Note: Descriptions are shown in the official language in which they were submitted.
CA 02261~07 1999-01-14
ETHOXYLATED STJRFACTANTS
This application is a divisional of co-pending Canadian
Application Serial No. 2,158,248.
Field of the Invention
This invention pertains to ethoxylated alcohol
surfactants.
Backqround of the Invention
The use of acidic cleaning compositions containing
organic water-soluble synthetic detergents, solvents, and/or
detergent builders for bathroom cleaning tasks are known.
However, such compositions are not usually capable of
providing superior hard surface cleaning for all of the
soils encountered in a bathroom. An exception is the
compositions of U.S. Pat. No. 5,061,393, Linares and Cilley,
issued Oct. 29, 1991.
The object of the present invention is to provide
additional detergent compositions which also provide good
and/or improved cleaning for all of the usual hard surface
cleaning tasks found in the bathroom, including the removal
of hard-to-remove soap scum and hard water deposits, and
improved sudsing characteristics.
Summary of the Invention
Parent Canadian Application No. 2,158,248 relates to an
acidic aqueous hard surface detergent composition
comprising: (a) a detergent surfactant system which
comprises a mixture of amphoteric-non-zwitterionic and
nonionic detergent surfactants wherein said amphoteric-non-
zwitterionic detergent surfactant has the generic formula:
RC(O)-N(R1)-(CH2)n-N(Rl)-CH2-C(O)-OH wherein RC(O)- is a C814
hydrophobic fatty acyl moiety containing from about 8 to
about 14 carbon atoms which, in combination with the
nitrogen atom, forms an amido group, each n is from 1 to 3,
and each Rl is hydrogen or a Cl2 alkyl or hydroxy alkyl
.. .. ..
CA 02261~07 1999-01-14
group and wherein said nonionic detergent surfactant
contains a C6l0 alkyl group and from about 2.5 to about 12
ethylene oxide groups and has an HLB of from about 6 to
about 18, the nonionic detergent surfactant being present at
a level of from about 0.5~ to about 6~ and the ratio of
nonionic surfactant to amphoteric, non-zwitterionic
surfactant being from about 1:4 to about 3:1; (b) optional
hydrophobic solvent that provides a primary cleaning
function selected from the group consisting of: alkyl and
cycloalkyl hydrocarbons and halohydrocarbons, alpha olefins,
glycol ethers having the formula R1O-(R2O-)mH wherein each
is an alkyl group which contains from about 4 to about 8
carbon atoms, each R2 is either ethylene or propylene, and m
is a number from 1 to about 3, and the compound has a
solubility in water of less than about 20%; diols having
from about 6 to about 16 carbon atoms in their molecular
structure; benzyl alcohol; n-hexanol; phthalic acid esters
of Cl_4 alcohols; and mixtures thereof, the solvent, when
present, being at a level of from about 1~ to about 15~; and
(c) polycarboxylate detergent builder selected from the
group consisting of: dicarboxylic acids having from about 2
to about 14 carbon atoms between the carboxyl groups; citric
acid; builders having the generic formula: R5- [O-CH(COOH)CH-
(COOH)]nR5 wherein each R5 is selected from the group
consisting of H and OH and n is a number from about 2 to
about 3 on the average; chelating agents having the formula:
R-N(CH2COOM) 2 wherein R is selected from the group
consisting of: -CH2CHaCH2OH; -CH2CH (OH) CH3; -CH2CH (OH) CH2OH;
- CH ( CH2OH ) 2 i - CH3; - CH2 CH2OCH3; - C ( O ) - CH3; - CH2 - C ( O ) - NH2;-CH2CH2CH2OCH3; -C(CH2OH)3; and mixtures thereof; and each M
is hydrogen; and mixtures thereof, the builder, when
present, being at a level of from about 2~ to about 14~;
said composition having a pH of from about 1 to about 5.5,
and from about 2 to about 4 when said dicarboxylic acid
detergent builder is present.
The present invention provides nonionic detergent
surfactant which is an ethoxylated alcohol in which the
alcohol contains an alkyl group containing from six to
-- 2
CA 02261~07 1999-01-14
eleven carbon atoms and in which there are from about three
to about twelve ethoxy moieties in a peaked distribution
such that at least about 70~ and less than about 95~ of the
molecules by weight have an ethoxy content within about two
ethoxy moieties of the average ethoxy content.
In yet another embodiment of parent Application No.
2,158,248 is provided the process of cleaning hard surfaces
comprising the step of: spraying said surfaces with an
acidic aqueous hard surface detergent composition
comprising: (a) a detergent surfactant system which
comprises: a mixture of amphoteric and nonionic detergent
surfactants, said amphoteric detergent surfactant being
selected from the group consisting of: C8 l4 amidoalkylene
glycinate detergent, cocoylamidoethyleneamine-N-
(hydroxyethyl)-2-hydroxypropyl-1-sulfonate, C8l0 fatty acyl
amidoethyleneamine-N-(methyl)ethyl sulfonate, cocoylamido-
ethylene-amine-N-(methyl)acetates, cocoylamidoethylene-
amine-N-(hydroxyethyl)acetates, cocoylamidopropylamine-
N-(hydroxyethyl)acetates, substituted amino propionates, and
mixtures thereof including analogs and homologs thereof, as
their water-soluble salts, or acids; (b) optional
hydrophobic solvent that provides a primary cleaning
function; and (c) polycarboxylate detergent builder, said
composition having a pH of from about 1 to about 5.5, and
from about 2 to about 4 when said polycarboxylate detergent
builder comprises dicarboxylate detergent builder.
