speelgoed

SCREENING OF PLASTIC TOYS

FOR CHEMICAL COMPOSITION AND HAZARDS Market surveillance in the Netherlands Voedsel en Waren Autoriteit July 2005

VWA, report ND05o610/01, July 2005

CONTENT

page 1. INTRODUCTION 1

1.1. Migration from toys 1 1.2. Legal aspects 1 1.3. Previous research 2 1.4. Research aim 3

2. EXPERIMENTAL 4

2.1. Sampling 4 2.2. Screening of the toys 4 2.3. Composition of materials 4 2.4. Screening of additives 4

3. RESULTS AND DISCUSSION 5

3.1. Sampling 5 3.2. Polymer composition of the plastic toys 5 3.3. Migrating compounds 7

4. CONCLUSIONS 15 5. LITERATURE 16 ANNEX I: Abbreviations ANNEX II: Overview of the sampled toys ANNEX III: Overview of the additives found


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 cis-poly(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


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

VWA, report ND05o610/01, July 2005 1

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 production 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].


• 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.


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.


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).


14%

12%

73%

1%

unknown EU China Taiwan

43%

28%

5% 4% 7%13%

bath toys teething rings building bricks

rattles dolls others

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. 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.


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 PC 5 3 PE 14 8 PP 25 13 PUR 7 4 NR 6 3 PS 5 3 Co-polymers with styrene 10 5 Others 6 3 Total 186 100

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.

PVC polyvinylchloride ABS acrylonitril butadiene styrene co -polymer EVA ethylene vinyl acetate PC polycarbonate PE polyethene PP polypropene PUR polyurethane NR natural rubber - cis-poly(isopren e) PS polystyrene

25%

23% 10% 3%

8%

13%

4%3%3%5%3%

PVC

ABS

EVA

PC

PE

PP

PUR

NR

PS

co-polymers with styrene

others


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 Freq. Found in Monom ers / oligomers 1,1’-dicyano-2-methyl-4-(p-cyanophenyl)propene - 4 PS, SEBS 1,2-diphenylcyclobutane 3018-21-1 3 ABS, PS 1,6-dioxacyclododecane-7,12-dione 777-95-7 5 EVA, PPEAA, PUR 4-phenylcyclohexene 4994-16-5 13 ABS ABS oligomers - 29 ABS, ABS/PVC alloy, PMMA/PBMA, PUR bisphenol A (BPA) 80-05-7 5 PVC cis-1,2-diphenylcyclobutane 7694-30-6 11 ABS, ABS/PVC alloy methylene diphenyl diisocyanate 101-68-8 2 EVA, PUR o-phenylenediacetonitrile 613-73-0 2 ABS pentadecanenitrile 18300-91-9 1 ABS PS oligomers - 32 ABS, EVA, PIPMA, PMMA/PBMA, PGA, PP, PS, PUR,

PVC, SBR trans-1,2-diphenylcyclobutane 20071-09-4 29 ABS, ABS/PVC alloy, PMMA/PBMA, PS, SBR Alcohols 1-dodecanol 112-53-8 5 PVC 1-hexadecanol 36653-82-4 3 PVC 1-nonanol 143-08-8 2 PVC 1-tetradecanol 112-72-1 8 PVC, SEBS 2-ethylhexanol 104-76-7 8 ABS, EVA, PGA, PVC, PVC/NBR Amides cis-9-octadecenamide (oleamide) 301-02-0 12 NR, EVA, PE, PP, PS, SBR hexadecanamide (palmitamide) 629-54-9 8 NR, EVA, PE o-toluene sulfonamide 88-19-7 4 NR, PE, PPEAA, PUR p-toluene sulfonamide 70-55-3 11 NR, PE, PPEAA, PP, PUR, PVC


Compound CAS-nr Freq. Found in Antioxidants 2,2’-methylene-bis(6-tert-butyl-p-cresol) 119-47-1 8 ABS, ABS/PVC alloy, NR 2,6-di-tert-butyl-p-cresol (BHT) 128-37-0 41 ABS, NR, EVA, PE, PPEAA, PP, PS, PUR, PVC, SBR 3,5-di-tert-butyl-4-hydroxybenzaldehyde 1620-98-0 1 PP 4-(1,1-dimethylpropyl)-phenol 80-46-6 8 PVC 4,4’-thiobis(6-tert-butyl-m-cresol) 96-69-5 1 EVA 4-nonylphenol 104-40-5 34 ABS, PIPMA, PVC, SBR 4-tert-octylphenol 140-66-9 6 PIPMA, PVC nonylphenol isomers 25154-52-3 37 PIPMA, PVC, SBR Compound for dyes and inks 1-(2-methoxy-1-methylethoxy)-2-propanol 20324-32-7 2 PVC 1-(2-methoxypropoxy)-2-propanol 13429-07-7 3 PVC 1-(phenylazo)-2-naphthalenol 842-07-9 2 ABS, PS isophorone 78-59-1 5 EVA, PUR Fatty acids and derivates 9,12-octadecadienoic acid (linoleic acid) 60-33-3 7 NR, PE 9-octadecenoic acid (elaidic acid) 112-79-8 5 PVC 9-octadecenoic acid (oleic acid) 112-80-1 18 ABS, NR, PVC dodecanoic acid (lauric acid) 143-07-7 9 ABS, NR PE, PVC hexadecanoic acid (palmitic acid) 57-10-3 21 ABS, ABS/PVC alloy, NR, PE, PS, PVC hexadecanoic acid (palmitic acid) butyl ester 111-06-8 5 PVC methyl 7-octadecenoate 28010-28-8 2 ABS octadecanoic acid (stearic acid) 57-11-4 10 ABS, NR, PE octadecanoic acid (stearic acid) butyl ester 123-95-5 5 PVC palmityl oleate 22393-86-8 6 PVC Flame retardants bis(2-ethylhexyl) hydrogen phosphite 3658-48-8 7 ABS, PVC tri(2-chloroethyl)phosphate 115-96-8 2 EVA, PUR triphenyl phosphate 115-86-6 6 ABS, PS, PVC triphenyl phosphite 101-02-0 2 PVC Flavour or fragrance (1R)-(+)-trans -pinane 4863-59-6 1 PVC 2-phenylmethyleneoctanal 101-86-0 1 PVC 3-ethoxy-4-hydroxybenzaldehyde 121-32-4 1 PVC butyl butyrate 109-21-7 10 PVC endo-bornyl acetate 76-49-3 1 PVC methyl 3-oxo-2-pentylcyclopentaneacetate 24851-98-7 4 NR, PUR, PVC Hydrocarbons 1-heptadecene 6765-39-5 4 PVC 1-nonadecene 18435-45-5 9 ABS, PE, PVC 1-octadecene 112-88-9 33 ABS, NR, PE, PVC 2,2,4,6,6-pentamethylheptane 13475-82-6 6 EVA, PP, PVC 2,6,10,14-tetramethylhexadecane 638-36-8 5 PE, PP, PVC 2,6,11-trimethyldodecane 31295-56-4 6 PP, SEBS 3,7-dimethyldecane 17312-54-8 3 PP, SEBS E-5-eicosene 74685-30-6 7 NR, PE, PVC cyclododecane 294-62-2 40 ABS, PIPMA, PVC cyclohexadecane 295-65-8 26 ABS, ABS/PVC alloy, PE, PVC


