Phthalates in consumer products

Providing an insight into the regulations surrounding the presence of phthalate plasticisers.

Phthalates are a group of chemical plasticisers that are frequently added to polymer formulations to change the flexibility and durability of the final plastic. These substances are commonly used to soften polyvinyl chloride (PVC), combatting the naturally very rigid and hard properties of unplasticised PVC (‘uPVC’) to create a much softer and malleable final material.

Their use is not only confined to PVC, as polyurethane (PU), paint, inks and adhesives can also contain phthalate plasticisers. In addition, plasticised materials can be found in many products, including polymeric footwear solings, plastic packaging, children’s toys, personal protective equipment (PPE) and other consumer products.

Phthalate plasticisers alter the physical properties of the plastics by weakening the bonds between the polymer chains. This makes them not so tightly bonded to each other, which results in increased flexibility. The oils in plasticisers are not chemically bound to the polymer, but lie between the polymer strands. This results in plasticisers being highly mobile, creating a potential migration pathway for discolouration problems where dark-coloured materials can transfer their colour to light-coloured materials.

Health concerns

Concerns have been raised about phthalate plasticisers, due to possible hormonal effects on people who are exposed to them over a period of time. As such, these substances are described as ‘endocrine disruptors’. Exposure to phthalates can occur through various routes, the most concerning being ingestion, which makes infants most at risk of being exposed due to their hand-to-mouth behaviour. This is why the first phthalate restrictions only applied to toys and childcare items. However, as a result of more research data being produced, this is no longer the case, as it has been identified that exposure to these phthalates can be through a number of different routes of exposure.

Therefore, children are no longer the only demographic considered to be at risk. The research stated that not only does exposure occur through ingestion, but also via prolonged contact with skin and inhalation of air in indoor environments. The study revealed that there was a risk not only for the consumer but also the worker. Hence, the European Chemical Agency (ECHA) decided to widen the scope and amend REACH (Regulation (EC) No 1907/2006) Annex XVII entry 51, covering restrictions on plasticised toys or childcare items, to any article containing plasticised materials. Detailed information about phthalates that are restricted can be found in this article.

Alternatives to phthalates

There are other chemicals which can be used as plasticisers instead of phthalates. These include adipate-based plasticisers which are used for low-temperature applications, and other aliphatic esters based on dicarboxylic acids, such as sebacates and maleates. There are also moves towards natural plasticisers, including epoxidised vegetable oils. However, when switching to an alternative plasticiser system, there may be a need to alter the plasticiser level and possibly the production process, as each individual plasticiser will behave differently and modify the handling properties of a polymer to differing degrees.

The wide range of uses of PVC and other plasticised compounds in the manufacture of footwear, apparel, luggage, PPE and other consumer products will place different demands on materials in terms of performance. Product specifications need to evaluate key physical parameters. This will help to ensure that any move away from phthalate plasticisers meets the requirements of the consumer’s expectations for the intended level of performance from the material and the finished product.

European restrictions

REACH Annex XVII. Specific phthalates are restricted in Europe under REACH Annex XVII entries 51, 52 and 72, and in the UK under UK REACH which currently matches the EU REACH requirements. Since July 2020, DEHP, BBP, DBP and DIBP have been restricted in articles containing plasticised materials at 0.1 per cent or above by mass under entry 51. The article should not be placed on the market if either the individual concentration of each phthalate, or the sum of the four phthalates in the plasticised material, is greater than 0.1 per cent.

Under entry 52, DINP, DIDP and DNOP are restricted in toys and childcare articles which can be placed in the mouth by children in concentrations greater than 0.1 per cent by weight of the plasticised material. A ‘childcare article’ is defined as any product ‘intended to facilitate sleep, relaxation, hygiene, the feeding of children or sucking on the part of children’. A summary of the entry 51 and 52 restrictions is detailed in table 1 below.

Table 1: Phthalate restrictions listed in REACH Regulation (EC) 1907/2006 Annex XVII entries 51 and 52
Phthalate	Acronym	CAS number
Bis (2-ethylhexyl) phthalate	DEHP	117-81-7
Dibutyl phthalate	DBP	84-74-2
Benzyl butyl phthalate	BBP	85-68-7
Di-isobutyl phthalate	DIBP	84-69-5
Di-isononyl phthalate	DINP	28553-12-0 and 68515-48-0
Di-isodecyl phthalate	DIDP	26761-40-0 and 68515-49-1
Di-n-octyl phthalate	DnOP	117-84-0

Entry 72 concerns substances that are classified as ‘carcinogenic’ (may cause cancer), ‘mutagenic’ (may be capable of inducing genetic mutation) or classified as toxic for reproduction, and includes 33 different substances. Five phthalates are restricted to a maximum of 1,000 mg/kg (individually or sum of the phthalates) and the scope of the restriction applies to textile materials in footwear and clothing (see table 2).

