JPH0977908A - Resin composition and molded product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition in which the rate of utilization of a lowly evaporable active compound is improved by controlling its bleed and to obtain a molded product therefrom. SOLUTION: This resin composition comprises 100 pts.wt. resin, 0.01-200 pts.wt. active compound and 0.1-100 pts.wt. evaporable plasticizer having a vapor pressure of 0.001mmHg or above at 20 deg.C and satisfying the formula: P1/P2>=2 (wherein P1 is the vapor pressure of the plasticizer at 20 deg.C and P2 is the vapor pressure of the compound at 20 deg.C) and a molded product is also produced therefrom.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a molded product which can control the rate at which an active compound having a low transpiration property is released from the molded product to give a molded product with an improved utilization rate of the active compound. . More specifically, a resin composition that stably holds an active compound in a molded product under sealed conditions and releases an appropriate amount of the active compound from the molded product under open conditions, resulting in a molded product with improved utilization of the active compound. And a molded article thereof

[0002]

2. Description of the Related Art Conventionally, a resin composition containing an active compound in a resin and a molded product thereof have been known, and molded products of various shapes can be obtained at a relatively low cost, so that they can be used in a wide variety of fields. Used in. These are effective in that the active compound is gradually released from the molded body by transpiration or so-called bleeding, in which the active compound oozes to the surface of the molded body, and exhibits its effect.

[0003]

In the case of an active compound having a low transpiration property, it is almost never released from the molded product by transpiration, but is mainly released from the molded product by bleeding. Bleed occurs when a compound having a saturated dissolution amount or more (supersaturated amount) in the molded product is retained in the molded product, and a supersaturated component (= active compound compounding amount-active compound in the molded product). This is a phenomenon in which the supersaturated component moves to the surface of the molded product with time until the saturated dissolution amount) moves to the surface of the molded product. Therefore,
In the case of a molded product obtained from a resin composition containing an active compound in an amount exceeding the saturated dissolution amount, the active compound bleeds to the surface of the molded product over time, but the saturated dissolution amount of the active compound in the resin is constant. It is usually difficult to control the bleeding start time and the bleeding rate of the active compound from the molded product. Further, since the active compound having a saturated dissolution amount or less is retained in the resin relatively stably, the active compound is hardly released from the molded body after the supersaturated component bleeds. Furthermore, in the case of a molded product obtained from a resin composition containing an active compound in an amount exceeding the saturated dissolution amount, the supersaturated active compound is released over time during storage / preservation of the molded product. It is not preferable because it causes bleeding to the surface of the molded product during storage to cause a defective appearance or stains the surface of other materials that come into contact with it.
Further, when the supersaturated active compound is released during storage / preservation of the molded article, the object other than the target object (for example, the tare of the molded article or When the active compound adheres to the hands of the person who wears the molded product at the start of use, the period for which the molded product releases the active compound is shorter than the desired period, or the active compound is not released from the molded product when desired. And the like may lead to a decrease in the utilization rate of the active compound.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a resin composition containing an active compound and a volatile plasticizer in a resin has a bleeding amount of the active compound with low volatile property, The present invention has been completed by finding out that a molded product with controlled bleeding start time and bleeding speed can be obtained. That is, the present invention comprises 100 parts by weight of a resin, 0.01 to 200 active compounds.
And 0.1 to 100 parts by weight of a vaporizable plasticizer having a vapor pressure of 0.001 mmHg or more at 20 ° C., and
The vapor pressure of the volatile plasticizer at 20 ° C. (P1) and the vapor pressure of the active compound at 20 ° C. (P2) are calculated by the formula: P
The present invention provides a resin composition satisfying 1 / P2 ≧ 2 and a molded product obtained by molding the resin composition. INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide a molded product having characteristics in which the amount of active compound bleeding, the bleeding start time and the speed are controlled.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the amount of a saturated dissolution of an active compound in a resin composition is increased by the action of a transpiration plasticizer, and a molded product obtained from the resin composition under a sealed condition is Bleed is suppressed. On the other hand, under open conditions,
With the evaporation of the fugitive plasticizer, the saturated dissolution amount of the active compound in the molded product decreases, and as a result, a peculiar release behavior that the supersaturated active compound bleeds from the molded product can be realized. The term "sealing conditions" as used herein refers to conditions under which an environment that suppresses the evaporation of the transpiration plasticizer from the molded product is achieved, for example, achieved by sealing the molded product with a material having a gas barrier property or the like. it can.

