Professional Documents
Culture Documents
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The term detergents used in this thesis applies only to those products
used for fabric cleaning and not for personal use or cleaning other media.
Furthermore, the product developed is for use in a dry powder detergent, the
detergent consists of granulated components and has the form of a dry powder
prior to use.
Most powder detergents consist of 5 classes of components:
1. Surfactants, i.e. surface active components,
2. builders, for removal of calcium and magnesium ions from the washing
water,
3. bleach systems, for removal of organic colors of fabrics,
4. enzymes, which catalyze biochemical reactions,
5. minors, such as perfume and anti-foam components.
The surfactants perform two functions. The first is the lowering of the
surface tension to enhance the removal of fatty material from the fabrics. The
second is the formation of micelles which act as reservoirs for the removed fatty
material by solubilizing it.
Calcium and magnesium ions are impurities present in the washing water
which cause precipitation of anionic and soap detergents. This causes a decrease
in the efficiency of the surfactants and the unwanted effect of precipitates on
clothing. To remove the calcium and magnesium ions builders are used. This is
done by precipitation (precipitative builders, e.g. sodium carbonate), complex
forming (e.g. sodiumtripolyphosphate) and by ion-exchange with the aid of
zeolites.
Bleaches are used to remove organic colors from fabrics. The color of the
stains is often derived from a complicated organic molecule having a variety of
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reactive or unsaturated groups and bonds. The oxidizing agent attacks these
molecules and oxidizes them to less complicated molecules that are commonly
colorless.
Enzymes are used to breakdown complex biomolecules, the following
types are most common in detergents:
- amylases, for the breakdown of starches (potato, pasta),
- proteases, for the breakdown proteins (blood, gravy, milk),
- lipases, for the breakdown of fats,
- cellulases, for fabric improvement.
Minor components in a detergent are perfume, optical brighteners, anti-
rediposition agents and anti-foam agents.
In the existing powder detergents all these components are dissolved
simultaneously in the washing water. However, since some of the components
are not compatible with each other, sequential release of the components in the
washing water could potentially make more efficient use of these components
compared to simultaneous action.
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Increasing the washing performance by sequential release of the
components or the incorporation of several washing stages is not a new idea.
Already in 1960 a two phase washing stage was described in a patent [US
3,042,621]. The general idea of this patent is that a detergent contains many
components, some of which are not compatible to an extent that they deactivate
each other. To solve this problem the individual components are dosed
sequentially to the washing water, so preventing interaction between different
components.
Ideally, this principle of sequential dosing should be implemented in the
powder detergent as an additional function of the product. This is the main goal
of the products developed in this thesis: the development of a powder
formulation that can dose detergent components sequentially to the washing
water.
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Stability is an important issue in detergents. Detergents contain very
mobile components even in a dry state (non-ionic surfactants) and can take up
water during storage. This can cause problems due to the deactivation of several
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components. Products that are likely to have a positive effect on the stability
(i.e. formulations that have a protective barrier for active components) are
preferred.
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In any situation and for any product the consumer would like to have a
product that is convenient to use and has a good performance. A controlled or
sequential release detergent is likely to have an improved performance
compared to a traditional detergent. An additional advantage is that the
traditional powder formulation is preserved and thus the washing habits of the
consumer do not have to be changed.
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Detergents are flushed away together with the washing water. The
washing water from a washing machine forms an important part of the
domestic wastewater. In the past several components of detergents have caused
environmental problems. Examples are the first synthetic detergents that used
non-biodegradable surfactants that caused excessive foam forming in water
purification plants and the use of sodiumtriphospate as builders which caused
excessive algal growth in surface water.
The use of a controlled release detergent would enhance the efficiency of
the used components and thus reduce the amount necessary in a detergent. Less
material means a lower concentration in the wastewater and thus a more
environmental friendly use of detergents.
Related to this environmental issue is the increasing pressure from the
European governments to reduce the impact of detergents on the environment.
The reduction of the environmental impact of detergents is described in the
European Commission's adoption of “a Recommendation for Good
Environmental Practice for Household Laundry Detergents” [http://www.
eubusiness.com/environ/980723co. htm].
The Recommendation is based on a voluntary measure, the
Environmental Code of Practice, proposed by A.I.S.E. (Association
Internationale de la Savonnerie, de la Détergence et des Produits d'Entretien)
representing more than 90% of the European detergents industry.
It sets the following targets: by the year 2002, compared with 1996, the
total amount of energy used per wash cycle should be reduced by 5%; the
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The world detergent market (the word detergent only applies to those
products used for fabrics cleaning) was worth $25.62 billion in 1993. The
competition in the business is fierce with as biggest manufacturers on the
market Proctor & Gamble, Unilever, Henkel and Colgate.
