Antibacterial and antifungal composition

Abstract

An antibacterial and antifungal composition comprising (A) at least one member selected from the group consisting of dehydroacetic acid, sorbic acid and their alkali metal salts and (B) at least one member selected from the group consisting of o-phenylphenol and its alkali metal salts, p-chloro-m-xylenol, 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline and its salts and chelates, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile and N-(fluorodichloromethylthio)phthalimide. The antibacterial and antifungal effects can be synergistically increased when the component (A) is employed in combination with the component (B).

Description

BACKGROUND OF THE INVENTION

The present invention relates to a composition useful as antibacterial and antifungal agent, and more particularly to a composition mainly containing dehydroacetic acid, sorbic acid or their alkali metal salts.

It is well known that dehydroacetic acid, sorbic acid and their alkali metal salts are useful as antibacterial and antifungal agents. The toxicity of these antibacterial and antifungal agents is so low that their addition to foods is permitted, and they are agents of very high safety. Therefore, if these agents are usable in any fields such as general industrial products and agricultural products, to say nothing of foods, the usefulness of these agents becomes very great. However, the antibacterial and antifungal effects thereof are not always satisfactory, and they are restricted in the application to industrial products such as paints, sizing agents and adhesives.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided an antibacterial and antifungal composition comprising (A) at least one member selected from the group consisting of dehydroacetic acid, sorbic acid and their alkali metal salts and (B) at least one member selected from the group consisting of o-phenylphenol and its alkali metal salts, p-chloro-m-xylenol, 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline and its salts and chelates, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile and N-(fluorodichloromethylthio)phthalimide. The synergistic effect on the antibacterial and antifungal properties is very remarkable, when the component (A) is employed in combination with the component (B), and the composition of the invention can be availably employed as antibacterial and antifungal agents in various industrial products and agricaltural products.

DETAILED DESCRIPTION

There are employed, as the component (A) of the composition of the invention, dehydroacetic acid, sorbic acid and their alkali metal salts such as sodium dehydroacetate, potassium dehydroacetate, sodium sorbate and potassium sorbate. These compounds may be employed alone or in admixture thereof.

Examples of a compound employed as the component (B) of the composition of the invention are o-phenylphenol and its alkali metal salts shown by the following formula: ##STR1## wherein X is hydrogen or an alkali metal, p-chloro-m-xylenol shown by the following formula: ##STR2## 2-(4-thiazolyl)-1H-benzimidazole shown by the following formula: ##STR3## 8-hydroxyquinoline shown by the following formula: ##STR4## salts of 8-hydroxyquinoline with organic or inorganic acids such as hydrochloric acid, sulfuric acid and acetic acid, e.g. 8-hydroxyquinoline sulfate of the formula: ##STR5## chelates of 8-hydroxyquinoline with metals such as copper and zinc, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate shown by the following formula: ##STR6## tetrachloroisophthalonitrile shown by the following formula: ##STR7## and N-(fluorodichloromethylthio)phthalimide shown by the following formula: ##STR8## These compounds may be employed anone or in admixture thereof.

The components (A) and (B) may be employed in any proportions. In general, it is desirable to employ the component (B) in an amount of 1% to 40% by weight based on the total weight of the composition, since the particularly remarkable synergistic effect can be obtained. As stated before, the feature of the present invention is that the antibacterial and antifungal effects of dehydroacetic acid, sorbic acid or their alkali metal salts can be remarkably increased by the combination use with a slight amount of the component (B). Although the compounds employed as the component (B) are known as antibacterial and antifungal agents, it has now been found that synergistic antibacterial and antifungal effect unexpected from a single use of various known antibacterial and antifungal agents can be obtained, when among known antibacterial and antifungal agents the component (A) and the component (B) are particularly combined. When the content of the component (B) is less than 1% by weight, sufficient synergistic effect cannot be obtained. Also, even if the component (B) is employed in an amount of more than 40% by weight, the synergistic effect is not increased. Further, the compounds employed as the component (B) are relatively expensive and also the toxicity is higher than the component (A) and, therefore, the use of the component (B) in an amount of more than 40% by weight not only be uneconomical, but also may impair the low toxicity which is the feature of the composition of the present invention.

The adding amount of the composition varies depending on the kind of the products to be added. In general, sufficient antibacterial and antifungal effects can be obtained in an amount of 50 to 8,000 p.p.m.

Auxiliary agents such as other bactericides, other fungicides, surface active agents and perfumes may be incorporated in the composition of the invention, as occasion demands.

The composition of the present invention is applicable to any industrial products and agricultural products which require the annihilation or the prevention of propagation of bacteria and fungi, such as paints, sizing agents, petroleum products, plastic moldings, fibers, leathers, woods, paper goods, cosmetics, pharmacuticals, medical appliances, industrial equipments and building materials (putties, fiber boards, particle boards, gypsum boards), fruits, grains and vegetables.

The present invention is more particularly described and explained by means of the following Examples, in which all % are by weight unless otherwise noted.

