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Patent 2460435 Summary

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(12) Patent Application: (11) CA 2460435
(54) English Title: AQUEOUS COMPOSITIONS FOR TREATING A SURFACE COMPRISING A POLYMERIC BIGUANIDE
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 1/72 (2006.01)
  • C11D 1/66 (2006.01)
  • C11D 1/825 (2006.01)
  • C11D 3/32 (2006.01)
  • C11D 3/37 (2006.01)
  • C11D 11/00 (2006.01)
(72) Inventors :
  • BARNABAS, MARY VIJAYARANI (United States of America)
  • POLICICCHIO, NICOLA JOHN (United States of America)
  • SHERRY, ALAN EDWARD (United States of America)
  • WOLFF, ANN MARGARET (United States of America)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(71) Applicants :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(74) Agent: DIMOCK STRATTON LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2002-10-08
(87) Open to Public Inspection: 2003-04-17
Examination requested: 2004-03-16
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2002/032197
(87) International Publication Number: WO2003/031546
(85) National Entry: 2004-03-16

(30) Application Priority Data:
Application No. Country/Territory Date
60/328,006 United States of America 2001-10-09

Abstracts

English Abstract




The present invention relates to a composition having a pH of less than about
7, for treating a hard surface comprising: at least one low residue surfactant
and/or an alkyl ethoxylate surfactant; and a polymeric biguanide.


French Abstract

La présente invention concerne une composition présentant un pH inférieur à environ 7 et permettant de traiter une surface dure. Cette composition comprend au moins un agent de surface à faible teneur en résidus et/ou un agent de surface d'éthoxylate d'alkyle, ainsi qu'un biguanide polymérique.

Claims

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



What is claimed is:

1. A composition having a pH of 7 or less, for treating a hard surface
comprising:
at least one low residue surfactant and/or an alkyl ethoxylate surfactant; and
a
polymeric biguanide.

2. A composition according to claim 1 wherein the pH is from 5 to 7, and the
low
residue surfactant is a C8-C16 alkyl poly glycoside.

3. A composition according to any of the preceding claims, wherein the pH is
achieved using an organic acidifying agent, preferably using an organic
acidifying
agent is selected from the group consisting of tartaric acid, lactic acid and
citric
acid and mixtures thereof more preferably using citric acid.

4. A composition according to any of the preceding claims, wherein said low-
residue surfactant is selected from the group consisting of zwitterionic
surfactants
and amphoteric surfactants, and non-ionic surfactants comprising at least one
sugar moiety and mixtures thereof; preferably said low-residue surfactant is
selected from the group consisting of sulfobetaines, ampho glycinates, ampho
propionates, betaines, poly alkyl glycosides, sucrose esters, and mixtures
thereof
more preferably said low-residue surfactant is selected from the group
consisting
of sulfobetaines and poly alkyl glycosides, and mixtures thereof.

5. A composition according to any of the preceding claims, wherein the alkyl
ethoxylate surfactant is selected from the group consisting of comprising from
8
to 18 carbon atoms in the hydrophobic chain length, and an average of 1 to 15
ethylene oxide moieties per surfactant molecule and mixture thereof.

6. A composition according to any of the preceding claims, wherein said
polymeric biguanide is an oligo- or poly-hexamethylene biguanide or a salt
thereof or a mixture thereof, preferably said polymeric biguanide is poly
(hexamethylene biguanide) hydrochloride.

7. A composition according to any of the preceding claims, wherein the pH is
achieved using from 0.01 % to 30% of an acidifying agent; and wherein the
level
of said low-residue surfactant and/or an alkyl ethoxylate surfactant is from
0.01%

46



to 15%; the level of biguanide is from 0.01 % to 20%; and the pH of the
aqueous
composition is from 0.5 to 7.

8. A composition according to claim 3 wherein at recommended use levels, the
level of said organic acidifying agent is from 0.01 % to 3.0%, preferably from
0.05% to 2.0%, more preferably from 0.1 % to 1.0%; the level of said low-
residue
surfactant and/or an alkyl ethoxylate surfactant is from 0.01 % to 1.5%,
preferably
from 0.01 % to 1.0%, more preferably from 0.03% to 0.75%; the level of said
polymeric biguanide is from 0.01 % to 2.0%, preferably from 0.01 % to 1.0%,
more
preferably from 0.02% to 0.75%; and the pH of the aqueous composition is from
0.5 to 7, preferably from 1.0 to 6.0, more preferably from 2.0 to 5.5.

9. A composition according to any of the preceding claims, wherein the total
level
of solids does not exceed 3% by weight of the aqueous composition.

10. A composition according to any of the preceding claims, that additionally
comprises from 0.5% to 25% of a solvent or a mixture thereof.

11. A composition according to claim 10, wherein said solvent has a vapour
pressure of 6.66 Pa (0.05 mm Hg at 25°C and atmospheric pressure).

12. A composition according to any of the preceding claims, that additionally
comprises a hydrotrope or a mixture thereof, preferably a hydrotrope selected
from the group consisting of alkyl ethoxylates comprising from 8 to 18 carbon
atoms in the hydrophobic group and at least an average of 15 ethoxylate groups
per hydrophobic group and mixtures thereof.

13. A composition according to any of the preceding claims, wherein said
surfactant is selected in order to provide an Extracompa® black shiny
ceramic tile
treated with said composition with a gloss-meter reading such that at a 95%
confidence level, the composition does not cause a significant loss in gloss
on
the tiles, relative to clean untreated tiles, when tested with a BYK-Gardner
micro-
TRI-gloss gloss-meter® using a 60° angle setting.

14. A composition according to any of the claims 1 to 12, wherein said
surfactant
is selected in order to provide an Extracompa® black shiny ceramic tile
treated

47


with said composition with a gloss-meter reading such that at a 95% confidence
level, composition causes a significant gain of gloss, relative to identical
compositions not comprising the polymeric biguanide, when tested with a BYK-
Gardner micro-TRI-gloss gloss-meter~ using a 60° angle setting.

15. A method of cleaning hard surfaces comprising the step of contacting said
surface with an aqueous composition according to any of the preceding claims.

16. A method of cleaning hard surfaces according to claim 15 wherein said
method additionally comprises the step of wiping said surface during and/or
after
the step of contacting said surface with said aqueous composition, preferably
wherein said step of wiping said surface is performed by contacting said
surface
with a cleaning tool selected from the group consisting of sponges, cloths,
cellulose strings or strips, clean paper or commercially available paper
towels, or
pre-moistened wipe laminates or absorbent disposable cleaning pads.

17. A method of cleaning according to any of claims 15 and 16 wherein said
aqueous composition is applied, preferably sprayed, onto said cleaning tool
prior
to and/or during the wiping of said surface.

18. A method of cleaning according to claim 15 wherein the cleaning of a
surface
is accomplished by using said liquid composition in conjunction with a sponge,
cloth, brush, paper or paper towel.

48


Description

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



CA 02460435 2004-03-16
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AQUEOUS COMPOSITIONS FOR TREATING A SURFACE
Field of the Invention
The present invention relates to antimicrobial compositions for treating a
surface,
in particular to aqueous liquid compositions. The compositions comprise a
polymeric biguanide. Aqueous compositions according to the present invention
were found to exhibit a superior filming/streaking and shine
2o retention/enhancement profile, as measured using a standard gloss-meter,
whilst
providing excellent disinfecting and/or antimicrobial benefits.
Background of the Invention
Liquid compositions for treating hard surfaces, such as, kitchen and bathroom
surfaces, eyeglasses, and surfaces that require cleaning in industry for
example
surfaces of machinery or automobiles are known in the art. Such compositions
can be used as such in a neat cleaning operation or in diluted form. Such
compositions are often used in combination with conventional wiping products
or
3o more recently in combination with absorbent disposable cleaning pads.
Conventional wiping products are typically natural or synthetic sponges, soft
or
scouring pads, brushes, cloths, paper towels. Such wiping products can be
used,
as desired, in combination with cleaning implements comprising a handle for
tough to reach areas or for the cleaning of floors, walls, or other large area
surfaces either inside or outside the home, in office settings or in
commercial or


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WO 03/031546 PCT/US02/32197
public establishments. Such devices can also have the wiping element combined
or built into the handle such as sponge mops, string mops and strip mops.
Pre-moistened wipe cleaning products in the form of laminates are commercially
available. One example is Swifter Wet~, a tri-laminate wipe that comprises an
aqueous composition impregnated on a point-bonded floor sheet, a cellulosic
reservoir core and a spunbond attachment sheet. Such products are further
detailed in WO 2000-2000US26401, incorporated herein by reference.
o Absorbent disposable cleaning pads represent a new method of cleaning,
geared
toward achieving outstanding end result. These disposable pads are
advantageous in that they not only loosen dirt, but also absorb more of the
dirty
solution as compared to conventional cleaning tools or pre-moistened wipes. As
a result, surfaces are left with reduced residue and dry faster. The use of
disposable pads comprising super-absorbent polymer, i.e., absorbent disposable
cleaning pads are particularly advantageous in that the polymer improves the
mileage, longevity, reuse-ability and economic value of the pads. Such pads
are
disclosed in U.S. Pat. No 6,048,123; 6,003,191; 5,960,508; and 6,101,661;
incorporated herein by reference. The pads can be used as stand-alone products
or in combination with an implement comprising a handle, particularly for the
cleaning of floor surfaces. An example of such a product is currently sold by
Procter and Gamble under "Swifter WETJET°".
A commonly known problem in treating hard surfaces is the formation of films
and/or streaks on surfaces treated therewith. Indeed, after the treatment of a
hard surface with a liquid composition, the formation of visible residues
(streaks)
and/or shine reducing films after drying can often be observed.
Furthermore, the addition of an antimicrobial agent, to compositions intended
to
3o wipe and clean surfaces, increases the tendency of filming/streaking on
said
hard. The filming/streaking is particularly problematic when treating glossy
surfaces, such as porcelain, chrome and other shiny metallic surfaces, tiles
etc.
It is therefore an object of this invention to provide a composition that
shows a
filming/streaking performance benefit (low or substantially no formation of
streak
and/or film-formation).
2


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It has now been found that the above objective can be met by a composition for
treating a hard surface having a pH of about 7 or less and comprising at least
one
low-residue surfactant and/or an alkyl ethoxylate surfactant; and a polymeric
biguanide.
It is an advantage of this invention to provide aqueous compositions, either
in
dilutable or in neat form that can be used in conjunction with sponges,
cloths,
rags, paper towels and the like. Such products can function as stand-alone
1o products or can be used in combination with conventional cleaning
implements
including sponge mops, string mops, strip mops or used with an absorbent
disposable cleaning pad that is optionally attached to a cleaning implement
comprising a handle and mop head.
It is another an advantage that judicious selection of surfactant and
composition
pH, can result in an enhancement of the gloss on the tiles, either versus
clean
untreated tiles, or tiles treated with a base composition that lacks the
polymeric
biguanide.
2o It is another advantage of this invention to provide disinfecting or
antimicrobial
compositions that leave little or no visible residue on hard surfaces.
Furthermore,
such compositions can be used in conjunction with cleaning tools with or
without
cleaning implements (defined herein after), including sponges, cellulose
strings or
strips, clean paper or commercially available paper towels, or absorbent
disposable cleaning pads or substrate.
Advantageously, the compositions herein may be used to treat shiny and matt
hard-surfaces made of a variety of materials like glazed and non-glazed
ceramic
tiles, vinyl, no-wax vinyl, linoleum, melamine, glass, plastics, plastified
wood.
A further advantage of the present invention is that an excellent cleaning
performance is obtained on different types of stains and soils.
Background art
3


