# 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

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### 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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### 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 EPAto 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 oftheir 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 oftheir commercial use. 

## CONTAINS NO CBI
10003 Woodloch Forest Drive, The Woodlands, Texas 77380 Tel.: 281-719-6000 Fax.: 281-719-6416 www.huntsman.comMs. 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 ofthe 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 IndustryAffairs 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 ofgloves for MDI containing mixtures, in particular OCF offered to the general public

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## ( Huntsman Division (PU, PP, AdMat) PU Region (US, EAME, Asia) EAME Product (OCF, SPF, SPF kits, FRresins, Polyurea, Adhesives, Adhesives Coatings, Elastomers, Sealants, Other) Is test data available? (Ifanswer is "NO", please save this YES form and email itto Michelle Koenig. If"YES", continue survey). Is this information considered Confidential Business NO Information (CBI)? Yes orNo Chemical Composition ofthe fonnulated products (e.g polyurethane polyurethane, polyurea) BriefName ofthe study conducted (e.g. "Frankel Home Risk Calculation ofisocyanate Testing"). emission at workplaces during processingreactive PU adhesives 1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 2 Curing (surface) orExposure (airborne)? Curing 3 RelevantData Summary

- Indicate variables studied e.g. RT environmental conditions, ventilationrates, temperature, 200g adhesive humidity, catalysts/reactantspresent, proportioning/mixing, application site (indoors oroutdoors); quantity ofproduct used, application method and square footage covered. 4 Test lab methods/ Instruments used/Detection levels, QC Unclear, but standard methods measures, levels ofdetection Experimental Parameters (samplingtimes, strategy) ? 5 SummarizedTestDataResults Fully curedafter 300 minutes. Althoughtopic relates to industrial setting. The adhesives canbe used byprofessionals/consumers? as well 6 SensitivityAnalysis (ifany) ? 7 Identify location ofabove data in document- Pages/Para (e.g. Slide 20 Pg2 Para4) 8 Was Reoccupancytime determined? No 9 Ifanswerto 8 is yes, indicatereoccupancytime. 10 Exposure limits (occupational and generalpopulation limits) 0.05 mg/m3 No EAME general population limit inEU 11 Quantitative Testing: Indicate whetherunreacted diisocyanates were present, type ofsurface, andresults obtained at each intervalmeasured 12 OtherData on Curing: TackFree time, cuttable, expansion time, lighttraffic, readyto use etc 13 Datarelated to formation ofbyproducts, particularly substances that continueto off-gas over time.

## )

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# Risk Calculation of Isocyanate Emission at

Workplaces during Processing Reactive Polyurethane Adhesives
Presented by: Co-Author(s):

Company

Congress Partners 

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### Dr. Jasmin Trautmann Thomas Hensel, lnstitutfor 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

HINTERWALDNER

CONSVLTING



# v VIIKEIIIZ._ .. / Risk Calculation of Isocyanate Emission at 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

• Berufsgenossens.choft Druck

und Papierverorbeitung

--- _ ____.../ ..__./Motivation Motivation for measuring occupational

exposure

1.) Extensive data base for an overview of isocyanate concentration at
workplaces.
2.) • Comparison of different climate conditions: humidity, application temperature, exhaustion.

• Evaluation of available analytical techniques and their sources of error.
(Additional simulation of workplaces at the IF AM.)

3.) Detailed description of the workspace environment; Evaluation of the

assumed factors. BG

• Bervfsgeno$senschoft Druck

und Papierverarbeitung • Fraunhofer lnstitut Fertigungstechnik Materialforschung 2Outline

I. Polyurethane adhesives

II. Isocyanate air concentration

Ill. Air sampling methods

IV. Monomer exposure

v. Summary I Conclusions

BG

• Berufsgenosse. nsch<;Jft Druck

und Popierverorbe1tung

· .. __ / II Fraunhofer lnstitut Fertigungstechnik Materialforschung 3 **'"--~/**Section I

I • Polyurethane adhesives

BG Berufsgenossenschoft Druck vnd Popierverorbeitvng li Fraunhofer lnstitut Fertigungstechnik Materialforschung 4I Polyurethane adhesives Application areas

• Bookbinding

• Automotive interior trim

• Wood coatings Application methods

• Spray application

• Slot nozzle application

• Roller application
BG

• Berufsgenossenschaft Druck

und Popierverorbeitung B Fraunhofer lnstitut Fertigungstechnik Materialforschung 5I 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.

BG li

• Bervfsgenossensc.haft Druck

vnd Popierverorbeitung Fraunhofer lnstitut Fertigungstechnik Materialforschung 6IPolyurethaneadhesivesOccupationalDisease14012010080604020019951996 199719981999200020012002200320042005BG•BerufsgenossenschaftDruckundPopierverarbeitung.._____/1-----1verifiedoccupationaldiseasenoinsuranceeventc::::::Jverifiedoccupationaldisease,withandwithoutdissabilitypension-a-reportedoccupationaldiseaseInallindustrybranchesOccupationaldiseaseNo.BK1315Source:BK-DOKofHVBGIJJFraunhoferlnstitutFertigungstechnikMaterialforschung7''--'Section II II Isocyanate air concentration .BG Berofsgenossenschoft Drock

und Popierverorbeitung IJ Fraunhofer lnstitut Fertigungstechnik Materialforschung 8II Isocyanate air concentration Monomers
PI Qo Q NCO 4,4'-MDI HOI BG

• Berufsgenossenschoft Druck

und Popierverorbeitvng

__ j NCO

NCO **~**

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9 **~**

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CH2

**~ ~**  2{20 ocyN-Q **~NCO** C

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l[_J ocN-Q CH 2 ...... 2,4'-MDI **(it~)** 2,2' -MDI CH3 NCO PMDI CH3 **OCN~NCO** JDJI: 0,021 **HP~** oc)

NCO 2,4-TDI 2,6-TDI IJ Fraunhofer lnstitut Fertigungstechnik' Materialforschung 9 **"--~----**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/m 3

= 0,005 ml/m 3 (ml/m 3

or ppm)

• 5 min exposure limit: AGW x 2 Xn Inhalation is the important

exposure route of lsocyanates .

**~** BG .. Bervfsgenossenschoft Druck

vnd Popierverorbeitung • Fraunhofer lnstitut Fertigungstechnik Materialforschung 10II Isocyanate air concentration Estimation of occupational

exposure Measured MDI air concentration on adhesive work places

50 45 40 ........ 35
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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)

BG

• Berufsgenossenschoit Druck

und Popierverorbeitvng !I Fraunhofer lnstitut Fertigungstechnik Materialforschung 11Section Ill Ill Air sampling methods

• BG Bervfsgenossenschoft Druck unci Popierverorbeitung !I Fraunhofer lnstitut Fertigungstechnik Materialforschung 12Ill Air sampling methods
Air sampling methods Direct Reading Instruments. Advantages: immediate results, ease of use (color reaction), inexpensive Disadvantages: Not so accurate or precise as indirect sampling methods.

Pumped detector badge; visually matched with reference color comparator Paper tape instrument

Useful for an estimation of diisocyanate emission

BG

• Bervfsgenossensc.hoft

Druck und Popierverarbeitung II Fraunhofer lnstitut Fertigungstechnik Materlalforschung 13 **'~** /Ill Air sampling methods Indirect (derivatization) method

• Pumped filter or impinger trapping medium.

• Fast infield reaction of the diisocyanates with a derivatization reagent.

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.... Analytical instruments High Pressure Liquid Chromatography -+ Advantage: Good sensitivity, selectivity
Disadvantage: Method requires standards and analytical facilities. Advantage: Accurate method, usable for a validation of working places

BG

• Bervfsgenossenschoft Druck

und Popierverorb.eitung II Fraunhofer lnstitut Fertigungstechnik Materialforschung 14I Ill Air sampling methods Derivatization reagents for the evaluation of isocyanates
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

• Berufsgenossenschoft Druck

und Popierverorbeitung Detection UV/ FLD/ECD MS UV/ FLD UV, ECD UV/FLD FLD/ECD ,'-.. __ / Advantage/ Disadvantage TRIG estimation, light sensitive Expensive, non-routine method, impinger method, excess reagent can be evaporated Polyisocyanates difficult, good separation of monomers, sublimes in hot wet conditions
TRIG estimation, lower specivity, but higher stability than 2PP TRIG estimation, MAP not commercial available TRIG estimation li Fraunhofer lnstitut Fertigungstechnik Materialforschung 15 "---·-/Ill Air sampling methods Measurement time and distance

Lab test PU Hotmelt, MDI - 5 wt. %>, heated to 140°C 200 g adhesive Small room BG

• Berufsgeno$senschoft Druck

vnd Papierverarbeitvng 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

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0

20 40 60 80 100 120 140 160 180 200 distance [em] IJ Fraunhofer lnstitut Fertigungstechnik Materialforschung 16Ill 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
BG

• Berofsgenossenschaft Druck

und Po

pi erverorbe itung

, _______ / HPLC, 2PP cal. Air concentration (MDI) in J.lg/m 3 278 2 283 12 color indicator (poly MDI scale) J.lg/m 3 48 0 82 0 color indicator (MDI scale) J.lg/m 3 305 0 450 0 II Fraunhofer lnstitut Fertigungstechnilc Materlalforschung 17 **'~/**Ill Air sampling methods polyMDI adhesive, RT, spray application HPLC, 2PP cal. color indicator

color indicator

Air concentration (poly MDI scale)

(MDI scale) 1Jg/m 3

(MDI)

in 1Jg/m 3 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!

