HK1008165A - Controlled release composition containing volatile compound - Google Patents

Description

Controlled release compositions containing volatile compounds

The present invention relates to a controlled release composition for the controlled release of volatile compounds. More particularly, the present invention relates to a controlled release composition suitable for releasing volatile compounds contained therein in a controlled manner in a confined space or room or in an open space.

The controlled release of volatile compounds such as fragrances and essential oils is achieved by mixing the volatile compounds with ethylene vinyl acetate resins and the like, or by adding the volatile compounds to cyclodextrins, or by mixing the volatile compounds with naturally occurring shellac resins, among other methods.

However, these conventional methods have problems in that the melting point of the synthetic resin such as ethylene vinyl acetate resin is high, volatile compounds are easily volatilized when mixing with the synthetic resin to reduce the yield thereof, and the plasticizing effect of the volatile compounds greatly softens the resulting composition to weaken the sustained release of the synthetic resin. If cyclodextrin is used, cyclodextrin itself is expensive and it is not easy to control the release rate because volatile compounds are released only within a certain humidity range and it is released rapidly if the humidity is too high.

Meanwhile, naturally occurring shellac resin is superior in safety and control of release rate, but its release properties are easily changed depending on humidity. When it is melted by heating to be mixed with the volatile compound, it is easily hardened to lower its workability during production or the workability of the resulting mixed composition.

In view of this situation, there is a great need for a controlled release composition containing volatile compounds which is superior in terms of controlled release of the volatile compounds, especially in terms of controlled release of the volatile compounds in a confined space or room or in an open space, without the problems of variation in release rate due to humidity and hardening during production.

As a result of the observation and study conducted in order to solve the above problems, it was found that rosin naturally releases volatile compounds from a mixture of volatile compounds and rosin even without any special physical means and that rosin makes the release of the compounds unexpectedly smooth, and that it is chemically more stable than conventional shellac and does not have the above-mentioned problems of the change of release rate due to humidity and the easiness of hardening during the production. Further studies have shown that the simultaneous use of a plasticizer makes the preparation of a controlled-release composition easier, the properties more stable, and excellent processability, which have led to the completion of the present invention.

Accordingly, the present invention provides the following: 1) a controlled release composition comprising a volatile compound and rosin in a proportion of 0.1 to 100 parts by weight, in particular 0.2 to 30 parts by weight, of the volatile compound per 100 parts by weight of rosin. 2) The controlled release composition of claim 1), wherein the volatile compound is allyl isothiocyanate. 3) The controlled-release composition described in 1) or 2) above, further comprising a plasticizer, preferably 1 to 25 parts by weight per 100 parts by weight of the rosin. 4) The controlled-release composition described in the above 3), wherein the plasticizer is at least one selected from the group consisting of fatty acid, fatty acid ester, phosphoric acid ester and wax group. 5) The controlled release composition as described in any of 1) to 4) above, wherein the total content of the rosin and the volatile compound is at least 60% by weight based on the total weight. 6) The controlled release composition according to any one of 1) to 5) above, which may be in the form of a tablet, a powder, a granule or a tablet. 7) The controlled-release composition according to any one of 1) to 5) above, which may be adhered to one or both sides of a film-or sheet-like substrate. 8) The controlled release composition of any one of 1) to 5) above, which may be sandwiched between two substrates, in particular the composition is sandwiched between a non-oriented polypropylene film and a polyester film. 9) The controlled release composition of any one of 1) to 5) above, which is sandwiched in a fibrous substrate.

Brief description of the drawingsthe accompanying drawings:

FIG. 1 shows a graph of the remaining percentage of volatile compounds contained in examples 1-3 and comparative examples 1-3 versus time (days) under isothermal, iso-wet conditions.

FIG. 2 shows a graph of the remaining percentage of volatile compounds contained in examples 4-6 and comparative examples 4-6 versus time (days) under isothermal, iso-wet conditions.

