Note: Descriptions are shown in the official language in which they were submitted.
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CLEANING COMPOSITIONS
Field of the invention
The present invention relates to cleaning compositions, especially to
thickened liquid cleaning compositions exhibiting effective cleaning
performance and viscosity.
Backaround of the invention
Efficient cleaning performance and viscosity of the cleaning compositions are
25 two requirements which drive consumer acceptance of cleaning products.
Indeed, viscosity enables cleaning compositions to remain long enough on the
surface to provide an effective cleaning action. Such a requirement is of
particular utility in cleaning compositions intended to be applied "as is" to
non-horizontal structurai surfaces such as walls, windows and sanitary
30 fittings such as sinks, baths, showers, wash basins and WCs. More
particularly, viscosities of 10 cps to 4000 cps are suitable. On the other
hand, effective cleaning is important, especially on greasy and oily soils
and/or where the composition is thereafter diluted.
35 It is therefore an object of the present invention to provide cleaning
compositions having effective cleaning performance and viscosity.
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The Applicant has now found that the combination of a surfactant system,
comprising a short chain surfactant and a long chain surfactant, and a
polycarboxylate polymer in a liquid cleaning composition fulfils such a need.
5 Another advantage of the present invention is that it provides stable
compositions, especially in presence of a bleach component.
Another advantage of the present invention is that it provides liquid cleaning
compositions which are safe to the user when said composition is sprayed
10 onto the surface to be treated.
Summarv of the invention
The present invention is a liquid cteaning composition comprising:
i)-a surfactant system comprising a short chain surfactant and a long chain
surfactant, said surfactants comprising a hydrophobic portion and a
20 hydrophilic portion, wherein the chain length of the hydrophobic portion of
the short chain surfactant is C6 to C10 and the chain length of the
hydrophobic portion of the long chain surfactant is C1 1 to C20 carbon
atoms; and
25 ii)-a polycarboxylate polymer;
with the proviso that where the chain length of the hydrophobic portion of
the short chain surfactant is C6 to Cg, the short chain and the long chain
surfactant are presenl in a weight ratio of said short chain to said long chain
30 surfactant of less than 4:1.
The present invention further encompasses the use of a polycarboxylate
polymer in a liquid cleaning composition, in a sprayed form, for preventing or
reducing inhalation of said composition by the user as said composition is
3 5 sprayed .
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In a further aspect of the invention, there is provided a method for cleaning a
hard surface by applying on said surface an effective amount of a
composition of the present invention.
Detailed descriDtion of the invention
Surfactant svstem
A surfactant system is an essential feature of the invention. The surfactant
system comprises a short chain surfactant and a long chain surfactant. All
surfactants have in common that they comprise a hydrophobic portion and a
hydrophilic portion.
For the purpose of the invention, where the chain length of the hydrophobic
portion of the short chain surfactant is C6 to Cg, the short chain and the long
chain su, factant are present in a wei~ht ratio of said short chain to said longchain surfactant of less than 4:1, preferably less than 2:1, more preferably
less than or equal to 1 :1 .
Short chain surfactant
By short chain surfactant, it is meant herein surfactants which comprise a
C6-C 10 alkyl chain as their hydrophobic portion. Such short chain
surfactants are accordingly those conventionally used in this field, but with a
shorter alkyl chain. Suitable short chain surfactants for use herein are
selected from the group consisting of C6-C10 alkyl sulphates (C6-C10S04),
alkyl ether sulphates (C6-C1 o(OCH2CH2)eS04), alkyl sulphonates (C6-
C1 0S03), alkyl succinates (C6-C1 oOOCCH2CH2COOZ), alkyl carboxylates
(C6-C10COOM), alkyl ether carboxylates (C6-C10(ocH2cH2)ecooM)r alkyl
sarcosinates (C6-C1 oCON (CH3)R), alkyl sulpho succinates (C6-
C1 oOOCCH(S03M)CH2COOZ), capped alkyl ethoxylates (C6-
C 1 o(OCH2CH2)fOR, capped alkyl ethoxylates carboxylates (C6-
C1 o(OCH2CH2)f(CH2)COOR, amine oxides (C6-C1 oRR'NO), and betaines
(C6-C10N + (CH3)2CH2COO-). In the formulae in brackets, e is from O to 20,
f is from 1 to 16, preferably 1 to 5, Z is M or R, M is H or any counterion
..
