Source: http://www.docstoc.com/docs/31213587/Laundry-Additive-Product---Patent-4220562
Timestamp: 2014-09-20 16:23:21
Document Index: 580274829

Matched Legal Cases: ['application No. 7711151', 'application No. 7711151', 'application No. 7711151', 'application No. 8989', 'application No. 8989', 'application No. 7711151']

Laundry Additive Product - Patent 4220562
United States Patent: 4220562
4,220,562
Additive products are provided for use in the washing of textiles
comprising a mixture of an organic peroxy bleach precursor, a cationic
surfactant and an alkoxylated nonionic surfactant of HLB 8-17 in water
releasable combination with a non-particulate substrate, the additive
products being adapted for addition to conventional inorganic
persalt-containing detergent liquors to enhance the removal of bleachable
Spadini; Gianfranco L. (Newcastle upon Tyne, GB2), Tolliday; Ian D. (Oakham, GB2), McRitchie; Allan C. (Blyth, GB2)
05/919,531
27273/77
8777/78
8988/78
510/513  ; 427/242; 510/295; 510/307; 510/312; 510/313; 510/314; 510/350; 510/535
C11D 1/835&amp;nbsp(20060101); C11D 17/04&amp;nbsp(20060101); C11D 3/39&amp;nbsp(20060101); C11D 1/38&amp;nbsp(20060101); C11D 1/62&amp;nbsp(20060101); C11D 1/72&amp;nbsp(20060101); C11D 001/62&amp;nbsp(); C11D 007/32&amp;nbsp(); C11D 017/00&amp;nbsp()
252/8,610,90,95,99,102,528,547,182,186,542,545,98 427/242 428/260,265,279
3989638
1.  A laundry additive product adapted for the removal of stains and consisting essentially of
(a) a substrate comprising a non-particulate solid article in the form of a sheet, block, ring, ball, rod or tube, said article possessing sufficient structural integrity under wash conditions to be recovered substantially intact at the end of
the laundry cycle, in water releasable combination with,
(b) an organic peroxy compound precursor selected from the group consisting of imides, acyl hydrazides, acylated oximes, anhydrides, and esters wherein the weight ratio of the precursor to the substrate lies in the range from 30:1 to 1:10, and
(c) a surfactant system comprising an alkoxylated nonionic surfactant having an HLB in the range 8.0-17.0 and a cationic surfactant having the empirical formula:
wherein R.sup.1 is a hydrophobic organic group containing alkyl chains optionally including aryl groups and which may also contain ether linkages, ester linkages, or amide linkages, and containing a total of from 8 to 20 carbon atoms, m is a
number from one to three, and no more than one R.sup.1 can have more than 16 carbon atoms when m is 2 or more than 12 carbon atoms when m is 3, R.sup.2 is a substituted or unsubstituted alkyl group containing from one to four carbon atoms or a benzyl
group, provided that not more than one such benzyl group is directly attached to each Y group, x is a number from zero to three, the remainder of any carbon atom positions being filled by hydrogens, Y is selected from the group consisting of ##STR16## L
is a number from 1 to 4, Z is a water-soluble anion in a number to give electrical neutrality, the cationic surfactant being water dispersible in admixture with the nonionic surfactant, the weight ratio of the nonionic surfactant to the cationic
surfactant being in the range 20:1 to 1:2, the weight ratio of the surfactant system to the substrate being in the range 20:1 to 1:5.
2.  A laundry additive product according to claim 1 wherein the alkoxylated nonionic surfactant is a C.sub.10 -C.sub.18 linear or branched chain alcohol ethoxylate.
3.  A laundry additive product according to claim 2 wherein the nonionic surfactant is a primary C.sub.10 -C.sub.15 substantially linear alcohol ethoxylate containing from seven to fifteen ethylene oxide groups per alcohol group.
4.  A laundry additive product according to claim 3 wherein the weight ratio of nonionic surfactant to cationic surfactant is within the range 10:1 to 1:1.
5.  A laundry additive product according to claim 4 wherein the weight ratio of nonionic surfactant to cationic surfactant is within the range 5:1 to 3:2.
6.  A laundry additive product according to claim 4 wherein the weight ratio of the surfactant system to the substrate is within the range 10:1 to 1:2.
7.  A laundry additive product according to claim 6 wherein the weight ratio of the surfactant system to the substrate is within the range of 8:1 to 1:1.
8.  A laundry additive product according to claim 7 wherein the weight ratio of the precursor to the substrate lies in the range 8:1 to 1:4.
9.  A laundry additive product according to claim 8 wherein the weight ratio of the precursor to the substrate lies in the range 5:1 to 1:2.
10.  A laundry additive product adapted for the removal of stains and consisting essentially of
(b) an organic peroxy compound precursor selected from the group consisting of imides, acyl hydrazides, acylated oximes, anhydrides, and esters wherein the weight ratio of the precursor to the substrate lies in the range 8:1 to 1:4 and
(c) a surfactant system comprising an alkoxylated nonionic surfactant having an HLB in the range 8.0-17.0 and a cationic surfactant having the emperical formula:
wherein R.sup.1 is a hydrophobic organic group containing alkyl chains optionally including aryl groups and which may also contain other linkages, ester linkages, or amide linkages, and containing a total of from 8 to 20 carbon atoms, m is a
group, provided that not more than one such benzyl group is directly attached to each Y group, X is a number from zero to three, the remainder of any carbon atom positions being filled by hydrogens, Y is selected from the group consisting of ##STR17## L
11.  A laundry additive product according to claim 10 wherein the cationic surfactant is such that it has the structure (1), L is 1, R.sup.1 is selected from C.sub.10 -C.sub.20 alkyl and C.sub.10 -C.sub.15 alkylbenzyl, m is 1 or 2, R.sub.2 is
selected from --CH.sub.2 C.sub.6 H.sub.5, --CH.sub.3, --CH.sub.2 CH.sub.2 OH and --CH.sub.2 CHOHCH.sub.3, x is 2 or 3 and Z is a halide, methosulphate, sulphate or carboxylate.
12.  A laundry additive product according to claim 11 further comprising detergent components selected from the group consisting of surfactants other than those specified in (c) of claim 1, suds modifiers, chelating agents, softeners, anti-static
agents, anti-redeposition and soil suspending agents, optical brighteners, perfumes, enzymes and mixtures of the foregoing, the weight ratio of the precursor to the detergent components being in the range from 500:1 to 10:1.
13.  A laundry additive product according to claim 11 wherein the weight ratio of nonionic surfactant to cationic surfactant is within the range 10:1 to 1:1.
14.  A laundry additive product according to claim 13 wherein the weight ratio of nonionic surfactant to cationic is within the range 5:1 to 3:2.
15.  A laundry additive product according to claim 12 wherein the amount of the detergent component or components is such that the total component:substrate weight ratio is less than 10:1.
16.  A laundry additive product according to claim 15 wherein the chelating agent is selected from the group consisting of ethylene diamine tetramethylene phosphonic acid, nitrilo trimethylene phosphonic acid, diethylene triamino pentamethylene
phosphonic acid and alkali metal or ammonium salts thereof.
17.  A laundry additive product according to claim 15 incorporating as an adjuvant, a suds modifier selected from C.sub.20 -C.sub.24 fatty acids, copolymers of ethylene oxide with a hydrophobic group formed by condensing propylene oxide with
propylene glycol, polydialkyl siloxanes and mixtures thereof with silica, microcrystalline waxes, triazine derivatives and mixtures of any of the foregoing.
18.  A laundry additive product according to claim 17 including as adjuvant C.sub.16 -C.sub.18 fatty acid.
19.  A laundry additive product according to claim 18 wherein the weight ratio of the nonionic-cationic surfactant mixture to the C.sub.16 -C.sub.18 fatty acid is in the range 1:5 to 4:1.