FIG. 3 shows a graph of the remaining percentage of volatile compounds contained in examples 7-9 and comparative examples 7-9 versus time (days) under isothermal, iso-wet conditions.

FIG. 4 shows a graph of the remaining percentage of volatile compounds contained in examples 10-12 and comparative examples 10-12 versus time (days) under isothermal, iso-wet conditions.

FIG. 5 shows a graph of the remaining percentage of volatile compounds contained in examples 13-18 and comparative examples 13-15 versus time (days) under isothermal, iso-wet conditions.

FIG. 6 is a graph of the percent remaining volatile compounds contained in example 22 versus time (days) using relative humidity as a parameter.

FIG. 7 shows a graph of the remaining percentage of volatile compounds contained in comparative example 16 versus time (days) with relative humidity as a parameter.

Rosins useful in the present invention include, for example: natural rosins containing one or two organic acids, such as abietic acids (e.g., abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, etc.) and pimaric acids (e.g., d-pimaric acid, iso-d-pimaric acid, levopimaric acid, etc.); and processed rosins produced in various countries of the world, such as rosin gum, tall oil rosin, wood rosin, denatured rosin obtained by hydrogenation, disproportionation, polymerization, etc. of the above-mentioned rosins, and rosin esters (e.g., rosin glycerin ester) obtained by esterification of the above-mentioned rosins. These rosins are thermoplastic solids at ambient temperature and have melting points of about 80 ℃ to 130 ℃. These, in which the melting point does not exceed 110 ℃ and in particular does not exceed 100 ℃, advantageously lower the melting temperature of the rosin in the preparation of the composition according to the invention and reduce, to the greatest extent possible, the gasification and loss of volatile compounds, which will be mentioned later, when mixed with rosin.

The volatile compounds for use in the present invention may be, for example: one or more of a variety of natural and synthetic compounds that can be in the form of a vapor that produces fragrance, odor, bacteria, fungi, insect and other beneficial effects and that volatilizes in the environment in which the composition of the present invention is used. In particular, volatile compounds are preferably those which have an equilibrium vapor pressure of at least 0.001mmHg, especially not less than 0.003mmHg, at the ambient temperature, e.g., room temperature, at which the composition of the present invention is used.

Examples of volatile compounds, including natural and synthetic substances, are: pinene, limonene, linalool, menthol, terpene alcohols, eugenol, acetophenone, lavender oil, hinoki oil, eucalyptus oil, peppermint oil [ from mentha ], rose oil, mustard oil, hinoki oil, 4-isopropyl cycloheptadienone, chlorine dioxide, thiocyanic acid compounds, isothiocyanate compounds, allyl isothiocyanate and the like.

When the content of the volatile compound is too small relative to the content of the rosin, it is difficult to release the volatile compound continuously. Conversely, if the content is too large, the rosin is not well released, and some volatile compounds increase the plasticity of the rosin, resulting in maximum softening of the resulting mixed composition, so that it cannot be made into the desired product form. Therefore, the content of the volatile compound is 0.1 to 100 parts by weight, preferably 0.2 to 30 parts by weight, more preferably 1 to 25 parts by weight per 100 parts by weight of the rosin.

The use of the plasticizer in the present invention facilitates mixing and kneading at the time of preparation of the composition of the present invention, which results in a smaller amount of volatile compounds volatilized during the preparation, and reduces and prevents dispersion unevenness caused by volatilization of volatile compounds in the composition. The plasticizer may be any as long as these effects can be achieved, and it may be, for example: fatty acids, fatty acid esters, phosphate esters, waxes, and the like.

Examples of fatty acids include stearic acid and lauric acid. The fatty acid ester may be, for example: sorbitan laurate, dibutyl sebacate or the like. As the phosphate ester, there can be used, for example: 2-ethylhexyl diphenyl phosphate, and the like. The wax may be, for example: ester waxes of fatty acids, such as vegetable waxes (e.g., carnauba wax and cotton wax) and animal waxes (e.g., beeswax and wool wax), and higher monohydric or dihydric alcohols, montan wax, ozokerite wax, microcrystalline wax, vaseline, and the like.

