Note: Descriptions are shown in the official language in which they were submitted.
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Title: CLEANING FORMULATIONS FOR CHEMICALLY
SENSITIVE INDIVIDUALS: COMPOSITIONS AND METHODS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Prov'l. Appl. Ser. No.
61/982,877
filed 23 April 2014, which is hereby incorporated by reference in its
entirety.
BACKGROUND OF THE DISCLOSURE
FIELD OF THE DISCLOSURE
[0002] The present disclosure relates to cleaning compositions in general, and
cleaning compositions well suited for those individuals, who experience
multiple
chemical sensitivities (MCS), in particular. Individuals with MCS are
virtually unable
to use commercially available cleaners. The instant disclosure concerns the
selection of
ingredients and methods for formulating and evaluating a series of cleaning
products
for use by any person, including individuals with MCS.
[0003] Cleaning product compositions that are suitable for cleaning clothing,
dishware, countertops and other hard surfaces have been commercially prepared,
marketed, and sold to consumers for over two hundred years. As cleaning
technology
progressed, environmental and safety issues sometimes lagged behind
discoveries in
cleaning efficacy. For example, in the late 1950's and early 1960's, it was
found that
synthetic surfactants that had supplanted natural soap products exhibited poor
biodegradability, and were building up in waste water streams; streams laden
with
tenacious foam were widespread, and tremendous efforts were focused on finding
alternatives. In the 1970's, certain builder compounds also came under
scrutiny for
their environmental impact, such as eutrophication on inland lakes and ponds.
In the
search for alternate builder materials, one candidate material,
nitrilotriacetic acid, NTA,
was found to be a very promising candidate. Fortunately, before it reached
mass
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distribution, safety tests showed that it could transport heavy metals across
placental
membranes, which was thought of as potentially harmful to developing fetuses.
[0004] These examples, among others, has led to attention being paid to safety
on par
with that of cleaning performance; in fact, attention to the issue has
resulted in
numerous very effective ingredients being removed from commerce. By and large,
most cleaning ingredients currently in use have resolved many of the issues of
the past,
and now there is widespread effort to understand the potential after-effects
of cleaning
ingredients as far as acute toxicity, chronic toxicity, carcinogenicity,
mutagenicity,
teratogenicity, and hormone disruption are now commonly looked at before
ingredients
are brought to market.
[0005] One further phenomenon that has received attention in the last few
years is the
effect of cleaning compositions on chemically sensitive individuals. In
westernized
countries, asthma and related atopic disorders such as eczema and hay fever
are now
major public health concerns, due to their high prevalence--approximately 20%
of the
people in the United States are estimated to be sufferers. Understandably,
there is
concern associated with significant ill health and high societal and
healthcare costs.
Multiple scientific studies have raised concerns about the potential for
consumer
products to cause or exacerbate asthma or asthma-like responses.
[0006] While the removal of dyes and fragrances from cleaning products have
alleviated responses of some sensitive individuals, there are a considerable
number of
consumers who are not able to use commercially-available products for reasons
that
until now have not been well-understood. These individuals are forced to use
centuries-
old cleaners such as vinegar and baking soda, products that are lacking in
cleaning
efficacy, but are a last resort for these individuals. Unfortunately, while
the mechanism
whereby these individuals become highly and multiply sensitized is not
understood,
when they do become sensitized, there is no known cure of reversal of
debilitating
responses. Products are therefore needed that are not only designed for these
individuals, but for a general population that is possibly but unknowingly
vulnerable to
acquiring multiple chemical sensitivities.
[0007] In recent years, more and more products are being sold which claim to
be
"green", "environmentally friendly", "natural", "organic", "sustainable",
etc., with the
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implication that such products contain ingredients that are bio-based, or at
least have
lower levels of petrochemical ingredients. While some of these products have
been
based on well-founded technology, the actions of some have caused
environmental
advocates as well as the media to warn against the phenomenon of trying to
promote a
product's credentials through dubious claims as "greenwashing." Although some
regulatory agencies, such as the EPA and FDA, provided regulations and
standards for
environmentally hazardous substances and food and drugs respectively, there is
no
similar agency that specifically covers cleaning products. In addition, none
of these
agencies have developed clear guidelines for the terms "natural", "green",
"environmentally friendly" or the like. There are some organizations, which
provide
lists of approved natural components and standards for components based on
standardized test methods which measure, toxicity, biodegradability and other
factors
for determining the naturalness and environmental impact of a given product.
However
there is little guidance on issues like, use of "eco-hybrids" or "hybrid
surfactants" that
are comprised of both petroleum and plant based chemistries, which is
contributes to
the ongoing problem of "greenwashing".
[0008] There is perhaps a larger problem with the implication that no matter
how
"green" or "natural" a product might be, that such products may imply that
they are
safer for consumers than other mainstream products. While standards have been
established to measure the degree of bio-basis of a product, the need for
standards to
better promote the safety of such products has received too little attention,
much less
been established. No organizations can certify the overall safety of consumer
cleaning
products, in particular towards consumers that suffer from multiple chemical
sensitivities.
[0009] In addition to proximate effects of potentially deleterious
ingredients,
increasing attention has turned toward understanding conveyance of such
chemicals
from the household to the larger environment. Indeed it has been reported that
the
exhaust coming out of a dryer vent has detectable amounts of volatile organic
compounds (VOCs) in all tested commercially available detergent products. See
A.C.
Steinemann, L.G. Gallagher, A.L. Davis, and I.C. MacGregor, "Chemical
Emissions
from Residential Dryer Vents During Use of Fragranced Laundry Products," Air
Quality, Atmosphere and Health, 6 (2011) 151-156. VOCs from consumer products
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can migrate outdoors and thus impact outdoor air quality. According to
California Air
Resources Board 1990 statistics, some 265 tons of VOCs were released into
California
air from the use of consumer products each day. See B. Bridges, "Fragrance:
Emerging
Health and Environmental Concerns," Flavour and Fragrance Journal, 17 (2002)
361-
371. This makes it difficult for a customer trying to make an environmentally
conscious decision to purchase cleaning products that will not release harmful
VOCs
into the atmosphere.
[0010] In summary, cleaning products available in the market today do not
explicitly
address all aspects of consumer safety. While the vast majority of cleaning
product
manufacturers ensure that their products cause minimal acute and chronic
toxicity
problems, exposure to cleaning product chemicals has been associated with the
development and exacerbation of asthma and related disorders. However,
consumers
who may desire to lessen their exposure to harmful chemicals by purchasing
safe
cleaning products are unable to do so because product ingredients are not
fully
disclosed on labels. Further, the ingredient profiles of cleaning products
that are
claimed to be green are remarkably similar to those not labeled green, causing
confusion in the minds of consumers looking for safe cleaning products.
Indeed,
experts on indoor air quality have shown the presence of known carcinogens and
hazardous air pollutants even in cleaning products that are free of fragrances
and dyes.
DESCRIPTION OF THE RELATED ART
[0011] U.S. Pat. Nos. 6,973,362 and 7,096,084 to Long, et at., teach a method
for
evaluating chemical components based on their function in the product. The
methods
taught by Long require first the function of a given raw material in a product
first be
identified, and then a set of predetermined criteria be applied based on the
function of
the raw material, to determine the raw material's designated environmental
class rating,
which is then given an environmental grade of from 1-3. The problem with this
method
is that it requires an individual, burdensome analysis of each component of a
composition to arrive at a final value for the composition as a whole. In
addition, it
requires that the individual components be analyzed by their function and one
or more
components in a composition may have multiple functions. Furthermore, this
method
requires knowledge of all the components, their percentages in the formulation
and their
functions in a given formulation, which makes testing products off the shelf
impossible
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or impractical because the required information is often not readily
available. The end
result is that although this method provides a standardized method for
measuring the
environmental impact of a given chemical formulation, it too is burdensome and
requires too much information about the components and their functions to make
it
practical for use in testing a wide range of compositions that are available
on store
shelves.
[0012] International Publications Nos. W02007099294, W02009024743, and
W02009024747 assigned to Reckitt Benckiser Group, plc, teach compositions for
toilet
cleaning and hard surface cleaning which are "environmentally acceptable," but
the
application does not clearly define what is meant by "environmentally
acceptable". The
publications merely teach cleaning compositions, which do not have high levels
of
volatile organic compounds or VOCs, and exclude certain acids, solvents,
chelating
agents and thickeners. While these applications teach certain "environmentally
acceptable" compositions, it does not establish any criteria or test methods
which could
be used to determine if other compositions meet this criteria other than those
compositions which may have the same exact ingredients as those taught in the
application.
[0013] Similarly, U.S. Pat. Nos. 5,990,065 and 6,069,122 assigned to Procter &
Gamble teach compositions for dishwashing detergents that contain natural
surfactants
and solvents, but they do not teach a method or criteria of determining
whether a
composition is "natural" or a means of measuring the natural components in a
given
composition. These patents merely teach a means of making a particular
dishwashing
composition that contains some natural ingredients.
SUMMARY OF THE DISCLOSURE
[0014] The present disclosure concerns a new scientific protocol for the
formulation
of cleaning products to minimize the triggering of asthma or other
immunological
responses in humans. In addition to improving the outlook for symptom-free
cleaning,
products generated according to the criteria described herein, while virtually
non-
petroleum based, are equivalent in performance to existing cleaning products
on the
market.
DEFINITIONS
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[0015] In the present specification and claims, reference will be made to
phrases and
terms of art which are expressly defined for use herein as follows:
[0016] Active ingredient or active material refers to entities that contribute
to the
cleaning of stains and soils and/or disinfecting of fabrics or surfaces. A
chemical
mixture as procured from suppliers may be diluted with a solvent such as
water, which
serves no purpose in cleaning and/or disinfection; in such case, the active
ingredient
refers only to the portion of the chemical mixture that serves a purpose to
clean and/or
disinfect. This term does not generally include aesthetic ingredients such as
fragrance
materials, colorants, viscosity modifiers, preservatives, or the like.
[0017] Biologically based carbon or bio-based carbon is carbon derived from
plant
or animal sources that have lived up until the relatively recent past. It is
distinguished
from carbon derived from fossil sources such as coal, subterranean natural
gas, oil or
petroleum-based carbon. Bio-based carbon is characterized by the presence of
radioactive 14C, unlike fossil sources of carbon in which radioactive 14C is
depleted or
entirely absent.
[0018] Chemical allergy describes the adverse health effects that my result
when
exposure to a chemical elicits an immune response in an individual. Chemical
allergens
are produce reactions similar to allergens such as pollens, weeds, and dander,
but
appear to be generated when lower-molecular weight chemicals function as
haptens and
bind to carrier macromolecules. See M.H. Karol, O.T. Macina, and A.
Cunningham,
"Cell and molecular biology of chemical allergy," Ann Allergy Asthma Immunol.
87
(2001) 28-32.
[0019] Cleaning composition or cleaning formulation as used herein refers to a
mixture of ingredients assembled together for the purpose of providing an aid
to the
removal of dirt, soil, grime, food waste, etc., from a surface or individual.
A cleaning
composition may be formulated for use in cleaning laundry, hard surfaces such
as
dishes, kitchen surfaces, bathrooms, glass, mirrors, etc., and may be
comprised of both
of active ingredients and aesthetic ingredients. A cleaning composition is
distinguished
from a product that is primarily a single cleaning active, such as a bar of
soap. A
cleaning composition is typically the product presented for sale to consumers.
[0020] Greenwashing as used herein refers to the practice of making or making
a
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false, misleading, or inflated green marketing claims. This practice was
expanded upon
in December 2007 by the environmental marketing firm TerraChoice. See "The Six
Sins of GreenwashingTm," A 'Green Paper' by TerraChoice Environmental
Marketing
Inc. (November 2007); http://www.sinsofgreenwashing.com/index6b90.pdf. This
article
is incorporated herein by reference in its entirety.
[0021] Haptens are small molecules that are not immunogenic on their own, but
which can conjugate to a carrier protein. The protein-hapten conjugate can
induce an
immune response. Haptens can enter the body through numerous routes, such as
skin
absorption, inhalation, ingestion and the olfactory pathways. Once inside the
body, the
haptens can impact any organ or system. Some of these materials are known to
cause
both skin and respiratory sensitization. It has also been found that skin
contact may
play a role in respiratory sensitization. See M.H. Karol, O.T. Macina, and A.
Cunningham, "Cell and molecular biology of chemical allergy," Ann Allergy
Asthma
Immunol. 87 (2001) 28-32.
[0022] Headspace or headspace technology as used herein concerns measurement
and characterization of components present in the space above a particular
composition
or ingredient. Headspace analysis involves removing volatile compounds from
the
headspace surrounding an object or other material of interest using either an
inert gas or
by establishing a vacuum. The compounds are then trapped and analyzed with
techniques such as gas chromatography, mass spectrometry or Carbon-13 NMR.
(See,
for example, en.wikipedia.org/wiki/Headspace technology).
[0023] Modern carbon refers to carbon derived from modern life forms, either
plant
or animal. It is distinguished from carbon derived from fossil sources such as
coal,
subterranean natural gas, oil or petroleum-based carbon. It is characterized
by presence
of radioactive NC in its make-up, which is depleted in feedstocks sourced from
fossil
carbon.
[0024] Product refers to a cleaning composition or cleaning formulation
offered for
commercial sale. The term can be understood to be synonymous with cleaning
composition or cleaning formulation.
[0025] Renewable carbon source or renewably sourced carbon is synonymous with
modern carbon, and refers to carbon sourced from non-primitive or non-ancient
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sources, i.e., it is not derived from fossil sources, which is coal,
subterranean natural
gas, oil or petroleum-based carbon. Renewable carbon source or renewably
sourced
carbon derives from modern life forms, either plant or animal, and is labeled
as
renewable because it is relatively easily replenished relative to fossil
carbon, which
takes millennia if not eons to form. It is characterized by presence of
radioactive 14C in
its make-up, which is depleted in feedstocks sourced from fossil carbon.
[0026] Soap as used herein refers to saponified animal fats and vegetable
oils. Soap
is understood to be distinguishable from synthetic surfactants, builders, pH
adjusters,
solvents, soil release agents, antimicrobials, enzymes and bleaching agents.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0027] The instant disclosure concerns a multi-tiered approach to screening
ingredients for suitability for use in cleaning products, formulating cleaning
products
that contain acceptable ingredients, and evaluating the resulting cleaning
products thus
formulated. As all cleaning products are combinations of raw materials, which
individually may constitute mixtures, the chance of including undesirable
chemicals in
cleaning products is therefore high without an appropriate screening process.
MODERN CARBON-BASED INGREDIENTS
[0028] Radiocarbon dating and analysis is a commonly used process to date
carbon-
based artifacts and remains within the field of archeology. More recently,
radiocarbon
dating has been used for testing a variety of different products including but
not limited
to: personal care products, wipes, lubricants, plastics, cleaning products,
gardening
products, etc. The subject is discussed extensively in "Determining the Modern
Carbon Content of Biobased Products Using Radiocarbon Analysis", by G.A.
Norton
and S.L. Devlin, from Iowa State University, published by Bioresource
Technology 97
(2006) 2084-2090; the article in its entirely is herein incorporated by
reference.
