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Substitution of Cobalt Driers and Methyl Ethyl Ketoxime
6 Environmental and health screening
An environmental and health screening has been performed of the existing and alternative driers and anti-skinning
agents in order to learn more about which alternatives that may or may not be relevant from a health and
environmental point of view. Alternatives with an inferior environment and health profile in the screening will not be
worth testing as the goal is to find more environmental and health friendly alternative primary driers and
anti-skinning agents.
The environmental and health screening of cobalt driers and alternatives, and hydroquinone, methyl ethyl ketoxime
and alternatives, has been performed based on the classification of the substances combined with ready available
information, /21/. The risk phrases for ecotoxicity as well as human toxicity or the corresponding criteria are used in
the allocation of an environmental and human score to the substances. The risk phrases can be used as the
following examples illustrate:
| Aquatic ecotoxicity |
Score 4:
R50 (very toxic)
|
Score 2:
R51 (toxic)
|
Score 1:
R52 (harmful)
|
| Human toxicity |
Score 8:
R26-27-28 (very toxic)
R45 (may cause cancer)
|
Score 4:
R23-24-25 (toxic)
|
Score 1:
R20-21-22 (harmful)
R38-37-38 (irritating)
|
In the screening it is not only relevant to look upon the active ingredient of the drier products and anti-skinning
agents. It is also necessary to include an assessment of the other components such as organic solvents and drying
accelerators, as the purpose is to improve the entire profile of the products.
The active ingredient (i.e. the metallic component for the driers) is dissolved in one or more organic solvents. The
solvents are also scored for their human toxicological effects and will be included in the evaluation of the different
drier products and the different anti-skinning agents.
Some of the alternative drier products also contain a drying accelerator to enhance the catalytic effect of the drier.
These drying accelerators are also scored for their human toxicological effects.
Only very few of the substances in the drier products or in the anti-skinning agents are given an environmental score
as only few substances are classified due to environmental hazards.
6.1 Screening of the drier products
The results of the screening are presented in Table 6.1 The screening has predominantly been based on information from the
suppliers presented in material safety data sheets, /22/. Where readily available information was available on
specific substances (and where the substances were specified with CAS-numbers), this information has been
included in the screening as well. This especially applies for the cobalt compounds, which are considered possible
carcinogens by IARC, /23/.
The classification applied to the organic solvents (the petroleum distillates) has also been checked in the "European
list of dangerous substances", /24/. In case of deviation from the classification given in the MSDS the classification
