JPH0640811A - Industrial germicide and industrial method for sterilization - Google Patents

Abstract

PURPOSE:To obtain an industrial germicide comprising a dihalogenated glyoxime diacylate or a dihalogenated glyoxime derivative and further other industrial germicidal ingredients in combination as an active ingredient and capable of manifesting excellent germicidal action. CONSTITUTION:The industrial germicidal and bacteriostatic agent comprises a dihalogenated glyoxime diacylate of formula I [R' is (halogenated) 1-4C alkanoyl; X is halogen] (e.g. dichloroglyoxime diacetate) as an active ingredient or a dihalogenated glyoxime diacylate of formula II [R is H or (halogenated) 1-4C alkanoyl; X is halogen] and a well-known industrial germicidal ingredient (with the proviso that 4,5-dichloro-1,2-dithiol-3-one is excluded) as an active ingredient. One or more compounds selected from organic nitrogen- and sulfur- based, organic bromine-based, organic nitrogen-based or organosulfur-based compounds are preferably used as the industrial germicidal ingredient. This germicide is capable of manifesting strong germicidal effects on various microorganisms by adding a small amount thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to industrial sterilization, bacteriostatic agents and sterilization / bacteriostatic methods. More specifically, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oils, fiber oils, paints, antifouling paints, paper coating liquids, latexes, pastes, etc. The present invention relates to an industrial sterilization, bacteriostatic agent, sterilization, and bacteriostatic method useful for preservative, sterilization, and bacteriostatic.

[0002]

2. Description of the Related Art Conventionally, in the papermaking process in the paper and pulp industry and in the cooling water system in various industries, slimes caused by bacteria and fungi are generated, and there are obstacles such as deterioration of product quality and production efficiency. Are known. In addition, many industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, and sizing agents are apt to be rotted or contaminated by bacteria or fungi, which spoils the product and reduces its value.

Many fungicides have been used to prevent damage by these microorganisms. Traditionally, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to humans and seafood,
Its use has been regulated because it causes environmental pollution. Recently, relatively low toxicity of methylenebisthiocyanate, 1,2-benzisothiazolin-3-one and 5-chloro-2-methyl-4-isothiazoline-3. An organic nitrogen-sulfur system represented by -one, 2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide,
1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, organic bromine system represented by bistribromomethylsulfone, and 4,5-dichloro-1,
Compounds such as organic sulfur compounds represented by 2-dithiol-3-one are widely used as industrial fungicides (see "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Society for Antibacterial and Antifungal Agents in 1986). ).

[0004] Dichloroglyoxime is known to exhibit a growth-inhibiting effect on typical Gram-negative and Gram-positive bacteria [Dirasat 13 (7), 185 to 188 (1986)]. However, it is not known that a synergistic bactericidal effect is exhibited in combination with other drugs. Further, it is not known that the dihalogenated glyoxime diacylates have more effective bactericidal properties.

[0005]

The above-mentioned dichloroglyoxime has a bactericidal action but is relatively weak. Therefore, it is an object of the present invention to provide a bactericide having a strong bactericidal effect against various microorganisms even when added in a small amount.

[0006]

Thus, according to the present invention, the general formula (I '):

[0007]

[Chemical 3] (In the formula, R'is an alkanoyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and X is a halogen atom.) An industrial fungicide containing a dihalogenated glyoxime diacylate as an active ingredient. Will be provided.

According to the present invention, the general formula (I):

[0009]

[Chemical 4] (In the formula, R represents an alkanoyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and X represents a halogen atom.) And a known halogenated industrial bactericidal component However, hereinafter, an industrial bactericidal agent containing 4,5-dichloro-1,2-dithiol-3-one) as an active ingredient is provided.

The present invention is based on the discovery of the fact that dihalogenated glyoxime diacylates surprisingly exhibit a remarkable bactericidal action and can be used as a bactericide superior to dihalogenated glyoximes. Also, by using other industrial bactericidal components in combination with the dihalogenated glyoxime derivative, a bactericidal action superior to that of each is exhibited, that is, the antibacterial spectrum is expanded, and the bactericidal action is enhanced, which is a synergistic effect of the two. It is thought to be due to.

