JPH037205A - Industrial antifungal and mildewproofing agent and composition of same agent - Google Patents

Abstract

PURPOSE:To obtain an industrial antifungal and mildewproofing agent useful for preventing generation of obstruction owing to microorganism propagating in various industrial products and raw material of the products with exhibiting excellent bacteriostatic action, etc., against fungi and molds containing specific isothiazoline compound as active ingredient. CONSTITUTION:One or more isothiazoline compounds expressed by the formula (X is H or Cl), e.g. 4,5-dichloro-2-(n-octyl)-4-isothiazoline-3-on are contained in the aimed industrial antifungal and mildewproofing agent, and further, one or more compounds expressed by the formula and at least one species selected from methylene bisthiocyanate, 2,2-dibromo-3-nitrylopropionamide or hexabromodimethyl sulfone, etc., are contained in the aimed industrial antifungal and mildewproofing composition as active ingredients. The compound expressed by the formula is dissolved in solvent, according to the object, and is used by directly mixing with an industrial product or raw material of the product, or spraying on an industrial product.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrial anti-stone and anti-fungal agent and an anti-dent and anti-fungal composition for preventing damage caused by microorganisms propagating on various industrial products and their raw materials.

Loneliness and distortion In recent years, microbial damage caused by bacteria and fungi has occurred in various industrial products and their raw materials, and countermeasures have become a problem. In other words, the occurrence of these microorganisms causes a significant decline in the performance, quality, etc. of industrial products.
Conventionally, various fungicides and fungicides have been used as countermeasures.

However, the industrial antibacterial and fungicidal agents that have been used in the past only have either anti-orchid action or bactericidal action, and are only effective against bacteria or fungi, so they are not sufficient. There were few that exhibited sufficient antibacterial and antifungal performance.

Furthermore, even if they had sufficient performance, many of them had poor stability (and poor practicality).

For example, in Japanese Patent Publication No. 61-31081, 2-n-
Although octyl-4-isothiaprin-3-one has been disclosed, the problem is that this compound has a low antibacterial effect against bacteria. Furthermore, 5-chloro-2-(n-octyl)-4-isothiazolin-3one is disclosed in JP-A-61-53201, but this compound itself has a problem of poor stability. . Furthermore, JP-A No. 597
104 and JP-A-60-19704 disclose 1,2-benzisothiazolin-3-one. However, since this compound itself has a small antibacterial effect against bacteria, it is used as a composition with other bactericidal agents.

In addition, Japanese Patent Publication No. 58-1082 and Special Publication No. 58-1982
Publication No. 4682 and others disclose compositions of metal salts, alkali metal salts, or alkaline earth metal salts of isothiazolone compounds and known compounds; however, when a drug containing these metal salts is added to a latex emulsion, There is a problem in that a shock occurs and the value of the product is lost.

SUMMARY OF THE INVENTION An object of the present invention is to provide an industrial antibacterial and antifungal agent and a composition for preventing damage caused by microorganisms that propagate in various industrial products and their raw materials.

We discovered that 4,5-dichloro-2-(n-octyl)-4-isothiazolin-3-one and 5-chloro-2
It has been discovered that -(n-octyl)-4-isothiazolin-3-one exhibits excellent bacteriostatic activity against both bacteria and molds, and also exhibits bactericidal activity against bacteria,
We succeeded in solving the above problems.

The present invention will be explained in detail below.

The characteristics of the industrial antibacterial and fungicidal agent according to the present invention for the purpose of
ounce contains 5-chloro to 2-(n-octyl)-4-isothiazolin-3-one or a mixture of both as active ingredients.

Furthermore, the present invention provides the above-mentioned compounds or a mixture of both, methylene bisthiocyanate, 2,2 dibromo-3
-Nitrilopropionamide, Il, 3-dibromo-5
, 5-dimethylhydantoin, 4,5-dichloro-1,
2-dithiol-3-one, hexabromodimethylsulfone, hexachlorodimethylsulfone and 2-(4-thiocyanomethylthio)hendithiazole, furthermore, 1
．． 2-benzisothiazolin-3-one, 2-(n-octyl)-4-isothiazolin-3-one, 12 dibromo-2,4-dicyanobutane, 1,4-bis(bromoacetoxy)butene, 1,2 -di(bromoacetoxy)propane, L2,3-tris(bromoacetoxy)propane, 2-(4-thiazolyl)-henzimidazole, 2,4.5.6-titrachloroisophthalonitrile, N-(fluorodichloro An industrial antibacterial and antifungal composition containing as an active ingredient at least one member selected from the group consisting of methylthio)-phthalimide and N,N-dimethyl-N-(fluorodichloromethylthio)-N-phenylsulfamide. Things are also included as features.