is presented as a note to the table and the score is presented in brackets.
Table 6.1
Environmental
and health
screening of
driers.
| Codes |
Substance |
Metal |
% |
Classification / Labelling |
Health score |
Environ-mental score |
| Co |
Cobalt 2-ethylhexanoate |
Co |
40-70 |
Xi R38 |
81 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
|
Xn R65 |
1 (8) |
|
| Mn |
Manganese 2-ethylhexanoate |
Mn |
30-60 |
Xi R38 |
1 |
|
| Traditional |
Naphtha (petroleum),
hydrated heavy4 |
|
40-70 |
Xn R65,66 |
1 (8) |
|
| |
2-(2-ethoxyethoxy)
ethanol |
|
0-6 |
Xi R36 |
1 |
|
| Mn1 |
Manganese compound3 |
Mn |
2.5-10 |
? |
? |
|
| |
(2-methoxymethylethoxy)
propanol9 |
|
50-100 |
Not classified |
0 (4) |
|
| |
n-Butanol |
|
2.5-10 |
Xn R10-22-37/38-41-67 |
4 |
|
| |
1,10-phenanthroline |
|
2.5-10 |
T, N R25-50/53 |
4 |
4 |
| |
Diethylenglycol
monobutyl ether |
|
2.5-10 |
Xi R36 |
1 |
|
| |
2-ethylhexanoic acid |
|
<2.5 |
Xn R63 |
8 |
|
| |
White spirit5 |
|
<2.5 |
R10, Xn R65 |
1 (8) |
|
| Mn2 |
Manganese salt of C6-19
branched fatty acid
and naphthenic acid3 |
Mn |
<43 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<48 |
Xn R65,66 |
1 (8) |
|
| |
Amino complexing agent |
|
<2.6 |
Xn R20/21/22 |
1 |
|
| Mn3 |
Manganese salt of C6-19
branched fatty acid3 |
Mn |
<52 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<44.5 |
Xn R65,66 |
1 (8) |
|
| |
Amino complexing agent3 |
|
<10 |
Xn R20/21/22 |
1 |
|
| Mn4 |
Manganese salt of C6-19
branched fatty acid |
Mn |
10-25 |
Xi R38 |
1 |
|
| |
(2-methoxymethylethoxy)
propanol9 |
|
50-100 |
Not classified |
0 (4) |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
2.5-10 |
Xn R65,66 |
1 (8) |
|
| |
2,2'-bipyridyl11 |
|
2.5-10 |
Xn R20/21/22 |
1 (0) |
|
| |
2-(2-butoxyethoxy)ethanol |
|
<2.5 |
Xi R36 |
1 |
|
| Mn5(w) |
Manganese salt of C6-19
branched fatty acid3 |
Mn |
<47 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<9 |
Xn R65,66 |
1 (8) |
|
| |
Amino complexing agent3 |
|
<2.6 |
Xn R20/21/22 |
1 |
|
| |
2-methylpentane-2,4-diol |
|
<4 |
Xi R36/38 |
1 |
|
| |
Highly refined mineral oil |
|
<12 |
- |
0 |
|
| |
Ethoxylated alcohols, C12-14 |
|
<11.5 |
Xi R41, N50 |
4 |
4 |
| |
2-(2-butoxyethoxy)
ethanol |
|
<1 |
Xi R36 |
1 |
|
| Mn6(w) |
Manganese
dipropionate
Manganese(II) isooctanoate
Manganese isononate
|
Mn
Mn
Mn |
10-30
10-30
10-30
|
Xi R38
Xi R38
Xi R38
|
1
1
1
|
|
| |
White spirit5 |
|
10-30 |
R10, Xn R65 |
1 (8) |
|
| |
2-butoxyethanol |
|
5-15 |
Xn R20/21/22, Xi R36/38 |
1 |
|
| |
2,2'-bipyridyl11 |
|
1-10 |
T, R25, Xn R21, R52/53 |
4 (0) |
1 |
| Mn7 |
Manganese 2-ethylhexanoate |
Mn |
2.5-10 |
Not mentioned10 |
(1) |
|
| |
Xylene, mixture of isomers |
|
25-50 |
Xn R10, Xi R20/21,38 |
1 |
|
| |
n-butanol |
|
25-50 |
Xn R10-22-37/38-41-67 |
4 |
|
| |
White spirit5 |
|
10-25 |
Xn R10-65 |
1 (8) |
|
| |
Ethylbenzene |
|
2.5-10 |
F, Xn R11-20 |
1 |
|
| |
1,10-phenanthroline |
|
2.5-10 |
T, N R25-50/53 |
4 |
4 |
| |
2-ethylhexanoic acid |
|
<2.5 |
Xn R63 |
8 |
|
| V1 |
Vanadium organophosphate |
V |
<59.5 |
Xn R22 |
