HUNTSMAN 

Enriching lives through innovation 

Huntsman International LLC's 

Response to EPA's 

Voluntary Information 

Request for Information 

Relating to Curing Rates 

for Polyurethane Products 

Submitted: 

December 10, 2012 
( 

f'· '\) 1\- - ~ & ~ o ~ QT- J-011- o~ ~a-.­

HUNTSMAN 

.COntains· ~o tar 

Enriching lives through innovation 

December 10, 2012 

Sent by Federal Express and by Email to sleasman.katherine@epamail.epa.gov and 

leslie.cronkhite@epamail.epa.gov 

U.S. Environmental Protection Agency 

Leslie Cronkhite (7405M) 

Chemical Control Division 

Office of Pollution Prevention and Toxics 

Office of Chemical Safety and Pollution Prevention 

EPA East Building 

1201 Constitution Avenue, N.W. 

MC: 7401M Room 3166 

Washington, DC 20004 

Subject: Huntsman International LLC's ("Huntsman") Response to 

EPA's Voluntary Information Request for 

Information Relating to Curing Rates for Polyurethane Products 

Dear Ms. Cronkhite: 

-

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~ 

c... 

> O:;:o z -of"'l1 t -on \.0 -fj"'rj 

., ('"')-

co< :X _rrt 

- ('"')0 ..• 

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Huntsman is responding to the EPA's request dated September 19, 2012 for information 

relating to curing rates for polyurethane products. We understand from the letter that 

EPA will use this information as part of a quantitative exposure assessment. We look 

forward to more dialog with the EPA to continue the safe use of polyurethane products. 

As a leading supplier of polyurethane products to industrial customers, safety is at the 

core of Huntsman's guiding principles. With numerous production and research 

facilities globally, as well as a team of knowledgeable scientific experts, Huntsman is 

committed to lending our expertise to further the EPA's evaluation. In this spirit, 

Huntsman conducted an extensive review of all internal documents globally and across 

all relevant business divisions, and is pleased to submit the attached documents as a 

full and comprehensive response to your request. 

EPA's correspondence states that this request relates to curing rates of polyurethane 

products intended to further react and thus undergo "curing" as part of their commercial 

use. Huntsman has carefully considered all its products and has determined that the 

products relevant to EPA's inquiry are specifically: one-component foam, spray foam, 

DIY spray foam kits, adhesives, coatings and sealants. Huntsman concluded that other 

products fall outside the scope of EPA's inquiry as they are not intended to further react 

as part of their commercial use. 

CONTAINS NO CBI 

10003 Woodloch Forest Drive, The Woodlands, Texas 77380 

Tel.: 281-719-6000 Fax.: 281-719-6416 www.huntsman.com 
Ms. Leslie Cronkhite 

U.S. EPA 

Office of Pollution Prevention and Toxics 

December 10, 2012 

For our products that are responsive to EPA's query, Huntsman is providing all relevant 

studies, memos, unpublished data or any other documents which contain either 

(i) measurement of isocyanate functional groups during curing and/or (ii) investigations 

of re-occupancy time. Associated information such· as product type, intended final use, 

test methods, qualitative data (e.g., surface wipe sampling) over time, tack free time is 

provided for the above cases, when available. Please note that we are not submitting 

public documents authored by third parties that are readily accessible in the public 

domain. 

For your convenience, a table of contents summarizing the documents being submitted 

is provided in the attachment. Each document is also appended with a cover sheet 

summarizing key aspects of the information requested. 

Please do not hesitate to contact me if you have further questions. I can be reached at 

281-719-4914 or by email at monica_n_karamagi@huntsman.com. 

Sincerely, 

Monica Karamagi 

Regional Marketing and Industry Affairs Manager 
Section 1 

Section 2 

Section 3 

Section 4 

Section 5 

EPA Voluntary Information Request 

Table of Contents 

Risk Calculation of isocyanate emission at workplaces during 

processing reactive PU adhesives 

Danish consumer study 

Air monitoring investigation during spray application in a residential 

house and surroundings 

Reaction document for the Risk Reduction Strategy for consumer 

exposure for MDI, includes OCF Airborne concentrations of MDI 

FEICA position paper on the use of gloves for MDI containing 

mixtures, in particular OCF offered to the general public 
) 

) 

i 

-~I 
( Huntsman Division (PU, PP, AdMat) PU 

Region (US, EAME, Asia) EAME 

Product (OCF, SPF, SPF kits, FR resins, Polyurea, Adhesives, Adhesives 

Coatings, Elastomers, Sealants, Other) 

Is test data available? (If answer is "NO", please save this YES 

form and email it to Michelle Koenig. If"YES", continue 

survey). 

Is this information considered Confidential Business NO 

Information (CBI)? Yes or No 

Chemical Composition of the fonnulated products (e.g polyurethane 

polyurethane, polyurea) 

BriefName of the study conducted (e.g. "Frankel Home Risk Calculation of isocyanate 

Testing"). emission at workplaces during 

processing reactive PU adhesives 

1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 

2 Curing (surface) or Exposure (airborne)? Curing 

3 Relevant Data Summary - Indicate variables studied e.g. RT 

environmental conditions, ventilation rates, temperature, 200g adhesive 

humidity, catalysts/reactants present, proportioning/mixing, 

application site (indoors or outdoors); quantity of product 

used, application method and square footage covered. 

4 Test lab methods/ Instruments used/ Detection levels, QC Unclear, but standard methods 

measures, levels of detection 

Experimental Parameters (sampling times, strategy) ? 

5 Summarized Test Data Results Fully cured after 300 minutes. 

Although topic relates to industrial 

setting. The adhesives can be used 

by professionals/consumers? as 

well 

6 Sensitivity Analysis (if any) ? 

7 Identify location of above data in document- Pages/Para (e.g. Slide 20 

Pg2 Para4) 

8 Was Reoccupancy time determined? No 

9 If answer to 8 is yes, indicate reoccupancy time. 

10 Exposure limits (occupational and general population limits) 0.05 mg/m3 

No EAME general population limit 

inEU 

11 Quantitative Testing: Indicate whether unreacted 

diisocyanates were present, type of surface, and results 

obtained at each interval measured 

12 Other Data on Curing: Tack Free time, cuttable, expansion 

time, light traffic, ready to use etc 

13 Data related to formation ofbyproducts, particularly 

substances that continue to off-gas over time. 
) 
Paper Xlll.3 

Risk Calculation of Isocyanate Emission at 

Workplaces during Processing Reactive 

Polyurethane Adhesives 

Presented by: 

Co-Author(s): 

Company 

Congress Partners 

EuPIA 

'··~ .... .!>~.,_,.,.,.... .......... .... 

A sot.tor ol CEPE t~is.bl 

Dr. Jasmin Trautmann 

Thomas Hensel, lnstitut for 

Statutory Accident Insurance and 

Prevention in Printing and Paper 

Converting Industry 

Fraunhofer Institute for 

Manufacturing Technology and 

Applied Materials Research 

Wiener Str. 12 

28359 Bremen 

GERMANY 

+49 421 2246-643 

+49 421 2246-430 

jt@ifam.fraunhofer.de 

HINTER WALDNER 

CONSVLTING 

v 

VIIKEIIIZ 
._ .. / 

Risk Calculation of Isocyanate Emission a

Workplaces during Processing Reactive 

Polyurethane Adhesives 

Dr. Jasmin Trautmann 

Fraunhofer Institute for Manufacturing Technology and 

Applied Materials Research, Bremen 

Dr. Thomas Hensel 

Institution for Statutory Accident Insurance and Prevention 

for the Printing and Paper Converting Industry, Wiesbaden 

Fraunhofer lnstitut 

Fertigungstechriik 

Materialforschung 

BG 

• 

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_ ____.../ 
Motivation 

Motivation for measuring occupational exposure 

1.) Extensive data base for an overview of isocyanate concentratio

workplaces. 

2.) • Comparison of different climate conditions: humidity, applica

temperature, exhaustion. 

• Evaluation of available analytical techniques and their source

(Additional simulation of workplaces at the IF AM.) 

3.) Detailed description of the workspace environment; Evaluation 

assumed factors. 

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• 

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Outline 

I. Polyurethane adhesives 

II. Isocyanate air concentration 

Ill. Air sampling methods 

IV. Monomer exposure 

v. Summary I Conclusions 

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• 

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· .. __ / 

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Section I 

I 

• 

Polyurethane adhesives 

BG 

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I Polyurethane adhesives 

Application areas 

• Bookbinding 

• Automotive interior trim 

• Wood coatings 

Application methods 

• Spray application 

• Slot nozzle application 

• Roller application 

BG 

• 

Berufsgenossenschaft 

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I Polyurethane adhesives 

• lsocyanates: R- N=C=O) 

e.g.:4,4'-Methylenebis(phenyl isocyanate) (MDI) 

as basic module of the 

• Polyurethane (PUR) adhesives 

-> macromolecular matter that consists of a mixture of 

Isocyanate-monomers (1-1 0% ), oligomers and polycyclic 

pre polymers. 

• lsocyanates react fast with humidity or amines. 

• They do not smell. 

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I Polyurethane adhesives 

Occupational Disease 

140 

120 100 

80 

60 

40 

20 

0 

1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 

BG 

• 

Berufsgenossenschaft 

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.._ ____ / 

1-----1 verified o

disease 

insuranc

c::::::J verified o

disease, 

without d

pension 

-a-reported 

occupatiodisease 

In all industry 

Occupational 

Source: BK-D

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Section II 

II Isocyanate air concentration 

.BG Berofsgenossenschoft 

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II Isocyanate air concentration 

Monomers 

PI 

Qo 

Q 

NCO 

4,4'-MDI 

HOI 

BG 

• 

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__ j 

NCO 

NCO ~ -;:?) I 9 I ~ CH2 ~ ~ 2{20 ocyN-Q ~NCO C 

I) l[_J ocN-Q 

CH2 ...... 

2,4'-MDI (it~) 2,2' -MDI CH3 NCO PMDI CH3 OCN~N

JDJI: 0,021 HP~ 

NCO 

2,4-TDI 2,6-

Fraunhofe
II Isocyanate air concentration 

MD I classification 

• Risk class K3 defined in Germany by TRGS 905 -

possible carcinogenic action 

• Xn; R20- Injurious to health when inhalated 

• Xi; R36/37/38- Irritating to eyes, respiratory system 

and skin 

• R42/43 - May cause sensitization by inhalation and 

skin contact ~ S 

• AGW (Occupational Exposure Limit Value): 

0,05 mg/m3 = 0,005 ml/m3 (ml/m3 or ppm) 

• 5 min exposure limit: AGW x 2 

Inhalation is the important exposure route of lsoc

~ BG 

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II Isocyanate air concentration 

Estimation of occupational exposure 

Measured MDI air concentration on adhesive work places 

50 

45 

40 

........ 35 

""' E 

........ 30 

tn ~ 25 

...... 

-

c 20 ~ 15 

10 

5 

0 

2 C-PUR reactive- solvent- AGW 

Hotmelt based PUR 

Source: M. Wirts, Gefahrstoffe- Reinhaltung der Luft, Vol 61, Iss 5, 181-186 (2001) 

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Section Ill 

Ill Air sampling methods 

• 

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Ill Air sampling methods 

Air sampling methods 

Direct Reading Instruments. 

Advantages: immediate results, ease of use (color reaction), inexpens

Disadvantages: Not so accurate or precise as indirect sampling metho

Pumped detector badge; 

visually matched with 

reference color comparator Paper tape instr

Useful for an estimation of diisocyanate emission 

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Ill Air sampling methods 

Indirect (derivatization) method 

• Pumped filter or impinger trapping medium. 

• Fast infield reaction of the diisocyanates with a derivatization reagent

\ 

,, 

I \ ~~ ,J b..~A-CUHtteOU!Iet 

I I 

lmpinger Filter 

lt ~~}. 

:~:~ 

l :~: I ~~SupportPad It .....___, 

I I 

lt - 1 1 _cueettemg It , (mid<le) 

I I 

::~- 1 I -

:: 

~~Cusottainllll 

I I \._ , 

I J ::::-._ 

l .... 

Analytical instruments 

High Pressure Liquid Chromatography -+ Advantage: Good sensitivity

Disadvantage: Method requires standards and analytical facilities. 

Advantage: Accurate method, usable for a validation of working 

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I 

Ill Air sampling methods 

Derivatization reagents for the evaluation of isocyana

Dervatization reagent 

9-(N-Methylaminomethyl)anthracene 

(MAMA) 

Di-n-butylamine (DBA) 

1-(2-Pyridyl)piperazine (2PP) 

1-(2-Methoxyphenyl)piperazine 

(MPP,MOPP,2MP) 

1-(9-Anthracenylmethyl)-piperazine 

(MAP) 

Tryptamine 

BG 

• 

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Detection 

UV/ 

FLD/ECD 

MS 

UV/ FLD 

UV, ECD 

UV/FLD 

FLD/ECD 

,'-.. __ / 

Advantage/ Disadvant

TRIG estimation, light sen

Expensive, non-routine me

impinger method, 

excess reagent can be evap

Polyisocyanates difficu

good separation of monom

sublimes in hot wet cond

TRIG estimation, lower specivity

stability than 2PP 

TRIG estimation, MAP not co

available 

TRIG estimation 

Fraunhofe
Ill Air sampling methods 

Measurement time and distance 

Lab test 

PU Hotmelt, 

MDI - 5 wt. %>, 

heated to 140°C 

200 g adhesive 

Small room 

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300 

250 

!=)' 

.§ 

C) 

2. 200 

!: 

0 

:t::i ~ 1: 150 

(!) 

CJ 

!: 

0 

CJ 

I.. 100 

cu 

-

c ~ 50 

-+--30 min 

--11-15 min 

__..._5 min 

0 I I • I 

~-· I I • 

0 20 40 60 80 100 120 140 160 180 200 

distance [em] 

Fraunhofe
Ill Air sampling methods 

Lab test, PU Hotmelt: MDI- 5 wt. 0/o, heated to 140°C, 

200 g adhesive, Small room 

15 min, 10 em distance 

15 min, 50 em distance 

5 min, 10 em distance 

5 min, 50 em distance 

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HPLC, 2PP cal. 

Air concentration 

(MDI) in J.lg/m3 

278 

2 

283 

12 

color indicator 

(poly MDI scale) 

J.lg/m3 

48 

0 

82 

0 

color indi

(MDI scale) 

305 

0 

450 

0 

Fraunhofe
Ill Air sampling methods 

polyMDI adhesive, RT, spray application 

HPLC, 2PP cal. color indicator color indic

Air concentration (poly MDI scale) (MDI scale) 

(MDI) in 1Jg/m3 1Jg/m3 

12 min, 1 0 em distance 149 - -

12 min, 50 em distance 18 4 19 

5 min, 10 em distance 419 - -

5 min, 50 em distance 2 0 0 

But don't use the paper badges for 30 minute measurements! 

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Section IV 

IV Monomer exposure 

• 

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IV Monomer exposure 

Which parameters influence the emission? 

Temperature 

25.000,-----------------------

2o.ooo I I....-4.4'-MDI fraction of 1C PU I ~ I 

ff ~1s.ooo 1 '~HUI d1spers1on aaneswe 1 // 

2: 

ffi1o.ooo t------------------.. fl=.~--.... 

Vl 

s.ooo I .:7~,..... / I 

20 30 

• 

40 50 60 

Temperatur [°C] 

BG 

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70 80 

600 

500 

:c 400 

1 a 300 

ffi 

(/) 200 

100 

0 

20.000 

18.000 

16.000 

:c 14.000 

:§ 12.000 

10.000 ~ 8,000 

w 

(/) 6.000 

4.000 

2.000 

Monomer c

b 

. ~"'.(.:' //' 

;'/ ~ /' 

v / 

/ 

/ 

// 

20 40 

Content o

1\ -+- 1C-PU Adhesive, 2.4'-MDI traction I• : \ 

\ 

I 

.......,. 

---

2C..PU 

1C-PU 

Adhesive 

Adhesive, 4.4'-MDI traction I based on 4.4'-MDI 

""" ~ ........__.__ ~ "'-

0 so 100 nme[min] 250 300 350 

j 

' ll 

I 

400 

., 

Fraunhofe
IV Monomer exposure 

Temperature dependence of the emission rates 

2,8x1 Os 

2,6x1 0 s 

.----. 

..c 2,4x1 Os N 

E 2,2x1 05 ........... 

0) 

::::1. 

___, 2,0x1 Os 

QJ 

+-' 1 ,8x1 Os C"Ci 

!.,...., 

c 1 ,6x1 Os 

0 

Vl 1 ,4x1 Os 

l/) 

E 1 ,2x1 Os 

QJ 

u 1 ,Ox1 Os 

'+-

4 u 8,0x1 0 QJ 

n. 6,0x1 04 Vl 

4,0x1 0 4 

2,0x1 04 

0,0 

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-•- standard PU-Hotmelt 

-•- emission reduced PU-Hotmelt 

PU decompositio

! 

·--------• • 

130 140 150 160 

temperature [° C] 

170 

Fraunhofe
IV Monomer exposure 

Definition of influencing factors 

1. Step: Development of an equation system 

and definition of influencing factors 

c . =jJ +jJ . + +jJ . + + .... jJ . + + + 

air 0 1 J 1 2 J 2 12 J lJ 2 

cair = air concentration [j.Jg/m3 ] 

f = factor like adhesive temperature, air flow 

p =constant 

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· IV Monomer exposure 

Estimation of occupational exposure limits 

Regression analysis and statistical evaluation: Pareto plot 

en 

2 

ca 

E ~ w 

0) 

0 

..c 

t:: 

0 

162 

-125 122 

-74 

residual monomer exhaustion adhesive temperature measurement dis

~ .BG 

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"'-/ ---~ -·------·-

influencing factors 

Fraunhofe
IV Monomer exposure 

Horizontal and vertical distribution of isocyanates 

Diisocyanate emission decrease with: 

• Rising humidity 10 

9 

• Lower monomer content 8 -11- with source exha

• Good exhaustion 

"'E 

.._ 7 

Cl 

2: 6 

---without source ex

t: 

0 

• Lower application temperature ~ 5 ~ c 4 

(]) 

• High air volume (.) 3 t: 0 (.) 