■4,5-dichloro-2-(n~octyl)-4-isothiazoline-3- used as an active ingredient in the present invention
5-chloro-2-(n-octyl)-4-isothiazolin-3-one has the following formulas (1) and (2).

■ ■ These compounds have extremely strong efficacy against both bacteria and fungi in plastics, starch pastes, latex emulsions, organic adhesives, textile products, leather products, cutting oils, etc. at commonly used concentrations. Therefore, it can be effectively used as an antibacterial and antifungal agent for these industrial products and raw materials. Further, the compound C has the feature that it can be easily formulated into a formulation by being soluble in organic solvents or plasticizers, such as ethyl cellosolve, Hensen, toluene, xylene, acetone, methyl isobutyl ketone, ethyl acetate, dioctyl phthalate, and tricresyl phosphate.

In particular, 4,5-dichloro-2-(n-octyl)-4-
Inthiazolin-3-one has excellent stability and has 10ffiff1% each of ethyl acetate, ethyl cellosolve, and toluene.
The molten solution shows no decomposition when stored at 55°C for 60 days, and 0.1 to 10% of dioctyl phthalate
Even when each solution was held at 200°C for 2.0 minutes, no decomposition was observed.

In addition, each of the above-mentioned compounds used as active ingredients in the present invention is
When used in plastics, adhesives, etc., the solubility in water is extremely low, so the elution of solvents is suppressed, and the antibacterial and antifungal effect lasts for a long time.

When using the above compound as an industrial antibacterial and antifungal agent, it must be dissolved in a container appropriate for the purpose and then directly blended into the target industrial product and its raw materials, or the industrial product It can be applied as a spraying agent.

For the antibacterial and antifungal treatment of industrial products and their raw materials (i), the use of the above-mentioned compounds alone can provide sufficient effects;
Particularly in fields where damage caused by bacteria is significant, when this compound is used in combination with other known bactericidal compounds, extremely good antibacterial and antifungal effects can be obtained.

Known bactericidal compounds used here include methylene bisthiocyanate, 2,2-dibromo-3-nitrilopropionamide, 1,3-dibromo-5,5-dimethylhydantoin, and 4,5-dichloro-1,2-dithiol.・3
-one, hexabromodimethylsulfone, hexachlorodimethylsulfone, and 2-(4-thiocyanomethylthio)henzuthiazole.

These known fungicidal compounds include 4,5-dichloro-2(
n-octyl)-4-isothiazolin-3-one or 5
Chloro-2-(n-octyl)-4-isothiazoline-
The blending ratio of 3-one or a mixture of both is not particularly limited, but in terms of -a, it is about 1:10 to 10:1 (weight ratio).

In addition, the isothiazoline compound according to the present invention exhibits extremely good antibacterial and antifungal effects when mixed with a known antifungal compound. -benzisothiazoline-3-
on, 2-(n-octyl)-4isothiazoline-3-
1,2-dibromo-2,4-dicyanobutane, 1
, 4-bis(bromoacetoxy)butene, 1,2-di(bromoacetoxy)propane, 1,2゜3-tris(bromoacetoxy)propane, 2-(4-thiazolyl)-benzimidazole, 2, 4,5.6-titrachloroisophthalonitrile, N-(fluorodichloromethylthio)-phthalimide and N,N-dimethyl-N-
(Fluorodichloromethylthio)-N-phenylsulfamide and the like.

These known antifungal compounds and 4,5-dichloro-2(
n-octyl)-4-isothiazolin-3-one or 5
The blending of -chloro-2-(n-octyl)-4-isothiazolin-3-one or a mixture of the two is not particularly limited, but -numerically, it is about 1:10 to 10:1 (weight ratio).

