Skin sensitising, skin corrosive and skin irritating substances in textiles, leather, furs and hides A consultant study conducted by Cattermole Consulting Inc. and Colour Connections

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Skin sensitising, skin corrosive and skin irritating substances in textiles, leather, furs and hides – identification of relevant substances and assessment of alternatives

A consultant study conducted by Cattermole Consulting Inc. and Colour Connections

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The Swedish Chemicals Agency is supervisory authority under the Government. We work in Sweden, the EU and internationally to develop legislation and other incentives to promote good health and improved environment. We monitor compliance of applicable rules on chemical products, pesticides and substances in articles and carry out inspections. We review and authorise pesticides before they can be used. Our environmental quality objective is A Non-toxic Environment.

© Swedish Chemicals Agency. Stockholm 2019.

Article number: 511 320.

About the report

Amanda Cattermole from Cattermole Consulting Inc. and Phil Patterson from Colour Connections Consultancy ltd authored the study. The scope and the focus of the report has been settled by the Swedish Chemicals Agency, but the analysis, the reasoning and the conclusion of the report itself is the sole responsibility of the authors. With regard to the opinions and conclusions presented in the report, they are entirely those of the authors and do not necessarily reflect the Swedish Chemicals Agency’s point of view. The analysis and results from the study is used as background material and input for a proposal for a REACH restriction on skin sensitising substances in textiles, leather, skin and fur, which is done in collaboration between the Swedish Chemicals Agency and the French Agency for Food and Occupational Health (ANSES)

Update 2019-05-28: In a previous version of the report some pieces of information that should have been included in the spreadsheets in Appendix 1 and 3 were missing. These pieces of information have now been included.

Preface

The Swedish Chemicals Agency provided lists with over 400 chemical substances that are classified as skin irritants, skin corrosives or skin sensitisers or a combination thereof. In addition, ANSES studied 26 chemicals that were believed to be implicated in cases of harm to consumers. Some of the chemicals from the ANSES study are classified as skin irritants, skin corrosives or skin sensitisers although some were not classified. After consolidation and removal of duplicates, there were 346 unique chemical substances for further review.

This study was designed to first determine which of the 346 substances were relevant to textiles and leather production, which may be present on finished textile and leather articles at point of sale, and finally which ones may be present at levels that may cause reactions to the skin as either skin irritants, corrosives or sensitizers or a combination thereof.

Once a list was identified, quantities of each chemical substance used in the manufacture of textiles and leather sold in the EU, were estimated using a created volume reckoner and from existing statistics of the EU fibre and leather market.

Where possible, and feasible, safer alternatives, costs, volume trends and technical challenges of introducing those alternatives to market were shared for each chemical on the list.

The authors believe that some chemicals on the list of ‘substances that can potentially be present at levels that could potentially cause harm to consumers via skin contact’ can be treated as groups rather than as individual chemicals e.g. Chromium salts or Diisocyanates.

Content About the report ............................................................................................... 3

Preface............................................................................................................... 3

List of Figures ................................................................................................... 6

List of Tables .................................................................................................... 6

Summary ........................................................................................................... 7

Sammanfattning ............................................................................................... 9

1 Background ......................................................................................... 11

2 An overview of textile processing ..................................................... 13 2.1 Textile processing ......................................................................................................... 13 2.2 Leather processing ........................................................................................................ 15 2.3 Textile and leather formulations .................................................................................... 16

3 Method ................................................................................................. 19 3.1 Phase I – Relevance, screening and validation ............................................................ 19 3.2 Preliminary categorisation ............................................................................................. 21 Assumptions ................................................................................................................................ 22 3.2.1 Expert verification .......................................................................................................... 23 3.3 Phase II – Possible consumer exposure ....................................................................... 24 3.3.1 Knowledge via test data ................................................................................................ 24 3.3.2 Elimination of chemical substances based on physical properties ............................... 24 3.3.3 Elimination of irritants and corrosives that are present at levels too low to cause a skin

reaction .......................................................................................................................... 25 3.3.4 Estimation of worst case ppm’s present on a finished article ....................................... 25 3.3.5 Further information to aid downstream prioritisation ..................................................... 27 3.3.6 Consolidation of five lists [end of phase I] into two lists [end of phase II] ..................... 27 3.4 Phase III – Volumes and alternatives ........................................................................... 28 3.4.1 Volume ready reckoner ................................................................................................. 28 EU tonnages used in the calculations ........................................................................... 29

3.4.2 Alternatives and costs ................................................................................................... 30

4 Results ................................................................................................. 31 4.1 Discussion of results ..................................................................................................... 32 4.1.1 Groups of chemicals ..................................................................................................... 34 4.1.1.1 (Meth)acrylates ..................................................................................... 34

4.1.1.2 Antimicrobials ....................................................................................... 34

4.1.1.3 Chromium compounds ........................................................................... 34

4.1.1.4 Nonylphenol ethoxylates (NPEO’s) ........................................................... 35

4.1.1.5 Diisocyanates ....................................................................................... 35

4.1.1.6 Dyes .................................................................................................... 36

4.1.1.7 Intermediates ....................................................................................... 36

4.1.1.8 Solvents ............................................................................................... 36

4.1.2 Final thoughts ................................................................................................................ 36

5 Reference List ..................................................................................... 37

6 Appendix 1 .......................................................................................... 39

7 Appendix 2 .......................................................................................... 58

8 Appendix 3 .......................................................................................... 67

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List of Figures Figure 1. Visual of the textile supply chain 15

Figure 2. Representation of a drum of a chemical formulation used in textile and leather processing 17

Figure 3. High - level approach of the entire project 19

Figure 4. Global fibre production 29

Figure 5. Visual representation of the priority sense check 33

List of Tables Table 1. Typical chemical substances in chemical formulations 18

Table 2. Criteria for substances that may be present on finished articles 21

Table 3. Initial screening categorization prior to verification 23

Table 4. Chemical concentration ranges for formulations and finished articles 26

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Summary The Swedish Chemical Agency provided a list of 346 chemical substances mostly1 classified as skin sensitising, skin corrosive and skin irritating substances or a combination thereof. These substances may or may not be used in textile and leather supply chains, and may or may not be present on finished articles.

This report documents the approach taken for the three phases of the project

PHASE I - Identify substances on the list that are used in the production textiles, leather, furs and hides, and that are likely to be present in finished articles.

PHASE II - Gather information about levels in formulations, use patterns and potential consumer exposure

PHASE III – Estimate approximate volumes. Identify if and how the substances can be substituted, and the approximate costs of substitution.

The report includes an overview of the method and results, and three accompanying PDF´s (available as appendices) that contain detailed information about each chemical substance that may be present on finished articles.

The first PDF is called the “IN-List.” It is a list of chemicals that may be present on finished articles. The second PDF is a tool called the volume ready reckoner that the authors created to estimate potential volumes of chemicals used in the leather and textile industry that are imported into Europe. The 3rd PDF is a visual representation that provides a “priority sense check”, further explained as the IN-List of chemicals, sorted by priority and ranked from A-D.

The “IN list” captures chemical name and CAS number, use/function, where in the supply chain the chemical is used (deliberately or unintentionally), volumes, estimated ppm levels for articles at point of sale, alternatives, costs, recommendations and suggested priorities (A through D), for each substance or group of chemical substances, where applicable.

Textile and leather manufacturing is complicated. It consists of a series of processing steps where chemicals are used and removed by washing and rinsing or applying heat. Some substances may be present in chemical formulations but are unlikely to be present on finished articles. The wet processor uses some substances intentionally, such as dyes and coatings, but also some unintentionally, such as preservatives, antioxidants, stabilizers etc. Some chemicals are present as residuals, unreacted monomers or intermediates. Some chemicals are designed to stay on the product, whereas others are used to aid manufacturing such as catalysts, lubricants, detergents etc.

The report documents the method used to screen, and verify by industry experts, which of the 346 substances may be present on finished articles at point of sale.

Quantities of chemicals, and where they are used, were determined by creating a volume ready reckoner for each chemical substance used in the manufacture of textiles and leather sold in the EU. (Estimating the amount of chemicals used in the manufacture of textiles and leather sold in the EU can be no more than qualitative: Assumptions and calculations are provided for each substance in the PDF).

