JPS5980450A - Antifungal packaging bag - Google Patents

Abstract

PURPOSE:An antifungal packaging bag, formed from a film of a polyolefin resin, composition containing a small amount of (ethyl)vanillin, capable of suppressing the growth of molds, and suitable to packaging of feeds, fertilizers and foods, etc. CONSTITUTION:A packaging bag obtained by forming a film from a polyolefin resin composition containing at least 0.01wt%, preferably 0.05-1wt%, vanillin and/or ethylvanillin, and using the resultant film. The (ethyl)vanillin is incorporated in the above-mentioned resin by either one of dry blending and masterbatching methods. The film is formed easily by the extrusion inflation molding or T-die molding method.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-fungal packaging bag, and more particularly to a packaging bag with excellent anti-fungal properties suitable for packaging feed, fertilizer, food, etc.

Currently, paper bags (for example, a three-layer kraft paper bag combined with a plastic film inner bag) are the mainstream packaging bags for livestock feed such as cattle, pigs, and chickens. Because the feed is mainly made of glaze, rice bran, etc.), vegetable oil cake, molasses, etc., and contains moisture, bacteria and microorganisms in the air can grow during storage and transportation of the packaged feed. mold. Conventionally, the method of adding fungicides such as sodium propionate directly to the feed has been used to suppress mold in such feed, but it has not been possible to sufficiently suppress the growth of mold, and the long-term storage of the feed has been difficult. In addition, when mixing fungicides into feed, it tends to be uneven, and it takes a lot of time and money to mix it uniformly. .

The inventors of the present invention have conducted various studies to solve the conventional problems in packaging for feed, etc., and have found that the packaging bag itself is extremely easy to manufacture, and the packaging bag itself has excellent anti-fungal properties. We were able to develop a bag.

That is, the present invention is an anti-fungal packaging bag made of a film of a polyolefin resin composition containing at least 0,407% by weight of vanillin and/or ethylvanillin.

The film constituting the antifungal packaging bag of the present invention is a film obtained by molding a polyolefin resin composition containing at least 0.07% by weight of vanillin and ethylvanillin.

Various types of polyolefin resins can be used. Examples include low density polyethylene, high density polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, and the like. Two or more types of these polyolefin resins may be used as a blend. In the present invention, the selection and use of polyolefin resins in particular are advantageous in imparting antifungal properties to packages, since the polyolefin resin film cabanillin and/or ethyl vanillin can be easily volatilized in a sustained manner. Because there is.

It is already known that vanillin and ethyl vanillin used in the present invention have fungicidal properties, but if they are packaged in a film made from a resin composition combined with a specific resin called polyolefin resin, it is possible to It was discovered for the first time in the present invention that the growth of mold on food products and the like can be extremely effectively prevented.

Currently, vanillin and ethyl vanillin are used as feed flavoring (
Flavoring agents) are widely used as palatable flavors, especially for infant animals.Mata vanillin and ethyl vanillin are also added as flavors to foods such as ice cream. In addition, vanillin and ethyl vanillin are not only substances that have a fungicidal effect, but also can increase the commercial value of the packaging bag itself based on their aromatic properties, and can also improve the animal's preference for the packaged feed. Effects such as being able to do this can also be obtained.

The content of vanillin and/or ethylvanillin in the present invention is at least 0.07% by weight, preferably 0.07% by weight in the resin composition. Oj weight% or more. If the content is too low, a sufficient antifungal effect cannot be obtained. Further, the upper limit of the content of vanillin and/or ethyl vanillin is usually about 3% by weight, preferably about 1% by weight based on the resin composition. If the content is too large, film formability will deteriorate.

Various methods can be used to blend vanillin and/or ethyl vanillin into polyolefin resins, but usually the resin and vanillin and/or ethyl vanillin are directly mixed in a solid form such as powder during film production. There is a direct tri-blend method in which vanillin and/or ethyl vanillin are blended into the resin at a high concentration, and a masterbatch is prepared in advance, and this masterbatch is diluted with polyolefin resin during film production. There is a master patch method. In addition, as a method for manufacturing a master patch in the latter method, (1) blending vanillin and/or ethyl vanillin in a polyolefin resin (preferably low density polyethylene or ethylene/vinyl acetate copolymer resin) at a high concentration; (2) A method of adding vanillin and/or ethyl vanillin to the ethylene/vinyl acetate copolymer resin in the coexistence of a solvent and impregnating them into the resin under heating. The latter method is particularly preferred.

In such a masterbatch method, the concentration of vanillin and/or ethyl vanillin blended into the polyolefin resin (master patch) is usually about 7 to 10% by weight, preferably about 2 to 6% by weight. In addition, the solvent used in method (2) has an affinity for the ethylene/vinyl acetate copolymer resin to be impregnated, and can swell it, but cannot dissolve it, and vanillin And/or a material that can dissolve ethyl vanillin and promote diffusion impregnation, and that can promote volatilization of vanillin and/or ethyl vanillin in a formed film is preferable. Examples of such solvents include terpene hydrocarbons such as α-limonene, aromatic esters such as benzyl benzoate, and aromatic alcohols such as benzyl alcohol.

