JP2000281912A - Antibacterial composite material which can be incinerated without forming dioxins and method for molding same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite material excellent in antibacterial properties and capable of being incinerated without forming dioxins by including calcined dolomite in a matrix resin. SOLUTION: A matrix resin such as a thermoplastic resin, a thermosetting resin, a natural plastic, a pulp, a synthetic rubber, or a natural rubber is compounded with 3-20 wt.%, desirably, 3-15 wt.% or 1-7.5 g/m2, desirably, 3-7.5 g/m2, of calcined dolomite having a particle diameter of 1-15 μm, desirably, 1-10 μm and, optionally, additives such as a blowing agent, a lubricant, a colorant, a pigment, a heat stabilizer, an ultraviolet stabilizer, an antioxidant, a plasticizer, a curing agent, a catalyst, a filler, a reinforcement, an extender, an antistatic agent, a flame retardant, and an antibacterial/antimold. The obtained composite material is molded into a bag or into e.g. a drip sheet for use in a pack of a product such as a fishery product. Such molding can develop an antibacterial action in a short time to keep the contents fresh for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel antibacterial composite material capable of suppressing the generation of dioxins during incineration, and a method of forming the same.

[0002]

2. Description of the Related Art In the processing of plastics, compounding agents and additives such as plasticizers, antioxidants, fillers and antistatic agents are indispensable. Antibacterial and antifungal agents are also one of the essential additives for some plastics, and depending on the application, are not limited to the type of plastic and are also essential components. For example, the damage of plastics caused by microorganisms is commonplace today, and it often requires some kind of antibacterial treatment other than sensitive plastics such as soft vinyl chloride resin and urethane resin.

[0003] Antibacterial and antifungal agents used in plastics currently provided can be roughly classified into organic and inorganic.

[0004] Organic antibacterial and antifungal agents, which are conventionally known as bactericides, can withstand heating during processing of plastics and have long-lasting properties when kneaded into plastic products. Stable ones are used, and typical organic antibacterial and antifungal agents include 2- (4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) -phthalimide, 2,3,5,6 -Cytochloro-4- (methylsulfonyl) -pyridine, 1
0,10'-oxybisphenoxyarsine, trimethoxysilyl-propyloctadecyl ammonium chloride, 2-n-octyl-4-isothiazolin-3-one, bis (2-pyridylthio-1-oxide) zinc and the like.

However, these organic antibacterial and antifungal agents diffuse into the environment from plastic processed products due to volatilization and elution and exhibit an immediate effect. Therefore, their expiration dates are relatively short, and their effects on the human body and the like are relatively small. It can be said that it is strong. In addition, some of the organic antibacterial and antifungal agents are suspected to be teratogenic, and some of the waste are toxic. Furthermore, it is particularly safe in applications where it is desired to be safe in all stages of processing, use and disposal, such as the potential toxicity of antibacterial and antifungal agents themselves, toxicity when gasifying, and toxicity of thermal decomposition products. It can be said that there is a difficulty in securing the sex. In addition, some of the organic antibacterial and antifungal agents have a processing temperature of plastic (200 ° C or less, such as soft vinyl chloride resin, but most of them have a processing temperature of 20 ° C).
0 ° C or higher, and even near 300 ° C. )) Has heat resistance as a single item, but when added to plastics, it may decompose at lower temperatures to yellow the resin or adversely affect molding. Furthermore, such organic antibacterial and antifungal agents are relatively expensive.

On the other hand, inorganic antibacterial and antifungal agents include silver, copper,
Most metal-substituted antibacterial and antifungal agents carry an antibacterial metal such as zinc on an inorganic ion exchanger or porous carrier such as zirconium phosphate, zeolite, hydroxyapatite, silica / alumina, and silica gel. However, silver-based inorganic antibacterial agents which are effective and highly safe are generally used in many cases. With these inorganic antibacterial and antifungal agents,
Although the above problems such as organic antibacterial and antifungal agents do not occur, metal ions as active ingredients catalytically degrade the base resin of plastics, and silver inorganic antibacterial agents, especially light (ultraviolet rays) Some of them have difficulty in light fastness, for example, they change into metallic silver and easily discolor. Further, such an inorganic antibacterial and antifungal agent also needs to be carried on an inorganic ion exchanger or a porous body, and requires a predetermined number of manufacturing steps, and is therefore relatively expensive. In addition, since these conventional inorganic antibacterial and antifungal agents hardly volatilize and elute like organic antibacterial and antifungal agents, those dispersed on the surface of plastic molded products such as processed products are bacteria and fungi. Since the effect is produced only by contact with the base material, a known inorganic material is added at a predetermined ratio to the base resin (or the resin component of the paint which is a raw material of the coating when forming an antibacterial coating film on the plastic surface). Even if a plastic (or an antibacterial coating film on a plastic surface) is processed by adding and mixing an antibacterial and antifungal agent, a product having a sufficient antibacterial property cannot be produced.
In addition, inorganic antibacterial materials including composite ceramics with a new and extremely high antibacterial property at a predetermined ratio to base resin, etc.
Even if a plastic or the like is processed by adding and mixing a fungicide, a product having an antibacterial property exceeding the conventional level could not be produced.

