ZDHC Manufacturing Restricted Substance List
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ZDHC MRSL V2.0

Background

The ZDHC Manufacturing Restricted Substances List (ZDHC MRSL) is a list of chemical substances. These substances are banned from intentional use in facilities processing textile materials, leather, rubber, foam, adhesives and trim parts in textiles, apparel, and footwear. Using chemical formulations that conform to the ZDHC MRSL allows suppliers to assure themselves, and their customers, that banned chemical substances are not intentionally used during production and manufacturing processes. 

The ZDHC MRSL goes beyond the traditional approaches to chemical restrictions, which only apply to finished products (Product Restricted Substances List - PRSL). This approach helps to protect consumers while minimising the possible impact of banned hazardous chemicals on production workers, local communities, and the environment.

Chemical formulations covered by restrictions in the ZDHC MRSL include, but are not limited to, cleaners, adhesives, paints, inks, detergents, dyes, colourants, auxiliaries, coatings and finishing agents used during raw material production, wet processing, process machinery maintenance, wastewater treatment, sanitation, and pest control. ZDHC MRSL limits apply to substances in commercially available formulations, not those from earlier stages of chemical synthesis.

The ZDHC Foundation Roadmap to Zero Programme would like to acknowledge the vital role of the experts comprising the MRSL Advisory Council who independently and objectively evaluated the proposed compound additions to the MRSL and made the decision on the compounds added to  this version of the ZDHC MRSL.

Purpose

The ZDHC MRSL offers brands and suppliers a single, harmonised list of chemical substances banned from intentional use during manufacturing and related processes in supply chains of the textile, apparel, and footwear (including leather and rubber) industries (the Industry). 

Version 2.0 applies to textiles, leather, rubber, foam and adhesives, recognising that these materials use different processes. Filters for each material ensure limits reflect the processes. 

Notes

The information in this ZDHC MRSL V2.0 is provided for information only. Whilst ZDHC takes every reasonable effort to make sure that the information is as accurate as possible, ZDHC makes no claims, promises, or guarantees about the accuracy, completeness, or adequacy of the contents of this document.

"Meeting the requirements of the ZDHC MRSL V2.0 does not

a) replace applicable national environmental or workplace safety restrictions. Worker exposure to chemical substances listed in this document, along with other hazardous substances, must not exceed occupational exposure limits

b) guarantee compliance with or take the place of legal or regulatory requirements relating to the use, storage, and transport of chemical products."

The ZDHC MRSL V2.0 does not replace legal or brand-specific restrictions on hazardous substances in finished products, including the material components of them.

DISCLAIMERS

In no event will ZDHC (and/or any related ZDHC majority owned legal entities) or the Directors or staff thereof be liable and ZDHC expressly disclaims any liability of any kind to any party for any loss, damage, or disruption caused

a) by errors or omissions, whether such errors or omissions result from negligence, accident, or any other cause and/or

b) from any use, decision made, action taken, or any other kind of reliance on the ZDHC MRSL V2.0 by a reader or user of it and/or

c) for any results obtained or not obtained from the use of the ZDHC MRSL V2.0

d) by any updates to the ZDHC MRSL V2.0

ZDHC MRSL Chapters

Chapter 1: ZDHC MRSL

This applies to chemical formulations and substances used during creation and wet processing of textile fibres, and during creation and processing of (coated) fabrics, leather, rubber, foam and adhesives. 

Group A: Supplier Guidance 

Group A substances are banned from intentional use in facilities that process raw materials and manufacture finished products.

Group B: Formulation Limit

Group B substances are restricted to concentration limits in chemical formulations commercially available from chemical suppliers. These limits ban intentional use while allowing for reasonable expected manufacturing impurities, which should be consistently achievable by responsible chemical manufacturers.

Chapter 2: ZDHC Archived Substances

Archived substances, or those without strong evidence of current use in Industry, but with clear evidence of historical use. 

Chapter 3: ZDHC MRSL Candidate List

Found in Chapter 3 of the ZDHC MRSL. Proposed ZDHC MRSL additions can meet listing criteria, as described in the Principles and Procedures, yet lack safer alternatives at scale. Including such substances on the Candidate List encourages the innovation of alternatives.