In addition to containing the vanillin and/or ethyl vanillin, the polyolefin composition produced in this manner can also contain stabilizers, colorants, fillers, antistatic agents, etc. that are usually added to polyolefin resins. .

Various methods can be used to form a polyolefin resin composition containing vanillin and/or ethyl vanillin into a film, but in general, extrusion inflation molding and T-die molding are simple and easy. ,
preferable. In order to form a film from such a resin composition, the resin composition may be formed into a single layer film, or may be formed into a multilayer (laminated) film of this resin composition and another resin. good. Coextrusion inflation molding and T-die molding are also advantageously used when molding into a multilayer film.

To manufacture the packaging bag of the present invention using a single layer film of a polyolefin resin composition containing vanillin and/or ethyl vanillin or a multilayer film with other resins, only such a single layer film or multilayer film is used for packaging. It may be made into a bag, or it may be made into a multilayered packaging bag by stacking such single layer or multilayer film and another resin film in two or more layers. Even when the packaging bag of the present invention is manufactured using the above multilayer film alone, or when the packaging bag of the present invention is manufactured by stacking the films in a multilayer structure of two or more layers, It is desirable that the packaging bag is constructed such that a film layer of a polyolefin resin composition containing vanillin and/or fly methyl vanillin is located in the innermost layer of the finished packaging bag. In addition, vanillin and/or ethyl vanillin is difficult to permeate and diffuse through the outside of such an inner layer, in which a film layer of a polyolefin resin composition containing vanillin and/or ethyl vanillin is positioned (hereinafter simply referred to as "difficult to diffuse"). ”
It is more preferable that the packaging bag is covered with a film. Examples of difficult-diffusion films in such cases include nylon, polyester, cellophane,
Examples include films such as aluminum foil.

Further, as specific examples of combinations for producing the multilayer film for packaging bags of the present invention by the above-mentioned coextrusion inflation molding method, etc., for the double layer film, for example, low density polyethylene or ethylene/vinyl acetate copolymer is used. and high-density polyethylene are extruded and laminated into a two-layer film using a coextrusion inflation molding method, etc., and this two-layer film is formed into a packaging bag with a low-density polyethylene or ethylene-vinyl acetate copolymer layer on the inside and a high-density polyethylene layer on the outside. A packaging bag is formed with the density polyethylene layer positioned thereon. In addition, as a three-layer film, for example, the inner and outer layers are made of low-density polyethylene, the inner layer is made of ethylene/vinyl acetate copolymer, and the middle layer is made of high-density polyethylene using a similar extrusion method. This three-layer film is then used as a packaging bag. In any case, vanillin and/or ethyl vanillin is contained in the resin layer serving as the inner layer of the packaging bag as described above.

The thickness of the film of the vanillin- and/or ethylvanillin-containing polyolefin resin composition used in the production of the packaging bag of the present invention is not particularly limited and can be appropriately selected depending on the application, but generally hand/! ~200μ is sufficient.

When feed, fertilizer, and food products are packaged using the packaging bag of the present invention, vanillin and/or ethyl vanillin contained in the polyolefin resin film of the packaging bag gradually migrates to the surface of the film. ) The volatilized vanillin and ethyl vanillin diffuse into the packaging bag and reach not only the inner surface of the packaging but also the contents, making it possible to effectively prevent the growth of mold as a whole. As described above, if the packaging bag is configured so that the outside of the polyolefin resin film layer containing vanillin and/or ethyl vanillin is covered with a hard-diffusible film layer, the hard-diffusible film layer can contain vanillin and/or ethyl vanillin. Dissipation (loss) of ethyl vanillin into the outside air can be effectively prevented.

Thus, the packaging bag of the present invention has significantly superior antibacterial properties compared to conventional paper bags and plastic bags, and can be used extremely advantageously for preserving feed, fertilizer, food, and the like. In addition, foods suitable for packaging with the packaging bag of the present invention include:
Examples include grains such as rice, wheat, and soybeans, livestock meat, marine products, and processed products thereof.

In addition, the method of packaging using the packaging bag of the present invention requires less time and effort in the blending process and cost compared to the conventional method of directly mixing and blending the fungicide with the feed etc. before filling it into the bag. etc. can be omitted.

Hereinafter, the present invention will be further explained in detail by giving Examples. "Parts" described in Examples refer to "parts by weight."

Example / 97 parts of ethylene/vinyl acetate copolymer (Mitsubishi Yuka Co., Ltd. trade name Yucalon Ever X-j 02 grade),
3 parts of benzyl benzoate was added and stirred under to-toc heating to perform a heating impregnation treatment to obtain an impregnated resin. Adding 20 parts of a benzyl benzoate solution of ethyl vanillin with an ethyl vanillin concentration of 20% by weight to gO parts of this impregnated resin,
The mixture was stirred and impregnated at a temperature of 33 to 60 C to obtain a masterbatch of an ethylene/vinyl acetate copolymer resin composition containing ethyl vanillin at a concentration of 80% by weight.

