JPH09278962A - Antibacterial film for food packaging - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial food-packaging film having various film properties necessary for food-packaging use such as self-tackiness, transparency and antifogging property and exhibiting high antibacterial property while keeping the above film properties. SOLUTION: This antibacterial food-packaging film contains 100 pts.wt. of a polyvinyl chloride resin, 5-50 pts.wt. of a plasticizer, 0.3-3.0 pts.wt. of a stabilizer, 0.02-1.0 pts.wt. of a hydrotalcite, 0.1-5.0 pts.wt. of an antifogging agent and 0.02-2.0 pts.wt. of an antibacterial composition. The antibacterial composition is e.g. a material produced by exchanging the metal ion of an inorganic oxo acid salt with an antibacterial metal ion, exchanging the metal ion of magnesium metasilicate aluminate with an antibacterial metal ion or attaching or combining an antibacterial metal component to colloidal particles of an inorganic oxide such as SiO2 or TiO2 having an average particle diameter of <=500nm and constituting a colloidal solution.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyvinyl chloride-based film for food packaging, which has high antibacterial properties and is also excellent in self-adhesiveness, transparency and antifogging property.

[0002]

2. Description of the Related Art A polyvinyl chloride-based film for food packaging has come to be used in large quantities as a packaging material for fresh foods in parallel with the establishment of self-service (supermarket) sales. Also, in general households, due to the widespread use of refrigerators and microwave ovens, a large amount of this type of film is used as a packaging material for food storage and cooking applications.

Regarding the polyvinyl chloride-based film for food packaging used for these purposes, self-adhesiveness necessary for food packaging, freshness retention due to appropriate gas permeability, anti-fog property, and stretch. And transparency are required.

By the way, as a method of imparting antibacterial properties to an organic polymer film, an inorganic composition having an antibacterial action is used, and this inorganic composition is dispersed in the organic polymer.
A method of forming this into a film and a method of applying the inorganic composition having the antibacterial action to the surface of the organic polymer film are known. As this type of inorganic composition having antibacterial properties, those in which antibacterial ions are supported on zeolite or aluminosilicate are known.

Also in the film for food packaging, in order to impart antibacterial property, an antibacterial composition in which antibacterial ions such as silver are supported on zeolite or aluminosilicate is used, and the antibacterial composition is made of an organic polymer. It is known to disperse it in a film and form it into a film.

[0006]

However, the above-mentioned conventionally known granular bodies of the antibacterial composition have poor dispersibility, so that the self-adhesiveness, transparency and antifogging property are significantly impaired. Therefore, the wrapping property of the food to be packaged and the product value at the time of displaying the product in the food store are impaired, and a satisfactory product for use in food packaging cannot be obtained.

When an antibacterial composition is added to a vinyl chloride resin, chlorine released from the resin during thermoforming is
When combined with a metal ion such as silver that develops antibacterial properties, insoluble silver chloride or the like is produced, and thus the added antibacterial composition is consumed, the antibacterial properties are significantly reduced.

By the way, even if the antibacterial composition is consumed in the molding process as described above, in order to develop the necessary antibacterial property, a large amount of the antibacterial composition is expected in consideration of the consumption of the antibacterial composition in advance. It is considered that the substance is added to the vinyl chloride resin.

However, if the amount of the antibacterial composition to be added is large, the film properties for food packaging, which is essential, are impaired. On the other hand, if the addition amount is within a range that satisfies the film properties for food packaging, high antibacterial properties cannot be imparted due to the relationship with the consumption amount of the antibacterial composition as described above.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide various film characteristics such as self-adhesiveness, transparency, and antifogging property required for being used for food packaging. An object of the present invention is to provide a film for packaging an antibacterial food, which has high antibacterial properties while ensuring this.

[0011]

In order to achieve the above object, the inventors of the present invention have intensively studied a polyvinyl chloride resin compound composition for food packaging having antibacterial properties, and as a result, the present invention has been completed. I arrived.

