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EN 71-5

EUROPEAN STANDARD

NORME EUROPÉENNE

EUROPÄISCHE NORM

June 2013

ICS 97.200.50

Supersedes EN 71-5:1993

English Version

# Safety of toys - Part 5: Chemical toys (sets) other than experimental sets

Sécurité des jouets - Partie 5: Jeux chimiques (coffrets) autres que les coffrets d'expériences chimiques

Sicherheit von Spielzeug - Teil 5: Chemisches Spielzeug (Sets) ausgenommen Experimentierkästen

This European Standard was approved by CEN on 29 May 2013.

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

Management Centre: Avenue Marnix 17, B-1000 Brussels

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

Ref. No. EN 71-5:2013: E

2 3

## Foreword

This document (EN 71-5:2013) 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of an identical text or by endorsement, at the latest by December 2013, and conflicting national standards shall be withdrawn at the latest by December 2013.

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 71-5:1993.

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(s).

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

The significant changes from the previous edition of this standard are detailed in Annex F.

This standard is Part 5 of the European Standard for safety of toys, EN 71.

This Part 5 of the EN 71 series is intended to be read in conjunction with EN 71, Part 1, Part 2 and Part 3, particularly the Introduction and Clause 1 of Part 1.

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, Classification of toys — Guidelines, CEN Technical Report CEN/TR 15071, Safety of toys — National translations of warnings and instructions for use in EN 71, and CEN Technical Report CEN/TR 15371, Safety of toys — Replies to requests for interpretation of EN 71-1, EN 71-2, and EN 71-8.

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

According to the CEN-CENELEC Internal Regulations, the national standards organisations 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 is intended to reduce the risks which may present health hazards to a child when the chemical toys are used as intended or in a foreseeable way, bearing in mind the behaviour of children.

When using these chemical toys, potential risks should be kept to a minimum by inclusion of appropriate information to give special attention to possible hazards, risks and other problems.

Chemical Abstract Service Registry Number (CAS) and European Inventory of Existing Chemical Substances Number (EINECS) given in various tables are provided for information purposes only.

6

## 1 Scope

This European Standard specifies requirements and test methods for the substances and materials used in chemical toys (sets) other than experimental sets. These substances and mixtures are:

• those classified as dangerous by the EC-legislation applying to dangerous substances and dangerous mixtures [5];
• substances and mixtures which in excessive amounts could harm the health of the children using them and which are not classified as dangerous by the above mentioned legislation; and
• any other chemical substance(s) and mixture(s) delivered with the chemical toy.

NOTE The terms “substance” and “mixture” are defined in the REACH regulation No. (EC)1907/2006 and in the CLP regulation (EC) No. 1272/2008.

Additionally, requirements are specified for markings, warnings, safety rules, contents list, instructions for use and first aid information.

This Part of EN 71 applies to:

• plaster of Paris (gypsum) moulding sets;
• ceramic and vitreous enamelling materials supplied in miniature workshop sets;
• oven-hardening plasticised PVC modelling clay sets;
• plastic moulding sets;
• embedding sets;
• adhesives, paints, lacquers, varnishes, thinners and cleaning agents (solvents), supplied or recommended in model sets.

## 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 ISO 3104, Petroleum products — Transparent and opaque liquids — Determination of kinematic viscosity and calculation of dynamic viscosity (ISO 3104)

EN ISO 3219, Plastics — Polymers/resins in the liquid state or as emulsions or dispersions — Determination of viscosity using a rotational viscometer with defined shear rate (ISO 3219)

EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696)

EN ISO 22854, Liquid petroleum products — Determination of hydrocarbon types and oxygenates in automotive-motor gasoline — Multidimensional gas chromatography method (ISO 22854)

## 3 Terms and definitions

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

7

### 3.1 chemical toy

toy intended for the direct handling of chemical substances and mixtures and which is used in a manner appropriate to a given age-group and under the supervision of an adult

[SOURCE: EN 71-4:2013, 3.1]

### 3.2 experimental set

chemical toy where the experimental and explorative character in playing with single chemical substances and mixtures along strict instructions dominates over the creative ideas of the user

[SOURCE: EN 71-4:2013, 3.2]

### 3.3 plaster of Paris (gypsum) moulding set

toy containing moulds into which a mixture of water and gypsum is poured and allowed to harden

NOTE 1 to entry: The gypsum consists predominantly of calcium sulfate hemihydrate CaSO4 · 0,5 H2O.

NOTE 2 to entry: Plaster of Paris (gypsum) moulding sets are for example used for preparing figures and plates.

### 3.4 ceramic and vitreous enamelling materials supplied in miniature workshop set

toy containing ceramic glazes and vitreous enamels (transparent, opaque or coloured) which after addition of water are painted on ceramic and metallic bodies to obtain smooth coatings, after which it is dried and fired at temperatures above 700 °C

### 3.5 oven-hardening plasticised PVC modelling clay set

toy to be used for creating all kinds of figures, brooches, fashion jewellery etc. prepared by hardening in the oven at temperatures between (100–130) °C

### 3.6 plastic moulding set

toy to be used in substitution of ceramic materials to create decorative articles or models by fusion of a polymer by heating in an oven up to a maximum of 180 °C

### 3.7 embedding set

toy to be used to preserve certain products in a transparent material

### 3.8 model set

product used to assemble and coat models which are supplied with or recommend adhesives, paints, lacquers, varnishes, thinners and cleaning agents

NOTE 1 to entry: Examples for these models are motorcars, aeroplanes, houses and ships.

non-metallic substance capable of joining materials by surface bonding (adhesion) and the bond possessing adequate internal strength (cohesion)

### 3.10 water-based paints and lacquers

water based pigmented material which when applied in a liquid form to a surface, forms after a time a dry adherent film or coating

8

### 3.11 solvent based paints and lacquers

solvent based pigmented material which when applied in a liquid form to a surface, forms after a time a dry adherent film or coating

### 3.12 varnish

low viscosity lacquer

### 3.13 thinners and cleaning agents

solvents

products which are intended to obtain the required viscosity of paints and lacquers and to clean tools and brushes

## 4 Plaster of Paris (gypsum) moulding sets

NOTE Basically plaster of Paris (gypsum) is not a harmful material, but if the powder is inhaled or swallowed, it may form hard clots in the lungs or in the stomach.

### 4.1 Marking

The primary packaging shall in addition to the marking required in Clause 9 bear the following:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 5 years.

### 4.2 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”;
• “If swallowed: Wash out mouth with water, drink some fresh water. Do not induce vomiting. Seek immediate medical advice.”.

### 4.3 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Do not place the material in the mouth.”;
• “Do not inhale dust or powder.”;
• “Do not apply to the body.”.
9

## 5 Ceramic and vitreous enamelling materials supplied in miniature workshop sets

### 5.1 Chemical mixtures

These ceramic glazes and vitreous enamels are ready-made mixtures consisting of substances and mixtures given in Table 1. In each mixture there shall be not more than one of the pigments given in Table 1 with the limit for the pigment in the glaze. The maximum mass of each ready-made mixture in a set shall not exceed 50 g.

NOTE A ceramic glaze is a vitrified inorganic silicate material. A ceramic frit is a vitrified inorganic silicate material incorporating a pigment. These ready-made mixtures of silicate glazes are incorporating metal oxides and other compounds.

Table 1 — Chemical mixtures
Chemical substance/mixture CAS-Number EINECS-Number
Calcium silicate hydrate (clay) 1344-96-3 -
Kaolin (china clay) 1332-58-7 -
Sparingly soluble silicate glazes, e.g. enamel and ceramic frits 65997-18-4 266-047-6
Pigments CAS-Number EINECS-Number
Copper oxide 0,25 % 1317-38-0 215-269-1
Di-iron trioxide 5 % 1309-37-1 215-168-2
Ferro-zirconium silicate 5 % 68412-79-3 270-210-7
Tin dioxide 10 % 18282-10-5 242-159-0
Vanadium-zirconium silicate 5 % 68186-95-8 269-057-9
(x)Aluminium-(y)cobalt (z)oxide 3 % 1333-88-6
Zirconium orthosilicate 15 % 10101-52-7
Zirconium-praseodymium silicate 5 % 68187-15-5 269-075-7

### 5.2 Marking

The primary packaging shall in addition to the marking required in Clause 9 bear the following warnings:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 5 years.

### 5.3 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”.
10

### 5.4 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Do not inhale powder.”;
• “Do not place the powder in the mouth.”;
• “Do not apply to articles intended to come into contact with food and drink.”;
• “Keep the set away from food and drink.”;
• “The firing process is not part of the function of the toy. Therefore keep children away during the firing process and do not inhale gases emitted.”.

## 6 Oven-hardening plasticised PVC modelling clay sets

### 6.1 Chemical substances

These modelling clay sets shall consist of PVC (polyvinylchloride) and plasticisers and may contain modifiers, fillers (e.g. China clay) and colourants. Only plasticisers given in Table 2 shall be used.

The maximum content of plasticisers in the mixture shall not exceed 30 %.

The vinyl chloride monomer content shall be below 1 mg/kg (see [11]).

Table 2 — Plasticisers in oven-hardening plasticised PVC modelling clay sets
Chemical substance CAS-Number
Adipic acid polyesters -
Alkylsulfonic acid esters (C12 to C20) of phenol -
Di-isononyl cyclohexane-1,2-dicarboxylate (DINCH) 166412-78-8
Phthalic acid esters with straight-chain aliphatic (C6 upwards except C8) alcohols and mixtures of these esters -
Tributyl acetylcitrate 77-90-7
Tris(2-ethylhexyl) acetylcitrate 144-15-0

During heating of these materials at the maximum permitted temperature and duration, the limits given in Table 3 shall not be exceeded for the emission of the listed toxic substances when tested according to 11.4.

Table 3 — Limits for the emission of substances from oven-hardening plasticised PVC modelling clay
Substance Limit
mg/kg
Benzene 5
Toluene 15
Xylenes 25
11

### 6.2 Marking

The primary packaging shall in addition to the marking required in Clause 9 bear the following warning:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 8 years.

### 6.3 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of accidental overheating and inhalation of poisonous gases: Remove person to fresh air and seek immediate medical advice.”.

### 6.4 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• ”Do not place the material in the mouth.”;
• ”Do not exceed a hardening temperature of 130 °C or harmful gases may be produced.”;
• ”Do not exceed a hardening time of 30 minutes.”;
• ”The hardening process is not part of the function of the toy and should be carried out by the supervising adult.”;
• ”Use a domestic oven thermometer, e.g. bimetal, to measure the temperature.”;
• ”Do not use a glass thermometer.”;
• “Do not heat the material and cook food at the same time in a domestic oven”;
• ”Do not use a microwave oven.”.

## 7 Plastic moulding sets

### 7.1 Polystyrene granules

#### 7.1.1 Chemical substances

These sets shall contain uncoloured and coloured polystyrene granules in accordance with Table 4.

Table 4 — Polystyrene
Chemical substance CAS-Number EINECS-Number
Polystyrene with monomer content of styrene ≤ 500 mg/kg 9003-53-6 -
- 12

#### 7.1.2 Marking

The primary packaging shall in addition to the marking required in Clause 9 bear the following warnings:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 10 years.

#### 7.1.3 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of accidental overheating and inhalation of poisonous gases: Remove person to fresh air and seek immediate medical advice.”.

#### 7.1.4 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Do not exceed a melting temperature of 180 °C.”;
• “The melting process is not part of the function of the toy and should be carried out by the supervising adult.”;
• “Use a domestic oven thermometer, e.g. bimetal, to measure the temperature.”;
• “Do not swallow material.”;
• “Do not heat the material and cook food at the same time in a domestic oven.”;
• “Do not use a glass thermometer.”;
• “Do not exceed the maximum recommended processing period.”;
• “Do not use a microwave oven.”.

### 7.2 Embedding sets

#### 7.2.1 General

Substances classified as dangerous substances (see [5]) shall not be used in embedding sets.

NOTE Substances such as gelatine or agar could be utilised with suitable preservation.

Only preservatives permitted in foodstuffs (see [9]) and/or cosmetics, except those preservatives which are only allowed in cosmetic products that are rinsed-off after use, (see [10]) shall be used.

#### 7.2.2 Packaging

The name(s) of any preservative(s) used shall be indicated on the primary packaging.

13

#### 7.2.3 Marking

The packaging shall in addition to the marking required in Clause 9 bear the following warnings:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 5 years.

#### 7.2.4 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “If swallowed: Wash out mouth with water, drink some fresh water. Do not induce vomiting. Seek immediate medical advice.”.

#### 7.2.5 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rule:

• “Do not place the preserved material in the mouth.”.

## 8 Adhesives, paints, lacquers, varnishes, thinners and cleaning agents (solvents) supplied or recommended in model sets

### 8.1 General

Adhesives, paints, lacquers, varnishes, thinners and cleaning agents (solvents) supplied in model sets shall comply with the requirements in Clause 8. The instructions included in the set shall mention only adhesives, paints, lacquers, varnishes, thinners and cleaning agents (solvents) that comply with the requirements in Clause 8.

#### 8.2.1 Water-based adhesives

##### 8.2.1.1 General

Water-based adhesives shall consist of water and basic materials. Only basic materials given in Table 5 shall be used. Additionally, water based adhesives may contain special materials given in Table 6 or Table 8, preservatives, fillers and modifiers.

Only preservatives permitted in foodstuffs (see [9]) and/or cosmetics, except those preservatives which are only allowed in cosmetic products that are rinsed-off after use, (see [10]) shall be used.

Basic materials for water-based adhesives shall be in accordance with Table 5.

14
Table 5 — Basic materials for water-based adhesives and water-based paints and lacquers
Chemical substance CAS-Number EINECS-Number
Acrylic polymers - -
Hydrophilic polyurethane containing neither free isocyanate-groups nor aromatic amino-compounds - -
Polymers and copolymers of monomers permitted for materials intended to come into contact with foodstuffs - -
Poly(vinyl acetate) 9003-20-7 -
Poly(vinyl alcohol) 9002-89-5 209-183-3

The basic materials shall be appropriate for food contact (see [11]). The migration solvent shall be water, grade 3 according to EN ISO 3696. The contact time shall be approximately 60 min at approximately 40 °C.

