JPH04290806A - Bactericide composition - Google Patents

Abstract

PURPOSE:To provide a bactercide composition having an antibacterial activity against all kinds of microbes, exhibiting an extremely high antibacterial activity, having excellent stability and persistance on the antibacterial activity in a wide pH range, and not affecting products containing the bactericide. CONSTITUTION:A bactericide composition comprises (A) the clathrate compound of 5-chloro-2-methyl-4-isothiazolin-3-one and (B) one or more bactericides selected from methylene bisthiocynate, 1,2-benzoisothiazolin-3-one, 4,5-dichloro-2-octy-3- isothiazolone and dichlorophen, exhibits the above-mentioned activities due to their synergistic actions, and is employed for the cooling water systems of various industrial plants. The weight ratio of the components A:B is 1:5 to 50:1, when B is methylene bisthiocyanate or 1,2-benzoisothizoline; and 1:20 to 200:1 when B is dichlorophen.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides a novel bactericidal composition, more specifically, a novel bactericidal composition for industrial use that has extremely excellent antibacterial activity against all types of bacteria and has an excellent long-lasting antibacterial effect over a wide range of pH. The present invention relates to a disinfectant composition.

0002

[Prior Art] In the cooling water systems of various industrial plants, slime consisting of bacteria, filamentous fungi, algae, etc. is generated in the system, resulting in decreased thermal efficiency, blockage of water pipes, corrosion of metal materials of pipes, etc. It is known that failures often occur. In addition, in pulp and paper making systems, slime consisting mainly of microorganisms such as bacteria and filamentous fungi is formed on the inner wall surface of the system using various additives such as cellulose and starch as nutrients. Peeling can cause undesirable situations such as contamination as foreign matter in the product and deterioration of product quality, or inducing paper breakage in the papermaking process, hindering continuous operation, and significantly reducing production efficiency. . Particularly in the pulp and paper industry, large amounts of additives such as starch, latex, and casein are used, and these additives serve as nutritional sources for the growth of microorganisms, causing them to rot and cause product deterioration. This is a major cause. In addition, in related fields such as water-based paints rich in organic substances, emulsion paints, emulsion adhesives, metal processing oils, latex, starch pastes, and paper coating fluids, microorganisms can cause deterioration in product quality and productivity. It is known that various problems such as Conventionally, microbial disorders such as bacteria, filamentous fungi, yeast, and algae in various industrial fields have been treated with antibacterial agents because they are relatively simple and economical to implement. Conventionally, this antibacterial agent
Thiocyanate compounds, halocyanacetamide compounds, isothiazolone compounds, and the like are often used. However, thiocyanate-based compounds have a weak bactericidal activity, and when used for a long period of time, they tend to become resistant to slime-constituting bacteria, and in particular, they have weak antibacterial activity against Microbacterium, which often appears as slime-constituting bacteria. ing. In addition, halocyanoacetamide-based compounds have excellent fast-acting bactericidal properties and exhibit stable bactericidal activity that is less affected by the number of bacteria in treated water, so they can be used as bactericidal agents for water systems contaminated with microorganisms. However, this type of bactericide has the drawbacks of poor sustainability of its effect and weak antibacterial activity against filamentous fungi. On the other hand, 5-chloro-2-methyl-4-isothiazolin-3-one is known as a typical isothiazolone compound, and this compound has excellent antibacterial activity against both bacteria and fungi. However, it has the drawback that it is not fast-acting, and its antibacterial activity is easily affected by the number of bacteria, and as the number of bacteria increases, the antibacterial activity decreases markedly. Furthermore, since 5-chloro-2-methyl-4-isothiazolin-3-one lacks stability in neutral or alkaline liquids, the sustainability of its antibacterial effect may not always be fully satisfactory depending on the target water quality. It was not possible. In particular, the effect has not always been sufficient for the preservative treatment of metal processing oils, paints, latex, etc., which require long-term preservative effects. Furthermore, although this 5-chloro-2-methyl-4-isothiazolin-3-one is prepared and commercialized as an aqueous solution, it usually contains a large amount of metal salts such as nitrate as a stabilizer. When this disinfectant composition is added to emulsion-based adhesives, paints, metal working oils, latex, etc., it has the disadvantage that it destroys the emulsion and adversely affects the product. In order to improve these drawbacks, the present inventors first discovered an antibacterial agent containing a halocyanoacetamide compound and an inthiazolone clathrate compound (Japanese Patent Application No. 1-99752). However, an antibacterial agent that combines these two types of compounds shows a significant improvement in antibacterial activity due to their excellent synergistic effect compared to when either one is used alone, and although stable antibacterial activity can be obtained, The halocyanoacetamide compound has short-lasting bactericidal activity, and its efficacy is significantly reduced in an alkaline system, resulting in a weak bactericidal effect against mold, so it has not always been satisfactory.

