JPH0573140B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) 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) Packaging using conventional packaging materials without air permeability as described above can prevent the bad odor of the contents from evaporating, but when the containers are opened, It is inconvenient to handle because the foul odor that permeates the inside 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 Problems) That is, the present invention provides 99.9 to 50 parts by weight of a thermoplastic resin other than a thermoplastic polyurethane resin and a deodorizing component.
The deodorizing resin composition is comprised of 0.1 to 50 parts by weight, and is characterized in that the deodorizing component is comprised of a zinc compound and an aluminum sulfate. 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. , polystyrene, polyamide, polyester, cellulose acetate, and other synthetic or modified thermoplastic resins, and all of these thermoplastic resins can be easily obtained from the market and used. These thermoplastic resins may be either solid or liquid such as paste. 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 aluminum sulfate used in the present invention is
These are aluminum sulfate [(Al ₂ (SO ₄ ) ₃ ] and potassium aluminum sulfate [(KAl(SO ₄ ) ₃ ]), and aluminum sulfate is particularly preferred. The main feature of the present invention is that the above-mentioned The point is that a zinc compound and an aluminum sulfate are used in combination. That is, it is known in the prior art to use ferrous salts as a deodorizing component, but such ferrous salts are used in thermoplastic resins. When kneaded into a thermoplastic resin, the ferrous salt changes color and turns the thermoplastic resin brown due to the high processing temperature of the thermoplastic resin, reducing the deodorizing effect and reducing the commercial value of the molded product. In addition, aluminum salts are sometimes used as deodorizing ingredients, but aluminum salts are effective against amine-based malodorous components such as ammonia, but they are effective against sulfur such as hydrogen sulfide. It had almost no effect on the malodorous components of the system.In the present invention, a zinc compound is used instead of such a ferrous salt, and by using this in combination with an aluminum sulfate, heat can be reduced. Even at high processing temperatures when kneading deodorizing ingredients into plastic resin, 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 aluminum sulfate, 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. As for the deodorizing component made of zinc compound and aluminum sulfate, the ratio of their usage is also important.If the total amount is 100 parts by weight, the zinc compound is 10 to 90 parts by weight, and the aluminum is 10 to 90 parts by weight. The proportion of sulfate 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 various shapes made of the above-mentioned deodorizing resin composition, 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) Conventionally, it has been known to use ferrous salt as a deodorizing component, but when such a deodorizing component is kneaded into a thermoplastic resin, etc., the processing temperature of the thermoplastic resin, etc. 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 resin 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 aluminum sulfate, a high Even at processing temperatures, the deodorizing ingredients do not impair their deodorizing effect.
In addition, there is no brown discoloration of the deodorizing component, and it can exhibit a deodorizing effect that is greater than the sum of the deodorizing effects of zinc compounds and aluminum sulfate, and is effective against not only amine-based but also sulfur-based malodorous components. It also showed sufficient deodorizing effect. 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. (Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the text, parts and percentages are based on weight unless otherwise specified. Example 1 Mixture 1 consisting of 99 parts of low density polyethylene and zinc carbonate and aluminum sulfate in a weight ratio of 10:3
40mm extruder (L/D=28, CR=3.1, screw with dullage, cylinder temperature 130℃, screw rotation speed)
70 rpm) to obtain a pellet-shaped 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 thickness of about 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 to 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 film was prepared in the same manner as in Example 1 except that one part each of zinc carbonate and aluminum sulfate was used alone as the deodorizing component in Example 1, and their deodorizing properties were tested in the same manner as in Example 1. As a result of the measurement, 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 aluminum sulfate
5th part

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[Table] Comparative Example 2 A film was prepared in the same manner as in Example 2, except that 5 parts of each of zinc oxide and aluminum sulfate were used alone as deodorizing components in Example 2, and the films were treated in the same manner as in Example 2. When the deodorizing properties were measured, the results shown in the table below were obtained.

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[Table] Example 3 Polypropylene 95 parts Zinc carbonate and aluminum potassium sulfate 5:
5 mixture 5 parts

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[Table] Comparative Example 3 A film was prepared in the same manner as in Example 3, except that 5 parts each of zinc carbonate and potassium aluminum sulfate were used alone as deodorizing components in Example 3, and they were treated 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 3:7 mixture of zinc chloride and aluminum sulfate
2nd part

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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 aluminum sulfate were used alone as deodorizing components in Example 4. When the deodorizing properties 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 aluminum potassium sulfate at a weight ratio of 10:4 was blended with 80 parts of high-density polyethylene, and the following procedure was carried out in the same manner as in Example 1.
A deodorizing resin composition of the present invention having a deodorizing component concentration of 20% 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 aluminum sulfate = 10:3) were mixed for 2 minutes at 1500 rpm in a Henschel mixer, and then mixed in a 40 mm extruder (L/D = 28 , CR=
3.1, screw with dullage, cylinder temperature
The mixture was kneaded at 200 to 215° C. and a screw rotation speed of 90 rpm to obtain a pellet-shaped deodorizing resin composition of the present invention. This was diluted 10 times with natural resin, spun at 200-215℃ using a spinning machine, and stretched 3 times.
Made of 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 deodorizing test Put 1 g of the above deodorizing fiber into a 300 ml Erlenmeyer flask, then add 1 ml of 800 ppm sodium sulfide aqueous solution and 1 N sulfuric acid.
0.1 ml was added, the mouth was sealed with paraffin, and the hydrogen sulfide was completely gasified. after that,
The flask was stored at 25°C, and after a certain period of time, the hydrogen sulfide (ppm) in the flask was measured using a Kitagawa detector tube.The results were as follows.

[Table] Comparative Example 5 A deodorizing fiber was prepared in the same manner as in Example 6, except that 30 parts each of zinc acetate and aluminum sulfate were used alone as deodorizing components in Example 6, and the same method as in Example 6 was used. When their deodorizing properties were measured, the results shown in the table below were obtained.

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Claims (1)

[Scope of Claims] 1. A deodorizing resin composition comprising 99.9 to 50 parts by weight of a thermoplastic resin other than a thermoplastic polyurethane resin and 0.1 to 50 parts by weight of a deodorizing component, wherein the deodorizing component comprises a zinc compound and an aluminum sulfate. A deodorizing resin composition comprising: 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 aluminum sulfate. 3. The deodorizing resin composition according to claim 1, wherein the aluminum sulfate is aluminum sulfate or aluminum potassium sulfate.