SCREENING OF PLASTIC TOYS FOR CHEMICAL COMPOSITION AND HAZARDS Market surveillance in the Netherlands

Voedsel en Waren Autoriteit

July 2005

CONTENT page 1.

INTRODUCTION 1.1. Migration from toys 1.2. Legal aspects 1.3. Previous research 1.4. Research aim

1 1 1 2 3

2.

EXPERIMENTAL 2.1. Sampling 2.2. Screening of the toys 2.3. Composition of materials 2.4. Screening of additives

4 4 4 4 4

3.

RESULTS AND DISCUSSION 3.1. Sampling 3.2. Polymer composition of the plastic toys 3.3. Migrating compounds

5 5 5 7

4.

CONCLUSIONS

15

5.

LITERATURE

16

ANNEX I: Abbreviations ANNEX II: Overview of the sampled toys ANNEX III: Overview of the additives found

VWA, report ND05o610/01, July 2005

SUMMARY and KEYWORDS Many toys for children under the age of three years are partly or totally made of plastic. In these plastics, additives are used to alter the properties of the material or to improve the production process. These additives, but also unreacted starting substances and impurities, can migrate from the plastic. As young children chew and suck frequently on their toys, they can ingest a certain amount of these compounds. In February 2005 113 samples of plastic toys were sampled to obtain an indication of the used materials and additives. Selection of the samples was based on about three criterions. The sample existed partly or entirely of plastic. In addition it was judged if whether or not it was expected that the toy would be given to children under the age of three and if it was likely that this group of children would chew and suck on the toy. The main part of the samples (73%) originated from China. Bath and teething toys were the largest group, because of the possibility of mouthing by children. Polyvinylchloride (PVC, 25%) and acrylonitril butadiene styrene co-polymer (ABS, 23%) were found frequently. PVC is often found in the soft parts of the toys, ABS in the hard parts. In addition, the polyolefines such as polyethylene (PE, 8%) en polypropylene (PP, 13%) were often found. Ethylene vinyl acetate (EVA) was found in 10% of the samples, often in the soft parts of (cooling) teething rings. Other plastics that were found are cispoly(isoprene), i.e., natural rubber, and co-polymers with styrene (except for ABS). In total 285 different migrants were found in the screening. The following groups of additives were found: monomers, oligomers, intermediates, antioxidants, compounds for dyes and inks, flame retardants, plasticisers, lubricants, UV-stabilisers and agents for vulcanisation. Several decomposition products, by -products or impurities were found also. Several (groups of) compounds can be appointed as a chemical hazard category: bisphenol A, phenol, nonylphenol, 2-ethylhexanoic acid, phthalates, plasticisers in general, nitrosamines / nitrosatable substances and primary aromatic amines, due to their toxicological profile and their frequency of occurrence. These hazard categories are eligible for further research. The diisocyanates and the styrene dimers and trimers may form a hazard also. Due to their occurrences in this screening or the limited literature available about their toxicology, it is advisable to follow the development in these groups closely, instead of performing further research. Due to the aim of the study, to give an overview of the used materials and additives in plastic toys, no actions were taken towards the producers or importers of the toys. The results of the present study will be used as an input for future market surveillances on the hazard category of chemicals mentioned before, and/or development of methods by the laboratory. It is recommended to repeat the screening in a few years to monitor shifts in used materials and additives and to follow new developments.

Keywords: Toys, chemical screening, identification, migrants

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SAMENVATTING en TREFWOORDEN Veel speelgoed voor kinderen onder de drie jaar wordt gedeeltelijk of geheel gemaakt van kunststof. In dit kunststof worden vaak additieven gebruikt om de materiaaleigenschappen te verbeteren of het productieproces te optimaliseren. Deze additieven, maar ook niet-gereageerde uitgangsstoffen en vervuilingen kunnen migreren uit het kunststof. Jonge kinderen bijten en sabbelen veel op hun speelgoed. Zo ontstaat het risico dat deze stoffen door het kind worden ingeslikt en in het lichaam worden opgenomen. In februari zijn 113 monsters plastic speelgoed bemonsterd om een indicatie te verkrijgen over de gebruikte kunststoffen en additieven. De selectie van de monsters was gebaseerd op een drietal criteria. Het monster moest gedeeltelijk of geheel bestaan uit plastic. Daarnaast werd er beoordeeld of het te verwachten was dat het speelgoed gegeven zou worden aan kinderen onder de drie jaar en of het waarschijnlijk was dat deze groep kinderen zou sabbelen op het speelgoed. Het overgrote deel van de monsters komt uit China. Bad- en bijtspeeltjes vormden de grootste groep, dit zijn speeltjes die jonge kinderen snel en veel in de mond zullen nemen. Polyvinylchloride (PVC, 25%) en acrylonitril-butadieen-styreen co-polymeer (ABS, 23%) zijn het meest gevonden. PVC werd vaak gevonden in de zachtere delen v an het speelgoed, ABS vaak in de hardere delen. Daarnaast zijn de polyolefines als polyetheen (PE, 8%) en polypropeen (PP, 13%) ook vaak gevonden. Etheen-vinyl-acetaat (EVA) werd gevonden in 10% van de monsters, vaak in de zachte delen van (koel)bijtringen. Andere kunststoffen die zijn gevonden, waren cis-poly(isopreen) (natuurlijk rubber) en co-polymeren met styreen (uitgezonderd ABS). In totaal zijn er 285 verschillende chemische stoffen gevonden tijdens de screening op gebruikte additieven. De volgende groepen stoffen werden gevonden: monomeren, oligomeren, intermediairen, antioxidanten, stoffen voor verf en inkt, brandvertragers, weekmakers, glijmiddelen, UV -stabilisatoren en stoffen voor de vulkanisatie. Daarnaast zijn er afbraakproducten, bijproducten en vervuilingen gevonden. Verschillende (groepen van) stoffen kunnen worden aangemerkt als een gevaarscategorie: bisfenol A, fenol, nonylfenol, 2-ethylhexaanzuur, ftalaten, weekmakers in het algemeen, nitrosamines / nitroseerbare verbindingen en primaire aromatische amines, allen vanwege hun toxicologische profielen en hun voorkomen. Deze risicogroepen komen in aanmerking voor verder onderzoek. Ook de diisocyanaten en de styreen dimeren en trimeren kunnen een gevaar vormen. Vanwege hun voorkomen in deze screening en de beperkte literatuur over hun toxicologisch profiel, wordt al advies gegeven de ontwikkelingen in het gebruik in speelgoed van deze twee groepen nauwlettend te volgen. Vanwege het doel van dit onderzoek, een overzicht geven van de gebruikte materialen en additieven in kunststof speelgoed en het traceren van potentieel gevaarlijke stoffen daarin, zijn geen maatregelen genomen tegen de producenten of importeurs van het speelgoed. Het resultaat zal leiden tot toekomstig onderzoek van de risicogroepen en/of ontwikkeling van methoden door het lab. Het strekt de aanbeveling om deze screening over een paar jaar te herhalen om verschuivingen in gebruikte materialen en additieven en nieuwe ontwikkelingen op te sporen. Trefwoorden: speelgoed, chemische screening, identificatie, migranten

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1. INTRODUCTION 1.1. Migration from toys The greater part of the toys sold in the Netherlands consists of plastic, either entirely (for example plastic blocks) or partly (for example the plastic head of a doll with a body made of textile). These plastics are made by the polymerisation of one or more compounds, so-called monomers. Each polymer has different properties, which can be used by the manufacture of the product. To alter the properties of a polymer or to improve the production process, additives are added to the polymer. Most of these additives do not bind to the polymer, so the possibility of migration of these additives from the plastic arises. Young children tend to mouth everything and they like to suck and chew on their toys. By doing this they can extract and ingest a certain amount of these additives. A frequently used group of additives in plastic are plasticisers. The addition of plasticisers softens the material, which makes it a better material for the pro duction of toys. The main part of soft plastic toys is made of polyvinylchloride (PVC). Pure PVC is a hard and brittle plastic. Phthalates are often used as plasticiser in PVC, but there are many substitutes that can also be used for this purpose. The amou nt of added plasticisers may rise up to 50% of the weight of the toy. Because of these high percentages a considerable amount of these plasticisers can migrate from the plastic when children suck and chew on their plastic toys. As certain phthalates have reprotoxic properties, these chemicals are considered to be a risk for children. Other additives that are used to alter the plastic or to improve the production process are for example colorants, lubricants, antioxidants and stabilisers. Besides these add itives, degradation products and by -products that are formed during undesired by -reactions are capable to migrate from the plastic. This is the case for azo-colorants and the primary aromatic amines that arise as degradation products. Quite a few primary aromatic amines are human carcinogenic. Besides additives and by -products, unreacted monomers and starting substances are capable of migration. Polyurethane (PUR) is formed by a condensation reaction between polyols and diisocyanates. These diisocyanates can migrate from PUR [5.1]. Polycarbonate (PC) consists of the monomers bisphenol A and a diphenylcarbonate. PC can contain a small amount of bisphenol A, which can migrate from the plastic [5. 2]. It is known that bisphenol A can act hormone disturbing. 1.2. Legal aspects In annex 2, part A (general requirements), paragraph 10 of the Decree on Toys (Food and Commodities Act) [5. 3] and in Directive 88/378/EEC [5.4] it is required for toys and childcare articles not to impose any danger on the child’s health or to form any danger to physical injuries by swallowing, inhalation or contact with the skin, mucous membranes or eyes, arising from the chemical composition. This means that compounds that migrate from the plastic by sucking or biting on it shall not be dangerous for the health of the child. The European Committee for Standardisation (CEN) has started the working group CEN/TC 52/WG 9. This working group has evaluated standards for several organic chemical compounds in toys [5.5]. Three standards are prepared by this workgroup concerning the risks associated with the presence of organic chemical compounds in toys: • pr EN 71-9 “Safety of toys – Part 9: Organic chemical compounds – Requirements”. In this standard requirements for the migration or content of certai n hazardous compounds from toys and toy materials are specified. [5.6] • pr EN 71-10 “Safety of toys – Part 10: Organic chemical compounds – Sample preparation and extraction procedures”. In this standard sample preparations and extraction procedures for establishing the release or content of organic compounds from toys are specified [5. 7].