1 Some of the chemicals are not harmonized classified for the endpoints but were included in the list since they were found in finished products via testing

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Where appropriate, chemicals with similar chemical properties (e.g. ‘diisocyanates’ or ‘chromium compounds’) were grouped together when looking at volumes and alternatives.

Finally, where appropriate, priorities and recommendations for legislation, such as “ban” or “create limit values at point of sale” were provided for groups of substances to help prioritize eventual toxicological work. The Swedish Chemicals Agency might however come to a different conclusion.

In this study, 116 chemical substances on the provided list were identified as potentially being present on finished articles, and the authors propose that these move forward for additional toxicological and socioeconomic review.

The authors used advice from toxicologists from the Swedish Chemicals Agency to exclude any irritants that will not conceivably be present on finished articles above 10,000 ppm and any corrosives that will not conceivably be present on finished articles above 1,000 ppm.

All skin sensitizers that can be present at ppm levels or above are included in the final list in this report– those that are present at levels that a toxicologist deems will not cause skin sensitization at the levels indicated in this report can be subsequently removed.

The Swedish Chemicals Agency may opt to go beyond the skin sensitization definition and consider levels at which a pre-sensitized individual reacts to a skin sensitizer, and in this case a toxicologist would need to consider lower threshold values.

The authors have provided comments and recommendations for each listed chemical or chemical group.

In some cases it is relatively straightforward to select readily available alternatives (e.g. dyes). In other cases it is recommended that some chemicals remain in use, but tight controls are enforced on allowable levels on finished articles (e.g. some dye/chemical intermediates, diisocyanates).

There are some chemicals on the list where further, detailed discussions with the chemical industry are required to ensure phase-outs and substitutions do not have regrettable consequences (e.g. the use of in-can preservatives and solvents in formulations).

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Sammanfattning

Kemikalieinspektionen har tagit fram en lista på 346 kemiska ämnen, där de flesta2 ämnena har en harmoniserad klassificering som allergiframkallande för huden, frätande på huden eller irriterande på huden. Ämnena skulle kunna förekomma i leverantörskedjor för textilier och läder, och de skulle kunna förekomma i färdigproducerade varor som säljs i butiker.

I det här dokumentet beskrivs den arbetsmetod som använts för projektets tre faser:

FAS I – Identifiera vilka kemikalier på listan som används i produktionen av textilier,läder, päls och skinn, och som sannolikt förekommer i färdiga produkter.

FAS II – Inhämta information om halter i kemiska formuleringar, användningsmönsteroch konsumentens potentiella exponering.

FAS III – Uppskatta ungefärliga volymer. Identifiera om och hur kemikalierna kansubstitueras, och ungefärlig kostnad för substituering.

I rapporten ingår en översikt av metod och resultat, samt tre bifogade PDF-filer (vilka finns som bilagor) innehållande utförlig information om alla kemiska ämnen som kan förekomma i färdiga varor.

Den första PDF-filen är ”IN-Listan”. Detta är kemikalier som kan finnas i färdiga produkter. Den andra PDF-filen är ett verktyg som kallas ”volymberäknaren”, som författarna skapat för att uppskatta potentiella volymer för de kemikalier som används i läder- och textilindustrin och importeras till Europa. Den tredje PDF-filen är en visualiserad ”prioriteringskontroll”, vilket kan förtydligas som IN-Listans kemikalier sorterade efter prioritet, ordnade från A till D.

På ”IN-Listan” visas kemiskt namn och CAS-nummer, användning/funktion, var i leverantörskedjan som ämnet används (avsiktligt eller oavsiktligt), volymer, uppskattad ppm-halt för varor vid försäljning, alternativ, kostnad, rekommendationer och föreslagen prioritet (A till D) för varje ämne eller grupp av kemiska ämnen, i förekommande fall.

Tillverkning av textilier och läder är en komplicerad process, bestående av ett flertal bearbetningssteg där kemikalier används och avlägsnas genom tvättning och sköljning, eller genom att tillföra värme. Vissa ämnen kan finnas i kemiska formuleringar men förekommer sannolikt inte i färdiga varor. I våtprocessen används vissa ämnen avsiktligt, till exempel färgämnen och ämnen för ytbehandling, medan andra används även oavsiktligt, till exempel konserveringsmedel, antioxidanter, stabiliseringsmedel osv. En del kemikalier förekommer i form av spårämnen, oreagerade monomerer eller intermediärer. Vissa kemikalier är avsedda att finnas kvar i varan, medan andra används som hjälp i produktionen, till exempel katalysatorer, smörjmedel, tvättmedel osv.

I rapporten anges den metod som används för att testa och med industriella experter verifiera vilka av de 346 ämnena som kan förekomma i färdiga varor i som säljs i butik.

Kemikaliernas kvantitet, och var de används, bestäms genom att göra en volymberäkning för varje kemiskt ämne som används i tillverkningen av textilier och läder sålda i EU. (Uppskattningar av den mängd kemikalier som används i tillverkningen av textilier och läder sålda i EU kan endast vara kvalitativa: antaganden och beräkningar anges för varje ämne i

2 Några av ämnena saknar en harmoniserad klassificering för faroegenskaperna, men inkluderas i listan eftersom de har identifierats förekomma i färdigproducerade varor i butiker via kemiska tester.

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volymberäknings-PDF-filen). Där så är lämpligt har kemikalier med liknande kemiska egenskaper (t.ex. ”diisocyanater” eller ”kromföreningar”) grupperats tillsammans när volymer och alternativ beaktas.

Slutligen anges även, där så är lämpligt, prioriteringar och rekommendationer till lagstiftning, till exempel ”förbud” eller ”reglera gränsvärden i varor i butik” för olika ämnesgrupper för att underlätta prioritering av eventuella toxikologiska och samhällsekonomiska utredningar. Kemikalieinspektionen kan dock komma till andra slutsatser.

I studien identifierades 116 kemiska ämnen på listan som potentiellt förekommande i färdiga varor. Författarna föreslår att dessa utvärderas ytterligare ur ett toxikologiskt och samhällsekonomiskt perspektiv.

Utifrån råd från toxikologer på Kemikalieinspektionen exkluderade författarna irriterande ämnen som inte kan tänkas förekomma i färdiga varor i halter över 10 000 ppm och frätande ämnen som inte kan tänkas förekomma i färdiga varor i halter över 1 000 ppm.

Alla hudsensibiliserande ämnen som kan förekomma i ppm-halter eller mer finns med i slutlistan för rapporten – de ämnen som förekommer i halter som en toxikolog bedömer inte orsakar hudsensibilisering vid den halt som anges i rapporten kan sedermera tas bort från listan. Kemikalieinspektionen kan välja att gå längre än definitionen för hudsensibilisering och även beakta halter som ger en redan sensibiliserad individ en allergisk reaktion. I dessa fall behöver en toxikolog räkna med lägre tröskelvärden.

Författarna ger kommentarer och rekommendationer för varje kemiskt ämne eller grupp av kemiska ämnen på listan. I vissa fall är det relativt enkelt att välja andra tillgängliga alternativ (t.ex. färgämnen). I andra fall rekommenderas att vissa kemikalier även fortsatt används, men med hårda kontroller av tillåtna halter i de färdiga varorna (t.ex. vissa intermediärer för färgämnen/kemikalier, diisocyanater).

För några kemikalier på listan krävs ytterligare, utförliga diskussioner med den kemiska industrin så att utfasningar och substitueringar inte får negativa konsekvenser (t.ex. användning av konserveringsmedel eller lösningsmedel i kemiska formuleringar).

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1 Background Production and processing of textiles, leather, furs and hides can involve a number of skin sensitising, skin corrosive and skin irritating substances that may remain in finished articles of clothing, footwear and other articles that come in contact with the human skin.

REACH3 (EC 1907/2006) is a regulation of the European Union, adopted to improve the protection of human health and the environment from the risks that can be posed by chemicals, while enhancing the competitiveness of the EU chemicals industry.

Restriction of chemicals constitutes a legal instrument under REACH, which can be used to protect human health and the environment from unacceptable risks posed by chemicals. REACH-restrictions are normally used to limit or ban the manufacture, placing on the market or use of a substance, but can impose any relevant condition, such as requiring technical measures or specific labels. A restriction may apply to any substance on its own, in chemical products or in an article, including imported products and articles.