Compound CAS-nr Freq. Found in cyclotetradecane 295-17-0 12 PPEAA, PUR, PVC n-docosane 629-97-0 24 ABS, PE, PP, PS, PVC, SBR, SEBS n-dodecane 112-40-3 8 ABS, PP, PVC, SEBS n-eicosane 112-95-8 18 ABS, PE, PP, PS, PVC n-heneicosane 629-94-7 12 PE, PP, PVC, SEBS n-heptacosane 593-49-7 5 PP n-heptadecane 629-78-7 20 ABS, NR, EVA, PE, PP, PS, PUR, PVC n-hexadecane 544-76-3 25 NR, EVA, PE, PP, PUR, PVC n-nonadecane 629-92-5 12 EVA, PE, PP, PVC n-octadecane 593-45-3 30 EVA, PE, PP, PS, PVC, SEBS n-pentadecane 629-62-9 30 NR, EVA, PE, PIPMA, PP, PS, PUR, PVC, SEBS n-tetracosane 646-31-1 5 PE, PP, PS, PVC n-tetradecane 629-59-4 35 NR, PE, PIPMA, PP, PS, PUR, PVC, SBR, SEBS squalene 7683-64-9 9 NR, EVA, PE, PS, SBR Intermediates 2-ethylhexanoic acid (2-EHA) 149-57-5 40 PIPMA, PGA, PVC adipic acid 124-04-9 1 PVC benzoic acid 65-85-0 15 PVC phenol 108-95-2 4 ABS, ABS/PVC alloy, PVC p-tert-butyl benzoic acid 98-73-7 3 PVC Plasticisers 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 6846-50-0 17 PIPMA, PVC, SBR 2,2,4-trimethyl-3-carboxyisopropyl pentanoic acid isobutyl ester

- 7 PIPMA, PVC

2-ethyl hexanoic acid butyl ester 68443-63-0 3 PIPMA, PVC 2-ethyl hexanoic acid dodecyl ester - 23 PVC 2-ethylhexyl diphenyl phosphate 1241-94-7 2 ABS, PVC benzyl butyl phthalate (BBP) 85-68-7 2 PUR butyl benzoate 136-60-7 5 PIPMA, PVC di(2-ethylhexyl) adipate (DEHA) 103-23-1 21 PC, PP, PUR, PVC di-(2-ethylhexyl) phthalate (DEHP) 117-81-7 19 ABS, NR, EVA, PC, PE, PP, PVC di(2-ethylhexyl) sebacate 122-62-3 3 PVC di-(2-methylpropyl) phthalate (DMPP) 84-69-5 4 NR, EVA, PVC dibutyl phthalate (DBP) 84-74-2 10 NR, EVA, PP, PUR, PVC, SBR diethyl phtalate 84-66-2 3 NR, PUR diisononyl phthalate (DINP) 28553-12-0 5 PVC diisooctyl adipate 1330-86-5 9 ABS, PVC diisooctyl phthalate (DIOP) 27554-26-3 5 NR, PVC di-n-nonyl phthalate (DNP) 84-76-4 5 PVC di-n-octyl phthalate (DnOP) 117-84-0 5 PP, PS, PVC dioctyl adipate 123-79-5 3 PVC dipropyleneglycol dibenz oate 27138-31-4 1 ABS oligomers of polymer plasticisers - 23 PIPMA, PUR, PVC acetyl tributyl citrate (ATBC) 77-90-7 7 ABS, NR, EVA, PGA, PVC, PVC/NBR tributyl aconitate 7568-58-3 4 PGA, PVC, PVC/NBR tri-n-butyl citrate 77-94-1 9 ABS/PVC alloy, PGA, PVC, PVC/NBR UV-stabilisers 1,3-diphenyl-1,3-propanedione 120-46-7 2 PVC 2-(2’-hydroxy-3’,5’-di-t-butylphenyl)-5-chlorobenzotriazole

3864-99-1 2 ABS

benzophenone 119-61-9 8 NR, PE, PIPMA, PVC, SBR


Compound CAS-nr Freq. Found in Vulcanisation 2-phenyl-2-propanol 617-94-7 18 ABS, ABS/PVC alloy, SEBS acetophenone 98-86-2 10 ABS dibenzylamine 103-49-1 5 NR Other compounds 1-(1,1-dimethylethyl)2-methyl-1,3-propanediyl isobutyrate

74381-40-1 10 EVA, PVC

2-hydroxybenzimidazole / o-phenylene urea 615-16-7 2 NR 2-methy l-3H-benz[e]indene 150096-60-93 ABS 3-(o-azidophenyl)propanol - 3 PVC dehydroabietic acid 1740-19-8 3 ABS di(2-ethylhexyl) ether 10143-60-9 3 PVC E-15-heptadecenal - 12 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 C16) 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.