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1

•

pr EN 71-11 “Safety of toys – Part 11: Organic chemical compounds – Methods of analysis”. In this standard the methods for the analysis of toys and toy materials extracts prepared according to the procedures from prEN 71-10 are specified [5.8]. These three standards should be read in conjunction with each other. The standards have passed the stage of formal vote, but have not been officially published and are consequently not referred to in the Directive 88/378/EEC [5.4]. In 1999 the EU promulgated a ban on the placing on the market of toys and childcare articles intended to be placed in the mouth by children under three years of age made of soft PVC containing one or more of the substances di-iso-nonyl phthalate (DINP), di-2-ethylhexyl phthalate (DEHP), dibutyl phthalate (DBP), di-iso-decyl phthalate (DIDP), di-n-octyl phthalate (DNOP), and butylbenzyl phthalate (BBP) [5.9]. This decision 1999/ 815/EEC applies to toys and childcare articles made of, or in part made of, soft PVC containing more than 0.1 % by weight of one or more of these phthalates. Because of the risk or the potential risk of some of the phthalates for the health of the young child it is decided to adapt this decision into Directive 76/769/EEC [5.10]. This adaptation will become valid in 2005. From that moment it will be prohibited to use more than 0.1 % by weight of DEHP, DBP and BBP in toys and childcare articles for children under the age of three years. DINP, DNOP and DIDP will be prohibited in toys and child carearticles intended to be placed in the mouth by children under three years. The limit for these phthalates will be 0.1% by weight. 1.3. Previous research Several market surveillances have been performed by the Dutch Food and Consumer Product Safety Authority / Inspectorate for Health Protection and Veterinary Public Health (VWA / KvW) to the migration of chemical compounds, mainly phthalates, from toys made or partly made of plastic. In 1999 the VWA / KvW sampled 66 toys and examined the samples for used material and release of DINP [5.11]. 34 out of 66 samples consisted of PVC. These samples were tested for the release of DINP by means of the so-called ‘Head-over-Heels method’ [5.12]. The release of DINP varied between 0,49 and 4,39 µg/min/10 cm2. In 2001 the VWA / KvW sampled 62 plastic toys. The toys were examined for amount of plasticisers [5. 13]. Several samples from the surveillance of 1999 [5. 11] were sampled again. 47 out of 62 samples (76%) consisted of plasticised PVC. DINP (79%) and DEHP (43%) were often found as plasticiser. The migration of these two plasticisers was determined. For DINP the migration varied from 0,25 to 4,85 µg/min/10 cm2, for DEHP from 0,58 to 5,22 µg/min/10 cm2. Besides phthalates, acetyl tributyl citrate (ATBC), tributyl citrate and diisononyl adipate were found. Moreover flame-retardants, lubricants, antioxidants and other compounds were found to a lesser extent. The chemical safety of the craze in the summer of 2004, the so-called ‘scoubidou’ strings has been examined by the VWA / KvW [5.14]. This research was started after questions and complaints of consumers about a certain stench that some of these strings cause. In addition Germany published reports that these strings could contain up to 30 weight percent of plasticisers. The scoubidou strings are made of plasticised PVC. 61 Different types of scoubidou strings were sampled and examined for plasticisers. DEHP was the principal plasticiser that was used in the scoubidou strings. DINP and DBP were also often found. The content of plasticisers varied from 5 to 28 weight percent. The release of DEHP varied between 0,1 and 3,2 µg/min/10 cm2. Furthermore, the release of organotin compounds was also determined. In 3 of the 61 samples dibutyltin was found in contents of 183, 544 and 608 mg/kg. The migration was determined of 2 samples and was approximately 3,8 µg/min/10 cm2. The National Institute for Public Health and the Environment (RIVM) carried out a risk assessment for the organotin compounds as well as the plasticisers.

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They concluded that the health risk for children caused by the release of the plasticisers is negligible. However, the release of dibutyltin approaches the health limit (LOAEL, lowest observed adverse effect level). The VWA / KvW also conducted five market surveillances to the chemical aspects of toys [5.15]. In one of these studies, the migration of isophorone and phenol from bath toys and other in flatable swim toys was determined. Phenol and isophorone are used as solvent for printing inks. Phenol is also used as preservative. Bath toys are often made of soft plastic. 60 Samples have been examined and no release of phenol was observed in any of the 60 toys. Isophorone was found in 50% of the toys with values from 0,02 up to 0,4 mg/L. One sample had a release of 1,12 mg/L, but even this value was much lower than the migration limit of 3 mg/L, as set in prEN71-9 [5.6]. 1.4. Research aim The aim of this screening is to get an indication of the used materials and additives in plastic toys for children under the age of three. One of the results of the present study will be to reveal trends and to appoint (groups of) additives or compounds as a risk group or a group of concern. Special attention will be paid to compounds that may have carcinogenic, mutagenic and/or reprotoxic effects. These results will lead to future market surveillance and/or development of methods.

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2. EXPERIMENTAL 2.1. Sampling Sampling took place in February 2005. A total of 113 toys were sampled that consisted entirely or partly of plastic. The toys were sampled at different locations, like baby shops, toyshops, drug stores and department stores. In total 50 different companies were inspected, all over the Netherlands. The sampling was selective; in addition to the criterion that the toy should consist of plastic, two criteria were afforded to determine whether the toy was suitable for this screening. First, it was judged whether or not it was expected that the toy would be given to children under the age of three to play with, second, if it was likely that this group of children would chew and suck on the toy. 2.2. Screening of the toys The VWA / KvW developed a method for the screening of food contact materials [5. 16]. The Food and Commodities Act (Warenwet) prescribes a large number of migration limits for food contact materials. Testing of the migration of all possible additives according to the official methods would be very labour-intensive. It is a very fast method as compared to the testing of the migration of all possible additives. This screening method is also very effective for the screening of plastic toys for used materials and additives. This screening consists of two steps; first the identification of the plastic and second the extraction of the material. This extract will be screened for the potential migrants. An estimation of the level of the migrant in the material will be made. 2.3. Composition of materials The composition of the material of the plastic toys was determined by FT-IR (Fourier Transformed Infra Red) according to Standard Operation Procedure (SOP) CHE01-ND511 [5.17]. Some of the samples consisted of different kinds of materials (or appeared to exist). In these cases sub samples were made. A circle with a diameter of 23 mm was punched out of the toy. A reflection spectrum of this material is made by means of a Perkin Elmer apparatus. Four scans have been recorded from 4000 to 450 cm -1 with a resolution of 4,0 cm-1. 2.4. Screening of additives For the screening of the migrants SOP SIG01-ND425 [5.17] was used. Approximately 300 mg of the fine dispersed materials was weighed into a tube. To this material 2 mL internal standard solution in diethyl ether was added. This internal standard solution contained 15 µg/mL dodecane. The tube was sealed and placed into an ultrasonic bath during 30 minutes. The solution was transferred to a vial, possibly after filtration. The solution was analysed with GS-MS (Gas chromatography - Mass spectrometry).

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3. RESULTS AND DISCUSSION 3.1. Sampling In Annex II, Table 4 an overview is given with the details of every sample, i.e., a description of the toy, the country of origin, age indications, and other information on the packaging with regard to the type of material used. In Figure 1 a summary is presented for the country of origin of the sampled toys. The majority of the samples (73%) were made in and imported from China. In Figure 1 it is also shown which types of toys were sampled for this screening. Bath and teething toys cover the main part because children under the age of three will play a lot with these toys. Furthermore, these toys will be mouthed a lot by this group of children.

1%

14%

5% 12%

4%

7% 13%

28%

73%

unknown

43%

EU

China

Taiwan

bath toys

teething rings

building bricks

rattles

dolls

others

Figure 1: Country of origin of the sampled toys (left part) and kind of sampled toys (right part) (n=113). 47 Of the 113 sampled toys (42%) did not have an indication of age. On 13 samples (12%) it was indicated that the toy was suitable for children from the age of 0 months. On 15 samples (13%) it was indicated that the toy was suitable for children older than three years. Nevertheless these toys are likely to be given to children younger than three years to play with, because of their appearance in morphology and colours. Therefore, these products were included also in the screening. Information on the kind of plastic or materials that were used was indicated on the packaging of 25 samples. In Annex II, Table 4, this information is given for each sample. The information on the packaging will be compared with the results of the screening. 9 Samples consisted of a combination of plastic and textile. In Table 1 these data are summarised. Table 1: Information on the packaging concerning the materials used (n=113). Number of samples Natural latex 4 Polyester 4 PP (polypropylene) 2 Others 4 No PVC (polyvinylchloride) 6 Phthalate free 8 3.2. Polymer composition of the plastic toys The materials of which the toys consisted are determined by FT-IR. In Table 2 a summary is given of the used materials in toys sampled in this screening. In Annex II, Table 4, the material composition of each sample can be found. One sample consisted of textile and this sample was not further examined.

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44 Of the remaining 112 samples consisted of two or more sub samples, because different materials were used. So, in total 186 (sub) samples were examined by FT-IR and GC-MS. In Figure 2 the used materials in toys are presented graphically. Table 2: Used materials in toys sampled for this screening. Material Amount % PVC 48 25 ABS 42 23 EVA 18 10 PVC PC 5 3 ABS PE 14 8 EVA PP 25 13 PC PUR 7 4 PE NR 6 3 PP PS 5 3 PUR Co-polymers with styrene 10 5 NR Others 6 3 PS Total 186 100

polyvinylchloride acrylonitril butadiene styrene co -polymer ethylene vinyl acetate polycarbonate polyethene polypropene polyurethane natural rubber - cis-poly(isopren e) polystyrene

PVC ABS 23%

10%

EVA

3% 8%

PC PE PP

13%

25% 3%

5%

4% 3% 3%

PUR NR PS co-polymers with styrene others

Figure 2: Used materials in the plastic toys sampled for this screening (n=186 (sub) samples). PVC and ABS were found frequently in toys sampled for this screening. PVC was often used in soft plastic toys or in the soft parts of toys. It was mainly used in bath toys. ABS was frequently found in the hard parts of the toys, for example the teething rings or rattles. ABS is a co-polymer of acrylonitrile, butadiene and styrene. The polyolefines, like PP en PE were found in 21% of the (sub) samples. EVA, also a polyolefin, was frequently found in the soft parts of the (cooling) teething rings. EVA approaches elastomeric materials, like cis-poly(isoprene (NR) with respect to softness and flexibility. These results can be compared with the results of the market surveillance on plasticisers in PVC toys of 2001 [5.13]. In 2001 47 of the 62 sampled toys (76%) consisted of plasticised PVC. Other materials found were EVA, PE, PP, SBR, polyisoprene (NR), PUR and polydimethylsiloxane. A short comment is that in 2001 specific soft plastic toys made of PVC were sampled. The results of this screening indicate that PVC is still frequently used as soft plastic. Nevertheless, other materials as polyolefines and several rubbers with styrene as monomer are developing as an alternative for PVC for soft (parts of) plastic.

