⇒ PREAMBLE—NOT PART OF THE SPECIFICATION ⇐

In order to promote public education and public safety, equal justice for all, a better informed citizenry, the rule of law, world trade and world peace, this legal document is hereby made available on a noncommercial basis, as it is the right of all humans to know and speak the laws that govern them.

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⇒ END OF PREAMBLE—NOT PART OF THE SPECIFICATION ⇐

EN 71-7

EUROPEAN STANDARD

NORME EUROPÉENNE

EUROPÄISCHE NORM

April 2014

ICS 97.200.50

Supersedes EN 71-7:2002

English Version

Safety of toys - Part 7: Finger paints - Requirements and test methods

Sécurité des jouets - Partie 7: Peintures au doigt Exigences et méthodes d'essai

Sicherheit von Spielzeug - Teil 7: Fingermalfarben Anforderungen und Prüfverfahren

This European Standard was approved by CEN on 8 February 2014.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels

© 2014 CEN

All rights of exploitation in any form and by any means reserved worldwide for CEN national Members.

Ref. No. EN 71-7:2014 E

3

Foreword

This document (EN 71-7:2014) has been prepared by Technical Committee CEN/TC 52 “Safety of toys”, the secretariat of which is held by DS.

This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2014 and conflicting national standards shall be withdrawn at the latest by October 2014.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.

This document supersedes EN 71-7:2002.

This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports essential requirements of EU Directive 2009/48/EC.

For relationship with EU Directive 2009/48/EC, see informative Annex ZA, which is an integral part of this document.

EN 71, Safety of toys, consists of the following parts:

NOTE 1 In addition to the above parts of EN 71, the following guidance documents have been published: CEN Report, CR 14379:2002, Classification of toys - Guidelines, CEN Technical Report CEN/TR 15071:2005, Safety of toys - National translations of warnings and instructions for use in EN 71 and CEN/TR 15371:2013, Safety of toys - Replies to requests for interpretation of EN 71-1, EN 71-2, and EN 71-8.

This part 7 of the EN 71 series is intended to be read in conjunction with EN 71, part 1. 4

NOTE 2 Words in italics are defined in Clause 3 (Terms and definitions).

According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.

5

Introduction

This European Standard contains requirements which are intended to reduce the risks to children when finger paints are used as intended or in a foreseeable way, bearing in mind the behaviour of children. It is intended to complete the essential safety requirements of Directive 2009/48/EC by providing special requirements for finger paints.

It is recognized that finger paints when compared to other toy products present different risks because of the intended use by fingers or hands and the age of the child. For example, prolonged skin contact or possible ingestion of paint material cannot be ruled out. Therefore, the safety requirements outlined in other parts of EN 71 needed to be expanded upon for finger paints. In order to address the risks associated with the use of finger paints by children, this part of EN 71 contains requirements relating to preservatives as well as other ingredients that may be used in the manufacture of finger paints and requirements relating to impurities, migration of certain elements and other attributes.

Chemical Abstract Service Registry Number (CAS), European Inventory of Existing Chemical Substances Number (EINECS) or Colour Index Number given in the tables are provided for information purposes only.

6

1 Scope

This part of EN 71 specifies requirements for the substances and materials used in finger paints and applies to finger paints only.

Additional requirements are specified for markings, labelling and containers.

2 Normative references

The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.

EN 71-3, Safety of toys - Part 3: Migration of certain elements

EN 71-12, Safety of toys - Part 12: N-Nitrosamines and N-nitrosatable substances

EN ISO 787-9, General methods of test for pigments and extenders - Part 9: Determination of pH value of aqueous suspension (ISO 787-9)

3 Terms and definitions

For the purposes of this document, the following terms and definitions apply.

3.1 finger paint

aqueous semi-solid or liquid, coloured mixture specially designed for children to apply directly to suitable surfaces with the fingers and hands

3.2 colourant

pigment or dyestuff

NOTE 1 to entry: For definitions of pigment and dyestuff, see EN ISO 4618.

3.3 extender

material in granular or powder form, insoluble in the medium and used to modify or influence certain physical properties

[SOURCE: EN ISO 4618:2006, 2.98]

3.4 humectant

substance that delays the drying process

3.5 binding agent

water soluble or miscible, non-volatile component that binds the paint to the surface to which it has been applied

3.6 preservative

substance that prevents the growth of undesirable micro-organisms

7

3.7 surfactant

surface active substance

3.8 embittering agent

substance that gives the product a bitter taste

4 Requirements

NOTE The requirements of this standard apply to finger paints in the form used by the child. In the case of powdered finger paints (for example to which water might be added before use) the requirements apply to the finger paint prepared according to the manufacturer's instructions.

4.1 General

Finger paints shall not contain dangerous substances or mixtures in amounts which can harm the health of children using them.

NOTE 1 For more information, see Directive 1999/45/EC [2] and Regulation No. (EC) 1272/2008 [1].

Finger paints shall not fulfil the criteria of any of the following hazard classes:

NOTE 2 The classification is detailed in Regulation (EC) No. 1272/2008 [1] (Annex I, Part 3: Health Hazards).

4.2 Colourants

4.2.1

Only colourants and colouring materials which are not fulfilling the hazard criteria in 4.1 shall be used in finger paints.

NOTE A non-exhaustive list of commonly used colourants, subject to meeting purity requirements, is given in Annex A consisting of colourants falling in one or more of the following categories: Colourants permitted for use in food and/or cosmetics and other pigments which meet the general requirements of 4.1.

