Crosslinking cotton with poly(itaconic acid) and in situ polymerization of itaconic acid: Fabric mechanical strength retention

Polycarboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton fabrics. Previously, we found that itaconic acid (IA) polymerized in situ on cotton fabric and also in an aqueous solution in the presence of a K₂S₂O₈/NaH₂PO₂ initiation system. Both poly(itaconic acid) (PIA) and the polymer formed by in situ polymerization of IA are able to crosslink cotton cellulose, thus imparting wrinkle resistance to cotton. In this research, we compared the performance of the cotton fabric crosslinked by PIA and that crosslinked by in situ polymerization of IA. The fabric treated with PIA and that treated with IA had similar wrinkle recovery angles. The cotton fabric treated with IA, however, lost more tensile strength than that treated with PIA due to cellulose degradation. We determined the magnitude of the fabric tensile strength loss attributed to crosslinking by separating the tensile strength loss due to cellulose degradation from the total tensile strength loss, and found that the tensile strength loss caused by crosslinking for the fabric treated with PIA was significantly higher than that for the fabric treated with IA. This can probably be attributed to more concentrated crosslinkages formed on the near surface of the PIA‐treated cotton fabric. PIA had poorer penetration into the amorphous cellulose region in fiber interior due to its much larger molecular size, thus increasing its concentration on the fabric's near surface. The data also suggest that more concentrated crosslinkages on the fabric surface reduced fabric abrasion resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2023–2030, 2003     

Combination of a hydroxy‐functional organophosphorus oligomer and a multifunctional carboxylic acid as a flame retardant finishing system for cotton: Part I. The chemical reactions

Multifunctional carboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid (BTCA), have been used as crosslinking agents for cotton cellulose to produce wrinkle‐resistant cotton fabrics and garments. Polycarboxylic acids were used to bond hydroxy‐functional organophosphorus oligomer to cotton, thus imparting durable flame retarding properties to the cotton fabric. This research investigated the chemical reactions between the hydroxy‐functional organophosphorus compound and BTCA on cotton. BTCA crosslinks cotton cellulose through the formation of a 5‐membered cyclic anhydride intermediate and esterification of the anhydride with cellulose. In the presence of the organophosphorus compound, BTCA reacts with both the organophosphorus compound and cellulose, thus functioning as a binder between cotton cellulose and the organophosphorus compound and making the flame retarding system durable to laundering. The cotton fabric treated by the combination of the organophosphorus compound and BTCA demonstrated lower wrinkle resistance and less tensile strength loss than that treated by BTCA alone. The phosphorus retention on the cotton fabric after one home laundering cycle was approximately 70%. Copyright © 2003 John Wiley & Sons, Ltd.     

Modification of wrinkle resistance of cotton fabric

Cotton fabrics were treated with montmorillonite (MMT) so as to improve the wrinkle‐resistant properties of the cotton fabrics. The MMT in emulsion form was applied by padding method to the cotton fabrics, and the wrinkle‐resistant properties of the MMT‐treated cotton fabrics and the wrinkle‐resistant properties of MMT‐treated cotton fabrics were consequently improved. Furthermore, different instrumental methods were used for studying the distribution of MMT particles on the cotton fabric surface. It was noted that near nano‐scale MMT particles were adhered on the fiber surface, and in addition, the particles size played an important role in influencing the wrinkle‐resistant properties of the cotton fabric. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3700–3707, 2006     

Objective measurement of fabric properties of the plasma‐treated cotton fabrics subjected to cocatalyzed wrinkle‐resistant finishing

The wrinkle resistance treatment together with plasma pretreatment is especially very important to cotton fabrics because of their high wrinkling tendency. However, the processes improved the wrinkle recovery property of cotton fabrics, but, at the same time, may worsen the fabric handle, which is an important factor when designing the end‐uses of fabric because handling of fabric also a critical factor for purchasing decision. The Kawabata Evaluation System for Fabrics (KES‐F) measures the scale of “basic hand” and “total hand” values determined by the combined results of sensory tests conducted by the instrumental measurements. In the present article, the effects of plasma treatment and catalyzed 1,2,3,4‐butanetetracarboxylic acid (BTCA) treatment on the fabric yellowing are also studied. The results found that the wrinkle‐resistant treatment had a negative effect on the tensile properties, shearing properties, bending properties, and surface friction and variation, whereas the compressional properties are improved by the treatment. In addition, the plasma treatment improves the tensile properties and bending properties but not the compressional properties, shearing properties, and surface friction and variation. Besides, it is concluded that these treatments can influence not only the fabric handle but also the yellowness of fabrics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymeric multifunctional carboxylic acids as crosslinking agents for cotton cellulose: Poly(itaconic acid) and in situ polymerization of itaconic acid

