11 Egypt. J. Chem. 60, No. 2, pp. 161- 180 (2017) Herbal Textile Finishes – Natural Antibacterial Finishes for Cotton Fabric A. El-Shafei, M.K. El-Bisi, S. Zaghloul * and R. Refai Textile Research Division, Pre-treatment and Finishing of Cellulosic Fibers Department, National Research Centre (Scopus affiliation ID: 60014618), 33 Behooth Street, Dokki, P.O. Box 12622, Cairo, Egypt. I MPROVEMENT of physical properties in an addition to imparting antimicrobial properties to cotton fabric and modified cotton fabric by using herbal in the presence of softeners is the target of the present work, first of all modification of cotton fabric was done during cationization process by the means of cationized agent, namely, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (Quat-188); also, cotton fabric was modified during carboxymethylation process of it. Then treatments of cotton and modified cotton fabrics were carried out by different concentration of both Neem and Tulsi Extract as essential oil in the presence of Silicon Micro Emulsion (SiME) or Nonionic softeners for improving the performance of the treated fabric. Physical properties evaluations of the treated fabric were done by monitoring tensile strength, elongation, roughness, water absorbency (wettability). Finally, the treated fabrics were evaluated as antimicrobial and characterized by the mean of Scanning Electron Microscope (SEM). Keywords: Cotton, Antibacterial, Textile Finishing, Herbal, Medical textile, Essential oil. Recently, it has been observed that antimicrobial finishing of textile fabrics have a great interest in scientific researches [1-4]. Currently, a lot of materials based textile used in hospitals or hotels are conductive to cross infection or transmission of diseases caused by micro-organisms. In the textile industry, fabrics for hygienic or medical use have a great importance. Generally, imparting antimicrobial characteristics to textile materials may be done by chemical methods or by incorporating functional agents physically onto fabrics in addition to textile finishing using nano-materials [5,6]. The antimicrobial characteristics of such textile fabrics may be classified into two categories, temporarily or durably functional fabrics. It’s easy to achieve temporary biocidal properties in the finishing process of textile fabrics, but it's also easy to lose during fabrics laundering [7]. Generally, durability has been achieved by a common technology, a slow releasing technique. According to such technique, *Corresponding author e-mail: [email protected] DOI: 10.21608/ejchem.2017.541.1001 © 2017 The National Information & Documentation Center (NIDOC) 162 A. El-Shafei et al. incorporation of sufficient antimicrobial agents onto fabrics may be done by the process of wet finishing. Deactivation of bacteria by slowly releasing the biocide from the substances will be done by the treated fabrics. However, if the antibacterial agents are impregnated in materials without covalent bond linkages it will be completely vanish. Many successful examples of chemically incorporated technique have been noted. In the textile industry, cotton is widely utilized due to its super properties. The final step of chemical process is the finishing process, improving quality and serviceability of materials. Textile softening considered one of the most important finishing processes of many after treatment steps in a fabric chemical processing industry [8]. Silicon finishes consider one of the most important softeners which are recognized as the best finishing agents for improving the fabrics softening, increasing textiles aesthetic feel and also imparting best hand softening. Silicon finishes have many advantages as it has been responsible for imparting softening to textile over the years, in addition to producing the optimum handle for apparel textiles with comfort characteristics [9,10]. Presented an interesting challenge amino silicon is known for imparting extremely soft handle properties. Nowadays, amino silicon elastomers consider one of the most efficient softeners in textile finishing field. In the application of such amino softeners onto fabrics, these amino groups are belongs to cationic species that have attraction ability to the negatively charged fabric. This fact is true for fabrics based cotton, because it demands a negatively charged surface in aqueous medium, leading to improve performance, deposition and durability of softener coating [11]. There is very important demand for antibacterial fabrics based on eco-friendly agents which not only associated because of microbial growth on fabrics. The utilization of the products of natural herbal such as Eucalyptus, aloe Vera and leaf of tulsi......etc as antimicrobial agent for imparting antibacterial properties to textile fabrics is very limited. Natural herbals can be exploited as an attractive eco-friendly instead of synthetic antimicrobial agents for textile application due to its low cost and its lower incidence of adverse reactions compared with synthetic agents. The cotton clothes, by virtue of its characterization