JPH07258002A - Germicide for water based system containing reducing material - Google Patents

Abstract

PURPOSE:To obtain a germicide for industrial use exhibiting a specific germicidal effect even in a system containing reducing materials by using 2,2'- dihydroxy-5,5'-dichlorodiphenylmethane or a specific compound combined with the game. CONSTITUTION:A germicide for industrial use consisting of 2,2'-dihydroxy-5,5'- dichlorodiphenylmethane of the formula I as an effective ingredient or a brominated acetic acid ester or an isothiazoline-3-one-based compound of the formula II combined with the same as the effective component and exhibiting an excellent germicidal effect for a long period of time even in a water system containing reducing materials. As reducing materials in water sulfite ion, thiosulfate ion, hydrogen sulfide, etc., are cited. As the isothiazoline-3-one-based compound of the formula II, e.g. 5-chloro-2-methyl-4isothiazoline-5--one, etc., are cited. As the ester of brominated acetic acid, e.g., 1,4-bis(bromoacetoxy)-2-butene, etc., are cited. A germicidal efficiency is more enhanced by using those compounds in combination.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a new industrial fungicide. More specifically, the present invention relates to an industrial bactericide that exhibits a stable bactericidal effect for a long period of time even in an aqueous system containing a reducing substance.

[0002]

2. Description of the Related Art In the raw material preparation process and papermaking process in the paper manufacturing industry, bacteria and fungi breed as slime by using cellulose and various additives as nutrient sources.
When such slime peels off from the wall surface, it is mixed in the product as a foreign substance, which lowers the product quality, or induces paper breakage in the papermaking process to impede continuous operation, resulting in a significant decrease in production efficiency. Bring a situation.
In the papermaking process, rosin-based sizing agents, starch, gelatin, latex, casein, etc. are used in large quantities as additives, and since all of these additives serve as nutrient sources, microorganisms are easily proliferated. . BACKGROUND ART Conventionally, in various industrial fields, treatment with bactericides has been performed against microbial disorders such as bacteria and fungi, because their implementation is relatively simple and economical. However, in a system in which a reducing substance such as sulfite ion or thiosulfate ion is present, the efficacy of conventional antibacterial agents and bactericides is remarkably reduced, and stable operation is hindered. Further, in a system such as starch or latex where decay is progressing, reducing substances such as hydrogen sulfide are generated, and it has been a serious problem that the effectiveness of conventional preservatives is significantly impaired. As a sterilization method in the presence of such a reducing substance, a method of using a conventional sterilizing agent after oxidatively decomposing the reducing substance with a chlorine-based agent has been used. However, in the papermaking process, the concentration of the reducing substance in the system fluctuates with time, so it was difficult to always decompose appropriately and stably. Therefore, when a conventional bactericidal agent is used in such a paper manufacturing process, it is necessary to add a large amount of the reducing substance concentration or more, which is economically impossible. Therefore, at present, there is no choice but to deal with it by frequently cleaning the inside of the system.

[0003]

Under these circumstances, the present invention provides an industrial bactericide that exhibits a stable and excellent bactericidal effect even in a system containing a reducing substance. It was done for the purpose.

[0004]

Means for Solving the Problems The present inventor has conducted extensive studies to develop an industrial bactericidal agent that exhibits a specific bactericidal effect even in a system in which a reducing substance as described above is present. It was found that the objective can be achieved by combining 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane with a specific compound, and found that The present invention has been completed based on the above. That is, the present invention relates to (1) 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane-containing reducing agent-containing aqueous fungicide containing (2) 2,2'-dihydroxy-5,5 as an active ingredient. '-Dichlorodiphenylmethane and brominated acetic acid ester-containing reducing agent-containing aqueous fungicide, and
(3) A reductive substance-containing aqueous fungicide containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane, an isothiazolin-3-one compound and a brominated acetic acid ester as active ingredients.

The present invention will be described in detail below. 2,2′-dihydroxy-5, which is used in the fungicide of the present invention,
5′-dichlorodiphenylmethane is a compound represented by the formula [1].

