Number

434-EN

Section

General Section

Use

Abstract

As part of the ZDHC commitment by 2020, “…eliminate the use of all per- and poly-fluorinated compounds (PFCs) from all products sells by Jan 2015”, C&A started “PFCs Ban“ project from 2012 . This case will show the approach how C&A worked with one of the chemical suppliers and major functional fabric suppliers on the PFCs ban pilot by alternative chemical with fully evaluation on process, safety and cost.

Substituted substances

Alternative Substances

Reliability of information

Evidence of implementation: there is evidence that the solution was implemented and in use at time of publication

Reason substitution

ecotoxicity
other reasons

Hazard Assessment

Substance to be substituted: Many polyfluorocarbons (PFCs) which are often used as water repellents pose severe risks to human health and the environment. Alternative substances: The alternative is an aqueous emulsion of dendrimers and polymers with a proprietary composition. Functionalized polymers are irritant to eyes and skin (H315, H319). The water base mixture also contains glycols classified as irritant to eyes, and cationic surfactants that are corrosive when concentrated and toxic to aquatic organisms. The product (as a whole) does not have to be labelled according to EU regulations for mixtures/preparations. The MSDS is available on request from the producer or user. None of the mentioned alternative substances is listed on the Substance Database according to SUBSPORTplus Screening Criteria (SDSC). » Check the Substance Database according to SUBSPORTplus Screening Criteria (SDSC)

Description of Substitution

Background Per and poly-fluorinated chemicals (PFCs) are widely used in the production process like carpets, leather/apparel, textile/upholstery, paper and packaging; coating and coating additives, Industrial and household cleaning products, pesticides and insecticides, while in textile industry they are mainly used to provide Durable Water Repellent (DWR) properties to the final products cause the PFCs treatment could reduce the surface tension of the fiber. But certain chemicals appeared high risk to both human health and environment after decades of research. Studies have found small quantity of PFOS and PFOA in water across the world, moreover, the potential release of PFOS derivatives’ (Figure1) widespread exposure route include ingestion of food and water, use of commercial products, and so on. Toxicological studies show that PFOS and PFOA accumulate primarily in serum, kidney, and liver, meanwhile epidemiologic studies have shown an association between PFOS and bladder cancer. Pilot for alternative From 2012 C&A connected worldwide chemicals suppliers for the first assessment based on the information of all advanced technology. After full screen, the company cooperated with three chemical suppliers by different technology for the final evaluation. Below case will share experience with one of the chemical suppliers from the project, the RUDOLF GROUP. As PFCs are mainly used for DWR properties, the company finalized nine types of fabrics (four kinds of 100% Nylon, four kinds of 100 % Polyesters and one kind of 94/6 Poly/Spandex), which are mainly used for functional shells as the pilot simples. In 2013, the company launched pilot with major functional fabric suppliers for the bulk production and technical supported by the RUDOLF GROUP with its advanced technology BIONIC-FINISH®ECO (finishing product ®RUCO-DRY ECO). The whole pilot not just focused on the final performance but also the cost for the new process which include DWR chemical, finishing chemical, manpower, facility, chemical waste, energy and risk cost. Performance and experiences for the alternative C&A picked pilot samples to qualified third party for water repellency performance by the method, ISO 4920:1981 spray test. The results shared that all types of finished fabric with the spray rating 4, slight random sticking or wetting of upper surface, which fulfill water repellency requirement on functional shells. From the pilot both C&A and nominated fabric mills found few issues, like color changing. Supported by the RUDOLF GROUP, the company tried to figure out the root cause and the solution. • Fabric Color Changing: Fabrics may experience a large color change before/after DWR finishing or coating like any other new technologies. The additional laboratory scale is necessary to settle the new dyeing recipe and DWR finishing condition. • Water Repellent Performance: To achieve the same functional performance as by PFCs, below actions may needed as below by the new technology: a. Chemical residuals, for example some of the detergents, woven oil and raising softner in the fabric may affect the final performance. Make sure the washing should be sufficient after dyeing, if necessary, suggest add additional cleanser in order to remove the residuals remained in the fabric. b. The oven condition for the new technology should be 160-170?x40-60S that the temperature is higher than the normal one. Also the higher speed should be avoided which may affect the crosslinking of the water-repellent agent. c. Cause the ®RUCO-DRY ECO’s surface tension is higher than PFCs, to achieve the same DWR performance, higher alternative product dosage is required. Additionally, for lightweight fabrics, higher pick-up ratio is necessary. • FTOH Cross-contamination: FTOH may exist in wet processes and oven which used for the former PFCs technology. Fully cleaning is required for the chemical stirred tank, finishing tank and roller. Meanwhile, the oven refreshing is necessary to make the air without any FTOH residuals. After the full analysis of the whole new process’s cost, compared with former process by PFCs, the average price based on all functional fabrics was 2%-4% higher. The Alternative Assessment To assess the chemical and hazardous performance of ®RUCO-DRY ECO, C&A worked with the RUDOLF GROUP for further research. The alternative product was under the scope of Dendrimer-based repellent chemistry with both OEKO-TEX® Standard 100 and Bluesign® criteria. It is not based on perfluorinated compounds. The test of qualified third party showed that the alternative product contained no PFCs above detection limit. Dendrimers are repetitively branched molecules leading to monodisperse, tree-like structures. The synthesis of monodisperse polymers demands a high level of synthetic control, which can only be achieved through step-by-step reaction, in which the dendrimer is built up by one monomer layer at a time.[2] Fluorocarbon-free dendrimers are based on hydrocarbon or polyurethane chemistry. Cross-linking is commonly achieved by chemical binding of the dendrimers with isocyanates to the fibre. Glycols are added as solvents and cationic surfactants in small amounts act as emulsifiers.[3] According to the MSDS, the alternative product was not required to be labeled according to Directive 1999/45/EC. The product contains 5-15% of an unknown functionalized polymer, which is skin and eye irritating group 2 (H315 + H319), and 1-5% of propane-1,2-diol. The product was easily biodegradable (>80%) in the OECD 302B test. The product has not been tested for ecotoxicity but, by read across, the acute eco-toxicity for fish was estimated to LC50 >100 mg/L, and the EC-50 for sewage sludge bacteria was >100 mg/L.[4] C&A searched propane-1,2-diol, CAS.57-55-6 via Pharos® for the further assessment results. By GreenScreen® method, certain chemical was assigned a GreenScreen® Benchmark Score of 2 (“Use but Search for Safer Substitutes”) as it has Moderate Group I Human Toxicity (reproductive toxicity (R) and developmental toxicity (D)). While by Cradle to Cradle® method, its Reproductive Toxicity (Repro + Dev) and Climatic Relevance were Green Hazard.[5] It was an acceptable result but the company will work with the RUDOLF GROUP for safer solvent. Further Approach As one of the founding member of the Zero Discharge of Hazardous Chemicals (ZDHC), C&A had stared its action since 2013 to make sure PFCs eliminated in the whole supply chain as below: • RSL & MRSL: Not only PFOA and PFOS, but whole PFCs group were limited by C&A. Total 90 functional fabric samples were picked for PFCs random check in 2015 and 2016 that no PFCs were found. • Chemical Management: the company had updated the “Approved Alternatives to Perfluorinated Compounds (PFC)” on 2015 that only DWR chemicals on the list were allowed for its suppliers in the process. To achieve the “Clean Factory”, if any PFCs from chemical inventory list or factory tour was found, action plan was required by the supplier side to make sure PFCs would not be used in all process but not only for the company. C&A will work with chemical and fabric suppliers for further assessment of alternative chemicals approved and application of potential alternatives to achieve the “Closing and Slowing the Loop” approach.

