Preven&ng(hazardous(substances(from(reaching( …Preven&ng(hazardous(substances(from(reaching(fashion(ar&cles. The(Science(behind(it(Prof.(F.(Javier(Sardina Center(for(Research(on(Biological(Chemistry(and(Molecular

Preven&ng hazardous substances from reaching fashion ar&cles. The Science behind it

Prof. F. Javier Sardina Center for Research on Biological Chemistry and Molecular Materials

University of San&ago de Compostela, SPAIN

Istanbul, June 11th, 2015

EKOTEKS LABORATUVAR VE GÖZETİM HİZMETLERİ A.Ş.

8th Interna=onal 'Safe Produc=on, Safe Product' Symposium

For their prevalence and level of toxicity: -‐  Restricted Arilamines -‐  Formaldehyde -‐  Heavy metals -‐  Chromium(VI)

There are many chemical substances of concern for the manufacturer of tex&le ar&cles . Some are of more concern than others, for different reasons.

For their level of toxicity (rare): -‐  Chlorophenols -‐  Pes&cides -‐  Polycyclic Aroma&c Hydrocarbons -‐  Asbestos

For their impact on the environment: -‐  Phthalates -‐  Perfluorocarbons...

Others (also rare): -‐  Dimethyl fumarate -‐  Organo&n compounds...

Preven&ng what? Hazardous substances

Why are they in my ar&cle?

CLOTHING

BLEACHING

SCOURING

DESIZING

MERCERISING FIB. SYNTHESIS

FIBER YARN FABRIC

DYEING

LAUNDRY

FINISHING

PRINTING

TANNING

POL. PREP.

DYEING

Dyestuffs & Auxiliaries

Chemical Industry

They may come from materials and/or from manufacturing processes.

pH

Chlorophenols Pes&cides

Arylamines

Arylamines Formaldehyde Heavy metals Chromium(VI) Chlorophenols Phthalates

But, is there really a problem? For instance, let us examine the percentage of garments in which banned arylamines were detected during the period 2012-‐2014 (total number of styles surveyed: 233,000).

0,00

1,00

2,00

3,00

4,00

5,00

6,00

7,00

2012S 2012W 2013S 2013W 2014S 2014W

Percen

tage/ra=

o

Year/Season (S = Summer, W = Winter)

% of styles with detec&ons of banned arylamines (2012-‐2014)

% of styles with detec=ons of arylamines

Ra=o of parts with detec=ons per style

This downward trend is not spontaneous. It is the product of a lot of hard work!

Can we be more specific?

There are 24 different banned arylamines, each one of them arising from a different problema&c material or manufacturing process.

ARYLAMINE % MAIN COUNTRIES AFFECTED 4,4ʹ′-‐Diaminodiphenylmethane 48,3 Portugal, China, Turkey, Spain, Morocco 2,4-‐Diaminotoluene 11,5 China, Spain, Portugal, Turkey, Morocco Benzidine 7,7 China, India, Pakistan, Turkey, Bangladesh 4-‐Choroaniline 6,9 Portugal, China, India, Turkey, Morocco, Bangladesh, Pakistan 4-‐Aminoazobenzene 6,7 China, Pakistan o-‐Toluidine 3,8 Spain, Portugal, Turkey, Morocco, India, China o-‐Dianisidine 2,9 China, India, Pakistan, Bangladesh 3,3'-‐Dichlorobenzidine 2,6 China, Turkey, Pakistan, Portugal 4-‐Aminobiphenyl 1,9 India, Spain, China, Turkey, Pakistan, Morocco, Portugal 2,4-‐Dimethylaniline 1,7 Spain, Pakistan, Portugal, Turkey, Morocco 2,6-‐Dimethylaniline 1,5 Spain, Pakistan, Portugal, Turkey, Norocco o-‐Anisidine 1,1 China, Spain, Portugal, Bangladesh 5-‐Nitro-‐o-‐toluidine 0,9 China, Bangladesh, Pakistan, India

By looking at the data on the table, the task of finding which material or process gives rise to each specific arylamine (in each country) does not appear to be an easy one. I shall tell you now how we address this conundrum and try to prevent the presence of banned arylamines in fashion ar&cles.