Table 2: Phthalate restrictions listed in REACH Regulation (EC) 1907/2006 Annex XVII entry 72
Phthalate	Acronym	CAS number
1,2-Benzenedicarboxylic acid, di-C6-8-branched alkyl esters, C7-rich (also known as Di-isoheptyl phthalate)	DIHP	71888-89-6
Bis(2-methoxyethyl) phthalate	DMEP	117-82-8
Di-n-hexyl phthalate	DnHP	84-75-3
Di-n-pentyl phthalate	DnPP (DPENP)	131-18-0
Di-isopentyl phthalate	DIPP	605-50-5

REACH SVHCs. ‘Substances of Very High Concern’ (SVHCs) fall under the ‘authorisation’ category of REACH. This process aims to ensure that substances associated with health or environmental concerns are progressively replaced by less dangerous options.

There are currently 16 phthalates listed as SVHCs as indicated in table 3.

Table 3: Phthalates included in the Candidate List of Substances of Very High Concern (SVHC) published on 14th June 2023
Phthalate	Acronym	CAS number
Bis (2-ethylhexyl) phthalate	DEHP	117-81-7
Dibutyl phthalate	DBP	84-74-2
Benzyl butyl phthalate	BBP	85-68-7
Di-isobutyl phthalate	DIBP	84-69-5
1,2-Benzenedicarboxylic acid, di-C6-8-branched alkyl esters, C7-rich (also known as Di-isoheptyl phthalate)	DIHP	71888-89-6
Bis(2-methoxyethyl) phthalate	DMEP	117-82-8
Di-n-hexyl phthalate	DnHP (DHEXP)	84-75-3
Di-n-pentyl phthalate	DnPP (DPENP)	131-18-0
Di-isopentyl phthalate	DIPP	605-50-5
Dicyclohexyl phthalate	DCHP	84-61-7
1,2-Benzenedicarboxylic acid, di-C7-11-branched and linear alkyl esters	DHNUP	68515-42-4
1,2-Benzenedicarboxylic acid, dipentylester, branched and linear	PP*	84777-06-0
n-pentyl-isopentyl phthalate	PIPP	776297-69-9
1,2-Benzenedicarboxylic acid, dihexyl ester, branched and linear	DHP	68515-50-4
Di-isohexyl phthalate	DIHxP	71850-09-4
bis(2-ethylhexyl) tetrabromophthalate covering any of the individual isomers and/or combinations thereof	_	26040-51-7
*PP is the sum of DIPP, DnPP and PIPP

Suppliers of articles containing any SVHCs at a concentration greater than 0.1 per cent by weight of the entire article must identify them to their customers and give sufficient information to ensure the product is used safely. Notification to ECHA in the EU and the Health and Safety Executive (HSE) in the UK is also required if, in addition to the 0.1 per cent limit being exceeded, the total amount of the SVHC being imported into either the EU or UK market is greater than one tonne per annum. Please click here to read a SATRA Spotlight article explaining EU SVHC obligations.

US restrictions

CPSIA. There is also phthalate legislation specific to the USA. This is contained within Section 108 of the Consumer Product Safety Improvement Act of 2008, which is commonly referred to as the ‘CPSIA’. The CPSIA is enforced by the Consumer Product Safety Commission (CPSC) and requires importers and manufacturers to comply with Federal legislation, which includes specific limits for the amount of phthalates that children’s toys and childcare articles can contain.

CPSIA section 108 (as updated by 82 FR 49938), requires less than 0.1 per cent of eight phthalates: DEHP, DBP, BBP, DINP, DnPP, DnHP, DCHP and DIBP, to be present (see table 4). Under this legislation, a child’s toy is considered to be ‘a consumer product designed or intended by the manufacturer for a child 12 years of age or younger, for use by the child when the child plays’. A childcare article is defined as ‘a consumer product designed or intended by the manufacturer to facilitate sleep or the feeding of children age three and younger, or to help such children with sucking or teething’.

