Polyencapsulated Dry Film Paint Preservative:

A Better Alternative

Dr. Prakash Pathare

Director,
MELZER, Unique Chambers, F. C. Road, Pune 411 004. INDIA.
th
Presented at Novel Biocide II Conference, European Coatings, Berlin, Feb 24/25 , 2005.
Visit : www.melzerspeciality.com
E mail: [email protected]

Introduction:

Dry film preservatives in Paints have recently attracted lot of attention. There are two major
issues, performance and toxicity. Performance is a critical property, which shows money’s worth
to a customer, but the related toxicity concerns of leached preservatives from the film are more
alarming to everyone. A lot is being talked about and many efforts are made to ensure
minimization of likely toxicity threats. The governing body which issues biocide product
directives on usage of certain active substances in such formulations reviews both the aspects
from time to time, as and how further data on toxicity of certain molecules is being made
available. However, much needs to be thought and talked on this complex subject.

Many formulated products are available as dry film preservatives. All formulations are based on
known and registered molecules, and each formulator supports his product with the data available
on performance of formulation. There are formulations, such as those based on OIT, Diuron,
Carbendazim as one set of products, which are most studied chemistries today; and other newer
ones based on IPBC, Chlorothalonils, Zinc pyridinethiol-oxide complex, etc., and their
combinations. Almost all formulators seem to offer almost identical percentage combinations of
actives once a choice is made for doing the formulations. Carbendazim has been by far a major
constituent of film preservatives.

In April 2004, carbendazim was shifted from Class III to Class II substance; this decision was
based on the microbial/mutagenic studies related to carbendazim as a molecule (and not from its
quantity emitted from the dry film of paints, or its estimate, to guide by) and apprehensions were
expressed on its ill effects on masses. It has not been clarified whether and how the emitted
quantities of carbendazim from the dry paint film are going to affect the mass population and to
what extent. It is worth making a note that very large quantity of carbendazim is being used in
pesticide formulations, especially for soft skin fruit crops, as compared to the quantum involved
in preservative formulations. BPD now restricts its content usage as one of the components of dry
film preservative to below 1000 ppm in final paint. It is feared that such a decision may lead to an
unusual and multiple “Crisis of Confidence” for Paints sector to face. If the replacement of
carbendazim is to be attempted from the available actives at hand, sufficient data is not available
to guarantee performance and toxicity profile. Secondly the fear always exists that the story of
carbendazim may get repeated for next molecule in use later. This situation forces the Biocide
Industry to look for newer ways of formulations, which need to be applicable to all molecules and
it is expected to open new technological advances.

A Few observations in the past:

It is common to find variation in the performance of dry film preservatives and such
variation is acceptable too, but occasionally it reaches below-par level in tropical

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countries. Unfortunately, when below-par performance is observed, there is no
quantifying answer available to draw a concluding line why it occurred. All answers
thereafter appear to be subjective, such as deterioration of film by microbial infestation
after unusual weathering, which was said to be due to high rainfall, persistent humidity or
moisture and sunlight, weaker film, poor film thickness, and, a variety of answers, which
are related to both, formulation of paints and application methods of paints. None of them
are arguably absurd, but as said above, since these appear to be subjective in absence of
quantification criteria, they may become unacceptable to many.

One of the remedies, or a proactive solution, helplessly suggested under such conditions by a
biocide formulator is to increase the dosage of dry film preservative.

What is subtly suggested by increase in dosage?

1. There could be significant loss by migration/leach out ( or emission) of preservative from

dry film, (which is due to the assigned reasons such as excessive solubilization due to
weathering, rainfall, humidity, moisture, weaker porous film; all of them leading to
depletion of actives), which is expected to get compensated by increased dosage.

2. There could be insufficient presence/ unequal distribution of preservative in the dry film
(which is shown by assigned reasons, such as, high film thickness and presence of
gradient of distribution of preservative across this thickness, imbalanced paint
formulation, variation due to paint application methods, and similar reasons) and the
increase of dosage is expected to compensate for such non-uniformity.

What needs to be understood?

Most dry film preservatives are formulated products with multiple numbers of active molecules,
and therefore, the picture as above is more complicated than imagined. Apart from the quantum
of presence of the preservative in the dry film, and whether it is sufficient or not, which molecule
from the combination gets depleted more and which molecule is distributed in what way in the
dry film are more critical and decisive factors. Therefore, it is better to assume that both decide
the performance of dry film.