That is, the invention according to claim 1 is based on 100 parts by weight of a polyvinyl chloride resin, and a plasticizer of 5 to 50.
Parts by weight, stabilizer 0.3 to 3.0 parts by weight, hydrotalcites 0.02 to 1.0 part by weight, antifog agent 0.1 to 5.0
By weight, the antibacterial composition is contained in an amount of 0.02 to 2.0 parts by weight.

According to the invention of claim 2, the antibacterial composition is
The metal ion of an inorganic oxoacid salt is ion-exchanged with a metal ion having antibacterial properties.

The invention according to claim 3 provides an antibacterial composition,
The metal ion of magnesium aluminometasilicate is ion-exchanged with a metal ion having an antibacterial property.

The invention according to claim 4 provides an antibacterial composition,
It is characterized in that the inorganic oxide colloidal particles constituting the colloidal solution are adhered or combined with a metal component having antibacterial properties.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the antibacterial food packaging film according to the present invention will be described in detail below.

This antibacterial food packaging film comprises a polyvinyl chloride resin, a plasticizer, a stabilizer, hydrotalcites, an antifogging agent and an antibacterial composition.

The polyvinyl chloride resin contains a vinyl chloride homopolymer and vinyl chloride in an amount of 10% by weight or more,
It is a copolymer, a graft copolymer, or a block copolymer with this and a copolymerizable monomer. Examples of the comonomer, ethylene, propylene, olefins such as polybutene, vinyl acetate, vinyl laurate, acrylic acid ester, saturated vinyl ester such as methacrylic acid methyl ester, unsaturated alkyl ester, alkyl vinyl ether such as lauryl vinyl ether, Examples thereof include maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, vinylidene fluoride and the like. Further, polyvinyl chloride is, for example, acrylonitrile-butadiene-styrene, ethylene-vinyl acetate, chlorinated polyethylene, methacrylic acid methyl ester-butadiene-.
A halogen-containing resin such as a polymer blend with a three-dimensional polymer of styrene or the like, a post-treated product of polyvinyl chloride with an alcohol or the like, or a post-chlorinated product.

As the plasticizer to be blended as the first component, epoxidized linseed oil, epoxidized soybean oil, epoxidized oils such as epoxidized fatty acid alkyl ester, and linear or branched alkyl groups having 6 to 10 carbon atoms. Adipic acid esters, tributyl acetyl citrate, hydroxy polycarboxylic acid esters such as acetylated triethyl, dibasic acid esters of fatty acids such as di-n-butyl sebacate, pentaerythritol ester, glycol esters such as diethylene glycol benzoate Kind,
Examples thereof include phosphoric acid esters such as triphenyl phosphate and tricresyl phosphate, glycerin diacetomonolaurate, chlorinated paraffin and polyester plasticizers. These are used alone or in combination of two or more.

The amount of the plasticizer added is appropriately adjusted within the range of 5 to 50 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, depending on the type of food to be packaged, the packaging form, the packaging method and other applications.

The stabilizer to be added as the second component is acetic acid, propionic acid, heptanoic acid, 2-ethylhexylic acid, caprylic acid, capric acid, lauric acid, palmitic acid, myristic acid, stearic acid, undecylenic acid, isostearic acid. Acid, 12-hydroxystearic acid, isodecanoic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, docosanoic acid, eicoic acid, nodecanoic acid, behenolic acid, tallow fatty acid, coconut oil fatty acid, soybean oil fatty acid, tung oil fatty acid, and Mixture of naturally occurring fatty acids such as rice sugar oil fatty acid, lactic acid, citric acid, gluconic acid, sorbic acid, rosin acid, acetoacetic acid, benzoic acid, naphthenic acid, salicylic acid, p-tert-butylbenzoic acid, isopropylbenzoic acid, ethyl Benzoic acid, toluic acid, xylyl acid, 5-tert- Corruptible acid and monovalent carboxylic acids such as cyclohexyl carboxylic acid, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Divalent or polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, clophthalic acid, aminophthalic acid, oxyphthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, isoconic acid and aconitic acid, and their monocarboxylic acids. Included are calcium and zinc salts such as ester carboxylic acids.