4.2.2

Finger paints shall not contain azo colourants that by cleavage of one or more azo groups can produce the primary aromatic amines listed in Tables 1 and 2 when tested in accordance with the test method specified in Annex D.
8

4.3 Preservatives

Finger paints shall be preserved using only the preservatives listed in Annex B. The determination of preservatives shall be in accordance with the methods approved under EU Cosmetics Legislation, where available (see Directive 82/434/EEC [6], Directive 83/514/EEC [7], Directive 85/490/EEC [8], Directive 93/73/EEC [9], Directive 95/32/EC [10], Directive 96/45/EC [11]). When tested in accordance with these methods, the maximum concentrations specified in the column ”maximum allowed concentration” of Table B.1 and the limitations and requirements specified in the column ”Limitations and requirements” of Table B.1 shall be observed.

4.4 Migration of certain elements

When tested in accordance with EN 71-3 the concentration of elements shall not exceed the limit values specified in EN 71-3.

4.5 Limits for impurities

4.5.1 Limits for primary aromatic amines

4.5.1.1
The primary aromatic amines listed in Table 1 shall not be determinable when tested in accordance with the test method in Annex D.
Table 1 — Primary aromatic amines
Primary aromatic amines CAS number
Benzidine 92–87–5
2-Naphthylamine 91–59–8
4-Chloro-2-methyl-aniline (4-Chloro-o-toluidine) 95–69–2
4-Aminobiphenyl 92–67–1
4.5.1.2
Finger paints shall not contain carcinogenic primary aromatic amines (see Table 2 for a nonexhaustive list of relevant substances) in a total amount exceeding 20 mg/kg, with no individual primary aromatic amine exceeding 10 mg/kg, when tested in accordance with Annex D. The limitation does not apply to aromatic aminocarboxylic acids or aminosulfonic acids.
Table 2 — Other carcinogenic primary aromatic amines (non-exhaustive list)
Carcinogenic primary aromatic amineCAS number
o-Aminoazotoluene (4-o-tolyazo-o-toluidine)97–56–3
2-Amino-4-nitro-toluene (5-Nitro-o-toluidine)99–55–8
4-Chloroaniline106–47–8
2,4-Diaminoanisole615–05–4
4,4'-Diaminodiphenylmethane (4,4'-Methylenedianiline)101–77–9
3.3'-Dichlorobenzidinea91–94–1
3,3'-Dimethoxybenzidine119–90–4
3.3'-Dimethylbenzidine119–93–7
3,3'-Dimethyl-4,4'-diaminodiphenylmethane838–88–0
p-Cresidine (6-Methoxy-m-toluidine)120–71–8
2,2’-Dichloro-4,4’-methylenedianiline
(4,4'-Methylene-bis-2-chloroaniline)
101–14–4
4,4'-Oxydianiline101–80–4
4,4'-Thiodianiline139–65–1
o-Toluidine95–53–4
2,4-Xylidine95–68–1
2,6-Xylidine87–62–7
4-Amino-3-fluorophenol399–95–1
6-Amino-2-ethoxynaphthalene293733–21–8
2-Methoxyaniline (o-anisidine)90–04–0
4-Aminoazobenzene60–09–3
4-Methyl-m-phenylenediamine (Toluene-2,4-diamine)95–80–7
2,4,5-Trimethylaniline137–17–7
Aniline62–53–3
a For certain pigments limit values for 3,3’-Dichlorobenzidine are given Annex A.

4.5.2 Limits for other impurities

Finger paints shall not contain the impurities specified in Table 3, column 1 above the limits specified in column 2 when colourants specified in Table 3, column 3 are used, when tested in accordance with Annex E.

Table 3 — Impurities in finger paints
ImpurityLimit mg/kgFinger paints of concern
Polychlorinated biphenyls2Finger paints containing colourant products containing chlorine or manufactured in chlorinated solvents
Hexachlorobenzene5Finger paints containing colourant products containing chlorine or manufactured in chlorinated solvents
Benzo (a) pyrene0,05Only for finger paints containing carbon black

4.6 Taste and smell

Finger paints shall not be sweetened, flavoured or fragranced.

An embittering agent in accordance with the following list (see Table 4) shall be added in order to discourage and minimize the ingestion of paint. The bitterness shall stay in the product during product lifetime.

The bitterness should be sensorically detectable in a dilution with water 1:100.

10
Table 4 — Embittering agents
Embittering agentCAS number
Naringin/td>CAS 10236–47–2
denatonium benzoate/td>CAS 3734–33–6

NOTE The relative bitterness of these substances is approximately 1:3000 (naringin : denatonium benzoate). The following levels have been found suitable: naringin 1 %; denatonium benzoate 0,0004 % (4 mg/kg).

4.7 pH-value

The pH-value of the finger paint shall be between 4,0 and 10,0 when tested in accordance with EN ISO 787-9.

4.8 Binding agents, extenders, humectants and surfactants

Only binding agents, extenders, humectants and surfactants which are not fulfilling the hazard criteria in 4.1 shall be used in finger paints.

NOTE 1 See Annex C for a list of compounds known to be commonly used.

NOTE 2 The classification is detailed in Regulation (EC) No. 1272/2008 [1] (Annex I, Part 3: Health Hazards).

4.9 N-Nitrosamines

When tested in accordance with EN 71-12 the concentration of N-nitrosamines shall not exceed the limit values specified in EN 71-12.

4.10 Containers

The containers used for finger paints shall not possess a form, odour, colour, appearance, packaging, labelling, volume or size, such that it is likely that consumers, especially children, will confuse them with foodstuffs and in consequence place them or the finger paints in their mouths, or suck or ingest them.

