FIELD OF THE INVENTION
[0001] This invention relates to laundry products adapted to provide grease and oil removal
benefits and more especially to laundry products in non-particulate solid form that
incorporate amine surfactants.
BACKGROUND TO THE INVENTION
[0002] Detergent compositions containing alkyl amine surfactants are known in the art, particularly
for the purpose of degreasing metals and other hard surfaces. Examples of such compositions
in liquid form are disclosed in BP 1438948, USP 3468804 and South African Application
No. 6806992, while exemplary particulate detergent compositions are disclosed in DTAS
1034307. A further application of amines as surfactants is in the dry cleaning of
textiles, a typical disclosure being that in DTAS 1057275.
[0003] Fabric-softening products comprising amines absorbed on non-particulate substrates,
designed for addition to drum dryers, have also been suggested in USP 4077891, USP
3895128 and Belgian Patent No. 840402.
[0004] Whilst the prior art has disclosed the use of amines as surfactans useful in degreasing
applications, it has not recognised the benefits that can be obtained by the combination
of certain such amines with nonionic surfactants in a form suitable for use in an
aqueous textile laundering process.
[0005] Accordingly, the present invention seeks to provide a product in solid non-particulate
form adapted to provide enhanced grease and oily soil removal from textiles in an
aqueous textile cleaning bath.
SUMMARY OF THE INVENTION
[0006] According to one aspect of the present invention there is provided a laundry detergent
product adapted to provide grease and oily soil removal from textiles comprising
(a) a non-particulate flexible substrate in water releasable combination with
(b) a primary, secondary or tertiary amine or salt thereof, containing a total of
not more than 40 carbon atoms in the amine radical, at least one, but not more than
two groups in the amine radical containing an alkyl or alkenyl group of at least 8
carbon atoms, and
(c) a surfactant selected from water soluble anionic and ethoxylated nonionic surfactants
and mixtures thereof,
[0007] the amount of (c) present in the mixture being from 0.1 to 10 parts by weight per
part of the amine moiety of (b) the mixture being water dispersible
or water soluble at 30°C, the total amount of (b) and (c) being from 0.1 to 30 parts
by weight per part of (a) .
[0008] Preferably, the amine is a primary or tertiary amine or amine salt containing not
more than 20 atoms in the amine radical and most preferably the amine is a mono C
12-14 alkyl primary or tertiary amine salt. Mixtures of amines or amine salts can be used.
[0009] In accordance with a further aspect of the invention, there is provided a method
of making a laundry product adapted to provide grease and oily soil removal comprising
the steps of
(a) mixing a primary, secondary or tertiary amine or amine salt containing not more
than 40 carbon atoms and at least one but not more than two alkyl or alkenyl groups
of at least 8 carbon atoms in the amine radical, with an anionic or ethoxylated nonionic
surfactant in an amount of from 0.1 to 10 parts by weight of nonionic or anionic surfactant
per part of amine or amine radical, together with from 0 to 10 parts per part of amine
or amine radical, of a processing aid selected from C12-18 fatty acids, polyethylene glycols of MWt > 4000, inorganic and organic thickening
agents as hereinafter defined, and mixtures thereof
(b) forming a fluid mass of the mixture
(c) treating a flexible non-particulate substrate with the fluid mass so as to impregnate
and/or coat the substrate and
(d) causing the fluid mass to solidify on the substrate to provide from 0.1 to 30
parts by weight of the mixture per part by weight of the substrate.
DETAILED DESCRIPTION OF THE INVENTION
The amine
[0010] The amines suitable for the purposes of the present invention are saturated or unsaturated
primary, secondary and tertiary amines or salts thereof, in which the amine portion
of the molecule contains not more than 40 carbon atoms and in which at least one and
not more than two of the organic groups attached to the nitrogen atom in the amine
portion contain an alkyl or alkenyl chain of at least 8 carbon atoms.
[0011] The organic group or groups containing more than 8 carbon atoms can be saturated
or unsaturated aliphatic in nature, as in material derived from naturally occurring
oils and fats such as coconut and palm oil, tallowfat and soya bean oil and marine
oils. These aliphatic groups can also be derived from synthetic hydrocarbon materials
such as Ziegler olefins and OXO alcohols and can be substantially linear or highly
branched in nature. The aliphatic groups may form part of an aralkyl group such as
an alkyl-benzyl group in which the alkyl portion can have from 8-15 carbon atoms and
can be derived from any of the sources given above.
[0012] The remaining group or groups in amines useful in the present invention are selected
from hydrogen, C
1-C
7 alkyl, C
l-C
4 hydroxy alkyl and benzyl moieties. Preferred groups are hydrogen, methyl and hydroxy
ethyl, and no more than one benzyl should be attached directly to the nitrogen atom.