Hazardous substances footprint To address the problem we need more detailed informa&on on the occurrence of specific banned substances in specific parts of garments, footwear, etc. The manufacturing processes, materials and technologies used leave a hazardous substances footprint on the ar&cles.

ARYLAMINES IN LEATHER ARYLAMINE % TOTAL % Main Fabrics % Threads and Comp. % Prints % Shoes

4-‐Aminoazobenzene 23,8 7,6 21,2 0,0 1,5 4,4ʹ′-‐Diaminodiphenylmethane 21,7 11,7 28,3 25,0 23,3 Benzidine 19,5 9,3 18,5 0,0 5,6 o-‐Toluidine 11,9 18,2 21,2 12,1 30,3 3,3ʹ′-‐Dimethoxybenzidine 4,3 8,3 50,0 0,0 0,0

ARYLAMINES IN CELLULOSIC FABRICS ARYLAMINE % TOTAL % Main Fabrics % Threads and Comp. % Prints % Foams

4,4ʹ′-‐Diaminodiphenylmethane 40,2 6,2 23,8 44,2 Benzidine 14,4 34,0 46,2 4,5 2,4-‐Diaminotoluene 11,1 10,7 5,0 24,8 54,5 3,3'-‐Dimethoxybenzidine 8,7 47,4 40,0 5,3 4-‐Chloroaniline 6,6 23,6 38,9 27,8 3,3ʹ′-‐Dichlorobenzidine 6,0 1,5 35,4 40,0

ARYLAMINES IN SYNTHETIC FABRICS ARYLAMINE % TOTAL % Main Fabrics % Threads and Comp. % Prints % Foams

4,4ʹ′-‐Diaminodiphenylmethane 56,5 10,1 36,5 30,4 4-‐Aminoazobenzene 17,8 41,9 47,6 1,6 2,4-‐Diaminotoluene 9,0 5,2 6,2 8,2 74,2 o-‐Anisidine 3,4 55,6 25,0 8,3 o-‐Toluidine 2,9 25,8 22,6 45,2 3,3ʹ′-‐Dichlorobenzidine 2,7 0,0 75,9 17,2

Manufacturing Epidemiology But this is just the beginning. Now we need to understand how the presence of specific arylamines in specific parts of the garments are related to the materials, processes and technologies used for manufacturing the ar&cles. Let me walk you through some relevant examples, so you can appreciate the process that we follow to address (and, hopefully, solve) the problem.

It is the banned arylamine most frequently detected, by far. Why? We use an inves&ga&ve tool to trace the origins of hazardous processes: MANUFACTURING EPIDEMIOLOGY.

First, we try to establish whether there is a clear associa&on of the banned substance to specific parts of the garments

PART % OCCURRENCE Posi=onal print 29,2 Con=nuous print 9,0 Main fabric/secondary fabric/shell/body 6,8 Applique/bow/ribbon/patchwork/patch/flower 6,8 Trimming/rib/piping/neck/strap/trim/binding/collar/placket/cuff 6,6 Printed label 5,5 Label (no embrodery, back label of jeans, for example) 4,5 Embroidery/lace/yarn 3,7

In this case, most detec&ons of the arylamine are linked to PRINTS and SMALL PARTS

H2N NH24,4'-Diaminodiphenylmethane (MDA)

Manufacturing Epidemiology

Secondly, we try to establish if the materials, technologies and processes used in the manufacturing of the affected parts may give rise to the banned substance

PRINTS


H2N NH2

4,4'-Diaminodiphenylmethane (MDA)

NH

NH

O

ON

O

ON

Blocked isocyanate

N NC C

OO

Contaminant if not prepared properly

During Printing

MATERIALS OK for MDA? Pigments or dyes YES Acrylic or PU Pastes YES CURING PROMOTERS (Catalysts) NO

But this is old news (we had already discovered this last year). So what is new?

Manufacturing Epidemiology We discovered that the World is very small indeed. A Japanese chemical manufacturer was supplying the same catalyst to several European chemical companies, which were reselling the product under different commercial names.



