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Patent 2309715 Summary

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(12) Patent Application: (11) CA 2309715
(54) English Title: METHOD FOR CLEANING USING MICROWAVES AND A BLEACHING COMPOSITION
(54) French Title: PROCEDE DE NETTOYAGE METTANT EN OEUVRE DES MICRO-ONDES ET UNE COMPOSITION DE BLANCHIMENT
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/39 (2006.01)
  • A61L 2/12 (2006.01)
  • A61L 2/18 (2006.01)
  • C11D 3/395 (2006.01)
  • C11D 3/43 (2006.01)
  • C11D 11/00 (2006.01)
  • C11D 17/04 (2006.01)
(72) Inventors :
  • HUTTON, HOWARD DAVID (United States of America)
  • GOLDSTEIN, ALAN SCOTT (United States of America)
  • CASPER, NANCY NIEHAUS (United States of America)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY
(71) Applicants :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(74) Agent: DIMOCK STRATTON LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 1998-11-13
(87) Open to Public Inspection: 1999-05-27
Examination requested: 2000-05-10
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1998/024192
(87) International Publication Number: US1998024192
(85) National Entry: 2000-05-10

(30) Application Priority Data:
Application No. Country/Territory Date
60/065,721 (United States of America) 1997-11-14

Abstracts

English Abstract


A method is disclosed for removing stains and/or odors and for disinfecting
plastics, and other surfaces by contacting a substrate containing a liquid or
gel treating composition with the surface and subjecting it to microwaves. The
treating composition is a cleaning or detergent composition and includes a
bleaching agent. The method is also very effective in disinfecting and
deodorizing surfaces.


French Abstract

L'invention concerne un procédé qui permet d'éliminer les taches et/ou les odeurs et de désinfecter des plastiques et autres surfaces en mettant un substrat contenant un liquide ou une composition de traitement au gel au contact de ladite surface et en l'exposant à des micro-ondes. Cette composition de traitement est un produit nettoyant ou une composition détergente incluant un agent de blanchiment. Le procédé est également très efficace pour désinfecter et désodoriser des surfaces.

Claims

Note: Claims are shown in the official language in which they were submitted.


21
What is claimed is:
1. A method for treating surfaces characterized by the steps of:
(a) contacting said surface with a substrate containing an effective amount of
a
treating composition including a bleaching agent and a solvent which generates
heat under microwave radiation;
(b) subjecting said surface and said substrate to microwaves for an effective
amount of time such that said treating composition foams onto said surface,
thereby treating said surface.
2. A method according to Claim 1 wherein said substrate is selected from the
group
consisting of comminuted wood pulp, creped cellulose wadding, hydrogel-forming
polymer gelling agents, creped tissues, creped nonwovens containing fibers
characterized
by absorbent polymers, modified cross-linked cellulose fibers, capillary
channel fibers,
absorbent foams, thermally bonded airlaid materials, absorbent sponges,
synthetic staple
fibers, polymeric fibers, peat moss, and combinations thereof.
3. A method according to Claims 1-2 further characterized by the step of
adding
water to said surface or substrate prior to said step (b).
4. A method according to Claims 1-3 wherein said surface is selected from the
group
consisting of ceramic, plastic, dishware, dentifrice/dentures,
surgical/medical equipment,
baby bottles, wood, glass, and mixtures thereof.
5. A method according to Claims 1-4 wherein said bleaching agent is selected
from the
group consisting of:
a) diacyl peroxide;
b) a source of hydrogen peroxide and bleach activator;
c) a source of hydrogen peroxide;
c) a chlorine bleach; and
d) mixtures thereof.
6. A method according to Claim 5 wherein said treating composition is further
characterized by an ingredient selected from the group consisting of
surfactant, solvent,
clay, water, polycarboxylate thickeners, baking soda, carbonates, phosphates,

22
hydrobenzoic acid, dicarboxylic acid, siloxanes, perfumes, bleach catalysts,
and mixtures
thereof.
7. A method according to Claims 1-6 wherein said effective amount of time is
from 30
seconds to 5 minutes, preferably from 30 seconds to 3 minutes.
8. A method according to Claims 1-7 wherein said microwaves have an
electromagnetic radiation wavelength of from 1cm to 1m.
9. A method according to Claims 1-8 wherein said bleaching agent is a diacyl
peroxide
selected from the group consisting dibenzoyl peroxide, dianisoyl peroxide,
benzoyl gluaryl
peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl
peroxide,
dinaphthoyl peroxide, substituted dinaphthoyl peroxide, and mixtures thereof.
10. A method according to Claims 1-9 wherein said treating composition is a
gel or
liquid detergent composition characterized by weight:
(a) from 0.1% to 60% of said bleaching agent which is selected from the group
consisting of:
i) diacyl peroxide having the general formula:
RC(O)OO(O)CR1
wherein R and R1 can be the same or different;
ii) a source of hydrogen peroxide;
iii) a source of hydrogen peroxide and a bleach activator;
iv) a chlorine bleach; and
v) mixtures thereof;
(b) from 0% to 95% of a solvent;
(c) from 0% to 50% of a surfactant; and
(d) from 0% to 7% of a thickener.

