CA1209875A

CA1209875A - Laundry additive products

Info

Publication number: CA1209875A
Application number: CA000431547A
Authority: CA
Inventors: Maxim C. Brooks; Stephen P. Cassidy
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1982-07-03
Filing date: 1983-06-30
Publication date: 1986-08-19
Also published as: EP0099197A2; DE3376017D1; JPS5974198A; ES8507604A1; EP0099197A3; EP0099197B1; ES523769A0; ATE33039T1

Abstract

LAUNDRY ADDITIVE PRODUCTS

ABSTRACT

A laundry additive product comprising a solid laundry additive composition containing discrete agglomerated particles of storage sensitive detergency additive dispersed in a matrix of organic materials having a melting completion temperature of less than 85°C, the additive composition being in water-releasable combination with a unitary, water-insoluble carrier. A preferred storage-sensitive additive is a detergency enzyme. The compositions have improved storage-stabillty, dust control, reproducibility and convenience of use.

Description

i LAUNDRY ADDITIVE PRODUCTS

This invention relates to laundry additive products.
In particular, it relates to laundry additive products for cleaning clothes and the like in domestic and commercial ~ashing machines, the additive product containing a storage-sensitive detergency additive material.
It is widely recognized that the function of a detergenoy additive material can be significantly impaired in detergent and other laundry compositions by interaction between the additive material and other components o~ the composition or even with air. For example, detergency enzymes can be deleteriously affe~ted by interaction with bleaches, sequestrants, acids and bases, surfactallts and air perfumes and bleach activators can be dele~eriously affecte~ by interaction with bleaches; cationic fabric conditior.ers c~n be deleteriously affected by interaction with anionio surfact~nts; fluorescers can be deleteriously affected by interaction ~rlth bleaches and cationic sucfactants; and suds-sllppressors can also be deleteriously affectea by in~eraction with surfactants~ Moreover, the consumer acceptibility o~ a prodllct can also be significantly re~uced as the result of physical interactions between a lallndry additive material and other ~omponents o~
a composition. For instance, a speckled detergent containin~ a ~Jater-soluble dye can lose its aesthetic appeal as a result of migration of the d~e into the detergent base formula, an effect which can be signifieantly enhanced by the presence in the detergent composition oE a nonionic surfact2nt component.
One approach adopted in the art for minimizing storage-stability problems for sensitive inqredients is to agglo~erate the sensitive ingredient, for example by e~trusion, wet agglomeration~ etc and to add th~ resulting agglo~erate to a detergent base powder. British Patents ~.~

~2~

1,~04,123, 1,441,416 and 1,395,006 are representative of this general approach. The technique suffers a number of disadvantages, ho--Jever. For example, physical segregation problems caused by differences in particle ~ize and/or bulk density between the agglomerate and the base powder can contribute to reduced aesthe~ic appeal and reproducibility ` of performanc~. More importantly, the agglomera~es are prone to interparticle abrasion which can lead to partial or even total disintegration of the agglomerates with c~ncomitant problems o~ reduced storage stability and increased dust formation.
The Applicants have now discovered that laundry additive materials having improved storage-stability can be provided ~y dispersing agglomerated particles of the additive material in an organic matrix of defined thermal characteristics and which is combined in water-releasable manner with a ~;ater-insol~ble, unitary carrier. The resultin~ laundry additive products have improved storage-stability, convenience and reproducibiiity in use and recluc~d problems of dust formation.
Accordingly, the present invention provides a laundry additive product comprising:
(a) a solid laundry additive composition comprising discrete agglomerated particles of storage-sensitive detergency ~5 additive dispersed in a water-soluble or water-dispersible matrix of organic materials having a melting completion temperature of less than 85~C, wherein the storage-sensitive detergency additive has an average particle size of less than about 100 microns and wherein the 3~ agglomerated particles thereof have a particle size of from 150 to about 2000 microns~ wherein the organic matrix comprises at least 15% of an organic binding agent selected from the group consisting of polyethylene glycols of molecular weight greater that 1000, C12 C24 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range of from - 2a ~

about 40,000 to about 700,000, C14-C24 fatty alcohols ethoxylated with from about 14 to about 100 moles of ethylene oxide, and mixtures thereof, the laundry additive composition being in water-releasable combination with (b) a unitary water-insoluble carrier wherein said carrier is selected from the group consisting of (i) a flexible sheet-like substrate wherein the composition is coated onto or impregnated into said substrate, and (ii) a water-impermeable or water-frangible pouch having the composition incorporated therein.
The storage-sensitive detergent additive is suitably selected from detergency enzymes, bleaches,bleach activators and bleach catalysts, photoactivators, dyes, fluorescers, suds suppressors, perumes, fabric conditioning ayents, and hydrolysable surfactants. Mighly preferred are detergency enzymes, especially proteases, amylases and mixtures thereof. The laundr~ additive product will als~
usually incorporate an antagonist material responsible for the deleterious effect on storage stability of the additive;
alternatively, the additive material will be sensitive to storage in the presence of some environmental factor such as air, moisture, or sunlight. Preferred laundry additive materials and their specific antagonists are listed below:
Additive Antagonist i) Detergency En~ymes Bleaches, Sequestrants, Acids~ Bases or Surfactants ii) Bleaches Bleach Activators or Catalysts, Acids or Bases iii~ Bleach Activators or Bleaches, Acids or Bases ~leach Catalysts iv3 Pho~oactivators Nonionic Surfactants v) Dyes Nonionic Surfactants vi) Fluorescers Bleaches or Cationic Surfactants 20 vii) Suds con~rollers Surfactants viii) Perfumes Bleaches iY.) Fabric Conditioning A~ents Anionic Surfactants x) ~ydrolysable Surfactants Acids or Bases The laun~ry additive composition preferably comprises 2S at least about 40~, more pre~erably at least about 5~%, especially at least about 60~ of organic matrix materials having a melting completion temperature of less than about 85C. Th'ese in turrl each preferably~have a melting completion temperature of less than about 75C, more preferably less than about 7DC~ The additive compos;tion itself desirably has a sotening temperature oE at least about 35C, more preferably at least about 40C, especially at least about 50~C, and a penetrometer hardness of less tnan abollt 10, more preferably less than about 7~
In preEerred embodiments, the laundry additive product contains at least about 5~, preEerably at least about 15~ by w~ight of the o~s~tion of water-soluble or water-dispersible ~2~

