Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS OF CLEANING ENAMEL SURFACES
Technical field
The present invention relates to a process of cleaning enamel surfaces with a
liquid acidic composition.
Background of the invention
Compositions for cleaning enamel surfaces are well known in the art.
Liquid compositions having an acidic pH for cleaning enamel surfaces have
been extensively described in the art, especially in hard surface cleaning
application (e.g., bathroom cleaner).
Indeed, it is known to use acidic compositions to clean enamel surfaces as
such
formulations show good soap scum removal performance and limescale removal
performance. Soap scum and limescale are soils that frequently occur on
enamel surfaces, especially enamel surfaces located in bathrooms, kitchens and
the like.
However, there are some limitations to the convenience of acidic compositions
employed as enamel surface cleaner. In particular it is know, that enamel
surfaces are sensitive to acids and may be severely damaged by acidic
compositions used to clean said surfaces.
It is thus and aspect of the present invention to provide a process of
cleaning
enamel surfaces with an acidic composition which is safe to said enamel
surfaces while exhibiting a good cleaning performance on a variety of soils.
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It has now been found that the above aspect is met by a process of cleaning an
enamel surface with a liquid acidic composition comprising an enamel safe
buffering system.
Advantageously, said process of cleaning enamel surfaces rnay be used on
various enamel surfaces. Enamel surfaces can be found in various places, e.g.,
in households : in kitchens (sinks and the tike); in bathrooms (tubs, sinks,
shower tiles, bathroom enamelware and the like); in washing machines; and
dishes.
A further advantage of the process as described herein is that the
compositions
used to clean enamel surfaces show good stain/soil removal performance.
More particularly, the liquid acidic compositions show good stain/soil removal
performance on various types of stains/soils in particular : greasy soils,
e.g.,
greasy soap scum or greasy soils found in kitchens; limescale; mold; mildew;
and other tough stains found on enamel surfaces.
Background art
EP-B-580 838 and EP-A-647 706 disclose hard surface cleaning compositions
comprising a surfactant and optionally ammonium hydroxide as a buffer.
However, said applications do not disclose a process of cleaning enamel
surfaces with a liquid acidic composition as described herein.
US 4,501,680 discloses acidic liquid detergent compositions comprising
mixtures of organic acids, an ether of diethylene glycol and a surfactant.
Summary of the invention
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The present invention encompasses a process of cleaning an enamel surface
with a liquid acidic composition comprising an enamel safe buffering system
wherein said buffering system comprises a salt having : an anion selected from
the group consisting of hydroxide and carbonate; and a cation that has an
ionic
radius larger than 115 pm; with the proviso that no ethers of diethylene
glycol
are present in said composition.
In a preferred embodiment said cation having an ionic radius larger than 115
pm
is selected from the group consisting of a potassium ion, an ammonium ion, a
cesium ion, a barium ion and a quaternary ammonium ion.
In another preferred embodiment said composition further comprises a source of
acidity.
In another preferred embodiment said composition further comprises a
surfactant.
The present invention further encompasses the use of an enamel safe buffering
system in a composition to clean an enamel surface wherein said buffering
system comprises a salt having : an anion selected from the group consisting
of
hydroxide and carbonate; and a cation that has an ionic radius larger than 115
pm; whereby said composition is safe to enamel.
Detailed descrietion of the invention
The process of treating a hard-surface
The present invention encompasses a process of treating an enamel surface
with a liquid acidic composition comprising an enamel safe buffering system as
described herein. In a preferred embodiment said acidic liquid composition is
contacted with said enamel surface.
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By "enamel surface" it is meant herein any kind of surface being made of or
coated with enamel.
By "enamel" it is meant titanium or zirconium white enamel or titanium or
zirconium white powder enamel used as a coating for metal (e.g., steel)
surfaces
preferably to prevent corrosion of said metal surfaces.
Enamel surfaces can typically be found in houses : e.g., in bathrooms or in
kitchens : e.g., tiles, sinks, showers, shower wash basins, WCs, tubs, sinks,
fixtures and fittings and the like. Furthermore, cookware, dishes and the like
may
have an enamel surface. Enamel surfaces may also be found on household
appliances which may be coated with enamel on their inside andlor outside
surface including, but not limited to, heating boiler, washing machines,
automatic
dryers, refrigerators, freezers, ovens, microwave ovens, dishwashers and so
on.
Further enamel surfaces may be found in industrial, architectural and the like
applications. Examples of enamel surfaces found in said applications include
enamel surfaces on or in tanks, pipelines, reaction vessels, pumps, chemical
processing equipment, mechanical equipment, heat exchangers, hot water
tanks, signs, silos or architectural panels.
The liquid acidic composition of the present invention may be contacted to the
surface to be treated in its neat form or in its diluted form.
By "diluted form", it is meant herein that said liquid composition is diluted
by the
user typically with water. The composition is diluted prior to use to a
typical
dilution level of 10 to 400 times its weight of water, preferably from 10 to
200
and more preferably from 10 to 100. A usually recommended dilution level is a
1.2% dilution of the composition in water.
By "in its neat form", it is to be understood that the liquid compositions are
applied directly onto the enamel surface to be treated without undergoing any
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dilution, i.e., the liquid compositions herein are applied onto the hard-
surface as
described herein.
A preferred process of cleaning an enamel surface according to the present
invention, is to apply the composition in diluted form without rinsing the
hard-
surface after application in order to obtain good soil/stain removal
performance.
Another preferred process of treating a enamel surface, is to apply the
composition, described by the present invention, either in neat or diluted
form,
leave it on said surface to act, optionally wipe said surface with an
appropriate
instrument, e.g., a sponge, and then preferably rinse said surface with water.
The enamel surfaces to be treated may be soiled with a variety of soils, e.g.,
greasy soils (e.g., greasy soap scum, body grease, kitchen grease or
burntlsticky food residues typically found in a kitchen and the like) or so
called
"limescale-containing stains". By "limescaie-containing stains" it is meant
herein
any pure limescale stains, i.e., any stains composed essentially of mineral
deposits, as well as limescale-containing stains, i.e., stains which contain
not
only mineral deposits like calcium and/or magnesium carbonate but also soap
scum (e.g., calcium stearate) and other grease (e.g. body grease).
Cleaning performance test method
The dilute cleaning performance may be evaluated by the following test method:
tiles of enamel are prepared by applying to them a representative
grease/particulate artificial soil followed by ageing. The test compositions
and
the reference composition are diluted (e.g., composition:water 1:50 or 1:100),
applied to a sponge, and used to clean the tiles with a Sheen scrub tester.
The
number of strokes required to clean to 100% clean is recorded. A minimum of 6
replicates can be taken with each result being generated in duplicate against
the
reference on each soiled tile.
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The test method for evaluating neat cleaning performance is identical to above
except that the test compositions and reference are used undiluted and that
after cleaning a rinsing cycle is performed with clean water.
Greasy soap scum cleaning performance test method
In this test method enamel white tiles (typically 24 cm * 4 cm) are covered
with
typical greasy soap scum soils mainly based on calcium stearate and artificial
body soils commercially available (e.g., 0.3 grams with a sprayer). The soiled
tiles are then dried in an oven at a temperature of 140°C for 20
minutes and
then aged overnight at room temperature (around 20°C-25°C). Then
the soiled
tiles are cleaned using 3 ml of the liquid composition of the present
invention
poured directly on a Spontex~ sponge. The ability of the composition to remove
greasy soap scum is measured through the number of strokes needed to
perfectly clean the surface. The lower the number of strokes, the higher the
greasy soap scum cleaning ability of the composition.