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-p-cresol (BHT) was found 41 times in several polymers. Antioxidant 2246 or 2,2’-methylene-bis(6-tert-butyl-p-cresol) 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.


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 flame-retardants 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 toC34 were found in this screening. These are among other things oligomers originating from polyolefines (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 C17. 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.


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.


2,2,4-trimethyl-1,3-pentanediol diisobutyrate and its by -product or degradation product 2,2,4-trimethyl-3-carboxyisopropyl 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 used 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-t-butylphenyl)-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-2-propanol 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.


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, cis-poly(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.


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.


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.: 84852-15-

3, 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.

VWA, report ND05o610/01, July 2005 Annex I

ANNEX I: Abbreviations List of the most used abbreviations: ABS acrylonitril – butadiene – styrene co-polymer AP alkyl phenol ATBC acetyl tributyl citrate BBP benzyl butyl phthalate BHT 2,6-di-tert-butyl-p-cresol BPA bisphenol a DBP dibutyl phthalate DEHA di(2-ethylhexyl) adipate DEHP di(2-ethylhexyl) phthalate DIDP diisodecyl phthalate DINP diisononyl phthalate DNOP di-n-octyl phthalate EVA ethylene vinyl acetate FT-IR fourier transformed infra red GC-MS gas chromatography - mass spectrometry LOAEL lowest observed adverse effect level MDI methylene diphenyl diisocyanate NOAEL no observed adverse effect level NR natural rubber or cis-poly(isoprene) PBMA polybutylmethacrylate PE polyethylene PGA polyglycolide PIPMA polyisopropy lmethacrylate PMMA polymethylmethacrylate PP polypropene PPEAA poly(propylene-ethylene-acrylic acid) PUR polyurethane PVC polyvinylchloride SAN styrene – acrylonitril co-polymer SBR styrene – butadiene rubber SEBS styrene – ethylene – butadiene – styrene co-polymer TDI tolerable daily intake UV ultra violet

ANNEX II: Overview of the sampled toys Table 4: Overview of the sampled toys (n=112) Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found 44085747 bricks in plastic mushroom PP - - PP 44085917 rubber duck with noise - Germany PE 44085925 man in car - Germany man PE car PP 44085933 bath hippo with little ones 3 year + (small parts) China hippo little PVC hippo big PVC 44085941 3 baby toys - China ABS 44085968 baby doll vinyl 3 year + (small parts) China PVC 44085976 3 wiggle dolls 12 months + China ABS 44085984 ducks to string - China PE 44085992 pig with noise - China ABS 44086018 cock with noise - China cock ABS feet PVC / NBR 44086026 duck with noise - China ABS / PVC alloy 44086034 teething key ring - China key PE ring PS 44086042 blue rubber duck - China PVC 44086069 8 bath toys - China PVC 44086085 beach toys PP - Italy PP 44086093 doll with moving parts holder of ABS / rubber band - China ABS 44086107 butterfly with noise 1 year + China button ABS handle PS transparent plastic SAN 44086115 army rubber duck 3 year + (small parts) China PVC 44086123 rattle and teething ring 3 months + China ABS 44086131 caterpillar rattle 3 months + China ring (soft plastic) EVA caterpillar (hard plastic) ABS 44086158 building bricks 18 months + China PP 44086166 ladybird with bricks 9 months + France ladybird PP bricks PP

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Annex II VW

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

Annex II

Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found 44086174 bath toys - China PVC 44309858 squirt bath toys in net phthalate free 3 year + (long cord) - PVC 45306178 rattle - The Netherlands grip PE sphere blue SBR sphere transparent SBR 45306186 (luminous) pink rubber duck 3 year + (small parts) China PVC 45306194 cow -rattle 3 months + China cow ABS ring ABS 45306216 8 bath toys - China PVC 45306275 (cooling) teething ring 0 months + China soft plastic EVA ring PGA fish yellow ABS fish transparent ABS 45306364 rubber duck - - PVC 45306372 rubber duck, colour changing - China PVC 45306399 play ball - - PVC 45306402 bath dinosaur with little ones - China dinosaur little PVC dinosaur big PVC 45306429 magical ball 3-12 months China ring coloured ABS ring transparent PC 45309738 cooling teething ring - China soft plastic filled with water EVA soft plastic teething ring PUR hard plastic teething ring ABS 45309746 teething ring with doll and music polyester 3-15 months China ring little ABS ring big PE 45309754 bath penguin with little ones - China rubber ring transparent PVC rubber ring blue PVC penguin little PVC penguin big PVC 45309762 bath toys with fishing rod 3 year + China fish PE fishing rod PE 45309797 teething key ring 3 months + China key ABS ring PE 45309819 rubber duck with sun glasses - China PVC

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Annex II

Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found 45309827 bath toys 0 months + China PVC 45309835 teething key ring 3 months + China key PP ring PP 45309843 digger with equipment 3 year + (small parts) China equipment PE digger PP bottom digger PS wheels PP 45309894 animal train with light and noise 10 months + China doll ABS carriage ABS 45309908 building bricks 3 year + (small parts) China PP 45309975 rubber duck 0 months + China ABS 45309983 teething rings - - PS 45310019 squirt bath toys all ages China PVC 45310027 rubber duck phthalate free - China PIPMA 45310035 blue rubber duck - China PVC 46174038 pink doll 0 months + China SBR 46174046 bath toys in a net 3 year + China PVC 46174054 bath book PVC free - - PUR 46174097 bath book with elephant 2 year + - PUR 46174119 bath book with rabbit PVC free - - EVA 46981197 cooling teething ring 0 months + - soft plastic EVA hard plastic ABS 46981227 pink ball with threads 5 year + (small parts) China SEBS 46981235 soap in animal shape - China PVC 46981243 (cooling) teething ring frog 3 months + China soft plastic EVA hard plastic ABS 46981251 (cooling) teething ring fish 3 months + China soft plastic EVA hard plastic ABS 46981278 (cooling) teething ring 4 months - 3 year Austria soft plastic EVA soft plastic blue PP hard plastic PC 46981286 little frog natural rubber latex 0 months + - NR 46981308 squirt shark - Spain NR 46981316 bath book with bear EVA (no PVC) - - PE

