JPH09286704A - Paradichlorobenzene composition, production of the same and preparation consisting of the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having potent insecticidal and deodorizing actions, and useful as an insecticide for a cloth and a deodorizing agent for a toilet, etc. SOLUTION: This paradichlorobenzene composition obtained by dissolving or dispersing 0.001-10wt.% vaporizable additive (e.g.; a plant essential oil) and 0.001-10wt.% retentive agent (e.g.; a natural rubber) consisting of a polymer capable of being dissolved or dispersed with a molten dichlobenzene and as a solid or a rubber state at an ambient temperature into a molten liquid obtained by melting 80-99,998wt.% paradichlorobenzene, and coagulating the obtained mixed solution by rapidly cooling on the cooling surface of an indirect cooling coagulating device. In the composition, the vaporizable additive and the retentive agent are almost uniformly dispersed in the inside of the solid paradichlorobenzene, and it is preferable to have >=30% uniform volatility of paradichlorobenzene with the vaporizable additive. Also, the mean solid growing rate in thickness direction of the growing solid from the cooling surface of the indirect cooling device is preferably 1-15mm/min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition containing paradichlorobenzene as a main component, a method for producing the same, and a preparation containing the composition as a main component. TECHNICAL FIELD The present invention relates to a composition of paradichlorobenzene in which a retaining agent made of a rubber-like polymer is contained in a substantially uniform dispersion state, a method for producing the same, and a preparation.

[0002]

BACKGROUND OF THE INVENTION Paradichlorobenzene has a strong insect and deodorant action, and its tablets are used as insect repellents for clothing and toilets. This paradichlorobenzene tablet is formed by tableting a certain amount of paradichlorobenzene crystals into a predetermined shape, for example, a tablet shape, a ball shape or a bar shape, and storing the tablet together with clothing in a container such as a closet. When placed in a box, paradichlorobenzene sublimes from the tablets, and the gas component is volatilized in the storage device to exert an insect-repellent effect, and when installed in a toilet or the like, exhibits a deodorant effect.

However, this paradichlorobenzene has a peculiar odor, and even under normal use conditions, if the amount of vaporized gas components increases, it becomes a pungent pungent odor. Therefore, as a method of reducing this irritating odor, a liquid flavor component is spray-adhered to the surface of a flaky paradichlorobenzene solid material, and then crushed, tableted and molded to be used as a tablet. As a result, the pungent odor of paradichlorobenzene is alleviated by the fragrance component that is vaporized together with the gas component of paradichlorobenzene.

However, in this case, since the fragrance component is exclusively attached to the surface of the flaky paradichlorobenzene, the fragrance component volatilizes first,
There is a problem that it is difficult to emit the fragrance for a long period of time, the fragrance of the fragrance component is strong at the beginning of use, and the fragrance becomes weaker as the product is used, and finally only the irritating odor peculiar to paradichlorobenzene is generated.

Conventionally, the addition amount of the perfume component which can be added to solid paradichlorobenzene is usually 0.01 to 0.3% by weight, preferably 0.1 to 0.3% by weight. Has been done. This is because if the amount added is less than 0.01% by weight, the effect of alleviating the pungent odor peculiar to paradichlorobenzene is less effective, and if it is more than 0.3% by weight, the added perfume ingredients are liquid. Since it is present on the surface of paradichlorobenzene at room temperature, this additive exudes to the tablet surface during tableting. In addition, when the paradichlorobenzene tablet is used, the additive may adhere to clothing and the like and cause stains and the like.

Further, the paradichlorobenzene tablet is required to have a strength capable of maintaining its shape at a minimum, but as the concentration of the liquid additive increases, the strength of the tablet decreases correspondingly, and usually 0.3% by weight. If it exceeds the range, it becomes difficult to impart the strength sufficient to maintain the tablet shape. Therefore, from this point as well, it has been said that the amount of the liquid additive such as a fragrance component that can be added to the solid paradichlorobenzene for tablet production is limited to about 0.3% by weight.

It is known that paradichlorobenzene tablets are added with an aromatic substance having an insecticidal and fungicidal action such as menthone to enhance the insecticidal and antifungal effects and reduce the irritating odor peculiar to paradichlorobenzene. In addition, a natural plant essential oil having an insect repellent action such as lemongrass oil, thyme white oil, and pimento oil is added to paradichlorobenzene.
There is also known a method of improving the insect repellent action and reducing the irritating odor peculiar to paradichlorobenzene by mixing in an amount of -30% by weight (JP-A-5-286818).

However, even in this method, since 0.5% by weight or more of the additive is added to the surface of the flaky paradichlorobenzene solid substance, problems such as exudation during tableting and reduction in tablet strength occur. And 1 to 10 in the tablet
It has been difficult to mix in wt% aroma substances and natural plant essential oils.

Further, in JP-A-6-199605, a natural plant essential oil or an extract component thereof is dissolved in a melt of paradichlorobenzene, or a mixture of paradichlorobenzene and a natural plant essential oil or an extract component thereof is used. By melting and then allowing the resulting melt to cool naturally, or by rapidly cooling in ice water, paradichlorobenzene solids in which the natural vegetable essential oil or its extract components are contained in the paradichlorobenzene solids and this The formulation used is proposed.

However, when the paradichlorobenzene melt in which the additive consisting of natural plant essential oil or its extractives is dissolved is allowed to cool and coagulate, the paradichlorobenzene slowly coagulates and the additive exudes in the process. The concentration of the additive contained in the solidified paradichlorobenzene solidified due to separation is low, most of the additive is exuded and adhered to the surface of the solid, and 0.5% by weight or more of the additive is present. Even when the solid paradichlorobenzene obtained by using the above method is tableted, only about 0.3% by weight remains inside the tablet. Further, the tablet strength was such that it was crushed when squeezed by hand.

Further, in the method of rapidly cooling and solidifying the paradichlorobenzene melt in which the additive composed of the natural vegetable essential oil or its extract component is dissolved, it is necessary to dehydrate the obtained paradichlorobenzene solid product, In addition to the troublesome waste water treatment, about 300 ppm of water remains inevitable in solid paradichlorobenzene, which causes the paradichlorobenzene tablets, which should be white, to turn brown (change to brown) when used. However, there is a problem that the appearance and usability are impaired.

[0012] Furthermore, paradichlorobenzene is solidified during storage due to its nature and becomes a lump, which makes it difficult to handle during tableting. Therefore, in order to prevent this, it is solidified at the time of preparing flakes or in the prepared flakes. It is known to add inhibitors. For example, in JP-A-62-148435 and JP-B-42-1006, paradichlorobenzene containing an anti-caking agent composed of an organic acid amide or the like in the range of 0.005 to 1.0 wt% as an additive. A method for producing a flaky paradichlorobenzene solid substance in which the melt is solidified with a drum flaker and the surface of which is covered with an anti-caking agent is disclosed, and at this time, in a vat cooled to 20 ° C. It is also disclosed to solidify a paradichlorobenzene melt containing 0.005 to 1.0 wt% anti-caking agent into flakes.

However, the operating conditions are not specified in these publications, and since the additive remains so as to cover the surface of the solid material, the additive is localized and the initial solidification occurs. Although the preventive effect can be exerted, it was difficult to exert a sufficient anti-caking effect for a long time because the additive was volatilized during storage.

Further, JP-A-48-15836 describes that a colorant is sprayed on the surface of solid paradichlorobenzene to color the solid paradichlorobenzene, and Japanese Patent Publication No. 49-13966. In the publication, there is proposed a method of preparing an appropriately colored paradichlorobenzene flake by mixing solid paradichlorobenzene with a high concentration of a colorant and white paradichlorobenzene flake without the addition of a colorant. .

However, in the former method, it is difficult to maintain the color for a long time because the colorant is present only on the surface of the solid matter, and in the latter method, the colorant and paradichlorobenzene are not maintained. Due to the poor affinity between them, paradichlorobenzene flakes are added
In addition, there is a problem that it is difficult to color the film uniformly.

On the other hand, Japanese Patent Laid-Open No. 204402/1990 discloses that an active agent such as paradichlorobenzene is 1.0 at the maximum.
As a technique for adding up to wt%, an insect repellent has been proposed in which the active agent is adhered to a porous material such as zeolite, mechanically mixed with the sublimable agent such as naphthalene, and then tablet-molded. . However, such an insect repellent has the effect of increasing the amount of volatilization of the active agent per unit time by adhering the active agent to the surface of the void portion of the porous material, while only the active agent volatilizes first. There is a problem that ends up.

