Note: Descriptions are shown in the official language in which they were submitted.
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
1
METHODS FOR TREATING GLASSWARE SURFACES USING CORROSION
PROTECTION AGENTS
FIELD OF THE INVENTION
The present invention relates to methods for treating glassware surfaces, for
example
dishes and glasses, using corrosion protection agents, especially corrosion
protection agents
comprising zinc-containing materials. Methods using corrosion protection
agents that form a part
of a treatment system and/or are incorporated in a composition of matter are
also provided.
BACKGROUND
Automatic dishwashing detergents constitute a generally recognized distinct
class of
detergent compositions whose purpose can include breaking down and removing
food soils;
inhibition of foaming; promoting the wetting of wash articles in order to
minimize or eliminate
visually observable spotting and filming; removing stains such as might be
caused by beverages
such as coffee and tea or by vegetable soils such as carotenoid soils;
preventing a buildup of soil
films on wash ware surfaces; and reducing tarnishing of flatware without
substantially etching or
corroding or otherwise damaging the surfaces of glasses or dishes. The problem
of glassware
surface corrosion during washing the cycle in the automatic dishwashing
process has long been
known. Current opinion is that the problem is the result of two separate
phenomena. On one hand,
the high pH needed for cleaning causes silica hydrolysis. This dissolved
silica/ate (together with
silicates added purposely to prevent china and metal corrosion) deposit on the
glasswaresurface
leading to iridescence and clouding. On the other hand, builders cause
corrosion. The builders
will chelate metal ions on glassware surfaces, which results in metal ion
leaching and renders a
less durable and chemical resistant glass. After several washes in an
automatic dishwashing
appliance, both phenomena can cause significant corrosion damage to glassware
surfaces such as
cloudiness, scratches, and streaks that results in consumer dissatisfaction.
Most consumers agree that corrosion of glassware surfaces, resulting from use
of
automatic dishwashing (ADW) appliances, is one of their most serious unmet
needs. One
approach to reducing glassware surface corrosion is to provide corrosion
protection agents
comprising water-soluble metal salts (such as zinc salts of chloride, sulfate
or acetate) to afford
some measure of glassware surface protection. Another approach is reduce
precipitate formation,
caused by the introduction of soluble zinc salts in a high pH environment, by
spraying a solution
of the water-soluble zinc salt onto granular polyphosphate particles. Another
approach is to
combine soluble zinc and a chelant. Another approach is to use insoluble zinc
salt to control the
release of Zn2+ ions in the rinse to avoid filming. Another approach is to
provide an automatic
dishwashing composition with a mixture of disilicate and metasilicate. Another
approach is to
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
2
provide an additive to an automatic dishwashing composition, such as, a
copolymer of an
organomineral siliconate, which is obtained by condensation polymerization of
an alkali metal
disilicate and an alkali metal siliconate. Another approach is to provide an
alkali metal silicate
partially substituted with calcium, magnesium, strontium or cerium as a
counterion. Another
approach is the use of metal salts, particularly of aluminum, wherein the
metal salt is sequestered
to form a metal salt-sequestrant complex, such as, an aluminum (III)-
sequestrant complex. In yet
another approach, a fast-dissolving aluminum salt is used but this aluminum
salt is combined with
greater than about 10 wt. % silicate in high alkalinity products.
Thus, while there are many approaches available, there is still a continuing
need to
develop alternative methods of reducing glassware surface corrosion using
corrosion protection
agents such that significant glasscare benefits are achieved yet the problem
of glassware surface
corrosion is reduced.
SUMMARY OF THE INVENTION
The present invention relates to domestic, institutional, industrial, and/or
commercial
methods of using corrosion protection agents, especially certain zinc-
containing materials, such
as, particulate zinc-containing materials (PZCMs) and zinc-containing layered
materials
(ZCLMs), for treating glassware surfaces in automatic dishwashing appliances.
The corrosion
protection agents described herein can be used in alone, in combination with
detergent
compositions, or as part of a treatment system and/or composition of matter to
reduce glassware
surface corrosion in automatic dishwashing processes.
In accordance with one aspect, a method of reducing glassware surface
corrosion in an
automatic dishwashing appliance comprising the step of contacting a glassware
surface with a
corrosion protection agent is provided. The corrosion protection agent
comprises: (a) an effective
amount of certain zinc-containing materials, such as, PZCMs and ZCLMs; and (b)
optionally an
adjunct ingredient.
In accordance with another aspect, a method of reducing glassware surface
corrosion
using a treatment system is provided. A corrosion protection agent comprising
an effective
amount of certain zinc-containing materials, such as, PZCMs and ZCLMs, can be
part of the
treatment system for reducing glassware surface corrosion in an automatic
dishwashing appliance.
In accordance with another aspect, a method of reducing glassware surface
corrosion using a
composition of matter is provided. The composition of matter comprises a wash
liquor that
comprises a corrosion protection agent comprising certain zinc-containing
materials, such as,
PZCMs and ZCLMs. In accordance with another aspect, a process of manufacturing
a corrosion
protection agent is provided. The process comprises the steps of (a) providing
and (b) combining
certain zinc-containing materials, such as, PZCMs and ZCLMs; and (c)
optionally, adding an
adjunct ingredient to form the corrosion protection agent.
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
3
DRAWING DESCRIPTION
Fig. 1 represents the structure of a zinc-containing layered material.
