JPH11335207A - Industrial antimicrobial composition and antimicrobial method - Google Patents

Abstract

[57] [Abstract] [Problem] Papermaking process water in paper and pulp industry, cooling water for various industries and slime prevention of washing water, heavy oil sludge,
It is useful for antiseptic and antibacterial use of metalworking oils, fiber oils, paints, coating liquids for paper, latex, paste, etc.
For disperse bacteria in water, for slime on the wall,
Provided are an industrial antibacterial agent composition and an antibacterial method which exhibit excellent effects when added at a low concentration. SOLUTION: (A) 2,2-dibromo-3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene- An industrial antibacterial composition comprising 1,1-dioxide, and (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol And (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an industrial antibacterial agent composition and an antibacterial method. More specifically, the present invention provides
Papermaking process water in the paper and pulp industry, slime prevention for cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, fiber oil agent, paint, coating liquid for paper, latex,
The present invention relates to an industrial antibacterial composition and an antibacterial method useful for preserving and antibacterial paste.

[0002]

2. Description of the Related Art Conventionally, slime caused by bacteria and fungi is generated in papermaking processes in the paper and pulp industries and in cooling water systems in various industries, causing problems such as deterioration in quality of products and reduction in production efficiency. It has been known. In addition, many industrial products, such as heavy oil sludge, metalworking oils, textile oils, paints, various latexes, and pastes, cause decay and contamination by bacteria and fungi, and contaminate products, lowering their commercial value. Let it. Many antibacterial agents have been used to prevent damage by these microorganisms. In the old days, organic mercury compounds and chlorinated phenol compounds were used.However, these drugs are highly toxic to the human body and seafood, and their use has been regulated to cause environmental pollution. Organic nitrogen-based compounds, organic halogen-based compounds, and organic sulfur-based compounds having relatively low toxicity are widely used as industrial antibacterial agents (Encyclopedia of Fungicides and Fungicides, Japan Society of Fungicides and Fungi, published in 1986) . However, these antibacterial agents have low antibacterial activity against certain bacteria and fungi, and when applied to actual systems, require extremely high concentration of addition and are economically inefficient. When used, only bacteria having high resistance to the antibacterial agent propagate in the system, and the antibacterial effect is significantly reduced at the concentration of the antibacterial agent conventionally used. For this reason, a method has been proposed in which a plurality of antibacterial agents are used in combination in order to expect a so-called synergistic effect. For example, U.S. Pat.
No. 28,198 discloses 2,2-dibromo-3- as a composition having an unexpected synergistic effect on microorganisms.
Compositions containing nitrilopropionamide and 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide have been proposed. Further, as a combination exhibiting a synergistic effect, JP-A-60-231603 contains 3-bromo-3-nitropentane-2,4-diol and 2,2-dibromo-3-nitrilopropionamide. A bactericidal agent was proposed, and Japanese Patent Publication No. 7-8072
No. 7 proposes an industrial disinfectant containing 2,2-dibromo-2-nitro-1-methylethanol and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. ing. However, these compositions
Although it has improved antimicrobial efficacy, its effect has not always reached a satisfactory level when applied to real systems. Slime control agents belong to industrial antibacterial agents,
Although it is used for a very wide range of applications, there is a problem to be solved in the conventional methods for evaluating slime control agents.
That is, conventionally, the selection of the slime control agent
It has been carried out by evaluating the antibacterial effect of the drug on bacteria dispersed in water and the growth inhibitory effect. However, it has recently been found that the effect of the drug on dispersing bacteria in water and the effect on slime are not always correlated (JC Nickel, I. Ruseska, J. et al.
B. Wright, J.M. W. Coasterton, An
timicrobial Agents and Che
mother. , 27 (4) 619-624 ('8
5), Tobramycin Resistance o
f Pseudomonas aeruginosa C
cells growing as a Biofilm on
Urinary catheter materialia
l. ). Therefore, it is necessary to evaluate the effect of the antibacterial agent on slime not only against bacteria dispersed in water but also against slime growing on the wall surface in water. Under these circumstances, there is a need for an industrial antibacterial agent which is effective at a low concentration for both disperse bacteria and slime.

