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Introduction to EN 71 Part 9 – 11

EN 71-9:2005 + A1:2007 Organic Chemical Compounds – Requirements

EN 71-10:2005 Organic Chemical Compounds – Sample Preparation and Extraction

EN 71-11:2005 Organic Chemical Compounds – Method of Analysis

The Toy(s) Safety Directive states that toys must not present a health hazard by ingestion, inhalation, skin or mucous membrane contact.

In the past, the only standard used to assess these risks has been EN71 part 3. However, Part 3 is limited in that it only considers risks presented by 8 heavy elements through ingestion.

The EN71 Part 9 – 11 address this limitation by evaluating the risks from certain organic chemicals through all possible contact routes.

Requirements of EN 71-9:2005 + A1:2007

The following Table summarizes the requirements of EN 71-9:2005 + A1:2007

     Types of toys covered under EN71-9:2005 + A1:2007

      (1) Toys intended to be mouthed by children under 3 years of age;

      (2) (3) (4) Toys, or their accessible components, with a mass of 150g or less intended to be played with in the

                        hands by children under 3 years of age;

      (5) (6) Toys or their accessible components intended for children under 3 years of age;

      (7) (8) (9) Mouthpiece components of mouth-actuated toys

      (10) Inflatable toys with a surface greater than 0.5m² when fully inflated;

      (11) (12) (13) Toys worn over the mouth or nose;

      (14) (15) Toys which the child can enter;

      (16) Components of graphic instruments sold as toys or used in toys;

      (17) Wooden toys (and their accessible components) for indoor use;

      (18) Wooden toys (and their accessible components) for outdoor use;

      (19) Toys and components of toys which mimic food;

      (20) Solid toy materials intended to leave a trace;

      (21) Coloured accessible liquids in toys;

      (22) Non-coloured accessible liquids in toys;

      (23) Modelling clay, play clay and similar, except those chemical toys addressed by EN71- 5;  

      (24) Balloon-making compounds;

      (25) Imitation tattoos with adhesive;

      (26) Imitation jewellery

a = excluding polymeric coatings with a thickness of less than 500 μm

Testing in accordance with EN 71-9:2005 + A1:2007

Depending on the types of toys, one or more of the following substance(s) will be addressed:

Flame retardants

Colourants

Primary aromatic amines

Monomers

Solvents-migration

Solvents-inhalation

Wood preservatives

Preservatives

Plasticisers

Textile materials

EN 71-9 has requirements controlling the presence of certain colourants; primary aromatic amines and volatile solvents in textile materials used in particular types of toys.  For toys intended for children less than 3 years of age containing accessible textile components there are also requirements for two flame retardants and formaldehyde (see 4.3.1 of EN 71-9).

Fabrics commonly used by the toy industry include Velboa, Brushed Tricot, Velour and Microfleece:

  Velboa – a soft, medium weight, short-pile textile with a velvety feel

  Brushed Tricot – a polyester (or less frequently a polyamide) material often used as a lining

  Velour – a closely woven, cut-pile fabric normally of cotton, wool or man-made fibre

  Microfleece – a lightweight, double-sided polyester microfibre.

Chemically these materials are usually polyester, ‘acrylics’ (polyacrylonitrile), cotton or polycotton (a blend of cotton and polyester).

Colourants

The 16 colourants controlled by EN 71-9 belong to one of the following classes of dyestuffs: Disperse dyes, Solvent dyes, Basic dyes and Acid dyes.  Apart from the Solvent dyes, they can all be used to colour textiles.  The analytical method described in EN 71-11 is able to identify and semi-quantify all 16 controlled colourants at the same time using the same analytical conditions.  Therefore, analysis for any one colourant will also determine the presence of the others.  Moreover, with suitable adaptations the method can be used to identify many other colourants.  However, textile materials are not usually analysed by this rather complicated method unless they have been shown not to be colourfast when tested by the first-action method elaborated in Annex A of EN 71-10.  This method, adapted from EN ISO 105-E04, is relatively inexpensive to perform and assesses the likelihood of colourants being transferred from textiles to the child’s mouth or skin.