I... 2 "(U 

i3 1 ~ 0 

-1 

0 100 200 300 

measurement distance [em] 

Depending on these parameters the emission decreases in th

·horizontal dimension. ~ BG 

.. 

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IV Monomer exposure 

Horizontal and vertical distribution of isocyanates 

Beside the main factors the vertical distribution has one more 

influencing factor: 

Thermal lift -+ 

Hot diisocyanate vapor 

or aerosol 

is lifted by the 

surrounding air 

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25 f..lg/m3 MDI ~~1il 4 meter 

14 f..lg/m3 MDI ~:5!!ft'3"':li!lf ':rnwr~ 3 meter 

11f..lg/m3 MDI &lliBBilfl 1.7 mete

7 llgfm3 MDI ground fl

Fraunhofe
Section V 

V Summary I Conclusions 

• 

BG 

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V Summary 

• Direct testing methods are not valid for validation of workplaces. 

• Direct testing methods can be used for a first estimation. 

• Indirect testing methods are accurate as long as skilled personne

them. 

• Diisocyanate air distribution is depending on many factors: 

- Kind of monomer 

Kind of adhesive 

Humidity 

Monomer content 

- Exhaustion 

- Application temperature 

Air volume 

Thermal lift 

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,.---- ___ 

V Conclusions 

Derived recommendations: 

exhaustion 

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better 

exha

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V Conclusions 

Derived recommendations : 

• Emission reduced adhesives 

• Low application temperature 

• Smart exhaustion 

• High enough air volume 

• Think about breakdown situation 

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..

. 

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Fraunhof
,.-

• 

BG 

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Thank you for your attention! 

Fraunhofe
• "--~/ BG Berufsgenossens.choft Druck und Popierverorbeitvng Fraunhof
Huntsman Division (PU, PP, AdMat) PU 

Region (US, EAME, Asia) EAME 

Product (OCF, SPF, SPF kits, FR resins, Polyurea, Adhesives, OCF & Adhesives 

Coatings, Elastomers, Sealants, Other) 

Is test data available? (If answer is "NO", please save this YES 

form and email it to Michelle Koenig. If"YES", continue 

survey). 

Is this information considered Confidential Business NO 

Information (CBI)? Yes or No 

Chemical Composition of the formulated products (e.g polyurethane 

polyurethane,_golyurea) 

BriefName of the study conducted (e.g. "Frankel Home Danish consumer study 

Testing"). 

1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 

2 Curing (surface) or Exposure (airborne)? Exposure/ curing 

3 Relevant Data Summary - Indicate variables studied e.g. 

environmental conditions, ventilation rates, temperature, 

humidity, catalysts/reactants present, proportioning/mixing, 

application site (indoors or outdoors); quantity of product 

used, application method and square footage covered. 

4 Test lab methods/ Instruments used/ Detection levels, QC OSHA47 

measures, levels of detection 1.2 PP HPLC-UV 

25 ng/ml 

Experimental Parameters ( sampling times, strategy) Car window adhesive 

sampling of 12 minutes 

Exposure during applying: Sample 

taken at breathing zone 

Sampling 6 minutes:as close as 

possible to product [worst case] 

Curing: directly after applying with 

new filter for 2 hours after 

applying 

OCF 

160-180 grs applied 

Sampling 25 em above product for 

15 minutes 

Floor adhesive 

200 grs over 25cm X40 em surface 

area. Sampling at 25 em above 

product for 15 minutes 

5 Summarized Test Data Results All results < detection limit 

6 Sensitivity Analysis (if any) 

7 Identify location of above data in document - Pages/Para (e.g. Pg22/23 

Pg2 Para4) Section 4.4 pg 41 

8 Was Reoccupancy time determined? No 

9 If answer to 8 is yes, indicate reoccupancy time. 
10 Exposure limits (occupational and general population limits) No EAME general population limit 

inEU 

11 Quantitative Testing: Indicate whether unreacted 

diisocyanates were present, type of surface, and results 

obtained at each interval measured 

12 Other Data on Curing: Tack Free time, cuttable, expansion 

time, light traffic, ready to use etc 

13 Data related to formation ofbyproducts, particularly 

substances that continue to off-gas over time. 

I 
i 

\ 

DANISH MINISTRY 

OF THE ENVIRONMENT 

Environmental 

Protection Agency 

Survey and health assessment of 

selected respiratory sensitizers in 

consumer products 

Helie Buchardt Boyd 

DTC Health and Environment 

Betty BOgel Mogensen 

National Environmental Research Institute 

Survey of Chemica I Substances in Consumer 

Products, No. 82 2007 
The Danish Environmental Protection Agency will, when opportunity 

offers, publish reports and contributions relating to environmental 

research and development projects financed via the Danish EPA 

Please note that publication does not signify that the contents of the 

reports necessarily reflect the views of the Danish EPA 

The reports are, however, published because the Danish EPA finds that 

the studies represent a valuable contribution to the debate on 

environmental policy in Denmark. 
Table of contents 

FOREWORD 

SUMMARY 

INTRODUCTION 

1 METHODS 

2 INVENTORY OF CONSUMER PRODUCTS, WHICH MAY 

5 

7 

9 

12 

CONTAIN ANY OF THE FIVE R42 SUBSTANCES 14 

2.1 GLUTARALDEHYDE, CAS 111-30-8 14 

2.1.1 Conclusion 15 

2.2 CYCLOHEXANE-1 ,2-DICARBOXYLIC ANHYDRIDE (UNSPEC.), CAS 

85-42-7 15 

2.2.1 Conclusion 16 

2.3 HEXAHYDR0-4-METHYLPHTHALIC ANHYDRIDE, CAS 19438-60-916 

2.3.1 Conclusion 17 

2.4 METHYL TETRAHYDROPHTHALIC ANHYDRIDE, CAS 11070-44-3 17 

2.4.1 Conclusion 18 

2.5 METHYLENE DIPHENYL DIISOCYANATE, CAS 26447-40-5; 5873-

54-1; 101-68-8 18 

2. 5.1 Conclusion 20 

2.6 RESULTSOFINQUIRIES 20 

2. 7 RESULTS OF SEARCH FOR PRODUCTS WITH LIKELY EMISSION OF 

THE FIVE SUBSTANCES 20 

3 RESULTS OF EMISSION ANALYSIS FROM SELECTED 

CONSUMER PRODUCTS 22 

3.1 ANALYSIS OF MDI EMISSION FROM VARIOUS CONSUMER 

PRODUCTS 22 

3.1.1 Sample treatment and collection 22 

POLYURETHANE ONE COMPONENT SEALANT AND ADHESIVE 23 

FLOOR ADHESIVE 

HAIR CONDITIONER 

23 

23 

HAIR SPRAY WITH POLYURETHANE AS DECLARED INGREDIENT24 

POLYURETHANE RAIN COAT 

FOAM MATTRESS AND SPRING MATTRESS 

3.1.2 Method of analysis 

EXTRACTION 

CHROMATOGRAPHY 

3.1.3 Calculation of detection limit 

3.1.4 Results 

24 

24 

25 

25 

25 

26 

26 

3 
3.2 ANALYSIS OF PHTHALIC ANHYDRIDE DERIVATIVES IN CONSUMER 

PRODUCTS 26 

3.2.1 Sample tl'eatment and collection 27 

3.2.2 Results of phthalic anhydl'ide measurements 30 

3.3 ANALYSIS OF GLUTARALDEHYDE IN CONSUMER PRODUCTS 32 

3.3.1 Results of glutal'aldehyde measurements 33 

4 EXPOSURE AND RISK ASSESSMENT 35 

4.1 CYCLOHEXAN-1 ,2-DICARBOXYLIC ANHYDRIDE (UNSPEC.), CAS 

85-42-7 35 

4.1.1 Hazards 35 

4.1.2 Limit values 36 

4.2 HEXAHYDR0-4-METHYLPHTHALIC ANHYDRIDE, CAS 19438-60-936 

4.2.1 Hazards 38 

4.2.2 Limit values 38 

4.3 PHTHALIC ANHYDRIDE, METHYL TETRAHYDRO- (UNSPEC.), CAS 

11070-44-3 38 

4.3.1 Hazards 40 

4.3.2 Limit values 40 

4.3.3 Exposul'e and l'isk assessment fol' consumel's fol' all the above 

phthalic anhydride derivatives 40 

4.4 METHYLENEDIPHENYLDIISOCYANATE, CAS 2644 7-40-5, 5873-54-

1 AND 101-68-8 41 

4.4.1 Hazards 42 

4.4.2 Limit values 43 

4.4.3 Exposul'e and J'isk characterisation for consumers 44 

4.5 GLUTARALDEHYDE, CAS 111-30-8 45 

4.5.1 Hazards 45 

4.5.2 Limit values 47 

4.5.3 Exposure and l'isk characterisation for consumers 47 

5 CONCLUSION 49 

6 REFERENCE LIST 51 

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Foreword 

This project was carried out with DTC Health and Environment, a business 

unit of 

DHI Water and Environment, as project leader, and NERI (National 

Environmental Research Institute) as partner. 

DTC carried out the initial search for relevant products containing respiratory 

sensitizers. 

Project assistant Hanne S0rensen, DTC, made the tracking and purchases of 

most of the products analyzed. 

Toxicologist Inge S0borg reviewed the first phase report. and Chief 

toxicologist Karl-Heinz Cohr carried out the quality control of the final 

report. 

Secretary Vibeke Salmon carried out the text editing and translation. 

At the NERI, Senior Scientist Betty BCtgel Mogensen, planned, executed and 

reported the chemical emission analysis with the aid of laboratory technicians 

Inga Jensen and Kitty Petersen. Quality control on the performed analyses 

was carried out by Betty BCtgel Mogensen. 

The project was carried out for the Danish Environmental Protection Agency 

(DEPA) on contract no. 7041-0513 under the programme for surveys on 

chemical substances in consumer products. 

The primary contact person in DEPA for this project was Annette Ejersted, 

who was initially seconded by Lea Frimann Hansen, and later Frank Jensen. 

The project was initiated in March 2006 with final delivery in November 

2006. 

5 
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Summary 

In 2004, the Danish EPA issued a revised list of unwanted substances 

(Orientering fra Milj0styrelsen, nr. 8, 2004). The criteria for inclusion in this 

list were among others the classification of the substances. One of the criteria 

was classification R42: "May cause sensitization by inhalation". Five 

substances are on the list exclusively because of this classification: 

Cyclohexan-1 ,2-dicarboxylic anhydride (unspec.), CAS 85-42-7 

Hexahydro-4-methylphthalic anhydride, CAS 19438-60-9 

Phthalic anhydride, Methyltetrahydro- (unspec.), CAS 11070-44-3 

Methylendiphenyldiisocyanate (MDI), CAS 26447-40-5, 5873-54-1 and 

101-68-8 

Glutaraldehyde, CAS 111-30-8 

The purpose of the present project was to 

1. Make an inventory of consumer product types that may contain any of 

the five R42-substances. 

2. Examine, if consumers actually are exposed to the substances when 

using such products. 

3. Assess, if the exposure is large enough to cause health effects in the 

consumers 

The inventory below was created by searching SPIN - database on substances 

in preparations in Nordic countries, the INCI list, and data from earlier 

projects on consumer products. In addition, five trade associations and retail 

stores were asked about their knowledge on the matter, and the literature was 

searched for cases of respiratory sensitization due to any of the five substances 

in consumer products. 

All in all, 19 products were sampled for inclusion in an emission analysis. The 

number of products within each group is given in parenthesis. 

The following consumer products may contain phthalic anhydride derivatives: 

• Nail Lacquer (6) 

• Two-component epoxy adhesive (2) 

The following consumer products may contain glutaraldehyde: 

• Cosmetic products (mouth washes and creams) (O) 

• Disinfectants (O) 

• Film developers for consumers (O) 

• Paper handkerchiefs and toilet paper (2) 

The following consumer products may contain monomeric MDI: 

• PU-foam articles, such as mattresses (2) 

• One component spray foam or adhesive (2) 

7 
• Boat and car repair kits (1) 

• Two-component adhesives and putties (O) 

• Liquid roof coating (O) 

• Hot melt adhesives (O) 

• Floor adhesives (1) 

• Polyurethane materials in clothing (1) 

• Spray hair fixatives and conditioner (2) 

When searching the market it was not possible to obtain cosmetic products, 

disinfectants, nor film developers with glutaraldehyde. Neither was it possible 

to obtain two-component adhesives and putties, liquid roof coating, nor hot 

melt adhesives with a content of monomeric MDI. 

All purchases were carried out while pretending to be ordinary consumers, not 

professionals. Although some of the outlets visited are also used by 

professionals, we were not offered products intended only for professionals. 

This indicates a fairly good separation between the markets for consumers 

and the markets for professionals, at least pertaining to these kinds of 

products. 

Emissions from the 19 products were analyzed under realistic and, in some 

cases also extreme use conditions. No emissions of the respiratory sensitizers 

from the 19 products obtained could be detected by chemical analysis. Hence, 

no risk of sensitisation to phthalic anhydrides, MDI or glutaraldehyde can be 

attributed to any of the products analyzed. 

8 

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Introduction 

In 2004, the Danish EPA issued a revised list of unwanted substances 

(Orientering fra Milj0styrelsen, nr. 8, 2004). The criteria for inclusion in this 

list were among others the classification of the substances. One of the criteria 

was classification R42: "May cause sensitization by inhalation". Five 

substances are on the list exclusively because of this classification: 

Cyclohexan-1 ,2-dicarboxylic anhydride (unspec.), CAS 85-42-7 

Hexahydro-4-methylphthalic anhydride, CAS 19438-60-9 

Phthalic anhydride, Methyltetrahydro- (unspec.), CAS 11070-44-3 

Methylendiphenyldiisocyanate (MDI), CAS 2644 7-40-5, 5873-54-1 and 

101-68-8 

Glutaraldehyde, CAS 111-30-8 

Exposure to these five substances through consumer products is virtually 

unknown, and the Danish EPA needs more knowledge of the use of these 

substances in consumer products, and the emission of the five substances 

from products containing the substances. 

The purpose of the present project was to 

1. Make an inventory of what kind of consumer products may contain 

any of the five R42-substances. 

2. Examine, if consumers are actually exposed to the substances when 

using such products. 

3. Assess, if the exposure is large enough to cause health effects in the 

consumers 

Products, which are exclusively used in the occupational setting and lead only 

to occupational exposure, are outside the scope of this project. 

The final goal of the project is to present an assessment of the health risk of 

the consumers from the five R42 substances. 

The project was divided into two phases: 

1. Inventory of the kind of consumer products, which may contain any 

of the five R42 substances 

2. Exposure assessment and assessment of health risks 

9 
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1 Methods 

For the phase 1 survey the occurrence of the five substances has been 

searched in the sources given below. 

Data on the use of the five respiratory sensitizers have been collected in SPIN 

-database on substances in preparations in Nordic countries. 

The INCI list (International Nomenclature of Cosmetic Ingredients) has been 

searched for occurrence of the five substances. 

In addition, data have been retrieved from earlier projects on consumer 

products published on the web page of the Danish Environmental Protection 

Agency. 

The following trade associations and retail stores have been requested to 

provide available data on the use of some or all of the five substances: 

Plastindustrien i Danmark 

Danmark Farve- og Lakindustri 

COOP Danmark 

Dansk Supermarked 

Association of Danish Cosmetic, Toiletries, Soap and Detergent Industries 

(SPT) 

Glutaraldehyde has been searched on the Internet via Coogle using the search 

words "disinfection" and "glutaraldehyde". 

In the database PubMed, additional searches have been made for cases of 

respiratory sensitization due to any of the five substances in consumer 

products. 

After having established the type of consumer products most likely containing 

the five substances, products have been searched and sampled by personal 

purchase in retail outlets, both physically and on the Internet. 

The purchased products were delivered to the National Environmental 

Research Institute for emission analysis. 

12 

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13 
2 Inventory of consumer products, 

which may contain any of the five 

R42 substances 

2.1 Glutaraldehyde, CAS 111-30-8 

Synonyms: Glutaral; 1 ,5 pentanedial 

The SPIN database has registered 428 preparations with glutaraldehyde in 

Finland, Norway, Sweden and Denmark in 2003. Ofthese, 139 preparations 

are registered in Denmark. Some of the 428 preparations are registered as 

consumer preparations in Norway and Sweden. The industrial use for which 

the preparations are registered in Denmark is: 

• Farming of animals 

• Hospital activities 

• Human and health services 

• Manufacture of paints, varnishes and similar coating, printing inks and 

mastics 

• Manufacture of food and beverages 

• Dentists 

• Painting 

• Manufacture of machinery and equipment 

• Other motor vehicle services 

• "All kinds of activities" 

• Private households with employed persons 

The use category for which the preparations have been registered in Denmark 

is: 

• Non-agricultural pesticides and preservatives 

• Biocides - pesticides for non-agricultural uses 

• Reprographic agents 

• Photochemicals 

• Developers - for developing pictures, but not photographic film 

• Paints, lacquers and varnishes 

• Colouring agents 

• Cleaning/washing agents 

• Disinfecting agents 

Glutaraldehyde is permitted in cosmetics as a preservative (no. 26, VI, 1 ,48). 

The maximum permitted concentration is 0.1% and it is banned in aerosol 

and spray products. Labelling with "Contains glutaraldehyde" is mandatory, 

if the concentration in the final products exceeds 0.05%. 

The INCI name for glutaraldehyde is Glutaral. 

14 

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The search on the internet by Coogle for disinfectants containing 

glutaraldehyde gave only products intended for use in food industry and 

agriculture. No sale to private consumers could be identified. 

A search for glutaral on the internet by Coogle turned up one body lotion 

containing Glutaral. This body lotion was sold from a French internet page, 

claiming that it helps against staphylococci adherence to the skin. 

A search among the previous surveys of chemical substances in consumer 

products revealed that glutaraldehyde residues may be present in paper 

handkerchiefs and toilet paper in concentrations of up to 0.08 kg/t (1). 

