SSPC-TU 8

September 20, 2019

SSPC: The Society for Protective Coatings

TECHNOLOGY UPDATE No. 8

Safe Use and Handling of Isocyanate-Containing Polyurethane and
Polyurea Coatings for Industrial Maintenance Applications

1. Background Information it may contain isocyanates. However, some polyurethane

coatings are fully reacted. That is, all of the NCO groups
Polyurethane is the name used for the material formed are chemically changed to polyurethane groups prior to
by the chemical reaction of a hydroxyl or —OH-containing packaging for shipment. Examples of such coatings would be
polyol, and a polyisocyanate hardener that contains multiple most one-package, clear, polyurethane wood varnishes sold
isocyanate (NCO) groups. Polyisocyanate hardeners are at retail home improvement stores. Polyurethane coatings
formulated into several different types of coatings systems, used for industrial maintenance painting typically consist of
including one-component moisture cure urethanes, a “paint” or “resin” component that needs to be mixed with a
two component polyurethanes, and two component “hardener” or “catalyst” component prior to application. These
polyurea coatings. In a one-component or moisture-cure coating systems will contain unreacted isocyanate groups at
polyurethane, the polyisocyanate reacts with water in the the time of application to the substrate. The hardener is the
atmosphere to fully cure. In a two-component system, the part that typically contains the unreacted isocyanate. The
polyisocyanate reacts with a resin having reactive hydrogen isocyanate groups begin to react immediately upon contact
groups, which can include acrylic, polyester, polyether, vinyl, with the components in the coating system to form the
castor oil, amine, etc. The polyurethane or polyurea coating polyurethane film. It is the unreacted isocyanate groups that
resulting from these chemical reactions is the foundation of require workers to wear appropriate PPE. Once the coating
performance properties, including durability, corrosion and system has fully cured, the isocyanate groups are no longer
chemical resistance, and color and gloss retention. Aliphatic present in the coating film.
polyurethane and polyurea coatings are resistant to the sun’s Because the two parts of the coating system are
ultraviolet (UV) radiation, increasing their color and gloss packaged separately, the supplier often provides two different
stability while maintaining a functional non-chalking surface. SDSs, one for the “paint” side and one for the “catalyst”
Aromatic polyurethane and polyureas provide chemical, side. The “catalyst” or “hardener” will contain primarily
abrasion, and corrosion-resistance properties, but are not as polyisocyanate and a small percentage (less than 0.5%) of
UV-resistant as their aliphatic counterparts. diisocyanate monomer. Section 3 of the SDS (Composition/
High-performance polyurethane coatings can contain Information on Ingredients) should identify the specific type
a variety of components including solvents, pigments, of isocyanate (diisocyanate monomer/polyisocyanate) along
additives, and other resins along with the polyisocyanate with its percent composition in the product. When reviewing
resins. These ingredients can present certain potential health the SDS, it is important to understand specific words, terms
hazards if one is exposed to a sufficiently high dosage during and acronyms common to polyurethane coating systems
the coating process. This is why the applicator and any other such as:
workers in the application area must be properly protected.
All coatings, including those containing polyisocyanates, can • Isocyanates: organic compounds consisting of
be applied safely when safe work practices are followed and one nitrogen, one carbon and one oxygen atom
proper personal protective equipment (PPE) is worn. attached by a double bond and illustrated by the
This technology update focuses on U.S. safety chemical formula NCO. Isocyanates are a family
and health regulations on the isocyanates in industrial of highly reactive chemicals that are widely used
maintenance coatings. Regulations in other countries may to make polyurethane coatings as well as flexible
vary. foam and rigid foam insulation.
• Diisocyanate (monomers): these are isocyanates
2. Worker Exposure that contain two NCO functional groups and
because of their functionality are widely used in
2.1 RECOGNITION OF HAZARD: In order to determine the polyurethane industry; common examples
whether a particular coating contains isocyanates, one should of monomeric isocyanates used in coating
refer to the container label and the safety data sheet (SDS). systems include Aliphatic Diisocyanates such
If a coating is referred to as a polyurethane or a polyurea, as 1,6-hexamethylene diisocyanate (HDI),

This standard, developed by the SSPC C.5.1 Committee on Worker Safety, was first
issued in November 2004 and revised in September 2019.