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Aqueous compositions comprising polymeric biguanides are known in the art. For
example, WO 98/56253 discloses a composition comprising a carrier and a
polymeric biguanide compound in the form of its salt with an organic acid
containing from 4 to 30 carbon atoms such as poly (hexamethylene biguanide)
stearate. These compositions comprising poly (hexamethylene biguanide) exhibit
high antimicrobial, especially antibacterial activity, and exhibit increased
solubility
in organic media, especially organic liquids. U.S. 5,141,803 discloses
compositions for use in hard surfaces comprising biguanide antimicrobial
compounds. EP 0 185 970 describes liquid disinfectant preparations for use on
1o hard surfaces comprising specific oligo-hexamethyl biguanides, specific
microbiocidically active phenolic compounds and, optionally builders. U.S.
6,045,817 discloses an antibacterial cleaning composition (pH >_ 7.5)
comprising
(1 ) 0.05%-1 % of a cationic polymer having a charge density of 0.0015 or
higher,
(2) 0.2-5% of a zwitterionic surfactant, and (3) 0.2-5% of a biguanide
compound.
Much effort has recently been devoted to the search and identification of a
low
residue composition that provides antimicrobial effectiveness. For example, US
pat. Nos. 6,159,924, 6,090,771, and 5,929,016 disclose low residue aqueous
hard surface cleaning compositions comprising quaternary amine compounds, an
organic solvent system and selected surfactant combinations. However, none of
the compositions in the art are found to be completely satisfactory.
Summary of the Invention
The present invention relates to aqueous liquid composition (i) having a pH of
about 7 or less and comprising (ii) at least about one low-residue surfactant
and/or an alkyl ethoxylate surfactant; and (iii) a polymeric biguanide.
The compositions simultaneously deliver excellent cleaning properties against
3o acid- and alkaline-sensitive soils, excellent filming/streaking properties
on a
variety of hard surfaces and high biocidal effectiveness against relevant Gram
positive and Gram negative organisms found in consumer homes, public
domains, or commercial establishments.
Accordingly, the compositions of the present invention are preferably used for
wiping and cleaning various surfaces, preferably hard surfaces.
4


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Detailed Description of the Invention
Definitions
By 'cleaning tool' it is meant any material used to clean surfaces. A cleaning
tool,
as defined herein, must directly contact the surface to be cleaned. Cleaning
tool
materials include conventional cleaning aids such as sponges, cloths,
cellulose
strings or strips, paper or commercially available paper towel, as well as
novel
cleaning tools including floor wipe laminates and absorbent disposable
cleaning
pads.
By 'implement' or 'cleaning implement', it is meant any material used in
conjunction with cleaning tools to make the cleaning job easier, more
efficient or
~5 more convenient. Cleaning implements consist of mop heads or short or long
pole attachments with or without the mop heads, or other means used to attach,
in any manner possible, a cleaning tool.
By 'absorbent' it is meant any material or laminate that can absorb at least
about
20 1 gram of de-ionized per gram of said material.
By 'absorbent disposable cleaning pad' it is meant an absorbent pad that is
typically used for a cleaning job and then disposed of. Absorbent disposable
cleaning pads can range from simple dry absorbent non-woven structures to
25 multi-layered absorbent composites. While it is understood that some pad
designs can be used, stored and re-used, the amount of re-use is limited and
is
typically determined by the ability of the pad to continue to absorb more
liquid
and/or dirt. Unlike conventional systems such as sponge mops, strip and string
mops, which are considered fully re-usable, once saturated, an absorbent
3o disposable pad is not designed to be reversed by the consumer to get it
back to
its original state.
Aaueous Composition
35 The composition of the present invention is formulated as a liquid
composition. A
preferred composition herein is an aqueous composition and therefore,
preferably
5


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comprises water more preferably in an amount of from about 50% to about 99%,
even more preferably of from about 60% to about 98% and most preferably about
70% to about 97% by weight of the total composition.
The aqueous compositions of the present invention comprise a pH of about 7 or
less and at least about one surfactant so as to lower the contact angle
between
the compositions and relevant hard surfaces, thereby assisting the wetting of
such surfaces. The compositions also include a polymeric biguanide compound,
which in the presence of the surfactant, acts as a hydrophilic wetting agent
and
1o preferably as an antimicrobial compound. In a preferred embodiment, the
surfactant is a low residue surfactant, as further described herein. In
another
highly preferred embodiment, the aqueous compositions also comprise at least
one water-soluble solvent with a vapour pressure of greater than about 0.05 mm
Hg at 1 atmosphere pressure (about 6.66 Pa).
The solids content of the aqueous compositions of the present invention, at
usage levels is generally low, preferably from about 0% to about 4%, more
preferably from about 0.05% to about 3%, most preferably from about 0.10% to
about 2.0%. Those skilled in the art will recognize that the aqueous
compositions
of the present invention can be made in the form of about 5X, about 10X, or
even
higher concentrates as desired, and then diluted prior use. This is expected
particularly when the aqueous composition is sold as a liquid intended to be
diluted in a bucket or other receptacle. The making of concentrated solutions
can
also be beneficial if the aqueous composition must be transported.
Composition pH
The aqueous compositions have a pH of about 7 or less. It is found that the
filming and streaking benefits are not observed, or are substantially
attenuated, at
a pH higher than about 7. The pH range of the compositions is preferably from
about 0.5 to about 7, more preferably from pH about 1.0 to about 6, more
preferably from pH about 2 to about 5.5, and most preferably from pH about 2.5
to about 5.
6


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In one preferred embodiment, the aqueous composition has a pH of from about 5
to about 7 and does not include an acidifying agent. In this embodiment the
benefits of the invention are most noteworthy when the aqueous composition
comprises at least about one surfactant selected from the group consisting of
C8-
16 poly alkyl glycosides.
Acidifying agent
In the preferred embodiment wherein the aqueous composition herein comprises
at least one acidifying agent, the pH range of the compositions is preferably
from
about 0.5 to about 7, more preferably from pH about 1.0 to about 6, more
preferably from pH about 2 to about 5.5, and most preferably from pH about 2.5
to about 5. A suitable acid for use herein is an organic and/or an inorganic
acid,
most preferably an organic acid. Suitable organic acids are monomeric,
oligomeric or polymeric organic acids.
Examples of a suitable organic acids include acetic acid, glycolic acid,
lactic acid,
succinic acid, adipic acid, malic acid, tartaric acid, lactic acid,
polyacrylic acid,
2o poly-aspartic acid, and the like. Highly preferred organic acids are
selected from
the group consisting of succinic acid, glutaric acid, adipic acid, lactic
acid, tartaric
acid and citric acid. For cost, availability, buffering capacity and
regulatory
reasons, citric acid (food grade desired but not required) is most preferred.
A typical level of organic acid for product is from about 0.01 % to about 30%,
preferably from about 0.05% to about 10% and more preferably from about 0.1
to about 7.5% by weight of the total composition. At the actual product use
levels,
following recommended product dilution, if any, a typical level of organic
acid is of
from about 0.01 % to about 3%, preferably from about 0.05% to about 2% and
3o more preferably from about 0.1 % to about 0.75% by weight of the total
composition. The specific level of acid will depend on the magnitude and type
of
the benefits sought. Higher levels promote improved cleaning of acid-sensitive
soils while lower levels provide better filming streaking. The most preferred
levels
have been found to provide a combination of adequate buffering capacity,
excellent cleaning and good filming/streaking properties. As such, organic
acids
7


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
selected from the group consisting of citric acid, tartaric acid and lactic
acid are
highly preferred. -
In a preferred embodiment, the compositions are applied on hard surfaces
soiled
with hard watermarks, limescale andlor soap scum, and the like. Such soils are
frequently encountered on bathroom surfaces. Accordingly, the compositions
herein may further comprise acid or base buffers to adjust pH as appropriate.
Low-residue surfactant:
In a particularly preferred embodiment, the composition according to the
present
invention comprises a low-residue surfactant or a mixture thereof.
By "low-residue surfactant" it is meant herein any surfactant that mitigates
the
appearance of either streaks or films upon evaporation of the aqueous
compositions comprising said surfactant. A low residue surfactant-containing
composition may be identified using either gloss-meter readings or expert
visual
grade readings. The conditions for the determination of what constitutes a low-

residue surfactant are one of the following: (a) less than about 1.5% gloss
loss on
2o black shiny porcelain tiles, preferably on black shiny Extracompa~
porcelain tiles
used in this invention; or (b) lack of significant filming and/streaking as
judged by
one skilled in the art. One of the important advantages of the low residue
surfactant is that it requires less polymeric biguanide compound for gloss
enhancement, relative to non-low residue surfactants. This can be important in
light of cost considerations, potential stickiness issues delivered by higher
concentrations of the polymeric biguanide, andlor concerns over the ability to
completely strip a more concentrated polymeric biguanide film.
Whilst not wishing to be limited by theory, it is believed that low-residue
3o surfactants exhibit a reduced tendency for inter-molecular aggregation.
With less
aggregation of surfactant molecules to form visible macromolecular complexes
following evaporation of water from the aqueous compositions, the remaining
residue is less visible, resulting in fewer streaks. Unlike conventional non-
ionic
surfactants such as alkyl ethoxylates and alkyl phenol ethoxylates, which
exhibit
rich phase chemistry, the "low residue" surfactants do not easily form
anisotropic
macromolecular structures in water, which helps make the film which they form
s


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upon dry-down from solution less visible. Indeed, the residue is observed to
be
nearly colorless, leading to films that are essentially not visible to the
naked eye
or in some instances, films that enhance the gloss of the treated tiles.
As identified within this invention there care three classes of low-residue
surfactants: selected non-ionic surfactants, and zwitterionic surfactants and
amphoteric surfactants and mixtures thereof. One class of low residue
surfactants is the group of non-ionic surfactants that include a head group
consisting of one or more sugar moieties. Examples include alkyl
polyglycosides,
especially poly alkyl glucosides, and sucrose esters. The chain length of
these
non-ionic surfactants is preferably about C6 to about C18, more preferably
from
about C8 to about C16. The hydrophilic component of these surfactants may
comprise one or more sugar moieties liked by glycosidic linkages. In a
preferred
embodiment, the average number of sugar moieties per surfactant chain length
is
~ 5 from about 1 to about 3, more preferably from about 1.1 to about 2.2.
The most preferred non-ionic low residue surfactants are the
alkylpolysaccharides that are disclosed in U.S. Patents: U.S. No. 5,776,872,
Cleansing compositions, issued July 7, 1998, to Giret, Michel Joseph;
Langlois,
2o Anne; and Duke, Roland Philip; U.S. Pat. No 5,883,059, Three in one ultra
mild
lathering antibacterial liquid personal cleansing composition, issued March
16,
1999, to Furman, Christopher Allen; Giret, Michel Joseph; and Dunbar, James
Charles; etc.; U.S. Pat No. 5,883,062, Manual dishwashing compositions, issued
March 16, 1999, to Addison, Michael Crombie; Foley, Peter Robert; and
25 Allsebrook, Andrew Micheal; and U.S. Pat. No. 5,906,973, issued May 25,
1999,
Process for cleaning vertical or inclined hard surfaces, by Ouzounis,
Dimitrios
and Nierhaus, Wolfgang.
Suitable alkyl polyglucosides for use herein are disclosed in U.S. Patent No.
30 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about 10 to
about 16 carbon atoms and polysaccharide, e.g., a polyglycoside, hydrophilic
group containing from about 1.3 to about 10, preferably from about 1.3 to
about
3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing
35 saccharide containing about 5 or about 6 carbon atoms can be used, e.g.,
glucose, galactose, and galactosyl moieties can be substituted for the
glucosyl
9


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moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-,
etc.
positions thus giving a glucose or galactose as opposed to a glucoside or
galactoside.). The intersaccharide bonds can be, e.g., between the one
position
of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions of
the
preceding saccharide units. The glycosyl is preferably derived from glucose.
Optionally, there can be a polyalkyleneoxide chain joining the hydrophobic
moiety
and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide.
Typical hydrophobic groups include alkyl groups, either saturated or
unsaturated,
1o branched or unbranched containing from about 8 to about 18, preferably from
about 10 to about 16, carbon atoms. Preferably, the alkyl group can contain up
to
about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to
about 10, preferably less than about 5, alkyleneoxide moieties. Suitable alkyl
polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-,
and
hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses
and/or
galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
2o The preferred alkylpolyglycosides have the formula:
R20(~nH2n0)t(9lucosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
contain from about 10 to about 18, preferably from about 12 to about 14,
carbon
atoms; n is about 2 or about 3, preferably about 2; t is from 0 to about 10,
preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3
to
about 3, most preferably from about 1.3 to about 2.7. The glycosyl is
preferably
3o derived from glucose. To prepare these compounds, the alcohol or
alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source
of glucose, to form the glucoside (attachment at the 1-position). The
additional
glycosyl units can then be attached between their 1-position and the preceding
glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominantely the 2-
position.


