Le procédé d'obtention du cuir à partir de peaux est appelé tannage. Il agit par stabilisation chimique du collagène. Il permet de transformer la peau en un matériau stable et durable. Actuellement, plus de 90% de la production mondiale de cuir est effectuée avec du sulfate de chrome, et les effluents du tannage contiennent des quantités importantes de ce sel métallique qu'il faut impérativement traiter par des procédés couteux. L’objectif de ce projet est de proposer une alternative, durable et écologique, au chrome pour le tannage. Dans ce but, des composés organiques ont été synthétisés et leur capacité à stabiliser le collagène a été évaluée par différentes méthodes. Des essais à petite échelle ont été réalisés sur du collagène pur et la capacité de stabilisation du collagène par ces composés organiques a été évaluée par DSC. Les composés organiques sélectionnés suite à ces essais ont été testés sur des peaux entières en tannerie. / The manufacturing process used to obtain leather from skin is called tanning. It acts by chemical stabilization of collagen, which transforms the skin into a stable and durable material. Currently, more than 90% of the production of leather worldwide is carried out with chromium sulfate. Therefore, tanning effluents produce significant quantities of this metal salt, which must be treated by expensive processes. The purpose of this project is to offer a sustainable alternative to chromium for tanning. To this end, organic compounds have been synthesized and their ability to stabilize collagen has been evaluated by different methods. Small-scale tests were carried out on collagen and its stabilization by these organic compounds was evaluated by DSC. The organic compounds selected after these tests were then tested on hides.

This thesis considers the fruit of the tara tree (Caesalpinia spinosa) as a sustainable source for tanning agents and proposes alternatives to the commercial mineral salts and vegetable extracts to comply with an increasing demand that concerns lower carbon footprint and health safety. Taxonomy of the tree is described and the substances contained in the fruit are chemically characterized in order to justify that tara farm forestry is economically viable and to secure a potential worth. The value chain is fully described from fruit collection in remote Andean regions to the export for the most important leather markets. Although tara tannins have been used in the leather industry and its properties being well known, the experimental part of the work aims to optimize innovative formulations using tara as wet-white pre-tanning agent. Combinations with a selected syntan used for wet white and final article recipes are proposed / Esta tesis considera el fruto del árbol de tara (Caesalpinia spinosa) como fuente sostenible de taninos para la curtición del cuero y propone alternativas para las sales minerales y los extractos vegetales como respuesta a la creciente demanda para reducir el impacto medioambiental y la seguridad de los artículos de consumo. Se describe la taxonomía del árbol así como la caracterización de su fruto para justificar la silvicultura como práctica económicamente viable y asegurar su valor y la cadena desde la recolección de los frutos en las regiones andinas hasta la exportación a los mercados más importantes de la industria del cuero. Aunque los taninos de la tara ya se usan para la fabricación de cueros desde épocas remotas y sus propiedades están reconocidas, la sección experimental de este trabajo se orienta a optimizar fórmulas innovadoras utilizando la tara como agente de curtido wet-white. Se proponen fórmulas para artículos finales.

Content: As it is known in the tanning sector, in recent times, the so-called wet-white and/or metal-free concepts have had a certain increase. For example, in the automotive sector, the wet-white tanning system, carried out with glutaraldehyde and tannins, has been widely diffused. In fact, car manufacturers offer, for interior furnishings, leather not only for high-end cars but increasingly also in the lower segments. The components on which the leather upholstery is applied are mainly steering wheel, seats, dashboard and panels. Therefore, the use of leather also in this context must be able to meet both the aesthetic/performance criteria and the environmental ones; environmental criteria should also consider the air quality of the interior of a motor vehicle. In practice, the interior furniture consisting of finished leather must be able to release a few volatile substances and, at the same time, provide a typical smell of leather. Considering, therefore, the diffusion of alternative chrome tanning systems for the different uses, in this work, wet-white (glutaraldehyde and tannins) will be investigated, both from the point of view of the performance characteristics and from the ecotoxicological ones. and leathers deriving from the latest generation of metal-free tanning. For the characterization of Volatile Organic Compounds (VOC) the GC-MS will be used coupled with the 'Purge and Trap' technique with the aim of obtaining information on the new substances used in the wetwhite / metal free production process and then avoiding undesired effects during use (eg bad smell, SVHC substances, etc.) Take-Away: metal-free automotive VOC

