REACH entry 72 requirements

Investigating an essential piece of European legislation applicable to the clothing, footwear and furniture industries.

One of the most significant REACH (‘Registration, Evaluation, Authorisation and Restriction of Chemicals’) updates in recent years came into effect on 1^st November 2020, with restrictions for 33 substances listed in Commission Regulation (EU) 2018/1513 under entry 72 of REACH Annex XVII. These restrictions are applicable to textiles, with clothing and footwear being two of the article types that are specifically mentioned.

However, there are important exemptions that will be highlighted in this article, which will also identify these 33 substances which SATRA customers need to consider in order for compliance with this legislation to be demonstrated.

‘CMRs’

REACH Annex XVII entry 72 concerns substances that are classified as ‘carcinogenic’ (may cause cancer), ‘mutagenic’ (may be capable of inducing genetic mutation) or are toxic for reproduction. There are different categories for these substances (which are collectively called ‘CMRs’), depending on the amount of scientific evidence about their effects on humans.

‘Category 1A’ substances are known human carcinogens, mutagens or reproductive toxicants, whereas those in ‘Category 1B’ are presumed human carcinogens, mutagens or reproductive toxicants based on animal studies. There are also substances classified as ‘Category 2’ CMRs.

Nevertheless, there is only limited evidence of their suspected effects, so entry 72 chemical restrictions are based on Categories 1A or 1B. REACH Annex XVII entries 28, 29 and 30 already restrict Category 1A and 1B CMRs that are classified in table 3.1 of Annex VI in the Classification, Labelling and Packaging (CLP) Regulation (EC) No.1272/2008. Substances and mixtures containing CMRs will be labelled with the pictogram shown in figure 1.

The CLP Regulation’s purpose is to ensure a high level of protection for both human health and the environment by setting detailed criteria for the labelling of substances and mixtures. The 33 substances listed in entry 72 of REACH Annex XVII are restricted in articles. As a result, they were added as a separate entry to those already listed in entries 28, 29 and 30.

Textiles and entry 72

Entry 72 was introduced to reduce CMRs being added to textiles through impurities in the production process, or to prevent them from being intentionally added to give specific properties. Footwear and clothing are specifically listed under the scope of the restriction due to those articles potentially being worn in close proximity to the skin for long periods of time.

Therefore, if CMR substances were present, there would be a high potential risk of exposure for consumers. The same is true for similar articles made from textiles, such as bed linen, blankets, towels and upholstery, and such items are also listed in the regulation.

Although footwear and clothing are specifically named under the scope of the restriction, the main focus of the restriction is textiles. Therefore, footwear and clothing made entirely out of natural leather, fur or hide are not covered by the scope of the restriction. This is also the case for parts of articles containing natural leather, fur or hide, due to the different chemical substances and manufacturing processes used in the production of textiles.

The exemption of leather, fur and hide is particularly significant for the footwear and furniture industries, and this should be made clear in brand owner- and retailer-restricted substances lists so that these materials are assessed against appropriate legislative requirements.

An explanatory guide published by the European Commission excludes footwear components such as non-textile fasteners and decorative attachments – for example, slide fasteners (‘zips’ or ‘zippers’), touch-and-close fasteners, eyelets and buckles – from the scope of the restriction. This implies that other non-textile components of footwear, including rubber and polymeric sole units, are included and therefore should comply with the entry 72 restrictions.

Before they are confirmed, new regulations and restrictions proposed by the European Commission are considered for economic and social factors, as well as safety concerns. Personal protective equipment (PPE) under the scope of Regulation (EU) 2016/425 and medical devices (Regulation (EU) 2017/745) are both exempted from the entry 72 restrictions, due to the need for that equipment to fulfil specific safety and functional requirements. The potential benefit from ensuring that restricted substances were not present was deemed to be outweighed by their functionality as medical devices and protective equipment.

Substances restricted in entry 72

Information on all the substances listed in entry 72 is included in tables 1 to 7. These detail possible uses for each substance and the maximum allowable limits.

