JPH0912411A - Base, composition and production process of allyl isothiocyanate preparation - Google Patents

Abstract

PURPOSE: To obtain a base for an allyl isothiocyanate(AIT) preparation and an AIT composition usable for the production of an AIT preparation having any AIT content and giving a uniform AIT preparation having definite AIT content without causing the thermal curing of shellac. CONSTITUTION: This base for an AIT preparation contains shellac and a compound giving a viscosity of 1,000-50,000cP at 80 deg.C as a mixture of 0.2 pts.wt. of the compound and 1 pt.wt. of shellac. The AIT composition contains AIT, shellac and the above compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a base for an allyl isothiocyanate (hereinafter referred to as AIT) preparation, an AIT composition, a method for producing an AIT preparation, and a method for preventing variations in the AIT content in the AIT preparation.

[0002]

2. Description of the Related Art AIT, which is a component of horseradish and the like, has an excellent antibacterial action such as bactericidal, antibacterial, and antifungal action, and has no harmful effect on the human body. Since it is not shown, its usefulness as a fungicide for foods and the like is drawing attention.

AIT has a strong irritating odor peculiar to itself, and has a problem that the irritating odor adheres to foods and the like when used at a high concentration. For this reason, it is necessary to effectively exhibit the antimicrobial effect with the smallest possible amount. Advantageously, AIT vapor that evaporates from highly volatile AIT also has a high antimicrobial effect, and the vapor can effectively exhibit the antimicrobial effect even in a small amount.

However, since the volatility of AIT is extremely high, if the AIT is used as it is, the concentration of the AIT vapor in the atmosphere gas with which the antimicrobial-treated product is brought into contact with the product will increase in a short time, and the effect will be persistent. There is a fear of chipping, odor to the antimicrobial-treated product, and adverse effects due to penetration of AIT vapor into the antimicrobial-treated product.

Therefore, a preparation in which the release rate of AIT vapor can be freely controlled and the concentration of AIT vapor in the atmosphere gas with which the antimicrobial-treated product contacts can be freely controlled according to the antimicrobial-treated product or the treatment method. The development of is awaited. In particular, the development of a formulation that can maintain the AIT concentration in the atmospheric gas at a desired concentration for a long time is desired.

As a form of the AIT preparation satisfying this requirement, it is preferable that it is easy to use depending on the system used and easy to process. From this point of view, conventionally, AIT is supported on a carrier to control the release rate of AIT vapor, AIT is packaged with a film having AIT vapor permeability, and AIT is cyclodextrin (hereinafter referred to as CD That is, the material is included in a powder or granules in which the volatility is suppressed, and the powder or the like is kneaded with a resin to be processed into a film. Non-woven fabric, coated or processed, micro-encapsulated by various methods such as core solvation method and spray dry method to reduce volatility to powder or granules, and There has been proposed a material which is kneaded into a thermoplastic synthetic resin and processed into a film shape or a sheet shape.

However, the one in which AIT is simply supported on a carrier cannot sufficiently suppress the strong volatility of AIT, and is not easily processed into another form. In the case where AIT is packaged with an AIT vapor-permeable film, the rate of release of AIT vapor depends on the thickness of the film, so the control of the rate of release is limited, and
It is difficult to release T vapor slowly and stably, and applicable systems are also limited. In addition, the CD inclusion is expensive in CD itself, and AIT vapor is not released unless it is a system with a certain humidity or higher. Conversely, if the humidity is too high, the AIT inclusion force of the CD becomes weak and the AIT rapidly increases. However, there is a problem that the emission rate of AIT vapor cannot be controlled. In addition, microencapsulation of AIT is not suitable for industrial production because the AIT yield in the manufacturing process is extremely poor and mass production is difficult, and the microcapsule is destroyed by applying external force to release AIT vapor. However, there is a problem in that the rate of discharge of AIT vapor cannot be controlled. Further, when AIT is kneaded into a thermoplastic synthetic resin, the yield of AIT is extremely poor as in the case of microencapsulation and it is not suitable for industrial production. Further, since AIT has the property of attacking many synthetic resins, a sheet or film made by kneading AIT into such synthetic resin is swollen or swells over time, which is practical. Not suitable as a material. In addition, synthetic resin that is not attacked by AIT
AIT vapor impermeability, even if AIT is kneaded
The disadvantage is that it emits almost no steam.