The liauid acidic composition
The liquid acidic compositions according to the present invention are
preferably
aqueous compositions. Therefore, they may comprise from 70% to 99%,
preferably from 75% to 95% and more preferably from 85% to 95% by weight of
the total composition of water.
The liquid compositions of the present invention are acidic and therefore
preferably have a pH below 7, preferably from 1 to 6.5, more preferably from 1
to 5, even more preferably from 2 to 5 and most preferably from 2 to 4.
The compositions according to the present invention are advantageously
chemically stable, i.e., there are virtually no chemical reactions between the
different ingredients of the compositions, and physically stable, i.e., that
no
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phase separation occurs when stored in rapid aging test (RAT), i.e., storage
at
50 °C for 10 days.
A proviso of the present invention is that the compositions do not contain
ethers
of diethylene glycol. By "ethers of diethylene glycol" it is meant any mono-
lower
alkyl ether or phenyl ether of diethylene glycol as welt as benzyl ether of
diethylene glycol and mixtures thereof. By "lower alkyl ether of diethylene
glycol"
it is meant C2-6 alkyl ether of diethylene glycol.
Buffering sYStem
As an essential ingredient the compositions used in a process according to the
present invention comprise a buffering system.
Said buffering system comprises a salt having : an anion selected from the
group consisting of hydroxide and carbonate; and a cation that has an ionic
radius larger than 115 pm.
Typically the compositions of the present invention may comprise from 0.1 % to
5%, preferably of from 0.1 % to 4% and more preferably of from 0.1 % to 3% by
weight of the total composition of a buffering system.
Preferably the salt is one whose cation has an ionic radius of at least 125
pm,
more preferably of at least 130 pm, even more preferably of at least i35 pm,
and most preferably of at least 140 pm.
Examples of suitable cations in said salt are potassium ions (ionic radius of
K+ is
133 pm), ammonium ions (ionic radius of NH4+ is 142 pm), cesium ions (ionic
radius of Cs+ is 167 pm), barium ions (ionic radius of Ba2+ is 134 pm) or
quaternary ammonium ions.
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Other suitable cations having an ionic radius larger than 115 pm include Ac3+,
Ag+, Am3+, Ar+, Au+, Ba+, Ca+, Cd', Ce+, Ce3+, Fr+, H + H Z+ + 3+ z+
g , g , La , La , Pb ,
Ra2+, Rb+, Srz+, Th4+, TI+ and Zr+.
Sodium has an ionic radius of 112 pm and is therefore, not suitable as cation
in
said buffer ingredient.
Preferably the cation in said salt is selected from the group consisting of a
potassium ion, an ammonium ion, a cesium ion, a barium ion and a quaternary
ammonium ion. More preferably the cation in said salt is a potassium ion or an
ammonium ion.
The anion in said salt is a hydroxide or a carbonate. By "hydroxide" it is
meant
an OH- ion. By "carbonate" it is meant an HC03- or C03z- ion.
Examples of suitable salts to be part of said buffering system are selected
from
the group consisting of potassium hydroxide (KOH), potassium carbonate
(K2C03), potassium bicarbonate (KHC03), ammonium hydroxide (NH40H),
ammonium carbonate ((NH4)2C03), ammonium bicarbonate (NH4HC03), cesium
hydroxide (CsOH), barium hydroxide (Ba(OH)2), barium carbonate (BaC03) and
mixtures thereof.
Preferably the salt is selected from the group consisting of potassium
hydroxide
(KOH), potassium carbonate (K2C03), potassium bicarbonate (KHC03),
ammonium hydroxide (NH40H), ammonium carbonate ((NH4)ZC03), ammonium
bicarbonate (NH4HC03), cesium hydroxide (CsOH), barium hydroxide (Ba(OH)2),
barium carbonate (BaC03) and mixtures thereof. More preferably the salt is
selected from the group consisting of potassium hydroxide, ammonium
hydroxide and mixtures thereof.
Preferably the buffering system consists of one ore more salts as described
above.
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The present invention is based on the finding that a process of cleaning
enamel
with a liquid acidic composition comprising an enamel safe buffering system as
described herein is safe to enamel surfaces.
Another aspect of the present invention is the use of an enamel safe buffering
system in a composition to clean an enamel surface wherein said buffering
system comprises a salt having : an anion selected from the group consisting
of
hydroxide and carbonate; and a cation that has an ionic radius larger than 115
pm; whereby said composition is safe to enamel.
By "safe to enamel surfaces" it is meant herein that the acidic compositions
as
described herein do not damage enamel surfaces as other acidic compositions
may potentially do.
Damage to enamel surfaces may be caused by small cations, i.e., cations
having an ionic radius of 115 pm or less, present in acidic compositions used
to
clean said enamel surfaces. Said small cation can penetrate and spread through
the superficial layers of the crystalline lattice of enamel. Said small
cations may
eventually replace cations originally present in said superficial layers of
the
crystalline lattice of enamel and/or otherwise modify said superficial layers
of the
crystalline lattice of enamel. Thereby, the enamel surface looses its
smoothness
and consequently its gloss. The loss of gloss is perceived as damage to an
enamel surface.
Whilst not wishing to be bound by theory, it is believed that the relatively
big
cations as employed in the buffering system according to the present invention
with a cation ionic radius larger than 115 pm can not penetrate and spread
through the superficial layers of the crystalline lattice of enamel. Thus, the
compositions used in a process to clean an enamel surface as described herein
is safe to said enamel surfaces.
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The degree of enamel damage can be determined by the following enamel
damage test method
Enamel damage test method
A few drops of the composition according to the present invention are placed
on
an enamel surface (e.g., an enamel tile) afterwards, the surface is covered
with
a watch glass. After 15 minutes, the watch glass is removed, the enamel
surface
is rinsed with water (either demineralised or tap) and then wiped dry. Visual
examination (visual grading) or gloss measurements of the surface allow to
verify whether the product is safe (no difference of gloss versus the
untreated
enamel surface) or unsafe (difference of gloss versus the untreated enamel
surface) to enamel.
Optional source of acidity
The compositions according to the present invention are formulated as acidic
compositions. Therefore, said compositions may as a highly preferred optional
ingredient comprise a source of acidity.
Typically, the sources of acidity to be used herein may be any organic or
inorganic acid well-known to those skilled in the art, or a mixture thereof.
Suitable organic acids for use herein, are those selected from the group
consisting of citric acid, malefic acid, lactic acid, glycolic acid, succinic
acid,
glutaric acid and adipic acid, and mixtures thereof. A mixture of said acids
suitable for use herein is commercially available from BASF under the trade
name Sokalan~ DCS. A preferred organic acid for use herein is citric acid.
Preferably, the inorganic acids for use herein have a pKa of less than 3.
Suitable
inorganic acids for use herein, are those selected from the group consisting
of
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sulphuric acid, chloridric acid, phosphoric acid, nitric acid, and mixtures
thereof.
A preferred inorganic acid for use herein is sulfuric acid.
When present, the compositions of the present invention comprise a source of
acidity between 0.5% and 10%, preferably between 1 % and 8%, and most
preferably between 2% and 6% by weight of the total composition.
Optional surfactant
The liquid compositions of the present invention may preferably comprise a
surfactant. Surfactants may be desired herein as they further contribute to
the
cleaning performance of the compositions of the present invention.
Surfactants to be used herein include nonionic surfactants, cationic
surfactants,
anionic surfactants, zwitterionic surfactants, amphoteric surfactants, and
mixtures thereof.