[0029] The article on determining modern carbon content describes the process
of
radiocarbon dating for the determination of bio-based content in a
formulation. Several
carbon isotopes are present in nature,
13C and 14C. The 12C is a stable isotope and
the 14C is an unstable isotope and undergoes radioactive decay. The 14C is
produced in
the atmosphere where it is oxidized to CO2 and CO2 is then absorbed by plants
until the
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12C/14C ratio in all living matter is essentially the same as that in the
atmosphere. When
something dies, it stops absorbing carbon and the amount of 14C diminishes
with time,
as it naturally undergoes radioactive decay. The rate of decay for the 14C is
measurable
and can be calculated. The decay rate for 14C is slow, about 5730 years,
relative to the
movement of carbon through the food chain, from plants to animals to bacteria.
All
carbon in biomass at earth's surface contains atmospheric levels of 14C
whereas
petrochemical feedstock that has been dead and in the ground for millions of
years will
have little to no 14C. Therefore, material derived from a recently living
plant will have
an abundance of 14C that is approximately equal to that in the atmosphere,
whereas
petrochemical feedstocks will not have a 14C signature.
[0030] By knowing the feedstocks of individual components of a molecule, one
can
estimate its amount of bio-based or modern carbon. For example, if all the
component
carbons of an ingredient are from plant- or animal-basis, it is deemed 100%
bio-based
or modern carbon; if only half of the component carbons are from bio-based or
modern
sources, while the other half of the component carbons are from non-modern
sources
such as coal, subterranean natural gas, oil or petroleum-based carbon, then
the
ingredient is 50% bio-based or modern carbon. This number, designated as
Percent
Modern Carbon (pMC), has been described by others as Biorenewable Carbon Index
(BCI) or Renewable Carbon Index (RCI), and is used synonymously herein. As
long as
one is knowledgeable about the source of all the carbons in the molecule of
interest,
that is, whether they are derived from modern carbon sources or non-modern
carbon
sources, one can estimate the Percent Modern Carbon (pMC) using Equation (1):
Estimated pMC = (number of carbons from modern carbon sources) x 100% (1)
(total number of carbons from all sources)
[0031] Alternatively, one can analyze for bio-based or modern carbon content,
alternately termed Percent Modern Carbon (pMC), can be carried out by standard
test
methodology such as radiocarbon analysis, according to ASTM method D6866-05,
which relies on analyzing the sample for radioactive 14C. Using 14C analysis
and
calculations, one can determine or confirm the amount of carbon in a material
from
fossil carbon, which is coal, oil or petroleum-based carbon. By measuring the
amount
of radioactive carbon in a sample, the amount of modern carbon or bio-based
carbon
can be determined. As one can understand, the Percent Modern Carbon (pMC),
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Biorenewable Carbon Index (BCI) or Renewable Carbon Index (RCI) is a measure
of
the percent of modern or biobased carbon in an individual ingredient or in a
composition.
[0032] The Percent Modern Carbon (pMC), Biorenewable Carbon Index (BCI) or
Renewable Carbon Index (RCI) only refers to the element, carbon, in the
molecule or
compound. Therefore, it is an index of the ratio of new, modern, bio-based
carbon to
"old", typically petrochemical-based carbon. pMC (as well as its synonymous
terms
BCI and RCI) does not refer to any other elements such as H, N, 0, S, etc.
that may be
present in a compound. One complication in the calculation of pMC is that
inorganic
carbon, such as that from the carbonates, would be included as "old" carbon,
although it
might originate from a "natural" mineral source. However, laboratories do have
ways
to deal with this complication experimentally and can account for mineral-
based
carbon. Materials with 100% modern carbon or bio-based carbon have no fossil
carbon
or petroleum based carbon and are considered carbon from renewable resources.
[0033] The radioactive carbon dating analysis that serves as the bases for
pMC/BMI/RCI may be performed using American Society of Testing Materials
(ASTM) method D6866-05, which is herein incorporated by reference. ASTM D6866-
05 describes various techniques for measuring radioactive carbon using 1)
accelerator
mass spectrometry (AMS), 2) benzene synthesis, or 3) carbon dioxide
absorption, also
known as the carbon dioxide cocktail method. For benzene synthesis or carbon
dioxide
absorption methods, a liquid scintillation counter (LSC) is used to detect
byproducts of
the 14C decay process. When preparing a sample for radiocarbon analysis, the
sample
composition maybe dehydrated, to prepare the sample for testing. Depending on
the
method used for radiocarbon analysis, the degree of uncertainty may vary
slightly.
Using ASTM method D6866-05, the degree of uncertainly is approximately 1 to
2%.
Using an LSC, the degree of uncertainly reaches approximately 3%. When using
the
AMS method or the benzene synthesis method to measure NC, radioactive carbon
count
must be corrected for isotropic fractionation to obtain a corrected
radiocarbon count.
The carbon dioxide cocktail method does not require a correction for isotropic
fractionation. The radioactive carbon dating process and analysis may be done
for
whole compositions or for individual components of compositions, and any
combinations or variations thereof
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[0034] In a first aspect, a method for determining the suitability of
ingredients for use
in the novel cleaning compositions described herein involves performing an
assessment
of the bio-basis of the ingredient, either through the estimation means
described above
or by analytical data such as that described in ASTM D6866-05. It is
preferable that
ingredients used herein are predominantly, if not entirely, renewably sourced,
i.e.,
biologically-based or bio-based, as well as readily and completely
biodegradable. It has
been found in the course of the present work that individuals with Multiple
Chemical
Sensitivities or MCS may tolerate ingredients with higher content of modern
carbon
better than ingredients high in content of non-modern carbon, such as
petrochemicals.
According to one aspect of the instant disclosure, therefore, cleaning
ingredients--and
preferably all formula ingredients--are selected to contain at least 80%, and
more
preferably at least 85% bio-based or modern carbon, more preferably at least
90% bio-
based or modern carbon, and most preferably 100% bio-based or modern carbon.
It is
preferred that the entire formulation be at least 90% bio-based or modern
carbon, more
preferably greater than about 95% bio-based or modern carbon, and most
preferably
greater than about 99% bio-based or modern carbon.
SELECTION OF INGREDIENTS
[0035] It has been determined in the course of the present work described
herein that
even ingredients that claim or analyze to be 100% bio-based can contain
undesirable
contaminants, such as low levels of residual petrochemical solvents,
catalysts, or unsafe
by-products. Hence, it is important to also analyze for materials that contain
known
hazardous volatile organic compounds (VOCs) and carcinogens, and/or that may
contain potential "telltale" indicators for petrochemicals, such as phenyl
derivatives.
This is typically accomplished by conducting a headspace analysis of the
ingredient
under consideration for use in a particular cleaning formulation. Methods have
been
developed for this purpose, most specifically EPA Compendium Method TO-15,
"Determination Of Volatile Organic Compounds (VOCs) In Air Collected In
Specially-
Prepared Canisters And Analyzed By Gas Chromatography/Mass Spectrometry
(GC/MS)," EPA, 1999, and U.S. EPA Method TO-11A, "Determination of
Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High
Performance Liquid Chromatography (HPLC)," EPA, 1999.
[0036] The analytes from such a headspace determination can be compared
against
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authoritative lists of hazardous ingredients, such as can be found in the
Clean Air Act¨
Toxic and Flammable Substances for Accidental Release Prevention list, the
Clean Air
Act¨ Hazardous Air Pollutant list, the Comprehensive Environmental Response,
Compensation, and Liability Act¨Hazardous Substance list, the Clean Water Act¨
Priority Pollutant list, the Emergency Planning & Community Right to Know Act¨
Toxic Release Inventory Chemical list, the Federal Insecticide, Fungicide, and
Rodenticide Act¨Registered Pesticide list, the Occupational Safety and Health
Act¨
Air Contaminants list, and/or the Resource Conservation and Recovery Act¨
Hazardous Constituents list. In another aspect, therefore, a method for
determining the
suitability of an ingredient for use in novel cleaning compositions as
described herein
involves determining the level of VOCs that may be contributed to a final
formulation
by performing a headspace analysis on the ingredient. In a similar aspect, a
method for
determining the suitability of a cleaning composition for use with individuals
that
exhibit MCS involves determining the level of VOCs in the headspace of the as-
formulated cleaning composition. It may be understood that physiological
responses
may differ for each contaminant, and most preferably none of the analytes
found in the
headspace is to be found on the authoritative lists. Analytes that might be
found on the
authoritative lists should be present at levels below about 100 jig/m3, more
preferably
below 10 jig/m3.
[0037] Finally, through working with individuals that exhibit MCS in the
course of
the instant work, it has been determined that it is advantageous that cleaning
compositions essentially contain no active components that have a vapor
pressure
exceeding 0.1 mm Hg at 20 C. It is further desirable to screen out chemicals
that may
react with proteins to form protein-hapten conjugates. Without being bound by
theory,
it is believed that moieties such as surfactant residues that have a chain
length of greater
than 8 carbon atoms are insufficiently reactive with proteins to form protein-
hapten
complexes. Alternatively, it is postulated that any protein-hapten conjugate
having
greater than an 8-carbon atom chain length that may form, are present in
concentrations
that are lower than a threshold level needed to trigger an immunogenic
response. As
such, it is preferred to formulate cleaning products that contain ingredients,
especially
surfactants with hydrophobic carbon chains that are essentially devoid of
carbon chains
of 8 or less. In other words, surfactants and other moieties having greater
than 8-carbon
chain lengths are especially preferred.
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[0038] It is further advantageous for a cleaning composition to also be devoid
of
impurities that have a vapor pressure exceeding 0.1 mm Hg at 20 C. Impurity or
impurities as used herein therefore refer to an ingredient that is not
knowingly or
intentionally desired to be incorporated into a cleaning composition of the
instant
disclosure by a formulator or other individual, as will be readily understood
by one
skilled in the relevant art. In yet another aspect, therefore, a method for
determining the
suitability of ingredients for use in novel cleaning compositions as described
herein
involves selecting ingredients that contain no active component that has a
vapor
pressure exceeding 0.1 mm Hg at 20 C. In still another aspect, a method for
determining the suitability of ingredients for use in formulating the novel
cleaning
compositions described herein involves selecting ingredients that contain no
impurities
that have a vapor pressure greater than 0.1 mm Hg at 20 C.Marketing studies
have
confirmed that consumers associate fragrance substantivity with increased
cleanliness.
However, multiple scientific studies have implicated fragrances as being the
culprit in
exacerbating or causing deleterious health effects in susceptible individuals
or entire
segments of the population. It is therefore preferable to incorporate
fragrances that are
known to not cause deleterious effects. Without being bound by theory, the
incorporation of optically active isomers of fragrance molecules in their
naturally
occurring form is favored as possibly having less adverse effects than their
synthetic
analogs.
EVALUATION OF INGREDIENTS AND FORMULATIONS
[0039] Once candidate ingredients are identified and tested as described
above, they
are evaluated for use in potential cleaning formulations using a blind study
protocol.
The blind studies used in the course of the instant work were comprised of a
specially
selected panel of volunteers. Volunteers diagnosed with both multiple chemical
sensitivities (MCS) and asthma have been found to be able to detect the
presence of
problematic chemicals, even at low levels. A panel comprised of just such
individuals
was used for many aspects of the studies conducted herein. While animals use
olfactory-mediated defense systems to detect, locate and identify predators in
their
surrounding environment, it has been found that human subjects are similarly
able to
discriminate among negative odors accurately. See E.A. Krusemark and W. Li,
"Enhanced olfactory sensory perception of threat in anxiety: An event-related
fMRI
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study," Chemosensory Perception, 5 (2012) 37-45; the article in its entirely
is herein
incorporated by reference.
[0040] In fact, people with MCS have demonstrated an ability to detect harmful
chemicals at levels far lower than the rest of the population. In the course
of the instant
work, at least one individual with MCS was used to rank prospective
ingredients for
acceptability in cleaning formulations based upon sensory responses, which
included
olfactory as well as skin contact. Instrumental analyses were then implemented
to
correlate results with sensory ratings from the human panel, and to identify
and/or
quantify the chemicals detected and deemed to be potentially harmful to
humans.
Ingredients that were deemed acceptable by the human panel and the
instrumental
analyses were then used as raw materials for cleaning products described
herein. It is
believed that this level of pre-screening and testing represents a first in
the world for
consumer cleaning product formulations work, and has provided an unprecedented
level of safety testing for consumer products. Accordingly, in one aspect of
the
technology newly presented and described herein, a method for providing
cleaning
formulations for use by the general public and chemically-sensitized
individuals, in
particular, involves:
1. assessing the bio-basis of an ingredient or ingredients for use in a
cleaning product;
2. evaluating the ingredient or ingredients from step 1. for acceptability
by at least one individual who manifests multiple chemical sensitivities; and
3. formulating a cleaning product using the acceptable ingredient or
ingredients from step 2; wherein each ingredient contains at least 80% pMC.
[0041] As a double-check on the safety of cleaning product formulation
ingredients,
they can be evaluated for the presence or absence of potentially harmful
volatile organic
carbon (VOC) compounds. In a recent publication it was found that 37 products
emitted 156 different VOCs, with an average of 15 VOCs per product. Of these
156
VOCs, 42 VOCs are classified as toxic or hazardous under U.S. federal laws,
and each
product emitted at least one of these chemicals. See A. Steinemann, "Volatile
Emissions from Common Consumer Products," Air Quality, Atmosphere & Health,
March 2015; the article in its entirely is herein incorporated by reference.
Emissions of
carcinogenic hazardous air pollutants (HAPs) from green fragranced products
were not
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significantly different from regular fragranced products. The most common
chemicals
in fragranced products were terpenes which, interestingly, were not found to
be present
in fragrance-free formulations. Of the volatile ingredients found in the
headspace of
these products, fewer than 3% were disclosed on any product label or material
safety
data sheet (MSDS).
[0042] After the acceptance of ingredients is established via the methods
identified
above, cleaning products using these approved chemicals may then be formulated
and
evaluated for efficacy. As it is recognized that combinations of effects can
cause
antagonistic responses, evaluations of fully formulated products were then
carried out
via sensory evaluation and VOC analysis. This permits further evaluation of
the
suitability of product formulations and the ability to assess product
performance as
compared with existing cleaning products. This was done on a qualitative
rating scale
both for cleaning efficacy and for presumed safety.
[0043] Accordingly, in another aspect, a method for providing cleaning
formulations
for use by chemically-sensitized individuals in addition to the general
public, involves:
1. assessing the bio-basis of an ingredient or ingredients for use in a
cleaning product;
2. evaluating the ingredient or ingredients from step 1. for acceptability
by at least one individual who manifests multiple chemical sensitivities;
3. formulating a cleaning product using the acceptable ingredient or
ingredients from step 2; and
4. performing a VOC headspace analysis of the cleaning product
formulated in step 3, wherein a headspace analysis of less than about 100
jig/m3 is
regarded as acceptable.
[0044] In yet another aspect, a method for providing cleaning products for use
by
chemically-sensitized individuals as well as for the general public, involves,
in addition
to steps 1. through 4. above, at least one of the steps of:
5. confirming the cleaning efficacy of a cleaning product formulated
according to steps 1. through 4. above; and
6. evaluating the cleaning product formulated according to steps 1.
through 4. above for acceptability for use by at least one individual who
manifests
multiple chemical sensitivities.
