Note: Descriptions are shown in the official language in which they were submitted.
~S~7~6
Fabric Conditioning Article,
method of manufacturing same, and
method of conditioning clothes therewith
The present invention is concerned with an article
useful for conditioning clothes in an laundry dryer during
the drying cycle which article has a pattern thereon which
is substantially removed from the article during the course
o~ the drying cycle thereby indicating to the user of the
article that the conditioning agent which the article
contained has been substantially used up during the course
of the drying cycle.
Various dryer added fabric conditioning a~ents for
use in automatic laundry dryers for the purpose of
conditioning clothes such as to provide softness and/or
antistatic properties thereto or bacteriostatic or
fungicidal properties thereto are known in the art. Such
articles comprise a fibrous, woven or nonwoven flexible
substrate coated or impregnated with a suitable fabric
conditioning agent or a flexible polyurethane foam
substrate impregnated with a suitable fabric conditioning
agent which will transfer from the substrate to the
clothes to be conditioned during the drying cycle in an
automatic laundry dryer. Frequently the user of such an
article will attempt to reuse the article on a subsequent
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~lS27~6
bundle of clothes and will be disappointed that the
conditioning achieved from the first use is not repeated
for the second.
The present invention provides a decorative pattern
on the substrate which is visible to the user at the time
the substrate is initially place in a laundry dryer with
the clothes to be conditioned and which pattern substant-
ially disappears from the substrate during the course of -
the drying cycle. The disappearance of the pattern is
intended to indicate to the user that the conditioning
agent has been substantially used up and that the substrate
therefore does not contain a sufficient amount of
conditioning agent to render the article useful a second
or subsequent time. According to the present invention
there is provided an article useful for conditioning
clothes in a laundry dryer during the drying cycle which
comprises a flexible polyurethane foam substrate
impregnated with an effective amount of a conditioning
agent and having on at least one surface of the substrate
a pattern formed by an ink which adheres to the surface,
is stable to the conditioning agent and is stable during
the impregnation of the substrate with the conditioning
agent, and which pattern substantially disappears from
the substra~e during this drying cycle. The conditioning
agent comprises a fabric softening agent, an antistatic
agent, a fabric softening and antistatic agent, a bacterio-
static or a fungicide~
The ink used to print the pattern on
the substrate preferably comprises a titanium dioxide
(TiO2) water-based ink containing a suitable binder. The
loading of ~hk,measuredas dried in~ is preferably from 0.05
to 60 gm 2 within the patterned area. When the conditioning
agent is a fabric softening and antistatic agent one
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;27~?6
suitable class are cationic quaternary ammonium salts
or a cationic quaternary ammonium salt in combination
with a suitable nonionic su~actant. Any quaternary
ammonium salt or combination of quaternary ammonium
salt and/or suitable nonionic su~actant which salt,
mixture of salts or mixture is known in the art to
exhibit fa~ric softening and antistatic effect and which
is compatible for impregnation into a flexible poly-
urethane foam substrate may be used.
Particularly useful cationic quaternary ammonium
salts are: dodecyltrimethyl ammonium chloride;
didodecyldimethyl ammonium chloride;
tetradecyltrimethyl ammonium chloride;
ditetradecyldimethyl ammonium chloride;
pentadecyltrimethyl ammonium chloride;
dipentadecyldimethyl ammonium chloride;
didodecyldiethyl ammonium chloride;
didodecyldipropyl ammonium chloride;
. ditetradecyldiethyl ammonium chloride;
ditetradecyldipropyl ammonium chloride;
ditallowdiethyl ammonium chloride;
ditallowdipropylammonium chloriae;
tallowdimethyl benzyl am~lonium chloride;
tallowdiethyl benzyl ammonium chloride;
dodecyltrimethyl ammonium methyl sulphate;
didodecyldiethyl ammonium acetate;
tallowtrimethyl ammonium acetatè
tallowdimethyl benzyl ammonium nitrite;
ditallowdipropyl ammonium phosphate;
tallowtrimethyl ammonium chloride;
tallowdimethyl (3-tallowalkoxpropyl) ammonium
chloride;
. ~.,
~57~73~
ditallow dimethyl ammonium chloride;
ditallow dimethyl ammonium methyl sulphate;
icosyltrimethyl ammonium chloride;
di-icosyldimethyl ammonium chloride;
methyl-l-coco amido ethyl-2-coco imidazolinium
methyl sulphate;
methyl-l-soya amido ethyl-2~soya imidazolinium
methyl sulphate;
methyl-l-tallow amido ethyl-2-tallow imidazolinium
methyl sulphate;
methyl-l-oleyl amido ethyl-2-oleyl imidazolinium
methyl sulphate; and
methyl-l-tallow amido ethyl-2-tallow imidazolinium
chloride.