The dossier proposing the restriction contains background information such as the identity of the substance and justifications for the proposed restrictions. It includes the identified risks, any information on alternatives to the substance and the costs, as well as the environmental and human health benefits, resulting from the restriction.4

The Swedish Chemicals Agency and the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) are preparing a proposal for a restriction of skin sensitising, skin corrosive and skin irritating substances in textiles, leather, fur and hide under the REACH regulation. The preliminary scope of the restriction proposal is for textile clothing and related accessories, leather and fur clothing and related accessories, home textiles including furnishings, bed and bath, carpets, mats and rugs, fashion accessories, footwear and handbags, backpacks and briefcases.

As of March 2018, 1,846 substances with a harmonised classification as either skin sensitising category 1/1A/1B, skin corrosive category 1/1A/1B and/or skin irritant category 2 have been identified. In addition, there are 10 substances with an adopted RAC opinion for either of these classifications that are not yet included in Annex VI of the CLP Regulation.

Based on information on use from the sources below, the Swedish Chemicals Agency have identified approximately 6,000 substances potentially used in textiles, leather, furs and/or hides. In addition, another approximate 6,000 substances with structural similarities to these have been identified.

Out of the approximate 12,000 substances (the total substance list) potentially used in textiles, leather, furs and/or hides, 320 substances have at least one of the harmonised classifications listed above. An additional 26 chemicals, identified in the ANSES (2018) study are known to be used in clothing and footwear, have also been added to the list of 320 substances. These 346 substances are called the screening list and they are passed on to phase I where relevance, screening and validation with regard to usage in textile, leather, hides or furs is assessed.

3 Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC) No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Commission Directives 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC. 4 For more information on restrictions under REACH, see https://echa.europa.eu/regulations/reach/restriction

https://echa.europa.eu/regulations/reach/restriction

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These substances were obtained either from the ANSES study “Assessment of the skin sensitising/irritant effects of chemicals found in footwear and textile clothing” published in April 2018 or from the lists shown below.

The IUCLID database,

The Swedish Products Register,

The SIN list,

The Colour Index database,

CpCAT database (US EPAs product database),

KemI’s textile list (unpublished),

CLP database (ECHA),

SPIN database (Nordic Product Register data),

The aim of the report is threefold

PHASE I - Identify substances on the 346 substance “screening list” that are used in the production of textiles, leather, furs and hides, and that are likely to be present in any of the finished articles.

PHASE II - Gather information about levels in formulations, use patterns and potential consumer exposure, and narrow down the “screening list” to an IN-List, which consist of substances identified as potentially being present on finished articles´.

PHASE III – Estimate approximate volumes, identify if and how the substances can be substituted, and the approximate costs of substitution.

https://www.anses.fr/en/system/files/CONSO2014SA0237RaEN.pdfhttps://www.anses.fr/en/system/files/CONSO2014SA0237RaEN.pdf

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2 An overview of textile processing To better explain the approach to identify chemical substances that may be present on finished textile articles and leather, a brief overview of textile manufacturing, the textile supply chain, and textile chemical formulations is provided.

Textiles are broadly divided into 3 different types

Synthetic fibres such as polyester, nylon and acrylic,

Natural fibres such as cotton, wool and linen

Manmade fibres derived from cellulosic wood pulp. This includes rayon, modal and lyocell.

Any of these fibres can be knitted or woven into textiles. The processing steps between knitted and woven textiles are similar except knitted fabrics require knitting oils5 to lubricate the knitting machinery, and woven fabrics require sizing agents (e.g. starch or poly vinyl acetate) to facilitate weaving. The size is subsequently removed in additional processing steps.

Many steps transform a fibre into a finished textile article. Each step requires chemical substances, sometimes applied as the chemicals themselves, but often contained within chemical formulations. These formulations are applied to fibres, yarns, fabrics or garments, usually in the presence of water.

The following sequential steps provide a high level overview of the processes that a textile article endures as it moves through the supply chain towards its finished state.

2.1 Textile processing6 1. Fibres are produced. Natural fibres such as cotton and linen are normally grown with

the addition of fertilisers and pesticides, whereas synthetic fibres such as polyester and nylon are usually produced from oil.

2. The fibres are spun into yarns. (Continuous filament synthetic yarns are produced as the fibre is formed)

3. The yarns are either woven or knitted into a fabric. 4. The fabric is prepared for dyeing by scouring, bleaching and neutralising the bleach. 5. The fabric is dyed and/or printed. 6. Any unfixed dye is washed off to meet colourfastness requirements. 7. The fabric is finished with the application of basic softeners or performance

chemicals and dried at typically 140°C for drying or higher than 160°C for curing.

8. Some products, such as denim jeans, are garment washed in industrial laundries to create abrasion patterns and a “washed down” casual aesthetic.

5 There is a slight chance that knitting oils may be present on a finished textile if the textile has not been thoroughly washed during processing. This however is not common. Good manufacturing practices always include a thorough wash off of chemicals. 6 The order of the steps may vary, depending on the desired end state of the product. For example, for yarn dye patterns on woven fabric, the yarn is prepared and dyed prior to weaving. In some cases, even the fibre is dyed.

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Most chemicals used in wet processing serve a particular purpose during a process, after which they are removed. However, some chemicals, such as dyes and chemical finishes, are intended to stay on the finished article at point of sale.

Additionally chemicals may be present in finishing formulations that serve no purpose on the finished article (e.g. preservatives in chemical formulations, chemicals that control pH etc.) but that will be present at point of sale unless there is a subsequent laundry process.

One of the last steps in the manufacturing process is to dry the article, using high temperatures. During this process volatile chemicals can evaporate, dramatically reducing the amounts present on the finished article. [For reference the EU uses a boiling point of 250oC in its definition of volatile organic compounds (VOC’s)].

Figure 1 below, shows the textile supply chain and all of the places where chemical formulations are added and then removed.

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Figure 1. Visual of the textile supply chain. In summary, most chemicals that are used in textile processing are not present on finished articles at the point of sale.

2.2 Leather processing The leather supply chain also follows a series of sequential steps; however the steps are different, and the chemical substances required in leather processing are also different.

The following steps transform an animal skin7, also known as a hide, into a finished leather article.

1. The hide is stripped of hair, and excess flesh and fatty tissue is removed. 2. The hide is preserved and made durable using a series of processing steps known as

tanning. Usually chromium compounds are present in tanning, which are particularly hazardous to workers.

3. The hide is dyed and then grease, or a synthetic alternative, is added to improve the hand feel and aesthetics.

4. The hide is further treated to help prepare it for its final use. (Shoes, jackets, accessories etc.)

7 Animal hides are made into leather via a series of manufacturing steps. An animal hide would not be sold directly to a consumer until it has gone through some textile processing.

For this assignment, fur can be considered as leather with hair. Examples are sheepskin and animal pelts used to make jackets and other types of apparel items. Both leather and fur need to be treated so that they become durable and can attract dyes and other performance chemicals that provide a set of functional benefits.

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5. Finally, the hide is finished to provide additional functionality. A significant proportion of leather has a synthetic coating applied to enhance aesthetics and / technical performance.

2.3 Textile and leather formulations In addition to understanding textile and leather wet processing, it is also important to understand what types of chemical substances may reside in the formulations used to process textiles and leather.

Upstream synthesis of chemicals (at the chemical manufacturer) usually involves relatively simple chemical building blocks to form chemical ‘intermediates’. Chemical intermediates are reacted to form the desired chemical species –a dye or an emulsifying agent or a softener etc. Catalysts speed up chemical reactions, and very few reactions involve entirely pure (uncontaminated) reagents or have 100% conversion to the desired chemical species.

Chemical formulations such as dyes, softeners etc. are therefore contaminated with impurities, unreacted building blocks, unreacted chemical intermediates, by-products from unwanted side-reactions and catalysts. Removal of such contaminants is costly and unlikely given the cost-conscious fashion industry.

Chemical formulators create formulations for use by wet processors; this involves substances to aid solubility, stability, applicability and other necessary functions.

A formulation, whether it is a dye, a detergent or a softener, always consists of a number of individual chemical substances. Some are intentionally added, whereas others may be unintentionally present.

