Note: Descriptions are shown in the official language in which they were submitted.
WO 92/17523 ~ 2 ~ PCr~]S9Z/U2256
NONIONIC SOIL REL~ASE AGENTS
TECHN I CAL F I ELD
ThjS ;nVent;On relates to nonionic oligomers which function
as improved soil release agents (sra's), and which are useful in
laundry compositions, especially fabric softener compositions, and
the like.
~ACKGROUND OF~ y~NTION
A "sDil release" e ffect is produced when fabrics, especially
fabrics having a synthetic f;ber COmPOnent, are immersed in an
aqueous laundry or rinsR bath ;n a domestic or institutional
setting wherein the aqueous bath comprises various PO1Ymer;C On
oligomeric ester soil release agents (sra's), typically at low
lev2ls such as five to a few tens of parts per million. The
polymers or oligomers depos~t onto the fabric surface to provide a
soil-release finish thereto. Soil release is distinct from the
usual clean~ng effect of laundry detergent surfactants and
builders, in that a mul~-wash effect ~s secured, e.g., fabrics
repetltively laundered tend to be cleaned progressively more
easily over two, thr~e or four wash-wear cycles, and some soil
antiredeposition benefit is also often secured. SQj1 release is
especially pronounced on polyester fabrics, but good results are
also secured on polyester/cotton blends. Soil release benefits
are also seen on nylons and acrylics.
Soil release in an aqueous laundry context is rather differ-
ent from industrial finishing of yarns and fibers, warp-sizing and
the like, in terms of the general kinds of sra compositions which
work best. This may be a consequence of some substantial differ-
ences in processing conditions. In any event, laundry sra's of
the type herein are typically applled to fabrics in washing
machines, either in the presence of noninterfering detersive
surfactants, or, more preferably9 in the presence of cationic
fabric softening agents. The sra typically dep3sits to only a
limited extent on the fabrics. In contrast, industrial finishing
is commonly done in highly controllable process equipment, such as
padders.
Typically the textile is clean, and the concentr~tion of
cleaning agents or softening agents (if any) tends to be low, at
W o 92/17523 ~ 3 ~ PCT/VS92/02256
2 -
least at the stage at which it is desired to exhaust a soil
release treatment onto the textile substrate.
Just as there are technical differences between launbering
and industrial finishing, so too are there considerable differ-
ences between laundry composition types, such as laundry deter-
gents, laundry softeners, laundry bleaches, and the like. Such
laundry compositions are also prepared in various forms, such as
granular, liquid, gl, paste-form, and dryer-added products.
Formulators in the laundry arts are acutely aware that various
forms of laundry compositions have inherent formulation con-
straints. For example, solid-formulated compositions need ingred-
ients generally capable of dispersing or dissolving in aqueous
laundry baths, while liquid formulae commonly need ingredients
which are freely mixable without excessive chemical or physical
interaction such as phase changes or precipitation.
In particular, modern iaundry compositions are now becoming
available in popular "concentrate" form. For example, liquid
fabric softeners have now been commercial ked which contain
cationic softener ingredtents at concentrations on the order of
3-fold higher than fabric softeners available heretofore. It w~ll
be appreciated that the formulation of such compositions in
shelf-stable form and at reasonable viscosity ranges can be
difficult. Formulation and performance difficulties are~ of
course, accentuated when attempts are made to incorporate addi-
tional functional ingredients, such as sra's, into such
compositions.
Accordingly, there is a continuing search for effective,
compatible, easy-to-formulate sra's for use ~n laundry
compositions.
The present invention provides effective nonionic sra's which
are suitable for use in laundry compositions. The ~nvention also
provides nonionic sra's which are particularly use~ul in combina-
tion with cationic fabric softeners. Moreover, many of the sra's
herein do not excessively increase the viscosity of liquid fabric
softener compositions, even when formulated as softener
nconcentrates".
WO 92/17523 ~ 'd'' PC~/US92/0~256
U.S. Patent 4,711,730 to Gosselink and D~ehl, December 8,
1987, relates to capped 1,2-propylene terephthalate - polyoxy-
ethylene terephthalate polyesters useful 21S soil release agents in
laundry detergents and fabric softener compositions, including
concentrates.
Additional references in the field~ als cited in Gosselink and
Diehl, include the following.
A. ~ ~.bLb~]35~ ~911_ ~ 1-55-
Polve~ters used in laundrY dete75}~ L~55L555
U.S. Patent 4,116~885 to Derstadt et al, issued September 26,
1978, discloses laundry detergent compositions containing 0.15% to
25% (most preferably 0~5YD to 10/~) of an ethylene terephthalate/PEG
terephthalate soil release polyester, such as MILEASE T, having an
1~ average molecular weight of 5,000 to 200,000 (prefPrably 10,000 to
50,000). These detergent compositions further contain 5% to 95%
(most preferably 10X to 2S%) of certain compatible alcohol sulfate
and alkylethyoxy sulfate detergent surfactants and no more than
10% of other incompatible anionic surfactants such as the linear
alkyl benzene sulfonates~
U.S. Patent 4,132,680 to Nicol, issued January 2, 1979, also
discloses laundry detergent compositions having soil release
properties which contain 2% to 95% (preferably 10X to 60%) of a
detergent surfactant and 0.15% to 25X (most preferably 1% to 10%~
of an ethylene terephthalate/PEG terephthalate (mole ratio of
65:35 to 80:20) soil release polyester having a molecular weight
of 10,000 to 50,000, e.g., MILEASE T. These compositions further
comprise 0.05X to 15% (most preferably 0.1% to 5%) of a component
which disassociates in aqueous solution to y~eld quaternary
ammonium cations having one to three CO-C2~ alkyl groups. These
cations are taught by N~col to improve the deposition.of the soil
release polyester on the laundered ~abric. See column 11, lines
14-21.
B. Use of Dolvesters in rinse-added products to impart soil
release pro~erties
Canadian Patent 1,100,262 to Becker et al, issued May 55,
1981, discloses fabric softener compositions containing 1X to 80%
(preferably 5X to 50%) of a fabric-softening agent such as
ditallow dimethyl ammonium chloride in combination with 0.5% to
WO 92/17~23 . PCI/VS92/02~56
- 4 -
25% (preferably 1% to l~/o) of certa;n choline fatty acid esters.
These softening compositions preferably include 0.5% to 10%
(preferab1y 1% to 5%) of an ethylene terephthalate/PEG
terephthalate soil release polyester such as PERMALOSE or ZELCON.
U.S. Patent 3,893,929 to Basadur, issued July 8, 1975,
discloses rinse-added acidic solutions containing a soil release
agent ~ade from a dibasic carboxylic acid (preferably terephthalic
acid), a polyalkylene glycol (preferably a PEG having a molecular
weight of 1,300 to 1,800) and an alkylene glycol ~ethylene,
propylene or butylene glycol). Preferred soil release agents have
a molecular weight of from 3,000 to 5,000. Cationic fabric
softeners SUch ~s ditallow dimethyl ammonium chloride can be
included in these compositions, but are said to be not preferred
"since they tend to retard the deposition of the soil release
agent on the polyester fibers at acidic pH." See column 7, lines
54-~9.
U.S. Patent 3,712,873 to Zenk, issued January 23, 1973,
d~scloses text~le treating compositions applied by spraying or
padding which comprise lX to 5~ of a soil release polyester of the
type disclosed in the Basadur patent. These compos~tions can
additisnally contain up to 4% of a quaternary ammonium compound
having one Cl~-C22 alkyl group. The combination of this
quaternary a~monium compGund with the polyester ls described as
improving the soil-release tharacteristic of the treated fabric.
~enk also states that other quaternary ammonium compounds, such as
ditallow dimethyl ammonium chloride, did not give the same
superior performance. See column 3, lines 57-61.
C. Use of ~olvesters in drYer-added produc_s to im
r~leasç roQerti~s
U.S. Patent 4,238,~31 to Rudy et al, issued December 9, 1980,
discloses dryer-added products which contain a "distribut~ng
agent" such as polyethylene glycol and an adjuvant applied to the
fabric which c~n be a soil release agent. Soil release agents
disclosed include polyacrylic resins, polyvinyl alcohol and
3~ PERMALOSE TG polyesters ~see Example 8).
D. Use. of DolYesters in fabric or texti~ trea~
solutions wh~ch are heat cured to imDart _soil release
~nd~o~ antlstatic ProDerties
WO 92/1 7523 2 ~ PCr/VS92~02256
U.S. Patent 3,S12,920 to Dunlap, issued May 9, 1970,
discloses low molecular weight alkylene glycol/polyalkylene glycol
terephthalic acid polyesters which are used in resin treating
baths containing starch or cellulose derivatives to impart soil
release properties to cotton/polyester ~abrics after heat curing.
