Polymer containing low-temperature volatile components

Abstract

To develop a technology that allows low-boiling-point components to be stably incorporated even under high-temperature loads, and to provide a technology for incorporating low-boiling-point components into a polymer.SOLUTION: A polymer incorporating silicon oxide is produced by first causing silica to contain low-boiling-point components and then end-capping the silica with two-dimensional monolayer silicon oxide.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin containing a low-temperature volatile component, a fiber containing a low-temperature volatile component, and a processed product thereof. In the present invention, the term "low-temperature volatile component" refers to a component that is volatile at room temperature and provides a desirable effect to a user or a polymer. [Background technology]

[0002] Contact with blood-sucking insects such as mosquitoes and ticks, as well as nuisance and unsanitary insects such as cockroaches, can lead to the spread of infectious diseases such as mosquito-borne malaria and yellow fever, and to the transmission of viruses that cause fatal high fevers via ticks. Contact with nuisance and unsanitary animals such as cockroaches can also cause microbial contamination. In response to these circumstances, various resins incorporating pyrethroids have been developed to combat blood-sucking insects, as have various methods for controlling their release. However, incorporating low-temperature decomposable pyrethroids into resins with high melting points poses many challenges, limiting their range of application (see, for example, Patent Documents 1 to 6). Furthermore, the effect of pyrethroids in these products is known to be suppression of blood-sucking by repellency rather than insecticidal effect (https: / / tanatiku.com / kazuma / 1024). Pyrethroids have a low volatility temperature of around 100°C, making them a volatile component of the present invention. However, incorporating them into polymers presents challenges, and only a limited number of polymers incorporating them have been developed.

[0003] Under these circumstances, we came up with the idea of ​​contributing to society by developing technology to incorporate low-boiling-point components into high-melting-point polymers. However, while there are technologies for supporting these low-boiling-point components in polymers and diffusing them into the surrounding area, and technologies for applying low-boiling-point components such as insect repellents directly to the skin to repel insects (see, for example, Patent Documents 7 and 8), there has been no attempt to incorporate these components into polymers, process them into threads, or apply them to mosquito nets or clothing. These components are liquid under normal conditions, for example, at 25°C under 1 atmosphere, and in a molten polymer state (140-300°C), they tend to volatilize easily and are difficult to incorporate into polymers, which makes them difficult to incorporate. The same situation exists for other low-boiling-point components such as fragrances and biopheromones.

[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 have 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 can be formed, and then stacked as necessary, silicon oxide similar to graphene or a silicon oxide having a layered structure similar to graphite can be obtained, resulting in silicon oxide with unique, particularly specific, adsorption and release properties. They then speculated that impregnating this silicon oxide with a low-boiling component, such as a fragrance ingredient, followed by end-capping could result in controlled release of the low-boiling component. Such silicon oxide was not known, and incorporating it into a polymer would require high temperatures, but it was not known that low-boiling components could be stably incorporated 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 low boiling point component to be stably blended even under high temperature load.

[0010] In light of this situation, the present inventors have sought a technology that allows low-boiling point components to be stably incorporated even under high temperature loads, and as a result of extensive research and effort, they have discovered that by incorporating fragrance into silica and then incorporating silicon oxide end-capped with two-dimensional monolayer silicon oxide, it is possible to stably incorporate low-boiling point components into polymers, and have completed this invention. Therefore, the present invention is as follows. <1> A polymer made by incorporating a low-boiling component into silica and then end-capping it with two-dimensional single-layer silicon oxide. <2> The silicon oxide to be end-capped is characterized in that it is silicon oxide 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 at low temperature. <1> The polymer described in <3> The end-capping silicon oxide is electrically conductive. <1> or <2> The polymer described in <4> 4. The polymer according to claim 1, wherein the end-capping silicon oxide has a peak only at 0 Θ° in powder X-ray analysis. <5> The silicon oxide end-capping is characterized in that the tetraalkoxysilane is tetraethoxysilane. <1> ~ <4> 10. The polymer according to any one of claims 1 to 9. <6> The end-capping silicon oxide surfactant is decaglycerol monostearate; <1> ~ <5> 10. The polymer according to any one of claims 1 to 9. <7> The silicon oxide end-capping 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> 10. The polymer according to any one of claims 1 to 9. <9> The low-boiling component contained in the polymer has a boiling point of 70 to 200°C at 1 atmosphere. <1> ~ <8> The polymer according to any one of the above items, wherein the volatile component is: Effects of inventions containing biopheromones such as (Z)-8-DODECEN-1-YL ACETATE, cooling ingredients such as menthol and thymol, and insecticidal ingredients such as pyrethroids