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such as those known in the art, including Na, K, Li, NH4, amine, R and R' are
C1-Cs alkyl groups, possibly functionalized with hydroxyl groups, R and R'
are preferably C1-C3, most preferably methyl. The compositions according to
the present invention may comprise any of the above surfactants alone, or
any combination thereof, depending on the end use envisioned.
Preferred short chain surfactants for use herein are hypochlorite compatible,
e.g surfactants which contain no functionalities (such as ether linkages,
unsaturation, some aromatic structures or hydroxyi groups) which are
susceptible of oxidation by the hypochlorite bleach. More preferably, the
short chain surfactants for use herein are anionic short chains. Preferably, theanionic short chain surfactants comprise a C7-Cg alkyl chain as their
hy~rophobic portion. Preferred anionic short chain surfactants among the one
above disclosed are the alkyl sulphates and alkyl sulphonates. Most preferred
anionic short chain surfactants are selected from the C7-Cg alkyl sulphates,
C7-Cg alkyl sulphonates and mixtures thereof. A most preferred short chain
surfactants for use herein is octyl sulphate. Such short chain anionic
surfactants can be made by well known sulphation or sulphonation processes
followed by neutralisation, but said anionic short chain surfactants are more
conveniently commercially available, for instance from Rhone Poulenc under
the trade name Rhodapon(~) OLS, from Witco under the trade name Witconate
~), or from Albright and Wilson under the trade name Empimin~). A preferred
commercially available compound is Empimin~) LV33.
According to the present invention, the compositions comprise from 0.1% to
5%, preferably 0.3% to 4% by weight, more preferably from 0.6% to 2.5%
by weight, of short chain surfactants.
Long chain surfactants
Long chain surfactants for use herein are those which comprise a C1 1-C20
alkyl chain as their hydrophobic portion. Suitable long chain surfactants are
selected from C1 1-C20 alkyl sulphates (C1 1-C20S04), alkyl ether sulphates
(C1 1-C20(0CH2CH2)eS04), alkyl sulphonates (C1 1-C20S03), alkyl aryl
sulphonates (C1 1-C20arylso3)~ alkyl succinates ~C1 1-
C2000CCH2CH2COOZ), alkyl carboxylates (C1 1-C20COOM), alkyl ether
carboxylates ~C1 1-C20(0CH2CH2)eCOOM), alkyl sarcosinates (C1 1-
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C20CON~CH3)R), alkyl sulpho succinates (C1 1-
C2000CCH~S03M)CH2COOZ), capped alkyl ethoxyiates (C1 1-
C20(ocH2cH2)foR~ capped alkyl ethoxylates carboxylates (C1 1-
C20(ocH2cH2)f(cH2)cooR~ amine oxides (C1 1-C20RR'NO), and betaines
(C1 1 -C20N + R1 R2R3COO-) wherein R1, R2, R3 are independently C1 -C6
alkyl, hydroxy alkyl or other substituted C1-C6 alkyl groups. In the formulae
in brackets, e is from O to 20, f is from 1 to 16, preferably 1 to 5, Z is M or
R, M is H or any counterion such as those known in the art, including Na, K,
Ei, NH4, amine, R and R' are C1-Cs alkyl groups, possibly functionalized with
hydroxyl groups, R and R' are preferably C1-C3, most preferably methyl. The
compositions according to the present invention may comprise any of the
above surfactants alone, or any combination thereof, depending on the end
use envisioned.
Preferred long chain surfactants for use herein are hypochlorite compatible,
e.g surfactants which contain no functionalities ~such as ether linkages,
unsaturation, some aromatic structures or hydroxyl groups) which are
susceptible of oxidation by the hypochlorite bleach.
