JPS6016914A - Slow-releasing perfumery composition and its preparation - Google Patents

Abstract

PURPOSE:To provide a slow-releasing perfumery composition which can be miniturized easily in the form of granules, etc., by coating the surface of a solid particle containing a perfumery, an inert carrier and a binder at specific ratios with a film-forming polymer, etc., thereby enabling the easy setting of the rate of release of the perfumery component. CONSTITUTION:A slow-releasing perfumery composition having the above effects can be produced by preparing a solid particle composed mainly of (A) a perfumery, (B) an inert carrier, and (C) a binder which is soluble preferably in a solvent compatible with the component A (e.g. a polysaccharide derivative such as polysaccharide and/or cellulose derivative), and optionally containing (D) a perfume stabilizer together with the component A, and coating the surface of the particle with (E) a film-forming polymer (e.g. a polysaccharide and/or its derivative) preferably soluble in a solvent having a boiling point of <=120 deg.C or a mixture of said polymer and (F) inorganic powder. The weight ratios of A:B, B:C, and E:F are 1:(0.3-10), 1:(0.1-3) and 1:(0-4), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improved sustained release perfume compositions and methods of making 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 a method in which the fragrance liquid is directly dispersed in the form of a mist, a method in which the fragrance is solidified using rubber, silica gel, activated carbon, etc. as a base material and vaporized at room temperature or by heating, and a container with a limited opening area. There have been proposed methods such as storing the fragrance in a sublimable substance and dispersing the fragrance in a sublimable substance and volatilizing it together with the sublimable substance.

However, there are drawbacks such as the fact that it is not possible to obtain a fragrance composition that is small in size or in the form of granules.

Recently, granular fragrance-emitting substances have been developed, in which a blended fragrance is retained in granular activated alumina, and the surface thereof is coated with a thin film of a cellulose compound that has permeability (Japanese Patent Publication No. 7423/1983), or a hygroscopic adsorbent. Aromatic tablets (Japanese Patent Laid-open No. 53-69
No. 840) has been proposed.

However, in the former case, the initial release rate of the perfume tends to be high, and the release of ζ2 is not sufficiently controlled, and there is a lot of loss of the perfume 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 such conventional technical problems, and it is a film-forming polymer or a film-forming material that covers the surface of solid particles mainly consisting of a fragrance, an inert carrier, and a binder. The coating is coated with a mixture of a synthetic polymer and an inorganic powder, and the weight ratio of the fragrance to the inert carrier is 1:0.3 to 1:10, and the weight ratio of the inert carrier to the binder is 0. The present invention relates to a sustained release fragrance composition in which the weight ratio of film-forming polymer to inorganic powder is 1 to 1:3 and 1 to 1:4, and a method for producing the same.

According to the present invention, it is possible to easily obtain a compact scented body 2 in the form of granules, as required, which has a fragrance retaining property not seen in conventional products. Furthermore (the second is the amount of inert carrier,
It is possible to set the release rate of the fragrance by changing the surface area of the particles, the thickness of the coating, etc. of the binder (it is possible to set the release rate of the fragrance by changing the surface area of the particles, the thickness of the coating, etc.). Therefore, the release rate of fragrance components with different vapor pressures can be adjusted according to the present invention. By preparing a fragrance composition with a set temperature and then mixing and blending, it is possible to provide a stable aroma with no change in fragrance from the initial stage to the final stage of release.Also, according to the present invention The manufacturing method of the fragrance composition suppresses the loss of fragrance during manufacturing,
It has the advantage that the release rate of fragrance can be easily set.
(It is an industrial manufacturing method with a ft cost.

The fragrance targeted by the present invention may be a single component or may be a pre-mixed fragrance. Incidentally, a fragrance stabilizer may be used together with the fragrance if necessary, and in this case, an appropriate fragrance stabilizer is selected from ultraviolet ray confiscation agents and antioxidants.

The inert carrier is preferably one that adsorbs or absorbs the fragrance well and is inert to the fragrance.C:
Examples include inorganic powders such as silicic anhydride, various silicates, and talc, and organic powders such as cellulose powder and polysaccharides and polysaccharide derivatives such as starch.

