Note: Descriptions are shown in the official language in which they were submitted.
1 31 7~49
IR-304/
925F
SUGAR ESTERS AS DETERGENCY BOOSTERS
BACKGROUND OF THE INVENTION
_ ~ .
(1) Field of the Invention
This invention relates to an improved heavy duty
laundry detergent composition. More partlcularly, the invention
is directed to a heavy daty detergent composition having
incorporated therein a sugar ester which provides detergency
boosting properties to the detergent composition. A preferred
embodiment of the invention is directed to a non-aqueous liquid
heavy duty laundry detergent compositlon having activated
detergency.
(2) Description of the Prior Art
The use of various sugar derivatives in laundry
detergent compositions is known.
It is well known in the art that certain alkyl
glycosides, particularly long chain alkyl glycosides, are surface
active and are useful as nonionic surfactants in detergent
compositions. Lower alkyl glycosides are not as surface active
as their long chain counterparts. Alkyl glycosides exhibiting
the greatest surface activity have relatively long-chain alkyl
groups. These alkyl groups yenerally contain about 8 to 25
carbon atoms and preferably about 10 to 14 carbon atoms.
Long chain alkyl glycosides are commonly prepaeed from
saccharides and long chain alcohols. However, unsubstituted
saccharides such as glucose are insoluble in hi~her alcohols and
thus do not react together easily. Therefore, it i8 common to
first convert the saccharide to an intermediate, lower alkyl
glycoside which is then reacted with the long chain alcohol.
Lower alkyl glycosldes are commercially available and are
1 3 1 7849
62301-1536
commonly prepared by reacting a saccharide with a lower alcohol
in the presence of an acid ca~alyst. Butyl glycoside is often
employed as the intermediary.
The use of long chain alkyl glycosides as a
surfactant in detergent compositions and various methods of
preparing alkyl glycosides is disclosed~ for example, in U.S.
Patents 2,974,134; 3,547,828; 3,59~,86S and 3,721,633. The use
of lower alkyl glycosides as a viscosity reducing agent in
aqueous liquid and powdered deter~ents is dlsclo~ed in U.S.
Patent 4,~8,981.
Acetylated sugar esters, such asl for example,
gluco.~e penta acetate, glucose tetra acetate and sucrose octa
ace~ate, have been known for years as oxygen bleach activators.
The use of acetylated sugar derivatives as bleach activators is
disclosed in U.S. Patents 2,955,905; 3,901,819 and 4,0~6,090.
SUMMARY OF THE INVENTION
In accordance with the present invention, a highly
detersive heavy duty nonionic laundry detergent composition is
prepared by the incorporation of a sugar ester into a nonionic
detergent composition. The sugar esters act as detergency
boosters. The sugar esters may be incorporated into detergent
compositions which may be formulated into liquid or powdered
~orm. Both powdered aqueous and non-agueous liquid
~ormulations may advantageously be produced although far
greater benefits are derived when used in a non-aqueou~
detergent composition.
The inven~ion therefore provides a heavy duty laundry
detergent composition comprising a nonionic sur~actant, a
bleaching agent, a bleach actlvator and, as a detergency
booster, a sugar ester esterifled with at least one fatty acid
chain.
A
1 3 1 7 ~ ~ q 62301-1536
The invention also provides a non-aqueous heavy duty
laundry composition comprisiny a suspension of insoluble
particles of builder salt, a bleaching agent, a bleach
activator and, as a detergency booster, a sugar ester
containlng at leas~ one fatty acid chain, dispersed in liquid
nonionic surfactant.
There ls no disclosure in the prior art of the use of
sugar based surfactants as detergency boosters.
DETAILED DESCRIPTION OF THE INVENTION
Optimum grease/oil removal is achieved where the
nonionic surfactant has an HLB (hydrophilic-lipophlic balance)
2a
1 3 1 7~9
of from about 9 to about 13, particularly from about 10 to about
12, good detergency being related to the existence of rod-like
micelles which exhibit a high oil uptake capacity. Optimal
detergency for a given nonionic surfactant is obtained between
the cloud point temperature, the temperature at which 2. pnase
rich in nonionic surfactant separates in the wash solution, (CPT)
and the phase inversion (coalescence) temperature (PIT). Within
this narrow temperature range or window there exists a water rich
microemulsion domain containing a high oil/surfactant ratio.
This window varies from one nonionic detergent to another. It is
about 30C (37-65C) for a C-13 secondary fatty alcohol
ethoxylated with an average of 7 ethylene oxide chains and is
much smaller, about 10C (33-37C) for an ethoxylated-
propoxylated fatty alcohol. Ideally, ~ince a heavy duty
detergent must perform from low temperatures (30C) to high
temperatures (90C), the CPT should not be above 30 to 40C and
the PIT should not be below 90C.
