JPH107892A - Antimicrobial macromolecular composition and antimicrobial packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which comprises a polyester prepared by copolymerization of an acid component, an alcohol component and a lower fatty acid glycerol ester, can be used as a packaging material for foods required to be safe with persistent antimicrobial effect. SOLUTION: This macromolecular composition comprises a polyester which is prepared by copolymerization of (A) an acid component (for example, terephthalic or adipic acid), (B) an alcohol component (for example, ethylene glycol, ε-caprolactone) and (C) a lower fatty acid glycerol ester component (for example, monocaprylin or monolaurin). In an embodiment, the objective compositicon is extruded singly or, when necessary, in combination thereof with a film-forming thermoplastic resin into film to give a packaging material is for forming bags or pouches. In another case, the composition is, for example, injected into a packaging material of a container form.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial polymer composition which can be used as a packaging material for foods requiring safety, and an antibacterial packaging material using the same. .

[0002]

2. Description of the Related Art As antibacterial packaging materials for foods, safety is required, so that wasabi extract (allyl isothionate cyanate), shiitake extract (polyacetylene compound), hinokitiol and basic A method has been adopted in which a substance having antibacterial properties such as protein protamine and the like is coated on the surface of a film for production.

[0003] However, since the substance having antibacterial properties has a high volatility and does not have heat resistance, the antibacterial effect does not last much.

It is conceivable that a substance having antibacterial properties is kneaded into the film, but the substance having antibacterial properties bleed out to the surface alone has a weak antibacterial effect.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such a problem, and it is an object of the present invention to use it in a packaging material for foods requiring safety. It is an object of the present invention to provide an antibacterial polymer composition which can maintain the antibacterial effect and maintain the contents of the antibacterial product by maintaining the antibacterial effect, and a packaging material having the antibacterial property using the same.

[0006]

The antibacterial polymer composition according to claim 1 is characterized by comprising a polyester obtained by copolymerizing an acid component, an alcohol component and a glycerin lower fatty acid ester component.

According to a second aspect of the present invention, there is provided a packaging material having antibacterial properties, wherein an antibacterial polymer composition comprising a polyester obtained by copolymerizing an acid component, an alcohol component and a glycerin lower fatty acid ester component is used. Things.

Hereinafter, the antimicrobial polymer composition and antibacterial packaging material according to the present invention will be described in detail.

The acid components constituting the copolymerized polyester include terephthalic acid, phthalic acid, isophthalic acid, aromatic carboxylic acids such as naphthalenedicarboxylic acid and paraoxybenzoic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacin And aliphatic carboxylic acids such as acids.

The alcohol component includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, and cyclohexanedimethanol. And the like. In addition, oxyacids such as γ-butyrolactone and ε-caprolactone are exemplified.

The glycerin lower fatty acid ester component includes monocabrylin, monocabulin, monolaurin and the like.

Then, the acid component, alcohol component and glycerin lower fatty acid ester component are copolymerized (condensed) to obtain an antibacterial polymer composition comprising a polyester.

The antibacterial polymer composition thus obtained is extruded alone or together with a thermoplastic resin constituting a heat sealing layer provided as required, into a film, to form a packaging material for bag making. May be produced, or a container-shaped packaging material may be produced by injection molding.

Further, the application of the antibacterial polymer composition according to the present invention is not limited to food packaging materials, and it can be injection-molded, so that it can be used in kitchens and baths where antibacterial properties are required. Household goods used, cards used at hospitals, etc.
It is a wide variety.

[0015]

According to the antibacterial polymer composition of the present invention, glycerin lower fatty acid ester, which has antibacterial properties and exerts a wide variety of fungi, is used as a part of the copolymer. The antibacterial effect lasts.

According to the antibacterial packaging material according to the second aspect of the present invention, the preservability of the contents to be packaged is improved.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail.

Example 1 (Synthesis of lower fatty acid ester) 46 g of glycerin was dissolved in 200 ml of pyridine at room temperature, and 300 g of trityl chloride dissolved in 1000 ml of pyridine was added dropwise to the system under light shielding. C. and reacted for 6 hours. After completion of the reaction, pyridine was distilled off under reduced pressure, and the residue was extracted with ethyl acetate / water. The ethyl acetate layer was dried and concentrated. The residue was recrystallized from benzene to obtain glycerin ditrityl ether (a) (yield: 55%).