3.3 parts of the masterbatch and low-density bolieterenta
parts were mixed and the vanillin concentration was adjusted to 0. /≠wt% bound low-density polyethylene (melt index 00) 9/no O minutes) resin composition, -//- high-density polyethylene (melt index 0.0.91)
1710 minutes), the inner and outer layers were formed into low-density polyethylene resin composition films by coextrusion inflation molding in a molten state, and the middle layer was formed into a high-density polyethylene film.The film thickness composition ratio of inner layer: middle layer: outer layer was made using of/:
, 2:/(Total film basisness/30μ) A tubular laminated film was produced.

This tubular laminated film (width soomrr)
The tube was cut into a length of Qmm and the end of the tube was heat sealed to form a bag. This bag contains cattle feed [l, 3% by weight of sugars, 33% by weight of grains, 7% by weight of vegetable oil meal, 7% by weight of others (calcium carbonate, calcium phosphate, etc.) 3 total 20
Filled and heat sealed. The obtained packaged feed is shown below.
The mold was left to stand under the conditions described in Note 7, and the state of mold growth was visually observed.

The results were as shown in Table-/.

Example 2 To 20 parts of the same ethylene-vinyl acetate copolymer used in Example 1, 70 parts of a benzyl benzoate solution of vanillin (vanillin concentration 20% by weight) was added,
Impregnation treatment was performed by heating and stirring at a temperature of 33 to 60 °C for about ≠ hours to obtain a masterbatch of an ethylene/vinyl acetate copolymer resin composition containing vanillin at a concentration of 2% by weight.

Low density polyethylene (melt index O1/) 93
7 parts of the masterbatch of the above ethylene/vinyl acetate copolymer resin composition was added to 1 part, and the vanillin content concentration was 0.
/% by weight of a resin composition was obtained. This resin composition was molded into a tubular film with a thickness of 3 μm by extrusion inflation molding.

This film tube (width! 00mm) is 100mm
The bag was cut into a length, and the end of the tube was heat-sealed to form a bag, which was then filled with the same feed and zokf as in Example, heat-sealed, and subjected to the same test as in Example. The results are shown in Table 1.

Example 3 3 parts of benzyl benzoate was added to 7 parts of the same ethylene/vinyl acetate copolymer used in Example/, and the same heated impregnation treatment as in Example/ was carried out to obtain an impregnated resin. . Separately, a mixture of so parts of ethyl vanillin and 30 parts of fly 9 was dissolved in benzyl benzoate to obtain a benzyl benzoate solution having a mixture concentration of ethyl vanillin and vanillin of 20% by weight.

Next, 20 parts of the above benzyl benzoate solution was added to the above impregnated resin go part, and heated and impregnated in the same manner as in Example 1 to obtain a concentration of 2% by weight of each of ethyl vanillin and vanillin. A masterbatch of an ethylene/vinyl acetate copolymer resin composition was obtained.

Add 2 parts of the master batch of the above ethylene/vinyl acetate copolymer resin composition to 3 parts of ethylene/vinyl acetate copolymer (Yukalon HE60 grade manufactured by Mitsubishi Yuka Co., Ltd.; vinyl acetate content 3%). The resulting resin composition was used as the inner layer (thickness/30μ), Nine-6 resin was used as the outer layer (thickness/jμ), and the intermediate layer was Modic (manufactured by Mitsubishi Yuka Co., Ltd.) as an adhesive resin. The film was molded into a tube-shaped laminated film using a coextrusion inflation molding method using a thickness of 100 μm/jμ). The concentrations of vanillin and ethyl vanillin in the inner resin layer of the obtained film were o and o, respectively.
g% by weight.

This film tube (width! θOmm) is 100 m
The bag was cut into a length of m, heat-sealed to form a bag, filled with cow feed in the same manner as in Example 1, and subjected to the same test. The results are shown in Table 7.

A comparative paper bag (a commercially available feed bag with three layers of kraft paper as the outer bag and a low-density polyethylene film as the inner bag) was made with a width of J' 00.
The bag was cut to a size of mm x vertical dimension QQ mm, and the ends were sealed using a sewing machine.Into the resulting bag, 0173% by weight of sodium propionate was directly mixed and blended as a fungicide. Other than that, the same cattle feed as in Example/20kIi
was filled and sealed using a sewing machine. The obtained packaged feed was tested under the same conditions as in Example. The results were 9 as shown in Table 1.

Table-/ Note) The test was as follows.

Test A: Leave in a constant temperature and humidity chamber at tioc temperature and 0% humidity for 2 months.

Exam B...June! 3-/Otsu- from March 3rd to July 3rd piled up outdoors for a month (open pile) The number of bags is 70 bags).

Judgment method: Judgment is made by visually observing the state of mold growth in both tests.

As is clear from the test results in Table 1, the feeds packaged in the packaging bags of each example developed mold, whereas the conventional feeds blended with sodium propionate and packaged in paper feed bags developed mold. No mold growth was observed.

Patent Applicant: 3.'Rhikoyu: Chemical Co., Ltd., etc./Name

Claims (1)

[Claims] /, vanillin and h/and fly vanillin at least 0
．． An anti-bacterial packaging bag formed from a film of a polyolefin resin composition containing 7% by weight of O.