The alkylene glycols which can be used to make these polyesters
include ethylene ylycol, 1,2-propylene glycol, 1,3-propylene
glycol, butylene glycol and mixtures thereoF. The polyalkylene
glycols which can be used include PEG, polybutylene glycol and
mixtures thereof which have an average molecular weight of 200 to
20,000 (preferably 1,000 to 5,000).
U.S. Patent 3,416,9~2 to McIntyre et al, issued December 17,
1968, discloses polyester antistatic agents which can contain a
water-solvatable polymeric group such as a polyoxyalkylene group
having an average molecular weight of from 300 to 6,000.
Preferred polyoxyalkylene groups are the PEG's having an average
molecular weight of from 1,000 to 4,000. Treatment is carried out
by applying an aqueous dispersion of the polyester in the presence
of an ant1Oxidant, followed by heating to a temperature above 90-C
to obta~n a durable coating of the polyester on the treated
artlcle. Example 6 d~scloses one such polyester formed by the
catalyzed reaction of dimethyl terephthalate, ethylene glycol and
an 0-methyl poly(oxyethylene~glycol having an average molecular
weight of 350. A 20% solution of this polyester in benzyl alcohol
was used to impart antistatic properties to a polyester fabric.
Example 7 discloses a 20h aqueous solution o~ a similar polyester
used to impart antistatic properties to a polyester fabric.
U.S. Patent 4,427,557 to Stockburger, issued January 24,
1984, discloses low molecular weight copolyesters (2,000 to
10,000) formed by the react1On of ethylene glycol, a PEG having an
average molecular weight of 200 to 1,000, an aromatic dicarboxylic
acid (e.g., dimethyl terephthalate), and a sulfonated aromatlc
dicarboxylic acid (c.g., dimethyl 5-sulfoisophthalate). The PEG
can be replaced, in part, with monoalkylethers of PEG such as the
methyl, ethyl and butyl ethers. A dispersion or solution of the
copolyester is applied to the textile material and then heat set
at elevated temperatures (90-C to 1~0-C) to impart durable soil
release properties. See also the McIntyre et al patent, where
Example 2 discloses a random copolyester used to impart antistatic
W 0 92/17523 2 ~ 6-- Pcr/vs92/o2256
properties which is formed by reacting dimethyl terephthalate,
sodium dimethyl sulfoisophthalate, ethylene glycDl and a PEG
having an aYerage molecular weight of 1,540.
In addition, there are several disclosures in the art of
polyesters, more particularly their lower molecular weight
oligomers, capable of acting as sra's in laundry products. The
earlier disclosures relate to modified polyester-type materials
which are not necessarily oligomeric and wh k h contain segments
without particular end-caps. They derive from e~hylene glycol/
dimethyl terephthalate randomly interspersed w~th polyether
segments deriving from polyethylene glycol. See, for example,
U.S. Patent 3,962,1~2, Micol et al, issued June 8, 1976, U.S.
Patent 4,116,885, Derstadt et al, issued September 7, 1978,
Canadian Patent 1,100,262, Becker et al, issued May 5, 1381, U.S.
Patent 4,238,531, Rudy et al, issued December 9, 1980, and British
Patent Application 2,172,608, Crossin, published September 24,
1986.
More recent developments in the field of sra's for laundry
detergent appl~cations include certain end-capped ester oligomers,
such those generally disclosed in United States patents to
Gosselink: see, for example, U.S. Patent 4,702,857, ~ssued October
77, 1987, U.S. Patent 4,721,580, issued January 26, 1988 and U.S.
Patent 4,877,896, Maldonado, Trinh and Gosselink~ ~ssued October
31, 1989.
SUMMARY OF THE INVENTION
The present lnvention encompasses soil release agents which
comprise the oligomeric ester~fication product of a reaction
~ixture which comprises:
(a) optionally, but preferably, a source of C~-C,
alkoxy-terminated (preferably, methoxy-terminated)
polyethoxy units R~-~OCH2CH2)x-O- or, optionally,
mixtures of said terminated polyethoxy units which
incorporate small amounts of propoxy units;
(b) a source of terephthaloyl units or~ optionally, mixtures
of terephthaloyl and small amounts of isophthaloyl
units;
(c) a source of poly(oxyethylene)o%y units -(OCH2CH2)y-0-;
td) a source of oxyiso-propyleneoxy units
WO 92/17523 ~ ) PCI /U!~92/û2256
- 7 -
5H3
-OCHCH20-; and
(e3 a source of oxyethyleneoxy units -OCH2CH20-;
said soil release agents being further characterized by haYing a
mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units of at
least about 0.5:1.
Thus, the so;l release agents herein comprise, fDr example,
the esterification reaction product of a reaction mixture
comprising:
~a) CH3(0CH2CH2)liOH;
~b~ dimethyl terephthalate;
(c) polyethylene glycol 1500 (E3
(d) 1,2-propylene glycol; and
(e) ethylene glycol;
wherein the mole ratio of oxyethyleneoxy units:o~yiso-propyleneoxy
units ls at least about 0.5:1, preferably at least about 1.25:1.
Such soil release agents differ from the sr~'s disclosed by
Gossel~nk and Diehl, U.S. Patent 4,711,730, cited above, 1n that
they contain oxyethyleneoxy units. The sra's of this ~nvention
20 unexpectedly exhibit better performance than those of the '730
; patent.
~hile not intending to be li~ited by theoretical or struc-
: tural considerat~on, it is believed that the pref~rred sra's of
this invention are characterized by the general formula:
2~ O O rO 0
~ Rlo-lcH2c~2o)x L R2 m LC ~ C0(cH2cH20)y n
O O
C~C - O (CH2CH20)%-Rl
wherein R1 is lower (e.g., C~-C4) alkyl, especially methyl; and R2.
is a mixture of both H and CM3 ~i.e., both ethylene and
isopropylene moieties are present in the molecular structure~ to
provide a mole ratio o~ oxyethyleneoxy:oxyisopropyl2neoxy of at
least about 0.5:1, pre~erably at least about 1.25:1.
In the formula depicted, x, y, m and n are integers within
the following ranges:
W O 92/17~23 h ~ 7 8 - ~CT/US92/02256
~road Preferred Most Preferred
x 6 100 6-~3 12^30
y 6-100 12-77 12-~0
m 0O75-30 1.5-25 2.25-20
S n 0.25-20 0.5-15 0.75-12
m+n~1* 1-5 1.2-4.5 1.5-4
n+1
*This term indicates the average number of adjacent terephthalate
units before interruption by a PEG unit.
It is to be understood tha~ the mole ratio of oxyethyleneoxy:
oxypropyleneoxy units can be varied to meet the needs of the
formulator. For example, for use with fabric softeners, this
ratio is preferably at least about 0.75:1, more preferably at
least about 1.25:1. For use in liquid detergents, some product
haziness may occur at these ratios, so the formulator may elect to
select a somewhat lower ratio, e.g., 0.5:1.
~he invention also encompasses laundry compositions such as
detergents, softeners, rinse aids, and the like, comprising at
least about 0.1X, preferably from about 0.2Yo to about 10% by
weight, of the forego~ng sra's.
Preferred fabric softener compositions herein typically
comprise from about 0.3% to about 3% by weight of the sra and from
about 3X to about 25% by we~ght of a fabric softener component.
A dilutable liquid fabric softener compos~tion eonc2ntrate
comprises:
(a) from about 10X to about 32% by weight of a eationic
fabric softener;
(b) from about 4X to about 20% by weight of an imidazolinium
fabric softener; and
(c) from about 1% to about 5Y by weight of the sra.
Typical laundry detergent compositions herein comprise
eonventlonal detersiYe surfaotants, optional builders, optional
earriers, and from about 0.1X to about 10Z by weight of the sra.
Preferred laundry detergents comprise from about 0.3% to about 3X
by weight of said scil release agent and at least about 3h~
preferab~y from about 3% to about 200XD by weight of a fatty acid
polyhydroxy amide surfactant, especially C12-C18 fatty aoid
N-~ethylglucamide.