This means that a lot of research is and has been done to improve the
washing characteristics or efficiency of the detergent. In the past this has led to
several revolutions in the detergent industry which were very profitable to
some manufacturers [1]. Examples are the addition of hydrogen peroxide to the
detergent (a mixture of perborate and silicate or Per-sil) in 1907. In the fifties the
first synthetic detergents emerged on the market that reduced the energy use of
the washing machines considerably, additionally a low-foaming detergent was
introduced (Dixan) that improved the washing performance of drum-type
washing machines. In the sixties the first enzymes were introduced into
detergents (Biotex). The enzymes improved the removal of protein stains. The
use of enzymes implied reduction of the temperature of the washing water,
which caused a reduced efficiency of the hydrogen peroxides. To solve this
problem Unilever introduced bleach activators in the seventies. A big change in
the eighties was the removal of phosphates from the formulation in favor of
zeolites.
A new dry powder detergent with controlled or sequential release would
be a new development giving improved washing characteristics and therefore a
competitive advantage.
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There are some specific demands that the release profile of an active
component in a controlled release formulation for use in a detergent should
fulfill:
1. An (beforehand) adjustable lag-time (the time without any release of the
contents) up to 45 minutes,
2. a pulse release of the active component in the washing water after the lag-
time,
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Controlled release formulations that have a positive influence on the
stability of the active components (i.e. form a protective barrier to any other
components) are preferred.
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The formulation should consist of particulate matter in the size range of
300 and 1000 µm. this ensures that the formulation can be incorporated into
existing powder detergents, without any segregation, dusting or flowability
problems.
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Some active components in detergents (proteases, bleaches) can be a
potential health hazard to consumers or operators in the production plant. To
ensure there is no contact of the active with the consumer or operator the
formulation should be physically stable and should have sufficient mechanical
properties to prevent premature exposure of the active.
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In this thesis no attempt is made to calculate the cost price of the
formulations. This means that it is possible that components are used that
would not be economically feasible in a real life detergent. On the other hand
we discarded formulations beforehand that would have needed an excessive
expensive component such as tailor made polymers.
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All the production methods used in thesis are also used on a larger scale
in bulk production plants. No attempts were made to produce formulations that
would imply the use of a very complicated production method, which are
common in for example the pharmaceutical industry, such as coated tablets
with laser-drilled holes.
Also the production processes for the formulations described in this thesis
should be as environmental friendly as possible. This means that the use of
organic solvents in the production processes is not allowed. Therefore the
production of the products described in this thesis required no organic solvents.
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To prevent sedimentation of water-insoluble remains on the substrate (i.e.
clothes) the formulation should preferably consist entirely or for a large part of
water-soluble components.
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on the amount of liquid diffused into the capsule. The application is that a
solution of hydrogen peroxide, in which contact lenses are disinfected, is
neutralized after a certain lag-time by a component present in the capsule. In
this way the contact lenses are given sufficient time to be disinfected by the
hydrogen peroxide without bringing the persons eye in contact with the strong
oxidizing agent.
Ueda et al have a patent [7] and published three articles [8-10] about a
particulate pulse release device which they named a Time controlled Explosion
System (TES). It consists of an inert core (polystyrene balls or non-pareil sucrose
beads) coated with respectively a drug layer, a swelling agent layer (low-
substituted hydroxypropylcellulose) and a water-insoluble layer
(ethylcellulose). When water diffuses through the ethylcellulose coating the
hydroxypropylcellulose layer will swell and rupture the ethylcellulose layer
inducing immediate release.
The lag-time is controlled by the thickness of the outer ethylcellulose
membrane. They found that the water permeation rate through the outer
coating is correlated with the reciprocal of the membrane thickness.
Hydroxypropylcellulose (HPC) was chosen as the swelling agent because
the swelling of this polymer is independent of the pH of the environment in
which it is immersed. Therefore the formulation has a release profile
independent of the pH. Another claimed advantage of this formulation is that
the release depends only on the swelling of the HPC layer and thus is
independent of the solubility of the drug in contrast to formulations depending
on release by diffusion of the drug through a rate limiting membrane. One
condition has to be met to achieve this swelling layer thickness dependent
release rate: the swelling layer has to be sufficiently thick to prevent premature
diffusion and dissolution of water into the drug layer.
The drug, HPC and ethylcellulose layers were applied in a fluid bed from
an organic solution.