Accordingly, the compositions according to the present invention may comprise
up to 15%, more preferably from 0.5% to 8%, even more preferably from 0.5%
to 8%, and most preferably 0.5% to 8% by weight of the total composition of a
surfactant.
Suitable nonionic surfactants for use herein include a class of compounds,
which may be broadly defined as compounds produced by the condensation of
alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic
compound, which may be branched or linear aliphatic (e.g., Guerbet or
secondary alcohol) or alkyl aromatic in nature. The length of the hydrophilic
or
polyoxyalkylene radical which is condensed with any particular hydrophobic
group can be readily adjusted to yield a water-soluble compound having the
desired degree of balance between hydrophilic and hydrophobic elements.
Accordingly suitable nonionic synthetic detergents include
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(i) The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products of alkyl phenols having an alkyl group containing
from 6 to 20 carbon atoms in either a straight chain or branched chain
configuration, preferably from 8 to 14, and more preferably from 8 to 12
carbon atoms, with ethylene oxide. Said ethylene oxide is typically present
in amounts of from 3 to 25, preferably from 10 to 25 moles of ethylene
oxide per mole of alkyl phenol. The alkyl substituent in such compounds
may be derived from polymerized propylene, diisobutylene, octane, and
nonane; Examples of this type of nonionic surfactants include Triton N-57~
a nonyl phenol ethoxylate (5E0) from Rohm & Haas and Imbentin 0200~
an octyl phenol ethoxylate (20E0) from KOLB.
(ii) Those derived from the condensation of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene diamine
products which may be varied in composition depending upon the balance
between the hydrophobic and hydrophilic elements which is desired.
Examples are compounds containing from 40% to 80% polyoxyethylene by
weight and having a molecular weight of from 5000 to 11000 resulting from
the reaction of ethylene oxide groups with a hydrophobic base constituted
of the reaction product of ethylene diamine and excess propylene oxide,
said base having a molecular weight of the order of 2500 to 3000.
Examples of this type of nonionic surfactants include certain of the
commercially available TetronicTM compounds, marketed by BASF.
(iii) The condensation product of aliphatic alcohols having from 2 to 24
carbon
atoms, in either straight chain or branched chain configuration, preferably
from 6 to 22, more preferably from 6 to 28, and even more preferably 8 to
18 carbon atoms, with from 2 to 35, preferably from 4 to 25, more
preferably from 5 to 18, and even more preferably 3 to 15 moles of
ethylene oxide. Examples of this type of material are a coconut alcohol
ethylene oxide condensate having from 5 to 18 moles of ethylene oxide per
mole of coconut alcohol, the coconut alcohol fraction having from 9 to 14
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carbon atoms. Other examples of this type of nonionic surfactants include
certain of the commercially available Dobanol~, Neodol~ marketed by
Shell or Lutensol~ from BASF. For example Dobanol~ 23.5 (C12-C13
E05), Dobanol~ 91.5 (C9-C11 E05), Dobanol~ 91.8 (C9-C11 E08) and
Lutensol~ A030 (C12-C14 E030).
Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl group
ranges from 10 to 18 carbon atoms and two alkyl groups range from 1 to 3
carbon atoms; the alkyl groups can contain hydroxy substituents; specific
examples are dodecyl di(2-hydroxyethyl)amine oxide and tetradecyl
dimethyl phosphine oxide.
(v) The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol; The
hydrophobic portion of these compounds will preferably have a molecular
weight of from 1500 to 1800 and will exhibit water insolubility. The addition
of polyoxyethylene moieties to this hydrophobic portion tends to increase
the water solubility of the molecule as a whole, and the liquid character of
the product is retained up to the point where the polyoxyethylene content is
50% of the total weight of the condensation product, which corresponds to
condensation with up to 40 moles of ethylene oxide. Examples of
compounds of this type include certain of the commercially available
PluronicTM surfactants, marketed by BASF.
Also useful as a nonionic surfactant are the alkylpalysaccharides disclosed in
U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic
group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon
atoms and polysaccharide, e.g., a polyglycoside, hydrophilic group containing
from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7
saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can
be used, e.g., glucose, galactose, and galactosyl moieties can be substituted
for
the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-
, 3-,
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4-, etc. positions thus giving a glucose or galactose as opposed to a
glucoside or
galactoside.) The intersaccharide bonds can be, e.g., between the one position
of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions of
the
preceding saccharide units.
Optionally, and less desirable, there can be a polyalkyleneoxide chain joining
the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide
is ethylene oxide. Typical hydrophobic groups include alkyl groups, either
saturated or unsaturated, branched or unbranched containing from 8 to 18,
preferably from 10 to 16, carbon atoms. Preferably, the alkyl group can
contain
up to 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to
10,
preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides
are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses
and/or
galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl tetra-, yenta-, and hexaglucosides.
The preferred alkylpolyglycosides have the formula:
R20(CnH2n0~(glucosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyi, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups
contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10,
preferably
from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably
derived
from glucose. To prepare these .compounds, the alcohol or alkylpolyethoxy
alcohol is formed first and then reacted with glucose, or a source of glucose,
to
form the glucoside (attachment at the 1-position). The additional glycosyl
units
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can then be attached between their 1-position and the preceding glycosyl units
2-, 3-, 4- and/or 6- position, preferably predominantely the 2- position.
Other suitable nonionic surfactants for use herein include polyhydroxy fatty
acid
amides of the structural formula
O R1
II
(I) R2-C-N-Z
wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a
mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most
preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably
straight chain C7-C1 g alkyl or alkenyl, more preferably straight chain Cg-C17
alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or
mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will
be
derived from a reducing sugar in a reductive amination reaction; more
preferably
Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose,
lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn
syrup can be utilized as well as the individual sugars listed above. These com
syrups may yield a mix of sugar components for Z. It should be understood that
it is by no means intended to exclude other suitable raw materials. Z
preferably
will be selected from the group consisting of -CH2-(CHOH)n-CH20H, -
CH(CH20H)-(CHOH)n_1-CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH20H,
where n is an integer from 3 to 5, _inclusive, and R' is H or a cyclic or
aliphatic
monosaccharide, and alkoxylated derivatives thereof. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
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In Formula (I), R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-
isopropyl,
N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
Other suitable nonionic surfactants for use herein include the amine oxides
corresponding to the formula:
RR'R"N-~O
wherein R is a primary alkyl group containing from 6 to 24 carbons, preferably
from 10 to 18 carbons, and wherein R' and R" are, each, independently, an
alkyl
group containing 1 to 6 carbon atoms. The arrow in the formula is a
conventional
representation of a semi-polar bond. The preferred amine oxides are those in
which the primary alkyl group has a straight chain in at least most of the
molecules, generally at least 70%, preferably at least 90% of the molecules,
and
the amine oxides which are especially preferred are those in which R contains
from 10 to 18 carbons and R' and R" are both methyl. Exemplary of the
preferred amine oxides are the N-hexyldimethylamine oxide, N-
octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyl
dimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyl
dimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine
oxide, N-docosyldimethylamine oxide, N-tetracosyl dimethylamine oxide, the
corresponding amine oxides in which one or both of the methyl groups are
replaced with ethyl or 2-hydroxyethyl groups and mixtures thereof. A most
preferred amine oxide for use herein is N-decyldimethylamine oxide.
