JPS6136722B2

JPS6136722B2 -

Info

Publication number: JPS6136722B2
Application number: JP53161821A
Authority: JP
Inventors: Masayasu Hasegawa; Hideo Nishikawa; Yasuo Kotani
Original assignee: Nippon Synthetic Chemical Industry Co Ltd
Current assignee: Mitsubishi Chemical Corp
Priority date: 1978-12-26
Filing date: 1978-12-26
Publication date: 1986-08-20
Also published as: JPS5587704A

Description

[Detailed description of the invention]

デヒドロ酢酸、ソルビン酸、あるいはそれらの
塩はいずれも低毒性の防菌防黴剤として有用であ
る。しかし、塗料、糊剤、接着剤用等、工業用製
品の防菌防黴剤として使用する場合、必ずしもそ
の効力が充分といえず、用途範囲に制限がある。
しかして防菌力、防黴力の向上のため従来から各
種の防菌剤、防黴剤を組合せ抗菌スペクトルを広
げることが試みられているが、通常はそれぞれの
薬剤が有する効果が相加平均的でしか得られず、
飛躍的な効力改善効果は認め難いのが実状であ
る。しかるに本発明者等は(A)デヒドロ酢酸又はそ
の塩あるいはソルビン酸又はその塩の少なくとも
１種と(B)２，４，５，６−テトラクロロイソフタ
ロニトリルとからなる組成物は相乗的防菌、防黴
効果が向上することを見出し本発明を完成するに
至つた。本発明の(A)，(B)はいずれも防菌剤、防黴剤とし
て公知であるが、これらを併用する場合、前記の
如き効果が得られることは従来の知見からは到底
予想出来ないことである。本発明の(A)成分はデヒドロ酢酸、ソルビン酸又
はその塩の少くとも１種である。塩としてはデヒ
ドロ酢酸ナトリウム、デヒドロ酢酸カリウム、ソ
ルビン酸ナトリウム、ソルビン酸カリウム等が挙
げられる。一方(B)成分は一般式 Dehydroacetic acid, sorbic acid, or their salts are all useful as low-toxicity antibacterial and fungicidal agents. However, when used as an antibacterial and fungicidal agent for industrial products such as paints, pastes, and adhesives, its effectiveness is not necessarily sufficient, and its range of use is limited.
However, attempts have been made to widen the antibacterial spectrum by combining various antibacterial and antifungal agents in order to improve their antibacterial and antifungal abilities. It can only be obtained by
The reality is that it is difficult to recognize a dramatic improvement in efficacy. However, the present inventors have found that a composition comprising (A) at least one of dehydroacetic acid or its salt or sorbic acid or its salt and (B) 2,4,5,6-tetrachloroisophthalonitrile has a synergistic protective effect. The present invention was completed after discovering that the anti-bacterial and anti-mildew effect is improved. Both (A) and (B) of the present invention are known as antibacterial agents and antifungal agents, but it is impossible to predict from conventional knowledge that the above-mentioned effects will be obtained when these are used together. That's true. Component (A) of the present invention is at least one of dehydroacetic acid, sorbic acid, or a salt thereof. Examples of the salt include sodium dehydroacetate, potassium dehydroacetate, sodium sorbate, potassium sorbate, and the like. On the other hand, component (B) has the general formula

