JPH09188601A - Oily material-containing paradichlorobenzene formulation and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oily material-containing paradichlorobenzene formulation without bleeding of the oily material, capable of uniformly volatilizing with the oily material, leaving no solid residue after volatilization and useful as insecticides for clothing, deodorants for toilets, etc. SOLUTION: This oily material-containing paradichlorobenzene formulation is obtained by adding a hold-back agent (e.g. a diester of phthalic acid) which suppresses volatilization of the oily material to 100 pts.wt. paradichlorobenzene containing >=0.1 pt.wt. volatile oily material (natural essential oil, a natural essential oil extract, a perfume, a pyrethroid-based insecticide, etc.) almost uniformly dispersed in paradichlorobenzene. Paradichlorobenzene and the oily material are preferably volatilized almost uniformly within 40% degree of nonuniform volatilization. The uniform rate dispersed in paradichlorobenzene is preferably <=15% specific degree of dispersion. The concentration of the hold-back agent is preferably 0.1-500 pts.wt. against the oily material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a paradichlorobenzene preparation containing an oily substance and a method for producing the same. Specifically, the present invention relates to an insect repellent and a deodorant obtained by mixing an oily substance such as a volatile natural essential oil or a fragrance with paradichlorobenzene.

[0002]

Conventionally, paradichlorobenzene has been used as one of insect repellents for clothing. This para-dichlorobenzene has a peculiar odor and does not necessarily feel comfortable to everyone, and various fragrances have been added to improve the fragrance tone. Further, recently, a solid paradichlorobenzene mixture containing a substance having a high insecticidal effect and a component that works synergistically with paradichlorobenzene to enhance the insecticidal effect has been proposed.

Further, as a deodorant for toilets, paradichlorobenzene is tablet-molded into a spherical shape and used by throwing it into a male toilet or by hanging it around the toilet. Further, it has been proposed that a fragrance is added to soften a peculiar odor like the insect repellent.

As paradichlorobenzene, flaky paradichlorobenzene solids containing an anti-caking agent are made into bags and sold. In the conventional manufacturing method, in order to mix oily substances such as fragrances and other insect repellent components into this solid substance, flakes or pulverized into powder, and after adding the oily substance to the surface by pulverization mixing or the like. It is made to adhere and compressed into tablets.

[0005]

For this reason, since most of the usual flavors and natural essential oils are oily substances, addition of more than 0.1 part by weight of paradichlorobenzene by the conventional method will result in oiling by tableting. The substance exuded or could not be formed into a tablet when it exceeded 0.3 parts by weight. As a result, the amount of the liquid additive added has been limited to 0.3 parts by weight. On the other hand, JP-A-47-2953
6 and Japanese Patent Laid-Open No. 2-204402 allow addition of an oily substance in excess of 0.3 parts by weight by adding a solid porous chemical, but there is a problem that a solid residue remains after use.

When the oily substance has a high volatility, it volatilizes first during storage, or volatilizes earlier than sublimation of paradichlorobenzene during use, and the expected effect cannot be obtained. It was

The present inventors have completed the present invention as a result of intensive research aimed at solving the above problems.

That is, the object of the present invention is to prevent the oily substance from leaching out from the paradichlorobenzene, and to keep the oily substance and the paradichlorobenzene in a substantially equal state during the storage of the product and the use thereof without any loss of the oily substance or the paradichlorobenzene. Another object of the present invention is to provide a paradichlorobenzene preparation which can be volatilized and does not leave a solid residue after the paradichlorobenzene preparation is completely volatilized.

Further, in order to enhance the insect and / or deodorant (aromatic) effect, paradichlorobenzene in which a relatively large amount of an oily substance is retained in the preparation by controlling the crystallization speed or the like and keeping the oily substance dispersed substantially uniformly To provide a method for producing a paradichlorobenzene preparation containing an oily substance in which volatilization of the oily substance is controlled by using a solid substance and adding a holding agent at the time of producing the solid substance or at the time of tableting. .