The volatile plasticizer used in the present invention is 20 ° C.
The organic compound has a vapor pressure of 0.001 mmHg or more. From the viewpoint of further promoting the bleeding of the active compound from the molded body, an organic compound having a value of 0.01 mmHg or more is more preferable, and an organic compound having a value of 0.1 mmHg or more is particularly preferable. The upper limit of the vapor pressure at 20 ° C. of the vaporizable plasticizer is not particularly limited, but from the viewpoint of moldability, it is usually preferable that the boiling point be the melt molding temperature of the resin composition or higher. From this viewpoint, the upper limit of the vapor pressure of the transpiration plasticizer is usually 100 mmHg or less, 10 mmHg or less is more preferable from the viewpoint of moldability, and 1 mmHg or less is particularly preferable.

Further, from the viewpoint of the above-mentioned effect of more stably retaining the active compound in the resin composition, it is more preferable that the compatibility with the resin and the active compound is good. Compatibility can be expressed in terms of solubility or miscibility, and is one important factor that determines (saturated) solubility. The degree of compatibility or the (saturated) solubility can be estimated from the solubility parameter and the dielectric constant, but experimentally, the following methods are generally known. Solubility in polyvinyl chloride can be determined by repeating a bleed test with a test sheet consisting of a resin, a fugitive plasticizer and an active compound under conditions in which the fugitive plasticizer does not evaporate (reference: polyvinyl chloride-its basis). And application- (Kinki Chemical Society, Vinyl Section, ed., P356-357 (1988) Nikkan Kogyo Shimbun). Solubility in other resins such as polyolefin resins can be determined by the same method.

Evaporable plasticizers are known in the art, such as liquid esters (hereinafter sometimes simply abbreviated as liquid) at room temperature (23 ° C.), liquid alcohols, liquid ketones, fragrances,
It can be selected from animal and plant essential oils and the like. As the liquid ester, phthalic acid esters, linear dibasic acid esters, phosphoric acid esters and the like can be exemplified. Specific examples of transpiration plasticizers suitable for the present invention include dimethyl adipate, dimethyl glutarate, dimethyl succinate, dimethyl phthalate, diethyl phthalate, triethyl phosphate, tributyl phosphate, dimethyl maleate, dimethyl. Examples include succinate. The amount of the volatile plasticizer is 100 parts by weight of the resin from the viewpoint that the active compound is more stably retained in the resin composition and that the volatile plasticizer can be more stably retained in the resin composition. With respect to 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight,
It is more preferably 5 to 30 parts by weight.

The active compound to be used in the present invention means insect repellent / insecticide, repellent, repellent, antibacterial / mildewproof, antifouling, depending on the purpose of use of the molded article obtained by molding the resin composition of the present invention. Organic compounds having activity for weeding, plant growth regulation, transdermal treatment, rust prevention, slipperiness, anti-blocking properties, surface activity, antistatic properties, etc., used alone or in combination of two or more. be able to. The vapor pressure of the active compound used in the present invention is not particularly limited as long as it satisfies the relationship with the vapor pressure of the volatile plasticizer described later, but the active compound by vaporization in the step of (melting) processing the resin composition From the viewpoint of preventing the disappearance of the above, the vapor pressure at 20 ° C. is preferably less than 0.01 mmHg, more preferably less than 0.001 mmHg, and even more preferably an organic compound having a low evaporation rate of less than 0.0001 mmHg. When using an insect repellent / insecticidal active compound as the active compound,
Examples of the insecticidal active compound include various insecticidal active compounds and insect growth regulating active compounds. Further, a compound (synergist) having a role of enhancing the effect of the insect repellent compound may be used in combination.

As the insecticidal active compound, at least one selected from commonly used insecticides, for example, pyrethroid compounds, phenylpyrazole compounds, organic phosphorus compounds, carbamate compounds, juvenile hormone-like compounds, etc. Can be selected from the above compounds.
As a specific example, as the pyrethroid compound,
Permethrin, allethrin, d-allethrin, dd-allethrin, plaethrin, cyphenothrin, phenothrin, d-phenothrin, d-resmethrin, empentrin, fenvalerate, fenpropasulin, cyhalothrin, cyfluthrin, etofenprox, tralomethrin, esbiosulin, transflurin. Surin, terarethulin and the like, organophosphorus compounds, fenitrothion, naredo, fenthion, cyanophos, chlorpyrifos, diazinon, calclophos, salithione, diazinon, etc., carbamate compounds, methoxydiazone, propoxur, carbaryl, fenobucarb and the like. Can be mentioned. Insect growth controlling active compounds include pyriproxyfen, mesoprene, hydroprene,
Diflubenzuron, cyromazine, phenoxycarb, renuenuron and the like can be used. Further, as synergists, piperonyl butoxide and cinepyrine-22
2, octachlorodipropyl ether and the like.