EXAMPLE 1

A liquid culture medium of pH 7.0 containing 1% of peptone, 1% of meat extract and 0.1% of sodium chloride was prepared and sterilized, and 10 ml. portions thereof were poured into L-shaped tubes. After adding a prescribed amount of an antibacterial, antifungal composition consisting of the components (A) and (B) as shown in Table 1 to each tube, 0.1 ml. (number of cells: 5.times.10.sup.4 cells/ml.) of an aqueous suspension of bacteria as shown in Table 1 was added to each tube. The thus prepared culture liquor contained 5.times.10.sup.2 cells per milliliter. The culture was carried out at 37.degree. C. for 48 hours with reciprocal shaking, and the state of the growth of bacteria was then observed by measuring the number of cells in 1 ml. of the culture liquor.

The results are shown in Table 1.

TABLE 1__________________________________________________________________________ Amount of Antibacterial, antifungal composition composition Number of (A)/(B) added cellsBacteria Component (A) Component (B) by weight (p.p.m.) (cells/ml.)__________________________________________________________________________Staphylococ- Sodium dehydroacetate N-(fluorodichloro- 95/5 500 25 .times. 10cus aureus methylthio)phthalimide 95/5 1000 3 .times. 10 90/10 500 18 .times. 10 90/10 1000 0 80/20 500 17 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 19 .times. 10.sup.5 100/0 1000 18 .times. 10.sup.3 0/100 25 11 .times. 10.sup.8 0/100 50 10 .times. 10.sup.5 0/100 100 7 .times. 10.sup.4 0/100 200 6 .times. 10.sup.2Staphylococ- Potassium sorbate N-(fluorodichloro- 95/5 500 30 .times. 10cus aureus methylthio)phthalimide 95/5 1000 6 90/10 500 22 .times. 10 90/10 1000 0Staphylococ- Potassium sorbate N-(fluorodichloro- 80/20 500 14 .times. 10cus aureus metylthio)phthalimide 80/20 1000 0 60/40 500 0 100/0 500 25 .times. 10.sup.7 100/0 1000 9 .times. 10.sup.5 0/100 25 11 .times. 10.sup.8 0/100 50 10 .times. 10.sup.5 0/100 100 7 .times. 10.sup.4 0/100 200 6 .times. 10.sup.2Staphylococ- Sorbic acid N-(fluorodichloro- 95/5 500 25 .times. 10cus aureus methylthio)phthalimide 95/5 1000 0 90/10 500 15 .times. 10 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 21 .times. 10.sup.6 100/0 1000 5 .times. 10.sup.3 0/100 25 11 .times. 10.sup.8Staphylococ- Sorbic acid N-(fluorodichloro- 0/100 50 10 .times. 10.sup.5cus aureus methylthio)phthalimide 0/100 100 7 .times. 10.sup.4 0/100 200 6 .times. 10.sup.2Bacillus Sodium dehydroacetate Sodium o-phenylphenolate 95/5 500 9 .times. 10subtilis 95/5 1000 7 90/10 500 8 .times. 10 90/10 1000 0 80/20 500 6 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 23 .times. 10.sup.7 100/0 1000 9 .times. 10.sup.4 0/100 25 3 .times. 10.sup.7 0/100 50 15 .times. 10.sup.4 0/100 100 6 .times. 10.sup.3 0/100 200 9 .times. 10Bacillus Potassium sorbate Sodium o-phenylphenolate 95/5 500 15 .times. 10subtilis 95/5 1000 2 90/10 500 12 .times. 10 90/10 1000 1 80/20 500 6 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 7 .times. 10.sup.8 100/0 1000 5 .times. 10.sup.7 0/100 25 3 .times. 10.sup.7 0/100 50 15 .times. 10.sup.4 0/100 100 6 .times. 10.sup.3 0/100 200 9 .times. 10Bacillus Sorbic acid Sodium o-phenylphenolate 95/5 500 15 .times. 10subtilis 95/5 1000 0 90/10 500 7 .times. 10 90/10 1000 0 80/20 500 3 .times. 10Bacillus Sorbic acid Sodium o-phenylphenolate 80/20 1000 0subtilis 60/40 500 0 100/0 500 13 .times. 10.sup.6 100/0 1000 18 .times. 10.sup.4 0/100 25 3 .times. 10.sup.7 0/100 50 15 .times. 10.sup.4 0/100 100 6 .times. 10.sup.3 0/100 200 9 .times. 10Staphylococ- Sodium dehydroacetate 2-(4-Thiazolyl)-1H- 95/5 500 21 .times. 10cus aureus benzimidazole 95/5 1000 6 .times. 10 90/10 500 20 .times. 10 90/10 1000 9 80/20 500 19 .times. 10 80/20 1000 8 60/40 500 8 .times. 10 60/40 1000 5 100/0 500 19 .times. 10.sup.5 100/0 1000 18 .times. 10.sup.3Staphylococ- Sodium dehydroacetate 2-(4-Thiazolyl)-1H- 0/100 25 4 .times. 10.sup.9cus aureus benzimidazole 0/100 50 4 .times. 10.sup.8 0/100 100 10 .times. 10.sup.6 0/100 200 5 .times. 10.sup.4Staphylococ- Potassium sorbate 2-(4-Thiazolyl)-1H- 95/5 500 25 .times. 10cus aureus benzimidazole 95/5 1000 8 .times. 10 90/10 500 24 .times. 10 90/10 1000 15 80/20 500 31 .times. 10 80/20 1000 15 60/40 500 29 .times. 10 60/40 1000 10 100/0 500 25 .times. 10.sup.7 100/0 1000 9 .times. 10.sup.5 0/100 25 4 .times. 10.sup.9 0/100 50 4 .times. 10.sup.8 0/100 100 10 .times. 10.sup.6 0/100 200 5 .times. 10.sup.4Staphylococ- Sorbic acid 2-(4-Thiazolyl)-1H- 95/5 500 30 .times. 10.sup.2cus aureus benzimidazole 95/5 1000 15 .times. 10 90/10 500 41 .times. 10 90/10 1000 35 80/20 500 17 .times. 10 80/20 1000 10 60/40 500 6 .times. 10 60/40 1000 5 100/0 500 21 .times. 10.sup.6 100/0 1000 5 .times. 10.sup.3 0/100 25 4 .times. 10.sup.9 0/100 50 4 .times. 10.sup.8 0/100 100 10 .times. 