MXPA97005004A - Composition and - Google Patents

Abstract

The present invention relates to the use of a 2- (C3-5 alkyl) -BIT or 2-aralkyl-BIT such as 2-phenylethyl-BIT as a fungicide for plastic materials. 2-n-butyl-B is preferred

Description

COMPOSITION AND USE DESCRIPTION OF THE INVENTION The present invention relates to the use of the 2-alkyl- and 2-aralkyl-l, 2-benzisothiazolin-3-ions as biocides for the protection of plastic materials and especially their use as fungicides, including compositions thereof. 1,2-benzisothiazolin-3-ones (from hereinafter referred to as "BIT") and their use as biocides is well known in the art. GB 848,130 describes BITs containing inter alia a 2-substituent alkyl containing at least 4 carbon atoms or a 2-benzyl group substituted by halogen. These compounds are said to possess useful antibacterial and antifungal activity and are of pharmaceutical, veterinary and agricultural biocides use. US 3,517,022 discloses BITs containing inter alia a 2-substituted alkyl having from 4 to 24 carbon atoms and wherein the phenyl ring of BIT is substituted by a halogen, C 1-4 alkyl or C 4 -4 alkoxy Such compounds are to be useful in industrial biocides, especially agricultural fungicides and also pesticides.

GB 1,531,431 describes the 2- (C1_3 alkyl) -BIT- and its use as industrial biocides, including fungicides, in aqueous systems and paint films. More recently, EP 475,123 has proposed the use of 2- (n-alkyl of Cg_g) -BIT as industrial biocides and especially fungicides for paints and plastics. These compounds are to be effective particularly against Scopulariopeis brevicaulis. In addition, the 2- (n-alkyl of Cg_g) -BIT are established to have much higher activity against fungal mold than the 2- (C-.Y-EIT alkyl of GB 1,531,431.) Indeed, the data presented which shows that 2-n-octyl-BIT is more active than 2-n-hexyl-BIT and both are significantly more active than 2-methyl-BIT against fungi and yeasts. -alkyl-BIT are very active against fungi that deteriorate plastic materials and contrary to the recent teachings of the EP 475,123, the activity of these compounds against the important fungi in plastic materials, currently decreases with an increase in the number of carbon atoms in 2-alkyl chain It has also been found that some 2-aralkyl-BIT derivatives are also very active against these particular fungi and plastic materials.

In addition, an important property which is required for plastics fungicides is the ability to withstand the processing conditions, to which the material is subjected during the manufacturing process such as extrusion. This generally involves heating plastic materials to temperatures in excess of 140 ° C. It is therefore important that the fungicide present stability at high temperatures and low volatility under such conditions. It has been found that the most active BIT derivatives have a high volatility to make them available as fungicides for plastic materials and that the 2-alkyl group must contain not less than 3 carbon atoms. The 2-aralkyl-BIT derivatives have low and very advantageous volatility. Yet another important requirement for a fungicide for plastic materials is that it must be able to formulate with plasticizers and stabilizers which are commonly used in the plastics manufacturing industry and that the fungicides have high resistance to discoloration in use and longevity of effect. under various conditions to which the treated plastic materials are exposed in use. It has been found that certain 2-alkyl and 2-aralkyl-BIT derivatives (hereinafter "ABIT") meet the requirements mentioned in the above, especially with respect to "the volatility and activity against fungi that deteriorate plastic materials. According to the invention, the use of 2-alkyl- and 2-aralkyl-BIT derivatives of Formula 1 is provided as fungicides for plastic materials wherein R1 is hydroxy, halogen, C1_2alkyl or alkoxy R is C3_5alkyl, cycloalkyl or aralkyl which contains at least 2 carbon atoms attached to the aryl group with the nitrogen atom and wherein the alkyl group or aryl may be optionally substituted; and n is from 0 to 4. Preferably, the halogen is bromide and especially chlorine. The substituent R1 is preferably located in the 5- and / or 6- position of the BIT molecule and is especially localized in the 6-position.

An especially preferred embodiment is where n is zero. When R is alkyl it can be linear or branched but is preferably linear. Examples of such alkyl groups are n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl and 2-methylbutyl. When R is cycloalkyl, cyclopentyl is preferably. When R is alkyl, it preferably contains 4 carbon atoms and is especially n-butyl. When R aralkyl is, it is preferably 2-arylethyl and especially 2-phenylethyl. When the alkyl group or the aryl portion of the aralkyl group represented by R is substituted, the substituent is preferably hydroxy, halogen or nitrile.

