JPS6363229B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sustained release product comprising a calcium phosphate compound. There are known sustained-release materials in which a substance to be released, such as a fragrance, is adsorbed to a sustained-release substance (activated carbon, silica gel, felt, sawdust, synthetic resin composite) as a base material (fragrance is explained below as a typical example). be. The following are the main properties required for sustained release substances. It must be able to adsorb more than a predetermined amount of fragrance, it must have excellent retention of the adsorbed fragrance, and it must also release the fragrance little by little over a long period of time, and it must not cause any chemical changes in the adsorbed fragrance. As is well known, fragrances are originally volatile organic compounds, and their effectiveness as fragrances is expressed by their volatility. However, among known sustained-release substances, substances with a large adsorption amount tend to be unsuitable for long-term use because they have poor fragrance retention, and may also cause chemical changes in the fragrance. be. In view of the current situation, the present inventor has conducted various studies and found that Ca is in the range of 1.0 to 2.0 mol per mol of P and the specific surface area by BET method is 50 to 300.
The present inventors have discovered that a calcium phosphate compound within the range of m ² /g has all of the above-mentioned properties required for a sustained release substance, and have completed the present invention. That is, in the present invention, Ca/P (molar ratio) = 1.0 to 2.0, and the specific surface area by BET method is 50 to 300.
The ^present invention relates to a calcium phosphate-based sustained release material (hereinafter referred to as the first invention of the present application), which is formed by adsorbing a fragrance onto a base material made of a calcium phosphate-based compound having a particle size of m 2 /g. A base material made of the calcium phosphate compound of the first invention of the present application, which is pressure-molded as it is, may be destroyed during the impregnation operation in a perfume or its alcohol diluted system. According to the research of the present inventor, when a calcium phosphate compound is formed into a spherical molded body with a diameter of approximately 1 to 10 mm using a water-soluble polymer as a binder, the properties of ~ as a sustained release substance are not impaired in any way. It was found that the destruction phenomenon during perfume impregnation was reduced. That is, the present invention further provides a calcium phosphate compound having a Ca/P (molar ratio) of 1.0 to 2.0 and a specific surface area of 50 to 300 m ² /g by the BET method as a base material, and a water-soluble polymer as a binder. The present invention relates to a calcium phosphate sustained release material (hereinafter referred to as the second invention of the present application), which is formed by adsorbing a fragrance to a spherical molded product having a diameter of 1 to 10 mm. In the first invention of the present application, Ca/P (molar ratio) = 1.0 to 2.0, from the viewpoints of adsorption of the fragrance, retention and sustained release of the adsorbed fragrance, low chemical influence on the adsorbed fragrance, etc. Specific surface area by BET method = 50 ~
It is essential to use a calcium phosphate compound with an area of 300 m ² /g as the base material. If the Ca/P (molar ratio) is less than 1.0 or greater than 2.0, there is a tendency for the adsorbed fragrance to change in quality.
Ca/P (molar ratio) is preferably 1.5 to 1.7. Calcium phosphate having a Ca/P (molar ratio) of 1.5 to 1.7 is known as hydroxyapatite. Also, the specific surface area by BET method is 50m ² /g
If the amount is less than 300 m ² /g, the amount of fragrance adsorbed is insufficient, whereas if it is more than 300 m 2 /g, the amount of adsorption is sufficient, but the retention and sustained release properties tend to deteriorate. The specific surface area is more preferably 100 to 250/g. The calcium phosphate compound may be used as a powder as it is in a container, or may be used as a pressure-molded product without using a binder. Furthermore, it may be granulated mechanically using a granulator. In the second invention of the present application, a diameter of 1 to 10 mm is obtained by adding a binder made of a water-soluble polymer to a base material made of a calcium phosphate compound similar to the first invention of the present application.
A spherical molded product of about mm size is used as a sustained release body. In the second invention of the present application, a fibrous substance may be used in combination with a binder. The spherical molded article in the second invention of the present application is preferably manufactured by an in-liquid curing method known as a method for manufacturing microcapsules. For example, when using hydroxyapatite with a Ca/P (molar ratio) of about 1.5 to 1.7 as a base material, a mixture containing a hydroxyapatite aqueous suspension, a water-soluble polymer, and a fibrous substance as necessary. is dropped into a bath containing a curing agent for the water-soluble polymer through an orifice,
After curing in a bath, a spherical molded product can be obtained by washing with water and drying. The particle size of the molded body can be determined by adjusting the concentration of water-soluble polymer in the mixture (i.e. particle size of the mixture), droplet size, dropping distance, etc.
It can be adjusted arbitrarily. Water-soluble polymer-curing agent systems include sodium alginate-Ca ⁺⁺ (calcium ions derived from water-soluble calcium salts such as calcium chloride and calcium nitrate), polyvinyl alcohol-borax or formaldehyde, and carboxymethyl cellulose-Fe ^{3 +} etc. are exemplified. The amount of water-soluble polymer used relative to the calcium phosphate compound is usually about 1 to 10 parts by weight per 100 parts by weight of the former. If necessary, the fibrous material used in the second invention of the present application can more effectively prevent the phenomenon of destruction of the sustained release body during perfume impregnation, and increase the number of communication holes in the sustained release body to prevent the substance to be released. It increases the adsorption amount of , improves its retention, and exhibits sustained release over a longer period of time. Such fibrous materials include various natural and synthetic fibers, including protein fibers such as silk and wool, cellulose fibers such as cotton, linen, and pulp, mineral fibers such as asbestos, and polyamide fibers. Examples include synthetic fibers such as polyester, polyester, polyacrylonitrile, polyvinyl alcohol, and polyvinylidene chloride. The fibrous material preferably has a length of about 100 to 350 μm and a thickness of about 10 to 50 μCm.
