JP3504802B2 - Organic polymer molded article containing pyroelectric substance - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic polymer molded article containing a pyroelectric substance and inorganic particles carrying metal ions. More specifically, the present invention relates to a highly functional organic polymer molded article having a freshness-retaining action for foods and fresh flowers, a bactericidal action, etc., and the organic polymer molded article of the present invention has the above-mentioned characteristics. By utilizing it, it can be extremely effectively used as a packaging material for foods, fresh flowers, various containers for foods, and the like.

[0002]

BACKGROUND ART Tourmaline represented by tourmaline is widely known to exhibit pyroelectricity (also referred to as pyroelectricity or pyroelectricity). And pyroelectric minerals such as tourmaline,
Due to the stimulating effect on the "tender point" (so-called "pot") based on its unique property of pyroelectricity, it improves the physical symptoms such as the promotion of blood circulation, the promotion of metabolism, and the improvement effect of independence neuropathy and the promotion of health. It is known to have a function. Therefore, for the purpose of promoting blood circulation, promoting metabolism, improving other physical symptoms and promoting health, organic polymer molded products such as clothes and bedding that are often worn on or in contact with the body Various proposals have been made so far to include pyroelectric minerals such as tourmaline (JP-A-2-169764 and JP-A-6-1848).
08, JP-A-6-228808 and Japanese Utility Model Laid-Open No. 5
22579 publication).

On the other hand, in recent years, there has been an increasing demand for packaging materials and containers capable of maintaining the freshness of foods, and research and development of plastic-based food packaging materials and containers with freshness-retaining properties have been conducted. It is being actively conducted. However, tourmaline typified by tourmaline, pyroelectric minerals such as tourmaline are extremely expensive, and thus are conventionally used for food packaging materials and containers, which are often discarded as consumables. Therefore, little research has been conducted on the influence of pyroelectric substances on the freshness of foods.

[0004]

SUMMARY OF THE INVENTION Under the above circumstances, the present inventors have
Research has been conducted for the purpose of developing materials that can maintain the freshness of foods. Regarding pyroelectric substances that have been used in textile products for the purpose of promoting health, we have conducted various studies on their functions and actions from the viewpoint completely different from conventional applications, and as a part of that, we have developed packaging for food products. We examined the use for timber and containers. As a result, the pyroelectric substance alone does not contribute much to maintaining the freshness of the food, but if a predetermined metal ion is used in combination with the pyroelectric substance, the freshness of the food can be maintained for a long time even if a small amount of the pyroelectric substance is used. It was found that it can be held well. As a result of further studies based on such findings, it was found that the combined use of pyroelectric substances and metal ions preserves the freshness of not only food but also fresh flowers for a long period of time. . Therefore, based on these findings, plastic films and sheets often used for packaging foods and fresh flowers, containing inorganic particles holding metal ions with pyroelectric substances in plastic containers and the like. , Packaging foods, fresh flowers, etc. using these molded products, found that the freshness of the product was kept good over a long period of time, and found that it could be kept for a long time, and based on those findings The present invention has been completed.

Therefore, the present invention is an organic polymer molded article characterized by containing inorganic particles retaining metal ions together with a pyroelectric substance.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As described above, the organic polymer molded article of the present invention,
In addition to the pyroelectric substance, it contains inorganic particles retaining metal ions (hereinafter referred to as “metal ion retaining inorganic particles”). In the organic polymer molded article of the present invention, even if the pyroelectric substance and the metal ion-retaining inorganic particles are added to the organic polymer constituting the molded article, or the surface of the organic polymer molded article is pyroelectrically charged. The substance and / or the metal ion-holding inorganic particles may be attached so as not to fall off. Therefore, the term "organic polymer molded article containing inorganic particles retaining metal ions (metal ion retaining inorganic particles) together with the pyroelectric substance" in the present invention means a pyroelectric substance and a metal ion retaining inorganic material. Both particles that are added and mixed in the organic polymer that constitutes the molded article, and those that are adhered to the surface so that the pyroelectric substance and the metal ion-retaining inorganic particles do not fall out of the molded article. Include.