[Chemical 1] There are various industrial fungicides used for water systems, and examples thereof include thiocyanate compounds, halocyanoacetamide compounds, isothiazolone compounds, dithiocarbamic acid compounds, and benzylammonium chloride compounds. . However, although all of these industrial bactericides have considerable effects in ordinary water systems, when the water system contains a reducing substance, its efficacy is extremely reduced, and it has little practicality. On the other hand, 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane used in the reducing-substance-containing aqueous disinfectant of the present invention is characterized by exhibiting sufficient disinfecting power even in an aqueous system containing sulfite ion or thiosulfate ion. have. Furthermore, 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane can also be used as its sodium salt and potassium salt.

2,2'-Dihydroxy-5,5'-of the present invention
The bactericidal agent in which dichlorodiphenylmethane and brominated acetic acid esters are used in combination or in which both are mixed has an even more excellent bactericidal effect in a reducing substance-containing water system. Two,
Examples of the brominated acetic acid ester used together with 2'-dihydroxy-5,5'-dichlorodiphenylmethane include:
For example, methyl monobromoacetate, ethyl monobromoacetate, phenyl monobromoacetate, methyl dibromoacetate, ethyl dibromoacetate, 1,2-bis (monobromoacetoxy) ethane, 1,2-bis (monobromoacetoxy) propane, 1,2- Bis (monobromoacetoxy) butane, 1,4-bis (monobromoacetoxy) butane, 1,
4-bis (monobromoacetoxy) butene, 1,2-bis (dibromoacetoxy) ethane, 1,2-bis (dibromoacetoxy) propane, 1,2-bis (dibromoacetoxy) butane, 1,4-bis (dibromo) Examples thereof include acetoxy) butane and 1,4-bis (dibromoacetoxy) butene. 2,2'-dihydroxy-
The ratio of 5,5'-dichlorodiphenylmethane and the brominated acetic acid ester to be used is not particularly limited, but a ratio of both of them in a weight ratio of 1:20 to 20: 1 can be particularly preferably used. 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and brominated acetic acid esters are
Each may be added separately to the water system, or it is also possible to use a mixture of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and brominated acetic acid esters in a fixed ratio in advance. The bactericide containing the 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane, isothiazolin-3-one compound and brominated acetic acid ester of the present invention has a particularly excellent bactericidal effect in a reducing substance-containing water system. Have

Isothiazoline-3-used in the present invention
On-type compounds have the general formula [2]

[Chemical 2] (In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, R ² represents a hydrogen atom or a halogen atom, R ³ represents a hydrogen atom or a halogen atom, or R ² and R ³ is a compound represented by condensation to form an aromatic ring.
-Chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-ethyl-3-isothiazolone, 4,5-dichloro-2-octyl-3-isothiazolone, 4,5-benzisothiazoline-3- On can be mentioned. In the case of the present invention, 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and the isothiazolin-3-one compound may be added independently, but 2,2'-dihydroxy-5,5 '-Dichlorodiphenylmethane is the host molecule and isothiazoline-3
Since the -one compound can serve as a guest molecule to form an inclusion compound, it is preferably added in the form of an inclusion compound. However, for the purpose of the present invention, it is not always necessary that a strict intermolecular compound is formed, and those having a weight ratio of 1:20 to 20: 1 can be preferably used.

2,2'-Dihydroxy-5,5'-of the present invention
Examples of the brominated acetic acid ester used in combination with dichlorodiphenylmethane and an isothiazolin-3-one compound include, for example, methyl monobromoacetate, ethyl monobromoacetate, phenyl monobromoacetate, and methyl dibromoacetate.
Ethyl dibromoacetate, 1,2-bis (monobromoacetoxy) ethane, 1,2-bis (monobromoacetoxy)
Propane, 1,2-bis (monobromoacetoxy) butane, 1,4-bis (monobromoacetoxy) butane, 1,
4-bis (monobromoacetoxy) butene, 1,2-bis (dibromoacetoxy) ethane, 1,2-bis (dibromoacetoxy) propane, 1,2-bis (dibromoacetoxy) butane, 1,4-bis (dibromo) Examples thereof include acetoxy) butane and 1,4-bis (dibromoacetoxy) butene. 2,2'-dihydroxy-
5,5'-dichlorodiphenylmethane and isothiazoline-
The ratio of the 3-one compound and the brominated acetic acid ester to be used is not particularly limited, but it is particularly preferable to use the ratio of the total weight of the former two and the weight of the latter of 1:20 to 20: 1. Can be used. The clathrate compound and the brominated acetic acid ester may be separately added to the aqueous system, or the clathrate of 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and the isothiazolin-3-one type compound may be added in advance. It is also possible to use a mixture of the compound and the brominated acetic acid ester in a fixed ratio.