As described above, conventionally, there has been no practical AIT preparation capable of freely controlling the release rate of AIT vapor and being compatible with various systems. Therefore, the present inventors
It has been found that shellac is promising as a base for AIT preparations that can provide such AIT preparations. However, the present inventors have found that the heating during kneading shellac and AIT volatilizes the AIT and the AIT content in the preparation is not constant, which tends to cause variations. Such a problem is remarkable especially when the AIT content in the AIT preparation is small, and in this case, there is a problem that the shellac is thermally hardened by heating, and further devising is required for industrial production. there were.

The object of the present invention is to obtain A of any AIT content.
A base and an AIT composition for an AIT preparation which can be used in the production of an IT preparation without requiring excessive heating, do not cause a constant variation in the AIT content in the AIT preparation, and do not cause heat curing. To provide. Another object of the present invention is to provide a method for producing such an AIT preparation and a method for preventing variations in the AIT content in the AIT preparation. The present invention is a novel invention in itself.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a base or AIT composition for AIT preparation containing shellac and a specific compound described later. It was found that the use of the above eliminates the need for excessive heating during production, the AIT content in the AIT preparation is constant and does not cause variations, and the thermosetting of shellac does not occur, and the present invention has been completed. Further, according to the base material and the AIT composition for an AIT formulation of the present invention, the release rate of the AIT vapor of the AIT formulation can be controlled more freely, and the moldability of the AIT formulation can be improved depending on the compound used. Also found.

That is, the present invention is as follows. (1) Shellac and 0.2 for 1 part by weight of shellac
The viscosity at 80 ° C. when kneading at a ratio of 1 part by weight is 1,
A base for an AIT formulation, which comprises a compound having a range of 000 to 50,000 cP. (2) 0.03 to 1 of the compound per 1 part by weight of shellac
The base for AIT preparation according to (1), which is contained in a ratio of parts by weight. (3) The compound is a monobasic acid ester, a dibasic acid ester,
It is any one selected from the group consisting of phosphate ester, aliphatic polyhydric alcohol and wax (1) or (2)
The base for the AIT formulation described. (4) AIT, shellac, and a compound containing a compound capable of adjusting the viscosity at 80 ° C. when kneaded at a ratio of 0.2 part by weight to 1 part by weight of shellac in the range of 1,000 to 50,000 cP. AIT composition to do. (5) 0.03 to 1 of the compound relative to 1 part by weight of shellac
The AIT composition according to (4), wherein the AIT composition is contained in a proportion of parts by weight. (6) The compound is a monobasic acid ester, a dibasic acid ester,
Any one selected from the group consisting of phosphate ester, aliphatic polyhydric alcohol and wax (4) or (5)
AIT composition as described. (7) In any one of (4) to (6), the AIT composition is used for any purpose selected from the group consisting of antimicrobial, insect repellent, preservative, freshness preservation and preservation. AIT composition as described. (8) The viscosity at 80 ° C. when kneaded at a ratio of 0.2 parts by weight to 1 part by weight of shellac is 1,000 to 50,
A method for producing an AIT preparation, which comprises a step of kneading shellac and AIT in the presence of a compound having a range of 000 cP. (9) 0.03 to 1 of the compound with respect to 1 part by weight of shellac
The method for producing an AIT preparation according to (8), wherein the AIT preparation is contained in a proportion of parts by weight. (10) The compound is a monobasic acid ester, a dibasic acid ester,
Any one selected from the group consisting of phosphate esters, aliphatic polyhydric alcohols and waxes (8) or (9)
A method for producing the described AIT preparation. (11) In the production of the AIT formulation, in the presence of a compound which makes the viscosity at 80 ° C. when kneaded at a ratio of 0.2 part by weight to 1 part by weight shellac in the range of 1,000 to 50,000 cP, A method for preventing variation in AIT content in an AIT formulation, which comprises a step of kneading shellac and AIT. (12) 0.03 to 1 of the compound per 1 part by weight of shellac
(11) The method for preventing dispersion of the AIT content in the AIT preparation, which is contained in a weight ratio of (11). (13) The compound is a monobasic acid ester, a dibasic acid ester,
Any one selected from the group consisting of phosphate ester, aliphatic polyhydric alcohol and wax (11) or (12)
A method for preventing variation in the AIT content in the described AIT preparation.

The shellac used in the present invention is a resinous substance secreted by a larva, Trichophyton lactis, which is parasitic on legumes such as bilmanem and kutch, and mulberry plants such as pearl oyster and Indian bodice. Bleached, purified and used. Although its chemical composition has not been clarified, it is believed that the main component is a natural condensation product in which oxycarboxylic acids are bonded to each other as a lactone.

