Manufacturing Restricted Substances List

Zero Discharge of Hazardous Chemicals Programme
1 BackgroundIn the Zero Discharge of Hazardous Chemicals (ZDHC) Joint Roadmap, Version 2, ZDHC member brands
committed to define and develop a Manufacturing Restricted Substances List (MRSL) for the apparel andfootwear industry. The MRSL addresses hazardous substances potentially used and discharged into theenvironment during manufacturing and related processes, not just those substances that could be present infinished products.

2 Purpose

The ZDHC MRSL will assist brands, their supply chains and the broader industry to adopt a harmonised
approach to the control of hazardous substances used to process textile and trim materials in apparel andfootwear. Natural leather and metal trim parts are excluded from the scope of this MRSL version. 1 The MRSL
should be communicated to raw material suppliers, including wet-processing facilities and sub-contractors
and factories assembling or manufacturing garments and footwear. ZDHC brands expect that material
suppliers and factories will communicate with their chemical suppliers to ensure that the listed substances
are not present in chemical formulations above established limits.
Note: The MRSL does not replace applicable national environmental or workplace safety restrictions. Worker
exposure to the listed and other hazardous substances must not exceed occupational exposure limits andchemical formulations must comply with all applicable legal restrictions, including any subsequent
restrictions that establish stricter limits. The ZDHC MRSL does not replace legal or brand-specific restrictions
on hazardous substances in finished products.

3 Definitions
MRSL

The ZDHC MRSL is a list of chemical substances subject to a usage ban (see Usage Ban, p. 2). The MRSL
applies to chemicals used in facilities that process textile materials and trim parts for use in apparel andfootwear. The MRSL does not apply to natural leather processing or production of metal trim parts.
Chemicals on the MRSL include ingredients potentially used in cleaners, solvents, adhesives, stabilizers,
paints, inks, detergents, dyes, pigments, auxiliaries, coatings and finishing agents used for wet-processing,maintenance, waste water treatment, sanitation and pest control. There should be no intentional use of the
MRSL-listed substances in facilities that process materials used in the production of apparel and footwear.
MRSL limits apply to substances in commercially available chemical formulations and not those from earlier
stages of chemical synthesis.
Note: Threshold Limit values on restricted substances in chemical formulations are in some cases
substantially higher than limits on restricted substances in finished products. This is because substances infinished products are usually found in smaller concentrations than in the chemical formulations used to
produce them. Chemical formulations are highly concentrated before dilution upon application to textiles
and other materials.

1 Hazardous substances in metal trim parts are more properly controlled by material or finished product limits. Hazardous

substances potentially used during natural leather processing will be addressed in the next version of the MRSL. Special
considerations of the chemistry involved made it necessary for the ZDHC Group to separately address leather processing at a later
date.

June 2014

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1Chemical Substance

A chemical substance is a chemical element and its compounds in the natural state or obtained by any
manufacturing process (REACH, 2014). 2 A chemical substance is usually identifiable by a single, unique
Chemical Abstracts Service (CAS) number or Color Index (CI) number. The ZDHC MRSL focuses on chemical
substances listed by CAS number and CI number, but it also includes groups of substances for which listing
individual substances is not practical.

Commercial Chemical Formulation

A commercial chemical formulation is usually a proprietary blend of several chemical substances that isavailable for purchase from chemical suppliers under their own trade name.

Usage Ban

A usage ban indicates that the MRSL-listed chemical substance or group of substances may not be used toachieve a desired function or effect during production of the raw material or product (that is, no intentionaluse). This usage ban extends to other uses within a facility like cleaning and maintenance. Due to theexistence of manufacturing impurities in chemical formulations, a minor or trace amount of the restricted
substance is permitted. Chemical formulations containing restricted substances that exceed limits are notcompliant with the MRSL.

4 MRSL Creation Process

The ZDHC MRSL includes relevant substances from the original 11 priority chemical groups in the Joint
Roadmap along with additional substances discussed with qualified experts from the ZDHC TechnicalAdvisory Committee (TAC) and member brands. Several of the listed substances are regulated in finishedproducts and have been successfully restricted by brands for years. Their inclusion on the list is consistent
with existing industry standards.

