U.S. patent application number 11/499226 was filed with the patent office on 2008-02-07 for use of fragrance compositions for the prevention of the development of indole base malodours from fecal and urine based soils.
This patent application is currently assigned to Takasago International Corporation. Invention is credited to Emmanuel Julien Aussant, Maud Bernadette Bassereau, Stuart Bernard Fraser, Jonathan Frank Warr.
Application Number | 20080032912 11/499226 |
Document ID | / |
Family ID | 39029944 |
Filed Date | 2008-02-07 |
United States Patent
Application |
20080032912 |
Kind Code |
A1 |
Warr; Jonathan Frank ; et
al. |
February 7, 2008 |
Use of fragrance compositions for the prevention of the development
of indole base malodours from fecal and urine based soils
Abstract
The present invention relates to the use of fragrance
compositions, said fragrance compositions comprising fragrance
compounds selected among: aldehydes, .alpha.,.beta.-unsaturated
aldehydes, alcohols, ketones, and mixtures thereof in any home and
personal care product, each fragrance compound being able to
restrict the formation of indole to less than 0.01 ppm (wt/wt)
after 24 hours incubation at room temperature in an airtight sealed
vessel of suitable fresh human urine containing 0.28% by weight of
each fragrance compound in order to prevent the development of
indole based malodours from faecal and urine based soils.
Inventors: |
Warr; Jonathan Frank;
(Paris, FR) ; Bassereau; Maud Bernadette; (La
Garenne Colombes, FR) ; Aussant; Emmanuel Julien;
(Paris, FR) ; Fraser; Stuart Bernard; (Little
Neston, GB) |
Correspondence
Address: |
MERCHANT & GOULD PC
P.O. BOX 2903
MINNEAPOLIS
MN
55402-0903
US
|
Assignee: |
Takasago International
Corporation
Tokyo
JP
|
Family ID: |
39029944 |
Appl. No.: |
11/499226 |
Filed: |
August 4, 2006 |
Current U.S.
Class: |
512/1 |
Current CPC
Class: |
A61K 8/33 20130101; A61K
8/35 20130101; A61Q 13/00 20130101 |
Class at
Publication: |
512/1 |
International
Class: |
A61K 8/00 20060101
A61K008/00 |
Claims
1. A method of employing fragrance compositions, said fragrance
compositions comprising fragrance compounds selected among:
aldehydes, .alpha.,.beta.-unsaturated aldehydes, alcohols, ketones,
and mixtures thereof in any home and personal care product, each
fragrance compound being able to restrict the formation of indole
to less than 0.01 ppm (wt/wt) after 24 hours incubation at room
temperature in an airtight sealed vessel of suitable fresh human
urine containing 0.28% by weight of each fragrance compound,
comprising preventing the development of indole based malodours
from faecal and urine based soils.
2. The method according to claim 1, wherein the fragrance
composition comprises at least 2.5% to 100%, preferably 10% to
100%, more preferably 20% to 100% and even more preferably 40% to
100% by weight of fragrance compounds selected among aldehydes,
.alpha.,.beta.-unsaturated aldehydes, alcohols, ketones and
mixtures thereof.
3. The method according to claim 1, wherein the fragrance
composition comprises 2.5% to 100%, preferably 10% to 100%, more
preferably 20% to 100% and even more preferably 40% to 100% of
fragrance compounds of fragrance compounds selected among
aldehydes, .alpha.,.beta.-unsaturated aldehydes and mixtures
thereof.
4. The method of claim 1, in which the aldehydes,
.alpha.,.beta.-unsaturated aldehydes, alcohols, ketones and
mixtures thereof, do not decrease by no more than 60% by weight,
preferably by no more than 30% by weight.
5. A method of employing fragrance compositions containing 2.5% to
100% by weight of the fragrance compounds selected among
acetophenone, aldehyde C-11, aldehyde C-10, benzaldehyde,
benzophenone, cinnamic aldehyde, citronellal, citral, heliobouquet,
trans 2-hexenal, trans 2-hexenol, perilla aldehyde, perilla
alcohol, Veltol Plus or their mixtures, comprising inhibiting
malodours containing an indole group when incorporated into any
home or personal care product.
6. A method of employing fragrance compositions containing 10% to
100% by weight of any of the fragrance compounds selected amongst
acetophenone, aldehyde C-11, aldehyde C-10, benzaldehyde,
benzophenone, cinnamic aldehyde, citronellal, citral, heliobouquet,
trans 2-hexenal, trans 2-hexenol, perilla aldehyde, perilla
alcohol, Veltol Plus or their mixtures, comprising inhibiting
malodours containing an indole group when incorporated into any
home or personal care product.
7. A method of employing a fragrance composition as defined in
claim 1, for fragrancing lavatory products such as rim blocks,
cistern blocks and liquid rim blocks.
8. A method of employing a fragrance composition as defined in
claim 1, wherein the fragrance composition is in fibrous absorbent
articles such as tampons, sanitary towels, babies' nappies, toddler
pants, incontinence products and other devices intended for
absorption of bodily excretions.
9. A method of employing a fragrance composition as defined in
claim 1, wherein the fragrance composition is in household cleaning
products such as hard surface cleaners, soft furnishing cleaners,
and room fresheners.
10. A method of employing a fragrance composition as defined in
claim 1, wherein the fragrance composition is incorporated in
animal litter.
11. A method of employing a fragrance composition as defined in
claim 1, wherein the fragrance composition is in trigger spray
cleaners for soft furnishings.
12. A method of employing a fragrance composition as defined in
claim 1, wherein the fragrance composition is in carpet cleaning
products.
13. A method of employing a compound selected among acetophenone,
aldehyde C-11, aldehyde C-10, benzaldehyde, benzophenone, cinnamic
aldehyde, citronellal, citral, heliobouquet, trans 2-hexenal, trans
2-hexenol, perilla aldehyde, perilla alcohol, Veltol Plus or their
mixtures, comprising inhibiting indole.