Too small an amount of plasticizer does not perform any function and is generally added in excess, although in doing so, depending on the nature of the plasticizer, it excessively softens the resulting composition, which may make it difficult to make it into the desired product form. Thus, the plasticizer is used in an amount of 0.1 to 100 parts by weight, preferably 1 to 25 parts by weight, per 100 parts by weight of the rosin. Particularly preferred proportions of the composition within the scope of the invention are: the volatile compound is 1-25 weight parts and the plasticizer is 1-25 weight parts per 100 weight parts of rosin.

Plasticizers include those which improve mixing and kneading during preparation of the compositions of the invention, as well as the processability of the resulting compositions and the maintenance of the morphology of the final product. Examples of such plasticizers include the various waxes described above, which may be used in amounts greater than the other plasticizers.

The controlled-release composition of the present invention may further contain various conventional additives such as coloring agents, binding preventive agents, etc. as long as the object of the present invention is not hindered. It is to be noted that when the total content of the rosin and the volatile compound in the controlled-release composition of the present invention is too small, various problems such as poor control of release, poor processability, poor maintenance of the form of the final product, etc. are caused due to insufficient content of the rosin; short volatilization time due to too small content of volatile compounds, etc. Therefore, the total content of the rosin and the volatile compound in the controlled-release composition of the present invention is preferably at least 60% (by weight), and particularly preferably not less than 80% (by weight).

In preparing the controlled-release composition of the present invention, in order to prevent oxidative decomposition of other ingredients added, particularly rosin, a volatile compound may be added to and mixed with rosin that has been melted by heating in air or an inert atmosphere such as nitrogen and carbon dioxide. When a plasticizer is used, it may be mixed with the rosin first, or it may be added to the rosin together with the volatile compound.

The volatile compounds for use in the present invention may be liquid or solid at room temperature. The liquid may be added alone or in powder form carried by a conventional suitable carrier which does not react with the volatile compound, such carriers being, for example: pulp, paper, cellulose particles, zeolites, alumina, silica gel and calcium silicate. When solid at room temperature, it may be added in powder form.

Since the volatile compounds are essentially completely volatile, it is industrially important to minimize the amount of gasification and loss during the preparation of the compositions of the invention, particularly due to the high temperatures involved in mixing, to the greatest extent possible. For this reason, it is preferable to lower the melting temperature of the rosin during the preparation process to, for example, not more than 100 ℃, preferably 75 to 90 ℃. In general, it is preferable to use the following methods: the mixing is effected completely in a short time using a closed type mixer such as a Henschel mixer, immediately after mixing, cooling as required, shaping it into a desired form while cooling and hermetically packaging the final product. When plasticizers are used, the volatile compounds are first thoroughly mixed in a closed space with the desired amount of plasticizer, which aids their incorporation into the rosin.

The controlled-release composition of the present invention can be used in various ways according to various purposes of use. For example, the controlled release composition of the present invention is separately prepared into a tablet (plata), a powder, a tablet or a specially shaped block.

In addition, the controlled release composition of the present invention can be used in combination with various substrates. Examples of such substrates include solid and non-foamed films and sheets obtained by extrusion molding of plastics (e.g., cellophane, polyolefins such as polyethylene and polypropylene, nylon, polyester, etc.). In addition, foamed films and sheets obtained by extrusion foaming of the above-mentioned plastics, nonwoven and woven products of plastic fibers, papers, flat sheets of cellulose pulp and crepe papers, and the like can also be used as the base sheet.