5 Product information

5.1 General

Markings shall be clearly visible, easily legible, indelible, understandable and accurate. All markings shall be in the national language(s) of the country(ies) of sale.

NOTE EN 71–1 contains further marking requirements.

If the container is also the primary packaging all information under 5.2.1 shall also be given on the container. All information shall draw the attention of users or their supervisors to the inherent hazards and risks of harm involved in using the finger paint and to the way of avoiding such hazards and risks.

5.2 Marking

5.2.1 Primary packaging

NOTE Primary packaging is referred to as consumer packaging in Directive 2009/48/EC or as outer packaging in Regulation EC No. 1272/2008.

11
5.2.1.1 Manufacturer's identification

The primary packaging shall bear the name, trade name and/or trade mark and the address of the manufacturer, his authorized representative or the importer.

5.2.1.2 Labelling phrases

The primary packaging shall carry the following warning:

“Warning. Children under 3 years of age should be supervised by adults.”

The word “Warning” may be followed by, e.g. an exclamation mark or other punctuation marks. The word

“Warning” may be written in capital letters.

Finger paints supplied in powder form shall additionally bear the following warning:

“Warning. Mix with water in accordance with the instructions before giving to a child.”

Finger paints supplied in powder form should bear instructions that indicate how to mix with water and in particular, the correct ratio of water to powder. This information may alternatively be placed in documentation supplied with the toy.

Additionally there shall be information included for finger paints supplied as a powder to avoid inhalation of the powder.

5.2.1.3 Indication of preservative(s) and embittering agent(s)

The primary packaging shall be labelled with an indication of the preservative(s) and embittering agent(s) used.

Preservatives shall be identified by their chemical name or INCI (name) or E-number, where available.

5.2.2 Container

The container shall bear the name, trade name and/or trade mark and the address of the manufacturer, his authorized representative or the importer.

Manufacturers shall ensure that their toys bear a type, batch, serial or model number or other element allowing their identification, or, where the size or nature of the toy does not allow it, that the required information is provided on the packaging or in a document accompanying the toy.

12

Annex A (informative)
Non-exhaustive list of colourants which are commonly used in finger paints, and need to be in compliance with both the general and specified purity requirements

General Requirements

The colourants used in the manufacture of finger paints should be of technical quality and a purity suitable for the intended use. The composition of the colourant shall be known to the manufacturer of the finger paint and made available to the competent authorities on request.

Specific Requirements

When using the colourants of Table A.1 in finger paints it is important to apply the restrictions and specifications set out in column 6 of this table.

Table A.1 — Organic colourants which are commonly used in finger paints
No.ColourC.I. Generic NameaCI numberCAS numberRestrictions, specifications and information
1YellowPigment Yellow 1116802512–29–0See footnote b
Amine limits.
Excess coupling component e less than 1 000 ppm
2Pigment Yellow 3117106486–23–3See footnoteb
Amine limits.
Excess coupling component e less than 1 000 ppm
3Pigment Yellow 12210906358–85–63,3’-dichlorobenzidine ≤ 5 mg/kg
4Pigment Yellow 13211005102–83–0See footnote d
3,3’-dichlorobenzidine ≤ 5 mg/kg
5Pigment Yellow 14210955468–75–73,3’-dichlorobenzidine ≤ 5 mg/kg
6Pigment Yellow 17211054531–49–13,3’-dichlorobenzidine ≤ 5 mg/kg
7Pigment Yellow 74117416358–31–2Amine limits.
Excess coupling component e less than 1 000 ppm
8Pigment Yellow 1385630030125–47–4
9YellowPigment Yellow 1395629836888–99–0
10Pigment Yellow 15113980
11Pigment Yellow 1541178168134–22–5Amine limits.
Excess coupling component e less than 1 000 ppm
12Pigment Yellow 15520031068516–73–4
13Pigment Yellow 1855629076199–85–413
14Natural Yellow 3 75300 458–37–7 E 100
Food grade, see current European legislation (Directive 2008/128/EC [15])
15Natural Yellow 6 75100 27876–94–4
16Natural Yellow 26
“Food Orange 5”
75130 E 160 a
Food grade, see current European legislation (Directive 2008/128/EC [15])
17Natural Yellow 27 75135 502–65–8 E 160 d
Food grade, see current European legislation (Directive 2008/128/EC [15])
18 Orange Pigment Orange 13 21110 3520–72–7 Amine limits and coupling component e limits Combinations with Pigment Black 7 shall be checked for release of 3,3’ dichlorobenzene
3,3’-dichlorobenzidine ≤ 5 mg/kg
19Pigment Orange 34 21115 15793–73–4 Amine limits and coupling component e limits Combinations with Pigment Black 7 shall be checked for release of 3,3’ dichlorobenzene
3,3’-dichlorobenzidine ≤ 5 mg/kg
20 Orange Pigment Orange 43 71105 4424–06–0 See footnote b
21Pigment Orange 71 561200 86432–50–8
22Pigment Orange 73 56117 84632–59–7
23Natural Orange 4 75120 1393–63–1 E 160 b
Food grade, see current European legislation (Directive 2008/128/EC [15])
24 Red Pigment Red 48:2 15865:2 c 7023–61–2
25Pigment Red 57:1 15850:1 c 5281–04–9
26Pigment Red 63:1 15880:1 6417–83–0
27Pigment Red 68 15525 5850–80–6
28Pigment Red 83 58000:1 104074–25–1
29Pigment Red 122 73915 980–26–7 See footnote d
30Pigment Red 181 73360 2379–74–0
31Pigment Red 214 200660 82643–43–4
32Pigment Red 242 20067 52238–92–3
33Pigment Red 254 56110 84632–65–5
34Pigment Red 255 561050 54660–00–3
35Pigment Red 264 561300
36Pigment Red 272 561150 14
37Natural Red 4 75470 1390–65–4, 1260–17–9 E 120 Food grade, see current European legislation (Directive 2008/128/EC [15])
38 Violet Pigment Violet 19 73900 1047–16–1 See footnote d
39Pigment Violet 23 51319 215247–95–3, 6358–30–1See footnote d
40 Blue Pigment Blue 15 74160 147–14–8, 12239–87–1, 27614–71–7, 68987–63–3, 16040–69–0Limits as specified in existing chemical regulations in EU (see reg. (EC) No. 1709/2006 “REACH, Annex XVII) respectively EU member states Pigment Blue 15:2 and 15:4 are surface treated. Before using surface treated substances, manufacturers are well advised to contact their suppliers regarding composition and hazards.
41Pigment Blue 16 74100 574–93–6 See footnote d
42Pigment Blue 60 69800 81–77–6
43 Green Pigment Green 7 74260 1328–53–6 See footnote b
44Pigment Green 36 74265 14302–13–7
45Natural Green 3 75810 8049–84–1,11006–34–1 E 140 and E 141
Food grade, see current European legislation (Directive 2008/128/EC [15])