14. A method according to claim 7, for the preparation of a
fragrance composition for preventing the development of indole
based malodours from fecal and urine based soils.
Description
TECHNICAL FIELD OF INVENTION
[0001] The invention relates to fragrances and fragrance
ingredients which can be used in a variety of products to prevent
the development of malodours derived from the action of
micro-organisms on excreted matter such as urine or faeces. The
present invention aims to prevent the creation of malodorous
compounds based on indole and related compounds.
BACKGROUND OF THE INVENTION
[0002] Perfumes are used in many applications to mask malodours. A
particularly important category of malodours are, for example,
those resulting from substances transpired by or excreted by humans
in particular perspiration, urine, faeces or menstrual fluid, and
odours caused by animal urine or faeces, especially those of
domestic pets.
[0003] Malodours are usually caused by particularly odorous
substances such as sulphur compounds e.g. hydrogen sulphide, and
low molecular weight thiols and thioethers, nitrogen containing
compounds such as ammonia and amines including heterocyclic
compounds such as pyrazines and indoles, oxygen containing
compounds such as fatty acids and steroids. These malodorous
compounds are often created by the action of micro-organisms on
excreted material or during the digestion of food or drink. As
natural products the malodours are themselves complex mixtures, not
only of several compounds within each of the above categories but
also including members of all the categories to different degrees
depending on the source of the odour. Consequently preventing,
countering, reducing or destroying malodour is not
straightforward.
[0004] Various methods have been developed to counter or reduce
malodour beyond odour masking with strong fragrance. Activated
carbon and zeolites have been used as absorbents for malodours but
these are not suited for incorporation into many products.
Antimicrobial agents such as zinc compounds and Triclosan
(2',4',4'-trichloro-2-hydroxy-diphenyl ether) are used to kill
microorganisms involved in producing malodours, but many are
non-specific and can lead to imbalances in the natural
microflora.
[0005] U.S. Pat. Nos. 4,304,679; 4,322,308; 4,278,658 and 4,134,838
all describe fragrances which exhibit a deodorant action when
applied to human skin or when included in a laundry product. These
are believed to work by any or all of a variety of mechanisms:
reducing the vapour pressure of malodorous compounds, inhibiting
the enzymes which generate the malodours and combining with the
malodour to modify the perceived odour note.
[0006] U.S. Pat. No. 4,719,105 describes the use of cyclomethanols
and esters as low odour materials which can be used to mask
malodours without having unduly strong fragrances themselves.
[0007] US patent application 2004/0147416 describes the use of
cyclodextrins to trap malodorous molecules.
[0008] Malodours tend to become stronger over time as the
population of micro-organisms grows and malodour production
increases. Herein lies a major disadvantage of using perfumes to
mask malodour. While a perfume can mask a malodour just after
application, over time the intensity of the fragrance decreases,
whereas the malodour will in all probability increase in intensity
from the growing micro-organism colonies. The same argument can be
applied equally well to counteractants which work by reacting with
malodorous molecules, in time they will be overwhelmed by the
malodours. Their effect is to delay or reduce the intensity of the
malodour and as such this may be sufficient for some commercial
applications.
[0009] A different approach is to inhibit specific biological
pathways. Compounds which act more specifically include saturated
C.sub.3-C.sub.10 dioic acids which inhibit a sweat decomposing
esterase as described in DE patent application 4,343,265.
[0010] U.S. Pat. No. 6,183,731 describes the use of agents which
are inhibitors of 5.alpha.-reductase, such as octadecendioic acid
as a preventative agent for body malodour.
[0011] U.S. Pat. No. 5,395,555 teaches an aqueous cleaning
composition for carpets, rugs, and textiles, particularly useful in
reducing malodour of urine stains containing selected metal
sequestrants which is thought to deny heavy metals essential to the
micro-organisms' development.
[0012] However as mentioned earlier malodours are complex and such
approaches may not counter all the components of the malodour, so
it is more likely that they modify the nature of the odour which
again may be a worthwhile benefit but is only a partial solution to
the problem.
[0013] Aldehydes are sometimes cited as malodour counteractants.
U.S. Pat. No. 4,906,454 describes piroctone acid and a perfume with
a high concentration of aldehydes and/or ketones for use in
deodorants in preventing body malodours. U.S. Pat. No. 6,177,070
describes a deodorant product containing at least two different
aldehydes present in the form of addition compounds such as acetals
and hemi-acetals and an unsaturated compound. This is quite
different from the aldehydes in the present invention which are not
present as addition compounds but comprise part of the fragrance
added directly to the product.
[0014] US patent application 2005/0124512 describes the use of
fabric safe aldehydes (i.e. non discolouring) as components of air
or fabric freshening spray products which react with malodorous
components in air. There is nothing in this patent which teaches
that the aldehydes might inhibit odour formation especially that
they might do so in a non reactive way which leaves the fragrance
unimpaired.
[0015] U.S. Pat. No. 5,676,163 describes two classes of aldehydes
which act additively or synergistically to reduce the malodour of
tobacco smoke. Again the patent only teaches that aldehydes react
with some malodorous molecules and there is no evidence for the
prevention of biologically generated malodours.
[0016] US patent applications 2005/1087123 and 2005/0187124
describe compositions to be incorporated into solid and liquid
carpet cleaner and de-odourising products to remove malodours from
carpets. In US patent application 2005/0187123 aldehydes are
optional components of the mixture and there is no teaching beyond
their having an odour reaction and masking effect. However in
co-filed US patent application 2005/187124 aldehydes are described
as enzyme inhibitors whilst aldehydes and ketones are described as
odour reactants. No evidence is given as to which enzymes are
inhibited or which malodorous compounds reduced or prevented and
only benzaldehyde would be considered as a fragrance aldehyde among
the group of aldehydes cited and the efficacy of benzaldehyde is
not demonstrated in the examples.