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[0045] In a different aspect, a method for providing cleaning products that
are
particularly well suited for use by chemically-sensitized individuals,
includes:
1. assessing the bio-basis of an ingredient or ingredients for use in a
cleaning product;
2. evaluating the ingredient or ingredients from step 1. for acceptability
by at least one individual who manifests multiple chemical sensitivities;
3. formulating a cleaning product using the acceptable ingredient or
ingredients from step 2; and
4. performing a headspace analysis of the cleaning product formulated in
step 3; wherein assessing step 1. includes an analysis of the feedstock of the
ingredient
or ingredients according to ASTM method D6866-05 or one consistent therewith.
[0046] In still another aspect, a method for providing cleaning products
according to
the instant disclosure includes any of assessing steps 1. above, further
wherein the
assessing is achieved by analysis according to or consistent with ASTM D6866-
05.
[0047] In yet another aspect, a method for providing cleaning products that
are
particularly well suited for use by chemically-sensitized individuals as well
as the
general public, includes:
1. assessing the bio-basis of an ingredient or ingredients for use in a
cleaning product;
2. evaluating the ingredient or ingredients from step 1. for acceptability
by at least one individual who manifests multiple chemical sensitivities;
3. formulating a cleaning product using the acceptable ingredient or
ingredients from step 2; and
4. performing a headspace analysis of the cleaning product formulated in
step 3; wherein assessing step 1. includes an analysis of the feedstock of the
ingredient
or ingredients by analysis that may be according to ASTM method D6866-05, a
method
that is consistent therewith, by consulting appropriate tabulated material, or
by any
combination of the foregoing.
[0048] In yet still another aspect, a method for providing cleaning products
that are
particularly well suited for use by chemically-sensitized individuals as well
as the
general public, includes, in addition to any of steps 1. through 5. above, at
least one of
the following criteria:
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a. the ingredient or ingredients of step 1. have a pMC of at least 80%,
more preferably at least 85%, and most preferably at least 90%;
b. individual ingredients are evaluated for acceptability and deemed
suitable by at least one individual who manifests multiple chemical
sensitivities or
MCS;
c. the cleaning formulation has a pMC of at least 90%, more preferably at
least 95%, and most preferably at least 99%;
d. the headspace analysis reveals less than 1000 jig/m3 VOCs regulated
by governmental bodies;
e. the cleaning formulation is deemed acceptable by at least one
individual who manifests multiple chemical sensitivities or MC S.
[0049] In yet still another aspect, a cleaning product according to the
disclosure
herein that is particularly well suited for use by chemically-sensitized
individuals as
well as the general public, includes: a composition comprising at least one
ingredient
that is a non-soap cleaning active, wherein the ingredient has a pMC of at
least 80%,
wherein a headspace analysis of the composition reveals the absence of phenyl
compounds or their derivatives, wherein less than about 5% by weight of the
ingredients have a vapor pressure that is above 0.1 mm Hg at 20 C, wherein the
composition contains less than about 1% by weight of a fragrance material;
wherein
headspace analysis of the cleaning product reveals less than about 1000 jig/m3
VOCs
that are regulated by governmental bodies; and wherein the composition has
less than
0.1% by weight of ingredients that have been demonstrated to cause adverse
reactions
in chemically-sensitive individuals.
CLEANING FORMULATION COMPONENTS/INGREDIENTS
[0050] Cleaning formulations are generally comprised of a mixture of
ingredients,
each of which serves a purpose in the removal of soils and stains. Generally,
such
formulations can include one or more of the following active ingredients:
surfactants,
builders, pH adjusters, solvents, soil release agents, antimicrobials, enzymes
and
bleaching agents. Such formulations often include ingredients that are more
aesthetic
in their function: fragrance materials, dyes and colorants, viscosity control
agents,
pearlizing and opacifying agents, brighteners, preservatives, etc. A
discussion of the
types and best practice for incorporation of these materials follows.
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ANIONIC SURFACTANTS
[0051] Cleaning compositions according to the instant disclosure can contain
an
anionic surfactant. When an anionic surfactant is added to the compositions
described
hereinõ it can typically be added at a level from about 0.05% to about 15% by
weight,
preferably from about 0.05% to about 5% by weight, and more preferably from
about
0.1% to about 1% by weight of the composition. It is preferred that anionic
surfactants
have alkyl chain lengths greater than 10. It is further preferred that they be
sourced
from bio-based materials rather than petrochemicals. While this largely
eliminates
phenyl derivatives, it is envisioned that these materials could also be
sourced from bio-
based materials. It is yet further preferred that these materials be devoid of
contaminants such as 1,4-dioxane. While this largely eliminates ethoxylated
derivatives, it is envisioned that these materials can be sourced with a bio-
based source
of ethylene oxide, and that the 1,4-dioxane contaminant can be scrupulously
removed
or avoided during production.
[0052] Anionic surfactants suitable for use in the formulations discussed
herein
include C10-C14 alkyl sulfates and ethoxysulfates (e.g., Stepanol WA-EXTRA
from
Stepan Company), C10-C18 alkyl sulfonates, C10-C14 linear or branched alkyl
benzene
sulfonates, and Cio-C15 alkyl ethoxycarboxylate. Anionic surfactants may be
paired
with organic counterions or multivalent counterions in order to prevent
interference
with cationic species. Further examples of suitable surfactants are described
in
McCutcheon's Vol. 1: Emulsifiers and Detergents, North American Ed.,
McCutcheon
Division, MC Publishing Co., 1995, which is incorporated herein by reference.
[0053] In the course of the instant work, it was found that a number of
anionic
surfactants containing ethylene oxide, either through petrochemical or bio-
based
sources, contained detectable levels of 1,4-dioxane as a contaminant. Such
surfactants
are to be scrupulously avoided, with preference given to anionic surfactants
that have
no detectable level of 1,4-dioxane.
[0054] Highly preferred materials anionic surfactants are those that do not
cause any
significant color change, nor impart any discoloration, such as graying or
yellowing, to
the matrices into which they are introduced, or to fabrics to which they may
be applied,
either during treatment followed by drying and/or curing, or after the drying
and/or
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curing step followed by normal exposure to air, moisture or sunlight.
NONIONIC SURFACTANTS
[0055] The compositions can contain a nonionic surfactant. When a nonionic
surfactant is added to the composition, it can typically be added at a level
from about
0.05% to about 30% by weight, preferably from about 0.05% to about 20% by
weight,
and more preferably from about 0.1% to about 10% by weight of the composition.
[0056] Nonionic surfactants that are suitable for use herein include
alkylpolysaccharides, as disclosed in U.S. Patent
No. 4,565,647 to Llenado,
incorporated herein by reference. Especially preferred are those nonionic
surfactants
that have a hydrophobic group containing from about 10 to about 30 carbon
atoms,
preferably from about 10 to about 16 carbon atoms in addition to at least one
hydrophilic saccharide group such as glucose. Most preferred are
alkylpolysaccharides
whose hydrophobic groups are sourced from bio-based materials such as coconut
or
palm oil, and whose hydrophilic groups are source from bio-based materials, an
example of which is glucose sourced from corn. Certain alkylpolysaccharides
that
contain low levels of phenyl derivatives may also be acceptable for use with
the
formulations presented herein, providing the source of phenyl is bio-based.
[0057] Further suitable nonionic surfactants include addition products of
fatty
alcohols, fatty acids, and fatty amines (most preferably sourced from bio-
based
materials such as vegetable oils), coupled with alkoxylating agents such as
ethylene
oxide (E0), propylene oxide (PO), isopropylene oxide (IP0), or butylene oxide
(BO),
or a mixture thereof While most alkylene oxide units are derived from
petrochemicals
sources, and are as such not preferred, it is envisioned that they could be
derived from
bio-based sources in the future. Moreover, it was found that a number of such
ingredients had detectable levels of 1,4-dioxane as a contaminant. Such
sources of
alcohol alkoxylates must be scrupulously avoided, with preference given to
sources that
have no detectable level of 1,4-dioxane. Any of the alkoxylated materials of
the
particular type described hereinafter can be used as the nonionic surfactant.
Preferably,
the nonionic surfactant is selected from the group consisting of primary and
secondary
alcohol ethoxylates as well as mixtures thereof. Nonionic surfactants may also
contain
a mixture of alcohol ethoxylates and propoxylates and mixtures thereof Further
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examples of suitable surfactants are described in McCutcheon's Vol. 1:
Emulsifiers and
Detergents, North American Ed., McCutcheon Division, MC Publishing Co., 1995,
which is incorporated herein by reference.
[0058] Highly preferred nonionic surfactants are those that do not cause any
significant color change, nor impart any discoloration, such as graying or
yellowing, to
the matrices or fabrics into which they are introduced or applied, either
during
treatment followed by drying and/or curing, or after drying and/or curing
followed by
normal exposure to air, moisture or sunlight exposure.
AMPHOTERIC AND ZWITTERIONIC SURFACTANTS
[0059] The compositions of the present disclosure can contain amphoteric
and/or
zwitterionic surfactants. When an amphoteric or zwitterionic surfactant is
added to a
composition of the present disclosure, it can typically be added at a level
from about
0.05% to about 30%, preferably from about 0.05% to about 20% by weight, and
more
preferably from about 0.1% to about 10% by weight of the composition.
[0060] Suitable amphoteric surfactants include amine oxides having the formula
(R1)(R2)(R3)NO wherein each of R1, R2 and R3 is independently a saturated
substituted
or unsubstituted, linear or branched hydrocarbon chain containing from 1 to 30
carbon
atoms. Preferred amine oxide surfactants that can be used herein include amine
oxides
having the formula (R1)(R2)(R3)NO wherein R1 is a hydrocarbon chain having
from 1 to
30 carbon atoms, preferably from 10 to 20, more preferably from 10 to 16,
further
preferably from 10 to 12, and wherein R2 and R3 are independently substituted
or
unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4
carbon
atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl
groups. R1
may be a saturated substituted or unsubstituted, linear or branched
hydrocarbon chain.
Suitable amine oxides for use herein are, for instance, naturally derived C12-
C16 amine
oxides commercially available from Lonza Group and Stepan Company. It is
especially
preferred that the pendent alkyl groups R2 and R3 are derived from bio-based
sources,
such as wood alcohol.
[0061] Suitable zwitterionic surfactants for use with the formulations
presented
herein may contain both cationic and anionic hydrophilic groups on the same
molecule
at a relatively wide pH range. A typical cationic group is a quaternary
ammonium
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group, although other positively charged groups like phosphonium, imidazolium
and
sulfonium groups can be used. Typical anionic hydrophilic groups are
carboxylates and
sulfonates, although other groups like sulfates, phosphonates, and the like
can be used.
A generic formula for some zwitterionic surfactants that can be used herein is
R1-
N'(R2)(R3)R4X, wherein R1 is a hydrophobic group comprising from 10 to 30
carbon
atoms; R2 and R3 are each C1-C4 alkyl, hydroxyalkyl or other substituted alkyl
group
which can also be joined to form ring structures with the N; R4 is a moiety
joining the
cationic nitrogen atom to the hydrophilic group and is typically an alkylene,
hydroxy
alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is
the
hydrophilic group which is preferably a carboxylate or sulfonate group.
Preferred
hydrophobic groups R1 are bio-based alkyl groups containing from 10 to 24,
preferably
less than 18, and more preferably less than 16 carbon atoms. The hydrophobic
group
can contain unsaturation and/or substituents and/or linking groups such as
aryl groups,
amido groups, ester groups and the like. In general, the simple alkyl groups
are
preferred for cost and stability reasons. It is especially preferred if the
pendent alkyl
groups R2 and R3 could be derived from bio-based sources, such as methyl
groups
derived from bio-based sources such as wood alcohol. Examples of amphoteric
surfactants include alkylamphoglycinates, and alkyl iminopropionate. Highly
preferred
zwitterionic surfactants include betaine and sulphobetaine surfactants,
derivatives
thereof or mixtures thereof The betaine or sulphobetaine surfactants are
preferred
herein as they are particularly suitable for the cleaning of delicate
materials, including
fine fabrics such as silk, wool and other naturally derived textile materials.
Betaine and
sulphobetaine surfactants are also extremely mild to the skin and/or fabrics
to be treated
that come in contact with the user's skin.
[0062] Suitable betaine and sulphobetaine surfactants to be used herein
include the
betaine/sulphobetaine and betaine-like detergents wherein the molecule
contains both
basic and acidic groups which form an inner salt giving the molecule both
cationic and
anionic hydrophilic groups over a broad range of pH values. Some common
examples
of these detergents are described in U.S. Patent No. 2,082,275 to Daimler, et
at., U.S.
Patent No. 2,702,279 to Funderburk, et at., and U.S. Patent No. 2,255,082 to
Orthner,
et at., which are incorporated herein by reference. Further examples of
suitable
surfactants are described in McCutcheon's Vol. 1: Emulsifiers and Detergents,
North
American Ed., McCutcheon Division, MC Publishing Co., 1995, which is
incorporated
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herein by reference.
[0063] Highly preferred materials of this class of amphoteric and zwitterionic
surfactants are those that do not cause any significant color change, nor
impart any
discoloration, such as graying or yellowing, to the matrices into which they
are
introduced, or to fabrics to which they may be applied, either during
treatment followed
by drying and/or curing, or after the drying and/or curing step followed by
normal
exposure to the elements, such as air, moisture or sunlight exposure.
CATIONIC SURFACTANTS
[0064] The compositions of the present disclosure can contain a cationic
surfactant.
When a cationic surfactant is added to the compositions disclosed herein, it
can
typically be added at a level from about 0.05% to about 30% by weight,
preferably from
about 0.05% to about 20% by weight, and more preferably from about 0.1% to
about
10% by weight of the composition.
[0065] The cationic surfactant can optionally be one or more fabric softener
actives.
Preferred fabric softening actives according to the present disclosure include
amines
and quaternized amines. The following are examples of preferred softener
actives:
N,N-di(tallowyl-oxy-ethyl)-N.N-dimethyl ammonium chloride; N,N-di(canolyl-oxy-
ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-
(2-
hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-
(2-
hydroxyethyl) ammonium methyl sulfate; N,N-di(tallowylamidoethyl)-N-methyl, N-
(2-
hydroxyethyl) ammonium methyl sulfate; N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-
dimethyl ammonium chloride; N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride; N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl
ammonium chloride; N,N-di(2-canolyl-oxyethylcarbonyloxyethyl)-N,N-dimethyl
ammonium chloride; N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-
dimethyl ammonium chloride; N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-
ethyl)-
N,N-dimethyl ammonium chloride, N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl
ammonium chloride; N,N,N-tri(canolyl-oxy-ethyl)-N-methyl ammonium chloride; N-
(2-tallowyloxy-2-oxoethyl)-N-(tallowy1)-N,N-dimethyl ammonium chloride; N-(2-
canolyloxy-2-oxoethyl)-N-(canoly1)-N,N-dimethyl ammonium chloride; 1,2-
ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and 1,2-dicanolyloxy-3-
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N,N,N-trimethylammoniopropane chloride; and mixtures of the above actives.