organic binding agent having a melting-onset temperature of at least about 35C and a melting completion temperature of less than abo~t 8~C. Preferably, the binding agent is selected from polyethylene glycols of molecular weight greater than about 1000, C12-C24 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range from about 40,000 to about 700, ono, and C14-C24 fatty alcohols ethoxylated with from about 14 to about 100 moles of ethylene oxide. Highly preferred binding agents comprise at least about 40%~ especially at least about 50~ thereof of polyethyleneglycol having a molecular weight greater than about 4000.
The agglomerate component of the additive product generally comprises the detergency additive material together wi.h an agglomerating agent. In additionr the agglomerate can contain a solid diluent. The detergency additive and diluent are both pre~erably particulate in form with an average particle si~e of less than about 150 microns, more preferably less than 100 microns, especially less than 50 microns. A small particle size contributes to improved dispersability of the agglomerate. The physical integrity of the agglomerate should be such, however, to prevent disinte~ration during dispersion in the organic matrix. The average particle si~e of the agglomerate after dispersion is preferably at least about 100 microns, more preferably from about 150 microns ~o about 2000 microns.
The agglomerating agent can take the form of a carrier in which the detergency additive and, if p~esent, diluent are dispersed, or the agglomerating agent can simply act to promote physical adhesion of the component particles of the agglomerate. Alternatively the agglomerating agent can function as an encapsulating or coating agent for the detergency additive. Preferred carriers are water~soluble or water-dispersible organic materials having a melting 3S onset temperature of at least 35C, ~ore preferably at least 7~
( - 5 - ~

about 45C, especially at least about 50C and a melting ccmpletion temperature of at least a~iout 40~C, more preferably at least about 45C, especially at least 55~C, and of less th~n a~out 100C, more preferably less than about 85~C, especially less than about 75C. Desirably, the melting completion temperature of the carrier i~ at least about 5C greater than the softening temperature of the additive composition. Suit~ble organic carriers are again selected from polyethylene glycoIs of moleculcr ~eisht greater than about 1000, Cl~-C24 fatty acids 2nà esters and amides thereof, polyvi~yl pyrrolidone of molecular weight in tbe r~nge from abGut 40,000 to 2bout 700,G00, an~
C14-C24 fatty alcohols ethoxylated with from about 1~ to about 100 moles of ethylene oxide. Preferred diluents herein are inorganic and include al~ali metal, alkaline earth metal ~nd ammonium sulphates an~ chlorides, neutral and acid al~ali metal carbonates, orthophosphates and pyrophosphates, ~nd 21~ali metal crystalline ~n~ glassy polyphosphatesO Suitable water-insoluble but dispersible diluents include the finely-divided natural and synthetic silicas and silicates, especially smectite-type and kaolinite-t~-pe clays such as so~ium and calcium montmorillOnite, ~aolinite itself, aluminosilicates, and m~gnesium silicûtes and fibrous and microcryst211ine celluloses. Suitable adhesive materials include the organic carrier materials descri~ed above, water, aqueous solutions or dispersions of the inorganic diluent materials described above, polymer solutions ar.d latexes such as aqueous solutions of sodium carboxymethylcellulose, methylcellulose, polivin~lacetate, polyvinylGlcohol, dextrins, ethylene vinylacetate copolymer~ and acr~lic late~es. In the case of hydrolysable ar.d moisture sensitive additiv-es sufh as enzymes, however, the final moisture content of ~he acJglomerate should ~e no mcre than ~out 3~i.
In a highly preferred em~odi~ent, the additive cGmposition is co~ted on cr impregr.ated into ~ flexible, cheet-like su~strate at a ~eight ratio o composition:

~ 2 ~ 7 5 substrate (ie loadin~ ratio) of at least about 3:1, more preferably at least 5:1, especially at least about 6:1.
~lternatively, however, the additive composition can take the form of an aggregate of physically discrete solid bodies having the agglomerated particles of storage-sensitive detergency additive material dispersed therein, the aggregate being incorporated in a water-permeable or ~ater-frangible pouch.
The laundry additive products of the invention suitabl~ contain at least about 5~, preferably at least about 20~ of additive composition of organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof. Preerred nonionic surfactants have melting completion temperatures of less than about 85~ and form part of the matrix of organic materials. Pre~erred cationic surfactants have melting onset temperatures of at least about 35C and can either form part of the oxganic binding agent or be dispersed in the organic matrix.
Preferred anionic surfactants have melting completion temperatures in excess of about 100C and are dispersed in the organic matrix. Surfactants which are sensitive to alkaline or acid hydrolysis (eg al~yl sulphates~, ho~ever, can be incorporated in the organic matrix in the form of agglomerates. Of the above surfactants, highly preferred ~5 from the vie~rpoint of optimum detergency and agglomerate stability are anionic sulphonate and sulphate surfactants and/or water-soluble cationic surfactants and mixtures of these anicnic and/or cationic surEactants with water-soluble ethoxylated nonionic surfactants.
In a process embodiment of the inYention~ there is provided a process of making the laundry additive product defined herein cornprising the step of dispersing the agglvmerated particles of storage sensitive detergency additive in the matrix o~ organic materials under high shear conditions and at a temperature above the softening point of 5175i ) the additive composition but beneath the temperature and shear at which the agglomerated particles melt, decompose, or disintegrate.
T~le l~undry additive products of the irlver,tion Jill no~J be discussed in detail.
A preferred class of detergency additive material i~ a detergenc~ er.zyme. The enzyme is preferabl~- a hydrolysing enzyme and can be selected ~enerally from prote~ses, esterases, carbohydrases, and mixtures thereof. Examples of proteases suitable for use ~,erein are pepsin, trypsin~
chymotrypsin, collagenase, ~eratinase, elastase, subtilisin~
papa;n, bromelin, carboxypeptidase A and B, aminopeptidase, and aspergillopeptidase A and B. Preferred proteases are serine proteases which are active in the neutral to al~aline p}l range and are produced from microorganisms such as b~cteria, fungi or mould. A highly preferred prote~se is prepared by fermentation ~f a strain of Bacillus Subtilis.
Specific examples o~ carboh~dr~ses are maltase, saccharase~ amyl~ses, cellulase, pectinase, lysozyme, ~0 ~-glucosidase, and ~-glucosidase. Preferred are~-amylases of mould, cereal or bacterial origin.
Specific examples of esterases are gastric lipase, pancreatic lipase, plan~ lipases, phospholipases, cholineesterases and phosphot~ses.
A valuable feature of the enzyme embodi~ents of the in~ention is that the laundry additive product provides, in unitary form, the entire enzyme dosa~e for a single laun--- ~ering operation. This is hi~hly beneficial from the vie-~-poillt of enzyme handling and stability. Accordingly, the laundry additive products preferably comprise from about 0.~01 to about 0.5, more preferably from about O.Q03 to about 0.1~ of enzyme per unit Gf product (er.zyme expressed in pure forr,~ or protease and ~-amylase specifically~ the laundry additive products preferbly comprise from about 0.075 ~o about 15, more preferabl~ from about 0.15 to about 4~5 ,.~

~2~!~8~5 ~ - 8 -_ ~ _ ~nson units of protease per unit of product, and ~rom about