It is difficult to know exactly what substances are present in a formulation because the chemical industry is not required to disclose all intentionally added chemicals unless they are present at concentrations that would require labelling of the formulation according to the CLP. In most cases these labelling concentrations are 1%, or 0.1% for certain harmful substances.

Figure 2 is a diagram of a typical chemical formulation that shows the different ‘functional chemicals’ could be required to give the formulation the right consistency, quality and longevity.

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Figure 2. Representation of a drum of a chemical formulation used in textile and leather processing

Each drum consists of the active ingredients and a solvent, which may or may not be water, plus lower concentrations of other chemical substances that provide functions such as preserving agents, anti-oxidants, stabilisers etc. These functional chemicals play a critical role in the stability and quality of formulations, and in some cases, these substances may be unintentionally, but foreseeably present, on finished textiles. An explanation of the functions is explained in the Table 1 below.

Active Ingredient/s

Solvent

By-products

Preservative pH control

Anti- oxidant

Anti- reductant

Catalyst Stabiliser

Viscosity control

Contaminants

Wetting agent

Emulsifier

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Table 1. Typical chemical substances in chemical formulations

Function Definition

Active ingredient

The substance with a desired function that is deliberately applied to an article [e.g. a dye, a water repellent finish or a softener]. Sometimes the formulation is ‘passive’ and the active ingredient is simply transferred to the leather/textile [e.g. many softeners and dyes] Sometimes the formulation is reactive and the active ingredients react to form a different chemical on the leather/textile [e.g. some resins, coatings and binders]

Solvent Solvent is commonly water but can be organic or mixtures of chemical substances. Residues of solvents from upstream manufacturing processes may also be unintentionally present

Contaminants No chemicals used in leather/textile processes are 100% pure due to cost constraints. All contain impurities

By-products /intermediates /unreacted substances

No chemical process results in a 100% conversion of starting materials to the intended product – there are always unwanted side-reactions and by-products form upstream processes. Unreacted building blocks and intermediates may be present in a formulation.

Preservatives Preservatives are used to extend the shelf life of a formulation by preventing degradation by microbes.

Substances for pH control

Acids, alkalis and buffers are used to keep formulations at an appropriate pH for storage and application. Poor pH control can result in costly precipitation, coagulation etc.

Catalyst Active formulations (where curing/cross linking is required) may deliberately include a catalyst and residues of catalysts from upstream manufacturing may also be present

Wetting agent Detergents are used to ensure formulations can penetrate textiles/leather

Emulsifier Many formulations contain oils/water mixes that can only be stabilised by the use of an emulsifying agent

Anti-oxidant Some chemicals are degraded by oxidation (exposure to air). Anti-oxidants are used to protect against costly damage

Anti-reductant Some chemicals are degraded by reduction (exposure to reducing agents). Anti-reductants protect against costly damage

Viscosity control

Some formulations contain gels or diluents to adjust viscosity for optimum application

Stabilisers Required to maintain good conditions for the formulation during storage and/or of the chemical when applied to textiles leather

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3 Method The following three-phase approach was used to identify the chemicals from the screening list that needed volumes and availability of alternatives.

Figure 3. High-level approach of the entire project.

The outcome of the project is a list (the IN-List) of chemical substances that can potentially be present on articles at point of sale in concentrations that can potentially cause harm to consumers. In order to do that it is necessary to:

Establish if chemicals are used in the processing of textiles/leather or in the manufacture of chemicals for use in wet processing

Establish if they may still be present at point of sale, and at what concentrations, after going through industry standard processes (the authors have tended to err on the side of caution without looking at barely plausible, worst case scenarios)

3.1 Phase I – Relevance, screening and validation8

8 A source, used in phase I has been Haz-Map Information on Hazardous Chemicals and Occupational Diseases, U.S National Library of Medicine (2018).

PHASE 1 – Relevance, screening and validation

PHASE 2 – Possible consumer exposure

PHASE 3 – Qualitative tonnage and alternatives

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Some chemicals have a clear, single use (dyestuffs), some have multiple uses (some organotin compounds are used as catalysts and antimicrobials) and some chemicals have no obvious use in wet processing or in the manufacture of textile/leather chemicals.

Some of the research on each chemical substance provided historical uses, and the authors used their experience and industry contacts to determine to the best of their ability if these chemicals are still in use today.

The following questions were applied to each listed chemical and the responses for the “IN List” of chemicals were documented on the PDF in appendix 6.1

1 Is it used in textile or leather manufacturing? This high level question was designed to weed out irrelevant chemical substances not used in textile or leather manufacturing.

2 Is it used in upstream agriculture? Many of the chemical substances are classified as herbicides or pesticides that are not expected to be present on articles at point of sale, due to their upstream use.

3 Is it used in upstream chemical synthesis? Some of the substances are used by the chemical industry as building blocks or intermediates to make new chemicals, including dyes, pigments and other textile or leather auxiliaries. Residues may exist in chemical formulations, and there is a possibility that some may be present on articles at point of sale if they are present in formulations that are not washed off.

4 Does the wet processor deliberately use the substance during textile or leather processing? If a wet-processor deliberately uses the chemical substance, the likelihood of it remaining on finished articles may be significant. Dyes, softeners, tanning agents etc. are deliberately used in larger quantities, whereas preservatives, anti-oxidants, stabilisers, are not deliberately used, and may be present in smaller quantities.

5 Does a chemical formulator deliberately include it in a formulation? Chemical formulators use a variety of chemicals in a formulation, many of which are not disclosed on the safety data sheets. Ideally the response to this question should come from chemical formulators who have the knowledge about which functional chemicals are added to a formulation. If present in formulations that are intended to stay on finished articles, there is a chance they could be present on articles at point of sale.

6 Is the chemical unintentionally present in a formulation? Some chemical substances, such as residues, intermediates, monomers or contaminants are not intentionally present in the formulation. Although the concentration may be low, if present in formulations that are intended to stay on the finished articles, they could be present at point of sale.

7 Is the substance indented to stay on the product? Dyes, printing inks, softeners etc. are intended to stay on the article due to the function they provide. Process chemicals, such as catalysts, acids, alkalis, solvents, detergents, wetting agents, pesticides and “in-can” preservatives are not intended to stay on the product.

8 Is the chemical substance present in a finishing formulation and intended to stay on the product? If the answer is yes to this question, then presence of the chemical at point of sale is possible.

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3.2 Preliminary categorisation The eight questions helped determine relevance, intentional / unintentional use, and where in the supply chain / process the chemicals may come into contact with textiles or leather.

In phase I, chemicals irrelevant to textiles / leather and those that have no chance of being present at point of sale were eliminated so that more concentrated efforts could focus on chemicals of concern.

To help with this process, five provisional categories were created to provide industry experts with pre-screened, organised lists for their review. These categories are shown in Table 2.

Table 2. Criteria for substances that may be present on finished articles

Rank Criteria Rationale

1 Almost definitely present on textiles and / or leather at point of sale

Chemicals deliberately applied to textiles during wet processing and intended to stay there (e.g. dyes, softeners).

Chemicals known to be in formulations that are applied to textiles during wet processing and intended to stay there.

Chemicals known to be in fibres and are known to stay there throughout wet processing

Chemicals intentionally or unintentionally applied, and which are known to be present on some finished textiles (e.g. via RSL testing9)

Use patterns known

2 Realistic possibility of being present on textiles at point of sale

Chemicals that are known to be present in formulations (e.g. via MRSL testing) that are deliberately used/present during wet processing / finishing and that may be present at point of sale

Chemicals where literature suggests they are deliberately used/present during wet processing and they could be present at point of sale

Use patterns may not be fully known – or could be very isolated problems

3 Possible – but unlikely to be present on textiles at point of sale

Chemicals that are applied in up-stream processing (e.g. spinning, weaving, bleaching and dyeing) that should not be present at point of sale if good/normal practice is followed

9 RSL testing is conducted on finished articles. MRSL testing is conducted on chemical formulations. The authors have access to some RSL test data from clients. If the chemical is present on a RSL report, it means that it is present on a finished textile or leather, and that it was added either intentionally by the wet processor or was unintentionally used by the wet processor.

