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IndianJournal of Fibre & TextileResearch Vol. 18,March 1993, pp. 25-29

Evaluation of permethrin in industrial application on wool against trans/ucens and Anthrenus flavipes

VijayVeer" , RameshwarPrasad & K M Rao DefenceR & D Establishment,Gwalior 474 002,India Received15 May 1992; revised received 22 July1992; accepted 3 August1992

The effectivenessof permethrin in industrial applications on wool was studied againstthe larvae of Tinea translucensMeyrick (the tropical case-makingclothes ) and Anthrenus flavipes Le Conte (the furniture carpet beetle). Permethrin at 0.1% (on wool weight) was applied on fabrics at the dyeing and last scouring stages,and on wool tops at the dyeing stagein two woollen mills. Per- methrin-treated fabrics were found insectproof after 10 hand Imachine washings or 10 drycleanings or 28 days of sunlight exposure. But fabrics treated at 50-55°C and 70-75°C in the last scouring stage were not found insectproof after 10 drycleanings and 20 hand washings respectively. The treatment at higher temperatures(above 60°C) showed better exhaustionand fastnessof permethrin on the fabrics. About 1.5-10.5%of applied permethrin was lost in three and a half years storage in various climatic conditions of the country. The maximum loss of permethrin occurred in hot and high humid places.The treated fabrics and garmentswere found safeto the users.

Keywords: Anthrenus flavipes,Permethrin, Tinea translucens,Wool fabric

1 Introduction found it suitable for the insectproofing of carpets Certain species of beetle family, Dermes- which require low wet fastness. However, no such tidae (Coleoptera) and moth family, study has been carried out for fabrics which re- () are able to feed and derive nourish- quire high wet fastness, especially in Indian condi- ment from polymer like keratin. Their lar- tions. It has been observed that the effectiveness val feeding on woollen textiles and fur- and feath- of an insectproofing agent depends upon various er-lined clothing have resulted in heavy losses in factors such as the application methods and army depots as well as in industrial, commercial manufacturing processes, care claims of the fa- and domestic stores in India. For instance, brics and garments, insect species and its popula- have damaged barrack blankets worth Rs 1.4 mil- tion level, and climatic conditions!!. lion in an army depot in Kanpur. Among these In this paper, we report the results of mill trials insect species, Tinea translucens Meyrick (the with permethrin for insectproofing of woollen fa- tropical case-making clothes moth) and Anthrenus brics which are frequently cleaned and thus re- jlavipes Le Conte (the furniture carpet beetle) are quire high wet fastness. Permethrin was applied serious pests of wool2. on wool tops at the dyeing stage and on fabrics at There was no suitable chemical for durable the dyeing and last scouring stages and its fastness protection of wool fabrics and garments from in- on fabrics was studied after several washings/ sects' attacks after the ban on dieldrin (an orga- drycleanings, sunlight exposure, storage and users' nochlorine insecticide) in the seventies in India wearing. ~d elsewhere3. Subsequently, a number of chemi- cals were evaluated in various laboratories for 2 Materials and Methods their insectproofing activity of wool fabrics. Of these chemicals, permethrin (a synthetic pyreth- 2.1 Materials. ..0 ... roid) has shown, in laboratory studies4-8,a great Wool fabnc con~g 100 YoindIan VIrgm wool promise of meeting the criteria which a candidate of 40-45~ and weIghing 700 gim2 was used.. In insectproofing agent must satisfy9. In a mill trial tops dyemg treatment, scoured, carded Menno application of permethrin on carpet Byrne et aVo wool of 64s was used. , Permethrin [3-phenoxybenzyl (IR1S)-ciS"-trans- "To whomall correspondence may be addressed. 2, 2-dimethyl-3-(2, 2-dichlorovinyl)cyclopropane- -~ -.

