biocides

Barcelona 2011, Dr Helmut Kraus Slide 1

The New BPR

In SituGenerated Active Substances

Dr. Helmut Kraus, Lanxess Deutschland GmbH


On June 2009, proposal for a Regulation was adopted …… envisaged to come into force in January 1st, 2013.

„The scope of the proposed Regulation will be more extensive than

the current Directive covering … (besides treated material and food

contact materials) active substances generated in situ …“


Meaning of in situ?

- Wikipedia: 23 application fields for use

film: insitu.arte.tv (interactiv)

IT: in situ back up,…in situ algorithm

medicin: cancer before metastasis

chemistry: in the reaction mixture


BPD(R) definition of in situ generated active substances

- A substance that is not directly placed on the market

- Is generated intentionally via different means and exerts a biocidal activity during

its application (i.e. in the reaction mixture)

No metabolites

Multiple-Formaldehyde-releaser? (DMDMH-DCAR: not mentioned)

DMDMH = Dimethylol-dimethyl-hydantoin


Discussions about in situ during the BPD

Dossier requirements 2002:

- Data on the precursor chemicals and the in-situ generated

substance are necessary for a complete evaluation.

- Read across and waiving possibilities should be explored

- Cases ClO2, open air factor, Cu electrodes….?

9 cases are discussed in the MoD

Several TM and CA meeting documents

Draft TNG in 9/2010,…………….final draft?


The draft TNG CA-Sept10-Doc.6.2a

- Endorsed at 38th CA meeting, 6 months commenting phase until April 2011

Executive summary (exact citation)

• Products placed on the market with the intention to be used as biocidal products fall

within the scope of the BPD unless otherwise excluded, for example by Article 1(2) of

the BPD, and such products need to be authorised.

• Biocidal active substances that are not directly put on the market in biocidal products

but are formed in-situ at the place of intended use are, in many cases, also within the

current scope of the BPD and therefore need to be evaluated.

• When the use falls within the scope of the BPD, the precursor(s) and, if appropriate,

the in-situ generated active substance need to be listed in the Annex I entry of the

BPD.

• The dossier and the assessment report need to contain the appropriate information on

both precursor(s) and in-situ generated active substance in order to properly assess the

safe use of the biocidal product.


The draft TNG

Precursors

- Case 1 Precursor, intended to release the active during application, is placed on

the market. Precursor and in situ active -> Annex-1 entry

- Case 2 In situ active is released as product of a chemical reaction of two or more

chemicals. Different Annex-I entrys are possible

Special case ClO2: different chemicals can be used

- Case 3 In situ active is generated in an equipment from a general available precursor

Discussion, if it is really within the BPD/BPR.

equipment = biocidal product?

CA May 2011 Doc 5.6 „MSs do not want to register equipments….“


The draft TNG

Methods of in situ generation

1. Formation (within the application); e.g Formaldehyde(Fa)-releasers,

Phosphine from Al-phosphide

2. Chemical reaction, e.g. Chloramine from Ammoniumsalt and Hypochlorite,

Peracids from carboxylic acid „oxygen“

3. Electrolysis, e.g. ClO2 from sodium chlorite

Cl2 from sodium chloride (includes sea water)

4. Hydrolysis, e.g. Chlorine from Hypochlorite

Hypohalous species from hydantoins


The draft TNG

On site versus in situ

- Concentrated actives are formulated within a plant, formulated and used on site

- The active is the biocidal product and has to be registered, including this on site

mixing step

In situ generation within plants?

„If equipments have to be registered, plants should not be closed, if such

devices a part of the plant“ citation from discussion at CA July 2011…?

key word - portable or not ???

NB: The difference between portable or not could be a screw in the wall!


Examples

1. Formaldehyde(Fa) releaser (donor)

O-releaser: RO-CHOH + H2O -> HCHO + ROH quick release, 2 under evaluation

N-releaser: R2N-CHOH + H2O -> HCHO + R2NH slow release, 12 under evaluation

(dep. pH)

- The Fa and Fa releaser companies (FABI) shared a common Fa core dossier

- Data of releaser, Fa and alcohol/amine had been submitted within the Fa releaser dossiers

- Formaldehyde itself is only supported in PT 2, 3, 20, 22, RMS DE

- The Fa releaser are supported in the PTs 2, 6,11,12,13 several RMS


Examples

Unclear situation about the progress

- The core dossier (1st version, FABI) has been evaluated by RMS DE.

- Comments with new data submitted in 1/2011; DCAR of Fa (4 PTs) not published.

- Running evaluation of the Annex XV Fa dossier sent to ECHA by France

- FREG, (Fa-Releaser Evaluation Group) actions?

- DCAR DMDMH(PT 6, 13) has been published as a first „Fa-report“ in June 2011(PL)

- The evaluated Fa core dossier was applied including comments by FABI and DE

- PT 6,13, i.e. Fa not supported: biocidal products and articles (waterbased applications)

(can) contain free Fa; Product registrations?

- Fa content in a.s. and b.p. is < 0,1%, full neglect of Fa,

risk assessments in applications: full hydrolysis to Fa and DMH

1. Formaldehyde releaser


Examples

2. Chlorine generatorFacts

- Chlorine is produced mostly be electrolysis of sodium chloride

- As no NaCl is marketed for the generation of Cl2(fools?), there is no need for registration(BPD)

- „The generating equipment is no biocidal product“ (Landgericht München, 1/2011), a big gap

Thought starter: Tons of Cl2 are generated and delivered within wide hotel ressorts with many

swimming pools and water fun parks

The use of Cl2 is evaluated in the BPD for PT 2, but this (mis)use should be

exempted?

