Note: Descriptions are shown in the official language in which they were submitted.
~2~8~55
~.
s
E~RIC CONDITIONING AGENTS AND COMPOSITIONS
.,~
1-, Nabil George Kardouche
~. Philip Joseph Vincent Giardina
,
TECHNICAL FIELD
~i 5 Thisinvention relates to novel fabric conditioning
ayents and compositions which are especialiy useful in a laundry
process that involves washing followed by drying in a machine
dryer at elevated temperatures. Fabric cleaning and/or stain
', removal is provided in the washer; and fabric conditioning, i.e.l0 softening and destaticization, is provided principally in the
d ryer .
.,,
~ BACKGROUND ART
, , .
There have been a great many disclosures of compo-
sitions which, when used separately, provide detergency, stain
, 15 rernovai and fabric conditioning benefits. By fabric conditioning:- is meant improving softness, i . e. making its "handle" or texture
; more smooth, pliable and fluffy to the touch; and also reducing
static "cling" in the fabrics, i.e. destaticizing. Perhaps the most
~; common fabric conditioners known in the art are cationic com-
,~~ 20 pounds, especially quaternary ammonium and imidazolinium salts.
These compounds are ~widely r,1arketed for home use in the form of
liquid emulsions. They must be added to the home laundry in the
rinse cycle, not the wash, because cationic fabric conditioners
: interact with anionic substances present in the wash, such as
-` 25 anionic surfactants and builder saits, thereby rendering both
~' relatively ineffective. A commercial ~abric conciitioner of this
type is DOWNY (~) The Procter ~ Gamble Company.
. Another type of compound known for this purpose
comprises certain tertiary amines, as disclosed in Kenyon, Cana-
30 dian Patent no. 1,087,352 issued October 14, 1980. Clay as a
fabric ,conditioning ingredient is disclosed in Storm et al, U.S.
Patent No. 4,062,647 issued [)ecember 13, 1977.
,
t
~2~3!35~ - -
--2--
.
-Certain compositions are already known th3t provide
~ ......................................................... .
fabrics with a detergency treatment in a washer combined with a
degree of fabric conditioning treatment in a subsequent machine
dryer. Compositions of this kind are known in the art as
:5 îhrough-the-wash fabric comditioners, and are convenient to use
in that they do not require the use of a second product in the
rinse cycle or in the dryer to accomplish the fabric conditioning
objective. Baskerville, Jr. and Schiro,
disclose in U.S. patent 3,936,537 issued on February
7~ 10 3, 1976 a composition of this type wherein the fabric conditioning
agents are quaternary ammonium compounds.
The compositions of Baskerville et al comprise a r!~ixture
of two components: one component is granular and consists of
surfactant, cletergency builder, and other conventional detergent
:-15 adjuncts; while the other component consists of particles ranging
in size from 10 to 500 microns which comprise an intimate mixture
of a quaternary ammonium compound and a dispersion inhibitor in
the form of a solid organic r aterial which can be a paraffin wax,
alcohol, aliphatic carboxylic acid, or an estcr or polyethoxylate
~o thereof which has a solubility in water of 50 ppm. max. at 25GC,
:~ancl has a softening point in the range of 100 to 200F (about 38
to 93 C.).
A cornmercial cleaning/conditioning product which has
utilked the teachings of Baskerville, Jr. et al is BOLD-3 (~) The
25 Procter ~ Gamble Company.
Through-the-wash compositions utilizing a mixture of
tertiary amines and clay as fabric conditioner are disclosed in
Crisp et al , European Patent Publication no. 0 ,û1 1,340 published
May 28, 1980.
6attrell, in U.5. Patent no. 4,292,035 issued September
29, 1981, prepared through-the-wash compositions whercin fabric
softening was accomplished by a complex of clay with ccrtain
nitrogen containing organic compounds defined as primary, secon-
s~ dary and tertiary ar;lines and their water soluble or water dis-
35 pers;ble salts and organic quaternary ammoniur~, phosphonium and
sulfonium compounds. The water soluble or water dispersable
:"
.--
J ' l1~
~2~
-- --3--
saits that were eY~emplified ~Nere those hzving, as their anion,
' ~ hydroxide, chloride, bromide, sulfate or methosulfate. An
-~ example of salts of this kind was primary tallow amine hydro--' chloride.
. 5 Another means of providing fabric conditioning was
;C disclosed in Gaiser, U.S. Patent no. 3,442,692 issued May 6,
1969, as an article of man-Jfacture comprising a fabric c,onditioning
.~ composition in conjunction with a clispensing means for use in a
rnachine dryer. Preferred articles had the fabric conditioning
10 composition releasably affixed to an absorbent substrate, such as
a nonwoven tissue, in the form of an impregnate or coating of
q cationic fabric conditioning agent. The use of ccrtain polyols,
,~ especially sorbitan csters, as auxiliary fabric conditioning agents
~ in products of this kind is disclosed in Zaki et al, U . 5 . Patent
. . .
,~ 15 4, 022, 938 issued 1~,2y 1 O, 1977 . A commercial product that has
o utilized the teachings of Gaiser ana Z21ci et al is BOUNCE (~
The Procter ~ Gamble Company.
.~ Fabric conditioning articles of the Gaiser type whereinthe fabric conditioning composition was comprised of certain amine
salts are disclosed by l~ardouche in U.~. P3tent 4,2~7,155 issued
,,Y, December 2, 1980, This patent
; alluded to the possibility of adding these amine salts to the wash
, cycle or to the rinse cycle of a typical washing operation, and
apparently envisaged~a softening process taking place during the
one or the other of those tv o processes, respectively.
Clear distinctions between arnines, amides, amine salts,
quaternary ammonium salts, and other classes of nitrogen-con-
- taining chemical compounds appear in every textbook of organic
cheraistry. Fieser and Fieser in Organic Chemistry, 2nd Ed.,
Heath, Boston U.S.A. 11~50) point out a number of such distinc-
tions in chapter 10 beginning at page 220. Amine salts are
characterized as typically odorless, nonvolatile solids, even
though the amines from which they are derived are odoriferous
gases or liquids. The salts are ionic in nature in the solid state.
35 and possess characteristically sharp melting points which are
.~ higher than those of the corresponding amines. Low molecular
..
!
~2~85S
- --4--
.,,
3 . weight amine salts are readily soluble in water and exist in the
; solution in ionized condition.
SUMMARIZED DlSCLOSlJRE OF THE I~VEi~lTlON
One embodiment of this invention is a salt of a tertiary
5 amine and a carboxylic acid in the novel form of discrcte nodules.
These nodules have been found suitable for marketing as a fabric
; conditioning agent to be added to a laundry wash liquor at the
beginning of the cycle, along with a conventional detergent
product. The particle size of these amine salt nodules is from
10 about O . 05 to about 2 mm ., and the melting point is preferably
from about 35 to about 115 C.
-- The tertiary amine used to prepare the amine salt of
this invention has the formula
' P'2
P1 - N - R3
wherein R1, R2 and R are each, Independently, saturated or
-~ unsaturated and wherein R1 is a long chain aliphatic group hav-
ing from 12 to 22 carbon atoms and R2 and R3 are the same or
- different from each other and are selected from the group con-
20 sisting of aliphatic groups containing from 1 to 22 carbon atoms,
,i hydroxyalkyl groups of the formula -R40H wherein R4 is an
alkylene group having from 1 'to 3 carbon atoms, and alkyl ether
groups having the formula R5o(cnH2no)m- wherein R5 is hydro-
gen or an alkyl or alkenyl group having from 1 to 20 carbon
25 atoms, n is 2 or 3, and rn is from 1 to 20.
The carboxylic acid used to prepare the amine salt of
this invention has the formula
R6 ~ C - OH
30 wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or
aralkyl group having 1 to 22 carbon atoms, or a substituted
.,,
i:~
i~
~iLZ~ 55
5 -
alkyl, alkenyl, aryl, aikaryl, or aralkyl group having from 1 to
: 22 carbon aton s wherein the substituents are selected from the
group consisting of halogen, carboxyl, or hydroxyl.
The amine salt is formed by reacting the amine and the
5 carboxylic acid together to form a melt, which is then chilled in a
manner that produces discrete nodules. SLJitable nodulizing
processes are prilling, flalcing on a chill roll, and cooling in a
scraped wall heat exchanger followed by extruding.
A second embodiment of this invention is a fabric
10 conditioning/stain removal composition which comprises a blend of
the amine salt nodules described supra with nodules of enzyme,
I ~
~~ pero>(y bleach or porphine bleach prepared in a conventional
' manner.
