JP2019001768A - Pest controlling microcapsule composition, and fiber and unwoven fabric structure treated by microcapsule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce a pest repellent microcapsule which can contain various pest repellents and has excellent washing durability, and to improve the pest repellent property by treating this in combination with a binder. Providing textile and non-woven structures. SOLUTION: A pest repellent microcapsule composition which is a pest repellent that can prevent pests from approaching and in which a pest repellent is encapsulated inside a microcapsule wall made of a synthetic resin fragilely produced by friction. The pest repellent component content concentration is 1 to 60 (wt / wt)%, preferably 5 to 50 (wt / wt)%, and the average particle size of the pest repellent microcapsules is 0.1 to 50 μm, preferably 0.1 to 50 μm. Pest repellent microcapsule composition of 0.1 to 25 μm. A fiber / non-woven fabric structure in which the amount of the pest repellent microcapsule composition adhered is 0.5 to 30 g / m2. [Selection diagram] Fig. 1

Description

  The present invention relates to a method for producing a microcapsule preparation containing a substance having a pest repellent effect and a fiber / nonwoven fabric structure obtained by processing the same.

2. Description of the Related Art Conventionally, pest repellent clothing that prevents pests from approaching when worn by a user by applying predetermined pest repellent treatment (chemical treatment, physical treatment) to the clothing fabric is known. For example, fishing clothes disclosed in Patent Document 1 are known as pest repellent clothes subjected to chemical treatment, and disclosed in Patent Document 2 as pest repellent clothes subjected to physical treatment. Working underwear is known.

  A fishing garment (insect repellent clothing) by chemical treatment disclosed in Patent Document 1 includes a front fabric and a back fabric, and one of the front fabric and the back fabric is made of a fabric subjected to a predetermined treatment. The other is composed of a fabric that has been treated differently from the fabric that has been subjected to a predetermined treatment, and one of the front fabric and the back fabric is treated with an insect repellent treatment, specifically, a treatment solution that has a repellent effect. It consists of an insect repellent fabric that has been subjected to an insect repellent treatment that coats the repellent layer on the surface of the fabric by dipping the fabric.

  Moreover, the work underwear (insect repellent clothing) by physical treatment disclosed in Patent Document 2 is intended to be able to work comfortably without being damaged by bee stings as underwear for mountain forest work. The mesh is made of an elastic material that does not absorb sweat, and the back is provided with protrusions to reduce the contact area to the skin and maintain a thickness of about 15 mm. By providing a nipple at the end of the water channel and collecting it in a bag, it is comfortable without stickiness, and by wearing work clothes on the work underwear, it has a thickness of about 15 mm It is constructed as protective clothing that protects the body and prevents needles such as mosquitoes, spiders and sparrow bees from reaching.

JP 2010-144264 A JP 2012-097392 A

  However, the conventional pest repellent clothing described above, in particular, the pest repellent clothing (fishing clothes) subjected to chemical treatment has the following problems.

  In other words, the chemical treatment method is basically performed by immersing the fabric in a repellent treatment solution, so the thickness of the coat layer due to the treatment solution adhering to the surface of the fabric must be thin. . Therefore, for general clothing, there is not much different from the method of spraying treatment liquid with repellent effect by spray method, and the repellent effect cannot be maintained for a long time, and the coat layer is solidified by drying Therefore, it is not possible to sufficiently generate odors which are harmful to pests. Eventually, there was room for further improvement from the practical viewpoint of ensuring sufficient repellent performance and sustaining for a long period of time. For this reason, combined use with various functional finishing agents has been difficult.

  The problem to be solved by the present invention is a method for producing a microcapsule encapsulating a pest repellent that solves the above-described contents, and a fiber / nonwoven fabric structure obtained by using it in combination with various functional finishing agents.

  As a result of intensive studies to solve the above problems, the present invention has found that the problem can be solved by microencapsulating a pest repellent.

  By processing the microcapsule of the present invention into a fabric, it is possible to show a pest repellent effect derived from the pest repellent contained therein, and further show high washing durability at the same time by using an appropriate combined binder, a fiber / nonwoven fabric structure Things can be manufactured.