1 |
|
| |
Glycolether |
|
|
?? |
? |
|
| V2 |
Vanadium
neodecanoate
Potassium 2-ethylhenanoate
|
V
K
|
10-30
10-30
|
Xi R38
Xi R38
|
1
1
|
|
| |
White spirit5 |
|
30-50 |
R10, Xn R65 |
1 (8) |
|
| |
Neodecanoic acid |
|
10-20 |
Not classified |
0 |
|
| |
2-(2-butoxyethoxy)ethanol |
|
1-10 |
Xi R36 |
1 |
|
| |
Diethylenglycol |
|
1-10 |
Xi R22 |
1 |
|
| V3(w) |
Confidential |
V |
|
?? |
? |
|
Drying
accelerator
|
2-butoxyethanol |
None8 |
78 |
Xn R20/21/22, Xi R36/38 |
1 |
|
| |
2,2'-bipyridyl11 |
|
19 |
T, R25, Xn R21, R52/53 |
4 (0) |
1 |
| |
Water |
|
3 |
Not classified |
0 |
|
| Al |
Aluminium complex, organic3 |
Al |
80-90 |
R10, Xi R41 |
4 |
|
| |
Solvent naphtha (petroleum), medium heavy, aliphatic hydrocarbons6,7 |
|
20-50 |
Xn R65 |
1 (4) |
|
| Ca |
Calcium octoate2 |
Ca |
<42 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum), hydrated heavy4 |
|
<57.5 |
Xn R65,66 |
1 (8) |
|
| |
2-(2-butoxyethoxy)ethanol |
|
<3.5 |
Xi R36 |
1 |
|
| Ba |
Barium salt of C6-12 fatty acid |
Ba |
<40 |
Xn R20/22 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<44.5 |
Xn R65,66 |
1 (8) |
|
| |
2-ethylhexanoic acid |
|
<15.5 |
Xn R63 |
8 |
|
| |
2-methylpentane-2,4-diol |
|
<2.5 |
Xi R36/38 |
1 |
|
| |
2-(2-butoxyethoxy)ethanol |
|
<2 |
Xi R36 |
1 |
|
| Bi |
Bismuth salt of C8 carboxylic acid3 |
Bi |
50-100 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
5-25 |
Xn R65,66 |
1 (8) |
|
| K |
Potassium octoate2 |
K |
<72 |
Xi R38 |
1 |
|
| |
2-(2-butoxyethoxy)
ethanol |
|
<26.5 |
Xi R36 |
1 |
|
| |
C3-24 fatty acid |
|
<5.5 |
Xn R22,36 |
1 |
|
| Sr |
Strontium(II)octanoate |
Sr |
<4 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<38 |
Xn R65,66 |
1 (8) |
|
| |
C3-24 fatty acid |
|
<18.5 |
Xn R22,36 |
1 |
|
| |
2-(2-butoxyethoxy)
ethanol |
|
<3.5 |
Xi R36 |
1 |
|
| Zn |
Zinc 2-ethylhexanoate |
Zn |
30-60 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
40-70 |
Xn R65,66 |
1 (8) |
|
| |
2-(2-ethoxyethoxy)
ethanol12 |
|
0-5 |
Xi R36 |
1 (0) |
|
| Zr |
Zirconium octoate2 |
Zr |
<46 |
Xi R38 |
1 |
|
| |
Naphtha (petroleum),
hydrated heavy4 |
|
<55 |
Xn R65,66 |
1 (8) |
|
| |
2-(2-butoxyethoxy)
ethanol |
|
<2.5 |
Xi R36 |
1 |
|
1. Dermatitis of allergenic type. Indication of a carcinogenic
effect in human populations. IARC: Possibly carcinogenic to humans (Group 2B),
/23/.
2. Octanoate?.
3. Confidential.
4. Carc2;R45 Xn;R65 according to the List of dangerous substances
/24/. The difference in classification for the substance is
due to different MSDS's from different suppliers, and may also be due to how updated
the MSDS's are.
5. Carc2;R45 R10 Xn;R48/20-65 according to the List of dangerous
substances /24/.
6. R10 Xn;R48/20-65 according to the List of dangerous substances
/24/.
7. The substance is adopted at the List of undesirable substances,
/25/.
8. The product is drying accelerator.
9. QSAR models indicate that the solvent can produce airway allergy,
/26/. Not classified according to the list of dangerous substances
/24/.
10. Classification not mentioned on the American MSDS –
but probably Xi, R38.