A third er~bodiment of this invention is a through-the-
15 wash fabric cleaningifabric conditioning composition which com-
prises a blend of the amine salt nodules described supra with
, detergent granules containing a detergency builder and an ani-
onic, nonionic, arnphoteric or zwitterionic surfactant.
' In its processing embodiment, this invention provides a
20 process for conditioning fabrics which comprises the steps of (a)
contacting the fabrics with an effective amount of the amine salt
defined above in nodule form, and (b) subjecting the fabrics to a
temperature within the range from about 40 C. to about 95 C.
The nodules are preferably applied to the fabrics from an aqueous
25 bath, more preferably a laundry wash or rinse liquor; and the
fabrics are preferably caused to tumble in relative rlotion to each
,XA~' other while being subjected to the heat.
;'. This invention recognizes that a fabric conditioning
- agent for through-the-wash applications should be present in a
30 form that can be added to the wash; survives the wash and rinse
processes virtually unscathed; and is entrapped within the fabrics
when they are wrung out or spun before drying. Furthermore,
the chemical entity of which the fabric conditioning agent is
comprised should distribute well on and through the fabrics in a
35 mechanical drying process, and should be intrinsically a compound
that eFfectively softens and effectively destaticizes fabrics. The
'
8~Sr;~
~, ~h
--6--
. .~
t,~ amine salt nodules herein described meet each and every one of
,r, . ~ .
i` these varied criteria exceptionally well.
The amine salts utilized in this invention effectively
perform fabric softening and destaticizing functions. It is not
5 represented that amine salts are superior to conventional fabric
; conditioners when used conventionally in the laundry rinse. What
~~~ has not been taught or suggested ;n the prior art is that amine
salts, when in the form of discrete nodules, constitute a through-
;~ the-wash fabric conditioning ayent that accomplishes results never
10 before achieved. These nodules, when added at the beginning of
the wash cycle, pass through the wash and the rinse cycles
virtually unaffected by other rlaterials that are present, and in
turn do not themselves affect those other materials. This occurs
~ whether the nodules are added, together with a conventional
- 15 detergent composition, in the forrn of a separate fabric condi-
tioning agent, or as part of a fabric conditioning/stain removal
composition; or whether the nodules are added as part of a fabric
cleaning/conditioning product which constitutes the sole functional
composition in the laundry bath. Accordingly, this invention
20 makes possible for the first time the economic formulation of a
, multi-purpose product that cleans as well as comparable single-
purpose detergent compositions and conditions fabrics as well as
comparable single purpose fabric conditioniny agents. Compro-
mises are no longer necessary.
All compositional erhbodiments of this invention are
through-the-wash products. They all utilize amine salt nodule
technology which provides superior performance to such products
than compositions disclosed heretoFore.
The several embodiments of this invention are improve-
30 ments over the prior art in a number of different dimensions.
Amine salt nodules, when used as a single purpose product, make
possible the convenience of addiny an effective fabric conditioner
to the laundry at the same tirne as a conventionai detergent
product is added, thereby eliminating the neecl to add anythiny to
;~ 35 the laundry at a different time, e.g. in the rinse or in the
dryer .
. ~ ~
';:
.,
~L%~38S5
. . ~
7-
The fabric conditioning/stain removal product of this
- invention is a multi-purpose laundry additive that also can be put
''7 into the laundry tub along with the regular laundry detergent
product. Laundry additives containing enzyrnes and/or bleach are
. 5 widely sold to boost the effectiveness of ordinary detergent
`;`-~ products, for example B I Z ~) The Procter ~ Gamble Company .
This invention makes possible an improved laundry additive that
, also effectively conditions the fabrics.
A fabric cleaning/conditioning product makes possible a
10 single laundry product that effectively combines the two func-
i tions, cleaning and conditioning. It is simple and convenient to
A~ use, and does not require adding anything to the laundry at a
different time.
Conventional cationic fabric conditioners suffer from a
15 serious disaavantage in through-the-wash products: they are
partially soluble under washing conditions. They interact with
the anionic substances present in -the laundry liquor, especially
thc anionic surfactants often used. This interaction negates the
effectiveness of whatever materials are involved therewith. The
- ~ 20 result is less effective softening, less effective destaticization,
~- and less effective detergency than would otherwise be obtained.
Previous attempts to protect these materials from contact with the
laundry liquor, as disclosed for example in ~askerville et al cited
: hereinbefore, have resulted in particles having melting points so
25 low that they are not assured of surviving unscathed through the
wash cycle, especially when hot water is used.
~r, In contrast therewith, the amine salts of this invention
exist in the form of ion pairs within discrete nodules. Their high
and sharp melting points cause them to neither appreciably melt
- 30 nor dissolve in the laundry baths at the mildly elevated temper-
atures and at the pH's encountered in the wash and in the rinse,
respectively. Accordingly, the functions of the fabric condi-
tioner, the surfactant, the builder and indeed all other ingredi-
ents are accomplished just as though the products were utilized
35 independently.
..
, ~ g
: ~Z~1355
~,
, ~, `, ~
, ' DETAILED DESCRIPTION OF THE INVENTIO~J
, r~;
The components of this invention in its several embodi-
: ments are described individually as follows:
- The Essential Fabric Conditioning Compounds
.
5 The fabric conclitioning compounds essential to this
i~ invention are carboxylic acid salts of a tertiary amine which has
;~ at least one long aliphatic chain containing from about 12 to about
22 carbon atoms.
The tertiary ar ine salts are 2 direct procluct of the
reaction between a tertiary amine and a carboxylic acid.
The tertiary amines utilized in the present invention
- have the formula
R2
~1 ~ N - R3
15 wherein R1~ Rz and R3 are each, independently, saturated or
unsaturated and wherein R1 is a long chain aliphatic group
having from 12 to 22 carbon atoms and R2 and R3 are the same or
different from each other and are selected from the CJrOUp con-
sisting of aliphatic groups containing from 1 to 22 carbon atoms,
20 hydroxyalkyl groups of the formula -R40H wherein ~4 is an
alkylene group having 1 to 3 carbon atoms, and alkyl ether
groups having the formula R50(CnH2nO)m- wherein R5 is l~ydro-
-~5 gen or an alkyl or alkenyl group having from 1 to 20 carbon
atoms, n is 2 or 3, and m is from 1 to 20. Preferred amines are
: 25 those wherein P~1 is an aliphatic alkyl chain having from 12 to 22
carbon atoms, R2 iS an aliphatic alkyl chain having from 12 to 22
carbon atoms, and R3 is an aliphatic alkyl chain llaving from 1 to
3 carbon atoms. Especially preferred amines are those wherein
R1 and R2 are each, independently, a satura-ted linear alkyl chain
30 having from 16 to 18 carbon atoms, and R3 is methyl.
Examples of specific tertiary amines arc: lauryldimethyl-
amine, myristyldiethylamine, stearyldimethylamine, tallowdimethyl-
amine, coconutdimethylamine, dilaurylrnethylamine, distearyl-
,
.. . . . . .
s~
;, _ 9 _
.~ .
methylamine~ ditallowmethylamine, oleyldimethylamine, ~ioleyl-
~ propylamine, lauryldi(3-hydroxypropyi)amine, stearyldi(2-hy-
^~ droxyethyl)amine, trilaurylamine, laurylethylmethylamine, and
~(OC2H4)1 00H
C 11 N
(C2H4) 1 oOH
:~ The carboxylic acids utilized in the present invention
have the formula
: O
.. ,~ I I
i~ 10 R6 - C - OH
~ .,
wherein R6 iS hydrogen, or an alkyl, alkenyl, arvl, alkaryl or
aralkyl ~roup having 1 to 22 carbon atoms, or a substituted
- alkyl, alkenyl, aryl, alkaryl, or aralkyl group having of from 1
to 22 carbon atoms wherein the substituents are selected from the
group consisting of halo~3en, carboxyl, or hydroxyl. Preferred
fatty acids are those wherein F'`6 iS a long chain, unsubstituted
-. alkyl or alkenyl group l-aving from 11 to 21 carbon atoms; more
preferably a saturatecl linear alkyl group having from 15 to 17
carbon atoms.
Examples of specific carboxylic acids are: formic acid,
; acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid,
,
benzoic acid, 4-hydroxybenzoic acid, 3-chloro benzoic acid,
4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl~-
- 25 benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid,
(4-hydroxyphenyl)acetic acid, and phthalic acid.
Preferred carboxylic acids are lauric, myristic, palmitic,
stearic, oleic and mixtures thereof.
