Polymer in Adcote 522
File No: NA/926
April 2001
NATIONAL INDUSTRIAL CHEMICALS NOTIFICATION
AND ASSESSMENT SCHEME
FULL PUBLIC REPORT
Polymer in Adcote 522
This Assessment has been compiled in accordance with the provisions of the Industrial Chemicals
(Notification and Assessment) Act 1989 (the Act) and Regulations. This legislation is an Act of the
Commonwealth of Australia. The National Industrial Chemicals Notification and Assessment
Scheme (NICNAS) is administered by the National Occupational Health and Safety Commission
which also conducts the occupational health & safety assessment. The assessment of environmental
hazard is conducted by the Department of the Environment and the assessment of public health is
conducted by the Department of Health and Aged Care.
For the purposes of subsection 78(1) of the Act, copies of this full public report may be inspected by
the public at the Library, National Occupational Health and Safety Commission, 92-94 Parramatta
Road, Camperdown NSW 2050, between the following hours:
Monday - Wednesday 8.30 am - 5.00 pm
Thursday 8.30 am - 8.00 pm
Friday 8.30 am - 5.00 pm
Copies of this full public report may also be requested, free of charge, by contacting the
Administration Coordinator on the fax number below.
For enquiries please contact the Administration Coordinator at:
Street Address: 92 -94 Parramatta Rd CAMPERDOWN NSW 2050, AUSTRALIA
Postal Address: GPO Box 58, SYDNEY NSW 2001, AUSTRALIA
Telephone: (61) (02) 9577 9514 FAX (61) (02) 9577 9465
Director
Chemicals Notification and Assessment
TABLE OF CONTENTS
FULL PUBLIC REPORT...........................................................................................................3
1. APPLICANT ..................................................................................................................3
2. IDENTITY OF THE CHEMICAL.................................................................................3
3. PHYSICAL AND CHEMICAL PROPERTIES.............................................................3
3.1 Comments on Physico-Chemical Properties ..........................................................4
4. PURITY OF THE CHEMICAL.....................................................................................4
5. USE, VOLUME AND FORMULATION......................................................................5
6. OCCUPATIONAL EXPOSURE ...................................................................................5
7. PUBLIC EXPOSURE ....................................................................................................6
8. ENVIRONMENTAL EXPOSURE................................................................................6
8.1 Release ...................................................................................................................6
8.2 Fate .........................................................................................................................7
9. EVALUATION OF TOXICOLOGICAL DATA...........................................................8
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS ...............................................8
11. ASSESSMENT OF ENVIRONMENTAL HAZARD ...............................................8
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS ...................................................................................................................8
13. RECOMMENDATIONS .........................................................................................10
14. MATERIAL SAFETY DATA SHEET....................................................................10
15. REQUIREMENTS FOR SECONDARY NOTIFICATION ....................................11
16. REFERENCES.........................................................................................................11
NA/926
FULL PUBLIC REPORT
Polymer in Adcote 522
1. APPLICANT
Rohm and Haas Australia Pty Ltd of Floor, 969 Burke Road Camberwell VIC 3124 (ACN
004 513 188) have submitted a limited notification statement in support of their application
for an assessment certificate for Polymer in Adcote 522.
2. IDENTITY OF THE CHEMICAL
The chemical name, CAS number, molecular and structural formulae, molecular weight,
spectral data, and details of the polymer composition and import volume have been exempted
from publication in the Full Public Report and the Summary Report.
Adcote 522 (59 % w/w notified polymer).
Marketing Name:
3. PHYSICAL AND CHEMICAL PROPERTIES
The following physico-chemical data are from Adcote 522 polymer solution in ethyl acetate,
unless otherwise stated.
amber liquid
Appearance at 20癈 & 101.3 kPa:
77癈 (ethyl acetate)
Boiling Point:
1.06
Specific Gravity:
the notified polymer is not volatile
Vapour Pressure:
6 mg/L
Water Solubility:
Partition Co-efficient
not determined (see comments below)
(n-octanol/water):
the polymer linkages may undergo hydrolysis under
Hydrolysis as a Function of pH:
extreme temperature and pH
not determined (see comments below)
Adsorption/Desorption:
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no dissociable groups are present
Dissociation Constant:
not applicable as the notified polymer is only used in
Particle Size:
solution
4癈 (closed cup)
Flash Point:
Upper Explosive Limit = 11.5 %
Flammability Limits:
Lower Explosive Limit = 2.2 % (ethyl acetate)
426癈 (ethyl acetate)
Autoignition Temperature:
not explosive
Explosive Properties:
the notified polymer contains isocyanate groups which
Reactivity/Stability:
will react with acids, bases, amines, alcohols and water
3.1 Comments on Physico-Chemical Properties
The water solubility was determined using a modified flask method (Pazdra 2001). The
notified polymer (~0.5 g) was weighed into double filtered deionised water (50 mL, Millipore
water filtered through a 0.2 祄 filter), the solution was shaken for 24 h and equilibrated for
another 24 h. After equilibration, the sample was filtered and an aliquot was dried at 105oC.
