COLORED SPECKLES
Cross Reference to Related Applications
This application claims priority to US Provisional Patent Application Number
61/236,707, entitled "Colored Speckles" which was filed on August 25, 2009, and
which is entirely incorporated by reference herein.
Field of the Invention
This invention relates to non-bleeding and quick color releasing colored speckles
for use in granular laundry detergents and other consumer products. The
speckles are comprised of a porous carrier, a releasing agent, and a coloring
agent.
Background of the Invention
Recently there has been an increasing trend towards the incorporation of colored
speckles into particulate laundry detergent compositions and other consumer
products. Dyes and pigments have been widely used to produce colored
speckles that serve aesthetic purposes only. Novel effects such as release of
color into the wash water and hueing of fabrics, however, tend to require higher
colorant loadings. There is, particularly at these higher colorant loadings, a
fabric staining risk associated with dye and pigment use. Thus, the need exists
for colored speckles for use in detergent compositions and other consumer
products that can serve both an aesthetic purpose and also provide the novel
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effects of release of color and hueing of fabrics without staining the substrates
that come into contact with the colored speckles.
Additionally, the inclusion of colored speckles in granulated laundry detergents
presents the problem of bleeding or transferring of color onto the powdered
detergent surrounding the speckle. This results in the base powder becoming
colored, which is a highly undesirable effect. Thus, the need exists for colored
speckles for use in detergent compositions which do not bleed or transfer to the
surrounding base powder.
Attempts by others to include colored speckles in detergents include, for
example, USPN 4,097,418 to Rolfes. This patent discloses the use of colored
speckles in granular detergent compositions. The colored speckles are
comprised of a water soluble inorganic alkaline salt which acts as a carrier for
the coloring agent. The coloring agent may be a water-soluble dye or a waterinsoluble
pigment. USPN 6,541,437 to Mata et al. discloses the use of glassy
phosphate particles as carriers for dyes and/or pigments. The colored particles
may be added to a detergent formulation to aid in improving its cleaning
performance.
Yet another example includes WO 2006/099964 A1 to Andrade et al. which
discloses the use of a speckle granule comprised of a clay mineral carrier and a
mica pigment. To increase the rate of dispersion of the granule in the wash
liquor, this reference teaches the inclusion of a soluble builder salt, such as
3
sodium tripolyphosphate, admixed with the clay in the granule. A water-soluble
polymeric coating, such as polyvinyl alcohol, may also be added to the granule,
to help prevent the mica from leaving the clay during storage and handling.
The problems associated with previous attempts by others to include colored
speckles in detergents include fabric staining from the colorant used in the
speckles, bleeding and transferring of the colorant to the surrounding detergent
powder, and failure of the speckle to release the colorant rapidly into the wash
water. The present disclosure addresses and overcomes these problems.
The colored speckles of the present disclosure are ideally suited for providing
color to various other compositions including, but not limited to granular
detergent compositions (such as laundry detergent compositions). The colored
speckles may provide non-staining, aesthetically-pleasing features to textile
substrates treated therewith. They also resist bleeding or transferring to the
surrounding detergent composition. Furthermore, the colored speckles of the
present disclosure quickly release color from the porous carrier and provide
desirable color to the wash water. For these reasons, and others that will be
described herein, the present colored speckles represent a useful advance over
the prior art.
Brief Summary of the Invention
Provided herein is a colored speckle comprising a majority by weight of at least
one porous carrier material; at least one releasing agent selected from the group
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consisting of salt compounds, sugar compounds, alkoxylated aromatic
compounds, glycols, high molecular weight alcohols, solvents having a boiling
point above 60°C, and mixtures thereof; and at least one coloring agent.
Yet another alternative includes a colored speckle comprising a majority by
weight of at least one porous carrier material selected from clays, silicas,
zeolites, metal oxides, diatomaceous earth, mica, talc, chalk, gypsum-containing
compounds, leaded zinc oxide, zinc oxide, zinc sulfide, lithopone, titanium
dioxide, calcium sulfate, antimony oxide, magnesium silicate, barytes, basic lead
carbonate, calcium carbonate, calcium sulfate, barium sulfate, calcium silicate,
silica flatting agents, aluminum silicate, hydrous aluminum silicates, magnesium
silicates, calcium metasilicate, sodium-potassium-aluminum silicate, sodium
tripolyphosphate, sodium silicate, soda ash-containing compounds, and
combinations thereof; at least one releasing agent selected from the group
consisting of salt compounds, sugar compounds, alkoxylated aromatic
compounds, glycols, high molecular weight alcohols, solvents having a boiling
point above 60°C, and mixtures thereof; and at least one polymeric coloring
agent.
Further provided herein is a colored speckle comprising at least one porous
carrier material, wherein the at least one porous carrier material is characterized
by having a plurality of pores, a first layer comprising at least one releasing
agent, wherein the releasing agent is in direct contact with at least a portion of
the plurality of pores of the at least one porous carrier material, and a second
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layer comprising from about 0.01% to about 10% by weight of at least one
coloring agent, wherein the colorant agent is in direct contact with at least a
portion of the releasing agent layer.
Further provided herein is a colored speckle comprising at least one porous
carrier material, wherein the at least one porous carrier material is characterized
by having a plurality of pores, and a mixture of at least one releasing agent and
at least one coloring agent.
Another embodiment includes a method for forming a colored speckle
comprising the steps of providing at least one porous carrier material; applying at
least one releasing agent to the at least one porous carrier material to form a
carrier-releasing agent composite; and applying at least one coloring agent to
the carrier-releasing agent composite to form the colored speckle.
Yet another alternative is a method for forming a colored speckle comprising the
steps of providing at least one porous carrier material; applying a mixture of at
least one releasing agent and at least one coloring agent to the at least one
porous carrier material to form the colored speckle.
Detailed Description of the Invention
All U.S. and foreign patents and U.S. patent applications disclosed in this
specification are hereby incorporated by reference in their entirety.
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The present disclosure relates to non-bleeding and quicl^ color releasing colored
speckles for use in granular detergent compositions. The colored speckles are
comprised of porous granules made from water-dispersible or water soluble
materials which act as a carrier for a coloring agent and a releasing agent. The
porous carrier provides good resistance to color bleeding into the surrounding
detergent composition. The combined use of a releasing agent with the carrier
allows for quick release (i.e. in less than 5 minutes) of the coloring agent from
the carrier and into the wash water. Herein, the present disclosure describes a
colored speckle and a method for making the colored speckle which drastically
improves the coloring agent release time, while still preserving the bleed
resistance that the carrier provides.
The term "non-staining" as used herein, generally refers to a coloring agent, or a
composition that contains such a coloring agent, that may be washed or
removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with
relatively little effort and without staining the substrate to an appreciable extent.
The term "non-bleeding," as used herein, generally refers to a coloring agentcontaining
composition that does not substantially color the material surrounding
the composition under conditions wherein the material is not intended to be
colored. For example, the colored speckles of the present invention will
generally be considered to be "non-bleeding" if the colored speckles fail to
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substantially color the surrounding powdered detergent in its unused state (i.e.
while it remains in the package).
Without being bound by theory, it is believed that a porous granule, or carrier,
has, by virtue of its form and/or structure, an abundance of pores both on its
surface as well as in its interior that have a certain distribution of sizes, depths
and tortuosity. A coloring agent applied to porous granules would be drawn into
these pores via capillary action, thereby being more "protected" or "shielded"
from the external environment than if it were to rest only on the surface of the
granule, which is believed to occur in a non-porous material contacted with a
coloring agent. Furthermore, it is believed that the physical "protection" or
"shielding," due to the porous nature of the granule, is a contributing factor to
providing bleed protection to a colored speckle that contains the granule. Thus,
when present in wash water, the release rate of the coloring agent from such
porous granules may then depend on the rate of disintegration, swelling or
dispersion of the granule. These factors may result in a slower release of color
from porous granules as compared to non-porous granules (again, where the
coloring agent would be present only on the outer surface of the granule).
Another factor to consider is the interaction between the coloring agent and the
material comprising the porous granule (e.g. clay). Favorable interaction
between the coloring agent and the granule, or carrier, which may be provided
by such by binding forces, adsorption, and the like, may further enhance the
bleed resistance of the resulting colored speckle. However, if the interaction is
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too strong, it could inhibit the release rate of the coloring agent from the colored
speckle into the wash water, even if the colored speckle granules disintegrates
rapidly.
To eliminate or reduce the possibility that this interaction between the coloring
agent and the carrier granule will hinder the release of the coloring agent, the
coloring agent may be applied to the carrier in such a way that it is in contact
(either absorbed or adsorbed) with a releasing agent, rather than with the carrier.
The releasing agent acts to prevent and/or reduce the coloring agent's
interaction with the inner walls of the pores of the granule. The coloring agent
may be primarily in contact with the releasing agent, rather than with the
surfaces of the carrier.
In one non-limiting embodiment, this structural arrangement of carrier to
releasing agent to coloring agent may be achieved by adding a releasing agent
to the inner walls or surfaces of the porous granule before application of the
coloring agent. Forces such as capillary action may draw the coloring agent into
the pores where the coloring agent is shielded from the external environment.
This allows the coloring agent to be primarily in physical contact with the
releasing agent and not in direct contact with the walls or surfaces of the porous
granule, or carrier.
Without being bound by theory, it is believed that modification of the porous
granule with a releasing agent results in a release rate of the coloring agent from
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the porous granules that is independent of the many factors that could
detrimentally affect it (e.g. that would slow down the release rate). These factors
include the rate of swelling, disintegration and dispersion of the porous granule
or of the binding and/or adsorption forces that hold the coloring agent to the
porous granule. As a result, the porous granule, or carrier, having a releasing
agent applied thereto, provides the desired dual benefit of bleed stability and
rapid color release in wash water.
Additionally, the amount of releasing agent required to deliver rapid release of
the coloring agent from the porous granules may be directly dependent on the
"porosity" of the granules, carriers, which includes factors like pore size
distribution, depth and tortuosity of the pores, and the rate of disintegration of the
granules. It is also believed that the strength of the interaction between the
coloring agent and the carrier or carrier material may also have an effect on
these desired features.
