JPS59139268A - Gradual release type aromatic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sustained release composition with excellent long-lasting fragrance effect.

Indoor air fresheners emit and deodorize the washrooms and toilets of buildings, the interior of cars, etc., and many of these types of air fresheners are solid from the standpoint of ease of use. For solid fragrances, fragrances are incorporated into aqueous gels such as agar, gelatin, and CMC, or fragrances are impregnated and adsorbed into porous substrates such as activated carbon, silica gel, and alumina gel. The effective period for releasing the fragrance is short, and although the latter has a long fragrance retention period, the fragrance may become inferior due to denaturation of the fragrance. In order to prevent inferiority of fragrance, if activated alumina is formed into a tablet shape and then adsorbed with fragrance, the molded product tends to disintegrate after adsorption, and the fragrance retention is insufficient.

As a result of various studies on the above-mentioned problems regarding conventional solid fragrances, the present inventor found that it is suitable to use alkyl group-bonded silica gel as a support for holding fragrances. Therefore, an object of the present invention is to provide a sustained-release fragrance composition that has a long fragrance retention period and less chemical modification of the fragrance by impregnating alkyl group-bonded silica gel with a liquid fragrance. Another object of the present invention is to create a sustained-release fragrance that can control the volatilization rate of the fragrance and promote and homogenize its impregnation into the alkyl group-bonded silica gel by mixing the liquid fragrance with a non-dissociable surfactant. An object of the present invention is to provide a composition.

The alkyl group-bonded silica gel used in the present invention is produced by silane treatment of a synthetic or natural porous inorganic material, and the porous inorganic material contains alumina, magnesia, unreacted silicate, etc. in addition to the main silica gel. You can leave it there. Preferably, the alkyl group-bonded silica gel is generally a fine powder with an average particle size of 50 μm or less, and is produced by treating the surface of porous silica gel with silane, and at that time, water in the silica gel is sufficiently removed at high temperature. It requires that. In this surface treatment, a Grignard reaction or an amino compound may be used, but silica gel is generally used with the following formula: (wherein R1 and R2 are methyl or chloro groups, n
is 0 or a positive number. ) is preferably treated with an organic chlorosilane to form a Si-O-Si bond. When chemically bonding silanes, the chain length of the organic alkyl group generally increases to increase the retention and adsorption of liquid fragrances, especially non-polar fragrances and non-dissociative surfactants. big. For this reason, it is better for the organic alkyl group to have a large number of carbon atoms, preferably from 8 to 30 carbon atoms. is chemically bonded to silica gel and used alone or as a mixture.

Approximately 8.5 to 9.0 x 10-6 mol/
There is a silanol group of m2, and when this is reacted with, for example, organic alkyltrichlorosilane, a maximum of about: 3.0
~4.2 x 10-6 mol/m2 of organic alkylsilane is bonded to the silanol group, and depending on the selection of reaction conditions, the organic alkylsilane is bonded in a single layer, or in two or three layers. may be in the polymer state. Therefore, the selection of organic alkyltrichlorosilane is important to eliminate the large number of silanol funds, and also to cap silanol groups and unreacted chloro groups, which can be geographically introduced with trimethylsilyl groups, to attach alkyl groups to them. secondary silylation) may also be applied. In this capping process, unreacted chloro groups are converted into methoxy groups using methanol, and then trimethylsilylated, thereby achieving almost complete surface treatment and trimethylating as many bare silica-like silanol groups as possible geographically. Therefore, it has the advantage of better retention of liquid fragrance.

The liquid fragrance used in the present invention may be any natural or synthetic fragrance as long as it can be adsorbed and retained by the alkyl group-bonded silica gel. limonene, myrcene, carene,
Monoterpene hydrocarbons such as pinene, sesquiterpene hydrocarbons such as caryophylene, santare, and cedrene, diterpene hydrocarbons such as camphorene, aromatic hydrocarbons such as paracymene, geranyl acetate, citronellyl acetate, benzyl benzoate, etc. Examples include aliphatic or aromatic carboxylic acid esters. Liquid fragrances are usually used as mixed fragrances, and preservatives such as resinoids and oleoresins are added as necessary before and after impregnation, and aromatic alcohols such as ethyl alcohol and isopropyl alcohol or their aqueous solutions are added to promote fragrance generation. may be added in an appropriate amount. The amount of liquid fragrance is 3 to 50% by weight based on the alkyl group-bonded silica gel.
If it is less than 5% by weight, adequate fragrance cannot be obtained;
Even if it is used in an amount exceeding 0% by weight, the fragrance release effect will not improve.

In addition, it is preferable to mix the liquid fragrance with an appropriate amount of a non-dissociable surfactant, since the rate of volatilization of the fragrance can be controlled and the impregnation of the alkyl group-bonded silica gel can be promoted and uniformed.