BG

• Bervfsgenossenschoft Druck

und Popierverorbeitung II Fraunhofer lnstitut Fertigungstechnik Materlalforschung 18Section IV IV Monomer

exposure

• BG Berufsgenossenschoit Druck und Popierverorbeltung .,

- Fraunhofer lnstitut Fertigungstechnik Materialforschung 19IV 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 Berufsgenossensc:hoft Druck und Popierverorbeitung 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 content

b . **~"'.(.:'** //' ;'/ **~** /'

v

/ / / // 20 40 60 80 Content

of HOI [mg/g]

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

: \ I

--- 1C-PU Adhesive, 4.4'-MDI traction

\

.......,. 2C..PU Adhesive based on 4.4'-MDI

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

0 so 100 nme[min] 250 300 350 j ' ll I 400 ., Ill Fraunhofer lnstitut Fertigungstechnik Materialforschung 100 120 20IV Monomer exposure Temperature dependence of the emission rates

2,8x1 Os 2,6x1 0 s .----. 2,4x1 Os
..c N E 2,2x1 0 5
........... 0) ::::1. 2,0x1 Os

___, QJ 1 ,8x1 Os
+-' C"Ci !.,...., 1 ,6x1 Os

c 0 1 ,4x1 Os

Vl l/) E 1 ,2x1 Os

QJ 1 ,Ox1 Os

u '+- 4

u 8,0x1 0

QJ n. 6,0x1 0 4

Vl 4,0x1 0 4 2,0x1 0 4 0,0 BG

• Berufsgeno$senschoft Druck

unci Popierverorbeitung -•- standard PU-Hotmelt -•- emission reduced PU-Hotmelt PU decomposition

! ·-------- • •

130 140 150 160 temperature [° C] 170 IJj Fraunhofer lnstitut Fertigungstechnik Materialforschung 21 ·, __ /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/m 3 ]

f = factor like adhesive temperature, air flow

p =constant
BG

• Bervfsgeno.ssenschoft Druck

und Popierverorbeitung II Fraunhofer lnstitut Fertigungstechnik. Materialforschung 22· 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 distance

**~** .BG .. Berufsgenosse.nschoft Druck

und Popierverorbeitung

"'-/ **---~** -·------·- influencing factors II Fraunhofer lnstitut Fertigungstechnik Materialforschung 23 '-,_ ... /IV Monomer exposure Horizontal and vertical distribution of isocyanates Diisocyanate emission decrease with:

• Rising humidity

10 9

• Lower monomer content

8 -11- with source exhaustion

• Good exhaustion "'E

7 .._ Cl 2: 6 ---without source exhaustion

t: 0

• Lower application temperature

**~** 5 **~** 4 c (])

• High air volume (.) 3

t: 0 (.) I... 2 "(U i3 1 **~** 0 -1 0 100 200 300 400 measurement distance [em] Depending on these parameters the emission decreases in the
·horizontal dimension.

**~** BG .. Berufsgenossenschaft Druck

vnd Popierverorbeitung • Fraunhofer lnstitut Fertigungstechnik Materialforschung 24IV 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 BG

• Berufsgenossenschaft Druck

und Popierverorbeitung 25 f..lg/m 3

MDI **~~1il** 4 meter

14 f..lg/m 3

MDI **~:5!!ft'3"':li!lf ':rnwr~**  3 meter 11f..lg/m3 MDI &lliBBilfl 1.7 meter

7 llgfm 3 MDI ground floor B Fraunhofer lnstitut Fertigungstechnik Materialforschung 25 ......__ _..--'Section V V Summary I Conclusions

• BG Berufsgeno.ssenschoft Druck und Popierverorbeitung - • Fraunhofer lnstitut Fertigungstechnik Materialforschung 26V 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 personnel works with

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 BG

• Berufsgeno,ssenschaft Druck

und Papi

erverorbe itung II Fraunhofer lnstitut FertigungstechnikMaterialforschung 27,.---- ___ V Conclusions Derived recommendations: exhaustion
BG

• Berufsgenossenschaft Druck

und Popierverorbeitung better exhatrstion = • Fraunhofer lnstitut Fertigungstechnik Materialforschung 28V Conclusions Derived recommendations

:

• Emission reduced adhesives

• Low application temperature

• Smart exhaustion

• High enough air volume

• Think about breakdown situation

BG ..

. - Bervfsgenossenschoft Druck

vnd Popierverorbe1tung IJ Fraunhofer lnstitut Fertigungstechnik Materialforschung 29 **~/**,.- • BG Berufsgenossenschoft Druck und Popierverorbeitung Thank you for your attention! ll!li - Fraunhofer lnstitut Fertigungstechnik Materialforschung 30• **"--~/** BG Berufsgenossens.choft Druck und Popierverorbeitvng Fraunhofer lnstitut Fertigungstechnik Materialforschung 31 ••Huntsman Division (PU, PP, AdMat) PU Region (US, EAME, Asia) EAME Product (OCF, SPF, SPFkits, FRresins, Polyurea, Adhesives, OCF & Adhesives Coatings, Elastomers, Sealants, Other) Is test data available? (Ifanswer 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 orNo Chemical Composition ofthe formulated products (e.g polyurethane polyurethane,_golyurea) BriefName ofthe study conducted (e.g. "FrankelHome Danish consumerstudy Testing"). 1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 2 Curing (surface) orExposure (airborne)? Exposure/curing 3 Relevant Data Summary

- Indicate variables studied e.g. environmental conditions, ventilationrates, temperature, humidity, catalysts/reactantspresent, proportioning/mixing, application site (indoors or outdoors); quantity ofproduct used, application method and square footage covered.
4 Test lab methods/Instruments used/Detection levels, QC OSHA47 measures, levels ofdetection 1.2 PPHPLC-UV 25 ng/ml Experimental Parameters ( samplingtimes, strategy) Car window adhesive sampling of 12 minutes Exposure during applying: Sample taken at breathingzone 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 productfor 15 minutes Flooradhesive 200 grs over25cmX40 em surface area. Sampling at 25 em above product for 15 minutes 5 SummarizedTestDataResults Allresults 

### <detection limit 6 SensitivityAnalysis (ifany) 7 Identify location ofabove data in document

- Pages/Para (e.g. Pg22/23 Pg2Para4) Section4.4 pg41 8 Was Reoccupancy time determined? No 9 Ifanswerto 8 is yes, indicate reoccupancytime.10 Exposure limits (occupational andgeneralpopulationlimits) No EAME generalpopulationlimit inEU 11 Quantitative Testing: Indicate whetherunreacted diisocyanates were present, type ofsurface, andresults obtained at eachintervalmeasured 12 OtherData onCuring: TackFreetime, cuttable, expansion time, lighttraffic, readyto use etc 13 Datarelatedto formation ofbyproducts, particularly substances that continue to off-gas overtime.

Ii \ 

### DANISH MINISTRY OF THE ENVIRONMENT Environmental ProtectionAgency



# 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 ofChemicaISubstances in Consumer Products, No. 

## 82 2007TheDanishEnvironmental ProtectionAgency will, when opportunity offers, publish reports and contributions relating to environmental research and developmentprojects financed via the DanishEPA Please note that publication does not signify thatthe contents ofthe reports necessarily reflect the views of the Danish EPA Thereports 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 CONSUMERPRODUCTS, WHICH MAY 

### 5 7 9 12
CONTAINANYOFTHEFIVE 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 METHYLTETRAHYDROPHTHALIC 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 OFEMISSION ANALYSIS FROM SELECTED CONSUMERPRODUCTS 22 3.1 ANALYSIS OF MDI EMISSION FROM VARIOUS CONSUMER PRODUCTS 22 

### 3.1.1 Sample treatmentandcollection 22 POLYURETHANEONECOMPONENTSEALANT ANDADHESIVE 23 FLOORADHESIVE HAIR CONDITIONER 23 23 HAIRSPRAYWITHPOLYURETHANEASDECLAREDINGREDIENT24 POLYURETHANERAINCOAT FOAMMATTRESSANDSPRINGMATTRESS 

### 3.1.2 Methodof analysis EXTRACTION CHROMATOGRAPHY 

### 3.1.3 Calculation of detection limit 3.1.4 Results 24 24 

### 25 25 25 

### 26 26



### 33.2 ANALYSIS OF PHTHALIC ANHYDRIDE DERIVATIVES IN CONSUMER PRODUCTS 26 

### 3.2.1 Sample tl'eatmentandcollection 27 3.2.2 Results of phthalicanhydl'idemeasurements 30 3.3 ANALYSIS OF GLUTARALDEHYDE IN CONSUMER PRODUCTS 32



### 3.3.1 Results of glutal'aldehydemeasurements 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 Limitvalues 36 4.2 HEXAHYDR0-4-METHYLPHTHALIC ANHYDRIDE, CAS 19438-60-936 

### 4.2.1 Hazards 38 4.2.2 Limitvalues 38 4.3 PHTHALIC ANHYDRIDE, METHYLTETRAHYDRO- (UNSPEC.), CAS 11070-44-3 38



### 4.3.1 Hazards 40 4.3.2 Limitvalues 40 4.3.3 Exposul'eandl'iskassessmentfol'consumel'sfol'allthe above phthalicanhydride derivatives 40 4.4 METHYLENEDIPHENYLDIISOCYANATE, CAS 26447-40-5, 5873-54- 1 AND 101-68-8 41



### 4.4.1 Hazards 42 4.4.2 Limitvalues 43 4.4.3 Exposul'e andJ'iskcharacterisationfor consumers 44 4.5 GLUTARALDEHYDE, CAS 111-30-8 45 

### 4.5.1 Hazards 45 4.5.2 Limitvalues 47 4.5.3 Exposure andl'iskcharacterisationforconsumers 47 5 CONCLUSION 49 

### 6 REFERENCE LIST 

### 51



### 4 I !

,,

### I j

\ I /

# Foreword

This projectwas carried outwith DTC Health and Environment, a business unit of DHIWater and Environment, as project leader, and NERI (National Environmental Research Institute) as partner. DTC carried outthe initial search for relevant products containing respiratory sensitizers. Projectassistant Hanne S0rensen, DTC, made the tracking and purchases of most ofthe products analyzed. Toxicologist Inge S0borg reviewed the first phase report. and Chief toxicologist Karl-Heinz Cohr carried outthe quality control ofthe final report. SecretaryVibeke Salmon carried outthe text editing and translation. At the NERI, Senior Scientist Betty BCtgel Mogensen, planned, executed and reported the chemical emission analysis with the aid oflaboratory technicians IngaJensen and Kitty Petersen. Quality control on the performed analyses was carried outby Betty BCtgel Mogensen. Theproject was carried outfor the Danish Environmental Protection Agency (DEPA) on contract no. 7041-0513 underthe programme for surveys on chemical substances in consumer products. The primary contact person in DEPA for this projectwas Annette Ejersted, who was initially seconded by Lea Frimann Hansen, and later FrankJensen. The projectwas initiated in March 2006 with final delivery in November 2006.



