Note: Descriptions are shown in the official language in which they were submitted.
~2~
LAUNDRY ADDITIVE PRODUCTS
This invention relates to laundry additive products.
In partieular, it relates to laundry additive products for
cleaning clothes or other fabrics or for providing an ad~unct
laundering benefit, the additive product comprising a water-
insoluble substrate and a laundry-additive composition coated
on or impregnated into the substrate.
Laundry additive products based on water-insoluble
substrates are now well known in the art. For example, US-
A-3,422,692, Gaiser, issued May 6,1969 discloses a method for
softening and eontrolling static on fabrics in a laundry
washing maehine or dryer using a fabrie conditioning
eomposition coated on a substrate. UK-~-1,586,769 teaches a
laundry additive produet eontaining an organic peroxy compound
preeursor eombined with a solid article, particularly a sheet-
like, water-insoluble substrate. US-A-4,170,565, Flesher
et al, relates to an artiele for cleaning fabrics yielding
sequential release of surface-active components, consisting of
a surface-active composition contained between two layers of
water-insoluble substrate of defined air permeability.
A key eonstraint of a substrate-based laundry-additive
produet, partieularly for use as a detergent or detergent
additive for washing elothes and the like, is the ability to
load a relatively large amount of the laundry additive
composition onto the substrate and simultaneously to aehieve
rapid and complete release of ~he additive eomposition during
the eourse of the launderin~ operation. This i5 to be
contrasted with articles of the eleaning eloth variety used
in the washing and serubbing of hard surfaces such as dishes
and eounter tops and whieh rely on physieal rubbiny and
serubbing during use to assure the release of the proper
amount of eleansing eomposition for the cleaning operation.
Sueh artieles àre generally designed for multiple repeated
use and are formulated, therefore, to release only a small
proportion of the total cleaning composition during any
single use of the artiele.
.
~y
~2~L03ll9~
-- 2
To achieve rapid release of laundry additive composition,
it is generally found desirable to utilize a substrate of low
basis weight. Particularly acceptable fxom this viewpoint are
single layer substrates impregnated with or carrying a coating
of the laundry additive composition. As a result of high
loading and low substrate basis weight, therefore, laundry
additive products having optimum performance for general
detergency use inevitably have a hlgh composition substrate
weight ratio (referred to herein as loading ratio).
From the viewpoint of processing, product aesthetics,
and storage characteristics, however, designing a laundry
additive product having a high loading ratio raises a number
of intractible problems. First and foremost, the flexibility
of the substrate xapidly diminishes at high loading ratio and
the product becomes increasingly rigid and board-like. Not
only is this disliked by consumers but it also raises
processing problems associated with composition flaking from
the sheet, and manufacturing and packaging problems associated
with folding the article into a form which is compact and
convenient for use. Where, on the other hand, the additive
composition is made sufficiently soft and plastic to mitigate
flexbility problems, the articles become quite sticky and
uncom~ortable to touch and associated problems of handling and
storage (blocking phenomena etc) become increasingly important.
It has now been found that by selecting certain laundry
additive compositions of defined melting characteristics and
cextain sheet-like apertured substrates of defined aperture
siæe and density and by coating the substrate so as to cover
and ~ill only a defined proportion oE the substrate apertures,
laundr~ additive products can be provided which simultaneously
meet the mutual constraints of high loading, good release
characteristics, and excellent flexibility and product feel
characteristics.
The present invention thus provides a laundry additive
product having a high compositlon:substrate ratio together
with excellent product flexibility characteristics, which is
not sticky to handle and which is easy to manufacture, use and
store, and which can be used in a laundering operation to
clean clothes and other ~abrics effectively and conveniently
4Q or to provide additional laundering benefits.
` ~,t
~2~03~
According to the present invention, there is provided
a laundry additive product comprising:
(a) a solid laundry additive composition having a softening
temperature of at least about 35C and comprising at
least about 40% of a water-soluble or water-dispersible
matrix of organic materials having a melting completion
temperature of less t~an about 85C, and
(b) a flexible, sheet-like apertured substrate having an
aperture density of from about 10 to about 30 apertures
per sq cm of sheet and wherein the apertures, on
average, have a width of from about 0.5mm to about 5mm
and a length of from about 0.8mm to about 5mm, the
substrate carrying a water releasable coating of the
laundry additive composition and having areas of
uncoated apertures and areas wherein the coating covers
the apertures and extends between opposing surfaces of
the substrate, the ratio of areas of uncoated to coated
apertures being in the range from about 15:1 to about
1:3 and wherein the weight ratio of composition:
substrate is at least about 5:1.