and proximity to human skin, provide perfect medium for the adherence, propagation and transfer of infection causing microbial species, in cases where work wears are worn, in places e.g. food industry, clinics, hospitals, and hygiene as bullies and elders wears who need more care. The presence and also growth of such microorganisms can lead to problem of elder health, and textile deterioration [11]. Egypt. J. Chem. 60, No. 2 (2017) Herbal Textile Finishes – Natural Antibacterial … 163 As we know, the additives applied to fabrics may be attacked by microbes in addition to such fabrics can lose its functional properties e.g. tensile strength, color strength and elasticity, so a special type of finishing agent which may called antimicrobial finishing is required to overcome the deleterious effect of microorganisms on fabrics. Hence, these is an urgent demand for antibacterial fabrics based on eco-friendly natural agent which help for reducing effectively the ill effects associated cause by the growth of microbes on fabrics in addition to comply with the requirements imposed by regulating agencies [12]. Essential oils and plant extracts are included to natural biocides which may be used in textile as antimicrobial finishing because it play an even growing role and widely known for fungicidal and bactericidal [13]. Natural antimicrobial agents have many advantages because it has non toxic nature and non-allergenic and do not lead to microbial resistance problems. Neem consider one of the richest source of antimicrobial compounds, neem leaves yield glycerides of saturated and also unsaturated fatty acids, stearic and oleic acid are the main fatty acid [14]. Leaves mainly yield quercetin and neem bacterial as well as a number of liminoids. Quercetin is known to have anti- malarial, antifungal, antibacterial and antiviral properties. This may perhaps account for curative properties of leaves for scabies and sores. Medicinal effect derived from neem in effective against skin diseases, cough and breathing problem. Tulsi (Ocimum sanctum) are belongs to labiates family which consist of leaves ocinum santumlin. From ancient times leaves of tulsi are used as an antimicrobial, insecticidal diaphoretic. It has suitable antimicrobial activity for textile materials application. The main chemical constituents of tulsi are: ursolic acid, rosmarinic acid, oleanolic acid, eugenol, carvacrol, linalool, and β- caryophyllene these essential present in the tulsi is responsible for its anti-viral and antibacterial properties [15]. The aim of the present work was focused at investigating the performance of silicon micro emulsion and nonionic softener-in the presence of oil of the herbal like tulsi and neem extract. The essential oil of the herbal products imparts cotton based clothes one or more functional properties in addition to its own softening functions in one step process, these functions as antibacterial activity (oil property) and smoothness(softening agent property). Herbal oil used due to their lesser toxicity and better antimicrobial activity for treating various infectious diseases. The treated fabrics will monitor for physical-chemical properties like, tensile strength and elongation at break, surface roughness, wettability, and antimicrobial activity. Selected samples will subject to SEM. Egypt. J. Chem. 60, No. 2 (2017) 164 A. El-Shafei et al. Materials and Methods Cotton fabric Mill desized, scoured and bleached cotton fabric, plain weave, supplied by El-Nasr Company for spinning weaving and Dyeing El-Mahallah El-Kubra, Egypt. The fabric was further purified in the laboratory by washing at 100oC for 60 min using a solution containing 2 g/L, Na CO and 1 g/L, non-ionic 2 3 surfactant. The fabric was then washed several times with boiling water then with cold water and finally dried at ambient conditions. Chemicals Sodium hydroxide, acetic acid, hydrochloric acid, monochloroacetic acid and sodium carbonate were of laboratory grade chemicals. 3-chloro-2- hydroxypropyl trimethyl ammonium chloride (69%), of technical grade chemicals was kindly supplied under the commercial name Quat-188 by Aldrich, amino functional silicon softener, micro emulsion (SiME) and nonionic softener was kindly supplied form by Tex Chem Egypt Co., Ltd. The Carboxymethylation of cotton fabric (CMC) Cotton fabric was partially carboxymethylated (CMC) by a method similar to those previously reported [16]. Hence, bleached cotton fabric samples were impregnated with 15 wt. % aqueous NaOH for 5 min at room temperature followed by squeezing to a wet pick up of 100% then dried at 60oC for 5 min. The alkali treated samples were steeped in aqueous solution of ammonium salt of monochloroacetic acid (0-3 mol) for 5 min at room temperature. These samples were then squeezed to 100% wet pick up, sealed in plastic bags and heated at 80 oC for 1 h then washed and dried at room temperature. Cationization of the cotton fabric Cationization of cotton fabric was carried out using pad-dry-cure method. Experimental procedure adopted was as follows, Quat-188 (3-chloro-2- hydroxyl