JPS6117802B2 - - Google Patents
Info
- Publication number
- JPS6117802B2 JPS6117802B2 JP1557777A JP1557777A JPS6117802B2 JP S6117802 B2 JPS6117802 B2 JP S6117802B2 JP 1557777 A JP1557777 A JP 1557777A JP 1557777 A JP1557777 A JP 1557777A JP S6117802 B2 JPS6117802 B2 JP S6117802B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- thiophthalimide
- active compound
- weight
- carbamate
- 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
Links
- 150000001875 compounds Chemical class 0.000 claims description 31
- TZBMYJDWCZGTTJ-UHFFFAOYSA-N 1h-benzimidazol-2-yl(methyl)carbamic acid Chemical compound C1=CC=C2NC(N(C(O)=O)C)=NC2=C1 TZBMYJDWCZGTTJ-UHFFFAOYSA-N 0.000 claims description 10
- YCEPJUIXZAFSKQ-UHFFFAOYSA-N 5,6-dichloro-7-(fluoromethyl)-3-sulfanylideneisoindol-1-one Chemical compound ClC1=C(Cl)C(CF)=C2C(=O)NC(=S)C2=C1 YCEPJUIXZAFSKQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003641 microbiacidal effect Effects 0.000 claims description 8
- 229940124561 microbicide Drugs 0.000 claims description 4
- -1 dichlorofluoromethyl-carbamate Chemical compound 0.000 claims description 3
- 239000002855 microbicide agent Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- PFEFOHMLVFUELJ-UHFFFAOYSA-N 3-sulfanylideneisoindol-1-one Chemical compound C1=CC=C2C(=O)NC(=S)C2=C1 PFEFOHMLVFUELJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000123 paper Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 241000233866 Fungi Species 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 244000005700 microbiome Species 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000002538 fungal effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 241000228245 Aspergillus niger Species 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 241000223602 Alternaria alternata Species 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000223261 Trichoderma viride Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000221955 Chaetomium Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 241000122818 Aspergillus ustus Species 0.000 description 1
- 241000223678 Aureobasidium pullulans Species 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- 241001149956 Cladosporium herbarum Species 0.000 description 1
- 241000235646 Cyberlindnera jadinii Species 0.000 description 1
- 241000195619 Euglena gracilis Species 0.000 description 1