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/24192
METHOD FOR CLEANING USING MICROWAVES AND A BLEACHING COMPOSITION
TECHNICAL FIELD
The invention generally relates to the field of bleaching compositions. More
specifically, the invention relates to a method for cleaning or otherwise
removing stains.
odors and microbes from surfaces by contacting a substrate having a bleaching
composition impregnated or otherwise contained therein. and subjecting the
surface and
substrate to microwaves. The composition is a liquid or gel detergent
composition. This
method provides enhanced cleaning and improved stain removal on plastics,
ceramics and
other surfaces. The bleaching composition comprise a bleaching agent,
preferably diacyl
peroxide in a liquid or gel formulation.
BACKGROUND OF THE INVENTION
Detergents used for washing tableware (i.e., glassware, china, silverware,
plastic,
etc.) or kitchenware in the home or institution have long been known.
Dishwashing in the
seventies is reviewed by Mizuno in Vol. 5, Part III of the Surfactant Science
Series, Ed.
W.G. Cutler and R.C. Davis, Marcel Dekker, N.Y., 1973, incorporated by
reference. The
particular requirements of cleansing tableware and leaving it in a sanitary,
essentially
stainless, residue-free state has indeed resulted in so many particular
compositions that
the body of art pertaining thereto is now recognized as quite distinct from
other cleansing
product art. Additionally, the body of art pertaining to fabric cleaning is
immense and
encompasses many formulations designed for stain removal, many including
bleaches.
However, consumers continue to experience problems with stain removal on
various surfaces, including typical kitchenware surfaces. In particular,
formulators have
experienced difficulties in formulating detergents which remove both
hydrophobic and
hydrophilic stains. Typically for stain removal, formulators have turned to
chlorine
bleach or sources of hydrogen peroxide and bleach activators.
Numerous substances have been disclosed in the art as effective bleach
activators.
One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED
provides effective hydrophilic cleaning especially on beverage stains, but has
limited
performance on hydrophobic stains, dingy stains and body soils. Another type
of
activator, such as nonanoyloxybenzenesulfonate (HOBS) and other activators
which
generally comprise long chain alkyl moieties, is hydrophobic in nature and
provides
excellent performance on dingy stains and carotenoid stains.
It would seem that a combination of bleach activators, such as TAED and NOBS,
would provide an effective detergent composition which would perform well on
both

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WO 99/25802 PCT/US98/24192
hydrophilic and hydrophobic soils and stains. However, many of the hydrophilic
activators developed thus far, including TAED, have been found to have limited
efficacy.
especially at wash water temperatures below 60°C. Another consideration
in the
development of consumer products effective on both types of soils is the
additional costs
associated with the inclusion of two or more bleach activators. Accordingly,
it is of
substantial interest to the manufacturers of bleaching systems to find a less
expensive
type of bleaching activator.
Chlorine bleaches are effective for stain and/or soil removal. While chlorine
bleach is a very effective cleaning agent, it is not compatible with a variety
of detergent
ingredients and may require lengthy soaking time in which the bleach and the
stained
surface must remain in contact to ensure stain removal.
Another known bleaching source is diacyl peroxides (DAPS). Although DAPS
have been disclosed for use in the laundry and anti-acne area, they have had
limited
success in liquid or automatic dishwashing detergent area. In the laundry
field, certain
diacyl peroxides have been disclosed as beneficial in cleaning tea stains from
fibrous
material. Recently, DAPS have been used to improve stain removal performance
on
plastics. Another problem facing formulators is stability of the bleaching
agents and
other individual ingredients over time, especially in liquid products. This is
particularly
true for DAPS under alkaline conditions.
As a consequence to the above-identified problems, there has been a
substantial
amount of research to develop bleaching systems which are stable and effective
in liquid
formulations and in which the amount of soaking time need-to remove stains is
greatly
reduced. Recently, certain bleaching agents have been applied directly to a
surface and
subjected to microwaves. Such a method of cleaning performs efficiently and
effectively
under mixed soil load conditions, especially mixtures of hydrophobic and
hydrophilic
soils. The bleaching agent is contained in a detergent composition which has
the property
of removing stains, especially tea, fruit juice and carotenoid stains objected
to by the
consumer from plastic dishware, glass, wood, and many other known surfaces
when
exposed to microwaving from any typical household or commercial microwave.
However, one problem associated with the aforementioned method involving
microwaving a bleach-containing detergent composition is that the detergent
composition
is usually in liquid form and sprayed onto the surface to be cleaned by the
consumer. As
a consequence of this, the dosing or amount of the detergent sprayed onto the
surface is
not uniform and is subject to misuse which can interfere with the overall
cleaning
performance. For example, excess amounts of the detergent composition can be
unnecessarily applied to the surface, thereby adding to the costs associated
with removing

CA 02309715 2000-OS-10
WO 99/25802 PC?/US98/24192
or otherwise cleaning the surfaces. On the other hand, insufficient amounts of
the
detergent composition may be sprayed on the surface resulting in poor or
little
performance. Additionally, the liquid spray on method only permits a
relatively low
amount of solvent such as water to be used, which in turn, reduces the
duration of
microwaving before the detergent dries up and is nonresponsive to microwaves.
Accordingly, there is a need for method by which plastic, ceramic and other
surfaces can be efficiently and effectively cleaned without using excessive or
insufficient
amounts of a tieating composition and subjecting the composition to misuse
which
inhibits the cleaning performance.
SUMMARY OF THE INVENTION
The invention provides a method by which surfaces, such as tableware, can be
cleaned using a substrate containing a detergent composition containing a
bleaching
agent. The method involves taking the substrate, such as a sponge, that has
been
impregnated with the bleach-containing detergent composition and contacting
the
substrate with the surface to be cleaned, sanitized or deodorized and
subjecting both the
substrate and surface to microwaves. The detergent composition foams during
microwaving which delivers the detergent composition uniformly to the surface.
Optionally, water can be added to prolong the response time to microwaves for
enhanced
cleaning.
By "effective amount" or "stain removal-improving amount", it is meant a
bleaching agent is any amount capable of measurably improving stain removal
(especially of tea stains and carotenoid stains) from the surface, i.e.,
soiled dishware,
when it is washed by the consumer. In general, this amount may vary quite
widely. By
"tough food cleaning" herein is meant the ability to clean burned-on, dried-
on, or baked-
on foods. Examples include burned on lasagna, dried on egg, and burned on beef
grease.
All percentages and proportions herein are by weight, and all references cited
are hereby
incorporated by reference, unless otherwise specifically indicated.
In accordance with one aspect of the invention, a method of treating soiled,
stained or otherwise infected surfaces is provided. The method comprises the
steps of:
(a) contacting the surface with a substrate containing an effective amount of
a treating
composition including a bleaching agent and a solvent which generates heat
under
microwave radiation; (b) subjecting the surface and the substrate to
microwaves for an
effective amount of time such that the treating composition foams onto the
surface,
thereby treating the surface.
In accordance with another aspect of the invention, a product for treating
surfaces
is provided. The product comprises a substrate containing a treating
composition

