=
=
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Organization
International Bureau
(43) International Publication Date
(10) International Publication Number
2 December 2004 (02.12.2004) PCT WO 2004/104156 Al
(S1) International Patent Chasstieath CHD 37395, DE, DK, DM, DZ BC, FE, BG, ES, FI,
308, 306 Gil, GM, FIR, HU ID, 1, IN, I, JP, KF
(21) International Application Numnbe
PCT/AIS20040015473
(22) International Filing Date: 18 May 2004 (18.052008)
(25) Filing Language:
(26) Publi
ton Language:
(30) Priority Data:
107840,968 19 May 2003 (19.05.2003)
us
(71) Applicant (for all designated States except US): COL+
GATE-PALMOLIVE COMPANY [US/US]; 300 Park
Avenue, New York, NY 10022 (US).
(72) Inventor; and
(78) Inventor/Applicant (for US only): MERCADO,
Hedeliza, Malonzo [CAICAJ; 19 Cromwell Road,
borough, Ontario MU 3N1 (CA).
(74) Agents PARK, Ellen, K; COLGATE-PALMOLIVE
COMPANY, 909 River Road, PO. Box 1343, Piscataway,
NJ 08855-1343 (US).
(1) Designated States (unless vherwise indicated, for every
Kind of national protection avaiable): AE
AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD,
MG, MK, MN, MW, MX, MZ, NA, NI, NO. NZ, OM, Pt
PH, PL, PI, RO,RU, SC, SD, SE, SG, SK, SL,S¥, J, TM.
1S, UZ, VC, VN, YU, ZA, 7M,
sy
Designated States (unless otherwise indicated, for every
ind of regional protection available: ARIPO (BW, GH,
GM, KE, LS, MW, MZ, NA, SD, SI, SZ, TZ, UG, ZM,
2), Burasian (AM, AZ, BY, KG, KZ, MD, RU, TI, TM)
European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FL
GR, HU, IE, IT, LU, MC, NL, PL, PE, RO,
‘TR), OAPI (BF, BJ, CF. CG, Cl, CM, GA, GN, GQ.
SN, TD, TG).
Declarations under Rule 4
= ts 10 applicants entitlement to apply for and be granted a
patent (Rule 4.17(i) forall designations
‘othe applicant's entitlement to claim the priority ofthe
earlier application (Rule 4.17(ii) for all designations
Published
with international search report
before the expiration of the time limit for amending the
claims and t0 be republished in the event of receipt af
‘amendments
For nwo-leter codes and other abbreviations, refer to the "Gull
lance Notes on Codes and Abbreviations” appearing at the begin-
hing of each regular issue ofthe PCT Gacete
(8) Title: BATHROOM CLEANING COMPOSITION
(67) Abstract: A bathroom cleaning composition containing a chlorine containing bleach, that is effective in removing mold and
mildew as well as removing soap scum.WO 2004/104156 PCT/US2004/015473
BATHROOM CLEANING COMPOSITION
Backaround of the invention
Bathroom cleaning consists of removing mold and mildew as well as soap scum.
Hypochlorite is the best in Killing and removing mold and mildew organisms/stains in
damp places such as the bathroom. Unfortunately, the existing hypochlorite containing
products have @ poor performance in removing soap scum,
‘Soap scum is mostly the precipitated calcium/magnesium salts of the fatty acid
chain present in the soap with some multivalent cations depending on the hardness of
the water supply, particulate dirt, lint and some skin cells. Such dirt composition is very
difficult to be removed with alkaline products. Hence, historically, dedicated products
such as acid base and non-bleach alkaline products containing solvents are used solely
for soap scum removal with the drawback of not being able to effectively remove mold
and mildew. Consequently, another product, typically with hypochlorite is used in
tandem to remove mold and mildew.
Hypochlorite products require high level of alkalinity for stability reason. Couple
with the very limited as well as very costly solvent materials that can be compatible with
hypochlorite, makes it very challenging to develop a hypochlorite containing product for
its mold and mildew performance that can provide superior soap scum removal.
The instant invention discloses a hypochlorite product that provides superior
soap Scum removal in the laboratory testing and still is effective in removing mold and
mildew.
U.S. Patent 5,972,239 teaches an acidic bleaching solution containing a chlorine
deactivating agent.