The compound used in the present invention means that the viscosity at 80 ° C. when kneading at a ratio of 0.2 part by weight to 1 part by weight of shellac is in the range of 1,000 to 50,000 cP, and AIT It is a compound that does not react with. Preferably, the viscosity at 80 ° C. when kneading at a ratio of 0.2 parts by weight to 1 part by weight of shellac is 1,500 to 3
It is a compound having a range of 10,000 cP. If the viscosity is less than 1,000 cP, the shape cannot be maintained during molding, and if it exceeds 50,000 cP, uniform kneading during production becomes impossible.

Here, the viscosity is measured at 80 ° C. using a B type viscometer (BH type viscometer, manufactured by Tokyo Keiki Co., Ltd.).

The compound used in the present invention is not particularly limited as long as it satisfies the above characteristics, but for example, monobasic acid ester, dibasic acid ester, phosphoric acid ester, aliphatic polyhydric alcohol or wax is preferable. Examples of the monobasic acid ester include benzoic acid esters such as benzyl benzoate and phenyl benzoate, and acetic acid esters such as glyceryl triacetate and 2-ethylhexyl acetate. Examples of the dibasic acid ester include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and ethyl phthalyl ethyl glycolate, adipates such as dimethyl adipate and dibutyl adipate,
Examples thereof include sebacates such as dimethyl sebacate and dibutyl sebacate. Examples of the phosphoric acid ester include tributyl phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate and the like. Examples of the aliphatic polyhydric alcohol include glycerin, triethylene glycol and the like. Examples of the wax include rosin and beeswax. These compounds may be used in combination of two or more kinds. Among them, 2-ethylhexyldiphenyl phosphate, rosin, and triethylene glycol are preferable from the viewpoint of good compatibility with shellac and excellent safety.

From the viewpoint of increasing the release rate of AIT vapor, triethylene glycol and 2-ethylhexyldiphenyl phosphate are preferable, and from the viewpoint of reducing the release rate of AIT vapor, rosin is preferable. Further, rosin is preferable from the viewpoint of moldability.

The AIT used in the present invention may be of natural origin or synthetic origin. Further AIT1
The AIT-containing composition is not limited to the single agent consisting of 00%. When used in foods, it is preferable to use those derived from natural products. Also, the method for synthesizing AIT is not particularly limited. Examples of the AIT-containing composition include a powdery or granular material in which AIT is supported on a carrier.
As the carrier used here, any carrier may be used as long as it can carry AIT and has no influence on reactivity or the like with respect to AIT. Examples thereof include commonly used inert carriers such as pulp, paper, cellulose particles, zeolite, alumina, silica gel and calcium silicate.

The base for the AIT preparation of the present invention comprises shellac and the above compound. The base for the AIT formulation of the present invention varies depending on the compound used and the like, but it is preferable that the above compound is contained in a ratio of 0.03 to 1 part by weight to 1 part by weight of shellac, and more preferably shellac. The compound is contained in an amount of 0.05 to 0.3 parts by weight with respect to 1 part by weight. If the proportion of the compound in the base is less than 0.03 parts by weight with respect to 1 part by weight of shellac, the viscosity tends to be high, and it tends to be difficult to prevent heat curing. If it exceeds 1 part by weight, Generally, moldability tends to deteriorate.

The base is, for example, shellac and the compound in a kneader, usually 70 to 100 ° C., preferably 75 to 100 ° C.
It is prepared by heating and kneading at 85 ° C.

The AIT composition of the present invention comprises AIT, shellac and the above compounds. AIT of the present invention
The ratio of the amount of AIT, shellac and compound in the composition varies depending on the yield of AIT, the AIT content in the final AIT preparation, the compound and manufacturing conditions used, the purpose of use of the AIT preparation, etc. On the other hand, 0.001 to 0.4 part by weight of AIT, compound 0.
It is preferably from 03 to 1 part by weight. If the ratio of the compound in the AIT composition is less than 0.03 parts by weight with respect to 1 part by weight of shellac, the viscosity becomes high, and it tends to be difficult to prevent thermosetting, and if it exceeds 1 part by weight. Generally, moldability tends to deteriorate.

In the base and AIT composition for the AIT preparation of the present invention, various additives usually used, for example, a plasticizer, a coloring agent, and an anti-adhesion agent, are used within the range not deviating from the object of the present invention. , An anti-adhesion agent, etc. may be included.