In the present invention, any substance that exhibits pyroelectricity (pyroelectricity or pyroelectricity) can be used as the "pyroelectric substance". Representative examples of the pyroelectric material that can be used in the present invention include pyroelectric minerals such as tourmaline and sycamore, and tourmaline, which is one of tourmaline, is preferably used. When the pyroelectric substance is used in the form of fine particles or fine powder, its surface area is increased and its pyroelectric function is sufficiently exerted, and the effect of maintaining the freshness of foods and fresh flowers is further enhanced, which is preferable. . Moreover, the uniform dispersibility of the pyroelectric substance in the organic polymer molded product, the molding processability when the molded product is manufactured using the organic polymer material containing the pyroelectric substance, the damage prevention of the molded product, In order to prevent the occurrence of spots, surface roughness, etc., the strength of the molded product to be obtained, and when the pyroelectric substance is attached to the molded product, the pyroelectric substance should be finely divided from the viewpoints of its adhesion strength and difficulty in falling off. It is preferably used in the form of powder or fine particles. From the above-mentioned point, in general, the average particle diameter of the pyroelectric substance is preferably 5 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less.

It is important that the organic polymer molded article of the present invention contains the metal ion-retaining inorganic particles together with the pyroelectric substance. The metal ion-supporting inorganic particles may be contained in the molded product or may be attached to the surface of the molded product so as not to fall off. Specific examples of the metal ions held by the inorganic particles include metal ions selected from silver, zinc, copper, gold, platinum, iron, nickel, cobalt, lead, chromium and tin. The above-mentioned metal ions may be held alone in the inorganic particles, or two or more kinds may be held in the inorganic particles. In particular, when the organic polymer molded article of the present invention is a packaging material or container for food, or a molded article used for their production (such as a sheet or film), from the viewpoint of safety and hygiene, silver, It is preferable to use one or more kinds of ions of a metal selected from zinc, copper, gold, platinum and iron, which are held in inorganic particles.

The inorganic particles for holding the metal ions are inorganic particles which do not show deterioration of the organic polymer molded product, and are safe when the organic polymer molded product is used for foods. Any excellent inorganic particles can be used. Among them, it is preferable to use inorganic particles having an ion exchange ability and a metal ion adsorption ability and a high metal ion retention ability. Representative examples of preferred inorganic particles include inorganic particles having an ion exchange capacity such as zeolite, zirconium phosphate, and calcium phosphate, and among them, zeolite is more preferred. When zeolite is used as the inorganic particles, if it is sufficiently dried by heating to reduce the water content, the molding processability at the time of molding by adding the zeolite holding metal ions to the organic polymer becomes good. Moreover, it is preferable because it is possible to prevent the strength of the obtained molded product from decreasing.

The average particle size of the inorganic particles for holding the metal ions is preferably 3 μm or less.
It is preferably at most μm, more preferably at most 1 μm. When the average particle size of the inorganic particles is larger than 3 μm, the molding process tends to become defective when added to the organic polymer, and the strength of the resulting molded article tends to be low, and the surface tends to be roughened or roughened. On the other hand, when the average particle size of the inorganic particles is too small (usually 0.1 μm or less),
The particles tend to undergo secondary agglomeration, resulting in poor molding processability, deterioration of the strength of the molded product, and bumps and surface roughness.

The metal ion-retaining inorganic particles preferably have a high concentration of metal ions. For example, in the case where the inorganic particles are zeolite having an ion exchange capacity, 90% or more of the ion exchange capacity is metal. It is preferably ion-exchanged with ions, and when the metal ions are retained by the physical adsorption capacity of the inorganic particles, the metal ions are adsorbed at 90% or more of the saturation. Good.

The metal ion-retaining inorganic particles are usually obtained by impregnating the inorganic particles with an aqueous solution containing the above-mentioned silver, zinc, and other metal ions, and then drying. There is no limitation, and any inorganic particles that retain metal ions at a high concentration can be used.