More preferably, the long chain surfactants for use herein are anionic long
chains. Preferably, the long chain anionic surfactants for use hereln comprise
a C1 1-C1g~ more preferably a C12-C14 alkyl chain as their hydrophobic
portion or a C 1 1 -C 1 8 alkyl aryl chain, more preferably a C 1 1 -C 1 8 alkylbenzene chain. Preferred anionic long chain surfactants among the one above
disclosed are alkyl sulphates and/or alkyl aryl sulphonates. Most preferred are
the C12-C14 alkyl sulphates and/or C1 1-C14 alkyl benzene sulphonates.
Preferred alkyl sulphates for use herein are selected from sodium tallow alkyl
sulphate, sodium lauryl sulphate and mixtures thereof. A preferred
commercially available compound is Empicol~ 0298tF from Albright and
Wilson. Preferred alkyl aryl sulphonates for use herein are commercially
available from Albright and Wilson.
Other particularly suitable long chain surfactants herein are betaine
surfactants of the formula C1 1-C2oN+R1R2R3COO- wherein R1, R2, R3 are
independently C1-C6 alkyl, hydroxy alkyl or other substituted C1-C6 alkyl
groups, preferably C1-C4 alkyl, more preferably selected from methyl, ethyl,
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propyl and most preferably methyl. Suitable alkyl betaines are C1 1-C20 alkyl
dimethyl betaine, preferably C1 1-C1 4 alkyl dimethyl betaine such as pure cut
C12 alkyl dimethyl betaine commercially available from Hoechst.
5 Compositions according to the present invention comprise from 0.1% to 5%,
preferably from 1% to 3% by weight of the total compositions of said long
chain surfactants.
Where amine oxide is used as a long chain surfactant, it is preferred for
10 convenient use of the composition that the level of said long chain amine
oxide surfactant is present at a level of from 0.1% to 2% by weight of the
composition. Above such levels, the composition may tend to be too viscous
to be easily usable.
t5 turthermore, the use of long chain amine oxide surfactants in the cleaning
composition of the invention which provide etrecLi~/e cleaning and viscosity
performance is especially surprising as the Applicant has found that in the
absence of a polycarboxylate polymer, a problem encountered with the use of
such amine oxide is that the activity of the short chain surfactant is hindered
20 by said long chain amine oxide su-tactaot, so that the cleaning performance
of the short chain surfactant does not act to its best performance.
Not to be bound by theory, it is believed that the amine oxide surfactant,
especially long chain amine oxides, and the short chain surfactant are trapped
25 in the cylindrical l--i~ system, formed by the amine oxide surfactants, that
generates the viscosity. As a result, the short chain surfactant is not
completely free to move and loses part of its cleaning power.
The Applicant has now found that the use of a polycarboxylate polymer not
30 only overcomes the problem but also supports the cleaning efficiency of the
surfactant system, even in the presence of long chain amine oxide
surfactants.
35 Polvcarboxvlate polvmer
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Another essential component of the invention is a polycarboxylate polymer.
The polycarboxylate polymers, contrary to cellulosic polymers such as guar
gum or xanthum gum, are more stable in presence of hypochlorite bleach,
provide better thickening efficiency and also a higher yield value. Such high
5 yield value is of particular utility where the composition is packaged in a
spray-type dispenser.
The polymers for use herein preferably have a molecular weight of from
200.000 to 5.000.000, preferably from 500.000 to 4.500.000, more
preferably from 1.000.000 to 4.000.000. Most preferred polymers for use
herein contain from 0.5% to 4% by weight of a cross-linking agent, wherein
the cross-linking agent tends to interconnect linear strands of the polymers to
form the resulting cross-linked products. Suitable cross-linking agents include
the polyalkenyl polyethers. Polycarboxylate polymers include the polyacrylate
15 polymers. Other monomers besides acrylic acid can be used to form these
polymers including such monomers as maleic anhydride which acts as a
source of additional carboxylic groups. The molecular weight per carboxylate
group of monomers containing a carboxylate group typically varies from 25
to 200, preferably from 50 to 150, more preferably from 75 to 125. Further
20 other monomers may be present in the monomeric mixture, if desired, such
as ethylene and propylene which act as diluents.