【式】で示される２，４，５，６−テトラクロロイソフタロ
ニトリルである。該フタロニトリルはLD₅₀が
10g／Kgと非常に低毒性であるので、これと(A)と
を組合せた本願の防菌防黴組成物は極めて安全性
に優れたものである。 (A)成分と(B)成分の混合比率は特に制限はない
が、(B)成分の混合率を(A)に対して１〜40重量％程
度とする場合、特に相乗効果が顕著であるので、
かかる範囲で使用するのが望ましい。本願組成物の使用量は対象物の種類によつて変
わるので一概に規定は出来ないが、通常は50〜
8000ppm程度添加すれば、防菌防黴効果が充分
発揮される。又、本発明の組成物には必要に応じて他の防菌
剤、防黴剤、界面活性剤、香料等、適宜、助剤を
添加することも可能である。本発明の組成物は防菌、防黴の要求される工業
的製品のいずれにも添加し得る。例えばかかる例
として、各種の塗料、糊料、石油製品、プラスチ
ツク成型品、繊維類、皮革類、更には木材類、紙
加工品、医療器械、産業用施設や建築物の部品
等、各種の対象物が挙げられる。更に穀類、果
実、野菜等の農作物への使用も可能である。次に実例を挙げて本発明の組成物を更に詳しく
説明する。実例１ポテトデキストロース寒天培地に表に示す様な
濃度になる様に(A)，(B)両成分を加え、更に表に示
す様な糸状菌胞子懸濁液を滴下し、28℃の恒温器
中で２週間培養し、生育の有無を測定した。但し＋：生育 ±：やや生育 −：生育せず
にて表示した。It is 2,4,5,6-tetrachloroisophthalonitrile represented by the formula: The phthalonitrile has an LD ₅₀ of
Since it has a very low toxicity of 10g/Kg, the antibacterial and antifungal composition of the present invention, which is a combination of this and (A), has extremely excellent safety. There is no particular restriction on the mixing ratio of component (A) and component (B), but when the mixing ratio of component (B) is approximately 1 to 40% by weight relative to (A), the synergistic effect is particularly remarkable. So,
It is desirable to use it within this range. The amount of the composition of the present invention to be used varies depending on the type of object, so it cannot be unconditionally prescribed, but it is usually 50~
If added at around 8000ppm, the antibacterial and antifungal effect will be fully demonstrated. Further, it is also possible to add other appropriate auxiliary agents to the composition of the present invention, as necessary, such as other antibacterial agents, antifungal agents, surfactants, and fragrances. The composition of the present invention can be added to any industrial product requiring antibacterial and antifungal properties. For example, various objects such as various paints, pastes, petroleum products, plastic molded products, textiles, leather, wood, processed paper products, medical equipment, parts of industrial facilities and buildings, etc. Things can be mentioned. Furthermore, it can also be used for agricultural products such as cereals, fruits, and vegetables. Next, the composition of the present invention will be explained in more detail by giving examples. Example 1 Add both ingredients (A) and (B) to a potato dextrose agar medium to the concentrations shown in the table, then drop a filamentous fungus spore suspension as shown in the table, and place in a thermostatic oven at 28℃. The cells were cultured for two weeks, and the presence or absence of growth was measured. However, +: Growth ±: Slight growth −: No growth.

【表】【table】

【表】実施例２トリプトン0.5％、酵母エキス0.5％、ブドウ糖
0.1％、リン酸２カリウム0.1％、寒天２％を含有
する培地に次表の濃度になる様に(A)，(B)両成分を
加え、各種の細菌を植菌して、37℃で、４日間培
養しその生育の有無を調べた。[Table] Example 2 Tryptone 0.5%, yeast extract 0.5%, glucose
Both components (A) and (B) were added to a medium containing 0.1% dipotassium phosphate, 0.1% dipotassium phosphate, and 2% agar at the concentrations shown in the table below, inoculated with various bacteria, and incubated at 37℃. The cells were cultured for 4 days and the presence or absence of growth was examined.

