JPH0573141B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a deodorizing resin composition, and more specifically, an object of the present invention is to provide a deodorizing molded product suitable for packaging various malodorous articles. (Prior Art) Conventionally, deodorizing agents for various sources of malodor have been widely used, and in order to package various malodorous articles, non-permeable plastic films, aluminum foils, and metals are mainly used. Containers, glass containers, etc. are used. (Problems to be Solved by the Invention) Conventional packaging using non-breathable packaging materials as described above can prevent the odor of the contents from evaporating, but when the containers are opened, It is inconvenient to handle because the foul odor that is pervading the air evaporates outside all at once. As a result of intensive research to solve the above-mentioned drawbacks of the prior art, the inventor of the present invention has developed a plastic film,
When manufacturing molded products such as plastic sheets or plastic containers, when a specific substance is included in the thermoplastic resin used, the resulting molded product, for example, a packaging material, has excellent deodorizing properties, The present invention was completed based on the finding that the drawbacks of the prior art as described above can be solved. (Means for solving the problem) That is, the present invention provides a deodorizing resin composition comprising 99.9 to 50 parts by weight of a thermoplastic resin and 0.1 to 50 parts by weight of a deodorizing component, in which the deodorizing component is a zinc compound and an aliphatic polyester. This is a deodorizing resin composition characterized by comprising a carboxylic acid. Next, to explain the present invention in more detail, the present inventor has conventionally conducted various studies on deodorizing resin compositions and molded products obtained therefrom, but by blending a specific combination of deodorizing compounds,
The present invention was completed based on the finding that resin compositions and molded articles that exhibit a remarkable synergistic effect can be obtained compared to when each deodorizing compound is used alone. The thermoplastic resin used in the present invention refers to polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, and vinylon, which have been conventionally used for molding various molded products such as plastic films, plastic sheets, plastic containers, fibers, etc. These thermoplastic resins are synthetic or modified thermoplastic resins such as polystyrene, polyamide, polyester, and cellulose acetate, and all of these thermoplastic resins can be easily obtained and used on the market. It may be in a liquid form such as a paste or the like. The individual deodorizing components used in the present invention are all known compounds, and the zinc compounds include various zinc compounds, such as zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate, and zinc carbonate. and organic zinc salts such as zinc acetate, zinc oxalate, zinc citrate, zinc fumarate, and zinc formate, particularly preferred are zinc white (zinc oxide) and zinc carbonate. The aliphatic polycarboxylic acid used in the present invention is
For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, methylmaleic acid, methylfumaric acid, itaconic acid, citraconic acid, mesaconic acid, acetylenic acid, malic acid, methylmalic acid. acids, di- or tricarboxylic acids such as citric acid, isocitric acid, tartaric acid, or salts thereof, and particularly preferred in the present invention are citric acid, fumaric acid, or salts thereof. The main feature of the present invention is that the above zinc compound and aliphatic polycarboxylic acid are used in combination as a deodorizing component. That is, it is known in the prior art that ferrous salts are used as deodorizing ingredients, but when such ferrous salts are kneaded into thermoplastic resins, etc., the processing temperature of the thermoplastic resins must be Because of the high ferrous salt, the ferrous salt discolored and colored the thermoplastic resin brown, reducing the deodorizing effect and significantly lowering the commercial value of the molded product. In the present invention, a zinc compound is used instead of such a ferrous salt, and by using this in combination with an aliphatic polycarboxylic acid, the deodorizing component is kneaded into a thermoplastic resin. Even at high processing temperatures, the deodorizing ingredients do not lose their deodorizing effect.