Examples of the mite-preventing active compound include miticide agents such as trifluoromethanesulfonic acid anilide compounds and pyrethroid compounds. The repellent active compound is a compound having an effect of repelling insects,
N, N-diethyl-m-triamide, carane-3,4-
A repellent such as diol can be exemplified. Examples of the antibacterial / antifungal and antifouling active compounds include isothiazoline compounds such as N-phenylbenzisothiazolone-3, 4,6-
Examples thereof include pyridylpyrimidine compounds such as dimethyl-2- (6-phenylpyridin-2-yl) pyrimidine, antibacterial / antifungal agents and antifouling agents such as oxonic acid and binazine. Herbicides, plant growth control, transdermal treatment, rust prevention, slipperiness, anti-blocking properties, surface active, antistatic and other active compounds, respectively, commercially available herbicides, plant growth regulators, rust preventives, lubricants, Examples thereof include anti-blocking agents, surfactants and antistatic agents.

In the combination of the volatile plasticizer and the active compound used in the present invention, the formula: P1 / P2 ≧ 2 (wherein P1 represents the vapor pressure of the volatile plasticizer at 20 ° C., P2 represents the active compound). Indicates vapor pressure at 20 ° C)
To meet. When P1 / P2 <2, the difference between the vapor pressure of the transpiration plasticizer and the vapor pressure of the active compound is small,
The effect of the inventive release behavior of the active compounds from the shaped bodies under open conditions is reduced. From the viewpoint of further enhancing the effect of the release behavior of the present invention, the ratio of P1 to P2 is P1.
/ P2 ≧ 5 is more preferable, P1 / P2 ≧ 10 is further preferable, and P1 / P2 ≧ 1000 is particularly preferable. P1
The larger the value of / P2, the more preferable, and the upper limit thereof is not particularly limited, but is usually 10 ¹⁰ or less.

The ratio of the compounding amount of the transpiration plasticizer to the compounding amount of the active compound in the present invention is appropriately determined according to the required bleeding characteristics and the purpose of use. For example, in order to realize the adjustment of the bleeding start timing of the active compound, the compounding amount may be determined as follows. That is, in order to cause the bleeding of the active compound to start immediately after the start of use, even if the transpiration plasticizer slightly evaporates, the concentration of the active compound in the resin composition becomes supersaturated. The amount ratio of the transpiration plasticizer to the amount may be set low. Further, in order to start bleeding of the active compound after a lapse of a certain time from the start of use, the concentration of the active compound in the resin composition does not become supersaturated unless a certain proportion of the volatile plasticizer evaporates. Thus, the amount ratio of the transpiration plasticizer may be set high. The saturated solubility of the active compound in the resin can be determined by the same method as in the case of the volatile plasticizer described above. The amount of transpiration plasticizer reduced by transpiration (amount of transpiration) can be determined by a method such as measuring the change with time of the amount of transpiration plasticizer remaining in the molded product in advance.

The timing at which the bleeding of the active compound starts can be controlled by changing the vapor pressure of the volatile plasticizer, in addition to the method of changing the ratio of the volatile plasticizer to the active compound. Can also be adjusted. That is, in order to start bleeding of the active compound early, a vaporizable plasticizer having a higher vapor pressure may be used, and conversely, in order to slow it, a vaporizable plasticizer having a lower vapor pressure may be used. You can use it. Further, the adjustment of the bleeding start timing of the active compound can also be adjusted by the addition amount of the bleeding accelerator described later. Adjusting the bleed rate can also be accomplished by these methods. Higuchi et al.'S quasi-stationary assumption (reference: Higuchi et al., J. Pharm. Sci., V
50,874 (1961)) is applied to the present invention, the bleed rate of the active compound in the present invention is proportional to the surface area of the molded product, the square root of the diffusion coefficient of the active compound and the supersaturated content of the active compound. From this finding, when controlling the bleed rate of the active compound, for example, in order to increase the bleed rate, the supersaturated content of the active compound may be increased. Further, by using a transpiration plasticizer having a high transpiration rate, for example, a transpiration plasticizer having a high vapor pressure, the bleeding rate at the initial stage of use can be increased.

