JPH032235A - Polymer molded article containing isothiocyanic acid ester - Google Patents

Abstract

PURPOSE:To obtain the subject polymer molded article for packaging material of food, leather product, etc., containing isothiocyanic acid ester, capable of preventing occurrence of a mildew and proliferation of a microorganism by releasing isothiocyanic acid ester from the surface of molded article and having antimicrobial properties in itself. CONSTITUTION:The aimed high polymer molded article obtained by melting and blending (A) 40 pts. wt. absorbing agent (e.g. sepiolite fine powder), with (B) 60 pts. wt. polyethylene and molding the blend into film or sheet and permeating and absorbing (C) a liquid like or gaseous isothiocyanic acid ester into the molded article so as to release the isothiocyanic acid ester from the surface of molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a polymer molded article containing an isothiocyanate ester.

(Prior art and its problems) Various foods, glass products such as lenses, leather products such as leather boots, leather jumpers, and fur coats.

Mold growth is observed in industrial products such as starch-based or cellulose-based paints and glues, which significantly reduces their high-volume value or necessitates disposal.

Furthermore, even if mold does not occur, the value of the product may be significantly impaired or the product may need to be disposed of due to the proliferation of harmful microorganisms.

For example, in foods, etc., problems of fermentation and food poisoning occur due to proliferation of bacteria.

BACKGROUND ART Conventionally, in order to prevent the growth of mold on articles, it has been known to hermetically package the articles with a packaging material together with an oxygen absorber to maintain the oxygen concentration inside the package at 1% or less. Although this method can effectively prevent the growth of aerobic mold, it cannot be an effective means of preventing the proliferation of anaerobic bacteria that cause food poisoning and fermentation. .

In addition, to prevent the growth of mold and the proliferation of general bacteria,
It is also known to hermetically package an article together with an ethanol generating agent in a packaging material, and to fill the inside of the package with ethanol vapor. However, in this method, the ethanol used is expensive and a satisfactory effect cannot be obtained unless it is used in a relatively large amount.

Furthermore, although many antifungal and antibacterial agents have been known, most of these chemical agents are toxic to the human body, which poses the problem of severe restrictions on their use. There is.

(Problems to be solved by the invention) An object of the present invention is to solve the above-mentioned problems encountered in conventional methods of preventing the growth of mold and preventing the growth and proliferation of harmful microorganisms, and to provide a polymer molded product that itself has antibacterial properties. shall be.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors have found that isothiocyanate ester, the main component of wasabi, has excellent effects as an antibacterial agent even when used in extremely small amounts. In addition to discovering that this isothiocyanate ester has excellent permeability to polymer materials, they focused on the fact that it permeates through polymer molded articles such as polyethylene and polypropylene, and completed the present invention.

That is, according to the present invention, there is provided a polymer molded article containing an adsorbent adsorbing an isothiocyanate ester, the polymer allows the isothiocyanate ester to permeate, and the inthiocyanate ester is diffused from the surface of the molded article. A polymer molded article containing an isothiocyanate ester is provided.

It has been known from experience that wasabi has antibacterial, antifungal, and anticorrosion effects.

However, industrial agents such as antibacterial agents, antifungal agents, and freshness-preserving agents that contain isothiocyanate ester, the main component of wasabi, as an active ingredient have not yet been developed.
Polymer molded articles containing isothiocyanate esters, such as those of the present invention, are completely unknown.

As used herein, antibacterial properties mean bactericidal properties, bacteriostatic properties, antibacterial properties, etc. against aerobic bacteria and anaerobic bacteria.

As the isothiocyanate ester in the present invention, various esters of isothiocyanate are used, but preferably allyl isothiocyanate ((J12=C
HCH, NC3) and isothiocyanic acid alkyl esters (RNC3, R: alkyl group) are used.

In the present invention, mustard oil can be used as it is.

In order to produce the polymer molded article of the present invention, it is sufficient to prepare a polymer composition containing an adsorbent in advance and mold it into the desired shape.The shape of the molded article can be arbitrary. , container shape, sheet shape.

Various shapes such as a film shape and a pellet shape are included. As the adsorbent contained in the polymer, various conventionally known adsorbents can be used. For example, 5 such things include:
sepiolite, attapulgite, balgorskite,
Examples include soda zeolite, mordenite, silica, alumina, and zeolite. The content of the adsorbent is 5 to 60% by weight, usually 10 to 40% by weight, based on the entire molded article. Further, as the polymer, any polymer can be used, such as polyethylene, polypropylene, and ethylene/vinegar, as long as it is permeable to polyolefins such as vinyl copolymers or isothiocyanate esters such as copolymers thereof.

Next, a polymer molded article (hereinafter also simply referred to as a molded article) containing an adsorbent is brought into contact with an isothiocyanate ester in liquid or vapor form. Examples of the method of contacting the molded article with the isothiocyanate ester in vapor form include a method of holding the molded article in the vapor of the isothiocyanate ester or a gas containing the same, such as air or nitrogen. Through this contact treatment, the vapor of the isothiocyanate ester permeates into the molded article and is adsorbed and retained by the adsorbent in the molded article. Methods for contacting the molded product with the inthiocyanate ester in liquid form include spraying or coating the molded product with a liquid isothiocyanate ester or a solution thereof, or a method of contacting the molded product with a liquid isothiocyanate ester or its solution. Examples include a method of immersing a molded article in the solution. Even in such a treatment, the isothiocyanate ester permeates into the molded article from the contact interface in vapor form and is adsorbed and retained by the adsorbent in the molded article.

