EN 71-5:1993/A1:2006

SLOVENSKI STANDARD
01-marec-2006
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Safety of toys - Part 5: Chemical toys (sets) other than experimental sets - Amendment
A1
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
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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.

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

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.
Add under "Introduction",
st
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
th
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.
st
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"
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
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
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.
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
nm
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)
m
W ×10000
where
M is the content of the metal in the sample, in mass-%;
m
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)
m
W ×10000
where
M is the content of the metal in the sample, in mass-%;
m
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.
m
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).
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
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).
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.
a
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
a
Polymeric plasticizer derived from adipic acid and polyhydric alcohols.
b
Polyester adipate.
NOTE  Trade names for adipic acid polyesters are examples for those types of plasticizers.

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)
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.

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

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.
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.
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.
Reflux gently for 6 h ± 30 min.
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.
12.3.7.2 Extraction of adipic acid polyesters
Repeat 12.3.7.1 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.
12.3.7.3 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 has evaporated, transfer the flasks A and B to an oven (12.3.3.3) 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.
12.3.7.4 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 12.3.6 (omitting the sample and extraction steps) and
12.3.7.1. 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.
12.3.7.5 GC-MSD determination of phthalic acid esters, citric acid esters and alkylsulfonic acid
esters
After completing weighing as described in 12.3.7.1 add (50 ± 2) ml of hexane to flask A.
Stopper flask A and swirl the hexane to completely dissolve the plasticizer 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 plasticizer present.
Transfer a portion of the hexane into a capped vial for GC-MS analysis (conditions as described in 12.3.3.14).
Compare the obtained GC-MS spectra to known spectra or ester standards to allow qualitative identification of
plasticizers 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.
12.3.7.6 ATR-FT-IR identification of adipic acid polyesters
After completing weighing as described in 12.3.7.2 add (50 ± 2) ml of methanol to flask B.
Stopper flask B and swirl the methanol to completely dissolve the plasticizer 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.
12.3.8 Evaluation of Results
12.3.8.1 Calculation of solvent-extractable content containing plasticizers
12.3.8.1.1 Content of hexane extractable material , in % (m/m), identified as phthalic, citric and
alkylsulfonic acid esters by GC-MS
W −W
A+E A
M = ×100 (16)
Hexane
W
S
where
M is the content of hexane extractable material, in % (m/m);
Hexane
W is the mass of flask A and extract, in g;
A+E
W  is the mass of flask A, in g;
A
W  is the mass of sample, in g.
S
12.3.8.1.2 ) Content of methanol extractable material , in % (m/m), identified as adipic acid polyester
by ATR-FT-IR
W −W
B+E B
M = ×100 (17)
Methanol
W
S
where
M is the content of methanol extractable material, in % (m/m);
Methanol
W is the mass of flask B and extract, in g;
B+E
W  is the mass of flask B, in g;
B
W  is the mass of sample, in g.
S
12.3.8.1.3 Content of combined (hexane + methanol) extractable material % (m/m)
M = (16) + (17) (18)
te+p
where
M is the content of total extractable material content including plasticizer, in % (m/m).
te+p
NOTE Values for combined (hexane + methanol) extractable material content < 30 % will not require further
characterisation of individual plasticizers and should be reported as % (m/m) total extractable material content if it can be
shown that only plasticizers in Table 17 are used.
12.3.8.2 Calculation and identification of plasticizer content by GC-MS analysis
12.3.8.2.1 Identification of plasticizers
Record the plasticizers identified according to 12.3.7.5 and 12.3.7.6.
12.3.8.2.2 Calculation of plasticizers content by GC-MS
12.3.8.2.2.1 Content of phthalic acid ester, in % (m/m), by GC-MS
c ×250(ml)× f
e1
M = (19)
PAE
W ×10000
S
where
M is the phthalic acid ester content, in % (m/m);
PAE
c  is the concentration of extract solution, in µg/ml;
e1
f  is the dilution factor;
W  is the mass of sample, in g.
S
c = (W ) −W (20)
e1 A+E A
where
c  is the concentration of extract solution, in µg/ml;
e1
W is the mass of flask A and extract, in g;
A+E
W  is the mass of flask A, in g.
A
12.3.8.2.2.2 Content of citric acid ester, in % (m/m), by GC-MS
c ×250(ml)× f
e2
M = (21)
CAE
W ×10000
S
where
M is the citric acid ester content, in % (m/m);
CAE
c  is the concentration of extract solution, in µg/ml;
e2
f  is the dilution factor;
W  is the mass of sample, in g.
S
c = (W ) −W (22)
e2 B +E B
where
c  is the concentration of extract solution, in µg/ml;
e2
W is the mass of flask B and extract, in g;
B+E
W  is the mass of flask B, in g.
B
12.3.8.2.2.3 % (m/m) Alkylsulfonic acid ester content by GC-MS
c ×250(ml)× f
e
M = (23)
AAE
W ×10000
S
where
M is the alkylsulfonic acid ester content, in % (m/m);
AAE
c  is the concentration of extract solution, in µg/ml;
e
f  is the dilution factor;
W  is the mass of sample, in g.
S
12.3.9 Test report
The test report shall contain 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:
- identified plasticizers;
- content of hexane extractable material , in % (m/m);
- content of methanol extractable material identified as adipic acid polyester by ATR-FT-IR, in % (m/m);
- content of combined (hexane + methanol) extractable material, in % (m/m);
- content of phthalic acid ester by GC-MS, in % (m/m);
- content of citric acid ester by GC-MS, in % (m/m);
- alkylsulfonic acid ester content by GC-MS; in % (m/m);
d) any deviation from the test procedure specified;
e) date of test.
12.4 Determination of the emission of benzene, toluene and xylenes from oven hardening
plasticised PVC modelling sets and plastic moulding sets
12.4.1 Principle
The determination of the emission of benzene, toluene and xylenes from oven-hardening plasticised PVC
modelling 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.
12.4.2 Standards and reagents
Table 28 — Standards
Chemical CAS No.
Toluene 108-88-3
Benzene 71-43-2
o-Xylene 95-47-6
m-Xylene 108-38-3
p-Xylene 106-42-3
Table 29 — Solvents
Chemical CAS No.
Methanol 67-56-1
NOTE Alternatively a high boiling solvent such as
dodecane (free of the compounds to be analysed) may be used
instead of methanol in order to reduce the vapour pressure in
the head space vial. This is especially relevant when the head
space vial is not pressurized (see headspace conditions
12.4.3.2).
12.4.3 Apparatus
12.4.3.1 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 ), 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

