JPS6324971B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel fragrance substance,
This is the result of research aimed at developing fragrances or cosmetics that absorb moisture at appropriate temperatures and emit a harmonious fragrance. The present invention can be applied to daily necessities and industrial goods that require fragrance, as well as odor removers, insect repellents, bath products, and other products, and its uses are extremely wide. [Conventional technology] Conventionally known fragrance products include incense, incense sticks, scented bags, scented sponges, scented plastics, and scented gels. It has been difficult to preserve and emit a harmonious aroma over a long period of time, ranging from the notes to the middle notes and even the base notes. In response to this, the present inventors have so far carried out various developments, including "Production method of perfume composition and heated fragrance product containing the same" (Nippon Tokuko Publication No. 58-12027). In particular, at least one metal-containing wood material selected from the group consisting of aluminum alcoholates, silicate esters, titanate esters, zirconate esters, and hydrolysates thereof in "scented wood materials" (Nittokuko 1972-23122). We have invented aromatic wood materials consisting of densifying agents, fragrances, and wood materials, including mono-, di-, and triesters of zirconic acid, and aqueous dispersions, alcohol solutions, sol solutions, and gel solutions containing these. Those impregnated with wood materials absorb fragrances well,
They have elucidated techniques such as clarifying the need for preservation. Since then, we have continued to devote our efforts to creating new fragrance products, and we have now finally completed the present invention. [Means for Solving the Problems] That is, the present inventors have developed a powder material impregnated with a fragrance in an anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water. and a powder made by adhering a fragrance to an organic material, and this fragrance contains fillers, excipients, hydrophilic agents, exothermic agents, foaming agents, colorants, brighteners, and energizers. He invented a scented product containing at least one material selected from the group consisting of agents. [Function] A typical manufacturing method for an anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water is "Amorphous zirconium phosphosilicate and its manufacturing method" (Japanese Patent Application Publication No. 59-26912), but most of them are highly acidic, that is, pH 3 to 5.
It is a compound of However, a commercially available product equivalent to this is "Zirconium Complex ZPS" manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., and after analyzing and examining its properties, it can be used effectively in the present invention. should be selected. This zirconium compound powder impregnated with a fragrance is a powder of the above-mentioned porous zirconium phosphosilicate neutral compound, in which top notes, i.e., fragrance ingredients with poor retention and high volatility, are added in a gaseous or non-aqueous solution. It is mixed in a liquid form and impregnated and adsorbed, and there is no problem even if a small amount of a middle note, that is, a fragrance with intermediate volatility and retention (modifier) is blended with the top note, but the base note should be removed as much as possible.
Neutral here means that when the zirconium phosphate silicate compound comes into contact with water, the pH of the aqueous solution is 5.
-8 In the sense of a neutral salt, which is particularly preferably 5.5 to 7.5, this is important in order not to change the fragrance tone of an adsorbed fragrance or a powder in which a fragrance is attached to an organic material. It was discovered that when the pH deviates from this, that is, when the pH becomes lower than 5 or higher than 8, the fragrance tone deteriorates significantly. Ideally, in order to adsorb fragrances to zirconium phosphosilicate, it would be best to separately impregnate the above-mentioned powders with single fragrances belonging to the top notes, but this would complicate the process and would not allow uniformity of the emitted fragrance. Since the top notes are lost, blended top notes are often used. The limit amount of top notes that can be impregnated into the powder is 10% by weight for 60-80 mesh powder and 50% by weight for 150-200 mesh powder, and the practical impregnation amount is 3-6% by weight for the former. %, the latter being 10-30% by weight. The granules used in this test mainly had a porous surface with a pore radius of about 10 angstroms, and the specific surface area measured by the BET method was 100 to 400 m ² /g. The impregnated and adsorbed top notes rapidly release the top notes in the presence of water with a relative humidity of 85% or higher or in water, but this effect slows down in the middle notes.
Base notes are impractical because the release is extremely slow. Therefore, the middle and base notes should be powdered by other methods to increase the surface area and adjust their volatility to the top notes. The middle note and the base note, which are powder themselves, can be designed to simply be ground, this powder is attached to the surface of an organic material, and then the fine powder is evaporated.