The compositions can also contain an optional buffering
system to help maintain the acidic pH and the balance
typically being an aqueous solvent system and minor
ingredients. The compositions can be formulated either as
concentrates, or at usage concentrations, either thickened
or unthickened, or can be packaged in a container having
means for creating a spray or foam to make application to
hard surfaces more convenient.
CA 02261~07 1999-01-14
Detailed Descri~tion of the Invention
(a) The Deterqent Surfactant Systems
In accordance with the invention described in parent
Application No. 2,158,248, the detergent surfactant system
is selected from the group consisting of: detergent
surfactant systems which comprise either: (1) a mixture of
nonionic and zwitterionic detergent surfactants as disclosed
in U.S. Pat. No. 5,061,393, preferably a fatty acyl
amidoalkylenebetaine; (2) a mixture of amphoteric
(non-zwitterionic), preferably N-(Ca14 acylamidoalkylene)-
amidoglycinate, and nonionic detergent surfactant; or, less
desirably, (3) a low sudsing, nonionic detergent surfactant
that is C610E3l2, preferably C810E38, nonionic detergent
surfactant, the amount of ethoxylation being selected to
give the appropriate HLB, at a level of at least about 0.1~,
preferably from about 1% to about 5~, the nonionic detergent
surfactant in (1) and (2) preferably being one that has a
short chain, i.e., C6l0E3l2, more preferably being either a
C8 or mixture of C8 and ClO alkyl nonionic detergent
surfactants with the C8 being at least about 0.1% of the
mixture, said low sudsing nonionic detergent surfactant
optionally being a mixture of high HLB and low HLB nonionic
detergent surfactants, and, optionally, but preferably, the
nonionic detergent surfactant in all of the above surfactant
combinations comprises short chain (C6l0) nonionic detergent
surfactant having a "peaked distribution," i.e., at least
about 70~ of the molecules have a content of ethoxy moieties
within about two of the average, the content of said peaked
short chain nonionic detergent surfactant preferably being
at least about 0.1~. As mentioned hereinbefore, these
shorter chain nonionic detergent surfactants, and especially
those having a peaked distribution, are superior for use
with the zwitterionic and/or amphoteric (non-zwitterionic)
detergent surfactants.
The varied types of soils that may be encountered
include oily/greasy soils and soap scum. The detergent
surfactant systems of this invention provide good
performance for all of the common types of soil encountered
-- 4
CA 02261~07 1999-01-14
in the bathroom while providing superior sudsing
characteristics. Specifically, the peaked distribution
short chain nonionic detergent surfactants provide superior
quantities of foam which quickly breaks to provide good
rinsing. The short chain nonionic detergent surfactants are
surprisingly effective when used with the betaine,
especially amido-betaine type of zwitterionic detergent
surfactant.
AmPhoteric (Zwitterionic) Deterqent Surfactants
Zwitterionic detergent surfactants contain 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 sulfonium and phosphonium
groups can also be used. The typical anionic hydrophilic
groups are carboxylates and sulfonates, although other
groups like sulfates, phosphates, etc., can be used. A
generic formula for some preferred zwitterionic detergent
surfactants is:
R-N(~)(R2)(R3)R4X(-)
wherein R is a hydrophobic group; R2 and R3 are each Cl4
alkyl, hydroxy alkyl or other substituted alkyl group which
can also be joined to form ring structures with the N; 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 about one to
about four carbon atoms; and X is the hydrophilic group
which is preferably a carboxylate or sulfonate group.
Preferred hydrophobic groups R are alkyl groups
containing from about 8 to about 22, preferably less than
about 18, more preferably less than about 16, carbon atoms.
The hydrophobic group can contain unsaturation and/or
substituents and/or linking groups such as aryl groups,
amido groups, ester groups, etc. In general, the simple
alkyl groups are preferred for cost and stability reasons.
CA 02261~07 1999-01-14
A specific "simple" zwitterionic detergent surfactant
is 3-(N-dodecyl-N,N-dimethyl)-2-hydroxypropane-1-sulfonate,
available from the Sherex Company under the trade name
"Varion HC".
Other specific zwitterionic detergent surfactants have
the generic formula:
R-C(o)-N(R2)-(CR32)n-N(R2)2(')-(CR32)n-So2(-) -
wherein each R is a hydrocarbon, e.g., an alkyl group
containing from about 8 up to about 20, preferably up to
about 18, more preferably up to about 16 carbon atoms, each
(R2) is either a hydrogen (when attached to the amide
nitrogen), short chain alkyl or substituted alkyl containing
from one to about four carbon atoms, preferably groups
selected from the group consisting of methyl, ethyl, propyl,
hydroxy substituted ethyl or propyl and mixtures thereof,
preferably methyl, each (R3) is selected from the group
consisting of hydrogen and hydroxy groups, and each n is a
number from 1 to about 4, preferably from 2 to about 3; more
preferably about 3, with no more than about one hydroxy
group in any (CR32) moiety. The R groups can be branched
and/or unsaturated, and such structures can provide
spotting/filming benefits, even when used as part of a
mixture with straight chain alkyl R groups. The R2 groups
can also be connected to form ring structures. A detergent
surfactant of this type is a Cl0l4 fatty acylamidopropylene-
(hydroxypropylene)sulfobetaine that is available from the
Sherex Company under the trade name "Varion CAS
Sulfobetaine".
Compositions of this invention containing the above
hydrocarbyl amido sulfobetaine (HASB) can contain more
perfume and/or more hydrophobic perfumes than similar
compositions containing conventional anionic detergent
surfactants. This can be desirable in the preparation of
consumer products. Perfumes useful in the compositions of
this invention are disclosed in more detail hereinafter.