In the absence of credible evidence that the 16 controlled colourants are not present or a declaration of colourfastness, textile materials used in toys intended for children under 3 years of age, and those worn over the mouth or nose, should initially be tested by the first-action method.  Note that this first-action method cannot on its own be used to show non-compliance to EN 71-9.

Primary aromatic amines:

Exactly the same toys and toy materials that have requirements for colourants also have a requirement not to contain any of the 9 primary aromatic amines listed in Table 2C of EN 71-9.  These carcinogenic amines are likely to be associated with certain azo dyestuffs.  However, unlike the requirements in the EC Marketing & Use Directive (2002/61/EC), the standard does not apply to all textile and leather toys, nor does it require the reductive degradation of any azo colourants present before analysis for the amines.  For textile and leather toy materials the requirements in the Directive are potentially more onerous but not directly comparable to the standard – the limits in EN 71-9 are lower than the Directive but apply only to the free-amine content.  Additionally, EN 71-9 has a requirement for aniline not to be detected as one of the primary aromatic amines, whereas the Directive currently has no such requirement.  If analysis is being carried out to check compliance with the Directive, it is extremely easy to assess compliance with the standard at the same time, and vice versa.

In exactly the same way that textile materials are not normally analysed for colourants unless they have first been shown to leach colour when tested for colourfastness, the same textile materials do not need to be routinely tested for the presence of primary aromatic amines unless they have already been shown not to be colourfast.  If azo dyes have not been used, it is unlikely that the textile will contain carcinogenic primary aromatic amines.

Solvents (inhalation):

There are requirements for textiles used in toys that children can enter (e.g. tents) and for those that are worn over the nose and mouth (e.g. masks) not to release certain volatile solvents above amounts set for individual substances.  Trichloroethylene (which is used to degrease wool) and nitrobenzene should not be detectable.

The solvent limits most likely to be exceeded are those for cyclohexanone and isophorone (3,5,5-trimethyl-2-cyclohexene-1-one).  These solvents, which have a strong, unpleasant odour, are often found present in toys, particularly plastic inflatable toys, which have a printed surface.  A toy containing a textile material that has a printed plastic coating may also contain and release these solvents into the atmosphere, especially when the toy is first taken out of its packaging.

Xylenes are used as a solvent in the manufacture of polyester fibres and in cotton finishing.  It is possible that traces may remain in a textile material after manufacture but a toy would be unlikely to exceed the volatile limit for xylenes unless it contained a large area of contaminated textile material (e.g. a tent).

Flame-retardants:

EN 71-9 has a requirement that two specific phosphate flame-retardants are not present in accessible textile materials used in toys intended for children under 3 years of age.  These 2 flame-retardants are more likely to be found in textile materials that are back-coated with plastics such as PVC than with the textile fabric itself.  However, since the analytical method involves solvent extraction it is likely that a plastic back coating containing these flame-retardants will cause the textile material to fail the standard.  Man-made fibres such as polyester are more likely to be flame retarded with organic compounds than natural fibres such as cotton and wool.  In the absence of documentary evidence, toys intended for children under 3 years of age containing accessible non-woven textiles or textile materials comprising man-made fibres need to be tested to show compliance.  Tri-o-cresyl phosphate, the most toxic tricresyl phosphate, is far less likely to have been used than tris(2-chloroethyl) phosphate, but since the analytical method determines each of these flame retardants there is no extra cost involved in looking for both.  It should be noted that the analytical method for flame-retardants elaborated in EN 71-11 can also be used to determine pentabromodiphenyl ether (PBDPE, pentabromodiphenyl oxide) and octabromodiphenyl ether (OBDPE, octabromodiphenyl oxide) and so can be used to demonstrate compliance with Directive 2003/11/EC.