Thus suitable amines include
[0013]
tallow alkyl amine
tallow methyl amine
tallow dimethyl amine
.tallow diethyl amine
coconut alkyl amine
coconut methyl amine
coconut dimethyl amine
myristyl alkyl amine
myristyl methyl amine
myristyl dimethyl amine
lauryl ethyl amine
lauryl diethy l amine
n-decyl benzyl amine
n-dodecyl dihydroxyethyl amine
n-dodecyl dibutyl amine
n-dodecyl amine
cetyl dimethyl amine
di-octyl amine
di-octyl methyl amine
C11 -C13 alkylbenzyl amine
C11 -C13 alkylbenzyl dimethyl amine di-cetyl methyl amine
di-tallow methyl amine
di-tallow hydroxyethyl amine
di-myristyl ethyl amine
di-lauryl hydroxyethyl amine
[0014] Mixtures of any of the above may be employed.
[0015] Synthesis of the amines can be by any of the methods well-known in the art and which
form no part of the present invention.
[0016] The amines may be present as such or in the protonated form as salts. For this purpose
any of the conventional anions can be used, viz. halides (chlorides, bromides and
iodides) sulphates, silicates, methosulphates, borates, phosphates and carboxylates.
Suitable carboxylates include formates, acetates, propionates and the C
12-C
18 fatty acid carboxylates derived from naturally occurring triglycerides, especially
stearates.
[0017] The amine salts may be formed prior to the processing of the product or may in certain
instances be formed in situ in a manner to be described.
[0018] Preferred amines are the alkyl primary and tertiary amines in which the alkyl group
is derived from middle cut coconut alcohol, hardened tallow or synthetic C
12 -C
13 alcohol produced by olefin build-up. Although the invention embreres the use of amines
containing up to 40 carbon atoms; it has been found that the grease and oily soil
efficiency declines as the amine molecular weig increases i.e., a larger amount of
amine or amine is required to achieve the same level of performance Accordingly, preferred
amines are those containing not more than 20 carbon atoms in the amine radical and
only one group contains more than 8 carbon atoms. In the most preferred embodiments
of the invention the amines are primary C
12- C
14 alkyl amines or tertiary C
12-C
14 dimethyl amines.
[0019] In the preferred embodiments of the invention, the amines are utilised as salts,
the most preferred embodiments being those in which the amine salts, particularly
the long chain carboxylates, are formed iu situ during the processing of the product.
The co-surfactant
[0020] An essential component of the present invention is a co-surfactant which may be nonionic
or anionic in character. Suitable nonionic detergent materials for the purposes of
the present invention can be broadly defined as compounds produced by the condensation
of alkylene oxide groups having a hydrophilic nature with an organic hydrophobic compound
having a reactive hydrogen atom. The hydrophobic groups may be aliphatic or alkylaromatic
in nature and the size of the polyoxyalkylene group which is condensed with any particular
hydrophobic group can be readily adjusted to provide a water soluble compound having
the desired balance between hydrophilic and liphophilic characteristics.
[0021] Examples of suitable nonionic detergents include
1. The polyethylene oxide condensates of alkyl phenol, e.g. the condensation products
of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either
a straight chain branched chain configuration, with ethylene oxide, the said ethylene
oxide being present in amounts equai to 5 to 25 moles of ethylene oxide per mole of
all phenol. The alkyl substituent in such compounds may be derived, for example, from
polymerised propylE di-isobutylene, octene and nonene. Other examples include dodecylphenol
condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed
with 15 moles of ethylene oxide per mole of phenol; nonylphenol condensed with 20
moles of ethylene oxide per mole of nonylphenol and di-iso-octylphenol condensed with
15 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 branched chain configuration, with
from 1 to about 30 moles of alkylene oxide per mole of alcohol. Preferably, the aliphatic
alcohol comprises between 9 and 15 carbon atoms and is ethoxylated with between 2
and 12, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol.
Such nonionic surfactants are preferred from the point of view of providing good to
excellent detergency performance on fatty and greasy soils, and in the presence of
hardness sensitive anionic surfactants such as alkyl benzene sulphonates. The preferred
surfactants are prepared from primary alcohols which are either linear (such as those
derived from natural fats or prepared by the Ziegler process from ethylene, e.g. myristyl,
cetyl, stearyl alcohols), or partly branched such as the Dobanols and Neodols which
have about 25% 2-methyl branching (Dobanol and Neodols being Trade Names of Shell)
or Synperonics, which are understood to have about 5O% 2-methyl branching (Synperonic
is a trade name of I.C.I.) or the primary alcohols having more than 50% branched chain
structure sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic
surfactant falling within the scope of the invention include Dobanol 45-4, Dobanol
45-7, Dobanol 45-11, Dobanol 91-3, Dobanol 91-6, Dobanol 91-8, 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 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 16 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 generally falls in the range of about 1500 to 1800. Such
synthetic nonionic detergents are available on the market under the trade name of
"Pluronic" supplied by Wyandotte Chemicals Corporation.