Other suitable nonionic surfactants for the purpose of the invention are the
phosphine or sulfoxide surfactants of formula:
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R R' R" A-~O
wherein A is phosphorus or sulfur atom, R is a primary alkyl group containing
6-
24 carbons, preferably 10-18 carbons, and wherein R' and R" are, each,
independently selected from methyl, ethyl and 2-hydroxyethyl. The arrow in the
formula is a conventional representation of a semi-palar bond.
In a preferred embodiment herein suitable nonionic surfactants to be used are
polyethylene oxide condensates of alkyl phenols, polyethylene oxide
condensates of alkyl alcohols, alkylpolysaccharides, or mixtures thereof.
Highly
preferred are Cg-C20, preferably Cg-C12 alkyl phenol ethoxylates having from 3
to 25, preferably 10 to 25 ethoxy groups and C2-C24, preferably Cg-C1 g
alcohol
ethoxylates having from 2 to 35, preferably from 4 to 25, more preferably from
5
to 18 and most preferably from 3 to 15 ethylene oxide units, and mixtures
thereof.
Suitable zwitterionic surfactants for use herein contain both basic and acidic
groups which form an inner salt giving both cationic and anionic hydrophilic
groups on the same molecule at a relatively wide range of pH's. The typical
cationic group is a quaternary ammonium group, although other positively
charged groups like phosphonium, imidazolium and sulfonium groups can be
used. The typical anionic hydrophilic groups are carboxylates and sulfonates,
although other groups like sulfates, phosphonates, and the like can be used.
A generic formula for preferred zwitterionic surfactants for use herein (i.e.,
betaine and/or suifobetaine) is
R1-N+(R2)(R3)R4X_
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-Cg alkyl, hydroxy alkyl
or other substituted C1-Cg alkyl group; R3 is C1-Cg alkyl, hydroxy alkyl or
other
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substituted C1-C6 alkyl group which can also be joined to R2 to form ring
structures with the N, or a C1-Cg carboxylic acid group or a C1-C6 sulfonate
group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic
group
and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing
from 1 to 10 carbon atoms; and X is the hydrophilic group which is a
carboxylate
or sulfonate group, preferably sulfonate group.
Preferred hydrophobic groups R1 are aliphatic or aromatic, saturated or
unsaturated, substituted or unsubstituted hydrocarbon chains that can contain
linking groups such as amido groups, ester groups. More preferred R1 is an
alkyl group containing from 1 to 24, preferably from 8 to 18, and more
preferably
from 10 to 16 carbon atoms. These simple alkyl groups are preferred for cost
and stability reasons. However, the hydrophobic group R1 can also be an amido
radical of the formula Ra-C(O)-NRb-{C(Rc)2)m, wherein Ra is an aliphatic or
aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon
chain containing from 8 up to 20 carbon atoms, preferably an alkyl group
containing from 8 up to 20, preferably up to 18, more preferably up to 16
carbon
atoms, Rb is either a hydrogen a short chain alkyl or substituted alkyl
containing
from 1 to 4 carbon atoms, preferably a group selected from the group
consisting
of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures
thereof,
more preferably methyl or hydrogen, Rc is selected from the group consisting
of
hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3,
more
preferably 3, with no more than one hydroxy group in any (C(Rc)2) moiety.
Preferred R2 is hydrogen, or an alkyl or substituted alkyl containing from 1
to 4
carbon atoms, preferably a group selected from the group consisting of methyl,
ethyl, propyl, hydroxy substituted. ethyl or propyl and mixtures thereof, more
preferably methyl. Preferred R3 is a C1-C4 carboxylic acid group, a C1-C4
sulfonate group, or an alkyl or substituted alkyl containing from 1 to 4
carbon
atoms, preferably a group selected from the group consisting of methyl, ethyl,
CA 02349535 2004-06-22
19
propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more
preferably
methyl. Preferred R4 is (CH2)n wherein n is an integer from 1 to 10,
preferably
from 1 to 6, more preferably is from 1 to 3.
Some common examples of betaine/sulphobetaine are described in U.S. Pat.
Nos. 2,082,275, 2,702,279 and 2,255,082,
Examples of particularly suitable alkyldimethyl betaines include coconut-
dimethyl
betaine, lauryi dimethyi betaine, decyl dimethyi betaine, 2-(N-decyl-N, N-
dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl
dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl
dimethyl betaine. For example Coconut dimethyl betaine is commercially
available from Seppic under the trade name of Amonyl 265~. Lauryl betaine is
commercially available from Albright 8 Wilson under the trade name Empigen
BB/L~.
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Poulenc under the trade name Mirataine H2C-HA ~.
Particularly preferred zwitterionic surfactants for use in the compositions of
the
present invention are the sulfobetaine surfactants as they deliver optimum
grease cleaning benefits.
Examples of particularly suitable sulfobetaine surfactants include tallow
bis(hydroxyethyl) sulphobetaine, cocoamido propyl hydroxy sulfobetaines which
are commercially available from Rhone Pouienc and Witco, under the trade
name of Mirataine CBS~ and Rewoteric AM CAS 15~ respectively.
Further examples of amidobetaineslamidosulfobetaine include
cocoamidoethylbetaine, cocoamidopropyl betaine or C»-G~4 fatty
acylamidopropytene(hydropropylene)sulfobetaine. For example C,~-C,a fatty
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acylamidopropylene(hydropropylene)sulfobetaine is commercially available from
Sherex Company under the trade name "Varion CAS~ sulfobetaine".
Suitable amines for use herein are according to the following formula RR'R"N
wherein R is a saturated or unsaturated, substituted or unsubstituted, linear
or
branched alkyl groups containing from 1 to 30 carbon atoms, and preferably
from 1 to 20 carbon atoms and wherein R' and R" are independently saturated
or unsaturated, substituted or unsubstituted, linear or branched alkyl groups
containing from 1 to 30 carbon atoms or hydrogen. Particularly preferred
amines
to be used according to the present invention are amines having the following
formula RR'R"N wherein R is a saturated or unsaturated, linear or branched
alkyl group containing from 1 to 30 carbon atoms, preferably from 8 to 20,
more
preferably from 6 to 16, most preferably from 8 to 14 carbon atoms and wherein
R' and R" are independently substituted or unsubstituted, linear or branched
alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3
carbon
atoms, and more preferably are methyl groups, or mixtures thereof.
Suitable amines for use herein are for instance C,2 dimethyl amine, coconut
dimethyl amine, C,z-C,6 dimethyl amine. Said amines may be commercially
available from Hoechst under the trade name Genamin~, AKZO under the trade
name Aromox~ or Fina under the trade name Radiamine~.
Suitable quaternary ammonium surfactants for use herein are according to the
formula R1 R2R3R4N+ X-, wherein X is a counteranion such as halogen, methyl
sulphate, methyl sulphonate, or hydroxide, R1 is a saturated or unsaturated,
substituted or unsubstituted, linear or branched alkyl group containing from 1
to
carbon atoms, preferably from 12 to 20, more preferably from 8 to 20 carbon
atoms and R2, R3 and R4 are independently hydrogen, or saturated or
unsaturated, substituted or unsubstituted, linear or branched alkyl groups
containing from 1 to 4 carbon atoms, preferably from 1 to 3 and more
preferably
methyl. In highly preferred quaternary ammonium surfactants herein R1 is a
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21
C10-C1g hydrocarbon chain, most preferably C12, C14, or Clg, and R2, Rg and
R4 are all three methyl, and X is halogen, preferably bromide or chloride,
most
preferably bromide.