The method for producing an AIT preparation of the present invention is characterized by kneading heat-melted shellac and AIT in the presence of the above-mentioned compound, and usually the base or AIT composition for the AIT preparation is used. Specifically, the AIT
The base for the formulation is melted under a nitrogen atmosphere at a temperature of 100 ° C. or lower, preferably 70 to 90 ° C., more preferably 75 to 85 ° C., and the AIT, for example, in a liquid state, or the AIT as a carrier. In the state of supported powdery or granular material, it is charged into this and cooled and solidified / formed to form A.
Prepare IT formulation.

When a temperature higher than 100 ° C. is used as the melting temperature, the AIT is volatilized, the AIT content in the AIT preparation is not constant and varies, and the shellac tends to be thermoset. Further, the yield of AIT is deteriorated, the release rate of AIT vapor of the obtained AIT preparation is increased, and the surface tends to be fouled. Further, it is preferable that the cooling and solidification be performed as soon as possible because the yield of AIT increases.

The charged amount of each composition at the time of manufacturing is AI
As described in the base and the AIT composition for the T preparation, the desired release rate of the AIT vapor and the melted AIT preparation in consideration of the yield of AIT and the AIT content in the final AIT preparation. It is appropriately selected according to the viscosity of the base or AIT composition.

The amount of each composition in the AIT preparation which is the final product is appropriately selected according to the application. For example, when an AIT preparation is used for the purpose of antibacterial lunch, freshness preservation of fresh foods, etc., AIT may be released in a minute amount and rapidly, and it depends on the compound used, but 1 part by weight of shellac. Against AIT 0.002-0.02
By weight, the amount of the compound is preferably about 0.05 to 0.3 part by weight, and specific preferred compounds include triethylene glycol and 2-ethylhexyl diphenyl phosphate. Further, when it is used for the purpose of preventing insects and mildew in clothes dance, or when it is used as a mildew-proof wallpaper or insect-proof sheet / filter, it is sufficient that AIT is released in a minute amount and in a sustained release, and 1 weight of shellac. AIT 0.05 to 0.4 parts by weight, compound 0.03 to
The amount is preferably about 1 part by weight, and a specific preferred compound is rosin.

The form of the AIT preparation produced according to the production method of the present invention is not particularly limited and may be appropriately selected depending on the purpose of use. For example, plate-shaped, block-shaped, powder-shaped, and granular AIT preparations, and base materials [for example, cellophane, polyolefin (polyethylene, polypropylene, etc.), plastic plate-shaped bodies such as polyester, nylon, vinyl chloride (film or Non-woven fabric such as rayon, polypropylene, polyester, wood, etc.
Woven cloth, paper, etc.] and AIT preparations obtained by adhering to or mixed with it.

The plate-shaped or block-shaped AIT preparation can be molded and manufactured according to the above-mentioned manufacturing method. Furthermore, by crushing this or by heat-melting A
By ejecting the IT composition from a nozzle, a powdery or granular preparation can be produced.

The AIT preparation adhered to the base material can be prepared, for example, by coating the surface of the base material with the heat-melted AIT composition and dipping. The AIT preparation mixed with the plastic plate-like base material can be produced by molding a powdery or granular AIT preparation into the raw material resin to form a plastic plate-like body. Further, the AIT preparation, which is mixed with a base material such as paper, non-woven fabric, and woven fabric, has the above-mentioned powdery substance and granular substance kneaded in the fibers constituting the paper, non-woven fabric, woven fabric, and the like. Examples thereof include fibers, which constitute paper, non-woven fabric, woven fabric, etc., and an AIT preparation in the form of powder or granules, which is kneaded in advance in an adhesive, and the fibers are used to prepare paper, non-woven fabric, etc. It can be prepared by

As described above, by using the method for producing an AIT preparation including the step of kneading shellac and AIT in the presence of the compound, the compound can be kneaded at a lower temperature than when the compound is not used. AIT formulations can be manufactured without the need for undue heating. Therefore,
It is possible to avoid the problems that AIT is volatilized during the production, the AIT content in the AIT preparation is not constant and varies, and the shellac is thermally cured.

A method for preventing the variation of the AIT content in the AIT preparation is characterized in that it comprises a step of kneading shellac and AIT in the presence of the above compound in the preparation of the AIT preparation. Is done.