Process for ZDHC MRSL Revision

After the release of a new version of the ZDHC MRSL a transition period applies. This lets the Industry prepare for implementation of the new version. The current transition period is twelve months, beginning on January 1st 2020. During this time, both versions of the ZDHC MRSL remain active and it’s possible to certify against them.

Chapter 1: ZDHC MRSL (Manufacturing Restricted Substance List)

Alkylphenol (AP) and Alkylphenol Ethoxylates (APEOs): including all isomers

Potential Uses in Apparel and Footwear Textile Processing

APEOs can be used as or found in: detergents, scouring agents, spinning oils, wetting agents, softeners, emulsifier/dispersing agents for dyes and prints, impregnating agents, de- gumming for silk production, dyes and pigment preparations, polyester padding and down/feather fillings.

Substance
Nonylphenol (NP),mixed isomers
Nonylphenolethoxylates (NPEO)
Octylphenolethoxylates (OPEO)
Octylphenol (OP),mixed isomers
Anti- Microbials & Biocides

Potential Uses in Apparel and Footwear Textile Processing

These substances have biocidal properties, making it useful for various preservation applications.

Substance
o-Phenylphenol (+salts)
Permethrin

In most situations, deliberate use is not permitted. However, it should be noted that Permethrin is approved for use on PT18 under BPR and is permitted for use on wool curtains and carpets, rugs and floor coverings. Permethrin is permitted for PPE use (EU 2016/425, EPA registered product, APVMA Registered Product, PMRA Registered Product, etc.). Also, its use is sometimes stipulated for certain end uses such as military. All efforts should be made to maximise the durability of the chemical finish and to minimise losses to the environment.

Triclosan
Chlorinated Parafins

Potential Uses in Apparel and Footwear Textile Processing

These are used occasionally as flame retardants in certain industries. In leather formulations, these are also used as fat liquoring agents.

Substance
Short-chain Chlorinatedparaffin (C10– C13)
Medium-chain Chlorinatedparaffins (MCCPs) (C14-C17)
Chlorobenzenes and Chlorotoluenes

Potential Uses in Apparel and Footwear Textile Processing

Chlorobenzenes and Chlorotoluenes (chlorinated aromatic hydrocarbons) can be used as carriers in the dyeing process of polyester or wool/polyester fibres. They can also be used as solvents.

Substance
1,2-dichlorobenzene
Other isomers of mono-, di-, tri-, tetra-, penta- and hexa- Chlorobenzene and mono-, di-, tri-, tetra- and penta- chlorotoluene
Chlorophenols

Potential Uses in Apparel and Footwear Textile Processing

Chlorophenols are polychlorinated compounds used as preservatives or pesticides. Pentachlorophenol (PCP) and tetrachlorophenol (TeCP) have been used in the past to prevent mould when storing/ transporting raw hides and leather. They are now regulated and should not be used.

Substance
Pentachlorophenol (PCP)1
Tetrachlorophenol(TeCP)1
2,4-dichlorophenol2
2-chlorophenol2
2,5-dichlorophenol2
2,6-dichlorophenol2
2,4,6-trichlorophenol2
3,5-dichlorophenol2
2,4,5-trichlorophenol2
2,3-dichlorophenol2
3,4-dichlorophenol2
3-chlorophenol2
4-chlorophenol2
2,3,4-trichlorophenol2
3,4,5-trichlorophenol2
2,3,5-trichlorophenol2
2,3,6-trichlorophenol2
Dyes – Azo (Forming Restricted Amines)

Potential Uses in Apparel and Footwear Textile Processing

Azo dyes and pigments are colourants that incorporate one or several azo groups (-N=N-) bound with aromatic compounds. Thousands of azo dyes exist, but only those that degrade to form the listed cleavable amines are restricted. Azo dyes that release these amines are regulated and should no longer be used for the dyeing of textiles. Please find a non-exhaustive list of dyes which can form restricted amines in the appendix.

