Submission of informat
ion on
TEMPLATE
for third party submission of information on alternatives for
Applications for Authorisation
NON-CONFIDENTIAL
Legal name of submitter(s):
ETAD Ecological and Toxicological Association of
Dyes and Organic Pigments Manufacturers
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
TABLE OF CONTENTS
1. ALTERNATIVE ID AND PROPERTIES ......................................................................... 3
2. TECHNICAL FEASIBILITY ........................................................................................ 3
3. ECONOMIC FEASIBILITY ......................................................................................... 3
4. HAZARDS AND RISKS OF THE ALTERNATIVE............................................................. 3
5. AVAILABILITY ....................................................................................................... 9
6. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVE .................... 9
7. OTHER COMMENTS ................................................................................................ 9
REFERENCES ............................................................................................................ 9
APPENDIXES ............................................................................................................. 9
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
2
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
1. ALTERNATIVE ID AND PROPERTIES
[Insert text here]
2. TECHNICAL FEASIBILITY
[Insert text here]
3. ECONOMIC FEASIBILITY
[Insert text here]
4. HAZARDS AND RISKS OF THE ALTERNATIVE
With regard to the described hazards of the alternative substances we have a different view.
Colorant producers present on the international market and with manufacturing sites worldwide
already submitted to ECHA REACH dossiers on most organic pigments discussed as alternatives.
Based on the current knowledge of the substances and of the manufacturing processes such
alternative colorants have a less problematic toxicological profile compared to lead chromates.
The comments can be found in various similar documents (0012-05, 0012-06, 0012-09, 001210,0012-11,0012-12). The page number may vary.
4.1 DIARYLIDE PIGMENTS – DIARYLIDES – ALTERNATIVE 3
No.
Page No.
28
32
Quote
Production of semi-products is very
dangerous and pollutive. When breaking
down into constituent parts the pigments
yield dangerous classified substances.
Limitations for these releases have already
been set in European legislation for
example for food packaging.
48
53f
58f
In Appendix 1 we have given an overview
of warnings from market suppliers
(excluding the applicant) regarding the
various alternatives. These warnings and
independent research generally support
the views below which are the summarised
opinion of the applicant regarding the risks
Comment
The production can take place mainly in closed
systems, i.e. occupational exposure can be
excluded. Additionally, through appropriate
waste treatment, these organic semi-products
can be decomposed to toxicological harmless
compounds.
The thermal degradation of azo diarylide
pigments in polymers is a long known issue. A
corresponding publication from ETAD clarified
already in 1990 under which conditions the
breakdown occurs, with specific references to
the different applications. The document is a
well-known reference also outside the
association.
Non-classified pigment grades of PO. 34, PY.
13 and PY. 83 are available on the market.
Experimental data on all four pigments has
been collected and generated for the purpose of
registration under REACH at the tonnage band
of > 1000 tpa (PY. 13 and PY. 13) and
100/1000 tpa (PO. 34, PO. 13).
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
3
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
of the alternatives in this group.…
- Some of the pigments in the group are
classified as carcinogenic due to impurities
(PO.34), or have MSDS warnings of being
sensitisers (PO. 13, PO. 34) or causing
other toxic effects (PY.13, PY.83);
In general, all four pigments are not toxic upon
acute ingestion, not irritating to skin and eyes
and do not cause skin sensitization in
experimental animals. No adverse effect after
repeated exposure, no genotoxicity or
reproductive toxicity was observed. The
pigments are not considered to be carcinogenic
and no hazard for the environment was
identified. As regards the specific warnings:
(PO34): Carcinogenic due to impurities - This
description is based on a MSDS from
CHEMTREC, as written on P110.
These impurities are described as carbon black
and ethylbenzene. These impurities are not
mentioned in the entries for PO34 REACHregistration, and no corresponding classification
is triggered for the registered products.
(PO 13, PO 34): warning of being sensitisers This description is based on MSDS from Lansco
Colour (PO 13) and from CHEMTREC, as
written on P 109 and 110, respectively. See
general comment above.
Additionally, concerning PO34 the above
mentioned MSDS says “May cause silicosis due
to crystalline silica presence.” This implies that
the toxic effect is caused by silica and not by
PO34.
(PY13, PY83): causing other toxic effects
Concerning PY13, there are no such
descriptions in Annex 1 P109-117. It might be a
typo.
Concerning PY83, the MSDS from CHEMTREC,
P 116, says “May be fatal to swallow and long
term exposure may cause permanent brain and
nervous system damage + may cause corrosion
/ irritation.” This MSDS contradicts the above
information submitted for REACH, a CHEMTREC
product-specific classification is a possible
explanation.
