U.S. patent number 3,861,870 [Application Number 05/357,130] was granted by the patent office on 1975-01-21 for fabric softening compositions containing water-insoluble particulate material and method.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Francis Louvaine Diehl, James Byrd Edwards.
United States Patent |
3,861,870 |
Edwards , et al. |
January 21, 1975 |
FABRIC SOFTENING COMPOSITIONS CONTAINING WATER-INSOLUBLE
PARTICULATE MATERIAL AND METHOD
Abstract
Fabric softening compositions with improved conditioning
properties comprising a cation-active fabric softener and certain
substantially water-insoluble particulate materials are described.
The compositions permit the simultaneous attainment of softening,
ease of ironing, anti-wrinkling and appearance benefits of fabrics
treated therewith.
Inventors: |
Edwards; James Byrd (Roselawn,
OH), Diehl; Francis Louvaine (Wyoming, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
23404419 |
Appl.
No.: |
05/357,130 |
Filed: |
May 4, 1973 |
Current U.S.
Class: |
510/516; 510/522;
510/525; 8/115.6 |
Current CPC
Class: |
D06M
15/11 (20130101); C08F 10/00 (20130101); D06M
13/46 (20130101); D06M 23/00 (20130101); C11D
3/001 (20130101); D06M 15/233 (20130101); C11D
3/37 (20130101); D06M 15/423 (20130101); C11D
1/62 (20130101); C11D 3/124 (20130101); C08F
4/025 (20130101); D06M 13/463 (20130101); D06M
15/256 (20130101); C08F 10/00 (20130101); C08F
4/69 (20130101) |
Current International
Class: |
C11D
3/12 (20060101); C11D 3/00 (20060101); D06M
15/423 (20060101); D06M 23/00 (20060101); D06M
15/37 (20060101); D06M 15/233 (20060101); D06M
15/256 (20060101); D06M 13/46 (20060101); D06M
15/11 (20060101); D06M 13/00 (20060101); D06M
13/463 (20060101); C11D 1/38 (20060101); D06M
15/21 (20060101); C11D 1/62 (20060101); D06M
15/01 (20060101); C11D 3/37 (20060101); D06c
019/00 () |
Field of
Search: |
;252/8.6,8.8
;8/115.6,137 ;117/139.5CF,139.5A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Claims
We claim:
1. A fabric softening composition comprising
a. from about 0.5% to about 95% by weight of a cation-active fabric
softener compound having from one to two straight-chain organic
groups of from 8 to 22 carbon atoms; and
b. from about 95% to about 0.01% by weight of a substantially
water-insoluble particulate material having
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1;
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree.C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
2. A composition in accordance with claim 1 wherein the
cation-active softener compound has the formula ##SPC5##
wherein R is hydrogen or an aliphatic group of from 1 to 22 carbon
atoms; R.sub.1 is an aliphatic group having from 12 to 22 carbon
atoms; R.sub.2 and R.sub.3 are each alkyl groups of from 1 to 3
carbon atoms; and x is an anion selected from halogen, acetate,
phosphate, nitrate and methyl sulfate radicals.
3. A composition in accordance with claim 2 wherein the
substantially water-insoluble particulate material is selected from
the group consisting of surface-modified starch,
poly(methylmethacrylate), poly(tetrafluoroethylene), polystyrene,
poly(styrenedivinylbenzene), poly(vinyltoluene),
poly(melamineformaldehyde-ureaformaldehyde),
poly(ureaformaldehyde), glass beads, glass microballoons, starch,
and mixtures thereof.
4. A liquid fabric softening composition comprising
a. from about 1% to about 30% by weight of a cation-active fabric
softener compound having from 1 to 2 straight-chain organic groups
of from 8 to 22 carbon atoms; and
b. from about 0.01% to about 10% by weight of a substantially
water-insoluble particulate material having:
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1,
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree.C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
5. A composition in accordance with claim 4 wherein the
cation-active fabric softener compound is present in an amount from
about 2% to about 25% by weight.
6. A composition in accordance with claim 5 wherein the
substantially water-insoluble particulate material is present in an
amount from about 0.1% to about 6% by weight.
7. A composition in accordance with claim 6 wherein the
cation-active softener compound has the formula ##SPC6##
wherein R is hydrogen or an aliphatic group of from 1 to 22 carbon
atoms; R.sub.1 is an aliphatic group having from 12 to 22 carbon
atoms; R.sub.2 and R.sub.3 are each alkyl groups of from 1 to 3
carbon atoms; and x is an anion selected from halogen, acetate,
phosphate, nitrate and methyl sulfate radicals.
8. A composition in accordance with claim 7 wherein the
substantially water-insoluble particulate material is selected from
the group consisting of surface-modified starch,
poly(methylmethacrylate), poly(tetrafluoroethylene), polystyrene,
poly(styrenedivinylbenzene), poly(vinyltoluene),
poly(melamineformaldehyde-ureaformaldehyde),
poly(ureaformaldehyde), glass beads, glass microballoons, starch,
and mixtures thereof.
9. A solid fabric softening composition comprising
a. from about 1% to about 60% by weight of a cation-active fabric
softener compound having from 1 to 2 straight-chain organic groups
of from 8 to 22 carbon atoms; and
b. from about 0.1% to about 50% by weight of a substantially
water-insoluble particulate material having:
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1;
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree.C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
10. A composition in accordance with claim 9 wherein the
cation-active fabric softener is used in an amount from about 5% to
about 40% by weight.
11. A composition in accordance with claim 10 wherein the
substantially water-insoluble particulate material is present in an
amount from about 0.2% to about 25% by weight.
