JPH10273556A - Melt-moldable biodegradable antibacterial deodorizing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a melt-moldable biodegradable antibacterial deodorizing material which is spontaneously biodegraded and disappears when kept buried in soil and is used as a plastic molding material. SOLUTION: This material is prepd. by mixing and melting a thermoplastic polymer with an alkaline earth metal and/or a transition metal, a thermally reactive monomer, a cellulose aggregate, a water-retaining agent, and a polymn. initiator. The alkaline earth metal and/or the transition metal is used in the form of its carbonate, hydrogencarbonate, lactate, butyrate, oxalate, phosphate, sulfate, benzoate, sorbate, or propinonate, as its halide, as at least two of these compds., and/or as a natural substance contg. the metal. The aggregate is in the form of a power or particles of vegetable fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable biodegradable antibacterial deodorizing material which can be used as an earth-friendly biodegradable plastic molding material.

[0002]

2. Description of the Related Art In recent years, the spread of plastic molded articles has been remarkable, and it has become a necessity in daily life. In daily life, maintaining a comfortable environment and maintaining health is the biggest issue. Thus, in recent times, air purifiers and the like have become widespread in order to maintain a comfortable environment, but none of the products have a sufficient deodorizing function and antibacterial function.

[0003] Conventional antibacterial deodorizing products include metal salts and chlorine-based products.
It was formed by blending a phenol-based or silicate-based compound with plastic, and its antibacterial and deodorizing function was extremely low, and it was difficult to maintain its function for a long period of time. Therefore, development of a safe and comfortable product having both an antibacterial function and a deodorizing function is expected for familiar plastic molded articles used in daily life.

[0004]

Most of the conventional deodorized products are made of inorganic materials such as activated carbon and zeolite, and their free forming cannot be performed. Therefore, the present invention uses a material that can be melt-molded in the same manner as a general-purpose plastic product, and exerts a biodegradable function and an antibacterial deodorizing function on a familiar plastic molded product used in daily life. The aim is to maintain and maintain a comfortable environment and health.

[0005]

Means for Solving the Problems The present invention aims to enhance the functionality of familiar plastic products used in daily life and to use a thermoplastic polymer as a main raw material for securing a comfortable living environment. It is intended to supply a moldable biodegradable antibacterial deodorizing material.

That is, according to the present invention, an alkaline earth and / or transition metal, a thermoreactive monomer, a cellulose aggregate, a water retention agent and a polymerization initiator are coexistent in a thermoplastic polymer, and these are kneaded and melted. It is made of a biodegradable antibacterial deodorant material that can be melt-molded and obtained by the above method.

The object of the present invention is to enhance the function of a plastic molded article. By adding a small amount at the time of molding a general-purpose thermoplastic polymer, its antibacterial deodorizing function is remarkably improved and a comfortable living environment is secured. Can contribute to.
In the case of conventional inorganic materials such as activated carbon and zeolite, the intended function and physical strength are significantly reduced by the melt molding process. In addition, the inorganic material has poor compatibility with the thermoplastic polymer, and cannot be subjected to advanced processing such as being exposed as a foreign substance on the surface of the plastic molded body.

As a result of repeated research and development of antibacterial and deodorizing materials capable of high processing by melt molding, the present inventors have found that the addition of a transition metal and the use of a synergistic effect of a heat-reactive monomer allow the addition of a small amount of an additive. In addition to finding the effect of significantly improving the antibacterial deodorizing function over a long period of time by using only the amount, it was discovered in the course of research that a biodegradable function was developed by coexistence of a cellulose aggregate and a water retention agent.

[0009] With the completion of the present invention, a biodegradable antibacterial deodorizing material using a thermoplastic polymer as a main raw material for enhancing the functions of familiar plastic products used in daily life and for ensuring a comfortable living environment. Supply becomes possible and has great significance from the viewpoint of environmental conservation.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polymer in the present invention includes low molecular weight structures such as polyethylene, polypropylene and polyvinyl chloride, but the present invention is applicable to all other general-purpose plastic raw materials. Is the feature.

The heat-reactive monomer in the present invention has a cationic dissociating group and / or an anionic dissociating group. The cationic dissociating groups include strongly acidic and weakly acidic dissociating groups. , Carboxyl group, sulfonic acid group, oxosulfonic acid group, phosphoric acid group, sulfoethyl group,
Examples include a sulfomethyl group and a carbomethyl group.