26 INDIANJ. FIBRETEXT. RES., MARCH 1993 carboxylate] with cis/trans ratio of 40/60 was durel2 where the assessmentof fabric damage was. used in the form of a 25% (w/v) self-emulsifiable made on the basis of fabric weight loss and visible concentrate containing 7% (w/v) ionic and non- damage to the naked eyes. A fabric is considered ionic emulsifier (ethylene oxide condensate) and proofed to the larvae of textile pests if the mean .1% stabilizer in a solvent supplied by MIs Bharat w~ight loss of four test samples is less than 15 mg Pulverising Mills Ltd, Bombay. or 20 mg in anyone of the samples and/or no surface cropping and holes are visible to the 2.2 Methods 1 th . naked eyes. In control samp es, e mean welgh t 2.2.1 ApplicationofPerrnethrin to WoolFabric and loss of four samples should not be less than 35 WoolTops mg or 25 mg in a single sample. Also, not more Permethrin treatment trials were carried out at than 25% of larvae should die or pupate during two woollen mills located in Kanpur and Ludhia- the experiment of 14 days. na. Permethrin at 0.1% on wool weight was appli- ed during dyeing of wool fabric and tops and at 2.2.3 Estimationof PermethrinResidue on Wool Fabric the last scouring stage of fabric. The details of andin SpentbathLiquor permethrin treatments are given in Table 1. Be- After conditioning at 27:t 1°C and 65:t 5% RH fore adding to the treatment baths, peI:methrin for 12 h, about 10 g of permethrin-treated wool was diluted with 3 times water. This solution was material was soxhlet extracted. Extraction was added to the cold bath (40-50°C) having previ- done with 2-methoxyethanol for about 6 h at a ously wetted fabrics and tops and then circulated rate of 6 solvent exchanges/h. Permethrin was es- for 6-7 min. Lastly, dye and auxiliaries were timated using a gas chromatograph equipped with added to the dyebath and the temperature was a flame ionisation detector. The other conditions raised to boiling (90-95°C) in 30 min. Iv scouring were as follows: column-a glass column with 2% application, a permethrin premix solution was OV-17 on chromosorb W AW, DMCS, 1 metre, added to bath having previously scoured, wetted 3 rom i.d.; carrier gases flow: nitrogen -76 ml/ fabric and no detergent. The temperature of the min, hydrogen-40 ml/min, air-300 ml/min; ov- treatment bath was then raised to 70-75°C where en temp., 263°C; detector and injector temp., it was maintained for 45 min. In one set of scour- 290°C. At these conditions, the retention time for ing treatment, temperature was maintained at 50- permethrin was 250 sec and the sample analysis 55°C. The dyebath-treated material was rinsed time, 18 min. twice with water and then hydroextracted, while Permethrin from spentbath liquor was extracted the fabric treated at scouring stage was only hy- by saturating 100 ml of liquor with sodium sulph- droextracted. Dyed tops after hydroextraction ate and shaking it with 10 ml xylene fo.r 2 h. The were sun-dried for 3-4 days before spinning. organic phase was recovered and analyzed by the gas chromatograph with conditions as given 2.2.2 LarvalFeeding Test (Bioassay) above. Larval feeding tests were carried out with 10 weeks old larvae of Anthrenus flavipes and 25-27 2.2.4 Fast:nessTests days old larvae of Tin~a translucens at 27:t 1°C The hand washing and drycleaning were done and 65:t 5% RH following the standard proce- as described earlier3 and exposure to sun light

TableI-Details of permethrintreatment Treatment PerrnethrinWool-to- pH of Durationof Temp.of Permethrinrecovered on stage applied liquor bath treatment treatment % oww ratio min DC Unfinished Spentliquor Finished fabric %w/v fabric % oww % oww Fabricdyeing" 0.1 1 : 20 6 45 Boil 0.094 0.0005 0.085 Topsdyeingb 0.1 1: 30 4 45 Boil 0.071 0.0008 0.051 Lastscouring 0.1 1: 20 6 45 50-55 0.05 0.0015 0.047 0.1 1: 20 6 45 70-75 0.068 0.0008 0.064 aDye-2% MIR Zadalaon(Navy blue colour); Auxiliaries-0.5% Amolan FP, 4% Ammonium sulphate, and 1%Acetic acid. bDye-Ranolan(O.G. colour); Auxiliaries-4% Glauber salt; 2% Ammonium sulphate and 1 % Acetic acid. ""- ~-