An additional search for cases of respiratory allergy resulting from exposure to 

glutaraldehyde emission from consumer products was carried out in the 

database PubMed. Several cases of asthma resulting from occupational 

exposure to glutaraldehyde containing disinfectants were found, but none 

were related to private use. Cases of exposure to glutaraldehyde in the private 

setting, were only found in relation to contact dermatitis, but not to 

respiratory hypersensitisation. 

2.1.1 Conclusion 

With regard to glutaraldehyde containing consumer products, we should look 

for: 

• Cosmetic products (mouth washes and creams) 

• Disinfectants 

• Film and picture developers for consumers 

• Paper handkerchiefs and toilet paper 

2.2 Cyclohexane-1,2-dicarboxyl ic anhydride (unspec.), CAS 85-42-7 

Synonyms: hexahydro-1 ,3-isobenzofurandione 

hexahydrophthalic anhydride 

The SPIN database has registered 57 preparations with cyclohexane-1, 2-

dicarboxylicanhydride (CDA) in the Nordic countries in 2003. Of these, 38 

preparations are registered in Denmark. None of the 57 preparations are 

registered as consumer preparations. The industrial use for which the 

preparations are registered in Denmark is: 

• Manufacture of other transport equipment 

• Sale, maintenance and repair of motor vehicles and motor cycles; retail 

sale of automotive fuel 

• Manufacture of aircraft and spacecraft (includes repair of air planes (2)) 

• Motor vehicle painters 

The use category for which the preparations have been registered in Denmark 

is: 

• Paints, lacquers and varnishes 

In Sweden, CDA is also used for curing agents in plastic. 

15 
Hence, CDA may occur as a residual monomer in consumer products. 

In cosmetics, CDA may occur as a monomer in different film forming 

polymers used in e.g. nail lacquer. CDA as such is not found on the INCI list. 

In a declaration, it might be listed as phthalic anhydride in the kind of polymer 

used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. 

We do not know if CDA or only phthalic anhydride is actually employed in 

the phthalic anhydride copolymers. 

In 2002, the information centre for Environment and Health published a list 

of products containing unwanted substances. Among these were nine nail 

lacquers containing phthalic anhydride according to the product declaration 

(3). 

An additional search in PubMed for cases of respiratory sensitization gave 

several hits indicating that occupational exposure to epoxy resins and their 

hardeners is a common reason for respiratory sensitization to CDA (4,5,6). 

No cases of CDA allergy from private use of epoxy products were found in 

the PubMed database. However, as two-component epoxy products are 

available for private use, some of these were sampled for CDA emission 

testing. 

2.2.1 Conclusion 

With regard to CDA containing or -emitting products, two-component epoxy 

adhesives and nail lacquer were considered relevant for emission analysis. 

2.3 Hexahydro-4-methylphthal ic anhydride, CAS 19438-60-9 

Synonyms: Hexahydro-4-methylphthalsyreanhydrid, 

Hexahydro-5-methyl-1 ,3-isobenzofurandione 

In 2003, the SPIN database has registered 3 preparations with hexahydro-4-

methylphthalic anhydride (HMPA) in the Nordic countries. None of these 

were registered in Denmark. In fact, all three were registered in Sweden, and 

none of these were consumer preparations. 

Industrial use categories are: 

• Manufacture of chemicals and chemical products 

• Manufacture of rubber and plastic products 

• Manufacture of electrical machinery and apparatus 

• Heat transferring agents 

• Adhesives, binding agents 

Hence, HPMA may occur as a residual monomer in consumer products. 

In cosmetics, HPMA may occur as a monomer in different film forming 

polymers used in e.g. nail lacquer. HPMA as such is not found on the INCI 

list. On a declaration, it might be listed as Phthalic anhydride in the kind of 

16 

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polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane 

Copolymer. 

We do not know if HPMA or only phthalic anhydride is actually employed in 

the phthalic anhydride copolymers. 

In 2002, the information centre for Environment and Health published a list 

of products containing unwanted substances. Among these were nine nail 

lacquers, which contained phthalic anhydride according to the product 

declaration (3) . 

Ari additional search in PubMed for cases of respiratory sensitization gave a 

few hits indicating that occupational exposure to epoxy resins, their 

hardeners, and unsaturated polyester resins (UP resins) is a common reason 

for respiratory sensitization to HPMA (5,7,8). No consumer product related 

cases were found during this search. 

2.3.1 Conclusion 

With regard to HPMA containing or -emitting products, we decided to 

sample 

two-component epoxy adhesives and nail lacquer. 

2.4 Methyltetrahydrophtha I ic anhydride, CAS 11070-44-3 

Synonyms: MTHPA 

tetrahydromethyl-1, 3-iso benzofurandione 

In 2003, the SPIN database has registered 5 preparations with 

methyltetrahydrophthalic anhydride (MTHPA) in 2003. None ofthese were 

registered in Denmark. In fact, all five were registered in Sweden. and none of 

these were consumer preparations. 

Industrial use categories are: 

• Manufacture of chemicals and chemical products 

• Manufacture of rubber and plastic products 

• Manufacture of electrical machinery and apparatus 

• Process regulators 

• Heat transferring agents 

• Curing agents for plastic 

• Others not mentioned specifically 

Hence, MTHPA may occur as a residual monomer in consumer products. 

In cosmetics, MTHP A may occur as a monomer in different film forming 

polymers used in e.g. nail lacquer. MTHPA as such is not found on the INCI 

list. On a declaration, it might be listed as phthalic anhydride in the kind of 

polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane 

Copolymer. 

17 
We do not know if MTHPA or only phthalic anhydride is actually employed 

in the phthalic anhydride copolymers. 

In 2002, the information centre for Environment and Health published a list 

of products containing unwanted substances. Among these were nine nail 

lacquers containing phthalic anhydride according to the product declaration 

(3). 

An additional search in PubMed for cases of respiratory sensitization gave a 

few hits indicating that occupational exposure to epoxy resins, their 

hardeners, and unsaturated polyester (UP) resin is a common reason for 

respiratory sensitization to MTHPA (5,7,8). No consumer product related 

cases were found during this search. 

2.4.1 Conclusion 

In conclusion, with regard to MTHP A containing or -emitting products, we 

decided to sample two-component epoxy adhesives and nail lacquer. 

2.5 Methylene diphenyl diisocyanate, CAS 26447-40-5; 5873-54-1; 101-68-8 

Synonyms: 1, 1 '-methylenebis (isocyanato) benzene, 

MDI 

In 2003 The SPIN database has registered 308 preparations with MDI in The 

Nordic countries. Ofthese, 148 preparations are registered in Denmark. 

Some of the 308 preparations are registered as consumer preparations in 

Norway and Sweden. The industrial use for which the preparations are 

registered is: 

• Construction 

• Manufacture of motor vehicles, trailers and semi-trailers 

• Manufacture of basic metals 

• Manufacture of furniture 

• Manufacture of rubber and plastic products 

• Manufacture of wood and products of wood and cork, except furniture; 

manufacture of articles of straw and plating materials 

• Wholesale trade and commission trade, except of motor vehicles and 

motorcycles 

• Private households with employed persons . 

• Sale, maintenance and repair of motor vehicles and motorcycles; repair of 

personal and household goods 

• Manufacture of electrical machinery and apparatus 

• Manufacture of pulp, paper and paper products 

• Manufacture of chemicals and chemical products 

• Manufacture of other transport equipment 

• Floor and wall covering except floor planning 

• Joinery installation 

• Painting 

The use categories for preparations registered in Denmark are: 

• Paints, lacquers and varnishes 

18 

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• Adhesives, binding agents 

• Curing agents 

• Construction materials 

• Process regulators 

• Fillers 

• Flooring materials Qoint-less floors) 

Deeming from this, MDI or residues of MDI might be emitted from 

consumer products, such as boat and car repair kits, furniture (mattresses), 

two-component adhesives and putties, flooring and wall paper. Polyurethane 

materials in clothing may also emit MDI. 

Secondary exposure to MDI may occur when polyurethane materials are 

processed by grinding or heating (9). 

MDI has been subject to an EU risk assessment, published in 2005 (10). One 

of the conclusions for consumers was that there is a need for limiting risks, 

since health risks due to combined occupational and consumer exposure 

could not be excluded with regard to sensitization (dermal contact and 

inhalation exposure). 

In the EU risk assessment report, possible exposure to free MDI from the 

following products has been identified: 

• Spray (PU-foam) 

• Putty/filler in cartridge 

• Liquid glue for wood 

• Paints 

Spray foam or One Component Foam (OCF): MDI-based OCF is offered in 

the consumer market and to professional tradesmen for use as a filler in small 

gaps in buildings (e.g. around window frames, between floor boards etc). In 

this context, the word 'spraying' is not entirely appropriate. The OCF is 

supplied in pressurised cans and is applied through a pre-expansion tube 

(always part of the package). The product is released from the nozzle as 

viscous foam, rather than as a sprayed aerosol. Curing starts immediately and 

moves from the outside inwards. Therefore, emission and hence potential 

exposure virtually ceases once the outer coat has been cured. However, 

Sweden has a warning when using the one-component frothed foam. 

PU wood adhesives are used for waterproof bonding and on moist wood. 

Flooring adhesives are used for wood-parquet. 

PU paint is used as a primer for liquid roof coating, with a long in-service life 

( 10 to 15 years), and for decorative painting. It is confirmed by industry that 

hot melt adhesives are currently offered to the D.I.Y. (do-it-yourself) market. 

According to industry, even 2-component products are offered to the D.I.Y. 

market. One company stated: 

"Moreover, other products normally offered only to the craftsmen can reach 

end-consumers by self-service at craftsmen retailers". However, it is very 

unlikely that the consumer's working conditions are ever appropriate for the 

use of 2-component products containing free MDI (10). 

19 
A search in the INCI list for the three CAS numbers connected with MDI 

showed no result. A second search on "MDI" gave three copolymers, in 

which MDI may have been used, and may therefore emit residual monomer: 

PEG-8/SMDI copolymer, CAS 39444-87-6 

PPG-12/SMDI copolymer, CAS 9042-82-4 

PPG-51/SMDI copolymer, CAS 9042-82-4 

These substances are copolymers of the respective PEG's and saturated MDI 

monomer. They are used as hair conditioning agents, hair fixative, plasticizer, 

skin-conditioning agent (emollient and miscellaneous), in eye shadows, 

foundations, miscellaneous makeup preparations , and moisturizing 

preparations (11). 

Since the present project deals with the substances as respiratory sensitizers 

we considered it prudent to test the emission of MDI from aerosol hair 

fixatives with the above mentioned polymers on the ingredient list. 

2.5.1 Conclusion 

With regard to MDI containing and -emitting products, we decided to look 

for samples of the following products: 

• PU-foam articles, such as mattresses 

• One component spray foam 

• Boat and car repair kits 

• Two-component adhesives and putties 

• Liquid roof coating 

• Hot melt adhesives 

• Floor adhesives 

• Polyurethane materials in clothing 

• Spray hair fixatives 

2.6 Resu Its of inquiries 

Answers to general inquiries about the knowledge of inclusion of any of the 

five substances in consumer products were given from: 

COOP 

Dansk Supermarked A/S 

The Association of Plastic Industries in Denmark. 

Danmarks Farve- og Lakindustri 

Association of Danish Cosmetic, Toiletries. Soap and Detergent Industries 

(SPT) 

None of these respondents were aware of the presence of any such products 

on the Danish market. 

2.7 Resu Its of search for products with I ikely emission of the five 

substances 

Glutaraldehyde 

20 
The search for products containing glutaraldehyde was very difficult. The 

search for film and picture developers with content of glutaraldehyde, and not 

exclusively for occupational use, was negative after several telephone 

inquiries .. One inquiry led us to a company who thought they might provide a 

developer with glutaraldehyde for youth schools with classes in photography. 

However, upon further investigation, this company was not able to deliver any 

such developer. Upon this, we concluded that the use of glutaraldehyde in 

developers for hobby use seems to have been phased out. 

Next, we thought glutaraldehyde might be present in disinfectants for home 

use or mouth washes. Telephone inquiries and store searches revealed no 

such thing. 

Finally, since glutaraldehyde according to our investigation may be found in 

paper towels and paper handkerchiefs we purchased some toilet paper and 

some kitchen rolls made of recycled paper. 

Phthalic anhydride derivatives 

Two component epoxy adhesives were readily available from do-it-yourselfmarkets, so samples of these products were purchased and sent for analysis 

for emission phthalic anhydride derivatives. 

Nail lacquers containing polymers based on phthalic anhydride derivatives 

were identified in stores by scrutiny of the INCI declaration. The nail lacquers 

were chosen according to place of the polymers in the INCI declaration, since 

ingredients are supposed to be mentioned in order of falling concentration. 

Hence, if the polymer is mentioned as one of the first ingredients the nail 

lacquer was preferred for sampling rather than the one where the polymer was 

mentioned later. This was thought to give the best chance of measuring the 

emission, if any would be present. 

MDI 

Consumer products made with polyurethane, MOl-copolymer or MDI was 

easier to find, although some discrepancy in information regarding the 

content of residual MOl-monomer in adhesives and joint fillers were found. 

Cosmetic products were sampled if the ingredient list contained MDI based 

polymers or copolymers. 

We purchased samples of car window adhesive, floor adhesive, joint filler, 

PU-rainjacket, hairspray and conditioner, and mattresses. 

21 
3 Results of emission analysis from 

selected consumer products 

The products that were purchased and submitted for analysis are listed in 

annex 2. 

3.1 Ana lysis of MDI emission from various consumer products 

Collection and analysis of air samples were carried out according to OSHA 

(Occupational Safety and Health Administration, U.S. Department of 

Labour), method 4 7 for analysis of MD I in the occupational environment. 

Air samples are collected by sucking a known amount of air through a glass 

fibre filter, which is coated with 1-(2-pyridyl)piperazin (l-2PP). Together 

with MDI 1-2PP forms a complex, which absorbs UV-light. The filter is 

extracted with acetonitril:dimethylsuphoxide (90: 10) and is analysed by 

HPLC with UV detector (254 nm). 

3.1.1 Sample treatment and collection 

The purpose of the collection was to treat the sample in a way as close to the 

user situation as possible. 

Car window adhesive 

A car window was placed on a table (see figure 1). The sample was opened, 

and the adhesive was squeezed out of the container with a joint gun while 

distributing it along the edge of the window pane. After this, the adhesive was 

covered with the moulding that protects the window pane during transport, 

mimicking the placement of the window in the car frame (realistic work 

scenario). 

During the out-squeezing and distribution of the adhesive, air was sampled 

from a height equal to the position of the nose of the user. Application of the 

adhesive lasted 12 minutes (realistic work scenario). 

After this, the filter was exchanged with an un-exposed filter, and air was 

sampled right over the adhesive in nose height for two hours. 

The remainder-·of the adhesive was squeezed out of the container, and air was 

sampled over the adhesive for six minutes (maximum exposure). 

22 
Figure 1. Application of adhesive to car window 

Polyurethane one component sealant and adhesive 

Sealant (160-180 g) was squeezed out in stripes on a non-absorbing surface 

placed in a plastic tray (see figure 2 below). Collection of sample was carried 

out 25 em above the sealant. The collection of air and expression of sealant 

was started simultaneously and continued for 15 minutes. 

Floor adhesive 

Approximately 200 g of the thin fluid adhesive was spread over an area of 

approximately 25x40 cm2

• (see figure 2 below). Suction took place 25 em 

above the surface for 15 minutes counting from the opening of the bottle. 

Hair conditioner 

A large handful of conditioner (app. 25 g) was spread over an area of app. 

25x30 cm2 (see figure 2 below). Air was collected 25 em above the area for 15 

minutes counting from the opening of the container. 

23 
Figure 2. Hair conditioner. The plastic tray with non-absorbing material was used for sealant. 

adhesive, hair conditioner, and hair spray. 

Hair spray with polyurethane as dedared ingredient 

Hair spray was sprayed out over a non-absorbing surface of 25x30 cm2 

placed in a plastic tray (see figure 2 above). Spray for 10 seconds, pause for 

10 seconds, and spray for 10 seconds. Air was collected 25 em above the area 

for 15 minutes. 

Polyurethane rain coat 

Collection of air was started as soon as the plastic bag around the rain coat 

was opened. The rain coat was spread out and turned over and around several 

times during the air collection. Air was collected 25 em above the rain coat for 

15 minutes. 

Foam mattress and spring mattress 

Collection of air was started when the plastic cover was removed. The 

mattress was placed on the floor, and air was collected 25 em above the 

surface for 7 hours (see figure 3 below). During this time the mattress was sat 

on and walked on every half hour. 

The sampling air flow velocity was 1 Llmin in all samplings. 

24 
Figure 3. Collection of air sample over mattress. 

3.1.2 Method of analysis 

Extraction 

The filters were extracted with 4 mL acetonitril:dimethyl sulfoxide (90: 1 O). 

Chromatography 

The extract was analyzed on HPLC (Agilent 11 00) 

Method 1: 

Column: Zorbax XDB 5f1 C8 from Agilent, length 150 mm, diameter 4,6 

mm. Mobile phase: 50% acetonitril and 50% O,OSM ammoniumacetate in 

MilliQ water (pH 6.07), isocratic. Flow velocity 1 mL/min. Temperature 25° 

C. Injection volume 25 fll. 

Retention time 4.333 min. 

Method 2: 

Column: Prodigy, 5f1 from Phenomenex, length 250 mm, diameter 4,6 mm. 

Mobile phase 50% acetonitril, 50% ammoniumacetate in MilliQ water (pH 

6.07), isocratic. Flow velocity 1 mL/min. Temperature 25° C. Injection 

volume 25 fll. 

Retention time 10.98 min. 

Detection 

Detection was carried out at 254 nm on a G1314A VWD variable wavelength 

detector from Agilent. 

The extracted samples were analyzed against a row of standard solutions of 

MDI derivatized with 1-2PP in the concentrations 10, 25, 50, 100, 250, and 

500 ng/ml. The standard curve was linear within the entire concentration 

span. 

The lowest concentration of standard solution which gave a signal 

significantly different from the base line was 25 ng/ml. 

