JP4141018B2 - Industrial antibacterial agent composition and antibacterial method - Google Patents

Description

（式中のＸはハロゲン原子、Ｙは水素原子またはハロゲン原子、Ｒは水素原子またはアルキル基を示す）で表されるハロシアノアセトアミド化合物と
（Ｂ）４，５−ジクロロ−１，２−ジチオール−３−オンまたはメチレンビスチオシアネートおよび
（Ｃ）２−ブロモ−２−ブロモメチルグルタロニトリルの３成分を含有することを特徴とする工業用抗菌剤組成物である。
【０００９】
さらにこれら３種の有効成分を有する工業用抗菌剤組成物を、抄紙工程白水または工業用水系組成物に１〜２００００ｐｐｍの割合で同時にまたは別々に添加することを特徴とする抗菌方法である。
【００１０】
【発明の実施の形態】
本発明の（Ａ）成分であるハロシアノアセトアミド系化合物としては、例えば２−クロロ−３−ニトリロプロピオンアミド、２−ブロモ−３−ニトリロプロピオンアミド、２，２−ジクロロ−３−ニトリロプロピオンアミド、２，２−ジブロモ−３−ニトリロプロピオンアミドなどが含まれるが、とくに殺菌力に優れた２，２−ジブロモ−３−ニトリロプロピオンアミドが望ましい。
【００１１】
本発明のハロシアノアセトアミド系化合物と４，５−ジクロロ−１，２−ジチオール−３−オンは殺菌力に優れ、またメチレンビスチオシアネートと２−ブロモ−２−ブロモメチルグルタロニトリルは静菌力に優れるという一般的特徴とともに、それぞれ対象とする微生物のスペクトルが異なるので適当な配合割合で総合的な相乗効果を得ることができる。しかし３種成分のうち１種または２種の配合量が極端に低いとその相乗効果が期待できないため、３成分の割合としては成分（Ａ）の１重量部に対して、成分（Ｂ）および成分（Ｃ）の割合がそれぞれ０．０１〜１０重量部、好ましくは０．１〜１重量部の含有割合が望ましい。
【００１２】
この抗菌剤組成物による抗菌方法としては、上記３種の有効成分を含有した抗菌剤組成物を抄紙工程中または水系組成物へ１〜２００００ｐｐｍの範囲で添加してもよいし、または上記３種の有効成分をそれぞれ別々に、合計で１〜２００００ｐｐｍの範囲になるように添加してもよい。
【００１３】
この抗菌剤組成物の製剤化に際して用いられる溶媒、その他の成分は特に限定されるものではないが、微生物が増殖する抄紙工程水や水系組成物などの薬剤添加対象物が水を主としているため、溶媒としては比較的親水性のもの、例えばエチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ヘキシレングリコールなどのグリコール系溶剤、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル系溶剤やプロピレンカーボネートなどが望ましい。これらは単独あるいは２種以上を組合わせて用いるとともに、３種の有効成分を溶解できる添加量が必要である。
【００１４】
また界面活性剤としては非イオン系界面活性剤、陰イオン系界面活性剤、両イオン系界面活性剤などが使用できるが、製剤安定性からポリオキシエチレンノニルフェニルエーテルなどの非イオン系界面活性剤が適当である。その他必要に応じて安定剤などの添加剤を使用できる。
【００１５】
【実施例】
次に本発明を実施例および比較例をあげて説明するが、本発明はこれらに限定されるものではない。また下表に示した配合比率はすべて重量％である。
なお、各実施例および比較例の抗菌剤組成物は、表に示す各成分を常温において混合、溶解することによって調製した。
【００１６】
実施例１〜６
表１に示す抗菌剤組成物を調製し、試験例１〜３によりその性能を評価した。
【００１７】
【表１】

【００１８】
（注）
（＊１）２，２−ジブロモ−３−ニトリロプロピオンアミド （ＤＢＮＰＡローム・アンド・ハース社製）
（＊２）４，５−ジクロロ−１，２−ジチオール−３−オン （マイクロバン８６ ２０％エチレングリコールモノメチルエーテル液 吉富製薬社製）
（＊３）メチレンビスチオシアネート （ＭＢＴ ローム・アンド・ハース社製）
（＊４）２−ブロモ−２−ブロモメチルグルタロニトリル （Ｔｅｋｔａｍｅｒ３８ カルゴン社製）
【００１９】
比較例１〜９
表２に示す抗菌剤組成物を調製し試験例１〜３によりその性能を評価した。
【００２０】
【表２】

