JP2542324B2 - Industrial sterilization and antiseptic composition - Google Patents

Industrial sterilization and antiseptic composition

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Publication number
JP2542324B2
JP2542324B2 JP5086002A JP8600293A JP2542324B2 JP 2542324 B2 JP2542324 B2 JP 2542324B2 JP 5086002 A JP5086002 A JP 5086002A JP 8600293 A JP8600293 A JP 8600293A JP 2542324 B2 JP2542324 B2 JP 2542324B2
Authority
JP
Japan
Prior art keywords
dichloroglyoxime
sterilization
industrial
antiseptic
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP5086002A
Other languages
Japanese (ja)
Other versions
JPH06298607A (en
Inventor
恭至 二田
真弓 小田桐
英奇 菅野
誠康 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JUNSEI KAGAKU KK
Fuji Sangyo Co Ltd
Original Assignee
JUNSEI KAGAKU KK
Fuji Sangyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JUNSEI KAGAKU KK, Fuji Sangyo Co Ltd filed Critical JUNSEI KAGAKU KK
Priority to JP5086002A priority Critical patent/JP2542324B2/en
Publication of JPH06298607A publication Critical patent/JPH06298607A/en
Application granted granted Critical
Publication of JP2542324B2 publication Critical patent/JP2542324B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は各種工業用水、例えば、
紙、パルプ工業における抄紙工程水、或いは、金属加工
油、繊維油剤、水性塗料、ラテックス、でんぷんのり
液、でんぷんスラリ−、クレ−スラリ−等の工業用殺
菌、防腐剤に関するものである。特に、紙、パルプ工業
における抄紙工程水中のスライムを発生させる微生物に
対する殺菌剤に関する。
The present invention relates to various industrial waters such as, for example,
The present invention relates to water for papermaking in the paper and pulp industries, or industrial sterilizing and preservative agents such as metalworking oils, fiber oils, aqueous paints, latexes, starch pastes, starch slurries, and clay slurries. In particular, it relates to a bactericide against microorganisms that generate slime in the papermaking process water in the paper and pulp industries.

【0002】[0002]

【従来の技術】従来から多くの工業製品、例えば金属加
工油、水性塗料、ラテックス、でんぷんのり液、でんぷ
んスラリ−、クレ−スラリ−等では細菌による腐敗によ
る汚染が多大の損害を与えている。また、紙パルプ工業
における抄紙工程水に発生するスライムにより品質の低
下や紙切れによる生産効率の低下などの損失を生じる事
が知られている。この様なスライム等の発生は、細菌、
糸状菌、酵母類等の多種多様な微生物が関与している。
これらの腐敗又はスライムを抑制又は殺菌する手段とし
て、工業用殺菌、防腐剤を使用して防腐殺菌処理を行っ
ており、特に製紙工程中に発生するスライムに対しては
種々のスライム防除剤を加えて殺菌処理を行ってきた。
2. Description of the Related Art Conventionally, many industrial products such as metalworking oils, water-based paints, latexes, starch pastes, starch slurries and clay slurries have been seriously damaged by spoilage by bacteria. Further, it is known that slime generated in water in the papermaking process in the paper and pulp industry causes a loss such as a decrease in quality and a decrease in production efficiency due to paper shortage. Occurrence of such slime is caused by bacteria,
A wide variety of microorganisms such as filamentous fungi and yeasts are involved.
As a means for suppressing or sterilizing these putrefaction or slime, industrial sterilization is performed antiseptic sterilization treatment using an antiseptic, and especially for slime generated during the papermaking process, various slime control agents are added. Have been sterilized.