The bactericide of the present invention is a reducing environment,
For example, excellent bactericidal activity is exhibited even in an environment in which a reducing substance is present at 5 mg / l (sulfite ion equivalent) or more. In the above general formulas (I ′) and (I), “C1 to C4 optionally substituted with a halogen atom” represented by R and R ′
"Alkanoyl group having 1 to 4 carbon atoms" in "alkanoyl group" is, for example, acetyl, propionyl, n-
Examples include butyryl and isobutyryl. Of these, acetyl and propionyl are particularly preferable.

The "halogen atom" in the "halogen atom" represented by X in the above formula and the "alkanoyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom" represented by R and R'is chlorine. , Bromine, fluorine or iodine atoms. Chlorine is particularly preferable. As the dihalogenated glyoxime represented by the above formula (I),
Examples thereof include dichloroglyoxime, dibromoglyoxime, difluoroglyoxime and diiodoglyoxime, with dichloroglyoxime being particularly preferred.

Examples of the halogenated glyoxime diacylate derivative represented by the above formula (I ') include dichloroglyoxime diacetate, dichloroglyoxime dipropionate, dichloroglyoxime di-n-butyrate, dichloroglyoxime di-iso-butyrate, dichloro. Examples thereof include glyoxime bis (chloroacetate), chloroglyoxime diacetate, and chloroglyoxime dipropionate. Of these, dichloroglyoxime dipropionate is particularly preferable.

Other industrial germicidal components used in the present invention include organic nitrogen-sulfur compounds, organic bromine compounds, organic nitrogen-based compounds, and organic sulfur-based compounds. Examples of the organic nitrogen-sulfur compounds include alkylenebisthiocyanates such as methylenebisthiocyanate and ethylenebisthiocyanate; 5-chloro-2-methyl-4-
Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-
Examples thereof include 3-isothiazolone compounds such as isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one or a complex of magnesium chloride or calcium chloride with these, or a complex of these with a metal salt. Among these compounds, alkylenebisthiocyanate is methylenebisthiocyanate, 3-isothiazolone compound or 5-chloro-2-methyl-4 as a complex of these with a metal salt.
-Isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octylisothiazolin-3-one or a complex thereof with magnesium chloride or calcium chloride is used. preferable.

As the organic bromine compound, 2-
Bromo-2-nitropropane-1,3-diol, 1,1-dibromo-1-nitro-2-propanol, 2,2-dibromo-
2-nitro-1-ethanol, 2-bromo-2-nitro-1-ethanol, 1,1-dibromo-1-nitro-2-acetoxyethane, 1,1-dibromo-1-nitro-2-acetoxypropane, 2-bromo-2-nitro-1,3-diacetoxy-propane, tribromonitromethane, β-bromo-β-nitrostyrene, 5-bromo-5-nitro-1,
3-dioxane, 5-bromo-2-methyl-5-nitro-
Organic bromonitro compounds such as 1,3-dioxane and 2- (2-bromo-2-nitroethenyl) furan; 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-
Organic bromocyano compounds such as bromomethylglutaronitrile; 1,2-bis (bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane, 1,4-bis (bromoacetoxy) -2-butene, 1, 2,3-tris (bromoacetoxy) propane, methylenebisbromoacetate, benzyl bromoacetate, N-bromoacetamide, 2-
Examples thereof include organic bromocarboxylic acid esters or amides such as bromoacetamide and 2-hydroxylethyl-2,3-dibromopropionate. 2 of these compounds
-Bromo-2-nitropropane-1,3-diol, 2-bromo-2-nitro-1-ethanol, 2,2-dibromo-2
-Nitro-1-ethanol, 2-bromo-2-nitro-
1,3-diacetoxy-propane, 2,2-dibromo-3-nitrilo-propionamide, β-bromo-β-nitrostyrene, 5-bromo-5-nitro-1,3-dioxane, 1,2-
Bis (bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane, 1,4-bis (bromoacetoxy)-
Preference is given to using 2-butene, 1,2,3-tris (bromoacetoxy) propane.