[0022] For the purposes of obtaining optimum grease and oily soil removal the nonionic surfactant
should have a lower consolute temperature in the range 25-65°C preferably in the range
30-50 C . Preferred nonionic surfactants having this characteristic are the ethoxylated
primary or secondary C
9-C
15 alcohols containing 2-12 ethylene oxide groups per mole of alcohol, more particularly
the C12-C15 alcohols containing 6-9 ethylene oxide groups per mole of alcohol. Particularly
preferred nonionics are these marketed under the trade names Dobanol 45-7 and Dobanol
45-9 by Shell Oil Company.
[0023] Synthetic anionic surfactants can also be employed as co-surfactants in the products
of the present invention.
[0024] A highly preferred class of anionic detergents includes water-soluble salts, particularly
the alkali metal, ammonium and alkanolammonium salts of organic sulfuric 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
sulfonic acid or sulfuric 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 sulfates, especially those obtained by sulfating the higher alcohols (C
8-C
18) carbon atoms produced by reducing the glycerides of tallow or coconut oil. and sodium
and potassium alkyl benzene sulfonates, in which the alkyl group contains from about
9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g.
those of the type described in USP 2,220,099 and 2,477,383. Especially valuable are
linear straight chain alkyl benzene sulfonates in which the average of the alkyl group
is about 11.8 carbon atoms, abbreviated as C
11.8 LAS.
[0025] A preferred alkyl ether sulfate surfactant component of the present invention is
a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean)
carbon chain length within the range of about 12 to 16 carbon atoms, preferably from
about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation
of from about 1 to 4 moles of ethylene oxide.
[0026] Other anionic detergent compounds herein include the sodium alkyl glyceryl ether
sulfonates, especially those ethers of higher alcohols derived from tallow and coconut
oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium
or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about'l
to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain
about 8 to about 12 carbon atoms.
[0027] Other useful anionic detergent compounds herein include the water-soluble α-sulfonated
fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and
from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic
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 sulfates containing from
about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene
oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon
atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, expecially
14 to 18 carbon atoms, and s-alkyloxy alkane sulfonates containing from about 1 to
3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane
moiety.
[0028] Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures
of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical
and mixtures thereof, the cation being an alkali metal preferably sodium; and from
about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon
atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having
an alkali metal cation, preferably sodium
[0029] As stated earlier, the co-surfactant may comparative nonionic or anionic surfactant
or a mixture of the two, the relative proportions in such a mixture not being of importance
for the purpose of the present invention. The total amount of the co-surfactant should
be such as to provide from 0.1 to 10 parts by weight of co-surfactant per part of
amine, preferably from 1 to 10 parts by weight and most preferably from 1.5 to 5 parts
by weight.
[0030] A requirement of the product of the invention is that the aminc-co-surfactant mixture
should be water soluble or water-dispersible at 30
0C. In the most preferred embodiments of the invention in which the non-particulate
substrate is a fibrous non-woven sheet, the composition embodying the amine-cosurfactant
mixtu should also be solid at this temperature. Mixtures of amines and nonionic and/or
anionic surfactants do not have a sharply defined melting point and the requirement
that the mixture be solid at 30
0C is also intended to
that the mixture should not soften at 30
0C and below.
The non-particulate substrate
[0031] The third essential component of the present invention is a flexible non-particulate
substrate with which the other components are in water-releasable combination. In
the context of the present invention, a water-releasable combination is one that is
capable of being separated by water through solution, dispersion, leaching, softening
or melting.
[0032] The substrate itself may be water-soluble or water insoluble and in the latter case,
it should possess sufficient structural integrity under the conditions of the wash
to be recovered from a washing machine at the end of the laundry cycle. Structures
that are water-disintegratable i.e., that break down in aqueous media to individual
fibres or insoluble particles are not considered satisfactory for the purposes of
the present invention.
[0033] Water soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol
and water soluble polyvinyl pyrrolidone polymers, which can be formed into non-woven
and woven fibrous structures. Suitable water insoluble materials include, but are
not restricted to, natural and synthetic fibres, foams, sponges and films.