【0003】これらの殺菌、防腐剤として環状窒素硫黄
系化合物、臭素系化合物、チオシアン系化合物、四級ア
ンモニウム系化合物等の単独またはこれらの混合物が使
用されている事が知られている。しかし、近年は環境保
安問題によりあまり毒性の強い薬剤が使用できず、ま
た、これらの化合物類は使用上においても欠点を有して
いる物が多い。例えば、従来の薬剤は低濃度では薬剤効
果が不充分であったり、薬剤が人体に刺激性を有した
り、或いは、長期に使用した場合には耐性がつきやすい
とか、悪臭等が悪影響を与える欠点を有している。特
に、スライムの発生を抑制するスライムコントロ−ル剤
は、その使用上から環境汚染について配慮しなければな
らない。
It is known that a cyclic nitrogen-sulfur compound, a bromine compound, a thiocyan compound, a quaternary ammonium compound, or the like, or a mixture thereof is used as a sterilizing and antiseptic agent. However, in recent years, highly toxic drugs cannot be used due to environmental safety problems, and many of these compounds have drawbacks in use. For example, conventional drugs have insufficient drug effects at low concentrations, the drugs are irritating to the human body, or they tend to become resistant when used for a long period of time, and bad odors, etc. adversely affect. It has drawbacks. In particular, a slime control agent that suppresses the generation of slime must take into consideration environmental pollution from the viewpoint of its use.

【0004】[0004]

【発明が解決しようとする課題】本発明者らは、上記の
点を考慮して環境汚染を生じることなく低濃度で有効な
殺菌、防腐能を有する工業用殺菌、防腐剤を開発すべく
種々検討を重ねた結果、ジクロログリオキシムと他の殺
菌剤とを組み合わせる事によって相乗的な殺菌効果を有
する工業用殺菌、防腐剤を見出し、本発明を完成したも
ので、本発明の目的は低濃度で薬剤効果の十分な工業用
殺菌、防腐剤を提供するものである。
DISCLOSURE OF THE INVENTION In consideration of the above points, the present inventors have developed various industrial sterilization and antiseptic agents having a low concentration and effective sterilization and antiseptic properties without causing environmental pollution. As a result of repeated studies, an industrial sterilizer having a synergistic bactericidal effect by combining dichloroglyoxime and another fungicide, an antiseptic agent was found, and the present invention has been completed. It provides an industrial sterilizing and antiseptic agent having a sufficient drug effect.

【0005】[0005]

【課題を解決するための手段】本発明の要旨は、ジクロ
ログリオキシム
The gist of the present invention is dichloroglyoxime.

【0006】[0006]

【化4】 Embedded image

【0007】と、2−(4−ヒドロキシフェニル)−2
−オキソアセトヒドロキシモイルクロリド
And 2- (4-hydroxyphenyl) -2
-Oxoacetohydroxymoyl chloride

【0008】[0008]

【化5】 Embedded image

【0009】及び、α−クロロベンズアルドキシムアセ
テ−ト
And α-chlorobenzaldoxime acetate

【0010】[0010]

【化6】 [Chemical 6]

【0011】の化合物よりなる群より選ばれた少なくと
も一種類以上の化合物とを有効成分とする工業用殺菌、
防腐組成物である。すなわち、ジクロログリオキシムは
強力な殺菌活性を有しており、他方、上記の2個の化合
物群の単独化合物は殺菌力は弱いものであるが、ジクロ
ログリオキシムと組み合せることによって相乗的な殺菌
効果が得られた。しかも、本発明で使用するジクロログ
リオキシム(以下、DCGという)は、水中で下記の反
応によりオキサロヒドロキサム酸或いはオキサロヒドロ
キシム酸と塩酸とを経て蓚酸とヒドロキシルアミンに分
解され、これらは何れも生分解される環境に安全な化合
物となるので、本発明の工業用殺菌、防腐組成物は、特
に、スライムコントロ−ル剤として使用した場合、環境
汚染を生じることなく極めて強力な殺菌、防腐剤として
作用する。
Industrial sterilization containing at least one compound selected from the group consisting of compounds as an active ingredient,
It is an antiseptic composition. That is, dichloroglyoxime has a strong bactericidal activity, while the single compounds of the above two compound groups have weak bactericidal activity, but when combined with dichloroglyoxime, they have a synergistic bactericidal activity. The effect was obtained. Moreover, the dichloroglyoxime (hereinafter referred to as DCG) used in the present invention is decomposed into oxalic acid and hydroxylamine via the oxalohydroxamic acid or oxalohydroxymic acid and hydrochloric acid by the following reaction in water, and both of them produce Since it becomes a compound safe to the environment to be decomposed, the industrial sterilization and antiseptic composition of the present invention, especially when used as a slime control agent, as an extremely powerful sterilization and antiseptic agent without causing environmental pollution. To work.