Fig. 2 represents a comparison of glassware surface strength using specular
reflection IR
DETAILED DESCRIPTION
It has surprisingly been found that glassware in automatic dishwashing can be
protected
using methods of treating glassware surfaces by contacting glassware with
corrosion protection
agents containing certain zinc-containing materials, such as, particulate zinc-
containing materials
(PZCMs) and zinc-containing layered materials (ZCLMs). This is especially true
in soft water
conditions where chelating agents and builders can damage glassware by
chelating metal ions in
the glass structure itself. Thus, even in such harsh ADW environments, glass
damage from
surface corrosion can be reduced with the use of ZCLMs in ADW detergent
compositions without
the negative effects associated with the use of metal salts, such as: (a)
increased cost of
manufacture; (b) the need for higher salt levels in the formula due to poor
solubility of the
insoluble material; (c) the thinning of gel detergent compositions by
interaction of the metal ions,
for example Al3+ ions and Zn2+ ions, with the thickener material; or (d) a
reduction in the cleaning
performance for tea, stains by interfering with the bleach during the entire
wash cycle. It has also
surprisingly been found that the glass care benefit of the ZCLM is
significantly enhanced when
the ZCLM is dispersed prior to adding to or during the process of
manufacturing the corrosion
protection agent. Achieving good dispersion of the ZCLM particles in the
corrosion protection
agent significantly reduces agglomeration of the ZCLM particles in the wash
liquor.
In the methods described herein, any suitable corrosion protection agent may
be used,
alone or in combination with a composition of matter (such as the wash
liquor), and/or as part of a
treatment system comprising a kit having an effective amount of certain zinc-
containing materials,
such as, PZCMs and ZCLMs. By "effective amount" herein is meant an amount that
is sufficient,
under the comparative test conditions described herein, to reduce glassware
surface corrosion
damage on treated glassware through-the-wash.
PARTICULATE ZINC-CONTAINING MATERIALS (PZCMs)
Particulate zinc-containing materials (PZCMs) remain mostly insoluble within
formulated
compositions. Examples of PZCMs useful in certain non-limiting embodiments may
include the
following:
Iraof ga~aic Materials: zinc aluminate, zinc carbonate, zinc oxide and
materials containing
zinc oxide (i.e., calamine), zinc phosphates (i.e., orthophosphate and
pyrophosphate), zinc
selenide, zinc sulfide, zinc silicates (i.e., ortho- and meta-zinc silicates),
zinc silicofluoride, zinc
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
4
borate, zinc hydroxide and hydroxy sulfate, zinc-containing layered materials,
and combinations
thereof.
Natural Zinc-corataifaing Materials l Ores and Minerals: sphalerite (zinc
blende),
wurtzite, smithsonite, franklinite, zincite, willemite, troostite,
hemimorphite, and combinations
thereof.
Organic Salts: zinc fatty acid salts (i.e., caproate, laurate, oleate,
stearate, etc.), zinc salts
of alkyl sulfonic acids, zinc naphthenate, zinc tartrate, zinc tannate, zinc
phytate, zinc
monoglycerolate, zinc allantoinate, zinc urate, zinc amino acid salts (i.e.,
methionate,
phenylalinate, tryptophanate, cysteinate, etc), and combinations thereof.
Polymeric Salts: zinc polycarboxylates (i.e., polyacrylate), zinc polysulfate,
and
combinations thereof.
Physically Adsorbed Forms: zinc-loaded ion exchange resins, zinc adsorbed on
particle
surfaces, composite particles in which zinc salts are incorporated (i.e., as
corelshell or aggregate
morphologies), and combinations thereof.
Zifac Salts: zinc oxalate, zinc tannate, zinc tartrate, zinc citrate, zinc
oxide, zinc carbonate,
zinc hydroxide, zinc oleate, zinc phosphate, zinc silicate, zinc stearate,
zinc sulfide, zinc
undecylate, and the like, and combinations thereof.
Commercially available sources of zinc oxide include Z-Cote and Z-Cote HPI
(BASF),
and USP I and USP II (Zinc Corporation of America).
PHYSICAL PROPERTIES OF PZCM PARTICLES
In the methods described herein, many benefits of using PZCMs in corrosion
protection
agents require that the Zn2+ ion be chemically available without being
soluble. This is termed
"zinc lability". Certain physical properties of the PZCM have the potential to
impact zinc lability.
We have developed more effective corrosion protection agents based on
optimizing PZCM zinc
lability.
Some PZCM physical properties that can impact zinc lability may include, but
are not
limited to: crystallinity, surface area, and morphology of the particles, and
combinations thereof.
Other PZCM physical properties that may also impact zinc lability of PZCMs
include, but are not
limited to: bulls density, surface charge, refractive index, purity level, and
combinations thereof.
Crystallinity
A PZCM having a less crystalline structure may result in a higher relative
zinc lability.
One can measure crystal imperfections or crystalline integrity of a particle
by full width half
maximum (FWHM) of reflections of an x-ray diffraction (XRD) pattern. Not
wishing to be
bound by theory, it is postulated that the larger the FWHM value, the lower
the level of
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
crystallinity in a PZCM. The zinc lability appears to increase as the
crystallinity decreases. Any
suitable PZCM crystallinity may be used. For example, suitable crystallinity
values may range
from about 0.01 to 1.00, or from about 0.1 to about 1.00, or form about 0.1 to
about 0.90, or from
about 0.20 to about 0.90, and alternatively, from about 0.40 to about 0.86
FWHM units at a 200
(~13° 28, 6.910 reflection peak.