Content: The purpose of this paper is to study the influence of acrylic resins on the properties of the hide when added in the pickling-tanning stage of a wet white process. Among retanning products, acrylic resins are very frequently used because they lend very good properties to the hide on account of their high affinity for chromium. When applied during chrome tanning, these resins provide the hides with high fullness, due to the strong interaction of the carboxylate groups with chromium. Extensive bibliography is available on the application of acrylic resins in wet blue, where it is observed that the properties they provide to the hides depend basically on the type of monomers and molecular weight. However, less information is found when these products are applied in wet white tanning. In this study, 9 resins with different molecular weights and different monomer compositions were selected. Resins were applied to pelt leathers of Spanish origin split at 3.5 mm. Hides were cut along the backbone. A standard process was applied to the left halves and the same process adding the resin was applied to the right halves. The resin was added after adjusting the salt of the bath and before adding the pickling acids. The COD was measured before and after adding formic and sulfuric acid, and the shrinkage temperature and the degree of whiteness of the tanned hide were assessed. Hides were retanned and fatliquored with a standard process, and degree of softness, thickness, color intensity and organoleptic properties (fluffiness, compactness and grain tightness) were assessed. Leather shrinkage under temperature was also assessed, and images of leather sections were obtained by scanning electron microscopy (SEM). While acrylic resins did not increase shrinkage temperature, they did fix and/or deposit themselves in the interfibrillary spaces of the hide; indeed, highly reduced COD values after acidification in the pickling stage were observed. This study shows that homopolymeric acrylic resins provided fuller and fluffier hides, while the rest of resins practically did not improve the physical and organoleptic properties of the hides. Take-Away: Homopolymeric acrylic resins provided full er and fluffier hides, while the rest of resins practically did not improve the physical and organoleptic properties of the hides Wet white tanning improvement

Content: A combination of processing techniques and speciality chemicals has been developed to target environmental issues and legislation in the European leather industry, especially for automotive upholstery leather. This process combines new techniques in the beamhouse process through to the tanning process. Initial work on several different individual concepts showed some excellent improvements, but when these concepts have been brought together to form a single strategic process the advantages and improvements have exceeded expectations. The process demonstrates a reduction in the use of salt, formic acid and sulphuric acid. After more than two years of trials from small scale to full production in an automotive leather production environment, we are able to present independently test results showing the benefits of following this system. Briefly these include Improvement in tear and tensile strength results. Improved clarification with less suspended solids in the supernatant. Reduced COD in the supernatant and higher biodegradability COD/BOD. Less TDS in the supernatant. Chloride content reduction in the supernatant Sludge generation reduction. Less organic residues derived from the hide. Take-Away: A simple technique and small modifications to existing processing methods will reduce dramatically the environmental effects of wet white / chrome free tanning. This process can be used in any country in the world and answers many questions regarding reducing salt, BOD, COD, TDS etc.

Content: Different tanning materials endow leather with varying colors observable in undyed leathers. Periodateoxidized starch tanned leathers have a yellow tinge or light brown color and get darker with age. The color change in situ is ascribable to iodate ions that are byproducts of periodate oxidation. Iodate ions undergo reduction to form iodine molecules that are yellow or brown in low or at higher concentrations. This study focuses on the removal of iodate ions from Dialdehyde Tapioca Starch (DTS) using a simple precipitation method. Preparation of DTS is by periodate oxidation and precipitation of iodate ions using an inorganic precipitant. The experiments for manufacturing wet-white leathers used pickled goatskins and DTS (unmodified and modified) tanning agents at various percentages based on pelt weight. Glutaraldehyde (GTA) tanning was the control. The percentage removal of iodate ions in modified DTS was 98%. Both unmodified and modified DTS had an aldehyde content of 70%. FT-IR and 1H-NMR confirmed the aldehyde groups. GTA, unmodified, and modified DTS tanned leathers had shrinkage temperatures of 80, 87, and 89°C, respectively. The physico-mechanical properties of the control and experimental leathers are comparable. GTA tanned leather had the typical brown color associated with GTA tannages. The ‘b’ color value of unmodified DTS tanned leather was high confirming yellowing of leathers upon ageing. Wet-white leather tanned with modified DTS had no discernible color change. Analysis of the spent tan liquor shows a reduction in the BOD, COD, TS, and TDS load when compared to GTA tanning system evincing the biodegradability of DTS. This study has overcome the drawback associated with periodate-oxidized starch tanning agents, viz. leather darkening over time, considering the chemical and physico-mechanical properties of the resultant leathers. The novel iodate free DTS can be scaled-up for commercial availability. Take-Away: Removal of iodate ions from periodate-oxidized starch before its use as a tanning agent is imperative to avoid leather color change over time. This study reports the successful removal of iodate ions from Dialdehyde Tapioca Starch (DTS). Wet-white leather tanned with the modified DTS had no observable color change upon ageing.