Further, as an auxiliary agent of the above-mentioned stabilizer, trisnonyl phosphite, 2-tert-butyl-α
(3-tert-butyl-4-hydroxyphenyl) p
-Cumenylbis (p-nonylphenol) phosphite, 4,4'-isopropylidene-diphenylalkyl (C12-C15) phosphite, tris (2,4-te)
organic phosphites such as rt-butylphenyl) phosphite, tris (dinonylphenyl) phosphite, distearylpentaerythritol-diphosphite, stearoylbenzoylmethane, benzoylacetylmethane, benzoylhexanoylmethane, benzoylocta Noylmethane, diacetylbenzoylmethane,
Β-diketones such as lauroylbenzoylmethane, dibenzoylmethane, oleylbenzoylmethane and β-diketones
Metal complex salts of diketones can be added.

The amount of stabilizer added depends on the molding method, molding equipment,
The amount is appropriately adjusted in the range of 0.3 to 3.0 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin according to the product application.

The hydrotalcites compounded as the third component are represented by the following general formula (1).

[0025] ^{_{Mg +2 1-X A l X}} (OH) 2 A 2- x / 2 · mH 2 O ... (1) ( in the formula, Mg ⁺² is of Mg or Mg and Zn solid solution, A ^2-
Is CO ₂ or SO ₄ , x is 0 <x ≦ 0.5, and m is a positive real number. )

By incorporating such hydrotalcites, the antibacterial property of the antibacterial composition can be maintained. That is,
By mixing hydrotalcites, a metal or metal ion that captures and stabilizes chlorine that is released during thermoforming of vinyl chloride resin and develops antibacterial properties such as silver is combined with chlorine components and insoluble silver chloride, etc. It is possible to maintain the antibacterial properties of the compounded antibacterial composition, since it is possible to suppress the generation of

The use of hydrotalcites as a heat stabilizer for vinyl chloride resins is known to give a color to the resin after thermoforming, but it is a major component of the antibacterial composition. When hydrotalcites are used in combination with magnesium aluminometasilicate, which is the above, the problem of coloring of this kind can be remarkably improved.

The hydrotalcites are used in the range of 0.02 to 1.0 part by weight based on 100 parts by weight of the polyvinyl chloride resin.

Examples of the antifogging agent added as the fourth component include monoglycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid ester, and the like.
These are used alone or in combination of two or more.

The amount of antifogging agent added is in the range of 0.1 to 5.0 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, depending on the type of food to be packaged, the packaging form, the packaging method and other applications. Adjust accordingly.

The antibacterial composition to be added as the fifth component is divided into two types having an inorganic oxoacid salt and inorganic oxide colloidal particles as a base material, and each has the following characteristics.

An antibacterial composition containing an inorganic oxo acid salt as a base material is amorphous and has a particle size of 2 μm or less, particularly 0.5 μm.
The following is preferable, and it has ion exchange capacity and is insoluble in water. An example of such a device is disclosed in Japanese Patent Laid-Open No. 03-275627. Such insolubility in water makes it difficult for the antibacterial composition to elute at the time of packaging food, etc., and enables the antibacterial property to be maintained for a long time. Further, it is amorphous and has a particle size of 0. When it is 0.5 μm or less, it is possible to sufficiently satisfy various properties such as self-adhesiveness, transparency and antifogging property required for the food packaging film. Therefore,
This kind of antibacterial composition can be applied within a range of particle size that can satisfy both long-term antibacterial property and various properties such as self-adhesiveness.

Examples of the above-mentioned inorganic oxo acid salts include magnesium aluminometasilicate, calcium silicate, calcium titanate, sodium antimonate and the like. In particular, from the viewpoint of safety and the effect of preventing the resin from being colored when used in combination with the fourth component, it is preferable to use magnesium aluminometasilicate. Examples of the antibacterial metal ion that is ion-exchanged with the inorganic oxo acid salt include Ag, Cu, Zn, and Sn, and these are used alone or in combination of two or more.