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Annex II

Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found 46981324 bath book with elephant PVC free - - EVA 46981332 bath book and bubbles blow < 3 year (normal use) China EVA 46981359 rubber duck - Germany NR 46981367 8 bath toys - China PVC 46981375 teething ring with soft toy no phthalate containing PVC 0 months + China EVA 46981383 bath penguin with little ones - China penguin little PVC penguin big PVC 48476953 teething ring with zebra polyester 0 months + China PC 48476961 teething keys with noise PVC / phthalate free 3-18 months China butterfly SBR music box ABS ring ABS 48476988 teething ring with noise 3 months + China cow SBR moon ABS ring PP 48477119 teething ring with doll 3-12 months China PE 48477127 teething ring with lion head polyester - China EVA 48477135 rattle and teething ring 3 months + China sphere PC joint ABS / PVC alloy 48477194 play key with noise 3 months + China little ring PP big ring PP car ABS key ABS 48477208 play radio with noise polyester 6 months + China coloured plastic ABS transparent plastic ABS 48477216 play phone with noise 6 months + China ABS / PVC alloy 48477224 teething ring with snake 3 months + China PUR 48477232 teething key ring with noise 18 months + China hanger ABS key PP ring PP 48477259 cooling teething ring 0 months + - soft plastic EVA hard plastic ABS 48477267 duck with bricks 6-18 months China duck yellow PP duck little PP brick PP

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Annex II

Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found 48477275 rattle with monkey 6 months + China sucker ABS flower ABS 48477283 teething ring with bear no phthalate containing PVC 0 months + China PS 48477291 rattle and teething ring 3 months + China ring big black SEBS ring big white PP ring transparent PC little ring PP 48477305 rattle and teething ring 6 months + China coloured plastic ABS transparent plastic ABS 48477313 cooling teething ring - Switzerland soft plastic PPEAA hard plastic PP cooling teething ring soft EVA 48477356 bird with ball textile 12 months + China textile 48477364 8 bath toys - China PVC 48477372 teething ring with soft toy EVA 57150351 bath toys - - yellow PVC white PVC blue PVC 57150378 cooling teething ring - China leaf SEBS soft plastic EVA hard plastic ABS 57150386 cooling teething ring - China soft plastic EVA hard plastic ABS 57150394 rubber duck 1 year + Poland PVC 57150408 squirt bath toys 10 months + Belgium PVC 57150416 bath frog with little ones phthalate free 3 year + (small parts) China rubber ring transparent PVC rubber ring green PVC bag PVC frog PVC 57150424 rubber duck with a net for bath toys phthalate free 3 months + China PVC 57150432 bath elephant with little ones - China elephant little PIPMA elephant big PVC 57150459 bath book - China PUR 57150467 rubber duck with little ones phthalate free 3 year + (small parts) China duck little PVC

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Annex II

Sample Description Kind of material (packaging) Age warning Country of origin Description sub sample Material found duck big PVC 57150475 rattle 3-9 months (box)

2-5 months (sticker) Taiwan PUR

57150483 letter bricks - - PE 57150491 yellow rubber ducks 6 months + China PVC 57150505 squeak dog natural rubber latex 0 months + The Netherlands NR 57150513 bath toy natural rubber latex 3 months + The Netherlands NR 57150521 cooling teething ring and rattle 0 months + China teething ring EVA sphere soft PUR sphere hard ABS stick PMMA / PBMA ring (hard) PP ring (soft black) PPEAA ring (soft white) PP 57150548 3 rubber ducks - China PVC 57150564 knot ball 3 year + China SEBS 57150572 cooling teething ring and rattle - - PE 57150599 2 bath frogs 3 year + China PVC 57150602 2 rubber ducks 3 year + China PVC 57150629 little frog natural rubber latex 0 months + The Netherlands NR 57150637 net with bath toys - China animals PVC fishing net ABS

VWA/KvW


Annex II

VWA, report ND05o610/01, July 2005 Annex III

ANNEX III: Overview of the additives found Table 5: Overview of the additives found in the sampled toys. Additives CAS nr. Type of material TotalNo additives found - EVA 2 PC 2 PE 2 PP 1 SBR 1 SEBS 1 textile 1 Total 10 Alcohols 1-dodecanol 112-53-8 PVC 5 1-hexadecanol 36653-82-4 PVC 3 1-nonanol 143-08-8 PVC 2 1-octadecanol 112-92-5 PVC 1 1-tetradecanol 112-72-1 PVC 7 SEBS 1 2-ethylhexanol 104-76-7 ABS 1 EVA 1 PGA 1 PVC 4 PVC / NBR 1 2-methyl-1-hexadecanol 2490-48-4 PVC 1 2-methyl-6-methylene-2-octanol 53219-21-9 PVC 1 Total alcohols 29 Amides 2-fluoroimidazole-5-carboxylic acid amide - PVC 1 cis-9-octadecenamide (oleamide) 301-02-0 NR 5 EVA 1 PE 1 PP 1 PS 2 SBR 2 hexadecanamide (palmitamide) 629-54-9 NR 5 EVA 1 PE 2 octadecenamide (stearamide) 124-26-5 EVA 1 o-toluene sulfonamide 88-19-7 NR 1 PE 1 PPEAA 1 PUR 1 p-toluene sulfonamide 70-55-3 NR 2 PE 1 PPEAA 1 PP 1 PUR 1 PVC 5 tetradecanamide (myristamide) 638-58-4 NR 1 638-58-4 NR 1 EVA 1 Total amides 40