5 MRSL Instructions

Group A: Raw Material and Finished Product Supplier Guidance•

Substances are banned from intentional use in facilities that process raw materials and manufacturefinished products. Refer to the AFIRM Restricted Substances Guidance for the lowest agreed uponmaterial or finished product limits among AFIRM brands: http://www.afirm-group.com/rsl-guidance/.
See brand RSLs for individual requirements.

Group B: Chemical Supplier Formulation Limit•

Substances are restricted to concentration limits in chemical formulations commercially available fromchemical suppliers. These limits ban intentional use while allowing for reasonable expected
manufacturing impurities that should be consistently achievable by responsible chemical
manufacturers. 3

2 “A chemical element and its compounds in the natural state or obtained by any manufacturing process, including any additivenecessary to preserve its stability and any impurity deriving from the process used, but excluding any solvent which may beseparated without affecting the stability of the substance or changing its composition.”
http://www.reachonline.eu/REACH/EN/REACH_EN/article3.html. Accessed May 8, 2014.

3 Material Safety Data Sheets (MSDS) only list substances present at concentrations of 1000 ppm or greater. Suppliers must

communicate with chemical suppliers to ensure MRSL limits are met.

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ZDHC MRSLCAS No.

Substance

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

General Techniques forAnalysing Chemicals

Alkylphenol (AP) and Alkylphenol Ethoxylates (APEOs): including all isomers
104-40-5,
11066-49-2
25154-52-3
84852-15-3
140-66-9
1806-26-4
27193-28-8
9002-93-1
9036-19-5
68987-90-6
9016-45-9
26027-38-3
37205-87-1
68412-54-4
127087-87-0

Nonylphenol (NP), mixed isomers

250 ppm

Octylphenol (OP), mixed isomers

250 ppm

Octylphenol ethoxylates (OPEO)

No intentional use

Nonylphenol ethoxylates (NPEO)

500 ppm

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

Liquid chromatography-Mass
spectrometry (LC-MS),
Gas chromatography-Mass
spectrometry (GC-MS)

500 ppm

Chlorobenzenes and Chlorotoluenes
95-50-1

1,2-dichlorobenzene

Other mono-, di-, tri-, and tetra-, hexa-, penta-, chlorobenzenes andmono-, di-, tri-, and tetra-, hexa-, penta-, chlorotoluenes
Chlorophenols
25167-83-3
87-86-51000 ppm
No intentional use

Tetrachlorophenol (TeCP)

Sum = 200 ppm

Sum = 20 ppm

Pentachlorophenol (PCP)
No intentional use

Mono-, di-, and tri- chlorophenols

June 2014

Sum = 50 ppm

Chlorobenzenes and chlorotoluenes (chlorinatedaromatic hydrocarbons) can be used as carriers in thedyeing process of polyester or wool/polyester fibres.
They can also be used as solvents.

GC-MS

Chlorophenols are polychlorinated compounds usedas preservatives or pesticides. Pentachlorophenol(PCP) and tetrachlorophenol (TeCP) are sometimes
used to prevent mould and kill insects when growing
cotton and when storing/transporting fabrics.
PCP/TeCP can also be used as a preservative in print
pastes.

GC-MS

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ZDHC MRSLCAS No.

Substance

General Techniques forAnalysing Chemicals

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

No intentional use

200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm
200 ppm

Azo dyes and pigments are colourants thatincorporate one or several azo groups(-N=N-) bound with aromatic compounds. Thousandsof azo dyes exist, but only those which degrade toform the listed cleavable amines are restricted. Azo
dyes that release these amines are regulated andshould no longer be used for dyeing of textiles.

LC, GC

No intentional use

250 ppm

Navy Blue colourants are regulated and should nolonger be used for dyeing of textiles.

