JPH0641442A - Resin composition which indicates drug deficacy medicine - Google Patents

Abstract

PURPOSE:To obtain the resin composition by which the shelf life of a product of a definite shelf life can be visually judged by changing its hue, by mixing a thermoplastic resin with a volatile electron-accepting organic compound and a difficultly volatile electron-donating coloring organic compound. CONSTITUTION:The composition is prepared by melt-mixing a thermoplastic resin with a volatile electron-accepting organic compound and a difficultly volatile electron-donating coloring organic compound. This composition can be heat-processed at a temperature below the heat decomposition temperature of the electron-accepting organic compound or the electron-donating coloring organic compound. The thermoplastic resins to be used may be any one that does not cause the coloration of the electron-donating coloring organic compound and are exemplified by a branched low-density polyethylene and a high-density polyethylene. Examples of the coloring organic compounds used include rhodamine lactams, fluorans and triphenylmethanephthalides. Examples of the electron- accepting organic compounds used include resorcinol, cresol and salicyclic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a drug effect indicating resin composition. More specifically, fungicides, fungicides, herbicides,
Plant growth regulators, pheromones, juvenile hormone mimetics,
The present invention relates to a drug effect indicating resin composition capable of visually identifying the effective period of products such as insecticides, repellents, deodorants, fragrances, and pharmaceuticals, which have a limited effective period, by a change in color tone.

[0002]

2. Description of the Related Art As a time indicator, there is provided a pharmaceutical composition comprising a color-developing organic compound component, a second component for developing the color, and a third component for decolorizing the system when added to a system in which these two agents are colored. Mainly spread and held on a base material such as paper or non-woven fabric, and the coloring or decoloring due to the action of one of the three components remaining after volatilization of the third or second component and the coloring organic compound. The phenomenon in which the effect is observed is correlated with the disappearance of the volatile active ingredient over time, and the effective period is observed (for example, JP-A-62-235562, JP-A-6-62562).
3-60901 and Japanese Patent Application Laid-Open No. 2-290591) are conventionally known. However, these methods require the above three components to cause a color change.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention accurately and visually discriminate the end point of a drug effect and the residual amount of a drug effect ingredient within the effective period by a simple color change caused by the action between the two ingredients. The present invention has been accomplished by discovering a drug-effect-indicating resin composition that makes it possible.

[0004]

[Means for Solving the Problems] That is, the present invention provides a drug effect indicating resin composition obtained by melt-kneading a thermoplastic resin, an electron-accepting organic compound having volatility, and an electron-donating color-forming organic compound. It is about.

In the drug effect indicating resin composition of the present invention, the electron-donating color-developing organic compound which is in a colored state in the presence of the electron-accepting organic compound is accompanied by volatilization of the electron-accepting organic compound after a certain period of time. It is characterized in that the discoloring action at the time of erasing is used as an indicator of drug effect (indicator).

The thermoplastic resin of the present invention can be heat-processed at a temperature not higher than the thermal decomposition temperature of the volatile electron-accepting organic compound or the electron-donating color-forming organic compound, and does not cause the electron-donating color-forming organic compound to develop a color. As long as it is a branched low-density polyethylene, ethylene and a carbon number of 4 to 1
Linear low-density polyethylene, high-density polyethylene, a copolymer of (ethylene and / or butene-1) and propylene, (vinyl acetate and / or acrylic ester) Copolymers with ethylene, polyolefin-based thermoplastic resins such as polypropylene, styrene-butadiene rubber, synthetic rubber such as ethylene-propylene-diene rubber, vinyl chloride-based thermoplastic resins, polyesters, nylons, and the like. Alternatively, two or more kinds can be mixed and used.

In selecting the thermoplastic resin in the present invention, since the decoloring at the end of use may be insufficient, additives such as an additive, a plasticizer, a catalyst residue for coloring the electron-donating color-developing organic compound may be removed. Those that do not contain a component having an electron accepting property are preferable.