Multifunctional carboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton. In previous research we found that maleic acid (MA) and itaconic acid (IA) polymerize in situ on cotton fabric at elevated temperatures when both potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂) are present, thus imparting wrinkle resistance to the treated cotton fabric. We also found that MA and IA polymerize in aqueous solutions in the presence of K₂S₂O₈ and NaH₂PO₂. In this research, we compared the effectiveness of poly(itaconic acid) (PIA) applied to cotton fabric as a polymer and IA applied as a monomer and allowed to polymerize in situ for crosslinking cotton cellulose. We found that IA is more effective in esterifying cotton cellulose and imparting a high level of wrinkle resistance to the fabric as it polymerizes in situ than PIA applied as a polymer. We also found that tensile strength loss of the cotton fabric crosslinked by IA polymerizing in situ as a function of fabric wrinkle recovery angle is practically the same as that crosslinked by PIA applied as a polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 319–326, 2001     

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     

Formaldehyde-free durable-press finishes

Durable-press finishing agents that neither contain nor release formaldehyde when applied to cotton fabrics are reviewed and compared with conventional N-methylolamides in regard to fabric wrinkle resistance, smooth drying properties, strength retention and yellowing imparted. The need for agents that are not derived from formaldehyde results from international recognition that formaldehyde is a probable human carcinogen. When formaldehyde-free cellulose crosslinking agents are screened to eliminate those having toxicity, odour and environmental problems of their own, the most likely candidates are seen to be polycarboxylic acids and 1,3-dimethyl-4, 5-dihydroxy-ethyleneurea (also known as DHDMI). These differ in cost and effectiveness, and will require further research and development to become fully practical.     

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     

Effect of plasma pretreatment on the wrinkle‐resistance properties of cotton fibers treated with a 1,2,3,4‐butanetetracarboxylic acid–sodium hypophosulfite system with titanium dioxide as a cocatalyst

A 1,2,3,4‐butanetetracarboxylic acid (BTCA)–sodium hypophosulfite (SHP) wrinkle‐resistance system played an important role in improving the wrinkle‐resistance properties of cotton fibers. In this study, titanium dioxide (TiO₂) was used as a cocatalyst to further enhance the wrinkle‐resistance properties of BTCA–SHP‐treated cotton fabrics, that is, those treated with (1) 5% BTCA and 10% SHP; (2) 5% BTCA, 10% SHP, and 0.1% TiO₂; and (3) 5% BTCA, 10% SHP, and 0.2% TiO₂. In addition, the effect of plasma as a pretreatment process on the wrinkle‐resistance properties of the three treatment systems was also studied. The experimental results reveal that the wrinkle‐resistance properties of cotton fibers were improved after different wrinkle‐resistance treatments. In addition, the plasma pretreatment further enhanced the wrinkle‐resistance treatments to different extents, depending on the process parameters. Scanning electron microscopy images confirmed that such plasma pretreatment conditions imparted the best crosslinking effect on the cotton fibers. However, the wrinkle‐resistance‐treated cotton specimens had lower tensile strength and tearing strength values compared to the control sample, whereas the plasma pretreatment and cocatalyst may have compensated for the reduction in the mechanical strength caused by the wrinkle‐resistance agents. In this article, the optimum conditions for the plasma pretreatment on the basis of the result of the wrinkle‐recovery angle were analyzed with an L₉(3)³ orthogonal array testing strategy technique. The results showed that plasma treatment conditions with (1) a 10 mm/s speed, (2) a 0.1 L/min oxygen flow rate, and (3) a 4‐mm jet‐to‐substrate distance together caused a significant improvement in the wrinkle‐resistance properties of the cotton fibers treated with the three different BTCA treatments. Moreover, the treatment speed was the dominant factor, followed by jet‐to‐substrate distance and oxygen flow rate, in affecting the extent of improvement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photocatalytic functional cotton fabrics containing benzophenone chromophoric groups