In the present invention, as described above, even if the pyroelectric substance and the metal ion-retaining inorganic particles are contained in the molded product, or the surface of the molded product is not removed by using a binder such as an adhesive resin. You may make it adhere like this. In particular,
When the molded product intended to contain the pyroelectric substance and / or the metal ion-retaining inorganic particles is a thin film or the like,
Since it may be difficult to incorporate the pyroelectric substance and / or the metal ion-retaining inorganic particles into the thin film, in that case, a method of adhering to the surface of the film by using a binder may be used. Good.

However, the method of adhering the pyroelectric substance and the metal ion-retaining inorganic particles to the surface of the molded article by using the binder is as a binder when the molded article is used for food or the like. It is necessary to select a nontoxic and safe one, and it is necessary to firmly hold the pyroelectric substance or metal ion-holding inorganic particles attached to the surface of the molded product with a binder so that they do not fall off. In addition, a separate step of later attaching the pyroelectric substance or the metal ion-retaining inorganic particles to the surface of the molded article by using a binder is required, so that the pyroelectric substance is added to the organic polymer material. It is desirable to add the metal ion-retaining inorganic particles and perform molding to produce an organic polymer molded product containing them.

In the organic polymer molded article of the present invention, for example, the pyroelectric substance and the metal ion-retaining inorganic particles may be uniformly dispersed and contained in the entire molded article, or in the central portion or the surface portion of the molded article. The content (distribution) of the pyroelectric substance and / or the metal ion-retaining inorganic particles may be different from each other (for example, the pyroelectric substance and the metal ion-retaining inorganic particles are provided only on one of the inner side and the surface side of the molded article). Or when the contents of those substances are made different between the inside and the surface side), the pyroelectric substance and the metal ion-retaining inorganic particles may be distributed in layers in the molded article. (For example, when a pyroelectric substance is contained on the surface side of a molded product and metal ion-retaining inorganic particles are contained on the inside, a metal ion retaining inorganic particle is contained on the surface side of the molded product and a pyroelectric substance is contained on the inside. If pyroelectric A two-layer structure of an organic polymer layer containing and an organic polymer layer containing metal ion-retaining inorganic particles), or a pyroelectric substance and metal ion-retaining inorganic particles are randomly contained in a molded article. You may keep it. In short, when the molded product of the organic polymer is viewed as a whole, it is sufficient that both the pyroelectric substance and the metal ion-retaining inorganic particles are contained in each other.

The type, shape, and shape of the organic polymer molded article of the present invention
The structure, form, etc. are not particularly limited, and for example, film,
It may be a sheet, a plate, a hollow molded product, a molded product, a tray obtained by press molding or vacuum molding a film or sheet, other molded products, a foam molded product, a laminated molded product and the like. Further, even if those molded articles are formed only of the organic polymer, the organic polymer and other materials (for example, paper,
It may be a laminated body formed by combining a cloth, a metal foil, etc.), or a composite molded article other than the laminated structure. Furthermore, the organic polymer constituting the organic polymer molded article of the present invention may be composed of one type of organic polymer, a blend of two or more types of organic polymers, or two or more types of organic polymers. The polymer may be laminated in layers.

The organic polymer molded article of the present invention can be produced by any conventionally known method depending on the type of molded article, the type of organic polymer constituting the molded article, the shape, structure, use of the molded article and the like. The organic polymer molded articles of the present invention which can be produced and therefore are, for example, extrusion molded articles, extrusion blow molded articles,
Injection molded products, injection blow molded products, calendar molded products, vacuum molded products, press molded products, foam molded products, laminated molded products, cast molded products, slush molded products, powder molded products, bead molded products, etc. May be.

The content of the pyroelectric substance and the metal ion-holding inorganic particles in the organic polymer molded article depends on the type of molded article,
It can be adjusted according to the shape and structure (for example, whether it is a laminated structure or a single layer structure), the application, etc. However, in general, a molded article [hereinafter sometimes referred to as “molded article (A)”] containing both the pyroelectric substance and the metal ion-retaining inorganic particles in the same layer (including a single-layer molded article) It is preferable that the contents of the pyroelectric material and the metal ion-retaining inorganic particles are each 0.1% by weight or more and the total content of both is 20% by weight or less. And the total content of both is 1
It is more preferably 0% by weight or less.