The amount of this surfactant is 10 to 500% based on the liquid fragrance.
Preferably, it is % by weight. The non-dissociative surfactant has the general formula: (wherein R is a C8-Cl2 alkyl group, n
is a positive number from 2 to l5. ) alkylphenol polyethenoxy ether, general formula: R-O-(CH2CH2O)n-H (wherein R is a C12-C18 alkyl group, n is 3-1
It is a positive number of 5. ), or a polyethenoxyalkylol of the general formula: (wherein R is a C12 to C18 alkyl group, and m and n are the same or different positive numbers of 1 to 10) An example is amide.

The obtained aromatic composition may be stored in a breathable container as it is as a powdered fragrance, or may be used by being sealed in a bag made of non-woven fabric, paper, or a plastic film with ventilation holes, or it may be used as an artificial flower or accessory. It may also be attached. After impregnating liquid fragrance into alkyl group-bonded silica gel, add aromatic alcohol and/or non-dissociative surfactant to form a slurry, adhere to a glass plate or plastic sheet, and dry in the air or heat. Since it is in the form of a thin layer, it may be used by storing it in a breathable container.

The aromatic composition of the present invention may be compression-molded by applying appropriate pressure after further mixing fine powder of an extender. This bulking agent is generally insoluble in the liquid fragrance and has a particle size of 30 μm.
One or more of the following alkyl group-bonded silica gel, magnesium aluminate metasilicate, aluminum or magnesium stearate, methyl cellulose, hydroxypropyl cellulose, starch, modified starch, lactose, and fatty acid esters of sugars. The amount of filler is
10~ of alkyl group-bonded silica gel impregnated with liquid fragrance
If it is less than 10% by weight, the strength of the molded article will be low, and if it exceeds 50% by weight, it is unfavorable in terms of fragrance retention. Compositions mixed with fillers usually have a weight of 1 to 5 tons/cm2.
Compress into tablets using pressure. The obtained molded product may be stored in a breathable container in the same manner as described above, or may be attached to an air-conditioning/heating entrance as an aroma generator, or used in combination with an electric heater.

The aromatic composition of the present invention can also be molded by suspending it in a gel-like substance, and for this purpose, an aqueous polymeric substance, an organic solvent, an aqueous medium, etc. are used. Examples of aqueous polymeric substances include carrageenan, agar, gelatin, sodium alginate, and polyvinyl alcohol; examples of organic solvents include polyhydric alcohols such as glycerin, ethylene glycol, and polyethylene glycol; and water-insoluble resins and colorants. , preservatives, organic or inorganic salts, surfactants, etc. may be added. The gelling agent may be a metal salt of a fatty acid instead of the aqueous polymeric substance described above, such as sodium or potassium salts of stearic acid, palmitic acid, oleic acid, magnesium salts or calcium salts of stearic acid, lauric acid, palmitic acid, etc. One or more kinds of salts may be used, and alkaline soaps are particularly preferred. These soaps contain organic solvents such as ethanol, propylene glycol, hexylene glycol,
-Methyl-3-methoxyglycol, isoparaffinic hydrocarbon, etc. may be added one or more kinds, and a small amount of water may be used. In the case of this molding, the aqueous molecular substances or metal salts of fatty acids, organic solvents, aqueous media, etc. are heated to 70 to 95°C to completely dissolve and mix, and then cooled down to some extent, and then the aromatic composition of the present invention is prepared. A solid aromatic composition stable in a gel state is obtained by adding ingredients, coloring agents, preservatives, etc., thoroughly mixing and suspending the mixture, and then pouring it into a suitable mold and allowing it to cool. The obtained molded product can be used as a room air freshener when stored in a suitable container.

Since the aroma composition according to the present invention is manufactured by impregnating a liquid fragrance into an alkyl group-bonded silica gel, the liquid fragrance is retained and adsorbed by the alkyl group-bonded silica gel, and the shelf life of the fragrance is improved. is long. This composition can be molded into a powder, a disc, or a desired shape to suit the intended use, and the shape of the molded product remains stable after molding. The rate of volatilization of fragrance can be controlled. Moreover, in alkyl group-bonded silica gel, the amount of residual silanol is extremely small, so hydrogen bonds between silanol groups and active functional groups of polar compounds such as water and amines hardly occur, unlike in activated silica gel.

Therefore, even if the aroma composition of the present invention is used for a long period of time, it has the advantage that polar compounds in the air are less likely to be adsorbed and react with the fragrance, resulting in denaturation of the fragrance and recessive fragrance.

Next, the present invention will be explained by examples.

Example 1 Alkyl group-bonded silica gel is produced by reacting silica gel from which water has been removed at 400° C. with trichlorooctadecylsilane, and then methoxylating unreacted chloro groups and then trimethylsilylation.