25 
3.1.3 Calculation of detection limit 

The detection limit depends on the collected amount of air. Collection in 12 

minutes corresponds to 12litres of collected air. 

The filter was extracted with 4 ml of solvent. 25 ng/ml in 4 ml corresponds to 

100 ng in 12 1 of air, corresponding to 8 ng/ 1 air or 8 pg/m3 of air. 

The detection limits for the different analyses appear from table 1 below. 

3.1.4 Results 

In some of the chromatogrammes, which were obtained by the HPLC method 

1. one peak was situated very close to the MDI peak. All samples were 

therefore reanalyzed with HPLC method 2, which showed that there was no 

MDI in any of the samples. The analytical result for the collected air samples 

are shown in table 1 below. 

Table 1 Concentration of MDI in the collected air samples 

Sample DMU no. Collected Concentration of Limit of 

amount of air, MDI, !191m3 detection 

L f.J~/m3 

1 ATMI 12 n.d. 8 

Car window adhesive 2006-460 

Realistic work scenario 

1 - 120 n.d. 0.8 

2 hours following work 

process 

1 - 6 n.d. 17 

Maximum exposure 

11 ATMI 15 n.d. 7 

Sealant 2006-918 

17 ATMI 15 n.d. 7 

Adhesive /sealant 2006-924 

6 ATMI 15 n.d. 7 

Floor adhesive 2006-913 

5 ATMI 15 n.d. 7 

Hair conditioner 2006-912 

4 ATMI 15 n.d. 7 

Hair spray 2006-911 

9 ATMI 15 n.d. 7 

Rain coat 2006-916 

19 ATMI 420 n.d. 0.2 

Foam mattress 2006-

1037 

18 ATMI 420 n.d. 0.2 

Spring mattress 2006-

1038 

3.2 Analysis of phthalic anhydride derivatives in consumer products 

The following phthalic anhydride derivatives are comprised by the analytical 

method: 

Cyclohexane-1 ,2-dicarboxylic anhydride (unspec.) (HHPA), CAS 85-42-7 

Hexahydro-4-methylphtalic anhydride (HHMPA), CAS 19438-60-9 

Methyltetrahydrophtalic anhydride (unspec.) (MTHPA), CAS 11070-44-3 

Collection and analysis of phthalic anhydride derivatives was carried out after 

a method described by Welinder and Gustavsson in 1992 (12). The method 

26 
was described for MTHP A. but it is also applicable to other phthalic 

anhydride derivatives. 

Air samples were collected by sucking a known amount of air through a little 

glass column packed with glass wool and two layers of XAD-2, which adsorbs 

the anhydrides. XAD-2 is extracted with toluene which is analyzed for 

phthalic anhydride derivatives by gas chromatography with mass 

spectrometry detection (GC-MS). 

3.2.1 Sample treatment and collection 

The purpose of the sample collection was to treat the samples in a way, which 

as close as possible to the normal way of application. 

Nail Lacquer 

A glass plate was placed on top of a drawing of ten rectangles the size of 

fingernails (1.2 em x 2 em). Nail Lacquer was applied in an even, thick layer 

with the supplied brush, which was dipped in the bottle. Air was collected 25-

32 em above the glass plate for 10 min., and the pump was started when the 

bottle was opened and the application started (see figure 4 below). 

In addition, 10 drops of nail lacquer was put on a watch glass, and air was 

sucked from right above the watch glass for 10 min. to simulate maximum 

exposure. 

27 
Figure 4: Application of nail lacquer on glass plate. Air is sucked through XAD-2 column, which is 

placed in nose height over the nail lacquer. 

Epoxy adhesive 

Epoxy adhesive is a two-component adhesive. Half of each tube was squeezed 

out on a glass plate, and the two parts were mixed with the supplied spatula or 

a cotton swab. As long as the adhesive was liquid, it was used for gluing 

various surfaces (app. 8 min.). The air sample was taken in nose height above 

the work surface for 1 0 minutes with start of the pump when the adhesive was 

first squeezed out (see figure 5 below) 

Figure 5: Application of epoxy adhesive. Air is sucked through an XAD-2 column, which is placed in 

nose height above the work surface. 

The sampling air flow velocity was 1 !/min during all collections. 

Control of method 

A standard solution of the three phthalic anhydride derivatives in toluene was 

aerated with nitrogen at 3 7° C. Air was collected just above the surface for 1 0 

min. During this a part of the anhydrides were liberated, and it was made 

possible to perform a positive qualitative control of the method of collection 

and extraction. 

Analytical method 

Extraction: The tips of the XAD-2 column were removed with a pair of pliers. 

500 pL toluene was added and the content of the column (XAD and glass 

wool) was pushed out into a 4 mL capped vial and the column was rinsed 

with an additionalSOO pL of toluene. The extraction was performed for 20 

minutes in ultrasound bath. The toluene extract was aspirated with a 1 mL 

plastic syringe and filtered through a 0.2 pm filter. 

28 

\ 

) 
Chromatography: The extracts were analyzed by GC-MS (Turbomass from 

Perkin Elmer) 

Column: Rtx 200 MS from Retstek, length 30m, diameter 0.25 mm, film 

thickness 0.25)lm. Carrier gas: helium with a flow velocity of 2 mL/min. 

Injection volume 1)1L. Injection temperature 300° C. Temperature program 

of the oven: 100° C for 5 minutes increasing to 230° C with so C a minute, 

hold for 10 minutes, then increasing to 280° C with 25° C a minute, hold for 

10 minutes. The column was changed to a new one of same type after analysis 

of the two first samples. 

Detection: The substances were detected by mass spectrometry after electro 

impact (EI+) ionisation. Collection of masses appears from table 2 below. 

29 
Table 2: Analysis parameters for phthalic anhydrides on GC-MS 

Substance CAS nr Collection time Retention time Mass 

[Minutes] [Minutes] m/z 

Cyclohexane-1,2- 85-42-7 7-12 11.43 54 

dicarboxylic 67 

anhydride (unspec.) 82 

(HHPA) 

Hexahydro-4- 19438-60-9 12-18 12.72 54 

methyl phthalic 12.79 81 

anhydride 96 

(HHMPA) 

Methyltetrahydroph 11070-44-3 12-18 12.94 79 

thalic anhydride 13.01 93 

(unspec.) 13.36 94 

(MTHPA), 

The samples were analyzed against a series of standard solutions of 1, 5, 10, 

50, and 100 ng/mL. The calibration curve was linear in the entire area of 

measurement. The lowest concentration of standard solution, which gave a 

signal significantly different from the noise on the baseline was 5 ng/mL. 

Calculation of detection limit 

The detection limit depends on the collected amount of air. In the realistic 

work scenarios the exposure time was 8-10 minutes corresponding to 8-10 

litres of air. 

The column was extracted with 1 mL solvent. 5 ng/mL in 1 mL corresponds 

to 5 ng in 8-10 L of air corresponding to 0.5-0.6 j.lg/m3 of air. 

3.2.2 Results of phthalic anhydride measurements 

The chromatogrammes for a standard solution and the method control run 

before change of GC column is seen in figure 6 and 7 below. 

11.43 10 

'A 

1 .77 

1 .7 

1 .94 

std 500 ppb 

Figure 6: Chromatogram of standard solution of the three phthalic anhydride derivatives. 

30 
max std test 

11.44 10 1 .80 

12. 3 13.38 

o-l;:;:;;;;:;;;;;:;;:;:;;:;:;;,.,..,..,.....,;:;:;;=;:;;;;:;;:;;:;:;;:;;;:....,......,.._,..,.,.,... ....... ...,......,......,.,..,.,..,....,....,.......,,...,..,.....,.....,........,....,...,""T'"'..,...."1' Time 

11.00 11.20 11.40 11.60 11.80 12.00 12.20 12.40 12.60 12.80 13.00 13.20 13.40 13.60 13.80 14.00 

Figure 7: Chromatogram for control of method for collection and extraction of three phthalic 

anhydride derivatives. 

None of the phthalic anhydride derivatives were detected in any of the air 

samples (see table 3 below) 

Table 3: Concentration of phthalic anhydride in selected products 

DMU Collected Concen- Detection 

no. amount of air tration limit 

[L] [JJg/m3] 

2 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

461 

3 ATMI 10 n.d. 0.5 

Two-component adhesive 2006-

462 

10 ATMI 10 n.d. 0.5 

Two-component adhesive 2006-

917 

12 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

919 

13 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

920 

14 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

921 

15 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

922 

16 ATMI 10 n.d. 0.5 

Nail lacquer 2006-

923 

31 
3.3 Analysis of glutaraldehyde in consumer products 

Collection and analysis of air samples was carried out according to OSHA 

method 64 (13) for analysis of glutaraldehyde in the occupational 

environment. 

Air samples were collected by sucking a known amount of air through a silica 

column (Sep-Pak) coated with 2,4-dinitrophenylhydrazine (DNPH). 

Together with DNPH glutaraldehyde forms a derivative, which can be 

analyzed by HPLC and UV -detection. 

Sample treatment and collection 

The intention with the air collection was to treat the sample in a way that 

closely resembles the use scenario. 

Kitchen roll 

Collection of air was begun when the package of 4 kitchen rolls was opened. 

One roll was rolled out and crumpled up as if it was going to be used for 

wiping, while the three other rolls were left standing on the table. The 

collection time was 10 minutes. 

Toilet paper 

Collection of was begun when the package of 8 toilet rolls was opened. All 8 

rolls were put out on the table. One roll was unrolled partly (approx. 2 m). 

The other rolls were squeezed and turned somewhat during the first 5 

minutes. The collection time was 10 minutes. 

The flow velocity of the air sampling was 1 Llmin. at all collection sessions. 

The collection was performed with Sep-Pak DNHP-Silica cartridge from 

Waters (14). 

Analytical method 

Elution: the Sep-Pak column was eluted with 5 ml of acetonitril. 

Chromatography: The eluate was analyzed on HPLC (Agilent 11 00) 

Column: Nova-pak, 4]1 C18 from Waters, length 150 mm, diameter 3,9 mm. 

Pre column C18 (Waters). 

Method 1 

Mobile phase A: 100% acetonitril, B: 0, 1% phosphoric acid in Milli-Q water. 

Flow velocity 1,0 mVmin. Gradient: 55% A increasing to 100% A at 8 

minutes. Falling to 55% A at 9 minutes, hold until20 min. 

Method2 

Mobile phase A: 100% acetonitril, B: 50% metanol +50% MilliQ water. Flow 

velocity 1 mL!min. Gradient: 40% A increasing to 100% A at 40 min. Falling 

to 40% A at 41 min, hold until 55 min. 

Temperature 25° C. Injection volume: 20 ]11. 

Detection: The samples were detected at 360 nm on a G 1314A VWD 

variable wavelength detector from Agilent. Retention time: 5.66 minutes. 

The samples were analyzed with elution method 1 against standard solutions 

of 10, 25, 50, 100, 250, and 500 ng/mL. The calibration curve was linear in 

the entire measuring range. The lowest concentration of standard solution, 

32 

\ 

! 
which gave a signal significantly different from the noise on the base line, was 

10 ng/mL. 

With elution method 1, the samples and the blank gave a signal in the 

chromatograms close to glutaraldehyde. The samples were therefore analyzed 

again with elution method 2, and all samples were analyzed with and without 

spiking with 500 ng/ml glutaraldehyde. Elution method 2 could separate 

glutaraldehyde from the peak in the samples. Hence, this peak does not come 

from glutaraldehyde. The applied method of analysis detects a host of 

aldehydes and ketones, and one of these may have been present in the 

ambient air. 

Calculation of detection limit 

The detection limit depends on the collected amount of air. At the realistic use 

scenarios the exposure time was 10 minutes corresponding to 1 0 L of air. 

The column was extracted with 5 mL of solvent. 10 ng/mL in 5 mL 

corresponds to 50 ng in 10 L air corresponding to 5 pg/m3 air. 

3.3.1 Results of glutaraldehyde measurements 

Table 4. Concentration of glutaraldehyde in selected consumer products 

Product DMU no. Collected Concen- Limit of detection 

volume of tration [!Jglm3] 

air [L] 

7 ATMI 10 n.d. 5 

Kitchen roll made from 2006-914 

recycled paper 

8 ATMI 10 n.d. 5 

Toilet paper made from 2006-915 

recycled paper 

33 
34 
( 

\ 4 Exposure and risk assessment 

4.1 Cyclohexan-1,2-dicarboxyl ic anhydride (unspec.), CAS 85-42-7 

Synonyms: hexahydrophthalic anhydride, HHPA 

hexahydro-1 ,3-isobenzofurandione 

Molecular formula: C8H100 3 

Molecular weight: 154.1 7 

Structural formula: 

0 () 0 

Cyclohexan-1,2-dicarboxylic anhydride (HHPA) is a solid substance at room 

temperature. (15). 

Melting point: 34° C (15) 

Vapour pressure: 0. 01 hPa at 20° C ( 15) 

Boiling point: 296° Cat 1013 hPa (15) 

Vapour density: not found 

Water solubility: very low solubility in water, and is slowly reacting with water 

(15). 

Odour threshold, air: not found 

Conversion factor at 20° C, 1 atm.: 1 ppm= 6.293 mg/m3 

1 mg/m3 = 0.159 ppm (16) 

4.1.1 Hazards 

Cyclohexan-1, 2-dicarboxylic anhydride (HHP A) has the following 

classification: 

Xi: Irritant 

Xn: Sensitising 

R41: Risk of serious damage to eyes 

R42/43: May cause sensitization by inhalation and skin contact 

The occurrence of HHPA in chemical consumer products (preparations), 

other than cosmetics, will not appear on the labeL when the concentration is 

below 0.1%. 

35 
As other cyclic acid anhydrides, HHPA is an irritant because of formation of 

corresponding acids in wet surroundings. 

HHP A rarely ~nduces contact allergy of the skin (delayed type 

hypersensitivity), but more easily induce IgE-mediated contact urticaria. This 

only comes about after initial respiratory sensitization, and subsequent skin 

contact. 

The mechanism of respiratory sensitization is mainly IgE mediated allergy 

both in animal studies and when exposed workers have been investigated. In 

the respiratory challenge tests bronchial obstruction has been verified, as well 

as development of inflammation (16). 

HHPA has caused both sensitization and work-related symptoms at exposure 

levels as low as 10-50 ]1g/m3

• The level of exposure needed to cause specific 

IgE antibody production and work-related symptoms in mucous membranes 

and respiratory organs may be less than 10 ]1g/m3 ( 16). No information on the 

duration needed to induce respiratory sensitization was found. 

There is cross sensitivity to MHHPA (see below). 

The critical effect is sensitization. 

4.1.2 Limit values 

No health based limit values for HHPA have been found, but a limit value 

should be below 10 ]1g/m3 to ensure absence of sensitizing effect. 

4.2 Hexahydro-4-methylphtha I ic anhydride, CAS 19438-60-9 

Synonyms: MHHP A. 5-methyl- hexahydro-1 ,3-isobenzofurandione 

Molecular formula: C9H1

P3 

Molecular weight: 168.19 

Structural formula: 

0 

MHHPA is an oily liquid at room temperature. 

Melting point: - 30° C- -29° C (16, 17) 

Boiling point: 120° C at 130 Pa ( 16) 

Vapour density: not found 

Vapour pressure: not found 

Water solubility: 36 g/1 at 20° C (17) 

Odour threshold, air: not found 

Conversion factor at 20° C, 1 atm.: 1 ppm= 6.865 mg/m3 

36 

\ 

i 
lmg/m3 = 0.146 ppm 

37 
4.2.1 Hazards 

MHHPA has the following classification: 

Xi: Irritant 

Xn: Sensitising 

R 41: Risk of serious damage to eyes 

R42/43: May cause sensitization by inhalation and skin contact 

The occurrence of MHHP A in chemical consumer products (preparations), 

other than cosmetics, will not appear on the label, when the concentration is 

below 0.1%. 

As other cyclic acid anhydrides, MHHPA is an irritant because of formation 

of corresponding acids in wet surroundings. It rarely induces contact allergy 

of the skin but more easily induces IgE-mediated contact urticaria. The 

mechanism of respiratory sensitization is mainly IgE mediated allergy both in 

animal studies and when exposed workers have been investigated. In the 

respiratory challenge tests bronchial obstruction has been verified, as well as 

development of inflammation (16). 

The critical effect is sensitization . 

. There is cross-sensitivity to HHPA. 

MHHPA has caused both sensitization and work-related symptoms at 

exposure levels as low as 10-50 pg/m3

• The level of exposure needed to cause 

specific IgE antibody production and work-related symptoms in mucous 

membranes and respiratory organs may be less than 10 pg/m3 (16). 

4.2.2 Limit values 

No health based limit values for MHHPA have been found, but a limit value 

should be below 10 rg/m3 to ensure absence of sensitizing effect. 

4.3 Phtha I ic anhydride, Methyl tetra hydro- (unspec.), CAS 11070-44-3 

Synonyms: Tetrahydromethylphthalic anhydride, 1 ,2,3,6-tetrahydro-4-

methylphthalic anhydride, MTHP A. 

Molecular formula:C9H100 3 

Molecular weight: 166.19 

Structural formula (1 ,2,3,6-tetrahydro-4-methylphthalic anhydride, CAS 

26590-20-5, shown): 

38 

\ 

I 
0 

39 
Melting point: -38° C (18) 

Boiling point: 150° Cat 13.5 hPa, 210° Cat 136 hPa (18) 

Vapour density: none found 

Vapour pressure: not found 

Water solubility: 176.4 g/1 at 20° C (18) 

Odour threshold, air: none found 

Conversion factor at 20° C, 1 atm.: 1 ppm= 6.783 mg/m3 

1 mg/m3 = 0.147 ppm (16) 

4.3.1 Hazards 

MTHP A has the following classification: 

Xi: Irritant 

Xn: Sensitising 

R 41: Risk of serious damage to eyes 

R42/43: May cause sensitization by inhalation and skin contact 

The occurrence of MTHPA in chemical consumer products (preparations), 

other than cosmetics, will not appear on the label, when the concentration is 

below 0.1%. 