[0003]

SUMMARY OF THE INVENTION The present invention relates to papermaking process water in the paper and pulp industry, slime prevention for cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, fiber oil agent, paint and paper. It is useful as an antiseptic and antibacterial agent for coating liquids, latex, and sizing agents. The purpose of the present invention is to provide an antibacterial agent composition and an antibacterial method.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies using a slime adhesion monitor capable of evaluating the effect on slime adhered to a wall surface. 3,3,4, which are antibacterial agents of
It has been found that 4, -tetrachlorotetrahydrothiophene-1,1-dioxide has a function of preventing the attachment of microorganisms, rather than a bactericidal activity, and furthermore, 2,2-dibromo-3-nitrilopropionamide and 2,2 A known industrial antibacterial composition containing two components of -dibromo-2-nitroethanol, further containing a small amount of 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide. Compared with the combination of the two components, the present inventors have found that the synergistic antibacterial effect on a wider variety of microorganisms is enhanced and that the effect of preventing slime from being adhered for a long period is exhibited. The present invention has been completed based on this finding.
That is, the present invention relates to (1) (A) 2,2-dibromo-
It is characterized by containing 3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide. Industrial antimicrobial composition,
(2) The weight ratio of (A) 2,2-dibromo-3-nitrilopropionamide to (B) 2,2-dibromo-2-nitroethanol is from 1:99 to 99: 1, and (A)
The total amount of 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1- The weight ratio of the dioxide is 1:10 to 1
The antibacterial composition for industrial use according to item (1), wherein the composition is 00: 1.
(3) (A) 2,2-dibromo-3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1 , 1-dioxide; and (4) the weight of (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol The ratio is 1: 99-9
9: 1, and the total amount of (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4,- The weight ratio of tetrachlorotetrahydrothiophene-1,1-dioxide is from 1:10 to 100: 1, and (A) 2,2
-Dibromo-3-nitrilopropionamide and (B)
2,2-dibromo-2-nitroethanol and (C) 3,
3,4,4, -tetrachlorotetrahydrothiophene-1,
(3) The antibacterial method according to (3), wherein the total concentration of 1-dioxide is 0.01 to 200 mg / liter.
Is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial antibacterial composition of the present invention comprises:
Component (A) contains 2,2-dibromo-3-nitrilopropionamide, component (B) contains 2,2-dibromo-2-nitroethanol, and component (C) contains 3,3. And a ternary system containing 1,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. Here, the industrial antibacterial agent includes a slime control agent for various industrial water systems, a preservative for industrial products, and a bacteriostatic / bacteriostatic agent. In the composition of the present invention,
2,2-Dibromo-3-nitrilopropionamide used as the component (A) is a compound represented by the formula [1].

Embedded image In the composition of the present invention, 2,2- used as the component (B)
Dibromo-2-nitroethanol is a compound represented by the formula [2].

Embedded image In the composition of the present invention, 3,3,4,4, -tetrachlorotetrahydrothiophene used as the component (C)
1,1-dioxide is a compound represented by the formula [3].

Embedded image

In the industrial antimicrobial composition of the present invention,
There is no particular limitation on the ratio of the components (A), (B) and (C), but the weight ratio of the components (A) and (B) is 1:99 to 99: 1.
Is preferably 30:70 to 95: 5, more preferably 50:50 to 90:10. The ratio of the total amount of the components (A) and (B) to the component (C) is not particularly limited, but the weight ratio of the total amount of the components (A) and (B) to the component (C) is 1%. : 10 to 100: 1
Is preferably 50:50 to 98: 2, and more preferably 75:25 to 95: 5. The weight ratio of the component (A) to the component (B) is 1: 9.
9 to 99: 1, and the weight ratio of the total amount of the components (A) and (B) to the component (C) is 1:10 to 100: 1. In addition, it can exhibit both antibacterial property against disperse bacteria in water and an effect of preventing slime from adhering. The form of the industrial antimicrobial composition of the present invention is not particularly limited, and may be, for example, a one-part type containing all of the components (A), (B) and (C), or
Component (A), component (B) and component (C) can be separately added as a two-part type consisting of an agent containing one component and an agent containing two components. It is also possible to use a three-pack containing each of the component (B) and the component (C). Among these, a liquid one-part antibacterial agent containing the components (A), (B) and (C) is easy to handle and can be suitably used.

