Two-step durable press treatment of cotton fabric

In this paper cotton fabrics were treated by two different methods with polycarboxylic acids (citric acid and butanetetracarboxylic acid) for durable press performance. The first was a two-step method in which the fabric was initially treated with citric acid and then treated by butanetetracarboxylic acid. The other was a mixed method in which the fabric was treated with a solution containing the two mixed polycarboxylic acids. Following the treatments, the wrinkle recovery angle, strength and strength retention of the resulting fabric were measured and compared.     

Improving the antibacterial activity of cotton fabrics finished with triclosan by the use of 1,2,3,4‐butanetetracarboxylic acid and citric acid

For producing antibacterial textiles, the conventional finishing processes have high productivity and low processing costs, but textiles finished in these ways exhibit low durability against laundering. Therefore, cotton fabrics were bleached with hydrogen peroxide, finished with triclosan, and then treated with polycarboxylic acids such as 1,2,3,4‐butanetetracarboxylic acid (BTCA) and citric acid (CA) as crosslinking agents to provide durable antibacterial properties. The surface of fibers treated with BTCA had a greater crosslinked area, and the surfaces of fabrics treated with CA were exposed to greater amounts of deformation due to the mechanical and chemical influences after 50 launderings. The bleaching and finishing treatments did not dramatically affect the breaking strength. However, the polycarboxylic acid treatment (both BTCA and CA) alone showed reductions in the breaking strength when the acid concentration was increased. The polycarboxylic acids were fairly effective against both bacteria, even at lower concentrations, when they were applied to stand‐alone cotton fabrics, whereas the antibacterial activity decreased somewhat after the use of polycarboxylic acid and triclosan in the same recipes. Adding polycarboxylic acids to the antibacterial finishing recipes enhanced the durability after 50 launderings, and the durability of the recipes containing BTCA was much higher than that of the recipes containing CA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Application of polycarboxylic acid sodium salt in the dyeing of cotton fabric with reactive dyes

In this study, the effects of polycarboxylic acid sodium salt on the dyeing of cotton with reactive dyes were evaluated by measuring and comparing the K/S values and dyeing fastnesses of the dyed cotton fabric samples. Results showed that the K/S value and dyeing fastness of cotton fabrics dyed with polycarboxylic acid sodium salt, substituting inorganic salts as exhausting agent were close to that of with sodium chloride when dip‐dyeing process was used. While, in pad‐dry dyeing, the K/S value of cotton fabric samples dyed with polyacid salts as exhausting agent was higher than that of with sodium sulfate, and the dyeing fastnesses of these samples were nearly the same. The dyeing mechanism of cotton fabric with reactive dye, using polycarboxylic acid sodium salt as exhausting agent was analyzed. The dyeing exhausting mechanism of reactive dye seems different when the inorganic salt and polycarboxylic acid sodium salt were used as exhausting agent in the dyeing of cotton fabric with reactive dye. The polycarboxylic acid sodium salt, as weak electrolyte, increased the dye‐uptake of reactive dye on cotton fabric not only by screening negative charges on cotton surface, but also by the effect of salting‐out or hydrophobic combination. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Factors affecting the dyeability of cotton crosslinked with polycarboxylic acid

Improved dyeing properties of cotton crosslinked with polycarboxylic acids are produced by addition of reactive nitrogenous additives, such as alkanolamines and hydroxyalkyl quaternary ammonium salts, to the treatment formulation. Both N-methylolamides and polycarboxylic acids are effective for crosslinking cotton and bonding reactive nitrogenous additives to the cellulosic substrate, but dyeing characteristics of the finished fabrics are very different. In this study, the influence of the reactive additives and dyebath pH on the colour yields of cotton crosslinked with polycarboxylic acids and then dyed with anionic dyes were determined. Emphasis is on the dyeing properties of cotton finished with 1,2,3,4-butanetetracarboxylic acid or citric acid non-formaldehyde crosslinking agents, and alkanolamine hydrochloride or hydroxyalkyl quaternary ammonium salt additives.     