EPA Patent 0,875,552 teaches an acidic limescale removing composition
containing an acid
EPA Patent 0,630,963 teaches an acid microemulsion composition designed to
remove soap scum.WO 2004/105156 PCT/US2004/015473
Summary of the Invention
The present invention relates to a bathroom cleaning composition which
removes soap scum as well as mold and mildew, wherein the bathroom cleaning
composition contains a chlorine containing bleach, a surfactant, a viscosity control
agent, a corrosion inhibitor, a sequestrant builder, an agent to reduce bleach odor on
skin, a perfume, a foam control agent and water.
An object of the instant invention is to provide a bathroom cleaning composition
that removes soap scum as well as mold and mildew.
To achieve the foregoing and other objects in accordance with the purpose of the
invention, as embodied and broadly described herein the novel bathroom cleaning
composition contains a surfactant, a chlorine containing bleach, at least one viscosity
control agent, a corrosion inhibitor, a sequestrant builder, a bleach odor reducing agent,
a perfume, a foam control agent and water, wherein the composition does not contain
hydrogen peroxide or sodium montmorillonite and the composition has a pH of at least
9.
Detailed Description of the invention
The present invention relates to a bathroom cleaning composition which
comprises by weight:
(a) 0.1% to 10%, more preferably 0.5% to 5.0% of a chlorine bleach
compound;
(b) 0.5% to 5%, more preferably 2.0% to 4% of an amine oxide surfactant;
(€) 0.05% to 3.0% of an alkali metal hydroxide such as sodium hydroxide or
potassium hydroxide;
(4) 0.1% to 3% of an alkali metal silicate which is a corrosion inhibitor;
(e) 0.25% to 5% of a phosphate builder salt which is a sequestration builder
salt;
() 0 to 1.5%, more preferably 0.1% to 1% of a fatty acid which functions as a
viscosity control agent;WO 2004/104156 PCT/US2004/015473
3
(@) 0.001% to 0.10% of a silicone foam control agent;
(h) 0.01% to 0.6%, more preferably 0.1% to 0.5% of a perfume;
() 0 t0.0.0010%, more preferably 0.00005% to 0,0006% of a bleach odor
reducing agent;
() the balance being water, wherein the composition has a pH of about 9 to
about 14.
Amine oxide semi-polar nonionic surfactants used in the instant composition
comprise compounds and mixtures of compounds having the formula
p
Ry (CoH40)nN-F0
Rg
wherein Ry is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl
radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms,
Rg and Rg are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or
3-hydroxypropyl, and n is from 0 to 10. Particularly preferred are amine oxides of the
formula:
Ro
-
Rg
wherein Ry is a C12.16 alkyl and Rg and Rg are methyl or ethyl, The above ethylene
oxide condensates, amides, and amine oxides are more fully described in U.S. Pat. No.
4,316,824 which is hereby incorporated herein by reference.
Although any chlorine bleach compound may be employed in the compositions
of this invention, such as dichloro-isocyanurate, dichloro-dimethyl hydantoin, or
chlorinated TSP, alkali metal or alkaline earth metal, e.g. potassium, lithium,
magnesium and especially sodium, hypochlorite is preferred. A solution containing
0.1% to 10.0% by weight of sodium hypochlorite contains or provides the necessaryWO 2004/105156 PCT/US2004/015473
4
percentage of available chlorine. 0.5% to 5% by weight of available chlorine is
especially preferred. For example, sodium hypochlorite (NaOCl) solution of from 11 to
13% available chlorine in amounts of 1.0% to 79%, preferably 4.0 to 40.0%, can be
advantageously used.
‘The preferred long chain fatly acids used in the instant compositions are the
higher aliphatic fatty acids having from 8 to 22 carbon atoms, more preferably from 10
to 20 carbon atoms, and especially preferably from 12 to 18 carbon atoms, inclusive of
the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical may be
saturated or unsaturated and may be straight or branched. Straight chain saturated
fatty acids are preferred. Mixtures of fatty acids may be used, such as those derived
from natural sources, such as tallow fatty acid, coco fatty acid, soya fatty acid, etc., or
from synthetic sources available from industrial manufacturing processes.
Thus, examples of the fatty acids include, for example, decanoic acid,
dodecanoic acid, palmitic acid, myristic acid, stearic acid, tallow fatty acid, coco fatty
acid, soya fatty acid, mixtures of these acids, etc. Stearic acid and mixed fatty acids,
eg. stearic acid/palmitic acid, are preferred,
When the free acid form of the fatty acid is used directly it will generally
associate with the potassium and sodium ions in the aqueous phase to form the
corresponding alkali metal fatty acid soap. However, the fatty acid salts may be directly
added to the composition as sodium salt or potassium salt, or as a polyvalent metal
salt, although the alkali metal salts of the fatty acids are preferred fatty acid salts.