Further, the organic polymer molded article may be a laminated molded article [hereinafter referred to as "molded article (B)"] having a layer containing only a pyroelectric substance and a layer containing only metal ion-holding inorganic particles. ], The content of the pyroelectric substance in the layer containing the pyroelectric substance is 0.1 to 20% by weight, more preferably 1 to 5% by weight based on the weight of the organic polymer constituting the layer. % By weight, and the content of the metal ion-retaining inorganic particles in the layer containing the metal ion-retaining inorganic particles is 0.1 to 20 based on the weight of the organic polymer forming the layer.
It is preferable to set the content by weight, more preferably 1 to 5% by weight.

When the content of each of the pyroelectric substance and the metal ion-retaining inorganic particles in the above-mentioned molded product (A) is less than 0.1% by weight, the molded product (A) is packed into foods and fresh flowers. When used for such purposes, it becomes difficult to sufficiently exert its freshness-retaining action and sterilizing action. On the other hand, in the molded product (A), when the total content of the pyroelectric substance and the metal ion-holding inorganic particles exceeds 20% by weight, the processability in manufacturing the molded product becomes poor, and In addition, the surface is roughened and the mechanical strength is lowered, so that it becomes difficult to obtain a good molded product.

Further, in the above-mentioned molded product (B), the content of the pyroelectric substance in the layer containing the pyroelectric substance is 0.
If the content is less than 1% by weight and / or the content of the metal ion-retaining inorganic particles in the layer containing the metal ion-retaining inorganic particles is less than 0.1% by weight, the molded article (B)
When used for foods and fresh flowers, it becomes difficult to sufficiently exert its freshness-retaining action and bactericidal action. On the other hand, in the molded article (B), the content of the pyroelectric substance in the layer containing the pyroelectric substance exceeds 20% by weight, and / or the metal ion-retaining inorganic substance in the layer containing the metal ion-retaining inorganic particles. If the content of the particles exceeds 20% by weight, the processability at the time of molding may be poor, or the molded product may have bumps, surface roughening, or decrease in mechanical strength.
It becomes difficult to obtain a good molded product.

In both the above-mentioned molded product (A) and molded product (B), the inorganic particles in the metal ion-retaining inorganic particles are replaced with metal ions at an ion exchange rate of 90% or more when viewed as the entire molded product. In the case of the above, the pyroelectric substance: metal ion holding inorganic particles = 1: 0.2
It is desirable that the molded product contains the pyroelectric substance and the metal ion-retaining inorganic particles in an amount of 1 to 1 (weight ratio), because the freshness-retaining action and the sterilizing action can be effectively exhibited.

The thickness of the organic polymer molded article of the present invention is
It can be appropriately adjusted according to the type of molded product, the strength required for the molded product, the use of the molded product, etc., and is not particularly limited. Among them, when the organic polymer molded article of the present invention is a film or sheet used as a packaging material for foods and fresh flowers, in the case of a molded article obtained by vacuum molding or press molding the film or sheet, From the viewpoint of maintaining practical strength, it is preferable that the average value of the thickness is 10 μm or more. The upper limit of the thickness is not particularly limited, but from the viewpoint of cost, it is preferably 3 mm or less, and the thickness is 3 m.
Even if it is higher than m, the effect of maintaining freshness is often not further improved, and the cost is increased.

As the organic polymer constituting the organic polymer molded article of the present invention, any organic polymer which can produce a molded article can be used, including thermoplastic polymers and thermosetting resins. Although any of the organic polymers can be used, a thermoplastic organic polymer is preferable because the desired molded article can be easily and smoothly manufactured by the various molding methods described above. In particular, when the organic polymer molded article of the present invention is a film or sheet, or a tray or other container obtained by further vacuum-forming or press-molding them, those molded articles are formed from a thermoplastic polymer. It is preferable from the viewpoints of moldability and handleability of the molded product.