It is preferred, however, that the alkyl group and the aryl portion are not substituted. Particularly useful effects have been obtained when R is n-butyl and especially 2-phenylethyl. The ABIT is incorporated into plastic materials to be protected at a concentration at which the ABIT exhibits some control of mushroom growth up to high concentrations. Preferably, the amount of ABIT is less than 1.5%, more preferably less than 1.0%, particularly less than 0.7% and especially less than 0.5% by weight based on the weight of plastic material. The useful effects have been obtained when the amount of ABIT is less than 0.25% and even less than 0.1% by weight of plastic materials. The ABIT must be stable to the temperature conditions to which the plastic materials are manufactured. Preferably, it is stable above 180 ° C, more preferably above 200 ° C and especially above 250 ° C. It is preferred that the heating weight loss of 25 to 160 ° C at a heating rate of 10 ° C / minute is less than 10%, more preferably less than 6% and especially less than 2%. As mentioned in the above, the ABIT is commonly formulated with a plasticizer or stabilizer which is suitable for use with plastic materials to be protected. Thus, according to another aspect of the invention, a composition comprising a plasticizer or stabilizer and an ABIT is provided. The plasticizer or stabilizer is any of those commonly used in the plastics manufacturing industry. A liquid is preferred and is especially an ester derivative of mono- and dicarboxylic acids and linear or branched alcohols, epoxidized fatty acid esters and epoxidized vegetable oils. Examples of these plasticizers and stabilizers are phthalates, particularly dialkyl phthalates, such as dioctyl phthalate, di- (2-ethylhexyl) phthalate, dinonyl phthalate and di-isodecyl alato, epoxidized octyl stearate and epoxidized soybean oil; and the phosphate esters of the general formula 0 = P (OR 2) 3, wherein R 2 is hydrocarbyl, especially aryl such as phenyl and more especially C 1-4 alkyl, which may be linear or branched. Examples of such alkyl groups are methyl, ethyl, isopropyl, butyl and tert-butyl. Examples of other esters are adipates, sebacates and trimellitates of linear or branched alcohols, especially those alcohols containing from 8 to 10 carbon atoms and low molecular weight oligo- and polyesters such as those obtainable by reacting 1,3-butanediol with adipic acid . The composition may contain more than one ABIT.