LC

Dyes – Azo (Forming Restricted Amines)
101-14-4
4,4’-methylene-bis-(2-chloro-aniline)
101-77-9
4,4’-methylenedianiline
101-80-4
4,4’-oxydianiline
106-47-84-chloroaniline
119-90-4
3,3’-dimethoxylbenzidine
119-93-7
3,3’-dimethylbenzidine
120-71-8
6-methoxy-m-toluidine
137-17-7
2,4,5-trimethylaniline
139-65-1
4,4’-thiodianiline
60-09-34-aminoazobenzene
615-05-4
4-methoxy-m-phenylenediamine
838-88-0
4,4’-methylenedi-o-toluidine
87-62-72,6-xylidine
90-04-0o-anisidine
91-59-82-naphthylamine
91-94-1
3,’3-dichlorobenzidine
92-67-14-aminodiphenyl
92-87-5
Benzidine
95-53-4o-toluidine
95-68-1
2,4-Xylidine
95-69-24-chloro-o-toluidine
95-80-7
4-methyl-m-phenylenediamine
97-56-3o-aminoazotoluene
99-55-85-nitro-o-toluidine
Dyes – Navy Blue Colourant
118685-33-9
Component 1: C39H23ClCrN7O12S∙2Na
Not AllocatedJune 2014

Component 2: C46H30CrN10O20S2∙3Na

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ZDHC MRSLCAS No.

Substance

Dyes – Carcinogenic or Equivalent Concern
1937-37-7
C.I. Direct Black 38
2602-46-2
C.I. Direct Blue 6
3761-53-3
C.I. Acid Red 26
569-61-9
C.I. Basic Red 9
573-58-0
C.I. Direct Red 28
632-99-5
C.I. Basic Violet 142475-45-8
C.I. Disperse Blue 1
2475-46-9
C.I. Disperse Blue 3
2580-56-5
C.I. Basic Blue 26 (with Michler’s Ketone > 0.1%)
569-64-2
C.I. Basic Green 4 (malachite green chloride)
2437-29-8
C.I. Basic Green 4 (malachite green oxalate)10309-95-2
C.I. Basic Green 4 (malachite green)
82-28-0
Disperse Orange 11

General Techniques forAnalysing Chemicals

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

No intentional use

250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm

Most of these substances are regulated and should nolonger be used for dyeing of textiles.

LC

No intentional use

250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm

Disperse dyes are a class of water-insoluble dyes thatpenetrate the fibre system of synthetic or
manufactured fibres and are held in place by physicalforces 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 beused for dyeing of textiles.

LC

Dyes – Disperse (Sensitizing)
119-15-3
12222-97-8
12223-01-7
12236-29-2
13301-61-6
23355-64-8
2581-69-3
2832-40-8
2872-48-2
2872-52-8
3179-89-3
3179-90-6
3860-63-7
54824-37-2
12222-75-2
61951-51-7
6373-73-5
730-40-556524-77-7

June 2014

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

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ZDHC MRSLCAS No.

Substance

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

General Techniques forAnalysing Chemicals

Flame Retardants
115-96-8
1163-19-5
126-72-7
32534-81-932536-52-0
5412-25-9
545-55-1
59536-65-1
79-94-73194-55-6
3296-90-0
13674-87-8
85535-84-8

Tris(2-chloroethyl)phosphate (TCEP)
Decabromodiphenyl ether (DecaBDE)
Tris(2,3,-dibromopropyl)-phosphate (TRIS)
Pentabromodiphenyl ether (PentaBDE)
Octabromodiphenyl ether (OctaBDE)
Bis(2,3-dibromopropyl)phosphate (BIS)
Tris(1-aziridinyl)phosphine oxide) (TEPA)
Polybromobiphenyls (PBB)
Tetrabromobisphenol A (TBBPA)
Hexabromocyclodecane (HBCDD)
2,2-bis(bromomethyl)-1,3-propanediol (BBMP)
Tris(1,3-dichloro-isopropyl) phosphate (TDCP)
Short-chain chlorinated Paraffins (SCCP)(C10-C13)

No intentional use

250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm
250 ppm

Flame retardant chemicals are rarely used to meet
flammability requirements in children’s clothing andadult products. They should no longer be used inapparel and footwear.