【００２１】
（試験例１）抄紙工程白水に対する殺菌力評価
「試験方法」下記対象試料に、実施例および比較例で得た抗菌剤組成物を有効成分の合計濃度として２５または５０ｐｐｍ添加したあと３０分または６０分間培養し、この試料の菌数を変性ワックスマン寒天平板混釈法で測定した。すなわち培養した試料液の一定量を滅菌シャーレにとり、溶解した変性ワックスマン寒天培地を注入し、混釈したあと固化させ、これを３０℃の恒温室内で２日間培養後、形成されたコロニー数をカウントした。
対象試料：Ｓ製紙会社抄紙工程白水、上質紙抄造、ｐＨ７．１
生菌数：２．３×１０⁷ ＣＦＵ／ｍｌ
「試験結果」試験結果を、増減値差として表３に示した。
増減値差：［抗菌剤無添加試料のコロニー数（対数値）−抗菌剤添加試料のコロニー数（対数値）］で示し、増減値差が大きいほど殺菌効力が大きいことを表す
「考察」表３に示したように、比較例１〜９の有効成分１〜２種の抗菌剤組成物の増減値差は０．５〜３．２であるのに比べて、実施例１〜６の有効成分３種の抗菌剤組成物の増減値差は３．４〜＞６．０と明らかに大きい値を示しており、３種混合の抗菌剤組成物は抄紙工程白水に対して顕著な殺菌力を示すことが確認された。
【００２２】
【表３】

【００２３】
（試験例２）抄紙工程白水に対する静菌力評価
「試験方法」下記対象試料を無菌濾過したものに、実施例および比較例で得た抗菌剤組成物を有効成分の合計濃度として５または１０ｐｐｍ添加したあと、１０倍濃度変性ワックスマン液体培地を１％添加、対象試料を接種用として１％添加した。３０℃における試料液の濁度を経時的に記録する微生物増殖曲線によって、比濁法による立上がり時間を測定した。
対象試料：Ｓ製紙会社抄紙工程白水、上質紙抄造、ｐＨ７．１
生菌数：２．３×１０⁷ ＣＦＵ／ｍｌ
「試験結果」試験結果を、立上がり時間の差として表４に示した。
立上がり時間の差：［抗菌剤添加試料の立上がり時間−抗菌剤無添加試料の立上がり時間］で示し、時間差の値が大きいほど静菌力が大きいことを表す。
「考察」表４に示したように、比較例１〜９の有効成分１〜２種の抗菌剤組成物の立上がり時間の差は６〜１５であるのに比べて、実施例１〜６の有効成分３種の抗菌剤組成物の立上がり時間の差は１６〜２４と明らかに大きい値を示しており、３種混合の抗菌剤組成物は抄紙工程白水に対して顕著な静菌力を示すことが確認された。
【００２４】
【表４】

【００２５】
（試験例３）デンプンスラリーに対する防腐効力評価
「試験方法」Ｔ社カチオン化タピオカデンプンを１０％スラリー液（ｐＨ６．３）とし、滅菌ポリプロピレン瓶に各３０ｇを分注、抗菌剤組成物を所定量添加した後、あらかじめ腐敗させたデンプンスラリー（菌数：４．５×１０⁷ ）を１％接種した。これを３０℃の密閉静置条件下で培養し、ＴＧＣ寒天平板混釈法によって経時的に生菌数を測定した。また生菌数測定後、腐敗品を１週間毎に１％接種した。
「試験結果」生菌数の測定結果は下記の基準をもって表し、その結果を表５に示した。
− ： １０² 未満
＋ ： １０² 以上 １０⁴ 未満
++ ： １０⁴ 以上 １０⁶ 未満
+++ ： １０⁶ 以上 １０⁷ 未満
++++ ： １０⁷ 以上
「考察」表５に示したように、比較例１〜９の有効成分１〜２種の抗菌剤組成物の２１日目の評価結果は++〜++++であるのに対して、実施例１〜６の有効成分３種の評価結果は−〜＋であり、３種混合の抗菌剤組成物はデンプンスラリーに対して顕著な防腐効力を示すことが確認された。
【００２６】
【表５】