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The information given on the packaging concerning the materials used is compared to the composition of material of the corresponding samples [Annex II]. In most case the information on packaging of the sample corresponded with the results obtained in this screening, as can be seen in Annex II, Table 4. Striking was that 3 out of 8 samples, of which the information on the packaging claimed that the product was phthalate free, contained one or more phthalates. 3.3. Migrating compounds In the 186 sub samples, 285 different migrating substances were found. Only the migrants with a peak height of twice the internal standard are given. In Annex III, Table 5 an overview is given of the substances that were found. In Table 3 these results are summarised. In this summary only the compounds are shown that were found three times or more. Striking or unexpected compounds that were found once or twice are also given. In the explanation below the different groups of additives and compounds will be discussed. Because of the method used in this screening, it should be emphasized that the results of this screening are just an indication of the compounds used. If possible, an indication is given of the reason or function of certain found compounds or groups of compounds and as well as the toxicity of these compounds. In this way, certain hazard categories can be appointed. Whether a compound may form a hazard or not, is based on literature and the classification in Annex I of Directive 67/548/EEG [5.18]. The trends in this screening can result in further research of certain (groups of) compounds or development of methods by the laboratory. Because of the aim of this research, to give an overview of the used materials and additives in plastic toys, no actions were taken towards the producers or importers of the toys. Table 3: Summary of compounds found in this screening (n=186 (sub) samples) Compound CAS-nr Monom ers / oligomers 1,1’-dicyano-2-methyl-4-(p-cyanophenyl)propene 1,2-diphenylcyclobutane 3018-21-1 1,6-dioxacyclododecane-7,12-dione 777-95-7 4-phenylcyclohexene 4994-16-5 ABS oligomers bisphenol A (BPA) 80-05-7 cis-1,2-diphenylcyclobutane 7694-30-6 methylene diphenyl diisocyanate 101-68-8 o-phenylenediacetonitrile 613-73-0 pentadecanenitrile 18300-91-9 PS oligomers -

Freq. Found in

trans-1,2-diphenylcyclobutane

20071-09-4 29

PS, SEBS ABS, PS EVA, PPEAA, PUR ABS ABS, ABS/PVC alloy, PMMA/PBMA, PUR PVC ABS, ABS/PVC alloy EVA, PUR ABS ABS ABS, EVA, PIPMA, PMMA/PBMA, PGA, PP, PS, PUR, PVC, SBR ABS, ABS/PVC alloy, PMMA/PBMA, PS, SBR

Alcohols 1-dodecanol 1-hexadecanol 1-nonanol 1-tetradecanol 2-ethylhexanol

112-53-8 36653-82-4 143-08-8 112-72-1 104-76-7

5 3 2 8 8

PVC PVC PVC PVC, SEBS ABS, EVA, PGA, PVC, PVC/NBR

Amides cis-9-octadecenamide (oleamide) hexadecanamide (palmitamide) o-toluene sulfonamide p-toluene sulfonamide

301-02-0 629-54-9 88-19-7 70-55-3

12 8 4 11

NR, EVA, PE, PP, PS, SBR NR, EVA, PE NR, PE, PPEAA, PUR NR, PE, PPEAA, PP, PUR, PVC

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4 3 5 13 29 5 11 2 2 1 32

7

Compound Antioxidants 2,2’-methylene-bis(6-tert-butyl-p-cresol) 2,6-di-tert-butyl-p-cresol (BHT) 3,5-di-tert-butyl-4-hydroxybenzaldehyde 4-(1,1-dimethylpropyl)-phenol 4,4’-thiobis(6-tert-butyl-m-cresol) 4-nonylphenol 4-tert-octylphenol nonylphenol isomers

CAS-nr

Freq. Found in

119-47-1 128-37-0 1620-98-0 80-46-6 96-69-5 104-40-5 140-66-9 25154-52-3

8 41 1 8 1 34 6 37

ABS, ABS/PVC alloy, NR ABS, NR, EVA, PE, PPEAA, PP, PS, PUR, PVC, SBR PP PVC EVA ABS, PIPMA, PVC, SBR PIPMA, PVC PIPMA, PVC, SBR

Compound for dyes and inks 1-(2-methoxy-1-methylethoxy)-2-propanol 1-(2-methoxypropoxy)-2-propanol 1-(phenylazo)-2-naphthalenol isophorone

20324-32-7 13429-07-7 842-07-9 78-59-1

2 3 2 5

PVC PVC ABS, PS EVA, PUR

Fatty acids and derivates 9,12-octadecadienoic acid (linoleic acid) 9-octadecenoic acid (elaidic acid) 9-octadecenoic acid (oleic acid) dodecanoic acid (lauric acid) hexadecanoic acid (palmitic acid) hexadecanoic acid (palmitic acid) butyl ester methyl 7-octadecenoate octadecanoic acid (stearic acid) octadecanoic acid (stearic acid) butyl ester palmityl oleate

60-33-3 112-79-8 112-80-1 143-07-7 57-10-3 111-06-8 28010-28-8 57-11-4 123-95-5 22393-86-8

7 5 18 9 21 5 2 10 5 6

NR, PE PVC ABS, NR, PVC ABS, NR PE, PVC ABS, ABS/PVC alloy, NR, PE, PS, PVC PVC ABS ABS, NR, PE PVC PVC

Flame retardants bis(2-ethylhexyl) hydrogen phosphite tri(2-chloroethyl)phosphate triphenyl phosphate triphenyl phosphite

3658-48-8 115-96-8 115-86-6 101-02-0

7 2 6 2

ABS, PVC EVA, PUR ABS, PS, PVC PVC

Flavour or fragrance (1R)-(+)-trans -pinane 2-phenylmethyleneoctanal 3-ethoxy-4-hydroxybenzaldehyde butyl butyrate endo-bornyl acetate methyl 3-oxo-2-pentylcyclopentaneacetate

4863-59-6 101-86-0 121-32-4 109-21-7 76-49-3 24851-98-7

1 1 1 10 1 4

PVC PVC PVC PVC PVC NR, PUR, PVC

Hydrocarbons 1-heptadecene 1-nonadecene 1-octadecene 2,2,4,6,6-pentamethylheptane 2,6,10,14-tetramethylhexadecane 2,6,11-trimethyldodecane 3,7-dimethyldecane E-5-eicosene cyclododecane cyclohexadecane

6765-39-5 18435-45-5 112-88-9 13475-82-6 638-36-8 31295-56-4 17312-54-8 74685-30-6 294-62-2 295-65-8

4 9 33 6 5 6 3 7 40 26

PVC ABS, PE, PVC ABS, NR, PE, PVC EVA, PP, PVC PE, PP, PVC PP, SEBS PP, SEBS NR, PE, PVC ABS, PIPMA, PVC ABS, ABS/PVC alloy, PE, PVC

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Compound cyclotetradecane n-docosane n-dodecane n-eicosane n-heneicosane n-heptacosane n-heptadecane n-hexadecane n-nonadecane n-octadecane n-pentadecane n-tetracosane n-tetradecane squalene

CAS-nr 295-17-0 629-97-0 112-40-3 112-95-8 629-94-7 593-49-7 629-78-7 544-76-3 629-92-5 593-45-3 629-62-9 646-31-1 629-59-4 7683-64-9

Freq. Found in 12 PPEAA, PUR, PVC 24 ABS, PE, PP, PS, PVC, SBR, SEBS 8 ABS, PP, PVC, SEBS 18 ABS, PE, PP, PS, PVC 12 PE, PP, PVC, SEBS 5 PP 20 ABS, NR, EVA, PE, PP, PS, PUR, PVC 25 NR, EVA, PE, PP, PUR, PVC 12 EVA, PE, PP, PVC 30 EVA, PE, PP, PS, PVC, SEBS 30 NR, EVA, PE, PIPMA, PP, PS, PUR, PVC, SEBS 5 PE, PP, PS, PVC 35 NR, PE, PIPMA, PP, PS, PUR, PVC, SBR, SEBS 9 NR, EVA, PE, PS, SBR

Intermediates 2-ethylhexanoic acid (2-EHA) adipic acid benzoic acid phenol p-tert-butyl benzoic acid

149-57-5 124-04-9 65-85-0 108-95-2 98-73-7

40 1 15 4 3

PIPMA, PGA, PVC PVC PVC ABS, ABS/PVC alloy, PVC PVC

17 7

PIPMA, PVC, SBR PIPMA, PVC

3 23 2 2 5 21 19 3 4 10 3 5 9 5 5 5 3 1 23 7 4 9

PIPMA, PVC PVC ABS, PVC PUR PIPMA, PVC PC, PP, PUR, PVC ABS, NR, EVA, PC, PE, PP, PVC PVC NR, EVA, PVC NR, EVA, PP, PUR, PVC, SBR NR, PUR PVC ABS, PVC NR, PVC PVC PP, PS, PVC PVC ABS PIPMA, PUR, PVC ABS, NR, EVA, PGA, PVC, PVC/NBR PGA, PVC, PVC/NBR ABS/PVC alloy, PGA, PVC, PVC/NBR

Plasticisers 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 6846-50-0 2,2,4-trimethyl-3-carboxyisopropyl pentanoic acid isobutyl ester 2-ethyl hexanoic acid butyl ester 68443-63-0 2-ethyl hexanoic acid dodecyl ester 2-ethylhexyl diphenyl phosphate 1241-94-7 benzyl butyl phthalate (BBP) 85-68-7 butyl benzoate 136-60-7 di(2-ethylhexyl) adipate (DEHA) 103-23-1 di-(2-ethylhexyl) phthalate (DEHP) 117-81-7 di(2-ethylhexyl) sebacate 122-62-3 di-(2-methylpropyl) phthalate (DMPP) 84-69-5 dibutyl phthalate (DBP) 84-74-2 diethyl phtalate 84-66-2 diisononyl phthalate (DINP) 28553-12-0 diisooctyl adipate 1330-86-5 diisooctyl phthalate (DIOP) 27554-26-3 di-n-nonyl phthalate (DNP) 84-76-4 di-n-octyl phthalate (DnOP) 117-84-0 dioctyl adipate 123-79-5 dipropyleneglycol dibenz oate 27138-31-4 oligomers of polymer plasticisers acetyl tributyl citrate (ATBC) 77-90-7 tributyl aconitate 7568-58-3 tri-n-butyl citrate 77-94-1 UV-stabilisers 1,3-diphenyl-1,3-propanedione 2-(2’-hydroxy-3’,5’-di-t-butylphenyl)-5chlorobenzotriazole benzophenone

VWA, report ND05o610/01, July 2005

120-46-7 2 3864-99-1 2

PVC ABS

119-61-9

NR, PE, PIPMA, PVC, SBR

8

9

Compound Vulcanisation 2-phenyl-2-propanol acetophenone dibenzylamine Other compounds 1-(1,1-dimethylethyl)2-methyl-1,3-propanediyl isobutyrate 2-hydroxybenzimidazole / o-phenylene urea 2-methy l-3H-benz[e]indene 3-(o-azidophenyl)propanol dehydroabietic acid di(2-ethylhexyl) ether E-15-heptadecenal

CAS-nr

Freq. Found in

617-94-7 98-86-2 103-49-1

18 10 5

ABS, ABS/PVC alloy, SEBS ABS NR

74381-40-1 10

EVA, PVC

615-16-7 2 150096-60-93 3 1740-19-8 3 10143-60-9 3 12

NR ABS PVC ABS PVC ABS, PVC

Monomers and oligomers Bisphenol A (BPA) is used as a monomer for polycarbonate (PC), but in this survey it was only found in PVC (in 5 out of 48 sub samples PVC, 10%), where it probably was used as chain-terminator to end the polymerisation of PVC or as an antioxidant for polymers or plasticisers. This compound is classified as reprotoxic category 3 according to Annex I of Directive 67/548/EEG [5. 18]. In prEN 71-9 a migration limit for bisphenol A is given of 0.1 mg/L [5.6]. Bisphenol A can therefore be considered as a hazard category. In this screening several styrene oligomers were found. These compounds are by -products in the manufacturing of PS, ABS and other polymers with styrene. PS oligomers were found 32 times, mainly in ABS, but also in several other polymers. Styrene is sometimes used as a cross-linking agent in polymers with unsaturated bindings PS oligomers are then formed as by -product. . Styrene is classified as harmful (Xn) and irritating (Xi), according to Directive 67/548/EEG [5. 18]. ABS oligomers are found 29 times, mainly in ABS polymers. In prEN 71-9 a migration limit for styrene is given of 0.75 mg/L [5. 6]. Trans- and cis-1,2-diphenylcyclobutane, two styrene dimers, were found several times, mainly in ABS, but also in PS and SBR. These and other styrene oligomers and their metabolites are suspected of having an endocrine effect [5.19], but little literature is available at the moment. The same applies for 4-phenylcyclohexene (found 13 times in ABS), a by -product formed during the polymerization of styrene-butadiene latex (like ABS). Due to their suspected endocrine effect, these styrene dimers and trimers may form a hazard. Several nitriles were found, mainly in ABS. Based on their chemic al structure and their occurrence in ABS, it is possible that these compounds are decomposition products of the polymer ABS. Methylene diphenyl diisocyanate (MDI) is classified harmful (Xn) and irritating (Xi) according to Annex I of Directive 67/548/EEG [5.18]. MDI and other isocyanates are used as a monomer in the polymerisation of polyurethane (PUR). Some of these isocyanates are classified as carcinogen category III [5. 18]. If the percentage of PUR used in toys increases, the migration of isocyanates may form a hazard. Alcohols Several so-called fatty alcohols (with an alkyl chain length varying from C 9 to C 16) were found in this screening, mainly in PVC. These alcohols are often used as che mical intermediate or as an internal lubricant. Lubricants are used to reduce adhesion and viscosity of the polymer. They can facilitate the production process of polymers, internal lubricants by providing lubrication on molecular level, between the polymer chains.