VDAYVEER e~aL: EVALUAnON OF PERMErnRIN ONWOOL AS INSECI'PROOFING AGENT 27

was done as per the Indian standard specific- weaving processes. In fabric treatment, 9% of p.er- ations14.Machine washing was done with an auto- methrin was lost. In scouring treatment, 50-68% matic Saviour AX 303 using 0.2% neutral soap. of the applied amount of permethrin was re- covered on unfinished fabrics and slightly less 2.2.5 Toxicity of TreatedWool Material to Adults of Pest (about 2-3%) permethrin was estimated on fin- Species ished fabrics. At lower temperature (50-55°C), The toxicity of treated wool material to adults permethrin exhaustion on fabric was 50% which of Anthrenus flavipes and Tinea trans/ucens was is 18% less than that at slightly higher tempera- determined according to the method given by Bry ture(70-75°C). et aL6 where 2-3 days old 10 adults of test species Thus, about 26% more permethrin is exhausted were released in a 0.25 1 glass jar on a sample of on fabric at fabric dyeing stage than at scouring 5 cm roam which substantially covered the bot- stage. This is mainly due to the high temperature tom of the jar. The mouth of the jar was covered in dyebath which gives better penetration of per- with a piece of muslii1 cloth held by a rubber methrin into the wool fibres. In top dyeing treat- band. This w"as replicated four times. Controls ment, 20% permethrin. was lost between the un- consisted of untreated fabrics only. The jars were finished and finished fabric stages. This loss of kept in a dark cabinet at 27 :f: 1°C and permethrin may be mainly due to sun drying of 65 :f: 5% RH and the adult mortality was deter- tops. Duffield5 has also reported that about 23% mined after 24, 72 and 96 h of exposure. The of applied permethrin was decomposed in dye- jars were then returned to the holding cabinet for bath treatment. an additional 6 weeks to determine whether any Permethrin residues in spentbath liquors were adult was able to oviposit. 0.0005 and 0.0008% (w/v) for fabric and tops dyebath treatments respectively. In scouring treat- 2.2.6 StorageStability ofPermethrin on Treated Fabrics ments at 50-55°C and 70-75.°C, permethrin resi- The stability of permethrin on wool fabrics was dues were estimated to be 0.60015 and 0.008% determined by storing them for more than 3 years (by wt) respectively. in seven stores located in different parts of the . lima . d ' ..fr 3 .ras1 ., t Bess0 fPe rmethn' n onTreatedFabrics country haVIng c tic con ltions varyrng om Data on permethrin residues recovered on extreme cold to. extreme hot and mol~t to. dry. treated fabrics after various fastness tests are giv- Aged wo<:>lfabncs were .tested .b<:>thbiologically en in Tables 2 and 3. It is observed that 3ll the and cheffilcally to ~etermme their msectproofness treated fabrics were found insectproof against the and for the degradation of the compound. larvae of both the pest species after various fast- ,. .ness tests, except the 20 times washed fabric 2.2.7 Users,AcceptanceTnalo~theTreatedFa~ncs treated at scouring stage and 10 times drycleaned A .users accept~ce tnal was carned out by fabric treated at 50-55°C in scouring stage. The weanng treated ~abncs by ~e volunteers for o~e chemical analysis showed that 0.008% (owf) per- year. !he user~ ac.ceptability wa~ recorde~ m methrin was present on 10 times drycleaned and prescnbed questionalres. Used fabncs were blOas- 20 times washed fabrics (Tables 2 and 4). It is in- sayed and chemoassayed. teresting to note that a small amount of permeth- ..rin (5-8%) was lost in dyebath-treated fabrics dur- 3 Results and D~scusslon, , .ing drycleaning while the loss was 61-62% in tops A total of 6 tnals were camed ou~ m tw~ ~s. treated fabrics. This difference may be due to the Checks for the levelne~s of perm~thnn applic.allon presence of some grease in wool which absorbed were ~ade by cheffil~al analysIs <;>nun?mshed permethrin and was removed in drycleanings. The and finished wool fabncs. Pe~ethnn. residue re- same effect was also reported by Byrne et aL1°. covered on treated wool fabncs and m spentbath liquor are shown in Table 1. It is observed that in 3.2 StorageStability of Permethrin dyebath treatment, 71 and 94% of applied Fabrics treated at dyebath and scouring stages amount of permethrin was exhausted onto the were stored in 7 different stores for three and a tops and fabrics respectively, but only 51 and half years. The chemical analyses of the stored fa- 85% of permethrin was recovered on finished fa- brics showed that 1.5-10.5% of permethrin was brics in tops. and fabric treatment respectively. lost during exposure in these stores (Table 5). The Thus, the maximum loss of permethrin (about maximum amount of permethrin (8-10.5%) was 20%) was observed in tops treatment; this loss lost on stored fabrics in hot and high humid occurs mainly during sun drying, spinning and places like Jodhpur and Silcher. ---