In preparation of self‐decontamination clothing materials in high reactivities against toxic agents, photoactive benzophenone chromophoric groups were incorporated into cotton fabrics. The cotton fabrics were treated by using 4‐hydroxybenzophenone as a reagent, 1,2,3,4,‐butanetetra carboxylic acid (BTCA) as a crosslinker, and sodium hypophosphite as a catalyst. The fabric treatment was conducted by a pad‐dry‐cure method. The benzophenone chromophoric group incorporated cotton fabrics were characterized by FTIR, SEM, TGA, and so on. The results confirmed the expected structures of the benzophenone chromophoric group modified and BTCA crosslinked cotton fabrics. The treated cotton fabrics demonstrated radical reactivities and antibacterial activity under UV irradiation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Improving easy care nonformaldehyde finishing performance using polycarboxylic acids via precationization of cotton fabric

Cotton fabric were first subjected to quaternization (cationization) reaction using 3‐chloro‐2‐hydroxypropyl trimethyl ammonium chloride commercially known as Quat®‐188. Cationization was carried out under different conditions for optimization of the preparation of cationized cotton with different degrees of cationization, using the pad‐batch method. Also, established was the optimal condition for cationization that involves Quat‐188/NaOH molar ratio 1/2 at 70°C for 4 h. Besides, a thorough investigation of factors affecting reaction of these cationized cotton with citric acid (CA) or 1,2,3,4‐butanetetracarboxylic acid (BTCA) was carried out with a view of improving the ease of care characteristics of nonformaldehyde finishing. The dependence of fabric performance as measured by strength properties, dry wrinkle recovery angles, whiteness index, and dyeability with reactive dyes was also evaluated. It was postulated that reaction of cationized cotton with either CA or BTCA involves estercrosslinking as well as ionic crosslinking. This, indeed, was largely positively reflected on the fabric performance especially when the properties of both uncationized cotton were compared with those of the cationized cotton. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2697–2704, 2006     

Cetylpyridinium chloride cationic finishing improves the dyeing and antibacterial properties of madder dyed cotton

In this work, after cationic pretreatment of cotton fabric with cetylpyridinium chloride (CPC), the compound of citric acid (CA) and succinic acid (SUA) were used as crosslinking agents to dye cotton fabrics with natural madder dye to improve the dyeing and antibacterial properties and realise the multifunctional finishing of cotton fabric. The effects of mordant dyeing, CA + SUA crosslinked dyeing, and CPC/CA + SUA crosslinked dyeing on the microstructure and properties of cotton fabrics were compared. The dyeing by the three processes occurred primarily in the amorphous zone of the fibres, and all kept the original crystalline form of the cotton. CA + SUA crosslinked dyeing and CPC/CA + SUA crosslinked dyeing increased the thermal stability of the cotton fabric. CPC/CA + SUA crosslinked dyed cotton obtained excellent dyeing results with the colour depth value (K/S) of 12.3 and rubbing fastness and washing fastness of levels 4–5, and the levelness and dye permeability were acceptable. Furthermore, the antibacterial rate against Escherichia coli and Staphylococcus aureus reached 99.99%, and the ultraviolet protection factor (UPF) reached 50+. Moreover, the wrinkle recovery angle (WRA) increased by 55% compared with raw cotton. This showed that CPC/CA + SUA crosslinked dyed cotton had excellent antibacterial, anti-ultraviolet, and anti-wrinkle performances.     

Concurrent dyeing and finishing: V. One-bath dyeing and easy-care finishing of cotton fabrics with acid dyestuffs and N-methylol compounds using different catalytic systems

A number of catalysts have been used for effecting concurrent dyeing and easy-care finishing of cotton fabric with acid dyes and N-methylol finishing agents. Factors affecting the process, such as the nature and concentration of catalyst, the finishing agent, the additive and the dye as well as curing temperature, were investigated. Evaluation of the simultaneously dyed and finished fabric was made with respect to colour strength, wrinkle recovery and fastness properties. The results obtained indicate that, of the eleven catalysts used, ammonium persulphate is the best for effecting concurrent dyeing and finishing of cotton fabric using acid dye and dimethyloldihydroxyethylene urea (DMDHEU).     