Further, in JP-A-7-206605, as an insect repellent for compost, a pesticidal component composed of paradichlorobenzene containing an insecticidal component is mixed with a cellulosic compound such as ethyl cellulose, hydroxyethyl cellulose or the like for shaping. Insect repellents have been proposed. However, this insect repellent is formed by blending a small amount of a cellulosic compound, and a part of the surface of the paradichlorobenzene powder is melted by the adiabatic compression during the shaping, and the cellulose powder is deposited there. As a result of being coated, the volatilization of para-zirrolobenzene is suppressed (delayed), and thus the insect-control effect of para-zirrolobenzene is impaired and there is a problem that it cannot be fully exhibited.

Further, in JP-A-8-81324, as a technique for producing a flaky insect repellent composition comprising paradichlorobenzene containing about 0.5% by weight of natural vegetable oil or its extract component, paradichlorobenzene and natural There has been proposed a production method for obtaining a flake-like solidified product by rapidly cooling a mixed solution of vegetable oil or the like with stirring while using cold temperature of cold water. However, in the case of this manufacturing technique, one side is 1 to 3 as shown in the examples and the like.
Since it is obtained by slowly solidifying a mm-shaped rectangular flaky solidified product over about 30 minutes, the productivity is low, and natural vegetable oils, etc. are localized in the solid thickness direction of paradichlorobenzene. However, there is a problem that it is not uniformly dispersed (diffusion occurs in the concentration distribution). In particular, there is also a problem that the volatilization of the natural vegetable oil becomes uneven due to the uneven distribution of the natural vegetable oil.

In addition to this, conventionally, some insect repellents and the like constituted by using the following polymers in combination have been proposed, but each of them has various problems.

For example, Japanese Examined Patent Publication No. 47-27937 discloses an insecticide formed by blending a styrene-butadiene copolymer resin with a volatile insecticidal component in a proportion of 5 to 30% of the total resin. There is. However, since the resin is the main component of this insect repellent, the volatile insecticidal component with low volatility does not produce sufficient insecticidal effect due to its less volatilization, and in the production thereof, injection molding, extrusion molding, etc. are required. In order to adopt it, it is necessary to use an expensive molding machine exclusively for plastic, and when using it, there is almost no change in weight or appearance at the stage when the volatilization of volatile components is completed, so there is no need to change the insect repellent. There were problems such as difficulty in distinguishing.

Further, Japanese Patent Laid-Open No. 6-207162 discloses a volatilization type preparation containing a thermosensitive polymer as a volatilization inhibitor to suppress volatilization of a volatilization component. Since it volatilizes or volatilizes the volatile components in the aqueous composition by gelling at high temperatures, it is limited to liquid formulations and formulations that volatilize the active ingredient through micropores or capillaries. However, it cannot be applied to solid-state preparations.

Further, Japanese Examined Patent Publication No. 59-27784 discloses a preparation such as an aromatic agent in which a large amount of a liquid volatile chemical is absorbed in a thermoplastic elastomer. However, this exemplifies a case where paradichlorobenzene is made into a liquid with camphor and a fragrance to be absorbed by a polybutadiene-based thermoplastic elastomer, but since it is difficult to absorb a large amount of paradichlorobenzene, the main component is paradichlorobenzene. A formulation cannot be formed, and it is difficult to tablet mold a thermoplastic elastomer having absorbed paradichlorobenzene, and there is a problem that the formulation form is restricted. Further, in order for the thermoplastic elastomer to sufficiently absorb the liquid volatile chemicals, it is necessary to leave both of them for about 1 day, resulting in poor productivity.

[0023]

Therefore, it is an object of the present invention to allow a relatively large amount of a volatile additive exceeding 0.3 parts by weight to exude in a solid state in a substantially uniform dispersed state. Without being contained, and without changing the volatility of paradichlorobenzene, the volatility of the volatile additive at the initial stage of use (4 weeks after use) is sufficiently suppressed, and the volatility after that is controlled arbitrarily. It is intended to provide a paradichlorobenzene composition in which the components of paradichlorobenzene and a volatile additive are vaporized at a desired ratio over a long period from the initial stage of use to the latter stage of use.

Another object of the present invention is that the volatile additive is contained in the solid material in a substantially uniform dispersion state in this manner, and the volatility of the volatile additive is appropriately adjusted according to the volatilization of paradichlorobenzene. It is an object of the present invention to provide a method for industrially producing a controlled paradichlorobenzene composition.

Further, another object of the present invention is that the additives are contained in the preparation in a substantially uniform dispersion state, and it is desired that the paradichlorobenzene and the volatile additive are desired for a long period from the initial stage of use to the latter stage of use. It is to provide a paradichlorobenzene preparation that can be volatilized in a ratio.

[0026]

[Means for Solving the Problems] That is, according to the present invention, 80 to 99.998% by weight of paradichlorobenzene, 0.001 to 10% by weight of a volatile additive, and room temperature which can be dissolved or dispersed in molten paradichlorobenzene. And 0.001 to 10% by weight of a suspending agent composed of a solid or rubbery polymer, and the volatile additive and the suspending agent are substantially uniformly dispersed in the solid body of paradichlorobenzene. is there.

The present invention also provides paradichlorobenzene 8
0 to 99.998% by weight in a molten liquid, 0.001 to 10% by weight of a volatile additive, and a suspending agent composed of a solid or rubbery polymer at room temperature which can be dissolved or dispersed in molten paradichlorobenzene 0 0.001 to 10% by weight is dissolved or dispersed, and the obtained mixed liquid is rapidly cooled and solidified on the cooling surface of the indirect cooling and solidification device to solidify the volatile additive and the suspending agent. A method for producing a paradichlorobenzene composition for obtaining a solid product of chlorobenzene.

Further, the present invention is obtained by formulating the above paradichlorobenzene composition, in which the volatile additive and the retention agent are contained in a substantially uniform dispersion state. Paradichlorobenzene preparation.

In the present invention, the paradichlorobenzene used as a raw material may be one produced by any production method as long as it can be formulated as an insect repellent or deodorant, and is not particularly limited. There is no. Also,
There is no particular limitation on the shape of the solid paradichlorobenzene formed by adding a volatile additive, a holding agent, a colorant, etc. to this paradichlorobenzene, and is peeled off as a flaky solid from the cooling surface of the indirect cooling solidification device. Further, it may be in the shape as it is, or may be crushed or classified by a sieve or the like to be easily prepared into a formulation, for example, a granule.

In the present invention, volatile additives added to such paradichlorobenzene solids include plant essential oils, extract components of plant essential oils, animal extracts, fragrances, pyrethroid insecticides, synthetic insect repellent insecticides. One or a mixture of two or more selected from agents and volatile anti-caking agents, which are appropriately selected depending on the application of the paradichlorobenzene preparation finally produced and used alone or in combination. It

For example, when a paradichlorobenzene preparation is used as an insect repellent for clothing, when three kinds of components, a plant essential oil having an insect repellent action, a plant essential oil having a bactericidal or fungicidal action and a perfume are used in combination, a perfume is used. The stimulating odor peculiar to paradichlorobenzene is mitigated by the masking effect of, and the insect repellent effect of this paradichlorobenzene and the insect repellent effect of the plant essential oil and the bactericidal or fungicidal effect exert a synergistic effect, and the clothing is protected from harmful insects, fungi or mold. You can protect more strongly.

Among these volatile additives, plant essential oils,
Most of the extract components of plant essential oils, animal extracts, fragrances and pyrethroid insecticides are liquid at room temperature. Some volatile additives are solid at room temperature, but after being dissolved in a suitable solvent (eg, plant essential oil, anti-caking agent) to form a liquid,
Alternatively, it can be directly dissolved in the paradichlorobenzene melt and uniformly dissolved or dispersed.

Examples of the vegetable essential oil of this additive include, for example,
Insect repellent nutmeg oil, clove oil, sage oil, thyme oil, lavender oil, basil oil, cypress oil, lemongrass oil, cassia oil, pimento oil, moon peach oil, and bitter almond oil with deodorant effect. , Cypress oil, nutmeg oil, geranium oil, lavender oil, lime oil, peppermint oil, vetiver oil, sweet orange oil, thyme oil, etc., and mustard oil having antibacterial or fungicidal effect, horseradish oil, horseradish oil, thyme oil , Clove oil, nutmeg oil, cypress oil and the like.

The extract components of plant essential oil include, for example, α-binene, eugenol, tsuyon, which has an insect repellent effect,
Thymol, hinokitiol, cinnamic aldecht,
Carvacrol, benzaldehyde, α-binene, geraniol, citronellal, linalool, limonene, menthol, linalyl acetate, amylcinnamic aldehyde, methyl anthraninate, isoeugenol, allyl cabronate, isobutyl acetate, benzyl acetate, etc. , Isoamyl salicylate, citral, decyl aldehyde, hydroxycitronellal, isoamyl acetate, etc., and isopropyl methylphenols such as thymol, carvacrol, and biozole, which have bactericidal or fungicidal action, and allyl isoforms, which also have bactericidal or antifungal action. Examples thereof include isothiocyanates such as thiocyanate, trans-4-methylthio-3-butenyl isothiocyanate, and phenylethyl isothiocyanate.