### 56 JI

# Summary

In 2004, the Danish EPA issued a revised list ofunwanted substances (Orientering fra Milj0styrelsen, nr. 8, 2004). The criteria for inclusion in this list were among others the classification ofthe substances. One ofthe criteria was classification R42: "May cause sensitization byinhalation". Five substances are on the list exclusively because ofthis 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 ofthe present projectwas to 1. Make an inventory ofconsumer producttypes that may contain any of the five R42-substances. 2. Examine, ifconsumers actually are exposed to the substances when using such products. 3. Assess, ifthe exposure is large enough to cause health effects in the consumers The inventorybelow was created by searching SPIN

- database on substances in preparations in Nordic countries, the INCI list, and data from earlier projects on consumerproducts. In addition, five trade associations and retail stores were asked about their knowledge on the matter, and the literature was searched for cases ofrespiratory sensitization due to any ofthe five substances in consumerproducts. All in all, 19 products were sampled for inclusion in an emission analysis. The number ofproducts within each group is given in parenthesis. The following consumer products may contain phthalic anhydride derivatives:
• Nail Lacquer (6) • Two-componentepoxy adhesive (2) The following consumer products may contain glutaraldehyde:
• Cosmetic products (mouth washes and creams) 

### (O) • Disinfectants 

### (O) • Film developers for consumers 

### (O) • Paperhandkerchiefs 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 roofcoating (O) 

## • Hotmelt adhesives (O) 

## • Floor adhesives (1) 

## • Polyurethane materials in clothing 

### (1) 

## • Sprayhair fixatives and conditioner (2) When searching the marketitwas not possible to obtain cosmetic products, disinfectants, nor film developers with glutaraldehyde. Neither was it possible to obtaintwo-component adhesives and putties, liquid roofcoating, nor hot melt adhesives with a content ofmonomeric MDI. All purchaseswere carried out while pretending to be ordinary consumers, not professionals. Although some ofthe 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, atleast 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 ofthe respiratory sensitizers from the 19 products obtained could be detected bychemical analysis. Hence, no risk ofsensitisation to phthalic anhydrides, MDI or glutaraldehyde can be attributed to any ofthe products analyzed.



### 8 )

\ l

# Introduction

In 2004, the Danish EPA issued a revised list ofunwanted substances (Orientering fra Milj0styrelsen, nr. 8, 2004). The criteria for inclusion in this list were among others the classification ofthe substances. One ofthe criteria was classification R42: "May cause sensitization byinhalation". Five substances are on the list exclusively because ofthis 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 Exposure to these five substances through consumer products is virtually unknown, and the Danish EPA needs more knowledge ofthe use ofthese substances in consumerproducts, and the emission ofthe five substances from products containing the substances. The purpose ofthe presentprojectwas to 1. Make an inventory ofwhatkind ofconsumerproducts may contain any ofthe five R42-substances. 2. Examine, ifconsumers are actually exposed to the substances when using such products. 3. Assess, ifthe 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 ofthis project. The final goal ofthe projectis to present an assessment ofthe health risk of the consumers from the five R42 substances. The projectwas divided into two phases: 1. Inventory ofthe kind ofconsumerproducts, which may contain any ofthe five R42 substances 2. Exposure assessment and assessment ofhealth risks



### 9

### 1011

# 1 Methods

Forthe phase 1survey the occurrence ofthe five substances has been searched in the sources given below. Data onthe use ofthe five respiratory sensitizers have been collected in SPIN -database on substances in preparations in Nordic countries. The INCI list (International Nomenclature ofCosmetic Ingredients) hasbeen searched for occurrence ofthe five substances. In addition, data have been retrieved from earlier projects on consumer products published on the web page ofthe DanishEnvironmental Protection Agency. The following trade associations and retail stores have beenrequested to provide available data on the use ofsome or all ofthe five substances: Plastindustrien i Danmark DanmarkFarve- og Lakindustri COOP Danmark Dansk Supermarked Association ofDanish Cosmetic, Toiletries, Soap and DetergentIndustries (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 ofthe five substances in consumer products. After having established the type ofconsumer products mostlikely containing the five substances, products have been searched and sampled by personal purchase in retail outlets, both physically and onthe Internet. The purchased products were delivered to the National Environmental Research Institute for emission analysis.



### 12 

## )

### 13

# 2 Inventory of consumer products, which may contain any ofthe 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 ofthe 428 preparations are registered as consumer preparations in Norway and Sweden. The industrial use for which the preparations are registered in Denmarkis:
• Farming ofanimals • Hospital activities • Human and health services • Manufacture ofpaints, varnishes and similar coating, printing inks and mastics • Manufacture offood and beverages • Dentists • Painting • Manufacture ofmachinery and equipment • Othermotor vehicle services 

### • "All kinds ofactivities" • 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, butnotphotographic 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 itis banned in aerosol and spray products. Labelling with "Contains glutaraldehyde" is mandatory, ifthe concentration in the final products exceeds 0.05%. The INCI name for glutaraldehyde is Glutaral.

14 

## )The search on the internetby 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 onthe internetby 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 ofchemical substances in consumer productsrevealed that glutaraldehyde residues may be present in paper handkerchiefs and toilet paper in concentrations ofup to 0.08 kg/t (1). An additional search for cases ofrespiratory allergy resulting from exposure to glutaraldehyde emission from consumer products was carried outin the database PubMed. Several cases ofasthma resulting from occupational exposure to glutaraldehyde containing disinfectants were found, butnone were relatedto private use. Cases ofexposure to glutaraldehyde in the private setting, were only found in relation to contact dermatitis, butnot 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 • Paperhandkerchiefs 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. Ofthese, 38 preparations are registered in Denmark. None ofthe 57 preparations are registered as consumerpreparations. The industrial use for which the preparations are registered in Denmarkis:
• Manufacture ofothertransport equipment • Sale, maintenance and repair ofmotorvehicles and motor cycles; retail sale ofautomotive fuel • Manufacture ofaircraft and spacecraft (includes repair ofair 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.



### 15Hence, CDA may occur as a residual monomerin consumer products. In cosmetics, CDA may occur as a monomerindifferent film forming polymers used in e.g. nail lacquer. CDA as such is notfound onthe INCI list. In a declaration, it might be listed as phthalic anhydride in the kind ofpolymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. We do not know ifCDA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers. In 2002, the information centre for Environment and Health published a list ofproducts 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 ofrespiratory sensitization gave several hits indicating thatoccupational exposure to epoxy resins and their hardeners is a commonreason for respiratory sensitization to CDA (4,5,6). No cases ofCDA allergy from private use ofepoxy products were found in the PubMed database. However, as two-component epoxy products are available for private use, some ofthese were sampled for CDA emission testing. 2.2.1 Conclusion With regard to CDA containing or -emitting products, two-component epoxy adhesives and nail lacquerwere considered relevantfor emission analysis.
2.3 Hexahydro-4-methylphthalic 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 ofthese were registered in Denmark. In fact, all three were registered in Sweden, and none ofthese were consumer preparations. Industrialuse categories are:
• Manufacture ofchemicals and chemical products • Manufacture ofrubber and plastic products • Manufacture ofelectrical machinery and apparatus • Heattransferring agents • Adhesives, binding agents Hence, HPMA may occur as a residual monomer in consumerproducts. In cosmetics, HPMA may occur as a monomerin different film forming polymersused in e.g. nail lacquer. HPMA as such is notfound on the INCI list. On a declaration, it mightbe listed as Phthalic anhydride in the kind of

16 --""\polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer. We do not know ifHPMA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers.

In 2002, the information centre for Environment and Health published a list ofproducts 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 ofrespiratory sensitization gave a few hits indicatingthat 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 productrelated 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 MethyltetrahydrophthaIic anhydride, CAS 11070-44-3 Synonyms: MTHPA tetrahydromethyl-1,3-isobenzofurandione 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 consumerpreparations. Industrialuse categories are:
• Manufacture ofchemicals and chemical products • Manufacture ofrubber and plastic products • Manufacture ofelectrical machinery and apparatus • Process regulators • Heattransferring agents • Curing agents for plastic • Others notmentioned specifically Hence, MTHPA may occur as a residual monomerin consumer products. In cosmetics, MTHP A may occur as a monomerin different film forming polymersused in e.g. nail lacquer. MTHPA as suchis notfound onthe INCI list. Ona declaration, it might be listed as phthalic anhydride in the kind of polymer used, e.g. Phthalic Anhydride/Benzoic Acid/Trimethylolpropane Copolymer.

17We do notknow ifMTHPA or only phthalic anhydride is actually employed in the phthalic anhydride copolymers. In 2002, the information centre for Environment and Health published a list ofproducts 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 ofrespiratory 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 consumerproductrelated cases were found during this search. 2.4.1 Conclusion In conclusion, with regard to MTHPA containing or -emittingproducts, 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 ofthe 308 preparations are registered as consumer preparations in Norway and Sweden. The industrial use for which the preparations are registered is:
• Construction • Manufacture ofmotorvehicles, trailers and semi-trailers • Manufacture ofbasic metals • Manufacture offurniture • Manufacture ofrubber and plastic products • Manufacture ofwood and products ofwood and cork, except furniture; manufacture ofarticles ofstraw and plating materials • Wholesale trade and commission trade, except ofmotor vehicles and motorcycles • Private households with employed persons . • Sale, maintenance and repair ofmotorvehicles and motorcycles; repair of personal and household goods • Manufacture ofelectrical machinery and apparatus • Manufacture ofpulp, paper and paper products • Manufacture ofchemicals and chemical products • Manufacture ofother 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 \ j



### \• Adhesives, binding agents • Curingagents • Construction materials • Process regulators • Fillers • Flooring materials Qoint-less floors) Deemingfrom this, MDI or residues ofMDI mightbe emitted from consumer products, such as boatand carrepair kits, furniture (mattresses), two-component adhesives and putties, flooring and wall paper. Polyurethane materials in clothingmay also emit MDI. Secondary exposure to MDI may occur when polyurethane materials are processed bygrinding orheating (9). MDI has been subject to anEU risk assessment, published in 2005 (10). One ofthe conclusions for consumers was that there is a need for limiting risks, since health risks due to combined occupational and consumer exposure could notbe 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 Sprayfoam or One ComponentFoam (OCF): MDI-based OCF is offered in the consumermarket 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 OCFis suppliedinpressurised cans and is applied through a pre-expansion tube (always part ofthe package). The product is released from the nozzle as viscous foam, ratherthan as a sprayed aerosol. Curingstarts immediately and moves from the outside inwards. Therefore, emission and hence potential exposure virtually ceases oncethe outer coathas been cured. However, Sweden has a warning when using the one-componentfrothed foam. PUwood adhesives are used for waterproofbonding and on moist wood. Flooring adhesives are used for wood-parquet. PU paint is used as a primerfor liquid roofcoating, with a long in-service life (10 to 15 years), and for decorative painting. Itis confirmed by industrythat hotmelt adhesives are currently offered to the D.I.Y. (do-it-yourself) market. According to industry, even 2-componentproducts are offered to the D.I.Y. market. One companystated: "Moreover, otherproducts normally offered onlyto the craftsmen can reach end-consumersby self-service atcraftsmenretailers". However, it is very unlikely that the consumer's working conditions are ever appropriate for the use of2-componentproducts containing free MDI (10).