Examples of organic nitrogen compounds include α-chlorobenzaldoxime, α-chlorobenzaldoxime acetate; N, 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride; dichloroisocyanate, sodium dichloroisocyanurate, trichloro. Chlorinated isocyanuric acid compounds such as isocyanuric acid; quaternary ammonium compounds such as decalinium chloride, alkylisoquinolinium bromide, benzalkonium chloride; methyl 2-benzimidazolylcarbamate, 3-iodo-2-
Carbamic acid such as propargyl butylcarbamic acid or its ester; 1- [2- (2,4-dichlorophenyl)]
-2 '-[(2,4-dichlorophenyl) methoxy] ethyl-
3- (2-phenylethyl) -1H-imidazolium chloride, 1- [2- (2,4-dichlorophenyl) -2-
(2-Propenyloxy) ethyl] -1H-imidazole and other imidazole compounds; 2- (2-furyl) -3-
(5-Nitro-2-furyl) -acrylic acid amide, 2-
Amide compounds such as chloroacetamide; amino alcohol compounds such as N- (2-hydroxypropyl) -aminomethanol and 2- (hydroxymethylamino) ethanol; 2-pyridinethiol sodium-1-oxide, 5-chloro-2 , 4,6-Trifluoroisophthalonitrile, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile, 1-bromo-3-chloro- Examples include 5,5-dimethylhydantoin, N- (2-methyl-1-naphthyl) maleimide, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylenedichloride] and the like. Of these compounds, α-chlorobenzaldoxime, 5-chloro-2,4,6-trifluoroisophthalonitrile and 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile are particularly preferable.

The organic sulfur compounds include 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, 4,3
5-dichloro-1,2-dithiol-3-one, dithio-2,2 '
-Bis-1-benzmethylamide, bis (trichloromethyl) sulfone, bis (tribromomethyl) sulfone,
Examples thereof include ethylene thiuram monosulfide and 2-hydroxypropyl methanethiosulfonate.

Of these compounds, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, bis (trichloromethyl) sulfone and bis (tribromomethyl) sulfone are preferred. Other bactericides include 3-acetoxy-1,1,2-triiodo-1-propene, glutardialdehyde, dichlorophen, hydrogen peroxide, maleic anhydride and the like.

Thus, according to one aspect of the present invention, there is provided an industrial germicide comprising a dihalogenated glyoxime diacylate and a known industrial germicidal component. Further, according to another aspect of the present invention, there is provided an industrial germicide comprising a dihalogenated glyoxime and a known industrial germicidal component. Among the compounds used in the present invention, the dihalogenated glyoxime which is one component of the present invention can be easily synthesized by halogenating the glyoxime.

The dihalogenated glyoxime diacylate can be synthesized by acylating the dihalogenated glyoxime synthesized as described above by a known method. That is, it can be obtained by reacting a dihalogenated glyoxime with an acid anhydride under an acid catalyst or by reacting a dihalogenated glyoxime with an acid chloride in the presence of triethylamine.

In the combination of the dihalogenated glyoxime, which is the active ingredient of the present invention, and other industrial bactericidal ingredients, the ratio at which a synergistic effect is exhibited is 20: 1 to 1:20.
Is suitable, and it is preferably 5: 1 to 1:10. Further, the ratio (weight ratio) at which the synergistic effect is exhibited in the combination of the dihalogenated glyoxime diacylate and the known industrial sterilizing component is 50: 1.
It is suitable to be set to ˜1: 20, and 20: 1 to 1:10
Is more preferable. In any case, one or more kinds of industrial sterilizing components may be used in combination.

The active ingredient of the present invention is preferably used in the form of a liquid preparation, particularly an aqueous preparation. But,
The present invention is not limited to this, and may be used in the form of powder or the like depending on the intended use.

When the system to be sterilized is various water systems such as process water in the papermaking process and industrial cooling water, a liquid formulation, especially an aqueous formulation is usually used. That is, it can be prepared by dissolving the active ingredient in water and / or a hydrophilic solvent, and further adding a surfactant if necessary.

As the hydrophilic organic solvent, amides such as dimethylformamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether. ,
Glycol ethers such as tripropylene glycol monomethyl ether, alcohols having up to 8 carbon atoms or esters such as methyl acetate or ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate and propylene carbonate. It is also possible to use an aqueous solvent which is a mixture of water and water.