12. A composition in accordance with claim 11 wherein the
cation-active fabric softener is selected from the group consisting
of
i. quaternary ammonium compounds of the formula ##SPC7##
wherein R is hydrogen or an aliphatic group of from 1 to 22 carbon
atoms; R.sub.1 is an aliphatic group having from 12 to 22 carbon
atoms; R.sub.2 and R.sub.3 are each alkyl groups of from 1 to 3
carbon atoms; and X is an anion selected from halogen, acetate,
phosphate, nitrate, and methyl sulfate radicals; and
ii. imidazolinium salts of the formula ##SPC8##
wherein R.sub.6 is an alkyl containing from 1 to 4 carbon atoms,
R.sub.5 is an alkyl containing from 1 to 4 carbon atoms or a
hydrogen radical, R.sub.8 is an alkyl containing from 1 to 22
carbon atoms, R.sub.7 is an alkyl containing from 8 to 22 carbon
atoms, and X is an anion.
13. A composition in accordance with claim 12 wherein the
substantially water-insoluble particulate material is selected from
the group consisting of surface-modified starch,
poly(methylmethacrylate, poly(tetrafluoroethylene), polystyrene,
poly(styrenedivinylbenzene), poly(vinyltoluene),
poly(melamineformaldehyde-ureaformaldehyde),
poly(ureaformaldehyde), glass beads, glass microballoons, starch,
and mixtures thereof.
14. A composition in accordance with claim 13 wherein the
quaternary ammonium fabric softener is selected from the group
consisting of tallow trimethyl ammonium chloride; ditallow dimethyl
ammonium chloride; ditallow dimethyl ammonium methyl sulfate;
dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow)
dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride;
dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium
chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate;
dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl
ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow
dimethyl ammonium nitrate; di(coconut-alkyl) dimethyl ammonium
chloride.
15. A method for treating fabrics to impart desirable fabric-care
benefits, said method comprising treating fabrics in an aqueous
liquor comprising:
a. from about 0.2 ppm (part per million) to 5,000 ppm of a
cation-active fabric softener compound having from 1 to 2
straight-chain organic groups of from 8 to 22 carbon atoms; and
b. from about 0.2 ppm to 1,000 ppm of a substantially
water-insoluble particulate material having:
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1;
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree.C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
16. A method in accordance with claim 15 wherein the cation-active
fabric softener compound is used in a amount from about 2.5 ppm to
about 1,000 ppm.
17. A method in accordance with claim 16 wherein the substantially
water-insoluble particulate material is selected from the group
consisting of surface-modified starch, poly(methylmethacrylate),
poly(tetrafluoroethylene), polystyrene,
poly(styrenedivinylbenzene), poly(vinyltoluene),
poly(melamineformaldehyde-ureaformaldehyde),
poly(ureaformaldehyde), glass beads, glass microballoons, starch,
and mixtures thereof.
Description
BACKGROUND OF THE INVENTION
This invention relates to fabric softening compositions which
comprise in addition to conventional fabric softening agents a
substantially water-insoluble particulate material. These
compositions impart to fabrics treated therewith in a conventional
manner a series of fabric-care benefits including anti-wrinkling,
ease of ironing, softening, folding ease, enhanced fabric
drapability and appearance improvement, which cannot be achieved
simultaneously from the use of softening and fabric conditioning
compositions known in the art.
Modern fabric-softening and conditioning compositions, washing
machines and dryers are subject to continuous improvement with a
view to achieve a series of fabric benefits such as, for example,
softening, body, anti-wrinkling, ease of ironing, and improvement
in appearance. As of yet, however, no single fabric conditioning
composition is available capable of providing textiles treated
therewith in the conventional matter with a broad spectrum of
fabric-care benefits as, for example, referred to hereinbefore.
For example, present day fabric softeners impart a softness to the
fabric (actually this softness is best likened to a tactile
sensation of lubricity, which is distinguishable from fabric
softness occasioned by enhanced fabric bulkiness) and control of
electrostatic charge. Modern day washing machines and dryers by
means of elaborate cycles and temperature control are able to
markedly improve the extent of fabric wrinkling. Other products
such as well-known laundry starches, if desired in combination with
particulate organic constituents having a melting point below
ironing temperatures, impart when applied after the washing cycle,
crease permanence and ease of ironing benefits and also impart a
body to the fabric, i.e., a sizing effect.
The softening compositions of this invention, however, impart all
of these and other benefits simultaneously when applied in a
conventional manner. That is, the softening compositions of this
invention, by some imperfectly understood physical-chemical
interaction at the fiber or yarn level, impart, through the rinse
cycle or in general through the conditioning operation, the
benefits enumerated, by way of example, hereinbefore. These
benefits are solely attributable to the presence of a substantially
water-insoluble particulate material as hereinafter defined in
combination with cation-active fabric softener compounds.
Fabric softening compositions on the basis of quaternary ammonium
compounds such as ditallowdimethylammonium chloride are known in
the art and have been commercialized for a decade as rinse
softening compositions. Other approaches to fabric softening
involve the use of various clay particles. For example, U.S. Pat.
No. 3,033,699, pertains to compositions and processes for improving
the anti-static properties of synthetic fiber yarns through the
application of an aqueous suspension of magnesium montmorillonite
clay and an alkali stabilized colloidal silica salt. U.S. Pat. No.
3,594,212 teaches that cellulosic fibrous materials can be softened
by treatment thereof with montmorillonite clays and polyamines or
polyquaternary ammonium compounds. U.S. Pat. No. 3,063,128
discloses a process for controlling static properties of synthetic
textile fibers and exhibiting moisture regain not exceeding 5%
through the application of an aqueous suspension of montmorillonite
to the fibers followed by drying such as to insure that at least
about 0.5% of the montmorillonite clays have been deposited on the
fibers. The co-pending applications; Gloss, U.S. Ser. No. 333,104,
filed Feb. 16, 1973, and Bernardino, Ser. No. 337,331, filed Mar.
2, 1973; relate to the use of smectite-type clays in fabric
softening compositions.
Other known fabric conditioning compositions containing various
particulate materials for the purpose of a specific function are
known in the art. Examples thereof are detergent scouring
compositions containing water-insoluble particulate materials,
which mostly have a particle diameter in the range from about 50 to
100 micrometers and a hardness of about 7 on the Moh scale.