The water solubility test was completed in triplicate and the average value was reported.
The terminal isocyanate groups are expected to hydrolyse on contact with water. The notified
polymer also contains linkages that may undergo hydrolysis, but this is unlikely in the
environmental pH range 4-9.
The partition coefficient has not been determined in consideration of its low water solubility
and likely hydrophobic nature, which indicates that partitioning into the n-octanol phase is
likely.
The adsorption/desorption was not determined, but the notifier has indicated that the polymer
is expected to be immobile in soil due to its composition, low water solubility and high
molecular weight.
The polymer is expected to remain stable under ambient conditions, except for reactions of
the terminal isocyanate groups. The notified polymer is designed to cross-link with other
polymers via these isocyanate groups.
4. PURITY OF THE CHEMICAL
high
Degree of Purity:
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Additives/Adjuvants:
Chemical name: ethyl acetate
CAS No.: 141-78-6
Weight percentage: approximately 40 %
Toxic properties: vapours are narcotic and irritate eyes and respiratory
tract (American Conference of Government Industrial
Hygienists, 1998)
NOHSC exposure standard 200 ppm TWA (NOHSC,
1995)
Chemical name: 1,1'-methylenebis[4-isocyanatobenzene]
Synonyms: 4,4'-MDI
CAS No.: 101-68-8
Weight percentage: <5%
Toxic properties: R20 Harmful by inhalation
R36/37/38 Irritating to eyes, respiratory system and
skin
R42 May cause sensitisation by inhalation (NOHSC,
1999a)
NOHSC exposure standard 0.02 mg/m3 TWA as
isocyanate with sensitiser notation (NOHSC, 1995)
5. USE, VOLUME AND FORMULATION
The notified polymer is used as one component of a two pack laminating adhesive for plastic
and/or aluminium films used to package dry food and in general packaging.
The notified polymer will not be manufactured in Australia, but will be imported as a
component in the product, Adcote 522. The estimated import quantity of the notified polymer
is less than 10 tonnes per annum during the first five years.
Adcote 522 is an ethyl acetate solution containing 59 % notified polymer. This will be
blended prior to use to produce an adhesive which is predominantly Adcote 522. Adcote 522
will be imported in 200 L steel drums.
6. OCCUPATIONAL EXPOSURE
Transport and storage
The notifier estimated that 5 waterside workers and 5-10 transport drivers and warehouse
workers will be involved in the transport and storage of the product containing the notified
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polymer. These workers could be exposed to the notified chemical only in the event of an
accident where the packaging is breached.
Laminating machine operator
At the laminating site, Adcote 522 is transferred by gravity through an attached tap from
200 L drums into a mixing vessel of 40-60 L capacity. It will be mixed with another
component of the adhesive system in the mixing vessel mechanically for 15 minutes. The
blended adhesive containing < 50 % notified polymer is pumped mechanically from the
mixing vessel to a holding vessel (about 20 L) of the laminating machine and further pumped
to an adhesive tray. The blended adhesive is applied by the gravure coating process where two
polymers and/or aluminium film are laminated together with the adhesive between the films.
Following completion of a run, unused adhesive in the laminating machine tray or reservoir is
transferred to a waste drum manually. The adhesive residues on the machinery are washed off
manually using rags and ethyl acetate.
There will be 2-4 laminating machine operators who may be exposed to the product
containing the notified polymer and the blended adhesive. The maximum potential exposure
for laminating machine operators is estimated to be 6-8 hours per day, 25 days per year. The
main routes for occupational exposure to the polymer will occur through skin and eye contact.
Contact with the notified polymer is possible during blending and transfer of adhesives, and
during cleaning. Laminating machinery operators wear safety glasses, impervious gloves,
overalls and safety boots during blending of the adhesive, transfer of the adhesive to
laminating machines, and cleaning of the machines. Blending vessels are situated in a bunded
area with local exhaust ventilation, while laminating machinery is either fitted with exhaust
ventilation ducts above the adhesive tray or in a wall or ceiling adjacent to the machinery.