Polycarboxylic acids as crosslinking agents for grafting cyclodextrins onto cotton and wool fabrics: Study of the process parameters

In this paper we describe a new method for the grafting of cyclodextrins (CDs)onto cotton or wool fabrics. The novelty principally concerns the chemical approach of the grafting reaction that was carried out in the presence of polycarboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid, citric acid, or polyacrylic acid. All types of native or CD derivatives could be used successfully as long as they carried enough remaining hydroxyl groups. For example, the amount of native β‐CD fixed onto the fabrics increased up to 12% in weight, whereas this value decreased to only 3% for the randomly methylated derivative of β‐CD (RAMEB). We observed that phosphorous salts, such as sodium mono‐ and dihydrogen phosphate or sodium dihydrogen hypophosphite, catalyzed the reaction. On the other hand, the conventional and convenient pad–dry–cure technique that is currently used at the industrial scale in textile processing was applied. We report that the polycarboxylic acids play the role of linking agent through an esterification (or amidification) reaction with the OH (or NH₂) groups of both CD and cotton (or wool) fibers. In addition, this reaction could lead to the graft of a copolymer formed between CD and the polycarboxylic acid. The reaction yield depends on the concentration and nature of the aforementioned reactants and catalysts and on the curing conditions (time and temperature). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1449–1456, 2002     

Infrared spectroscopy studies of cyclic anhydrides as intermediates for ester crosslinking of cotton cellulose by polycarboxylic acids. IV. In situ free radical copolymerization of maleic acid and itaconic acid on cotton

Polycarboxylic acids have been used as crosslinking agents for cotton fabrics and paper to replace the traditional formaldehyde‐based reagents. Previously, we found that a polycarboxylic acid esterifies cotton cellulose through the formation of a five‐membered cyclic anhydride intermediate. Both maleic acid (MA) and itaconic acid (ITA) are extremely difficult to polymerize under conditions normally used for free radical polymerization. It has been reported in the literature that treatment of cotton fabric with a mixture of MA and ITA significantly improved wrinkle‐resistance of the fabric. In this research, we investigated the in situ copolymerization of MA and ITA on cotton fabric. Fourier transform‐infrared spectroscopy was used to study the anhydride carbonyl formed on the cotton fabric treated with the mixtures of MA and ITA. A redox titration technique also was applied to determine the quantity of alkene double bonds on the treated fabric. It was found that free radical copolymerization of MA and ITA does not occur on the fabric at elevated temperatures when potassium persulfate is present as an initiator. It does occur, however, when both potassium persulfate and sodium hypophosphite are present on the fabric. The in situ copolymerization on the cotton fabric probably is initiated by a reduction–oxidation system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 327–336, 2000     

Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

柠檬酸抗皱整理对苎麻织物染色性能的影响

研究了多羧酸与纤维素分子的酯化反应机理和酒石酸钠的催化反应机理,探讨了酒石酸钠作非磷催化剂,柠檬酸抗皱整理工序对苎麻织物染色性能的影响,先染色后整理筛苎麻织物的抗皱性能、染色性能均较好。     

GMA改性磷酸腺苷的制备及其对棉织物的阻燃整理

为了提高磷酸腺苷单体在棉织物上的接枝改性程度及其阻燃效果，采用甲基丙烯酸缩水甘油酯（GMA）对一磷酸腺苷（AMP）、二磷酸腺苷（ADP）、三磷酸腺苷（ATP）进行改性，制得三种带有不饱和双键的阻燃单体AMP-m-GMA、ADP-m-GMA、ATP-m-GMA；然后通过紫外光接枝法将三种阻燃单体分别接枝到棉织物上，制备光接枝AMP-m-GMA、ADP-m-GMA和ATP-m-GMA阻燃棉织物；对三种阻燃单体进行了结构表征和热稳定性分析，并探究了三种阻燃单体光接枝阻燃棉织物的热稳定性、阻燃性能、燃烧行为和残炭结构。结果表明，三种磷酸腺苷通过GMA环氧基开环引入不饱和双键，且具有良好的热稳定性。相比于原棉织物，三种阻燃棉织物的最大热降解速率分别降低了60.0%、52.0%、60.0%，极限氧指数由16.1%分别提升到25.4%、27.4%、26.4%，织物热释放速率分别下降了15.09%、60.47%、37.82%，说明三种磷酸腺苷阻燃单体均有助于棉织物形成致密炭层，阻止热量扩散，获得良好的阻燃效果。其中，光接枝ADP-m-GMA阻燃棉织物的增重率可达22.4%，燃烧后损毁长度由30 cm缩短至14.2 cm，表现出更优异的阻燃性能。     