Additives CAS nr. Type of material TotalAntioxidants 1-[1-(4-methylthio)hexylidene] -4-phenylcyclohexane 113035-73-7 ABS 1 1-octanethiol 111-88-6 SBR 1 1-pentadecanethiol 25276-70-4 PVC 1 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) 88-24-4 ABS 1 2,2'-methylene-bis(6-tert-butyl-p-cresol) 119-47-1 ABS 6 ABS / PVC alloy 1 NR 1 2,4-di-tert-butylphenol 96-76-4 PP 1 2,6-di-tert-butyl-4-methylene-2,5-cyclohexadienone (BHT -quinone-methide) 2607-52-5 ABS 1 NR 1 2,6-di-tert-butyl-p-cresol (BHT) 128-37-0 ABS 1 NR 3 EVA 12 PE 4 PPEAA 2 PP 5 PS 2 PUR 6 PVC 3 SBR 3 2-nonylphenol 136-83-4 PVC 1 3,5-di-tert-butyl-4-hydroxybenzaldehyde 1620-98-0 PP 1 4-(1,1-dimethylpropyl)-phenol 80-46-6 PVC 8 4-(1-methyl-1-phenylethyl)-phenol 599-64-4 PC 1 4-(2,2,3,3-tetramethylbutyl)phenol 54932-78-4 PVC 1 4,4'-butylidenebis(6-tert-butyl-m-cresol) (SWP) 85-60-9 ABS / PVC alloy 1 4,4'-thiobis(6-tert-butyl-m-cresol) 96-69-5 EVA 1 4-[1-methyl-1-(4-phenoxyphenyl)ethyl] -phenol - ABS 1 4-nonylphenol 104-40-5 ABS 1 PIPMA 2 PVC 30 SBR 1 4-octylphenol 1806-26-4 PVC 2 4-tert-butylphenol 98-54-4 PVC 2 4-tert-octylphenol 140-66-9 PIPMA 1 PVC 5 diisopropyl phenol 2078-54-8 PE 1 methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 32687-78-8 PUR 1 nonylphenol isomers 25154-52-3 PIPMA 2 PVC 34 SBR 1 Total antioxidants 154 Compound for dyes and inks 1-(2-methoxy-1-methylethoxy)-2-propanol 20324-32-7 PVC 2 1-(2-methoxypropoxy)-2-propanol 13429-07-7 PVC 3 1-(phenylazo)-2-naphthalenol 842-07-9 ABS 1 PS 1 isophorone 78-59-1 EVA 3 PUR 2 Total dyes and inks 12


Additives CAS nr. Type of material TotalFatty acids and derivates 11-hexadecenoic acid 2416-20-8 NR 1 9,12-octadecadienoic acid (linoleic acid) 60-33-3 NR 6 PE 1 9-hexadecenoic acid 2091-29-4 NR 1 9-octadecenoic acid 2027-47-6 ABS 1 PVC 1 9-octadecenoic acid (elaidic acid) 112-79-8 PVC 5 9-octadecenoic acid (oleic acid) 112-80-1 ABS 1 NR 2 PVC 15 9-octadecenoic acid (oleic acid) eicosyl ester 22393-88-0 PVC 2 9-octadecenoic acid (oleic acid) octadecyl ester 17673-49-3 PVC 1 dodecanoic acid (lauric acid) 143-07-7 ABS 1 NR 6 PE 1 PVC 1 dodecanoic acid (lauric acid) phenyl ester 4228-00-6 PVC 1 hexadecanoic acid (palmitic acid) 57-10-3 ABS 10 ABS / PVC alloy 1 NR 5 PE 2 PS 1 PVC 2 hexadecanoic acid (palmitic acid) butyl ester 111-06-8 PVC 5 hexadecanoic acid (palmitic acid) tert-butyl ester 31158-91-5 PVC 1 isopropyl dodecanoate (isopropyl laurate) 10233-13-3 NR 1 methyl 7-octadecenoate 28010-28-8 ABS 2 methyl cis-9-octadecenoate 112-62-9 ABS 1 methyl dodecanoate (methyl laurate) 111-82-0 PVC 1 methyl hexadecanoate 112-39-0 ABS 1 methyl octadecanoate 112-61-8 ABS 1 octadecanoic acid (stearic acid) 57-11-4 ABS 5 NR 4 PE 1 octadecanoic acid (stearic acid) 2-methylpropyl ester 646-13-9 PVC 2 octadecanoic acid (stearic acid) butyl ester 123-95-5 PVC 5 octadecanoic acid ethenyl ester (vinyl stearate) 111-63-7 EVA 1 palmityl oleate 22393-86-8 PVC 6 tetradecanoic acid (myristic acid) 544-63-8 NR 1 tetradecanoic acid 1-methylethyl ester (isopropyl myristate) 110-27-0 PVC 1 Total fatty acids & derivates 107 Flame retardants (1-trimethylsilylethyl)diphenylphosphine oxide 23176-47-8 ABS 1 1,3-dichloro-2-propanol phosphate (3:1) 13674-87-8 PUR 1 9-(benzoyloxy)-9-borabicyclo[3.3.1]nonane 65212-33-1 PIPMA 1 bis(2-ethylhexyl) hydrogen phosphite 3658-48-8 ABS 1 PVC 6 diphenyl 5-methylheptylphosphate - PVC 1 tri(2-chloroethyl)phosphate 115-96-8 EVA 1 PUR 1 triphenyl phosphate 115-86-6 ABS 1 PS 1


Additives CAS nr. Type of material Total PVC 4 triphenyl phosphite 101-02-0 PVC 2 Total flame retardants 21 Flavour or fragrance (1R)-(+)-trans -pinane 4863-59-6 PVC 1 [1S-(1alpha,3abeta,4alpha,8abeta)]-decahydro-4,8,8-trimethyl-9-methylene-1,4-methanoazulene (longifolene)