As the resin used in the present invention, a resin suitable for the type of active compound to be used and its application can be selected. Specifically, polyolefins such as polyethylene, polypropylene and the like, ethylene-vinyl acetate copolymers, copolymers of ethylene with an organic carboxylic acid derivative having an ethylenically unsaturated bond such as ethylene-methyl methacrylate and the like, polychlorinated Vinyl, polyvinyl alcohol,
Thermoplastic resin such as polycarbonate, polyester, polystyrene and polymethylmethacrylate, thermosetting resin such as polyurethane and epoxy resin, or SBR,
For example, synthetic rubber such as EPDM. Among these resins, from the viewpoint of increasing the bleeding speed, a resin having a high mobility of the resin molecular chain and a low glass transition temperature is more preferable, and a resin that does not cause a chemical reaction or the like with an active compound is preferable. preferable. In particular, the thermoplastic resin has excellent shapeability and economical efficiency, and further, the solubility and diffusibility of the active compound can be controlled in a wide range by appropriately selecting the type of the thermoplastic resin and the type of the additive to be added. Therefore, it is more preferable as a material for controlling the bleeding of the active compound. Further, when molding and processing the resin composition of the present invention, the viewpoint of controlling the disappearance of the active compound and the volatile plasticizer by the decomposition of the active compound and the volatile plasticizer, the evaporation into the environment, the elution into the cooling water, and the like. Therefore, it is preferable to select, from the above-mentioned thermoplastic resins, a resin that can be molded at a temperature lower than the decomposition temperature or boiling point of the active compound or the volatile plasticizer.

The resin composition of the present invention may further contain, if necessary, a bleeding accelerator, a plasticizer other than the above-mentioned transpiration plasticizer (hereinafter sometimes simply referred to as a plasticizer), a stabilizer,
Fillers, colorants and the like can be appropriately added. Among them, the bleeding accelerator and the plasticizer are preferably used for the purpose of more effectively obtaining the activity such as improving the bleeding property of the active compound or improving the spreading effect of the bleeding active compound. it can. The bleeding accelerator can be used to improve the bleeding property of the active compound, and is preferably used to enhance the diffusivity, especially when the diffusibility of the active compound in the resin composition is low. it can.

As such a bleeding accelerator, the higher the diffusibility in the resin composition, the lower the solubility in the resin composition, and the higher the solubility in the transpiration plasticizer, the more preferable. In particular, carboxylic acid is preferable as the bleeding accelerator, and specific examples thereof include fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, and aromatic carboxylic acids such as benzoic acid, tartaric acid, fumaric acid, and malic acid. And dicarboxylic acids such as citric acid, and tricarboxylic acids such as citric acid. In addition, silicone compounds such as polydimethylsiloxane and polymethylphenylsiloxane, fluorine-based surfactants, and the like can also be exemplified as the bleeding accelerator. As described above, the blending amount of the bleeding accelerator can be appropriately set depending on the timing when bleeding of the active compound starts.
Usually, it is from 0.1 to 100 parts by weight, more preferably from 1 to 50 parts by weight, even more preferably from 5 to 20 parts by weight, based on 100 parts by weight of the resin.

When a resin such as polyvinyl chloride, polyester or polyvinyl alcohol is used in the resin composition of the present invention, a plasticizer usually used for imparting flexibility and processability can be added. . When using a resin having a high solubility of the active compound, such as polyvinyl chloride, it is preferable to use a plasticizer having a vapor pressure of less than 0.0001 mmHg and a low compatibility with the resin. By using such a plasticizer having low compatibility with the resin, the effect of lowering the saturated solubility of the active compound in the resin composition and further enhancing the bleeding property of the active compound can be expected. As such a plasticizer, diisononyl adipate, diisodecyl adipate, di2-ethylhexyl azelate, 2-ethylhexyl sebacate, epoxidized soybean oil, which are known as plasticizers having low compatibility with polyvinyl chloride resins, Examples include aliphatic polyesters.

The blending amount of these plasticizers is usually 100
The amount is 0.1 to 200 parts by weight, preferably 5 to 100 parts by weight, and more preferably 20 to 60 parts by weight with respect to parts by weight. The method of blending the active compound of the present invention with a resin such as a transpiration plasticizer is not particularly limited, and the raw materials are, for example,
After mixing using a mixer such as a Banbury mixer, a super mixer or an extruder, a powdery or pelletized resin composition can be obtained. Further, a molded body containing no active compound or transpiration plasticizer is preliminarily molded by the method described below, and the obtained molded body is immersed in a liquid containing the active compound and the volatile plasticizer, or the liquid is molded. The active compound and the transpiration plasticizer may be blended by a method of impregnating and absorbing the active compound and the transpiration plasticizer into the molded body by, for example, coating.