10.sup.6 0/100 200 5 .times. 10.sup.4Staphylococ- Sodium dehydroacetate Methyl 1-(butylcarba- 95/5 500 23 .times. 10cus aureus moyl)-2-benzimidazole- 95/5 1000 5 carbamate 90/10 500 21 .times. 10 90/10 1000 0Staphylococ- Sodium dehydroacetate Methyl 1-(butylcarba- 80/20 500 20 .times. 10cus aureus moyl)-2-benzimidazole- 80/20 1000 0 carbamate 60/40 500 0 100/0 500 19 .times. 10.sup.5 100/0 1000 18 .times. 10.sup.3 0/100 25 7 .times. 10.sup.6 0/100 50 9 .times. 10.sup.4 0/100 100 12 .times. 10.sup.2 0/100 200 5 .times. 10Staphylococ- Potassium sorbate Methyl 1-(butylcarba- 95/5 500 32 .times. 10cus aureus moyl)-2-benzimidazole- 95/5 1000 10 .times. 10 carbamate 90/10 500 19 .times. 10 90/10 1000 0 80/20 500 28 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 25 .times. 10.sup.7 100/0 1000 9 .times. 10.sup.5Staphylococ- Potassium sorbate Methyl 1-(butylcarba- 0/100 25 7 .times. 10.sup.6cus aureus moyl)-2-benzimidazole- 0/100 50 9 .times. 10.sup.4 carbamate 0/100 100 12 .times. 10.sup.2 0/100 200 5 .times. 10Staphylococ- Dehydroacetate Methyl 1-(butylcarba- 95/5 500 30 .times. 10cus aureus moyl)-2-benzimidazole- 95/5 1000 9 .times. 10 carbamate 90/10 500 15 .times. 10 90/10 1000 0 80/20 500 15 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 22 .times. 10.sup.5 100/0 1000 6 .times. 10.sup.3 0/100 25 7 .times. 10.sup.6 0/100 50 9 .times. 10.sup.4 0/100 100 12 .times. 10.sup.2 0/100 200 5 .times. 10Escherichia Sodium dehydroacetate Tetrachloroisophthalo- 95/5 500 9coli nitrile 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 7 .times. 10.sup.8 100/0 1000 9 .times. 10.sup.7 0/100 25 2 .times. 10.sup.5 0/100 50 9 .times. 10.sup.4 0/100 100 7 .times. 10.sup.2 0/100 200 3 .times. 10Escherichia Potassium sorbate Tetrachloroisophthalo- 95/5 500 25coli nitrile 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 6 .times. 10.sup.9 100/0 1000 12 .times. 10.sup.7Escherichia Potassium sorbate Tetrachloroisophthalo- 0/100 25 2 .times. 10.sup.5coli nitrile 0/100 50 9 .times. 10.sup.4 0/100 100 7 .times. 10.sup.2 0/100 200 3 .times. 10 Escherichia Dehydroacetic acid Tetrachloroisophthalo- 95/5 500 15coli nitrile 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 13 .times. 10.sup.8 100/0 1000 31 .times. 10.sup.6 0/100 25 2 .times. 10.sup.5 0/100 50 9 .times. 10.sup.4 0/100 100 7 .times. 10.sup.2 0/100 200 3 .times. 10Pseudomonas Sodium dehydroacetate 8-Hydroxyquinoline 95/5 500 9 .times. 10aeruginosa sulfate 95/5 1000 0 90/10 500 5 .times. 10 90/10 1000 0 80/20 500 8 .times. 10 80/20 1000 0 60/40 500 40 .times. 10 60/40 1000 0 100/0 500 15 .times. 10.sup.8 100/0 1000 2 .times. 10.sup.7 0/100 25 22 .times. 10.sup.6 0/100 50 21 .times. 10.sup.4 0/100 100 15 .times. 10.sup.2 0/100 200 4 .times. 10Pseudomonas Potassium sorbate 8-Hydroxyquinoline 95/5 500 18 .times. 10aeruginosa sulfate 95/5 1000 4 90/10 500 16 .times. 10 90/10 1000 0Pseudomonas Potassium sorbate 8-Hydroxyquinoline 80/20 500 17 .times. 10aeruginosa sulfate 80/20 1000 0 60/40 500 16 .times. 10 60/40 1000 0 100/0 500 15 .times. 10.sup.10 100/0 1000 7 .times. 10.sup.8 0/100 25 22 .times. 10.sup.6 0/100 50 21 .times. 10.sup.4 0/100 100 15 .times. 10.sup.2 0/100 200 4 .times. 10Pseudomonas Sorbic acid 8-Hydroxyquinoline 95/5 500 19 .times. 10aeruginosa sulfate 95/5 1000 10 90/10 500 21 .times. 10 90/10 1000 8 80/20 500 17 .times. 10 80/20 1000 0 60/40 500 14 .times. 10 60/40 1000 0Pseudomonas Sorbic acid 8-Hydroxyquinoline 100/0 500 9 .times. 10.sup.9aeruginosa sulfate 100/0 1000 8 .times. 10.sup.7 0/100 25 22 .times. 10.sup.6 0/100 50 21 .times. 10.sup.4 0/100 100 15 .times. 10.sup.2 0/100 200 4 .times. 10Pseudomonas Sodium dehydroacetate p-Chloro-m-xylenol 95/5 500 15 .times. 10aeruginosa 95/5 1000 0 90/10 500 13 .times. 10 90/10 1000 0 80/20 500 12 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 15 .times. 10.sup.8 100/0 1000 2 .times. 10.sup.7 0/100 25 8 .times. 10.sup.9 0/100 50 15 .times. 10.sup.6 0/100 100 18 .times. 10.sup. 4 0/100 200 13 .times.10.sup.2Pseudomonas Potassium sorbate p-Chloro-m-xylenol 95/5 500 20 .times. 10aeruginosa 95/5 1000 7 90/10 500 17 .times. 10 90/10 1000 5 80/20 500 15 .times. 10 80/20 1000 5 60/40 500 3 .times. 10 60/40 1000 0 100/0 500 15 .times. 10.sup.10 100/0 1000 7 .times. 10.sup.8 0/100 25 8 .times. 10.sup.9 0/100 50 15 .times. 10.sup.6 0/100 100 18 .times. 10.sup.4 0/100 200 13 .times. 10.sup.2Pseudomonas Sorbic acid p-Chloro-m-xylenol 95/5 500 18 .times. 10aeruginosa 95/5 1000 5 90/10 500 10 .times. 10 90/10 1000 0 80/20 500 9 .times. 10 80/20 1000 0 60/40 500 0 100/0 500 9 .times. 10.sup.9 100/0 1000 8 .times. 10.sup.7 0/100 25 8 .times. 10.sup.9 0/100 50 15 .times. 10.sup.6 0/100 100 18 .times. 10.sup.4 0/100 200 13 .times. 10.sup.2__________________________________________________________________________

