JPS6326081B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to industrial preservatives and antifungal agents.
More specifically, it is an agent for preventing staining of various industrial products by bacteria, fungi, etc., and its active ingredient is 4,5-dichloro-
The present invention relates to a non-aqueous industrial preservative and antifungal agent containing 1,2-dithiol-3-one and a polyvalent metal salt as an effect-enhancing component. The many damages caused by the action of microorganisms are not limited to diseases of humans and animals, damage to food and crops, etc.
It is used in a wide range of industrial chemicals and products, including electrical and electronic products, aluminum products, plastic products, building materials, paints, adhesives, cutting oils, and textile oils. On the other hand, 4,5-dichloro-1,2-dithiol-3-one is known as an industrial disinfectant. This compound has the following formula: It is a heterocyclic dithiol compound represented by
14294) etc. However, it has the disadvantage that its range of use is limited because it is an expensive drug. As a result of repeated research aimed at increasing the efficacy of 4,5-dichloro-1,2-dithiol-3-one, the present inventors discovered that 4,5-dichloro-1,2-dithiol-3-one
By using 1,2-dithiol-3-one and a polyvalent metal salt in combination, 4,5-dichloro-1,2-dithiol-3
We have discovered a surprising fact that the amount of -on added can be reduced. Thus, according to the present invention, there is provided a non-water-based industrial preservative and antifungal agent containing 4,5-dichloro-1,2-dithiol-3-one and a polyvalent metal salt as an effect-enhancing component. be done. In this invention, "non-use water system" means target systems such as various industrial chemicals and industrial products, excluding so-called industrial water systems such as industrial cooling water and paper manufacturing process water. Polyvalent metal salts used in this invention include polyvalent metal salts of aluminum, manganese, iron, nickel, copper, zinc, and tin. In this case, halides such as chlorides, bromides, fluorides, and iodides of these polyvalent metals, mineral acid salts such as sulfates and nitrates, and organic acid salts such as acetates and citrates are preferably used. Ru. Among these, water-soluble salts are preferred, and those contained in the form of chlorides are particularly preferred because they provide the highest amount of heavy metal ions supplied per weight. The blending ratio of these polyvalent metal salts is 4.5 by weight.
-dichloro-1,2-dithiol-3-one 1
0.05 to 1000, preferably 0.1 to 100 as a polyvalent metal. Preservation in this invention
Generally, liquid formulations of antifungal agents are preferred because they are easy to handle. There are various preparation methods, but for example, cellosolves such as ethylene glycol monoalkyl ether and ethylene glycol monophenyl ether, diethylene glycol are added to an aqueous solution of 4,5-dichloro-1,2-dithiol-3-one and the polyvalent metal salt. Carbitols such as monoalkyl ethers,
A homogeneous and transparent liquid composition can be obtained by mixing one or more hydrophilic organic solvents selected from glycols and glycols such as polyethylene glycol and dialkylene glycol. The amount of the preservative and antifungal agent of this invention varies slightly depending on the properties of the non-water-based industrial product, the usage environment, etc., but it is usually at least 0.05 to 1.0% by weight as an active ingredient to the product. Adding more than 5.0% by weight is economically wasteful. Specific target systems for the present invention include various paints, wall materials, polymer latexes, adhesives, pastes, cutting fluids, paper coating fluids, leather, fibers, plastics, wood and bamboo materials, etc. Examples include industrial products. The antiseptic and antifungal agent of this invention can be mixed into liquid industrial chemicals such as wall materials and adhesives when they are prepared, or applied to the surface of solid industrial products such as wood, textile products, and leather products. It is used by coating or forming a film with the agent of the present invention in the following dosage form. This treatment exhibits remarkable bactericidal and fungicidal effects based on the enhanced action of 4,5-dichloro-1,2-dithiol-3-one, making it possible to efficiently prevent damage caused by these microorganisms. In addition, the active ingredients 4, 5 used in this invention
-Dichloro-1,2-dithiol-3-one and the polyvalent metal salt may be added to the intended target system as separate formulations, in which case the same effect as a single formulation can be obtained. . When using such separate formulations, for 4,5-dichloro-1,2-dithiol-3-one, the components are added to a hydrophilic organic solvent and dissolved with stirring, and ethylene oxide of ethylenediamine is added to the solution. It is preferable to use a preparation homogenized by adding a propylene oxide copolymer adduct or an alkylolamide type nonionic surfactant, and for polyvalent metal salts, simply an aqueous solution may be used. Therefore, according to another aspect, the present invention provides a non-alcoholic product characterized in that 4,5-dichloro-1,2-dithiol-3-one is used in combination with a polyvalent metal salt as an potency-enhancing component. It also provides water-based industrial antiseptic and mold prevention methods. The present invention will be explained below with reference to test examples, formulation examples, and examples. Test example 1 (standard bacteria Pseudomonas aeruginosa IAM
Bactericidal effect on 1514) Pseudomonas aeruginosa IAM 1514 was planted in a bouillon medium and cultured at 37°C for 16 hours. Then add 0.1ml of new bouillon medium (10ml)
When the absorbance reached 0.65 to 0.70, the culture solution was diluted 100 times with sterile water, and 10 ml was dispensed into an L-shaped test tube. A predetermined drug was added to each sample and the samples were left in contact with each other for 1 hour using a shaker. this
The cells were planted in a standard agar medium, cultured for 48 hours in a flan vessel at 37°C, and the number of viable bacteria per ml of culture solution was measured. The results are shown in Table 1.

