JPH01221302A - Bactericide for industry and sterilization - Google Patents

Abstract

PURPOSE:To provide a bactericide for industry exhibiting excellent bactericidal potency even in a low concentration and showing stable bactericidal activity without lowering the potency even in systems containing reducible ions such as sulfite ions, by containing a specific acid anhydride as an active ingredient. CONSTITUTION:The bactericide contains as an active ingredient an acid anhydride of formula I [R1 is 2-3C divalent saturated or unsaturated hydrocarbon group (substituted with halogen, lower alkyl, lower alkenyl, etc.,) or divalent saturated or unsaturated six-membered ring hydrocarbon group (substituted with halogen, lower alkyl lower alkenyl, amino, nitro, etc.,)] or formula II [R2 and R3 are (halogenated) 1-18C alkyl, alkenyl, phenyl, lower alkylphenyl, pyridyl, etc.,] such as maleic anhydride, succinic anhydride, caproic anhydride or phthalic anhydride. The bactericide is used by being intactly added to industrial object systems to be sterilized such as water for paper-producing processes in paper pulp industry or after preliminarily formed into preparations.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Use This invention relates to an industrial disinfectant and a disinfection method. More specifically, it is useful as a preservative and sterilizer for papermaking process water, cooling water for various industries, metal processing oil, textile oil, water-based paint, paper coating fluid, latex, sizing agent, etc. in the Gion Pulbu industry. This article relates to certain industrial disinfectants and disinfection methods.

(b) Conventional technology Slime caused by bacteria and fungi has been generated in the paper making process of Gion Pulbu Industries and cooling water systems in various industries, causing losses such as deterioration of product quality and production efficiency. Are known.

In addition, many industrial products such as metal processing oils, textile oils,
Water-based paints, paper coating fluids, various latexes, glues, etc. are subject to great damage due to bacterial rot and fungal contamination.

Many disinfectants have been used to prevent damage caused by these microorganisms. In the old days, organic mercury compounds such as ethylmercury phosphate and phenylmercury acetate, and chlorinated phenol compounds such as pentachlorophenol and trichlorophenol were used. However, these drugs are highly toxic to humans and fish and shellfish, and cause environmental pollution, so their use is now regulated. Thiocyanate, 5-chloro-2-methyl-4
-Isothiazolin-3-one, 2-bromo-2-nitrobroban-1,3-diol, and the like are widely used as industrial fungicides.

On the other hand, in the field of foods, organic carboxylic acids are said to be effective as preservatives and antibacterial agents with lower toxicity, and specifically maleic acid and fumaric acid are known (Journal of the Japan Food Industry Association Vol. 1. 31 No. 8 p. 523-5
30, JP-A No. 60-244245, No. 57-17
Publication No. 6903).

Also, West German Offenlegungsschrift
Publication No. 2815400 (published on 18th IO, I979)
describes an aqueous solution containing percarboxylic acid (permaleic acid is disclosed as an example) as a disinfectant for medical and dental instruments and daily necessities.

(c) νJ to be solved by the invention However, when the above-mentioned low-toxicity organic carboxylic acids and percarboxylic acids having an antibacterial effect are used as a disinfectant in target systems such as papermaking process water in the pulp and paper industry,
The antibacterial effect in the above-mentioned target system is insufficient, and the desired bactericidal effect cannot be expected at all with practical aK. The inventors of this invention have conducted extensive research focusing on unsaturated dicarboxylic acids such as the above-mentioned organic carboxylic acids, and have surprisingly discovered the above-mentioned maleic acid, fumaric acid, etc. Compared to the corresponding organic carbonic acid, it has a bactericidal effect that is several times higher than that of the corresponding organic carbonic acid.
In addition, when the target system contains reducing ions such as subate ions, the bactericidal effect of the general-purpose industrial fungicides described above is already established, but this method They discovered that a stable bactericidal effect could be achieved without any significant reduction, and arrived at this invention.