Thermal characteristics of unsaturated dicarboxylic acid durable press finishing systems

Thermoanalytical (TA) studies including differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses were carried out to measure characteristics of dried mixtures based on two unsaturated polycarboxylic acids. Model 9% treatment (pad) solutions of maleic (M) and/or itaconic (I) acid, with and without potassium peroxydisulfate (K) as the free-radical initiator, were prepared with sodium hypophosphite (H) as the catalyst and vacuum oven-dried. DSC thermograms varied with each component; even the presence of a small amount of component K was evident. TG residue production and maximum rates of weight loss were the most useful thermal parameters. Residue/rate factors, used previously as predictors, were calculated. Previous studies indicated that high residues and low rates were indicators of combinations of reactants that resulted in good durable press treatments for fabrics. Residue/rate factors were used to rank the six mixtures that reflect actual fabric treatment combinations: MH, IH, MIH, and those same three with the initiator present. Rankings indicated that the presence of the initiator significantly increased the residue/rate factor for IHK and for MIHK. The presence of the initiator appears more beneficial to itaconic acid than to maleic acid. The rankings by the TA predictor agreed with textile properties measuring appearance and strength. © 1994 John Wiley & Sons, Inc.     

PREPARATION AND UTILIZATION OF CARBOXYL-CONTAINING CATION EXCHANGE CELLULOSE

A cation-exchange resin was synthesized by esterification of cellulose fibers, with α-hydroxy polycarboxylic acids (citric acid (CA), malic acid, or tartaric acid) in presence of sodium hypophosphite (SHP) as an esterification catalyst, followed by curing at high temperature. Factors affecting the reaction such as CA concentration, CA/SHP molar ratio, curing conditions (temperature and time), type of polycarboxylic acid, and type of cellulose substrate were studied. Reaction conditions were selected to prepare cation-exchange resins (cotton/CA), (jute/CA), (viscose /CA) having a carboxyl content of 132, 114, 112 meq/100 g, respectively. Potentiometric titration of the treated substrates reveals that they are weak cation exchangers having strength values (pK _a) of 5.6, 6.3, and 5.8 for cotton, viscose, and jute, respectively. Factors affecting the adsorption of some textile industry pollutants such as a basic dye or cupric cations by the prepared cation exchangers were investigated. The removal percent of these pollutants remarkably increases by increasing the pH (up to 10 in case of the dye and up to 6.7 in case of cupric ions after which precipitation of cupric hydroxide takes place).     

Use of lipoprotein lipase in the improvement of some properties of wool fabrics

Wool fabrics were pretreated with hydrogen peroxide in the presence of different stabilisers; namely, sodium silicate, magnesium sulphate and imino disuccinic acid sodium salt. The effect of stabiliser type and concentration on the properties of the treated wool were studied. Imino disuccinic acid sodium salt was found to be the most effective stabiliser for hydrogen peroxide when added to the bleaching bath of wool fabric. The effect of after‐treatment of the pre‐oxidised wool fabric with commercially produced lipoprotein lipase enzyme on its dyeability with acid and reactive dyes, as well as on some of its physico‐mechanical properties, was assessed. Chemical and microscopic analyses were conducted to assess changes in the chemical composition of wool treated with this system. Wool fabrics treated with hydrogen peroxide/imino disuccinic acid sodium salt/lipoprotein lipase enzyme exhibit improved wettability and, hence, dyeability with both acid and reactive dyes, as well as enhanced resistance to felting shrinkage and pilling, without severe deterioration in the fabric’s inherent properties.     

Infrared spectroscopic studies of the nonformaldehyde durable press finishing of cotton fabrics by use of polycarboxylic acids

A number of polycarboxylic acids have been used successfully as new nonformaldehyde cross-linking agents for cotton fabrics. In our previous research, Fourier transform infrared photoacoustic spectroscopy (FTIR/PAS) demonstrated the ability for characterizing ester cross-linkages in the finished cotton fabrics. In this research, the effects of different acid concentrations, different catalyst concentrations, different curing temperatures, and different curing times on the ester cross-linking of the cotton fabrics were determined by FTIR/PAS. The infrared spectroscopic data were also correlated to durable press (DP) ratings. FTIR appears to be useful for evaluating the effectiveness of polycarboxylic acids as cross-linking agents for cotton fabrics. FTIR definitely complements the existing methods for evaluating finished textile fabrics.     