Thermoplastic particulate materials are also known in the art and
have been used in connection with laundering and conditioning
operations, mainly for the purpose of textile finishing, ease of
ironing, and sizing. These thermoplastic materials are softened or
fused during, e.g., ironing thereby providing a sizing to the
fabric.
The prior art teachings, however, aim at achieving specific
functions and objectives which, as regards the properties of the
particulate materials, i.e., water-insolubility, shape, integrity,
particle size diameter, hardness, presence of exchangeable alkaline
earth metal ions and melting (softening) temperatures, are
essentially different from the physical properties of the
water-insoluble particulate materials which qualify for use in the
compositions of the instant invention.
In any event, prior art fabric conditioning compositions containing
the particulate materials referred to hereinbefore do not produce
the fabric conditioning benefits of the instant compositions, and
in many cases, tend to impart harshness or stiffness to the
fabric.
Accordingly, it is an object of the present invention to provide
fabric softening compositions comprising cation-active fabric
softener compounds and water-insoluble particulate materials which
impart anti-wrinkling, ease of ironing, softening, anti-static,
folding ease, enhanced fabric drapability and appearance benefits
to fabrics treated therewith.
It is an additional object of the present invention to provide
fabric softening compositions capable of conditioning fabrics
treated therewith with a view to obtaining a degree of enhanced
tactile and appearance properties by reference to what results from
the use of fabric softening compositions applied in a conventional
manner, i.e., during the rinsing operation.
By utilization of certain particulate materials capable of
conferring desirable fabric benefits when present in combination
with cation-active fabric softener compounds, these above-described
objectives can now be attained and fabric softening compositions
formulated which are capable of imparting to fabrics treated
therewith a series of desirable properties including
anti-wrinkling, ease of ironing, fabric softening, anti-static,
folding ease, enhanced fabric drapability, and appearance
benefits.
SUMMARY OF THE INVENTION
The instant invention provides softening compositions which are
capable of imparting a broad range of desirable properties to
fabrics treated therewith. Such compositions comprise:
a. from about 0.5% to about 95% by weight of a cation-active fabric
softener compound having from one to two straight-chain organic
groups of from 8 to 22 carbon atoms; and
b. from about 95% to about 0.01% by weight of a substantially
water-insoluble particulate material having:
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1;
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree. C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
In its method embodiment, the present invention provides a process
capable of simultaneously imparting a series of desirable
fabric-care benefits to textiles treated therewith. Such method
comprises treating textiles in a liquor comprising:
a. from about 0.2 ppm (part per million) to 5,000 ppm of a
cation-active fabric softener compound having from one to two
straight-chain organic groups of from 8 to 22 carbon atoms; and
b. from about 0.2 ppm to 1000 ppm of a substantially
water-insoluble particulate material having;
i. an average particle size in the range from about 1 to about 50
micrometers;
ii. a shape having an anisotropy of about 5:1 to 1:1;
iii. a hardness of less than about 5.5 on the Moh scale;
iv. a melting point above about 150.degree.C; and
v. substantial freedom from exchangeable calcium and magnesium
ions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to fabric softening compositions
capable of imparting a series of fabric-care benefits to fabrics
treated therewith.
These compositions comprise (1) a cation-active fabric softener
compound; and (2) a substantially water-insoluble particulate
material.
Unless indicated to the contrary, the "percent" indications stand
for "percent by weight."
The essential cation-active fabric softener compound will normally
be employed in the compositions of this invention in an amount from
about 0.5% to about 95%. Obviously, depending upon physical state
and intended use of a particular composition, the amount of
cationic fabric softener can vary. For example, a liquid softening
composition preferably comprises from about 1% to about 30%,
especially from about 2% to about 25% of said cationic softener.
If, in liquid compositions, more than about 30% is used, product
stability problems may occur, such as, for example, thickening and
the possible formation of undesired gel. If less than 0.5% is used,
excessive amounts of softener composition are required to achieve
acceptable softening, i.e., this creates uneconomical conditions as
regards storage and handling of low-active formulae. Solid,
granular or powdered, softening compositions of this invention
preferably comprise from about 1% to about 60%, especially from
about 5% to about 40% of cation-active ingredient; the upper limit
being dependent upon the physical state of the softening ingredient
and, if applicable, upon the amount of drying and/or granulating
carrier material to be added for obtaining a solid softening
composition. The lower cation-active limit, as for the liquid
softening composition, is based on economical and performance
considerations, i.e., handling cost versus overall fabric benefits
desirable from a given amount of solid softening composition.
The cation-active organic fabric softener compounds, for use in the
compositions of this invention, are known fabric-softening
compounds. Generally, these comprise cationic nitrogen-containing
compounds such as quaternary ammonium compounds and amines and have
one or two straight-chain organic groups of at least eight carbon
atoms. Preferably, they have one or two such groups of from 12 to
22 carbon atoms. Preferred cation-active softener compounds include
the quaternary ammonium softener compounds corresponding to the
formula ##SPC1##
wherein R is hydrogen or an aliphatic group of from 1 to 22 carbon
atoms; R.sub.1 is an aliphatic group having from 12 to 22 carbon
atoms; R.sub.2 and R.sub.3 are each alkyl groups of from 1 to 3
carbon atoms; and X is an anion selected from halogen, acetate,
phosphate, nitrate and methyl sulfate radicals.
