SE176992C1

SE176992C1 -

Info

Publication number: SE176992C1
Authority: SE
Publication date: 1961-01-01

Description

Uppfinnare: W N Cannon Prioritet begard frdn den 17 fait 1958 (Amerikas Forenta Stater) Denna upppfinning avser nya preparat for kontroll av mikrobiell fororening av ekonomiskt viktiga organiska suspensioner och emulsioner. Manga vattenhaltiga organiska emulsioner och suspensioner, vilka allmant kunna betecknas som vattenhaltiga organiska kolloider, aro utsatta for angrepp av en mangfald mikroorganismer, innefattande bakterier, jastsvampar och andra svampar. Pa grund av den industriella betydelsen air manga av dessa organiska kolloider ar det onskvart att skydda dem Iran mikrobangrepp eller alternativt att avbryta bakterie- eller svamputvecklingen, om den redan borjat. Exempel pa industriellt viktiga kolloider, vilka det ãr Onskvart att skydda mot mikrobiell fOrorening, aro polystyrenbutadienemulsioner f Or larger, vatten-oljeemulsioner, sasom de sa kallade losliga oljeemulsioner, som anvandas for maskinbearbetningsandamal, smorfettsanalysprov, latexemulsioner, uretanskum och suspensioner och pastor, sasom starkelsepasta, pappersmassa, kaseinfarger. Inventor: W N Cannon Priority Required from 17 Fait 1958 (United States of America) This invention relates to new preparations for controlling microbial contamination of economically important organic suspensions and emulsions. Many aqueous organic emulsions and suspensions, commonly referred to as aqueous organic colloids, are susceptible to attack by a variety of microorganisms, including bacteria, yeasts and other fungi. Due to the industrial importance of many of these organic colloids, it is advisable to protect them from micro-infestation or, alternatively, to stop the development of bacteria or fungi, if it has already begun. Examples of industrially important colloids which are unsafe to protect against microbial contamination are polystyrene butadiene emulsions or larger, water-oil emulsions, such as the so-called soluble oil emulsions, used for machining purposes, butterfat analysis samples, latex emulsion samples, , pulp, casein dyes.