In particular, PY83 showed no specific target
organ toxicity, either by single or by repeated
exposure.
48
54
59
There is already primary legislation
regarding the release Primary Aromatic
Amines (3-3’ dichlorobenzidine) setting a
limit in plastics that is already hard to
meet but in coatings there is no residue
over 10 ppb permitted
There are grades of PY 83 available which
meet the requirements of Resolution AP (89) 1
on the use of colorants in plastic materials
coming into contact with food. Among others
this Resolution sets a limit for primary aromatic
amines (including 3-3'dichlorbenzidine) of <
500 ppm for pigments. This requirement for the
pigment will result in a negligible exposure
through potential migration from the coloured
plastic material.
48
54
59
…The intermediate factory needs to be a
so-called ATEX facility– ergo constructed to
deal with explosives and considering how
many accidents are still occurring, this
problem is not theoretical and world-wide
production of diarylide pigments causes
much more immediate damage than PY.34
and PR.104.
The production can proceed safely by using
suitable equipment and following safe handling
procedures.
…Due to the health hazards of the
precursor DCB, the manufacture is
mandatorily happening in closed systems
Even in China or in India, safe production can
be achieved by using suitable equipment and
following safe handling procedures.
48
54
59
Accidental explosions have been reported in the
past, but, to the best of our knowledge, due to
mistakes occurred during production.
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
4
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
with full PPE for personnel – of course in
India and China (which are the main
sources) this requirement is rarely fulfilled
4.2
No.
48
54
59
…Azo substances are also known to
degrade into the environment under
slightly acidic conditions – the higher the
acidity the faster the degradation.
Diarylides pigments do not show such
tendency, as reported in many available
publications and specifically addressed by the
corresponding endpoints in their REACH
registrations.
48
54
59
…There is already primary legislation
regarding the release Primary Aromatic
Amines (3-3’dichlorobenzidine) setting a
limit in plastics that is already hard to
meet but in coatings there is no residue
over 10 ppb permitted.
The Resolution AP (89) 1 on the use of
colorants in plastic materials coming into
contact with food sets a limit for primary
aromatic amines (including 33'dichlorbenzidine) of < 500 ppm for pigments.
This requirement for the pigment will result in a
negligible exposure through potential migration
from the coloured plastic material.
48
54
59
…The increased use of the xylene solvent
is also an issue that contributes to the
environmental and human exposure to
hazardous substances. This illustrates that
shifting to diarylides is not benificial.
Production processes exist where very little
xylene is used for diarylide pigments and in
particular no xylene is used for the diarylides
pigments used as lead chromium substitutes.
48
54
59
…Furthermore diarylides are known to
generate carcinogenic by-products during
their Decomposition.
The thermal degradation of azo diarylide
pigments in polymers is a long known issue. A
corresponding publication from ETAD clarified
already in 1990 under which conditions the
breakdown occurs, with specific references to
the different applications. The document is a
well-known reference also outside the
association.
ORGANIC PIGMENTS - DIANISIDINE – ALTERNATIVE 4
Page No.
54
61
Quote
55
61
…Azo substances are also known to
degrade into the environment under
slightly acidic conditions – the higher the
acidity the faster the degradation; there is
evidence that humans may metabolise the
Azo substance to its carcinogenic parent
compound.
Diarylide pigments do not show such tendency,
as reported in various available publications
and specifically addressed by the corresponding
endpoints in REACH registrations dossiers of
diarylide pigments. Organic pigments in
general, due to their high insolubility, share the
same lack of bioavailability.
55
61
…When the pigment degrades – which it
does very easily due to its poor durability –
it will release its carcinogenic molecules –
unlike the PY.34 and PR.104 molecules
that are poorly soluble these ones are
soluble and very dangerous.
See comment above.
61
x
…There is already primary legislation
regarding the release Primary Aromatic
Amines (3,3’-dichlorobenzidine ) setting a
limit in plastics that is already hard to
meet but in coatings there is no residue
The Resolution AP (89) 1 on the use of
colorants in plastic materials coming into
contact with food sets a limit for primary
aromatic amines (including 33'dichlorbenzidine) of < 500 ppm for pigments.
…The intermediate used in the
manufacture of these pigments is 3,3’dianisidine is presumed to have
carcinogenic potential for humans. The
manufacture is mandatorily happening in
closed systems with full PPE for personnel.
In India and China (which are now almost
the only sources) this requirement is rarely
fulfilled.