2,D00 to about 400,000, more prefera~ly from about 4~000 to about 120,000 maltose units of~ -amylase per unit of product. Protease activity is measured against Novo 5 Alcalase protease as standard using the method of Dunn &
Brotherton, Analyst, 96, 159-163 (1971). Amylase activity is measured as described in P. Bernfeld, AdV. in Enzymol., 12,379 (1959), but using starch substrate buffered to pB 6 with a sodium acetate (4.1%)/acetic acid buffer solution, a sample concentration of 0.05g/litre or a multiple dilution thereof, a digestion temperature of 37C and a digestion time of 5 ~inutes. The amylase then has one activity unit for each 0.4mg of maltose hydrate produced during hydrolysis.
The storage-sensitive deterqency additive CaJ; 21SG ~e represented by bleaches, ~leach activators ~nd bleac~l cata-lysts. Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, so--dium persilicate and urea~hydrogen peroxide addition products and the clathrate 4Na2SO4:2H2O~:lNaCl.
Suitable organic bleaches include peroxylauric acid, peroxyoctanoic aoid, peroxynonanoic acid, peroxydecânoic acid, diperoxydodecanedioic acid, diperox~azelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxyisophthalic acid. Peroxyacid bleach precursors suitable herein are disclosed in Ul~-A-20409~3, highly preferred being perace~ic acid ~leach ~recursors such as tetraacetylethylenediamirle, tetraacDtylmethylenedi.amine, te~raacetylhe~ylenediamine, sodium p-acetoxyben~ene sulphonate, tetraacetylgl~couril, pentaacetylglucose, octaacetyllactose, and methyl O-acetoxy benzoate. Bleach precursors can be used at a precursor: unitary carrier ratio within the range from about 30:1 to about 1:10, prefera~ly from about 8:1 to a~out 1:2, while bleaches can be used -~Z~ 375 at a bleach:unitary carrier ratio from about 30:1 to about 1:4, preferably from about 10:1 to about 1:1. Bleach catalyst systems suitable for use herein ;nclude chela~ed transition metal catalysts as described in U.S. Patent No.
4,430,243, issued February 7, 1984.
The storage sensitive detergency additive can also be represented by sud-suppressors, especially materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds controlling agents include polydimethylsiloxanes having a molecular wei~ht in the range from about ~00 to about 200,000 and a kinematic viscosity in the range from about 20 ~o about 2,000,00b mm/s, prefer~bly from about 3000 to about 30,0~0 mm/s, and mixtures of siloxanes and hydrophobic s;lanated ~prefera~ly trimethylsilanated) silica having a particle si~e in the range from about 10 millimicrons to about 20 millimicrons and a speoific surface area above about 50 m2/g. Suitable ~axes incl~de microcrystalline waxes having a melting point in the rancJe from about 65~C to about 100~C, a molecular weight in the range from about 400-1000, and a penetration value oE at least 6, measured at 77~C by ~STM-D1321, and also paraffin waxes, synthe~ic ~axes and natural w~xes.
Suitable phosphate esters include mono- and/or di-C16-C22 alkyl or alkenyl phosphate esters~ and the corresponding ~ono- and/or c~i al~yl or al~enyl ether phosp~ates oontaining up to 6 ethoxy groups p~r molecule.
Other storage-sensitive detergency additives include bleach-sensitive fluorescers such as'Blackophor'MBBH (Bayer ~G) and Tinopa~' CBS and E~S ~Ciba Geigy); nonionic surfactant-coluble dyes an~ photoactivat~rs as disclosed in U.S. Pate~t No. 4,417~994 issued ~ov3~r 29, 1983, highly ~l~f~l~d mater~ls being zinc phthalocyanine tri- and te~r~n1lrhnn~tes;
bleach-sensitive perfu~es; ~nionic surfactant-sensitive fabric conditionin~ agents suoh as di-C12-C2~ al~yl or alken~l amines and am~oniu~ salts; and hydrolysable * r~ Tr~rl~
** Trad~E~k ~2`~
suriactants such as the Cl~-C16 al~yl an(i alli~l ether sulphates.
The agglomerates of storage-sensitive detergency additive can be prepared by any appropriate agglomeration technique, for example by extrusion with a molten organic carrier or by dispersing liquid organic carrier or adhesive onto a moving bed of the storage sensitive additive, optionally in admixture with a solid diluent, in for example a pan agglomerator, Schugi mixer or fluidized bed apparatus>
Turning to the laundry additive composition, this is in solid form at ambient temperatures (25C and below) and preferab~y has a softening te~perature of at least about 35C, more preferably at least about 40C, especially at least about 50C~ Ry softeniny temperature is meant the temperature at which there is transition from plastic-flow to viscous-~lQw properties; at ambient temperatures, therefore, ~he composition ta~es the form of a plastic solid havin~ a non~zero yield stress. The hardness of the compositions at ambient tempera~ures can be determined by standard methods, for example, by ~he penetrometer-based t~chnique o~ IP49 (or the tec~lnically equivalent ~STM-D5 or BS4691). Thus, laundr~ ac;ditive composi~ions preferred for use herein have a penetration under a lOOg load at 25C
after 15 seconds under IP~9 of less than about ln (measured in tenths of a millimetre), more prefera~ly less than about 7. The so~tening temperature of the composition, on the other hand, is taken herein to be the temperature ~t which the IP~9 15 second penetration exceeds a~out 30.
The laundry additive composition herein comprises a matrix of organic ~aterials o~ defined meltin~
charact~ristics. ~elting completion temperatures are determined using a Dupont 910 Differential Scanning Calorimeter with Mechanical Cooling Accessory and R90 Thermal Analyser as follosJs. A 5-10 mg sample of the organic material containing no free water or solvent is encapsulated in a hermetically sealed pan with an empty pan as reference. The sample is initially heated until molten and then rapidly cooled (at about 20-30C/min) to -70~C

Thermal analysis is then carried out a a heating rate of 10~C/min using sufficient amplification of~T signal (ie temperature difference between sample and reEerence -vertical axis) to obtain an endotherm-peak signal:baseline noise ratio of better than 10:1. The melting completion temperature is then the temperature corresponding to the intersection of the tangential line at the steepest part of the endotherm curve at the high temperature end o~ the endotherm, with the horizontal line, parallel to the sample temperature axis, through the highest temperature endotherm peak~
The or~anic materials constituting the matrix have a melting completion temperature of less than about 85C. In addition, the laundry additive products of the invention 1~ preferably contain at least about 5~ by wei~ht of composition o~ binding agent defined as organic material haviny a melting completion temperature o less than 85C, preEerably less than about ~0C, especially less than about 70C, an~ a melting onset temperature of at least 35C~
preferably at least 40C, especially at least 50C. The melting onset temperature can once again be determined by thermal analysis as des~ribed above and is taken to be the sample temperature at the pOil)t of intersection of the base line with a tangent ~o the steepest part of the endotherm nearest the low temperature end of the endotherm.
In a highly preferred em~odiment, the additive composition is coated on or impregnated into a flexi~le sheet~ e substrate at a weight ratio of composition:
substrate of at least aboùt 3:1, pre~erably at least about 5:1~ Preferred substrates for use herein are apertured non~loven fabrics which can generally be defined as adhesively bonded fibrous or Eilamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or comprising fibrous mats, in ~hich the fibres or filaments are distributed haphazardly or in random array (i.e. an array of fibres in a carded web wherein partial orientation of the fibres is frequently present as .~ell as a completely ha~hazard distributional I

7~
-- 12 -- !