As other cyclic acid anhydrides, MTHPA is an irritant because of formation 

of corresponding acids in wet surroundings. It rarely induces contact allergy 

of the skin but more easily induces IgE-mediated contact urticaria. The 

mechanism of respiratory sensitization is mainly IgE mediated allergy both in 

animal studies and when exposed workers have been investigated. In the 

respiratory challenge tests bronchial obstruction has been verified, as well as 

development of inflammation ( 16) . 

Among MTHPA-exposed workers, even at low levels of exposure (5-20 

rg/m3

) 56% had allergy symptoms of the eyes and upper airways, 9% had 

asthma, and 16% had MTHPA specific IgE antibodies. The corresponding 

numbers were 65%, 11%, and 22% in the more heavily (20-150 rg/m3

) 

exposed groups (16). 

The critical effects for MTHPA are irritation of mucous membranes of the 

eyes and airways and sensitization-induced work-related diseases. 

Sensitization, work-related rhinoconjunctivitis, and asthma have been verified, 

for workers exposed to MTHPA levels of 5-20 rg/m3 (16). 

4.3.2 Limit values 

No health based limit values for MTHPA have been found, but a limit value 

should be below 5 rg/m3 to ensure absence of sensitizing effect. 

4.3.3 Exposure and risk assessment for consumers for all the above phthalic 

anhydride derivatives 

The emission of the three phthalic anhydride derivatives was measured during 

realistic use scenarios for 6 nail lacquers and 2 two-component epoxy 

adhesives. 

40 

', / 

\ I 
The results of these emission measurements were all below the detection limit 

of 0.5 j1g/m3

. This is at least 10 times below the lowest level of 5 j1g/m3

, which 

has been found to induce respiratory sensitization. 

Nail lacquers were chosen for emission measurements, because allergic 

contact dermatitis cases have been found in the literature. These cases were 

caused by phthalic anhydride used in the copolymer base of the nail lacquers 

( 19). The nail lacquers chosen were selected among those with phthalic 

anhydride copolymers listed among the very first on the ingredients list, 

meaning that the highest concentrations of phthalic anhydride derivatives 

would be expected in these particular nail lacquers. 

Epoxy adhesives were chosen because phthalic anhydrides are known to be 

part of these products, and occupational exposure via epoxy resins has been 

reported to cause allergic rhinitis and conjunctivitis (20). 

Since no measurable emission from the selected nail lacquers and epoxy 

adhesives could be found, the risk of respiratory sensitization must be 

considered to be low. 

There is a slight possibility that people who have acquired respiratory allergy 

from other sources. e.g. occupationally, may react to very minute amounts in 

consumer products. However, no such reactions toward consumer products 

have been found in the literature. 

4.4 Methylenediphenyldiisocyanate, CAS 26447-40-5, 5873-54-1 and 101-

68-8 

Synonyms: MDI 

The possible isomeric forms of MDI are: 

4,4'-methylenediphenyl diisocyanate, CAS 101-68-8 

2,4'-methylenediphenyl diisocyanate, CAS 5873-54-1 

2,2'-methylenediphenyl diisocyanate, CAS 2536-05-2 

Molecular formula:C15H10N20 2 

Molecular weight: 250.26 

Structural formula (4,4'-MDI. CAS no. 101-68-8 shown): 

Polymeric MDI is a dark amber viscous liquid while the pure 4,4' MDI is a 

white waxy solid. The odour of MDI is slightly musty (10). 

Melting point: 34 - 43° C (1 0) 

Boiling point: 314-364° C (10) 

Vapour density: not found 

Vapour pressure: <0.014 Pa (2,4'-MDI) 

<0.002 Pa (4,4'-MDI) 

<0.005 Pa (polymeric MDI), all at 20° C (10) 

41 
Water solubility: Determination of the MDI solubility in water is difficult 

because of the high reactivity of the NCO groups towards OH groups, e.g. in 

water giving rise to aromatic amines. Consequently it is not possible to 

measure the solubility of MDI in water using the EC standard methods. 

Odour threshold, air: none found 

Conversion factor at 20° C, 1 atm.: 1 ppm= 10.22 mg/m3 

1 mg/m3 = 0.098 ppm (21) 

4.4.1 Hazards 

MDI has the following classification: 

Xn: Harmful 

Xi: Irritant 

Xn: Sensitising 

R20: Harmful by inhalation 

R36/37/38: Irritating to eyes, respiratory system, and skin 

R42/43: May cause sensitization by inhalation and skin contact 

The occurrence of MDI in chemical consumer products (preparations), other 

than cosmetics, will not appear on the label, when the concentration is below 

0.1 %. However, even below 0.1% the product should be labelled. "Contains 

isocyanates. See information provided by the manufacturer". If the product is 

an article there is no such requirement for labelling. 

In the EU risk assessment report (1 0) a different classification was proposed: 

Xn: Carcinogenic, category 3 

Xn: Harmful 

Xi: Irritant 

Xn: Sensitising 

R20: Harmful by inhalation 

R36/37/38: Irritating to eyes, respiratory system, and skin 

R42/43: May cause sensitization by inhalation and skin contact 

R 40: Limited evidence of a carcinogenic effect 

R 48/20: Harmful: danger of serious damage to health by prolonged exposure 

through inhalation 

Strictly speaking MDI should be classified as toxic by inhalation on the basis 

of a 4-hour LCSO of 490 mg/m3

• However, a consensus was reached among 

European experts (Directive 67/548/EEC; 25th ATP, i.e. Dir. 98/8/EC, 

0.].30.12.1998) to 

consider this value as irrelevant in terms of real-life exposure, because such 

high values are said not to be achievable except under experimental testing 

conditions. This pragmatic reasoning is acceptable provided that such high 

concentrations are indeed never achieved, even through misuse or (further) 

technological changes in work processes. Consequently it is proposed to 

classify MDI as harmful by inhalation. Taken together, in terms of pure 

hazard characterisation MDI is toxic by inhalation. However, if one considers 

the exposure assessment, it is reasonable to consider MDI as harmful only 

and to apply the risk management phrase 'harmful by inhalation' (1 0). 

42 

) 
It should be noted that since the vapour pressure of MDI (4,4') is only 0.002 

Pa at room temperature it is only possible to reach a saturated air 

concentration of 0.0197 ppm or 0.2 mg/m3

• In order to reach a concentration 

of as much 9S 490 mg/m3 it is necessary to heat the MDI, which in turn will 

condensate and form particles, not vapour, in the indicated concentration. 

For irritant effects a NOAEL of 0.5 mg/m3 was found (10). 

Animal data as well as studies in humans provide clear evidence of possible 

skin sensitization due to MDI. Animal studies indicate that MDI is a strong 

allergen. Human case reports describe the occurrence of allergic contact 

dermatitis due to MDI skin exposure (1 0). 

MDI is a potential respiratory sensitizer in animals and humans. Animal 

studies have shown that respiratory sensitization can be induced by skin 

contact with MDI. The quantitative relationships between exposures 

(concentration, duration, rate of exposure, route of exposure) have not been 

established. At the present time it is not possible to define reliable exposureresponse relationships with regard to the risk of sensitization for MDI. The 

current knowledge/state of the art in this field does not yet allow deciding a 

threshold level for sensitization. Because animal data support the hypothesis 

that respiratory hypersensitivity may be induced by skin contact and because 

such possibility has not been excluded in studies involving humans, it is 

reasonable to consider that it is not only important to reduce inhalation 

exposure but also to avoid skin contact (1 0) . 

The mechanism behind isocyanate-related hypersensitivity is still obscure. 

Several publications indicate that complex immunological reactions are 

involved in the sensitization process to MDI. Immediate allergic, late allergic 

and dual-phase responses can occur. Humoral as well as cellular immunity 

may be involved in the pathogenesis of hypersensitivity due to isocyanates. 

The specific humoral response can be IgE as well as IgG mediated. Crossreactivity with other isocyanates has been described in several publications 

(10). 

There is inadequate evidence of carcinogenicity in humans and limited 

evidence in experimental animals ( 1 0). which is the reason the EU risk 

assessment report proposed as classification as carcinogenic in category 3. 

In conclusion, dermal and respiratory sensitization seems to be the most 

critical effects. 

4.4.2 limit values 

The Danish occupational limit value is 0.005 ppm or 0.05 mg/m3 (22). This is 

a time weighted average (TWA) over 8 hours. In practise, the Danish ceiling 

limit (for a random 15 minute measuring period) is twice the TWA i.e. 0.01 

ppm or 0.1 mg/m3

• 

The American Conference of Governmental Industrial Hygienists (ACGIH) 

has recommended the same limit as a time weighted average (21). The 

ACGIH notes that the recommended limit may not necessarily protect 

susceptible workers from possible sensitization or an allergic reaction in 

previously sensitized individuals. 

43 
The Occupational Safety and Health Administration (OSHA) of the US 

department of Labor has set a permissible exposure limit of 0.02 ppm or 0.2 

mg/m3 as a ceiling limit (23). 

4.4.3 Exposure and risk characterisation for consumers 

The EU risk assessment report finds that as respiratory hypersensitivity may 

be induced by skin contact, respiratory and skin sensitisation due to MDI 

cannot be excluded during spray painting, the use of one component foam, 

during gluing or using a putty/filler cartridge or during the use of a hot melt 

adhesive. However, there is already sufficient information available upon 

which to base a conclusion (iii) for this endpoint for all scenarios: there is a 

need for limiting the risks; risk reduction measures which are already being 

applied shall be taken into account. (Specific attention should be paid to the 

situation where a subject has an occupationally acquired sensitisation to MDI) 

(10). 

The EU risk assessment report considers chronic toxicity from the use of 

consumer products containing MDI of less concern as consumer exposure of 

the identified products is expected to occur on occasional events of short 

duration. For chronic toxicity and carcinogenicity, conclusion (ii) is reached 

for all scenarios: there is at present no need for further information or testing 

or risk reduction measures beyond those which are being applied already (1 0). 

In the present investigation we were not able to find hot melt adhesive 

containing MDI nor MDI containing spray paint for private consumers on 

the Danish market. 

The products that were tested for emission of MDI were: car window 

adhesive, mattresses, one component adhesives and sealers, polyurethane 

rain-coat, floor adhesive, and a hair conditioner. 

No emission of MDI could be detected under the testing conditions. 

We have not examined exposure scenarios involving the grinding or thermal 

removal of MDI containing material. Such secondary exposure is known to be 

a hazard in the occupational setting (9), but only normal, predictable 

consumer exposure has been the scope of this project. 

With limits of detection varying from 0.2-17 ]1g/m3 and no emission found in 

the different exposure scenarios, the exposure is well below the occupational 

exposure limit of 50 ]1glm3

• Hence, the risk of inducing hypersensitivity during 

the use of the available consumer products made with MDI seems very low. 

It is important that consumers follow instructions to avoid skin contamination, 

since dermal sensitization can lead to general sensitization, thus causing risk of 

respiratory allergy with asthma-like symptoms upon later exposure by 

inhalation. 

In the case of already acquired hypersensitivity towards MDI or other 

isocyanates, occupationally or accidentally, even small exposures by inhalation 

from consumer products like window sealing foams, may cause an outbreak of 

respiratory allergy with asthma-like symptoms (10). 

44 
4.5 Glutaraldehyde,CAS111-30-8 

Synonyms: Glutaral; 1 ,5-pentanedial 

A colourless oily liquid. Commercial solutions often have an amber tint and 

an odour similar to spoiled fruit. 

Molecular formula: C5H80 2 

Molecular weight: 1 00 .1Z 

Structural formula: 

0~0 

Boiling point: 187-189° C (with decomposition) 

Vapour density: 3.4 (air=1) 

Vapour pressure: 16.5 mmHg (Z.Z kPa) at zoo C. There is some confusion 

about the purity of the test substance used: IUCLID (1996) gives the same 

value for pure glutaraldehyde and for a 50% aqueous solution, ACG IH 

(1991) gives a vapour pressure of0.015Z mmHg (Z.O Pa at zoo C) for a 50% 

solution. In 

SUBFAC (a computer model), vapour pressures (zoo C) has been calculated 

to Z4.9 mmHg for a 100% solution, 19.4 mmHg for a 50% solution, and Z.7 

mmHg for a Z% solution (Z4). In ZOOl, ACGIH gave a vapour pressure of 

0.10Z mmgHg for a 50% solution, and 0.003 mmHg for a Z% solution (Zl). 

Odour threshold, air: 0.14 ppm (0.17 mg/m3

) 

Conversion factor at zoo C, 1 atm.: 1 ppm= 4.Z mg/m3 

1 mg/m3 = O.Z40 ppm 

Data taken from (Z4). 

4.5.1 Hazards 

Glutaraldehyde has the following classification: 

RZ3/Z5: Toxic by inhalation and if swallowed. 

R34: Causes burns. 

R4Z/43: May cause sensitization by inhalation and skin contact. 

R50: Very toxic to aquatic organisms. 

with the following classification limits in products: 

Concentration 

c 50% 

Z5% c <50% 

10% C<Z5% 

Z% C< 10% 

1% C<Z% 

0,5% c < 1% 

Classification 

T, N; RZ3/Z5-34-4Z/43-

50 

T; RZZ-Z3-34-4Z/43 

C; RZO/ZZ-34-4Z/43 

Xn; RZO/ZZ-37 /38-41-

4Z/43 

Xn; R36/37/38-42/43 

Xi; R36/37 /38-43 

45 
The occurrence in chemical consumer products, other than cosmetics, will 

not appear on the label, when the concentration is below 0.1 %. 

Inhalation studies in mice and rats showed no carcinogenic activity when 

exposed to air concentrations of 62.5- 250 ppb (0.0625- 0.250 ppm) 6 

hours a day, 5 days a week for 104 weeks (25). 

Inhalation allergy in the occupational setting has occurred in several cases, 

particularly during cold sterilization of hospital equipment and use of 

glutaraldehyde containing chemicals during radiographic processing. 

Symptoms vary from watering of eyes, rhinitis, respiratory difficulty, nausea 

to headache. The vapours from glutaraldehyde may act as an irritant to 

bronchial and laryngeal mucous membranes, and prolonged exposure could 

produce localized edema and other symptoms of allergic response, including 

asthma. In these cases, the air concentrations in the breathing zone varied 

from 0.05 ppm to 0.12 ppm. In the cases where information on air 

concentration was not given, the workers had worked with preparations 

containing 2- 3.6% glutaraldehyde (25). 

Numerous symptoms have been found in individuals with exposure to less 

than 0.05 ppm glutaraldehyde, which is the recommended peak exposure 

limit in many countries (26). One such case was described in a 61-year-old 

nurse, an ex-smoker, who began working in a renal dialysis unit in 1976 (22 

years before). 

Ten years later, she experienced sporadic and mild episodes of chest tightness 

and shortness of breath related to exposure to formalin, which was used to 

sterilize artificial kidney machines. In 1994, formalin was replaced with 2% 

glutaraldehyde, which she handled daily in an open environment. She was 

symptomless until February 1998, when she developed symptoms of irritation 

of the eyes and upper respiratory tract, dyspnea on exertion, dry cough, and 

episodic attacks of wheezing, which she associated which glutaraldehyde 

exposure. 

Her symptoms were progressively severe, and she had an acute asthma attack 

requiring hospitalization. She then took sick leave, during which she slowly 

recovered. After 3 months with medical treatment, she was symptom free, and 

she was clinically evaluated. 

She underwent a the specific bronchial challenge test with activated 2% 

glutaraldehyde aqueous solution painted on a cardboard in a 7m3 challenge 

chamber for 10 min. No changes FEV 1 (forced expiratory volume in one 

second) were observed in a 24 hour monitoring period. However, at the end 

of this period, the methacholine inhalation test became positive (PC20 0. 7 4 

mg/ml, PC20: precise concentration of methacoline where FEV1 falls by 20%). 

One week later, the challenge test with 2% glutaraldehyde was repeated, and it 

elicited an early asthmatic response. Although no late reaction was observed, a 

recurrent nocturnal asthmatic reaction occurred in the following days. 

Similar cases of rhinitis and asthma have been diagnosed by specific 

bronchial challenge with glutaraldehyde concentrations in the range of 0.064-

0.081 mg/m3

, which is well below the ceiling limit of 0.8 mg/m3 (0.2 ppm) in 

Denmark or even the more stringent 0.05 ppm ceiling limit in many other 

46 

) 
I 

\ 

countries. Cross reactivity between formaldehyde and glutaraldehyde has 

been suggested. 

The type of mechanism responsible for glutaraldehyde inquced asthma is not 

known because IgE specific antibodies have not been demonstrated in 

affected subjects, or can be detected in only a small percentage of workers 

with symptoms related to work with glutaraldehyde (27). 

According to the American Conference of Industrial Hygienists (ACG IH) no 

clear dose-response relationships in humans have been established for 

airborne glutaraldehyde exposure. Reported industry experience indicates an 

absence of glutaraldehyde-induced skin or respiratory sensitizations for 

workers routinely exposed to airborne glutaraldehyde concentrations ranging 

from 0.01 to 0.34 ppm (21.26). 

4.5.2 limit values 

In Denmark, the occupational exposure limit is 0.2 ppm (0.8 mg/m3

), and this 

a ceiling limit (22). 

The American Conference of Industrial Hygienists (ACGIH) recommends a 

threshold limit value- ceiling of 0.05 ppm (21). 

In Denmark, a general limit (a so-called C-value) of 0.001 mg/m3 for ambient 

air has been calculated (24). The C-value is a limit value for how much an 

installation may contribute to air pollution. 

4.5.3 Exposure and risk characterisation for consumers 

In general. it was very difficult to obtain consumer products with a content of 

glutaraldehyde. No cosmetic products were found, even though 

glutaraldehyde is a permitted ingredient with restrictions. 

Glutaraldehyde may sometimes be used as a disinfectant during the 

manufacture of paper towels, toilet paper and the like. The two samples taken 

did not emit any detectable amounts of glutaraldehyde, i.e. the emission was 

below 5f1g/m3

• This is well below the Danish occupational exposure limit, and 

at the level of general limit for ambient air. 

Hence no risk of respiratory sensitization to glutaraldehyde can be attributed 

to these paper samples. 