It can also contain other fungicides and / or algicides to broaden the spectrum of activity of the composition. Examples of other fungicides and algicides include 2-alkyl-BIT such as 2- (n-hexyl) -BIT, 2- (2-ethylbutyl) -BIT, 2- (2-ethylhexyl) -BIT, 2-octylisothiazolin-3 -one, oxy-bis-10, 10-phenoxarsine, trichloromethyl mercaptophthalimide; ureas such as 2- (3,4-dichlorophenyl) -1,1-dimethylurea and 2- (4-isopropylphenyl) -1,1-dimethylurea; halogenated pyridines with 4-alkylsulfonyl such as 2, 3, 5, 6-tetrachloro-4- (methylsulfonyl) -pyridine and 2, 3, 6-trichloro-4- (isopropylsulfonyl) -pyridine; tetrachloro-isophthalonitrile; benzimidazomethyl carbamate; thiocyanatomethyl-thiobenzothiazole; methylene bis-oxyethylene, iodopropargyl-n-butyl carbamate; triazines such as 2-tert-butylamino-4-ethylamino-6-methylmercapto-1,3,5-triazine and 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine; N- (1-methyl-1-naphthylmaleamide, dichlorofluanide, (fluoro) -captan and (fluoro) -folpet Where the composition contains an additional fungicide and / or algicide is preferably present at a concentration of less than 50%, greater preference less than 30% and especially less than 10% by weight relative to the amount of ABIT As mentioned herein above, fungicides for plastic materials require a careful balance of microbiological activity and volatility and here any additional fungicide and / or algicide should not significantly impair the properties and performance in the use of ABIT For this reason it is preferred that the composition contains only an ABIT The 2-alkyl-BIT of formula 1 are generally liquid at 20 to 25 ° C and easily dissolved in plasticizers or stabilizers.The aralkyl-BIT are solids of 20 to 25 ° C but can be easily dissolved in plasticizers or stabilizers if they are necessarily by heating .Where high ABIT concentrations are required in plasticizers or stabilizers and this exceeds their solubility at ABIT, it can be dispersed in the plasticizer or stabilizer by means of a suitable dispersant particularly a nonionic dispersant. A preferred dispersant is the product of the reaction of a hydroxy carboxylic acid and an amine or a salt thereof. Especially preferred are the dispersing agents of the formula 2 Y . CO. ZR3 2 wherein Z is a divalent linking group which is attached to the carbonyl group through an oxygen atom or nitrogen atom; R3 is a primary, secondary or tertiary amino group or a salt thereof with an acid, or a quaternary ammonium salt; and Y is a residue of a polyester chain, which is linked with the group -CO-, derived from a hydroxycarboxylic acid of the formula HO-X-COOH 3 wherein X is a saturated or unsaturated divalent aliphatic group containing at least 8 carbon atoms and in which there are at least 4 carbon atoms between the hydroxy and carboxylic acid groups, or mixture of such as hydroxycarboxylic acid and a carboxylic acid which is free of hydroxyl groups. The group X is preferably an alkylene or alkenylene group and preferably contains not more than 30 carbon atoms, and especially not more than 20 carbon atoms. Examples of suitable hydroxycarboxylic acids of the formula 3 are 12-hydroxystearic acid, ricinoleic acid, 12-hydroxydecanoic acid and 6-hydroxycaproic acid. The divalent linking group represented by Z is preferably of the formula 1 or -O-A- Ñ-A- wherein T 1 is a hydrogen atom, an alkyl group of Cl-22 ° ethylene and A is an alkylene, cycloalkylene, heterocycloalkylene group or a hydroxyalkylene group containing from 2 to 6 carbon atoms. When T ^ is alkyl, it is preferably Ci-6 alkyl and when A is heterocycloalkylene it is preferably piperazine. When T1 and A both are ethylene, the groups T1 and A together with the nitrogen atom to which they are attached and the nitrogen atom of the amino group, R3 can form a piperazino ring. As examples of the radicals represented by T ^, methyl, ethyl, n-propyl, n-butyl and octadecyl can be mentioned. As examples of the radicals represented by A may be mentioned ethylene, trimethylene, tetramethylene, hexamethylene and beta-hydroxytrimethylene. The primary, secondary and tertiary amino groups represented by R3 are preferably of the formula t2 in which T2 and T3 are each independently hydrogen, alkyl of C-L_22 substituted C1_22 alkyl, aralkyl, cycloalkyl or T2 and T3 can together with the nitrogen atom to which they are attached form a 5 or 6 membered ring. When T2 or T3 is alkyl, it is preferably C- ^ g alkyl, such as methyl. When T2 or T3 is cycloalkyl, it is preferably cyclohexyl and when T2 and T3 form a ring, it is preferably a piperidino ring, morpholino or especially a piperazino ring. When T2 or T3 is aralkyl it is preferably benzyl. The quaternary amino groups represented by R 3 are preferably of the formula: T2 wherein T4 is hydrogen, alkyl of ^? .22 'substituted C1_22 alkyl, aralkyl or cycloalkyl and is an anion. It is preferred that T4 is C1_6 alkyl, such as methyl. In the special case where T2 and T3 together with the nitrogen atom to which they are attached form a piperazine ring, either one or the nitrogen atoms can be alkylated and either the nitrogen ring can form a salt or a compound of nitrogen. quaternary ammonium. As examples of the radicals represented by T2, T3 and T4 may be mentioned alkyl such as methyl, ethyl, n-propyl, n-butyl and octadecyl, hydroxy-lower alkyl such as β-hydroxyethyl and cyclohexyl. The acids used to form the salts with the amino groups or which contain the anion W may be any inorganic acid or an organic acid, such as hydrochloric acid, sulfuric acid, benzenesulfonic acid, methanesulfonic acid or benzoic acid. It is especially preferred that the anion results from the formation of a quaternary ammonium group, for example chloride, bromide or methosulfate.

The preparation of these dispersing agents is described in the patent GB 1373660 initially granted. Alternatively, the dispersing agent is the product of the reaction of a poly (lower alkylene) imine with a polyester having a free carboxylic acid group. The preferred polyester is derived from a hydroxycarboxylic acid of the formula 3 HO - X - COOH as defined in the above. The polyester is preferably reacted with the poly (lower alkylene) imine in a weight ratio between 1: 1 and 50: 1 and more preferably between 2: 1 and 20: 1. The term "lower alkylene" refers to an alkylene group containing from 2 to 4 carbon atoms and the preferred poly (lower alkylene) imine is polyethylene imine, which is available either in a substantially linear form or in a branched form. Preferably the polyethyleneimine is branched and especially branched in high form in which at least 20% of the nitrogen atoms are present as tertiary amino groups. The molecular weight of the suitable poly (lower alkylene) imines is generally greater than 500, preferably greater than 5000 and more especially in the range of 10,000 to 100,000.