Particle Size
The PZCM particles in the corrosion protection agent may have any suitable
average
particle size. In certain non-limiting embodiment, it is has been found that a
smaller particle size
is directly proportional to an increase in relative zinc lability (%).
Suitable average particle sizes
include, but not limited to: a range of from about 10 nm to about 100 microns,
or from about 10
nm to about 50 microns, or from about 10 nm to about 30 microns, or from about
10 nm to about
20 microns, or from about 10 nm to about 10 microns, and alternatively, from
about 100 nm to
about 10 microns. In another non-limiting embodiment, the PZCM may have an
average particle
size of less than about 15 microns, or less than about 10 microns, and
alternatively less than about
5 microns.
Particle Size Distribution
Any suitable PZCM particle size distribution may be used. Suitable PZCM
particle size
distributions include, but are not limited to: a range from about 1 nm to
about 150 microns, or
from about 1 nm to about 100 microns, or from about 1 nm to about 50 microns,
or from about 1
nm to about 30 microns, or from about 1 nm to about 20 microns, or from about
1 nm to about 10
microns, or from about 1 nm to about 1 micron, or from about 1 nm to about 500
nm, or from
about 1 nm to about 100 nm, or from about 1 nm to about 50 nm, or from about 1
nm to about 30
nm, or from about 1 nm to about 20 nm, and alternatively, from about 1 nm or
less, to about 10
nm.
ZINC-CONTAINING LAYERED MATERIALS (ZCLMs)
As already defined above, ZCLMs are a subclass of PZCMs. Layered structures
are those
with crystal growth primarily occurring in two dimensions. It is conventional
to describe layer
structures as not only those in which all the atoms are incorporated in well-
defined layers, but also
those in which there are ions or molecules between the layers, called gallery
ions (A.F. Wells
"Structural Inorganic Chemistry" Clarendon Press, 1975). For example, ZCLMs
may have Znz+
ions incorporated in the layers and/or as more labile components of the
gallery ions.
Many ZCLMs occur naturally as minerals. Common examples include hydrozincite
(zinc
carbonate hydroxide), basic zinc carbonate, aurichalcite (zinc copper
carbonate hydroxide),
rosasite (copper zinc carbonate hydroxide) and many related minerals that are
zinc-containing.
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
6
Natural ZCLMs can also occur wherein anionic layer species such as clay-type
minerals (e.g.,
phyllosilicates) contain ion-exchanged zinc gallery ions. Other suitable ZCLMs
include the
following: zinc hydroxide acetate, zinc hydroxide chloride, zinc hydroxide
lauryl sulfate, zinc
hydroxide nitrate, zinc hydroxide sulfate, hydroxy double salts, and mixtures
thereof. Natural
ZCLMs can also be obtained synthetically or formed in situ in a composition or
during a
production process.
Hydroxy double salts can be represented by the general formula:
~Mz+~_XMz+I+X(OH)3(t-Y>~+ An (1=3Y)in~nHzO
where the two metal ions may be different; if they are the same and
represented by zinc, the
formula simplifies to [Zn,+X(OH)a]2"~ 2x AvnH20 (see Morioka, H., Tagaya, H.,
Karasu, M,
Kadokawa, J, Chiba, K Izzorg. Chem. 1999, 38, 4211-6). This latter formula
represents (where
x=0.4) common materials such as zinc hydroxychloride and zinc hydroxynitrate.
These are
related to hydrozincite as well, when a divalent anion replaces the monovalent
anion.
Commercially available sources of zinc carbonate include zinc carbonate basic
(Cater
Chemicals: Bensenville, IL, USA), zinc carbonate (Shepherd Chemicals: Norwood,
OH, USA),
zinc carbonate (CPS Union Corp.: New York, NY, USA), zinc carbonate (Elementis
Pigments:
Durham, UK), and zinc carbonate AC (Bruggemann Chemical: Newtown Square, PA,
USA).
The abovementioned types of ZCLMs represent relatively common examples of the
general category and are not intended to be limiting as to the broader scope
of materials that fit
this definition.
Any suitable ZCLM in any suitable amount may be used in the methods described
herein.
Suitable amounts of a ZCLM include, but are not limited to: a range: from
about 0.001% to about
20%, or from about 0.001% to about 10%, or from about 0.01% to about 7%, and
alternatively,
from about 0.1% to about 5% by weight of the composition.
ZCLM GLASS NETWORK STRENGTHENING MECHANISM
It is well known that silica glass is a continuous three-dimensional (3D)
network of
corner-shared Si-0 tetrahedra-lacking symmetry and periodicity (see W. H.
Zachariasen, J. Am.
Chem. Soc. 54, 3841, 1932). Si4+ ions are network forming ions. At the vertex
of each
tetrahedron, and shared between two tetrahedra, is an oxygen atom known as a
bridging oxygen.
Mechanical glass surface properties, such as chemical resistance, thermal
stability, and
durability, may depend on the glassware surface structure itself. Without
wishing to bound by
theory, it is believed that when some network forming positions are occupied
by zinc compounds
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
7
or Zn2+ ions, the mechanical properties of the glassware surface structure
improve (see G. Calas
et al. C. R. Chimie 5 2002, 831-843).