The electron-donating color-developing organic compound is a compound in which color development in the presence of the electron-accepting organic compound and decoloring due to the disappearance of the electron-accepting organic compound reversibly occur at room temperature, and the compound is difficult to vaporize. There is no particular limitation as long as it is a compound, and various conventionally known compounds such as rhodamine lactams,
Fluoranes, triphenylmethanephthalides, phenothiazines, indolylphthalides, spiropyrans,
Compounds such as leuco auramines can be used.

More specifically, for example, rhodamine B b
ase, N-phenylrhodamine lactam, crystal violet lactone, malachite green lactone, 1,3-
Dimethyl-6-diethylaminofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, N-
Examples include 3,3-trimethylindolinobenzospiropyran and ethylleucomethylene blue. The electron-donating color-forming organic compounds may be used alone or in combination of two or more.

The electron-accepting organic compound in the present invention may be any one as long as it has volatility at room temperature or under heating, and when the resin composition of the present invention is used as an indicator, volatilization of the active ingredient in the target product is carried out. In consideration of the properties, those having an appropriate volatility under desired use conditions can be used. For example, phenols such as resorcinol, cresol and naphthol, phenolic carboxylic acids such as salicylic acid, benzyl alcohol, alcohols such as 1-octanol, carboxylic acids such as stearic acid and myristic acid, and parachlorometaxylenol showing antifungal activity. , Orthophenylphenol, 3-methyl-4-isopropylphenol, 3-aceto-6-methyl-2-pyrronone, oxybenzoic acid lower alkyl esters and the like can be used alone or in combination of two or more. In particular, in the present invention, when these volatile electron-accepting organic compounds are compounds having a medicinal effect, the resulting resin composition should always know the residual effect state and the end point of use without error regardless of the use conditions. A direct drug-effect-indicating resin composition capable of

The blending amounts of the volatile electron-accepting organic compound and the electron-donating color-forming organic compound can be arbitrarily changed depending on the thermoplastic resin to be used and also in consideration of a desired color tone and effective period. However, usually, the thermoplastic resin 100
0.001 to 50 parts by weight, 0.0
001 to 5 parts by weight. If the compounding amounts of the volatile electron-accepting organic compound and the electron-donating color-forming organic compound are 0.001 parts by weight and less than 0.0001 parts by weight, discoloration is unclear, and 50 parts by weight each, If the amount exceeds 5 parts by weight, the composition bleeds to the surface, resulting in discoloration. Further, antioxidants, ultraviolet absorbers, light stabilizers, anti-blocking agents, fillers, transpiration regulators, fragrances, dyes, dyes, pigments and the like can be added appropriately within the range not impairing the object of the present invention. For example, in the present invention, the object of the present invention can be achieved with a change in color tone. Since it turns yellow, it can be used as an indicator.

The drug effect indicating resin composition obtained by melt-kneading the thermoplastic resin of the present invention, the volatile electron-accepting organic compound and the electron-donating color-forming organic compound is, for example, a film, a sheet or various kinds. In the form of a molded article of this shape, and using it as a time indicator together with various products having a specific effective period in the form of attachment or juxtaposition,
It can be used for the purpose of knowing the shelf life of the product.

As another embodiment of the present invention, a drug efficacy indicating resin composition obtained by melt-kneading a thermoplastic resin, a volatile electron-accepting organic compound, an electron-donating color-forming organic compound and a drug. Is mentioned. Examples of the drug used include pesticides, drugs, epidemics, hygiene drugs and industrial drugs. More specifically, fungicides, fungicides, insecticides having repellent activity, repellents, pheromones, Examples include juvenile hormone-mimicking substances, herbicides, plant growth regulators, deodorants, and flavors such as animal and plant essential oils and synthetic flavors. More specifically, empentryn, allethrin, praresulin, chlorpyrifos, dichlorvos, fenitrothion, esbiosulin, permethrin, cyphenothrin, d-phenothrin, d-resmethrin, fenvalerate, fenpropasulin, cyhalothrin, cyfluthrin, etofenprox, tralomethrin, Insecticides such as etofenflox and diazinon, repellents such as diethyltoluamide, (E) -1-
(4-chlorophenyl) -4,4-dimethyl-2-
(1,2,4-triazol-1-yl) -pent-1
-En-3-ol, 1- (4-chlorophenyl)-
4,4-Dimethyl-2- (1H-1,2,4-triazol-1-yl) -pent-3-ol, 5- (4-chlorophenyl) -3,4,5,9,10-penta aza tetracyclododecene [5,4,10 ^2,6, 0 ^8,11] 3,9-diene, (E)-1-cyclohexyl-4,4-dimethyl-2- (1,2,4-triazole - Plant growth regulators such as 1-yl) -pent-1-en-3-ol, 4-chloro-2- (α-hydroxybenzyl) isonicotinanilide, 3,5-dioxo-4-propionylcyclohexanecarboxylic acid salt , Essential oils of animals and plants such as hinoki essential oil and hiba essential oil. The blending amount of these can be appropriately selected according to various conditions.