With regard to the substrate, this preferably has an aperture
density of from about 13 to about 26, more preferably from
about 16 to about 23 apertures per sq cm of sheet, a basis
weight of from about 10 to about 70 grams/sq metre, more
preferably from about 20 to about 50 grams/sq metre and a
hydrophobic binder resins content of from abou~. 12~ to about
25~, more preferably from about 16% to about 22% by weight
of total substrate. The apertures themselves are generally
symmetrical about a longitudinal axis (ie they have mirror
symmetry) and preferably have, on average, a width of from
about 0O7 to about 2.5mm and a length of from about 1.7mm
to abo~ut 4mm. The area of the apertures, on the other hand,
is prefexably from about 0.7mm to about 7mm2, more preferably
from about 0.8mm to about 3.5mm , and the ratio of length:
width is from 1:1 up to preferably about 6:1, more preferably
about 4:1. These parameters are highly preferred from the
viewpoint of achieving the optimum ratio of areas of uncoated
to coated apertures and the complete filling of coated
apertures from one surface of the substrate to the other.
~7
~2103Ul
The substrate apertures herein can be elongate in shape
(for example, generally elliptical or diamond-shaped) in which
case the apertures preferably have a width of from about 0.8
mm to about 1.5mm and a length of from about 2mm to about 3.5
mm. In preferred embodiments, however, the apertures are
generally square-shaped with a side dimension of from about
1 to 2.5mm. As used herein, "length" refers to the dimension
of the principal (ie longest) longitudinal axis, and "width"
is the maximum dimension perpendicular to this axis.
As far as loading ratio is concerned (ie the weight ratio
of composition:substrate) this preferably is at least about
6:1 and more preferably at least 7:1. Moreover the ratio of
the areas of uncoated to coated apertures in the final product
is preferably from about 6:1 to about 1:2, more preferably
from about 4:1 to about l:l.
Turning to the laundry additive composition, this
preferably comprises at least about 50~, more preferably at
least about 60% of organic matrix materials; these in turn
each preferably have a melting completion tèmperature of less
than about 75C, more preferably less than about 70C. The
laundry additive composition itself desirably has a softening
temperature of at least about 40C, especially at least about
50C.
In preferred embodiments, the laundry additive product
contains at least about 5%, preferably at least about 15~ by
weight of composition of water-soluble or water-dispersible
organic binding agent having a melting-onset temperature of
at least 35C and a melting completion temperature of less
than about 85C. Preferably, the binding agent is selected
from polyethylene glycols of molecular weight greater than
about 1000, C12-C18 fatty acids and esters and amides thereof,
polyvinyl pyrrolidone of molecular weight in the range from
about 40,000 to about 700,000, and Cl4-C24 fatty alcohols
ethoxylated with from about 14 to about lO0 moles of
ethylene oxide.
Highly preferred from the viewpoint of optimum
flexibility and feel characteristics combined with excellent
water-dispersibility at high loading ratios are polyethylene-
glycols having a molecular weight greater than about 4,000,
preferably greater than about 7,000, these materials
preferably comprising at least about 40~, more preferably at
~ f'
~"
~3~
least about 50~ of the organic bindlng agent.
The laundry additive products of the invention suitably
contain at least about 5%, prefexably at least about 20% of
additive composition of organic detergent selected from
anionic, nonionic and cationic surfactants and mixtures thereof.
Preferred nonionic surfactants have melting completion
temperatures of less than about 85C and form part of the
matrix of organic materials. Preferred catlonic surfactants
have melting onset temperatures of at least about 35C and can
form either part of the organic binding agent or can be
dispersed in the organic matrix. Preferred anionic surfactants
have melting completion temperatures in excess of about 100C
and are dispersed in the organic matrix.
Other functional solid ingredients can also be present
as a dispersion in the organic matrix, especially inorganic
or organic peroxy bleaches which preferably comprise at
least about 5~ by weight of additive composition, and/or
organic peroxy acid bleach precursors which preferably comprise
at least about 2~ by weight of additive composition. Other
~0 suitable functional ingredients include detergency enzymes,
fluorescers, photoactivatorsj sequestrants, bleaching
catalysts, and suds-controlling agents.
The laundry additive products of the invention will now
be discussed in detail.
Preferred substrates for use herein are apertured
nonwoven fabrics which can generally be defined as adhesively
bonded fibrous or filamenkous products, having a web or carded
fibre stxucture (where the fibre strength is suitable to allow
carding) or comprising fibrous mats, in which the fibres or
filaments are distributed haphazardly or in random array (i.e.
an array of fibres in a carded web wherein partial orientation
of the ~ibres is frequently present as well as a completely
haphazard distributional orientation) or substantially aligned.
~he fibres or filaments can be natural (e.g. wool, silk, wood
pulp, jute, hemp, cotton, linen, sisal, or ramie), synthetic
(e.g.rayon, cellulose, ester, polyvinyl derivatives, polyole-
fins, polyamides, or polyesters) or mixtures of any of the
above.
Generally, non-woven cloths are made by air or water
laying processes in which the fibres or filaments are first
cut to desired lengths from long strands, passed into a water
or air stream, and then deposited onto a screen through which
the fibre-laden air or water is passed. The deposited fibres
or filaments are then adhesively bonded together, dried,
cured and otherwise treated as desired to form the non-woven
cloth.
