JPH0378432B2 - - Google Patents

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a deodorizing resin composition, and more specifically, its purpose is to provide a deodorizing molded product suitable for packaging various malodorous articles, etc. .

(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.

(Problem to be solved by the invention) Conventional packaging using non-breathable packaging materials 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 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 producing 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 and the above-mentioned The present invention was completed based on the finding that the drawbacks of the prior art such as the above can be solved.

(Means for Solving the Problems) 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 ferrous salt and a fumarate. A deodorizing resin composition characterized by comprising an acid and/or a salt thereof.

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. The present invention was completed based on the finding that a resin composition that exhibits a remarkable synergistic effect can be obtained as 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 form or a liquid form.

The individual deodorizing components used in the present invention are all known compounds, and the ferrous salts include:
Various ferrous salts, such as inorganic ferrous salts such as ferrous sulfate, ferrous chloride, ferrous phosphate, ferrous nitrate, ferrous carbonate, ferrous acetate, ferrous oxalate, etc. Organic ferrous salts such as monoferrous, ferrous citrate, ferrous fumarate, and ferrous formate can be used, but ferrous sulfate is particularly preferred.

The main feature of the present invention is that the above-mentioned ferrous salt and fumaric acid and/or its salt 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 Due to the high ferrous salt, the ferrous salt discolors and turns the thermoplastic resin brown, reducing the deodorizing effect and significantly lowering the commercial value of molded products. By using a ferrous salt in combination with fumaric acid and/or its salt, the ferrous salt impairs the deodorizing effect even at high processing temperatures when kneading the deodorizing ingredient into the thermoplastic resin. figure,
Furthermore, it was discovered that the ferrous salt causes little brown discoloration, and together with the deodorizing effect of fumaric acid and/or its salt, it exerts a deodorizing effect that is greater than the sum of the unique deodorizing effects of each compound. .

As for the deodorizing ingredients made of ferrous salt and fumaric acid and/or its salts as described above, their usage ratio is also important.If the total amount is 100 parts by weight, ferrous salt is The proportion of fumaric acid and/or its salt is 90 to 10 parts by weight, and the object of the present invention is best achieved in such a combination and blending ratio.

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. High concentration (for example, 10 to 50% by weight) for later dilution with additive-free thermoplastic resin
It may also be in the form of a masterbatch containing deodorizing ingredients at a concentration of .

The deodorizing resin composition of the present invention as described above is useful for producing deodorizing molded articles.

The deodorizing molded article made of the deodorizing resin composition of the present invention is a molded article of various shapes made of the above-mentioned deodorizing resin composition, for example, a packaging material made of a plastic film or sheet, or a deodorizing resin composition made of the deodorizing resin composition of various shapes. It is a molded product such as a container of any shape formed by the method.

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 desired deodorizing molded article can be obtained.

(Action/Effect) In the prior art, it is known that ferrous salt is used as a deodorizing component, but when such ferrous salt is kneaded into thermoplastic resin, Due to the high processing temperature of the resin, the ferrous salt discolored and colored the thermoplastic resin brown, reducing the deodorizing effect and significantly reducing the commercial value of resin molded products. In such a ferrous salt, fumaric acid/or its salt,
Preferably, by using fumaric acid and its salt in combination, the ferrous salt does not impair its deodorizing effect even at high processing temperatures when kneading the ferrous salt into the thermoplastic resin. The ferrous salt has little brown discoloration and can exhibit a deodorizing effect that is greater than the sum of the deodorizing effects of the ferrous salt and fumaric acid and/or its salt.

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 explained in more detail by giving examples and comparative examples. In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 99 parts of low-density polyethylene with a weight ratio of 10:3:
Blend 1 part of the mixture consisting of ferrous sulfate, fumar, and sodium fumarate in No. 1, mix in a mixer, and use a 40 mm extruder (L/D = 28, CR = 3.1, screw with dullage, cylinder temperature 130 ° C, screw The mixture was kneaded at a rotational speed of 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 wall thickness of approximately 50 microns.