WO 92/17523 ~ PCr/ L1S92/02256
g
The invention also encompasses a method for providing a soil
release finish on fabrics by contacting said fabrics with an
aqueous medium containing at least about 2 ppm of the foregoing
sra's. In a preferred mode, the method comprises contacting the
fabrics with an aqueous bath comprising at least 3 ppm (preferably
from about 4 ppm to about 25 ppm) of the foregoing sra's an~ at
least about 10 ppm (preferably frnm about 30 ppm to about 100 ppm)
of a cat~oni~ fabric softener for a period of at least about 1
minute (preferably from about 1 minute to about 10 minutes~ before
sPparating the fabrics from the aqueous bath. (It will be
appreciated that even lower levels of the sra's ran be effeetive
with multicycle treatments.) It will be appreciated that such
methods can readily be carried out during the rinse cycle in a
conventional automatic washing machine.
All percentages, ratios and proportions herein are by weight,
unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
The sra's of the present invention are prepared by esterifi-
cation of the hydroxyl- and carboxylate-substituted reactants
disclosed herelnabove. The following Examples further 1llustrate
the preparation of sra's according to this invention, but are not
intended to be limiting thereof.
E~L~
Synthesis of a Polvmer of PolY(Ethylene Glycol) Meth~l Ether
of MW 750._~limet~vl T~eQhthalate, PolY~Ethvlene Glycol~ of MW
1500. Ethvlene Gl~y~L,~L~u~L ene G1YCQ1 - TO a 250 ml, three-
neck, round bottom flask equipped with a magnetic stlrring bar,
modified Clais2n head, condenser tset for distillation), thermo-
meter, and temperature controller (THERM-O-WATCH, I2R) is added
poly(ethylene glycol) methyl ether of MW 750 (Aldrich, 50.0 g,
0.067 mol), dimethyl terephthalate (35.6 9, 0.183 mol),
poly~ethylene glycol~ of MW 1500 (Aldrich, 50.0 9, 0.033 mol),
ethylene glycol ~Baker, 7.2 9, 0.116 mol), 1,2-propylene glycol
(Fisher, 8.9 9, 0.117 mol), hydrated monobutyltin o%ide (M&T
Chemicals, 0.30 9, 0.2% of total reaction weight), and butylated
hydroxytoluene (Calbiochem, 0.1~ 9, 0.1% of total reaction
weight). This mixture ~s heated to 180-~ and maintained at that
temp~rature overnight under argon as methanol and water distill
from ~he reaction vessel. A 13C-NMR(DMSO-d6) shows a residual
WO92/17523 j,,~ ~6~ 7 PCI/US92/0~256
- 10 -
resonance for methyl esters at ~52 ppm. The temperature is raised
to 200~C for 5 hours, and then additional ethylene glycol (7.2 9,
0.116 mol) and propylene glycol (8.9 9, 0.117 mol) are added. The
temperature is lowered to 190-C, where it is maintained overnight.
A 13C-NMR(DMS0-d6) shows this stage of the reaction to be complete
by the disappearance of the resonance for methyl esters. The
mater;al is transferred to a 1 llter, single neck, round bottom
flask and heated gradually over about 20 minutes to 230-C in a
Kugelrohr apparatus (Aldrich) at about I.5 mm Hg and maintained
there for 1 hour. The ~lask is then allowed to air cool quite
rapidly to near room temperature under vacuum (-30 min.). The
reaction yields 124.1 9 of soft brown solid. The lH-NMR(DMS0-d6)
shows a very intense resonance at about 3.5 ppm for the poly(oxy-
ethylene) segments, a resonance at about 8.0 ppm for the tere-
phthalates, resonances at about 1.4 ppm for the methyl group of
doubly esterified propylene glycol, and at about 4.7 ppm for
doubly esterified ethylene glycol. Comparison of the resonances
at 1.4 and 4.7 ppm indicates that the mole ratio of ethylene
glycol-derived units to propylene glycol-derived units is approxi-
mataly 2.2:1. Th~s is referred to as the E/P ratio. The
13C-NMR(DMS0-d6) is also consistent with the desired polymer
structure, showing resonances at 70.2 (polyoxyethylene segments),
16.5 ppm (CH3 of doubly esterif;ed propylene glycol), 63.6 ppm
~doubly ester;fied ethylene glycol~, and 58.4 ppm (CH~OCH2CH20-).
The absence of resonances at about 60 ppm for any monoesters of
ethylene glycol (-C(O)OCH2CH20H) or at about 20 ppm for the methyl
group of one of the isomeric monoesters of propylene glycol
(-C(O)OCH(CH3)CH20H) indicates that the degree of polymer kation
is high.
An oligomer w~th a lower E/P ratio may be obtained using the
same synthesis conditions except that the in1tial ratio of ethyl-
ene glycol:propylene glycol is reduced. Typically, ~n initial
glycol ratio of about 0.25:1 gives a final E/P ratio of about
0.5:1.
~e~LE_ll
PQlymer of Eth~Lene _Gl~c~ Di~ethvl Terephthalate
- Into
a 5 liter, three necked, round bottom flask equipped with magnetic
WO92/17523 ~-J; i U ~ PCr/US9~/02256
- 11 -
stirring, heating mantle, internal thermometer, distillation head,
condenser set for distillation, inlet for inert gas, and THERM-0-
WATCH (I2R) for temperature control, are placed the following:
G_ams Moles Source
Ethylene glycol 130.2 2.1 MCB
Dimethyl terephthalate 640.2 3.3 Aldrich
Poly(ethylene glycol) 3Q0 0.4 Union Carbide
methyl ether MW 750
Poly(ethylene glycol) 1500 1.0 Union Carbide
of MW 1500
1,2-propylene glycol 322 ~i.2 Fisher
Hydrated monobutyltin oxide 5.5 M&T Chem
(FASCAT 4100)
Butylated hydroxy toluene (BHT) 3.2 Calbiochem
The system is stirred as the temperature is gradual-ly raised
to 185'C and held there for 28 hours as methanol distills from the
reaction. Then a fritted glass inlet tube is inserted to near the
bottom of the flask and inert gas is passed through at a high rate
w~th the temperature gradually raised to 240-C. Thls is continued
for approximately 13 hours. The resulting polymer 1s allowed to
cool to give about 2400 g of a soft solid which is mostly soluble
in water at room temperature when tested by stirring overn~ght at
a 10% solids level. The lH-NMR(d6 DMS0) shows a very intense
resonance at about 3.45 ppm for the polyoxyethylene s~gments, a
complex resonance at about 8.05 ppm for the terephthalates,
resonances at about 1.4 ppm for the methyl group of doubly
esterified propylene glycol 9 and at about 4.7 ppm for doubly
esterif~ed ethylene glycol. Comparison of the resonances at 1.4
and 4.7 ppm indicates that the mole ratio of ethylene glycol-
derived unlts to propylene glycol-derived units is approximately
1.5:1. This is referred to as the E/P ratio. The l3C-NMR(d6-
DMS0) is also consistent with the desired polymer structure,
showing resonances at 7~.~ ppm (polyoxyethylena segments), 16 ppm
~CH3 of doubly ester~fied propylene glycol), 63.6 ppm (doubly
3~ ~sterified ethylene glyool~, and a very tiny peak t 58 ppm
(CH30CH20-). The virtual absence of resonances at about 60 ppm
for any monoesters of ethylene glycol ~-C(O)OCH2CH2DH) or at about
20 ppm for one of the isomerie monoesters of propylenP glycol
w o 92/17523 PCT/~92/02256
2 1 ~ 12 -
((-C~O)OCH(CH3)CH20H) indicates that the degree of polymerization
is high.