orientation) or substantially aligned. The fibres or filaments can be natural ~e.g. wool, silk, wood pulp, jute, hemp, c~tton, linen, sisal, or ramiP), synthetic (e.g.
rayonj cellulose~ ester~ polyvinyl derivatives, polyolefins, polyamides, or polyesters~ or mixtures of any o~ the abvve.
Generally, non-~oven cloths are made by air or water laying processes in which the fibres or filaments are first cut to desired lengths rom long s~rands, passed in~o a water or air stream, and then deposited onto a screen through which the fibre-laden air or water is passed. The deposited fibres or ~ilaments are then adhesively bonded together, dried, cured and otherwise treated as desired to for~ the non-woven clo~h.
Preferably, the non-woven clo~h is made from cellulosic ribres, particularly from regenerated cellulose or rayon, whieh are lubrica~ed with standard textile lubricant such as sodium oleate. Preferably the fibres are ~rom about 4 to about 50 mm, especially from about 8mm to about 2Um~, in length and are from about 1 to about 5 denier ~Denier is an internationally recognised unit in yarn measure, corresponding to the weight in ~rams of a 9,000 meter length of yarn). PreEerably the fibres are at least partially orierltated haphazardly, particularly substantially hapha2ardly, and are adhesively bonded together wi~h hydrophobic or su~stantiall~ llydrophobic binder-resin, particu~arly with a nonionic self-crosslin~ing acrylic polymer or polymers. In highly preferred embodiments, the cloth comprises ~rom about 75% to about 8~%, especially from about 7~S to about 84% fibre and from about 12% to about 25~, especially from about 16~ to about 22% hydrophobic binder-resin polymer by ~eight and has a basis weight of from about 10 to about 70, preferably from 2~ to 58 g~m2.
Suitable hydrophobic binder-resins are ethylacrylate resins * **
such as'Primal'HA24'Rhoplex'H~8 and HA16 ~Rohm and Haas Inc) and mixtures thereof.
Tne 1exible substrate for use herein is preferably an apertured substrate having an aperture density of ~rnm about 10 to about 30, preferably fro~ about 13 to about 26, more * ~r;l~pm~rk ** Tr~m~rk 13 ~ $87~

pref~r~bl~ from 16 to about 23 apertures per sq cm of sheet, ~iher~in the apertures, on average, have a width of from about 0.5mm to about 5mm and a length of from about 0.8mm to about 5mm, the substrate carrying a water releasable coatin~
of the laundry additive composition and having areas of uncoated apertures and areas ~Iherein the coating covers the apertures and extends between opposing surfaces of the substrate, the ratio of areas of uncoated to coated apertures bein~ in the range from about 15:1 to about 1:3.
The apertures themselves are generally symmetrical a~out a longitudinal axis ~ie they have mirror symmetry) and preferably have, 02~ average, a width of Erom about 0.7 to about 2.5mm and a length of from about 1.7mm to about 4mm.
The area of the apertures, on the other hand~ is preferably from about 0 7mm2 to about 7mm2, more preferably ~rom about O.~mm2 to about 3.5mm2, and the ratio of l~n~th:~idth is from 1:1 up to preferabl~ abou~ 6:1, more pre~era~ly about 4:1. These parameters are highly preferred Erom the viewpoint of achievin~ the optimllm ratio `of areas of u~coated to coated apartures and the complete filling of coated apertures frorn on~ surface of the substrate to the other .
Ttle substrate apertures herein can be elongate in s~?ape ~Eor example, qenerally elliptical or diamond-shapedj in which case the apertur~s preferably have a width oE from ahout 0. 8mln to about 1. 5mm and a len~th oE ~rom about 2mm to about 3.5mm.In preferred ~m~odiments, however, the a~ertures are generllly s~uare-shaped with a side dimension of from about 1 to 2.5mln. ~s used herein, nlength" refers to-the dil~ension of the principal (ie lon~est) lon~itudinal axis, and "wi~lth~ is the ~aximum ~imension perpendicular to this a~is.
As far as loading ratio is concerned ~ie the wei~ht ratio o~ com~osition:substrate) this pre~erably is at least about 6:1 and more preEerably at least 7~ loreover the ratio of the areas of uncoated to coated apertures in the ~inal ~roduct is preferably frol~ about 6:1 to about 1:2, ~2~87`5 ~ore preferably from about 4:1 to about 1:1.
~n example of an apertured non-woven substrate suitable herein is a regenerated cellulose sheet of 1.5 denier fibres bonded with R},oplex ~]A B binder (fibre:bind~r ratio o~ about 77:23~ having a basis weight of about 35 g/m2 and about 17 apertures/cm20 The apertures are generally ~lliptical in shape and are in side-by-side arrangement~ The apertures have a width of about 0~9mm and a length of about 2.5mm measured in a relaxed condition.
Another highly preferred substrate based on 1.5 denier regenerated cellulose fibres with'Rhoplex HA8'binder has a fibre:binder ratio of about 82:18, a basis weight o about 35g/m2, and about 22 apertures/cm2. In this example, the aper~ures are generally square-shaped with a width (relaxed) of about-l.lmm. The apertures are again disposed in side-by-~ide arrangement~
The size and shape of the substrate sheet ~or each unit of product is a matter of choice and is determined principall~ ~y factors associated with ~he convenience vf its use. Thus the sheet should not be so small as ~o become trapped in the crevices of the machine or the clothes bein~
washed or so large as to be awkward to pac~a~e and dispense from the container in which it is sold. For the purposes of the present invention shee~s ranging in plan area from about 130 cm2 to about 1300 cm2 are acceptable, the preferred area lying in the range of from about 520 cm2 to about 780 cm2 .
In another em~odiment~ the laundry additive composition takes the form of an aggre~ate of physically discrete so~id bodies having the agglomerated particles of storage-sensitive detergency additive dispersed therein, the aggregate being incorporated in a water permeable or water-frangible pouch. Suitable pouch materials include aper.ured substrates as described above, the relative dimensions of the aggregate and substrate apertures being such as to prevent "sifting~ of laundry additive composition through the apertures during mechanical handling.
Alternatively, the pouch material can contain a * Trademark 37~