[0007] A liquid one-pack antibacterial agent containing the components (A), (B) and (C) is prepared by dissolving the components (A), (B) and (C) in an organic solvent. Can be
It can also be formulated as an aqueous suspension containing the components (A), (B) and (C). When the components (A), (B) and (C) are dissolved in an organic solvent to prepare a formulation, the organic solvent used is an antibacterial target system of various water systems such as process water for a papermaking process and cooling water for a factory. In the case of, it is preferable to use a hydrophilic organic solvent in consideration of dispersibility and solubility of the active ingredient. As the hydrophilic organic solvent, for example, glycol ethers such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, methanol Alcohols such as ethanol, propanol, butanol, hexanol and 2-ethylhexanol, esters such as methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate and propylene carbonate, dimethyl Examples include amides such as formamide and dimethylacetamide. When formulated as an aqueous suspension containing the components (A), (B) and (C), the components (A), (B) and (C) may be prepared using a ball mill or an attritor. Can be wet-ground to form an aqueous suspension. When producing an aqueous suspension, a thickener such as xanthan gum, ramzan gum, guar gum, or a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant can be used as a dispersant. . Also,
When the antibacterial target system is an oil system such as heavy oil sludge, cutting oil, oil paint, or the like, it is preferable to use a hydrocarbon-based solvent such as heavy oil, kerosene, or spindle oil to make a liquid one-pack antibacterial agent. When a one-component antibacterial agent is formed using a hydrocarbon-based solvent, the various surfactants described above can be used.

The method of using the industrial antibacterial agent composition of the present invention is not particularly limited, and is used for papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, fiber oil agent. , Paint, paper coating liquid, latex, sizing agent and the like. The amount of addition is not particularly limited and can be selected according to the target object, environmental conditions, purpose of use, etc., but in many cases,
The sum of the concentrations of the components (A), (B) and (C) is 0.01.
２００200 mg / l, preferably 0.1-200 mg / l.
More preferably, it is 50 mg / liter. If the total concentration of the components (A), (B) and (C) is less than 0.01 mg / liter, the antibacterial action may be insufficient.
The total concentration of the components (A), (B) and (C) is 200 mg.
/ Liter, the antibacterial property against disperse bacteria in water and the slime prevention effect are fully exhibited, and the total concentration is 200 mg
Additions in excess of / liter are usually unnecessary.
The industrial antimicrobial composition containing the component (A), the component (B) and the component (C) of the present invention has a function of significantly preventing the growth and adhesion of microorganisms in various industrial target systems. Particularly, it is extremely useful as an antibacterial agent such as a slime control agent for water in a paper making process, a coating solution for paper and a sizing agent.

In the antibacterial method of the present invention, 2,2-dibromo-3-nitrilopropionamide is used as the component (A), 2,2-dibromo-2-nitroethanol as the component (B), and 3 as the component (C). , 3,4,4, -Tetrachlorotetrahydrothiophene-1,1-dioxide is added. There is no particular limitation on the application of the method of the present invention, for example,
Papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, heavy oil sludge, metalworking oil agent, fiber oil agent,
Examples include paint, coating liquid for paper, latex, and paste. In the method of the present invention, the ratio of the amounts of the components (A), (B) and (C) is not particularly limited, but the weight ratio of the components (A) and (B) is 1:99 to 99: 1, preferably from 30:70 to 95: 5, and more preferably from 50:50 to 90:10. Further, the total added amount of the components (A) and (B) and (C)
There is no particular limitation on the ratio of the added amounts of the components, but the components (A) and (B)
The weight ratio of the total amount of the components to the component (C) is from 1:10 to 100:
1, preferably 50:50 to 98: 2, and more preferably 75:25 to 95: 5. The weight ratio of component (A) to component (B) is 1:
By setting the weight ratio of the total amount of the components (A) and (B) to the component (C) to 1:10 to 100: 1, the amount of addition is low even when the concentration is low. It can effectively antibacterial disperse bacteria in water and effectively prevent slime from adhering.