The existence of both a CPT and a PIT are related to
the unique charac~er of the polyethylene oxide chain. The chain
monomeric element can adopt two configurations, a trans-
configur~tion, and a gauche, cis-type configuration. The
enthalpy difference between both configurations is small, but the
hydration is very different. The trans-configuration is the most
s~able, and is easily hydrated. The gauche configuration is
somewhat higher in eneryy and does not become hydrated to any
significant extent. At low temperature the trans-configuration
is preponderant and the polymeric chain is soluble in water. As
temperature rises kT becomes rapidly greater than the enthalpy
difference between configurations and the proportion of guache
configurated monomeric units increases~ Rapidly, the number of
1 31 7~9
hydration water molecules drops, and the polymer solubility
decreases.
The nonionic surfactant which exhibits a PIT close to
the CPT is accordingly very temperature sensitive. One way to
reduce the temperature sensitivity is to use a nonionic
surfactant with a hydrophilic part different from polyethylene
oxide. However, since commercially available nonionic
surfactants are based on polyethylene oxide, the only cost
effective route is to add a cosurfactant which can co-micellize,
giving less temperature sensitive mixed micelles.
Various types Qf cosurfactant sy~tems are known in the
prior art, some of which include nonionic detergents and tertiary
amide oxides or amphoteric detergents. Amphoterics have been
known for years for their detergency boo~tlng properties. One
lS amphoteric detergent used as a cosurfactant and which has
particularly good detergency boosting activity in combination
with a nonionic detergent are betaine detergents and alkyl
bridged betaine detergents having the general formoli
12 1l
Rl~N+-R4-c-o- and
R3
O 1 2 il
Rl-CH2-C-NH-(CH2)3-N+-R4-C-O-
R3
respectively, wherein
Rl is an alkyl radical containing from about l0 to abo~t 14
carbon atoms R2 and R3 are each selected from the group
cons tlng of methyl and ethyl rad1cals~ and R4 is selected frcm ¦
13178119
the group consisting of methylene, ethylene and propylene
radicals.
A suitable betaine surfactant ls
+
5Cl~-H2~-N -CH2-C-O~
whereas a suitable alkylamidobetaine i9
e IH3 8
C12-H25-C-NH(CH2)3-N+-CH2-C-o-
CH3
Sulfobetaines, such as
o CH3 OH
12-H25-C-NH-(CH2)3-N+-CH2-CH-CH2-S
CH3
: ~: : :
have also ~een found to exhibit good detergency boosting
properties when used in combination wlth nonionic detergents.
A betaine exhibits both a positive charge and a
negative charge. It is electrically neutral as are nonionic
surfactants. The quaternary ammonium is essential to maintain
the positive charge even in alkaline ~olution. It is well known
that ions are easily hydrated and that the hydration does not
vary much with temperature. ~etaine surfactants can accordingly
be used as a cosurfactant. In addition, although free amines
react rapidly with peracids to give amlne oxides which consume
1317~49
bleach moieties and surfactant molecules, a betaine is the only
nitrogen containing structure which is stable in the presence of
an organic peracid Ipresent as is or generated by reaction
between perborate and a bleach activator such as TAED).
The addition of betaine to a nonionic detergent
significantly improves oily soil removaL. Although the most
significant improvement is achieved at '30C, important benefits
are obtained at 60C and especially at 40C. However, on an
industrial scale, betaines are only available in aqueous solution
and hence cannot be used as an additive in non-aqueous liquid
detergent compositions.
Detergency boosting properties have not previously been
disclosed for sugar esters. Potentiating or synergestic effects
between sugar esters and nonionlc surfactants have now been
discovered and are herein claimed. Sugar esters have been found
to be effective detergency boosters and can efficiently replace
betaines, as a cosurfactant, in nonionic detergents. Sugar
esters have been found to perform ~imilar to betaines in both
powdered and aqueous liquid heavy duty laundry detergents.
However, unlike betaine detergents, sugar esters may be
advantageously employed in non-aqueous liquid detergent
compositions and have been found to have significant detergency
boosting efficiency in non-aqueous liquid laundry detergents.
Non~aqueous liquid detergents are known as having poor detergency
at high temperatures due to the presence of low phase inversion
temperature nonionic. Sugar esters have been found to increase
the detergency of non-aqueous liquid detergents, especially at
temperatures of 60C and above, a temperature range where non-
aqueous detergent products are known to be less efficient.