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Zwitterionic surfactants represent a second class of highly preferred low
residue
surfactants. Zwitterionic surfactants contain both cationic and anionic groups
on
the same molecule over a wide pH range. The typical cationic group is a
quaternary ammonium group, although other positively charged groups like
sulfonium and phosphonium groups can also be used. The typical anionic groups
are carboxylates and sulfonates, preferably sulfonates, although other groups
like
sulfates, phosphates and the like, can be used. Some common examples of
these detergents are described in the patent literature: US Pat. No.
2,082,275,
2,702,279 and 2,255,082, incorporated herein by reference.
A generic formula for some preferred zwitterionic surfactants is:
R-N+(R2)(Rs)(Ra.)X ,
wherein R is a hydrophobic group; R2 and R3 are each a C1-4 alkyl hydroxy
alkyl
or other substituted alkyl group which can be joined to form ring structures
with
the N; R4 is a moiety joining the cationic nitrogen to the hydrophilic anionic
group,
and is typically an alkylene, hydroxy alkylene, or polyalkoxyalkylene
containing .
from one to four carbon atoms; and X is the hydrophilic group, most preferably
a
2o sulfonate group.
Preferred hydrophobic groups R are alkyl groups containing from about 6 to
about 20 carbon atoms, preferably less than about 18 carbon atoms. The
hydrophobic moieties can optionally contain sites of instauration and/or
2o substituents and/or linking groups such as aryl groups, amido groups, ester
groups, etc. In general, the simple alkyl groups are preferred for cost and
stability
reasons. A specific example of a "simple" zwitterionic surfactant is 3-(N-
dodecyl-
N,N-dimethyl)-2-hydroxypropane-1-sulfonate available from the Degussa-
Goldschmidt Company under the tradename Variori HC~.
Other specific zwitterionic surfactants have the generic formula:
R-C(O)-N(R~)-(CR32)n-N(R2) 2+-(CR32)n-SO3
wherein each R is a hydrocarbon, e.g., an alkyl group containing from about 6
to
about 20, preferably up to about 18, more preferably up to about 16 carbon
11


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
atoms, each (R2) is either a hydrogen (when attached to the amido nitrogen),
short chain alkyl or substituted alkyl containing from about 1 to about 4
carbon
atoms, preferably groups selected from the group consisting of methyl, ethyl,
propyl, hydroxy substituted ethyl and propyl and mixtures thereof, more
preferably methyl, each (R3) is selected from the group consisting of hydrogen
and hydroxyl groups, and each n is a number from about 1 to about 4, more
preferably about 2 or about 3, most preferably about 3, with no more than
about 1
hydroxy group in any (CR32) moiety. The R group can be linear or branched,
saturated or unsaturated. The R2 groups can also be connected to form ring
1o structures. A highly preferred low residue surfactant of this type is a C12-
14
acylamidopropylene (hydroxypropylene) sulfobetaine that is available from
Degussa-Goldschmidt under the tradename Rewoteric AM CAS-15U~.
Compositions of this invention containing the above hydrocarbyl amido
sulfobetaine can contain more perfume and/or hydrophobic perfumes than similar
compositions containing conventional anionic surfactants. This can be
desirable
in the preparation of consumer products.
Other very useful zwitterionic surfactants include hydrocarbyl, e.g., fatty
alkylene
2o betaines. These surfactants tend to become more cationic as pH is lowered
due
to protonation of the carboxyl anionic group, and in one embodiment have the
generic formula:
R-N(R~ )2+-(CR22)n-COO-,
wherein R is a hydrocarbon, e.g., an alkyl group containing from about 6 to
about
20, preferably up to about 18, more preferably up to about 16 carbon atoms,
each
(R~) is a short chain alkyl or substituted alkyl containing from about 1 to
about 4
carbon atoms, preferably groups selected from the group consisting of methyl,
3o ethyl, propyl, hydroxy substituted ethyl and propyl and mixtures thereof,
more
preferably methyl, (R2) is selected from the group consisting of hydrogen and
hydroxyl groups, and n is a number from about 1 to about 4, preferably about
1. A
highly preferred low residue surfactant of this type is Empigen BB~, a coco
dimethyl betaine produced by Albright & Wilson.
12


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In another equally preferred embodiment, these betaine surfactants have the
generic formula:
R-C(O)-N(R2)-(CR32)~ N(R~) 2+-(CR32)n-C%00-
wherein each R is a hydrocarbon, e.g., an alkyl group containing from about 6
to
about 20, preferably up to about 18, more preferably up to about 16 carbon
atoms, each (R2) is either a hydrogen (when attached to the amido nitrogen),
short chain alkyl or substituted alkyl containing from about 1 to about 4
carbon
1o atoms, preferably groups selected from the group consisting of methyl,
ethyl,
propyl, hydroxy substituted ethyl and propyl and mixtures thereof, more
preferably methyl, each (R3) is selected from the group consisting of hydrogen
and hydroxyl groups, and each n is a number from about 1 to about 4, more
preferably about 2 or about 3, most preferably about 3, with no more than
about 1
hydroxy group in any (CR32) moiety. The R group can be linear or branched,
saturated or unsaturated. The R2 groups can also be connected to form ring
structures. A highly preferred low residue surfactant of this type is TEGO
Betain
F~, a coco amido propyl betaine produced by Degussa-Goldschmidt.
2o The third class of preferred low-residue surfactants comprises the group
consisting of amphoteric surfactants. These surfactants function essentially
as
zwitterionic surfactants at acidic pH. One suitable amphoteric surfactant is a
C8-
C16 amido alkylene glycinate surfactant ('ampho glycinate'). Another suitable
amphoteria surfactant is a CB-C16 amido alkylene propionate surfactant ('ampho
propionate'). These surfactants are essentially cationic at acidic pH and have
the
generic structure:
R-C(O)-(CH2)~-N(R~ )-(CH2)X-COOH,
3o wherein R-C(O)- is a about C5 to about C15, pre hydrophobic fatty acyl
moiety,
each n is from about 1 to about 3, each R1 is preferably hydrogen or a C1-C2
alkyl or hydroxyalkyl group, and x is about 1 or about 2. Such surfactants are
available, in the salt form, from Degussa-Goldschmidt chemicals under the
tradename Rewoteric AM~. Examples of other suitable low residue surfactants
include cocoyl amido ethyleneamine-N-(methyl) acetates, cocoyl amido
13


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ethyleneamine-N-(hydroxyethyl) acetates, cocoyl amido propyleneamine-N-
(hydroxyethyl) acetates, and analogs and mixtures thereof.
Other suitable, amphoteric surfactants being either cationic or anionic
depending
upon the pH of the system are represented by surfactants such as dodecylbeta-
alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine
with
sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072, N-
higher alkylaspartic acids such as those produced according to the teaching of
U.S. Pat. No. 2,438,091, and the products sold under the trade name
"Miranol~",
1o and described in U.S. Pat. No. 2,528,378, said patents being incorporated
herein
by reference.
Low-residue surfactants contribute to the filming/streaking performance (i.e.,
low
or substantially no streaks- and/or film-formation) of the compositions
according
to the present invention. Whilst not wishing to be limited by theory, it is
believed
that the bulky sugar moieties of alkyl polyglycosides and sucrose esters
function
to inhibit the aggregation of surfactant that occurs upon evaporation of water
in
the aqueous solutions of the present invention. It is also believed that the
zwitterionic and amphoteric surfactants show reduced aggregation relative to
2o conventional surfactants because the intra-molecular electrostatic
attractions
between the anionically and cationically charged groups are stronger than the
intermolecular surfactant-surfactant attractions. This results in a reduced
tendency for molecular assembly that inhibits visible residue.
In a preferred embodiment according to the present invention, the low-residue
surfactant herein is selected in order to provide an Extracompa~ black shiny
porcelain tile treated with the composition herein with a gloss-meter reading
such
that at a 95% confidence level, the composition does not cause a significant
loss
in gloss on the tiles, relative to clean untreated tiles, when tested with a
BYK
3o gloss-meter~ using a 60° angle setting. The above test is performed
as
described herein below.
By 'not significant loss in gloss', it is meant herein that the mean
difference in
gloss between tiles treated with two separate treatments using 15 readings for
each is not statistically significant ( a =0.05). Similarly, by 'significant
enhancement (or gain) in gloss', it is meant herein that the mean difference
in
14


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WO 03/031546 PCT/US02/32197
gloss between tiles treated with two separate treatments using 15 readings for
each is statistically significant ( a =0.05). In these filming/streaking
tests,
statistical significance is established at the 95% confidence level ( a
=0.05), using
a one-tailed test and pair-wise statistical treatment of the samples. All
samples
are assumed to exhibit a normal distribution with equal variances. Using the
raw
data, t-tests are calculated and compared to the critical t statistic. When
the
calculated t-test exceeds t-critical, the samples are 'significantly'
different. When
t-calculated is less than t-critical, the samples are not 'significantly'
different. The
direction of the significance is determined by sign of the mean differences
(i.e.,
'either mean treatment 8', 'mean 8 (PHMB-noPHMB)' or 'mean 8 (PHMB-Quat)'.
For example, if the mean gloss for a treatment is higher than that of the
untreated
tile, and t calculated exceeds t-critical, then the data suggest that at a 95%
confidence level ( a =0.05) the treatment has a significantly higher gloss
than the
untreated tile. The statistics treatment of dependent paired samples ('mean
treatment 8') and independent paired samples ('mean 8 PHMB-noPHMB' or
'mean ~ (PHMB-Quat') can be found in Anderson, Sweeney and Williams,
Statistics for Business and Economics, 6t" edition, West Publishing Company,
1996, incorporated herein by reference. The statistics can be conveniently run
using the statistical function in Microsoft Excel. Excel provides a P-value,
which
2o corresponds to the level of significance of the results. P-values below
0.05
indicate statistical significance at a =0.05; P-values above 0.05 indicate no
statistical significance at a =0.05.
In another preferred embodiment according to the present invention, the low
residue surfactant herein is selected in order to provide an Extracompa~ black
shiny ceramic tile treated with the compositions herein with a gloss-meter
reading
such that at a 95% confidence level, the composition causes a significant
enhancement/gain of gloss, relative to tiles treated with a similar
composition not
comprising the polymeric biguanide, when tested with a BYi< gloss-meter~ using
so a 60° angle setting. The above test is performed as described herein
below.
Low-residue surfactants can be present in the compositions of this invention
at
levels from about 0.01 % to about 15%, preferably of from about 0.01 % to
about
10%, and more preferably of from about 0.03% to about 0.75% by weight of the
total composition. At actual product use levels, following recommended product
dilution, if any, the low-residue surfactants are typically present at levels
from