Schultz and Kleinebudde [11] wrote an article on a device similar to the
bursting devices discussed before. In this case the formulation is somewhat
simpler, it consists of a water-soluble core coated with a water-insoluble film-
former (cellulose acetate). Release depends on the increase of the core volume
due to the diffusion of water though the coating. The coating is not totally
ruptured but pores are formed when a certain amount of water has diffused
into the core. Through these pores the active ingredient is released. Changing
the ratio between water-soluble and water-insoluble material in the core alters
the release profile from a release controlled by drug diffusion through the
coating to a pulse release profile.
In a follow up article [12] Schultz and Kleinebudde describe the relation
between the release properties and the mechanical properties of free cellulose
acetate films. They found that they could influence the release properties by
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using plasticizers in the cellulose acetate film with varying water solubility. The
water solubility of the plasticizer influenced the water permeability of the
coating and the dissolution rate of the plasticizer from the film. Also the amount
of plasticizers had a pronounced influence on the release properties.
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into the water removing any remaining active bleach in the medium. Finally the
enzyme is released which is than protected from deactivation by bleach.
To achieve this release profile Olson used several formulations. One
formulation is a core consisting of enzyme and filler coated with a bleach
neutralizing compound and a delayed release coating. Another formulation
described consists of two types of cores, enzyme and bleach-neutralizing cores,
each coated with different amounts or types of delayed release coating in such a
way that the bleach-neutralizing compound is released before the enzyme. As
bleach-neutralizing compound Olson used sodium-perboratemonohydrate or
sodium sulphate. As delayed release coatings were used sodiumcarboxymethyl-
cellulose and hydroxypropylcellulose.
No data is given for the release properties of the formulations but the
inventor aims at a delayed release of 2-6 minutes for the bleach neutralizing
compound and 0.5-2 minutes later the enzyme release.
Economics laboratory Inc. have a patent [19] on a formulation that should
improve the cleaning performance of enzymes by reversing the strategy of
Olson i.e. delaying the release of the oxidant bleach. This is achieved by coating
bleach particles. However, they state that the encapsulation of the bleaches to
protect the enzymes alone is not sufficient. This is due the instantaneous release
of bleaches caused by damaged or imperfectly coated capsules. Therefore
reducing agents are incorporated to deactivate small amounts of bleach from
damaged capsules to prevent premature deactivation of enzymes by these
bleaches. An example is a potassium dichloro-isocyanurate bleach encapsulated
in ethylene vinyl acetate which was added to 2 liters of water. In the water was
dissolved an enzyme, a detergent and a reducing agent. It was seen that the
release of the bleach in the water was delayed for 5 minutes after which the
enzyme activity rapidly decreased to zero.
Proctor & Gamble [20-24] has patents that describe formulations with a
similar goal as the patent from Olson; controlled release of an enzyme
compared to another compound. The release of the enzyme can be delayed
compared to another compound, or, the release of another compound is delayed
compared to the enzyme. Furthermore Proctor & Gamble do not restrict the
patents to just enzymes, also the delayed release of other compounds is
described such as a peroxyacid bleach compared to a surfactant.
For example in WO patent 97/235593 [21] the delayed release of a calcium
chelating agent is described. The calcium chelating agent acts as a water
softener and increases the stain removal. When the chelating agent is released
immediately in the washing water from the beginning of the washing process
the calcium in the water is immediately removed. Proctor & Gamble claim that
this can cause problems for the enzyme activity because some enzymes are only
active when a certain amount of calcium ions are present in the water. To solve
this problem the dissolution of the chelating agent is delayed. Delayed release is
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now the granulation process could not be sufficient controlled. The reasons
were that during enzyme granulation a thick and not easily removable layer of
the solid material builds up on the granulator wall. Furthermore the mixture of
salt and enzyme powder is difficult to granulate in the high-shear mixer since
the transition from sufficiently wetted to an over wetted mixture requires a very
small amount of water. Novo solved this problem by including the cellulose
fibres, they are believed to be responsible for preventing buildup on the walls
and for affording a greater control of particle growth.
In another patent of Novo [30] a device for two kinds of enzymes is
described. It consists of a core of a primary enzyme, cellulose fibers and sodium
sulphate, coated with a sustained release layer which itself is surrounded by a
shell comprising of the secondary enzyme mixed with binder, filler, and
granulating agents. Finally this shell is coated with a non-dusting layer (PEG
4000). For example, the primary enzyme is a protease and the secondary a
lipase, so the lipase is released fast in the washing water and the protease
slowly which improves the stability of the lipases in the washing water. The
sustained release layer can be a mono-, di-, trigyceride of a fatty acid (Grindtek
MSP90).