The drug effect-indicating resin composition of the present invention comprises a thermoplastic resin, a volatile electron-accepting organic compound, and an electron-donating color-forming property by a conventional kneading method using a pressure type Banbury or an extruder. It can be produced by melt-kneading an organic compound, and optionally a drug.

The use form of the drug efficacy indicator resin composition of the present invention is not particularly limited, and various shapes of injection molded articles, nets, non-woven fabrics, fibers, sheets, films, etc. can be used depending on the desired discoloration period. It can be used after being processed into the above shape or wrapped with a breathable film or a non-woven fabric. In addition, the drug effect-indicating resin composition of the present invention controls the discoloration period, or prevents evaporation loss of the electron-accepting organic compound during processing or molding, or the electron-donating color-forming organic compound and / or electron. In order to prevent bleeding of the receptive organic compound, it can be appropriately processed and used by a method used for a usual thermoplastic resin such as multilayer extrusion molding, composite spinning, extrusion lamination molding and the like.

The color change period of the drug-effect indicating resin composition of the present invention depends on the volatility of the electron-accepting substance and the diffusibility of the electron-accepting substance in the thermoplastic resin. By changing the composition and the shape of the resin composition, it can be set to an arbitrary length for several hours to several years.

[0017]

The drug effect indicating resin composition of the present invention is extremely easy to manufacture, store and use, and can be used in various forms, and its effective period can be arbitrarily set for several hours to several years. It has many excellent features such as the ability to be set, and the effective period can be visually and easily determined.

[0018]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 Ethylene-methyl methacrylate copolymer as a thermoplastic synthetic resin (Aklift WH202 manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight, 4 parts by weight of parachlorometaxylenol (hereinafter referred to as PCMX) having an antifungal effect as an electron-accepting organic compound having volatility, and rhodamine B base (Taoka Chemical Industry Co., Ltd. (0.04 parts by weight) was melt-kneaded by using a shearing pressure kneader (manufactured by Moriyama Seisakusho Co., Ltd.) with shear heat generation, and then was fed into an extruder and extruded to form hot-cut pellets. A drug effect indicating resin composition was obtained.

Continually, three kinds of three layers inflation die (caliber 1
00 mm) in a multi-layer inflator, and the above-mentioned drug efficacy indicating resin composition is passed through an extruder having a diameter of 40 mm to the middle layer of the die at a melting zone of 170 ° C. and a die temperature of 150 ° C. for 9 kg / h. Was supplied at a discharge amount of. Low density polyethylene (Sumikasen CE2559 manufactured by Sumitomo Chemical Co., Ltd.) was supplied to the inner layer and the outer layer at a discharge rate of 3 kg / h under the conditions of a melting zone of 180 ° C and a die temperature of 150 ° C.
The resin supplied to each layer is bonded inside the die to form a tubular body having a three-layer sandwich structure (outer layer / intermediate layer / inner layer) with a blow-up ratio of 2.4, a frost line distance of 200 mm, and a take-up speed of 4.2 m / min. Picked up under conditions, folding diameter 320mm,
The overall thickness of each layer is 0.1mm, which is sandwiched between low-density polyethylene and a drug efficacy indicator resin composition composed of outer layer 0.02mm / middle layer 0.06mm / inner layer 0.02mm.
A three-layer film of