The water-based disinfectant containing a reducing substance of the present invention is
It retains a strong bactericidal effect for a long time in an aqueous system containing a reducing substance such that an ordinary bactericide for water system loses its effect in a short time. Examples of the reducing substance existing in the water system include sulfite ion, thiosulfate ion, hydrogen sulfide and the like, and an aqueous system containing 5 ppm or more of these can be considered as a reducing substance-containing water system. The reducing agent-containing water-based disinfectant of the present invention has a strong bactericidal effect even in an aqueous system containing less than 5 ppm of reducing agent, but in an aqueous system containing less than 5 ppm of reducing agent, a conventional aqueous disinfectant is used. Also, a nearly satisfactory bactericidal effect can be obtained. The method of using the reducing-substance-containing aqueous fungicide of the present invention is not particularly limited, but it is preferable to use the active ingredient dissolved or dispersed in water or an organic medium. When used in a dispersed state in a medium, the smaller the particle size, the more preferable, and practically, it is advantageous that the fine powder passes through 100 mesh. The organic medium is not particularly limited, for example, ethylene glycol, propylene glycol, glycerin, diethylene glycol, alcohol such as polyglycerin, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monobutyl ether, liquid paraffin, further xylene, toluene. And the like, plant oils such as castor oil, soybean oil, olive oil, and rapeseed oil, terpenes such as cypress oil, and surfactants such as polyoxyethylene alkyl ether. These dispersion media may be used alone or in combination of two or more.

The addition amount of the reducing substance-containing bactericidal agent for aqueous systems of the present invention is appropriately selected depending on the kind of the sterilizing object to which the bactericidal agent is applied. Usually, when the sterilizing object is an aqueous system in a papermaking process, that is, slime. When used as a control agent, a good bactericidal effect can be obtained if the reducing substance-containing aqueous bactericidal agent is used so that the total amount of active ingredients is 0.1 to 100 g / m ³ . There is no particular limitation on the method of adding the reducing substance-containing aqueous bactericide of the present invention to the aqueous system,
Composition or inclusion compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and isothiazolin-3-one compound and brominated acetic acid ester , 2'-dihydroxy- can be added simultaneously.
Composition of 5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and isothiazolin-3-one compound or clathrate compound and brominated acetic acid ester at the same place in water system Can be added separately, and further 2,2'-dihydroxy-
Composition of 5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and isothiazolin-3-one compound or clathrate compound and brominated acetic acid ester in different places of water system It can be added separately.

In the reducing substance-containing aqueous fungicide of the present invention, as a stabilizer, if desired, for example, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, xanthan gum,
Rhamzan gum, sodium polyacrylate, polyacrylamide, alkyl methacrylate / diethylaminoethyl methacrylate copolymer, alkyl methacrylate / N-vinyl-2-pyrrolidone copolymer, alkyl methacrylate / polyethylene glycol methacrylate copolymer, dodecyl fumarate / diethylaminoethyl Methacrylate copolymer, styrene / maleic acid copolymer, sodium naphthalenesulfonate-formalin condensate, sodium melaminesulfonate-formalin condensate, sodium lauryl sulfate, sodium laurylbenzenesulfonate, polyoxyethylene alkyl ether, polyalkylene glycol Carbamic acid ester,
Alkylbenzene sulfonic acid, nonionic surfactant, etc. can be used. The reducing-substance-containing aqueous fungicide of the present invention is not only used as a slime control agent in the paper manufacturing industry, but is effective for all aqueous compositions containing a reducing substance, for example, starch,
It can be used as an antiseptic for casein, SBR latex, paint, an antiseptic for adhesives, an antiseptic in a system using a metal working oil such as cutting oil, and the like. When the reducing substance-containing aqueous bactericidal agent of the present invention is used as these preservatives, the addition amount thereof is preferably selected to be 1 to 2000 g / m ³ .