(d) Means for solving ag Thus, according to this invention, general formula (I).○! 1 [In the formula, R1 is a divalent saturated or unsaturated hydrocarbon group having 2 or 3 carbon atoms, which may be substituted with a halogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkylidene group (however, In the case of saturated hydrocarbon groups,
The carbon atom may be bonded via an oxygen or sulfur atom), or may be substituted with a halogen atom, a lower alkyl group, a lower alkenyl group, an amino group, a nitro group, or a carboxyl group (2). A saturated or unsaturated six-membered ring hydrocarbon group (however, opposing carbon atoms in the six-membered ring may be bridged with a methylene or ethylene group)], or the general formula n) ++ (In the formula, R2 and R3 are the same or different and may be substituted with a halokene atom, an alkyl or alkenyl group having 1 to 8 carbon atoms, a phenyl group, a lower alkylphenyl group, a phenyl lower alkyl group) An industrial fungicide is provided which contains an acid anhydride represented by the following formula (representing a phenyl lower alkenyl group or a pyridyl group) as an active ingredient.

In the definition of the acid anhydride of formula (f) used in this invention, a divalent saturated carbon having 2 or 3 carbon atoms (the arsenic group includes alkylene groups such as ethylene and trimethylene, and unsaturated Examples of hydrocarbon groups include vinylene and 1.3
- alkenylene groups such as propenylene; Hydrogen in such hydrocarbon groups may be optionally substituted with a halogen atom, a lower alkyl group, a lower alkenyl group, a lower alkylidene group, etc. Examples of the halogen atom include chlorine, bromine, iodine and fluorine. It will be done.

In addition, "lower j" in lower alkyl groups, lower alkenyl groups, and lower alkylidene groups means having 1 to 6 carbon atoms.For example, examples of lower alkyl groups include methyl, ethyl, propyl, and butyl groups. , pentyl group,
Examples include hexyl group. Further, examples of the lower alkenyl group include a vinyl group, an allyl group, an isopropenyl group, and the like. Furthermore, examples of the lower alkylidene group include a methylene group and an ethylidene group. In addition, in the case of a saturated hydrocarbon group, each carbon atom may be bonded via oxygen or an integer, for example, -c-o-'
Examples include c-1-C-S-C- group.

In addition, the 21 saturated but unsaturated six-membered ring hydrocarbon groups that meet C in the definition of the acid anhydride of formula (I) include 0-phenylene group, 1.2-chlorohexylene group, 1.2- Examples include a cyclohexenylene group and the like. The six-membered hydrocarbon group includes the aforementioned halogen atom, lower alkyl group,
It may be optionally substituted with an alkenyl group, an amino group, a nitro group, a carboxyl group, etc. Furthermore, opposing carbon atoms in the six-membered ring may be bridged by a methylene group or (I) ethylene group.

Specific examples of acid anhydrides represented by the general formula (D) include succinic anhydride, itaconic anhydride, glutaric anhydride, dimethylglutaric anhydride, maleic anhydride, and citraconic anhydride (monomethylmaleic anhydride). , dichloromaleic anhydride, dimethylmaleic anhydride, glutaconic anhydride, diglycolic anhydride, thiodiglycolic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, ditrophthalic anhydride Acid, 4-methylphthalic anhydride, tetrahydrofucric anhydride, methyltetrahydrophthalic anhydride, 3-aminophthalic anhydride, 3-(2'-methyl-2'-butene)-5-
Methyl-1,2,3,6-tetrahydrophthalic anhydride,
6-Methyl-4-cyclohexene-1,2,3-tricarboxylic acid-1,2-anhydride, 3,4-dimethyl anhydride
6-(2-methyl-1-propenyl)-4-cyclohexene-1,2-dicarboxylic acid, 1,2-chlorohexanedicarboxylic anhydride, methyl-1,2-7chlorohexanenocarboxylic anhydride, Anhydrous-5-norbornene-2,3-
carbonic acid, methyl-5-norbornene-2,3 anhydride
-Dicarboxylic acid, chlorendic anhydride, 1-methyl anhydride-
4-isopropyl-entobicyclo'2.2.2]
Examples include 5-hexene-2,3-dicarboxylic acid.