Examples of binders include polysaccharides such as starch, pullulan, and xanthan gum, polysaccharide derivatives such as cellulose derivatives, and synthetic polymers such as polyamides, polyesters, polyethers, and vinyl polymers. Binders that are soluble in compatible solvents are preferred.

The film-forming polymer is preferably one that allows fragrance to pass through to an appropriate degree, and these include starch, pullulan, polysaccharides such as xanthan gum, polysaccharide derivatives such as cellulose derivatives, polyamide, polynisdel, polyether, vinyl polymers, etc. Examples include synthetic polymers. Among these, it has film-forming properties that dissolve in solvents with a boiling point of 120°C or higher! Combination is considered suitable. However, even if an inorganic powder is mixed with this film-forming polymer as necessary, this will have the effect of making it easier to control the release rate of the fragrance that passes through the coating layer. It will be done. 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 are used as the above-mentioned binders and film-forming polymers, but among these, particularly those that are decomposed by bacteria or enzymes and do not accumulate in nature are used. It is desirable to have a limited selection.

The sustained release fragrance composition of the present invention is composed of the fragrance described above, a fragrance stabilizer, an inert PE compound, a binder, a film-forming polymer, an inorganic powder, etc. From the standpoint of achieving the purpose, it is desirable that the proportions of each of these components be as follows. Note that each component is not limited to one type, and there is no problem in using two or more types of components in the same category in combination.

Solid particle fragrance 0.5 to 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 /1 With a composition of combinations that total 100% within each of the above ranges,
And as mentioned above, the weight ratio of the fragrance and the inert carrier is 1.
: 0.3 to 1:10, the weight ratio of the inert carrier to the binder is 1:0.1 to 1:3, and the ratio of the film-forming polymer to the inorganic powder in the coating layer is 0 to 1: 4 (it is preferable to choose 2), so that the fragrance content is 0.
．． If it is less than 5% by weight, the fragrance release rate +V will be extremely small and the fragrance effect will not be exhibited, and the -fragrance content will be 60% by weight.
Nothing beats %Z! l! ! There are disadvantages such as increased loss of fragrance during IM and difficulty in controlling the release rate. On the other hand, if the binder content is less than 1%, the evaporation rate of the fragrance during production increases.

In either case, the release rate of the perfume can be set to a desired rate (rff) by selecting the appropriate ratios of perfume, inert carrier, binder, film-forming polymer, and inorganic powder.

The sustained release fragrance composition of the present invention is produced as follows.

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 fingers. 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 (in powder form) is added and mixed, the solvent of the binder is added and kneaded, and preferably the average particle size is adjusted using a suitable granulating device. 0
．． It is made into granules (solid particles) of 3 to 10 mm. It is desirable that the binder solvent used at this time 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, which is disadvantageous. It is.

2. The surface of the solid particles produced in this way is coated with a film-forming polymer or a mixture of a film-forming polymer and an inorganic powder. A method of spraying and drying a solvent solution of a film-forming polymer or a C2 inorganic powder suspended in the solvent solution while maintaining the solid particles in a fluid state, or (b) a method of drying the solid particles with a C2 film A solvent solution of the forming polymer is added and mixed, and then this mixture l:
Granular C by adding inorganic powder: After dividing, if necessary, drying under fluidized conditions can be mentioned.

In the method (a) above, solid particle flow conditions I:
It is desirable that the coating operation is carried out under conditions where the temperature of the solid particles is low, and specifically, it is 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 the fragrance during the spraying operation, which is disadvantageous, and if it is too low, the evaporation of the solvent in the sprayed liquid will be extremely slow, causing particles to stick together. Uniform coverage will not be achieved. As the solvent for the film-forming polymer, it is preferable to use a solvent with an Hr/point of 120°C or less; if the solvent has a boiling point higher than 120'C, evaporation is slow and particles tend to stick together. Furthermore, in such a case, it is necessary to set the temperature of the solid particles above 50° C. to promote the evaporation of the solvent, resulting in an inconvenience that the evaporation loss of the fragrance increases.