- GLMHLMZCDUFDAU-UHFFFAOYSA-N FNS(=O)(=S)NC(Cl)Cl Chemical compound FNS(=O)(=S)NC(Cl)Cl GLMHLMZCDUFDAU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000761677 Jaaginema geminatum Species 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- WIQNFSGDOCMACM-UHFFFAOYSA-O OC[S+](C1=CC=CC=C1N1)C1=S Chemical compound OC[S+](C1=CC=CC=C1N1)C1=S WIQNFSGDOCMACM-UHFFFAOYSA-O 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241001236817 Paecilomyces <Clavicipitaceae> Species 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 241001123663 Penicillium expansum Species 0.000 description 1
- 241000206744 Phaeodactylum tricornutum Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241001279364 Stachybotrys chartarum Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001504046 Stichococcus bacillaris Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 239000004557 technical material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/26—Oxidation products of dithiocarbamic acid derivatives, e.g. thiuram sulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/02—Curing raw hides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Microbiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、ベンゾイミダゾリル−メチル−カル
バメート及びジクロロフルオロメチル−チオフタ
ルイミドから成る活性化合物の新規な相乗作用性
の組合せに関する。
植物における広汎なカビによる疾病を、宿主に
損害を与えることなく撲滅する（combating）の
ための殺菌カビ剤（fungicidal agent）としてベ
ンゾイミダゾリル−アルキル−カルバメートを使
用することは知られている（西ドイツ公開公報第
1620175号）。たとえば、トリクロロメチル−チオ
フタルイミド、ジクロロフルオロメチル−チオフ
タルイミドの如きハロゲノメチル−チオフタルイ
ミド及び（N′−フルオロジクロロメチル−チ
オ）−スルフアミド〔farbe＋lack77、888〜890
（1971）〕が殺微生物作用（microbicidal action）
を有することは知られている。殺微生物剤として
１−メチロール−２−チオノ−１，２−ジヒドロ
ベンゾチアゾールの使用は西ドイツ公開公報第
2201457号から知られている。
しかしながら、これらの化合物を個別に使用す
る場合には、それらの活性スペクトルにギヤツプ
があるので、微生物に対して不満足なものであ
る。この問題を解決するために、ベンゾイミダゾ
リル−メチル−カルバメート及び３，５−ジメチ
ル−テトラヒドロ−１，３，５−チアジアジン−
２−チオンから成る活性化合物の組合せが既に知
られている（西ドイツ公告公報第2150219号）。活
性化合物のこの公知の組合せの不利は、ホルムア
ルデヒド蓄積質物質（formaldehyd depot
substance）としての３，５−ジメチル−テトラ
ヒドロ−１，３，５−チアジアジン−２−チオン
が中程度しか安定でなく、それ故に環境的要因の
影響下に容易に分解することにある。
本発明は、活性成分として、ベンゾイミダゾリ
ル−メチル−カルバメート及びジクロロフルオロ
メチル−チオフタルイミドを、それのみ又は希釈
剤もしくは担体との混合物として含有して成る殺
微生物組成物を今回提供する。本発明の活性化合
物の組合せは特に高殺微生物活性を有する。
更に、本発明は材料を微生物に対して保護する
方法を提供するものであり、この方法は本発明に
従う組成物を材料に適用するか又は配合すること
より成る。
驚くべきことに、本発明に従う活性化合物の組
合せの殺微生物活性、特に殺菌殺カビ活性
（fungicidal activity）は個々の活性化合物の作用
の総和より相当高いものである。故に、真正の相
乗的効果が存在する。活性化合物の組合せは当技
術分野の価値ある強化を示すものである。
ベンゾイミダゾリル−メチル−カルバメートの
製造は既知である（米国特許明細書第3010968
号）。
ジクロロフルオロメチル−チオフタルイミドは
米国特許明細書3285929号に従つて製造すること
ができる。
上記活性化合物の組合せ中の活性化合物の重量
比は、相対的に広い範囲内で変えることができ
る。一般に、ベンゾイミダゾリル−メチル−カル
バメート１重量部につきジクロロフルオロメチル
−チオフタルイミド１〜25重量部好ましくは２〜
12重量部である。
本発明に従う活性化合物の粒径は広い範囲内で
変えることができる。一般に、100〜350ミクロン
好ましくは150〜300ミクロンの粒径を有する活性
化合物が使用される。
ベンゾイミダゾリル−メチル−カルバメート１
重量部ジクロロフルオロメチル−メチル−チオフ
タルイミド２〜10重量部との組合せは特に有効で
ある。
本発明に従う活性化合物の組合せは微生物に対
して強い作用を示す。挙げることができる微生物
の例は菌カビ（fungi）、酵母及び藻類（algae）。
挙げることができる菌カビ及び酵母の例はペニ
シリウムグラウクム（Penicillium glaucum）、ク
モノスカビ（Rhinopus nigricans）、黒色麹菌ク
ロカビ（Aspergillus niger）、プリユラリアプリ
ユランス（Pullularia pullulans）、アルテルナリ