a The Colour Index is published by The Society of Dyers and Colourists, PO Box 244, Perkin House 82 Grattan Road, Bradford, West Yorkshire BD1 2JB, United Kingdom, www.colour-index.org. Colourants are classified using both their CI Generic name and their constitution number. These relate only to the “essential colourant” as defined by the Colour Index. The CAS numbers given are also taken from this database and again refer only to the “essential colourant”.

b This substance is restricted in Regulation (EC) No 1223/2009 [5] as follows: “Not to be used in eye products” or “Not to be used in products applied to mucous membranes”, as applicable.

c The insoluble barium, strontium and zirconium lakes, salts and pigments of these colourants are also permitted. According to Directive 2009/48/EC requirements on these elements need to be taken in consideration.

d This substance is restricted in Regulation (EC) No 1223/2009 [5] as follows: ” Rinse-off products”.

e Azo colourants are typically formed by a reaction sequence of diazotisation of a primary aromatic amine which is referred to as the diazo component, followed by reaction (aka coupling) with a compound having active methylene groups referred to as a coupling component.

15
Table A.2 — Non organic colourants which are commonly used in finger paints
No. Colour C.I. Generic Namea CI number CAS number Restrictions, specifications and information
46 Yellow Pigment Yellow 42 77492 51274–00–1 Iron oxide yellow E 172
Food grade, see current European legislation (Directive 2008/128/EC [15])
47 Red Pigment Red 101 77491 1309–37–1 E 172
Food grade, see current European legislation (Directive 2008/128/EC [15])
48 Blue Pigment Blue 29 77007 1317–97–1,57455–37–5 Ultramarine
49 White Pigment White 4 77947 1314–13–2 Zinc Oxide
50Pigment White 6 77891 13463–67–7 E 171 Food grade, see current European legislation (Directive 2008/128/EC [15])
51Pigment White 18 77220 207–439–9, 208–915–9E 170
Chalk Food grade, see current European legislation (Directive 2008/128/EC [15]) Mixture Calcium carbonate, Magnesium carbonate
52Pigment White 19 77004, 770058047–76–5 Aluminium silicate, hydrated
53Silver 77820 E 174
Food grade, see current European legislation (Directive 2008/128/EC [15])
54Pigment White 21 77120 7727–43–7 Blancfixe
55Pigment White 25 77231 91315–45–6 Gypsum
56Aluminium, zinc, magnesium and calcium stearates-
57 Black Pigment Black 6 77266 1333–86–4 Carbon black food contact quality
58Pigment Black 7 77266 1333–86–4 Carbon black food contact quality
59Pigment Black 11 77499 12227–89–3 E 172
Food grade, see current European legislation (Directive 2008/128/EC [15]) 16
60 Brown Pigment Metal 3 77480 7440–57–5 E 175
Gold Food grade, see current European legislation (Directive 2008/128/EC [15])
61 Orange Ferrous oxide 77489
Not in CI online
Ferrous oxide E 172 (Mix)
Food grade, see current European legislation (Directive 2008/128/EC [15])
a The Colour Index is published by The Society of Dyers and Colourists, PO Box 244, Perkin House 82 Grattan Road, Bradford, West Yorkshire BD1 2JB, United Kingdom, www.colour-index.org. Colourants are classified using both their CI Generic name and their constitution number. These relate only to the “essential colourant” as defined by the Colour Index. The CAS numbers given are also taken from this database and again refer only to the “essential colourant”.
17