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September 20, 2019

isophorone diisocyanate (IPDI), and methylene the label or SDS, it is advisable to contact a product safety
bis(4-cyclohexylisocyanate (HMDI); and Aromatic specialist from the coating supplier for additonal information.
Diisocyanates such as 2,4 and 2,6-toluene Most SDSs provide a department name and phone number
diisocyanate (TDI) and 4,4-diphenylmethane for those individuals seeking additional health and safety
diisocyanate (MDI). The monomeric diisocyanates information.
have occupational exposure limits: (Occupational
Safety and Health Administration (OSHA)(1) 2.2 EVALUATION: Once it has been established
Permissible Exposure Limit [PEL]; American that a particular coating system contains a diisocyanate
Conference of Governmental Industrial Hygienists or polyisocyanate, the workplace atmosphere should be
(ACGIH)(2) Threshold Limit Value [TLV]; U.S. characterized to determine the airborne concentration. Air
Centers for Disease Control, National Institute sampling is the preferred method of evaluating the airborne
for Occupational Safety and Health (NIOSH)(3) concentration in the work environment. Table 1 is a summary
Recommended Exposure Limit [REL]); and are of the 2017 OSHA, ACGIH and NIOSH occupational
generally the focus of most exposure-monitoring exposure limits (OELs) for commonly used diisocyanate
(air-sampling) studies. Therefore, the percent monomers and polyisocyanates.
content of the diisocyanate monomer within the Federal OSHA permits states to develop and operate
catalyst or hardener and the isocyanate-to-resin their own job safety and health enforcement programs,
ratio are important characteristics associated with referred to as an OSHA-approved State Plan. States with
the coating system in assessing the potential for approved plans include AK, AZ, CA, CT, HI, IL, IN, IA,
worker exposure. KY, MD, MI, MN, NJ, NM, NV, NY, NC, OR, SC, TN, UT,
• Polyisocyanates: compounds that contain three VA, VT, WA, and WY. States must have PELs equal to or
or more NCO functional groups. To reduce the lower than Federal OSHA limits. It is important to check the
vapor hazards associated with lower molecular diisocyanate PELs when applying coatings in a region with
weight diisocyanate monomers (i.e., 1,6-HDI), an OSHA-approved State Plan.
polyisocyanate forms of these diisocyanates were For all diisocyanate monomers except TDI, the 8-hour
developed and have significantly reduced the Time Weighted Average (TWA) airborne concentration
monomer content in many product formulations. exposure limit or guideline is 5 parts per billion parts of air
Polyisocyanate compounds are derived from (5 ppb). In February 2016, the 8-hr TLV-TWA for TDI was
diisocyanate monomers either by directly linking lowered to 1 ppb and the 15-minute Short Term Exposure
the specific diisocyanate monomer within the Limit (STEL) to 5 ppb.1 With regard to HDI polyisocyanates,
product to form larger compounds referred to as a past health studies suggest that they are less potent in
homopolymer or by reacting the monomer with a causing allergy and asthma than 1,6-HDI monomer.2
polyol (polyalcohol) or amines to form a prepolymer. Therefore, HDI polyisocyanates have a higher exposure
Polyisocyanates or prepolymer compounds are limit value. The MGL (and Oregon OSHA PEL) for HDI
characterized by high molecular weight and a low polyisocyanates is 0.5 milligrams per cubic meter (mg/m3)
evaporation rate at ambient temperatures. NCO as an 8-hour TWA and 1.0 mg/m3 as a 15-minute STEL3,(4).
groups associated with a polyisocyanate can only The units of measurement for HDI polyisocyanates are
be an inhalation hazard if mechanically aerosolized expressed in a mass-to-volume ratio (mg/m3) and not in a
(e.g., sprayed) or heated in the work environment volume-to-volume ratio (ppb) because HDI polyisocyanates
to temperatures well above 100 ºF (38ºC). typically do not exist as a vapor in the work environment.
Polyisocyanate compounds are not assigned an HDI polyisocyanates can only be measured within an
occupational exposure limit (OEL) by the ACGIH, aerosol (i.e., coating mist) during a spray application. SDSs
federal OSHA or NIOSH. Some manufacturers often list the applicable airborne concentration guidelines or
and state OSHA agencies have published OELs standards in Section 8 (Exposure Controls). Another source
for polyisocyanates that are typically established for diisocyanate monomer exposure standards is the ACGIH
at a higher value than OELS for the diisocyanate Guide to Occupational Exposure Values.1
monomers. Monitoring of the workplace air to determine
concentrations of isocyanates is a key step in determining
If the applicator suspects that a particular coating the effectiveness of engineering controls as well as in
contains isocyanates but cannot find any mention of them on determining the type of respiratory protection and other
personal protective equipment which may be required.
(1)
U.S. Dept. of Labor, Occupational Safety and Health Administration (OSHA), Office of
Public Affairs - Room N3647, 200 Constitution Ave., Washington DC 20210, or contact Specific sampling and analytical techniques have been
via internet at http://www.osha.gov/readingroom/html
developed to determine these levels.
(2)
American Conference of Governmental Industrial Hygienists (ACGIH), 1330 Kemper
Meadow Drive, Suite 600, Cincinnati OH 45240, <http://www.acgih.org>
(3)
U.S. Centers for Disease Control, National Institute for Occupational Safety and Health
(NIOSH), 200 Independence Avenue, SW, Washington, DC 20201,<https://www.cdc.
(4)
Oregon Department of Consumer and Business Services, Oregon OccupationalSafety
gov/niosh/>, and Health Division, 350 Winter St. NE, Room 430 Salem, OR. 97309-0405. Phone
int+1-503-947-7448.

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TABLE 1
SUMMARY OF 2017 OSHA, ACGIH AND NIOSH
OCCUPATIONAL EXPOSURE LIMITS FOR COMMONLY USED DIISOCYANATE
MONOMERS AND POLYISOCYANATES

Chemical CAS # ACGIH TLV OSHA PEL NIOSH REL

5 ppb (34 µg/m3)
1,6-HDI 5 ppb (34 µg/m3) (8-hr TWA)
822-06-0 Not Established
Diisocyanate (8-hr TWA) 20 ppb (140 µg/m3)
Ceiling Limit
HDI Polyisocyanate
(1,6-HDI
28182-81-2 Not Established Not Established Not Established
homopolymer)
1 ppb (7 µg/m3)
(8-hr TWA) Lowest Feasible
2,4 and 2,6-TDI 584-84-9; 20 ppb (140 µg/m3)
5 ppb (36 µg/m3) Concentration
Diisocyanate 91-08-7 Ceiling Limit
(15-min STEL)
5 ppb (50 µg/m3)
4,4’-MDI 5 ppb (50 µg/m3) 20 ppb (200 µg/m3)
101-68-8 (8-hr TWA)
Diisocyanate (8-hr TWA) Ceiling Limit
20 ppb (200 µg/m3)
2-4’-MDI
5873-54-1 Not Established Not Established Not Established
Diisocyanate
2-2”-MDI
2536-05-2 Not Established Not Established Not Established
Diisocyanate
Polymeric MDI 9016-87-9 Not Established Not Established Not Established
5 ppb (45 µg/m3)
IPDI 5 ppb (45 µg/m ) 3
(8-hr TWA)
4098-71-9 Not Established
Diisocyanate (8-hr TWA) 20 ppb (180 µg/m3)
(15-min STEL)
HMDI 5 ppb (54 µg/m3) 10 ppb (110 µg/m3)
5124-30-1 Not Established
Diisocyanate (8-hr TWA) Ceiling Limit

Note: ppb is read parts per billion; µg/m3 is read micrograms per cubic meter.