Figure 1 depicts a zinc-containing layered structure with crystal growth
primarily
occurring in two dimensions. Zn2+ ions are incorporated in the layers and/or
as more labile
components of the gallery ions. For example, ZCLMs, such as synthetic zinc
carbonate
hydroxide (ZCH) or natural-occurring hydrozincite (HZ), may have the formula:
3Zn(OH)2.2ZnC03 or Zn5(OH)6(C03)z,
and consist of Zn2+ ions forming brucite type hydroxide layers with some
octahedral vacancies as
shown in Fig 1. Some of the Zn2+ ions are positioned just above and below the
vacant sites
outside the hydroxide layers in tetrahedral (Td) coordination. Interlayer
anions are weakly bound
to the Td Zn2+ ions completing the Td coordination. In the wash liquor, an ADW
detergent
composition with labile Td Zn2+ ions is stable at the typical alkaline pH.
When a ZCLM is present in the wash water, the cationic charge on the brucite
type
hydroxide layers is the driving force for interaction with the negatively
charged glass surface.
This leads to efficient deposition of zinc compounds or Zn2+ ions on the glass
surface such that
very low level of ZCLMs are needed to deliver a benefit. Once the brucite type
hydroxide layers
are placed in contact with the glass, zinc compounds or Znz+ ions can readily
deposit on the glass
and fill in the vacancies created by metal ion leaching and silica hydrolysis
commonly occurring
with ADW products. Thus, new zinc compounds or Zn2+ ions, introduced as glass
network
formers, strengthen the glass and prevent glass corrosion during further
washes.
CORROSION PROTECTION AGENTS AND COMPOSITIONS OF MATTER
The methods described herein provide at least some glassware surface corrosion
protection to glassware surfaces when treated with the corrosion protection
agent during at least
some portion of the wash cycle.
In one non-limiting embodiment, a corrosion protection agent comprises an
effective
amount of a ZCLM, such that when the ZCLM is placed in contact with the
glassware surface, an
amount of zinc compounds or Zn2+ ions is deposited on and/or within the
imperfections or
vacancies in the glassware surface. For example, the treated glassware surface
may have zinc
compounds or Zn2+ ions present from about 1 nm up to about 1 micron, or from
about 1 nm to
about 500 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about
50 nm, or from
about 1 nm to about 20 nm, and alternatively, from about 1 nm to about 10 nm
above and/or
below the treated glassware surface.
In another non-limiting embodiment, a composition of matter comprises a wash
liquor,
which comprises a corrosion protection agent comprising an effective amount of
a ZCLM, in an
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
8
automatic dishwashing appliance during at least a part of the wash cycle,
wherein from about
0.0001 ppm to about 100 ppm, or from about 0.001 ppm to about 50 ppm, or from
about 0.01 ppm
to about 30 ppm, and alternatively, from about 0.1 ppm to about 10 ppm of a
ZCLM may be
present in the wash liquor.
Any suitable pH in an aqueous corrosion protection agent containing a ZCLM may
be
used in the methods described herein. In certain embodiments, a suitable pH
may fall anywhere
within the range of from about 6.5 to about 14. For example, certain
embodiments of the
corrosion protection agent have a pH of greater than or equal to about 6.5, or
greater than or equal
to about 7, or greater than or equal to about 9, and alternatively, greater
than or equal to about
10Ø
ADJUNCT INGREDIENTS
Any suitable adjunct ingredient in any suitable amount or form may be used.
For a
example, a detergent active and/or rinse aid active, adjuvant, and/or
additive, may be used in
combination with a ZCLM to form a composite corrosion protection agent.
Suitable adjunct
ingredients include, but are not limited to, cleaning agents, surfactant (for
example, anionic,
cationic, nonionic, amphoteric, zwitterionic, and mixtures thereof), chelating
agent/sequestrant
blend, bleaching system (for example, chlorine bleach, oxygen bleach, bleach
activator, bleach
catalyst, and mixtures thereof), enzyme (for example, a protease, lipase,
amylase, and mixtures
thereof), alkalinity source, water softening agent, secondary solubility
modifier, thickener, acid,
soil release polymer, dispersant polymer, thickeners, hydrotrope, binder,
carrier medium,
antibacterial active, detergent filler, abrasive, suds suppresser, defoamer,
anti-redeposition agent,
threshold agent or system, aesthetic enhancing agent (i.e., dye, colorants,
perfume, etc.), oil,
solvent, and mixtures thereof.
Dispersant Polymer
Any suitable dispersant polymer in any suitable amount may be used.
Unsaturated
monomeric acids that can be polymerized to form suitable dispersant polymers
(e.g.
homopolymers, copolymers, or terpolymers) include acrylic acid, malefic acid
(or malefic
anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,
citraconic acid and
methylenemalonic acid. The presence of monomeric segments containing no
carboxylate radicals
such as methyl vinyl ether, styrene, ethylene, etc. may be suitable provided
that such segments do
not constitute more than about 50% by weight of the dispersant polymer.
Suitable dispersant
polymers include, but are not limited to those disclosed in U.S. Patent Nos.
3,308,067; 3,308,067;
and 4,379,080.
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
9
Substantially non-neutralized forms of the polymer may also be used in the
corrosion
protection agents. The molecular weight of the polymer can vary over a wide
range, for instance
from about 1000 to about 500,000, alternatively from about 1000 to about
250,000. Copolymers
of acrylamide and acrylate having a molecular weight of from about 3,000 to
about 100,000, or
from about 4,000 to about 20,000, and an acrylamide content of less than about
50%, and
alternatively, less than about 20%, by weight of the dispersant polymer can
also be used. The
dispersant polymer may have a molecular weight of from about 4,000 to about
20,000 and an
acrylamide content of from about 0% to about 15%, by weight of the polymer.