475-20-7 ABS 1

1,1,4,4-tetramethyl-6-ethyl-7-acetyl-1,2,3,4-tetrahydronaphthalene 88-29-9 PVC 1 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl cyclopenta[g][2]benzopyran 1222-05-5 PVC 1 2-hydroxybenzoic acid pentyl ester 2050-08-0 PVC 1 2-phenylmethyleneoctanal 101-86-0 PVC 1 3-ethoxy-4-hydroxybenzaldehyde 121-32-4 PVC 1 butyl butyrate 109-21-7 PVC 10 D-germacrene 23986-74-5 ABS 1 endo-bornyl acetate 76-49-3 PVC 1 eremophilene 10219-75-7 ABS 1 isolongifolene 1135-66-6 ABS 1 isomaturnin 62706-44-9 ABS 1 methyl 3-oxo-2-pentylcyclopentaneacetate 24851-98-7 NR 2 PUR 1 PVC 1 Total flavour or fragrance 26 Hydrocarbons 1,1,4,6,6-pentamethylheptyl benzene 55134-07-1 ABS 1 10-methylnonadecane 56862-62-5 PIPMA 1 11-decyldocosane 55404-55-3 PP 1 1-docosene 1599-67-3 NR 1 1-heptadecene 6765-39-5 PVC 4 1-hexadecene 629-73-2 NR 1 PVC 3 1-methyldodecylbenzene 4534-53-6 PP 1 1-nonadecene 18435-45-5 ABS 2 PE 1 PVC 6 1-octadecene 112-88-9 ABS 1 NR 6 PE 1 PVC 25 1-pentadecene 13360-61-7 PVC 1 PVC / NBR 1 1-tetradecene 1120-36-1 PVC 2 2,2,4,6,6-pentamethylheptane 13475-82-6 EVA 2 PP 1 PVC 3 2,3-dimethylnonane 02884-06-2 PGA 1 PVC / NBR 1 2,6,10,14,18-pentamethyl-2,6,10,14,18-eicosapentaene 75581-03-2 ABS 1 2,6,10,14-tetramethylhexadecane 638-36-8 PE 1 PP 3 PVC 1 2,6,10,14-tetramethylpentadecane 1921-70-6 PE 1 PP 1 PVC 1


Additives CAS nr. Type of material Total2,6,10-trimethylpentadecane 3892-00-0 ABS 1 PE 1 PVC 1 2,6,11-trimethyldodecane 31295-56-4 PP 5 SEBS 1 E-2-tetradecene 35953-53-8 PUR 1 3,7-dimethyldecane 17312-54-8 PP 2 SEBS 1 3-methylheptadecane 6418-44-6 PP 1 3-phenyldodecane 2400-00-2 ABS 1 5,5-dimethyl-1,2-dipropyl-1,3-cyclopentadiene - PVC 1 E-5-eicosene 74685-30-6 NR 4 PE 1 PVC 2 E-5-octadecene 7206-21-5 NR 1 5-propyl tridecane 55045-11-9 PE 1 7-pentadecyne 22089-89-0 PVC 1 Z-8-hexadecene - PP 1 cholestane 481-21-0 ABS 1 cyclododecane 294-62-2 ABS 3 PIPMA 2 PVC 35 cycloeicosane 296-56-0 PVC 1 cyclohexadecane 295-65-8 ABS 4 ABS / PVC alloy 1 PE 1 PVC 20 cyclotetradecane 295-17-0 PPEAA 1 PUR 1 PVC 10 dodecyl benzene 123-01-3 ABS 1 isomers of alkanes - SBR 1 n-docosane 629-97-0 ABS 1 PE 2 PP 10 PS 2 PVC 7 SBR 1 SEBS 1 n-dodecane 112-40-3 ABS 1 PP 2 PVC 4 SEBS 1 n-dotriacontane 544-85-4 PVC 1 n-eicosane 112-95-8 ABS 1 PE 2 PP 9 PS 2 PVC 4 n-heneicosane 629-94-7 PE 1 PP 7 PVC 3 SEBS 1


Additives CAS nr. Type of material Totaln-heptacosane 593-49-7 PP 5 n-heptadecane 629-78-7 ABS 1 NR 1 EVA 2 PE 2 PP 6 PS 1 PUR 1 PVC 6 n-hexacosane 630-01-3 PP 1 n-hexadecane 544-76-3 NR 1 EVA 1 PE 5 PP 7 PUR 3 PVC 8 n-nonadecane 629-92-5 EVA 2 PE 1 PP 4 PVC 5 n-octadecane 593-45-3 EVA 3 PE 3 PP 15 PS 2 PVC 6 SEBS 1 n-pentacosane 629-99-2 PP 2 n-pentadecane 629-62-9 NR 1 EVA 1 PE 2 PIPMA 1 PP 8 PS 1 PUR 2 PVC 13 SEBS 1 n-tetracosane 646-31-1 PE 1 PP 1 PS 1 PVC 2 n-tetradecane 629-59-4 NR 2 PE 1 PIPMA 1 PP 12 PS 1 PUR 2 PVC 14 SBR 1 SEBS 1 n-tetratriacontane 14167-59-0 PP 1 n-tricosane 638-67-5 PP 1 PVC 2 n-tridecane 629-50-5 PS 1