At present, a number of sampling and analytical • OSHA Method 47 (MDI)

methods are available for monitoring isocyanates in the • NIOSH Method 5521 (TDI, MDI, HDI, IPDI, HMDI
work environment. Care must be taken to ensure that • ISO 17734 Asset (EZ4™-NCO Dry Sampler for
the appropriate method is chosen before sampling is TDI, HDI, IPDI,and MDI
performed in the work area. Isocyanates are highly reactive
compounds , therefore methods used for monitoring airborne All of the methods listed above are effective when
concentrations must be capable of trapping and derivatizing the isocyanate exists as a vapor in the work environment.
the isocyanate (NCO group) to a stable urea derivative as Isocyanate manufacturers have made minor modifications to
they are being sampled. The most common isocyanate OSHA Methods 42 and 47. These modifications were made
air-sampling methods are published by OSHA and NIOSH. to improve the collection efficiency of isocyanates during
In addition, an International Standards Organization(5) air sampling. Many national laboratories have adopted
isocyanate sampling and analytical method has recently these modifications; for example, coating the glass-fiber
been published. The most common sampling and analytical filters used in these methods with 2 milligrams (mg) of 1-(2-
methods for diisocyanates are listed below: pyridyl) piperazine (PP) compared to 0.1 mg PP in OSHA
Method 42 and 1.0 mg PP in OSHA Method 47. Isocyanate
• OSHA Method 42 (TDI, HDI, IPDI, HMDI) manufacturers also recommend using a 13-mm glass-fiber
• OSHA Method PV2125 1,6-HDI polyisocyanate filter mounted in a Swinnex® holder versus a standard
37-mm glass-fiber filter when sampling for MDI.
(5)
International Organization for Standardization (ISO), Case Postale 56, Geneva
CH-1211, Switzerland. In the United States, ISO standards may be obtained from the
American National Standards Institute (ANSI) at <http://www.ansi.org>

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September 20, 2019

For spray painting applications, isocyanate manufacturers has been developed which can be used to accurately
recommend using modifications to NIOSH Method 5521 determine airborne concentrations of polyisocyanates during
and OSHA Method 47 which involve using glass impingers spray application of coatings.
containing a derivatizing solution (PP/toluene). These Evaluation of worker exposure to diisocyanates has
modifications improve the NIOSH and OSHA sample focused primarily on air sampling. However, there is growing
methods so that they more efficiently collect and analyze interest in assessing for unreacted isocyanates on surfaces
isocyanate aerosols (i.e., spray mist particles as well as due to the need to prevent skin contact with this chemical.
vapors). This has led to the use of wipe test kits to evaluate for surface
Industrial hygiene consultants or national laboratories contamination. The technology for evaluating for surface
that perform isocyanate analysis should be contacted for contamination of isocyanates is not as advanced as that for
help in selecting the proper air-sampling method. Various airborne monitoring. To check for surface contamination, wipe
factors affect the isocyanate sampling method chosen. For test kits are available from Colorimetric Laboratories Inc.((6))
example, the method of application (e.g., spray, brush, roller) (CLI Surface Swype™), and ChemTeq((7)) (ChemWipes™).
of the coating system, the physical state of the isocyanate Both of these wipe test products are qualitative assessment
likely to be present in the air being sampled (i.e., vapor and/ tools and rely on a color change to assess for the presence
or aerosol), and the specific isocyanate or polyisocyanate to of the diisocyanate monomer. The degree of color change
be evaluated. The air-sampling techniques may include the on the wipe pad provides a visual indication of the degree
use of impingers, filters, denuders; or some combination of of surface contamination. A positive response using the
each of these devices. wipe pad does not represent employee exposure, only
Direct reading instruments are available for measuring that an unreacted isocyanate group exists on the surface.
airborne HDI, TDI or MDI vapors in the work environment. The information should be used to assess safe work (i.e.,
The direct reading instruments draw air across a chemically employees removing PPE in work areas), personal hygiene
impregnated carrier (i.e., amine treated paper tape). The and housekeeping practices.
diisocyanate (NCO group) reacts with the chemical on the One of several important properties to characterize the
tape to produce a color reaction. The color change is read potential for a diisocyanate/polyisocyanate to exist in the air
optically by the instrument which is converted to a digital during brush and roll applications is the vapor pressure since
display reading in ppb. It must be pointed out, however, that evaporation will be the predominant method to generate
these direct read instruments are not suitable for monitoring airborne polyisocyanate and isocyanate monomers. All
in spray application environments since the spray coating spray applications involving an isocyanate result in potential
mist droplets can coat the optics and/or the treated paper aerosol (spray mist) exposure. Therefore, vapor pressure
tape and give erroneous readings. These instruments may is not an important characteristic to consider for spray
be used to evaluate airborne diisocyanate monomer vapor applications. Generally, a low vapor pressure is associated
concentrations during non-spray applications such as: mixing, (6)
Colorimetric Laboratories, Inc., 1261A Rand Road, Des Plaines, IL 60016-
repackaging, batchmaking, coil coating, and brush/roller/ 3402. Phone: int+1-847-803-3737, <http:www.clilabs.com>
squeegee application. To date, no direct reading instrument ChemTeq, 800 West 24th Street, Suite B, Norfolk, VA 23517. Phone: int+1-757-622-
(7)