Substance
4,4-oxydianiline
4,4-methylene-bis-(2-chloro-aniline)
3,3-dimethoxylbenzidine
4,4-methylenedianiline
4-chloroaniline
3,3-dimethylbenzidine
6-methoxy-m-toluidine
4,4-thiodianiline
4-aminoazobenzene
2,4,5-trimethylaniline
o-anisidine
4,4-methylenedi-o-toluidine
3,'3-dichlorobenzidine
4-methoxy-m-phenylenediamine
2,6-xylidine
2-naphthylamine
o-toluidine
Benzidine
4-chloro-o-toluidine
4-aminodiphenyl
4-methyl-m-phenylenediamine
2,4-xylidine
o-aminoazotoluene
5-nitro-o-toluidine
2-Naphthylammoniumacetate
4-chloro-o-toluidinium chloride
4-methoxy-m-phenylene diammonium sulphate; 2,4-diaminoanisole sulphate
2,4,5-trimethylaniline hydrochloride
Dyes – Carcinogenic or Equivalent Concern

Potential Uses in Apparel and Footwear Textile Processing

Most of these substances are regulated and should no longer be used for the dyeing of textiles.

Substance
C.I. Basic Violet 14
C.I. Direct Black 38
C.I. Direct Blue 6
C.I. Acid Red 26
C.I. Direct Red 28
C.I. Basic Red 9
C.I. Disperse Blue 1
C.I. Basic Blue 26 (with Michler’s Ketone > 0.1%)
C.I. Disperse Blue 3
C.I. Basic Green 4 (Malachite Green Oxalate)
C.I. Basic Green 4 (Malachite Green Chloride)
Disperse Orange 11
C.I. Basic Green 4 (Malachite Green)
C.I. Acid Violet 49
Basic violet 3 with >0.1% of Michler´s Ketone
Dyes – Disperse (Sensitising)

Potential Uses in Apparel and Footwear Textile Processing

Disperse dyes are a class of water- insoluble dyes that penetrate the fibre system of synthetic or manufactured fibres and are held in place by physical forces without forming chemical bonds. Disperse dyes are used in synthetic fibre (e.g. polyester, acetate, polyamide). Restricted disperse dyes are suspected of causing allergic reactions and should no longer be used for dyeing of textiles.

Substance
Disperse Yellow 39
Disperse Brown 1
Disperse Yellow 1
Disperse Blue 102
Disperse Blue 106
Disperse Orange 37/59/76
Disperse Orange 1
Disperse Yellow 3
Disperse Red 11
Disperse Red 1
Disperse Red 17
Disperse Yellow 49
Disperse Blue 7
Disperse Blue 26
Disperse Yellow 9
Disperse Blue 124
Disperse Blue 35
Disperse Orange 3
Disperse Blue 35
Dyes – Navy Blue Colourant

Potential Uses in Apparel and Footwear Textile Processing

Navy Blue Colourant is regulated and should no longer be used for the dyeing of textiles.

Substance
Component 1: C39H23Cl-CrN7O12S 2Na
Component 2: C46H-30CrN10O20S2 3Na
Flame Retardants

Potential Uses in Apparel and Footwear Textile Processing

Flame retardant chemicals are rarely used to meet flammability requirements in children’s clothing and adult products. They should no longer be used in apparel and footwear.
All Halogenated Flame Retardants are banned from intentional use that means including but not exclusive the list below;

Substance
Octabromodiphenyl ether (OctaBDE)
Tris(2-chloroethyl)phosphate (TCEP)
Tris(2,3,-dibromopropyl)-phosphate (TRIS)
Bis(2,3-dibromopropyl)phosphate (BIS)
Decabromodiphenyl ether (DecaBDE)
Pentabromodiphenyl ether (PentaBDE)
Tris(1-aziridinyl)phosphineoxide) (TEPA)
Tetrabromobisphenol A(TBBPA)
Tris(1,3-dichloro-isopropyl)phosphate (TDCP)
Polybromobiphenyls (PBB)
2,2-bis(bromomethyl)-1,3-propanediol (BBMP)
Hexabromocyclododecane(HBCDD)
Boric acid
Decabromobiphenyl (DecaBB)
Disodium tetraborate, anhydrous
Disodium octaborate
dibromopropylether
Diboron trioxide
Heptabromodiphenyl ether (HeptaBDE)
Dibromobiphenyls (DiBB)
Monobromodiphenylethers (MonoBDEs)
Monobromobiphenyls (MonoBB)
Hexabromodiphenyl ether (HexaBDE)
Nonabromobiphenyls (NonaBB)
Nonabromodiphenyl ether (NonaBDE)
Polybromobiphenyls (Polybrominated biphenyls) (PBBs)
Octabromobiphenyls (OctaBB)
Tetraboron disodium heptaoxide, hydrate
Tetrabromodiphenyl ether (TetraBDE)
Tribromodiphenylethers (TriBDEs)
Tris-(2-chloro-1-methylethyl)phosphate (TCPP)
Glycols / Glycol Ethers