The amount of the fibrous material to be used relative to the calcium phosphate compound is preferably about 5 to 20 parts by weight per 100 parts by weight of the former. Substances to be adsorbed and retained in the sustained-release body of the present invention include perfumes that can volatilize into the atmosphere under normal conditions, and perfumes that diffuse outside the sustained-release body in the presence of moisture or by heating. Examples of such fragrances are as follows. 1 Natural fragrances... Ziya incense, Reineko incense, Dragon lily incense, Abyss oil, Bergamot oil, Boarose oil, Rosewood oil, Rosemary oil, Orange flower oil, Lemon oil, Grapefruit oil, Cardamom oil, Cinnamon oil, Konyaku oil, Mitsuthyamatsuka oil, spearmint oil, diasmine absolute, Borneo camphor oil, etc. 2 Synthetic fragrances...ethyl acetoacetate, anethole,
Amylcinamic aldehyde, ethyl isovalerate, isoamyl acetate, undecalactone, vanillin, ethylene bramylate, eugenol, ethyl caprylate, allyl caproate, ethyl caproate, l-carvone, cumin aldehyde, cinnamic alcohol, geraniol, Dimethylbenzylcarbinyl acetate, citral, citronellol, dihydrdiasmone,
Dimethylbenzyl carbinol, tetrahydrolinalool, terpineol, β-naphthyl ethyl ether, nonalactone, hydroxycitronellal, β-phenylethyl alcohol,
Ethyl phenyl acetate, benzyl acetate, benzyl alcohol, maltol, musk, n-
Methyl anthranilic acid, menthol, ionone,
Linalool, limonene, etc. 3. Mixed fragrances: rose, diasmine, lilac, osmanthus, carnation, miyuge, etc. The sustained release material of the present invention has excellent fragrance absorption, retention and sustained release properties, is strong, and has a smooth surface and excellent appearance as a molded product, so it can be used for indoor use, toilet use, automobile use, etc. It is useful as a sustained release form of Example 1 Calcium hydroxide aqueous suspension with a concentration of 10% by weight 7.4
1.47 kg of phosphoric acid aqueous solution with a concentration of 40% by weight was gradually added at room temperature while stirring vigorously to form hydroxyapatite.
Approximately 1 kg of powder obtained by dehydrating the product, washing with acetone, drying and crushing, Ca/P (molar ratio) = approx.
1.64, and the specific surface area by BET method was 180 m ² /g. When 5 g each of the thus obtained hydroxyapatite powder was taken and molded at a pressure of 100 kg/ ^cm2 , a prismatic molded body was impregnated with the various fragrances shown in Table 1 for 3 hours, and the adsorption results shown in Table 1 were obtained. It was done. When the fragrance-adsorbing molded article obtained above was left at room temperature, the fragrance continued to emit for more than three months. Comparative Example 1 When 5 g of commercially available granular silica gel was impregnated with various fragrances shown in Table 1 for 3 hours, the adsorption results shown in Table 1 were obtained. When silica gel adsorbed with these fragrances was left at room temperature, it stopped emitting fragrance within two months. Example 2 500g of hydroxyapatite powder obtained in Example 1
is granulated using a granulator using approximately 500 c.c. of methyl alcohol as a wetting agent, and dried to form granules with a diameter of approximately 6 mm.
Obtained 450g. When 5 g of each of these granules were impregnated with various fragrances shown in Table 1 for 3 hours, the adsorption results shown in Table 1 were obtained. When the fragrance-adsorbing granules obtained above were left at room temperature, the fragrance continued to emit for more than three months. Example 3 After adding 100 g of sodium alginate powder under stirring to a hydroxyapatite aqueous suspension with a concentration of 10% by weight,
100g of pulp fiber was added and dispersed. Furthermore, the Ca/P (molar ratio) of hydroxyapatite is approximately 1.64, BET
The specific surface area determined by the method was 130 m ² /g. The resulting mixed solution was dropped into a calcium chloride aqueous solution with a concentration of 10% by weight at a rate of 800 ml/hr to obtain a spherical cured product, which was then washed with water and dried to form a spherical molded product (spherical diameter approximately 3 mm). Obtained 2.2Kg. 5 g of each of the obtained spherical molded bodies was taken and perfume was adsorbed in the same manner as in Example 1. The results were as shown in Table 1. The fragrance-adsorbing molded article continued to emit a fragrance for more than three months when left at room temperature. Example 4 A spherical molded product weighing 2.1 kg was obtained in the same manner as in Example 2 except that pulp fibers were not used. The amount of adsorption of various fragrances in the obtained spherical molded body was determined by the first
As shown in the table, the fragrance adsorption molded article emitted a fragrance for more than 3 months when left at room temperature. 【table】

Claims (1)

[Scope of Claims] 1. A calcium phosphate-based additive obtained by adsorbing a fragrance onto a base material made of a calcium phosphate-based compound having a Ca/P (molar ratio) of 1.0 to 2.0 and a specific surface area of 50 to 300 m ² /g by the BET method. Release. 2 Spherical molding with a diameter of 1 to 10 mm using a calcium phosphate compound as a base material with Ca/P (molar ratio) = 1.0 to 2.0 and a specific surface area of 50 to 300 m ² /g by BET method and a water-soluble polymer as a binder. Calcium phosphate sustained-release product made by adsorbing fragrance to substances.