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

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of an identical text or by endorsement, at the latest by December 2013, and conflicting national standards shall be withdrawn at the latest by December 2013.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:

• Part 1: Mechanical and physical properties
• Part 2: Flammability
• Part 3: Migration of certain elements
• Part 4: Experimental sets for chemistry and related activities
• Part 5: Chemical toys (sets) other than experimental sets
• Part 7: Finger paints — Requirements and test methods
• Part 8: Activity toys for domestic use
• Part 9: Organic chemical compounds — Requirements
• Part 10: Organic chemical compounds — Sample preparation and extraction
• Part 11: Organic chemical compounds — Methods of analysis
• Part 12: N-Nitrosamines and N-nitrosatable substances;
• Part 13: Olfactory board games, gustative board games, cosmetic kits and gustative kits;
• Part 14: Trampolines for domestic use.

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.

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.

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.

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.

3.9 adhesive

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

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.”.

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.

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.”.

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]).

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.

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.

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.

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 Adhesives

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.

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.

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

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.

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.

8.2.2.3 Contact adhesives

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

8.2.2.4 Special adhesives

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

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.

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.

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];

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.

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.

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.”.

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.

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:

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.

10.3 Advice for adult supervision

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.

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.

11.2.2.2 Reagents

11.2.3 Apparatus

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

11.2.3.1 Platinum crucible.

11.2.3.2 Muffle furnace, or relevant equipment, temperature range: up to (1 000 ± 50) ºC.

11.2.3.3 Analytical balance, precision 0,1 mg.

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).

11.2.3.5 Atomic emission spectrometer.

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.

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.

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).

$M_m=\frac{\left(c_{\mathrm{sample}}⨉c_{\mathrm{blank}}\right)⨉V⨉f}{W⨉\mathrm{10\; 000}}$(1)

where

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

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

c_blank 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):

$M_{mo}=\frac{\left(c_{\mathrm{sample}}⨉c_{\mathrm{blank}}\right)⨉V\times f⨉f_m}{W⨉\mathrm{10\; 000}}$(2)

where

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

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

c_blank 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;

f_m is the calculation factor of metal to metal oxide.

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

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.

$\mathrm{Co}O⨉\mathrm{2,360\; 7}={\mathrm{CoO.Al}}_2{O}_3$ (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.

${\mathrm{Pr}}_2{O}_3⨉\mathrm{1,555\; 8}={\mathrm{Pr}}_2{O}_3+\mathrm{ZrSi}{O}_4$(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.

$V_2{O}_5⨉\mathrm{1,919\; 8}=V_2{O}_4+\mathrm{ZrSi}{O}_4$(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 Fe₂O_{3 total} , V₂O_{5 total}, Pr₂O_{3 total} and ZrO_{2 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.

$({\mathrm{Pr}}_2{O}_3+\mathrm{ZrSi}{O}_4)⨉\mathrm{0,240\; 1}=\mathrm{Zr}{O}_2\text{(a)}$(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.

$(V_2{O}_4+\mathrm{ZrSi}{O}_4)⨉\mathrm{0,352\; 9}=\mathrm{Zr}{O}_2\text{(b)}$(7)

The ZrO₂ (a) and ZrO₂ (b) amounts shall be added and subtracted from ZrO_2total.

$\mathrm{Zr}{O}_{2\mathrm{total}}-(\mathrm{Zr}{O}_2\text{(a)}+\mathrm{Zr}{O}_2\text{(b)})=\mathrm{Zr}{O}_2\text{(c)}$(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.

${\mathrm{Fe}}_2{O}_3⨉\mathrm{2,147\; 8}={\mathrm{Fe}}_2{O}_3+\mathrm{ZrSi}{O}_4$(9)

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

$\left({\mathrm{Fe}}_2{O}_3+\mathrm{ZrSi}{O}_4\right)\times \mathrm{0,359\; 3}=\mathrm{Zr}{O}_2\text{(d)}$(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.

$\mathrm{Zr}{O}_2\text{(e)}\times \mathrm{1,487}6=\mathrm{Zr}\mathrm{Si}{O}_{4\mathrm{pure}}$(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.