11. At present not classified according to the List of dangerous
substances /24/. The difference in classification for the substance
is due to different MSDS's from different suppliers, and may also be due to how
updated the MSDS's are.
12. At present not classified according to the List of dangerous
substances /24/.
Xi Irritant.
Xn Harmful.
N Environmental dangerous
R10 Flammable
R20/22 Harmful by inhalation or if swallowed.
R20/21/22 Harmful by inhalation, in contact with skin or if swallowed.
R21 Harmful in contact with skin.
R22 Harmful if swallowed.
R36 Irritating to eyes.
R36/38 Irritating to eyes and skin.
R36/37/38 Irritating to eyes, the respiratory system and to the
skin.
R38 Irritating to the skin.
R40 Limited evidence of a carcinogenic effect.
R41 Risk of serious damage to the eyes.
R45 May cause cancer.
R48 Danger of serious damage to health by prolonged exposure.
R48/20 Harmful: danger of serious damage to health by prolonged
exposure through inhalation.
R48/20/22. Harmful: danger of serious damage to health by prolonged
exposure through inhalation or if swallowed.
R50/53 Very toxic to aquatic organisms, may cause long-term adverse
effects in the aquatic environment
R63 Possible risk of harm to unborn child.
R65 Harmful: may cause lung damage if swallowed.
R66 Repeated exposure may cause skin dryness or cracking.
R67 Vapours may cause drowsiness and dizziness.
6.1.1 Evaluation of the driers
The drier included in the screening is the cobalt drier:
and alternative driers:
- Manganese compounds (e.g. manganese 2-ethylhexanoate)
- Vanadium compounds (e.g. vanadium organophosphate and vanadium neodecanoate)
As primary driers rarely are used on their own a number of secondary driers are also included in the screening.
A preliminary search for toxicological information has been done for the active substances in the driers. Only cobalt
2-ethylhexanoate has been found explicit in the common databases, but the information is sparse.
Cobalt 2-ethylhexanoate has been scored 8 due to indication of carcinogenic effect in human populations. IARC
(International Agency for Research on Cancer) evaluate cobalt and cobalt compounds as possibly carcinogenic to
humans (Group 2B), which cause the cobalt compounds to end up with a health score of 8, /23/. Furthermore the
substance can result in dermatitis of the allergenic type. According to the MSDS cobalt 2-ethylhexanoate is
classified as Xi, R38 (Irritating to skin), resulting in a score 1. Although the MSDS indicate a score 1 for the cobalt
compound, the information found in the literature has been used in the screening.
The manganese driers are classified Xi, R38 (Irritating to skin), resulting in a score 1. The rest of the alternative
driers are classified as Xi, R38 (Irritating to skin) or Xn, R22 (Harmful if swallowed), resulting in a score 1. For a
single drier product the content is confidential, therefore no classification or health score is given.
Of the alternative secondary driers the aluminium complex is scored 4 due to the potential risk for eye irritation (a
classification of Xi, R41 (Risk of serious damage to eyes).
Evaluation of the primary driers by using the screening method excludes the cobalt drier. Of secondary driers the
aluminium complex is excluded.
6.1.2 Evaluation of the organic solvents
The organic solvents can be divided in two groups: petroleum distillates (more or less well defined
substances/group of substances) and specific substances. The petroleum distillates are present in most of the drier
products whereas the other substances are present in one or more of the drier products.
The petroleum distillates are:
| • Naphtha (petroleum) – hydrated heavy | (CAS-no. 64742-48-9) |
| • White spirit (Stoddard solvent) | (CAS-no. 8052-41-3) |
| • Solvent naphtha (petroleum) medium heavy aliphatic hydrocarbon | (CAS-no. 64742-88-7) |
| • Highly refined mineral oil | (CAS-no. 8042-47-5) |
The petroleum distillates (with the exception of highly refined mineral oil) are classified as Xn, R65 (Harmful: may
cause lung damage if swallowed) and/or R66 (Repeated exposure may cause skin dryness or cracking), depending
on the supplier, leading to score 1. According to the "European list of dangerous substances", /24/ these substances
are classified as T, R45 (carc2; May cause cancer) or Xn, R48/20 (Danger of serious damage to health by
prolonged exposure via inhalation) leading to score 8 and 4 respectively. The petroleum fraction "highly refined
mineral oil" has no classification and hence a score of 0.