As the surfactant, a cationic, anionic, nonionic or amphoteric surfactant is suitable, and a nonionic surfactant is preferable from the viewpoint of stability as a preparation. Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts (ethylene oxide is abbreviated as EO hereinafter), alkylphenol (EO) adducts, fatty acid (EO) adducts, and polyhydric alcohol fatty acid esters. (EO) adduct, higher alkylamine (EO)
O) adduct, fatty acid amide (EO) adduct, fat and oil (EO) adduct, propylene oxide [P. Abbreviated as O] (EO) copolymer, alkylamine (PO)
(EO) copolymer adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, alkylolamide and the like. The mixing ratio of these preparations is such that the total amount of the bactericide active ingredient is 1 to 50 parts by weight, and the amount of the surfactant is at least 0.
It is preferably 01 parts by weight, and the balance is preferably a hydrophilic organic solvent.

When the system to be sterilized is an oil system such as heavy oil sludge, cutting oil, oil paint, etc., it is preferable to use a hydrocarbon solvent such as kerosene, heavy oil or spindle oil to prepare a liquid agent, and various surface active agents are used. Agents may be used.

Further, for the system to be sterilized in which the active ingredient of the present invention can be directly dissolved or dispersed, it can be used directly or as a powder formulation diluted with a solid diluent (eg kaolin, clay, bentonite, CMC etc.). Alternatively, various surfactants may be used. Also, depending on the combination,
The preparation may be prepared with only the active ingredient without a solvent or a surfactant.

The amount of the composition of the present invention to be added varies depending on the combined active ingredients and the object to be sterilized. In particular, when the composition is added to the process water system of the papermaking process or the industrial cooling water system, it is As a concentration for suppressing growth (bacteriostatic concentration), when a dihalogenated glyoxime is used in combination with a known industrial bactericidal component, the concentration is usually 0.0
5 to 20 mg / l, 0.0 when the dihalogenated glyoxime diacylate is used alone or when the dihalogenated glyoxime diacylate is used in combination with a known industrial sterilizing component.
Addition of about 5 to 20 mg / l is sufficient.

In the case of bactericidal use, the concentration of the active ingredient is 0.1 to 20 mg / l when the dihalogenated glyoxime is used in combination with a known industrial bactericidal ingredient, and the dihalogenated glyoxime diacylate or dihalogen is used. When the diacylates of the modified glyoxime are used in combination with a known industrial sterilizing component, the purpose can be achieved at 0.5 to 50 mg / l.

In the method of the present invention, when the above-mentioned active ingredients are added at the same time, it is convenient to use the same preparation as described above, but they are separated from each other in terms of long-term storage stability of the preparation. When it is preferable to add them or when they are added separately, they are used as separate formulations. From this point of view, there is provided an industrial sterilization method characterized in that the above-mentioned active ingredients are added to the system to be industrially sterilized simultaneously or separately.

Even when they are added separately, it is usually convenient to make them into liquid formulations. For example, such a preparation can be prepared by adding the above-mentioned organic solvent or surfactant. In addition, the active ingredient of the present invention can be used directly or as a powder for a sterilizing or bacteriostatic target system in which it can be directly dissolved or dispersed.

According to the above-mentioned method, the addition concentration of the active ingredient, the mixing ratio of the dihalogenated glyoxime derivative and the other industrial sterilizing component vary depending on the type and amount of the bacterium to be sterilized and the type of industrial sterilizing component. It suffices to consider the above-mentioned addition concentration and blending ratio.

[0033]

EXAMPLES The present invention is illustrated by the following synthetic examples, formulation examples, examples and comparative examples. Synthetic Example 1 [Synthesis of glyoxime] 32.8 g of hydroxylamine sulfate was dissolved in 70 ml of water, and 29.0 g of 40% glyoxal solution was added dropwise to the mixture. Further, 40% aqueous sodium hydroxide solution was added to neutralize the mixture, and after 30 minutes, the precipitated white crystals were recrystallized from water to obtain 10.6 g of the title compound (mp178).
C).