EXAMPLE III
Pol~ler ._of Ethvlene G1YCO1~ D;methY1 TereDhtha1ate~
PolY(Ethvlene ~1YCO1 ) MethYl Ether of MW 750. Pol~(EthYlene
G1YCO1)_Of MW 1500~ and_l.2-ProPYlene~ - Into a 5 liter,
three necked, round bottom flask equipped with magnetic stirring,
heating mantle, internal thermometer, distillation head, condenser
set for distillation, inlet for inert gas, and THE~M-0-WATCH (I2R)
for temperature control, are placed the following:
Grams Moles ~rce
Ethylene glycol 408 6.5~ Fisher
Dimethyl terephthalate 1024 5.28 Aldrich
Poly(ethylene glycol) 480 0.64 Aldrich
methyl ether MW 750
Poly(ethylene glycol) 2400 1.60 Aldrich
of MW 1500
1,2-propylene glycol 510 6.71 Mallinkrodt
Hydrated monobutyltin cxlde 3 M&T Chem
(FASCAT 4100)
Butylated hydroxy toluene (BHT) 3 Calbiochem
The syst~m is stirred as the te~perature is gradually raised
from }75-C to 195-C over a 36 hour period as 290 9 of distillate
~mostly methanol) is collected. The temperature is then raised to
210-C for 18 hours as more distillate is collected. Then a
fritted glass inlet tube is inserted to near the bottom of the
flask and inert gas is passed through at a high rate with the
temperature maintatned at 200'C. This is continued for
approximately 4 days as a small amount of addltional distillate
collects. The resulting polymer ls allowed to cool to give about
3800 9 of a soft solid which is about 65~ soluble in water at room
temperature when tested by stirring overnight at a 10% solids
level. (In lower solids-content solutions, the fraction dissolv-
ing appears to be considerably higher.) The 1H-NMR(d6-DMS0) shows
a very intense resonance at about 3.45 ppm for the polyoxyethylene
segments, a eomplex resonance at about 8.05 ppm for the tere-
phthalates, resonanoes at about I.4 ppm for the methyl group for
doubly esterified propylene glycol, and at about 4.7 ppm for
doubly esterified ethylene glycol. Çomparison of the resonances
. ~ ,
w o 92t17523 ,.,.~ PCT/US92/02256
- 13 -
at 1.4 and 4.7 ppm indicates that the mole ratio of ethylene
glycol-~erived units to propylene glycol-derived units is
approximately 2.6:1. This is referred to as the E/P ratio. The
13C-NMR(d6-DMS0) is also consistent with the desired polymer
structure, showing resonances at 70.2 ppm (polyoxyethylene
segments), 16 ppm (CH3 of doubly esterified propylene glycol),
63.6 ppm (doubly esterified ethylene glycol), and a Yery tiny peak
at 58 ppm (CH~OCH2CH20-). The virtual absence of resonances at
about 60 spm for any monoesters of ethylene glycol
(-C(O)OCH2CH20H) or at about 20 ppm for one of the isomeric
monoesters of propylene glycol (-C(O)OCH(CH3)CH20H) indioates that
the degree of polymerization is high.
Fabric Treatment ComDositions
The sra's according to this invention can be employed in a
variety of circumstances where it is desired to impart a soil
release finish to fabrics, especially in a laundering operation.
For example, the sra's herein can be added directly to a laundry
or rinse bath of an automatic washing machine. Alternatively, the
sra's can be sprayed onto fabrics during an ironing operation. In
another mode, the sra's can be deposited onto fabrics during a
laundry drying operation in an automatic clothes dryer.
In a preferred ~ode, the sra's herein are depos;ted onto
fabrics fro~ an aqueous bath containing a fabric softener, such as
the cationic fabric softeners well known in the art. Indeed,
various sra's can be selected from those disclosed herein which
are quite compatible with cationics and do not disadYantageously
increase the viscosities of even the "triple-concentrate" liquid
fabric softener products that have recently come onto the market.
In general, the lower molecular weight sra's will result in lesser
increases in viscosities. Accordingly, preferred compositions
herein provide both a fabric softener component and an sra
component, and are designed to prov~de a fabric softening ~and
antistatic) benef~t concurr~ntly with a soil release conditioning.
The following is intended to assist the formulator in the
manufacture of combined fabric softener/so;l release compositions,
but is not int~nded to be limiting thereof.
L;qu;d Fabric So~teners - The liquid fabric softener composi-
tions of the present invention comprise an effective amount of the
sra's hereinabove defined. ~hat is an "effective amount" will
WO 9~/17523 f~ ~ g ~; 2 ~ 7 PCI`/U~i9~/02256
^ 14 -
depend upon the particular sra's used, the particular type of
fabric softener formulation and the benefits desired. Usually,
the sra's are effective when included in an amount from absut 0.01
to about lO~o by weight of the composition. In terms of soil
release benefits, preferred fabric softener compositions can
comprise from about G.1 to about 5% by weight of the sra's, but
typically comprise ~rom about 0.3 to about 3% by weight of these
compounds.
The fabric softener composit~ons of the present invention
further co~prise from about 2 to abo~t 5~% (preferably from about
3 to about 25%) by weight fabric softener components. For regular
s~rength (lX) fabric softener compositions9 the fabric softener
component typically comprises from about 3 to about 10% by weight
of the composition. For concentrated (e.g., 3X) fabric softener
compositions, the fabric softener component typically comprises
from about 15 to about 25X by weight of the composition.
The fabric softener component typically comprises a mono- or
dithigher alkyl) quaternary ammonium salt or mixtures of such
salts. See U.S. Patent 37928,213 to Temple et al, issued December
23, 1975, especlally column 2, line 57 to column 4, line 34, and
U.S. Patent 4,399,045 to Burns, issued August 16, 1983, especially
column 4, line ~3 to column 7, line 2 (herein lncorporated by
reference~, which disclose suitabl~ guaternary a~cnium salts. By
"higher alkyl" as used ~n the context of the quaternary ammonium
salts herein is meant alkyl groups having from 8 to 30 carbon
atoms t pre~erably from 12 to 22 carbon atoms. Examples of such
conventional quaternary ammonium salts include:
1. mononitrogen quaternary a~monium salts having the
formula:
R2
R1 - N~ - R3 A-
~2
wherein R1 is an aliphatic CI2-C22 hydrocarbon group; R2 is a
C1-C~ saturated alkyl or hydroxyalkyl group. R3 is selected from
R1 (preferred~ or R2 groups and A is an anion such as chloride,
bromide or methyl sulfate.
Examples of suitable mononitrogen quaternary ammonium salts
are mono tallowtrimethylammonium chloride ~MTTMAC), ditallowdi-
WO92/17523 ~ . 3~ ~ 7 PCT/US92/02256
1~
methylammonium chloride (DTDMAC), ~itallowdimethylammonium methyl
sulfate, di(hydrogenated tallow)dimethylammonium chloride,
dibehenyldimethylammonium chloride, dihexadecyldimethylammonium
chloride, dioctadecyldimethylammonium chloride, dieicosyldimethyl-
ammonium chloride, didocosyldimethylammonium chloride;
di(hydrogenated tallow)dimethylammoni Lm methyl sulfate;
dihexadecyldiethylammonium chloride; ditallowdipropylammonium
bromide; di~coconutalkyl)dimethylammoniunl chloride; and mixtures
thereof;
2. diamide quaternary a~monium salts having the formula:
o R6
R4 - C - NH - R3 ^ N+ - R5 NH - C - R~ A-
R,
wherein R~ is an aliphatic C12-C~2 hydrocarbon group; R3 and Rs
are each divalent alkylene group having 1 to 3 carbon atoms; R6 is
a Cl-C~ saturated alkyl or hydroxyalkyl group; R7 is R6 or the
moiety (CaH2aO)bH, wherein a is 2 or 3 and b is from 1 to about 5;
and A is an anion.
Examples of suitable diamide quaternary ammonium salts are
methylbis(tallowamidoethyl)(2-hydroxy~thyl)ammonium methyl sul-
fate, methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)-
ammonium methyl sulfate, and bis(2-hydrogenated tallowamidoethyl3-
ethoxylatedammonium methyl sulfate; these materials are available
from Sherex Chemical Company under the trade names VARISOFT 222,
YARISOFT 220 and VARISOFT 110;
3. quaternary imidazolinium salts such as 1-methyl-1-
tallowamido-ethyl-2-tallowimida~olinium methyl sulfate (sold under
the trade name VARISOFT 475), 1-methyl-1-(hydrogenated tallow-
amidoethyl)-2-tallowimidizolium methyl sulfate (sold under the
trade name VARISOFT 445), 1-ethylene-bis(2-tallow-1-methyl-
imidazolinium methylsulfate) (sold under the trade name VARISOFT
: . 6112); and 1-methyl-2-tallow-3~tallowamidoethyltallowylamino)-ethyl~imidazolinium methylsulfate (sold under the trade name
VARISOFT 3012).
For concentrated fabrîe softener compositions, a preferred
fabric sGftener component comprises: (A) from about 2 to about
15~ by weight mononitrogen quaternary ammonium salts; (B) from O
to about 14% by weight diamide quaternary ammonium salts; tC) from
about 2 to about 13% by weight quaternary imidazolinium salts; the
WO 92/17523 PCI/US92/~2256
h ~ .L ~
- 16 - .
total amount of salts A, B and C being from about 15 to about
22.5% by weight. See U.S. Patent 4,399,045 to Burns, issued
August 16, 1983, which is incorporated by reference.