-- 6
CA 02261~07 1999-01-14
Other zwitterionic detergent surfactants useful, and,
surprisingly, preferred, herein include hydrocarbyl, e.g.,
fatty, amidoalkylenebetaines (hereinafter also referred to
as "HABn). These detergent surfactants, which are more
cationic at the pH of the composition, have the generic
formula:
R-C(O)-N (R2) - (CR32) n~N (R2) 2(+) - (CR32) n~C (O) O(-)
wherein each R is a hydrocarbon, e.g., an alkyl group
containing from about 8 up to about 20, preferably up to
about 18, more preferably up to about 16 carbon atoms, each
(R2) is either a hydrogen (when attached to the amido
nitrogen), short chain alkyl or substituted alkyl containing
from one to about four carbon atoms, preferably groups
selected from the group consisting of methyl, ethyl, propyl,
hydroxy substituted ethyl or propyl and mixtures thereof,
preferably methyl, each (R3) is selected from the group
consisting of hydrogen and hydroxy groups, and each n is a
number from 1 to about 4, preferably from 2 to about 3; more
preferably about 3, with no more than about one hydroxy
group in any (CR32) moiety. The R groups can be branched
and/or unsaturated, and such structures can provide
spotting/filming benefits, even when used as part of a
mixture with straight chain alkyl R groups.
An example of such a detergent surfactant is a C1014
fatty acylamidopropylenebetaine available from the Miranol
Company under the trade name "Mirataine CBn.
The level of zwitterionic detergent surfactant, when
present in the composition, is typically from about 0.01~ to
about 8~, preferably from about 1~ to about 6~, more
preferably from about 2~ to about 4~. The level in the
composition is dependent on the eventual level of dilution
to make the wash solution. For cleaning, the composition,
when used full strength, or the wash solution containing the
composition, should contain from about 0.01~ to about 8~,
preferably from about 1~ to about 6~, more preferably from
about 2% to about 4~, of the zwitterionic detergent
-- 7
CA 02261~07 1999-01-14
surfactant. Concentrated products will typically contain
from about 0.02~ to about 16~, preferably from about 4~ to
about 8~ of the zwitterionic detergent surfactant.
Nonionic Deterqent Surfactant or Cosurfactant
Compositions of the invention described in parent
Application No. 2,158,248 contain nonionic detergent
surfactant, either alone, or as part of a mixture with a
zwitterionic, or amphoteric, detergent surfactant
("cosurfactant") to provide cleaning and emulsifying
benefits over a wide range of soils. Nonionic detergent
surfactants useful herein include any of the well-known
nonionic detergent surfactants that have an HLB of from
about 6 to about 18, preferably from about 8 to about 16,
more preferably from about 8 to about 10. Mixtures of high
and low HLB nonionic detergent surfactants can also be used.
High HLB nonionic detergent surfactants have an HLB above
about 12, preferably above about 14, and more preferably
above about 15, and low HLB nonionic detergent surfactants
have an HLB of below about 10, preferably below about 9, and
more preferably below about 8.5. The difference between the
high and low HLB values should preferably be at least about
4.
The nonionic detergent surfactant preferably should
comprise the peaked nonionic detergent surfactants mentioned
hereinbefore. A "peaked" nonionic detergent surfactant is
preferably one in which at least about 70~, more preferably
at least about 80~, more preferably about 90~, of the
molecules, by weight, contain within two ethoxy groups
(moieties) of the average number of ethoxy groups. Peaked
nonionic detergent surfactants have superior odor as
compared to nonionic detergent surfactants having a "normal"
distribution in which only about 60~ of the molecules
contain within two ethoxy groups of the average number of
ethoxy groups.
Also, surprisingly, the short chain (C610) nonionic
detergent surfactants, and especially the peaked short chain
nonionic detergent surfactants, when combined with
-- 8
... .
CA 02261~07 1999-01-14
amphoteric and/or zwitterionic detergent surfactants,
especially those that contain a carboxy group, in the acidic
compositions, provide superior sudsing properties. The suds
(foam) is superior both in quantity and in the speed with
which the suds break as compared to similar combinations
with conventional nonionic detergent surfactants and the
peaked surfactants are better than similar short chain
nonionic detergent surfactants having a normal distribution.
The HLB of the peaked short chain nonionic detergent
surfactants is typically from about 6 to about 18,
preferably from about 8 to about 16, more preferably from
about 8 to about 10, and, as before, mixed low and high HLB
short chain peaked nonionic detergent surfactants should
differ in HLB by at least about 4. In the typical "peakedn
distribution at least about 70~, preferably at least about
80~, and more preferably at least about 90~, but less than
about 95~, of the nonionic detergent surfactant contains a
number of ethoxy moieties within two of the average number
of ethoxy moieties.
One preferred nonionic detergent surfactant is either
an octyl polyethoxylate, or mixtures of octyl and decyl
polyethoxylates with from about 0.1~ to about 15~,
preferably from about 1~ to about 5%, of said octyl
polyethoxylate. Another preferred polyethoxylate is a
mixture of C6, C8, and Cl0 polyethoxylates containing from
about 40~ to about 80~, preferably from about 50~ to about
70~, by weight ethoxy moieties in a peaked distribution.
This latter polyethoxylate is especially desirable when the
composition is to be used both at full strength and with
dilution.
Typical of the more conventional nonionic detergent
surfactants useful herein are alkoxylated (especially
ethoxylated) alcohols and alkyl phenols, and the like, which
are well known from the detergency art. In general, such
nonionic detergent surfactants contain an alkyl group in the
C62z, preferably C6l0, more preferably all C8 or mixtures of
C8l0, as discussed hereinbefore, and generally contain from
about 2.5 to about 12, preferably from about 4 to about 10,
g
CA 0226l~07 l999-0l-l4
more preferably from about 5 to about 8, ethylene oxide
groups, to give an HLB of from about 8 to about 16,
preferably from about 10 to about 14. Ethoxylated alcohols
are especially preferred in the compositions of the present
5 type.