[0034] The substrate may have any one of a number of physical forms such as sheets, blocks,
rings, balls, rods or tubes. Such forms should be amenable to unit usage by the consumer,
i.e., they should be capable of addition to the washing liquor in measured amounts,
such as individual sheets, blocks or balls and unit lengths of rods or tubes. Certain
of these substrate types can also be adapted for single or multiple uses and can accept
loadings up to 30 times the substrate weight.
[0035] A highly preferred substrate type is a sheet, the form of which is the most advantageous
for releasing material rapidly into a wash liquour, particularly under the limited
time conditions prevailing in automatic washing machine cycles. Preferably the sheet
is water pervious i.e., water can pass from one surface of the sheet to the opposite
surface and, for film type substrates, perforation of the sheet is desirable. The
most preferred form of the substrate is a sheet of woven or non-woven fabric or a
thin sheet of cellular plastic material. Woven fabric sheets can take the form of
a plain weave natural or synthetic fibre of low fibre count/unit length, such as is
used , for surgical dressings, or of the type known as cheese cloth.
[0036] Loading limitations on non-woven sheet type substrates limit the amount of material
that can be applied to the sheet to a maximum of about ten times the sheet weight.
Suitable material which can be used as sheet-type substrates include, among others,
sponges, paper and woven and non-woven cloth.
[0037] As the name implies, a sponge sheet will be in the form of an absorbent foam-like
material. The term "absorbent foam-like material" is intended to encompass three dimensional
absorptive materials such as "gas blown foams", natural sponges and composite fibrous
based structures such as are disclosed in US Patent Nos. 3311115 and 3430630 specifically
incorporated herein by reference. Synthetic organic polymeric plastics material such
as polyether, polyurethane, polyester, polystyrene, polyvinylchloride, nylon, polyethylene
and polypropylene are most often employed and a particularly preferred material of
this type is a hydrophilic polyurethane foam in which the internal cellular walls
of the foam have been broken by reticulation. Foams of this type are described in
detail in Dulle US Patent No. 3794029 which is hereby specifically incorporated by
reference. A preferred example of this foam type comprises a hyrophilic polyurethane
foam of density about 0.038 g/cubic centimetres with a cell count of between 8 and
40 cells per cm. , preferably about 24 to 32 per cm. available from the Scott Paper
Company, Eddystone, Pennsylvania, USA, under the Registerd Trade Mark "Hydrofoam".
[0038] Paper sheets can also be used in products of the present invention provided that
they possess sufficient wet strength to maintain their integrity during use. A paper-based
sheet of a type suitable for the purpose of the inventions is disclosed in BP 1370112,
the disclosures of which are hereby specifically incorporated by reference.
[0039] The preferred non-woven cloth substrates usable in the invention herein can generally
be defined as adhesively bonded fibrous or filamentous products, having a web or carded
fibre structure where the fibre strength is suitable to allow
or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly
or in
array (i.e., an array of fibres in a carded web
partial orientation of the fibres is frequently
as well as a completely haphazard distributional orientation) or substantially aligned.
The fibres of filaments can be natural (e.g. wool, sil, jute, hemp, cotton, linen,
sisal, or ramie) or synthetic (e.g. rayon, cellulose, or polyesters).
[0040] Methods of making non-woven cloths are not a part of this invention and being well
known in the art, are not described in detail herein. Generally, such cloths are made
by air or water laying processes in which the fibres or filaments are first cut to
lengths from long strands, passed into a water or
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. Non-woven
cloths made of polyesters, polyamides, vinyl resins, and other thermoplastic fibres
can be spunbonded, i.e., the fibres are spun out onto a flat-surface and bonded (melted)
together by heat or by chemical reactions.
[0041] The absorbent properties desired herein are particularly easy to obtain with non-woven
cloths and are provided merely by building up the thickness of the cloth, i.e., by
superimposing a plurality of carded webs or mats to a thickness adequate to obtain
the necessary absorbent properties, or by allowing a sufficient thickness of the fibres
to deposit on the screen. Any diameter or denier of the fibre (generally up to about
10 denier) can be used, inasmuch as it is the free space between each fibre that makes
the thickness of the cloth directly related to the absorbent capacity of the cloth,
and which further makes the non-woven cloth especially suitable for impregnation by
means of intersectional or capillary action. Thus, any thickness necessary to obtain
the required absorbent capacity can be used.
