06/July/2016

Call for evidence on the use of formaldehyde releasers on

their own, in mixtures or in articles by workers, professionals
and consumers.
Background document

Objective

To gather information for the investigation report on the uses of formaldehyde releasers which
will be used to support the Commission’s decision if a preparation of an Annex XV restriction
dossier on formaldehyde and formaldehyde releasers is warranted. Information from as many
relevant stakeholders as possible is needed and includes information on uses and tonnages, in
the first place, but also information on emissions and exposures of formaldehyde releasers
included in table 1, table 2 and table 3 below in this document can be submitted. Also
information on other formaldehyde releasers than identified so far (see tables included in this
document) is needed.

This call for evidence targets interested parties such as companies (manufacturers, suppliers,
distributors, importers etc.), trade associations and any other stakeholders or Member State
Authorities holding relevant information. Specific questions are addressed on certain issues of
particular interest.

Therefore, anyone who could be affected by this possible restriction or who holds relevant
information is kindly invited to provide responses before 27/09/2016.

For any clarifications on completing the questionnaire, please contact the ECHA Restriction
Formaldehyde group at echa-restriction-formaldehyde@echa.europa.eu.

Background

On 3 December 2015, ECHA received a request by the European Commission to investigate

formaldehyde releasers and their uses in the EU (see:
http://echa.europa.eu/documents/10162/13641/echa_annex_xv_restriction_proposals_en.pdf).

ECHA is currently investigating possible formaldhyde releasers and their use in the EU with the
aim to support the EU Commission to decide whether to request ECHA to prepare an Annex XV
dossier for restriction on formaldehyde and whether formaldehyde releasers should be part of
this restriction dossier.

Formaldehyde is harmful to human health. The current harmonised classification for

formaldehyde according to CLP Regulation (Regulation EU No 1272/2008) is Carcinogenic 1B,
Mutagenic 2, Acute Tox. 3 (inhalation, contact with skin, oral), Skin Sensitiser 1 and Skin
Corrosive 1B. Moreover, ECHA’s Committee for Risk Assessment has issued opinions on three
formaldehyde releasers in regards their classification and labelling (see table 2).

Formaldehyde is included in the Community Rolling Action Plan (CoRAP). The evaluation of the
substance was a joint activity performed by France (leading the evaluation) and the
Netherlands, where France was responsible for addressing concerns to workers and the
Netherlands had the responsibility for addressing concerns for consumers and general
population.

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Based on the evaluation, ECHA has decided on 6 October 2015 to request the registrants of
formaldehyde to provide further information regarding the registered substance and where
relevant, to update their Chemical Safety Report, especially the exposure scenarios covering
use by consumers. The deadline for submitting the information to ECHA is by 13 October 2017
(see ECHA’s decision: Formaldehyde - Substance evaluation - CoRAP - ECHA ).

In September 2015 France announced its intention to prepare an analysis of the most
appropriate risk management option (RMOA) for the substance (see the intention:
http://echa.europa.eu/addressing-chemicals-of-concern/substances-of-potential-concern/pact/-
/substance-rev/10309/term.

ECHA’s current investigation on formaldehyde releasers aims also to support France and the
Netherlands in their work with formaldehyde.

Formaldehyde is also included on the list of substances for which the Commission has launched
a public consultation due to a possible restriction of CMRs (Categories 1A and 1B) in textile
articles and clothing for consumer use according to article 68(2). The consultation ended on 22
March 2016. See further information: http://ec.europa.eu/growth/tools-
databases/newsroom/cf/itemdetail.cfm?item_id=8299.

Simultaneously with this call for evidence, ECHA is making a screening of the registration
dossiers. ECHA’s investigation of formaldehyde releasers begins with the substances listed as
formaldehyde releasers in the Annex V of the Cosmetic Product Regulation 1223/2009.
Furthermore, ECHA continues to investigate formaldehyde releasers included in table 2 of the
scientific article by de Groot A.C. et al. (2009)
http://onlinelibrary.wiley.com/doi/10.1111/j.1600-0536.2009.01582.x/epdf.