Preferably, the non-woven cloth is made from cellulosic
fibres, particularly from regenerated cellulose or rayon,
which are lubricated with standard textile lubricant such as
sodium oleate. Preferably the fibres are from about 4 to
about 50 mm, especlally from about 8mm to about 20mm, in
length and are from about 1 to about 5 denier (Denier is an
internationally recognised unit in yàrn measure, corresponding
to the weight in grams of a 9,000 meter length of yarn).
Preferably the fibres are at least partially orientated
haphazardly, particularly substantially haphazardly, and are
adhesively bonded together with hydrophobic or substantially
hydrophobic binder-resin, particularly with a nonionic self-
crosslinking acrylic polymer or polymers. In highly preferredembodiments, the cloth comprises from about 75% to about 88%,
especially from about 78% to about 84% fibre and from about
12~ to about 25%, especially from about 16~ to about 22~
hydrophobic binder-resin polymer by weight and has a basis
weight of from about 10 to about 70, preferably from 20 ~o
50 g/m2. Suitable hy~ophobic bin~ r-resins are ethylacrylate
resins such as Primal A24 Rhoplex A8 and HA16 (Rohm and
Haas, Inc) and mixtures thereof.
The substrate apertures, which extand between opposite
~urfaces of the substrate, are normally in a pattern and are
formed during lay-down of the fibres to produce the substrate.
Exemp~ary apertured non-woven substrates are disclosed in US
Patent Nos. 3,741,724, 3,930,086 and 3,750,237.
An example of an apertured non-woven substrate suitable
herein is a regenerated cellulose sheet of 1.5 denier flbres
bonded with Rhoplex HA 8 binder (fibre:binder ratio of about
77:23) having a basis weight of about 35 g/m2and about 17
apertures/cm . The apertures are generally ellipitical in
shape and are in side-by-side arrangementO The apertures
~,~
0~
have a width of about 0.9mm and a length of about 2.5mm
measured in a relaxed condition. Another highly preferred
substrate based on 1.5 denier regenerated cellulose fibres
with Rhoplex HA8 binder has a fibre:binder ratio of about
82:18, a basis weight of about 35g/m2, and about 22 apertures
/cm . In this example, the apertures are generally square-
shaped with a width (relaxed) of about l.lmm. The apertures
are again disposed in side-by-side arrangement.
The size and shape of the substrate sheet for each unit
of product is a matter of choice and is determined principally
by factors associated with the convenience of lts use.
Thus the sheet should not b~ so small as to become trapped in
the crevices of the machine or the clothes being washed or so
large as to be awkward to package and dispense from the
container in which it is sold. For the purposes of the present
invention sheets ranging in plan area from about 130 cm to
about 1300 cm are acceptable, the preferred area lying in the
range of from about 520 cm2 to about 780 cm2O
Turning to the laundry additive composition, this is in
solid form at ambient temperatures (25C and below) and
preferably has a softening temperature of at least about 35C,
more preferably at least about 40C, especially at least
about 50C. By softening temperature is meant the temperature
at which there is transition ~rom plastic-flow to viscous-flow
properties; at ambient temperatures, therefore, the
composition takes the form of a plastic solid having a non-
zero ~ield stress. The hardness of the compositions at
ambient temperatures can be determined by standard m~thods,
~or e~ample, by the penetrometer-based technique o~ IP49
(or the technically equivalent ASTM-D5 or BS4691). Thus,
laundry additive compositions preferred for use herein have a
penetration under a lOOg load at 25C after 15 seconds under
IP49 of less than about 10 (measured in tenths of a millimetre~,
more preferably less than about 7. The softening temperature
of the composition, on the other hand, is taken herein to be
the temperature at which the IP49 15 second penetration
exceeds about 30.
The laundry additive composition herein comprises a
matrix of organic materials having defined melting
~lo~
characteristics. Melting completion temperatures are
determined using a Dupont 910 Differential Scanning
Calorimeter with Mechanical Cooling Accessory and R90 Thermal
Analyser as follows. A 5-10 mg sample of the organic
material containing no free water or solvent is encapsulated
in a hermetically sealed pan with an empty pan as reference.
The sample is initially heated until molten and then rapidly
cooled ~at about 20-30C/min) to -70C. Thermal analysis
is then carried out at a heating rate of 10C/min using
sufficient amplification of ~T signal (ie temperature
di~ference between sample and reference - vertical axis) to
obtain an endotherm-peak signal:baseline noise ratio of
better than lO:l. The melting completion temperature is
then the temperature corresponding to the intersection of
the tangential line at the steepest part of the endotherm
curve at the high temperature end of the endotherm, with the
horiæontal line, parallel to the sample temperature axis,
through the highest temperature endotherm peak.