Examples of the organic polymer constituting the organic polymer molded article of the present invention include polyethylene terephthalate, polybutylene terephthalate, and other polyesters;
Polyethylene, polypropylene, other polyolefins; ethylene-vinyl acetate copolymers; ethylene-
Methyl (meth) acrylate-based copolymer; nylon 6, nylon 66, nylon 11, nylon 610, nylon 612, other polyamides; polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer Vinyl chloride-based polymers such as polymers; polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymers, vinylidene chloride-vinyl acetate copolymers and other vinylidene chloride-based polymers; styrene-based polymers; polycarbonates; polyvinyl alcohol-based polymers Fluorine-based resins; thermoplastic elastomers; cellulose acetate; regenerated cellulose and the like.

The method for producing the organic polymer molded article of the present invention is not limited at all, and it is conventionally known depending on the type of molded article, the type, shape, structure, application of the organic polymer constituting the molded article. It can be produced by any method, for example, extrusion molding, extrusion blow molding, injection molding, injection blow molding, calendar molding, vacuum molding, press molding, as described above.
It can be produced by methods such as foam molding, laminate molding, cast molding, slush molding, powder molding, and bead molding.

Further, as a method for adding the pyroelectric substance and / or the metal ion-retaining inorganic particles in the case of producing an organic polymer molded article containing the pyroelectric substance and / or the metal ion-retaining inorganic particles in the molded product, Include, but are not limited to, a method of adding a pyroelectric substance and / or metal ion-holding inorganic particles during or immediately after the polymerization of the organic polymer; a pyroelectric substance and / or in the organic polymer. A method of adding a metal ion-retaining inorganic particle to prepare a masterbatch and using the masterbatch; an arbitrary step until the polymer becomes a molded article in an organic polymer (for example, a step of producing polymer pellets, melt molding) Examples of the method include adding a pyroelectric substance and / or metal ion-holding inorganic particles in a step). Then, in the case of the above-mentioned addition method, for example, a method of adding to a raw material slurry for producing an organic polymer, a method of adding a prepolymer after production of the prepolymer immediately before polycondensation, an organic polymer It can be carried out by adopting a method of adding immediately after the production of the coalescence and while it is still in a liquid state.

The molded article of the organic polymer of the present invention is preferably used in the form of a film or sheet, particularly as a packaging material or container for fresh products such as foods and fresh flowers. In that case, the film or sheet is For example, (i) a layer containing or adhering only a pyroelectric substance,
A laminated film or laminated sheet comprising a layer containing or adhering only metal ion-retaining inorganic particles; (ii) a single-layer film or single-layer sheet containing or adhering both a pyroelectric substance and metal ion-retaining inorganic particles;
It can be in the form of.

The above-mentioned laminated film or laminated sheet (i) can be produced by a conventionally known lamination molding method such as extrusion lamination, coextrusion, hot lamination, dry lamination, and wet lamination. The single-layer film or single-layer sheet of (ii) above can be produced by a conventionally known molding method such as T-die extrusion molding, inflation extrusion molding, calender molding, and casting molding. The film or sheet may be stretched or unstretched.

In addition to the pyroelectric substance and the metal ion-retaining inorganic particles, the organic polymer molded article of the present invention has been conventionally prepared in accordance with the type of organic polymer constituting the molded article, the use of the molded article, etc. Various additives used in molded articles such as UV stabilizers, antioxidants, flame retardants, antistatic agents, colorants, lubricants, antibacterial agents, insect / anti-mite agents, deodorants, and ultraviolet absorbers. , A matting agent, a heat storage agent, etc. may be contained.