19A 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 beenused, and may therefore emitresidual 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 ofthe respective PEG's and saturated MDI monomer. Theyare 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 itprudentto test the emission ofMDI from aerosol hair fixatives with the above mentioned polymers onthe ingredient list. 

### 2.5.1 Conclusion With regard to MDI containing and -emittingproducts, we decided to look for samples ofthe following products:
• PU-foam articles, such as mattresses • One componentsprayfoam • Boat and carrepair kits • Two-component adhesives and putties • Liquid roof coating • Hotmelt adhesives • Floor adhesives • Polyurethane materials in clothing • Spray hair fixatives
2.6 Resu Its of inquiries Answers to general inquiries about the knowledge ofinclusion ofany ofthe five substances in consumerproducts were given from: COOP Dansk Supermarked A/S The Association ofPlastic Industries in Denmark. Danmarks Farve- og Lakindustri Association ofDanish Cosmetic, Toiletries. Soap and Detergent Industries (SPT) None ofthese respondents were aware ofthe presence ofany such products on the Danish market.
2.7 Resu Its ofsearch for products with Iikely emission ofthe five substances 

### Glutaraldehyde

20The search for products containing glutaraldehyde was very difficult. The search for film and picture developers with content ofglutaraldehyde, and not exclusively for occupational use, was negative after several telephone inquiries
..One inquiry led us to a company who thought they mightprovide a developer with glutaraldehyde for youth schools with classes in photography. However, upon further investigation, this companywas not able to deliver any such developer. Upon this, we concluded that the use ofglutaraldehyde in developers for hobbyuse seems to have been phased out. Next, we thoughtglutaraldehyde might be presentin disinfectants for home use ormouthwashes. Telephone inquiries and store searches revealed no such thing. Finally, since glutaraldehyde according to ourinvestigation maybe found in papertowels and paperhandkerchiefs we purchased some toilet paper and some kitchen rolls made ofrecycled paper. 

### Phthalicanhydride derivatives Two componentepoxy adhesives were readily available from do-it-yourselfmarkets, so samples ofthese products were purchased and sentfor analysis for emission phthalic anhydride derivatives. Nail lacquers containing polymers based on phthalic anhydride derivatives were identified in stores by scrutiny ofthe INCI declaration. The nail lacquers were chosen according to place ofthe polymers in the INCI declaration, since ingredients are supposed to be mentioned in order offalling concentration. Hence, ifthe polymer is mentioned as one ofthe 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 ofmeasuring the emission, ifany would be present. 

### MDI Consumer products made with polyurethane, MOl-copolymer orMDI was easier to find, although some discrepancy ininformation regarding the content ofresidual MOl-monomerin adhesives andjointfillers were found. Cosmetic products were sampled ifthe ingredientlist contained MDI based polymers or copolymers. We purchased samples ofcar window adhesive, floor adhesive,jointfiller, PU-rainjacket, hairspray and conditioner, and mattresses.

21

# 3 Results of emission analysis from selected consumer products

The products thatwere purchased and submitted for analysis are listed in annex 2.
3.1 Ana lysis ofMDI emission from various consumer products Collection and analysis ofair sampleswere carried out according to OSHA (Occupational Safety and Health Administration, U.S. Departmentof Labour), method 4 7 for analysis ofMDIin the occupational environment. Air samples are collected by sucking a known amount ofair 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 HPLCwith UV detector (254 nm). 3.1.1 Sample treatment and collection The purpose ofthe collection was to treat the sample in a way as close to the user situation as possible. 

### Car windowadhesive A car window was placed on a table (see figure 1). The sample was opened, and the adhesive was squeezed out ofthe container with ajointgun while distributingitalong the edge ofthe window pane. After this, the adhesive was covered with the moulding that protects the window pane during transport, mimicking the placement ofthe window in the car frame (realistic work scenario). Duringthe out-squeezing and distribution ofthe adhesive, air was sampled from a height equal to the position ofthe nose ofthe user. Application ofthe adhesive lasted 12 minutes (realistic work scenario). After this, the filter was exchanged with anun-exposed filter, and air was sampled right over the adhesive in nose height for two hours. The remainder-·ofthe adhesive was squeezed out ofthe container, and air was sampled over the adhesive for six minutes (maximum exposure).

22Figure 1. Application of adhesive to car window 

### Polyurethane one componentsealantandadhesive Sealant (160-180 g) was squeezed outin stripes on a non-absorbing surface placed in a plastic tray (see figure 2 below). Collection ofsample was carried out 25 em above the sealant. The collection ofair and expression ofsealant was started simultaneously and continued for 15 minutes. 

### Flooradhesive Approximately 200 g ofthe thin fluid adhesive was spread over an area of approximately 25x40 cm2• (see figure 2below). Suction took place 25 em above the surface for 15 minutes counting from the opening ofthe bottle. 

### Hairconditioner A large handful ofconditioner (app. 25 g) was spread over an area ofapp. 25x30 cm2 (see figure 2 below). Air was collected 25 em above the area for 15 minutes counting from the opening ofthe container.

23Figure 2. Hair conditioner. The plastic tray with non-absorbing material was used for sealant. adhesive, hair conditioner, and hair spray. 

### Hairspraywithpolyurethaneasdedaredingredient Hair spray was sprayed outover a non-absorbing surface of 25x30 cm2 placed in a plastic tray (see figure 2 above). Sprayfor 10 seconds, pause for 10 seconds, and spray for 10 seconds. Air was collected 25 em above the area for 15 minutes. 

### Polyurethanerain coat Collection ofair was started as soon as the plastic bag around the rain coat was opened. The rain coatwas spread out and turned over and around several times during the air collection. Air was collected 25 em above the rain coatfor 15 minutes. 

### Foammattressandspringmattress Collection ofair 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 onevery halfhour. The sampling air flow velocity was 1Llmin in all samplings.

24Figure 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 extractwas analyzed onHPLC (Agilent 1100) Method 1: Column: ZorbaxXDB 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 1mL/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 1mL/min. Temperature 25° C. Injection volume 25 fll. Retention time 10.98 min. 

### Detection Detectionwas carried out at 254 nm on a G1314A VWD variable wavelength detector from Agilent. The extracted samples were analyzed against a row ofstandard 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 ofstandard solution which gave a signal significantly differentfrom the base line was 25 ng/ml.

25

### 3.1.3 Calculation ofdetection limit The detection limit depends on the collected amount ofair. Collection in 12 minutes corresponds to 12litres ofcollected air. The filter was extracted with 4 ml ofsolvent. 25 ng/ml in 4 ml corresponds to 100 ng in 12 1ofair, correspondingto 8 ng/ 1air or 8 pg/m3 ofair. The detection limits for the different analyses appear from table 1below. 

### 3.1.4 Results In some ofthe 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 thatthere was no MDI in any ofthe samples. The analytical result for the collected air samples are shown in table 1below. Table 1Concentration of MDI in the collected air samples Sample DMU no. Collected Concentration of Limit of amount ofair, 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 2hours 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 ofphthalic anhydride derivatives in consumer products The following phthalic anhydride derivatives are comprised bythe 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 ofphthalic anhydride derivatives was carried out after a method described byWelinder and Gustavsson in 1992 (12). The method

26was described for MTHP 

### A. butit is also applicable to otherphthalic anhydride derivatives. Air samples were collected by sucking a known amount ofair through a little glass column packed with glass wool and two layers ofXAD-2, which adsorbs the anhydrides. XAD-2 is extracted with toluene which is analyzed for phthalic anhydride derivatives by gas chromatographywith mass spectrometry detection (GC-MS). 3.2.1 Sample treatment and collection The purpose ofthe sample collection was to treatthe samples in a way, which as close as possible to the normal way ofapplication. 

### NailLacquer A glass plate was placed on top ofa drawing often rectangles the size of fingernails (1.2 emx 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 ofnail lacquer was puton a watch glass, and air was sucked from rightabove the watch glass for 10 min. to simulate maximum exposure.

27Figure 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. 

### Epoxyadhesive Epoxy adhesive is a two-component adhesive. Halfofeachtube was squeezed outon 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 startofthe pump when the adhesive was first squeezed out (see figure 5below)

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. 

### Controlof method A standard solution ofthe three phthalic anhydride derivatives in toluene was aerated with nitrogen at 37° C. Air was collectedjustabove the surface for 1 0 min. Duringthis a partofthe anhydrides were liberated, and it was made possible to perform a positive qualitative control ofthe method ofcollection and extraction. 

### Analyticalmethod Extraction: The tips ofthe XAD-2 column were removed with a pair ofpliers. 500 pL toluene was added and the content ofthe column (XAD and glass wool) was pushed outinto a 4 mL capped vial and the column was rinsed with an additionalSOO pL oftoluene. The extractionwas performed for 20 minutes in ultrasound bath. The toluene extractwas 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 of2 mL/min. Injection volume 1)1L. Injection temperature 300° C. Temperature program ofthe 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 ofsame type after analysis ofthe two first samples. Detection: The substances were detected by mass spectrometry after electro impact (EI+) ionisation. Collection ofmasses appears from table 2 below.



### 29Table 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 methylphthalic 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 ofstandard solutions of 1, 5, 10, 50, and 100 ng/mL. The calibration curve was linear in the entire area of measurement. The lowest concentration ofstandard solution, which gave a signal significantly different from the noise on the baseline was 5 ng/mL. Calculation ofdetection limit The detection limit depends on the collected amount ofair. In the realistic work scenarios the exposure time was 8-10 minutes corresponding to 8-10 litres ofair. The column was extracted with 1mL solvent. 5 ng/mL in 1 mL corresponds to 5 ng in 8-10 L ofair corresponding to 0.5-0.6 j.lg/m3 ofair. 3.2.2 Results of phthalic anhydride measurements The chromatogrammes for a standard solution and the method control run before change ofGC 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 ofthe three phthalic anhydride derivatives.