[0042] The choice of binder-resins used in the manufacture of non-woven cloths can provide
substrates possessing a variety of desirable traits. For example, the absorbent capacity
of the cloth can be increased, decreased, or regulated by respectively using a hydrophilic
binder-resin, a hydrophobic binder-resin or a mixture thereof in the fibre bonding
step. Moreover, the hydrophobic binder-resin, when r:,ed singly or as the predominant
compound of a hydrophobic- hydrophilic mixture, provides non-woven cloths which are
especially useful as substrates when the surfactant- substrate combinations disclosed
herein are used in an automatic washer.
[0043] When the substrate herein is a non-woven cloth made from fibres, deposited haphazardly
or in randc array on the screen, the compositions exhibit excellent strength in all
directions and are not prone to tear or separate when used in the washer. Apertured
non-woven substrates are also useful for the purposes of the present invention. The
apertures, which extend between opposite surfaces of the substrate are normally in
a pattern and are formed during laydown of the fibres to produce the substrate. Exemplary
apertured non-woven substrates are disclosed in US Patent Nos. 3,741,724, 3,930,086
and 3,750,237, the disclosures of which are specifically incorporated herein by reference.
[0044] Preferably, the non-woven cloth is water-laid or air-laid and is made from cellulosic
fibres, particularly from regenerated cellulose or rayon, which are lubricated with
standard textile lubricant. Preferably, the fibres are from 45 to 50 mm in length
and are from 1.5 to 5 denier (Denier
internationally recognised unit in yarn measure, corresponding to the weight in grams
of a
length of yarn). Preferably, the fibres are a least partially orientated haphazardly,
particularly substantially haphazardly, and are adhesively bonder together with hydrophobic
or substantially hydrophobic binder-resin, particularly with a nonionic self- crosslinking
acrylic polymer or polymers. Conveniently, the cloth comprises about 70% fibre and
30% binder-resin polymer by weight and has a basis weight of from 10 to about 100,
preferably 20 to 60 grammes per square yard.
[0045] A particularly preferred example is an air-laid non-woven cloth comprising 70% regenerated
cellulose (American Viscose Corporation) and 30% hydrophobic binder-resins (Rhoplex
HA-8 on one side of the cloth, Rhoplex HA-16 on the other; Rohm & Haas, Inc.). The
cloth has a thickness of 4 to 5 mils., a basis weight of about
28
g. per square metre and an absorbent capacity of 6. A 30 cm length of the cloth 21 cm.
wide, weighs about 1.78 grams. The fibres are 1/4 in length, 1.5 denier and are orientated
substantially haphazardly. The fibres are lubricated with sodium oleate.
[0046] A further preferred substrate is a water-laid, non-woven cloth commercially available
from C.H. Dexter Co. Inc. The fibres are regenerated cellulose, about 0.95 cm. in
length, about 1.5 denier, and are lubricated with a similar standard textile lubricant.
The fibres comprise about 70% of the non-woven cloth by weight and are orientated
substantially haphazardly; the binder-resin (HA-8) comprise about 30% by weight of
the cloth. The substrate is about 4 mils. thick, and it has a basis weight of about
28 g. per square metre and an absorbent capacity of 5.7. One foot length of the cloth,
21 cm. wide, weighs about 1.66 grams.
[0047] The total loading of water releasable components on the substrate should be such
as not to exceed 30 times the substrate weight and in the case of sheet-type substrates
should be limited to 10 times the substrate weight, preferably from 2-7 times the
substrate weight. The size and shape of the substrate is a matter of choice and is
determined principally
associated with the convenience of its use.
type substrate should not be so small as
crevices of the machine or the
or so large as to be awkward
dispense from the container in which it is sold. For the purposes of the present invention
sheets ranging in plan area from 185 sq. cm. to 1850 sq. cm. are acceptable, the preferred
area lying the range of from 740 to 1480 sq. cm for foamed sheets. Such a size has
the additional advantage of being too large to be swallowed by e.g., small children,
thereby minimising the risk of internal damage from ingestion of the materials absorbed
on the substrate.
Optional components
[0048] A wide range of optional components can be applied to the substrate, subject only
to loading limitations, compatibility with the other components and feasibility of
incorporation. Thus organic surfactants other than those identified as essential components
can also be applied provided that their presence does not detract from the grease
and oily soil removal capability of the combination of the present invention. Other
materials, such as organic chelating agents, anti-redeposition agents, suds modifying
agents, fluorescers, perfumes, pigments and dyes can also be incorporated. The invention
is particularly adapted to be used in conjunction with the product disclosed in German
Patent Application DTOS, 2744642 published April 13th.1978, the disclosures of which
are specifically incorporated herein by reference. DTOS 2744642 teaches the incorporation
of an organic peroxy bleach precursor on a flexible non-particulate substrate, for
the purpose of providing enhanced removal of oxidisable stains from textiles when
added to a laundry wash liquor containing an inorganic persalt.