Additional investigation is made on substance identified as formaldehyde releasers in biocidal

review (table 3 extracted from formaldehyde releasing biocidal active substances included in
the Commission delegated Regulation (EU) No 1062/2014 (the Review Programme
Regulation)).

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 06/July/2016

Table 1: List of formaldehyde releaser based on the scientific article of de Groot, A.C.
et al. (2009).

(A) Chemicals for which adequate clinical data are available to identify them as
formaldehyde-releasers beyond doubt

Commonly used IUPAC name Other synonyms Current trade namesi CAS number
name

Benzylhemiformal Phenylmethoxymethan (Benzyloxy)methanol Akyposept®B [Preventol® 14548-60-8

(INCI) ol D2; See there]

Bioban CS 1135® 4,4- Bioban CS 1135® 81099-36-7

Dimethyloxazolidine; (ingred.
3,4,4- 75673-43-7
trimethyloxazolidine and 51200-
87-4)

Bioban CS 1246® 5-Ethyl-3,7-dioxa-1- 7-Ethylbicyclo- Bioban CS-1246® 7747-35-5

azabicyclo[3.3.0] oxazolidine Chemtan A60®
octane Oxazolidine-E®
Zoldine ZE®

Bioban P-1487® 4-[2-(Morpholin-4- Mixture of Bioban P-1487® 37304-88-4

ylmethyl)-2-nitro- nitrobutylmorpholine (ingred. 1854-
butyl]morpholine; and 23-5
4-(2-nitrobutyl) ethylnitrotrimethylen and 2224-44-
morpholine edi morpholine 4)

2-Bromo-2- As in column 1 Bromonitropropanedi Bronopol®; Chemynol 52-51-7

nitropropane-1,3- ol; Bronopol BP®; Myacide Pharma
diol (INCI) BP®; Onyxide 500®

Diazolidinyl urea 1-[1,3- N,N’- Abiol Forte®; Germall 78491-02-8

(INCI) bis(hydroxymethyl)-2, bis(hydroxymethyl)ur II®; Liposerve DU®; Nipa
5-dioxo-imidazolidin-4- ea Biopure
yl]-1,3- 200®
bis(hydroxymethyl)
urea

Dihydroxydimethyl 4,5-Dihydroxy-1,3- Dimethylolglyoxalure Fixapret® (various); 68411-81-4

olethyleneurea, bis(hydroxymethyl)- a, methylated Freerez PKF®; Knittex
methylated imidazolidin-2- one, LE®; Permafresh®
methylated (various); Sumitex®
(various)

1,3-Dimethyl-4,5- 4,5-Dihydroxy-1,3- Fixapret NF® 3923-79-3

dihydroxyethyleneu dimethylimidazo- lidin-
rea 2-one

Dimethylhydantoin 5,5- Formaldehyde, 26811-08-5

formaldehyde Dimethylimidazolidine- polymer with
resin*** 2, 4-dione, 5,5-dimethyl-2,4-
formaldehyde imidazolidinedione;
DMHF

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Commonly used IUPAC name Other synonyms Current trade namesi CAS number
name

Dimethyloldihydrox 4,5-Dihydroxy-1,3-bis 1,3- Fixapret® (various); 1854-26-8

yethyleneurea (hydroxymethyl)- Bis(hydroxymethyl)- Permafresh® (various)
imidazolidin-2- one 4,5-dihydroxy-2-
imidazolidinone

Dimethylolethylene 1,3- Fixapret AH® 136-84-5

urea Bis(hydroxymethyl)
imidazolidin-2-one

Dimethylolpropylen 1,3- DMPU; Fixapret PH®; Knittex 3270-74-4

eurea Bis(hydroxymethyl) Tetrahydro-1,3- PRS®
-1,3-diazinan-2-one bis(hydroxymethyl)-
1H- pyrimidin-2-one