The amount of the fatty acid or fatty acid salt stabilizer to achieve the desired
enhancement of physical stability wil depend on such factors as the nature of the fatty
acid or its salt, the nature and amount of the thickening agent, detergent active
compound, inorganic salts, other ingredients, as well as the anticipated storage and
shipping conditions.
Alkali metal (e.g. potassium or sodium) silicate, which provides alkalinity and
protection of hard surfaces, such as fine china glaze and pattern, is generally employedWO 2004/105156 PCT/US2004/015473
5
in an'amount ranging from 0.1 to 3 weight percent, preferably 0.2 to 2.5 weight percent
in the composition. The sodium or potassium silicate is generally added in the form of
an aqueous solution, preferably having NazO:SiO2 or K20:SiO2 ratio of 1:1.3 to 1:2.8.
A preferred silicate is sodium metasilicate.
A preferred solid phosphate builder salt used in the instant composition is an
alkali metal polyphosphate such as sodium tripolyphosphate ("TPP"). One suitable
TPP is sold under the name Thermphos NW. The particles size of the Thermphos NW
TPP, as supplied is usually averages 200 microns with the largest particles being about
400 microns. In place of all or part of the alkali metal polyphosphate one or more other
detergent builder salts can be used. Suitable other builder salts are alkali metal
carbonates, phosphates, silicates, lower polycarboxylic acid salts, and polyacrylates,
polymaleic anhydrides and copolymers of polyacrylates and polymaleic anhydrides and
polyacetal carboxylates.
Specific examples of such builders are sodium carbonate, potassium carbonate,
sodium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate,
potassium pyrophosphate, sodium hexametaphosphate, sodium sesquicarbonate,
sodium mono and diorthophosphate. The builder salts can be used alone with the
amine oxide nonionic surfactant or in an admixture with other builders.
Essentially, any compatible anti-foaming agent can be used in the instant
composition. Preferred anti-foaming agents are silicone anti-foaming agents. These
are alkylated polysiloxanes and include polydimethy| siloxanes, polydiethyl siloxanes,
polydibuty! siloxanes, phenyl methyl siloxanes, trimethysilanated silica and
triethylsilanated silica. A suitable anti-foaming agent is Silicone TP201 or Silicone RD
from Union Carbide.
The perfumes that can be used in the instant composition includes any perfume
that is compatible with bleach.WO 2004/105156 PCT/US2004/015473
6
The instant compositions can optionally contain a bleach odor reducing agent
which is preferably ethyl tricyclo [5.2.1.0] decan-2-carboxylate such as Fruitate™
which is available from the KAO Corporation.
Ableach stabilizer can be optionally used in the instant composition at a
concentration of 0.0004 wt. % to 0.1 wt. %. A preferred bleach stabilizer is sodium
metaperiodate.
A polymeric thickening agent can be optionally used in the instant composition at
a concentration of 0.05 wt. % to 2.5 wt. %. A preferred polymeric thickening agent is
crosslinked polyacrylic acid-type thickening agents which are the products sold by B.F.
Goodrich under their Carbopol trademark, especially Carbopol 941, which is the most
ion-insensitive of this class of polymers, and Carbopol 940 and Carbopol 934. The
Carbopol resins, also known as "Carbomer,” are hydrophilic high molecular weight,
crosslinked acrylic acid polymers having an average equivalent weight of 76, and the
general structure illustrated by the following formula:
wo
A
1
‘
H
SO
Carbopol 941 has a molecular weight of about 1,250,000; Carbopol 940 a molecular
weight of 4,000,000 and Carbopol 934 a molecular weight of approximately 3,000,000.
The Carbopol resins are crosslinked with polyalkenyl polyether, e.g. 1% of a polyalkyl
ether of sucrose having an‘average of 5,8 alkyl groups for each molecule of sucrose.
Further detailed information on the Carbopol resins is available from B.F. Goodrich,
see, for example, the B.F. Goodrich catalog GC-67, Carbopol® Water Soluble Resins.
As used herein "polyacrylic acid-type" refers to water-soluble homopolymers of
acrylic acid or methacrylic acid or water-dispersible or water-soluble salts, esters or
amides thereof, or water-soluble copolymers of these acids of their salts, esters or
amides with each other or with one or more other ethylenically unsaturated monomers,WO 2004/105156 PCT/US2004/015473
7
such as, for example, styrene, maleic acid, maleic anhydride, 2-hydroxyethylacrylate,
acrylonitrile, vinyl acetate, ethylene, propylene, and the like.