VWA, report ND05o610/01, July 2005

10

2-Ethylhexanol was found 8 times in different kinds of polymers (4 times in PVC). This compound is used as starting material for esters that can be used as plasticisers. The main part of the 2-ethylhexanol is used to produce the plasticiser DEHP, but it is also used to produce 2-ethylhexyl adipate, 2-ethylhexyl sebacate, and so on. Besides this 2-ethylhexanol is also a starting material for lubricants and other compounds. Amides o-Toluene sulfonamides and p-toluene sulfonamides were found in several polymers, 4 and 11 times respectively. Toluene sulfonamides are used in coloured lacquer layers. Further more these amides are used as an alternative for phthalate plasticisers for PVC. The so-called fatty amides are derivates of fatty acids like oleic acid (oleamide) and palmitic acid (palmitamide). These amides are used as external or internal lubricants in PVC, polyolefines and other polymers. Antioxidants Plastic generally ages rapidly after exposure to light, oxygen and heat, leading to a los s of strength, stiffness or flexibility and discoloration. Several types of antioxidants can be used to prevent this aging process, like phenolic antioxidants, organophosphorous compounds, and hindered amines. In this screening mainly hindered phenolic an tioxidants were found. Hindered phenolic antioxidants are H -donors that deactivate the radicals, which are responsible for the aging process. These phenolic antioxidants are used alone or in combination with (sometimes several) other antioxidants, for examples thioesters. 2,6-Di-tert-butyl-pcresol (BHT) was found 41 times in several polymers. Antioxidant 2246 or 2,2’-methylene-bis(6-tert-butyl-pcresol) was found 8 times, mainly in ABS. Several alkyl phenols (AP) were found during this screening. 4-(1,1-Dimethylpropyl)-phenol, 4-nonylphenol and nonylphenol isomers and 4-tert-octylphenol are the most common in this screening. These APs are used in the preparation of antioxidants (for example tris(nonylphenol) phosphate), curing agents and heat stabilisers for polymers or as antioxidant itself. In addition APs are degradation products of alkylphenol etoxylates, which are used as surfactants. Nonylphenol is classified as reprotoxic category 3, C (corrosive) and N (dangerous for the environment) according to Annex I of Directive 67/548/EEG [5. 18]. Nonylphenol may interact with the endocrine system. The oral NOAEL (no observed adverse effect level) for reproductive effects is 15 mg/kg/day [5.20]. In the market surveillance of 2001 for plasticisers in PVC toys, nonylphenol was also often found, in 13 out of 47 PVC samples (28%) [5.13]. In the present study 30 out of 48 PVC samples contained nonylphenol (63%). Because of the possibility to act hormone disturbing, the alkyl phenols and nonyl phenol in special are considered as a potential hazard category. Compounds for dyes and inks Isophorone was found 5 times in PUR and EVA. This compound is used as solvent for printing inks in bath books and it is classified as carcinogen category 3 and Xn (harmful) [5. 18]. In 2004 the VWA / KvW investigated the migration of isophorone and phenol from bath toys [5. 15, see also section 1.3]. Isophorone was found in 50% of the toys, but the values were much lower than the migration limit of 3 mg/L, as set in prEN 71-11 [5.8]. In this screening isophorone is again only found in bath books. The azo dye 1-(phenylazo)-2-naphthalenol or Sudan I was found twice in this screening. This yellow colorant is classified as carcinogen category 3 and Xn (harmful) [5. 18]. Azo dyes can form primary aromatic amines (PAA), which can be carcinogenic and/or mutagenic. 22 Of these aromatic amines are prohibited in textile and leather products. One of the priorities of the VWA/KvW is to rule out the primary aromatic amines in consumer products. A method to determine primary aromatic amines is available. This method is valid for textile, but also for plastics. VWA, report ND05o610/01, July 2005

11

Propylene glycol ethers, like 1-(2-methoxy-1-methylethoxy)-2-propanol and 1-(2-methoxypropoxy)-2-propanol are primary used as solvents in paints and inks. Fatty acids and derivates Several fatty acids and their esters were found during this screening. These compounds originate from several oils such as coconut oil (lauric acid) or palm oil (palmitic acid). These acids and their esters are used as internal lubricants. Metallic salts of fatty acids are used as stabilisers and plasticisers in the manufacturing of plastics. Flame-retardants Organic phosphates such as triphenyl phosphate (found 6 times) are used as flame-retardants. These flameretardants are added to suppress or delay the propagation of flames through the material. In addition to organic phosphates, halogenated hydrocarbons (with bromide or chloride) and inorganic compounds (with for example boron) can work as a flame-retardant. In this screening mainly phosphorous compounds were found. The phosphorus compounds are not solely used as flame -retardants. Aryl and alkyl aryl phosphates can also be used as plasticisers. Triphenyl phosphate is an example of the latter. In prEN 71-9 a migration limit for triphenyl phosphate is given of 20 µg/L [5.6], when used as plasticiser. Phosphite compounds may also be used as an antioxidant or as lubricant. Chlorinated alkyl phosphates are only used as flame-retardants. For tri(2-chloroethy l) phosphate prEN 71-9 gives a migration limit of 50 mg/kg [5. 6]. Flavour or fragrance Several compounds that are used for flavours or fragrances were found in this screening. Most of the compounds were found in sample 46981235. This sample was a liquid soap in a PVC packaging. Apparently these compounds are able to migrate in the PVC. These flavour and/or fragrance compounds are often found in nature, but nowadays often most of them are made synthetically. Butyl butyrate was found 10 times in PVC. Butyl butyrate is used as a fragrance, but it can also be used as a solvent. Hydrocarbons Hydrocarbons are compounds that consist only of a carbon (C) backbone with hydrogen (H) attached to it. Among these hydrocarbons are saturated hydrocarbons, unsaturated hydrocarbons (alkenes and alkynes) and aromatic hydrocarbons. Many alkanes with a chain length varying from C 12 toC 34 were found in this screening. These are among other things oligomers originating from poly olefines (PP and PE). Linear alkanes together with isoalkanes and cycloalkanes originate from the so-called paraffin wax. This wax is used as an external lubricant in PVC and other polymers. External lubricants help the polymer to slip over other surfaces, for example the processing equipment. Alkanes are also used as a solvent. Alkenes were also found with chain lengths varying from C 14 to C 17. These alkenes are used as starting compounds for several additives and polymers. Besides that these alkenes are formed as by -product in the olefin polymerisation. In this screening some aromatic hydrocarbons were found. These compounds are probably reaction products or decomposition products, but their origin is not clear.

VWA, report ND05o610/01, July 2005

12

Intermediates 2-Ethylhexanoic acid (2-EHA) was found 40 times, mainly in PVC. This compound is used as an intermediate for plasticisers (as DEHP and DEHA) and stabilisers. It is classified as reprotoxic category 3 [5. 18]. 2-EHA is also a known metabolite of DEHP. 2-EHA can be appointed as a hazard category. Phenol was found 4 times in ABS or PVC. It is used as an intermediate in organic synthesis, for example in the synthesis of bisphenol A and alkyl phenols (AP). It is classified as mutagen category 3 and T (toxic) [5.18]. Phenol is also used as a solvent for printing inks and preservative. In prEN 71-9 a migration limit for phenol was set at 15 mg/L [5.6]. In 2004 the VWA / KvW investigated the release of ph enol from bath toys [5.15]. No release of phenol was found during that screening. Now, only in one bath toy phenol was found, the other three samples were rattles made of hard plastic. Due to its toxicological profile, phenol can be considered as a hazard category. Benzoic acid was found 15 times in PVC. Benzoic acid is used as an intermediate for other compounds, for example dibenzoate plasticisers, which are used in PVC and polyvinylacetate. Benzoic acid is used as a preservative in the food industry, but also in non-food applications, like finger paint. The acute toxicity of benzoic acid is low, but it can cause an allergic reaction [5. 21]. Plasticisers Several types of plasticisers were found in this screening. These plasti cisers are used to make the plastic soft and flexible. They are mainly found in PVC, but also in other plastics. The main groups of plasticisers found in this screening are the adipates and the phthalates. Phthalates can be hormone -disturbing, reprotoxic or even suspected carcinogenic. Adipates and other plasticisers as citrates, esters with 2-ethylhexanoic acid or dibenzoates can be used as replacement for these phthalates. 12 Different phthalates were found, including 5 out of the 6 phthalates (DEHP, DINP, DBP, BBP and DNOP) mentioned in the Commission Decision 1999/815/EG [5. 9, see also section 1.2]. Phthalates are esters of alcohols and phthalic acid. DEHP was found in 19 different toys of which 9 times in PVC. DEHP is classified as reprotoxic category 2 and as T (toxic) [5.18]. Dibutyl phthalate (DBP) was found 10 times, in several plastics, whereas benzyl butyl phthalate (BBP) was found twice. Both compounds are classified as reprotoxic category 2 and 3, as T (toxic) and N (dangerous for the environment). Because of the potential risk of DEHP, BBP and DBP and the potential hazard of the other phthalates, this group is considered as a hazard category. Di(2-ethylhexyl) adipate (DEHA) was found 21 times, mainly in PVC. The CSTEE (Scientific Committee on Toxicity, Ecotoxicity and the Environment) has written an opinion about the toxicological characteristics and risks of certain citrates and adipates used as a substitute for phthalates [5. 22]. They state that DEHA may have the same toxicological profile as DEHP, but less potent. The most sensitive effect is the foetotoxicity with a NOAEL in the order of 30 mg/kg bw/day. With these results a TDI (tolerable daily intake) was established of 0.3 mg/kg bw. Other adipates that were found are dioctyl adipate, dihexyl adipate, diisobutyl adipate, diisononyl adipate and diisooctyl adipate. The latter was found the most, 4 times in ABS and 5 times in PVC. In this screening two citrates were found, acetyl tributyl citrate (7 times) and tri-n-butyl citrate (9 times), mainly in PVC. In the opinion of the CSTEE these two citrates were evaluated [5. 22]. For acetyl tributyl citrate (ATBC) a NOAEL of 100 mg/kg bw/day was established, but besides that the CSTEE concludes that the toxicological data was insufficient. Limited toxicological data are available for tributyl citrate. Esters with 2-ethylhexanoic acid were often found, especially the ester with dodecanol (23 times). Also 2-ethylhexyl butyrate and 2-ethylhexyl sebacate were found. The acute toxicity of the latter is low and limited data were found about carcinogenicity and reprotoxicity [5.23]. Based on the available data 2-ethylhexyl sebacate is neither considered as a carcinogen nor it has shown reprotoxic effects.

