Note: Descriptions are shown in the official language in which they were submitted.
~ W096~3482 r~
2 I q4053
PROCESS FOR NAKING GR~NU~AR DETERGENTS AND DETERGENT
COMPOSITIONS COMPRISING NONIONIC SURFACTANT
The present invention relates to improving storage
stability and physical properties of granular detergents
which are rich in nonionic surfactant. In particular the
invention relates to a process for incorporating a certain
class of nonionic surfactants, namely polyhydroxy fatty
acid amides, into granular detergent compositions.
The use of nonionic surfactants in granular detergents has
been widely discussed in the prior art. In particular,
detergent compositions comprising ethoxylated nonionic
surfactants and polyhydroxy fatty acid amides have been
described in W09206160, published on 16th April 1992.
W096/03482 2 ~ 9 4 0 5 3 ~ S ~5 ~
WO9206160 discloses compositions which comprise ethoxylated
nonionic 5urfactant and polyhydroxy fatty acid amides, and
granulation processes for making them ~Examples 14, 15,
20). The mixed nonionic systems are granulated with
zeolite, carbonate and, optionally, citrate. Water may also
be present during the granulation step, but there is no
suggestion of the use of an organic structuring agent.
The Applicants co-pending application EP93870075.4, filed
on 30th April 1993, describes a process for granulating
nonionic surfactants wherein a polymer is premixed with
nonionic surfactant to increase its viscosity prior to
granulation. Organic polymers such as PVP are preferred.
Polyhydroxy fatty acid amides are also disclosed as
optional ~ -nts which may also have a structuring
effect.
The previous applications have been con~-nn-d with
providing excellent stain removal performance, especially
on greasy / oily stains. Particles which retain good
hAn~l;ng properties during storage and which dissolve
rapidly upon contact with water in order to release their
active ingredients to the site of the stains are required
for commercial purposes. It has been found that the need
for good handling properties and rapid rates of dissolution
tend to impose conflicting re~uirements upon the
formulator.
~ W096/03482 2 1 ~053
The present invention deals with the problem of these
conflicting requirements by incorporating an organic
~ structuring agent, selected from the family of glyceride
fats, which provides sufficient structure to the nonionic
surfactant granules to give the required h~n~l; ng
properties, and which still permits rapid rates of
dissolution.
The present invention provides a process for making
nonionic surfactant particles having excellent stain
removal performance by providing high bulk density
detergent particles which have a high activity of n~nion;c
surfactants which are efficient stain removers.
The present invention also provides a process for making
nonionic surfactant particles which are stable upon
storage, and which in particular do not "leak" liquid
nonionic surfactant into the container when stored.
Nonionic surfactant "leakagen, if not prevented, leads to
cardboard containers being stained and also to product
caking. Both of these undesirable consequences are avoided
by the present invention.
The present invention also provides a means for structuring
a nonionic surfactant system with an organic structuring
agent which is both weight- and cost-efficient.
W096/03482 21 94~53 r.~
Summary of the Invention
The present invention provides a process for making a
granular laundry detergent ~-~nent or composition havinrg
a bulk density of at least 650 g/1 comprising the steps
of ;
a) dissolving a structuring agent in a nonionic surfactant
to form a pumpable premix,.wherein the nonionic surfactant
comprises polyhydroxy fatty acid amide at a level of at
least 3% (by weight of the ~ t or composition), and
wherein the structuring agent comprises a glyceride; and
b) granulating said premix.
It is preferred that the glyceride structuring aqent is a
triglyceride, especially glycerol tristearate.
The nonionic surfactant comprises polyhydroxy fatty acid
amide and optionally also comprises ethoxylated nonionic
surfactant, the ratio of polyhydroxy fatty acid amide to
ethoxylated nonionic surfactant being at least 1:4, and
preferably from 1:4 to 4:1.
The preferred pumpable premix comprises:
a) from 10% to 70% by weight of ethoxylated nonionic
surfactant;
b) from 10~ to 70% by weight of polyhydroxy fatty acid
amide;
21 9~53
WO 96/03482 . ~1/6~J~ a
s
c) from 0.1% to 20% by weight of glyceride;
d) from 0% to 20~ by weight of fatty acid; and
~ optionally water.