The organic polymer molded article of the present invention can be effectively used for applications utilizing its freshness-retaining function and bactericidal action, and particularly packaging materials for foods, packaging containers, storage containers, etc. Can be used as When the organic polymer molded article of the present invention is used in food, for example, even if the food is wrapped by using the organic polymer film or sheet as it is,
Even if a bag or the like is manufactured from an organic polymer film or sheet and food is put in the bag, the organic polymer film or sheet is vacuum-formed or press-molded to manufacture a container such as a tray and the food is put in the container. May be included. Further, the organic polymer molded article of the present invention, in the form of an injection molded container or other mold-molded container, put food in it, even if distributed and sold, also put the food in those containers It may be saved. Furthermore, the molded product of the organic polymer of the present invention may be formed into a bottle, a can, or the like, which is filled with a liquid food for distribution, sale, storage, or the like. Therefore, when the organic polymer molded product of the present invention is used for food, it may be a disposable molded product or a molded product such as a durable container that can be repeatedly used. In the case where the organic polymer molded article of the present invention is a container having a certain thickness, the inner layer portion of the container is made to contain a large amount of pyroelectric substance and metal ion-retaining inorganic particles, and the gas barrier property and the like are added as necessary. A laminated container in which other excellent materials are laminated may be used.

When the organic polymer molded article of the present invention is used for packaging and storage of foods, discoloration of foods,
It is possible to prevent or reduce deterioration and spoilage, and maintain good food freshness for a long period of time. In that case, the type of food is not particularly limited, and fresh food products such as meat, seafood, vegetables, fruits and eggs, processed products thereof, and other foods that have a high water content and cannot be stored for a long time Even if the content is small, it can be effectively used for any food or the like for which deterioration prevention is desired.

The organic polymer molded product of the present invention is also suitable as a packaging material for fresh flowers. When the organic polymer molded product of the present invention is used, discoloration and wilting of fresh flowers are reduced. The flowers and leaves can be kept in good color and condition for a long time.For example, when fresh flowers are packaged and transported by the packaging material of the present invention, the quality of fresh flowers can be kept good for a long time.
Fresh flowers with high commercial value can be provided to consumers. The kind of fresh flowers that can be used for the packaging material of the present invention is not particularly limited, and it can be used as a packaging material for various fresh flowers such as orchids, roses, lilies, tulips, gerberas and carnations.

When the organic polymer molded article of the present invention containing a pyroelectric substance and metal ion-retaining inorganic particles is used as a packaging material or container for foods and fresh flowers, it may be prepared according to the size and shape of the foods and fresh flowers, for example , As described above, in the form of a sheet or film having a rectangular shape or other shapes, or a band, a bag, a molded product such as a tray or a container, and wrapping food or fresh flowers in the sheet, bundling with a band, or a bag. It can be used by placing the molded product in contact with the food or fresh flowers when packaging the food or fresh flowers with another packaging material. Further, when the organic polymer molded product of the present invention is a foam molded product, it may be a container having properties such as cushioning property (cushioning property) and heat insulating property as well as properties such as freshness-retaining action and sterilizing action. it can. However, when used as a packaging material or a container, the form is not limited to the above.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 (1) Polyethylene terephthalate (intrinsic viscosity = 0.
73) based on its weight tourmaline (Brazilian)
Fine powder (average particle size 1 μm or less) was added at a rate of 5% by weight, and this was melt-kneaded at 280 ° C. in a screw type extruder, extruded from an I-type die onto a casting drum, and then cooled. The film was biaxially stretched to produce a film having a thickness of 20 μm [film (a)]. (2) Polyethylene terephthalate (intrinsic viscosity = 0.
75) Zeolite fine powder ion-exchanged (ion-substituted) with silver ions and zinc ions based on the weight thereof
(Shinagawa Fuel Co., Ltd. "Zeomic") was added at a ratio of 2% by weight to produce a biaxially stretched film in the same manner as in the above (1) [film (b)]. (3) In the above (1) and (2), the film (a) and the film (b) were thermocompression-bonded through a heating roller at 260 ° C. to be laminated and integrated to produce a sheet-shaped molded product of the present invention. (4) Broccoli (about 10 cm) was prepared using the sheet-shaped molded product (length × width = 30 cm × 30 cm) obtained in (3) above.
0 g) was completely wrapped and stored in a refrigerator at 5 ° C., and the state of broccoli after 3 days, 1 week and 10 days was visually observed, and it was as shown in Table 1 below. . (5) In addition, using the sheet-shaped molded product (length × width = 30 cm × 30 cm) obtained in (3) above, beef (about 10
0 g) was completely wrapped and stored in a refrigerator at 5 ° C., and the condition of beef after 3 days, 1 week and 2 weeks was visually observed, and the results are shown in Table 2 below. It was