propyl-trimethyl ammonium chloride was mixed in solution with sodium hydroxide. Cotton fabric was padded through this mix and squeezed to wet-pick up of 100%. The fabric was dried at 40oC for 15 min and then cured at 120oC for 15 min. At the end, the sample was washed with water and 1% acetic acid then washed several times with water and finally dried at ambient conditions. Fabric treatment The untreated cotton, carboxymethyl cotton and cationized cotton fabric were padded twice to about 100% wet pickup with an aqueous formulation containing either 5% of silicon micro emulsion or 5% nonionic softener in presence of 5, 10, 15 % of either neem extract or tulsi oil for both softener separately, (Homogenizer was used to get homogenous solution) followed by drying at 100oC for 5 min and curing 140oC for 3 min in a circulating air oven. The treated fabric samples were then washed in with 2 g/L Egyptol to remove excess and unfixed reactants as well as products and dried at room temperature. Egypt. J. Chem. 60, No. 2 (2017) Herbal Textile Finishes – Natural Antibacterial … 165 The treated fabrics characterization was investigated by SEM and in additional to its antibacterial properties. Testing and analysis Antimicrobial activity The antimicrobial activity of the treated fabrics was examined on staphylococcus aureus, and Escherichia coli, by antimicrobial agar diffusion test according to AATCC Test Method 147-1988. Wettability: was assessed in terms of drop disappearance, measured by allowing a drop of water to fall on the sample recording the time required for drop disappearance (AATCC standard test method). Roughness: was measured according to AATCC standard test method using a Surfacoder (1700a). Scanning Electron Microscopy (SEM): was studied using a scanning electron probe microanalyzer (type JXA-840A) – Japan. Tensile strength Tensile strength of the fabric samples was determined by the ASTM Test Method D5035. A Q-Test 1/5 tensile tester was used. Three specimens for each treated fabric were tested in the warp direction and the average value was recorded to represent the fabric breaking load (Lb). Results and Discussion Effect of the Neem extract concentration on the performance of the treated fabric in presence of SiME Table 1 shows the effect of different concentrations (0-15%) of neem extract in formulation bath containing SiME softener with concentration 5% on physical properties of blank and modified cotton fabric such as tensile strength, elongation at break, roughness and wettability it is observed that there is no significant change in tensile strength for the cationized cotton compared with CMC, and cotton fabric. All of substrates have improvements in its elongation at break. The roughness was improved by change neem extract concentrations which accompanied by an improvement in the surface roughness at same SiME concentrations this may be related to increasing the surface negativity for the reaction of carboxymethylation which results in an increase adhesion of the fabric. Silicon as finishing agent also imparts textiles soft feeling and water repellent properties, such water repellency character is attributed to methyl groups which are oriented and attracted to the fiber surface via silicon links. Egypt. J. Chem. 60, No. 2 (2017) 166 A. El-Shafei et al. TABLE 1. Effect of concentration of Neem extract in the presence of SiME. Neem Conc Cotton CMC Cationic % 0 5 10 15 0 5 10 15 0 5 10 15 Tensile 77 73 75 76 74 75 75 73 70 70 70 69 strength(kg) Elongation 20 18 15 14 28 26 26 26 18 16 16 16 at break (%) Roughness 17.6 17.3 16.0 16.0 20.0 16.9 15.9 15.0 17.0 16.3 15.0 15.0 (μm) Wettability < 3 < 3 < 3 < 3 < 3 < 3 < 3 < 3 <3 >3 >3 >3 (Sec) Also there’s no change in the wettability with changing neem extract concentrations for untreated and CMC cotton from the blank cotton, but the cationized cotton fabric, wettability decreased (more than 3 seconds), this is due to the hydrophobic character of the deposited silicon film onto the treated cationized fabric [17] and also for the adsorbed organic molecules of the neem extract on the fabric [18]. The antibacterial properties of the fabric treated with Neem Extract in presence of SiME softener Figure 1 shows the effect of neem extract concentration 15g/L on the antibacterial properties of the treated fabric expressed as inhibition zone diameter in presence of silicon micro emulsion for gram +ve bacterial (staphylococcus aureus) and gram -ve (Escherichia coli). The antibacterial activity for the CMC is higher than the other cationized cotton or blank fabric, this is due to: (1) The presence of SiME molecules would certainly open up the structure of cotton there by establish better adsorption of neem extract particles. (2) Hydrophobicity of these molecules by virtue of their carboxylic group enhances the swell-ability of cotton fabric and, therefore, diffusion and adsorption of neem extract. Egypt. J. Chem. 60, No. 2 (2017) Herbal Textile Finishes – Natural Antibacterial … 167 Fig.1. The Antibacterial properties of cotton fabric and modified cotton fabric treated with Neem oil