Because of their excellent softening efficacy and ready
availability, preferred cationic softener compounds of the
invention are the dialkyl dimethyl ammonium chlorides, wherein the
alkyl groups have from 12 to 22 carbon atoms and are derived from
long-chain fatty acids, such as hydrogenated tallow. As employed
herein, alkyl is intended as including unsaturated compounds such
as are present in alkyl groups derived from naturally occurring
fatty oils. The term "tallow" refers to fatty alkyl groups derived
from tallow fatty acids. Such fatty acids give rise to quaternary
softener compounds wherein R and R.sub.1 have predominantly from 16
to 18 carbon atoms. The term "coconut" refers to fatty acid groups
from coconut oil fatty acids. The coconut-alkyl R and R.sub.1
groups have from about 8 to about 18 carbon atoms and predominate
in C.sub.12 to C.sub.14 alkyl groups. Representative examples of
quaternary softeners of the invention include tallow trimethyl
ammonium chloride; ditallow dimethyl ammonium chloride; ditallow
dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium
chloride; di(hydrogenated tallow) dimethyl ammonium chloride;
dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium
chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated
tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl
ammonium chloride; dihexadecyl dimethyl ammonium acetate; ditallow
dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate;
di(coconut-alkyl) dimethyl ammonium chloride.
An especially preferred class of quaternary ammonium softeners of
the invention correspond to the formula ##SPC2##
wherein R and R.sub.1 are each straight chain aliphatic groups of
from 12 to 22 carbon atoms and X is halogen, e.g., chloride.
Especially preferred are ditallow dimethyl ammonium chloride and
di(hydrogenated tallow-alkyl) dimethyl ammonium chloride and
di(coconut-alkyl) dimethyl ammonium chloride, these compounds being
preferred from the standpoint of excellent softening properties and
ready availability.
Suitable cation-active amine softener compounds are the primary,
secondary and tertiary amine compounds having at least one
straight-chain organic group of from 12 to 22 carbon atoms and
1,3-propylene diamine compounds having a straight-chain organic
group of from 12 to 22 carbon atoms. Examples of such softener
actives include primary tallow amine; primary hydrogenated-tallow
amine; tallow 1,3-propylene diamine; oleyl 1,3-propylene diamine;
coconut 1,3-propylene diamine; soya 1,3-propylene diamine and the
like.
Other suitable cation-active softener compounds herein are the
quaternary imidazolinium salts. Preferrred salts are those
conforming to the formula ##SPC3##
wherein R.sub.6 is an alkyl containing from 1 to 4, preferably from
1 to 2, carbon atoms, R.sub.5 is an alkyl containing from 1 to 4
carbon atoms or a hydrogen radical, R.sub.8 is an alkyl containing
from 1 to 22, preferably at least 15, carbon atoms, R.sub.7, an
alkyl containing from 8 to 22, preferably at least 15, carbon
atoms, and X is an anion, preferably methyl sulfate or chloride
ions. Other suitable anions include those disclosed with reference
to the cationic quaternary ammonium fabric softeners described
hereinbefore. Particularly preferred are those imidazolinium
compounds in which both R.sub.7 and R.sub.8 are alkyls of from 12
to 22 carbon atoms, e.g.,
1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4,5-dihydroimidazolinium
methyl sulfate;
1-methyl-1-[palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium
chloride.
Other cationic quaternary ammonium fabric softeners, which are
useful herein include, for example, alkyl (C.sub.12 to
C.sub.22)-pyridinium chlorides, alkyl (C.sub.12 to C.sub.22)-alkyl
(C.sub.1 to C.sub.3)-morpholinium chlorides, and quaternary
derivatives of amino acids and amino esters.
The cationic fabric softeners mentioned above can be used singly or
in combination in the practice of the present invention.
Operability of the essential substantially waterinsoluble
particulate component for use in the compositions of the instant
invention is dependent on a series of characteristics; namely, (1)
an average particle size from about 1.0 to about 50, preferably
from about 5 to about 30 micrometers; (2) a shape having an
anisotropy of about 5:1 to 1:1; (3) a hardness of less than about
5.5 on the Moh scale; (4) a melting (softening) temperature above
about 150.degree.C; and (5) substantial freedom from exchangeable
calcium and magnesium ions. Said particulate component is used in
the instant compositions in an amount from about 0.01% to about
95%. As with the cationic component, the level of particulate
material can vary widely, depending upon physical state and
intended use of a particular composition. For example, liquid
softener formulations normally have a level of particulate material
from about 0.01% to about 10%, preferably from 0.1% to 6%, more
preferably from 0.2% to 4 %. The upper limit is normally dictated
by the material possibility for incorporating a given amount of
particulate component without disturbing the liquid state of the
composition, i.e., to avoid, for example, gelatinization, phase
separation and precipitation. As with the cation-active softener,
the lower limit is based on economical and performance
considerations, i.e., a further reduction of softener compound
entails that excessive amounts of softening composition are needed
to achieve the inventive advantages. The solid softening
compositions of this invention preferably contain from about 0.1%
to about 50%, more preferably from about 0.2% to about 25% of the
essential particulate component. Increasing the level of
particulate ingredient above the upper limit (95%) does not procure
additional performance advantages.
The average particle size of the substantially water-insoluble
particulate component is within the range from about 1 to about 50,
preferably from about 5 to about 30 micrometers. The particle
diameter limitation appears to relate to the diameters of
(commercially) available textile fibers which fall mostly within
the range of about 10 to about 30 micrometers. Accordingly, the use
of particulate water-insoluble materials having an average diameter
of more than about 50 micrometers will not provide the fabric
benefits enumerated hereinbefore. On the other hand, the use of
particulate water-insoluble materials having an average particle
size diameter of less than about 1 micrometer will not provide the
overall fabric benefits obtainable through the practice of this
invention.
The substantially water-insoluble particulate component is further
characterized by an anisotropy (axial ratio) of about 5:1 to 1:1.
The determination of particle size can be based on the measurement
of the projection area of the water-insoluble particle or on the
linear measures of this projection area. Or, in other words, the
loose particle resting on its surface of maximum stability, the
long and intermediate axis are normally horizontal and the short
axis vertical. In that context, the term "long axis" represents the
maximum overall length of the particle; "intermediate axis" stands
for the maximum dimension of a particle in a direction
perpendicular to the long axis; whereas "short axis" represents the
maximum dimension in a direction perpendicular to the plane
containing the long and intermediate axis. The meaning of
anisotropy represents the ratio of long axis to short axis for a
specific particulate material. Preferred for use in the
compositions of this invention are particulate materials having an
anisotropy within the range from about 3:1 to about 1.1:1.