For example, in the case of maleic anhydride, the substituents include monomethyl maleic anhydride, monoethyl maleic anhydride, monopropyl maleic anhydride, monobutyl maleic anhydride, monopentyl maleic anhydride, and monopentyl maleic anhydride. Acid, dimethyl maleic anhydride, diethyl maleic anhydride, dipropyl maleic anhydride, dibutyl maleic anhydride, nopentyl maleic anhydride, diethyl maleic anhydride, methylethyl maleic anhydride, methylpropyl maleic anhydride, methylbutyl maleic anhydride, methyl Pentyl maleic anhydride, methyl ethyl maleic anhydride, ethylpropyl maleic anhydride,
Ethylbutyl maleic anhydride, ethylpentyl maleic anhydride, ethylchloromaleic anhydride, propylbutyl maleic anhydride, propylpentyl maleic anhydride, proylhequinle maleic anhydride, butylpentyl maleic anhydride, butylhequinle maleic anhydride, pentylhequinle maleic anhydride, monochloro Maleic anhydride, monobromo maleic anhydride, monoiodo maleic anhydride,
Monofluoro maleic anhydride, dichloromaleic anhydride, mbromomaleic anhydride, short maleic anhydride,
Difluoromaleic anhydride, methylchloromaleic anhydride, methylbromomaleic anhydride, methyliodomaleic anhydride, methylfluoromaleic anhydride, ethylchloromaleic anhydride, ethylbromomaleic anhydride, ethyliodomaleic anhydride, ethylfluoromaleic anhydride, propyl Chloromaleic anhydride, propyl bromo maleic anhydride, propyl iodo maleic anhydride, propyl fluoro maleic anhydride, butyl chloro maleic anhydride, butyl bromo maleic anhydride, butyl iodo maleic anhydride, butyl fluoro maleic anhydride, pentyl chloro maleic anhydride, Examples include pentylbromomaleic anhydride, pentyliodomaleic anhydride, pentylfluoromaleic anhydride, hexylchloromaleic anhydride, hexylchloromaleic anhydride, hexyliodomaleic anhydride, hexylchloromaleic anhydride, and the like.

Among these, maleic anhydride, citraconic anhydride, dichloromaleic anhydride, succinic anhydride, itaconic anhydride, glutaric anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, methyl-1,2-cyclohexanedicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-anhydride norbornene-2,3-dicarboxylic acid,
Preference is given to using diglycolic anhydride, thiodiglycolic anhydride or glutaconic anhydride.

On the other hand, in the definition of the acid anhydride represented by the general formula (II), the halogen atom, lower alkyl, and lower alkenyl include the various ones mentioned above. Specific examples of the acid anhydride represented by the general formula (II) include acetic anhydride, trimethylacetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, bis(chloroacetic anhydride), propionic anhydride, and anhydride. Pentafluoropropionic acid, butyric anhydride, hebutafluoro-n-butyric anhydride, valeric anhydride, caproic anhydride, enanthic anhydride, caprylic anhydride,
pelargonic anhydride, capric anhydride, lauric anhydride,
Examples include myristic anhydride, valmitic anhydride, stearic anhydride, crotonic anhydride, methacrylic anhydride, ammizoic anhydride, corticic anhydride, toluic anhydride, and nicotinic anhydride. Among these, acetic anhydride, propionic anhydride,
It is preferable to use butyric anhydride, valeric anhydride, caproic anhydride, enanthic anhydride, caprylic anhydride, capric anhydride, fragrant anhydride, or trichloroacetic anhydride.

Among the acid anhydrides of general formulas (I) and (II) mentioned above, the most preferred are maleic anhydride, notraconic anhydride, (
g (hydric acid, caproic anhydride, dinandoic anhydride,
The compounds of this invention which are 5-norhorne-2,3-nocarboxylic anhydride, methyl-5-norhorne-2,3-nocarboxylic anhydride, phthalic anhydride, ammonium anhydride, fragrant acid, methyltetrahydrophthalic anhydride and glutaconic anhydride As the active ingredient of the industrial fungicide, one or more of the moeki acid dihydrates may be used.