Synthesis Example 2 [Synthesis of chloroglyoxime and dichloroglyoxime] 8.8 g of glyoxime obtained by the method of Synthesis Example 1 is dissolved and mixed in 100 ml of methanol. Chlorine gas was blown into this little by little and mixed. At this time, the temperature in the system is 10 to
Hold at 12 ° C. When the reaction product was measured with HPLC over time, first, chloroglyoxime was produced (reaction A), and then dichloroglyoxime was produced (reaction B).
did.

[0035]

[Chemical 5] The reaction was stopped at A, the solvent was removed, and the residue was recrystallized from water to give white crystals of chloroglyoxime (mp 156 ° C) (yield 36%). When the reaction was stopped at B, the solvent was removed, and the residue was recrystallized from methanol, white crystals of dichloroglyoxime (mp 199 ° C) (I, R = H, X =
Y = Cl) was obtained (yield 55%).

Synthesis Example 3 [Synthesis of dichloroglyoxime diacetate] 2.0 g (0.0) of dichloroglyoxime (Compound No. 6)
127 mol), 20 ml of dichloroethane, and 2.4 g (0.0306 mol) of acetic acid chloride are stirred while cooling with an ice bath. After adding 3.1 g (0.0307 mol) of triethylamine to this, a further 30
Stir for a minute. After washing twice with 15 ml of water and concentrating the dichloroethane solution under reduced pressure, white crystals of dichloroglyoxime diacetate (Compound No. 2) were obtained (yield 3
0%).

Compound No. 2-5 was also synthesized in the same manner as above except that the corresponding acid chloride was used. Table 1 shows the structural formulas and physical property values of the diacylates produced as described above. In Table 1, compound numbers 1 to 5 are diacylates of the present invention, and the numerical value of dichloroglyoxime of compound number 6 is shown for comparison.

[0038]

[Table 1]

Formulation Example 1 Dichloroglyoxime diacetate 10 parts by weight Dimethyl glutarate 90 parts by weight Formulation Example 2 Dichloroglyoxime dipropionate 10 parts by weight Dimethyl glutarate 90 parts by weight Formulation Example 3 Dichloroglyoxime di-n-butyrate 5 Parts by weight dimethyl glutarate 95 parts by weight formulation example 4 dichloroglyoxime diisobutyrate 5 parts by weight dimethyl glutarate 95 parts by weight formulation example 5 bis (chloroacetyl) dichloroglyoxime 10 parts by weight dimethyl glutarate 90 parts by weight The abbreviations for the reagent agents are shown in Table 2.

[0040]

[Table 2] Other formulation examples are shown in Tables 3 to 5.

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

Test Example 1 [Test for confirming bactericidal effect against bacteria] Pseudomonas aeru which is a gram-negative bacterium generally found in process water in the paper and pulp industry, cooling water for various industries, etc.
Using ginosa and Staphylococcus aureus, a Gram-positive bacterium, the minimum concentration (mg) of a drug that can sterilize a viable cell count of 10 ⁶ cells / ml or more to 10 ³ cells / ml or less (bactericidal rate 99.9% or more) / l).

The measuring method is as follows. A bacterial solution pre-cultured in a broth medium is added to physiological saline so that the viable cell count becomes 10 ⁶ cells / ml or more, and a drug is added to this, and the mixture is added at 37 ° C. for 1 hour. After shaking, the number of surviving bacteria was measured, and the minimum concentration at which 99.9% or more of the initial number of bacteria was killed was determined. The test results are shown in Table 6.

[0046]

[Table 6]

Test Example 2 [Test for confirming bactericidal effect on yeast] Candida albicans was used to sterilize a viable cell count of 10 ⁵ cells / ml or more to 10 ² cells / ml or less (bactericidal rate 99.9%).
The minimum concentration (mg / l) of the possible drug was determined.

The measuring method is as follows:
The number of viable bacteria is 10 ^FiveMore than pieces / ml
And add the drug to it and shake at 37 ° C for 1 hour.
The number of surviving bacteria was measured, and the initial number of bacteria was 9
The minimum concentration at which 9.9% or more was killed was determined. Test results
It shows in Table 7.