The amine salt is formed by a simple addition reaction,
30 well known in the art, whereby the tertiary amine is dissolved in
a solverlt such as methanol, ethanol, propanol, etc., and the acid
is added to the amine solution. Alternativeiy, the amine and acid
can simply be mixed and melted together with stirring to form the
~2~855
1 0
salt. The molten arnine salt can then be solidified by cooling to
room temperature. If the acid used to form the amine salt is a
polybasic acid (e.g., oxalic acid), the salt can be monobasic or
poiybasic, i.e., either one or more of the acid groups can be
- 5 utilized to neutralize the amine.
The formation of amine salts proceeds according to the
`~ following reaction:
O R~ O
- R -C-O-t-l + R1-N-R3 - ~ R -IC-O (3 (3 1 2
R3
If the reaction is carried out in a lower alcohol solvent
ï~i medium, the salt precipitates from solution, and can be recovered. either by filtration and/or evaporation of the solvent. Preferably
the amine and acid pair used in preparing amine salts of the
15 present invention should be chosen so as to produce amine salts
having a melting point somewhere within the range of from about
35 C. to 115 ~C. lmore preferably 35 C. -to 85 C.; most pref-
erably 55-65 C. ) . Such salts will be solid at room temperature
but will melt at typical machine dryer operating temperatures.
- 2û Amine salts having melting points higher than this range can be
used in the present invention by formulating them into composi-
tions which contain other materials as disclosed hereinafter so
- that the formulated composition has a melting point within the
desired range.
, 25 A molar ratio of amine to fatty acid of about 1:1 results
in the formation of the purest amine salt and the sharpest melting
point. If ratios higher or lower than this are used, the end
product of this reaction will contain the amine salt plus unreacted
amine or unreacted carboxylic acid, respectively. These unre-
- 30 acted compounds affect the nodules in a simi lar manner as do the
organic substances discussed in the section hereinafter which is
entitlecl "Auxiliary Fabric Conditioning Agents and Additives".
Accordingly the considerations involved in changing the molar
ratio of amine to fatty acid are dealt with therein.
Preferred amine salts for use herein are those wherein
the amine moiety is a C1 2 to C22 alkyl or alkenyl dimethyl amine
-
~ 8~55
. ~t~ r 1 1 ~
or a di-C12 to C22 alkyl or alkenyl methyl amine, and the acid
moiety is a C12 to C22 alkyl or alkenyl monocarboxylic acid. The
amine and the acid, respectively, used to form the amine salt will
often be of mixed chain lengths rather than single chain lengths,
5 since these materials are normally derived from natural fats and
oils, or synthetic processes which produce a mixture of chain
~ri lengths. Also, it is often desirable to utilize mixtures of dif-
ferent chain lengths in orcier to modify the physical or perfor-
mance characteristics of the softening compositions.
An especially preferred amine salt is methylditallowamine
.~ hydrotallowate, where the term tallow refers to the mixture of
alkyl moieties derived from tallow and the term tallowate refers to
the mixture of fatty acid moieties derived from tallow. This
compound can also be referred to as methylditallowammonium
.~ 15 tallowate or sometimes as rnethylditallowamine tallowate. Other
preferred amine salts for use in the present invention are
- stearyldimethylamine hydrostearate, stearyldimethylamine hydro-
`~ palmitate, distearylmethylamine hydropalmitate, distearylr:lethyl-
. amine hydrolaurate, and mixtures thereof. A particularly pre-
s 20 ferred mixture is stearyldimethylamine hydrostearate and
;~ distearylmethylamine hydrnmyristate.
The fabric conditioning compounds of this invention are
present in the detergent composition in the form of separate and
discrete nodules. The term "nodule" is used generically herein to
25 mean any discrete physical form that has been made by chilling
-i, from a mel t. One process for making such nodules is prilling,
;~, e.g. in a tower. Another process is flaking on a chill roll. Still
another method is based on cooling in a scraped wall heat ex-
changer and then extrudiny. Grinding or other comminuting
: 30 processes can also be employed. It is also possible to produce
very ~iny particles in the manner described supra, and then form
the nodules of this invention by a process involving agglomer-
ation, pelletizing, briquetting, or the like. All these processes
are conventional and well known in the art in relation to other
35 materials.
,, 5
~.
-
''' ~
~Z0~ ii5
~ - 1 2-
. ,
~j It is intended that the fabric conditioning agents func-
tion primarily in the dryer, and accordingly it is undesirable that
they melt or dissolve to any great extent in the washer. Time,
temperature and degree of agitation are not under the control of
the product formulator, so nodules must be rnade that survive
5 well over the entire range encountered in the rcal world of
manual and automatic washing processes, soaking and pretreating,
high and low temperature.
The fabric conditionin~ nodules, whether in the form of
prills, flakes, noodles, or other discrete particles, are of such a
10 size and composition that they become trapped, i.e. entangled in
~;, the clothes as discrete particles when spun or wrung out at the
end of the rinse cycle. They remain with the fabrics when
,
transferred to a mechanical drier and then melt, spread, and
condition the fabrics when heated to the worlcing temperature of a
15 mechanical dryer.
Configuration of the nodules also affects performance in
the dryer. The larger nodules will ter)d to be entrapped by the
outer surfaces of the fabrics, while the smaller nodules will
penetrate further toward the inner fibers. Thus larger nodules
, 20 tend to exert a stronger destaticizing efrect, which is a fabric
;~
surface phenomenon; while smaller nodules tend to exert a
stronger softening effect, which is in part a Function of how
~, individual fibers slide upon one another. Nodule penetration into
the fabrics is very much affected by the geometry of the nodule
25 as well as its size, decreasin~ in order from spheres to cylinders
to plates (e.g. from prills to noodles to flakes). This provides
another degree of freedom for the artisan to tailor make nodules
: to suit his particular purposes in the dryer as well as in the
wash and rinse.
An approximation for the purpose of this invention is
that the controlling dimension is the mean distance of the shortest
paths from the central points of the nodules to the surface.
Thus, ~or spheres or cylinders, this dimension i5 the radius for
ellipsoids, the minor radius; for plates, half the thickness of the
5 plates. For convenience, the phrases nodule size and particle
.'
',~
~s
, .. . ....
813S5
....
--1 3--
, t.
v
:; size as used herein will refer to twice this dimension; i.e. the
. ~ r,~'
~- diameter of spheres or cylinders, the thickness nf plates, etc.
U:,ing this definition of nodule size, sizes from about
0.05 to about 2 mm. are satisfactory; sizes from about 0.1 to
5 about 1 mm. are preferred; and sizes from about 0.2 to about
0.7 mm. are especially preferred.
Auxiliary Fabrics Conditioning Agents and Additives
-
.
~5
~$The cleaning/conditioning compositions of this invention
can be formulated with the fabric conditioning compounds dis-
10 cussed supra as the sole conditioning agents of the composition.
Alternatively, however, it is possible to utilize other conditioning
agents as well.
Mineral substances. One class of auxiliary fabric
conditioning agent is smectite clay. This mineral is disclosed in
;15 Storm et al, cited hereinbefore, as having both fabric softening
ar,d destaticizing properties. Clay particles carry through the
washing and rinsing cycles of a laundry process, became trapped
in the fabrics, and are available to condition the fabrics after
4.;subsequent drying. Inasmuch as -the mechanisms by which fabric
20 are conditioned by amine salts and by clay are different, a skilled
artisan is abie to utilize both technologies -to formulate a product
to best meet his specific needs . I n general terms, amine salt is a
- ~good softening agent and an especially good destaticizing agent,
,'while clay is a good softening agent. A blend of the two utili~es
;,fi25 these properties to great advantage and is a preferred compo-
sition. Suitable amounts of clay are within the range f rom about
1 % to about 20 % by weight of thc composition, preferably from
about 2 % to about 12 %. Clay can be added to the detergent
granule portion of the compositions, or in limited proportions can
30 be part of -the amine salt nodules.
As described in Storm et al, preferred smectite clays
have a cation exchange capacity of at least 60 meq. /100 gm. and
can be sodium or calcium montmorillonites; lithium, sodium or
magnesium saponites; or lithium, sodiun or magneshlm hectorites .
ss
--l 4--
3,~ Sodium montmorillonites are especially preferred, an example of
',7 which is Gelwhite GP (~1 which is marketed by Georgia Kaolin
Company .