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4 Very unlikely to be present on textiles at point of sale

Used in up-stream synthesis – maybe to make the building blocks that make the final chemical

Only used in very up-stream activities such as agriculture with the expectation they will be washed away during multi-stage wet processing

Chemicals that are highly volatile and would be expected to vaporise before being placed on sale

5 Irrelevant – Not used in textiles

No known use in textiles incl. upstream synthesis

The following assumptions and preliminary research were used to place chemicals in the appropriate provisional category

Assumptions 1. Chemical substances only used in agriculture will be removed during subsequent wet

processing and will not be present in articles at point of sale.

2. Chemical substances only deliberately used in upstream chemical synthesis (building blocks, intermediates and solvents) will be washed out during wet processing. They will only be present at point of sale if they are present in finishing formulations, coating formulations and pigment printing formulations that are intended to stay on the product.

3. Chemical substances deliberately applied during the dyeing or finishing stage of textile manufacturing and the tanning, dyeing and finishing stage of leather processing that are intended to stay on the finished article will probably be present. (Reactive dyes are the exception because they completely change during the textile processing.)

4. Chemicals with a low boiling point may be removed during the drying step of textile manufacturing (typically 140 oC for drying and higher than160 oC for curing), which usually occurs at the end of the textile manufacturing process. Water will still evaporate at temperatures lower than 100 oC; therefore it is assumed that chemicals with boiling points similar to or lower than water will evaporate during drying. Even chemicals with boiling points up to 200 oC will be reduced during drying.

5. Chemicals categorised as skin sensitisers, corrosives or irritants are not often used in textile and leather manufacturing in 100% form; they tend to be present in chemical formulations at lower concentrations, and these formulations are applied in relatively small amounts. Some listed chemicals may be present on finished articles but not at levels that can potentially cause harm to consumers. However during phase I, any chemical thought to have the potential to be present at any concentration was included at this stage (some irritants and corrosives were subsequently ruled out after discussion with toxicologists at Swedish Chemicals Agency, see page 29 for more information)

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6. Textile and leather manufacturing is conducted under normal “Industry practice” conditions. For example, unfixed dye is washed off to achieve good colourfastness, and all chemicals are used for their specific intended purpose. (E.g. a chemical that is used to preserve a formulation would not be used as an antimicrobial finish on a textile.)

For phase I, a single, consolidated list was created that contained all substances provided by the Swedish Chemicals Agency (in total three lists of substances were originally provided). The total number of chemicals on the three lists was 441. The list was culled by eliminating 95 duplicate chemical substances, which left 346 chemical substances that were considered in scope of this study.

The initial screening by the authors yielded preliminary information that was then sent to industry experts for comments and verification, see Table 3

Table 3. Initial screening categorisation by authors prior to expert verification

Criteria Number

Definitely present on textiles and /or leather at point of sale 62

Realistic possibility of being present on textiles at point of sale 80

Possible – but unlikely to be present on textiles at point of sale 78

Very unlikely to be present on textiles at point of sale 92

Irrelevant, not used in textiles 38

3.2.1 Expert verification The authors conducted a preliminary categorisation using their expertise and experience in textile chemistry, dye chemistry and textile wet processing.

However industry experts, who may have more knowledge of use patterns and chemical properties, were asked to comment and provide additional input on the preliminary categorisation.

The chemical substances in each of the tabs was sent to the following expert groups

The ZDHC technical working group

The AFIRM Group

TEGEWA (trade association representing the German Chemical Industry)

ETAD (Ecological and Toxicological Association of Dyes and Organic Pigments Manufacturers.

Nimkartec

Bluesign

VF who own the ChemIQ data – test data on textile formulations. The information provided by the expert reviewers broadly supported the initial categorisation, although a few chemicals did move to a different category.

If a knowledgeable industry expert provided information to confirm that a chemical was definitely used, it was moved to one of the two higher priority categories. If a single expert

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commented that a chemical was “not used,” but there was evidence from RSL or MRSL testing to show it was sometimes detected, it was not eliminated.

The information provided by industry experts was also valuable in phase II of the project where final decisions to include the chemical in the list of chemicals that can potentially be present at levels that could potentially cause harm to consumers via skin contact (the IN-List) were made.

3.3 Phase II – Possible consumer exposure The goal of this phase was to take the five categories, identified in the initial screening, and consolidate them into two groups:

IN-List. Chemical substances that could potentially be present on final textile or leather articles at levels that could potentially cause harm to consumers.

OUT-List. Chemical substances that will not be present on final textile or leather articles, or will not be present at levels that could potentially cause harm to consumers.

This was achieved by examining available RSL (finished product testing) and MRSL (formulation testing) test data, and by estimating the amount, in parts per million, of the substance that may be present on the finished article.

More detailed research into use patterns and physical properties of the chemical substances was conducted to help ascertain whether they could realistically be present in articles at point of sale.

3.3.1 Knowledge via test data The author’s had access to test data in the form of restricted substance list (RSL)10 and manufacturing restricted substance list (MRSL) test reports:

1. RSL (finished product testing) Listed chemicals detected in finished articles provided incontrovertible evidence that the chemicals can be present at point of sale. It also provides insights into the intended, or unintended presence on articles. A positive test does not mean that the substance is intentionally added, but it does mean that it is present on a finished article.

2. MRSL (formulation) testing This test data was obtained from Chem IQ, and it provided incontrovertible evidence that some listed chemicals are present in some formulations. The amounts present can vary, as can the types of formulations a listed chemical is found. If listed chemicals are found in finishing formulations, coating formulations or pigment printing formulations, it is assumed they can be present on articles at point of sale (subject to boiling points, chemical instability etc). If listed chemicals are only detected in formulations used in upstream processing (e.g. scouring assistants) it is unlikely they will be present in finished articles.

3.3.2 Elimination of chemical substances based on physical properties

10 Restricted substances lists relating to specific restrictions on finished textile and leather products were referenced (such as OekoTex and Bluesign), as were lists and documents relating to specific restrictions for chemicals in textile and leather formulations (such as the ZDHC MRSL, the AFIRM Chemical Guidance Document and Chem IQ).

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Some listed chemicals are clearly used or present in wet processing and / or in the manufacture of chemicals / chemical formulations, but can be discounted from being present on finished articles due to their physical properties and / or where they are used in the process. The following questions were considered:

1. What is the likelihood of the chemical substance being washed off during textile or leather processing? Highly water-soluble substances used upstream are likely to be washed off during subsequent processing and are therefore not likely to be present on finished articles. Chemicals added in finishing, coating or pigment printing would have little chance of being washed off even if they are soluble.

2. Will the boiling point or lack of stability mean that the chemical will be removed by heat during either drying or curing or both? Chemicals with low boiling points will almost definitely be removed during drying, and some listed chemicals (e.g. hydrazine) are so fundamentally unstable that they will react to form other substances and therefore would not be present at point of sale.

3.3.3 Elimination of irritants and corrosives that are present at levels too low to cause a skin reaction

Just because a listed chemical is present on a finished article does not mean it is present at levels that will cause a reaction.

After discussion with toxicologists at the Swedish Chemicals Agency, it was determined that:

a) For a chemical categorised as an irritant to be problematic, it would need to be present above 10,000 ppm on the finished article. Any irritants that will not be present above 10,000 ppm were excluded from phase III of this study.

b) For a chemical categorised as a corrosive to be problematic, it would need to be present above 1,000 ppm on the finished article. Any corrosives that will not be present above 1,000 ppm were excluded from phase III of this study.

For skin sensitisation, an individual has to be exposed to a given concentration of a chemical, and once sensitised, they can react to much lower concentrations.

The authors (Cattermole Consulting Inc. and Colour Connections Consultancy Ltd.) believe that articles should be controlled to levels that preclude the onset of skin sensitisation whereas the report commissioners (the Swedish Chemicals Agency) believe that articles should be controlled to the [lower] levels at which a sensitised individual can suffer an allergic reaction.

Neither of these limits has been established for the listed chemicals and therefore all skin sensitisers that can potentially be present at ppm levels have been included.

It is conceivable that in due course a toxicological study could eliminate some skin sensitisers if they are deemed to be never present at levels that can cause sensitization and/or allergic reactions for sensitised individuals.