EXAMPLE 2

A 5% aqueous solution of starch was prepared and sterilized, and 100 ml. portions thereof were poured into 200 ml. bottles. After adding a prescribed amount of an antibacterial, antifungal composition consisting of the components (A) and (B) as shown in Table 2 to each bottle and thoroughly agitating, 1 ml. (number of fungi: 5.times.10.sup.6 fungi/ml.) of an aqueous suspension of fungi as shown in Table 2 was added to each bottle and was agitated again. The thus prepared aqueous solution contained 5.times.10.sup.4 fungi per gram. The bottles were then sealed and allowed to stand at 30.degree. C. for a week. The state of the growth of fungi was observed by measuring the number of fungi in 1 g. of the aqueous solution.

The results are shown in Table 2.

TABLE 2__________________________________________________________________________ Amount of Antibacterial, antifungal composition composition Number of (A)/(B) added fungiFungi Component (A) Component (B) by weight (p.p.m.) (fungi/g.)__________________________________________________________________________Trichoderma Sodium dehydroacetate N-(fluorodichloro- 95/5 100 4 .times. 10viride methylthio)phthalimide 95/5 500 0 90/10 100 2 .times. 10 90/10 500 0 80/20 100 8 80/20 500 0 60/40 100 0 100/0 100 29 .times. 10.sup.8 100/0 500 34 .times. 10.sup.5 0/100 5 7 .times. 10.sup.7 0/100 25 16 .times. 10.sup.6 0/100 50 33 .times. 10.sup.4 0/100 100 5 .times. 10.sup.2Trichoderma Potassium sorbate N-(fluorodichloro- 95/5 100 8 .times. 10viride methylthio)phthalimide 95/5 500 0 90/10 100 5 .times. 10 90/10 500 0 80/20 100 7Trichoderma Potassium sorbate N-(fluorodichloro- 80/20 500 0viride methylthio)phthalimide 60/40 100 0 100/0 100 27 .times. 10.sup.10 100/0 500 9 .times. 10.sup.8 0/100 5 7 .times. 10.sup.7 0/100 25 16 .times. 10.sup.6 0/100 50 33 .times. 10.sup.4 0/100 100 5 .times. 10.sup.2Trichoderma Dehydroacetic acid N-(fluorodichloro- 95/5 100 3 .times. 10viride methylthio)phthalimide 95/5 500 0 90/10 100 0 80/20 100 0 60/40 100 0 100/0 100 25 .times. 10.sup.8 100/0 500 30 .times. 10.sup.5 0/100 5 7 .times. 10.sup.7 0/100 25 16 .times. 10.sup.6 0/100 50 33 .times. 10.sup.4Trichoderma Dehydroacetic acid N-(fluorodichloro- 0/100 100 5 .times. 10.sup.2viride methylthio)phthalimideCladosporium Sodium dehydroacetate Sodium o-phenylphenolate 95/5 500 8 .times. 10resinae 95/5 1000 5 90/10 500 5 90/10 1000 0 80/20 500 5 80/20 1000 0 60/40 500 0 100/0 500 31 .times. 10.sup.6 100/0 1000 28 .times. 10.sup.3 0/100 25 8 .times. 10.sup.10 0/100 50 18 .times. 10.sup.8 0/100 100 34 .times. 10.sup.6 0/100 200 5 .times. 10Cladosporium Potassium sorbate Sodium o-phenylphenolate 95/5 500 15 .times. 10resinae 95/5 1000 3 90/10 500 10 .times. 10Cladosporium Potassium sorbate Sodium o-phenylphenolate 90/10 1000 0resinae 80/20 500 9 80/20 1000 0 60/40 500 0 100/0 500 13 .times. 10.sup.6 100/0 1000 25 .times. 10.sup.3 0/100 25 8 .times. 10.sup.10 0/100 50 18 .times. 10.sup.8 0/100 100 34 .times. 10.sup.6 0/100 200 5 .times. 10Cladosporium Dehydroacetic acid Sodium o-phenylphenolate 95/5 500 7 .times. 10resinae 95/5 1000 0 90/10 500 4 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 10 .times. 10.sup.5 100/0 1000 9 .times. 10.sup.3Cladosporium Dehydroacetic acid Sodium o-phenylphenolate 0/100 25 8 .times. 10.sup.10resinae 0/100 50 18 .times. 10.sup.8 0/100 100 34 .times. 10.sup.6 0/100 200 5 .times. 10Aspergillus Sodium dehydroacetate 2-(4-Thiazolyl)-1H- 95/5 500 7 .times. 10niger benzimidazole 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 18 .times. 10.sup.10 100/0 1000 30 .times. 10.sup.4 0/100 25 37 .times. 10.sup.8 0/100 50 18 .times. 10.sup.5 0/100 100 11 .times. 10.sup.3 0/100 200 4 .times. 10Aspergillus Potassium sorbate 2-(4-Thiazolyl)-1H- 95/5 500 21 .times. 10niger benzimidazole 95/5 1000 3 90/10 500 3 .times. 10 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 7 .times. 10.sup.10 100/0 1000 37 .times. 10.sup.8 0/100 25 37 .times. 10.sup.8 0/100 50 18 .times. 10.sup.5 0/100 100 11 .times. 10.sup.3 0/100 200 4 .times. 10Aspergillus Dehydroacetic acid 2-(4-Thiazolyl)-1H- 95/5 500 5 .times. 10niger benzimidazole 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 17 .times. 10.sup.10Aspergillus Dehydroacetic acid 2-(4-Thiazolyl)-1H- 100/0 1000 25 .times. 