[0017] US patent application 2002/0010447 describes two categories
of aldehydes for malodour reduction in fibrous absorbents for
bodily fluids. The categories of aldehydes which are claimed to
work synergistically are aliphatic aldehydes and aldehydes which
have an sp2 hybridised carbon in the alpha position to the aldehyde
carbon. Again there is nothing in the text to suggest that the
aldehydes have any inhibitory effect beyond chemical reaction or
vapour pressure reduction.
[0018] US patent application 2003/0044309 describes mixtures of two
types of aldehydes for malodour counteraction in carpet cleaners
but all of the examples described intimate mixing of the test
formulation with the malodour source allowing for chemical
reaction. Nowhere does the document suggest that indole based
malodours might be prevented.
[0019] From all of the prior art references and examples, aldehydes
with the specific exception of formaldehyde are predominantly
considered to work by chemical reaction with a pre-existing odorant
rather than the specific prevention of indole based malodours.
Formaldehyde is well known as an antimicrobial agent which is
frequently incorporated into formulations directly or in the form
of any of several derivatives which release formaldehyde
slowly.
[0020] Thus while it is apparent from the prior art that there are
many methods which attempt to prevent malodour, none are completely
satisfactory. The present invention describes a simple and
inexpensive way to prevent the development of some of the
components of urinous or fecal malodours via specific ingredient
selection within the fragrance incorporated into a wide range of
household and personal care products.
SUMMARY OF THE INVENTION
[0021] The present invention relates to the use of fragrance
compositions, said fragrance compositions comprising fragrance
compounds selected amongst aldehydes, .alpha.,.beta.-unsaturated
aldehydes, alcohols, ketones and mixtures thereof in any home or
personal care product, each fragrance compound being able to
restrict the formation of indole to less than 0.01 ppm (wt/wt)
after 24 hours incubation at room temperature in an airtight sealed
vessel of suitable fresh human urine containing 0.28% by weight of
each fragrance compound in order to prevent the development of
indole based malodours from faecal and urine based soils.
[0022] In the present specification the "home or personal care
products" designate all the products usually used in the care of
the home and body, particularly:
a) rim block products, cistern block or liquid rim block products,
b) hard surface liquids, gel or paste household cleaners, c) soft
furnishing cleaners or refreshers particularly liquid sprays, d)
air fresheners, e) animal litters, f) personal care fibrous liquid
absorptive devices such as sanitary towels, babies nappies or
incontinence products,
[0023] A particularly preferred form of the invention relates to
the use of fragrance compositions comprising of fragrance compounds
selected among: aldehydes, .alpha.,.beta.-unsaturated aldehydes,
alcohols and ketones as defined above, but without themselves
decreasing in concentration by no more than 60% by weight,
preferably no more than 30% by weight after 24 hours incubation at
room temperature in an airtight sealed vessel of suitable fresh
human urine containing 0.28% by weight of each fragrance compound
for use in any home or personal care product in order to prevent
the development of indole based malodours from faecal and urine
based soils.
[0024] A further preferred form of the invention relates to the use
of fragrance compounds selected among: aldehydes,
.alpha.,.beta.-unsaturated aldehydes and allylic alcohols which
satisfy the indole inhibition test as defined above for use in any
home or personal care product in order to prevent the development
of indole based malodours from faecal and urine based soils.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 shows, GC MS chromatograph for indole showing the
mass abundance for m/e 117 characteristic of indole at a retention
time of 19.14 minutes also characteristic of indole under the GC
conditions employed, for the blank (file URIN39.D) and the active
fragrance composition of example 2 (file URIN40.D)
DETAILED DESCRIPTION OF THE INVENTION
[0026] The present invention relates to the use of fragrance
compositions comprising fragrance compounds, preferably containing
2.5% to 100%, more preferably containing 10% to 100%, even more
preferred is 20% to 100% and especially preferred is 40% to 100% by
weight of fragrance compounds which are selected amongst aldehydes,
.alpha.,.beta.-unsaturated aldehydes, alcohols or ketones and
mixtures thereof, each fragrance compound being able to restrict
the formation of indole to less than 0.01 ppm (wt/wt) after 24
hours incubation at room temperature in an airtight sealed vessel
of suitable fresh human urine containing 0.28% by weight of each of
the said fragrance compounds in order to prevent the development of
indole based malodours from faecal and urine based soils.
[0027] A particularly preferred form of the invention relates to
the use of fragrance compositions comprising of fragrance
compounds, preferably containing 2.5% to 100%, more preferably
containing 10% to 100%, even more preferred is 20% to 100% and
especially preferred is 40% to 100% of which are selected amongst:
aldehydes, .alpha.,.beta.-unsaturated aldehydes, alcohols and
ketones and mixtures thereof, as defined above, without themselves
decreasing in concentration by no more than 60% by weight,
preferably no more than 30% by weight after 24 hours incubation at
room temperature in an airtight sealed vessel in the above defined
conditions, for use in home and personal care products in order to
prevent the development of indole based malodours from faecal and
urine based soils.
[0028] The effective compounds of the invention are fragrance
materials which are aldehydes, .alpha.,.beta.-unsaturated
aldehydes, alcohols or ketones which pass the indole inhibition
test, i.e. which are able to restrict the formation of indole to
less than 0.01 ppm (wt/wt) of indole compounds after 24 hours
incubation at room temperature in an airtight sealed vessel in the
above defined conditions.
Suitable Fresh Human Urine
[0029] Urine is a variable material and it has been found that not
all batches of urine are suitable for conducting the indole
inhibition test. Hence it is essential that a blank sample of fresh
human urine is tested at the same time as the samples containing
the candidate fragrance compounds and only if this blank urine
samples complies with certain criteria can the result of the
fragrance compound test be accepted as valid. In order to ensure
that the fresh human urine is suitable, the urine should have less
than 0.01 ppm (wt/wt) indole at the start of the experiment and
after 24 hours storage at room temperature in an airtight sealed
vessel it should contain between 0.25 ppm (wt/wt) and 1.25 ppm
(wt/wt) indole as determined by the test method described below.