Formaldehyde:

Formaldehyde is most likely to be present in cotton and cotton-containing fabrics such as polycotton that have been treated to give crease resistance and dimensional stability.  It can also be released from finishes used on polyester fibres and from binders used in textile printing.  Testing to EN ISO 14184-1 is relatively straightforward: however, it should be noted that the extraction test method is different from that recommended for child use and care articles in CEN TR 13387:2004.

Plastic materials

EN 71-9 has requirements controlling the presence of certain monomers, solvents and plasticisers in polymeric materials used in particular types of toys.

When assessing plastic toy materials it is important that sufficient information on the chemical composition is obtained to identify which polymeric

components are present; i.e. whether the plastic is a copolymer (made from 2 monomers), a terpolymer (made from 3 monomers) or a blend (alloy) of two or more polymers. 

With this knowledge, better decisions can be taken on the likelihood of one or more monomers or solvents controlled by EN 71-9 being released and thus needing analysis using EN 71-10 & 11.

Polymeric materials used by the toy industry include:

Acrylonitrile-butadiene-styrene terpolymer [ABS] – a hard plastic that can, inter alia, be alloyed with polycarbonate, polyurethane and poly(vinyl chloride)

Ethylene-vinyl acetate copolymer [EVA] – a flexible (rubbery), transparent plastic made by copolymerising ethylene with about 6% vinyl acetate.

Polyacrylates [PAc], also known as ‘acrylics’ – a family of polymers which include: poly(acrylic acid), polyacrylamide and polyacrylonitile.  ‘Acrylates’ and ‘Methacrylates’ are thermoplastic resins made from acrylic esters (e.g. ethyl acrylate) and methacrylic ester (e.g. methyl methacrylate).

Polyamide [PA] – a polymer formed by a reaction of a diamine and a carboxylic acid, for example, hexamethylene diamine with adipic acid (Nylon 66), or the polymerisation of ε-caprolactam (Nylon 6).

Polycarbonate [PC] – a hard, clear plastic made from bisphenol A.  It can be alloyed with many other plastics such as ABS, acrylics and poly(butylene terephthalate).

Polyethylene [PE] – this translucent plastic can exist in low density (LDPE), medium density (MDPE) and high density (HDPE) forms according to its method of manufacture.  It can be copolymerised with vinyl acetate, ethyl acrylate and acrylic acid.

Poly(ethylene terephthalate) [PET] – a polyester made by a condensation reaction between diethyl terephthalate and ethylene glycol.  This plastic can be blended with polycarbonate.

Poly(methyl methacrylate) [PMMA] – a clear, hard, polyacrylate (acrylic polymer) that can be copolymerised with styrene and alloyed with PVC.

Polyoxymethylene [POM], also known as Acetal (polyacetal) – a rigid, tough, translucent plastic made by the polymerisation of formaldehyde.

Polypropylene [PP] – a semi-rigid, translucent plastic formed by the polymerisation of propylene that can be alloyed (blended) with poly(vinyl chloride), and plasticized by elastomers such as nitrile rubbers.

Polystyrene [PS] – available in general-purpose, expanded and high-impact (HIPS) grades, this plastic can be alloyed with poly(phenylene ether), also called polyphenylene oxide, and copolymerised with ‘acrylates’ and ‘methyacrylates’.

Polyurethane [PU] – a thermoset elastomer that can be blended with ABS and polycarbonate.

Poly(vinyl chloride) [PVC] – a widely used plastic, often heavily plasticised.  It can be copolymerised with other monomers such as vinyl acetate and methyl acrylate, and alloyed with many other plastics.  Because of the wide variety and high percentages of additives used in ‘PVC’, this plastic is the one most likely to present problems in complying with the requirements in EN 71-9.

Thermoplastic elastomer [TPE] – a synthetic rubber commonly formed by the polymerisation of styrene with butadiene, isoprene or other reactive olefin.  It can be alloyed with other polymers such as poly(phenylene ether).
Kraton® polymers are commercial block-copolymer elastomers based mainly on styrene; several types are available: styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/propylene-styrene (SEPS) and polyisoprenes.  SIS has been used to make teethers.  Some of these elastomers have been used as a replacement for PVC in some applications.