See also: Advances in OPTICAL and ELECTRON MICROSCOPY, Vol. 3, R.
Barer and V. E. Cosslett, ACADEMIC PRESS 1969, London and New
York.
The essential particulate component for use herein has a hardness
of less than about 5.5 on the Moh scale. The hardness as so
measured is a criterion of the resistance of a particular material
to crushing. It is known as being a fairly good indication of the
abrasive character of a particulate ingredient. Examples of
materials arranged in increased order of hardness according to the
Moh scale are as follows: h(hardness)-1:talc; dried filter-press
cakes, soap-stone, waxes, aggregated salt crystals; h-2: gypsum,
rock salt, crystalline salt in general; h-3: barytes, chalk,
brimstone, calcite; h-4: fluorite, soft phosphate, magnesite,
limestone; h-5: apatite, hard phosphate, hard limestone, chromite,
bauxite; h-6: feldspar, ilmenite, hornblendes; h-7: quartz,
granite; h-8: topaz; h-9: corrundum, emery; and h-10: diamond.
Suitable particulate materials have a hardness of less than about
5.5 on the Moh scale. Although some fabric-care benefits can be
obtained from particulate materials having a Moh hardness of, for
example 7, it is submitted that as regards overall benefits said
particulate materials do not qualify for use in the instant
compositions. The reason for this being unknown, it is assumed,
without being bound to this theory and limited as a result thereof,
that as a result of excessive particle hardness, fiber and yarn
damage occur which adversely affect the fabric, particularly
through cumulative action resulting from multicycle
textile-treating operations.
The substantially water-insoluble particulate material has a
melting point about 150.degree.C. Particulate materials havinga
melting point below that temperature do not provide the fabric
benefits because of their tendency to melt and accordingly spread
through the fabric thereby giving body to the fabric which is
commonly known as sizing. This is undesirable in the context of
this invention and the particulate materials must be such as to
maintain under ironing conditions, i.e., above around 150.degree.C,
their integrity and shape as said characteristics are essential for
the attainment of the fabric-care benefits derivable from the uses
of the compositions of the instant invention.
In addition, the particulate material must be substantially
water-soluble as its function depends upon its integrity, shape,
firmness, etc. as described in detail hereinbefore. It should be
recognized, however, that minor parts of the particulate
ingredient, preferably not more than 20%, can be water-soluble
without markedly decreasing the performance advantages.
The water-insoluble particulate materials are substantially free of
exchangeable calcium and magnesium ions. The presence of
exchangeable alkaline earth metal ions such as calcium and
magnesium in the particulate materials appears to increase their
hydrophilic properties. This results in enhanced swellability
characteristics, which, in turn, constitute an obstacle to the
uniform and stable enmeshing of particulate material within the
fiber structure. As a result, particulate materials having
exchangeable calcium and magnesium ions in their structure detract
from attaining overall fabric benefits as described
hereinabove.
Preferred for use in the instant compositions are surface-treated
starch derivatives such as "DRY-FLO" starch manufactured by
NATIONAL STARCH PRODUCTS, New York. DRY-FLO starches are
surface-modified starches bearing hydrophobic moieties which have
been reacted with the starch molecule through the formation of
ester and ether linkages. As a result of its chemical modification,
these starch derivatives are water-repellant and accordingly
substantially water-insoluble. Dry-Flo starches have an average
particle size diameter of about 9-11 micrometers.
Additional substantially water-insoluble particulate materials
suitable for use in the compositions of the instant invention
include: ##SPC4##
Average Particle Range Particle Ingredient Size .mu.m Size .mu.m
______________________________________ fine glass micro- balloons
(ECCO- SPHERES.sup.(4) 8 5-15 glass beads PF 12-R (coated).sup.(5)
17 5-45 glass beads PF-11.sup.(5) 30 10-50 glass beads
(unispheres).sup.(5) 22 15-37 glass microballons (ECCOSPHERES
IG).sup.(4) 30 -- glass beads PF-12.sup.(5) 17 5-44 glass beads
PF-12S.sup.(5) 17 -- ______________________________________
.sup.(4)Emerson & Cuming; Canton, Mass. .sup.(5)Cataphote
Corp.; Jackson, Miss.
See also: (1) Technical Data Sheet for "Teflon" 7A; and brochure re
"Typical Properties Common to All Granular Teflon FFE-Fluorocarbon
Resins," No. A-43044; both being issued by DuPont de Nemours; (2)
Catalog of Small Glass Beads, issued by Microbeads Division,
Cataphote Corporation, Jackson, Mississippi; particularly documents
MB-111-DS-5/72; MB-IV-DS-5/72; MB-V-LP-5/72; and MB-VII-LP-5/72;
and (3) Technical Information Brochure concerning ECCOSPHERES,
hollow glass and ceramic microspheres, MICROBALLOONS, issued by
Emerson and Cuming, Inc., Canton, Mass.; the above documents being
hereby incorporated by reference.
Another substantially water-insoluble particulate component for use
in the instant compositions is a starch granule having, in addition
to the essential parameters as defined in the claims, a swelling
power of less than about 15 at a temperature of 65.degree.C.
Modification of the starch granules in a matter such as to render
it more soluble by gelatinizing, derivatizing, or degrading is to
be avoided to the extent it leads to starches which can lose their
firm shape and also do not qualify for use in the present
invention. Soluble or gelatinizable starches having a swelling
power of more than about 15 to 65.degree.C are less suitable as
they tend to lose their individual shape and consequently run into
the fiber which, in turn, leads to undesirable stiffness of
fabrics.