NOTE: The authors were requested to include any substances that formed part of the ANSES study (2018) if they could potentially be present in a finished article, even though some were not categorised as skin sensitisers. The authors agreed to include some of those chemicals but not others, and any disagreement has been highlighted in the final “IN list” PDF in appendix I.

3.3.4 Estimation of worst case ppm’s present on a finished article

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In anticipation of a toxicological study to further rationalize the number of chemicals, (and to help with estimation of chemical volumes) the amount (in ppm) of chemicals that could be present on finished articles was estimated.

The amounts of deliberately applied chemicals can vary. For example, pale shades require significantly less dye than dark shades, and coatings can be applied in thick or thin layers. In addition, the amount of unintended contaminants and residual building blocks, intermediates and solvents can also vary.

Due to these variations, the amounts present (shown in the final “IN-List” PDF) are estimates designed to give some level of appreciation of the order of magnitude of contamination and application.

The authors have erred on the side of caution and levels represent “what could be present if applied at the highest likely level at the latest feasible time in the process.”

In the final results “IN-List” PDF, there is an indication of ‘high’, ‘medium’, ‘low’ and ‘very low’ for the estimated amount of a chemical substance in a formulation and on the final article. The assumptions made are shown in Table 4.

Table 4. Chemical concentration ranges for formulations and finished articles

Textile or leather chemical formulations

Range Concentration Rationale

Very low < 100 ppm By-products, contaminants, preservatives, wetting agents, anti-oxidisers etc.

Low Between 100 and 1000 ppm

By-products, contaminants, preservatives, wetting agents, anti-oxidisers etc.

Med Between 1000 and 10000 ppm

Active ingredients, solvents

High > 10,000 ppm This usually represents the active ingredient in a textile formulation such as a dye or a softener. The percentage will usually be between 10 and 70% with most of the remaining being the solvent

Leather or textile articles

Very low < 10 ppm Residuals, contaminants & substances used upstream

Low Between 10 and 100 ppm

Some residuals may be present in this concentration or chemicals that are unintentionally used by the wet processor

Med Between 100 and 1000 ppm

Some residuals may be present in this concentration or chemicals that are unintentionally used by the wet processor

High > 1000 ppm This concentration is for chemicals that are added intentionally especially at the dyeing and finishing stages of the supply chain

NOTE: The amount of a chemical substance in a formulation does not directly translate to the amount on an article because of physical properties (e.g. evaporation), the point in the wet process it is applied, and the potential for chemical reactions to occur (e.g. diisocyanates may be present at huge percentage amounts in a formulation, but they should fully react and be non-detectable on a finished product in a properly controlled process.)

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3.3.5 Further information to aid downstream prioritisation The authors have included any chemical substance they believe could potentially be present at levels that could potentially cause harm to consumers and indicative ppm levels on finished articles.

In order to estimate total volumes of listed chemicals in the EU market, and to evaluate overall risk to consumers, the type of articles that can be affected by a particular chemical, and the percentage of the market those articles represent was considered.

For example, alkylphenyl ethoxylates (APEO’s) could be applied, intentionally or unintentionally, to any textile or leather article, thus representing 100% of the market. These chemicals are surfactants that are added to many formulations including detergents and softeners, both of which are used ubiquitously in textile and leather wet-processing. They are therefore likely to be a higher priority than a chemical that is only applied to wool, which has a 1% textile market share.

Where possible, the authors tried to get information about the “likelihood of use” to give an appreciation of how frequently the listed chemical may be included / present in either formulations or deliberately applied to textiles or leather. Without full information from every global wet processor, chemical manufacturer and formulator, this is an impossible task. However, the authors know that some chemicals are still widely used, (APEO’s for textiles and leather and chromium compounds in leather tanning). Others are now rarely used (organotin compounds for textile finishing and triclosan as an antimicrobial finish) on textiles.

The information documented in the “IN-List” PDF is provided in good faith. The authors accept that definitive information that contradicts their views may arrive from the industry via the ECHA call for information and evidence, which is ongoing in parallel to this study.

The authors have provided information to allow readers and the Swedish Chemicals Agency to prioritise chemical substances, but they have not removed any chemical from the list if the information suggests it could be a low priority.

The authors have not made judgment calls on the “relative harmfulness” of any of the chemical substances that could be present on finished articles other than the advice from the toxicologists regarding elimination of corrosives and irritants if not present above the aforementioned levels.

Information on the types of product the chemicals may be found on (‘all textiles’, ‘all textiles and leather’, ‘cotton textile only’, ‘rubber coated textiles only’ etc) is provided in the “IN-List” PDF.

3.3.6 Consolidation of five lists [end of phase I] into two lists [end of phase II] The final step of phase II, was to consolidate the chemical substances into two lists (the IN-list and the OUT-List). This was achieved by implementing all of the steps discussed in the method. The two lists can be described as

Chemical substances that could potentially be present on final textile or leather articles (the IN-List) at levels that could potentially cause harm to consumers.

Chemical substances that will not present on final textile or leather articles, or will not be present at levels that could potentially cause harm to consumers (the OUT-List).

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3.4 Phase III – Volumes and alternatives For chemical substances that can potentially be present on finished articles at levels that potentially cause harm to consumers, part of the approach was to:

a) Estimate the approximate total volume of each chemical substance used in the manufacture of textile and leather articles sold in the EU.

b) Identify, where possible and appropriate, alternatives for the listed chemicals and provide some information on associated costs and technical challenges.

Getting accurate information on volumes without a legal requirement for chemical formulators to disclose accurate information on the content of formulations, and without access to confidential sales data from all global chemical suppliers, is an impossible task.

Therefore models and estimates were used to generate figures to demonstrate the approximate scale of usage. (See the volume ready reckoner available in appendix II).

NOTE: Many chemicals on the list are not restricted or completely banned and are therefore registered with ECHA for manufacture or import. It is impossible to determine if the registered chemicals are solely used for textiles or leather, but those registration volumes do give some indication of the tonnages in circulation across all industries.

Some of the chemicals on the list do not have an ECHA registration, which suggests that deliberate use / permitted import does not occur, and that the only usage is outside the EU. This may be a consideration for further prioritisation of substances.

3.4.1 Volume ready reckoner To estimate the potential quantity of chemical substances used in textile and leather manufacture, a simple excel-based calculator, the volume ready reckoner, was created and used, and it is available as a PDF in appendix II).

The data used in the volume ready reckoner were:

A. An estimate of the total volume of textiles and leather used in the EU per annum. B. An estimate of the percentage of textiles and leather that can potentially be affected by

the specific listed chemical (e.g. all textiles and leather = 100%, acrylic only = 2% of textiles, polyester only = 55% of textiles, coated/pigment printed textiles = 15% of all textiles). It is estimated by the authors that 15% of textiles are coated or pigment printed, 30% of leather products are coated or pigment printed and 1% of textiles / leather is rubber coated.

C. An estimate of the likelihood that a listed chemical substance is present in a formulation of a given type – for example

a. Assume an in-can preservative is present in 1 in 50 formulations b. Assume that a rubber accelerator is present in 1 in 20 rubber formulations

D. It was assumed that an average of 10 chemical formulations are used in a wet process. If a listed chemical is assumed to be present in 1 in 50 formulations, it will be present in 1 in 5 (20%) of potentially affected articles.

E. An estimate of the percentage of a listed chemical that is deliberately applied, or the percentage of a chemical that is unintentionally applied (by weight of substrate). For example, for chemicals in formulations, the amount applied by exhaustion methods is calculated by assuming that a chemical formulation is applied at 2 g/l at a liquor ratio

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of 10:1. (so 2 g/l of a formulation applied at 10:1 liquor ratio is an intentional add-on of the total formulation of 2%. If a specific chemical is present at 1 % in a formulation, the amount added is 1% of 2 % = 0.02%)

A figure for the annual volume of a chemical used in the manufacture of textile or leather articles sold in the EU, in tonnes, is calculated as follows

V = A x B% x D% x E%

V = (Annual Tonnage of textiles or leather sold in the EU) x (% of articles that are potentially affected) x (% likelihood of the chemical being present in an article ) x (% of chemical applied)

Figure 4. Global fibre production. Source: Tecnon Orbichem. http://www.orbichem.com/userfiles/APIC%202014/APIC2014_Yang_Qin.pdf

The information in the table above provides estimates for total fibre consumption (for all end uses in all global markets) and a breakdown by fibre type

EU tonnages used in the calculations

The global market for textile fibres was approximately 100 million tonnes in 2018.

