Safety of toys - Part 5: Chemical toys (sets) other than experimental sets - Amendment A1

Migrated from Progress Sheet (TC Comment) (2000-07-10): TC forecasts modified (TC resolution 48/2000, 2000-05-05)

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

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

Varnost igrač - 5. del: Kemijske igrače (kompleti), razen kompletov za kemijske poskuse – Dopolnilo A1

General Information

Status
Withdrawn
Publication Date
28-Feb-2006
Withdrawal Date
03-Jul-2013
Current Stage
9900 - Withdrawal (Adopted Project)
Start Date
01-Jul-2013
Due Date
24-Jul-2013
Completion Date
04-Jul-2013

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SLOVENSKI STANDARD
SIST EN 71-5:1995/A1:2006
01-marec-2006
9DUQRVWLJUDþGHO.HPLMVNHLJUDþH NRPSOHWL UD]HQNRPSOHWRY]DNHPLMVNH
SRVNXVH±'RSROQLOR$

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

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

Sécurité des jouets - Partie 5: Jouets chimiques (coffrets) autres que les coffrets

d'expériences chimiques
Ta slovenski standard je istoveten z: EN 71-5:1993/A1:2006
ICS:
97.200.50 ,JUDþH Toys
SIST EN 71-5:1995/A1:2006 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
EUROPEAN STANDARD
EN 71-5:1993/A1
NORME EUROPÉENNE
EUROPÄISCHE NORM
January 2006
ICS 97.200.50
English Version
Safety of toys - Part 5: Chemical toys (sets) other than
experimental sets

Sécurité des jouets - Partie 5: Jeux chimiques (coffrets) Sicherheit von Spielzeug - Teil 5: Chemisches Spielzeug

autres que les coffres d'expériences chimiques (Sets) ausgenommen Experimentierkästen

This amendment A1 modifies the European Standard EN 71-5:1993; it was approved by CEN on 7 December 2005.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for inclusion of this

amendment into the relevant national standard without any alteration. Up-to-date lists and bibliographical references concerning such

national standards may be obtained on application to the Central Secretariat or to any CEN member.

This amendment exists in three official versions (English, French, German). A version in any other language made by translation under the

responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,

Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,

Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels

© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 71-5:1993/A1:2006: E

worldwide for CEN national Members.
---------------------- Page: 2 ----------------------
EN 71-5:1993/A1:2006 (E)
Contents Page

Foreword ..........................................................................................................................................................3

12 Test methods.......................................................................................................................................6

12.1 General ................................................................................................................................................6

12.2 Determination of elements in ceramic and vitreous enamelling materials ....................................6

12.3 Determination of plasticizers in oven hardening polyvinyl chloride (PVC) modelling clay

sets.....................................................................................................................................................11

12.4 Determination of the emission of benzene, toluene and xylenes from oven hardening

plasticised PVC modelling sets and plastic moulding sets...........................................................23

12.5 Determination of styrene content in polystyrene granules ...........................................................27

12.6 Identification and determination of substances in photographic processing sets .....................29

12.7 Determination of organic solvents ..................................................................................................50

12.8 Combined approach for the determination of plasticizers 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 ............................................................................70

Annex A (normative) Environmental, health and safety precautions.........................................................81

Annex B (informative) Solvent content in different matrices and permitted maximum

concentration ....................................................................................................................................82

Annex C (informative) Preliminary test method for the determination of elements in ceramic and

vitreous enamelling materials..........................................................................................................83

Annex D (informative) Validation of test methods .......................................................................................84

Annex ZA (informative) Clauses of this European Standard addressing essential requirements or

other provisions of EU Directives....................................................................................................85

Bibliography...................................................................................................................................................86

---------------------- Page: 3 ----------------------
EN 71-5:1993/A1:2006 (E)
Foreword

This European Standard (EN 71-5:1993/A1:2006) has been prepared by Technical Committee CEN/TC 52

“Safety of toys”, the secretariat of which is held by DS.