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
about 0.01 % to about 1.5%, more preferably from about 0.01 % to about 10%,
and more preferably of from about 0.03% to about 0.75% by weight of the total
composition. Importantly, the Applicant has found that the use of a low
residue
surfactant in combination with a conventional surfactant (i.e., non- low
residue)
can mitigate filming and/or streaking issues relative to similar compositions
that
only use the conventional surfactant.
Polymeric biguanide:
1o As an essential ingredient the composition according to the present
invention
comprises a polymeric biguanide. Any polymeric biguanide known to those
skilled
in the art may be used herein.
Polymeric biguanides are characterised in comprising at least one, preferably
about 2 or more, biguanide moieties according to the following formula:
-NH-C(=NH)-NH-C(=NH)-NH-
In the context of the compositions of this invention, the polymeric biguanide
are
oligo- or poly alkylene biguanides or salts thereof or mixtures thereof. More
preferred polymeric biguanides are oligo- or poly hexamethylene biguanides or
salts thereof or mixtures thereof.
In a most preferred embodiment according to the present invention said
polymeric biguanide is a poly (hexamethylene biguanide) or salt thereof
according to the following formula:
-~-(CH2)3-N H-C(=N H )-NH-C(=N H )-N H-(CH2)3-]n-
3o wherein n is an integer selected from about 1 to about 50, preferably about
1 to
about 2p, more preferably about 9 to about 18. More preferably said biguanide
antimicrobial agents is a salt of a poly (hexamethylene biguanide) according
to
the following formula:
-[-(CH2)3-NH-C(=NH)-NH-C(=NH)-NH-(CH2)s-]n- .nHX
16


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
wherein n is an integer selected from about 1 to about 50, preferably about 1
to
about 20, more preferably about 9 to about 18, and HX is salt component,
preferably HCI.
None of the non-polymeric materials will work- the polymer is needed for
wetting.
A most preferred poly (hexamethylene biguanide) hydrochloride (PBG) wherein in
the above formula n=12, is commercially available under the trade name
Vantocil
P~, Vantocil IB~ or Cosmocil CQ~ from Avecia. Another suitable PHMB wherein
1o n=15, is commercially sold by Avecia under the tradename Reputex 20~. The
choice of poly (hexamethylene biguanide) hydrochloride, as the most preferred
polymeric biguanide antimicrobial for the compositions of this invention is
driven
by its unusually good filming and streaking properties within the scope of the
compositions disclosed herein, and by its regulatory status as an approved
antimicrobial active for hard surface cleaning applications in the European
Union
(Biocidal Products Directive) and in the United States (EPA actives list).
The Applicant has found that the micro-effectiveness of PHMB is optimized at
relatively low concentrations of organic acid. For example, the effectiveness
of
2o PHMB as an antimicrobial active in a composition of the invention
comprising
about 0.25% citric acid is enhanced relative to a similar composition
comprising
1 % citric acid. This is advantageous since lower concentrations of acid tend
to
result in improved filming and streaking benefits, all while promoting good
antimicrobial efficiency.
Typically the compositions herein may comprise up to about 20%, preferably
from
about 0.01 % to about 10%, more preferably from about 0.02% to about 7.5 %, by
weight of the total composition of a polymeric biguanide. At the actual
product
use levels, following recommended product dilution, if any, the compositions
3o herein may comprise up to about 2%, preferably from about 0.01 % to about 1
%,
more preferably from about 0.02% to about 0.75%, by weight of the total
composition of a polymeric biguanide. Those skilled in the art will appreciate
that
the level of polymeric biguanide antimicrobial agent is dependent on the
magnitude of the antimicrobial benefits sought. For hygiene claims in Europe,
s5 and sanitization, and 'Limited Disinfection' benefits in Canada and the
United
States, lower levels of polymeric biguanide antimicrobial agent, up to about
17


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WO 03/031546 PCT/US02/32197
0.20%, are sufficient. For complete biocidal effectiveness against Gram
positive
and Gram negative micro-organisms, it is recommended that at least about
0.20%, more preferably about 0.25% most preferably about 0.30% polymeric
biguanide compound be included in the aqueous composition. Higher levels of
biguanide antimicrobial agent may be needed, up to about 1.5%, for
particularly
tough to kill microorganisms such as Trychophyton or other fungi.
Optional components
Surfactant:
The compositions of the present invention can incorporate, in addition to the
essential low-residue surfactants, 'non low-residue' surfactants. These can be
non-ionic, anionic, cationic, zwitterionic or amphoteric, and mixtures
thereof. The
required surfactant is defined as any material with a hydrophobic component
consisting of a hydrocarbon moiety with between about 6 carbon atoms and
about 20 carbon atoms, and a hydrophilic head group. The purpose of the
surfactant is improved wetting of the hard surfaces to be treated. The wetting
properties of the surfactant are essential to the compositions of the
invention. The
2o hydrophobic tail of the surfactant can be linear or branched, aliphatic
aromatic.
The hydrophilic head group can consist of any group such that provides wetting
properties. Said surfactant may be present in the compositions according to
the
present invention in amounts of from about 0.01 % to about 15%, preferably of
from about 0.01 % to about 10%, and more preferably of from about 0.02% to
about 7.5% by weight of the total composition. At actual product use levels,
the
low residue surfactants are typically present at levels from about 0.01 % to
about
1.5%, more preferably from about 0.01 % to about 10%, and more preferably of
from about 0.03% to about 0.75% by weight of the total composition.
3o More specifically, groups of non-ionic surfactants that can be used in the
context
of the following invention are as follows:
(i) The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products of alkyl phenols having an alkyl group containing
from about 6 to about 12 carbon atoms in either a straight chain or branched
chain configuration, with ethylene oxide, the said ethylene oxide being
1S


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
present in amounts equal to about 10 to about 25 moles of ethylene oxide
per mole of alkyl phenol. The alkyl substituent in such compounds may be
derived from polymerized propylene, diisobutylene, octane, and nonane.
(ii) Those derived from the condensation of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene diamine
products, which may be varied, in composition depending upon the balance
between the hydrophobic and hydrophilic elements, which is desired.
Examples are to increase the water-solubility of the molecule as a whole
1o and the liquid character of the products is retained up to the point where
polyoxyethylene content is about 50% of the total weight of the
condensation product; compounds containing from about 40% to about 80%
polyoxyethylene by weight and having a molecular weight of from about
5000 to about 11000 resulting from the reaction of ethylene oxide groups
with a hydrophobic base constituted of the reaction product of ethylene
diamine and excess propylene oxide, said base having a molecular weight
of the order of about 2500 to about 3000.
The condensation product of aliphatic alcohols having from about 6 to about
18 carbon atoms, in either straight chain or branched chain configuration,
with ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof,
e.g., a coconut alcohol ethylene oxide condensate having from about 3 to
about 15 moles of ethylene oxide per mole of coconut alcohol, the coconut
alcohol fraction having from about 10 to about 14 carbon atoms; such
materials are commonly known as 'alkyl alkoxylates' or 'alcohol alkoxylates'.
In some cases, an alkyl ethoxylates can have capping groups, meaning that
they have the structure R1-(EO)XR2, where R1 is a C6-C18 linear or
branched moiety, x is from about 1 to about 15 and R2, the capping group,
is a about C1 to about C8 hydrocarbyl moiety.
(iv) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl
group
ranges from about 10 to about 18 carbon atoms and two alkyl groups range
from about 1 to about 3 carbon atoms; the alkyl groups can contain hydroxy
substituents; specific examples are dodecyl di(2-hydroxyethyl)amine oxide
and tetradecyl dimethyl phosphine oxide.
19


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Although not preferred, the condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with propylene
glycol are also suitable for use herein. The hydrophobic portion of these
compounds will preferably have a molecular weight of from about 1500 to about
1800 and will exhibit water insolubility. The addition of polyoxyethylene
moieties
to this hydrophobic portion tends to increase the water solubility of the
molecule
as a whole, and the liquid character of the product is retained up to the
point
where the polyoxyethylene content is about 50% of the total weight of the
condensation product, which corresponds to condensation with up to about 40
o moles of ethylene oxide. Examples of compounds of this type include certain
of
the commercially available Pluronic~ surfactants, marketed by BASF.
Chemically, such surfactants have the structure (EO)X(PO)y(EO)~ or
(PO)X(EO)Y(PO)Z wherein x, y, and z are from about 1 to about 100, preferably
about 3 to about 50. Pluronic~ surfactants known to be good wetting
surfactants
~5 are more preferred. A description of the Pluronic~ surfactants, and
properties
thereof, including wetting properties, can be found in the brochure entitled
BASF
Performance Chemicals Plutonic~ & Tetronic~ Surfactants", available from
BASF and incorporated herein by reference.
2o Also not preferred, although suitable as non-ionic surfactants herein are
the
condensation products of ethylene oxide with the product resulting from the
reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of
these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from about 2,500 to
25 about 3,000. This hydrophobic moiety is condensed with ethylene oxide to
the
extent that the condensation product contains from about 40% to about 80% by
weight of polyoxyethylene and has a molecular weight of from about 5,000 to
about 11,000. Examples of this type of non-ionic surfactant include certain of
the
commercially available Tetronic~ compounds, marketed by BASF.
Other non-ionic surfactants, though not preferred, for use herein include
polyhydroxy fatty acid amides of the structural formula:
O R1
(I) R~-C-N-Z


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a
mixture thereof, preferably C1-Cq. alkyl, more preferably C1 or C2 alkyl, most
preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably
straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17
alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or
mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl
chain with at least about 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
o preferably will be derived from a reducing sugar in a reductive amination
reaction;
more preferably Z is a glycityl. Suitable reducing sugars include glucose,
fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials,
high dextrose corn syrup can be utilised as well as the individual sugars
listed
above. These corn syrups may yield a mix of sugar components for Z. It should
be understood that it is by no means intended to exclude other suitable raw
materials. Z preferably will be selected from the group consisting of -CH2-
(CHOH)n-CH20H, -CH(CH~OH)-(CHOH)n_1-CH20H, -CH~-
(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from about 3 to about
5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and
alkoxylated
o derivatives thereof. Most preferred are glycityls wherein n is 4,
particularly -CH~-
(CHOH)q.-CH~OH.
In Formula (I), R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-
isopropyl,
N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl, R~-CO-N< can be, for
example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide,
palmitamide, tallowamide, etc., Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-
deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-
deoxymaltotriotityl, etc.
so Another type of suitable non-ionic surfactants for use herein are the 2-
alkyl
alkanols having an alkyl chain comprising from about 6 to about 16, preferably
from about 7 to about 13, more preferably from about ~ to about 12, most
preferably from about 8 to about 10 carbon atoms and a terminal hydroxy group,
said alkyl chain being substituted in the a position (i.e., position number 2)
by an
s5 alkyl chain comprising from about 1 to about 10, preferably from about 2 to
about
8 and more preferably about 4 to about 6 carbon atoms.
21