The composition may be combined with a substrate to form, for example: a layered structure wherein the controlled release composition is applied to one or both sides of said non-foamed or foamed film or sheet; sandwich or multi-layer structures further comprising a layer of different films, sheets, nonwovens, textiles or papers on said coating, in which structures fibrous substrates, such as nonwovens and textiles of plastic fibers, paper, flat sheets of cellulose pulp and crepe paper, etc., are covered on the surface of the coating; impregnating a structure wherein the composition is sandwiched between fibers of said fibrous substrate; or other structures. The controlled-release composition contained in the above-mentioned layered structure, sandwich structure, multi-layered structure or impregnated structure may be a continuous product (non-powdery product) obtained after cooling and solidifying the molten composition. Alternatively, powders or granules of the composition may be forcibly rubbed into the substrate. In the case of the above-described sandwich structure, one of the films sandwiching the composition may be a gas permeable film such as a non-oriented polypropylene film, and the other film may be a gas impermeable film such as a polyester film, so that the layer of the controlled release composition between the two films mainly or completely functions as a volatile compound on only one side, which is particularly preferred in the present invention.

Since the controlled-release composition of the present invention is thermoplastic, it can be easily prepared in various forms as mentioned above. For example, the preparation process comprises: pouring the composition of the invention into a casting mould immediately after its preparation while it is still in the molten state; alternatively, if it has cooled immediately to a solid, the solid is then heated to melt, or coated on the surface of the substrate, or otherwise the substrate is immersed in a bath of molten composition. To obtain a powdered composition, the aforesaid product in the form of flakes or blocks may be ground to a powder, or made by spraying it from a nozzle immediately after the composition is still molten and then cooled, or by grinding the sprayed and cooled product as required.

The controlled-release composition of the present invention, in which the volatile compounds in vapor form have different release rates, can be prepared by determining the kind of the volatile compounds or controlling their amount. For example, when the volatile compound is allyl isothiocyanate (hereinafter abbreviated as AIT), the release rate can be controlled to an extremely slow degree, so that the compound can be released continuously or controllably over a long period of time to maintain its antimicrobial action, freshness-retaining action, insecticidal action, etc. for a long period of time, or the rate can be slightly increased to safely preserve items which are easily spoiled in a short period of time, such as packaged snack foods.

The volatile compound is preferably added in an appropriate amount depending on its properties or the purpose of use. For example, when the volatile compound used is AIT, and the composition of the present invention is used for preventing deterioration of packed snack foods, freshness of fresh foods, etc., it is desirable that a small amount of AIT be rapidly released, and in this case, the preferred amount is about 0.2 to 20 parts by weight per 100 parts by weight of rosin plus AIT. When the composition is used in a wardrobe to protect against insects and mildew or as a mildew-proof wallpaper stick or board or filter, it is desirable that a small amount of AIT be released in a very controlled manner, and in this case the preferred amount is about 0.2 to 15 parts by weight of AIT per 100 parts by weight of rosin.

The AIT controlled release composition of the invention can be used for diffusing fragrance, antimicrobial action, antibacterial action, insecticidal action, insect prevention action, fungicidal action, mildewproof action, fresh-keeping action, antiseptic action and the like. For example, since it has bactericidal and bacteriostatic effects against aerobic bacteria and anaerobic bacteria, as well as fungicidal, fungistatic and antimycotic effects, it can be suitably used in foods and various products in which growth and reproduction of harmful microorganisms cause various problems. In addition, it can be used as a preservative for keeping food fresh and preventing food from rotting and fermenting, and as a preservative for leather products, books and art (especially antiques). In addition, the composition of the present invention and the controlled-release agent containing the same can exterminate or eliminate pests, and can be used as an insect repellent for building materials, agricultural products and clothes.

Antimicrobial agents may be combated with microorganisms including, for example: fungi such as mold and yeast, bacteria such as Staphylococcus, Escherichia coli, Salmonella typhi, Vibrio, and other harmful microorganisms.