40% of the global textile fibre market is used in technical textiles and 60% is used in apparel and home textiles (source http://www.tikp.co.uk/)

Approximately 30% of global textile sales are accounted for in the EU. (source: Wazir Advisors).

The figure used for the total EU market for apparel and home textiles is therefore:

100,000,000 x 60% x 30% = 18,000,000 tonnes

The global market for leather is approximately 7 million tonnes

Approximately 84% is used in footwear, apparel and furniture (source: www.ukleather.org)

http://www.orbichem.com/userfiles/APIC%202014/APIC2014_Yang_Qin.pdfhttp://www.ukleather.org/

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The EU is assumed to account for approximately 30% of sales (in line with textiles). The figure used for the total EU market for apparel and home is therefore:

7,000,000 x 84% x 30% = 1,760,000 tonnes

3.4.2 Alternatives and costs Unit costs for bulk quantities of chemicals were obtained via internet searches of trade chemical websites that included Alibaba and Zauba. These websites are useful because they provide industrial quantities of chemicals and their associated costs.

A cost range, in metric tonnes, for all chemicals on the “in list” was identified so that once alternatives were identified, the cost between the chemical to be substituted with the safer alternative could be compared.

The following method was used. Each CAS number in the “IN-List” was placed in the search bar of the trade chemical websites. The resulting costs were provided as a range. In many cases the quoted costs were applicable to a volume in metric tonnes. However, this was not always the case. If prices for smaller quantities were shown, the quantity and resulting costs were mostly recalculated to show metric tonnes. These costs merely reflect the cost at the time of the search, which occurred during the month of July 2018.

Costs could not be found for all chemicals on the “IN- List.” This could be due to several reasons including: the chemical may not be produced anymore, the chemical may be a residual, or the chemical may not be available on the websites that were used for the search.

The search for alternatives was conducted in the following three ways:

1. Websites that focus on providing alternatives to hazardous chemicals such as SubSport and the ChemSec Marketplace.

2. Search phrases including “alternatives to chromium tanning for leather” and “alternatives to nonylphenol ethoxylates”. Some searches led to some specific references for alternatives and these are captured in the PDF document that accompanies the report.

3. Contacting experts in the chemical and apparel industry. If known alternatives were suggested (such as silver ions (which may be regrettable substitution based on other aspects) replacing triclosan) further research was conducted to gather technical challenges and costs where possible.

The USEPA developed their Safer Choice program and is a leader in Alternatives Assessments. Several alternatives assessments of certain hazardous chemicals, including flame-retardants, some phthalates and nonphenyl ethoxylates have been conducted, and hence this was an excellent resource.

Finding alternatives to dyes was assumed to be straightforward because there are numerous dyes similar in shade to the dye that needs to be substituted. It was also assumed that the costs of the dyes would be similar and that no technical challenges would occur.

In some cases the authors do not think that substitution is required. Instead, control of process parameters are needed to ensure levels of certain chemicals at point of sale do not cause problems for consumers. This is discussed in the results section of the report and in the IN-List PDF.

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4 Results The results are a high level overview of insights and information about each chemical substance that is garnered from the method described previously.

Three documents (appendix I, II, III) capture detailed information about each chemical substance that was deemed to possibly be present on finished textiles and or leather articles,

1. The “In-List” PDF11 (appendix I) is a list of chemicals that the authors suggest might be of concern. The list is provided with the following details

a. Chemical name / CAS number b. Details of deliberate usage by wet processor / deliberate inclusion by

formulator / presence as unwanted residue or contamination

c. The types of product potentially affected d. Approximate levels of the chemical in formulations and finished articles e. The likelihood of being present in a potentially affected product type f. The approximate volume used in EU textiles / leather g. Any existing legal restrictions h. Information to help prioritise chemicals should further rationalisation of the list

be required

i. A recommendation from the authors as to whether they feel the chemical should definitely be of concern, probably of concern, possibly be of concern or whether the chemical is only on the list because its presence has been requested by the Swedish Chemicals Agency.

2. The volume ready reckoner PDF12, available in appendix II, provides a summary of the calculations conducted on each chemical. The output was approximate volume(s) of each chemical substance that may be used in textiles and/or leather. All assumptions made by the authors are captured in the document.

11 The 13 page IN-list PDF contains detailed information about each chemical and includes

1. The harmonised categorization, name and CAS number, the function and use for each chemical

2. Responses to the questions outlined on page 19 and 20 of this report, the types of products affected and the % of textile and leather products that may be affected.

3. Volume information, prioritization recommendations, alternatives and cost. 12 The volume ready reckoner provides information on both textile and leather products. In some cases, a chemical is used in both textile and leather production (e.g.methacrylates on page 1 of the volume ready reckoner) some are used in textiles only (e.g., disperse dyes on page 3 of the volume ready reckoner) and some for leather only (e.g., Thiocyanic acid, (2-benzothiazolylthio)methyl ester, a leather fungicide on page 1of the volume ready reckoner).

The grey shaded areas on the document means that the chemical substances are treated as a group rather than as individual chemicals substances. (Methacrylates, chromium compounds, etc)

The yellow highlighted cells represent the estimated total volume of each chemical and should be added together if that chemical is used in both textiles and leather.

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3. The priority sense checklist13, available in appendix III, is the “IN-List” chemicals, sorted by priority ranked from A-D. This is explained in the discussion section below.

4.1 Discussion of results A total of 12014 chemical substances were identified as potentially present in textile or leather at levels that could potentially cause harm to consumers via skin contact.

The authors believe an important next step is for many of these substances to be reviewed by a toxicologist to determine their relative harmfulness, so that they can be further prioritised.

A priority ranking for each substance or group of substances that was include and is shown in the priority sense check PDF from A – D, where

“A” means the chemical is of concern because the chemical is known to be in widespread use and is known to be harmful.

“B” means the chemical probably is of concern because it may be harmful but is not commonly used and /or is only potentially present in a small number of product types

“C” means the chemical could be of concern despite it being rarely used / present on articles or current use not confirmed

“D” means the authors do not think the chemical is of concern but the Swedish Chemicals Agency asked for it to be included

The authors have always erred on the side of caution and included certain chemicals that could be considered ‘marginal’ where their use was not confirmed, or where the use patterns indicate there is a very low likelihood of the chemicals being present on finished articles.

To give a simple sense check, a simple at-a-glance chart was created to show (for leather and textiles separately):

The percentage of the total textile/leather market that can potentially be affected by a chemical – ranging from almost zero to 100% (as per the ready reckoner).

The likelihood that the chemical could be found on finished articles (this is presented as a progress bar and gives a qualitative ‘high’, ‘medium’, ‘low’, ‘very low’, ‘almost non-existent’ risk).

The approximate ppms present in a worst-case scenario (this is also shown as a schematic to show ‘very high’, ‘high’, ‘medium’ or ‘low levels’).

The priority sense checker is qualitative but, taken with the commentary in the main spreadsheet, can inform the reader whether a chemical could be of concern or potentially be omitted.

13 The Priority sense check PDF contains 3 pages. It contains

The harmonization classification, CAS number and name, the category, class and function and the suggested prioritization ranking from A-D

An “at-a-glance” visual that is designed to show the approximate percentage of leather or textiles that may be affected by the chemical, the risk of being present, and the worse case PPM (low, medium and high) for textiles and leather.

14 Some do include a request by the Swedish Chemicals Agency based on the ANSES report

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The priority sense check was sorted by priority, function and then by CAS number. Readers will tend to see that lower priority chemicals have a very low chance of being present on finished articles - but in many cases not low enough to definitely rule them out.15 Figure 5 shows the thought process using different examples.

Figure 5. Visual representation of the priority sense check

In some cases, the authors recommended that certain chemical substances be treated as a group, which are highlighted and discussed in more detail below.

Chemical substances can be grouped by chemical likeness (diisocyanates) or function (dyes, in-can preservatives). For some groups, all chemicals within the group can be treated in the same way. For other groups an evaluation by the toxicologist of each substance within the group might be necessary.