CA 02309715 2000-OS-10
WO 99125802 PCT/US98/2419~
including a bleaching agent and a solvent which generates heat under microwave
radiation, the product further including instructions for using of the
treating composition
comprising the steps of: (a) contacting a surface with the substrate; and (b)
subjecting the
surface to microwaves for an effective amount of time to treat the surface.
Accordingly, it is an object of the invention it is an object of the invention
to
provide a method by which plastic, ceramic and other surfaces can be
efficiently and
effectively cleaned without using excessive or insufficient amounts of a
treating
composition. These and other objects, features and attendant advantages of the
present
invention will become apparent to those skilled in the art from a reading of
the following
detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The method of the invention essentially includes the steps of contacting the
surface to be treated with a substrate containing a treating composition and
subjecting
both the substrate and surface to microwaves. Optionally, water can be added
to the
surface in order to prolong the response time to microwaves. This is a
significant
improvement over a typical liquid treating composition which has a limited
amount of
water or other solvent contained therein. Specifically, by using a spray-on
liquid treating
composition, the user would have to add water in addition to the sprayed on
liquid
composition which is counter-intuitive to conventional liquid spray-on
treatment
composition use, or the user would be required to spray on large mounts of the
treatment
composition which is difficult to persuade consumers to do as they feel they
are wasting
or incorrectly using excessive amounts of the composition. By contrast, the
substrate in
the present invention can be loaded with water or other solvent at higher
amounts than
that which would be present in the liquid spray on treatment composition
usage, and
optionally, additional water can be added as part of the method which is not
counter-
intuitive to normal consumer usage of substrate-like products.
The treating composition is preferably a detergent composition which contains
a
bleaching agent. In preferred embodiments of the method invention, the
treating
composition further comprises an ingredient selected from the group consisting
of
surfactant, solvent, clay, water, polycarboxylate thickeners, baking soda,
carbonates,
phosphates, hydrobenzoic acid, dicarboxylic acid, siloxanes, perfumes, bleach
catalysts,
and mixtures thereof. The treating composition can be in a variety of forms
including a
liquid, gel or granules.
Although this method can be employed to assist in bleaching the surface for
any
desired purpose, examples of likely uses include one or more of the following:
stain
removal, stain reducing, deodorizing, or disinfecting. Preferably, the surface
is selected

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/24192
from the group consisting of ceramic, plastic, dishware. dentifrice/dentures,
surgical/
medical equipment, baby bottles, wood, glass, and mixtures thereof. The
surface after
being treated with the bleach-containing detergent composition is then
subjected to
microwaves for an effective amount of time to "treat" the surface to the
desired end
result, i.e. stain reduction, deodorizing, disinfecting. Typically an
"effective amount of
time" is from about 30 seconds to about 5 minutes, preferably from about 30
seconds to
about 3 minutes, and most preferably from about 1 minute to 2 minutes. During
this
effective amount of time, the treating composition on and/or in the substrate
foams
uniformly onto the surface and delivers the bleaching agent, which in tum,
cleans the
stains, deodorizes and or disinfects the surface. This provides a dramatically
unexpectedly large increase in performance as compared to simply spraying or
otherwise
applying the treating composition to the surface.
Preferred aspects of the treating composition described herein include having
the
bleaching agent selected from the group consisting of diacyl peroxide, a
source of
hydrogen peroxide and bleach activator, a source of hydrogen peroxide, a
chlorine bleach,
and mixtures thereof. Another highly preferred treating composition is a gel
or liquid
detergent composition comprising by weight: (a) from about 0. I % to about 60%
of said
bleaching agent which is selected from the group consisting of: i) diacyl
peroxide
having the general formula:
RC(O)00(O)CRI
wherein R and Rl can be the same or different; ii) a source of hydrogen
peroxide; iii) a
source of hydrogen peroxide and a bleach activator; iv) a chlorine bleach; and
v) mixtures
thereof; (b) from 0% to about 95% of a solvent; (c) from 0% to about 50% of a
surfactant;
and (d) from 0% to about 7% of a thickener. Another highly preferred treating
composition is a gel detergent composition comprising by weight: (a) from
about 0. I
to about 10% of a diacyl peroxide having the general formula:
RC(O)00(O)CR1
wherein R and R1 can be the same or different; (b) from 0% to about 50% of a
surfactant;
and (c) from 0% to about 7% of a thickener; the composition having a neat pH
of from
about 3 to about 10; and such that said diacyl peroxide remains undissolved in
said
composition.
Substrate - The substrate used in the method invention provided herein can be
any
material capable of carrying, holding, containing or otherwise delivering the
bleach-
containing detergent composition. In certain preferred embodiments, the
treating

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/24192
composition is in gel form and impregnated in the substrate so that it can be
conveniently
packaged and stored on a commercially large scale. Preferably. the substrate
is selected
from the group consisting of comminuted wood pulp, creped cellulose wadding,
hydrogel-forming polymer gelling agents, creped tissues, creped nonwovens
containing
fibers comprised of absorbent polymers, modified cross-linked cellulose
fibers, capillary
channel fibers, absorbent foams, thermally bonded airlaid materials, absorbent
sponges,
synthetic staple fibers, polymeric fibers, peat moss, and combinations
thereof. The most
preferred substrate is an absorbent sponge.
Microwaves - By microwaving herein is meant exposing said surface treated with
said compositions to microwave electromagnetic radiation. This is by any
conventional
means such as by placing the surface in a typical microwave such as used in
homes and
microwaving the surface for a sufficient time. Microwaves have an
electromagnetic
radiation wavelength of from about lcm to about lm, preferably from about 3cm
to about
30cm, more preferably from about 11 cm to about 13cm. See Aust. J. Chem.,
1995, 48
[10], 166-1692, Developments in Microwave-Assisted Organic Chemistry, by
Strauss
and Trainor.
Bleaching-Agents
Suitable bleaching for use herein are listed below:
Diacyl Peroxide Bleaching Species - The composition of the present invention
preferably contain diacyl peroxide of the general formula:
RC(O)00(O)CR1
wherein R and R1 can be the same or different and are hydrocarbyls, preferably
no more
than one is a hydrocarbyl chain of longer than ten carbon atoms, more
preferably at least
one has an aromatic nucleus.
Examples of suitable diacyl peroxides are selected from the group consisting
dibenzoyl peroxide, dianisoyl peroxide, benzoyl gluaryl peroxide, benzoyl
succinyl
peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide, dinaphthoyl
peroxide,
substituted dinaphthoyl peroxide, and mixtures thereof, more preferably
dibenzoyl
peroxide, dicumyl peroxide, diphthaloyl peroxides and mixtures thereof. A
particularly
preferred diacyl peroxide is dibenzoyl peroxide.
Hydrogen Peroxide Source - The compositions of the present invention may
comprise a source of oxygen bleach, preferably a source of hydrogen peroxide
with or
without a selected bleach activator. The source of hydrogen peroxide is
typically any
common hydrogen-peroxide releasing salt, such as sodium perborate or sodium
percarbonate. Hydrogen peroxide sources are illustrated in detail in Kirk
Othmer Review
on Bleaching and include the various forms of sodium perborate and sodium
percarbonate