There is little potential for exposure to the notified polymer after it has been incorporated in
packaging materials, because it will be sandwiched between two impervious layers and also
crosslinked and not separately available for exposure.
7. PUBLIC EXPOSURE
The notified polymer is not available for sale to the public and will be used as an ingredient in
laminating adhesive products for use in food and other packaging applications. The potential
for public exposure to the notified polymer during transport, reformulation or disposal is
likely to be low. There is little potential for exposure of the public to the notified polymer in
packaging materials, because it will be sandwiched between two impervious layers and also
crosslinked and not separately available for exposure.
8. ENVIRONMENTAL EXPOSURE
8.1 Release
The notifier has estimated the following amounts of the polymer solutions may be lost from
the sources specified as a result of the formation and use of the adhesive:
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15 kg per annum
Spills:
15 kg per annum
Residues in the import containers:
10.5 kg per annum
Equipment cleaning:
105 kg per annum
Unused blend:
The total amount of notified polymer that may be wasted during its use is likely to be less
than 150 kg/year when 5 tonnes of Adcote 522 are imported.
It is anticipated that spills of the polymer solution and blended polymer adhesive will be
contained within the plant through the bunding systems in place. As the polymer solution will
be used in small batch quantities, it is expected that any spills will be small in volume. Spills
will be collected using absorbent material and removed by a licensed industrial waste
contractor to a licensed waste landfill site.
Machinery will be manually cleaned with rags and solvent and waste from this process will be
disposed of to landfill by licensed hazardous waste contractors.
It is expected that import drums containing residual polymer solution will be used to collect
waste solvent and unused blended adhesive, and when finished with, collected by a licensed
hazardous waste contractor. The liquid contents will be incinerated and the drums with any
residual solid will be disposed of to a licensed waste landfill site.
The remainder of the notified polymer will be incorporated into packaging materials.
8.2 Fate
Spills of polymer solution or blended laminating adhesive containing the notified polymer
will be collected on absorbent material and disposed of in landfill. Waste generated from
cleaning machinery with rags and solvent will also be disposed of in landfill. In landfill, the
polymer is unlikely to separate from the absorbent material; any free polymer would associate
with the soil matrix and not leach into the aquatic compartment due to the low water
solubility of the notified polymer.
Residual polymer solution and unused blended adhesive will be incinerated by licensed
hazardous waste contractors and the empty import drums with any remaining residual solid
material will be disposed of in landfill. Incineration would be expected to produce water
vapour and oxides of nitrogen and carbon. In landfill, the polymer would not be expected to
escape from the drums; any free polymer would associate with the soil matrix and not leach
into the aquatic compartment due to its low water solubility. The majority of the notified
polymer will follow the fate of the packaging in which it is incorporated. It is expected that
the majority of packaging will be disposed of in domestic landfill. Upon eventual degradation
of the packaging films between which the polymer is sandwiched, it is expected that the
polymer would become part of the soil matrix and not be leached from the soil due to its low
water solubility.
The polymer is not expected to cross biological membranes, due to its high molecular weight,
and should not bioaccumulate (Connell, 1990).
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9. EVALUATION OF TOXICOLOGICAL DATA
No toxicology data were submitted. The notified polymer contains reactive isocyanate
functional groups which can cause local irritant and allergic reactions (NOHSC, 1990).
10. ASSESSMENT OF ENVIRONMENTAL EFFECTS
No ecotoxicity data were submitted.
11. ASSESSMENT OF ENVIRONMENTAL HAZARD
Release of the notified polymer to the aquatic compartment from spills during formulation is
not expected, as processing plants will be bunded and any spills will be collected on
absorbent material and disposed of in landfill. Waste polymer generated from cleaning
equipment and discarded packaging will be disposed of in landfill. In landfill, the polymer is
unlikely to be mobile in the soil environment and is expected to very slowly degrade to gases
such as carbon dioxide through abiotic and biotic processes. The environmental hazard of the
notified polymer in landfill is expected to be low.
Incineration by licensed hazardous waste contractors of the notified polymer in waste from
drum residues and unused blended adhesive would be expected to produce water vapour and
oxides of carbon and nitrogen.
The high molecular weight of the notified polymer should prevent bioaccumulation. The
overall environmental hazard is therefore expected to be low.