Specific examples of nonionic detergent surfactants
useful herein include: octyl polyethoxylates (2.5) and (5);
decyl polyethoxylates (2.5) and (5); decyl polyethoxylate
(6); mixtures of said octyl and decyl polyethoxylates with
at least about 10~, preferably at least about 30~, more
preferably at least about 50~, of said octyl polyethoxylate;
and coconut alkyl polyethoxylate (6.5) . Peaked cut nonionic
detergent surfactants include a C810E5 in which the
approximate distribution of ethoxy groups, by weight, is
15 0=1.2; 1=0.9; 2=2.4; 3=6.3; 4=14.9; 5=20.9; 6=21.5; 7=16.4;
8=9.4; 9=4.1; 10=1.5; 11=0.5; and 12=0.1 and a C810E7 in
which the approximate distribution of ethoxy groups, by
weight, is 0=0.2; 1=0.2; 2=0.5; 3=1.5; 4=6.0; 5=10.2;
6=17.2; 7=20.9; 8=18.9; 9=13.0; 10=7.0; 11=3.0; 12=1.0;
20 13=0.3; and 14=0.1.
A detailed listing of suitable nonionic surfactants,
of the above types, for the detergent compositions herein
can be found in U.S. Pat. No. 4, 557,853, Collins, issued
Dec. 10, 1985. Commercial sources of such surfactants can
25 be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North
American Edition, 1984, McCutcheon Division, MC Publishing
Company.
The nonionic surfactant component can comprise as
little as 0.01~ of the compositions herein, especially when
used with another detergent surfactant, but typically the
compositions will contain from about 0.5~ to about 6~, more
preferably from about 1~ to about 4~, of nonionic
cosurfactant, and when the short chain CB or C810 polyethoxy-
late detergent surfactant is used alone, the amount is from
35 about 0.1~ to about 15%, preferably from about 1~ to about
8~, more preferably from about 2% to about 6~.
-- 10 --
CA 02261~07 1999-01-14
The ratio of nonionic surfactant to zwitterionic or
amphoteric (non-zwitterionic) detergent surfactant is
typically from about 1:4 to about 3:1, preferably from about
1:3 to about 2:1, more preferably from about 1:2 to about
1:1.
Amphoteric (Non-zwitterionic) Detergent Surfactant
These detergent surfactants are similar to the
zwitterionic detergent surfactants, but without the
quaternary group. However, they contain an amine group that
is protonated at the low pH of the composition (below pH
5.5), to form a cationic group, and they may also possess an
anionic group at these pHs.
One suitable amphoteric detergent surfactant is a
C8l4 amidoalkylene glycinate detergent surfactant. These
detergent surfactants are essentially cationic at the acid
pH.
The glycinate detergent surfactants herein preferably
have the generic formula, as an acid, of:
O Rl Rl o
RC - N - (CH2)n - N - CH2 - C - OH
wherein
RC- is a C8l4, preferably C8l0, hydrophobic fatty acyl moiety
containing from about 8 to about 14, preferably from about 8
to about 10, carbon atoms which, in combination with the
nitrogen atom, forms an amido group, each n is from 1 to 3,
and each Rl is hydrogen (preferably) or a Cl2 alkyl or
hydroxy alkyl group. Such detergent surfactants are
available, e.g., in the salt form, for example, from Sherex
under the trade name "Rewoteric AM-Vn, having the formula:
-- 11 -
._
CA 02261~07 1999-01-14
C7C (O) NH (CH2) 2N (CH2CH2OH) CH2C (O) O(~)Na(~).
Not all amphoteric detergent surfactants are
acceptable. Longer chain glycinates and similar substituted
amino propionates provide a much lower level of cleaning.
Such propionates are available as, e.g., salts from Mona
Industries, under the trade name "Monateric 1000", having
the formula:
C7C (O) NH(CH2)2N(CH2CH2OH)CH2CH2C(O)O(~)Na(+).
Cocoylamido ethyleneamine-N-(hydroxyethyl)-2-
hydroxypropyl-1-sulfonate (Miranol CS); Ca lo fatty acyl
amidoethyleneamine-N-(methyl)ethyl sulfonate; and analogs
and homologs thereof, as their water-soluble salts, or
acids, are amphoterics that provide good cleaning.
Preferably, these amphoterics are combined with the short
chain nonionic detergent surfactants to minimize sudsing.
Examples of other suitable amphoteric (non-
zwitterionic) detergent surfactants include:
cocoylamido ethyleneamine-N-(methyl)acetates;
cocoylamido ethyleneamine-N-(hydroxyethyl)acetates;
cocoylamido propyl amine-N-(hydroxyethyl)acetates; and
analogs and homologs thereof, as their water-soluble
salts, or acids, are suitable.
Optional Anionic Detergent Surfactant
Typical optional anionic detergent surfactants are the
alkyl- and alkyl(polyethoxylate) sulfates, paraffin
sulfonates, olefin sulfonates, alpha-sulfonates of fatty
acids and of fatty acid esters, and the like, which are well
known from the detergency art. In general, such detergent
surfactants contain an alkyl group in the Cg22 preferably
Cl0l8, more preferably C12l6, range. The anionic detergent
surfactants can be used in the form of their sodium,
potassium or alkanolammonium, e.g., triethanolammonium
CA 02261~07 1999-01-14
salts. C12-1B paraffin-sulfonates and alkyl sulfates are
especially preferred in the compositions of the present
type.