### 30max 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 ofthree phthalic anhydride derivatives.
None ofthe phthalic anhydride derivatives were detected in any ofthe air samples (see table 3 below) Table 3: Concentration ofphthalic anhydride in selected products DMU Collected Concen- Detection no. amountofair 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

313.3 Analysis ofglutaraldehyde in consumer products Collection and analysis ofair samples was carried out according to OSHA method 64 (13) for analysis ofglutaraldehyde in the occupational environment. Air samples were collected by sucking a known amount ofair through a silica column (Sep-Pak) coated with 2,4-dinitrophenylhydrazine (DNPH). Together with DNPH glutaraldehyde forms a derivative, which canbe analyzed byHPLC and UV-detection. Sample treatment and collection The intention with the air collection was to treatthe sample in a way that closely resembles the use scenario. Kitchen roll Collection ofair was begunwhen the package of4 kitchen rolls was opened. One roll was rolled out and crumpled up as ifit 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 ofwas begun when the package of8 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 ofthe air sampling was 1Llmin. at all collection sessions. The collection was performed with Sep-PakDNHP-Silica cartridge from Waters (14). Analytical method Elution: the Sep-Pak column was eluted with 5 ml ofacetonitril. Chromatography: The eluate was analyzed on HPLC (Agilent 1100) Column: Nova-pak, 4]1 C18 from Waters, length 150 mm, diameter 3,9 mm. Pre column C18 (Waters). Method1 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 1mL!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 1against 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 ofstandard solution,

32 \ !which gave a signal significantly different from the noise onthe base line, was 10 ng/mL. With elution method 1, the samples andthe blank gave a signalin 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 ofanalysis detects a host of aldehydes and ketones, and one ofthese may have been presentin the ambient air. 

### Calculation of detection limit The detection limit depends onthe collected amount ofair. At the realistic use scenarios the exposure time was 10 minutes corresponding to 1 0 L ofair. The column was extracted with 5 mL ofsolvent. 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 ofdetection 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: C8H 10

### 0 3 Molecularweight: 154.17 Structural formula:

0 () 0 Cyclohexan-1,2-dicarboxylic anhydride (HHPA) is a solid substance atroom 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: notfound Water solubility: very low solubility in water, and is slowly reacting with water (15). Odourthreshold, air: notfound Conversion factor at 20° C, 1atm.: 1ppm= 6.293 mg/m3 1mg/m3 = 0.159 ppm (16) 4.1.1 Hazards Cyclohexan-1,2-dicarboxylic anhydride (HHPA) has the following classification: Xi: Irritant Xn: Sensitising R41: Risk ofserious damage to eyes R42/43: May cause sensitization byinhalation and skin contact The occurrence ofHHPA in chemical consumer products (preparations), other than cosmetics, will not appear on the labeL when the concentration is below 0.1%.

35As other cyclic acid anhydrides, HHPA is an irritant because offormation of corresponding acids inwet surroundings. HHPA rarely**~nduces** contact allergy ofthe skin (delayed type hypersensitivity), butmore easily induce IgE-mediated contact urticaria. This only comes aboutafter initial respiratory sensitization, and subsequent skin contact. The mechanism ofrespiratory 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 beenverified, as well as development ofinflammation (16). HHPA has caused both sensitization and work-related symptoms at exposure levels as low as 10-50 ]1g/m3• The level ofexposure 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 bebelow 10 ]1g/m3 to ensure absence ofsensitizing effect.
4.2 Hexahydro-4-methylphthaIic anhydride, CAS 19438-60-9 Synonyms: MHHP

### A. 5-methyl- hexahydro-1,3-isobenzofurandione Molecular formula: C9H 1

## P 3 Molecularweight: 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: notfound Vapour pressure: not found Watersolubility: 36 g/1 at 20° C (17) Odourthreshold, air: not found Conversion factor at 20° C, 1atm.: 1ppm= 6.865 mg/m3

36 \i

### lmg/m3 = 

### 0.146 ppm

374.2.1 Hazards MHHPA has the following classification: Xi: Irritant Xn: Sensitising R41: Risk ofserious damage to eyes R42/43: Maycause sensitization byinhalation and skin contact The occurrence ofMHHPA 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 offormation ofcorresponding acids in wet surroundings. Itrarely induces contact allergy ofthe skin but more easily induces IgE-mediated contact urticaria. The mechanism ofrespiratory 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 ofinflammation (16). The critical effectis 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 ofexposure 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, buta limit value should be below 10 rg/m3 to ensure absence ofsensitizing effect.
4.3 PhthaIic anhydride, Methyltetrahydro- (unspec.), CAS 11070-44-3 Synonyms: Tetrahydromethylphthalic anhydride, 1,2,3,6-tetrahydro-4- methylphthalic anhydride, MTHPA. Molecularformula:C 9H 10

### 0 3 Molecularweight: 166.19 Structural formula (1 ,2,3,6-tetrahydro-4-methylphthalic anhydride, CAS 26590-20-5, shown):



### 38 \ I0



### 39Melting 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, 1atm.: 1ppm= 6.783 mg/m3 1mg/m3 = 0.147 ppm (16) 4.3.1 Hazards MTHP A has the following classification: Xi: Irritant Xn: Sensitising R41: Risk ofserious damage to eyes R42/43: Maycause sensitization by inhalation and skin contact The occurrence ofMTHPA in chemical consumer products (preparations), other than cosmetics, will not appear onthe label, when the concentration is below 0.1%. As other cyclic acid anhydrides, MTHPAis an irritantbecause offormation ofcorresponding acids in wet surroundings. Itrarely induces contact allergy ofthe skin but more easily induces IgE-mediated contact urticaria. The mechanism ofrespiratory sensitization is mainly IgE mediated allergy bothin animal studies and when exposed workers have been investigated. In the respiratory challenge tests bronchial obstruction has been verified, as well as development ofinflammation (16)
. Among MTHPA-exposed workers, even at low levels ofexposure (5-20 rg/m3 ) 56% had allergy symptoms ofthe 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 ofmucous membranes ofthe eyes and airways and sensitization-induced work-related diseases. Sensitization, work-related rhinoconjunctivitis, and asthma have been verified, for workers exposed to MTHPA levels of5-20 rg/m3 (16). 4.3.2 Limitvalues No health based limit values for MTHPA have been found, buta limit value should be below 5 rg/m3 to ensure absence ofsensitizing effect. 4.3.3 Exposure and risk assessment for consumers for all the above phthalic anhydride derivatives The emission ofthe three phthalic anhydride derivatives was measured during realistic use scenarios for 6 nail lacquers and 2 two-component epoxy adhesives.

40 ', /

\ IThe results ofthese emission measurements were all below the detection limit of0.5 j1g/m3

. This is at least 10 times below the lowest level of5j1g/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 ofthe 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 thatthe highest concentrations ofphthalic anhydride derivatives would be expected in these particular nail lacquers. Epoxy adhesives were chosen because phthalic anhydrides are known to be part ofthese 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 ofrespiratory sensitization mustbe considered to below. There is a slight possibility thatpeople who have acquired respiratory allergy from other sources. e.g. occupationally, may react to very minute amounts in consumerproducts. 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 ofMDI 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 Molecularformula:C 15H 10N2

### 0 2 Molecularweight: 250.26 Structuralformula (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 ofMDI is slightly musty (10). Melting point: 34

- 43° C (10) Boiling point: 314-364°C (10) Vapour density: notfound Vapour pressure: <0.014 Pa (2,4'-MDI) <0.002 Pa (4,4'-MDI) <0.005 Pa (polymeric MDI), all at 20° C (10)

41Water solubility: Determination ofthe MDI solubility in water is difficult because ofthe high reactivity ofthe NCO groups towards OH groups, e.g. in water giving rise to aromatic amines. Consequently it is notpossible to measure the solubility ofMDI in water using the EC standard methods. Odourthreshold, air: none found Conversion factor at 20° C, 1atm.: 1ppm= 10.22 mg/m3 1mg/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 ofMDI 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 bythe manufacturer". Ifthe product is an article there is no such requirement for labelling. In the EU risk assessment report 

### (10) 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 byinhalation and skin contact R 40: Limited evidence ofa carcinogenic effect R 48/20: Harmful: danger ofserious damage to health by prolonged exposure through inhalation Strictly speaking MDI should be classified as toxic by inhalation on the basis ofa 4-hour LCSO of490 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 ofreal-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. Takentogether, in terms ofpure hazard characterisation MDI is toxic byinhalation. However, ifone considers the exposure assessment, it is reasonable to consider MDI as harmful only and to apply the risk management phrase 'harmful by inhalation'

### (10).

42 

## )It should be noted that since the vapour pressure ofMDI (4,4') is only 0.002 Paatroom temperature it is only possible to reach a saturated air concentration of0.0197 ppm or 0.2 mg/m3• In orderto reach a concentration ofas 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. Forirritant effects a NOAEL of0.5 mg/m3 was found (10). Animal data as well as studies in humans provide clear evidence ofpossible skin sensitization due to MDI. Animal studies indicate that MDI is a strong allergen. Human case reports describe the occurrence ofallergic contact dermatitis due to MDI skin exposure (10). MDI is a potential respiratory sensitizer in animals and humans. Animal studies have shown thatrespiratory sensitization canbe induced by skin contactwith MDI. The quantitative relationships between exposures (concentration, duration, rate ofexposure, route ofexposure) have notbeen established. At the presenttime it is notpossible to define reliable exposureresponse relationships with regard to the risk ofsensitization for MDI. The currentknowledge/state ofthe art in this field does notyet allow deciding a threshold level for sensitization. Because animal data supportthe hypothesis that respiratory hypersensitivity may be inducedby skin contactand because such possibility has notbeenexcluded in studies involving humans, it is reasonable to consider thatitis not only importantto reduce inhalation exposure butalso to avoid skin contact 

### (10)
. 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 inthe pathogenesis ofhypersensitivity due to isocyanates. The specific humoral response canbe IgE as well as IgG mediated. Crossreactivity with otherisocyanates has been described in several publications (10). There is inadequate evidence ofcarcinogenicity in humans and limited evidence in experimental animals ( 1 0). which is the reason the EU risk assessment reportproposed as classification as carcinogenic in category 3. In conclusion, dermal and respiratory sensitization seems to be the most critical effects. 4.4.2 limitvalues 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 ofGovernmental Industrial Hygienists (ACGIH) has recommended the same limit as a time weighted average (21). The ACGIH notes that the recommended limit may notnecessarily protect susceptible workers from possible sensitization or an allergic reaction in previously sensitized individuals.