12. ASSESSMENT OF PUBLIC AND OCCUPATIONAL HEALTH AND SAFETY
EFFECTS
No toxicological information has been provided for the notified polymer. Any toxicological
studies on the notified polymer would be influenced by the effects of the added 1,1'-
methylenebis[4-isocyanatobenzene] (4,4'-MDI) and therefore it is not appropriate to classify
the notified polymer against the NOHSC Approved Criteria for Classifying Hazardous
Substances (NOHSC, 1999b). Since the notified polymer has high NAMW, absorption across
biological membranes and resultant systemic toxicity would be restricted. However, it
contains reactive isocyanate functional groups which can cause local irritant and allergic
reactions (NOHSC, 1990). The product Adcote 522 contains an excess of 4,4'-MDI, which is
on the NOHSC List of Designated Hazardous Substances (NOHSC, 1999a) as a respiratory
sensitiser and skin, eye and respiratory irritant. The product Adcote 522 is therefore classified
as a hazardous substance, and given risk phrases: R36/37/38 - irritating to eyes, respiratory
system and skin; R42 - may cause sensitisation by inhalation. The concentration of 4,4'-MDI
is below the cutoff for application of the risk phrase R20.
The MSDS for Adcote 522 lists a large number of potential health effects, relating chiefly to
the hazards associated with the isocyanate groups of the notified polymer and the excess 4,4'-
MDI, and also to the inhalation hazard of the solvent ethyl acetate.
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Adcote 522 is a Class 3 Dangerous Good (flammable liquid) due to the solvent content.
Occupational health and safety
There is little potential for significant health risk to the notified polymer in the transport and
storage of the product containing this polymer.
Potential exposure to the polymer in Adcote 522 will be during the blending and transfer of
adhesives, particularly manual transfer, and when cleaning equipment. Exposure to the
notified polymer via inhalation is expected to be minimal due to its low volatility. Inhalation
exposure to the product should however be stringently controlled due to the hazard associated
with the excess 4,4'-MDI. Exposure to the notified polymer is most likely to be by skin
contact. However, laminating machine operators are instructed to wear safety glasses,
impervious gloves (nitrile or butyl rubber), overalls and safety boots when handling Adcote
522 and the blended adhesives. In addition, blending vessels are situated in a bunded area
with local exhaust ventilation. Laminating machinery is either fitted with exhaust ventilation
ducts above the adhesive tray, or in a wall or ceiling adjacent to the machinery.
Due to the health effects of 4,4'-MDI the health risk to laminating operators is of concern, as
exposure and therefore irritation of the skin and eyes, and sensitisation may occur during
transfer and cleaning operations. Laminating machine operators must wear safety glasses,
impervious gloves, overalls and safety boots when handling Adcote 522 and the blended
adhesives and respiratory protection must be worn if there is a risk of exposure to 4,4'-MDI.
4,4'-MDI has a NOHSC exposure standard of 0.02 mg/m3 TWA (as isocyanate, equivalent to
0.12 mg/m3 4,4'-MDI) and 0.07 mg/m3 STEL, with a `sensitiser' notation (NOHSC, 1995).
However, it is noted that the ACGIH TLV for MDI is 0.051 mg/m3 TWA (American
Conference of Government Industrial Hygienists, 1998). Precautions to prevent exposure to
isocyanates must be taken by all personnel, especially those who have had prior contact or
suffer from any form of compromised respiratory function (NOHSC 1990). Isocyanates are on
Schedule 3 in NOHSC Model Regulations for the Control of Workplace Hazardous
Substances - substances for which health surveillance is required (NOHSC 1994a).
The notified polymer becomes unavailable for absorption once it is incorporated in the
laminated material. The health risk for workers in the packaging industry, and in distribution
and retailing, is considered to be negligible.
Public health
It is expected that public exposure to the notified polymer in its liquid state will be limited,
except in the rare event of an accidental spill. The notified polymer used in an adhesive in
food and other packaging will be encapsulated within an inert, very high molecular weight
film matrix, rendering the notified polymer biologically unavailable. Public contact with the
notified polymer in packaging is further limited as the adhesive containing the notified
polymer is sandwiched between two layers of polymer and/or aluminium film, restricting any
dermal contact. Consequently the public hazard from exposure to the notified polymer
through all phases of its life cycle, is considered to be low.
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13. RECOMMENDATIONS
Due to the presence of excess 4,4'-MDI, which is a Schedule 3 sensitiser, health surveillance
must be conducted for workers potentially exposed to Adcote 522 or mixtures containing the
adhesive.
