The New BPR

In Situ
Generated Active
Substances
Dr. Helmut Kraus, Lanxess Deutschland GmbH
Barcelona 2011, Dr Helmut Kraus Slide 1

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)

Barcelona 2011, Dr Helmut Kraus Slide 2

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

Barcelona 2011, Dr Helmut Kraus Slide 3

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

Barcelona 2011, Dr Helmut Kraus Slide 4

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?

Barcelona 2011, Dr Helmut Kraus Slide 5

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.

Barcelona 2011, Dr Helmut Kraus Slide 6

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.

Barcelona 2011, Dr Helmut Kraus Slide 7

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

Barcelona 2011, Dr Helmut Kraus Slide 8

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!

Barcelona 2011, Dr Helmut Kraus Slide 9

Examples
1. Formaldehyde(Fa) releaser (donor)
O-releaser: RO-CHOH + H2O -> HCHO + ROH quick release,
N-releaser: R2N-CHOH + H2O -> HCHO + R2NH slow release,
(dep. pH)

2 under evaluation
12 under evaluation

- 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
- The Fa releaser are supported in the PTs

Barcelona 2011, Dr Helmut Kraus Slide 10

PT 2, 3, 20, 22,
2, 6,11,12,13

RMS DE
several RMS

Examples
1. Formaldehyde releaser
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
Barcelona 2011, Dr Helmut Kraus Slide 11

Examples
2. Chlorine generator
Facts
- 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 Mnchen, 1/2011), a

big gap

Thought starter: Tons of Cl2 are generated and delivered within wide hotel ressorts with many
Thought
swimming pools and water fun parks
starter
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.

Barcelona 2011, Dr Helmut Kraus Slide 12

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)

Barcelona 2011, Dr Helmut Kraus Slide 13

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 foruse of biocidal products (Chapter I, Article 1, 2a)

Barcelona 2011, Dr Helmut Kraus Slide 14

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 pHequilibrium 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.

Barcelona 2011, Dr Helmut Kraus Slide 15

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)

Barcelona 2011, Dr Helmut Kraus Slide 16

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?

Barcelona 2011, Dr Helmut Kraus Slide 17

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

Barcelona 2011, Dr Helmut Kraus Slide 18

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

Barcelona 2011, Dr Helmut Kraus Slide 19

Thank you
for listening
Questions?

Barcelona 2011, Dr Helmut Kraus Slide 20

Contact details:

Dr. Helmut Kraus

LANXESS Deutschland GmbH
Material Protection Products
D-51369 Leverkusen, Germany
Chempark, Building Q 18-1, Room 856
E-Mail: helmut.kraus@lanxess.com
Phone: +49(0)214/30-25077

Barcelona 2011, Dr Helmut Kraus Slide 21