##### 8.2.1.2 Liquid adhesives for paper and wood
###### 8.2.1.2.1 General

Special materials for adhesives for paper and wood shall be in accordance with Table 6.

Table 6 — Special materials for adhesives for paper and wood and water-based paints and lacquers
Chemical substance CAS-Number EINECS-Number
Cellulose ethers (e.g. carboxymethylcellulose, methylcellulose) 9004-67-5 -
Dextrin 9004-53-9 232-675-4
Gum arabic 9000-01-5 232-519-5
Starch or modified starch 9005-25-8 232-679-6

Special additives for adhesives for paper and wood shall be in accordance with Table 7.

15
Table 7 — Special additives for liquid adhesives for paper and wood
Chemical substance CAS-Number EINECS-Number
Butyl glycolate (Butyl hydroxyacetate) < 3 % 7397-62-8 230-991-7
Caprolactam < 5 % 105-60-2 203-313-2
Glycerol 56-81-5 200-289-5
Polyacrylamide 9003-05-8 -
Poly(acrylic acid) 9003-01-4 -
Polyethylene glycol 25322-68-3 -
Poly(methacrylic acid) 25087-27-7 -
Polypropylene glycol 25322-69-4 -
Sodium salts of fatty acids (C14 upwards) - -
Sorbitol 50-70-4 200-061-5
2-(2-Butoxyethoxy)ethyl acetate < 3 % 124-17-4 204-685-9
Xylitol 87-99-0 201-788-0

The polymers given in Table 7 shall be appropriate for food contact (see [11]). The migration solvent shall be water grade 3 according to EN ISO 3696. The contact time shall be approximately 60 min at approximately 40 °C.

###### 8.2.1.2.2 Packaging

The capacity of the containers for water-based adhesives in a set shall not be more than 100 ml. The name(s) of any preservative(s) used shall be indicated on the primary packaging.

###### 8.2.1.2.3 Marking

The adhesive container shall in addition to the marking required in Clause 9 bear the following warnings:

“Warning. Not suitable for children under (*) years. For use under adult supervision.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 3 years.

###### 8.2.1.2.4 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of skin contact: Wash affected area with plenty of water.”;
• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”.
##### 8.2.1.3 Adhesive sticks for paper
###### 8.2.1.3.1 General

Special materials for adhesive sticks for paper shall be in accordance with Tables 6, 7 and 8.

16
Table 8 — Special material for adhesive sticks for paper
Chemical substance CAS-Number EINECS-Number
Poly(vinyl pyrrolidone) 9003-39-8 -
-

The special materials shall be appropriate for food contact (see [11]). The migration solvent shall be water grade 3 according to EN ISO 3696. The contact time shall be approximately 60 min at approximately 40 °C.

###### 8.2.1.3.2 Packaging

The mass of the adhesive stick in a set shall not exceed 50 g.

###### 8.2.1.3.3 Marking

The packaging, if any, or the adhesive stick container shall in addition to the marking in Clause 9 bear the following warning:

“Warning. Not suitable for children under (*) years. For use under adult supervision.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 3 years.

###### 8.2.1.3.4 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of skin contact: Wash affected area with plenty of water.”;
• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”.

#### 8.2.2 Solvent-based adhesives

##### 8.2.2.1 General

Solvent-based adhesives consist of basic material specified in Tables 5, 6 and 8 and basic materials from the relevant sub-clauses under 8.2.2. Further they consist of substances from Tables 7 and 12 with the limits given there and may additionally contain fillers, modifiers and plasticisers. Plasticisers shall be appropriate for food contact (see [11]) or be in accordance with Table 13).

NOTE 1 Certain phthalate plasticisers are restricted in toys, see E.4.

The content of plasticiser in these adhesives shall not exceed 8 %. The content of modifiers shall not exceed 3 %.

For solvent-based adhesives containing petroleum fractions, the n-hexane content shall not exceed 0,5 %.

The final mixture containing petroleum fractions shall not be classified with R48/20 and/or H372.

NOTE 2 The classifications are detailed in Directive 67/548/EEC [6] and Regulation (EC) No. 1272/2008 [5].

##### 8.2.2.2 Multi-purpose adhesives

Basic materials for multi-purpose adhesives shall be in accordance with Table 9.

17
Table 9 — Basic materials for multi-purpose adhesives
Chemical substance CAS-Number EINECS-Number
Acrylic polymers 9003-01-4 -
Cellulose nitrate 9004-70-0 -
Poly(vinyl acetate) 9003-20-7 -
Vinyl acetate copolymers - -
##### 8.2.2.3 Contact adhesives

Basic materials for contact adhesives shall be in accordance with Table 10.

Table 10 — Basic materials for contact adhesives
Chemical substance CAS-Number EINECS-Number
Polymers and copolymers of monomers permitted for materials intended to come into contact with foodstuffs - -
Polyurethane 73561-64-5 -
##### 8.2.2.4 Special adhesives

Basic materials for special adhesives shall be in accordance with Table 11.

Table 11 — Basic materials for special adhesives
Chemical substanceCAS-NumberEINECS-Number
Acrylic polymers
Polymers and copolymers of monomers permitted for materials intended to come into contact with foodstuffs
Polystyrene9003-53-6
Vinyl chloride copolymers

The basic materials shall be appropriate for food contact (see [11]). The migration solvent shall be water, grade 3 according to EN ISO 3696. The contact time shall be approximately 60 min at approximately 40 °C.

18
Table 12 — Solvents in solvent-based adhesives
Chemical substance/mixtureCAS-NumberEINECS-Number
Acetone (Dimethyl ketone)67-64-1200-662-2
Cyclohexane < 3 %110-82-7203-806-2
Pentan-3-one (Diethyl ketone)96-22-0202-490-3
Ethyl acetate141-78-6205-500-4
Ethanol (Ethyl alcohol)64-17-5200-578-6
Propan-2-yl acetate (Isopropyl acetate)108-21-4203-561-1
Propan-2-ol (Isopropyl alcohol)67-63-0200-661-7
Methyl acetate79-20-9201-185-2
Butan-2-one (Methyl ethyl ketone)78-93-3201-159-0
3-Methylbutan-2-one (Methyl isopropyl ketone)563-80-4209-264-3
n-Butyl acetate123-86-4204-658-1
n-Propyl acetate109-60-4203-686-1
1-Methoxypropan-2-ol107-98-2203-539-1
1,1-Dimethoxyethane534-15-6208-589-8
Petroleum fraction (60 to 140) °C64742-89-8265-192-2
Petroleum fraction (135 to 210) °C64742-88-7265-191-7

The maximum content of 1-methoxypropan-2-ol shall be 20 %.

If the product contains Petroleum fraction (60 to 140) °C and/or Petroleum fraction (135 to 210) °C, the viscosity of the product shall exceed 20,5 mm2/s when tested in accordance with EN ISO 3104 or EN ISO 3219.

Table 13 — Plasticisers in solvent-based adhesives and solvent-based paints, lacquers,
PlasticiserCAS-Number
Tributyl acetylcitrate77-90-7
Tri(2-ethylhexyl) acetylcitrate144-15-0
Alkylsulfonic acid esters (C12 to C20) of phenol91082-17-6
Di-isononyl cyclohexane-1,2-dicarboxylate
(DINCH)
166412-78-8

2,2-Bis(4-hydroxyphenyl)propane diglycidyl ether (BADGE), bis(hydroxyphenyl)methane diglycidyl ether (BFDGE) and Novolac glycidyl ethers (NOGE), together with their derivatives shall not be used as modifiers for adhesives.

NOTE Key

BADGE - 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, Bisphenol-A diglycidyl ether [1675-54-3];

19

BFDGE - bis(hydroxyphenyl)methane diglycidyl ether, Bisphenol-F diglycidyl ether [39817-09-9];

NOGE - Novolac glycidyl ethers [28064-14-4] and [9003-36-5].

##### 8.2.2.5 Packaging

The content of the container in a set shall not exceed 15 g.

##### 8.2.2.6 Marking

The primary packaging of the set shall in addition to the marking required in Clause 9 bear the following warnings:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 8 years.

The individual container shall be marked according to 9.3.

##### 8.2.2.7 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of skin contact: Wash affected area with plenty of water.”;
• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”;
• “In case of inhalation: Remove person to fresh air.”.
##### 8.2.2.8 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Keep away from ignition sources.”;
• “Do not allow adhesive to come into contact with the skin, the eyes and the mouth.”;
• “Do not swallow material.”;
• “Do not inhale fumes.”.

### 8.3 Water-based paints and lacquers

#### 8.3.1 General

Water-based paints and lacquers shall consist of water and basic materials. Only basic materials given in Table 5 shall be used. Additionally, water-based paints and lacquers may contain special materials given in Table 6 and organic solvents and film-forming agents given in Table 14 or Table 7, colouring agents, preservatives, fillers and modifiers.

20

The content of organic solvents and film-forming agents shall not exceed 10 %. Only preservatives permitted in foodstuffs (see [9]) and/or cosmetics, except those preservatives which are only allowed in cosmetic products that are rinsed-off after use, (see [10]) shall be used.

Table 14 — Organic solvents and film-forming agents
Chemical substance/mixtureCAS-NumberEINECS-Number
Di(2-methylpropyl)ester of aliphatic dicarboxylic acids (C20 to C33)
(maximum 2 % as film-forming agents)
Ethanol (Ethyl alcohol)64-17-5200-578-6
Mixture of aliphatic esters and alcohols (C12 to C14)
(maximum 2 % as film-forming agents)
1-Methoxypropan-2-ol107-98-2203-539-1
Propan-1,2-diol (Propylene glycol)57-55-6200-338-0
2-Methylpentane-2,4-diol (Hexylene glycol)107-41-5203-489-0
Propan-2-ol (Isopropyl alcohol)67-63-0200-661-7

#### 8.3.2 Packaging

The content of the container in a set shall not exceed 100 ml.

The name(s) of any preservative(s) used shall be indicated on the primary packaging.

#### 8.3.3 Marking

The packaging or the container shall in addition to the marking required in Clause 9 bear the following warning:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 8 years.

#### 8.3.4 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of skin contact: Wash affected area with plenty of water.”;
• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”;
• “In case of inhalation: Remove person to fresh air.”.
21

#### 8.3.5 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Do not allow material to come into contact with the eyes.”;
• “Do not place material in the mouth.”;
• “Do not inhale vapours.”.

### 8.4 Solvent-based paints, lacquers, thinners and cleaning solvents

#### 8.4.1 General

Solvent-based paints and lacquers shall consist of solvents and basic materials. Only basic materials given in Table 15 and solvents given in Table 14 and Table 16 shall be used. Paints and lacquers shall not contain more than 2 % of 2-methylpropan-1-ol or n-butanol and not more than 20 % 1-methoxypropan-2-ol.

Additionally, solvent-based paints and lacquers may contain colourants, fillers and modifiers. The content of modifiers shall not exceed 3 %.

For solvent-based paints and lacquers prepared with nitrocellulose the content of plasticiser shall not exceed 5 %.

Plasticisers shall be appropriate for food contact (see [11]) or be in accordance with Table 13.

NOTE 1 Certain phthalate plasticisers are restricted in toys, see E.4.

Thinners and cleaning solvents shall contain only substances and mixtures given in Tables 14 and 16 except film-forming agents. 2-Methylpropan-1-ol, n-butanol and 1-methoxypropan-2-ol shall not be used in thinners and cleaning agents.

For solvent-based paints, lacquers, thinners and cleaning solvents containing petroleum fractions the nhexane content shall not exceed 0,5 %. n-Hexane shall only occur in these solvents as a contaminant of petroleum fractions.

The final mixture containing petroleum fractions shall not be classified with R48/20 and/or H372.

NOTE 2 The classifications are detailed in Regulation (EC) No. 1272/2008 [5].

Pressurised containers (aerosols) shall not be used for paints, lacquers, thinners or cleaning solvents.

Table 15 — Basic materials
Chemical substanceCAS-NumberEINECS-Number
Acrylic polymers
Alkyd polymers
Nitrocellulose9004-70-0
22
Table 16 — Solvents
Chemical substance/mixtureChemical substance/mixtureCAS-NumberEINECS-Number
Glycerol triacetateGlycerol triacetate102-76-1203-051-9
2-Methylpropan-1-ol (iso-Butanol)2-Methylpropan-1-ol (iso-Butanol)78-83-1201-148-0
Butan-2-one (Methyl ethyl ketone)Butan-2-one (Methyl ethyl ketone)78-93-3201-159-0
1-Methoxypropan-2-ol1-Methoxypropan-2-ol107-98-2203-539-1
1-methoxypropan-2-yl acetate1-methoxypropan-2-yl acetate108-65-6203-603-9
Butan-1-ol (n-Butanol)Butan-1-ol (n-Butanol)71-36-3200-751-6
3-Methoxybutyl acetate3-Methoxybutyl acetate4435-53-4224-644-9
Petroleum fraction (60 to 140) °CPetroleum fraction (60 to 140) °C64742-89-9
Petroleum fraction (135 to 210) °CPetroleum fraction (135 to 210) °C64742-88-7265-191-7

If the product contains Petroleum fraction (60 to 140) °C and/or Petroleum fraction (135 to 210) °C, the viscosity of the product shall exceed 20,5 mm2/s when tested in accordance with EN ISO 3104 or EN ISO 3219.

#### 8.4.2 Packaging

The maximum content of the container in a set shall not exceed:

• 15 ml for liquids with a flash point < 23 °C and initial boiling point > 35 °C;
• 50 ml for liquids with a flash point ≥ 23 °C.

NOTE For information regarding packaging and labelling, including child-resistant fastenings, see [5] and EN ISO 8317 [2].

#### 8.4.3 Marking

The primary packaging shall in addition to the marking required in Clause 9 bear the following warning:

“Warning. Not suitable for children under (*) years. For use under adult supervision.

Read the instructions before use, follow them and keep them for reference.”.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below 8 years.