20.  A laundry additive product according to claim 19 wherein the weight ratio of the nonionic-cationic surfactant mixture to the C.sub.16 -C.sub.18 fatty acid is in the range 1:3 to 3:2.
21.  A laundry additive product adapted for the removal of stains and consisting essentially of
(a) a substrate in flexible sheet form in water releasable combination with
(b) an organic peroxy compound precursor selected from tetraacyl C.sub.2 -C.sub.6 alkylene diamines wherein the weight ratio of the precursor to the substrate lies in the range from 5:1 to 1:2 and
(c) a surfactant system comprising a nonionic surfactant selected from primary C.sub.10 -C.sub.15 substantially linear ethoxylates containing from about seven to about 15 ethylene oxide groups per alcohol group and a cationic surfactant of
R.sub.1 (R.sup.2).sub.3 N.sup.+ Z
wherein R.sub.1 is selected from C.sub.10 -C.sub.20 alkyl and C.sub.10 -C.sub.15 alkyl benzyl, R.sub.2 is selected from --CH.sub.2 C.sub.6 H.sub.5, --CH.sub.3, --CH.sub.2 CH.sub.2 OH, and --CH.sub.2 CHOHCH.sub.3, provided that not more than one
R.sub.2 group is --CH.sub.2 C.sub.6 H.sub.5 and Z is selected from halide, methosulphate, sulphate and carboxylate, the cationic surfactant being water dispersible in admixture with the nonionic surfactant, the weight ratio of the nonionic surfactant to
the cationic surfactant being in the range 5:1 to 3:2 and the weight ratio of the surfactant system to the substrate being in the range 8:1 to 1:1.
22.  A laundry additive product according to claim 21 further comprising an organic adjuvant selected from organic chelating agents, suds modifiers, anti redeposition agents and optical brighteners, and mixtures of the foregoing, the amount of
such adjuvants being such that the total adjuvant:substrate weight ratio is less than 10:1.  Description
In the Applicants&#39; Swedish patent application No. 7711151-6 published on Apr.  6, 1978 there is disclosed a laundry additive product comprising:
The above disclosed invention is especially adapted for the removal of oxidisable stains from textiles when used in conjunction with conventional inorganic persalt-containing detergent compositions.  It has now been found that certain mixtures of
nonionic and cationic surfactants incorporated together with the organic peroxy compound precursor in water releasable combination with a non-particulate substrate provide enhanced removal of a broad range of stains especially greasy and oily stains.
The effect is further increased when the additive product is used in conjunction with a conventional heavy duty laundry detergent containing an anionic surfactant and an inorganic persalt.
wherein R.sup.1 is a hydrophobic organic radical containing alkyl chains, and/or aryl groups and which may also contain ether linkages, ester linkages, or amide linkages and containing a total of from 8 to 20 carbon atoms, m is a number from one
to three, and no more than one R.sup.1 can have more than 16 carbon atoms when m is 2, or more than 12 carbon atoms when m is 3, R.sup.2 is a substituted or unsubstituted alkyl group containing from one to four carbon atoms or a benzyl group provided
that not more than one such benzyl group is directly attached to each Y group, x is a number from zero to three, the remainder of any carbon atom positions being filled by hydrogens, Y is selected from the group consisting of ##STR1## L is a number from
1 to 4, Z is a water-soluble anion in a number to give electrical neutrality, the cationic surfactant being water dispersible in admixture with the nonionic surfactant, the weight ratio of the nonionic surfactant to the cationic surfactant being in the
range 20:1 to 1:2, the weight ratio of the surfactant system to the substrate being in the range 20:1 to 1:5.
As used herein, an organic peroxy compond precursor is any organic compound capable of reaction with an inorganic peroxygen-containing compound in aqueous solution to give an organic peroxy compound having a bleaching performance at a temperature
of 70.degree.  C. and below, at least equivalent to that of the inorganic peroxygen containing compound under the same conditions.
Also as used herein, the terms inorganic peroxy bleach and inorganic persalt are intended to cover such salts as alkali metal perborates, percarbonates, persilicates and perpyrophosphates which produce hydrogen peroxide in aqueous solution rather
In a preferred aspect of the present invention, the cationic-nonionic surfactant mixture comprises a mono-C.sub.12 -C.sub.14 alkyl, tri- C.sub.1 -C.sub.4 alkyl quaternary ammonium salt, particularly the chloride or the methosulphate, and an
ethoxylated linear C.sub.14 -C.sub.18 primary alcohol containing an average of from about 5 to about 30 moles of ethylene oxide per mole of alcohol, the weight ratio of the nonionic to the cationic surfactant being in the range 5:1 to 3:2.
In a further preferred aspect of the invention, the organic peroxy compound precursor of each of the components of a mixture of such precursors is selected from the group consisting of anhydrides, esters, oximes and N-acylated compounds.
Preferably the precursor is one or more N-acetylated compounds of structure: ##STR2## where x can be 0 or any integer between 1 and 6 and is most preferably 0, 2 or 6.
In a method aspect of the invention, a method of making a laundry additive product comprises the steps of forming the nonionic-cationic surfactant system and the peroxy compound precursor into a fluid mass, impregnating a solid non-particulate
water permeable article with said mass and causing said mass to solidify.
Preferably the combination of the surfactant system and the precursor is mixed with a solid non-hygroscopic organic adjuvant to provide a melt having a viscosity of up to 5000 centipoises at 50.degree.  C., this melt constituting a fluid mass
with which the substrate is impregnated.
In accordance with the invention disclosed in Swedish patent application No. 7711151-6, the precursor or mixture thereof is normally added in a separate product to that containing the inorganic peroxy-containing compound although, as described
hereinafter, the precursor and the peroxygen-containing compound can be incorporated on a single substrate provided they are physically separated from each other.
Thus, the precursor or mixture of precursors and the inorganic peroxy bleach do not come into contact with each other except in the washing liquor.  The delivery of the precursor mixture to the wash liquor in water-releasable combination with a
non-particulate solid article avoids most of the stability problems encountered in prior art products and also permits control by the user of whether or not low temperature bleaching is to be employed and the level of bleaching that is to be used.  The
additive products of the present invention also enhance the human safety of low temperature bleaching of domestic laundry by materially increasing the difficulty of accidental ingestion of the combination.
The products of the present invention also provide an enhanced rate of release for the peroxy compound precursors into the wash liquor relative to that achieved from prior art granular products and this, in turn, improves the rate of conversion
into the organic peroxy bleaching species.  The disinfectant efficiency of the organic peroxy compounds is thereby improved and the harmful effects of catalase on the bleaching capability of residual inorganic peroxy bleach are reduced.
In the broadest aspect of the invention, any of the organic peroxy compound precursors described in the above mentioned Swedish patent application No. 7711151-6 can be employed either singly or in combination, but it has been found that where the
precursor or mixture of precursors comprises perbenzoic acid generating compounds, combinations thereof with at least one peracetic acid-generating compound in a weight ratio of from 5:1 to 1:5 provide an optimum balance of bleaching and colour safety
Thus anhydrides, esters, carbonates, acylated oximes, chloroformates and cyano compounds are all useful classes of organic peroxy compound precursors.  N-acylated compounds are also useful, typical examples being the imide, imidazole,
sulphonamide and triazine classes and certain acylated hydrazines.  Preferred classes of materials are the anhydrides, esters, acylated oximes, imides and acylated hydrazines.
Particularly preferred compounds are N,N,N&#39;,N&#39;-tetra acetylated compounds of formula ##STR3## in which x can be 0 or an integer between 1 and 6.  Where x is an integer between 1 and 6, the compounds are imides, examples being tetraacetyl
methylene diamine (TAMD) where x=1, tetra-acetyl ethylene diamine (TAED) where x=2, and tetraacetyl hexamethylene diamine (TAHD) where x=6.  Where x=0 the compound is tetraacetyl hydrazine (TAH).  TAHD and TAH are particularly preferred because of their
low melting points (59.degree.  C. and 83.degree.  C. respectively) which facilitates their processing in additive products of the present invention as described hereinafter.  All of these compounds and the process for making them are described in
British Pat.  No. 907,356 the disclosures of which are specifically incorporated herein by reference.