2223, <http://chemteq.net>

TABLE 2
VAPOR PRESSURE OF COMMONLY USED
DIISOCYANATE MONOMERS AND
POLYISOCYANATES)
Chemical CAS# Vapor Pressure
(mm Hg 20ºC)
HDI Polyisocyanate 28182-81-2 <1 x 10-6
HMDI Monomer 5124-30-1 1.5 x 10-5
MDI Monomer (4,4’-MDI) 101-68-8 <1 x 10-4
Polymeric MDI 9016-87-9 <1 x 10-4
IPDI Monomer 4098-71-9 0.0005
HDI Monomer 822-06-0 0.01
TDI Monomer (2,4 and 2,6 TDI) 584-84-9; 0.02
91-07-7

Note: For comparison, methyl ethyl ketone (MEK) has a vapor pressure of 78 mm Hg at 20ºC.
Courtesy of Covestro LLC

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with low potential for vapors to be emitted from the chemical. where there are few impediments to air movement (i.e., walls
Heating of the chemical will increase emissions, but it is good or structures that could decrease air movement through the
know the vapor pressure at room temperature. Several other work area), and where the volume of coating applied or the
factors including application method, rate of application, number of applicators would not cause a high generation rate
volume of material applied, ventilation/air movement through of coating vapors or aerosols. In most cases where general
the work area and other factors should be considered. ventilation practices are used, the workers will need to wear
Table 2 summarizes the vapor pressure of commonly used respiratory protection and PPE to prevent skin contact.
diisocyanate monomers and polyisocyanates. The likelihood of overexposure in non-spray, non-heated
applications of coatings containing polyisocyanates is
3. Control of Health Hazards reduced due to the low volatility and vapor pressure of these
materials. Hence, the application of polyurethane coatings by
3.1 ENGINEERING CONTROLS: Ideally, hazard brush, paint mitt, roller, or squeegee reduces the likelihood
control of vapor or spray mist is accomplished through of inhalation overexposure to airborne diisocyanate vapors.
engineering controls. Effective engineering controls should However, appropriate measures must be established to
be used whenever possible to reduce and/or eliminate prevent skin/eye contact during these applications.
worker exposure to all respiratory hazards.
3.2 RESPIRATORY PROTECTION: Good safety and
There are several engineering controls available to
health practices dictate that when isocyanate-containing
reduce exposure to vapors and mists during the use of
coatings are spray applied, respiratory protection should
industrial maintenance coatings including:
be worn. At least one manufacturer of diisocyanates/
polyisocyanates recommends air-supplied respirators
• Local exhaust ventilation (LEV)
for spray application if the airborne concentrations are
• Isolation principles
unknown or if they exceed ten times the appropriate airborne
• Alternative spray application techniques
concentration standards/guidelines.4 In such situations, a
• General ventilation (GV)
tight-fitting full-face supplied-air respirator or a loose-fitting
hood/helmet supplied-air respirator operated in a continuous
The most effective engineering control for spray
flow mode is appropriate. However, the same manufacturer
coating applications is a properly designed, maintained and
states that air-purifying respirators may be used under the
ventilated enclosure. An example of such a control would
following conditions:
be a commercially available ventilated spray booth. Spray
• if airborne concentrations are known to be less than
booths or spray rooms should be set up in such a way so that
10 times the standard/guideline concentration;
air flows through the coating application work area toward
• if the spraying is not being done in a confined
an exhaust air plenum or duct. The booths or rooms typically
space;
are designed for either lateral or down draft air movement
• if pre-filters are changed as needed to prevent
to help enhance the air exchange in the spray area. Air
excessive breathing resistance; and
should be exhausted through filters and directed outside the
• if appropriate change schedules are implemented
building. Whenever possible, local exhaust ventilation should
for the organic vapor cartridges (OVCs) in
be designed in accordance with the guidelines outlined in
accordance with 29 CFR 1910.134.
the ACGIH text titled “Industrial Ventilation: A Manual of
Recommended Practice for Design.”
Studies have shown that HDI polyisocyanates are
Isolation principles include automatic (i.e., robotic)
essentially non-volatile and become airborne only as
spray application techniques rather than manual spray.
mechanically generated aerosols during spray application.5
Isolating the spray application allows the worker to observe
Furthermore, these aerosols are efficiently collected by
the coating process from a separate location rather than
the particulate pre-filters of a spray painting air-purifying
being situated in the immediate spray area.
respirator.6,7,8,9 The same studies show that these pre-filters
Use of alternative application equipment (e.g., airless,
did not fail by allowing breakthrough of the aerosol. Rather,
HVLP, or electrostatic spray equipment) may help reduce
they simply became increasingly clogged until airflow
spray mist generation during spray painting. In addition, the
resistance was too great to allow easy breathing. Therefore,
use of spray gun extensions may help reduce the amount of
when breathing resistance becomes noticeably higher
spray mist in the breathing zone of the painter.
during use, the respirator wearer need only replace the used
General ventilation, sometimes referred to as dilution
pre-filters with new ones.
ventilation, involves using man-cooling fans or blowers to
An industry study10 conducted by an isocyanate
move high volumes of “fresh” outside air through a work
manufacturer has shown that:
area. The “fresh” outside air mixes with the air contaminants
• Organic vapor respirator cartridges demonstrated a
generated from the application and reduces the airborne
collection efficiency for HDI vapors greater than 99.6%
chemical concentration. This type of ventilation may be
for 40 hours.
adequate for coatings that do not contain toxic materials,

