JPH0729886B2 - Antibacterial and antifungal gel alcohol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an easy-to-produce gel alcohol composition for bactericidal and mildew proofing, which utilizes the bactericidal action of lower alcohols.

[Prior Art] The bactericidal properties of lower alcohols have been well known,
Used as alcohol vapor for antibacterial and antifungal applications such as food and feed. However, if the source of such alcohol vapor remains liquid, even if alcohol is placed in a bag-like container and placed in the system, it may come into direct contact with the contents due to liquid leakage due to vibration or shock. Always exists.

Therefore, as represented by Japanese Patent Publication No. 55-2273, powdered ethanol prepared by adsorbing ethanol to a carrier such as starch, cellulose, silicon dioxide or the like may be used, or JP-A-56-3090.
In Japanese Patent Laid-Open No. 3, a leak is prevented by using gelled ethanol formed by gelling ethanol with a condensation reaction product of D-sorbitol and benzaldehyde.

[Problems to be Solved by the Invention] However, in the powdered ethanol represented by JP-B-55-2273, the sterilization effect is inferior in sustainability because the adsorbed ethanol vaporization rate is too fast, and There is a problem such as the smell of ethanol being transferred to the contents. Regarding this point, in JP-A-56-30903, the evaporation rate is suppressed by using gel-like ethanol. Such a gel-like material is obtained by adding a condensation reaction product of D-sorbitol and benzaldehyde to ethanol. Since it is produced by a method such as heating, melting, cooling, and gelling, there is a problem that the operation is complicated.

As described above, it is still insufficient to obtain a gel alcohol excellent in the sustainability of the bactericidal effect by a simple production method by any of the conventional methods.

[Means for Solving the Problems] Therefore, as described above, the present inventors have an advantage that the gel state is more effective in suppressing the evaporation rate of alcohol than the powder state, and exhibits the antibacterial and antifungal effect for a long time. In order to improve the conventional drawbacks of the gel containing alcohol, in the case of using a polyvinyl alcohol (hereinafter abbreviated as PVA) resin having a specific degree of polymerization and saponification, Furthermore, they have found that such an object can be achieved, and have completed the present invention.

That is, the present invention provides "a PVA-based resin 10 having a polymerization degree of 400 or more and a saponification degree of 40 to 55 mol%.
A gel alcohol composition for antibacterial and antifungal treatment, which comprises 0 to 0 parts by weight of 70 to 300 parts by weight of an alcohol having 1 to 3 carbon atoms. It is.

A feature of the present invention is to use a gel-like material in which a lower alcohol is contained in a PVA resin having a specific weight degree and a saponification degree range. As a result, a gel alcohol composition for bactericidal and mildew-proofing, which has an excellent sustaining effect of bactericidal effect, can be obtained by a simple operation.

The PVA resin of the present invention may be not only a saponified product of polyvinyl acetate but also a saponified product of a copolymer obtained by copolymerizing a small amount of components other than vinyl acetate.

As components other than vinyl acetate, for example, ethylene, propylene, isobutylene, α-octene, α-dodecene, α
-Olefins such as octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, unsaturated acids such as itaconic acid or salts or mono- or dialkyl esters thereof, acrylonitrile, nitriles such as methacrylonitrile, Amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, N-
Examples thereof include acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.

Further, PVA which has been post-modified such as acetalized, glyoxalized, acetoacetylated, esterified, sulfonated or cationized can also be used.

The polymerization degree of the PVA-based resin of the present invention is 400 or more, preferably 50.
It is 0 or more. If it is less than 400, the PVA resin is dissolved in alcohol and becomes a paste.

The degree of saponification of the PVA resin of the present invention is 40 to 55 mol%, preferably 45 to 55. If it is less than 40 mol%, the PVA-based resin will be dissolved in alcohol as in the above case. When it exceeds 55 mol%, the PVA resin becomes powdery and does not form a gel.

As the alcohol of the present invention, those having 1 to 3 carbon atoms can be used, and examples thereof include methanol, ethanol, 1-propanol, and 2-propanol.

The mixing ratio of the PVA-based resin of the present invention and the alcohol is 70 to 300 parts by weight, preferably 100 to 250 parts by weight, based on 100 parts by weight of the PVA-based resin. If it is less than 70 parts by weight, the amount of alcohol contained is too small and the sterilizing ability is too low, which is not practical. If it exceeds 300 parts by weight, phase separation will occur and gelation will not occur.

The PVA-based resin of the present invention is produced by saponifying a polyvinyl acetate-based resin in alcohol, and is generally obtained in paste form immediately after saponification. Therefore, when such resin is used in powder form, paste It is adjusted by distilling off the solvent therein and, if necessary, drying and then pulverizing the obtained block by a method such as pulverizing.

In producing the gel alcohol composition of the present invention using the powder, a predetermined amount of alcohol is added to the powder PVA-based resin and the mixture is stirred and mixed at room temperature.

Further, in order to produce the gel body of the present invention from a paste-like material, the alcohol of the present invention is used as a solvent during polymerization or saponification, and the solvent is evaporated from the obtained paste-like saponified product to the proportion of the present invention. If so, a gel alcohol can be obtained as it is.

When the alcohol used at the time of polymerization or saponification is different from the alcohol used at the time of gel production, the paste-like saponified product may be replaced with the required alcohol by any means.