アテヌイス（Alternaria tenuis）トルラウテイリ
ス（Torula utilis）、カンジダクルセイ
（Candida cruseu）、及び鵞口瘡カンジダ
（Candida albicans）である。
挙げることができる藻類の例はフエオダクチル
ムトリコルヌツムボーリン
（Phaeodactylumtricorutum Bohlin）、ユーグレ
ナグラシリスレブス（Euglena gracilis
Klebs）、オシラトリアゲミナタメネギニ
（Oscillatoria geminata Meneghini）及びスチコ
コツタスバチラリスネゲリ（Stichococcus
bacillaris Naeseli）。
本発明は微生物による分解に対して工業材料を
保護するための活性化合物の組合わせに関する。
工業材料は、たとえば、接着剤、にわか、紙及び
厚紙（cardboard）、布（texile）、革、木材、塗
料、石膏（plaster）、微生物の作用により損害を
受けるか又は損なわれ得る包装内容物である。本
発明に従う活性化合物の混合物は、接着剤、布及
び紙を保護するために特に好適である。
活性化合物の該新規組合せはたとえば、溶液、
懸濁液、ペースト及び粉末の如き通常の処方に転
化することができる。
活性化合物の該新規組合せはそれ自体で、それ
らの処方の形態で及びそれから調製した使用形態
において使用することができる。それらは通常の
方法において、たとえば、保護されるべき材料中
に均質に分解させること又は工業材料を含浸、被
覆もしくは噴霧することにより使用することがで
きる。
使用する活性化合物の組合せの量は微生物の性
質及び出現率（incidence）、細菌数（germ
count）並びに培地に依存する。使用するために
は、使用すべき最適量は各々の場合における一連
の試験により決定することができる。しかしなが
ら、一般に、活性化合物の混合物を処理されるべ
き材料の0.01〜1.0重量％を使用すれば十分であ
る。
本発明に従う活性化合物の組合せは有利な広範
な作用スペクトルを有する。本発明に従う活性化
合物を適当な方法で使用する場合には、排出液中
に現われる該活性化合物の組合せの濃度は生物学
的浄化においてやつかいな程のものではない。
本発明に従う活性化合物の組合せは、これまで
に入手可能な殺微生物剤をより有効な剤で有利に
代替し且つ微生物を撲滅するのに必要な剤の量を
有利に減少させることを可能ならしめる。
実施例１におけるコーテイングの耐カビ性を決定
する試験。
この試験は、Defence Standards
Laboratories Maribyrnong／Australiaの報告219
に基づき下記の如く実施する：滑らかな原紙試験
片を試験すべき生成物で両側を被覆しそして８日
間温室で乾燥する。熟成のために、塗料被覆の一
部を24℃で24時間流水で線上するか又は40〜60℃
で８日間新しい空気にさらすか或いは110時間乾
燥キセノン試験に付す。このようにして調製した
試料の５×５cm切片をペトリ皿中グルコース栄養
培地上に別々に置き、そしてかきの菌カビの胞子
（spores）懸濁液で汚染する：黒色麹菌 クロカ
ビ、プリユラリアプリユランス、アルテルナリア
スペシアレス（Alternaria speciales）、ペニシリ
ウムシトリウム（Penicillium citrium）、スタキ
ボトリスアトラ（Stachybotrys atra）、ペシロミ
セスバリオテイ（Paecilomyces varioti）、クラ
ドスポリウムヘルバム（Cladosporium
herbarum）、アスペルギルスウスツス
（Aspergillus ustus）及びアスペルギルスフラブ
ス（Aspergillus flavus）。
汚染した皿を28〜30℃及び90〜95％の相対大気
湿度で貯蔵し、そして３週間後に評価する。この
試験の後試料が菌カビを含まないままであれば被
覆は耐菌カビ性であるとみなす。
実施例 １
アルキド樹脂をベースとする市販の入手可能な
光沢塗料の耐菌カビ性を上記した試験方法により
試験する。本発明に従う活性化合物の混合物の相
乗効果を証明するために、(a)ペンゾイミダゾリル
−メチル−カルバメート（以下BCMと称する）
0.075％及び(b)ジクロロフルオロメチル−チオフ
タルイミド（以下DCFPと称する）0.198％並び
に(c)本発明に従う活性化合物0.273％（BCM0.075
％及びDCFP0.198％から成る）を光沢塗料に加
える（各々のばあいにおいてフイルム重量を基準
にして）。個々の活性化合物を試験に先立ち光沢
塗料中に溶解する。
試験後の評価は下記の通りである：
The present invention relates to a novel synergistic combination of active compounds consisting of benzimidazolyl-methyl-carbamate and dichlorofluoromethyl-thiophthalimide. The use of benzimidazolyl-alkyl-carbamates as fungicidal agents for combating a wide range of fungal diseases in plants without causing damage to the host is known (West German Opening Publication). No.
No. 1620175). For example, halogenomethyl-thiophthalimides such as trichloromethyl-thiophthalimide, dichlorofluoromethyl-thiophthalimide and (N'-fluorodichloromethyl-thio)-sulfamide [farbe+lack 77, 888-890
(1971)] has a microbicidal action.