Fastness and dyeability improvement of wool fabric pretreated with oxalate derivatives

Wool fabrics were pretreated with calcium and sodium oxalate in acidic and alkaline pH media. The pretreated and untreated fabric samples were then dyed in the same bath with acid dyes by the exhaustion technique. The pretreated fiber sample surfaces were observed using a scanning electron microscope. The color strength and fastness properties of the fabrics were investigated. The results of the study showed that pretreatment with oxalate derivatives can be used as a means of improving the dyeability of wool fibers. As the dyed, pretreated wool fabrics had higher color strength and fastness results than the untreated wool fabrics, the mechanical properties were affected negatively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Citric Acid Used as a Cross-Linking Agent for Grafting β-Cyclodextrin onto Wool Fabric

Modification of woolen fabrics were achieved by grafting β-cyclodextrin and β-chloro triazinylcyclodextrin in the presence of citric acid (CA) as cross-linking agent and phosphorous salts such as sodium hypophosphite (SHP) and sodium dihydrogen phosphate (SDP) using the pad dry cure technique. CA is expected to react with the β-CD (or wool) hydroxyl groups and wool terminal amino groups, to form ester cross-linkages or ionic bonds. The improved properties of wool fabrics were evaluated using urea bisulfite solubility test, tensile strength, elongation and crease recovery angle. Also, yellowness index and scanning electron microscopy were performed. Woolen fabrics treated with CA alone and CA/ CD shows antimicrobial properties.     

Cation exchange finishing of nonwoven polyester with polycarboxylic acids and cyclodextrins

We describe a chemical method for the finishing of polyester nonwoven fabrics that aimed to obtain ion exchange textiles. This approach was based on the use of polycarboxylic acids (PCA) and cyclodextrins as carbohydrate compounds and finishing agents, respectively. It was observed that the reaction between these reactants yielded a crosslinked polymer that was physically anchored onto the fibers. This polymer can be considered as a resin issued from the esterification between the COOH groups of the PCA with the OH groups of the carbohydrate. As the esterification reaction was not complete, many free carboxylic groups remained on the surface of the coating polymer. This feature offered the ion exchange properties to the textile support. In this article, we described the pad‐dry‐cure process and showed the influence of the curing parameters (time and temperature), the nature, and the concentration of the components and the pH of the impregnating bath. The grafting rate (in wt %) and the ion exchange capacity (IEC) were observed in parallel. First, it was observed that the best IEC capacity (that could reach 1 mmol/g) was obtained when an ideal compromise was applied between time and temperature of curing. We also evidenced that IEC depended on the nature and on the concentration of the PCA (chosen among citric acid, 1,2,3,4‐butanetetracarboxylic acid, and polyacrylic acid) and on the pH of the impregnating bath. Finally, it was observed that cyclodextrins were more appropriate than starch as finishing coreactants. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3730–3738, 2007     

Physical properties of crosslinked cellulose catalyzed with nano titanium dioxide

Four different carboxylic acids, 1,2,3,4‐butane tetracarboxylic acid (BTCA), maleic acid (MA), succinic acid (SUA), and citric acid (CA), were used as crosslinking agents to treat cotton fabrics in the presence of nanometer titanium dioxide (TiO₂) as a catalyst under UV irradiation. The dry crease recovery angle (DCRA) and wet crease recovery angle (WCRA) values of the treated fabrics were ranked BTCA > MA > CA > SUA and the tensile strength retention (TSR) values were ranked BTCA < MA < CA < SUA at a given resin concentration, catalyst concentration, and irradiation time period. The physical properties of the treated fabrics for nanometer silver/nanometer titanium dioxide (Ag/TiO₂) catalyst showed the same tendency. At a given DCRA, the WCRA values were ranked in the order BTCA ≒ MA > CA ≒ SUA; and at a given value of the TSR, the WCRA and DCRA values were both ranked in the order BTCA > MA > CA > SUA. The softness values of the carboxylic acid treated fabrics in the presence of nanometer TiO₂ catalyst were all better than that of the untreated fabric. Surface deposition of the treated fabrics for BTCA, which contains one vinyl double bond and four carboxylic acid groups, was higher than that for CA, which contains no vinyl double bond. IR spectra and electron spectroscopy for chemical analysis survey spectra showed the ester bond crosslink between the cellulose molecule and the various acids used in this study. The values of DCRA, WCRA, and add‐on of the CA crosslinked fabrics for the mixed catalysts were in the order ZrO₂/TiO₂ < SiO₂/TiO₂ < Ag/TiO₂. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2450–2456, 2005     

