Dimethylsiloxane is particularly preferably used as the basic skeleton. By using an epoxy-modified siloxane and an amino-modified siloxane in combination, a film can be formed uniformly and firmly on the fiber surface, and the durability of the insect repellent performance is significantly improved.

In the present invention, an extremely excellent insect repellent effect can be obtained with a small amount of insect repellent, epoxy-modified siloxane and amino-modified siloxane.

[0018] The concentration of insect repellent used is generally 0.05 to 3%.
(based on fiber weight) is preferable. The amount of mono- to trimeric cyclodextrin having an average molecular weight of 3000 or less is the same molar amount or slightly larger (1.1 times the molar amount) than the mole amount of the insect repellent.

If the concentration of the insect repellent used is less than 0.05%, the effect will be insufficient, and if it exceeds 3%, it will be unfavorable in terms of safety and economy. When an insect repellent encapsulated with cyclodextrin is used, the duration of the effect is extended by 1.5 to several times compared to when it is used without cyclodextrin inclusion, and the washing resistance is also improved.

The ratio of epoxy-modified siloxane to amino-modified siloxane is 5-95:95-5, preferably 10-90:9.
It is applied in a weight ratio ranging from 0 to 10. The durability of the pest control agent cannot be maintained unless the amount of these siloxanes attached to the fibers is 0.1% or more (based on the fiber weight, hereinafter abbreviated as %owf) in the total amount of epoxy-modified siloxane and amino-modified siloxane. It is possible, but if the concentration exceeds 3.0% owf, the insect repellent effect will decrease at a certain insect repellent concentration, so it will be necessary to increase the insect repellent concentration, and there will be problems in passing through the processing process after spinning. This is not desirable as it tends to occur.

[0021] In the present invention, the insect repellent is applied during the production process of acrylic fibers while the wet-spun fibers are in a primary swollen state, and then dried, crimped, and heat-relaxed in sequence. We will implement it.

In the present invention, the fiber to which the insect repellent is applied is in a primary swollen state, and in this swollen state, the unclathrated and clathrated organic insect repellents are not only on the surface of the fiber but also inside the fiber. It is possible to apply penetration up to In other words, if this primary swelling state is expressed as the degree of swelling, then degree of swelling (%) = [(W1 - W2)/W2] x 10
0W1: Weight after immersing approximately 1 g of fiber in 100 cc of water at 20°C for over 1 hour, and then dehydrating it in a centrifuge for 10 minutes with a centrifugal force of 100 G. W2: Weight of the dehydrated fiber after it is completely dried at 110°C. While ordinary acrylic fibers have a swelling degree of 15-30%, in the primary swelling state, the swelling degree is 50-500%, which means that the fiber structure is very loose, and the target unencapsulated and encapsulated fibers are The environment is extremely ideal for applying insect repellents.

[0023] The fiber in the primary swollen state refers to the state of the fiber before the drying process after spinning the usual spinning dope for forming acrylic fibers in a coagulation bath, passing through the drawing and washing processes, and before the drying process, and it varies depending on the manufacturing conditions. However, although the degree of primary swelling differs depending on the process, the value increases as it goes to the front of the process.
Low degree of fiber formation. When applying the insect repellent in the present invention, it is not limited as long as the fibers are under primary swelling, but it is preferable that the degree of swelling is 150 to 300%, which is a substantial degree of fiber formation after stretching and washing.

The polymer of the acrylonitrile fiber in the present invention is not particularly limited, and may be an acrylonitrile homopolymer or a copolymer. As the acrylonitrile copolymer, any polymer containing at least 40% by weight of acrylonitrile and having fiber-forming ability can be used. Examples of the copolymerization component include acrylic acid, methacrylic acid, or their alkyl esters, vinyl acetate, vinylidene chloride, sodium allylsulfonate, sodium methallylsulfonate, sodium vinylsulfonate, and sodium styrenesulfonate. It will be done.