Carrier
The carrier is preferably in the form of a porous granule which is characterized
by having a plurality of pores. The colored speckle may be comprised of a
majority by weight of the carrier. The material used to produce the porous
granule may be characterized as a water dispersible material. Suitable carrier
materials that may be granulated to form these porous granules, or carriers, may
be selected from compounds containing and/or including, but not limited to clays,
silicas, zeolites, metal oxides, diatomaceous earth, mica, talc, chalk, gypsum10
containing compounds, leaded zinc oxide, zinc oxide, zinc sulfide, lithopone,
titanium dioxide, calcium sulfate, antimony oxide, magnesium silicate, barytes,
basic lead carbonate, calcium carbonate, calcium sulfate, barium sulfate,
calcium silicate, silica flatting agents, aluminum silicate including hydrous
aluminum silicates, magnesium silicates, calcium metasilicate, sodiumpotassium-
aluminum silicate, and the like, and combinations thereof. Suitable
examples of water soluble carriers include detergency builders such as sodium
tripolyphosphate, sodium silicate, soda ash-containing compounds, and the like,
and combinations thereof.
Examples of clay materials include bentonite, kaolin, smectite, illite, chlorite,
hormite, beidelite, sepiolite, alunite, hydrotalcite, nontronite, hectorite,
attapulgite, pimelite, muscovite, willemseite, minnesotaite, antigorite, amesite,
china clay, halloysite, and the like, and combinations thereof. Commercially
available examples of suitable clay carriers include Pelben® 10 and Pelben® 35
(available from Buntech, a Brazilian company). Suitable examples of clay
powders include Argel® 10 and Argel® 40 (available from Buntech).
Bentonites are clays that are comprised primarily of, and whose properties are
typically dictated by a smectite clay mineral (e.g. montmorillonite, hectorite,
nontronite, etc.). Smectites are generally comprised of stacks of negatively
charged layers (wherein each layer is comprised of two tetrahedral sheets
attached to one octahedral sheet; the tetrahedra formed by silicon and oxygen
atoms and the octahedra formed by aluminum and oxygen atoms together with
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hydroxyl radicals) balanced and/or compensated by alkaline earth metal cations
(e.g. Ca^"" and/or Mg^*) and/or alkali metal cations (eg. Na"" and/or K""). The
relative amounts of the two types (alkaline earth metal and alkali metal) of
cations typically determine the swelling characteristic of the clay material when
placed in water. Bentonites, in which the alkaline earth metal cation Ca^"^ is
predominant (or is in a relative majority), are called calcium bentonites; whereas,
bentonites in which the alkali metal cation Na"" is predominant (or is in a relative
majority) are called sodium bentonites.
The term "natural," as used herein with respect to clay material, refers to the
presence of the mineral in deposits found in the earth (formed via modification of
volcanic ash deposits in marine basins by geological processes). Accordingly, a
natural deposit of bentonite containing primarily (or a relative majority of) Na*
cations is referred to as "natural sodium bentonite;" whereas, a natural deposit of
a bentonite predominantly containing (or containing a relative majority of) Ca^*
cations is referred to as "natural calcium bentonite,"
Synthetic analogues of Na and Ca bentonite may also be synthesized (by using
hydrothermal techniques, for example). "Synthetic sodium bentonite" may also
refer to bentonite obtained by treatment of calcium bentonite with, but not limited
to, sodium carbonate or sodium oxalate (to remove the calcium ion and
substitute it with a sodium ion). This treatment can be varied to impart different
levels of ion-exchange or Na"^ for Ca^"" substitution. Herein, these materials are
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referred to as "partially activated" and "fully activated" grades of clay material,
respectively (with "fully" referring to maximum exchange of Ca^"" for Na"").
One of the reasons for converting calcium bentonite into synthetic sodium
bentonite is to impart greater swelling properties to othenwise (relatively) nonswelling
calcium bentonite. There is also an aesthetic benefit associated with
synthetic sodium bentonite that is lacking in natural sodium bentonite. Natural
sodium bentonite (generally, irrespective of the part of the world in which the
deposit is located) is colored. The color ranges from brown to yellow to gray. By
comparison, natural calcium bentonite has a more aesthetically pleasing white
color. Consequently, synthetic sodium bentonite that is obtained by treatment of
this white calcium bentonite is also white. As a result, natural calcium bentonite
and synthetic sodium bentonite find more widespread use in the detergent
industry, as compared to natural sodium bentonite.
Applicants' studies have shown considerable differences in the propensity of
certain coloring agents to stain fabrics depending on the type of bentonite clay
(in the form of a colored clay speckle or colored clay powder) to which the
coloring agents have been applied (natural sodium vs. natural calcium bentonite;
natural sodium bentonite vs. synthetic sodium bentonite; partially vs. fully
activated synthetic sodium bentonite). It has been discovered that, at equal
color loading, natural sodium bentonite display considerably lower propensity for
staining than calcium bentonite. It has also been discovered that, at equal color
loading, synthetic sodium bentonite exhibits lesser staining risk than calcium
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bentonite. However, at equal color loading, even fully activated synthetic sodiunn
bentonite shows greater staining than natural sodium bentonite. The same
observations were made independent of whether the color was applied to a
bentonite speckle or a bentonite powder.
Without being bound by theory, it is believed that clays with higher swelling
properties provide reduced staining risk for coloring agents applied thereto.
However, the appearance of a colored speckle made from natural sodium
bentonite may need to be improved, due to the yellow/gray/brown coloration of
the natural sodium bentonite. The considerable reduction in the staining risk
observed by the use of natural sodium bentonite indicates that it may be possible
to blend natural sodium bentonite with a whiter bentonite (such as calcium
bentonite or synthetic sodium bentonite or mixtures thereof), thereby resulting in
a speckle with a whiter appearance than a 100% natural Na-bentonite speckle,
but with lower staining risk than 100% Ca and synthetic sodium Bentonite
speckles.
The material used to produce the porous granule may also be a water soluble
material that does not have a rapid rate of dissolution (e.g. phosphates). The
term "rapid" is intended to describe a dissolution rate that will allow the quick
and/or instant release of the coloring agent into a wash water solution.
It may be preferable that the carrier exhibits a particular range of particle size, as
determined, for example, by sieving techniques according to ASTM D1921 - 06
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("Standard Test Method For Particle Size (Sieve Analysis) of Plastic Materials").
Alternative methods known to those skilled in the art may also be utilized for
determining particle size. For example, other sieving techniques may be used or
electronic laboratory equipment known for determining particle size may
alternatively be employed. For the carriers of the present invention, it may be
preferably that the carriers exhibit an average particle size of about 0.1mm to
about 2mm, more preferably an average particle size of about 0.3mm to about
1.2mm.
Coloring Agent
The coloring agent of the present invention is preferably a polymeric colorant.
The term "polymeric colorant" generally refers to a colorant having at least one
chromophore portion attached to at least one oligomeric or polymeric chain,
wherein the chain has at least three repeating units. The oligomeric or polymeric
constituent can be bound to the chromophore via any suitable means, such as a
covalent bond, an ionic bond, or suitable electrostatic interaction. Generally, the
polymeric colorant may be characterized by having an absorbance in the range
of between about 300 nanometers and about 900 nanometers, as measured by
UV-vis spectroscopy.
15
As a function of its manufacturing process, the poiynneric colorant has a
molecular weight that is typically represented as a molecular weight distribution.
Accordingly, the molecular weight of the polymeric colorant is generally reported
as an average molecular weight, as determined by its molecular weight
distribution.
The chromophore group of the colorant may vary widely, and may include
compounds characterized in the art as dyestuffs or as pigments. The actual
group used will depend to a large extent upon, for instance, the desired color
and colorfastness characteristics. The chromophore group may be attached to at
least one polyalkyleneoxy-substituent through a suitable linking moiety of
nitrogen, oxygen, sulfur, etc.
Examples of chromophore groups include nitroso, nitro, azo (including monoazo,
disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal
complexes thereof), stilbene, diarylmethane, triarylmethane, xanthene acridine,
quinoline, methine (including polymethine), thiazole, indamine, indophenol,
azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including
anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine, flavanthrone,
pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other
structures formally related to anthraquinone), indigoid (including thioindigoid),
phthalocyanine chromophore groups, and mixtures thereof.
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Examples of suitable polymeric chains are polyalkyleneoxy chains. The term
"polyalkyleneoxy," as used herein, generally refers to molecular structures
containing the following repeating units: -CH2CH2O-, CH2CH2CH2O-, -
CH2CH2CH2CH2O-, -CH2CH(CH3)0-, -CH2CH(CH2CH3)0- CH2CH2CH(CH3)0-,
and any combinations thereof.
Typical of such groups which may be attached to the chromophore group are the
polymeric epoxides, such as the polyalkylene oxides and copolymers thereof.
Typical polyalkylene oxides and copolymers of same which may be employed to
provide the colorants include those made from alkylene oxide monomers
containing from two to twenty carbon atoms, or more preferably, from two to six
carbon atoms. Examples include: polyethylene oxides; polypropylene oxides;
polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene
oxides, polypropylene oxides and polybutylene oxides; and other copolymers
including block copolymers, in which a majority of the polymeric substituent is
polyethylene oxide, polypropylene oxide and/or polybutylene oxide. Further,
such polyalkyleneoxy group may have an average molecular weight in the range
of from about 132 to about 10,000, preferably from about 176 to about 5000.