In addition, by combining and using together as described above,
A synergistic antibacterial and antifungal effect can be obtained, with minimal It is possible to sterilize and prevent the growth of bacteria and fungi in industrial products and their raw materials.

When applying the antibacterial and antifungal agent of the present invention to various industrial products and their raw materials, it can be directly mixed at a concentration range of 1 to 3000 ppm as an active ingredient, or it can be mixed directly with an active ingredient concentration range of 1 to 3000 ppm, or
It is best to dilute it to about 1,000 times and spray it directly in the form of a solution.

The antibacterial activity and bactericidal activity of the antibacterial and antifungal agent of the present invention will be specifically explained below with reference to Examples.

Example 1 Selection 1 tube shield holder V (1) Test bacteria (bacteria) A: Bacillus subtilis (Bacillus 5ub)
tilis) B: Staphylococcus aureus (Staphylococcus aureus) C:
Escherichia coli
li) D: Pseudomonas aerginosa (molds) E: Aspergillus niger
niger) F; Cladosporium cladosporioides
rioides) G: Chaetomium globosum (Cha
etomium globosum) H: Alternaria alternate ■ = Fusarium oxysporum yeast> J: Saccharomyces cervisi ae)
(2) Test method 4.5-dichloro-2-(n-octyl)-4-isothiazolin-3-one (hereinafter abbreviated as DOCT) or 5
- Bouillon agar medium (bacteria) containing a predetermined concentration of chloro-2-(n-octyl)-4-isothiapurin-3-one (hereinafter abbreviated as MC0T), and potato agar medium (
After pouring 1 ml of mold and yeast into a Petri dish and solidifying it, a precultured suspension of the test bacteria was inoculated in a striped pattern with one platinum loop.
After the bacteria were left at 37° C. for 2 days, the growth state was observed and the minimum growth inhibitory concentration (MrC) was determined.

In addition, to evaluate the bactericidal power against bacteria, the active ingredient compound of the present invention is added at a predetermined concentration to an aqueous suspension of pre-cultured test bacteria, and after 3 hours of shaking contact, a portion of the solution is taken. Bacterial viability was determined by meat extract bouillon agar culture.

(3) Test results Table 1 shows the minimum inhibitory concentration (MIC) for each microorganism.

Next, a suspension of spores of 5 types of fungi was uniformly sprayed, and 4 degrees of sterilization against bacteria was shown in Table 2.
After culturing for a week, the growth of fungal hyphae on the vinyl wallpaper was observed. The results are shown in Table 3.

Table 3 From the above results, DCOT and MCOT had a growth-inhibiting effect on all microorganism groups, including bacteria, mold, and yeast, and were also observed to have a bactericidal effect on bacteria.

Example 2 DCOT or MC0T dissolved in dioctyl phthalate was added to the vinyl wallpaper compounding component at a concentration of 5 to 110% in terms of compound.
0pp was added to make vinyl wallpaper.

Prepare an agar plate medium in a Petri dish, place a 30 mm square vinyl wallpaper on the medium after solidification, and place (E) of Example 1 on top of this.
, (F), (G), (H), (1) -: No mold growth.

+: Mold occurrence is 5% or less.

+: 5 to 20% occurrence of cahi.

+1+: Mold occurrence is 20% or more.

As can be seen from Table 3, the antibacterial and antifungal agent of the present invention is 20pp.
The addition of ffl prevented the growth of mold on vinyl wallpaper.

Example 3 A suspension of 4 types of bacteria and 5 types of fungi described in Example 1 was added to 10 latex emulsion liquids, and DCOT or MCOT was added individually to a predetermined concentration at 28°C. After being left in a thermostatic chamber for 4 weeks, the latex emulsion was examined for malodor and mold growth.

Furthermore, DCOT, 2,2-dibromo-3-nitrilopropionamide (hereinafter abbreviated as DBNPA), 4.5 dichloro-1,2-dithiol-3-one (hereinafter abbreviated as DCDT), and hexabromodimethylsulfone (hereinafter abbreviated as HB) (abbreviated as S) was mixed, added to a predetermined concentration, and tested in the same manner. The results are shown in Table 4.