~ The premix may subsequently be granulated with a powder,
said powder preferably being selected from the group
consisting of aluminosilicate, carbonate, bicarbonate,
silicate, sulphate, citrate and mixtures thereof, and ratio
of the premix to the powder being at least 1:4, pre~erably
between 1:4 and 4:1.
The granular laundry detergent composition or ~ ~~t of
the present invention typically comprise:
a) up to 35% (preferably from 10% to 35%, and more
preferably 15% to 25%~ by weight of ethoxylated
nonionic surfactant;
b) from 3% to 80% (preferably 3% to 35~, and more
preferably 5% to 15%) by weight of polyhydroxy fatty
acid amide;
c) from 0.01% to 10% (preferably 0.5% to 8%) by weight
of glyceride;
d) up to 10% (preferably 0.1% to 5%) by weight of
fatty acid; and
e) from 10% to 90% (preferably 25% to 86.99%, and more
preferably 50% to 79.4%) by weight of a powder, said
~ powder being selected from the group consisting of
aln~inn.~;licate~ carbonate, bicarbonate, silicate,
sulphate, citrate and mixtures thereof.
W096/03482 21 94~53 r~ ,3, ~
Detailed Description of the Invention
The process aspect of the present invention comprises two
essential steps. The first process step i5 the formation of
a nonionic surfactant premix which comprises a structuring
agent. The second process step is the processing of the
surfactant premix into the form of a granular detergent
having the desired physical properties of bulk density,
flow properties and storage characteristics.
The first process step of the invention is the preparation
of a structured nonionic surfactant premix. This premix
comprises two essential ~n~nts which will be described
in more detail below. These ~~t~ are the n~ni~n;~
surfactant (comprising polyhydroxy fatty acid amide) and
the glyceride structuring agent. In the first process step
the glyceride structuring agent is dissolved or slurried in
the nonionic surfactant.
The second process step may be based upon any of the
techniques of forming granules which are known to the man
skilled in the art. However, the most preferred granulation
techniques for use in the present invention are fine
dispersion of the structured nonionic surfactant paste
premix in the presence o~ powders. One example of such a
process is to pump or spray the surfactant paste premix
into a high shear mixer. The high shear conditions in the
~ W096/03482 2~ 940~3 rc~ s
mixer break up the surfactant paste premix into small
droplets and distribute those droplets onto and around the
powder. The process is often described as "agglomeration".
Another example of such a process is to spray the
surfactant paste premix onto a powder under low shear
conditions (such as a rotating drum). In this case the
energy to break the paste into fine droplets comes at the
spray nozzle, and in the low shear mixer the droplets are
absorbed on to the surface, or into the pores of the
powder. Preferred granulation processes are described in
more detail below.
Nonionic Surfactant
Polyhydroxy fatty acid amides.
Polyhydroxy fatty acid amides may be prepared by reacting a
fatty acid ester and an N-alkyl polyhydroxy amine. The
preferred amine for use in the present invention is N-(R1)-
CH2(CH20H)4-CH2-OH and the preferred ester is a C12-C20
fatty acid methyl ester. Most preferred is the reaction
product of N-methyl glucamine (which may be derived from
glucose) with C12-C20 fatty acid methyl ester.
~ethods of manufacturing polyhydroxy fatty acid amides have
been described in WO 92060~3, published on 16th April,
W096/03482 r~
2~ 94053 ~
1992. This application describes the preparation of
polyhydroxy fatty acid amides in the presence of solvents.
In a highly preferred embodiment of the invention N-methyl
glucamine is reacted with a C12-C20 methyl ester. It also
says that the formulator of granular detergent compositions
may find it convenient to run the amidation reaction in the
presence of solvents which comprise alkoxylated, P~peciAlly
ethoxylated ~EO 3-8) C12-C14 alcohols (page 15, lines 22-
27). This directly yields nonionic surfactant systems which
are preferred in the present invention, such as those
comprising N-methyl glucamide and C12-C14 alcohols with an
average of 3 ethoxylate groups per molecule.
Other Nonionic Surfactants
Suitable nonionic surfactants include compounds produced by
the cnn~Pncation of alkylene oxide groups (hydrophilic in
nature) with an organic hydrophobic compound, which may be
aliphatic or alkyl aromatic in nature. The length of the
polyoxyalkylene group 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.