This Amendment to the European Standard EN 71-5:1993 shall be given the status of a national standard,

either by publication of an identical text or by endorsement, at the latest by July 2006, and conflicting national

standards shall be withdrawn at the latest by July 2006.

This European Standard 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(s), see informative Annex ZA, which is an integral part of this European

Standard.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following

countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic,

Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,

Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden,

Switzerland and United Kingdom.
---------------------- Page: 4 ----------------------
EN 71-5:1993/A1:2006 (E)
Add under "Introduction",
following the 1 paragraph:
Part 6: Graphical symbol for age warning labelling
Part 7: Finger paints — Requirements and test methods

Part 8: Swings, slides and similar activity toys for indoor and outdoor family 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
following the 6 paragraph:

Under a mandate given to CEN by the European Commission, test methods were developed to determine the

migration and emission of the following substances or compounds, respectively:
• elements in ceramic and vitreous enamelling materials;

• plasticizers in oven hardening poly (vinyl chloride) (PVC) modelling clay sets;

• toluene, xylene and benzene in oven hardening plasticized PVC modelling clay sets and plastic moulding

sets;
• styrene in plastic moulding sets;
• substances in photographic processing sets;
• organic solvents in adhesives, lacquers, paints etc. and
• modifiers, film builders and plasticizers in paints and lacquers.

Five lead laboratories worked out the relevant test methods. In a second step the developed test procedures

were validated by the lead and peer review laboratories using specially manufactured or specially selected

samples (see Annex D). All test methods have been supervised by CEN/TC 52/WG 5 which also developed

EN 71-4.
th th
The 7 to 12 paragraph in the "Introduction" shall be deleted.
Replace the 1 sentence under Clause 1 "Scope" by

This part of EN 71 specifies requirements and test methods for the substances and materials used in chemical

toys (sets) other than experimental sets.
Amend the standard text in Clause 2 to read

The following referenced documents are indispensable for the application of this European Standard. For

dated references, only the edition cited applies. For undated references, the latest edition of the referenced

document (including any amendments) applies.
Add under Clause 2 "Normative references"
---------------------- Page: 5 ----------------------
EN 71-5:1993/A1:2006 (E)

EN 14517:2004, Liquid petroleum products — Determination of hydrocarbon types and oxygenates in petrol

— Multidimensional gas chromatography method

EN ISO 3696:1995, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987)

Delete the following references

ISO 3696:1987, Water for analytical laboratory use; specifications and test methods

---------------------- Page: 6 ----------------------
EN 71-5:1993/A1:2006 (E)
Add the following clause:
12 Test methods
12.1 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.
12.2 Determination of elements in ceramic and vitreous enamelling materials
12.2.1 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.
12.2.2 Standards and reagents
12.2.2.1 Standards
NOTE These elemental standard solutions are commercially available.
Table 16 — Standards
Chemical Concentration
mg/l
Copper 1 000
Iron 1 000
Praseodymium 1 000
Cobalt 1 000
Zirconium 1 000
Vanadium 1 000
Tin 1 000
12.2.2.2 Reagents
Table 17 — Reagents
Chemical Concentration
Di-lithium tetraborate (Li B O)
2 4 7
Hydrochloric acid
ρ(HCl) = 1,12 g/ml
---------------------- Page: 7 ----------------------
EN 71-5:1993/A1:2006 (E)
12.2.3 Apparatus

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

provided.
12.2.3.1 Platinum crucible

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

12.2.3.3 Analytical balance, precision 0,1 mg
12.2.3.4 Glassware (beaker, funnel, volumetric flask and pipettes)

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

12.2.3.5 Atomic emission spectrometer
12.2.4 Preparation of standard solutions
12.2.4.1 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 (12.2.2.1) into a 100-ml volumetric flask. Add 10 ml

of hydrochloric acid (12.2.2.2), mix and make up to the mark with water.