The shape and molding method of the molded article of the present invention are not limited as long as it is obtained by molding the above-mentioned resin composition. Depending on the desired use conditions and purpose of the molded product, for example, animal collars, ear tags, medals, etc., various shapes such as rod-shaped, flat-plate-shaped, mesh-shaped, round-shaped, spherical-shaped, fan-shaped, triangular-shaped, etc. Or in the form of net, fiber, non-woven fabric, sheet, film or the like. The term “ear tag” as used herein refers to an insect repellent product that is worn on the ears of livestock or the like to control the pests and the like flying in order to maintain good health of the livestock and the like.

Examples of the molding method include known molding methods such as injection molding, extrusion molding, press molding and slush (powder) molding. Further, depending on the purpose of improving the mechanical properties during use, increasing the concentration of the active compound on the surface of the molded body, or improving the process moldability, multilayer extrusion molding, multicolor injection molding, composite spinning, extrusion lamination are appropriately performed. It can be processed and used by various methods used in conventionally known thermoplastic resins such as molding. The resin composition layer of the present invention in the molded body may be arranged in any layer depending on the purpose.

The method of use and application of the molded article of the present invention are not particularly limited, and the active compound having a low transpiration property can be used particularly preferably in an application and use environment in which release is relatively difficult. Specifically, depending on the activity of the active compound and the purpose of use of the molded body, insect repellent / insecticide, fungicidal / mildewproof, antifouling, weeding, plant growth control, transdermal treatment, rustproofing, slipperiness The molded product can be used to obtain activities such as anti-blocking property, surface activity, and antistatic property. For example, a dripping film containing a surfactant, an antistatic film containing an antistatic agent,
Alternatively, it can be used for applications such as animal insect repellent devices containing insect repellent active ingredients (for example, animal insect repellent collars, animal insect repellent ear tags, etc.). In particular, since the molded product of the present invention can appropriately control the bleeding timing of the insect repellent active ingredient and has a high utilization rate of the insect repellent active ingredient, it can be obtained by molding the resin composition of the present invention for animals. By attaching an insect repellent collar, an animal insect repellent ear tag, an animal insect repellent medal, etc. to an animal, a higher insect repellent effect can be obtained.

[0023]

INDUSTRIAL APPLICABILITY As described above, the present invention achieves controlled release of an active compound from a molded article by bleeding. The purpose of controlled release is to enhance the effect of the active compound by releasing the required amount of the active compound when and where it is needed, and many methods for achieving controlled release have been proposed. There is. According to the present invention, this object can be achieved, and a simple and economical method of controlled release can be provided. The present invention can be more suitably used for active compounds having low transpiration. Further, according to the present invention, the active compound is stably retained in the resin composition under the sealed condition, and the active compound bleeds with the evaporation of the volatile plasticizer during the use under the open condition. The release behavior can be realized, the utilization rate of the active compound can be improved, and excellent activity can be stably obtained for a long period of time. It is also possible to control the timing at which bleeding of the active compound begins.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. [Example 1] Using a super mixer, the raw materials were charged at about 30 ° C and gradually heated to 130 ° C, and then at about 80 ° C.
By cooling to below, a powdery resin composition having the formulation shown in Table 1 was obtained. Next, the sheet obtained by kneading for 5 minutes using a roll heated to 160 ° C. was pelletized with a sheet pelletizer. Molding temperature 1 using this pellet
Press molding at 80 ℃, length 8cm, width 5.2c
A sheet of m and a thickness of 3 mm was obtained (the surface area of this sheet was about 91 cm ² ). This sheet was hung in a circulating oven set at 35 ° C. for 3 days under open conditions, and then the components bleeding on the surface were wiped off with paper (Kimwipe, made by Tojo Kimberley), and the weight was measured using a balance. The amount of bleed under the open condition was measured by precisely weighing. At the same time, this sheet is sealed with aluminum foil, and after aging at 35 ° C. for 3 days, the components bleeding on the surface and the components adhering to the aluminum foil are wiped off and precisely weighed in the same manner as above. By
The amount of bleed under the sealed condition was measured. Further, in order to grasp the appearance state during storage at high temperature, the appearance state of the sheet when stored in a closed state at 50 ° C. for 3 days was visually observed. Table 3 shows the results. A large amount of bleeding was observed under the open condition as compared with Comparative Example 1 described later, and only a slight amount of bleeding was observed under the closed condition, and the external appearance of the sheet during the sealed storage was good.