The tex&le produc&ons of three countries in par&cular were adversely affected (2012-‐1014). H2N NH2


COUNTRY % of DETECTIONS of MDA PORTUGAL 17,8 TURKEY 16,5 CHINA 15,5 SPAIN 14,7 MOROCCO 9,1

But, what else is new? Let us turn to SMALL PARTS



PART % OCCURRENCE Posi&onal print 29,2 Con&nuous print 9,0 Main fabric/secondary fabric/shell/body 6,8 Applique/bow/ribbon/patchwork/patch/flower 6,8 Trimming/rib/piping/neck/strap/trim/binding/collar/placket/cuff 6,6 Printed label 5,5 Label (no embrodery, back label of jeans, for example) 4,5 Embroidery/lace/yarn 3,7

What is the common link (material or process)?



ADHESIVES are used to temporarily alach many types of small parts to the main or secondary fabric before the final s&tching

“Removable pressure sensi&ve adhesives (PSA) are an important market. Their uses range from removable memo notes, to protec&ve films, to manufacturing aids. When good weatherability and clarity is required, solvent based acrylic PSAs are onen used. These materials typically consist of a func&onalized acrylic co-‐polymer crosslinked with a covalent crosslinker such as a polymeric isocyanate. This type of system exhibits good clarity and very stable proper&es over a long period of &me. Blocked polymeric isocyanate can func&on as an effec&ve crosslinker for removable acrylic solu&on adhesives. The blocked isocyanate can be mixed with a hydroxy func&onal acrylic adhesive to form a one component adhesive with proper&es very similar to two component adhesives crosslinked with unblocked polymeric isocyanates. The blocked isocyanate has the advantage of having a much longer shelf life which allows prac&cal produc&on of a one package, isocyanate crosslinked, acrylic adhesive.”

Solu&a, Inc.

Where have we heard this before?

H2N NH2


NH

NH

O

ON

O

ON

Blocked isocyanate

N NC C

OO

Contaminant if not prepared properly

Moisture


TDA is the second most frequently detected banned arylamine H2N

CH3

NH2

2,4-Toluylenediamine (TDA)

TECHNOLOGY % OCCURRENCE COUNTRY % OCCURRENCE SPONGE + FOAM + CUSHION 35,0 CHINA 21,4 PRINTS 15,6 SPAIN 20,5 LINING + INTERLINING 13,3 PORTUGAL 11,6 FILLING + MELANGE 12,6 TURKEY 9,9 INSOCK 8,7 MOROCCO 7,7 LABEL 4,2 VIETNAM 6,8 LEATHER 3,9 INDIA 3,7 TRIMMING 1,7 TUNISIA 3,7 SYNTHETIC/FAKE LEATHER 1,5 PAKISTAN 3,2 CORD 1,2 BANGLADESH 2,5

In this case, most detec&ons of the arylamine are linked to: -‐  LAMINATED FOAMS, from decomposi&on of polyurethane-‐based foams

at high temperature -‐  PRINTS, from TDA-‐based blocked isocyanates used as curing catalysts


ARYLAMINE % OCCURRENCE MAIN COUNTRIES AFFECTED Benzidine 7,7 China, India, Pakistan, Turkey, Bangladesh 4-‐Aminoazobenzene 6,7 China, Pakistan 4-‐Aminobiphenyl 1,9 India, Spain, China, Turkey, Pakistan, Morocco, Portugal

Benzidine

H2N H2NNH2N

N

H2N

4-Aminobiphenyl 4-Aminoazobenzene

PART % OCCURRENCE OF BENZIDINE Main fabric/secondary fabric/shell/body 23,7 Cord/rope/string 13,5 Embroidery/lace/yarn 9,0 Lining 5,8 Applique/bow/ribbon/patchwork/patch/flower 5,1 Sleeves fabric 4,5 Tassel 4,5 Interlinning/interlayer/non woven 4,5 Trimming/rib/piping/neck/strap/trim/binding/collar/placket/cuff 3,8

PART % OCCURRENCE OF 4-‐AMINOAZOBENZENE Linning 29,8 Tape/zipper tape/neck tape 10,5 Cord/rope/string 10,5 Main fabric/secondary fabric/shell/body 9,4 Trimming/rib/piping/neck/strap/trim/binding/collar/placket/cuff 9,4 Interlinning/interlayer/non woven 5,2 Embroidered label 4,2

What do they have in common?