[0011] According to the present invention, it is possible to provide a technique that enables a low boiling point component to be stably blended 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. 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. The silicon oxide of the present invention can be obtained by weighing out the above components, stirring at 30-50°C, confirming the formation of an emulsion, 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 the end-capped silicon oxide of the present invention while preventing the formation of sp3 hybrid orbitals. The end-capped silicon oxide of the present invention has π electrons and a graphene-like structure, allowing it to encapsulate compounds within a 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 the electron affinity allows for controlled release. 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 and stably incorporated 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 that can be encapsulated or adsorbed include fragrances, insect repellents, insecticides such as pyrethroids, and biopheromones. Among these, insecticides such as pyrethroids and biopheromones are particularly preferred, as they have been the most difficult to control to date. Preferred examples include biopheromones such as (Z)-8-DODECEN-1-YL ACETATE, cooling agents such as menthol and thymol, and insecticides such as pyrethroids. These can be used alone or in combination. These components are preferably adsorbed onto silica or silicon oxide in an amount of 0.1 to 5 times the amount of the silica or silicon oxide, followed by end-capping with 0.1 to 5 times the amount of silicon oxide used for end-capping, followed by blending with the polymer melt. Suitable examples of such polymers include polyethylene, polypropylene, PET, polybutylene terephthalate, polyamide, and polylactic acid. The final blend is preferably 100 to 100,000 ppm.

[0014] When incorporating a low-boiling component, the low-boiling component is first adsorbed onto the silicon oxide to be impregnated, and then the silicon oxide of the present invention is produced and end-capped by forming the silicon oxide of the present invention on the surface of the silicon oxide adsorbed with the low-boiling component according to the following procedure. Specifically, end-capping was performed by adding 9.1 g of decaglycerin monolaurate, 3 g of triethanolamine, 2.22.5 g of orthotetraethoxysilane, and 0.1 g of tetramethylammonium to 100 ml of n-hexane, 2.5 ml of amyl alcohol, and 50 ml of water, heating to 70°C with stirring to form an emulsion, and maintaining the temperature at 70°C for 24 hours to gradually hydrolyze the orthotetraethoxysilane and form 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, and then air-dried at 70°C for 24 hours to obtain 10 g of silicon oxide. PXRD showed a peak at 0Θ°, but no other peaks or inflection points. This identified the silicon oxide as 2D-single-layer silicon oxide. Micrographs also showed that the particle size was 2-5 nm and that the silicon oxide had a planar layered structure.

[0015] The present invention will be described in more detail below with reference to examples. [Example] Example 1

[0016] Silicon oxide for end-capping of the present invention was prepared for structural confirmation 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 producing 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 revealed a peak at 0°C, 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.

[0017] 10 g of (Z)-8-DODECEN-1-YL ACETATE was encapsulated in 10 g of ordinary silica with a hexagonal double layer structure. The PXRD of the silica used is shown in Figure 2. The inclusion was performed by directly mixing the two.

[0018] The inclusion silica was end-capped using the following procedure. 9.1 g of decaglycerol monolaurate, 3 g of triethanolamine, 2.22.5 g of orthotetraethoxysilane, and 0.1 g of tetramethylammonium were added to 10 g of inclusion silica, 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, centrifuged, and the solid was 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 inclusion silicon oxide.

[0019] 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 master batch, and 395g of polybutylene terephthalate was added to 5g of the master batch, melted, and pellets were produced. When these pellets were spun, thread with insect attractant properties was produced. Industrial applicability

[0020] 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, which is obtained by incorporating a low-boiling component into silica and then end-capping the resulting mixture with two-dimensional single-layer silicon oxide.

2. The polymer according to claim 1, characterized in that the silicon oxide to be end-capped is silicon oxide obtained 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.

3. 3. The polymer of claim 1, wherein the end-capping silicon oxide is electrically conductive.

4. 4. The polymer according to claim 1, wherein the end-capping 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 end-capping is tetraalkoxysilane or tetraethoxysilane.

6. 6. The polymer of any one of claims 1 to 5, wherein the end-capping silicon oxide surfactant is decaglycerol monostearate.

7. 7. The polymer according to claim 1, wherein the silicon oxide end-capped amine and / or organic amine is triethanolamine and / or 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.

9. 9. The polymer according to claim 1, wherein the low-boiling point component contained in the polymer has a boiling point of 70 to 200°C.

10. The polymer according to any one of claims 1 to 9, wherein the low-boiling point component contained in the polymer is selected from the group consisting of (Z)-8-DODECEN-1-YL ACETATE ((Z)-8-dodecen-1-yl acetic acid), menthol, thymol, and pyrethroid.

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