The level of usage of organic peroxy compound precursor will naturally be dependent on a number of factors eg.  the size of the fabric load in the machine, the level of bleaching performance desired, the amount of inorganic persalt in the
conventional detergent products and the usage of the detergent product, the bleaching efficacy of the organic peroxy species derived from the precursor and the efficiency of conversion of the precursor into that peroxy species.  It is conventional with
compound should be in the range 10 ppm to 80 ppm. This level of available oxygen should be attained within the normal wash cycle time ie., within 15 to 25 minutes depending on the particular wash cycle being employed.
For a machine having a liquid capacity in use of 20 to 30 liters, such a level of available oxygen requires the delivery of from 1 gr to 20 gr of organic peroxy compound precursor assuming quantitive conversion.  This figure will increase
although the number of units to be used to deliver a given quantity of precursor is a matter of choice.  Normally the weight of precursor per delivery will lie in the range 3 to 10 grs.
The grease and oil removal component of the present invention comprises a mixture of a water-soluble, cationic surfactant and an alkoxylated nonionic surfactant of defined HLB range, the weight ratio of the two surfactants being within the range
20:1 to 1:2, preferably 10:1 to 1:1, and most preferably 5:1 to 3:2.  The nonionic surfactants used in the compositions may be alkoxylated aliphatic alcohols, alkyl phenols, esters, amides and fatty acids having an HLB within the range 8.0-17.0.  The
aliphatic alcohols include linear and branched chain primary and secondary C.sub.8 -C.sub.22 alcohols, the alkyl phenols are the C.sub.6 -C.sub.12 alkyl phenols, and the fatty esters, fatty amides and fatty acids are those having a C.sub.12 -C.sub.18
alkyl group in the acyl residue.  The preferred alkoxylating group is ethylene oxide.
Suitable nonionic surfactants based on alphatic alcohols are condensation products of primary and secondary alcohols with from about 4 to about 30 moles of ethylene oxide.  The alkyl chain of the aliphatic alcohol can either be straight or
branched and generally contains from about 8 to about 22 carbon atoms.  Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of
about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).  Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9, marketed by
Union Carbide Corporation, Dobanol 45E9, marketed by Shell Chemical Company, and Kyro EO, marketed by The Procter &amp; Gamble Company.  Other suitable alcohol ethoxylates include:
______________________________________ Tallow (C.sub.16 -C.sub.18) alcohol (E.sub.25)  Linear (C.sub.14 -C.sub.15) alcohol (E.sub.5)  (C.sub.14 -C.sub.15) alcohol (E.sub.7)  (C.sub.12 -C.sub.13) alcohol (E.sub.6)  (C.sub.9 -C.sub.11) alcohol
(E.sub.5)  Branched (C.sub.10 -C.sub.13) alcohol (E.sub.4)  Linear (s-C.sub. 11 -C.sub.15) alcohol (E.sub.5)  (s-C.sub. 11 -C.sub.15) alcohol (E.sub.7)  (S-C.sub. 11 -C.sub.15) alcohol (E.sub.9)  ______________________________________
Alcohol ethoxylates such as those disclosed in British Pat.  No. 1,462,134, incorporated herein by reference, are also useful in the present invention.
Suitable alkyl phenol ethoxylates include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said
ethylene oxide being present in an amount equal to 8 to 20 moles of ethylene oxide per mole of alkyl phenol.  The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, di-isobutylene, and the like.  Examples of
compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of
ethylene oxide per mole of phenol; and di-isooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.  Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by the GAF Corporation, and Triton
X-45, X-114, X-100 and X-102, all marketed by the Rohm &amp; Haas Company.
______________________________________ Linear C.sub.8 Alkyl phenol (E.sub.5)  C.sub.8 Alkyl phenol (E.sub.8)  C.sub.9 Alkyl phenol (E.sub.6)  C.sub.9 Alkyl phenol (E.sub.9).  ______________________________________
______________________________________ Sorbitan monooleate (E.sub.5)  Sorbitan trioleate (E.sub.20)  Sorbitan monostearate (E.sub.4)  Sorbitan tristearate (E.sub.20)  ______________________________________
Other nonionic surfactants useful herein include the condensation products of ethylene oxide with the product resulting from the condensation of propylene oxide with propylene glycol.  Surfactants of this type are available commercially from the
Wyandotte Chemicals Corporation under the names &quot;Tetronic&quot; and &quot;Pluronic&quot; respectively.
Particularly preferred materials are the primary linear and branched chain primary alcohol ethoxylates, such as C.sub.14 -C.sub.15 linear alcohols condensed with 7-15 moles of ethylene oxide available from Shell Oil Company under the &quot;Dobanol&quot;
Trade Mark and the C.sub.10 -C.sub.13 branched chain alcohol ethoxylates obtainable from Liquichimica SA under the `Lial` Trade Mark.
wherein each R.sup.1 is a hydrophobic organic group containing alkyl chains, alkenyl chains, alkyl benzyl chains, alkyl phenyl chains, ether linkages, alkylene groups, alkenylene groups, ester linkages, and amide linkages totalling from about 8
to 20 carbon atoms and which may additionally contain or be attached to a polyethylene oxide chain containing up to about 20 ethoxy groups, and m is a number from one to three.  No more than one R.sup.1 in a molecule can have more than 16 carbon atoms
when m is 2 and no more than 12 carbon atoms when m is 3.  R.sup.2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R.sup.2 in a molecule being benzyl, and x is a number from 0 to 3.  The
remainder of any carbon atom positions on the Y group are filled by hydrogens.  Y is selected from the group consisting of: ##STR4## L is a number from 1 to 4, and Z is a water-soluble anion, such as halide, methylsulfate, hydroxide, or nitrate anion,
particularly preferred being chloride, bromide or iodide anions, in a number to give electrical neutrality of the cationic component.  The particular cationic component to be included in a given system depends to a large extent upon the particular
nonionic component to be used in this system, and is selected such that it is at least water-dispersible, or preferably water-soluble, when mixed with said nonionic surfactant.  It is preferred that the cationic component be substantially free of
hydrazinium groups.  Mixtures of these cationic materials may also be used in the compositions of the present invention.
When used in combination with nonionic surfactants, these cationic components provide excellent soil removal characteristics, confer static control and fabric softening benefits to the laundered fabrics, and inhibit the transfer of dyes among the
laundered fabrics in the wash solution.
However, L may be greater than 1, such as in cationic components containing 2 or 3 cationic charge centers.  Other cationic materials which are useful in the compositions of the present invention include phosphonium, sulfonium, and imidazolinium
Where Y is ##STR6## and m=1 it is preferred that x is equal to 3.  R.sup.2 is typically C.sub.1 -C.sub.4 alkyl, hydroxyalkyl or benzyl(no more than one benzyl group being permissible) but is usually a methyl group.  A preferred structure is where
one R.sup.2 group is hydroxyethyl.  Cationic surfactants of this mono long chain type include those in which R.sup.1 is a C.sub.10 -C.sub.20 alkyl group more preferably a C.sub.10 -C.sub.16 alkyl group or a C.sub.10 -C.sub.15 alkylbenzyl group.