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1

Rosin (1000G, trade mark AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) and phosphoric acid ester (100G, 2-ethylhexyl diphenyl phosphate: trade mark #41, manufactured by Daihachi Chemical Industry Co., Ltd.) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and a primary reagent d-limonene (100G) was poured therein. After the rotary mixer was rotated at 500rpm for 5 minutes, the mixture was cooled to be hard to obtain a limonene-containing controlled-release composition in the form of a block. Example 2

A limonene-containing block-shaped controlled-release composition was prepared under the same method and conditions as in example 1, except that 2000G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) was used. Example 3

A limonene-containing block-shaped controlled-release composition was prepared under the same method and conditions as in example 1, except that 500G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) was used. Example 4

Rosin (1000G, trade mark AA-G, manufactured by Arakawa Chemical industry Co. Ltd.) and phosphate ester (100G, 2-ethylhexyl diphenyl phosphate: trade mark #41, manufactured by Daihachi Chemical industry Co., Ltd.) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and AIT (100G) was poured therein. After the rotary mixer was rotated at 500rpm for 5 minutes, the mixture was cooled to be hard to obtain a controlled-release composition in the form of a block containing AIT. Example 5

Bulk controlled release compositions containing AIT were prepared in the same manner and under the same conditions as in example 4, except that 2000G of rosin (trade name: AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) was used. Example 6

Bulk controlled release compositions containing AIT were prepared in the same manner and under the same conditions as in example 4, except that 500G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) was used. Example 7

Rosin (1000G, trade mark AA-G, manufactured by Arakawa Chemical industry Co. Ltd.) and fatty acid (100G, sorbitan fatty acid ester: trade mark L-10(F), manufactured by Kao Corporation) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and a primary reagent d-limonene (100G) was poured therein. After the rotary mixer was rotated at 500rpm for 5 minutes, the mixture was cooled to be hard to obtain a limonene-containing controlled-release composition in the form of a block. Example 8

A limonene-containing block-shaped controlled-release composition was prepared under the same method and conditions as in example 7, except that 2000G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) was used. Example 9

A limonene-containing block-shaped controlled-release composition was prepared under the same method and conditions as in example 7, except that 500G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) was used. Example 10

Rosin (1000G, trademark AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) and fatty acid (100G, sorbitan fatty acid ester: trademark L-10(F), manufactured by Kao Corporation) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUING COMPANY, LIMITED), and AIT (100G) was poured therein. After the rotary mixer was rotated at 500rpm for 5 minutes, the mixture was cooled to be hard to obtain a controlled-release composition in the form of a block containing AIT. Example 11

Bulk controlled release compositions containing AIT were prepared in the same manner and under the same conditions as in example 10, except that 2000G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) was used. Example 12

With the exception of using 500G of rosin (trademark AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.), a bulk controlled-release composition containing AIT was obtained under the same method and conditions as in example 10. Examples 13 to 15

Bulk controlled release compositions containing AIT of example 13 (1000g of rosin, rosin: AIT 100: 10), example 14 (2000 g of rosin, rosin: AIT 100: 5), and example 15 (500 g of rosin, rosin: AIT 100: 20) were prepared by the methods and conditions of examples 10 to 12, respectively, except that no fatty acid ester was used. Examples 16 to 18

Bulk controlled release compositions containing AIT of example 16 (rosin: AIT 100: 1), example 17 (rosin: AIT 100: 50) and example 18 (rosin: AIT 100: 75) were prepared according to the method and conditions of example 10, respectively, except that no fatty acid ester was used and different amounts of AIT were used. Example 19

The controlled-release composition containing AIT of example 4 was coated on a 20 μm-thick non-oriented polypropylene film immediately after mixing in a Henschel mixer, and then covered with a 25 μm-thick polyester film, thereby obtaining a controlled-release preparation having a 3-layer structure. The thickness of the controlled release composition layer in the article after cooling was 10 μm. Example 20

The controlled release composition containing AIT of example 5 was prepared into a controlled release preparation having a 3-layer structure using the same film in the same manner as in example 19. After cooling, the thickness of the controlled release composition layer in the article was 10 μm. Example 21

The controlled release composition containing AIT of example 6 was prepared into a controlled release preparation having a 3-layer structure using the same film in the same manner as in example 19. After cooling, the thickness of the controlled release composition layer in the article was 10 μm. Example 22