Examples of quaternary ammonium surfactants are myristyl trimethylammonium
methyl sulphate, cetyl trimethylammonium methyl sulphate, lauryl trimethyl
ammonium bromide, stearyl trimethyl ammonium bromide (STAB), cetyl
trimethyl ammonium bromide (CTAB) and myristyl trimethyl ammonium bromide
(MTAB). Highly preferred herein are lauryl trimethyl ammonium salts. Such
trimethyl quaternary ammonium surfactants may be commercially available from
Hoechst, or from Albright & Wilson under the trade name Empigen CM~.
Cationic surfactants suitable for use in compositions of the present invention
are
those having a long-chain hydrocarbyl group. Examples of such cationic
surfactants include the ammonium surfactants such as alkyldimethyiammonium
halogenides, and those surfactants having the formula:
[R2(OR3)yl[R4(OR3)y12R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms
in
the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -
CH2CH(CH3~, -CH2CH(CH20H~, -CH2CH2CH2-, and mixtures thereof; each
R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl,
benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having
a molecular weight less than 1000, and hydrogen when y is not 0; R5 is the
same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2
plus R5 is not more than 18; each y is from 0 to 10 and the sum of the y
values
is from 0 to 15; and X is any compatible anion.
CA 02349535 2004-06-22
22
Other cationic surfactants useful herein are also described in U.S. Patent
4,228,044, Cambre, issued October 14, i 980,
Amphoteric and ampholytic detergents which can be either cationic or anionic
depending upon the pH of the system are represented by detergents such as
dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting
dodecylamine with sodium isethionate according to the teaching of U.S. Pat.
No.
2,658,072, N-higher alkylaspartic acids such as those produced according to
the
teaching of U.S. Pat. No. 2,438,091, and the products sold under the trade
name "Miranol", and described in U.S. Pat. No. 2,528,378,
Additional synthetic detergents and listings of
their commercial sources can be found in McCutcheon's Detergents and
Emulsifiers, North American Ed. 1980,
Suitable anionic surfactants for use herein are all those commonly known by
those skilled in the art. Preferably, the anionic surfactants for use herein
include
alkyl sulphonates, alkyl aryl sulphonates, alkyl sulphates, alkyl alkoxyiated
sulphates, Cg-C2p alkyl alkoxylated linear or branched Biphenyl oxide
disulphonates, or mixtures thereof.
Suitable alkyl sulphonates for use herein include water-soluble salts or acids
of
the formula RS03M wherein R is a Cg-C20 Linear or branched, saturated or
unsaturated alkyl group, preferably a Cg-C1 g alkyl group and more preferably
a
C10-C1g alkyl group, and M is H or a ration, e.g., an alkali metal ration
(e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.,
methyl-, dimethyl-, and trimethyl ammonium rations and quaternary ammonium
rations, such as tetramethyl-ammonium and dimethyl piperdinium rations and
quaternary ammonium rations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
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23
Suitable alkyl aryl sulphonates for use herein include water-soluble salts or
acids
of the formula RS03M wherein R is an aryl, preferably a benzyl, substituted by
a
C6-C20 linear or branched saturated or unsaturated alkyl group, preferably a
Cg-C1g alkyl group and more preferably a C10-C16 alkyl group, and M is H or a
cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium,
calcium,
magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-,
dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations,
such as tetramethyl-ammonium and dimethyl piperdinium cations and
quaternary ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like).
An example of a C~4-C~6 alkyl sulphonate is Hostapur~ SAS available from
Hoechst. An example of commercially available alkyl aryl sulphonate is Lauryl
aryl sulphonate from Su.Ma.. Particularly preferred alkyl aryl sulphonates are
alkyl benzene sulphonates commercially available under trade name Nansa~
available from Albright&Wilson.
Suitable alkyl sulphate surfactants for use herein are according to the
formula
R1 S04M wherein R1 represents a hydrocarbon group selected from the group
consisting of straight or branched alkyl radicals containing from 6 to 20
carbon
atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the
alkyl
group. M is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium,
lithium, calcium, magnesium and the like) or ammonium or substituted
ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and
quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl
piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the
like).
Particularly preferred branched alkyl sulphates to be used herein are those
containing from 10 to 14 total carbon atoms like Isalchem 123 AS~. Isalchem
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24
123 AS~ commercially available from Enichem is a C,2_,3 surfactant which is
94% branched. This material can be described as CH3-(CH2)m-
CH(CHzOS03Na)-(CHZ)~-CH3 where n+m=8-9. Also preferred alkyl sulphates
are the alkyl sulphates where the alkyl chain comprises a total of 12 carbon
atoms, i.e., sodium 2-butyl octyl sulphate. Such alkyl sulphate is
commercially
available from Condea under the trade name Isofol~ 12S. Particularly suitable
liner alkyl sulphonates include C~2-C,6 paraffin sulphonate like Hostapur~ SAS
commercially available from Hoechst.
Suitable alkyl alkoxylated sulphate surfactants for use herein are according
to
the formula RO(A)mS03M wherein R is an unsubstituted Cg-C20 alkyl or
hydroxyalkyl group having a C6-C20 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1g alkyl or hydroxyalkyl, A is an
ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6,
more
preferably between 0.5 and 3, and M is H or a cation which can be, for
example,
a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well
as alkyl propoxylated sulfates are contemplated herein. Specific examples of
substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
and quaternary ammonium canons, such as tetramethyl-ammonium, dimethyl
piperdinium and rations derived from alkanolamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the like. Exemplary
surfactants
are C12-C1g alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)SM), C12-C18
alkyl polyethoxylate (2.25) sulfate (C12-C18E(2.25)SM), C12-C1g alkyl
polyethoxylate (3.0) sulfate (C12-C18E(3.0)SM), and C12-C1g alkyl
polyethoxylate (4.0) sulfate (C12-C18E(4.0)SM), wherein M is conveniently
selected from sodium and potassium.
Suitable Cg-C2p alkyl alkoxylated linear or branched diphenyl oxide
disulphonate surfactants for use herein are according to the following
formula:
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WO 00/27983 PCT/US99/26603 -
p
S03-X+ S03-X+
wherein R is a Cg-C20 linear or branched, saturated or unsaturated alkyl
group,
preferably a C12-C1g alkyl group and more preferably a C14-C16 alkyl group,
and X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium,
lithium, calcium, magnesium and the like). Particularly suitable C6-C20 alkyl
alkoxylated linear or branched diphenyl oxide disulphonate surfactants to be
used herein are the C12 branched di phenyl oxide disulphonic acid and C16
linear di phenyl oxide disulphonate sodium salt respectively commercially
available by DOW under the trade name Dowfax 2A1 ~ and Dowfax 8390~.
Other anionic surfactants useful herein include salts (including, for example,
sodium, potassium, ammonium, and substituted ammonium salts such as mono-
di- and triethanolamine salts) of soap, Cg-C24 olefinsulfonates, sulphonated
polycarboxylic acids prepared by sulphonation of the pyrolyzed product of
alkaline earth metal citrates, e.g., as described in British patent
specification No.
1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene oxide); alkyl ester sulfonates such as C14-16 methyl ester
sulfonates;
acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide
ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates,
N-
acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated C12-C1g monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated Cg-C14
diesters), acyi sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described below), alkyl polyethoxy carboxylates such as those of the formula
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26
RO(CH2CH20)kCH2C00-M+ wherein R is a C8-C22 alkyl, k is an integer from
0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated
resin acids are also suitable, such as rosin, hydrogenated rosin, and resin
acids
and hydrogenated resin acids present in or derived from tall oil. Further
examples are given in "Surface Active Agents and Detergents" (Vol. I and II by
Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et
al. at Column 23, line 58 through Column 29, line 23.