Suitable modified
polyacrylate copolymers include, but are not limited to the low molecular
weight copolymers of
unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766,
and 5,084,535; and
European Patent No. 0,066,915.
Other suitable dispersant polymers include polyethylene glycols and
polypropylene
glycols having a molecular weight of from about 950 to about 30,000, which can
be obtained
from the Dow Chemical Company of Midland, Michigan. Such compounds for
example, having
a melting point within the range of from about 30°C to about
100°C can be obtained at molecular
weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are
formed by the
polymerization of ethylene glycol or propylene glycol with the requisite
number of moles of
ethylene or propylene oxide to provide the desired molecular weight and
melting point of the
respective and polypropylene glycol. The polyethylene, polypropylene and mixed
glycols are
referred to using the formula:
HO(CH2CH20) (CH2CH(CH3)O) (CH(CH3)CH20)OH
m n
wherein m, n, and o are integers satisfying the molecular weight and
temperature requirements
given above.
Suitable dispersant polymers also include the polyaspartate, carboxylated
polysaccharides, particularly starches, celluloses and alginates, described in
U.S. Pat. No.
3,723,322; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat.
No. 3,929,107; the
hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and
starch hydrolysates
described in U.S. Pat No. 3,803,285; the carboxylated starches described in
U.S. Pat. No.
3,629,121; and the dextrin starches described in U.S. Pat. No. 4,141,841.
Suitable cellulose
dispersant polymers, described above, include, but are not limited to:
cellulose sulfate esters (for
example, cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose
sulfate,
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
methylcellulose sulfate, hydroxypropylcellulose sulfate, and mixtures
thereof), sodium cellulose
sulfate, carboxymethyl cellulose, and mixtures thereof.
In certain embodiments, a dispersant polymer may be present in an amount in
the range
from about 0.01% to about 25%, or from about 0.1% to about 20%, and
alternatively, from about
0.1% to about 7% by weight ofthe composition.
Carrier Medium
Any suitable carrier medium in any suitable amount in any suitable form may be
used.
Suitable carrier mediums include both liquids and solids depending on the
forni of the corrosion
protection agent desired. A solid carrier medium may be used in dry powders,
granules, tablets,
encapsulated products, and combinations thereof. Suitable solid carrier
mediums include, but are
not limited to carrier mediums that are non-active solids at ambient
temperature. For example,
any suitable organic polymer, such as polyethylene glycol (PEG), may be used.
In certain
embodiments, the solid carrier medium may be present in an amount in the range
from about
0.01% to about 20%, or from about 0.01% to about 10%, and alternatively, from
about 0.01% to
about 5% by weight of the composition.
Suitable liquid carrier mediums include, but are not limited to: water
(distilled, deionized,
or tap water), solvents, and mixtures thereof. The liquid carrier medium may
be present in an
amount in the range from about 1 % to about 90%, or from about 20% to about
80%, and
alternatively, from about 30% to about 70% by weight of the aqueous
composition. The liquid
carrier medium, however, may also contain other materials which are liquid, or
which dissolve in
the liquid carrier medium at room temperature, and which may also serve some
other function
besides that of a carrier. These materials include, but are not limited to:
dispersants, hydrotropes,
and mixtures thereof.
The corrosion protection agent can be provided in a "concentrated" system. For
example,
a concentrated liquid composition may contain a lower amount of a suitable
carrier medium,
compared to conventional liquid compositions. Suitable carrier medium content
of the
concentrated system may be present in an amount from about 30% to about 99.99%
by weight of
the concentrated composition. The dispersant content of the concentrated
system may be present
in an amount from about 0.001% to about 10 % by weight of the concentrated
composition.
PRODUCT FORM
Any suitable product form may be used. Suitable product forms include, but not
limited
to: solids, granules, powders, liquids, gels, pastes, semi-solids, tablets,
water-soluble pouches, and
combinations thereof. The corrosion protection agent may also be packaged in
any suitable form,
for example, as part of a treatment system comprising a kit, which may
comprise (a) a package;
(b) an effective amount of a zinc-containing layered material; (c) optionally,
an adjunct
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
11
ingredient; and (d) instructions for using the corrosion protection agent to
reduce glassware
surface corrosion. The corrosion protection agent, as part of the treatment
system, may be
formulated in a single- and/or mufti-compartment water-soluble pouch so that
negative
interactions with other components are reduced.
The corrosion protection agent suitable for use herein can be dispensed from
any suitable
device, including but not limited to: dispensing baskets or cups, bottles
(pump assisted bottles,
squeeze bottles, etc.), mechanic pumps, mufti-compartment bottles, capsules,
mufti-compartment
capsules, paste dispensers, and single- and mufti-compartment water-soluble
pouches, and
combinations thereof. For example, a mufti-phase tablet, a water-soluble or
water-dispersible
pouch, and combinations thereof, may be used to deliver the corrosion
protection agent to any
suitable solution or substrate. Suitable solutions and substrates include but
are not limited to: hot
and/or cold water, wash and/or rinse liquor, hard surfaces, and combinations
thereof. The multi-
phase product may be contained in a single or mufti-compartment, water-soluble
pouch. In
certain embodiments, a corrosion protection agent may comprise a unit dose
which allows for the
controlled release (for example delayed, sustained, triggered, or slow
release). The unit dose may
be provided in any suitable form, including but not limited to: tablets,
single- and multi-
compartment water-soluble pouch, and combinations thereof. For example, the
corrosion
protection agent may be provided as a unit dose in the form of a mufti-phase
product comprising a
solid (such as a granules or tablet) and a liquid andlor gel separately
provided in a multi-
compartment water-soluble pouch.