10.sup.4niger benzimidazole 0/100 25 37 .times. 10.sup.8 0/100 50 18 .times. 10.sup.5 0/100 100 11 .times. 10.sup.3 0/100 200 4 .times. 10Penicillium Sodium dehydroacetate Methyl 1-(butylcarba-citrinum moyl)-2-benzimidazole- 95/5 500 23 .times. 10 carbamate 95/5 1000 8 90/10 500 2 .times. 10 90/10 1000 0 80/20 5000 5 80/20 1000 0 60/40 500 0 100/0 500 17 .times. 10.sup.5 100/0 1000 35 .times. 10.sup.4 0/100 25 13 .times. 10.sup.8 0/100 50 19 .times. 10.sup.6 0/100 100 9 .times. 10.sup.3 0/100 200 3 .times. 10Penicillium Potassium sorbate Methyl 1-(butylcarba-citrinum moyl)-2-benzimidazole- 95/5 500 19 .times. 10 carbamate 95/5 1000 9 90/10 500 10 .times. 10 90/10 1000 1 80/20 500 7 80/20 1000 0 60/40 500 0 100/0 500 4 .times. 10.sup.9 100/0 1000 12 .times. 10.sup.7 0/100 25 13 .times. 10.sup.8 0/100 50 19 .times. 10.sup.6 0/100 100 9 .times. 10.sup.3 0/100 200 3 .times. 10Penicillium Sorbic acid Methyl 1-(butylcarba-citrinum moyl)-2-benzimidazole- 95/5 500 8 .times. 10 carbamate 95/5 1000 5 90/10 500 5 .times. 10 90/10 1000 2Penicillium Sorbic acid Methyl 1-(butylcarba-citrinum moyl)-2-benzimidazole- 80/20 500 0 carbamate 60/40 500 0 100/0 500 7 .times. 10.sup.7 100/0 1000 40 .times. 10.sup.5 0/100 25 13 .times. 10.sup.8 0/100 50 19 .times. 10.sup.6 0/100 100 9 .times. 10.sup.3 0/100 200 3 .times. 10Aspergillus Sodium dehydroacetate Tetrachloroisophthalo- 95/5 100 2niger nitrile 95/5 500 0 90/10 100 0 80/20 100 0 60/40 100 0 100/0 100 25 .times. 10.sup.10 100/0 500 18 .times. 10.sup.7 0/100 5 7 .times. 10.sup.4 0/100 25 8 .times. 10.sup.3 0/100 50 3 .times. 10Aspergillus Potassium sorbate Tetrachloroisophthalo- 95/5 100 13 .times. 10niger nitrile 95/5 500 0 90/10 100 0 80/20 100 0 60/40 100 0 100/0 100 33 .times. 10.sup.11 100/0 500 7 .times. 10.sup.10 0/100 5 7 .times. 10.sup.4 0/100 25 8 .times. 10.sup.3 0/100 50 3 .times. 10Aspergillus Sorbic acid Tetrachloroisophthalo- 95/5 100 10.times. 10niger nitrile 95/5 500 0 90/10 100 0 80/20 100 0 60/40 100 0 100/0 100 32 .times. 10.sup.10 100/0 500 5 .times. 10.sup.9Aspergillus Sorbic acid Tetrachloroisophthalo- 0/100 5 7 .times. 10.sup.4niger nitrile 0/100 25 8 .times. 10.sup.3 0/100 50 3 .times. 10Aspergillus Sodium dehydroacetate 8-Hydroxyquinoline 95/5 500 3niger sulfate 95/5 1000 0 90/10 500 2 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 18 .times. 10.sup.7 100/0 1000 30 .times. 10.sup.4 0/100 25 10 .times. 10.sup.6 0/100 50 7 .times. 10.sup. 3 0/100 100 6 .times. 10.sup.2 0/100 200 6 .times. 10Aspergillus Potassium sorbate 8-Hydroxyquinoline 95/5 500 13 .times. 10niger sulfate 95/5 1000 0 90/10 500 8 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 7 .times. 10.sup.10 100/0 1000 37 .times. 10.sup.8 0/100 25 10 .times. 10.sup.6 0/100 50 7 .times. 10.sup.3 0/100 100 6 .times. 10.sup.2 0/100 200 6 .times. 10Aspergillus Dehydroacetic acid 8-Hydroxyquinoline 95/5 500 2niger sulfate 95/5 1000 0 90/10 500 2 90/10 1000 0 80/20 500 0 60/40 500 0Aspergillus Dehydroacetic acid 8-Hydroxyquinoline 100/0 500 10 .times. 10.sup.7niger sulfate 100/0 1000 25 .times. 10.sup.4 0/100 25 10 .times. 10.sup.6 0/100 50 7 .times. 10.sup.3 0/100 100 6 .times. 10.sup.2 0/100 200 6 .times. 10Aspergillus Sodium dehydroacetate p-Chloro-m-xylenol 95/5 500 10 .times. 10niger 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 18 .times. 10.sup.7 100/0 1000 30 .times. 10.sup.4 0/100 25 14 .times. 10.sup.9 0/100 50 16 .times. 10.sup.6 0/100 100 12 .times. 10.sup.4 0/100 200 5 .times. 10Aspergillus Potassium sorbate p-Chloro-m-xylenol 95/5 500 15 .times. 10niger 95/5 1000 0 90/10 500 5 .times. 10 90/10 1000 0 80/20 500 0 60/40 500 0 100/0 500 7 .times. 10.sup.10 100/0 1000 37 .times. 10.sup.8 0/100 25 14 .times. 10.sup.9 0/100 50 16 .times. 10.sup.6 0/100 100 12 .times. 10.sup.4 0/100 200 5 .times. 10Aspergillus Dehydroacetic acid p-Chloro-m-xylenol 95/5 500 6 .times. 10niger 95/5 1000 0 90/10 500 0 80/20 500 0 60/40 500 0 100/0 500 10 .times. 10.sup.7Aspergillus Dehydroacetic acid p-Chloro-m-xylenol 100/0 1000 25 .times. 10.sup.4niger 0/100 25 14 .times. 10.sup.9 0/100 50 16 .times. 10.sup.6 0/100 100 12 .times. 10.sup.4 0/100 200 5 .times. 10__________________________________________________________________________