Organic substances. A second class of auxiliary fabric
5 conditioning agents includes cationic compounds such as quater-
nary ammonium compounds, quaternary imidazoliniurn compounds
'; and polyarlido quaternized biurets. Also included in this class
are nonionic compounds such as protonated dipolyethoxy monoalkyl
~; amine; C1 0-C26 fatty acid esters of mono- or polyhydroxy alcoholsl0 containing 1-12 carbon atoms, especially glycerol esters; sorbitan
-, esters, especially sorbitan mono- and di-esters of C1 2-C20 fattyacids; and tertiary amines which have an iso-electric point from
8.3 to 9.8 and the structure R1R2P~3N where R1 is an alkyl group
having from 1 to 6 carbon atoms and R2 and R3 arc C1 0-C26
15 linear alkyl or alkenyl groups.
The abovementioned cationic and nonionic compounds are
most effectively employed by incorporating therm into the amine
salt nodules of this invention. Even within the nodules, how-
ever, they should be ernployed in limited quantities, inasmuch as
20 they tend to increase the solubility, lower the melting point, and
broaden the rnelting point range. Suitable quantities of com-
pounds of this type, when used at all, are from about l % to
about 200 % based on the weight of the nodules, preferably from
about 1 % to about 40 %. A person skilled in the art will recog-
25 nize that compounds' that are highly water soluble or have amelting point greatly different from the amine salts themselves will
appreciably affect the properties of the nodules, and accordingly
those compounds will be appropriate for use in relatively lower
amounts than cornpounds that are less water soluble and have
; 30 mel ting points closer to those of the amine salts . I lowevcr, these
auxiliaries can be useful because a suitable material can acJjust
physical properties into the ~esired range for an amine salt
nodule whose chemical fabric conclitioning properties are good but
whose physical properties are not altogether satisfactory alone.
35 This tlechnique can be employed, for example, to use an amine
"
-
LZ~8S5
5--
. 1
3 ~ salt that is a good softener but has too high a melting point when
pure .
Another class of compounds that can be optionally
,~ added to the nodules influence the properties of the nodules but
:' 5 are not themselves fabric conditioning agents. Such compounds
are herein referred to as fabric condi tioning additives . Among
'~' materials of this kind are ethoxylated surfactants, fatty alcohols
and acids, waxes, resins and solvents. The same considerations
~ ~ apply as for the cationic and nonionic conditioning agents de-
-!~ 10 scribed above, and they can be used in the same proportions.
~ As discussed hereinbefore, use of a molar excess of
`~ either the amine or the carboxylic acid used to synthesi~e the
q, amine salts of this invention will result in unreacted amounts of
whichever of these two ingre~lients is used in excess. The same
- 15 general considerations apply to these unreacted ingredicnts that
apply to the same ingredients when added separately, and apply
to the cationic and nonionic conditioning agents and the condi-
tioning additives discussed above.
,
Surfactant
According to one embodiment of this invention there is
, , .
utilized a surfactant selected from the group consisting of
anionic, nonionic, ampholytic and zwitterionic detergents and
mixtures thereof.
, Preferred anionic non-soap surfactants are water soluble
25 salts of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy
ether sulfate, paraffin sulfonate, alpha-olefin sulfonate, alpha-
sulfocarboxylates and their esters, alkyl glyceryl ether sulfonate,
fatty acid monoglyceride sul fates and sulfonates, alkyl phenol
polyethoxy ether sulfate, 2-acyloxy-alkane-1-sulfonate, and
30 beta-alkyloxy alkane sulfonate. Soaps are also preferred anionic
su rfac tants .
Especially preferred alkyl benzene sulfonates have about
9 to about 15 carbon atoms in a linear or branched alkyl chain,
more especially about 11 to about 13 carbon atorns. Especiaily
35 preferred alkyl sulfate has about 8 to about 22 carbon atoms in
.~
i,
~IL2~81~55
.~ . , .
--1 6--
the alkyl chain, more especially from about 12 to about 18 carbon
atoms. Especially preferred alkyl polyethoxy ether sulfate has
about 10 to about 18 carbon atorns in the alkyl chain and has an
;- avera~e of about 1 to about 12 -CH2CH2O- groups per molecule,
5 especially about 10 to about 16 carbon atoms in the alkyl chain
and an average of about 1 to about 6 -CH2CH2O- groups per
' molecule.
Especially preferred paraffin sulfonates are essentially
~,~ linear and contain from about 8 to about 24 carbon atoms, more
10 especially from about 14 to about 18 carbon atorns. Especially
preferred alpha-olefin sulfonate has about 10 to about 24 carbon
.~c atoms, more especially about lL~ to about 16 carbon atoms; alpha-
olefin sulfonates can be made by reaction with sulfur trioxide
followed by neutralization under conditions such that any sultones
15 present are hydrolyzed to the corresponding hydroxy alkane
sulfonates. Especially preferred alpha-sulfocarboxylates contain
`- From about 6 to about 20 carbon atoms; included herein are not
only the salts of alpha-sulfonated fatty acids but also their esters
made from alcohols containing about 1 to about 14 carbon atoms.
Especially preferred alkyl glyceryl ether sulfates are
ethers of alcohols having about 1 û to about 18 carbon atoms, more
especially those derived from coconut oil and tallow. Especially
- preferred alkyl phenol polyethoxy ether sulfate has about 8 to
about 12 carbon atoms in the alkyl chain and an average of about
25 1 to about 10 -C~12CH2O- grJups per molecule. Especially pre-
ferred 2-acyloxy-alkane-1-sulfonates contain from about 2 to about
9 carbon atoms in the aryl group and about 9 to about 23 carbon
atoms in the alkane moiety. Especially preferred beta-alkyloxy
alkane sulfonate contains about 1 to about 3 carbon atoms in the
30 alkyl ~3roup and about 8 to about 20 carbon atoms in the alkyl
moiety .
The alkyl chains of the foregoing non-soap anionic
surfactants can be derived from natural sources such as coconut
oil or tallow, or can be made synthetically as for example using
35 the ~ie~3ler or Oxo processes. Water solubility can be achieved
by using alkali metal, ammonium, or alkanolammonium cations;
~L2~ 355
--17--
sodium is preferred. Ma~nesium and calcium are preferred ca-
tions under circumstances described by Belgian Pat. No. ~'~3,636
, invented by Jones et al, issued December 30, 1976. r.lixtures of
: anionic surfactants are contemplated by this invention; a pre-
ferred mi>~ture contains alkyl benzene sulfonate having 11 to 13
carbon atoms in the alkyl group and alkyl polyethoxy alcohol
sulfate having 10 to 16 carbon atoms in the alkyl ~roup and an
average degree of ethoxylation of 1 to 6.
,~ Especially preferred soaps contain about 8 to about 24
carbon atoms, more especially about 12 ~o about 18 carbon atoms.
Soaps can be made by direct saponification of natural fats and
~, oils such as coconut oil, tallow and fish oil, or by the neutral-
, . .
ization of free fatty acids obtained from either natural or syn-
thetic sources. The soap cation can be alkali metal, ammonium or
alkanolammonium; sodium is preferred.
Preferred nonionic surfactants are water soluble com-
- pounds produced by the con~ensation of ethylene oxide with a
hydrophobic compound such as an alcohol, alkyl phenol, poly-
propoxy glycol, or polypropoxy ethylene diamine.
Especially preferred polyethoxy alcohols are the conden-
sation product of 1 to 30 mols of ethylene oxide with 1 ~ol of
branched or straight chain, primary or secondary aliphatic alcohol
; having fror~ about 8 to a~out 22 carbon atoms; r~ore especially 1
to 6 mols of ethylene~ oxide condensed with 1 mol of straight or
~3 25 branched chain, primary or secondary aliphatic alcohol having
from about 10 to about 16 carbon àtoms; certain species of poly-
~, ethoxy alcohols are commercially available from the Shell Chemical
- Company under the trade name "Neodol"* Especialiy preferred
polyethoxy alkyl phenols are the condensation product of about 1
to about 30 mols of ethylene oxide with 1 mol of alkyl phenol
having a branched or straight chain alkyl group containing abouL
- 6 to about 12 carbon atoms; certain species of polyethoxy alkylphenols are commercially available from the GAF Corporation
,~ under the trade name " Igepal" .*
Especially preferred polyethoxy polypropoxy glycols are
commercially available from E~ASF-Wyandotte under the trade name
'' * l'rademark
~2~ S5
--1 8--
;~
-. "Pluronic"* Especially preferreci conciensates of ethylene oxide
-. with the reaction product of propylene oxicie and ethylene diamine
are commercially available from BASF-Wyandotte under the trade
~ name "Tetronic".