Uppfinningen avser ett preparat, som effektivt forhindrar tillvaxten av mikroorganismer i vattenhaltiga organiska kolloider, vilket preparat innefattar i blandning 1) en viktdel etylmerkuritiosalicylsyra (C-HgS • C01-14COOH dar substituentgrupperna vid bensenringen befinna sig i ortostallning) eller ett vattenlosligt salt &ray och 2) frau omkring 4 till omkring 100 viktdelar o-fenylfenol eller ett vattenlosligt salt darav. Uppfinningen avser vidare en vattenhaltig organisk kolloid, innehallande for antimikrobverkan omkring 10 till omkring 200 miljondelar av etylmerkuritiosalicylsyra eller doss vattenlosliga salter och omkring 100 till omkring 2000 miljondelar av o-fenylfenol eller dess vattenlOsliga salter. De riya preparaten enligt uppfinningen innefatta i kombination etylmerku ritiosalicylsyra och o-fenylfenol eller deras vattenlosliga katjoniska salter. Lampliga katjoniska salter innefatta metallsalter, sasom natrium- och kaliumsalterna, och metalloid-salter, sasom ammonium och aminsalterna. De relativa mangderna av etylmerkuritiosalicylsyran och o-fenylfenolen, som anvandas i preparaten enligt dennna uppfinning, kunna varieras mom vida granser. Det visar sig emellertid, att det vidaste spektrat av antimikrobiell effektivitet uppnas, nar o-fenylfenolen foreligger i kombination i storre mangd an etylmerkuritiosalicylsyran. De foredragna preparatcn innehalla darfor exempelvis fran omkring 4 till omkring 100 viktdelar o-fenylfenol per viktdel etylmerkuritiosalicylsyra. Maximal antimikrobiell effektivitet uppnas vanligen, nar preparaten innehalla omkring 10 till omkring 50 viktdelar o-fenylfenol per viktdel etylmerkuritiosalicylsyra. De ovanstaende forhallandena mellan bestandsdelarna anvandas aven nar bestandsdelarna anvandas i form av sina salter. Antimikrobmedlen kunna inforlivas var for sig i kolloiden, som skall skyddas, men for att forenkla anvandningen forenas medlen vanligen i lampliga proportioner i ett koncentrat, vilket darefter sattes till kolloiden i tillracklig mangd for uppnaende av den onskade antimikrobverkan. The invention relates to a composition which effectively prevents the growth of microorganisms in aqueous organic colloids, which composition comprises in mixture 1) a part by weight of ethyl mercuritiosalicylic acid (C-HgS • CO ) from about 4 to about 100 parts by weight of o-phenylphenol or a water-soluble salt thereof. The invention further relates to an aqueous organic colloid, containing for antimicrobial action about 10 to about 200 million parts of ethyl mercuritiosalicylic acid or dose of water-soluble salts and about 100 to about 2000 million parts of o-phenylphenol or its water-soluble salts. The rich compositions of the invention in combination comprise ethyl mercury triosalicylic acid and o-phenylphenol or their water-soluble cationic salts. Suitable cationic salts include metal salts, such as the sodium and potassium salts, and metalloid salts, such as ammonium and the amine salts. The relative amounts of the ethyl mercuritiosalicylic acid and o-phenylphenol used in the compositions of this invention can be varied widely. It is found, however, that the broadest spectrum of antimicrobial efficacy is obtained when the o-phenylphenol is present in combination in greater amounts than the ethyl mercuritiosalicylic acid. The preferred compositions therefore contain, for example, from about 4 to about 100 parts by weight of o-phenylphenol per part by weight of ethyl mercuritiosalicylic acid. Maximum antimicrobial efficacy is usually achieved when the compositions contain about 10 to about 50 parts by weight of o-phenylphenol per part by weight of ethyl mercuritiosalicylic acid. The above ratios between the ingredients are also used when the ingredients are used in the form of their salts. The antimicrobial agents can be incorporated separately into the colloid to be protected, but to facilitate use, the agents are usually combined in appropriate proportions in a concentrate, which is then added to the colloid in sufficient quantity to achieve the desired antimicrobial effect.

Koncentratet kan ha formen av ett torrt pulver eller en losning, antingen vattenhaltig eller joke vattenhaltig, eller en suspension. Det fOredragna koncentratet är en vattenlosning av en blandning i lampliga proportioner av vattenlosliga salter av etylmerkuritiosalicylsyra och o-fenylfenol. Organiska losningsmedelslosningar eller -suspensioner av antimikrobmedlen eller deras salter kunna anvandas for beredning av koncentrat. Exempel pa organiska losningsmedel, som kunna anvandas for detta andamal, Oro xylen, alko- 2— — hol, propylenglykol och polyetylenglykol. For effektiv mikrobkon.troll bar etylmerkuritiosalicylsyran och o-fenylfenolen foreligga i den organiska kolloiden, som skall skyddas, i en en mangd av omkring 10 till omkring 200 miljondelar (raknat pa vikt) av den. forra och omkring 100 till omkring 2000 miljondelar av den senare. De koncentrationer, som skola anvandas, aro desamma oberoende av huruvida antimikrobmedlen anvandas i sin syraform eller i sin saltform. The concentrate may be in the form of a dry powder or a solution, either aqueous or joke aqueous, or a suspension. The preferred concentrate is an aqueous solution of a mixture in appropriate proportions of water-soluble salts of ethyl mercuritiosalicylic acid and o-phenylphenol. Organic solvent solutions or suspensions of the antimicrobials or their salts may be used for the preparation of concentrates. Examples of organic solvents which can be used for this purpose are oro xylene, alcohol, propylene glycol and polyethylene glycol. For effective microbial control, the ethyl mercuritiosalicylic acid and o-phenylphenol should be present in the organic colloid to be protected in an amount of about 10 to about 200 parts per million (by weight) of it. the former and about 100 to about 2000 parts per million of the latter. The concentrations to be used are the same regardless of whether the antimicrobials are used in their acid form or in their salt form.