【００２７】
【発明の効果】
以上のように、ハロシアノアセトアミド系化合物、４，５−ジクロロ−１，２−ジチオール−３−オンまたはメチレンビスチオシアネートおよび２−ブロモ−２−ブロモメチルグルタロニトリルの３成分を組合わせることにより抄紙工程での強力な殺菌力、長時間にわたる静菌力、さらに水系組成物での長期間にわたる防腐効力を合わせ持った抗菌組成物および抗菌方法の提供が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention is to prevent adhesion of slime derived from microorganisms including bacteria and fungi during the papermaking process in the field of paper pulp industry, or paint, latex, starch slurry liquid, paper coating color, washing water, TECHNICAL FIELD The present invention relates to an antibacterial agent composition and an antibacterial method for preventing industrial water-based compositions based on water such as cooling water, adhesives and metalworking oils from being spoiled, discolored and deteriorated in physical properties due to microbial contamination. .
[0002]
[Prior art]
In the pulp and paper industry, a large amount of water is required in the papermaking process. Since various organic substances are dispersed and dissolved in the water, microorganisms such as bacteria and fungi propagate using the various organic substances as nutrient sources. In order to produce a viscous metabolite, the papermaking raw material dispersed during the papermaking process, such as pulp and filler, is taken in, and slime is formed on the wall surface or flow box in the chest of water. The formed slime gradually increases and eventually breaks off and is incorporated into the paper together with papermaking raw materials such as pulp and appears as foreign matter on the paper, resulting in a decrease in quality. Also, recently, paper is made at a very high speed, and in the worst case, it can cause paper breakage, leading to a decrease in productivity.
[0003]
Also, industrial water-based compositions based on water, such as coating liquids, latexes, starch slurry liquids, etc., are spoiled by contamination with these bacteria, resulting in deterioration of physical properties such as odor generation, viscosity reduction and pH fluctuation. Cause strain or clogging of the strainer, coloring, contamination by foreign substances.
[0004]
Therefore, various antibacterial agents have been used so far to prevent deterioration due to microbial factors. For example, in order to prevent generation of slime in the papermaking process, 2,2-dibromo-3-nitrilopropionamide (DBNPA), 4,5-dichloro-1,2-dithiol-3-one (DCDT), which has a very strong bactericidal activity And methylene bis-thiocyanate (MBTC), 1,2-bis (bromoacetoxy) ethane (BBAE), 1,4-bis (bromoacetoxy) -2-butene (BBAB), etc. In addition, as a preservative for the purpose of preventing deterioration of various aqueous compositions, 5-chloro-2-methyl-4-isothiazoline- having excellent bacteriostatic power and excellent stability in aqueous compositions 3-one (Cl-MIT), 1,2-benzisothiazolin-3-one (BIT), 2,2-dibromo-2-nitroethanol (DBNE), 2-bromine 2-nitropropane-1,3-diol (BNP) and 2-bromo-2-bromomethyl glutaronitrile (BBMG, 1,2-dibromo-2,4-dicyanobutane) and the like are used.
[0005]
On the other hand, when these antibacterial agents are used alone and for a long period of time, resistant bacteria are likely to appear. Thus, conventionally, a method of using these agents in combination with two or three types has been taken. For example, the combination of two components includes a combination of 2,2-dibromo-3-nitrilopropionamide and methylene bisthiocyanate in JP-A-57-114502, 2,2-dibromo-3- A number of combinations including nitrilopropionamide and 4,5-dichloro-1,2-dithiol-3-one have been disclosed. Examples of combinations of the three components include combinations of 2,2-dibromo-3-nitrilopropionamide, methylenebisthiocyanate and 2,2-dibromo-2-nitroethanol in JP-A-7-25708, and JP-A-7-187920. 2,2-dibromo-3-nitrilopropionamide, a combination of 4,5-dichloro-1,2-dithiol-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one Has been. These combinations have shown good efficacy against the microorganisms of the papermaking process and aqueous compositions where a single agent has been used for a long time, but on the other hand, the combination of these two or three components is also long-term Since new resistant bacteria due to use have begun to appear, development of an antibacterial agent effective at a low concentration having further bactericidal and bacteriostatic activity is desired.
[0006]
[Problems to be solved by the invention]
The present invention is to provide an antibacterial agent effective against a wide range of microorganisms having a strong bactericidal or bacteriostatic power, which was insufficient with conventional combinations, in order to meet the above-mentioned demand. .
[0007]
[Means for Solving the Problems]
As a result of intensive studies on various combinations of antibacterial components in order to solve this problem, the present inventors have found that halocyanoacetamide compounds, 4,5-dichloro-1,2-dithiol-3- Industrial antibacterial composition comprising three components of on- or methylenebisthiocyanate and 2-bromo-2-bromomethylglutaronitrile as active ingredients has good bactericidal, bacteriostatic and industrial properties against white water in the papermaking process even at low concentrations The present invention has been completed by finding out that it is an excellent antibacterial agent composition having an antiseptic effect on an aqueous composition.
[0008]
That is, the present invention provides (A) the general formula