Particularly preferred for use in the present invention are
nonionic surfactants such as the polyethylene oxide
cnn~Prqates of alkyl phenols, e.g., the cnndPnqAtion
products of alkyl phenols having an alkyl group containing
~ W096/03482 2 1 9 4 0 ~ 3 P~ . C ~ ,~5
from about 6 to 16 carbon atoms, in either a straight chain
or branched chain configuration, with from about 1 to 25
moles of ethylene oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble cnnAPncation
products of aliphatic alcohols containing from 8 to 20
carbon atoms, in either straight chain or branched
configuration, with an average of from 1 to 25 moles of
ethylene oxide per mole of alcohol. Particularly preferred
are the c~n~n~ation products of alcohols having an alkyl
group containing from about 9 to 15 carbon atoms with from
about 2 to 10 moles of ethylene oxide per mole of alcohol;
and con~n~ation products of propylene glycol with ethylene
oxide. Most preferred are c~n~n~ation products of alcohols
having an alkyl group containing from about 12 to 15 carbon
atoms with an average of about 3 moles of ethylene oxide
per mole of alcohol.
Many of the nonionic surfactants which fall within the
definitions given above have are liquid at temperatures
below 40~C (that is to say the solidification temperature
is below 40~C). ~he present invention has been found to be
particularly useful for such nonionic surfactants.
Structuring Agent
. .
The structuring agents of the present invention should
preferably having a melting point of at least 40~C, and
W096/03482 2 1 9 4 0 5 3 r~ r ~
~o
more preferably at least 60~C. Glycerides suitable for use
as structuring agents in the present invention include
tri-, di- and mono-glycerides.
Triglycerides are described in Kirk-Othmer, Encyclopedia of
Chemical technology, 3rd Edition, Wiley, Volume 9, page 795
onwards. Triglycerides are fats which may be derived from
vegetable, animal and marine sources. A generalised
triglyceride has the structure:
H2 C O C O R
I
H C O C O R'
I
H2 C O C O R"
Preferably R, R' and R" are alkyl chains having between 1
and 26 carbon atoms, more preferably between 12 and 22
carbon atoms. For example when R = R' = R" = C17 H 35 the
triglyceride is called tristearin or glycerol tristearate.
When R = R' = R" = CH3 the triglyceride is glycerol
triacetate. Hardened tallow triglyceride is particularly
preferred for use as a structuring agent for use in the
present invention. Preferably the glyceride has an iodine
value of less than 1.
21 94~53
W096/~3482
11
Diglycerides and monoglycerides may be derived from
triglycerides by hydrolysis to give :
H2 C O C O R H2 C O C O R
H C O C O R' or H C O H
H2 C O H H2 C O H
diglyceride monoglyceride
Processing the Structured Paste Premix
The paste premix including the structuring agent may be
prepared in any suitable manner, but will typically be a
simple mixing process. Any type of mixer may be used to
prepare the premix, especially a dynamic mixer. The mixing
equipment will need to be selected to handle the relatively
high viscosities that the structured paste premix will
reach. The exact viscosity will depend on the composition
of the structured paste premix, and on the processing
temperature. Preferably the processing temperature is
greater than 50~C, more preferably greater than 60~C and
most preferably greater than 70~C.
In a particularly preferred ~o~;r~nt of the present
invention the temperature of the paste premix is controlled
w096~3482 21 9 ~ 0 53 ~ ~5~ /~a ~
to the required processing temperature ~and viscosity) by
passing it through a scraped surface heat exchanger, such
as a Chemetator ~, before the subsequent granulation step.
The structured paste premix may be subsequently granulated
by various process means. Preferred means are described in
more detail below.
Fine Dispersion Mixing and Granulation
Suitable pieces of equipment in which to carry out the fine
dispersion mixing or granulation of the present invention
are mixers of the FukaeR FS-G series ~-nllf~ctllred by Fukae
Powtech Kogyo Co., Japan; this apparatus is essentially in
the form of a bowl-shaped vessel accessible via a top port,
provided near its base with a stirrer having a
substantially vertical axis, and a cutter positioned on a
side wall. The stirrer and cutter may be operated
independently of one another and at separately variable
speeds. The vessel can be fitted with a cooling jacket or,
ii' necessary, a cryogenic unit.