Thus minimum sufficiency of preservative in dry film is one aspect, whereas whether it is
distributed and thereafter retained in the film in the same ratio of components or not, as
formulated, is another issue deciding the long-term performance, and both need to be studied.

Some missing links in the subject:

Biocide Industry so far has not systematically addressed one important topic to debate and study.

It is whether the dry film preservatives are expected to perform by way of some kind of gradual
surface leach-out, i.e., by way of freshening of anti-microbial activity at the surface of the film, or
by way of their uniform presence in the (top-most layer…?…) of dry film, creating a resistance,
or barrier to microbial attack. Leach-out (or emission) is an observation from the reality. Most
often, it seems to have been assumed that ‘leach-out from film surface’ is a way of activation of
surface to resist attack from microbes. If that assumption is to be carried forward as a modality of
action, what needed to have been studied and then defined are:

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 (a) Ideal rate of leach out of each component, w.r.t. film thickness
(b) Combined rate of leach-out,
(c) Effect of leach-out of one component on ‘preservative balance’, and
(d) Leach-out rate vs. performance.

The data as above becomes essential, based on which formulation-optimization could be carried
out. Also required is the determination of minimum threshold concentration of each molecule for
the on-set of microbial deterioration after leach out, if ‘leaching’ is assumed as a mode of action.

Above data is required at least for an ideal system, if not for practical cases to get very explicit
understanding on such biocides. It is difficult to derive the same. Since ‘leach out of molecules
from the formulated preservatives’ in dry film is real life situation for some reasons, (in spite that
it is unregulated), Biocide Industry appears to have accepted it, as if it is ‘desirable way’ of
getting the performance. How far and how much ‘leaching’ is permissible needs to be probed too.

The immediate thought thereafter is, ‘controlling unregulated leach out to minimum’ may offer
better environment safety and performance too. This presents a new direction of research on
biocides.

Points of initiation of present work:

As said, the degree of leaching-out or emission of actives and thereafter deterioration of film by
microbial attack seems to vary. It needs to be understood that certain components of dry film
preservative formulations, as also paint formulations, seem to increases “the solubility” of the
active molecules of preservatives. These are:

1. Surface active agents/emulsifiers

2. Coalescing solvents
3. Other functional chemicals used to derive specific properties, such as flow, leveling of
film, removal of air-bubbles, etc., all of which are again SAAs.

Further, most dry film preservatives are prepared as aqueous dispersions using sufficiently large
quantities of SAA in formulations. Use of SAA to get stable dispersion often leads to increased
(pseudo-) solubility of otherwise difficult to solubilize active molecules. This needs to be
accepted as a threat to performance of such formulations, as aqueous dispersions.

It is also necessary to find out what happens to SAA when film dries, how and the extent to which
SAA can lead to micro-canalizing while the film goes to dry state from aqueous phase, whether
SAA are first to show migration to surface while film dries and finally how soon from the dry
film by heavy on-slaught of rain. Further topics to debate and study are, whether coalescing
solvents help the process of solubilising such SAA-coated active molecules of preservatives, or
they suppress it by de-stripping SAA from the grains of active substances; how SAA may
increase the porosity of the film, and thereafter increase the chances of microbial attack on the
dry film surface through created voids. No study has been reported so far to get answers, though
this author in the context of Hygiene Coatings had raised these issues. But by virtue of these
arguments, it becomes clear that one has to work to avoid the excessive usage of SAA while
formulating a dry film preservative, which might resolve most of these issues.

Use of polymeric SAA, which may combine with polymer matrix of paints, is one solution (1)
and it is greatly advocated in recent times, as the migration of such SAA gets arrested.

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Secondly, it is a worth to note that ‘uniform presence of dry film preservative in the dried paint
film’ is far bigger subject than it appears. Unfortunately, this subject also has remained un-
addressed so far from Biocide Industry.

Basic question: What is ‘Uniform Presence’?

There are two points to question:

1. Whether there is a likelihood of existence of distribution gradient of ‘dry film preservative’

across the film thickness, or is it that its presence is uniform across the film thickness? (Refer to
Fig. IA and I B).

Generally it is assumed and claimed that the dry film preservative is almost uniformly available
across the film thickness. Whether it is so or not cannot be easily detected.