28 INDIAN J. FIBRE TEXT. RES.,MARCH 1993

3.3 Toxicity of Treated Fabricsto Adults of PestSpecies withIn 24 h and all died within 48 h. No adult Samples of fabrics treated at dyebath and mortality of Anthrenus flavipes was observed af- scouring stages were exposed to the adults of ter 48 h exposure, but 72-100% adults were pests and the results are sbown in Table 6. All the knockdown. All adult beetle died within 96 h of adults of Tinea translucens died within 24 h of exposure. After 6 weeks exposure, no live or exposure. In case of Anthrenus flavipes, 85-91% dead larva of pest species was observed. How- adults were knockdown but no mortality was ob- served after 24 h exposure, 6-10% adults died af- ( ter 48 h exposure and all the adults died after Table 4-Bioassay of pennethrin-treatedfabric at last scour- 96 h exposure. ing stageat 50-55°C after hand washingsand drycleanings On exposure to 10 times drycleaned treated fa- brics, 72-92% adults of Tinea translucens died Fastnesstest Visible damage Wt. loss Assessment mg Cropping" Holeb Table 2-Pennethrin levels in fastnesstests on fabric treated Tineatranslucens with pennethrin (0.1% on wool weight) Nil 1 A 0.48 Proof Pennethrin(% oww)recovered on treatedfabric Hand wash Fastness 5 1 A 0.375 Proof test Fabric dyeing Tops dyeing Last scouring 10 1-2 A 5.09 Proof" Hand wash Drycleaning 5 0.072 (15.2) 0.038 (25.4) 0.039 (39) 5 1-2 A 5.57 Proof 10 0.061 (28.2) 0.028 (45) 0.036 (43.7) 10 2-3 B 15.87 Not proof 20 0.028(67) 0.012(76.4) 0.008a(87.5) Control 3-4 B-C 41.34 Machine wash 5 0.066 (22) 0.030 (41.1) 0.034 (46.8) A nthrenusflavipes 10 0.05 (41.1) 0.021 (48.8) 0.020(68.7) Nil 1 A 1.17 Proof Drycleaning Hand wash 5 0.08 (5.8) 0.0196(61.5) 0.035 (45.3) 5 1-2 A 4.51 Proof 10 0.078 (8.2) 0.019(62.7) 0.018(71.8) 10 1-2 A 4.96 Proof Sunlightexposure, . 16 weeks 0.045 (47) 0.030(41.1) 0.03 (53.1) Drycleanmg 5 1-2 A 9.91 Proof Wearingfor 10 3 B 48.20 Not proof one year 0.065 (23.5) -0.042 (34.3) Control 4 D 104.3

Figures in parenthesesshow the percentageloss of initial resi- aCropping (Surface damage): I-Not detectable; 2-Very due ofpennethrin on finishedfabric. slight; 3-Moderate; 4-Very heavy. aNot proofed against the larvae of Tinea translucensand bHole: A-No detectabledamage; B-Yarns partially severed; Anthrenusjlavipes. C- Fewsmall holes; D-Severallarge holes.