It is to be understood that because the colorants may not ordinarily be
chemically bound to the carrier, the precise chemical identity of the end group on
the polyalkyleneoxy group may not be critical insofar as the proper functioning of
the colorant is concerned in the composition. With this consideration in mind,
certain most preferred colorants will be defined wherein certain end groups will
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be identified. Such recitation of end groups is not to be construed as limiting the
invention in its broader embodiments in any way. According to such a most
preferred embodiment the colorants may be characterized as follows:
R{A[(aIkyleneoxy constituent)nRi]m}x
wherein R is an organic chromophore group, A is a linking moiety in said organic
chromophore group selected from the group consisting of N, O, S or CO2, the
alkylene moiety of the alkyleneoxy constituent contains from 2 to about 4 carbon
atoms, n is an integer of from 2 to about 230, m is 1 when A is O, S, CO2 and 1
or 2 when A is N, x is an integer of from 1 to 5, and the product of n times x
times m (n.m.x) is from 2 to about 230, and Ri is a member of the group
consisting of
o
—OCH2C-OH —SH —OH
o
—NH2 _o-c-NH2
o o
II II
—0-P—j —O-C-R2
k
and sulfonates and sulfates of each of the members of said group, wherein R2 is
H, an alky! radical containing up to about 20 carbon atoms or carboxy-terminated
alkyl radical containing up to about 20 carbon atoms, j and k are OH, OM or OR3
wherein M is a cation moiety of an alkali metal, an alkaline earth metal, transition
metal, e.g., nickel, etc. or ammonium, and R3 is an alkyl radical containing up to
about 20 carbon atoms.
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The oligomeric constituent can be any suitable constituent including, but not
limited to, oligomeric constituents selected from the group consisting of (i)
oligomers comprising at least three monomers, or repeating units, selected from
the group consisting of C2-C20 alkyleneoxy groups, glycidol groups, and glycidyl
groups, (ii) aromatic or aliphatic oligomeric esters conforming to structure (I)
O / R2 (I) •- ^ -" g
and (ill) combinations of (i) and (ii). In structure (I), R2 and R3 are independently
selected from the group consisting of hydrogen and C1-C10 alkyl groups, f is an
integer between and including 1 and 10, and g is any positive integer or fraction
between and including 1 and 20. As will be understood by those of ordinary skill
in the art, suitable values for g include both integers and fractions because the
length of the oligomeric constituent on the individual polymeric colorant
molecules may vary. Thus, the value for g represents an average length of the
ester chain for a given sample or collection of polymeric colorant molecules. In
certain embodiments, the polymeric colorant can comprise one or more
oligomeric constituents consisting of three or more ethylene oxide monomer
groups.
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Exemplary polymeric colorants include Liquitint® polymeric colorants, Cleartint®
polymeric liquid concentrate colorants, Reactint® polymeric colorants, and
Palmer® polymeric colorants, all of which are available from Milliken Chemical, a
division of Milliken & Company of Spartanburg, SC. Liquitint® polymeric
colorants are characterized in that they are water soluble, non-staining,
colorants. They are widely used in laundry detergents, fabric softeners, and
other consumer and industrial cleaning products. Liquitint® polymeric colorants
are generally bright liquid colorants which exhibit excellent solubility in water, are
compatible with other chemicals present in their end-use formulations, and are
easy to handle. Liquitint® polymeric colorants may be used to provide color in
both aqueous and solid systems. The unique polymeric nature of Liquitint®
polymeric colorants provides reduced staining to skin, textiles, hard surfaces,
equipment, and the like.
Cleartint® polymeric liquid concentrate colorants are specially designed liquid
colorants often used for coloring clarified polypropylene articles. These colorants
may be incorporated into polypropylene resins easily without detrimentally
affecting the clarity of the article to provide transparent, clear and brightly colored
polypropylene articles. Cleartint® liquid concentrate polymeric colorants are
oligomeric coloring materials which combine the exceptional aesthetics of dyes
with the migration resistance of pigments. These colorants may be used as light
tints to mask residual haze, or they may be used for deep, rich shades that are
not possible with pigment colorants. Cleartint® liquid concentrate polymeric
colorants allow clarified polypropylene to rival the beauty of higher cost plastic
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materials. The technical and physical property benefits of clarified polypropylene
may be exploited without sacrificing product aesthetics.
Reactint® polymeric colorants are liquid polymeric colorants useful for coloring
polyurethane and other thermoset resins. These colorants are reactive
polymeric colorants that consist of chromophores which are chemically bound to
polyols. This arrangement allows the polymeric colorant to react into the
polyurethane polymer matrix. Unlike pigment pastes, which are dispersions of
solid particles in a liquid carrier, Reactint® polymeric colorants are 100%
homogeneous liquids that are soluble in polyol and will not settle over time.
Because of this pure liquid and easy to disperse nature, it is possible to blend
Reactint® colorants in-line and on-the-fly, while producing polyurethane foams
and resins.
Palmer® polymer colorants are liquid colorants specially developed for use in
washable applications, such as in markers, paints and other art products. They
contain no heavy metals, are non-toxic, and have excellent non-staining
properties on skin, fabric and other surfaces. Palmer® polymeric colorants
have very good compatibility with aqueous ink formulations and provide bright
colors.
It is also contemplated to be within the scope of the present invention that other
colorants may be utilized as the coloring agent. For example, a colorant
selected from one or more of the following classes may be suitable for use as
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the coloring agent in the colored speckle: acid dyes, basic dyes, direct dyes,
solvent dyes, vat dyes, mordant dyes, indigoid dyes, reactive dyes, disperse
dyes, sulfur dyes, fluorescent dyes; pigments, both organic and inorganic;
natural colorants; and the like.
Releasing Agent
The releasing agent is generally used to effectuate the quick release of the
coloring agent from the carrier. The releasing agent may be any material that is
soluble or miscible in water at room temperature, though for ease of processing,
it may be advantageous to use materials with moderate-to-high solubility in water
(e.g. 20g-200g releasing agent/1 OOg water at 20°C). It may be advantageous if
the releasing agent is a solid in its pure form at room temperature. The solid
releasing agent may be ionic in nature (e.g. salts such as magnesium sulfate,
sodium sulfate, sodium carbonate, sodium chloride, and the like), non-ionic (e.g.
sugars such as sucrose, fructose, and the like), or a mixture of ionic and nonionic.
The releasing agent may also be a water-dispersible solid. However, in such
instances, the coloring agent may exhibit a weaker binding affinity for the water
dispersible releasing agent than for the carrier and/or the carrier material.
Suitable examples of such releasing agents may be dependent upon and
specific to the desired coloring agents utilized for the colored speckles.
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The releasing agent may also be a soluble or miscible material that is not a solid
at room temperature. Rather, the releasing agent may be a liquid or a wax in its
pure form at room temperature. Some examples of these types of releasing
agents include alkoxylated aromatic compounds (such as alkoxylates of mtoluidine),
glycols (such as polyethylene glycol), high molecular weight alcohols
(such as ethanol, propanol, hexanol, and butanol), solvents having a boiling
point above 60°C (such as dipropyl ether, ethylene glycol dimethyl ether, and
toluene), and the like, and mixtures thereof.
The alkoxylated form of m-toluidine may be alkoxylated with one or more of the
following groups: ethylene oxide (EO), propylene oxide (PO), butylene oxide
(BO), and any mixtures thereof. The average number of groups forming the
alkoxylated portion of m-toluidine may be from about 1 to about 200, more
preferably from about 1 to about 100, and most preferably from about 1 to about
50.
One potential advantage of a solid releasing agent is that, in theory, it may be
"fixed" at any position along the inner walls of the pores of the carrier granule (in
the form of a coating on the walls of the pores, wherein the coating may be
discontinuous or continuous) to form a non-migrating physical barrier between
coloring agent and the carrier. For rapid color release into solution, it may be
particularly advantageous to have the releasing agent "fixed" inside the pores but
close the carrier granule surface so that a sustained rapid release of the coloring
agent into wash water solutions months or years after the speckles are produced
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is achieved. This effect may not be achievable with liquid releasing agents,
since they may continue to migrate into the core of the granule over time.
The amount of releasing agent present in the colored speckle may vary
depending upon the nature of the porous carrier material or carrier and the
desired performance of the resulting colored speckle. It may be desirable that
the amount of releasing agent is enough to achieve sufficient release of the
coloring agent into wash water. Greater amounts of releasing agent would not
compromise the enhancement in the release rate, but too much releasing agent
would compromise the bleed protection that the porous carrier provides. As a
result, the optimum ratio of porous carrier to releasing agent may be the highest
carrier to releasing agent ratio at which enhanced color release is enabled and
which does not compromise bleed protection.
Thus, it may be desirable that the weight ratio of carrier to releasing agent is in
the range of 1000:1 to 1:1, more preferably 500:1 to 1:1, even more preferably
from 50:1 to 1:1, and most preferably from 20:1 to 1.5:1. In other instances, it
may be preferable that the weight ratio of carrier to releasing agent is 5 parts by
weight of carrier to 2 parts by weight of releasing agent.
Optional Additives
Optional additives that may be included in the colored speckles include
perfumes, enzymes, bleach activators, bleaches, bleach catalysts, bleach
24
stabilizers, foam regulators (foam boosters and antifoam agents), fluorescent
whitening agents, soil repellents, corrosion inhibitors, soil antiredeposition
agents, soil release agents, dye transfer inhibitors, builders, complexing agents,
ion exchangers, buffering agents, and mixtures thereof. Bleed inhibitors such
as film forming polymers or polymeric coatings may also be included. These
additives may be included in addition to the coloring agent or as the sole active
ingredient into the porous carrier that has been modified with the releasing
agent.
Methods For Forming the Colored Speckle
One method for forming the colored speckles of the present invention includes
the steps of providing a carrier, loading the carrier into a rotating drum or other
suitable mechanical device, and providing heat to the drum. The heat source
may include any suitable source of heat that is capable of sufficiently elevating
the temperature of the carrier. For example, a heat gun may be utilized. The
drum may or may not have baffles or other protrusions attached to its interior
walls.
Heat may be applied to the rotating drum in order to elevate the temperature of
the carrier to a temperature range of between SCC and 90°C, more preferably
between 40°C and SOX.
25
After the temperature of the carrier reaches its desired temperature range, a
releasing agent may be added to the rotating drum. The releasing agent may be
added, preferably in the form of an aqueous solution (for instance, a salt
solution), to the drum using any conventional means for adding materials to a
container. For example, the releasing agent may be sprayed into the drum. The
releasing agent thus comes into contact with the heated carrier. The releasing
agent may provide a substantially uniform coating on and/or into the carrier
The releasing agent may then be absorbed via capillary action into the pores of
the heated carrier. By evaporating of the water from the aqueous releasing
agent solution, the releasing agent is deposited on the inner walls or surface of
the pores of the porous granules. After completion of this step, the heat source
may be removed.