Next, 57.6 g of ditrityl ether (a)
Was dissolved in 500 ml of tetrahydrofuran (THF) at room temperature, and 200 ml of pyridine was added. The system is cooled to 10 ° C. or lower, and 16.5 g of caprylic acid chloride (n = 6) dissolved in 100 ml of THF is added dropwise under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was stirred at 10 ° C. or lower for 30 minutes, returned to room temperature, and stirred for 5 hours.

After completion of the reaction, THF and pyridine were distilled off under reduced pressure, the residue was extracted with benzene / water, and the benzene layer was dried and concentrated. The residue was recrystallized from benzene / ethanol to obtain an intermediate product (b) (yield: 70%).

14.0 g of the intermediate product (b) was added to 50 ml of acetic acid.
And 50 ml of a 25% hydrogen bromide acetic acid solution was added dropwise at room temperature. After stirring for 30 minutes after the dropwise addition, the system was cooled to 5 ° C. or less,
The deposited precipitate was separated by filtration, and the filtrate was distilled off under reduced pressure. The residue was dissolved in methylene chloride, washed with a 5% aqueous NaHCO ₃ solution and a saturated aqueous NaCl solution, dried and concentrated. The residue was purified by silica gel column chromatography to obtain a lower fatty acid ester (c) (yield: 75%).

[0022]

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Here, R ₁ is an alcohol protecting group for a primary hydroxyl group as described below.

[0024]

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R ₂ is R ₂ ＲCH ₃ (CH ₂ ) _n
However, n = 6,7,8,9,10.

(Copolymerization) Dimethyl terephthalate 38.8
g, butanediol 36.0 g, the lower fatty acid ester (c) synthesized above 87.2 g, and antimony (III) oxide
0.1 g of the mixture was subjected to transesterification at 140 to 240 ° C. under a nitrogen stream. After the methanol generated in the reaction was distilled off, 40.4 g of sebacic acid was added, and 200
The esterification reaction is carried out at ~ 250 ° C and 240
Condensation polymerization was performed at -280 ° C for 5 hours to obtain an antibacterial polymer composition (molecular weight: about 15,000).

Example 2 (Synthesis of lower fatty acid ester) 2,2-dimethyl-1,2
13.2 g of 3-dioxetane-4-methanol was added to THF
It was dissolved in 500 ml, and 200 ml of pyridine was added.
Reduce the temperature of the system to 10 ° C or less, and add 100 ml of THF under a nitrogen atmosphere.
Was added dropwise to 19.1 g of caprylic acid chloride (n = 8). After completion of the dropwise addition, the mixture was stirred at 10 ° C. or lower for 30 minutes, returned to room temperature, and stirred for 5 hours.

After completion of the reaction, THF and pyridine were distilled off under reduced pressure, the residue was extracted with an ethyl acetate / water system, and the ethyl acetate layer was dried and concentrated. The residue was purified by silica gel column chromatography to obtain an intermediate product (d) (yield:
70%).

Next, 14.3 g of the intermediate product (d) was added to THF 2
Dissolve in 100 ml and add dropwise 100 ml of 0.1N HCl. After the addition, the mixture was hydrolyzed in a suspended state at room temperature for 2 hours. After completion of the reaction, liquid separation was performed, and the organic layer was neutralized with a 5% aqueous NaHCO ₃ solution, washed with a saturated aqueous NaCl solution, dried, and concentrated. The residue was purified by silica gel column chromatography to obtain a lower fatty acid ester (e) (yield: 85).
%).

[0030]

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(Copolymerization) Dimethyl terephthalate 38.8
g, 24.8 g of ethylene glycol, 98.4 g of the lower fatty acid ester (e) synthesized above, and germanium oxide (I
V) A transesterification reaction of 0.1 g of the mixture was performed at 160 to 220 ° C under a nitrogen stream. After distilling off methanol generated during the reaction, adipic acid 29.2 g, isophthalic acid 3
3.2 g was added, esterification was performed at 200 to 240 ° C, and then condensation polymerization was performed at 260 to 280 ° C under reduced pressure for 4 hours to obtain an antibacterial polymer composition (molecular weight: about 1).
8000).