It is known to have The use of 1-methylol-2-thiono-1,2-dihydrobenzothiazole as a microbicide is described in West German Open
Known from number 2201457. However, when these compounds are used individually, they are unsatisfactory against microorganisms due to gaps in their activity spectra. To solve this problem, benzimidazolyl-methyl-carbamate and 3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-
Active compound combinations consisting of 2-thiones are already known (DE 2150219). A disadvantage of this known combination of active compounds is that formaldehyd depot substances
3,5-dimethyl-tetrahydro-1,3,5-thiadiazine-2-thione as a substance is only moderately stable and therefore easily decomposes under the influence of environmental factors. The present invention now provides microbicidal compositions comprising as active ingredients benzimidazolyl-methyl-carbamate and dichlorofluoromethyl-thiophthalimide, either alone or in admixture with a diluent or carrier. The active compound combinations according to the invention have particularly high microbicidal activity. Furthermore, the invention provides a method for protecting materials against microorganisms, which method consists in applying or formulating a composition according to the invention to the materials. Surprisingly, the microbicidal activity, in particular the fungicidal activity, of the active compound combination according to the invention is considerably higher than the sum of the effects of the individual active compounds. Therefore, there is a genuine synergistic effect. The combination of active compounds represents a valuable addition to the art. The preparation of benzimidazolyl-methyl-carbamates is known (U.S. Pat. No. 3,010,968).
issue). Dichlorofluoromethyl-thiophthalimide can be prepared according to US Pat. No. 3,285,929. The weight ratios of the active compounds in the active compound combinations mentioned above can be varied within a relatively wide range. Generally, from 1 to 25 parts by weight of dichlorofluoromethyl-thiophthalimide per part by weight of benzimidazolyl-methyl-carbamate, preferably from 2 to 25 parts by weight of dichlorofluoromethyl-thiophthalimide.
12 parts by weight. The particle size of the active compounds according to the invention can vary within wide limits. Generally, active compounds with a particle size of 100 to 350 microns, preferably 150 to 300 microns, are used. Benzimidazolyl-methyl-carbamate 1
A combination with 2 to 10 parts by weight of dichlorofluoromethyl-methyl-thiophthalimide is particularly effective. The active compound combinations according to the invention exhibit a strong action against microorganisms. Examples of microorganisms that may be mentioned are fungi, yeasts and algae. Examples of fungal molds and yeasts that may be mentioned are Penicillium glaucum, Rhinopus nigricans, Aspergillus niger, Pullularia pullulans, Alternaria tenuis. ) Torula utilis, Candida cruseu, and Candida albicans. Examples of algae that may be mentioned are Phaeodactylum tricornutum Bohlin, Euglena gracilis
Klebs), Oscillatoria geminata Meneghini and Stichococcus
bacillaris naeseli). The present invention relates to a combination of active compounds for the protection of industrial materials against degradation by microorganisms.
Industrial materials include, for example, adhesives, glue, paper and cardboard, texile, leather, wood, paints, plaster, packaging contents that can be damaged or spoiled by the action of microorganisms. be. The active compound mixtures according to the invention are particularly suitable for protecting adhesives, fabrics and paper. The novel combination of active compounds can be applied, for example, to solutions,
It can be converted into conventional formulations such as suspensions, pastes and powders. The novel combinations of active compounds can be used as such, in the form of their formulations and in the use forms prepared therefrom. They can be used in the customary manner, for example by disintegrating homogeneously into the material to be protected or by impregnating, coating or spraying the technical material. The amount of active compound combination used depends on the nature and incidence of the microorganisms, the number of germs
count) and medium dependent. For use, the optimum amount to be used can be determined in each case by a series of tests. However, it is generally sufficient to use a mixture of active compounds in an amount of 0.01 to 1.0% by weight of the material to be treated. The active compound combinations according to the invention have an advantageously broad spectrum of action. If the active compounds according to the invention are used in a suitable manner, the concentration of the active compound combinations present in the effluent is not of a difficulty in biological remediation. The active compound combination according to the invention makes it possible to advantageously replace hitherto available microbicides with more effective agents and to advantageously reduce the amount of agent required to eradicate microorganisms. . Test to determine mold resistance of the coating in Example 1. This exam is based on the Defense Standards
Laboratories Maribyrnong/Australia Report 219
The procedure is as follows: a smooth base paper specimen is coated on both sides with the product to be tested and dried in a greenhouse for 8 days. For aging, part of the paint coating is lined with running water for 24 hours at 24°C or at 40-60°C.