  In the present invention, any insect repellent encapsulated in the microcapsule can be selected, but volatile compounds such as toluamides and piperidines and pyrethroids are particularly suitable.

A product containing a large amount of the above-mentioned pest repellent results in a cost-effective product, but 1 to 60 (wt / wt)%, preferably 5 to 5 in order to maintain appropriate fluidity, stability and efficacy. It is necessary to be configured within a range of 50 (wt / wt)%. If it is less than 5%, the amount of treatment of the pest repellent microcapsule composition to the non-woven fabric / fiber increases in order to develop pest repellent efficacy, resulting in a low industrial utility value. If it exceeds 50 (wt / wt)%, the increase in the viscosity will cause an increase in the viscosity, so that the working efficiency will be reduced, and if it exceeds 60 (wt / wt)%, aggregation or gelation will occur, making formulation difficult. The concentration is the peak area value analyzed by gas chromatograph.

  The average particle size of the microcapsules used in the present invention is 0.1 to 50 μm, preferably 0.1 to 25 μm. If the thickness is less than 0.1 μm, the film formation becomes insufficient, so that the pest repellent effect becomes unstable when processed into a fiber / nonwoven fabric, and at the same time the viscosity increases during production, making formulation difficult. If it exceeds 25 μm, physical destruction occurs when the fiber / nonwoven fabric is processed, so that the pest repellent effect of the fiber / nonwoven fabric product becomes unstable. When the thickness is 50 μm or more, water separation of the preparation occurs after production, and stabilization becomes difficult. In addition, the average particle diameter adopts the value of d50 analyzed by the laser diffraction method.

  The method for producing the microcapsules of the present invention can be produced by using a method using a coacervation method, an interfacial polymerization method, an in-situ method, a sol-gel method, and the interfacial polymerization method is particularly simple and has a wide range of use. Suitable for aqueous production.

  As wall materials for microcapsules, melamine, polyurea, polyurethane, polyacrylate, methyl cellulose, ethyl cellulose, polyvinyl alcohol, gelatin, gum arabic, poly vinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polyethylene, polymethacrylate, polyamide, Polyvinyl acetate, styrene maleic acid copolymer resin and the like can be mentioned, and among them, melamine and polyurethane are preferable from the viewpoint of ease of production and sustainability of effects. In addition, it is suitable for uses that release the inclusions by exerting physical changes to the capsule and destroying them, and particularly for uses that exert effects by gradually radiating without giving physical changes, Depending on the purpose, the average particle diameter described in (0013), the production method described in (0014) and the type and amount of microcapsule wall agent can be obtained by changing the structure and thickness of the microcapsule wall, It is required that the insect repellent effect is stably exhibited when necessary.

  In order to stably exhibit the pest repellent effect, it is required that the pest repellent component is stably maintained over time, and it is a general technique to check by applying a certain load. From the correlation between the component retention stability and efficacy of the microcapsules based on the present invention, the pest repellent component content has a weight loss rate of 0.1% or more and less than 50%, preferably 0%, after heating at 100 ° C. for 168 hours. It has been found that it is effective to be 1% or more and less than 25%. When the weight loss rate is 50% or more, the pest repellency is lowered within 90 days, so the industrial utility value is low. Moreover, when the weight loss rate is 25% or more and less than 50%, the pest repellent effect is stable for 180 days or more, but since the washing resistance is unstable, the industrial utility value is limited. On the other hand, it has been found that when the weight loss rate is less than 25%, the washing resistance can be stably obtained. Further, when the weight loss rate is less than 0.1%, a reverse phenomenon is often seen in which the effectiveness before washing is lowered.

  The form of the microcapsule according to the present invention is dispersed in water or an organic solvent, preferably dispersed in water, and the capsule is physically changed to break and release the inclusion. It is effective.