Base or AIT for the AIT formulation of the present invention
According to the AIT formulation using the composition, the release rate of the AIT vapor can be controlled, and the control mode can exhibit sustained antibacterial action, freshness keeping action, insect repellent action and the like. it can. A released from AIT formulation
The rate of IT vapor can be adjusted by, for example, the amount of charged AIT, the type and amount of the compound, the production conditions (melting temperature, cooling temperature, the time thereof, etc.). Normal,
The larger the amount of AIT charged, the faster the release rate of AIT vapor, and the smaller the amount, the slower the release rate of AIT vapor, which tends to be continuously released. Further, by using the compound as described above, the release rate of AIT vapor can be increased or decreased. This allows various AIs
Various embodiments of AIT formulations with release rates of T vapor can be made.

Further, by using the above-mentioned compounds such as rosin, the moldability of AIT preparations and the like having a large AIT content can be improved.

The AIT composition of the present invention can be used for the purpose of antimicrobial, insect repellent, freshness preservation, preservative or preservation. That is, the AIT composition of the present invention has, for example, sterilization against aerobic bacteria and anaerobic bacteria, bacteriostatic action, fungicidal action against mildew, fungistatic action, antifungal action, etc. It is preferably used as an AIT formulation for various articles in which multiplication is a problem. Also, the AI of the present invention
The T composition is also useful as a preservative effective for preventing spoilage and fermentation of foods, etc., and also as a preservative for leather products, books and works of art (particularly antiquities). Furthermore, the AIT of the present invention
The composition also has an action of killing or repelling harmful insects, and is also useful as an insect repellent for building materials, agricultural products, clothing and the like. Examples of the microorganisms to be subjected to the antimicrobial include fungi such as molds and yeasts, bacteria such as staphylococci, Escherichia coli, salmonella, vibrio, algae, and other harmful microorganisms.

As the processed products targeted by the AIT composition of the present invention, various products in which the proliferation of harmful microorganisms is a problem, such as processed livestock products, processed seafood products, agricultural products, cooked foods, processed food products. , Feedstuffs, packaging materials, building materials, etc., such as agricultural products, fresh flowers, marine products, etc. where deterioration of freshness is a problem, and building materials, agricultural products, food materials, clothing, etc., which are affected by pests.

[0035]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples.

Example 1 79 parts by weight of shellac, 20 parts by weight of triethylene glycol (viscosity at 80 ° C. when kneaded at a ratio of 0.2 parts by weight relative to 1 part by weight of shellac: 7,500 cP) and 1 part by weight of AIT. Was used as the AIT composition. First, shellac and triethylene glycol are kneader (PN
V-1H, manufactured by Irie Shokai Co., Ltd., the same applies hereinafter), melted at 80 ° C. for 1 hour in a nitrogen atmosphere, added AIT thereto, and kneaded by heating at 80 ° C. for 15 minutes. 20 μm
Was coated on the polyethylene terephthalate (PET) film to obtain a coating thickness of 20 μm to obtain a film-shaped AIT preparation.

Example 2 79 parts by weight of shellac, 20 parts by weight of rosin (viscosity at 80 ° C. when kneaded at a ratio of 0.2 parts by weight relative to 1 part by weight of shellac: 28,000 cP) and AIT1
Part by weight was the AIT composition. First, shellac and rosin are melted with a kneader at 80 ° C. for 2 hours in a nitrogen atmosphere, AIT is added thereto, and further at 80 ° C. for 15 minutes,
Kneaded with heat. Then, it is cooled at room temperature for 24 hours to form a block, which is then crushed with a crusher to obtain an average particle size of 500
A granular AIT preparation of m was obtained.

Example 3 Example 1 was repeated except that triethylene glycol was replaced with benzyl benzoate (viscosity at 80 ° C. when kneading at a ratio of 0.2 part by weight to 1 part by weight shellac: 2,000 cP). Similarly, an AIT preparation was obtained.

Example 4 60 parts by weight of shellac and 2-ethylhexyl diphenyl phosphate (viscosity at 80 ° C. when kneaded at a ratio of 0.2 parts by weight with respect to 1 part by weight of shellac: 6,30)
0 cP) 30 parts by weight and AIT 10 parts by weight were used as the AIT composition. First, shellac and 2-ethylhexyldiphenyl phosphate were melted in a kneader at 80 ° C. for 1 hour in a nitrogen atmosphere, AIT was added thereto, and the mixture was heated and kneaded at 80 ° C. for 15 minutes. This is 12 μm
The PET film was coated to a coating thickness of 20 μm to obtain a film-shaped AIT preparation.