VWA, report ND05o610/01, July 2005

13

2,2,4-trimethyl-1,3-pentanediol diisobutyrate and its by -product or degradation product 2,2,4-trimethyl-3carboxyisopropyl pentanoic acid isobutyl ester were also often found. This compound has a low acute toxicity, but the long-term effects are not clear because of limited data [5. 23]. Summarizing, the health risks of plasticisers (often used as substitutes for phthalates) are not always clear, most of the time due to limited toxicological data, as in the case for the citrates, the adipates and the other plasticisers mentioned above. The level of plasticisers in plastic can amount up to 50% by weight. Thus, it makes it possible that a significant amount can leach when a child chews and sucks on their toy. For these reasons the whole group of plasticisers can be considered as a hazard category. UV-stabilisers Benzophenone and its derivatives are us ed as photo-initiator in the ultra-violet (UV) curing of inks. Furthermore, they are used as an UV-absorber. These compounds absorb the harmful UV-light that eventually changes the physical and optical properties of the polymer. The material can lose colour or fade. Besides benzophenone, benzotriazole and its derivatives are also widely used as UV-absorber. In this screening 2-(2’-hydroxy-3’,5’-di-tbutylphenyl)-5-chlorobenzotriazole and 2-(2-hydroxy-5-methyl-phenyl)benzotriazole (Drometrizole) were found. Vulcanisation During the vulcanisation process the polymer chains react with the vulcanisation agents to form a 3D network. This 3D cross linked network gives the rubber its typical elasticity, as is the case for NR (cis-poly(isoprene)), but also for ABS, SBR and SEBS. Sulphur or organic peroxides are used for this cross-linking, they react with the C=C bond in the polymer. To accelerate the process, vulcanisation accelerators are used. Dicumylperoxide is a vulcanisation agent with an average speed. As by -products acetophenone and 2-phenyl-2propanol are formed, which were both found in this screening. Acetophenone was found 10 times in ABS and 2-phenyl-2-propanol was found 18 times, mainly in ABS. Dibenzylamine was found 5 times in NR. Natural latex, gained from the rubber tree (Hevea brasiliensis), is a polymer of isoprene (2-methylbutadiene). For the vulcanisation of natural rubber accelerators (for example carbamates) are used [5.24]. Nitrosamines and nitrosatable compounds are formed as a by -product in this reaction. Dibenzylamine is a so-called nitrosatable substance, which can react with nitrogen oxides to nitrosamines, in this case N-nitrosodibenzylamine (NDBA). NDBA and other nitrosamines are (suspected) carcinogens and therefore this group of compounds can be appointed as a hazard category. Nitrosamines and nitrosatable substances are also found in latex balloons [5. 24]. Appropriate national regulations on the migration limit of nitrosamines and nitrosatable substances from balloons and labelling are expected to become valid at the end of 2005. The latex samples from this screening will be examined for nitrosamines and nitrosatable substances later this year, together with other toys made of latex. Other compounds It is very difficult to find the origin and/or the toxicity of the compounds named in this category. Some general reasons for the occurrence of these compounds, besides the function as additive, may be the decomposition of polymers, polymerisation catalysts or additives, impurities of starting materials and/or reaction products of the various additives. E-15-heptadecenal was found 12 times in PVC or ABS. The origin of this compound remains unclear and no toxicological data were found. Besides this several isobutyrate esters were found. Some esters of isobutyrate are used in the flavour and fragrance industry, but others are used as plasticisers (see plasticisers) or are decomposition products of esters of isobutyrate, which are used as plasticiser.

VWA, report ND05o610/01, July 2005

14

4. CONCLUSIONS For this screening 113 toys were sampled. The selection criterions were that these samples consisted entirely or partly of plastic and were intended for children under three years. Furthermore it was judged if it was likely that this group of children would mouth the toy. The main part of the sampled toys (73%) is made in China. Bath and teething toys cover the main part of the sampled toys. Some samples consisted of two or more sub samples, because different materials were used. A total of 186 samples was examined in this screening. The polymer composition of the toys was determined by FT-IR. PVC was used in 26% of the samples and was often found in the soft parts. ABS was found in 23% and was merely in the hard parts of the toys. The polyolefines such as PP and PE were found in 21% of the toys. Other plastics that were used are EVA, cispoly(isoprene) and copolymers with styrene (except from ABS). On average the information on the packaging corresponded with the results of the polymer composition. 3 Out of 8 samples, of which the information on the packaging claimed that the product was phthalate free, contained one or more phthalates. The samples were screened for the residual compounds and monomers by GC -MS. In total 285 different potential migrants were found. The following groups of additives were found: monomers, oligomers, intermediates, antioxidants, compounds for dyes and inks, flame retardants, plasticisers, lubricants, UV -stabilisers and agents for vulcanisation. In addition several decomposition products, by -products and impurities were found. Bisphenol A, phenol, nonylphenol, 2-ethylhexanoic acid, primary aromatic amines, phthalates and plasticisers in general can be appointed as chemical hazard categories, due to their toxicological profile and their frequency of occurrence. The nitrosamines and nitrosatable substances, which are often found in balloons, are also found in latex toys. These hazard categories will be eligible for further research. The diisocyanates and the styrene dimers and trimers may form a hazard also. Due to their occurrences in this screening or the limited literature available about their toxicology, it is advisable to follow the development in these groups closely, instead of performing research. The aim of this study was to give an overview of the used materials and additives in plastic toys. Therefore, no actions were taken towards the producers or importers of the toys. The results of the present study will be used as an input for future market surveillances that are specific for the identified chemical hazard categories, and/or development of methods by the laboratory. It is recommended to repeat the screening in a few years to monitor shifts in used materials and additives and to follow new developments.

VWA, report ND05o610/01, July 2005

15

5. LITERATURE 5.1

M.J. den Otter, K. Bouma, F.M. Nab & A.J.J. van Peursem, December 2004, Controle van kunststof verpakkingen en gebruiksartikelen voor levensmiddelen. Report ND04o042/01; VWA / Keuringsdienst van Waren Noord.

5.2

C. Bredey, P. Fjeldalz, I. Skjevraky & H. Herikstad, Increased migration levels of bisphenol A from polycarbonate baby bottl es after dishwashing, boiling and brushing. Food Additives and Contaminants, July 2003, Vol. 20, No. 7, 684–689

5.3

Warenwetbesluit Speelgoed (Warenwet) van 29 mei 1991. Staatsblad 1991, 269. Koninklijke Vermande B.V. (Lelystad)

5.4

Council Directive 88/378/EEC of 3 May 1988 on the approximation of the laws of the member states concerning the safety of toys. Official Journal L187, 16/07/1988 P.001-0013.

5.5

Final report of the work of CEN/TC 52WG 9. Risk Assessment, August 2002.

5.6

prEN 71-9 Safety of toys – part 9. Organical chemical compounds – requirements.

5.7

prEN 71-10 Safety of toys – part 10: Organical chemical compounds – sample preparation and extraction.

5.8

prEN 71-11 Safety of toys – part 11 Organical chemical compounds – methods of analysis.

5.9

Commission Decision 1999/815/EG of 7 December 1999, Official Journal, L315, 09/12/1999, page 46-49.

5.10

Council Directive 76/769/EEC of 27 July 1976 on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations. Official Journal L 262 , 27/09/1976 P. 0201 – 0203.

5.11

K. Bouma, B.A. Douwes & D.J. Schakel, February 2000, Diisononylphthalate release from PVC toys. Report NDFCM001/01; Keuringsdienst van Waren Noord.

5.12

W.H. Köneman, September 1998. Phthalate release from soft PVC baby toys, report of the Dutch Consensus Group. RIVM report 613320 002.

5.13

K. Bouma & D.J. Schakel, June 2001, Plasticisers in soft PVC toys. Report NDTOY002/01; Keuringsdienst van Waren Noord.

5.14

K. Bouma, F. Dannen, A.J.J. van Peursem, L. Steendam, C.I.H.M. Nieman, B.A. Douwes & D.J. Schakel, September 2004, Chemische veiligheid van Scoubidou touwtjes. Report ND04o061/01; VWA / Keurings dienst van Waren Noord.

5.15

K. Bouma & H.R. Reus, September 2004, Market Surveillance on toy safety. Report ND04o063/01; VWA / Keuringsdienst van Waren Noord.

5.16

D. van Battum & J.B.H. van Lierop, 1988. Testing of food contact materials in the Netherla nds. Food Additives and Contaminants, 14(6-7), 555-560.

VWA, report ND05o610/01, July 2005

16

5.17

Quality handbook of the Inspectorate for Health Protection.

5.18

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. Official Journal P 196, 16/08/1967 P. 0001 – 0098

5.19

S. Kitamura et al. March 2003, Estrogenic effect of styrene oligomers after metabolic activation by rat liver microsomes. Environmenta l Health Perspectives, 2003, 111(3), p 329-334.

5.20

European Union Risk Assessment of: 4-nonylphenol (Branched) and nonylphenol - CAS No.: 84852-153, 25154-52-3 - EINECS No.: 284-325-5, 246-672-0; 2002. (http://europa.eu.int)

5.21

Concise International Chemical Assessment Document 26, benzoic acid and sodium benzoate. World Health Organization, Geneva, 2000.

5.22

Opinion on the toxicological characteristics and risks of certain citrates and adipates used as a substitute for phthalates as plasticisers in certain soft PVC products; Scientific Committee On Toxicity, Ecotoxicity and the Environment (CSTEE), adopted on 28th of September 1999.

5.23

F. Stuer-Lauridsen, S. Mikkelsen, S. Havelund, M. Birkved & L.P. Hansen, 2001, Environmental and health assessment of alternatives to phthalates and to flexible PVC. Environmental project No. 590. Miljøprojekt.

5.24

M.J. den Otter & K. Bouma, January 2005, Migration of N -nitrosamines and N-nitrosatable substances from latex balloons. Report ND04o063/02; VWA / Keuringsdienst van Waren Noord.

