JPH05320616A - Resin composition for detecting electron-accepting substance and molded article prepared therefrom - Google Patents

Abstract

PURPOSE:To enable an easy visual discrimination of the change in color tone by compounding a thermoplastic resin with an electron-donating color-developing org. compd. in a noncolored state. CONSTITUTION:This compsn. is obtaind by compounding 100 pts.wt. thermoplastic resin with 0.0001-5 pts.wt. electron-donating color-developing org. compd. selected from the group consisting of a Rhodamine lactam compd., a fluoran compd., a triphenylmethane phthalide compd., a phenothiazine compd., an indolyl phthalide compd., a spiropyran compd., a leucoauramine compd., a phenol, a phenolcarboxylic acid, an alcohol, a carboxylic acid, a dialkyl oxalate, and 3-aceto-6-methyl-2-pyronone in a noncolored state. The compsn. is molded into an article having a specific surface area of 10cm<-1> or higher.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for detecting an electron-accepting substance. More specifically, the presence or absence of electron-accepting substances such as phenols, phenolcarboxylic acids, alcohols, carboxylic acids, dialkyl oxalates or 3-aceto-6-methyl-2-pyrronone can be visually detected by changing the color tone. The present invention relates to a resin composition for detecting an electron-accepting substance and a molded article thereof which can be discriminated from each other.

[0002]

2. Description of the Related Art Conventionally, electron-accepting substances such as phenol, phenolcarboxylic acid, alcohol and carboxylic acid are
Widely used in various applications such as mildew proofing, antibacterial, sterilization, cleaning, and lubricants. For example, parachlorometaxylenol,
Electron-accepting substances such as orthophenylphenol and 3-methyl-4-isopropylphenol are used as antifungal agents, but as a method for detecting the disappearance of these substances, there is absolutely nothing to do with the presence of antifungal agents. A time indicator which can be visually discriminated by a change in color tone by utilizing other factors (for example, JP-A-57-168158, JP-A-62-142564, and JP-A-62-62).
No. 180726) is known.

[0003]

However, in the above method, the disappearance of the electron-accepting substance and the discoloration period of the time indicator do not always match, the discoloration largely depends on the use conditions, and the reliability is low. There are problems that it is complicated and that closed packaging is required to prevent discoloration during storage.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the production, storage, use, etc. are extremely simple, and the existence and disappearance of an electron-accepting substance are eliminated. The present invention has been accomplished by finding a sensing material for an electron accepting substance that can be visually and easily discriminated. That is, the resin composition for detecting an electron-accepting substance or a molded product thereof (hereinafter referred to as a detecting material) in the present invention contains an electron-donating color-forming organic compound in a decolorized state in a thermoplastic resin. It is a thing. The electron-accepting substance detection material according to the present invention is such that when the electron-accepting substance is present in the atmosphere, the electron-accepting substance is dissolved in the detection material,
By diffusion, the electron-donating color-forming organic compound becomes a colored state, and conversely, it returns to the initial decolored state with the disappearance of the electron-accepting substance. It is characterized by being used for.

The electron-accepting substance detecting material of the present invention is prepared by a kneading method using a pressure type Banbury or an extruder.
It can be produced by melt-kneading a thermoplastic resin and an electron-donating color forming organic compound. The blending amount of the electron-donating color-forming organic compound can be arbitrarily changed depending on the thermoplastic resin to be used and in consideration of the desired color tone and effective period, but generally it is 0 per 100 parts by weight of the thermoplastic resin. 0.0001 to 5 parts by weight. If the amount of the electron-donating color-forming organic compound is less than 0.0001 parts by weight, discoloration is unclear, and if it exceeds 5 parts by weight, color fading easily occurs due to bleeding on the surface of the composition. Absent.

The mode of use of the electron-accepting substance detecting material of the present invention is not particularly limited, and may be processed into various shapes such as injection molded articles, nets, non-woven fabrics, fibers, sheets and films, or It can be used by wrapping it with a film or non-woven fabric, but if the specific surface area of the melt-molded product is 10 cm ^-1 or more, the electron-accepting substance in the sensing material will dissolve and diffuse rapidly. Preferably
The upper limit is within the range where molding can be performed. When the value of the specific surface area of the molded product is less than 10 cm ^-1 , generally, until a constant coloring state is achieved, except when the solubility and the diffusibility of the electron-accepting substance in the thermoplastic resin are extremely large. The time will be very long.

Further, the electron-accepting substance detecting material of the present invention is used for controlling the dissolution and diffusion of the electron-accepting substance in the thermoplastic resin or for preventing the bleeding of the electron-donating color forming organic compound. It may be appropriately processed and used by a method generally used for thermoplastic resins such as multilayer extrusion molding, composite spinning, extrusion lamination molding and the like.