Only if the urine blank conforms with both criteria can the results
for any fragrance compound tested be considered valid. If the urine
blank does not meet both criteria then the results for any
fragrance compound tested must be discarded and a new batch of
urine tested.
[0030] Without wishing to be bound by theories, it seems that the
compounds of the invention interfere with the biological process of
tryptophan metabolism rather than as a reagent. That many of the
effective compounds remain little changed whilst being highly
effective is an important benefit for the present invention. If
compounds react with malodours then the fragrance note must change
which presumably diminishes the quality of odour carefully created
by the perfumer.
[0031] In a preferred aspect of the invention the change in
aldehyde, alcohol or ketone concentrations is less than 60%
preferably less than 30%, so maintaining the original fragrance
note.
[0032] For those aldehydes, alcohols and ketones which decrease
over time it is possible that they may react with ammonia or other
amine species but this is not desirable nor the major aspect of the
invention. However, due to the complexity of different product
formulations, fragrances within those formulations, and malodours,
any or all of which may affect the availability of active agents
for reaction, as well as the inherent reactivity of individual
compounds we do not wish to speculate further on this point.
Perfume Composition
[0033] In the context of this specification a "fragrance
composition", which is also named "perfume composition" is an
essential part of the invention. The term "perfume composition"
means any mixture, i.e. more than one chemical species, of
odiferous materials including materials which act as malodor
counteractants. A wide variety of chemicals are known for perfumery
use, including materials possessing the required chemical
functional groups of the invention aldehydes,
.alpha.,.beta.-unsaturated aldehydes, alcohols, including allylic
alcohols and ketones but also including alkenes, esters, ethers,
nitriles, amines, oximes, acetals, ketals, thiols, acetals etc.
Without wishing to be limited, the perfume compounds will
preferably have molecular weights of less than 325 atomic mass
units, preferably less than 300 mass units and more preferably less
than 275 mass units to ensure sufficient volatility to be
perceivable. Furthermore the perfume compounds will have molecular
weights greater than 100 mass units, preferably greater than 120
mass units as lower masses may be too volatile to inhibit malodour
generation for any length of time. Furthermore ingredients of the
fragrance compositions will not contain strongly ionizing
functional groups such as sulphonates, sulphates, or quaternary
ammonium ions which prevent volatilisation.
[0034] Naturally occurring plant and animal oils and exudates
comprising complex mixtures of various chemical components are also
known for use as perfumes, and such materials can be used herein.
Perfume compositions of the present invention can be relatively
simple in their composition with a minimum of two perfume or
fragrance ingredients or can comprise highly complex mixtures of
natural and synthetic chemical components, chosen to provide any
desired odour. Perfume ingredients are described more fully in S.
Arctander, Perfume Flavors and Chemicals. Vols. I and II,
Montclair, N.J., and the Merck Index, 8th Edition, Merck & Co.,
Inc. Rahway, N.J., both are incorporated herein by reference.
[0035] Not all fragrance compounds possessing the aldehyde, alcohol
and ketone groups are effective in preventing indole derived
malodours. The indole inhibition test is therefore described as a
way of determining which compounds are effective.
[0036] The selection of the appropriate fragrance compounds useful
in the present invention may be easily made by the person skilled
in the art by detecting the indole inhibition effect provided by
those fragrance compounds by measuring formation of indole after 24
hours incubation at room temperature in an airtight sealed vessel
of fresh suitable human urine containing 0.28% by weight of each
fragrance compound and comparing the indole formation with a
control stored in the same conditions. The formation of indole may
be determined by any analysis techniques well known by the person
skilled in the art, for example by detecting the characteristic
ions of indole under standard GC-MS conditions.
[0037] The aldehydes, .alpha.,.beta.-unsaturated aldehydes,
alcohols, ketones, or mixtures thereof which are useful for the
invention purposes are those which restrict the formation to less
than 0.01 ppm (wt/wt) of indole under the above conditions.
[0038] Room temperature is defined as being within 18.degree. C. to
22.degree. C.
Indole Inhibition Test
[0039] Advantageously, the appropriate fragrance compounds may be
selected by using the following preferred indole inhibition test
which comprises the following steps: [0040] A) 0.02 g of fragrance
and 0.02 g of Tergitol 15-s-12 was added to 7 g of fresh human
urine in a 20 ml Headspace vial sealed with a PTFE faced septum and
well mixed for 10 minutes using a magnetic stirrer. For a blank to
test the suitability of a batch of fresh human urine, 7 g of human
urine was used with 0.02 g of demineralised water and 0.02 g of
Tergitol 15-s-12. If a control was required, to test the efficacy
of product base for example, the control contained 7 g of human
urine to which was added 0.02 g of fragrance, minus the active
agents and 0.02 g of Tergitol 15-s-12. [0041] B) The vials are
placed in an autosampler tray at room temperature. [0042] C) At
different times the headspace in the vials is sampled for 5 minutes
at 35.degree. C. by an SPME fibre (PDMS fibre ex Supelco) after 10
minutes at 35.degree. C. (incubation time). [0043] D) The SPME
fibre is desorbed 1 minute at 265.degree. C. from a CTC Combipal
autosampler and injected in splitless mode onto an Agilent GC-MS
5973N with a HP-INNOWAX column (30 m.times.0.25.times.0.25). (Oven
conditions: 50.degree. C. during 2 min-to 250.degree. C. at
10.degree. C./min-250.degree. C. during 5 minutes). [0044] E) Under
the above GC-MS conditions, indole has a retention time of 19.14
minutes, and can be recognised by its characteristic ions (m/z 117,
m/z 89 and m/z 90). [0045] F) In the range of values determined in
this work, the area of the indole peak (117) is linearly related to
the actual concentration in the vial, and was used without further
correction to establish the concentration of indole in "Active" and
"Blank" and if present any "Control" fragrances. [0046] G) The
material is deemed to be active if the indole concentration in the
test sample is below 0.01 ppm (wt/wt) after 24 hours incubation at
room temperature and the indole in the blank samples is between
0.25 ppm (wt/wt) and 1.25 ppm (wt/wt) indole after 24 hours storage
at room temperature. [0047] H) The change in the active ingredient
concentration is determined by comparing measurements at the start
of the experiment and after 24 hours using appropriate
characteristic ions.