Further, examples of animal extracts include musk, ambergris, civet and the like. Also,
Examples of the fragrance include synthetic fragrances, natural fragrances, and perfumes. Synthetic perfume, benzaldehyde, α-pinene, geraniol, cirotoneral, 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-betaenyl isothiocyanate Examples thereof include thiocyanate and chlorobutanol. As natural fragrances, flower fragrances such as rose, jasmine, carnation, fruity fragrances such as peach, strawberry, apple banana, melon, bergamot,
Citrus flavors such as mandarin and bitter orange, spicy flavors such as glove, cinnamon and nutmeg, wood scents such as sandalwood and cedarwood, sweet scents such as absolute honey, and grass scents such as absolute violet leaves. The natural single-use perfume of. Examples of the perfume flavoring agents include lira, heliotrope, acacia, lily, plum, chrysanthemum, cyclamen, chouge, and the like, which are flavors obtained by mixing natural flavors and natural products.

As the pyrethroid insecticide,
For example, empentryn, allethrin, resmethrin,
Examples include phenothrin. These insecticides are widely used alone or as a mixture because of their weak odor, but their initial volatility was lower than that of paradichlorobenzene because of their low vapor pressure. However, in the present invention, if the pyrethroid insecticide is used as one of the additives, the synergistic effect of the two is exhibited.

Examples of anti-caking agents include ethylene glycol, diethylene glycol, triethylene glycol and their derivatives, benzyl alcohol and its derivatives, organic acid amides and their derivatives, silicone oil, triethylene glycol derivatives and dimethyl phthalate. , Phthalic acid esters such as diethyl phthalate, dibutyl phthalate and dioctyl phthalate, and tetraalkoxysilanes. Of these, the anti-caking agent having volatility is also used as a volatilizing additive.

If desired, other additives such as colorants may be added to the paradichlorobenzene solid matter in addition to the volatile additives. As the colorant, for example, aminoketone dyes, arzaline dyes, coumarin dyes,
Examples thereof include benzopyran dyes, xanthene pigments, flavin pigments and the like. These colorants are solid at room temperature, but are easily dissolved or dispersed in the paradichlorobenzene melt.

The retaining agent used in the present invention is a solid or rubber-like polymer (including oligomer) at room temperature (around 20 ° C.) that can be dissolved or dispersed in molten paradichlorobenzene, and is volatile. It is a polymer that has affinity with the agent. The following can be used as the polymer that constitutes the retaining agent.

For example, vinyl acetate resin, carbonate resin, polystyrene, acrylic resin, polyethylene glycol, polyvinyl chloride, carboxyvinyl polymer, ketone resin, vinyl polypropionate, polyacrylate,
Thermoplastic resins such as polyvinylphenol, polyparamethylstyrene, polyvinyl alcohol, polyvinyl ether, polyphenyl ether, and polybutadiene, and AB
One or more polymers selected from general-purpose or engineering plastics typified by copolymer resins such as S, AS, AAS, ACS, MBS, PET and EVA. This type of polymer is readily available and inexpensive, and various kinds of polymers can be selected and used according to the properties of the volatile additive, and can be easily dissolved in paradichlorobenzene (and again when cooled). The polymer form such as pellets, powder, etc. can be arbitrarily selected.

Further, one selected from thermosetting resins such as polyurethane, epoxy resin, unsaturated polyester, melamine resin, urea resin, silicone resin and phenyl resin.
Or two or more polymers. This type of polymer is readily available and inexpensive, and can also be swollen and evenly dispersed in paradichlorobenzene (since it does not dissolve even when heat is added, it is not dissolved after the paradichlorobenzene is volatilized). It remains in polymer form).

Further, polyurethane, polyvinyl acetate, acrylic resin, polychloroprene, polyester polyol, NBR, SBR, ethylene copolymer resin, adhesive resin such as natural rubber, EVA, polyamide, polyester, atactic polypropylene, etc. One or two or more polymers selected from the above-mentioned resins for heat-sensitive adhesives.
Polymers of this type can be dissolved in paradichlorobenzene at low temperatures and become solid at the temperature at which paradichlorobenzene solidifies. In addition, it is available in the form of a polymer such as granules or pellets, and many have compatibility with both paradichlorobenzene and the volatile additive.

Further, it is one or more polymers selected from natural polymers such as natural rubber, ethyl cellulose, methyl ethyl cellulose, propyl cellulose and ethyl hydroxy cellulose. This type of polymer has low toxicity and flexibility at low temperature, is tough, has compatibility with paradichlorobenzene and volatile additives, and contains a relatively large amount of volatile additives. be able to.

Further, butadiene / styrene TPR, polyether / polyester TPR, polyether / polyurethane TPR, ethylene propylene rubber / polypropylene TPR, ethylene propylene rubber / polyethylene T
It is one or more polymers selected from thermoplastic elastomers that exhibit elasticity at room temperature, such as PR and polybutadiene / polybutadiene TPR. In this type of polymer, a portion having a weak intermolecular bond and a portion having a strong intermolecular bond coexist, which has a high effect of retaining a perfume and the like, and is easily dissolved or swollen in paradichlorobenzene.

Each of these polymers (a general-purpose or engineering plastic represented by a thermoplastic resin or a copolymer resin, a thermosetting resin, a resin for an adhesive, a resin for a heat-sensitive adhesive, a natural polymer, a heat showing elasticity at room temperature Plastic elastomers, etc.) may be used in combination (two or more) together. The polymer used as the retaining agent preferably has an average molecular weight of 1,000 or more and a degree of polymerization of 20 or more. Furthermore, regarding the type, the type of the additive, the polarity, which is related to the affinity with the volatile additive,
It is determined according to compatibility, electron affinity, pKa, presence of active hydrogen, and the like.

In the paradichlorobenzene composition of the present invention, the mixing ratio of paradichlorobenzene, the volatile additive and the retaining agent is basically 80 to 99.998% by weight,
It is 0.001 to 10% by weight and 0.001 to 10% by weight. The mixing ratio of paradichlorobenzene is determined as the difference between the total amounts of volatile additives and suspending agents. When an anti-caking agent is added to prevent the solidification of the paradichlorobenzene solid during storage, the addition amount is preferably 0.001 to 0.05% by weight.

Regarding the amount of the volatile additive to be added, whether or not the kind, a single kind of additive or the like is added, or
Whether multiple kinds of additives or the like are added, and further, depending on the dosage form and application of the paradichlorobenzene preparation prepared by using this solid paradichlorobenzene, it is basically in the range of 0.001 to 10% by weight. And preferably in the range of 0.05 to 2.0% by weight. Further, the addition amount is more preferably 0.3% by weight or more, which was difficult to add in the conventional paradichlorobenzene preparation. If the total amount added exceeds 10% by weight, the viscosity of the mixed solution of paradichlorobenzene or the like becomes high and it becomes difficult to handle, even if the holding agent is added to the maximum.
The strength of the paradichlorobenzene solid substance and the preparation produced using the same is weakened, and the preparation becomes sticky, which is not preferable. On the other hand, if it is less than 0.001% by weight, the fragrance peculiar to paradichlorobenzene cannot be alleviated especially in the case of a fragrance.

Regarding the addition amount of the holding agent, the kind, the kind of the volatile additive, the polarity, the vapor pressure (volatility) at normal temperature and the addition amount, and the volatile property of the volatile additive are determined. It is basically 0.
001 to 10% by weight, preferably 0.05
The range of up to 1.0% by weight is preferred. This addition amount is 10% by weight
When it exceeds the limit, paradichlorobenzene sublimes and volatilizes and disappears when used as a formulation, but the retention agent remains as a residue without volatilization, making it difficult to determine the latter stage of use of the formulation (end point of volatilization). In addition, in the process of producing paradichlorobenzene, the viscosity of the melt of paradichlorobenzene becomes high, which may make it difficult to handle. On the other hand, if it is less than 0.001% by weight, the volatilization suppressing effect (retention effect) of the volatilizable additive by the retaining agent cannot be sufficiently exhibited. Therefore, the more the retention agent is, the more likely the volatilization of the volatile additive is to slow down, and when a volatile additive with low volatility is used, more retention agent residue remains,
It is necessary to determine the amount of the retention agent added in consideration of these factors.