Preferred polycarboxylate polymers for use herein are the polyacrylate
polymers. Commercially available polymers of the polyacrylate type include
25 those sold under the trade names Carbopol@), Acrysol~MCS-1, Polygel~, and
Sokalan~9. Most prefe.,ed polyacrylate polymers are the copolymer of acrylic
acid and alkyl (Cs-C1o) acrylate, commercially available under the tradename
Carbopol@) 1623, Carbopol~3) 695 from BF Goodrich, and copolymer of acrylic
acid and maleic anhydride, commercially available under the tradename
30 Polygel~9 DB, Polygel~9 DV, Polygel~9 DA, from 3V Chemical company.
Mixtures of any of the polycarboxylate polymers, herein before described,
may also be used.
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The polymer is present in an amount of from 0.1 % to 4% by weight,
preferably 0.3 to 4% by weight, more preferably 0.4% to 1.5% by weight of
the composition.
5 The Applicant has now surprisingly found that the present polymer performs
dual functions when it is incorporated in the composition herein, said
functions being not only to thicken but also to support the cleaning
performance of the surfactant system.
ODtional comDonents
10 The compositions according to the present invention may comprise a number
of optional ingredients such as bleaching agents, fatty acids, radical
scavengers, antimicrobial compounds, builders, chelants, buffers,
bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators,
soil suspenders, dye transfer agents, brighteners, anti dusting agents,
15 dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
A highly preferred optional ingredient according to the present invention is a
hypochlorite bleaching agent, preferably an alkali metal hypochlorite.
Advantageously, the compositions of the invention are stable in presence of
20 this bleaching agent. Although alkali metal hypochlorites are preferred other hypochlorite compounds may also be used herein and can be selected from
calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for
use herein is sodium hypochlorite. Compositions according to the present
invention comprise said hypochlorite bleaching agents such that the content
25 of active chlorine in the compositions is from 0.1% to 4%, preferably from
1% to 2% by weight.
Another optional component of the present invention is an alkali metal salt of
a Cg-C1g fatty acid. Said fatty acids are used as suds suppressors. Suitable
30 fatty acids for use herein can be any Cg-C18 fatty acid, preferably fully
saturated, preferably a sodium, potassium or lithium salt, more preferably the
sodium salt. Suitable fatty acids may be selected from caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures of
fatty acids suitably hardened, derived from natural sources such as tallow,
.
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coconut oil, ground oil and babassu oil. Compositions according to the
present invention comprise from 0.1% to 2%, preferably less than 0.6% by
weight of the composition of fatty acids.
A further optional component of the present invention is a radical scavenger.
Said radical scavengers are used as stabilisers. A suitable radical scavenger
for use herein is the aromatic molecule containing a carboxylic group ring
substitution. Suitable examples of radical scavengers for use herein include
the meta and para-chlorobenzoic acid, benzoic acid, meta- ortho- and para-
methoxybenzoic acid, meta nitrobenzoic acid, para bromobenzoic acid,
salicylic acid, 5-sulphosalicylic acid, 3,5-dimethyl salicylic acid and paratoluic
acid. Of the above materials, ortho-methoxybenzoic acid is preferred.
Compositions according to the present invention comprise from 0.01% to
1.5% by weight, preferably from 0.1% to 0.8% by weight and more
preferably from 0.2% to 0.5% by weight of the composition of radical
scavengers.
An optional requirement of the compositions according to the present
invention is that the pH is greater than 10, preferably greater than 1 1, more
preferably greater than 12. This is achieved by the addition of from 0.4% to
2% of a caustic alkali. Suitable caustic alkalis for use herein include sodium
and potassium hydroxide. Compositions according to the present invention
comprising hypochlorite preferably have a pH greater than 12 for hypochlorite
stability.
The compositions according to the present invention are preferably a~ueous
and preferably comprise from 80% to 95%, more preferably from 85% to
90% of water.