Such effect~ are due to the Eact that the hydrophilic
13178~')
part of the surfactant ~sugar) is not significantly temperature
sensitive and remains water soluble at higher temperatures.
Although the solubility in water of the ethylene ox~Lde chain
diminishes a9 temperature rises, the presence of the -OH group in
the sugar moiety significantly decreases the whole surfac~ant
temperature sensitivity so the mixed micelle (nonionic and sugar
ester) remains stable in a wider temperature range than the
micelle of the nonionic detergent alone.
Food grade 100~ active sugar esters were tested for
their detergency boosting properties. Glucose ester S 1670, a
stearic acid derivative having an HLB of 16 and glucose ester L
1570, a lauric acid derivative having an HL8 of 15 were each
tested using EMPA and ~REFELD as soils at isothermal wash
temperatures o 40C, 60, and 90C. In the following test,
soiled cotton fabric swatches were washed for a period of 30
minutes in a wash solution containing 1.59 TPP (sodium
tripolyphosphate) and 2g of surfactant mixture in 600 ml of tap
water. The following surfactant mixtures A, B, and C were
tested.
Surfactant A = nonionic surfactant (ethoxylated-
; propoxylated C13-C15 fatty alcohal)
Surfactant B = Surfactant A ~ L 1S70
Surfactant C = Surfactant A ~ S 1670
- 13178'~q
Table 1 shows the detergency results of various
nonionic surfactant:sugar ester ratios .
TABL~ 1
SUGAR ESTER DETERGENCY
_ . . . .
Surfactant Ratio of nonionic Isothermic wash temperature
Mixture to sugar ester 40C 60C 90C
Soil - EMPA on cotton
: 10 Delta Rd Value
A 18.2 17.7 6.4
B 9:1 18.8 17.1 10.2
8:2 19.~ 16.6 16.7
7:3 20.1 20.5 16.9
C ~:1 19.2 20.1 16.2
. 8:2 7.3 13~4 14.2
: Soil - ~R~FELD on cotton
Delta Rd Value
A 4.6 11.4 11.4
B 9:1 4.5 11.9 12.0
8:2 4.9 13.2 13.6
7:3 5.9 13.3 14.3
: C 9:1 5.5 11.5 13.2
B:2 7.3 13.4 14.2
i From the above table, the excellent performance of
sugar esters as a cosurfactant with a nonionic surfactant is
cleaely evidenced. Although dellvering a benefit at 40C,
detergency is greatly increased at 90C. Since the detergency of
non-aqueous lilluld detergents ba ed on ethoxy1ated-pcopoxylated
1 31 ~49
fatty alcohol nonionic surfactants drop at high temperatures due
to the reduced solubility of the surfactant as temperature rlses
the addition of a sugar fatty ester as a cosurf2ctant greatly
increases detergency.
Any sugar, esterified with at least one long ch~in
fatty acid, may be used as a potential detergency booster.
Fatty acids having at least 10 carbon atoms or more being
preferred. More preferable are fatty acids having 12 to 22 carbon
atoms. Stearic acid (C18) is especially preferr~d. It is to be
understood that the nature of the hydrophilic head group can ~e
extended to any sugar derivative such as, for example, glucose or
sucrose and variations and op~imizations will be apparent to
those skilled in the art. Unlike polyethyleneoxLde based
nonionic surfactants, the HLB of sugar derivatives is adjusted by
; 15 the number of hydrocarbon chains per sugar unit rather than by
the hydrophilic chain length. Sugar esters may be incorporated
into any detergent composition, liquid or powdered, containin~ a
high level of nonionic surfactant.
Although the sugar esters of this invention can
advantageously be employed in both powdered and aqueous liquid
detergent compositions, other objects of the invention will
become more apparent from the following detailed description of a
preferred embodiment wherein a detergent composition is provided
by adding to a non-aqueous liquid suspension an amount of sugar
ester effective to provide the needed detergency boosting
properties.
The nonionic synthetic organic detergents employed in
the practice of the invention may be any of a wide variety of
such compounds, which are well known and, for example, are
described at length in the tex~ Surface Active A~ents, Vol. II,
1 3 1 7 8 4 9 62301-1536
by Schwartz, Perry and ~erch, published ln 1958 by Interscience
Publlshers, and in McCutcheon's Deterqents and_Emulsifiers,
1969 Annual. Usually, the nonionic detergents are poly-lower
alkoxylated lipophiles wherein the deslred hydrophile~lipophile
balance is obtained from addition of a hydrophilic poly-lower
alkoxy group to a lipophilic moiety. A preferred class of the
nonionic detergent employed is the poly-lower alkoxylated
hi0her alkanol wherein the alkanol is of 10 to 18 carbon atoms
and wherein the number of moles of lower alkylene oxide (of 2
or 3 carbon atoms) is from 3 to 12. Of such material~ it is
preferred to employ those whereln the higher alkanol is a
hiqher fatty alcohol of 10 to 11 or 12 to 15 carbon atoms and
which contain from 5 to 8 or 5 to 9 lower alkoxy groups per
mole. Preferably, the lower alkoxy is ethoxy but in some
instances, it may be desirably mixed with propoxy, the latter,
if present, often being a minor (less than 50%) proportion.