The product of the reaction of hydroxycarboxylic acid and poly (lower alkylene) imine is a salt or an amide depending on the severity of the reaction conditions employed. The salt and / or amide can be partially neutralized with an acid, especially mineral acid or can be alkylated, the added alkyl group is optionally substituted, by means of the reaction with an alkyl sulfate such as dimethyl sulfate, where up to a salt It is also formed. The preparation of the reaction product of hydroxycarboxylic acid and poly'-lower alkylene imine is described in GB 2,001,083. A particularly useful dispersing agent is the product of the reaction obtained from about 2 moles of poly (12-hydroxystearic acid) with an acid value of 35 mg, KOH / g and 1 mol of dimethylaminopropylamine and quaternized with dimethyl sulfate as described in Comparative Example C of EP 127,325. This dispersing agent is hereinafter referred to as "Dispersant 1". Another dispersing agent, particularly useful is the product of the reaction obtained from about 3.3 equivalents by weight of poly (12-hydroxystearic acid) and 1 equivalent by weight of polyethyleneimine with an average molecular weight of about 20,000. This is prepared in a manner similar to Agent A in GB 2,001,083 and is hereinafter referred to as "Dispersant 2". The amount of dispersant, if present, is preferably from 0.1 to 20%, more preferably from 1 to 10%, especially from 3 to 10% and most preferably from 3 to 7% by weight based on the total weight of the dispersant. the composition. The composition preferably also contains a stabilizer to inhibit storage sedimentation. Examples of stabilizers are clays that occur naturally such as bentonite and particularly organically modified bentonite clay and polymers of elevated PM such as PVC. As described herein above, ABIT is used as a biocide and especially as a fungicide for the protection of plastic materials, especially polymeric, organic plastics from microbiological degradation. The .ABIT is particularly suitable for polyurethane materials and especially organic polymeric materials that contain a plasticizer or stabilizer such as those polymerized polyvinyl halide derivatives such as polyvinyl chloride.

(PVC). PVC plasticizer is commonly used both in the home and in the industry and is used in clothes, furniture, bathroom curtains, treads, waterproof membranes and those where the article that contains or is made of PVC, is exposed to moisture or mold conditions. The amount of plasticizer present in the plastic materials varies within the limits and is determined by the degree of flexibility required in the manufactured material. It is typically between 1 to 50% by weight of the plastic material. Thus, as yet another aspect of the invention, a composition comprising an ABIT and a plastic material is provided. ABITs are made by processes readily known in the art such as those described in GB 484,130, in which a 2-chlorosulfenylbenzoyl chloride is reacted with an alkylamine or an aralkylamine. Some of the ABITs are new. Thus, as another aspect of the invention, there is provided a compound of formula 1, wherein R is -CH (CH3) CH2CH2CH3, -CH (C2H5) CH2CH3, -CH2CH2CH (CH3) CH3, -CH2CH (CH3 CH3, -CH2CH (CH3) C2H5 and cyclopentyl and R1 and n are as defined herein. The present invention in all aspects is further illustrated and described in the following examples in which all parts are by weight unless otherwise indicated.

Example 1 and Comparative Example A A recipe for Agar of Potato Dextrose Agar (2 parts, ex Oxoid), Tryptone Soy Broth is prepared (10 parts, ex Oxoid) and Agar (14 parts, ex Oxoid) is made up to 1 liter and has a pH of 6.5. Aliquots of the ABIT are added under test of a 0.1% w / w solution in dioctyl phthalate diluted with 3 ml with dioctyl phthalate to give a final concentration in the agar recipe of 1.25, 2.5, 5, and 30 ppm. After the ABIT solution is added to the agar and homogenizing, the plates are emptied and allowed to settle. These plates are then inoculated with a suspension of 105 spores of the following fungi of deterioration of plastic materials. Aureobasidium pull ulans (AP) CM1 145194 Fusarium solanii (FS) CM1 172506 Penicillium funiculosus (PF) CM1 114933 Scopulariopsis brevicaulis (SB) CM1 49528 Streptoverticillium waksmanii (SW) NCIB 1091 The inoculated plates were incubated for 4 days at 20 ° C and the concentration of the .ABIT determined at which the growth of the fungi is suppressed. The results are given in Table 1 below, which refer to the ABIT of formula 1, where n is zero and R is as indicated. These show that 2-ethyl- and 2- (n-propyl) -BIT exhibit a slightly higher total activity compared to the control and a better activity against both of AP and SB. 2-ethyl-BIT is more active against FS.