#### 8.4.4 First aid information

The instructions for use shall in addition to the general first aid information in 10.2 d) contain the following:

• “In case of skin contact: Wash affected area with plenty of water.”;
• “In case of eye contact: Wash out eye with plenty of water, holding eye open. Seek immediate medical advice.”;
• “If swallowed: Wash out mouth with water, drink some fresh water. Do not induce vomiting. Seek immediate medical advice."; 23
• “In case of inhalation: Remove person to fresh air.”.

#### 8.4.5 Safety rules

The instructions for use shall in addition to the rules required in 10.4 contain the following safety rules:

• “Keep away from ignition sources.”;
• “Do not allow product to come into contact with the skin and the eyes.”;
• “Do not place material in the mouth.”;
• “Do not inhale vapours.”.

## 9 Marking

### 9.1 General

Markings shall be visible, easily legible, indelible and in the national language(s) of the country of sale.

If the container is too small to carry all the information necessary an additional instruction leaflet shall be supplied with the package.

### 9.2 Marking of the primary packaging

#### 9.2.1 General

The primary packaging shall indicate any dangerous substances or dangerous mixtures (see [5]) that are recommended but not included in the toy.

NOTE Examples for dangerous substances or dangerous mixtures that are recommended but not included in the toy are adhesives, paints or lacquers.

#### 9.2.2 Manufacturer’s identification

The primary packaging shall bear the name, registered trade name or registered trade mark of the manufacturer or the importer and the address at which they can be contacted.

NOTE If the manufacturer (declaring himself as a manufacturer by putting his name and address on the toy) is outside the Community and the products are placed on the EU market by an importer, the toy will bear two addresses: the one of the manufacturer and the one of the importer.

Chemical toy (sets) shall bear a type, batch, serial or model number or other element allowing their identification.

#### 9.2.3 Warning phrases

The primary packaging shall bear the relevant warning phrases in Clauses 4 to 8. An uppercase letter size of a minimum height of 7 mm shall be used for the word "Warning" (as recommended under “Marking” in Clauses 4 to 8) on primary packaging.

### 9.3 Marking of individual containers and any packagings

The individual containers and packagings (including primary packaging) shall bear the following information:

24
1. If the substance/mixture is classified as dangerous (see [5]), the name of the chemical substance or mixture as given in the relevant table(s) and clause(s).
2. Where relevant, the required pictogram(s) and the required H- and P- phrases (see [5]).

NOTE For information on transitional provisions on classification, labelling and packaging of substances and mixtures see Regulation (EC) No 1272/2008, art. 61.

## 10 Instructions for use

### 10.1 General

The instructions for use shall be given in the national language(s) of the country of sale.

The marking of the primary packaging according to 9.2.3 shall be repeated on the cover of the instructions for use.

### 10.2 Contents list

The contents list shall contain the following information:

1. where relevant, the name(s) of the chemical(s) supplied;
2. where relevant, the H-and P-phrases specified in Regulation (EC) No. 1272/2008 [5] appropriate to each particular substance and mixture;

NOTE 1 For information on transitional provisions on classification, labelling and packaging of mixtures see Regulation (EC) No 1272/2008 [5], art. 61.

NOTE 2 H- and P-phrase information is required for all dangerous substances and dangerous mixtures supplied in these sets even if a derogation from labelling is permitted by EU legislation (e.g. for small quantities of certain dangerous substances).

3. where relevant and if the substances/mixture is classified according to Regulation (EC) No 1272/2008 [5], an empty space shall be provided in which the telephone number of the local poison centre (central office for first aid information) or hospital, if possible, should be entered in case of intake by accident of dangerous substances;
4. general first aid information as follows:

1. “In case of doubt seek medical advice without delay: Take the chemical and/or product together with the container with you.”;
2. “In case of injury always seek medical advice.”;

NOTE 3First aid information may also be found in the instructions for carrying out the activity.

5. specific first aid information specified in Clauses 4 to 8 when appropriate.

Where appropriate, the advice for adults shall contain the following information:

1. This chemical toy is not suitable for children under (*) years. For use under adult supervision. Keep this chemical toy set out of reach of children under (*) years old. 25
2. Read and follow these instructions, the safety rules and the first aid information and keep them for reference.
3. Incorrect use of chemicals can cause injury and damage to health. Only carry out those activities which are listed in the instructions.
4. Because children’s abilities vary so much, even within age groups, supervising adults should exercise discretion as to which activities are suitable and safe for them. The instructions should enable supervisors to assess any activity to establish its suitability for a particular child.
5. The supervising adult should discuss the warnings, safety information and the possible hazards with the child or children before commencing the activities. Particular attention should be paid to the safe handling of alkalies, acids and flammable liquids.
6. The area surrounding the activity should be kept clear of any obstructions and away from the storage of food. It should be well lit and ventilated and close to a water supply. A solid table with a heat resistant top should be provided.”.
7. The working area should be cleaned immediately after carrying out the activity.

(*) The age is to be specified by the manufacturer, authorised representative or importer. It shall not be below the requirements for the age limits specified within Clauses 4 to 8.

### 10.4 Safety rules

The following safety rules shall be given:

• “Keep younger children under the specified age limit and animals away from the activity area.”;
• “Store chemical toys out of reach of young children.”;
• “Wash hands after carrying out activities.”;
• “Clean all equipment after use.”;
• “Do not use any equipment which has not been supplied with the set or recommended in the instructions for use.”;
• “Do not eat, drink or smoke in the activity area.”;

and, where appropriate, the special safety rules given in Clauses 4 to 8.

### 10.5 Instructions for carrying out the activities

Detailed information on how to perform each activity shall be given.

The activities, where relevant, should be evaluated by the manufacturer.

Any known hazards arising from the use of the toy should be detailed.

### 10.6 Spills and disposal of chemicals

Where relevant, information on the handling of spills and on the disposal of used chemicals shall be given.

The instructions for disposal shall take account of national regulations for the disposal of such chemicals.

26

## 11 Test methods

### 11.1 General

All chemicals used for analysis shall be of analytical grade (pro analysis) or, if unavailable, the best technical grade. Water shall be of grade 3 according to EN ISO 3696 or of a comparable quality, and demonstrably free from analytes of interest.

The precision of volumetric glassware should be grade A.

The analysis of chemical toys and chemical toy materials for chemical compounds shall be performed in accordance with the methods of analysis described in this 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.

### 11.2 Determination of elements in ceramic and vitreous enamelling materials

#### 11.2.1 Principle

The ceramic or enamel sample is submitted to a melting digestion using dilithium tetraborate. After the dissociation the fused product is extracted by means of diluted hydrochloric acid. The individual metals are determined by atomic emission spectrophotometry.

#### 11.2.2 Standards and reagents

##### 11.2.2.1 Standards

NOTE These elemental standard solutions are commercially available.

Table 17 — Standards
ChemicalConcentration
mg/l
Copper1 000
Iron1 000
Praseodymium1 000
Cobalt1 000
Zirconium1 000
Tin1 000
##### 11.2.2.2 Reagents
Table 18 — Reagents
ChemicalConcentration
Dilithium tetraborate (Li2B4O7)
Hydrochloric acidρ(HCl) = 1,12 g/ml
27

#### 11.2.3 Apparatus

NOTE As there is no standardised equipment on the market only general detailed user's instructions could be provided.

##### 11.2.3.4 Glassware (beaker, funnel, volumetric flask and pipettes).

Before use all glass equipment shall be cleaned using 10 % hydrochloric acid (per volume).

#### 11.2.4 Preparation of standard solutions

##### 11.2.4.1 Multi-element standard solution I

c (Cu, Fe, Pr, Co, Zr, V, Sn) = 10 mg/l

Pipette (1,0 ± 0,01) ml of each of the 1 000 mg/l standards (11.2.2.1) into a 100-ml volumetric flask. Add 10 ml of hydrochloric acid (11.2.2.2), mix and make up to the mark with water.

The multi-element standard solution I may be stored for a month in a refrigerator at (4 ± 2) ºC.

##### 11.2.4.2 Multi-element standard solution II

c (Cu, Fe, Pr, Co, Zr, V, Sn) = 5,0 mg/l

Pipette (50 ± 0,05) ml of the multi-element standard solution I into a 100-ml volumetric flask. Add 10 ml of hydrochloric acid (11.2.2.2), mix and make up to the mark with water.

This solution shall be freshly prepared.

##### 11.2.4.3 Multi-element standard solution III

c (Cu, Fe, Pr, Co, Zr, V, Sn) = 1,0 mg/l

Pipette (10 ± 0,02) ml of the multi-element standard solution I into a 100-ml volumetric flask. Add 10 ml of hydrochloric acid (11.2.2.2), mix and make up to the mark with water.

This solution shall be freshly prepared.

#### 11.2.5 Blank solution

Add 10 ml hydrochloric acid to 90 ml water in a polyethene- or polytetrafluorethene (PTFE)-flask.

#### 11.2.6 Sampling

Obtain three test portions from each colour of the material and treat them separately.

NOTE Homogenisation of the test portions is not necessary because the materials have been melted and are very finely ground.

28

#### 11.2.7 Sample preparation

Weigh (0,1 ± 0,05) g to the nearest 0,001 g of each test portion in a platinum crucible. Add 1 g of dilithium tetraborate to the crucible and mix carefully. Heat the crucible in a muffle furnace to (1 000 ± 50) ºC for (120 ± 5) min.

After cooling to approximately 500 ºC remove the crucible from the muffle furnace and transfer it into a glass of water. Add 20 ml of hydrochloric acid. Heat the solution to boiling point and let it boil until complete dissolution of the sample occurs. Transfer the solution into a 250-ml volumetric flask and filled up to the mark. If silicon dioxide is precipitated, remove it by filtration.

#### 11.2.8 Procedure

Determine the elemental concentrations using the wavelengths according to Table 19. In case of spectral interference choose an alternative appropriate wavelength.

Table 19 — Wavelengths
ElementWavelength
nm
Copper (Cu)324,752
Iron (Fe)259,942
Praseodymium (Pr)422,285
Cobalt (Co)228,616
Zirconium (Zr)339,198
Tin (Sn)189,932

After the verification of the calibration function the samples are measured.

Determine the blank solutions before analysing the solutions.

Recalibrate the analytical instruments frequently. To avoid memory effects perform also checks with the blank solution.

#### 11.2.9 Evaluation of results

##### 11.2.9.1 General

The mean value of three test portions shall be given.

The metal contents are calculated according to Formula (1).

${M}_{m}=\frac{\left({c}_{\mathrm{sample}}\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}{c}_{\mathrm{blank}}\right)\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}V\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}f}{W\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}10 000}$(1)

where

Mm is the content of the metal in the sample, in % (m/m);

csample is the concentration of the metal in the analytical solution, in mg/l;

29

cblank is the concentration of the metal in the blank value solution, in mg/l;

V is the volume of the sample solution, in ml;

f is the dilution factor;

W is the weighed portion of the sample, in g.

The calculated contents of elements are compared with the maximum permitted element concentrations in the compounds given in Table C.1. If these concentrations are not exceeded, the requirements of EN 71-5 are fulfilled.

If a metal concentration calculated according to Formula (1) is exceeded, the concentration of the relevant permitted compound shall be calculated according to 11.2.9.2.

The metal oxide contents are calculated according to Formula (2):

${M}_{mo}=\frac{\left({c}_{\mathrm{sample}}\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}{c}_{\mathrm{blank}}\right)\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}V\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}f\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}{f}_{m}}{W\phantom{\rule{.2em}{0ex}}⨉\phantom{\rule{.2em}{0ex}}10 000}$(2)

where

Mmo is the content of the metal oxide in the sample, in % (m/m);

csample is the concentration of the metal in the analytical solution, in mg/l;

cblank is the concentration of the metal in the blank value solution, in mg/l;

V is the volume of the sample solution, in ml;

f is the dilution factor;

W is the weighed portion of the sample, in g;

fm is the calculation factor of metal to metal oxide.

For the conversion factor fm for the individual metals see Table 20.

Table 20 — Conversion factors
CompoundElementConversion factor
Copper oxide (CuO)Cu1,251 8
Di-iron trioxide (Fe2O3)Fe1,429 7
Dipraseodymium trioxide (Pr2O3)Pr1,170 3
Cobalt oxide (CoO)Co1,271 5
Zirconium dioxide (ZrO2)Zr1,350 8
Divanadium pentoxide (V2O5)V1,785 2
Tin dioxide (SnO2)Sn1,269 6
30
##### 11.2.9.2 Calculation of the pigment contents in the enamel samples
###### 11.2.9.2.1 Calculation of the concentration of copper oxide (CuO) and tin dioxide (SnO2)

The concentration of copper oxide and tin dioxide shall be calculated according to Formula (2).

###### 11.2.9.2.2 Calculation of the concentration of aluminium cobalt oxide (CoO.Al2O3)

The concentration of aluminium cobalt oxide shall be calculated by multiplying the amount of CoO calculated according to Formula (2) by the factor 2,360 7.

$\mathrm{Co}O⨉2,360 7={\mathrm{CoO.Al}}_{2}{O}_{3}$ (3)

###### 11.2.9.2.3 Calculation of the concentration of praseodymium zirconium silicate (Pr2O3 + ZrSiO4)

The concentration of praseodymium zirconium silicate shall be calculated by multiplying the amount of Pr2O3 calculated according to Formula (2) by the factor 1,555 8.

${\mathrm{Pr}}_{2}{O}_{3}⨉1,555 8={\mathrm{Pr}}_{2}{O}_{3}+\mathrm{ZrSi}{O}_{4}$(4)

###### 11.2.9.2.4 Calculation of the concentration of vanadium zirconium silicate (V2O4 + ZrSiO4)

The concentration of vanadium zirconium silicate shall be calculated by multiplying the amount of V2O5 calculated according to Formula (2) by the factor 1,919 8.

${V}_{2}{O}_{5}⨉1,919 8={V}_{2}{O}_{4}+\mathrm{ZrSi}{O}_{4}$(5)

###### 11.2.9.2.5 Calculation of the concentration of di-iron oxide (Fe2O3), iron zirconium silicate (Fe2O3 + ZrSiO4) and zirconium ortho silicate (ZrSiO4)

Calculate the Fe2O3 total , V2O5 total, Pr2O3 total and ZrO2 total concentration according to Formula (2).