[0010]

In order to achieve the above object, the present invention comprises a solid paradichlorobenzene containing paradichlorobenzene and a volatile oily substance substantially uniformly dispersed in the paradichlorobenzene. A paradichlorobenzene preparation comprising an oily substance, characterized in that the paradichlorobenzene and the oily substance are substantially evenly volatilized by adding a holding agent for controlling the volatilization of the oily substance. And

In addition, a step of mixing a volatile oily substance and a retaining agent in molten paradichlorobenzene and uniformly dispersing them, and cooling the mixed solution obtained in the previous step to remove the oily substance and the retaining agent in paradichlorobenzene. A method for producing a paradichlorobenzene preparation containing an oily substance, which comprises a step of obtaining a uniformly dispersed solid matter, and a step of tableting the solid matter, and a volatile oil volatile to molten paradichlorobenzene. A step of mixing and evenly dispersing the substances, a step of cooling the mixed solution obtained in the previous step to obtain a solid substance in which an oily substance is substantially uniformly dispersed in paradichlorobenzene, and a holding agent on the surface of the solid substance. The gist of the invention is a method for producing a paradichlorobenzene preparation containing an oily substance, which comprises a step of adhering a solid substance and a step of tablet-molding a solid substance.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the present invention, the oily substance to be mixed with paradichlorobenzene is not particularly limited as long as it is a volatile oily substance. A substance having a high volatility is preferably used in consideration of utilizing the character of the present invention. For example, as a fragrance, benzaldehyde, α-pinene, geraniol, citronellal, linalool, limonene, menthol, linalyl acetate, amylcinnamic aldehyde, methyl anthranate, isoeugenol, allyl caproate, geraniol, isobutyl acetate, benzyl acetate, isoamyl salicylate,
Citral, decyl aldehyde, hydroxycitronellal, isoamyl acetate, thujone, thymol, carvacrol, hinokitiol, biozole, allyl isothiocyanate, butenyl isothiocyanate, phenyl isothiocyanate, trans-4-methylthio-3-butenyl isothiocyanate. , Chlorobutanol, and the like. Further, for example, as a natural essential oil, bitter almond oil, cypress oil, nutmeg oil, which is a plant extracted oil,
Examples include geranium oil, lavender oil, lime oil, peppermint oil, vetiver oil, sweet orange oil, thyme oil, clove oil, sage oil, basil oil, and hiba oil. Also, musk which is an animal extract as animal extract oil,
Ambergris, civet and the like, or a compound thereof (for example, ambrooxide known as an ambergris-like component) may be dissolved in a suitable solvent and used as an essential oil. Further, as the natural essential oil extract, a liquid component or a solid component which is a constituent component of the essential oil may be used alone or in combination. The solid component may be dissolved in a suitable solvent and used as an oily substance.

The present invention is also suitable for the case where a substance having a low volatility and exhibiting an effect even in a small amount is retained in paradichlorobenzene in a stable manner and is volatilized evenly with paradichlorobenzene. Can be used for Examples thereof include pyrethroid compounds such as empensulin, allethrin, resmethrin, permethrin, etofenprox, tetramethrin, flamethrin, phenothrin, and prarethrin. Alternatively, an oily substance obtained by dissolving a solid volatile substance in a suitable solvent may be used.

The agent which can be used as the retaining agent in the present invention is not particularly limited as long as it can stably retain the oily substance substantially uniformly dispersed in paradichlorobenzene, but as a result of extensive studies on various compounds The dialkyl phthalate shown in FIG. 1 is preferably used as the retaining agent.

[0016] R1 and R2 may be the same or different. The carbon numbers of R1 and R2 are preferably about 1 to 12, respectively.

For example, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisopropyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dioctyl phthalate, didecyl phthalate, didodecyl phthalate, dinonyl phthalate, phthalate. Acid dilauryl, decyl isooctyl phthalate, butyl dodecyl phthalate, butylbenzyl phthalate, butyl lauryl phthalate, and other phthalic acid diesters, and two phthalic acid ethyl methyl ester, phthalic acid ethyl propyl ester, and phthalic acid Examples thereof include butyl octyl ester, but are not limited thereto.

Further, as a substance having a high retaining effect like the above-mentioned dialkyl phthalate, a triethylene glycol derivative is preferable, and examples thereof include esters or ethers of triethylene glycol. Examples of the acid that forms an ester with triethylene glycol include formic acid, acetic acid, propionic acid, and benzoic acid. Further, examples of the alcohol that forms an ether with triethylene glycol include methyl alcohol, ethyl alcohol, propyl alcohol, benzyl alcohol and the like. Furthermore, the two substituents of the triethylene glycol may also both be the same ester or different esters, both the same ether or different ethers, or esters and ethers. Similarly, a diethylene glycol derivative may be used.

In addition, a benzyl alcohol derivative may be used as the retaining agent. Examples of the benzyl alcohol derivative include nuclear-substituted benzyl alcohol such as benzyl alcohol and tetrafluorobenzyl alcohol, and ester derivatives such as benzyl benzoate and benzyl acetate. An ether derivative such as methylbenzyl ether, or an unscented or slightly fragrant compound having a benzyl group as a part of the structure is preferable.

As the holding agent, silicone oil such as dimethylpolysiloxane or diphenylpolysiloxane or liquid paraffin is suitable.