Particularly preferred is N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride,
where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-
oxy-
ethyl)-N,N- dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-
(2-
hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-
(2-
hydroxyethyl) ammonium methyl sulfate; and mixtures thereof. Additional fabric
softening agents useful herein are described in U.S. Patent No. 5, 643,865 to
Mermelstein, et at.; U.S. Patent No. 5,622,925 to de Buzzaccarini, et at.;
U.S. Patent
No. 5,545,350 to Baker, et at.; U.S. Patent No. 5,474, 690 to Wahl, et at.;
U.S. Patent
No. 5,417,868 to Turner, et at.; U.S. Patent No. 4,661,269 to Trinh, et at.;
U.S. Patent
No. 4,439,335 to Burns; U.S. Patent No. 4,401,578 to Verbruggen; U.S. Patent
No.
4,308,151 to Cambre; U.S. Patent No. 4,237,016 to Rudkin, et at.; U.S. Patent
No.
4,233,164 to Davis; U.S. Patent No. 4,045,361 to Watt, et at.; U.S. Patent No.
3,974,076 to Wiersema, et at.; U.S. Patent No. 3,886,075 to Bernadino; U.S.
Patent No.
3,861, 870 to Edwards, et at.; and European Patent Application publication No.
472,178, to Yamamura, et at.; all of said documents being incorporated herein
by
reference.
[0066] Other suitable cationic surfactants include ethoxylated quaternary
ammonium
surfactants. Some preferred ethoxylated quaternary ammonium surfactants
include
PEG-5 cocoammonium methosulfate; PEG-15 cocoammonium chloride; PEG-15
oleoammonium chloride; and bis(polyethoxyethanol) tallow ammonium chloride.
While these cationic surfactants are not preferred due to the ethylene oxide
units usually
being petrochemically-based, it is envisioned that the ethylene oxide units
could also be
bio-based. Further examples of suitable surfactants are described in
McCutcheon's Vol.
1: Emulsifiers and Detergents, North American Ed., McCutcheon Division, MC
Publishing Co., 1995, which is incorporated herein by reference.
[0067] The counterion to these cationic surfactants may be selected, without
limitation, from the group consisting of fluoride, chloride, bromide, iodide,
chlorite,
chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate,
acetate,
lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate,
benzoate, and
salicylate, and the like. Highly preferred materials of this class of cationic
surfactants
and their counterions are those that do not cause any significant color
change, nor
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impart any discoloration, such as graying or yellowing, to the matrices into
which they
are introduced, or to fabrics to which they may be applied, either during
treatment
followed by drying and/or curing, or after the drying and/or curing step
followed by
normal exposure to the elements, such as air, moisture or sunlight exposure.
BUILDERS AND pH ADJUSTERS
[0068] Builders are materials used to boost the performance of surfactants
used for
cleaning. Their best builder compounds react with multivalent cations,
"softening"
water by removing "hardness" ions (e.g., calcium and magnesium) that bind with
surfactants, reducing their effectiveness. Moreover these hardness ions can
react with
stains, making them more difficult to remove. Some builders also modify
solution pH
to provide alkalinity, which aids cleaning (stain neutralization,
saponification, surface
modification). Further, some builders can disperse and/or suspend soils, due
to their
ability to modify the surface charge on the soils that come into solution.
[0069] Adjustment of pH may be carried out by including a small quantity of an
acid
in the formulation. Because no strong pH buffers need be present, only small
amounts
of acid may be required. The pH may be adjusted with inorganic or organic
acids, for
example hydrochloric acid or alternatively with monobasic or dibasic organic
acids,
such as acetic acid, maleic acid or in particular glycolic acid. Additional
acids that can
be used include, but are not limited to, methyl sulfonic, hydrochloric,
sulfuric,
phosphoric, citric, maleic, and succinic acids.
[0070] Adjustment of pH may be carried out by including a small quantity of a
base
in the formulation. Because no strong pH buffers need be present, only small
amounts
of base may be required. The pH may be adjusted with inorganic bases,
including, but
not limited to, alkali metal or alkaline earth metal salts of hydroxides,
carbonates,
bicarbonates, borates, sulfonates, phosphates, phosphonates and silicates. The
pH may
be adjusted with organic bases, including, but not limited to, salts of
monocarboxylic
acids, salts of dicarboxylic acids, salts of citric acid and other suitable
organic acids
with water soluble conjugate bases presented previously herein. The pH may be
adjusted with organic bases such as the alkanolamines including methanol,
ethanol and
propanol amines, including dimethanol-, diethanol- and dipropanolamines, and
including trimethanol-, triethanol- and tripropanolamines.
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[0071] Highly preferred materials of this class of pH adjusters are those that
do not
cause any significant color change, nor impart any discoloration, such as
graying or
yellowing, to the matrices into which they are introduced, or to fabrics to
which they
may be applied, either during treatment followed by drying and/or curing, or
after the
drying and/or curing step followed by normal exposure to the elements, such as
air,
moisture or sunlight exposure.
SOLVENTS
[0072] The cleaning compositions can contain organic solvents that act as
diluents,
coupling agents, and to some extent aid cleaning. It is preferred that such
solvents be
bio-based, and while many solvents are typically obtained from petrochemical
sources,
it is envisioned that they could be derived from bio-based sources. Further
preferred
are solvents that do not appreciably contribute to VOCs.
[0073] Examples of organic solvents include, but are not limited to, Ci-C6
alkanols,
Ci-C6 diols, C1-C10 alkyl ethers of alkylene glycols, C3-C24 alkylene glycol
ethers,
polyalkylene glycols, short chain carboxylic acids, short chain esters,
isoparaffinic
hydrocarbons, mineral spirits, alkylaromatics, terpenes, terpene derivatives,
terpenoids,
terpenoid derivatives, formaldehyde, and pyrrolidones. Alkanols include, but
are not
limited to, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and
hexanol,
and isomers thereof Diols include, but are not limited to, methylene,
ethylene,
propylene and butylene glycols. Alkylene glycol ethers include, but are not
limited to,
ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene
glycol
monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol
monobutyl
ether, diethylene glycol monohexyl ether, propylene glycol methyl ether,
propylene
glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol
monobutyl ether,
propylene glycol t-butyl ether, di- or tri-polypropylene glycol methyl or
ethyl or propyl
or butyl ether, acetate and propionate esters of glycol ethers. Short chain
esters include,
but are not limited to, glycol acetate, and cyclic or linear volatile
methylsiloxanes.
Water insoluble solvents such as isoparaffinic hydrocarbons, mineral spirits,
alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes
derivatives can
be mixed with a water-soluble solvent when employed.
SOIL RELEASE AGENTS
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[0074] The composition can include a soil release agent that is present from
about 0%
to about 5% by weight, preferably from about 0.05% to about 3% by weight, and
more
preferably from about 0.1% to about 2% by weight of the composition. Polymeric
soil
release agents useful in the present disclosure include co-polymeric blocks of
terephthalate and polyethylene oxide or polypropylene oxide, and the like. A
preferred
soil release agent is a copolymer having blocks of terephthalate and
polyethylene oxide.
While most terephthalate and alkylene oxide units are derived from
petrochemicals
sources, and are as such not preferred, it is envisioned that they could be
derived from
bio-based sources. These polymers may be comprised of repeating units of
ethylene
terephthalate and polyethylene oxide terephthalate at a molar ratio of
ethylene
terephthalate units to polyethylene oxide terephthalate units from about 25:75
to about
35:65, and the polyethylene oxide terephthalate containing polyethylene oxide
blocks
having molecular weights from about 300 to about 2000. The molecular weight of
this
type of polymeric soil release agent can be in the range from about 5,000 to
about
55,000. Suitable soil release agents are disclosed in U.S. Patent Nos.
4,702,857 to
Gosselink, 4,711,730 to Gosselink, et at., 4,713,194 to Gosselink; 4,877,896
to
Maldonado, et at.; 4,956,447 Gosselink, et at.; and 4,749,596 to Po, et at.;
all of which
are incorporated herein by reference. Especially desirable optional
ingredients are
polymeric soil release agents comprising block copolymers of polyalkylene
terephthalate and polyoxyethylene terephthalate, and block copolymers of
polyalkylene
terephthalate and polyethylene glycol. The polyalkylene terephthalate blocks
may
preferably comprise ethylene and/or propylene groups. Many such soil release
polymers are nonionic, for example, the nonionic soil release polymer
described in U.S.
Patent No. 4,849,257 to Borcher, Sr., et at., which is incorporated herein by
reference.
The polymeric soil release agents useful in the present disclosure can include
anionic
and cationic polymeric soil release agents. Suitable anionic polymeric or
oligomeric
soil release agents are disclosed in U.S. Patent No. 4,018,569 to Chang, which
is
incorporated herein by reference. Other suitable polymers are disclosed in
U.S. Patent
No. 4, 808,086 to Evans, et at., which is incorporated herein by reference.
[0075] Highly preferred materials of this class of soil release polymers are
those that
do not cause any significant color change, nor impart any discoloration, such
as graying
or yellowing, to the matrices into which they are introduced, or to fabrics to
which they
may be applied, either during treatment followed by drying and/or curing, or
after the
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drying and/or curing step followed by normal exposure to the elements, such as
air,
moisture or sunlight exposure.
ANTISTATIC AGENTS
[0076] The composition can include antistatic agents, which can be present at
a level
from about 0% to about 5% by weight, preferably from about 0.005% to about 5%
by
weight, more preferably from about 0.05% to about 2% by weight, and further
preferably from about 0.2% to about 1% of the composition. While many of these
compounds are derived from petrochemical sources, and are as such not
preferred, it is
envisioned that they could be derived from bio-based sources. Preferred
antistatic
agents of the present disclosure include cationic surfactants, including
quaternary
ammonium compounds such as alkyl benzyl dimethyl ammonium chloride; dicoco
quaternary ammonium chloride; coco dimethyl benzyl ammonium chloride; soya
trimethyl quaternary ammonium chloride; hydrogenated tallow dimethyl benzyl
ammonium chloride; and methyl dihydrogenated tallow benzyl ammonium chloride.
Other preferred antistatic agents of the present disclosure are alkyl
imidazolinium salts.
Other preferred antistatic agents are the ion pairs of, e.g., anionic
detergent surfactants
and fatty amines, or quaternary ammonium derivatives thereof, e.g., those
disclosed in
U.S. Patent No. 4,756,850 to Nayar, which is incorporated herein by reference.
Other
preferred antistatic agents are ethoxylated and/or propoxylated sugar
derivatives; while
most alkylene oxide units are derived from petrochemicals sources, and are as
such not
preferred, it is envisioned that they could be derived from bio-based sources.
Preferred
antistatic agents include monolauryl trimethyl ammonium chloride, hydroxycetyl
hydroxyethyl dimethyl ammonium chloride (available from BASF Corporation under
the trade name DEHYQUART E), and ethyl bis(polyethoxyethanol) alkyl ammonium
ethyl sulfate (available from Evonik Corporation under the trade name VARIQUAT
66), polyethylene glycols, polymeric quaternary ammonium salts (such as those
available from Rhodia Group under the MIRAPOL trade name), quaternized
polyethyleneimines, vinylpyrrolidone/methacrylamidopropyl trimethylammonium
chloride copolymer (available from Ashland Inc. under the trade name GAFQUAT
HS-
100), triethonium hydrolyzed collagen ethosulfate (available from Angene
Chemical
under the trade name QUAT-PRO E), and mixtures thereof
[0077] Highly preferred materials of this class of antistatic agents are those
that do
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not cause any significant color change, nor impart any discoloration, such as
graying or
yellowing, to the matrices into which they are introduced, or to fabrics to
which they
may be applied, either during treatment followed by drying and/or curing, or
after the
drying and/or curing step followed by normal exposure to the elements, such as
air,
moisture or sunlight exposure.
FRAGRANCE MATERIALS
[0078] While not preferred due to their propensity to induce untoward symptoms
in
sensitized individuals, it has been discovered that truly natural, bio-based
fragrance
materials may be added to the composition. It appears that preferred fragrance
materials are comprised of extracts of natural products, upon which no
additional
functionalization reactions have been carried out. Further, preferred
fragrance materials
should not have been isolated in such a way as to introduce petrochemical
solvents,
which appear to further exacerbate symptoms of sensitization. Such materials
may
have been isolated by methods well-known to the industry such as extraction
with
suitable solvents, supercritical fluid extraction, steam distillation,
rectification, and
expression. It is also foreseen that by adding fragrance sources such as plant
materials
directly to the product, and relying on the product matrix itself to extract
the desired
fragrance notes, one can obtain desired fragrance notes.
[0079] The selection of the perfume or perfumes maybe based upon the
application,
the desired effect on the consumer, and preferences of the formulator. The
perfume
selected for use in the compositions and formulations of the present
disclosure may
contain ingredients with odor characteristics which are preferred in order to
provide a
fresh impression on the surface to which the composition is directed, for
example, those
which provide a fresh impression for fabrics. Such perfume may be preferably
present
at a level from about 0.01 % to about 5% by weight, preferably from about
0.05% to
about 3% by weight, and more preferably from about 0.1 % to about 2% by weight
of
the total composition.
[0080] Preferably, the fragrance materials are mixtures comprising multiple
ingredients selected from the group consisting of aromatic and aliphatic
esters having
molecular weights from about 130 to about 250; aliphatic and aromatic alcohols
having
molecular weights from about 90 to about 240; aliphatic ketones having
molecular
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weights from about 150 to about 260; aromatic ketones having molecular weights
from
about 150 to about 270; aromatic and aliphatic lactones having molecular
weights from
about 130 to about 290; aliphatic aldehydes having molecular weights from
about 140
to about 200; aromatic aldehydes having molecular weights from about 90 to
about 230;
aliphatic and aromatic ethers having molecular weights from about 150 to about
270;
and condensation products of aldehydes and amines having molecular weights
from
about 180 to about 320; and mixtures thereof
[0081] Highly preferred materials of this class of fragrances and perfumes are
those
that do not cause any significant color change, nor impart any discoloration,
such as
graying or yellowing, to the matrices into which they are introduced, or to
fabrics to
which they may be applied, either during treatment followed by drying and/or
curing, or
after the drying and/or curing step followed by normal exposure to the
elements, such
as air, moisture or sunlight exposure.
ANTIMICROBIALS AND PRESERVATIVES
[0082] Antimicrobials and/or preservatives can be used with the formulations
presented herein. Typical concentrations for biocidal effectiveness of these
compounds
may range from about 0.001% to about 0.8% by weight, preferably from about
0.005%
to about 0.3% by weight, and more preferably from about 0.01% to 0.2% by
weight of
the usage composition. The corresponding concentrations for the concentrated
compositions are from about 0.003% to about 2% by weight, preferably from
about
0.006% to about 1.2% by weight, and more preferably from about 0.1% to about
0.8%
by weight of the concentrated compositions.