Particularly preferred compositions of this class include C.sub.12 alkyl trimethyl ammonium bromide, C.sub.12 alkyl dimethyl hydroxyethyl ammonium bromide, C.sub.12 alkyl dimethyl hydroxypropyl ammonium bromide, C.sub.12 alkyl dimethylbenzyl ammonium
chloride and their counterparts based on middlecut coconut alcohol as the source of the alkyl group.  Other counter ions such as methosulphate, sulphate, sulphonate and carboxylate can also be used particularly with the hydroxyalkyl-substituted
Specific examples of hydroxyalkyl substituted compounds are the C.sub.10 -C.sub.16 dimethyl hydroxyethyl ammonium laurates, palmitates, oleates and stearates.  These compounds have a waxy physical form and are relatively non-hygroscopic, thereby
facilitating their incorporation into the additive products of the invention.
Where m is equal to 2, only one of the R.sup.1 chains can be longer than 16 carbon atoms.  Thus ditallowdimethylammonium chloride and distearyldimethylammonium chloride, which are used conventionally as fabric softeners and static control agents
in detergent compositions, may not be used as the cationic component in the surfactant mixtures of the present invention.  Preferred di-long chain cationics of this type include those in which x is equal to 2 and R.sup.2 is a methyl group.  In this
instance it is also preferred that R.sup.1 is a C.sub.8 to C.sub.12 alkyl group.  Particularly preferred cationic materials of this class include di-C.sub.8 alkyldimethylammonium halide and di-C.sub.10 alkyldimethylammonium halide materials.
Where m is equal to 3, only one of the R.sup.1 chains can be greater than 12 carbon atoms in length.  The reason for this chain length restriction, as is also the case with the di-long chain cationics described above, is the relative insolubility
of these tri- and di-long chain materials.  Where tri-long chain alkyl materials are used, it is preferred that R.sup.2 is a methyl group.  In these compositions it is preferred that R.sup.1 is a C.sub.8 to C.sub.11 alkyl group.  Particularly preferred
tri-long chain cationics include trioctylmethylammonium halide, and tridecylmethylammonium halide.
Cationic surfactants of this type can be prepared by techniques well known to those skilled in the art and which do not form part of the present invention.  However a particularly preferred technique the subject of our copending British
application No. 8989/78 filed Mar.  1978 and entitled &quot;Process for making detergent compositions&quot; comprises the quaternisation of a tertiary amine in a liquid polyethylene oxide condensate reaction medium which is itself a component of the present
invention.  The resultant mixture of a cationic surfactant and a polyethylene oxide condensate can be applied directly to the substrate without isolation of the cationic surfactant per se.
The technique involves dissolving or dispering a normally non-volatile tertiary amine, containing one or more long chain hydrocarbon residues, in a nonionic polyethoxylate condensate.  A relatively volatile quaternising agent having a boiling
point less than 200.degree.  C., preferably less than 100.degree.  C., and most preferably less than ambient temperature, is reacted with this mixture to form the cationic surfactant.  The mixture of cationic surfactant and ethoxylate is normally a
dispersion which is solid at ambient temperatures and liquid at temperatures greater than approximately 45.degree.  C. but certain preferred hydroxyalkyl group containing quaternary ammonium surfactants having a long chain carboxylate counter ion are
miscible with polyethoxylated nonionic surfactants and form clear solutions.
Specific examples of these preferred quaternary ammonium surfactants are myristyl dimethyl hydroxyethyl ammonium stearate, lauryl dimethyl hydroxyethyl ammonium palmitate, and lauryl dimethyl hydroxyethyl ammonium oleate.  These compounds are
non-crystalline low melting solids having acceptable water solubility together with low hydroscopicity and provide, in combination with nonionic surfactants, enhanced grease and oily stain removal.
Because of their waxy nature and their high affinity for conventional solvents these hydroxyalkyl group-containing quaternary ammonium surfactants are very difficult to prepare in the solvent-free solid state and the above-described technique is
a convenient way to obtain them in a form suitable for the purposes of the present invention.
Another useful type of cationic component which is described in U.S.  patent application Ser.  No. 811218, J. C. Letton, filed June 29, 1977, and incorporated herein by reference, has the formula ##STR7## wherein R.sup.1 is C.sub.1 to C.sub.4
alkyl or hydroxyalkyl; R.sup.2 is C.sub.5 to C.sub.30 straight or branched chain alkyl or alkenyl, alkyl benzene, or ##STR8## R.sup.3 is C.sub.1 to C.sub.20 alkyl or alkenyl; a is 0 or 1; n is 0 or 1; m is from 1 to 5; Z.sup.1 and Z.sup.2 are each
selected from the group consisting of ##STR9## and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the compound at least water-dispersible,
preferably selected from the group consisting of halide, methylsulfate, hydroxide, and nitrate preferably chloride, bromide or iodide.
In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is environmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen-containing
segment.  These preferred cationic components are useful in nonionic/cationic surfactant mixtures which have a ratio of nonionic to cationic of from about 10:6 to about 20:1.  However, when used in the composition of the present invention, they are used
in surfactant mixtures which have nonionic to cationic ratios of from about 10:2 to about 10:6, particularly from about 10:3 to 10:5, most preferably about 10:4.  These preferred cationic surfactants may also be used in the detergent systems defined in
U.S.  patent application Ser.  No. 811,220 Murphy, filed June 29, 1977 and incorporated herein by reference, in nonionic to cationic ratios of from about 8:1 to 20:1.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula ##STR10## as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse
Particularly preferred examples of this type of cationic surfactant include stearoyl choline ester quaternary ammonium halides (R.sup.2 =C.sub.17 alkyl), palmitoyl choline ester quaternary ammonium halides (R.sup.2 =C.sub.16 alkyl), myristoyl
choline ester quaternary ammonium halides (R.sup.2 =C.sub.13 alkyl), lauroyl choline ester ammonium halides (R.sup.2 =C.sub.11 alkyl), and tallowoyl choline ester quaternary ammonium halides (R.sup.2 =C.sub.16 -C.sub.18 alkyl).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, where p may be from 0 to 20.  ##STR11##
in the presence of an acid catalyst material.  The reaction product is then used to quaternize triethanolamine, forming the desired cationic component.
Another type of novel, particularly preferred cationic material, described in U.S.  patent application Ser.  No. 811219, J. C. Letton, filed June 29, 1977, incorporated herein by reference, are those having the formula ##STR12## in the above
formula, each R.sup.1 is a C.sub.1 to C.sub.4 alkyl or hydroxy-alkyl group, preferably a methyl group.  Each R.sup.2 is either hydrogen or C.sub.1 to C.sub.3 alkyl, preferably hydrogen.  R.sup.3 is a C.sub.4 to C.sub.30 straight or branched chain alkyl,
alkenylene, or alkyl benzyl group, preferably a C.sub.8 to C.sub.18 alkyl group, most preferably a C.sub.12 alkyl group.  R.sup.4 is a C.sub.1 to C.sub.10 alkylene or alkenylene group.  n is from 2 to 4, preferably 2; y is from 1 to 20, preferably from
about 1 to 10, most preferably about 7; a may be 0 or 1; t may be 0 or 1; and m is from 1 to 5, preferably 2.  Z.sup.1 and Z.sup.2 are each selected from the group consisting of ##STR13## and wherein at least one of said groups is selected from the group
consisting of ester, reverse ester, amide and reverse amide.  X is an anion which will make the compound at least water-dispersible, and is selected from the group consisting of halides, methylsulfate, hydroxide and nitrate, particularly chloride,
bromide and iodide.
These novel cationic surfactants may be used in nonionic/cationic surfactant mixtures in a ratio of nonionic component to cationic component of from about 10:6 to about 20:1.  When these surfactants are used in the compositions of the present
invention they are used in nonionic to cationic ratios of from about 10:6 to about 10:2.  They may also used in the nonionic/cationic surfactant mixtures disclosed in U.S.  patent application Ser.  No. 811,220, Murphy, filed June 29, 1977 and
incorporated herein by reference, wherein the ratio of nonionic component to cationic component would be from about 8:1 to about 20:1.  These surfactants, when used in the compositions, of the present invention, yield excellent particulate soil, body
soil, and grease and oil soil removal.  In addition, the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of dyes in the washing solution.  Further, these novel cationic surfactants are
environmentally desirable, since both their long chain alkyl segments and their nitrogen segments are biodegradable.