Two questions arise. If a gradient exists, what is the criterion of determining efficacy of the
preservative? If the presence of the preservative is uniform, what is the mechanism of
protection? (what is mode of action?)

In relative terms, the answers to above are somewhat easier to find, if a preservatives has single
active component.

2. As said earlier, almost all dry film preservatives are formulated from multi-components,
such as anti-algal, anti-fungal, anti-bacterial speciality molecules. A few molecules have
multiple functions. Their ratio in the formulations is apparently fixed and most formulators use
the same ratio (but adopt different ways to get stable dispersions). It is assumed under normal
conditions, that the same ratio of components, as formulated, will uniformly exist in the dry
film, to give each site of dry film the same protection value, and it will be so, irrespective of
mode of action of preservative.

Rather, dry film preservative formulations having multiple components are made with these
assumptions, and it is expected to show always a uniform distribution in dry film.

There is no particular reason why each molecule of the preservative-composition would not get
randomly distributed in the film, instead of remaining in the same ratio ‘in associative manner’
at all times in the matrix of dry film. A non-uniform distribution of components will definitely
lead to variation of the performance of the dry film, as a few patches of dry film will not have
sufficient protection from the microbial attack due to absence of one or more active molecules
in that zone. (Refer to Fig. IIA and IIB).

2.a) More specifically, what is the meaning of ‘the synergy’ that such multi-component blend of
a dry film preservative creates, if this mixture is least likely to retain ‘uniform associative ratio
of components’ in the film, as added? Biocide Industry very cautiously or rarely uses the word
‘Synergy’ today, due to many other issues arising out of combination of actives in a
formulation, and due to BPDs. Nevertheless, these need to be addressed in future with proper
data.

Synergy may falsely indicate today to many that the present ratio of each molecule in the
preservative formulation is perfectly optimized, but once again, this aspect has not been
confirmed in the past.

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 Also please note that “Synergy” seems to exist in Nature, it could be perceived and let us accept
its necessity when one derives a formulation. Interestingly, a report on ‘Synergy Index of
Biocides’ exists (2) but it may require further refinement in light of what is said above.

Brown: Substrate Blue: Dry film Brown: Substrate Blue: Dry film

Fig I A Fig I B Fig. II A Fig II B

Uniform and non-uniform distribution Uniform and non-uniform distribution

of single preservative molecule in dry film of multi-components preserve. in dry film

2.b) Further, Brownian Dynamism is absent in highly viscous materials as also in a state
leading to dry film, which is responsible to create and maintain uniformity of a mixture in
liquid state. Therefore, how can one assure that the same ratio of formulation of actives will get
retained till the film dries? (Till phase difference occurs). The individual active molecules can
randomly disperse according to their surface properties and remain anywhere in the film.

Secondly, why should one assume now, that the present ratio of such molecules in multi-
components preservative formulation is a right ratio, and that, no component of it is in excess
above the optimum requirement? In addition, there are likely economic implications,
sometimes of excessive usages of some components, in order to get the best average results,
apart from toxicity concerns, and both are not studied so far.

These questions are applicable for all compositions of dry film preservatives, and not related to
those popularly based on OIT, carbendazim and diuron. In fact these questions are raised for all
‘synergy systems’ (Synergy is ideally defined later) and also for all formulations, where there is
likely existence of phase difference from liquid to solid, and not for paints alone, like
adhesives, paper boards etc., as individual system in operation.

3. Once the knowledge about these aspects is available, the dry film preservatives will stand to
create revolution. These will meet the environment safety norms.

4. Such doubts do not arise today for wet-state preservatives, since Brownian motions in a
liquid will always create a dynamic uniformity of composition of preservative, even if wet-state
preservative is a multi-component blend. For pasty or viscous compositions, this uniformity
may not be completely achievable, and therefore, wet state preservatives will also need to be
reviewed from the angle of ‘synergy’ and will be a subject of review in future.

The questions raised above suggested a change in formulation-technique whereupon the present
work initiated.

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Objectives of the work:
1. To ensure a mechanism of uniform presence of each component of such preservative in dry
film, and

2. To minimize the leach out.

Both were viewed as dependent on each other, which was a bold assumption.

Further objective:

“Synergy” and what could be the ideal synergistic combination (which means optimization of
content of each molecule in presence of each other, from all angles, to form an ideal workable
system) was listed under the next programme of study. This study is not over.