However, many middle notes and base notes are liquid to semi-solid and often form into droplets and have a small surface area, so it is necessary to forcibly turn them into powder and expand them. The present inventors conducted tests to determine whether various powder materials were suitable for the present invention, and found that due to their porous nature, when in contact with water,
It has been recognized that organic materials that do not cause any reaction when mixed with or pressure molded with anhydrous zirconium phosphosilicate compounds with a pH of 5 to 8 are most preferable from the standpoint of aroma preservation. . Inorganic materials generally cause some reactions, or there are concerns that they may, and they may harm the aroma, so it is safer not to use them. Typical organic materials include wood powder, hay powder, dry fruit powder, dried pollen, grass root bark powder, bamboo powder, carbon black, graphite powder,
Cellulose powder, protein powder, leather powder, silk thread powder, synthetic resin powder, starch powder, paper powder, polysaccharide or glucoside powder, dried seaweed powder, etc. alone or in a mixture of two or more, when used in the present invention. It is better to reduce the moisture content as much as possible. These powders are used after being ground into 50 to 350 mesh pieces. When using this, it is actually possible to change the base organic material used depending on the fragrance, for example, the middle note is sprayed on wood powder and attached, and the base note is made into a solution and sprayed on cellulose powder and dried. It is extremely effective. Once the powder impregnated with the fragrance and the powder with the fragrance attached are prepared in the above manner, these are then blended to form a fragrance, depending on the purpose of use. Therefore, it is necessary to adjust the blending amounts of both, and this blending must be carried out in a mixer in the absence of moisture as a general rule. When blending, careful consideration is required to determine the ratio of the pure components of the top note, middle note, and base note while testing the fragrance under the conditions of use. When performing the above formulation, it is preferable to include at least one material selected from the group consisting of fillers, excipients, hydrophilic agents, exothermic agents, foaming agents, colorants, brightening agents, and energizing agents. . The filler is a powder that has the above porosity and has a pH of 5 to 8 and does not have any adverse effect on the anhydrous zirconium phosphate silicate compound, organic materials, and fragrances when it comes into contact with water. When using an inorganic powder, use a powder with a small specific surface area and no attached water, such as alumina, zinc white, calcium carbonate, barium sulfate, talc, calcined kaolin, mica, silicon oxide, calcium silicate (wollastonite),
Selected from asbestos, titanium oxide, etc. Excipients are substances that help them to be molded into a certain shape when pressurized.In addition to some of the fillers mentioned above, lactose, polysaccharides, starch, cellulose powder, and synthetic resins Powder etc. have this effect,
Although too hard materials such as inorganic powders are unsuitable, organic binders are suitable for this purpose. The hydrophilic agent is added to promote the release of fragrance by replacing the fragrance with water, and includes glycol, glycerin, saccharides, polyols, polyalkylene polyols, surfactants, or water-soluble neutral inorganic salts. The exothermic agent is added to raise the temperature of the fragrant substance through water absorption, and can be used as a powder or in the form of microcapsules. Typical examples include calcium oxide, magnesium oxide, barium oxide, and anhydrous substances that change into salts that generate heat or compounds with water of crystallization by absorbing water, and in some cases generate heat of neutralization. Also effective are mixtures of A blowing agent is a chemical that rapidly volatilizes the aroma, especially the middle and base notes, and the gas generated here is a compound that continuously generates carbon dioxide gas or a gas mainly composed of carbon dioxide. Coloring agents are dyes and pigments that are added to enhance the commercial value of the scented products and scented molded products of the present invention, and to indicate that they are unused, in use, or have been used. This is added to display the operating temperature. Brighteners include wax luster, glass luster,
It is added when metallic luster is required, and polyethylene wax, animal and plant wax, glass powder, and metal powder are used. To achieve a metallic appearance, metal vacuum evaporation, sputtering evaporation, and aluminum are used. Paste, aluminum powder, nickel powder, bronze powder, etc. are used. An electrifying agent is an antistatic agent used to prevent dust from adhering to the scented molded product, an agent used to prevent charging and ignition when mixing fragranced powder, and an agent used when using electrical heating. It is an electrical heating agent and a thermal conductivity improver. Commonly used current-carrying agents are quaternary awamonium salts, quaternary phosphonium salts, conductive polymers, charge transfer complexes, graphite, metal powders, etc., and one or two of them may be used in combination. When molding a compound as described above, the presence of moisture is avoided as much as possible, unlike in normal powder molding. That is, when a binder for molding is required, wax, polyolefin, polybutadiene, polyisoprene, polyvinyl chloride, polyvinyl acetate, vinyl chloride vinyl acetate copolymer, acrylonitrile, styrene copolymer,
Polystyrene, acrylate copolymer, methacrylate copolymer, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl butyral, rubber, petroleum resin, coumaron/indene resin, polyterpene resin, 100% phenolic resin,
A small amount of organic solvent solution such as cellulose ester may be used, but condensation resin binders (such as phenolic resins, melamine resins, urea resins) that may generate moisture during pressure molding, especially during heating and pressure molding, and It is not preferable to use highly hydrophobic binders (eg, silicone resins, fluorine resins), etc. The present inventors have combined the above-mentioned raw materials to produce a large number of aromatic products of excellent quality. The product of the present invention becomes a fragrance that has a sustained release property when exposed to moisture in the air, and when it is forced to absorb moisture or comes into direct contact with water, it quickly evaporates the aroma. It becomes a fragrance. This product can be used as a powder or granule in a bag, etc., or as a molded product in a specific shape. In the case of a molded product containing a foaming agent, each may be molded into a laminated product, or the pellets of the foaming agent and the pellets of the fragrance may be lightly mixed together and placed in a bag, etc. You may also serve it. [Examples] In order to further clarify the technical content of the present invention, examples will be given and explained below. Example 1 An anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water (ZSP-100 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., specific surface area 350 m ² /