[0048] FIG. 1 compares the indole peaks for a blank, control sample
and active fragrance composition of example 2 in a liquid rim
block.
[0049] A calibration line has been derived to quantify indole by
making up a series of standard solutions containing accurately
measured amounts of indole in fresh human urine and Tergitol
15-s-12 which were measured according to the method described. This
calibration is essentially linear to 0.01 ppm of indole and below
that level the indole cannot be quantified. Tergitol 15-s-12 is a
trade name of the Dow Chemical company for a commercial grade of a
secondary alcohol ethoxylate surfactant. It is also available from
Sigma Aldrich. Tergitol 15-s-12 and identical products from other
suppliers have the Chemical abstracts number CAS 68131-40-8.
Tergitol 15-s-12 acts as a solubilising agent for fragrance
ingredients which might not be directly soluble in urine at that
concentration.
[0050] The efficacy of fragrances in products may be detected by
using the above defined protocol starting from an aliquot of
fragranced product containing 0.02 g of fragrance compound was
added to 7 g of fresh suitable human urine in a 20 ml headspace
vial sealed with a PTFE faced septum and well mixed for 10 minutes
using a magnetic stirrer. For a blank, to assess the suitability of
the urine, 0.02 g of demineralised water and 0.02 g of Tergitol
15-s-12 was added to 7 g of an identical sample of human urine and
for any control, to assess whether other parts of the formulation
could inhibit urine formation, the same weight of product
containing 0.02 g of fragrance, minus any known active ingredients
was added to another 7 g of human urine taken from the same batch
as is used for the sample and blank.
[0051] There is a benefit to selecting aldehydes,
.alpha.,.beta.-unsaturated aldehydes, alcohols and ketones which do
not change concentration during the course of the indole inhibition
test, since the fragrance note will not be adversely affected by
depletion of the effective fragrance compounds. This can be
determined by measuring the fragrance concentration in the sample
containing the test cocktail at the start and end of the indole
inhibition test as described in step I of the test. If the
difference between the measurements is less than 60% preferably
less than 30% then the material is considered as not to have
changed sufficiently to alter the fragrance note and to be
particularly preferred.
[0052] The present invention also relates to the use of a fragrance
compound selected among acetophenone, aldehyde C-11, aldehyde C-10,
benzaldehyde, benzophenone, cinnamic aldehyde, citronellal, citral,
heliobouquet, trans 2-hexenal, trans 2-hexenol, perilla aldehyde,
perilla alcohol, and veltol Plus or their mixtures, as indole
inhibitors.
[0053] The invention also relates to the use of a fragrance
compound selected among: acetophenone, aldehyde C-11, aldehyde
C-10, benzaldehyde, benzophenone, cinnamic aldehyde, citronellal,
citral, heliobouquet, trans 2-hexenal, trans 2-hexenol, perilla
aldehyde, perilla alcohol, and veltol Plus or their mixtures, for
the preparation of a fragrance composition intended to prevent the
development of indole based malodours from faecal and urine based
soils.
Optional Ingredients
[0054] It is often desirable to combine methods to counter or
prevent the development of malodours. Thus the following are
optional ingredients which may be used advantageously in some of
the products to reduce malodour still further. Because of the
diverse range of products from which the invention may be delivered
not all of the optional ingredients would be suitable for all of
the potential product applications but those skilled in the
formulation of these products will recognise which ingredients are
suitable and which are not.
Sequestrants
[0055] Examples of sequestrants which have antimicrobial and enzyme
inhibitory effects in their own right or may potentiate the
efficacy of conventional biocides include aminocarboxylates such as
ethylene diamine tetraacetic acid (EDTA), diethylene
triaminepentaacetic acid, amino phosphonates, such as
hydroxyethane-dimethylene-phosphonic acid, ethylene diamine
tetra(methylene phosphonic) acid, diethylene triamine penta(methyl
phosphonic) acid, and their salts either used individually or in
admixture. Especially preferred are the biodegradable sequestrants,
exemplified by, but not limited to, S,S-ethylene diamine disuccinic
acid, and its salts or glutamic acid N,N-diacetic acid tetra sodium
salts (Dissolvine GL-38 ex Akzo Nobel) and combinations thereof.
Because of the diversity of product forms and the possibility that
some products could be diluted in water which may have a
significant calcium and magnesium content, "hard water", the
sequestrant can be included at any of a wide range of
concentrations in formulations from 0.01-0.5%.
Antimicrobial Agents
[0056] Broad spectrum antimicrobial agents which might
advantageously be used in conjunction with the present invention
are: cationic agents such as quaternium 15, benzalkonium chloride,
cetrimonium chloride, myristalkonium chloride, cetylpyridinium
chloride, lauryl pyridinium chloride and the like. Non limiting
examples of acids and their associated anions which have
antimicrobial properties include sorbic acid, benzoic acid, and
dehydroacetic acid. Other antimicrobials include benzyl alcohol,
phenylethyl alcohol, DMDMhydantoin, imidazolidinylurea, 2
bromo-2-nitropropane-1,3-diol and 4,4-dimethyloxazolidine. Phenolic
antimicrobials which might be used include chloroxylenol, salicylic
acid, and isothiazoline derivatives sold under the Kathon (Lonza)
and Proxel and Proxemal (Astra Zeneca) trade names.
Malodour Absorbers
[0057] Malodour absorbers include zinc ricinoleate sold as Tego Deo
by Degussa and cyclodextrins as described in U.S. Pat. Nos.
5,942,217; 5,955,093 and 6,033,679. Other absorbents which may be
used in pet litter trays and might absorb malodours include clays
or zeolites.