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
NOTE Other conditions may be used, provided they give better or comparable results.
Carrier gas: Helium
Ramp Initial temperature Hold time Rate Final temperature Final hold time
°C min °C/min °C min
1 35 10 7 150
2 150 0 20 220 6
Solvent Typical retention time Solvent Typical retention time
min min
benzene 3,4 m-xylene 10,5
toluene 5,6 o-xylene 12,3
Detector conditions for benzene, toluene and xylenes determination:
Quantification ions   Main target ion m/z
Benzene     78
Toluene     91
Xylenes     91
12.4.3.2 Headspace analysis conditions
Balanced-pressure system (the vial pressurized 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 pressurized 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).
Pressurization 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
Pressurization time: 4 min
Thermostatting time: 30 min
Withdrawal time: 0,2 min
12.4.3.3 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.
12.4.3.3.1 Analytical balance, precision 0,1 mg
12.4.3.3.2 Refrigerator, capable of maintaining a temperature of (4 ± 2) ºC
12.4.3.3.3 Brown glass vials for headspace sampling
12.4.3.3.4 Volumetric glass pipettes, 0,5 ml, 1 ml, 2 ml, 10 ml and 20 ml capacity
12.4.3.3.5 Brown glass volumetric flasks, 10 ml, 20 ml, 50 ml and 100 ml capacity
12.4.3.3.6 Syringe, 1 000 µl capacity
12.4.4 Preparation of standard solutions
Weigh accurately approximately 100 mg of each standard (benzene, toluene, m-, p-, o-xylene) and 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 (12.4.3.3.3 and 12.4.3.3.5) at (4 ± 2) ºC. The stock standard
solution shall be used within one month. The standard solutions shall be freshly prepared.
12.4.5 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.
12.4.6 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 (12.4.4) 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.
12.4.7 Procedure
Prior to injection, heat each test portion in the head space GC system for exactly 30 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 12.4.3.1.
12.4.8 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.
12.4.9 Test report
The test report shall contain, as a minimum, the following:
f) type and identification of the product and/ or material tested;
g) a reference to this European Standard;
h) the results of the tests expressed as:
benzene emitted from PVC or polystyrene, in mg/kg;
toluene emitted from PVC or polystyrene, in mg/kg;
xylene emitted from PVC or polystyrene, in mg/kg;
i) any deviation from the test procedure specified;
j) date of test.
12.4.10 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 exactly 30 min for every test portion. The temperature of the
headspace thermostatting compartment is needed to be controlled to exactly 130 ºC for PVC based modelling
clays and 180 ºC for polystyrene granules.
The septum of the headspace vial shall have no influence on the result (inertness, no emissions, no
adsorption).
12.5 Determination of styrene content in polystyrene granules
12.5.1 Principle
The amoun
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