$\mathrm{Zr}{O}_2\text{(c)}\times \mathrm{2,783}6={\mathrm{Fe}}_2{O}_3+\mathrm{Zr}\mathrm{Si}{O}_4$(13)

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

$F{e}_2{O}_3+\mathrm{Zr}\mathrm{Si}{O}_4\times \mathrm{0,465\; 6}=F{e}_2{O}_3\left(a\right)$(14)

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

${\mathrm{Fe}}_2{O}_{3\mathrm{total}}⨉{\mathrm{Fe}}_2{O}_3\text{(a)}={\mathrm{Fe}}_2{O}_{3\mathrm{pure}}$(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.

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.

11.3.2.2 Reagents

11.3.3 Apparatus

11.3.3.2 Spark-proof heating mantle/water bath.

11.3.3.4 Desiccator chamber.

11.3.3.5 150-ml or 250-ml glass stoppered flat bottomed flask.

11.3.3.7 Soxhlet cellulose thimble.

11.3.3.8 Water-cooled glass condenser.

11.3.3.9 Cotton wool.

11.3.3.10 Glass volumetric flask.

11.3.3.11 General volumetric glassware.

11.3.3.12 Stainless steel scalpel blade.

11.3.3.13 Attenuated Total Reflectance Fourier Transform Infra Red Spectrometer (ATR-FT-IR).

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

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.

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

Figure 1 — Total ion chromatogram of a mixture of phthalates

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.

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

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.

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.

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.

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

$M_{\mathrm{Hexane}}=\frac{W_{A+E}⨉W_A}{W_S}\times 100$(16)

where

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

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

W_A is the mass of flask A, in g;

W_S 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

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

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

W_B is the mass of flask B, in g;

W_S 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)

where

M_te+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 Calculation of plasticisers content by GC-MS

$M_{\mathrm{PAE}}=\frac{c_{\mathrm{e1}}\times 250\left(\mathrm{ml}\right)\times f}{W_s\times \mathrm{10\; 000}}$(19)

where

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

c_e1 is the concentration of phthalic acid ester in extract solution, in μg/ml;

f is the dilution factor;

W_S is the mass of sample, in g.

$c_{\mathrm{e1}}=\left(W_{A+E}\right)-W_A$(20)

where

c_e1 is the concentration of extract solution, in μg/ml;

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

W_A is the mass of flask A, in g.

$M_{\mathrm{CAE}}=\frac{c_{e2}\times 250\left(\mathrm{ml}\right)\times f}{W_s\times \mathrm{10\; 000}}$(21)

where

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

c_e2 is the concentration of citric acid ester in extract solution, in μg/ml;

f is the dilution factor;

W_s is the mass of sample, in g.

$c_{e2}=\left(W_{B+E}\right)-W_B$(22)

where

c_e2 is the concentration of extract solution, in μg/ml;

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

W_B is the mass of flask B, in g.

$M_{\mathrm{AAE}}=\frac{c_e\times 250\left(\mathrm{ml}\right)\times f}{W_s\times \mathrm{10\; 000}}$(23)

where

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

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

f is the dilution factor;

W_S 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.

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

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.

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.

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

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.

11.4.3.3.3 Brown glass vials for headspace sampling.

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.

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.

11.5.2 Standards and reagents

11.5.2.1 Standards

11.5.2.2 Reagents

11.5.3 Apparatus

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.

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

Acquisition data: 2 scan/s

11.5.3.2 General equipment and glassware used in laboratory.

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.

11.5.3.7 Volumetric flask and volumetric pipettes.

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:

$M_{\mathrm{st}}=\frac{c_{\mathrm{st}}\times 15}{W_s\times \mathrm{1\; 000}}$(24)

where

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

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

W_s 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.

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

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.

11.6.3 Standards and reagents

11.6.3.1 Standards

11.6.3.2 Reagents

11.6.4 Apparatus

11.6.4.6 General volumetric glassware.

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

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

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

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.