Table 1 Example or R AP FS PF SB SW Example Comp. A Etilo 20 5 1.25 20 1.25 1 n-propyl 20 20 1.25 20 1.25 Control _ 30 20 1.25 30 1.25 Footnote to Table 1 Control is 2- (n-octyl) -isothiazolin-3-one.

Example 2 and Comparative Examples B to D Example 1 is repeated with the following ABIT as indicated in Table 2 below and the concentration of the determined chemistry at which fungal growth is suppressed. The results are given in Table 2 below and shows that 2- (n-butyl) -BIT is more active against the five fungi that deteriorate the plastic materials than both the 2- (n-hexyl) and 2- (n) compounds -octyl) -BIT described in EP 475,123 including a high activity against SB, especially when compared to 2- (n-octyl) -BIT. In general, 2- (n-butyl) -BIT is similar to the control. Taken with the results of Example 1, they are in a general trend of decreased activity against plastic materials ^ deteriorated as the length of the alkyl chain of the ABIT is increased. The 2-benzyl-BIT has an activity which is intermediate between (n-hexyl) - and 2 (n-octyl) -BIT. This decrease in activity with the rate of increase of carbon atoms in chain 2 - ABIT alkyl found by those major fungi impaired for plastic materials is opposite to that described for the fungus such as Aspergillus niger as described in EP 475,123.

Table 2 Example or R AP FS PF SB SW Comp Example 2 n-butyl 5 20 1.25 1.25 5 B n-hexyl 5 > 30 2.5 2.5 20 C n-octyl > 30 > 30 > 30 20 > 30 D benzyl 30 > 30 2.5 5 30 Control _ 1.25 20 1.25 2.5 2.5 Footnote of Table 2 Control is as set forth in Example 1 Examples 3 and 4 and Comparative Examples E and F Example 1 is repeated again with the ABIT listed in Table 3, except that a mixture of dioctyl phthalate and 50/50 dioctyl adipate is used in place of the dioctyl phthalate used in Example 1. The results given in Table 3 below show that n-pentyl-BIT has similar activity for Control and is greater than n- heptyl-BIT, especially against AP and FS. These results are again consistent with the decreased activity as length of the 2-alkyl chain of ABIT is increased. The branched chain compound, 2-ethylbutyl-BIT (Comparative Example E of Table 3) exhibits activity similar to the linear chain analog (Comparative Example B of Table 2) with equal loss of activity against FP. The 2-phenylethyl compound exhibits very high activity against all five deteriorators and is superior with respect to 2- (n-alkyl) -BIT and also 2-benzyl-BIT (Comparative Example D of Table 2).

Table 3 Example as R AP FS PF SB SW Comp Example 3 n-pentyl 5 20 1.25 1.25 1.25 E 2-ethylbutyl 5 30 20 1.25 20 F n-heptyl 20 > 30 2.5 1.25 1.25 4 2-phenylethyl 1.25 1.25 1.25 1.25 1.25 Control - 2.5 20 2.5 1.25 1.25 Footnote of Table 3 Control is as indicated in Table 1.

Examples 5 to 7 and Comparative Example A The ABITs listed in Table 4 below were heated in air on a Differential Scanning Calorimeter (DSC) of 25-300 ° C at a heating rate of 10 ° C / minute and the stability of the temperature is determined together with the previous temperature which evaporation occurs and also the loss of weight by 160 ° C which represents the temperature at which the PVC is manufactured. These results indicate that at least 3 carbon atoms in the alkyl chain of ABIT is required for adequate thermal stability to withstand manufacturing temperatures for PVC plastic materials. When these results are combined with the antifungal data of Examples 1 to 4 of ABIT, wherein R represents C3_5 alkyl is the optimal compromise for a fungicide to protect against deteriorated fungi in plasticizers of PVC plastic materials. The activity of 2-phenylethyl-BIT is combined with its physical properties such as thermal stability which shows this compound to be superior as an antifungal agent for PVC plastic materials compared to 2-alkyl-BIT, especially when compared to the activity of 2-benzyl-BIT as recorded in Example 2.