[0083] Preservatives are especially preferred when organic compounds that are
subject to microorganisms are added to the compositions of the present
disclosure,
especially when they are used in aqueous compositions. When such compounds are
present, long term and even short-term storage stability of the compositions
and
formulations becomes an important issue since contamination by certain
microorganisms with subsequent microbial growth often results in an unsightly
and/or
malodorous solution. Therefore, because microbial growth in these compositions
and
formulations is highly objectionable when it occurs, it is preferable to
include a
solubilized water-soluble, antimicrobial preservative, which is effective for
inhibiting
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and/or regulating microbial growth in order to increase storage stability of
the
preferably clear and often aqueous compositions and formulations of the
present
disclosure.
[0084] Typical microorganisms that can be found in laundry products include
bacteria, for example, Bacillus thurigensis (cereus group) and Bacillus
sphaericus, and
fungi, for example, Aspergillus ustus. Bacillus sphaericus is one of the most
numerous
members of Bacillus species in soils. In addition, microorganisms such as
Escherichia
coli and Pseudomonas aeruginosa are found in some water sources, and can be
introduced during the preparation of aqueous solutions of the present
disclosure. It is
preferable to use a broad spectrum preservative, for example, one that is
effective on
both bacteria (both Gram positive and Gram negative) and fungi. A limited
spectrum
preservative, for example, one that is only effective on a single group of
microorganisms, for example, fungi, can be used in combination with a broad
spectrum
preservative or other limited spectrum preservatives with complimentary and/or
supplementary activity. A mixture of broad-spectrum preservatives can also be
used.
Antimicrobial preservatives useful in the present disclosure can be biocidal
compounds,
that is, substances that kill microorganisms, or biostatic compounds, that is,
substances
that inhibit and/or regulate the growth of microorganisms.
[0085] Preferred antimicrobial preservatives include those that are water-
soluble and
are effective at low levels. While such compounds are commonly derived from
petrochemicals sources, and are as such not preferred, it is envisioned that
they could be
derived from bio-based sources. In general, the water-soluble preservatives
that may be
used include organic sulfur compounds, halogenated compounds, cyclic organic
nitrogen compounds, low molecular weight aldehydes, quaternary compounds,
dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof
Examples
of preservatives useful with the formulations presented herein include, but
are not
limited to, the short chain alkyl esters of p-hydroxybenzoic acid (commonly
known as
parabens); N-(4-chloropheny1)-N-(3,4-dichlorophenyl) urea (also known as 3,4,4-
trichlorocarbanilide or triclocarban); 2,4,4-trichloro-2'-hydroxydiphenyl
ether,
commonly known as Triclosan0); a mixture of about 77% 5-chloro-2-methy1-4-
isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one, a broad
spectrum
preservative available from the Dow Chemical Company as a 1.5% aqueous
solution
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under the trade name KATHON CG; 5-bromo-5-nitro-1,3-dioxane, available from
BASF Corporation under the trade name BRONIDOX L; 2-bromo-2-nitropropane-1,3-
diol, available from Dow Chemical Company under the trade name BRONOPOL; 1,1-
hexamethylenebis(5-p-(chlorophenyl)biguanide) (commonly known as
chlorhexidine)
and its salts, for example, with acetic and digluconic acids; a 95:5 mixture
of 1,3-
bis(hydroxymethyl)-5,5-dimethy1-2,4-imidazolidinedione and 3-buty1-2-
iodopropynyl
carbamate, available from Lonza Group under the trade name GLYDANT Plus; N41,3-
bis (hydroxymethy1)2,5 -dioxo-4-imidazo lidiny1]-N,N'-bis (hydroxy-methyl)
urea,
commonly known as diazolidinyl urea, available from Ashland Inc. under the
trade
name GERMALL II; N,N"-methylenebis-[N'- [1 -(hydroxymethyl)-2,5 -dioxo-4-
imidazolidinyl]urea] (commonly known as imidazolidinyl urea), available, for
example,
from 3V-Sigma under the trade name ABIOL, from Induchem USA, Inc. under the
trade name UNICIDE U-13, and from Ashland Inc. under the trade name GERMALL
115; polymethoxy bicyclic oxazolidine, available from Ashland Inc. under the
trade
name NUOSEPT; formaldehyde; glutaraldehyde; polyaminopropyl biguanide under
the
trade name COSMOCIL CQ or MIKROKIL from Lonza Group; and mixtures thereof.
In general, however, the preservative can be any organic preservative material
that is
appropriate for applying to a fabric. With respect to the embodiments
presented herein,
such preservative(s) will preferably not cause damage to a fabric appearance,
for
example, through discoloration, coloration, or bleaching of the fabric. If the
antimicrobial preservative is included in the compositions and formulations of
the
present disclosure, it is preferably present in an effective amount, wherein
an "effective
amount" means a level sufficient to prevent spoilage or prevent growth of
inadvertently
added microorganisms for a specific period of time. Preferred levels of
preservative are
from about 0.0001% to about 0.5% by weight, more preferably from about 0.0002%
to
about 0.2% by weight, further preferably from about 0.0003% to about 0.1% by
weight,
of the composition. Optionally, the preservative can be used at a level that
provides an
antimicrobial effect on the treated fabrics.
[0086] The composition may suitably use an optional solubilized, water-soluble
antimicrobial active, useful in providing protection against organisms that
become
attached to the treated material. The
free, uncomplexed antimicrobial, e.g.,
antibacterial, active provides an optimum antibacterial performance.
Sanitization of
fabrics can be achieved by the compositions of the present disclosure
containing,
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antimicrobial materials, e.g., antibacterial halogenated compounds, quaternary
compounds, and phenolic compounds. Some of the more robust antimicrobial
halogenated compounds which can function as disinfectants/sanitizers as well
as finish
product preservatives, and are useful in the compositions of the present
disclosure
include 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known as
chlorhexidine, in addition to its salts, e.g., with hydrochloric, acetic and
gluconic acids.
The digluconate salt is highly water-soluble, at about 70% by weight in water,
while the
diacetate salt has a solubility of about 1.8% weight in water. When
chlorhexidine is
used as a sanitizer with the formulations discussed herein, it can typically
be present at
a level from about 0.001% to about 1.0% by weight, preferably from about
0.002% to
about 0.3% by weight, and more preferably from about 0.01% to about 0.1% by
weight
of the usage composition. In some cases, a level from about 1% to about 2% by
weight
may be needed for virucidal activity. Other useful biguanide compounds include
COSMOCIL CQ, VANTOCIL IB, including poly (hexamethylene biguanide)
hydrochloride. Other useful cationic antimicrobial agents include the bis-
biguanide
alkanes. Usable water soluble salts of the above are chlorides, bromides,
sulfates, alkyl
sulfonates such as methyl sulfonate and ethyl sulfonate, phenylsulfonates such
as p-
methylphenyl sulfonates, nitrates, acetates, gluconates, and the like. Non-
limiting
examples of useful quaternary compounds include: (1) benzalkonium chlorides
and/or
substituted benzalkonium chlorides such as commercially available BARQUAT
(available from Lonza), MAQUAT (available from Pilot Chemical), VARIQUAT
(available from Evonik), and HYAMINE (available from Lonza); (2) dialkyl
quaternary
such as BARDAC products of Lonza, (3) N-(3- chloroally1) hexaminium chlorides
such
as DOWICIDE and DOWICIL available from Dow; (4) benzethonium chloride such
as HYAMINE 1622 from Lonza; (5) methylbenzethonium chloride represented by
HYAMINE 10X supplied by Lonza, (6) cetylpyridinium chloride such as Cepacol
chloride available from of Merrell Labs.
[0087] Preferred antimicrobial compounds for use herein include quaternary
ammonium compounds containing alkylor substituted alkyl groups, alkyl amide
and
carboxylic acid groups, ether groups, unsaturated alkyl groups, and cyclic
quaternary
ammonium compounds, which can be chlorides, dichlorides, bromides,
methylsulphates, chlorophenates, cylcohexyl sulphamates or salts of the other
acids.
Among the useful cyclic quaternary ammonium compounds are the following:
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alkylpyridinium chlorides and/or sulphates, the alkyl group being preferably
cetyl,
dodecyl or hexadecyl group; -alkylisoquinolyl chlorides and/or bromides, the
alkyl
group being preferably dodecyl group. Particularly suitable quaternary
ammonium
compounds for use herein include alkyldimethylbenzyl ammonium chloride, octyl
decyl
dimethylammonium chloride, dioctyl dimethyl ammonium chloride, didecyl
dimethyl
ammonium chloride, alkyl dimethyl ammonium saccharinate, cetylpyridinium and
mixtures thereof
[0088] It is also envisioned that certain inorganic materials based on silver,
copper, or
clays materials such as DragoniteTM Halloysite clay (Applied Minerals, New
York, NY)
may be suitable for this purpose. Silver and copper materials may be embedded
within
the packaging matrix, so as to keep liquids contained therein preserved.
[0089] Highly preferred materials of this class of antimicrobials and
preservatives are
those that do not cause any significant color change, nor impart any
discoloration, such
as graying or yellowing, to the matrices into which they are introduced, or to
fabrics to
which they may be applied, either during treatment followed by drying and/or
curing, or
after the drying and/or curing step followed by normal exposure to the
elements, such
as air, moisture or sunlight exposure.
DYES AND COLORANTS
[0090] Colorants can be added to the formulations disclosed herein. As many
people
manifest sensitivity to synthetic dyes, they are not preferred. However,
certain natural
colorants such as chlorophyll may be suitable for incorporation herein.
Pigments,
which are insoluble colorants, may also be suitable for incorporation in the
formulations
described herein. Typical concentrations of these compounds may range from
about
0.001% to about 0.8% by weight, preferably from about 0.005% to about 0.3% by
weight, and more preferably from about 0.01% to 0.2% by weight of the
composition.
[0091] Colorants and dyes, especially bluing agents, can be optionally added
to the
compositions of the present disclosure for visual appeal and performance
impression.
When colorants are used, they may be used at extremely low levels to avoid
fabric
staining.
[0092] Highly preferred materials of this class of dyes and colorants are
those that do
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not effectively bind to or permanently dye or color fabrics treated by use of
the
compositions disclosed herein, nor cause any significant color change, nor
impart any
discoloration, such as graying, to the matrices into which they are
introduced, or to
fabrics to which they may be applied, either during treatment followed by
drying and/or
curing, or after the drying and/or curing step followed by normal exposure to
the
elements, such as air, moisture or sunlight exposure.
VISCOSITY CONTROL AGENTS
[0093] Optionally added viscosity control agents can be organic or inorganic
in
nature and may either lower or raise the viscosity of the formulation. While
many such
compounds are commonly derived from petrochemicals sources, and are as such
not
preferred, it is envisioned that they could be derived from bio-based sources.
Examples
of organic viscosity modifiers to lower viscosity are aryl carboxylates and
sulfonates
(for example including, but not limited to benzoate, 2-hydroxybenzoate, 2-
aminob enzo ate, benzenesulfonate, 2-hydroxyb enzenesulfonate, 2-
aminobenzenesulfonate), fatty acids and esters, fatty alcohols, and water-
miscible
solvents such as short chain alcohols. Examples of inorganic viscosity control
agents
are water-soluble ionizable salts. A wide variety of ionizable salts can be
used.
Examples of suitable salts are the halides and acetates of ammonium ion and
the group
IA and HA metals of the Periodic Table of the Elements, for example, calcium
chloride,
lithium chloride, sodium chloride, potassium chloride, magnesium chloride,
ammonium
chloride, sodium bromide, potassium bromide, calcium bromide, magnesium
bromide,
ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium
iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures
thereof
Calcium chloride is preferred. The ionizable salts are particularly useful
during the
process of mixing the ingredients to make the compositions herein, and later
to obtain
the desired viscosity. The amount of ionizable salts used depends on the
amount of
active ingredients used in the compositions and can be adjusted according to
the desire
of the formulator. Typical levels of salts used to control the composition
viscosity are
from 0 to about 10% by weight, preferably from about 0.01% to about 6% by
weight,
and more preferably from about 0.02% to about 3% by weight of the composition.
[0094] Viscosity modifiers or thickening agents can be added to increase the
ability
of the compositions to stably suspend water-insoluble articles, for example,
perfume
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microcapsules. Such materials include hydroxypropyl substituted guar gum (such
as
that available from Rhodia Group under the trade name JAGUAR HP200),
polyethylene glycol (such as that available from Dow Chemical Corporation
under the
trade name CARBOWAX 20M), hydrophobically modified hydroxyethylcellulose
(such as that available from the Ashland Inc. under the trade name NATROSOL
Plus),
and/or organophilic clays (for example, hectorite and/or bentonite clays such
as those
available from Elementis Specialties under the name BENTONE 27, 34 and 38 or
from
Eckart America under the trade name BENTOLITE L; and those described in U.S.
Patent No. 4,103,047 to Zaki, et at., which is herein incorporated by
reference). These
viscosity raisers or thickeners can typically be used at levels from about
0.5% to about
30% by weight, preferably from about 1% to about 5% by weight, more preferably
from about 1.5% to about 3.5% by weight, and further preferably from about 2%
to
about 3% by weight, of the composition.
[0095] Highly preferred materials of this class of thickeners and viscosity
control and
viscosity modifiers are those that do not cause any significant color change,
nor impart
any discoloration, such as graying or yellowing, to the matrices into which
they are
introduced, or to fabrics to which they may be applied, either during
treatment followed
by drying and/or curing, or after the drying and/or curing step followed by
normal
exposure to the elements, such as air, moisture or sunlight exposure.
PEARLIZING AND OPACIFYING AGENTS
[0096] Examples of pearlizing or opacifing agents that can be added to the
compositions disclosed herein include, but are not restricted to, glycol
distearate,
propylene glycol distearate, and glycol stearate. Some of these products are
available
from PMC Group under the KEMESTER trade name. While many such compounds
are commonly derived from petrochemicals sources at present, and are as such
not
preferred, it is envisioned that they could be derived from bio-based sources
at some
future point.
[0097] Highly preferred materials of this class of pearlizing and opacifying
agents are
those that do bind to treated fabrics, nor cause any significant color change
nor impart
any discoloration, such as whitening, graying or yellowing, to the matrices
into which
they are introduced, or to fabrics to which they may be applied, either during
treatment
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followed by drying and/or curing, or after the drying and/or curing step
followed by
normal exposure to the elements, such as air, moisture or sunlight exposure.
ANTIOXIDANTS AND SUNSCREEN MATERIALS
[0098] Examples of antioxidants that can be added to the compositions of
herein are
propyl gallate, available from Eastman Chemical Products, Inc. under the trade
names
TENOX PG and TENOX 5-1, and dibutylated hydroxytoluene, available from UOP
Inc. under the trade name SUSTANE BHT. Also preferred are antioxidants for
providing sun-fade protection for fabrics treated with composition of the
present
disclosure, such antioxidants being described in EP0773982, and incorporated
herein by
reference. Preferred antioxidants include 2-(N-methyl-N-cocoamino)ethy1-3',5'-
di-tert-
buty1-4'-hydroxybenzoate; 2-(N, N- dimethyl-amino)ethy1-3 ',5 '- di-tert-
buty1-4'-
hydroxyb enzo ate ; 2-(N- methyl-N- co co amino)ethy1-3 ',4',5 '-trihydroxyb
enzo ate ; and
mixtures thereof, more preferably 2-(N-methyl-N-cocoamino)ethy1-3',5'-di-tert-
buty1-4'-
hydroxy benzoate. Of these compounds, the butylated derivatives are preferred
in the
compositions of the present disclosure because tri-hydroxybenzoates have a
tendency to
discolor upon exposure to light. While many such compounds are commonly
derived
from petrochemicals sources, and are as such not preferred, it is envisioned
that they
could be derived from bio-based sources in the future. The antioxidant
compounds of
the present disclosure demonstrate light stability in the compositions of the
present
disclosure. Light stable as used herein means that the antioxidant compounds
disclosed
herein do not discolor when exposed to either sunlight or simulated sunlight
for
approximately 2 to 60 hours at a temperature of from about 25 C to about 45 C.