Potential Uses in Apparel and Footwear Textile Processing

In apparel and footwear, glycols have a wide range of uses including as solvents for finishing/ cleaning, printing agents, and dissolving/ diluting fats, oils, and adhesives (e.g. in degreasing or cleaning operations).

Substance
Ethylene glycol dimethylether
2-methoxyethylacetate
2-ethoxyethanol
2-methoxyethanol
Bis(2-methoxyethyl)-ether
2-ethoxyethyl acetate
2-methoxypropylacetate
Triethylene glycol dimethyl ether
Halogenated Solvents

Potential Uses in Apparel and Footwear Textile Processing

In apparel and footwear, halogenated solvents are used as finishing/ cleaning and printing agents, for dissolving/ diluting fats, oils and adhesives (e.g. in degreasing or cleaning operations).

Substance
Methylene chloride
Trichloroethylene
Tetrachloroethylene
Benzylchloride
1,2-dichloroethane
Organotin Compounds

Potential Uses in Apparel and Footwear Textile Processing

Organotins are a class of chemicals combining tin and organics such as butyl and phenyl groups. Organotins are predominantly found in the environment as antifoulants in marine paints, but they can also be used as biocides (e.g. antibacterials), catalysts in plastic and glue production and heat stabilisers in plastics/rubber. In textiles and apparel, organotins are associated with plastics/rubber, inks, paints, metallic glitter, polyurethane products and heat transfer material.

Substance
Dibutyltin (DBT)
Mono-, di- and tri-methyltin derivatives
Mono-, di- and tri-octyltin derivatives
Mono-, di- and tri-phenyltin derivatives
Mono- and tri-butyltin derivatives
Dipropyltin compounds (DPT)
Tetraethyltin Compounds (TeET)
Tripropyltin Compounds (TPT)
Tetrabutyltin compounds (TeBT)
Tetraoctyltin compounds (TeOT)
Tricyclohexyltin (TCyHT)
Other/ Miscellaneous Chemicals
These are other chemicals/ substances/ process with a usage ban.
Substance
Borate, zinc salt

Borate, zinc salt can be used as a flame retardant but also in paints, pigments, and adhesives.

Bisphenol A

Bisphenol A (BPA) is a precursor chemical used along with other chemicals to create some plastics and resins. It is commonly used to harden plastics.

Thiourea

Thiourea is used in many formulations to increase the solubility.

Quinoline

Contaminant of dispersing agents in disperse dyes.

Silica (particles of respirable size)

Respirable particles of silica are often generate during the process of sand blasting.

AEEA [2-(2-aminoethylamino)ethanol]

AEEA is used a.o. in chelating agents, surfactants and fabric softeners.

Perfluorinated and Polyfluorinated Chemicals (PFCs)
Durable water, oil and stain repellent finishes based on long-chain PFC’s are banned from intentional use. There are two methods of manufacture of PFCs referred to as electrofluorination and telomerisation. PFC’s made by the electrofluorination method have by-products associated with them called perfluoroalkyl sulphonates with the most common being the C8 species Perfluorooctane sulphonate (PFOS). The deliberate use of any PFCs made by electrofluorination with a chain length of C6 or above is not permitted. The detection of any PFOS analogue as where the chain length is 6 units or longer will trigger a failure [i.e. PFHS and above]. These types of PFCs are typically used in home textiles. PFC’s made by the telomerisation method have by-products associated with them called perfluorocarboxylic acids with the most common being the C8 species perfluorooctanoic acid (PFOA). The deliberate use of any PFCs made by telomerisation with a chain length of C8 or above is restricted. ZDHC plans to further restrict the use of PFCs in future revisions and details can be found in the candidate list is not permitted. The detection of any PFOA analogue as where the chain length is 8 units or longer will trigger a failure (i.e. PFOA and above). These types of PFCs are typically used in clothing and footwear.