Here, the volatilization ratio (characteristics) of paradichlorobenzene and the volatile additive in the paradichlorobenzene composition and the preparation thereof of the present invention is represented by the following uniform volatility or specific uniform volatility.

First, for the degree of uniform volatility, a volatilization test is carried out using a paradichlorobenzene composition or its formulation, and the concentration of the volatile additive remaining in the composition (or formulation) remaining at that time is measured. Therefore, the volatilization ratio of the volatile additive is indicated in a contradictory manner, and the following calculation formula is used: Uniform volatility (%) = [concentration of the volatile additive in the remaining composition (or formulation) ÷ initial concentration Concentration of volatile additives in the composition (or formulation)] × 100. In the volatilization test, the composition or the formulation is 25
For a predetermined period (1
It was allowed to stand for 8 weeks) and the concentration of the volatile additive contained in the remaining composition or formulation was measured by quantitative analysis by gas chromatography.

On the other hand, the specific volatility is 1 week, 2 weeks,
It shows the volatilization ratio of the volatile additive by the average value of the uniform volatility at the time of 4 weeks (1 month) and 8 weeks (2 months). The following formula, specific even volatility (%) = ( Equilibrium volatility at 1st week + Even volatility at 2nd week + Even volatility at 4th week + Even volatility at 8th week) / 4

The uniform volatility is 100 (%)
In the case of, the volatilization test shows that the volatilization ratio of paradichlorobenzene and the volatilizable additive are 100%.
When it is smaller than 100%, the volatile additive tends to volatilize faster, and when it is larger than 100%, paradichlorobenzene tends to volatilize faster. Therefore, the closer the degree of uniform volatilization is to 100%, the more the paradichlorobenzene and the volatile additive are volatilized substantially evenly. In addition, this even volatility is (4
From the viewpoint of preventing the volatilizable additive from volatilizing excessively over paradichlorobenzene (after elapse of a week), it is preferably at least 30% or more.

If the specific even volatility is 100%, it means that the paradichlorobenzene and the volatile additive are substantially evenly volatilized over a long period of 2 months.
Further, when it is less than 100%, the volatile additive tends to volatilize faster, and when it is more than 100%, paradichlorobenzene tends to volatilize faster. .

This specific even volatility may be arbitrarily set according to the purpose of use and the form of the paradichlorobenzene preparation, but when a volatile additive having a higher volatility than paradichlorobenzene is used, With conventional paradichlorobenzene preparations, etc., the volatilization is more volatile than that of paradichlorobenzene, and the specific even volatilization rate is 20%.
Since the tendency was as follows, in order to achieve the effect of the volatile additive over a long period of time, it is desirable to set the specific even volatility to be 30% or more, preferably 70% or more.

In the present invention, it is possible to select the amount and type of the suspending agent added so that the uniform volatility or the specific uniform volatility becomes a predetermined value.

Further, in the present invention, a volatile additive,
At least one of a retaining agent, a fragrance, a coloring agent, and a volatile anti-caking agent may be added to the inside of the solid substance of the paradichlorobenzene solid substance and further attached to the surface of the solid substance. The additive or the like attached to the surface of the solid material may be the same as or different from the additive or the like contained in the solid material. The amount of the additive or the like to be attached to the surface of the solid material is preferably 0.3% by weight or less for the convenience of tablet molding. In this way, by adhering additives and the like to the surface of the solid material, it is possible to formulate the additive and to include more additives and the like in the formulation (particularly tablets) obtained by tableting. it can.

Next, in the method for producing the paradichlorobenzene composition of the present invention, basically, a volatile additive and a suspending agent satisfying the above mixing ratio are added to the melt of paradichlorobenzene in the above mixing ratio. Alternatively, in addition to the volatile additive and the suspending agent, a colorant or the like added as necessary may be dissolved or dispersed, and the resulting mixed liquid may be rapidly cooled and solidified on the cooling surface of the indirect cooling solidification device. , It may be a batch type or a continuous type.

As a method for dissolving additives, suspending agents and the like in the paradichlorobenzene melt, since paradichlorobenzene has a melting point of 53.degree.
It may be heated to 3 to 170 ° C., preferably 60 to 120 ° C. to be melted, and predetermined additives and the like may be added to and dissolved in the melt, and paradichlorobenzene and predetermined additives and the like may be previously prepared. It may be mixed, and the mixture may be heated to 53 to 170 ° C, preferably 60 to 120 ° C to be melted.
Then, at this time, in order to prevent solidification due to heat dissipation, it is preferable to keep the whole or a part of the apparatus warm from the outside by using a heat source such as steam or hot water.

The indirect cooling and solidifying apparatus for rapidly cooling and solidifying the thus obtained solution may be any one as long as it has a cooling surface and can be rapidly cooled. For example, dip feed type, side Examples thereof include feed type and top feed type drum flakers, belt flakers and the like. From the viewpoint of economy, dip feed type drum flakers are preferable.

The cooling rate by such an indirect cooling / solidifying apparatus is slightly different depending on the kinds and amounts of the added additives, holding agents and coloring agents, but preferably the thickness of the solid growing from the cooling surface. A direction average solid growth rate of 1 to 15 mm / min, more preferably 2 to 10 mm / min,
The optimum value is 2.5 to 7 mm / min, which makes it possible to obtain a solid paradichlorobenzene composition in which additives, retaining agents and the like are contained in the solid material in a substantially uniform dispersion state. If this average solid growth rate is slower than 1 mm / min, the segregation of crystals will proceed during solidification (crystallization), and it will be difficult to incorporate additives and the like into the solid in a substantially uniform dispersion state, and cooling will be difficult. It is not economical because the productivity per solidification surface is low. On the other hand, when the speed is higher than 15 mm / min, the primary particles of the crystal become finer, the existence ratio of the crystal grain boundary of the additive becomes high, and the exudation easily occurs during tableting. In addition, the temperature of the cooling surface must be lowered, which is not economical.

The cooling rate can be controlled by controlling the temperature of the paradichlorobenzene melt in the dip, the temperature of the cooling surface of the solidification device, the temperature of the paradichlorobenzene melt and the cooling surface when a dip feed type flaker is used. It can be performed by controlling contact conditions such as contact time and flow, atmosphere temperature and the like.

By the way, the precipitation of solids on the cooling surface of the indirect cooling / solidifying apparatus proceeds from this cooling surface in the direction of the solution, that is, in the vertical direction from the cooling surface. When the solid growth rate per unit time in the vertical direction is defined as the solidification rate, the thermal conductivity of paradichlorobenzene is small,
This solidification rate decreases as the paradichlorobenzene solids grow. That is, the solidification rate of the solidified near the cooling surface of the indirect cooling / solidification apparatus is high, and the solidification rate of the solidified at a position distant from the cooling surface is low.
Therefore, the solid paradichlorobenzene has a concentration distribution of additives and the like in the thickness direction, and the purity of the paradichlorobenzene solidifies in the thickness direction of the solidified product solidified from the cooling surface of the solidification device. Tends to be high, and conversely, the concentration of additives and the like tends to be low.

Therefore, the layer thickness of the solid matter formed on the cooling surface of the indirect cooling and solidifying apparatus by quenching the solution is usually 0.5 to 2 mm, preferably 0.8 to 1.5 mm. Is good. If the layer thickness of the formed solid is in this range, it is possible to suppress changes in the concentration of additives, etc. due to changes in the coagulation rate of the solution, to a level that does not pose a problem, and to make the volatile additives and retention agents substantially uniform. And the like are preferred for obtaining a solid product of paradichlorobenzene.

Here, particularly with respect to the volatile additive, a substantially uniform dispersion state means that there is little or little difference in concentration distribution in the thickness direction with respect to the content of the volatile additive in the entire paradichlorobenzene composition. It means that. That is, about 30% of the upper layer portion including the surface in the thickness direction,
About 30% of the lower layer including the surface in the thickness direction, and
The concentration of the volatile additive contained in the middle layer portion of about 30% between the upper layer portion and the lower layer portion is 15% or less, preferably 10% or less, relative to the average of the additive concentration of the whole solid matter. It is in a state of being within.

The above-mentioned specific dispersity (%) is calculated by the following formula: Specific dispersity (%) = {[(additive concentration of upper layer part, middle layer part or lower layer part)-(additive concentration of the whole solid)) Absolute value of]
(Additive concentration of the whole solid)} × 100, and a substantially uniform dispersion state means that the relative dispersity (%) of each of these upper layer portion, middle layer portion and lower layer portion is within 15%, preferably Means within 10%. When the specific dispersity exceeds 15%, it indicates that the additive is localized in the portion exceeding the specific dispersion, and specifically, problems such as bleeding during tableting tend to occur.