GC-MS

50 ppmGlycols
111-96-6
110-80-5
111-15-9
110-71-4
109-86-4
110-49-670657-70-4
112-49-2

Bis(2-methoxyethyl)-ether
2-ethoxyethanol
2-ethoxyethyl acetate
Ethylene glycol dimethyl ether
2-methoxyethanol
2-methoxyethylacetate
2-methoxypropylacetate
Triethylene glycol dimethyl ether
1,2-dichloroethane
Methylene chloride
Trichloroethylene
Tetrachloroethylene

No intentional use

50 ppm50 ppm50 ppm50 ppm50 ppm50 ppm50 ppm50 ppm

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

No intentional use

5 ppm
5 ppm
40 ppm
5 ppm

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

High-performance liquid
chromatography (HPLC), LC-MS

Halogenated Solvents
107-06-2
75-09-2
79-01-6
127-18-4

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GC-MS

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ZDHC MRSLCAS No.

Substance

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

No intentional use

20 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm
5 ppm

Organotins are a class of chemicals combining tin andorganics 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 inplastic and glue production and heat stabilizers inplastics/rubber. In textiles and apparel, organotins areassociated with plastics/rubber, inks, paints, metallic
glitter, polyurethane products and heat transfer
material.

General Techniques forAnalysing Chemicals

Organotin Compounds
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple
Multiple

Dibutyltin (DBT)
Dimethyltin (DMT)
Monobutyltin (MBT)
Monoctyltin (MOT)
Dioctyltin (DOT)
Tricyclohexyltin (TCyHT)
Trioctyltin (TOT)
Tripropyltin (TPT)
Tributyltin (TBT)
Trimethyltin (TMT)
Triphenyltin (TPhT)
Tetrabutyltin (TebT)

GC-MS, low resolution mass
spectrometry (LRMS)

Polycyclic Aromatic Hydrocarbons (PAHs)
50-32-8
120-12-7
129-00-0
191-24-2
192-97-2
193-39-5
205-82-3
205-99-2
206-44-0
207-08-9
208-96-8
218-01-9
53-70-3
56-55-3
83-32-985-01-8
86-73-7
91-20-3

June 2014

Benzo[a]pyrene (BaP)
Anthracene
PyreneBenzo[ghi]perylene
Benzo[e]pyrene
Indeno[1,2,3-cd]pyrene
Benzo[j]fluoranthene
Benzo[b]fluoranthene
Fluoranthene
Benzo[k]fluoranthene
Acenaphthylene
Chrysene
Dibenz[a,h]anthracene
Benzo[a]anthracene
Acenaphthene
Phenanthrene
Fluorene
Naphthalene

20 ppm

No intentional use

Sum = 200 ppm

Polycyclic aromatic hydrocarbons (PAHs) are naturalcomponents of crude oil and are a common residue
from oil refining. PAHs have a characteristic smell
similar to the smell of car tires or asphalt. Oil residues
containing PAHs are added to rubber and plastics as asoftener or extender and may be found in rubber,plastics, lacquers and coatings. PAHs are often foundin the outsoles of footwear and in printing pastes ofscreen prints. PAHs can be present as impurities in
Carbon Black. They also may be formed from thermal
decomposition of recycled materials during
reprocessing.

GC-MS

Naphthalene: Dispersing agents for textile dyes may
contain high residual naphthalene concentrations dueto the use of low quality naphthalene derivatives(e.g., poor quality naphthalene sulphonate
formaldehyde condensation products).

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ZDHC MRSLCAS No.