When forming fibers from an acrylonitrile polymer, inorganic substances such as titanium oxide, colorants, carbon black, and antibacterial agents are added to the spinning dope in order to impart functionality such as matting, coloring, conductivity, and antibacterial properties. It is also possible to add organic matter. The spinning stock solution is prepared by dissolving the acrylonitrile polymer in an organic solvent such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc., as well as an inorganic solvent such as nitric acid, rhodan salt, zinc chloride, etc. The fibers are preferably spun in a coagulation bath mainly consisting of a mixture of the same solvent and water as used in the spinning dope, followed by stretching and washing steps to obtain fibers in a primary swollen state. In the present invention, unclathrated and clathrated insect repellents, epoxy-modified siloxanes, and amino-modified siloxanes are applied to the fibers obtained by this method, but the application may be carried out in one bath or in multiple baths of two or more baths. It may also be applied in a mixed bath or a single bath. When applying epoxy-modified siloxane and amino-modified siloxane to fibers in separate baths, it is preferable from the viewpoint of durability to apply the epoxy-modified siloxane first and then apply the amino-modified siloxane. The unclathrated and clathrated fibers to which the insect repellent and siloxane have been applied are sequentially dried, crimped, and heat-relaxed to form tow or cut raw cotton.

The fibers obtained according to the present invention can pass through the spinning, weaving and finishing processes without any problems in the same way as ordinary acrylic fibers, and can be made into products such as carpets and blankets. The resulting products have a soft touch and feel similar to untreated textiles, are wash resistant and have a long-lasting insect repellent effect, especially against mites.

[0027]

[Examples] The present invention will be explained below with reference to Examples.

[0028] The insect repellent effect was determined using 5 m of 300 Dermatophagoides mites, 150 mg of culture medium, and 0.2 g of fiber for evaluation.
Raised at 25°C x 75% RH in a screw tube for 4
The number of ticks inhabited after 8 hours was measured, and the mortality rate was determined. The mortality rate is calculated using the following formula. Mortality rate (%) = [(A-B)/A] x 100A: Total number of mites used. B: Total number of mites living after 48 hours. The degree of swelling was determined according to the calculation method shown in the text.

[0029]

[Example 1] An acrylonitrile polymer containing 94.2% by weight of acrylonitrile, 5.3% by weight of vinyl acetate, and 0.5% by weight of sodium methacrylate was dissolved in dimethylacetamide to a concentration of 18.0% by weight. As a spinning stock solution,
Using a spinneret with a hole diameter of 0.07 mmφ and a hole number of 40,000 H, it was spun into a coagulation bath of a 30.0% by weight aqueous solution of dimethylacetamide at a temperature of 40°C, and after washing with water, it was stretched 5.5 times and the primary material had a swelling degree of 250. A swollen fiber was obtained. Solution A is prepared by dispersing isobornylthiocyanoacetate (hereinafter abbreviated as IBTA) in this fiber with a nonionic surfactant. Solution B dispersed with an activator, Solution C made by emulsifying epoxy-modified siloxane represented by formula (3) with polyoxyethylene (POE) nonylphenyl ether, and amino-modified siloxane represented by formula (4). After applying liquid D emulsified with POE nonylphenyl ether as shown in Table 1, it was dried and densified in a roller dryer at 140°C, mechanically crimped, and after moist heat relaxation treatment at 140°C, it was cut to form Bright 2d. ×51mm raw cotton No. 1 (present invention), No. 2 to 6 (comparative examples) were obtained.

For comparison, raw cotton produced without adding insect repellent or siloxane to the primary swollen fibers during the above spinning was dyed with 0.1% owf of IBTA and epoxy modified using a package dyeing machine. Siloxane is 0.3%
wf, amino-modified siloxane was attached by post-processing with B liquid, C liquid, and D liquid so that it was 0.3% owf, and 10
After drying and film forming treatment at 0°C for 10 minutes, raw cotton No. 7
(Comparative example) was obtained.

These raw cotton No. After spinning a 50% blend of 1 to 7 and normal acrylic fiber Bright 2D x 51mm that has not been treated with insect repellent using a worsted spinning machine to a count of 2/48 meters, knitted fabrics were produced. The insect repellent effect of the specimens, which were subjected to dyeing treatment, softening treatment, washing treatment according to JIS 103 method, and dry cleaning treatment with petroleum solvent, was evaluated in terms of mortality rate. The results are shown in Table 1.

From this, raw cotton No. When samples Nos. 5 and 6 were treated under practical dyeing conditions (100° C. x 30 minutes), the insect repellent volatilized and fell off to a large extent, and had no practical product performance at all. Also, raw cotton No. 2 to 4 and No. 7 is the raw cotton No. 7 in terms of insect repellent effect, washing resistance, and dry cleaning resistance. 1 (the present invention).