The shape of the solid paradichlorobenzene obtained by the method of the present invention is flaked when peeled off from the cooling surface of the indirect cooling and solidification apparatus. Also, if necessary, crush,
The required particle size can be adjusted by an operation such as classification.

The paradichlorobenzene composition of the present invention comprises
If necessary, it is formulated into dosage forms such as tablets, granules and powders,
As a paradichlorobenzene formulation in which a volatile additive and a retention agent or a coloring agent and the like in addition to these are contained in the formulation in a substantially uniform dispersion state, an insect repellent, an insect repellent and a deodorant,
It is used for various purposes such as insect repellents and antifungal agents. Of such preparations, tablets obtained by tableting paradichlorobenzene solids can contain a relatively large amount of volatile additives in the tablet in a substantially uniform dispersed state,
It is preferable as a dosage form because it is easy to handle.

The uniform volatility of this preparation is preferably at least 30% or more from the viewpoint of preventing the volatilizable additive from volatilizing excessively than paradichlorobenzene at the initial stage of use (after 4 weeks). . Further, the uniform volatility of this preparation is more preferably 60% or more 8 weeks after the use from the viewpoint of allowing the paradichlorobenzene and the volatilizable additive to volatilize in good balance over a long period of time. Further, it is desirable that the specific even volatility of this preparation is 100% depending on the purpose of use.

In the present invention, a preparation comprising a paradichlorobenzene composition is produced by the above-mentioned production method without adding a holding agent, and the holding agent is added to the surface of the solid product of the paradichlorobenzene. Further, it may be obtained by adding a colorant or the like as needed, crushing and mixing, and then tableting. However, in the para-dichlorobenzene preparation thus obtained, the retention agent is not contained inside the para-dichlorobenzene composition (solid), so the volatile additive decreases with time when stored for a long time. If possible, it is desirable to confine it inside the solid paradichlorobenzene.

[0070]

In the present invention, the composition of paradichlorobenzene or the formulation thereof can easily contain 0.3% by weight or more of the volatile additive, and the volatile additive or the suspending agent can be contained therein. , Colorants, etc. are almost evenly dispersed, and when this is used as an insect repellent or deodorant etc., the retention agent containing a volatile additive is exposed on the surface as paradichlorobenzene sublimes and its volatility Since most or part of the additive volatilizes while being released from the holding agent, the volatilization of the volatile additive is controlled by the holding agent. At this time, volatilization of paradichlorobenzene is not particularly suppressed by the retaining agent. As a result, the components of paradichlorobenzene and the volatile additive can be volatilized at a desired ratio over a long period from the initial stage of use to the latter stage of use.

Further, according to the production method of the present invention, the paradichlorobenzene melt containing a volatile additive, a suspending agent, and if necessary, a coloring agent, etc. is rapidly cooled through the cooling surface of the indirect cooling and solidification apparatus. Before the paradichlorobenzene, the volatile additive, the retention agent or the colorant is segregated from the solution, the solution is solidified and the additives are contained in the obtained solid material in a substantially uniform dispersion state. . Furthermore, 0.3% by weight or more of additives can be easily contained in the formulation obtained by formulating the obtained composition, and volatile additives and retention agents are contained in a substantially uniform dispersion state. In particular, the additives are contained in the tablet obtained by tableting in a substantially uniform dispersion state.

[0072]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples.

Example 1 98.9 kg of para-dichlorobenzene [manufactured by Nippon Light Metal Co., Ltd .: liquid para-dichlorobenzene (purity: 99.9% or more)] was charged into a stainless steel container capable of being heated externally, and heated to 90 ° C. to prepare para-dichlorobenzene. Melt, 0.6 kg (0.60% by weight) of thyme oil (purified thyme oil) as a volatile additive having an insect-repellent action in the melt, and a polyurethane resin (made by Bayer Germany, Product Name: Desmo Call 500 #) 0.5kg
(0.50% by weight), blue dye [Nippon Kayaku Co., Ltd. trade name: S-B-N] 1 g (1 ppm) and yellow dye [Nippon Kayaku Co., Ltd. trade name: KS-Y-]. 016] 3 g (3 p
pm) was added and dissolved with stirring to obtain a green solution 1.

On the other hand, apart from this solution 1, 0.85% by weight of thyme oil, 0.71% by weight of polyurethane resin, 1.4 g of blue dye and 4.2 of yellow dye of the same kind as described above.
A solution 2 of paradichlorobenzene was prepared by adding and dissolving g of paradichlorobenzene. Then, the solution 2 was charged into the bottom (dip) of a dip feed type 0.3 m ³ drum flaker to prepare for the production of the paradichlorobenzene composition.

Next, in order to continuously prepare the paradichlorobenzene composition, the above-mentioned solution 1 was continuously replenished so that the liquid level of the dip did not change, and the cooling water temperature 10
C., dip solution temperature 68.degree. C., solidification time 17 seconds on the cooling surface (drum surface), the solution was rapidly quenched continuously on the surface of the drum flaker, and the average solid growth rate in the thickness direction was 4.6 mm / A flaky paradichlorobenzene solid having a thickness of 1.1 mm was prepared in minutes.

The respective concentrations (contents) of the volatile additive in the upper layer portion, the middle layer portion and the lower layer portion of the obtained solid paradichlorobenzene and their average values, and the specific dispersity of the volatile additive were respectively measured. The results are shown in Table 1. Upper echelon,
The additive concentration in the middle layer and the lower layer was cut out from the upper layer and the lower layer including the surface and the middle layer between them as samples by about 30% each in the thickness direction, dissolved in dichloromethane and dissolved in dichloromethane. Quantitative analysis was performed according to. As is clear from the results of Table 1, thyme oil is dispersed substantially uniformly inside the solid substance, and is contained in a proportion of 0.60% by weight based on the whole solid substance. Further, the obtained paradichlorobenzene composition was a solid material in which thyme oil was dispersed in a substantially uniform state with a semitransparent green color and no uneven color.

Next, the solid paradichlorobenzene composition thus obtained is crushed and molded into a molding machine (tabletting machine).
Was used to prepare a disk-shaped tablet having a diameter of 21 mm, a thickness of about 7 mm and a weight of about 4 g to prepare a paradichlorobenzene tablet. Then, two each of the preparations at this time were packaged with a breathable wrapping paper in which a polyethylene film was laminated on a non-woven fabric whose gas permeability was adjusted with viscose, and this packaging state was used as a preparation.

Uniform dispersity of the obtained tablets at 1, 2, 4 and 8 weeks, residual ratio of paradichlorobenzene (PDCB),
The specific volatility, the degree of thyme oil bleeding during tableting and after standing for 8 weeks in an atmosphere of 25 ° C., and the degree of residue were measured or observed. Table 2 shows the results. Regarding the degree of even dispersion and the volatilization rate of PDCB, the formulation was placed on a Petri dish in a constant temperature air blow dryer in an atmosphere of 25 ° C, and the concentration of thyme oil in the formulation remaining after each week and the weight change rate of paradichlorobenzene were measured. Measured and determined. As for the residue, 20 unpackaged preparations were placed on a Petri dish in a constant temperature air blow dryer at 25 ° C atmosphere and left for 10 days to completely sublimate paradichlorobenzene. Was measured and calculated.

As is clear from the results in Table 2, there was no rapid volatilization of thyme oil in the initial stage (4th week), and the respective uniform volatilization rates were substantially constant, and the specific volatilization uniform volatilization rate was 10%.
Since it is 0.9, paradichlorobenzene and thyme oil are volatilized in a substantially equal proportion over a long period of time. Moreover, this tablet has sufficient tablet strength, and neither thyme oil oozes on the surface of the tablet at the time of tableting and at 8 weeks. Moreover, it was confirmed that the thyme oil was stably retained in the paradichlorobenzene, and the thyme oil was volatilized so as to match the sublimation of the paradichlorobenzene. The stimulating odor peculiar to paradichlorobenzene observed at this time was not observed until the end of the sublimation. Furthermore, when the residue was examined, it was found to be small particles composed of a mixture of a high boiling point component of thyme oil and a polyurethane resin.

Comparative Example 1 Paradichlorobenzene was produced under the following conditions and method without adding a polyurethane resin as a retaining agent.
That is, 99.5 kg of paradichlorobenzene and 0.5 g (0.5 weight percent) of thyme oil were mixed in a glass bottle and dissolved under heating at 90 ° C.
The liquid level height (thickness) was poured into a flat stainless steel container floated on the water in the constant temperature water tank adjusted to 2, so that the liquid surface height (thickness) was about 9 mm, and allowed to stand, and solidified for 30 minutes. At this time, the average solid growth rate in the thickness direction was 0.23 mm / min.