In the method of the present invention, the amounts of the components (A), (B) and (C) are not particularly limited and can be selected according to the object, environmental conditions, purpose of use and the like. ,
In many cases, the total concentration of the components (A), (B) and (C) is preferably from 0.01 to 200 mg / liter, more preferably from 0.1 to 50 mg / liter. The sum of the concentrations of the components (A), (B) and (C) is 0.
When the amount is less than 01 mg / liter, the antibacterial action may be insufficient. If the sum of the concentrations of the components (A), (B) and (C) is 200 mg / l, the antibacterial property against the dispersing bacteria in water and the slime prevention effect are sufficiently exhibited, and the total concentration is 200 mg / l. Excess additions are usually unnecessary. In the method of the present invention, there is no particular limitation on the method of adding the component (A), the component (B), and the component (C).
The component, the component (B) and the component (C) can be mixed in advance and added simultaneously, or the components (A) and (B)
One of the components (C) and the remaining two components can be separately added, and further, the components (A), (B) and (C) can be separately added. According to the antibacterial method of the present invention, in various industrial target systems, it is possible to remarkably prevent the growth and adhesion of microorganisms, and in particular, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries. Slime that is generated on the surface of the soil, prevents the growth of bacteria such as heavy oil sludge, metal working oil, fiber oil, paint, paper coating liquid, latex, and paste, thereby preventing decay.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, the effect of preventing slime adhesion was evaluated by the following method. Slime adhesion monitor combining an external cylinder made of SUS304 with an inner diameter of 100 mm and a volume of 488 ml and an internal cylinder made of SUS304 having a diameter of 36 mm (Japanese Unexamined Patent Publication No.
No. 75065. ) Was used. White water or artificial white water is continuously led to the outer cylinder so that the water temperature is 30 ° C and the residence time is 20 minutes, and the inner cylinder is 255 rp.
m, and the rotation torque of the inner cylinder was measured with a Brookfield torque meter [Toki Sangyo Co., Ltd., RE500H type]. If slime adheres to the internal cylinder over time and grows, the frictional resistance of the internal cylinder surface increases, and the value of the rotational torque increases. Using this principle, the time is taken on the horizontal axis, the rotational torque is taken on the vertical axis, the value of the rotational torque is shown on a personal computer every minute, and the time at which the value of the rotational torque starts to increase is defined as the slime deposition start time. . The value obtained by subtracting the slime adhesion start time when using white water or artificial white water without adding the antibacterial agent composition from the slime adhesion start time when using white water or artificial white water to which the antibacterial agent composition is added is defined as the delay time. ,
It was used as an index of the slime adhesion preventing effect of the antibacterial agent composition.

Production Example 1 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3, 2.5 parts by weight of 3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 67.
By mixing 5 parts by weight, an industrial antibacterial composition A was produced. Production Example 2 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 5,4, -Tetrachlorotetrahydrothiophene-1,1-dioxide 5.0 parts by weight and diethylene glycol monomethyl ether 65.
By mixing 0 parts by weight, an industrial antibacterial composition B was produced. Production Example 3 (A) 20.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 10.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 2.5 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 6
By mixing 7.5 parts by weight, an industrial antibacterial agent composition C was produced. Production Example 4 (A) 20.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 10.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 5.0 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 6
By mixing 5.0 parts by weight, an industrial antibacterial agent composition D was produced. Production Example 5 (A) 12.5 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 7.5 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 2.5 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 77.
By mixing 5 parts by weight, an industrial antibacterial composition E was produced. Preparation Example 6 (A) 12.5 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 7.5 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 5,4, -Tetrachlorotetrahydrothiophene-1,1-dioxide 5.0 parts by weight and diethylene glycol monomethyl ether 75.
By mixing 0 parts by weight, an industrial antibacterial composition F was produced. The industrial antimicrobial compositions A to F produced in Production Examples 1 to 6 had a weight ratio of the component (A) to the component (B) of 62.5: 3.
7.5 to 83.3: 16.7, and the weight ratio of the total amount of the component (A) and the component (B) to the component (C) is 80:20 to 92.3:
7.7.

Reference Example 1 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol and 70% by weight of diethylene glycol monomethyl ether. By mixing 0 parts by weight, an industrial antibacterial composition a was produced. Reference Example 2 (A) 20.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 10.0 parts by weight of 2,2-dibromo-2-nitroethanol and 70.0 parts by weight of diethylene glycol monomethyl ether Was blended to produce an industrial antimicrobial composition b. Reference Example 3 (A) 12.5 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 7.5 parts by weight of 2,2-dibromo-2-nitroethanol and 80.0 parts by weight of diethylene glycol monomethyl ether Was blended to produce an industrial antimicrobial composition c. Reference Example 4 (A) 2,5.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide and 75.0 parts by weight of diethylene glycol monomethyl ether were blended to prepare an industrial antibacterial composition d. Reference Example 5 (B) 25.0 parts by weight of 2,2-dibromo-2-nitroethanol and diethylene glycol monomethyl ether 7
By mixing 5.0 parts by weight, an industrial antibacterial agent composition e was produced. Reference Example 6 (C) 2,3,4,4, -Tetrachlorotetrahydrothiophene-1,1-dioxide (25.0 parts by weight) and diethylene glycol monomethyl ether (75.0 parts by weight) were blended to obtain an industrial antibacterial composition. f was produced. The industrial antimicrobial compositions a to c produced in Reference Examples 1 to 3 contain the components (A) and (B) but do not contain the component (C), and were produced in Reference Example 4. Industrial antimicrobial composition d
Is a composition containing only the component (A), and the industrial antibacterial agent composition e produced in Reference Example 5 contains only the component (B), and the industrial antibacterial composition produced in Reference Example 6. The agent composition f contains only the component (C).