The heat-reactive monomer having a cationic dissociating group includes, for example, acrylic acid, methacrylic acid, styrenesulfonic acid and 2-acrylamide-2.
-Methylpropanesulfonic acid and the like, and heat-reactive monomers that can be converted into a cationic dissociation group include, for example, styrene, acrylonitrile, glycidyl methacrylate and glycidyl acrylate.

The anionic dissociating group of the heat-reactive monomer in the present invention includes a strongly basic dissociating group and a weakly basic dissociating group, such as an ammonium group, an amino group, a methylamino group, a dimethylamino group and a diethylamino group. There is.

The heat-reactive monomer having an anionic dissociating group includes, for example, vinylbenzyltrimethylammonium salt, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminomethyl methacrylate, tertiary butyl There are aminoethyl acrylate, tertiary butylaminoethyl methacrylate, dimethylaminopropyl acrylamide and the like, and styrene and glycidyl methacrylate as heat-reactive monomers that can be converted into anionic dissociative groups as well as cationic dissociative groups.

The heat-reactive monomer having a cationic dissociating group and / or an anionic dissociating group in the present invention includes:
Irradiating the above monomer with ionizing radiation to increase the polymerization degree to 6000
Controlled below, a molecular structure containing both a dissociable functional group and a reactive double bond is used.

The ionizing radiation source used for the polymerization of the thermoreactive monomer of the present invention includes α-rays, β-rays, γ-rays, accelerating electron beams,
There are X-rays, ultraviolet rays, etc., which can be arbitrarily selected according to the production scale and purpose.

The cellulose aggregate used in the present invention comprises starch,
Corn starch, konjac powder, gelatin powder, agar powder,
Flour, vegetable cellulose such as peat moss is desirable, but methylcellulose, carboxymethylcellulose,
The effect of expressing biodegradability can be exhibited by mixing with one or more of hydroxyethyl cellulose and the like.

As the water retention agent used in the present invention, polyethylene oxide having a molecular weight of 100,000 to 300,000 is effective.
Sodium pantothenate, sodium ascorbate,
It can be arbitrarily selected from low molecular weight substances such as sodium polyacrylate, acrylamide, dimethylacrylamide, hydroxyethyl methacrylate, hydroxypropyl acrylate, vinylpyrrolidone, and dimethylacrylamide according to the purpose.

The polymerization initiator used in the present invention includes azo-based and peroxide-based initiators, such as azobisisobutylnitrile (AIBN) and azobismethylbutylnitrile (AM
BN), azobiscyclohexanecarbonitrile (AC
HIN) can be arbitrarily selected.

[0020]

EXAMPLE 1 A mixture of 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 10 parts of N, N-dimethylacrylamide, 2 parts of hydroxyethyl methacrylate, 1 part of aldohexose, 17 parts of ethyl alcohol, and 50 parts of water Was sufficiently deoxygenated, and irradiated with 10 kGy of γ-rays. This solution was dispersed in 10 parts, mixed with 25 parts of powdered polyethylene (Flocene A1003), and thoroughly stirred while drying with a Hensyl mixer. Then, 50 parts of starch, 5 parts of calcium carbonate, 4 parts of talc, and 5 parts of polyethylene oxide were mixed.
After mixing 1 part of AIBN and 1 part of AIBN, material pellets of a biodegradable antibacterial deodorizing material were prepared with a pelletizer.

This material pellet was formed into a filter chip by an extruder. This was placed in a 300-liter closed container, and 100 ppm of ammonia gas was added. As a result, the ammonia concentration in the container was 25 pp after 30 minutes.
m, 17 ppm after 60 minutes, 9 ppm after 120 minutes,
After 180 minutes, it was reduced to 5 ppm or less, showing an excellent deodorizing effect.

A section of a filter chip of a biodegradable antibacterial deodorizing material was used for 1 × 10 ³ viable E. coli (Escheri).
Chia coli IFO-3301) solution and cultured at 34 ° C. for 18 hours. As a result, the number of viable bacteria in the E. coli solution was 10 or less, and an excellent antibacterial effect was confirmed.

A filter chip of a biodegradable antibacterial deodorizing material was buried 10 cm under the lawn and dug up one month later. As a result, there was no trace of the filter chip, and only a slight residue was confirmed, and it disappeared by biodegradation. Was being processed.