[0012]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, each code | symbol in an Example and a comparative example means the following. Drug A: 2,2-dibromo-3-nitrilopropionamide 20% by weight and diethylene glycol 80% by weight
Mixture of. Drug used B: 4,5-dichloro-1,2-dithiol-3
A mixture of 10% by weight of on and 90% by weight of diethylene glycol monomethyl ether. Drug used C: 5-chloro-2-methyl-4-isothiazolin-3-one 10% by weight and diethylene glycol 90
Wt% mixture. Drug used D: A mixture of 50% by weight of 1,4-bis (bromoacetoxy) -2-butene and 50% by weight of ethylene glycol monomethyl ether. Drug E used: A mixture of 10% by weight of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and 90% by weight of diethylene glycol monomethyl ether. Drug used F: clathrate compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and 5-chloro-2-methyl-4-isothiazolin-3-one (inclusion ratio about 7:
3) A mixture of 10% by weight and 90% by weight of water.

Examples 1 to 4 and Comparative Examples 1 to 8 Using a white water sample collected from a white water silo of a medium quality paper manufacturing machine of a paper mill, the bactericidal effect and the growth inhibitory effect of the drug were investigated. White water sample with no reducing substance added and sodium thiosulfate 50pp as reducing substance
A total of 3 types of test water were prepared by adding m and 100 ppm. Use these test waters with phosphate buffer (1/50
The pH was adjusted to 6.8 with M). The test chemicals shown in Table 1 were added to these test waters so that the concentration of the active ingredient in the test chemicals was 20 ppm, and the mixture was shaken at 30 ° C. for 30 minutes. Separately, for test water containing no added chemicals, 3
Shaking was performed at 0 ° C. for 30 minutes, and these were used as blank tests. After the shaking for 30 minutes was completed, the number of bacteria in each test water was measured, and compared with the result of the blank test, the sterilization rate in each test water was determined by the following formula.

[Equation 1] The results are shown in Table 1.

[0014]

[Table 1]

The chemicals used in Comparative Examples have a relatively good bactericidal effect on test water to which sodium thiosulfate is not added, and show a bactericidal rate of 85.0 to 99.8%. ing. However, the bactericidal effect of the chemicals used in the comparative examples was remarkably reduced against the test water containing sodium thiosulfate, and the bactericidal rate was 51.4% even at the highest level, and was 10% or less in most cases. In some cases, the number of bacteria is the same as the test water. On the other hand, in the examples using the reducing substance-containing aqueous bactericide of the present invention, not only an excellent bactericidal effect was shown against test water to which sodium thiosulfate was not added, but sodium thiosulfate was added. Even in test water, a sterilization rate of 90% or more was always obtained.
Further, when the results of Examples 1 to 4 are examined in detail, 2,2 ′
2,2'-dihydroxy-5,5 'rather than Example 1 using -dihydroxy-5,5'-dichlorodiphenylmethane.
Example 2 using the inclusion compound of -dichlorodiphenylmethane and 5-chloro-2-methyl-4-isothiazolin-3-one had a higher sterilization rate, and further,
It can be seen that Examples 3 and 4 in which 4-bis (bromoacetoxy) -2-butene was used in combination had a higher sterilization rate. Examples 5 to 8 and Comparative Examples 9 to 16 Using the respective test waters prepared in Examples 1 to 4 and Comparative Examples 1 to 8, the test waters and the broth medium were mixed so that the concentration of the test water was 5%. did. These samples were kept at 30 ° C., the number of bacteria was measured every 4 hours, the time when the number of bacteria exceeded 10 times the initial value was determined, and this was defined as the growth inhibition time. The results are shown in Table 2.