In Example 1 and Comparative Example 1, the effect of preventing slime was evaluated using artificial white water. Artificial white water (pH
7.0, 30 ° C), BOD1 using starch as a nutrient source
And a culture medium containing a plurality of bacterial species using the artificial white water as a medium.
^It was continuously added so as to be ⁷ CFU / ml. The antimicrobial composition has a total of the concentrations of the components (A), (B) and (C),
10 mg / L or 20 mg / L each time in the system
Intermittent infusions were performed 3 times a day, ie, every 8 hours, to maintain 5 minutes. When tested without adding the antibacterial agent composition to this artificial white water, the slime adhesion onset time was 10 hours. Example 1 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 2.5 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 67.
An industrial antibacterial agent composition A containing 5 parts by weight was mixed with the components (A), (B) and (C) in a total amount of 10 mg in the system.
When infused to maintain 15 g / l for 15 minutes, the onset time for slime deposition was 43 hours and thus the lag time was 33 hours. The total concentration of the components (A), (B) and (C) is 20 mg / liter in the system.
When injected to maintain 5 minutes, the slime onset time was 77 hours and thus the lag time was 67 hours. When the industrial antimicrobial composition B was injected at a maintenance concentration of 10 mg / l for 15 minutes, the delay time was 35 hours. When the industrial antimicrobial composition B was injected at a maintenance concentration of 20 mg / l for 15 minutes, the delay time was 72 hours. Industrial antibacterial agent composition C, maintenance concentration 10 mg for 15 minutes
Per liter of injection, the lag time is 22
The lag time was 58 hours when infused to a maintenance concentration of 20 mg / liter for 15 minutes. When the industrial antimicrobial composition D was injected at a maintenance concentration of 10 mg / l for 15 minutes, the delay time was 28 hours. When the industrial antimicrobial composition D was injected at a maintenance concentration of 20 mg / l for 15 minutes, the delay time was It was 69 hours. When the industrial antimicrobial composition E was injected at a maintenance concentration of 10 mg / liter for 15 minutes, the delay time was 22 hours,
When infused to a maintenance concentration of 20 mg / l for 15 minutes, the lag time was 48 hours. When the industrial antibacterial agent composition F was injected so as to have a maintenance concentration of 10 mg / liter for 15 minutes, the delay time was 23 hours. When the industrial antimicrobial composition F was injected so that the maintenance concentration was 20 mg / liter for 15 minutes, the delay time was as follows. 56 hours.

Comparative Example 1 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol and 70% by weight of diethylene glycol monomethyl ether. 0 parts by weight of the industrial antimicrobial composition a was added to the system so that the total concentration of the components (A) and (B) was 1 in the system.
When infused to maintain 0 mg / liter for 15 minutes, the onset time for slime deposition was 24 hours and thus the lag time was 14 hours. Further, the component (A) and
(B) The total concentration of the components is 20 mg / liter
When infused to hold for minutes, the onset of slime deposition was 40 hours, and thus the lag time was 30 hours. The industrial antimicrobial composition b was maintained at a concentration of 1 for 15 minutes.
The delay time was 14 hours when infused to 0 mg / l and 23 hours when infused to a 20 minute maintenance concentration of 15 mg for 15 minutes. Industrial antibacterial agent composition c, maintenance concentration 10 mg for 15 minutes
/ L when injected to give a lag time of 10
The lag time was 15 hours when infused to a maintenance concentration of 20 mg / liter for 15 minutes. When the industrial antimicrobial composition d was injected so as to have a maintenance concentration of 10 mg / liter for 15 minutes, the delay time was 13 hours. When the industrial antimicrobial composition d was injected so as to have a maintenance concentration of 20 mg / liter for 15 minutes, the delay time was as follows. 20 hours. When the industrial antimicrobial composition e was injected at a maintenance concentration of 10 mg / liter for 15 minutes, the delay time was 7 hours,
When infused to a maintenance concentration of 20 mg / liter for 5 minutes, the lag time was 11 hours. When the industrial antimicrobial composition f was injected at a maintenance concentration of 10 mg / l for 15 minutes, the delay time was 9 hours. When the industrial antimicrobial composition f was injected at a maintenance concentration of 20 mg / l for 15 minutes, the delay time was 16 hours. Table 1 summarizes the results of Example 1 and Comparative Example 1.