Other similar mixers found to be suitable for use in the
process of the invention include DiosnaR V series ex Dierks
& Sohne, Germany; and the Pharma MatrixR ex T K Fielder
Ltd., England. Other mixers believed to be suitable for
use in the process of the invention are the EujiR VG-C
_ _ _ _ . . = . .
~ W096/03482 2 1 ~4053
13
series ex Fuji Sangyo Co., Japan; and the RotoR ex
Zanchetta & Co srl, Italy.
Other preferred suitable equipment can include EirichR,
series RV, manufactured by Gustau Eirich Hardheim, Germany;
LodigeR, series FM for batch mixing, or series CB and KM,
either separately or in series for continuous
mixing/agglomeration, manufactured by Lodige MA~hin~nh~ll
GmbH, Paderborn Germany; DraisR T160 series, manufactured
by Drais Werke GmbH, MAnnheim Germany; and WinkworthR RT 25
series, manufactured by Winkworth M~h;nery Ltd.,
Berkshire, England.
The Littleford Mixer, Model #EM-130-D-12, with internal
chopping blades and the C~lisinArt Food Processor, Model
#DCX-Plus, with 7.75 inch (19.7 cm~ blades are two examples
of suitable mixers. Any other mixer with fine dispersion
mixing and granulation capability and having a residence
time in the order of 0.1 to 10 minutes can be used. The
"turbine-type" impeller mixer, having several blades on an
axis of rotation, is preferred. The invention can be
practiced as a batch or a continuous process.
Further Processing Steps
The granular ,- _~n~ntS or compositions obtained by the
process described herein may be suitable for use directly,
2 1 ~ 3
W096/03482 ~I/U~
14
or they may be treated by additional process steps.
Commonly used process steps include drying, cooling and/or
dusting the granules with a finely divided flow aid. In
addition the granules may be blended with other ~ p~ A~t~s
in order to provide a composition suitable for the desired
end use.
Any type of mixer or dryer (such as fluid bed dryers) may
be found to be suitable for this purpose.
The finely divided flow aid, if used, may be chosen from a
wide variety of suitable ingredients such as zeollte,
silica, talc, clay or mixtures of these.
Normally the detergent compositions made according to the
present invention may include a wide range of other
ingredients and components which are known to the man
skilled in the art to have a function in the washing
process. Typical examples of such ingredients which may be
used in detergent compositions are given below. These
optional ingredients may be co-granulated with the nonionic
surfactant by the process of the present invention, or,
alternatively, they may be granulated by separate means and
subsequently combined with the nonionic surfactant
granulates of the present invention by dry mixing,
spraying-on etc.
WO 96/03482 r C I; ~J ~, c I / D
~ 21 ~4053
~s
Anionic Surfactants
Alkyl Ester Sulfonate Surfactant
Alkyl Ester sulfonate surfactants hereof include linear
esters of Cg-C20 carboxylic acids ~i.e. fatty acids) which
are sulfonated with gaseous SO3 according to "The Journal
of the American Oil Chemists Society"' 52 (1975), pp. 323-
329. Suitable starting materials would include natural
fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, espe~i~lly
for laundry applications, comprises alkyl ester sulfonate
surfactants of the structural formula:
R3 - CH - C - OR
I
SO3M
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
21 94a53
W096/03482 r~
16
diethanolamine, and triethanolamine. Preferably, R3 is
C10-Cl6 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R is C14 C16 alkyl-
Alkyl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or
acids or the formula ROS03~ wherein R preferably is a C10-
C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having
a C10-C20 alkyl component, more preferably a C12-C18 alkyl
or hydroxyalkyl, and ~ is H or a cation, e.g., an alkali
metal cation (e.g., sodium, potassium, lithium), or
a~monium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl i cations and quaternary ammonium
cations, such as tetramethyl-ammonium and dimethyl
piperdinium cations and quarternary ammonium cations
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C12 16 are preferred for lower
wash temperatures (e.g., below about 50~C) and C16 18 alkyl
chains are preferred for higher wash temperatures (e.g.,
above about 50~C).