The fabric softener cumponent can also comprise certain
di~higher alkyl) cyclic a~ines, typica11y as a mixture with a
quaternary ammonium salt(s). These c~yclic amines haYe the
formula:
~ICH2)c -
Q~ N - Z - R3
C
Rg
wherein c is 2 or 3, preferably 2; R8 and Rg are, independently, a
C~-C30 alkyl or alkenyl group, preferably CIl-C22 alkyl, more
preferably C~s-CI~ alkyl, or mixtures of such alkyl radicals, such
I5 as those ~btained from coconut oil, "soft~ ~nonhardened) tallow,
and hardened tallow; Q is CH or N, preferably N; Z is
- RIo - T - C -
wherein T ~s O or NRI~, RIl being H or C~-C~ alkyl, preferably H;
and RIo is a divalent CI-C3 alkylene or (C2H~OJd group, wherein d
is a number of from I to 8, or Z is RIo.
Specific examples of such amines are as follows: I-tallow-
amidoethyl -2-tdl lowimidazoline; I-(2-CI 4 _ ~ ~ -alkyl-amidoethyl)-~-
CI3-C~-alkyl-4,5-dihydro-imidazole; I-stearylamidopropyl-2-
stearyl.imidazoline; and I-tallowamidobutyl-2-tallowpiperidine.
These amides and methods for their preparation are fully
described in British Application 8,508,I30, filed March 2R, I985
by Koenig and deBuzzacarini which is herein incorporated by
reference. (See also U.S. Patent 4,711,730, column 28.)
C. Optional Ingredients
I. Acids and Bases - When cyclic amines are pres~nt in the
fabric soften~r ccmponent, the pH oF the fabric softener composi-
tion is important for proper dispersion of the amtnes. Moreover,
a somewhat ac~d~c pH is preferred for hydrolytie stabillty of ~he
soil release compounds of the present inYention. Therefore, acids
and/or bases can be added to the composition to adjust its pH.
The amount of acid or base should be such that the pH of the
dispersion, after mixing, is in the range from about 2.5 to about
6.5.
WV 92/17523 2 :L ~ ~3 ~ 3 ' PCT/US92/02256
- 17 -
Examples of suitable acids include the inorganic mineral
acids, carboxylic acids, in particular the low mo1ecular weight
(Cl-C3) carboxylic acids, and alkanesulfonic acids.
Suitable inorganic acids include HCl, H2SO~, HNO3 and H3PO~.
Suitable organic acids include formic, acetic, methanesulfonic and
ethanesulfonic acid. Preferred acids are hydrochloric, phos-
phoric, formic and methanesulfonic acid.
Suitable bases include NaOH and Na2CO3.
2. Organic solvent - The fabric softener compositions of
the present inven~ion can be formulated without the use of any
organic solvent. However, the presence of organic solvents (for
example, low molecular weight, water miscible aliphatic alcohols)
does not harm the storage stability, the viscosity, or the
softening performance of the compositions. Examples of such
solvents include ethanol and isopropanol.
Typically, the quaternary ammonium salt(s) (or cyclic amine)
will be obtained from a supplier of bulk chemicals in solid form
or as a solution in an organic solvent, e.g., isopropanol. There
is no need to remove such a solvent in making the compositions.
Indeed, additional sol~ent can be added, if this is dee~ed
desirable.
3. Optional Nonionics - The fabric soFtener compositions
optionally contain nonionics as have been disclosed for use in
softener compos~tions. Such nonionics and the usa~e levels have
been disclosed in U.S. Patent 4,454,049~ to Mac6ilp et al, issued
June 12, 1984, which is incorporated by reference.
Speci~ic examples of nunionics suitable for the fabric
softener compositions herein include glycerol esters (e.g.,
glycerol monostearate), fatty alcohols (e.g., stearyl alcohol),
and alkoxylated fatty alcohols. The nonionic, if used, is
typically used at a level in the range of from about 0.5 to about
- 10% by weight of the composition.
Although generally considered as having fabric softening
properties, the nonionics are not consid~red part of the fabric
softening compunent for the purposes of calculating the amount of
fabric softening component in the composition.
4. Optional Silicone Component - The fabr;c softening
composition aptionally contains an aqueous emulsion of a predomi-
nantly linear polydialkyl or alkyl aryl siloxane in which the
wo 92/17523 ~ ~ 18 - Pcr/usg2/o22s6
alkyl groups can have from one to five carbon atoms and can be
wholly or partially fluorinat2d. Suitable silicones are poly-
dimethyl siloxanes having a visc05ity at 25-C in the range from
about 100 to about 100,000 centistokes, preferably in the range
from about 1,000 to about 12,000 centistokes.
The ionic charge characteristics of the silicone as used in
the combination can be important in determining both the extent of
deposition and the evenness of distribtJtion of the silicone and
hence the properties of a fabric treated therewith.
Silicsnes having cationic character show an enhanced tendency
to deposit. Silicones found to be of value in providing fabric
feel benefits have a predominantly linear character and are
preferably polydialkylsiloxanes in which the alkyl.group is most
commonly methyl. Such silicone polymers are frequently manufac-
tured commercially by emulsion polymerization using a strong acid
or strong alkali catalyst in the presence of a nonionic or mixed
nonionic-anionic emulsifier system.
The optional silicone component also embraces a silicone of
cationic character which is defined as being one of: (a) a
predo~inantly linear poly di C1-Cs alkyl- or C1-alkyl, aryl-
polysiloxan~, prepared by emulsion po7ymerizatinn us~.ng a cationic
surfactant as emulsifier; (b) an alpha-omega-di quaternized di
C~-Cs or Cl-Cs alkyl, ~ryl siloxane polymer; or (c) an amino-
functional di (C,-C5 alkyl or alkyl aryl siloxane polymer in which
the amino group may be substituted and may be quaternized and in
which the degree of substitution (d.s.) lies in the range 0.001 to
0.2, preferably 0.01 to 0.073; provided that the viscosity at 25'C
of the silicone is from about 100 to about 100,000 centistokes.
The fabric softening compos~tions herein can contain up to
about 10%, preferably frDm about 0.1% to about 5%, of the silicone
component.
: 5. Other Optional Ingredients - In order to further improve
the stability of the fabric softener ~omposit~ons hereint and
further adjust their viscosities9 these compos~tions can contain
relatively small amounts of electrolytes (e.g., O.IX-3%), such as
; NaCl, KBr, LiCl, MgCl2 or CaC12.
The fabric softener compositions can also optionally contain
other ingrcdients known to be suitable for use in textile soften-
ers. Such adjuvants include perfumes, preservatives, germicides,
WO 92/17~523 ~ r~ rl PCT/l~S92/02256
- 19 -
colorants, dyes, fungicides, stabilizers, brighteners and opaci-
fiers. These adiuvants, if used, are normally added at their
conventional leYels (ca. 0.1%-5%). HoweYer, in the case of
composition ingredients utilized for a f2brie treatment effect,
e.g., perfumes, these materials can be added at higher than normal
levels, corresponding to the degree of coneentration of the
product.
The balance of the liquid fa~ric softener compositions of the
present invent~on is water.
The following illustrates liquid compositions of the
foregoing type.
EXAMeLE_IV
A fabric softener base composition is prep~red from the
following ingredients:
Inqredient ~t. %
Ditallowdimethylammonium chloride 4.33
1-methyl-1-tallowamidoethyl-2-tallow-
lmidazolinium methyl sulfate (VARISOFT 475) 1.0
Ethanol 0.7
Isopropanol 0.1
Perfume 0.42
Dye o.1
Minors* up to 0.1
~ Water Balance
- 25 ipreservative, NaCl, NaOH, H2SO~, antioxidant solut~on.
To this base composition is added lX by weight of the sra's of
Examples I and II, respectively, to provide fabric softening/sra
co~positions IVA and IVB.
~eL~
Regular strength and concentrated fabrk softener base
compositions are prepared from the following ingredients:
iç~ Wt. %
V VI YII VIII
D~tallowdimethylan~nonium chloride 3.65 7.7 2.33 7.0
1-tallowamidoethyl-2-tallowimida~oline3.65 14.3 4.33 3.0
Tallowtrimethylammonium chloride O.5 0.5
Polydimethylsiloxane
~viscosity 5,000 cen~istokes) 0.2 ~.6 1.33 4.0
W O 92~17523 PCT/US92/02256
Id3 ?~l7~ ? ~ ~ - 20 -
Perfume 0.25 0.45 0.25 0.45
Minors* 0.13 0.13 0.13 0.13
HCl --- to pH 4 --~
Water --- Balance --- --^
5~CaCl 2 ~ dye, bacter;cide
To regul~r strength base compositions V and VII are added 0.5% by
weight of the sra's of Examples I and III, respectively. To
concentrated base compositions VI and VIII are added 1.5% by
weight oF the sra's of Examples I and II, respectiv~ly.