Example 5 Viscosity at 80 ° C. when 2-ethylhexyldiphenyl phosphate was kneaded at a ratio of 0.2 part by weight to 1 part by weight of shellac (12,000 parts by weight of shellac).
AIT preparation was obtained in the same manner as in Example 4 except that the AIT preparation was replaced with 0 cP).

Example 6 75 parts by weight of shellac, 20 parts by weight of rosin and AIT
5 parts by weight was used as the AIT composition. First, shellac and rosin were melted in a nitrogen atmosphere at 80 ° C. for 1 hour in a kneader, AIT was added thereto, and the mixture was heated and kneaded at 80 ° C. for 15 minutes. Then, it is cooled at room temperature for 24 hours to form a block, which is then crushed with a crusher to obtain an average particle size of
A 0 μm granular AIT formulation was obtained.

Example 7 Same as Example 6 except that the rosin was replaced with dibutyl sebacate (viscosity at 80 ° C. when kneaded at a ratio of 0.2 part by weight to 1 part by weight shellac: 8,700 cP). Then, an AIT preparation was obtained.

Example 8 An AIT preparation was obtained in the same manner as in Example 6 except that triethylene glycol was used instead of rosin.

Example 9 45 parts by weight of shellac, 40 parts by weight of rosin and AIT
15 parts by weight was used as the AIT composition. First, shellac and rosin were melted in a nitrogen atmosphere at 80 ° C. for 1 hour in a kneader, AIT was added thereto, and the mixture was heated and kneaded at 80 ° C. for 15 minutes. Then, it cooled at room temperature for 24 hours, and obtained the block-shaped AIT formulation.

Example 10 An AIT preparation was obtained in the same manner as in Example 4 except that a polypropylene non-woven fabric (basis weight 15 g) was used instead of the 12 μm PET film.

Comparative Example 1 99 parts by weight of shellac and 1 part by weight of AIT were used as an AIT composition. First, shellac and AIT were put in a kneader and heated and kneaded at 95 ° C. for 15 minutes in a nitrogen atmosphere.
This is coated on a 20μm PET film with a coating thickness of 20μm
To obtain an AIT formulation.

Comparative Example 2 99 parts by weight of shellac and 1 part by weight of AIT were used as an AIT composition. First, shellac and AIT were put in a kneader and heated and kneaded at 95 ° C. for 15 minutes in a nitrogen atmosphere.
Then, the mixture was cooled at room temperature for 24 hours to form a block, which was further pulverized by a pulverizer to obtain a granular A having an average particle size of 500 μm.
An IT formulation was obtained.

Comparative Example 3 Triethylene glycol was kneaded at a ratio of 0.2 parts by weight to ethanol (1 part by weight of shellac at 80 ° C.).
Viscosity: 800 cP), but after kneading by heating in the same manner as in Example 2 and then cooling at room temperature for 24 hours, it did not solidify.

Comparative Example 4 Rosin was used as a zeolite (0.
Viscosity at 80 ° C. when kneaded at a ratio of 2 parts by weight: 5
Although heat kneading was carried out in the same manner as in Example 2 except that the kneading was carried out in the same manner as in Example 2, shellac was thermoset during kneading, and uniform kneading became difficult.

Comparative Example 5 85 parts by weight of shellac and 15 parts by weight of AIT were added to the AIT
It was a composition. First, shellac and AIT were put in a kneader and heated and kneaded at 80 ° C. for 1 hour in a nitrogen atmosphere.
Then, it cooled at room temperature for 24 hours, but did not solidify.

Experimental Example 1: Variation in AIT content For the above Examples 1 to 3 and Comparative Examples 1 to 4, AIT
AIT content in the composition and AI after molding the AIT formulation
The T contents were compared. The AIT content in the AIT preparation was measured by gas chromatography after extracting the sample with dichloromethane. Table 1 shows the results.

[0052]

[Table 1]

As can be seen from Table 1, the AIT content in the AIT preparations of Examples showed less variation and less loss than the Comparative Examples.

Experimental Example 2: Presence or Absence of Thermal Curing The presence or absence of thermal curing was visually confirmed when the AIT compositions of Examples 1 and 2 and Comparative Examples 1 and 4 were kneaded at the temperatures shown in Table 2 for 2 hours. did. Here, “with thermosetting” means that fluidity is lost and uniform kneading is impossible, and “without thermosetting” means that fluidity is maintained and uniform kneading is possible. Table 2 shows the results.