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Such suitable compounds are commercially available, for instance, as the
Isofol
~ series such as Isofol~ 12 (2-butyl octanol) or Isofol~ 16 (2-hexyl decanol)
commercially available from Condea.
A detailed listing of suitable non-ionic surfactants useful in this invention
can be
found in U.S. Pat. No. 4,557,853, Collins, issued December 10t", 1985 and
incorporated herein by reference.
Among non-low residue non-ionic surfactants, those formed by the reaction of
an
alcohol with one or more ethylene oxides, are most preferred. These
surfactants
are prone to form highly visible films in the absence of polymeric biguanides.
However, the Applicant has found that addition of low to moderate levels
(e.g.,
about 0.05% to about 0.30%) of the biguanides of the invention to compositions
~5 results in significant toning of the visible film, and leads to enhanced
gloss on tile
that is aesthetically pleasing. In effect, the polymeric biguanides of the
invention
are effective and efficient in removing alkyl ethoxylate-produced visible
films from
tiles. Non-limiting examples of groups of these preferred non-low residue
alkyl
alkoxylates include Neodol~ surfactants (Shell), Tergitol~ surfactants (Union
2o Carbide) and Icconol~ surfactants (BASF). One specific example is Neodol 91-

6~, an alkyl ethoxylate comprising from 9 to 11 carbon atoms and an average of
6 moles of ethoxylation made by Shell.
Anionic surfactants are not preferred, particularly as stand-alone
surfactants, but
25 can also be used in the present invention. Suitable anionic surfactants for
use
herein include alkali metal (e.g., sodium or potassium) fatty acids, or soaps
thereof, containing from about 8 to about 24, preferably from about 10 to
about
20 carbon atoms, linear of branched C6-C16 alcohols, C6-C12 alkyl sulfonates,
C6-C18 alkyl sulfates 2-ethyl-1-hexyl sulfosuccinate, C6-C16 alkyl
carboxylates,
3o C6-C18 alkyl ethoxy sulfates.
The fatty acids including those used in making the soaps can be obtained from
natural sources such as, for instance, plant or animal-derived glycerides
(e.g.,
palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale
oil, fish oil,
35 tallow, grease, lard and mixtures thereof). The fatty acids can also be
synthetically prepared (e.g., by oxidation of petroleum stocks or by the
Fischer-
22


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
Tropsch process). Alkali metal soaps can be made by direct soapification of
fats
and oils or by the neutralization of the free fatty acids which are prepared
in a
separate manufacturing process. Particularly useful are the sodium and
potassium salts of the mixtures of fatty acids derived from coconut oil and
tallow,
i.e., sodium and potassium tallow and coconut soaps.
Other suitable anionic surfactants for use herein include water-soluble salts,
particularly the alkali metal salts, of organic sulphuric reaction products
having in
the molecular structure an alkyl radical containing from about 8 to about 22
carbon atoms and a radical selected from the group consisting of sulfonic acid
and sulphuric acid ester radicals. Important examples of these synthetic
detergents are the sodium, ammonium or potassium alkyl sulfates, especially
those obtained by sulfating the higher alcohols produced by reducing the
glycerides of tallow or coconut oil; sodium or potassium alkyl benzene
sulfonates,
~5 in which the alkyl group contains from about 9 to about 15 carbon atoms,
especially those of the types described in U.S. Pat. Nos. 2,220,099 and
2,477,383, incorporated herein by reference; sodium alkyl glyceryl ether
sulfonates, especially those ethers of the higher alcohols derived from tallow
and
coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and
sulfonates;
2o sodium or potassium salts of sulphuric acid esters of the reaction product
of one
mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and
about three
moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene
oxide
ether sulfates with about four units of ethylene oxide per molecule and in
which
the alkyl radicals contain about 9 carbon atoms; sodium or potassium salts of
25 alkyl ethylene oxide ether sulfates with about four units of ethylene oxide
per
molecule and in which the alkyl radicals contain 6 to 18 carbon atoms; the
reaction product of fatty acids esterified with isothionic acid and
neutralized with
sodium hydroxide where, for example, the fatty acids are derived from coconut
oil; sodium or potassium salts of fatty acid amide of a methyl taurine in
which the
3o fatty acids, for example, are derived from coconut oil; and others known in
the art,
a number being specifically set forth in U.S. Pat. Nos. 2,486,921, 2,486,922
and
2,396,278, incorporated herein by reference. Other suitable anionic
surfactants
include C6-C18 alkyl ethoxy carboxylates, C8-C18 methyl ester sulfonates, 2-
ethyl-1-hexyl sulfosuccinamate, 2-ethyl-1-hexyl sulfosuccinate and the like.
23


CA 02460435 2004-03-16
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Cationic surfactants are not preferred but can be used at low levels in
compositions of the present invention are those having a long-chain
hydrocarbyl
group. Examples of such cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those surfactants having the
formula:
[R2(OR3)yl[R4(OR3)y~2R5N+X_
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
1o carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of
-CH2CH2-, -CH2CH(CHg)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -
CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
~5 polymer having a molecular weight less than about 1000, and hydrogen when y
is
not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of
carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to
about
and the sum of the y values is from 0 to about 15; and X is any compatible
anion.
Other cationic surfactants useful herein are also described in U.S. Patent No.
4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
Solvents
As an optional but highly preferred ingredient the composition herein
comprises
one or more solvents or mixtures thereof. Solvents can provide improved
filming
and/or streaking benefits. Whilst not wishing to be limited by theory, it is
believed
that solvents disrupt micelle formation, thus reducing surfactant aggregation.
As
3o such, they act as gloss toning agents, reducing gloss loss or promoting
gloss
gain on the surfaces of the present invention. Solvents are also beneficial
because of their surface tension reduction properties help the cleaning
profile of
the compositions disclosed herein. Finally, solvents, particularly solvents
with
high vapour pressure, specifically vapour pressures of about 0.05 mm Hg at
25°C
and 1 atmosphere pressure (about 6.66 Pa) or higher, can provide cleaning and
filming and/or streaking benefits without leaving residue.
24


CA 02460435 2004-03-16
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Solvents for use herein include all those known in the art for use in hard-
surface
cleaner compositions. Suitable solvents can be selected from the group
consisting of: aliphatic alcohols, ethers and diethers having from about 4 to
about
14 carbon atoms, preferably from about 6 to about 12 carbon atoms, and more
preferably from about 8 to about 10 carbon atoms; glycols or alkoxylated
glycols;
glycol ethers; alkoxylated aromatic alcohols; aromatic alcohols; terpenes; and
mixtures thereof. Aliphatic alcohols and glycol ether solvents are most
preferred,
particularly those with vapour pressure of about 0.05 mm Hg at 25°C and
1
atmosphere pressure (about 6.66 Pa).
Aliphatic alcohols, of the formula R-OH wherein R is a linear or branched,
saturated or unsaturated alkyl group of from about 1 to about 20 carbon atoms,
preferably from about 2 to about 15 and more preferably from about 5 to about
12, are suitable solvents. Suitable aliphatic alcohols are methanol, ethanol,
propanol, isopropanol or mixtures thereof. Among aliphatic alcohols, ethanol
and
isopropanol are most preferred because of their high vapour pressure and
tendency to leave no residue.
2o Suitable glycols to be used herein are according to the formula HO-CR1 R2-
OH
wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated
aliphatic hydrocarbon chain and/or cyclic. Suitable glycols to be used herein
are
dodecaneglycol and/or propanediol.
In one preferred embodiment, at least one glycol ether solvent is incorporated
in
the compositions of the present invention. Particularly preferred glycol
ethers
have a terminal C3-C6 hydrocarbon attached to from one to three ethylene
glycol
or propylene glycol moieties to provide the appropriate degree of
hydrophobicity
and, preferably, surface activity. Examples of commercially available solvents
3o based on ethylene glycol chemistry include mono-ethylene glycol n-hexyl
ether
(Hexyl Cellosolve~) available from Dow Chemical. Examples of commercially
available solvents based on propylene glycol chemistry include the di-, and
tri-
propylene glycol derivatives of propyl and butyl alcohol, which are available
from
Arco under the trade names Arcosolv~ and Dowanol~.
25


CA 02460435 2004-03-16
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In the context of the present invention, preferred solvents are selected from
the
group consisting of mono-propylene glycol mono-propyl ether, di-propylene
glycol
mono-propyl ether, mono-propylene glycol mono-butyl ether, di-propylene glycol
mono-propyl ether, di-propylene glycol mono-butyl ether; tri-propylene glycol
mono-butyl ether; ethylene glycol mono-butyl ether; di-ethylene glycol mono-
butyl
ether, ethylene glycol mono-hexyl ether and di-ethylene glycol mono-hexyl
ether,
and mixtures thereof. "Butyl" includes normal butyl, isobutyl and tertiary
butyl
groups. Mono-propylene glycol and mono-propylene glycol mono-butyl ether are
the most preferred cleaning solvent and are available under the tradenames
Dowanol DPnP~ and Dowanol DPnB~. Di-propylene glycol mono-t-butyl ether is
commercially available from Arco Chemical under the tradename Arcosolv PTB~.
In a particularly preferred embodiment, the cleaning solvent is purified so as
to
minimize impurities. Such impurities include aldehydes, dimers, trimers,
oligomers and other by-products. These have been found to deleteriously affect
product odour, perfume solubility and end result. The inventors have also
found
that common commercial solvents, which contain low levels of aldehydes, can
cause irreversible and irreparable yellowing of certain hard surfaces. By
purifying
the cleaning solvents so as to minimize or eliminate such impurities, surface
2o damage is attenuated or eliminated.
Though not preferred, terpenes can be used in the present invention. Suitable
terpenes to be used herein monocyclic terpenes, dicyclic terpenes and/or
acyclic
terpenes. Suitable terpenes are: D-limonene; pinene; pine oil; terpinene;
terpene
derivatives as menthol, terpineol, geraniol, thymol; and the citronella or
citronellol
types of ingredients.
Suitable alkoxylated aromatic alcohols to be used herein are according to the
formula R-(A)n-~H wherein R is an alkyl substituted or non-alkyl substituted
aryl
3o group of from about 1 to about 20 carbon atoms, preferably from about 2 to
about
15 and more preferably from about 2 to about 10, wherein A is an alkoxy group
preferably butoxy, propoxy and/or ethoxy, and n is an integer of from about 1
to
about 5, preferably about 1 to about 2. Suitable alkoxylated aromatic alcohols
are
benzoxyethanol and/or benzoxypropanol.
26