The solid thus obtained was taken out of the container, and a part thereof was collected for analysis. As in Example 1, the volatility of the solid in the upper layer portion, middle layer portion and lower layer portion was measured. Each concentration (content) of the additive and its average value, and the specific dispersity of the volatile additive were measured. The results are shown in Table 1. As is clear from the results in Table 1, thyme oil is localized near the upper layer of the solid matter. Further, it was visually observed that the surface of the obtained solid material had some liquid material.

Then, using the obtained solid paradichlorobenzene, a tablet was produced in the same manner as in Example 1, and then two tablets each were packaged to prepare a tablet. The tablet was prepared in the same manner as in Example 1. The degree of uniform dispersion, the PDCB residual rate, the degree of specific uniform volatilization, the degree of bleeding, and the degree of residue were measured or observed. Table 2 shows the results.

As is clear from the results in Table 2, since the uniform volatilization rate at the initial stage (4th week) is 6.7%, and the specific volatilization uniform volatility rate is 8.9, From this, it can be seen that only thyme oil has already volatilized first. Further, in this tablet, oozing of an oily substance was confirmed during tableting, and only 0.3% by weight of thyme oil was contained inside the tablet. In addition, the same exudation was confirmed even from the first day of use, and stains considered to be thyme oil were observed on the packaging material. Furthermore, this tablet is so hard that it can be crushed with a light hand grip,
The tablet strength was extremely low. Then, after 1 week, an irritating odor peculiar to paradichlorobenzene was observed.

Comparative Example 2 With respect to the solution 1, the polyurethane resin as the retaining agent was not added, and the amount of paradichlorobenzene was changed to 99.5 kg and the amount of thyme oil was changed to 0.5 kg (0.5% by weight). Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of thyme oil added to the solution 2 was changed to 0.7% by weight.

Regarding the obtained solid matter, each concentration (content) and its average value of the volatile additive in the upper layer portion, the middle layer portion and the lower layer portion of the solid matter and the average value thereof were added in the same manner as in Example 1. The specific dispersity of the agent was measured. Table 1 shows the results
Shown in

Further, using the obtained solid paradichlorobenzene, a tablet was produced in the same manner as in Example 1, and then two tablets each were packaged to prepare a tablet. The tablet was prepared in the same manner as in Example 1. Each degree of uniform dispersion, PDCB residual rate, degree of specific even volatilization, degree of each bleeding, and degree of residue were measured or observed. Table 2 shows the results. As is clear from the results of Table 2, in addition to the uniform volatilization rate at the initial stage (4th week) being 9.6%, the specific volatilization uniform volatility rate was 10.4.
Therefore, it can be seen that only thyme oil has already been volatilized from the beginning of use. Further, no oozing of an oily substance onto the surface of this tablet was observed during the 8th week during tableting, but from the 1st week an irritating odor peculiar to paradichlorobenzene was observed. Furthermore, when the strength of this tablet was examined, the strength was such that it collapsed when squeezed by hand.

FIG. 1 shows the time-dependent changes in the uniform volatility of the paradichlorobenzene preparations of Example 1 and Comparative Examples 1 and 2. As is clear from the result of FIG. 1, in the cases of Comparative Examples 1 and 2, both of them showed a value of less than 20% in the uniform volatility at the first week and thereafter. Only volatilized first, but in the case of Example 1, the uniform volatility is always 100%.
The values before and after indicate that paradichlorobenzene and thyme oil are almost evenly volatilized.

Example 2 For solution 1, no dye was added, 97.1 kg of paradichlorobenzene and 2.4 kg of thyme oil were added.
Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of thyme oil added to Solution 2 was changed to 3.0% by weight (2.4% by weight).

Regarding the obtained solid matter, in the same manner as in Example 1, each concentration (content) of the volatile additive in the upper layer portion, the middle layer portion and the lower layer portion of the solid substance and its average value, and further the volatile addition The specific dispersity of the agent was measured. Table 1 shows the results
Shown in As is clear from the results in Table 1, the thyme oil was dispersed almost uniformly inside the solid substance, and 2.3% of the whole solid substance was obtained.
It is contained in a proportion of 4% by weight.

Using the obtained solid paradichlorobenzene, a tablet was produced in the same manner as in Example 1, and then two tablets each were packaged to prepare a tablet. The tablet was prepared in the same manner as in Example 1. Each degree of uniform dispersion, PDCB residual rate, degree of specific even volatilization, degree of each bleeding, and degree of residue were measured or observed. Table 2 shows the results. As is clear from the results in Table 2, there is no rapid volatilization of thyme oil in the initial stage (4th week), and the specific volatilization uniform volatilization degree is 113.3. Therefore, paradichlorobenzene and thyme oil are almost equal. It volatilizes over a long period of time. In addition, this tablet has sufficient tablet strength, and no thyme oil oozes on the surface of the tablet at the time of tableting and at 8 weeks, and bleeding continues until the sublimation of paradichlorobenzene ends. There was no dashi. Also, the pungent odor peculiar to paradichlorobenzene did not reach the end of the sublimation. Further, the amount of the residue was almost equivalent to the addition ratio of the added polymer as the retention agent. Furthermore, when the strength of this tablet was examined in the same manner as in Comparative Example 2, the strength was such that the shape could be maintained even if it was gripped by hand.

Example 3 For the solution 1, no dye was added, 94.0 kg of paradichlorobenzene and 5.5 kg of thyme oil were added.
Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of thyme oil added to the solution 2 was changed to 6.5% by weight in addition to (5.5% by weight).

Regarding the obtained solid matter, in the same manner as in Example 1, the respective concentrations (contents) of the volatile additive in the upper layer portion, the middle layer portion and the lower layer portion of the solid substance and their average values, and further the volatile addition The specific dispersity of the agent was measured. Table 1 shows the results
Shown in As is clear from the results in Table 1, the thyme oil was dispersed almost uniformly inside the solid substance, and was 5.9% based on the whole solid substance.
It is contained in a proportion of 2% by weight.

Using the obtained solid paradichlorobenzene, a tablet was produced in the same manner as in Example 1, and then two tablets each were packaged to prepare a tablet. The tablet was prepared in the same manner as in Example 1. Each uniform dispersion degree, PDCB volatilization rate, specific uniform volatilization degree, degree of each bleeding, and degree of residue were measured or observed. Table 2 shows the results. As is clear from the results in Table 2, there is no rapid volatilization of thyme oil in the initial stage (4th week), and the specific volatilization uniform volatilization degree is 141.7. Therefore, paradichlorobenzene and thyme oil are almost equal. It volatilizes over a long period of time. In addition, this tablet has sufficient tablet strength, and no thyme oil oozes on the surface of the tablet at the time of tableting and at 8 weeks, and bleeding continues until the sublimation of paradichlorobenzene ends. There was no dashi. Also, the pungent odor peculiar to paradichlorobenzene did not reach the end of the sublimation. Furthermore, when the strength of this tablet was examined in the same manner as in Example 2, the strength was such that the shape could be maintained even if it was picked up by hand.

Here, the relationship between the addition amount of the volatile additive and the degree of uniform volatilization of the paradichlorobenzene preparation in Examples 1 to 3 and Comparative Example 2 is shown in FIG. As is clear from the results of FIG. 2, in the case of Comparative Example 2 in which the retaining agent was not added, the volatile additive was contained in the solid of paradichlorobenzene in an amount of 0.5% by weight. Even if it is contained, it volatilizes in the initial stage, but in the case of the example, only 0.5 to 0.6% by weight of the retention agent is contained.
By adding it, it becomes possible to confine the volatile additive to the inside of the solid material by up to about 5 times (Example 3),
Moreover, volatilization of the additive can be suppressed. Further, from the results of Table 2, since the residual ratio of paradichlorobenzene in the example is not significantly different from that in Comparative example 2, addition of the suspending agent does not suppress the volatilization of paradichlorobenzene. I understand.

Example 4 With regard to the solution 1, the dye was not added, the paradichlorobenzene was changed to 97.5 kg, and the amount of the polyurethane resin serving as a retention agent was changed to 2.0 kg (2.0% by weight). Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of the polyurethane resin added was changed to 2.3% by weight. Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed substantially uniformly inside the solid substance, and is contained in a proportion of 5.92% by weight based on the whole solid substance. Also, as is clear from the results in Table 2, the even volatility at 8 weeks was 14
At 09.0, the specific volatilization uniform volatilization degree is 436.2, and the PDCB volatilization rate at 8th week is 19.2, so the volatilization of thyme oil in the latter period of use is extremely controlled, while the paradigm Volatilization of chlorobenzene is increasing. Further, this tablet had sufficient tablet strength, and leaching of thyme oil did not occur until the sublimation of paradichlorobenzene was completed. The pungent odor peculiar to paradichlorobenzene did not reach the end of sublimation, though the volatilization of thyme oil was extremely controlled in the latter stage of use. Furthermore, when the strength of this tablet was examined in the same manner as in Example 2, the strength was such that the shape could be maintained even if it was picked up by hand. Regarding the tablet strength, it was confirmed that the tablets of Examples 5 to 9 described later have the same strength.

