JPS6229056B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to improved sustained release perfume compositions and methods for producing the same. Generally, fragrances (including deodorants) are volatile and their effects are temporary, so various attempts have been made to gradually release fragrances over a long period of time. Conventional fragrances include methods in which the fragrance liquid is directly dispersed in the form of a mist, methods in which the fragrance is solidified using rubber, silica gel, activated carbon, etc. as a base material and volatilized at room temperature or under heat, and methods in which the open area of the fragrance is limited. There have been proposed methods such as storing the perfume in a sublimable container and dispersing the perfume in a sublimable substance and volatilizing it together with the sublimable substance. However, these methods have drawbacks such as requiring special equipment to volatilize the fragrance, insufficient persistence of the fragrance, and the inability to obtain a compact fragrance composition such as granules. . In addition, recently, granular fragrance materials (Special Publications 1983-1983-1) have been developed, in which granular activated alumina is made to hold a blended fragrance, and then its surface is coated with a thin film of an air-permeable cellulose compound.
7423), or aromatic tablets in which fragrance is adsorbed on a hygroscopic adsorbent, then molded, and coated with a polymeric coating agent to such an extent that the fragrance evaporates upon heating (Japanese Patent Laid-Open No. 53-69840). is proposed. However, in the former case, the initial release rate of the fragrance tends to be high, the release is not sufficiently controlled, and there is a lot of loss of the fragrance during production. The latter also has the disadvantage that fragrance is not released at room temperature. The present invention was completed as a result of intensive research in view of the conventional technical problems, and it is made by granulating inert carrier powder adsorbed with fragrance using a binder. It is coated with a continuous layer-like coating layer made of a mixture of a polymer or a film-forming polymer and an inorganic powder and is permeable to the fragrance, and the weight ratio of the fragrance and the inert carrier is 1:0.3 to 0.3. 1:10, the weight ratio of the inert carrier to the binder is 1:0.1 to 1:3, and the weight ratio of the film-forming polymer to the inorganic powder is 1:0 to 1:0.
The present invention relates to a sustained release fragrance composition with a ratio of 1:4 and a method for producing the same. According to the present invention, it is possible to easily obtain a compact, granular fragrance body as required, which has aroma retention properties not found in conventional products. Furthermore, by varying the amount of inert carrier, the amount of binder, the surface area of the particles, the thickness of the coating, etc., it is possible to set the release rate of the perfume. Therefore, according to the present invention, perfume components with different vapor pressures are made into a perfume composition with respective release rates set, and then mixed and formulated, it is possible to create a stable formulation without any change in fragrance from the initial stage to the final stage of release. It can provide a unique aroma. Furthermore, the method for producing a fragrance composition of the present invention has the advantage of minimizing the loss of fragrance during production and making it possible to easily set the release rate of the fragrance, and is a low-cost industrial manufacturing method. The fragrance targeted by the present invention may be a single component or may be a pre-mixed fragrance. Incidentally, a fragrance stabilizer is used along with the fragrance if necessary, and in this case, a suitable fragrance stabilizer is selected from ultraviolet absorbers and antioxidants. The inert carrier is preferably one that adsorbs or absorbs the fragrance well and is inert to the fragrance, such as inorganic powders such as silicic anhydride, various silicates, and talc, cellulose powder, and starch. Examples include organic powders such as polysaccharides and polysaccharide derivatives. In addition, as binders, starch, pullulan,
Polysaccharides such as xanthan gum, polysaccharide derivatives such as cellulose derivatives, polyamides, polyesters,
Synthetic polymers such as polyether and vinyl polymers are exemplified, but binders that are soluble in solvents that are compatible with perfumes are particularly preferred. For film-forming polymers, it is necessary that the resulting film is moderately permeable to fragrances, and this includes polysaccharides such as starch, pullulan, and xanthan gum, polysaccharide derivatives such as cellulose derivatives, polyamides, and polyesters. Examples include synthetic polymers such as , polyether, and vinyl polymers. Among these, film-forming polymers that dissolve in solvents with a boiling point of 120° C. or lower are preferred. Therefore, an inorganic powder may be mixed with this film-forming polymer if necessary.
According to this, it is possible to more easily control the rate of release of the fragrance that passes through the coating layer. Examples of inorganic powders used for this purpose include silicic anhydride, various silicates, and talc. Incidentally, waxes such as stearic acid may be used in combination with this film-forming polymer as a film-forming agent. Natural or synthetic polymeric substances can be used as the above-mentioned binder and film-forming polymer, but among these, those that are decomposed by bacteria or enzymes and are not accumulated in nature are selected. This is desirable. The sustained release fragrance composition of the present invention is composed of the fragrance described above, a fragrance stabilizer, an inert carrier, a binder, a film-forming polymer, an inorganic powder, etc.