EXAMPLE 3

A 2% of aqueous solution of carboxymethyl cellulose was prepared and adjusted to pH 7. After adding antibacterial, antifungal composition consisting of the components (A) and (B) to the solution in a concentration as shown in Table 3, a slight amount of a putrid carboxymethyl cellulose was added to the solution. The solution was stored in an air-conditioned room at 37.degree. C. and the putrefraction of the solution was obserbed with the lapse of time.

The results are shown in Table 3, in which symbols are as follows:

-: No putrefaction +: Putrefaction TABLE 3__________________________________________________________________________Antibacterial, antifungal composition Concent- Concent- Time elapsed ration ration After After AfterComponent (A) (p.p.m.) Component (B) (p.p.m.) 1 week 2 weeks 3 weeks__________________________________________________________________________Sodium dehydroacetate 500 Sodium o-phenylphenolate 10 - - -Potassium sorbate 500 Sodium o-phenylphenolate 50 - - --- 0 Sodium o-phenylphenolate 100 - + +Sodium dehydroacetate 2000 -- 0 - - +Potassium sorbate 2000 -- 0 - + +-- 0 -- 0 + + +__________________________________________________________________________

EXAMPLE 4

An antibacterial, antifungal composition was added to a 6% aqueous solution of glue in a concentration as shown in Table 4. The solution was stored in an air-conditioned room at 50.degree. C. and the decrease of the viscosity due to putrefaction was observed with the lapse of time.