in presence of SiME. Effect of Tulsi oil concentration of on the performance of the treated fabric in presence of SiME Table 2 shows the effect of change in concentration of tulsi as essential oil on the performance of cotton fabric and modified cotton fabric at same concentration (5%) of SiME. The tensile strength and elongation at break decrease with increasing the concentration of tulsi oil for the cotton fabric, CMC and also for the cationized fabric. There is no change in the roughness of both cotton and cationized cotton fabric, but there were some improvement in the roughness of CMC which can be attributed to the concept that the amino silicon can form a hydrophilic film on the fabric and reduce the surface roughness [17]. Egypt. J. Chem. 60, No. 2 (2017) 168 A. El-Shafei et al. TABLE 2. Effect of concentration of Tulsi extract in the presence of SiME. Cotton CMC Cationic Tulsi Conc 0 5 10 15 0 5 10 15 0 5 10 15 Tensile 77 65 63 60 74 70 68 64 70 67 64 61 strength(kg) Elongation 20 18 16 16 28 24 23 23 18 17 17 16 at break (%) Roughness 17.6 17.5 17.4 17.3 20 17.9 15.5 14.9 17 17 17.6 17.5 (μm) Wettability <3 <3 <3 <3 <3 >3 >3 >3 <3 >3 >3 >3 (Sec) For the wettability, it is clear that the wetting property of the treated fabric with tulsi oil is less than the untreated fabrics. This is due to adsorbed organic molecules of the tulsi oil on the fabric and also for the hydrophobic character of the deposited silicon film onto the treated cotton [17]. Antibacterial activity of the treated fabrics in presence of tulsi oil and SiME softener Figure 2 shows the antibacterial activity of the treated fabrics in presence of tulsi oil and SiME softener it was found that all treated fabrics display antibacterial activity regarding both Staphylococcus aureus and Escherichia coli, and cotton fabric display antibacterial activity (14.5 mm) greater than both CMC (13 mm) and cationic fabric (9.5 mm) regarding Escherichia coli (G -ve) and also cotton fabric and CMC treated fabric have higher antibacterial activity (17 mm) regarding Staphylococcus aureus (G +ve) compared with cataionic fabric (16 mm). It was indicated in research that the agents of antibacterial attach to the surface of fiber by bond formation and then deactivate the cell membrane of microorganisms during ionic and physical phenomenon [19]. In addition, such antibacterial agent penetrates and deactivates the cell wall of the microorganisms via electron chemical mode of action, resulting in the leakage of metabolites that can probably inhabit the reproducing or functionalizing of microorganisms [20]. Egypt. J. Chem. 60, No. 2 (2017) Herbal Textile Finishes – Natural Antibacterial … 169 Fig 2. The antibacterial activity of the treated fabrics in presence of tulsi oil and SiME softener. Egypt. J. Chem. 60, No. 2 (2017) 170 A. El-Shafei et al. Effects of the Neem extract concentration on the performance of the treated cotton fabric in presence of Nonionic softener Table 3 shows that increasing the neem extract concentration from (5-15 %) in the presence of 5% concentration of non-ionic softener is accompanied by decreasing of tensile strength and elongation at break for cotton fabric and modified cotton fabric. Table 3 also shows that, by increasing the neem extract there was be an improvement on the fabric roughness for the CMC fabric which not attributed for the cotton and cationized cotton. The treatments of CMC fabric with nonionic softener/neem extract lead to improvement of the surface roughness and homogenously all grooves and ditches were covered. This may be explained by the mean of carboxymethylation reaction which leads to increase surface negativity of the fibers causing highly adhesion with nonionic softener/ Neem extract. TABLE 3. Effect of Neem concentration on the performance of the treated cotton fabric in presence of non-ionic softener. Cotton CMC Cationic Neem Conc 0 5 10 15 0 5 10 15 0 5 10 15 Tensile strength 77 61 62 64 74 63 63 66 70 59 57 54 (kg) Elongation at 20 16 16 16 28 23 23 16 18 16 16 17 break (%) Roughness (μm) 17.6 18 18 17 20 17.3 16.5 15.8 17 17.6 17.1 17.5 Wettability (Sec) <3 <3 <3 <3 <3 >3 >3 >3 <3 <3 <3 <3 Table 3 shows decreasing of the wettability for the cotton and cationized cotton, this is may be due to adsorption of the organic molecules in the Neem extract on the fabric and the hydrophobic film of nonionic softener as previously noted. But the wettability is increase for CMC fabric due to hydrophobicity of their carboxylic groups leading to enhancement the smell- ability of cotton fabric. Figure 3 shows the antibacterial activity based on inhibition zone for S. aureus and E-Coli, It was found that for S-aureus inhibition zone for CMC is higher (12.5 mm) compared with both the cotton fabric (2.5 mm) and cationized fabric (3.5 mm). But regards E-Coli it was found that both cotton fabric and cationized fabric which was treated with the neem extract did not affected and doesn’t show antibacterial activity against E-coli compared with CMC which show antibacterial properties with 9.5 mm inhibition zone. Egypt. J. Chem. 60, No. 2 (2017)