Example 2 (1) 4% by weight of the same tourmaline fine powder used in Example 1 based on the weight of polyethylene (MI = 2), the same as that used in Example 1 Zeolite fine powder ion-exchanged (ion-substituted) with silver ions and zinc ions was added at a ratio of 2% by weight, and this was melt-kneaded at 160 ° C. in a screw-type extruder and extruded upward in a tubular shape from a ring die, After cooling, a film having a film thickness of 20 μm was manufactured. (2) The film obtained in (1) above (length x width = 30)
cm x 30 cm) and broccoli (approx. 100 g)
Was completely wrapped and stored in a refrigerator at 5 ° C., and the state of broccoli after 3 days, 1 week and 10 days was visually observed, and the results are shown in Table 1 below. (3) Beef (about 100 g) was completely wrapped using the film (length × width = 30 cm × 30 cm) obtained in the above (1) and stored in a refrigerator at 5 ° C.
When the state of beef after day, one week and two weeks was visually observed, it was as shown in Table 2 below.

Example 3 (1) Vinylidene chloride / vinyl chloride (85/15; weight ratio) vinylidene chloride-based copolymer was mixed with 4% by weight of the same fine powder of tourmaline as used in Example 1. And Example 1
3% by weight of zeolite fine powder ion-exchanged (ion-substituted) with the same silver ion and zinc ion as used in the above was added, and this was added in a screw type extruder at 200 ° C.
A film having a thickness of 30 μm was produced by an inflation molding method in which the mixture was melt-kneaded with, extruded upward in a tube shape from a ring die, supercooled at 10 ° C. in a cooling tank, and then blown with air at 25 ° C. to expand. (2) The film obtained in (1) above (length x width = 30)
cm x 30 cm) and broccoli (approx. 100 g)
Was completely wrapped and stored in a refrigerator at 5 ° C., and the state of broccoli after 3 days, 1 week and 10 days was visually observed, and the results are shown in Table 1 below. (3) Beef (about 100 g) was completely wrapped using the film (length × width = 30 cm × 30 cm) obtained in the above (1) and stored in a refrigerator at 5 ° C.
When the state of beef after day, one week and two weeks was visually observed, it was as shown in Table 2 below.

Comparative Example 1 Except that 4 wt% of the same tourmaline fine powder used in Example 1 was added without adding the zeolite fine powder ion-exchanged (ion-substituted) with silver ions and zinc ions. Was produced in the same manner as in Example 3, and the freshness retaining effect on broccoli and beef was examined in the same manner as in Example 3, and the results are shown in Tables 1 and 2 below. It was

Comparative Example 2 Without adding tourmaline fine powder, 3 wt% of only zeolite fine powder ion-exchanged (ion-substituted) with the same silver ions and zinc ions as used in Example 1 was added. A film was produced in the same manner as in Example 3 except for the above, and the freshness-keeping effect on broccoli and beef was examined in the same manner as in Example 3, and the results were as shown in Tables 1 and 2 below. there were.

Comparative Example 3 A film was produced in the same manner as in Example 3 except that neither tourmaline fine powder nor zeolite fine powder ion-exchanged (ion-substituted) with silver ions and zinc ions was added. Using the same, the freshness retaining effect on broccoli and beef was examined in the same manner as in Example 3, and the results are shown in Tables 1 and 2 below.
It was as shown in.