[0016]

[Table 1]

As can be seen from Table 1, even if the concentration of the active ingredient in the added industrial antibacterial composition is the same, (A)
2,2-dibromo-3-nitrilopropionamide,
(B) 2,2-dibromo-2-nitroethanol, (C) 3,
3,4,4, -tetrachlorotetrahydrothiophene-1,
Example 1 in which the industrial antibacterial agent composition of the present invention containing three components of 1-dioxide was injected, Comparative Example 1 in which the industrial antibacterial agent composition containing only two components or one component was injected.
It can be seen that the delay time is clearly longer than that of the first embodiment, and a remarkable synergistic effect among the three components is exerted on the prevention of slime adhesion.

In Example 2 and Comparative Examples 2 and 3, the effect of preventing slime adhesion was evaluated for white water from a paper mill. As white water, white water (pH 7.5, unit water consumption 25 m ³ / T, collected from a neutral high-quality papermaking machine of a paper mill, BO
D850 mg / l, bacterial composition: Bacillus, Pseudomonas, Flavobacterium, Alcaligenes), and the antimicrobial composition was added to the sum of the concentrations of the components (A), (B) and (C) However, evaluation was performed in the same manner as in Example 1 and Comparative Example 1 except that intermittent injection was performed three times a day, that is, every 8 hours so that 25 mg / liter was maintained in the system every time for 15 minutes. When tested without adding the antibacterial agent composition to white water collected from this neutral high-quality papermaking machine, the slime deposition start time was 18 hours. Example 2 (A) 2,2-dibromo-3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and
(C) The test was performed by injecting three components of 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide into white water. When the weight ratio of component (A), component (B), and component (C) was 59: 36: 5, the slime deposition start time was 63 hours, and thus the delay time was 45 hours. The test was conducted by further changing the weight ratio of the components (A), (B), and (C). Table 2 shows the weight ratio of component (A), component (B), and component (C), and the delay time. Comparative Example 2 (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol
The test was performed by injecting the components into white water. (A) component and
When the weight ratio of the component (B) is 63:37, the slime deposition start time is 46 hours, and thus the delay time is 2 hours.
8 hours. The test was conducted by further changing the weight ratio between the component (A) and the component (B). Table 2 shows the weight ratio of the components (A) and (B) and the delay time. Comparative Example 3 (C) A test was conducted by injecting only one component of 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide into white water. The slime onset time was 30 hours and thus the lag time was 12 hours. Table 2 shows the results of Example 2 and Comparative Examples 2 and 3.

[0019]

[Table 2]

As can be seen from Table 2, even if the concentration of the active ingredient in the added industrial antibacterial composition is the same, (A)
2,2-dibromo-3-nitrilopropionamide,
(B) 2,2-dibromo-2-nitroethanol, (C) 3,
3,4,4, -tetrachlorotetrahydrothiophene-1,
Example 2 in which three components of 1-dioxide were injected was
The delay time is clearly longer than in Comparative Example 2 in which only the component was injected, and in Comparative Example 3 in which only one component was injected, and a remarkable synergistic effect among the three components was exhibited with respect to the prevention of slime adhesion. It can be seen that the antibacterial spectrum has expanded. For example, when a mixture of (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol at a weight ratio of 2: 1 is injected, the delay time is 27 hours. , While (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide alone was injected with a delay time of 12 hours,
A mixture of (A) 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol at a weight ratio of 2: 1 was further added to (C) 3,3,4,4, When tetrachlorotetrahydrothiophene-1,1-dioxide is added, the lag time extends to 48-59 hours.