A very similar formulation is described in a more recent patent (US
5733763) [31] with the difference that the production of the formulation is now
completely carried out in a drum-granulator. This is done by sequential
addition of the components to the granulator. Novo claims that this method is
easier to scale-up compared to for example fluid bed coating methods.
A delayed release formulation of Novo for peroxidase enzymes is
described in WO patent 95/33039 [32]. The formulation is developed for dye-
transfer inhibition, i.e. inhibition of fabric-to-fabric transfer of dye during
washing. Dye-transfer inhibition is achieved by bleaching of the washing water
(i.e. removal of coloration by degradation of dye dissolved in the washing
liquor) by enzymatic means. The enzymes used for dye-transfer inhibition are
peroxidases together with an accelerator. The peroxidase enzymes should be
released in the washing water when the other oxidation-sensitive components,
such as other enzymes, have been able to perform their intended function. This
is achieved by applying 10 to 40-w/w% water-insoluble coating on a core with a
comparable composition as in the patent described above [30].
Another reservoir device (a device consisting of a core with therein the
active ingredient surrounded by a release rate limiting coating) in relation to
detergents is made by EKA Nobel [33] it consists of a core of a bleaching agent
with a filler coated with a hydrophobic substance with therein dissolved
surfactants and containing water swellable grains. The water swellable grains
will absorb water and expand in volume. This expansion will break the
hydrophobic coating and thereby inducing fast dissolution of the bleaching
agent. The surfactants dissolved in the hydrophobic coating increase the rate of
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water absorption. The core consists out of a peroxy bleaching agent and a filler
such as sodium sulphate. The hydrophobic coating is a natural occuring
polymer, such as an animal or vegetable fat, because they are cheap and
environmental friendly. To improve the mechanical strength and moisture-
barrier properties of the coating, synthetic polymers like polyethylene or ethyl
cellulose are incorporated. Preferred swellable grain materials are cold water
soluble starch and starch derivatives. The microcapsules are prepared by
making a suspension of the cores and the swellable grains in the molten coating
material with therein dissolved a surfactant. The suspension is fed to a rotating
disc and active or passive cooling solidifies the formed droplets. Fluid bed
coating of the cores is also possible.
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initial stage should be 10-11 for about 5 minutes and the completion of the
washing cycle should be at a pH level of 8-9.
The inventor gives several suggestions how delayed release of the acid
should take place. Most ideally the acid should be pumped into the washing
machine with an external pump at a certain point in time. In this way a pulse
release of the acid is obtained and the decrease in pH can be controlled most
ideally.
A more practical solution is the coating of citric acid particles with 10-
w/w % paraffin wax. The paraffin wax provides in a delay in the release in that
it must first be melted or dissolved by the washing water before the acid is
effectively released into the washing solution. The effective pH curve obtained
by this formulation is a first-order decrease of the pH, without an initial period
with a constant high pH, until the final pH is reached.
Another option is generating acid by chemical hydrolysis of a methylester
of an acid. The release rate can be adjusted by changing the substituent R on the
acid with the general formula ROCH3. Comparison of different types of esters
listed illustrates that methyl glycolate hydrolyzes relatively slowly. Faster
reactivity, and thus faster acid release, is observed with the other esters having
substituted reactive groups of -Cl, -Cl2 and -NO2. The release profile obtained is
first order in kinetics.
The final example given is the control of the acid release rate by changing
the chain length in aliphatic dicarboxylic acids. The higher the number of
carbon atoms in the chain the longer the dissolution time and thus the slower
the acid release rate. In this way a release profile is obtained similar to the
previous example.
The third and most recent patent (US5716923) [36] describes the coating of
sodium percarbonate bleach with alkali metal carbonate and an alkali metal
sulfate salt. The coating is applied because the sodium percarbonate is relatively
unstable in a detergent environment especially in moist or warm atmospheres.
The coating gives a retention of the solution of the bleach in the washing water
and this normally means a decrease in washing performance. However when a
controlled pH release method is used the cleaning performance can be
enhanced. To achieve this controlled pH release method the author suggests the
use of coated acid particles. The recommended acid to use is citric acid because
it has the advantage of providing builder capacity to the wash solution. As a
coating a dual coating is preferred with an inner coating of wax (paraffin with a
melting point in the range 50 ºC to 90ºC) and an outer silica coating. This dual
coating allows for improved particle flow and control over the dissolution rate.
As a production method the author suggests agglomeration or spraying the
solutions on a moving bed of particles.
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The conclusion we can draw from the available literature is that a device
which consists of a core with therein the active surrounded by a protecting and
release rate controlling coating is the most used in pulse release devices.
Advantages are the strict separation between the release rate controlling
part and the part containing the active which are essential conditions if a pulse
release profile is desirable, and the protective function of the coating which acts
as a barrier to other harmful components.