Table 4 Example R Stability of Start of Loss of No. temperature evaporation weight (%) (° C) (° C) by 160 ° C n-propyl 240 130 5.5 6 n-butyl 260 96 * 5.1 7 2-phenylethyl > 250 > 200 0 A ethyl 235 107 10.6 Footnote of Table 4 * the lower figure is due to a trace of the solvent Examples 8 to 15 and Comparative Examples A. G and H The fungal stearase activity in PVC was determined by the following fluorescein diacetate protocol. The PVC samples were prepared by adding the ABIT of the required aliquot of a 1% solution (w / w) of the compound dissolved in dioctyl phthalate and dioctyl adipate 50/50 to give 100, 250, 750, 2250 and 6750 ppm chemistry in the final sample of PVC. The PVC sample has the following composition: 100 parts, PVC resin (Corvic S 67/100) 2 parts, Zn / Ca stabilizer (Lankromark LN 138) 3 parts, Co plasticizer (Lankroflex ED6) 25 parts, plasticizer (phthalate of di-iso-octyl) (DOP) 25 parts, plasticizer (di-octyl adipate) (DOA) 0.5 parts, calcium stearate dispersant 0.2 parts, stearic acid mold release agent ppm ABIT A PVC sheet is prepared mixing the above ingredients until homogenizing and then rolling and mixing in a double laminate for 90 seconds at 160 ° C. The sheet was then cut into pieces and samples (2 cm x 5 cm) were prepared by pressing between two sheets of steel at 160 ° C and 8 tons of pressure for 5 minutes. The duplicated PVC samples are placed on a surface of a bed or a vermiculated bed moistened and sprayed with a spore suspension to 10% of the fungi of five damaging fungi listed in Example 1, which have been prepared in a salt solution. minimum comprising 2.0 parts of sodium nitrate, 0.7 parts of potassium diacid phosphate, 0.3 parts of dipotassium acid phosphate, 0.5 parts of potassium chloride, 0.5 parts of magnesium sulfate heptahydrate and 0.01 parts of ferrous sulfate heptahydrate, all in 1 liter giving a pH value of 6 to 6.5. The inoculated samples were then incubated for 7 days at 21 ° C. The samples were then removed and placed in individual bottles containing 6 ml of the solution buffer at a pH of 7.6 prepared from 0.06 M disodium phosphate (862.5 ml) and 0.06 M sodium diacid orthophosphate (137.5 ml) and also 1 ml of fluorescein diacetate (FDA) in dry acetone. The samples are then incubated for 30 minutes at 37 ° C to develop the colorful reaction. The absorbance of each solution is measured at 490 nm using a spectrophotometer. This colorful reaction is an esterase measurement expressed by means of fungi and indicates the deterioration of the plasticizer fungus. Before the evaluation by FDA analysis, the samples were also visually evaluated for fungal growth using a stereomicroscope after 1 month of incubation at 25 ° C and 95% relative humidity. Parallel experiments were also carried out on samples, which have been placed outdoors for 100 hours on an Atlas ES-25 Climameter at a cam set at 7 with a water cycle at 2 minutes, every 10 minutes and with continuous UV radiation.

The results are given in Tables 5 and 6 below. The FDA analysis of Table 5 for samples not placed outdoors at a level of 100 and 250 ppm confirms the reduction in activity against five fungi that deteriorate plastic materials with an increase in the number of carbon atoms in the chain 2 -alkyl. This is still manifested due to some loss of ABIT that has occurred in the case of the analogous lower alkyl chain during the manufacture of the samples. After placing outdoors, however, the trend is reversed and the protection against the increase of the fungus with the increase of the carbon atom index in group 2 -alkyl. This is more clearly observed at the 750 ppm ABIT level. The fungal growth trend in Table 6 is less clear although it is against a tendency to reduce activity with an increase in the carbon atom number in group 2 -alkyl. This is most clearly shown by the untreated data at 250 and 750 ppm applied from ABIT. The tendency after placing outdoors is less clear. However, when the data in Tables 1 to 6 are combined, suitable ABITs for plastic materials are compromised between high temperature stability, volatility and activity against fungal deterioration. In the case of ABITs that contain a chain 2 -alqui lo, this commitment is centered on the 2 - (ali lo of C3 _ 5) -BIT.