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17

ANNEX I: Abbreviations List of the most used abbreviations: ABS AP ATBC BBP BHT BPA DBP DEHA DEHP DIDP DINP DNOP EVA FT-IR GC-MS LOAEL MDI NOAEL NR PBMA PE PGA PIPMA PMMA PP PPEAA PUR PVC SAN SBR SEBS TDI UV

VWA, report ND05o610/01, July 2005

acrylonitril – butadiene – styrene co-polymer alkyl phenol acetyl tributyl citrate benzyl butyl phthalate 2,6-di-tert-butyl-p-cresol bisphenol a dibutyl phthalate di(2-ethylhexyl) adipate di(2-ethylhexyl) phthalate diisodecyl phthalate diisononyl phthalate di-n-octyl phthalate ethylene vinyl acetate fourier transformed infra red gas chromatography - mass spectrometry lowest observed adverse effect level methylene diphenyl diisocyanate no observed adverse effect level natural rubber or cis-poly(isoprene) polybutylmethacrylate polyethylene polyglycolide polyisopropy lmethacrylate polymethylmethacrylate polypropene poly(propylene-ethylene-acrylic acid) polyurethane polyvinylchloride styrene – acrylonitril co-polymer styrene – butadiene rubber styrene – ethylene – butadiene – styrene co-polymer tolerable daily intake ultra violet

Annex I

VWA/KvW Noord, report ND05o610/01, July June2005 2005

ANNEX II: Overview of the sampled toys Table 4: Overview of the sampled toys (n=112) Sample 44085747 44085917 44085925

Description bricks in plastic mushroom rubber duck with noise man in car

Kind of material (packaging) PP

Age warning -

Country of origin Germany Germany

3 year + (small parts)

China

3 year + (small parts) 12 months + -

China China China China China China

44086026 duck with noise 44086034 teething key ring

-

China China

44086042 44086069 44086085 44086093 44086107

1 year +

China China Italy China China

44086115 army rubber duck 44086123 rattle and teething ring 44086131 caterpillar rattle

3 year + (small parts) 3 months + 3 months +

China China China

44086158 building bricks 44086166 ladybird with bricks

18 months + 9 months +

China France

44085933 bath hippo with little ones 44085941 44085968 44085976 44085984 44085992 44086018

3 baby toys baby doll 3 wiggle dolls ducks to string pig with noise cock with noise

blue rubber duck 8 bath toys beach toys doll with moving parts butterfly with noise

vinyl

PP holder of ABS / rubber band

Description sub sample

man car hippo little hippo big

cock feet key ring

button handle transparent plastic

ring (soft plastic) caterpillar (hard plastic)

Annex II

ladybird bricks

Material found PP PE PE PP PVC PVC ABS PVC ABS PE ABS ABS PVC / NBR ABS / PVC alloy PE PS PVC PVC PP ABS ABS PS SAN PVC ABS EVA ABS PP PP PP

VWA/KvW Noord, report ND05o610/01, July 2005

Sample 44086174 44309858 45306178

Description bath toys squirt bath toys in net rattle

Kind of material (packaging)

Age warning 3 year + (long cord) -

Country of origin China The Netherlands

45306186 (luminous) pink rubber duck 45306194 cow -rattle

3 year + (small parts) 3 months +

China China

45306216 8 bath toys 45306275 (cooling) teething ring

0 months +

China China

45306364 45306372 45306399 45306402

-

China China

45306429 magical ball

3-12 months

China

45309738 cooling teething ring

-

China

3-15 months

China

45309754 bath penguin with little ones

-

China

45309762 bath toys with fishing rod

3 year +

China

45309797 teething key ring

3 months +

China

45309819 rubber duck with sun glasses

-

China

phthalate free

rubber duck rubber duck, colour changing play ball bath dinosaur with little ones

45309746 teething ring with doll and music

polyester

Description sub sample

grip sphere blue sphere transparent cow ring soft plastic ring fish yellow fish transparent

Annex II

dinosaur little dinosaur big ring coloured ring transparent soft plastic filled with water soft plastic teething ring hard plastic teething ring ring little ring big rubber ring transparent rubber ring blue penguin little penguin big fish fishing rod key ring

Material found PVC PVC PE SBR SBR PVC ABS ABS PVC EVA PGA ABS ABS PVC PVC PVC PVC PVC ABS PC EVA PUR ABS ABS PE PVC PVC PVC PVC PE PE ABS PE PVC

VWA/KvW Noord, report ND05o610/01, July 2005

Sample Description 45309827 bath toys 45309835 teething key ring

Annex II

Age warning 0 months + 3 months +

Country of origin China China

45309843 digger with equipment

3 year + (small parts)

China

45309894 animal train with light and noise

10 months +

China

45309908 45309975 45309983 45310019 45310027 45310035 46174038 46174046 46174054 46174097 46174119 46981197

3 year + (small parts) 0 months + all ages 0 months + 3 year + 2 year + 0 months +

China China China China China China China -

46981227 pink ball with threads 46981235 soap in animal shape 46981243 (cooling) teething ring frog

5 year + (small parts) 3 months +

China China China

46981251 (cooling) teething ring fish

3 months +

China

46981278 (cooling) teething ring

4 months - 3 year

Austria

0 months + -

Spain -

building bricks rubber duck teething rings squirt bath toys rubber duck blue rubber duck pink doll bath toys in a net bath book bath book with elephant bath book with rabbit cooling teething ring

46981286 little frog 46981308 squirt shark 46981316 bath book with bear

Kind of material (packaging)

phthalate free

PVC free PVC free

natural rubber latex EVA (no PVC)

Description sub sample key ring equipment digger bottom digger wheels doll carriage

soft plastic hard plastic

soft plastic hard plastic soft plastic hard plastic soft plastic soft plastic blue hard plastic

Material found PVC PP PP PE PP PS PP ABS ABS PP ABS PS PVC PIPMA PVC SBR PVC PUR PUR EVA EVA ABS SEBS PVC EVA ABS EVA ABS EVA PP PC NR NR PE

VWA/KvW Noord, report ND05o610/01, July 2005

Sample 46981324 46981332 46981359 46981367 46981375 46981383

Description bath book with elephant bath book and bubbles blow rubber duck 8 bath toys teething ring with soft toy bath penguin with little ones

Age warning < 3 year (normal use) 0 months + -

Country of origin China Germany China China China

0 months + 3-18 months

China China

3 months +

China

3-12 months 3 months +

China China China

3 months +

China

6 months +

China

48477216 play phone with noise 48477224 teething ring with snake 48477232 teething key ring with noise

6 months + 3 months + 18 months +

China China China

48477259 cooling teething ring

0 months +

-

48477267 duck with bricks

6-18 months

China

48476953 teething ring with zebra 48476961 teething keys with noise

Kind of material (packaging) PVC free

no phthalate containing PVC

polyester PVC / phthalate free

48476988 teething ring with noise

48477119 teething ring with doll 48477127 teething ring with lion head 48477135 rattle and teething ring

polyester

48477194 play key with noise

48477208 play radio with noise

polyester

Description sub sample

penguin little penguin big butterfly music box ring cow moon ring

sphere joint little ring big ring car key coloured plastic transparent plastic

Annex II

hanger key ring soft plastic hard plastic duck yellow duck little brick

Material found EVA EVA NR PVC EVA PVC PVC PC SBR ABS ABS SBR ABS PP PE EVA PC ABS / PVC alloy PP PP ABS ABS ABS ABS ABS / PVC alloy PUR ABS PP PP EVA ABS PP PP PP

VWA/KvW Noord, report ND05o610/01, July 2005

Sample Description 48477275 rattle with monkey

Kind of material (packaging)

Age warning 6 months +

Country of origin China

48477283 teething ring with bear 48477291 rattle and teething ring

no phthalate containing PVC

0 months + 3 months +

China China

48477305 rattle and teething ring

6 months +

China

48477313 cooling teething ring

-

Switzerland

12 months + -

China China

-

-

57150378 cooling teething ring

-

China

57150386 cooling teething ring

-

China

57150394 rubber duck 57150408 squirt bath toys 57150416 bath frog with little ones

1 year + 10 months + 3 year + (small parts)

Poland Belgium China

3 months + -

China China

3 year + (small parts)

China China

48477356 48477364 48477372 57150351

bird with ball 8 bath toys teething ring with soft toy bath toys

57150424 rubber duck with a net for bath toys 57150432 bath elephant with little ones Annex II

57150459 bath book 57150467 rubber duck with little ones

textile

phthalate free

phthalate free

phthalate free

Description sub sample sucker flower ring big black ring big white ring transparent little ring coloured plastic transparent plastic soft plastic hard plastic cooling teething ring soft

yellow white blue leaf soft plastic hard plastic soft plastic hard plastic

rubber ring transparent rubber ring green bag frog elephant little elephant big duck little

Material found ABS ABS PS SEBS PP PC PP ABS ABS PPEAA PP EVA textile PVC EVA PVC PVC PVC SEBS EVA ABS EVA ABS PVC PVC PVC PVC PVC PVC PVC PIPMA PVC PUR PVC

VWA/KvW Noord, report ND05o610/01, July 2005

Sample

Description

Kind of material (packaging)

57150475 rattle 57150483 57150491 57150505 57150513 57150521

letter bricks yellow rubber ducks squeak dog bath toy cooling teething ring and rattle

57150548 57150564 57150572 57150599 57150602 57150629 57150637

3 rubber ducks knot ball cooling teething ring and rattle 2 bath frogs 2 rubber ducks little frog net with bath toys

natural rubber latex natural rubber latex

natural rubber latex

Age warning

Country of origin

3-9 months (box) 2-5 months (sticker) 6 months + 0 months + 3 months + 0 months +

Taiwan

3 year + 3 year + 3 year + 0 months + -

China China China China The Netherlands China

China The Netherlands The Netherlands China

Description sub sample duck big

teething ring sphere soft sphere hard stick ring (hard) ring (soft black) ring (soft white)

animals fishing net

Material found PVC PUR PE PVC NR NR EVA PUR ABS PMMA / PBMA PP PPEAA PP PVC SEBS PE PVC PVC NR PVC ABS

Annex II

ANNEX III: Overview of the additives found Table 5: Overview of the additives found in the sampled toys. Additives No additives found

CAS nr. -

Alcohols 1-dodecanol 1-hexadecanol 1-nonanol 1-octadecanol 1-tetradecanol

112-53-8 36653-82-4 143-08-8 112-92-5 112-72-1

Type of material EVA PC PE PP SBR SEBS textile Total

Total 2 2 2 1 1 1 1 10

PVC PVC PVC PVC PVC SEBS 104-76-7 ABS EVA PGA PVC PVC / NBR 2490-48-4 PVC 53219-21-9 PVC Total alcohols

5 3 2 1 7 1 1 1 1 4 1 1 1 29

Amides 2-fluoroimidazole-5-carboxylic acid amide cis-9-octadecenamide (oleamide)

301-02-0

hexadecanamide (palmitamide)

629-54-9

octadecenamide (stearamide) o-toluene sulfonamide

124-26-5 88-19-7

p-toluene sulfonamide

70-55-3

tetradecanamide (myristamide)

638-58-4 638-58-4

1 5 1 1 1 2 2 5 1 2 1 1 1 1 1 2 1 1 1 1 5 1 1 1 40

2-ethylhexanol

2-methyl-1-hexadecanol 2-methyl-6-methylene-2-octanol

VWA, report ND05o610/01, July 2005

PVC NR EVA PE PP PS SBR NR EVA PE EVA NR PE PPEAA PUR NR PE PPEAA PP PUR PVC NR NR EVA Total amides

Annex III

Additives Antioxidants 1-[1-(4-methylthio)hexylidene] -4-phenylcyclohexane 1-octanethiol 1-pentadecanethiol 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) 2,2'-methylene-bis(6-tert-butyl-p-cresol)

CAS nr.