Additives CAS nr. Type of material Total PUR 1 PVC 2 phenyldodecane (isomers) - EVA 1 phenyltridecane (isomers) - EVA 1 squalene 7683-64-9 NR 5 EVA 1 PE 1 PS 1 SBR 1 Total hydrocarbons 432 Intermediate 2-ethyl hexanoic acid 149-57-5 PIPMA 2 PGA 1 PVC 37 3-nitrophthalic acid 603-11-2 PUR 1 PVC 1 adipic acid 124-04-9 PVC 1 benzoic acid 65-85-0 PVC 15 di-2-ethylhexyl chloroformate 24468-13-1 PVC 1 phenol 108-95-2 ABS 2 ABS / PVC alloy 1 PVC 1 p-tert-butyl benzoic acid 98-73-7 PVC 3 Total intermediate 66 Monomers / oligomers 1-(3-cyanophenyl)-2-phenylethane 34176-91-5 PE 1 1,1'-dicyano-2-methyl-4-(p-cyanophenyl)propene - PS 3 SBR 1 1,2-diphenylcyclobutane 3018-21-1 ABS 1 PS 2 1,3-diphenylpropane 1081-75-0 PS 1 1,6-dioxacyclododecane-7,12-dione 777-95-7 EVA 1 PPEAA 1 PUR 3 2-phenylpropene 98-83-9 ABS 1 SEBS 1 4-(4-pentylcyclohexyl)-benzonitrile 62788-05-0 PVC 1 4-phenylcyclohexene 4994-16-5 ABS 13 ABS oligomers - ABS 25 ABS / PVC alloy 2 PMMA / PBMA 1 PUR 1 bisphenol A (BPA) 80-05-7 PVC 5 cis-1,2-diphenylcyclobutane 7694-30-6 ABS 10 ABS / PVC alloy 1 cyano-4-(cyanomethyl)-benzeneacetic acid ethyl ester 134882-04-5 ABS 1 dibutyl itaconate 2155-60-4 PGA 1 PVC 1 diphenyl carbonate 102-09-0 PC 2 methylene diphenyl diisocyanate 101-68-8 EVA 1 PUR 1 o-phenylenediacetonitrile 613-73-0 ABS 2 p-acetylcumyl alcohol - PE 1


Additives CAS nr. Type of material Totalpentadecanenitrile 18300-91-9 ABS 1 polyester urethane oligomers - PUR 2 PS oligomers - ABS 14 EVA 4 PIPMA 1 PMMA / PBMA 1 PGA 1 PP 1 PS 2 PUR 3 PVC 4 SBR 1 styrene 100-42-5 ABS 1 trans-1,2-diphenylcyclobutane 20071-09-4 ABS 23 ABS / PVC alloy 1 PMMA / PBMA 1 PS 3 SBR 1 trans-1,3-diphenylcyclobutane 25558-23-0 PS 1 Total monomers / oligomers151 Other compounds (r)-1-[N-1-pivaloylamino-1-ethyl] naphthalene - PVC 1 1-(1,1-dimethylethyl)2-methyl-1,3-propanediyl isobutyrate 74381-40-1 EVA 1 PVC 9 1-(4-bromophenyl)-3-phenyl-2-propen-1-one 2403-27-2 ABS 1 1,3-diisopropyl benzene 99-62-7 ABS 1 1',4-dihydroxy-2,3'-dimethyl[1,2'-binaphthalene] -5,5',8,8'-tetrone 20175-84-2 ABS 1 1,4-diisopropyl benzene 100-18-5 ABS 1 1,9-dimethyl-3,4-dihydro-b-carboline - ABS 1 11H-[1]benzopyrano[4,3-b]indol-6-one 91622-64-9 PVC 1 13-(t-butyl)-3,3-dimethoxy-9,11,15-trimethyl-4-oxatricyclo[8.5.0.0(2,6)]pentadeca-1,6,8,10,12,14-hexaen-5-one

115401-37-1 PVC 1

1-ethylquinolinium iodide 634-35-5 SAN 1 1-heneicosyl formate 77899-03-7 PP 1 1-methoxy-4-octylbenzene 67698-82-2 PVC 2 1-methyl-5,8-dimethoxy-1,2,3,4-tetrahydro-1,4-iminonaphthalene - PVC 1 1-phenyl-1,3-butanedione 93-91-4 PVC 1 2-(1-methyl-2-pyrryl)imidazoline - PVC 1 2-(2-butoxyethoxy)ethyl acetate 124-17-4 SBR 1 2,2-dimethyl-1-(2-hydroxy-1-isopropyl)propyl isobutyrate 74367-33-2 PVC 1 2,3-dihydro-1,1,3-trimethyl-3-phenyl-1H-indene 3910-35-8 PUR 1 2,4-diphenyl-4-methyl-1-pentene 6362-80-7 PUR 1 PVC 1 2-[(4-methoxyphenyl)amino] -3,6-dioxo-1,4-cyclohexadiene-1-carboxylic acid 92544-18-8 PVC 2 2-dodecyloxyethanol 4536-30-5 PVC 1 2-ethyl-3-hydroxyhexyl isobutyrate 74367-31-0 PVC 1 2-exo-methyl-3-methylenebenzonornornene 151123-60-3 PIPMA 1 2-hydroxybenzimidazole / o-phenylene urea 615-16-7 NR 2 2-methyl-3H-benz[e]indene 150096-60-9 ABS 3 2-oxo-3-(2-propenyl)-cyclohexanecarboxylic acid methyl ester 51414-47-2 PVC 1 2-phenoxyethanol 122-99-6 PUR 1 2-phenylthio-1-naphthalenecarbonitrile 103408-14-6 ABS 1 2-propenoic acid n-pentadecyl ester - ABS 1