exposed to fresh air for 8 days or subjected to a 110 hour dry xenon test. 5 x 5 cm sections of the samples prepared in this way are placed separately on glucose nutrient medium in Petri dishes and contaminated with a suspension of spores of the oyster fungus mold: Aspergillus niger, Aspergillus niger, Puriularia aprinus. Lance, Alternaria speciales, Penicillium citrium, Stachybotrys atra, Paecilomyces varioti, Cladosporium
herbarum), Aspergillus ustus and Aspergillus flavus. The contaminated dishes are stored at 28-30°C and 90-95% relative atmospheric humidity and evaluated after 3 weeks. If the sample remains mold-free after this test, the coating is considered mold-resistant. Example 1 The fungal resistance of commercially available gloss paints based on alkyd resins is tested according to the test method described above. In order to demonstrate the synergistic effect of the mixture of active compounds according to the invention, (a) penzimidazolyl-methyl-carbamate (hereinafter referred to as BCM)
(b) 0.198% of dichlorofluoromethyl-thiophthalimide (hereinafter referred to as DCFP) and (c) 0.273% of the active compound according to the invention (BCM 0.075%).
% and DCFP (consisting of 0.198%) to the gloss paint (in each case based on the film weight). The individual active compounds are dissolved in the gloss paint prior to testing. Post-test evaluation is as follows:
【表】
試験の結果は被覆を熟成するために使用した特
定の手段に依存しない。
菌カビによるラツカーフイルムの汚染を防止す
るべき場合には、上記光沢塗料はフイルムの重量
に対してジクロロフルオロメチル−チオフタルイ
ミド1.5％の添加を必要とする。活性化合物とし
てベンゾイミダゾリル−メチル−カルバメートを
光沢塗料に加える場合に、菌カビによる汚染を防
止するためには、固形分に対してベンゾイミダゾ
リル−メチル−カルバメート0.8％が必要であ
る。
これらの数字から、本発明に従う活性化合物の
組合せに対する相乗効果を決定することが可能で
ある。Kull〔Applied Microbiology9，538〜541
（1961）〕に従えば、下記関係が成り立つ：
ＱＡ／Ｑａ＋ＱＢ／Ｑｂ＝Ｘ
Ｘ＝１ 付加を意味する。
Ｘ＝＞１ 拮抗作用を意味する。
Ｘ＝＜１ 相乗作用を意味する。
0.8＝Qa＝耐菌カビ性被覆を与えるBCMの濃度。
1.5＝Qb＝耐菌カビ性被覆を与えるDCFPの濃
度。
0.075＝ＱA＝実施例１に従う混合物中における耐
菌カビ性被覆を与えるBCMの量。
0.198＝ＱB＝実施例１に従う混合物中の、耐菌カ
ビ性被覆を与えるDCFPの量。
これはＸ＝0.23（相乗作用を意味する）を与え
る。
実施例 ２
紙（90〜100ｇ／cm2）の重量に対してBCM／
DCFP＝1/6 0.4％を下記の組成の紙パルプスラ
リー〔原質（stock）コンシステンシー１％、PH
値4.8中に均質に分散させる：漂白した亜硫酸パ
ルプ39.9％漂白したカバ材硫酸塩パルプ39.9％、
市販の入手可能な増白剤0.2％、市販の入手可能
な樹脂サイズ剤２％、クレー15％及びミヨウバン
３％、このパルプスラリーから製造した紙は顕著
に耐菌カビ性である：原質処理システム（stock
handling system）は紙製造期間中スライムを含
まないままであり、その結果他の抗スライム剤の
使用は不必要である。
該紙の耐菌カビ性を下記の如く試験する：円形
の紙試料（直径４cm）をペトリ皿中、試験菌カビ
〔トリコデルマビリデ（Trichoderma viride）、
ケトミウムグロボスムクンゼ（Chaetomium
globosum Kunze）、黒色麹菌クロカビ及びアル
テルナリアテヌイス〕により予め感染させてある
栄養培地上に置く。30℃及び90〜95％相対大気湿
度で８〜14日間貯蔵した後、前記活性化合物を含
まない紙は上記試験菌カビの増殖（growth）に
より完全に覆われ、一方前記した如くして製造し
た紙はこれらの極端な条件下ですらカビを含まな
いままである。
他方、BCM1％又はDCFP1％（各々の場合に
紙の重量に対して）の添加は、耐菌カビ性の紙を
もたらさない。Kullの式（実施例１参照）により
Ｘ＜0.40の相乗作用が計算される。
実施例 ３
市販の入手可能な壁原紙（raw−paper）を、
乾燥サイズ剤に対してBCM／DCFP＝1/9 0.25
％を含有するデンプンサイズ剤で被覆する。
紙の重量は80ｇ／m2である。接着剤の層は８
ｇ／m2（乾燥後）である。このようにして製造さ
れた自己接着性壁原紙は下記試験により示される
如く耐菌カビ性である。
試験片（直径4.5cm）を、菌カビを含み且つ腐
敗した壁紙から単離した菌カビ（トリコデルマビ
リデ、ケトミウムグロボスムクンゼ、黒色麹菌ク
ロカビ及びアルテルナリアテヌイス、を含む）で
予め感染させてあるペトリ皿中の寒天栄養培地上
に置く。30℃及び90〜95％相対大気湿度で１週間
貯蔵後、試験片は依然として菌カビを含まない。
同じ条件下に、活性化合物を含まない接着剤の層
を有する壁原紙はこの時点で試験菌カビの増殖で
ある完全に覆われるに到る。
実施例 ４
BCM／DCFPとの混合物及びBCMとTCP（ト
リクロロメチル−チオフタルイミド）との混合物
について、種々の混合割合の下で、３種の微生物
に対する作用（最小発育阻止濃度MIC）を試験
し、実施例１におけると同様にしてＸ値を算出し
た。結果を以下に示す。