In the present invention, the electron-donating color-forming organic compound is reversible at room temperature in terms of color development in the presence of an electron-accepting substance and disappearance of the electron-accepting substance or decolorization due to the presence of the electron-donating substance. There is no particular limitation as long as it is a compound that occurs in, various conventionally known compounds, for example, rhodamine lactams, fluoranes, triphenylmethanephthalides, phenothiazines, indolylphthalides, spiropyrans, leuco Compounds such as auramines can be used.

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

The electron-accepting substance that can be detected in the present invention is not particularly limited as long as it is a compound that brings an electron-donating color-forming organic compound into a colored state, and the detection material of the present invention is appropriately used for various purposes. Can be used. Examples of electron-accepting substances include resorcin, cresol, parachlorometaxylenol, orthophenylphenol, 3-methyl-4-isopropylphenol, phenols such as naphthol, phenolcarboxylic acids such as salicylic acid, alcohols such as methanol and ethanol. Kind,
Examples thereof include carboxylic acids such as stearic acid and myristic acid, dialkyl oxalate, and 3-aceto-6-methyl-2-pyranone. In particular, when the electron-accepting substance is a drug exhibiting some activity, it can be a direct sensing material for drug efficacy, which allows the operator to visually know the residual effect state of the actual drug activity.

The thermoplastic resin in the present invention may be any one that can be heat-processed at a temperature not higher than the thermal decomposition temperature of the electron-donating color-forming organic compound and can disperse the electron-donating color-forming organic compound in a decolored state. Branched low-density polyethylene, linear low-density polyethylene which is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, high-density polyethylene, a copolymer of ethylene and / or butene-1 and propylene, vinyl acetate and And / or copolymers of acrylic acid ester and ethylene, olefin-based thermoplastic resins such as polypropylene, styrene-butadiene rubber, synthetic rubber such as ethylene-propylene-diene rubber, vinyl chloride-based thermoplastic resins, polyester, nylon and the like. The
These may be used alone or in combination of two or more.

The thermoplastic resin according to the present invention must be free of components having an electron accepting property such as additives, plasticizers, catalyst residues, etc., which cause the electron donating color forming organic compound to form a color. Furthermore, within the range that does not impair the object of the present invention, that is, within the range that does not develop an electron-donating color-forming organic compound, a fungicide, fungicide, herbicide, plant growth regulator, pheromone, juvenile hormone. Pseudo substances, insecticides, repellents, deodorants, fragrances, pharmaceuticals, antioxidants, ultraviolet absorbers, light stabilizers, antiblocking agents, fillers, transpiration regulators, fragrances, dyes, pigments and the like can be used as appropriate. For example, when a yellow pigment and an electron-donating color-forming organic compound that develops red color are used, the yellow color before use changes to reddish brown in the presence of the electron-accepting substance, and the yellow color disappears as the electron-accepting substance disappears. Return to.

[0013]

The sensing material for electron-accepting substance of the present invention is
Manufacture, storage, use, etc. are extremely simple, and the existence and disappearance of the electron-accepting substance can be visually and directly discriminated from each other, which is an excellent material for detecting the electron-accepting substance.

[0014]

EXAMPLES Next, the present invention will be explained with reference to examples, but the present invention is not limited to these. Example 1 Ethylene-methyl methacrylate copolymer as a thermoplastic synthetic resin (Sumitomo Chemical Co., Ltd. Acryft WH202)
100 parts by weight, 0.04 parts by weight of Rhodamine B base (manufactured by Taoka Chemical Industry Co., Ltd.) as an electron-donating color-developing organic compound are melt-kneaded by using a shear heating in a closed pressure kneader (manufactured by Moriyama Seisakusho). After the lowering, the mixture was fed into an extruder and extruded to carry out hot cutting to form pellets. Subsequently, a multi-layer inflation device equipped with a three-kind three-layer inflation die (diameter 100 mm) was used, and a caliber 40 was used for the middle layer of the die.
The above pellets are melted through a 170 mm extruder zone 170
It was supplied at a discharge rate of 9 kg / h under the condition that the die temperature was 150 ° C. Low density polyethylene (Sumikasen F208-O manufactured by Sumitomo Chemical Co., Ltd.) was supplied to the inner layer and the outer layer at a melting rate of 180 ° C and a die temperature of 150 ° C at a discharge rate of 3 kg / h. The resin supplied to each layer is bonded inside the die, and a tubular body having a three-layer sandwich structure (outer layer / intermediate layer / inner layer) is blow-up ratio 2.0, frost line distance 200 mm, take-up speed 4.2 m / min. Accepted on condition,
A detection material for an electron-accepting substance in the form of a three-layer film having a folding diameter of 320 mm and a thickness of each layer of 0.02 mm for the outer layer / 0.06 mm for the intermediate layer / 0.02 mm for the inner layer and having a total thickness of 0.1 mm was obtained. .. The specific surface area of this sensing material is about 200 cm
^{It was -1} , and the rhodamine B base was in a decolored state in the detection material, which was almost the same in appearance as the film containing no rhodamine B base. As an electron-accepting substance, 3 g of p-cresol has a volume of 300 cm ³ and a caliber of 6
The detection material cut in a semicircular shape having a diameter of 6 cm was placed in the bottom of a wide-mouth bottle having a diameter of 6 cm, and a half of the diameter area of the wide-mouth bottle was covered with a lid. This sensing material turned reddish purple in the presence of the electron-accepting substance, and disappeared as the electron-accepting substance disappeared due to volatilization and became colorless and transparent.