Rosin (1000G, trade mark AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) and phosphate ester (120G, 2-ethylhexyl diphenyl phosphate: trade mark #41, manufactured by Daihachi Chemical Industry Co.Ltd.) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and AIT (60G) was poured therein. The rotary mixer was rotated at 500rpm for 5 minutes. Then, a controlled-release preparation having a 3-layer structure was prepared in the film and method used in example 19. After cooling, the thickness of the controlled release composition layer in the article was 10 μm. Comparative example 1

D-limonene (1.5g) was fired at a thickness of about 3mm into a dish 50mm in diameter. Comparative example 2

Rosin (1500G, trade mark AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) and phosphoric acid ester (1G, 2-ethylhexyl diphenyl phosphate: trade mark #41, manufactured by Daihachi Chemical Industry Co.Ltd.) were heated to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED) to melt and liquefy them, and a primary reagent d-limonene (1G) was poured therein. The rotary mixer was rotated at 500rpm for 5 minutes. The mixture is cooled to harden to provide a composition in the form of a mass comprising limonene. Comparative example 3

Except that 500G of rosin (trade name: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.), 1000G of phosphoric acid ester (2-ethylhexyl diphenyl phosphate: trade name: #41, manufactured by Dailhachi Chemical Industry Co.Ltd.) and 1000G of d-limonene were used, a viscous composition containing limonene was obtained in the same manner and under the same conditions as in example 1. Comparative example 4

AIT (1.5g) was cast in 50mm diameter dishes at a thickness of about 3 mm. Comparative example 5

Rosin (1500G, trade mark AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) and phosphoric ester (1G, 2-ethylhexyl diphenyl phosphate: trade mark #41, manufactured by Daihachi Chemical Industry Co.Ltd.) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and AIT (1G) was poured therein. The rotary mixer was rotated at 500rpm for 5 minutes. The mixture was cooled to harden to obtain a bar composition containing AIT. Comparative example 6

Except that 500G of rosin (trade name: AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.), 1000G of phosphoric acid ester ((2-ethylhexyl diphenyl phosphate) ester: trade name: #41, manufactured by Daihachi Chemical Industry Co.Ltd.) and 1000G of AIT were used, a viscous composition containing limonene was obtained in the same manner and under the same conditions as in example 4. Comparative example 7

AIT (1.5g) was poured in a thickness of about 3mm into a dish of 50mm diameter (same as in comparative example 1). Comparative example 8

Rosin (1500G, trade mark AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.) and a fatty acid ester (1G, sorbitan fatty acid ester: trade mark L-10(F), manufactured by Kao Corporation) were melted and liquefied by heating to 85 ℃ in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED), and a primary reagent d-limonene (1G) was poured therein. After the rotary mixer was rotated at 500rpm for 5 minutes, the mixture was cooled to be hard to obtain a limonene-containing cake composition. Comparative example 9

Except that 500G of rosin (trademark AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.), 1000G of a fatty acid ester (sorbitan fatty acid ester: trademark L-10(F), manufactured by Kao Corporation) and 1000G d-limonene were used, in the same manner and under the same conditions as in example 7, to obtain a viscous composition containing limonene. Comparative example 10

AIT (1.5g) was cast in 50mm diameter dishes (same as comparative example 4) at a thickness of about 3 mm. Comparative example 11

Rosin (1500G, trademark AA-G, manufactured by Arakawa Chemical Industry Co.Ltd.) and 1G of a fatty acid ester (sorbitan fatty acid: trademark L-10(F), manufactured by Kao Corporation) were melted and liquefied in a 20q Henschel mixer (manufactured by MITSUI MINING COMPANY, LIMITED) by heating to 85 ℃ and AIT (1G) was poured therein. The rotary mixer was rotated at 500rpm for 5 minutes. The mixture was cooled to harden to obtain a bar composition containing AIT. Comparative example 12