Assumptions:

Two assumptions were made at the beginning of the work.

a) The uniformity of preservative-presence gets disturbed and the film deteriorates, and
b) There is uncontrolled emission of actives from the dry film and the film deteriorates.

These assumptions were, in the first place, contradicting the present promotion-principles of dry
film preservatives. Biocide Industry claimed other way round to promote the use of such
preservatives for over a decade in the past and which the Paint Industry accepted. The new
thought was likely to make the previous claims on such formulations as worthless! However,
there is no suggestion of this kind while reporting this work.

Available Direction for the work on dry film preservative:

The thoughts as above finally led to Encapsulation of the active molecules in a polymer matrix
and deciding not to use monomeric surface-active agents while formulating dispersion, as a new
way of initiating a formulation of a dry film preservative. It was found to give great results. The
word ‘Polyencapsulation’ is introduced here to denote the process of delivery of an active
substance, or the combination of more actives through a polymer, in a definite manner and in
summarization of this process. Use of polymeric surfactants of low surface activity along with
other polymeric substances as modifiers is made as ‘ composite polymer base’ for carrying out
encapsulation and finally achieving stable aqueous dispersions.

The results obtained from this approach are now being reported in short.

This work is being termed as ‘Application Research on Delivery System of Preservatives’.

Microencapsulation has application across a very broad range of industries, e.g. the first
applications provided the print industry with the ability to provide copies without carbon paper!
Further, enhanced encapsulation techniques are recently commercialized (3, 4, 5, 6) in the attempt
to make drug-delivery in health-care use very specific to location of action, optimize the dosage
of drug and reduce the unwanted after effects. By following encapsulation, pharma industry could
handle certain labile preparations with extra-ordinary ease too. Microencapsulation is a process
by which very tiny droplets or particles of liquid or solid material are surrounded or coated with a

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continuous film of (polymeric) material. These micro-capsules have a number of benefits such as
converting liquids to solids, keeping reactive compounds separate from others, providing
environmental protection, improved material handling properties, etc., The active ingredient-
capsule is further protected against:

• high temperatures
• the effects of weathering
• pressure
• water
• degradation in air, etc.,

Table I: Typical properties of Encapsulated materials.

Characteristic Benefits for user

Can be suitably changed. Both dry powder and paste forms are possible, micro-
Solubility in water
capsule can be wet processed without solubilising the materials
Can protect actives from evaporation, or early decomposition, able to survive
Temperature
exposure to high temperatures
Release mechanism Active can be targeted to specific location for release
From a few cells to hundreds of cell, micronized powder can be used, non-
Particle size
flying, non-dusting characteristics could be built.
Oxidation Can reduce oxidative degradation, prolonging shelf life.
Performance under Release mechanism can be related to, or by fracture. The materials can
pressure withstand high pressures and shear force
UV protection Natural UV filter can be built.

Principal of the encapsulation process: schematically shown in Fig. III (7)

A B

C
Polymer

(In Fig III above, a micro-particle is shown to enter a polymer matrix, followed by another and a
micro-bead gets formed. Several micro-beads can be accommodated in one larger “enclosure” of
the polymer, forming a capsule. These capsules suspended in aqueous medium can then be lowered
into the system. Polymer can be chosen in such a way that it can exert an electrostatic orientation
across its chain length in aqueous phase and thereby can suspend itself. It could be a polymeric
SAA with mild surface activity. A self-suspension of such polymer-enclosed capsules in aqueous

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 medium may appear either as a stable dispersion or as a paste. This principle was used in
encapsulation reported here. The choice of polymeric substances was crucial.)

Schematic Manufacturing Process is shown in Fig. IV (One of the two standardized processes)

Additives and
Catalyst

Micronized / liquid jet

Active molecule

Organic ‘solvent’ Filtration

(different phase)

Polymeric SAA (monomer) wet

Particulate mass
monomer
Partial polymerization
over the particles
and stabilization

Final Aqueous
Suspension of
Preservative

Further details on the actual processes are not disclosed here.

The work now being reported is also being called as a step towards ‘Value Enhancement of
Actives’

The encapsulated preservatives so obtained showed good stability as aqueous dispersion, have
workable flow and consistency. These show no appreciable change in the rheology on storage at
ambient temperatures. All of them are compatible with most paint systems, at the pH range 3.5
to10.5. The pH of formulations is in the range 6 to 8, and most often it is around neutral. No
particular odour is observed.