Det är mycket averraskande, att preparaten enligt denna uppfinning, som innehalla etylmerkuritiosalicylsyra och o-fenylfenol samt deras losliga salter, ha sa hog effektivitet for konservering av organiska kolloider, eftersom ingendera foreningen sjalv effektivt forhindrar eller kontrollerar fororening av kolloiderna. I vissa av de industriellt viktiga kolloiderna, sasom losliga oljeemulsioner for maskinverkt3-gsverkstader, vilka innehalla svarvspan och annat metallavfall, f8religger sannolikhet far fororening av emulsionen med tunga metaller, sarskilt koppar. Sasom bekant forstores etylmerkuritiosalieylsyra efter flagon tid genom inverkan av kopparjoner narvaro av syre, och det liar tidigare varit brukligt att infora ett stabiliseringsmedel for etylmerkuritiosalicylsyran, om kopparfarorening kunde forutses. De vanligen anvanda etylmerkuritiosalicylsyrastabilisatorerna, exerapelvis etylendiamin, etanolamin och etylendiamintetrafittiksyra, kunna anvandas i preparaten enligt uppfinningen, om endast kopparfororening befaras. Om emellertid aven andra tunga metaller dro ndrvarande, och i synnerhet om jam n aven am narwarande, anvandas foretradesvis andra stahilisatorer fOr etylmerkuritiosalicylsyra, sasom 8-hydroxikinolin, his-salicylaletylendiamin, bis-salicylalo-fenylendiamin, och beslaktade fiireningar med liknande stabiliseringsformaga. F8r de fiesta industriella anvandningar bOr stabiliseringsmedlet yam . nfirvarande minimalt i omkring samma koncentration sam etylmerkuritiosalicylsyran, och maximalt i en mangd som Or omkring tva ganger koncentrationen av etylmerkuritiosalicylsyran. En loslig oljeemulsion avsedd att anvandas for maskinverktyg, innehallande 50 miljondelar etylmerkuritiosalicylsyra och 1000 miljondelar o-f enylfenol som konserveringsmedel, skulle lunda exempelvis Oven innehalla Iran 50 till 100 miljondelar 8-hydroxikinolin eller bissalicylaletylendiamin som stabiliseringsmedel f 5r etylmerkuritiosalicylsyran. pa samma satt skulle ett koncentrat, lampligt fOr tillsats till en loslig ojeemulsion for maskinverktyg, innehallande 2 % etylmerkuritiosalicylsyra och % o-fen-ylfenol som deras natriumsalter, innehalla frail 2 till 4 % av ett stabiliseringsmedel av ovan angiven typ. It is very surprising that the compositions of this invention, which contain ethyl mercuritiosalicylic acid and o-phenylphenol and their soluble salts, have such a high efficiency for preserving organic colloids, since neither compound itself effectively prevents or controls contamination of the colloids. In some of the industrially important colloids, such as soluble oil emulsions for machine tool workshops, which contain lathe chips and other metal waste, there is a likelihood of contamination of the emulsion with heavy metals, especially copper. As is well known, ethyl mercuritiosalicylic acid is enlarged after a short time by the action of copper ions in the presence of oxygen, and it has previously been customary to introduce a stabilizer for ethyl mercuritiosalicylic acid, if copper impurity could be predicted. The commonly used ethylmercuritiosalicylic acid stabilizers, for example ethylenediamine, ethanolamine and ethylenediaminetetrafitic acid, can be used in the compositions of the invention if only copper contamination is feared. However, if other heavy metals are present, and especially if present, other stabilizers are preferably used for ethyl mercuritiosalicylic acid, such as 8-hydroxyquinoline, his-salicylalethylenediamine, bis-salicylalophenylenediamine, and similar stabilizing compounds. For most industrial uses, the stabilizer should be yam. present minimally in about the same concentration with the ethyl mercuritiosalicylic acid, and maximally in an amount as Or about twice the concentration of the ethyl mercuritiosalicylic acid. A loose oil emulsion intended for use in machine tools, containing 50 parts per million of ethyl mercuritiosalicylic acid and 1000 parts per million of o-phenylphenol as a preservative, would, for example, also contain 50 to 100 parts per million of 8-hydroxyquinoline or bissalicylalethylenediamine 5-stabilizing uricillin. similarly, a concentrate suitable for addition to a soluble oil emulsion for machine tools containing 2% ethylmercuritiosalicylic acid and% o-phenylphenol as their sodium salts would contain from 2 to 4% of a stabilizer of the above type.