Potential Uses in Apparel and Footwear Textile Processing

PFOA and PFOS may be present as unintended by-products in long-chain commercial water, oil and stain repellent agents. PFOA also may be in used in the production for polymers like polytetrafluoroethylene (PTFE).

Substance
Perfluorooctane sulfonate (PFOS) and related substances
Perfluorooctanoic acid (PFOA) and related substances
Phthalates – including all other esters of ortho-phthalic acid

Potential Uses in Apparel and Footwear Textile Processing

Esters of ortho-phthalic acid (phthalates) are a class of organic compounds commonly added to plastics to increase flexibility. They sometimes are used to facilitate moulding of plastic by decreasing its melting temperature. Phthalates can be found in:
- Flexible plastic components (e.g. PVC)
- Print pastes
- Adhesives
- Plastic buttons
- Plastic sleevings
- Polymeric coatings

Substance
Di-n-octyl phthalate(DNOP)5
Bis(2-methoxyethyl)phthalate (DMEP)5
Di-iso-decyl phthalate(DIDP)5
Di(ethylhexyl) phthalate(DEHP)5
Di-isononyl phthalate(DINP)5
Di-n-hexyl phthalate(DnHP)5
Butyl benzyl phthalate(BBP)5
Dibutyl phthalate (DBP)5
Dinonyl phthalate (DNP)5
Diethyl phthalate (DEP)5
Di-n-propyl phthalate(DPRP)5
Di-cyclohexyl phthalate(DCHP)5
Di-isobutyl phthalate(DIBP)5
Di-iso-octyl phthalate(DIOP)5
1,2-benzenedicarboxylic acid, di-C7-11 branched and liearalkyl esters (DHNUP)5
1,2-benzenedicarboxylic acid, di-C6-8 branched and liearalkyl esters , C7-rich (DIHP)5
Diisopentylphthalates5
Di-n-pentylphthalates5
Polycyclic Aromatic Hydrocarbons (PAHs)

Potential Uses in Apparel and Footwear Textile Processing

Oil containing PAHs are added to rubber and plastics as a softener or extender and may be found in rubber, plastics, lacquers, and coatings. Within the footwear producing industry, PAHs are often found in the outsoles of footwear and in printing pastes for screen prints. PAHs can be present as impurities in carbon black dyestuffs.

Substance
Benzo[a]pyrene
Pyrene3,4
Benzo[ghi]perylene3,4
Benzo[j]fluoranthene3,4
Anthracene3,4
Indeno[1,2,3-cd]pyrene3,4
Benzo[e]pyrene3,4
Benzo[b]fluoranthene3,4
Benzo[k]fluoranthene3,4
Fluoranthene3,4
Acenaphthylene3,4
Dibenz[a,h]anthracene3,4
Chrysene3,4
Phenanthrene3,4
Acenaphthene3,4
Fluorene3,4
Naphthalene3
Benzo[a]anthracene3,4
Total Heavy Metals
Listed metals are banned from intentional use in textile manufacturing/ finishing unless stated differently. The total heavy metal limits do not apply to products containing a listed metal as an inherent compositional part (e.g. metal-complex colorants, the double salts of certain cationic colourants or extenders like barium sulfate). In these cases, the extractable content of the corresponding metal has to be considered. Alternatively, the total content will be communicated to the customers, who will determine whether their final product will comply with the corresponding RSL(s) requirements.

Potential Uses in Apparel and Footwear Textile Processing

Although typically associated with leather tanning, chromium VI also may be used in the dyeing of wool (after the chroming process).