In addition, there is no brown discoloration of the deodorizing components, and together with the deodorizing effect of aliphatic polycarboxylic acids, it is possible to deodorize not only amine-based malodorous components but also sulfur-based deodorizing components. It was discovered that the deodorizing effect is greater than the sum of the deodorizing effects. In the deodorizing component made of a zinc compound and an aliphatic polycarboxylic acid or its salt as described above, the ratio of their use is also important.If the total amount is 100 parts by weight, the zinc compound will be 10 to 90 parts by weight. On the other hand, the proportion of aliphatic polycarboxylic acid is 90 to 10 parts by weight, and in such a combination and blending ratio, the objects of the present invention are best achieved. The deodorizing resin composition of the present invention has the above two components as essential components, but it also includes various conventionally known additives for resins, such as colorants, fillers, extender pigments, plasticizers, stabilizers, and ultraviolet absorbers. Agents and the like can be added as desired. The deodorizing resin composition of the present invention can be obtained by simply mixing the above components, or may be obtained by melt-kneading the mixture and granulating it into pellets or the like. Furthermore, it may be in the form of a masterbatch containing a high concentration (for example, 10 to 50% by weight) of the deodorizing component for later use by diluting with an additive-free thermoplastic resin. The deodorizing resin composition of the present invention as described above is useful for producing deodorizing molded articles. Deodorizing molded products include molded products of the above-mentioned deodorizing resin composition in various shapes, such as packaging materials made of plastic films or sheets, or containers of arbitrary shapes made by molding the deodorizing resin composition by various methods. It is a molded product such as. Forming of such films, sheets, containers, etc.
It can be easily carried out using various conventionally known conditions using conventionally known inflation devices, presses, calenders, extrusion molding machines, spinning machines, blow molding machines, injection molding machines, vacuum molding machines, etc. A deodorizing molded product can be obtained. (Action/Effect) It is well known that ferrous salts are used as deodorizing ingredients, but when such deodorizing ingredients are kneaded into thermoplastic resins, etc., the processing temperature of the thermoplastic resins may vary. Because of the high ferrous salt content, the ferrous salt discolors and turns the thermoplastic resin brown, reducing the deodorizing effect and significantly lowering the commercial value of resin molded products. In contrast, in the present invention, a zinc compound is used instead of such ferrous salt,
By using this in combination with aliphatic polycarboxylic acid or its salt, the deodorizing component does not lose its deodorizing effect even at high processing temperatures when kneading the deodorizing component into the thermoplastic resin. There is no brown discoloration, and it can exhibit a deodorizing effect that is greater than the sum of the deodorizing effects of zinc compounds and aliphatic polycarboxylic acids.
It showed a sufficient deodorizing effect against sulfur-based malodorous components. Therefore, when molded articles, such as packaging materials, made of the deodorizing resin composition of the present invention are used to package articles with strong malodors, such as fish and fish products, various pickles, and various other foods, the odor emitted from the molded articles, such as packaging materials, can be reduced. Since the packaging material itself absorbs the odor, strong odor will not spread to the surrounding area even when these packages are opened. For the same reason, it is also effective for packaging not only food but also various household garbage, factory waste, etc. In addition to the above-mentioned packaging materials, the deodorizing resin composition of the present invention can also be used in deodorizing molded articles, such as granular deodorizing agents, in places where foreign odors or malodors occur or accumulate.
It is useful as a raw material for deodorizing wall coverings, floor coverings, deodorizing fibers, textiles, and other molded products. (Example) Next, the present invention will be specifically described with reference to Examples. In the text, parts or percentages are based on weight unless otherwise specified. Example 1 99 parts of low-density polyethylene was blended with 1 part of a mixture of zinc carbonate and fumaric acid at a weight ratio of 10:3, mixed in a mixer, and transferred to a 40 mm extruder (L/D=
28, CR=3.1, screw with dullage, cylinder temperature 130℃, screw rotation speed 70rpm)
The mixture was kneaded to obtain a pellet-like deodorizing resin composition of the present invention. Next, the above deodorizing resin composition was passed through an inflation device (30 mm extruder, 50 mm inner diameter inflation die, cylinder temperature 140°C, screw rotation speed).
60 rpm) to obtain a polyethylene film with a wall thickness of approximately 50 microns. The deodorizing properties of this deodorizing sheet were investigated and the results were as follows. Ammonia deodorization test The above deodorizing sheet was cut into 50 mm x 210 mm, and the two cut sheets were hung in an umbrella shape in a 300 ml Erlenmeyer flask, then 100 ml of 42 ppm ammonia water was added, and the mouth was sealed with paraffin. , the ammonia was completely gasified. Thereafter, the flask was stored at 25°C, and after a certain period of time the ammonia (ppm) in the flask was measured using a Kitagawa detector tube.The results were as follows.