### 43The Occupational Safety and Health Administration (OSHA) ofthe US department ofLaborhas set a permissible exposure limit of0.02 ppm or 0.2 mg/m3 as a ceiling limit (23). 4.4.3 Exposure and risk characterisation for consumers The EU risk assessment reportfinds that as respiratory hypersensitivity may be induced by skin contact, respiratory and skin sensitisation due to MDI cannotbe excluded during spraypainting, the use ofone componentfoam, during gluing orusing a putty/filler cartridge or during the use ofa hot melt adhesive. However, there is already sufficient information available upon which to base a conclusion (iii) for this endpointfor all scenarios: there is a need for limiting the risks; risk reduction measures which are alreadybeing applied shall be taken into account. (Specific attention shouldbe 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 ofless concern as consumer exposure of the identified products is expected to occur on occasional events ofshort duration. For chronic toxicity and carcinogenicity, conclusion 

### (ii) is reached for all scenarios: there is atpresent no need for further information or testing orrisk reduction measuresbeyond those which are being applied already (10). In the presentinvestigation we were not able to find hot melt adhesive containing MDI nor MDI containing spray paintfor private consumers on the Danish market. The products thatwere tested for emission ofMDI were: carwindow adhesive, mattresses, one component adhesives and sealers, polyurethane rain-coat, floor adhesive, and a hair conditioner. No emission ofMDI could be detected under the testing conditions. We have not examined exposure scenarios involving the grinding orthermal removal ofMDI containing material. Suchsecondary exposure is known to be a hazard in the occupational setting (9), but only normal, predictable consumer exposure has been the scope ofthis project. With limits ofdetection 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 of50 ]1glm3• Hence, the risk ofinducing hypersensitivity during the use ofthe available consumer products made with MDI seemsvery low. Itis importantthatconsumers 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 ofalready acquired hypersensitivity towards MDI or other isocyanates, occupationally or accidentally, even small exposures byinhalation 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 ambertint and an odoursimilarto spoiled fruit. Molecularformula: C5H80 2 Molecularweight: 1 00.1Z Structuralformula:



## 0~0 Boiling point: 187-189°C (with decomposition) Vapour density: 3.4 (air=1) Vapourpressure: 16.5 mmHg (Z.Z kPa) at

## zoo C. There is some confusion about the purity ofthe test substance used: IUCLID (1996) gives the same value for pureglutaraldehyde and for a 50% aqueous solution, ACGIH (1991) gives a vapour pressure of0.015Z mmHg (Z.O Pa at

## zoo C) for a 50% solution. In SUBFAC (a computermodel), vapourpressures 

## (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). Odourthreshold, air: 0.14 ppm (0.17 mg/m3 ) Conversion factor at

## zoo C, 1atm.: 1ppm= 4.Z mg/m3 1mg/m3 = O.Z40 ppm Datataken from (Z4). 4.5.1 Hazards Glutaraldehyde has the following classification: RZ3/Z5: Toxic byinhalation and ifswallowed. R34: Causesburns. R4Z/43: May cause sensitization byinhalation 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

45The occurrence in chemical consumer products, other than cosmetics, will not appear onthe label, when the concentrationis below 0.1%. Inhalation studies in mice and rats showed no carcinogenic activity when exposed to air concentrations of62.5- 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 ofhospital equipment and use of glutaraldehyde containing chemicals during radiographic processing. Symptomsvary from watering ofeyes, rhinitis, respiratory difficulty, nausea to headache. Thevapours from glutaraldehyde may act as an irritantto bronchial and laryngeal mucous membranes, and prolonged exposure could produce localized edema and other symptoms ofallergic response, including asthma. In these cases, the air concentrations in the breathingzone varied from 0.05 ppmto 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). Tenyears later, she experienced sporadic and mild episodes ofchest tightness and shortness ofbreath 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 ofirritation ofthe eyes and upperrespiratory tract, dyspnea on exertion, dry cough, and episodic attacks ofwheezing, 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 chamberfor 10 min. No changes FEV1 (forced expiratoryvolume in one second) were observed in a 24 hour monitoring period. However, at the end ofthis period, the methacholine inhalation testbecame positive (PC20 0.7 4 mg/ml, PC20: precise concentration ofmethacoline where FEV 1falls 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 ofrhinitis and asthma have been diagnosed by specific bronchial challenge with glutaraldehyde concentrations in the range of0.064- 0.081 mg/m3
, which is well below the ceiling limit of0.8 mg/m3 (0.2 ppm) in Denmarkor 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 ofmechanism responsible for glutaraldehyde inquced asthma is not known because IgE specific antibodies have notbeen demonstrated in affected subjects, orcanbe detected in only a small percentage ofworkers with symptoms related to work with glutaraldehyde (27). Accordingto the American Conference ofIndustrial Hygienists (ACGIH) no clear dose-response relationships in humans have been established for airborne glutaraldehyde exposure. Reported industry experience indicates an absence ofglutaraldehyde-induced skin orrespiratory sensitizations for workers routinely exposed to airborne glutaraldehyde concentrations ranging from 0.01 to 0.34 ppm (21.26). 4.5.2 limitvalues In Denmark, the occupational exposure limit is 0.2 ppm (0.8 mg/m3), and this a ceiling limit (22). The American Conference ofIndustrial Hygienists (ACGIH) recommends a threshold limitvalue- ceiling of0.05 ppm (21). In Denmark, a general limit (a so-called C-value) of0.001 mg/m3 for ambient air has been calculated (24). The C-value is a limitvalue forhow much an installationmay contribute to airpollution. 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 ingredientwith restrictions. Glutaraldehyde may sometimes be used as a disinfectant during the manufacture ofpapertowels, toilet paperand the like. The two samples taken did not emitany detectable amounts ofglutaraldehyde, i.e. the emission was below 5f1g/m3• Thisis well below the Danish occupational exposure limit, and at the level ofgeneral limit for ambient air. Hence no risk ofrespiratory sensitization to glutaraldehyde canbe attributed to these papersamples. No cases ofsensitization to glutaraldehyde in consumer products have been found in the literature. The risk ofrespiratory sensitization to glutaraldehydevia consumerproducts mustbe considered very low, bothbecause oflow availability, non-detectable emissions, and absence ofcases in the literature. It is possible that consumers with already acquired sensitization towards glutaraldehyde orformaldehyde from other sources may react to even small residual concentrations ofglutaraldehyde 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

## ( 

# 5Conclusion

The purpose ofthe presentprojectwas to
• Make aninventory ofconsumerproducttypes that may contain any of the five R42-substances. • Examine, ifconsumers actually are exposed to the substances when using such products. • Assess, ifthe 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 ofsampled products within each group is given in parenthesis. The following consumer products may contain phthalic anhydride derivatives:

• Nail Lacquer (6) • Two-componentepoxy adhesive (2) The following consumer products maycontain glutaraldehyde:
• Cosmetic products (mouth washes and creams) 

### (O) • Disinfectants 

### (O) • Film developers for consumers (0) • Paper handkerchiefs, kitchen roll and toilet paper (2) Thefollowing 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) • Liquidroofcoating (0) • Hot melt adhesives 

### (O) • Floor adhesives (1) • Polyurethane materials in clothing (1) • Sprayhair fixatives and conditioner (2) Whensearching the Danish market it was not possible to obtain cosmetic products, disinfectants, norfilm developers with glutaraldehyde. Neitherwas it possible to obtain two-component adhesives and putties, liquid roofcoating, nor hotmelt adhesives with a content ofmonomeric MDI. All purchases were carried out while pretendingto be ordinary consumers, not professionals. Although some ofthe outlets visited are also used by professionals, we were not offered products intended only for professionals. This indicates a fairly good separationbetween the markets for consumers and the markets for professionals, at least pertaining to these kinds of products.



### 49No emissions ofthe respiratory sensitizers from the 19 products obtained could be detected by chemical analysis. Hence, no risk ofsensitisation to phthalic anhydride derivatives, MDI or glutaraldehyde canbe attributed to any ofthe products analyzed. 

### Phthalicanhydride derivatives Forthe phthalic anhydride derivatives the risk ofrespiratory sensitization from consumer products mustbe 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 productsthatwere tested for emission ofMDI were: carwindow adhesive, mattresses, one component adhesives and sealers, polyurethane rain-coat, floor adhesive. and a hair conditioner. No emission ofMDI could be detected under the testing conditions. We have not examined exposure scenarios involving the grinding orthermal removal ofMDI containing material. Such secondary exposure is known to be a hazard in the occupational setting, butonly normal. predictable consumer exposure has been the scope ofthis project. With limits ofdetection varying from 0.3-17 ]1g/m3the exposure is well below the occupational exposure limit of50 11g/m3• Hence, the risk ofinducing hypersensitivity during the use ofthe available consumer products made with MDI seems very low. Itis 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. Inthe case ofalready acquired hypersensitivity towards MDI or other isocyanates, occupationally oraccidentally, even small exposures by inhalation from consumer products like window sealing foams, can cause an outbreak of allergic asthma (10)
. 

### Glutaraldehyde The productsthatwere tested for glutaraldehyde emission was toilet paper and kitchen roll made ofrecycled paper. No other consumer products with a probable emission ofglutaraldehyde could be obtained. No emission ofglutaraldehyde could be detected in the analyzed products. Therisk ofrespiratory sensitization to glutaraldehyde via consumer products mustbe considered very low, both because oflow availability, non-detectable emissions, and absence ofcases in the literature.