No cases of sensitization to glutaraldehyde in consumer products have been 

found in the literature. 

The risk of respiratory sensitization to glutaraldehyde via consumer products 

must be considered very low, both because of low availability, non-detectable 

emissions, and absence of cases in the literature. 

It is possible that consumers with already acquired sensitization towards 

glutaraldehyde or formaldehyde from other sources may react to even small 

residual concentrations of glutaraldehyde in consumer products. However, 

since no such cases were found in the literature to confirm this, the risk must 

be considered very low. 

47 
48 
( 

5 Conclusion 

The purpose of the present project was to 

• Make an inventory of consumer product types that may contain any of 

the five R42-substances. 

• Examine, if consumers actually are exposed to the substances when 

using such products. 

• Assess, if the exposure is large enough to cause health effects in the 

consumers 

All in all, 19 products were sampled for inclusion in an emission analysis. The 

number of sampled products within each group is given in parenthesis. 

The following consumer products may contain phthalic anhydride derivatives: 

• Nail Lacquer (6) 

• Two-component epoxy adhesive (2) 

The following consumer products may contain glutaraldehyde: 

• Cosmetic products (mouth washes and creams) (O) 

• Disinfectants (O) 

• Film developers for consumers (0) 

• Paper handkerchiefs, kitchen roll and toilet paper (2) 

The following consumer products may contain monomeric MDI: 

• PU-foam articles, such as mattresses (2) 

• One component spray foam or adhesive (2) 

• Boat and car repair kits (1) 

• Two-component adhesives and putties (0) 

• Liquid roof coating (0) 

• Hot melt adhesives (O) 

• Floor adhesives (1) 

• Polyurethane materials in clothing (1) 

• Spray hair fixatives and conditioner (2) 

When searching the Danish market it was not possible to obtain cosmetic 

products, disinfectants, nor film developers with glutaraldehyde. Neither was 

it possible to obtain two-component adhesives and putties, liquid roof coating, 

nor hot melt adhesives with a content of monomeric MDI. 

All purchases were carried out while pretending to be ordinary consumers, not 

professionals. Although some of the outlets visited are also used by 

professionals, we were not offered products intended only for professionals. 

This indicates a fairly good separation between the markets for consumers 

and the markets for professionals, at least pertaining to these kinds of 

products. 

49 
No emissions of the respiratory sensitizers from the 19 products obtained 

could be detected by chemical analysis. Hence, no risk of sensitisation to 

phthalic anhydride derivatives, MDI or glutaraldehyde can be attributed to 

any of the products analyzed. 

Phthalic anhydride derivatives 

For the phthalic anhydride derivatives the risk of respiratory sensitization 

from consumer products must be considered very low. 

There is a slight possibility that people, who have acquired respiratory allergy 

to phthalic anhydride derivatives from other sources, e.g. occupationally. may 

react to very minute amounts in consumer products, such as nail lacquers and 

epoxy adhesives. However, in the literature no information was found to 

confirm such reactions toward consumer products. 

MDI 

The products that were tested for emission of MDI were: car window 

adhesive, mattresses, one component adhesives and sealers, polyurethane 

rain-coat, floor adhesive. and a hair conditioner. 

No emission of MDI could be detected under the testing conditions. 

We have not examined exposure scenarios involving the grinding or thermal 

removal of MDI containing material. Such secondary exposure is known to be 

a hazard in the occupational setting, but only normal. predictable consumer 

exposure has been the scope of this project. 

With limits of detection varying from 0.3-17 ]1g/m3 the exposure is well below 

the occupational exposure limit of 50 11g/m3

• Hence, the risk of inducing 

hypersensitivity during the use of the available consumer products made with 

MD I seems very low. 

It is important that consumers follow instructions to avoid skin contamination, 

since dermal sensitization can lead to general sensitization, thus causing risk of 

allergic asthma upon later exposure by inhalation. 

In the case of already acquired hypersensitivity towards MDI or other 

isocyanates, occupationally or accidentally, even small exposures by inhalation 

from consumer products like window sealing foams, can cause an outbreak of 

allergic asthma (1 0) . 

Glutaraldehyde 

The products that were tested for glutaraldehyde emission was toilet paper 

and kitchen roll made of recycled paper. No other consumer products with a 

probable emission of glutaraldehyde could be obtained. 

No emission of glutaraldehyde could be detected in the analyzed products. 

The risk of respiratory sensitization to glutaraldehyde via consumer products 

must be considered very low, both because of low availability, non-detectable 

emissions, and absence of cases in the literature. 

50 

\ 

) 
6 Reference List 

1. Abi1dgard A, Mikkelsen SH, Lauridsen FS. Survey of chemcial substances in paper 

handkerchiefs and toilet paper. Copenhagen: Danish Environmental Protection Agency; 2003. 

34. Survey of chemcial Substances in Consumer Products) 

2. Cohr,K.-H. Epoxy products which may contain phthalic anl1ydride derivatives are not only used 

in aircraft manufacture, but also aircraft repair. 2006. 

3. Gmn Information. Produkter med u0nskede kemiske stoffer 2002. 

4. Drexler H, Schaller KH, Nielsen J, Weber A, Weihrauch M, Welinder H, et al. Efficacy of 

measures of hygiene in workers sensitised to acid anhydrides and the influence of selection bias 

on the results. Occup Environ Med. 1999;56(3):202-5. 

5. Nielsen J, Welinder H, Jonsson B, Axmon A, Rylander L, Skerfving S. Exposure to 

hexahydrophthalic and methylhexahydrophthalic anhydrides--dose-response for sensitization and 

airway effects. Scand J Work Environ Health. 2001;27(5):327-34. 

6. Nielsen J, WelinderH, Ottosson H, Bensryd I, Venge P, Skerfving S. Nasal challenge shows 

pathogenetic relevance of specific lgE serum antibodies for nasal symptoms caused by 

hexal1ydrophthalic anhydride. Clin Exp Allergy. 1994;24(5):440-9. 

7. Kanerva L, Hyry H, Jolanki R, Hytonen M, Estlander T. Delayed and inm1ediate allergy caused 

by methylliexahydrophthalic anhydride. Contact Dern1atitis. 1997;36(1):34-8. 

8. Tarvainen K, Jolanki R, Estlander T, Tupasela 0, Pfaffli P, Kanerva L. lmmtmologic contact 

urticaria due to airborne methylhexahydrophthalic and methyltetrahydrophthalic anhydrides. 

Contact Dern1atitis. 1995;32(4):204-9. 

9. Pratt C, Engelund B, Dansk Toksikologi Center. Sekundrer eksponering for isocyanater. 

Rekvireret arbejde for BAR Industri 2001. 

10. European Commission- European Chemicals Bureau. European Union Risk Assessment Report. 

CAS no. 26447-40-5. Methylenediphenyl diisocyanate (MDI). 2005.; vol. 59). 

11. Pepe RC, We1111inger JA, and McEwenjr GN, editors. International cosmetic ingredient 

dictionary and handbook. Vol.l-4 [Medium (Data File): Compact disc]. Cosmetic, Toiletry, and 

Fragrance Association, Washington, D.C. [updated 2001]. 

12. Welinder Hand Gustavsson C. Detennination ofmethyltetrahydrophtalic anhydride in air. 

Sampling, analysis and occupational exposure levels. The Am1als of Occupational Hygiene. 

1992;36:189-97. 

13. U.S.Department of Labor. Occupational Safety & Health Administration. Method 64. 

Glutaraldehyde. http://www.osha.gov/dts/sltc/methods/organic/org064/org064.html 2006. 

14. Waters. Vejledning i brug afSep-Pak DNPH-silica cartridge. 2006. 

15. European Commission- European Chemicals Bureau. IUCLID Dataset. Cyclohexane-1,2-

dicarboxylic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/85427.pdf2000. 

16. Keskinen H. The Nordic Expert Group for Criteria Documentation of Health Risks from 

Chemicals and the Dutch Expert Committee on Occupational Standards. - 136: Cyclic acid 

anhydrides. Solna: Arbetslivsinstitntet; 2004. (Arbete och hiilsa; 2004:15 

17. European Conunission- European Chemicals Bureau. IUCLID dataset. 19438-60-9 hexahydro4-methylphthalic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/!9438609.pdf2000. 

51 
18. European Commission- European Chemicals Bureau. IUCLID Dataset. 11070-44-3 

tetrahydromethylphthalic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/11070443.pdf2000. 

19. Gach JE, Stone NM, Finch TM. A series offour cases of allergic contact dermatitis to phthalic 

anhydride/trin1ellitic anhydride/glycols copolymer in nail varnish. Contact Dennatitis. 

2005;53(1):63-4. 

20. Yokota K, Johyajama Y, Yamaguchi K, Takeshita T, Morimoto K. Exposure-response 

relationships in rhinitis and conjunctivitis caused by methyltetrahydrophthalic anhydride. Int 

Arch Occup Environ Health. 2006;72: 14-8. 

21. ACGIH. Documentation of the Threshold Limit Values and Biological Exposure Indices.- [2]: 

E-0. 7 ed. Cincinnati, Ohio: ACGIH (American Conference ofGovermnental Industrial 

Hygenists) Worldwide; 2001. 

22. Arbejdstilsynet. At-vejledning. Stoffer og materialer- C.0.1 Grrensevrerdier for stoffer og 

materialer. 2005. 

23. U.S.Department ofLabor OS&HA. Regulations (Standards- 29 CFR). TABLE Z-1 Limits for 

Air Contaminants.- 1910.1000 TABLE Z-1. 

http://www.osha.gov/pls/oshaweb/owadisp.show document?p table=STANDARDS&p id=999 

6. 2006. 

24. Jelnes JE, Nielsen E. Toxicological Evaluation and Limit Values for Methyl Tertiary-butyl ether 

(MTBE), Fom1aldehyde, Glutaraldehyde and Furfural. 

http:/ /www.mst.dk/udgiv/Publications/1999/87 -7909-563-1/pdf/87 -7909-562-3 .PDF 

Miljostyrelsen, Denmark; 1999.[70] 

25. HSDB. Glutaraldehyde. RN: 111-30-8. http://toxnet.nlm.nih.gov/cgi-bin/sis/htrnlgen?HSDB 

2005. 

26. Takigawa T, Endo Y. Effects of glutaraldehyde exposure on human health. J Occup Health. 

2006;48(2):75-87. 

27. Quirce S, Gomez M, Bombin C, Sastre J. Glutaraldehyde-induced asthma. Allergy. 

1999;54(1 0): 1121-2. 

52 
Huntsman Division (PU, PP, AdMat) PU 

Region (US, EAME, Asia) EAME 

Product (OCF, SPF, SPF kits, FR resins, Polyurea, Adhesives, SPF 

Coatings, Elastomers, Sealants, Other) 

Is test data available? (If answer is "NO", please save this YES 

form and email it to Michelle Koenig. If"YES", continue 

survey). 

Is this information considered Confidential Business NO 

Information (CBI)? Yes or No 

Chemical Composition of the formulated products (e.g polyurethane 

polyurethane, polyurea) 

BriefName of the study conducted (e.g. "Frankel Home Air monitoring investigation 

Testing"). during spray application in a 

residential house and surroundings 

1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 

2 Curing (surface) or Exposure (airborne)? Exposure 

3 Relevant Data Summary- Indicate variables studied e.g. 

environmental conditions, ventilation rates, temperature, 

humidity, catalysts/reactants present, proportioning/mixing, 

application site (indoors or outdoors); quantity of product 

used, application method and square footage covered. 

4 Test lab methods/ Instruments used/ Detection levels, QC ISO 17734-1:2006 

measures, levels of detection 

Experimental Parameters (sampling times, strategy) Interior air analysis 

Personal exposure 

5 Summarized Test Data Results Page 45 

6 Sensitivity Analysis (if any) 

7 Identify location of above data in document - Pages/Para (e.g. CPI/SPFA 

Pg2 Para4) PU EU SPF EPA VIR 003 - - -

8 Was Reoccupancy time determined? No 

9 If answer to 8 is yes, indicate reoccup_ancy time. 

10 Exposure limits (occupational and general population limits) 0.05 mg/m3 

No EAME general population limit 

inEU 

11 Quantitative Testing: Indicate whether unreacted 

diisocyanates were present, type of surface, and results 

obtained at each interval measured 

12 Other Data on Curing: Tack Free time, cuttable, expansion 

time, light traffic, ready to use etc 

13 Data related to formation ofbyproducts, particularly 

substances that continue to off-gas over time. 
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0 0 
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) 

Huntsman Division (PU, PP, AdMat) PU 

Region (US, EAME, Asia) EAME 

Product (OCF, SPF, SPF kits, FR resins, Polyurea, Adhesives, OCF 

Coatings, Elastomers, Sealants, Other) 

Is test data available? (If answer is ''NO", please save this YES 

form and email it to Michelle Koenig. If"YES", continue 

survey). 

Is this information considered Confidential Business No 

Information (CBI)? Yes or No 

Chemical Composition of the formulated products (e.g Polyurethane 

polyurethane, polyurea) 

BriefName of the study conducted (e.g. "Frankel Home Reaction document for the Risk 

Testing"). Reduction Strategy for consumer 

exposure for MDI, includes 

OCF Airborne concentrations of 

MDI 

1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 

2 Curing (surface) or Exposure (airborne)? Exposure 

3 Relevant Data Summary- Indicate variables studied e.g. Results collected by the industry 

environmental conditions, ventilation rates, temperature, Samples taken during the use of 

humidity, catalysts/reactants present, proportioning/mixing, OCF while fixing window & door 

application site (indoors or outdoors); quantity of product frames at renovation site and new 

used, application method and square footage covered. building. 

4 Test lab methods/ Instruments used/ Detection levels, QC Possibly reported in individual 

measures, levels of detection studies listed 

Experimental Parameters (sampling times, strategy) Sample times reported from 7 to 24 

minutes re. p 10 

5 Summarized Test Data Results Low levels well below exposure 

limits in general 

6 Sensitivity Analysis (if any) Possibly reported in individual 

studies listed 

7 Identify location of above data in document - Pages/Para (e.g. p10 

Pg2 Para4) 

8 Was Reoccupancy time determined? No 

9 If answer to 8 is yes, indicate reoccupancy time. - 10 Exposure limits (occupational and general population limits) 0.05 mg/m3 

No EAME general population limit 

inEU 

11 Quantitative Testing: Indicate whether unreacted The OCF product is released from 

diisocyanates were present, type of surface, and results the nozzle as a viscous foam. 

obtained at each interval measured Curing (incl. reaction of the 

diisocyanates) starts immediately 

and moves from the outside 

inwards. 

12 Other Data on Curing: Tack Free time, cuttable, expansion - time, light traffic, ready to use etc 

13 Data related to formation ofbyproducts, particularly - ( substances that continue to off-gas over time. 
( .! 

( ,, ......... ·· 

Reaction document for the risk 

reduction strategy for consumer 

exposure for MDI 

03/08044/KDV 

July 2005 
Information on the rapporteur : 

BE Rappo1•teur : 

Federal Public Service of Public Health, Safety of the Food-Chain and Environment 

DG Public Health: Envirorunent 

Mr. R. Moreau, General Director 

Service of Risk Management 

R.A.C. Vesalius 

Pachecolaan 19 box 5 

B~1010 Brussels 

Belgium 

contact point: Cathcline.dantinne@health.fgov.be 

Report prepared by 

ECOLAS 

Lange Nieuwstraat 43 

B2000 Antwerp 

Belgium 

Tel: +32/3/233.07.03 

Fax: +32/3/233.81.20 

Mail: ecolas@ecolas.be 

Web: www.ecolas.be 

In collaboration with: 

BURAS 

Rijvisschestraat 118, Box 3 

9052 Gent 

Belgium 

Tel: +32/9/257.13.99 

Fax: +32/9/257.13.98 

Mail: info@euras. be 

Web: www.euras.be 

( 

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ECOLAS Content 

0./. ... - Se//igentprojecttitel: draft (datum) of niets lndien finaal 

CONTENT 

CONTENT ............................................................... :~~ ................ JI.IIIIIIIIIII'I'II'IIfl:llll••••tiiiiiiii'IIJ'IJIIWIIIIIIII····-·I 

LIST OF ABBREVIATIONS ................................... III:IIII:IIIIII1111111111TIIIIIIItiltlllllllllllliiiiiiiiiii1111111111111111111III 

LIST OF ANNEXES ............................................................ III'I··-······················1'111111111111111111111111111'11111 v 

1 INTRODUCTION IIIIICIIIIII.IIIIJIIIIJ.IIIIIIIIIIIIIIII'IIIII'IIfla•••tiii.IIIII.IIIIIIIIIIIIIIYIIIIIIIIIIII:IIlllllllllllrlllfiiii'IIIYIIIII 1 

1.1 Conclusions from the risk assessment report .......................................................................... 1 

1.2 Outcome of the presentation of the risk reduction strategy to the risk reduction group ............. 2 

2 TOXICITY fOR fERTILITY llltllllll'llltlll'llli'IIIIIIII'IWIIlltllll:tlllllllllllllllllll'lllllllllllllli.IJIIIIIIIIIIIIIWIWIInllll:tlllll 5 

3 EFFECTIVENESS OF THE PROPOSED RISK REDUCTION STRATEGY FOR CONSUMER 

EXPOSURE ..................................................................................... :1 ••••••••••••••• :1.11111'············ 7 

( 

.... 3.1 Introduction,,,,.,, ••.• ,,, .•.•.. ,··~··-·······'**' ........................... ,,, ....................................................... 7 

3.2 risk reduction proposal •....•......• ,. .....•....•...•. ,. ............................................................................. 7 

3.3 Elements in support of the proposed risk reduction measures ................................................. 8 

3.3.1 Relative contribution of dermal and inhalation exposure ......................................................... 8 

3.3.2 Risks for irritation .••••••.• "'JI'"'*············~~··~·····,,, .... , ..................... , ........... ,.,,,.,,,., ........... , .. , .. ,, ....... 9 

3.3.3 Risks for sensitlsatfon ......................................................................................................... 11 

3.3.4 Proportionality of measures ................................................................................................ 11 

3.4 Differentiating safe from unsafe products ............................................................................ 12 

4 CONCLUSIONS ............................. ,ltiiiiiiiiiiiiiiiiiiiiiiiii'II111111111I11:1····:11:11111111AIIIIIIIJIIIIII··············· .. ·············13 

LITERATURE •~~~•••••••~t•••••••••••••••••••••••s••••:r••:r••:r••••••••••••••••••••••••••••••••••••••:~••••w•"••••••••••••••••~•••••Jr••••••••• 15 

ANNEXES •••••••••••••••••••••••••••••••••••••••••••••• , ........................................ , ••••• IUIIIIIIII'fll'llllll······· .. ·············17 

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ECOLAS Ust of abbreviations 

0./. ... -Selligentprojectt/tel: draft (datum) of n/ets indlen finaal 

LIST OF ABBREVIATIONS 

MDI Mathylened!phenyl diisocya nate 

MOS Margin of safety 

OCF One component foam 

PPE Personal protection equipment 

RAR Risk assessment report 

( 

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£COLAS list of annexes 

o.;. ... ~ Se!ligentprojecttitel: draft (datum} of niets indien finaa/ 

LIST OF ANNEXES 

Annex 1: Letter from Stelnel regarding MDI containing hot melt adhesives .......................................... 11 

Annex 2: Letter from AKPU regarding recognised cases of proven sensitisation amongst OCF users ...... 11 

( 

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ECOLAS Introduction 

O.j. ... - Selligentprojecttitel: draft (datum) of niets indien tina a/ 

1 INTRODUCTION 

1.1 CONCLUSIONS FROM THE RISK ASSESSMENT REPORT 

The risk assessment report for methylenediphenyl diisocyanate came to the following conclusions: 

FOR THE ENVIRONMENT: 

ii) There Is at present no need for further information and/or testing and for risk reduction measures 

beyond those which are being applied already 

FOR HUMAN HEALTH: 

Workers 

i) There is need for further information and/or testing 

iii) There is a need for limiting the risks; risk reduction measures which are already being applied shall be 

taken into account 

Conclusion (i) (on hold) was reached because: 

• The current database does not adequately cover the toxicity for fertility. The collection of 

additional Jnformatian·-·should~··however, not delay the imptementatlon-·of ap.proprlate control 

measures needed to address the concerns related to other endpoints (conclusion (i) on hold). 