Substance
Arsenic (As)
Cadmium (Cd)
Mercury (Hg)
Lead (Pb)
Chromium (VI)
Antimony
Chromium
Barium
Selenium
Tin
Nickel
Copper
Cobalt
Silver
UV absorbers

Potential Uses in Apparel and Footwear Textile Processing

These are frequently used in formulations to be stable to the influences of light and UV

Substance
2-(2H-benzotriazol-2-yl)-4-(tert-butyl)-6-(sec- butyl) phenol (UV-350)
2-benzotriazol-2-yl-4,6-di-tert-butylphenol (UV-320)
2,4-Di-tert-butyl-6-(5-chlorobenzotriazole-2-yl) phenol (UV-327)
2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (UV-328)
Volatile Organic Compounds (VOC)

Potential Uses in Apparel and Footwear Textile Processing

These Volatile Organic Compounds (VOC) should not be used in textile auxiliary chemical preparations. They are associated with solvent-based processes like solvent-based polyurethane coatings and glues/ adhesives. They should not be used for any kind of facility cleaning or spot cleaning.

Substance
Benzene
o-cresol
p-cresol
Xylene
m-cresol

Chapter 2: ZDHC MRSL Candidate List

(Free) Analine

Potential Uses in Apparel and Footwear Textile Processing

Used for indigo and to manufacture AZO Dyes (especially the leather dyes).

Substance
(Free) Aniline
ADCA

Potential Uses in Apparel and Footwear Textile Processing

ADCA is used as a foaming/ blowing agent for rubber applications.

Substance
Diazene-1,2-dicarboxamide [C,C`-azodi(formamide), ADCA]
Cyclic Siloxanes
Substance
D5
D6
D4
Dimethylfumarate
Substance
Dimethylfumarate (DMFu)
Dyes – Carcinogenic or Equivalent Concern

Potential Uses in Apparel and Footwear Textile Processing

Green dye

Substance
C.I. Basic Green 4 leuco base
Flame Retardants

Potential Uses in Apparel and Footwear Textile Processing

Flame retardant chemicals are rarely used to meet flammability requirements in children’s clothing and adult products.

Substance
Trixylyl phosphate (TXP)
Tri-o-cresyl phosphate
Trimethyl phosphate
Formaldehyde

Potential Uses in Apparel and Footwear Textile Processing

Formaldehyde has many uses in printing, interlinings, stiffeners, etc.

Substance
Formaldehyde
Perfluorinated and Polyfluorinated Chemicals (PFCs)

Potential Uses in Apparel and Footwear Textile Processing

Used as water repellent, stain repellent and in certain cases to improve the colour fastness properties.

Substance
PFCs (excluding current restrictions)
Phenol

Potential Uses in Apparel and Footwear Textile Processing

Phenol is not deliberately used in textiles or footwear but trace amounts of phenol can be found in many chemical formulations.

Substance
Phenol
Solvents

Potential Uses in Apparel and Footwear Textile Processing

There are many uses for solvents from adhesives, coated textiles, prints, etc.

Substance
2-methoxypropanol
Toluene
Methanol
Ethylbenzene
2-(2-methoxyethoxy)-ethanol
N-Methyl-2-Pyrrolidone; 1-methyl-2-pyrrolidone (NMP)
Dimethyl formamide; N,N-dimethylformamide (DMFa)
N,N-dimethylacetamide (DMAC)
Total Heavy Metals

Potential Uses in Apparel and Footwear Textile Processing

Besides in dyes and pigments, metals are used as raw material for trims and other components.

Substance
Metals (Non -dye /pigment)

Chapter 3: ZDHC MRSL Archived Substances List

Substance
Substance
Dyes – Carcinogenic or Equivalent Concern

Potential Uses in Apparel and Footwear Textile Processing

Most of these substances are regulated and should no longer be used for the dyeing of textiles.

Substance
C I Solvent yellow 2
D&C Red No. 19
C.I. Solvent yellow 14
Other/Misceleanous Chemicals

Potential Uses in Apparel and Footwear Textile Processing

Dye

Substance
Auramine hydrochloride
Solvents

Potential Uses in Apparel and Footwear Textile Processing

In the past, it was used to make several types of polymers, resins, and textiles, but its use is now highly restricted.

Substance
Bis(chloromethyl) ether