On the other hand, at present, dioxins generated from incinerators installed in various parts of the country and ash of incinerators also contain a considerable amount of dioxins.

[0008] Here, dioxins, which are generally attracting attention as environmental pollutants, are polychlorinated dibenzoparadioxins (PCDDs), and 75 kinds of homologues (isomers) depend on the number and location of chlorine molecules substituted. Including).
In addition, polychlorinated dibenzofurans (PCDFs), which are usually produced together with these PCDDs and have similar chemical structures and properties, are also 135.
A group of compounds having different homologs. Recently, various chlorine compounds have been the subject of debate as dioxin-related substances, but their evaluation has not necessarily been finalized, and dioxin-related substances detected in the environment are generally mixtures of complex homologs. For this reason, in this specification, both PCDDs and PCDFs (including homologs) as environmental pollutants are combined into dioxins. These compounds are extremely stable in the environment, are often highly toxic to living organisms, are a group of substances having no usefulness to human beings, and are not commercially produced. Dioxins are produced as a small amount of impurities as by-products in the production of various chemical substances, such as preservatives such as phenol chloride, etc., and are mixed into products and sold to the market. In some cases, it is released directly as waste. In the case of landfilling of industrial waste, dioxin as an impurity may leak due to flooding and contaminate groundwater, etc.The most important source is the incineration of municipal solid waste, which accounts for the majority of the amount generated. It is generated by a thermochemical reaction such as In other words, with the development of modern chemical industry, the use of organic chlorine compounds has increased worldwide, and these substances have been disposed of due to aging, etc. and disposed of as general waste such as municipal waste or separated as industrial waste and incinerated. At that time, generation of dioxins has become a problem. In particular, in Japan, most of the general waste is incinerated due to the small land area and few places for landfill disposal.
According to a 1994 survey, the number of municipal solid waste incinerators in Japan was close to 2,000, and the amount of incinerated waste was 3,7 per year.
Million tons is considerably higher than other countries, and is increasing year by year. ), It has been reported that 78-88% of the generation of dioxins is due to the incineration of municipal solid waste. Also, incineration of waste oil, waste plastic, sludge, etc. is widely performed, but incineration is the most important source of dioxins including these. In addition, medical waste is usually incinerated in small incineration facilities provided in medical facilities, but operation control is not sufficiently performed, and the amount of dioxins generated is limited to urban areas. It is considered to be at the same level as solid waste.

Next, various research reports have been made on the mechanism of the generation of dioxins by a thermochemical reaction such as the incineration of municipal solid waste, but at present, using the chemical structural formula (Chemical Formula 1) shown below. As summarized in the `` Schematic diagram of dioxin formation mechanism from organic matter by incineration of garbage '', small molecule compounds such as phenol chloride and benzene chloride generated by decomposition of organic matter are formed by condensation at high temperature. It is generally considered that ash produced by incineration is synthesized from carbon skeleton and chlorine under the catalytic action of the surface of ash (de novo synthesis).

[0010]

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In order to suppress the emission of dioxins generated during incineration of waste as described above, the first priority is to reduce the amount of waste to be incinerated. To control emissions, complete combustion including combustion management minimizes production from furnaces (boilers).
Furthermore, development is being promoted from the viewpoint that it is important to take measures in an exhaust gas treatment system using a combination of various technologies.

Of these, to achieve complete combustion, a high combustion gas temperature, a sufficient gas residence time, sufficient gas agitation in the furnace and mixing with secondary air are necessary. Automatic combustion control combining body technology and fuzzy control has been put to practical use. However, since it is necessary to maintain a high combustion gas temperature, running costs and maintenance costs are high, and the inner wall of the incinerator is rapidly deteriorated. Therefore, it is necessary to use a refractory material having better high temperature heat resistance. In addition, automatic combustion control, which combines furnace body technology and fuzzy control, cannot be easily handled in existing incinerators or small-scale incineration facilities that do not require them, and there is a problem that repair costs are high and there is a problem of about 2,000. It is practically difficult to install such equipment in municipal solid waste incinerators and other incinerators near the city.