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

12.2.4.2 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, mix and make up to the mark with water.
This solution shall be freshly prepared.
12.2.4.3 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, mix and make up to the mark with water.
This solution shall be freshly prepared.
12.2.5 Blank solution

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

12.2.6 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.
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EN 71-5:1993/A1:2006 (E)
12.2.7 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 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.
12.2.8 Procedure

Determine the elemental concentrations using the wavelengths according to Table 18. In case of spectral

interference choose an alternative appropriate wavelength.
Table 18 — Wavelengths
Element Wavelength
Copper (Cu) 324,752
Iron (Fe) 259,942
Praseodymium (Pr) 422,285
Cobalt (Co) 228,616
Zirconium (Zr) 339,198
Vanadium (V) 292,399
Tin (Sn) 189,932
After the verification of the calibration function the samples are measured.
Determine the blank solutions before analysing the solutions.

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

solution.
12.2.9 Evaluation of results
12.2.9.1 General
The mean value of three test portions shall be given.
The metal contents are calculated according to Equation (1):
(c −c )×V × f
sample blank
M = (1)
W ×10000
where
M is the content of the metal in the sample, in mass-%;
---------------------- Page: 9 ----------------------
EN 71-5:1993/A1:2006 (E)
c is the concentration of the metal in the analytical solution, in mg/l;
sample
c is the concentration of the metal in the blank value solution, in mg/l;
blank
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 the concentrations are exceeded, the concentration of compounds have to be calculated according to

Equation (2) and 12.2.9.2:
(c −c )×V × f × f
sample blank m
M = (2)
W ×10000
where
M is the content of the metal in the sample, in mass-%;
c is the concentration of the metal in the analytical solution, in mg/l;
sample
c is the concentration of the metal in the blank value solution, in mg/l;
blank
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 is the calculation factor of metal to metal oxide.
For the conversion factor f as to the individual metals see Table 19.
Table 19 — Conversion factors
Compound Element Conversion factor
Copper oxide (CuO) Cu 1,251 8
Di-iron trioxide (Fe O) Fe 1,429 7
2 3
Dipraseodymium trioxide (Pr O) Pr 1,170 3
2 3
Coblat oxide (CoO) Co 1,271 5
Zirconium dioxide (ZrO) Zr 1,350 8
Divanadium pentoxide (V O) V 1,785 2
2 5
Tin dioxide (SnO2) Sn 1,269 6
12.2.9.2 Calculation of the pigment contents in the enamel samples

12.2.9.2.1 Calculation of the concentration of copper oxide (CuO) and tin dioxide (SnO )

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

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EN 71-5:1993/A1:2006 (E)

12.2.9.2.2 Calculation of the concentration of aluminium cobalt oxide (CoO.Al O )

2 3

The concentration of aluminium cobalt oxide shall be calculated by multiplying the amount of CoO calculated

according to Equation (2) by the factor 2,360 7.
CoO ×× 2,360 7 = CoO.Al O (3)
2 3

12.2.9.2.3 Calculation of the concentration of praseodymium zirconium silicate (Pr O + ZrSiO )

2 3 4

The concentration of praseodymium zirconium silicate shall be calculated by multiplying the amount of Pr O

2 3
calculated according to Equation (2) by the factor 1,555 8.
Pr O ×××× 1,555 8 = Pr O + ZrSiO (4)
2 3 2 3 4

12.2.9.2.4 Calculation of the concentration of vanadium zirconium silicate (V O + ZrSiO )

2 4 4

The amount of vanadium zirconium silicate shall be calculated by multiplying the amount of V O calculated

2 5
according to Equation (2) by the factor 1,919 8.
V O ×××× 1,9198 = V O + ZrSiO (5)
2 5 2 4 4

12.2.9.2.5 Calculation of the concentration of di-iron oxide (Fe O ), iron zirconium silicate (Fe O +

2 3 2 3
ZrSiO ) and zirconium ortho silicate (ZrSiO )
4 4
Calculate the Fe O , V O , Pr O and ZrO concentration according to Equation (2).
2 3 total 2 5 total 2 3 total 2 total

If Pr O is present, then the concentration of (Pr O + ZrSiO ) shall be calculated according to Equation (4).