Preferred embodiments of this type of cationic component are the choline esters (R.sup.1 is a methyl group and Z.sup.2 is an ester or reverse ester group), particular formulas of which are given below.  ##STR14##
acid chloride.  The acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is the quaternized with a methyl halide to form the desired choline ester compound.  Another way of preparing these compounds is by the
direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst.  The reaction product formed is then quaternized with methylhalide or used
to quaternize trimethylamine to form the desired choline ester compound.
The amount of the nonionic-cationic mixture is such that the surfactant mixture:substrate weight ratio lies in the range 20:1 to 1:5, preferably from 10:1 to 1:2, and most preferably from 8:1 to 1:1.  In preferred executions using non-woven sheet
substrates of approximately 100 sq.  ins.  plan area and .perspectiveto.3 grs./sheet basis weight, the loading of nonionic-cationic surfactant mixture is in the range 4-15 grs./sheet.
Where the nonionic-cationic surfactant mixture is a liquid at normal temperatures, its phyical incorporation can take place in a number of ways.  Where the substrate comprises a non-sheet like reticulated foam article, direct impregnation of the
article by the mixture, either alone or with other components of the formulation can be used, employing methods known in the art and described in more detail hereinafter.  Where the substrate comprises a non-woven material or a foam article of sheet-like
form, it is preferred to mix the surfactant mixture with a compatible non-hygroscopic material of higher melting point to provide a waxy solid in which the surfactant is present in the form of a solid solution and/or as a dispersed phase.  The melting
point range and waxy nature of polyethylene glycols of molecular weight &amp;gt;4000 make them useful for this purpose, although their hygroscopicity under extreme conditions of humidity leads to high levels of moisture pick-up if appreciable amounts of such
glycols are used.  Other useful materials include C.sub.12 -C.sub.18 fatty acid alkanolamides.  However, the preferred materials are the higher fatty acids, particularly the C.sub.16 -C.sub.18 saturated fatty acids which are employed in an amount such
that the weight ratio of fatty acid to nonionic-cationic surfactant mixture is in the range 1:5 to 4:1, preferably 1:3 to 3:2 and most preferably 2:3 to 1:1.
Where the surfactant mixture is a solid at normal temperature but is molten at a temperature less than about 100.degree.  C. preferably less than about 80.degree.  C., the surfactant mixture itself can be used as the vehicle for incorporating
other non liquid components into the substrate.  Surfactant mixtures in which the nonionic is a high ethoxylate such as tallow alcohol (E.sub.25) and C.sub.14 -C.sub.15 primary alcohol (E.sub.15) are examples of this type.
it should possess sufficient structural integrity under the conditions of the wash to be recovered from the machine at the end of the laundry cycle.  Structures which are water disintegratable ie.  that break down in aqueous media to individual fibres or
insoluble particles are not considered satisfactory for the purposes of the present invention.
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, ie.  they should be capable of addition to the washing liquor in
Other devices and articles that can be adapted for use in dispensing the organic peroxy compound precursor in a washing liquor include those described in Dillarstone, U.S.  Pat.  No. 3,736,668, issued Jun.  5, 1973: Compa et al, U.S.  Pat.  No.
3,701,202, issued Oct.  31, 1972: Purgal, U.S.  Pat.  No. 3,634,947, issued Jan.  18, 1972: Hoeflin, U.S.  Pat.  No. 3,633,538, issued Jan.  11, 1972 and Rumsey, U.S.  Pat.  No. 3,435,537 issued Apr.  1, 1969.  All of these patents are incorporated
A highly preferred article herein comprises the organic peroxy compound precursor in water-releasable combination with a sheet and this should be flexible so as to make it compatible with the movement of the fabrics in the washing machine and to
surgical dressings, or of the type known as cheese cloth.  Loading limitations on non-woven sheet type substrates limit the amount of precursor that can be applied to the sheet, namely to a maximum required by the precursor: sheet weight ratio of about
herein, is intended to mean a substance with an absorbent capacity (ie.  values representing a substrate&#39;s ability to take up and retain a liquid) of up to approximately 12 times its weight of water.
Absorbent capacity values are then calculated in accordance with the formula given in said specification.  Based on this test, one-ply, dense, bleached paper (eg.  kraft or bond having a basis weight of about 32 pounds per 3,000 square feet, has
an absorbent capacity of 3.5 to 4; commercially available household one-ply towelling paper has a value of 5 to 6; and commercially available two-ply household towelling paper (a paper structure preferred herein) has a value of 7 to about 9.5.
structures comprise plies embossed with protuberances, the ends of which are mated and jointed; such a paper structure has a void volume of free space between the unembossed portion of the plies, as well as between the fibres of the paper sheet itself.
A non-woven cloth also had such space between each of its fibres.  The free space of non-woven cloth or paper, having designated physical dimensions, can be varied by modifying the density of the fibres of the paper or non-woven cloth.  Substances with a
high amount of free space generally have low fibre density; high density substrates generally have a low amount of free space.  Preferred substrates of the invention herein have up to about 90% free space based on the overall volume of the substrate&#39;s
A preferred paper substrate is a compressible, laminated, calendered, multi-ply absorbent paper structure.  Preferably, the paper structure has 2 or 3 plies and a total basis weight of from 14 to 90 pounds per 3,000 square feet and absorbent
capacity values within the range of 7 to 10.  Each ply of the preferred paper structure has a basis weight of about 7 to 30 pounds, per 3,000 square feet, and the paper structure can consist of plies having the same or different basis weights.  Each ply
is preferably made from creped, or otherwise extensible, paper with crepe percentage of about 15% to 40% and a machine direction (MD) tensile and cross-machine (CD) tensile of from about 100 to 1,500 grams per square inch of paper width.  The two outer
plies of a 3-ply paper structure or each ply of a 2-ply paper structure are embossed with identical repeating patterns consisting of about 16 to 2000 discrete protuberances per square inch, raised to a height of from about 0.010 inch to 0.40 inch above
the surface of the unembossed paper sheet.  From about 10% to 60% of the paper sheet surface is raised.  The distal ends (ie.  the ends away from the unembossed paper sheet surface) of the protuberances on each ply are mated and adhesively jointed
together, thereby providing a preferred paper structure exhibiting a compressive modulus of from about 200 to 800 inch-grams per cubic inch and Handle-O-Meter (HOM) MD and CD values of from about 10 to 130.
herein, as well as methods of its preparation, can be found in Edward R. Wells, U.S.  Pat.  No. 3,415,459, issued on Dec.  3, 1968, the full disclosure of which is hereby incorporated hereinto.
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 carding)
or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in random array (ie.  an array of fibres in a carded web wherein partial orientation of the fibres is frequently present as well as a completely haphazard
distributional orientation) or substantially aligned.  The fibres or filaments can be natural (eg.  wool, silk, jute, hemp, cotton, linen, sisal, or ramie) or synthetic (eg.  rayon, cellulose, or polyesters).
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
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, ie.  by superimposing a plurality of carded webs or mats to a thickness adequate to
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
Apertured non-woven substrates are also useful for the purpose 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 U.S.  Pat.  Nos.  3,741,724, 3,930,086 and 3,750,237, the disclosures of which are specifically incorporated herein by reference.
length and are from 1.5 to 5 denier (Denier is an internationally recognised unit in yarn 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.  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.
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 &amp; Haas,
Inc.).  The cloth has a thickness of 4 to 5 mils., a basis weight of about 24 grams per square yard, and an absorbent capacity of 6.  One foot length of the cloth 81/3&quot; 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.