Monomers:

There are requirements in EN 71-9 for certain types of toys that contain polymeric materials not to release acrylamide, bisphenol A, formaldehyde, phenol and styrene above set limits.  In the case of acrylamide, the limit is the analytical determination limit which is 0.02 mg/l.

Acrylamide: a water-soluble, crystalline solid used in the manufacture of polyacrylamide, a polymer unlikely to be found in toys.

Bisphenol A: a chemical used to make polycarbonate and some types of epoxy resins.  Bisphenol A is unlikely to be detected in plastic materials containing polycarbonate that are tested according to EN 71-10 & 11 unless the polycarbonate has been badly made, is badly degraded, or has been exposed to alkalis or solvents – even so, the limit in EN 71-9 is unlikely to be exceeded.

Formaldehyde: a volatile substance used in the manufacture of phenol/formaldehyde, melamine/formaldehyde and urea/formaldehyde resins and polyacetal.  The resins are mainly used as adhesives and to make resin-bonded wood-based materials such as plywood and chipboard.  Coatings made from urea-formaldehyde and plastics made from polyacetal are likely to release a small amount of formaldehyde unless the polyacetal has been surface treated to prevent this; the amounts are unlikely to exceed the limit set in Table 2D of EN 71-9.

Phenol: a substance with a low odour and taste threshold used in the manufacture of polyphenylene oxide and phenol/formaldehyde resins.  It has been found in PVC due to hydrolysis of certain stabilisers.  Polymeric materials containing PVC should be tested in the absence of a declaration that they do not contain or release phenol.  N.B. For inflatable toys this is not a formal requirement but an advisory one.

Styrene: a reactive chemical used in the manufacture of polystyrene, styrene-based elastomers (rubbers) and ABS and polyester (alkyd) resins.  Although polystyrene often contains residual styrene, its release from polystyrene is unlikely.  However, in the absence of migration data, testing should be carried out on styrene-based polymeric materials to establish whether they release significant quantities of styrene monomer.

Solvents (migration):

Trichloroethylene: may be present in PVC and elastomers.

Dichloromethane: used as a blowing agent for PU foams and as a solvent for polycarbonate resins; may be present as part of the adhesive used on seams.

2-Methoxyethyl acetate, 2-ethoxyethanol, 2-ethoxyethyl acetate, bis(2-methoxyethyl) ether and 2-methoxypropyl acetate: these glycol ethers and glycol ether acetate esters find use as solvents for lacquers and varnishes.  They are not likely to be found in uncoated polymers.

Methanol: a water-miscible alcohol unlikely to be associated with polymers.

Nitrobenzene: a very toxic pungent solvent that has been found present in EVA and polyurethane foams.  Along with aniline it has also been found in nigrosine dyes, which should not be used to colour toys.

Cyclohexanone: a pungent solvent, frequently released from coatings which have not been fully aired after application, especially from those used on PVC toys.

3,5,5-Trimethyl-2-cyclohexene-1-one, also known as isophorone: a solvent with a low-odour threshold that has been detected from coatings on PVC toys.

Toluene: used to soften plastics and in polyurethane manufacture; may be found in polyester resins.  Can be present in paints and as part of adhesive systems.

Ethylbenzene: occurs as residues in coatings; also used in styrene manufacture, has been found present in HIPS.

Xylenes: may be present in PVC and polyester resins, and as a residue in (phthalate) plasticisers.

Solvents (inhalation):

Many of the considerations that apply to textiles with respect to solvents also apply to polymeric materials.  The two methods detailed in Annex A of EN 71-11 will determine all the volatile solvents that have requirements in Table 2F of EN 71-9.  A limited number of toy types need to comply with these requirements; in the absence of suitable documentary evidence, testing is advised of those that do.

Toluene: used to soften plastics and in polyurethane manufacture; may be found in polyester resins.  Toluene can be present in paint and as part of adhesive systems.

Ethylbenzene: occurs as residues in coatings; also used in styrene manufacture, has been found present in HIPS.