EXAMPLE IX
A conoentrated fabric softener base composition 1s prepared
from the following ingredients:
Inqredient Wt. %
Dihydrogenatedtallowdimethylammonium
15chloride 13
I-methyl-l-tallowamidoethyl-2-
tallowimidazolinium mEthyl sulfate 3
Polar Brilliant Blue dye ~0 ppm
CaCl2 0.265
Perfume 0.,5
: Ethanol 0.92
Isopropanol l.36
~at~r Balance
- To this concentrated base composi.tion is added 1.5X by weight
of the sra's of Examples I, II and III, respecttvely, to provide
eoncentrated softener compos1tions plus sra IXA, IXB and IXC.
EXAMPL~ X
A preferred softener composit~on is as follows.
Inqredient Wt X of Fin31 Formyla
Premix
DTDMAC 4.00
MTTMAC 0.67
VARISOFT 475* 2.00
Deioniz~d water Balance
Silicone DC-1520 (antifoam) 0.02
HCl** 0.35
Lytron 621 (dye~ 0.75
SRA*** 2.25
W o g~/17523 2 ~ Iy ~ ?,_ , PCT/~S9x/02256
- 21 -
KATHON (preservative) 0.04
Poly(dimethyl siluxane)***~ 0.20
Perfu~e 0.30
* Imidazolinium fabric softener
** Enough to have the pH of final product at 3-3.5.
*** Prepared in the manner of Example I; E~P ratio 1.5.
*~**A 55% polydimethyl siloxane (35û cps~ emulsion tn water.
The Premix is blended with the Water Seat, then combined with
the Post Addition mix.
EXAMPLE XI
Using the ingredients illustrated in Example X, a 3X
concentrated fabric softener is prepared, as follows.
Inqredient Wt. Yo of Final Formula
Premi~
DTDMAC 14.67
VARISOFT 475 6.00
Water Seat
: Deionized water Balance
Silicone DC-1520 0.02
HCl* 0-35
Lytron 621 (dye) ~.75
SRA (E/P 1.5 per Example II) 1.50
~E~
KATHON 0.04
Poly(dimethyl siloxane) 0.54
P~rfume 1.05
*Enough to have the pH of final product at 3-3.5.
l~undrv Qetercen~ - Th~ sra's of the present invention are
also useful in certain laundry detergent ccmp3sitions to provide
~ soil r~lease properties. These compos~tions can be used aslaundry detergents, laundry additives, and laundry pre-treatments.
The laundry detergent composltions of the present invention
co~priss a soil r2lease component which contains an effectl~e
amount of the sra's previously defined. Nhat is an ~e ffective
amsunt" will depend upon the particultr sra's used, the particular
type of detergent formulation ~liquid, granular, etc.) and the
benefits desired. Usually, the sra's ar~ effective when include~
in an amount from about 0.01 to about 10% by weight of the
W O 92/17523 f~ 22 PCI`/US92/02256
composition. In terms of soil. release benefits, preferred laundry
detergent compositions can comprise from about 0.1 to about 5% by
weight of the sra's, but typically comprise from about Q.3 to
about 3% by weight of these compounds.
For granular detergent formulations, the sra component
typically comprises the sra compounds, plus any protective
enrobing material. In making granular detergent formulations, the
sra could be exposed to highly alkaline ~aterials such as NaOH and
KOH. The sra's, in part kular tho e haYing shorter backbones, can
be degraded by alkaline ~nvironments, especially those above a pH
of about 8.5. Accordingly, the sra's are preferably enrobed in a
material which protects them from the alkaline environment of a
granular detergent formulation yet permits the sra's to be
dispersed in the laundering operation.
Suitabl~ enrobing materials include the nonionic surfactants,
polyethylene slycols (PEG), fatty acids, fatty acid esters of
diols and polyols, anionic surfactants, film forming polymers and
mixtures of these materials. Examples of suitable nonionic
surfactant enrob~ng mater~als include some of those described
hereinafter as also being useful detersive surfactants in the
~: compositlons. Examples of suitable PEG enrobing materials are
those having an average M.W. of from about 2,000 to 15,00D,
preferably from about 3,000 to about 10,000 and most preferably
from about 4,000 to about 8,000. Examples of suitable fatty acid
enrobing materials are the higher ~atty acids having from 12 to 18
carbon atoms. Examples of suitable fatty acid ester enrobing
materials include the sorb~tan ~atty acid esters (e.g., sorbitan
~onolaurate). Other examples of suitable enrobing materials,
including anionic surfactants and film forming polymers, are
disclosed in U.S. Patent 4,486,327 to Murphy et al, ~ssued
December 4, 1984, which is incorporated by reference. The sra's
can be enrobed according to th~ methods diselosed in this Murphy
et al patent.
For liquid d~tergent formulations, the sra component can be
comprised entirely of sra's or can further include a water-soluble
organic solvent or a hydrotrope to aid ~n dissolving the srals.
Suitable organic solvents are usually aromatic and can include
ethyl benzoate, phenoxyethanol, methyl-o-toluate, 2-methoxybenzyl
WO 92/17523 !~ ? ~ 7 PCI~/US~2/02256
- ~3 -
alcohol and pyrrolidone. Suitable hydrotropes include the methyl
capped PEG's and shorter backbone polyesters. These short
backbone polyesters are more ~ater-soluble, and, accord;ngly, can
function as hydrotropes for the longer backbone, less
water-insoluble sra's.
The amount, or even the need for, organic solvents or
hydrotropes to prepare liquid detergent formulations containing
the sra's of the present ~nvention will depend upon the sra's
used, especially what fraction thereof is water-soluble, the
ingredients present in the laundry detergent sys~em, and whether
an is~tropic9 homogeneous liquid is desired. For isotropic liquid
detergent formulations, the sra's need to be dissolved as much as
possible which sometimes requires the use of organic solvents or
hydrotropes. Also, it is believed that dissolving the sra's in
liquid detergent formulations can make them more effective as so;l
release agents by facilitating dissolution in the wash liquor and
thereby the adsorption on target fabrics.
Laundry compositions of the present invention preferably
comprise from about 5 to about 75% by weight of a noninterfering,
Z0 preferably ronionic deters1ve surfactant. Preferably, the
non~onic detersive surfactant comprtses from about 10 to about 40%
by weight of the composition9 and most preferably from about 15 to
about 3~% by weight.
Suitable nonionic surfactants for use in laundry compositions
of the present invention are generally disclosed in U.S. Paten~
,929,678 to Laughlin et al, issued December 30, 1975 at column
13, line 14 through column 16, line 6 (herein incorporated by
reference). Classes of nonionic surfactants included are:
1. The polyethylene oxide condensates of alkyl phenols.
Examples of compounds of this type include nonyl phenol condensed
with about 9.5 moles of ethylene oxide per mole of nonyl phenol;
dodecylphenol condensed with about 12 moles of ethylene oxide per
! mole of phenol. Such materials are available as IGEPAL C0-630,
marketed by the 6AF Corporation, and Triton X-45, X-114, X-100,
and X-~02, all marketed by th@ Rohm & Haas Company.
2. The condensation products of aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide. The alkyl chain
of the aliphatic alcohol can either be straight or branched,
WO 92tl7!;23 PCI'/US92/02256
2 ~ 2 4
primary or secondary, and generally contains from about 8 to about
22 carbon atoms. Examples of such ethoxylated alcohols include
the condensation product of myristyl alcohol condensed with about
10 moles of ethylene oxide per mole of alcohol, and the condensa-
tion product of about 9 moles of ethylene oxide with coconut
alcohol (a mixture of fatty alcohols with alkyl chains varying in
length from 10 to 14 carbon atoms). E.xamples of commercially
available nonionic surfactants of this type include TERGITOL
15-S-9, marketed by Union Carbide Corporat~on, NEODOL 45^9, NEODOL
23-6.s, NEODOL 45-7, and NEODOL 45-49 marketed by Shell Chemical
Company, and KYRO EOB, marketed by The Procter & Gamble ~ompany.
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide
with propylene glycol. Examples of compounds of this type include
certain of the commercially available PLURONIC sur~actants,
marketed by Wyandotte Chemical Corporation.
4. The condensation products of ethylene oxide with ~he
product resulting from the reaction of propylene oxide and
ethylenediamine. Examples of this type of nonionic surfactant
include certain of the commercially available TETRONIC compounds,
marketed by ~yandotte Chemical Corporation.