Substance

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

General Techniques forAnalysing Chemicals

Perfluorinated and Polyfluorinated Chemicals (PFCs)
Beginning January 1, 2015: Durable water, oil and stain repellent finishes and soil release finishes (fluorinated polymers) based on long-chain technology are banned from intentional use byZDHC signatory brands. Long-chain compounds according to the OECD definition (http://www.oecd.org/ehs/pfc/) are based on long-chain perfluorocarboxylic acids (C8 and higher) and on longchain perfluoroalkyl sulfonates (C6 and higher).
The main contaminants of this technology include:••

Perfluoroalkyl sulfonates (PFSAs) with carbon chain lengths C6 and higher (e.g., PFOS, perfluorooctane sulfonate)
Perfluorocarboxylic acids with carbon chain lengths C8 and higher (e.g., PFOA, perfluorooctanoic acid)
Multiple335-67-1

Perfluorooctane sulfonate (PFOS) and related
substances

2 ppm (sum)No intentional use

Perfluorooctanoic acid (PFOA)

2 ppm

PFOA and PFOS may be present as unintended byproducts in long-chain commercial water, oil and stain
repellent agents. PFOA also may be in use forpolymers like polytetrafluoroethylene (PTFE).

LC-MS

Phthalates – including all other esters of ortho-phthalic acid117-81-7
117-82-8
117-84-026761-40-028553-12-0
84-75-3
84-74-2
85-68-7
84-76-4
84-66-2
131-16-8
84-69-5
84-61-727554-26-3
68515-42-4
71888-89-6

June 2014

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

Esters of ortho-phthalic acid (phthalates) are a classof organic compounds commonly added to plastics toincrease flexibility. They are sometimes used tofacilitate moulding of plastic by decreasing its melting
temperature.
No intentional use

Sum of all phthalates= 250 ppm

Phthalates can be found in:

GC-MS• Flexible plastic components (e.g., PVC)
• Print pastes• Adhesives• Plastic buttons• Plastic sleevings• Polymeric coatings

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ZDHC MRSLCAS No.

Substance

Group A: Raw Material
and Finished ProductSupplier GuidanceGroup B: Chemical SupplierCommercial Formulation
Limit

Potential Uses in Apparel and Footwear Textile
Processing

General Techniques forAnalysing Chemicals

Total Heavy Metals
Listed metals are banned from intentional use in textile manufacturing/finishing. Additionally, residual traces of antimony, zinc, copper, nickel, tin, barium, cobalt, iron, manganese, selenium andsilver in colourants are expected to comply with the Ecological and Toxicological Association of Dyes and Organic Pigments Manufacturers (ETAD) concentration limits (http://www.etad.com/).
7440-38-2

Arsenic (As)50 ppm

7440-43-9

Cadmium (Cd)20 ppm(50 ppm for pigments)
No intentional use

7439-97-6

Mercury (Hg)

4 ppm
(25 ppm for pigments)

7439-92-1

Lead (Pb)

100 ppm

18540-29-9

Chromium (VI)10 ppmArsenic and its compounds can be used in somepreservatives, pesticides and defoliants for cotton. It
is also associated with synthetic fibres, paints, inks,
trims, and plastics.
Cadmium compounds are found in or used as:
pigments (particularly red, orange, yellow and green),a stabilizer for PVC plastic, and in fertilizers, biocides
and paints (e.g., surface paints on zippers andbuttons).
Mercury compounds can be present in pesticides andcan be found as contamination in caustic soda
(NaOH). Mercury compounds may be used in paints(e.g., surface paints on zippers and buttons).
In apparel and footwear, lead may be associated withplastics, paints, inks, pigments and surface coatings.
Although typically associated with leather tanning,
chromium VI also may be used in the dyeing of wool
(after the chroming process).

Inductively coupled plasmaoptical emission spectrometry(ICP-OES), atomic absorption
spectroscopy (AAS)

Volatile Organic Compounds (VOC)
71-43-2

Benzene50 ppm

1330-20-7

Xylene500 ppm

95-48-7o-cresol

No intentional use

500 ppm

106-44-5

p-cresol

500 ppm108-39-4

m-cresol

500 ppm

June 2014

These volatile organic compounds should not be usedin textile auxiliary chemical preparations. They areassociated with solvent-based processes like solventbased polyurethane coatings and glues/adhesives.
They should not be used for any kind of facility
cleaning or spot cleaning.

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GC-MS

9