Table 3-Pennethrin residue on treatedfabric at last scouring Table 5-Pennethrin residueon wool fabricsstored in different stageat 50-55°C after hand washand drycleaning climatesof the country for threeand a half years Fastnesstest Permethrinresidue Locality Climate Pennethrinrecovered (% oww) on %oww Nil 0.047 Dyedfabric Scouredfabric Hand wash Kanpur Tropical 0.083 0.062 5 0.021 Jodhpur Hot dry 10 0.018 tropi<;al 0.078 0.061 Drycleaning Silchar Humid tropical 0.076 0.061 5 0.015 Bombay Tropical 0.082 0.062 10 0.008a Pathankot Tropical 0.079 0.063 Srinagar Temperate 0.080 0.061 aNotinsectproofed Gwalior Tropical 0.078 0.061 VUAYVEER etal: EVALUAllON OF PERMETHRIN ON WOOL AS INSECffROOFING AGENT 29

Table 6- Effect of exposingadults of Tineatranslucens and Anthrenusflavipes to wool fabricstreated at dyeingand lastscouring stagesinitially and after 10drycleanings After 24 h exposure After 48 h exposure After 96 h exposure Fabric Knockdown" Dead+ Moribundb Knockdown" Dead+ Moribundb Knockdown" Dead+ Moribundb Tineatranslucens Treatedat Dyeingstage 0 100 0 100 0 100 Last scouringstage 0 100 0 100 0 100 Dyeingstage and drycleaned10 times 8 92 0 100 0 100 Last scouringstage and drycleaned10 tinles 18 72 0 100 0 100 Anthrenusflavipes Dyeing stage 91 0 90 10 0 100 Last scouringstage 85 0 78 6 0 100 Dyeing stageand drycleaned10 times 60 0 100 0 0 100 Lastscouring stage and drycleaned10 times 35 0 72 0 0 100 aKnockdown- When adultsbecome immobilized afterexposure. bMoribund-When adults after knockdown become stationary and respond to probing by movements of legs, mouth parts or antennae.

ever, a few dead eggs of moth species were found Services, New Delhi, for help in conducting the on samples. In controls, several live larvae of both stor~ge stability tests, and to the Managers of the pest species were present. Cawnpore Woollen Mills, Kanpur, and Swadeshi

3.4 Users'Acceptance.Triai of TreatedFabrics Karyalathem to conduct (Textiles) trials Pvt in Ltd, their Ludhiana, mills. for allowing The treated fabncs were used by the volunteers ~o;- 0; year and w~re found safe. to user~. About References 3 Yoof permethrin was lost dunng weanng. 1 v ..,1.IJay veer, Pr asa d R&R ao,K MJ S tored 1': rod R es,27 .(1991) 185. 4 ConclusIon 2 Vijay Veer, PrasadR & Rao K M, Indian J TextRes, 14 Permethrin at 0.1% (on wool weight) can effect- (1989)169. ively protect the wool fabrics ana garments 3 MayfieldRJ, Text!'rog,11 (1982)1. throughout their useful life from the larval feedin 4 CarterSW&D~leld.PA,JTextInst,67(1976)77. ..g 5 DuffieldPA, PestlCSCI,8(1977) 279. ?f.Anthr~nus flavlpes and Tm~a translucens when 6 Bry R E, Simonaitis R A, Lang J H & Boatright R E, It IS applIed on tops at the dyemg stage and on fa- Soap,Cosmet Chem Spec, 52(1976) 31. brics at the last scouring stage of fabric manufac- 7 Friedman M, Ash J F, Bry R E & Sinlonaitis B, J Agric turing. However, for the treatment of fabric at the FoodChem,27(1979) 331. dyeing stage less than 0.1% oww permethrin m 8 MayfieldRJ&RussellIM,JTextInst,70(1979)53. .' ..ay 9 WaterhouseD F, Adv PestControl Res,2 (1958)207. be applIed for msectproofness when there IS no 10 Byrne K M, ShawT & SheplyJ D, J Soc Dyers Color, 97 wet process after the treatment. (1981)404. kn d 11 InternationalWool Secretariat,Technical Information Bul- Ac owle gement letinETB-3,(5)(1991). The authors are thankful to Dr R V Swamy, 12 ISO: 3998 (InternationalOrganization for Standardization), Director, and Dr P K Ramachandran, Emeritus 1977. Scientistt G' both of the Defence R & D Establish- 13 Vijay Veer, Prasad R & Rao K M, Proc, SympEntomol .., th . k . t t d Defence Services (Defence R & D Est., Gwalior), 1991, men, w all or, Lor err. een meres an con- 244. stant encouragement dunng the study. They are 14 Indian standard specificatiomIS: 686 (Indian Standards also thankful to the Director General, Ordnance Institution,New Delhi), 1957.