50 \)

# 6 Reference List

1. Abi1dgard A, Mikkelsen SH, LauridsenFS. Survey ofchemcial substances inpaper handkerchiefs andtoiletpaper. Copenhagen: DanishEnvironmental ProtectionAgency; 2003. 34. Survey ofchemcial Substances in Consumer Products) 2. Cohr,K.-H. Epoxyproducts whichmay containphthalic anl1ydride derivatives are notonly used in aircraftmanufacture, butalso aircraftrepair. 2006. 3. GmnInformation. Produktermedu0nskede kemiske stoffer2002. 4. DrexlerH, Schaller KH, NielsenJ, WeberA, Weihrauch M, WelinderH, et al. Efficacy of measures ofhygiene in workers sensitisedto acid anhydrides andthe influence ofselectionbias onthe results. OccupEnvironMed. 1999;56(3):202-5. 5. NielsenJ, WelinderH, Jonsson B, Axmon A, Rylander L, Skerfving S. Exposure to hexahydrophthalic andmethylhexahydrophthalic anhydrides--dose-response for sensitization and airway effects. ScandJ WorkEnviron Health. 2001;27(5):327-34. 6. NielsenJ, WelinderH, OttossonH, BensrydI, Venge P, Skerfving S. Nasal challenge shows pathogeneticrelevance ofspecificlgE serum antibodies for nasal symptoms causedby hexal1ydrophthalic anhydride. ClinExpAllergy. 1994;24(5):440-9. 7. KanervaL, HyryH, Jolanki R, Hytonen M, EstlanderT. Delayed and inm1ediate allergy caused bymethylliexahydrophthalic anhydride. ContactDern1atitis. 1997;36(1):34-8. 8. Tarvainen K, Jolanki R, EstlanderT, Tupasela0,Pfaffli P, Kanerva L. lmmtmologic contact urticariadue to airborne methylhexahydrophthalic andmethyltetrahydrophthalic anhydrides. Contact Dern1atitis. 1995;32(4):204-9. 9. PrattC, EngelundB, DanskToksikologi Center. Sekundrer eksponering for isocyanater. Rekvireret arbejde for BARIndustri 2001. 10. European Commission- European ChemicalsBureau. European Union Risk AssessmentReport. CAS no. 26447-40-5. Methylenediphenyl diisocyanate (MDI). 2005.; vol. 59). 11. Pepe RC, We1111ingerJA, andMcEwenjrGN, editors. International cosmeticingredient dictionary andhandbook. Vol.l-4 [Medium (DataFile): Compact disc]. Cosmetic, Toiletry, and Fragrance Association, Washington, D.C. [updated2001]. 12. Welinder HandGustavsson C. Detenninationofmethyltetrahydrophtalic anhydride in air. Sampling, analysis andoccupational exposure levels. TheAm1als ofOccupational Hygiene. 1992;36:189-97. 13. U.S.Department ofLabor.Occupational Safety & HealthAdministration. Method 64. Glutaraldehyde. http://www.osha.gov/dts/sltc/methods/organic/org064/org064.html 2006. 14. Waters. Vejledning i brug afSep-PakDNPH-silica cartridge. 2006. 15. European Commission- European ChemicalsBureau. IUCLID Dataset. Cyclohexane-1,2- dicarboxylic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/85427.pdf2000. 16. KeskinenH. TheNordicExpert Group for CriteriaDocumentation ofHealthRisks from Chemicals andtheDutchExpertCommittee on Occupational Standards.

- 136: Cyclic acid anhydrides. Solna: Arbetslivsinstitntet; 2004. (Arbete ochhiilsa; 2004:15 17. European Conunission- European Chemicals Bureau. IUCLID dataset. 19438-60-9hexahydro4-methylphthalic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/!9438609.pdf2000.



### 5118. European Commission- European Chemicals Bureau. IUCLID Dataset. 11070-44-3 tetrahydromethylphthalic anhydride. http://ecb.jrc.it/IUCLID-DataSheets/11070443.pdf2000. 19. GachJE, StoneNM, FinchTM. A series offourcases ofallergic contact dermatitis to phthalic anhydride/trin1ellitic anhydride/glycols copolymer in nail varnish. ContactDennatitis. 2005;53(1):63-4. 20. YokotaK, Johyajama Y, Yamaguchi K, TakeshitaT, Morimoto K. Exposure-response relationships in rhinitis andconjunctivitis causedbymethyltetrahydrophthalic anhydride. Int Arch OccupEnviron Health. 2006;72: 14-8. 21. ACGIH. Documentation ofthe ThresholdLimitValues andBiological Exposure Indices.- [2]: E-0. 7 ed. Cincinnati, Ohio: ACGIH (American Conference ofGovermnentalIndustrial Hygenists) Worldwide; 2001. 22. Arbejdstilsynet. At-vejledning. Stofferogmaterialer- C.0.1 Grrensevrerdier for stoffer og materialer. 2005. 23. U.S.Department ofLaborOS&HA. Regulations (Standards- 29 CFR). TABLEZ-1 Limits for Air Contaminants.- 1910.1000 TABLEZ-1. http://www.osha.gov/pls/oshaweb/owadisp.show document?p table=STANDARDS&p id=999 6. 2006. 24. Jelnes JE, NielsenE. Toxicological Evaluation andLimitValues for MethylTertiary-butyl ether (MTBE), Fom1aldehyde, Glutaraldehyde andFurfural. 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. TakigawaT, Endo Y. Effects ofglutaraldehydeexposure onhumanhealth. J Occup Health. 2006;48(2):75-87. 27. Quirce S, GomezM, BombinC, SastreJ. Glutaraldehyde-induced asthma. Allergy. 1999;54(10): 1121-2.



### 52Huntsman Division (PU, PP, AdMat) PU Region (US, EAME, Asia) EAME Product (OCF, SPF, SPF kits, FRresins, Polyurea, Adhesives, SPF Coatings, Elastomers, Sealants, Other) Is test data available? (Ifanswer 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 orNo Chemical Composition ofthe formulated products (e.g polyurethane polyurethane, polyurea) BriefNameofthe study conducted (e.g. "FrankelHome Air monitoring investigation Testing"). during spray application in a residentialhouse and surroundings
1 Diisocyanate Tested (MDI, TDI, HDI)? MDI 2 Curing (surface) orExposure (airborne)? Exposure 3 RelevantData Summary- Indicate variables studied e.g. environmental conditions, ventilationrates, temperature, humidity, catalysts/reactantspresent, proportioning/mixing, application site (indoors oroutdoors); quantity ofproduct used, application method and square footage covered.
4 Test lab methods/Instruments used/ Detection levels, QC ISO 17734-1:2006 measures, levels ofdetection Experimental Parameters (samplingtimes, strategy) Interior air analysis Personal exposure 5 SummarizedTest DataResults Page45
6 SensitivityAnalysis (ifany) 7 Identify location ofabove data indocument

- Pages/Para (e.g. CPI/SPFA Pg2 Para4) PU EU SPF EPA VIR 003

- - - 8 Was Reoccupancy time determined? No 9 Ifanswerto 8 is yes, indicate reoccup_ancy time. 10 Exposure limits (occupational andgeneralpopulation limits) 0.05 mg/m3 NoEAME generalpopulation limit inEU 11 Quantitative Testing: Indicate whetherunreacted diisocyanates were present, type ofsurface, andresults obtained at eachintervalmeasured 12 OtherData on Curing: TackFreetime, cuttable, expansion time, lighttraffic, readyto use etc 13 Datarelatedto formation ofbyproducts, particularly substances that continue to off-gas overtime.

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## )Huntsman Division (PU, PP, AdMat) PU Region (US, EAME, Asia) EAME Product (OCF, SPF, SPF kits, FRresins, Polyurea, Adhesives, OCF Coatings, Elastomers, Sealants, Other) Is test data available? (Ifanswer 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 orNo Chemical Composition ofthe formulatedproducts (e.g Polyurethane polyurethane, polyurea) BriefName ofthe study conducted (e.g. "FrankelHome Reaction document for the Risk Testing"). Reduction Strategy for consumer exposure for MDI, includes OCFAirborne concentrations of MDI 1 DiisocyanateTested (MDI, TDI, HDI)? MDI 2 Curing (surface) orExposure (airborne)? Exposure 3 RelevantData Summary- Indicate variables studied e.g. Results collectedbythe industry environmental conditions, ventilationrates, temperature, Samples taken duringthe use of humidity, catalysts/reactants present, proportioning/mixing, OCF while fixing window & door application site (indoors oroutdoors); quantity ofproduct frames atrenovation site and new used, application method and square footage covered. building. 4 Test lab methods/ Instruments used/Detection levels, QC Possiblyreportedin individual measures, levels ofdetection studies listed Experimental Parameters (samplingtimes, strategy) Sampletimes reported from 7to 24 minutes re. p10 5 Summarized Test DataResults Low levels wellbelow exposure limits in general 6 SensitivityAnalysis (ifany) Possiblyreported in individual studies listed 7 Identify location ofabove data in document

- Pages/Para (e.g. p10 Pg2Para4) 8 Was Reoccupancytime determined? No 9 Ifanswerto 8 is yes, indicate reoccupancytime. 

### - 10 Exposure limits (occupational andgeneral population limits) 0.05 mg/m3 No EAME general population limit inEU 11 Quantitative Testing: Indicate whetherunreacted The OCF product is releasedfrom diisocyanates were present, type ofsurface, andresults the nozzle as a viscous foam. obtained at eachintervalmeasured Curing (incl. reaction ofthe diisocyanates) starts immediately andmoves from the outside inwards. 12 OtherData on Curing: TackFreetime, cuttable, expansion 

# - time, lighttraffic, readyto use etc 13 Datarelatedto formation ofbyproducts, particularly 

# - ( substances that continue to off-gas overtime.( .!



### ( ,,

.........·· 

# 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 ofPublic Health, Safetyofthe 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 contactpoint: Cathcline.dantinne@health.fgov.be Report prepared by ECOLAS LangeNieuwstraat 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 

### (

( .1ECOLAS Content 0./.
... - Se//igentprojecttitel: draft(datum) of nietslndien finaal 

# CONTENT
CONTENT...............................................................

**:~~**................JI.IIIIIIIIIII'I'II'IIfl:llll••••tiiiiiiii'IIJ'IJIIWIIIIIIII····-·I LISTOF 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 ofthe presentation of the risk reduction strategy tothe risk reduction group.............2 2 TOXICITY fOR fERTILITY llltllllll'llltlll'llli'IIIIIIII'IWIIlltllll:tlllllllllllllllllll'lllllllllllllli.IJIIIIIIIIIIIIIWIWIInllll:tlllll5 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 ofthe proposed risk reduction measures .................................................8

3.3.1 Relative contribution of dermalandinhalation exposure.........................................................8 3.3.2 Risks forirritation.••••••.•

**"'JI'"'*············~~··~·····,,,**

# ...., ....................., ...........,.,,,.,,,.,..........., ..,

..,,....... 9 3.3.3 Risks forsensitlsatfon......................................................................................................... 11 3.3.4 Proportionalityof 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

( jECOLAS Ustof abbreviations 0./.
... - Selligentprojectt/tel: draft(datum) of n/etsindlen finaal 

# LIST OF ABBREVIATIONS MDI Mathylened!phenyl diisocyanate MOS Margin ofsafety OCF One component foam 

### PPE Personal protection equipment 

### RAR Risk assessment report 

## (

iii£COLAS listof annexes 

## o.;....**~** Se!ligentprojecttitel: draft(datum} of nietsindien 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



## (



# (_)

vECOLAS Introduction O.j.
... - Selligentprojecttitel: draft(datum) of nietsindien tinaa/ 

## 1 INTRODUCTION
1.1 CONCLUSIONS FROM THE RISK ASSESSMENT REPORT The risk assessment report for methylenediphenyl diisocyanate came to the following conclusions:
FORTHE 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/ortesting 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 otherendpoints (conclusion (i) on hold). Conclusion (iii) was reached because: 1

## (



## ( ECOLAS Introduction 

### 0./.
... •Se//igentprojecttitel: draft(datum) of nietsindien 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 indirectlyvia 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/ortesting 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 OFTHE PRESENTATION OFTHE 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 bythe 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 2ECOLAS Introduction 

### 0./.
... - Sel/igentprojecttite/: draft(datum) of nletsindfen finaa/ proved necessary these products should be removed from the market as being unsafe under the general safety obligation provisions ofthe 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.