Preferred se~T i-polar surfactants are water soluble amine
oxides containing one alkyl moiety of from about 10 to 28 carbon
atorns and 2 moieties selecte!d from the group consisting of alkyl
groups and hydroxyalkyl groups containing from 1 to about 3
~, carbon atoms, and especially alkyl dimethyl amine oxides wherein
10 the alkyl group contains from about 11 to 16 carbon atoms; water
soluble phosphine oxide detergents containing one alkyl moiety of
"~ about 10 to 28 carbon atoms and 2 moieties selected from the
.!.~
, group consisting of alkyl groups and hydroxyalkyl groups con-
taining from about 1 to 3 carbon atoms; and water soluble sulf-
15 oxicie detergents containing one alkyl r~oiety of frc-m about lO to
:- 2~ carbon atoms and a moiety selected trom the group consistingof alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Preferred ampholytic surfactants are water soluble
derivatives of aliphatic secondary and tertiary amines in which
20 the aliphatic moiety can be straight chain or branched anci
: wherein one of the aliphatic substituents contains from about 8 to
18 carbon atoms and one contains an anionic water-solubilizing
group, e.g. carboxy, sulfonate, sulfate, phosphate, or phos-
~ . phonate.
Preferred zwitterion!ic surfactants are water soluble
derivatives of aliphatic quaternary ammonium, phosphonium and
sulfonium cationic compounds in which the alipha~ic moieties can
be straight chain or branched, and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon atoms and one
30 contains an anionic water solubilizing group, especiaily alkyl-
dir;lethyl-ammonio-propane-sulfonates and alkyl-c:limethyl-ammonio-
hydroxy-propane-sulfonates wherein the alkyl ~roup in both types
contains from about 14 to 18 carbon atoms.
A typical listing of the classes anci species of surfac-
. 35 tants useful in this invention appear in U.S. Pat. No. 3,664,96i issued to l~orris on May 23, 1972,
* Trademark
~L2~ 51855
,
,: -19-
: This listing, and the ~oregoing recitation of
specific surfactant compounds and mixtures which can be used in
`; the instant compositions, are representative o~ such rnaterials but
~~ are not intended to be limiting.
Detergency Builder
., According tn one embodiment of this invention, there is
utilized a detergent builder selected from among any of the
conventional inorganic and organic water-soluble builder salts as
,' well as various water-insoluble builders. These water-soluble
;~ 10 builder salts serve to maintain the pH of the laundry solution in
the range of from about 7 to about 12, preferably frorn about 8 to
about 11. Furthermore, these builder salts enhance the fabric
cleaning performance of the overall detergent compositions while
at the same time they serve to suspend particulate soil released
from the surface of the fabrics and prevent its redeposition on
the fabric surfaces. ~dditionally, in certain compositions that
contain certain smectite clays as fabric softening agents, poly-
anionic builder salts cause these clays to be readily and homogen-
c eously dispersed throughout the aqueous laundering medium with
20 a minimum of agitation . The horT ogeneity of the clay dispersion is
necessary for the clay to function effectively as 2 fabric softener,
j~ while the ready dispersability allows granular detergent compo-
~ sitions to be formulated.
-' Non-limiting examples of suitable water-soluble, inor-
25 ganic alkaline detergent builder salts include alkali metal carbon-
ates, borates, phosphates, polyphosphates, bicarbonates and
silicates. Specific examples of such salts are sodium and potas-
sium tetraborates, perborates, bicarbonates, carbonates, tripoly-
phosphates, pyrophosphates, orthophosphates, and hexameta-
30 phosphates.
Examples of suitable organic alkaline detergency builder
salts are: (1 ) Water-soluble aminopolycarboxylates, e.g. sodium
and potassium ethylenediaminetetraacetates, nitrilotriacetates and
., ~J-(2-hydroxyethyl)-nitrilodiacetates; (2) Water-soluble salts of
-
-
, ~
~2q~3SS
-20-
phytic acid, e.g., sodium and potassium phytates-see U.$. Pat.
No. 2,739,942; (3) Water-soluble polyphosphonates~ including
specifically, sodium, potassium and lithium salts of ethane-l-
hydroxy-l, l-diphosphonic acid; sodium, potassium and lithium
salts of methylene diphosphonic acid; sodium, potassium and
lithium salts of ethylene diphosphonic acid; and sodium, pot-
assium and lithium salts of ethane-1,1,2-triphosphonic acid.
Other examples include the alkali metal salts of ethane-2-carboxy-
l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyl-
diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid,
ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tet-
raphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and
propane-1,2,2,3-tetraphosphonic acid; (4) Water-soluble salts of
polycarboxylate polymers and copolymers as described in U.S. Pat.
No. 3,308,067.
In addition, other polycarboxylate builders which can be
used satisifactorily include water soluble salts of mellitic
acid, citric acid, pyromellitic acid, benzene pentacarboxylic
acid, oxydiacetic acid, carboxymethyloxy-succinic acid and oxy-
disuccinic acid.
Certain zeolites or aluminosilicates ~nchan~e the functionof the alkaline metal pyrophosphate and add building capacity in
that the aluminosilicates sequester calcium hardness. One such
aluminosilicate which is useful in the compositions of the in-
vention is a crystalline water-insoluble hydrated compound of the
formula Naz (AlO2)z.(SiO2) xH2O, wherein z and y are integers of
at least 6; the molar ratio of z to y is in the range from 1.0 to
about 0.5, and x is an interger from about 15 to about 264; said
aluminosilicate ion exchange material having a particle size dia-
meter from about 0.1 micron to about 100 microns, preferably 1-10
microns; a calcium ion exchange capacity on an anhydrous basis of
at least about 200 milligrams equivalent of CaCO3 hardness per
gram; and a calcium ion exchange rate on an anhydrous basis of at
least about 2 grains/gallon/minute/gram. These synthetic alumin-
osilicates are more fully described in British Pat.
~1
12~35S
-21 -
~` No. 1,429,143 invcnted by Corkill et al, published Mar. 2~, 1976,
,
A second water-insoluble synthetic alu~inosilicate ion
-exchange material useful herein is ar~orphous in nature and has
-5 the formula Nax(xAlO2.5iO2), wherein x is a number from 1.0 to
1.2 and y is 1, said amorphous ma~erial being further charac-
terized by a Mg exchange~ capacity of from about 50 mg eq.
CaCO3/g. to about 190 mg eq. CaCO3/g. and a particle diameter
of from about 0.01 microns to about 5 microns. This ion ex-
10 change builder is more fully described in British Pat. ~io.
1,470,250 invented by B. H. Gedge e~ al, published Apr. 14,
1 977,
.:;
Enzyme
According to one embodiment of this invention there is
15 utili~ed an enzyme selecteo fror.1 the group consisting of protease,
arnylase and lipase. A disclosure of proteolytic enzymes suitable
for use in stain removal compositions appears in McCarty, U.S.
Patent 3,519,570 issued Jul~ 7, 1970. One method o~ preparing
enzyrne-containing nodules is also described therein.
A disclosure of amylolytic enzymes suitable for use in
stain removal compositions appears in t~esforges, U . 5 . Patent
3,661,786 issued Mayj 9, 1972. ~tabilization of enzymes by the
use of starch is also disclosed !by Desforges.
A disclosure nf discrete, shaped inorganic solids
r25 containing proteolytic or amylolytic enzymes appears in van
-Kampen et al, U.S. Patent 3,784,476 issued January 8, 1974.
The selected inorganic solids were soluble builder salts: sodium
and potassium sulfate and ortho-, pyro- and tripolyphosphates;
ammonium carbonate, bicarbonate and chioride; and the like.
30 Processes mentioned were milling, pelleting, extruding, stamping,
pressing, granulation, etc. to form ribbons, flakcs, threads,
spheres, noodles, tablets, pellets, granules, etc, Individual
particles were said to have a maxirnum dimension of not more than
15 mm . a minimum dirnension of not n~ore than 2 . 5 mm .; and
35 weigh between 0.05 and 100 mg~
,
SS
-22-
Extrusions ~ or~anic sol~ds contalning a num~er of
detergent adjuncts, includin~ enz~mes, are disclosed in Carter
et al, Canadian Patent 832,976 is-sued 3anuary 27, 1970. Suit-
able extrudable solids were said to be polyglycols; polyalkylene
oxides, C12-C20 alpha-olefin sulfonates; sodium N-coconut acid-
N-methyl taurate; condensa-tes between polyethylene oxide and
polypropylene oxide; nonionic surfactants; condensates of alky-
lene oxides with alcohols, alkyl phenols, amides, amines and acids;
soaps, starches and gelatinized starches; gelatin; and cellulose
derivatives.