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:

$V_s=\frac{V_t\times d_s}{c_{\mathrm{sst}}}$(25)

where

V_s is the volume of the solvent, in ml;

V_f is the volume of the flask, in ml;

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

d_s 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.

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.

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.

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.

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].

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.

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.

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.

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.

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.

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.

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.

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.

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)

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

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.

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

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).

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:

$M_{\mathrm{sol}}=\frac{W_s}{W\times 10}$(26)

where

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

W_S is the mass of solvent, in mg;

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:

$M_{\mathrm{sol}}=\frac{W_s\times f}{W\times \mathrm{0,5}}$(27)

where

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

W_S 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.

Test report, see 11.7.7.

11.7.2 Determination of total extract

11.7.2.1 Standards and reagents

11.7.2.1.1 Standards

None.

11.7.2.1.2 Reagents

11.7.2.2 Apparatus

11.7.2.2.2 Ultrasonic bath or shaker.

11.7.2.2.3 Rotary evaporator.

11.7.2.2.6 50-ml glass stoppered flat bottom flasks.

11.7.2.2.7 General volumetric glassware.

11.7.2.2.8 Desiccator chamber.

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.

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:

$M_r=\frac{W_r\times 100}{\mathrm{1\; 000}\times W}$(28)

where

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

W_r 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

11.7.3.3 Apparatus

11.7.3.3.1 Oven, capable of maintaining a temperature of (105 ± 2) °C.

11.7.3.3.2 Press for making potassium bromide pellets.

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.

Use an ATR cell for a measurement in reflection mode.

11.7.3.4 Sampling

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.

Figure 6 — FTIR-spectrum of nitrocellulose in reflection mode

11.7.4 Determination of plasticisers

11.7.4.1 Principle

The determination of plasticisers is performed by the GC-MS method described in 11.3.

NOTE If the residue from 11.7.2 is < 3 %, the determination of plasticisers is not necessary. In the presence of nitrocellulose, the determination of plasticisers is not necessary if the residue from 11.7.2 is < 5 %.

11.7.4.2 Standards and reagents

See 11.3.2.

11.7.4.3 Apparatus

See 11.3.3.

11.7.4.4 Preparation of the standard solution

See 11.3.4.

11.7.4.5 Procedure

In a 20-ml volumetric flask, add 5 ml of the solution of the extraction residue from 11.7.2.5 and fill up to the mark with hexane.

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

Transfer a portion of these solutions into a capped vial for GC-MS analysis.

Determine the plasticisers content in accordance with 11.3.7.5 and 11.3.7.6.

11.7.4.6 Evaluation of results

The plasticiser content in the sample is calculated as follows:

$M_P=\frac{c_p\times 20\left(\mathrm{ml}\right)\times 10}{W\times \mathrm{10\; 000}}\times f$(29)

where

M_P is the plasticiser content in the sample, in % (m/m);

c_p is the concentration of the plasticiser content in the sample solution, in µg/ml;

W is the mass of sample, in g;

f is the dilution factor.

11.7.5 Determination of film-forming agents

11.7.5.1 Principle

The film-forming agents are determined by GC-MS in the extract from 11.7.2.5.

11.7.5.2 Standards and reagents

11.7.5.2.1 Standards

11.7.5.2.2 Reagents

11.7.5.3 Apparatus

11.7.5.3.1 General volumetric glassware.

11.7.5.3.2 Analytical balance.

11.7.5.3.4 Gas chromatography with mass spectrometer detector (GC-MS).

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

Carrier gas: Helium

Injector temperature: 250 °C

Injection type: splitless

Injection volume: 1 µl

Detector temperature: 320 °C

Figure 7 shows typical chromatograms for film-forming agents.

Figure 7 — Chromatogram of film-forming agent substances 1 to 9

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

Carrier gas: Helium

Injector temperature: 250 °C

Injection type: splitless

Injection volume: 1 µl

Detector temperature: 320 °C

Figure 8 shows typical chromatograms for film-forming agents.