[0024]

Comparative Example 1 A commercially available activated carbon for deodorization was subjected to an ammonia gas adsorption test in the same manner as in Example 1. As a result, 80 ppm after 30 minutes, 70 ppm after 60 minutes, and 6 ppm after 120 minutes.
2ppm, only reduced to 60ppm after 180 minutes,
Even after 3 hours or more, it was impossible to remove up to half of the amount added, which was significantly different from the filter chip of the present invention.

As a result of conducting an antibacterial test under the same conditions, the number of viable bacteria after 20 hours had increased compared to that before the test, and no antibacterial function was observed.

Furthermore, a biodegradability test was conducted under the same conditions. As a result, no change in shape was observed even after one month, and no biodegradation function was confirmed.

[0027]

Example 2 10 parts of sodium styrenesulfonate, 10 parts of diethylaminoethyl methacrylate, 10 parts of sodium dodecylbenzenesulfonate, aldohexose 1
Part, azobismethylbutylnitrile 1 part, methyl alcohol 18 parts, after sufficiently deoxygenating a mixture of 50 parts of water,
Irradiated with a 1 kw ultraviolet lamp for 3 hours. Take 10 portions of this liquid and powder polyethylene (Flocene A1003) 3
After mixing with 0 parts and thoroughly stirring while drying with a Hensyl mixer, 40 parts of konjac powder, 4 parts of oyster shell powder, 5 parts of talc, 10 parts of polyethylene oxide, and 1 part of azobiscyclohexanecarbonitrile were mixed. Material pellets of biodegradable antibacterial deodorizing material were prepared with a pelletizer.

This material pellet was formed into a sheet by press molding. This was placed in a 300-liter closed container, and as a result of adding 100 ppm of trimethylamine, the concentration of trimethylamine in the container was 50 ppm after 30 minutes,
30 ppm after 60 minutes, 10 ppm after 120 minutes, 1
After 80 minutes, it was reduced to 5 ppm or less, showing an excellent deodorizing effect.

A section of the molded article of the biodegradable antibacterial deodorizing material was used for Escherichia coli having a viable cell count of 1 × 10 ^3.
coli IFO-3301) solution at 34 ° C, 1
As a result of culturing for 8 hours, the number of viable bacteria in the E. coli solution was 20 or less, and an excellent antibacterial effect was confirmed.

A molded body of the biodegradable antibacterial deodorizing material was buried 10 cm under the lawn and dug up one month later. As a result, there was no trace of the molded body, and only a slight residue was confirmed. Was being processed.

[0031]

COMPARATIVE EXAMPLE 2 The same operation as in Example 1 was carried out to conduct an adsorption test of trimethylamine on a commercially available ascorbic acid type deodorant. As a result, 95 ppm was obtained after 30 minutes and 90 pp after 60 minutes.
m, 80 ppm after 120 minutes, 85 ppm after 180 minutes
Even after 10 hours or more, it was impossible to remove up to half of the added amount of trimethylamine, which was significantly different from the molded article of the present invention.

As a result of conducting an antibacterial test under the same conditions,
After 20 hours, the number of viable bacteria was 5 × 10 ³ , which was higher than before the test, and no antibacterial function was observed.

As a result of conducting a biodegradability test under the same conditions,
Even after one month, the original shape was maintained, and no biodegradation function was confirmed.

[0034]

EXAMPLE 3 A mixture of 15 parts of acrylic acid, 10 parts of 2-acrylamido-2-methylpropanesulfonic acid and dimethylaminoethyl methacrylate, 5 parts of copper gluconate, 1 part of aldohexose, 19 parts of ethyl alcohol, and 50 parts of water Was sufficiently deoxygenated and irradiated with 10 kGy of γ-ray. 10 parts of this liquid was dispersed in powdered polyethylene (Flosen A).
1003) The resulting mixture was mixed with 10 parts, thoroughly stirred while being dried with a Hensyl mixer, and then pelletized with a kneading extruder. 20 parts of these pellets, powdered polyethylene 1
After mixing 5 parts, 50 parts of corn starch, 5 parts of calcium carbonate, 4 parts of talc, 5 parts of polyethylene oxide and 1 part of azobisisobutylnitrile, the mixture was formed into a filter chip by an extruder.