5. Semi-polar nonianic detergent surfactants which include
water-soluble amine oxides contain~ng one alkyl ~oiety of from
about 10 to 18 earbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from
1 to about 3 carbon atoms; water-soluble phosphine oxides contain-
ing one alkyl moiety of from about 10 to 18 carbon atoms and 2
moieties selected from the group consisting of alkyl groups and
hydroxyalkyl groups conta~nlng from about 1 to 3 carbon atoms; and
water-soluble sulfoxides contain1ng one alkyl moiety of from about
10 to 18 carbon atoms and a moiety selected from the group consist-
ing of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon
atoms. Preferred amine oxide det~rgent surfactants are C10-C
alkyl dimethyl amine oxide and C8-C~2 alkoxy ~thyl dihydroxy ethyl
amine oxide.
6. Alkylpolysaocharides disclosed in European Pat~nt
Application 70,074 to Ramon A. Llenado, published January 19,
1983~ having a hydrophobic group containing from about 6 to about
30 carbon atoms~ preferably from about 10 to about 16 carbon atoms
WO 92/17523 ~ PCl[`/US92/02256
- 25 -
and a polysaccharide, e.g., a polyglycoside, hydrophil;c group
containing fro~ about 1.5 to about 10, preferably from about 1.5
to about 3, most preferably from about 1.6 to about 2.6 saccharide
units.
7. Fatty acid amide detergent ~urfactants (see U.S. Patent
4,711,730, column 17, line 35, for a description of such
surfactants).
8. Fatty acid polyhydroxy amide surfactants; see U.S.
Patent 2,965,576, issued December 20, 1960; also 6B Patent
809,060.
Preferred nonionic detergent surfactants for use in laundry
compositions of the present invention are the ethoxylated alcohols
and alkylphenols, especially the condensation products of C12-C14
alcohols with from about 3 to about 7 moles of ethylene oxide per
mole of alcohol, e.g., C12-Ci3 alcohol condensed with about 6.5
moles of ethylene oxide per mole of alcohol. N-alkyl glucamine-
amide-type surfactants, as described in U.S. Patent 2,965,576 and
in British Patent 8~9,060, E. R. Wilson, const~tute another class
of preferred nonionic surfactants for use herein.
Laundry compositions of th~ present invention can also
compr~se from 0 to about 15% by weight (preferably from 0 to about
10X by weight) synthetic anlonic detergent surfactants. These
synthetic anionic detergent surfactants include the water-soluble
: salts, typically the alkali metal, ammonium and alkylolammonium
salts, of organic sul~uric reaction products having in their
molecular structure an alkyl group containing from about 10 to
- about 20 carbon atoms and a sulfonic acid of sulfuric acid ester
group. (Included in the term ~alkyl~ is the alkyl portion of acyl
groups.)
Examples of this group of synthetic anionic surfactants are
the sodium and potassium alkyl sulfates, especlally th~se obtained
by sulfating the higher alcohols (C8-Cl8 carbon atoms) and the
sodium and potassium alkylbenzenesulfonates in wh1ch the alkyl
group conta~ns from about 9 to about 15 carbon atoms, in straight
cha~n or branched chain configuration, e.g., those of the type
described in U.S. Patents 2,~20,Q99 and 2,477,383. Included in
this class of surfactants are the linear straight chain alkylben-
zenesulfonates in wh kh the average number of carbon atoms in the
alkyl group is from about 11 to 13~ abbreviated as C~l-C13LAS.
W o 92/17~23 P~T/VS92/02256
~ J~ ri - 26 -
Synthetic anionic surfactants also include: the C,0-C22
alkyl polyethoxylate sulfates; the sodium alkyl glyceryl ether
sulfonates; the water-soluble salts of esters of alpha-sulfonated
fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid group and from about 1 to 10 carbon ato~s in the ester
group; water-soluble salts of 2-acyloxy-alkane-1-su1fonic acids
containing from about 2 to 9 carbon ato0s in the acyl group and
frum about 9 to about 23 carbon atoms in the alkane moiety; alkyl
ether sulfates containing from about 10 to 20 carbon atoms in the
alkyl group and from about 1 to 30 ~oles o~ ethylene oxide;
water-soluble salts of olefin sulfonates containing from about 12
to 24 carbon atoms; and beta-alkyloxy alkanesulfonat2s containing
from about 1 to 3 carbon atoms in the alkyl group and from about 8
to 20 carbon atoms in the alkane moiety.
The laundry compositions of the present invention can also
include ampholytic, zwitterionic and cationic detergent surfact-
: ants, as well as alkali metal soaps.
Ampholytic surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or allphatlc deriva-
tives of heterocycl k secondary and tertiary amines ~n whlch the
al iphatic rad~cal can be straight chain or branched and wherein
one of the aliphatic substituents contains from about 8 to 18
carbon atoms ~nd at least one contains an anionic water-
solubilizing group, e.g., carboxy, sulfonate9 sulfate. See U.S.
Patent 3,929,678 to Laughlin et al, issued December 30, 1975 at
column 19, lines 18-35 (herein incorporated by reference) for
examples of ampholyt~c surfactants.
Zwitterionic surfactants can be broadly described as deriva-
t~ves of secondary and tertiary amines, d~rivatives of hetero-
cyclic secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary phosphonium or tert1ary sulfoniu~ compounds.
See U.S. Patent 3,929,678 to Laughlin et al, issued December 30,
1975 at column 19, l~ne 38 through column 22, line 48 (herein
incorporated by reference) for exa~ples of zwitterionic
surfactants.
Suitable cationic surfactants are dlsclosed 1n U.S. Patent
4,259,217 to Murphy, issued March 31, 1981, herein incorporated by
reference.
wo 92/17523 ~ ,J ,'~ ) Pcr/vs92tO2256
- 27 -
The alkali ~etal soaps which are useful include the sodium,
potassium, ammonium and alkylolammonium salts of higher fatty
acids containing ~rom about 8 to about 24 carbon atoms, preferably
from about 10 to about 20 carbon atoms.
The laundry detergent compositions of the present invention
can optionally comprise inorganic or organic detergent builders to
assist in mineral hardness contro1. Such builders will typically
comprise up to about 6~% by weight of the compositions; built
liquid formulations generally comprise from about lX to about 25%
by weight detergency builder, most preferably from about 3% to
about 20Yo by weight, while built granular formulations generally
: comprise from about 5% to about SO% by weight detergent builder,
most preferably from about 10% to about 30~ by weight.
A wide variety of detergent builders are known in the
: 15 literature, and it is not intended to reproduce a complete listing
of such materials herein. The formulator may refer, for example,
to U.S. Patent 4,711,730, beginning at column 19, for a typical
listing of such materials. However, for the conven~ence of the
formulator, and not by way of limitation, some representative
suitable detergency builders are listed hereinafter.
Suitable detergent builders include the crystalline alumino-
silicate ion exchange materials typically referred to as ~Zeolite
A~, ~Zeolite P~, and ~Zeolite xn, especially the zeolites having a
particle slze from about 0.1 to about 10 microns. Qptimum
zeolites for builder purposes exhib~t a calcium ion exchange rate
of at least about 4 grains/gallon/minute/gram/gallon. Amorphous
aluminosilicates, especially those having a magnesium ion exchange
rate of at least about 1 gra1n/gallon/minute/gram/gallan are also
useful. A method for producing aluminosilicate ~on exchange
materials is. disclosed in U.S. Patent 3,9859669. An especially
preferred hydrated aluminosilicate has the fo mula:
Na~2[(Al02)l2 (SiO2),2]-XH20
wherein x is from about 20 to about 30~ especially 28.
Other detergency builders include the water-soluble alkall
motal ~or ammonium) phosphates, polyphosphates, phosphonates,
carbonates, silicates, acetates, polyhydroxysulfonates and,
especially, polyearboxylates. Various polycarboxylate builders
are disclosed in U.S. Patents 3,30Q,067; 3,723,322; 4,144,226; and
4,246,495. The oxydisuccinates ~aka "oxodisuccinatesn) the
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- 2~ -
tartrate mono- and di-succinates, and citrate are specific
examples of preferred polycarboxylate builders for use herein.
The laundry detergent compositions herein can also optionally
include clay soil removal and/or antiredeposition agents, and such
materials are usually employed in ranges from about 0.1% to about
10% by wei~ht of the compositions. Such materials include various
ethoxylated amines, and the like, referred to in the above-cited
U.S. Patent 4,711,730. Another group of preferred clay soil
removal/antiredeposition agents are the cationic compounds
d~sclosed in European Patent Application 111,96~, published June
27, 1984. Such materials are also disclosed in eonsiderable
detail in U.S. Patent 4,711, 730, cited above.