Products for Application of the Invention
Lavatory Solid Rim Blocks and Cistern Blocks
[0058] One embodiment of the present invention relates to lavatory
blocks including those which are intended, in use, to be located
under the rim of a lavatory bowl or urinal such that, during a
flushing cycle, water from the cistern flows over the block thereby
dissolving a portion of the block. Such blocks are generally known
in the art as `rim blocks` and will be referred to as such or
simply as `blocks` herein. The invention also relates to so-called
cistern blocks which are placed in the cistern and dissolve slowly
in the water contained therein. It will be appreciated that the
solubility characteristics of these two products are quite
different, since one is constantly under water while the other has
intermittent short term contact with water. However they both
contain a surfactant, a filler, a fragrance which may contain
ingredients of the present invention and optionally bleaching
agents, germicides and anti-limescale agents. Typical formulations
are taught in international patent applications WO97/7721,
WO82/03532, European patent application 0 462 643, UK patent
application 2 178 442 and U.S. Pat. No. 4,874,536 all of which are
incorporated herein by reference.
Liquid Rim Blocks
[0059] Another embodiment of the fragrances of this invention
relates to lavatory cleaners known as liquid rim blocks. Liquid rim
blocks are devices that dispense liquid compositions directly into
a lavatory bowl from under the rim of said bowl. Such rim blocks
are usually attached by various means, such as hooks and the like,
to the rim of the lavatory bowl. Every time a toilet equipped with
a rim block is flushed, an amount of composition is dispensed into
the lavatory bowl. Examples of liquid rim blocks are given in
international application WO02/40792 which teaches a liquid
rim-block device having a suspension means and at least two
compartments for active substances. International application WO
02/04951 teaches a liquid rim block, a lavatory cleaning system
comprising a dispenser for dispensing a liquid composition from
under the rim of a lavatory bowl, wherein the composition has a
viscosity of greater than 2500 mPas. Other similar systems are
described in European patent application 0 775 741 and
International application WO01/94520 all of which are incorporated
herein by reference.
Liquid Hard Surface Cleaner Formulation
[0060] A further embodiment of the invention relates to hard
surface cleaner formulations also known as all purpose cleaners or
general purpose cleaners. They are a broad category of products
including isotropic liquids, thickened liquids with or without
abrasive or as a mousse. They can be used directly from the bottle
or after dilution in water. Various delivery methods have been
devised for the convenience of the user, some are sprayed onto
surfaces from trigger spray bottles, alternatively they can be
poured directly onto surfaces and removed for instance when a
lavatory is flushed. They may contain additional ingredients such
as acids for limescale removal, biocides for hygiene, or bleaches.
Consequently there are a broad range of formulations within this
category. Table 1 below summarises the main formulation ingredients
and levels (this is taken from Surfactant Science Series Vol 67
Liquid Detergents chapter on Specialty Liquid Household Surface
Cleaners p 479 table 4.) In all cases, except when oxidizing
bleaches (eg sodium hypochlorite or hydrogen peroxide) are
incorporated into the formulation, fragrances incorporating this
invention may be used as the fragrance within the product.
TABLE-US-00001 TABLE 1 Formulation Range For Household Cleaners
Amount Ingredient Example wt % Anionic surfactant Alkylbenzene
sulphonate, as 0 35 supplied by Shell as Dobs 055, alkane
sulphonate eg Hostaspur SAS60 Nonionic surfactant Ethoxylated
alcohol eg Neodol 9 11 1 35 6EO, mixed ethoxy/propoxy alcohol such
as the pluronic series from BASF, amine oxide, alkanolamides and
betaines Hydrotropes Sodium cumene sulphonate or 0 10 xylene
sulphonate Builder/sequestrant Citrates, EDTA salts, phosphonate 0
10 salts, lactic acid and polyacrylates Solvent Lower alcohols,
glycol ethers, 0.5 50 benzyl alcohol, or hydrocarbons eg limonene
Disinfectant Hypochlorite bleach, pine oil, lower 0 15 alcohols,
quaternary ammonium salts Perfume, colour, 0.1 3 thickening
polymer, sequestrant, preservatives Water To 100
Pet Litter
[0061] The increase in animal pet population has led to an
increasing use of animal litter materials. There are numerous
animal litter products available commercially and taught by prior
art. They are usually based on inexpensive materials such as
abundant natural minerals e.g. sand, granulated clays or zeolite,
or recycled waste cellulosic materials such as woodchips, sawdust,
shredded paper, pelleted or shredded recycled cloth, ground wood
bark, alfalfa or other vegetable matter such as ground corn husk.
In order to improve the performance of animal litters additional
materials are added to improve absorbancy, to clump the particles,
to ease disposal and odour treatment agents. U.S. Pat. No.
4,437,429 teaches using zeolite to control odours in clay based
litter. U.S. Pat. No. 3,789,717 combines bentonite clay with
alfalfa which supplies chlorophyll as a deodorizer. Fragrances of
the present invention can either be incorporated into the pet
litter during manufacture or added later in use.
Carpet Cleaners
[0062] Carpet cleaners come in several forms: powders, liquids,
foams and spray spot treatments. Many of these products have to be
used in conjunction with a specific cleaning machine especially if
large areas are to be treated. However a desirable attribute of
cleaning a carpet is to leave a pleasant smell so the products
generally contain a fragrance and fragrances of the present
invention are both suitable and desirable for application in carpet
cleaning products.
Air Freshener, Textile and Soft Furnishing Deodourising Sprays
[0063] Products for reducing or masking malodours in the air or on
textiles and soft furnishings are known, such as Glade by SC
Johnson and Febreze from Proctor and Gamble. These products are
designed to be sprayed into the air or onto surfaces. They can be
dispensed either from aerosols with a volatile propellant gas or
using a trigger spray which does not require propellant gas. US
patent application 2005/0124512 teaches a cyclodextrin containing
product in which non fabric discolouring aldehydes are incorporated
to react with amines in the air. Nowhere does the patent teach that
aldehydes might inhibit malodour formation without reacting
themselves. US patent application 2003/0044309 teaches an emulsion
composition containing a selection of fragrance aldehydes which
counter pre-existing malodours when in direct contact with fabrics
which again teaches reactive chemistry rather than prevention of
indole based malodour development. Fragrances incorporating indole
inhibiting materials can also be used advantageously in these
products.