Preferably the surfactants to be used herein as optional ingredients are
selected
from the group consisting of nonionic surfactants, cationic surfactants,
anionic
surfactants, zwitterionic surfactants_ 2r'nt7hntPrin cmrFactanfc ~r.ri
.r,~..+~~~~~
thereof. More preferably said surfactant is a nonionic surfactant or an
anionic
surfactant or a mixture thereof.
Other optional ingredients
The compositions herein may further comprise conventional enamel cleaning
ingredients. Preferably, the liquid compositions according to the present
invention may comprise a variety of optional ingredients depending on the
technical benefit aimed for and the surface treated.
Suitable optional ingredients for use herein include a solvent, a builder, a
chelant, a buffer, a bactericide, a hydrotrope, a colorant, a stabilizer, a
radical
scavenger, a vinylpyrrolidone homopolymer or copolymer, a polysaccharide
polymer, a bleach, a bleach activator, a preservative, a suds controlling
agent
like a fatty acid, an enzyme, a soil suspender, a dye transfer agent, a
brightener,
an anti dusting agent, a dispersant, a dye transfer inhibitor, a pigment, an
acid, a
dye and/or a perfume.
Solvent
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27
The compositions of the present invention may further comprise a solvent, as a
highly preferred optional ingredient.
Solvents are desired herein because they contribute to the greasy soils
cleaning
performance of the composition herein.
Suitable solvents for use herein include glycols or alkoxylated glycols,
alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols,
alkoxylated aliphatic branched alcohols, alkoxylated linear C~-C5 alcohols,
linear
C,-C5 alcohols, C8-C~4 alkyl and cycloalkyl hydrocarbons and halohydrocarbons
and mixtures thereof with the proviso that said solvent is not an ether of
diethylene glycol as described herein.
Suitable glycols to be used herein are according to the formula HO-CR1 R2-OH
wherein R1 and R2 are independently H or a CZ-C,o saturated or unsaturated
aliphatic hydrocarbon chain and/or cyclic. Suitable glycofs to be used herein
are
dodecaneglycol and/or propanediol.
Suitable alkoxylated glycols to be used herein are according to the formula R-
(A)n-R1-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from
1
to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10
carbon atoms, wherein R1 is a linear saturated or unsaturated alkyl of from 3
to
20 carbon atoms, preferably from 3 to 15 and more preferably from 3 to 10
carbon atoms, and A is an alkoxy group preferably ethoxy, methoxy, and/or
propoxy and n is from 1 to 5, preferably 1 to 2. Suitable alkoxylated glycols
to be
used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
Suitable alkoxylated aromatic alcohols to be used herein are according to the
formula R-(A)n-OH wherein R is an alkyl substituted or non-alkyl substituted
aryl
group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more
preferably
from 2 to 10 carbon atoms, wherein A is an alkoxy group preferably butoxy,
propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
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28
Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or
benzoxypropanol.
Suitable aromatic alcohols to be used herein are according to the formula R-OH
wherein R is an alkyl substituted or non-alkyl substituted aryl group of from
1 to
20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10
carbon atoms. For example a suitable aromatic alcohol to be used herein is
benzyl alcohol.
Suitable aliphatic branched alcohols to be used herein are according to the
formula R-OH wherein R is a branched saturated or unsaturated alkyl group of
from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5
to 12 carbon atoms. Particularly suitable aliphatic branched alcohols to be
used
herein include 2-ethylbutanol and/or 2-methylbutanol.
Suitable alkoxylated aliphatic branched alcohols to be used herein are
according
to the formula R-(A)n-OH wherein R is a branched saturated or unsaturated
alkyl
group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more
preferably
from 5 to 12 carbon atoms, wherein A is an alkoxy group preferably butoxy,
propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
Suitable alkoxylated aliphatic branched alcohols include 1-
methylpropoxyethanol
and/or 2-methylbutoxyethanol.
Suitable alkoxylated linear C,-C~ alcohols to be used herein are according to
the
formula R-(A)n-OH wherein R is a linear saturated or unsaturated alkyl group
of
from 1 to 5 carbon atoms, preferably from 2 to 4 carbon atoms, wherein A is an
alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of
from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic linear C,-C5
alcohols
are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol,
ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially
available under the trade name n-BPP~ from Dow chemical.
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29
Suitable linear C,-C5 alcohols to be used herein are according to the formula
R-
OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5
carbon atoms, preferably from 2 to 4 carbon atoms. Suitable linear C,-C5
alcohols are methanol, ethanol, propanol or mixtures thereof.
Other suitable solvents include butyltriglycol ether, ter amilic alcohol and
the like.
Particularly preferred solvents to be used herein are butoxy propoxy propanol,
benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures
thereof.
The preferred solvent for use herein is butoxy propoxy propanol (n-BPP).
Typically, the compositions of the present invention comprise from 0.1 % to
8%,
preferably from 0.5% to 5% and more preferably from 1 % to 3% by weight of the
total composition of a solvent.
Vinylpyrrolidone homopolymer or copolymer
The compositions of the present invention may comprise a vinylpyrrolidone
homopolymer or copolymer.
Typically, the compositions of the present invention may comprise from 0.01 %
to
5%, more preferably from 0.05% to 3% and most preferably from 0.05% to 1
by weight of the total composition of a vinylpyrrolidone homopolymer or
copolymer.
Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N-
vinylpyrrolidone having the following repeating monomer:
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H
I
C-CHI
I '
N
H2 C~ ~C=O
H2 C- CH2
n
wherein n (degree of polymerisation) is an integer of from 10 to 1,000,000,
preferably from 20 to 100,000, and more preferably from 20 to 10,000.
Accordingly, suitable vinylpyrrolidone homopolymers ("PVP") for use herein
have
an average molecular weight of from 1,000 to 100,000,000, preferably from
2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and most
preferably from 50,000 to 500,000.
Suitable vinyipyrrolidone homopolymers are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names
PVP K-15~ (viscosity molecular weight of 10,000), PVP K-30~ (average
molecular weight of 40,000), PVP K-60~ (average molecular weight of 160,000),
and PVP K-90~ (average molecular weight of 360,000). Other suitable
vinylpyrrolidone homopolymers which are commercially available from BASF
Cooperation include Sokalan HP 165~, Sokalan HP 12~.
Luviskol K30~, Luviskol K60~, Luviskol K80~, Luviskol K90~ and other
vinylpyrrolidone homopolymers known to persons skilled in the detergent field
(see for example EP-A-262,897 and EP-A-256,696).
Suitable copolymers of vinylpyrrolidone for use herein include copolymers of N-
vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof.
The aikylenically unsaturated monomers of the copolymers herein include
unsaturated dicarboxylic acids such as malefic acid, chloromaleic acid,
fumaric
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31
acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid,
acrylic acid,
N-vinylimidazole and vinyl acetate. Any of the anhydrides of the unsaturated
acids may be employed, for example acrylate, methacrylate. Aromatic
monomers like styrene, sulphonated styrene, alpha-methyl styrene, vinyl
toluene, t-butyl styrene and similar well-known monomers may be used.