To minimise occupational exposure to Polymer in Adcote 522 the following guidelines and
precautions should be observed:
Local exhaust ventilation should be used in all areas where Adcote 522 and mixtures
?br>
containing Adcote 522 are handled;
Personal and area atmospheric monitoring should be conducted for workers
?br>
potentially exposed to MDI in excess of the NOHSC exposure standard of 0.12 mg/m3
TWA. Employers should ensure that other relevant NOHSC exposure standards are
not exceeded in the workplace;
Workers must wear overalls, face/eye protection and butyl rubber or nitrile gloves
?br>
when handling Adcote 522 or mixtures containing the adhesive. Respiratory
protection must be worn if exposure to MDI is possible;
Spillage of the notified chemical should be avoided. Spillages should be cleaned up
?br>
promptly with absorbents which should be put into containers for disposal;
A copy of the MSDS should be easily accessible to employees.
?br>
If products containing the notified polymer are hazardous to health in accordance with the
NOHSC Approved Criteria for Classifying Hazardous Substances (NOHSC, 1999b),
workplace practices and control procedures consistent with State and Territory hazardous
substances regulations must be in operation.
Guidance in selection of goggles may be obtained from Australian Standard (AS) 1336
(Standards Australia, 1994) and Australian/New Zealand Standard (AS/NZS) 1337
(Standards Australia/Standards New Zealand, 1992); for industrial clothing, guidance may be
found in AS 2919 (Standards Australia, 1987) and AS 3765.2 (Standards Australia, 1990); for
impermeable gloves or mittens, in AS 2161 (Standards Australia/ Standards New Zealand,
1998); for occupational footwear, in AS/NZS 2210 (Standards Australia/ Standards New
Zealand, 1994a); for respirators, in AS/NZS 1715 (Standards Australia/ Standards New
Zealand, 1994b) and AS/NZS 1716 (Standards Australia/ Standards New Zealand, 1994c) and
other internationally acceptable standards.
14. MATERIAL SAFETY DATA SHEET
The MSDS for the notified polymer was provided in a format consistent with the National
Code of Practice for the Preparation of Material Safety Data Sheets (NOHSC, 1994b).
This MSDS was provided by the applicant as part of the notification statement. It is
reproduced here as a matter of public record. The accuracy of this information remains the
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responsibility of the applicant.
15. REQUIREMENTS FOR SECONDARY NOTIFICATION
Under the Act, the director must be informed if any of the circumstances stipulated under
subsection 64(2) of the Act arise, and secondary notification of the notified chemical may be
required. No other specific conditions are prescribed.
16. REFERENCES
American Conference of Government Industrial Hygienists (1998). TLVs and Other
Occupational Exposure Values.
Connell D. W. (1990) General characteristics of organic compounds which exhibit
bioaccumulation. In Connell D. W., (Ed) Bioaccumulation of Xenobiotic Compounds. CRC
Press, Boca Raton, USA.
National Occupational Health and Safety Commission (1990) Isocyanates, Australian
Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1994a) National Model Regulations
for the Control of Workplace Hazardous Substances [NOHSC: 1005 (1994)]. Australian
Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1994b) National Code of Practice for
the Preparation of Material Safety Data Sheets [NOHSC:2011(1994)]. Australian
Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1995) Adopted National Exposure
Standards for Atmospheric Contaminants in the Occupational Environment,
[NOHSC:1003(1995)]. In: Exposure Standards for Atmospheric Contaminants in the
Occupational Environment: Guidance Note and National Exposure Standards. Australian
Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1999a) List of Designated Hazardous
Substances [NOHSC:10005(1999)]. Australian Government Publishing Service, Canberra.
National Occupational Health and Safety Commission (1999b) Approved Criteria for
Classifying Hazardous Substances [NOHSC:1008(1999)]. Australian Government Publishing
Service, Canberra.
Pazdra, K (2001): Sample Report; Submission No. 200001157: Project Number 981109-
60922041: Woodstock Analytical Services (unpublished report).
Standards Australia (1990) Australian Standard 3765.2-1990, Clothing for Protection against
Hazardous Chemicals Part 2 Limited protection against specific chemicals. Standards
Association of Australia.
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Standards Australia (1994) Australian Standard 1336-1994, Eye protection in the Industrial
Environment. Standards Association of Australia.
Standards Australia/Standards New Zealand (1992) Australian/New Zealand Standard 1337-
1992, Eye Protectors for Industrial Applications. Standards Association of Australia/
Standards Association of New Zealand.
Standards Australia/Standards New Zealand (1994) Australian/New Zealand Standard 2210-
1994, Occupational Protective Footwear. Standards Association of Australia/Standards
Association of New Zealand.
Standards Australia/Standards New Zealand (1998) Australian/New Zealand Standard
2161.2-1998, Occupational protective gloves, Part 2: General requirements. Standards
Association of Australia/Standards Association of New Zealand.
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