Polymer containing insect repellent

Abstract

To provide a technique for blending an insect repellent in a polymer, by developing a technique capable of stably blending the insect repellent even to a high temperature load.SOLUTION: Mix tetraalkoxysilane with a surfactant, water, and an amine and / or an organic amine, generate silica while forming an emulsion, wash and remove components other than the silica, then low-temperature dry the resulting silica, incorporate an insect repellent into it, and then use silica capped with a two-dimensional monolayer to blend and form a polymer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an insect-repellent resin, an insect-repellent fiber, and processed products thereof. In the present invention, "insect repellent" refers to the effect of preventing contact with blood-sucking insects such as mosquitoes and mites, and unpleasant and unsanitary insects such as cockroaches. [Background technology]

[0002] Contact with blood-sucking insects such as mosquitoes and ticks, and unpleasant and unsanitary insects such as cockroaches, can lead to the spread of infectious diseases such as mosquito-borne malaria and yellow fever, and to infection with viruses that cause fatal high fevers transmitted by ticks. Contact with unpleasant and unsanitary animals such as cockroaches can also cause microbial contamination. Under these circumstances, various resins incorporating pyrethroids have been developed to combat blood-sucking insects, and various means for controlling the release of these drugs have also been developed. However, there are many difficulties involved in incorporating low-temperature decomposable pyrethroids into resins with high melting points, and it must be said that the range of application is narrow (see, for example, Patent Documents 1 to 6). Furthermore, it is known that the effect of pyrethroids in these products is to suppress blood-sucking by repellency rather than to kill insects ( https: / / tanatiku.com / kazuma / 1024)

[0003] Under these circumstances, we sought to maximize the repellent effect and came up with the idea of ​​using icaridin or DEET rather than pyrethroid insecticides to provide contact repellency. However, while there are technologies for supporting these repellent ingredients in low-melting polymers and diffusing them into the surrounding area, or for applying them directly to the skin (see, for example, Patent Documents 7 and 8), there has been no attempt to incorporate them into polymers, process them into threads, or apply them to mosquito nets or clothing. These ingredients are liquid under normal conditions, for example, at 25°C under 1 atmosphere, and when the polymer is molten (140-300°C), they tend to volatilize easily and are difficult to incorporate into the polymer, which is the cause of the aforementioned difficulty in incorporating them.

[0004] When blending such components into polymers, the idea of ​​impregnating MESO silica with them was considered, but this had the drawback of not being able to fully retain the components through simple impregnation.

[0005] On the other hand, it is common knowledge that silicon dioxide exists as an oxide of silicon with sp3 hybrid orbitals, and that its basic crystalline structure is a hexagonal bilayer structure, with these units stacking to form a three-dimensional structure. In recent years, it has become known that modifying the basic hexagonal bilayer structure can provide electrical properties and be useful as a microcapsule shell. Research on single-layer silicon dioxide with a non-stacked hexagonal bilayer structure has progressed, leading to the development of single-layer silicon dioxide with planar hexagonal bilayers and cyclic hexagonal bilayer silicon dioxide tubes (see, for example, Patent Documents 9, 10, and 11). Such hexagonal planar silica can be obtained by processing tetraalkoxysilane into an emulsion or liquid crystal using a surfactant, followed by baking.

[0006] On the other hand, it is known that some forms of silicon oxide have electrical conductivity (see, for example, Patent Document 12). Such silicon oxide generates heat when irradiated with microwaves, and because it is electrically conductive, it is thought to have free electrons and is silicon oxide with sp2 hybrid orbitals. Such silicon oxide is mostly recognized as fine particle silica, and its shape is lumpy when viewed under an electron microscope, with no planar structure confirmed. No attempt has been made to make it into a planar monolayer. It has also been disclosed that such silicon oxide can be obtained by firing naturally occurring plant-derived vitreous silica in a reducing atmosphere. Regarding silicon itself, a type called silicene is known that has a planar structure similar to that of graphene, but unlike graphene, it has a "packed ring structure," and although its electronic state is unclear, it is speculated to be in a special electronic state due to its ability to encapsulate calcium ( (https: / / www.tohoku.ac.jp / japanese / newimg / pressimg / tohokuuniv-press20141222_03web.pdf) As for silicon oxide, nothing other than a hexagonal double layer structure has been clarified.