This alkyl group-bonded silica gel (average particle size 10μ) 80
Put g and 30 g of lemon-based blended fragrance (manufactured by Ogawa Kogyo Co., Ltd.) into a 1 liter flask of a rotary evaporator, and
When rotated 40 times per minute at 0° C., the alkyl group-bonded silica gel is impregnated with fragrance in about 10 minutes, and when the rotation is continued for about 30 minutes, a smooth powdery aroma composition with good flowability is obtained.

If 5 g of this aroma composition is placed in a nonwoven bag and placed in a flush toilet, the fragrance will be retained for about 40 days.

After the end of this period, the fragrance volatility was measured and a good result of about 60 was obtained.

Example 2 30g of the lemon fragrance from Example 1 was added to Nonipole Soft SS.
-90 (manufactured by Sanyo Chemical Industries, Ltd.), and then put into a 2-liter flask together with 140 g of the alkyl group-bonded silica gel used in Example 1, and treated in the same manner as in Example 1. The fragrance is impregnated into the alkyl group-bonded silica gel in about 8 minutes, and a powdery fragrance composition is obtained after about 20 minutes.

When 5g of this aromatic composition was placed in a polyethylene film pack with ventilation holes and left in the washroom, the volatility of the fragrance was measured: 25% after 10 days and 36% after 20 days.
, 44% after 30 days, 52% after 40 days, 5 after 50 days
7% and 61% after 60 days.

Example 3 When Pelletex WL (manufactured by Miyoshi Oil Co., Ltd.) was used instead of Nonipole Soft SS-90 in Example 2 and the same treatment as in Example 2 was performed, the volatility of the fragrance after 60 days was 6.
It is 5%.

Example 4 20 g of the lemon-based blended fragrance used in Example 1 was added to 50 g of the alkyl group-bonded silica gel produced in Example 1.
Mix well in a liter beaker to moisten the powder. Then 5 g of the same alkyl group-bonded silica gel and 10 g of magnesium stearate are slowly added and mixing is continued for about 10 minutes. The obtained mixture is molded into a disk with a diameter of 10 mm and a thickness of 3 mm using a compression molding machine (pressure: 3 tons/cm).

This fragrance composition has an aromatic content of about 15% in air under natural ventilation.
There is a fragrance retention period of 0 days.

Example 5 To 70 g of the powder moistened in Example 4, 15 g of magnesium metasilicate and 7 g of aluminum stearate are added and mixing is continued for about 10 minutes.

When the obtained mixture is molded in the same manner as in Example 4, a fragrance composition with substantially the same fragrance retention period is obtained.

Example 6 In a mixture of 10 g of ethylene glycol and 150 g of water,
5 g of agar and 2 g of water-insoluble butadiene copolymer resin are added to a 1 liter beaker and heated to 95°C. When the agar is sufficiently dissolved, 8g of the aroma composition prepared in Example 1
Then add Oda's preservative, stir thoroughly, pour into a suitable mold, and cool.

The obtained aroma composition has shape stability of 50° C. or higher, and has a fragrance retention period of about 60 days.

Example 7 150 g of isoparaffinic hydrocarbon (trade name IP.Solvent 1620), 10 g of hexylene glycol, 10 g of sodium stearate and 1 g of water are placed in a 1 liter beaker and heated to 80°C. After stirring until the sodium stearate is sufficiently dissolved, the mixture is allowed to cool to 60°C. 15 g of the aromatic composition prepared in Example 1 is added thereto, thoroughly stirred, poured into a suitable mold, and cooled.

The obtained aroma composition has shape stability of 60° C. or higher, and has a fragrance retention period of about 80 days.

Example 8 Alkyl group-bonded silica gel is produced by reacting trichlorooctadecylsilane with silica gel from which water has been removed at 600°C. 70 g of this alkyl group-bonded silica gel (average particle size: 10 μm) and 25 g of Osmanthus-based blended fragrance (manufactured by Ogawa Perfume Co., Ltd.) are treated in the same manner as in Example 1 to obtain a powdery aroma composition with good fluidity.

When 5 g of this aromatic composition is placed in a non-woven bag and left indoors under natural ventilation, the fragrance retains for approximately 30 days.

Example 9 To 50 g of the alkyl group-bonded silica gel produced in Example 8, 2.5 g of a lemon-based blended fragrance (manufactured by Soda Perfume Co., Ltd.) is added and thoroughly mixed in a 1-liter beaker to moisten the powder. Next, 20 g of the same alkyl group-bonded silica gel is gradually added, mixing is continued, and molding is carried out in the same manner as in Example 4.

This fragrance composition has an aromatic content of about 18% in air under natural ventilation.
There is a fragrance retention period of 0 days.

Claims (2)

[Claims] 1. 1. A sustained-release aroma composition, characterized in that a liquid fragrance is impregnated into a single substance or a mixture of alkyl group-bonded silica gel obtained by silane treatment of a porous inorganic material. 2. Composition according to claim 1, characterized in that, before impregnation, the liquid perfume is mixed with a non-dissociating surfactant.