The industrial disinfectant of this invention is particularly suitable for use in the paper pulp industry, cooling water for various industrial uses, metal processing oil, textile oil, water-based paint, paper coating liquid, latex, glue. It is useful for antiseptic and sterilizing agents, etc., but is not limited to these.

The acid anhydride, which is the active ingredient of the above-mentioned industrial disinfectant, may be added to the target system as it is, or may be used after being appropriately formulated in advance. For this preparation, conventional nonionic, anionic, cationic and amphoteric surfactants and liquid media having milk dispersing action are appropriately selected and used.

Examples of the above-mentioned nonionic surfactants include polyoquinoethylene algyl ether, borioquinoethylene alkyl phenyl ether, polyoquinoethylene polyokine propylene copolymers, etc., and examples of the anionic surfactants include aliphatic highly soluble alcohols. Examples of the cationic surfactant include sulfuric acid ester sodium salt and alkylhenzenosulfonic acid, and examples of the cationic surfactant include alkyltrimethylammoniumolite and the like. Examples of the liquid medium used include, but are not limited to, methquine butyl acetate, methquinoethyl acetate, dioxane, dimethyl sulfokide, trimethylformamide, trichloroethane, propylene carbonate, etc. Please consider your gender when choosing. Although it is preferable that the organic solvent is dehydrated and dried in advance, this treatment may be omitted.

In particular, when it is used in a target system immediately after preparation, an aqueous solvent or the like may be used as the water tank.

The amount of the acid anhydride used in the industrial disinfectant of this invention is determined so that when used in the target system, the amount of the active ingredient can be present in the system. The amount of the active ingredient varies depending on the target system, but for example, when used as a slime control agent in the papermaking process, it is 0.5 to 500% based on the amount of inflow water.
ppm (active ingredient amount, below) 3 times a day, 10~
For example, it may be added in a shocking manner for 60 minutes. For slime control in cooling water systems, use 05 to 500p based on the amount of water held.
For example, pm may be added in a shocking manner once or twice a week. When used as a preservative or fungicide for various industrial products, the purpose can usually be achieved by adding 3 to 500 ppm, although this varies depending on the type of product, storage period, etc.

In the above formulation, the acid anhydride is 5 to 50% by weight in the formulation.
Preferably, it is prepared so that it can be contained.

In addition, when actually using the chemical of this invention, it is not necessary to use it in combination with other known bactericidal agents or algaecides. In particular, when used in combination with a specific drug, it is possible to obtain a synergistic bactericidal effect.

Here, as drugs that exhibit a synergistic effect when used in combination, alkylene bis-thionoanates such as methylene bis-thionoanate and ethylene histhionoanate;
Propionamides such as 2,2-dibromo-3-nitrilopropionamide, 1.2-his(bromoacetoxy)ethane, 1,4-his(bromoacetoxy)-2-butene, 1,2-bis(chloroacetoxy) ) ethane, 1.
2-bis(iodoacetoquino)ethane, 1,4-bis(
halogenated acetate ester derivatives such as chloroacetoquine)-2-butene, 1,2-dithiol-3-one derivatives such as 4,5-dichloro-1,2-dithiol-3-one, 2.2- Dibromo-2-nitroethanol, 1.1
-dibromo-1-nitropropanol-2.1.1-'
; Fromo 1-nitro 2-acetoxoethane, 1.
1-dibromo-1-nitro-2-acetoxypropane,
Aliphatic nitro alcohol derivatives such as 2-bromo-2-nitro-1,3-diacetoxypropane, 2-bromo-2-nitro-1,3-propanediol, 1,2-benzisothiazolin-3-one, 2 -Methyl-5-C-1,2-isothiazolin-3-one, 2-methyl-1,
Examples include isothiazolones such as 2-isothiasily:/-3-one and complexes of these metal salts.

Therefore, the present invention also provides a combination drug that exhibits such a synergistic effect. Appropriate combined roles (weight ratio) in this case are as shown in the table below.