Example 5 With respect to the solution 1, no dye was added, 94.0 kg of paradichlorobenzene and 5.5 kg of thyme oil were added.
Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of white thyme oil added to the solution 2 was changed to 5.8% by weight in addition to (5.5% by weight). Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed in the solid substance substantially uniformly and is contained at a ratio of 5.76% by weight based on the whole solid substance. Further, as is clear from the results of Table 2, the even volatility at the 8th week was 29
At 50.6, the specific volatilization uniform volatility is 829.9, and the PDCB residual rate at 8 weeks is 8.2.
The volatilization of thyme oil in the latter period of use is extremely controlled, while the volatilization of paradichlorobenzene is rapidly increasing. Further, this tablet had sufficient tablet strength, and slight bleeding was observed on the tablet surface both during tableting and at 8 weeks, but this was not a problem for practical use. . In addition, the bleeding did not proceed further until the end of sublimation. The pungent odor peculiar to paradichlorobenzene did not reach the end of sublimation, though the volatilization of thyme oil was extremely controlled in the latter stage of use.

Example 6 With respect to the solution 1, no dye was added, 89.0 kg of paradichlorobenzene, 5.0 kg (5.0% by weight) of the polyurethane resin as a retaining agent, and thyme oil were added. While changing to 6.0 kg (6.0 wt%), the addition amount of the polyurethane resin in the solution 2 was 6.0.
Paradichlorobenzene was produced in the same manner as in Example 1 except that the amount of thyme oil added was changed to 7.2% by weight. Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed in the solid substance substantially uniformly, and is contained in a proportion of 6.34% by weight based on the whole solid substance. In addition, as is clear from the results in Table 2, the even volatility at the 8th week was 62%.
At 9.9, the specific volatilization uniform volatility is 252.2, and the PDCB volatilization rate at 8 weeks is 14.4.
The volatilization of thyme oil in the latter period of use is extremely controlled, while the volatilization of paradichlorobenzene is rapidly increasing. Further, this tablet had sufficient tablet strength, and leaching of thyme oil did not occur until the sublimation of paradichlorobenzene was completed. The pungent odor peculiar to paradichlorobenzene was not reached until the end of sublimation, though the volatilization of thyme oil was controlled in the latter stage of use.

Example 7 With respect to the solution 1, the dye was not added, the content of the paradichlorobenzene was changed to 99.45 kg, and the amount of the polyurethane resin as the retention agent was changed to 0.05 kg (0.05% by weight). Regarding 2, the paradichlorobenzene composition and its preparation were produced in the same manner as in Example 1 except that the amount of the polyurethane resin added was changed to 0.07% by weight. Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed in the solid substance substantially uniformly and is contained in a proportion of 0.58% by weight based on the whole solid substance. Further, as is clear from the results in Table 2, the even volatility gradually decreased with each passing week, and the specific even volatility was 45.9. Further, this tablet had sufficient tablet strength, and leaching of thyme oil did not occur until the sublimation of paradichlorobenzene was completed. The pungent odor peculiar to paradichlorobenzene did not exist until the end of the sublimation.

Example 8 For solution 1, 98.5 k of paradichlorobenzene was added.
g, the amount of polyurethane resin added as a retention agent is 1.0k
A paradichlorobenzene composition and its preparation were produced in the same manner as in Example 1 except that the amount of the polyurethane resin added to the solution 2 was changed to 1.3% by weight, while changing the amount to 1.0 g (1.0% by weight). did. Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed in the solid substance substantially uniformly and is contained in a proportion of 0.58% by weight based on the whole solid substance. Further, as is clear from the results in Table 2, the specific even volatility was 65.8. Further, this tablet had sufficient tablet strength, and leaching of thyme oil did not occur until the sublimation of paradichlorobenzene was completed. The pungent odor peculiar to paradichlorobenzene did not exist until the end of the sublimation.

Example 9 Dibutyl phthalate (DBP) 0.0 as an anti-caking agent
A paradichlorobenzene composition and its preparation were produced in the same manner as in Example 8 except that 34 kg (0.034% by weight) was added to the solution 1 and 0.05 kg was also added to the solution 2. Further, as in Example 1, predetermined measurements of the solid matter were performed and the results are shown in Table 1, and the predetermined measurements and observations of the formulation were performed and the results are shown in Table 2.

As is clear from the results shown in Table 1, thyme oil is dispersed in the solid material substantially uniformly and is contained in a proportion of 0.50% by weight based on the whole solid material. Moreover, as is clear from the results in Table 2, the even volatility gradually decreased with each passing week, and the specific even volatility was 63.6. Further, this tablet had sufficient tablet strength, and leaching of thyme oil did not occur until the sublimation of paradichlorobenzene was completed. The pungent odor peculiar to paradichlorobenzene did not exist until the end of the sublimation.

[0107]

[Table 1]

[0108]

[Table 2]

Here, FIG. 3 shows the relationship between the addition amount of the retaining agent and the even volatilization degree of the paradichlorobenzene preparation in Examples 1, 7 to 9 and Comparative Example 2. As is clear from the results of FIG. 3, the uniform volatility tends to increase as the amount of the holding agent added increases. Further, in order to volatilize thyme oil (0.55 or 0.60% by weight), which is a volatile additive, most evenly with paradichlorobenzene,
It can be seen that about 0.5% by weight of polyurethane is required. On the other hand, when it is desired to volatilize the thyme oil intensively in the early stage of use, it can be controlled by gradually reducing the amount of polyurethane added according to the degree.

Examples 10 to 18 Paradichlorobenzene compositions and their preparations were produced in the same manner as in Example 8 except that the kind of the retaining agent was changed to the following polymeric materials. -Example 10 ... Polycarbonate compound [A2200 manufactured by Idemitsu Petrochemical Co., Ltd.]-Example 11 ... ABS compound [Electrochemical Co., Ltd.]
Manufactured by CL] -Example 12 ... SBS-based thermoplastic elastomer [Tufprene A manufactured by Asahi Kasei Co., Ltd.]-Example 13 ... vinyl acetate resin [Sakunol manufactured by Electrochemical Co., Ltd.]-Example 14 ... polystyrene resin [ Dainippon Ink Co., Ltd.
GX9365] -Example 15 ... Ethyl cellulose [manufactured by Sansho Co., Ltd., N-
4] -Example 16 ... Ethyl hydroxyethyl cellulose [Tokyo Kasei Co., Ltd., first grade reagent] -Example 17 ... Polyethylene glycol [Wako Pure Chemical Industries, Ltd., CAFO154 (average molecular weight 1500)]-Example 18 … Acrylic resin [Asahi Kasei Co., Ltd., Tell powder 80N]

Further, in the same manner as in Example 8, the obtained solid matter was subjected to predetermined measurement, and the results are shown in Table 3 and
The formulation was subjected to predetermined measurements and observations, and the results are shown in Table 4. No irritating odor peculiar to paradichlorobenzene was observed until the end of sublimation in any of the examples. Furthermore, the strength of the tablets obtained in Examples 10 to 18 was examined in the same manner as in Example 2. As a result, the strength of any of the tablets was such that the shape could be maintained even if they were grasped by hand. .

Comparative Example 3 Example 1 was changed except that the polyurethane resin was changed to cellulose powder (TR-101 manufactured by Asahi Kasei Apicel Co., Ltd.).
A paradichlorobenzene composition and its preparation were produced in the same manner as in. Further, similar to Example 1, the obtained solid product was subjected to predetermined measurement and the result is shown in Table 3, and the formulation was subjected to predetermined measurement and observation, and the result is shown in Table 4. As is clear from the results in Table 4, the specific even volatilization degree was 10.8, and the thyme oil was volatilized earlier than the paradichlorobenzene. It was found that the porous polymer did not dissolve in paradichlorobenzene and the effect of suppressing the volatilization of thyme oil was not obtained.

[0113]

[Table 3]

[0114]

[Table 4]

FIG. 1 shows the changes over time in the uniform volatility of the paradichlorobenzene preparations of Examples 10 to 18 and Comparative Example 3. As is clear from the result of FIG. 1, even if the retention agent is added at the same addition amount of 0.5% by weight,
It can be seen that the uniform volatility (in other words, the retention effect of the volatile additive) differs depending on the type of the polymer, such as solubility in paradichlorobenzene, properties such as polarity, and affinity for thyme oil. This shows that the volatilization ratio of paradichlorobenzene and the volatile additive can be adjusted by changing the type of the holding agent.