3 

## (

\ )ECOLAS Toxicityforfertility O.j....

- Sel/igentprojecttitel: drafl:(datum) of n/etsindien finaal 

## 2 TOXICITY FOR FERTILITY Regarding the need for further information to assess the toxicity for fertility of MDI 1 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 thattoxicity 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 HDI 1 slipw_identical outcomes, anyfoetotoxicity is secondary to maternal toxicity confined to the respiratory tract. While no fe1tility studies are available for MDI 1 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 MDI 1 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., Ifany 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 ofthese 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 ( !

\.£COLAS Effediveness of theproposedriskredudion strategy O.j.
... - Se/l!gentprojectt/te/: draft(datum) of nfetslndien finaa/ 

## 3 EFFECTIVENESS OF THE PROPOSED RISK REDUCTION STRATEGY FOR CONSUMER EXPOSURE 3.1 INTRODUCTION The risk assessment report assessed 4exposure 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 ofone 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 ofone 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 outthat MDI contalni1J9
...

**Rm~ucts** should only be used in well ventilated areas and that long sleeves and proper PPE (pair ofsuitable gloves

L
..·-·---·-------·-·-- ..··· added to the package) should be worn at all time during use of MDI containing products.

7 

## (



## (

## (

( :.l ECOLAS Effectivenessof theproposedriskredudion strategy 

## o.;.... -Sel/igentprojectt/tel: draft(datum) of nletslndien flnaal


### 3.3 ELEMENTS IN SUPPORT OF THE PROPOSED RISK REDUCTION MEASURES (march 2005) 3.3.1 Relative contribution ofdermal and inhalation exposure Ifthe defaultvalues 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:
Spraypainting One component Gluein{b

**palnttn~** Hotmelt 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 etal (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 ofthickness >0.22 mm - 2 hours protection; - • Polyethylene gloves ofthickness >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 oftotal 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 ofdermal and Inhalation exposure can be calculated for the various scenarios:
8ECOLAS Effediveness oftheproposedriskredudion strategy 

## o.;.... -Se//fgentprojecttltel: draft(datum) of nietslndlenlinaal
Spraypainting , One component G/uetng, painting" Hotmeltadhesive 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 oftotal uptake in OCF scehario ofover 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 

### Eyeirritation Eye irritation due to splashes or aerosols can only take place for spray painting and the use of MDI containing paint. For one component foam 1 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 

### (



# (.·

## (

( ECOlAS Effectiveness of theproposedriskreduction strategy 0./.
... - Selligentprojecttfte!: draff:(datum) ofnietsindien finaa/ 3.3.2.3 

## Respiratorytractirritation
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 doorframes. 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 ofactivity. • New building: Insulation of 13 windows consecutively durin"g 12 minutes. Personal sample taken covering the whole period of activity. The results ofthese new measurements are the following:
Sample description Sample time (minutes) MD!(mg/m3) Individual samples 1 window 7 < 0.00015 2windows 

### + part of door 4 0.00307 2windows 

### + part ofdoor 12 <0.00003 Whole period samples 5windows 

### + 1door 24 0.00079 13windows 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 ofone 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/m 3 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 ofthe newest design are still put on the market. 

### 10£COLAS EffediVeness oftheproposedriskreduction strategy 

## o.;....

**~** Se!!igentprojecttitel: draft(datum) of nletsindien 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 (Pauluhn 1 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: Letterfrom AKPU regarding recognised cases of proven. sensitisation amongst OCF users 

### 3.3.4 Proportionality of measures 

## (

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 doorand 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: 

### Companysize (cans/year) EU25 Non-EU >20,000,000 2 1 >10,000,000

**~** <20,000,000 

### 4 0 11i \



## (



# ()

...... ECO/AS Effectiveness of theproposedriskreduction strategy 0./.
... - Se/ligentprojecttitel: draft(datum) of nletsindlen 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) ofsuch 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 acertain 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 higherthe 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 ofthe 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 (ifany) 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
.



### 12ECOLAS Effectiveness of theproposedriskreduction 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 aconclusion i) always on hold for the fertility
o The use of PPE 

### by consumers is uncertain even 

### ifthey are provided with the product
. o the measure 1marketing 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 andUse Directive) of MDIproducts."

1OJ L262, 27.9.1976, p. 201 13 \ I

## (



# ( ,) £COlAS Literature 

## o.;....

**~** Sef//gentprojecttltel: draft(datum) of nietslndlen finaal 

# LITERATURE API (2002); PMDIUserGuidelines forProtective ClothingSelection; Technical Bulletin AX178, 6 pp. Leibold, E., Hoffmann, H.D. and Hildebrand, B. (1998);

**14 C~Methylenbisphenyllsocyanate**  

# t 1C-MDI) - Studyofthe absorption altersingle dermalandIntradermaladministration In rats; BASF Aktiengesellshaft Toxicology, Ludwigshafen/Rhein, Draft report project no. 0180431/946010, III projectno. 126-EU-MTX in RAR (2003) RAR (2003); Draftriskassessmenton methylenedlphenyld//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 Assessmentfornewnotified

**substance~** Commission Regulation {EC) No 1488/94on RiskAssessmentfor existingsubstances andDirective 98/8/ECofthe European Parliamentandofthe Councilconcerning the placingof biocidal products on the market Pauluhn, J. (2002); Critical analysis ofbiomonltorlng endpoints for measuring exposure to polymeric

**dlphenyl-methane-~4'-dilsocyanate** {MDI) in rats: a comparison of markers ofexposure andmarkers of effect;Arch. Toxicol., 76, pp 13-22 in RAR (2003)

15ECOLAS Annexes 

## o.;.... -Se/1/gentprojectt/tel: draft(datum) of nietslndlen finaal



## (

( 

# ANNEXES


# ( )

17i \



# (..J £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 ofAug. 

### 24, 200I, discussed two 

## types ofholt. 

## nwU guns1 

### the su

**l~:dJm.ft** 

### old 

### (HaJte1 ') und new 

### (neue) type. 

### Thus 

### test '+V1W IlfHHk\ 

### beforethe decision to 

### Bm.1nch the 

## ;m)(Juct

**And~** 

### as n result ofthi."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

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**l'•·r.~th~>~t l:!lt'ety·r~gl•lnt<ll'}'**  Mfnirs 

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······-·····"'·-

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## ( ECOI.AS Annexes 0./.

... -Se/1/gentprojecttite/: draft(datum) of nletsfnd!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** Laau4 B-1160**Brus~el** · Belgie Tilburg 10.06.05
DearMr.left's, europeon DCF produce' oommll"ee

# k

HerebyIwouldli.ke to declare thatnone ofmy members repo1tedthatiu the**la~t** approximately 25 yean there ha; been to their l:nowledge anyone ofrecognised case ofproven**.~emilisatioll**reaction, I.e. identified allergk inhnlntit•e or sl:inreaction**dt~e** to the exposme\'enus MDI**ba~ed** polyllrethane**foam~.** Themembm ofAKPU**repres~mt** about 9 5**~.-:,**oftheproducers ofone componentfoaminEurope.

' lil Unfortunately Icauuot give you ndetailednumberofemployee; ofthese compauie; because there 

### i{ .u-.: ofvery**dift~rent** $iZe andareproducing inmanycase$ awide nmge ofproducts.
I

AKPU Dr. )..f.F.A.van**Die~;r,en** Pre!;ident

20Huntsman Division (PU, PP, AdMat) PU Region (US, EAME, Asia) EAME Product (OCF, SPF, SPF kits, FRresins, Polyurea, Adhesives, OCF Coatings, Elastomers, Sealants, Other) Is test data available? (Ifanswer 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 orNo Chemical Composition ofthe formulated products (e.g Polyurethane polyurethane, polyurea) BriefName ofthe study conducted (e.g. "FrankelHome FEICApositionpaper onthe use Testing"). ofgloves for MDI containing mixtures, inparticular OCF offered to the generalpublic 1 Diisocyanate Tested (MDI, TDI, HDI)? 2 Curing (surface) orExposure (airborne)? 3 RelevantData Summary- Indicate variables studied e.g. environmental conditions, ventilationrates, temperature, humidity, catalysts/reactantspresent, proportioning/mixing, application site (indoors oroutdoors); quantity ofproduct used, application method and square footage covered. 4 Testlab methods/ Instruments used/Detection levels, QC measures, levels ofdetection 

## ( Experimental Parameters (samplingtimes, strategy) 5 SummarizedTest Data Results
6 SensitivityAnalysis (ifany) 7 Identify location ofabove data in document

- Pages/Para (e.g. Pg2Para4) 8 Was Reoccupancytime determined? 9 Ifanswerto 8 is yes, indicate reoccupancytime. 10 Exposure limits (occupational andgeneralpopulationlimits) 11 Quantitative Testing: Indicate whetherunreacted diisocyanates were present, type ofsurface, andresults obtained at eachinterval measured 12 OtherData on Curing: TackFreetime, cuttable, expansion time, lighttraffic, readyto use etc 13 Datarelatedto formation ofbyproducts, particularly 

### - substances that continue to off-gas overtime.( \



### ( 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 athird 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 ofpoor ve.nti· lation unless a protective mask \\i.th an appropri;ne g>1; filter (i.e type A1 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 2to 4 minutes since the OCF container is completely empty within this timeframe. OCF products present afoam 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.

2/3( 

### 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 athickness 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

3/3

# CONTAINS NO CB.I