From the viewpoint of achieving the objective of the present invention, which is sustained release, it is desirable that the proportions of these components used are as follows. Note that each component is not limited to one type each, and there is no problem in using two or more types of components in the same category in combination. Solid particle fragrance 0.5-60% by weight Perfume stabilizer 0-6 〃 Inert carrier 10-50 〃 Binder 1-30 〃 Coating layer film-forming polymer 5-50 〃 Inorganic powder 0-30 〃 Each of the above It is desirable that the composition is a combination that makes up a total of 100% within the range, and as mentioned above, the weight ratio of fragrance and inert carrier is 1:0.3 to 1:0.3.
1:10, the weight ratio of inert carrier to binder is 1:1.
It is necessary to select the composition so that the ratio of the film-forming polymer to the inorganic powder in the coating layer is 0.1 to 1:3 and 1:0 to 1:4. If the fragrance content is less than 0.5% by weight, the release rate of the fragrance will be extremely low and the fragrance effect will not be exhibited.
On the other hand, if the fragrance content exceeds 60%, there will be a lot of fragrance loss during production, and there will be problems such as difficulty in controlling the release rate. On the other hand, the binder is 1
If the composition is less than %, the evaporation loss of the fragrance during production will be large. In any case, fragrance, inert carrier, binder,
By selecting an appropriate ratio of the film-forming polymer and the inorganic powder, the release rate of the fragrance can be set to a desired value. The sustained release fragrance composition of the present invention is prepared by first granulating an inert carrier powder adsorbing a fragrance using a binder solution dissolved in a solvent compatible with the fragrance, and then drying it to form solid particles, (a) While maintaining the solid particles in a fluid state, spray a solution of a film-forming polymer in a solvent with a boiling point of 120°C or less or a mixed solution of this with an inorganic powder onto the entire surface of the solid particles, or (b) dry the solid particles. It is manufactured by adding a solution of the film-forming polymer in the above-mentioned solvent to coat the entire surface thereof, adding an inorganic powder thereto to keep it in a granular form, and then drying it. To explain this in more detail, first, a fragrance, an inert carrier, and, if necessary, a fragrance stabilizer are charged and mixed in a mixer, so that the fragrance is adsorbed onto the inert carrier. At this time, the perfume may be diluted with a suitable organic solvent to achieve more uniform mixing.
Next, a solvent solution of the binder is added and kneaded, or after the binder is added and mixed in powder form, a solvent for the binder is added and kneaded, and the average particle size is preferably 0.3 using a suitable granulating device. ~10mm granules (solid particles). The binder solvent used at this time must be compatible with the fragrance; if a solvent that is not compatible with the fragrance is used, the fragrance may be liberated from the particle surface during granulation. It's inconvenient. Next, a coating layer is formed on the surface of the solid particles produced in this way with a film-forming polymer or a mixture of a film-forming polymer and an inorganic powder. The coating operation under flow conditions is preferably carried out under conditions where the temperature of the solid particles is low, and specifically preferably carried out under a temperature condition in the range of 5°C to 50°C. If this temperature is too high, there will be a lot of evaporation loss of fragrance during the spraying operation, which is inconvenient.
On the other hand, if it is too low, the evaporation of the solvent in the spray liquid will be extremely slow, particles will stick to each other, and uniform coating will not be achieved. In addition, it is necessary to use a solvent for the film-forming polymer with a boiling point of 120°C or lower; if the solvent has a boiling point higher than 120°C, evaporation is slow and particles tend to stick together. In such cases, the temperature of the solid particles may be increased to 50°C to promote evaporation of the solvent.