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WO 99/25802 PCT/US98124192
and modified forms. An "effective amount" of a source of hydrogen peroxide is
any
amount capable of measurably improving stain removal (especially of tea and
tomato
stains) from the soiled surface compared to a hydrogen peroxide source-free
composition
when the soiled surface is washed by the consumer.
The preferred source of hydrogen peroxide used herein can be any convenient
source, including hydrogen peroxide itself. For example, perborate, e.g.,
sodium
perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium
carbonate
peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxy-
hydrate,
urea peroxyhydrate, or sodium peroxide can be used herein. Sodium perborate
monohydrate and sodium percarbonate are particularly preferred. Mixtures of
any
convenient hydrogen peroxide sources can also be used.
Another source of hydrogen peroxide is enzymes. Examples include Lipoxidase,
glucose oxidase, peroxidase, alcohol oxidases, and mixtures thereof.
Bleach Activators - Numerous conventional bleach activators are known. See for
example activators referenced hereinabove in the background as well as U.S.
Patent
4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
Nonanoyloxybenzenesulfonate (HOBS) or acyl lactam activators may be used, and
mixtures thereof with TAED can also be used. See also U.S. 4,634,551 for other
typical
conventional bleach activators. Also known are amido-derived bleach activators
of the
formulae: R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L wherein R1 is an alkyl
group containing from about 6 to about 12 carbon atoms, R2 is an aikylene
containing
from 1 to about 6 carbon atoms, RS is H ar alkyl, aryl, or alkar~rl containing
from about 1
to about 10 carbon atoms, and L is any suitable leaving group. Further
illustration of
bleach activators of the above formulae include (6-
octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)-
oxybenzenesulfonate,
(6-decanamidocaproyl)oxyben2enesulfonate, and mixtures thereof as described in
U.S.
Patent 4,634,551. Another class of bleach activators comprises the benzoxazin-
type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October
30, 1990.
Still another class of bleach activators includes acyl lactam activators such
as octanoyl
caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,
decanoyl
caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl
valerolactam,
undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethyl-hexanoyl
valerolactam,
t-butylbenzoylcaprolactam, t-butylbenzoylvalerolactam and mixtures thereof.
The
present compositions can optionally comprise aryl benzoates, such as phenyl
benzoate,
and acety triethyl citrate.

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WO 99/25802 PCT/US98/2419=
Quaternary Substituted Bleach Activators - The present compositions can also
comprise quaternary substituted bleach activators (QSBA). QSBA's herein
typically have
the formula E-[Z]n-C(O)-L, wherein group E is referred to as the "head", group
Z is
referred to as the "spacer" (n is 0 or 1, i.e., this group may be present or
absent, though its
presence is generally preferred) and L is referred to as the "leaving group".
These
compounds generally contain at least one quaternary substituted nitrogen
moiety, which
can be contained in E, Z or L. More preferably, a single quaternary nitrogen
is present
and it is located in group E or group Z. In general, L is a leaving group, the
pKa of the
corresponding carbon acid (HL) of which can lie in the general range from
about 5 to
about 30, more preferably, from about 10 to about 20, depending upon the
hydrophilicity
of the QSBA. pKa's of leaving groups are further defined in U.S. Pat. No.
4,283,301.
Preferred QSBA's herein are water-soluble but have a tendency to partition to
a
definite extent into surfactant micelles, especially into micelles of nonionic
surfactants.
Leaving groups and solubilizing tendencies of quaternary moieties which can be
present in the QSBA's are further illustrated in U.S. 4,539,130, Spt. 3, 1985
incorporated
by reference. This patent also illustrates QSBA's in which the quaternary
moiety is
present in the leaving group L.
British Pat. 1,382,594, published Feb. 5, 1975, discloses a class of QSBA's
found
suitable for use herein. In these compounds, Z is a poly(methylene) or
oligo(methylene)
moiety, i.e., the spacer is aliphatic, and the quaternary moiety is E. U.S.
4,818,426 issued
Apr. 4., 1989 discloses another class of QSBA's suitable for use herein. These
compounds are quaternary ammonium carbonate esters wherein, with reference to
the
above formula, the moiety Z is attached to E via a carbon atom but is attached
to the
carbonyl moiety through a linking oxygen atom. These compounds are thus
quaternary
ammonium carbonate esters. The homologous compounds wherein the linking oxygen
atom is absent from Z are likewise known and are useful herein. See, for
example, U.S.
5,093,022 issued March 3, 1992 and U.S. 4,904,406, issued Feb. 27, 1990.
Additionally,
QSBA's are described in EP 552,812 A1 published July 28, 1993, and in EP
540,090 A2,
published May 5, 1993.
Chlorine Bleach - Any chlorine bleach typically known in the art is suitable
for
use herein. Preferred chlorine bleaches for use herein include sodium
hypochlorite,
lithium hypochlorite, calcium hyposhlorite, chlorinated trisodium phosphates,
and
mixtures thereof. For more about chlorine bleaches see Surfactant Science
Series, Vol. 5,
Part II, pages 520-26.
Other Ingredients - Detersive ingredients or adjuncts optionally included in
the
instant compositions can include one or more materials for assisting or
enhancing