  The microcapsule fiber / nonwoven fabric treatment method according to the present invention is performed by diluting and dispersing in water or an appropriate organic solvent together with the functional processing agent used together, and spraying or coating or dipping the fiber directly onto the fiber. In order to uniformly treat the fibers, a dipping method is desirable. Moreover, the material which comprises a fiber and a nonwoven fabric is not specifically limited.

In order to exert the effect of the microcapsule based on the invention, depending on the contained pest repellent and its content, the content of the encapsulated microcapsule having a pest repellent content of 30 (wt / wt)% is 0.5 to It is desirable to treat uniformly at 30 g / m ² .

  In recent years, functionally processed products for fiber / nonwoven fabric products generally require resistance to washing, and it is necessary to use a binder for fiber processing in order to improve washing durability. The microcapsule based on the present invention and the functional processing agent to be used together also need to use a binder in order to exert washing durability, and a general fiber processing binder can be used. There is a need to. For example, it is required to use a single binder or a combination of a plurality of binders out of binders made of isocyanate polymer, urethane polymer, acrylic polymer, and silicon polymer. Further, depending on the combination of binders used, it is possible to prevent the removal of the processing agent by applying the processing agent, and in accordance with the principle similar to “Patent No. 595664”, compared with the microcapsule wall agent alone described in (0016). A part of the repellent component is infiltrated into a synthetic resin such as a binder, so that a stable and sustained effect can be expected.

  The functional processing agent used in combination is not particularly limited, and commercially available products can be used. For example, “Amorden NAZ-30” (manufactured by Daiwa Chemical Industry Co., Ltd.), deodorizing agent “Zobatac NANO-20” (manufactured by Daiwa Chemical Industry Co., Ltd.) and the like can be used as antibacterial and deodorant finishing agents. .

  The fiber / nonwoven fabric product to which the present invention is applied refers to all items to be washed.

Hereinafter, the embodiment will be described in detail. Unless otherwise indicated, it is g / m ² . Further, the present invention is not limited to these examples.

[Examples 1 and 2]
N, N-diethyl-3-methylbenzamide was used as a pest repellent 1, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate was used as a pest repellent 2, and 30 parts thereof were combined with styrene-maleic acid. Capsule slurry containing a pest repellent 1 or 2 after being put into an emulsifier aqueous solution containing a polymerized resin, emulsified so that the particle diameter is in the range of 0.1 to 25 μm, and then stirred to add and react with the melamine resin. Got. The formalin in the obtained capsule slurry was removed to adjust the moisture, and the sample with 100 parts as the whole was designated as pest repellent microcapsules 1 and 2.

[Examples 3 and 4]
(0024) 30 parts of the described pest repellent 1, 2 and isocyanate resin are mixed, put into an emulsifier aqueous solution containing a polyvinyl alcohol aqueous solution, and emulsified so that the particle diameter is in the range of 0.1 to 25 μm. While stirring, the reaction initiator was added and reacted to obtain a capsule slurry containing the pest repellent 3 or 4. The water content of the obtained capsule slurry was adjusted, and the sample with 100 parts as a whole was designated as pest repellent microcapsules 3 and 4.

[Processing method of Examples 1 to 4]
An aqueous dispersion was prepared according to the prescription in Table 1 described in (0034) below, and a cotton broad cloth (manufactured by Tanigami Shoten Co., Ltd., 100% blending rate, 120 g / m ² basis weight), PET tropical cloth ((Co., Ltd.) ) Dipped into both of Tanigami Shoten, 100% mixing rate, basis weight 150 g / m ² ), dried at 80 ° C. for 10 minutes, and further set at 150 ° C. for 2 minutes to obtain a test sample. Moreover, the thing which performed washing 10 times based on JISL0217: 103 method was used as the sample after washing using the washing | cleaning detergent for clothes for washing durability performance evaluation.

  The test results for both fabrics are given in (0034), with Table 2 for cotton broad cloth and Table 3 for PET tropical cloth.