Additives CAS nr. Type of material Total2-propenoic acid n-tridecyl ester - ABS 1 3-(2-cyclopentenyl)-2-methyl-1,1-diphenyl-1-propene - PS 1 3-(2-ethoxyethenyl)pyridine - PVC 1 3-(o-azidophenyl)propanol - PVC 3 3-benzoyl-2-t-butyl-oxazolidin-5-one - PVC 1 3-benzyl-4-bromo-1,2,3-triazole-1-oxide - PS 1 3-benzyloxy-1,2-diacetyl-1,2-propanediol 13754-10-4 PE 1 3-chloro-tricyclo[4.3.1.13,8]undecane 27011-47-8 PVC 1 3-phenyl-2-methylindole 4757-69-1 ABS 1 3-pyridinecarboxylic acid 59-67-6 PVC 1 4-hydroxybenzoic acid 99-96-7 EVA 2 4-isoquinolinamine 23687-25-4 ABS 1 5-fluoro-1,1,3,3-tetramethyl-1,3-dihydroisobenzofuran - PE 1 8,14-dihydro-nor-salutaridine 15444-28-7 PP 1 9-hydroxypyrimido[1,6-a]pyrimidine-4-one - PVC 1 9-methylanthracene 779-02-2 PS 1 acetyl cedrene 32388-55-9 PVC 1 benzoic acid undecyl ester - PVC 1 decyloxy benzene 35021-67-1 PUR 1 dehydroabietic acid 1740-19-8 ABS 3 di(2-ethylhexyl) ether 10143-60-9 PVC 3 dibenzylamine 103-49-1 NR 5 dienestrol 4-phenyl-1,2,4-triazoline-3,5-dione adduct 64490-50-2 SBR 1 dihydroxy-p-diisopropylbenzene 2948-46-1 PE 1 dioctyl ether 629-82-3 PGA 1 dodecanal 112-54-9 PVC 1 E-15-heptadecenal - ABS 6 PVC 6 homoandrostane 54482-31-4 ABS 1 methyl 3-hydrox ybenzoate 19438-10-9 EVA 2 methyl 4-hydroxybenzoate 99-76-3 EVA 1 methyl-4,6-decadienyl ether - PVC 1 N-[1-(4-chlorophenyl)-3-phenyl-2-propyn-1-ylidene)ethylamine - EVA 1 octahydro-4,7-methano-1H-indene 6004-38-2 ABS 1 octyloxy benzene 1818-07-1 PUR 1 p-isopropyl acetophenone 645-13-6 ABS 2 tetramethylsuccinonitrile 3333-52-6 ABS 1 trifluoracetic acid n-tridecyl ester - PVC 1 tripropylene glycol 24800-44-0 PVC 1 Total other compounds 106 Plasticisers 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 6846-50-0 PIPMA 1 PVC 15 SBR 1 2,2,4-trimethyl-3-carboxyisopropyl pentanoic acid isobutyl ester - PIPMA 1 PVC 6 2-ethyl hexanoic acid butyl ester 68443-63-0 PIPMA 2 PVC 1 2-ethyl hexanoic acid decyl ester - PVC 1 2-ethyl hexanoic acid dodecyl ester - PVC 23 2-ethyl hexanoic acid hexadecyl ester - PVC 2 2-ethyl hexanoic acid tetradecyl ester - PVC 1 2-ethylhexyl butyrate 25415-84-3 PVC 1


Additives CAS nr. Type of material Total2-ethylhexyl diphenyl phosphate 1241-94-7 ABS 1 PVC 1 benzyl butyl phthalate (BBP) 85-68-7 PUR 2 butyl 2-ethylhexyl phthalate (BEHP) 85-69-8 PVC 1 butyl benzoate 136-60-7 PIPMA 3 PVC 2 butyl methylpropyl phthalate (BMPP) 17851-53-5 NR 1 di(2-ethylhexyl) adipate (DEHA) 103-23-1 PC 1 PP 4 PUR 2 PVC 14 di-(2-ethylhexyl) phthalate (DEHP) 117-81-7 ABS 2 NR 4 EVA 1 PC 1 PE 1 PP 1 PVC 9 di(2-ethylhexyl) sebacate 122-62-3 PVC 3 di-(2-methylpropyl) phthalate (DMPP) 84-69-5 NR 1 EVA 1 PVC 2 dibutyl phthalate (DBP) 84-74-2 NR 1 EVA 3 PP 1 PUR 2 PVC 2 SBR 1 didecyl phthalate (DDcP) 84-77-5 PVC 1 diethyl phtalate 84-66-2 NR 2 PUR 1 dihexyl adipate 110-33-8 PVC 1 diisobutyl adipate 141-04-8 ABS 1 diisononyl adipate 33703-08-1 PVC 2 diisononyl phthalate (DINP) 28553-12-0 PVC 5 diisooctyl adipate 1330-86-5 ABS 4 PVC 5 diisooctyl phthalate (DIOP) 27554-26-3 NR 1 PVC 4 diisopropyl phthalate (DIPP) 605-45-8 PVC 2 di-n-nonyl phthalate (DNP) 84-76-4 PVC 5 di-n-octyl phthalate (DnOP) 117-84-0 PP 1 PS 1 PVC 3 dioctyl adipate 123-79-5 PVC 3 dipropyleneglycol dibenzoate 27138-31-4 ABS 1 oligomers polymer plasticisers - PIPMA 1 PUR 3 PVC 19 tributyl acetylcitrate 77-90-7 ABS 1 NR 1 EVA 1 PGA 1


Additives CAS nr. Type of material Total PVC 2 PVC / NBR 1 tributyl aconitate 7568-58-3 PGA 1 PVC 2 PVC / NBR 1 tri-n-butyl citrate 77-94-1 ABS / PVC alloy 1 PGA 1 PVC 6 PVC / NBR 1 Total plasticisers 209 UV-stabilisers 1,3-diphenyl-1,3-propanedione 120-46-7 PVC 2 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole 3864-99-1 ABS 2 2-(2-hydroxy-5-methyl-phenyl)benzotriazole 2440-22-4 PUR 1 2-hydroxy-4-octyloxy benzophenone 1843-05-6 ABS 1 benzophenone 119-61-9 NR 1 PE 2 PIPMA 1 PVC 3 SBR 1 bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate 52829-07-9 ABS 1 Total UV-stabilisers 15 Vulcanisation 2-phenyl-2-propanol 617-94-7 ABS 16 ABS / PVC alloy 1 acetophenone 98-86-2 ABS 10 dibenzylamine 103-49-1 NR 5 Total vulcanisation 32 Total 1405

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