The specific substances are:
| • (2-Methoxymethylethoxy)propanol | (CAS-no. 34590-94-8) |
| • Neodecanoic acid | (CAS-no. 26896-20-8) |
| • 2-(2-Ethoxyethoxy)ethanol | (CAS-no. 111-90-0) |
| • 2-(2-Butoxyethoxy)ethanol | (CAS-no. 112-34-5) |
| • 2-Methylpentane-2,4-diol | (CAS-no. 107-41-5) |
| • 2-Butoxyethanol | (CAS-no. 111-76-2) |
| • Diethylenglycol | (CAS-no. 111-46-6) |
| • Xylene | (CAS-no. 1330-20-7) |
| • Ethylbenzene | (CAS-no. 100-41-4) |
| • n-butanol | (CAS-no. 71-36-3) |
| • 2-Ethylhexanoic acid | (CAS-no. 149-57-5) |
The first two mentioned substances (2-Methoxymethylethoxy)propanol (dipropylen glycol monoethyl ether) and
neodecanoic acid are scored 0 because of no classification. However, use of QSAR models indicates that the
solvent (2-Methoxymethylethoxy)propanol can produce airway allergy, but not in normal use. Furthermore, one of
the known metabolites of the solvent is considered as genotoxic. QSAR models indicate that the solvent probably
do not have any effects on the external environment /26/.
The next 7 substances are all scored 1 whereas n-butanol is scored 4 because of the classification R41 (Risk of
serious damage to eyes). Finally, the last mentioned substance 2-ethylhexanoic acid are classified as Xn R63
(Possible risk of harm to unborn child) leading to a score 8.
In addition to petroleum distillates and specific substances a number of unspecified substances are present:
- Fatty acid ester (not further specified)
- C3-24 Fatty acid
- Glycolether
- Alcohols, C12-14, ethoxylated
The first three mentioned substances are scored 1 based on the classification given on the MSDS for the actual
drier products. Ethoxylated alcohols, C12-14 is scored 4 because of the classification R41 (Risk of serious
damage to eyes). Furthermore, the ethoxylated alcohols are as the only solvent given an environmental score of 4,
because of the labelling N R50 ("Very toxic to aquatic organisms").
Evaluation of the organic solvents by using the screening method excludes the petroleum distillates, the solvent
2-ethylhexanoic acid, and the ethoxylated alcohols, C12-14.
6.1.3 Evaluation of the drying accelerators
Drying accelerators are used in some of the alternative driers to enhance the drying abilities. The drying accelerators
used are:
| • 2,2'-Bipyridyl | (CAS-no. 366-18-7) |
| • 1,10-phenathroline | (CAS-no. 66-71-7) |
| • Amino complexing agent | (CAS-no. confidential) |
2,2'-Bipyridyl is one of the substances that differs in classification depending on the supplier. 2,2'-Bipyridyl is
scored 1 due to a classification of Xn R20/21/22 (harmful by inhalation, in contact with skin or if swallowed) at one
supplier, but scored 4 due to a classification of T, R25, Xn R21 (toxic if swallowed, harmful in contact with skin) at
another supplier. However, 2,2'-Bipyridyl is at present not on the list of dangerous substances /24/.
1,10-phenathroline is scored 4 because of the classification T, R25 (toxic if swallowed). The amino complexing
agent is confidential and is found in two alternative driers. In both cases the amino complexing agent is scored 1
because of a classification of Xn R20/21/22 (harmful by inhalation, in contact with skin or if swallowed).