Comment
Even in China or in India, production can be
achieved safely by using suitable equipment
and following safe handling procedures.
Additionally, even if more soluble in comparison
with lead chromates, PO16 still is a quite
insoluble substance.
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
5
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
over 10 ppb permitted.
This requirement for the pigment will result in a
negligible exposure through potential migration
from the coloured plastic material.
54
61
…PO. 16 is itself sometimes noted as a
suspected human carcinogen;
PO 16:
61
x
…The increased use of the xylene or other
solvent is also an issue that degrades the
environment/health benefit of shifting to
diasinides.
Production processes exist where xylene is not
used in the PO 16 production.
Experimental data on acute and subacute
toxicity in rats as well as genotoxicity has been
made public by MHLW Japan. The acute oral
toxicity (OECD 401) was found to be greater
than 2000 mg/kg bw and no mortality occurred.
No adverse findings were observed in the
subacute oral study at the limit dose (OECD
407). PO 16 did not cause genotoxicity in the
Ames test with Prival modification for azo
compounds (OECD 471) and in the
chromosome aberration test in vitro (OECD
473). All studies were reported to be performed
under GLP.
4.3
ORGANIC PIGMENTS – AZO BENZIMIDAZOLONES – ALTERNATIVE 5
4.4
ORGANIC PIGMENTS – MONOAZO – ALTERNATIVE 6
4.5
ORGANIC PIGMENTS – SPECIALTY AZO – ALTERNATIVE 7
4.6
ORGANIC PIGMENTS – OTHER ORGANICS – ALTERNATIVE 8
No.
4.7
No.
Page No.
80
94
101
Quote
PY. 110 and PY. 138 both have extremely
dangerous production with intermediate
products required that are unstable or
solvents that are toxic.
In the case PY.110 it is the use of PCl in
manufacture and the need to use
dangerous
solvents
dichlorobenzene
(Carcinogen cat. 2), POCl3 or
trimethylbenzene (causes chronic solvent
induced encephalopathy). Furthermore 1,4
- Benzenediamine and Tetrachlorophthalic
anhydride
both
substances
dermal
sensitiser and known
cause of occupational asthma are used as
an intermediate in the production of
PY.110…
Comment
Safe production can be achieved by using
suitable equipment and following safe handling
procedures.
DPP PR. 254 – ALTERNATIVE 9
Page No.
82
97
103
Quote
Comment
…The manufacture is done as follows:…
The synthesis steps provided do not reflect a
scientific sound manufacturing process for PR
254. A suitable reference can be found, e.g., in
“Industrial Organic Pigments, W. Herbst, K.
Hunger (Second Edition), VCH”.
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
6
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
85
101
107
The production of DPP is very dangerous
due to the acids needed in the
production….
The production of DPP is mainly conducted
under alkaline conditions. To our knowledge,
acids are used only for neutralization and the
process can be performed under controlled
conditions.
4.8 ALTERNATIVES PROPOSED BY SWEDEN IN ITS RESTRICTION PROPOSAL –
ALTERNATIVE 10
No.
Page No.
86
102
109
Quote
There are no known toxicity studies for this
substance but the MSDS sheet advises the
use of respirators and personal protective
equipment due to possible skin
sensitisation97. Furthermore PR.2 is
mainly manufactured in China – all known
sources are heavily contaminated with
PCBs and deemed so hazardous that no
western manufacturers wishes to use the
pigment.
88
103
111
…Pigment Red 57……The substance is a
known respiratory and skin sensitizer
according to the risk statements that
accompany it.
88
103
112
Pigment Red 122…The production of this
pigment is also highly pollutive with 5-8 kg
of phosphates emitted to surface waters
for every 1 kg of pigment produced.
C.I. Pigment Yellow 12
…The substance is dangerous when in the
presence of strong oxidizing agents and
explosive.
104
Comment
PR 2 has been registered for REACH, and the
pigment dossier contains key toxicity studies as
well as supporting studies and read-across
references. The skin sensitisation labelling is
also based on the evaluation of existing data.
No other toxicity is supported by the provided
studies.
Accordingly to its REACH dossier in the >1000
tpa range, the pigment was registered in
Europe by seven companies, most of them
present on the international market and with
manufacturing sites worldwide. It is also
manufactured by other companies with the
same profile. Independently from the
production site, PR 2 grades are available
which will comply with Resolution AP(89)1.
In general, non-classified pigment grades of PR
2 are commercially available; these grades
show PCBs contents below 50 ppm; specific
grades with PCBs contents below 25 ppm are
available as well. PR 2 is widely used in
Europe, mainly for printing ink applications.