[0049]

[Table 7]

Test Example 3 [Test for confirming bactericidal effect against mold] The minimum concentration (mg / l) of a drug that suppresses the growth of Aspergillus niger was determined. Using Czapek medium as the medium,
Inoculate a fixed amount of spores from a preserved strain that had been precultured on a slope and suspend it in sterile water (10 ml), shake at 7 ° C for 7 days, and then add the mycelium to the medium. The concentration at which no growth was observed was determined. The results are shown in Table 8.

[0051]

[Table 8]

Test Example 4 [Test for sterilizing power against white water in high-quality neutral papermaking process] White water (pH measured by a high-quality papermaking machine of a certain paper mill)
7.8, Pseudomonas genus, Bacillus genus, Staphylococcus genus, Micrococcus genus, Flavobacterium genus) was added to the drug, shaken at 37 ° C for 1 hour, and the number of surviving bacteria was measured. , Initial bacterial count (8.1 x 10 ⁶
The minimum concentration at which more than 99.9% of cells / ml) was killed was determined. The results are shown in Table 9.

[0053]

[Table 9]

Test Example 5 [Test for sterilizing power against white water in newspaper acidic papermaking process] White water (pH 4.
6, reducing substance SO ₃ ^{2 -} terms 11 ppm, Pseudomonas, Staphylococcus, Alcaligenes, Flavobacterium, the addition of agents to the Bacillus genus mainly), shaken for one hour at 37 ° C., then The number of surviving bacteria was measured, and the initial number of bacteria (2.5 × 10 ⁶ cells / ml) was 99.9.
The minimum concentration at which 100% or more was killed was determined. The results are shown in Table 10.

[0055]

[Table 10]

Test Example 6 [Efficacy Confirmation Test as Industrial Water-Based Slime Control Agent] Slime generated in an open circulation cooling tower was dispersed in industrial water and filtered with No. 2 filter paper to give a test water ( pH:
7.2, viable cell count: 2.0 × 10 ⁶ cells / ml, bacterial species: Pseudo
monas sp., Flavobacterium sp., Alcaligenes sp., Ba
cillus sp.).

The broth medium added to the test water is placed in a pre-sterilized L-type test tube. Then, a predetermined amount of each drug was added thereto, and the mixture was cultured at 30 ° C. with shaking. After 24 hours, the turbidity due to the growth of bacteria was measured by the absorbance at 660 nm to determine the effect. The minimum amount of addition of each drug at which an increase in absorbance is not observed, that is, the minimum growth inhibitory concentration (MIC 2
4Hr) was obtained and is shown in Table 11.

[0058]

[Table 11]

Test Example 7 [Effect confirmation test for white water at a paper mill (Part 1)] White water collected from a certain paper mill (I) was filtered with No. 2 filter paper to give a test water (papermaking: fine paper). (Acidic papermaking), p
H: 4.3, SO ₃ ^2- : 0 mg / l, viable cell count: 5.5 × 10
⁵ cells / ml, Species: Pseudomonas sp., Flavobacterium s
p., Alcaligenessp., Bacillus sp.).

The broth medium added to the test water is placed in a previously sterilized L-type test tube. Then, a predetermined amount of each drug was added thereto, and the mixture was cultured at 30 ° C. with shaking. After 24 hours, the turbidity due to the growth of bacteria was measured by the absorbance at 660 nm to determine the effect. The minimum amount of addition of each drug at which an increase in absorbance is not observed, that is, the minimum growth inhibitory concentration (MIC 2
4Hr) was obtained and is shown in Table 12.

[0061]

[Table 12]

Test Example 8 [Effect Confirmation Test for White Water at Paper Mill (Part 2)] White water collected from a certain paper mill (II) to (V) was filtered with No. 2 filter paper to be used as test water (each). An explanation of white water is shown in Table 17.).

The broth medium added to the test water is placed in a previously sterilized L-type test tube. Next, a predetermined amount of each drug was added thereto, and the cells were cultured with shaking at 30 ° C., and the absorbance was measured at 660 nm every hour. The time (t) from the start of measurement until the increase in absorbance due to the growth of bacteria exceeds 0.1 was determined.