Results:

The detailed discussion on the results is restricted, as it forms a separate subject by itself. It will
be presented along with the results related to other dry film preservative systems.

The microbial performance study (relative performance) of the dry film preservatives with almost
identical composition and at identical dosage (1.5 % w/w of wet 40% pvc paint) was carried out.
Commercially available conventional dry film preservative was a reference material to the
Polyencapsulated dry film preservative. In this study, both systems were subjected to leach-outs
by the method suggested earlier (8), and microbial studies were performed thereafter for an
extended period in the same manner. Another set of study was after artificial weathering. The
weathering at Florida site was also carried out.

What was the degree of leach out of the active molecules by above method (8) from the film
containing preservative was not known in the past, as a method to determine such data is
unknown. ‘A stagnant leach out in a water column’ has been devised now as a new method to

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explore an indicative leaching behavior of encapsulated preservative vs. non-encapsulated one
from the respective dry films It gave (statistical) average leach outs of respective preservatives.
The details about this method will be presented along with full details on the study. This method
is not a true picture of dynamism involved in real life leach out by weathering and heavy rain.
However, the consistent results from stagnant study as above are indicators of slightly (by 0.2-
1.4%) lower leach-out as a combined percentage from polyencapsulated preservatives, as
compared to leach out of actives from other preservatives. This pattern was observed irrespective
of film thickness. It was a significant observation. Perhaps, stagnated leach-out rate and dynamic
leach-out rate would differ, but the pattern is expected to remain the same.

In the end, the microbial study suggested that polyencpsulated dry film preservative has fared
very well to retain the structure of the film without algal and fungal growth. The distinguishing
difference between the preservative-panels was noticed by the least roughness and black spotting
on paint film of polyencapsulated preservative, when the laboratory inoculations on freely
suspended films and panels were discontinued, and the panels were left to follow natural weather
conditions for the further period of two months thereafter.

One question is always raised, what is the ideal dosage of dry film preservative? Can this answer
be dependent on the formulation of the preservative alone? Can one suggest a definite dosage?
No answer is available, as most depends on paint formulation, and subjectivity mentioned at the
beginning of this text seems to continue. However polyencapsulated preservative, in general, is
making a difference in performance, as found from the relative study, where as much
quantification as possible was attempted for giving performance rating.

How to verify whether Polyencapsulation really occurred?

This question was most important in this work, as every step of this work had presumed that one
can ‘bind’ the three actives together and therefore, their ratio, as added, could be the same at any
location in the dry film. It may probably create the ‘synergy’ by such uniformity of presence.

In order to confirm this, cryo-TEM (transmission electron microscopy) were carried out (9).

cryo-TEM is a tool to investigate the assembly, regulation and orientation of macromolecules and
micromolecules in a complex aqueous phase by electron transmission microscopy. It allows
visualization of delicate assembly of Amphiphilics and macromolecules in aqueous phase.

Amphiphilics are defined as surfactants, water, polymer etc, and their combinations. The solids
could be any active particle, enzyme, extenders etc.,

Applicable to : Particle size: 5 to 500 nm

Recording as : Thin aqueous film
Structural picture : Brownian movements arrested at temp of liquid nitrogen or
In dried state, if permissible to dry.

The two samples were Microcheck MZ 33 and Sample A. Sample A is said to be a reference
material in this study, which is another commercially known dry film preservative from a biocide
manufacturer, and was chosen to compare the results.

Following techniques were used for microscopy.

1. Transmission recording using Bright Field

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 2. Cross Polars
3. DIC (differential interference contrast)
4. SEM (scanning electron microscopy)

The details on sample preparation for recordings are available on request.

1. In Summary, the Sample A (reference sample) showed that it has several crystalline rods
or needle shaped particles along with many fine particles randomly placed, and they
undergo Brownian motion and are carried along with the medium, they have no particular
compositional consistency or togetherness with each other.

2. Whereas in the sample of Microcheck MZ 33, the individual fine particles, whether
needles or crystals, are almost absent, but aggregates appear as large mass consisting of
agglomerated crystalline solids, both needles and crystals, held together. (Association of
solids).