Particularly suitable zwitterionic quaternary
ammonium compounds are:
3-(N -icosyl-N,N-dimethylammonio)-2-hydroxypropane-
l-sulphonate;
3-(N -icosyl-N,N-dimethylammonio)propane-l-sulphonate;
3-(N -icosyl-N,N-di(2-hydroxyethyl)ammonio)-2-
hydroxypropane-l-sulphonate;
3-(N-docosyl-N,N-dimethylammonio)-2-hydroxypropane-
l-sulphonate;
3-(N-docosyl-N,N-dimethylammonio)propane-l-sulphonate;
3-(N-docosyl-N,N-bis-(2-hydroxyethyl)ammonio)-2-
hydroxypropane-l-sulphonate;
3-(N-tetrac~l-N,N-dimethylammonio)-2-hydroxypropane-
l-sulphonate;
3-(N-tetracosyl-N,N-dimethylammonio)propane-l-
sulphonate;
~ 1J 527~6
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3-(N-tetracosyl-N,N-bis(2-hyd~yethyl)ammonio)-2-
hydroxypropane-l-sulphonate;
3-(N-hexacosyl-N,N-dimethylammonio)-2-hydroxypropane-
l-sulphonate;
S 3-(N-hexacosyl-N,N-dimethylammonio)propane-l-sulphonate;
3-(N -icosyl-N-ethyl-N-methylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-docosyl-N-ethyl-N-methylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-tetracosyl-N-ethyl-N-methylammonio)-2-hydroxy-.
propane-l-sulphonate;
3-(N - henicosyl-N,N-dimethylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-tr-i-cosy~N,N-dimethylammonio~-2-hydroxypropane-
l-sulphonate;
3-(N-tricosyl-N-ethyl-N-methylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-tricosyl-N,N-dimethylammonio)propane-l-sulphonate;
3-(N-pentacosyl-N,N-dimethy].ammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-(2-methoxydocosyl)-N,N-dimethylammonio)-2-
hy~roxypropane-l-sulphonate;
3-(N-heptacosyl-N,N-dimethylammonio)propane-l-
sulphonate;
3-(N-octacosyl-N,N-dimethylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-nonacosyl-N,N-dimethylammonio)-2-hydroxy-
propane-l-sulphonate;
3-(N-triacontyl-N,N-dimethy~ammonio)propane-l-
sulphonate;
3-(N-(3,5-dioxatetracosyl)-N,N-dimethylammonio)-2-
hydroxypropane-l-sulphonate.
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^` ~15;~706
Suitable anionic sulphonates include:
sodium or potassium 2-acetoxydocosylsulphonate;
ammonium 2-acetoxydocosylsulphonate;
diethanolammonium 2-acetoxydocosylsulphonate;
sodium or potassium 2-acetoxytricosyl ~ulphonate;
sodium or potassium 2-acetoxytetracosyl sulphonate;
sodium or potassium 2-acetoxypentacosyl sulphonate;
sodium or potassium 2-acetoxyhexacosyl sulphonate;
sodium or potassium 2-acetoxyheptacosyl sulphonate;
sodium or potassium 2-acetoxyoctacosyl sulphonate;
2-acetoxynonacostyl sulphonate;
2-acetoxytriacontyl sulphonate;
2-acetoxyheni~riacontyl sulphonate; and
2-acetoxydotriacontyl sulphonate.