The organic materials constituting the matrix have a
melting completion temperature of less than about ~5C. In
addition, the laundry additive products of the invention
preferably contain at least about 5% by weight of composition
of binding agent de~ined as organic material having a melting
completion temperature of less than 85C, preferably less
than about 80C, especially less than about 70C, and a melting
onset tempexature o~ at least 35C, preferably at least 40C,
esp~cially at least 50C. The melting onset temperature can
once again be determined by thermal analysis as described
a~ove and i~ taken to be the sample temperature at the point
of intersection of the base line with a tangent to the
steepest part of the endotherm nearest the low temperature
end of the endotherm.
The laundry additive products of the invention can be
supplemented by all manner of laundering and detergency
components. Suitably, the additive products can contain
from about 5~ to about 100%, preferably from about 20% to
about 100%, more preferably from about 35% to about 75% of
organic detergent selected from anionic, nonionic and
cationic surfactants and mixtures thereof. Anionic
3~
surfactants preferably comprise from about 7~ to about 38%,
more pxeferably from about 15~ to about 30~ by weight of
composition; nonionic surfactants from about 8% to about 32%,
more preferably from about 12% to about 25% by weight of
composition; and cationic surfactants from about 5~ to about
30%, more preferably from about 8% to about 20% by weight
of composition.
The anlonic surfactant can be any one or more of the
materials used conventionally in laundry detergents.
Suitable synthetlc anionic surfactants are water-soluble
salts of alkyl benzene sulphonates, alkyl sulphates, alkyl
polyethoxy e~le~ sulphates, paraffin sulphonates, alpha-
olefin sulphonates, alpha-sulpho-carboxylates and their esters,
alkyl glyceryl ether sulphonates, fatty acid monoglyceride
sulphates and sulphonates, alkyl phenol polyethoxy ether
sulphates, 2-acyloxy alkane-l-sulphonate, and beta-alkyloxy
alkane sulphonate.
A particularly suitable class of anionic surfactants
includes water-soluble salts, particularly the alkali metal,
ammonium and alkanolammonium salts of organic sulphuric
reaction products having in their molecular structure an
alkyl or alkaryl group containing from about 8 to about 22,
especially from about 10 to about 20 carbon atoms and a
sulphonic acid or sulphurlc acid ester group. (Included in
the term "alkyl" is the alkyl portion of acyl groups).
Examples of this group of synthetic detergents which form
part of the detergent compositions of the present invention
are the sodium and potassium alkyl sulphates, especially those
obtained by sulphating the higher alcohols (C8_18) carbon
atoms produced by reducing the glycerides of tallow or
coconut oil and sodium and potassium alkyl benzene
sulpho~nates, in which the alkyl group contains from about 9
to about 15, especially about 11 to about 13, carbon atoms,
in straight chain or branched chain configuration, e.g. those
of the type described in U.S.P. 2,220,099 and 2,~77,383 and
those prepared from alkylbenzenes obtained by alkylation with
straight chain chloroparaffins (using aluminium trichloride
catalysis) or straight chain olefins (using hydrogen
fluoride catalysis). Especially valuable are linear straight
~0 chain alkyl benzene sulphonates in which the average of the
Q3~1~
- 10 -
alkyl group is about 11.8 carbon atoms, abbreviated as C11 8
LAS, and C12-Cl5 methyl branched alkyl sulphates.
Other anionic detergent compounds herein include the
sodium C10 18 alkyl glyceryl ether sulphonates, especially
those ethers of higher alcohols derived from tallow and
coconut oil; sodium coconut oil fatty acid monoglyceride
sulphonates and sulphates; and sodium or potassium salts of
alkyl phenol ethylene oxide ether sulphate contalning about
l to about 10 units of ethylene oxide per molecule and
wherein the alkyl groups contain about 8 to about 12 carbon
atoms.
Other useful anionic detergent compounds herein include
the watex-soluble salts or esters of ~-sulphonated fatty acids
containing from about 6 to 20 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-l-sulphonic acids
containing from about 2 to 9 carbon atoms in the acyl group and
from about 9 to about 23 carbon atoms in the alkane moiety;
alkyl ether sulphates containing from about 10 to 18,
especially about 12 to 16, carbon atoms in the alkyl group
and from about 1 to 12, especially 1 to 6, more especially
l to 4 moles of ethylene oxide; water-soluble salts of
olefin sulphonates containing from about 12 to 24,
preferably about 14 to 16, carbon atoms, especially those made
by reaction with sulphur trioxide followed by neutralization
under conditions such that any sultones present are hydrolysed
to the corresponding hydroxy alkane sulphonates; water-
soluble salts of paraffin sulphonates containing from about
~ to 24~ especially 14 to 18 carbon atoms, and ~-alkyloxy
alkane sulphonates containing from about l to 3 carbon atoms
ill the alkyl group and from about 8 to 20 carbon atoms in the
alkane moiety.