Figure 8 — Chromatogram of film-forming agent Luwax E

11.7.5.4 Preparation of standard solutions

11.7.5.4.1 Stock solutions

Prepare each stock solutions of film-forming agents, substances 1 to 9 of Table 62 by dissolving 200 mg of each substance in 100 ml of diethyl ether (c = 2 000 mg/l).

Prepare a stock solution of Luwax E by dissolving 50 mg of the substance in 10 ml of a 0,5 M potassium hydrogen carbonate solution in methanol (c = 5 µg/µl).

11.7.5.4.2 Calibration solutions

Prepare calibration solutions of substances 1 to 9 containing a mixture of the components from the stock solutions by appropriate solvent dilutions using pipettes into 100-ml glass volumetric flasks and making up to the mark with diethyl ether. Table 65 shows the concentration of each analyte in the calibration solution.

Prepare calibration solutions of Luwax E from the stock solution by appropriate solvent dilutions using pipettes into 20-ml vials.

Remove the solvent by a stream of nitrogen, then add 2 g of potassium carbonate and 0,2 g of potassium hydrogen carbonate.

Dissolve the content of each vial with 4 ml of water. After cooling to room temperature, add 2 ml of di-isopropyl ether and 200 µl of dimethyl sulfate. Crimp the vials and put in an oven or a water bath for 1 h at 65 °C. Shake the vials every 5 min.

Remove the ether phase with a small pipette and transfer into a small vial for analysis by GC-MS. Table 66 shows the concentration of Luwax E in the calibration solutions.

11.7.5.4.3 Stability of the standard solutions

The stock solutions can be stored in a refrigerator at (4 ± 2) °C for 3 months.

The diluted standard solutions can be stored in a refrigerator at (4 ± 2) °C for a week.

11.7.5.5 Sampling

See 11.7.2.3.

11.7.5.6 Procedure

Dilute 1 ml of the solution of the extraction residue prepared in 11.7.2.5 in a 100-ml volumetric flask with diethyl ether.

Analyse the sample solution by GC-MS in the full-scan mode (conditions described in 11.7.5.3.4). Select characteristic mass numbers of each component with the help of their full scan spectrum in order to quantify them most sensitive in the SIM-modus (see Table 64).

If a film-forming agent is detected, the recovery is performed by standard addition as follows:

Analyse the sample in duplicate. Analyse the first test portion directly as described above. Analyse the second test portion with a known amount of analyte (standard solution) added according to 11.7.2.5 and 11.7.5.6.

For expediency, the recovery/standard addition may be performed at the same time as the identification.

11.7.5.7 Evaluation of results

The amounts of the film-forming agents are calculated from the peak areas of the individual components by calibration curves that are constructed using the calibration solutions.

Calculate the recovery using the concentration of the analyte of the two test portions.

$\mathrm{rec}=\frac{\left(c_{\mathrm{fa}+\mathrm{std}}-c_{\mathrm{fa}}\right)}{c_{\mathrm{std}}}\times 100$(30)

where

rec is the recovery, in % (m/m);

c_{fa + std} is the concentration of film-forming agent plus standard addition, in mg/l;

c_fa is the concentration of the film-forming agent, in mg/l;

c_std is the concentration of standard solution added, in mg/l.

The concentration of the film-forming agents in the sample, corrected for recovery, is calculated as follows:

$M_{\mathrm{fa}}=\frac{c_{\mathrm{fa}}\times 2\times 100}{\mathrm{1\; 000}\times \mathrm{1\; 000}\times W}\times \frac{100}{\mathrm{rec}}$(31)

where

M_fa is the film-forming agents’ content, in % (m/m);

c_fa is the concentration of the film-forming agents, in mg/l;

W is the mass of sample, in g;

rec is the recovery, in % (m/m).

11.7.6 Determination of the modifiers

The contents of the modifiers are calculated from the residue content, plasticisers content and film-forming agents’ content calculated in accordance with 11.7.2.6, 11.7.4.6 and 11.7.5.7.