In Example 3 and Comparative Example 4, a starch coating solution for papermaking used in a high-quality papermaking machine of a papermaking factory was collected and subjected to an antiseptic test. PH 9.6 collected
The starch coating solution for paper making of above was left at room temperature in advance to rot, and the decayed coating solution was diluted with a viable cell count of 8.5 × 10 ⁸ / ml.
Was mixed with a fresh starch coating solution for papermaking so as to obtain a test solution. The pH of the test solution is 9.6,
Bacillus, Pseudomonas, Alcaligenes and Flavobacterium. After dispensing this test solution into a sterile test tube, the industrial antibacterial composition was added with the components (A) and (B).
Component (C) was added so that the total concentration of the components would be 30 mg / liter. After storing the test tube in a thermostat at 30 ° C. for 5 days, the number of surviving bacteria in the test solution was measured by an agar plate dilution method. Example 3 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 2.5 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 67.
5 When the industrial antimicrobial composition A containing parts was added to the test solution, the survival cell count after 5 days was not more than 10 ² / ml. Preservative tests were similarly performed using the industrial antimicrobial compositions B, C, D, E and F. As a result, the number of surviving bacteria after 5 days was 10 ² cells / ml or less in all the tests.

Comparative Example 4 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol and 70% by weight of diethylene glycol monomethyl ether. When the industrial antimicrobial composition a containing 0 parts by weight was added to the test solution, the number of surviving bacteria after 5 days was 2.
It was 3 × 10 ⁵ cells / ml. When the industrial antimicrobial composition b was added to the test solution, the number of surviving bacteria after 5 days was 7.9 × 10 ⁵
Pcs / ml. When the industrial antibacterial composition c was added to the test solution, the number of surviving bacteria after 5 days was 5.2 × 10 ⁵ cells / ml. When the industrial antimicrobial composition d was added to the test solution,
The number of surviving bacteria after 5 days was 6.1 × 10 ⁵ cells / ml. When the industrial antimicrobial composition e was added to the test solution, the number of surviving bacteria after 5 days was 8.5 × 10 ⁴ cells / ml. When the industrial antimicrobial composition f was added to the test solution, the number of surviving bacteria after 5 days was 4.8 × 10 ³ cells / ml. The test tube was placed in a 30 ° C. incubator without adding the industrial antibacterial composition to the test solution.
After storage for 5 days, the number of surviving bacteria after 5 days was 6.0 × 10 ⁸
Pcs / ml. Table 3 summarizes the results of Example 3 and Comparative Example 4.

[0023]

[Table 3]

As can be seen from Table 3, even if the concentration of the active ingredient in the added antimicrobial composition is the same, (A) 2,2
-Dibromo-3-nitrilopropionamide, (B) 2,
2-dibromo-2-nitroethanol, (C) 3,3,4,
An industrial antibacterial agent composition of the present invention containing three components of 4, -tetrachlorotetrahydrothiophene-1,1-dioxide comprises a starch coating solution adjusted to a viable cell count of 8.5 × 10 ⁸ cells / ml. When added to the test solution, the number of surviving bacteria after 5 days is all 10 ² cells / ml or less, while the comparative example in which an industrial antibacterial composition containing only two or one component is injected In 4, the number of surviving bacteria after 5 days was 4.8 × 10 ³
７7.9 × 10 ⁵ cells / ml. From these results, the antimicrobial composition of the present invention containing the three components (A), (B) and (C) has an overwhelmingly small number of surviving bacteria and a starch coating solution for papermaking. It can be seen that a remarkable synergistic effect of the three components was exerted on the preservation of the antibacterial and the antibacterial spectrum was expanded.