Annex B (normative)
List of preservatives allowed for use in finger paints

Table B.1 — Preservatives
Ref. nr.SubstanceEC-NumberCAS- NumberMaximum allowed concentrationLimitations and requirements
1Benzoic acid
sodium benzoate
200–618–2,
208–534–8
65–85–0,
532–32–1
0,5 % (acid)
2Ammonium benzoate,
calcium benzoate,
potassium benzoate,
magnesium benzoate,
MEA-benzoate,
methyl benzoate,
ethyl benzoate,
propyl benzoate butyl benzoate,
isobutyl benzoate,
isopropyl benzoate,
‘ phenyl benzoate
217–468–9,
218–235–4,
209–481–3,
209–045–2,
224–387–2,
202–259–7,
202–284–3,
219–020–8,
205–252–7,
204–401–3,
213–361–6,
202–293–2
1863–63–4,
2090–05–3,
582–25–2,
553–70–8,
4337–66–0,
93–58–3,
93–89–0,
2315–68–6,
136–60–7,
120–50–3,
939–48–0,
93–99–2
0,5 % (acid)
3Propionic acid,
ammonium propionate,
calcium propionate,
magnesium propionate,
potassium propionate,
sodium propionate
201–176–3,
241–503–7,
223–795–8,
209–166–0,
206–323–5,
205–290–4
79–09–4,
17496–08–1,
4075–81–4,
557–27–7,
327–62–8,
137–40–6
2 % (acid)
4Hexa-2,4-dienoic acid and its salts:
Sorbic acid,
calcium sorbate,
sodium sorbate,
potassium sorbate
203–768–7,
231–321–6,
231–819–3,
246–376–1
110–44–1,
7492–55–9,
7757–81–5,
24634–61–5
0,6 % (acid)
5Paraformaldehyde30525–89–40,1 % (free formaldehyde)Oral products limit
6Biphenyl-2-ol (o-Phenylphenol)
sodium o-phenylphenate,
potassium o-phenylphenate,
MEA o-phenylphenate
201–993–5 205–055–6,
237–243–9,
282–227–7
90–43–7,
132–27–4,
13707–65–8,
84145–04–0
0,2 % expressed as the phenol
7Pyrithione zinc236–671–313463–41–70,5 %
8Inorganic sulphites and hydrogen- sulphites:
Sodium sulfite,
ammonium bisulfite,
ammonium sulfite,
potassium sulfite,
potassium hydrogen sulfite,
sodium bisulfite,
sodium metabisulfite,
potassium metabisulfite
231–821–4,
233–469–7,
233–484–9,
233–321–1,
231–870–1,
231–548–0,
231–673–0,
240–795–3
7757–83–7,
10192–30–0,
10196–04–0,
10117–38–1,
7773–03–7,
7631–90–5,
7681–57–4,
16731–55–8
0,2 % (as free SO2)
9Chlorobutanol200–317–657–15–80,5 %
104-Hydroxybenzoic acid,
methylparaben,
potassium ethylparaben,
potassium paraben,
sodium methylparaben,
sodium ethylparaben,
ethylparaben,
sodium paraben,
potassium methylparaben,
calcium paraben,
phenylparaben
99–96–7,99–76–3,
36457–19–9,
16782–08–4,
5026–62–0,
35285–68–8,
120–47–8,
114–63–6,
2611–07–2,
69959–44–0,
17696–62–7
202–804–9,202–785–7,
253–048–1,
240–830–2,
225–714–1,
252–487–6,
204–399–4,
204–051–1,
247–464–2,
274–235–4,
241–698–9
0,4 % (as acid) for single ester, 0,8 % (as acid) for mixtures of esters18
113-Acetyl-6-methylpyran-2,4 (3H)-dione and its salts:
Dehydroacetic acid,
sodium dehydroacetate
208–293–9,
224–580–1
520–45–6,
4418–26–2,
16807–48–0
0,6 % (as acid)
12Formic acid,
sodium formate
200–579–1,
205–488–0
64–18–6,
141–53–7
0,5 % (as acid)
133,3’-Dibromo-4,4’-hexamethylenedioxydi- benzamidine and its salts (including isethionate) (Dibromohexamidine Isethionate)299–116–493856–83–80,1 %
14Undec-10-enoic acid and its salts:
Undecylenic acid,
potassium undecylenate,
sodium undecylenate,
calcium undecylenate,
TEA-undecylenate,
MEA-undecylenate
203–965–8,
222–264–8,
215–331–8,
282–908–9,
260–247–7
112–38–9,
6159–41–7,
3398–33–2,
1322–14–1,
84471–25–0,
56532–40–2
0,2 % (as acid)
155- Pyrimidinamine, 1,3-bis (2- ethylhexyl) hexahydro-5-methyl- (Hexetidine)205–513–5141–94–60,1 %
162-Bromo-2-nitropropane-1,3- diol (Bronopol)200–143–052–51–70,1 %Avoid formation of nitrosamines
172,4-Dichlorobenzyl alcohol217–210–51777–82–80,15 %
181-(4-Chlorophenyl)-3-(3,4- dichlorophenyl) urea (Triclocarban)202–924–1101–20–20,2 %Purity criteria:3,3’,4,4’- Tetrachloro- azobenzene < 1 ppm, 3,3’,4,4’- Tetrachloro- azoxybenzene < 1 ppm
195-Chloro-2- (2,4- dichlorophenoxy) phenol (Triclosan)222–182–23380–34–50,3 %
20Chloroxylenol201–793–888–04–00,5 %
21N,N″-methylenebis[N′-[3-(hydroxymethyl)- 2,5-dioxoimidazolidin-4-yl]urea] (Imidazolidinyl urea)254–372–639236–46–90,6 %
22Poly(methylene),.alpha.,.omega.- bis[[[(aminoiminomethyl)amino]iminomethy l] amino]-, dihydrochloride (Polyaminopropyl biguanide)70170–61–5,
28757–47–3,
133029–32–0
0,3 %
232-Phenoxyethanol204–589–7122–99–61,0 %
24Methenamine100–97–0202–905–80,15 %
25Methenamine 3-chloro-allylochloride (Quaternium-15)223–805–04080–31–30,2 %19
261-(4-Chlorophenoxy)-1-(imidazol-1-yl)-3,3- dimethylbutan-2-one (Climbazole)253–775–438083–17–90,5 %
271,3-Bis (hydroxymethyl)-5,5- dimethylimidazolidine-2,4-dione (DMDM Hydantoin)229–222–86440–58–00,6 %
281-Hydroxy-4-methyl-6-(2,4,4- trimethylpentyl) 2-pyridon and its monoethanolamine salt (Piroctone Olamine)272–574–250650–76–5,
68890–66–4
0,5 %
292,2’-methylenebis(6-bromo-4- chlorophenol) (Bromochlorophene)239–446–815435–29–70,1 %
304-Isopropyl-m-cresol (o-Cymen-5-ol)221–761–73228–02–20,1 %
31Mixture of 5-Chloro-2-methyl-isothiazol- 3(2H)-one and 2-methylisothiazol-3(2H)- one with magnesium chloride and magnesium nitrate247–500–726172–55–4,
2682–20–4,
55965–84–9
0,000 8 % (of a mixture in the ratio 3:1 of 5- chloro-2- methylisothiazol 3(2H)-one and 2- methylisothiazol- 3 (2H)-onea
322-methylisothiazol-3(2H)-one (MIT)220–239–62682–20–40,01 %a
332-Benzyl-4-chlorophenol (Chlorophene)204–385–8120–32–10,2 %
342-Chloroacetamide201–174–279–07–20,3 %
35N,N″-bis(4-chlorophenyl)-3,12-diimino- 2,4,11,13-tetraazatetradecanediamidine and its digluconate, diacetate and dihydrochloride: Chlorhexidine,
Chlorhexidine Diacetate,
Chlorhexidine Digluconate,
Chlorhexidine Dihydrochloride
200–238–7,
200–302–4,
242–354–0,
223–026–6
55–56–1,
56–95–1,
18472–51–0,
3697–42–5
0,3 % (as chlorhexidine)
36Alkyl (C 12–22) trimethyl ammonium bromide and chloride:
Behentrimonium chloride,
cetrimonium bromide,
cetrimonium chloride,
laurtrimonium bromide,
laurtrimonium chloride,
steartrimonium bromide,
steartrimonium chloride
241–327–0,
200–311–3,
203–928–6,
214–290–3,
203–927–0,
214–294–5,
203–929–1
17301–53–0,
57–09–0,
112–02–7,
1119–94–4,
112–00–5,
1120–02–1,
112–03–8
0,1 %
374,4-Dimethyl-1,3-oxazolidine257–048–251200–87–40,1 %The pH of the finished product may not be lower than 6.
38N-(Hydroxymethyl)-N-(dihydroxymethyl- 1,3-dioxo-2,5-imidazolidinyl-4)-N’- (hydroxymethyl) urea (Diazolidinyl Urea)278–928–278491–02–80,5 %
39Benzenecarboximidamide, 4,4’-(1,6- hexanediylbis (oxy))bis- and its salts (including isethionate and p- hydroxybenzoate): Hexamidine,
Hexamidine diisethionate,
Hexamidine paraben
211–533–5,
299–055–3
3811–75–4,
659–40–5,
93841–83–9
0,1 %
40Pentane-1,5-dial (Glutaraldehyde, Glutaral)203–856–5111–30–80,1 %20
413-(p-Chlorophenoxy)-propane-1,2 diol (Chlorphenesin)203–192–6104–29–00,3 %
42Sodium N-hydroxymethyl-glycinate274–357–870161–44–30,5 %
43Benzenemethanaminium, N,N-dimethyl-N- [2-[2-[4-(1,1,3,3,-tetramethylbutyl)phenoxy] ethoxy] ethyl]-, chloride (Benzethonium Chloride)204–479–9121–54–00.1 %
a For additional labelling requirements for mixtures containing substances with sensitizing properties, see Regulation (EC) No. 1272/2008 [1]. Mixtures containing substances with sensitizing properties in certain concentrations shall be labelled: “Contains (name of sensitising substance). May produce an allergic reaction”.
21