【0012】[0012]

【化7】 [Chemical 7]

【0013】次に本発明について詳細に述べる。本発明
の二種以上の化合物は、通常、種々の方法によって混合
し、それぞれの対象系に添加して用いられる。これら化
合物の混合手段としては、これら化合物を溶解する共通
の有機溶媒に溶解し、しかる後、それぞれの溶液を混合
する。その際、必要に応じて界面活性剤を添加する事に
より製剤が可能である。
Next, the present invention will be described in detail. The two or more compounds of the present invention are usually mixed by various methods and added to each target system for use. As a means for mixing these compounds, these compounds are dissolved in a common organic solvent, and then the respective solutions are mixed. At that time, a formulation can be prepared by adding a surfactant if necessary.

【0014】適当な共通の有機溶媒としてはエチレング
リコ−ル(EG)、メトキシポリエチレングリコ−ル
(M−PEG)、ジエチレングリコ−ルモノメチルエ−
テル(MDG)等のグリコ−ル系溶剤があげられる。ま
た、それぞれの化合物を、別々に対象系に添加しても良
く、DCGと他の化合物との混合割合は、ジクロログリ
オキシム:他の薬剤が0.1:9.9〜9.9:0.
1、好ましくは9:1〜4:6である。そして、工業用
殺菌、防腐剤の対象系に添加する割合は系の種類によっ
て異なるが通常有効成分で0.1〜30ppm、好まし
くは0.5〜10ppmである。
Suitable common organic solvents include ethylene glycol (EG), methoxypolyethylene glycol (M-PEG), diethylene glycol monomethyl ether.
Examples include glycol-based solvents such as Tell (MDG). Further, each compound may be added to the target system separately, and the mixing ratio of DCG and the other compound is 0.1: 9.9 to 9.9: 0 for dichloroglyoxime: other drug. .
1, preferably 9: 1 to 4: 6. The ratio of the industrial sterilization and preservative added to the target system varies depending on the type of the system, but is usually 0.1 to 30 ppm, preferably 0.5 to 10 ppm as the active ingredient.

【0015】[0015]

【実施例】次に実施例によって本発明を更に詳細に説明
するが、本発明はこれに限定されるものではない。な
お、表において、それぞれの化合物を次のように表示す
る DCG ジクロログリオキシム HPAHCI 2−(4−ヒドロキシフェニル)−2−
オキソアセトヒドロキシモイルクロリド CBA α−クロロベンズアルドキシムアセテ−ト
EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the table, each compound is represented as follows: DCG dichloroglyoxime HPAHCI 2- (4-hydroxyphenyl) -2-
Oxoacetohydroxymoyl chloride CBA α-chlorobenzaldoxime acetate

【0016】実施例1 ジクロログリオキシムと他の化合物、HPAHCIとC
BAを表1に示した比率に混合し、その比率での最小殺
菌濃度(MBC)を求めた。使用菌株として標準菌E.
coli JCM1649株を使用し行った。試験法と
しては、生理食塩水にE.coli JCM1649株
を106個/ml位になるように接種したものをL字培
養管に取り、所定の有効成分濃度(40,20,10,
5,2.5,1.3,0.6,0.3,0.15pp
m)になるように薬剤を添加し30℃のモノ−振盪機で
1時間培養後の生菌数を常法(SPC法)で測定し9
9.9%殺菌した最小濃度(MBC)を測定した。これ
らの結果を図1及び図2に示す。図1においてCBA1
00%、40ppm以上とは有効成分としてCBAを1
00%使用した場合の最小殺菌濃度が40ppm以上で
あることを意味するものである。
Example 1 Dichloroglyoxime and other compounds, HPACI and C
BA was mixed in the ratio shown in Table 1, and the minimum bactericidal concentration (MBC) at that ratio was determined. Standard strain E.
E. coli JCM1649 strain was used. As a test method, physiological saline was added to E. coli. E. coli JCM1649 strain was inoculated to about 10 6 cells / ml and placed in an L-shaped culture tube to give a predetermined active ingredient concentration (40, 20, 10,
5,2.5,1.3,0.6,0.3,0.15pp
m) was added with a drug, and the viable cell count after 1 hour of culturing on a mono-shaker at 30 ° C. was measured by a conventional method (SPC method).
The minimum concentration (MBC) sterilized by 9.9% was measured. These results are shown in FIG. 1 and FIG. In FIG. 1, CBA1
00%, 40ppm or more means 1 CBA as an active ingredient
This means that the minimum bactericidal concentration when used at 00% is 40 ppm or more.