The antibacterial composition using inorganic oxide colloidal particles as a base material has a mean particle size of 500 nm which constitutes a colloidal solution.
The following inorganic oxide colloidal particles such as SiO ₂ and TiO ₂ have Ag, Cu, Zn, and
It is a composition in which components such as Sn are attached or combined. For example, Japanese Patent Laid-Open No. 07-33616 is applicable to this.
There is one disclosed in Japanese Patent Application Laid-Open Publication No. H10-26095. This kind of antibacterial composition is in the form of a colloidal solution and has an extremely small particle size, so that it has excellent dispersibility and does not impair self-adhesiveness, transparency, antifogging and the like. Furthermore, since the antibacterial composition is leached on the film surface together with the compounding material such as a plasticizer and an antifogging agent due to its properties, the concentration of the antibacterial composition on the film surface can be kept high.

The antibacterial composition using the inorganic oxo acid salt as a base material and the antibacterial composition using inorganic oxide colloidal particles as a base material are both 100 parts by weight of polyvinyl chloride resin. To 0.02 to 2.0 parts by weight.

Incidentally, in addition to the polyvinyl chloride resin, if necessary, pigments, lubricants, fillers, plate-out inhibitors, antioxidants, release agents, viscosity reducing agents, surfactants,
A fluorescent agent, a surface treatment agent, a cross-linking agent, a reinforcing agent, a processing aid and the like can be included.

[0037]

EXAMPLES Next, examples of the antibacterial food packaging film according to the present invention will be described with reference to comparative examples, but the present invention is not limited to the description of these examples. Absent.

In this example, the components shown in Table 1 were blended, hot blended with a Henschel type heater mixer, transferred to a cooler mixer and cooled, and the blend thus obtained was subjected to T-die. It was formed into a film by the method.

In Example 1, as the antibacterial composition, a metal ion of magnesium aluminometasilicate having a particle size of 0.5 μm or less and having a particle size of 0.5 μm or less was ion-exchanged with a metal ion having an antibacterial property.

In Example 2, an antibacterial composition was used in which a metal component having an antibacterial property was attached to or combined with colloidal inorganic oxide colloidal particles of SiO ₂ and TiO ₂ having a mean particle size of 500 nm or less. .

As Comparative Example 1, a known zeolitic antibacterial composition was used, and as Comparative Example 2, an antibacterial composition was not added.

With respect to the films of the above Examples and Comparative Examples, the transparency, self-adhesiveness, antifogging property and antibacterial property were evaluated by the test methods shown below, and the evaluation results are shown in Table 1.
Also described in the inside.

The transparency was measured using an automatic haze meter (NDH-24 type manufactured by Nippon Denshoku Industries Co., Ltd.) and a gloss meter (GM-3D type manufactured by Murakami Color Co., Ltd.). It is preferable that the food packaging film has a high light transmittance and a low haze.

In the evaluation of self-adhesiveness, a T-peel peel strength in 250 mm width of the film was measured using Strograph R2 manufactured by Toyo Seiki Co., Ltd., and this was taken as the adhesive strength.

The evaluation results of transparency and self-adhesiveness were compared with the measured values of the film obtained in Comparative Example 2, and the reduction rate was as follows. That is, 0
A decrease rate of less than 3% is indicated by "⊚", a decrease rate of less than 5% is indicated by "○", and a decrease rate of 5% or more is indicated by "x".

The antifogging property was evaluated as follows. That is, 200 ml of distilled water having a water temperature of 20 ± 3 ° C. is put in a 500 ml beaker, a film is attached to the beaker opening so that no wrinkles are formed, and this is immediately put in a commercial refrigerator kept at a temperature of 0-3 ° C., The change in the state of the film surface was observed.