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The most important goal of the product developed in this thesis is the
enhanced performance of a dry powder detergent by sequential release of the
active ingredient in the washing water. To achieve this goal the product
developed in this thesis should fulfill certain demands the most important
being:
1. an (beforehand) adjustable lag-time (the time without any release of the
contents) up to 45 minutes,
2. a pulse or immediate release of the active components in the product in the
washing water after the lag-time,
3. it should consist out of particulate matter in the size range 0.3-1.0 mm,
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21. Cullen, K., Detergent composition comprising enzyme and delayed release mechanism. patent
# : WO 97/23593; The Proctor & Gamble Company; 1997; ; p. 1-27.
22. Jeffrey, J., J.S. Park, and G.M. Baillely, Detergents containing a surfactant and a delayed
release peroxyacid bleach system. patent # : US5755992; The Proctor & Gamble company;
1998; ; p. 1-26.
23. Baston, G.M., J. Jeffrey, and G.M. Baillely, Detergents containing an enzyme and a delayed
release peroxyacid bleaching system. patent # : WO 95/28467; The Proctor & Gamble
Company; 1995; GB; p. 1-17.
24. Baillely, G.M., J. Jeffrey, and J.S. Park, Detergents containing a surfactant and a delayed
release enzyme. patent # : WO95/28466; The Proctor & Gamble company; 1995; ; p. 1-15.
25. Arnold, R.E., et al., Enzyme containing granules coated with hydrolyzed polyvinyl alcohol or
copolymer thereof. patent # : 5324649; Genencor International Inc.; 1994; US patent; p. 1-
12.
26. Dale, A.D., et al., Coated enzyme-containing granule. patent # : US5879920; Genencor
International Inc.; 1999; US; p. 1-7.
27. Andela, C., et al., Process for dust-free enzyme manufacture. patent # : WO 94/26883; Gist
Brocades N.V.; 1994; NL; p. 1-13.
28. Markussen, E.K. and P. Falholt, Granulate detergent enzyme product, method for production
thereof, use thereof, and detergent containing such product. patent # : WO 89/08694; Novo
industri A/S; 1989; DK; p. 1-22.
29. Kadam, K.L., Granulation processes for industrial enzymes., in Granulation technology for
bioproducts., K.L. Kadam, Editor. 1990, CRC press: Boca Raton, Florida. p. 297-313.
30. Markussen, E.K. and P. Falholt, Enzyme containing granulate and method for production
thereof. patent # : WO 90/09440; Novo Nordisk A/S; 1990; DK; p. 1-25.
31. Markussen, E.K. and P. Falholt, Enzyme granulate formed of an enzyme-containing core and
an enzyme-containing shell. patent # : US5733763; Novo Nordisk A/S; 1998; Denmark; p.
1-15.
32. Damhus, T. and D.A. Petersen, Dye-transfer inhibitory preparation and detergent
composition comprising such a preparation. patent # : WO95/33039; Novo Nordisk; 1995;
Denmark; p. 1-6.
33. Langemo, L., R.E. Sparks, and I.C. Jacobs, Bleaching agent. patent # : EP 0 573 731 A1;
EKA Nobel industries AB; 1992; Sweden; p. 1-9.
34. Barnes, S.G., Improved detergent bleach composition and method of cleaning fabrics. patent # :
EP0290081; Unilever NV; 1988; ; p. 1-6.
35. Kong, S.B., S.D. Ratcliff, and D.S. Steichen, Method and product for enhancing bleaching
with in situ peracid formation. patent # : EP0396287; The Clorox Company; 1990; US; p. 1-
9.
36. MacBeath, F.S., Laundry detergent containing a coated percarbonate and an acidification agent
to provide delayed lowered pH. patent # : US5716923; The Proctor & Gamble Company;
1998; US; p. 1-11.
37. Cornelissens, E.G., Detergent composition containing an alkali carbonate. patent # :
US4210550; Akzo NV; 1980; Netherlands; p. 1-5.
38. Falotico, A.J., S.A. Bolkan, and L.R. Mazzola, Carbonate built laundry detergent
composition containing a delayed release polymer. patent # : US 5496376; Church & Dwight
Co., Inc,.; 1996; ; p. 1-11.
39. Rahse, W., et al., Feste Wertstoffbereitungen fur die mehrstufige Textilwasche. patent # :
DE4438850 A1; Henkel KGaA; 1996; Deutschland; p. 1-18.
40. Starch, M.S., Delayed release antifoam additives patent # : EP890303315; Dow corning (US);
1989; US; p. 1-5.
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