【0017】図1及び図2により明らかなように、ジク
ロログリオキシムは、α−クロロベンズアルドキシムア
セテ−トや2−(4−ヒドロキシフェニル)−2−オキ
ソアセトヒドロキシモイルクロリドを組み合わせる事に
よって考えられないほど低いMBCを示した。
As is clear from FIGS. 1 and 2, dichloroglyoxime was considered by combining α-chlorobenzaldoxime acetate and 2- (4-hydroxyphenyl) -2-oxoacetohydroxymoyl chloride. It showed an unbelievably low MBC.

【0018】実施例2 新聞紙を抄造しているA製紙会社の白水(酸性)を用い
て表1に示した薬剤について殺菌試験を行った。
Example 2 A sterilization test was carried out on the chemicals shown in Table 1 using white water (acidic) manufactured by A Paper Manufacturing Company, which produces newspaper.

【0019】[0019]

【表1】 [Table 1]

【0020】方法として供試白水に表1に示した薬剤を
一定量(20ppm、10ppm)添加し30℃で1時
間振盪培養後の生菌数を常法(SPC法)で測定し薬剤
無添加と対比する。結果を表2に示す。なお、比較のた
め、薬剤無添加又はDCG、HPAHCl、及びCBA
の各化合物を単独使用した場合についても上述と同様の
試験を行った。表2より明らかにジクロログリオキシム
は他の薬剤と組み合わせることによって相乗的に殺菌力
が強化された。
As a method, a certain amount (20 ppm, 10 ppm) of the drug shown in Table 1 was added to the test white water, and the viable cell count after shaking culture at 30 ° C. for 1 hour was measured by a conventional method (SPC method) and no drug was added. Contrast with. Table 2 shows the results. For comparison, no chemicals added or DCG, HPAHCl, and CBA
The same test as described above was performed when each of the above compounds was used alone. It is clear from Table 2 that dichloroglyoxime synergistically enhanced the bactericidal activity by combining with other drugs.

【0021】[0021]

【表2】 [Table 2]

【0022】実施例3 コ−ト原紙を抄造しているB製紙会社の白水(中性)を
用いて表1に示した薬剤について殺菌試験を行った。結
果を表3に示す。なお、比較のため、薬剤無添加又はD
CG、HPAHCl、及びCBAの各化合物を単独使用
した場合についても上述と同様の試験を行った。表3よ
り明らかにジクロログリオキシムは他の薬剤と組み合わ
せることによって相乗的に殺菌力が強化された。
Example 3 A sterilization test was carried out on the chemicals shown in Table 1 using white water (neutral) of a paper manufacturing company B, which manufactures the base paper for the coat. The results are shown in Table 3. For comparison, no drug added or D
The same test as above was carried out when each of the compounds CG, HPAHCl, and CBA was used alone. It is clear from Table 3 that dichloroglyoxime synergistically enhanced the bactericidal activity by combining with other agents.

【0023】[0023]

【表3】 [Table 3]

【0024】[0024]