A detailed listing of suitable anionic detergent
surfactants, of the above types, for the detergent
compositions herein can be found in U.S. Pat. No. 4,557,853,
Collins, issued Dec. 10, 1985. Commercial sources of such
surfactants can be found in McCutcheon's EMULSIFIERS AND
DETERGENTS, North American Edition, 1984, McCutcheon
Division, MC Publishing Company.
The optional anionic detergent cosurfactant component
can comprise as little as 0.001~ of the compositions herein
when it is present, but typically the compositions will
contain from about 0.01~ to about 5~, more preferably from
about 0.02~ to about 2~, of anionic detergent cosurfactant,
when it is present. Anionic detergent surfactants are
desirably not present, or are present only in limited
amounts to promote rinsing of the surfaces.
(b) The Optional Hydrophobic Solvent
In order to obtain the best cleaning, especially of
lipid soils, it is necessary to use a hydrophobic solvent
that has cleaning activity. The solvents employed in the
hard surface cleaning compositions herein can be any of the
well-known "degreasing" solvents commonly used in, for
example, the dry-cleaning industry, in the hard surface
cleaner industry and the metal working industry. The level
of hydrophobic solvent is preferably, and typically, from
about 1~ to about 15~, preferably from about 2~ to about
12~, most preferably from about 5~ to about 10~.
Many of such solvents comprise hydrocarbon or
halogenated hydrocarbon moieties of the alkyl or cycloalkyl
type, and have a boiling point well above room temperature,
i.e., above about 20~C.
The formulator of compositions of the present type will
be guided in the selection of solvent partly by the need to
provide good grease-cutting properties, and partly by
aesthetic considerations.
CA 02261~07 1999-01-14
Generically, the glycol ethers useful herein have the
formula Rl-O-(R2O)-H wherein each Rl is an alkyl group which
contains from about 4 to about 8 carbon atoms, each R2 is
either ethylene or propylene, and m is a number from 1 to
about 3, and the compound has a solubility in water of less
than about 20~, preferably less than about 10~, and more
preferably less than about 6~. The most preferred glycol
ethers are selected from the group consisting of dipro-
pyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl
ether, diethyleneglycolmonohexyl ether, monoethyleneglycol-
monohexyl ether, monoethyleneglycolmonobutyl ether, and
mixtures thereof.
The monopropyleneglycolmonobutyl ether (butoxypropanol)
solvent should have no more than about 20~, preferably no
more than about 10~, more preferably no more than about 7~,
of the secondary isomer in which the butoxy group is
attached to the secondary atom of the propanol for improved
odor.
Solvents for these hard surface cleaner compositions
can also comprise diols having from 6 to about 16 carbon
atoms in their molecular structure. Preferred diol solvents
have a solubility in water of from about 0.1 to about
20 g/100 g of water at 20~C. The diol solvents in addition
to good grease cutting ability, impart to the compositions
an enhanced ability to remove calcium soap soils from
surfaces such as bathtub and shower stall walls. These
soils are particularly difficult to remove, especially for
compositions which do not contain an abrasive.
Other solvents such as benzyl alcohol, n-hexanol, and
phthalic acid esters of Cl4 alcohols can also be used.
Terpene solvents and pine oil, are usable, but are
preferably not present.
(c) The PolYcarboxylate Deterqent Builder
Polycarboxylate detergent builders useful herein,
include the builders disclosed in U.S. Pat. No. 4,915,854,
Mao et al., issued Apr. 10, l99O. Suitable detergent
builders preferably have relatively strong binding constants
for calcium under acid conditions.
- 14 -
CA 02261~07 1999-01-14
Preferred detergent builders include dicarboxylic acids
having from about 2 to about 14, preferably from about 2 to
about 4, carbon atoms between the carboxyl groups. Specific
dicarboxylic detergent builders include succinic, glutaric,
and adipic acids, and mixtures thereof. Such acids have a
pKl of more than about 3 and have relatively high calcium
salt solubilities. Substituted acids having similar
properties can also be used.
These dicarboxylic detergent builders provide faster
removal of the hard water soils, especially when the pH is
between about 2 and about 4.
Other suitable builders that can be used include:
citric acid, and, especially, builders having the generic
formula:
R5-[o-CH(CooH)CH(CooH)]nR5
wherein each R5 is selected from the group consisting of H
and OH and n is a number from about 2 to about 3 on the
average. Other preferred detergent builders include those
described in the U.S. Pat. No. 5,051,212, Culshaw and Vos,
issued Sept. 24, 1991, for "Hard-Surface Cleaning
Compositions. n
In addition to the above detergent builders, other
detergent builders that are relatively efficient for hard
surface cleaners and/or, preferably, have relatively reduced
filming/streaking characteristics include the acid forms of
those disclosed in U.S. Pat. No. 4,769,172, Siklosi, issued
Sept. 6, 1988. Still others include the chelating agents
having the formula:
R-N(cH2cOoM) 2
wherein R is selected from the group consisting of:
CA 02261~07 1999-01-14
-CH2CH2CH2OH; -CH2CH(OH)CH2; -CH2CH(OH)CH2OH; -CH(CH2OH) 2 i
-CH3; -CH2CH2OCH3;
-C-CH3; -CH2-C-NH3;
Il 11
O O
-CH2CH2CH2OCH3; -C(CH2OH)3; and mixtures thereof; and each M
is hydrogen.
The chelating agents of the invention are present at
levels of from about 2% to about 14% of the total
composition, preferably about 3% to about 12~, more
preferably from about 5~ to about 10~.
The acidic detergent builders herein will normally
provide the desired pH in use. However, if necessary, the
composition can also contain additional buffering materials
to give a pH in use of from about 1 to about 5.5, preferably
from about 2 to about 4.5, more preferably from about 2 to
about 4 pH is usually measured on the product. The buffer
is selected from the group consisting of: mineral acids such
as HC1, HNO3, etc. and organic acids such as acetic, etc.,
and mixtures thereof. The buffering material in the system
is important for spotting/filming. Preferably, the
compositions are substantially, or completely free of
materials like oxalic acid that are typically used to
provide cleaning, but which are not desirable from a safety
standpoint in compositions that are to be used in the home,
especially when very young children are present.