The value of t when no drug is added is to, the drug is Xppm
If the value of t at the time of addition is tx, the growth inhibition time Tx is T
It is obtained by x = tx-to. Table 1 shows the Tx value of each drug
3 to 16 are shown.

[0065]

[Table 13]

[0066]

[Table 14]

[0067]

[Table 15]

[0068]

[Table 16]

[0069]

[Table 17]

Test Example 9 [Efficacy Confirmation Test for White Water at Paper Mill (Part 3)] 2 mg / l of each agent was added to white water collected from the paper mill (VI), and the number of viable bacteria was measured after shaking at 30 ° C. for 30 minutes. (Extract: Medium paper, pH: 7.3, SO ₃ ^2- 15 mg / l, viable cell count: 1.0 x 10 ⁷ cells / ml, bacterial species: Pseudomonas sp., F
lavobacterium sp., Alcaligenes sp., Bacillus s
p.). The results are shown in Table 18.

[0071]

[Table 18]

Test Example 10 [Test for confirming antibacterial effect against white water at a paper mill] White water collected from a certain paper mill (VII) was filtered with No. 2 filter paper to obtain test water (paper: newspaper, pH: 5). .4, S
O ₃ ²⁻ : 10 mg / l, viable cell count: 1.1 × 10 ⁶ cells / ml, bacterial species: Pseudomonas sp., Flavobacterium sp., Alcaligen
es sp., Bacillus sp.).

Liquid broth medium added to test water is placed in a pre-sterilized L-type test tube. Next, a predetermined amount of each drug was added thereto, and the mixture was cultured at 30 ° C. with shaking. After 24 hours, the turbidity due to the growth of bacteria was measured by the absorbance at 660 nm to determine the effect. The minimum addition amount that does not show the increase in absorbance of each drug, that is, the minimum growth inhibitory concentration (MIC
24 Hr) was determined and is shown in Table 19.

Test Example 11 [Effect confirmation test for white water at a paper mill (Part 4)] White water collected from a certain paper mill (VIII) was filtered with No. 2 filter paper to be used as a test water. The test water containing liquid broth medium is placed in a pre-sterilized L-type test tube. Next, 0.5 mg / l of each drug was added thereto, and the cells were cultured with shaking at 30 ° C., and the absorbance was measured at 660 nm every hour. The time (t) from the start of measurement until the increase in absorbance due to the growth of bacteria exceeds 0.1 was determined.

The value of t when no drug is added is to, the drug is xppm
If the value of t at the time of addition is tx, the growth inhibition time Tx is T
It is obtained by x = tx-to. Table 2 shows the Tx value of each drug
It shows in 0.

[0076]

[Table 19]

[0077]

[Table 20]

Test Example 12 [Bactericidal efficacy confirmation test (No. 1)] White water (pH) collected from a high-quality paper machine of a certain paper mill.
7.2, Pseudomonas genus, Flavobacterium genus, Alcaligenes genus, Bacillus genus) to which 0.5 mg / l of single drug and compound drug of Compound No. 2 were added respectively, and
After shaking at 30 ° C. for 30 minutes, the viable cell count was measured (initial cell count 3.8 × 10 ⁶ cells / ml,). The results are shown in Table 21.

[0079]

[Table 21]

Test Example 13 [Bactericidal efficacy confirmation test (Part 2)] White water (pH) collected by a newspaper making machine of a certain paper mill.
5.1, reducing substance SO ₃ ^2- conversion 8 mg / l, Pseudomonas spp, Bacillus spp, Flavobacterium spp, Staphylococcus spp.
After shaking for minutes, the number of surviving cells was measured (initial cell number: 7.8 × 10 ⁵ cells / ml). The results are shown in Table 22.