Add 10 parts of American lemon oil to 100 parts of 100 mesh powder with a pH of 5.5 when in contact with water with vigorous stirring and allow sufficient absorption and impregnation. On the other hand, an alcohol solution containing 1 part of heavy distillate of American lime oil (a mixture of citral, linalool, geraniol, terpineol, borneol, terpinen-4-ol, etc.) was sprinkled on 10 parts of Eucaria spicata wood powder. After thorough mixing, the alcohol is evaporated under reduced pressure. Furthermore, on the other hand, an alcoholic solution containing 0.1 part of labdanum oil is sprinkled on 1 part of diatomaceous earth and dried to form a powder. 7 parts of the powder containing the above lemon oil, 2 parts of the powder containing the heavy fraction of lime oil, and 1 part of the powder containing labdanum oil were mixed to obtain a fragrance. Example 2 An anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water (ZSP-100 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., specific surface area 350 m ² /
Add 10 parts of American lemon oil to 100 parts of 100 mesh powder with a pH of 5.5 when in contact with water with vigorous stirring and allow sufficient absorption and impregnation. On the other hand, an alcohol solution containing 1 part of heavy distillate of American lime oil (a mixture of citral, linalool, geraniol, terpineol, borneol, terpinen-4-ol, etc.) was sprinkled on 10 parts of Eucaria spicata wood powder. After thorough mixing, the alcohol is evaporated under reduced pressure. Furthermore, on the other hand, an alcoholic solution containing 0.1 part of labdanum oil is sprinkled on 1 part of diatomaceous earth and dried to form a powder. 7 parts of powder containing the above lemon oil, 2 parts of powder containing heavy distillate of lime oil, 1 part of powder containing labdanum oil, 10 parts of talc powder, 1 part of 2% polyvinyl acetate solution, and yellow A trace amount of the dye was placed in an internal ribbon mixer, mixed vigorously, and then compressed into a molded fragrance product. The resulting tablets are placed in a waterproof paper bag impregnated with polyamide resin and epoxy resin, sealed, and then wrapped in a polyethylene bag for complete packaging. The resulting paper-bag tablets absorb moisture and emit a fresh, pure, yet calming lemon fragrance, and are used as a portable fragrance for indoor use, as well as as an air freshener for bathrooms and bathtubs. served. Example 3 An anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water (ZSP-100 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., specific surface area 450 m ² /g,
200 mesh powder with PH6.4) when in contact with water
Add 20 parts of British lavender oil to 100 parts while stirring vigorously, then seal in a container and store for about a month. On the other hand, 7 parts of lauan wood powder is impregnated with 1 part of lavender oil distillation residue oil as an alcohol solution. The above-mentioned powder containing lavender oil and powder containing lavender distillation residue oil were mixed to produce a fragrance. Example 4 An anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water (ZSP-100 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., specific surface area 370 m ² /g,
200 mesh powder with PH7.5) when in contact with water
Add 20 parts of British lavender oil to 100 parts while stirring vigorously, then seal in a container and store for about a month. On the other hand, 7 parts of lauan wood powder is impregnated with 1 part of lavender oil distillation residue oil as an alcohol solution. The above powder containing lavender oil, powder containing lavender distillation residue oil, and a trace amount of purple dye are mixed thoroughly in a mortar and then tableted into the shape of a lavender flower bud to form a product. This product can be used as an air freshener for car interiors and toilets, and gradually absorbs moisture to emit a fragrance. Example 5 Instead of the lavender oil in Example 3, the perfume shown in the following table was impregnated, and the organic materials shown in the table below were attached to the organic materials shown in the table below. Blend.

〔Effect of the invention〕

The fragrant substances and fragrant molded products shown in the present invention are one type of fragrance or cosmetics that absorb moisture at an appropriate temperature and emit a fragrance, and are based on the gist of the present invention and related techniques. daily necessities, industrial products, odor removers, insect repellents, insecticides, etc. that require fragrance using
It can produce and provide bath products. The incense tones are incense, incense, perfume (floral, fruity,
Notes such as green, animal, balsamic, chypre, fusea, aldehyde, bouquet, oriental, modern, fresh, tobacco, etc.), flavors (notes such as fruity, spicy, citrus, milky, beans, mint, meat, nutty, green, etc.) ) and other chemical compounds across a wide range of odors. The products of the present invention can be in the form of powders or various molded forms, and in some cases, their appearance can be made aesthetically pleasing. The method of use is very simple, and the degree of fragrance release can be easily guaranteed by the content of the fragrance. Therefore, it must be said that the present invention has extremely great industrial utility value.

Claims (1)

[Claims] 1. Powder impregnated with a fragrance in an anhydrous zirconium phosphate silicate compound that is porous and has a pH of 5 to 8 when in contact with water, and a fragrance attached to an organic material. Fragrance substances mainly composed of powder. 2. Mainly consists of a powder made of an anhydrous phosphoric acid zirconium silicate compound impregnated with a fragrance, which is porous and has a pH of 5 to 8 when in contact with water, and a powder made of an organic material with a fragrance attached. characterized in that it contains at least one material selected from the group consisting of fillers, excipients, hydrophilic agents, exothermic agents, blowing agents, coloring agents, brightening agents, and energizing agents. A scented substance. 3 Claim 2 in which the scented substance is molded
Fragrance substances listed in section.