The Aqueous Solvent SYstem
The balance of the formula is typically water.
Non-aqueous polar solvents with only minimal cleaning action
like methanol, ethanol, isopropanol, ethylene glycol,
propylene glycol, and mixtures thereof are usually not
present. When the non-aqueous solvent is present, the level
of non-aqueous polar solvent is from about 0.5~ to about
10~, preferably less than about 5% and the level of water is
from about 50~ to about 97%, preferably from about 75% to
about 95%.
- 16 -
CA 02261~07 1999-01-14
O~tional Inqredients
The compositions herein can also contain other various
adjuncts which are known to the art for detergent
compositions so long as they are not used at levels that
cause unacceptable spotting/filming. Non-limiting examples
of such adjuncts are:
Enzymes such as proteases;
Hydrotropes such as sodium toluene sulfonate, sodium
cumene sulfonate and potassium xylene sulfonate; and
Aesthetic-enhancing ingredients such as colorants and
perfumes, providing they do not adversely impact on
spotting/filming in the cleaning of glass. The perfumes are
preferably those that are more water-soluble and/or volatile
to minimize spotting and filming.
HYdrotroPes
Hydrotropes are highly preferred optional ingredients.
In addition to providing the normal benefits associated with
hydrotropes, e.g., phase stability and/or viscosity
reduction, hydrotropes can also provide improved suds
characteristics. Specifically, when the zwitterionic and/or
amphoteric detergent surfactants contain a carboxy group as
the anionic group, the hydrotrope can improve both the
quantity of suds generated, especially when the product is
dispensed from a sprayer or foamer, and, at the same time,
reduce the amount of time required for the foam to "break",
i.e., the time until the foam has disappeared. Both of
these characteristics are valued by consumers, but they are
usually considered to be mutually incompatible. The
hydrotropes that provide the optimum suds improvements are
anionic, especially the benzene and/or alkyl benzene
sulfonates. The usual examples of such hydrotropes are the
benzene, toluene, xylene, and cumene sulfonates. Typically,
these hydrotropes are available as their salts, most
commonly the sodium salts. Preferably, the hydrotrope is
present in at least about molar equivalency to the
zwitterionic and/or amphoteric detergent surfactants.
Typical levels of hydrotropes are from about 0.1% to about
5%, preferably from about 1% to about 3%.
- 17 -
CA 02261~07 1999-01-14
Perfumes
Most hard surface cleaner products contain some perfume
to provide an olfactory aesthetic benefit and to cover any
"chemical" odor 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 odor of the
product itself, rather than impacting on the subse~uent odor
of the surface being cleaned. However, some of the less
volatile, high boiling perfume ingredients can provide a
fresh and clean impression to the surfaces, and it is
sometimes desirable that these ingredients be deposited and
present on the dry surface. Perfume ingredients are readily
solubilized in the compositions by the nonionic and
zwitterionic detergent surfactants. Anionic detergent
surfactants will not solubilize as much perfume, especially
substantive perfume, or maintain uniformity to the same low
temperature.
The perfume ingredients and compositions of this
invention 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 Cumm;n~, issued
Mar. 20, 1979; 4,209,417, Whyte, issued Jun. 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 perfume is
roughly proportional to the percentages of substantive
perfume material used. Relatively substantive perfumes
contain at least about 1~, preferably at least about 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 vapor pressures lower than
that of the average perfume material. Also, they typically
have molecular weights of about 200 or above, and are
- 18 -
CA 02261~07 1999-01-14
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, isobornyl acetate, camphene,
cis-citral (neral), citronellal, citronellol, citronellyl
acetate, paracymene, decanal, dihydrolinalool,
dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol,
geranial, geraniol, geranyl acetate, geranyl nitrile,
cis-3-hexenyl acetate, hydroxy-citronellal, d-limonene,
linalool, linalool oxide, linalyl acetate, linalyl
propionate, methyl anthranilate, alpha-methyl ionone, methyl
nonyl acetaldehyde, methyl phenyl carbinyl acetate,
laevo-menthyl acetate, menthone, iso-menthone, myrcene,
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 about 95% of d-limonene.
Examples of moderately volatile perfume ingredients
are: amyl c; nn~m; C aldehyde, iso-amyl salicylate,
beta-caryophyllene, cedrene, c; nn~mi c alcohol, coumarin,
dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol,
iso-eugenol, flor acetate, heliotropine, 3-cis-hexenyl
salicylate, hexyl salicylate, lilial (para-tertiary-butyl-
alpha-methyl hydroc;nn~m;c aldehyde), gamma-methyl ionone,
nerolidol, patchouli alcohol, phenyl hexanol, betaselinene,
trichloromethyl phenyl carbinyl acetate, triethyl citrate,
- 19 -
CA 02261~07 1999-01-14
vanillin, and veratraldehyde. Cedarwood terpenes are
composed mainly of alpha-cedrene, beta-cedrene, and other
Cl5H24 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-
hexamethylcyclo-penta-gamma-2-benzopyran), hexyl cl nn~m' c
aldehyde, lyral (4-(4-hydroxy-4-methyl pentyl)-3-
cyclohexene-10-carboxaldehyde), methyl cedrylone, 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, but more
water-soluble materials are preferred, as stated
hereinbefore, since such materials are less likely to
adversely affect the good spotting/filming properties of the
compositions.