Next, the coloring agent, preferably in the form of an aqueous solution, may be
added to the carrier-releasing agent composite that remains in the rotating drum.
The coloring agent may be added to the drum using any conventional means for
adding materials to a container. For example, the coloring agent may be
sprayed into the drum. The coloring agent thus comes into contact with the
carrier-releasing agent composite. The coloring agent may provide a
substantially uniform coating on and/or into the carrier-releasing agent
composite. The resulting colored speckle may have a final color-on-speckle
loading of 0.01% to 10%, more preferably of 0.1% to 5%.
26
The colored speckles may then be dried. Drying may be accomplished by any
conventional means known for drying particulate materials.
The general methods for preparing the colored speckle described herein may not
be construed as limiting the scope of the present invention. It should be
possible, by way of alternative processing methods, to combine the carrier,
releasing agent and coloring agent to produce a colored speckle which exhibits
similar release profiles for the coloring agent, as well as other desired features,
as the colored speckles produced by the general methods described herein and
by their equivalent methods as known to those skilled in the art. For instance, it
may be possible to combine the releasing agent and the coloring agent together
into a mixture and then spray or otherwise apply the mixture to the carrier. It
might also be possible to subsequently add additional coloring agent to the
carrier. Also, it may be possible that a colored speckle having the desired
characteristics may be manufactured by adding the carrier, the releasing agent,
and the coloring agent together in one step.
Examples
The invention may be further understood by reference to the following examples
which are not to be construed as limiting the scope of the present invention.
The indication of "N/A" is used when no data or no additional data is available.
27
A. Preparation of Colored Speckles
One or more of the following procedures was used to prepare the colored
speckles:
Procedure 1
A coloring agent was sprayed directly on the carrier and no releasing agent was
used. The procedure was performed according to the following steps:
1. The carrier was loaded into a rotating drum with baffles. The drum
continued rotating for the entire procedure.
2. The coloring agent was sprayed onto the carrier in the rotating drum to
form the colored speckles.
3. The colored speckles were then allowed to air dry overnight.
Procedure 2
A releasing agent was applied to the carrier, followed by the addition of a
coloring agent. The procedure was performed according to the following steps:
1. The carrier was loaded into a rotating drum with baffles. Heat was applied
from a heat gun angled at the side of the barrel. The temperature of the
carrier was then monitored. The drum continued rotating for the entire
procedure.
2. A solution of releasing agent in water was made.
3. After the temperature of the carrier reached 60°C, the releasing agent
solution was sprayed Into the rotating drum. After all of the releasing
agent solution had been added, the heat was turned off.
28
4. The carrier-releasing agent composite granules were then sprayed with a
coloring agent that had been diluted with water to form the colored
speckles. The amount of water for the dilution was determined by the
final target color loading desired on the speckle.
5. The colored speckles were then allowed to air dry overnight.
Procedure 3
The releasing agent was combined with the coloring agent to form a releasing
agent-coloring agent mixture prior to being added to the carrier. The procedure
was performed according to the following steps:
1. The carrier was loaded into a rotating drum with baffles. The drum
continued rotating for the entire procedure.
2. A solution comprising one part by weight of Liquitint® Blue HP coloring
agent (at 100% solids content) and 3 parts by weight of m-toluidine
having, on average, 5 ethylene oxide groups attached to it was made.
3. The releasing agent-coloring agent solution was sprayed onto the carrier
in the rotating drum.
4. The colored speckles were then allowed to air dry overnight.
Procedure 4
For some samples, Argel® 10 (a commercially available powder clay product),
was used as the carrier. In order to granulate the powder into a particulate form,
samples utilizing Argel® 10 were exposed to the following procedure prior to
formation of the colored speckles;
29
1. 50g Argel® 10 clay carrier material was put into a plastic beaker.
2. 12g of water was dripped into the plastic beaker with a pipette.
3. The mixture was mixed with a wooden spatula until the water was
absorbed into the clay carrier material (the material appeared dry at this
point).
4. The water-day material was then put into a food processor and mixed on
the "grind" setting for a few seconds until the material formed uncolored
porous carrier particles of the appropriate size.
5. The uncolored carrier particles were then placed on a piece of aluminum
foil and dried in a 75°C oven.
6. Further modifications to these uncolored speckles are detailed in
Procedures 1, 2 & 3, as indicated for each example.
Procedure 5
1. 30g of bentonite powder was measured into a small food processor.
2. The desired amount of color was measured out into a small beaker and
diluted with 7.2g
of water.
3. The colored solution was then blended into a powder a little at a time. If
the powder
began to agglomerate, the sample was put Into a 60°C oven until dry,
then pulverized in the food processor. The final powder was passed
30
through a No. 25 sieve. The material that passed through the sieve was
used for testing.
B. Spot Staining Test Procedures
The following test procedures were used to evaluate fabric staining:
Spot Staining Test Procedure A
1. Spread the test fabric piece (100% white cotton fabric) in a flat tray having
dimensions of 36x24x6 cm.
2. Pour 2 liters of cold water into the tray.
3. Sprinkle detergent powder containing 3% colored speckles evenly on the test
fabric and let it stand for 90 minutes.
4. After soak time, rinse fabric under running water and let it air dry.
5. Check the fabric for any visible stains.
6. If staining is observed, wash the fabric in cold water with a detergent that
does not contain the colored speckles to see if the stain remains. If the stain
washes out completely, then it is not considered a problem.
The numerical rating scale for visual observations of stains on the test fabric was
as follows; 5 = no staining, 4 = very light amount of staining, 3 = light amount of
staining, 2 = medium amount of staining, 1 = heavy amount of staining.
31
SpoTStaining Test Procedure B
1. Spread the test fabric piece (100% wliite cotton fabric) in a plastic tub iiaving
dimensions of 36x24x6 cm. Tlie dimensions of tiie fabric piece are close to
that of the tub.
2. Pour 0.5 liters of cold (room temperature) water into the tub.
3. Sprinkle 2g of colored speckles evenly on the test fabric and let it stand for 90
minutes.
4. After soak time, rinse the fabric twice in a tub of tap water and let it air dry.
5. Visual observations of the fabric were made for any visible stains.
6. Steps 1-5 were repeated to obtain a duplicate test sample. Results provided
will be an average of the two test samples.
C. Tests and Evaluation
The following tests were carried out in order to evaluate certain properties of the
colored speckles:
Test 1: Benefit of Modifying the Carrier with Releasing Agent
Test 2: Applicability to Other Porous Carriers
Test 3: Use of Other Releasing Agents
Test 4: Bleed Resistance of Colored Speckles
Test 5: Stain Testing of Colored Speckles
Test 6: Benefit of Modifying the Carrier with Releasing Agent:
Applicability to Other Classes of Polymeric Colorants and
Commercial Dyes
Test?: Evaluation of Staining in Natural vs. Synthetic Clay
Carrier Materials
Test 8: Evaluation of Staining in Natural vs. Synthetic (Partially
32
and Fully Activated) Clay Carrier Materials
Test 9: Evaluation of Staining in Natural vs. Synthetic Clay
Carrier Materials As Affected by Particle Size
TEST 1: Benefit of Modifying the Carrier with Releasing Agent
This test illustrates the novel effect and benefit achieved by modifying the porous
carrier with a releasing agent.
The following colored speckles were prepared:
Example 1A^
Ingredients Amount (grams)
Pelben® 10 (pre-granulated sodium-bentonite 50
clay carrier)
Magnesium Sulfate (releasing agent) 35
LIquitint® Blue HP (polymeric colorant coloring agent) 1
Comparative Example 1A^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Blue HP (polymeric colorant coloring agent) 1
Example 1B^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 9
Liquitint® Blue HP (polymeric colorant coloring agent) 1
33
Example 1C^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Blue HP (polymeric colorant coloring agent) 1
Example 1D^
Ingredients Amount (grams)
Pelben® 35 (pre-granulated sodium-bentonite 50
clay carrier)
Magnesium Sulfate (releasing agent) 35
Liquitint® Blue HP (polymeric colorant coloring agent) 1
Comparative Example ID"*
Ingredients Amount (grams)
Pelben® 35 (clay carrier) 50
Liquitint® Blue HP (polymeric colorant coloring agent) 1
^Samples made via Procedure 1.
^Samples made via Procedure 2.
The resulting colored speckles were added to Tide® powder laundry detergent.
One gram of the speckle-containing detergent was added to a clear plastic cup
which contained 150mL of cold water. This mixture was gently stirred with a
cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and
34
then the mixture was stirred again with a cotton swap for 5 seconds.
The color of the wash water in the plastic cup was then observed to see if it
changed to blue and to determine if sediment was present in the bottom of the
cup. The speckles were also evaluated for various parameters such as
quickness of the color release into the wash water. "Sedimenf refers to the
dispersed, water insoluble carrier that settles to the bottom of the cup under
gravity. This sediment may have varying degrees of color depending on how
much of the color has released into the wash water solution. The observation of
no sediment being present is intended to describe that all visible traces of color
have come off the speckles; it is not intended to describe the actual absence of
solid uncolored sediment.
Test results are shown in Table 1 below.
Table 1: Benefit of Modifying the Carrier with Releasing Agent
35
Sample WashVVater Sediment Present? Comments
After 1 I After 5 After 1 I After 5
Minute Minutes Minute Minutes
Amount of sediment at 1 minute
was less than amount of sediment
in Comp. Example 1A at 5
minutes.
Example Extremel Wash water at 1 minute was more
1A Yes Yes y low A most 5,ue in color than wash water of
amount. None. ^^^p ^^g^p,^ ^^ ^^ 5 ^.^^^^^
Stirred briefly and sediment was
gone at 5 minutes.
Amount of sediment at 1 minute
y®[^. was about equal to Comp.
Example ^ ^^ Example 1A at 1 minute.
No than Yes Yes ^^.^^^^ ^^.^^^ ^^^ sediment was
P " ] ^ still present after 5 minutes.