In the present invention, in order to volatilize the paradichlorobenzene and the oily substance substantially uniformly, it is preferable that the specific even volatilization rate is within 40%. Furthermore, it is preferably within 25%. In addition, the initial, middle period of use,
When the latter period is averaged, it is preferably within 20%.

Here, the specific even volatilization rate is obtained by the following equation.

Absolute value of specific even volatilization rate (%) = 100-{(concentration of oily substance in residual preparation or solid matter / concentration of oily substance in initial preparation or solid matter) × 100}, that is, substantially uniform volatilization Means that the smaller the specific even volatilization rate, the more uniform the content is, and the content of the oily substance in paradichlorobenzene hardly changes with time.

The uniform ratio of the oily substance in the present invention dispersed in the solid paradichlorobenzene is as follows:
The specific dispersity is preferably within 15%.

The specific dispersity of 15% or less means that there is almost no difference or a small difference in concentration distribution in the thickness direction of the solid matter. That is, the upper layer portion 3 including the upper surface in the thickness direction
The concentration of the oily substance contained in the 0% portion, the 30% portion of the lower layer portion including the lower surface in the thickness direction and the 30% portion of the middle layer portion between the upper layer portion and the lower layer portion is A state in which the relative dispersity is within 15% with respect to the average concentration is shown. If the specific dispersity exceeds 15%, it indicates that the oily substance is localized in the portion beyond that, and specifically, exudation or the like tends to occur during tableting. The paradichlorobenzene solid obtained by dispersing and holding a relatively large amount of an oily substance and a retentive agent in the solid obtained in the present invention can be obtained by crystallization on an indirect surface using an indirect cooling solidification device such as a drum flaker. It is a flaky paradichlorobenzene solid substance having a thickness of about 5 to 3 mm.

Specific dispersity (%) = [{(upper layer of solid,
Absolute value of (concentration of oily substance in middle layer or lower layer)-(concentration of oily substance in whole solid matter) / (concentration of oily substance in whole solid matter)] × 100 A colorant is added to the paradichlorobenzene preparation of the present invention. It can be contained, and when it is colored, it is preferable to uniformly disperse and hold it together with an oily substance, and it is also possible to add it to a solid substance of paradichlorobenzene and crush it into tablets to color it.

The concentration of the oily substance contained in the paradichlorobenzene preparation of the present invention depends on the type and presence or absence of addition of a coloring agent, or a single oily substance is contained, or an oily substance containing a mixture of a plurality of substances is contained. Or, depending on the dosage form of this paradichlorobenzene preparation and the purpose of use, 0.1 to 5 parts by weight is preferable,
The range of 0.3 to 1.0 parts by weight is preferable.
Therefore, the concentration of the oily substance contained in the solid paradichlorobenzene used in the preparation is preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 1 part by weight.

The concentration of the retention agent for controlling the volatilization of the oily substance in the present invention is the kind and concentration of the oily substance, the ratio of the volatilization of the oily substance and paradichlorobenzene to be controlled, and the amount of residue remaining after sublimating the paradichlorobenzene preparation. Depending on the amount, it is preferably 0.1 to 500 parts by weight with respect to the oily substance. The concentration of the retaining agent is 0.5 parts by weight of the oily substance
20 parts by weight is more preferred. If it is 0.1 part by weight or less, there is no sufficient volatilization control effect, and if it is 500 parts by weight or more, the effect of the oily substance is diminished.

The larger the amount of the holding agent added, the slower the volatilization of the oily substance, that is, the higher the specific even volatilization rate. However, when the volatility of the oily substance is low, the residue after sublimating paradichlorobenzene Since a large amount remains, the addition amount may be determined by adding these.

(Note that the concentration of the oily substance is 0.3 parts by weight to 100 parts by weight of paradichlorobenzene as described above.
When the content of the retaining agent is 0.5 parts by weight to 20 parts by weight with respect to the oily substance in the case of 1.0 parts by weight, it is 0.0015 parts by weight to 0.2 parts by weight when converted to 100 parts by weight of paradichlorobenzene. Become. ) The paradichlorobenzene solid matter used in the present invention is formulated into a dosage form such as a tablet, if necessary, and as a paradichlorobenzene preparation in which an oily substance is contained in the formulation in a substantially uniform dispersion state, an insect repellent, an insect repellent and a deodorant agent. It is used in various applications such as agents, deodorants, insect repellents and mildew proofing agents.

The retainer for controlling the volatilization of the oily substance in the present invention makes the preliminarily prepared oily substance substantially uniform even if it is added in the step of producing the paradichlorobenzene solid in which the oily substance is substantially uniformly dispersed. A holding agent may be attached to the surface and added in the process of formulating the dispersed paradichlorobenzene solid.