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Suitable aromatic alcohols to be used herein are according to the formula R-OH
wherein R is an alkyl substituted or non-alkyl substituted aryl group of from
about
1 to about 20 carbon atoms, preferably from about 1 to about 15 and more
preferably from about 1 to about 10. For example a suitable aromatic alcohol
to
be used herein is benzyl alcohol.
When present, solvents are found to be most effective at levels from about
0.5%
to about 25%, more preferably about 1.0% to about 20% and most preferably,
about 2% to about 15%.
Hydrotropes:
Hydrotropes are advantageously used to ensure solubility of the aqueous
composition compositions, and in particular to ensure adequate perfume
1s solubility. Hydrotropes include the sulfonates of toluene, xylene and
cumene,
sulfates of naphthalene, anthracene, and higher aromatics, and C3-C10 linear
or
branched alkyl benzenes, C6-C8 sulfates such as hexyl sulfate and 2-ethyl-1-
hexyl sulfate, short chain pyrrolidones such as octyl pyrrolidone, and the
like.
Other preferred hydrotropes include the oligomers and polymers comprising
2o polyethylene glycol. In a particularly preferred embodiment, alkyl
ethoxylates
comprising at least an average of about 15 moles of ethylene oxide, more
preferably at least about 20 moles of ethylene oxide per mole chain length
(alcohol) are advantageously employed. Unlike conventional hydrotropes, the
preferred alkyl ethoxylate hydrotropes are found to have little or no impact
on the
25 filming and streaking properties of the compositions of the present
invention. ,
When present, hydrotropes are preferably used at solution weight percent of
from
about 0.01 % to about 5%, more preferably about 0.01 % to about 0.5%, still
more
preferably about 0.03% to about 0.25%.
3o The liquid compositions according to the present invention may comprise a
variety of other optional ingredients depending on the technical benefit aimed
for
and the surface treated. Suitable optional ingredients for use herein include
polymers, buffers, perfumes, colorants, pigments and/or dyes.
35 Filmin /sg-freaking cleaning and antimicrobial performance
27


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The Applicant has found that the compositions according to the present
invention
comprising a pH of about 7 or less, surfactants) and the polymeric biguanide
show very low or even no filming/streaking ("filming/streaking performance
benefit") when used on a hard surface, preferably when used on a shiny hard
surface. The overall filming and streaking profiles of surfaces treated with
the
compositions of the invention benefits are particularly good when the
surfactant is
a low residue surfactant.
So as to reduce the overall level of filming and/or streaking while still
providing
antimicrobial benefits in a hard surface cleaner context, proper selection of
the
components in the aqueous solution is essential. The polymeric biguanide
induces substantially no, preferably no, incremental visible film or streak
negatives when used in combination with a composition with pH of about 7 or
less and surfactant as described herein to treat a hard surface. Without being
bound by theory, it is believed that the polymeric biguanide compound acts as
a
wetting polymer at pH of about 7 or less and in the presence of surfactant. As
such, it functions as a hydrophilic agent, helping evenly distribute the
aqueous
composition throughout the surface to be treated. It is believed that the
polymeric
biguanide forms a colorless, uniform film on the treated hard surfaces,
2o attenuating or masking the streaks and/or films due to other components in
the
composition, or enhancing the shine/gloss of the treated surface when the
other
components in the composition do not cause streaking and/or filming issues.
Additionally, the biguanide compound does not interact very strongly with
charged surfaces, meaning that the primary interaction is between surfactants,
solvents (i.e., cleaning agents) and the surface to be treated. As a result,
the
biguanide compound has a lower tendency to bind on hard surfaces and leave
films and streaks. The wetting ability of the polymeric biguanide material in
this
context is very surprising given that the alternative cationic antimicrobial
actives,
quaternary ammonium surfactants, are very poor wetting compounds. By
3o quaternary ammonium surfactants, it is meant all surfactants of the form
R1 R2R3R4N+, wherein R1 is a C8 to C18 alkyl group, R2 and R3 are C1 to C18
alkyl groups, benzyl groups or substituted benzyl groups and R4 is a methyl
group. Such materials are widely available commercially and are sold by Lonza
Corporation and Stepan Corporation as effective antimicrobial compounds.
Quaternary ammonium compounds exhibit hydrophobic behavior in aqueous
media. As such, they de-wet the surfaces being treated. This leads to non-
2s


CA 02460435 2004-03-16
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uniform cleaning and drying, and undesirable accelerated aggregation of the
solids on the surfaces upon evaporation of the water from the aqueous
composition. This leads to high levels of streaks. Moreover, quaternary
ammonium compounds are highly charged chemical species that will bind to
negatively charged surfaces, including glass and ceramic. Once bound to these
surfaces, their removal can require use of a second treatment comprising
anionic
surfactants and the like, for removal of the quaternary ammonium compounds
(quats). This is highly undesirable. In one-step cleaning applications, quats
will
build up on negatively charged surfaces. The polymeric biguanide compounds,
within the framework provided by the compositions of this invention, are
excellent
wetting agents and do not strongly bind anionic surfaces. The polymeric
biguanide surface film is clean and strip-able, meaning that it is easily
removed
and replaced in subsequent cleaning applications. Additionally, the
hydrophilic
nature of the polymer helps the wetting of floors in next-time cleaning
applications. In instances wherein the polymeric biguanides are used to clean
vertical tiles (for example bathroom shower tiles), the compositions "sheet"
water
very well ensuring even-ness of cleaning or easier rinsing of tiles.
The magnitude of the gloss improvement provided by the polymeric biguanides of
2o the present invention, relative to similar compositions not comprising
polymeric
biguanides, will depend on the level of polymer incorporated. Increased levels
of
polymer will provide increased gloss. The Applicant has found that it is
relatively
straightforward to increase the gloss of untreated tiles with the compositions
herein when said compositions comprise, at usage levels, at least about 0.3%
polymeric biguanide and more preferably at least about 0.5% polymeric
biguanide. The exact level will depend upon the nature of the cleaning tool
used
in the cleaning process. Cleaning tools that tend to absorb the polymeric
biguanide will also reduce the amount deposited on hard surfaces. Examples are
string and strip cellulosic cleaning tools, and wipe laminates such as Swifter
3o Wet~.
Despite the hydrophilic behavior on surfaces, the polymeric biguanides within
the
context of the compositions of the invention are shown to exhibit strong
antimicrobial properties comparable to those of quaternary ammonium
surfactants.
29


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According to the present invention, the compositions are selected so as to
maximize the gloss on a standard black shiny porcelain tile described
hereinafter.
The Applicant has found that the polymeric biguanide compound assists in gloss
enhancement or retention. More specifically, the gloss readings provided by
compositions that comprise the polymeric biguanide compound are equal or
better than the gloss readings provided by identical compositions lacking the
polymeric biguanide compound. Even more surprisingly, the compositions of the
invention provide gloss retention or enhancement of clean untreated tiles.
That is,
the polymeric biguanide compound preserves or enhances the shine benefits of
the clean tiles.
Aqueous compositions comprising low-residue surfactant, lotion pH of about 7
or
less, and polymeric biguanide compound are found to provide effective
antimicrobial properties and excellent filming and streaking attributes when
wiped
on hard surfaces. That is, according to the present invention, aqueous acidic
hard
surface cleaning compositions comprising low residue surfactant and polymeric
biguanide compounds can be used with traditional cleaning tools, including but
not limited to, sponges, cloths, cellulose strings and strips, paper,
commercially
available paper towels, soft or scouring pads, brushes, and the like. These
2o cleaning tools can optionally be used in combination with an implement for
increased ease of use and improved area coverage. In one application the
compositions are packaged in a bottle or other container as concentrated
product, and are then diluted with water, optionally in a bucket, prior to
being
used as cleaning compositions. In a particularly preferred embodiment, the
aqueous compositions are provided in the form of a "spray and mop" product. In
this context, the liquid compositions are packaged in bottle or other
receptacle
that allows easy dosing directly on floors, preferably by spraying, then by
wiped
using a conventional mop or other cleaning implement. "Spray and mop" kits may
be sold as a combined package comprising lotion and cleaning implement, or as
liquid cleaner solution to be used in conjunction with implements or cleaning
cloths or pads as desired by individual users. The compositions may be
packaged and marketed in the form of floor wipes comprising said compositions.
In another highly preferred embodiment, the aqueous compositions herein are
used conjunction with an absorbent disposable cleaning pad.
30


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Packaging form of the aaueous compositions
The aqueous compositions can be packaged in any container that allows proper
dispensing of product. Such packages include, but are not limited to capped
s bottled, and spray bottles. The packages can be made of any material known
in
the art, such as plastic or glass.
In a preferred embodiment, the aqueous compositions are sold in combination
with other cleaning tools and/or implements. For example, the compositions can
1o be sold together with sponges or sponge mops. Alternatively, the
compositions
are bundled with commercial paper towels, or with string or strip mops. In one
preferred embodiment, the aqueous compositions are packaged in spray bottles
and bundled, or co-branded with a cleaning implement (spray and mop
application). In a highly preferred embodiment, the aqueous compositions of
the
15 present invention are packaged with absorbent disposable cleaning pads
and/or
cleaning implements. Kits can also be sold where such pads are combined with a
dispensing bottle containing aqueous compositions of the invention, optionally
packaged together with a cleaning implement. These latter embodiments can be
advantageously marketed and sold as 'starter kits', designed to help consumers
20 leverage all of the power of the aqueous compositions.
Process for cleaning a surface
In a preferred embodiment, the present invention encompasses a process of
2s cleaning a surface, preferably a hard surface, comprising the step of
contacting,
preferably wiping, said surface using an aqueous composition of the present
invention. In a preferred embodiment of the present application, said process
comprises the steps of contacting parts of said surface, more preferably
soiled
parts of said surface, with said aqueous composition. By "hard-surfaces", it
is
3o meant herein any kind of surfaces typically found in houses like kitchens,
bathrooms, or in car interiors or exteriors, e.g., floors, walls, tiles,
windows, sinks,
showers, shower plastified curtains, wash basins, WCs, dishes, fixtures and
fittings and the like made of different materials like ceramic, vinyl, no-wax
vinyl,
linoleum, melamine, glass, any plastics, plastified wood, metal or any painted
or
35 varnished or sealed surface and the like. Hard-surfaces also include
household
31


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appliances including, but not limited to, refrigerators, freezers, washing
machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
Test methodologies
The filming and streaking test methodologies shown below illustrate the
benefits
of the compositions of the present invention.
Filming and streaking_for conventional cleaning tools: sponges
Test Tiles:
Extracompa~ black glossy ceramic tiles, obtained from Senio (via Tarroni 1
48012 Bagnacavallo (RA), Italy), with dimensions 20 cm X 20 cm X 1 cm are
employed as the test surface. Prior to use, the tile surfaces are washed with
soap
and water. They are then rinsed with about 500 ml distilled water and wiped
dry
using paper towel, preferably using a low-binder clean paper towel such as
Scott~ paper towels. Approximately five milliliters of a 50% water, 50% 2-
propanol solution mix is applied from a squirt bottle to the surface of the
tiles,
spread to cover the entire tile using clean paper towel and then wiped to
dryness
2o with more paper towel. The application of the water/2-propanol treatment is
repeated and the tiles are allowed to air dry for five minutes. The test tiles
are
positioned on a horizontal surface, completely exposing the ceramic surface
prior
to testing. Prior to initiating the wiping with test products, the tiles gloss
readings
for the cleaned tiles are measured and recorded. The measurement is performed
using a 'BYK Gardner micro-TRI-gloss' gloss-meter using the 60° angle
setting.
The gloss-meter is manufactured by BYK-Gardner, and is available under catalog
number is GB-4520. The gloss of each tile is analytically measured at the four
corners and the center of the tile, and the readings averaged. Tests are then
conducted on single test tiles with a total of 3 replicates to ensure
reproducibility.
Test sponges:
So as to exemplify the use of conventional implements with the aqueous
compositions of the present invention, the following protocol is used for
sponges.
Sponges with dimensions 14 cm X 9 cm X 2.5 cm purchased from VWR
Scientific, catalog No. 58540-047, cut to size by cutting each sponge in
thirds
along the width of the sponge, washed in a conventional washing machine with
32