Benzidine

H2N H2NNH2N

N

H2N

4-Aminobiphenyl 4-Aminoazobenzene

They are regarded as low value parts so, in some parts of the World, they are dyed with dyestuffs of inferior quality, which contain banned arylamines as impuri&es. But Alibaba ships anywhere, so the problem may appear anywhere.

BENZIDINE COUNTRY % OCCURRENCE

CHINA 30,9 INDIA 29,0 PAKISTAN 9,6 TURKEY 8,9 BANGLADESH 5,8 MOROCCO 3,9 PORTUGAL 3,7 SPAIN 2,3 VIET NAM 2,3

4-‐AMINOAZOBENZENE COUNTRY % OCCURRENCE

CHINA 71,4 PAKISTAN 6,1 BANGLADESH 4,2 SPAIN 4,0 PORTUGAL 3,4 MOROCCO 3,3 VIETNAM 2,1 INDIA 1,3 TURKEY 1,1

Over dyeing with low quality direct dyes is also a high risk prac&ce. Dyestuffs bought in small quan&&es onen&mes are of inferior quality and contain banned arylamines as contaminants.


Most, if not all, detec&ons of this banned arylamine are associated with parts dyed or printed with pigments. Especially, but not necessarily, in black, brown or green hues. Why?

ARYLAMINE % MAIN COUNTRIES AFFECTED 3,3'-‐Dichlorobenzidine 2,6 China, Turkey, Pakistan, Portugal

PART % OCCURRENCE Posi=onal print 26,2 Interlinning/interlayer/non woven 18,5 Con=nuous print 13,8 Trimming/rib/piping/neck/strap/trim/binding/collar/placket/cuff 9,2

3,3'-Dichlorobenzidine

H2N NH2

Cl

Cl

The culprit is, usually, THE LACK OF INFORMATION, because the origin of this banned arylamine is the use of mixtures of orange or brown pigments (based on C.I. Pigment Orange 13 or Pigment Orange 34) and black pigments (based on C.I. Pigment Black 7). -‐  Pigments Orange 13 and 34 contain 3,3’-‐dichlorobenzidine, but they

are totally insoluble, so they can be used safely. -‐  Pigment Black 7 is capable of (partly) solubilising other pigments if

mixed with them, so now 3,3’-‐dichlorobenzidine can be detected. -‐  We believe that this is a general phenomenon, so excercise due care

when prin&ng with mixtures that contain Pigment Black 7.

Manufacturing Epidemiology ARYLAMINE % MAIN COUNTRIES AFFECTED

4-‐Choroaniline 6,9 Portugal, China, India, Turkey, Morocco, Bangladesh, Pakistan ClH2N

4-Chloroaniline

-‐  84% of the detec&ons/fails for 4-‐chloroaniline are associated with ar&cles dyed in BLACK (cause: use of low quality C.I. Reac&ve Black 5-‐based dyestuffs).

-‐  33% of detec&ons/fails of 4-‐chloroaniline in printed garments are associated with ar&cles printed in BLACK (printed with low quality reac&ve dyestuffs based on C. I. Reac&ve Black 5).

COUNTRY % OCCURRENCE PORTUGAL 30,2 CHINA 20,0 INDIA 11,6 TURKEY 10,4 MOROCCO 8,2 BANGLADESH 6,7 PAKISTAN 5,2

Beware specially if you are dyeing with high loads of C.I. Reac&ve Black 5-‐based dyestuffs (9-‐10% of dyestuff). Why? All Reac&ve Black 5-‐based dyestuffs are contaminated with 4-‐chloroaniline. We have detected 4-‐chloroaniline (at levels > 20 mg/kg) in applica&ons dyed with 9% dyestuff contaminated with 150 mg/kg of 4-‐chloroaniline.