Xylenes: may be present in PVC; residue in (phthalate) plasticisers.

Mesitylene: may be found in PVC and acrylic resins.

Trichloroethylene: may be present in PVC and elastomers.

Dichloromethane: used as a blowing agent for PU foams; can be present as part of adhesive systems.

Hexane: used as a solvent in rubber cements; has been found in expanded polystyrene and in polyurethane foams (from its use as a blowing agent).

Nitrobenzene: a very toxic pungent solvent that has been found present in EVA and polyurethane foams.

Cyclohexanone: a pungent solvent, commonly released from coatings which have not been fully aired after application, especially those used on PVC inflatable toys.

3,5,5-Trimethyl-2-cyclohexene-1-one (isophorone): a solvent with a low-odour threshold that has been released from coatings used on PVC inflatable toys.

Plasticisers:

Unsurprisingly, flexible plastics are more likely to have been plasticised than hard, rigid plastics.  Such plastics are also more likely to release other chemical substances when subjected to migration testing.

EN 71-9:2004 only has requirements for 4 phosphate plasticisers, substances that incidentally can also be used to impart flame-retardant properties to polymers.  Future editions of the standard are likely to control more plasticisers but when EN 71-9 was agreed there was uncertainty over the relative toxicity of alternative plasticisers (especially with respect to some of the phthalate plasticisers) and the intentions of the European Community over their control.  The 4 controlled phosphate flame retardants are classified as hazardous substances and should not be used in toys that are likely to be mouthed.  The limit is 0.03 mg/l, the determination limit of the method in the aqueous extract of the toy material.  It should be noted that the analytical method described in EN 71-11 can be used to identify and detect many other commonly-used organic plasticisers.

Triphenyl phosphate: a substance that has been used to plasticize PVC, vinyl copolymers (for example, vinyl chloride–vinyl acetate), phenol-formaldehyde resins, phenylene oxide resins and varnishes.  Triphenyl phosphate has been used in conjunction with antimony trioxide to flame-retard wendy-houses.

Tri-o-cresyl phosphate, tri-m-cresyl phosphate & tri-p-cresyl phosphate: these substances are collectively known as tricresyl phosphate or tritolyl phosphate.  Because of its toxicity, tri-o-cresyl phosphate is also controlled as a flame retardant.  Tricresyl phosphates have been used to plasticize and flame retard: PVC, elastomers, phenolic resins, nitrocellulose lacquers and poly(vinyl acetate) [PVA] varnishes.

Polymeric materials – Solvents and Monomers

The following table applies to the listed polymerics in “pure” or homo-polymer form only, when fabricated under normal manufacturing processes. Blends, alloys and co-polymers (other than those listed) should be considered to have an elevated risk.

What is an organic compound?

An organic compound is any member of a large class of chemical compounds whose molecules contain carbon; for historical reasons discussed below, a few types of compounds such as carbonates, carbon oxides and cyanides, as well as elemental carbon are considered inorganic.The study of organic compounds is termed organic chemistry, and since it is a vast collection of chemicals (over half of all known chemical compounds), systems have been devised to classify organic compounds. A few of the compound classes based on the functional groups they carry are as follows:

·               Acid anhydrides

·               Acyl halides

·               Alcohols

·               Aldehydes

·               Alkanes

·               Alkenes

·               Alkynes

·               Amides

·               Amines

·               Aromatics

·               Azo compounds

·               Carboxylic acids

·               Esters

·               Ethers

·               Haloalkanes

·               Imines

·               Ketones

·               Nitriles

·               Nitro compounds

·               Organometallic compounds

·               Phenols

·               Polymers, including all plastics

·               Thiols

 Many organic compounds are also of prime importance in biochemistry:

·               Antigens

·               Polysaccharides, carbohydrates and sugars

·               Enzymes

·               Hormones

·               Lipids and fatty acids

·               Neurotransmitters

·               Nucleic acids

·               Proteins, peptides and amino acids

                   Vitamins

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