It will be noted that the conglutinated granules of
McCarty, the shaped solids of Van Kampen et al, and the noodles
of Carter et al, are all encompassed by the term nodules as used
herein.
Pexoxy Bleach
According to one embodiment of this invention there is
utilized a peroxy bleach. ~he peroxy bleach can be inorganic or
organic, and if the former can optionally contain a peroxy bleach
activator.
By inorganic peroxy bleaches are meant inorganic peroxy-
hydrates; examples are alkali metal salts of perborates, per-
carbonates, persulfates, persilicates, perphosphates, and per-
polyphosphates.
Preferred inorganic peroxy bleaches are the sodium and
potassium salts of perborate monohydrate and perboxate tetra-
hydrate. Sodium perborate tetrahydrate is especially preferred.
By organic peroxy bleach is meant urea peroxide
CO(NH2)2.H2O2 or an organic peroxy acid or anhydride or salt
thereof which has the general formula
O~
%~ 55
Si ' ,~ --2 3--
-
wherein R is an alkylene group containing from 1 to about 20
carbon atoms, preferably 7 to 16 carbon atoms, or a phenylene
~^.group and Y is hydrogen, halogen, alkyl, aryl or any group
.
~,.,. which provides an anionic moiety in aqueous solution. Such Y
!~;, 5 groups can include, for example,
. . -- .
O O
.~ 11 /1
-C-OM, . -C-0-01~,1 or -:-OM
wherein M is H or a water-soluble, salt-forming cation.
Tne organic peroxyacids and salts thereof operable in
the instant invention can contain either one or two peroxy groups
-~ and can be either aliphatic or aromatic. When the organic per-
oxyacid is aliphatic, the unsubstituted acid has the general
-~ formula
'' 15 ~0
~- HO-O-C-(CH2)n-Y
:,
~, where Y, for example, can be CH3, CH2CI,
~S'
', O O O
-OM, -S-OM or -~-O-OM
'`~ 20 ~
~,~, and n can be an integer from 1 to 20. Diperazelaic acid (n = 7)
and diperdodecanedioic acid ~n - 10) are the preferred compounds
,~ of this type. The alkylene linkage and/or Y lif alkyl) can con-
tain halogen or other noninterfering substituents.
' 25 When the organic peroxyacid is aromatic, the unsub-
stituted acid has the general formula
~3 0
H~O-O-C-C6H4-Y
,- wherein Y is hydrogen, halogen, alkyl,
,, . ,:, . .. . .. . . .
i
~2~35iS
-24-
.';; O O
-C-OM , -S-OM or -C-O-OM
. O
for example. The percarboxy and Y groupings can be in any
relative position around the aromatic ring. The ring and/or Y
`~ group (if alkyl) can contain any noninterfering substituents suchas halogen ~roups. Examplles of suitable aromatic peroxyacids
and salts therof include monoperoxyphthalic acid, diperoxyt~re-
phthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt
10 of diperoxyterephthalic acid, m-chloroperoxybenzoic acid, p-nitro-
~-3 peroxybenzoic acid, ancJ diperoxyisophthalic acid.
; Of all the above described organic peroxyacid com-
,~ounds, the most preferred for use in the instant compositions
are diperdodecanedioic acid and diperazelaic acid.
Bv peroxy bleach activator is meant an organic peracid
precursor containing one or more acyl groups which is susceptible
to perhvdrolysis. The preferred activators are those of the
N-acyl or O-acyl-conmpound type containing an acyl radical R-CO-
wherein R is a hydrocarbon group having from 1 to 8 carbon
atoms. If the radicals R are aliphatic, they preferably contain 1
to 3 carbon atoms while, if they are aromatic, they preferably
contain up to 8 carbon atoms. R may be unsubstituted Qr substi-
-:, tuted with C1 3 alkoxy groups, halogen atoms, nitro- or nitrilo
groups. Aromatic radicals, In! particular, rnay be chloro- and/or
~: 25 nitro-subs~ituted. Examples of activators coming within this
. definition are certain N-diacetylated arnines, N-alkyl-N-suifonyl
carbonamides, N-acylhydantoins, cyclic N-acylhydrazides, triacyl
cyanurates, benzoic and phthalic anhydrides, O,N,N-trisubsti-
tuted hydroxyl amines, N,N'-diacyl-suifurlamides, 1,3-diacyl-4,5-
30 dialkyloxy-imidazolidines, acyla~ed ç31ycolurils and carboxylic
esters as disclosed in de Luque, IJ.S. patent 4,240,920 issued
December 23~ 1980. Another
useful peroxy bleach activator is C7 Cg acyl oxybenzene sulfo-
nate.
:,
~ ,,"!
~2(~15 I!~SS
--25-
Special advantages of using a combination of porphine
:_ and peroxy bleaches are also disclosed by de Luque. Combina-
tions of enzyme and peroxy bleach are disclosed by McCarty (Il),
- U.S. Patent 3,553,139 issued January 5, 19710
Halogen Bleach
-.;.
According to one embodir~ent of this invention tl-ere is
utilized a halogen bleach. Examples of suitable halogen bleaches
~,~ are N-chloro and N-bromo alkane sulfonamides and, more prefer-
ably, trichloro isocyanuric acid and sodium and potassium
dichloroisocyanurates.
Porphine Bleach
,~
. ~ According to one embodiment of this invention there is
. utilized a porphine bleach. This can be a porphine or a mono-,
di-, tri-, or tetra aza porphine; metal-free or metallated with
Zn(ll), Ca(ll~, Cd(ll), Mg(ll), Sc(lll), Al(lll) or Sn(lV); and
solubilized with one or more solubilizing groups which can be
anionic, nonionic or cationic in nature. The porphine bleaches
.: disclosed by Sakkab in U.S. patent no. 4,255,273 issued March
,~ 10, 1981 are suitable for use in this invention.
'~ 20
Preferred porphine bleaches are zinc or aluminum
phthalocyanine sulfonate.
Optional Ingredients
It is to be understood that the fabric cleaning/con-
:
'-. 25 ditioning compositions of the present invention can contain other
components commonly used in detergent compositions. Soil sus-
pending agents such as water-soluble salts of carboxymethyl-
cellulose, carboxyhydroxymethylcellulose, copolymers of maleic
anhydride and vinyl ethers, polyacrylic acid and salts thereof,
and polyethylene glycols having a molecular weight of about 400
to 10,000 are common components of detergent compositiOns and
can be used at ievels of about o, 5 s~ to about 10 ~ by weight.
,;
12~ 35~ii
~. .
~ .
--26--
` . Dyes, pigments, optical brighteners, and perfumes can be added
in varying ar.~ounts as desired.
- Other materials such as fluorescers, antiseptics, ~ermi-
cides, anti-tarnish agents, anti-corrosion agents, and anti-caking
' 5 agents such as sodium sulfosuccinate and sodium benzoate may
-, also be added. Other materials used in detergent compositions
that can be used herein are suds boosters, suds depressants,
fillers such as sodium sulfate, pH buffers, and hydrotropes such
.. as sodium toluene sulfonate and urea.
Other optional materials are related to fabric condi-
tioning: finishing agents, sizing agents, and anti-wrinkling
a~3ents such as corn starch which is disclosed in Belgian patent
~- no. 811,082 issued August 16, 1974
Processes of Manufacture and Use
The amine salt nociules of the instant invention are
prepared by the process described hereinbefore. In one embodi-
ment of this invention, they are marketed in this form as a fabric
conditioning a~ent without further processing. They are used by
- 20 simply adding to the beginning of the wash at the same time as
detergent is added; the user is then relieved of the need to adcl
additional ma$erials to ~he laundry at any later stage of the
~; washing, rinsing and; mechanical drying cycleO A suitable amount
of amine salt nodules in undiluted form to be added to a home
25 washer handling 8 pounds of clothes is in the range of 1 to 20
'~ g rams .
For convenience in dispensing or for other reasons it
may be desired to admix some other substance in discrete nodular
form to the a~ine salt nodules before packaging. A skilled
30 formulator is free to select the amount and type of diluent from
among substances that are inert, cheap, convenient, safe and
avai lable .
In a second embodiment of this invention, the amine sal-t
nodules are blended with an enzyme, peroxy bleach, haloyen
35 bleach, and/or porphine bleach to provide a combination fabric
.j
*
~ ~. ...
,~ 1;;~1)8BSCi
. !1 , 27
., ~
J ~.` conditioning and stain removal product. These four types of
stain removal ingredients have been defined hereinbefore.