Regarding the evaluation standard of the anti-fogging property, "⊚" indicates that there are few water drops, "○" indicates that there are a few water drops but within the allowable range, and "x" indicates that there are many water drops. did.

Regarding the evaluation of antibacterial property, Staphylococcus aureus was used as a test bacterium, and the antibacterial property of the film was evaluated by the mortality rate. The test method was to cut the films of the above Examples and Comparative Examples to a size of 50 mm × 50 mm, put each of the cut films in a sterilized petri dish, and put them in a culture solution of Staphylococcus aureus (10 ⁴ cells / ml). 0.5)
ml was inoculated, and the inoculated product was allowed to stand at 35 ° C. for 24 hours, and then the mortality reduction rate was calculated according to the viable cell count method. In addition, when the sign of the mortality rate is negative, it means that the number of bacteria is increased.

Details of the compounding materials used in the above examples are as follows.・ Polyvinyl chloride resin: TK, a product of Shin-Etsu Chemical Co., Ltd.
-1100 ・ Diisononyl adipate: Mitsubishi Chemical Vinyl Co., Ltd. product DINA ・ Epoxidized linseed oil: Asahi Denka Kogyo Co., Ltd. product O-
180 ・ Stabilizer: Akishima Chemical Industry Co., Ltd. product FD-30 ・ Hydrotalcite: Kyowa Chemical Industry Co., Ltd. product Alcamizer-4 ・ Polyglycene fatty acid ester: Riken Vitamin Co., Ltd. product O-71D ・ Antibacterial composition A : Catalyst Kasei Kogyo Co., Ltd. product AIS-N
AZ320 ・ Antibacterial composition B: Catalytic Chemicals Co., Ltd. product ATOMY
BALL ・ Antibacterial composition C: Silver zeolite antibacterial agent

[0050]

[Table 1]

[0051]

The antibacterial food packaging film according to the present invention comprises 5 to 50 parts by weight of a plasticizer, 0.3 to 3.0 parts by weight of a stabilizer and 100 parts by weight of a polyvinyl chloride resin. Talcite 0.02 to 1.0 part by weight, antifogging agent 0.
1 to 5.0 parts by weight and 0.02 to 2.0 parts by weight of the antibacterial composition. With such a formulation, a film that can achieve both high antibacterial properties and various film properties such as self-adhesiveness, transparency, and antifogging properties required for food packaging can be obtained. It is presumed that such an effect is based, for example, on the compounding action of hydrotalcites (maintaining the antibacterial property of the antibacterial composition).

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C08K 3/34 KGN C08K 3/34 KGN (72) Inventor Shinichi Ota 1245 Morisoejima Shimodate City, Ibaraki Hitachi Boarden Inside Shimodate Factory (72) Inventor Katsuhiro Shirono 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Catalyst Kasei Kogyo Co., Ltd. Inside Wakamatsu Factory (72) Inventor Atsushi Tanaka 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka Kasei Industry Co., Ltd. Wakamatsu factory

Claims (4)

[Claims] 1. A plasticizer of 5 to 50 parts by weight, a stabilizer of 0.3 to 3.0 parts by weight, and a hydrotalcite of 0.02 to 1.0 part by weight based on 100 parts by weight of a polyvinyl chloride resin. ,
Antifogging agent 0.1-5.0 parts by weight, antibacterial composition 0.02-
An antibacterial food packaging film comprising 2.0 parts by weight. 2. The antibacterial composition according to claim 1, wherein the metal ion of the inorganic oxoacid salt is ion-exchanged with the metal ion having antibacterial property. the film. 3. The antibacterial composition is characterized in that the metal ion of magnesium aluminometasilicate is ion-exchanged with a metal ion having antibacterial property.
The antibacterial food packaging film described. 4. The antibacterial food according to claim 1, wherein the antibacterial composition is obtained by adhering or combining an inorganic oxide colloidal particle forming a colloidal solution with a metal component having an antibacterial property. Packaging film.