The concentration of the modifiers in the solvent-based adhesives is calculated as follows:

$M_{m,\mathrm{sba}}=r-M_p$(32)

where

M_m,sba is the content of modifiers in solvent-based adhesives, in % (m/m);

r is the content of residue, in % (m/m);

M_p is the content of plasticisers, in % (m/m).

The content of the modifiers in the solvent-based paint and lacquers is calculated as follows:

$M_{m,\mathrm{sbpl}}=M_r-M_{\mathrm{fa}}-M_p$(33)

where

M_m,sbpl is the content of modifiers in solvent-based paints and lacquers, in % (m/m);

M_r is the content of residue, in % (m/m);

M_fa is the content of film-forming agents, in % (m/m);

M_P is the content of plasticisers, in % (m/m).

11.7.7 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); 80
3. results of the tests recorded as:
   1. list of substances identified;
   2. total content of plasticisers, film-forming agents and modifiers, in % (m/m), rounded to 0,1 %;
4. any deviation from the test procedure specified;
5. date of test.

Annex A (normative)
Environmental, health and safety precautions

When preparing this standard, consideration was given to the minimisation of environmental impacts caused by the use of the methods of analysis.

It is the responsibility of the analyst to use safe and proper techniques in handling materials in the methods of analysis specified in this European Standard.

• Consult manufacturers for specific details such as material safety data sheets and other recommendations.
• Wear protective goggles and coats in all laboratory areas.
• Be careful about the substances, which are toxic and/or human carcinogens.
• A fume cupboard shall be used during preparation of organic solvent solutions.
• Solvents shall be disposed in accordance with environmental requirements.

Annex B (informative)
Organic solvents

Annex C (informative)
Maximum permitted element concentrations for the compounds permitted in ceramic and vitreous enamelling materials

Table C.1 can be used to determine whether a metallic element is present in a ceramic or vitreous enamelling material in an amount that is in accordance with the requirements of Table 1. If an element concentration calculated according to 11.2.9.1 exceeds the maximum permitted concentration in the relevant compound in column 5 of Table C.1, the concentration of the permitted compound should be calculated according to 11.2.9.2.

NOTE Some of the compounds to be determined are not stoichiometric.

Annex D (informative)
Validation of test methods

The methods described in this standard were developed and validated using a peer-review protocol based on that used by the AOAC. The validation data obtained during the development of the methods met the repeatability limits of acceptability based on the statistical experimental values derived by Horwitz [13].

The peer-review system makes allowance for the limited range of samples, matrices and equipment used by the participating laboratories. A consequence of this approach is that no data from extensive laboratory trials was available for validation purposes.

Annex E (informative)
Rationale

E.1 General remark

Chemical toys are defined in the Directive 2009/48/EC. Applying this definition the safety of chemical toys is dealt with mainly in EN 71-4 and EN 71-5.

This part sets requirements and test methods for those chemical toys (sets) where playing with chemical substances and mixtures includes more creative and artistic ideas of the user beside the handling within the given instructions for use.

The broad variety of chemical toys in this standard is reflected also in the diverse requirements on the nature of inorganic and organic substances and mixtures. Concurrently this standard sets important assumptions on the safe handling of chemical substances and mixture by requiring adequate apparatus and protective equipment where necessary, transfers the warning requirements from Directive 2009/48/EC in the practical implementation. A major aspect for the safe handling of the chemical substances and mixtures is given by applying the warning, managing the packaging having instructions for use and safety rules and first aid requirements for each of these toys. Only the combination of these requirements ensures safe playing with chemical toys under the supervision by an adult.

The extensive and detailed requirements on substance-classes like basic materials, plasticisers, preservatives, solvents, reaction-by-products are added by test methods for major safety issues of these substances and mixtures.

E.2 Primary packaging (4.1; 5.2; 6.2; 7.1.2; 7.2.2; 8.2.1.2.2; 8.2.2.6; 8.3.2; 8.4.3; 9.2)

The primary packaging is presented at the point of sale. Due to the nature of a set, several items may be combined in a primary packaging. Individual items may be packed separately in suitable packaging devices (e.g. wrapping, containers).