water-Erangible seam or re~ions of low wet stren~th which rupture to allow egress of the additive composition d~ring the wash cycle.
The laundry additive products o~ the invention can be supplemented by all manner of laundering and detergency .cornponents. suitably, the additive products can contain at least about 5%, preferably from about 2~ to about 90%, more preferably from about 35% to about 75% of organic de~er~ent selected from anionic, nonionic ~nd cationic surfactants and mixtures thereof. Anionic surfactants preerably comprise from about 7% to about 38%, more preferably from about 15~
to about 30% ~y weight o-f composition; nonionic surfactants from about 8~ to about 3~%t more preferably from about 12%
to about 25% by weight of composition; and cationic 1~ surfactants from about 5~ to about 30%, more preferably from about 8% to about 20Qo by weight of compo~ition.
The anionic suractant can be any one or more oE the mat~rials used conventionally in laundry detergents~
Suitable synthetic anior.ic surfactants are water~oluble salts of al~yl benzene sul~honates, alkyl sulphates, alkyl polyetho~y ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpllo-car~)o~ylates and their est~rs, alkyl glyceryl ether sulphonates, fatty acid ~nono~lyceride sulphates ~nl3 sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy alkan~-l-sulphonclteJ
and beta-alkyloxy alkane sul~honate.
A particularly sui~able`class of anionic surEactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanQlaT~Tnonium salts or organic sulphuric reaction llr~ducts having in their molecular structure an alkyl or al~;aryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester yroup.
(Included in the term "alkyl" is t~e alkyl portion of acyl groups). Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C8 18) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain coniguration, e.g. those of the type described in U.S.P. 2,~20,099 and 2,477,383 and those prepared from al~ylben~enes obtained by alkylation with straight chain chloroparaffins (using aluminiuln trichloride catalysis) or straight chain ole~ins (using ~]ydrogen fluoride catalysis)~ Especially`valuable are linear straight chain al~;yl benYene sul~honates in which the average of the alkyl ~roup is a~out 11.8 carbon atoms, ab~)reviated as Cll ~ LAS, and C12 C15 y all~yl sulphates.
Other anionic detergent compounds herein include the sodium Cl0 18 alkyl glycer~l ether sulphonates, especially those ethers o higher alcohols derived ~rom tallow and coconut oil; sodiuln COCOtlUt oil fa~ty acid monoglyceride sulphonates and sulphates; and sodium or potassium salts of alkyl phenol et~ylene oxide ether sulphate containing about 1 to about 10 units of ~thylene oxide per molecule and wherein the alkyl groups colltain about 8 to about 12 carbon atoms.
Other useful anionic detergent compounds herein include the water-soluble salts or esters cf.x-sulphonated fatty acids containing from about 6 to 20 carbon atoms in the fat~ acid group and f rol!l about 1 to 1~ carbon atoms in the ester group; ~later-soluble salts of 8~5 ~ - 17 -2-acyloxy-alkane-1-sulphonic acids containing from ~bout 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moi~ty; alkyl ether sulphates containing from about 10 to 18, especially about 12 to 16, carbon atoms in the alkyl group and from about 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates eontaining from about 12 to 24, preferably aout 1~ to 16, carbon atoms, especially those made by reaction with sulphur trioxide followed by neutralization under conditions such that an~ sultones present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-soluble salts of paraffin sulphonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ~-alk~.~oxy alkane sulphonates containing from about 1 ~o 3 carbon atoms in the alkyl ~roup and Erom abou~ 8 to 2~ carbon atoms in the alkane moiety.
The alkane chains oE the fvre~oing non-soap anionic sur~actants can be derived from natural sources such as coc~nut oil or tallowJ or can be made synthetically as for example usin~ the 2iegler or Oxo processes. Water solubility c~n be achieved by using alkali metal, ammonium o~ al~anolammonium cations; sodium is preferred~ Suitable fatty acid soaps can be selected from the ordinary alkali 2~ metal ~sodium, potassium~, ammonium, and al~ylolammo~ium salts of higher fatty acids containing from a~out 8 to about 2~, preEerably from about 10 to about 22 and especially from -- about 16 to about 22 carbon atoms in the alkyl chain.
Suitable fat~y acids can be obtained from natural sources such as, for instance, ~rom soybean oil, castor oil, tallow, ~hale and fish oils, grease, lard and mixtures thereof).
The fatty acids also can be synthetically prepared (e~g., by the oxidation o~ petroleum, or ~y hydrogenation of carbon m~noxid~ by the ~ischer-Tropsch process). ~esin acids are suitable such as rosin and those resin acids in tall oil.
Naphthenic acids are al50 suitable. Sodium and potassium soaps c~n be made b~ direct saponiEication of the ats and - :L~ -oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process.
Particularly useful are the sodium and potassium salts o the mixtures of fatty acids derived from tallo~7 and S hydrogenated fish oil.
Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulfonate and sulfate surfactants in a ~ei9ht ratio of from about 5:1 to about 1:5, preferably from about 5:1 to about 1:1, more preferably from about 5:1 to about 1.5:1. Especially preferred is a mixture of an al~yl benzene sulfonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an al~yl sulfate having from 10 to ~0, pre~erably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulfate havin~ Erom 10 to 2~, preferahly 10 to 16 carbon atoms in the al~l radical and an avera~e degree of ethoxylation o~ 1 to 6, having an alkali metal cationt prefer~bly sodium.
The nonionic surEactants useful io the present invention are condensates oE ethylene oxide with a hydrophobic moiety to provide a surEactant having an average hydrophilic-lipop~ilic balance (~ILB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.$. The hydro~hobic moiety may be alipI)atic or aromatic in nature and the len~th oE the po].yoxy~th.~lene ~roup ~hiclI i5 condensed ~ith any particular hydrophobic group can be readily adjusted to yield a ~ater-sol~bl~ compound having the desired degree of balance bet~een hydrop`nilic and hy~rophobic ~lements.
Examples of suitable nonionic surEactants include:
1. The polyethylene oxide conden~ates of alkyl phenol, e.g. Lhe condensation products o. alkyl phenols having an alkyl g~oup containing from 6 to 12 carbon atoms in either a straight chain or branched chain conEiguration, with ethylene o;~ide, the said ethylene ovide being present in amounts equal to 3 to 30, preferabl~ 5 to 14 moles of ethylene oxide per mole of alkyl phen~l. The alkyl substituent in such compounds ma~ be derived, for example, from polymerised propylene, di-isobu~ylene! octene and nonene. Other examples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles OL e~hylene oxide per mole of phenol; nonylphenol and di-isooctylphenol condensed with 13 moles of ethylene oxide.
2. The condensation product of primary or secon~ary ali-~0 phatic alcohols having from 8 to 24 carbon atoms, in ei~her straight chain or branched chain configuration, with from 2 ~o about 4~ moles, preferably 2 to about 9 moles of ethylene oxide per mole of ~lcohol. Preferably, the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably hetween 3 and 8 moles o ethylene oxide pe,r mole o aliphatic alcohol. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural ats or, prepared by the ~iegler process from ethylener e.~g. myristyl, cetyl, stearyl alcohols), or partly branched such as the 'Lutensols,'Dobanols~and~l~eodols~which have about 25~ 2-methyl bran_hing '(Lutensol'being a trademax~ of BASF, 'Dobanolland'l~Jeodol' being trademarks of Shell), or'Synper-onics, which are understood to ha~e about 50~ 2-methyl bran-chin~ (Synpe~onic is a trademark of I~Col~) or the primar~
alcohols having more than 50~ branched chain structure sold under the trademark 'Lial'by Liquichimica. Specific exam-ples of nonionic surfactants falling within the scope of the inven~ioll includeiDobanol 45~4','Dobanol 45-7" Dobanol 45-9', 'Dobanol 91-2. 5t bobanol 91-3, bobanol 91-4'~'Dobanol 91-6, 'Dobanol 91-8J 'Dobanol 23-6.5' '~ynperonic 6','Synperonic 14, the condensation products of coconut alcohol with an average o~ between 5 and 12 mol~s of ethylene oxide per mo-le of alco-hol, the coconut alkyl portion having f~om 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an avera~e oE between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion com~rising essentially ~`
. o between 16 and 22 carbon atoms. Secondary linear alkyl eth-oxylates are aiso suitable in the pres~nt compositionst es~
pecially those ethoxylates of the~Tergitor series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
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 ~enerally falls in the ran~e of about 1500 to 1800.
Such synthe~ic nonionic detergents are availablP on the market under the trademark Of ~Pluronic~
supplied by Wyandotte Chemicals Corporation.
Especially preferred nonionic surfactan~s for use herein are the Cg-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole o alcohol.
Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surEactants of a semi-polar ~0 nature, for example ami~ne oxides, Suitable surfactants of the amine oxide class have the general formula I