[0081]

[Table 22]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location A01N 37/34 106 8930-4H 37/50 8930-4H 41/10 Z 8930-4H 43/80 102 8930-4H 47/48 8930-4H

Claims (14)

[Claims] 1. A compound represented by the general formula (I ′): (In the formula, R'is an alkanoyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and X is a halogen atom.) An industrial fungicide containing a dihalogenated glyoxime diacylate as an active ingredient. . 2. General formula (I): (In the formula, R represents an alkanoyl group having 1 to 4 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and X represents a halogen atom.) And a known halogenated industrial bactericidal component However, 4,5-dichloro-1,2-dithiol-3-one is excluded hereinafter) as an active ingredient. 3. The industrial bactericidal agent according to claim 2, wherein the industrial bactericidal component is one or more compounds selected from organic nitrogen-sulfur-based, organic bromine-based, organic nitrogen-based or organic sulfur-based compounds. . 4. The organic nitrogen-sulfur compound is methylenebisthiocyanate or 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-. A 3-isothiazolone compound such as 2-n-octyl-isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one, 1,2-benzisothiazolin-3-one or a complex of these with a metal salt. The industrial germicide according to claim 2 or 3. 5. The organic nitrogen-sulfur compound is methylenebisthiocyanate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one or 4,5-dichloro-. 2-n-octyl-isothiazolin-3-one.
The industrial bactericide described in 1. 6. The organic bromine compound is 2,2-dibromo-
Organic bromocyano compounds such as 3-nitrilopropionamide and 2-bromo-2-bromomethylglutaronitrile; 2-bromo-2-nitropropane-1,3-diol,
2,2-dibromo-2-nitro-1-ethanol, 2-bromo-2-nitro-1-ethanol, 1,1-dibromo-1-
Nitro-2-propanol, 1,1-dibromo-1-nitro-2-acetoxyethane, 1,1-dibromo-1-nitro-
2-acetoxypropane, 2-bromo-2-nitro-1,
3-diacetoxy-propane, tribromonitromethane,
β-bromo-β-nitrostyrene, 5-bromo-5-nitro-1,3-dioxane, 5-bromo-2-methyl-5-
Organic bromonitro compounds such as nitro-1,3-dioxane;
Or 1,2-bis- (bromoacetoxy) -ethane, 1,2-bis (bromoacetoxy) -propane, 1,4-bis- (bromoacetoxy) -2-butene, methylenebisbromoacetate, benzyl bromoacetate, 1,2,3-tris (bromoacetoxy) propane, N-bromoacetamide,
The industrial bactericide according to claim 2 or 3, which is an organic bromoacetate ester or amide such as 2-bromoacetamide. 7. The organic bromine compound is 2,2-dibromo-
3-Nitrilopropionamide, 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitro-1-ethanol, 2-bromo-2-nitro-1-ethanol, 2-bromo 2-Nitro-1,3-diacetoxypropane, 1,2-bis (bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane, 1,4-bis (bromoacetoxy) -2-butene, β -Bromo-β-nitrostyrene, 5-bromo-5-nitro-1,3-dioxane or 1,
The industrial fungicide according to any one of claims 2, 3 and 6, which is 2,3-tris (bromoacetoxy) propane. 8. The organic nitrogen compound is α-chlorobenzaldoxime, 5-chloro-2,4,6-trifluoroisophthalonitrile, 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile. The industrial germicide according to claim 2 or 3. 9. The organic sulfur compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, bis (tribromomethyl) sulfone, bis (trichloromethyl) sulfone or claim 2. 3. The industrial fungicide according to 3. 10. The compounding ratio (as a weight ratio) of the compound represented by the formula (I) and a known industrial sterilizing component is 50: 1.
The industrial bactericide according to any one of claims 2 to 9 which is ˜1: 20. 11. The compounding ratio (as a weight ratio) of the compound represented by the formula (I) and a known industrial sterilizing component is 20: 1.
The sterilizer for industrial use according to any one of claims 2 to 10, which is ˜1: 10. 12. An industrial sterilization method comprising sterilizing by adding a compound represented by formula (I) and a known industrial sterilizing component to a system for industrial sterilization simultaneously or separately. 13. Known industrial sterilizing components are claimed in claims 3 to 7.
The industrial sterilization method according to claim 12, which is the compound according to any one of claims 1 to 10. 14. The compound of formula (I) and a known industrial bactericidal component are used in a ratio of 50: 1 to 1:20 (weight ratio) and at a concentration of 0.05 to 50 mg / l. The industrial sterilization method according to 12 or 13.