2 3 2 3 4

The amount of ZrO (a) shall be calculated by multiplying the concentration of (Pr O + ZrSiO ) by the factor

2 2 3 4
0,240 1.
(Pr O + ZrSiO ) ×× 0,240 1 = ZrO (a) (6)
2 3 4 2

If V O is present, the concentration of (V O + ZrSiO ) shall be calculated according to Equation (5).

2 5 2 4 4

(b) shall be calculated by multiplying the concentration of (V O + ZrSiO ) by the factor

The amount of ZrO
2 2 4 4
0,352 9.
(V O + ZrSiO ) ×××× 0,352 9 = ZrO (b) (7)
2 4 4 2
The ZrO (a) and ZrO (b) amounts shall be added and subtracted from ZrO .
2 2 2 total
ZrO - (ZrO (a) + ZrO (b)) = ZrO (c) (8)
2 total 2 2 2

The concentration of iron zirconium silicate (Fe O + ZrSiO ) shall be calculated from the amount of Fe O

2 3 4 2 3
calculated according to Equation (2).
The amount of Fe O shall be multiplied by the factor 2,147 8.
2 3
Fe O * 2,147 8 = Fe O + ZrSiO (9)
2 3 2 3 4

The amount of ZrO (d) shall be calculated by multiplying the concentration of (Fe O + ZrSiO ) by the factor

2 2 3 4
0,359 3.
(Fe O + ZrSiO ) ×× 0,359 3 = ZrO (d) (10)
2 3 4 2

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

2 2 2 2 2
---------------------- Page: 11 ----------------------
EN 71-5:1993/A1:2006 (E)
ZrO (c) - ZrO (d) = ZrO (e) (11)
2 2 2

The amount of ZrSiO is calculated by multiplying the ZrO (e) concentration by the factor 1,487 6.

4 pure 2
ZrO (e) ×××× 1,487 6 = ZrSiO (12)
2 4 pure

If ZrO (c) < ZrO (d) the concentration of (Fe O + ZrSiO ) is calculated by multiplying the ZrO (c)

2 2 2 3 4 2
concentration by the factor 2,783 6.
ZrO (c) ×× 2,783 6 = Fe O + ZrSiO (13)
2 2 3 4

The amount of Fe O (a) is calculated by multiplying the concentration of (Fe O + ZrSiO ) by the factor

2 3 2 3 4
0,465 6.
Fe O + ZrSiO ×××× 0,465 6 = Fe O (a) (14)
2 3 4 2 3

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

2 3 pure 2 3 2 3
total
Fe O - Fe O (a) = Fe O (15)
2 3 total 2 3 2 3 pure
12.2.10 Test report
The analytical report shall contain as a minimum the following information:
a) type and identification of the product and/or material tested;
b) a reference to this European Standard;

c) 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;
d) any deviation from the test procedure specified;
e) date of test.

12.3 Determination of plasticizers in oven hardening polyvinyl chloride (PVC) modelling clay

sets
12.3.1 Principle

The plasticizer content is determined by solvent extraction to quantitatively extract the plasticizer 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

plasticizer content can be determined by evaporating off the solvent and weighing the solvent residue and

identifying the plasticizer by Attenuated Total Reflectance-Fourier Transform-Infra Red (ATR-FT-IR)

Spectrometry.

Determination of plasticizer(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 plasticizers in solvent-based adhesives and solvent-

based paints and lacquers (see 12.8.4).
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EN 71-5:1993/A1:2006 (E)
12.3.2 Standards and reagents
12.3.2.1 Standards

NOTE The given substances (except citrates) are examples for the requirements in Table 17.