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9
cleaning performance, treatment of the surface to be cleaned, or designed to
improve the
aesthetics or ease of manufacture of the compositions. Other adjuncts which
can also be
included in compositions of the invention at their conventional art-
established levels,
generally from 0% to about 20% of the composition, preferably at from about
0.1 % to
about 10%, include one or more processing aids, color speckles, dyes, fillers,
bleach-
compatible enzymes, germicides, alkalinity sources, hydrotropes, stabilizers,
perfumes,
solubilizing agents, carriers. In general, materials used for the production
of detergent
compositions herein are preferably checked for compatibility with the
essential
ingredients used herein.
In the preferred embodiments, additional ingredients such as water-soluble
silicates (useful to provide alkalinity and assist in controlling corrosion),
dispersant
polymers (which modify and inhibit crystal growth of calcium and/or magnesium
salts),
chelants (which control transition metals), builders such as citrate (which
help control
calcium and/or magnesium and may assist buffering action), and alkalis (to
adjust pH) are
present. Additional bleach-improving materials such as bleach catalysts may be
added.
Solvent - The solvent of the present invention is of the type which the diacyl
peroxide will dissolve in. The preferred solvents are selected based upon the
solubility
parameter value of the diacyl peroxide employed. The solubility parameter
value of a
compound is available from literature sources such as Polymer Handbook. Values
obtained by experiments are preferred. If the solubility parameter value is
not available
in the literature, the value can be calculated by using any of the methods
described by
Robert F. Fedor's article "A Method of Estimating Both the Solubility
Parameters &
Molar Volumes of Liquids", Polymer Engineering & Science, February, 1974, Vol
14,
No. 2. Once the solubility parameter value is obtained of the diacyl peroxide,
solvents
are selected having a solubility parameter which fall within the diacyl
peroxide solubility
parameter.
Said solvent is preferably selected from the group consisting of N-alkyl
pyrrolidones, such as N-ethyl pyrrolidone, diacetone alcohol, long chain
(greater than C6)
alkyl ethers, cyclic alkyl ketones, and mixtures thereof. Amines, ethers and
short chain
(less than C6) primary and secondary alcohols are preferably not present.
Without being
limited by theory, it is believed that the presence of these compounds may
introduce
stability problems. Thus, when diacyl peroxide and solvent are present in the
compositions of this invention, it is further preferable that the amount of
amine, ether, or
primary or secondary alcohol be limited to no more than about 5%, preferably
no more
than about 3%, by weight of the composition.

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/2419:
Surfactants - Nonlimiting examples of surfactants useful herein include the
conventional C I I -C I g alkyl benzene sulfonates ("LAS") and primary,
branched-chain
and random C I 0-C20 alkyl sulfates ("AS"), the C 10-C I g secondary (2,3)
alkyl sulfates of
the formula CH3(CH2)x(CHOS03-M~) CH3 and CH3 (CH2)y(CHOS03-M~) CH~CH3
where x and (y + 1 ) are integers of at least about 7, preferably at least
about 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl sulfate,
the C 10-C 1 g alkyl alkoxy sulfates ("AEx S"; especially EO 1-7 ethoxy
sulfates). C ~ 0-C I g
alkyl alkoxy carboxylates (especially the EO I-5 ethoxycarboxylates), the C I
0-C 18
glycerol ethers, the C I 0-C 1 g alkyl polyglycosides and their corresponding
sulfated
polyglycosides, and C I 2-C I g alpha-sulfonated fatty acid esters.
If desired, the conventional nonionic and amphoteric surfactants such as the C
1 ~-
C 1 g alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl
ethoxylates
and C6-C I 2 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy),
C I 2-C 1 g betaines and sulfobetaines ("sultaines"), and the like, can also
be included in the
overall compositions. The C 10-C I g N-alkyl polyhydroxy fatty acid amides can
also be
used. Typical examples include the C I 2-C I g N-methylglucamides. See WO
9,206,154.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides,
such as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl
C I ~-
C I g glucamides can be used for low sudsing. C I 0-C2p conventional soaps may
also be
used. If high sudsing is desired, the branched-chain C 1 p-C 16 soaps may be
used.
Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional
useful surfactants are listed in standard texts.
Preferably, anionic surfactants are used herein. Without being limited by
theory,
it is believed that the use of anionic surfactants maximizes both cleaning
performance and
removal of residual bleach from the surface being treated.
One example of a group of surfactants suitable for use herein are those
selected
from the group consisting of alkyl ether sulfate, long chain (greater than
about C7) alkyl
.ethoxylate, linear alkyl benzene sulfonate (LAS), alkyl (ether) carboxylates,
alkyl
polyglucaside (APG), and mixtures thereof.
Thickeners - Thickeners for use herein can be selected from clay,
polycarboxylates, such as Polygel~, gums, carboxymethyl cellulose,
polyacrylates, and
mixtures thereof. The preferred clay type herein has a double-layer structure.
The clay
may be naturally occurring, e.g., Bentonites, or artificially made, e.g.,
Laponite~.
Laponite~ is supplied by Southern Clay Products, Inc. See The Chemistry and
Physics
of Clavs, Grimshaw, 4th ed., 1971, pages 138-155, Wiley-Interscience.