Further, the following two methods are preferable as the method of incorporating the oily substance and the retaining agent into the solid paradichlorobenzene.

In the step of mixing the volatile oily substance and the holding agent in the molten paradichlorobenzene and uniformly dispersing them, the oily substance and the holding agent are separately added to the molten paradichlorobenzene to dissolve or disperse the oily substance. It is also possible to add a retainer to the above and stir it, and then add it to molten paradichlorobenzene to disperse it substantially uniformly.

Further, in the step of cooling used in the present invention to obtain a solid substance in which an oily substance and a retaining agent are dispersed substantially uniformly in paradichlorobenzene, crystallization is carried out by using an indirect cooling device such as a drum flaker. Speed from 1mm / min to 15
It may be crystallized by cooling at a rate of mm / min.

Further, in the step of tablet-molding the solid material, the conventional tableting machine used for tableting paradichlorobenzene alone or paradichlorobenzene containing a trace amount of additives can be used as it is. .

In the paradichlorobenzene preparation containing the oily substance constituted as described above, first, the oily substance is held in the paradichlorobenzene in a substantially uniform dispersion state, and the volatilization of the oily substance is controlled by the holding agent. ing.

Then, paradichlorobenzene sublimes at a constant speed. Further, the oily substance existing on the surface of paradichlorobenzene is volatilized at a constant speed. The oily substance is exposed to the surface of paradichlorobenzene at a constant rate by sublimation of paradichlorobenzene. For this reason, oily substances usually volatilize at a faster rate than the rate of sublimation of paradichlorobenzene. By adding a holding agent to this, volatilization of the oily substance is controlled, and the oily substance can be volatilized at a rate close to the rate of sublimation of paradichlorobenzene. This volatilization is effective insect repellent and /
Or it represents an odor-preventing (aroma) effect. Finally, both the paradichlorobenzene and the oily substance are completely vaporized and disappear at the same time. At this time, if the holding agent or the like is volatile, it disappears, and if it is non-volatile or hardly volatile, it remains as a residue.

[0038]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.

[0039]

Example 1 99.5 kg of paradichlorobenzene was charged into a stainless steel container, melted at 90 ° C., and 0.5 kg (0.5 part by weight) of thyme oil as an oily substance and triethylene glycol dichloride as a holding agent. Acetate 30
g (0.03 parts by weight) was added and stirred to dissolve. Separately, a solution of paradichlorobenzene adjusted to a concentration of 0.7 parts by weight of thyme oil and 0.04 parts by weight of triethylene glycol diacetate was placed in the dip (bottom part) of a 0.3 m ² dip-feed type drum flaker, While replenishing the solution so that the liquid level of the dip does not change, the solution is rapidly cooled at a cooling water temperature of 20 ° C, a dip temperature of 65 ° C, and a solidification time of 20 seconds on the cooling surface to obtain an average solid in the thickness direction. A flaky paradichlorobenzene solid having a thickness of 1.2 mm was prepared at a growth rate of 3.6 mm / min. Further, the flaky paradichlorobenzene solid substance was crushed and compressed to obtain a tablet-shaped paradichlorobenzene preparation.

Test results obtained by measuring and observing the physical properties and properties of paradichlorobenzene solids and paradichlorobenzene preparations produced in Examples and Comparative Examples of the present invention are shown in Tables 1 and 2 (Examples 1 to 4 and Comparative Example 1). Table 3 (Comparative Examples 2-3, Examples 5-7), Table 4 (Examples 8-12),
The results are shown in Table 5 (Examples 13 to 17). (Detailed properties have been described in each of the examples and comparative examples) Table 6 summarizes the evaluations of the examples and comparative examples based on these test results.

The measurement items, observation items and evaluation items are as follows, and the test conditions were as follows: day 0 (at the start), 1 day after the tablets were left naked on a Petri dish under an atmosphere of 40 ° C. Measurement on the 2nd, 3rd, 7th day
Observations were made.

<< Regarding Paradichlorobenzene Solids (Table 1) >>-Name of Added Retention Agent-Retention Agent Concentration (parts by Weight): Concentration of Retention Agent Contained in Solids (Concentration of Retention Agent to Oily Substance 1
The concentration of the retaining agent with respect to 00 parts by weight is shown in parts by weight. ) -Containing oily substance name-Oiling substance concentration (parts by weight): upper layer of flaky solid matter,
Middle layer, lower layer, and overall average oily substance concentration-Specific dispersity (%): Calculated from the above oily substance concentration using the mathematical formula described in the detailed description-Exudation: When solids were tableted The properties were observed and the exudation of oily substance was observed.