If Pr2O3 is present, then the concentration of (Pr2O3 + ZrSiO4) shall be calculated according to Formula (4).

The amount of ZrO2 (a) shall be calculated by multiplying the concentration of (Pr2O3 + ZrSiO4) by the factor 0,240 1.

$\left({\mathrm{Pr}}_{2}{O}_{3}+\mathrm{ZrSi}{O}_{4}\right)⨉0,240 1=\mathrm{Zr}{O}_{2}\text{(a)}$(6)

If V2O5 is present, the concentration of (V2O4 + ZrSiO4) shall be calculated according to Formula (5).

The amount of ZrO2 (b) shall be calculated by multiplying the concentration of (V2O4 + ZrSiO4) by the factor 0,352 9.

$\left({V}_{2}{O}_{4}+\mathrm{ZrSi}{O}_{4}\right)⨉0,352 9=\mathrm{Zr}{O}_{2}\text{(b)}$(7)

The ZrO2 (a) and ZrO2 (b) amounts shall be added and subtracted from ZrO2total.

$\mathrm{Zr}{O}_{2\mathrm{total}}-\left(\mathrm{Zr}{O}_{2}\text{(a)}+\mathrm{Zr}{O}_{2}\text{(b)}\right)=\mathrm{Zr}{O}_{2}\text{(c)}$(8)

The concentration of iron zirconium silicate (Fe2O3 + ZrSiO4) shall be calculated from the amount of Fe2O3 calculated according to Formula (2).

The amount of Fe2O3 shall be multiplied by the factor 2,147 8.

${\mathrm{Fe}}_{2}{O}_{3}⨉2,147 8={\mathrm{Fe}}_{2}{O}_{3}+\mathrm{ZrSi}{O}_{4}$(9)

31

The amount of ZrO2 (d) shall be calculated by multiplying the concentration of (Fe2O3 + ZrSiO4) by the factor 0,359 3.

$\left({\mathrm{Fe}}_{2}{O}_{3}+\mathrm{ZrSi}{O}_{4}\right)×0,359 3=\mathrm{Zr}{O}_{2}\text{(d)}$(10)

If ZrO2 (c) > ZrO2 (d) the difference ZrO2 (c) - ZrO2 (d) is used to calculate ZrO2 (e).

$\mathrm{Zr}{O}_{2}\text{(c)}·\mathrm{Zr}{O}_{2}\text{(d)}=\mathrm{Zr}{O}_{2}\text{(e)}$(11)

The amount of ZrSiO4 pure is calculated by multiplying the ZrO2 (e) concentration by the factor 1,487 6.

$\mathrm{Zr}{O}_{2}\text{(e)}×1,487\phantom{\rule{.2em}{0ex}}6=\mathrm{Zr}\mathrm{Si}{O}_{4\phantom{\rule{.2em}{0ex}}\mathrm{pure}}$(12)

If ZrO2 (c) < ZrO2 (d) the concentration of (Fe2O3 + ZrSiO4) is calculated by multiplying the ZrO2 (c) concentration by the factor 2,783 6.

$\mathrm{Zr}{O}_{2}\text{(c)}×2,783\phantom{\rule{.2em}{0ex}}6={\mathrm{Fe}}_{2}{O}_{3}+\mathrm{Zr}\mathrm{Si}{O}_{4}$(13)

The amount of Fe2O3 (a) is calculated by multiplying the concentration of (Fe2O3 + ZrSiO4) by the factor 0,465 6.

$F{e}_{2}{O}_{3}+\mathrm{Zr}\mathrm{Si}{O}_{4}×0,465 6=F{e}_{2}{O}_{3}\left(a\right)$(14)

The concentration of the pure di-iron oxide (Fe2O3 pure) is the difference between (Fe2O3) total and Fe2O3 (a).

${\mathrm{Fe}}_{2}{O}_{3\phantom{\rule{.2em}{0ex}}\mathrm{total}}⨉{\mathrm{Fe}}_{2}{O}_{3}\text{(a)}={\mathrm{Fe}}_{2}{O}_{3\phantom{\rule{.2em}{0ex}}\mathrm{pure}}$(15)

#### 11.2.10 Test report

The test report shall contain, as a minimum, the following:

1. type and identification of the product and/or material tested;
2. a reference to this European Standard (i.e. EN 71-5:2013);
3. the results of the tests expressed as x % (m/m) pigment content rounded to 0,01 % (m/m), but not more than three significant digits;
4. any deviation from the test procedure specified;
5. date of test.

### 11.3 Determination of plasticisers in oven-hardening polyvinyl chloride (PVC) modelling clay sets

#### 11.3.1 Principle

The plasticiser content is determined by solvent extraction to quantitatively extract the plasticiser from a known weight of PVC material using a Soxhlet extractor. Hexane is used to extract phthalic acid esters, citric acid esters and alkylsulfonic acid esters. Methanol is used to extract adipic acid polyesters. Indicative plasticiser content can be determined by evaporating off the solvent and weighing the solvent residue and identifying the plasticiser by Attenuated Total Reflectance-Fourier Transform-Infra Red (ATR-FT-IR) Spectrometry.

Determination of plasticiser(s) content is by Gas Chromatography-Mass Spectrometry (GC-MS) for phthalic acid esters, alkylsulfonic acid phenyl ester and citric acid esters. Adipic acid esters are quantified gravimetrically.

32

This method is also partly used for the determination of plasticisers in solvent-based adhesives and solventbased paints and lacquers (see 11.7.4).

#### 11.3.2 Standards and reagents

##### 11.3.2.1 Standards

NOTE The given substances (except citrates) are examples for the requirements in Table 13.

Table 21 — Phthalic acid esters
ChemicalCAS No.
bis(2-ethylhexyl) phthalate (DEHP)117-81-7
di-isononyl phthalate (DINP)28553-12-0
di-isodecyl phthalate (DIDP)26761-40-0
benzyl butyl phthalate (BBP)85-68-7
di-n-butyl phthalate (DBP)84-74-2
di-n-hexyl phthalate (DNHP)84-75-3
di-n-heptyl phthalate (DNHpP)3648-21-3
di-n-octyl phthalate (DNOP)117-84-0
di-n-nonyl phthalate (DNP)84-76-4
di-n-decyl phthalate (DDP)84-77-5

NOTE 1 The chemicals DEHP, DINP, DIDP, BBP, DNOP and DBP can be used for analytical purposes for modelling clays. They are not permitted for the use in PVC modelling clays. However, they are examples for plasticisers according to the requirements in 8.2.2 and 8.4.

NOTE 2 The technical grade of the substances DINP and DIDP is typically a mixture of isomers and homologues.

33
Table 22 — Adipic acid polyesters
Hexanedioic acid, polymer with propane-1,2- diol, acetatePalamoll a 632 & 63655799-38-7
Hexanedioic acid, polymer with butane-1,3-diol and butane-1,4-diol, acetatePalamoll a 646150923-12-9
Hexanedioic acid, polymer with 2,2-dimethyl- propane-1,3-diol and propane-1,2-diol, isononyl esterPalamoll a 652208945-13-5
Hexanedioic acid, polymer with butane-1,4-diol and 2,2-dimethyl-propane-1,3-diol, isononyl esterPalamoll a 654 & 656208945-12-4
Hexanedioic acid, polymer with 2,2-dimethyl- propane-1,3-diol and 3-hydroxy-2,2- dimethylpropanoic acid, isononyl esterPalamoll a 858208945-11-3
No chemical inventory name availableParaplex b G-4039363-92-3
a Polymeric plasticiser derived from adipic acid and polyhydric alcohols.
NOTE Trade names for adipic acid polyesters are examples for those types of plasticisers.
Table 23 — Citric acid esters
ChemicalCAS No.
Tributyl acetylcitrate77-90-7
Tris(2-ethylhexyl) acetylcitrate144-15-0
Table 24 — Alkylsulfonic acid esters
ChemicalCAS No.
Alkylsulfonic phenyl ester91082-17-6
##### 11.3.2.2 Reagents
Table 25 — Solvents
ChemicalCAS No.

#### 11.3.3 Apparatus

##### 11.3.3.1 Analytical balance,
precision 0,1 mg.
##### 11.3.3.3 Oven,
capable of maintaining a temperature of (105 ± 5) ºC.
34
with siphon cup.
##### 11.3.3.14 Gas chromatograph with mass spectrometer detector (GC-MS).

Column: 50 % Phenyl - 50 % dimethylpolysiloxane (ZB-50), 30 m x 0,25 mm (ID) x 0,25 µm (film thickness)

Carrier gas: Helium

Flow rate: 0,8 ml/min

Injector temperature: 290 °C

Injection volume: 2 μl

Injection type: splitless

Transfer line temperature : 280 °C

Detector scan range: 50 m/z to 550 m/z

Run time: 37 min

Oven program:
RampInitial Temperature
°C
Hold time
min
Rate
°C/min
Final Temperature
°C
Final hold time
min
160110290
2290553205

Quantitation ions: Main Target ion m/z

Phthalic acid esters: 149

Citric acid esters: 157

Alkylsulfonic acid esters: 94

Typical chromatograms for the phthalic acid esters are shown in Figure 1 and Figure 2.

35

NOTE 1, 2, 4, and 6 are non-permitted substances

Figure 1 — Total ion chromatogram of a mixture of phthalates

36

Figure 2 — Total ion chromatogram of a mixture of phthalates

#### 11.3.4 Preparation of standard solutions

##### 11.3.4.1 Stock solutions

Prepare stock solutions of the phthalic, citric and alkylsulfonic acid esters dissolved in hexane.

37
Table 26 — Stock solutions I
Stock solutionSolventEsterConcentration
µg/ml
Phthalic acid ester 1ahexanedi-isononyl phthalate (DINP)5 000
Phthalic acid ester 1bhexanedi-isodecyl phthalate (DIDP)5 000
Phthalic acid ester 1chexanebis(2-ethylhexyl) phthalate (DEHP)
benzyl butyl phthalate (BBP)
di-n-butyl phthalate (DBP)
di-n-hexyl phthalate (DNHP)
di-n-heptyl phthalate (DNHpP)
di-n-octyl phthalate (DNOP)
di-n-nonyl phthalate (DNP)
di-n-decyl phthalate (DDP)
500
500
500
500
500
500
500
500
Citric acid ester 3ahexanetributyl acetylcitrate500
Citric acid ester 3bhexanetris(2-ethylhexyl) acetylcitrate1 000
Alkylsulfonic acid ester 4hexanealkylsulfonic acid phenyl ester5 000

Prepare stock solutions of the adipic acid polyesters dissolved in methanol.

Table 27 — Stock solutions II
Stock solutionSolventEsterConcentration
µg/ml
Adipic acid polyester 2amethanolPalamoll 632 or 6365 000
Adipic acid polyester 2bmethanolPalamoll 6465 000
Adipic acid polyester 2cmethanolPalamoll 6525 000
Adipic acid polyester 2dmethanolPalamoll 654 or 6565 000
Adipic acid polyester 2emethanolPalamoll 8585 000
Adipic acid polyester 2fmethanolParaplex G-405 000

NOTE Primarily the stock solutions for adipic acid polyesters are used for identification purposes.

##### 11.3.4.2 Calibration solutions

Prepare calibration solutions (Std 1 to Std 5) containing a mixture of the components from the stock solutions by appropriate solvent dilutions using pipettes into 100-ml glass volumetric flasks and making to the mark with hexane. Table 28 shows the concentration of each analyte in the calibration solution.

38
Table 28 — Calibration solutions
Stock solutionConcentrations
µg/ml
Std 1Std 2Std 3Std 4Std 5
Stock solution 1a50125250375500
Stock solution 1b50125250375500
Stock solution 1c1015202530
Stock solution 3a1015202530
Stock solution 3b50100150200250
Stock solution 41015202530
##### 11.3.4.3 Stability of standard solutions

Stability tests have shown that the plasticiser stock solutions and the calibration solutions can be stored for 6 months in a refrigerator at (4 ± 2) ºC.

#### 11.3.5 Sampling

Commercially modelling clays are generally presented as rectangular blocks presented in retail packs. Representative test portions of the modelling clay can be taken without further treatment.

#### 11.3.6 Sample preparation

For each sample pre-heat two flat bottomed flasks (11.3.3.5) marked A and B in an oven (11.3.3.3) at (105 ± 5) °C for (30 ± 5) min.

Remove the flasks from the oven and allow to cool in a desiccator for (30 ± 5) min.

After cooling, accurately weigh the flasks and record the masses.

Using a scalpel or other appropriate cutting equipment, cut small representative pieces (< 5 mm) from the centre and sides of the sample.

Weigh (1 ± 0,2) g to the nearest 0,1 mg of the cut pieces of sample into a Soxhlet thimble and add approximately 0,2 g of cotton wool to the top of the thimble to form a plug to prevent any inorganic filler escaping from the thimble.

#### 11.3.7 Procedure

NOTE It is essential to observe all safety precautions when handling chemicals and apparatus. The use of appropriate air extraction systems needs to be observed.

##### 11.3.7.1 Extraction of phthalic acid esters, citric acid esters and alkylsulfonic acid esters

Add approximately (50 ± 1) ml of hexane into a flask A.

NOTE 1 Depending on the size of the glassware and in order to reach the overflow level and have a proper reflux, the volume of hexane can be adjusted.

Place the Soxhlet thimble into the Soxhlet extractor and connect flask A, Soxhlet extractor and condenser together and place onto a heating mantle.

39

Reflux gently for (6 ± 0,5) h.

After 6 h switch off the mantle and allow sufficient time for the hexane to cool.

Decant any excess hexane left in the Soxhlet extractor into flask A.

NOTE 2 Collection of evaporated solvent for environmental protection is advised.

##### 11.3.7.2 Extraction of adipic acid polyesters

Repeat 11.3.7.1 using the pre-weighed flask B and approximately (50 ± 1) ml of methanol.