15 The estimated amount of a chemical in ppm that may be present on a finished article column in the “In-List” PDF shows the worst-case scenario on either textiles or leather. This is based on knowledge/estimate, but the number is largely educated guesswork unless there is knowledge of RSL test data (e.g. Cr Vi, APEO's, Isocyanates etc). It is based on

How much is deliberately applied or present in formulations, When in the process it is applied (early on or in a finishing formulation), Physical properties (does it volatilise etc?).

The priority sense check is designed to give an at a glance visual to show

How commonly chemicals are used/present in formulations, What percentage of textiles/leather can be affected What the worst-case ppm's are.

The priority sense check is separated into both textiles and leather, which shows whether there is a leather problem, a textiles problem or both.

The bars in the priority sense check visual are not to scale. They have been slightly increased to show “tiny ppm” amounts. If they were drawn to scale, these amounts would not be visible on the schematic that is provided.

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There are some that can be considered collectively as a group when looking at volumes, socio-economic analysis substitutions and, ultimately, restrictions.

4.1.1 Groups of chemicals Not all of the chemical substances are discussed in the results section. However, each one can be found with the relevant detail, in the spreadsheet that accompanies the report.

4.1.1.1 (Meth)acrylates There are four (meth)acrylates, mostly found as residues in acrylic coatings and binders.

(Meth)acrylates have been prioritised as an “A Group” because they are used in large quantities for coatings and binders, which are intended to stay on finished products.

Acrylates (also known as polyacrylates or acrylics) are either sold in pre-polymerised form or as un-polymerised for in-situ polymerisation. The levels of (meth)acrylates present in in-situ polymerisation formulations can be very high.

The recommendation is to control the amount of (meth)acrylates on a finished product rather than ban the chemicals, and seek advice from a toxicologist to suggest if a group restriction is appropriate or whether tailored limits are required.

There are no known alternatives although vinyl acetate monomers and polyurethanes (potentially regrettable substitution) may be further investigated.

NOTE: Methacrylates with low boiling points from the original list are not included on the IN-List.

4.1.1.2 Antimicrobials Antimicrobials represent a large group of chemical substances (at least fifteen on the IN-List) and can be sub-categorised into biocides, pesticides, fungicides, herbicides, in-can preservatives and antimicrobial finishes on articles. They can also be sorted by chemical similarity.

Some antimicrobials have more than one function and can therefore not be treated as a group.

Some are approved for use and listed on the Biocidal Products Regulation (BPR, Regulation (EU) 528/2012).16 Banning these or limiting their use may be a challenge. Where applicable, alternatives have been suggested, depending on the end-use of the antimicrobial.

Antimicrobials, due to their function, tend to be reactive, hazardous chemicals. The recommendation is to have an “industry-wide” conversation to identify the safest and most effective antimicrobial for its intended function. The most relevant function identified in the list is “in-can” preservatives that increase the shelf life of chemical formulations.

From a prioritisation perspective, substances that fall into the A, B and C prioritisation ranking have been identified. Suggested alternatives have been included, but the key message is for the chemical industry to weigh in on the recommendation given their knowledge and visibility into the specific antimicrobials / preservatives used to preserve chemical formulations.

4.1.1.3 Chromium compounds

16 https://eur-lex.europa.eu/eli/reg/2012/528/oj

https://eur-lex.europa.eu/eli/reg/2012/528/oj

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There are eight chromium compounds that may or may not be used in leather tanning. Some have been used historically and it is unclear if they are all still used today.

Alternatives to chromium VI salts are chromium III salts, but these may be oxidized to chromium VI during processing or subsequent transportation / storage / use. Additional alternatives include vegetable tanning and aldehydes such as glutaradehydes, but they also have their share of health and safety issues.

Chromium compounds have been prioritized as an “A group.” The recommendation is to have a chromium VI restriction for the group because they are used in large quantities and present at point of sale on leather goods.

The authors could have excluded several specific compounds on the basis of relevance / current use but are of the opinion that a general Chromium VI restriction is sensible.

4.1.1.4 Nonylphenol ethoxylates (NPEO’s) Nonylphenol ethoxylates are surfactants and there are six in this group. Although restricted in the EU, they are still widely and deliberately used in textile and leather processing in other territories and may be present on finished products.

NPEO’s have been prioritised in the “B group” because although they are deliberately used and detected in RSL testing, failures above 1,000 ppm, the threshold for corrosives, are rare and failures above 10,000 ppm, the threshold irritants, are very rare.

The recommendation is to consider them for regulation if scientific evidence clearly demonstrates sensitisation / irritation / corrosive behaviour (currently not categorised)

There are two breakdown products of nonylphenol ethoxylates, which are not intentionally used or added to formulations and therefore no alternatives would exist. These breakdown products have been prioritised as “C group” because they have been detected in RSL testing but they are never present above 1000 ppm.

The recommendation is to remove them from the list if the categorisation doesn't change or if they are categorised only as corrosives because they will not be present above 1000 ppm. However, they should be kept on the list if scientific evidence demonstrates sensitisation / irritation / corrosive behaviour (currently not categorised).

A list of alternatives has been vetted by the USEPA and is included in the spreadsheet.

4.1.1.5 Diisocyanates There are seven diisocyanates and they are mostly used to make polyurethanes. There are alternatives to polyurethane coatings including acrylic binders, but no alternatives to diisocyanates.

Polyurethane is sometimes sold in pre-polymerised form with diisocyanates present as low-level contamination, and sometimes sold un-polymerised for in-situ polymerisation. The levels of diisocyanate present in in-situ polymerisation formulations are very high.

Diisocyanates have been prioritised as an “A group” because they are used in large quantities and have been detected in RSL testing. Diisocyanates should not be present if products are properly cured (Correct amounts ingredients, catalysts, curing conditions and potentially washing).

The recommendation is to manage diisocyanates as a group, permit upstream use and control residuals on products at point of sale. A limit value should be suggested for finished products

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at point of sale, and a toxicologist will need to advise whether to have tailored limits or a single limit for all diisocyanates.

4.1.1.6 Dyes There are 14 dyes on the list: 2 acid, 1 basic, 2 direct and 9 disperse dyes. Acid dyes colour leather, wool, nylon and silk, basic dyes colour acrylic, direct dyes colour cellulosic fibres and disperse dyes are used to dye polyester.

The dyes have been categorised as a “Group B” prioritisation because they are intentionally added and meant to stay on a product. Single dyestuffs are not used in huge quantities and alternatives should be readily available.

The recommendation is that each dye in the group should be restricted because it may be used in high quantities, and if fastness is low, it could cause problems. The fastness of disperse dyes is often poor because of poor processing.

Some of these dyes have been registered through ECHA by specific companies who may have a strong point of view regarding a restriction in the absence of strong toxicological data to validate the restriction.

4.1.1.7 Intermediates There are several intermediates (some for dye synthesis and some for other chemicals) and due to their differing properties and use patterns they have not been treated as a group.

Intermediates are normally present as residuals in formulations where the downstream user (wet processor) has no option in choosing or using them and they are rarely present on finished articles.

Whilst a restriction on some intermediates on finished articles may be sensible to protect consumers, care has to be taken with regard to substitutions, as these are building blocks from which many useful and important chemicals are manufactured.

4.1.1.8 Solvents Solvents, like antimicrobials need to be considered individually. Some exist as residues from upstream chemical synthesis and, where they are used deliberately in formulations, it is impossible to suggest alternatives without knowing the specific chemical that they are dissolving.

4.1.2 Final thoughts The authors have produced a list of chemicals with a potential concern.

This is based on the fact that these chemicals can potentially be present at levels that could potentially cause harm to consumers via skin contact.

It is recommended that a toxicological review of the skin sensitising and non-classified chemicals is conducted to establish the levels at which problems can occur, with a view to removing those that will not be present at levels where harm can occur.

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5 Reference List The following resources were used to help determine the function of the chemical substance

Committee Meeting presentation

Yang, Quin, Michelle, (2014). “Global Fibres Overview : Synthetic Fibres Raw Materials”. http://www.orbichem.com/userfiles/APIC%202014/APIC2014_Yang_Qin.pdf

Database

ECHA-CL inventory, “inform