Room Air Fresheners
[0064] Products for freshening or fragrancing general ambient air
countering malodours or repelling insects devices include devices
which have no power source and work by diffusion or by electrical
heating a wick in contact with a liquid reservoir so that the rate
of fragrance can be controlled. Such devices can be mains powered
so called plug-in fresheners as described in U.S. Pat. No.
6,917,754 or battery powered so portable or for use in a motor
vehicle. Optionally the device may use an atomizing spray to
disperse the fragrance or contain an electrically powered fan.
Fragrance compositions of the present invention can be dispersed by
these freshener devices and settle on surfaces to prevent malodour
developing.
Fibrous Articles Intended for the Absorption of Bodily Fluids
[0065] Considerable success has been achieved in the design of
products intended to absorb and retain human and animal waste
materials. The construction of articles such as disposable diapers
and training pants, sanitary napkins and tampons and incontinence
products for example has become sophisticated with the addition of
elastics, barrier layers superabsorbing polymers and the like to
retain more waste and prevent leakage. Reference may be made to
U.S. Pat. Nos. 4,846,823; 5,932,495 or 4,335,722 which are
incorporated herein by reference for descriptions of the
technology. The control of odour remains a challenge that is
exacerbated by the technical improvements mentioned above, which
has led to larger quantities of waste being contained in products
designed to require changing less frequently.
[0066] Attempts to prevent such odours from forming or to absorb
those formed have often involved antimicrobial treatments. The use
of additives such as activated carbon, zeolites, metals such as
copper, metal oxides, alumina hydrate, minerals such as holmite,
laconite, kaolin and modifications of molecular sieves have been
suggested as well as the use of acid/base interactions to
neutralize the various odor forming components. U.S. Pat. No.
6,031,147 teaches the use of surfactants to suppress the odour in
disposable absorbent products. US patent application 2002/0010447
also teaches several of the above and also the use of a mixture of
two types of aldehydes but it does not teach that aldehydes prevent
the development of malodours associated with indolic compounds, nor
that the aldehydes are unchanged by the interaction. In spite of
these efforts, there remains a need to control odours better.
EXAMPLE 1
Identification of Active Fragrance Compounds
[0067] A sample of fresh human urine is divided into equal portions
and a fragrance containing one or more of the effective materials
was added as described in the Indole Inhibition Test. Control
samples were prepared in which inactive compounds were substituted
and a third unfragranced blank was also prepared to determine the
suitability of the urine. The samples were stored and after 24
hours the indole content and fragrance active content is measured
by gas chromatography with mass spectrometric (GCMS) detection.
Those formulations containing active ingredients prevented the
formation of indole while both the unfragranced and the alcohol
containing control samples had much greater quantities of indole
present. Also for the active compounds a GCMS measurement indicated
the extent to which the compound was itself consumed as part of the
process. In table 2 the decrease in fragrance components has been
classified into 3 categories and the letter Y indicates the
appropriate category for the compounds which have been measured.
The absence of a letter Y in any category means that the decrease
has not been measured for that compound.
TABLE-US-00002 TABLE 2 Examples of effective materials Decrease in
Fragrance Compounds after 24 hours (%) Active Compounds/CAS Nos 0
30% 0 60% >60% Acetophenone 98-86-2 Benzaldehyde 100-52-7 Y
Benzophenone 119-61-9 Cinnamic aldehyde 104-55-2 Y Citronellal
5949-05-3 Trans 2 hexenal 6728-26-3 Y Trans 2 hexenol 928-95-0
Aldehyde C11 112-44-7 Y Citral 5392-40-5 Y Aldehyde C-10 112-31-2
Perilla aldehyde 2111-75-3 Y Perilla alcohol 536-59-4 Veltol Plus
4940-11-8 Y Heliobouquet 1205-17-0 Y = Yes
[0068] The following compounds were found to be ineffective at
reducing indole levels in urine over 24 hours.
Inactive Compounds/CAS Nos:
Benzyl alcohol 100-51-6
Phenyl ethyl alcohol 60-12-8
Cinnamic alcohol 104-54-1
Citronellol 106-22-9
Alcohol C10 112-30-1
Hexyl cinnamic aldehyde 101-86-0
Amyl cinnamic alcohol 101-85-9
Kovanol 31906-04-4
Anisic Alcohol 105-13-5
Dimethyl Octenone 2550-11-0
Dimethyl Octanol 106-21-8
.alpha. Damascone 24720-09-0
Phenylacetaldehyde 122-78-1
Lilial 80-54-6
Laurinal 107-75-5
Geraniol 106-24-1
Nerol 106-25-2
B Ionone 14901-07-6
Cyclamen aldehyde 103-95-7
Myrac aldehyde 37677-14-8
Vanillin 121-33-5
Ethyl vanillin 121-32-4
Canthoxal 5462-06-6
Cuminic aid 122-03-2
Phenoxanol 55066-48-3
Triplal 68039-49-6
EXAMPLE 2
Performance from a Liquid Rim Block
[0069] The active composition of Table 3 (example 2) was mixed into
a liquid rimblock formulation having the composition of example 6
of which 0.25 g was added to 7.0 g of a fresh suitable human urine
sample to give 0.02 g of active fragrance as described in part B of
the indole inhibition test. After 24 hours the indole content was
measured and the result shown as file URIN40.D in FIG. 1.