Cut the above film to 50 mm x 200 mm, hang the two cut films like an umbrella inside a 300 ml Erlenmeyer flask, then add 10 micro liters of 42 ppm ammonia water and seal the mouth with parafilm. The ammonia (ppm) in the flask was observed using a Kitagawa detector tube after a certain period of time, and the results were as follows.

1 day, 2 days, 9 days later Blank 25 25 25 Invention product 23 20 15 Comparative example 24 23 21 Note: The blank is a polyethylene film of the same thickness and size molded from polyethylene without any deodorizing component added, and the comparative example is a polyethylene film of the same thickness and size molded from polyethylene without any deodorizing component added. This is an example of using ferrous iron alone.

In addition, bags were made from each of the above-mentioned blank, inventive product, and comparative example films, and thawed small fish were placed in the bags and left to stand. When the bags were opened after 3 days,
The foul odor inside the bag made from the film of the present invention was slight, whereas in the case of the blank, a strong foul odor was diffused. The film of the comparative example was strongly colored brown, whereas the film of the present invention was hardly colored.

Examples 2 to 4 A plastic packaging material of the present invention was obtained in the same manner as in Example 1 except for using the following components, and its performance was measured in the same manner as in Example 1, and the results were as follows.

Example 2 High-density polyethylene 95 parts 8:1.5:0.5 mixture of ferrous sulfate, fumaric acid and potassium fumarate 5 parts After 1 day After 2 days After 9 days Blank 25 25 25 Invention product 10 7 3 Comparative example 23 20 18 Implementation Example 3 Polypropylene 95 parts 8.5:1.5 mixture of ferrous chloride and potassium fumarate 5 parts After 1 day After 2 days After 9 days Blank 25 25 25 Inventive product 10 7 4 Comparative example 23 20 18 Example 4 Polystyrene 98 parts First sulfuric acid 8.7:1.3 mixture of iron and fumaric acid 2 parts 1 day later 2 days later 9 days later Blank 25 25 25 Invention product 21 18 16 Comparative example 23 21 20 Example 5 Weight ratio of 80 parts high density polyethylene to 10:3:1
A deodorizing resin composition of the present invention having a deodorizing component concentration of 20% was obtained in the same manner as in Example 1 by blending 20 parts of a mixture of ferrous sulfate, fumaric acid and lithium fumarate.

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 deodorizing ingredients (ferrous sulfate, fumaric acid and sodium fumarate = 10:3:
1) Mix 30 parts and use a Henschel mixer.
Mix for 2 minutes at a rotation speed of 1500 rpm, then knead with a 40 mm extruder (L/D = 28, CR = 3.1, screw with dullage, cylinder temperature 200-215°C, screw rotation speed 90 rpm) to form pellets. A deodorizing resin composition of the present invention was obtained. This was diluted 10 times with a natural resin, spun at 200 to 215°C using a spinning machine, and stretched 3 times to obtain a 15 denier fiber.

1 g of the above deodorizing fibers was bundled and placed in a 300 ml Erlenmeyer flask, followed by 10 micro liters of 28% ammonia water, and the mouth was sealed with parafilm to completely gasify the ammonia. After a certain period of time had elapsed, ammonia (ppm) in the flask was measured using a Kitagawa detector tube, and the results were as follows.

30 minutes 120 minutes 180 minutes Blank 7500 7200 7100 Invention product 2500 1300 700

Claims (1)

[Claims] 1. 99.9 to 50 parts by weight of thermoplastic resin and deodorizing component
A deodorizing resin composition comprising 0.1 to 50 parts by weight, wherein the deodorizing component comprises a ferrous salt and fumaric acid and/or a salt thereof. 2. The deodorizing resin composition according to claim 1, wherein the deodorizing component comprises 10 to 90 parts by weight of ferrous salt and 90 to 10 parts by weight of fumaric acid and/or its salt.