When DCOT and MCOT were added alone at 50 ppm,
Furthermore, by combining DCOT with various chemicals, it was possible to prevent rot and mold growth in the latex emulsion with the addition of 20 ppm.

Example 4 Emulsified cutting oil was added to water to prepare emulsified oil.

DCOT and MCOT were added to the mixture to a predetermined concentration, and seed sludge generated in the cutting oil was added. This was placed in a Smith fermentation tube with a volume of 20 m2, cultured at 37°C, and the amount of gas generated each day was measured. Furthermore, D.C.O.T.
and methylene bisthiocyanate (hereinafter abbreviated as MBTC)
were mixed at a ratio of 50:50 (weight ratio) and tested in the same manner.

The results are shown in Table 5.

From the above results, DCOT and MCOT alone have a
By adding 0 ppm, and further by adding 20 ppm in combination with MBTC, it was possible to completely prevent spoilage of the emulsified cutting oil.

Example 5 Parts in this example represent weight.

150 parts of dioctyl phthalate, 5 parts of chlorinated paraffin,
Blowing agent (azodicarbonamide) 7 parts, stabilizer (lead stearate) 3 parts, calcium carbonate 25 parts, flame retardant (antimony dioxide) 1.2 parts, mineral spirits 3 parts, D
An additive agent for polyvinyl chloride was prepared by thoroughly mixing 4 parts of COT (compound of the present invention).

Heat this solvent in an oil bath at 200°C for 20 minutes,
When the residual rate of DCOT was examined by gas chromatography (internal standard substance method), no decomposition was observed.

Gas chromatography conditions Column: Silicon 0V-17.5%, W DMCS 60-80 mesh 1m x 3
mm Glass oven temperature: 200°C, rapid rise to 260°C after 8 minutes Inlet temperature: 270°C Carrier gas: Nitrogen, 40 ml/m jn Detector: FID Internal standard: Di-n-butyl phthalate Example 6 Parts and percentages in this example represent weight.

DCOT 2%, New Ball PE75 C Sanyo Chemical■
] 2%, Demol N [Kako Atlas (■)] 2%, carboxymethyl cellulose sodium 1%, water 83%, and 1,2-benzisothiazolin-3-one (hereinafter abbreviated as BIT), a known antifungal compound. , 2-(n-octyl)isothiapurin-3-one (hereinafter abbreviated as OCT),
A suspension was prepared by adding 10% of each of 2,4,5,6-titrachloroxophthalonitrile (hereinafter abbreviated as TNP) and mixing and pulverizing the mixture.

0.05.0, 5.0.1.0.2 of each drug to the urethane polymer and the urethane latex applied to it.
A test piece (3 cm x 3 cm) of artificial leather containing 10% of the artificial leather was placed on a bouillon agar medium, sprayed with the mold mixed suspension used in Example 1, and the mold on the sample surface was cultured at 28°C for 14 days. The growth condition was observed. Furthermore, the same test was conducted using a known antifungal agent alone, and the results were compared.

The results are shown in Table 6.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) Contains one or two types of isothiazoline compounds represented by (in the formula, X represents a hydrogen atom or Cl) as an active ingredient An industrial antibacterial and antifungal agent. (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) One or two types of isothiazoline compounds represented by (in the formula, X represents a hydrogen atom or Cl) and methylene bisthiocyanate , 2,2-dibromo-3-nitrilopropionamide, 1,3-dibromo-5,5-dimethylhydantoin, 4,5-dichloro-1,2-dithiol-3
-one, hexabromodimethylsulfone, hexachlorodimethylsulfone and 2-(4-thiocyanomethylthio)benzothiazole, 1,2-benzisothiazoline-
3-one, 2-(n-octyl)-4-isothiazolin-3-one, 1,2-dibromo-2,4-dicyanobutane, 1,4-bis(bromoacetoxy)butene, 1,
2-di-(bromoacetoxy)propane, 1,2,3
-tris(bromoacetoxy)propane, 2-(4-
thiazolyl)-benzimidazole, 2,4,5,6-
at least one selected from the group consisting of tetrachloroisophthalonitrile, N-(fluorodichloromethylthio)-phthalimide and N,N-dimethyl-N-(fluorodichloromethylthio)-N-phenylsulfamide. An industrial antibacterial and antifungal composition containing as an ingredient.