[0049] A preferred optional ingredient in the product of the present invention is a processing
aid which serves as a plasticiser for the other materials
during their application onto or into the substrate and also enhances the tactile
aesthetics of the product. Suitable materials for this function include C
12-C
18 fatty acids and polyethylene glycols of MWt > 4000 more preferably MWt ; 6000.
[0050] Thickening agents are also useful ingredients in
of the present invention and are defined as
increase the viscosity or reduce the
the mixture such as silica, talc,kaolinite
morillonite as well as High MWt organic materials
cellulose derivatives, alginates, axyasrylates and starch.
[0051] of the optional ingredients
parts by weight per part of
the case of ingredients such as dyes,
and perfumes and can be as high as 10 parts per part of substrate for surfactants.
More commonly however, for one-time-use products, the level of incorporation for individual
optional ingredients such as chelating agents, surfactants and bleach precursors is
in the range 0.1-3.0 parts by weight per part of substrate.
[0052] The product of the present invention can be made in a variety of ways and is not
critically dependent on any particular manufacturing route. Thus aqueous or non-aqueous
solutions and dispersions and molten mixtures of the components can be formed and
applied to the flexible non-particulate substrate. One technique of application is
by immersion of the substrate in the component solution or dispersion followed by
removal of the excess liquor by squeeze rolls.
[0053] In this method, the mixture of amine, surfactants etc., in liquid form, is placed
into a pan or trough which can be heated, if necessary, to maintain the contents in
liquid form. To the liquid mixture is then added any further additive. A roll of absorbent
substrate is then set up on an apparatus so that it can unroll freely. As the substrate
unrolls, it travels downwardly and, submersed, passes through the pan or trough containing
the liquid mixture at a slow enough speed to allow sufficient impregnation. The treated
substrate then travels, at the same speed, upwardly and through a pair of rollerswhich
squeeze off excess bath liquid. The impregnated substrate is then cooled to room temperature,
after
lengths, and subsequently packaged any or used.
[0054] The rollers used resemble squeeze rolls" used by those in the paper and paper-making
art; they can be made of hard rubber or steel. Preferably, the rollers are adjustable,
so that the orifice between their respective surfaces can be regulated to control
the amount of the liquid on the substrate.
[0055] In another method of application, the amine and other ingredients in liquid form
is sprayed onto an absorbent substrate as it unrolls. The unrolled substrate web is
arranged to slide over the spray nozzle which comprises a horizontally disposed tube
formed with a slit extending along its top surface. The molten slurry of amine co-surfactant
mixture and any additives mixed therewith is forced through the slit into the substrate
and the excess liquid is then squeezed off by the use of squeeze rollers. A melt temperature
in the range of 40
o-80
oC preferably 45°-75°c is used and the molten material should have a viscosity of less
than 5000 centipoises at 50°C, preferably no more than 500 centipoises.
[0056] Other variations include the use of metal "nip" rollers onto the leading or entering
surfaces of which the impregnating mixture is sprayed, which variation allows the
absorbent paper to be treated, usually on one side only, just prior to passing between
the rollers wherein excess liquid is squeezed off. This variation additionally involves
the use of metal rollers which can be heated to maintain the impregnating mixture
as a liquid A further method involves separately treating a desired number of the
individual plies of a multi-ply paper and subsequently adhesively joining the plies
with a known adhesive-joiner
this provides a composition which can be
on one of its outer sides, yet contains
plies, each of which is treated on both
sheet-type substratcs of the
any of the above techniques can be
the most convenient process has been found
employing a molten mixture of the components at a temperature in the range 40-100
oC. For systems of this type that contain suspended solids, some refinements are desirable
in order to prevent segregation of the suspended solids and also to prevent build-up
of solidified molten material over long periods of operation.
[0057] In the modified process for handling a suspension of solids in a melt the suspension
in the form of a uniform dispersion is fed into a v-shaped trough formed by the generally
upright portion of the face of a heated, rotating horizontal roll and a plate inclined
thereto so as to leave a small clearance between the bottom of the plate and the roll
face. A thin coating of suspension is carried downwards through the clearance and
is transferred to a second horizontal roll in contact with the first but rotating
in the opposite direction. This second roll is in contact with a continuously advancing
web of substrate material and its direction of rotation is such as to make its direction
of movement opposite to that of the substrate at the point of contact. Under these
conditions the coating on the roll transfers to the substrate and impregnates it without
any build-up of the suspended solids occurring on the roll. In order to ensure uniform
distribution of the molten suspension the impregnated substrate is preferably passed
over one or more further counter rotating rolls that serve to spread the suspension
evenly over the substrate before it is cooled in an air stream to solidify the impregnating
material
[0058] In order to provide a mixture having suitable characteristics i.e., solidification
over a range of temperature to give a waxy rather than a crystalline solid, ccrtain
of the amine-co-surfactant mixtures suitable for the purposes of the invention need
to be blended with a plasticising or thickening agent.