Two of the substances have an environmental classification. The solvent 1,10-phenathroline is classified as N,
R50/53 "Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment" resulting
in the highest environmental score – a score 4. 2,2'-Bipyridyl is by one supplier classified as R52/53 (harmful to
aquatic organisms, may cause adverse long term effects in the aquatic environment) resulting in an environmental
score of 1.
Evaluation of the drying accelerators by using the screening method excludes 1,10-phenathroline.
6.1.4 Overall evaluation of the drier products
The screening of the driers shows that if the primary cobalt driers can be substituted with the primary driers
manganese or vanadium, the health profile will improve just taking the metal component into account.
Some of the alternative drier products do contain components (organic solvents or drying accelerators) with
undesirable health and/or environmental effects. In a substitution it is therefore necessary to look upon the entire
product and not just the active metallic compound. However, this is not only valid for the alternative drier products
as also the existing cobalt driers contain solvents with undesirable health effects.
Based on the conducted screening it is recommended to avoid the following drier products:
- The drier products based on cobalt
- The drier product containing 2-ethylhexanoic acid
- The drier products containing petroleum distillates or at least systems with high content of petroleum distillate
- The drier products containing the drying accelerator 1,10-phenathroline
- The drier products containing ethoxylated alcohols, C12-14
The screening also shows that of the secondary driers the aluminium driers should be avoided.
To improve the environment and health profile of air-drying products as much as possible, alternative driers with the
best profile of organic solvents and drying accelerators should be used if technical possible. This means that driers
dissolved in solvents like petroleum distillates and 2-ethylhexanoic acid should be avoided, and that driers
containing 2,2-bipyridyl as drying accelerator should be preferred to those containing 1,10-phenathroline (at
present classification). Of the mentioned undesirable substances the petroleum distillates are used in the largest
amount in the drying compounds. The petroleum distillates content varies between 2.5 and 70% (mostly between
30-50%), whereas 2-ethylhexanoic acid and 1,10-phenathroline are used in smaller concentrations of <2.5% and
2.5-10% respectively. The petroleum distillates are therefore the far most important substances to avoid in driers.
As petroleum distillates today still are present in almost every drier product, both the primary and the secondary, it
is impossible to avoid them completely, but products with a low content of petroleum distillates should of course be
preferred.
Overall, the screening of the drier products shows that a substitution of the primary drier cobalt with manganese or
vanadium will improve the health profile of the drier product. However, in spite of the fact that some alternative
drier products do contain constituents, which have undesirable health and/or environmental effects, it is relevant to
test them in order to learn if they in practise will be alternatives to the existing cobalt driers, as they overall have a
better score by use of the screening method. Only one manganese drier, Mn7, was not included in the testing as
one drier, Mn1, with a better profile was available from the same manufacturer.
Furthermore, it should be mentioned, that some of the constituents in the alternative drier products were not
available until the very end of the project, and therefore some alternatives with a more negative health profile also
has been tested in the project.
6.2 Screening of the anti-skinning agents / antioxidants
The results of the screening are presented in Table 6.2. The screening has been based on information from the suppliers
presented in material safety data sheets, /22/.
For two of the alternative anti-skinning agents confidential information has been received from the supplier to be
able to verify the classification from the MSDS.
Table 6.2
Environmental and health screening of anti-skinning agents.