〔Ａ〕 ケトミウムグロボスムに対する試験Table: The results of the test are independent of the specific means used to age the coating. If contamination of the Lutzker film by fungi is to be prevented, the gloss coating described above requires the addition of 1.5% dichlorofluoromethyl-thiophthalimide, based on the weight of the film. If benzimidazolyl-methyl-carbamate is added as active compound to gloss paints, 0.8% of benzimidazolyl-methyl-carbamate, based on the solids content, is required to prevent contamination with fungi. From these numbers it is possible to determine the synergistic effect for the active compound combinations according to the invention. Kull〔Applied Microbiology9, 538-541
(1961)], the following relationship holds: Q A /Qa+Q B /Qb=X X=1 means addition. X=>1 means antagonism. X=<1 means synergism. 0.8 = Qa = concentration of BCM that gives a fungi-resistant coating. 1.5 = Qb = concentration of DCFP that gives a fungi-resistant coating. 0.075 = Q A = amount of BCM in the mixture according to Example 1 giving a fungi-resistant coating. 0.198 = Q B = amount of DCFP in the mixture according to Example 1 giving a fungi-resistant coating. This gives X=0.23 (meaning synergy). Example 2 BCM/
DCFP=1/6 0.4% was added to paper pulp slurry with the following composition [stock consistency 1%, PH
Homogeneously dispersed in value 4.8: Bleached sulfite pulp 39.9% Bleached birchwood sulfate pulp 39.9%,
Commercially available brightener 0.2%, commercially available resin sizing agent 2%, clay 15% and alum 3%, the paper made from this pulp slurry is significantly resistant to fungi: stock treatment System (stock
The handling system remains slime-free during paper manufacturing, so that the use of other anti-slime agents is unnecessary. The fungal resistance of the paper is tested as follows: A circular paper sample (4 cm in diameter) is placed in a Petri dish with the test fungus [Trichoderma viride, Trichoderma viride,
Chaetomium globos mukunzee (Chaetomium
globosum Kunze), Aspergillus niger and Alternaria tenuis]. After storage for 8-14 days at 30° C. and 90-95% relative atmospheric humidity, the active compound-free paper was completely covered with growth of the test fungus mold, while the paper prepared as described above The paper remains mold-free even under these extreme conditions. On the other hand, addition of 1% BCM or 1% DCFP (in each case relative to the weight of the paper) does not result in a mold-resistant paper. Synergy for X<0.40 is calculated by Kull's formula (see Example 1). Example 3 Commercially available wall paper (raw-paper) was
BCM/DCFP=1/9 0.25 for dry sizing agent
Coat with starch sizing agent containing %. The weight of the paper is 80g/ m2 . 8 layers of adhesive
g/m 2 (after drying). The self-adhesive wall paper thus produced is resistant to fungi and mold, as shown by the following tests. Test specimens (4.5 cm in diameter) were pre-infected with fungal molds (including Trichodermaviride, Chaetomium globos mukunzee, Aspergillus niger and Alternaria tenuis) containing fungal molds and isolated from decayed wallpaper. Place on agar nutrient medium in a petri dish. After storage for one week at 30° C. and 90-95% relative atmospheric humidity, the specimens remain mold-free.