. Blue coloration and sediment
^^^^^ ^ -.^^ .. „^ .. „^ amount about equal to Example
1C Yes Yes None None ^A. ^^„u„„i,v,uli., u««„.
1A; may be slightly better.
Blue coloration and sediment
Example amount about equal to Examples
^^ Yes Yes None None lA^and 1C. or possibly slightly
Sediment amount at 5 minutes
was less than amount at 1 minute.
Comparat^ ^^^^ ^^^^^ ^^^ ^^^ ^^^^ ^^ ^
^ ^f^'^ M Extremel y Y minute; it was a very, very slight
^^ ^° y slight ^®^ ^®^ blue at 5 minutes.
Even after stirring at 5 minutes,
sediment remained.
No color
seems to be
carried out
r. „ .:., J- . After stirring, a very mild Ceo cEm x1.pra>Davm_r aptl,ie^v NMo NMo s.Np,AeA rodJel •o-iscm eot*o e,nlo fnt.*r . t.X m_,lso .ei. ton dv,ou.ie ,mft. e rv see5r.n-r Ayt'. cwcooal,,loso r rs. wt.i.l,al, s^p roe^bs' seenrt,v aenjd d.. coSo enjd t*ba-i m liu•n eeen d*tj
sediment
was
\ \ I I present, i
36
The test results illustrate that the modification of the clay carrier with a releasing
agent (e.g. MgS04 salt) leads to a substantial decrease in the amount of time it
takes to release the coloring agent from the colored speckle. A releasing agent
may therefore be used to make a quick color-releasing speckle with a porous
clay carrier.
TEST 2: Applicability to Other Porous Carriers
This test illustrates that similar quick, color-releasing, non-bleeding, and nonstaining
speckles can be produced with other porous carriers containing a
releasing agent and a coloring agent.
The following colored speckles were prepared:
Example 2A^
Ingredients Amount (grams)
Granulated chalk (gypsum) 25
Magnesium sulfate (releasing agent) 17.5
Liquitint® Blue HP (polymeric colorant coloring agent) 0.87
Comparative Example 2A^
Ingredients Amount (grams)
Granulated chalk (gypsum) 25
Liquitint® Blue HP (polymeric colorant coloring agent) 0.51
37
^Samples made via Procedure 1.
^Samples made via Procedure 2.
The resulting colored speckles were added to Tide® powder laundry detergent.
One gram of the speckle-containing detergent was added to a clear plastic cup
which contained 150mL of cold water. This mixture was gently stirred with a
cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and
then the mixture was stirred again with a cotton swap for 5 seconds.
The color of the wash water in the plastic cup was then observed to see if it
changed to blue and to determine if sediment was present in the bottom of the
cup. The speckles were also evaluated for various parameters such as
quickness of the color release into the wash water. "Sediment" refers to the
dispersed, water insoluble carrier that settles to the bottom of the cup under
gravity. This sediment may have varying degrees of color depending on how
much of the color has released into the wash water solution. The observation of
no sediment being present is intended to describe that all visible traces of color
have come off the speckles; it is not intended to describe the actual absence of
solid uncolored sediment.
Test results are shown in Table 2 below.
Table 2: Applicability to Other Porous Carriers and
Their Effect on the Rate of Color Release
38
The test results illustrate that the modification of the chalk (e.g. gypsum) carrier
with a releasing agent (e.g. MgS04 salt) leads to a substantial decrease in the
amount of time it takes to release the coloring agent from the colored speckle.
The releasing agent can therefore be used to make a quick color-releasing
speckle with a porous chalk carrier.
Furthermore, test results provided herein illustrate that modification with a
releasing agent leads to a decrease in the release time of the coloring agent
from the colored speckle, regardless of the chemical nature of the porous carrier
(e.g. clay or chalk).
TEST 3: Use of Other Releasing Agents
I Instant
Sample Release of Sediment Present? Comments
Color?
After 1 Minute After 5 Minutes
Yes. As soon ^^^^^.^^ ^^^^ The detergent
_ , _. as water hits ^„ . ... ., . . . . .. contained
Example 2A tt,^„i^rein ^ seconds w h No disintegration 2.8% of the
r^""-"' no™LSd^ ^'^"- -'"-<'
the cup. ^ speckle.
Tiny amount of
None of the color released The detergent
P .. speckles during the course contained
ExamDle2A ^°- disintegrated, of 5 minutes. 2.8% of the
"^ even after stirring. After stirring, still colored
No color release. no disintegration speckle.
\ I I at all. This test illustrates the use of other water soluble materials as releasing agents
and their effect on the rate of color release.
39
The following colored speckles were prepared:
Example 3A^' '^
Ingredients Amount (grams)
Granulated Argel® 10 (clay carrier) 50
Alkoxylated m-toluidine with 5E0 groups 0.75
(releasing agent)
Stripped Liquitint® Blue HP (100% solids) 0.25
Comparative Example SA^"*
Ingredients Amount (grams)
Granulated Argel® 10 (clay carrier) 50
Liquitint® Blue HP (polymeric colorant coloring agent) 0.25
Example 3B^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 25
Sodium sulfate (releasing agent) 3.9
Liquitint® Blue HP (polymeric colorant coloring agent) 0.85
Example 3C^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 25
Soda Ash (releasing agent) 3.9
Liquitint® Blue HP (polymeric colorant coloring agent) 0.85
40
Example 30^"*
Ingredients Amount (grams)
Granulated Argel® 10 (clay carrier) 50
Sodium chloride (releasing agent) 17.5
Liquitint® Blue HP (polymeric colorant coloring agent) 1.75
Example 3E^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Sucrose (releasing agent) 35
Liquitint® Blue HP (polymeric colorant coloring agent) 1.74
^Samples made via Procedure 1.
^Samples made via Procedure 2.
^Samples made via Procedure 3.
^Samples made via Procedure 4.
The resulting colored speckles were added to Tide® powder laundry detergent.
One gram of the speckle-containing detergent was added to a clear plastic cup
which contained 150mL of cold water. This mixture was gently stirred with a
cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and
then the mixture was stirred again with a cotton swap for 5 seconds.
41
The color of the wash water in the plastic cup was then observed to see if it
changed to blue and to determine if sediment was present in the bottom of the
cup. The speckles were also evaluated for various parameters such as
quickness of the color release into the wash water. "Sediment" refers to the
dispersed, water insoluble carrier that settles to the bottom of the cup under
gravity. This sediment may have varying degrees of color depending on how
much of the color has released into the wash water solution. The observation of
no sediment being present is intended to describe that all visible traces of color
have come off the speckles; it is not intended to describe the actual absence of
solid uncolored sediment.
Test results are provided in Table 3.
Table 3: Use of Other Releasing Agents and Their Effect on the Rate of Color
Release
42
Sample Observations Comments
After 1 Minute After 5 IVIinutes N/A
Solution stirred
Color release Small amount of after 5 minutes
Example 3A occurred, but very, sediment was and the sediment
very light blue color. present. Colored disappeared.
Sediment was solution was a mild Solution was still a
present. blue. mild blue.
0.5% color on
onprkiP^ speckle. Solution
bpecKies stirred after 5
Comparative disintegrated wrth g^,^^;^^ ^^^^^^ ^^^ ^^_
Example 3A cdor stilh" th^enr ^^^^^ J^^^ ^^^ ^^^^^ ^^^/^ ^^ ^^^
solution, but it was ^'"^ °^^^ ^ "^*""*^^- sediment still
definitely blue. P^^^^"*; ^,^t ^ ^ ^^
' was definitely blue.
Solution blue after 30
seconds of stirring.
No instant release of Most speckles gone,
color. Solution blue Little sediment The detergent
Example 3B after 30 seconds of remained. Speckles contained 2.8% of
stirring. Most speckles completely the colored
gone. Little sediment, disintegrated. After speckle.
Speckles completely stirring, 50-60% of
disintegrated. sediment
disappeared.
Instant release of Solution blue after 30
color (blue before seconds of stirring,
stirring). Most speckles gone. ^. He^ic^mcn^
Solution blue after 30 Little sediment . HVPO/
Example 3C seconds of stirring. remained. Speckles containea 2.0/0 or
Most speckles gone. completely coiorea
Little sediment. disintegrated. After specKie.
Speckles completely stimng, 50-60% of
disintegrated. sediment
disappeared.
I ^+o«t r^i^^o^ «f Stirred briefly and
nstant release of o .. i. x . , . x-,.
^ , , , color. Small amount ^""f ^ " ; ° " " * °^ sed.ment was st,ll
Example 3D ^^^^^^^ ^33 sediment was present, but much
^ ^ ^ „ . present. less Yp^r esent. ^ minu a.t eftse.r 5
fnstant release of \nstanX release of
color. color.
Wash water turned Wash water turned
Example 3E blue on addition of blue on addition of
water. water.
Very, very little Very, very little
sediment present. sediment present.
43
The test results illustrate that modification of the clay carrier with water soluble
materials, other than MgS04 salt, also leads to a substantial decrease in the
amount of time it takes to release the coloring agent from the colored speckle.
The test results also show that the addition of alkoxylated m-toluidine to the
coloring agent, prior to application to the earner, appears to aid in the release of
coloring agent from the carrier, as evidenced by the lack of colored sediment
present in Example 3A in comparison to Comparative Example 3A.
TEST 4: Bleed Resistance of Colored Speckles
This test compares the bleed resistance of the colored speckles of the present
invention. The colored speckles of Example 1A, which were made from a
porous carrier modified with a releasing agent, were tested. In addition,
Example 4A was prepared as described below and was also tested for bleed
resistance. In general, Example 4A was made by spraying the same color used
in Example 1A onto a carbonate carrier and protecting, or coating, the coloring
agent with bleed prevention coatings.
The following sample, representing an alternative route to quick color-releasing
speckles, was prepared:
Comparative Example 4
Ingredients Amount (percent)
Soda Ash (granular carrier) 86.22
Corn Oil (bleed inhibitor) 6.89
44
Starch coating (coating/bleed inhibition agent) 5.17
Liquitint® Blue HP (polymeric colorant coloring agent) 1.72
For Comparative Example 4, the Liquitint® Blue HP polymeric colorant was first
sprayed onto the soda ash granules followed by the spray application of the corn
oil and then the starch coating to the colorant-containing soda ash granules,
according to methods described in Procedure 2.