[0007] In light of these prior art techniques, the present inventors hypothesized that by generating silicon oxide at the gas-liquid interface or elsewhere and constructing a planar structure, a single layer of sp2 hybridized silicon oxide could be formed, and then stacked as needed, silicon oxide similar to graphene or a silicon oxide having a layered structure similar to graphite could be obtained, resulting in silicon oxide with unique, particularly specific, adsorption and release properties. They embarked on the development of such silicon oxide. They speculated that impregnating such silicon oxide with a repellent and then end-capping it would enable controlled release of the repellent. Such silicon oxide was not known, and incorporating it into a polymer would require high temperatures, but it was not known that a repellent could be incorporated stably even under such high-temperature loads. [Prior art documents] [Patent documents]

[0008] [Patent documents] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-001533 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-127020 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-063494 [Patent Document 4] Japanese Patent Application Publication No. 08-245324 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-255702 [Patent Document 6] Japanese Patent Application Publication No. 2023-35859 [Patent Document 7] Special Publication No. 2014-523446 [Patent Document 8] Japanese Patent Application Laid-Open No. 2007-039342 [Patent Document 9] WO2019 / 40915 Brochure [Patent Document 10] Patent No. 4590544 [Patent Document 11] Patent No. 5322042 [Patent Document 12] Japanese Patent Application Publication No. 2020-87899 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention was made under these circumstances, and an object of the present invention is to provide a technology that allows a repellent to be stably formulated even under high temperature load.

[0010] In light of this situation, the inventors of the present invention have sought a technology that allows the repellent to be stably incorporated even under high temperature loads, and as a result of extensive research and effort, they have discovered that by incorporating an insect repellent into two-dimensional monolayer silicon oxide and then incorporating silicon oxide end-capped with two-dimensional monolayer silicon oxide, the repellent can be stably incorporated into a polymer, leading to the completion of this invention. Therefore, the present invention is as follows. <1> A polymer made by mixing tetraalkoxysilane, a surfactant, water, and an amine and / or an organic amine to form an emulsion while generating silicon oxide, washing and removing components other than silicon oxide, and then drying at low temperature to impregnate the silicon oxide with an insect repellent, and then end-capping the silicon oxide with two-dimensional monolayer silicon oxide. <2> The silicon oxide is characterized in that it is produced by mixing tetraalkoxysilane, a surfactant, water, and an amine and / or an organic amine to form an emulsion, generating silicon oxide, washing and removing components other than silicon oxide, and then drying at low temperature. <1> The polymer described in <3> The silicon oxide is electrically conductive. <1> or <2> The polymer described in <4> The silicon oxide has a peak only at 0Θ° in powder X-ray diffraction. <1> ~ <3> 10. The polymer according to any one of claims 1 to 9. <5> The silicon oxide is characterized in that the tetraalkoxysilane is tetraethoxysilane. <1> ~ <4> 10. The polymer according to any one of claims 1 to 9. <6> Silicon oxide, surfactant is decaglycerol monostearate, <1> ~ <5> 10. The polymer according to any one of claims 1 to 9. <7> Silicon oxide is characterized in that the amine and / or organic amine is triethanolamine and / or tetraalkylammonium salt. <1> ~ <6> 10. The polymer according to any one of claims 1 to 9. <8> The polymer substrate is selected from polyalkylene, polyalkylene terephthalate, and polyamide. <1> ~ <7> The polymer according to any one of claims 1 to 5.

[0011] According to the present invention, a technique can be provided that allows a repellent to be stably formulated even under high temperature load. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram showing the results of X-ray analysis of the silicon oxide powder of the present invention in Example 1. [Figure 2] FIG. 1 shows the results of powder X-ray analysis of a typical hexagonally layered silica flake. [Figure 3] 1 is a micrograph of the silicon oxide of the present invention in Example 1 (a photograph as a substitute for a drawing). Modes for carrying out the invention

[0013] The silicon oxide used in the end-capping of the present invention is characterized by having a single layer structure of silicon oxide with sp2 hybrid orbitals. Here, silicon oxide with a single layer structure of sp2 hybrid orbitals can be confirmed by the following facts, and conversely, these properties can be used to define the silicon oxide with a single layer structure of silicon oxide with sp2 hybrid orbitals of the present invention. Such silicon oxide may form a layered structure due to tautomerization between the silicon-oxygen double bond and the silicon-carbon single bond, which exhibits an affinity interaction. <Things to check> 1. In powder X-ray diffraction, there is a peak only at 0Θ°, and there is no inflection point, which indicates that there is only one crystal plane and that it is in a single-layer state. 2. It is electrically conductive, which indicates that π electrons originating from sp2 hybrid orbitals exist as free electrons. 3. Even in a layered state, the particle size is 10 nm or less.