Dimethylol urea 1,3- N,N’- Kaurit S®; Methural®; 140-95-4

(INCI) Bis(hydroxymethyl) Bis(hydroxymethyl)ur Permafresh 477®;
urea ea; Carbamol; Urofix®
Dihydroxymethylurea
;
N,N’-dimethylolurea;
Dimethylurea;
Oxymethurea (MI);
Urea formaldehyde

DMDM hydantoin 1,3- Dimethyloldimethyl- Cosept DM®; Dekafald®; 6440-58-0

(INCI)** Bis(hydroxymethyl)-5, hydantoin; Glydant® (2000, XL-
5-dimethyl- 1,3-dimethylol-5,5- 1000); Lanodant DM®;
imidazolidine-2,4-dione dimethyl- hydantoin; Mackstat DM®;
DMDMH Microcare DH®

Ethylene urea Imidazolidin-2-one 2-Imidazolidinone 120-93-4

(MI); 2-
Oxoimidazolidine

Forcide 78® Iii (Z)-3-(Bis(2- 2- Forcide® 78iii 77044-78-1

hydroxyethyl)amino)- Hydroxymethylamino
2- (2-hydroxyethyl- - ethanol-tri-N-
(hydroxymethyl)amino ethylhydroxy-2-
) amino-methylene
prop-2-en-1-ol

Forcide 78® IIiv 1,3,5-Triethyl-1,3,5- (b) Hexahydro-1,3,5- (b) Vancide-TH®; 7779-27-3 (b)
triazinane (b) triethyl-s-triazine; Forcide® 78v
(b) Triethyl-
trimethylenetriamine
mixture of (a)
triazinetriethanol
(see there) and
(b) hexahydro-1,3,5-
triethyl-1,3,5-
triazine

Formaldehyde Formaldehyde Formalin; Methanal; 50-00-0

(INCI, MI)* Methyl aldehyde;
Oxymethylene

Glyoxalurea 4,5- Dihydroxyethyleneur 3720-97-6

Dihydroxyimidazolidin- ea;
2-one Glyoxalmonoureine

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 06/July/2016

Commonly used IUPAC name Other synonyms Current trade namesi CAS number
name

Imidazolidinyl urea 3-[3-(Hydroxymethyl)- Bis(methylolhydantoi Germall 115®; Liposerve 39236-46-9

(INCI, MI)* 2,5-dioxo- n urea) methane; IU®; Nipa Biopure 100®;
imidazolidin-4-yl]-1- Imidurea (MI) Protacide U-13®; Unicide
[[[3- (hydroxymethyl)- U-13®
2,5-dioxo-
imidazolidin-4-yl]
carbamoylamino]meth
yl]urea

MDM hydantoin 1-(Hydroxymethyl)- 1-Hydroxymethyl- Glycoserve® 116-25-6

(INCI) 5,5-dimethyl-imi- 5,5-dimethyl
dazolidine-2,4-dione hydantoin
(MI); MDMH;
Methylol dimethyl
hydantoin;
Monomethylol
dimethyl hydantoin

Methenamine Not available Aminoform; Cystamine®; 100-97-0

(INCI, MI)** Formamine; Urotropine®;Vulkacit
Hexamethylene H30®
tetramine;
Hexamine;
Methenamide

N,N’- 5-Methyl-3-[(5- Grotan OX® 66204-44-2

Methylenebis(5- methyloxazolidin-
methyloxazolidine) 3-yl)
methyl]oxazolidine

4,4’- 4-(Morpholin-4- Bismorpholinomethan 5625-90-1

Methylenedimorpho ylmethyl)morpholine e;
line Dimorpholinomethan
e;
4,4’-methylenebis-
morpholine

N-Methylol- 2-Chloro-N - Chloroacetamide-N - Grotan DF-35® 2832-19-1

chloracetamide (hydroxymethyl) methylol
acetamide

Methylol urea Hydroxymethylurea N- 1000-82-4

(hydroxymethyl)urea
;
Methyl hydroxyurea;
Mono(hydroxymethyl
)urea;
Monomethylolurea;