Under the same conditions, the wall paper with a layer of adhesive without active compound now becomes completely covered with test fungal growth. Example 4 A mixture of BCM/DCFP and a mixture of BCM and TCP (trichloromethyl-thiophthalimide) was tested for its effect on three types of microorganisms (minimum inhibitory concentration MIC) under various mixing ratios, The X value was calculated in the same manner as in Example 1. The results are shown below. [A] Test for ketomium globosum
【表】 〔Ｂ〕 黒色麹菌クロカビに対する試験【table】 [B] Test against Aspergillus black mold
【表】 〔Ｃ〕 アルテルナリアテヌイスに対する試験【table】 [C] Test against Alternaria tenuis
Claims (1)
ル−カルバメート及びジクロロフルオロメチル−
チオフタルイミドから成る活性化合物の組合せを
含有することを特徴とする殺微生物剤。 ２ 前記活性化合物の組合せにおいて、ベンゾイ
ミダゾリル−メチル−カルバメート１重量部につ
きジクロロフルオロメチル−チオフタルイミド１
〜25重量部ならしめる特許請求の範囲第１項記載
の殺微生物剤。[Claims] 1. Benzimidazolyl-methyl-carbamate and dichlorofluoromethyl-carbamate as active ingredients.
A microbicide characterized in that it contains a combination of active compounds consisting of thiophthalimide. 2 In the active compound combination, 1 part by weight of benzimidazolyl-methyl-carbamate contains 1 part by weight of dichlorofluoromethyl-thiophthalimide.
25 parts by weight of the microbicide according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762607031 DE2607031C2 (en) | 1976-02-20 | 1976-02-20 | Benzimidazolyl carbamate-based microbicidal agent |
| DE19762607030 DE2607030A1 (en) | 1976-02-20 | 1976-02-20 | Antimicrobials for paints, paper and adhesives - contg. benzimidazole carbamate, tetramethyl-thiuram disulphide and (1)-methylol-(2)-thiono-(1,2)-dihydro-benzthiazole |
| DE19762607033 DE2607033C3 (en) | 1976-02-20 | 1976-02-20 | Microbicidal agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52102428A JPS52102428A (en) | 1977-08-27 |
| JPS6117802B2 true JPS6117802B2 (en) | 1986-05-09 |
Family
ID=27186757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1557777A Granted JPS52102428A (en) | 1976-02-20 | 1977-02-17 | Germicide |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS52102428A (en) |
| CH (1) | CH603045A5 (en) |
| GB (1) | GB1542829A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03226202A (en) * | 1990-01-31 | 1991-10-07 | Fuji Electric Co Ltd | Collector head for pantograph |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61118303A (en) * | 1984-11-15 | 1986-06-05 | Katayama Chem Works Co Ltd | Industrial germicide |
| JPH10109912A (en) * | 1996-10-04 | 1998-04-28 | Akio Suganuma | Antimicrobial composition |
-
1977
- 1977-02-16 GB GB646777A patent/GB1542829A/en not_active Expired
- 1977-02-16 CH CH192577A patent/CH603045A5/xx not_active IP Right Cessation
- 1977-02-17 JP JP1557777A patent/JPS52102428A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03226202A (en) * | 1990-01-31 | 1991-10-07 | Fuji Electric Co Ltd | Collector head for pantograph |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52102428A (en) | 1977-08-27 |
| CH603045A5 (en) | 1978-08-15 |
| GB1542829A (en) | 1979-03-28 |
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