[Evaluation of mosquito repellent performance]
30 test mosquitoes are released on a test gauge, and a fiber / nonwoven fabric or a fiber / nonwoven fabric product in which pest repellent microcapsules are processed is wrapped around the arm of the monitor and exposed to the gauge for a certain period of time. During this time, the number of mosquitoes stopped on the fiber / nonwoven fabric or the fiber / nonwoven fabric product after the insect pest repellent microcapsule wound on the arm is processed to calculate the resting rate and the repelling rate. The standard of the repellent effect is 70% or more before washing and 50% or more after 10 washings.

[Evaluation of anti-mite performance]
JIS L 1920 2007: Follow the entry prevention method. The standard of the mite prevention effect is 70% or more before washing and 50% or more after 10 washings.

[Concentration analysis]
The control sample was extracted with methanol, and the component concentration was calculated from the known reference concentration using a gas chromatograph (GC-2014, manufactured by Shimadzu Corporation).

[Particle size distribution measurement]
D50 was measured for the control sample using a laser diffraction particle size distribution analyzer (SALD-7000, manufactured by Shimadzu Corporation).

[Examples 5 to 8]
Combined processing of pest repellent microcapsules 1 to 4 and antibacterial deodorant finishing agent “Amorden NAZ-30” (manufactured by Daiwa Chemical Industry Co., Ltd.).

[Examples 9 to 12]
Combined processing of pest repellent microcapsules 1 to 4 and deodorant processing agent “Zobatac NANO-20” (manufactured by Daiwa Chemical Industry Co., Ltd.).

[Processing methods of Examples 5 to 12]
An aqueous dispersion was prepared in accordance with the formulation of Table 4 described in (0044) below and Table 7 described in (0045), and a cotton broad cloth (manufactured by Tanigami Shoten Co., Ltd., 100% mixing rate, 120 g / m) ² ) Immerse both PET tropical cloth (manufactured by Tanigami Shoten Co., Ltd., 100% mixing rate, 150 g / m ² basis weight), dry at 80 ° C. for 10 minutes, and then set at 150 ° C. for 2 minutes. A test sample was obtained. Moreover, the thing which performed washing 10 times based on JISL0217: 103 method was used as the sample after washing using the washing | cleaning detergent for clothes for washing durability performance evaluation.

  The test results of the fabric subjected to the antibacterial and deodorizing treatment are described in (0044). Table 5 shows the cotton broad cloth and Table 6 shows the PET tropical cloth. Moreover, the test result of the cloth which performed the deodorizing process was described in [0045], and the cotton broad cloth was set to Table 8, and the PET tropical cloth was set to Table 9.

[Evaluation of antibacterial performance]
Measurement was carried out by an antibacterial test / quantitative test of a textile product based on JIS L 0217 2015 using a bacterial solution absorption method. Staphylococcus aureus NBRC 12732 (Staphylococcus aureus) was used as a test bacterium.

  Antibacterial activity value = {log (control sample / viable count after culture) -log (control sample / viable count immediately after inoculation)}-{log (test sample / viable count after culture) -log (test sample / viable count immediately after inoculation) number)}

  The antibacterial activity value ≧ 2.2 is determined to be effective by the Fiber Evaluation Technology Council. A control sample is also generally a raw fabric of a test sample.

[Evaluation of deodorization performance]
This is the method defined by the Textile Evaluation Technology Council.
An ammonia permeation tube is set on the permeator, and the ammonia gas concentration is adjusted to 100 ppm while flowing nitrogen gas. A sample cut to 100 cm ² is put into a 5 L plastic bag, 3 L of the above-described ammonia gas is injected, and left in a sealed state for 2 hours. Thereafter, measurement is performed with a detection tube.

Weight loss rate = {(blank test measurement value−test sample measurement value) / (blank test measurement value)} × 100
A blank test is a measured value of a detector tube when ammonia gas is put in a plastic bag without a sample and left in the same manner for 2 hours.

[Comparative Example 1]
5 parts of the pest repellent 2 is put into an emulsifier aqueous solution containing a styrene maleic acid copolymer resin, emulsified so that the particle diameter is in the range of 0.1 to 25 μm, and then the melamine resin is added while stirring to react. Capsule slurry containing the pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was designated as a pest repellent microcapsule 5.