Built-in lubrication on cotton fabrics

Partial cotton esters of long chain fatty acids of low degrees of substitution (D.S.<0.20) have been prepared by a variety of methods. In particular, the effects of the introduction of a stearoyl or an oleoyl group into the cellulose matrix on fabric properties, such as softness of hand and wrinkle recovery, have been studied. Attempts have been made to compare fabric properties of partial esters of like D.S. prepared by various methods of esterification and effect of a chemically attached alkanoyl group with effect of the same group deposited or adsorbed on the surface of the cotton fabric. Consideration has been given to the size of the alkyl group, its orientation on the surface of the fiber and its hydrophobicity. Data indicate that resistance to abtasion of cottons chemically modified with long chain alkyl groups is reduced whenever the finished fabric has high dry wrinkle recovery. High dry wrinkle recovery is obtained after esterification of cotton in nonaqueous media. Improvement in resistance to abrasion is pronounced when the alkyl group has not been chemically combined with the cellulose matrix in the absence of water, and usually is obtained when the finished cottons possess only high wet wrinkle recovery. One of eight papers being published from the Symposium “Surface Active Agents in the Textile Industry,” presented at the AOCS Meeting, New Orleans, April 1970. So. Utiliz. Res. Dev. Div., ARS, USDA.     

Effects of crosslinking agents,dyeing temperature,and pH on mechanical performance and whiteness of silk fabric

The effects of bleaching and dyeing conditions on abrasion resistance, tear strength, and whiteness of silk fabrics were studied. Different crosslinking agents at various concentrations were introduced into the silk fabrics under various dyeing temperatures and pH. The results indicated that the oxidatively bleached silk fabric exhibited better mechanical properties than those of reductively bleached silk fabric. Sodium citrate was found to be the most suitable crosslinking agent for enhancing the abrasion resistance and tear strength of the silk fabrics with no significant effect on the whiteness. The mechanical property improvements of sodium citrate–dyed silk fabric were attributed to a chemical reaction between –COOH groups and amino acid side chains in silk fabric, the mechanism proposed in this work. Increasing sodium citrate resulted in improved mechanical properties and whiteness, but the opposite trend was found with increasing dyeing temperature. An optimum pH for dyeing the silk fabric in this work was 5.5. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1000–1007, 2004     

Flame resistant cotton fabrics prepared by radiation-initiated polymerization with vinyl phosphonate oligomer and N-methylolacrylamide

Radiation-initiated polymerization of vinyl phosphonate oligomer (molecular weight 500–1000) and N-methylolacrylamide from aqueous solutions was investigated with cotton printcloth, flanelette, and sateen fabrics and with cotton (50%)–polyester (50%) flannelette fabrics. Determinations were made of the effects of radiation dosage, mole ratio of vinyl phosphonate in the oligomer to N-methylolacrylamide in aqueous solution, concentration of reactants, wet pickup of solutions on fabrics, and irradiation of both dry and wet fabrics on efficiency of conversion of oligomer and monomer in solution to polymer add-on. The effects of vinyl phosphonate oligomer and N-methylolacrylamide radiation-initiated polymerization on some of the textile properties of cotton printcloth and on flame resistances of cotton and cotton–polyester fabrics were evaluated. The breaking strength of modified cotton printcloth was about the same as that of unmodified fabric; however, the tearing strength and flex abrasion resistance of modified fabric were reduced. The textile hand of the modified printcloth fabrics that had flame resistance indicated: interaction between cellulose and vinyl phosphonate oligomer–poly(N-methylolacrylamide) and uniform deposition in the fibrous cross section (transmission electron microscopy); surface areas of heavy deposits of oligomer–polymer (scanning electron microscopy); and phosphorus located throughout the fibrous cross section (energy dispersive x-ray analysis). Polymerization of vinyl phosphonate oligomer and N-methylolacrylamide was radiation initiated with cotton–polyester fabric; however, this modified fabric did not have flame-resistant properties.     