Annex C (informative)
Ingredients used in the manufacture of finger paints

In accordance with current knowledge the following ingredients are used:

a) Binding agents:

b) Extenders:

22

c) Humectants:

d) Surfactants:

23

Annex D (normative)
Method for the detection of certain azo colourants and determination of free primary aromatic amines

D.1 General

For the detection of certain azo colourants, the sample is treated with sodium dithionite in a citrate buffer (pH 6) at 70 °C in a sealed vessel. Upon reductive cleavage, the resultant amines are extracted with MTBE by means of a “kieselguhr” type SPE column, e.g. Chromabond® XTR, or equivalent.1 The ether extract is carefully concentrated with a rotary evaporator or an equivalent sample concentrator and the residue is dissolved in acetonitrile or other suitable solvent, depending upon the detection/determination procedure to be used.

1 This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the product named. Equivalent products may be used if they can be shown to lead to the same results.

The detection/determination of amines resulting either from the reductive cleavage method or already present in the sample as free primary aromatic amines is performed by high performance liquid chromatography with a diode-array detector (HPLC/DAD) or by capillary gas chromatography with mass-selective detector (GC-MS).

The amines shall be identified by at least one of the chromatographic separation techniques described in this annex. Unless an unequivocal identification is achieved (e.g. by using GC-MS and comparing retention times with known standards), confirmation of positive results shall be achieved by a suitable alternative separation technique (to avoid possible misinterpretation from, for example, isomers of the amines to be identified).