Table 1: Substances in REACH Annex XVII entry 72 and their uses – miscellaneous
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
Benzene	71-43-2	5 mg/kg	Could be a contaminant in solvent-based cleaning agents
Formaldehyde	50-00-0	75 mg/kg	Preservative, anti-creasing and anti-shrinkage treatment, stiffening agent
N-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone (NMP)	872-50-4	3,000 mg/kg	Used as an industrial solvent, especially in adhesives and leather finishes
N,N-dimethylacetamide (DMAC)	127-19-5		Solvent in adhesive industry and used in the production of plasticisers and synthetic fibres such as PU and acrylic
N-N-dimethylformamide, dimethyl formamide (DMFa)	68-12-2		Used in the production of acrylic fibres, polyurethanes, adhesives, synthetic leathers and surface coatings
Quinoline	91-22-5	50 mg/kg	Industrial solvent in the manufacture of dyes and chemical intermediates

Formaldehyde

The inclusion of formaldehyde under entry 72 was the first European-wide restriction imposed on this substance in articles. In high concentrations, formaldehyde is toxic by ingestion, inhalation or skin contact, and is capable of causing severe skin burns or damage to the eyes. In addition, formaldehyde is believed to be a widespread allergen, with some people being very sensitive even at low concentrations.

Formaldehyde can be used as a preservative, especially for natural textiles. It can also be used as a finish to increase textiles’ crease resistance – for example, in the production of wrinkle-resistant clothing. Additionally, when reacted with phenol, urea or melamine, formaldehyde forms resins which are commonly used as adhesives. The maximum permitted amount of formaldehyde in textiles is 75 mg/kg.

PAHs

Polycyclic aromatic hydrocarbons (PAHs) may pose a risk to human health by ingestion, skin absorption or inhalation. Studies with animals have shown that exposure may cause eye irritation and vomiting, as well as long-term effects such as an increased risk of cancers of the stomach, skin, bladder and liver.

It is this increased long-term risk of causing cancers that justified the inclusion of PAHs into entry 50 of REACH Annex XVII in December 2015. That restriction is only applicable to rubbers and plastics that will be in contact with the skin, and requires eight PAHs to be present at less than 0.5 mg/kg in toys and less than 1 mg/kg for other articles.

The entry 50 restriction is directly relevant to articles where the plastic will be in contact with the skin (for instance, with flip-flops, handbags or faux-leather upholstery). Eight of the 33 substances in entry 72 are PAHs, and these are the same eight as listed in entry 50. The PAH entry 72 restrictions for footwear also include plastics and coated textiles that are not in contact with the skin, which has broadened the scope of existing PAH restrictions.

PAHs are not intentionally added to plastics or rubbers, but could be present as impurities. ‘Carbon black’ is a commonly used pigment in black rubbers and plastics. PAHs can be formed through the burning of fossil fuels, and carbon black can be manufactured by the partial combustion of oil or natural gas. Black rubbers and plastics generally contain carbon black as a pigment, so they are more likely to contain PAHs than other colours.

Nevertheless, all colours of rubbers and plastics may contain process oils, plasticiser oils or extender oils (which are added to modify and cheapen processing or plasticiser oils). These may also be manufactured from coal, crude oil or petrol, and could therefore contain some PAH impurities.

Table 2: Substances in REACH Annex XVII entry 72 and their uses – PAHs
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
Benz[a]anthacene	56-55-3	1 mg/kg	Could be contaminants in extender oils or carbon black pigment
Benz[e]acephenanthrylene	205-99-2
Benzo[a]pyrene, benzo[def]chrysene	50-32-8
Benzo[e]pyrene	192-97-2
Benzo[j]fluoranthene	205-82-3
Benzo[k]fluoranthene	207-08-9
Chrysene	218-01-9
Dibenz[a,h]anthracene	53-70-3

Disperse dyes and quinoline

‘Disperse dyes’ are a group of substances based on small, insoluble molecules. These are applied as a dispersion to synthetic fabrics that would not normally dye well with traditional dyeing techniques. In addition to their classification as Category 1A or 1B carcinogens, it has been estimated that approximately 5 per cent of the human race show an allergic response to disperse dyes, with individuals having different tolerance levels.