Example 2 Except that the formulation shown in Table 1 was used, aging was carried out at 35 ° C. for 3 days under the open and sealed conditions in the same manner as in Example 1, and then the amount of bleed was measured. . Further, the external appearance of the sheet when stored in a sealed state at 50 ° C. for 3 days was visually observed. Table 3 shows the results. A large amount of bleed was observed under the open condition as compared with Comparative Examples 2 and 3 described later, and a small amount of bleed was observed under the closed condition, and the external appearance of the sheet during the sealed storage was good.

[Comparative Examples 1 to 3] Except that the formulation shown in Table 1 was carried out in the same manner as in Example 1, under the conditions of opening and sealing, aging was carried out at 35 ° C. for 3 days, and then the amount of bleed was adjusted. It was measured. Further, the external appearance of the sheet when stored in a sealed state at 50 ° C. for 3 days was visually observed. Table 3 shows the results. Although bleeding is recognized under the open condition,
Almost the same amount of bleeding was observed even under the sealed condition, the appearance of the sheet when stored in a sealed condition was poor, and a large amount of adhesion was observed on the aluminum foil used for the packaging material.

[Comparative Example 4] Comparative Example 3 except that DOA which is a plasticizer having a higher compatibility than DIDA was used instead of DIDA.
In the same manner as above, open and sealed conditions, 35 ℃, 3
After performing aging for a day, the amount of bleed was measured. Further, the external appearance of the sheet when stored in a sealed state at 50 ° C. for 3 days was visually observed. Table 3 shows the results.
Almost no bleed was observed under both open and closed conditions.

[Examples 3 to 8] Powdery resin compositions having the formulations shown in Table 2 were obtained using a super mixer, and the powders were injection molded at a molding temperature of 180 ° C to give
An animal collar-shaped molded article having a length of 35 cm, a width of 1 cm and a thickness of 3 mm was obtained (the surface area of this molded article was about 91 cm 2). In the same manner as in Example 1, the bleed amount was measured after aging this molded product at 35 ° C. for 3 days under open and sealed conditions. In addition, the appearance of the molded product was visually observed at 50 ° C. for 3 days in a sealed state. Table 3 shows the results. A large amount of bleed was observed under the open condition, and a small amount of bleed was observed under the closed condition, and the appearance of the sheet when stored in a closed condition was also good.

Example 9 The molded product used in Example 6 was
Aging was performed at 23 ° C. and 35 ° C. for 28 days, and the bleed amount during this period was measured every 7 days. The results are shown in Table 4. Even after repeated wiping, a large amount of bleeding was observed as compared with Comparative Example 5 under the open condition, and only a slight amount of bleeding was observed under the closed condition. In addition, when the composition analysis of the components bleeding when aging under open conditions for 14 days was carried out using gas chromatography,
At 23 ° C, SUM was 32%, DIDA was 56%, isostearic acid was 12%, and at 35 ° C, SUM was 30%, DIDA was 58% and isostearic acid was 12%.

Comparative Example 5 The bleed amount was measured after aging was performed for 3 days at 35 ° C. under open and sealed conditions in the same manner as in Example 3 except that the formulation shown in Table 2 was used. . Further, the external appearance of the sheet when stored in a sealed state at 50 ° C. for 3 days was visually observed. Table 3 shows the results. Although bleeding is recognized under the open condition,
Almost the same amount of bleeding was observed even under the sealed condition, and the appearance of the sheet when stored in the sealed condition was poor.

Comparative Example 6 The molded product used in Comparative Example 5 was
Aging was performed at 23 ° C. and 35 ° C. for 28 days, and the amount of bleeding during this period was measured every 7 days. The results are shown in Table 5. Even after repeated wiping, bleeding was observed under the open condition, but almost the same amount of bleeding was observed even under the sealed condition, and the appearance of the sheet when stored in a sealed state was poor. A lot of adhesion was recognized. Further, the amount of bleed when repeatedly wiped off tended to decrease. When the composition analysis of the bleeding component when aged for 14 days under the open condition was carried out by gas chromatography, SUM 31%, DIDA6
9%, SUM 36% and DIDA 64% at 35 ° C.