~xemplary o~ such compounds are those wherein the alkanol is of
12 to 15 carbon atoms and which contain about 7 ethylene oxide
groups per mole e.g. Neodol 25-7 and Meodol* 23-6.5, whlch
products are made by Shell Chemical Company, Inc. The former
i9 a condensation product of a mixture of hlgher fatty alcohols
averaging about 12 to 15 carbon atoms, with about 7 moles of
ethylene oxide and the latter is a corresponding mixture
wherein the carbon atom content of the higher fatty al~ohol is
12 to 13 and the number of ethylene oxide groups present
averages about 6.5. The higher alcohols are primary alkanols.
Other examples of such detergents include Tergitol* 15-S-7 and
Tergitol 15-S-9, both of which are linear secondary alcohol
ethoxylate~ made by Union Carbide ~orporatlon. The former is a
mixed ethoxylation product o~ an 11 to 15 carbon
A *Trade-mark 10
1 31 7~9
atom linear secondary alkanol with ~even moles of ethylene oxide
and the latter is a similar product but with nine moles of
ethylene o~ide being reacted.
Also useful in the present composition as a component
of the nonionic detergent are higher molecular weight no~ionics,
such as Neodol 45-11, which are ~imilar ethylene oxide
condensation products of higher fatty alcohols with the higher
fatty alcohol being of 14 to 15 carbon atoms and the number of
ethylene oxide groups per mole being about 11. Such products are
also made by Shell Chemical Company.
An e~pecially useful clas of nonionics are represented
by the commercially well known class of nonionics sold under the
trademark Plurafac. The Plurafacs are the reaction product of a
higher linear alcohol and a mixture of ethylene and propylene
oxides, containing a mixed chain of ethylene oxide and propylene
oxide, terminated by a hydroxyl group. Examples~include Plurafac /
RA30, Plurafac RA40 (a C13~C15 fatty alcohol ~ondensed with 7
moles propylene oxide and 4 moles ethylene oxide), Plurafac D25
(a C13-C15 atty alcohol condensed with 5 moles propylene oxide
and lO moles ethylene oxide)j Plurafac B26, and Plurafac RA50 (a
mixture of equal parts Plurafac D25 and Plurafac RA40).
Generally, the mixed ethylene oxide-propylene oxide
fatty alcohol condensation products can be represented by the
general ormula
:
~ 25 Ro(c2H4o)p~c3H6o)9H
: .
wherein R i5 a straight or branched, primary or secondary
aliphatic hydrocarbon, preferably alkyl or alkenyl, especially
preferably alkyl, of from 6 to 20, preferably 10 to 18,
1 31 7~
especially preferably 14 to 18 carbon atoms, p is a number o~
from 2 to 12, preferably 4 to 10, and q is a number of from 2 to
7, preferably 3 to 6. The~e surfactants are advantageously used
where low foaming characteristics are desired. In addition they
have the advantage of low gelling temperature.
Another group of liquid nonionics are available from
Shell Chemical Company, Inc. under the Dobanol trademark:
Dobanol 91-S is an ethoxylated Cg-Cll fatty alcohol with an
average of 5 moles ethylene oxide; Dobanol 25-7 is an ethoxylated
C12 Cls fatty alcohol with an average of 7 moles ethylene oxide.
In the preferred poly-lower alkoxylated higher
alkanols, to obtain the best balance of hydrophilic and
lipophilic moieties, the number of lower alkoxies wi:ll ususally
be from 40~ to 100% of the number of carbon atoms in the higher
alcohol, preferably 40% to 60~ thereof and the nonionic detergent
will preferably contain at least 50% of such poly-lower alkoxy
higher alkanols. The alkyl groups are generally linear although
branching may be tolerated, such as at a carbon next to or two
carbons removed from the terminal carbon of the straight chain
and away from the ethoxy chaln, if such branched alkyl is not
more than three carbons in length. Normally, the proportion of
carbon atoms in such a branched configuration will be minor
rarely exceeding 20% of the total carbon atom content of the
alkyl. Similarly, although linear alkyls which are terminally
joined to the ethylene oxide chains are highly preferred and are
considered to result in the best combination of detergency and
blodegradibility medial or secondary joinder to the ethylene
oxide in the chain may occur. It is usually in only a minor
proportion of such alkyls, generally less than 20~ but, as is in
the cases of the mentioned Tergitols, may be greater. Alsol
~31784~
when propylene oxide is present in the lower alkylene oxide
chain, it will usually be less than 20% thereof and preferably
less than 10% thereof.