[0059] For amine-co-surfactant mixtures melting in the optimum range i.e., 50°-80°C, a processing
aid is not essential in the preferred method of manufacture of products in accordance
with the invention. Such mixtures inherently possess the correct viscosity characteristics
for satisfactory application to the substrate and indeed may themselves be used as
carriers for other, optional, ingredients, such as chelating agents, high melting
point bleach precursors and soil suspending agents. Nevertheless, additives of a waxy
character may still be employed in order to provided robustness to the process, for
example, by reducing dust or by modifying the range of temperatures over which the
application process can be carried out. The additives may also servea funtional purpose
in the productby enhancing the rate of release and dissolution of the amine-co-surfactant
mixture in aqueous media and by modifying the tactile impression created by the product.
[0060] As previously mentioned the amine can be incorporated as such or in the form of an
amine salt. The latter form is preferred and a highly preferred salt is a long chain
ratty acid salt of the amine. This salt can be formed prior to the mixture of the
components and their application to the substrate but more preferably the salt is
formed in situ in the molten
mixture by reaction of the free
the chosen fatty acid. A slight excess
acid is added relative to that required for
reaction with the amine and this acts
in the manner described above.
made in accordance with the present
adapted to provide grease and oily soil benefits when used as the sole source of detergent
for a standard 3.5 k
g load of soiled fabrics in a conventional washing machine holding 20 litres of water.
[0061] However, these benefits are also observed when the product is employed as an additive
to commercially available, heavy-duty laundry detergents containing from 5-15% anionic
and or nonionic surfactants and from 10-80% inorganic builder salts. Such commercially
available detergents are normally used at a product concentration in the range 0.1%-1.0%
by weight. For both types of use the product should be added with the soiled fabrics
at the beginning of-the wash cycle. The invention is illustrated in the following
examples in which parts and percentages are on a weight basis unless otherwise stated.
EXAMPLE I
[0062] 150 g. of powdered n-dodecylamine hydrochloride are added to 500 g. of C
14-C
15 primary alcohol (a substantially linear alcohol with < 25% 2-methyl branching) condensed
with an average of seven moles of ethylene oxide per mole of alcohol and the mixture
heated to 70°C with agitation to give a homogeneous dispersion. The dispersion is
transferred to a hold tank before being pumped to the applicator which comprises a
head formed with a rectangular slot orifice having a length of 25 cms. The applicator
head extends laterally of, and is in contact with the surface of, a continuous web
of 0.5 cm thick Hydrofoam
2 polyurethane foam substrate which is drawn from a reel past the orifice by a system
of rolls. After impregnation by the mixture, the treated substrate is cooled and rewound
on to a product reel before being cut into pieces approximately 25 cms square.
[0063] Each sheet contains 5.0 g. of alcohol ethoxylate and 1.5 g. of amine hydrochloride
and provides grease and oily-soil removal when added to a 3.5 kg load of soiled fabrics
in 20 litres of water at 30°C. A similar benefit is also seen when the sheet is added
together with 3.5 kg of soiled fabrics to 20 litres of a wash liquor containing any
one of the following detergent compositions at 0.625% product concentration.
[0064] In the above formulation the amine can be replaced by any one of dodecyl dimethyl
amine, lauryl dihydroxycthy lamine, myristyl amine, decyl diethylamine, dioctyl amine
and tallow dimethyl amine.
[0065] Also in the above formulation the nonionic co- surfactant can be replaced by: Tallow
alcohol condensed with respectively 11 and 25 moles of ethylene oxide per mole of
alcohol, Dobanol 45-9, a C
14-C
15 primary alcohol condensed with an average of nine moles of ethylene oxide per mole
of alcohol, Dobanol 45-11, a C
14-C
15 primary alcohol condensed with an average of eleven moles of ethylene oxide per mole
of alcohol, Neodol 23-6 a C
12-C
13 primary alcohol condensed with an average of six moles of ethylene oxide per mole
of alcohol, marketed by the Shell Oil Co., Synperonic (RTM) A7, A9, All, A14 and A20,
a range of primary C
13-C
15 alcohols with about 50% 2-methyl branching condensed with an average of respectively
7, 9, 11, 14 and 20 moles of ethylene oxide per mole of alcohol supplied by Imperial
Chemical Industries Ltd., Lial 125E4,a highly branched C
12-C
15 primary alcohol condensed with four moles of ethylene oxide per mole of alcohol and
Lial 169E11, a C
16-C
19 highly branched primary alcohol condensed with an average of eleven moles of ethylene
oxide per mole of alcohol supplied by Liquichimica SA, Tergitol (RTM) 15S6, 15S9 and
15S11,C
11-C
15 secondary alcohols condensed with an average of 6, 9 and 11 moles ethylene oxide
respectively per mole of alcohol supplied by Union Carbide Corporation and sucrose
ester ethoxylates.