[Comparative Example 2]
30 parts of the pest repellent 2 is added to an aqueous emulsifier solution containing a styrene maleic acid copolymer resin, and after emulsification so that the average particle size is less than 0.1 μm, the melamine resin is added and reacted with stirring. A capsule slurry containing the pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was designated as a pest repellent microcapsule 6.

[Comparative Example 3]
30 parts of the pest repellent 2 is put into an aqueous emulsifier solution containing a styrene maleic acid copolymer resin, and after emulsification so that the average particle size is in the range of 25 to 50 μm, the melamine resin is added while stirring to react. A capsule slurry containing the pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was designated as pest repellent microcapsule 7.

An aqueous dispersion was prepared according to the prescription in Table 10 described in (0051) below, and a cotton broad cloth (manufactured by Tanigami Shoten Co., Ltd., 100% mixing rate, basis weight 120 g / m ² ) and PET tropical cloth ((Co., Ltd.) ) Dipped into both of Tanigami Shoten, 100% mixing rate, basis weight 150 g / m ² ), dried at 80 ° C. for 10 minutes, and further set at 150 ° C. for 2 minutes to obtain a test sample. Moreover, as washing durability performance evaluation, the thing which performed continuous washing (based on JISL0217: 103 method) 10 times was made into the sample after washing.

  Both fabrics were subjected to the mosquito repellent test described in (0028) to (0029). Moreover, the test result was described in (0051), the cotton broad cloth was set to Table 11, and the PET tropical cloth was set to Table 12.

[Comparative Example 4]
30 parts of the pest repellent 2 was put into an emulsifier aqueous solution containing a styrene maleic acid copolymer resin, emulsified so that the average particle size was in the range of 0.1 to 25 μm, and then the melamine resin was prepared in Example 1 while stirring. A capsule slurry containing a pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was designated as pest repellent microcapsule 7.

[Comparative Example 5]
30 parts of the pest repellent 2 was put into an emulsifier aqueous solution containing a styrene maleic acid copolymer resin, emulsified so that the average particle diameter was in the range of 0.1 to 25 μm, and then the melamine resin was compared with Comparative Example 4 while stirring. A capsule slurry containing a pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was designated as a pest repellent microcapsule 8.

[Comparative Example 6]
30 parts of the pest repellent 2 was put into an emulsifier aqueous solution containing a styrene maleic acid copolymer resin, emulsified so that the average particle size was in the range of 0.1 to 25 μm, and then the melamine resin was prepared in Example 1 while stirring. The capsule slurry containing the pest repellent 2 was obtained. The formalin in the obtained capsule slurry was removed to adjust the water content, and a total sample of 100 parts was used as a pest repellent microcapsule 9.

An aqueous dispersion was prepared according to the prescription in Table 13 described in (0059) below, and a cotton broad cloth (manufactured by Tanigami Shoten Co., Ltd., 100% blending rate, basis weight 120 g / m ² ) and PET tropical cloth (Co., Ltd.) ) Dipped into both of Tanigami Shoten, 100% mixing rate, basis weight 150 g / m ² ), dried at 80 ° C. for 10 minutes, and further set at 150 ° C. for 2 minutes to obtain a test sample. Moreover, as washing durability performance evaluation, the thing which performed continuous washing (based on JISL0217: 103 method) 10 times was made into the sample after washing.

Both fabrics were subjected to the mosquito repellent test described in (0028) to (0029). Moreover, the test result was described in (0059), the cotton broad cloth was set to Table 14, and the PET tropical cloth was set to Table 15.
In addition, the pest repellent microcapsules 1 and 7 to 9 are subjected to the heat residual rate test described in the following (0057) to measure the residual amount of the pest repellent contained in the capsule.

[Weight loss measurement test]
An appropriate amount of a control sample is collected, dried for 168 hours in an absolutely dry environment at 100 ° C., sampled, extracted with methanol, and then known using a gas chromatograph (GC-2014, manufactured by Shimadzu Corporation). The residual concentration was calculated from the reference concentration.