0003

Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional disinfectants, has extremely high antibacterial activity, and has excellent stability and sustainability of antibacterial activity over a wide range of pH. The purpose of this invention is to provide a disinfectant composition that does not have a negative effect on products.

0004

[Means for Solving the Problems] As a result of intensive research to develop a fungicide composition having the above-mentioned preferable properties, the present inventors have found that 5-chloro-2-methyl-4-isothiazoline-3- The inventors have discovered that the object can be achieved by a composition that combines a clathrate compound of 100% and a specific bactericidal agent, and based on this knowledge, they have completed the present invention. That is, the present invention provides a clathrate compound of (A) 5-chloro-2-methyl-4-isothiazolin-3-one, and (B
) Containing at least one fungicide selected from methylene bisthiocyanate, 1,2-benzisothiazolin-3-one, 4,5-dichloro-2-octyl-3-isothiazolone, and dichlorophene. The present invention provides a disinfectant composition comprising:

[0005] The present invention will be explained in detail below. In the composition of the present invention, the host compound used in the clathrate compound of 5-chloro-2-methyl-4-isothiazolin-3-one used as component (A) is -Isothiazolin-3-one may be included therein to form a clathrate compound, and there is no particular limitation, for example, 1,1,6,6-tetraphenyl-2
, 4-hexadiyn-1,6-diol, 1,1-bis(2,4-dimethylphenyl)-2-propyn-1-ol, 1,1,4,4-tetraphenyl-2-butyl-
1,4-diol, 1,1'-bi-2-naphthol, 1
, 1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyn-1,6-diol, 9,1
0-bis(4-methylphenyl)-9,10-dihydroanthracene-9,10-diol, 1,1-bis(4
-hydroxyphenyl)cyclohexane, N,N,N'
N'-(tetracyclohexyl)-[1,1'-biphenyl]-2,2'-dicarboxamide, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, deoxycholic acid, 2,5-dicarboxyamide, Polymolecular host compounds such as -t-butylhydroquinone are preferably used.

These host compounds and 5-chloro-2-
The inclusion compound with methyl-4-isothiazolin-3-one is usually solid. Further, the content of 5-chloro-2-methyl-4-isothiazolin-3-one in the clathrate compound is usually selected within the range of 10 to 40% by weight. In the composition of the present invention, methylene bisthiocyanate, 1,2-benzisothiazoline-3-
At least one fungicide selected from 1, 4,5-dichloro-2-octyl-3-isothiazolone, and dichlorophene is used.

The above component (A) in the composition of the present invention and (
When one type of methylene bisthiocyanate is used as the bactericidal agent for component (B), the blending ratio with component B) is usually as follows:
Polymerization ratio 1:5 to 50:1, weight ratio 1:5 to 50:1 when one type of 1,2-benzisothiazolin-3-one is used, 4,5-dichloro-2-octyl-3-
When one type of isothiazolone is used, the weight ratio is selected within the range of 1:30 to 300:1, and when one type of dichlorophene is used, the weight ratio is selected within the range of 1:20 to 200:1. Moreover, the above-mentioned (B) component bactericide may be used in combination of two or more types.

Although there are no particular restrictions on the method of using the fungicide composition of the present invention, it is advantageous to use it as a flowable agent by dispersing it in water or an organic dispersion medium. In this case, from the viewpoint of dispersibility in the dispersion medium, the smaller the particle size of the component (A) and component (B), the more preferable it is, and for practical purposes, it is preferable that the component (A) and the component (B) be a fine powder that passes through 100 mesh. It is. The organic dispersion medium is not particularly limited; for example, alcohols such as ethylene glycol, propylene glycol, glycerin, and polyglycerin; liquid paraffin; alkylbenzenes such as xylene and toluene; castor oil, soybean oil, olive oil, Vegetable oils such as rapeseed oil; terpenes such as cypress oil; surfactants such as polyoxyethylene alkyl ether, etc. can be used. One type of these dispersion media may be used, or two or more types may be used in combination.