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• Neither saturation of the cartridge with solvent vapors nor taken to ensure the safety of the persons involved with the
variation of the relative humidity resulted in breakthrough spray application, as well as other persons working in the
of HDI vapor. area who have the potential for skin contact with uncured
• There was no evidence of desorption or migration of HDI material. Because of the high potential for skin contact
within the cartridge during storage at room temperature from overspray particles during spray applications, it is
overnight for five nights, after repeated exposures to recommended that a permeation resistant suit or coverall
high concentrations of HDI and solvents day-after-day with a hood be worn, as well as gloves and work shoes that
for five days. remain at the facility or job site.
If direct skin contact with an isocyanate-containing liquid
Therefore, for coatings containing HDI polyisocyanates occurs, immediately remove contaminated clothing. Wipe
and a small amount of unreacted HDI monomer, there is off the isocyanate product using dry towels or other similar
evidence that a respirator equipped with organic vapor absorbent fabric. If readily available, apply a polyglycol-
cartridges and P-100 particulate prefilters will provide good based cleanser (e.g., Colorimetric Laboratories, Inc. (CLI)
protection against isocyanate exposure for 40 hours of use. D-TAM Skin Cleanser) or corn oil. Wash with soap and
However, the user must ensure that the cartridge service warm water and pat dry. If a polyglycol-based cleanser is not
life is not exceeded for other coating ingredients such as available, wash with soap and warm water. Organic solvents
solvents. Of course, as with any respirator use situation, (e.g. MEK) should not be used for skin cleaning since they
a respirator program, as mandated by OSHA respirator wash oils out of the skin and can cause secondary reactions.
standard, 29 CFR 1910.134, must be in place. If a coating is accidentally splashed onto the skin, the
worker should stop work immediately, wipe off as much as
3.3 PERSONAL PROTECTION - SKIN: When manually possible using a dry towel, and wash with soap and water.
handling the hardener or “catalyst” during tasks such as If some coating does cure onto the skin, it is better to let it
pouring and mixing, it is important to take appropriate wear off than to try to remove it by drastic means such as
measures to prevent direct skin contact. This precaution also harsh solvents.
applies during applications involving brushes, paint mitts
or rollers. Any area of the skin that could potentially come 3.3.1 Guidance Concerning Protective Coveralls:
in contact with an isocyanate-containing coating must be Coverall suggestions for applicators in ascending order of
covered by a permeation-resistant barrier (e.g., nitrile, butyl, their relative protective value are shown in Table 3.
or neoprene gloves, neoprene apron, work clothes and/or One method to check whether one has the proper
coverall). The actual PPE chosen will vary depending upon level of protection is to periodically examine the inside of
the application method and the potential for skin contact. the suit looking for any color or stickiness indicating coating
penetration or permeation (note: to prevent dermal contact
Spray Applications: Since spray application increases with isocyanates, use a gloved hand for this examination.)
the potential for skin contact, stringent precautions must be An alternative is to use an analytical method such as swipe

TABLE 3
COVERALL SUGGESTIONS FOR APPLICATORS1
(IN ASCENDING ORDER OF PROTECTIVE VALUE)

Conditions Types of Coveralls
Intermittent Spraying
Good ventilation Dupont™ Tyvek® 400 (or higher)
Small amount of overspray Kimberly Clark KleenGuard A20
No splash potential
Continuous Spray
Moderate amount of overspray DupontTM Tychem® 2000 (or higher) ™
Moderate splash potential Kimberly Clark KleenGuard A40™
Potential to rub against freshly coated surfaces Kappler™ ProVent® 7000

Heavy and continuous overspray DupontTM Tychem® 4000 (or higher)

Heavy splash potential Kimberly Clark KleenGuard A70™
Coverall surface becomes thoroughly wetted with coating Kappler™ Zytron® 100
1
The products listed above were known to provide appropriate protection at the time of publication of this revision. The committee should be advised of additional equally effective
products that may become available in the future.

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testing to test for isocyanate contamination on the inside of develop an allergic sensitization is remote. However, an
the coverall. If there is evidence of breakthrough, use of the allergic respiratory reaction in a previously sensitized person
next more protective level of coverall is indicated. might occur at exposures below the odor threshold (i.e.,
when a person smells the material) and exposure limits or
3.3.2 Medical Testing: All persons who are to be guidelines for the specific isocyanate involved.
assigned to a work area where isocyanates are used should The environmental risk associated with isocyanate-
undergo a pre-placement medical evaluation. Special containing coatings appears to be minimal under normal
attention should be directed to pre-existing diseases of the application and removal conditions. There is no evidence
respiratory system or abnormal pulmonary function. that the application or removal of isocyanate-containing
Each employee should complete a medical and coating creates any significant risk to the environment
occupational disease questionnaire. A history of current provided that basic control on spills and clean up of removed
asthma, respiratory allergies, such as hay fever associated materials is performed. This is because isocyanates react
with cough or other breathing difficulties or extensive active with environmental moisture to produce essentially non-toxic
eczema, are possible reasons for restricting persons from and inert polyureas.
jobs in which they could be exposed to isocyanates.
In addition to completing a medical questionnaire, 4.1 EVALUATION OF THE HAZARD: Regulated area
persons who may be assigned to jobs with potential monitoring can be conducted around the areas where field
isocyanate exposure should undergo a physical examination, application occurs to quantify the potential risk to the public.
including a thorough skin inspection, examination of the heart This could be conducted using low or high flow personal
and lungs, and a baseline pulmonary function test (PFT). A sampling pumps in accordance with previously identified
medical determination should be made of the person’s ability NIOSH, OSHA, and other sampling methods. Typically,
to wear respiratory protective equipment. Referral to an exposures below the Action Level (1/2 of the PEL or TLV)
occupational health or pulmonary specialist is recommended are considered acceptable levels of exposure to unprotected
in all cases where evaluation results are abnormal. workers. Also, state and federal EPA do have suggested
New workers should have a medical follow-up during the limits in place for protecting the public.
first 6 to 12 months following medical clearance to work in an
area involving potential isocyanate exposure. This follow-up 4.2 HANDLING PRACTICES: Suggested handling
should be in the form of a brief medical questionnaire. practices to reduce potential isocyanate exposures through
Workers should undergo an annual medical evaluation spills and releases include:
including a pulmonary function test looking for a decrease • Automatically pump isocyanates from drums to the
of 10-20% or more from the individual’s base-line PFT, and/ process equipment where possible.
or development of respiratory symptoms. Further medical • Store isocyanate-containing products in tightly
evaluation by an occupational health and/or pulmonary closed containers, in areas protected from weather
specialist is needed if a persistent reduction of 10-20% or (i.e., rain), and in well-ventilated areas. Do not
more is detected. tightly reseal opened isocyanate containers if
If a worker develops respiratory distress when working moisture contamination is suspected.
with these products, he/she should be removed from • The isocyanate-water reaction produces carbon
exposure and be examined by a physician. If hypersensitivity dioxide gas that can pressurize sealed containers
to isocyanates has developed, the worker must be removed and may cause explosive rupture.
from further exposure to any isocyanate-containing product. • Keep isocyanate-containing coatings and removed
At present, there is no conclusive screening test suitable materials separate from potential ignition sources.
for detecting persons most likely to become sensitized to
isocyanates. Therefore, it is essential to examine all cases of 4.3 SPILL CONTROL PROCEDURE: It is important
absence due to illness, especially if related to the respiratory to read and be knowledgeable of the information contained
system, to determine an individual’s ability to continue work within Section 6 of the Safety Data Sheet (SDS) before
with isocyanate-containing products. responding to a chemical spill. The following highlights
some important items to remember when responding to an
4. Environmental and Public Health Risks isocyanate spill:
• Notify management and the site’s spill response
The public health risk associated with isocyanate-containing team
coatings includes the potential of respiratory sensitization • Isolate the area and prevent access of unauthorized
through repeated or high exposures to isocyanates in the individuals
ambient air. Although unlikely for the general public, skin • Wear necessary personal protective equipment
irritation and allergic reactions might occur through direct (PPE)
skin contact. Public health risk is difficult to quantify. The • Control the source of the leak and contain released
likelihood that the public adjacent to a coating project would material