In the exhaust gas treatment system, the treatment temperature has been lowered, the dust removal performance has been improved, and the adsorption effect has been utilized. The bag filter has been lowered, the powdered activated carbon has been sprayed, the activated carbon-based adsorption tower has been removed. Catalyst (titanium-vanadium,
A technique for decomposing and removing dioxins by using a noble metal (based on a noble metal) and further reducing the use of chemical inhibitors (such as triethanolamine and hydrogen peroxide) have been developed. However, the method of lowering the temperature of the bag filter, spraying powdered activated carbon, and removing it with an activated carbon-based adsorption tower cannot suppress the generation of dioxins, and activated carbon cannot selectively adsorb dioxins, and other than dioxins. Since other components in the exhaust gas are also adsorbed, their adsorption life is short, and they need to be replaced frequently.In addition, to dispose of the activated carbon that has adsorbed the recovered dioxins, it must be separately decomposed and made harmless. Is required, the number of steps required to reach the final processing stage increases, and the cost increases. Also, the method of decomposing and removing dioxins with a catalyst (titanium / vanadium-based, noble metal-based) cannot suppress the production of dioxins. For example, activated carbon fibers may contain several angstrom particles of gold (precious metal) or iron oxide particles. It has been reported that dioxins can be decomposed when used as an exhaust gas filter in which (e) is uniformly dispersed (supported). However, the use of a noble metal catalyst such as gold inevitably increases costs. However, existing incinerators or small-scale incineration facilities cannot easily cope with them, and there is a problem that repair costs are high.
It is practically difficult to install such facilities in municipal solid waste incinerators and other incinerators near 000, and there are also issues that need to be cleared for practical use, such as determination of durability as a future task. However, much time is required for practical use. Furthermore, the reduction technology using chemical inhibitors (triethanolamine, hydrogen peroxide solution, etc.) only achieves reduction of dioxin generation,
It is not possible to sufficiently suppress the generation of such chemicals, and chemical inhibitors such as triethanolamine and aqueous hydrogen peroxide are relatively expensive, and they require considerable care in their handling and storage. A person with sufficient knowledge of the substance must be available, and it is not possible to deploy such equipment and specialists in incineration facilities, including municipal incinerators and other small incineration facilities, which are close to 2,000. In addition to the practical difficulties, it is also practically difficult to supply the chemical inhibitors needed to treat 37 million tonnes of waste annually in the country.

[0014] Further, as an inhibitor of hydrogen chloride, conventionally,
Although calcite (CaCO ₃ ) is used, in the case of incinerators, the reaction efficiency is poor in the primary combustion chamber, so it is usually used in a process after the secondary combustion chamber, and the generation of dioxin is suppressed. Couldn't be a solution.

On the other hand, in general, dolomite (dolomite; a complex carbonate of calcium and magnesium CaMg (CO ₃ ))
₂ or a rock mainly composed of this) is a soil conditioner for agriculture, etc. (magnesium lime fertilizer) through a crushing process after mining work
In addition to being used as dolomite plaster by calcining, it is currently used as a raw material for sheet glass and as a dolomite clinker for lining steelmaking furnaces and hearth stamps. In addition, dolomite ore and calcined dolomite are produced and processed at low cost in Japan and overseas, and can be said to have sufficient supply capacity.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composite material having excellent antibacterial properties and capable of suppressing the generation of dioxins when incinerated, and a method of forming the same. Things.

Another object of the present invention is to provide an antibacterial agent which can be stably obtained in large quantities at a low cost, has an antibacterial property, and suppresses the generation of dioxins when incinerated. And a molding method for the same.

[0018]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on a substance having antibacterial properties and capable of suppressing the generation of dioxins when incinerated. Calcined dolomite suppresses the generation of dioxins, is also extremely useful for decomposing the dioxins generated, and can also exhibit antibacterial properties semipermanently, and has heat resistance and light resistance. Because it is not degraded in the manufacturing stage when added to plastics and causes yellowing of the resin and does not adversely affect the molding process, its safety has also been confirmed (it is a food additive), By adding the calcined dolomite to the base material without using a carrier or the like, a composite material can be formed, so that it can be used for many products, and even if the obtained composite material has sufficient resistance, And the generation of dioxins when the composite material is incinerated (along with other municipal waste), and the dioxins in the exhaust gas and its incinerated ash can be extremely low. In addition, they have found that the present invention is more effective and useful, and have completed the present invention. That is, the object of the present invention is achieved by an antibacterial composite material capable of suppressing the generation of dioxins during incineration described in the following (1) to (9) and a molding method thereof.

(1) A composite material characterized by containing calcined dolomite and capable of suppressing the generation of dioxins during incineration.