[0009] In the fungicide composition of the present invention, as a stabilizer, for example, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, xanthan gum, rhamsan gum,
Sodium polyacrylate, polyacrylamide, alkyl methacrylate/diethylaminoethyl methacrylate copolymer, alkyl methacrylate/N-vinyl-
2-pyrrolidone acrylate copolymer, alkyl methacrylate/polyethylene glycol methacrylate copolymer, dodecyl fumarate/diethylaminoethyl methacrylate copolymer, styrene/maleic acid copolymer,
Sodium naphthalene sulfonate formalin condensate, sodium melamine sulfonate formalin condensate, sodium lauryl sulfate, sodium lauryl benzene sulfonate, polyoxyethylene alkyl ether, succinimide, succinic acid ester, polyalkyl glycol carbonate, polyalkylene glycol carbamine Acid esters, alkylbenzenesulfonic acids, nonionic surfactants, and the like can be used.

[0010] The amount of the disinfectant composition of the present invention to be added is appropriately selected depending on the type of object to be sterilized to which the composition is applied. When used, the total amount of active ingredients of component (A) and component (B) is 0.1 to 10 g/
m3, and when the object to be sterilized is a synthetic resin emulsion, starch paste, paint, metal working oil, or color coating fluid, that is, when used as a preservative, the total amount of active ingredients is 1 to 2000 g. /m3.

[0011]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these Examples in any way.

Example 1 3 weights of CMI clathrate compound with a weight ratio of 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter abbreviated as CMI)/1,1'-biphenol of 1/1.9 A fungicide composition was prepared containing 3 parts by weight of methylene bisthiocyanate, 0.12 parts by weight of sodium naphthalene sulfonate-formalin condensate, 0.1 parts by weight of xanthan gum, and 93.68 parts by weight of water.

Example 2 4 parts by weight of a CMI clathrate compound with a CMI/deoxycholic acid weight ratio of 1/2.6, 1,2-benzisothiazoline-3
-one 4 parts by weight, polyvinylpyrrolidone 0.16 parts by weight, polyvinyl alcohol 0.5 parts by weight, and water 91.34 parts by weight.
A disinfectant composition was prepared consisting of parts by weight.

Example 3 CMI/1,1-bis(2,4-dimethylphenyl)-
3 parts by weight of CMI clathrate compound with 2-propyn-1-ol weight ratio 1/1.8, 4,5-dichloro-2-octyl-
A disinfectant composition was prepared consisting of 3 parts by weight of 3-isothiazolone, 0.12 parts by weight of sodium laurylbenzenesulfonate, 5 parts by weight of carboxymethyl cellulose, and 88.88 parts by weight of water.

Example 4 CMI clathrate compound 5 with a CMI/1,1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyn-1,6-diol weight ratio of 1/3.5 parts by weight, 5 parts by weight of dichlorophene, 0.1 parts by weight of polyvinylpyrrolidone, 0.3 parts by weight of polyacrylamide, and 89.6 parts by weight of water.
A disinfectant composition was prepared consisting of parts by weight.

Comparative Example 1 3 parts by weight of a CMI clathrate compound with a CMI/1,1-bis(4-hydroxyphenyl)cyclohexane weight ratio of 1/1.8, 0.03 parts by weight of polyvinylpyrrolidone, and 0.1 parts by weight of Ramsan gum. and 98.87 parts by weight of water.

Comparative Example 2 CMI/1.1bis(2,4-dimethylphenyl)-2
- Propyn-1-ol 3 parts by weight of CMI clathrate compound with a polymerization ratio of 1/1.8, 3 parts by weight of monobromocyanoacetamide, 0.05 parts by weight of polyvinylpyrrolidone, 5 parts by weight of carboxymethyl cellulose, and 88.95 parts by weight of water. A fungicide composition was prepared consisting of:

Comparative Example 3 3 parts by weight of methylene bisthiocyanate, 0.06 parts by weight of sodium naphthalene sulfonate-formalin condensate,
A fungicide composition was prepared consisting of 0.05 parts by weight of xanthan gum and 96.89 parts by weight of water.

Comparative Example 4 A disinfectant composition was prepared consisting of 4 parts by weight of 1,2-benzisothiazolin-3-one, 0.08 parts by weight of polyvinylpyrrolidone, 0.5 parts by weight of polyvinyl alcohol, and 95.42 parts by weight of water. did.