(Hereinafter, blank spaces) Further, according to the present invention, there is provided an industrial sterilization method characterized by adding the above-mentioned acid anhydride to the system to be sterilized, and a method of adding the acid anhydride and the above-mentioned combination drug to the system to be sterilized. An industrial sterilization method is provided. Preferred acid anhydrides, systems to be sterilized, formulation forms, concomitant drugs, and amounts added are as described above.

In the industrial disinfectant and disinfection method of the present invention, it is desirable to use a disinfectant that does not contain a substantial amount of peroxide. A substantial amount (e.g. acid anhydride 1
It is said that when a bactericide is added to water, it produces percarboxylic acid and has a bactericidal effect when it contains peroxide (0.1 mole per mole or more), and in a system where reducing ions are present, This is because the reducible ions are oxidized by the percarboxylic acid, which is disadvantageous.

(E) Examples The present invention will be explained below using formulation examples and test examples, but is not limited thereto.

In addition, in the formulation examples and test examples, maleic anhydride was replaced with compound I.
, dichloromaleic anhydride was designated as compound (2), monomethyl maleic anhydride, and inic acid was designated as compound (2).

Furthermore, "Compound I, ■ or ■" indicates that the preparation was carried out for each.

Formulation Example 1゜Compound I or ■ or [[20 parts by weight Pluronic L-6410 parts by weight (polyoxyethylene polyoxypropylene copolymer,
Product name: Asahi Denka Kogyo (Mai)) 3-methoxybutyl acetate 70 parts by weight Formulation Example 2 Compound I or II 10 parts by weight Compound I [I 1
0 parts by weight Pluronic L-64 (same as above)
5 parts by weight 3-methoxybutyl acetate
75 weight, yy Formulation Example 3゜ Compound I or H or I 10 parts by weight Pluronic L-64 (same as above) 5 parts by weight 3-methoxybutyl acetate 85 parts by weight Formulation Example 4゜ Compound 1 10 parts by weight Compound U 10 parts by weight Pluronic L-64 (same as before) 5
Parts by weight 3-methoxybutyl acetate 7
5 parts by weight Formulation Example 5 Compound [10 parts by weight Compound ff 10M
Amount of compound I [I
10 parts by weight Pluronic L-64 (same as before)
5 parts by weight 3-methoxybutyl acetate
65 parts by weight Test example 1. Bacterial killing test Suspend various types of bacteria in physiological saline so that the number of bacteria is approximately 108 sea bream/1a. This is a formulation example! Add emulsions of various concentrations to the mixture and shake at 37°C for 1 hour. After shaking, the number of surviving bacteria was measured, and the initial count of 99.
More than 9% is killed, making the f2 concentration the effective a change.

The results are shown in Table 1.

Table 1 The numerical value indicates the effective concentration (4π9/Q) of the active ingredient.

As is clear from Table 1, the compound of the present invention exhibits a bactericidal effect with lower sensitivity than maleic acid or fumaric acid.

Test example 2. Mold inhibition test Inoculate Czapek-Dox medium with various molds.

Then, the emulsion of Formulation Example 1 (compound I) was added at various concentrations. Shaking culture was carried out in a thermostatic chamber at 27° C. for 7 days, and the concentration at which no mycelial growth was observed was defined as the effective concentration.

The results are shown in Table 2.

The values in Table 2 indicate the effective concentration (mg#) of the active ingredient. - As is clear from Table 2, the compounds of the present invention exhibited approximately 2 to 10 times more efficacy than maleic acid and fumaric acid.

Test Example 3 Yeast Inhibition Test Various yeasts isolated from slime from a certain paper mill and an emulsion of Formulation Example 3 (compound ■) were added to a YM liquid medium to a predetermined concentration, and the mixture was incubated at a constant temperature of 27°C. Cultured with shaking. After 24 hours, the concentration at which no turbidity of the medium was observed was defined as the effective concentration.

The results are shown in Table 3.

Table 3 The numerical value indicates the effective if (mg/ρ) of the active ingredient.

As is clear from Table 3, the compounds of the present invention exhibited a more remarkable inhibitory effect on slime-constituting yeasts than maleic acid or fumaric acid.