NOTE 1 Some amines may be thermally unstable and cannot be determined by gas chromatography.

The quantification of the amines is performed by HPLC/DAD or GC-MS.

NOTE 2 Some of the amines are cleaved under the reductive conditions in D.6.2 according to Table D.1:

Table D.1
Amine compoundCleavage products
o-Aminoazotolueneo-Toluidine, 2-Methyl-p-phenylendiamine
2-Amino-4-nitrotoluene4-Methyl-m-phenylenediamine
4-Amino-azo-benzenep-Phenylenediamine, Aniline
4-Aminoazobenzene is reductively cleaved to p-phenylenediamine and aniline; o-aminoazotoluene is reductively cleaved to 2-methyl-p-phenylenediamine and o-toluidine; and 2-Amino-4-nitrotoluene is reduced to 4-methyl-m-phenylenediamine.

A prohibited azo colourant is deemed to be present in the finger paint if, on reductive cleavage, one or more of the amines listed in Tables 1 and 2 is present in a concentration exceeding 30 mg/kg.

Each primary aromatic amines listed in Table 1 is deemed to be determinable at levels exceeding 5 mg/kg.

24

D.2 Reagents

Reagent-grade chemicals are to be used, if nothing else is specified.

D.2.1

Methanol

D.2.2

Acetonitrile

D.2.3

tert-Butyl methyl ether (MTBE)

D.2.4

Citrate/sodium hydroxide buffer, c(trisodium citrate) = 0,06 mol/l, pH 6, preheated to 70 °C or 37 °C: Dissolve 12,6 g citric acid monohydrate and 6,4 g sodium hydroxide in 900 ml water. Adjust the volume to 1 L.

NOTE 'Ready-for-use' solution, Merck-Nr. 1.09437, has been found suitable.2

2 This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the product named. Equivalent products may be used if they can be shown to lead to the same results.

D.2.5

Sodium dithionite solution, freshly dissolved in water, ρ = 200 mg/ml

D.2.6

Porous, granular “kieselguhr” SPE column

NOTE Chromabond® XTR has been found suitable.2

D.2.7

Anhydrous sodium sulphate

D.2.8

Certified amine standards, primarily those listed in Tables 1 and 2

NOTE The amines in Tables 1 and 2 are human carcinogens or cancer suspect agents (Cat. 1A and 1B). The handling of these chemicals requires the utmost care and commensurate safety measures.

D.2.9

Internal standards (IS) for gas chromatography
D.2.9.1
IS 1: 2,4,5-Trichloroaniline, CAS No. 636-30-6
D.2.9.2
IS 2: 4-Amino-2-methylquinoline, CAS No. 6628-04-2
D.2.9.3
IS 3: Tributylphosphate, CAS No. 126-73-8

D.2.10

Standard solutions
D.2.10.1
Stock solution of aromatic amines

Prepare a stock solution containing 100 mg/l of each aromatic amine (D.2.8) in methanol (D.2.1). This solution shall be stored in the absence of light at (−18 ± 2) °C.

D.2.10.2
Calibration solutions

Prepare six calibration solutions in the range 0,1 mg/l to 5,0 mg/l by dilution of the aromatic amines stock solutions (D.2.10.1) into (100 ± 0,1) ml volumetric flasks using MBTE (D.2.3). Before making up to the final volume, add 0,1 ml of internal standard (D.2.10.3) to each calibration solution in order to obtain a final internal standard concentration of 1 mg/l. The calibration solutions are ready for GC-MS analysis.

D.2.10.3
Internal standard solution
25

Prepare a stock solution of each internal standard (D.2.9.1 to D.2.9.3) at 10,0 mg/l in methanol (D.2.1).

D.2.10.4
Recovery solution of aromatic amines

Prepare a recovery solution containing 10 mg/l of each aromatic amine (D.2.10.1) in methanol (D.2.1). This solution shall be stored in the absence of light at (−18 ± 2) °C.

The stability of all calibration solutions should be checked regularly. These should be stable for up to 6 months when stored in the dark at (−18 ± 2) °C.

NOTE The solvent used will depend on the chromatographic method chosen for analysis.

D.3 Apparatus

Ordinary laboratory equipment, and

D.3.1

50 ml conical flask of temperature-resistant glass with tight-fitting cap

D.3.2

Water bath, capable of maintaining a temperature of (37 ± 2) °C and (70 ± 2) °C.

D.3.3

Column made from glass or polypropylene, 25 mm to 30 mm internal diameter, 140 mm to 150 mm length, filled with about 20 g porous, granular “kieselguhr” SPE material, fitted on the outlet with a glass fibre filter (or commercial SPE column).

NOTE Chromabond® XTR (Macherey-Nagel Catalogue No. 730 507) has been found suitable.3

3 This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the product named. Equivalent products may be used if they can be shown to lead to the same results.

D.3.4

Vacuum rotary evaporator or equivalent low temperature sample concentration system

D.3.5

Pipettes 10 ml, 5 ml, 2 ml, 1 ml

D.4 Instrumentation

The analysis shall be performed using equipment selected from the following list

D.4.1

HPLC with gradient-elution and DAD

D.4.2

GC with MS

D.5 Sampling procedure

Homogenize the sample by stirring thoroughly.

D.6 Procedure

D.6.1 Sample preparation

For both the detection of certain azo colourants, and the determination of ‘free’ primary aromatic amines, a representative sample of approximately 1,0 g is weighed accurately into a 50 ml conical flask (D.3.1).