[Table] Note: The blank is a sheet with no deodorizing ingredients added (the same applies below).
Hydrogen sulfide deodorization test Cut the above deodorizing sheet into 50 mm x 200 mm, put one cut sheet into a 300 ml Erlenmeyer flask, and then add 1 ml of 800 ppm sodium sulfide aqueous solution and 0.1 N sulfuric acid.
A milliliter was added, the mouth was sealed with paraffin, and the hydrogen sulfide was completely gasified. Then 25
The hydrogen sulfide (ppm) in the flask was measured using a Kitagawa detector tube after a certain period of time after being stored at ℃.The results were as follows.

[Table] In addition, bags were made from the above-mentioned blank film and the film of the invention product, and thawed small fish were placed in the bag and left to stand. When the bag was opened after 3 days, it was found that the bag was made from the film of the invention product. While the odor inside the bag was slight, in the case of the blank, a strong odor was diffused. Comparative Example 1 A sheet was prepared in the same manner as in Example 1, except that one part each of zinc carbonate and fumaric acid was used alone as the deodorizing component in Example 1, and the deodorizing properties of the sheet were evaluated in the same manner as in Example 1. When measured, the results shown in the table below were obtained.

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[Table] Examples 2 to 4 A plastic packaging material of the present invention was obtained using the following ingredients and in the same manner as in Example 1, and its performance was measured in the same manner as in Example 1. It was hot. Example 2 High density polyethylene 95 parts 8:2 mixture of zinc oxide and fumaric acid 5 parts

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[Table] Comparative Example 2 A sheet was prepared in the same manner as in Example 2, except that 5 parts each of zinc oxide and fumaric acid were used alone as deodorizing ingredients in Example 2, and the sheet was prepared in the same manner as in Example 2. When the deodorizing properties of were measured, the results shown in the table below were obtained.

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【table】 Example 3 Polypropylene 95 parts 5 parts of a 5:5 mixture of zinc carbonate and citric acid

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[Table] Comparative Example 3 A sheet was prepared in the same manner as in Example 3, except that 5 parts each of zinc carbonate and citric acid were used alone as deodorizing ingredients in Example 3, and the sheet was prepared in the same manner as in Example 3. When the deodorizing properties of were measured, the results shown in the table below were obtained.

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【table】 Example 4 Polystyrene 98 parts 2 parts of a 3:7 mixture of zinc chloride and fumaric acid

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[Table] Comparative Example 4 A film was prepared in the same manner as in Example 4, except that 2 parts each of zinc chloride and citric acid were used alone as deodorizing ingredients in Example 4, and the sheet was prepared in the same manner as in Example 4. When the deodorizing properties of were measured, the results shown in the table below were obtained.

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[Table] Example 5 20 parts of a mixture consisting of zinc oxide and fumaric acid at a weight ratio of 10:4 was blended with 80 parts of high-density polyethylene, and the same procedure as in Example 1 was carried out to obtain a deodorizing component concentration of 20.
% of the deodorizing resin composition of the present invention was obtained. This deodorizing resin composition was diluted 20 times with additive-free high-density polyethylene, and was molded using a blow molding machine (45 mm screw, screw rotation speed 30 rpm, cylinder temperature 200°C) into a 1 mm thick, 60 mm diameter, high A bottle-shaped molded product with a length of 170 mm was obtained. In this container,
When the container was sealed with partially rotten meat and opened after being left for 3 days, the odor was significantly weaker than in the case of the same container with no deodorizing ingredients added. Example 6 70 parts of polypropylene and 30 parts of a deodorizing component (zinc acetate and fumaric acid = 10:3) were mixed in a Henschel mixer at a rotation speed of 1500 rpm for 2 minutes, and then in a 40 mm extruder (L/D = 28 , CR=3.1, screw with dullage, cylinder temperature 200 to 215
The deodorizing resin composition of the present invention in the form of pellets was obtained by kneading at a screw speed of 90 rpm. Dilute this 10 times with natural resin and use a spinning machine.
The fibers were spun at 200-215°C and stretched three times to obtain a 15 denier fiber. When the deodorizing properties of this deodorizing fiber were investigated, the results were as follows. Ammonia deodorization test 1g of the above deodorizing fiber was placed in a 300ml Erlenmeyer flask, and then 10% of 28% ammonia water was added.
Micron liters were added, the mouth was sealed with paraffin, and the ammonia was completely gasified. Thereafter, the flask was stored at 25°C, and after a certain period of time the ammonia (ppm) in the flask was measured using a Kitagawa detector tube.The results were as follows.

[Table] Hydrogen sulfide deodorization test Put 1 g of the above deodorized fiber into a 300 ml Erlenmeyer flask, then add 1 ml of 800 ppm sodium sulfide aqueous solution and 0.1 N sulfuric acid.
A milliliter was added, the mouth was sealed with paraffin, and the hydrogen sulfide was completely gasified. Then 25
The hydrogen sulfide (ppm) in the flask was measured using a Kitagawa detector tube after a certain period of time after being stored at ℃.The results were as follows.

[Table] Comparative Example 5 Deodorizing fibers were prepared in the same manner as in Example 6, except that 30 parts each of zinc acetate and fumaric acid were used alone as deodorizing ingredients in Example 6, and When the deodorizing properties of the deodorizing fibers were measured, the results shown in the table below were obtained.

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Claims (1)

[Claims] 1. 99.9 to 50 parts by weight of thermoplastic resin and deodorizing component
1. A deodorizing resin composition comprising 0.1 to 50 parts by weight, wherein the deodorizing component comprises a zinc compound and an aliphatic polycarboxylic acid. 2. The deodorizing resin composition according to claim 1, wherein the deodorizing component comprises 10 to 90 parts by weight of a zinc compound and 90 to 10 parts by weight of an aliphatic polycarboxylic acid. 3. The deodorizing resin composition according to claim 1, wherein the aliphatic polycarboxylic acid is fumaric acid or a salt.