【table】

【table】

[Consideration]

As is clear from the test results, when using 4,5-dichloro-1,2-dithiol-3-one alone, in order to reduce the number of bacteria to 10 ³ cells/ml or less, 0.9 mg is required as shown in Test No. 55. / necessary, whereas in the present invention, 4,5-dichloro-1,2-dithiol-3-one and a polyvalent metal salt are used as a polyvalent metal of 0.57 to
2.47mg/Test No. 4, 6, by combined use
As shown in 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, the amount of 4,5-dichloro-1,2-dithiol-3-one added was reduced to 0.4 mg/half or less. can be reduced. (4,5-dichloro-
The efficacy of 4,5-dichloro-1,2-dithiol-3-one is remarkable by using 1,2-dithiol-3-one as 1 and a polyvalent metal salt as a polyvalent metal in a weight ratio of 1.4 to 6.2. It can be seen that this is enhanced. ) Also, test No. 29-32, 34-36, 41, 42, 45, 46,
4,5-dichloro-1,2-dithiol-3-one as 1 as shown in 48, 49, 51, 52
_4,5 - _dichloro-
It can be seen that the efficacy of 1,2-dithiol-3-one is significantly enhanced. In particular, as shown in Test No. 32, 4,5-dichloro-1,2-dithiol-
It is possible to reduce the amount of 3-one added to 1/9. In addition, as shown in Test Nos. 57-59, 61, 62, 64-68, 4,5-dichloro-1,2-dithiol-
The weight ratio of ZnCl ₂ is 1.8 as Zn with 3-one as 1.
It can be seen that the efficacy of 4,5-dichloro-1,2-dithiol-3-one is significantly enhanced when used in combination so that the amount of 4,5-dichloro-1,2-dithiol-3-one becomes . [(Note) The specific gravity of the sample is approximately equal to 1. The same applies to the following test examples. ] Test Example 2 (Bactericidal effect on standard bacteria Bacillus subtilis 168) The effect of the present invention was tested using the same test method as Test Example 1, except that the standard bacteria was replaced with Bacillus subtilis 168. The results are shown in Table 2.

[Table] Test Example 3 (Bactericidal effect on standard bacteria Staphylococcus aureus IAM 1011) The effect of the present invention was tested using the same test method as Test Example 1, except that the standard bacteria was replaced with Staphylococcus aureus IAM 1011. The results are shown in Table 3.

【table】

[Consideration]

As shown in Test Example 2, 4,5-dichloro-
1,2-dithiol-3-one as 1
By using AlCl ₃ 6H ₂ O in a weight ratio of 2.2 to 110 as Al, as shown in Test Example 3, 4,5-dichloro-1,2-dithiol-
AlCl ₃ 6H ₂ O in weight ratio with 3-one as 1
It can be seen that the efficacy of 4,5-dichloro-1,2-dithiol-3-one is significantly enhanced by using the 4,5-dichloro-1,2-dithiol-3-one in combination so that the value is 1.4 to 28. Test Example 4 (Effect on fungi) Dispense the liquid culture medium into 10 ml L-shaped tubes, and add the drug to each concentration. Aspergillus niger was used as a test bacterium, suspended in 10 ml of spore suspension from a slant culture medium, added 0.1 ml each to the above L-shaped tube, and cultured with shaking at 27°C for 72 hours. do. After 72 hours, the presence or absence of bacterial colonies is visually observed to determine the effectiveness. All culture media and equipment were sterilized. The results are shown in Table 4.