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WO 03/031546 PCT/US02/32197
detergent and then washed in plain water in a washing machine 3 times so as to
strip the sponge finishes. The sponges are then allowed to dry in a working
fume
hood for 48 hours. The dimensions of the dry sponges after air-drying are
about 9
cm X 4.5 cm X 2.5 cm. Dry test sponges are weighed (5 ~ 1 grams). Distilled
water is then added at a load factor of 2 grams water per gram sponge so as
moisten the sponge. Using a disposable pipette, the damp sponges are then
dosed with 3 ml of test product. The dosing is done so as to evenly cover one
of
the four large faces of the sponge (area of about 14 cm X 9 cm), preferably
the
one with the smallest size visible pores.
Wiping Procedure:
A hand-held damp sponge is then positioned with the length of the sponge
(i.e.,
14 cm) positioned parallel to the top left-hand side of the tile, and is then
made to
wipe the tile from left to right, right to left, left to right, right to left,
and left to right
motions, proceeding from the upper left hand side of the tile to the lower
right
hand side of the tile, so as to as evenly as possible cover the whole tile.
The
wiping motion is made continuously from side to side as described above, and
the final pass is completed past the end of the tile. The total wiping time is
about
3-4 seconds.
~o
Testing with other conventional cleaning tools can be conducted in analogous
manner. For experiments conducted with paper and commercially available paper
towels, the cleaning tools are not pre-moistened and the treatments are
directly
placed on tile. All conventional cleaning tools are constructed so as to have
substantially similar length and width dimensions as the sponges herein
described.
Grading:
Grading is performed within 30 minutes after the tiles have been wiped. For
each
3o test product (which consists of a and impregnated lotion), the wiping
procedure
described above is performed five times. The tiles are allowed to air dry at
ambient conditions (20°C-25°C at a relative humidity of 40-50%)
and then
graded. Tiles are graded using visual grades and gloss-meter readings. Two
sets
of measurements are selected since the gloss-meter measurements allow for an
analytical estimate of filming, while the visual grades advantageously employ
human visual acuity for the identification of streaks and blotchy areas. The
two
33


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grades are viewed as complementary and usually show similar trends. Visual
grading is done with 5 expert panelists such that the panelists do not know
the
identity of the specific products tested. Visual grading of is conducted using
a 0 to
4 scale, where 4 indicates a very streaky/filmy end result and 0 is a
completely
perfect end result. Tile residue is analytically measured using a 'BYK-Gardner
micro-TRI-gloss' gloss-meter using a 60° angle setting. The gloss-meter
is
manufactured by BYK-Gardner and is available as catalog item number GB-
4520. Once the tiles are dry (air dried at ambient conditions), the gloss of
each
tile is analytically measured with the gloss-meter at the four corners and the
center of the tile, and the readings averaged. The averages for each of the 3
tiles
tested are computed and then averaged. This 'average of averages' is then
compared to the 'average of averages' computed on the pre-cleaned tiles; the
standard deviation for gloss loss (gain) is obtained using all 15 gloss
readings,
wherein each gloss measurement recorded corresponds to the difference
between clean and treated tile (mean 8). The overall appearance of tiles will
depend on both, the amount of streaking and the amount of filming on the
tiles.
Filming and streaking for absorbent disposable cleaning pads
2o Test Tiles:
The test tiles are prepared in the section entitled filming and streaking
conventional cleaning tools: sponges.
Test pads:
Pads used are those commercially available in the US as "Swiffer WETJET~". For
the purposes of the test the pad is cut down to a dimension of 11.5 X 14.5 cm
along the width of the pad in order to scale it down so it can effectively be
used
to clean the tile which has dimensions of 20 cm X 20 cm X 1 cm as described
above. After cutting the edges, the pad is sealed with two-sided tape to
prevent
3o super-absorbent polymer from leaching out. The pad is then attached to a
handle
with a mop head. The implement head can be made using an implement such as
that sold as "Swifter~", taking the head portion only and cutting it down to
10.5
X11.5 cm (thus creating a mini implement to go with the reduced size pads used
in the experiments). The pad can be attached with tape onto the Swiffer~ mini
implement or with Velcro.
34


CA 02460435 2004-03-16
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Wiping Procedure:
Prior to wiping the flaps on the WETJET~ pad are opened as per usage
instructions. Three ml of the test solution are then applied at the bottom of
the tile
(3 mm above edge of bottom) using a pipette and spread along the full width of
the tile trying to achieve even coverage. The implement comprising the WETJET~
pad is then placed over the solution at the bottom left hand corner of the
tiles,
and then made to wipe the complete surface of the test tiles in five un-
interrupted
over-lapping wipe motions: first from left to right, then repeated right to
left. The
wiping motion is made continuously from side to side as described above, and
the final pass is completed past the end of the tile. On the last wiping
strokes as
the edge of the tile is reached, it is important that the.flap on the leading
edge of
the WETJET° pad contacts the surface in order to smooth out the
solution at the
edges. Tests are conducted on single test tiles with a total of 3 replicates
to
ensure reproducibility. While a fresh aliquot of 3 ml of solution is applied
to each
~5 test tile, the same pad is used for all replicates (pad has sufficient
mileage to
cleaning multiple tiles). Wiping time duration is about 5 seconds per tile.
Experimental data and Examples
2o The following examples are meant to exemplify compositions used in a
process
according to the present invention but are not intended to limit or otherwise
define
the scope of the present invention. The aqueous compositions are made by
combining the listed ingredients in the listed proportions to form homogenous
mixtures (solution weight % unless otherwise specified).
The aqueous compositions A-P are used in conjunction with sponges for a
general cleaning application, and are prepared from a base product lacking
surfactant and polymeric biguanide. The base product includes: 0.05% C12-14
E021, 0.5% citric acid, 2% propylene glycol n-butyl ether (Dowanol PnB~), 8%
3o ethanol and 0.1 % perfume, and the remainder, excluding the hole left for
surfactant and polymer/antimicrobial agent, up to 100%, water. Surfactant and
polymer/antimicrobial agent are then incorporated into the base product.
Compositions A-P have a pH near 2.5.
Compositions Q-X are used in conjunction with a disposable absorbent pad to
illustrate a floor cleaning application. The compositions are prepared from a
base


CA 02460435 2004-03-16
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product lacking surfactant and polymeric biguanide. The base product includes:
0.125% citric acid (except compositions W and X), 2% propylene glycol n-butyl
ether (Dowanol PnB), and 0.05% perfume, and the remainder, excluding the hole
left for surfactant (0.03%) and polymer/antimicrobial agent (0.05% if
present), up
to 100%, water. Surfactant and polymer/antimicrobial agent are then
incorporated
into the base product. Compositions Q-V have a pH of about 2.5; compositions
W and X have a pH of about 6.
Compositions AA-AH illustrate the benefits of the organic acid comprising at
least
one hydroxyl group within the scope of this invention. The base products for
these compositions comprise: 0.22% C12-14 sulfobetaine, 0.05% C12-14 E021,
0.5% acidifying agent (except for treatments AG and AH which use lower levels
of inorganic acid), 2% propylene glycol n-butyl ether (Dowanol PnB), 8%
ethanol
and 0.1 % perfume, and the remainder, excluding the hole left for polymeric
~5 biguanide, up to 100%, water. Compositions AA-AH have a pH of about 2.5.
Compositions used with conventional cleaning tools: sponges
A B C D E F G H 1 J


Surfactants


C12-14 0.22 0.22 0.22 --- --- --- --- --- --- ---
sulfobetaine


C8-16 APG** ___ ___ ___ 0.22 0.22 0.22 ___ ___ ___ ___


Coco betaine***--- --- --- --- --- 0.22 0.22 --- ---


09-11 E06****___ ___ ___ _ __ __ ___ ___
0.220.22



Antimicrobials


PHMBt ___ 0.3 ___ ___ 0.3 ___ ___ 0.3 ___ 0.3


ADBAC$ ~ ~ ~ ~ I I I I I I
___ ___ 0 ___ ___ 0.3 ___ ___ ___ ___
3


1C L M N O P


Surfactants


Am ho ro innate 0.22 0.22 --- --- --- 0.22
V*


C12-14 sulfobetaine****--- --- 0.22 --- --- ---


Coco betaine (V*) ~ ~ I I I
~ --- --- --- 0.22


36


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
C9-11 EO6**** --- --- -- -- 0.22 ---



Pol mer


PHMBt --- 0.3 1.0 1.0 1.0 1.0


AA AB AC AD AE AF AG AH


Surfactants


C8-16 APG** 0.22 0.22 0.22 0.220.22 0.22 0.22 0.22



Or anic Acid


Tartaric acid 0.5 0.5 --- --- --- --- --- ---


Lactic acid --- --- 0.5 0.5 --- --- --- ---


DAGS ___ ___ ___ ___ 0.5 0.5 ___ ___


H drochloric --- --- --- --- --- --- 0.02 0.02
acid



Pol mer


PHMBt --- 0.3 --- 0.3 --- 0.3 --- 0.3


* Cocoamido propyl sulfobetaine made by Goldschmidt under the tradename
Rewoteric CAS 15-U~
** Alkyl PolyGlucoside made by Cognis under the tradename Plantaren 2000~
*** C12-16 dimethyl betaine made by Albright & Wilson under the trade name
Empigen BB/L~
**** Alkyl ethoxylate (6) made by Shell Chemical under the trade name Neodol
91-6~
(V*) N-coconut fatty acid amidoethyl N-hydroxyethyl amino propionic acid,
sodium salt, made by Degussa-Goldschmidt under the trade name Rewoteric AM
KSF 40~
t Poly (hexamethylene biguanide) made by Avecia under the tradename Vantocil
IB~
$ Alkyl Dimethyl Benzyl Ammonium Chloride made by Lonza under the
tradename Barquat 4280~
oDiacids: Adipic, glutaric and succinic manufactured by Rhodia as a commercial
mixture.
37


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
Compositions used in conjunction with absorbent disposable cleaning pads:
Q R S T U V W X


Surfactants


C12-14 0.03 0.03 0.03 --- --- --- --- ---
sulfobetaine


C8-16 APG** --- --- --- 0.03 0.03 0.03 0.03 0.03



Or anic Acid


Citric Acid 0.125 0.125 0.125 0.125 0.1250.125 --- ---



Antimicrobials


PHMBt --- 0.05 --- --- 0.05 --- --- 0.05


ADBAC$ --- --- 0.05 --- 0.05 --- ---


* Cocoamido propyl sulfobetaine made by Goldschmidt under the tradename
s Rewoteric CAS 15-U~
** Alkyl PolyGlucoside made by Cognis under the tradename Plantaren 2000~
fi Poly (hexamethylene biguanide) made by Avecia under the tradename Vantocil
I B~
o $ Alkyl Dimethyl Benzyl Ammonium Chloride made by Lonza under the
tradename Barquat 4280~
Filming and streaking experimental results
15 The data below are tabulated in terms of gloss-meter measurements and
visual
grades. As indicated in the experimental section, the gloss-meter readings
(mean
treatment 8) are computed as a difference in gloss between tiles treated with
the
experimental compositions herein and that for the corresponding clean,
untreated
tiles. The clean tiles all have 60° angle gloss readings between 91 and
94. Gloss
20 losses (gains) are computed as differences in readings. Positive values
represent
a loss in gloss. Negative values () suggest a gain in gloss. The mean gloss
loss
(gain) caused by treatments versus untreated tiles (mean treatment 8), and
associated statistical significance are calculated. The mean gloss (gain) on
tile
38