Paraformaldehyde* Formaldehyde Paraform; Aldacide®; Formagene® 30525-89-4

Poly(oxymethylene)

Polyoxymethylene Not available Melamine, polymer 9003-08-1

melamine (INCI)*** with formaldehyde;
Melamine/formaldehy
de resin; Nanoplast

Polyoxymethylene Formaldehyde; urea Polynoxylin; Karbamol® (B/M); 9011-05-6

urea (INCI)*** Urea– formaldehyde Kaurit® (285FL, 240);
resin; Uformite®

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 06/July/2016

Commonly used IUPAC name Other synonyms Current trade namesi CAS number
name

Urea, polymer with

formaldehyde

Preventol D2®vi Phenylmethoxymethox Bis(benzyloxy)metha Preventol D2®. This 2749-70-4

y- ne; trade name
Methylbenzene Mixture of is also often used for
hydroxymethylene benzylhemiformal
and
polyhydroxymethylen
e monobenzylether;
1,1’-
(Methylenebis(oxyme
thylene)) bis-benzene

Propyleneglycol Not available

hemiformal

Quaternium-15 N -(3- Cosept 200®; Dowicide 4080-31-3

(INCI, MI)** Chloroallyl)hexaminiu Q®; Dowicil® (75, 200)
m chloride;
Chloroallylhexaminiu
m chloride;
1-(3-Chloroallyl)-
3,5,7-triaza-1-
azonia- adamantane
chloride;
Hexamethylene
tetramine chloroallyl
chloride

Sodium Not available Glycine, N- Suttocide A® 70161-44-3

hydroxymethyl- (hydroxymethyl)-,
glycinate (INCI)* sodium salt (1:1);
N-
hydroxymethylglycine
(mono)sodium salt;
Sodium N -
(hydroxymethyl)glyci
nate

Tetramethylol 2,4,6,8- Tetrakis(hydroxymet Fixapret 140® 5395-50-6

acetylenediurea Tetrakis(hydroxymethy hyl) glycoluril;
l)- Tetramethylolglycolur
2,4,6,8- il
tetraazabicyclo[3.3.0]
octane-3,7-dione

Tris(N- 2-[4,6-Bis(2- Hexahydro-1,3,5- Forcide 78® (see there); 4719-04-4

hydroxyethyl) hydroxyethyl)1,3,5- tris(hydroxyethyl)tria Grotan® (B, BK, HD);
hexahydrotriazine triazinan-2-yl]ethanol zine; Onyxide 200®; Roksol T
Triazinetriethanol; 1–7®
Trihydroxyethylhexah
ydro s-triazine;
1,3,5-
Trihydroxyethylhexa-
hydrotriazine

Tris(hydroxymethyl 2-(Hydroxymethyl)-2- Nitromethylidynemet Tris Nitro® 126-11-4

)-nitromethane nitropropane- 1,3-diol hanol;
(INCI, MI) Trimethylolnitrometh

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Commonly used IUPAC name Other synonyms Current trade namesi CAS number
name

ane; Tris nitro


Substances included in Annex V of the Cosmetic Product Regulation (EC No 1223/2009) and in the opinion of The
Scientific Committee on Cosmetic Products and Non-Food Products Intended for Consumers (The determination of
certain formaldehyde releasers in cosmetic products, 2002):
http://ec.europa.eu/health/ph_risk/committees/sccp/documents/out188_en.pdf
 Substances included in Annex V of the Cosmetic Product Regulation but not in the “The determination of certain
formaldehyde releasers in cosmetic products, 2002”
*** resins (formaldehyde is used as a starting material in the chemical industry for the production of condensed resins)

(B) Chemicals for which adequate clinical data are lacking to identify them as formaldehyde-releasers beyond doubt

5-Bromo-5-nitro- 5-Bromo-5-nitro-1,3-dioxane Bromonitrodioxane Bronidox®; 30007-47-7