ABS SBR PVC ABS ABS ABS / PVC alloy NR 2,4-di-tert-butylphenol 96-76-4 PP 2,6-di-tert-butyl-4-methylene-2,5-cyclohexadienone (BHT -quinone-methide) 2607-52-5 ABS NR 2,6-di-tert-butyl-p-cresol (BHT) 128-37-0 ABS NR EVA PE PPEAA PP PS PUR PVC SBR 2-nonylphenol 136-83-4 PVC 3,5-di-tert-butyl-4-hydroxybenzaldehyde 1620-98-0 PP 4-(1,1-dimethylpropyl)-phenol 80-46-6 PVC 4-(1-methyl-1-phenylethyl)-phenol 599-64-4 PC 4-(2,2,3,3-tetramethylbutyl)phenol 54932-78-4 PVC 4,4'-butylidenebis(6-tert-butyl-m-cresol) (SWP) 85-60-9 ABS / PVC alloy 4,4'-thiobis(6-tert-butyl-m-cresol) 96-69-5 EVA 4-[1-methyl-1-(4-phenoxyphenyl)ethyl]-phenol ABS 4-nonylphenol 104-40-5 ABS PIPMA PVC SBR 4-octylphenol 1806-26-4 PVC 4-tert-butylphenol 98-54-4 PVC 4-tert-octylphenol 140-66-9 PIPMA PVC diisopropyl phenol 2078-54-8 PE methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 32687-78-8 PUR nonylphenol isomers 25154-52-3 PIPMA PVC SBR Total antioxidants Compound for dyes and inks 1-(2-methoxy-1-methylethoxy)-2-propanol 20324-32-7 PVC 1-(2-methoxypropoxy)-2-propanol 13429-07-7 PVC 1-(phenylazo)-2-naphthalenol 842-07-9 ABS PS isophorone 78-59-1 EVA PUR Total dyes and inks

VWA, report ND05o610/01, July 2005

113035-73-7 111-88-6 25276-70-4 88-24-4 119-47-1

Type of material

Total 1 1 1 1 6 1 1 1 1 1 1 3 12 4 2 5 2 6 3 3 1 1 8 1 1 1 1 1 1 2 30 1 2 2 1 5 1 1 2 34 1 154 2 3 1 1 3 2 12

Annex III

Additives Fatty acids and derivates 11-hexadecenoic acid 9,12-octadecadienoic acid (linoleic acid)

CAS nr.

Type of material

2416-20-8 60-33-3

9-hexadecenoic acid 9-octadecenoic acid

2091-29-4 2027-47-6

9-octadecenoic acid (elaidic acid) 9-octadecenoic acid (oleic acid)

112-79-8 112-80-1

9-octadecenoic acid (oleic acid) eicosyl ester 9-octadecenoic acid (oleic acid) octadecyl ester dodecanoic acid (lauric acid)

22393-88-0 17673-49-3 143-07-7

dodecanoic acid (lauric acid) phenyl ester hexadecanoic acid (palmitic acid)

4228-00-6 57-10-3

hexadecanoic acid (palmitic acid) butyl ester hexadecanoic acid (palmitic acid) tert-butyl ester isopropyl dodecanoate (isopropyl laurate) methyl 7-octadecenoate methyl cis-9-octadecenoate methyl dodecanoate (methyl laurate) methyl hexadecanoate methyl octadecanoate octadecanoic acid (stearic acid)

111-06-8 31158-91-5 10233-13-3 28010-28-8 112-62-9 111-82-0 112-39-0 112-61-8 57-11-4

octadecanoic acid (stearic acid) 2-methylpropyl ester octadecanoic acid (stearic acid) butyl ester octadecanoic acid ethenyl ester (vinyl stearate) palmityl oleate tetradecanoic acid (myristic acid) tetradecanoic acid 1-methylethyl ester (isopropyl myristate)

646-13-9 123-95-5 111-63-7 22393-86-8 544-63-8 110-27-0

NR 1 NR 6 PE 1 NR 1 ABS 1 PVC 1 PVC 5 ABS 1 NR 2 PVC 15 PVC 2 PVC 1 ABS 1 NR 6 PE 1 PVC 1 PVC 1 ABS 10 ABS / PVC alloy 1 NR 5 PE 2 PS 1 PVC 2 PVC 5 PVC 1 NR 1 ABS 2 ABS 1 PVC 1 ABS 1 ABS 1 ABS 5 NR 4 PE 1 PVC 2 PVC 5 EVA 1 PVC 6 NR 1 PVC 1 Total fatty acids & derivates 107

Flame retardants (1-trimethylsilylethyl)diphenylphosphine oxide 1,3-dichloro-2-propanol phosphate (3:1) 9-(benzoyloxy)-9-borabicyclo[3.3.1]nonane bis(2-ethylhexyl) hydrogen phosphite

23176-47-8 13674-87-8 65212-33-1 3658-48-8

diphenyl 5-methylheptylphosphate tri(2-chloroethyl)phosphate

115-96-8

triphenyl phosphate

115-86-6

VWA, report ND05o610/01, July 2005

ABS PUR PIPMA ABS PVC PVC EVA PUR ABS PS

Total

1 1 1 1 6 1 1 1 1 1

Annex III

Additives

CAS nr.

Type of material PVC PVC Total flame retardants

Total 4 2 21

triphenyl phosphite

101-02-0

4863-59-6 475-20-7

PVC ABS

1 1

88-29-9 1222-05-5 2050-08-0 101-86-0 121-32-4 109-21-7 23986-74-5 76-49-3 10219-75-7 1135-66-6 62706-44-9 24851-98-7

PVC PVC PVC PVC PVC PVC ABS PVC ABS ABS ABS NR PUR PVC Total flavour or fragrance

1 1 1 1 1 10 1 1 1 1 1 2 1 1 26

Hydrocarbons 1,1,4,6,6-pentamethylheptyl benzene 10-methylnonadecane 11-decyldocosane 1-docosene 1-heptadecene 1-hexadecene

55134-07-1 56862-62-5 55404-55-3 1599-67-3 6765-39-5 629-73-2

1-methyldodecylbenzene 1-nonadecene

4534-53-6 18435-45-5

1-octadecene

112-88-9

1-pentadecene

13360-61-7

1-tetradecene 2,2,4,6,6-pentamethylheptane

1120-36-1 13475-82-6

2,3-dimethylnonane

02884-06-2

2,6,10,14,18-pentamethyl-2,6,10,14,18-eicosapentaene 2,6,10,14-tetramethylhexadecane

75581-03-2 638-36-8

2,6,10,14-tetramethylpentadecane

1921-70-6

ABS PIPMA PP NR PVC NR PVC PP ABS PE PVC ABS NR PE PVC PVC PVC / NBR PVC EVA PP PVC PGA PVC / NBR ABS PE PP PVC PE PP PVC

1 1 1 1 4 1 3 1 2 1 6 1 6 1 25 1 1 2 2 1 3 1 1 1 1 3 1 1 1 1

Flavour or fragrance (1R)-(+)-trans -pinane [1S-(1alpha,3abeta,4alpha,8abeta)]-decahydro-4,8,8-trimethyl-9-methylene1,4-methanoazulene (longifolene) 1,1,4,4-tetramethyl-6-ethyl-7-acetyl-1,2,3,4-tetrahydronaphthalene 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl cyclopenta[g][2]benzopyran 2-hydroxybenzoic acid pentyl ester 2-phenylmethyleneoctanal 3-ethoxy-4-hydroxybenzaldehyde butyl butyrate D-germacrene endo-bornyl acetate eremophilene isolongifolene isomaturnin methyl 3-oxo-2-pentylcyclopentaneacetate

VWA, report ND05o610/01, July 2005

Annex III

Additives 2,6,10-trimethylpentadecane

CAS nr. 3892-00-0

2,6,11-trimethyldodecane

31295-56-4

E-2-tetradecene 3,7-dimethyldecane

35953-53-8 17312-54-8

3-methylheptadecane 3-phenyldodecane 5,5-dimethyl-1,2-dipropyl-1,3-cyclopentadiene E-5-eicosene

6418-44-6 2400-00-2 74685-30-6

E-5-octadecene 5-propyl tridecane 7-pentadecyne Z-8-hexadecene cholestane cyclododecane

7206-21-5 55045-11-9 22089-89-0 481-21-0 294-62-2

cycloeicosane cyclohexadecane

296-56-0 295-65-8

cyclotetradecane

295-17-0

dodecyl benzene isomers of alkanes n-docosane

123-01-3 629-97-0

n-dodecane

112-40-3

n-dotriacontane n-eicosane

544-85-4 112-95-8

n-heneicosane

629-94-7

VWA, report ND05o610/01, July 2005

Type of material ABS PE PVC PP SEBS PUR PP SEBS PP ABS PVC NR PE PVC NR PE PVC PP ABS ABS PIPMA PVC PVC ABS ABS / PVC alloy PE PVC PPEAA PUR PVC ABS SBR ABS PE PP PS PVC SBR SEBS ABS PP PVC SEBS PVC ABS PE PP PS PVC PE PP PVC SEBS

Total 1 1 1 5 1 1 2 1 1 1 1 4 1 2 1 1 1 1 1 3 2 35 1 4 1 1 20 1 1 10 1 1 1 2 10 2 7 1 1 1 2 4 1 1 1 2 9 2 4 1 7 3 1

Annex III

Additives n-heptacosane n-heptadecane

n-hexacosane n-hexadecane

n-nonadecane

n-octadecane

n-pentacosane n-pentadecane

n-tetracosane

n-tetradecane

n-tetratriacontane n-tricosane n-tridecane

VWA, report ND05o610/01, July 2005

CAS nr. 593-49-7 629-78-7

Type of material PP ABS NR EVA PE PP PS PUR PVC 630-01-3 PP 544-76-3 NR EVA PE PP PUR PVC 629-92-5 EVA PE PP PVC 593-45-3 EVA PE PP PS PVC SEBS 629-99-2 PP 629-62-9 NR EVA PE PIPMA PP PS PUR PVC SEBS 646-31-1 PE PP PS PVC 629-59-4 NR PE PIPMA PP PS PUR PVC SBR SEBS 14167-59-0 PP 638-67-5 PP PVC 629-50-5 PS

Total 5 1 1 2 2 6 1 1 6 1 1 1 5 7 3 8 2 1 4 5 3 3 15 2 6 1 2 1 1 2 1 8 1 2 13 1 1 1 1 2 2 1 1 12 1 2 14 1 1 1 1 2 1

Annex III

Additives

CAS nr.

phenyldodecane (isomers) phenyltridecane (isomers) squalene

7683-64-9

Intermediate 2-ethyl hexanoic acid

149-57-5

PIPMA PGA PVC 603-11-2 PUR PVC 124-04-9 PVC 65-85-0 PVC 24468-13-1 PVC 108-95-2 ABS ABS / PVC alloy PVC 98-73-7 PVC Total intermediate

2 1 37 1 1 1 15 1 2 1 1 3 66

34176-91-5 PE PS SBR 3018-21-1 ABS PS 1081-75-0 PS 777-95-7 EVA PPEAA PUR 98-83-9 ABS SEBS 62788-05-0 PVC 4994-16-5 ABS ABS ABS / PVC alloy PMMA / PBMA PUR 80-05-7 PVC 7694-30-6 ABS ABS / PVC alloy 134882-04-5 ABS 2155-60-4 PGA PVC 102-09-0 PC 101-68-8 EVA PUR 613-73-0 ABS PE