Alkyl Alkoxylated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are
water soluble salts or acids of the formula RO(A)mS03~
wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl
2 1 94053
W096l03482 1~ 5
17
group having a ClO-C24 alkyl component, preferably a C12-
C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater
than zero, typically between about 0.5 and about 6, more
preferably between about 0.5 and about 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 cations, such as
tetramethyl-ammonium, dimethyl piperdinium and cations
derived from alkanolamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C18 alkyl
polyethoxylate (1.0) sulfate, C12-C18E(1-~)M)~ C12-C18
alkyl polyethoxylate (2.25) sulfate, C12~C18E(2-25)M), C12-
C1g alkyl polyethoxylate (3.0) sulfate Cl2-C1gE~3.0), and
C12-C18 alkyl polyethoxylate (4.0) sulfate C12-C1gE(4.0)M),
wherein M is conveniently selected from sodium and
potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive
purposes can also be included in the laundry detergent
compositions of the present invention. These can include
W096/03482 2 1 9 ~ 0 5 3 ~ 5
salts (including, for example, sodium, potassium, ammonium,
and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, C9-C20 linear
alkylbenzenesulphonates, C8-C22 primary or secondary
alkanesulphonates, C8-C24 olefinsulphonates, 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~; acyl glycerol sulfonates, fatty
oleyl glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl
taurates, alkyl sucr;n~-tes and sulfosuccinates,
monoesters of sulfosuccinate ~Pspe~i~lly saturated and
unsaturated C12-C18 monoesters~ diesters of sulfosuccinate
(especially saturated and unsaturated C6-C14 diesters),
acyl sarcosinates, sulfates of alkylpolysaccharides such as
the sulfates of alkylpolyglucoside, branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of
the formula RO(CH2CH2O)kCH2COO-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
~ W096/034~2 2 ~ 9 4 0 5 3 . ~
,9
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 ~herein incorporated by
reference).
When ;nclll~ed therein, the laundry detergent compositions
of the present invention typically comprise from about 1 %
to about 40 %, preferably from about 3 % to about 20 % by
weight of such anionic surfactants.
Other Surfactants
The laundry detergent compositions of the present invention
may also contain cationic, ampholytic, zwitterionic, and
semi-polar surfactants, as well as nonionic surfactants
other than those already described herein, including the
semi-polar nonionic amine oxides described below.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
those having one long-chain hydrocarbyl group. Examples of
such cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those
surfactants having the formula :
RlR2R3R4N+X-
wherein R1 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each
W096/03482 20 2 1 ~4053
of R2, R3, R4 is independently C1-C4 alkyl, C1-Cq hydroxy
alkyl, benzyl, and -(C2~4)x~ where x has a value from 2 to
5, and X~ is an anion. Not more than one of R2, R3, R4
should be benzyl.
The preferred alkyl chain length for R1 is C12-C1s,
particularly where the alkyl group is a mixture of chain
lengths derived from coconut or palm kernel fat, or is
derived synthetically by olefin build up or OX0 alcohols
synthesis. Preferred groups for R2, R3, R4 are methyl and
hydroxyethyl groups, and the anion X may be selected from
halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds for use
herein are:
coconut trimethyl ammonium chloride or bromide
coconut methyl dihydroxyethyl ammonium chloride
or bromide
decyl triethyl ammonium chloride or bromide
decyl dimethyl hydroxyethyl ammonium chloride
or bromide
C12-14 dimethyl hydroxyethyl ammonium chloride
or bromide
myristyl trimethyl ammonium methyl sulphate
lauryl dimethyl benzyl ammonium chloride or bromide
lauryl methyl (ethenoxy)4 ammonium chloride or
bromide
The above water-soluble cationic components of the
compositions of the present invention, are capable of
_ W096/03482 r~ 5
21 9~53
21
existing in cationic form in a 0.1% aqueous solution at
pH10.
Other cationic surfactants useful herein are also described
in U5 Patent 4,228,044, Cambre, issued October 14, 1980,
incorporated herein by reference.
When included therein, the laundry detergent compositions
of the present invention typically comprise from 0 4 to
about 25 %, preferably form about 3 % to about 15 ~ by
weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the
laundry detergent compositions of the present invention.