EXAMPLE II
[0066] 150 g. of powdered n-dodecylaminc hydrochloride are added to 500 g. of Dobanoj 45-7
nonionic surfactant and 450 g. of technical grade stearic acid and the mixture is
heated with agitation to 7
00C to provide a uniform dispersion. This is then pumped to an applicator assembly comprising
two heated horizontally disposed,steel-faced rolls. The first roll is provided with
an inwardly inclined plate extending the length of the roll so as to form a v-shaped
trough therebetween, the bottom of the trough being constituted by the nip between
the roll and the bottom edge of the plate, the direction of rotation of the roll being
downward at the nip so as to provide a bead of material on the roll surface. The other
roll has a faster speed of rotation in the same direction as the first so that a thin
coating of the dispersion is transferred from one roll to the other,at the nip between
the rolls, and is carried around the second roll. The second roll is in contact with
a continuous web of substrate material and at the point of contact the direction of
movement of the roll surface is opposed to the direction of movement of the web so
that the dispersion is wiped off the roll on to the substrate. The substrate is a
25 cm wide web of apertured non-woven fibre formed of regenerated cellulose fibres
bonded with an ethyl acrylate binder (70% fibre 30% binder solids) having a basis
weight of 40 g. per sq. metre and 17 apertures/ sq. cm., available from Chicopee Manufacturing
Co., Milltown, New Jersey U.S.A. under the Code No. AK 30ML1379.
[0067] After impregnation, the substrate web passes over two further counter rotating heated
rolls that provide
before being
in a cooled a stream and wound onto a product reel. The roll of impregnated substrate
is subsequently cu. and folded to give sheets of size approximately 25cm x 25cm (weight
25 gr.) each bearinga total weight of
[0068] The sheets have a smooth slightly sandy feel.
EXAMPLE III
[0069] Example II is repeated with the addition to the molten dispersion of 150g of Tallow
alcohol and 120g of Polyethylene glycol 6000. The sheets so formed have a waxy feel
and each contains
In the above example, the Dobanol 45-7 can be replaced by sodium C
12 alkyl benzene sulphonate or by sodium C
12 alkyl sulphate. In the above example, the n-dodecyl amine hydrochloride can be replaced
by coco dimethyl amine hydrochloride or by primary tallow amine hydrochlcride to give
a similar product.
EXAMPLE IV
[0070] Example III is repeated except that 300 g of
stearate are added to the molten
place of the dodecylamine hydrochloride.
mxiture is a homogeneous melt, as the
melts at approximately 50°C and is
the remaining ingredients The sheet produced has a smooth non- gritty
[0071]
[0072] An identical product is obtained if the amine stearate is formed in situ in the melt
by addition of 170 g amine and 130 g stearic acid separately to the mixture of the
other ingredients at 70°C.
EXAMPLE V
[0073] Example III is repeated replacing the n-dodecyl amine hydrochloride in the dispersion
by 75 g of ditallow methyl amine hydrochloride to give a sheet product comprising
The sheet so formed has a waxy, slightly sandy feel and provides similar grease and
oil-removal benefits to those provided by the products of Examples I-IV. A sheet used
with a heavy duty laundry detergent product at a concentration of 125 grs. product
in 20 litres of water also gave some fabric softening benefits. In the above example
the 75g of ditallow methyl amine hydrochloride is replaced by lOOg of a 3:1 mixture
of ditallowmethyl amine hydrochloride and C
12-14 alkyl dimethyl amine stearate and satisfactory cleaning together with some fabric
softening is obtained.
[0074] The tallow alcohol, polyethylene glycol, Dobanol 45-7 and stearic acid are mixed
and heated with agitation to a temperature of 70°C. The coco dimethylamine is then
added and the mixture held for 15 minutes to ensure complete conversion of the amine
to the salt. The remaining ingredients are then added as finely powdered solids and
mixed well to form a homogeneous dispersion which is then applied to a cellulosic
substrate following the procedure in Example II to give a smooth sheet product that
contains (per sheet)