(2) The particle size of the calcined dolomite is 1
The composite material according to the above (1), wherein the thickness is from 10 to 10 μm.

(3) The composite material according to the above (1) or (2), which is a film or a sheet.

(4) The composite material according to any one of the above (1) to (3), which is formed in a multilayer.

(5) The above (4), wherein the calcined dolomite is contained in at least one surface portion.
A composite material according to claim 1.

(6) The content of the calcined dolomite is
3 based on the total weight of the component containing calcined dolomite
(1) to (10) above,
The composite material according to any one of (5).

(7) The content of calcined dolomite in the component containing calcined dolomite is 3 to 5 g / m ^2.
The composite material according to any one of the above (1) to (5), wherein

(8) A composite material having antibacterial properties characterized by being molded using a compounded material obtained by mixing calcined dolomite with a base material, and capable of suppressing the generation of dioxins during incineration. Forming method.

(9) The amount of the calcined dolomite is
The method for forming a composite material according to the above (8), wherein the amount is 3 to 20% by weight based on the total weight of the compounded material obtained by mixing the calcined dolomite.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The composite material of the present invention is characterized by containing calcined dolomite. This has antibacterial properties and can suppress the generation of dioxins during incineration. That is, it can be applied to many molded products requiring antibacterial properties, and is extremely excellent in versatility, so that it can be applied to all existing molded products. In addition, decompose and adsorb dioxins generated when incinerating waste containing vinyl chloride, which is a problem at present, and chlorine compounds such as hydrogen chloride, which is one of the raw materials, and chlorine-based gas. Therefore, the generation of dioxins derived from the composite material of the present invention can be suppressed, and the generated dioxins can be sufficiently decomposed.

Here, the dolomite refers to CaMg (CO ₃ ) _2, a composite carbonate of calcium and magnesium, which is also called dolomite or dolomite, or a rock mainly composed of CaMg (CO ₃ ) ₂ . When this dolomite is heated, 70
At 0 to 800 ° C., the MgCO _{3 component} decomposes to release CO _2, and becomes a calcined product of calcium carbonate (CaCO ₃ ) and magnesium oxide (MgO) (hereinafter also simply referred to as calcined dolomite A). Thus, CaCO ₃ is decomposed to release CO ₂ , and has a property of being a calcined product of calcium oxide (CaO) and magnesium oxide (MgO) (hereinafter, also simply referred to as calcined dolomite B). Therefore, the above-mentioned calcined dolomite is a calcined dolomite A containing magnesium oxide and calcium carbonate as main components,
It shall contain at least one of calcined dolomite B containing magnesium oxide and calcium oxide as main components.

First, the composite material of the present invention may be any one which is composited by adding calcined dolomite to a base material.

The form of the composite material of the present invention is not limited at all, and may be a coated product, a rod, a tube, a foam,
It can take any form such as a plate (sheet), a molded product, a film, etc., and may be one in which different kinds of raw materials are formed in a multilayer (laminated), and in this case, it is fired into at least one layer. It is sufficient that dolomite is contained, but preferably, a layer required to have antibacterial properties, for example,
When applied to packaging materials containing perishable perishable foods, which are strongly required to have antibacterial properties, it is particularly useful to increase the antibacterial performance by containing baked dolomite on the inner surface layer for perishable foods. In addition, a layer having a high risk of generating dioxins derived from the composite material of the present invention upon incineration, for example, a layer formed and processed using a chlorine-containing aromatic resin essential for the production of dioxins as a base material. The use of calcined dolomite is particularly useful in suppressing the generation of dioxins during incineration. Furthermore, in any use mode, antibacterial properties can be exhibited, and the generation mechanism of dioxins has not been sufficiently elucidated, and when incinerated together with other general waste, chlorine-containing aromatic resin is used. It is possible that even if it is not incinerated in any environment, it is possible to suppress the generation of dioxins, even if it does not have a dolomite. It is preferable.

The particle size of the calcined dolomite used in the composite material of the present invention is not particularly limited, and the particle size of the optimal particle size may be appropriately selected and used according to the form of the composite material. , 1 to 15 μm, preferably 1 to 1
0 μm, more preferably 1 to 5 μm. If the particle size of the calcined dolomite is less than 1 μm, the cost required for pulverization is high, and dust is easily generated during handling, which is not preferable. If the particle size of the calcined dolomite exceeds 15 μm, the cost of adjusting the particle size increases, and particularly in the case of a film form, it is not preferable because it may hinder thinning.