These homopolymers or copolymers are characterized by their high molecular
weight, in the range of from 500,000 to 10,000,000, preferably 500,000 to 5,000,000,
especially from 1,000,000 to 4,000,000, and by their water solubility, generally at least
to an extent of up to 5% by weight, or more, in water at 25°C.
These thickening agents are used in their lightly crosslinked form wherein the
crosslinking may be accomplished by means known in the polymer arts, as by
irradiation, or, preferably, by the incorporation into the monomer mixture to be
polymerized of known chemical crosslinking monomeric agents, typically
polyunsaturated (e.g. diethylenically unsaturated) monomers, such as, for example,
divinylbenzene, divinylether of diethylene. glycol, N,N"-methylene-bisacrylamide,
polyalkenylpolyethers (such as described above), and the like. Typically, amounts of
crosslinking agent to be incorporated in the final polymer may range from 0.01 to 1.5,
percent, preferably from 0.05 to 1.2 percent, and especially, preferably from 0.1 to 0.9
percent, by weight of crosslinking agent to weight of total polymer. Generally, those
skilled in the art will recognize that the degree of crosslinking should be sufficient to
impart some coiling of the otherwise generally linear polymeric compound while
maintaining the crosslinked polymer at least water dispersible and highly water-
swellable in an ionic aqueous medium. It is also understood that the water-swelling of
the polymer which provides the desired thickening and viscous properties generally
depends on one or two mechanisms, namely, conversion of the acid group containing
polymers to the corresponding salts, e.g. sodium, generating negative charges along
the polymer backbone, thereby causing the coiled molecules to expand and thicken the
aqueous solution; or by formation of hydrogen bonds, for example, between the
carboxyl groups of the polymer and hydroxyl donor. The formet mechanism is
especially important in the present invention, and therefore, the preferred polyacrylic
acid-type thickening agents will contain free carboxylic acid (COOH) groups along theWO 2004/105156 PCT/US2004/015473
8
polymer backbone. Also, it will be understood that the degree of crosslinking should not
be so high as to render the crosslinked polymer completely insoluble or non-dispersible
in water or inhibit or prevent the uncoiling of the polymer molecules in the presence of
the ionic aqueous system
The present bathroom cleaning compositions are readily made by simple mixing
methods from readily available components which, on storage, do not adversely affect
the entire composition. The viscosity of the light duty liquid composition desirably will
be at least water thin of about 5 centipoises (cps) at room temperature, but may be up
to 200 centipoises as measured with a Brookfield Viscometer using a number 21
spindle rotating at 20 or 50 rpm. The pH of the composition is from 9 to 14, more
preferably 10 to 13. The pH of the composition can be adjusted by the addition of
NazO (as caustic soda) to the composition.
Description of the Preferred Embodiments
Example 4
Soap Scum Removal Test
Several soap scum tests had been conducted with efficacy performance ranging
from 80% to 98% versus the control, which is either a nonbleach product position to
remove soap scum or an acidic product. A comparison of a bleach prototype products
versus a number of control samples was made.
Test Procedure:
The laboratory method consists of soiling ceramic tiles with a synthetic soap
scum stain by baking the stain on the tiles. The stain, which was sprayed evenly on the
tiles consist of:
Isopropanol 135 grams
Calcium stearate 9.18 grams
Magnesium stearate ‘5.82 grams
Calco oil blue ZV dye 0.4 gram
The soap scum stain contains a blue dye to aid visual testing.WO 2004/104156 PCT/US2004/015473
9
The Gardner Heavy Duty Tester WG6700 was used to simulate the scrubbing
action on the tiles. The number of stroke which was constant across all the products
being compared was established using a control product that provided 95% cleaning
There were five tiles being used per product. The degree of cleaning power was
measured visually by 10 panelists. A replicate was always done.
Formula:
The prototype formulas in wt. % that were used are:
[ TA (wt %) |B (wt %) TC (wt. %)
Naor 3 3 1
Amine oxide a7 25 40)
Fatty acid = = 07
laQH | 08 0.8 4.0
‘odium sifcate 0.92 0.82 0.92
‘odium tripolyphosphate anhydrous 17 20 3.0
FFruitate™ 0.0007 0.0004 0.0004
[Foam control agent 0.003 0.003 0.003
Stabilizer 0.0035 | 0.0035 | 0.0035
Perfume: 5 = 028 |
‘oftened water - [10700 | to 100_|_to 100
Miscosity, cps Water thin | water thin | 35
The tests results showed the following:
pH Results
[Shower power spray ra 100,
Pine cleen multi purpose gel 2.45, 31
Ajax bathroom gel 3.15 85
lAjax power gel 66 34
Formula A 13.03 80
[Formula B 13.10 94 }
Formula C 13.11 98 |
While Pine Cleen Multi Purpose Gel was acidic, surprisingly, it performed poorly
in removing soap scum. The B and C formulas presented, even though they are
alkaline with bleach, performed almost comparable to the control product which was
acid base.