The results are shown in Table 4, in which symbols are as follows:

-: No decrease of viscosity +: Decrease of viscosity TABLE 4__________________________________________________________________________Antibacterial, antifungal composition Concent- Concent- Time elapsed ration ration After After AfterComponent (A) (p.p.m.) Component (B) (p.p.m.) 1 week 2 weeks 3 weeks__________________________________________________________________________Sodium dehydroacetate 1000 Sodium o-phenylphenolate 50 - - -Potassium sorbate 2000 Sodium o-phenylphenolate 50 - - --- 0 Sodium o-phenylphenolate 200 + + +Sodium dehydroacetate 5000 -- 0 - - +Potassium sorbate 5000 -- 0 - - +-- 0 -- 0 + + +__________________________________________________________________________

EXAMPLE 5

An antibacterial, antifungal composition was added to an ethylene-vinyl acetate copolymer emulsion containing polyvinyl alcohol as an emulsifier in a concentration as shown in Table 5. A slight amount of a putrid emulsion was added to the emulsion and the number of cells was immediately measured. The emulsion was then stored in an air-conditioned room at 30.degree. C., and after 3 weeks, the number of cells in the emulsion was measured again to determine the preservative and fungicidal effects.

The results are shown in Table 5.

TABLE 5__________________________________________________________________________Antibacterial, antifungal composition Concent- Concent- Number of cells (cell/g.) ration ration Before storage After 3 weeksComponent (A) (p.p.m.) Component (B) (p.p.m.) Fungi Yeast Bacteria Fungi Yeast Bacteria__________________________________________________________________________Potassium de- Sodium o-phe-hydroacetate 3000 nylphenolate 100 51 .times. 10.sup.6 15 .times. 10.sup.6 7 .times. 10.sup.3 <10.sup.2 <10.sup.2 2 .times. 10.sup.2Potassium Sodium o-phe-sorbate 4000 nylphenolate 200 35 .times. 10.sup.6 19 .times. 10.sup.6 5 .times. 10.sup.3 <10.sup.2 <10.sup.2 4 .times. 10.sup.2-- Sodium o-phe- 0 nylphenolate 1000 25 .times. 10.sup.6 19 .times. 10.sup.6 9 .times. 10.sup.3 31 .times. 10.sup.5 22 .times. 10.sup.5 9 .times. 10.sup.3Sodium de- 5000 --hydroacetate 0 30 .times. 10.sup.6 26 .times. 10.sup.6 6 .times. 10.sup.3 72 .times. 10.sup.4 18 .times. 10.sup.4 6 .times. 10.sup.3Potassium --sorbate 5000 0 17 .times. 10.sup.6 24 .times. 10.sup.6 6 .times. 10.sup.3 10 .times. 10.sup.6 29 .times. 10.sup.5 5 .times. 10.sup.3-- 0 -- 0 51 .times. 10.sup.6 18 .times. 10.sup.6 8 .times. 10.sup.3 23 .times. 10.sup.7 25 .times. 10.sup.6 8 .times. 10.sup.3__________________________________________________________________________

EXAMPLE 6

A 10% aqueous solution of a polyvinly alcohol sizing agent was prepared and divided into three portions. To the first portion was added no medicine, to the second portion was added 2,000 p.p.m. of sodium dehydroacetate, and to the third portion were added 1,000 p.p.m. of sodium dehydroacetate and 100 p.p.m. of p-chloro-m-xylenol. Epicoccum sp. was inoculated to each of the three portions, and they were placed in an incubator at 30.degree. C. and allowed to stand for 14 days.

In the first and second portions, development of fungi was observed after 3 and 5 days, respectively, but in the third portion no development of fungi was observed.

The above procedure was repeated except that, as the component (B), 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline sulfate, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile or N-(fluorodichloromethylthio)phthalimide was employed instead of p-chloro-m-xylenol. The same results as above were obtained with respect to all the above compounds.

EXAMPLE 7

The procedures of Example 6 were repeated except that potassium sorbate was employed instead of sodium dehydroacetate.

With respect to all tests using six components (B) in Example 6, in the first and second portions development of fungi was observed after 4 to 6 days, respectively, but in the third portion no development of fungi was observed.

EXAMPLE 8

An antibacterial, antifungal composition was prepared by admixing 95 g. of sodium dehydroacetate as the component (A) and 5 g. of the component (B) shown in Table 6. The composition was added to a 18% solution of a crotonic acid-vinyl acetate copolymer in a concentration of 2,500 p.p.m., 5,000 p.p.m. or 7,500 p.p.m. to give three kinds of the coating solutions.

Each solution was sprayed onto two sides of a fancy mat (10.times.10 cm.) in an amount of 2 g. on each side, and was then dried at 140.degree. C. for 2 minutes.

The coated fancy mats were allowed to stand under a saturated humidity at 25.degree. C., and the state of the growth of fungi was observed with the lapse of time.