Example 3 (Synthesis of Lower Fatty Acid Ester) Pentaerythritol 1
3.6 g was dissolved in 500 ml of water at room temperature. After dissolution,
A small amount of dilute hydrochloric acid was added and then 15.9 benzaldehyde.
g was slowly added dropwise and vigorously stirred to produce white crystals. After the addition, the mixture is further stirred for 2 hours.
The precipitate was separated by filtration, repeated with ice-cold water, washed, and recrystallized from water to obtain monoacetal (f) (yield: 55%).

10.6 g of monoacetal (f) was added to THF5
Dissolve in 00 ml and add 200 ml of pyridine. The system was cooled to 10 ° C. or lower, and 33.0 g of caprylic acid chloride (n = 6) dissolved in 100 ml of THF was added dropwise under a nitrogen atmosphere. After completion of the dropwise addition, return to room temperature for 30 minutes at 10 ° C or
Stirred for hours.

After completion of the reaction, THF and pyridine were distilled off under reduced pressure, the residue was extracted with ethyl acetate / water, and the ethyl acetate layer was dried and concentrated. The residue was generated by silica gel column chromatography to obtain an intermediate product (g) (yield: 65).
%).

Next, 11.6 g of the intermediate product (g) was added to acetic acid 2
The mixture was dissolved in 00 ml, 2.0 g of 5% Pd / C was added, and hydrogenolysis was performed at room temperature. After completion of the reaction, Pd / C was separated by filtration, the filtrate was concentrated under reduced pressure, and the residue was formed by silica gel column chromatography to obtain lower fatty acid ester (h)
Was obtained (yield: 80%).

[0036]

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(Copolymerization) Dimethyl terephthalate 9.8
g, butanediol 9.0 g, the lower fatty acid ester (h) 19.4 g synthesized above, and antimony (III) oxide 0.1 g.
1 g and a mixture of zinc acetate 0.1 g under a nitrogen stream 140-
A transesterification reaction was performed at 240 ° C. After distilling off the methanol generated during the reaction, 10.1 g of sebacic acid was added, the esterification reaction was performed at 200 to 250 ° C, and the condensation polymerization was performed at 240 to 280 ° C under reduced pressure for 5 hours to obtain an antibacterial polymer. A composition was obtained (molecular weight: about 16,000).

(Evaluation) The antibacterial properties were evaluated in Examples 1 to 3 above.
Resin was extruded into a 30 μm thick film and a 30 μm thick low density polyethylene (L
DPE) film coated with a mixture of caprylic acid monoglyceride and oleic acid monoglyceride (Comparative Example 1), and a low-density polyethylene film (Comparative Example 2) were cut into 25 × 25 mm each, and Penicilln roqueforti, Aspergillus niger, M
ucor racemosus was planted and placed on the culture.

Then, Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for the prevention of mold growth.

[0040]

[Table 1]

In the above table,-means that no mold has grown. + Indicates that the mold is growing, and the number of + indicates the degree of growth of the mold.

From the above table, it is found that Examples 1 to 3
No mold growth was observed even after 0 days, but it can be seen that mold growth was observed after 20 days in Comparative Example 1.

[0043]

According to the antibacterial polymer composition according to the first aspect of the present invention, a glycerin lower fatty acid ester which has antibacterial properties and is effective for a wide variety of bacteria can be used as a copolymer. Antimicrobial effect lasts because it has as a part.

According to the antibacterial wrapping material according to the second aspect of the present invention, the preservability of the contents to be wrapped is improved.

Therefore, the antimicrobial polymer composition which can be used as a packaging material for foods requiring safety and which has an improved antimicrobial effect to improve the preservability of the contents and a use thereof. The present invention can provide a packaging material having antibacterial properties.

Claims (2)

[Claims] An antibacterial polymer composition comprising a polyester obtained by copolymerizing an acid component, an alcohol component and a glycerin lower fatty acid ester component. 2. An antibacterial packaging material using an antibacterial polymer composition comprising a polyester obtained by copolymerizing an acid component, an alcohol component and a glycerin lower fatty acid ester component.