CA 02309715 2000-OS-10
WO 99125802 PCT/US98I2y19=
Bleach catalysts - If desired. detergent compositions herein may additionally
incorporate a catalyst or accelerator to further improve bleaching or starchy
soil removal.
Any suitable bleach catalyst can be used. The compositions will comprise from
about
0.0001 % to about 0.1 % by weight of bleach catalyst.
Typical bleach catalysts comprise a transition-metal complex, for example one
wherein the metal coordinating ligands are quite resistant to labilization and
which does
not deposit metal oxides or hydroxides to any appreciable extent under the
conditions of
cleaning herein. Such catalyst compounds often have features of naturally
occurring
compounds such as enzymes but are principally provided synthetically. Highly
preferred
accelerators include, for example, the cobalt 3+ catalysts, especially
{Co(NH3)SCl}~+or
equivalents thereof with various alternate donor ligands. Such complexes
include those
formerly disclosed for use in laundry compositions in U.S. Pat. 4,810,410 to
Diakun et al,
issued March 7, 1989. The active species thereof is believed to be
{Co(NH3)5(OOH)}2+
and is disclosed in J. Chem. Soc. Faraday Trans., 1994, Vol. 90, 1105-1114.
Alternate
catalysts or accelerators are the noncobalt transition metal complexes
disclosed in this
reference, especially those based on Mo(VI), Ti(IV), W(VI), V(V) and Cr(VI)
although
alternate oxidation states and metals may also be used. Such catalysts include
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. 5,244,594;
U.S.
5,194,416; U.S. 5,114,606; and EP Nos. 549,271 A 1, 549,272 A 1, 544,440 A2,
and
X44,490 Al; preferred examples of these catalysts include MnIV2(p-O)3(TACN)2-
(pF6)2~ MnIII2(w-O)1(N~-OAc)2(TACN)2(C104)2~ M~'~IV4(!~-O)6(TACN)4(CIO4)4~
MnIIIMnIV4-(p_O)1(p-OAc)2-(TACN)2-(C104)3, MnIV-(TACN)-(OCH3)3(PF6), and
mixtures thereof wherein TACN is trimethyl-1,4,7-triazacyclononane or an
equivalent
macrocycle; though alternate metal-coordinating ligands as well as mononuclear
complexes are also possible and monometallic as well as di- and polymetallic
complexes
and complexes of alternate metals such as iron or ruthenium are all within the
present
scope. Other metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243
and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to
enhance
bleaching is also reported in the following United States Patents: 4,728,455;
5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
Transition metals may be precomplexed or complexed in-situ with suitable donor
ligands selected in function of the choice of metal, its oxidation state and
the denticity of
the ligands. Other complexes which may be included herein are those of U.S.
Application Ser. No. 08/210,186, filed March 17, 1994. Other suitable
transition metals
in said transition-metal-containing bleach catalysts include iron, cobalt,
ruthenium,
rhodium, iridium, and copper.

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/24192
1 '_'
Builders - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders can
be used. Builders are typically used in fabric laundering compositions to
assist in the
removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically
comprise at least about 1% builder. Liquid formulations typically comprise
from about
5% to about 50%, more typically about S% to about 30%, by weight, of detergent
builder.
Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by
the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, physic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2: I and layered silicates,
such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12,
1987 to H. P.
Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst
(commonly abbreviated herein as "SKS-6"). NaSKS-6 can be prepared by methods
such
as those described in German DE-A-3,417,649 and DE-A-3,742,043. Other layered
silicates, such as those having the general formula NaMSix02x+1 ~yH20 wherein
M is
sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number from 0
to 20 can be used herein. Various other layered silicates from Hoechst include
NaSKS-S,
NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates
as disclosed in German Patent Application No. 2,321,001 published on November
15,
1973.
Aluminosilicate builders may be useful in the present invention.
Aluminosilicate
builders include those having the empirical formula:
Mz(zA102)y]~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0
to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. A
method for producing aluminosilicate ion exchange materials is disclosed in
U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline
aluminosilicate ion exchange materials useful herein are available under the
designations

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/24192
13
Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially
preferred
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2[(A102)12(Si02)12~'xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As used
herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanola.mmonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972.
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on
May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,158,63; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, S-
trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the
various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such
as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium
salt), are polycarboxylate builders of importance for liquid detergent
formulations due to
their availability from renewable resources and their biodegradability.
Oxydisuccinates
are also especially useful in such compositions and combinations.
Also suitable in the compositions of the present invention are the 3,3-
dicarboxy-4-
oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent
4,566,984,
Bush, issued January 28, 1986. Laurylsuccinates are the preferred builders of
this group,

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/2419:
14
and are described in European Patent Application 86200690.5/0,200,263,
published
November 5. 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4.144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into
the compositions alone, or in combination with the aforesaid builders,
especially citrate
and/or the succinate builders, to provide additional builder activity.
Various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other
known
phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,400,148
and 3.422,137) can also be used.
Enzymes - Suitable enzymes include proteases, amylases, lipases, cellulases,
peroxidases, and mixtures thereof of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. Preferred selections are influenced by
factors such as
pH-activity and/or stability optima, thermostability, and stability to active
bleach,
detergents, builders and the like. In this respect bacterial or fungal enzymes
are preferred,
such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount".
The term
"cleaning effective amount" refers to any amount capable-educing a cleaning,
stain
removal, soil removal, whitening, deodorizing, or freshness improving effect
on surfaces
such as dishware and the like. In practical terms for current commercial
preparations, the
compositions herein may comprise from 0.001% to 5%, preferably 0.01%-1% by
weight
of a commercial enzyme preparation. Protease enzymes are usually present in
such
commercial preparations at levels sufficient to provide from 0.005 to 0.1
Anson units
(AU) of activity per gram of composition.
The preparation of protease enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The
Netherlands;
as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and
Protease B as
disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.
See also
a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to
Novo. Enzymatic detergents comprising protease, one or more other enzymes, and
a
reversible protease inhibitor are described in WO 9203529 A to Novo. Other
preferred

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98124192
1~
proteases include those of WO 951091 A to Procter & Gamble . When desired, a
protease having decreased adsorption and increased hydrolysis is available as
described
in WO 907791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents
suitable herein is described in WO 9425583 to Novo.
Amylases suitable herein, especially for, but not limited to automatic
dishwashing
purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;
RAPIDASE~. International Bio-Synthetics, Inc. and TERMAMYL~, Novo.
FUNGAMYL~ from Novo is especially useful. Engineering of enzymes for improved
stability, e.g., oxidative stability, is known. See, for example J. Biological
Chem., Vol.
260, No. 11, June 1985, pp 6518-6521 Preferred amylases include (a) an amylase
according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994.
Other
amylases include variants having additional modification in the immediate
parent as
described in WO 9510603 A and are available from the assignee, Novo, as
DURAMYL~
. Other particularly preferred oxidative stability enhanced amylase include
those
described in WO 9418314 to Genencor International and WO 9402597 to Novo.
Cellulases usable herein include those disclosed in U.S. 4,435,307,
Barbesgoard et
al, March 6, 1984. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-
2.095.27~ and DE-OS-2.247.832. CAREZYME~ (Novo) is especially useful. See also
WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154,
as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application
53,20487,
laid open Feb. 24, 1978. Other suitable commercial lipases include Amano-CES,
lipases
ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673
from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. LIPOLASE~ enzyme derived from Humicola lanuginosa and
commercially available from Novo, see also EP 341,947, is a preferred lipase
for use
herein. Lipase and amylase variants stabilized against peroxidase enzymes are
described
in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to
Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g.,
percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
prevention
of transfer of dyes or pigments removed from surfaces during the wash to other
surfaces
present in the wash solution. Known peroxidases include horseradish
peroxidase,