The alkane chains of the foregoing non-soap anionic
suxactants can be derived from natural sources such as
coconut oil or tallow, or can be made synthetically as for
example using the Ziegler or Oxo processes. Water solubility
can be achieved by using alkali metal, ammonium or alkanol~
ammonium cations; sodium is preferred. Suitable fatty acid
soaps can be selected from the ordinary alkali metal (sodium,
potassium), ammonium, and alkylolammonium salts of higher
fatty acids containing from about 8 to about 24, preferably
from about 10 to about 22 and especially from about 16 to
'~L\~
, .
about 22 carbon atoms in the alkyl chaln. Suitable fatty
acids can be obtained from natural sources such as, for
instance, from soybean oil, castor oil, tallow, whale and
fish oils, grease, lard and mixtures thereof). The fatty
acids also can be synthetically prepared (e.g., by the
oxidation of petroleum, or by hydrogenation of carbon monoxide
by the Fischer-Tropsch process). Resin acids are suitable
such as resin and those resin acids in tall oil. Napthenic
acids are also suitable. Sodium and potassium soaps can be
made by direct saponification of the fats and oils or by the
neutralization of the free fatty acids which are prepared in
a separate manufacturing process. Particularly useful are
the sodium and potassium salts of the mixtures of fatty acids
derived from tallow and hydrogenated fish oil.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulfonate and sulfate
surfactants in a weight ratio of from about 5:1 to about 1:5,
preferably from about 5:1 to about 1:1, more preferably from
about 5:1 to about 1.5:1. Especially preferred is a mixture
of an alkyl benzene sulfonate having from 9 to 15, especially
11 to 13 carbon atoms in the alkyl radical, the cation being
an alkali metal, preferably sodium; and either an alkyl sulfate
having from 10 to 20, preferably 12 to 18 carbon atoms in the
alkyl radical or an ethoxy sulfa-te having from 10 to 20,
pxeferably 10 to 16 carbon atoms in the alkyl radical and an
average degree o~ ethoxylation of 1 to 6, having an alkali metal
cation, preferably sodium.
The nonionic surfactants useful in the present invention
are condensates o ethylene oxide with a hydrophobic moiety
to provide a suxfactant having an average hydrophilic-
lipophilic balance (HLB) in the range from about 8 to 17,
preferably from about 9.5 to 13.5, more preferably from
about 10 to about 12.5. The hydrophobic moiety may be
aliphatic or armoatic in nature and the length of the
polyoxyethylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-
soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
Examples of suitable nonionic surfactants include:
1. ~he polyethylene oxide condensates of alkyl phenol, e.g.
the condensation products of alkyl phenols having an alkyl
~Z~3~3~
- 12 -
group containing from 6 to 12 carbon atoms in either a
straight chain or branched chain configuration, with
ethylene oxide, the said ethylene oxide being present in
amounts equal to 3 to 30, preferably 5 to 14 moles o~ ethylene
oxide per mole of alkyl phenol. The alkyl substituent in
such compounds may be derived, for example, from polymerised
propylene, di-isobutylene, octene and nonene. Other examples
include dodecylphenol condensed with 9 moles of ethylene
oxide per mole of phenol; dinonylphenol condensed with 11
moles of ethylene oxide per mole of phenol; nonylphenol and
di-isooctylphenol condensed with 13 moles of ethylene oxide.
2~ The condensation product of primary or secondary
aliphatic alcohols having from 8 to 24 carbon atoms, in
either straight chain or ~ranched chain configuration, with
from 2 to about 40 moles, preerably 2 to about 9 moles of
ethylene oxide per mole of alcohol. Preferably, the
aliphatic alcohol comprises between 9 and 18 carbon atoms
and is ethoxylated with between 2 and 9, desirably between 3
and 8 moles of ethylene oxide per mole of aliphatic alcohol.
The preferred surfactants are prepared from primary alcohols
which are either linear (such as those derived from natural
fats or, prepared by the Ziegler proces~ from ethylene, e.g.
myristyl, cetyl~ stearyl alcohols), or partly branched such
as the Lutensols, Dobanols and Neodols which have about 25
2-methyl branching (Lutensol being a Trade Mark of B~S~,
Dobanol and Neodol being Trade Marks of Shell), or
Synperonics, which are understood to have about 50~ 2-methyl
branching (S~nperonic is a Trade Mark of I.C.I.) or the
primary alcohols having more than 50~ branched chain structure
30 sold under the Trade Name Lial by Liquichimica. Specific
examples of nonionic surfactants falling within the scope of
the i~vention include Dobanol 45-4, Dobanol 45-7, Dobanol
45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol
91-~, Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic
14, the condensation products of coconut alcohol with an
average of between 5 and 12 moles of ethylene oxide per mole
of alcohol, the coconut alkyl portion having from 10 to 14
carbon atoms, and the condensation products of tallow
alcohol with an average of between 7 and 12 moles of ethylene
30~
oxide per mole of alcohol, the tallow portion comprising
essentially between 16 and 22 carbon atoms. Secondary
linear alkyl ethoxylates are also suitable in the present
compositions, especially those ethoxylates of the Tergitol
series having from about 9 to 15 carbon atoms in the alkyl
group and up to about 11, especially from about 3 to 9,
ethoxy residues per molecule.