Conclusion (iii) was reached In the RAR because: 

• Health risks due to occupational exposure cannot be excluded with regard to lrrltation1 both skin 

and eyes (incidentally by splashing or hand contact with eyes), for unprotected workers on 

building sites (for downstream users). There is a need for limiting_t.~~.!-~~~:~on-buildfn'g sites:·· · 

( 

• Health risks due to occupational exposure cannot be excluded with regard to respiratory tract (. ,; 

Irritation (for both chemical in.~u.~t_ry:_~.~~- 9.ownstre~m users). 

• Health risks due to occupational exposure cannot be excluded with regard to sensitisation (dermal 

contact and inhalation exposure) (for both chemical Industry and downstream users). 

• Health risks due to occupational exposure cannot be excluded with regard to repeated inhalation 

(for both chemical industry and downstream users). 

Consumers 

i) There is need for further information and/or testing 

iii) There Is a need for limiting the risks; risk reduction measures which are already being applied shall be 

taken into account 

Conclusion (i) (on hold) was reached because: 

• The current database does not adequately cover the toxicity for fertility. The collection of 

additional information should, however, not delay the implementation of appropriate control 

measures needed to address the concerns related to other endpoints (conclusion (i) on hold). 

Conclusion (iii) was reached because: 

1 
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ECOLAS Introduction 

0./. ... • Se//igentprojecttitel: draft (datum) of niets indien ffnaa/ 

• Risk reduction measures should be considered that will ensure protection of consumers from eye 

and skin and respiratory tract irritation1 respiratory and skin sensitisation, and lung effects induced 

by short-term repeated exposure. Specific attention should be paid to the situation where a 

subject has an occupationally acquired sensitisation to MDI. 

Man exposed indirectly via the environment 

ii) There is at present no need for further Information and/or testing and for· risk reduction measures 

beyond those which are being applied already · 

Combined exposure: worker/consumer/indirectly via the environment 

i) There Is need for further Information and/or testing 

iii) There is a need for limiting the risksj risk reduction measures which are already being applied shall be 

taken into account 

Conclusion (i) (on hold) was reached because: 

• The current database does not adequately cover the toxicity for fertility. The collection of 

additional information should, however1 not delay the implementation of appropriate control 

measures needed to address the·concerns related to other endpoints (conclusion (i) on hold). 

Conclusion (iii) was reached because: 

' 

• Health risks due to combined occupational and consumer exposure cannot be excluded with 

regard to irritation (eyes, skin1 respiratory tract). 

• Health risks due to combined occupational and consumer exposure cannot be excluded with 

regard to sensitisation (dermal contact and Inhalation exposure). • 

• Health risks due to combined occupational and consumer ·exposure cannot be excluded with 

regard to repeated inhalation exposure. 

1.2 OUTCOME OF THE PRESENTATION OF THE RISK REDUCTION 

STRATEGY TO THE RISK REDUCTION GROUP 

The risk reduction recommendations regarding worker exposure: 

• to establish at community level an occupational exposure limit value for MDI [according to 

Directive 98/24/EEC]. 

• ·employers using MDI for uses identified as a concern in the risk assessment should take note of 

any sector specific guidance developed at national level based on the practical non-binding 

guidance, to be published and available from the Commission as foreseen under Article 12(2) of 

Council Directive 98/24/EC (Chemical Agents Directive). 

were accepted by the risk reduction group. 

However, the risk reduction recommendations regarding consumer exposure: 

• to consider at Community level marketing and use restrictions in Council Directive 76/769/EEC 

(Marketing and Use Directive) of MDI products put on the market without sufficient PPE and 

handling Instructions 

• Member States should carry out an active and effective market surveillance of the situation in 

their territories concerning the presence of MDI containing consumer products and to notify the 

Commission through the Rapid Alert System of Directive 2001/95/EC (General Product Safety). If 

2 
ECOLAS Introduction 

0./. ... -Sel/igentprojecttite/: draft (datum) of nlets indfen finaa/ 

proved necessary these products should be removed from the market as being unsafe under the 

general safety obligation provisions of the Directive 2001/95/EC. 

were found to be insufficiently supported because the PPE (mainly gloves) will offer insufficient protection 

towards inhalation exposure and respiratory tract irritation and sens!tlsation can not be ruled out by the 

useofpPE. . ...... . 

Another remark that was made is that no recommendations were made regarding the need for further 

information and/or testing for the aspect toxicity for fertility. ~-·" .. ·····-··-··· · · · 

This note has as a purpose to answer the questions and concerns raised during the risk reduction group 

meeting. 

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ECOLAS Toxicity for fertility 

O.j.... - Sel/igentprojecttitel: drafl: (datum) of n/ets indien finaal 

2 TOXICITY FOR FERTILITY 

Regarding the need for further information to assess the toxicity for fertility of MDI1 the Risk Assessment 

GrOu-p decided to take a conclusion I( on hold ) until the finalisatlon of the RRS. As response comments 

on the fertility the Industry provide this statement (Industry comments on the report 'Methylenedlphenyl 

diisocyanate (MDI): reproductive toxicology): 

"The toxicological database for inhaled MDI demonstrates consistently that toxicity is asso~§ted only ~ith __ 

the portal of entry1 any other manifestations of toxicity are secondarY to this. Consideration of the 

potentiErof-M-DI to induce any developmental toxicity makes the same conclusion1 the limited 

foetotoxicity observed is seconaary to the toxicity induced in the dams, and this Is confined\ to· the ' 

respiratory tract. Developmental toxicity studies with other diisocyanates1 TDI and HDI1 slipw_identical 

outcomes, any foetotoxicity is secondary to maternal toxicity confined to the respiratory tract. While no 

fe1tility studies are available for MDI1 sub-chronic and chronic studies all show toxicity confined to the 

respiratory tract. Fertility studies with TDI and MDI show no effects on reproductive parameters, all 

effects are confined to the respiratory tract. Hence the databases for MDI1 TDI and HDI all show that ( 

primary toxicity for diisocyanates is to the respiratory tract, other effects1 such as foetotoxicity in 

developmental studies1 are secondary to this. This relationship applies to TDI and HDI when tested in 

fertility studies in the rat and is considered to apply equally to MDI, i.e., If any effects were to be seen in 

a fertility study, these would occur only as a secondary effect of the toxicity to the respiratory system of 

theexposed rats. 

Protection against respiratory tract toxicity will protect against any secondary effects and the need to 

adopt OELs to protect against the sensitising potential of these chemicals provides enhanced safeguards. 

Taking all these points into account, it is concluded that reproductive toxicity is not an f?.~qpoint of 

concern for MDI." 

5 

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£COLAS Effediveness of the proposed risk redudion strategy 

O.j. ... - Se/l!gentprojectt/te/: draft (datum) of nfets lndien finaa/ 

3 EFFECTIVENESS OF THE PROPOSED RISK REDUCTION 

STRATEGY FOR CONSUMER EXPOSURE 

3.1 INTRODUCTION 

The risk assessment report assessed 4 exposure scenarios for consumers: 

t~ spray paintingj 

t~ use of one component foamj 

• glueing, painting or using a putty/filler cartridge; 

• use of a hot melt adhesive. 

For all of the exposure scenarios it was found that there is no need for risk reduction measures beyond 

those which are applied already for the aspects of acute toxicity, chronic toxicity/carclnogenity, 

mutagenicity and developmental toxicity. 

Skin and eye irritation from direct skin and eye contact in all 4 exposure scenarios can not be excluded. 

Respiratot)i.tract -irritation cannot be excluded during the use of one component foam and during the use 

ofa-fiot melt adhesive. The margin of safety for acute pulmonary irritation is found to be insufficient for 

the use of one component foam and during the use of a hot melt adhesive. A respiratory hypersensitivity, 

WfiTcflma{oe-mcfi.iced by skin contact, respiratory and skin sensitization due to MDI, can not be excluded 

in either of the 4 exposure scenarios. The margin of safety for lung effects induced by shorHerm 

repeated exposure is found to be insufficient for the use of one component foam and during the _ll~~ _of a 

hot melt adhesive. 

3.2 RISK REDUCTION PROPOSAL 

"To consider at Community level marketing and use restrictions In Council Directive 76/769/EEC 

{Marketing and Use Directive) of MDI products put on the market without sufficient PPE and handling 

instructions." 

As dermal exposure was assessed to make a significant contribution to consumer exposure for all 

scenarios, it is recommended to add at least a pair of suitable gloves to the product. Providing 

consumers with sufficient information together with the P_~~ '('Jill give an extra incentive to use the PPE. 

In the DIY-store, consumers should be provided with sufficient handling and use instructions together 

with the product. Therefore it should be the responsibility of the producers to provide this information to 

the store or together with the product. It is also important to indicate that a short description on the 

product itself maybe not sufficient and additional prescriptions should be included to the packaging on a 

separate paper. These handling an use instructions should at least point out that MDI contalni1J9 ... Rm~ucts 

should only be used in well ventilated areas and that long sleeves and proper PPE (pair of suitable gloves L .. ·-·---·-------·-·--.. ··· added to the package) should be worn at all time during use of MDI containing products. 

7 

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ECOLAS Effectiveness of the proposed risk redudion strategy 

o.;. ... -Sel/igentprojectt/tel: draft (datum) of nlets lndien flnaal 

3.3 ELEMENTS IN SUPPORT OF THE PROPOSED RISK REDUCTION 

MEASURES (march 2005) 

3.3.1 Relative contribution of dermal and inhalation exposure 

If the default values for workers (TGD, 1996): 

• respiratory volume: 10m3/day 

• body weight: 70 kg 

• absorption inhalation exposure: 100% 

are also applied to consumers, the following relative contribution of dermal and inhalation exposure can 

be calculated for the various scenarios: 

Spray painting One component Gluein{b palnttn~ Hot melt 

foam putty/filler adhesive 

Inhalation - 0.0061 mgfm3 - 0.025 mg/ma 

exposure 

Dermal exposure 5,35 mg/day · 535 mgfday 2940 mg/day 168 mg/day 

Uptake* 

Inhalation (100%) - 0.00087 mg/kg bw - 0.0036 mgjkg bw 

Dermal ( 1 o/o) 0.00076 mg/kg bw 0.076 mg/kg bw 0.42 m'g/kg bw 0.024 mg/kg bw 

Relative 

contribution 

Inhalation uptake - 1,12% - 13% 

Dermal uptake 100% 98,87% 100% 87% 

* In the RAR {2003) an uptake of 100% for Inhalation exposure and of 1% for dermal exposure (based on the 

experimental data of Leibold et al (1998)) was used. 

• According to the alliance for the Polyurethanes Industry (API,2002) light duty gloves offer already 

sufficient protection against polymeric MDI penetration: Nitrile rubber gloves of thickness >0.1 

mm - over 8 hours protectloni 

• PVC gloves of thickness >0.22 mm - 2 hours protection; -

• Polyethylene gloves of thickness >0.04 mm - 1 hour protection. 

The use of proper PPE (suitable gloves and long sleeves) will prevent dermal uptake and ultimately lead 

to a reduction of total uptake: · 

• from 0,076?7 mg/kg bw to 0,00087 mg/kg bw for one component foam; - . • from 0,0276 mg/kg bw to 0,0036 mg/kg bw for one component foam. 

In all scenarios, uptake will be 100% through inhalation upon using proper PPE, but total uptake will be 

d~creased by over98.9% for one component foam. 

Taking into account the updated inhalation exposure data (see 3.3.2.3), the following relative 

contribution of dermal and Inhalation exposure can be calculated for the various scenarios: 

8 
ECOLAS Effediveness of the proposed risk redudion strategy 

o.;. ... -Se//fgentprojecttltel: draft (datum) of niets lndlen linaal 

Spray painting , One component G/uetng, painting" Hot melt adhesive 

foam putty/filler 

Inhalation - 0.00307 mg/m3 - 0.0031 mg/m3 

exposure 

Dermal exposure 5,35 mg/day 535 mg/day 2940 mg/day 168 mg/day 

Uptake* 

Inhalation (100%) - 0.00044 mg/kg bw - 0.00044 mg/kg bw 

Dermal (1%) 0.00076 mg/kg 0.076 mg/kg bw 0.42 mg/kg bw 0.024 mg/kg bw 

bw 

Relative 

contribution 

Inhalation uptake - 0.58% - 1.8% 

Dermal uptake 100% 99.4% 100% 98.2% 

* In the RAR (2003) an uptake of 100% for inhalation exposure and of 1% for dermal exposure (based on the 

experimental data of Leibold et al (1998)) was used. 

The above data, based on the default values for workers for inhalation exposure and updated Inhalation 

exposure data Indicate that for all scenarios over 98% of total uptake results from dermal exposure. The 

use of proper PPE (suitable gloves and long sleeves) will prevent dermal uptake and ultimately lead to a 

reduction of total uptake in OCF scehario of over 99,4%:. 

• from 0,07644 mg/kg bw to 0,00044 mg/kg bw f?r one component foamj 

• from 0,02444 mg/kg bw to 0,00044 mg/kg bw for one component foam. 

In all scenarios, uptake will be 100% through inhalation upon using proper PPE, but total uptake will be 

decreased by over 98% for one component foam and hot melt adhesives. 

3.3.2 Risks for irritation 

3.3.2.1 Eye irritation 

Eye irritation due to splashes or aerosols can only take place for spray painting and the use of MDI 

containing paint. For one component foam1 the product exiting the can Is a reacting foam. For glueing, 

putty/filler and hot melt adheslves1 the product Is a highly viscous, reacting paste that will not give rise to 

splashes or aerosols during applications. 

In all scenarios, exposure to the eyes can take place through contact with contaminated gloves. 

3.3,2.2 Skin irritation 

Skin irritation can be excluded in all 4 scenarios if proper PPE (suitable gloves and long sleeves) are 

worn. 

9 

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ECOlAS Effectiveness of the proposed risk reduction strategy 

0./. ... - Selligentprojecttfte!: draff:(datum) ofniets indien finaa/ 

3.3.2.3 Respiratory tract irritation 

ONE COMPONENT FOAM 

In the RAR, measurements of 1985-1986 are mentioned indicating atmospheric concentrations of 

0.00017- 0.0061 mg;ms--of MDI during the use of OCF. The highest measured value of 0.0061 mgfm3 

was used in the risk assessment. 

One component foams have significantly altered since 1985-1986. Propellant gasses as wen as spraying 

nozzles have been optimised ever since. Industry provided new measurements of atmospheric 

concentration of MDI during the use of OCF. In this study, the presence of airborne MDI has been 

investigated during the use of one component foam spray cans at building sites to insulate windows and 

door frames. One was located at a renovation site and the other in a new building: 

• Renovation site: Insulation of 1 door and 5 windows consecutively during 24 minutes. Personal 

sample taken during every window or door being insulated and a personal sample covering the 

whole period of activity. 

• New building: Insulation of 13 windows consecutively durin"g 12 minutes. Personal sample taken 

covering the whole period of activity. 

The results of these new measurements are the following: 

Sample description Sample time (minutes) MD!(mg/m3) 

Individual samples 1 window 7 < 0.00015 

2 windows + part of door 4 0.00307 

2 windows + part of door 12 <0.00003 

Whole period samples 5 windows + 1 door 24 0.00079 

13 windows 16 <0.00009 

When the highest value during individual sampling (0.00307 mg MDI/m3 ) and a NOAEL of 0.5 mgfm3 

(Pauluhn, 2002) are used, a margin of safety of 163 can be calculated. 

As the NOAEL was determined by tests on rats and the observed Irritation effects were found to be 

reversible, a standard margin of safety of 100 (factor of 10 accounting for interspecles kinetics and 

dynamics and an additional factor of 10 accounting for human variability) can be applied to this specific 

case. Additionally, the exposure to such concentrations only takes place of a period of a few minutes, 

even for a DIY -job. This means that the new exposure data during use of one component foam indicate 

that there is no risk for respiratory tract irritation. 