As a consequence national regulations can occur what could lead to different

authorizations. Harmonizition is the key word!

Conclusion: Include devices for in situ generation in the BPR, in order to avoid

implementation deficits and legal uncertainty.

Thought

starter


Examples

2. Chlorine generator

Companies argue that the in situ generation is totaly out of the scope of the BPD/BPR; looking

for an unfair competition advantage.

BAuA (German authority) states in a legal advice, that after a transition period in 2017 such

generating equipment shall be registered as biocidal product;

i.e. closing the gap.

Attorney Dr Hohmann commented the draft TNsG document in April 2011: …we recommend

creating a mandatory authorization of the devices for in situ generation of active substances

(personal information)


Examples

2. Chlorine generator

Actual definition of a biocidal product in the BPR:

Biocidal products means

substances, mixtures, or articles in the form in which they are supplied to the user,

consisting of, containing or generating one or more active substances, with the

primary intention of destroying, deterring… any harmful organism by any means

other than mere physical or mechanical action.

In the 1st version the wording …“devices placed on the market…“ was included,

It is understood (?) that the 2nd definition retains devices and equipments which

generate in situ biocides.

NB: „The BPR lays down rules for…use of biocidal products…“ (Chapter I, Article 1, 2a)


Examples

3. Salts and the corresponding acids

- Sodium Warfarin is the only (noncovalent) salt at Annex-I, though Warfarin is at Annex-I.

- As it is produced from Warfarin and sodium hydroxyde, it should be regarded more as biocidal

product of the H-compound; especially because only Warfarin is efficious, not the salt.

- Potassium sorbate is mostly the commercial handling form of the active sorbinic acid.

- The acid, the active substance(!), is covered by the salt, only one dossier is sufficient for the

evaluation of all risks. (BauA document, CA-May08-Doc.8.5a)

- Benzoic acid DCAR: „…benzoates are included… , acidic pH…equilibrium moves to the

undissociated acid…, acid and benzoate can be considered together.“

- BIT-Na (and BIT-Li) have a big market share within BIT formulations.

- Only BIT dossiers are known, BIT-Na is the biocidal product in submitted BIT dossiers.

- BIT-Na was only identifed, but marketing proceeds tacitly.


Examples

3. Salts and the corresponding acids

- Salts of weak organic acids are exempted in the new draft TNG; no in situ case.

- The chapter Hydrolysis to form an acid-base pair, is dedicated to Cl2(Br2) generation from the

chemical reaction of hypocloric acid or halogen hydantoins with water.

- The hydrolysis of salts of weak organic acids to form the biocidal active H-compound is

regarded as a different process.

- Salts of phenolics, which are weak acids, are covered by the corresponding H-compounds;

see progress report of COM

- These salts are included as biocidal products in specific PTs of the phenol dossiers; all data are

submitted, a safe use evaluation is possible. After Annex-I-inclusion of the parent H-compound,

the salts will be registered as biocidal products

(Comment Lanxess to the draft TNG in April 2011)


Examples

4. Enhancer

- Amines are often used to enhance the biocidal activity of several biocidal actives

- The used amines show often more or less biocidal efficacy.

- Diamine(Lonza, Akzo) is the only (real) amine under evaluation

- N-Fa-releaser can contain efficient amine compound(s), released at application- Literature: P. E. Brutto, Tribology & Lubrication, March 2011, 26 – 31, about amine enhancers in Metall Working Fluids

- Not regulated in the BPD/BPR

- Postponed to the product authorization?

http://www.google.de/imgres?imgurl=http://www.bs-wiki.de/mediawiki/images/704px-Makino-S33-MachiningCenter-example.jpg&imgrefurl=http://www.bs-wiki.de/mediawiki/index.php/K%25C3%25BChlschmierstoffe&h=600&w=704&sz=53&tbnid=lUFKLijrRcOzRM:&tbnh=119&tbnw=140&prev=/search%3Fq%3Dk%25C3%25BChlschmierstoffe%26tbm%3Disch%26tbo%3Du&zoom=1&q=k%C3%BChlschmierstoffe&hl=de&usg=__ndJJvyrT_F8vLqYM4h2ZtdXuFVU=&sa=X&ei=Jt4mTp-XHIKAhQerhMGHCg&ved=0CD0Q9QEwBw


Transition period

Article 80 for in situ actives

- Applications for authorizations of substances and mixtures considered as biocidal

products because they generate active substances and which were available on the

market on 1. 1. 2013* shall be submitted latest by 1. 1. 2017*

1st Version: …authorizations of substances, mixtures and devices considered as…

- 6 months out phase period for substances and mixtures… which were available on

the market on 1.1.2013, but no application was submitted or refused.

- 12 months out phase period for existing stock

* provisional dates


Outlook

- Waiting for the final draft TNG (not published in 8/2011)

- The more extensive BP Regulation should cover precursor(s), actives

and devices in cases of in situ generation of active substances.

- Dossier and CAR need to contain all information about the whole process

in order to properly assess the safe use of the biocidal product.

- Pragmatic solutions should be created at the stage of Annex-I of the

active and not postponed to product authorization or other national

legislations


Thank you

for listening

Questions?


Contact details:

Dr. Helmut Kraus

LANXESS Deutschland GmbH

Material Protection Products

D-51369 Leverkusen, Germany

Chempark, Building Q 18-1, Room 856

E-Mail: [email protected]

Phone: +49(0)214/30-25077

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