3. The compounds formed by condensing ethylene oxide with
a hydrophobic base formed by the condensation of propylene
oxide with propylene glycol. The molecular weight of the
hydrophobic portion genexally falls in the range of about
1500 to 1800. Such synthetic nonionic detergents are
available on the market under the Trade Mark of "Pluronic"
supplied by Wyandotte Chemicals Corporation.
Especially preferred nonionic surfactants for use
herein are the Cg-Cl5 primary alcohol ethoxylates containing
3-8 moles of ethylene oxide per mole of alcohol, particularly
the C12-C15 primary alcohols containing 6-8 moles of ethylene
oxide per mole of alcohol.
Cationic surfactants suitable for use herein include
quaternary ammonium surfactants and surfactants of a semi-
polar natuxe, for example amine oxides.
Suitable surfactants of the amine oxide class have the
general formula I
Rl_ N ~ (CH2 ) 1 1~ ~R2
wherein R is a linear or branched alkyl or alkenyl group
havin~ 8 to 20 carbon atoms, each ~ is independently
~ om Cl_4 alkyl and ~(CnH2nO)mH where i is an
integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from
1 to 7, the sum total of CnH2nO groups in a molecule being
no more than 7.
In a preferred embodiment Rl has from 10 to 1~ carbon
atoms and each R2 is independently selected from methyl and
~(CnH2nO)mH wherein m is from 1 to 3 and the sum total of
CnH2nO groups in a molecule is no more than 5, preferably no
~21~3~91
- 14 -
more than 3. In a highly preferred embodiment, j is O and
each R is methyl, and R is C12-Cl~ alkyl.
Another suitable clas~ of amine oxide species is
represented by bis-amine oxides having the following sub-
stituents.
Rl tallo~ C16-cl8 alkyl; palmityl; oleyl; stearyl
R2 : hydrox~ethyl
i : 2 or 3
A specific example of this preferred class of bis-amine
oxides is: N-hydrogenated C16- C18 tallow alkyl-N,N',N'
tri-(2-hydroxyethyl) -propylene-l, 3-diamine oxide.
Suitable quaternary ammonium surfactants for use in
present composition can be defined by the general formula:
R3 _ N ~ (CH2)i - N 1 R4 z II
wherein R3 is a linear or branched alkyl, alkenyl or
alkaryl group having 8 to 16 carbon atoms and each R is
independently selected ~rom Cl ~ alkyl, Cl 4 alkaryl
and-(CnH2nO)m~ wherein i is an integer from 1 to 6, j
is O or 1, n is 2 or 3 and m is from 1 to 7, the sum
total of CnH2nO groups in a molecule being no more than
7, and wherein Z represents counteranion in number to
give electrical neutrality.
In a preferred embodiment, R3 has from 10 ta 14 carbon
atoms and each R4 is independently selected from methyl and
(CnH2nO)mH wherein m is from 1 to 3 and the sum total of
CnH2nO groups in a molecule is no more than 5, preferably no
more than 3. In a highly preferred embodiment j is 0, R is
selected from methyl, hydroxyethyl and hydroxypropyl and R3
is C12-C14 alkyl. Particularly preferred surfactants of
this class include C12 alkyltrimethylammonium salts C14
alkyltrimethylammonium salts coconutalkyltrimethylammonium
salts, coconutalkyldimethyl hydroxyethylammonium salts,
coconutalkyldimethylhydroxypropylammonium sal-ts, and C12
alkyldihydroxyethylmethylammonium salts.
~nother group of useful cationic compounds are the
~!
~2~
- 15 -
diammonium salts of formula II, in which j is 1, R3 is C12-
C14 alkyl, each R4 is methyl, hydroxyethyl or hydroxypropyl
and i is 2 or 3. In a particularly preferred surfactant of
this type, R3 is coconut alkyl, R4 iS methyl and i is 3.
The laundry additive products of the invention can
include various functional solid ingredients dispersed in
the organic matri~, especially peroxy bleaches and organic
pero~y acid bleach precursors. Suitable inorganic peroxygen
bleaches include sodium perborate mono-and tetrahydrate,
sodium percarbonate, sodium persilicate and urea-hydrogen
peroxide addition products and the clathrate 4Na2SO4:
2H202:1~aCl. Sui.table organic bleaches include peroxylauric
acid, peroxyoctanoic acid, peroxynonanoic acid,
peroxydecanoic acid, diperoxydodecanedioic acid,
diperoxyazelaic acid, mono- and diperoxyphthalic acid and
mono- and diperoxyisopthalic acid. Peroxyacid bleach
precursors suitable herein are disclosed in UK-A-~040983,
highly preferred being peracetic acid bleach precursors such
as tetraacetylethylenediamine, tetraacetylmethylenediamine,
tetraacetylhexylenediamine, sodium p-acetoxybenzene,
su~phonate, tetraacetylglycouril, pentaacetylglucose,
octaacetyllactose, and methyl 0-acetoxy benzoate. Bleach
precursors can be applied to substrate at a pracursor:
substrate ratio within the range from about 30:1 to about
l:lO, pre~erably from about 8:1 to about 1:2, while bleaches
can be applied to substrate at a bleach:substrate ratio from
about 30:1 to about 1:4, preferably from about lO:l to about
l:l. For improved stability, the bleach precursor and bleach
can be incorporated in physically separate locations of the
substrate.