Except that 500G of rosin (trademark: AA-G, manufactured by Arakawa Chemical Industry Co. Ltd.), 1000G of fatty acid ester (sorbitan fatty acid ester: trademark: L-10(F), manufactured by Kao Corporation) and 1000G of AIT were used, in the same manner and under the same conditions as in example 10, a viscous composition containing AIT was obtained. Comparative example 13

AIT (1.5g) was cast in 50mm diameter dishes (same as comparative examples 4 and 10) at a thickness of about 3 mm. Comparative example 14

In the same manner and under the same conditions as in example 11 except that no fatty acid ester was used, a bar composition containing AIT was obtained. Comparative example 15

In the same manner and under the same conditions as in example 12 except that no fatty acid ester was used, an AIT-containing bar composition was obtained. Comparative example 16

A 3-layer structured article comprising one layer (thickness 10 μm) of the AIT-containing composition was obtained under the same method and conditions as in example 22 except that 1000g of Shellac (pearll-N811, manufactured by Gifu Shellac manual co.ltd.) was used instead of rosin. Experimental example 1

About 3mm thick 1cm X1 cm samples prepared in examples 1 to 6 and comparative examples 1 to 6 described above were placed in a diameterIn a 50mm dish and placed in a temperature and humidity regulator (volume 64 m)³Air exchange rate of 60m³/hr) at 20 ℃ and a Relative Humidity (RH) of 65%, during which the 50mm diameter dishes are weighed at intervals. The weight loss was taken as the amount of volatile compounds volatilized and the percent volatilization was calculated as time. The results for examples 1 to 3 and comparative examples 1 to 3 are shown in FIG. 1, and the results for examples 4 to 6 and comparative examples 4 to 6 are shown in FIG. 2. The remaining percentages of volatile materials are shown in fig. 1 and 2, where each percentage is an average of 10 samples.

As can be seen from FIG. 1, the samples of examples 1-3 are superior in the release properties of volatile compounds and are significantly superior in the controlled release of d-limonene to the samples of comparative examples 1-3. Meanwhile, as can be seen from fig. 2, the samples of examples 4-6 are superior in the release properties of volatile compounds and are significantly superior to the samples of comparative examples 4 and 6 in the controlled release of AIT. Very small amounts of d-limonene were used in comparative example 2 and very small amounts of AIT were used in comparative example 5, and the volatile compounds did not continue to volatilize. Experimental example 2

The release properties and controlled release abilities of the 1cm × 1cm samples having a thickness of about 3mm prepared in the above-mentioned examples 7 to 12 and comparative examples 7 to 12 were measured in the same manner under the same conditions as in experimental example 1. The results for examples 7 to 9 and comparative examples 7 to 9 are shown in FIG. 3, and the results for examples 10 to 12 and comparative examples 10 to 12 are shown in FIG. 4. The remaining percentage of volatile material is shown in fig. 3 and 4, where each percentage value is an average of 10 samples.

As can be seen from FIG. 3, the samples of examples 7-9 are superior in the release properties of d-limonene and significantly superior in the controlled release of d-limonene to the samples of comparative examples 7 and 9. Meanwhile, as can be seen from fig. 4, the samples of examples 10 to 12 are superior in the release properties of AIT and significantly superior to the samples of comparative examples 10 and 12 in the controlled release of AIT. In comparative example 8, a very small amount of d-limonene was used, in comparative example 11, a very small amount of AIT was used and the volatile compounds did not continue to volatilize. Experimental example 3

The release properties and controlled release abilities of the 1cm × 1cm samples having a thickness of about 3mm prepared in the above-mentioned examples 13 to 18 and comparative examples 13 to 15 were measured in the same manner under the same conditions as in example 1. The results are shown in fig. 5, where the remaining percentage of volatile compounds is shown, which is the average of 10 samples.