Uppfinningen belyses narmare genom foljande speciella exempel. The invention is further illustrated by the following special examples.

Exempel 1. Example 1.

Ett vattenlosligt, antimikrobiellt font pulverpreparat beredes, genom noggrann blandning av 15 kg finfardelat natriuinetylmerkuritiosalicylat och 205 kg finfordelat natriumo-fenylfenat-tetrahydrat. Eventuellt kan omkring 30 kg 8-hydroxikinolin blandas nog-grant med de andra bestaridsdelania for astadkommande av en stabiliseringsverkan for natriummerkuritiosalicylatet vid den. tidpunkt, da. preparatet for anvandning inforlivas i en vattenemulsion eller -suspension. Det stabiliserade pulvret kan anvandas som konserveringsrnedeI genom att det i en mangd av omkring .0713 kg per 1000 kg sates till en styrenbutadienf arg med anvandning av kasein som modifieringsmedel for astadkommande av en slutlig koncentration i fargen av omkring 10 milj ondelar natriumetylmerkuritiosalicylat, 20 mijlondelar 8-hydroxikinolin och omkring 100 miljondelar natrium-o-fenylfenat. A water-soluble, antimicrobial font powder preparation is prepared by thoroughly mixing 15 kg of finely divided sodium methylmercuritiosalicylate and 205 kg of finely divided sodium o-phenylphenate tetrahydrate. Optionally, about 30 kg of 8-hydroxyquinoline can be thoroughly mixed with the other bistrids to provide a stabilizing effect of the sodium mercury thiosalicylate thereon. time, then. the preparation for use is incorporated into an aqueous emulsion or suspension. The stabilized powder can be used as a preservative by adding it in an amount of about 0713 kg per 1000 kg to a styrene-butadiene fiber using casein as a modifier to achieve a final concentration in the color of about 10 million parts of sodium ethyl mercuritiosalicylate, 8 ml. -hydroxyquinoline and about 100 parts per million sodium o-phenylphenate.

Exempel 2. 4,54 kg etylmerkuritiosalicylsyra ocb. 91 kg o-fenylfenol malas till en partikelstorlek av i genomsnitt omkring 10 mikron, blandas nog-grant och fordelas jamnt genom effektiv omraring i 378 1 av en vattenlosning innehallande omkring 5 viktprocent metylcellulosa med en viskositet av 4000 centipois. 0,45 kg av ovanstaende suspension kan sattas till 181 kg loslig starkelsepasta for astadkommande av en slutlig koncentration i pastan av 25 miljondelar etylmerkuritiosalicylsyra och 500 miljondelar o-fenylfenol. Starkelsepastan skyddas darigenom mot mikrobangrepp. Example 2. 4.54 kg of ethyl mercuritiosalicylic acid ocb. 91 kg of o-phenylphenol are ground to a particle size of on average about 10 microns, mixed thoroughly and evenly distributed by efficient stirring in 378 l of an aqueous solution containing about 5% by weight of methylcellulose having a viscosity of 4000 centipois. 0.45 kg of the above suspension can be added to 181 kg of loose starch paste to achieve a final concentration in the paste of 25 parts per million of ethyl mercuritiosalicylic acid and 500 parts per million of o-phenylphenol. The starch paste is thereby protected against microbial attack.