The swelling power is determined according to the mthod set forth
in Cereal Chem., 36, pp. 534-544 (1959) Harry W. Leach, et al. Ten
grams of starch are suspended in 180 ml. of distilled water in a
tared 250-ml. centrifuge bottle. The suspension is mechanically
stirred with a small stainless-steel paddle (0.75-in. wide, 1.5-in.
high) at a rate just sufficient to keep the starch completely
suspended (i.e., 200 r.p.m.) This low speed avoids shearing the
fragile swollen granules and consequent solubilization of the
starch. The bottle is lowered into a thermostatted water bath
maintained at a temperature of 65.degree.C (.+-.0.1.degree.C) and
held for 30 minutes, slow stirring being continued during this
period. The bottle is then removed, wiped dry, and placed on the
torsion balance. The stirrer is removed and rinsed into the bottle
with sufficient distilled water to bring the total weight of water
present to 200.0 g. (including the moisture in the original
starch). The bottle is stoppered, mixed by gentle shaking, and then
centrifuged for 15 minutes at 2,200 r.p.m. (i.e., 700 times
gravity). The clear supernate is carefully drawn off by suction to
within 1/4 in. of the precipitated paste. An aliquot of this
supernate is evaporated to dryness on the steam bath and then dried
for 4 hours in the vacuum oven at 120.degree.C. The percentage of
solubles extracted from the starch is calculated to dry basis. The
remaining aqueous layer above the sedimented starch paste is then
siphoned off as quantitatively as possible. The bottle and paste
are reweighed on the torsion balance, and the swelling power
calculated as the weight of sedimented paste per g. of dry-basis
starch.
Starches having a swelling power of more than 15 at 65.degree.C are
not suitable for use in the instant composition. Although the final
choice of starch which will meet requirements of this invention
depends upon the origin of the material and also upon process
conditions such as bleaching, degradation, and isolation applied to
a given species, suitable starches can, for example, be obtained,
from corn, wheat, and rice. Current potato and tapioca starches
have a swelling power exceeding 15 at a temperature of 65.degree.C
and, therefore, are not suitable for being used in the compositions
of this invention. More complete information concerning
water-insoluble starches, the processes for their preparation and
isolation from a variety of raw materials are well known [see, for
example: THE STARCH INDUSTRY, Knight, J. W., Pergamon Press, London
(1969)].
As explained hereinafter, however, without being limited as a
result thereof, it is thought that the parameters of the
particulate material for use in the instant compositions are
essential to the extent that said characteristics directly
contribute to the beneficial fabric properties.
These critical limitations as to the nature of the particulate
material were determined initially by actual experimentation. While
applicants will not be held by any theoretical interpretaton of
these critical limitations, it appears that the particulate
material interacts with the textile material at the fiber level to
impart the above enumerated benefits to the textile fabric as a
whole. In this respect it is to be noted that textile materials
consist essentially of assemblies of fine flexible fibers arranged
in more or less orderly geometrical arrays. Individual fibers
within the assembly are usually in a bent or twisted configuration
and are in various states of contact with neighboring fibers. When
the assembly is deformed the fibers move relative to each other and
this relative motion accounts to a large extent for the
characteristic flexibility of textile materials. To what extent a
given textile material will recover when a deforming force is
removed is largely determined by the nature of the interaction of
the individual fibers making up the textile material. Textile
fibers are viscoelastic and hence will exhibit delayed recovery
from strain. However, the large number of interfiber contact points
provide frictional restraints which further hinder the recovery
process. In most textile structures the area of interfiber contact
is probably less than 1% of the total fiber area. The force per
contact point is generally estimated to be within the range of 1 to
10 dynes.
It is with this view of textile materials that applicants
hypothesis going to explain the efficacy of particulate materials
in imparting the related effects of anti-wrinkling, ease of
ironing, softness, anti-static benefits and appearance improvements
can be appreciated. For purpose of conceptualization, this
hypothesis will hereinafter be referred to as the "ball bearing
effect." The conceptualization is useful in interpreting the
interaction of the particulate material and the textile matrix
under imposed forces of deformation.
By means of microscopic analysis and staining techniques, it has
been determined that textile fabrics treated in accordance with the
present invention are characterized by having discrete particulate
materials intimately dispersed, in a substantive fashion, in the
interstices of the fiber matrix. It is believed that these
particulate materials, so interfiberly positioned, act in the
manner of ball bearings to reduce interfiber forces during
deformation of the textile fabric as a whole. The gross effect is
the enhancement of visco-elastic recovery (anti-wrinkling effect)
and diminution of the forces operable at interfiber contact points
(ease of ironing effect). Under this conceptualization, and as
already referred to hereinbefore, the particle diameter limitation
is appreciated since most commercially available textile fibers
have diameters which fall within the range of about 10 to about 30
micrometers. Therefore, to be effective, the particulate material
of the invention must preferably be comparable to the textile fiber
diameters. The above-mentioned benefits are similarly related to
the presence of the particulate material at points within
interstices of individual fiber yarns. Microscopic examination of
textile yarns in cross section reveals that textiles treated in
accordance with the present invention have greater yarn diameters
than similar textile yarns which are distinguishable by the absence
of particulate materials. Apparently, the particulate materials
positioned in the interfiber spaces effectively open up the yarn
(apparent increase in bulk) resulting in a softer, fluffier textile
fabric. The anti-static benefit appears to be related to a change
in the resistivity of the fabric matrix containing the particulate
materials; for example, the copresence of chemically modified
starch granules such as DRY-FLO starch, in the textile fabric,
increases the equilibrium moisture content of the matrix, thereby
decreasing its resistivity and diminishing static build-up.
A particular embodiment of the present invention provides a method
for treating fabrics for simultaneously imparting fabric-care
benefits to textiles treated therewith. To that effect, the fabrics
are treated in an aqueous liquor comprising from about 0.2 ppm
(part per million) to about 5,000 ppm, preferably from about 2.5
ppm to about 1,000 ppm of a cation-active fabric softener. Suitable
and preferred cationic softening agents for use in the intant
method are the same as those which fit the composition aspect of
this invention; these species have been described in great detail
hereinbefore.