It is necessary to set the temperature above 0.degree. C., which causes the disadvantage that evaporation loss of fragrance increases. Further, the concentration of the film-forming polymer in the spray liquid is usually preferably in the range of 0.5 to 10% by weight. If necessary, inorganic powder is suspended and added to this spray liquid within the above-mentioned range, but this makes it easy to set the fragrance release rate to an appropriate level, and also makes it possible to This makes it difficult for the particles to stick together, and not only can a uniform coating layer be formed, but also allows the coating operation to be performed at a relatively low particle temperature. In the method (b) as well, by incorporating inorganic powder into the coating layer, it becomes easy to set the release rate of the fragrance to an appropriate level. Note that this drying can also be carried out under fluidized conditions, if necessary. Next, a specific example will be given. Example 1 30 parts by weight of soft silicic anhydride (trade name Aerosil, manufactured by Nippon Aerosil Co., Ltd.) was mixed with 30 parts by weight of α-limonene, and then cellulose acetate (trade name L-20, manufactured by Daicel Chemical Co., Ltd.) was added as a binder. 5% methylene chloride/ethanol (9/1 weight ratio) solution
180 parts by weight were added and kneaded and granulated using a known extrusion granulation device to obtain spherical and cylindrical elementary granules with an average particle diameter of 1 mm. Next, the elementary granules were spray coated with a 4% solution of ethyl cellulose (product name: Ethocel Standard, manufactured by Dow Chemical Company) in an ethanol/toluene (8/2 weight ratio) system in a fluidizer using air at 45°C as a fluidizing medium. Then, a coating of 30% by weight was formed on the elementary granules. The obtained fragrance composition is dissolved and extracted in acetone,
When analyzed by gas chromatography using methyl laurate as an internal standard, it was found that
It contained 32.0% by weight of α-limonene. Next, 313 mg of this fragrance composition was heated at 30°C and at a wind speed.
When placed under conditions of 0.5 m/sec and quantitatively analyzing the amount of α-limonene released by weight change and internal standard gas chromatography, the results shown in Table 1 were obtained. Example 2 The elementary granules obtained in Example 1 were used, and Example 1
Ethyl cellulose was spray coated in the same manner as above to form a coating of 40% by weight on the elementary granules.
When the obtained fragrance composition was analyzed in the same manner as in Example 1, it was found that it contained 30.1% by weight of α-limonene based on the total weight. Next, this fragrance composition
When the amount of α-limonene released was measured for 332 mg in the same manner as in Example 1, the results shown in Table 1 were obtained. Example 3 30 parts by weight of light silicic anhydride was mixed with 30 parts by weight of α-limonene, and then 180 parts by weight of a 10% solution of cellulose acetate in methylene chloride/ethanol (9/1 weight ratio) system was added as a binder. The mixture was kneaded and subjected to the same operation as in Example 1 to obtain elementary granules. Next, the elementary granules were spray coated with ethyl cellulose in the same manner as in Example 1 to form a coating of 40% by weight on the elementary granules. When the obtained fragrance composition was analyzed in the same manner as in Example 1, it was found that it contained 27.0% by weight of α-limonene based on the total weight. Next, α-
When the amount of limonene released was measured, the results shown in Table 1 were obtained.

[Table] From the data of each example in Table 1, it was confirmed that the release rate could be set by changing the amounts of the binder and film-forming substance. Comparative Example 1 Hydroxypropyl methylcellulose (product name: TC manufactured by Shin-Etsu Chemical Co., Ltd.) was added to powdered aluminum hydroxide.
-5R) as a binder, 30 parts by weight of activated alumina granulated and activated into spheres with an average particle size of 2 mm,
After adsorbing 10 parts by weight of α-limonene, a 6% solution of ethyl cellulose in ethanol/toluene (8/2 weight ratio) was spray coated under the same conditions as in Example 1. The evaporation loss was only 43%. Examples 4 to 6 Sustained-release fragrance compositions according to Examples 1 to 3, in which the types and contents of the fragrance, inert carrier, binder, and film-forming polymer are as shown in Table 2. was manufactured. All of these exhibited good sustained release properties. The abbreviations in Table 2 have the following meanings. (Abbreviation for binder, film-forming polymer) HPMC = Hydroxypropyl methyl cellulose CA = Cellulose acetate PVA = Polyvinyl alcohol HPC = Hydroxypropyl cellulose

[Table] Example 7 30 parts by weight of soft silicic anhydride was mixed with 30 parts by weight of α-limonene, and then 180 parts by weight of a 5% methylene chloride/ethanol (9/1 weight ratio) solution of cellulose acetate was added as a binder. The mixture was added and kneaded and granulated using a known extrusion granulation device to obtain spherical and cylindrical elementary granules with an average particle diameter of 1 mm. Next, a 4% solution of ethylcellulose in ethanol/toluene (8/2 weight ratio) was added to the elementary granules.
A suspension prepared by suspending 4 parts by weight of talc in 100 parts by weight was spray coated in a fluidizer using air at 36° C. as a fluidizing medium to form a coating of 40% by weight on the elementary granules. During the coating operation, no particle adhesion occurred and a good coating operation was achieved. The obtained fragrance composition is dissolved and extracted in acetone,
When analyzed by gas chromatography using methyl laurate as an internal standard, it was found that
It was confirmed that it contained 31.0% by weight of α-limonene, and that there was almost no evaporation loss of fragrance during operation. Next, 323 mg of this fragrance composition was heated at 30°C and at a wind speed.