Each sample tested for bleed resistance was prepared by adding 0.45 grams of
the colored speckles to 30 grams of Breeze powder laundry detergent (a
commercially available powder laundry detergent available from Unilever). The
mixture was then placed in an unlined cardboard box in a controlled environment
at 80% relative humidity and 37''C for a four week period of time. Each sample
was then visually evaluated for the amount of color bleed that was observed to
occur in the surrounchng powder laundry detergent.
Example 1A and Example 4A were compared and visually evaluated for bleed
resistance after four weeks in the Breeze powder laundry detergent. Example
1A appeared to exhibit significantly greater bleed resistance than Example 4A.
While Example 4A showed significant bleeding after 4 weeks, Example 1A
showed little to no bleed on the same detergent.
Thus, the test results illustrate that the use of a porous carrier modified with a
releasing agent provides a colored speckle that rapidly releases color into wash
water, but also displays good bleed resistance in humid conditions.
45
TEST 5: Stain TestinQ of Colored Speckles
This test illustrates the non-staining property of the colored speckles of the
present invention. Example 1B, as described herein, was independently added
Sample Surf® Tide® OMO Breeze Coral
ExampI 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4.5
e 1 B I I I I I I I I I I
Averag
c ® , 5 5 5 5 4.8
ExampI
e1B I I L_ \ 5 to the following powdered laundry detergents: Surf® (from Unilever), Tide®
(from Procter & Gamble), OMO (from Unilever), Breeze (from Unilever), and
Coral (from Unilever). Each sample was then tested according to Spot Staining
Test Procedure A described herein. Test results are provided in Table 5.
Table 5: Stain Testing of Colored Speckles
TEST 6: Benefit of Modifying the Carrier with Releasing Agent:
Applicability to Other Classes of Polymeric Colorants and Commercial
Pyes
This test illustrates the color release rate of polymeric colorants and commercial
dyes which have been added to carriers with and without the inclusion of a
releasing agent.
4S
Two types of colored speckles were prepared by independently adding coloring
agent or commercial dye to Pelben® 10 clay carrier. "Type A" colored speckles
were modified with 17 grams of magnesium sulfate releasing agent, as
described previously in Procedure 2, prior to the addition of the coloring agent.
"Type B" colored speckles did not include any magnesium sulfate releasing
agent, as described previously in Procedure 1, prior to the addition of the
coloring agent.
The following polymeric colorant coloring agents and commercial dyes were
tested:
Example 6A: Liquitini® Aztec Yellow lot 2009072027 (Phenyl
based Azo) with MgS04
Comparative Example 6A: Liquitint® Aztec Yellow lot 2009072027 (Phenyl
based Azo) with no MgS04
Example 6B: Liquitint® Orange X-96 (Bis-Azo) with MgS04
Comparative Example 6B: Liquitint® Orange X-96 (Bis-Azo) with no MgS04
Example 6C: Liquitint® Yellow LP lot E1279 (Methine Colorants)
with MgS04
Comparative Example 6C: Liquitint® Yellow LP lot E1279 (Methine Colorants)
with no MgS04
Example 6D: Liquitint® Red BL lot T1102 (H-Acid based Azo) with
MgS04
47
Comparative Example 6D: Liquitint® Red BL lot T1102 (H-Acid based Azo) with
no MgS04
Example 6E: Liquitint® Bright Blue/PC Cyan lot 2008242278
(Phthalocyanine) with MgS04
Comparative Example 6E: Liquitint® Bright Blue/PC Cyan lot 2008242278
(Phthalocyanine)
with no MgS04
Example 6F: Liquitint® Pink lot 2008469216 (Naphthol based Azo)
with MgS04
Comparative Example 6F: Liquitint® Pink lot 2008469216 (Naphthol based Azo)
with no MgS04
Example 6G: Liquitint® Violet CT (AMTC based Azo) with MgS04
Comparative Example 6G: Liquitint® Violet CT (AMTC based Azo) with no
MgS04
Example 6H: Liquitint® Red ST lot A1091 (Benzothiazole Azo) with
MgS04
Comparative Example 6H: Liquitint® Red ST lot A1091 (Benzothiazole Azo) with
no MgS04
Example 61: Liquitint® Patent Blue lot P1954 (TPM) with MgS04
Comparative Example 61: Liquitint® Patent Blue lot P1954 (TPM) with no
MgS04
Example 6J: FD&C Blue 1 lot HD138 (Water Soluble Commercial
Dye)
with MgS04
48
Comparative Example 6J: FD&CBlue 1 lot HD138 (Water Soluble Commercial
Dye)
with no MgS04
Example 6K: Solvent Blue 35 lot 07020KZ (Water Insoluble
Commercial Dye) with MgS04
Comparative Example 6K: Solvent Blue 35 lot 07020KZ (Water Insoluble
Commercial Dye) with no MgS04
Example 6L: Acid Blue 80 (Water Soluble Commercial Dye) with
MgS04
Comparative Example 6L: Acid Blue 80 (Water Soluble Commercial Dye) with
no MgS04
Example 6M: Direct Violet 9 lot C1141 (Azo Dye) with MgS04
Comparative Example 6M: Direct Violet 9 lot C1141 (Azo Dye) with no MgS04
The prepared colored speckles were added to Tide® powder laundry detergent
such that the detergent contained 2% by weight of the colored speckles. One
gram of the speckle-containing detergent was added to a clear plastic cup which
contained 150mL of cold water. This mixture was gently stirred with a cotton
swap for 30 seconds. The speckles were evaluated for quickness of the color
release into the wash water. Test results are provided in Table 6.
The following colored speckles were prepared:
49
Example 6A^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Aztec Yellow (polymeric colorant coloring agent) 1.36
Comparative Example 6A^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Aztec Yellow (polymeric colorant coloring agent) 1.02
Example 6B^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Orange X-96 (polymeric colorant coloring agent) 1.36
Comparative Example 6B^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Orange X-96 (polymeric colorant coloring agent) 1.02
50
Example 6C^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Yellow LP (polymeric colorant coloring agent) 1.36
Comparative Example 6C^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Yellow LP (polymeric colorant coloring agent) 1.02
Example 6D^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Red BL (polymeric colorant coloring agent) 1.36
Comparative Example 6D^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Red BL (polymeric colorant coloring agent) 1.02
Example 6E^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
51
Magnesium Sulfate (releasing agent) 17
Liquitint® Bright Blue (polymeric colorant coloring agent) 1.36
Comparative Example 6E^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Bright Blue (polymeric colorant coloring agent) 1.02
Example 6F^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Pink 1.36
(polymeric colorant coloring agent)
Comparative Example 6F^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Pink 1.02
(polymeric colorant coloring agent)
Example 6G^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
52
Liquitint® Violet CT (polymeric colorant coloring agent) 1.36
Comparative Example 6G^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Violet CT (polymeric colorant coloring agent) 1.02
Example 6H^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Red ST (polymeric colorant coloring agent) 1.36
Comparative Example 6H^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Liquitint® Red ST (polymeric colorant coloring agent) 1.02
Example 6!^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Liquitint® Patent Blue (polymeric colorant coloring agent) 1.36
Comparative Example 61^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
53
Liquitint® Patent Blue (polymeric colorant coloring agent) 1.02
Example 6J^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
FD&C Blue (commercial dye available from) 1.36
Spectrum Chemical Mfg. Co.)
Comparative Example 6J^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
FD&C Blue (commercial dye) 1.02
Example 6K^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Solvent Blue 35 (commercial dye available from 1.36
Aldrich Chemical Co.)
Comparative Example 6K^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Solvent Blue 35 (commercial dye) 1.02
Example 6L^
Ingredients Amount (grams)
54
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Acid Blue 80 (a commercial dye available from 4.27
Aceto)
Comparative Example 6L^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Acid Blue 80 (commercial dye) 3.2
Example 6M^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Magnesium Sulfate (releasing agent) 17
Direct Violet 9 (a commercial dye 0.67
available from Ciba)
Comparative Example 6M^
Ingredients Amount (grams)
Pelben® 10 (clay carrier) 50
Direct Violet 9 (commercial dye) 0.51
^Samples made via Procedure 1.
^Samples made via Procedure 2.
Table 6: Benefit of Modifying the Carrier with Releasing Agent:
Applicability to Other
Classes of Other Polymeric Colorants and Commercial Dyes
55
The test results illustrate that the colored speckles that were modified with a
releasing agent exhibited an enhanced rate of color release for all classes of
Sample Class Comments
Example 6A Much quicker color
Comparative Phenyl Based Azo release from salt
Example 6A modified sample
Example 6B Much quicker color
Corppara^jye Bis-Azo release from salt
,- , £.„ modified Example 6B samp^ le
Example 6C Much quicker color
Comparative Methine release from salt
Example 6C modified sample
Example 6D Much quicker color
Comparative H-Acid Based Azo release from salt
Example 6D modified sample
Example 6E Much quicker color
Comparative Phthalocyanine release from salt
Example 6E modified sample
Example 6F Much quicker color
Comparative Naphthol Based Azo release from salt
Example 6F modified sample
Example 6G No enhanced color
Comparative AMTC Based Azo release from salt
Example 6G modification
Example 6H Much quicker color
Comparative Benzothiazole Azo release from salt
Example 6H modified sample
Example 61 Much quicker color
Comparative TPM release from salt
Example 61 modified sample
Example 6J Much quicker color
Comparative Water Soluble Commercial Dye release from salt
Example 6J modified sample
Example 6K Much quicker color
Comparative Water Insoluble Commercial Dye release from salt
Example 6K modified sample
Example 6L No enhanced color
Comparative Water Soluble Commercial Dye release from salt
Example 6L modification
Example 6M Much quicker color
Comparative Azo Dye release from salt
Example 6M | modified sample
56
Liquitint® polymeric colorants, except for the AMTC-based Azo class
represented by Liquitint® Violet CT. Additionally, the test results illustrate that
the colored speckles that were modified with a releasing agent exhibited an
enhanced rate of color release for the FD&C Blue, Patent Blue, Solvent Blue,
and Direct Violet 9 commercial dyes. The test results illustrate that the release
rate of Acid Blue 80 from the clay carrier does not appear to be enhanced by
modification with magnesium sulfate releasing agent.