[Chemical 3]

[C4]

Dyeing conditions: Cachilon Red KGLH (cationic dye manufactured by Hodogaya Chemical Co., Ltd.) 0.1% owf
Cationogen PAN (cationic activator manufactured by Dai-ichi Kogyo Co., Ltd.) 1.0% owf acetic acid
1.0%o
wf pH=4.5
, LR=1:25, 100°C x 30 minutes. Soft finishing conditions: Taflon Sur (cationic softener manufactured by Dai-ichi Kogyo Co., Ltd.) 1.0% owf
LR=1:25, 40°C x 10 minutes.

[0034]

[Table 1] Amount applied: IBTA, %owf of pure siloxane.

[0035]

[Example 2] An acrylonitrile-based polymer having a composition of 59.0% by weight of acrylonitrile, 40.0% by weight of vinylidene chloride, and 1.0% by weight of sodium methallylsulfonate is added to dimethylformamide so that the polymer concentration is 25.0% by weight. The solution was dissolved to give a spinning dope, and spun into a coagulation bath consisting of a 50.0% by weight aqueous solution of dimethylformamide at 35°C using a spinneret with a pore diameter of 0.09 mm and a number of holes of 15,000 H. After washing with water, N,N-diethyl-m-toluamide (hereinafter abbreviated as "Deet") is preliminarily encapsulated in β-cyclodextrin having a molecular weight of 1135 and having a molecular weight of 90% in a fiber that has been stretched twice and has a swelling degree of 75%. , Deet was 0.1 for each of Solution E, which was dispersed with a nonionic surfactant, and Solution F, which was prepared by emulsifying the epoxy-modified siloxane represented by formula (5) with POE nonylphenyl ether.
5% owf, epoxy modified siloxane 0.3% owf
After drying and densifying in a roller dryer at 130°C, 0.2% of amino-modified siloxane was
After applying the same liquid D as used in Example 1 in the second bath so that it becomes
Bright 10 after applying wet heat relaxation treatment at ℃ and then cutting.
d×102mm raw cotton No. 8 (invention) was obtained.

For comparison, raw cotton No. 1 was prepared in the same manner as above, except that 0.5% owf of epoxy-modified siloxane was deposited in the first bath, and liquid D was not deposited in the second bath. 9 (comparative example) was obtained. The obtained raw cotton was dyed and finished in a wine color under the following conditions, and a regular acrylic fiber dull 8d x 102mm without anti-mite treatment was separately dyed and finished in the same color.
Semi-worsted and yarn count 1/5M to make a 50% blended yarn.
After spinning C, a mat is made from this spun yarn, and one part of it is washed 10 and 20 times in accordance with JIS103 method, and the other condition is a test for accelerated changes over time during use. They were left in a hot air dryer at 50°C for 100 hours, and their insect repellent effects were evaluated in terms of mortality rate. The results are shown in Table 2.

Staining conditions: Cachilon Yellow 3GLH
0.
01%owf Cachiron Red GLH
0.8%owf
Cachilon Blue GLH
0.008
%owf Cationogen AN Suha゜ (Daiichi Kogyo Seiyaku cationic activator) 1.0%
owf pH=4.5, LR
= 1:10, 100°C x 40 minutes. Finishing conditions: Taflon Spin 78ND (Daiichi Kogyo Seiyaku cationic softener) 1.0% owfLR = 1:25,
40℃ x 10 minutes.

[0038]

[Table 2] Amount applied: Deet, %owf of pure siloxane.

[0039]

[C5]

[0040]

Effects of the Invention: When an organic insect repellent is simply applied to fibers or fibers in a primarily swollen state, the efficacy lasts only 2 to 3 months. A clathrate compound using a specific cyclodextrin, an unclathrated insect repellent, and a specific siloxane are combined, and the unclathrated organic insect repellent is made by gradually infiltrating and adhering from the surface layer of the fiber to the inner layer. In addition to achieving an initial insect repellent effect, the sublimation rate of the clathrated organic insect repellent is suppressed, which is the so-called sustained release effect, so that the insect repellent function lasts for 3 to 4 years or more, and at the same time, the insect repellent does not easily fall off when washed. This made it possible to obtain a product with a very low amount of moisture, a good texture and touch with excellent softness and smoothness, and no problems in passing through the processing process.

Claims (1)

[Claims] Claim 1: When producing acrylic fibers, the degree of swelling after wet spinning, stretching and washing steps is 50 to 500.
%, an organic pest control agent, an organic pest control agent clathrated in 1-3 cyclodextrin having an average molecular weight of 3000 or less, an epoxy-modified siloxane, and an amino-modified siloxane are applied to the fiber in a primary swollen state, and then A method for producing insect repellent acrylic fiber, which comprises drying, crimping, and heat relaxation treatment.