These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines
in which the aliphatic radical can be straight- or branched
chain. One of the aliphatic substituents contains at least
8 carbon atoms, typically from about 8 to about 18 carbon
atoms, and at least one contains an anionic water-
solllhili7ing group e.g. carboxy, sulfonate, sulfate. See
U.S. Patent No. 3,929,678 to T.~lghlin et al., issued
December 30, 1975 at column 19, lines 18-35 (herein
incorporated by reference) for examples of ampholytic
surfactants.
2~ 94~53
W096r03482
22
When included therein, the laundry detergent compositions
of the present invention typically comprise form 0 ~ to
about 15 ~, preferably from about 1 ~ to about lO % by
weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
laundry detergent compositions. These surfactants can be
broadly described as derivatives of secondary and tertiary
amines, derivates of heterocyclic secondary and tertiary
amines, or derivatives of quaternary ammonium, quarternary
phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3,929,678 to T~ughl;n et al., issued December
30, 1975 at columns l9, line 38 through column 22, line 48
(herein incorporated by reference) for examples of
zwitterionic surfactants.
When included therein, the laundry detergent compositions
of the present invention typically comprise form 0 ~ to
about 15 %, preferably from about l ~ to about lO ~ by
weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about lO to
about 18 carbon atoms and 2 moieties selected from the
group consisting af alkyl groups and hydrocyalkyl groups
containing form ~about 1 to about 3 carbon atoms; water-
soluble phosphine oxides containing one alkyl moiety of
~ W096l03482 2 1 9 4 0 5 3
form about 10 to about 18 carbon atoms and 2 moieties
selected form the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3
carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula :
r~
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group
or mixtures thereof containing from about 8 to about 22
carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from about 2 to about 3 carbon atoms or mixtures
thereof~ x is form 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing form about 1 to about 3
carbon atoms or a polyethylene oxide group containing from
about 1 to about 3 ethylene oxide groups. The R5 groups
can be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
There amine oxide surfactants in particular include C1o-C18
alkyl dimenthyl amine oxides and Cg-C12 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the laundry detergent compositions
of the present invention typically comprise form 0 ~ to
W096/03482 2 1 ~ 4 0 5 3
24
about 15 %, preferably from about 1 ~ to about 10 ~ by
weight of such semi-polar nonionic surfactants.
Builders
Sodium aluminosilicate may take many forms. One example is
crystalline aluminosilicate ion exchange material of the
formula
Naz[(AlO2)z~(SiO2)y] xH2O
wherein z and y are at least about 6, the molar ratio of z
to y is from about 1.0 to about 0.4 and z is from about 10
to about 264. Amorphous hydrated al~ nS; 1; r~te materials
useful herein have the empirical formula
Mz(zAlo2~ysio2)
wherein M is sodium, potassium, ammonium or substituted
ammonium, z is from about 0.5 to about 2 and y is 1, said
material having a magnesium ion exchange capacity of at
least about 50 milligram equivalents of CaCO3 hardness per
gram of anhydrous aluminosilicate. Hydrated sodium Zeolite
A with a particle size of from about 1 to lO microns is
preferred.
The aluminosilicate ion exchange builder materials
herein are in hydrated form and contain from about 10% to
about 28~ of water by weight if crystalline, and
potentially even higher amounts of water if amorphous.
~ighly preferred crystalline aluminosilicate ion exchange
~ W096/03482 2~ 94053 ~ s
materials contain from about 18% to about 22% water in
their crystal matrix. The crystalline aluminosilicate ion
exchange materials are further characterized by a particle
size diameter of from about 0.1 micron to about 10 micro~s.
Amorphous materials are often smaller, e.g., down to less
than about 0.01 micron. Preferred ion exchange materials
have a particle size diameter of from about 0.2 micron to
about 4 microns. The term "particle size diameter" herein
represents the averaqe particle size diameter by weight of
a given ion exchange material as det~rmined by conventional
analytical techniques such as, for example, microscopic
determination utilizing a scanning electron microscope.
The crystalline all ino~s;licate ion exchange materials
herein are usually further characterized by their calcium
ion exchange capacity, which is at least about 200 mg
equivalent of CaC03 water hardness/g of Al inosilicate~
calculated on an anhydrous basis, and which generally is in
the range of from about 300 mg eq./g to about 352 mg eq./g.