TEST 7: Evaluation of Staining in Natural vs. Synthetic Clay Carrier Materials
The following samples were prepared generally according to Procedure 5,
unless otherwise noted by the Process Description.
Table 7: Natural and Synthetic Carrier Materials with Coloring Agent
Coloring
o 1 9®" 3" Carrier Material Process Description
Sample Loading *^
Amount
2% Liquitintd p-.^pn^s) m ..vnthPtir Converted from granulated form to
7-1 Violet DD f^eiDeni&iu synmeiic powder form and then colored in
rVDD^ sodium bentonite clay ^.
Pelben®35 natural Converted from granulated form to
7-2 2%VDD HeiDen^Jb natural powder form and then colored in
sodium bentonite clay T.
A ,^ An t I J- Already in powder form as
-7 n on/\/r^i-\ Arge® 40, natura sodium ,, t „ * *
7-3 2%VDD . ^. ., ', received from manufacturer;
bentonite c ay i j [ colored •in •la ub .
Already colored as received from
7 4 2°/ VDD Pelben® 10 + 20kg/ton manufacturer. Converted from
° VDD granulated form to powder form in
lab,
Already colored as received from
7-5 2% VDD Pelben® 35 + 2% VDD manufacturer. Converted from
granulated form to powder form in
lab,
Already colored as received from
7-6 3% VDD Pelben® 35 + 3% VDD manufacturer. Converted from
I [ I granulated form to powder form In
57
I I I lab.
Synthetic sodium bentonit Converted from granulated form to
7-7 2% VDD clay granules from powder form and then colored in
AMCOL® lab,
Synthetic sodium bentonit Converted from granulated form to
7-8 3% VDD clay granules from powder form and then colored in
AMCOL® lab,
7 Q 00/ x/nr. Calcium bentonite clay Converted from granulated form to
7-9 2% VDD granules from AMCOL® POwder form and then colored in
7 in .0/ x,nn Calcium bentonite clay Converted from granulated form to
7-10 3% VDD granules from AMCOL® Powder form and then colored in
Already colored as received from
7 11 2°/ VDD Calcium bentonite clay manufacturer. Converted from
° granules from AMCOL® granulated form to powder form in
lab^
Natural sodium Already in powder form as
7-12 2% VDD bentonite clay from Fisher received from manufacturer;
B-235 Lot#744491 colored in lab.
Natural sodium Already in powder form as
7-13 3% VDD bentonite clay from Fisher received from manufacturer;
B-235 Lot#744491 colored in lab.
2°/° Pelben® 10 svnthetic Converted from granulated form to
7-14 Ultramarine f^eioenuy lu synineiic powder form and then colored in
Blue(UMB) sodium bentonite clay |;^
A ,^ An t I -J- Already in powder form as
7-15 2% UMB Argel® 40. natural sodium ^^^^^ J ^ ^^^^ manufacturer;
bentonite clay ^^,^^^^ .^ ^^^
00/ r->- * o lu /RN H n tu *• Converted from granulated form to
-, ._ 2% Direct Pe ben® 10, synthetic . , y.. 7-16 xV/i.o l,e t. n9 sod.•iu m ube nit onit*e clIa y pr o. wder form and th en co,b red. .in
7-17 ^^PiT^ Argel® 40, natural sodium fecdv'l^d'fro^man^^^^^^
Violet 9 bentonite clay colored in lab.
rt 00/ r->- * r. lu /Rv ^ r, *u *• Converted from granulated form to
-, ._ 0.2% Direct Pe ben® 10, synthetic ^ , _ j.u i -4-
^-^ S Violet 9 sodium benionite clay P°^^^^ ^^^"^ ^"^ *h^" ^°'°^^^ '"
, ,^ 0.2% Direct Argel® 40. natural sodium ^'^^^^yj" P°^^^^ ^°;"^,^^
^-^9 Violet 9 bentonite clay ""^f'^^^ ^'Z manufacturer;
I \ [ I colored in lab.
58
Each of the samples in Table 7 was evaluated for staining according to Spot
Staining Test Procedure B. The test results are provided in Table 7-A.
Table 7-A: Spot Staining Test Results for
Natural vs. Synthetic Clay Carrier Materials
Visual Observations
Sample After Rinse & Dry
7-1 Very bad staining
7-2 No staining
7-3 No staining
-. . Very bad staining; equivalent to or
" worse than 7-1.
7-5 No staining
^ pj No staining; very mild hue; almost not
" observable
^ J Staining; much milder than 7-1, but
" significantly worse than 7-6
-. o staining; worse than 7-7; milder than
^'^ 7^1
7-9 Same as 7-7
7-10 Same as 7-8
_ .. Staining;/ as bad as 7-8 and 7-10;
" maybe slightly worse
7-12 No staining
7-13 No staining
7-14 No staining
7-15 No staining
7-16 Very bad staining
•J A-J Very bad staining, no observable
" difference between 7-16 and 7-17
7-18 Staining
7-19 Staining; noticeably milder than 7-18
The test results Indicate that, for equivalent Violet DD color loading, colored (with
Violet DD) natural sodium bentonite (Pelben® 35 or Argel® 40) powder provides
59
less staining than colored (with Violet DD) synthetic sodium bentonite (Pelben®
10) powder. This result appears to be true regardless of the source of the
natural sodium bentonite (e.g. Buntech or Fisher Scientific).
For equivalent, low (0.2%) Direct Violet 9 color loading, colored (with Direct
Violet 9) natural sodium bentonite (Pelben® 35 or Argel® 40) powder provides
less staining than colored (with Direct Violet 9) synthetic sodium bentonite
(Pelben® 10) powder. However, this effect appears to be lost at higher (2%)
Direct Violet 9 color loading.
For equivalent, Ultramarine Blue color loading, colored (with Ultramarine Blue)
natural sodium bentonite (Pelben® 35 or Argel® 40) powder provides equivalent
staining as colored (with Ultramarine Blue) synthetic sodium bentonite (Pelben®
10) powder.
For equivalent Violet DD color loading, colored calcium bentonite (powdered and
colored in lab) from AMCOL® provides equivalent staining as colored synthetic
sodium bentonite (powdered and colored in lab) from AMCOL®.
TEST 8: Evaluation of Staining in Natural vs. Synthetic (Partially and Fully
Activated) Clay Carrier Materials
The following samples were prepared according to Procedure 5. All of the
carrier materials were obtained from AMCOL®. Each of the partially activated
and fully activated bentonite carrier materials are synthetic sodium bentonites.
60
Table 8: Partially Activated, Fully Activated, and Natural Bentonite
Clay Powder Materials Colored with Liquitint® Violet DD Coloring Agent
I Coloring I
Sam pi Agent
e and Carrier Material
Loading
Amount
8 1 2°/ VDD Partially activated synthetic sodium
bentonite clay powder
Q o oo/ \ / n n foully activated synthetic sodium
o-dL. £. /o V U U i_ J. -J. 1 J bentonite clay powder
8-3 2% VDD Natural sodium bentonite clay powder
a A 00/x/nvm Partially actlvated synthetlc 8-4 3% VDD bi_e nit.o niti.e clIa y powdJe rs odlum
8 c oo/ y n n '^'-'"y activated synthetic sodium
" bentonite clay powder
8-6 3% VDD Natural sodium bentonite clay powder
Each of the samples in Table 8 was evaluated for staining according to Spot
Staining Test Procedure B. The test results are provided in Table 8-A.
Table 8-A: Spot Staining Test Results for
Natural vs. Synthetic (Partially and Fully Activated)
Clay Carrier Materials
~ I '. I Visual Observations
^^'"P'^ After Rinse & Dry
8-1 Moderate/Bad Staining
8-2 Noticeably Milder Staining than 8-1
„ » Easily the Mildest Staining when
compared to 8-1 and 8-2
8-4 Moderate/Bad Staining
8-5 Noticeably Milder Staining than 8-4
Q „ Easily the Mildest Staining when
I compared to 8-4 and 8-5
For equivalent Violet DD color loading, the colored (with VDD) natural sodium
bentonite powder provides less staining than the colored (with VDD) "activated"
61
grades of bentonite powder (both partially and fully activated grades, which are
synthetic sodium bentonites).
For equivalent Violet DD color loading, the colored (with VDD) fully activated
bentonite powder provides less staining that the colored (with VDD) partially
activated bentonite powder.
The test results show that as the clay carrier material becomes more like the
natural sodium bentonite, its propensity for fabric staining decreases. Without
being bound by theory, it is believed that this effect may be related to the
swelling properties of the clay carrier materials. Natural sodium bentonite tends
to exhibit the most swelling when placed in an aqueous environment, while
calcium bentonite tends to exhibit is the least amount of swelling. For synthetic
sodium bentonites (partially and fully activated), as more and more of the
calcium ions are substituted with sodium ions (by soda ash treatment of the
calcium bentonite for example), the swelling of the clay material progressively
increases.
TEST 9: Evaluation of Staining in Natural vs. Synthetic Clay Carrier Materials
As Affected by Particle Size
The following samples were prepared as described herein. Each sample was
then tested for staining according to Spot Staining Test Procedure B.
Part A - Dividing speckles by particle size
62
1. Sodium bentonite and calcium bentonite clay carrier material
(granules/speckles) from AMCOL® were independently sifted. The clay
carrier material that was retained by the #25 and #20 sieves for each of
the sodium and calcium bentonite materials were separated.
2. Pelben® 10 and Pelben® 35 bentonite from Buntech were independently
sifted and the clay carrier material that was retained by the #25 sieve for
each of the bentonite materials was kept separate.
Sample 9-1: Calcium Bentonite #25 (AMCOL®) + 3% VDD
1. 50g of the calcium bentonite clay carrier material that was retained by the
#25 sieve was put into the drum of a tumble mixer.