The content of the calcined dolomite is sufficient to allow the composite material to sufficiently exhibit antibacterial properties and to effectively suppress the generation of dioxins derived from the composite material during incineration. It is necessary. For this purpose, the content of the calcined dolomite is 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 3 to 10% by weight, based on the total weight of the component containing the calcined dolomite. Alternatively, the content of the calcined dolomite in the component containing the calcined dolomite is 1 to 7.5 g /
m ² , preferably 3 to 7.5 g / m ² , more preferably 3 to 7.5 g / m ² .
It may be prepared to be と 5 g / m ² . When the content of the calcined dolomite is less than 3% by weight or less than 1 g / m ² , the composite material cannot exhibit sufficient antibacterial properties, or dioxins derived from the composite material at the time of incineration. It is difficult to effectively suppress the occurrence of phenomena. On the other hand, when the content exceeds 20% by weight or 7.
When it exceeds 5 g / m ² , it is possible to sufficiently exhibit antibacterial properties in the composite material and to effectively suppress the generation of dioxins derived from the composite material during incineration.
Depending on the form of the composite material, its mechanical strength and moldability are reduced, and it may not be possible to finish in a desired form, or properties such as strength and stretchability required for a product may be insufficient.

The antibacterial composite material of the present invention desirably functions effectively as a dioxin generation inhibitor. That is, as a dioxin generation suppressing material, by putting the composite material of the present invention into waste and incinerating it, an amount sufficient to sufficiently suppress the generation of dioxins in all incinerated materials is contained. Is particularly preferred. From this viewpoint, the content of the calcined dolomite is 3 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the composite material.
More preferably 3 to 10% by weight, particularly preferably 3 to 5% by weight.
% By weight. When the content of the calcined dolomite is less than 3% by weight, it is not enough to act as a dioxin generation inhibitor, while when it exceeds 20% by weight, it can effectively act as a dioxin generation inhibitor. Depending on the form of the composite material, the mechanical strength and moldability may be reduced, and the composite may not be finished in a desired form, or the properties such as strength and stretchability required for the product may be insufficient. In order to function effectively as a dioxin generation inhibitor, the composite material satisfying the content of the calcined dolomite is required to be 5 parts by weight or more, preferably 10 parts by weight, based on 100 parts by weight of general waste such as municipal waste. As described above, it is more preferable that 15 parts by weight or more be mixed. However, general waste such as municipal waste 10
This is a value when an average of about 5 tons of an organic chlorine compound is mixed per 0 tons, and it is more preferable to conduct a small-scale experiment in advance to determine the necessary amount. This is due to the fact that, in recent years, the separation and collection of garbage has been promoted due to a partial charge, etc. This is because those that contribute can be added to the product in advance.

The properties of the calcined dolomite are shown in Table 1 below.
As shown in Tables 1 and 2, it can be seen that they have extremely high antibacterial properties and excellent dioxin generation inhibitory ability.

[0036]

[Table 1]

[0037]

[Table 2]

The antibacterial rate (%) in the above table was measured for both Escherichia coli and Staphylococcus by the following shaking method, because the powdered form of calcined dolomite was targeted.

Shaking method: A method for evaluating antibacterial activity applicable to powdered processed products, wherein a sample (inorganic antibacterial / fungicide and plastic in powder) is prepared in a phosphate buffer.
And the test bacteria are allowed to coexist, and the number of surviving bacteria is measured after shaking for a certain period of time. That is, a method in which the sample dispersed in the aqueous solution and the test bacteria are forcibly brought into contact with each other by shaking to confirm the effect.

The concentration of dioxins (toxic equivalent concentration) in the above table was measured using a general-purpose small and medium-sized garbage incinerator (manufactured by Youse Electric Co., Ltd.) in an amount of 100 parts by weight (10 parts by weight) of municipal solid waste.
0 kg) (including organic chloride compounds 5 such as vinyl chloride)
kg) and 10 parts by weight of calcined dolomite are mixed in advance and then charged into the incinerator, incinerated at an in-furnace temperature of 650 ° C., and exhaust gas is collected at appropriate intervals from the start of combustion. Dioxins in exhaust gas (PCDDs, P
The concentration (toxic equivalent concentration) of CDFs and their sum was measured. Further, after the incinerated material was completely incinerated, the concentration (toxic equivalent concentration) of dioxins (PCDDs, PCDFs and their sum) was also measured for the incineration ash in the furnace. The concentration of dioxins (equivalent toxic concentration) in these exhaust gas and ash (incinerated ash) can be obtained by bringing the sample gas and ash sampled to the Tottori Prefectural Insurance Corporation and collecting dioxin in the exhaust gas and ash. Concentration (toxic equivalent concentration)
Is the result of analysis by the Hiroshima Environmental Insurance Association.