[0055]

[Table 2]

Experimental Example 3: AIT Release Test AIT preparations prepared in Examples 4-5 (20 cm × 30 c)
m) were left at a constant temperature and humidity of 20 ° C. × 65% RH for 3 sheets each. From each, 10cm x 10c after every certain number of days
AIT contained in the sample fragment by cutting out m
Was extracted with dichloromethane, the residual AIT amount was calculated by analysis by gas chromatography, and each average value (n = 3) was determined. The AIT preparations prepared in Examples 6 to 8 were allowed to stand under the same conditions for 1 g each, and 0.05 g each was taken out every certain number of days, AIT was extracted with dichloromethane, and residual AI was obtained by gas chromatography.
The amount of T was measured and the average value (n = 3) of each was calculated.
The results are shown in FIG. 1 and FIG.

As can be seen from FIGS. 1 and 2, by selecting the compound to be used, the release rate of AIT can be controlled.

Experimental Example 4: Moldability The composition kneaded by heating in Example 9 and Comparative Example 5 was poured into a mass of 1 cm × 1 cm × 1 cm, cooled at room temperature for 24 hours, taken out from the mass, and the form was visually observed. I observed it. As a result, in Example 9, 1 cm × 1 cm × 1
Although it was a block shape of cm, Comparative Example 5 did not solidify and could not maintain its shape.

Experimental Example 5: Antimicrobial Action The AIT preparation film obtained in Example 4 was used in a total amount of 6 mg.
Samples were prepared by cutting to contain the AIT of. In addition, a dish containing desoxycholate agar medium was prepared, and a test material was prepared by coating the culture medium surface with a diluted solution of E. coli. Place the test material (dishes) in the lunch box, place the sample on the dish, cover the lunch box, and place it at 25 ° C for 2 hours.
The cells were cultured for 4 hours. As a control, the same experiment was conducted with the test material without the AIT preparation. The results after 24 hours from the culture are shown in Table 3.

[0060]

[Table 3]

Experimental Example 6: Antifungal activity Tatami mats The AIT preparation (nonwoven fabric) obtained in Example 10 is laid between tatami mats (size 20 cm x 20 cm, Okayama folk craft) and plywood, and at 30 ° C x 90% RH. Left unattended. As a control, a non-woven fabric was used. The generation of mold was observed 3 months after leaving and 6 months after. Table 4 shows the results.

[0062]

[Table 4]

Kitchen mold proof sheet Assuming a sink, plywood is used to make a box (50 x 50 x 50c).
2) were prepared. The AIT preparation (nonwoven fabric) obtained in Example 10 was laid on the bottom of one box. As a control, an unprocessed non-woven fabric was used in the other box. A petri dish coated with a mold on the surface of a PDA medium (manufactured by Nissui) was attached to the bottom surface, each side surface, and the top surface, and stored at room temperature (around 25 ° C) and high humidity (about 95% RH). The growth degree of mold was observed every week for up to 2 months. Table 5 shows the results.

[0064]

[Table 5]

Kneading into paint A test material was prepared by mixing the granular AIT preparation obtained in Example 6 with an acrylic aqueous paint at a ratio of 1%. The mold resistance test was conducted according to JIS Z 2911. An additive-free paint was used as a control. Table 6 shows the results.

[0066]

[Table 6]

Experimental Example 7: Insect repellent action 10 Petiocaridae were placed in a petri dish and covered with a breathable non-woven fabric. In a desiccator having a capacity of about 20 liters, the petri dish and 1 g of the granular AIT preparation prepared in Example 9 wrapped with a non-woven fabric were put. As a control, a desiccator containing only a petri dish containing scalloped mite was used. After 24 hours, the survival of each scalloped mite was observed. Table 7 shows the results.

[0068]

[Table 7]

Experimental Example 8: Freshness-retaining action Two cases of strawberries (30 pieces each) were prepared, one case was wrapped with the film-like AIT preparation prepared in Example 1, and the other was untreated as a control. It was similarly wrapped with polypropylene film. These were preserve | saved at about 20 degreeC, and the change of the strawberry was observed. Table 8 shows the results.

[0070]

[Table 8]

[0071]

INDUSTRIAL APPLICABILITY According to the present invention, an AIT preparation that can be used for the production of AIT preparations having any AIT content, does not cause the AIT content in the AIT preparations to be constant and does not fluctuate, and does not cause thermosetting shellac. Base and AI
A T composition can be provided. Moreover, according to the base and AIT composition for an AIT preparation of the present invention, the AIT of the AIT preparation is
The rate of vapor release can be controlled more freely, and by selecting the compound to be used, AIT
The moldability of the preparation can also be improved. Furthermore, since the shellac used in the present invention is a natural resin that has been widely and safely used in the fields of food and medical products, the AIT composition of the present invention can be suitably used in applications such as food. . In addition, shellac is biodegradable and has few environmental problems.