CA 02309715 2000-OS-10
WO 99125802 PCT/US98124192
16
ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed in WO 89099813 A, October 19,
1989 to
Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,53,139, January ~,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. 4,101,47, Place et al,
July 18,
1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful
for
liquid detergent formulations, and their incorporation into such formulations,
are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in
detergents
can be stabilized by various techniques. Enzyme stabilization techniques are
disclosed
and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,40 and
EP
200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also
described,
for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases,
xylanases
and cellulases, is described in WO 9401532 A to Novo.
Enzyme Stabilizing System - Enzyme-containing, including but not limited to,
liquid compositions, herein may comprise from about 0.001% to about 10%,
preferably
from about 0.005% to about 8%, most preferably from about 0.01 % to about 6%,
by
weight of an enzyme stabilizing system. Such stabilizing systems can, for
example,
comprise calcium ion, boric acid, propylene glycol, short chain carboxylic
acids, boronic
acids, and mixtures thereof, and are designed to address different
stabilization problems
depending on the type and physical form of the detergent composition. See
Severson,
U.S. 4,537,706 for a review of Borate stabilizers.
Stabilizing systems may further comprise from 0 to about 10%, preferably from
about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added to
prevent
chlorine bleach species present in many water supplies from attacking and
inactivating
the enzymes, especially under alkaline conditions. Suitable chlorine scavenger
anions
are widely known and readily available, and, if used, can be salts containing
ammonium
cations with sulfite, bisulfate, thiosulfite, thiosulfate, iodide, etc.
Antioxidants such as
carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic
acid (EDTA)
or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can
likewise
be used. Other conventional scavengers such as bisulfate, nitrate, chloride,
sources of
hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate
monohydrate
and sodium percarbonate, as well as phosphate, condensed phosphate, acetate,
benzoate,
citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures
thereof can be used
if desired.

CA 02309715 2000-OS-10
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17
Material Care Asents - The present compositions may optionally contain as
corrosion inhibitors and/or anti-tarnish aids one or more material care aeents
such as
silicates. Material Care Agents are preferred especially in countries where
electroplated
nickel silver and sterling silver are common in domestic flatware, or when
aluminium
protection is a concern and the composition is low in silicate. Material care
agents
include bismuth salts, transition metal salts such as those of manganese,
certain types of
paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid
salts. and mixtures
thereof and are preferably incorporated at low levels, e.g., from about 0.01 %
to about 5%
of the composition. A preferred paraffin oil is a predominantly branched
aliphatic
hydrocarbon comprising from about 20 to about 50, more preferably from about
25 to
about 45, carbon atoms with a ratio of cyclic to noncyclic hydrocarbons of
about 32 to 68
sold by Wintershall, Salzbergen, Germany as WINOG 70~. Bi(N03)3 may be added.
Other corrosion inhibitors are illustrated by benzotriazole, thiols including
thionaphtol
and thioanthranol, and finely divided aluminium fatty acid salts. All such
materials will
generally be used judiciously so as to avoid producing spots or films on
glassware or
compromising the bleaching action of the compositions. For this reason, it may
be
preferred to formulate without mercaptan anti-tarnishes which are quite
strongly bleach-
reactive or common fatty carboxylic acids which precipitate with calcium.
Chelating A;~ents - The detergent compositions herein may also optionally
contain
one or more iron and/or manganese chelating agents. Such chelating agents can
be
selected from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures therein,
all as
hereinafter defined.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates, ethylenediamine tetraproprionates, triethylenetetra-amine-
hexacetates,
diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use
herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S) isomer as described
in U.S.
Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 10% by weight of the detergent compositions herein. More preferably, if
utilized,

CA 02309715 2000-OS-10
WO 99/25802 PCT/US98/2419=
18
the chelating agents will comprise from about 0.1% to about 3.0% by weight of
such
compositions.
Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously
be utilized at levels from about 0.1 % to about 7%, by weight, in the
compositions herein,
especially in the presence of zeolite and/or layered silicate builders.
Suitable polymeric
dispersing agents include polymeric polycarboxylates and polyethylene glycols,
although
others known in the art can also be used. It is believed, though it is not
intended to be
limited by theory, that polymeric dispersing agents enhance overall detergent
builder
performance, when used in combination with other builders (including lower
molecular
weight polycarboxylates) by crystal growth inhibition, particulate soil
release peptization,
and anti-redeposition.
Bri htg ener - Any optical brighteners or other brightening or whitening
agents
known in the art can be incorporated at levels typically from about 0.05% to
about 1.2%,
by weight, into the detergent compositions herein. Commercial optical
brighteners which
may be useful in the present invention can be classified into subgroups, which
include,
but are not necessarily limited to, derivatives of stilbene, pyrazoline,
coumarin,
carboxylic acid, methinecyanines, diben2othiphene-5,5-dioxide, azoles, 5- and
6-
membered-ring heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of Fluorescent
Brightening
Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Product/Instructions - This invention also encompasses the inclusion of
instructions on the use of a product including a substrate containing the
treating
composition with the package or with other forms of advertising associated
with the sale
or use of the substrate. The instructions may be included in any manner
typically used by
consumer product manufacturing or supply companies. Examples include providing
instructions on a label attached to the container holding the substrate; on a
sheet either
attached to the container or accompanying it when purchased; or in
advertisements,
demonstrations, and/or other written or oral instructions which may by
connected to the
purchase or use of a product containing a substrate and the treating
composition.
Specifically the instructions will include a description of the use of the
substrate
in connection with microwaving. The instructions, for instance, may
additionally include
information relating to the length of microwaving time; the recommended
settings on the
microwave; the recommended positioning of the substrate relative to the
surface to be
cleaned. or whether soaking or rubbing is appropriate; the recommended amount
of
water, if any, to apply to the surface before and after treatment; other
recommended
treatment to accompany the microwave application.