These compositions have exceptionally good cleaning
properties. They also have good "shine" properties, i.e.,
when used to clean glossy surfaces, without rinsing, they
have much less tendency than e.g., phosphate built products
to leave a dull finish on the surface.
In a preferred process for using the products described
herein, and especially those formulated to be used at full
strength, the product is sprayed onto the surface to be
cleaned and then wiped off with a suitable material like
cloth, a paper towel, etc. It is therefore highly desirable
to package the product in a package that comprises a means
for creating a spray, e.g., a pump, aerosol propellant and
spray valve, etc. All parts, percentages, and ratios herein
are "by weight" unless otherwise stated. The invention is
illustrated by the following Examples.
- 20 -
CA 02261~07 1999-01-14
EXAMPLE I
Inqredient Wt.%
3-(N-dodecyl-N,N-dimethyl)-2-hydroxypropane-
l-sulfonate (DDHPS)l 2.0
5 Octyl polyethoxylate(2.5) (OPE2.5)1.1
Octyl polyethoxylate(6.0) (OPE6) 2.9
Butoxy Propoxy Propanol (BPP) 5.0
Succinic Acid 10.0
Sodium Cumene Sulfonate (SCS) 4.2
10 Water, Buffering Agents, and Minors up to 100
pH 3.0
Varion CAS
EXAMPLE II
Inqredient Wt.%
15 N-(Coconutamidoethylene)-N-(hydroxyethyl)-glycinel 2.0
Cgll Polyethoxylate (6) (C9lE6)2 2.0
BPP 8.0
Citric Acid 10.0
SCS 1.6
20 Water, Buffering Agents, and Minors up to 100
pH 2.97
1 Rewoteric AM-V
2 Neodol 91-6
- 21 -
CA 02261~07 1999-01-14
EXAMPLE I II
A B C
Inqredient Wt.% Wt.~ Wt.
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-
sulfonate (DDHPS)l 2.0
Cgll Polyethoxylate (6)
(C9lE6)2 2.0
CsloE6 _ 2.0 2.0
10 Cocoamido propyl betaine3 - 2.0
N-(Coconutamidoethylene)-N-
(hydroxyethyl)-glycine4 - - 2.0
BPP 8.0 8.0 8.0
Citric Acid 6.0 6.0 6.0
SCS 1.6 1.6 1.6
Water, Buffering Agents,
and Minors -------up to 100-------
pH 2.97 2.97 2.97
1 Varion CAS
2 Neodol 91-6
3 Betaine AMB-15
4 Rewoteric AM-V
The above compositions are tested for cleaning using a
moderate/heavy soap scum on tile. The test is run as
follows:
Standard soiled tiles that are used to provide a
reproducible, standard soiled surface are treated with each
product and five seconds later the surface is rubbed twice
with a Gardner Straight-line Washability Machine. All
treatments are full product and all treatments are the same.
Three expert judges grade the tiles using a scale in which
0 = no visible soil and 8 = "extreme soil".
The grades on the 0-8 scale are: A - 2.1; B - 1.2; and
C - 2.7 with an LSDos ~f about 0.7. B, especially, gives
good results. The improved performance of B is totally
unexpected and it is surprising that an amphoteric like the
glycinate that is essentially cationic at pH 5.5 is
satisfactory.
- 22 -
CA 02261~07 1999-01-14
EXAMPLE IV
A B C D
Inqredient Wt.% Wt.~ Wt.~ Wt.
3-(N-dodecyl-N,N-
5 dimethyl)-2-hydroxy-
propane-1-sulfonate
(DDHPS)1 2.0 2.0 2.0 2.0
Cgll Polyethoxylate (6)
(C9lE6) 2 2.0
C1oE63 - 2.0 - _
C8E64 - - 2.0
C6E6s - - - 2.0
BPP 8.0 8.0 8.0 8.0
Citric Acid 6.0 6.0 6.0 6.0
SCS 1.6 1.6 1.6 1.6
Water, Buffering Agents,
and Minors ------------up to 100-----------
pH 2.97 2.98 2.98 3.10
1 Varion CAS
2 Neodol 91-C
3 Sulfonic L10-6
4 Sulfonic L8-6
5 Sulfonic L6-6
The above formulas are tested as in Example III with
the results as follows (LSDg5 of 0.8): A - 2.3; B - 2.4;
C - 2.2; and D - 4.4. It is surprising that the lower
sudsinq C formula is equal to A and/or B formulas.
- 23 -
CA 02261~07 1999-01-14
EXAMPLE V
Glycinates
a B
Inqredient Wt.~ Wt.~ Wt.
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-sulfonate
(DDHPS)l 2.0
Cgll Polyethoxylate (6)
(C9lE6)2 2.0 2.0 2.0
C81oE6 ~ 2.0 2.0
Lauroamphoglycinate3 - 2.0
Tallow Glycinate4 - - 2.0
BPP 8.0 8.0 8.0
Citric Acid 6.0 6.0 6.0
SCS 3 0 3.0 3.0
Water, Buffering Agents,
and Minors ------up to 100------
pH 2.95 3.23 3.05
1 Varion CAS
Z Neodol 91-6
3 Rewoteric AM 2L-35
4 Rewoteric AM TEG
EXAMPLE V (Continued)
Propionates
D E
Inqredient Wt.~ Wt.
Cgll Polyethoxylate (6) (C9lE6)l 2.0 2.0
Cocoamphopropionate2 2.0
Sodium Lauryliminodipropionate3 - 2.0
BPP 8.0 8.0
Citric Acid 6.0 6.0
SCS 3 0 3.0
Water, Buffering Agents,
and Minors ----up to 100----
pH 3.34 3.37
l Neodol 91-6
2 Rewoteric AM 2CSF
3 Rewoteric AM LP
- 24 -
CA 02261~07 1999-01-14
EXAMPLE V (Continued)
Betaines
F G H
Ingredient Wt.~Wt.~ Wt.