Particularly suitable softening nonionics include:
~ hydroxydocosyldimethylphosphine oxide;
henicosylimethylethylphosphine oxide;
docosylmethylethylphosphine oxide;
tricosyldiethylphosphine oxide;
tricosyldimethylphosphine oxidei
tetracosyldi(2-hydroxyethyl)phosphine oxide;
pentacosyldimethylphosphine oxide;
icosylmethyl -2-hydroxybutylphosphine oY,ide;
icosyldibutylphosphine oxide;
docosylmethyl-3-hydroxybutylphosphine oxide;
hexacosyldiethylphosphine oxide;
heptacosyldimethylphosphine oxide;
octacosyldiethylphosphine oxide;
triacontyldimethylphosphine oxide;
icosyldimethylphosphine oxide;
~527~6
icosyldi (2-hydroxyethyl)phosphine oxide;
docosyldimethylphosphine oxidei
docosyldi(2-hydroxyethyl)phosphine oxide;
tetracosyldimethylphosphine oxide;
hexacosyldimethylphosphine oxide
icosyldiethylphosphine oxide;
docosyldiethylphosphine oxide;
tetracosyldi(2-hydroxyethyl)phosphine oxide;
icosylmethylethylphosphine. oxide;
henicosyldimethylphosphine oxide;
~-hydroxyicosyldimethylphosphine oxide;
icosyl -bis(~-hydroxyethyl)amine oxide;
icosyldimethylamine. oxide;
docosyldimethylamine oxide;
docosyl-~is(~-hdyroxyethyl)amine oxide;
tetracosyldimethylamine oxide;
tetracosyl-~is (~-hydroxyethyl)amine oxide;
hexacosyldimethylamine oxide;
hexacosyl-b~s (~-hydroxyethyl)amine oxide;
2-hydroxyicosyldimethylamine oxide;
icosylmethylethyl~nine oxide;
icosyldiethyl~nine oxide;
2-hydroxyicosyldiethylamine oxide;
henicosyldimethylamine oxide;
henicosyldiethylamine oxide;
docosyldiethylamine oxide;
tricosyldimethylamine oxide;
tricosyldiethylamine oxide;
tetracosyldiethylamine oxide;
~-hydroxytetracosyldimethylamine oxide;
pentacosyldimethylamine oxide;
hexacosyldiethylamine oxide;
icosylmethyl (2-hydroxypropyl)amine oxide;
111 527Cf~
-- 8 --
docosylbutylmethylamine oxidei
2-docosenyldimethylamine oxidei
2-methoxydocosyldimethylamine oxide;
heptacosyldimethylamine oxide;
octacosylmethylethylamine oxide;
octacosyldiethylamine oxide;
nonacosyldimethylamine oxide;
triacontyldiethylamine oxidei
3,6-dioxaoctacosyldimethylamine oxide;
2-hydroxy-4-oxatetracosyldimethylamine oxide;
6-stearamidohexyldimethylamine oxide;
glycerol-l-monolaurate;
glycerol-l-monomyristate;
glycerol-l-monopalmitate;
glycerol-l-monostearate;
glycerol-l-monobehenate;
glycerol-l-monlignicerate;
glycerol-l-monarachidoate;
glycerol-1,3-dipalmitate;
glycerol-1,3-distearate;
glycerol-l-palmitate-3-laurate;
glycerol-l-palmitate-3-stearate;
glycerol-1,3-dibehenate;
trilaurin;
trimyristin;
triolein;
tristearin;
-palmitodistearin;
~-stearopalmitolein;
~-palmitodistearin;
sobitan fatty acid esters (mentioned in U.S. Patent
No. 4,022,938 (Zaki, et al)
~527~6
In addition to the above mentioned nonionics which
function as the main or auxiliary softening agents in the
present invention, there is a second class of nonionics
which are also useful as melting point depressants and
transfer faciltators to the previously mentioned
softening compounds (quaternary a~nonium salts, anionic
and nonionic). Particularly suitable classes of these
compounds include the following:
polyoxyethylene fatty acid esters;
polyoxypropylene fatty acid esters;
polyoxyethylene fatty alcohol ethers.
When the conditioning agent is a quaternary ammonium
salt it will have at least one of the properties of
softening fabrics and conveying antistatic properties
on to fabrics.
The present invention also includes a method of
conditioning clothes in a laundry dryer during the drying
cycle, which method comprises placing in the dryer the
article according to the invention together with the
clothes to be conditioned.