Further, it is preferable that the concentration of the film-forming polymer in the spray liquid is usually in the range of 0.5 to 10%. Inorganic powder is suspended and added to this spray liquid within the above-mentioned range as required, but this makes it easy to set the fragrance release rate to an appropriate level, and also makes it easier to set the fragrance release rate to an appropriate level. The adhesion of the particles to each other occurs, reducing C2, which not only makes it possible to achieve uniform coating, but also allows the coating operation to be carried out at a relatively low particle temperature. (B)
In method (2), it is easier to set the fragrance release rate to an appropriate level by incorporating an inorganic powder into the coating layer.

Next [: I will give a specific example.

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. Methylene chloride/ethanol (9
18 parts of a 5% /1 weight ratio solution were added and kneaded and granulated using a known extrusion granulation device to obtain spherical and cylindrical composite granules with an average particle diameter of 1 mm.

Next, ethanol/ethanol of ethylcellulose (trade name: Ethocel Standard, manufactured by Dow Chemical Company) is added to the granules.
A 4% toluene (s/2 weight ratio) solution was spray coated in a fluidizer using air at 45°C as a fluidizing medium to form a 30% by weight coating on the composite granules.

The resulting fragrance composition was dissolved and extracted in acetone, and analyzed by gas chromatography using methyl laurate as an internal standard. It was found that 32.0% by weight of α-
Contains limonene.

Next, 313 pieces of this fragrance compound were heated at 30°C and at a wind speed of 0.
The sample was placed under conditions of 5 m and 7 seconds, and the amount of α-limonene released was measured by quantitative analysis using weight change and internal standard gas chromatography, and the yields shown in Table 1 were obtained.

Example 2 The elementary granules obtained in Example 1 were used and 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 resulting 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, the release of l2α-limonene was measured for this perfume composition 332m in the same manner as in Example 1, and 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 7 parts by weight of cellulose was added as a binder.
(D Methylene chloride/ethanol (9/1 g fft
Example 1
A cumulative granule was obtained in the same manner as above. Next, the cumulative 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 resulting perfume package 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, the amount of l-α-limonene released from this fragrance composition 370 was measured in the same manner as in Example 1.
The results shown in the table were obtained.

From the data of each 7+fa example in Table 1, it was confirmed that the rate of U release can be set by changing the amounts of the binder and film-forming substance.

Comparative Example 1 Hydroxy blow 16 to powdered aluminum hydroxide
- Bill methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name TC-5R)
) as a binder, granulated into spheres with an average particle size of 2 mm,
30 parts by weight of activated activated alumina, 1 part of α-limonene
After adsorbing 0 parts by weight, a 6% solution of ethylcellulose in ethanol/toluene (8/2Mi ratio) was spray coated under the same conditions as in Example 1.
- Limone yg was only 43% of the initial content and the evaporation loss was large.

Examples 4 to 6 Sustained-release fragrance compositions similar to Examples 1 to 3ζ2, 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)) TPMC-
Hydroxypropyl methylcellulose OA = Cellulose acetate PVA = Polyvinyl alcohol RP C-Hydroxybutylene cellulose Example 7 3 oitrs parts of soft silicic anhydride are mixed with 30 oitrs parts of α-limonene, and then methylene chloride of cellulose acetate is used as a binder. 180 parts by weight of a 5% /ethanol (9/1 weight ratio) solution was added and kneaded and granulated using a known extrusion granulation device to obtain spherical and cylindrical elementary granules with an average particle size of 1.

Next, 100 parts by weight of a 4% solution of ethanol/toluene (8/2 rainfall ratio) of Niethylcellrone [A, ψ own material] [a suspension of Nitalc quadruple ridges] was placed in a fluidizing device. Spray coating was performed using air at 36° C. as a moving medium to form a coating of 40% by weight on the granules. During the coating operation, no particle adhesion occurred and a good coating operation was achieved.