The compositions according to the present invention are prepared by
methods well known in the art such as the methods described in GB 1 329
086 with the exception of the polymer being pre-dispersed in an acidic water
solution of pH 3 and then neutraJised up to pH 7 before starting adding the
other components. The compositions according to the present invention can
then be prepared by mixing all of the ingredients in a non-metallic apparatus
at room temperature or in warm water. If fatty acid is used, it is melted
before being added to the mixture. Preferably, the surfactant blend is first
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prepared by adding the short chain surfactant to the long chain surfactants.
Other optionals such as perfume and the alkali metal hypochlorite are then
added whilst stirring. Colourants, if present, are added after all the other
ingredients have been mixed.
The compositions according to the present invention preferably have a
viscosity of from 10 cps to 4000 cps, more preferably from 50 cps to 2000
cps, most preferably from 150 cps to 1000 cps measured with a Carrimed
Rheometer at a temperature of 25~C and a shear rate of 15-35 s~1. Where
10 the composition is in a sprayed form, the viscosity of said spraying
compositions is preferably of from 15 cps to 40 cps.
The compositions of the present invention may be used for a variety of
cleaning purposes such as cleaning hard surfaces whereby said compositions
15 thickened nature results in longer adhesion to the surface than non-thickenedcompositions. By "hard surface" it is meant herein any surface like bathroom,
sanitary fittings such as sinks, showers, wash basins and WCs, kitchen,
sinks, cooker tops, table tops, refrigerators, walls, windows and the like.
20 Packaging form of the compositions
The compositions herein may be packaged in a variety of suitable detergent
packaging known to those skilled in the art. The liquid compositions herein
may desirably be pack~ge~l in manually operated spray dispensing containers,
25 which are usually made of synthetic organic polymeric plastic materials.
Accordingly, the pressnt invention also encompasses liquid cleaning
cornpGsilions of the invention packaged in a spray dispenser, preferably in a
trigger spray dispenser. Indeed, said spray-type dispensers allow to uniformly
apply to a relatively large area of a surface to be cleaned the liquid cleaning
30 compositions suitable for use according to the present invention; thereby
contributing to the cleaning properties of said compositions. Such spray-type
dispensers are particularly suitable to clean vertical surfaces. Surprisingly, the
spraying of a liquid composition containing a polycarboxylate polymer,
contrary to compositions which do not contain the polycarboxylate polymer,
35 has been seen beneficial for preventing or reducing inhalation of the
composition by the user as said composition is sprayed.
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1 1
The present avantage is preferably observed where the cleaning composition
is as defined hereinbefore. Accordingly, the use of a polycarboxylate polymer
in a liquid cleaning composition is provided, said composition being in a
5 sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed. Preferably, the liquid cleaning
composition is as defined hereinbefore.
Suitable spray-type dispensers to be used according to the present invention
10 include manually operated foam trigger-type dispensers sold for example by
Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types
of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al.
and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly
preferred to be used herein are spray-type dispensers such as T 8500(~) or T
8900(~commercially available from Continental Spray International or T 8100
~) commercially available from Canyon, Northern Ireland. In such a dispenser
the liquid composition is divided in fine liquid droplets resulting in a spray that
is directed onto the surface to be treated. Indeed, in such a spray-type
dispenser the composition contained in the body of said dispenser is directed
20 through the spray-type dispenser head via energy communicated to a
pumping mechanism by the user as said user activates said pumping
mechanism. More particularly, in said spray-type dispenser head the
composition is forced against an obstacle, e.g. a grid or a cone or the like,
thereby providing shocks to help atomise the liquid composition, i.e. to help
25 the formation of liquid droplets.
The present invention further encompasses a method for cleaning a hard
surface by applying on said surface an effective amount of a composition of
the invention. The said composition may be applied in its neat form or after
30 having been diluted with water. Preferably said composition is diluted up to
200 times its weight of water, preferably into 50 to 150 times its weight of
water and more preferably 75 to 95, before it is applied to said surface.
When the composition is diluted prior to use (to reach a total active level in
the order of 1.2%), the composition will still advantageously provide
35 effective cleaning performance. In the preferred embodiment of the method
of the present invention wherein said composition is applied to a hard-surface
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to be cleaned in its diluted form, it may not be necessary to rinse the surface
after the composition has been applied.