The compositions of the invention can be supplemented
by all manner of other laundering ingredients, including suds
controlling agents, fluorescers, photoactivators, enzymes,
sequestrants, fabric softeners and antis-tatic agen~s, soil
suspending agents etc, either as part of the matrix of
organic materials or as a dispersion therein~
Suitable suds control].ing agents include microcrystalline
waves having a melting point in the range from about 65C to
about 100C, a molecular weight in the range from about 400-
.
~2~
- 16 -
1000, and a penetration value of at least 6, measured at
77C by ASTM-D1321; silicone suds controlling agent as
disclosed in US 3,933,672, particularly polydimethylsiloxanes
having a molecular weight in the range ~rom about 200 to
about 200,000 and a kinematic viscosity in the range from
about 20 to about 2,000,000 Inm/S, preferably from about 3000
to about 30,000 mm/s, and mixtures of siloxanes and hydrophobic
silanated (preferably trimethylsilanated) silica having a
particle size in the range from a~out 10 millimicrons to
about 20 millimicrons and a specific surface area above
about 50 m2/g; and the self emulsifying suds suppressors
described in DE-A-2,646,126, published April 28, 1977.
Suitable fluorescers herein include Blackophor MBBH
(Bayer AG) and Tinopal CBS and EMS (Ciba Geigy). Suitable
photoactivators are disclosed in U.S. Patent 4,417,994
issued November 29, 1983, highly preferred materials being
zinc phthalocyanine tri- and tetrasulphonates.
Chelating agents that can be incorporated include
citric acid, nitrolotriacetic and ethylene diamine tetra
acetic acids and their salts, organic phosphonate derivatives
such as those disclosed in Diehl US Patent No. 3,213,030
issued 19 October, 1965; Roy US Patent No. 3,433,021 issued
14 January, 1968; Gedge US Patent No. 3,292,121 issued ~
January, 1968; and Bersworth US Patent No. 2,599,807 issued
10 June, 1952, and carboxylic acid builder salts such as those
disclosed in Diehl US Patent No. 3,308,067 issued 7 March,
1967. Preerred chelating agents include nitrilotriacetic
aaid (NTA), nitrilotrimethylene phosphonic acid (NTMP),
ethylene diamine tetra methylene phosphonic acid (EDTMP)
and diethylene triamine penta methylene phosphonic acid (DETPMP),
and these are incorporated in amounts such that the substrate
chelating agent weight ratio lies in the range from about
20:1 to about 1:5, preerably from about 5:1 to about 1:5 and
most preferably 3:1 to 1:1.
Antiredeposition and soil suspension agents also
constitute preferred components of the additive product of
- 17 -
the invention Cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose are examples
of soil suspension agents and suitable antiredeposition
agents are provided by homo- or co-polymeric polycarboxylic
acids or their salts in which at least two carboxyl radicals
are present separated by not more than two carbon atoms.
Highly preferred polymeric polycarboxylic aclds are
copolymers of maleic acid or maleic anhydride with methyl
vinyl ether, ethyl vinyl ether, ethylene or acrylic acid,
the polymers having a molecular weight in the range from
12,000 to 1,500,000.
A further description of suitable polymeric
polycarboxylic acids is provided in the Applicants' European
Patent Application No. 82301776.9 published October 20, 1982.
In a method of making the laundry-additive products of
the invention, a current of molten laundry-additive
composition is dispensed onto moving substrate at an
application rate of from about 100 to about 400 g/m2,
preferably from about 120 to about 320 g/m2 of substrate,
~0 so as to coat no more than about 70%, preferably no more than
about 45% of the apertures of the substrate. Thereafter,
the coated substrate is passed through smoothing and distri-
buting means arranged to smooth and distribute the coating
on the substrate with substantially no removal of coating
material from off the substrate.
The temperature of the melt generally lies in the range
from about 35C to about 85C, preferably from about 40C to
about 75C, more preferably from about 50C to about 70C
and the average particle size of solids dispersed in the me~t
ill preferably less than about 250 micron, more preferably
less than about 100 micron. In preferred embodiments, the
melt is dispersed from the nip of a pair of counter-rotating,
heated rollers having a nip setting of less than about 400
microns, preferably from about 150 to about 300 microns,
the substrate being arranged for movement counter to one
of the rollers and in contact therewith, whereby -the melt
is transferred to the substrate by a wiping action. Thereafter,
the substrate passes through smoothing and distributing
means, for example a pair of plates stationed on opposite
9~2~
- 18 -
sides of the substrate as a spacing of less than about 300
microns, preferably from about 120 to about 220 microns.