TABLE 5 FDA ANALYSIS Example and example Chemical concentration of the test (ppm) comparative R C | ima 100 23 750 2250 6750 8 n-propyl U sl tr - ND w ++ ++ sl ND 9 n-butyl u sl sl - ND w + ++ tr ND 10 n-pentyl- u tr - - ND w tr sl - ND 11 2 -phenyl - - ND ethyl w tr - - A ethyl or tr - - ND ++ si ++ ND G u ND sl sl - w ND + sl - H u + w ++ Control u ++ ++ Note foot of Table 5 u is untreated to the weather is treated outdoors ND without being determined G is trichloromethyl ercaptophthalimide H is oxy-bis-10, 10-phenoxarsine - is without absorbance at 490 nm tr is less than 0.1 of absorbance at 490 nm sl is 0.1-0.25 absorbance at 490 nm + is 0.25-0.5 absorbance at 490 nm ++ is greater than 0.5 absorbance at 490 nm TABLE 6 GROWTH OF HONGO Example and Chemical concentration of the test (ppm) Example R climate 100 250 300 750 2250 5 «750 Comparative 12 n-propyl u 3.3 0.0 ND 0.0 0.0 ND w 5.5 5.5 ND 3.3 0.0 ND 13 n-butyl or 1.1 1.1 ND 0.0 0.0 ND w 5.5 4.5 ND 4.5 0.0 ND 14 n-pentyl or 4.4 3.2 ND 2.3 ai ND w 4.3 4.4 ND 3.2 3.3 ND 2-phenyl-u 4.2 0.0 ND 0.0 0.0 ND ethyl 5.5 5.5 ND 3.3 0.0 ND A ethyl u 1.1 0.0 ND 0.0 0.0 ND w 5.5 3.2 ND 4.2 0.0 ND G u ND 2.2 ND 1.1 1.1 0.0 w ND 4.3 ND 2.2 1.1 0.0 H u 4.4 ND 0.0 ND ND ND w 5.5 ND 5.5 ND ND ND Control u 5.5 ND w 5.5 ND Foot of note in Table 6 Legends n, w and ND have the same meaning as in Table 5 G is trichloromethyl mercaptophthalimide H is oxy-bis-10, 10-phenoxarsine 0 is without growth in Test pieces 1 is less than 1% of the growth of the surface 2 is 1-10% of the growth of the surface 3 is 10-30% of the growth of the surface 4 is 30-70% of the growth of the surface 5 is Greater than 70% of the surface growth Example 16 a) Preparation of 2,2'-dithiodi-N- (3-methylbutyl) -dibenzamide The dithiodibenzoyl chloride (6.86 parts, 0.02 M) is added in portions with stirring at 0 to 5 ° C to a solution of isoamylamine (3.47 parts, 0.04M ex Aldrich) and triethylamine (4.04 parts, 0.04M ex Aldrich) in diethyl ether. An immediate precipitate forms. The reaction mixture is stirred for 16 hours while allowing the temperature to rise to about 20 ° C. The ether is then evaporated and the product washed with methanol (50 ml) and water (50 ml). The product is finally recrystallized from methanol as a white solid (6 parts, 69% theory, m.p. = 181-183 ° C.