The compact was placed in a 300-liter closed container, and 100 ppm of diethylamine gas was added. As a result, the concentration of diethylamine in the container was reduced to 70 pp after 30 minutes.
m, 60 ppm after 60 minutes, 40 pp after 120 minutes
m, after 180 minutes, decreased to 20 ppm or less, showing an excellent deodorizing effect.

A section of the molded article of the biodegradable antibacterial deodorizing material was subjected to Escherichia coli having a viable cell count of 1 × 10 ^3.
coli IFO-3301) solution at 34 ° C, 1
As a result of culturing for 8 hours, the number of viable bacteria in the E. coli solution was 5 or less, and an excellent antibacterial effect was confirmed.

A molded article of the biodegradable antibacterial deodorizing material was buried 10 cm under the lawn and dug up one month later. As a result, there was no trace of the molded article, and only a slight residue was confirmed. Was being processed.

[0038]

Comparative Example 3 An adsorption test of diethylamine on a commercially available flavono-based deodorant was performed in the same manner as in Example 1, and as a result, 98 ppm after 30 minutes, 95 ppm after 60 minutes, and 1 ppm.
90 ppm after 20 minutes, 85 ppm after 180 minutes and 10
Even after the lapse of time, it was impossible to remove half of the amount of diethylamine added, which was significantly different from the molded article of the present invention.

As a result of conducting an antibacterial test under the same conditions,
After 20 hours, the number of viable cells was 9 × 10 ³ , which is higher than that before the test, and no antibacterial function was observed.

As a result of conducting a biodegradability test under the same conditions,
Even after one month, no change in shape was observed at all, and no biodegradation function was confirmed.

[0041]

According to the present invention, an environmentally friendly biodegradable antibacterial deodorizing material is obtained. The present invention not only exerts a function in a molded body but also exerts a function as a raw material pellet in a former stage of molding. Therefore, it can be formed into any shape, and application to a wide range of applications can be expected.

Further, in the present invention, a small amount of a transition metal and a thermoreactive monomer having a cationic dissociating group and / or an anionic dissociating group are added to a thermoplastic polymer to produce a synergistic effect. The antibacterial deodorizing function was remarkably improved over a long period of time, and the biodegradable function was able to be exhibited by coexisting the cellulose aggregate and the water retention agent.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/32 C08K 3/32 5/098 5/098 C08L 3/04 C08L 3/04 101/00 101/00 // C08L 33/14 33 / 14 (72) Inventor Akihiko Mori 1915-1 Shinma, Shizuoka City, Shizuoka Prefecture (72) Inventor Nori 2-9-20 Sena Chuo, Shizuoka City, Shizuoka Prefecture (72) Inventor Shigeaki Ide 2104, Atsuhara, Fuji City, Shizuoka Prefecture -1 (72) Inventor Yasushi Shibuya 2659-15, Fuji-den, Shizuoka Prefecture (72) Inventor Akiko Takada 3-5-38 Sena Chuo, Shizuoka City, Shizuoka Prefecture

Claims (6)

[Claims] 1. A biodegradable antibacterial deodorizing material obtained by kneading and melting a thermoplastic polymer in the presence of an alkaline earth and / or transition metal, a thermoreactive monomer, a cellulose aggregate, a water retention agent and a polymerization initiator. . 2. The alkaline earth and / or transition metal added to the thermoplastic polymer is a salt or halide of carbonic acid, bicarbonate, lactic acid, butyric acid, oxalic acid, phosphoric acid, sulfuric acid, benzoic acid, sorbic acid or propionic acid. 2. The biodegradable antibacterial deodorizing material according to claim 1, comprising two or more of these compounds and / or a natural product thereof. 3. The biodegradable antibacterial deodorant according to claim 1, wherein the thermoreactive monomer added to the thermoplastic polymer has a main chain whose degree of polymerization is controlled to 6000 or less by ionizing radiation synthesis. material. 4. The biodegradable antibacterial deodorizing material according to claim 1, wherein the thermoreactive monomer to be added to the thermoplastic polymer has a low molecular structure having a cationic dissociating group and / or an anionic dissociating group. 5. The biodegradable antibacterial deodorizing material according to claim 1, wherein the cellulose aggregate coexisting with the thermoplastic polymer comprises powder and granules of vegetable fiber. 6. The thermoplastic polymer according to claim 2, wherein
A biodegradable antibacterial deodorizing material which can be kneaded as a composite with a general-purpose melt-molded material in the form of pellets or flakes treated with the composite additive described in the above item.