The results are shown in Table 6, in which symbols are as follows:

-: No growth .+-.: A little growth +: Growth (The more the number of the symbol +, the larger the growth.) TABLE 6__________________________________________________________________________ Concentration of composition Days elapsedComponent (B) (p.p.m.) 5 6 7 8 10 12 14__________________________________________________________________________p-Chloro-m-xylenol 0 - - + ++ +++ +++++ +++++ 2500 - - .+-. + +++ +++ ++++ 5000 - - - .+-. + ++ +++ 7500 - - - - - - -2-(4-Thiazolyl)-1H-benzimidazole 0 - + ++ +++ ++++ +++++ +++++ 2500 - - + + +++ +++ ++++ 5000 - - - .+-. + ++ +++ 7500 - - - - - - -8-Hydroxyquinoline sulfate 0 - + ++ +++ ++++ +++++ +++++ 2500 - - + + +++ +++ ++++ 5000 - - - .+-. + ++ +++ 7500 - - - - - - -Methyl 1-(butylcarbamoyl)-2-benz- 0 - + ++ +++ ++++ +++++ +++++imidazolecarbamate2500 - - + + +++ +++ ++++ 5000 - - - .+-. + ++ +++ 7500 - - - - - - -Tetrachloroisophthalonitrile 0 - + ++ + ++ ++++ +++++ +++++ 2500 - - .+-. + +++ +++ ++++ 5000 - - - - .+-. + ++ 7500 - - - - - - -N-(fluorodichloromethylthio)- 0 - + ++ +++ ++++ +++++ +++++phthalimide 2500 - .+-. + + +++ +++ ++++ 5000 - - - .+-. + ++ +++ 7500 - - - - - - -__________________________________________________________________________

EXAMPLE 9

A sizing solution containing 5% of wheat starch and a sizing solution containing 5% of casein were prepared, and thereto was added an antibacterial or antifungal agent as shown in Table 7. After adding a suspension of fungi consisting of Aspergillus niger, Penicillium citrinum, Cladosporium herbaum and Chaetomium globosum to each of the sizing solutions, the sizing solutions were placed in an incubator at 28.degree. C. and the state of the growth of fungi was observed with the lapse of time.

The results are shown in Table 7, in which symbols are as follows:

-: No growth .+-.: A little growth +: Growth (The more the number of the symbol +, the larger the growth.) TABLE 7__________________________________________________________________________Sizing Incubation dayssolution Antibacterial, antifungal agent 0 4 7 14 21 28__________________________________________________________________________Wheat starch None - + +++ ++++ ++++ ++++Casein " - - ++ +++ ++++ ++++Wheat starch Sodium dehydroacetate (500 p.p.m.) - - .+-. ++ +++ +++Casein " - - - + ++ +++Wheat starch Sodium dehydroacetate (475 p.p.m.) and p-Chloro-m-xylenol (25 p.p.m.) - - - - - -Casein Sodium dehydroacetate (475 p.p.m.) and - - - - - -- p-Chloro-m-xylenol (25 p.p.m.)Wheat starch Sodium dehydroacetate (475 p.p.m.) and - - - - - - 2-(4-Thiazolyl)-1H-benzimidazole (25 p.p.m.)Casein Sodium dehydroacetate (475 p.p.m.) and - - - - - - 2-(4-Thiazolyl)-1H-benzimidazole (25 p.p.m.)Wheat starch Sodium dehydroacetate (475 p.p.m.) and - - - - - - 8-Hydroxyquinoline sulfate (25 p.p.m.) -Casein Sodium dehydroacetate (475 p.p.m.) -nd - - - - - 8-Hydroxyquinoline sulfate (25 p.p.m.)Wheat starch Sodium dehydroacetate (475 p.p.m.) and - - - - - - Methyl 1-(butylcarbamoyl)-2-benzimidazole- carbamate (25 p.p.m.)Casein Sodium dehydroacetate (475 p.p.m.) and - - - - - - Methyl 1-(butylcarbamyl)-2-benzimidazole carbamate (25 p.p.m.)Wheat starch Sodium dehydroacetate (475 p.p.m.) and - - - - - - Tetrachloroisophthalonitrile (25 p.p.m.)Casein Sodium dehydroacetate (475 p.p.m.) and - - - - - - Tetrachloroisophthalonitrile (25 p.p.m.) Sodium dehydroacetate (475 p.p.m.) andWheat starch N-(fluorodichloromethylthio)phthalimide - - - - - - (25 p.p.m.)Casein Sodium dehydroacetate (475 p.p.m.) and - - - - - - N-(fluorodichloromethylthio)phthalimide (25 p.p.m.)__________________________________________________________________________

Claims

1. An antibacterial and antifungal composition comprising a mixture of:

(A) at least one member selected from the group consisting of dehydroacetic acid, and its alkali metal salts, wherein said member is contained within said composition in an amount 60-95% by weight, based on the total weight of the composition, and

(B) tetrachloroisophthalonitrile in a synergistically effective amount of from 1% to 40% by weight based on the total weight of the composition.

2. An antibacterial and antifungal composition as in claim 1, wherein said tetrachloroisophthalonitrile is contained within said composition in an amount of from 5% to 40% by weight based on the total weight of the composition.