Antioxidant compounds and free radical scavengers can generally protect dyes
from
degradation by first preventing the generation of single oxygen and peroxy
radicals, and
thereafter terminating the degradation pathways. Not to be limited by theory,
a general
discussion of the mode of action for antioxidants and free radical scavengers
is
disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages
128
- 148, Third Edition (1978) which is incorporated herein by reference.
[0099] The formulations that are the subject of the instant disclosure may
comprise an
organic sunscreen. Suitable sunscreens can have UVA absorbing properties, UVB
absorbing properties, or a combination of both. The formulations newly
presented
herein may preferably comprise a UVA absorbing sunscreen actives that absorb
UV
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radiation having a wavelength from about 320 nm to about 400 nm. Suitable UVA
absorbing sunscreen actives include dibenzoylmethane derivatives, anthranilate
derivatives such as methylanthranilate and homomethyl-l-N-acetylanthranilate,
and
mixtures thereof. Examples of dibenzoylmethane sunscreen actives are described
in
U.S. Patent No. 4,387,089 to De Polo; and in Sunscreens: Development,
Evaluation,
and Regulatory Aspects edited by N.J. Lowe and N.A. Shaath, Marcel Dekker, Inc
(1990), which are incorporated herein by reference. The UVA absorbing
sunscreen
active is preferably present in an amount to provide broad-spectrum UVA
protection
either independently, or in combination with, other UV protective actives that
may be
present in the composition.
Preferred UVA sunscreen actives include
dibenzoylmethane sunscreen actives and their derivatives. They include, but
are not
limited to, those selected from 2-methyldibenzoylmethane, 4-
methyldibenzoylmethane,
4- isopropyldibenzoylmethane, 4-tert-
butyldibenzoylmethane, 2,4-
dimethyldibenzoylmethane, 2, 5 - dimethyldib enzoylmethane, 4,4'-
diisopropylbenzoylmethane,4-(1,1-dimethylethyl)-4'- methoxydibenzoylmethane, 2-
methyl-5 -isopropyl-4'-methoxydib enzoylmethane, 2-
methy1-5-tert-buty1-4'-
methoxydibenzoylmethane, 2,4-dimethy1-4'-methoxydibenzoylmethane, 2,6-dimethy1-
4'-tert-buty1-4'-methoxydibenzoylmethane, and mixtures thereof Preferred
dibenzoyl
sunscreen actives include those selected from 4-(1,1-dimethylethyl)-4'-
methoxydibenzoylmethane, 4-isopropyldibenzoylmethane, and mixtures thereof A
more preferred sunscreen active is 4-(1,1-dimethylethyl)-4'-
methoxydibenzoylmethane,
which is also known as butylethoxydibenzoylmethane or Avobenzone, is
commercially
available under the names of PARSOL 1789 from DSM Nutritional Products, LLC
and
EUSOLEX 9020 from EMD Chemicals Inc./Rona. The
sunscreen 4-
isopropyldibenzoylmethane, which is also known as isopropyldibenzoylmethane,
is
commercially available from EMD Chemicals Inc./Rona under the name of EUSOLEX
8020. The formulations of the instant disclosure may preferably further
comprise a
UVB sunscreen active that absorbs UV radiation having a wavelength of from
about
290 nm to about 320 nm. The compositions may preferably comprise an amount of
the
UVB sunscreen active that is safe and effective to provide UVB protection
either
independently, or in combination with, other UV protective actives that may be
present
in the compositions. The compositions preferably comprise from about 0.1% to
about
16%, more preferably from about 0.1% to about 12%, and further preferably from
about
0.5% to about 8% by weight, of UVB absorbing organic sunscreen. A wide variety
of
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UVB sunscreen actives are suitable for use herein. Non-limiting examples of
such
organic sunscreen actives are described in U.S. Patent No 5,087,372 to Toyomot
and
U.S. Patent Nos. 5,073,371 and 5,073,372 both to Turner, et at., which are
incorporated herein by reference. Preferred UVB sunscreen actives are selected
from 2-
ethylhexy1-2-cyano-3,3-diphenylacrylate (referred to as octocrylene), 2-phenyl-
benzimidazole-5-sulphonic acid (PBSA), cinnamates and their derivatives such
as 2-
ethylhexyl-p-methoxycinnamate and octyl-p-methoxycinnamate, TEA salicylate,
octyldimethyl PABA, camphor derivatives and their derivatives, and mixtures
thereof
Preferred organic sunscreen actives include 2-ethylhexy1-2-cyano-3,3-
diphenylacrylate
(commonly named octocrylene), 2-phenyl-benzimidazole-5-sulphonic acid (PBSA),
octyl-p-methoxycinnamate, and mixtures thereof Salt and acid neutralized forms
of the
acidic sunscreens are also useful.
[00100] An agent may also be added to any of the formulations described in the
present disclosure to stabilize the UVA sunscreen and to prevent it from photo-
degrading on exposure to ultraviolet radiation and thereby maintaining its UVA
protection efficacy. Wide ranges of compounds have been cited as providing
these
stabilizing properties and should be chosen to compliment both the UVA
sunscreen and
the composition as a whole. Suitable stabilizing agents include, but are not
limited to,
those described in U.S. Pat. No. 5,972,316 to Robinson; U.S. Pat. No.
5,968,485 to
Robinson; U.S. Pat. No. 5,935,556 to Tanner, et at.; and U.S. Pat. 5,827,508
Tanner, et
at., which are incorporated herein by reference. Preferred examples of
stabilizing
agents for use in the present formulations disclosure herein include 2-
ethylhexy1-2-
cyano-3,3-diphenylacrylate (referred to as octocrylene), ethy1-2-cyano-3,3-
diphenyl-
acrylate-2-ethylhexy1-3,3-diphenylacrylate, ethyl-3,3-bis (4-
methoxyphenyl)acrylate,
and mixtures thereof.
[00101] Highly preferred materials of this class of antioxidants and sunscreen
actives
are those that do not cause any significant color change, nor impart any
discoloration,
such as graying or yellowing, to the matrices into which they are introduced,
or to
fabrics to which they may be applied, either during treatment followed by
drying and/or
curing, or after the drying and/or curing step followed by normal exposure to
the
elements, such as air, moisture or sunlight exposure.
[00102] The formulations of the present disclosure may preferably deposit from
about
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0.1 mg/g fabric to about 5 mg/g fabric of the sun-fade actives to reduce the
sun fading
of the fabric. Repeated treatment of fabric with formulations presented
herein, may
result in higher deposition levels, which contributes even further to the sun-
fading
protection benefit.
DYE TRANSFER INHIBITORS AND DYE FIXATIVES
[00103] The formulations disclosed herein can comprise from about 0.001% to
about
20% by weight, preferably from about 0.5% preferably to about 10% by weight,
and
more preferably from about 1 % to about 5% by weight of one or more dye
transfer
inhibitors or dye fixing agents.
[00104] Compositions and formulations of the present disclosure can contain
ethoxylated amines, amphoterics, betaines, polymers such as
polyvinylpyrrolidone, and
other ingredients that inhibit dye transfer. While many such compounds are
commonly
derived from petrochemicals sources, and are as such not preferred, it is
envisioned that
they could be derived from bio-based sources. Optional dye fixing agents can
be
cationic, and based on quaternized nitrogen compounds or on nitrogen compounds
having a strong cationic charge that is formed in situ under the conditions of
usage.
Cationic fixatives are available under various trade names from several
suppliers.
Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and
CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50
(February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz;
SANDOFIX TPS, ex Sandoz, is a preferred dye fixative for use herein.
Additional non-
limiting examples include SANDOFIX SWE (a cationic resinous compound) from
Sandoz, REWIN SRF, REWIN SRF-0 and REWIN DWR Crochet-Beitlich GMBH;
Tinofix ECO, Tinofix FRD and Solvent from Ciba-Geigy. Other cationic dye
fixing
agents are described in "After treatments for Improving the Fastness of Dyes
on Textile
Fibres", Christopher C. Cook, Rev. Prog. Coloration, Vol. XH, (1982). Dye
fixing
agents suitable for use in the formulations of the instant disclosure include
ammonium
compounds such as fatty acid-diamine condensates, inter alia, the
hydrochloride,
acetate, methosulphate and benzyl hydrochloride salts of diamine esters. Non-
limiting
examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamine
methosulphate, and monostearylethylene diaminotrimethylammonium methosulphate.
In addition, the N-oxides of tertiary amines; derivatives of polymeric
alkyldiamines,
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polyamine-cyanuric chloride condensates; and aminated glycerol dichlorohydrins
are
suitable for use as dye fixatives in the compositions of the presented herein.
[00105] Highly preferred materials of this class of dye transfer inhibitors
and dye
fixatives are those that do not cause any significant color change, nor impart
any
discoloration, such as graying or yellowing, to the matrices into which they
are
introduced, or to fabrics to which they may be applied, either during
treatment followed
by drying and/or curing, or after the drying and/or curing step followed by
normal
exposure to the elements, such as air, moisture or sunlight exposure.
CHLORINE SCAVENGERS
[00106] The compositions of the present disclosure may optionally comprise
from
about 0.01%, preferably from about 0.02%, more preferably from about 0.25% to
about
15%, further preferably to about 10%, and yet more preferably to about 5% of a
chlorine scavenger. In cases wherein the cation portion and the anion portion
of the
non-polymeric scavenger each react with chlorine, the amount of scavenger can
be
adjusted to fit the needs of the formulator. While many such compounds are
commonly
derived from petrochemicals sources, and are as such not preferred, it is
envisioned that
they could be derived from bio-based sources. Suitable chlorine scavengers
include
ammonium salts having the formula: [(R)3R'N]X wherein each R is independently
hydrogen, C1-C4 alkyl, C1-C4 substituted alkyl, and mixtures thereof;
preferably R is
hydrogen or methyl, more preferably hydrogen; R' is hydrogen C1-C10 alkyl, C1-
C10
substituted alkyl, and mixtures thereof. Preferably R is hydrogen and X is a
compatible
anion. Non-limiting examples include chloride, bromide, citrate, and sulfate;
preferably
X is chloride. Non-limiting examples of preferred chlorine scavengers include
ammonium chloride, ammonium sulfate, and mixtures thereof, preferably ammonium
chloride. Other chlorine scavengers include reducing agents such as
thiosulfate.
[00107] Highly preferred materials of this class of chlorine scavengers are
those that
do not cause any significant color change, nor impart any discoloration, such
as graying
or yellowing, to the matrices into which they are introduced, or to fabrics to
which they
may be applied, either during treatment followed by drying and/or curing, or
after the
drying and/or curing step followed by normal exposure to the elements, such as
air,
moisture or sunlight exposure.
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WETTING AGENTS
[00108] The formulations and compositions disclosed herein may contain as an
optional ingredient from about 0.005% to about 3.0% by weight, and more
preferably
from about 0.03% to 1.0% by weight of a wetting agent. Such wetting agents may
be
selected from polyhydroxy compounds. While many such compounds are commonly
derived from petrochemicals sources, and are as such not preferred, it is
envisioned that
they could be derived from bio-based sources. Examples of water soluble
polyhydroxy
compounds that can be used as wetting agents in the compositions disclosed
herein
include glycerol, polyglycerols having a weight-average molecular weight from
about
150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols
having a
weight-average molecular weight from about 200 to about 4000, preferably from
about
200 to about 1000, and more preferably from about 200 to about 600.
Polyoxyethylene
glycols having a weight-average molecular weight from about 200 to about 600
are
especially preferred. Mixtures of the above-described polyhydroxy compounds
may
also be used. A particularly preferred polyhydroxy compound is polyoxyethylene
glycol having a weight-average molecular weight of about 400, available from
Dow
Chemical Corporation under the trade name PEG-400.
[00109] Highly preferred materials of this class of wetting agents are those
that do not
cause any significant color change, nor impart any discoloration, such as
graying or
yellowing, to the matrices into which they are introduced, or to fabrics to
which they
may be applied, either during treatment followed by drying and/or curing, or
after the
drying and/or curing step followed by normal exposure to the elements, such as
air,
moisture or sunlight exposure.
ELECTROLYTES
[00110] Suitable inorganic salts for use as an optional electrolyte in the
present
compositions include MgI2, MgBr2, MgC12, Mg(NO3)2, Mg3(PO4)2, Mg2P207, Mg504,
magnesium silicate, NaI, NaBr, NaC1, NaF, Na3PO4, Na2503, Na2504, NaN035
Na4P205, sodium silicate, sodium metasilicate, sodium tetrachloroaluminate,
sodium
tripolyphosphate (STPP), Na25307, sodium zirconate, CaF2, CaC12, CaBr2, CaI2,
Ca504, Ca(NO3)2, KI, KBr, KC1, KF, KNO3, KI03, K2504, K2503, K3PO4, K4(P207),
potassium pyrosulfate, potassium pyrosulfite, LiI, LiBr, LiC1, LiF, LiNO3,
A1F3, A1C13,
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A1Br3, A113, Al2(SO4)3, Al(PO4), Al(NO3)3, aluminum silicate; including
hydrates of
these salts and including combinations of these salts or salts with mixed
cations e.g.
potassium aluminum A1K(SO4)2 and salts with mixed anions, e.g. potassium
tetrachloroaluminate and sodium tetrafluoroaluminate. Salts incorporating
cations from
groups Illa, IVa, Va, Vla, VIIa, VIII, Ib, and IIb on the periodic chart with
atomic
numbers greater than are also useful in reducing dilution viscosity but less
preferred due
to their tendency to change oxidation states and thus they can adversely
affect the odor
or color of the formulation or lower weight efficiency. Salts with cations
from group Ia
or IIa with atomic numbers greater than 20 as well as salts with cations from
the
lanthanide or actinide series are useful in reducing dilution viscosity, but
less preferred
due to lower weight efficiency or toxicity. Mixtures of above salts are also
useful.
[00111] Also preferred are quaternary ammonium salts, quaternary alkyl
ammonium
salts, quaternary dialkyl ammonium salts, quaternary trialkyl ammonium salts
and
quaternary tetraalkyl ammonium salts wherein the alkyl substituent comprises a
methyl,
ethyl, propyl, butyl or higher C5-C12 linear alkane radical, or combinations
thereof
Organic salts useful with the compositions presented herein include magnesium,
sodium, lithium, potassium, zinc, and aluminum salts of carboxylic acids,
including
formates, acetates, proprionates, pelargonates, citrates, gluconates,
lactates, and
aromatic acids such as benzoates, phenolates, and substituted benzoates or
phenolates,
such as phenolates, salicylates, polyaromatic acids, terephthalates, and
polyacids e.g.
oxylates, adipates, succinates, benzenedicarboxylates and
benzenetricarboxylates.