| Codes | Substance | % | Classification /
Labelling | Health
score | Environ.mental
score |
| Hydroquinone |
Hydroquinone |
|
Xn;R22 Carc3;R40 Xi;R41 R43 Mut3;R68 N;R50 |
8 |
4 |
| MEKO |
Butanone oxime (methyl ethyl ketoxime)1 |
|
Xn R21, 40, 41, 43 |
8 |
|
| Acetone oxime |
Acetone oxime |
10-25 |
Xn R22 R48/20/22 |
4 |
|
| |
(2-methoxymethylethoxy)propanol |
50-100 |
not classified |
0 |
|
| Amino/amido no. 1 |
Amino organic compound2 |
4-20 |
R10, Xn R20/21, R36/37/38 |
1 |
|
| |
Amido organic compound3 |
2-12 |
Xn R20/21/22 |
1 |
|
| |
Glycols (confidential) |
? |
not classified |
0 |
|
| Amino/amido no. 2 |
Amino organic compound2 |
4-20 |
R10, Xn R20/21, R36/37/38 |
1 |
|
| |
Amido organic compound3 |
2-12 |
Xn R20/21/22 |
1 |
|
| |
Naphtha (petroleum), hydrated heavy4 |
65-87 |
Xn R65,66 |
1 (8) |
|
| |
1-butoxy-2-propanol |
<6 |
Xi R36/38 |
1 |
|
| Phenolic no. 1 |
?? |
|
?? |
|
|
| Phenolic no. 2 |
Terpenes and terpenoids, turpentine-oil, a-pinene fraction |
<9.6 |
R10, Xn R20/21/22, R36 |
1 |
- |
| |
Naphtha (petroleum), hydrodesulfurized heavy |
<26.5 |
Xn R10 R48/20, R65/66/67 N R51/53 |
4 (8) |
2 |
| |
p-tert-butylphenol5 |
<20.7 |
Xi R36/37/38 |
1 (0) |
- |
| |
1-methoxy-2-propanol |
<13 |
R10 |
0 |
- |
| |
?? |
?? |
not classified |
0 |
- |
| Vitamin E |
Vitamin E (DL-alpha-tocopherol) |
|
|
|
|
1. Xn;R21 Carc3;R40 Xi;R41 R43 according to /24/.
2. No classification according to Danish EPA (2002). Self-classification
of Xn, R22 according to /27/.
3. No classification according to /24/.
4. Carc2;R45 Xn;R65 according to /24/.
5. At present not classified according to the List of dangerous
substances /24/.
Xi Irritant.
Xn Harmful.
R10 Flammable
R20/22 Harmful by inhalation or if swallowed.
R20/21/22 Harmful by inhalation, in contact with skin or if swallowed.
R21 Harmful in contact with skin.
R22 Harmful if swallowed.
R36 Irritating to eyes.
R36/37/38 Irritating to eyes, the respiratory system and to the
skin.
R38 Irritating to the skin.
R40 Limited evidence of a carcinogenic effect.
R41 Risk of serious damage to the eyes.
R43 May cause sensitisation by skin contact.
R45 May cause cancer.
R48/20 Harmful: danger of serious damage to health by prolonged
exposure through inhalation.
R48/20/22. Danger of serious damage to health by prolonged exposure
via inhalation or if swallowed.
R50 Very toxic to aquatic organisms.
R65 Harmful: may cause lung damage if swallowed
R66 Repeated exposure may cause skin dryness or cracking.
R67 Vapours may cause drowsiness and dizziness.
R68 May cause irreversible damage to health.
6.2.1 Evaluation of the anti-skinning agents
The anti-skinning agents included in the screening are:
- Methyl ethyl ketoxime
- Hydroquinone
and alternative anti-skinning agents:
- Acetone oxime
- Amino/amido organic compounds
- Terpenes and terpenoids, turpentine-oil, a-pinene fraction
- Vitamin E
Methyl ethyl ketoxime (butanone oxime) has been scored 8 due to possible risk of irreversible effects (Carc3;
R40).
The alternative anti-skinning agents are scored 1 except acetone oxime that is scored 4 due to the classification
R48/20/22 (Danger of serious damage to health by prolonged exposure via inhalation or if swallowed).
The amino/amido organic compounds are scored 1 according to the classification Xn R20/21, R36/37/38
("Harmful by inhalation and in contact with skin" and "Irritating to eyes, respiratory system and skin") or the
classification Xn R20/21/22 ("Harmful by inhalation, in contact with skin or if swallowed") on the MSDS.