Test example 4. White water in the papermaking process (pH 3,7 SOs'-3
Bactericidal power test against (containing 0 ppm) Formulation Example 1 was added to white water collected from newspaper manufacturing at a certain paper factory
(However, compound
Table 4 shows the results of measuring 2).

When the bacteria in this white water were isolated and the bacterial species was identified, it was confirmed that the bacteria belonged to the genus Pseudomonas and the genus Fura.

As is clear from Table 4, the compound of the present invention exhibits a remarkable bactericidal effect against bacteria in the white water of the papermaking process at a concentration of 10-15 mg/12, and is therefore useful as a slime control agent. Recognize. This is 1710 degrees a compared to the effective concentration of maleic acid and fumaric acid.

Test example 5. Preservation test of beetroot slurry An aqueous slurry containing 40% of oxidized beetroot is prepared, the slurry which has already spoiled is added thereto, and the slurry is dispensed into L-shaped test tubes while stirring uniformly. Formulation example 3 (f2f strain compound ■
) was added to give various concentrations, and the mixture was shaken at 37°C. The number of bacteria in the sample is measured orally and the preservative efficacy is determined.

The results are shown in Table 6.

Table 6 As is clear from Table 6, the compound of this invention has 200
mg#! It shows remarkable preservative effect.

Test Example 6 A test was conducted in the same manner as in Test Example 1 using the following various acid anhydrides A-CC.

Maleic anhydride (compound A), traconic anhydride (compound B), dichloromaleic anhydride (compound C), succinic anhydride (compound D),! itaconic acid hydrate (compound E), glutaric anhydride (compound F), phthalic anhydride (compound G),
Tetrachlorophthalic anhydride (Compound H), Tetrabromophthalic anhydride (Compound I), Trimellitic anhydride (Compound J), Tetrahydrophthalic anhydride (Compound K), Methyltetrahydrophthalic anhydride (Compound L), Anhydrous -1,
2-chlorohexanedicarboxylic acid (compound ~ [), methyl anhydride-1,2-sochlorohexanenocarboxylic acid (compound N), anhydride-5-norhornene-2,3-dicarboxylic acid (compound 0), methyl anhydride- 5-norbornene-2,3
-dicarboxylic acid (compound P), acetic anhydride (compound Q),
Propionic anhydride (compound R), butyric anhydride (compound S)
, valeric anhydride (compound T), caproic anhydride (compound U
), enanthic anhydride (compound v), caprylic anhydride (compound W), capric anhydride (compound X), benzoic anhydride,
acid (compound Y), trichloroacetic anhydride (compound Z), m
diglycolic acid anhydride (compound AA), thiodiglycolic anhydride (compound BB), glutaconic anhydride (compound CC
) The formulations used in the test are as follows.

Formulation Example 6 Compound A-B-C-E-F-L-M-N-AA or P
20 parts by weight Pluronic L-64
10 parts by weight (polyquine ethylene polyoxinopropylene copolymer, trade name: manufactured by Asahi Denka Kogyo Co., Ltd.) 3-methquine butyl acetate
70 parts by weight Formulation Example 7 Compound Q-R-S-T-U-V-W-X or Z
40 parts by weight Pluronic L-64 (same as above) 10 parts by weight 1.1.1-Trichloroethane
50 parts by weight Formulation Example 8 Compound D-G-H-I- to -0-Y-BB or CG
10 parts by weight Pluronic L-64 (same as above) 10 parts by weight propylene carbonate 80 parts by weight
These test examples were conducted in the same manner as Test Example 1 except that 50z9/C was added with sulfite ion (s o, ") as sulfite ion (s o, "), and the results are referred to as Test Example 6-1 and Test Example 6-2, respectively. The results are shown in Table 7.Comparative examples are shown in Table 8.As is clear from Tables 7 and 8, the efficacy of organic carboxylic acids is significantly reduced in the presence of sulfite ions, whereas
It can be seen that the compound of the present invention is stable even in the presence of sulfite ions and exhibits bactericidal efficacy.