A further preferred substrate is a water-laid, non-woven cloth commmercially available from C. H. Dexter Co.  Inc.  The fibres are regenerated cellulose, about 3/8&quot; 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 24 grams per square yard and an absorbent capacity of 5.7.  One foot length of the cloth, 81/3&quot; wide, weights about 1.66 grams.
A further class of substrate material that can be used in the present invention comprises an absorbent foam like material in the form of a sheet.  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 U.S.  Pat.  Nos.  3,311,115 and 3,430,630 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 U.S.  Pat.  No. 3,794,029 which is hereby specifically incorporated by reference.  A preferred example of this foam type comprises a hydrophilic
polyurethane foam of density about 0.596 grs.  per cubic inch with a cell count of between 20 and 100 cells per inch, preferably about 60 to 80 per inch available from the Scott Paper Company, Eddystone, Pennsylvania USA, under the Registered Trade Mark
&quot;Hydrofoam&quot;.
preferred area lying the range of from 80 to 160 square inches for non-woven substrates and 30 to 50 square inches for foamed sheets.  Such a size has the additional advantage of being too large to be swallowed by eg.  small children, thereby minimising
the risk of internal tissue damage from ingestion of the materials absorbed on the substrate.
In addition to the peroxy compound precursors, one or more other materials can be applied to the substrate either separately or together with the precursors, the only constraint on such materials being that the amount that can be incorporated is
restricted because of the loading limitations of the substrate.  For the substrate types preferred in the present invention the weight of optional component per sheet is unlikely to be more than 10 times the sheet weight, and preferably is less than 5
times the sheet weight, and preferably is less than 5 times the sheet weight.
The principal optional components are solid water soluble or water-dispersible organic adjuvants.  These adjuvants can fulfill a variety of functions in the product, such as processing and release aids, specific additives providing performance
improvement in the wash cycle and aesthetic ingredients.
One major ingredient can be a processing aid which serves as a plasticiser or thickener in the incorporation of the precursors into or onto the substrate.  However, in certain preferred compositions of the present invention, the cationic-nonionic
surfactant mixture itself serves as a processing aid as hereinbefore described, and thus little or no additional processing aid is required.  Certain other preferred cationic-nonionic mixtures, particularly those wherein the alkoxylated nonionic product
is of low HLB, require the use of a thickening adjuvant as described hereinbefore.  These adjuvants are solids that are mixed with the precursors and melted to provide mixtures having a viscosity of up to 5000 centipoises at 50.degree.  C. Typical solids
are polyvinyl pyrrolidone of M.Wt.  44,000-700,000, preferably 500,000-700,000 tallow alcohol ethoxylates containing from 5 to 30 ethylene oxide groups, C.sub.12 -C.sub.18 fatty acids and certain amides and esters thereof, sorbitan esters of C.sub.16
-C.sub.18 fatty acids and polyethylene glycols of molecular weight greater than 4,000.  As stated hereinbefore, preferred adjuvants are those having low hygroscopicity such as the C.sub.16 -C.sub.  18 saturated fatty acids.
can be employed as such.  Paraffin waxes can also be used in minor amounts.  Where the processing aid does not have any other function in the product, such as a surfactant component of the grease-removal surfactant mixture, its level of incorporation
will be such that the precursor:processing aid weight ratio will be in the range from 20:1 to 1:3, the latter value being for economic reasons.  However, the weight ratio of precursor:processing aid can be as low as 1:10 where the processing aid has
other functional properties such as surfactancy.  A further class of materials useful as a processing aid are the polyacrylamides of molecular weight .apprxeq.500,000 which are thixotropic water soluble polymers that can retain water in the solid state.
The organic peroxy compound precursor can be dissolved or dispersed in an aqueous mull of the polymer.  The mull is then fed to the substrate web and deposited to impregnate/coat the substrate whereupon it sets as a solid, but water soluble, gel.  This
particular class of materials is especially valuable for applying the organic peroxy compound precursors to water soluble substrates such as polyvinyl alcohols which tend to lose their water solubility when exposed to elevated temperatures.
As indicated above, a further type of adjuvant is a release aid that assists in releasing the precursors from the substrate upon addition of the product to a wash liquor.  In general, materials serving as processing aids are also suitable as
release aids but certain materials, notably stearic acid and polyethylene glycols of M.Wt.  4,000-6,000, are particularly effective when used in amounts such that the weight ratio of precursors:release aid lies in the range 20:1 to 1:2 particularly 4:1
to 1:1.  The benefits of the release aid are most clearly seen for water insoluble precursors such as 2,2-di-(4-hydroxyphenyl) propane diacetate.
In addition to the foregoing optional components, detergent ingredients other than inorganic bleaches can also be incorporated.  Thus, surfactants, in addition to the nonionic-cationic mixtures specified hereinbefore, suds modifiers, chelating
agents, anti-redeposition and soil suspending agents, optional brighteners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfumes and bleach catalysts can all be introduced into a wash liquor by means of
the additive products of the present invention, subject to the constraints imposed by the loading limitations of the substrate.
The surfactant can by any one or more surface active agents selected from anionic, zwitterionic, non-alkoxylated nonionic and amphoteric classes and mixtures thereof.  Specific examples of each of these classes of compounds are disclosed in
Laughlin &amp; Heuring U.S.  Pat.  No. 3,929,678 issued Dec.  30, 1975, which is hereby specifically incorporated herein by reference.
Preferred suds suppressing additives are described in U.S.  Pat.  No. 3,933,672 issued Jan.  20, 1976, Bartolotta et al., incorporated herein by reference, relative to a silicone suds controlling agent.  The silicone material can be represented
by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.  The silicone material can be described as siloxane having the formula: ##STR15## wherein x is from about 20 to about 2,000, and R and R&#39;
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German patent application DTOS No. 2646217, Gault et al, published Apr.  28, 1977, incorporated herein by reference.  An example of such a
compound is DC-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
1965, by Roy U.S.  Pat.  No. 3,433,021 issued Jan.  14, 1968, Gedge U.S.  Pat.  No. 3,292,121 issued Jan.  9, 1969, Bersworth U.S.  Pat.  No. 2,599,807 issued June 10, 1952, and carboxylic acid builders such as those disclosed in Diehl U.S.  Pat.  No.
phosphonic acid (EDTMP) and diethylene triamine penta methylene phosphonic acid (DETPMP), and the chelating agents are incorporated in amounts such that the substrate-chelating agent weight ratio lies in the range 20:1 to 1:5, preferably 5:1 to 1:5 and
most preferably 3:1 to 1:1.  Certain polybasic acids have been found to enhance the bleaching effect of organic peroxyacids produced when the products of the present invention are useful with conventional detergent composition, examples being EDTMP, NTMP
and DETPMP.  However, not all chelating polybasic acids are useful in this respect, while certain non-chelating polybasic acids, particularly succinic acid, do show efficacy.
Any of the conventional soil suspending and anti-redeposition agents can be included as optional components, examples being carboxymethyl cellulose and its derivatives and high M.Wt.  copolymers of maleic anhydride with methylvinyl ether or
A wide range of fabric softeners and antistatic agents can be included as optional compounds.  Exemplary cationic nitrogen compounds include the di- C.sub.16 -C.sub.18 alkyl, di- C.sub.1 -C.sub.4 alkyl quaternary ammonium salts, imidazolinium
salts and non-nitrogenous materials such as the sorbitan esters of C.sub.16 -C.sub.18 fatty acids.  A preferred fabric softening and antistatic composition suitable for incorporation into additive products of the present invention is disclosed in U.S.
Pat.  No. 3,936,537 issued Feb.  3, 1976 to R. Baskerville &amp; F. G. Schiro.  Compounds of this type are disclosed in German patent application OLS No. 2,516,104 published Oct.  30, 1975, specifically incorporated herein by reference.