Confidential information received from the supplier confirms that this score given is the maximum score for the
compounds. Neither the amino nor the amido organic compound is classified according to the list of dangerous
substances, /24/.
Since the testing phase of this project the formulation of the products containing the amino and amido organic
compound has been changed. The tests performed were on the amino/amido organic compound. Now, however,
the amido compound is no longer included in the formulation of the anti-skinning agent, as a better working
combination has been found.
Due to the present scores the amino/amido organic compound as well as the terpenes etc. can be recommended in
preference to hydroquinone, methyl ethyl ketoxime and acetone oxime.
6.2.2 Evaluation of the organic solvents
The organic solvents can be divided in two groups: petroleum distillates and specific substances. The petroleum
distillates are:
| • Naphtha (petroleum) – hydrated heavy | (CAS-no. 64742-48-9) |
| • Naphtha (petroleum) – hydrodesulfurized heavy | (CAS-no. 64742-82-1) |
The petroleum distillates are scored 1 and 4 based on classification as Xn R65/66 (Harmful: may cause lung
damage if swallowed and Repeated exposure may cause skin dryness or cracking) and Xn R48/20 (Danger of
serious damage to health by prolonged exposure by inhalation). According to the "European list of dangerous
substances" /24/ these petroleum distillates are classified as carc2; R45 Xn; R65 leading to a score 8.
The specific substances are:
| • (2-Methoxymethylethoxy)propanol | (CAS-no. 34590-94-8) |
| • 1-Butoxy-2-propanol | (CAS-no. 5131-66-8) |
| • 1-Methoxy-2-propanol | (CAS-no. 107-98-2) |
| • p-tert-Butylphenol | (CAS-no. 98-54-4) |
These substances are scored 1 due to classification as Xi R36/37/38 (Irritating to eyes, the respiratory system and
to the skin) except (2-methoxymethylethoxy)propanol and 1-methoxy-2-propanol which are scored 0. However,
p-tert-Butylphenol is at present not classified according to the list of dangerous substances /24/.
(2-Methoxymethylethoxy)propanol (dipropylen glycol monoethyl ether) is scored 0 because of no classification.
However, use of QSAR models indicates that this solvent can produce airway allergy, but not in normal use.
Furthermore, one of the known metabolites of the substance is considered as genotoxic. The QSAR models
indicate that the substance probably does not have any effects on the external environment, /26/.
Furthermore unspecified glycols are present in one of the anti-skinning agent systems. Based on the confidential
information received from the producer none of the glycols has to be classified and is therefore scored 0.
6.2.3 Overall evaluation of the anti-skinning agent systems
The screening of the anti-skinning agents shows that when only considering the active ingredients in the alternatives,
the health profile of air-drying products can be improved by substituting methyl ethyl ketoxime and hydroquinone
with the alternatives.
Some of the alternative anti-skinning agents contain organic solvents with undesirable health and/or environmental
effects, and the total health profile of the product depends of course also on the organic solvents used in the
product. However, even so, the profile is better than that of methyl ethyl ketoxime and hydroquinone.
Based on the conducted screening the following anti-skinning agent systems are recommended to be avoided:
- The anti-skinning agent system based on hydroquinone
- The anti-skinning agent system based on methyl ethyl ketoxime
- The anti-skinning agent system based on acetone oxime
- The anti-skinning agent system containing petroleum distillates or at least systems with high content of petroleum
distillate (e.g. the amino/amido compound dissolved in petroleum distillates)
The two anti-skinning agent systems based amino/amido organic compounds have the same classification as far as
regarding the anti-skinning agent. However, the amino/amido compounds dissolved in glycol are preferred in
preference to the system dissolved in petroleum distillate.
It should be mentioned, that some of the constituents in the alternative anti-skinning agents were not available until
the very end of the project, for which reason some alternatives with a more negative health profile also have been
tested in the project. Actually, for one anti-skinning agent no identity of the constituents was available for the
project. The anti-skinning agent is, however, tested anyway as the total number of alternatives is limited.
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