【発明の効果】以上述べたように、本発明はジクロログ
リオキシムと、2−(4−ヒドロキシフェニル)−2−
オキソアセトヒドロキシモイルクロリド及びα−クロロ
ベンズアルドキシムアセテ−トよりなる群より選ばれた
少なくとも一種類以上の化合物とを有効成分とすること
によって、それぞれの実施例に示されているように極め
て少量の使用によって相乗的に強力な殺菌、防腐性能を
示し、しかも、ジクロログリオキシムは、水中では環境
に無害な化合物に分解されるので、特に、紙、パルプ工
業における抄紙工程水中のスライムコントロ−ル剤とし
て有効である。
As described above, the present invention provides dichloroglyoxime and 2- (4-hydroxyphenyl) -2-
By using at least one compound selected from the group consisting of oxoacetohydroxymoyl chloride and α-chlorobenzaldoxime acetate as an active ingredient, an extremely small amount as shown in each Example. Synergistically shows strong bactericidal and antiseptic properties, and since dichloroglyoxime is decomposed into a compound harmless to the environment in water, it is particularly useful for slime control in the papermaking process water in the paper and pulp industry. Effective as an agent.

【図面の簡単な説明】[Brief description of drawings]

【図1】 実施例1のDCGとCBAとの混合薬剤の両
者の比率と最小殺菌濃度との関係図である。
FIG. 1 is a diagram showing the relationship between the ratio of both DCG and CBA mixed drugs of Example 1 and the minimum bactericidal concentration.

【図2】 実施例1のDCGとHPAHClとの混合薬
剤の両者の比率と最小殺菌濃度との関係図である。
FIG. 2 is a diagram showing the relationship between the ratio of both DCG and HPAHCl mixed drugs of Example 1 and the minimum bactericidal concentration.

【符号の説明】[Explanation of symbols]

横軸は薬剤の配合比率、縦軸は最小殺菌濃度を示す。 The horizontal axis represents the compounding ratio of the drug, and the vertical axis represents the minimum bactericidal concentration.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 菅野 英奇 埼玉県越谷市大間野町1−6 純正化学 株式会社埼玉研究所内 (72)発明者 高橋 誠康 東京都中央区銀座1−18−6共同ビル (銀座)フジ産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideki Sugano 1-6 Omano-cho, Koshigaya-shi, Saitama Pure Chemicals Co., Ltd. Saitama Laboratory (72) Inventor Masayasu Takahashi 1-18-6 Ginza, Chuo-ku, Tokyo Common building (Ginza) within Fuji Sangyo Co., Ltd.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 ジクロログリオキシム 【化1】 と、2−(4−ヒドロキシフェニル)−2−オキソアセ
トヒドロキシモイルクロリド 【化2】 及びα−クロロベンズアルドキシムアセテ−ト 【化3】 の化合物よりなる群より選ばれた少なくとも一種類以上
の化合物とを有効成分とする工業用殺菌、防腐組成物。
1. A dichloroglyoxime embedded image And 2- (4-hydroxyphenyl) -2-oxoacetohydroxymoyl chloride And α-chlorobenzaldoxime acetate Industrial bactericidal and antiseptic compositions containing, as an active ingredient, at least one compound selected from the group consisting of:
JP5086002A 1993-04-13 1993-04-13 Industrial sterilization and antiseptic composition Expired - Lifetime JP2542324B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5086002A JP2542324B2 (en) 1993-04-13 1993-04-13 Industrial sterilization and antiseptic composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5086002A JP2542324B2 (en) 1993-04-13 1993-04-13 Industrial sterilization and antiseptic composition

Publications (2)

Publication Number Publication Date
JPH06298607A JPH06298607A (en) 1994-10-25
JP2542324B2 true JP2542324B2 (en) 1996-10-09

Family

ID=13874469

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5086002A Expired - Lifetime JP2542324B2 (en) 1993-04-13 1993-04-13 Industrial sterilization and antiseptic composition

Country Status (1)

Country Link
JP (1) JP2542324B2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100710554B1 (en) * 1999-12-24 2007-04-24 에스케이 주식회사 Slimecide composition for paper manufacture and method of controlling slime using the same
JP5900976B2 (en) * 2012-09-18 2016-04-06 フジ産業株式会社 Industrial disinfectant composition with improved safety

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0640811A (en) * 1992-05-22 1994-02-15 Katayama Chem Works Co Ltd Industrial germicide and industrial method for sterilization

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0640811A (en) * 1992-05-22 1994-02-15 Katayama Chem Works Co Ltd Industrial germicide and industrial method for sterilization

Also Published As

Publication number Publication date
JPH06298607A (en) 1994-10-25

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