[0014] Such silicon oxide can be produced by mixing a tetraalkoxysilane, a surfactant, water, and an amine and / or an organic amine to form an emulsion while generating silicon oxide, washing and removing components other than silicon oxide, and then drying at low temperature. Preferred examples of the tetraalkoxysilane include low-carbon tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane. Preferred examples of the surfactant include nonionic surfactants that readily form lamellar structures, such as sorbitan monolaurate and decaglycerol monofatty acid esters, and cationic surfactants such as quaternary ammonium salts, such as tetramethylammonium chloride, tetramethylammonium bromide, and octadecyltrimethylammonium chloride. The content of these surfactants is preferably 0.1 to 10 times the amount of tetraethoxysilane. Cationic surfactants can also be used as organic amines (described below), and their use is particularly preferred because it allows for the reduction of the amounts of other surfactants and organic amines. Preferred examples of the organic amine include triethylamine, triethanolamine, arginine, lysine, and urea. These organic amines act as catalysts for the hydrolysis of tetraalkoxysilanes. Furthermore, since silicon oxide is formed at the emulsion interface, an organic solvent capable of dissolving tetraalkoxysilanes, rather than being mixed in any proportion, and water are required to form a reaction site. Mixed solvents of hydrocarbons such as cyclohexane and normal hexane and amyl alcohols having long-chain alkyl groups are preferred as these organic solvents, and the amount of organic solvent is preferably 1 to 100 times the amount of tetraalkoxysilane. The mixing ratio of the hydrocarbon to the alcohol having a long-chain alkyl group is preferably 1:99 to 99:1 by mass. The amount of water is preferably 0.1 to 10 times the amount of organic solvent.

[0015] The silicon oxide of the present invention can be obtained by weighing out the above components, stirring at 30-50°C, confirming that an emulsion has been formed, and then heating and stirring at a low temperature of 60-90°C for 12-48 hours to hydrolyze the mixture and form silicon oxide at the emulsion interface. After the reaction is complete, the solid silicon oxide is separated, washed with water and a solvent, and dried at 60-80°C, thereby obtaining silicon oxide to be impregnated with the repellent of the present invention while preventing the formation of sp3 hybrid orbitals.

[0016] The silicon oxide to be impregnated with the repellent of the present invention has π electrons and a graphene-like structure, allowing it to encapsulate compounds within its six-membered ring. Due to its electron affinity, it has a stronger adsorption ability than conventional silica, making it suitable for release control. Therefore, low-melting-point compounds can be encapsulated and stably incorporated into high-melting-point polymers such as polyamides, and their release can be controlled by the electron affinity. Furthermore, low-melting-point compounds can be encapsulated into conventional silica, which can then be coated (end-capped) with the silicon oxide of the present invention to stably incorporate into high-melting-point polymers such as polyamides. Such low-melting-point compounds can be encapsulated or adsorbed in an amount 0.5 to 5 times the amount of silicon oxide or silica. The amount of silicon oxide required for end-capping is preferably 0.5 to 5 times the amount of silicon oxide or silica used as the substrate. Preferred examples of low-melting-point compounds to be encapsulated or adsorbed include fragrances, insect repellents, insecticides such as pyrethroids, and biopheromones. Among these, insect repellents are particularly preferred because they are useful for preventing infection with malaria and dengue fever and overcoming drug resistance. Suitable examples of such insect repellents include icaridin, DEET, and lemon oil. These can be used alone or in combination. It is preferable to adsorb 0.1 to 5 times the amount of these components to silica or silicon oxide, then end-capping with 0.1 to 5 times the amount of silicon oxide for end-capping, and blending the resulting polymer melt. Suitable examples of such polymers include polyethylene, polypropylene, PET, polybutylene terephthalate, polyamide, and polylactic acid. It is preferable to blend the final amount to 100 to 100,000 ppm.

[0017] To incorporate the insect repellent, the repellent is first adsorbed onto silicon oxide to be impregnated, and then the silicon oxide of the present invention is formed on the surface of the silicon oxide to be impregnated with the insect repellent according to the following procedure, followed by end-capping: 9.1 g of decaglycerin monolaurate, 3 g of triethanolamine, 2.22.5 g of orthotetraethoxysilane, and 0.1 g of tetramethylammonium are added to 100 ml of n-hexane, 2.5 ml of amyl alcohol, and 50 ml of water, and the mixture is heated to 70°C with stirring to form an emulsion, which is then maintained at 70°C for 24 hours, gradually hydrolyzing the orthotetraethoxysilane and forming silicon oxide at the emulsion interface. After the reaction was completed, the mixture was returned to room temperature, the solid matter was centrifuged, washed three times with 50 ml of ethanol and three times with 50 ml of water, and then air-dried at 70°C for 24 hours to obtain 10 g of silicon oxide. PXRD showed a peak at 0 Θ°, with no other peaks or inflection points. This silicon oxide was therefore identified as 2D-single-layer silicon oxide. Microscopic images revealed particle sizes of 2-5 nm and a planar layered structure.