NOTE Depending on the size of the glassware and in order to reach the overflow level and have a proper reflux, the volume of methanol can be adjusted.

##### 11.3.7.3 Evaporation of the solvent and weighing

Place both flasks A and B on top of a steam bath and allow both the hexane and methanol to completely evaporate.

After the hexane and methanol have evaporated, transfer the flasks A and B to an oven (11.3.3.3) at (105 ± 5) °C.

After (30 ± 5) min remove both flasks A and B from the oven and cool in a desiccator.

After (30 ± 5) min cooling, accurately weigh both flasks A and B and record the masses.

Replace the flask in the oven, dry to constant mass until the difference between two consecutive weighings for each flask is not more than 0,000 5 g.

Record the masses and determine the solvent extractable content for both hexane and methanol.

##### 11.3.7.4 Blank determination

Determine the solvent blank residue content by evaporating 50 ml hexane and 50 ml methanol, respectively, in two pre-weighed flasks C and D following steps in 11.3.6 (omitting the sample and extraction steps) and 11.3.7.1. If the calculated blank residue value for a solvent is ≥ 0,001 g, the analysis is repeated using a different batch of solvent until the value for the blank is < 0,001 g.

##### 11.3.7.5 GC-MSD determination of phthalic acid esters, citric acid esters and alkylsulfonic acid esters

After completing weighing as described in 11.3.7.3, add (50 ± 2) ml of hexane to flask A.

Stopper flask A and swirl the hexane to completely dissolve the plasticiser extract.

Decant the solution into a 250-ml volumetric flask and by repeatedly rinsing of the flask using hexane, add to the 250-ml flask and make up to the mark.

Prepare (if necessary) further diluted solutions using hexane such that the final concentration in solution is within the linear calibration concentration for plasticiser present.

Transfer a portion of the hexane into a capped vial for GC-MS analysis (conditions as described in 11.3.3.14).

Compare the obtained GC-MS spectra to known spectra or ester standards to allow qualitative identification of plasticisers or any other compounds.

40

Plot a calibration graph of the response against the known standard concentrations.

From the calibration graph determine the response of ester found in the blank/sample and interpolate the concentration of ester in μg/ml correcting for any dilutions.

##### 11.3.7.6 ATR-FT-IR identification of adipic acid polyesters

After completing weighing as described in 11.3.7.3 add (50 ± 2) ml of methanol to flask B.

Stopper flask B and swirl the methanol to completely dissolve the plasticiser extract.

Decant the solution into a 250-ml volumetric flask and by repeatedly rinsing of the flask using methanol, add to the 250-ml flask and make up to the mark.

Compare the infrared spectra obtained with a suitable spectral data-base.

#### 11.3.8 Evaluation of results

##### 11.3.8.1 Calculation of solvent-extractable content containing plasticisers
###### 11.3.8.1.1 Content of hexane extractable material, in % (m/m), identified as phthalic, citric and alkylsulfonic acid esters by GC-MS

${M}_{\mathrm{Hexane}}=\frac{{W}_{A+E}⨉{W}_{A}}{{W}_{S}}×100$(16)

where

MHexane is the content of hexane extractable material, in % (m/m);

WA+E is the mass of flask A and extract, in g;

WA is the mass of flask A, in g;

WS is the mass of sample, in g.

###### 11.3.8.1.2 Content of methanol extractable material , in % (m/m), identified as adipic acid polyester by ATR-FT-IR

${M}_{\mathrm{Methanol}}=\frac{{W}_{B+E}-{W}_{B}}{{W}_{S}}⨉100$(17)

where

MMethanol is the content of methanol extractable material, in % (m/m);

WB+E is the mass of flask B and extract, in g;

WB is the mass of flask B, in g;

WS is the mass of sample, in g.

###### 11.3.8.1.3 Content of combined (hexane + methanol) extractable material % (m/m)

${M}_{\mathrm{te}+p}=\text{(16)}+\text{(17)}$(18)

41

where

Mte+p is the content of total extractable material content including plasticiser, in % (m/m).

Values for combined (hexane + methanol) extractable material content < 30 % will not require further characterisation of individual plasticisers and should be reported as % (m/m) total extractable material content if it can be shown that only plasticisers in Table 16 are used.

##### 11.3.8.2 Calculation and identification of plasticiser content by GC-MS analysis
###### 11.3.8.2.1 Identification of plasticisers

Record the plasticisers identified according to 11.3.7.5 and 11.3.7.6.

###### 11.3.8.2.2.1 Content of phthalic acid ester, in % (m/m), by GC-MS

${M}_{\mathrm{PAE}}=\frac{{c}_{\mathrm{e1}}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}250\left(\mathrm{ml}\right)\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}f}{{W}_{s}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}10 000}$(19)

where

MPAE is the phthalic acid ester content, in % (m/m);

ce1 is the concentration of phthalic acid ester in extract solution, in μg/ml;

f is the dilution factor;

WS is the mass of sample, in g.

${c}_{\mathrm{e1}}=\left({W}_{A+E}\right)-{W}_{A}$(20)

where

ce1 is the concentration of extract solution, in μg/ml;

WA+E is the mass of flask A and extract, in g;

WA is the mass of flask A, in g.

###### 11.3.8.2.2.2 Content of citric acid ester, in % (m/m), by GC-MS

${M}_{\mathrm{CAE}}=\frac{{c}_{e2}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}250\left(\mathrm{ml}\right)\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}f}{{W}_{s}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}10 000}$(21)

where

MCAE is the citric acid ester content, in % (m/m);

ce2 is the concentration of citric acid ester in extract solution, in μg/ml;

f is the dilution factor;

42

Ws is the mass of sample, in g.

${c}_{e2}=\left({W}_{B+E}\right)-{W}_{B}$(22)

where

ce2 is the concentration of extract solution, in μg/ml;

WB+E is the mass of flask B and extract, in g;

WB is the mass of flask B, in g.

###### 11.3.8.2.2.3 Alkylsulfonic acid ester content by GC-MS in % (m/m)

${M}_{\mathrm{AAE}}=\frac{{c}_{e}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}250\left(\mathrm{ml}\right)\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}f}{{W}_{s}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}10 000}$(23)

where

MAAE is the alkylsulfonic acid ester content, in % (m/m);

ce is the concentration of alkylsulfonic acid ester in extract solution, in μg/ml;

f is the dilution factor;

WS is the mass of sample, in g.

#### 11.3.9 Test report

The test report shall contain, as a minimum, the following:

1. type and identification of the product and/ or material tested;
2. a reference to this European Standard (i.e. EN 71-5:2013);
3. the results of the tests expressed as:
1. identified plasticisers;
2. content of hexane-extractable material , in % (m/m);
3. content of methanol-extractable material identified as adipic acid polyester by ATR-FT-IR, in % (m/m);
4. content of combined (hexane + methanol) extractable material, in % (m/m);
5. content of phthalic acid ester by GC-MS, in % (m/m);
6. content of citric acid ester by GC-MS, in % (m/m);
7. alkylsulfonic acid ester content by GC-MS; in % (m/m);
8. any deviation from the test procedure specified;
4. date of test.
43

### 11.4 Determination of the emission of benzene, toluene and xylenes from oven-hardening plasticised PVC modelling clay sets and plastic moulding sets

#### 11.4.1 Principle

The determination of the emission of benzene, toluene and xylenes from oven-hardening plasticised PVC modelling clay sets and plastic moulding sets made of polystyrene is performed by headspace gas chromatography with a mass spectrometer detector using the method of standard additions.

#### 11.4.2 Standards and reagents

Table 29 — Standards
ChemicalCAS No.
Toluene108-88-3
Benzene71-43-2
o-Xylene95-47-6
m-Xylene108-38-3
p-Xylene106-42-3
Table 30 — Solvents
ChemicalCAS No.
Methanol67-56-1

NOTE Alternatively a high boiling solvent such as dodecane (free of the compounds to be analysed) will be used instead of methanol in order to reduce the vapour pressure in the head space vial. This is especially relevant when the head space vial is not pressurised (see headspace conditions 11.4.3.2).

#### 11.4.3 Apparatus

##### 11.4.3.1 Gas chromatograph with mass spectrometer detector (GC-MS).

The measurement of benzene, toluene and xylenes require a gas chromatograph equipped with a split/splitless injector system coupled with a mass spectrometer detector.

Column: Crosslinked 5 % phenylmethylsiloxane, 95 % dimethylpolysiloxane (DB-VRX 1)), 30 m x 0,25 mm (ID) x 0,25 µm (film thickness).

Injection temperature: 300 ºC

Injection mode: split, splitless time, 0 min to 1,5 min

Interface temperature: 250 ºC

Ion source temperature: 250 ºC

Sampling time: from 2 min to 22 min

1 DB-VRX is an example of a suitable product available commercially. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product.

44

Mass range: from 30 m/z to 500 m/z

Acquisition data: 1 scan/s

Other conditions may be used, provided they give better or comparable results.

Carrier gas: Helium
RampInitial temperature
°C
Hold time
min
Rate
°C/min
Final temperature
°C
Final hold time min
135107150
21500202206
Continuation of Previous Table for Carrier Gas: Helium
SolventTypical retention time
min
SolventTypical retention time
min
benzene3,4m-xylene10,5
toluene5,6o-xylene12,3

Detector conditions for benzene, toluene and xylenes determination:

Quantification ions: Main target ion m/z

Benzene: 78

Toluene: 91

Xylenes: 91

##### 11.4.3.2 Headspace analysis conditions.

Balanced-pressure system, the vial pressurised with a carrier gas. After equilibrium has been reached the valve is switched for a specific amount of time to transfer the volatiles of the sample into the column.

Pressure-loop system, the vial pressurised with a carrier gas. Then a valve is turned and the loop is filled with the sample. Then the valve is turned again to transfer the volatiles of the sample into the column.

Pressurisation gas: He, set at 45 KPa

Thermostatting temperature: 130 ºC for test material based on PVC; 180 ºC for test material made of polystyrene

Needle temperature: 140 ºC for test material based on PVC, 190 ºC for test material made of polystyrene

Transfer line temperature: 140 ºC for test material based on PVC, 190 ºC for test material made of polystyrene

Injection time: 0,05 min

Pressurisation time: 4 min

Thermostatting time: 30 min

Withdrawal time: 0,2 min

45
##### 11.4.3.3 Other laboratory equipment.

Glassware should be cleaned, preferably rinsed with few millilitres of dichloromethane and dried before their use to avoid contamination of benzene, toluene and xylenes.

###### 11.4.3.3.1 Analytical balance,
precision 0,1 mg.
###### 11.4.3.3.2 Refrigerator,
capable of maintaining a temperature of (4 ± 2) ºC.
###### 11.4.3.3.4 Volumetric glass pipettes,
0,5 ml, 1 ml, 2 ml, 10 ml and 20 ml capacity.
###### 11.4.3.3.5 Brown glass volumetric flasks,
10 ml, 20 ml, 50 ml and 100 ml capacity.
###### 11.4.3.3.6 Syringe,
1 000 µl capacity.

#### 11.4.4 Preparation of standard solutions

Weigh accurately approximately 100 mg of each standard (benzene, toluene, m-, p-, o-xylene), dissolve in methanol and make up to 100 ml in a volumetric flask. Dilute this stock standard solution with methanol to produce standard solutions with a concentration of 5 µg/ml, 10 µg/ml, 20 µg/ml, 50 µg/ml and 100 µg/ml.

Solutions shall be handled in a glass container (11.4.3.3.3 and 11.4.3.3.5) at (4 ± 2) ºC. The stock standard solution shall be used within one month. The standard solutions shall be freshly prepared.

#### 11.4.5 Sampling

The applicable sample for the method is PVC modelling clay and polystyrene granules. Representative portions of material are taken without further homogenisation. Samples shall be stored in a sealed container before analysis in order to avoid losses of volatile substances.

#### 11.4.6 Sample preparation

No specific sample preparation is necessary. For PVC material take each test portion as a single piece of similar shape and weight.

Obtain test portions from each colour of the material, where possible, and treat them separately.

Weigh each test portion of (1 ± 0,05) g to the nearest 0,001 g into each of 5 headspace vials. Then, add 500 µl of the different standard solutions (11.4.4) to achieve standard additions of 2,5 µg, 5 µg, 10 µg, 25 µg and 50 µg, respectively.

Seal each vial quickly and store it at room temperature for 1 h.

#### 11.4.7 Procedure

Prior to injection, heat each test portion in the head space GC system for (30 ± 1) min at 130 ºC for analysis of test material based on PVC or 180 ºC for analysis of test material made of polystyrene. Analyse also an empty vial as blank in order to determine if there is contamination from the ambient air.

Analyse the samples using the GC conditions in accordance with 11.4.3.1.

46

#### 11.4.8 Evaluation of results

In a graph, plot the area for the individual component against the individual concentration added. The extrapolation of the straight line with the concentration axis in absolute value is the actual concentration of the analyte in the sample.

The regression coefficient (r) shall be better than 0,995.

#### 11.4.9 Test report

The test report shall contain, as a minimum, the following:

1. type and identification of the product and/ or material tested;
2. a reference to this European Standard (i.e. EN 71-5:2013);
3. the results of the tests expressed as:
1. benzene emitted from PVC or polystyrene, in mg/kg;
2. toluene emitted from PVC or polystyrene, in mg/kg;
3. xylene emitted from PVC or polystyrene, in mg/kg;
4. any deviation from the test procedure specified;
5. date of test.

#### 11.4.10 Critical control points

The volume of the standard shall be added to the surface of the lower part of the vial. Due to the volatility of the organic compounds, the vial shall be immediately well sealed.

Heating time of the toy material shall be (30 ± 1) min for every test portion. The temperature of the headspace thermostatting compartment shall be controlled to (130 ± 3) ºC for PVC based modelling clays and (180 ± 5) ºC for polystyrene granules.

The septum of the headspace vial shall have no influence on the result (inertness, no emissions, no adsorption).

### 11.5 Determination of styrene content in polystyrene granules

#### 11.5.1 Principle

The amount of styrene in polystyrene is determined by gas chromatography using mass spectrometry as detection system. Quantification is achieved using calibration with external standards of styrene monomer.