A further aspect of the present invention comprises
a method for producing the article of the invention which
comprises imprinting a desired pattern on a flexible
polyurethane foam substrate either prior to impregnation
o the polyurethane foam substrate with the conditioning
agent or subsequent to the impregnation. The ink used to
imprint the pattern must be one which adheres to the
substrate, is stable to the conditioning agent and if the
. ~SZ7~6
-- 10 --
pattern is applied prior to the impregnation step, the
ink must be stable during the impregnation step and the
ink must be such that the pattern substantially disappears
from the substrate during the drying cycle of a laundry
dryer. The fabric conditioning agent with which the
polyurethane foam substrate is impregnated may comprise
a fabric softening agent, an antistatic agent, a fabric
softening and antistatic agent, a bacteriostatic agent or
a funticide.
An ink which meets the above criteria is suitably
a titanium dioxide water-based ink containing a suitable
binder has been found to be particularly useful. The
loading of ink measured as dried ink within the
patterned area is preferably from 0.05 to 60 gm 2 of
finished product.
When the conditioning agent is a fabric softening
agent and antistatic agent, it is preferably a quaternary
ammonium salt, a mixture of such salts or a quaternary
ammonium salt in combination with a suitable nonionic
surfactant. When the fabric conditioning agent with
which the substrate is impregnated is a quaternary ammonium
salt or mixture of such salts, said compounds will have at
least one of the properties of softening fabrics and
conveying antistatic properties thereto.
Suitable quaternary ammonium salts and nonionic
surfactants have been described above.
The flexible po].yurethane foam substrate which is
preferred for use according to the present invention
preferably has a thickness of approximately 0.22 crn and
a density of approximately 24 Kg m . It is preferably
~S27~6
an open-celled polyurethane foam and preferably the pore
density is about 11 pores per cm2. If desired, the
substrate may be coloured to provide a contrast to the
ink which is used to form the pattern.
While with what is described above anv ink system
which meets the above set forth criteria may be used, one
particularly acceptable ink system is Aqualox II (registered
Trade Mark), white, which is an ink system of Inmont
Corporation. This ink consists of 35~ TiO2 in a water-
base with an acrylic binder. Many inks contain binders
or pigments which are readily dissolved into the active
system of the substrate of dryer-added fabric softeners
in conditioning agents and thus react with the substrate.
This would result in problems during the impregnation of
the substrate with the conditioning agent and would also
be likely to cause staining of the clothes during the
conditioning step in the dryer. Although the pattern
substantially disappears from the substrate during the
course of the drying cycle, the unique partial solvation
of the binder by the active system both permits the
transfer of conditioning agent and inhibits staining of
the clothes.
The desired pattern may be imprinted under the
flexible substrate by using any standard flexographic
printing press. The flexographic printing press utilises
a rotary flexible rubber plate in conjunction with a
rapid drying ink. While the preferred loading of ink,
measured as dry ink, within the patterned area as has
been described above as being within the range of 0.05 to
60 g m2, the preferred loading range is in the range of
0.05 to 4.2 g m 2.
~527~6
The following Example illustrates the present
invention.
Example
Aqualox II (registered Trade Mark), white, a TiO2
water-based ink available commercially from Inmont Corp.
Lodi, ~.J., U.S.A. was used to print a roll of polyurethane
foam. The open-celled polyurethane foam had a thickness
Gf 0.22 cm, a density of 24 Kg m 3 and a pore density of
11 pores cm 2. A flexographic printing unit, Model 45-6,
manufactured by Wolverine Flexographic Presses, FaYmington,
Michigan, U.S.A., was used along with a 55 durometer
synthetic rubber printing plate. The plate's raised
printing surface consisted of 25% of the total surface
area and individual designs were 1.48 cm2 in area. The
average dry ink loading onto the foam was 3.2 g m 2
within the printed areas, or approximately 0.8 g m 2
over the total surface of the foam.
The printed foam was then impregnated with a 5:3
mixture of dimethyl di-(hydrogenated-tallow)ammonium
methylsulphate polyethoxylated glycol ester in a liquid
state at 82C. The impregnation process is accomplished
via a pair of compression rollers neither of which showed
any visible evidence of ink solids either during or after
the run.
The finished printed and impregnated foam was then cut
into 7.6 x 17.8 cm sheets and evaluated in a standard
re~sidential clothes dryer. After a normal 50 minute drying
cycle the pattern had substantially disappeared leaving no
trace of any visible residue on the dark synthetic item
used in the testing bundle.
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