<< Regarding paradichlorobenzene preparation (Tables 2 to 5) >>-Name of additive-holding agent-Sublimation rate PDCB (parts by weight) with time: Sublimation rate of paradichlorobenzene preparation (abbreviated as PDCB) which decreases with time due to volatilization .

Change with time of residual oily substance concentration (parts by weight): concentration of oily substance contained in paradichlorobenzene preparation which decreases with time due to volatilization.

Specific relative volatilization rate (%): Calculated from the sublimation rate PDCB and the residual oily substance concentration using the mathematical formula described in the detailed description.

Residue: The amount of the non-volatile or hardly volatile substance contained in the paradichlorobenzene preparation (measured as 4 tablets of 5 g as 20 g of 5 tablets) remaining after the volatilization of the preparation was measured.

<< Evaluation (Table 6) >> Equal volatilization: A with a specific even volatilization rate of 25% or less on each day is A, and is 40% or less on each day or average 20.
Those within% were designated as B, and the others were designated as C. Exudation: As a result of observation, the case where no exudation was observed was designated as A, the case where slight exudation was observed was designated as B, and the case where obvious exudation was observed was designated as C.

Sensory evaluation: When the odor does not change until the volatilization of the paradichlorobenzene preparation is completed, it can be considered that the drug effect is exerted to the end, so it is set to A and no change in odor is felt, but paradichlorobenzene. The case where a peculiar odor was felt to be slightly strong was designated as B, and the case where the peculiar odor of paradichlorobenzene was felt strongly during the volatilization was designated as C.

Comprehensive evaluation: Considering the evaluation of each item, if there is at least one C, it is C, if there are more A than B, then A, and if B is more, B And

In the examples and comparative examples of the present invention, 4
Although it was observed by an acceleration test in an atmosphere of 0 ° C., when it is normally used as an insect repellent or a deodorant,
Since it is housed in a small bag such as a non-woven fabric and the volatilization speed is controlled, the aging period at room temperature corresponds to about 3 months, and in the example, a stable effect is exhibited from the actual start to the end of use.

[0051]

[Comparative Example 1] A solid paradichlorobenzene was produced in the same manner as in Example 1 except that triethylene glycol diacetate as a retainer was not added. Further, the solid matter was crushed and compressed to obtain a tablet-like paradichlorobenzene preparation.

When the appearance of the tablet was observed in the same manner as in Example, a slight exudation of an oily substance was observed on the tablet surface during tableting. Further, it was observed that the oily substance slightly exuded until the second day.

[0053]

[Comparative Example 2] 0.5 kg (0.5 parts by weight) of thyme oil as an oily substance was added to 99.5 kg of paradichlorobenzene, mixed and dissolved at 90 ° C, and floated on water at 20 ° C. Poured on a stainless steel bat with a thickness of about 9 mm,
It was solidified in about 30 minutes. The average solidification rate in the thickness direction at this time was 0.23 mm / min. (No addition of a holding agent) The solid substance after pulverization adhered to the surface of the liquid substance and felt tight. At the time of tableting, an oily substance exudes on the tablet surface,
The tablet shape could not be maintained by a normal tableting operation, and when tableting was forced, an oily substance exuded on the tablet surface, and only 0.2 part by weight of thyme oil was contained in the formulation. . Further, when the solid molded body was continuously observed until the third day, bleeding was confirmed until the third day.

[0054]

[Comparative Example 3] A paradichlorobenzene preparation was produced in the same manner as in Comparative Example 2 except that 0.03 parts by weight of dibutyl phthalate was added as a retainer during the pulverization of the solid matter.

As in Comparative Example 2, the solid matter after pulverization adhered to the surface of the liquid material and felt tight. At the time of tableting, an oily substance oozes out on the tablet surface, the tablet shape cannot be maintained by a normal tableting operation, and when the tablet is forcibly pressed, the oily substance oozes out on the tablet surface and 0. Only 19 parts by weight of thyme oil was included. Further, when the solid molded body was continuously observed until the third day, bleeding was confirmed until the third day.

[0056]

Example 2 99.5 kg of paradichlorobenzene was charged into a stainless steel container and melted at 90 ° C., and 0.5 kg (0.5 part by weight) of thyme oil as an oily substance and diethyl phthalate as a retaining agent were charged therein. 30 g (0.03 parts by weight) was added and stirred to dissolve. Separately, thyme oil 0.7
Parts by weight, a solution of paradichlorobenzene solution adjusted to a concentration of 0.04 parts by weight of diethyl phthalate, 0.3 m ² dip Feed type drum flaker dip (bottom)
The cooling water temperature was 19 ° C and the dip temperature was 65 ° C while supplementing the solution so that the liquid surface of the dip did not change.
The solution was rapidly cooled at a solidification time of 17 seconds on the cooling surface at a temperature of 1.1 ° C. at an average solid growth rate of 3.9 mm / min in the thickness direction.
A mm flaky paradichlorobenzene solid was prepared.
Further, the flaky paradichlorobenzene solid substance was crushed and compressed to obtain a tablet-shaped paradichlorobenzene preparation.