E.3 Minimum age (4.1; 5.2; 6.2; 7.1.2; 7.2.3; 8.2.1.2.3; 8.2.1.3.3; 8.2.2.6; 8.3.3; 8.4.3)

The minimum age of the user is specifically given for each type of toy described in the standard. For a given individual minimum age, not only the intrinsic dangerous nature of a chemical toy has been taken into account. Also intellectual and motoric abilities of the intended users are important for safe use of a chemical toy (set). Intended users should be able to follow instructions for use, to understand precaution requirements and they should be able to build, decorate or assemble the toy properly.

E.4 Phthalates (6.1 Table 2; 8.2.2; 8.4.1)

Besides those phthalates forbidden in toys (Regulation (EC) No 1907/2006, Annex XVII, No. 51 [8]) certain phthalates are specifically restricted (Regulation (EC) No 1907/2006, Annex XVII, No. 52 [8]).

The listing of certain phthalates restricted in toys as appropriate for food contact does not justify a use in toys.

E.5 Benzene (6.1, Table 3; 8.2.2.4, Table 12; 8.4.1, Table 16)

Benzene shall not be used in toys or parts of toys greater than 5 mg/kg in the free state ([8], Annex XVII, No. 5).

Benzene is not contained in oven-hardening plasticised PVC modelling clay. It can, however, be generated during heating and, consequently benzene emission can occur during heating of oven-hardening plasticised PVC modelling clay. Therefore, the benzene limit introduced in Table 2 addresses possibly occurring benzene emissions during heating in addition to the limits laid down in [8].

E.6 Preservatives (7.2.1; 8.2.1.1; 8.3.1)

Only preservatives allowed for food as well as preservatives allowed in cosmetics should be used in those chemical toys. The requirements take into account human ingestion and long term dermal exposure. Such chemical toys are neither intended for ingestion nor for long term dermal exposure (see first aid information) and thus maintain a very high level of consumer safety.

Annex F (informative)
Significant technical changes between this European Standard and the previous version

Annex ZA (informative)
Relationship between this European Standard and the Essential Requirements of EU Directive 2009/48/EC

This European Standard has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association to provide a means of conforming to Essential Requirements of the New Approach Directive 2009/48/EC of the European Parliament and of the Council of 18 June 2009 on the safety of toys.

Once this standard is cited in the Official Journal of the European Union under that Directive and has been implemented as a national standard in at least one Member State, compliance with the clauses of this standard given in Table ZA.1 confers, within the limits of the scope of this standard, a presumption of conformity with the corresponding Essential Requirements of that Directive and associated EFTA regulations.

WARNING — Other requirements and other EU Directives may be applicable to the product(s) falling within the scope of this standard.

Bibliography

[1]   EN 71-4:2013, Safety of toys — Part 4: Experimental sets for chemistry and related activities

[2]   EN ISO 8317, Child-resistant packaging — Requirements and testing procedures for reclosable packages (ISO 8317)

[3]   EN ISO 11885, Water quality — Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (ISO 11885)

[4]   ISO 2561, Plastics — Determination of residual styrene monomer in polystyrene (PS) and impactresistant polystyrene (PS-I) by gas chromatography

[5]   Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006

[6]   Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances

[7]   Directive 1999/45/EC of the European Parliament and of the Council of 31 May 1999 concerning the approximation of the laws, regulations and administrative provisions of the Member States relating to the classification, packaging and labelling of dangerous preparations

[8]   Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing a European Chemicals Agency

[9]   Regulation (EC) No 1333/2008 of the European Parliament and of the Council of 16 December 2008 on food additives

[10] Council Directive 76/768/EEC of 27 July 1976 on the approximation of the laws of the Member States relating to cosmetic products

[11] Commission Regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food

[12] Directive 2009/48/EC of the European Parliament and of the Council of 18 June 2009 on the safety of toys

[13] W. Horwitz, “Evaluation of Analytical Methods for Regulation of Foods and Drugs”, Anal. Chem. 1982, Nr. 54, 67A – 76A

[14] Identification and Analysis of Plastics by J. Haslam, H.A. Willis & D.C.M Squirrel 1981.