Catalysts of use herein are those that enhance the effect of the bleaching species.  Examples of such materials are the salts of transition metals of atomic number lying between 24 and 29, utilised in conjunction with a chelating agent.  Woods
U.S.  Pat.  No. 3,532,634 issued Oct.  6, 1970 and specifically incorporated herein by reference discloses perborate bleach compositions containing an organic peroxy bleach precursor and catalytic compounds of this type.
The compositions herein comprise a precursor together with a nonionic-cationic surfactant mixture and optionally other ingredients in water-releasable combination with a solid non-particulate substrate.  Preferably the substrate is absorbent and
the materials are impregnated therein.  Application of the materials can be carried out in any convenient manner, and many methods are known in the art.  For example, where the materials are in liquid form they can by sprayed onto a substrate as it is
manufactured.  Where the precursor is in liquid form, this can be a melt, and it is highly preferable that the precursors melt at a temperature below that at which they decompose on being heated.  Where the precursor is a solid at normal temperatures,
alternative liquid forms can be used such as solution in organic solvents which are volatilised after application, and slurries or suspensions of the finely divided solid in water or other liquid media, such as the surfactant mixture.
As previously indicated, inorganic peroxy bleaches and other materials reactive towards organic peroxy compound precursors can be incorporated in the additive products of the present invention provided that the precursor and the bleach (or other
material) are spatially separated from each other.
technique, bleach-substrate weight ratios of up to 15:1 can be obtained.  This level of loading is attainable with cellular substrates but substrates of fibrous character are limited in practice to weight ratios of about 5:1.  Furthermore, loading
affecting a given substrate&#39;s absorbent capacity is its free space.  Accordingly, when a precursor is applied to an absorbent substrate, it penetrates into the free space, hence the substrate is deemed impregnated.  The free space in a substrate of low
In one method of making an impregnated sheet-like substrate, the impregnating mixture is applied to absorbent paper or non-woven cloth by a method generally known as padding.  The mixture is preferably applied in liquid form to the substrate and
precursors and other ingredients which are normally solid at room temperature should first be melted and/or solvent-treated.  Methods of melting the ingredients and/or treating with a solvent are known and can easily be carried out to provide a
satisfactorily treated substrate.
In this method, the mixture of precursor, 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 absorbent substrate then travels, at the same speed, upwardly and through a pair of rollers which squeeze off excess bath liquid.  The impregnated substrate is then cooled to room temperature, after which it can be folded,
cut or perforated at uniform lengths, and subsequently packaged and/or used.
to control the amount of the liquid on the substrate.
In an exemplary execution of the invention, the precursor and other ingredients in liquid form, is sprayed onto 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 organic peroxy compound precursor 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.degree.-80.degree.  C. preferably 45.degree.-65.degree.  C. is used and the molten material should have a viscosity of less than 5000 centipoises at
50.degree.  C., preferably no more than 500 centipoises.
Other variations include the use of metal &quot;nip&quot; 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 compound; this provides a composition which can be treated on one of its outer sides, yet contains several other plies, each of
which is treated on both sides.
The above techniques can be employed with any of the compositions of the present invention but it has been found that for those systems containing suspended solids some modifications are desirable in order to prevent segregation of the solids in
the melt over long periods and also to prevent build-up of the solid components on the surface of the equipment.
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.
In order to provide a mixture having suitable characteristics ie.  solidification over a range of temperature to give a waxy rather than a crystalline solid, certain of the precursors suitable for the purposes of the invention need to be blended
with a plasticising or thickening agent.  For this purpose the peroxy compound precursors can be divided into three different types, namely:
In the high melting solid group it is preferred that the melting point be less than 150.degree.  C. although materials having melting points up to 250.degree.  C. can be processed by handling as a dispersion in a melt of another material.  Of
25.degree. C.  Benzoic anhydride 40.degree. C.  Methyl o-acetoxy benzoate  49.degree. C.  p-acetoxy acetophenone 52.degree. C.  Polyazelaic polyanhydride  55.degree. C.  Succinic acid dinitrile 55.degree. C.  Tetra acetyl hexamethylene diamine
59.degree. C.  2,2-di-(4-hydroxyphenyl) propane  diacetate 79.degree. C.  1-cyclo hexyl, 3-acetyl hydantoin  86.degree. C.  Tetra acetyl methylene diamine  94.degree. C.  Phenyl o-acetoxy benzoate  97.degree. C.  N-acetyl imidazole 102.degree. C.
Diacetyl dimethyl glyoxime  112.degree. C.  Triacetyl guanidine 112.degree. C.  o-acetoxy benzoic acid 135.degree. C.  1-phenyl 3 acetyl hydantoin  147.degree. C.  Tetra acetyl ethylene diamine  148.degree. C.  Tetra acetyl glycouril 237.degree. C.
Sodium Acetylphenol sulphonate  Very High  ______________________________________
For the high and low melting point types a water soluble or dispersible organic adjuvant is required that has a range of temperature over which it melts, the adjuvant serving to provide a matrix of acceptable physical properties when impregnated
on a non particulate substrate, together with acceptable viscosity temperature characteristics to facilitate impregnation itself.  It should also be non-hygroscopic.  The adjuvant can be a single material or more commonly a mixture of materials whose
overall physical properties are satisfactory.  Materials that fall into this category include the long chain fatty acids and their water-soluble or water dispersible esters, certain nonionic ethoxylates such as tallow alcohol ethoxylates having more than
10 ethylene oxide groups per mole of alcohol and high molecular weight polyethylene glycols.  Certain mixtures of cationic and nonionic surfactants, notably those incorporating a quaternary ammonium surfactant bearing a long chain carboxylate counter
ion, have also been found to be satisfactory components of the water soluble adjuvant.
irrespective of the washing cycle being employed, when the additive products of the present invention are fed into the machine at the same time as the fabric load.  For machines including a prewash cycle, addition of the additive product at the beginning
of the main wash cycle is preferred.
The invention is illustrated in the following non-limitative examples in which parts and percentages are by weight unless otherwise specified.  Reference herein to a test method for assessing the efficacy of peroxy compound precursors in forming
(0.05 grams) is added and the mixture is immediately titrated with 0.01 Molar sodium thiosulphate solution using an iodine indicator (`Iotect` available from British Drug Houses Limited) to the first end point (blue/black--colourless).  Precursors which
require a titre of greater than 2 mls of 0.01 M sodium thiosulphate are preferred materials for the purposes of the present invention.
250 grs of tetra acetyl ethylene diamine, 165 grs of technical grade stearic acid and 165 grs of behenic acid were mixed together and heated to 65.degree.  C. to form a uniform dispersion.  This was passed through a Premier Colloid Mill set to
operate at a slow speed with a clearance of 0.0005&quot;, and the dispersion was then held in an agitated tank at 70.degree.  C.
250 grs of Dobanol (RTM) 45E7 (a substantially linear C.sub.14 -C.sub.15 primary alcohol condensed with an average of 7 ethylene oxide groups per mole of alcohol), 60 grs of Polyethylene glycol 6000 and 100 grs of a petroleum wax identified as
Veba Wachs SP1044 available from Veba-Chemie AG West Germany were liquified in a separate agitated vessel, to which 100 grs of C.sub.12 -C.sub.15 alkyl dimethyl hydroxyethyl ammonium bromide, 25 grs of ethylene diamine tetra methylene phosphonic acid, 15
grs of sodium salt of methyl vinyl ether maleic anhydride copolymer of MWt approximately 240,000 and 5.0 grs of an optical brightener were added to form a uniform dispersion.  This was also passed through a Premier Colloid Mill having the same setting as
described above and the resultant dispersion was then added to the first dispersion and thoroughly mixed therewith.
The substrate was in the form of a length of non-woven apertured material of 12&quot; width disposed on a reel.  The substrate material comprised a poly ester wood pulp available from Chicopee Mfg Co., Milltown New Jersey USA, and identified as SK 650
WFX 577, having a basis weight of 50 grs/sq meter (corresponding to 3.8 grs per sheet of 120 sq ins.  area) and which contained approximately 80 apertures per sq ins.