Applying the sol–gel method to the deposition of nanocoats on textiles to improve their abrasion resistance

The thin-coat finishing of textiles carried out by the sol–gel methods gain greater and greater importance owing to their suitability for the versatile functionalization of textiles to impart to them properties being difficult and even impossible to obtain with the use of conventional finishing methods. This article presents the test results of the thin-coat protective finishing of cotton fabrics against abrasion. This treatment consists in depositing hybrid SiO₂*/Al₂O₃ sols synthesized from two precursors: (3-glycidoxypropyl)trimethoxy-silane and aluminum isopropoxide on fiber/fabric surface. The abrasion resistance of the fabric treated by the sol–gel method has been increased by about five times according to Martindale test and this effect is resistant to prolonged laundering. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

纳米氧化锌和纳米银对棉织物的多功能整理

以植物金银花提取物作为还原剂制备了纳米ZnO和纳米Ag,通过浸轧法将纳米ZnO单独整理以及将两者依次整理到棉织物上制备多功能棉织物(ZnO-棉织物、ZnO/Ag-棉织物).利用SEM、XRD、FTIR分析了整理前后棉织物的形貌和结构,并探讨了整理后棉织物的多功能性.结果表明,棉织物上的纳米粒子分布较均匀且发生了轻微团聚.与ZnO-棉织物相比,ZnO/Ag-棉织物对亚甲基蓝(MB)和红酒的降解率分别提高了7.09％和10.61％,说明纳米Ag提升了纳米ZnO的光催化活性.ZnO-棉织物经过10次洗涤后其纳米粒子含量虽有小幅下降,但对MB的降解率仍达到83.24％以上,说明负载纳米粒子后棉织物具有良好的自清洁能力和耐洗性能.此外,ZnO-棉织物和ZnO/Ag-棉织物的紫外防护系数(UPF)值分别达到33.23和41.06,对大肠杆菌和金黄色葡萄球菌的抑菌率均达到95％以上,表现出优良的抗紫外线性和抗菌性能.     

Abrasion phenomena in twill tencel fabric

The abrasion characteristics of Tencel fabrics were evaluated by Martindale abrasion and laundering, and the breakdown mechanism of fibers was surveyed by scanning electron microscopy. The fabric was subjected to pad‐dry‐cure treatment with two different types of modified dimethyloldihydroxyethylene urea resins (Reaktant DH and Reaktant FC). Although the degree of dry abrasion varied with different resins, the damage exhibited by individual fibers differed little from untreated to resin‐treated; the major mechanism of abrasion was through friction, and the mechanism of fiber failure was multiple splitting and transverse cracking. In untreated Tencel, the characteristic feature of wet abrasion was massive fibrillation, and in crosslinked fabrics, the wet abrasion mechanism was through fiber slippage and slicing action, although in the Reaktant FC‐treated fabric, the wet abrasion mechanism was more through slicing than through fiber splitting. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1391–1398, 2006     

棉织物的纳米银多功能整理

以植物还原剂——金银花提取物和化学还原剂——丙三醇,分别还原硝酸银,制备了两种纳米银溶液。采用浸渍法将上述制备的纳米银溶液分别对棉织物进行功能整理。利用SEM、EDS、XRD、FTIR分析整理前后棉织物的外观形貌及结构,并探讨了整理后的棉织物的抗紫外性能、不同洗涤次数后其含银量、色差和抗菌性能的变化。结果表明,纳米银粒子主要通过范德华力吸附在棉织物纤维素的无定形区;与化学还原法相比,植物还原法制备的纳米银粒径减小了约15nm,植物还原法制备的纳米银溶液整理后的棉织物经过50次洗涤后,棉织物表面的纳米银吸附量及色差变化不大,且对大肠杆菌和金黄色葡萄球菌的抑菌率仍旧达到99%以上,具有优异的抗菌性及良好的耐洗涤性能。另外,植物还原法制备的纳米银溶液整理后的棉织物紫外线防护系数(UPF)值达到了36.82,具有较好的抗紫外性能。