Finally, the coated substrate is cooled in a current of air.
The invention is illustrated in the following non-
limitative Examples in which parts and percentages are by
weight unless otherwise specified.
In the Examples, the abbreviations used have the
following designation:
LAS : Linear C12 alkyl benzene sulphonate
12/14 : Sodium C12-C14 alkyl sulphate
TAE : Hardened tallow alcohol ethoxylated with
n n moles of ethylene oxide per mole of
alcohol
C12Tl~AB : Cl~ alkyl trimethyl ammonium bromide
Dobanol 45-E 7 : A C 4-C15 primary alcohol condensed
wit~ 7 moles of ethylene oxide, marketed
by ~hell
PEG : Polyethylene glycol (MWt normally follows)
TAED : Tetraacetylethylenediamine
PAG : Pentaacetylglucose
AOBS : Sodium p-acetoxy benzene sulphonate
Silicone/Silica : 85% polydimethyl siloxane 15% silanated
silica
Porphine : Tri/tetra sulphonated zinc phthalocyanine
Gantrez ANll9 : Maleic anhydride/vinyl methyl ether
copolymer, believed to have an average
molecular weight of 240,000, marketed
by GAF. This material was prehydrolysed
with NaOH before addition.
30 Perborate : Anhydrous sodium perborate bleach of
empirical formula NaBO2.H202
EDTA : Sodiumethylenediaminetetraacetate
Bri~htener 1 : Disodium 4,4'-bis(2-morpholino-4-
anilino-s-triazin-6-ylamino)
stilbene-2:2'-disulphonate
Bright`ener 2 : Disodium 4,4'-bis(2;sulphonato styryl)
biphenyl
DETPMP : Diethylenetriamine penta(methylene
phosphonic acid), marketed by Monsanto
under the Trade name Dequest 2060
EDTMP : Ethylenediamine tetra(methylene phosphonic
acid), marketed by Monsanto, under the
Trade name Dequest 2041
3~
- 19 -
-
Substrate 1 : Non-woven fabric formed of 100%
unbleached crimped rayon fibres of 1.5
denier bonded with 23% polyacrylate
binder; basis weight 35 g/m2; 17
elliptical apertures/cm2; aperture
width 0.9mm; aperture length 2.5mm
Substrate 2 : Non-woven fabric formed of 100~
unbleached crimped rayon fi.bres of
1.5 denier bonded with 18% polyacrylate
binder; basis weight 35g/m2; 22 square-
shaped apertures/cm2; side dimension
l.lmm
EXAMPLES 1 to 6
haundry additive products according to the invention are
prepared as follows: For each product, the components of
the laundry additive composition are mi~ed at a temperature
of about 65C and passed through a Fryma Colloid Mill,
Model MK35-R/MZ 80R (made by M.M. Process Equipment Ltd
of M.M. House, Frogmore Road, Hemel Hempstead, Hertfordshire,
United Kingdom) in which the grinding faces are set to a
separation of about 180 microns~ The melt is then fed through
a pair of counterrotating rolls heated to 76C and having a
nip setting of 250 microns and is transferred to substrate
moving counter to one of the rollers by wiping. The coated
substrate is finally passed between a pair of static plates
having a spacing of 180 microns, air-cooled, and cut into
sheets of size 35 x 23cm.
EXAMPLES
1 2 3 4 5 6
30 LAS - 3 - - 5
C12/14As 3 6 3 3 8
T~E2S ~ 3 - _ _ 4
C12TMAB 2 - 4 3 - 3
Dobano~l 45E7 5 3 5 4 5
PEG 8000 5 5 7 6 7 8
TAED 5
PAG - 3 _ 3
AOBS
Silicone/Silica 0.3 0.2 0.2 0.2 0~3 0.3
40 Porphine - 0.2 - - - 0.3
3~L
- 20 -
Gantrez ANll9 O.3 - - O.8 - O.5
Perborate - ~ - 5
EDTA - - - 0.2
Brightener 1 - 0.3 0.1 - 0.2 0.1
Brightener 2 0.1 0.1 - 0.2 - 0.3
DETPMP 0.5 1 - - 0.8
EDTMP - - 1.5 0.5 - -
Moisture 0.8 0.5 0.6 0.2 0.5 0.7
Substrate 1 2.8 2.8 - 2.8
10 Substrate 2 - - 2.8 - 2.8 2.8
Percent Coated
Apertures 40 33 45 50 42 55
The above products are effective laundry detergents
combining a high composition:substrate ratio with excellent
flexibility, product release, feel and storage characteristics.