~ The formulator of a product of this type has a wide
-i range of compositions to choose from, according to his desire to
.; 5 emphasize the varied propcrties contributed by these different
- ingredients. In general terms, the five ranges of compositions
identified in the table below are suitable, wherein all fiyures
.: given are percentages based on the fabric conditioning/stain
-` removal compositions. Each entry in the table includes two
ran~es: the first is the broad range of operability, and the
~ second (in parentheses) is the narrower, more preferred range.
i~ With reference to composition e, it will be noted that, in addition
to the nurnerical limits, the composition is required to contain one
; or more of the enzyme or bleach additives.
v;
.~ 15 a b c d e
. .
, amine salt 1-99 % 1-95 ~1-99 . 5% 1-99.995~ 1-99.995
.' fabric conditioner (5-96) (5-90) (5-98) (5-99.92) (5-99.98)
enzyme 1-50 0-50
-~ (4-25) ~0-25)
peroxygen bleach 5-95 0-95
(10-80) (0-80)
halogen bleach 0 . 5-60 0-60
i (2-40) (0-40)
porphine bleach 0 . 005-12 0-12
(0.02-8) (0-8,
diluent balance bal. bal. bal. bal.
Optionally, other additives may be added to this fabric
conditioniny/stain removal product. These other additives in-
clude, but are not limited to, surfactant or detergent builder as
30 described hereinbefore and those materials described herein in the
section entitled Optional Ingredients. The term diluent as used
in the table above includes not only materials that may be desired
to control cost, but also to control density, improve prvcessing
.,
'~,
-:~
. ~
12~0 ~3855
-28-
..
'~ (e.g. flowability), or to contribute sorne type of performance
functionality other than fabric conditioning or stain removal.
I t is preferred that the components of thé fa~ric con-
ditioning/stain removal product are in noduiar form as broadly
5 defined hereinbefore. Nodulizing of the stain removal ingreclients
~,can be achieved by a number of methods which are wel I recog-
3nized in the art. As these ingredients are intended for use in
the wash, the nodules containing them should be water soluble or
water dispersable. F~eferences that describe specific useful
lO techniques are McCarty, U.S. Patent 3,519,570; van Kampen et al
U.S. Patent 3,784,476; and especially Carter et al, Canadian
Patent 832,976; all of which have been cited hereinbefore.
Particle si7e of the nodules of stain removal ingredients
is preferably from about 0.05 to about 2 mm. This dimension is
15 less critical than the comparable dimension of amine salt nodules,
-because the nodules of stain removai ingredients are expected
only to be stable in shipping and storage and to dissolve or
.,
disperse in the wash, while the nodules of amine salt must sur-
vive the wash and rinse and be of proper size to become trapped
/20 in the fabrics and function effectively in the dryer.
-~In a third embodiment of this invention, the amine salt
nodules are adrnixed by proportionation, batch or continuous,
with detergent granules. This provides a through-the-wash
,~fabric cleaning/fabric conditioning composition -that accomplishes
i~25 multiple functions in a single droduct.
The detergent granules can be formed by any of the
-conventional techniques i.e., by slurrying the individual compo-
nents in water and then atomking and spray-drying the resultant
mixture, or by pan or drum granulation of the components. A
'30 preferred method of spray drying compositions in granule form is
disclosed in U.S. Pat. Nos. 3,629,951 and 3,629,g55 issued to
Davis et al on December 28, 1971.
The fabric cleaningl Fabric conditioning compositions of
this invention contain an anionic, nonis)nic, ampholytic or zwitter-
35 ionic surfactant, preferably anionic; a detergency builder; and an
amine salt fabric conditioning agent in nodular form as defined
.
!
s
` ~2al~5S
j" --2 9--
....
'`~ herein. Preferably the surfactant is from about 1 % to about 50 %
;~............... by weight of the composition, more preferably from about 5 to-~ about 30 %, most preferably from 10 to 20 %. Preferably the
'~ detergency builder is from about 5 % to about 95 % by weight of
';' 5 the composition, preferably from about 10 % to about 60 %, most
preferably from 15 to 40 5l. Preferably the fabric conditioning
' agent is from about 1 to about 30 % by weight of the composition,
preferably from about 3 to about 20 %, most preferably from 5 to
15 %.
!~ 10 The fabric cleaning/fabric conditioning compositions of
: ~ this invention can also, optionally, contain other additives.
These other additives include, but are not limited to, the stain
removal agents disclosed hereinbefore, and those materials de-
'~ scribed herein in the section entitled Optional Ingredients. These
15 additives can be incorporated into the detergent granules or,
; optionally, they can be prepared in the form of separate water
-, soluble or water dispersable nodules as described hereinbefore.In this event, the amine salt nodules, the additive nodules, and
the detergent granules are all blended by proportionation to form
' 20 the final product.
,s, The pH of the fabric conditioning agents and the fabric
conditioning/stain removal compositions of this invention have no
~, particular significance, as the former do not dissolve and the pH
of the latter is dominated by that of the detergent product that is
25 added to the wash at the same!tir;le. The pH of the cleaning/con-
L~ ditioning compositions is controlled in the manner that is cus-
tomary for detergent compositions and is no more critical than is
usual for detergent compositions. Accordingly, the pH of 1 9~
:.- aqueous solutions of the fabric cleaning/conditioning compositions
ii 30 is preferably from about 8 to about 12, with 9-11 especially
preferrecl .
Each of the embodiments of the invention is intended to
..
be used in 3 laundry process comprising washing, rinsing and
drying, The washing step can be by hand or in a machine,
35 manual or automatic. Soaking is optional. Rinsing can also be
. . ,
by hand or by machine, wrung out or spun to remove excess
,j
' ~IL2V~355i
`~;
--30--
. water. Although drying can be accomplished without difficulty byhanging on a line or spreading out in the sun, the fabric condi-
tioning benefits of this invention are more pronounced when
drying takes place in a mechanical dryer. Sometimes referred to
as an automatic dryer, such a device tumbles the clothes with hot
J air, usually at a temperature of from about 40 to about 95 C.,
most often at temperatures of 50-95 C. The amine salt nodules
of this invention, which are entangled in the clothes leaving the
rinsing step, thereupon soften or melt, spreading upon the fabric
surfaces to destaticize them and penetrating toward the inner
fibers thereof to soften them.
-" INDUSTRIAL APPLICATION
. ,,;
- Thc following examples describe the formulation of
specific compositions of this invention and the benefits derived
therefrom. They are illustrative of the invention and are not to
be construed as limiting thereof.
Example 1.
",
Flakes of hydrogenated tallow fatty acid (mol. wt. 274)
in the amount of 21.95 pounds and chunks of di (hydrogenated
tallow) methyl amine ~mol. wt. 520) in the amount of 38.05 pounds
were separately added in equimolar amounts to a stainless steel
-`~ vessel. Heat was applied and the ingredients melted; with con-
tinuous agitation the amine salt formed and was held overnight at
1 80 F.
The amine salt melt was prilled by atomizing with air in
a two-fluid nozzle and dropping through a cold-air tower. Nod-
ules comprising predominantly spherical droplets (prills) were
removed from the bottom of the tower and screened through a 10
mesh screen (openings 1.65 mm. ) to remove a few coarse frag-
30 ments. The median particle size of the prills used was deter-
.
,;i
T 9~ Z ~ /B f B S C j
` ~ ~ji~
b
3 1--
4' ',
mined by sieve analysis to be 0.4 mm.; with 80 ~ of the clis-
- ~, tribution between about 0.2 and 0.7 mm., and 96 % between about
- 0 .1 and 0 . 9 mm.
- Detegent granules having composition A as shown in
5 Table I below were prepared by crutchins all ingredients and
spray-drying in a conventional manner.
'~
Table 1.
.;
Ingredient A B
C13 linear alkyl benzene sulfonate 12.0 parts12.0 parts
10 Neodol 23 - 6.5Ta 0.5 2.0
Sodium tripolyphosphate 19 . 0
, ,~ Sodium pyrophosphate - 8 . 0
;' Sodium aluminosilicate ~Zeolite A) - 20.0
' ` "7
Sodium silicate (1.6 mol ratio SiO~/Na2O) 1.9 5.7
15 Sodium carbonate - 15 . 0
Sodium toluene sulfonate 0 . S 1 . 0
Polyacrylic acid (mol. wt. 60,000) 1.0
' Sodiurn Sulfate balance balance
~,~ Minor Ingredientsb 0.5 0.3
,~ 20 liilater ~ 6 ~ 5
~, Total 66.6 parts 82.2 parts
,~
A fabric cleaning/co~ditioning composition was prepared
by blending 13 parts of the amine salt nodules, 5.4 parts sodium
tripolyphosphate, and 10.0 parts sodium carbonate with 66.6 parts
25 of detergent granules described above, to make Product I of this
.,.