Case/substitution evaluation

This case story from a user describes the substitution of perfluorinated compounds containing textile finish with an alternative PFC free finish. However, it was not possible to perform a full hazard assessment (e.g. potentially hazardous monomers etc.) as the full compositions are unknown to SUBSPORTplus. The PFC free finish might be a feasible alternative also for other PFC containing products, which can have severe negative environmental and health impacts.

State of implementation

In use

Enterprise using the alternative

See: Contact Information supplier

Availability ofAlternative

On the market

Type of information supplier

User

Contact

http://sustainability.c-and-a.com/footer-pages-top/contact-us/

Further information

[1]  Perfluooctane Sulfonate in the EnvironmentMichigan State University S. Maybery et al. 2001 Available at: https://www.researchgate.net/profile/Paul_Jones7/publication/228872560_Perfluooctane_Sulfonate_in_the_Environment/links/0deec5208db2c7c75f000000/Perfluooctane-Sulfonate-in-the-ENvironment.pdf

[2] ZDHC (2012). Durable Water and Soil Repellent Chemistry in the Textile Industry – A Research Report. P05 Water Repellency Project. Zero Discharge of Hazardous Chemicals (ZDHC). Available at: https://outdoorindustry.org/pdf/FINAL_ZDHC_P05_DWR%20Research_Nov2012.pdf

[3] UNEP (2012). Technical paper on the identification and assessment of alternatives to the use of perfluorooctane sulfonic acid in open applications. Persistent Organic Pollutants Review Commit-tee, United Nations Environment Programme, UNEP/POPS/POPRC.8/INF/17.

[4] Alternatives to perfluoroalkyl and polyfluoroalkyl substances (PFAS) in textiles, The Danish Environmental Protection Agency, 2015. Available at: https://www2.mst.dk/Udgiv/publications/2015/05/978-87-93352-16-2.pdf

[5] Pharos Project, available at: https://www.pharosproject.net

Date, reviewed

February 9, 2022