3. In order to re-confirm this and get further clarity on this, SEM recording was done. The
dried sample SEM recording confirmed the presence of similar agglomerates in
Microcheck MZ 33, which is absent in Sample A. The associated particles are actually
sol gels and micron gauge meter could not detect a large crust of hard particles of higher
size, though they appear as if these are having higher particle size than 10 microns.

4. The encapsulation and agglomeration in MZ 33 sample results into the particles in the
sample of MZ 33 not being carried around in surrounding water, which was used for
dilution, by Brownian motion of individual molecules. This association in MZ 33 could
be clearly seen, by way of comparison, in the SEM (SEI) recording in the dried state of
both the samples, thus confirming successful polyencapsulation.

(Microcheck MZ 33 is a registered product of MELZER)

The recordings of cryo-TEM are enclosed as miniature images. Please note, cryo-TEM study or
other tool may not be possible for paints in order to locate the preservative in dry film.

Conclusions and Remarks:

Though polyencapsulated preservatives have shown good result of dry film performance, what is
the mode of action of polyencapsulated preservatives is still a subject open for debate and study
hereafter. If leachability is assumed as the only method of activation of surface to resist microbial
growth, there is no conclusive evidence for its acceptance from above experimental data of
stagnated leach out study. Therefore, the uniform presence of preservative components is still an
indicative mode of action (forming an uniform barrier) for preservative to be efficient to perform.
The argument advanced in support of the same is as under:

‘Polyencapsulated’ preservative is not a hard crust of molecular composition in a polymer, in

which actives of preservatives are so deeply embedded that they remain permanently in that form.
Polyencapsulation becomes a delivery method of active molecules, as actives are held through
association with polymer. A force exerted by encapsulating polymer binds the actives together
through its polarity points and this composition is loaded in the paint by a simple post-
manufacturing stir-up. In all probability, the preservative composition remains in encapsulated

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form till the phase difference in paint starts occurring. There is no particular method to seek
evidence of this happening as on today. The phase change actually starts at brushing, spraying
like application methods (both have energy in-put) and completes at the drying point of paint.
Since the polymer chain is long, on which the active molecules are bound by associative forces,
the uniform presence of active molecules of preservative in dry film across its film thickness, is
most likely to be maintained. It happens due to two reasons, by stereo chemical effects (due to
long chain of the encapsulating polymer) as also by its partial locking with paint polymer. It will
be wrong to presume that individual molecules in polyencapsulated form are so deeply embedded
or surrounded by the encapsulating polymer that they cannot get released (emission by leaching)
for actions, as is a first impression of the user. If that were to be the case and accepted as likely
phenomenon, then by virtue of the same arguments, one has to accept that the active molecules of
most preservative would not have been available for normal leach out, whereby preservative
performance could not have been expected, once these get embedded in polymer matrix of paint
too. (Please note, polymer matrix of paints is definitely tougher than encapsulating polymer,
whereby paint withstands to the hardship that it suffers. If such tough polymer were to ‘embed’
the actives of preservative, the leach out would not have been noticed under normal conditions, as
it happens in most cases.) The point therefore is, polyencapsulation does not completely arrest the
leach out of actives (please refer to ‘Stagnated Leach out Tests’), but it is most likely to inhibit it;
it basically helps to deliver the preservative composition in the paint uniformly and retains it as
uniformly as one expects it to, till film dries; and that is the function and success of
encapsulation.

Therefore, ‘a uniform presence of active molecules in dry film as a barrier’ is a most likely
reason, and not ‘leaching’, which is responsible for the performance of such preservative. It is
however not a conclusion. (In spite of lower leach-out, the performance of polyencapsulated DFP
was better)

Algae require no particular surface situation to grow and it is not uncommon to see the algal
growth occurring on surface like glass too. For preventing algal growth, therefore, it is generally
presumed that preservative has to remain on the outermost surface. This encourages leachability
theory as a method of action of dry film preservatives to prevent algal deterioration. Why
polyencapsulated preservative showed sufficient resistance to algal growth is therefore a relevant
question from the view of leachability theory. Perhaps, what needs to be studied is the transition
point of surface growth to hard growth with respect to nature of algaecide as well as other
properties of the algaecide molecules and their role in maintaining surface activation. In this
particular composition, the presence of OIT, which inhibits algae, which is partially soluble in
water and easily leachable as liquid, might have helped to get the best balancing properties and
acted as a synergizer to other algaecide present in the formulation. (Also pl refer to solubility of
each component)

The concept of ‘Synergy from a Combination’ may probably take a new orientation hereafter,
once polyencapsulation of active blends and the resultant activity is well studied. There will be
acceptance to the word “SYNERGY”. This is most important development, as encapsulated
actives and their arrested leachability will force the governing bodies responsible for issuing
BPDs now to have re-look at the present BPDs as also to the synergy.