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
caused by the addition of PHMB (mean 8 (PHMB-noPHMB)) and associated
statistical significance is also reported. The mean gloss (gain) on tile
caused by
poly (hexamethylene biguanide) versus quaternary ammonium surfactant (mean
8 (PHMB-Quat)) and statistical significance are also reported.
In these tests, statistical significance is established at the 95% confidence
level
( a =0.05), using a one-tailed. test and pair-wise statistical treatment of
the
samples. All samples are assumed to exhibit a normal distribution with equal
variances. Using the raw data, t statistics are calculated and compared to the
t-
o critical statistic. When the calculated t test exceeds t-critical, the
samples are
'significantly different. When t-calculated is less than t-critical, the
samples are
not 'significantly' different. The direction of significance is determined by
the sign
of the mean differences (i.e., 'mean treatment 8', 'mean 8 (PHMB-noPHMB)' or
'mean 8 (PHMB-Quat)'. For example, if the treatment mean gloss for a treatment
~5 is higher than that of the untreated tile, and f-calculated exceeds t
critical, then
the data suggest that at a 95% confidence level ( a =0.05) the treatment has a
significantly higher gloss than the untreated tile. The statistic treatment of
dependent paired samples (mean treatment ~) and independent paired samples
((PHMB-noPHMB or mean ~ (PHMB-Quat)) can be found in Anderson, Sweeney
2o and Williams, Statistics for Business and Economics, 6t" edition, West
Publishing
Company, 1996, incorporated herein by reference. The statistics can be
conveniently run using the statistical function in Microsoft ExceITM.
The streaking grades are provided as 0-4 visual grades using 5 expert
panelists.
25 The mean grade and standard deviations are computed. The significance of
differences in visual grading is defined in analogous manner as described for
the
gloss-meter test.
39


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
A B C D E F G H I J


Gloss


Mean treatment0.6 (2.0)2.2 1.9 (1.9)3.0 1.7 (1.0)2.3 0.3
3


Treatment 8 0.22 0.63 1.34 1.11 0.540.75 0.48 0.46 0.87 0.42


Std. Dev.


Mean 8 Ref. (2.6) Ref. (3.8) Ref. (2.7)Ref. (2.0)


PHMB-noPHMB


b' (PHMB- Yes Yes Yes Yes


noPHMB)


Si nificant?


Mean 8 Ref. 4.2 Ref.(4.9)


PHMB-Quat


8 (PHMB-Quat) Yes Yes


Si nificant?



Visual


Mean grade 0.0 0.0 1.6 0.4 0.4 1.6 0.8 0.3 1.2 0.5


Treatment 8 0.06 0.09 0.41 0.25 0.280.3 0.33 0.19 0.4 0.25


Std. Dev.


Mean 8 Ref. 0.0 Ref. Ref. 0.5 Ref. 0.7


PHMB-noPHMB


8 (PHMB- No Yes Yes


noPHMB)


Si nificant?


Mean 8 Ref. 4.2


PHMB-Quat


8 (PHMB-Quat) Yes


Si nificant?




CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
K L M N O P


Gloss


Mean treatment 2.9 (1.3) (7.1 (9.1 (10.7)(8.8)
) )


s


Treatment 8 0.930.90 0.8 1.1 1.4 0.6


Std. Dev.


Mean 8 Ref.(4.2) (7.7) (11.0 (13.0)(11.7)


(PHMB- )


noPHMB


8 (PHMB- Ref.Yes Yes Yes Yes Yes


noPHMB) vs. vs. vs. vs.
A G I ~K


Si nificant?


Mean 8 (5.1 (8.1 (11 (7.5)
) ) )


(1 %PHMB- vs. vs. vs. vs.
B H J L


.3%PHMB



Visual


Mean grade 0.9 0.4 0.1 0.4 0.6 0.4


Treatment 8 0.280.15 0.16 0.23 0.46 0.23


Std. Dev.


Mean 8 Ref.(0.5) 0.1 (0.4) (0.6) (0.5)


(PHMB-


noPHMB


8 (PHMB- Ref.Yes No Yes Yes Yes


noPHMB) vs. vs. vs. vs.
A G I K


Si nificant?


Mean & 0.1 0.1 0.1 0.0


(1 %PHMg- vs. vs. vs. vs.
B H J L


.3%PHMB


Q R S T U V W X
41


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
Gloss


Mean 0.5 0.3 2.1 0.5 0.1 3.3 0.6 (1.9)


treatment
s


Treatment 0.65 0.36 1.44 0.450.4 1.46 0.7 0.33
8


Std. Dev.


Mean 8 Ref. (0.2) Ref.(0.5) Ref. (2.5)


(PHMB-


noPHMB


8 (PHMB- Ref. Yes Ref.Yes Ref. Yes


noPHMB)


Si nificant?


Mean 8 Ref. (1.8) Ref. (3.4)


PHMB-Quat


8 (PHMB- Ref. Yes Ref. Yes


Quat)


Si nificant?



Visual


Mean grade 1.2 0.7 2.8 1.1 0.3 2.5 1.0 0.7


Treatment 0.71 0.23 0.44 0.230.24 0.20 0.18 0.11
~


Std. Dev.


Mean 5 Ref. (0.6) Ref.(0.8) Ref. (0.3)


(PHMB-


noPHMB


8 (PHMB- Ref. Yes Ref.Yes Ref. Yes


noPHMB)


Si nificant?


Mean ~ Ref. (2.1 Ref. (2.3)
)


PHMB-Quat


8 (PHMB- Yes Yes


Quat)


Si nificant?


AA I AB I AC I AD I AE I AF' I AG I AH I
42


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
Gloss


Mean treatment1.2 (3.2) 5.4 0.3 4.9 0.3 0.7 (9.2)


8


Treatment 8 0.58 0.9 1.23 0.20 1.4 0.62 0.3 (3.2)


Std. Dev.


Mean 8 Ref. (4.2) Ref. (5.0) Ref. (4.6) Ref.(9.9)


(PHMB-


noPHMB


8 (PHMB- Ref. Yes Ref. Yes Ref. Yes Ref.Yes


noPHMB)


Si nificant?



Visual


Mean grade 0.6 0.2 1.5 0.2 3.2 0.3 1.5 0.5


Treatment 5 0.16 0.15 0.37 0.15 0.2 0.15 0.240.15


Std. Dev.


Mean 8 Ref. (0.4) Ref. (1.3) Ref. (2.9) Ref.(1.0)


(PHMB-


noPHMB


8 (PHMB- Ref. Yes Ref. Yes Ref. Yes Ref.Yes


noPHMB)


Si nificant?


Data interpretation for filming and streaking:
Sponges:
Compositions A-F illustrate the filming and streaking benefits provided by
compositions comprising polymeric biguanide as opposed to non-biguanide
containing compositions and alternatives that substitute quaternary ammonium
surfactant for the polymeric biguanide on an equal weight basis. In each case
it is
o found that quaternary ammonium surfactants have a significant deleterious
effect
on filming streaking properties relative to compositions not comprising the
quaternary ammonium surfactant, as 'measured analytically by gloss-meter
43


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
readings or by trained expert graders (compare filming/streaking results
obtained
for treatments A and D versus those obtained for treatments C and F).
Additionally, the polymeric biguanide-containing compositions (treatments A
and
D) significantly enhance the gloss of untreated tiles and provide a
significant
improvement versus compositions not comprising the polymeric biguanide.
Gloss enhancement of untreated tiles is also observed for treatment H and L,
which incorporate low residue surfactant, and this enhancement can be traced
directly to the inclusion of PHMB in the composition (compare gloss-meter and
expert grades for treatments H vs G and L vs. K).
Treatment J, which does not comprise a low residue surfactant does not enhance
the gloss of untreated tile. Note however, that increased amount of PHMB (1 %)
does result in gloss enhancement, i.e., compare treatments I, J and O..
Compositions M-P illustrate the impact of a higher PHMB level on tile gloss.
These compositions, with 1 % PHMB, provide increased gloss relative to
corresponding treatments B, H, J and L, which comprise 0.3% PHMB and
treatments A, G, I and IC, which do not comprise PHMB. However, the increased
2o gloss, as measured by the gloss-meter does not translate into any
improvement
in visual grade. The data suggest a point of diminishing returns in visual
grades
despite analytical gloss enhancement.
Compositions D, E and AA-AH illustrate the ability to use acids within the
scope
of this invention. Compositions comprising organic acid and inorganic acid all
show gloss and visual grade benefits for polymeric biguanide (compare
filming/streaking results for E vs. D, AB vs. AA, AD vs. AC, AF' vs. AE, and
AH
vs. AG).
3o Absorbent disposable cleaning pads:
In the case of the examples illustrating the use of a Swifter Wet JetTM (Q-X)
pad
in a floor cleaning application, the products with PHMB show an advantageous
trend for gloss and visual grades versus corresponding products without PHMB.
Thus, treatments R and U (with PHMB) have higher gloss retention means (mean
~) and visual grade means relative to treatments Q and T (without PHMB).
44


CA 02460435 2004-03-16
WO 03/031546 PCT/US02/32197
Finally, the mean gloss and visual grades for products R and U with PHMB are
significantly better than for corresponding products that incorporate
quaternary
ammonium antimicrobial agents (treatments S and V) instead of PHMB. Products
W and X also show the benefits of PHMB, in the absence of an acidifying agent.
Thus treatment X show significant gloss and visual grade advantages versus
treatment W.

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Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 2002-10-08
(87) PCT Publication Date 2003-04-17
(85) National Entry 2004-03-16
Examination Requested 2004-03-16
Dead Application 2011-02-07

Abandonment History

Abandonment Date Reason Reinstatement Date
2010-02-08 FAILURE TO PAY FINAL FEE
2010-10-08 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Request for Examination $800.00 2004-03-16
Registration of a document - section 124 $100.00 2004-03-16
Application Fee $400.00 2004-03-16
Maintenance Fee - Application - New Act 2 2004-10-08 $100.00 2004-03-16
Maintenance Fee - Application - New Act 3 2005-10-10 $100.00 2005-09-22
Maintenance Fee - Application - New Act 4 2006-10-10 $100.00 2006-09-29
Maintenance Fee - Application - New Act 5 2007-10-09 $200.00 2007-09-25
Maintenance Fee - Application - New Act 6 2008-10-08 $200.00 2008-09-24
Maintenance Fee - Application - New Act 7 2009-10-08 $200.00 2009-09-28
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
BARNABAS, MARY VIJAYARANI
POLICICCHIO, NICOLA JOHN
SHERRY, ALAN EDWARD
WOLFF, ANN MARGARET
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Description 
Date
(yyyy-mm-dd) 
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Claims 2009-04-29 7 282
Abstract 2004-03-16 1 65
Claims 2004-03-16 3 143
Description 2004-03-16 45 2,353
Cover Page 2004-05-14 1 28
Claims 2008-05-15 7 246
Description 2008-05-15 45 2,321
PCT 2004-03-16 6 216
Assignment 2004-03-16 7 288
Prosecution-Amendment 2007-11-15 8 392
Prosecution-Amendment 2008-05-15 27 1,323
Prosecution-Amendment 2008-10-29 4 184
Prosecution-Amendment 2009-04-29 13 653
Correspondence 2010-01-25 1 38
Prosecution-Amendment 2010-01-26 1 30
Correspondence 2010-02-09 1 13
Correspondence 2010-02-15 3 105