Another essential component for use in the aqueous liquor is
represented by substantially water-insoluble particulate materials
having: (1) an average particle size in the range from about 1 to
about 50 micrometers; (2) a shape having an anisotropy of about 5:1
to 1:1; (3) a hardness of less than about 5.5 on the Moh scale; (4)
a melting point above about 150.degree.C; and (5) substantial
freedom from exchangeable calcium and magnesium ions. The
particulate material is used in an amount from about 0.2 ppm to
about 1,000 ppm, preferably from about 0.5 ppm to about 500 ppm.
Suitable and preferred species are those which fit the composition
requirements of this invention; said species are described in
greater detail hereinbefore.
The aqueous liquor needed for carrying out the method of this
invention can, for example, be prepared by adding to a
substantially aqueous medium softening compositions corresponding
to the fabric softening compositions in this invention. Similar
results can also be obtained, however, by adding the individual
ingredients to an aqueous medium. As an example thereof, one may
consider adding to the aqueous medium a softening composition
containing all ingredients except the particulate material which is
to be added separately. It is also possible to prepare a softening
composition containing the cation-active agents and other usual
ingredients whereas the particulate material can be added in
combination with inerts like urea or with other minor
ingredients.
The particulate material can be admixed with a conventional
previously prepared fabric softening composition, or can be
incorporated together with the individual ingredients of the
composition prior to the mixing and uniformizing process. Whatever
route is selected for incorporating the essential particulate
component, care has to be taken to avoid processing steps which
might alter the native granular integrity of the particulate
material. As an example, excessive heating and grinding operations
must be avoided as these steps may contribute to a disruption of
the particulate material structure and accordingly render the
softening composition less effective for fabric conditioning
operations. As is well known to the skilled artisan, the
preparation of homogenous and storage stable liquid softening
compositions in accordance with this invention may require the
incorporation of phase stabilizers, suspending agents, thickeners,
and the like in the usual amounts.
The compositions of the instant invention can also contain
additonal ingredients to make them more attractive or more
effective and also inert fillers. For example, the composition of
this invention can contain thickeners, solubilizing agents, and
also minor amounts of detergent ingredients for the purpose of
rendering, for example, the liquid compositions hereof, more
storage stable and also in order to facilitate incorporation
therein of higher amounts of the essential ingredients. Dyes,
perfumes and anti-bacterial agents can be incorporated for
improving the aesthetics and for performance reasons. In the solid
softening compositions of this invention there can be present major
amounts of inerts such as urea, sodium sulfate and sodium
chloride.
The conditioning compositions of the present invention are
evaluated by certain tests upon textile fabrics treated therewith
as set forth below.
Anti-Static Test
A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35
polyester/cotton blend; 17% nylon; 18% Dacron) is treated for 10
minutes in a miniature agitator washer containing two gallons of
aqueous liquor containing the test softening compositions (as set
forth below). The temperature is 100.degree.F; water hardness 7
grains/gallon artificial hardness. The bundle comprises 5% by
weight of the softening liquor. The bundle is spin extracted prior
to being dried in a commercial dryer.
The static charge on each fabric is then measured by a standard
electrostatic technique within a Faraday cage. The sum of the
absolute values of the charges on all fabrics in the bundle,
divided by the sum of the area (yards.sup.2) of the total fabric
surface (2 sides of the fabric) is then computed. This so-called
"static value" (volts/yard.sup.2) correlates with gross
observations of the effects of static charges on fabric surfaces,
i.e., electrical shocks, sparks, fabric clinging, etc. Depending on
the fabric bundle tested, no static clinging is exhibited by
fabrics having a static value less than about 1.5 volts/yards.sup.2
; substantial static clinging is noted in fabrics having a static
value above 4.5 volts/yard.sup.2.
Anti-Wrinkling Test
A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35
polyester/cotton blends; 17% nylon; 18% Dacron) is treated for ten
minutes in a miniature agitator washer containing two gallons of
aqueous liquor containing the test softening compositions (as set
forth below). The temperature is 100.degree.F; water hardness 7
grains/gallon artificial hardness. The bundle is spin extracted
prior to being dried in a commercial dryer.
The extent of wrinkling on a given piece of fabric is then measured
by mounting the fabric on a flat, movable surface within a
light-tight box. A fine beam of light from a source above the
fabric impinges upon the fabric at an angle of 90.degree.. As the
mounted fabric is moved through a predetermined distance, a
miniature photocell affixed adjacent to the stationary light source
resonds to scattered light at an angle of 45.degree. to the fabric
surface. A plot of the light intensity measured by the photocell
versus the length of the fabric path traversed gives a profile
(curve) which is in all practical respects a facsimile of the
surface of the test fabric. That is, a smooth, unwrinkled fabric
gives essentially a straight line of constant light intensity
whereas a wrinkled fabric gives a series of peaks and minima. The
ratio of the absolute distance through which the fabric was moved
to the length of the plotted curve is quantitatively related to the
extent of wrinkling.
Ease of Ironing Test
A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35
polyester/cotton blends; 17% nylon; 18% Dacron) is treated for 10
minutes in a miniature agitator washer containing 2 gallons of
aqueous liquor containing the test softening compositions (as set
forth below). The temperature is 100.degree.F; water hardness 7
grains/gallon artificial hardness. The bundle is spin extracted
prior to being dried in a commercial dryer.
The ease of ironing of each fabric is then measured by using an
instrumented, but otherwise conventional, iron. In essence, the
iron by means of sensors fitted in its interior measures the amount
of effort required by an operator to smooth the surface of the test
fabric to a subjectively smooth appearance. The total amount of
work required to achieve this appearance is a function of the force
exerted on the iron (measured) and the distance traversed by the
iron in the plane of the fabric (measured). These tests are
performed against untreated controls.