~hen greater proportlons of non-terminally alkoxylated
alkanols, propylene oxide-containing poly-lower alkoxylated
alkanols and less hydrophile-lipophile balanced nonionic
detergent than mentioned above are employed and when other
nonionic detergents are used instead of the preferred nonionics
recited herein, the product resulting may not have as good
detergency, stability, and viscosity properties as the preferred
compositions. In some cases, as when a higher ~olecular weight
poly-lower alkoxylated higher alkanol is employed, often for its
detergency, the proportion thereof wlll be regulated or limited
in accordance with the results of routine experiments, to obtain
the desired detergency. Also, it has been found that it is only
rarely necessary to utilize the higher molecular weight nonionics
for their detergent properties since the preferred nonionics
described herein are excellent detergents and additionalIy,
permit the attainment of the desired viscos}ty in the liquid
detergent. Mixtures of two or more of these liquid nonionics can
also be used.
Furthermore, in the compositions of this invention, it
may often be advantageous to include compounds which function as
viscosity control and gel-inhibiting agents for the liquid
nonionic surface active agents such as low molecular weight ether
compounds which can be considered to be analogous in chemical
structure to the ethoxylated an/or propoxylated fatty alcohol
nonionic surfactants but which have relatively short hydrocarbon
chain lengths (C2-C~) and a low content of ethylene oxide (about
2 to 6 ethylene oxide units per molecule).
131784q
62301-1536
Suitable ether compounds can be repre~ented by the
followiny general formula
RO(CH2CH20~nH
wherein R is a C'2-C~ alkyl group, and n i5 a number of ~rom
about 1 to 6, on average.
Specific examples of suitable ether compounds include
ethylene glycol monoethyl ether ~C2H5-0-CH2CH20H~, diethylene
glycol monobutYl ether (C4Hg-0-(CH2CH20)2H)~ tetraethylene
glycol monobutyl ether (C8H17-0-(CH2CH20)4H), etc. Diethylene
glycol monobutyl ether is especially preferred.
Further improvements in the rheological properties of
the liquid detergent composition6 can be obtained by inc]uding
in the composition a small amount of a nonionic surfactant
whlch has been modified to covert a free hydroxyl group thereof
to a moiety having a free carboxyl group. As disclosed in
Canadian patent application Serial No. 478,379, the free
carboxyl group modified nonionic surfactants, which may be
broadly characterized as polyether carboxylic acids, function
to lower the temperature at which the liquid nonionic forms a
gel with water. The acidic polyether compound can also
decrease the yield stress of such dispersions, aiding in their
dispensibility without a corresponding decrease in their
stability against settling.
The invention detergent compositions also include
water soluble and/or water insoluble detergent builder salts.
Typical suitable builders include, for example, those disclosed
in U.S. Patents 4,316,812; 4,264,466 and 3,630,929. Water
soluble inorganic alkaline builder salts which can be usad
along
`! ~
1317~
with the detergent compound or in admixture with other builders
are alkali ~etal carbonates, borates, phosphates, polyphosphates,
bicaebonates, and silicates. Ammonium or substituted ammonium
salts can also be used. Speclfic examples of such salts are
sodium tripolyphosphate, sodium carbonate, ~odium tetrabofate,
sodium pyrophosphate, potassium pyrophosphate, sodium
hexametaphosphate, and potassium bicarbonate. Sodium
tripolyphosphate ~TPP) is especially p~eferred. The alkali metal
silicates are useful builder salts which al50 function to make
the composition anticorrosive to washing machine parts. Sodium
silicates o Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, especially
about 1/2 to 1/2.8 are preferred. Potassium silicates of the
same can also be used.
Another class of builders highly useful herein are the
water insolub:Le aluminosilicates, both of the crystalline and
amorphous type. Various crystalline zeolites (i.e.
aluminosilicates) are described in British Patent 1,504,168, U.S.
Patent 4,409,136 and Canadian Patents 1,Ot2,835 and 1,087,477.