5 Cgll Polyethoxylate (6)
(C9lE6)1 2.0 2.0 2.0
Cs1oE6 _ 2.0 2.0
Cocoamido Propyl Betaine2 2.0 - -
Cocoamido Propyl Betaine3 - 2.0
10 Lauryl Betaine4 - - 2.0
BPP 8.0 8.0 8.0
Citric Acid 6.0 6.0 6.0
SCS 3.0 3.0 3.0
Water, Buffering Agents,
and Minors -------up to 100--~
pH 3.03 3.01 3.12
1 Neodol 91-6
2 Rewoteric AM B14-U
3 Rewoteric AM B15-U
4 Rewoteric DML-35
The formulas in Example V are treated as in Example III
with the results as follows (LSDg5 at about 0.7): A - 1.3;
B - 1.4; C - 5.3; D - 3.34; E - 3.1; F - 1.3; G - 1.0; and
H - 1.8. Again, the betaines, especially, are surprisingly
good and the glycinate amphoteric is much better than the
adjacent propionate.
CA 02261~07 1999-01-14
EXAMPLE VI
B
InqredientWt.% Wt.%
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-sulfonate
(DDHPS)l 2.0 2.0
Cg,l Polyethoxylate (6)
(C9lE6) 2 2.0 2.0
BPP 8.0 8.0
10 Citric Acid 6.0
Succinic Acid - 6.0
SCS 3.0 3.0
Water, Buffering Agents,
and Minors ----up to 100---
pH 2.95 3.01
l Varion CAS
2 Neodol 91-6
The above formulas are tested as in Example III and
found equivalent, but when tested by exposing the wash
solutions to marble chips, which are representative of hard
water calcium carbonate deposits, B is indexed at 190 as
compared to A's 100. Also, on lower grade colored enamels,
B shows no discoloration, whereas A shows a slight
discoloration.
- 26 -
CA 02261~07 1999-01-14
-
EXAMPLE VII
Comparative
Example B
Ingredient Wt.~ Wt.
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-
sulfonate (DDHPS)l 2.0
Cocoylamido Propylene Betaine2 - 2.0
Cgll Polyethoxylate (6)
(C9lE6)3 2.0 2.0
BPP 8.0 8.0
Citric Acid 6.0 6.0
SCS 3 0 3 0
Water, Buffering Agents,
and Minors ----up to 100----
pH 2.95 3.01
l Varion CAS
2 Betaine AMB-15-V
3 Neodol 91-6
The above formulas are tested as in Example III. The
soap scum grade for A is 1.9 and for B is 0.9 with an LSD at
95~ of 0.6. The commercial product which is the market
leader has a grade of 5.1. B is clearly superior to both A
and the market leader.
EXAMPLE VIII
A B
Inqredient Wt.~Wt.
Ca-loE6 2.0 2.0
Cocoamido Propyl Betainel 2.0 2.0
BPP 8.0 8.0
Succinic Acid 6.0 6.0
SCS 1.6 1.6
Water, Buffering Agents, and Minors ---up to 100---
pH 2.00 4.5
1 Betaine AMB-15
CA 02261~07 1999-01-14
EXAMPLE IX
A B C
Inqredient Wt.% Wt.~ Wt.
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-
sulfonate (DDHPS)l 2.0
Cocoylamidopropyl Betaine2 - 1.75 1.75
Cgll Polyethoxylate 16)
(C9lE6)3 2.0
10 C8l0 Polyethoxylate (6)
(peaked cut C8loE6) 4 - 2.0 2.0
BPP 8.0 6.0 6.0
Citric Acid 6.06.0 6.0
SCS 3.0- 2.0
15 Water, Buffering Agents, and Minors ----up to 100---
pH 3.0 3.0 3.0
1 Varion CAS
2 Betaine AMB-15-V
3 Neodol 91-6
4 Peaked cut C8loE6 as described hereinbefore.
The above formulas are sprayed through T-8900 sprayers
available from Continental Sprayers, Inc. The C formula
provides better performance with less total active materials
than the comparative A formula. In addition, the
approximate volume of suds in cc of suds per cc of product
for the A, B, and C, formulas is: A - 3.6; B - 4.0; and
C - 5.9 while the approximate time for the suds to "break"
in seconds is: A - 9.25; B - 6.4; and C - 4Ø As can be
seen from this comparison, the effect of the hydrotrope, in
addition to selection of the zwitterionic detergent
surfactant containing the carboxy group, provides both more
suds and suds which break quicker.
CA 02261~07 1999-01-14
EXAMPLE X
_ B C
Ingredient Wt.~ _t.~ Wt.
3-(N-dodecyl-N,N-dimethyl)-
2-hydroxy-propane-1-
sulfonate (DDHPS)l 2.0
Cocoylamidopropyl Betaine2 - 1.75 1.75
Cgll Polyethoxylate (6)
(C9lE6) 3 2.0
10 C8l0 Polyethoxylate (6)
(peaked cut C8loE6) 4 - 2.0 2.0
BPP 8.0 6.0 6.0
Citric Acid 6.0 6.0 6.0
SCS 3.0 - 2.0
Xanthan Gum 0.230.23 0.23
Water, Buffering Agents, and Minors ----up to 100---
pH 3.0 3.0 3.0
1 Varion CAS
2 Betaine AMB-15-V
3 Neodol 91-6
4 Peaked cut C8loE6 as described hereinbefore.
Thickeners are desirable additives, for both spray and
non-spray products. The thickeners are preferably those
described in U.S. Pat. No. 5,232,632, Woo et al., at the
levels described in said patent.
- 29 -