[0016]

[Table 2]

The chemicals used in Comparative Examples have a relatively good growth inhibitory effect on test water to which sodium thiosulfate is not added, and show a growth inhibitory time of 12 to 16 hours. . However, with respect to the test water containing sodium thiosulfate, the growth-suppressing effect of the drug used in Comparative Example was significantly reduced, and the growth-suppressing time was 4 hours or 8 hours. On the other hand, in the examples using the reducing substance-containing aqueous fungicide of the present invention, not only does it show an excellent growth inhibitory effect on test water to which sodium thiosulfate is not added, but sodium thiosulfate is added. Even in the test water, the growth suppression time of 12 hours or 16 hours was always obtained. Examples 9 to 10 and Comparative Examples 17 to 18 An actual machine test was performed on a fine paper manufacturing machine of a paper mill. During the test period, the amount of reducing substance in white water varied in the range of 20 to 100 ppm in terms of sodium thiosulfate. The pH was 7.2 and the water temperature was almost constant at 30 ° C. The chemicals used were added by the following method. The test was continued for 4 days except for Comparative Example 17, and after 4 days, the machine was stopped and the amount of deposits (slime) in the system was observed.
It was judged by rank. The method of adding the used drug and the criteria for determining the effect are as follows.

Example 9: Method of adding drug to be used Example 9: The drug D to be used was added to cebuol three times a day every 8 hours at 100 ppm as an active ingredient of the drug against inflow water.
For 15 minutes, the drug E to be used was added to the white water recovery system polydisk filter 3 times a day every 8 hours for 15 minutes so as to be 100 ppm as an active ingredient of the drug in the inflow water. Example 10: Cebuol was supplemented with the drug D to be used 3 times a day every 8 hours by 100 pp as an active ingredient of the drug against influent water.
m was added for 15 minutes, and the used drug F was added to the white water recovery system polydisk filter 3 times a day every 8 hours for 15 minutes so that the active ingredient of the drug was 100 ppm with respect to the inflow water. . Comparative Example 17: Cebuol with the drug D used 3 times a day every 8 hours at 100 pp as the active ingredient of the drug against influent water.
m was added for 15 minutes, and the used drug A was added to the white water recovery system polydisk filter 3 times a day every 8 hours for 15 minutes so that the active ingredient of the drug was 100 ppm with respect to the inflow water. . Comparative Example 18: Cebuol was supplemented with the used drug D every 8 hours three times a day at 100 pp as the active ingredient of the drug against inflow water.
m was added for 15 minutes, and the used drug C was added to the white water recovery system polydisk filter 3 times a day every 8 hours for 15 minutes so that the active drug content was 100 ppm in the inflow water. Judgment Criteria Rank A: There is no stain in the system and there is no problem. Rank B: Dirt is seen around the dead space and the water line, but there is no particular problem. Rank C: Dirt is noticeable everywhere on the wall surface of the system,
I can manage it somehow. Rank D: The slime trouble makes it impossible to operate. The results are shown in Table 3. The reducing-substance-containing aqueous fungicide of Example did not cause any problem even after the test for 4 days, whereas the fungicide of Comparative Example 17 was subjected to the test after the spotted trouble of the product occurred on the 3rd day. I had to stop.
Further, even with the bactericide of Comparative Example 18, spot trouble occurred on the 4th day.

[0019]

[Table 3]

[0020]

EFFECTS OF THE INVENTION By using the reducing-substance-containing aqueous bactericide of the present invention, it is possible to prevent the generation of slime and the decay of the aqueous system for a long period of time even in the aqueous system in which the reducing substance is present. Can be stably operated, and deterioration of product quality can be prevented. Further, the cost required for slime control and the cost required for antiseptic can be reduced.

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Claims (3)

[Claims] 1. A bactericide for reducing water containing a reducing substance containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane as an active ingredient. 2. A reductive substance-containing bactericidal agent containing a reducing substance, which comprises 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and a brominated acetic acid ester as active ingredients. 3. A reductive substance-containing aqueous fungicide containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane, an isothiazolin-3-one compound and a brominated acetic acid ester as active ingredients.