(a~ Trade Mark, Shell Chernical Company, for the nonionic
~; surfactant prepared by condensing 6.5 r~ols of ethylene
oxide with a mixture of C~12 and C13 linear alcohols, and
, then topping to remove low molecular weight odor bodies.
. 30 (b) Perfume, brightener.
,i~
"
,
,~
.~
;. ~LZ~85~i
`., .~
--32--
~ :.
', invention. This product was tested for fabric destaticizing in
comparison with commercially available products as will now be
described .
~inety-nine grams of productC were added to a Sears
5 KENMOREd washing machine filled with 17 gallons of water having
a hardness of 6 grams per U.S. gallon (Ca :1~4g =3:1) at 95 F.
- A wash load consisti--g of 33 items of mixed natural and
synthetic fabrics weighing 5 ~ pounds was washed, rinsed in the
~P same hardness water, and spun. The fabric bundle was then
lO dried for 60 minutes in a Sears KENMOREd electric machine dryer
in a controlled humidity environment (air dew point = 0 C.).
The foregoing treatments were repeated for a commercial
fabric cleaning/conditioning product, not of this invention, iden-
~- tified herein as Product l l . The washing treatment was also
lS repeated for TIDE~, a commercial detergent containing no special
fabric conditioning ingredients. However when the fabrics
. washed with TlDEe were dried, a sheet of BOli~CEe was adcied to
the dryer along with the fabrics at the beginning of the drying
` cycle.
Static cling was deterr,lined by two rnethods. After
t drying, the bundle of dried fabrics was transferred to a Faraday
cage and the voltage was read. Individual fabrics were then
removed from the bundlc in the Faraday cage and any fabrics
-~'s which were clinging ~to one ~nother were noted; a low number
3,~ ' ! -
s 25 (c) Product usage was calculated as though the product
contained 100 parts, even though the figures reported
above add up to only 95 parts . The remainder, 5 . 0
parts, which was omitted for experimental convenience,
would have been filled in commercial practice with
additional sndium sulfate which contributes virtually
nothing to the performance of cleaning or fabric condi-
tioning compositions.
(d~ Registered tradcmark, Sears Roebuck ~ Company
(e) Registered trademarks, The Procter ~ Gamble Company
.,,
~ ~Z( 181~55
--33--
i ~ r
indicates better static cling. The voltage after all fabrics were
- removed was rated, and the voltage difference linitial minus final)
was recorded. A iow number indicates a low level of static cling.
The table below gives results for two comparative tests.
~ .
Voltage Dif~erenceFabrics Clinging
Product I 33
Product l l81 9
Product 1 30 0
TIDE/BOUNCE15 0
These results show tha~ the destaticization provided by
a fabric cleaning/conditioning composition of this invention is
considerably better than a currently marketed product of this
type, and is nearly as good as is provided by using two sepa-
rate-purpose products.
i, 15 Similar results are obtained when the amine salt is
mixed for only ten minutes after melting and before prilling.
,~;
Example 2.
A fabric cleaning/conditioning composition was prepared
by blending 13 parts of the amine salt nodules hereinbefore
20 described in Example 1, 82 parts of d~tergent granules A as
defined in Example 1, and 5 parts sodium montmorillonite clay.
This product identified herein as Product l l l of this invention was
tested for fabric softening in comparison with commercially avail-
able products as will now bc described.
Eight and one-half grams of product were added to a
~- tub of miniature washer filled with one and one-half gallons of
water having a hardness of 6 grams per U.S. gallon
(Ca :Mg -3:1 ) at 95 F. A wash load consisting of 4 fabric
swatches 15 inches square of cotton terry cloth and 2 fabric
,.,
r .
5~
- ~
~ZQ8~3SS
--311--
~, swatches 11 inches square each of polyamide, polyester and
cotton/ polyester blend was washed for 12 minutes, rinsed in the
same hardness water, and spun.
The foregoing treatments were repeated for Prcduct l l,
5 the commercial fabric cleaning/conditioning product not of this
- invention . The washing treatment was repeated twice for T I DE .When one set of fabrics washed with T I DE were rinsed, 3 . 9 ml . of
DOIII~NY were added to the tub.
.~ The damp fabrics from each treatment were dried sepa-
~j 10 rately for 60 minutes in an electric machine dryer. Softness of
- the terry cloth swatches was graded by an expert panel, result-
ing in the following (data in panel score units, LSD (9596) = 0.5).
., _
TIDE plus DO\Y~iY +1.4
?roduct l l l +1 . 3
: 15I'roduct l l O
Product I -O . 6
T I D E -2 . 1
' Fabrics treated wilh Product l l l, which contained amine
,~ salt nodules and clay, were virtually as soft as those treated
20 separately with the single purpose products TIDE and DOWNY.
These fabrics were distinctly softer than those treated with
Product l l which contained cationic softener agglomerates plus
clay as taught by Baskerville! et al cited hereinbefore. Fabrics
treated with Product 1, containing amine salt nodules as the sole
25 softening agent, were substantially softer than those washecl in
regular detergent, but were not so soft as those washed in a
- comparable through-the-wash composition containing clay.
Example 3.
Detergent granules having composition B as identified in
30 Table I above were prepared in the same manner as was used for
, "
-
.,.
_ -~
. ~ .i
3~Z~S5
; tj~'~' , -35-
-
composition A. A fabric cleaning/conditioning composition was
prepared by dry blendin~3 82.2 parts of detergent granules B
with 8.7 parts of the aminle salt nodu!es hereinbefore described in
:-~ Example 1. This product is herein identiFied as Product IV of
,-' 5 this invention. Another fabric cleaning/conditioning compositionwas prepared by dry blending 82.2 parts of detergent granules B
-~ with 15 . 6 parts of a fabric conditioning additive nodule comprising
~, 2.3 parts ditallowdimethylammonium chloride, 3.1 parts sodium
montr~orillonite clay and 5 .1 parts inert ingredients. This
lO product is herein identified as Product V which is not, however,
according to this invention but is a reference composition.
Products IV and V were tested for clay soil detergency
'~ ' using the following n ethod. Soiled swatches of cotton, poly-
est~r/cotton blend, and polyester were prepared by staining in a
L5 controlled rnanner with clav padded on from a water slurry and
- dried. h;iniwash tubs were filled with one U.S. gallon of water at
95 ~C. and having, respectively, 2, 8 or 12 grains per U.S.
gallon of ilar~ness (Ca :Ais =3:1 ), and approximately six grams
-, of productg were acided together with a speckle containing 0.03
,~ 20 grams of PEG 80001~ and 0.09 grams inert ingrec~ients. Swatches
were then washed in the test product and dried. Whiteness was
' deterr~ined using a Hunter Color Difference rneter, using the
- equation ~-(7L2 _ 40Lb)/700. Results were as follows, where
each entry in the table is a whiteness value avera~3ed over all 3
25 water hardnesses.
,,
Fabric Type Product IVProduct V
cotton 27 23
polyester/cotton blend 59 55
polyester 50 45
30 ~9) Product usayes were adjusted in the manner described in
footnote (c) in relation to Product 1.
(h) Polyethylene glyccl having a molecular weight of 8000.
-
; ~ ~
1"$ ~2~8~5S
5 . -36-
~` On every fabric type, the swatches washed in Product IV were
- significantly whiter (95 ~ statistical level) than those washed in a
corresponding manner in Product V.
~ Lipid soil removal was evaluated by washing swatches of 65
- - 5 polyester/35 cotton blend which had been soiled by panelists
rubbiny over their faces, cheeks and necks in a controlled man-
ner. The swatches were cut in half, and each half washed in the
two products separately in the manner described above, except
-: that speckles were not added. Grading was done by expert
a; 10 graders who compared the two halves of each original swatch
against each other. Results were as follows where entries in the
table are differences in panel score units between Product IV and
Product V (positive values mean Product IV is cleaner). Each
~: entry represents 10 panelists and 3 expert graders. The differ-
ences in 2 grain and 12 grain water are significant at the 95
- level.
- Panel Score Units
water hardness ( Product IV - Product V~
- 2 grain + 0. 84
20 8 grain + 0. 63
i' 12 grain + 0.96
",
.
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.,