PROCESS OF MANUFACTURE
Any suitable process having any number of suitable process steps may be used
to
manufacture the corrosion protection agents described herein in any suitable
form (e.g. solids,
liquids, gels). The corrosion protection agent may be formulated with any
suitable amount of
ZCLM in any suitable form either alone or in combination with an adjunct
ingredient. The
ZCLM that may be nonfriable, water-soluble or water-dispersible and/or may
dissolve, disperse
and/or melt in a temperature range of from about 20° C to about 70
° C. The corrosion protection
agent may be manufactured in the form of a powder, granule, crystal, core
particle, aggregate of
core particles, agglomerate, particle, flake, extrudate, grill, or as a
composite (e.g. in the form of a
composite particle, flake, extrudate, grill), and combinations thereof.
A composite corrosion protection agent in the form of a composite particle,
grill, flake
and/or extrudate may be made separately by mixing raw ZCLM particles in powder
form with the
desired adjunct ingredient (such as, surfactant, dispersant polymer and/or
carrier medium) in any
order. Using the composite corrosion protection agent tends to reduce
segregation. Thus, the
tendency of the corrosion protection agent to settle or agglomerate in the
final product is
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
12
decreased. Furthermore, an enhancement of the dispersion of ZCLM particles in
the wash liquor
is observed once the composite corrosion protection agent is delivered during
the wash cycle. It
has also been observed that by delivering an increased dispersion of the ZCLM
particles in the
wash liquor, a significant improvement in the glasscare surface corrosion
protection performance
occurs when compared to using the corrosion protection agent comprising raw
ZCLM particles, at
equal levels, without incorporating an adjunct ingredient.
When the above-mentioned composite corrosion protection agent comprises a one
or
more carrier components, the carrier components) may be heated to above their
melting point
before adding the desired components (such as for example, a ZCLM, and/or an
adjunct
ingredient). Carrier components suitable for preparing a solidified melt are
typically non-active
components that can be heated to above melting point to form a liquid, and are
cooled to form an
intermolecular matrix that can effectively trap the desired components.
The corrosion protection agent can also be incorporated into a powder,
granule, tablets
and/or solids placed in water-soluble pouch formulations by spraying a liquid
corrosion protection
agent (such as a mixture of ZCLM and a liquid carrier) onto the desired
components, for example,
solid base detergent granules. The liquid carrier can be, for example, water,
solvent, surfactant,
and/or any other suitable liquid whereby the corrosion protection agent can be
dispersed. The
above-mentioned spraying step may occur at any suitable time during the
corrosion protection
agent manufacturing process.
In certain embodiments, by directly mixing and/or dispersing raw ZCLM
particles into a
liquid carrier or composition, a liquid corrosion protection agent can be
made. The ZCLM can be
dispersed into water (and/or solvent) prior to the addition of other desired
components. When a
liquid corrosion protection agent is placed in a dispenser, such as a bottle
or water-soluble pouch,
sufficient dispersion of the ZCLM can be achieved in the liquid by stabilizing
the corrosion
protection agent in the composition, either alone or in combination with a
suitable adjunct
ingredient, without the need to make the above-mentioned composite particle,
grill, flake and/or
extrudate.
Another non-limiting embodiment comprises the process steps of forming a
molten
corrosion protection agent by mixing an effective amount of ZCLM into a molten
carrier medium
(such as polyethylene glycol). This molten corrosion protection agent may then
be sprayed, for
example, onto granules, powders and/or tablets if desired.
Another non-limiting embodiment is directed to process of forming a solid
corrosion
protection agent. This is use for granules, powders, tablets, and/or solids
placed in water-soluble
pouches. The process allows the above-described molten corrosion protection
agent to cool to a
solid before grinding to a desired particle size and form (such as, a
composite particle, grill, or
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
13
flake). Optionally, one or more adjunct ingredients may be added in any
amount, form, or order
to the molten carrier medium before the cooling step. The molten mixture can
also be extruded to
form an extrudate composite, then cooled and ground to a desired form and
particle size, if
necessary, and mixed as described above. These ground mixtures form the
desired corrosion
protection agent, and can be delivered for use in any number of applications
(i.e. alone or in
combination with ADW detergent compositions) in any one ox more of the above-
mentioned
forms to promote optimized corrosion protection performance on treated
glassware surfaces.