As can be seen from fig. 5, the samples of examples 13 to 18 were superior in the release performance of AIT and significantly superior in the controlled release of AIT to the samples of comparative examples 13 and 15. In comparative example 14, in which AIT was used in a very small amount, volatile compounds were not continuously volatilized. Experimental example 4

Samples of 20cm by 30cm were each cut from the controlled release preparations of examples 19 to 22 and subjected to a temperature and humidity conditioner (volume 64 m)³Air exchange rate of 60m³/hr) at 20 ℃ and 65% RH, during which the samples were weighed at intervals. The weight loss was taken as the amount of volatile compounds that were volatilized and the percent volatilization was calculated over time (average of three samples). As a result, each preparation showed stable AIT controlled-release ability over about 1.5 to 2 days. Experimental example 5

As samples, 6mg of AIT pieces were cut out from the controlled release preparations of examples 19 to 22, respectively. Meanwhile, the test substance was prepared by applying the E.coli dilution to the surface of deoxycholate agar medium in the dish. The test substance was placed in a standard lunch box and each sample was placed on it, and the box was then covered. The snack boxes were incubated at 25 ℃ for 24 hours. The test was performed with the test substance without AIT preparation as a control. After 24 hours incubation, no colonies were found on the surface of the medium with the example sample strips, whereas red colonies formed in the control. Experimental example 6

A10 cm by 10cm sample was cut from each of the controlled release preparations of example 22 and comparative example 16 to evaluate the stability of the controlled release preparation against humidity. The sample was placed in a temperature and humidity conditioner (volume 64 m)³Aeration rate of 60m³/hr) at 20 deg.C and RH of 20%, 65% and 95%, at certain time intervalsThe samples were weighed. The weight loss was taken as the amount of volatile compounds volatilized and the percent volatilization was calculated as time. The results for example 22 are shown in fig. 6 and the results for comparative example 16 are shown in fig. 7. The remaining percentages of volatile compounds are shown in fig. 6 and 7, which are the average of 10 samples.

Comparing the results of fig. 6 and fig. 7 shows that the composition of example 22 using rosin as a base material significantly reduces the effect of humidity on the controlled release ability, compared to comparative example 16 using shellac as a base material.

According to the present invention, a controlled release composition capable of controlling the release of volatile compounds, particularly its stable controlled release ability, which is not affected by humidity, can be obtained. When a plasticizer is used together, the controlled-release composition of the present invention can contain volatile compounds in high yield, so that a controlled-release composition having more stable quality can be easily prepared. The controlled release composition of the present invention can be suitably used for fragrance emission, antimicrobial action, antibacterial action, insecticidal action, insect-repellent action, fungicidal action, antifungal action, freshness-retaining action, preservative action and the like.

This application is based on Japanese application No.8-139301, the contents of which are incorporated herein by reference.

Claims (12)

1. A controlled release composition comprising a volatile compound and rosin in a proportion of 0.1 to 100 parts by weight of the volatile compound per 100 parts by weight of the rosin.

2. The composition according to claim 1, wherein the volatile compound is contained in an amount of 0.2 to 30 parts by weight per 100 parts by weight of the rosin.

3. A composition according to claim 1 or 2 wherein the volatile compound is allyl isothiocyanate.

4. The composition of any one of claims 1 to 3, further comprising a plasticizer.

5. The composition according to claim 4, wherein the plasticizer is used in an amount of 1 to 25 parts by weight per 100 parts by weight of the rosin.

6. A composition according to claim 4 or 5, wherein the plasticizer is at least one member selected from the group consisting of fatty acid, fatty acid ester, phosphoric acid ester and wax.

7. A composition according to any one of claims 1 to 6, comprising a total amount of rosin and volatile compounds of at least 60% by weight.

8. A composition according to any one of claims 1 to 7, which is in the form of a tablet, powder, granulate or tablet.

9. A composition according to any one of claims 1 to 7 which is adhered to one or both sides of a film or sheet-like substrate.

10. A composition according to any one of claims 1 to 7, which is sandwiched between two substrates.

11. A composition according to claim 10 wherein the two substrates are a non-oriented polypropylene film and a polyester film.

12. The composition of any one of claims 1-7, which is held in a fibrous substrate.