An example of amorphous zeolites useful herein can be found in
Belgium Patent 835,351. The zeolites generally have the formula
( M 2~ ) x ( A1 23 ) y - ( 5 i2 ) z - WH 2
:
where x is 1, y is from 0.8 to 1.2 and preferably 1, z is fcom
1.5 to 3.5 or higher and preferably 2 to 3 and W is from o to 9,
preferably 2.5 to 6 and M i~ pre~erably sodium. A typical
zeolite is type A or similar structure, with type 4A
particularly preferred. The pre~erred aluminosilicates have
calcium ion exchange capacities of about 200 milliequivalents per
gram or greater, e.g. 400 meq/g~
1 31 7~9
¦ Other materials such as clays, particularly of the
¦water insoluble types, may be useful adjuncts in compositions of
¦this invention. Particularly useful is bentonite. This material
¦is primarily montmorillonite which is a hydrated aluminum
¦silicate in which about 1/6th of the aluminum atoms may be
¦replaced by magnesium atoms and with which varying amounts of
¦hydrogen, sodium, potassium, calcium, etc., may be loosely
¦combined. The bentonite in its more purlfied form (i.e. free
¦from grit, sand, etc.) suitable for detergents invariably
¦ contains at least 50~ montmorillonite and thus its cation
¦ exchange capacity is at least about 50 to 75 meq per 100 g of
bentonite. Particularly preferred bentonites are the Wyoming or
Western U.S. bentonites which have been sold as Thixo-jels 1, 2,
l 3 and 4 by Georgia Kaolin Co~ These bentonites are kno~n to
¦ soften textiles as described in ~ritish Patents 401,413 and
461,221.
I Examples of organic alkaline sequestrant builder salts
¦ which can be used along with the detergent or in admixture with
other organic and inorganic builders are alkali metal, ammonium
¦ or sustituted ammonium, aminopolycarboxylates, e.g. sodium and
¦ potassium nitrilotriacetates (NTA) and triethanolammonium N-(2-
¦ hydroxyethyl)nitrileodiace~ates. Mixed salts of these
polycarboxylates are also suitable.
l Other su;table builders of the organic type include
2S ¦ carboxymethylsuccinates, tartronates and glycollates~ Of
¦ special value ar~ the polyacetal carboxylates. The polyacetal
¦ carboxylates and their use in detergent compositions are
¦ described in 4,144,226; 4,315,092 and 4,146,495. Other U.S.
Patents on similar builders include 4,141,676; 4,169,934;
4,201,858; 4,204,852 4,224,420î 4,225,6B5; 4,226,960; 4,233t422
1 3 ~ 7849
62301-1536
4,233,423; 4,302,564 and 4,303,777. Also relevant are Canadian
Patent Nos. 1,148,831; 1,131,092 and 1,174,934.
Since the compositions of this invention are
generally hlghly concen~rated, and, therefore, may be used at
relatively low dosages, it is desirable to supplement any
phosphate builder (such as sodium tripolyphosphate~ with an
auxiliary builder such as a polymeric carboxylic acid having
high calcium binding capacity to inhibit incrustation which
could otherwise be caused by formation of an insoluble calcium
phosphate. Such auxiliary builders are also well known in the
art. For example, mention can be made of Solcolan* CP5 which is
a copolymer o~ about equal moles of methacrylic acid and maleic
anhydride, completely neutralized to form the sodium salt
thereof.
In addition to detergent builders, various other
detergent additives or adjuvants may be present in the
detergent product to give i~ additional desired properties,
either of functional or aesthetic nature. Thus, there may be
included in the formulation, mlnor amounts of soil suspending
or antiredeposition agents, e.g. polyvinyl alcohol, fatty
amides, sodium carboxymethyl cellulose, hydroxy-propyl alcohol
methyl cellulose; optical brighteners, e.g. cotton, polyamide
and polyester brighteners, ~or example, stilbene, triazole and
benzidine sulfone composition , especially sulfonated
substituted triazinyl stilbene, sulfonated naphthotriazole
stilbene, benzidene sulfone, etc., most preferred are stilbene
and triazole combinations.
Bluing agents such as ultramarine blue; enzymes,
preferably proteolytic enzymes, such as subtilisln, bromelin,
papain, trypsin and pepsin, as well as amylase type enzymes,
lipase type enzymes, and mixtures thereo~t bacterlcides, e.g.
~Trade-mark 17
A'l`
1 31 78~q
tetrachlorosalicylanilide, hexachlorophene fungicidess dyes
pigments (water dispersible); preservativesS ultraviolet
absorbers anti-yellowing agents~ such as sodium carboxymethyl
cellulose (CMC), complex of C12 to C22 alkyl alcohol with C12 to
Clg alkylsulfate; pH modifiers and pH buffers; perfume; a~d anti-
foam agents or suds-suppressors, e.g. silicon compounds can also
be used.
sleaching agents are classified broadly for convenience
as chlorine bleaches and oxygen bleaches. The use of bleaching
agents as aids in laundering is well known. Of the many
bleaching agents used for household applications, the chlorine-
containing bleaches are most widely used at the present time.