Other optional ingredients which can be included in laundry
detergent compositions of the present invention in their conven-
tional art-established levels for use (i.e., from about 0% to
about 20%, by weight3 include solvents, bleaching agents, bleach
activators, corrosion inhibitors, dyes, fillers, optical brighten-
ers, germicides, pH-adjusting agents, enzymes, en~yme stabilizers,
perfumes, and the like. The inclusion of such optional ingredi-
ents in fully-formulated detergent compos~tions is a ~atter o~
discretion, according to the objectives of the formulator.
6ranular detergent compositions embodying the sra's of the
present 1nYent~on can be formed by dry-mix1ng the sra's into
compositions formed by ~therwise conventional techniques, conYen-
tional techniques, i.e., by slurrying the other individual compon-
ents in water and then atomizing and spray drying the resulting
mixture, or by pan or drum granulation nf the ingredients, or by
fluidized bed processes.
Liquid formulations can be 1n the form of single phase
(preferred~ compositions or can be in multiphase or "dispers10n"
form. Disperslons convent10nally employ viscosity modifiers to
produce systems having plastic shear characteristics to maintain
stable dispersions and to prevent phase separation or solids
settlement.
3~ ~hile the laundry detergent compositions of the present
invention are operative within a wide range of wash pH's, they are
partieularly suitable when formulated in liquids to provide a near
neutral wash pH, i.e., an initial pH of from a~Dut 6.0 to about
8.5 at eoncentrations of from about 0.1% to about 2X by weight in
w o 92tl7523 ~ ' PcT/U~92/02256
- 29 -
water at 20-C. The near neutral pH of such formulations is also
desirable to ensure long-term stability for the sra's. In such
formulations, the product pH is preferably from about 6.5 to about
8.5, and more preferably from about 7.0 to about 8Ø
The following illustrate specific embodiments of laundry
detergent compositions employing the sra's Df the present inven-
tion, but are not intended to be limiting thereof.
~eL~L
A liquid detergent composltion is as follows.
~nqredient ~ _X
SRA* 1 . O
Sodium Cl2 alkyethoxy (1) sulfate g.5
C12-C13 alcohol pDlyethoxylate 10.2
~12 -14 N-methyl glucamide 7.0
Ethanol 5.5
Sodium ethylenediamine tetraacetate 0.3
Minors and H2O Balance
*SRA per Example I, above.
~L~
A granular detergent composition is as follows.
Inaredient
SRA* 3.5
C~2-C13 alcohol polyethoxylate 20~0
MgS0~ 1.0
Zeolite 4A hydrate (1-10 ~icron) 26.0
Na2C03 18.3
NaHC03 15.0
Maxattse MP ~protease) 1.5
Brightener 1.2
~ater and minors to 10~
*SRA per Example II, above~ enrobed in polyethylene glycol avg.
m.w. 8,000.
~he composition of Example XIII is prepared using standard
ad~ix procedures to incorporate the sra.
As can be seen from $he foregoing, the sra's of the present
invention can be employed in laundry and softening compositions of
a type ~amiliar to formulators of fabric care coTpositions. In
alternative modes, the sra's herein can be directly added to, for
example, aqueous laundry rinse baths in conjunction with fabrics.
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~J i ~ 30 -
In yet another mode, the sra's herein can be releasably affixed to
sheet substrates, or the like, deslgned for use ;n automatic
clothes dryers. Such sheet substrates can additionally have
releasably affixed th reto various fabric suftener and/or anti-
static agents of types which are well-known in com~ercial prac-
tice. In use, damp fabrics are tumbled with the sheet substrates,
thereby causing the sra and, if present, optional fabric soften-
ers/antistatic agents, to be transferred ~rom the sheet substrate
onto the fabric surfaces. These and other modes of application of
the sra's to fabrics are also contemplateli herein.
~hile the foregoing Examples illustrate the preferred capped
sra's, the following 111ustrates the optional uncapped sra's also
encompassed by this invention. It will be appreciated that the
uncapped sra's can be used in laundry formulations, as disclosed
above.
EXAMPL XIY
Svnthesis of an UncaPPed Oliqomer of_pimethv L TereDhthalate,
PolY(Ethvlene GlycolL_IMW~I4501~ EthYlene G1YCO1~ and ProPYLe~ne
Glvcol ~wlth E/P-2.21 - To a 250 ml, three-neck, round bottom
flask equipped with a magnetic stlrring bar, modified Claisen
head, condenser (set ~or tistillation), thermometer, and tempera-
ture controller (THERM-O-WATCH, I2R) is added poly(ethylene
glycol) of MW 1450 (Unton Carbide, 93.3 9, o.as4 mol), dimethyl
terephthalate (25.0 9, 0.129 mol), ethylene glycol (Baker, 16.0 9,
0.258 mol), 1,2-propylene glycol (Fisher, 19.6 9, Q.~58 mol), and
hydrated monobutyltin oxide (M&T Chemicals, 0.27 9, 0.2% of total
reaction weight). This mixture is heated to 180-C and maintained
at that tempe~ature overnight under argon as methanol and water
distill from the react~on vessel. A l3C-NMRtDMS0-d6) shows this
stage of the reaction to be complete by ths dlsappearance of the
resonance for methyl esters at -52 ppm. The material is
transfe~red to a 500 ml, single neck, round bottom flask and
heated yradually over about 20 minutes to ~40'C in a Kugelrohr
apparatus (Aldrich) at about 1 mm Hg and maintained there for 40
minutes. The flask is then allowed to air cool quite rapidly to
near room temperature under vacuum (-30 minutes). The reaction
yields 94.8 g of orange soft solid. A l3C-NMR(DMS0-d6) shows a
resonance for -C~O)OCH2CH20C(0)- at -63.2 ppm (diester), a
resonance for -C(O~OCH2CH20H at -59.4 pp~ (monoester~9 and a large
W O 92/17~23 ~ !~ f~ ,1 PCT/US92/022~6
31 -
peak at -69.8 representing poly~oxyethylene) units. The ratio of
the diester peak height to the monoester peak height is about 5.8.
The appreciable concentration of end groups consisting of
monoesters of ethylene glycol shows thal; the product is a low
molecular weight polymer. The lH-NMR(DM'SO-d63 spectrum is also
consistent with the formation of a 10W molecular weight poly~er.
Peaks in the 1.1-1.3 pp~ region show an appreciable level of
monoesters of propylene glycol are present. The ratio of the area
of the peak for the methylene groups of diesters of ethylene
glycol at -4.7 ppm to the area of the peak for the ~ethyl group of
diesters of propylene glycol at -1.4 ppm is measured. From this,
the molar ratio of incorporated ethylene/propylene glycols (E/P
ratio) is calculated to be 2.2:1. The solubility is tested by
weighing a small amount of material into a vial, adding enough
distilled water to make a 5X by weight solution, and agitating the
vial vigorously. The material is soluble under these conditions.
As can be seen from the foregoing, a wide variety of fabric
softener compos~tlons and laundry detergent composltions can be
prepared us~ng the sra's herein. Indeed, modern l~quid fabric
softeners are currently being prov~ded as high liquid (H20J
concentrates (5X-6X) wh~ch are des~gned to be diluted with water
by the consumer, ~n-home. Thus, the cnncentration of ingredients
per Example XI, hereinabove, can be essentially doubled to provide
such high concentrates. Thus, compositions oomprising from about
lkX to about 32% by weight of cationic fabric softener (e.g.,
DTDMAC), from about 4% to about 20% by weight of i~idazolinium
fabric softener and from about lX to about SX by weight of the
sra's herein are also encompassed by this invent~on.
W~th regard to laundry detergent composltions, highly
preferred composttions comprise from about 0.3% to about 3Y by
weight of the sra's herein and, as the detersive surfactant, fro~
about 3Z to about 2~X -by weight of a fatty acid polyhydroxy amide
surfactant (see U.S. Pat~nt 2,965,5769 corresponding to &B
809,060, c~ted above, incorporated herei-n by reference~,
preferably ~n combination with from about 5YO to about 2~X by
weight of a sulfated or sulfonated anionic surfactant such as the
C 1 2 -c 1 a alkyl ben~ene sulfonates, C 1 2 -c 1 a alkyl ethoxy sulfonates
(avg. E0 3-10; preferred), along with conventional amounts
(15%-5~/o) of conventional builders, including such preferred
.
W ~ 92/17~23 P~T/US92/OZ256
2 ~ 17 - 32 -
builders as Zeolite A, oxydisuccinates, and mixtures thereof, the
balance of such compositions comprising conventional detergent
ingredients at conYentional levels.