The base material for the composite material of the present invention is not particularly limited, and may be any kind of polymer, such as resin, rubber, or pulp, preferably a flammable polymer. It can be a raw material. Further, it can be combined with a nonflammable base material (base material) such as a metal material such as aluminum or an inorganic material such as glass. That is, as the composite material of the present invention, primary processed products such as plastics, rubber, paper, and the like obtained by blending the base material with calcined dolomite and other additives (sub-materials) and molding the same; There is a processed product, and in such a composite material, the function and effect of the present invention can be sufficiently exerted.

In particular, molded plastic products (composite materials) using versatile resins as base materials can be applied to a wide range of fields, and have the advantage of being molded into any form.

As such a base material, for example, polyethylene, polypropylene, polystyrene, poly-p-
Xylylene, polyvinyl acetate, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, fluoroplastic, polyacrylonitrile, polyvinyl ether, polyvinyl ketone, polyether,
Polycarbonate, thermoplastic polyester, polyamide (nylons), diene plastic, polyurethane plastic, heat-resistant polymer (aromatic polyamide, polyphenylene, polyxylylene, polyphenylene oxide, polysulfone, aromatic heterocyclic polymer, ladder polymer, etc.) Thermoplastic resin (thermoplastic), phenolic resin, furan resin, xylene / formaldehyde resin, ketone / formaldehyde resin, urea resin, melamine resin, aniline resin, alkyd resin, unsaturated polyester resin, epoxy resin, triallyl cyanurate Resin, thermosetting resin (thermosetting plastic) such as formaldehyde resin of tris (2-hydroxyethyl) isocyanurate, acrolein resin, triazine resin, etc., natural Beam based plastic, cellulosic plastics, protein based plastics, natural plastic such as plastic, for example from starch, pulp, natural rubber, synthetic rubber and the like, and examples include poly tetrachlorethylene, polydimethylsiloxane (silicone),
Butyl rubber, polypropylene, polyethylene, hydrogenated polybutadiene, polybutadiene / styrene (85/1
5, 75/25, 60/40), polyisobutylene, polybutadiene, polybutyl acrylate, polyethyl hexyl methacrylate, polyethoxy methyl methacrylate, polypropyl acrylate, polystyrene, polysulfide (thiochol rubber), polystyrene divinyl benzene, polymethyl methacrylate, neoprene, Polybutadiene / acrylonitrile (75/2
5), polyethyl acrylate, polymethyl acrylate, polyurethane, ethyl cellulose, polyvinyl chloride, polyethylene glycol terephthalate (tetron), cellulose diacetate, cellulose dinitrate, polymethylenoxide (delulin), polyvinyl denchloride (salan), poly Examples thereof include methacrylonitrile and polyacrylonitrile. In particular,
Suitable for film and sheet materials include, for example, acrylonitrile-butadiene-styrene (AB
S); acrylonitrile-methyl acrylate copolymer (modified rubber); cellophane (regenerated cellulose); celluloses such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose triacetate; ethylene-tetrafluoroethylene copolymer Polymer (E
TFE), fluoroplastics such as tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychloroethylene-trifluoroethylene copolymer (PCTFE), polytetrafluoroethylene (PTFE), and polyvinyl fluoride (PVF) An ionomer;
Polyamides such as nylon-6, nylon-6,6, nylon-11 and nylon-12; polybutylene; polycarbonate; polyester (polyethylene terephthalate); low-density polyethylene (LDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDP).
E), polyethylene such as ultra high molecular weight polyethylene (UHMWPE); ethylene copolymer such as vinyl acetate and methyl acrylate; polyimide; polymethyl methacrylate (PMMA); polypropylene (extruded product, biaxially stretched product, etc.); Polystyrene (orientation grade, foam, etc.); Sulfone polymers such as polystyrene and polyether sulfone; Polyurethanelastomer; Polyvinyl alcohol; Polyvinyl chloride (Non-plasticized grade, plasticized grade, etc.); Vinyl chloride-acetate copolymer (Non-plasticized grade, plasticized grade, etc.). In particular, the film material is preferably a non-water-absorbing resin. For example, polyethylene, a polyolefin resin such as polypropylene, a polyester resin, a polystyrene resin, a nylon (polyamide) resin, an ethylene vinyl alcohol copolymer, Examples thereof include polyvinyl chloride resins. Furthermore, by laminating the base material on water-absorbent non-woven fabric and aluminum foil, the characteristics of each material (water absorption, water and oil resistance,
Since heat and light reflectivity and gas barrier properties can be further utilized, it can be used in many fields.