For example, when it is desired to volatilize the paradichlorobenzene and the volatile additive almost evenly from the initial stage of use to the latter stage of use (to ensure a specific even volatility of 60% or more), Example 1 First Example 1
It is preferable to select and use the kind of holding agent as used in 1, 13, 15, 16, 20. In addition, it is desirable to volatilize the volatile additive to some extent from the start of use (60% as the uniform volatility becomes 1 week, 2 weeks, 4 weeks, 8 weeks).
%, 50%, 40%, 30%), it is advisable to select and use the type of holding agent used in Examples 10, 12, 14, and 17.

Comparative Example 4 As solution 1, paradichlorobenzene 99.6 kg,
Thyme oil 0.4kg (0.4wt%), blue dye 1g
(1 ppm) and 3 g (3 ppm) of a yellow dye were prepared, and as the solution 2, thyme oil 0.
85% by weight, blue dye 1.4 ppm and yellow dye 4.2
A mixed solution of ppm was prepared. Next, as in Example 1, except that the cooling water temperature was 20 ° C., the dip solution temperature was 75 ° C., the solidification time on the cooling surface (drum surface) was 4 minutes, and flakes having a thickness of 1.7 mm were produced. Then, a flaky paradichlorobenzene solid substance was prepared. At this time, the average solid growth rate in the thickness direction was 0.42 mm / min.

Each concentration (content) of the volatile additive and its average value in the upper layer portion, the middle layer portion and the lower layer portion of the obtained paradichlorobenzene solid matter, and the specific dispersity of the volatile additive were measured. , Upper layer concentration 0.15% by weight, middle layer concentration 0.39% by weight, lower layer concentration 0.47
% By weight, average value: 0.35% by weight, specific dispersity: 57%. As is clear from this, when the paradichlorobenzene solid matter was prepared under the above-mentioned production conditions, it was found that the thyme oil was localized inside the solid matter and was not uniformly dispersed.

[0119]

INDUSTRIAL APPLICABILITY The solid paradichlorobenzene and its preparation of the present invention contain a volatile additive and a suspending agent consisting of a solid or rubbery polymer at room temperature in a substantially uniform dispersion state in the solid or preparation. Has been. Therefore, a relatively large amount of the volatile additive exceeding 0.3 parts by weight can be contained in the solid material, and the solid material can be contained without exuding. Further, the components of the paradichlorobenzene and the volatile additive can be volatilized at a desired ratio for a long period from the initial stage of use to the latter stage of use without changing the volatility of paradichlorobenzene. For example, it becomes possible to volatilize a desired volatilizable additive at a ratio equal to that of paradichlorobenzene.

Further, according to the production method of the present invention, it is possible to industrially advantageously produce a paradichlorobenzene composition in which a volatile additive and a retaining agent are contained in a solid material in a substantially uniform dispersion state. .

[Brief description of drawings]

FIG. 1 is a schematic diagram of Examples 1, 10 to 18 and Comparative Examples 1 to 1.
3 is a graph showing the change over time in the uniform volatility of the paradichlorobenzene preparation in Example 3.

FIG. 2 is a correlation diagram showing the relationship between the addition amount of the volatile additive and the even volatility of the paradichlorobenzene preparation in Examples 1 to 3 and Comparative Example 2.

FIG. 3 is a correlation diagram showing the relationship between the amount of the retention agent added and the even volatility of the paradichlorobenzene preparation in Examples 1, 7 to 9 and Comparative Example 2.

Claims (17)

[Claims] 1. Paradichlorobenzene 80-99.99
8% by weight, and volatile additives 0.001 to 10% by weight,
Retention agent consisting of solid or rubbery polymer at room temperature that can be dissolved or dispersed in molten paradichlorobenzene 0.00
A paradichlorobenzene composition comprising 1 to 10% by weight of a volatile additive and a suspending agent, which are dispersed substantially uniformly inside a solid product of paradichlorobenzene. 2. A uniform volatilization rate (after 4 weeks) showing the volatilization ratio of the paradichlorobenzene and the volatile additive is 30.
The paradichlorobenzene composition according to claim 1, wherein the content is at least%. 3. The retaining agent is vinyl acetate resin, carbonate resin, polystyrene, acrylic resin, polyethylene glycol, polyvinyl chloride, carboxyvinyl polymer, ketone resin, vinyl polypionate, polyacrylate, polyvinylphenol, polyparamethylstyrene. Thermoplastic resins such as polyvinyl alcohol, polyvinyl ether, polyphenyl ether, polybutadiene, and ABS, AS, AAS, ACS, MBS, PET,
The paradichlorobenzene composition according to claim 1, which is one or more polymers selected from general-purpose or engineering plastics typified by copolymer resins such as EVA. 4. The retention agent is one or more polymers selected from thermosetting resins such as polyurethane, epoxy resin, unsaturated polyester, melamine resin, urea resin, silicone resin and phenyl resin. Item 1
Paradichlorobenzene composition as described. 5. The holding agent is polyurethane, polyvinyl acetate, acrylic resin, polychloroprene, polyester polyol, NBR, SBR, ethylene copolymer resin,
The para-dichlorobenzene composition according to claim 1, which is one or more polymers selected from resins for adhesives such as natural rubber and resins for heat-sensitive adhesives such as EVA, polyamide, polyester and atactic polypropylene. . 6. The retaining agent is natural rubber, ethyl cellulose, methyl ethyl cellulose, propyl cellulose,
The paradichlorobenzene composition according to claim 1, which is one or more polymers selected from natural polymers such as ethylhydroxycellulose. 7. The butadiene-styrene T is the retaining agent.
PR, polyether / polyester TPR, polyether / polyurethane TPR, ethylene propylene rubber / polypropylene TPR, ethylene propylene rubber / polyethylene TPR, polybutadiene / polybutadiene TPR
The paradichlorobenzene composition according to claim 1, which is one or more polymers selected from thermoplastic elastomers that exhibit elasticity at room temperature. 8. The paradichlorobenzene composition according to claim 1, wherein the retaining agent is one or more polymers selected from all the polymers according to claims 3 to 7. 9. The paradichlorobenzene composition according to claim 1, wherein at least one of a colorant and an anti-caking agent is added to the inside of the solid substance of paradichlorobenzene. 10. The paradichlorobenzene composition according to claim 1, wherein the volatile additive is contained in the solid substance of paradichlorobenzene in a substantially uniform dispersion state with a relative dispersity of 15% or less. 11. The volatile additive is one or more selected from plant essential oils, plant essential oil extract components, animal extracts, fragrances, volatile anti-caking agents, insecticides and insect repellents. The paradichlorobenzene composition according to claim 1, which is 12. Paradichlorobenzene 80-99.9.
A volatile additive is added to a melt obtained by melting 98% by weight.
1 to 10% by weight and 0.001 to 10% by weight of a suspending agent composed of a solid or rubbery polymer which can be dissolved or dispersed in molten paradichlorobenzene at room temperature are dissolved or dispersed, and the resulting mixed solution is indirectly A method for producing a paradichlorobenzene composition, characterized in that a solid product of paradichlorobenzene in which a volatile additive and a holding agent are substantially uniformly dispersed is obtained by rapidly cooling and solidifying on a cooling surface of a cooling and solidifying device. 13. The paradichlorobenzene according to claim 12, wherein, when the mixed solution is rapidly cooled, the average solid growth rate in the thickness direction of the solid that grows from the cooling surface of the indirect cooling solidification device is in the range of 1 to 15 mm / min. A method for producing a composition. 14. A product obtained by formulating the paradichlorobenzene composition according to any one of claims 1 to 11, wherein the volatile additive and the suspending agent are substantially uniformly dispersed in the formulation. Paradichlorobenzene preparation characterized by being contained in. 15. The paradichlorobenzene preparation according to claim 14, wherein an even volatilization degree (at the time of 4 weeks) showing a volatilization ratio of paradichlorobenzene and the volatile additive in the preparation is 30% or more. 16. A retaining agent, or at least one of a colorant and anticaking agent, in addition to this retaining agent, is attached to the surface of the paradichlorobenzene composition according to any one of claims 1 to 11. The paradichlorobenzene preparation according to claim 14, which comprises: 17. Volatile additive 0.001 to 10% by weight
A paradichlorobenzene 80-99.998% by weight melted solution was rapidly cooled on the cooling surface of an indirect cooling and solidification device to obtain a solid product of paradichlorobenzene, and a holding agent composed of a solid or rubbery polymer at room temperature. 0.001-10
A paradichlorobenzene preparation characterized in that it is prepared by adhering weight% thereof.