In Example 4 and Comparative Example 5, antibacterial tests were performed on white water collected from a high-quality papermaking machine of a paper mill. From a high-quality neutral paper machine at a paper mill,
White water was collected. The pH of this white water is 7.6 and the number of viable bacteria is 6 ×
10 ⁷ cells / ml, and the preferred bacterial species were Bacillus, Pseudomonas, Flavobacterium and Micrococcus. After dispensing the white water into a sterile test tube, the industrial antibacterial agent composition was added with the total concentration of the components (A), (B) and (C) of 3 mg / L, 6 mg / L or 9 mg / L. It was added so that it might become. This was contacted at 30 ° C. for 15 minutes, and the number of surviving bacteria in each test solution was measured by an agar plate dilution method. Example 4 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol, (C) 3,3,4 2.5 parts by weight of 1,4, -tetrachlorotetrahydrothiophene-1,1-dioxide and diethylene glycol monomethyl ether 67.
When the industrial antimicrobial composition A containing 5 parts by weight was added so that the total concentration of the components (A), (B) and (C) was 3 mg / liter, the number of surviving bacteria was 2.9 × 10 ⁵ /
ml, and when added to be 6 mg / liter,
The number of surviving bacteria was 4.1 × 10 ⁴ cells / ml, and when added to 9 mg / l, the number of surviving cells was 3.0 × 10 ³ cells / ml. The antibacterial test was similarly performed using the industrial antibacterial compositions B, C, D, E and F. The results are shown in Table 4. Comparative Example 5 (A) 25.0 parts by weight of 2,2-dibromo-3-nitrilopropionamide, (B) 5.0 parts by weight of 2,2-dibromo-2-nitroethanol and 70.0 parts by weight of diethylene glycol monomethyl ether Is added so that the total concentration of the components (A) and (B) is 3 mg / liter, the number of surviving bacteria is 2.5 × 1
0 ⁶ a / ml, when added to a 6 mg / liter, Namazankin number was 2.4 × 10 ⁶ cells / ml, 9 mg /
When added to make up liters, the surviving bacterial count is 8.5.
× 10 ⁵ / ml. Industrial antimicrobial compositions b, c,
An antibacterial test was similarly performed using d, e, and f. The results are shown in Table 4.

[0026]

[Table 4]

As shown in Table 4, even if the concentration of the active ingredient in the added antibacterial agent composition was the same, (A) 2,2
-Dibromo-3-nitrilopropionamide, (B) 2,
2-dibromo-2-nitroethanol, (C) 3,3,4,
When the industrial antibacterial agent composition of the present invention containing three components of 4, -tetrachlorotetrahydrothiophene-1,1-dioxide was added to white water collected from a high-quality papermaking machine of a paper mill, the surviving bacterial count was And the effect of decreasing the number of surviving bacteria by increasing the amount of addition is remarkable. On the other hand, in Comparative Example 5 to which the industrial antibacterial agent composition containing only two components or one component was added, the degree of decrease in the number of surviving bacteria was small, and even when the amount added was increased, the number of surviving bacteria was reduced. The effect of the number reduction is not noticeable. From these results, the antibacterial agent composition of the present invention containing the three components (A), (B) and (C) was effective against bacteria in white water collected from a high-quality papermaking machine of a paper mill. Also, it can be seen that a remarkable synergistic effect of the three components is exhibited and the antibacterial spectrum is expanded.

[0028]

The industrial antibacterial composition and the antibacterial method of the present invention can be used in the paper and pulp industries to prevent slime in the water used in the papermaking process, various industrial cooling waters and washing waters, heavy oil sludge, metalworking oils and fibers. It is useful as an antiseptic and antibacterial agent for oils, paints, coating liquids for papers, latex, paste, etc., and has a remarkable effect on dispersing bacteria in water and slime on wall surfaces.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C02F 1/50 520 C02F 1/50 520K 520J 532 532C 532D 532E 532H 540 540B (72) Inventor Ayako Sekikawa 3-4 Nishishinjuku, Shinjuku-ku, Tokyo No. 7 Kurita Water Industries Ltd.

Claims (4)

[Claims] (A) 2,2-dibromo-3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene An industrial antibacterial composition comprising -1,1-dioxide. 2. The weight ratio of (A) 2,2-dibromo-3-nitrilopropionamide to (B) 2,2-dibromo-2-nitroethanol is from 1:99 to 99: 1, and (A) ) The total amount of 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4-tetrachlorotetrahydrothiophene-1,1 The weight ratio of the dioxide is 1:10
The industrial antibacterial composition according to claim 1, wherein the ratio is from 100 to 100: 1. 3. (A) 2,2-dibromo-3-nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene An antibacterial method comprising adding -1,1-dioxide. 4. The weight ratio of (A) 2,2-dibromo-3-nitrilopropionamide to (B) 2,2-dibromo-2-nitroethanol is from 1:99 to 99: 1,
(A) Total amount of 2,2-dibromo-3-nitrilopropionamide and (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4-,-tetrachlorotetrahydrothiophene-1 , 1-dioxide weight ratio is 1:10
１００100: 1, and (A) 2,2-dibromo-3
The sum of the concentrations of nitrilopropionamide, (B) 2,2-dibromo-2-nitroethanol and (C) 3,3,4,4, -tetrachlorotetrahydrothiophene-1,1-dioxide is 0.01 to The antibacterial method according to claim 3, wherein the antibacterial agent is added so as to be 200 mg / liter.