Comparative Example 5 3 parts by weight of 4,5-dichloro-2-octyl-3-isothiazolone, 0.0 parts by weight of sodium laurylbenzenesulfonate.
A disinfectant composition was prepared consisting of 0.6 parts by weight, 2 parts by weight of carboxymethylcellulose, and 94.94 parts by weight of water.

Comparative Example 6 5 parts by weight of dichlorophene, 0.0 parts by weight of polyvinylpyrrolidone.
05 parts by weight, 0.3 parts by weight of polyacrylamide, and 9 parts by weight of water.
A disinfectant composition was prepared consisting of 4.65 parts by weight.

Comparative Example 7 2-Bromo-2-nitropropane-1,3-diol 2
A disinfectant composition was prepared consisting of 0 parts by weight and 80 parts by weight of water.

Test Example 1 Metal Working Oil Preservation Test The test method was carried out as shown below, using an emulsion liquid obtained by diluting metal working oil 30 times as the test liquid (test liquid pH 8.5). That is, inoculum of rotten cutting oil was inoculated into the test liquid so that the number of bacteria was 107 to 108 cells/ml, and then 7 inoculated with the drugs of Examples 1 to 4 and Comparative Examples 1 to 7.
After adding 00 μg/ml, shaking culture was performed at 35°C. After storage for one day, the number of bacteria in the test solution was measured. Next, in the same manner as above, a predetermined amount of putrefactive bacteria is added to the test solution, and storage is continued under the same conditions as above, and the same operation is repeated for each storage period shown in Table 1. I looked into it. For comparison, a similar test was also conducted in the case where no drug was added. The results are shown in Table 1.

[0024]

[Table 1]

Test Example 2 Color Coating Liquid Preservation Test A color coating liquid (pH 9.5) was used as it was as a test liquid. Inoculum of the rotten color coating solution was inoculated into this test solution so that the number of bacteria was 10 7 to 10 8 cells/ml, and the same procedure as in Test Example 1 was carried out. Note that the amount of fungicide added was 1500 μg/ml. The results are shown in Table 2.

[0026]

[Table 2]

Test Example 3 Water-based paint anti-mold test Water-based paint was used as a sample and the method specified by JIS test method (JIS Z
2911), the antifungal effects of the fungicides of Examples 1 to 4 and Comparative Examples 1 to 7 were investigated. The test was conducted as follows. First, a filter paper was immersed in a paint containing 0.5% by weight of a bactericide, the paper stock was evenly applied, and the paper was dried (temperature 20°C,
75% humidity for 48 hours). Next, this filter paper has a diameter of 30 mm.
It was cut into a circle of mm and immersed in water at 20°C. Test pieces were prepared with different water immersion periods for 1, 7, and 14 days. Next, after drying each test piece, it was pasted on an agar plate medium based on glucose and peptone.
A mixed spore suspension of the following five types of mold was spread on top of the mold so that the number of mold spores was 105/ml, and after culturing at 30°C for one week, the effect was examined by visual observation using the following evaluation criteria. . For comparison, a test was also conducted on a sample without additives. The results are shown in Table 3.

Mixed spores Aspergillus niger, Penicillium funiculosum, Cladosporium cladosporioides, Aureobasidium pullulans, Gliocladium virens.

Evaluation Criterion 3: No bacterial growth is observed on the test piece. 2: The growth of the fungal system on the test piece does not exceed 1/3 of the total area. 1: Growth of fungal system on the test piece exceeds 1/3 of the total area.

[0030]

[Table 3]

[0031]

Effects of the Invention According to the present invention, the synergistic effect of the combination of the 5-chloro-2-methyl-4-isothiazolin-3-one clathrate compound and a specific bactericide has antibacterial activity against all bacterial species. It is possible to obtain a bactericidal composition which has an extremely high antibacterial activity and has an excellent long-lasting antibacterial effect over a wide range of pH.

Claims (1)

[Claims] Claim 1: (A) an inclusion compound of 5-chloro-2-methyl-4-isothiazolin-3-one; and (B) methylene bisthiocyanate, 1,2-benzisothiazolin-3-one;
A disinfectant composition comprising at least one disinfectant selected from 3-one, 4,5-dichloro-2-octyl-3-isothiazolone, and dichlorophene.