In addition, other known bactericides and other additives such as pigments may be added to the gel alcohol composition at the time of production or the like. In particular, at the time of production, polyalcohol such as glycerin, propylene glycol, polyethylene glycol, and sorbitol is appropriately mixed and produced to control the alcohol evaporation rate of the obtained gel alcohol or prevent the weathering of the gel body. It is possible to

The composition of the present invention is mainly a raw product such as bread, meat and fish,
It is particularly useful as an antibacterial and antifungal agent for foods such as dried foods, grains, vegetables and fruits, but is not limited to foods. When using, seal the target substance in any bag or container,
The composition of the present application may be added to this.

As the packaging form when using the composition of the present invention, it may be directly placed as it is unwrapped, or placed in a container such as a closed container or a bag composed of an alcohol permeable resin film. However, there is no particular limitation. Examples of commonly used alcohol permeable resins include polyethylene, polypropylene, ethylene-vinyl acetate copolymer PAV and the like.

[Action] The gel-like alcohol composition for antibacterial and antifungal of the present invention is obtained by a simple operation, and the PVA-based resin having a specific degree of polymerization and saponification used in the present invention is an alcohol to be contained. It has the effect of appropriately suppressing the evaporation rate of.

[Examples] Next, the present invention will be described in detail with reference to Examples.

(I) Production of gel alcohol Production Example 1 PVA powder having a degree of polymerization of 500 and a degree of saponification of 50 mol% has a purity of 99% in 20 g of PVA powder.
20 g of ethanol was added, and the mixture was stirred at room temperature for 30 minutes to obtain gel alcohol (A).

100 parts by weight of ethanol was contained with respect to 100 parts by weight of PVA.

Production Examples 2 to 10 Instead of the PVA powder of Production Example 1 and ethanol, the first
In the same manner as in the same example except that PVA, silicon dioxide, and alcohol shown in the table were used, gel alcohol (B)-
(F) and (a) to (d) were obtained, and the content of alcohol is also shown in Table 1.

(Ii) Antibacterial and antifungal performance test Example 1 (see FIG. 1) Diameter containing sterilized potato dextrose agar medium (20% by weight of potato leachate, 2% by weight of glucose, 1.5% by weight of agar, pH 5.0) A 9 cm Petri dish 1 is placed in the center of a paper box 2 with a width of 25 cm, a depth of 34 cm, and a height of 8 cm (the interior of which is laminated with polyethylene) without the top lid 3, and the following 5 types of mold spore suspensions are used. Was sprayed onto the surface of the agar medium to inoculate.

Aspergillus niger (IFO 6341) Penicillius funiculosum (IFO 6345) Rhizopus stronifer (IFO 31005) Gladosporium Cladosporioides (IFO 634
8) Ketomius Globosum (IFO 6347) Next, place the aluminum foil plate 5 on which 10 g of the gel alcohol (A) 4 is placed in the corner of the paper box 2, and then put the top lid 3 on it and allow the paper box to cool to room temperature. It was stored.

The upper lid 3 was taken daily and the extent of mold growing on the agar medium was observed.

Control Example 1 An experiment was performed in the same manner as in Example 1 except that the gel alcohol was not used, and the results are shown in Table 2.

Examples 2 to 5, Control Example 2 The same as in Example 1 except that the gel alcohols (B) to (F) and (d) shown in Table 1 were used instead of the gel alcohol (A). An experiment was conducted in the same manner as the example, and the results are shown in Table 2.

(Iii) Alcohol Evaporation Rate Suppression Test Using gel alcohols (A) to (C), (b), and (d) shown in Table 1, the evaporation amount of the contained alcohol with time is shown. The measurement was performed to determine the evaporation rate of alcohol.

The results are shown in Table 2.

[Measurement method]

 The sample was left at room temperature (22.5 ° C) and the weight change was measured.

[Effects] The PVA-based resin having a specific degree of polymerization and saponification degree used in the gel alcohol composition for antibacterial and fungi of the present invention has an effect of appropriately suppressing the evaporation rate of the contained alcohol. Therefore, the present invention is extremely useful industrially because the composition has excellent bactericidal activity and the production method of the composition is simple.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of a paper box (the interior is laminated with polyethylene) used for the antibacterial and antifungal performance test of the gel alcohol for antibacterial and antifungal of the present application. It is the figure which has arrange | positioned the dish of the aluminum foil which put the alcoholic alcohol. 1; Petri dish containing agar medium 2; Paper box (main body) (internal polyethylene laminate) 3; Paper box top lid (internal polyethylene laminate) 4; Gel alcohol 5; Aluminum foil dish Fig. 2 shows various types shown in Table 1 Alcohol (A)
It is a figure explaining the alcohol evaporation rate calculated | required in the ethanol evaporation rate suppression test of (C) and (b), (d). A: Evaporation rate of gel alcohol obtained in Production Example 1 in Table 1. B: Evaporation rate of gel alcohol obtained in Production Example 2 in Table 1. C: Evaporation rate of the gel alcohol obtained in Production Example 3 in Table 1. b; Evaporation rate of the powdery alcohol obtained in Production Example 8 in Table 1. d; Evaporation rate of the powdery alcohol obtained in Production Example 10 in Table 1. e; Evaporation rate of 99% pure ethanol.

Claims (1)

[Claims] 1. A polyvinyl alcohol resin having a degree of polymerization of 400 or more and a degree of saponification of 40 to 55 mol% is added to 100 parts by weight of a polyvinyl alcohol resin having 1 to 1 carbon atoms.
A gel-like alcohol composition for antibacterial and antifungal treatment, which comprises 70 to 300 parts by weight of the alcohol of 3 above.