The obtained fragrance composition 4 was dissolved and extracted in acetone and analyzed by gas chromatography using methyl laurate as an internal standard. It was found that α was 31.0% by weight based on the total Ml.
- It was confirmed that limonene was contained and there was almost no evaporation loss of fragrance during operation.

ζ2, this fragrance composition 323 town at 30℃, wind speed Q,
When placed under the condition of 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 3 were obtained.

Example 8 Using the composite granules obtained in Example 7, spray coating was performed in the same manner as in Example 7, and 65% by weight of the composite granules was applied.
A film was formed. When the obtained fragrance composition was analyzed in the same manner as in Example 7, it was found that it was 26.0% by weight based on the total weight.
of α-limonene was contained. Next, the amount of α-limonene released from this perfume composition 385rr1g+:1 was measured in the same manner as in Example 7, and the results shown in Table 3 were obtained.

Example 9 The composite granules obtained in Example 7 were used, and ethyl cellulose ethanol/toluene (8/2 weight ratio) system 4 was added to the composite granules.
A suspension of 1.5 wt. 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 284% by weight based on the total weight. Next, this fragrance composition 352
When the amount of diα-limonene released was measured in the same manner as in Example 7, the results as shown in Table 3 were obtained.

From the results shown in Table 3, it was confirmed that Examples 7 to 9 also exhibited excellent sustained release properties.

Example 10 50 parts by weight of the cumulative granules obtained in Example 7 C dihydroxypropyl methylcellulose (trade name TC-5R, manufactured by Shin-Etsu Chemical Co., Ltd.)
After adding and mixing 50 parts by weight of a 25% aqueous solution of , 40 parts by weight of talc was added, the mixture was divided into particles, and the mixture was fluidized and dried. The obtained fragrance composition was analyzed in the same manner as in Example 23-Example 7, and it was found that 2446 of the total amount of
It contained a significant amount of α-limonene.

Examples 11 to 13 □ According to Examples 7 to 9, the types and content of fragrance, inert extrusion, binder, film-forming polymer, and inorganic powder were as shown in Table 4. A release perfume composition was prepared. All of these exhibited good sustained release properties.

24- -25- -75

Claims (1)

[Scope of Claims] 1. The surface of solid particles made of a living body containing a fragrance, an inert carrier, and a binder is coated with a film-forming polymer or a mixture of a film-forming polymer and an inorganic powder,
The weight ratio of the fragrance and the inert carrier is 1:0.3 to 1:1.
0, the weight ratio of inert carrier and binder is 1: (1,
1 to 1:3, a sustained release fragrance composition 2 in which the weight ratio of the film-forming polymer to the fine filamentous powder is 1:0 to 1:4, together with the fragrance (with the addition and blending of two fragrance stabilizers) Sustained-release fragrance composition 3 according to claim 1, which has an average particle size of 0.3.
The sustained-release fragrance composition 4 according to claim 1, which is a granular material with 10 fins; a sustained release fragrance composition 5, a sustained release fragrance composition 6 according to claim 1, wherein the binder is one or more selected from the group consisting of polysaccharides and polysaccharide derivatives; Sustained-release fragrance composition 7 according to claim 1, wherein the film-forming polymer is soluble in a solvent having a boiling point of 120°C or lower.The film-forming polymer is selected from the group consisting of polysaccharides and polysaccharide derivatives. The sustained release fragrance composition 8 according to claim 1, which is one or more selected polysaccharide derivatives. Claim 5 or 7, wherein the polysaccharide derivative is a cellulose derivative. Sustained-release fragrance composition 9, in which a film-forming polymer or a film-forming polymer and an inorganic powder are added to solid particles mainly composed of a fragrance, an inert phase, and a binder while maintaining them in a fluid state. Method 10 for producing a sustained-release fragrance composition, characterized by spraying and drying a coating liquid containing a film-forming polymer solution to solid particles mainly consisting of a fragrance, an inert carrier, and a binder. A method for producing a sustained-release fragrance composition, which comprises mixing, adding an inorganic powder to the mixture, dividing the mixture into granules, and then drying the composition.