Elemental analysis: Theory: C at 64.8%, H at 7.3%, N at 6.3%, S at 14.4% Found: C at 64.1%, H at 6.9%, N at 6.3%, S at 14.4% b) Preparation of 2- (3-methylbutyl) -benzisothiazolin-3 -one The ida hinge (5.7 parts, 0.0128 M) is prepared as described above, dissolved in pyridine (75 ml) and iodine (3.26 parts) , 0.0128 M) is added in portions with stirring at 20 to 25 ° C. Initially, the iodine discolors rapidly but towards the end of the iodine addition, the reaction mixture becomes yellow-brown. After stirring for an additional 2 hours at 20 to 25 ° C, the reaction mixture becomes more colorless. The pyridine is then evaporated and the product is dissolved in toluene which is washed with aqueous sodium thiosulfate followed by water to remove traces of iodine. The toluene is then evaporated giving a pale yellow oil (5.3 parts, 94% theory) which solidifies during rest. The product is recrystallized from hexane p.f. = 55-56 ° C. Elemental Analysis: Theory: C at 65.1%, H at 6.6%, N at 6.4%, S at 14.6% Found: C at 65.1%, H at 6.8%, N at 6.3%, S at 14.5% Example 17 Preparation of the 2- (l-Methylbutyl) benzisothiazolin-3-one The 2-chlorosulfenylbenzoyl chloride (6 parts, 0.029 M) is dissolved in diethyl ether (30 ml) is added in drops of 0 to 3 ° C to a stirring solution of 1 -methylbutylamine (7.36 parts, 0.84 ex Aldrich) in diethyl ether (30 ml). The reagents are stirred for 16 hours while the temperature is allowed to rise to approximately 20 ° C. The ether solution is then sieved, washed with water and dried over magnesium sulfate. After evaporation of the ether, the product is obtained as a pale yellow gum (5.5 parts, 86% theory) which gradually solidifies during rest. This is recrystallized from hexane. p.f. = 52-54 ° C. Elemental analysis: Theory: C at 65.3%, H at 7.2%, N at 6.5%, S at 14.4% Found: C at 65.1%, H at 6.8%, N at 6.3%, S at 14.5% Example 18 Preparation of 2- (1-ethylpropyl) benzisothiazolin-3 -one This is prepared in a manner analogous to that described in Example 17, except that 2 - . 2-chlorosulfonyl (6.21 parts, 0.03 M) and 1-ethylbutylamine (8.7 parts, 0.2M ex Aldrich). The product is obtained as a pale yellow gum (6.4 parts, 96% theory), which solidifies during rest. This is recrystallized from hexane p.f. = 80-82 ° C. Elemental analysis: Theory: C at 64.8%, H at 5.7%, N at 6.3%, S at 14.5% Found: C at 65.1%, H at 6.8%, N at 6.3%, S at 14.5% Example 19 Preparation of 2-cyclopentyl isothiazolin-3-one This is prepared analogously to that described in Example 17, except that 2-chlorosulfenylbenzoyl chloride (5,175 parts, 0.025M) and cyclopentylamine (8.52 parts, ÍM ex Aldrich). The product is obtained as a yellow oil (5.9 parts) which is recrystallized from hexane. p.f. = 87-88 ° C.

Example 20 Preparation of 2- (2-methylpropyl) benzisothiazolin-3-one This is prepared by the process described in Example 17, except that it uses 2-chlorosulfenylbenzoyl chloride (4.14 parts, 0.02 M) and isobutylamine (7.95 parts, 0.08 M). The product is obtained (4 parts, 97% theory) as a pale yellow oil.

Examples 21 to 25 The following bisamides of the formula A were prepared by the process described in Example 19 (a) and converted to the substituted benzoxythiazolin-3-one (BIT) of the formula B by the process described in Example 19 (b) The analytical data and melting points are given in the following Tables 7a and 7b, in which the position of the substituent R1 is given by the BIT. The 2-alkyl-BIT and 2-aralkyl-BIT, the preparation of which are described in Examples 21 to 25, have similar protection to 2-n-butyl-BIT against deterioration of plastic materials.

H? > s heard tf er to i CP

Claims (10)

1. The use of a 2-alkyl or 2-aralkyl-BIT derivative of formula 1 as a fungicide for plastic materials; characterized in that R is C3_5 alkyl or aralkyl, which contains at least two carbon atoms linking the aryl group to the nitrogen atom.

2. The use according to claim 1, characterized in that R contains 4 carbon atoms.

3. The use according to claim 1, characterized in that the BIT derivative is 2- (n-butyl) -BIT or 2-phenylethyl-BIT.

4. A composition characterized in that it comprises a plasticizer or stabilizer and a 2-alkyl or 2-aralkyl-BIT derivative of the formula 1; wherein R is alkyl or aralkyl of C3_¡-, which contains at least 2 carbon atoms linking the aryl group to the nitrogen atom.

5. The composition according to claim 4, characterized in that the plasticizer or stabilizer is in an epoxidized vegetable ester or oil.

6. The composition according to claim 5, characterized in that the ester is dioctyl phthalate, dioctyl adipate or mixtures thereof.

7. The composition according to claim 5, characterized in that the vegetable oil is a soybean oil.

8. The composition according to any of claims 4 to 7, further characterized in that it comprises a dispersant.

9. A composition characterized in that it comprises a plastic material and a 2-alkyl or 2-aralkyl-BIT derivative of Formula 1; wherein R is C3_5 alkyl or aralkyl, which contains at least 2 carbon atoms linking the aryl group to the nitrogen atom.

10. The composition according to claim 8, characterized in that the plastic material is polyurethane or plasticizing PVC.