However, chlorine bleach has the serious disadvantage of being
such a powerful bleaching agent that it causes measurable
degradation of the fabric and can cause localized over-bleaching
when used to spot-treat a fabric undesirably stained in some
manner. Other active chlo~ine bleaches, such as chlorinated
cyanuric acid, although somewhat safer than sodium hypochlorite,
also suffer from a tendency to damage fabric and cause localized
over-bleaching. For these reasons, chlorine bleaches can seldom
be used on amide-containing fibers ~uch as nylon, silk, wool and
mohair. Furthermore, chlorine bleaches are par~icularly damaging
to many flame retardant agents which they render ineffective
after as little as five launderings.
Of the two major ~ypes of bleaches, oxygen-releasing
and chlorine-relea~ing, the oxygen bleaches, sometimes re~erred
to as non-chlorine bleaches or "all-fabric" bleaches, are more
advantageous to use in that oxygen bleaching agents are no~ only
highly effective in whitening fabrics and removing stains, but
they are also safer to use on colors. They do not attack
1317~49
fluorescent dyes commonly used as fabric brighteners or the
fabrics to any serious degree and they do not, to any
appreciable extent, cause yellowing of resin fabric finishes as
chlorine bleache~ are apt to doO Both chlorine and non-chlorine
bleaches use an oxidizing agent, such as sodium hypochlorite in
the case of chlorine bleaches and sodium perborate in the case of
non-chlorine bleaches, that reacts with and, with the help of a
detergent, lifts out a stain.
A~ong the various substances which may be used as
oxygen bleaches, there may be mentioned hydrogen peroxide and
other per compounds which give rise to hydrogen peroxide in
aqueous solution, such as alkali metal persulfates, perborates,
percarbonates, perphosphates, persilicates, perpyrophophates,
peroxides and mixtures thereof.
Although oxygen bleaches are not, as deleterious to
fabrics, one major drawback to the use of an oxygen bleach is he
high temperature and high alkality necessary to efficiently
activate the bleach~ Because many home laundering facilities,
particularly in the United States, employ quite moderate washing
¦ temperatures (20C, to 60C), low alkalinity and short soaking
¦ times, oxygen bleaches when used in such systems are capable of
only mild bleaching action. There is thus a great need for
substances which may be used to activate oxygen bleach at lower
temperatures.
Various activating agents for improving bleaching at
lswer temperatures are known. These activating aqents are
roughly divided into three groups, namely ~l) N-acyl compounds
such as tetracetylethylene diamine (TAED), tetraacetylglycoluril
and the like; (2) acetic acid esters of polyhydric alcohols such
as glucose penta acetate, sorbitol hexacetate, sucrose octa
i 31 7849
¦acetate and the like; and (3) organic acid anhydrides, such as
¦phthalic anhydride and succinic anhydride. The preferred bleach
activator being TAED. Oxygen bleach activators, such as TAED
function non-catalytically by co-reaction with the per compound
to form peracids, such as peracetic acid from TAED, or sa~ts
thereof which react more rapidly with oxidizable compounds than
the per co~pound itself. In accordance with this invention, the
peroxygen compound is used in admix~ure with an activator
therefor.
In a preferred form of the invention~ the mixture of
liquid nonionic surfactant and solid ingredients is subjected to
an attrition type of mill in which the particle sizes of the
l solid ingredients are reduced to less than about 10 microns, e.g.
¦ to an average particle size of 2 to 10 microns or even lower
lS ¦ (e.g. 1 micron). Preferably less than about 10%, especially less
l than about 5% of all the suspended particles have particle sizes
¦ greater than 10 ~icrons, compositions whose dispersed particles
are of such small size have improved stability against separation
I or settling on storage.
¦ In the grinding operation, it is preferred that the
¦ proportion of solid ingredients be high enough ~e.g. at least
about 40% such as about 50~) that the solid particles are in
contact with ea~h other and are not substantially shielded from
one another by the nonionic surfactant liquid. Mills which
employ grinding balls (ball mills~ or similar mill grinding
elements have given very good results. Thus, one may use a
laboratory batch attritor having 8 mm diameter steatite grinding
: balls. For larger scale work a continuously operating mill in
which there are 1 mm or 1.5 mm diameter grinding balls wockinq in
30 a very small gap between a stator and a rotor operating at a
13178-~9
relatively high speed ~e.g. CoBall mill) may be employed. When
using such a mill ! it is desirable to pass the blend of nonionic
suefactant and solids first through a mill which does not effect
such fine grinding (e.g. a colloid mill) to reduce the particle
size to less than 100 microns ~e.g. to about 40 micron ) prior to
the step of grinding to an average part~cle diameter below about
10 microns in the continuous ball mill.