When placed under conditions of 0.5 m/sec and quantitatively analyzing the amount of α-limonene released using weight change and internal standard gas chromatography, the results shown in Table 3 were obtained. Example 8 Using the elementary granules obtained in Example 7, spray coating was carried out in the same manner as in Example 7 to form a coating of 65% by weight on the elementary granules. When the obtained fragrance composition was analyzed in the same manner as in Example 7, it was found that it contained 26.0% by weight of α-limonene based on the total weight. Next, the amount of α-limonene released was measured for 385 mg of this perfume composition in the same manner as in Example 7, and the results shown in Table 3 were obtained. Example 9 The elementary granules obtained in Example 7 were used, and ethylcellulose ethanol/toluene (8/
2 weight ratio) A suspension of 1.5 parts by weight of talc in 100 parts by weight of a 4% solution of the system was spray coated in a fluidizer using air at 33°C as a fluidizing medium to form a 50% by weight coating on the elementary granules. Formed. When this perfume composition was analyzed in the same manner as in Example 7, it was found that α-limonene was contained in an amount of 28.4% by weight based on the total weight. Next, the amount of α-limonene released from 352 mg of this fragrance composition was measured in the same manner as in Example 7, and the results shown in Table 3 were obtained.

[Table] From the results in Table 3, it was confirmed that Examples 7 to 9 also exhibited excellent sustained release properties. Example 10 Hydroxypropyl methylcellulose (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 50 parts by weight of the elementary granules obtained in Example 7.
After coating by adding 50 parts by weight of a 25% aqueous solution of TC-5R), 40 parts by weight of talc was added to keep it granular and fluidized drying was carried out. When the obtained fragrance composition was analyzed in the same manner as in Example 7, it was found that the total weight of
It contained 24.6% by weight of α-limonene. Examples 11 to 13 Sustained release according to Examples 7 to 9, in which the types and contents of fragrance, inert carrier, binder, film-forming polymer, and inorganic powder are as shown in Table 4. A perfume composition was produced. All of these exhibited good sustained release properties.

【table】

Claims (1)

[Scope of Claims] 1. The entire surface of solid particles obtained by granulating inert carrier powder adsorbed with a fragrance using a binder is coated with a fragrance consisting of a film-forming polymer or a mixture of the same and an inorganic powder. The perfume and the inert carrier are coated with a continuous layer-like coating layer that is permeable to the fragrance, and the weight ratio of the fragrance and the inert carrier is 1:0.3 to 1:10, and the weight ratio of the inert carrier and the binder is 1:0.1 to 1:0.1. 1:3, the weight ratio of film-forming polymer and inorganic powder is 1:0 to
A sustained release fragrance composition with a ratio of 1:4. 2. The sustained-release fragrance composition according to claim 1, which comprises a fragrance stabilizer and a fragrance. 3. The sustained release fragrance composition according to claim 1, wherein the solid particles are granules having an average particle diameter of 0.3 to 10 mm. 4. The sustained release fragrance composition according to claim 1, wherein the binder is dissolved in a solvent that is compatible with the fragrance. 5. The sustained release fragrance composition according to claim 1, wherein the binder is one or more selected from the group consisting of polysaccharides and polysaccharide derivatives. 6. The sustained release fragrance composition according to claim 1, wherein the film-forming polymer is soluble in a solvent having a boiling point of 120°C or lower. 7. The sustained release fragrance composition according to claim 1, wherein the film-forming polymer is one or more selected from the group consisting of polysaccharides and polysaccharide derivatives. 8. The sustained release fragrance composition according to claim 5 or 7, wherein the polysaccharide derivative is a cellulose derivative. 9 The inert carrier powder adsorbing the fragrance is granulated using a binder solution dissolved in a solvent that is compatible with the fragrance, and then dried to form solid particles. A solvent solution of a film-forming polymer with a boiling point of 120°C or less or a mixed solution of this with an inorganic powder is sprayed onto the surface and dried to form a continuous layered coating layer that is permeable to perfume over the entire surface of the solid particles. 1. A method for producing a sustained-release fragrance composition, the method comprising: forming a sustained-release fragrance composition. 10 The inert carrier powder adsorbing the fragrance is granulated using a binder solution dissolved in a solvent compatible with the fragrance, and then dried to form solid particles, which are then granulated with the boiling point of the film-forming polymer at 120°C. The following solvent solution is added to coat the entire surface of the solid particles, an inorganic powder is added to this to maintain the granular shape, and the solid particles are then dried to form a continuous layered coating that is permeable to perfume on the entire surface of the solid particles. A method for producing a sustained release fragrance composition, which comprises forming a layer.