Formaldehyde

Formaldehyde is a totaly different case, since it is mostly associated with technologies which need a fixa&ve, such as pigment prints or dyeing with dyes with low affini&es for the crresponding fibers (basic or fluorescent dyes, for instance). Is this the whole story? Let us look at distribu&on of formaldehyde detec&ons (i. e. non-‐compliances) in baby garments made in the period 2013-‐2014.

In this period most detec&ons of formaldehyde were linked to PRINTS and SMALL PARTS. Does this sound familiar to you?

PART

BANGLADESH (%

)

CHINA (%

)

PORTU

GAL (%

)

TURKEY (%

)

Posi=onal Print 28,0 2,6 27,7 26,0 Con=nuous Print 9,8 10,4 2,1 15,3 Main fabric/Secondary fabric/Shell/Body 7,9 2,1 29,3 9,9 Trimming/Rib/Piping/Neck/Strap/Trim/binding/Collar/Placket/Cuff 8,5 19,3 8,8 8,8 Printed label 0,6 1,0 1,8 8,4 Lining 14,6 12,5 8,3 6,5 Embroidery/lace/Yarn 0,6 0,0 0,8 5,3 Applique/bow/ribbon/patchwork/patch/flower 0,0 2,6 5,7 4,6 Filling part /Foam 4,3 2,1 3,9 4,2

Formaldehyde

One case study allowed us to iden&fy one addi&onal source of worries in this area: We analyzed two very similar types of Lurex threads, made by the same manufacturer. There was only one apparent difference: the colour (the metallic components used were different). But there was a hidden difference, one showed unacceptable levels of formaldehyde, and the other was formaldehyde-‐free.

Formaldehyde level: 3 mg/Kg OK

Formaldehyde level: 21 mg/Kg KO

LUREX-‐POLYAMIDE

LUREX -‐VISCOSE

Formaldehyde

The Lurex threads were composed of only three parts: the tex&le core, the metallic layer, and an adhesive that binds them together. So the origin of the formaldehyde had to be the adhesive. There are several types of formaldehyde-‐based resins used as wood (urea-‐formaldehyde) and laminate (melamine-‐formaldehyde) adhesives. So we checked if urea or melamine were present in the Lurex threads, and yes, we found melamine in the golden thread (but not in the silver one) in levels analogous to those of formaldehyde. Thus, the preliminary conclusion was: a melamine-‐formaldehyde adhesive had been used in the manufacturing of the golden Lurex thread and that was the source of the formaldehyde detected.

We were able to secure a coil of the tex&le core of the golden Lurex thread, coated with the adhesive. An analysis showed high levels of both formaldehyde and melamine, thus confirming our preliminary conclusion.

So, again, watch out which kind of adhesives your are using while manufacturing your garments. They can be the source of, at least, banned arylamines and formaldehyde.

Phthalates

Phthalates are used as plas&cizers in plas&c materials. That is commmon knowledge in the tex&le manufacturing industry. •  So you need to worry about phthalates only if you have plas&c parts in your ar&cle (garment,

footwear or accessory) of if you are including plas&sol-‐based prints in it. Right? •  So you would not expect to find phthalates in something as removed from plas&cs as, say, paper.

Right?

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

SHOES BELTS BAGS LABELS

% of phthalates detec=ons per type of ar=cle

2012

2013

2014

Phthalates in fashion ar&cles are a moving target

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

PAPER PRINTS PU PLASTIC

% of phthalates detec=ons per type of material/technology

2012

2013

2014

Phthalates

Now let me tell you about a search triggered by a phone call that I got at home last August, about some strange findings discovered not far away from this very building. Our good friends of EKOTEKS played a key role in this findings, so I decided to call this story the EKOTEKS Mystery of Summer 2014. It all started with a shoe (well, several pairs of shoes actually).