In the preferred heavy duty liquid detergent
compositions of the invention, typical proportions (based on the
total composition, unless otherwise specified) of the ingredients
are as follows:
Suspended detergent builder, within the range of about
10 to 60~ such as about 20 to 50%, e.g. about 25 to 40~
Liquid phase comprising nonionic surfactant and
optionally dissolved gel-inhibiting ether compound, within the
range of about 30 to 70~, such as about 40 to 60~ this phase may
also include minor amounts of a diluent such as a glycol, e.g.
polyethylene glycol (e.g. "PEG 400"), hexylene glycol, etc. such
~; as up to 10%, preferably up to 5%, for example, 0.5~ to 2~. The
weight ratio of nonionic surfactant to ether compound when the
latter is present is in` the range o from about 100:1 to l:lr
preferably from about 50:1 to about 2:1.
Sugar ester of this invention, ~eom about 4~ to about
15~, preferably about 6 to about 8~.
Polyether carboxylic acid gel-inhlbiting compound, up
to an amount to supply in the range of about 0.5 to 10 parts
(e.g. about 1 to 6 parts, such as about 2 to 5 parts) of -COOH
(M.W. 45) per l00 parts of blend of such acid compound and
nonionic surfactant. Typically, the amount of the polyether
carboxylic acid compound is in the range of about 0.05 to 0.6
13178~
part, e.g. about 0.2 to 0.5 part, per part of the nonionic
surfactant.
Acidic organic phosphoric acid compound, as anti-
settling agent; up to 5%, for example, in the range of 0.01 to
5~, such as about 0.05 to 2~, e.g. about 0.1 to 1%.
Suitable ranges of the optional detergent additives
are: enzy~es - O to 2~, especially 0.7 to 1.3%; corrosion
inhibitors - about O to 40~, and preferable 5 to 30~; anti-foam
agents and suds-suppressors - O to 15~, preferably O to 5%, for
example 0.1 to 3~; thickening agent and dispersants - O to 15~,
for example 0.1 to 15%, for example 0.1 to 10%, preferably 1 to
5%; soil suspending or anti-redeposit~on agents and anti-
yellowing agents O to 10~, preferably 0.5 to 5%; colorants,
¦ perfumes, brighteners and bluing agents total weight 0~ to about
1 2~ and preferably 0~ to about 2~ and preferably 0% to about 1
pH modifiers and pH buffers - O to 5% preferably O to 2%:
bleaching agent - 0% to about 40~ and preferable 0% to about
25%, for example 2 to 20%. In the selections of the adjuvants,
they will be chosen to be compatible with the main constituents
o~ the detergent composition.
In this application, all proportions and peecentages
are by weight unless otherwi~e indicated. In the examples,
atmospheric pressure is used unless otherwise indicated.
Example
2S A concentrated non-aqueous built liquid detergent
cOmposition is formulated from the followlng ingredients in the
amounts specified. The composition is prepared by mixing and
finely grinding the following ingredient~ to produce a liquid
suspension. In preparing the mixture for grinding the solid
ingredient~ are added to the nonionic surfactant, with TPP being
1317~9
added last.
Wei~ht
Nonionic surfactant (etho~ylated-propoxylated 21
C13-C15 fatty alcc,hol)
Dowanol DB - nonionic surfactant 21 / ,
Glucose ester S 1670 (stearic acid deri.vative)
: Sodium tripolyphosphate (TPP) - builder salt 31.3
Sokalan CP5 - anti-encrustation agent 2
Dequest 2066 - sequestering agent 1
Sodium perborate monohydr~te - bleaching agent 9
Tetraacetylethylenediamine (TAED) - bleach acti~ator 4.5
Urea - stabilizer
Sodium carboxymethylcellulose (CMC) - anti-yellowing agent 1
Esperase enzym~ 0.8
Termamyl~ enzyme 0.2
: : Tinopal ~TS-X - optical brightener 0~4
: ~ Tio2 - whitening agent Q.2
: Perfume 0.6
: : : ` :
The above composition is stable in storage, dispenses
readily in cold wash water and imparts excellent detersive
: effects to:the wash load~
It i~ to be understood that the foregoing detailed
description is given merely by way of illustration and that
: 25 variations may be made therein without departing from the spirit
and scope of the invention.
23
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