Other useful organic salts include carbonates and/or hydrogen carbonate (HCO3-
1)
when the pH is targeted to be alkaline, alkyl and aromatic sulfates and
sulfonates, e.g.,
sodium methyl sulfate, benzene sulfonates and derivatives such as xylene
sulfonate, and
amino acids.
[00112] Electrolytes can comprise mixed salts of the above single salts, salts
neutralized with mixed cations such as potassium/sodium tartrate, partially
neutralized
salts such as sodium hydrogen tartrate or potassium hydrogen phthalate, and
salts
comprising one cation with mixed anions.
[00113] Highly preferred mixed salt materials comprising inorganic and organic
electrolytes are those that do not cause any significant color change, nor
impart any
discoloration, such as graying or yellowing, to the matrices into which they
are
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introduced, or to fabrics to which they may be applied, either during
treatment followed
by drying and/or curing, or after a drying and/or curing step that may be
followed by
normal exposure to air, moisture or sunlight.
[00114] Generally, inorganic electrolytes are preferred over organic
electrolytes for
better weight efficiency and lower costs. Mixtures of inorganic and organic
salts can be
used. Typical levels of electrolyte in the present compositions can be less
than about
10% by weight, preferably from about 0.5% to about 5% by weight, more
preferably
from about 0.75% to about 2.5% by weight, and further preferably from about 1
% to
about 2% by weight of the inventive composition.
ENZYMES
[00115] Additional desirable adjuncts may be enzymes (although it may be
preferred
to also include an enzyme stabilizer), including, but not limited to
hydrolases,
hydroxylases, cellulases, peroxidases, laccases, mannases, amylases, lipases
and
proteases. Proteases are one especially preferred class of enzymes. Typical
examples
of proteases include Maxatase and Maxacal from Genencor International,
Alcalase,
Savinase, and Esperase, all available from Novozymes North America, Inc. See
also
U.S. Pat. No. 4,511,490 to Stanislowski, et at., incorporated herein by
reference.
Further suitable enzymes are amylases, which are carbohydrate-hydrolyzing
enzymes.
It may also be preferred to include mixtures of amylases and proteases.
Suitable
amylases include Termamyl from Novozymes, North America Inc, and Maxamyl from
Genencor International Co. Still other suitable enzymes are cellulases, such
as those
described in U.S. Pat. No. 4,479,881 to Tai; U.S. Pat. No. 4,443,355 to
Murata, et at.;
U.S. Pat. No. 4,435,307 to Barbesgaard, et at.; and U.S. Pat. No. 3,983,082 to
Ohya, et
at., incorporated herein by reference. Yet other suitable enzymes are lipases,
such as
those described in U.S. Pat. No. 3,950,277 to Silver; U.S. Pat. No. 4,707,291
to Thorn,
et at.; U.S. Pat. Nos. 5,296,161 and 5,030,240 both to Wiersema, et at.; and
U.S. Pat.
No. 5,108,457 to Poulose, et at., incorporated herein by reference. The
hydrolytic
enzyme may be present in an amount of about 0.01-5%, more preferably about
0.01-
3%, and further preferably about 0.1-2% by weight of the detergent. Mixtures
of any of
the foregoing hydrolases are desirable, especially protease/amylase blends.
[00116] Highly preferred materials of this class of enzymes are those that do
not cause
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any significant residual odor or color change, nor impart any discoloration,
such as
graying or yellowing, to the matrices into which they are introduced, or to
fabrics to
which they may be applied, either during treatment followed by drying and/or
curing, or
after the drying and/or curing step followed by normal exposure to the
elements, such
as air, moisture or sunlight exposure.
BLEACHING AGENTS
[00117] The compositions disclosed herein may optionally comprise from about
0.01
%, preferably from about 0.02% by weight, more preferably from about 0.25% to
about
15% by weight, further preferably to about 10% by weight, and yet more
preferably to
about 5% by weight of a bleaching agent. Suitable bleaching agents include
peroxygen
and peroxide-releasing compounds. Peroxygen compounds include alkali metal
salts of
percarbonate, perborate and peroxymonosulfate. Peroxide compounds, including
hydrogen peroxide and compounds generating hydrogen peroxide in solution,
peroxyacids and precursors to peroxyacids and peroxyimidic acids, and metal
based
oxidants are also suitable. Suitable bleaching agents include preformed
peracids and
organic peroxides, including alkonyl and acyl peroxides such as tertiary butyl
peroxide
and benzoyl peroxide, and related alkonyl and acyl peroxide and superoxide
derivatives
of alkyls and arenes. Additionally, an appropriate bleach activator for the
active
oxygen source or peroxide may be present, such those found in Arbogast, et
at., U.S.
Pat. Nos. 5,739,327 and 5,741,437; Alvarez, et at.; U.S. Pat. No. 5,814,242,
Deline, et
at.; U.S. Pat. No. 5,877,315; and U.S. Pat. No. 5,888,419 to Casella, et at.,
which relate
to cyanonitrile derivatives; U.S. Pat. Nos. 4,959,187 and 4,778,816 to Fong,
et at.; U.S.
Pat. Nos. 5,112,514 and 5,002,691 to Bolkan, et al., and U.S. Pat. No.
5,269,962 to and
Brodbeck, et at., which relate to alkanoyloxyacetyl derivatives; and U.S. Pat.
Nos.
5,234,616, 5,130,045 and 5,130,044 to Mitchell, et at., all of which relate to
alkanoyloxyphenyl sulfonates; all of which are incorporated herein by
reference.
[00118] Highly preferred materials of this class of bleaching agents are those
that do
not cause any significant fabric damage or color change, nor impart any
discoloration,
such as graying or yellowing, to the matrices into which they are introduced,
or to
fabrics to which they may be applied, either during treatment followed by
drying and/or
curing, or after the drying and/or curing step followed by normal exposure to
the
elements, such as air, moisture or sunlight exposure.
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BRIGHTENERS
[00119] Optical brighteners, also referred to as fluorescent whitening agents
or FWAs,
have on been been used to impart whitening to fabrics during the laundering
process.
These fluorescent materials act by absorbing ultraviolet wavelength of light
and
emitting visible light, generally in the color blue wavelength ranges. The
FWAs settle
out or deposit onto fabrics during the wash cycle. These include the stilbene.
Stvrene,
and naphthalene derivatives, which upon being impinged by ultraviolet light,
emit or
fluoresce light in the visible wavelength. While many such compounds are
commonly
derived from petrochemicals s.'ources., and are as such not prekrred, it is
envisioned that
they could be derived from bio-based sources. It is also envisioned that by
being dyes,
there are individuals with MCS that may not be able tolerate their presence,
and as such
natural ingredients such as pigments that possess the ability to fluoresce may
be
preferable..
[00120] FW.As or brighteners are usefill for improving the appearance of
.fabrics,
which have become dingy through repeated scilings and washings. Due to the
cationic.
nature of the composition, it is preferred that the FWAs not be explicitly
anionic but
rather either nonionic; cationic; amphoteric; or neutralized, ion-paired
moieties of
anionic FWAs as described in Petrin, et al, U.S. Pat. No. 5,057,236. Preferred
anionic
FWAs for ion-pairing according to Petrin, et aL, '236 are Blankophor BBH, RKH
and
BHC, from Blankophor GmbH & Co, KG; and Tinopal 5BMX-C, CBS-X and RBS,
from BASF Corporation. Fluorescent whiteners most currently used in common
laundry compositions generally fall into a category referred to in the art as
diaminostilbene disulfonic acid-cyanuric chloride brighteners or DASC-
brighteners.
These compounds have the following general formula (T):
HNõ _EN CH=CH
Tr Y
SCh NA $01;INI
R"
(I)
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[00121] Examples of such DASC fluorescent whiteners include those sold by BASF
Corporation under the trade name "Tinopal", which are substituted stilbene
2,2'-
disulfonic acid products, e.g., disodium 4,4'-bis-((4-anilino-6-morpholino-
1,3,5-triazin-
2-yl)amino)stilbene-2,2'-disulfonate (sold as Tinopal AMS); disodium 4,4'-bis-
((4-
anilino-6-(N-2-hydroxyethyl-N -methyl amino)-1,3,5-triazin-2-yl)amino)stilbene-
2,2'-
disulfonate (sold as Tinopal 5BM); disodium 4,4'-bis-((4-anilino-6-(bis-(2-
hydroxyethyl)amino)-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (sold
as Tinopal
UNPA). Another example sold by Bayer Corporation is disodium 4,4'-bis-((4-
anilino-
6-methylamino)-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (sold as
Phorwite
HRS).
[00122] Examples of suitable FWAs can be found in U.K. Patent Nos. 1,298,577;
2,076,011; 2,026,054; 2,026,566; 1,393,042; and U.S. Pat. No. 3,951,960 to
Heath, et
at., U.S. Pat. No. 4,298,290 to Barnes, et at., U.S. Pat. No. 3,993,659 to
Meyer, U.S.
Pat. No. 3,980,713 to Matsunaga, et at., and U.S. Pat. No. 3,627,758 to Weber,
et at.,
incorporated herein by reference. See also, U.S. Pat. No. 4,900,468 to
Mitchell, et at.,
column 5, line 66 to column 6, line 27, incorporated herein by reference.
[00123] As stated above, most preferred are cationic, nonionic, and amphoteric
FWAs,
such as those cited in U.S. Pat. Nos. 4,433,975, 4,432,886, 4,384,121, all to
Meyer and
U.S. Pat. No. 4,263,431 to Weber, et at., and incorporated herein by
reference. Further
examples of suitable FWAs are described in McCutcheon's Vol. 2: Functional
Materials, North American Ed., McCutcheon Division, MC Publishing Co., 1995,
and
Encyclopedia of Chemical Technology, 11th volume, John Wiley & Sons, 1994,
both
of which are incorporated herein by reference. Other examples of fluorescent
brightening materials suitable for use with the formulations presented herein
may be
found in U.S. Pat. No. 6,251,303 to Bawendi, et at.; U.S. Pat. No. 6,127,549
to Hao, et
at.; U.S. Pat. No. 6,133,215 to Zeiger, et at.; U.S. Pat. No. 6,117,189 to
Reinehr, et at.;
U.S. Pat. No. 6,120,704 to Martini; and U.S. Pat. No. 6,162,869 to Sharma, et
at.,
incorporated herein by reference.
[00124] Highly preferred materials of this class of brighteners are those that
do not
cause any significant color change, nor impart any discoloration, such as
graying or
yellowing, to the fabrics to which they are applied, either during treatment
followed by
drying and/or curing, or after the drying and/or curing step followed by
normal
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exposure to the elements, such as air, moisture or sunlight exposure.
EXAMPLES and STUDIES
[00125] Using the novel assessment protocols defined herein, additional
cleaning
product formulation guidelines can be developed and promulgated and made
available
for cleaning product manufacturers. Following the processes disclosed and
described
herein, a series of products were formulated and tested against commercially
available
brands in each category, using standard industrial assay techniques. The
approach
taken to preparing the formu¨lations described herein is believed to be unique
in that it
links product safety, environmental stewardship and product performance.
Customers,
therefore, do not have to sacrifice product performance for safety and/or
sustainability.
STUDY 1: EFFECT OF PETROLEUM-BASED INGREDIENTS
[00126] As surfactants make up the majority of cleaning product formulations,
it is
highly important that their contributions be accounted for in individuals that
experience
MCS. In has been postulated that avoiding petrochemicals may be a first-tier
approach
in making safer cleaning products. Disappointingly, there are numerous
products on
the market that claim to be petrochemical-free, and yet are not acceptable to
some who
experience MCS. As such, a number of raw materials from typical source
manufacturers were evaluated in the course of the instant work for their
actual bio-
renewable carbon. Disappointingly, a number were found to contain hybrid
surfactants
of significant petrochemical content. The results are shown below in TABLE 1.
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TABLE 1: Surfactants and Percent Modern Carbon
Percent Modern
Surfactant Carbon (pMC)a
Sodium alkylbenzene sulfonate
0%
Lauramine oxide
0 A
Sodium lauryl sulfate
0%
C12-14 alcohol ethoxylate (7E0)
48%
Cocoamidopropyl betaine
64%
Cocoamidopropyl amine oxide
72%
Cocamide DEA
75%
Sodium coco ether (2E0) sulfate
75%
Cocodimethyl amine oxide
86%
C10-16 alkyl polyglucoside
100%
C8_10 alkyl polyglucoside
100%
Sodium coco sulfate
100 A
Sodium octyl sulfate (from bio-basis)
100%
Note to TABLE 1,
a Measure of the percent of modern or bio-based carbon in an ingredient or
composition, as estimated from evaluation of feedstocks of component carbons,
or
determined by ASTM D6866-05.
[00127] As may be readily observed, many surfactants possess a significant
portion,
that is 25% or more by weight, of petrochemical contribution. In other words,
despite
being positioned as "natural" surfactants, their Biorenewable Carbon Index
(and thus
their biorenewable carbon content) is less than 80% by weight. As such, it has
been
found that surfactants that are preferred for use with the compositions
described herein
are those having a Biorenewable Carbon Index of at least 80%, that is, with a
BCI of?
80%.
STUDY 2: EFFECT OF TRACE CONTAMINANTS
[00128] In a second study, it was surprisingly found that certain surfactants
that had a
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very high Biorenewable Carbon Index, even as high as 100%, could have adverse
effects on certain individuals with MCS. Without being bound by theory, it is
believed
that this phenomenon is due to the non-exact nature of the BCI or RCI
measurement (
3% by weight) vis-à-vis the low amounts of contaminants, perhaps much less
than 1%
by weight, that are present in certain ingredients. To test this hypothesis, a
number of
chemically sensitive individuals assessed four types of alkyl polyglucosides,
or APGs,
from three manufacturers, all of which have an apparent BCl/RCI of 100%. Each
of the
APG candidates was rated on a 3-point index:
Acceptable, Marginal, and
Unacceptable. The Marginal and Unacceptable candidates were then analyzed for
the
presence of trace contaminants. Surprisingly, those candidates all contained
detectable
amounts of phenyl derivatives (toluene, acetophenone), apparently owing to the
nature
of the catalyst used during manufacture and the fact that it was perhaps not
stripped out
prior to distribution. Candidates that were determined to be Acceptable did
not have
such phenyl residue. The results are shown in TABLE 2 below.
TABLE 2: Acceptability of Candidate Alkyl Polyglucosides
Percent Modern Acceptability
Surfactant Carbon (pMC)a Rating
Commercial APG Product A 100% Unacceptable
Commercial APG Product B 100% Unacceptable
Commercial APG Product C 100% Marginal
Commercial APG Product D 100% Acceptable
Note to TABLE 2.
a Measure of the percent of modern or bio-based carbon in an ingredient or
composition, as estimated from evaluation of feedstocks of component carbons,
or
determined by ASTM D6866-05.