1 3 1 1 2 1 1 1 3 1 1 1 13 25 2 1 1 5 10 1 1 1 1 2 1 1 2 1

3-nitrophthalic acid adipic acid benzoic acid di-2-ethylhexyl chloroformate phenol

p-tert-butyl benzoic acid Monomers / oligomers 1-(3-cyanophenyl)-2-phenylethane 1,1'-dicyano-2-methyl-4-(p-cyanophenyl)propene 1,2-diphenylcyclobutane 1,3-diphenylpropane 1,6-dioxacyclododecane-7,12-dione

2-phenylpropene 4-(4-pentylcyclohexyl)-benzonitrile 4-phenylcyclohexene ABS oligomers

bisphenol A (BPA) cis-1,2-diphenylcyclobutane cyano-4-(cyanomethyl)-benzeneacetic acid ethyl ester dibutyl itaconate diphenyl carbonate methylene diphenyl diisocyanate o-phenylenediacetonitrile p-acetylcumyl alcohol

VWA, report ND05o610/01, July 2005

Type of material PUR PVC EVA EVA NR EVA PE PS SBR Total hydrocarbons

Total 1 2 1 1 5 1 1 1 1 432

Annex III

Additives pentadecanenitrile polyester urethane oligomers PS oligomers

styrene trans-1,2-diphenylcyclobutane

trans-1,3-diphenylcyclobutane Other compounds (r)-1-[N-1-pivaloylamino-1-ethyl] naphthalene 1-(1,1-dimethylethyl)2-methyl-1,3-propanediyl isobutyrate 1-(4-bromophenyl)-3-phenyl-2-propen-1-one 1,3-diisopropyl benzene 1',4-dihydroxy-2,3'-dimethyl[1,2'-binaphthalene]-5,5',8,8'-tetrone 1,4-diisopropyl benzene 1,9-dimethyl-3,4-dihydro-b-carboline 11H-[1]benzopyrano[4,3-b]indol-6-one 13-(t-butyl)-3,3-dimethoxy-9,11,15-trimethyl-4oxatricyclo[8.5.0.0(2,6)]pentadeca-1,6,8,10,12,14-hexaen-5-one 1-ethylquinolinium iodide 1-heneicosyl formate 1-methoxy-4-octylbenzene 1-methyl-5,8-dimethoxy-1,2,3,4-tetrahydro-1,4-iminonaphthalene 1-phenyl-1,3-butanedione 2-(1-methyl-2-pyrryl)imidazoline 2-(2-butoxyethoxy)ethyl acetate 2,2-dimethyl-1-(2-hydroxy-1-isopropyl)propyl isobutyrate 2,3-dihydro-1,1,3-trimethyl-3-phenyl-1H-indene 2,4-diphenyl-4-methyl-1-pentene 2-[(4-methoxyphenyl)amino] -3,6-dioxo-1,4-cyclohexadiene-1-carboxylic acid 2-dodecyloxyethanol 2-ethyl-3-hydroxyhexyl isobutyrate 2-exo-methyl-3-methylenebenzonornornene 2-hydroxybenzimidazole / o-phenylene urea 2-methyl-3H-benz[e]indene 2-oxo-3-(2-propenyl)-cyclohexanecarboxylic acid methyl ester 2-phenoxyethanol 2-phenylthio-1-naphthalenecarbonitrile 2-propenoic acid n-pentadecyl ester

VWA, report ND05o610/01, July 2005

CAS nr. 18300-91-9 -

Type of material Total ABS 1 PUR 2 ABS 14 EVA 4 PIPMA 1 PMMA / PBMA 1 PGA 1 PP 1 PS 2 PUR 3 PVC 4 SBR 1 100-42-5 ABS 1 20071-09-4 ABS 23 ABS / PVC alloy 1 PMMA / PBMA 1 PS 3 SBR 1 25558-23-0 PS 1 Total monomers / oligomers151 PVC 74381-40-1 EVA PVC 2403-27-2 ABS 99-62-7 ABS 20175-84-2 ABS 100-18-5 ABS ABS 91622-64-9 PVC 115401-37-1 PVC

1 1 9 1 1 1 1 1 1 1

634-35-5 77899-03-7 67698-82-2 93-91-4 124-17-4 74367-33-2 3910-35-8 6362-80-7

1 1 2 1 1 1 1 1 1 1 1 2 1 1 1 2 3 1 1 1 1

92544-18-8 4536-30-5 74367-31-0 151123-60-3 615-16-7 150096-60-9 51414-47-2 122-99-6 103408-14-6 -

SAN PP PVC PVC PVC PVC SBR PVC PUR PUR PVC PVC PVC PVC PIPMA NR ABS PVC PUR ABS ABS

Annex III

Additives 2-propenoic acid n-tridecyl ester 3-(2-cyclopentenyl)-2-methyl-1,1-diphenyl-1-propene 3-(2-ethoxyethenyl)pyridine 3-(o-azidophenyl)propanol 3-benzoyl-2-t-butyl-oxazolidin-5-one 3-benzyl-4-bromo-1,2,3-triazole-1-oxide 3-benzyloxy-1,2-diacetyl-1,2-propanediol 3-chloro-tricyclo[4.3.1.13,8]undecane 3-phenyl-2-methylindole 3-pyridinecarboxylic acid 4-hydroxybenzoic acid 4-isoquinolinamine 5-fluoro-1,1,3,3-tetramethyl-1,3-dihydroisobenzofuran 8,14-dihydro-nor-salutaridine 9-hydroxypyrimido[1,6-a]pyrimidine-4-one 9-methylanthracene acetyl cedrene benzoic acid undecyl ester decyloxy benzene dehydroabietic acid di(2-ethylhexyl) ether dibenzylamine dienestrol 4-phenyl-1,2,4-triazoline-3,5-dione adduct dihydroxy-p-diisopropylbenzene dioctyl ether dodecanal E-15-heptadecenal homoandrostane methyl 3-hydrox ybenzoate methyl 4-hydroxybenzoate methyl-4,6-decadienyl ether N-[1-(4-chlorophenyl)-3-phenyl-2-propyn-1-ylidene)ethylamine octahydro-4,7-methano-1H-indene octyloxy benzene p-isopropyl acetophenone tetramethylsuccinonitrile trifluoracetic acid n-tridecyl ester tripropylene glycol Plasticisers 2,2,4-trimethyl-1,3-pentanediol diisobutyrate

2,2,4-trimethyl-3-carboxyisopropyl pentanoic acid isobutyl ester 2-ethyl hexanoic acid butyl ester 2-ethyl hexanoic acid decyl ester 2-ethyl hexanoic acid dodecyl ester 2-ethyl hexanoic acid hexadecyl ester 2-ethyl hexanoic acid tetradecyl ester 2-ethylhexyl butyrate

VWA, report ND05o610/01, July 2005

CAS nr. 13754-10-4 27011-47-8 4757-69-1 59-67-6 99-96-7 23687-25-4 15444-28-7 779-02-2 32388-55-9 35021-67-1 1740-19-8 10143-60-9 103-49-1 64490-50-2 2948-46-1 629-82-3 112-54-9 -

Type of material ABS PS PVC PVC PVC PS PE PVC ABS PVC EVA ABS PE PP PVC PS PVC PVC PUR ABS PVC NR SBR PE PGA PVC ABS PVC 54482-31-4 ABS 19438-10-9 EVA 99-76-3 EVA PVC EVA 6004-38-2 ABS 1818-07-1 PUR 645-13-6 ABS 3333-52-6 ABS PVC 24800-44-0 PVC Total other compounds

Total 1 1 1 3 1 1 1 1 1 1 2 1 1 1 1 1 1 1 1 3 3 5 1 1 1 1 6 6 1 2 1 1 1 1 1 2 1 1 1 106

6846-50-0

1 15 1 1 6 2 1 1 23 2 1 1

PIPMA PVC SBR PIPMA PVC 68443-63-0 PIPMA PVC PVC PVC PVC PVC 25415-84-3 PVC

Annex III

Additives 2-ethylhexyl diphenyl phosphate

CAS nr. 1241-94-7

benzyl butyl phthalate (BBP) butyl 2-ethylhexyl phthalate (BEHP) butyl benzoate

85-68-7 85-69-8 136-60-7

butyl methylpropyl phthalate (BMPP) di(2-ethylhexyl) adipate (DEHA)

17851-53-5 103-23-1

di-(2-ethylhexyl) phthalate (DEHP)

117-81-7

di(2-ethylhexyl) sebacate di-(2-methylpropyl) phthalate (DMPP)

122-62-3 84-69-5

dibutyl phthalate (DBP)

84-74-2

didecyl phthalate (DDcP) diethyl phtalate

84-77-5 84-66-2

dihexyl adipate diisobutyl adipate diisononyl adipate diisononyl phthalate (DINP) diisooctyl adipate

110-33-8 141-04-8 33703-08-1 28553-12-0 1330-86-5

diisooctyl phthalate (DIOP)

27554-26-3

diisopropyl phthalate (DIPP) di-n-nonyl phthalate (DNP) di-n-octyl phthalate (DnOP)

605-45-8 84-76-4 117-84-0

dioctyl adipate dipropyleneglycol dibenzoate oligomers polymer plasticisers

123-79-5 27138-31-4 -

tributyl acetylcitrate

77-90-7

VWA, report ND05o610/01, July 2005

Type of material ABS PVC PUR PVC PIPMA PVC NR PC PP PUR PVC ABS NR EVA PC PE PP PVC PVC NR EVA PVC NR EVA PP PUR PVC SBR PVC NR PUR PVC ABS PVC PVC ABS PVC NR PVC PVC PVC PP PS PVC PVC ABS PIPMA PUR PVC ABS NR EVA PGA

Total 1 1 2 1 3 2 1 1 4 2 14 2 4 1 1 1 1 9 3 1 1 2 1 3 1 2 2 1 1 2 1 1 1 2 5 4 5 1 4 2 5 1 1 3 3 1 1 3 19 1 1 1 1

Annex III

Additives

CAS nr.

tributyl aconitate

7568-58-3

tri-n-butyl citrate

77-94-1

UV-stabilisers 1,3-diphenyl-1,3-propanedione 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole 2-(2-hydroxy-5-methyl-phenyl)benzotriazole 2-hydroxy-4-octyloxy benzophenone benzophenone

120-46-7 3864-99-1 2440-22-4 1843-05-6 119-61-9

Type of material PVC PVC / NBR PGA PVC PVC / NBR ABS / PVC alloy PGA PVC PVC / NBR Total plasticisers

Total 2 1 1 2 1 1 1 6 1 209

PVC ABS PUR ABS NR PE PIPMA PVC SBR 52829-07-9 ABS Total UV-stabilisers

2 2 1 1 1 2 1 3 1 1 15

Vulcanisation 2-phenyl-2-propanol

617-94-7

acetophenone dibenzylamine

98-86-2 103-49-1

16 1 10 5 32 1405

bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate

VWA, report ND05o610/01, July 2005

ABS ABS / PVC alloy ABS NR Total vulcanisation Total

Annex III