PR57:1
Experimental data has been collected and
generated for the purpose of registration under
REACH at the tonnage band of > 1000 tpa.
Pigment Red 57:1 is not toxic upon acute
ingestion, skin contact and inhalation. It is not
irritating to skin and eyes and does not cause
skin sensitization in experimental animals. A
screening study for subacute toxicity and
repeated dose and reproductive toxicity showed
adverse effects on the kidney at high doses.
The pigment is a complex between an organic
acid and calcium and dissociates at extreme
pH, such as present in the stomach. Therefore,
solubility is higher than for other pigments and
uptake after ingestion is observed. The
analogue sodium salt (Pigment Red 57) did
not cause adverse effects in a life-long feeding
study starting with in utero exposure. The
substance will undergo testing for teratogenicity
and fertility in the near future. No genotoxicity
was observed. No hazard for the environment
was identified.
Current manufacturing processes exist which
incorporate a recovery step in the production,
allowing phosphates to be reused or recycled.
No autoflammability, flammability or explosive
properties have been shown by the studies
collected or generated for the REACH
registration of PY 12.
4.9 APPENDIX I
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
7
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
No.
Page No.
102
117
125
Quote
…PY.168…
Comment
PY168:
Experimental data has been collected and
generated for the purpose of registration under
REACH at the tonnage band of 100 - 1000 tpa.
Pigment Yellow 168 is not toxic upon acute
ingestion. A structural analogue was nontoxic
after single skin contact. It is not irritating to
skin and eyes and does not cause skin
sensitization in experimental animals. No
adverse effects were observed after repeated
exposure to a structural analogue in animal
studies. There is also no indication of a fertility
impairing effect or a developmental toxic /
teratogenic effect after administration of the
analogue. No genotoxicity was observed. No
hazard for the environment was identified.
102
117
125
…PY.183…
PY183:
Experimental data has been collected and
generated for the purpose of registration under
REACH at the tonnage band of 100 - 1000 tpa.
Pigment Yellow 183 is not toxic upon acute
ingestion, single skin contact and inhalation. It
is not irritating to skin and eyes and does not
cause skin sensitization in experimental
animals. No adverse effects were observed
after repeated exposure to an analogue
structure in animal studies. There is also no
indication of a fertility impairing effect or a
developmental toxic / teratogenic effect after
administration of the analogue. No genotoxicity
was observed. No hazard for the environment
was identified.
103
118
126
…PY.61…
PY61:
Experimental data has been collected and
generated for the purpose of registration under
REACH at the tonnage band of 10 - 100 tpa.
A structural analogue of Pigment Yellow 61 is
not toxic upon acute ingestion, Pigment Yellow
61 nontoxic after a single skin contact. The
analogue is not irritating to skin and eyes.
Pigment Yellow 61 does not cause skin
sensitization in experimental animals. No
adverse effects were observed after repeated
exposure to a structural analogue in animal
studies. There is also no indication of a fertility
impairing effect or a developmental toxic /
teratogenic effect after administration of the
analogue. No genotoxicity was observed at
analogue substances. No hazard for the
environment was identified.
103
118
126
…PY.62…
PY62:
Experimental data has been collected and
generated for the purpose of registration under
REACH at the tonnage band of 100 - 1000 tpa.
Pigment Yellow 62 is not toxic upon acute
ingestion. A structural analogue was nontoxic
after single skin contact. It is not irritating to
skin and eyes and does not cause skin
sensitization in experimental animals. No
adverse effects were observed after repeated
exposure in animal studies. There is also no
indication of a fertility impairing effect or a
developmental toxic / teratogenic effect. No
genotoxicity was observed. No hazard for the
environment was identified.
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
8
SUBMISSION OF INFORMATION ON ALTERNATIVES (NON-CONFIDENTIAL)
5. AVAILABILITY
[Insert text here]
6. CONCLUSION ON SUITABILITY AND AVAILABILITY OF THE ALTERNATIVE
[Insert text here]
7. OTHER COMMENTS
[Insert text here]
REFERENCES
[Insert text here]
APPENDIXES
[Insert text here]
[0012-03 - 0012-12, ] [PBr24, PY12, PY13, PY14, PY17, PY42, PY53, PY65, PY73, PY74, PY83, PY97, PY110,
PY138, PY139, PY151, PY153, PY154, PY155, PY184, PY194, PR101, PO13, PO16, PO34, PO36, PO67,
PO73, PR2, PR4, PR53:1, PR57:1, PR122, PR254, ] [March 17, 2014]
9