In the composite material of the present invention, if necessary, various conventionally known additives such as a foaming agent, a lubricant, a coloring agent, a pigment, a heat stabilizer, an ultraviolet stabilizer (ultraviolet absorber), Antioxidants (antioxidants), plasticizers, curing agents, catalysts, fillers, reinforcing materials, extenders, antistatic agents, flame retardants, antibacterial and antifungal agents, etc., fully exhibit their performance (functions). It may be appropriately contained within a possible range.

Next, the method for forming an antibacterial composite material capable of suppressing the generation of dioxins during incineration according to the present invention is not particularly limited. It is possible to apply a compounded material obtained by compounding the calcined dolomite, as well as the various additives described above, as necessary, to the resin or pulp of the base material as exemplified above. It is used for forming. Such a blending operation should be appropriately selected according to the form of the target composite material. (1) The base material, the calcined dolomite and other additives (sub-materials) are blended in appropriate amounts, and Liquid mixing using an appropriate solvent as necessary, and further impregnation, drying, pulverization, and granulation operations as needed, or by performing two or more operations sequentially, paste, solution, prepreg, A compound material in the form of resin-impregnated coated paper, premix, powder, pellet or the like may be formed, or (2) a base material, calcined dolomite and other additives (sub-materials) are compounded in appropriate amounts,
If necessary, a solid (powder) is mixed and kneaded using an appropriate solvent, and then kneaded, and further, if necessary, pulverized or granulated to form a kneaded material, powder, pellet, or other compounded material. good. Further, the subsequent forming / processing method should also be appropriately selected according to the form of the target composite material, and a forming method suitable for various compounding materials, for example, slash forming (paste), dip forming (Paste), casting (solution), foaming / foaming (solution, pellet),
Lamination molding (prepreg, resin-impregnated coated paper, sheet; one of the forms of compounded material obtained by further calendering or extruding a compounded material as a compounded material), powder molding (powder), compression molding (premix) , Powder, pellets), transfer molding (powder, pellets), injection molding (pellet), calendering (kneaded material), extrusion molding (sometimes blow-molded) (kneaded material), vacuum forming (sheet) Just do it. Further, such molded articles can be processed by appropriate processing. For example, conventionally known various molding methods can be applied, such as improvement of printability, crosslinking of a polymer by radiation, coating of a thin metal film on the surface of a molded article using vacuum evaporation, and the like.

[0046]

The present invention will now be described more specifically with reference to examples.

Example 1 As a base material, 100 parts by weight of polyethylene and a particle size of 5
Addition and mixing of 3 parts by weight of calcined dolomite having a thickness of 10 to 10 μm (used at 1000 to 1100 ° C.) are used to prepare a composite film of the present invention having a thickness of 20 to 30 μm by the T-die method. did.

Comparative Example 1 A general-purpose film having a thickness of 20 to 30 μm was prepared in the same manner as in Example 1 except that the calcined dolomite was not used.

The antibacterial properties (antibacterial properties against Escherichia coli and Pseudomonas aeruginosa and the freshness retention period) of the obtained composite film and general-purpose film were measured, and the results are shown in Tables 3 to 5 below.

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

The antibacterial rates in the above table were measured for both Escherichia coli and Pseudomonas aeruginosa by the pressurization method shown below, since the antibacterial rates were various processed plastic products (having a certain shape).

Pressurization method: a method for evaluating antibacterial activity that can be suitably applied to processed products of a fixed shape (many of various processed products of plastic correspond to this), and has a predetermined size (for example, 25 × 25 mm). ) Is a sample of plastic (here, a plastic film) in which a test bacterium is suspended in a 1% peptone aqueous solution in an appropriate amount (for example, 0.0
(Inoculate the number of initial bacteria shown in each table per sample). Next, a sterilized polyethylene film (30 × 30 mm) is brought into close contact with an appropriate temperature (for example,
0 ° C) and humidity (humidified state), and after 24 hours, an appropriate amount of S
The bacterial solution is washed out with a CDLP medium (for example, 10 ml), appropriately diluted, and then subjected to a plate pour method (SCDLP agar medium culture 3).
(2 ° C. for 6 hours).

The freshness in the above table is obtained by completely wrapping a fresh fish (in this case, using a turbo) in a composite film or a general-purpose film immediately obtained by immediately killing a fish (an instantly killed fish; a specimen). And a temperature of 10 ° C. or less (the temperature at the center is
At a temperature not exceeding 100 ° C.), and the test specimen is removed every 2 days (48 hours) by volatile basic nitrogen (VBN).
rogen) method. As a result of the analysis, a state in which 5 to 15 mg of VBN was contained per 100 g of muscle was evaluated as fresh, and the following 15 to 30 mg, 30 to 50 mg, and 50 mg were evaluated.
The above are evaluated as normal, initial putrefaction, and putrefaction, respectively, if fresh or normal, it is judged that they can be used for food, and if initial or putrefactive, they are putrid and cannot be used for food. It was determined.