The aluminosilicate ion exchange materials herein are still
further characterized by their calcium ion exchange rate
which is at least about 2 grains
Ca++/gallon/minute/gram/gallon of aluminosilicate
(anhydrous basis), and generally lies within the range of
from about 2 grains/gallon/minute/gram/gallon to about 6
grains/gallon/minute/gram/gallon, based on calcium ion
hardness. Optimum aluminosilicate for builder purposes
exhibit a calcium ion exchange rate of at least about 4
grains/gallon/minute/gram/gallon.
W096l03482 2 1 ~4053 F_llu~
26
The amorphous aluminosilicate ion exchange materials
usually have a Mg++ exchange of at least about 50 mg eq.
CaC03/g ~12 mg Mg++/g) and a Mg++ exchange rate of at lea6t
about l grain/gallon/minute/gram/gallon. Amorphous
materials do not exhibit an observable diffraction pattern
when examined by Cu radiation (1.54 Angstrom Units).
Aln~i n~s; 1 i cate ion exchange materials useful in the
practice of this invention are commercially available. The
aluminosilicates useful in this invention can be
crystalline or amorphous in structure and can be naturally
occurring aluminosilicates or synthetically derived. A
method for producing aluminosilicate ion exchange materials
is discussed in U.S. Pat. No. 3,985,669, Krummel et al.,
issued Oct. 12, 1976, incorporated herein by reference.
Preferred synthetic crystalline alnmin~silicate ion
exchange materials useful herein are available under the
designations Zeolite A, Zeolite B, Zeolite MAP and Zeolite
X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula
Na12[(Al~2)12(5iO2)l2] xH20
wherein x is from about 20 to about 30, especially about 27
and has a particle size generally less than about 5
microns.
~ W096103482 2 1 94 ~53 I~l/u~ ,~
other ingredients which are known for use in the
components and compositions may also be used as optional
ingredients in the present invention.
The granular detergents of the present invention can
contain neutral or alkaline salts which have a pH in
solution of seven or greater, and can be either organic or
inorganic in nature. The builder salt assists in providing
the desired density and bulk to the detergent granules
herein. While some of the salts are inert, many of them
also function as detergency builder materials in the
laundering solution.
Examples of neutral water-soluble salts include the alkali
metal, ammonium or substituted ammonium chlorides,
fluorides and sulfates. The alkali metal, and especially
sodium, salts of the above are preferred. ~odium sulfate
is typically used in detergent granules and is a
particularly preferred salt. Citric acid and, in general,
any other organic or inorganic acid may be incorporated
into the granular detergents of the present invention as
long as it is chemically compatible with the rest of the
agglomerate composition.
Other useful water-soluble salts include the compounds
~ commonly known as detergent builder materials. Builders
are generally selected from the various water-soluble,
alkali metal, ammonium or substituted ammonium phosphates,
W096/03482 2 1 9 4 ~ 3 L~ s ~ a
28
polyphosphates, phosphonates, polyphosphonates, carbonates,
silicates, borates, and polyhyroxysulfonates. Preferred
are the alkali metal, especially sodium, salts of the
above.
Specific examples of inorganic phosphate builders are
sodium and potassium tripolyphosphate, pyrophosphate,
polymeric metaphosphate having a degree of polymerization
of from about 6 Fo 21, and orthophosphate. Examples of
polyphosphonate builders are the sodium and potassium salts
of ethylene diphosphonic acid, the sodium and potassium
salts of ethane 1-hydroxy-1,1-diphosphonic acid and the
sodium and potassium salts of ethane, 1,1,2-trirhnsrh~nic
acid. Other rhoSrh~rus builder compounds are disclosed in
U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137;
3,400,176 and 3,400,148, incorporated herein by reference.
Examples of n~nrhosph~rus, inorganic builders are sodium
and potassium carbonate, bicarbonate, sesquicarbonate,
tetraborate decahydrate, and silicate having a molar ratio
of SiO2 to alkali metal oxide of from about 0.5 to about
4.0, preferably from about 1.0 to about 2.4. Layered,
crystalline silicates such as those supplied by Hoechst
under the name SKS-6 ~ may also be used.
As mentioned above powders normally used in detergents such
as zeolite, carbonate, bicarbonate, silica, silicate,
citrate, phosphate, perborate, etc. and process acids such
~ W096/03482 2 t 9 ~53
29
as starch, can be used in preferred embodiments of the
present invention.