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• Ventilate and remove ignition sources Additionally, the RCRA requirements discussed above
• Spread absorbent material completely over the apply to containers unless empty. The RCRA definition of
spilled liquid “empty” is such that all wastes have been removed that can
• Shovel the absorbent material into an approved be removed using common practices to remove materials,
metal container (i.e., 55-gallon salvage drum) e.g. pouring, pumping, and aspirating, and no more than 1
• Do not fill the metal container more than 2/3 full and inch of residue remains on the bottom of the container or
do not tighten the lid on the container for at least inner liner; or for containers  of 119 gallons or less: no more
72 hours than 3% by weight of the total capacity of the container
• Repeat application of absorbent material until all remains in the container or inner liner; or for containers of
liquid has been removed from the surface 119 gallons or more: no more than 0.3% by weight of the
• Decontaminate the isocyanate spill surface area total capacity of the container remains in the container or
using a neutralization solution (see SDS) inner line.11
• Move the container to an isolated, well-ventilated In two component polyurethanes, once the isocyanate
area to allow release of carbon dioxide gas catalyst has been added to the “paint” component, the
• Residual surface contamination can be checked for material will gel in the can within several hours. Once the
the isocyanate component using a wipe test pad coating has completely hardened, the isocyanate has
to verify decontamination is complete (e.g., CLI reacted to form the polyurethane and the disposal decision
Surface Swype™ or ChemTeq® ChemWipes) is based on the characteristics of the waste, including but not
• After 72 hours, seal the container, and properly limited to the amount of potentially ignitable residue solvent
dispose of absorbent material in accordance with still entrained in the material, the presence of heavy metals
existing federal, state, and local regulations or the presence of TDI.
• Using the neutralization solution, decontaminate Based on the above criteria, many isocyanate residues
tools, equipment and PPE which were used during and leftover isocyanate-containing coatings may be
the spill cleanup considered hazardous waste and must be characterized,
handled, and disposed of appropriately.
5. Waste Management
5.2 HANDLING, STORAGE, TRANSPORTATION,
5.1 IDENTIFICATION OF HAZARDOUS WASTE: AND DISPOSAL: Store isocyanate-containing waste in
Hazardous wastes are regulated as part of the Resource tightly sealed containers, unless moisture contamination
Conservation and Recovery Act (RCRA), 40 Code of Federal is suspected. If moisture contamination is suspected refer
Regulations (CFR) Parts 260-273(8). These regulations back to Sections 4.3 and 4.4. Store in a cool, well-ventilated
require a waste to be considered hazardous if it poses area. Comply with 40 CFR 260-273 regulations regarding
a potential hazard to human health or the environment. handling, storage, and disposal. Comply with 49 CFR 105-
Wastes are classified as hazardous if they are specifically 180 regulations relative to transportation of isocyanate-
listed by the EPA in the regulation or if they exhibit any of the containing materials.
characteristics identified in the regulation. Implement a Hazardous Waste Management Plan
Listed wastes are automatically identified as hazardous including procedures for:
by the EPA and require no additional testing. Solid and • Waste Minimization - This section should include
liquid (e.g. excess coating) wastes generated from the a description of the waste minimization efforts
use of toluene diisocyanate (TDI) are considered listed implemented.
wastes (U223), and should be treated as hazardous from • Waste Sampling, Testing, and Classification -
the point of generation through disposal. However, most This section should describe how liquid and solid
industrial maintenance coatings do not contain TDI. No isocyanate-containing wastes will be characterized
other isocyanates used in these coatings are listed as RCRA (i.e., through analysis or declaration), the sample
hazardous wastes. collection method, number of samples to be
Characteristic wastes are categorized as hazardous collected, and the type of laboratory analysis to be
if they exhibit characteristics of ignitability, corrosivity, conducted.
reactivity, or toxicity. Some isocyanate-containing wastes • Coating and Solvent Waste Handling and
may meet the characteristic of reactive or ignitable wastes. Storage - This section should include residues
One determination of an ignitable waste is a liquid having of waste in empty containers, container and
a flash point of less than 60°C (140 °F). Wastes generated storage area criteria, and labeling and signage
from the use of isocyanates should be subject to flash point requirements.
testing in accordance with RCRA requirements to determine • Transportation and Disposal - This section should
if they are hazardous. Reactive wastes include those that address who will obtain the EPA ID number (i.e., who
react violently with water. is the generator) and use of licensed transporters
and permitted disposal and incineration facilities.
(8)
CFRs may be obtained online at https://www.ecfr.gov/