Proper finishing treatments for sun‐protective cotton‐containing fabrics

To enhance both the performance and ultraviolet‐protection properties of cotton‐containing fabrics, attempts have been made to use poly(carboxylic acid)s as non‐formaldehyde durable‐press finishing agents alone or in combination with certain additives followed by posttreatment with metal salt solutions. Furthermore, simultaneous dyeing and resin finishing in the presence of triethanolamine hydrochloride (TEA · HCl) or citric acid (CA) as a reactive additive along with different anionic or cationic dyestuffs have been examined. The results reveal that the ester crosslinking of cotton‐containing fabrics in the absence or presence of chitosan (5 g/L), β‐cyclodextrin (20 g/L), or choline chloride (20 g/L) as an additive results in an improvement in the fabric resiliency as well as the ultraviolet‐protection properties. The extent of the improvement is determined by the type of poly(carboxylic acid), type of additive, type of substrate (i.e., cotton or cotton/polyester blend), and pretreatment history (i.e., grey, bleached, or bleached and mercerized). The posttreatment of easy‐care finished fabric samples with a copper acetate solution (5 g/L) results in a dramatic improvement in the ultraviolet‐protection factor, especially with bleached cotton, grey cotton/polyester blend, and bleached cotton/polyester fabric samples, regardless of the additive. Simultaneous dyeing and resin finishing with Reactive Black 5 and Direct Violet 31, in the presence of TEA · HCL as a reactive additive, or with Basilene Red PB, in the presence of CA as a reactive additive, result in a sharp increase in both the depth of shade and the ultraviolet‐protection values, regardless of the substrate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1024–1032, 2005     

Formation of five-membered cyclic anhydride intermediates by polycarboxylic acids: Thermal analysis and Fourier transform infrared spectroscopy

Butanetetracarboxylic acid (BTCA) has been used as the most effective nonformaldehyde crosslinking agent for cotton and wood pulp cellulose. Our previous research has indicated that a polycarboxylic acid esterifies cellulose in two steps: the formation of a five-membered cyclic anhydride intermediate by the dehydration of two adjacent carboxyl groups, and the reaction between cellulose and the anhydride intermediate to form an ester linkage. In this research, we investigated the formation of carboxylic anhydrides by BTCA and other polycarboxylic acids in powder forms, and as finishes applied to cotton fabric using thermal gravimetry, differential scanning calorimetry, and Fourier transform infrared spectroscopy. We found that BTCA and other polycarboxylic acids in powder forms start to form five-membered cyclic carboxylic anhydrides when the temperature reaches the vicinity of their melting points. The formation of carboxylic anhydride is accelerated above the melting points. We also found that BTCA forms anhydrides at lower temperatures when it is applied to cotton fabric as a finish. An increase in temperature increases both the amount of anhydride and the amount of ester formed on the cotton fabric. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2711–2718, 1998     

Novel feature of nano‐titanium dioxide on textiles: Antifelting and antibacterial wool

In this study, the antifelting and antibacterial features of wool samples treated with nanoparticles of titanium dioxide (TiO₂) were evaluated. To examine the antifelting properties of the treated samples, the fabric shrinkage after washing was determined. The antimicrobial activity was assessed through the calculation of bacterial reduction against Escherichia coli (Gram‐negative) and Staphylococcus aureus (Gram‐positive) bacteria. TiO₂ was stabilized on the wool fabric surface by means of carboxylic acids, including citric acid (CA) and butane tetracarboxylic acid (BTCA). Both oxidized samples with potassium permanganate and nonoxidized wool fabrics were used in this study. The relations between both the TiO₂ and carboxylic acid concentrations in the impregnated bath and the antifelting and antibacterial properties are discussed. With increasing concentration in the impregnated bath, the amount of TiO₂ nanoparticles on the surface of the wool increased; subsequently, lower shrinkage and higher antibacterial properties were obtained. The existence of TiO₂ nanoparticles on the surface of the treated samples was proven with scanning electron microscopy images and energy‐dispersive spectrometry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011