Table 20 — Phthalic acid esters
Chemical CAS No.
bis(2-ethylhexyl) phthalate (DEHP) 117-81-7
di-isononyl phthalate (DINP) 28553-12-0
di-isodecyl phthalate (DIDP) 26761-40-0
benzyl butyl phthalate (BBP) 85-68-7
di-n-butyl phthalate (DBP) 84-74-2
di-n-hexyl phthalate (DNHP) 84-75-3
di-n-heptyl phthalate (DNHpP) 3648-21-3
di-n-octyl phthalate (DNOP) 117-84-0
di-n-nonyl phthalate (DNP) 84-76-4
di-n-decyl phthalate (DDP) 84-77-5
NOTE 1 The chemicals DEHP, DINP, DIDP, BBP and DBP can be
used for analytical purposes for modelling clays. They are not permitted for
the use in PVC modelling clays. However, they are examples for
plasticizers according to the requirements in 9.2.2 and 9.4.
NOTE 2 The technical grade of the substances DINP and DIDP is
typically a mixture of isomers and homologues.
Table 21 — Adipic acid polyesters
Chemical Trade names CAS No.
Hexanedioic acid, polymer with propane-1,2- 55799-38-7
Palamoll 632 & 636
diol, acetate
Hexanedioic acid, polymer with butane-1,3-diol a
150923-12-9
Palamoll 646
and butane-1,4-diol, acetate
Hexanedioic acid, polymer with 2,2-dimethyl- a
208945-13-5
Palamoll 652
propane-1,3-diol and propane-1,2-diol, isononyl
ester
Hexanedioic acid, polymer with butane-1,4-diol a
208945-12-4
Palamoll 654 & 656
and 2,2-dimethyl-propane-1,3-diol, isononyl
ester
Hexanedioic acid, polymer with 2,2-dimethyl- a
208945-11-3
Palamoll 858
propane-1,3-diol and 3-hydroxy-2,2-
dimethylpropanoic acid, isononyl ester
No chemical inventory name available b
39363-92-3
Paraplex G-40
Polymeric plasticizer derived from adipic acid and polyhydric alcohols.
Polyester adipate.

NOTE Trade names for adipic acid polyesters are examples for those types of plasticizers.

---------------------- Page: 13 ----------------------
EN 71-5:1993/A1:2006 (E)
Table 22 — Citric acid esters
Chemical CAS No.
Tributyl acetylcitrate 77-89-4
Tris(2-ethylhexyl) acetylcitrate 144-15-0
Table 23 — Alkylsulfonic acid esters
Chemical CAS No.
Alkylsulfonic phenyl ester 91082-17-6
12.3.2.2 Reagents
Table 24 — Solvents
Chemical CAS No.
Hexane, analytical grade 110-54-3
Methanol, analytical grade 67-56-1
12.3.3 Apparatus
12.3.3.1 Analytical balance, precision 0,1 mg
12.3.3.2 Spark-proof heating mantle/water bath
12.3.3.3 Oven, capable of maintaining a temperature of (105 ± 5) ºC
12.3.3.4 Desiccator chamber
12.3.3.5 150-ml or 250-ml glass stoppered flat bottomed flask
12.3.3.6 Soxhlet glass extractor with siphon cup
12.3.3.7 Soxhlet cellulose thimble (Whatman or equivalent)
12.3.3.8 Water-cooled glass condenser
12.3.3.9 Cotton wool
12.3.3.10 Glass volumetric flask
12.3.3.11 General volumetric glassware
12.3.3.12 Stainless steel scalpel blade

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

---------------------- Page: 14 ----------------------
EN 71-5:1993/A1:2006 (E)
12.3.3.14 Gas chromatograph with mass spectrometer detector (GC-MS)

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

thickness)
Carrier gas: Helium
Flow rate: 0,8 ml/min
Injector temperature: 290 °C
Injection volume: 2 µl
Injection type: splitless
Transfer line temperature : 280 °C
Detector scan range: 50 m/z to 550 m/z
Run time: 37 min
Oven program:
Ramp Initial Temperature Hold time Rate Final Temperature Final hold time
°C min °C/min °C min
1 60 1 10 290
2 290 5 5 320 5
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.