The method is appropriate for the quantitative determination of styrene in an approximate analyte concentration range of (50 to 3 000) mg/kg of polystyrene.

47

#### 11.5.2 Standards and reagents

##### 11.5.2.1 Standards
Table 31 — Standard
Chemical
Styrene, stored at (4 ± 2) °C
##### 11.5.2.2 Reagents
Table 32 — Reagents
Chemical
Dichloromethane
Methanol

#### 11.5.3 Apparatus

##### 11.5.3.1 Gas chromatograph,
equipped with split/splitless injector and mass spectrometer detector GC-column capable of separating styrene from the mixture of solvents and fully resolving the additives in polystyrene, e.g.:

Column: Crosslinked 5 % phenylmethylsiloxane, 95 % dimethylpolysiloxane (DB-VRX), 30 m x 0,25 mm (ID) x 0,25 µm (film thickness) or equivalent.

Carrier gas: Helium

Using these conditions, typical retention time for styrene is about 12,5 min.

Table Delimiting Parameters for the Test
RampInitial temperature
°C
Hold time
min
Rate
°C/min
Final temperature
°C
Final hold time
min
135107150
21500202206

Injection conditions:

Injection temperature: 250 ºC

Injection volume: 2 µl

Injection mode: splitless, split valve closed from 0 min to 1,5 min

Detector conditions for styrene determination:

Detection system: quadrupole mass spectrometer

Mode: SIM (Selected Ion Monitoring) focused on ions: 104 m/z and 78 m/z

Interface temperature: 250 ºC

Ion source temperature: 250 ºC

Sampling time: from 3 min to 25 min

48

Acquisition data: 2 scan/s

##### 11.5.3.3 Analytical balance,
precision 0,1 mg.
##### 11.5.3.4 Centrifuge,
able to maintain at least 2 300 g.
##### 11.5.3.5 Refrigerator,
capable of maintaining a temperature of (4 ± 2) ºC.
##### 11.5.3.6 Glass containers
equipped with a glass stopper.

Plastic equipment shall be avoided and glassware shall be cleaned, rinsed with few millilitres of the mixture of solvents (dichloromethane and methanol) and dried before use.

#### 11.5.4 Preparation of the standard solutions

Prepare a stock standard solution by dissolving 80 mg of styrene in methanol and make up to 100 ml in a volumetric flask. Dilute this stock standard solution with a mixture of dichloromethane and methanol (2+1) (v/v) to produce calibration solutions with a concentration of 0,4 µg/ml, 1 µg/ml, 5 µg/ml, 10 µg/ml and 20 µg/ml.

Standard solutions shall be stored at (4 ± 2) ºC and used within two weeks of preparation.

#### 11.5.5 Sampling

Each colour of granules shall be tested separately.

#### 11.5.6 Sample preparation

No specific sample preparation is necessary.

#### 11.5.7 Procedure

Weigh (1,5 ± 0,1) g to the nearest 0,001 g of the test portion into a 50-ml conical flask with a glass stopper. Add 10,0 ml of dichloromethane. Gently shake the solution until complete dissolution of the polymer (can take up to 24 h). Then add 5,0 ml of methanol and agitate in order to precipitate the polymer. In order to complete the separation between the phases centrifuge the solution before analysis.

Analyse the calibration solutions by GC/MS using the conditions specified at 11.5.3.1. Construct a five-point calibration curve of response against styrene concentration (mg/ml). Then analyse the test portion solution using identical conditions.

#### 11.5.8 Evaluation of results

The concentration of styrene (mg/ml) in the sample solution is directly interpolated from the graph and the styrene content (mg/kg) in the sample calculated as follows:

${M}_{\mathrm{st}}=\frac{{c}_{\mathrm{st}}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}15}{{W}_{s}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}1 000}$(24)

where

49

Mst is the content of free styrene in polystyrene sample, in mg/kg;

cst is the concentration of styrene obtained from calibration graph, in mg/l;

Ws is the mass of the sample, in g.

The results expressed in mg styrene /kg polystyrene shall be reported as the average value from two or more determinations.

#### 11.5.9 Test report

The test report shall contain, as a minimum, the following:

1. type and identification of the product and/ or material tested;
2. a reference to this European Standard (i.e. EN 71-5:2013);
3. results of the tests reported as:
1. content of styrene, in mg/kg polystyrene;
4. any deviation from the test procedure specified;
5. date of test.

### 11.6 Determination of organic solvents

#### 11.6.1 General

Only certain solvents are permitted for use in chemical toys and in certain cases these solvents should not be present in excess of a maximum limit. The 27 solvents listed in Table 33 require identification at a minimum detection level of 0,2 %. Table B.1 provides information on the technique required for each type of sample and solvent.

50
Table 33 — Solvents / identification
SolventSubclause(s) and associated table(s) containing requirement(s)
Acetone (Dimethyl ketone)8.2.2, Table 12
Cyclohexane8.2.2, Table 12
Pentan-3-one (Diethyl ketone)8.2.2, Table 12
Ethyl acetate8.2.2, Table 12
Ethanol (Ethyl alcohol)8.2.2, Table 12; 8.3.1 and 8.3.1, Table 14
Propan-2-yl acetate (Isopropyl acetate)8.2.2, Table 12
Propan-2-ol (Isopropyl alcohol)8.2.2, Table 12; 8.3.1 and 8.3.1, Table 14
Methyl acetate8.2.2, Table 12
Butan-2-one (Methyl ethyl ketone)8.2.2, Table 12; 8.4.1, Table 16
3-Methylbutan-2-one (Methyl isopropyl ketone)8.2.2, Table 12
n-Butyl acetate8.2.2, Table 12
n-Propyl acetate8.2.2, Table 12
1-Methoxypropan-2-ol8.2.2, Table 12; 8.3.1, Table 14; 8.4.1, Tables 15 and 16
1,1-Dimethoxyethane8.2.2, Table 12
n-Hexane8.2.2, 8.4
Petroleum fraction (boiling range 60 °C to 140 °C)8.2.2, Table 12, 8.4.1, Table 16
Petroleum fraction (boiling range 135 °C to 210 °C)8.2.2, Table 12, 8.4.1, Table 16
Propane-1,2-diol (Propylene glycol)8.3 and 8.3.1, Table 14
2-Methylpentane-2,4-diol (Hexylene glycol)8.3 and 8.3.1, Table 14
Butan-1-ol (n-Butyl alcohol)8.4.1, Table 16
2-Methylpropan-1-ol (iso-Butanol)8.4.1, Table 16
1-methoxypropan-2-yl acetate8.4.1, Table 16
3-Methoxybutyl acetate8.4.1, Table 16
Butyl glycolate (Butyl hydroxyacetate)8.2.1.2.1, Table 7
Caprolactam8.2.1.2.1, Table 7
2-(2-Butoxyethoxy)ethyl acetate8.2.1.2.1, Table 7
Glycerol triacetate8.4.1, Table 16

The 12 solvents listed in Table 34 require determination at a minimum detection limit 0,1 %.

51
Table 34 — Solvents / determination
SolventPermitted maximum concentration
Butyl glycolate (Butyl hydroxyacetate)3 %
Caprolactam5 %
2-(2-Butoxyethoxy)ethyl acetate3 %
n-Hexane0,5 %
2-Methylpropan-1-ol (Isobutyl alcohol)2 %
Butan-1-ol (n-Butyl alcohol)2 %
Ethanol (Ethyl alcohol)10 % (total) in water-based paints and lacquers
Propan-2-ol (Isopropyl alcohol)
Propane-1,2-diol (Propylene glycol)
2-Methylpentane-2,4-diol (Hexylene glycol)
1-Methoxypropan-2-ol
1-Methoxypropan-2-ol20 % in solvent-based paints
NOTE The permitted maximum concentrations are provided for information purposes only.

#### 11.6.2 Principle

Solvents are identified either by headspace gas chromatography with a flame ionisation detector (HS-GC-FID) using two different columns for comparative identification, or by gas chromatography with a mass spectrometer detector (GC-MS).

Solvents are determined using one of the following techniques depending on the volatility of the solvent and the sample matrix:

1. Headspace gas chromatography with a flame ionisation detector (HS-GC-FID) for the determination of volatile solvents (boiling point ≤ 120 °C);
2. Gas chromatography with a mass spectrometer detector (GC-MS) for the determination of nonvolatile solvents (boiling point > 120 °C);
3. Gas chromatography with a flame ionisation detector (GC-FID) for the determination of propane-1,2diol.

For confirmation of the identification of petroleum fractions use EN ISO 22854.

52

#### 11.6.3 Standards and reagents

##### 11.6.3.1 Standards
Table 35 — Solvents
ChemicalCAS No.Density a
g/ml
Acetone67-64-10,791
Cyclohexane110-82-70,778
Pentan-3-one96-22-00,853
Ethyl acetate141-78-60,902
Ethanol64-17-50,785
Propan-2-yl acetate (Isopropyl acetate)108-21-40,872
Propan-2-ol67-63-00,785
Methyl acetate79-20-90,932
Butan-2-one78-93-30,806
3-Methylbutan-2-one563-80-40,805
Butyl acetate123-86-40,872
Propyl acetate109-60-40,888
1-Methoxypropan-2-ol107-98-20,922
1,1-Dimethoxyethane534-15-60,852
Propane-1,2-diol57-55-61,036
2-Methylpentane-2,4-diol107-41-50,925
1-Methoxypropan-2-yl acetate108-65-60,969
3-Methoxybutyl acetate4435-53-40,96
2-Methylpropan-1-ol78-83-10,803
Butan-1-ol71-36-30,810
n-hexane110-54-30,659
Petroleum fraction (boiling range 60 °C to 140 °C) b64742-89-8
Petroleum fraction (boiling range 135 °C to 210 °C) b64742-88-7
Butyl glycolate7397-62-81,019
Caprolactam105-60-2
2-(2-Butoxyethoxy)ethyl acetate124-17-40,978
Glycerol triacetate102-76-11,155
a The density values are those of the pure substance.
b The relevant petroleum fractions are not commercially available; the closest match has been referenced.
53
##### 11.6.3.2 Reagents
Table 36 — Reagents
ChemicalCAS No.
Dimethylformamide (DMF)68-12-2
Sodium chloride7647-14-5
Dichloromethane75-09-2
Methanol67-56-1
Sodium chloride, 10 % aqueous solution (saline)

#### 11.6.4 Apparatus

##### 11.6.4.1 Analytical balance,
precision 0,1 mg.
##### 11.6.4.2 Headspace vial,
glass, 22 ml with crimp cap.
20 ml.
50 ml.
100 ml.
##### 11.6.4.7 Variable positive displacement pipettes
(range 0,02 ml to 10,00 ml).
##### 11.6.4.8 Filter paper,
general purpose laboratory, medium retention, medium/fast flow rate, pore size 11 µm.
##### 11.6.4.9 Syringe filter,
nylon membrane, 0,45 µm.
##### 11.6.4.10 Syringe filter,
surfactant-free cellulose acetate (SFCA) membrane, 0,45 µm.
##### 11.6.4.11 Headspace gas chromatograph with flame ionisation detector (HS-GC-FID).

Polar column: Polyethylene glycol (ZB-Wax), 60 m x 0,32 mm (ID) x 0,5 µm (film thickness)

Non-polar column: Dimethylpolysiloxane (ZB-1), 60 m x 0,32 mm (ID) x 1,0 µm (film thickness)

Carrier gas: Helium

Split vent flow: 18 ml/min (GC without Headspace)

Column flow: 1,19 ml/min at 50 °C

Small flow at 220 °C

Column head pressure: 10,5 psi

Septum purge: 4 ml/min

Split vent flow: 51 ml/min (GC with Headspace)

Equilibration time: 45 min

Equilibration temperature: 80 °C

Injection type: split

Transfer line temperature: 250 °C

Detector temperature: 250 °C

Run time: 35 min

54
Oven program:
RampInitial temperature
°C
Hold time
min
Rate
°C/min
Final temperature
°C
Final hold time min
15012,5100
21000,5102205
##### 11.6.4.12 Gas chromatograph with mass spectrometer detector (GC-MS).

Column: 50% Phenylmethylpolysiloxane (ZB-50), 30 m x 0,25 mm (ID) x 0,25 μm (film thickness)

Carrier gas: Helium

Flow rate: 0,8 ml/min

Injector temperature: 290 °C

Injection volume: 2 μl

Injection type: split/splitless

Transfer line temperature: 280 °C

Detector scan range: 50 m/z to 550 m/z

Run time: 25 min

Oven program:
RampInitial temperature
°C
Hold time
min
Rate
°C/min
Final temperature
°C
Final hold time
min
140420280
22804203002
##### Gas chromatograph with flame ionisation detector (GC-FID).

Column: Polyethylene glycol (ZB-Wax), 30 m x 0,32 mm (ID) x 0,25 µm (film thickness)

Carrier gas: Helium

Flow rate: 1,6 ml/min

Injector temperature: 250 °C

Injection type: split (split ratio 100:1)

Injection volume: 0,2 µl

Transfer line temperature: 250 °C

Detector temperature: 250 °C

Run time: 35 min

Oven program:
RampInitial temperature
°C
Hold time
min
Rate
°C/min
Final temperature
°C
Final hold time
min
1500,55775
275441106

#### 11.6.5 Preparation of the standard solutions

NOTE Stability tests have shown that the solvent stock solutions (> 10 mg/ml) can be stored for 6 months in a refrigerator at (4 ± 2) ºC.

55
##### 11.6.5.1 Stock solutions for the identification and determination of solvents using HS-GC-FID

Prepare a 250 mg/ml (25 % m/v) stock standard solution for each solvent in Table 37 (except n-hexane) using a variable pipette (11.6.4.7) to deliver a calculated volume of solvent (equivalent to 12,5 g of solvent) into a 50-ml volumetric flask (11.6.4.4) and make up to the mark with DMF (11.6.3.2).