Formulas A, B and C were subjected to a stability test. After 12 weeks at RT and
40°C conditions, the values obtained were acceptable.WO 2004/104156 PCT/US2004/015473
10
Due to the high level of amine oxide in the formula C, foam test was conducted.
The formula C and the control, Shower Power Spray, have comparable lather profile as.
shown:
T Lather height, mi.
[Prototype Formula] Shower Power Spra
inital 0 t 0
[after Tmin- 18 16
mins. 15 15:
mins. 2 18
ffO mins 10 a
The cylinder inversion lather test was employed. This consists of measuring a
10 mis solution of the test product, placed it in a 2L cylinder and invert the capped
cylinder for 10 full inversion cycles. The height of the foam generated is measured in
ml. after 1, 3, 5 and 10 minutes. Replicate values are obtained and the average is
computed.WO 2004/105156 PCT/US2004/015473
she
WHAT IS CLAIMED IS
4. Abathroom cleaning composition which comprises by weight:
(a) 0.1% to 10% of a chlorine bleach compound;
(b) — 0.1% to 3% of an alkali metal silicate;
(c) 0.25% to 5% of a phosphate builder salt; and
(d) the balance being water.
2 A bathroom cleaning composition according to Claim 1, further including
an amine oxide surfactant.
3. A bathroom cleaning composition according to Claim 2 further including
0.1% to 1% of a fatty acid.
4, Abathroom cleaning composition according to Claim 3 further including
0.05% to 3.0% of an alkali metal hydroxide.
5. A bathroom cleaning composition according to Claim 4 further including
0.0001% to 0. 1% of a silicone foam control agent.
6 A bathroom cleaning composition according to Claim 5 further including
0.01% to 0.6% of a perfume.
7. Abathroom cleaning composition according to Claim 6 further including
ethyl tricyclo [5.2.17] decan-2-carboxylate.
8. Abathroom cleaning composition according to Claim 1 further including
0.1% to 2.5% of a polymeric thickening agent.
9. Abathroom cleaning composition according to Claim 1 further including a
nonphosphate builder saltnational Appiction No|
INTERNATIONAL SEARCH REPORT -/US2004/015473
PIASSIRCRTION OF SUBJECT MATTER
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A Us 6 036 789 A (WEIBEL A THOMAS) 1
14 March 2000 (2000-03-14)
column 1, lines 9-15; claim 4
column 3, lines 8-12; table 1
A WO 02/48299 A (RECKITT BENCKISER UK LTD ; 1
RECKITT BENCKISER INC (US); BENNETT MARK
TI) 20 dune 2002 (2002-06-20)
page 1, lines 7-17; claim 1
A US 6 200 941 B1 (O’DRISCOLL ERIN D ET AL) 1,2
13 March 2001 (2001-03-13)
column 3, lines 21-28; claims 1,2
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Us 6200941 BL
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13-03-2001
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us 6313082 B1 06-11-2001 WO 9843915 AL 08-10-1998
AU 6111798 A 22-10-1998
BR 9815467 A 23-10-2001
cA 2285003 AL 08-10-1998
EP 0867502 Al 30-09-1998
JP 2001517260 T 02-10-2001
PL 335976 AL 05-06-2000
sk 132299 A3 11-07-2000
Us 6036789 A 14-03-2000 6B 2334722 A 01-09-1999
nu 746421 B2 02-05-2002
aU 2574599 A 15-09-1999
cA 2319427 AL 02-09-1999
EP 1056823 Al 06-12-2000
wo 9943779 AL 02-09-1999
ZA 9901468 A 24-08-1999
wo 0248299 A 20-06-2002 6B 2370042 A 19-06-2002
AU 2307902 A 24-06-2002
BR 0116170 A 11-11-2003
cA 2431741 AL 20-06-2002
cN 1479781 T 03-03-2004
EP 1349910 AL 08-10-2003
wo 0248299 Al 20-06-2002
Us 2004072711 AL 15-04-2004
15-05-2002
27-03-1997
21-12-2000
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02-09-1998
02-09-1998
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29-06-1999
13-03-1997
13-03-1997
28-04-1981
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1134565 AL
531204 B2
5383979 A
1099609 AL
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