【表】【table】

【表】試験例１ポリビニルアルコールの10％水溶液糊剤を調製
した。これを３区に分け、１区には薬剤無添加、
２区にはデヒドロ酢酸ナトリウム2000ppmを添
加、３区にはデヒドロ酢酸ナトリウム1000ppm
と２，４，５，６−テトラクロロイソフタロニト
リル100ppmとを添加した。次に各にEpicocum
SPを植菌したのち、30℃の恒温器に入れ14日間
放置した。１区は３日で発黴した。２区は５日で
発黴した。３区は全く発黴がなかつた。試験例２ポリビニルアルコールの10％水溶液糊剤を調製
した。これを４区に分け、１区には薬剤無添加、
２区にはデヒドロ酢酸2000ppmを添加、３区に
はデヒドロ酢酸ナトリウム1000ppmと２，４，
５，６−テトラクロロイソフタロニトリル
10ppmとを添加、４区には２，４，５，６−テ
トラクロロイソフタロニトリル20ppmを添加し
た。以下、試験例１と同様にして発黴を観察し
た。１区は３日で発黴、２区及び４区は５日で発
黴したが、３区は全く発黴がなかつた。試験例３デヒドロ酢酸ナトリウムに代えてソルビン酸カ
リウムを用いた以外は試験例１と同一の実験を行
つた。その結果１区は４日で発黴、２区は６日で
発黴し、３区は全く発黴がなかつた。試験例４試験例２において１区には薬剤無添加、２区に
はソルビン酸カリウム2000ppmを添加、３区に
はソルビン酸カリウム1000ppmと２，４，５，
６−テトラクロロイソフタロニトリル10ppmと
を添加、４区には２，４，５，６−テトラクロロ
イソフタロニトリル20ppmを添加した以外は同
例と同一の実験を行つた。１区は３日で発黴、２
区及び４区は５日で発黴したが、３区は全く発黴
がなかつた。試験例５デヒドロ酢酸ナトリウム95gと２，４，５，６
−テトラクロロイソフタロニトリル5gを混合し
本願組成物を得た。これを花莚コート用樹脂原液
（クロトン酸−酢酸ビニル共重合体、濃度18％）
に組成物濃度が2500ppm、5000ppm、7500ppm
となる様に添加し３種のコード液を調製した。次に花莚（10×10cm）に上記コート液を各2g
表と裏にスプレー法にて吹きつけ、140℃で２分
間乾燥させた。処理された花莚を25℃の飽和湿度のもとに保存
し、経時的に黴の生育状況を観察した。その結果を表に示す。[Table] Test Example 1 A 10% aqueous solution glue of polyvinyl alcohol was prepared. This is divided into 3 sections, 1 section contains no additives,
2000ppm of sodium dehydroacetate was added to the 2nd area, 1000ppm of sodium dehydroacetate was added to the 3rd area.
and 100 ppm of 2,4,5,6-tetrachloroisophthalonitrile. Then Epicocum on each
After inoculating with SP, the cells were placed in a thermostat at 30°C for 14 days. Mold broke out in Ward 1 within three days. In the second ward, mold broke out in five days. There was no mold at all in Ward 3. Test Example 2 A 10% aqueous solution glue of polyvinyl alcohol was prepared. This is divided into 4 sections, 1 section has no additives,
In the 2nd section, 2000ppm of dehydroacetic acid was added, and in the 3rd section, 1000ppm of sodium dehydroacetate and 2,4,
5,6-tetrachloroisophthalonitrile
10 ppm of 2,4,5,6-tetrachloroisophthalonitrile was added to the 4th section. Thereafter, mold growth was observed in the same manner as in Test Example 1. Mold developed in Ward 1 after 3 days, and mold developed in Wards 2 and 4 within 5 days, but in Ward 3 there was no mold at all. Test Example 3 The same experiment as Test Example 1 was conducted except that potassium sorbate was used instead of sodium dehydroacetate. As a result, ward 1 developed mold in 4 days, ward 2 developed mold in 6 days, and ward 3 had no mold at all. Test Example 4 In Test Example 2, no drug was added to Group 1, 2000 ppm of potassium sorbate was added to Group 2, and 1000 ppm of potassium sorbate and 2,4,5,
The same experiment as in the same example was carried out except that 10 ppm of 6-tetrachloroisophthalonitrile was added, and 20 ppm of 2,4,5,6-tetrachloroisophthalonitrile was added to the fourth section. Ward 1 has mold in 3 days, 2
Ward and Ward 4 developed mold within five days, but Ward 3 had no mold at all. Test example 5 Sodium dehydroacetate 95g and 2,4,5,6
- 5 g of tetrachloroisophthalonitrile was mixed to obtain the composition of the present invention. Add this to the resin stock solution for flower coating (crotonic acid-vinyl acetate copolymer, concentration 18%).
The composition concentration is 2500ppm, 5000ppm, 7500ppm
Three types of code solutions were prepared by adding the following amounts. Next, apply 2g each of the above coating liquid to a flower pot (10 x 10cm).
It was sprayed onto the front and back sides and dried at 140°C for 2 minutes. The treated flowers were stored under saturated humidity at 25°C, and the growth of mold was observed over time. The results are shown in the table.

【表】試験例６小麦でんぷんを５％含有する糊液及びカゼイン
を５％含有する糊液を調製し、これに表に示す濃
度を薬剤を添加、更にAspergillus niger，
Pencillium citrinum，Cladosporium herbaum，
Chaetomium globosumからなる菌株の胞子懸濁
液を植菌した後、28℃の恒温器に入れ黴の生育状
況を調べた。その結果を示す。[Table] Test Example 6 A sizing liquid containing 5% wheat starch and a sizing liquid containing 5% casein were prepared, and chemicals were added to them at the concentrations shown in the table, and Aspergillus niger,
Pencillium citrinum，Cladosporium herbaum，
After inoculating a spore suspension of a strain of Chaetomium globosum, the mold was placed in a thermostat at 28°C and the growth status of mold was examined. The results are shown below.

【table】

Claims

[Claims]

1 (A) At least one of dehydroacetic acid or its salts or sorbic acid or its salts and (B) 2, 4, 5, 6
-An antibacterial and antifungal composition comprising tetrachloroisophthalonitrile.