When the appearance of the tablets when the solid material was tabletted was observed, the exudation of thyme oil was not confirmed. In addition, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was retained in the paradichlorobenzene almost stably, and the thyme oil was volatilized as the paradichlorobenzene sublimated. Was done.

[0058]

Example 3 Paradichlorobenzene solids and preparations were produced in the same manner as in Example 2 except that diethyl phthalate was replaced with dibutyl phthalate.

When the appearance of the tablets when the solid material was tabletted was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The retention of thyme oil was better than that of diethyl phthalate.

[0060]

Example 4 Paradichlorobenzene solids and preparations were produced in the same manner as in Example 2 except that diethyl phthalate was replaced with dioctyl phthalate.

When the appearance of the tablets when tableting the solid matter was observed, oozing of thyme oil was not confirmed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The retention of thyme oil was better than that of diethyl phthalate and dibutyl phthalate.

As the alkyl chain of the dialkyl phthalate used as the retention agent became longer, the concentration of the oily substance with time increased. This means that the longer the alkyl chain of the dialkyl phthalate used as the retention agent, the more stable the thyme oil is retained in the paradichlorobenzene. The amount of residue increased as the alkyl chain of the dialkyl phthalate used as the retention agent became longer. This means that the longer the alkyl chain of the dialkyl phthalate used as the retaining agent is, the more components remain without being sublimated finally.

[0063]

Example 5: Dibutyl phthalate 0.02 as a holding agent
Produced in the same manner as in Example 2 except that the amount was adjusted to be parts by weight.
Paradichlorobenzene solids and formulations were obtained.

When the appearance of the tablet when the solid material was compressed was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was better than that of diethyl phthalate, but slightly inferior to that of Example 3.

[0065]

[Example 6] 0.01% dibutyl phthalate as a holding agent
Paradichlorobenzene solid matter and a preparation were obtained in the same manner as in Example 2, except that the amount was adjusted to 5 parts by weight.

When the appearance of the tablets when the solid material was tabletted was observed, oozing of thyme oil was not confirmed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was better than that of diethyl phthalate, but slightly inferior to that of Example 3.

[0067]

[Example 7] 99.5 kg of paradichlorobenzene was charged into a stainless steel container and melted at 90 ° C, and 0.5 kg (0.5 part by weight) of thyme oil as an oily substance was added thereto and dissolved by stirring. . Separately, add 0.3 parts of paradichlorobenzene solution adjusted to a concentration of 0.7 part by weight of thyme oil.
Charge the dip (bottom) of a m ² dip-feed type drum flaker, and replenish the above-mentioned solution so that the liquid level of the dip does not change, cooling water temperature 19 ° C, dip temperature 65 ° C, The solid solution was rapidly cooled at a solidification time of 17 seconds to prepare a flaky paradichlorobenzene solid substance having a thickness of 1.1 mm at an average solid growth rate in the thickness direction of 3.9 mm / min. Further, triethylene glycol diacetate was spray-adhered to the flaky paradichlorobenzene solid substance to the paradichlorobenzene solid substance to adjust to 0.0285 parts by weight, and the mixture was crushed and compressed to obtain a tablet-like paradichlorobenzene preparation.

When the appearance of the tablet when the solid material was compressed was observed, no leaching of thyme oil was confirmed. Further, it was confirmed that thyme oil was stably retained in paradichlorobenzene, and thyme oil was volatilized as the paradichlorobenzene sublimated. The retentivity of thyme oil was slightly inferior to that of Example 1 in which triethylene glycol diacetate was dissolved in paradichlorobenzene and uniformly dispersed.

[0069]

Example 8 Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 3, except that thyme oil was replaced with lemongrass oil as the oily substance.

When the appearance of the tablets when the solid material was compressed was observed, no leaching of lemongrass oil was confirmed. In addition, no oozing was observed when the observation was continued until the third day, and the lemongrass oil was stably retained in the paradichlorobenzene, and the lemongrass oil was volatilized as the paradichlorobenzene sublimated. confirmed. The holding power of lemongrass oil was almost the same as that of thyme oil.

[0071]

Example 9 Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 2 except that benzyl alcohol was adjusted to 0.0350 parts by weight in place of diethyl phthalate as a retainer.