(Wherein X represents a halogen atom, Y represents a hydrogen atom or a halogen atom, R represents a hydrogen atom or an alkyl group) and (B) 4,5-dichloro-1,2-dithiol An industrial antibacterial agent composition comprising three components of -3-one or methylenebisthiocyanate and (C) 2-bromo-2-bromomethylglutaronitrile.
[0009]
Furthermore, it is an antibacterial method characterized in that the industrial antibacterial agent composition having these three active ingredients is added simultaneously or separately in a ratio of 1 to 20000 ppm to the papermaking process white water or the industrial aqueous composition.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the halocyanoacetamide compound as the component (A) of the present invention include 2-chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, 2,2-dichloro-3-nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide and the like are included, and 2,2-dibromo-3-nitrilopropionamide having particularly excellent bactericidal activity is desirable.
[0011]
The halocyanoacetamide compound of the present invention and 4,5-dichloro-1,2-dithiol-3-one are excellent in bactericidal activity, and methylenebisthiocyanate and 2-bromo-2-bromomethylglutaronitrile are bacteriostatic. In addition to the general feature of being excellent, the spectrum of the target microorganisms is different, so that a comprehensive synergistic effect can be obtained at an appropriate blending ratio. However, if the amount of one or two of the three components is extremely low, the synergistic effect cannot be expected. Therefore, the proportion of the three components is 1 part by weight of the component (A), and the component (B) and The proportion of component (C) is 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight.
[0012]
As an antibacterial method using this antibacterial agent composition, an antibacterial agent composition containing the above three kinds of active ingredients may be added in the range of 1 to 20000 ppm during the paper making process or to the aqueous composition, or the above three kinds These active ingredients may be added separately so as to be in the range of 1 to 20000 ppm in total.
[0013]
Solvents and other components used in formulating this antibacterial agent composition are not particularly limited, but because the drug addition target such as papermaking process water and aqueous composition in which microorganisms grow is mainly water, Solvents that are relatively hydrophilic, such as glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Glycol ether solvents and propylene carbonate are desirable. These are used alone or in combination of two or more, and an addition amount capable of dissolving the three active ingredients is required.
[0014]
As the surfactant, nonionic surfactants, anionic surfactants, amphoteric surfactants and the like can be used. However, nonionic surfactants such as polyoxyethylene nonylphenyl ether are used because of the stability of the preparation. Is appropriate. In addition, additives such as stabilizers can be used as necessary.
[0015]
【Example】
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these. The blending ratios shown in the table below are all by weight.
In addition, the antimicrobial agent composition of each Example and the comparative example was prepared by mixing and melt | dissolving each component shown to a table | surface at normal temperature.
[0016]
Examples 1-6
The antibacterial agent composition shown in Table 1 was prepared, and its performance was evaluated by Test Examples 1 to 3.
[0017]
[Table 1]

[0018]
(note)
(* 1) 2,2-dibromo-3-nitrilopropionamide (manufactured by DBNPA Rohm & Haas)
(* 2) 4,5-dichloro-1,2-dithiol-3-one (Microban 86 20% ethylene glycol monomethyl ether solution, manufactured by Yoshitomi Pharmaceutical Co., Ltd.)
(* 3) Methylenebisthiocyanate (MBT manufactured by Rohm and Haas)
(* 4) 2-Bromo-2-bromomethylglutaronitrile (Tektamer38 manufactured by Calgon)
[0019]
Comparative Examples 1-9
The antibacterial agent composition shown in Table 2 was prepared, and its performance was evaluated by Test Examples 1 to 3.
[0020]
[Table 2]