The obtained three-layer film was hung in a constant temperature and humidity chamber with a space volume of 9 m ^{3 under no} wind adjusted to a temperature of 20 ° C. and a humidity of 40%, and the color tone of the sample was observed with a color difference meter at regular intervals. (Measurement of color difference ΔE), antifungal effect test, and measurement of residual ratio of electron-accepting substance in sample. The residual amount of the electron-accepting organic compound was extracted by a Soxhlet extractor using acetone as a solvent and then quantified by gas chromatography to calculate the residual ratio of the electron-accepting substance. As shown in FIG. 1, the pink color of the three-layer film was gradually thinned as the residual ratio of the electron-accepting organic compound was decreased, and the transparent film was obtained due to the disappearance of the electron-accepting organic compound. This film was found to have antifungal effect for 48 days.

Example 2 The take-up speed in Example 1 was changed from 4.2 m / min to 9.0 m / min, and the thickness of each layer was 0.01 mm in the outer layer / 0.
A three-layer film was obtained in the same manner as in Example 1 except that 03 mm / inner layer was 0.01 mm and the total thickness was 0.05 mm.
The performance of the obtained three-layer film is shown in FIG. in this case,
Since the thickness of the film is smaller than that of Example 1, the residual ratio of the electron-accepting substance is reduced faster than that of Example 1, but the color of the film is also rapidly erased, and the color of the film is erased as in Example 1. It was confirmed that the residual state of antifungal activity and the end point of use can be known without error. Antifungal activity is 18
Lasted for days.

Example 3 The three-layer film obtained in Example 2 was treated at a temperature of 20.
Changes with time were observed in the same manner as in Example 2 except that the chest was placed in a drawer (space volume 0.2 m ³ ) installed in a windless room adjusted to 40 ° C. and 40% humidity. As the residual rate of the electron-accepting substance decreased, the pink color of the three-layer film gradually became light, and the disappearance of the electron-accepting substance resulted in a transparent film. In this case, the film was discolored and the antifungal effect was lost after 10 months elapsed.

Example 4 100 parts by weight of ethylene-vinyl acetate copolymer (Evatate H2020 manufactured by Sumitomo Chemical Co., Ltd.) and 2 parts by weight of empentryn (Vapourthrin manufactured by Sumitomo Chemical Co., Ltd.), which is an insect repellent, were melt-kneaded. After pelletizing, an insect repellent film having a thickness of 0.04 mm was obtained at a pressing temperature of 150 ° C. After laid drawer chest as well as the insect film 300 cm ² sections Example 2 Example 3 a section of a three-layer film 5 cm ² obtained in, and observed the change with time. After 10 months,
The residual rate of the empentryrin remaining on the insect-control film was about 5%, but no change in appearance was observed.
On the other hand, the three-layer film used in combination was almost decolored in 10 months, and the disappearance of the medicinal effect of the insect repellent film and the decoloration of the time indicator coincided with each other, and they were effective as a time indicator.

Example 5 The take-up speed in Example 1 was changed from 4.2 m / min to 0.9 m / min, and the thickness of each layer was 0.1 mm in the outer layer / 0.3 in the intermediate layer.
A three-layer film was obtained in the same manner as in Example 1 except that the inner thickness was 0.1 mm, the inner layer was 0.1 mm, and the total thickness was 0.5 mm.

Commercially available pet color (Dainippon Pyrethrum Co., Ltd.)
Flea collar made by S, color: white, shelf life: about 4 months, active ingredient: permethrin) Immediately after being attached to a cat, the above three-layer film cut into a length of 1 cm x 2 cm is attached to the flea collar. The change over time was observed. In this case, the three-layer film gradually disappeared from magenta and became transparent after 4 months, and was effective as a time indicator for the flea collar.

Example 6 In the same manner as in Example 1 except that orthophenylphenol (hereinafter referred to as OPP) was used in place of the parachlorometaxylenol used as the electron-accepting organic compound in Example 1, three steps were carried out. A layer film was obtained. The performance of the obtained three-layer film is summarized in FIG. As in Example 1, as the residual rate of the electron-accepting organic compound decreases, 3
The pink color of the layer film gradually faded, and the film became transparent due to the disappearance of the electron-accepting substance. Also, a sufficient antifungal effect was observed during the period when the film was colored. (The antifungal activity lasted for 18 days.)