Examples 2 to 7 The types of electron-accepting substances were selected (Example 2: methanol; Example 3: p-chloro-metaxylenol; Example 4: o-
Phenylphenol; Example 5: 3-methyl-4-isopropylphenol; Example 6: dehydroacetic acid; Example 7: dialkyl oxalate), except that the detection material was colored in the same manner as in Example 1. It was visually observed. In the case of any electron-accepting substance, as in Example 1, this sensing material turned reddish purple in the presence of the electron-accepting substance, and disappeared as it disappeared due to volatilization of the electron-accepting substance. became.

Example 8 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 / 0.0 in the intermediate layer.
A three-layer film was obtained in the same manner as in Example 1 except that 3 mm / inner layer was 0.01 mm and the total thickness was 0.05 mm. This sensing material was cut into a circle with a diameter of 5 cm, and the volume was 300 cm ³ .
After laying on the bottom of a wide-mouthed bottle having a diameter of 6 cm, 10 mg of 1-naphthol was added as an electron accepting substance, and the color development state of the detection material was visually observed. After adding the electron-accepting substance,
This detection material changed from colorless and transparent to magenta.

Examples 9 to 13 The kinds of electron-accepting substances were selected (Example 9: hydroquinone;
Example 10: Pyrogallol; Example 11: Bisphenol A; Example 12: Stearic acid; Example 13: Pyrocatechol) In the same manner as in Example 8, the color development state of the sensing material was visually observed. .. In each case, after the electron-accepting substance was added, this detection material changed from colorless and transparent to magenta.

Comparative Examples 1 to 3 At all, except that the electron-accepting substance was used (Comparative Example 1: Acetone; Comparative Example 2: 1,3,5-trioxane; Comparative Example 3: Hinokitiol). By the same method, the color development state of the detection material was visually observed, but in any case, discoloration of the detection material was not observed.

Comparative Examples 4 to 6 Completely the same as Example 8 except that an electron accepting substance was used (Comparative Example 4: Acetone; Comparative Example 5: 1,3,5-trioxane; Comparative Example 6: Hinokitiol). By the same method, the color development state of the detection material was visually observed, but in any case, discoloration of the detection material was not observed.

Claims (9)

[Claims] 1. A resin composition for detecting an electron-accepting substance, comprising a thermoplastic resin containing an electron-donating color-forming organic compound in a decolored state. 2. A molded resin product for detection, which comprises molding the resin composition according to claim 1. 3. The resin composition or resin molded product according to claim 1, wherein the amount of the electron-donating color forming organic compound is 0.0001 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 4. The value of the specific surface area of the resin molding is 10 cm ^−1.
The resin molding according to claim 2, which is the above. 5. The resin composition according to claim 1, wherein the thermoplastic resin is an olefinic thermoplastic resin, a synthetic rubber, a vinyl chloride thermoplastic resin, polyester, nylon, or a mixture of two or more thereof. Or a resin molding. 6. An olefinic thermoplastic resin is a branched low density polyethylene, a linear low density polyethylene which is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, a high density polyethylene, ethylene and / or butene. -1 and propylene copolymer, vinyl acetate and / or acrylic ester and ethylene copolymer, polypropylene, and the synthetic rubber is styrene-butadiene rubber,
The resin composition or resin molded product according to claim 5, which is ethylene-propylene-diene rubber. 7. An electron-donating color-forming organic compound is a rhodamine lactam, a fluorane, a triphenylmethanephthalide, a phenothiazine, an indolylphthalide, a spiropyran, a leuco auramine, or 2 of these.
The resin composition or resin molded product according to claim 1 or 2, which is a mixture of two or more kinds. 8. A method for detecting an electron-accepting substance using the molded article according to claim 2. 9. The method according to claim 8, wherein the electron-accepting substance to be detected is phenols, phenolcarboxylic acids, alcohols, carboxylic acids, dialkyl oxalate or 3-aceto-6-methyl-2-pyrronone.