Another relevant topic is to work upon the encapsulation systems for solvent based formulations
of preservatives. A need of dry film preservative with anti-mold properties is well underlined for
automotive coatings; a few of them are oven-dried paints, whereas self-curing 2K systems are
becoming very popular. Both require appropriate dosage of dry film preservative. Corrosion

11
control coatings also require dry film preservatives to avoid microbe-induced corrosion and
marine coatings are already using film preservative as anti-foulants, which are tin-free.

Biodegradation of encapsulated preservative systems is an area, which may be studied in future

for understanding and exploring the different aspects related to individual active molecule in
relation to the combination, but it may not show significant variation from the present status. This
is so, since as said above, ‘Polyencapsulation’ is an intermediate status of active molecules till
delivery point and not a permanent one to alter the molecular properties, like biodegradability.
There may not be any significant alteration in rate of biodegradation of actives.

Finally, to summarize, it certainly promises that ‘polyencapsulation of biocides’ offers better and
safer route and in future, it will be preferred mode of delivery of biocides in almost all systems.
This will shift the focus from searching new and safer molecules to the effective use of known
molecules. It will be done by way of carrying out more innovative formulations, wherein their
usage will be to minimum effective concentrations. A newer concept of ‘synergy from the
combination’ will emerge and get firmly established. It will lead to a change in the thoughts
related to BPDs, and all these together will create newer symbols in safety paradigm in this field.

Acknowledgements:
The Author gratefully acknowledges the contributions by the team of scientists, chemists and
microbiologists at MELZER led by Ms. Sheeba Swaminathan, Technical Manager, in this
revolutionary development, as it is globally first report of its kind in the field of BIOCIDES.

References:

1. Self Crosslinking Polymeric Dispersants used in Emulsion Polymerization, Presentation, A.J.P.

Buckmann, T. Nabuurs and G. C. Overbeek, Neo Resins, Waaliwilk, Netherlands.

2. Biocide Optimization: Blends of Actives,

Presentation, Karen Winkowski, International Speciality products, Wayne, NJ, USA.

3. Polymer Encapsulation and Polymer Microspheres.

US Patent 6022500, Aug. 2000

4. Encapsulation by Coating
EP 1190123B1 , Octo. 2002

5. Templating Solid Particles by Polymer

EP 116516A! , July 2001.

6. Encapsulation and Controlled release of food Ingredients

Ed. Sara J Risch and Gary A Reineccius, A C S Symposium Series, 1995.

7. The figures are adopted from Glatt Group presentations

8. A two for one Biocide for Latex Paints,

Laxmi Sadashivan, Usha Gandhi, Rohm and Haas, Spring House, PA, USA.

9. Dept of Biosciences, IITB, Mumbai, India, for cryo-TEM recordings.

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Annexure I:

cryo-TEM RECORDS:

Bright field Recording: Conventional Formulation:

Shows random distribution of actives

SAMPLE -A

DIC Recording of Conventional Formulation:

Shows random distribution of actives

SAMPLE -A

SEM Recording of Conventional Formulation:

Shows individual molecules

SAMPLE -A

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Bright Field Recording: NEW Formulation:
Shows “Association of molecules”

Microcheck MZ 33

DIC Recording of NEW Formulation :

Shows “Association of molecules”

Microcheck MZ 33

SEM Recording : NEW Formulation :

Shows “Associated molecules”

Microcheck MZ 33

14
Cross polar Recording: Conventional Formulation :
Shows more individual molecules

SAMPLE -A

Cross Polar Recording: Conventional Formulation:

Shows more individual molecules

SAMPLE -A

15
Cross Polar Recording: NEW Formulation:
Shows “Encapsulated Molecules”

Microcheck MZ 33

Cross Polar Recording: NEW Formulation:

Shows “Encapsulated Molecules”

Microcheck MZ 33

16