D.6.2 Reductive cleavage of azo colourants

26

Approximately, 15 ml of buffer (D.2.4), preheated to (70 ± 2) °C, is added to the sample. The conical flask is tightly closed and after brief vigorous shaking to homogenize the contents is kept at (70 ± 2) °C for (30 ± 2) min.

To achieve reductive cleavage of the azo colourants (3,0 ± 0,01) ml of sodium dithionite solution (D.2.5) is added to the conical flask. The conical flask is immediately tightly sealed, thoroughly shaken and kept again at (70 ± 2) °C for another (30 ± 2) min, and then cooled to ambient temperature within 2 min.

D.6.3 Extraction of soluble amines

For the determination of free aromatic amines (see 4.5.1.1 and 4.5.1.2), the reductive cleavage (D.6.2) is not carried out. Instead, approximately 20 ml of the buffer solution (D.2.4) preheated only to (37 ± 2) °C is added to the sample. The conical flask is tightly closed and after brief vigorous shaking to homogenize the contents is kept at (37 ± 2) °C about 30 min.

D.6.4 Solid phase extraction and concentration of amines

The solution from D.6.2 or D.6.3, as appropriate, is poured onto the SPE column without rinsing the conical flask with water or buffer. The aqueous phase is left for 30 min to absorb onto the column. The amines are then extracted twice with approximately 40 ml of MTBE as described below.

Before extracting the SPE column, the first 40 ml of MTBE is divided into portions of 2 × 10 ml and 1 × 20 ml for rinsing the conical flask. 10 ml of ether is added to the conical flask, it is closed and shaken vigorously. After allowing 30 min for the water phase to absorb onto the column, the MTBE is decanted from the conical flask onto the column leaving behind any residual water in the conical flask (Note: addition of 0,2 g of anhydrous sodium sulphate to dry the MTBE). The eluant is collected in a suitable glass container for evaporation. This operation is repeated with the remaining 10-ml and 20-ml portions of MTBE. Finally, the second 40 ml is poured directly onto the column.

The MTBE extract is carefully concentrated at a maximum temperature of 25 °C using a rotary evaporator with vacuum, or equivalent sample concentrator, to about 1 ml (do not allow the solution to go to dryness!). If MTBE is not the required chromatographic solvent, the remainder of the ether is carefully removed under a light flow of inert gas and the residue made up to 2,0 ml with acetonitrile in a graduated test tube. If MTBE is the required chromatographic solvent, the residue is quantitatively transferred to a small graduated tube and the volume made up to (2,0 ± 0,1) ml using washings from the container used in the rotary evaporator flask or sample concentrator.

During solvent removal, considerable losses of amines may occur if the process is not closely controlled (i.e. vacuum too high, temperature too high, high inert gas flow). The solvent removal should be performed under subdued light (avoid direct sunlight and if possible, direct fluorescent lightening).

If taken to dryness, each residue is immediately dissolved in (2,0 ± 0,1) ml of a suitable solvent, e.g. methanol in an amber glass flask, and subsequently analysed. If the analysis cannot be carried out immediately, the sample shall be stored at (–20 ± 2) °C.

The quantification of the amines is conducted using HPLC/DAD or GC-MS. If using GC-MS, internal standards shall be used.

NOTE Certain amines, e.g. 2,4-Toluenediamine and 2,4-Diaminoanisole, have a very low stability. If the extraction and concentration procedure is not carried out expediently, partial or total loss of amines can occur.

D.6.5 Chromatography

D.6.5.1 General

The following conditions have been found suitable for the detection/determination of primary aromatic amines. The analysis of finger paints shall be performed in accordance with the methods of analysis described in this 27 European Standard. Alternative methods of analysis or modifications to the procedures described are acceptable only if they are capable of achieving at least the accuracy and precision of the methods described in this European Standard; an adequate sensitivity; and have been validated to show that the results are equivalent to those of these standard methods.

NOTE It is reported that some amines are heat sensitive and may breakdown on heating when injected onto a GC column requiring an alternative detection technique to be used.

D.6.5.2 High pressure liquid chromatography (HPLC)

Eluent 1: Acetonitrile

Eluent 2: 0,575 g ammonium dihydrogenphosphate + 0,7 g disodium hydrogenphosphate in 1 000 ml water, pH 6,9

Column: HyPurity Advance 250 mm x 3 mm; 5 µm or equivalent, ThermoQuest Catalogue No. 21005–0035

Flow rate: 0,5 ml/min

Gradient: 0 min 15 % eluent 1, within 45 min linear to 75 % eluent 1

Column temperature: 40 °C

Injection volume: 5,0 µl

Detection: DAD, full spectral scan

Quantification: at 240 nm, 280 nm and 305 nm

28 Figure D.1 Example of HPLC-DAD chromatogram of 22 mixed aromatic amine standard at 240 nm using the conditions in D.6.5.2.

Figure D.1 — Example of HPLC-DAD chromatogram of 22 mixed aromatic amine standard at 240 nm using the conditions in D.6.5.2

29 Figure D.2 Example of HPLC-DAD chromatogram of 22 mixed aromatic amine standard at 280 nm using the conditions in D.6.5.2

Figure D.2 — Example of HPLC-DAD chromatogram of 22 mixed aromatic amine standard at 280 nm using the conditions in D.6.5.2

30 Figure D.3 Example of HPLC-DAD chromatogram of 22 mixed aromatic amine standard at 305 nm using the conditions in D.6.5.2