The molded product thus obtained has the property that the adsorbent present therein contains isothiocyanate ester and gradually releases the isothiocyanate ester, and the polymer constituting the molded product contains isothiocyanate. Since acid esters are permeable, vapor of the isothiocyanate ester is radiated from the surface of the molded article.

If it is desired to further suppress the amount of isothiocyanate ester released from the surface of the molded article, a polymer coating can be applied to the surface of the molded article. In this case, the above-mentioned polyolefin or copolymer thereof is used as the polymer. Coating methods include turning the polymer into a solution and spraying it.

A method of coating the surface of a molded article by a method such as a coating method or a dipping method can be adopted. Alternatively, a method may be employed in which a polymer is formed into a film and this is pressure-bonded or thermocompression-bonded to the surface of the molded product with or without an adhesive.

In addition, when the molded product is a film, sheet, etc., a polymeric film substantially impermeable to isothiocyanate esters can be laminated or coated on one surface of the molded product.

Further, when the molded article is a container, the outer surface thereof can be laminated or coated with a polymeric film that is substantially impermeable to isothiocyanate esters. In such a molded article, isothiocyanate ester is emitted from the side that is not coated with a film or coating. Examples of polymers that do not substantially allow isothiocyanate to pass through include polyester, polyamide, polyvinyl chloride, polyvinylidene chloride, etc. Isothiocyanate ester is released from its surface and has antibacterial properties by itself. Therefore 1
The molded article of the present invention can be advantageously used in fields where the occurrence of mold and the proliferation of microorganisms are problematic.

In the molded article of the present invention, the sheet or film can be used as a packaging material for hermetically packaging foods and other articles where microorganisms are likely to multiply. In articles hermetically packaged with such packaging materials, the antibacterial action of the isothiocyanate ester released from the surface of the film or sheet prevents the growth of mold as well as the proliferation of other microorganisms. Also,
Container-shaped molded articles can also be used as anti-fungal and anti-bacterial containers. The thread-like molded product can be used as a mold-proof and antibacterial mesh bag for fruits, vegetables, etc. by making it into a bag. Since isothiocyanate ester is generated from the surface of the pellet-shaped molded article, it can be used as an isothiocyanate ester generator. These isothiocyanate ester generators can be packaged in isothiocyanate ester-permeable packaging materials such as paper or polyethylene or polypropylene, and the package is sealed together with the food in the packaging material to maintain the freshness of the food. It can be performed.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Example After 40 parts of adsorbent (sepiolite fine powder) and 60 parts of polyethylene were melt-mixed, they were formed into a film to obtain a film containing the adsorbent with a thickness of about 50 cm, and one side of this film was A polyester film was laminated and adhered to the surface.

Next, this film was placed in an airtight container together with a petri dish containing liquid isothiocyanate ester (allyl isothiocyanate), sealed, and placed in a constant temperature bath at a temperature of 40 ° C.
After standing for 24 hours, the container was opened and the film was taken out. This film emits a mustard odor only from the polyethylene film surface.

It was confirmed that isothiocyanate ester was released.

Next, a bag was formed from this film, a cutter was inserted through the opening of the bag, and the opening was sealed by heat sealing. This package has a polyester film on the outer surface that is substantially impermeable to isothiocyanate ester,
Because it is IS.

No mustard odor was emitted from the outside.

For comparison, a cut mochi was similarly placed in a polyethylene bag and sealed by heat sealing.

When the above-mentioned packaged cut mochi was left at room temperature, mold growth was observed in the comparative cut mochi after 3 days, but mold growth was observed in the cut mochi wrapped in the film of the present invention after 1 month. However, no mold growth was observed.

Example 2 A laminated adhesive film of a polyethylene film and a polyester film containing the adsorbent shown in Example 1 was soaked in a 10% alcohol solution of inthiocyanic acid ester.
After being immersed for a period of time, it was taken out and dried. This film also emitted a mustard odor only from the polyethylene film surface, and it was confirmed that inthiocyanate ester was released.

Patent applicant: Minato Sangyo Co., Ltd. Representative Patent Attorney Toshiaki Ikeura (1 other person)

Claims (1)

[Scope of Claims] (1) A polymer molded article containing an adsorbent that has adsorbed isothiocyanate, the polymer allows the isothiocyanate to pass through, and the isothiocyanate ester is diffused from the surface of the molded article. A polymer molded product containing an isothiocyanate ester. (2) The molded article according to claim 1, wherein at least a portion of the surface is coated with an isothiocyanate-permeable polymer coating. (3) The molded article according to claim 1, wherein the molded article is a film or a sheet. (4) The molded article according to claim 3, wherein a film substantially impermeable to isothiocyanate esters is laminated and adhered to one surface of the film.