[0021]
(Test Example 1) Evaluation of bactericidal activity against white water in paper making process "Test method" 30 minutes or 60 minutes after adding 25 or 50 ppm of the antibacterial composition obtained in Examples and Comparative Examples to the following target samples as the total concentration of active ingredients After culturing for 1 minute, the number of bacteria in this sample was measured by a modified Waxman agar plate pour method. In other words, a certain amount of the cultured sample solution is taken in a sterile petri dish, poured into a denatured Waxman agar medium, mixed, solidified, and cultured in a constant temperature room at 30 ° C. for 2 days. I counted.
Samples: S Paper Company Papermaking Process White water, fine papermaking, pH 7.1
Viable count: 2.3 × 10 ⁷ CFU / ml
“Test results” The test results are shown in Table 3 as the difference between the increased and decreased values.
Increase / decrease value difference: [Consideration] table showing that the number of colonies of the antibacterial agent-free sample (logarithmic value) −the number of colonies of the antibacterial agent-added sample (logarithmic value)] indicates that the greater the increase / decrease value difference, the greater the bactericidal efficacy As shown in FIG. 3, the difference in increase / decrease of the active ingredient 1-2 antibacterial compositions of Comparative Examples 1-9 is 0.5-3.2, compared to the effectiveness of Examples 1-6. The difference in increase / decrease values of the three antibacterial compositions of the three components is clearly large, ranging from 3.4 to> 6.0. It was confirmed that
[0022]
[Table 3]

[0023]
(Test Example 2) Evaluation of bacteriostatic power against white water in papermaking process "Test method" Addition of 5 or 10 ppm of the antibacterial composition obtained in Examples and Comparative Examples to the following target sample aseptically filtered as the total concentration of active ingredients After that, 1% of 10-fold modified Waxmann liquid medium was added, and 1% of the target sample was added for inoculation. The rise time by the turbidimetric method was measured by a microbial growth curve in which the turbidity of the sample solution at 30 ° C. was recorded over time.
Samples: S Paper Company Papermaking Process White water, fine papermaking, pH 7.1
Viable count: 2.3 × 10 ⁷ CFU / ml
“Test results” The test results are shown in Table 4 as the rise time difference.
Rise time difference: expressed as [rise time of antibacterial agent-added sample-rise time of antibacterial agent-free sample], and the greater the time difference value, the greater the bacteriostatic power.
“Discussion” As shown in Table 4, the difference in the rise time of the antibacterial agent compositions of the active ingredients 1 to 2 of Comparative Examples 1 to 9 is 6 to 15 compared to Examples 1 to 6. The difference in the rise time of the three active ingredient antibacterial compositions is clearly a large value of 16 to 24, and the three antibacterial composition shows remarkable bacteriostatic activity against white paper in the paper making process. It was confirmed.
[0024]
[Table 4]

[0025]
(Test Example 3) Evaluation of antiseptic effect on starch slurry “Test Method” T Company Cationized tapioca starch was made into 10% slurry solution (pH 6.3), 30 g each was dispensed into a sterilized polypropylene bottle, and a predetermined amount of the antibacterial agent composition After the addition, 1% of a pre-septic starch slurry (the number of bacteria: 4.5 × 10 ⁷ ) was inoculated. This was cultured under sealed stationary conditions at 30 ° C., and the viable cell count was measured over time by the TGC agar plate pour method. In addition, after the viable count, 1% of the spoiled product was inoculated every week.
“Test results” The measurement results of the viable cell count were expressed according to the following criteria, and the results are shown in Table 5.
−: Less than 10 ² +: 10 ² or more and less than 10 ⁴
++: 10 ⁴ or more and less than 10 ⁶
+++: 10 ⁶ or more and less than 10 ⁷
++++: 10 ⁷ or more “Discussion” As shown in Table 5, the evaluation results on the 21st day of the active ingredient 1-2 antibacterial compositions of Comparative Examples 1-9 are ++-++++ In contrast, the evaluation results of the three active ingredients of Examples 1 to 6 are-to +, and the antibacterial composition of the three mixtures shows a remarkable antiseptic effect on the starch slurry. confirmed.
[0026]
[Table 5]

[0027]
【The invention's effect】
As described above, by combining the three components of the halocyanoacetamide compound, 4,5-dichloro-1,2-dithiol-3-one or methylenebisthiocyanate and 2-bromo-2-bromomethylglutaronitrile It is possible to provide an antibacterial composition and an antibacterial method that have both a strong bactericidal power in the papermaking process, a bacteriostatic power for a long time, and a long-term antiseptic effect in an aqueous composition.

Claims (3)

An industry characterized by containing three components: component (A) 2,2-dibromo-3-nitrilopropionamide , component (B) methylenebisthiocyanate and (C) 2-bromo-2-bromomethylglutaronitrile Antibacterial composition. The industrial antibacterial composition according to claim 1, wherein the component (B) and the component (C) are each 0.01 to 10 parts by weight with respect to 1 part by weight of the component (A). An antibacterial method comprising adding the industrial antibacterial agent composition according to claim 1 simultaneously or separately to white paper or an industrial aqueous composition at a rate of 1 to 20000 ppm.