[0018] The present invention will be described in more detail below with reference to examples. [Example] Example 1

[0019] The silicon oxide for repellent impregnation of the present invention was prepared according to the following procedure. Specifically, 9.1 g of decaglycerin monolaurate, 3 g of triethanolamine, 2.22.5 g of orthotetraethoxysilane, and 0.1 g of tetramethylammonium were added to 100 ml of n-hexane, 2.5 ml of amyl alcohol, and 50 ml of water. The mixture was heated to 70°C with stirring to form an emulsion. The mixture was then maintained at 70°C for 24 hours, gradually hydrolyzing the orthotetraethoxysilane and forming silicon oxide at the emulsion interface. After the reaction was completed, the mixture was returned to room temperature, centrifuged, and the solid was washed three times with 50 ml of ethanol and three times with 50 ml of water. It was then air-dried at 70°C for 24 hours to obtain 10 g of silicon oxide. PXRD showed a peak at 0°, with no other peaks or inflection points. This silicon oxide was therefore identified as 2D-single-layer silicon oxide. Furthermore, from the micrographs, the particle size was 2 to 5 nm and a planar layered structure was observed.

[0020] 10 g of this silicon oxide was inclusively mixed with 10 g of icaridin. The PXRD of the silica used is shown in Figure 2. The inclusion was carried out by directly mixing the two.

[0021] The clathrate silicon oxide was end-capped using the following procedure. 9.1 g of decaglycerin monolaurate, 3 g of triethanolamine, 2.22.5 g of orthotetraethoxysilane, and 0.1 g of tetramethylammonium were added to 10 g of clathrate silicon oxide, 100 ml of n-hexane, 2.5 ml of amyl alcohol, and 50 ml of water. The mixture was heated to 70°C with stirring to form an emulsion. The temperature was maintained at 70°C for 24 hours, gradually hydrolyzing the orthotetraethoxysilane and producing silicon oxide at the emulsion interface. After the reaction was completed, the mixture was returned to room temperature, and the solid was centrifuged and washed three times with 50 ml of ethanol and three times with 50 ml of water. The mixture was then air-dried at 70°C for 24 hours to yield 17 g of silicon oxide end-capped clathrate silicon oxide.

[0022] 95g of polybutylene terephthalate was melted at 250°C, 5g of the end-capped silicon dioxide was added, and the mixture was stirred and pelletized. This was used as a masterbatch, and 395g of polybutylene terephthalate was added to 5g of the masterbatch, melted, and pellets were produced. When these pellets were spun, thread with insect repellent properties was produced. Industrial applicability

[0023] The present invention is applicable to the production of high melting point polymers containing low melting point compounds.

Claims

1. A polymer containing silicon oxide end-capped with two-dimensional monolayer silicon oxide, which is prepared by mixing tetraalkoxysilane, a surfactant, water, and an amine and / or an organic amine to form an emulsion while producing silicon oxide, washing and removing components other than silicon oxide, and then drying at low temperature to impregnate the silicon oxide with an insect repellent.

2. 2. The polymer according to claim 1, wherein the silicon oxide is obtained by mixing tetraalkoxysilane, a surfactant, water, and an amine and / or an organic amine to form an emulsion, generating silicon oxide, washing and removing components other than silicon oxide, and then drying the resulting product at low temperature.

3. 3. The polymer according to claim 1, wherein the silicon oxide has electrical conductivity.

4. 4. The polymer according to claim 1, wherein the silicon oxide has a peak only at 0 Θ° in powder X-ray diffraction.

5. 5. The polymer according to claim 1, wherein the silicon oxide is tetraalkoxysilane and the tetraalkoxysilane is tetraethoxysilane.

6. The polymer according to any one of claims 1 to 5, wherein the silicon oxide is a surfactant and the surfactant is decaglycerol monostearate.

7. 7. The polymer according to claim 1, wherein the silicon oxide is an amine and / or an organic amine is triethanolamine and / or a tetraalkylammonium salt.

8. The polymer according to any one of claims 1 to 7, wherein the polymer substrate is selected from polyalkylenes, polyalkylene terephthalates, and polyamides.

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