Polymers
Also useful are various organic polymers, some of which
also may function as builders to improve detergency.
Included among such polymers may be mentioned sodium
carboxy-lower alkyl celluloses, sodium lower alkyl
celluloses and sodium hydroxy-lower alkyl c~ oses~ such
as sodium carboxymethyl cellulose, sodium methyl cellulose
and sodium hydroxypropyl cellulose, polyvinyl alcohols
(which often also include some polyvinyl acetate),
polyvinylpyrrolidone, polyacrylamides, polyacrylates and -
various copolymers, such as those of maleic and acrylic
acids. Molecular weights for such polymers vary widely but
most are within the range of 2,000 to 100,000.
Polymeric polycarboxylate builders are set forth in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967. Such
materials include the water-soluble salts of homo-and
copolymers of aliphatic carboxylic acids such as maleic
acid, itaconic acid, mesaconic acid, fumaric acid, aconitic
acid, citraconic acid and methylenemalonic acid.
W096/03482 2 1 9~053 r~ a
Other Optionals Ingredients
.
Other ingredients commonly used in detergent compositions
can be included in the ,_ -n~nts and compositions of th~
present invention. ~hese include color speckles, bl~arhing
agents and bleach activators, suds boosters or suds
suppressors, antitarnish and anticorrosion agents, soil
Sncp~n~;ng agents, soil release agents, dyes, fillers,
optical brighteners, germicides, pH adjusting agents,
n~nh~ r Alk~l;n;ty sources, hydrotropes, enzymes,
enzyme-stabilizing agents, and perfumes.
~ W096l03482 2 1 9 4 0 53
31
Examples
In these examples the following abbreviations have been
used :
Glucose Amide Polyhydroxy fatty acid amide (C16-C18 alkyl
N-methyl glucose amide)
C25E5 : C12-C15 alcohol ethoxylated with an average
of 5 ethoxy groups per molecule
Glyceride : glycerol tristearate
Hyfac : hydrogenated C16-C18 fatty acid
Zeolite : Zeolite A (hydrated)
Examples 1 to 7
1 2 3 4
a) Glucose 8.9 5.1 41.65 8.9
Amide
b) C25E5 20.8 11.9 17.85 20.8
c) Glyceride 1.8 1 3.5 5,3
d) ~yfac 3.5 2 7
e) Zeolite 62 77 27 62
21 94053
096/~3482 P~ 5
32
6 7 8
a) Glucose 9.5 14.9 20_8 8.9
Amide
b) C25E5 22 14.9 8.9 20.8
c) Glyceride 0.1 1.8 1.8 1.8
d) Hyfac 3.4 3.4 3.5 3.5
e) Zeolite 62 62 62 60
In each of examples l to 7 a mixture of polyhydroxy fatty
acid amide and ethoxylated nonionic surfactant was prepared
in the proportions required. Glyceride and hyfac were then
added successively and mixed to form the structured premix
maintained at 75~C.
The structured premix was then pumped into a high shear
batch mixer ~Eirich ~) together with the zeolite in the
proportions required. Granulation occurred within the high
shear mixer.
The granulates were subsequently processed through a low
shear mixer (rotating drum) to which an additional 3 parts
zeolite (by weight of the finished product) was added and
then cooled.
wo s6/034s2 2 1 9 4 ~) 5 3 ~ a
33
Example 8
The composition of example 1 was prepared in a continuous
process. The structured premix (35 parts by weight) was
sprayed into a high shear mixer (Loedige CB ~) at a
temperature of 55~C with 60 parts of zeolite A, and the
product from the exit of the high shear mixer was
subsequently fed into a low shear mixer (Loedige KM ~).
Finally, 5 parts zeolite (by weight of the f;n;~hed
product) was added in the low shear mixer.
Example 3
The continuous process of example 8 was repeated r~placing
60 parts of zeolite A by a mixture comprising 6.5 parts of
sodium carbonate and 53.5 parts of zeolite A. The granular
product formed was again treated by dusting with 5 parts of
zeolite A (by weight of the f;n;shed product).
Examples 10 to 16
Examples 1 to 7 were repeated, in each case on~nt (e),
the zeolite A, was replaced by a mixture of zeolite A and
sodium carbonate in a ratio of 1:2.