The molecular weight of the copolymer of vinylpyrrolidone is not especially
critical so long as the copolymer is water-soluble, has some surface activity
and
is adsorbed to the hard-surface from the liquid composition comprising it in
such
a manner as to increase the hydrophilicity of the surface. However, the
preferred
copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or
mixtures thereof, have a molecular weight of between 1,000 and 1,000,000,
preferably between 10,000 and 500,000 and more preferably between 10,000
and 200,000.
For example particularly suitable N-vinylimidazole N-vinylpyrrolidone polymers
for use herein have an average molecular weight range from 5,000 to 1,000,000,
preferably from 5,000 to 500,000, and more preferably from 10,000 to 200,000.
The average molecular weight range was determined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern
Methods of Polymer Characterization".
Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers
like PVPlvinyl acetate copolymers are commercially available under the trade
name Luviskol~ series from BASF.
The copolymers of vinylpyrrolidone for use in the compositions of the present
invention also include quaternized or unquaternized vinylpyrrolidone/
dialkylaminoalkyl acrylate or methacrylate copolymers.
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32
Such vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers
(quaternised or unquaternised) suitable to be used in the compositions of the
present invention are according to the following formula:
N O RI
CH-CH2 CH2 C
m
(C=O
O-R2-N+~R3)zRa.X
in which n is between 20 and 99 and preferably between 40 and 90 mol% and m
is between 1 and 80 and preferably between 5 and 40 mol%; R1 represents H or
CH3; y denotes 0 or 1; R2 is -CH2-CHOH-CH2- or CXH2x, in which x=2 to 18;
R3 represents a lower alkyl group of from 1 to 4 carbon atoms, preferably
methyl
or ethyl, or
CH2
R4 denotes a lower alkyl group of from 1 to 4 carbon atoms, preferably methyl
or
ethyl; X- is chosen from the group consisting of CI, Br, I, 1/2 S04, HS04 and
CH3S03. The polymers can be prepared by the process described in French
Pat. Nos. 2,077,143 and 2,393,573.
The preferred quaternized or unquaternized vinylpyrrolidone/dialkylaminoalkyl
acrylate or methacrylate copolymers for use herein have a molecular weight of
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33
between 1,000 and 7,000,000, preferably between 10,000 and 500,000 and
more preferably between 10,000 and 100,000.
Such vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers
are
commercially available under the name copolymer 845~, Gafquat 734~, or
Gafquat 755~ from ISP Corporation, New York, NY and Montreal, Canada or
from BASF under the tradename Luviquat~.
Preferred vinylpyrrolidone homopolymers or copolymers for use herein are the
vinylpyrrolidone homopolymers.
Polysaccharide polymer
The compositions of the present invention may comprise a polysaccharide
polymer.
Typically, the compositions of the present invention may comprise from 0.01 %
to
5%, more preferably from 0.05% to 3% and most preferably from 0.05 % to 1
by weight of the total composition of a polysaccharide polymer.
Suitable polysaccharide polymers for use herein include substituted cellulose
materials like carboxymethylcellulose, ethyl cellulose, hydroxyethyl
cellulose,
hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan and naturally
occurring polysaccharide polymers like xanthan gum, guar gum, locust bean
gum, tragacanth gum or derivatives thereof, or mixtures thereof.
Particularly polysaccharide polymers for use herein are xanthan gum and
derivatives thereof. Xanthan gum and derivatives thereof may be commercially
available for instance from Kelco under the trade name Keltrol RD~, Kelzan S~
or Kelzan T~. Other suitable Xanthan gum is commercially available by Rhone
Poulenc under the trade name Rhodopol T~ and Rhodigel X747~.
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34
Succinoglycan gum for use herein is commercially available by Rhone Poulenc
under the trade name Rheozan ~.
we
The liquid compositions according to the present invention may be coloured.
Accordingly, they may comprise a dye. Suitable dyes for use herein are stable
dyes. By "stable", it is meant herein a compound which is chemically and
physically stable in the acidic environment of the compositions herein.
Preservative
The compositions according to the present invention may further comprise a
preservative as an optional ingredient. Preservatives to be used herein
include
all those known to those skilled in the art ho hard-surface cleaner
compositions.
Preservatives are desired herein because they contribute to the stability of
the
compositions herein.
Suitable preservatives for use herein are diazolidinyl urea, methyl citrate,
propyl
4-hydroxybenzoate, sorbic acid, Na salt of p-hydroxybenzoate or gluteraldehyde
or a mixture thereof.
Radical scavenger
The compositions of the present invention may comprise a radical scavenger.
Suitable radical scavengers for use herein include the well-known substituted
mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates
and mixtures thereof. Preferred such radical scavengers for use herein include
di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone,
mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic
acid, catechol, t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-
t-
butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred
is
di-tert-butyl hydroxy toluene. Such radical scavengers like N-propyl-gallate
may
CA 02349535 2004-06-22
be commercially available from Nipa Laboratories under the trade name Nipanox
S1 ~.
Radical scavengers when used, are typically present herein in amounts up to
10% and preferably from 0.001 % to 0.5% by weight of the total composition.
The presence of radical scavengers may contribute to the chemical stability of
the compositions of the present invention.
Perfume
The compositions according to the present invention may further comprise a
perfume
Suitable perfumes for use herein include materials which provide an olfactory
aesthetic benefit and/or cover any "chemical" odour that the product may have.
The main function of a small fraction of the highly volatile, low boiling
(having low
boiling points), perfume components in these perfumes is to improve the
fragrance odour of the product itself, rather than impacting on the subsequent
odour of the surface being cleaned. However, some of the less volatile, high
boiling perfume ingredients provide a fresh and clean impression to the
surfaces, and it is desirable that these ingredients be deposited and present
on
the dry surface. Perfume ingredients can be readily solubilized in the
compositions, for instance by an anionic detergent surfactant, when present.
The perfume ingredients and compositions suitable to be used herein are the
conventional ones known in the art. Selection of any perfume component, or
amount of perfume, is based solely on aesthetic considerations.
Suitable perfume compounds and compositions can be found in the art including
U.S. Pat. Nos. : 4,145,184, Brain and Cummins, issued March 20, 1979;
4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7,
1985; and 4,152,272, Young, issued May 1, 1979,
In general, the degree of substantivity of a
CA 02349535 2004-06-22
36
perfume is roughly proportional to the percentages of substantive perfume
material used. Relatively substantive perfumes contain at least 1 %,
preferably at
least 10%, substantive perfume materials. Substantive perfume materials are
those odorous compounds that deposit on surfaces via the cleaning process and
are detectable by people with normal olfactory acuity. Such materials
typically
have vapour pressures lower than that of the average perfume material. Also,
they typically have molecular weights of 200 and above, and are detectable at
levels below those of the average perfume material. Perfume ingredients useful
herein, along with their odor character, and their physical and chemical
properties, such as boiling point and molecular weight, are given in "Perfume
and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the
author, 1969,
Examples of the highly volatile, low boiling, perfume ingredients are :
anethole,
benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bomyl
acetate, camphene, ciscitral (neral), citronellal, citronellvl, citronellyl
acetate,
para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl
carbinol, eucaliptol, geranial, geraniol, geranyl acetate, geranyl nitrite,
cis-3-
hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide,
linalyl
acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl
nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthyf acetate,
menthone, iso-menthone, mycrene, myrcenyl acetate, myrcenol, nerol, neryl
acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, beta-pinene, gamma-
terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate, and vertenex
(para-
tertiary-butyl cyclohexyl acetate). Some natural oils also contain large
percentages of highly volatile perfume ingredients. For example, lavandin
contains as major components : linalool; linalyl acetate; geraniol; and
citronellol.