Other tests such as, for example, softness (related to bulkiness),
ease of folding, fabric drapability and fragrance are assessed
subjectively by expert panelists against unmarked controls.
The following examples are illustrative of this invention.
BASE COMPOSITION
A liquid base fabric softening composition was prepared having the
following formula:
Ingredient Parts by Weight ______________________________________
Ditallowdimethylammonium chloride 5.25 Particulate material See
below Emulsifier, isopropanol, ethanol, dye, perfume, miscellaneous
1.5 Water Balance to 100 ______________________________________
A substantially water-insoluble particulate material was added to
the base composition prior to testing. The softening composition so
prepared was used at a concentration of 0.1% in the rinse water.
The fabric-care benefits represent reduced wrinkling and reduced
ironing efforts measured as previously described. In all cases, the
performance of the inventive formulations tested was compared to
the performance of an identical formulation which did not contain
particulate materials. Each of the particulate materials listed in
the table below provided a statistically significant (.alpha. =
0.05, one-tailed test) reduction in both wrinkling and ironing
efforts. The fabrics treated were polyester/cotton 65/35 and
cotton.
__________________________________________________________________________
Particulate Material Average Particle PPM in % in Softener Example
Particulate Material Size .mu.m Rinse-Solution Formulation
__________________________________________________________________________
I Glass micro balloons (ECCOSPHERES IG) 30 30 3 II
Poly(tetrafluorethylene) (MOLYKOTE 522) 10 30 3 III
Poly(ureaformaldehyde) 6 3 0.3 IV Poly(methylmethacrylate)
(syndiotactic) 18 3 0.3 V Glass beads PF-12S 17 3 0.3 VI Glass
beads PF-12T 17 3 0.3 VII "DRY-FLO"Starch 10 30 3 VIII
Poly(melamineformaldehyde/ureaformaldehyde) 5 3 0.3 IX Glass beads
(Unispheres) 22 3 0.3 X Glass beads PF-12R 17 3 0.3 XI
Poly(styrenedivinylbenzene) 6 3 0.3 XII Glass beads PF-11 30 3 0.3
__________________________________________________________________________
EXAMPLE XIII
A fabric softening composition having the formula given hereinafter
simultaneously imparts softening, ease of ironing, anti-wrinkling
and appearance improvements to fabrics treated therewith.
______________________________________ Ingredient Parts by Weight
______________________________________ Distearyl dimethyl ammonium
chloride 9.0 DRY-FLO starch; average particle size diameter: 10
.mu.m 1.5 Minor ingredients including emulsifier, isopropanol, dye,
perfume 2.0 Water Balance to 100
______________________________________
Substantially identical results are obtained when the distearyl
dimethyl ammonium chloride is replaced with an equivalent amount
of: tallow trimethyl ammonium chloride; ditallow dimethyl ammonium
methyl sulfate; dihexadecyl dimethyl ammonium chloride;
di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl
dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride;
didocosyl dimethyl ammonium chloride; di(hydrogenated tallow)
dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium
chloride; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl
ammoniumphosphate; ditallow dimethyl ammoniumnitrate; di(coconut
alkyl) dimethyl ammonium chloride; primary tallow amine; primary
hydrogenated-tallow amine; tallow-1,3-propylene diamine; oleyl
1,3-propylene diamine; coconut-1,3-propylene diamine; and soya 1,3
propylene diamine.
Substantially identical results are also obtained when the
distearyl dimethylammonium chloride is substituted by an equivalent
quantity of:
1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4,5-dihydroimidazolinium
methyl sulfate; and
1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium
chloride.
Substantially identical results are also obtained by substituting
DRY-FLO starch by an equivalent amount of poly(methylmethacrylate)
isotactic or syndiotactic form; poly(tetrafluoroethylene);
polystyrene; poly(styrenedivinylbenzene); polyvinyltoluene;
poly(melamineformaldehyde-ureaformaldehyde);
poly(ureaformaldehyde); fine glass micro-balloons; glass beads,
coated if desirable; and starch.
A broad range of fabric-care benefits are as well obtained when
distearyl dimethyl ammonium chloride is incorporated at a level of:
2,5%; 4,5%; 7%; 11%; 14.5%, 18 %; 20.5%; and 25%, respectively.
A broad range of fabric-care benefits are also obtained when the
DRY-FLO starch is used (in the formulation) at a level of: 0.2%,
0.8%; 1.2%; 2%; 3%; 4.5%; 6%, 7.2%; and 9%, respectively.
Solid fabric-conditioning compositions, which provide a broad range
of benefits to fabrics treated therewith, are prepared having the
following formulas:
PARTS BY WEIGHT Ingredients XIV XV XVI XVII XVIII XIX XX XXI
__________________________________________________________________________
Dioctadecyldimethyl ammonium chloride 55 20 30 Ditallow dimethyl
ammonium chloride 5 60 30 1-methyl-1-[(stearoylamide)-
ethyl]-2-heptadecyl-4,5 dihydroimidazolinium methyl sulfate 30 40
Urea 25 15 71 69.2 15 40 45 50 DRY-FLO starch: average particle
diameter 10.mu.m 13 50 20 0.8 20 18 20 16 Minors, including dye,
perfume, emulsifying agent, hydrotropes and moisture 7 5 4 10 5 2 5
4
__________________________________________________________________________
Substantially identical results are obtained when DRY-FLO starch is
replaced with an equivalent amount of: poly(methylmethacrylate)
isotactic or syndiotactic form; poly(tetrafluoroethylene);
polystyrene; poly(styrenedivinylbenzene); polyvinyltoluene;
poly(melamineformaldehyde-ureaformaldehyde);
poly(ureaformaldehyde); fine glass micro-balloons; glass beads,
coated if desirable; and starch. Substantially identical results
are also obtained when urea is replaced with an equivalent amount
of sodium sulfate, sodium chloride and the like fillers.
* * * * *