[0042]

[Table 1]

[0043]

[Table 2]

From the results shown in Table 1 above, the results of Examples 1 to 3 containing both tourmaline (pyroelectric substance) and fine zeolite powder (metal ion holding inorganic particles) holding silver ions and zinc ions were obtained. When broccoli is packaged using the molded product (film or sheet) of the present invention (packaging material for food), yellowing and rot of the broccoli do not occur even after 1 week, and the freshness thereof is kept good. It can be seen that the yellowness slightly occurs after 10 days, and the freshness of the broccoli is kept good for a long time. On the other hand, when the food packaging material of Comparative Example 1 containing only tourmaline (pyroelectric substance) is used, the food packaging material of Comparative Example 2 containing only metal ion-retaining inorganic particles, and tourmaline. When the food packaging material of Comparative Example 3 containing neither (pyroelectric substance) nor metal ion-retaining inorganic particles was used, yellowing of broccoli had already occurred 3 days later, and putrefaction started 1 week later. Moreover, it can be seen that the rot of broccoli is not maintained well after 10 days since the rotting is progressing.

Further, from the results of Table 2 above, Examples 1 to 3 containing both tourmaline (pyroelectric substance) and fine zeolite powder (metal ion-holding inorganic particles) holding silver ions and zinc ions. When beef was packaged using the food packaging material of No. 3 of the present invention, no change was observed in the beef until at least 3 days, its freshness was kept good, and a slight discoloration occurred after 1 week. It can be seen that the freshness of beef is kept good for a long time. On the other hand, when the food packaging material of Comparative Example 1 containing only tourmaline (pyroelectric substance) is used, the food packaging material of Comparative Example 2 containing only metal ion-retaining inorganic particles, and tourmaline. When the food packaging material of Comparative Example 3 containing neither (pyroelectric substance) nor metal ion-retaining inorganic particles was used, the red meat portion of the beef was already black and discolored after 3 days. After 1 week, discoloration and flesh hardening occurred, and 2
It can be seen that after a week, it will rot and the freshness of the beef will not be kept good.

[0046]

INDUSTRIAL APPLICABILITY The organic polymer molded article of the present invention containing a pyroelectric substance and metal ion-retaining inorganic particles, when used as a packaging material for food, a container for packaging and / or storage, etc. Prevents discoloration, deterioration, and decay of foods and keeps their freshness for a long time, and even when used as a packaging material for fresh flowers, it reduces discoloration and wilting of fresh flowers and makes them last longer. be able to. Then, the organic polymer molded article of the present invention contains the metal ion-retaining inorganic particles together with the pyroelectric material, so that the pyroelectric property of the pyroelectric material is amplified by the metal ion-retaining inorganic particles, and is expensive. The above effects can be satisfactorily exhibited without using a large amount of a pyroelectric substance.

Front page continued (72) Inventor Tomio Masuda 3-27-12 Hongo, Bunkyo-ku, Tokyo Okamoto Co., Ltd. (72) Kenji Hiramatsu 1-1239 Umeda, Kita-ku, Osaka, Osaka Kuraray Co., Ltd. (56) References Japanese Unexamined Patent Publication No. 6-136137 (JP, A) Actual Development No. 3-14127 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101 / 16

Claims (9)

(57) [Claims] 1. An organic polymer molded article comprising a pyroelectric substance and inorganic particles retaining metal ions. 2. The organic polymer molded article according to claim 1, wherein the organic polymer is a thermoplastic organic polymer. 3. The organic polymer molded article according to claim 1, wherein the metal ion is an ion of at least one metal selected from silver, zinc, copper, gold, platinum and iron. 4. The organic polymer molded product according to claim 1, wherein the organic polymer molded product is a film or a sheet. 5. An organic polymer molded article is produced by extrusion molding, extrusion blow molding, injection molding, injection blow molding, calendar molding,
The organic polymer molded product according to any one of claims 1 to 4, which is a molded product obtained by vacuum molding, press molding, foam molding, laminate molding, cast molding, slush molding or powder molding. 6. The organic polymer molded product according to claim 1, which is a packaging material for food or fresh flowers. 7. The organic polymer molded product according to any one of claims 1 to 5, wherein the organic polymer molded product is a container for food. 8. A pyroelectric substance and inorganic particles retaining metal ions are contained in the same organic polymer layer.
An organic polymer molded article according to any one of items 1 to 7. 9. The organic polymer according to claim 1, which has an organic polymer layer containing a pyroelectric substance and an organic polymer layer containing inorganic particles retaining metal ions. Molding.