CA 02309715 2000-OS-10
w0 99/25802 PCT/US98/24192
19
Process - Methods for producing diacyl peroxide particles for use in the
compositions herein wherein an abrasive particle is desired may include any
particle
making process commonly known in the art, including shear mixing. The diacyl
particles
for use herein can range in size from sub-micron (0.1 ) to about 100 microns.
A preferred
range is from about 1 to about 20 microns. Another process for making
particles follows:
Process Descriution - The diacyl peroxide raw material particles are dissolved
in
an appropriate solvent (n-ethylpyrrolidone) and added to the rest of the
formulation
(primarily water, surfactant and thickener) with stirring. This procedure
results in the in
situ precipitation of the diacyl peroxide particles, resulting in a dispersion
of small
homogeneous particles ranging in size of from about 1 to about 20 microns.
Optionally,
commercially available diacyl peroxide raw material particles can be used
which have
particle sizes on the order of 800 microns or more, although these are not
preferred.
Procedure for preparation of in situ particles: Laponite (33g, 6% active) is
dispersed in tap water ( 1 OOg) with stirring. Sodium Alkylethoxy sulfate (
14g, 70%
active) is stirred into the Laponite dispersion and Sodium bicarbonate ( 1 g,
100% active)
is added. In a separate container, Benzoyl peroxide (2g, 75% active) is
dissolved in N-
ethylpyrrolidone (lOg, 100% active) with stirring. This benzoyl peroxide
solution is then
poured into the Laponite and surfactant solution with stirring. The mixture
immediately
turns cloudy and results in a homogeneous dispersion of 10-50 micron benzoyl
peroxide
particles.
In order to make the present invention more readily understood, reference is
made
to the following examples, which are intended to be illustrati~ce only and not
intended to
be limiting in scope.
EXAMPLE
Ingredient A B C
C12-13 ~kYl ether sulfate3.0 3.0 __
(avg. -
ethoxy of 1 )
Magnesium chloride 0.3 0.3 -
hexahydrate
Magnesium silicatel 2.0 2.0 -
Potassium bicarbonate 1.0 1.0 -
Chlorine bleach - - 20.0
Acyl peroxide2 2.0 2.0 -
Perfume 0.2 0.2 -
Other (water, dye etc. to 100% to 100% to 100%
)

CA 02309715 2000-OS-10
WO 99/25802 PCT/US981:4192
Microwave Time 1 minute 30 seconds -
Added water 10 grams - -
Tomato on plastic (% 73% 66% I I
removal)
Tea on ceramic (% removal)85% 80% 90%
ICommercially available as Laponite RD~
2Acy1 Peroxides selected from dibenzoyl peroxide, dianisoyl peroxide, benzoyl
gluaryl
peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl
peroxide, dinaphthoyl peroxide, substituted dinaphthoyl peroxide, and mixtures
thereof.
Treating compositions A and B above are identical except that treating
composition A (liquid) is impregnated into and on an absorbent sponge material
in the
form of a 1 cm thick circular spong having a 5 cm diameter, while treating
composition B
is a sparyable liquid. Treating composition C is a conventional chlorine
bleach
composition. Ceramic and plastic cups, bowls etc. are stained by heating
tomato sauce
and/or tea under consumer relevant conditions in the microwave. The stained
items are
washed with a conventional light duty liquid dishwashing detergent that is
commercially
available under typical home wash conditions. The objects remain stained by
the tomato
and tea. An absorbent sponge impregnated with treating composition A (8-IO
grams) is
contacted with the stained item. An amount of treating composition B (8-10
grams) is
sprayed onto the stained item until the stained item is evenly coated with the
composition. The items treated with composition B are individually placed in a
typical
household microwave and microwaved on high setting for 30 seconds, while items
treated with the absorbent sponge are microwaved on high setting for 60
seconds. All the
items are then rinsed out. The treating composition C is applied to the items
and soaked
for 20 minutes, after which it was rinsed. The percent removal is estimated
visually
based on comparison with a stained control and a clean control. As can be seen
in this
Example, composition A as impregnated in the absorbent sponge in accordance
with the
invention unexpectedly allowsfor proper dosage while also exhibiting superior
stain
removal ability compared to compositions B and C which outside the invention.
Having thus described the invention in detail, it will be clear to those
skilled in the
art that various changes may be made without departing from the scope of the
invention
and the invention is not to be considered limited to what is described in the
specification.

Representative Drawing

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Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-12
Application Not Reinstated by Deadline 2002-11-13
Time Limit for Reversal Expired 2002-11-13
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2001-11-13
Letter Sent 2001-01-16
Letter Sent 2001-01-16
Letter Sent 2001-01-16
Letter Sent 2001-01-16
Inactive: Single transfer 2000-11-24
Inactive: Cover page published 2000-07-27
Inactive: First IPC assigned 2000-07-13
Inactive: Courtesy letter - Evidence 2000-07-11
Inactive: Acknowledgment of national entry - RFE 2000-07-07
Application Received - PCT 2000-07-04
All Requirements for Examination Determined Compliant 2000-05-10
Request for Examination Requirements Determined Compliant 2000-05-10
Application Published (Open to Public Inspection) 1999-05-27

Abandonment History

Abandonment Date Reason Reinstatement Date
2001-11-13

Maintenance Fee

The last payment was received on 2000-05-10

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

Patent fees are adjusted on the 1st of January every year. The amounts above are the current amounts if received by December 31 of the current year.
Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Fee History

Fee Type Anniversary Year Due Date Paid Date
MF (application, 2nd anniv.) - standard 02 2000-11-14 2000-05-10
Basic national fee - standard 2000-05-10
Request for examination - standard 2000-05-10
Registration of a document 2000-11-24
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
ALAN SCOTT GOLDSTEIN
HOWARD DAVID HUTTON
NANCY NIEHAUS CASPER
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 2000-05-09 20 1,278
Abstract 2000-05-09 1 41
Claims 2000-05-09 2 74
Cover Page 2000-07-26 1 35
Notice of National Entry 2000-07-06 1 201
Courtesy - Certificate of registration (related document(s)) 2001-01-15 1 113
Courtesy - Certificate of registration (related document(s)) 2001-01-15 1 113
Courtesy - Certificate of registration (related document(s)) 2001-01-15 1 113
Courtesy - Certificate of registration (related document(s)) 2001-01-15 1 113
Courtesy - Abandonment Letter (Maintenance Fee) 2001-12-10 1 183
Correspondence 2000-07-06 1 15
PCT 2000-05-09 10 348