Phthalates

The caller was fran&c, because several pairs of shoes that they intended to import into Turkey, through Istanbul, had been analyzed during the required Customs inspec&on and found to contain levels of phthalates non-‐compliant with the Turkish regula&ons. What went wrong?, he asked (as if I had a crystal ball, which of course I did not have), and what can we do to solve the problem, he urged me (as if I were not on vaca&on, about which he did not care at all). The plot thickened when he told me the part where the phthalates had been found: the insole. For those of you not familiar with shoe manufacturing, the insole is a piece of sturdy paper which forms the founda&on around which the whole shoe is constructed. Just a piece of paper, no plas&cs involved. So we started to work to unravel the mystery, and what we found len us perplexed and worried, because paper turned out not to be such a simple material as we thought it was.

Phthalates

Paper is made of cellulose fibers (no phthalate problem there) and fillers (chalk or clay, none of which contain phthalates). But then we found out that plas&cisers can be added to paper as components in dispersion glues (adhesives, again?) used to bind the cellulose fibers together. So apparently, someone had used dispersion glues plas&cized with phthalates in their manufacturing process to make the paper used to make the insoles which had been used to make the problema&c shoes (where does your value chain end?). Addi&onaly, we found that the insoles are usually made from recycled paper, so you also have to worry if the recycling has been performed correctly.

So, yet again, watch out which kind of adhesives your are using while manufacturing garments. They can be the source of at least, banned arylamines, formaldehyde and phthalates (to be con&nued?)

Insole Recycled paper containing phthalates

Phthalates detected > 1000 mg/Kg

Unsuccessful ink and adhesive removing process

in the paper mill

Adhesives incorporated to insole paper

to provide hydrophobicity, bust strength, tear strength,

folding endurance, etc.

Safe ProducJon: GMP Codes

Interna&onal Fashion Retailers are already adop&ng GOOD MANUFACTURING PRACTICES codes oriented towards safe/healthy produc&on and products. The most advanced of these codes include GMPs for: -‐  Manufacturing procesess -‐  Warehouses management and storage

condi&ons -‐  Internal traceability controls -‐  Dyestuffs and auxiliaries selec&on -‐  Safe dyeing, prin&ng, finishing and washing

condi&ons (all of the wet processes) -‐  Test/assay control protocols for:

-‐  Chemicals used -‐  Garments/ar&cles manufactured

-‐  And all the rest of the relevant processes involved in the manufacturing of tex&les that may influence safety (product health)

Ready ToManufacture

!"#$%&'(&)*(+,-.

Safe ProducJon: Choosing chemicals

Most of the problems detected start with a wrong (unsafe) choice of chemicals: dyestuffs, pigments and auxiliary chemicals: -‐  Residues of hazardous substances

are commonly found in commercial chemical products, some&mes in very high levels. These residues get transferred to the final ar&cles.

-‐  Residues of precursors of hazardous substances are also found in commercial chemical products. These may g i ve r i s e t o ha za rdous s u b s t a n c e s u n d e r s p e c i fi c circumstances.

What to do? To analyze and classify the commercially available tex&le chemicals with regards to their levels of hazardous substances and their precursors: The List, by Inditex (more than 8,500 chemical products classified in the 2nd edi&on).

ACHITEX MINERVA p. 3

ARCHROMA p. 21

ASUTEX p. 44

BASF p. 67

CHT-BEZEMA p. 90

DYSTAR p. 123

EVERLIGHT p. 173

HUNTSMAN p. 191

LONSEN p. 220

PULCRA CHEMICALS p. 233

SETAS p. 250

STAHL p. 265

TANATEX CHEMICALS p. 271

1. DYESTUFFS & AUXILIARIES

2. WATER & OIL REPELLENTS

3M p. 280

ARCHROMA p. 283

BASF p. 283

CHT-BEZEMA p. 283

PULCRA CHEMICALS p. 283

HUNTSMAN p. 283

RUDOLF p. 284

by

JANUARY 2015

THE LIST

Documents

Preven&ng(hazardous(substances(from(reaching( …Preven&ng(hazardous(substances(from(reaching(fashion(ar&cles. The(Science(behind(it(Prof.(F.(Javier(Sardina Center(for(Research(on(Biological(Chemistry(and(Molecular