Polymer containing fragrance

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 silicon oxide to contain low-boiling-point components and then end-capping the silicon oxide with two-dimensional monolayer silicon oxide.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin containing a fragrance, a fiber containing a fragrance, and a processed product thereof. In the present invention, "fragrance" refers to a component that is volatile at room temperature and gives a pleasant feeling to the user due to the volatile component. [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) On the other hand, like these ingredients, fragrances have a low evaporation temperature of around 100°C, and as with pyrethroids, incorporating them into polymers is difficult, and only a very limited number of polymers with fragrance have been developed.

[0003] Under these circumstances, we came up with the idea of ​​developing technology to incorporate low-boiling-point fragrances into high-melting-point polymers to contribute to nighttime repellency. However, while there are technologies that support low-boiling-point repellent ingredients, similar to these fragrances, in low-melting-point polymers and diffuse them into the surrounding area, or that apply them directly to the skin to repel insects (see, for example, Patent Documents 7 and 8), there has been no attempt to incorporate these ingredients 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 difficulties 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 developments, 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 fragrance component and then end-capping it would enable controlled release of the fragrance. Such silicon oxide was not known, and incorporating it into a polymer would require high temperatures, but it was not known that a fragrance could be stably incorporated even under such high-temperature conditions. [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 fragrance to be stably blended even under high temperature load.

[0010] In light of this situation, the inventors of the present invention have sought a technology that allows repellents to be stably incorporated even under high temperature loads, and as a result of extensive research and effort, they have discovered that by incorporating a fragrance into two-dimensional monolayer silicon oxide and then incorporating silicon oxide end-capped with two-dimensional monolayer silicon oxide, it is possible to stably incorporate the repellent into a polymer, and have completed the invention. Therefore, the present invention is as follows. <1> A polymer containing silicon oxide, which is made by incorporating fragrance 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 end-capping 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> 10. The polymer according to any one of claims 1 to 9. <9> The fragrance contained in the polymer has a boiling point of 70 to 200°C. <1> ~ <8> The polymer according to any one of the above. Examples of such fragrances include jasmine-like fragrance, rose-like fragrance, lavender-like fragrance, and eucalyptus-like fragrance.

[0011] According to the present invention, a technology can be provided that allows a fragrance 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). [Figure 4] FIG. 1 shows the FTLR of the perfume-containing silica of Example 1 end-capped with silicon oxide. 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 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.

[0016] 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, fragrances are particularly preferred, as they have been the most difficult to incorporate. Such fragrances preferably have a boiling point of 70 to 200°C, and specific examples include jasmine-like fragrances, rose-like fragrances, lavender-like fragrances, and eucalyptus-like fragrances. These can be used alone or in combination of two or more. These components are preferably adsorbed onto silica or silicon oxide in an amount of 0.1 to 5 times the amount of silica or silicon oxide, followed by end-capping with 0.1 to 5 times the amount of silicon oxide 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 blending amount is preferably 100 to 100,000 ppm.

[0017] To prepare the repellent, first adsorb the fragrance onto silicon oxide to be impregnated, then, according to the following procedure, form the silicon oxide of the present invention on the surface of the silicon oxide to be impregnated with the insect repellent-adsorbed fragrance. 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, and 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 yield 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.

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

[0019] The 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 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 jasmine-like fragrance 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 encapsulation was performed by directly mixing the two.

[0021] 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.

[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 pelletized. When these pellets were spun, threads with a jasmine-like fragrance were 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, which is obtained by incorporating a fragrance into silica and then end-capping the silica 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 perfume contained in the polymer has a boiling point of 70 to 200°C.

10. 10. The polymer according to claim 1, wherein the fragrance contained in the polymer is selected from the group consisting of jasmine-like fragrances, rose-like fragrances, lavender-like fragrances, and eucalyptus-like fragrances.

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