Why the detergent industry relies on a limited number of in-can preservatives

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Why the detergent industry relies on a limited number of in-can preservatives Background: in-can preservatives active substances under BPR (PT6) BPR currently allows the use of 50 active substances

1 Why the detergent industry relies on a limited number of in-can preservatives Background: in-can preservatives active substances under BPR (PT6) BPR currently allows the use of 50 active substances for PT6 (those that are approved or under review see the list in Appendix 1). However, in practice many of them are not used in detergents, cleaning and maintenance products, due to some limitations such as technical properties or classification. A survey performed in 2016 amongst A.I.S.E. members identified the following PT6 active substances as the most used by the detergents, cleaning and maintenance products industry: Active Substance % of Use BIT 74% MIT 72% CMIT/MIT (already approved) 55% Bronopol 32% Phenoxyethanol 23% OIT 19% Source: A.I.S.E. survey 2016 on the use of in-can preservatives (88 respondents representing around 60% of the EU turnover based on Euromonitor data) % of use = the figures indicate the % of respondents who indicated major or average use of the substance(s) versus the total number of respondents Overview of the different PT6 active substances and their applicability to detergents and cleaning products Isothiazolinones family: higher compatibility with cleaning products 1,2-benzisothiazol-3(2H)-one (BIT) Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (EINECS ) and methyl-2H-isothiazol-3-one (EINECS ) (Mixture of CMIT/MIT) 2-methyl-2H-isothiazol-3-one (MIT) octyl-2H-isothiazol-3-one (OIT) methyl-1,2-benzothiazol-3(2H)-one (MBIT) butyl-benzo[d]isothiazol-3-one (BBIT) Chloro-2-methyl-2H-isothiazol-3-one (CIT) This PT6 family is by far the most widely used in cleaning products, due to its broad spectrum of activity, high efficiency, compatibility with all formulation types and ingredients (such as enzymes that are a key technology in laundry detergents enabling low temperature washing), stability in all formulation types (e.g. stable at a wide range of ph 1 ), and affordable cost. 1 Except CMIT/MIT that is stable up to ph 8 October 2018 Page 1 of 5

2 Amongst this family the substances most widely used by the detergent industry are BIT, MIT, CMIT/MIT and OIT. The others are either not technically suitable (BBIT has a short shelf life) or new actives under BPR (MBIT and CIT) so that there is no experience from downstream users yet with those actives 2. Formaldehyde releasers family: issue with toxicological classification N,N -methylenebismorpholine (MBM) (ethylenedioxy)dimethanol (Reaction products of ethylene glycol with paraformaldehyde (EGForm)).alpha.,.alpha.,.alpha. -trimethyl-1,3,5- triazine-1,3,5(2h,4h,6h)-triethanol (HPT) ,3 -methylenebis[5-methyloxazolidine] (Oxazolidin/MBO) Sodium N-(hydroxymethyl)glycinate Tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)imidazo[4,5-d]imidazole-2,5 (1H,3H) dione (TMAD) Tetrakis(hydroxymethyl)phosphonium sulphate(2:1) (THPS) Methenamine 3-chloroallylochloride (CTAC) ,2,2 -(hexahydro-1,3,5-triazine-1,3,5- triyl)triethanol (HHT) ,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMH) a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c] oxazole (EDHO) cis-1-(3-chloroallyl)-3,5,7-triaza-1- azoniaadamantane chloride (cis CTAC) (benzyloxy)methanol Our industry is moving away from this technology since a couple of years due to classification issue: some formaldehyde releasers have been assigned a similar classification as formaldehyde i.e. carcinogen Cat. 1B, and it is expected that this classification will apply to all formaldehyde releasers. Phenols: not compatible with surfactants and smell issue 2-Phenoxyethanol Biphenyl-2-ol Sodium 2-biphenylate Chlorocresol Most of the phenols are not compatible with surfactants (core functional ingredients for detergency) and give bad smell to products. Phenoxyethanol does not present these technical restrictions (or to a much more limited extent) and due to its technical benefits, is of interest to the detergent industry. 2 MBIT and CIT are new active substances under BPR; as such there is no biocidal products containing those actives under transitional period. Downstream users have to wait for the BPR authorisation of biocidal products containing those actives before using them to preserve detergents and maintenance products. October 2018 Page 2 of 5

3 Acids: incompatible with all neutral and alkaline formulations L-(+)-lactic acid Hexa-2,4-dienoic acid (Sorbic acid) Peracetic acid Formic acid Potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate) PT6 active substances that are acids can be used only in acidic formulations (ph below 4-5), so this limits their use to very specific product categories such as fabric softeners or acidic cleaners. They cannot be used to preserve laundry detergents, dish washing liquids, all purpose cleaners that typically have a neutral or alkaline ph. In addition their activity/performance is quite limited. Others: Bronopol ,2 -dithiobis[n-methylbenzamide] (DTBMA) iodo-2-propynylbutylcarbamate (IPBC) Zinc pyrithione Pyridine-2-thiol 1-oxide, sodium salt (Sodium pyrithione) Tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (Dazomet) bromo-2-(bromomethyl)pentanedinitrile (DBDCB) ,2-dibromo-2-cyanoacetamide (DBNPA) Dodecylguanidine monohydrochloride Glutaral (Glutaraldehyde) Hydrogen peroxide Didecyldimethylammonium chloride (DDAC) Didecyldimethylammonium chloride (DDAC (C8-10)) N-(3-aminopropyl)-N-dodecylpropane- 1,3-diamine (Diamine) Reaction mass of titanium dioxide and silver chloride - p-[(diiodomethyl)sulphonyl]toluene N-(trichloromethylthio)phthalimide (Folpet) Benzyl Alcohol Ethanol Monochloramine generated from ammonium carbamate and a chlorine source Sodium Azide Amongst the other PT6 active substances, bronopol is the most widely used since, despite some technical limitations (cannot be used at alkaline ph), it is very effective against bacteria. The other PT6 substances are not widely used in cleaning products due to: - technical limitations such as: o formulation incompatibility: sodium pyrithione, DDAC, DDAC (C8-10), diamine, benzyl alcohol, dodecylguanidine monohydrochloride are not compatible with some surfactant types, that are present in many cleaning products as core functional ingredients for detergency; Dazomet hydrolyses in water October 2018 Page 3 of 5

4 o instability in formulations: hydrogen peroxide, reaction mass of titanium dioxide and silver chloride, monochloramine generated from ammonium carbamate and a chlorine source, DBNPA (short shelf life) o o narrow spectrum of activity: IPBC, p-[(diiodomethyl)sulphonyl]toluene limited efficacy: DBDCB, ethanol (high use levels required to observe preserving effect) - toxicological profile: examples include folpet (suspected of causing cancer), glutaraldehyde (classified as respiratory sensitiser), zinc pyrithione (recently proposed to be classified as toxic for reproduction Category 1B). Some are new actives under BPR (e.g. sodium azide) so that there is no experience from downstream users yet with those actives. [For details see Appendix 1] October 2018 Page 4 of 5

5 Appendix 1: List of PT6 active substances allowed under BPR and their relevance for the detergents, cleaning and maintenance products industry (file embedded below) October 2018 Page 5 of 5

ANNEX ANNEX. to the COMMISSION DELEGATED REGULATION (EU).../...

ANNEX ANNEX. to the COMMISSION DELEGATED REGULATION (EU).../... EUROPEAN COMMISSION Brussels, 28.11.2018 C(2018) 7778 final ANNEX ANNEX to the COMMISSION DELEGATED REGULATION (EU).../... amending Delegated Regulation (EU) No 1062/2014 as regards certain active susbtances/product-type