When the appearance of the tablet when the solid material was compressed was observed, no bleeding of thyme oil was confirmed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was Retention of thyme oil was inferior to that of diethyl phthalate of Example 12.

[0073]

Example 10 Diethylene glycol acetate butyl ether was replaced with diethyl phthalate as a holding agent in an amount of 0.1.
Paradichlorobenzene solid matter and a preparation were obtained in the same manner as in Example 2 except that the amount was adjusted to 0350 parts by weight.

When the appearance of the tablets when the solid material was compressed was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was inferior to that of diethyl phthalate of Example 2.

[0075]

Example 11 Liquid paraffin was adjusted to 0.0350 parts by weight in place of diethyl phthalate as a retainer, and thyme oil was replaced with 0.5 part by weight of thyme oil as an oily substance.
Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 2 except that 0.1 part by weight of sweet orange oil as a fragrance was added to 4 parts by weight to adjust the amount to 0.5 part by weight.

When the appearance of the tablets when the solid material was compressed was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and the thyme oil and the fragrance were stably retained in the paradichlorobenzene, and the thyme oil and the fragrance were volatilized as the paradichlorobenzene sublimated. Was confirmed. In addition, the fragrance of sweet orange oil, which is a fragrance, creates the scent of paradichlorobenzene and thyme oil,
This was the preferred mode. The holding power of thyme oil was almost the same as in Example 2.

[0077]

Example 12 Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 2, except that silicon oil was adjusted to 0.0350 parts by weight in place of diethyl phthalate as a retainer.

When the appearance of the tablet when the solid material was compressed was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was Although the retention of thyme oil was inferior to that of diethyl phthalate of Example 2, it was superior to that of diethylene glycol acetate butyl ether of Example 10.

[0079]

Example 13 As a retaining agent, from 0.0350 parts by weight of diethyl phthalate of Example 2 was added silicon oil 0.0175.
Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 2, except that a mixture of 1 part by weight and 0.0175 parts by weight of diethyl phthalate was adjusted to 0.0350 parts by weight.

When the appearance of the tablets when the solid matter was compressed was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was inferior to that of diethyl phthalate alone in Example 2, but was slightly superior to that of silicone oil alone in Example 12.

[0081]

Example 14 As an oily substance, ambroxide (solid) as a compound of ambergris extracted from sperm whale was dissolved in sweet orange oil as a solvent to obtain sperm whale oil.

Then, as a retaining agent, the amount of dibutyl phthalate was adjusted to 0.0350 parts by weight in place of diethyl phthalate,
Paradichlorobenzene solids and preparations were obtained in the same manner as in Example 2 except that thyme oil was changed to 0.5 parts by weight of mackerel whale oil as an oily substance.

When the appearance of the tablets when the solid material was tabletted was observed, no bleeding of the mackerel whale oil was confirmed. In addition, no oozing was observed when the observation was continued until the third day, and the sperm whale oil was stably retained in the paradichlorobenzene, and the sperm whale oil volatilized as the paradichlorobenzene sublimated. confirmed. In addition, the aroma of ambrooxide and sweet orange was a preferable mode because it smelled the odor peculiar to paradichlorobenzene. The holding power of sperm whale oil was almost the same as that of thyme oil.

[0084]

Example 15 The same dibutyl phthalate as in Example 3 was used as the retainer, but the amount added was adjusted to 0.0100 parts by weight to obtain a solid paradichlorobenzene product and a preparation.

When the appearance of the tablets when the solid material was tabletted was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was considerably inferior to that of Example 3.

[0086]

[Example 16] As a retainer, the same dibutyl phthalate as in Example 3 was used, but the amount added was adjusted to 0.1000 parts by weight and produced in the same manner as in Example 2 to prepare solid paradichlorobenzene and a formulation. Got

When the appearance of the tablets when tableting the solid material was observed, no thyme oil ooze was observed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was better than that of Example 3.

[0088]

Example 17 The same dibutyl phthalate as in Example 3 was used as the retainer, but the amount added was adjusted to 0.0200 parts by weight, and thyme oil was adjusted to 0.1 parts by weight as an oily substance. The procedure of Example 2 was repeated to obtain a solid paradichlorobenzene product and a preparation.

When the appearance of the tablet when the solid material was compressed was observed, no bleeding of thyme oil was confirmed. Moreover, no oozing was observed when the observation was continued until the third day, and it was confirmed that the thyme oil was stably retained in the paradichlorobenzene and that the thyme oil was volatilized as the paradichlorobenzene sublimated. It was The holding power of thyme oil was the best in this example.