【table】

[Consideration]

As shown in the test results, 4,5-dichloro-
1,2-dithiol-3-one as 1
_4,5 - _dichloro-
It can be seen that the effect of 1,2-dithiol-3-one is significantly enhanced. Formulation example 1 4,5-dichloro-1,2-dithiol-3-one 5 parts by weight diethylene glycol monomethyl ether
20 parts by weight Diethylene glycol 65 parts by weight Aluminum chloride hexahydrate 5 parts by weight Water 5 parts by weight These were mixed to obtain a uniform transparent liquid composition. Formulation example 2 4,5-dichloro-1,2-dithiol-3-one 5 parts by weight diethylene glycol monomethyl ether
20 parts by weight Diethylene glycol 65 parts by weight 50 w/w% zinc chloride aqueous solution 10 parts by weight These were mixed to obtain a uniform transparent liquid composition. Formulation example 3 4,5-dichloro-1,2-dithiol-3-one 5 parts by weight diethylene glycol monomethyl ether
85 parts by weight Manganese sulfate 4-6 hydrate 5 parts by weight Water 5 parts by weight These were mixed to obtain a uniform transparent liquid composition. Example 1 (Bactericidal test of cutting oil liquid) Cutting oil that had already spoiled and collected at a certain metal processing factory was added to a broth liquid medium and cultured with shaking for 24 hours to activate it and use it as a test bacterium. 30 times diluted cutting oil emulsion (PH.9.1) 9.9 in a 10ml L-shaped tube
ml and 0.1 ml of the above test bacteria to a predetermined concentration, the drug was shaken at 37°C, and the number of bacteria was measured after 1 hour. The results are shown in Table 5.

[Consideration]

As is clear from the test results, 4,5-dichloro-1,2-dithiol-3-one is
AlCl ₃ 6H ₂ O is 0.22 to 0.44 as Al, and ZnCl ₂ is
4,5-dichloro-1,2-dithiol-3 when used in combination so that Zn is 0.96 to 1.92
-on efficacy can be significantly enhanced. Example 2 (Paint preservative test) Commercially available acrylic and vinyl acetate paints
Rot paint per 500g (6 x 10 bacteria/ ⁶ pieces/
ml, filamentous fungi 8×10 ⁴ pieces/ml, yeast fungi 5×10 ⁴ pieces/ml
The drug was added to 50g of ml) and left in an egg rotator at 30°C. Odor, pigment aggregation, and mold growth on the upper part were visually observed over time. The results are shown in Table 6.

[Table] Similar results were obtained for acrylic and vinyl acetate paints. The meaning of each symbol in the above table is as follows. ...There is a strong smell of putrefaction, there is mold on more than 2/3 of the surface, there is strong agglomeration, or any of the following. ...There is a rotting odor, there is mold on 1/3 or more and less than 2/3 of the surface, there is aggregation, or any of the following conditions. +... Slight smell of rot, mold on less than 1/3 of the surface, slight agglomeration, any of the following conditions. −……No putrid odor, no mold, no aggregation, any of the following conditions. [Discussion] As is clear from the test results, 4,5-dichloro-1,2-dithiol-3-one is
MnSO _4.4 ~ _6H2O as Mn in weight ratio 0.53~
5.3, the efficacy of 4,5-dichloro-1,2-dithiol-3-one can be significantly enhanced. Example 3 A 15% water suspension of commercially available cornstarch was heated at 90°C.
The drug was added to the gelatinized mixture after heating for 15 minutes.
Thereafter, 1% by weight of rotten paste was added to the gelatinized product, and the mixture was left at 30° C. for 7 days. After standing, mold growth, putrid odor, and decrease in viscosity were observed. The results are shown in the 7th section.
Shown in the table.

【table】

[Table] +...Accepted.
−……Not acceptable.
[Discussion] As is clear from the test results, 4,5-dichloro-1,2-dithiol-3-one is
The weight ratio of AlCl ₃ 6H ₂ O to Al is 1.9, MnSO ₄
4,5- _dichloro -1,2-
The efficacy of dithiol-3-ones can be significantly enhanced.

Claims (1)

[Claims] 1 4,5-dichloro-1,2-dithiol-3
- A non-water-based industrial preservative and antifungal agent characterized by containing a polyvalent metal salt as an effect-enhancing ingredient. 2 4,5-dichloro-1,2-dithiol-3
The industrial preservative according to claim 1, characterized in that the polyvalent metal salt is contained in a weight ratio of 0.1 to 100 as a polyvalent metal, with -one being 1.
Antifungal agent. 3 The polyvalent metal salt is aluminum, manganese,
The industrial preservative and antifungal agent according to claim 1, which is a water-soluble salt of one or more polyvalent metals selected from iron, ferric, nickel, copper, zinc, and tin.