Comparative example A control was mixed with the same liquid rim
block formulation and gave the results in file URIN41.D in FIG. 1
while a blank sample containing 0.2 g of the liquid rim block
formulation in urine gave file URIN39.D in FIG. 1. It can be seen
the fragrance composition of the invention reduced indole
concentration below 0.01 ppm (wt/wt). Note that the dosage of
example 2 and comparative A in the liquid rim block represents
about 30% of the normal total fragrance dose.
TABLE-US-00003 TABLE 3 Effectiveness in a Liquid Rim Block -
Formulation of Active Components Example 2 Comparative Example A
Compound % Compound % Benzaldehyde 33.3 Benzyl alcohol 33.3
Cinnamic Aldehyde 33.3 Cinnamic alcohol 33.3 Phenylacetaldehyde
33.3 Phenylethyl alcohol 33.3
EXAMPLE 3
[0070] Table 4 below demonstrates a fragrance composition according
to the present invention containing 5% of active ingredient
suitable for use in household products, along with a control
fragrance comparative example B containing the corresponding
inactive alcohols to the active aldehydes.
TABLE-US-00004 TABLE 4 Example of Effective and Ineffective
Fragrances Example 3 Comparative Example B Compound % Compound %
Benzaldehyde 5 Benzyl alcohol 5 Geraniol 98% 20 Geraniol 98% 20
Geranium oil Egypt nat 2 Geranium oil Egypt nat 2 Verdox 5 Verdox 5
Manzanate 5 Manzanate 5 Musk t-93 5 Musk t-93 5 Phenyl acetaldehyde
10 Phenyl ethyl alcohol 10 Phenyl ethyl alcohol 42 Phenyl ethyl
alcohol 42 Phenylethylphenylacetate 5 Phenylethylphenylacetate 5
Rose oxide 1 Rose oxide 1
EXAMPLE 4
[0071] Table 5 demonstrates a fragrance composition according to
the present invention containing 23% of active ingredients and
suitable for use in household products, along with a control
fragrance comparative example C containing the corresponding
inactive alcohols to the active aldehydes
TABLE-US-00005 TABLE 5 Effective and Ineffective Fragrances Example
3 Comparative Example C Compound % compound % Adehyde C-10 FCC 2
Decanol 2 Aldehyde C8 1 Octanol 1 Allyl caproate 5 Allyl caproate 5
Benzaldehyde 10 Benzyl alcohol 10 Citral 10 Citronellol 10
Citronellol 10 Citronellol 10 Citronellyl nitrile 5 Citronellyl
Nitrile 5 Dihydromyrcenol 15 Dihydromyrcenol 15 Lemon oil 5 Lemon
oil 5 Terpineol alpha 35 Terpineol alpha 35 Triplal 2 2,4 dimethyl
cyclohex-3- 2 enyl methanol
EXAMPLE 5
Household Cleaner
[0072] Table 6 shows an example of a liquid household cleaner which
can be used to deliver fragrances of the invention.
TABLE-US-00006 TABLE 6 Household Cleaner Ingredient Purity Wt %
Secondary alkane sulphonate Hostapur 60 13.0 SAS 60 Alcohol
ethoxylate e.g. Neodol 91-6 EO 100 2.0 Lactic acid 100 0.5
Propylene glycol n butyl ether 0.5 Perfume of composition as in
example 3 100 0.35 Preservative dye other minors q.s. Water 100 To
100 Hostapur SAS 60 supplied by Clariant Neodol 91-6 supplied by
Shell Chemicals
EXAMPLE 6
Liquid Rim Block
[0073] Table 7 shows an example of a liquid rim block which can be
used to deliver fragrances of the invention
TABLE-US-00007 TABLE 7 Household Cleaner Ingredient Wt % Emulgin
HF70 16.7 1,2 Propylene glycol 4.0 Perfume of composition as in 8.0
example 3 Kathon CG 0.005 Natrosol 250MR 11.7 Dyes and other minors
q.s. Water To 100 Emulgin HF70 supplied by Cognis Kathon CG
supplied by Seppic Natrosol 250MR supplied by Hercules
EXAMPLE 7
[0074] Table 8 shows an example of an acidic toilet bowl cleaner
which can be used to deliver fragrances of the invention
TABLE-US-00008 TABLE 8 Toilet Bowl Cleaner Ingredient Purity Wt %
Secondary alkane sulphonate Hostapur 60 7.5 SAS60 Alcohol
ethoxylate eg Neodol 91-6 EO 100 3.0 C12/18Amine oxide 30 5.0
Citric acid 100 10 Perfume of composition as in example 3 100 0.4
Preservative dye other minors q.s. water 100 To 100
EXAMPLE 8
Concentrated Toilet Bowl Cleaner
[0075] Table 9 shows an example of a concentrated toilet bowl
cleaner which can be used to deliver fragrances of the
invention.
TABLE-US-00009 TABLE 9 Concentrated Toilet Bowl Cleaner Ingredient
Purity Wt % Secondary alkane sulphonate 60 12.0 Hostapur SAS60
Alcohol ethoxylate eg Neodol 100 9.0 91-7 EO Citric Acid 100 15
Phosphoric acid 15.0 Hordaphos CCMS 15.0 Perfume of composition as
in 100 0.8 example 3 Preservative dye other minors q.s. Water 100
To 100 Hordaphos CCMS supplied by Clariant
EXAMPLE 9
Acidic Abrasive Cleaner
[0076] Table 10 shows an example of an acidic abrasive liquid
household cleaner which can be used to deliver fragrances of the
invention
TABLE-US-00010 TABLE 10 Acidic Abrasive Cleaner Ingredient Purity
Wt % Secondary alkane sulphonate 60 5.3 Hostapur SAS60 Alcohol
ethoxylate eg Neodol 100 6.4 91-6 EO Lactic acid 100 3.3 Water 100
66.2 Perfume of composition as in 100 0.4 example 3 Preservative
dye other minors q.s. Quartz powder* 100 18.8 Water 100 To 100 *eg
Alsigra 25 from Alpha Calcit Fullstoff Gmbh
* * * * *