TEST RESULTS
The results of various tests on corrosion protection agents are presented in
Tables I-IX
and in Fig. 2. The luminescence and etching tests are run under the same
conditions using the
same or similar substrates (e.g. glasses, glass slides, and/or plates) unless
otherwise noted. In
each test, the substrate is washed for 50 to 100 cycles in a General Electric
Model GE2000
automatic dishwasher under the following washing conditions: 0 gpg water -
130°F, regular wash
cycle, with the heated dry cycle turned on. On the top rack of the GE 2000,
the following
substrates are placed: four (4) Libbey 53 non-heat treated 10 oz. Collins
glasses; three (3) Libbey
8564SR Bristol Valley 8 i/z oz. White Wine Glasses; three (3) Libbey 139 13
oz. English Hi-Ball
Glasses; three (3) Luminarc Metro 16 oz. Coolers or 12 oz. Beverage glasses
(use one size only
per test); one (1) Longchamp Cristal d'Arques 53/a oz. wine glass; and one (1)
Anchor Hocking
Pooh (CZ84730B) 8 oz. juice glass (when there are 1 or more designs per box-
use only one
design per test). On the bottom rack of the GE 2000, the following substrates
are placed: two (2)
Libbey Sunray No.15532 dinner plates 9 '/a in.; and two (2) Gibson black
stoneware dinner plates
#3568DP (optional- if not used replace with 2 ballast dinner plates).
All the glasses and/or plates are visually graded for iridescence after
washing and drying
using a 1- 5 grading scale (outlined below). All the glasses and/or plates are
also visually graded
for evidence of etching using the same 1- 5 grading scale used in the
iridescence test. The values
of grading scale are as follows: "1" indicates very severe damage to the
substrate; "2" indicates
severe damage to the substrate; "3" indicates some damage to the substrate;
"4" indicates very
slight damage to the substrate; and "5" indicates no damage to the substrate.
The luminescence test results are shown in Tables I-III and represent a
comparison of
substrate iridescence. The etching test results are shown in Tables IV-VII
represent a comparison
of etching grades. The x-ray photoelectron spectroscopy (XPS) test results are
shown in Table
VII and represent a comparison of zinc compound or Zn2+ ion deposition on
substrates using
hydrozincite.
Table I
Iridescence of glassware substrates washed 100 cycles with liquid gel
products:
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
14
Substrate Li uid Gel withoutLi uid Gel with
HZ 0.1% HZ
Libbe 53 av . of 4 lasses 1 5
B. Valle wine av . of 3 1 5
lasses
Luminarc av . of 3 lasses 1 5
LC Wine (1 lass 1 5
Sunray plate (avg. of 2 1 ~ S
plates) ~
Table II
Iridescence of glassware substrates washed 50 cycles with powder products:
Substrate Powder without Powder with 0.1%
HZ HZ
En lish Hi-Ball av . 3 4 4
lasses
B. Valle Wine av . 3 lasses) 5 5
Luminarc av .3 lasses 4 5
Sunray plate (avg of 2
plates)
Table III
Iridescence of glassware substrates washed 50 cycles with powder products:
Substrate Liquid gel withoutLiquid gel with
Zinc 0.1% Zinc
h drox sulfate h drox sulfate
En lish Hi-Ball (av . 3
3 lasses)
Luminarc av . 3 lasses 3 5
Supra late av . of 2 3 5
lates
Table IV
Etching-of~lassware substrates washed 100 cycles with liauid gel products:
Substrate Liquid Gel withoutLi uid Gel with
HZ 0.1% HZ
Libbe 53 av . of 4 lasses 1.9 4.5
B. Valle wine av . of 1.5 4.5
3 lasses
Luminarc av . of 3 lasses 1 4.2
LC Wine 1 lass 4 5
Table V
Etchin 'of e~lassware substrate washed 50 cycles with uowder products:
Substrate Powder without Powder with 0.1%
HZ HZ
En lish Hi-Ball avg. 3 2.5 . 3.5
glasses
B. Valle Wine av . 3 lasses 4.3 4.8
Luminarc av . 3 lasses 2.3 3.8
Pooh Juice Glass (1 lass) 2.5 3.5
Table VI
Etching of glassware substrate washed 50 cycles with liguid gel:
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
Substrate ~ Liquid Gel withoutLiquid gel with
Zinc 0.1 % Zinc
H drox Sulfate H drox Sulfate
En Iish Hi-Ball av . 3 lasses2 3,3
Luminarc av . 3 lasses 2.3 3.7
Table VII
Etching grades for addition of different amounts of Hydrozincites
Substrate Liquid Liquid Liquid Liquid Liquid
Gel Gel Gel with Gel Gel with
without with 0.15% with 1 % HZ
HZ 0.1 %HZ HZ 0.5%
HZ
Libbey 53 (avg. of 4 4.5 4.5 4.5 4.5
4 glasses)
Hi-Ball (avg. of 3 3 4.2 4.3 4.8 4.7
glasses)
Luminarc (avg. of 2 4.3 4.3 4.S 4.8
3 glasses)
It is observed that even a small amount of ZCLM (e.g. 0.1% HZ and/or 0.1% zinc
hydroxy sulfate) is sufficient to aid in maintaining iridescence and also
enables substantial anti-
etching benefits to treated glassware surfaces. The addition of O.I% HZ in the
Liquid Gel
detergent provides about 7 ppm active Zn2+ ions in the wash liquor.
Table VIII
Zinc Deposition on Glassware Surfaces in the presence of Hydrozincite
Substrate # of Liquid Liquid
cycles Gel Gel
without with
HZ 0.25%
HZ
Zn Si Zn Si
Libbey 53 (avg. of 4 glasses)1 ~ O.I2 23.30 0.51 25.23
Hi-Ball (avg. of 3 glasses)20 0.12 21.82 0.34 22.07
Luminarc (avg. of 3 glasses)50 0.18 21.84 0.47 19.75
It is also observed that the addition of a small amount of ZCLM (e.g. 0.25%
HZ) in the
formulation results in substantial zinc compound or Zn2+ ion deposition on
glassware surfaces. In
this test, it is also observed that the amount of zinc compounds or Zn2+ ions
deposited on the
glassware surface does not correlate with the number of wash cycles. While not
Wishing to be
bound by theory, the fact that zinc compounds or Zn2+ ions do not appear to
build up on the
glassware surface might indicate that a portion of the zinc compounds or Znz+
ions initially
deposited on the glassware surface are washed off and subsequently replenished
by rewashing.