Example 7 100 parts by weight of the drug-efficiency-indicating resin composition of Example 1 was used as a thermoplastic synthetic resin, ethylene-vinyl acetate copolymer (Evatate H2020 manufactured by Sumitomo Chemical Co., Ltd.), and a volatile electron acceptor. -Methyl-4- as the organic compound
In addition to 4 parts by weight of isopropylphenol, 0.1 parts by weight of Rhodamine B base (manufactured by Taoka Chemical Industry Co., Ltd.) as an electron-donating color-forming organic compound, and 0.1 parts by weight of a yellow pigment. A three-layer film was obtained in the same manner as in Example 1. In this case, 3-methyl-4-
With the evaporation of isopropylphenol, the color tone of the film changed to reddish brown at the beginning of use and yellow at the end point.
When the film was reddish, it showed a sufficient antifungal effect,
The yellowed film did not show antifungal activity.

Example 8 As a thermoplastic synthetic resin, ethylene-methyl methacrylate copolymer (Aklift WH202 manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight, resorcin 0.1 part by weight as an electron-accepting organic compound having volatility, and rhodamine B base as an electron-donating color developing organic compound (Taoka Chemical Industry Co., Ltd.)
0.05 parts by weight and volatile insect repellent empentryn (Sumitomo Chemical Co., Ltd. vaporthrin) 1
1 part by weight was melt-kneaded by using a shearing heat generator with a closed-type pressure kneader (manufactured by Moriyama Seisakusho Co., Ltd.), and was hot-cut into pellets by hot-cutting while being supplied to an extruder and extruded to obtain a drug efficacy indicating resin composition.

This drug effect indicating resin composition was molded at a pressing temperature of 150 ° C. into a sheet having a thickness of 0.5 mm. This sheet was suspended in a hot-air circulation type oven adjusted to a temperature of 60 ° C., sampled at regular time intervals, and the residual rate of the electron-accepting substance and empentrin in the observed sample was measured. The color of this sheet changed from dark reddish purple at the beginning to disappear with the evaporation of resorcin. In this case, since resorcin and empentrin evaporate at the same rate,
It is clear that this sheet can be used as an indicator of the insect repellent empentryn.

Comparative Example 1 Ethylene-methyl methacrylate copolymer as a thermoplastic synthetic resin (Aklift WH202 manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight, 0.05 part by weight of Rhodamine B base (manufactured by Taoka Chemical Industry Co., Ltd.) as an electron-donating color-developing organic compound, and pententrine (Vaporthrin manufactured by Sumitomo Chemical Co., Ltd.) which is a volatile insect repellent. A composition consisting of 11 parts by weight was kneaded and pelletized in the same manner as in Example 8, and then formed into a sheet having a thickness of 0.5 mm at a pressing temperature of 150 ° C.

Since this sheet did not contain an electron-accepting substance having volatility, it was in a decolored state (a slight coloration which is thought to be attributed to impurities of empentrin was observed) and was a transparent sheet. This sheet was hung in a hot air circulation type oven adjusted to a temperature of 60 ° C. in the same manner as in Example 8, and the residual rate of empentrin after 3 days was 0%, but no remarkable change in color tone was observed.

Comparative Example 2 As a thermoplastic synthetic resin, ethylene-methyl methacrylate copolymer (Acryft WH202 manufactured by Sumitomo Chemical Co., Ltd.)
100 parts by weight of bisphenol A as an electron-accepting organic compound having extremely low volatility as compared with empentryn.
1 part by weight, 0.05 part by weight of Rhodamine B base (manufactured by Taoka Chemical Industry Co., Ltd.) as an electron-donating color developing organic compound,
And kneading and pelletizing a composition consisting of 11 parts by weight of volatile insect repellent empentrin (Vaporthurin manufactured by Sumitomo Chemical Co., Ltd.) in the same manner as in Example 8,
A sheet having a thickness of 0.5 mm was formed at a pressing temperature of 150 ° C.