Lemon oil and orange terpenes both contain 95% of d-limonene.
Examples of moderately volatile perfume ingredients are : amyl cinnamic
aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol,
coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-
eugenol,
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37
flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial
(para-
tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone,
nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl
phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehyde.
Cedarwood
terpenes are composed mainly of alpha-cedrene, beta-cedrene, and other
C~5H24 sesquiterpenes.
Examples of the less volatile, high boiling, perfume ingredients are
benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gams-2-benzopyran), hexyl
cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-10-
carboxaldehyde), methyl cedryione, methyl dihydro jasmonate, methyl-beta-
naphthyl ketone, musk indanone, musk ketone, musk tibetene, and phenylethyl
phenyl acetate.
Selection of any particular perfume ingredient is primarily dictated by
aesthetic
considerations.
The compositions herein may comprise a perfume ingredient, in amounts up to
5.0%, preferably in amounts of 0.1 % to 1.5% by weight of the total
composition.
Chelating agent
Another class of optional compounds for use herein includes chelating agents.
Chelating agents may be incorporated in the compositions herein in amounts
ranging up to 10.0%, preferably 0.01 % to 5.0% by weight of the total
composition.
Suitable phosphonate chelating agents to be used herein may include alkali
metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene
phosphonate), as well as amino phosphonate compounds, including amino
aminotri(methyiene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates
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38
(NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine
yenta methylene phosphonates (DTPMP). The phosphonate compounds may
be present either in their acid form or as salts of different cations on some
or all
of their acid functionalities. Preferred phosphonate chelating agents to be
used
herein are diethylene triamine yenta methylene phosphonate (DTPMP) and
ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents
are commercially available from Monsanto under the trade name DEQUEST~~
Polyfunctionally-substituted aromatic chelating agents may also be useful in
the
compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to
Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine
N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or
substitutes
ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'-disuccinic
acids, especially the (S,S) isomer, have been extensively described in US
patent
4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine N,N'-
disuccinic acid is, for instance, commercially available under the tradename
ssEDDS~ from Palmer Research Laboratories.
Suitable amino carboxylates to be used herein include ethylene diamine tetra
acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate
(DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotri-acetates,
ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-
diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-
acetic
acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and
substituted ammonium salt forms. Particularly suitable amino carboxyiates to
be
used herein are diethylene triamine yenta acetic acid, propylene diamine
tetracetic acid (PDTA) which is, for instance, commercially available from
BASF
under the trade name Trilon FS~ and methyl glycine di-acetic acid (MGDA).
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Further carboxylate chelating agents to be used herein include salicylic acid,
aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
Bleaches
The liquid compositions herein may also comprise a bleaching component. Any
bleach known to those skilled in the art may be suitable to be used herein
including any peroxygen bleach as well as any hypohalite bleach.
Suitable peroxygen bleaches for use herein include hydrogen peroxide or
sources thereof. As used herein a source of hydrogen peroxide refers to any
compound which produces active oxygen when said compound is in contact with
water. Suitable water-soluble sources of hydrogen peroxide for use herein
include percarbonates, preformed percarboxylic acids, persilicates,
persulphates, perborates, organic and inorganic peroxides and/or
hydroperoxides.
Suitable hypohalite bleaches for use herein include chlorine releasing
components as, e.g., alkali metal hypochlorites. Advantageously, the
compositions according to the present invention are stable in presence of this
bleaching component. Although alkali metal hypochlorites are preferred, other
hypochlorite compounds may also be used herein and, e.g., can be selected
from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite
for use herein is sodium hypochlorite.
Bleach activators
In a preferred embodiment wherein the compositions of the present invention
that comprise a peroxygen bleach, said compositions may further comprise a
bleach activator.
By "bleach activator", it is meant herein a compound which reacts with
peroxygen bleach tike hydrogen peroxide to form a peracid. The peracid thus
CA 02349535 2001-04-27
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formed constitutes the activated bleach. Suitable bleach activators to be used
herein include those belonging to the class of esters, amides, imides, or
anhydrides.
Examples of suitable compounds of this type are disclosed in British Patent GB
1 586 769 and GB 2 143 231 and a method for their formation into a grilled
form
is described in European Published Patent Application EP-A-62 523. Suitable
examples of such compounds to be used herein are tetracetyl ethylene diamine
(TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxy
dodecanoic acid as described for instance in US 4 818 425 and nonylamide of
peroxyadipic acid as described for instance in US 4 259 201 and n-
nonanoyloxybenzenesulphonate (NOBS). Also suitable are N-acyl caprofactams
selected from the group consisting of substituted or unsubstituted benzoyl
caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyi
caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam
pentanoyl caprolactam or mixtures thereof. A particular family of bleach
activators of interest was disclosed in EP 624 154, and particularly preferred
in
that family is acetyl methyl citrate (ATC). Acetyl methyl citrate has the
advantage
that it is environmental-friendly as it eventually degrades into citric acid
and
alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical
stability in the
product upon storage and it is an efficient bleach activator. Finally, it
provides
good building capacity to the composition.
Packaginp 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 are
preferably packaged in conventional detergent plastic bottles.
In one embodiment the compositions herein may be packaged in manually or
electrically operated spray dispensing containers, which are usually made of
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41
synthetic organic polymeric plastic materials. Accordingly, the present
invention
also encompasses liquid cleaning compositions of the invention packaged in a
spray dispenser, preferably in a trigger spray dispenser or pump 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 compositions suitable for
use
according to the present invention. Such spray-type dispensers are
particularly
suitable to clean vertical surfaces.
Suitable spray-type dispensers to be used according to the present invention
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~ 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 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 the formation of liquid droplets.
Examples
These compositions were made comprising the listed ingredients in the listed
proportions (weight %).
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42
Ingredients: l II III IV V Vl VII VIII IX X X1
(% by weight)
Dobanol~ 91-8 1.3 1.5 - 3.5 - - - 2.5 - -
Isalchem 123 - 1.5 - 3.5 - 1.4 5.0 - - 3.0 3.0
AS~
Lutensol~ AO - - - - - 1.5 - 2.0 - - -
30
n-BPP 2.0 2.0 2.0 - 2.0 2.0 2.0 - 3.0 5.8 2.0
Citric Acid 3.5 3.5 3.0 3.5 3.5 3.5 - - - 5.5 3.5
Malefic Acid - - - - - - - - 2.5 - -
Luviskol K60~ 0.1 - - 0.050.1 - 0.1 - - 0.1 0.1
Kelzan T~ 0.3 0.6 - 0.3 - - - 0.3 - - 0.3
KOH 1.1 0.8 1.1 - - - 0.2 0.3 0.7 1.1 1.0
5
NH40H - - - 1.1 0.9 1.0 0.8 0.5 0.4 - -
Waters & Minors------------------------- p 00 -----___-_____-__-____-
____
u to ---
1
The pH of these
examples is
acidic.
Isalchem 123 AS~ is a branched alkyl sulphates commercially available from
Enichem.
Keizan T~ is a Xanthan gum supplied by Kelco.
Luviskol K60~ is a Polyvinylpyrrolidone supplied by BASF.
n-BPP is butoxy propoxy propanol commercially available from Dow Chemical.
Dobanol~ 91-8 is a C9-C" ethoxylated alcohol commercially available from
Shell.
Lutensol~ AO 30 is a C,2_,4 ethoxylated alcohol commercially available from
BASF.
All the above compositions are safe to enamel when used to treat enamel
surfaces.
