JP2009215271A - Biofilm releasant, and method for releasing biofilm - Google Patents

Abstract

【選択図】なし[PROBLEMS] To provide a biofilm remover that has low toxicity, is easy to handle, has no risk of corrosion to pipes and equipment, has no foaming property, and has a strong biofilm release effect when added at a relatively low concentration. provide.
A biofilm remover comprising a compound represented by the following general formula (I) as an active ingredient.
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a biofilm release agent and a biofilm release method.

  In cooling water systems for air conditioning, refrigeration, or various plants, biofilms adhere to piping and equipment in the system due to bacteria, filamentous fungi, algae, etc., resulting in reduced thermal efficiency, clogging of pipes, reduced flow rate, metal parts Failure such as corrosion is caused.

  For such biofilms, a method using a drug has been generally used, and as a drug used, a biofilm remover that peels or cleans the attached biofilm, or prevents biofilm adhesion. And slime control agent.

  Among these agents, slime control agents or bactericides reduce slime adhesion potential by keeping the microbial concentration in water low. In general, a slime control agent suppresses bactericidal or bacterial growth by inhibiting fungal enzyme reaction and cell membrane denaturing action. On the other hand, the biofilm remover mainly disperses bacterial aggregates by lowering the viscosity of an adhesive substance (generally a polysaccharide) outside the cells, and peels the biofilm from the adhesion surface. Therefore, even a drug effective as a slime control agent may not be effective as a biofilm release agent, and even if effective as a biofilm release agent, it may not be effective as a slime control agent.

  Here, as a biofilm remover, an organic disinfectant such as isothiazoline proposed in JP-A-5-157719 (Patent Document 1) or the like, or JP-A 2003-267811 (Patent Document 2). The chlorinated sulfamic acid proposed in the above is used, but its biofilm peeling force is low, and improvement is demanded.

In addition, a method of peeling a biofilm at once using a strong chlorinating agent or an oxidizing agent such as hydrogen peroxide is often performed. In addition to the need for neutralization after the treatment, the work becomes complicated, and there is a concern about corrosion of piping and equipment.
JP-A-5-157719 JP 2003-267811 A JP 2005-325036 A JP 2006-21105 A

  The present invention improves the above-mentioned conventional problems, that is, it is low in toxicity and easy to handle, there is no risk of corrosion to pipes and equipment, no foaming, and it is powerful when added at a relatively low concentration. An object of the present invention is to provide a biofilm release agent that can provide a biofilm release effect.

（但し、上記一般式において、Ｒ_１およびＲ_４は、炭素数１〜４の直鎖若しくは分岐の同一または異なるアルキレン基であり、Ｒ_２およびＲ_５は、水素原子、同一または異なるハロゲン原子、低級アルキル基または低級アルコキシ基であり、Ｒ_３は、炭素数２〜１２の直鎖若しくは分岐のアルキレン基であり、Ｒ_６は、炭素数１〜１８の直鎖若しくは分岐のアルキル基であり、Ｚ⁻は、水中で解離可能な陰イオンである。） In order to solve the above-mentioned problems, the biofilm remover of the present invention is a biofilm remover characterized by containing a compound represented by the following general formula (I) as an active ingredient as described in claim 1. .

(In the above general formula, R ₁ and R ₄ are linear or branched identical or different alkylene groups having 1 to 4 carbon atoms, R ₂ and R ₅ are hydrogen atoms, identical or different halogen atoms, A lower alkyl group or a lower alkoxy group, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, Z ⁻ is an anion that can be dissociated in water.

The biofilm remover of the present invention is the biofilm remover according to claim 1, wherein R ₁ and R ₄ are 3 or 4 positions of the pyridine ring. R ₂ and R ₅ are hydrogen atoms, R ₃ is a tetramethylene group, and R ₆ is a group selected from an octyl group, a decyl group, and a dodecyl group. , Z ⁻ is an anion dissociable in water.

  The biofilm remover according to the present invention is the biofilm remover according to claim 1, wherein the compound represented by the general formula (1) is 1,4-bis (3,3 ' -(1-decylpyridinium) methyloxy) butane salt.

  As described in claim 4, the biofilm remover of the present invention contains phthalaldehyde and / or glutaraldehyde as an active ingredient in the biofilm remover according to any one of claims 1 to 3. It is characterized by doing.

  According to a biofilm peeling method of the present invention, as described in claim 5, the biofilm peeling agent according to any one of claims 1 to 4 is added to aqueous water. It is a peeling method.

  The biofilm remover of the present invention has low toxicity and is easy to handle, does not cause corrosion to pipes and equipment, has no foaming property, and has a strong biofilm release effect when added at a relatively low concentration. Biofilm release agent.

  The biofilm remover of the present invention contains a compound represented by the following general formula (I) as an active ingredient.