2. 2.1g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
9.54%)
Sample 9-2: Calcium Bentonite #20 (AMCOL®) + 3% VDD
1. 30g of the calcium bentonite clay carrier material that was retained by the
#20 sieve was put into the drum of a tumble mixer.
2. 1.26g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
63
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
9.82%)
Sample 9-3: Natural Sodium Bentonite # 25 (AMCOL®) + 3% VDD
1. 50g of the sodium bentonite material that was retained by the #25 sieve
was put into the drum of a tumble mixer.
2. 2.1g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
9.58%)
Sample 9-4: Natural Sodium Bentonite #20 (AMCOL®) + 3%VDD
1. 30g of the sodium bentonite clay carrier material that was retained by the
#20 sieve was put into the drum of a tumble mixer.
2. 1.26g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
8.42%)
64
Sample 9-5: Pelben® 10 #25 (Buntech Synthetic Sodium Bentonite) + 3%VDD
1. 50g of tlie Pelben® 10 clay carrier material that was retained by the #25
sieve was put into the drum of a tumble mixer.
2. 2.1g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
12.17%)
Sample 9-6: Pelben® 35 #25 (Buntech Natural Sodium Bentonite) + 3%VDD
1. 50g of the Pelben® 35 clay carrier material that was retained by the #25
sieve was put into the drum of a tumble mixer.
2. 2.1g of Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water
(this is 3% color times 1.4 to compensate for color loss to the drum.)
3. The colored solution was then sprayed onto the clay carrier material while
the drum was rotating. The colored speckles thus produced were then
spread out flat on a piece of foil to dry overnight. (Final wt% moisture =
9.6%)
Table 9: Spot Staining Test Results for
Natural vs. Synthetic Clay Carrier Materials
Having Varying Particle Size
Sample Colored Clay Speckles After Rinse & Dry
Tl 3% VDD on AMCOL® Ca-Bentonite T , , ^ . .
Q-^ I speckles retained on sieve #25 | ^^^ ^^^ "^^'"'"9
65
~ I 3% VDD on AMCOL® Ca-Bentonite I ~ . . , . .
Q-^ speckles retained on sieve #20 Very bad staining
3% VDD on AMCOL® Natural Na- Highly reduced staining
9-3 Bentonite speckles retained on sieve compared to 9-1. Mild stains still
^ #25 present.
3% VDD on AMCOL® Natural Na- Highly reduced staining
9-4 Bentonite speckles retained on sieve compared to 9-1. Mild stains still
#20 present.
3% VDD on BUNTECH Synthetic Na-
9-5 Bentonite (Pelben 10) speckles Very bad staining
retained on sieve #25
3% VDD on BUNTECH Natural Na- Highly reduced staining
9-6 Bentonite (Pelben 35) speckles compared to 9-5. Mild stains still
I retained on sieve #25 | present.
For equivalent Violet DD color loading and equivalent speckle size, the colored
speckles containing natural sodium bentonite (Pelben® 35) provides less
staining than the colored speckles containing synthetic sodium bentonite
(Pelben® 10).
For equivalent Violet DD color loading and equivalent speckle size, the colored
speckles containing natural sodium bentonite (from AMCOL®) provides less
staining that the colored speckles containing calcium bentonite (from AMCOL®).
A trend of less fabric staining is observed (for equal color loading and in equal
particle size) with the transition from calcium or synthetic sodium bentonite to
natural bentonite on both powdered and granular forms of these clay carrier
materials. However, an increased risk of staining is observed with the transition
from powdered natural sodium bentonite to granular natural sodium bentonite for
the same loading of VDD.
66
Thus, the above description and examples show that the inventive colored
speckles provide both quick release of non-staining color and bleed resistance to
various detergent formulations with which they may be combined. As has been
described herein, the inventive colored speckles possess a significant advantage
over currently available colored speckles by allowing rapid release of color into
wash water, while still preserving bleed resistance and good non-staining
properties. As such, the present colored speckles represent a useful advance
over the prior art.
These and other modifications and variations to the present invention may be
practiced by those of ordinary skill in the art, without departing from the spirit and
scope of the present invention. Furthermore, those of ordinary skill in the art will
appreciate that the foregoing description is by way of example only, and is not
intended to limit the scope of the invention described in the appended claims.

We claim:
1. A colored speckle comprising:
a) a majority by weight of at least one porous carrier material;
b) at least one releasing agent selected from the group consisting of salt
compounds, sugar compounds, alkoxylated aromatic compounds, glycols,
high molecular weight alcohols, solvents having a boiling point above 60°C,
and mixtures thereof; and
c) at least one coloring agent.
2. The colored speckle of claim 1, wherein the at least one porous carrier material is
selected from clays, silicas, zeolites, metal oxides, diatomaceous earth, mica, talc,
chalk, gypsum-containing compounds, leaded zinc oxide, zinc oxide, zinc sulfide,
lithopone, titanium dioxide, calcium sulfate, antimony oxide, magnesium silicate,
barytes, basic lead carbonate, calcium carbonate, calcium sulfate, barium sulfate,
calcium silicate, silica flatting agents, aluminum silicate, hydrous aluminum
silicates, magnesium silicates, calcium metasilicate, sodium-potassium-aluminum
silicate, sodium tripolyphosphate, sodium silicate, soda ash-containing
compounds, and combinations thereof.
3. The colored speckle of claim 2, wherein the at least one porous carrier material is
clay.
68
4. The colored speckle of claim 1, wherein the at least one porous carrier material
exhibits an average particle size of between about 0.1mm and about 2mm.
5. The colored speckle of claim 1, wherein the at least one porous carrier material
exhibits an average particle size of between about 0.3mm and about 1.2mm.
6. The colored speckle of claim 1, wherein the salt compounds are selected from the
group consisting of magnesium sulfate, sodium sulfate, sodium carbonate, sodium
chloride, and mixtures thereof.
7. The colored speckle of claim 6, wherein the salt compound is magnesium sulfate.
8. The colored speckle of claim 1, wherein the sugar compound is selected from the
group consisting of sucrose, fructose, and mixtures thereof.
9. The colored speckle of claim 1, wherein the alkoxylated aromatic compound is mtoluidine
having five ethylene oxide groups attached thereto.
10. The colored speckle of claim 1, wherein glycol is polyethylene glycol.
11. The colored speckle of claim 1, wherein the at least one releasing agent exhibits
solubility in water of from about 20 grams to about 200 grams of releasing agent to
100 grams of water at 20°C.
69
12. The colored speckle of claim 1, wherein the ratio by weight of the at least one
porous carrier to the at least one releasing agent is in the range of about 1000:1 to
about 1:1.
13. The colored speckle of claim 1, wherein the coloring agent is selected from the
group consisting of polymeric colorants, acid dyes, basic dyes, direct dyes, solvent
dyes, vat dyes, mordant dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur
dyes, fluorescent dyes, inorganic pigments, organic pigments, natural colorants,
and mixtures thereof.
14. The colored speckle of claim 13, wherein the coloring agent is a polymeric
colorant.
15. The colored speckle of claim 14, wherein polymeric colorant is characterized by
having a chromophore group is selected from the group consisting of nitroso, nitro,
azo (including monoazo, disazo, trisazo, tetrakisazo, polyazo, formazan,
azomethine and metal complexes thereof), stilbene, diarylmethane, triarylmethane,
xanthene acridine, quinoline, methine (including polymethine), thiazole, indamine,
indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone
(including anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine,
flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and
70
other structures formally related to anthraquinone), indlgoid (Including thioindigoid),
phthalocyanine chromophore groups, and mixtures thereof.
16. The colored speckle of claim 1, wherein the colored speckle is characterized by
having a first layer of releasing agent applied to the porous carrier to form a
carrier-releasing agent composite.
17. The colored speckle of claim 16, wherein the carrier-releasing agent composite is
further characterized by having the at least one coloring agent applied to the
composite.
18. A powdered detergent formulation comprising the colored speckle of claim 1.
19. A colored speckle comprising:
a) a majority by weight of at least one porous carrier material selected from
clays, silicas, zeolites, metal oxides, diatomaceous earth, mica, talc, chalk,
gypsum-containing compounds, leaded zinc oxide, zinc oxide, zinc sulfide,
iithopone, titanium dioxide, calcium sulfate, antimony oxide, magnesium
silicate, barytes, basic lead carbonate, calcium carbonate, calcium sulfate,
barium sulfate, calcium silicate, silica flatting agents, aluminum silicate,
hydrous aluminum silicates, magnesium silicates, calcium metasilicate,
sodium-potassium-aluminum silicate, sodium tripolyphosphate, sodium
silicate, soda ash-containing compounds, and combinations thereof;
71
b) at least one releasing agent selected from the group consisting of salt
compounds, sugar compounds, alkoxylated aromatic compounds, glycols,
high molecular weight alcohols, solvents having a boiling point above 60°C,
and mixtures thereof; and
c) at least one polymeric coloring agent.
20. A colored speckle comprising:
(a) at least one porous carrier material, wherein the at least one porous carrier
material is characterized by having a plurality of pores,
(b) a first layer comprising at least one releasing agent, wherein the releasing
agent is in direct contact with at least a portion of the plurality of pores of the at
least one porous carrier material, and
(c) a second layer comprising from about 0.01% to about 10% by weight of at
least one coloring agent, wherein the colorant agent is in direct contact with at
least a portion of the releasing agent layer.
21. The colored speckle of claim 20, wherein the coloring agent is a polymeric
colorant.
22. A colored speckle comprising:
(a) at least one porous carrier material, wherein the at least one porous carrier
material is characterized by having a plurality of pores, and
(b) a mixture of at least one releasing agent and at least one coloring agent.
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23. A method for forming a colored speckle comprising the steps of:
(a) providing at least one porous carrier material;
(b) applying at least one releasing agent to the at least one porous carrier
material to form a carrier-releasing agent composite; and
(c) applying at least one coloring agent to the carrier-releasing agent composite
to form the colored speckle.
24. A method for forming a colored speckle comprising the steps of:
(a) providing at least one porous carrier material;
(b) applying a mixture of at least one releasing agent and at least one coloring
agent to
the at least one porous carrier material to form the colored speckle.
Dated this 13/01/2012