Formaldehyde releaser

A formaldehyde releaser, formaldehyde donor or formaldehyde-releasing preservative is a chemical compound that slowly releases formaldehyde. Formaldehyde-releasers are added to prevent microbial growth and extend shelf life.^[1] The intent of these compounds is that they release formaldehyde at levels that suppress microbial growth but sufficiently low to not threaten humans. The use of these chemicals in cosmetics has elicited controversy.

3D structure of Formaldehyde

Examples

Many compounds have been formulated a formaldehyde-releasers.^[2]

• Quaternium-15 (Dowicil 200; Dowicil 75; Dowicil 100; Dowco 184; Dowicide Q). It was used in low concentrations in cosmetics but has been banned in the EU since 2017 and a bill is under consideration in the US.^[3][4]
• DMDM hydantoin
• (ethylenedioxy)dimethanol (EDDM)
• (Benzyloxy)methanol (BHF, benzylhemiformal)^[2][5]
• 2,2',2-(Hexahydro-1,3-5-triazine-1,3,5-triyl-)triethanol (HHT)
• Tetramethylolacetylenediurea (TMAD)
• 1,3-Bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMH)
• 3,3'-Methylenebis[5-methyloxazolidine] (MBO)
• Imidazolidinyl urea (Germall 115) for cosmetics^{[citation needed]}
• Diazolidinyl urea (Germall II) for cosmetics^{[citation needed]}
• Tris(hydroxymethyl) nitromethane (Tris Nitro) for cosmetics^{[citation needed]}
• tris(N-hydroxyethyl) hexahydrotriazine (Grotan® BK)^[6]
• Sodium hydroxymethylglycinate for cosmetics^{[citation needed]}

Unintentional formaldehyde releasers

Some materials release formaldehyde unintentionally. These materials have also elicited considerable controversy, especially when these materials have household applications such as flooring. Examples:

• Delrin or Acetal
• Phenol formaldehyde resin
• Urea formaldehyde resin
• Melamine resin

Uses

They are found in fuels, cosmetics, toiletries, cleaning agents, adhesives, paints, lacquers, fertilizers, and metalworking fluids.^[2] They are found in lysing agent for cells for in vitro diagnostic reagents. Photo-chemicals and press room chemicals also contain these releasers.^[7]

Safety

Main article: formaldehyde § Safety

Formaldehyde is dangerous to human health.^[8][9] In 2011, the US National Toxicology Program described formaldehyde as "known to be a human carcinogen".^[10][11][12]

The danger of formaldehyde is a major reason for the development of formaldehyde releasers which release formaldehyde slowly at lower levels.^[13]

Allergic reaction

Levels of 200–300 p.p.m. formaldehyde in cosmetic products can cause contact dermatitis in short-term use on normal skin.^[13]

A patch test study found that DMDM hydantoin in cosmetic products could increase the risk of cosmetic dermatitis.^[13]

Some people have a contact allergy to imidazolidinyl urea causing dermatitis.^[14] Such people are often also allergic to diazolidinyl urea. In 2005–06, it was the 14th-most-prevalent allergen in patch tests (3.7%).^[15]

Cancer

Some consumer cosmetics contain quaternium-15 for its antimicrobial properties.^[16] The American Cancer Society states that although quaternium-15 releases formaldehyde, a known carcinogen in laboratory test animals at relatively high doses, because the amount of formaldehyde released from these products is low, it is unclear that avoiding quaternium-15 in cosmetics provides any health benefits.^[17] Even so, Johnson & Johnson announced plans to phase out its use of quaternium-15 in cosmetic products by 2015 in response to consumer pressure.^[18]

Importance

Formaldehyde in the EU is restricted to a maximum allowed concentration in finished products no greater than 0.2%.^[2] However, there are hidden sources of formaldehyde such as these formaldehyde releasers. As well, patch tests are prone to false positives at even low concentrations and not a reliable test.^[2]

Sensitization to formaldehyde has been decreasing since 1980 due in part to the replacement of formaldehyde by these formaldehyde releasers.^[2] As of 2009, frequency of sensitization to formaldehyde is stable at 2–3% in Europe.^[2] It might be as high as 9% in the USA.^[2][13]

Alternatives

There are three groups of broad-spectrum preservatives with the most safety and efficacy.^[19]

• Parabens
• Formaldehyde releasers
• Halogenated compounds

The FDA requires that cosmetics have an effective preservative, and microbial challenge testing is conducted. The EU's Cosmetic Directive 76/768/EEC requires the use of a preservative on an approved list.^[19]