Angle resolved XPS results (not shown) indicate that the zinc compounds or
Zn2+ ions are layered
on or incorporated within the treated glassware surface. It also appears that
the zinc compounds
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
16
or Zn2~ ions are substantially homogeneous within the first I O nm of the
glassware surface after
the wash cycle.
Crystalline Inte~rity Test
The crystalline integrity test is an indirect measure of ZCLM particle
crystallinity. The
FWHM (full width half maximum) of reflections of an x-ray diffraction (XRD)
pattern is a
measure of crystalline imperfections and is a combination of instrumental and
physical factors.
With instruments of similar resolution, one can relate crystal imperfections
or crystalline integrity
to the FWHM of the peaks that are sensitive to the paracrystalline property.
Following that
approach, crystalline distortionslperfection are assigned to various ZCLM
samples.
Three pealcs (200, ~13° 28, 6.9t~; 111, ~22° 28, 4.0~; 510,
36° 2~, 2.SA) are found to be
sensitive to lattice distortion, the 200 reflection is selected for the
analysis. The peaks are
individually profile-fitted using normal Pearson VII and Pseudo-Voigt
algorithms in Jade 6.1
software by MDI. Each peak is profile fitted 10 times with changes in
background definition and
algorithm to obtain average FWHM with standard deviations. The test results
are summarized in
Table IX.
Table IX
Crystallinity
Sample 200 Peak ReflectionRelative
Zinc
FWHM Std. Lability
Dev. (%)
Bru emann Zinc Carbonate , 0.0056 56.9
0.8625
Elementis Zinc Carbonate 0.7054 0.0024 51.6
Cater Zinc Carbonate#1 0.4982 0.0023 42.3
The crystallinity appears to be related to the FWHM of its source. Not wishing
to be
bound by theory, it is postulated that a lower crystallinity may aid in
maximizing zinc lability.
Stren~thenin~ Test Results
Fig 2 represents a comparison of glassware surface strength using specular
reflection IR
(IRRAS - Infrared reflection absorption spectroscopy). The substrate, a glass
microscopic slide,
is washed with commonly available detergent compositions using the same
washing conditions as
described above in the etching test. The microscopic slide spectra is
collected as % transmittance
spectra on a Digilab instrument (Bio-Rad) with a background collected of the
alignment mirror
supplied with the SplitPea accessory (Harrick Scientific Instruments), using a
low angle of
incidence for it's specular reflectance. Thus, the resulting spectra is a
reflectance spectra.
Strengthening of the glassware surface structure is correlated to IR spectral
changes in the
Si-O stretching vibration region. While not wishing to be bound by theory, it
is believed that the
reduction on the Si-O stretching vibration at 1050 cm-1 and above in the
spectrum of glass treated
CA 02542751 2006-04-13
WO 2005/037979 PCT/US2004/034554
17
with a liquid gel detergent composition containing a small amount of a ZCLM
(e.g. 0.1%-1% HZ)
can be attributed to the increase in roughness which is indicative of
glassware surface strength,
and to a decrease in the number of bridging Si-O bonds in the bulk glass which
is indicative of
glassware surface damage.
Little or no damage (i.e. higher strength) to glassware surfaces is observed
in glassware
surface treated with a liquid gel detergent composition having a small amount
of a ZCLM (e.g.
0.1%-1% HZ) versus a liquid gel detergent composition without ZCLM after 50
cycles. Since the
addition of a ZCLM to the liquid gel detergent composition leaves treated
glassware surface
IRRAS results unchanged (i.e. no' glassware surface damage), increased
glassware surface
strength is postulated.
With reference to the polymers described herein, the term weight-average
molecular
weight is the weight-average molecular weight as determined using gel
permeation
chromatography according to the protocol found in Colloids and Surfaces A.
Physico Chemical
& Engineering Aspects, Vol. 162, 2000, pg. 107-121. The units are Daltons.
The disclosure of all patents, patent applications (and any patents which
issue thereon, as
well as any corresponding published foreign patent applications), and
publications mentioned
throughout this description are hereby incorporated by reference herein. It is
expressly not
admitted, however, that any of the documents incorporated by reference herein
teach or disclose
the present invention.
It should be understood that every maximum numerical limitation given
throughout this
specification would include every lower numerical limitation, as if such lower
numerical
limitations were expressly written herein. Every minimum numerical limitation
given throughout
this specification will include every higher numerical limitation, as if such
higher numerical
limitations were expressly written herein. Every numerical range given
throughout this
specification will include every narrower numerical range that falls within
such broader numerical
range, as if such narrower numerical ranges were all expressly written herein.
While particular embodiments of the subject invention have been described, it
will be
obvious to those skilled in the art that various changes and modifications of
the subject invention
can be made without departing from the spirit and scope of the invention.
It will be clear to those skilled in the art that various changes and
modifications may be
made without departing from the scope of the invention and the invention is
not to be considered
limited to the embodiments and examples that are described in the
specification.