This sheet was in a state of being colored by bisphenol A and was a deep reddish purple. This sheet was suspended in a hot air circulation type oven adjusted to a temperature of 60 ° C. in the same manner as in Example 8, and the remaining rate of empentrin after 3 days was 0%.
However, since the residual ratio of bisphenol A was 99% at this point, no change in color tone was observed.

Examples 9-12 2 parts by weight of alkyl oxybenzoate shown in Table 1,
Rhodamine B base (Taoka Chemical Industry Co., Ltd.) 0.04
Parts by weight, 100 parts by weight of ethylene-methyl methacrylate copolymer (Akulift WH202 manufactured by Sumitomo Chemical Co., Ltd.),
5 parts by weight of a blue color masterbatch (manufactured by Sumika Color Co., Ltd., blue SPEM-5E065) and 2 parts by weight of empentryn (Sumitomo Chemical Co., Ltd. vaporsulin) are melt-kneaded, and then pelletized to form a medicinal effect indicating resin composition. I got a thing.
A three-kind three-layer inflation device is used to supply the above-mentioned drug efficacy indicator resin composition to the intermediate layer, and the inner layer and the outer layer are both low-density polyethylene (Sumikasen manufactured by Sumitomo Chemical Co., Ltd.).
CE2559) and each layer is composed of 0.01mm outer layer / 0.03mm middle layer / 0.01mm inner layer. A three-layer film was obtained. The purple three-layer film thus obtained was hung in a constant temperature and humidity chamber with a space volume of 9 m ³ in a windless condition adjusted to a temperature of 20 ° C. and a humidity of 40%,
The color tone change was observed and the residual amount of the alkyl oxybenzoate ester in the sample was analyzed at regular intervals. As the residual rate of alkyl oxybenzoate decreases, 3
The purple color of the layer film gradually faded, and the disappearance of the alkyl oxybenzoate ester resulted in a blue film.
The empentryn in the film disappeared after 15 days, which was in good agreement with the discoloration period of methyl paraoxybenzoate of Example 9 shown in Table 1. If the space volume becomes small, such as a chest of drawers, the empentryn that has already volatilized in the space is still effective against clothing pests and the actual effective period is extended. Also in that case, the film containing the lower alkyl ester of paraoxybenzoic acid having the discoloration period shown in Table 1 can be used as an indicator of the drug efficacy period by using it according to the size of the space volume. The color change period of each film is shown in Table 1.

[0035]

[Table 1]

Comparative Example 3 Rhodamine B base (Taoka Chemical Industry Co., Ltd.) 0.04
Parts by weight, 100 parts by weight of ethylene-methyl methacrylate copolymer (Akulift WH202 manufactured by Sumitomo Chemical Co., Ltd.),
5 parts by weight of a blue color masterbatch (manufactured by Sumika Color Co., Ltd., Blue SPEM-5E065) and 2 parts by weight of empentrine (Sumitomo Chemical Co., Ltd. vaporsulin) were melt-kneaded and pelletized. Using the equipment, the above pellets are supplied to the intermediate layer, and low density polyethylene (Sumitomo Chemical Co., Ltd.) is used for both the inner and outer layers.
Sumikasen CE2559) was supplied to obtain a three-layer film having the same overall thickness as that of Examples 9 to 12 and a thickness of 0.05 mm. The obtained three-layer film is blue and has a temperature of 20 ° C. and a humidity of 40.
%, The air volume was suspended in a constant temperature and humidity chamber with a volume of 9 m ³ and the color change was observed and the residual analysis of enpentrin in the sample was conducted at regular intervals. No change in color tone of the layered film was observed.