The volume of each volatile organic solvent required for a 50-ml volumetric flask can be calculated using the following formula:

${V}_{s}=\frac{{V}_{t}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}{d}_{s}}{{c}_{\mathrm{sst}}}$(25)

where

Vs is the volume of the solvent, in ml;

Vf is the volume of the flask, in ml;

csst is the concentration of the stock standard, in mg/ml;

ds is the density of the solvent, in mg/ml.

For n-hexane prepare a 100-mg/ml stock standard solution due to the lower miscibility of n-hexane in DMF.

Table 37 — Organic solvents for analysis by HS-GC-FID
Organic solvent
Acetone
Cyclohexane
Pentan-3-one
Ethyl acetate
Ethanol
Propan-2-yl acetate
Propan-2-ol
Methyl acetate
Butan-2-one
3-Methylbutan-2-one
Butyl acetate
Propyl acetate
1-Methoxypropan-2-ol
1,1-Dimethoxyethane
2-Methylpropan-1-ol
Butan-1-ol
n-hexane
56
##### 11.6.5.2 Stock solutions for the identification and determination of solvents using GC-MS

Prepare a 10-mg/ml stock standard solution for each organic solvent in Table 38 by weighing 1,00 g of solvent into a 100-ml volumetric flask (11.6.4.5) and making up to the mark with dichloromethane.

Table 38 — Organic solvents for analysis by GC-MS
Organic solvent
Butyl acetate
1-Methoxypropan-2-yl acetate
2-Methylpentane-2,4-diol
3-Methoxybutyl acetate
Butyl glycolate
2-(2-Butoxyethoxy)ethyl acetate
Caprolactam
Glycerol triacetate
Petroleum fraction (boiling range 60 °C to 140 °C)
Petroleum fraction (boiling range 135 °C to 210 °C)
##### 11.6.5.3 Stock solution for the identification and determination of propane-1,2-diol

Prepare a 10-mg/ml stock standard solution for propane-1,2-diol by weighing 1,00 g of propane-1,2-diol into a 100-ml volumetric flask and making up to the mark with dichloromethane.

##### 11.6.5.4 Calibration solutions

NOTE Stability tests have shown that the working solutions can be kept for 6 months in a refrigerator at (4 ± 2) ºC.

###### 11.6.5.4.1 Calibration solutions for the identification of solvents using HS-GC-FID

Prepare 50-mg/ml working solutions with the compositions shown in Table 39 to Table 43 by pipetting 10,00 ml of each appropriate 250-mg/ml stock standard solution (11.6.5.1) into four separate 50-ml volumetric flasks and making up to the mark with DMF.

Table 39 — Working solution 1
Organic solventStock standardWorking solution 1
Ethanol250 mg/ml50 mg/ml
Propan-2-ol250 mg/ml
1-Methoxypropan-2-ol250 mg/ml
57
Table 40 — Working solution 2
Organic solventStock standardWorking solution 2
Acetone250 mg/ml50 mg/ml
Ethyl acetate250 mg/ml
3-Methylbutan-2-one250 mg/ml
2-Methylpropan-1-ol250 mg/ml
Table 41 — Working solution 3
Organic solventStock standardWorking solution 3
1,1-Dimethoxyethane250 mg/ml50 mg/ml
Butan-2-one250 mg/ml
Propyl acetate250 mg/ml
Butan-1-ol250 mg/ml
Table 42 — Working solution 4
Organic solventStock standardWorking solution 4
Methyl acetate250 mg/ml50 mg/ml
Cyclohexane250 mg/ml
Butyl acetate250 mg/ml
Pentan-3-one250 mg/ml
Propan-2-yl acetate250 mg/ml

Prepare a 50-mg/ml working solution for n-hexane (see Table 43) by pipetting 25,00 ml of the 100-mg/ml nhexane stock standard solution into a 50-ml volumetric flask and making up to the mark with DMF.

Table 43 — Working solution 5
Organic solventStock standardWorking solution 5
n-hexane100 mg/ml50 mg/ml
###### 11.6.5.4.2 Calibration solutions for the identification of solvents in aqueous-based materials

Using a variable pipette, prepare calibration solutions (a and b) in saline (11.6.3.2) for working solution 1 in headspace vials (11.6.4.2) according to Table 44. Crimp each headspace vial tightly to achieve a good seal and shake each vial to homogenise the solution.

NOTE The saline solution is used to increase detection sensitivity by decreasing the solubility of organic molecules in the aqueous phase [salting-out effect].

58
Table 44 — Calibration solutions in saline for aqueous-based materials
CategoryVolume of 50 mg/ml working solution to be added
ml
Volume of 10 % saline to be added
ml
Total volume of working solution and saline
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a0,404,605,00202
b0,044,965,002,00,2
###### 11.6.5.4.3 Calibration solutions for the identification of solvents in solvent-based materials

Using a variable pipette, prepare calibration solutions (a and b) in DMF for each working solution 1 to 5 in headspace vials according to Table 45. Crimp each headspace vial tightly to achieve a good seal and shake each vial to homogenise the solution.

Table 45 — Calibration solutions in DMF for solvent-based materials
CategoryVolume of 50 mg/ml working solution to be added
ml
Volume of DMF to be added
ml
Total volume of working solution and saline
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a0,404,605,00202
b0,044,965,002,00,2
###### 11.6.5.4.4 Calibration solutions for the determination of solvents using HS-GC-FID

Depending on the matrix and the solvent being determined, prepare calibration solutions (a to e) for butan-1-ol, 2-methylpropan-1-ol, n-hexane, 1-methoxypropan-2-ol, ethanol and propan-2-ol by pipetting the specified amounts (according to Table 46 to Table 49) of DMF or saline (11.6.3.2), as required, and the appropriate working solution (11.6.5.4.1) or stock standard solution (11.6.5.1) into a headspace vial. Crimp each headspace vial tightly to achieve a good seal and shake to homogenise the solution.

Table 46 — Calibration solutions in DMF for butan-1-ol and 2-methylpropan-1-ol
CategoryVolume of working solution 2 or 3 to be added
ml
Volume of DMF to be added
ml
Total volume of working solution and DMF
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a0,804,205,00404,0
b0,404,605,00202,0
c0,204,805,00101,0
d0,104,905,005,00,5
e0,054,955,002,50,25
59
Table 47 — Calibration solutions in DMF for n-hexane
CategoryVolume of 100 mg/ml stock standard solution to be added
ml
Volume of DMF to be added
ml
Total volume of stock standard solution and DMF
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a1,004,005,0010010
b0,804,205,00808
c0,504,505,00505
d0,204,805,00202
e0,104,905,00101
Table 48 — Calibration solutions in DMF for 1-methoxypropan-2-ol
CategoryVolume of 150 mg/ml stock standard solution to be added
ml
Volume of DMF to be added
ml
Total volume of stock standard solution and DMF
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a1,203,805,0030030
b1,004,005,0025025
c0,604,405,0015015
d0,404,605,0010010
e0,204,805,00505
Table 49 — Calibration solutions in saline for 1-methoxypropan-2-ol, ethanol and propan-2-ol
CategoryVolume of 250 mg/ml stock standard solution to be added
ml
Volume of 10% saline to be added
ml
Total volume of stock standard solution and DMF
ml
Mass of solvent in headspace vial
mg
Equivalent concentration in sample
%
a0,804,205,0020020
b0,404,605,0010010
c0,204,805,00505
d0,084,925,00202
e0,044,965,00101
###### 11.6.5.4.5 Calibration solutions for the identification of solvents using GC-MS

Prepare calibration solutions (a and b) for each set of solvents (A to E) as shown in Table 50 by pipetting appropriate volumes of the appropriate 10 mg/ml stock standard solutions (11.6.5.2) into a series of 100-ml volumetric flasks and making up to the mark with dichloromethane.

60
Table 50 — Calibration solutions for identification of solvents by GC-MS
SetOrganic solventConcentration of calibration solution
(a)
mg/ml
Concentration of calibration solution
(b)
mg/ml
APropane-1,2-diol1,000,05
BButyl acetate
1-methoxypropan-2-yl acetate
2-Methylpentane-2,4-diol
3-Methoxybutyl acetate
0,020,005
CButyl glycolate
2-(2-Butoxyethoxy)ethyl acetate
0,250,05
DCaprolactam
Glycerol triacetate
0,020,005
EPetroleum fraction (boiling range 60 °C to 140 °C)
Petroleum fraction (boiling range 135 °C to 210 °C)
0,250,05
###### 11.6.5.4.6 Calibration solution for the determination of solvents using GC-MS

Prepare calibration solutions (a to e) in Table 51 for 2-(2-butoxyethoxy)ethyl acetate, butyl glycolate, caprolactam and 3-methylpentane-2,4-diol by pipetting the specified volume (according to Table 51 to Table 54) of the appropriate 10-mg/ml stock standard solution (11.6.5.2) into a series of 100-ml volumetric flasks and making up to the mark with dichloromethane.

Table 51 — Calibration solutions for 2-(2-butoxyethoxy)ethyl acetate
CategoryVolume of 10-mg/ml stock standard solution required
ml
Concentration of calibration solution
mg/ml
Equivalent concentration in samplea,b
%
a5,000,5020
b4,000,4016
c3,000,3012
d2,000,208
e1,000,104
a Assuming 1,000 g of sample is taken for analysis and the dilution in 11.6.5.4.1 is applied.
b For information purposes only
61
Table 52 — Calibration solutions for butyl glycolate
CategoryVolume of 10-mg/ml stock standard solution required
ml
Concentration of calibration solution
mg/ml
Equivalent concentration in samplea,b
%
a2,500,255
b2,000,204
c1,500,153
d1,000,102
e0,500,051
a Assuming 1,000 g of sample is taken for analysis and the dilution in 11.6.5.4.1 is applied.
b For information purposes only.
Table 53 — Calibration solutions for caprolactam
CategoryVolume of 10-mg/ml stock standard solution required
ml
Concentration of calibration solution
mg/ml
Equivalent concentration in samplea,b
%
a0,200,02010
b0,100,0105
c0,080,0084
d0,060,0063
e0,050,0052,5
a Assuming 1,000 g of sample is taken for analysis and the dilution in 11.6.5.4.1 is applied.
b For information purposes only.
Table 54 — Calibration solutions for 2-methylpentane-2,4-diol
CategoryVolume of 10-mg/ml stock standard solution required
ml
Concentration of calibration solution
mg/ml
Equivalent concentration in samplea,b
%
a0,500,05015
b0,250,0257,5
c0,100,0103
d0,0750,007 52,25
e0,0050,0051,5
a Assuming 1,000 g of sample is taken for analysis and the dilution in 11.6.5.4.1 is applied.
b For information purposes only.
62
###### 11.6.5.4.7 Calibration solutions for the determination of propane-1,2-diol using GC-FID

Prepare calibration solutions (a to e) for propane-1,2-diol by pipetting the specified volume (according to Table 55) of the 10-mg/ml propane-1,2-diol stock standard solution (11.6.5.3) into a series of 100-ml volumetric flasks and making up to the mark with dichloromethane.

Table 55 — Calibration solutions for the determination of propane-1,2-diol by GC-FID
CategoryVolume of 10-mg/ml stock standard solution required
ml
Concentration of calibration solution
mg/ml
Equivalent concentration in 1 g samplea,b
%
a5,000,5020
b4,000,4016
c3,000,3012
d2,000,208
e1,000,104
a Assuming 1,000 g of sample is taken for analysis and the dilution in 11.6.5.4.1 is applied.
b For information purposes only

#### 11.6.6 Sampling

For sampling the test portion is taken from the container. Samples are packaged in a variety of tubes and bottles that will release volatile components to the atmosphere on opening. On opening of the container the sample should be stirred using a glass rod to homogenise the sample, whenever possible. For samples ≤ 1 g the whole sample should be transferred immediately into a sampling tube or vial.

#### 11.6.7 Sample preparation

##### 11.6.7.1 General

To minimise loss of solvent, the samples shall be cooled in a refrigerator at (4 ± 2) °C for 1 h before opening.

##### 11.6.7.2 Sample preparation for identification and determination of solvents by HS-GC-FID

Weigh (1,0 ± 0,05) g to the nearest 0,001 g of the test portion into a headspace vial and record the mass. For aqueous samples add 5 ml of saline and for non-aqueous samples add 5 ml of DMF. Crimp the vial immediately, shake the vial to homogenise the solution.

##### 11.6.7.3 Sample preparation for identification of solvents by GC-MS

NOTE Direct injection of samples into a gas chromatograph is not advised; a suitable clean up of the sample is necessary. As the solvents identified by this technique have low volatility, minimal losses are expected.

###### 11.6.7.3.1 Solvent-based glue, thinner and paint samples

Weigh (1,0 ± 0,05) g to the nearest 0,001 g of the test portion into a 50-ml beaker and add 5 ml of dichloromethane. Dissolve the test portion by gentle swirling and filter into a 20-ml volumetric flask using filter paper (11.6.4.8) and make up to the mark using dichloromethane. Glue and the paint samples solutions might require additional filtering before injection into the GC-MS using a 0,45-µm nylon syringe filter (11.6.4.9). Pipette 1 ml of the sample solution into a crimped vial.

63
###### 11.6.7.3.2 Aqueous-based glue samples

Weigh (1,0 ± 0,05) g to the nearest 0,001 g of the test portion into a 50-ml beaker and add 5 ml of water. Dissolve the test portion by gentle swirling and filter into a 20-ml volumetric flask using filter paper and make up to the mark using methanol. Some solutions might require additional filtering before injection into the GCMS using a 0,45-µm surfactant-free cellulose acetate (SFCA) syringe filter (11.6.4.10). Pipette 1 ml of the sample solution into a crimped vial.

###### 11.6.7.3.3 Aqueous-based paint samples

Weigh (1,0 ± 0,05) g to the nearest 0,001 g of the test portion into a 50-ml beaker and add 5 ml of methanol. Dissolve the test portion by gentle swirling and filter into a 20-ml volumetric flask using filter paper (11.6.4.8) and make up to the mark using methanol. Some solutions might require additional filtering before injection into the GC-MS using a 0,45-µm SFCA syringe filter (11.6.4.10). Pipette 1 ml of the sample solution into a crimped vial.