The main substances used in Examples, Comparative Examples and Reference Examples are as follows. <Resin> -Resin A: Polyvinyl chloride (Sumitomo Chemical Co., Ltd., trade name: Summit (average degree of polymerization 1300 suspension polymerized product))-Resin B: Polyvinyl chloride (Sumitomo Chemical Co., Ltd., product name: Sumiritto (average polymerization degree of 1100 emulsion polymerization product)) <active compounds>, permethrin :( Sumitomo chemical Co., Ltd., trade name: Ekusumin, EXM substantially, a vapor pressure at 20 ℃: 5.5 × 10 ^{- 7} m
mHg) -d-phenothrin (Sumitomo Chemical Co., Ltd., trade name:
Abbreviated as Smithlin and SUM, vapor pressure at 20 ℃: 1.2 × 10 ^-6
mmHg) ・ Pyriproxyfen (Sumitomo Chemical Co., Ltd., trade name: Sumilab, abbreviated as SLV, vapor pressure at 20 ° C: 2.2 x 10
^-6 mmHg) <Evaporative plasticizer> -Mixed methyl ester of succinic acid, glutaric acid, and adipic acid (manufactured by Sanken Kako Co., Ltd., DBAM, vapor pressure at 20 ° C: 0.1 mmHg) -Triethyl phosphate ( Made by Kurogane Kasei Co., Ltd., product name: TE
P, vapor pressure at 20 ° C: 0.3 mmHg) <Plasticizer> -Diisodecyl adipate (manufactured by Sanken Kako Co., Ltd., DIDA
And vapor pressure at 20 ° C: 1 x 10 ^-7 mmHg) -Di-2-ethylhexyl adipate (manufactured by Sanken Kako Co., Ltd., DOA, vapor pressure at 20 ° C: 7 x 10 ^-7 mmHg). <Stabilizer> O-130P: Asahi Denka Kogyo Co., Ltd. (also used as epoxidized soybean oil and secondary plasticizer) LPZ-793L: Sakai Chemical (liquid barium-zinc stabilizer)

[0033]

[Table 1] Note) Numerical values represent parts by weight.

[0034]

[Table 2] Note) Numerical values represent parts by weight.

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

Example 10 The bleeding amount (mg / 91 cm ² ) was measured every 3 days at 35 ° C. in the same manner as in Example 7 except that the compounding amount of isostearic acid was 8 parts by weight.
It was shown to.

Example 11 The bleed amount (mg / 91 cm ² ) was measured every 3 days at 35 ° C. in the same manner as in Example 7 except that the compounding amount of isostearic acid was 4 parts by weight.
It was shown to.

[0040]

[Table 6] -Timed release can be realized by adjusting the blending amount of the bleeding accelerator.

Example 12 A resin molding of the present invention was obtained in the same manner as in Example 7 except that the amount of isostearic acid was 6 parts by weight. This molded product exhibited an excellent effect as a collar for animals. The sheet was hung in a circulation type constant temperature bath set at 35 ° C., and the surface and back of the sample were wiped with a paper (made by Tojo Kimberley, Kimwipe) about every one week. After the wiped paper was extracted and diluted with methanol, the active ingredient was quantitatively analyzed by liquid chromatography to measure the amount of bleed at the time of repeated wiping. The time-dependent changes in the amount of bleeding on the surface of the collar of Smithlin and Sumilab are shown in FIGS. 1 and 2. The bleed amount was calculated by dividing the quantitative value by liquid chromatography by the surface area of the collar (91 cm ² ) and the number of days elapsed since the previous wiping date (7 days in principle). A bleed of the active ingredient was observed for about 4 months.

Using a super mixer, the process shown in Table 7 is performed.
One powdery resin composition was obtained. Molding temperature of this powder 1
By injection molding at 50 ℃, length 35cm, width 1
cm shaped, 3 mm thick animal collar shaped molded product was obtained.
The surface area of the molded product is about 91 cm ²It is. ). This molded product
In the same manner as in Example 1 under open and sealed conditions,
The amount of bleed after aging at 35 ° C for 3 days
It was measured. In addition, the external appearance when stored in a sealed state at 50 ° C for 3 days
Was visually observed. The results are shown in Table 8.

[0043]

[Table 7]

[0044]