---------------------- Page: 15 ----------------------
EN 71-5:1993/A1:2006 (E)
Key
Y Response
X Time, in min
Mixture 1 (10 µµµµg/ml)
1. diethyl phthalate 6. di-cyclohexyl phthalate
2. di-n-butyl phthalate 7. di-n-octyl phthalate
3. di-n-hexyl phthalate 8. di-n-nonyl phthalate

4. benzyl butyl phthalate and bis(2-ethylhexyl) phthalate 9. di-n-decyl phthalate

5. di-n-heptyl phthalate
NOTE 1, 2, 4 and 6 are non-permitted substances.
Figure 1 — Total ion chromatogram of a mixture of phthalates
---------------------- Page: 16 ----------------------
EN 71-5:1993/A1:2006 (E)
Key
Y Response
X Time, in min
Mixture 2 (10 µµµµg/ml)
DBP . di-n-butyl phthalate
DEHP. benzyl butyl phthalate
BBP . bis(2-ethylhexyl) phthalate
DINP. di-iso-nonyl phthalate
Figure 2 — Total ion chromatogram of a mixture of phthalates
12.3.4 Preparation of standard solutions
12.3.4.1 Stock solutions

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

---------------------- Page: 17 ----------------------
EN 71-5:1993/A1:2006 (E)
Table 25 — Stock solutions I
Stock solution Solvent Ester Concentration
µg/ml
Phthalic acid ester 1a hexane di-isononyl phthalate (DINP) 5 000
Phthalic acid ester 1b hexane di-isodecyl phthalate (DIDP) 5 000
Table 25 (concluded)
Stock solution Solvent Ester Concentration
µg/ml
Phthalic acid ester 1c hexane bis(2-ethylhexyl) phthalate (DEHP) 500
benzyl butyl phthalate (BBP) 500
di-n-butyl phthalate (DBP) 500
di-n-hexyl phthalate (DNHP) 500
di-n-heptyl phthalate (DNHpP) 500
di-n-octyl phthalate (DNOP) 500
di-n-nonyl phthalate (DNP) 500
di-n-decyl phthalate (DDP) 500
Citric acid ester 3a hexane tributyl acetylcitrate 500
Citric acid ester 3b hexane tris(2-ethylhexyl) acetylcitrate 1 000
Alkylsulfonic acid ester hexane alkylsulfonic acid phenyl ester 5 000
Prepare stock solutions of the adipic acid polyesters dissolved in methanol.
Table 26 — Stock solutions II
Stock solution Solvent Ester Concentration
µg/ml
Adipic acid polyester 2a methanol Palamoll 632 or 636 5 000
Adipic acid polyester 2b methanol Palamoll 646 5 000
Adipic acid polyester 2c methanol Palamoll 652 5 000
Adipic acid polyester 2d methanol Palamoll 654 or 656 5 000
Adipic acid polyester 2e methanol Palamoll 858 5 000
Adipic acid polyester 2f methanol Paraplex G-40 5 000

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

12.3.4.2 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 27 shows the concentration of each analyte in the calibration solution.

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EN 71-5:1993/A1:2006 (E)
Table 27 — Calibration solutions
Concentrations
µg/ml
Stock solution Std 1 Std 2 Std 3 Std 4 Std 5
Stock solution 1a 50 125 250 375 500
Stock solution 1b 50 125 250 375 500
Stock solution 1c 10 15 20 25 30
Stock solution 3 (a) 10 15 20 25 30
Stock solution 3 (b) 50 100 150 200 250
Stock solution 4 10 15 20 25 30
12.3.4.3 Stability of standard solutions

Stability tests have shown that the plasticizer stock solutions and the calibration solutions can be stored for 6

months in a refrigerator at (4 ± 2) ºC.
12.3.5 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.

12.3.6 Sample preparation

For each sample pre-heat two flat bottomed flasks (12.3.3.5) marked A and B in an oven (12.3.3.3) 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.
12.3.7 Procedure

NOTE All safety precautions should be observed when handling chemicals and apparatus. The use of appropriate air

extraction systems should be observed.

12.3.7.1 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.
...

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