In the present invention, when used as an insect repellent or deodorant, an adsorbent or the like may be added to adsorb the residue. Therefore, it is preferable that the alkyl chain of the dialkyl phthalate is designed to be long and the holding power is increased if the specification is such that some residue may remain. In addition, the residues in Examples 1 to 13, Examples 15 to 17 and Comparative Examples 1 to 3 of the present invention are light yellow oil droplets remaining on the petri dish, and Example 14 is white crystalline. Was the residue of.

[0091]

INDUSTRIAL APPLICABILITY As described above in detail, the paradichlorobenzene preparation containing an oily substance according to the present invention can contain a relatively large amount of oily substance in paradichlorobenzene, and the oily substance exudes from the paradichlorobenzene preparation. Since neither the oily substance nor the paradichlorobenzene disappears first, the desired drug effect can be exerted. In addition, since the oily substance does not fall off even during storage of the product, it has various effects such as an increase in the reliability of the product.

The method for producing a solid product of paradichlorobenzene containing an oily substance according to the present invention has an effect that a solid product of paradichlorobenzene containing an oily substance can be easily obtained by cooling.

[0093]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Susumu Watanabe 2-21-14 Higashi-Ueno, Taito-ku, Tokyo Shiramoto Co., Ltd. (72) Inventor Yukihiro Sugiyama 161 Kambara, Anbara-gun, Shizuoka Nippon Light Metal Inside the Kambara Manufacturing Co., Ltd. (72) Inventor, Nobuhiko Hamana, 161 Kambara, Kambara-cho, Anbara-gun, Shizuoka Japan Light Metal Co., Ltd. Inside the Kambara Manufacturing Co., Ltd. (72) Minoru Kubo 3-2-4 Takaidahondori, Higashi-Osaka, Osaka Osaka Pharmaceutical Co., Ltd. (72) Inventor Yoshiaki Yoshioka 3-2-4 Takaidahondori, Higashiosaka-shi, Osaka Prefecture Osaka Pharmaceutical Co., Ltd.

Claims (10)

[Claims] 1. A paradichlorobenzene preparation comprising a paradichlorobenzene solid material containing paradichlorobenzene and a volatile oily substance substantially uniformly dispersed in the paradichlorobenzene, which is a retention agent for controlling the volatilization of the oily substance. A paradichlorobenzene preparation containing an oily substance, characterized in that the paradichlorobenzene and the oily substance are substantially evenly volatilized by adding an agent. 2. The paradichlorobenzene preparation containing an oily substance according to claim 1, wherein vaporizing the paradichlorobenzene and the oily substance substantially evenly is within a relative even volatilization rate of 40%. 3. The holding agent comprises one or more selected from phthalic acid diesters, triethylene glycol derivatives, diethylene glycol derivatives, benzyl alcohol derivatives, liquid paraffin, and silicone oil. Alternatively, a paradichlorobenzene preparation containing the oily substance according to claim 2. 4. The oil according to claim 1, wherein the oily substance is one or more selected from natural essential oils, natural essential oil extracts, fragrances and pyrethroid insecticides. Paradichlorobenzene preparation containing a substance. 5. The paradichlorobenzene solid material, wherein the oily substance is dispersed in the paradichlorobenzene solid material in a uniform proportion within a specific dispersity of 15% or less, according to any one of claims 1 to 4. A paradichlorobenzene preparation containing the oily substance described. 6. The paradichlorobenzene preparation containing an oily substance according to claim 1, wherein the oily substance is 0.1 part by weight or more based on 100 parts by weight of paradichlorobenzene. 7. The paradichlorobenzene preparation according to claim 1, wherein the concentration of the added retaining agent is 0.1 part by weight or more and 500 parts by weight or less based on the oily substance. 8. The paradichlorobenzene preparation containing an oily substance according to claim 1, wherein the paradichlorobenzene preparation is a tablet formed by tableting the paradichlorobenzene solid matter. 9. A step of mixing a volatile oily substance and a holding agent in molten paradichlorobenzene and uniformly dispersing them.
It is characterized by comprising a step of cooling the mixed solution obtained in the previous step to obtain a solid substance in which an oily substance and a holding agent are substantially uniformly dispersed in paradichlorobenzene, and a step of tableting the solid substance. A method for producing a paradichlorobenzene preparation containing an oily substance. 10. A step in which a volatile oily substance is mixed with molten paradichlorobenzene and uniformly dispersed, and a solid obtained by cooling the mixed solution obtained in the previous step to approximately uniformly disperse the oily substance in paradichlorobenzene. A method for producing a paradichlorobenzene preparation containing an oily substance, which comprises the steps of obtaining a product, a step of attaching a holding agent to the surface of the solid material, and a step of tableting the solid material.