(Margins below) Table 7 Table 8 Test Example 7 (Synergistic effect test) N. aeruginosa (slime isolate) is planted in a bouillon medium and cultured at the optimum temperature for growth (37°C). Dilute the culture solution to 1001 with sterile water to 10
Aliquot IIQ into L-shaped sterile test tubes.

Two types of compounds (A) and (B) were added thereto at various mixing ratios, and after mixing at 37° C. for 1 hour, the number of bacteria was measured. The required amount of the drug to be added to reduce the initial bacterial count (approximately 10'l/IC) to 1031/mQ or less was determined and shown as measurement graphs in FIGS. 1 to 8.

In this graph, the vertical axis shows the effective concentration of (A) maleic anhydride, and the groove axis shows the effective concentration of each concomitant drug (B).

...The additive effect appears on the diagonal line, but if there is an effective concentration inside of it, it will be a synergistic effect, and if it is outside it, it will be a countervailing effect.

The drug combinations for the data in each figure are shown below.

Figure 1: (A) Maleic anhydride (hereinafter referred to as MA) and (B)
Methylene bisthionate (hereinafter referred to as MBTC) Figure 2 (A) to IA and (B) 2,2-dibromo-3-nitrilopropionamide (hereinafter referred to as DBNPA) Figure 3 and (A)
) MA and (B) 1,2-bisbromoacetoquinethane (
(hereinafter referred to as BBAE) Figure 4 (A) M A and (B) 1,2-bisbromoacetoquino-2-butene (hereinafter referred to as BBAB) Figure 5: (A
) MA and (B) 4,5-dichloro-1,2-phthiol-3-one (hereinafter referred to as DCDT) Figure 6 ・(A) MA and CB) 2,2-dibromo-2-nitroethanol (hereinafter referred to as DCDT) DBNE) Figure 7: (A) MA and (B) 5-chloro-2-methyl-
Mixture of 4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (hereinafter referred to as M[T) Figure 8: (A) MA and (B) 2-bromo-2-nitro-
1,3-Diacetyloquinebroban (hereinafter referred to as BNDAP)
) As shown in this figure, it can be seen that a synergistic bacteriostatic effect can be obtained with each.

Test example 8. Synergistic bactericidal efficacy test (I) on white water in the papermaking process White water (pH:
4.2. SO*”-; 14 ppm Pseudomonas sp.

The preparations shown in Table 9 below were added to various concentrations of alkaline earth metals (mainly Bacillus bacteria), shaken at 37°C, and the number of viable bacteria was measured over time. The results are shown in Table 10.

Test Example 9 Bactericidal efficacy test for white water in the papermaking process White water (p
H: 7.4. S Os'-; 8 ppm, Flavobacterium, Micrococcus, Pseudomonas,
After adding the above preparation to a predetermined concentration to Bacillus (mainly bacteria belonging to the genus Bacillus), the mixture was shaken at 37°C and the number of viable bacteria was measured over time. The results are shown in Table 11.

(Left below) Table 11 From the results of Test Examples 8 and 9 above, component (A) and component (B
) was confirmed to have a clear synergistic bactericidal effect.

Test example! 0. White water in the papermaking process (pH 6, 2S O332
Test for bactericidal efficacy against (containing -50 pp) The above formulation was added to white water collected from a newspaper machine in a rack factory.
-dicarboxylic acid), Formulation Example 7 (however, compound V was used;
Enanthic anhydride) and Formulation Example 8 (using Tatsu Compound G, phthalic anhydride) were added to various concentrations,
Shake at 37°C. Table 12 shows the results of measuring the number of bacteria (cells/jlC) after 30 minutes. When the bacteria in this white water was isolated and identified, it was found that it was Pseudomonas (Pseud
omonas) genus, Alcaligenes (Alcalig)
ines) and Micrococc
Bacteria of the genus Us) were confirmed.

(Left below) Table 12 Test Example 11. @Kari slurry preservative test oxidized starch 40
Prepare an aqueous slurry containing %, add the already spoiled slurry and dispense into L-shaped test tubes with uniform stirring.