（但し、上記一般式において、Ｒ_１およびＲ_４は、炭素数１〜４の直鎖若しくは分岐の同一または異なるアルキレン基であり、Ｒ_２およびＲ_５は、水素原子、同一または異なるハロゲン原子、低級アルキル基または低級アルコキシ基であり、Ｒ_３は、炭素数２〜１２の直鎖若しくは分岐のアルキレン基であり、Ｒ_６は、炭素数１〜１８の直鎖若しくは分岐のアルキル基であり、Ｚ⁻は、水中で解離可能な陰イオンである。）

(In the above general formula, R ₁ and R ₄ are linear or branched identical or different alkylene groups having 1 to 4 carbon atoms, R ₂ and R ₅ are hydrogen atoms, identical or different halogen atoms, A lower alkyl group or a lower alkoxy group, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, Z ⁻ is an anion that can be dissociated in water.)

  Here, the compound represented by the general formula (I) is a compound known from JP-A-2005-325036 (Patent Document 3), JP-A-2006-21105 (Patent Document 4) and the like. Discovered the effectiveness of such a compound as a biofilm release agent in the process of studying an effective biofilm release agent, and reached the present invention.

  By adding the compound represented by the general formula (I), it is possible to denature and effectively peel the biofilm adhering to the device or the pipe.

In the general formula (1), R ₁ and R ₄ are methylene groups bonded to the 3 or 4 position of the pyridine ring, R ₂ and R ₅ are hydrogen atoms, and R ₃ is tetramethylene. R ₆ is a group selected from an octyl group, a decyl group and a dodecyl group, and Z ⁻ is an anion that can be dissociated in water, so that higher biofilm releasability can be obtained. preferable.

  Furthermore, when the compound represented by the general formula (1) is a salt of 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butane, higher biofilm peelability can be obtained. it can.

  A preferred range of the concentration of the compound represented by the general formula (1) to the aqueous water is usually 1 mg / L or more and 1000 mg / L or less. If the amount is less than 1 mg / L, the effect due to the addition may not be obtained. On the other hand, when the amount exceeds 1000 mg / L, the improvement in the biofilm peeling effect accompanying an increase in the amount added cannot be sufficiently obtained. A more preferable range is 5 mg / L or more and 100 mg / L or less.

  Furthermore, when the compound represented by the general formula (I) and phthalaldehyde and / or glutaraldehyde are added to the target water, high biofilm peelability can be obtained synergistically. In this case, the compound represented by the above general formula (1) and phthalaldehyde and / or glutaraldehyde may be used as one agent as a biofilm release agent, or it may be composed of agent A and agent B, The compound represented by the general formula (1) may be added to the agent A, and phthalaldehyde and / or glutaraldehyde may be added to the agent B, respectively, and necessary active ingredients can be added to the target aqueous water. Therefore, when both phthalaldehyde and glutaraldehyde are used in combination, they may be divided into three agents, agent A, agent B and agent C.

  At this time, it is preferable that the compounding ratio of the compound represented by the general formula (I) and phthalaldehyde and / or glutaraldehyde is 1:20 to 100: 1 (including the boundary value). If the blending is outside this boundary value, the effect of blending the two agents may not be sufficiently obtained. A more preferable blending ratio is 1: 5 to 20: 1 (including the boundary value). As described above, the preferable range of the addition concentration in the case of blending the two agents is that a sufficient effect can be obtained with a synergistic effect less than the addition of the compound represented by the general formula (1) alone. The total concentration of active ingredients is usually 1 mg / L or more and 100 mg / L or less. If it is less than 1 mg / L, the effect due to the addition may not be obtained. On the other hand, when the addition exceeds 100 mg / L, the improvement of the biofilm peeling effect accompanying the increase in the amount added cannot be obtained sufficiently. A more preferable range is 2 mg / L or more and 50 mg / L or less.

  In the biofilm release agent of the present invention, other components may be added as long as the biofilm release effect is not impaired, for example, acrylic acid-based, maleic acid-based, methacrylic acid-based, sulfonic acid-based, Itaconic acid-based or isobutylene-based polymers and copolymers thereof, phosphoric acid-based polymers, phosphonic acid, phosphinic acid, or water-soluble salts thereof such as 5-chloro-2-methyl Isothiazolone compounds such as -4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, hydrogen peroxide, hydrazine, chlorine-based disinfectant Sodium chlorate, etc.), bromine and iodine fungicides, glutaraldehyde, pyrithione compounds, dithiols Products, thiocyanate compounds such as methylenebisthiocyanate, ionene polymers, bis-quaternary ammonium salts other than the compounds represented by formula (I), quaternary ammonium salt compounds other than bis-quaternary ammonium salts, etc. Anti-slime agents, such as azoles such as benzotriazole and tolyltriazole, amine compounds such as ethylenediamine and diethylenetriamine, aminocarboxylic acid compounds such as nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, such as gluconic acid, Various water treatment agents such as organic carboxylic acids such as acid, oxalic acid, formic acid, tartaric acid, phytic acid, succinic acid, and lactic acid can be used in combination, and such cases are also included in the present invention.

  The biofilm peeling method of the present invention is carried out by adding the biofilm peeling agent as described above to water-based aqueous water in which a biofilm is attached to a pipe, waterway, equipment or the like.