HOT MELT ADHESIVES 

The risk assessment mentions atmospheric concentrations measured during the application of hot melt 

adhesives using specific heating guns, specially designed to minimize exposure of the operator to the 

glue. One of the heating guns tested was of a previous design while the other one was of the newest 

design. Measurements indicated atmospheric concentrations of 0.025 mg MDI/m3 for the heating gun of 

previous design and 0.0031 mg MDI/ma for the heating gun of the newest design during similar glueing 

activities. The value of 0.025 mg MDI/m3 has been used for the risk assessment although the hot melt 

adhesive producer clearly states that only heating guns of the newest design are still put on the market. 

10 
£COLAS EffediVeness of the proposed risk reduction strategy 

o.;. ... ~ Se!!igentprojecttitel: draft (datum) of nlets indien finaal 

Annex 1: Letter from Henkel regarding MDI containing hot melt adhesives 

When the exposure value for the heating gun of the newest design (0.0031 mg MDI/m3 ) and and a 

NOAEL of 0.5 mg;ms (Pauluhn1 2002) are used, a margin of safety of 161 can be calculated. 

As the NOAEL was determined by tests on rats and the observed irritation effects were found to be 

reversible, a standard margin of safety of 100 (factor of 10 accounting for interspecies kinetics and 

dynamics and an additional factor of 10 accounting for human variability) can be applied to this specific 

case. This means that the use of hot melt adhesives with the heating gun of the newest design indicate 

that there is no risk for respiratory tract irritation. 

Up to the current knowledge, there is for the moment only one company (the one for which the heating 

guns have been tested) that puts MDI~containing hot melt adhesives on the EU consumer market and the 

product sold on the EU market has been found to offer sufficient protection against respiratory tract 

Irritation. This does, however, not guarantee that similar products from other manufacturers or imported 

from outside the EU offer the same level of protection 

3.3.3 Risks for sensitisation 

Respiratory tract sensitlsation can never be excluded as no NOAEL could be determined for this effect. As 

respiratory tract sensitisation can be Induced by both inhalation and dermal contact, the use of suitable 

gloves and long sleeves will reduce total exposure for both the use of OCF and of hot melt adhesives by 

consumers. 

On the other hand, the European OCF producer committee (AKPU) has no knowledge of a recognised 

case of proven sensitisation over the last 25 years amongst OCF users1 implying that the risk for 

sensltlsatlon during OCF use by consumers can not be ruled out completely. 

Annex 2: Letter from AKPU regarding recognised cases of proven. sensitisation amongst OCF 

users 

3.3.4 Proportionality of measures 

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Some Member States were in favour of a marketing and use restriction for one component foams for the ( . ' 

consumer market. From the above arguments1 including new measurements of inhalation exposure 

during door and window insulation using these OCF, it becomes clear that: 

• over 99% of the total exposure during use of OCF results from dermal exposure for which the 

use of suitable gloves and long sleeves provide sufficient protectioni 

• total uptake to MDI upon use of one component foams can be reduced by over 99.4% by using a 

suitable pair of gloves and wearing long sleeves; 

• for the optimised propellant gas and spraying nozzle, margins of safety towards respiratory tract 

Irritation of 163 are obta!nedj 

• the risk of respiratory tract sensitisation can not be ruled out completely during the use of OCF. 

Production of OCF cans in the EU25 amounts to 75 - 100 million cans pro year by some 24 companies, 

distributed according to size in the following way: 

Company size (cans/year) EU25 Non-EU 

>20,000,000 2 1 

> 10,000,000 ~ <20,000,000 4 0 

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ECO/AS Effectiveness of the proposed risk reduction strategy 

0./. ... -Se/ligentprojecttitel: draft (datum) of nlets indlen flnaal 

>5,000,000 ~ <10,000,000 2 0 

> 1,000,000 ~ <51000,000 7 4 

<1,000,000 9 >5 

Some 25 - 35% of the produced cans are put on the consumer market. Retail value of the consumer 

market represents a value of about € 100,000,000. Margins are also higher on the consumer market. A 

marketing and use restriction on OCF for the consumer market would have a significant impact on this 

industry sector. As the share of cans . produced for the consumer market Is higher In the smaller 

companies ( <5,000,000 cansfyear)1 a marketing and use restriction for OCF on the consumer market 

might render those smaller companies non~vlab!e. 

The available data do not allow us to provide a complete overview of advantages and drawbacks of a 

marketing and use restriction for one component foams on the consumer market. Nevertheless, the 

limited information available points in the direction of a significant impact on the one component foam 

industry (especially on the smaller companies) of such marketing and use restriction for one component 

foams on the consumer market. 

3.4 DIFFERENTIATING SAFE FROM UNSAFE PRODUCTS 

A number of Member States suggested during the risk reduction group meeting to differentiate between 

safe and unsafe products based on the free MDI~content and to Install marketing and use restrictions for 

products containing free MDI above a certain level. 

Free MDI contents of products In the consumer market vary over broad ranges from 0,1% in spray 

painting over 2% in hot melt adhesives and 10% in OCF up to 35% in some adhesives. For all 

applications the free MDI reacts very quickly (almost instantaneously) with other reactive compounds 

(polyols or pr~polymers) in the system under the influence of air moisture. The higher the free MDI 

content, the higher the rate of reaction with other reactive compounds. In most cases1 an surface layer ls 

immediately formed, preventing the release of free1 unreacted MDI in the core of the material. 

The above holds especially true for one component foams. The product leaves the can through a pre~ 

expansion nozzle as a reacting and expanding foam and not as an aerosol. Reaction with atmospheric 

moisture Is virtually immediate (due to the high free MDI content) and a crust forms rapidly on the 

expanding foam, preventing unreacted free MDI (if any) to evaporate from the foam. 

Taking into account the above arguments, the free MDI content can not be used as a criterium to 

distinguish 'safe' from 'unsafe' products . 

12 
ECOLAS Effectiveness of the proposed risk reduction strategy 

0./. ... -Sel!igentprojecttite/.· draft {datum) of nlets lndien nnaal 

, 4 CONCLUSIONS 

Based on the facts that: 

• in the RAR no risk for inhalation exposure and uptake was detected for spray painting and 

gluelng, painting or using a putty/filler cartridge; 

• the industry doesn't provide any information that spray painting and glueing, painting or using a 

putty/filler cartridge continue to be scenarios for consumers {it is not the first destination of 

these products ). 

e based on new data from industry the margin of safety for respiratory tract Irritation was found 

sufficient for both one component foam and hot melt adhesive use; 

• the use of suitable gloves and long sleeves during OCF consumer exposure scenarios reduces 

uptake by over 99.4%, ·while respiratory tract sensltisatlon can result from both dermal and 

inhalation exposure; 

• a clear distinction between 'safe' and 'unsafe' products can not be made solely based on the free ( 

MDI content of the product; 

• the risk for sensitisation cannot be completely excluded ( no threshold ). 

• There is a conclusion i) always on hold for the fertility 

o The use of PPE by consumers is uncertain even if they are provided with the product . 

o the measure 1

marketing and use restrictions for OCF on the consumer market' could not be 

completely evaluated but there are indications that the economic impacts of such a measure 

would be consequential; 

the following risk reduction strategy Is proposed for consumer exposure: 

"to consider at Community level marketing and use restrictions In Council. Directive 76/769/EEc! 

(Marketing and Use Directive) of MDI products." 

1 OJ L 262, 27.9.1976, p. 201 

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£COlAS Literature 

o.;. ... ~ Sef//gentprojecttltel: draft (datum) of niets lndlen finaal 

LITERATURE 

API (2002); PMDI User Guidelines for Protective Clothing Selection; Technical Bulletin AX178, 6 pp. 

Leibold, E., Hoffmann, H.D. and Hildebrand, B. (1998); 14C~Methylenbisphenyllsocyanate t 1

C-MDI) -

Study of the absorption alter single dermal and Intradermal administration In rats; BASF Aktiengesellshaft 

Toxicology, Ludwigshafen/Rhein, Draft report project no. 0180431/946010, III projectno. 126-EU-MTX in 

RAR (2003) 

RAR (2003); Draft risk assessment on methylenedlphenyl d//socyanate {MDI)i Final Draft of 28/07/2003. 

Rapporteur : Federal Public Service of Public Health, Food-Chain, Security and Environment, DG 

Environment, Brussels, Belgium. 

TGD (1996); Technical Guidance Document ln support of Commission Directive 93/67/EEC -on Risk 

Assessment for new notified substance~ Commission Regulation {EC) No 1488/94 on Risk Assessment for 

existing substances and Directive 98/8/EC of the European Parliament and of the Council concerning the 

placing of biocidal products on the market 

Pauluhn, J. (2002); Critical analysis of biomonltorlng endpoints for measuring exposure to polymeric 

dlphenyl-methane-~4'-dilsocyanate {MDI) in rats: a comparison of markers of exposure and markers of 

effect; Arch. Toxicol., 76, pp 13-22 in RAR (2003) 

15 
ECOLAS Annexes 

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ANNEXES 

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£COLAS 

0./. .•• -Se/1/gentprojecttitef: draft (datum) of niets /ndlen finaaf 

Annex 1: Letter from Henkel regarding MDI containing hot melt adhesives 

06 •• July 21.105 

Pl!R- Hotmdt I used Gun 

Th(~ tcs~ i'(~IHJ.rt 91884~9~6A from MiljijaChemie of Aug. 24, 

200 I, discussed two types of holt. nwU guns1 the su l~:dJm.ft 

old (HaJte1') und new (neue) type. 

Thus test '+V1W IlfHHk\ before the decision to Bm.1nch the 

;m)(Juct 

And~ as n result of thi."l test only the SQ called new (nem.:) 

Cun was introduc~d in the market. 

J<in~l 1'1.-!gards 

H E T\ K E L KGnA 

!)i o'(o~l(u• 

l'•·r.~th~>~t l:!lt'ety·r~gl•lnt<ll'}' Mfnirs 

/ 

./ / .:' ;' " 

-' L ·"'· / / I 

;""?7~··- /' 

.. l--- . ,/~.--L-1 \\'. tJrbaim 

M~1.m~~~r 

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Annexes 

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ECOI.AS Annexes 

0./. ... -Se/1/gentprojecttite/: draft (datum) of nlets fnd!en finaal 

Annex 2: Letter from AKPU regarding recognised cases of proven sensitisation amongst OCF 

users 

ISOPA 

Attn. Secretarv Gener:~l 

Dr. ~·fike Jeff; 

E. Van Nieuwenlmv~e Laau 4 

B-1160 Brus~el · 

Belgie 

Tilburg 10.06.05 

Dear Mr .left's, 

europeon DCF produce' oommll"ee k 

Hereby I would li.ke to declare that none of my members repo1ted that iu the la~t approximately 25 

yean there ha; been to their l:nowledge any one of recognised case ofproven .~emilisatioll reaction, 

I.e. identified allergk inhnlntit•e or sl:in reaction dt~e to the exposme \'enus MDI ba~ed 

polyllrethane foam~. 

The membm of AKPU repres~mt about 9 5 ~.-:, of the producers of one component foam in Europe. 

'

lil Unfortunately I cauuot give you n detailed number of employee; of these compauie; because there 

i{ .u-.: of very dift~rent $iZe and are producing in many case$ a wide nmge of products. 

I 

AKPU 

Dr. )..f.F.A. van Die~;r,en 

Pre!;ident 

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Huntsman Division (PU, PP, AdMat) PU 

Region (US, EAME, Asia) EAME 

Product (OCF, SPF, SPF kits, FR resins, Polyurea, Adhesives, OCF 

Coatings, Elastomers, Sealants, Other) 

Is test data available? (If answer is "NO", please save this No 

form and email it to Michelle Koenig. If"YES", continue 

survey). 

Is this information considered Confidential Business No 

Information (CBI)? Yes or No 

Chemical Composition of the formulated products (e.g Polyurethane 

polyurethane, polyurea) 

BriefName of the study conducted (e.g. "Frankel Home FEICA position paper on the use 

Testing"). of gloves for MDI containing 

mixtures, in particular OCF offered 

to the general public 

1 Diisocyanate Tested (MDI, TDI, HDI)? 

2 Curing (surface) or Exposure (airborne)? 

3 Relevant Data Summary- Indicate variables studied e.g. 

environmental conditions, ventilation rates, temperature, 

humidity, catalysts/reactants present, proportioning/mixing, 

application site (indoors or outdoors); quantity of product 

used, application method and square footage covered. 

4 Test lab methods/ Instruments used/ Detection levels, QC 

measures, levels of detection 

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Experimental Parameters (sampling times, strategy) 

5 Summarized Test Data Results 

6 Sensitivity Analysis (if any) 

7 Identify location of above data in document - Pages/Para (e.g. 

Pg2 Para4) 

8 Was Reoccupancy time determined? 

9 If answer to 8 is yes, indicate reoccupancy time. 

10 Exposure limits (occupational and general population limits) 

11 Quantitative Testing: Indicate whether unreacted 

diisocyanates were present, type of surface, and results 

obtained at each interval measured 

12 Other Data on Curing: Tack Free time, cuttable, expansion 

time, light traffic, ready to use etc 

13 Data related to formation ofbyproducts, particularly - substances that continue to off-gas over time. 
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FEICA I Association of European Adhesives and Sealants Manufacturers 1 Use of gloves 

FEICA position paper on the use of gloves for MDI 

containing mixtures, in particular One Component 

Foam/OCF (PU Construction Foams) offered to the general 

public 

FEICA, the European Adhesive & Sealant Manufacturing Association is a multinational 

association representing the European Adhesive and Sealant Industry. With the support of 15 

national associations and several direct and affiliated members, FEICA coordinates, represents 

and advocates the common interests of our industry throughout Europe. In this regard FEICA 

aims at establishing a constructive dialogue with legislators in order to act as a reliable partner 

to resolve issues affecting the European Adhesive and Sealant Industry. 

Situation 

Commission Regulation EC No 552/2009 of June 22nd 2009 (Reach Annex XVII) introduces 

additional protective measures for many substances on the market. 

Methylenediphenyl diisocyanate (MDI) which is plac.ed on the market after 27 December 201 0, 

as a constituent of mixtures in concentrations equal to or greater than 0,1% by weight of MDI for 

supply to the general public, requires specific labeling as well as protective gloves. REACH 

defines placing on the market as supplying or making available, whether in return for payment 

or free of charge, to a third party, which means that no MDI containing mixture can be sold to 

the general public without protective gloves and the required labeling. The original text 

concerning MDI is given here: 

1 I 3 
FEICA 1 Association of European Adhesives and Sealants Manufacturers 1 Use of gloves 

56. Methylenediphenyl diisocy:ma.te 

{MDI) 

CAS No 26447·40·5 

EC No 247-714-0 

1. Sl1all not be plac-ed on the market after 27 December 2010, ns n 

constiruent of mixtures in concentrations equal to or greater th,,n O,l % 

b)• weight of MDI for supply ro the general public, unless st1pplier~ sh~ll 

ensure before the placing on the market that the packaging: 

(a) contain:; protective gloves which comply with the requirement: of 

Council Directive S9J6S6fEEC (••u•u••j; 

(b) h marked Vl:tibly, legiblr and indelibly as follows, nnd without 

prejudice to other Community legislation conceming the classification, 

p;~ckaging and labelling of submmces <~nd mixtures: 

#- Persons already sensitised to diisocyanates may develop allergic 

reactions when using this product. 

Persons suffering from asthma. eczema or sk.ln problems should 

avoid contact, including dermal contact, with this product. 

This product should not be used under conditions of poor ve.nti· 

lation unless a protective mask \\i.th an appropri;ne g>1; filter (i.e 

type A 1 according to Sti~ndard I!N H 38i) is used." 

2. By way of derogation, paragraph l('a.! ~hall not apply to hot melt 

adhe~ives. 

(>:""" .. ) 0! L 399, 30.12.1989, p. !S. 

Consumer exposure for this type of applications can be described as follows: 

During normal use, no OCF PU product comes in contact with gloves. The gloves serve as 

protection in case of accidental spillage. 

Single-use gloves are used for an application time of typically 2 to 4 minutes since the OCF 

container is completely empty within this timeframe. 

OCF products present a foam structure upon dispensing, so in case of spillage onto the 

gloves there is no liquid pressure applied to the gloves even if a consumer should completely 

immerse his or her hands into the foam. This way, the penetration force remains considerably 

lower than in a liquid such as pure MDI. 

Glove Testing 

Testing is performed according to EN 374 by an approved certification body, TOV Rheinland 

LGA (Leipzig) in order to confirm consumer protection against exposure to MDI. 

Testing was executed as follows: 

Permeation is tested for 1 0 minutes, which represents at least twice the actual exposure 

time 

Testing is performed with pure liquid MDI. 

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FEICA 1 Association of European Adhesives and Sealants Manufacturers 1 Use of gloves 

Glove seams are tested under air pressure as well as water pressure. 

- All CE marked gloves require a random series of gloves to pass all tests. 

MDI permeation of PE materials tested proves to be below detection limits. 

Seams of the gloves tested, with a thickness of 0,020 to 0,025 mm, proved to be reliable under 

these testing conditions. 

Conclusion 

The conclusion of the certified body is that the gloves tested provide adequate consumer 

protection against MDI exposure during the application of MDI containing mixtures, within a 

limited timeframe of at least 5 minutes, which fits the use of OCF products by the general public 

(as explained above). 

Based on the testing results obtained, FEICA adopts the following position: 

- PE gloves that have passed EN 374 tests such as executed by TOV Rheinland LGA, provide 

reliable consumer protection against MDI exposure while using OCF PU foam products. 

- By including gloves of this quality into the packaging of PU OCF foams, manufacturers 

comply with Commission Regulation EC No 552/2009 with respect to the required gloves 

according to Protective Equipment Directive 89/686 for the general public. 

- The test results are also applicable for applications of MDI containing mixtures other than 

OCF (such as PU adhesives and sealants),as confirmed by the testing institute (TOV Rheinland 

LGA). 

- The gloves will have to be replaced after 5 minutes in case of product spillage onto the 

gloves as prescribed by the testing report. 

October 27th 201 0 

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CONTAINS NO CB.I