##### 11.6.7.4 Sample preparation for determination of certain solvents by GC-MS

Determination of 2-(2-butoxyethoxy)ethyl acetate, butyl glycolate, caprolactam and 2-methylpentane-2,4-diol will require the sample solution prepared under 11.6.7.3 to be further diluted in dichloromethane or methanol, as appropriate, to ensure the concentration of the analyte is within the calibration range. The dilutions are shown in Table 56. Pipette 1 ml of the diluted sample solution into a crimped vial for analysis by GC-MS.

Table 56 — Dilution factors for the quantification of solvents by GC-MS and GC-FID
SolventDilutionDilution factor
2-(2-Butoxyethoxy)ethyl acetate1 ml in 150 ml dichloromethane150
Butyl glycolate1 ml in 10 ml dichloromethane10
Caprolactam1 ml in 250 ml dichloromethane250
2-Methylpentane-2,4-diol1 ml in 150 ml dichloromethane150
Propane-1,2-diol1 ml in 20 ml dichloromethane20
##### 11.6.7.5 Sample preparation for determination of propane-1,2-diol using GC-FID

Determination of propane-1,2-diol will require the sample solution prepared under 11.6.7.2 to be further diluted with dichloromethane or methanol, as appropriate, to ensure the concentration of the analyte is within the calibration range. The appropriate dilution is shown in Table 56. Pipette 1 ml of the diluted sample solution into a crimped vial for analysis by GC-FID.

#### 11.6.8 Procedure

##### 11.6.8.1 Identification of solvents using HS-GC-FID

For the identification of solvents in aqueous-based materials, a two-point calibration graph is constructed by the calibration solutions prepared at 11.6.5.4.2.

For the identification of solvents in solvent-based materials, a two-point calibration graph is constructed by the calibration solutions prepared at 11.6.5.4.3.

Analyse the calibration solutions by HS-GC-FID using the conditions specified at 11.6.4.13. The order of elution for the solvents in the chromatogram using a 60 m x 0,32 mm x 0,50 µm polar column (ZB-WAX) is shown in Figure 3 and Table 57.

64

Figure 3 — Chromatogram of a mixture of organic solvents by HS-GC-FID using a 60 m x 0,32 mm x 0,50 µm polar column (ZB-WAX)

Table 57 — Typical retention times for solvents using the polar column (ZB-WAX)
PeakSolventRetention time
min
PeakSolventRetention time
min
1n-Hexane6,1813Ethanol11,0
5Cyclohexane7,07143-Methylbutan-2-one11,1
61,1-Dimethoxyethane7,9315Propyl acetate12,5
7Acetone8,2816Pentan-3-one12,7
8Methyl acetate8,50172-Methylpropan-1-ol17,3
9Ethyl acetate9,75181-Methoxypropan-2-ol19,5
10Propan-2-yl acetate10,019Butan-1-ol20,1
11Butan-2-one10,220Dimethylformamide28,1
12Propan-2-ol10,7
65

Analyse the sample headspace vial prepared under 11.6.7.2 by HS-GC-FID using identical conditions as those used for the calibration solutions. Compare the sample chromatogram to known reference standards to allow identification of solvents or any other compounds. Confirmation of solvent identity is by comparison of retention times on an alternative non-polar column (ZB-1).

The order of elution for the solvents in the chromatogram using a 60 m x 0,32 mm x 1,00 µm non-polar column (ZB-1) is shown in Figure 4 and Table 58.

Figure 4 — Chromatogram of a mixture of organic solvents by HS-GC-FID using a 60 m x 0,32 mm x 1,00 µm non-polar column ZB-1

66
Table 58 — Typical retention times for solvents using the non-polar column (ZB-1)
PeakSolventRetention time
min
PeakSolventRetention time
min
1Ethanol7,10143-Methylbutan-2-one12,8
2Acetone7,6015Butan-1-ol13,0
3Propan-2-ol7,7715Propan-2-yl acetate
(Isopropyl acetate)
13,0
4Methyl acetate8,45161-Methoxypropane-2-ol13,7
8Butan-2-one10,117Cyclohexane14,1
91,1-Dimethoxyethane10,418Pentan-3-one14,6
10Ethyl acetate10,919Propyl acetate15,6
11n-Hexane11,122Dimethylformamide18,4
122-Methylpropan-1-ol11,5
NOTE On a non-polar column butan-1-ol and 1-methylethyl acetate might not be separated when analysed in the same solution.

Confirmation of the retention time and order of elution can be established by separately preparing and analysing directly the 250-mg/ml stock standard solutions (11.6.5.1).

##### 11.6.8.2 Identification of solvents using GC-MS

Analyse each set of calibration solutions (a and b) prepared under 11.6.5.4.5 by GC-MS using the conditions specified at 11.6.4.12 and construct a two-point calibration graph. The order of elution for certain solvents in the chromatogram is shown in Figure 5 and Table 59. For the identification of petroleum fraction (boiling range (60 to 140) °C) use a 60-m column.

67

Figure 5 — Chromatogram: Total ion chromatogram of a mixture of organic solvents by GC-MSD

Table 59 — Typical retention times for certain solvents analysed by GC-MS
CategorySolventsRetention time
min
Ion
m/z
1Propane-1,2-diol5,2945
2Butyl acetate5,5543
31-Methoxypropan-2-yl acetate6,6143
42-Methylpentane-2,4-diol7,3559/43
53-Methoxybutyl acetate7,7043/59
6Butyl glycolate10,057
72-(2-Butoxyethoxy)ethyl acetate10,848/87/57
8Glycerol triacetate11,053
9Caprolactam11,2113/55/85

Analyse the sample vial prepared under 11.6.7.3 by GC-MS using identical conditions as those used for the calibration solutions. Compare the sample chromatogram to known reference standards to allow identification of solvents or any other compounds.

##### 11.6.8.3 Determination of solvent content by HS-GC-FID

For each solvent identified at 11.6.8.1 that requires quantification by HS-GC-FID, analyse the appropriate calibration solutions prepared under 11.6.5.4.5 using the conditions specified at 11.6.4.11. For each identified solvent construct a five-point calibration curve of response against solvent concentration (mg/vial).

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Analyse the sample headspace vial prepared under 11.6.7.2 by HS-GC-FID using identical conditions as those used for the calibration solutions. From the calibration graph determine the solvent concentration in the sample vial (mg/vial) and calculate the percentage solvent content in the sample using Formula (26).

##### 11.6.8.4 Determination of solvent content using GC-MS

For each solvent identified at 11.6.8.2 that requires quantification by GC-MS, analyse the appropriate calibration solutions prepared under 11.6.5.4.5 using the conditions specified at 11.6.4.12. For each identified solvent construct a five-point calibration curve of response against solvent concentration (mg/ml).

Analyse the diluted sample solution(s) prepared under 11.6.7.4 by GC-MS using identical conditions as those used for the calibration solutions. From the calibration graph determine the solvent concentration in the diluted sample solution (mg/ml) and calculate the percentage solvent content in the sample using Formula (27).

##### 11.6.8.5 Determination of propane-1,2-diol by GC-FID

NOTE Propane-1,2-diol cannot be quantified on a non-polar column using the GC-MS conditions specified at 11.6.4.12 due to tailing effects of the chromatogram.

Analyse the calibration solutions prepared under 11.6.5.4.7 by GC-FID using the conditions specified at 11.6.4.13 and construct a five-point calibration curve of response against solvent concentration.

The retention time of propane-1,2-diol under these conditions is typically 16,5 min.

Analyse the diluted sample solution prepared under 11.6.7.5 by GC-FID using identical conditions as those used for the calibration solutions. From the calibration graph determine the propane-1,2-diol concentration in the diluted sample solution (mg/ml) and calculate the percentage propane-1,2-diol content in the sample using Formula (27).

##### 11.6.8.6 Blank determination
###### 11.6.8.6.1 HS-GS-FID blank determination

For each test, analyse a blank solution prepared under 11.6.7.2 by HS-GC-FID omitting the sample using the conditions specified at 11.6.4.11.

###### 11.6.8.6.2 GS-MS and GC-FID blank determination

For each test, analyse a blank solution prepared under 11.6.7.3 by GC-MS or CC-FID omitting the sample using the conditions specified at 11.6.4.12 or 11.6.4.13, as appropriate.

#### 11.6.9 Evaluation of results

##### 11.6.9.1 Calculation of solvent content by HS-GC-FID

The concentration of each solvent (mg/ml) in the sample solution is directly interpolated from the graph and the content of each solvent (%) in the sample calculated as follows:

${M}_{\mathrm{sol}}=\frac{{W}_{s}}{W\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}10}$(26)

where

Msol is the content of solvent, in % (m/m);

WS is the mass of solvent, in mg;

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W is the mass of sample, in g.

##### 11.6.9.2 Calculation of solvent content by GC-MS or GC-FID

The concentration of each solvent (mg/ml) in the sample solution is directly interpolated from the graph and the content of each solvent (% (m/m)) in the sample calculated as follows:

${M}_{\mathrm{sol}}=\frac{{W}_{s}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}f}{W\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}0,5}$(27)

where

Msol is the content of solvent, in % (m/m);

WS is the mass of solvent, in mg;

W is the mass of sample, in g;

f is the dilution factor.

#### 11.6.10 Test report

The test report shall contain, as a minimum, the following:

1. type and identification of the product and/ or material tested;
2. a reference to this European Standard (i.e. EN 71-5:2013);
3. results of the tests recorded as:
1. identification of solvent and technique used to identify the solvent HS-GC-FID / GC-MS / GC-FID;
2. content of each solvent identified, in % (m/m);
3. the total solvent content, being the sum of the individual solvent contents, in % (m/m);
4. any deviation from the test procedure specified;
5. date of test.

### 11.7 Combined approach for the determination of plasticisers in solvent-based adhesives and in solvent-based paints and lacquers, film-forming agents in paints and lacquers and modifiers in solvent-based paints and lacquers

#### 11.7.1 Principle

This method describes a procedure that is suitable for the quantification of plasticisers, film-forming agents and modifiers in solvent-based adhesives and in solvent-based paints and lacquers.

The sample is extracted with diethyl ether and the total extract is determined gravimetrically. The content of plasticisers in this extract is determined according to 11.3 (determination of plasticisers in oven-hardening PVC modelling clay sets). The film-forming agents are determined by gas chromatography with mass selective detector. The content of modifiers is calculated as the difference between the total extract and the amount of plasticisers and film-forming agents.

Nitrocellulose in solvent-based paints and lacquers is identified by IR-spectroscopy.

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Test report, see 11.7.7.

#### 11.7.2 Determination of total extract

##### 11.7.2.1 Standards and reagents

None.

###### 11.7.2.1.2 Reagents
Table 60 — Reagents
ChemicalCAS-No.
Diethyl ether60-29-7
Methanol67-56-1
Potassium hydrogen carbonate298-14-6
Sand
##### 11.7.2.2 Apparatus
###### 11.7.2.2.1 Centrifuge,
capable of achieving at least 1 900 g.
###### 11.7.2.2.4 Oven,
capable of maintaining a temperature of (110 ± 2) °C.
###### 11.7.2.2.5 Analytical balance,
precision 0,1 mg.
###### 11.7.2.2.9 Centrifuge tubes,
min. 30 ml with caps.
##### 11.7.2.3 Sampling

For sampling the test portion is taken from the container.

##### 11.7.2.4 Sample preparation

Homogenise the sample of paint or lacquer by stirring with a glass rod or a spatula before extraction. The adhesives are analysed without treatment.

##### 11.7.2.5 Procedure

Weigh (1,0 ± 0,1) g to the nearest 0,001 g of the test portion into a centrifuge tube, add a small amount of sand and 10 ml of diethyl ether. Close the centrifuge tube and place it in an ultrasonic bath for 15 min.

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Instead of the ultrasonic bath, an alternative extraction method may be used.

Centrifuge the tube for 5 min and transfer the supernatant liquid to a second centrifuge tube containing 10 ml of methanol. If a precipitate forms within a few minutes, separate by centrifuging. Transfer the supernatant into a weighed 50-ml glass stoppered flask and evaporate to dryness with a rotary evaporator. Dry the flask in an oven at (110 ± 2) °C. After drying, store the flask in a desiccator chamber till cooled. Then re-weigh and determine the amount of residue.

Reconstitute the residue in 50 ml of diethyl ether.

Use this solution for the determination of plasticisers and for the determination of film-forming agents.

##### 11.7.2.6 Evaluation of results

The residue content in the sample is calculated as follows:

${M}_{r}=\frac{{W}_{r}\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}100}{1 000\phantom{\rule{.2em}{0ex}}×\phantom{\rule{.2em}{0ex}}W}$(28)

where

Mr is the extractable material content, in % (m/m);

Wr is the mass of residue, in mg;

W is the mass of sample, in g.

#### 11.7.3 Identification of nitrocellulose

##### 11.7.3.1 Principle

Nitrocellulose in solvent-based paints and lacquers is identified by IR-spectroscopy.

##### 11.7.3.2 Reagents
Table 61 — Reagents
ChemicalCAS No.
Potassium bromide for IR-spectroscopy7758-02-3
##### 11.7.3.3 Apparatus
###### 11.7.3.3.3 Fourier transform infrared spectrometer (FTIR-Spectrometer) with attenuated total reflectance (ATR) cell.

Measurement range: 4 000 cm-1 to 400 cm-1

Scans: 32

Use a pellet holder for a measurement in transmission mode.

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Use an ATR cell for a measurement in reflection mode.

See 11.7.2.3.

##### 11.7.3.5 Sample preparation

Homogenise the sample of paint or lacquer by stirring with a glass rod or a spatula before extraction.

##### 11.7.3.6 Procedure

Dry the solvent-based paints at (105 ± 2) °C in an oven. Use the residue for the IR-analysis.

Press the dried residue on the window of the ATR-equipment of the FTIR-spectrometer.

NOTE The identification can also be performed in transmission mode.

##### 11.7.3.7 Evaluation of results

Compare the IR-spectrum of nitrocellulose given in Figure 6 with the relevant absorbances of the sample.