Three of the 33 substances in entry 72 are disperse dyes and, as with formaldehyde, this was the first European-wide restriction that applied to articles. All three disperse dyes are restricted in concentrations greater than 50 mg/kg. SATRA has developed the test method SATRA TM459:2024 – ‘The quantitative analysis of disperse dyes by LC-MS’ for the detection and quantification of the three restricted disperse dyes plus another of the entry 72 CMRs, quinoline. This is an industrial solvent used in the manufacture of dyes and chemical intermediates, and it has the same restriction as the disperse dyes of greater than 50 mg/kg.

Table 3: Substances in REACH Annex XVII entry 72 and their uses – disperse dyes
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
1,4,5,8-tetraaminoanthraquinone; C.I. disperse blue 1	2475-45-8	50 mg/kg	Textile dyes
Benzenamine, 4,4'-(4-iminocyclohexa-2,5-dienylidenemethylene)dianiline hydrochloride; C.I. basic red 9	569-61-9
[4-{4,4'-bis(dimethylamino) benzhydrylidene} cyclohexa-2, 5-dien-1-ylidene]di-methylammonium chloride; C.I. basic violet 3 with ≥ 0.1 per cent of Michler's ketone (EC number 202-027-5)	548-62-9

Azo dyes

There are 22 aromatic amines also restricted in entry 43 of REACH Annex XVII. This restriction only applies to dyed leathers and textiles that come into contact with the skin. These amines can be released by certain azo colourants, and have been proven to cause cancer. There are many thousands of different azo colourants that could theoretically be used to dye leathers and textiles, and the vast majority of these dyes will not release these carcinogenic aromatic amines. This has led to confusion that all azo dyes are banned, when in reality it is only a small number that are of concern.

Four of the 33 substances in entry 72 could undergo chemical reactions to form restricted azo colourants:

• 4-chloro-o-toluidinium chloride could form 4-chloro-o-toluidine
• 2-naphthylammoniumacetate could form 2-naphthylamine
• 4-methoxy-m-phenylene diammonium sulphate could form 4-methoxy-m-phenylenediamine
• 2,4,5-trimethylaniline hydrochloride could form 2,4,5 trimethylaniline.

Table 4: Substances in REACH Annex XVII entry 72 and their uses – azo dyes
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
4-chloro-o-toluidinium chloride	3165-93-3	30 mg/kg	Leather and textile dyes
2-naphthylammoniumacetate	553-00-4
4-methoxy-m-phenylene diammonium sulphate; 2,4-diaminoanisole sulphate	39156-41-7
2,4,5-trimethylaniline hydrochloride	21436-97-5

Phthalate plasticisers

Five phthalate plasticisers are listed in entry 72 and these may be present in order to make flexible polymeric coatings on coated textiles. Prints and coatings that are applied directly to textiles are also under the scope of the restriction. While the five plasticisers have not been previously restricted in REACH Annex XVII, they are listed as ‘substances of high concern’ (SVHCs) in the Candidate List for authorisation. As SVHCs, they are not restricted.

Nevertheless, there are legal obligations if more than 0.1 per cent of any of these plasticisers is present. The restriction in entry 72 also has the threshold of 0.1 per cent (equivalent to 1,000 mg/kg). However, this limit must not be exceeded individually or in combination with other phthalates in the entry and is a restriction on their presence in articles.