[Table 8] <Resin> Resin C: Polyvinyl chloride (Sumitomo Chemical Co., Ltd., trade name: Summit (average degree of polymerization: 800 suspension polymerized product)) Resin B: Polyvinyl chloride (Sumitomo Chemical Co., Ltd., Product name: Smilit (average degree of polymerization 1100 emulsion polymerized product) <Active compound> -Fenobucarb: (Sumitomo Chemical Co., Ltd. product name:
Osbach, BAK and vapor pressure at 20 ℃: 3.3 × 10
^-4 mmHg) <Stabilizer> -Bis (2,2,6,6-tetramethyl-4-piperidinyl sebatate (manufactured by Nissan Ferro Co., Ltd., trade name: NF
90) * 4,4'- isopropylidene diphenol alkyl (C12-C15) phosphite (Nissan Ferro Co., Ltd., brand name: NF915) * Bis (2,2,6,6-tetramethyl-4-piperidi) A mixture of nilsebatate and n-octadecyl-β- (4'-hydroxy-3,5-t-butylphenyl) propionate (manufactured by Nissan Ferro Co., Ltd., trade name: Nx-80).
3A) -Bisphenol A diglycidyl ether (Nissan Ferro Co., Ltd., trade name: 909) <Processing aid> -Low molecular weight polyethylene (Nissan Ferro Co., Ltd., trade name: Lub)

[Brief description of drawings]

FIG. 1 is a graph showing changes over time in the amount of bleeding on the collar surface of Smithlin and Sumilab in Example 12.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 53/02 A01N 57/14 D 57/14 C08J 5/06 CEV C08J 5/06 CEV C08L 101 / 00 C08L 101/00 A01N 53/00 502B 502C (72) Inventor Masa Sakurai 2-10-1 Tsukahara, Takatsuki City, Osaka Sumitomo Chemical Co., Ltd.

Claims (20)

[Claims] 1. A composition comprising 100 parts by weight of a resin, 0.01 to 200 parts by weight of an active compound, and 0.1 to 100 parts by weight of a volatile plasticizer having a vapor pressure at 20 ° C. of 0.001 mmHg or more. The vapor pressure at 20 ° C. (P1) and the vapor pressure of the active compound at 20 ° C. (P2) have the formula: P
A resin composition satisfying 1 / P2 ≧ 2. 2. The resin composition according to claim 1, wherein the volatile plasticizer is an ester which is liquid at room temperature (23 ° C.). 3. The vapor pressure of the active compound at 20 ° C. is 0.
The resin composition according to claim 1, which is less than 01 mmHg. 4. The active compound is an insect repellent, acaricide, repellent, antibacterial / antifungal agent, antifouling agent, herbicide, plant growth regulator,
The resin composition according to claim 3, which is at least one selected from transdermal therapeutic agents, rust preventives, lubricants, anti-blocking agents, surfactants and antistatic agents. 5. The resin composition according to claim 3, wherein the active compound is at least one selected from insect repellents, acaricides, repellents, fungicides / molds, and antifouling agents. 6. The resin composition according to claim 3, wherein the active compound is at least one selected from pyrethroid compounds, organic phosphorus compounds, carbamate compounds, and juvenile hormone-like compounds. 7. The resin composition according to claim 3, wherein the active compound is a pyrethroid compound and / or a juvenile hormone-like compound. 8. The resin composition according to claim 3, wherein the active compound is a carbamate compound and / or a juvenile hormone-like compound. 9. The resin composition according to claim 1, wherein the resin is a polyvinyl chloride resin. 10. A plasticizer having a vapor pressure at 20 ° C. of less than 0.0001 mmHg is added in an amount of 0.1 to 200 parts by weight.
Alternatively, the resin composition according to item 9. 11. The resin composition according to claim 1, wherein 0.1 to 100 parts by weight of a bleeding accelerator is added. 12. Vapor pressure (P1) of volatile plasticizer at 20 ° C. and vapor pressure of active compound at 20 ° C. (P2).
Is the resin composition according to claim 11, which satisfies the formula: P1 / P2 ≧ 5. 13. The resin composition according to claim 11, wherein the bleeding accelerator is a carboxylic acid. 14. A molded product obtained by molding the resin composition according to any one of claims 1 to 13. 15. An animal collar obtained by molding the resin composition according to any one of claims 5 to 8. 16. An animal ear tag obtained by molding the resin composition according to any one of claims 5 to 8. 17. A medal for animals obtained by molding the resin composition according to any one of claims 5 to 8. 18. 0.01 to 200 parts by weight of active compound, and 2
A liquid consisting of 0.1 to 100 parts by weight of a vaporizable plasticizer having a vapor pressure at 0 ° C. of 0.001 mmHg or more, and a vapor pressure (P1) of the vaporizable plasticizer at 20 ° C. and 2 of the active compound.
The vapor pressure (P2) at 0 ° C. is expressed by the formula: P1 / P2 ≧
A molded product obtained by impregnating a liquid satisfying 2. 19. A method for controlling bleeding of an active compound, which comprises using the molded article according to claim 14. 20. Use of the molded article according to claim 14 for controlling pests living on the body surface of animals.