Example 13 2 parts by weight of butyl paraoxybenzoate, 0.04 parts by weight of crystal violet lactone, and 100 parts by weight of low-density polyethylene (Sumikasen F208-0 manufactured by Sumitomo Chemical Co., Ltd.) were melt-kneaded, and then pelletized to obtain a medicinal effect. An indicator resin composition was obtained. This composition was press molded at a molding temperature of 160 ° C.,
A sheet having a thickness of 0.3 mm was obtained. The obtained dark blue sheet was hung in a constant temperature and humidity chamber having a space volume of 9 m ^{3 with} no wind adjusted to a temperature of 20 ° C. and a humidity of 40%, and a change in color tone was observed at regular time intervals. The erasing period of this sheet was one year.

Example 14 A dark blue sheet obtained in the same manner as in Example 13 except that the thickness was 0.6 mm was used, and the temperature was 20 ° C. and the humidity was 40%.
The sample was hung in a constant temperature and humidity chamber with a space volume of 9 m ³ adjusted with no wind, and color tone change observation was performed at regular time intervals. The erasing period of this sheet was 2 years.

Example 15 The dark blue sheet obtained in the same manner as in Example 13 except that the thickness was set to 1 mm was adjusted to a temperature of 20 ° C. and a humidity of 40% without air and a constant volume and a constant humidity of a space volume of 9 m ³ . Hanging in the room,
The color tone change observation was performed every time a certain period of time passed. The color of this sheet gradually faded, but it was a pale blue color even after two years. The erasing period of this sheet was 2 years or more.

[0040]

[Brief description of drawings]

FIG. 1 is a relationship diagram of an elapsed time, a PCMX residual rate, and a color difference ΔE in Example 1.

FIG. 2 is a relationship diagram of elapsed time, PCMX residual rate, and color difference ΔE in Example 2.

FIG. 3 is a relationship diagram of an elapsed time, an OPP residual rate, and a color difference ΔE in Example 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 27/06 KGP 9166-4J 67/00 KJT 8933-4J 77/00 KKU 9286-4J G01N 31 / 22 7906-2J 122 7906-2J // C09K 9/00 Z 7188-4H

Claims (9)

[Claims] 1. A drug efficacy indicating resin composition obtained by melt-kneading a thermoplastic resin, a volatile electron-accepting organic compound, and a hardly volatile electron-donating color-forming organic compound. 2. The drug effect indicating resin composition according to claim 1, wherein the volatile electron-accepting organic compound is a compound having a drug effect. 3. A drug effect indicating resin composition obtained by melt-kneading a thermoplastic resin, a volatile electron-accepting organic compound, a hardly volatile electron-donating color-forming organic compound, and a drug. 4. The thermoplastic resin is a polyolefin resin,
The drug efficacy indicating resin composition according to claim 1, which is a synthetic rubber, a vinyl chloride resin, polyester or nylon. 5. A volatile electron-accepting organic compound in an amount of 0.001 to 50 parts by weight and a hardly volatile electron-donating color-forming organic compound in an amount of 0.0 to 100 parts by weight of a thermoplastic resin.
The drug efficacy indicating resin composition according to claim 1, which is 001 to 5 parts by weight. 6. A hardly volatile electron-donating color-forming organic compound is a rhodamine lactam, a fluorane, a triphenylmethane phthalide, a phenothiazine, an indolyl phthalide, a spiropyran, a leuco auramine, Alternatively, the drug effect indicating resin composition according to claim 1, which is a mixture of two or more of these. 7. A volatile electron-accepting organic compound,
Resorcin, cresol, naphthol, salicylic acid, benzyl alcohol, 1-octanol, stearic acid,
Myristic acid, parachlorometaxylenol, orthophenylphenol, 3-methyl-4-isopropylphenol, 3-aceto-6-methyl-2-pyrronone, lower alkyl esters of oxybenzoic acid or these 2
The drug effect indicating resin composition according to claim 1, which is a mixture of one or more kinds. 8. A drug effect indicating resin composition obtained by melt-kneading a thermoplastic resin, an electron-accepting organic compound having a volatility, and an electron-donating color-developing organic compound having a low volatility, and having a limited shelf life. A time indicator that is attached to the product or used together as a time indicator. 9. The drug effect indicating resin composition according to claim 3, wherein the drug is an agricultural chemical, a drug, an epidemic preventive drug, a sanitary drug and an industrial drug.