Analysis

There are many ways to test and quantify formaldehyde.^[13] However these methods are not suitable for the determination of free formaldehyde in cosmetics with formaldehyde releasers since these methods often accelerate release of formaldehyde.^[20]

The physical method by 13C NMR spectroscopy does not affect the equilibrium between free and donor sources of formaldehyde and might be the best way to test for formaldehyde releasers.^[13]

References

1. Uhr, Hermann; Mielke, Burkhard; Exner, Otto; Payne, Ken R.; Hill, Edward (2013). "Biocides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. 1–26. doi:10.1002/14356007.a16_563.pub2. ISBN 978-3527306732.
2. De Groot, Anton C.; Flyvholm, Mari-Ann; Lensen, Gerda; Menné, Torkil; Coenraads, Pieter-Jan (2009). "Formaldehyde-releasers: Relationship to formaldehyde contact allergy. Contact allergy to formaldehyde and inventory of formaldehyde-releasers" (PDF). Contact Dermatitis. 61 (2): 63–85. doi:10.1111/j.1600-0536.2009.01582.x. hdl:11370/c3ff7adf-9f21-4564-96e0-0b9c5d025b30. PMID 19706047. S2CID 23404196.
3. "European Commission notifies bans, restrictions on CMRS in cosmetics". from the original on 3 January 2021. Retrieved 2 December 2019.
4. "The cosmetics industry has avoided strict regulation for over a century. Now rising health concerns has FDA inquiring". Retrieved 2 December 2019.
5. "Benzylhemiformal | Allergic Contact Dermatitis Database". from the original on 3 January 2021. Retrieved 2 December 2019.
6. https://core.ac.uk/download/pdf/12939269.pdf^{[bare URL PDF]}
7. "FORMALDEHYDE AND FORMALDEHYDE RELEASERS Investigation Report". Retrieved 2 December 2019.
8. "Formaldehyde", Formaldehyde, 2-Butoxyethanol and 1-tert-Butoxypropan-2-ol (PDF), IARC Monographs on the Evaluation of Carcinogenic Risks to Humans 88, Lyon, France: International Agency for Research on Cancer, 2006, pp. 39–325, ISBN 978-92-832-1288-1
9. "Formaldehyde (gas)", Report on Carcinogens, Eleventh Edition 2019-08-06 at the Wayback Machine (PDF), U.S. Department of Health and Human Services, Public Health Service, National Toxicology Program, 2005
10. Harris, Gardiner (2011-06-10). "Government Says 2 Common Materials Pose Risk of Cancer". New York Times. from the original on 2019-03-28. Retrieved 2011-06-11.
11. National Toxicology Program (2011-06-10). . National Toxicology Program. Archived from the original on 2011-06-08. Retrieved 2011-06-11.
12. National Toxicology Program (2011-06-10). (PDF). National Toxicology Program. Archived from the original on 2011-06-12. Retrieved 2011-06-11.
13. de Groot AC, van Joost T, Bos JD, van der Meeren HL, Weyland JW (1988). "Patch test reactivity to DMDM hydantoin. Relationship to formaldehyde allergy". Contact Dermatitis. 18 (4): 197–201. doi:10.1111/j.1600-0536.1988.tb02802.x. PMID 3378426. S2CID 221577901.
14. Review of toxicological data (NTP NIEHS)
15. Zug KA, Warshaw EM, Fowler JF Jr, Maibach HI, Belsito DL, Pratt MD, Sasseville D, Storrs FJ, Taylor JS, Mathias CG, Deleo VA, Rietschel RL, Marks J. Patch-test results of the North American Contact Dermatitis Group 2005–2006. Dermatitis. 2009 May–Jun;20(3):149-60.
16. de Groot, Anton C.; White, Ian R.; Flyvholm, Mari-Ann; Lensen, Gerda; Coenraads, Pieter-Jan (2010). "Formaldehyde-releasers in cosmetics: relationship to formaldehyde contact allergy". Contact Dermatitis. 62 (1): 2–17. doi:10.1111/j.1600-0536.2009.01615.x. PMID 20136875. S2CID 39758546.
17. "Formaldehyde". American Cancer Society.
18. "Johnson & Johnson to phase out potentially harmful chemicals by 2015". CBS News. Retrieved 2 December 2019.
19. "Alternative Cosmetic Preservatives - What are your options? - Chemists Corner". 5 November 2010. Retrieved 2 December 2019.
20. Brandão, Pedro Francisco; Ramos, Rui Miguel; Rodrigues, José António (2018). "GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers". Analytical and Bioanalytical Chemistry. 410 (26): 6873–6880. doi:10.1007/s00216-018-1287-0. PMID 30062513. S2CID 51880356.