  As described above, the present invention provides a fiber / nonwoven fabric or a fiber / nonwoven fabric product that can produce microcapsules containing various pest repellents and exhibits stable pest repellent effects without affecting the performance of the combined processing agent.

It is a figure which shows the fiber adhesion example of a pest repellent microcapsule by an electron microscope (Topcon Co., Ltd. scanning electron microscope SM-300). It is a figure which shows the cross-sectional example of a pest repellent microcapsule by an electron microscope (Topcon Co., Ltd. scanning electron microscope SM-300).

Claims (9)

  A pest repellent microcapsule composition, which is a pest repellent that can prevent pests from approaching, wherein a pest repellent is sealed inside a microcapsule wall made of a synthetic resin that can be broken by friction.   The composition of the synthetic resin constituting the capsule wall agent of the pest repellent microcapsule composition according to claim 1 is melamine, polyurea, polyurethane, polyacrylate, methylcellulose, ethylcellulose, polyvinyl alcohol, gelatin, gum arabic, polyvinylpyrrolidone, carboxy A pest repellent microcapsule composition comprising two or more components of methyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polyethylene, polymethacrylate, polyamide, polyvinyl acetate, and styrene maleic acid copolymer resin.     The pest repellent component of the pest repellent microcapsule composition according to claim 1 is alletrin, alphamethrin, imiprothrin, esbioslin, esfenvalerate, cypermethrone, beta-cypermethrone, α-cyano-3-phenyl- 2-methylbenzyl-2,2-dimethyl-2- (2-chloro-2-trifluoromethylvinyl) cyclopropane-1-propanecarboxylate, cycloprotorin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, dimethylfluthrin, Decametrin, Tetraflumethrin, Tetramethrin, Terrareslin, Tefluthrin, Deltamethrin, Tralomethrin, Transfluthrin, Bioareslin, Bioresmethrin, Fenpropatoline, Fenfluthrin, Fenvalerate, Phthalathin Bratrin, flamethrin, praretrin, profluthrin, violesmethrin, flucitrinate, flumtrin, fulvalinate, profluthrin, 5-benzyl-3-furylmethyl- (E)-(1R, 3S) -2,2-dimethyl-3- (2 -Oxothiolane-3-ylidenemethyl) cyclopropanecarboxylate, mesothrine, metfurthrin, resmethrin, silafluorene and other pyrethroid compounds and pyrethroids which are isomers of these compounds, or dimethyl phthalate, dibutyl phthalate, 2-ethyl-1,3 -Hexanediol, di-n-propylisocincomeronate, p-dichlorobenzene, di-n-butyl succinate, caran-3,4-diol, N, N-diethyl-3-methylbenzamide, 1- It is a volatile compound such as methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate, p-menthane-3,8-diol, ethyl 3- (N-butylacetaldehyde) propionate. Microcapsule composition.   The pest repellent microcapsule composition according to claim 3 has a pest repellent component content concentration of 1 to 60 (wt / wt)%, preferably 5 to 50 (wt / wt)%. Microcapsule composition.   The microcapsule composition for pest repellent, wherein the pest repellent microcapsule composition according to claim 4 has an average particle size of 0.1 to 50 µm, preferably 0.1 to 25 µm.   Regarding the pest repellent component content of the pest repellent microcapsule composition according to claim 5, the weight loss rate after heating and drying at 100 ° C. for 168 hours is 0.1% or more and less than 50%, preferably 0.1% or more and 25 A microcapsule composition for repelling pests, characterized by being less than%. Textile and nonwoven structure, wherein the adhered amount of pest repellent microcapsule composition according is 0.5 to 30 g / m ² to claim 6.   A fiber / nonwoven fabric structure characterized in that the pest repellent microcapsule composition according to claim 7 and any one of a binder comprising an isocyanate polymer, a urethane polymer, an acrylic polymer, and a silicon polymer are treated in combination. .   9. A fiber / nonwoven fabric structure, wherein the fiber / nonwoven fabric structure according to claim 8 is treated with an antibacterial and deodorizing agent, a deodorizing agent, and the like as a functional processing agent for fibers.