Exempel 3. 4,6 kg etylmerkuritiosalicylsyra och 117 kg o-fenylfenol losas i 148 1 xylen. Till losningen sattes som stabiliseringsmedel 9,1 kg bissalicylal-o-fenylendiamin. Ovanstaende losning kan sattas i en mangd av omkring 28 g per 19 1 till linolja, vilken skall inforlivas i olika fargblandningar, for astadkommande av larger, vilka forbli i huvudsak fria Iran fororening genom mikroorganismer. Example 3. 4.6 kg of ethyl mercuritiosalicylic acid and 117 kg of o-phenylphenol are dissolved in 148 l of xylene. To the solution was added as stabilizer 9.1 kg of bissalicylal-o-phenylenediamine. The above solution can be added in an amount of about 28 g per 19 liters of linseed oil, which is to be incorporated into various color mixtures, to provide larger ones, which remain substantially free of Iran contamination by microorganisms.

Exempel 4. 181 kg kommersiellt natrium-o-fenylfenattetrahydrat, innehallande omkring 2 % Overskott av natriumhydroxid och natriumkarbonat loses i 94 1 vatten. Till losningen sattes under omroring 9,2 kg etylmerkuritiosalicylsyra och 18,1 kg 8-hydroxikinolin. Den slutliga volymen installes pa. 295 1 genom tillsats av vat-ten. Losningen innehaller ett tillrackligt Overskott av alkali for att de vattenlosliga natriumsalterna av etylmerkuritiosalicylsyran och o-fenylfenolen skola bildas, och en klar lOsning erhalles. Det vattenhaltiga kancentratet kan sattas till en loslig oljeemulsion, som anvandes f8r maskinbearbetningsandamal, i — —3 en mangd av omkring 28 g koncentrat per 19 1 emulsion for astadkommande av i huvudsak frihet fran angrepp av mikroorganismer hos emulsionen. Example 4. 181 kg of commercial sodium o-phenylphenate tetrahydrate, containing about 2% Excess sodium hydroxide and sodium carbonate are dissolved in 94 l of water. To the solution were added with stirring 9.2 kg of ethyl mercuritiosalicylic acid and 18.1 kg of 8-hydroxyquinoline. The final volume is installed on. 295 1 by adding the water. The solution contains a sufficient excess of alkali to form the water-soluble sodium salts of the ethylmercuritiosalicylic acid and the o-phenylphenol, and a clear solution is obtained. The aqueous can concentrate can be added to a soluble oil emulsion used for machining purposes in an amount of about 28 g of concentrate per 19 liters of emulsion to provide substantially freedom from attack by microorganisms in the emulsion.

Claims

Patent claim:

A composition which forms inhibit the growth of microorganisms in aqueous organic colloids, which composition comprises in admixture 1) one part by weight of ethyl mercuritiosalicylic acid or a water-soluble salt derivative and 2) Iran about 1 to about 100 parts by weight of o-phenylphenol or a water-soluble salt thereof. .

Preparation according to claim 1, characterized in that it contains a mixture of sodium ethyl mercuritiosalicylate and sodium o-phenylphenolate.

Preparation according to claim 1 or 2, characterized in that it also contains a material which forms a stabilizing ethyl mercuritiosalicylic acid.

Aqueous organic colloid, characterized in that it contains a preparation according to any one of the patent claims 13.

Colloid according to claim 4, characterized in that it contains about 10 to about 200 million parts of ethyl mercuritiosalicylic acid or its water-soluble salts and about 100 to about 2000 million parts of o-phenylphenol or its water-soluble salts. Anfarda Publications: Stockholm 1961. Art. Boktr. P. A. Norstedt & Saner. 610089