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 SSPC-TU 8
September 20, 2019

• Contingency Plan and Training - This section 5. R. J. Rando and H. G. Poovey, “Development and
should include a description of the Preparedness, application of a dichotomous vapor/aerosol sampler for
Prevention, and Contingency Plan (PPCP); spill HDI-derived total Reactive Isocyanate Group,” Am. Ind.
control procedures; worker training; and record Hyg. Assoc. J. 60(6): 737-746 (1999).
keeping. 6. V. Dharmarajan, P. M. Uhrin, and D. R. Hackathorn,
• Implementation Forms - The section should “Evaluation of air purifying respirators in simulated
include implementation forms addressing site isocyanate based paint spraying operations,”
storage inspections, labeling requirements, unpublished study (Pittsburgh, PA: Bayer Corporation
emergency phone numbers, and hazard release [formerly Mobay Corporation]. 1982).
documentation forms. 7. J. F. Vasta, “Respirator Cartridge Evaluation for
• Training - Contractors may also wish to incorporate Isocyanate-containing Imron” and Centari” Enamels,”
hazard communication, flammable and combustible Am. Ind. Hyg. Assoc. J. 46, 1, p.39-44 (1985).
liquids, and personnel protective equipment training 8. C. Rosenberg and T. Tuomi, “Airborne Isocyanates
requirements as part of its program and training in in Polyurethane Spray Painting: Determination and
compliance with the OSHA regulations relative to Respirator Efficiency,” Am. Ind. Hyg. Assoc. J. 45, 2, p.
isocyanate exposures and handling of wastes. 117-121 (1984).
9. G. V. Croshaw and S. W. Horstman, “Air-purifying
6. Disclaimer Respirator Performance Against a Two-component
Polyurethane Spray Paint Aerosol,” Poster Session
6.1 This technology update is for information purposes at the American Industrial Hygiene Conference and
only. It is neither a standard nor a recommended practice. Exposition, May 21-26, at St. Louis, MO, 1989.
While every precaution is taken to ensure that all information 10. V. Dharmarajan, R. D. Ling and H. E. Myer, “Evaluation
furnished in SSPC technology updates is as accurate, of Organic-Vapor-Respirator Cartridge Efficiency for
complete, and useful as possible, SSPC cannot assume Hexamethylene Diisocyanate in the Presence of Organic
responsibility nor incur any obligation resulting from the use Solvents,” Applied Occupational and Environmental
of any materials, coatings, or methods specified herein, or of Hygiene Journal, Vol. 16, March 2001, p. 397-404.
the technology update itself. 11. U.S. Code of Federal Regulations, Title 40 Part 261.7,
“Residues of hazardous waste in empty containers”
6.2 This technology update does not attempt to address (Washington, DC: Office of the Federal Register, 2017),
problems concerning safety associated with its use. The p. 65.
user of this specification, as well as the user of all products
or practices described herein, is responsible for instituting 8. Bibliography
appropriate health and safety practices and for ensuring
compliance with all governmental regulations. Aliphatics Isocyanate Monomers – Health and Safety
Information: Desmodur H (HDI), Desmodur I (IPDI), and
7. References Desmodur W (HMDI), Covestro LLC, January 2017.
American Chemistry Council, “Environment, Health and
1. 2018 Guide to Occupational Exposure Values, Safety Industrial Hygiene and Workplace Monitoring
ACGIH Publication 0396 (ISBN: 978-1-607260-98-1), –Diisocyanates” .
(Cincinnati, OH: American Conference of Governmental <https://dii.americanchemistry.com/Environment-Health-
Industrial Hygienists, 2018). and-Safety/WorkerIndustry-Health-and-Safety-Guidance/
2. J. Pauluhn, P. Eidmann, and U. Mohr, “Respiratory Industrial-Hygiene-and-Workplace-Monitoring.html>
Hypersensitivity in Guinea Pigs Sensitized to 1,6-HDI: (April 2, 2018)
Comparison of Results Obtained with the Monomer “Automotive Refinishing Industry Isocyanate Profile,”
and Homopolymer of HDI,” Toxicology, Volume 171, 28 Science Applications International Corporation, May 1,
February 2002, pages 147-160. 1997. May be downloaded from <https://www.epa.gov/
3. State of Oregon, Oregon Administrative Rule 437, saferchoice/automotive-refinishing-safety-information>
Division 2, Subdivision Z-Toxic and Hazardous (April 2, 2018).
Substances, Air Contaminants, Table Z-2, page Z-26. Desmodur N, Hexamethylene Diisocyanate Based
Salem, OR: Oregon Occupational Safety and Health Polyisocyanates: Health and Safety Information,
Division. Available online at < http://osha.oregon.gov/ Covestro LLC, February 2016.
OSHARules/div2/div2Z-437-002-0382-air-cont.pdf> EPCRA(Emergency Planning and Community Right to
(April 2, 2018). Know Act), 42 U.S.C. 1011 et. seq. Text available
4. Aliphatics Isocyanate Monomers – Health and Safety at:<http://www.epa.gov/ceppo/lr-regs.htm#epcra>
Information: Desmodur H (HDI), Desmodur I (IPDI), and (April 2, 2018 Guide to Occupational Exposure Values
Desmodur W (HMDI), Covestro LLC, January 2017. (current year). Cincinnati, OH: American Conference of
Governmental Industrial Hygienists.