Table 4: Phthalate restrictions listed in Section 108 of the Consumer Product Safety Improvement Act of 2008
Phthalate	Acronym	CAS number
Bis (2-ethylhexyl) phthalate	DEHP	117-81-7
Dibutyl phthalate	DBP	84-74-2
Benzyl butyl phthalate	BBP	85-68-7
Di-isononyl phthalate	DINP	28553-12-0 (68515-48-0)
Di-isobutyl phthalate	DIBP	84-69-5
Di-n-pentyl phthalate	DnPP (DPENP)	131-18-0
Di-n-hexyl phthalate	DnHP (DHEXP)	84-75-3
Dicyclohexyl phthalate	DCHP	84-61-7

The CPSIA requires that all US manufacturers and importers must produce a Children’s Product Certificate (CPC). These certificates must be based on test reports from CPSC-accredited, independent third-party laboratories which are both accredited to ISO 17025 and are listed on the CPSC website. SATRA has such a facility, and our accredited laboratory identification number is 1223.

Exemptions from compulsory testing are granted to materials comprised of polyethylene (PE), polypropylene (PP), general purpose polystyrene (GPPS), medium impact polystyrene (MIPS), high impact polystyrene (HIPS), super high impact polystyrene (SHIPS) and acrylonitrile butadiene styrene (ABS), as long as the formulations demonstrate that the restricted phthalates were not used.

Californian Proposition 65. ‘Proposition 65’ (also known as the ‘Safe Drinking Water and Toxic Enforcement Act’) was published in 1986 as legislation applicable to the US state of California. This was brought into force as a way of informing citizens about exposures to chemicals that could cause cancer, birth defects or other reproductive harm. Proposition 65 requires suppliers to label their products containing chemicals identified as being carcinogenic or having adverse effect on development or reproductive health. The list is published by the Office of Environmental Health Hazard Assessment (OEHHA) and it is required to be updated at least annually. There are currently over 900 chemicals on the list.

The key requirement of Proposition 65 is for suppliers of consumer goods to ensure that a ‘clear and reasonable’ warning is provided to consumers if any of the substances listed are known or suspected to be present. In some cases, warnings are not required for products, even if they contain substances listed within Proposition 65. This occurs where the company can demonstrate that the level of exposure does not carry a significant risk. There are currently six phthalates included in Proposition 65 (see table 5).

Table 5: Phthalates listed in California Proposition 65
Phthalate	Acronym	CAS number
Bis (2-ethylhexyl) phthalate	DEHP	117-81-7
Dibutyl phthalate	DBP	84-74-2
Benzyl butyl phthalate	BBP	85-68-7
Di-isononyl phthalate	DINP	28553-12-0 and 68515-48-0
Di-isodecyl phthalate	DIDP	26761-40-0 and 68515-49-1
Di-n-hexyl phthalate	DnHP (DHEXP)	84-75-3

Testing for phthalates

The most commonly followed international testing standards to determine whether phthalates are present are EN ISO 16181:2021 (part 1 with solvent extraction and part 2 without solvent extraction) for ‘critical substances potentially present in footwear and footwear components’, and EN ISO 14389:2022 – ‘Textiles – Determination of the phthalate content – Tetrahydrofuran method’. EN ISO 14389 was updated in 2022 and included a broader list of phthalates to detect alongside some other minor changes. SATRA is able to carry out testing to the 2022 version of EN ISO 14389, as well as CPSC-CH-C1001-09.4 to comply with the CPSC requirements for phthalates in the USA.

Steps to compliance

Demonstrating that restricted phthalates are not present is mandatory for all consumer products sold within the EU, UK and in California, as well as for children’s items sold in the USA. A helpful summary of the restrictions discussed in this article can be found in table 6. There are a number of steps that can be taken to ensure that products comply with the requirements of restrictions. The auditing of raw materials and production processes, exchanging technical information throughout the supply chain and supplier declarations of conformity can all be used to provide information and assurance that restricted phthalates are not present in consumer products.

Table 6: Summary
Phthalate	REACH Annex XVII			REACH SVHC	CPSIA 2008	Prop 65
	entry 51	entry 52	entry 72
DEHP	√			√	√	√
DBP	√			√	√	√
BBP	√			√	√	√
DIBP	√			√	√
DINP		√			√	√
DIDP		√				√
DnOP		√
DnHP			√	√	√	√
DIHP			√	√
DMEP			√	√
DnPP			√	√	√
DIPP			√	√
DCHP				√	√
DHNUP				√
PIPP				√
DIHxP				√
PP				√
DHP				√
bis(2-ethylhexyl) tetrabromophthalate covering any of the individual isomers and/or combinations thereof				√

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