In the detergent compositions of the invention, the abbreviated component
5 identifications have the following meaning:
C8 AS : Octyl sulphate, available from Albright and Wilson,
under the tradename Empimin~ LV33
Alkyl : C12 alkyl dimethyl betaine commercially available from
betaine Hoechst
HLAS : C1 1-C14 alkyl benzene sulphonate available from
Albright and Wilson
24 AS : Sodium C12 - C14 alkyl sulphate, available from
Albright and Wilson, under the tradename Empicol(~
0298/F
24E3S : C12 - C14 sodium alkyl sulphate condensed with an
average of 3 moles of ethylene oxide per mole
Amine oxide : C12 - C14 amine oxide, commercially available under
the tradename Genaminox(~ LA from Hoechst
Polymer : Copolymer of acrylic acid and alkyl (Cs-C10) acrylate,
commercially available under the tradename Carbopol@)
1623 from BF Goodrich or copolymer of acrylic acid
and maleic anhydride, commercially available under the
tradename Polygel(B) DA from 3V Sigma company.
Fatty acid : C8 - C18 fatty acid
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nonionic : Capped ethoxylated carboxylate of formula C 12-
C14(0CH2CH2)XCH2COOR, wherein x is an integer
ranging from 2 to 4
The invention is illustrated in the following non-limiting examples, in which all
percentages are on a weight basis unless otherwise stated.
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Exam~le 1
The following compositions, according to the invention, were prepared:
Components A B C D E F G
24 AS 1.0 1.0 2.0 2.0 1.0 1.0 1.0
C8 AS 1.0 1.0 1.0 2.0 2.0 2.0 2.0
Polymer 0.8 0.8 1.2 1.0 1.0 1.5 0.3
Caustic - 1 .4 1 .4 1 . 51 .4 - 1 .0
Sodium hypochlorite - 1.4 1.0 1.0 1.4 1.4 1.4
Fatty acid - 0.2 0.3 0.3 0.2
Water and minors up to 100
10 Examole 2
The following compositions are in accordance with the invention
H I J K L
C8 AS 1.0 1.0 2.0 2.0 2.0
24AE3S 2.0 2.0 1.0 1.0 1.0
Polymer 0.8 1.0 1.2 1.0 0.4
nonionic 0.5 0.5 1.0 1.0 0.5
fatty acid 0.3 0.3 0.3 0.3 0.3
Caustic 1.4 1.4 1.4 1.4 1.0
sodium hypochlorite 1.4 1.6 1.6 1.4 1.4
Water and minors up to 100
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ExamPle 3
The following compositions are in accordance with the invention
M N 0 P Q R
amine oxide 0.4 0.4 0.8 - - -
24 AS - 2.0 2.0 - - -
Alkyl betaine - - - 2.0
HLAS - - - - 2.0 2.0
C8 AS 2.0 2.0 2.0 1.5 1.5 2.0
Polymer 0.8 0.8 0.8 1.1 1.1 0.8
Caustic 1.4 1.4 1.4 1.1 1.1 1.1
Sodium 1.4 1.4 1.4 1.1 1.1 1.4
hypochlorite
Water and minors up to 100
ExamPle 4
The following compositions were made and packaged in a spray-trigger
dispenser T 8500~:
S T U V X
C8 AS 2.0 2.0 3.0 1.5 2.0
HLAS - - - 2.0 0.5
24AS 1 .0 - 0. 3
24AE3S - 1.0
Polymer 0.3 0.4 0.4 0.3 0.4
nonionic - 0.5
fatty acid - 0.3 - 0.1 0.1
Caustic 1.0 1.0 1.0 1.0 1.0
sodium hypochlorite 1.4 1.4 1.4 1.1 1.1
Water and minors up to 100
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16
The above compositions, in a sprayed form, exhibited reduced inhalation of
said composition by the user as said composition was sprayed as compared
to compositions, in a sprayed form, which did not contain the
polycarboxylate polymer.