1,3-dioxane Dekasol®5 & 10
(INCI)**

1,6-Dihydroxy-2,5- 2-(Hydroxymethoxy) Dimethylol glycol; Dascocide 9®; 3586-55-8

dioxahexane ethoxymethanol 2,5-Dioxahexane- Nipacide FC®
1,6-diol;
(Ethylenedioxy)dimet
hanol;
Ethyleneglycoldiform
al

Hydantoin Imidazolidine-2,4-dione Glycolylurea; 461-72-3

2-Hydroxy-2-
imidazolin-4 (or 5)-
one

(Hydroxymethyl)- Not available 27636-82-4

5,5-dimethyl-2-4-
imidazolidinedione

3- As in column 1 4,4-Dimethyl-2,5- 16228-00-5

(Hydroxymethyl)- dioxo-1-
5,5- imidazolidenemethan
dimethylimidazolidi ol
ne-2,4- dione

Methylal (INCI, MI) Dimethoxymethane 2,4-dioxapentane; Anesthenyl® 109-87-5

Formal;
Formaldehyde
dimethyl acetal

N- 2- Troysan 174® 34375-28-5

Methylolethanolami (Hydroxymethylamino)ethanol
ne

**
Substances included in Annex V of the Cosmetic Product Regulation but not in the “The determination of certain
formaldehyde releasers in cosmetic products, 2002”

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 06/July/2016

Table 2: Formaldehyde releaser for which the Committee for Risk Assessment has
adopted opinions on harmonised classification

Name of the substance Reference

4,4'-methylenedimorpholine [MBM] http://echa.europa.eu/opinions-of-the-
committee-for-risk-assessment-on-proposals-
for-harmonised-classification-and-labelling/-
/substance-rev/12647/term
Reaction products of paraformaldehyde and 2- http://echa.europa.eu/opinions-of-the-
hydroxypropylamine (ratio 3:2); [MBO] committee-for-risk-assessment-on-proposals-
for-harmonised-classification-and-labelling/-
/substance-rev/12646/term
Reaction products of paraformaldehyde with http://echa.europa.eu/opinions-of-the-
2-hydroxypropylamine (ratio 1:1); [HPT] committee-for-risk-assessment-on-proposals-
for-harmonised-classification-and-labelling/-
/substance-rev/12645/term

Table 3: Formaldehyde releasers in the biocidal review

Entry
numbers in
the Review Substance Remarks
Programme
Regulation
(ethylenedioxy)dimethanol (Reaction products of
359
ethylene glycol with paraformaldehyde (EGForm))
Already in table 1 (CAS
368 Methenamine 3-chloroallylochloride (CTAC)
no: 4080-31-3)
2,2',2''-(hexahydro-1,3,5-triazine-1,3,5-
377
triyl)triethanol (HHT)
1,3-bis(hydroxymethyl)-5,5- Already in table 1 (CAS
393
dimethylimidazolidine-2,4-dione (DMDMH) no: 6440-58-0)
cis-1-(3-chloroallyl)-3,5,7-triaza-1-
797
azoniaadamantane chloride (cis CTAC)
7a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c]oxazole
444
(EDHO)
Already in table 1 (CAS
531 (benzyloxy)methanol
no:14548-60-8)
.alpha.,.alpha.',.alpha.''-trimethyl-1,3,5-triazine-
566
1,3,5(2H,4H,6H)-triethanol (HPT)
3,3'-methylenebis[5-methyloxazolidine]
656
(Oxazolidin / MBO)

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4,4’-methylenebis-
387 N,N'-methylenebismorpholine (MBM) morpholine already in
table 1
Already in table 1 (CAS
691 Sodium N-(hydroxymethyl)glycinate
no: 70161-44-3)
Tetrahydro-1,3,4,6-
382 tetrakis(hydroxymethyl)imidazo[4,5-d]imidazole-
2,5(1H,3H)-dione (TMAD)

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