STUDY 3: EFFECT OF CARBON CHAIN LENGTH
[00129] In the manufacture of surfactants, it can be assumed that a small
amount,
albeit a significant one, of feedstock remains unreacted. This amount can
often be less
than 1% by weight, but to individuals who are sensitive to such species, the
impact can
be significant. Often, this can result in an olfactory response as lower-chain
alcohols
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are quite odiferous, but to individuals with MCS, the impact is more
significant.
Without being bound by theory, it is believed that chemicals¨especially
surfactant
residues¨that have a chain length of eight carbon atoms or less may react with
proteins
to form protein-hapten complexes that trigger an immunogenic response.
Chemicals
that have a carbon chain length greater than eight carbon atoms may be
insufficiently
reactive with proteins to form protein-hapten complexes. Alternatively, it is
postulated
that any protein-hapten conjugates having greater than eight-carbon atom chain
lengths
that may form, are present in concentrations that are lower than a threshold
level needed
to trigger an immunogenic response. As such, a number of raw materials were
evaluated by a number of chemically sensitive individuals for acceptability
using the
same scale as above. The results are presented in TABLE 3 below.
TABLE 3: Effect of Carbon Chain Length of Surfactant Feedstock
Percent Modern Average Carbon Acceptability
Surfactant Carbon (pMC)a Chain Length Rating
Sodium octyl sulfate (from 100% 8 Unacceptable
bio-basis)
C8_10 alkyl polyglucoside 100% 9 Unacceptable
C10-16 alkyl polyglucoside 100% 13 Acceptable-
Unacceptable*
Sodium coco sulfate 100% 12 Acceptable
Notes to TABLE 3
a Measure of the percent of modern or bio-based carbon in an ingredient or
composition, as estimated from evaluation of feedstocks of component carbons,
or
determined by ASTM D6866-05.
* Response received was dependent upon the source of alkyl polyglucoside,
which in
turn was found to depend on the level of trace contaminants, as discussed
above.
STUDY 4: VOLATILE ORGANICS
[00130] As mentioned above, in an analysis of 37 commercial products,
Steinemann
(2015) found emissions of 156 different VOCs, with an average of 15 VOCs per
product. Of these 156 VOCs, 42 VOCs were classified as toxic or hazardous
under
U.S. federal laws, and each product emitted at least one of these chemicals.
Despite
inferences, the emissions of hazardous air pollutants (HAPs) from so-called
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fragranced products were not significantly different from non-green labeled
fragranced
products.
[00131] Without being bound to theory, the inventors believe that minimizing
or
eliminating sources of VOC can significantly reduce contaminants that may
introduce
hazardous air pollutants into consumer cleaning compositions. For example, the
vapor
pressure of ethanol at room temperature is about 45 mm Hg at 20 C, while that
of 1,3-
propanediol is 0.08 mm Hg, and that of glycerine is about 0.00018 mm Hg.
Substitution of ethanol with other low-volatility solvents can therefore not
only lower
the overall vapor pressure of a product, and but may reduce the likelihood of
untoward
effects on persons that suffer from MCS.
EXAMPLE 1: Effect of Carbon Chain Length of Surfactant Feedstock
[00132] A laundry detergent was formulated in accordance with the guidelines
presented above. Accordingly, 15.0 parts of alkyl polyglucoside (Triton CG-
600, 50%
active from Dow Chemical Company) were added to 63.1 parts deionized water
with
mixing, followed by 13.0 parts of sodium coco sulfate (Stepanol WA-Extra, 29%
active
from Stepan Company), 2.0 parts glycerine (Pricerene 9091 from Croda), 2.0
parts
boric acid, 2.0 parts oleic acid (Acme-Hardesty Co), 1.0 part sodium
gluconate, 1 part
sodium hydroxide, 0.1 part protease (Novozymes), 0.1 part calcium chloride,
0.1 part
sodium chloride, 0.05 parts amylase (Novozymes), and 0.05 parts preservative
(Neo lone M10, 10% active).
[00133] A portion of the resulting formulations, designated Sample F in TABLE
4
below, was then submitted for evaluation and analysis versus a commercially
available,
safety-positioned, unfragranced liquid detergent product, labeled Sample E in
TABLE
4 below. The samples were analyzed via two different methods: U.S. EPA
Compendium Method TO-15, "Determination Of Volatile Organic Compounds (VOCs)
In Air Collected In Specially-Prepared Canisters And Analyzed By Gas
Chromatography/Mass Spectrometry (GC/MS)," EPA, 1999, and U.S. EPA Method
TO-11A, "Determination of Formaldehyde in Ambient Air Using Adsorbent
Cartridge
Followed by High Performance Liquid Chromatography (HPLC)," EPA, 1999. The
second of the two analyses is specific for aldehydes such as formaldehyde and
acetaldehyde.
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[00134] TABLE 4 summarizes findings for the two laundry detergent samples.
Note
that reported analyte values were above a threshold of 1000 iAg/m3, thereby
ensuring
with some confidence that they are emitted from the products:
[00135] TABLE 4: HEADSPACE Analysis of Samples by EPA Method TO-15
Sample E Sample F
Compound CAS Number Liquid Laundry Liquid Laundry
Detergent Detergent
(>1000 gji /m3)a,b (> 10001.tg/m3)a'
3,5-Dimethyl-1-hexene 7423-69-0 Y N
Cyclotetradecane 295-17-0 Y N
2-Phenoxyethanol 122-99-6 Y N
Methyl octanoate 111-11-5 Y N
Trichloromethane 67-66-3 Y N
(chloroform)*
11-Bromoundecanoic acid 2834-05-1 Y N
Methyl undecanoate 1731-86-8 Y N
2-Propenoic acid, 1,7,7-
trimethyl-bicyclo[2.2.1]-
5888-33-5 Y Y
hept-2-y1 ester
Isobutyl nonyl oxalate Unknown Y Y
1-Undecanol 112-42-5 N Y
2-Methyl-cyclopentanol 24070-77-7 N Y
Pentadecane 629-62-9 N Y
Notes to TABLE 4:
* Known hazardous substance, cancer risk; bold = classified as toxic or
hazardous under
U.S. federal law.
aAbbreviations are used to indicate presence or absence of material in head
space: Y =
Yes;_N = No.
b
Sample E: Commercially available liquid laundry detergent
c Sample F: Laundry detergent formulated according to the instant disclosure,
described
in EXAMPLE 1, above.
[00136] The analytes were compared against eight Federal registers of
potentially
hazardous VOCs, per the study by Steinemann (2015). One analyte found in the
commercial product, chloroform, is present on all registries; this is in
agreement with
the study Steinemann (2015), wherein every product analyzed had at least one
such
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potentially hazardous VOC. Remarkably, chloroform was found to be absent in
the
liquid laundry detergent product prepared according to the instant
specification. In fact,
the product prepared according to the methods described herein did not have
one
chemical that appears on any of the registries of hazardous chemicals present
at a level
above 1000 [tg/m3. The results are summarized in Table 5 below.
TABLE 5: Headspace Analysis of Samples via EPA Method TO-15
Id40
Compound CAS Number
ori g 4
C
3,5-Dimethyl-1-hexene 7423-69-0 -- --
Cyclotetradecane 295-17-0 --
2-Phenoxyethanol 122-99-6 -- --
Methyl octanoate 111-11-5 --
Trichloromethane
67-66-3
(chloroform) *
11-Bromoundecanoic acid 2834-05-1 -- --
Methyl undecanoate 1731-86-8 -- --
2-Propenoic acid, 1,7,7-
trimethyl-
5888-33-5 --
bicyclo[2.2.1]hept-2-y1
ester
Isobutyl nonyl oxalate Unknown -- --
1-Undecanol 112-42-5 --
2-Methyl-cyclopentanol 24070-77-7 -- --
Pentadecane 629-62-9 -- --
Notes to TABLE 5
* Known hazardous substance, cancer risk; bold = classified as toxic or
hazardous
under U.S. federal law.
CAA-TFSa: Clean Air Act¨Toxic and Flammable Substances for Accidental
Release Prevention
CAA-HAPb: Clean Air Act¨Hazardous Air Pollutant
CERCLAc: Comprehensive Environmental Response, Compensation, and
Liability
Act¨Hazardous Substance
CWAd: Clean Water Act¨Priority Pollutant
EPCRAe: The Emergency Planning & Community Right to Know Act¨Toxic
Release Inventory Chemical
FIFRAf: Federal Insecticide, Fungicide, and Rodenticide Act¨Registered
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Pesticide
OSHAg: Occupational Safety and Health Act¨Air Contaminants
RCRAh: Resource Conservation and Recovery Act¨Hazardous Constituents
[00137] The two specimens, Samples E and F were then analyzed via U.S. EPA
Method TO-11A, which is specific for aldehydes such as formaldehyde and
acetaldehyde. Sample F, a composition prepared in accordance with the methods
described in the instant specification, had significantly less acetaldehyde
than
commercial product Sample B, and is absent of formaldehyde down to the
detection
limit. Results are summarized below in TABLE 6.
TABLE 6: Headspace Analysis of Samples via EPA Method TO-11A
Formaldehyde Acetaldehyde
parts per parts per
Sample billion (by ug/m3
billion (by ug/m3
volume) volume)
Commercial Liquid Detergent 18.8 23.09 7.45 13.42
(Sample E)a
Formulated Liquid Detergent (below (below 3.07 5.53
(Sample F)h detection detection
limit) limit)
Notes to TABLE 6
a Sample E: Commercially available liquid laundry detergent
b
Sample F: Laundry detergent formulated according to the instant disclosure,
described in EXAMPLE 1, above.
STUDY 5: REPRESENTATIVE FORMULATIONS
[00138] Based on the assessment criteria described herein, several cleaning
formulas
were generated in accordance with the methods described herein and found to be
highly
effective at cleaning. And yet, when evaluated by a panel of five individuals
that have
MCS, the formulas were found to be totally acceptable for use without
deleterious
physical effects. Representative formulas prepared and tested according to the
instant
specification are listed in TABLE 7 and results summarized in TABLE 8 below.
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[00139] TABLE 7: Representative Cleaning Formulas
Ingredient Sample F Sample G Sample H Sample I
Liquid Liquid All-Purpose General
laundry dishwashing cleaner bathroom
detergent detergent cleaner
Sodium coco sulfate, 29% 13.0% 45.0% -- --
active
Alkyl polyglucoside, 50% 15.0% 9.0% 3.0% 5.0%
active
Cocoamine oxide -- 12.0% -- --
Glycerine 2.5% 3.5% 1.5% --
Boric acid 2.0% -- --
Citric acid -- 0.25% -- 4.0%
Oleic acid 2.0% -- -- --
Sodium gluconate 1.0% -- -- --
Sodium hydroxide 1.0% -- -- --
Potassium citrate -- -- 0.5% --
Protease 0.1% -- -- --
Calcium chloride 0.1% -- -- --
Sodium chloride 0.1% -- -- --
Amylase 0.05% -- -- --
Preservative, 10% active 0.05% 0.05% 0.05% 0.05%
Water q.s. q.s. q.s. q.s.
Percent Modern Carbon 99.97% 97.96% 99.86% 99.92%
(pMC)a
Note to TABLE 7,
a Measure of the percent of modern or bio-based carbon in an ingredient or
composition, as estimated from evaluation of feedstocks of component carbons,
or
determined by ASTM D6866-05.
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TABLE 8: Use Results of Representative Cleaning Formulas
Sample F Sample G Sample H Sample I
Liquid Liquid All-Purpose General
Product laundry dishwashing cleaner bathroom
detergent detergent cleaner
Acceptable Yes Yes Yes Yes
Performance (versus
commercial products)
Acceptable Use Yes Yes Yes Yes
(without ill effects)?
[00140] In one aspect, a liquid laundry detergent that may be prepared
according to the
information presented herein and be well suited for use by chemically-
sensitive
individuals, contains: 1) 30% sodium coco sulfate, 29% active; 2) 15% alkyl
polyglucoside, 50% active; 3) 2.5% glycerine; 4) 2.0% boric acid; 5) 2.0%
oleic acid;
6) 1.0% sodium gluconate; 7) 1.0% sodium hydroxide; 8) 0.1% protease; 9) 0.1%
calcium chloride; 10) 0.1% sodium chloride; 11) 0.05% amylase; 12) 0.05%
preservative, 10% active; and the balance water, where all percents are
understood to
refer to weight percent. Furthermore, a liquid laundry detergent that may be
prepared
according to the methods presented herein and consistent with the above
composition
may be found to have a percent modern carbon (pMC) of approximately 99.97%.
[00141] In another aspect, a dishwashing detergent that may be prepared
according to
the information presented herein and be well suited for use especially by
chemically-
sensitized individuals, contains: 1) 45.0% sodium coco sulfate, 29% active; 2)
9.0%
alkyl polyglucoside, 50% active; 3) 12% cocamine oxide, 30%; 4) 3.5%
glycerine; 5)
0.25% citric acid; 6) 0.05% preservative, 10% active; and the balance water,
where all
percents are understood to refer to weight percent. Furthermore, a dishwashing
detergent that may be prepared according to the methods presented herein and
consistent with the above composition may be found to have a percent modern
carbon
(pMC) of approximately 97.96%
[00142] In yet another aspect, an all-purpose cleaner that may be prepared
according to
the information presented herein and be found to be well suited for use
especially by
chemically-sensitized individuals, contains: 1) 3.0% alkyl polyglucoside, 50%
active;
2) 1.5% glycerine; 3) 0.5% potassium citrate, 4) 0.05% preservative, 10%
active; and
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the balance water, where all percents are understood to refer to weight
percent.
Furthermore, an all-purpose cleaner that may be prepared according to the
methods
presented herein and consistent with the above composition may be found to
have a
percent modern carbon (pMC) of approximately 99.86%.
[00143] In still another aspect, a general bathroom cleaner that may be
prepared
according to the information presented herein and be found to be well suited
for use
especially by chemically-sensitized individuals, contains: 1) 5.0% alkyl
polyglucoside,
50% active; 2) 4% citric acid; 3) 0.05% preservative, 10% active; and the
balance
water, where all percents are understood to refer to weight percent.
Furthermore, a
general bathroom cleaner that may be prepared according to the methods
presented
herein and consistent with the above composition may be found to have a
percent
modern carbon (pMC) of approximately 99.92%.
[00144] It is to be noted that the foregoing samples and examples demonstrate
the
manner in which novel formulations and methods disclosed herein can be used to
provide cleaning products that exhibit enhanced hypoallergenicity and can be
generated
from sustainable sources without sacrificing cleaning efficacy. The foregoing
samples
and examples demonstrate the manner in which the compositions and methods
described herein provide screening for many recognized deleterious health
effects
without effectively sacrificing cleaning efficacy for the sake of
sustainability of
materials.
[00145] The instant disclosure presents information that has been described in
detail
herein with reference to specific embodiments, methods and examples. However,
these
specific embodiments should not be construed as narrowing the scope of the
formulations and methods described herein, but rather construed as
illustrative
examples. It is to be further understood that obvious embodiments,
modifications and
equivalents thereof are anticipated and are considered to be within the scope
of the
newly presented formulations and methods, without departing from the broad
spirit
contemplated herein. The subject matter of the instant disclosure is further
illustrated
and described in the claims that follow.
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