[Brief description of the drawings]

FIG. 1 AIT in AIT preparations obtained in Examples 4-5
It is a figure which shows the time-dependent change of the residual amount.

FIG. 2 AIT in the AIT formulations obtained in Examples 6-8
It is a figure which shows the time-dependent change of the residual amount.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Hideji Hirohama 1-8-10 Jiyugaoka, Kanazu-cho, Sakai-gun, Fukui Prefecture Rengo Co., Ltd. Fukui Laboratory (72) Inventor Yuichi Mizukami 1-chome, Chuo-ku, Osaka-shi, Osaka No.47 Midori Cross Castle East Branch Room (72) Inventor Taiji Sekiyama 1-1-47 Chuo-ku, Osaka City Osaka Prefecture Midori Cross Castle East Branch Office (72) Inventor Asami Takada Joto-ku Osaka City Osaka Prefecture 1-47 Chuo 1-Chome Midori Cross Castle East Branch Office

Claims (13)

[Claims] 1. Containing shellac and a compound which has a viscosity at 80 ° C. when kneaded at a ratio of 0.2 part by weight with respect to 1 part by weight of shellac in the range of 1,000 to 50,000 cP. Characteristic base for allyl isothiocyanate preparations. 2. The base for an allyl isothiocyanate preparation according to claim 1, which comprises the compound in an amount of 0.03 to 1 part by weight per 1 part by weight of shellac. 3. The allyl isothiocyanate preparation according to claim 1, wherein the compound is any one selected from the group consisting of a monobasic acid ester, a dibasic acid ester, a phosphoric acid ester, an aliphatic polyhydric alcohol and a wax. Base for. 4. Allyl isothiocyanate, shellac,
And the viscosity at 80 ° C. when kneaded at a ratio of 0.2 part by weight to 1 part by weight of shellac is 1,000 to 5
An allyl isothiocyanate composition, which comprises a compound having a range of 10,000 cP. 5. The allyl isothiocyanate composition according to claim 4, wherein the compound is contained in a proportion of 0.03 to 1 part by weight relative to 1 part by weight of shellac. 6. The allyl isothiocyanate composition according to claim 4 or 5, wherein the compound is any one selected from the group consisting of monobasic acid esters, dibasic acid esters, phosphoric acid esters, aliphatic polyhydric alcohols and waxes. Stuff. 7. The allyl isothiocyanate composition is used for any purpose selected from the group consisting of antimicrobial, insect control, antiseptic, freshness preservation and preservation. An allyl isothiocyanate composition described in 1. 8. A viscosity of 100 parts at 80 ° C. when kneaded at a ratio of 0.2 parts by weight to 1 part by weight of shellac.
A method for producing an allyl isothiocyanate preparation, which comprises a step of kneading shellac and allyl isothiocyanate in the presence of a compound having a range of 0 to 50,000 cP. 9. The method for producing an allyl isothiocyanate preparation according to claim 8, wherein the compound is contained in a proportion of 0.03 to 1 part by weight relative to 1 part by weight of shellac. 10. The allyl isothiocyanate preparation according to claim 8, wherein the compound is any one selected from the group consisting of monobasic acid esters, dibasic acid esters, phosphoric acid esters, aliphatic polyhydric alcohols and waxes. Manufacturing method. 11. In the production of an allyl isothiocyanate preparation, the viscosity at 80 ° C. when kneaded at a ratio of 0.2 parts by weight to 1 part by weight of shellac is 1,000 to 5 parts.
A method for preventing variation in the allyl isothiocyanate content in an allyl isothiocyanate preparation, which comprises a step of kneading shellac and allyl isothiocyanate in the presence of a compound having a range of 10,000 cP. 12. The method for preventing variation in the allyl isothiocyanate content in an allyl isothiocyanate preparation according to claim 11, wherein the compound is contained in a proportion of 0.03 to 1 part by weight relative to 1 part by weight of shellac. 13. The allyl isothiocyanate preparation according to claim 11, wherein the compound is any one selected from the group consisting of a monobasic acid ester, a dibasic acid ester, a phosphoric acid ester, an aliphatic polyhydric alcohol and a wax. For preventing variation in the content of allyl isothiocyanate in food.