  Examples of the biofilm remover of the present invention will be specifically described below.

<Example 1>
Eight slide glasses were immersed for 14 days in cooling water system water for cooling actually operating, and a biofilm was adhered to the slide glass surface. These were immersed in 500 mL of sterilized Tsukuba city water in a glass container so that the maximum plane was vertical, and the chemicals shown in Table 1 (no chemicals: including controls. Abbreviations in the table are shown outside Table 1) Then, the mixture was allowed to stand with stirring at 60 rpm.

  After 5 hours from the addition, the deposits remaining on the surface of each slide glass were wiped off and resuspended in 10 mL of sterilized ion-exchanged water, and the adenosine triphosphate (ATP) concentration was measured with an ATP analyzer (AF-100 manufactured by Toa DKK Corporation). It was measured. At this time, the lower the adenosine triphosphate concentration, the smaller the amount of attached microorganisms. The results are shown in Table 1 (in the table, “<10” indicates less than 10 pmol / L).

  According to Table 1, according to 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide, which is one of the compounds represented by the above general formula (I), extremely high biofilm peeling It turns out that an effect is acquired. In addition, a mixed addition system in which 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide and orthophthalaldehyde are added to 10 mg / L and 2 mg / L, respectively, and , 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide and glutaraldehyde were added at a mixing rate of 10 mg / L and 40 mg / L, respectively. Both adenosine triphosphate concentrations in the addition system were less than 10 pmol / L. Thus, in these mixed addition systems, a high effect is obtained due to the synergistic effect of the combined use of the drugs, and the biofilm is considered to be completely peeled off.

<Example 2>
1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide, which is one of the compounds represented by the above general formula (I), in the cooling water for cooling that is actually operating Was added to 25 mg / L. Before this addition and 1 hour after the addition, a part of the cooling tower lower water tank (about 10 cm ² ) was wiped off. These wiped deposits were each resuspended in 10 mL of sterilized ion-exchanged water, and the amount of adhered microorganisms was evaluated by measuring the concentration of these adenosine triphosphates.

  As a result, the adenosine triphosphate concentration in the sample before the drug was 1300 pmol / L, whereas the sample 1 hour after the addition of the drug obtained a result of 54 pmol / L. In addition, it was confirmed that 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butane dibromide provides a high biofilm peeling effect.

  At this time, the turbidity of the cooling water before the addition of the drug was 1 degree, but increased to 15 degrees 1 hour after the addition of the drug. This is thought to be due to the biofilm peeled off by the addition of the drug, and when this turbid matter was actually centrifuged and observed with a microscope, it was confirmed to be a microbial mass.

<Example 3>
1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide, which is one of the compounds represented by the above general formula (I), in the cooling water for cooling that is actually operating Was 8 mg / L and orthophthalaldehyde was added to 1 mg / L. Before this addition and 1 hour after the addition, a part of the cooling tower lower water tank (about 10 cm ² ) was wiped off. These deposits were resuspended in 10 mL of sterilized ion-exchanged water, and the amount of attached microorganisms was evaluated by measuring the concentration of these adenosine triphosphates.

  As a result, the adenosine triphosphate concentration was 950 pmol / L in the sample before the drug addition, whereas the sample after the drug addition was 18 pmol / L. Even in the actual cooling water system, It was confirmed that the use of 4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide and orthophthalaldehyde provides a very high biofilm peeling effect.

  At this time, the turbidity of the cooling water before the addition of the drug was less than 0.5 degrees, but increased to 12 degrees 1 hour after the addition of the drug. This is thought to be due to the biofilm peeled off by the addition of the drug, and when this turbid matter was actually centrifuged and observed with a microscope, it was confirmed to be a microbial mass.

Claims (5)

A biofilm remover comprising a compound represented by the following general formula (I) as an active ingredient.

(In the above general formula, R ₁ and R ₄ are linear or branched identical or different alkylene groups having 1 to 4 carbon atoms, R ₂ and R ₅ are hydrogen atoms, identical or different halogen atoms, A lower alkyl group or a lower alkoxy group, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, Z ⁻ is an anion that can be dissociated in water.) In the general formula (1), R ₁ and R ₄ are methylene groups bonded to the 3 or 4 position of the pyridine ring, R ₂ and R ₅ are hydrogen atoms, and R ₃ is tetramethylene. 2. The biofilm remover according to claim 1, wherein R ₆ is a group selected from an octyl group, a decyl group, and a dodecyl group, and Z ⁻ is an anion that can be dissociated in water.   The biofilm according to claim 1, wherein the compound represented by the general formula (1) is a salt of 1,4-bis (3,3 '-(1-decylpyridinium) methyloxy) butane. paint remover.   The biofilm remover according to any one of claims 1 to 3, which contains phthalaldehyde and / or glutaraldehyde as an active ingredient.   The biofilm peeling method characterized by adding the biofilm peeling agent of any one of the said Claim 1 thru | or 4 to aqueous water.