Table 5: Substances in REACH Annex XVII entry 72 and their uses – phthalates
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
1,2-benzenedicarboxylic acid; di-C 6-8-branchedalkylesters, C 7-rich	71888-89-6	1,000 mg/kg (individually or sum of phthalates present)	Plasticisers added to give flexibility to polymeric materials, especially PVC
Bis(2-methoxyethyl) phthalate	117-82-8
Diisopentylphthalate	605-50-5
Di-n-pentyl phthalate (DPP)	131-18-0
Di-n-hexyl phthalate (DnHP)	84-75-3

Extractable metals

The heavy metals lead, cadmium, arsenic and chromium VI contained in compounds that have already been included in entries 28, 29 or 30 of Annex XVII (that is, category 1A or 1B CMRs that are listed in the CLP Regulation mentioned earlier) are restricted to less than 1 mg/kg. Rather than a total amount, this is a maximum allowable concentration of that metal that can be extracted from the material.

Lead and cadmium salts are used as pigments or stabilisers in coated or synthetic textiles, arsenic compounds are sometimes incorporated into anti-microbial treatments, and chromium VI is on occasion found in a pigment or used as a catalyst in textile manufacturing.

Table 6: Substances in REACH Annex XVII entry 72 and their uses – extractable metals
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
Cadmium and its compounds (listed in Annex XVII, entries 28, 29, 30, appendices 1 to 6)	N/A	1 mg/kg after extraction	Metal salts might be used as stabilisers or pigments
Chromium VI compounds (listed in Annex XVII, entries 28, 29, 30, appendices 1 to 6)	N/A
Arsenic compounds (listed in Annex XVII, entries 28, 29, 30, appendices 1 to 6)	N/A
Lead and its compounds (listed in Annex XVII, entries 28, 29, 30, appendices 1 to 6)	N/A

NMP, DMFa and DMAC

Both 1-methyl-2-pyrrolidone (NMP) and dimethyl formamide (DMFa) have been included on the Candidate List of SVHCs for many years. Alongside N,N-dimethylacetamide (DMAC), their inclusion under entry 72 is the first EU restriction on these three chemicals.

SATRA has developed an in-house testing procedure – SATRA SOP CAT-067 – to detect and quantify NMP, DMFa and DMAC in order to meet the restriction of greater than 3,000 mg/kg for each individual substance.

Chlorotoluenes

Three chlorotoluenes are also included under entry 72. These substances are sometimes used as organic carriers for dyeing polyesters. They are also occasionally present as contaminants in organic solvents and as breakdown products from polyvinyl chloride (PVC), and are restricted above 1 mg/kg for each substance. These chlorotoluenes are:

• ∝,∝,∝,4-tetrachlorotoluene; p-chloro-benzotrichloride
• ∝,∝,∝-trichlorotoluene; benzotrichloride
• ∝-chlorotoluene; benzyl chloride.

Table 7: Substances in REACH Annex XVII entry 72 and their uses – chlorotoluenes
Substance	CAS number	Concentration limit by weight	Potential reasons why the substance may be found in consumer goods
∝,∝,∝,4-tetrachlorotoluene; p-chloro-benzotrichloride	5216-25-1	1 mg/kg	Could be contaminants in solvent-based cleaning agents, possible breakdown products from PVC
∝,∝,∝-trichlorotoluene; benzotrichloride	98-07-7
∝-chlorotoluene; benzyl chloride	100-44-7

Benzene

Benzene had existing restrictions for articles under REACH entry 5 for toys or parts of toys. The restriction (greater than 5 mg/kg) is the same in both entry 5 and 72, although the applicable articles under entry 72 mean the restrictions are no longer just limited to items that are intended for children.

Clothing, textiles and footwear

Entry 72 of REACH Annex XVII restricts 33 CMR substances which must not be present in clothing, textiles or footwear that have been placed on the market since 1^st November 2020. As previously mentioned, the restrictions apply to textiles, which means that leather, fur or hide contained in clothing, footwear or furniture are not covered by the scope of the restrictions.

Compliance with entry 72 is mandatory for applicable products sold both in the EU and the UK. It is important for manufacturers and retailers of applicable products to be aware of the restrictions. SATRA can assist customers with testing the 33 CMR substances listed.

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