The heated dispersion was fed to a trough located over the upper of two heated counter rotating rolls mounted one above the other, the trough and the nip clearance being adjusted to produce an even coating of dispersion on the lower roll, which
was operated at a lower temperature than the upper roll to assist the transfer of dispersion at the nip.
The substrate was drawn off the reel over feed rolls and past the lower heated roll in contact therewith, the rotation of the heated rolls being arranged such that the direction of movement of the coated roll surface and the substrate were
opposed to each other.  The consequent wiping action impregnated the substrate and the uniformity of the substrate loading was enhanced by passage over further heated rolls arranged to contact each side of the substrate.  The impregnated substrate was
then solidified in a current of air before being stored on a product reel and subsequently cut into sheets of approximately 120 sq ins area.
______________________________________ 5.0 grs TAED  5.0 grs Dobanol 45E7  1.2 grs Polyethylene glycol 6000  2.0 grs C.sub.12 -C.sub.15 alkyl dimethyl hydroxyethyl  ammonium bromide  0.5 grs Ethylene diamine tetra methylene phosphonic  acid  0.3
grs Sodium salt of methyl vinyl ether-  maleic anhydride copolymer MWt 240,000  0.1 grs Optical brightener  3.1 grs Stearic acid  3.1 grs Behenic acid  2.0 grs Veba Wax  22.3 grs  ______________________________________
Sheets made up as desribed above had a pleasant waxy feel, a low tendency to pick up moisture on storage and when used with a conventional anionic surfactant-based perborate-containing laundry detergent provided enhanced removal of both grease
and oil and oxidisable fabric stains.
The procedure of Example I was followed using C.sub.12 -C.sub.14 alkyl methyl dihydroxyethyl ammonium methosulphate as the quaternary ammonium surfactant.  The resulting sheets had acceptable feel and hygroscopicity characteristics.
The procedure of Example I was followed except that the cationic surfactant was C.sub.12.5 alkyl dimethyl hydroxy propyl ammonium triborate.  Sheets having acceptable feel and stain removal performance characteristics were producted.
______________________________________ 250 grs TAED  65 grs Stearic acid  165 grs Behenic acid.  ______________________________________
______________________________________ 60 grs PEG 6000  100 grs Veba Wax SP 1044  15 grs Sodium salt of vinyl methyl ether maleic  anhydride copolymer  25 grs Ethylene diamine tetra methylene phosphonic  acid  5 grs Optical brightener  420 grs of
a 40.5% solution of C.sub.1.25 alkyl  dimethyl hydroxyethyl ammonium stearate in  Dobanol 45E7*  ______________________________________ *Made in accordance with the process described hereinbefore and the  subject of our copending British Patent
application No. 8989/78 filed  March 7th 1978, and entitled `Process for making Detergent Compositions`.
______________________________________ 5.0 grs Dobanol 45E7  5.0 grs TAED  1.3 grs Stearic acid  3.1 grs Behenic acid  1.2 grs PEG 6000  2.0 grs Veba Wax  0.3 grs Vinyl methyl ether maleic anhydride  copolymer  0.5 grs EDTMP  0.1 grs Optical
brightener  3.4 grs C.sub.12.5 alkyl dimethyl hydroxyethyl  ammonium stearate  ______________________________________
and had a smooth waxy feel and a reduced tendency to pick up moisture on storage.  When used with a conventional laundry detergent containing anionic surfactant and sodium perborate bleach enhanced removal of a range of greasy oily stains and
oxidisable stains were noted.
______________________________________ 5 6 7 8 9 10 11  ______________________________________ TAED 5.0 5.0 5.0 5.0 5.0  TAMD 5.0  AOBS 5.0  C.sub.15 DMHEAB  2.0 2.0  CMDHEAMS 2.0 2.0  C.sub.12 -C.sub.14 DMHEAS 3.5 3.5 3.5  TAE.sub.25 5.0
C.sub.14- 15 E.sub.15  5.0 5.0  C.sub.14- 15 E.sub.7 5.0 5.0  S-C.sub. 11-15 E.sub.9  5.0 5.0  EDTMP 0.5 0.5 0.5 0.5  DETPMP 0.5 0.5 0.5  VME-MA  (MWt 240,000)  0.3 0.2 0.2 0.2 0.2 0.2  PEG 6000 1.5 1.0 1.5 1.0  PEG 10,000 1.5 1.0  C.sub.18 FA 3.0 3.0
6.0 3.0 6.0 6.0 6.0  C.sub.22 FA 3.0 3.0 3.0  Wax 2.0 2.0 2.0  85-15 0.2 0.2 0.2 0.2  OWA 0.1 0.1 0.1 0.1 0.1 0.1 0.1  Substrate 1 / / / / /  Substrate 2 / /  ______________________________________
C.sub.14 DMHEAB--C.sub.14 alkyl dimethyl hydroxyethyl ammonium bromide
C.sub.12 -C.sub.14 DMHEAS C.sub.12 -C.sub.14 alkyl dimethyl hydroxyethyl ammonium stearate
TAE.sub.25 --Tallow alcohol (E.sub.25)
C.sub.14-15 E.sub.15 --C.sub.14 -C.sub.15 primary alcohol (E.sub.15)
C.sub.14-15 E.sub.7 --C.sub.14 -C.sub.15 primary alcohol (E.sub.7)
S-C.sub.11-15 E.sub.9 --C.sub.11 -C.sub.15 secondary alcohol (E.sub.9)
C.sub.18 FA--Stearic acid
C.sub.22 FA--Behenic acid
Laundry additive product, Spadini, et al., Gianfranco L. Spadini, Ian D. Tolliday, Allan C. McRitchie, Application number 05 919-531, Cleaning Compositions For Solid Surfaces Auxiliary Compositions Therefor Or Processes Of Preparing The Compositions, Coating Processes, laundry additive, laundry detergent, Fabric treatment, De-mite Laundry Additive, detergent composition, carbon atoms, dust mites, cause irritation, washer and dryer, laundry product
This invention relates to detergent additive products intended for the washing of textiles and especially for the removal of stains from textiles, particularly oxidisable stains and those having an oily or greasy character.BACKGROUND OF THE INVENTIONIn the Applicants' Swedish patent application No. 7711151-6 published on Apr. 6, 1978 there is disclosed a laundry additive product comprising:(a) a substrate in the form of a non-particulate solid article in water releasable combination with(b) an organic peroxy compound precursor, wherein the weight ratio of the precursor to the substrate lies in the range 90:1 to 1:10.The above disclosed invention is especially adapted for the removal of oxidisable stains from textiles when used in conjunction with conventional inorganic persalt-containing detergent compositions. It has now been found that certain mixtures ofnonionic and cationic surfactants incorporated together with the organic peroxy compound precursor in water releasable combination with a non-particulate substrate provide enhanced removal of a broad range of stains especially greasy and oily stains. The effect is further increased when the additive product is used in conjunction with a conventional heavy duty laundry detergent containing an anionic surfactant and an inorganic persalt.SUMMARY OF THE INVENTIONAccordingly the present invention provides a laundry additive comprising:(a) a substrate comprising a non-particulate solid article in water-releasable combination with,(b) an organic peroxy compound precursor wherein the weight ratio of the precursor to the substrate lies in the range from 30:1 to 1:10 and(c) a surfactant system comprising an alkoxylated nonionic surfactant having an HLB in the range 8.0-17.0 and a cationic surfactant having the empirical formula--R.sub.m.sup.1 R.sup.2.sub.x Y.sub.L Z wherein R.sup.1 is a hydrophobic organic radical containing alkyl chains, and/or aryl groups and which may also contain ether linkages, ester linkages, or ami