9
SSPC-TU 8
September 20, 2019

Industrial Ventilation: A Manual of Recommended Practice U.S. Code of Federal Regulations (CFR) Title 40
for Design (latest edition). Cincinnati, OH: American “Protection of the Environment,” Washington, DC:
Conference of Governmental Industrial Hygienists. Office of the Federal Register. Many of these CFRs
ISO 17734 (latest revision) Determination of organonitrogen are available from local U.S. Government Printing
compounds in air using liquid chromatography and Offices or by downloading from the internet. The
mass spectrometry – Part 1: Isocyanates using search page for the Code of Federal Regulations is
dibutylamine derivatives. (Geneva: International <https://www.gpo.gov/fdsys/browse/collectionCfr.
Organization for Standardization) Covestro LLC, action?collectionCode=CFR> Consult the blue pages
Product Safety & Regulatory Affairs Resources/ of the
Information; Pittsburgh, PA; <http://www. local phone directory for offices in many major cities.
productsafetyfirst.covestro.com/> Of special interest are the following sections:
• Aliphatic Isocyanate Monomers Health & 40 CFR 100-149, Clean Air Act
Safety Brochure, January 2017 40 CFR 171-179, Hazardous Materials
• Hexamethylene Diisocyanate Based Transportation Act
Polyisocyanates (Desmodur® N Products), 40 CFR 261, Appendix II, Toxicity Characteristic
April 2003 Leaching Procedure
• Isocyanates: Questions and Answers about 40 CFR 262, Standards Applicable to Generators of
Safe Use and Handling, October 2015 Hazardous Waste
• Medical Surveillance Guidelines for Users of 40 CFR 264, Standards for Owners and Operators
Isocyanates, September 2017 of Hazardous Waste Treatment, Storage, and
NIOSH Method 5521, Isocyanates, Monomeric. NIOSH Disposal Facilities
Manual of Analytical Methods (NMAM), August 1994, 40 CFR 265, Interim Status Standards for Owners
Atlanta, GA: U.S. Centers for Disease Control, National and Operators of Hazardous Waste Treatment,
Institute for Occupational Safety and Health. Available Storage, and Disposal Facilities
online at < https://www.cdc.gov/niosh/docs/2003-154/ 40 CFR 265, Subpart C, Preparedness and
pdfs/5521.pdf> (April 2, 2018). Prevention
OSHA Method ORG-042, “1,6 Diisocyanates, 40 CFR 265, Subpart D, Contingency Plan and
1,6-Hexamethylene Diisocyanate (HDI); Toluene Emergency Procedures
2,6-Diisocyanate (2,6-TDI); Toluene-2,4- 40 CFR 265.16, Personnel Training
Diisocyanate (2,4-TDI),” March 1989, (Washington, 40 CFR 268, Land Disposal Restrictions
DC: U.S. Deparatment of Labor, Occupational 40 CFR 302, Designation, Reportable Quantities
Safety and Health Administration. Available and Notification
online at <https://www.osha.gov/dts/sltc/methods/ 40 CFR 355, Emergency Planning and Notification
organic/org042/org042.html> (April 2, 2018). U.S. Code of Federal Regulations (CFR) Title 33
OSHA Method PV2125, “1,6-Hexamethylene “Navigation and Navigable Waters”, Chapter 26,
diisocyanate homopolymer,” June 2003, (Clean Water Act). Text of this Act is available at
(Washington, DC: U.S. Deparatment of Labor, <https://www.gpo.gov/fdsys/pkg/CFR-1999-title33-
Occupational Safety and Health Administration. vol1/content-detail.html>
Available at https://www.osha.gov/dts/sltc/methods/ American Chemistry Council: Center for the Polyurethanes
partial/pv2125/pv2125.html (April 2, 2018). Industry; Environment, Health and Safety Resource
OSHA Method ORG-047, “Methylene Bisphenyl Document: Guidance for Working with Aliphatic
Diisocyanates, March 2016; <http://polyurethane.
Isocyanate (MDI),” March 1989, Washington,
americanchemistry.com/Resources-and-Document-
DC: U.S. Deparatment of Labor, Occupational
Library>
Safety and Health Administration. Available
NIOSH Safety and Health Topics Page on Isocyanates:
online at <https://www.osha.gov/dts/sltc/methods/
<www.cdc.gov/hiosh/topics/isocyanates/
organic/org047/org047.html> (April 2, 2018).
Colorimetric Laboratories, Inc., Des Plaines, IL; <http://
Streicher, Robert P., Reh, Christopher M., Key-Schwartz,
www.clilabs.com/>.
Rosa, Schlect, Paul C., and Cassinelli, Mary-Ellen,
Chemteq, Inc., Norfolk, VA: <http://www.chemteq.net>
“Determination of Airborne Isocyanate Exposure,”
Section K of NIOSH Manual of Analytical Methods.
Cincinnati OH: NIOSH, 1998.
. U.S. Code of Federal Regulations (CFR) Title 29 “Labor”,
Part 1910, Section 134 “Respiratory Protection,”
paragraphs (a) through (o). Washington, DC: Office of
the Federal Register, 1998. The search page for the
Code of Federal Regulations is https://www.gpo.gov/
fdsys/browse/collectionCfr.action?collectionCode=CFR

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Copyright ©
SSPC standards, guides, and technical reports are copyrighted
world-wide by SSPC: The Society for Protective Coatings. Any
photocopying, re-selling, or redistribution of these standards,
guides, and technical reports by printed, electronic, or any
other means is strictly prohibited without the express written
consent of SSPC: The Society of Protective Coatings and a
formal licensing agreement.

11