Formulation Example 6 (using Compound A; maleic anhydride), Formulation Example 7 (using Compound U: caproic anhydride), Formulation Example 8 (using Compounds 0 and Y; anhydrous-5-norbornene-2,3- Emulsions 1 of dicarboxylic acid and benzoic anhydride were added to the mixture at various concentrations, and the mixture was shaken at 37°C. The number of bacteria in the sample was measured over time to determine the antiseptic efficacy. The results are shown in Table 13.

Table 13 (f) Effect of the Invention As stated above, the bactericidal agent made of acid anhydride of the present invention has a invasive effect, especially against similar compounds (
-mylenic acid, fumaric acid). Furthermore, in a system containing reducing ions such as sulfite ions, the efficacy is not reduced and a stable bactericidal effect is exhibited. Therefore, compared to conventional similar drugs, it is possible to reduce the concentration added when aiming for the same rapid effect, which is extremely useful in terms of environmental pollution and economic efficiency.

Furthermore, by combining it with a specific known bactericidal agent, it is possible to express a superior bactericidal effect based on their synergistic action.

[Brief explanation of the drawing]

Figures 1 to 8 show the combination drugs of this invention, respectively! : It is a graph diagram for showing the multiplication effect. Figure 1 2E! ! 7 (3) D B N P A (m(+/I) 3rd
Figure 4 Figure (8) B 8 A EBm9/[) @ 5 Figure 6 (B) M I T (m9/I) Figure 8

Claims (1)

[Claims] 1. General formula (I): ▲ Numerical formulas, chemical formulas, tables, etc.▼・・・・・・(I) [In the formula, R_1 is a halogen atom, a lower alkyl group, a lower alkenyl group, or A divalent saturated or unsaturated hydrocarbon group having 2 or 3 carbon atoms that may be substituted with a lower alkylidene group (however, in the case of a saturated hydrocarbon group, carbon atoms are bonded via oxygen or sulfur atoms). ), or a divalent saturated or unsaturated six-membered hydrocarbon group optionally substituted with a halogen atom, a lower alkyl group, a lower alkenyl group, an amino group, a nitro group, or a carboxyl group (however, Opposing carbon atoms in the six-membered ring may be bridged with methylene or ethylene groups), or general formula (II): ▲ Numerical formulas, chemical formulas, tables, etc. ▼・・・・・・( II) (In the formula, R_2 and R_3 are the same or different and may be substituted with a halogen atom, and have a carbon atom number of 1 to 18
an alkyl or alkenyl group, a phenyl group, a lower alkylphenyl group, a phenyl lower alkyl group, a phenyl lower alkenyl group, or a pyridyl group) as an active ingredient. 2. The acid anhydride of formula (I) is maleic anhydride, citraconic anhydride, dichloromaleic anhydride, succinic anhydride,
Itaconic anhydride, glutaric anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, Methyl-1,2-cyclohexanedicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-anhydride
The industrial disinfectant according to claim 1, which is one or more selected from dicarboxylic acid, diglycolic anhydride, thiodiglycolic anhydride, and glutaconic anhydride. 3. The acid anhydride of formula (II) is selected from acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, enanthic anhydride, caprylic anhydride, capric anhydride, benzoic anhydride and trichloroacetic anhydride. The industrial fungicide according to claim 1, which is one or more selected fungicides. 4. An industrial sterilization method, which comprises adding the acid anhydride of general formula (I) or (II) according to claim 1 to a system to be industrially sterilized. 5. Acid anhydride of general formula (I) or (II) of claim 1, alkylene bisthiocyanates, propionamides, halogenated acetate derivatives, 1,2-dithiol-3-one derivatives , aliphatic nitroalcohol derivatives, and isothiazolones as an active ingredient. 6. Acid anhydride of general formula (I) or (II) of claim 1, alkylene bisthiocyanates, propionamides, halogenated acetate derivatives, 1,2-dithiol-3-one derivatives , aliphatic nitroalcohol derivatives, and isothiazolones, and one or more compounds selected from the group consisting of aliphatic nitroalcohol derivatives and isothiazolones are added to a system to be industrially sterilized.