Next, 100 parts by weight (100 kg) of municipal solid waste (containing 5 kg of an organic chlorine compound such as vinyl chloride) in a general-purpose general-purpose small / medium-sized garbage incinerator (manufactured by Youse Electric Co., Ltd.) Then, 10 parts by weight of the composite material in the form of a film obtained in the present example was mixed in advance for each lot, and then charged into the incinerator, incinerated at an in-furnace temperature of 650 ° C. Exhaust gas is collected at intervals, and dioxins (PCDDs, PCDFs)
s and their sum) (toxic equivalent concentration). After the incinerated material is completely incinerated, the incineration ash in the furnace also contains dioxins (PCDDs, PCDDs).
DFs and their sum) (toxic equivalent concentration) were measured. The results of each measurement (average value of each lot) are shown in Table 6 below. The concentration of dioxins (equivalent toxic concentration) in exhaust gas and ash (incinerated ash) was determined by bringing the sample gas and ash sampled to the Tottori Insurance Corporation, and dioxin in the exhaust gas and ash. Concentrations (equivalent concentrations of toxic substances) are the results of analysis by the Hiroshima Environmental Insurance Association.

[0057]

[Table 6]

[0058]

The composite material of the present invention can be formed into a fresh food container or bag, or formed into a drip sheet or the like to be put in a back product such as fish and shellfish, and used in a short time to have an antibacterial effect. An effect can be obtained, and a composite material capable of maintaining long-lasting freshness, particularly in the form of a composite film or sheet, can be obtained extremely easily and at low cost. Therefore, sufficient antibacterial properties can be exhibited against bacteria such as mutants of Escherichia coli such as O-157. Further, generation of dioxins can be effectively suppressed by incineration. In particular, the generation of dioxins can be extremely effectively suppressed at a sufficiently low temperature without incineration at a high temperature (800 ° C. or higher) necessary for decomposition of dioxins. Therefore, even if it is discarded together with general waste, it is derived from the composite material of the present invention.
The generation of dioxins can be suppressed, and furthermore, depending on the content of the composite material of the present invention, the generation of dioxins can be suppressed from the entire incinerated material. It has the advantage that it can be reduced to In particular, from the viewpoint of product liability, when incinerated as general waste, dioxins are generated, so collection is desired (furthermore, collection duty is required).
By using such a product, it is possible to efficiently incinerate it after recovery, which is useful.

As for the molding method, a conventional plastic or paper manufacturing technique can be applied, and the addition and mixing operation of calcined dolomite can be performed by using other additives (compounding agents). It is only necessary to add the auxiliary material when adding it to the base material, and this has the advantage that extremely high value-added products can be manufactured using existing manufacturing equipment as it is.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA01 AB21 AD02 AD06 AF52 AH19 BC01 4F100 AC10A AK04 AT00B BA01 BA02 DE01A JA20A JC00 YY00A 4H011 AA02 AA03 BA01 BB20 BC19 DA07 DC05 DG16 DH02 4J002 AA001 AB01 AC01 AB01 BD121 BF021 BG021 BG101 BQ001 CC011 CC031 CC121 CC131 CD001 CE001 CF001 CG001 CH001 CK021 CL001 CN031 DE206 FA086 GD00

Claims (9)

[Claims] 1. An antibacterial composite material containing calcined dolomite, which can suppress the generation of dioxins during incineration. 2. The calcined dolomite has a particle size of 1 to 10.
The composite material according to claim 1, wherein the composite material has a thickness of μm. 3. The composite material according to claim 1, which is a film or a sheet. 4. The composite material according to claim 1, wherein the composite material is formed in a multilayer. 5. The composite material according to claim 4, wherein at least one surface layer contains calcined dolomite. 6. The content of the calcined dolomite is 3 to 20 with respect to the total weight of the component containing the calcined dolomite.
The composite material according to any one of claims 1 to 5, wherein the composite material is% by weight. 7. The composite material according to claim 1, wherein the content of the calcined dolomite in the component containing the calcined dolomite is 3 to 5 g / m ² . 8. A method for forming an antibacterial composite material capable of suppressing the generation of dioxins during incineration, characterized by forming and processing a compounded material obtained by mixing fired dolomite with a base material. 9. The molding of a composite material according to claim 8, wherein the amount of the calcined dolomite is 3 to 20% by weight based on the total weight of the compounded material obtained by blending the calcined dolomite. Processing method.