R R
Rl _ N _ (CH~ R2 O _ O
wherein Rl is a linear or branched al~yl or alkenyl 2~ group having 8 to 20 carbon atoms, each R2 is independently selected rom Cl 4 alkyl and -(CnH2nO~mH ~here i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of CnH2nO groups in a molecule being no more than 7.
In a pre~erred emb~di~ent R has from lU to 14 carbon atoms and each ~2 is indPpendently selected from methyl and * Trademark h.~
~$875 ( -21 - ~

-(Cn~l2nO)mH wherein m is from 1 to 3 and the sum total of CnH2nO groups in a molecule is no more than 5, preerably no more than 3. In a highly preferred embodiment, j is O and each R is methyl, and Rl is C12-C14 alkyl.
Another suitable class of amine oxide species is represented by bis-amine oxides haviny the following substituents.

j: 1 R : tallow C16-C18 alkyl, palmityl; oleyl; stearyl R2: hydroxyethyl i : 2 or 3 A specific example of this preferred class o~ bis-amine oxid~s is: N-hydro~enated C16-C~ tallow alkyl-N,N',N'tri-(2-hydroxyethyl) -propylene-1,3-diamine oxide.
lS Suitable quatern~ry ammonium surfactants for use in the present composition can be defined by the ~eneral formula II:

R 3 - N - (C~l2)i ~ R4 Z II
R4 _ R4 wherein R3 i~ a linear or branched alkyll alkenyl or alkaryl grou~ havin~ n to 16 carbon atoms and each R4 is inclependently selected from Cl ~ alkyl, Cl 4 alkaryl and -(CnH~nO~m ~herein i is an integer from 1 to 6, j is O or 1, n is 2 or 3 and m is from 1 to 7, the sum total of Cn~l2nO groups in a molecule~
being no more than 7, and wherein Z represents a counteranion in number to give electrical neutrality, In a preferred embodiment/ R has from 1~ to 14 carboR
atoms and each R4 is independently selected from methyl and ~QH2nO)mH wher`ein m is from 1 to 3 and the sum total of CnH2nO groups in a molecule is no more than 5, Llreferably no more than 3. In a highly preferred embodiment j is 0, R~ is selected from meth~l, hydroxyethyl and hydroxypropyl and R3 is C12-C14 alkyl. Particularly ~2~$~75 ~ - 22 -preferred surfactants of this class include C12 alkyl trimethylammonium salts, C14 alkyltrimethylammonium salts, coconutalkyltrimethylamm~ni~m salts, coconutalkyldimethyl-hydroxyethylammonium salts, coconutalkyldimethylhydroxy-S propylammonium salts, and C12 alkyldihydroxyethylmethylammonium salts.
Another group of useful cationic compounds are the diammonium salts of formula II in ~hich j is 1, R3 is C12-Cl~ alkyl, each R4 is methyl, hydroxyethyl or hydroxyprop~l and i is 2 or 3. In a par~icularly preferred surfactant of this type, R3 is coconut alkylr R4 is methyl and i is 3.
Chelating agents that can be incorporated include citric acid, nitrilotriacetic and ethylene diamine tetra acetic acids and their salts, or~anic phosphonate derivatives such as those disclosed in Diehl US Patent No. 3,~13~030 issued 19 October, 1965; ~oy US Patent No~ 3,433,021 issued 14 January, 196~; Gedge US Patent No. 3,292,121 issued 9 January, 1968;
and Bersworth ~S Patent No. ~,599~807 issued 10 June, 1952, and c3rb~x~1ic acid builder salts such as those disclosed in Diehl US Patent No. 3,3~,067 issued 7 March, lg67.
Preferred chelating agents include nitrilotriacetic acid (NTA3, nitrilotrimethylene phosphonic acid (NTMP~, ethylene diamine tetra methylene phosphonic acid (E~Tr~p) and ~5 d:ietllylelle triamine penta methylene phosphonic acid (DE'rP~P), and these are incorporated in amoun~s such that the substrate chelatirlg agent ~7eight ratio lies in the range from about 20:1 to about 1:5, preferably from about 5:1 to about 1:5 and most preferably 3:1 to 1:1.
Antiredeposition and soil suspension agents ~lso constitute preferred components of the additive product of the invention. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hy~roxyethylcellulose are examples of soil suspension agents a~d suitable antiredeposi~ion agents are provided by homo- or co-polymeric polycarbo~ylic acids or their salts in which at lea5t two carboxyl radicals are present separated by not more ;

- -- 23 -- ` !

than two carbon at~ms.
Highly preferred polymeric polycarboxylic acids are cop~lymers of maleic acid ~r maleic anhydride Witll methyl vinyl ether, e~hyl vinyl ether, ethylene or acrylic acidJ the polymers having a molecular weight in the range from 12,000 to 1,500,000.
A further description of suitable polymeric polycarboxylic acids is provided in the Applicantsl European Patent Application No. 82301776.9, published October 20, 1982.
In a method of making the laundry ~dditive products of the invention, agglomerated particles of storage-sensitive detergency additive are dispersed in ~he ma~rix o organic materials under high-shear mixing conditions and at a temperature above the softening point of the additive composition but beneath the temperature and shear at which the agglomerates melt, decompose or disintegrate to provide, after dispersion, an average agglomerate size of at }east 100 microns, preferably from about 150 to about 300 microns. In a preferred process embodiment, the dispersion temperature is at least 5C ab~ve the softenin~ ~oint of the composition and, where the ag~lomerate incorporates a carrier, at least 5C beneath the meltins completion temperature and more preferably at least 5~C below the melting onset ~emperature of the carrier for the a~glomerated particles. Th~ actual ~5 temperature of the organic matrix during the dispersing step can ran~e from about 40C to about 75~C, preferably from about 50~ to abou~ 70C. Thèreaf~er, in the case of laundry additive products comprising an impregnated or coated substrate, a current vf the laundry-additive composition is dispensed onto a moving substrate at an application rate of from about 120 to about 400 g/m~t preEerably from about 120 to about 320 9/m2 of substrate. The melt can be dispensed from the nip of a pair of counter rotating~ heated rollers ha~ing a nip setting great~r than the average siz~ o the agglomerat~s, but preferably less than ~bout 400 microns, ore preferabl~ from about 150 to about 300 microns, the substrate being arranged ~or ~ovement counter to one o~ the rollers and in contact therewith, whereby the melt is .

( - 24 -transferred to the substrate by a wiping action. Thereafter~
the s~bstrate passes through smoothin~ and distributing - means, for example a pair of plates stationed on opposite sides of the substrate at a spacing of less than ~bout 300 micror.s, preferably from about 120 ~o about 220 microns~
~inally, the coated substrate is cooled in a current of air.
The invention is illustrated in the following non-limitative Examples in which parts and percentages are ~y weight unless other~lise specified.
In the Examples, the abbreviations used have the following designation:

~AS Linear C12 alkyl benzene sulphonate C1~14AS : Sodium C12-C14 alkyl sulphate TAEn : Hardened tallow alcohol ethoxylated wit~l n moles of ethylene oxide per mole of alcohol l;AO C12-C14 alkyl dimethyl am`ine amide C12TMAB : C12 alkyl trimethyl ammonium bromide C12 Amide : Coconut monoethanolamide 20 Dobanol 45-E-7 : ~ Cl,~-Cls primary alcohol ` cvnclensed with 7 moles of ethylene oxide, marketed by Shell Clay : Sodium montmorillonite PEG : Polyethylene glycol (M~it normally ~ollows) TAED : Tetraacetylethylenedia~ine Silicone/Silica : 20:1 mixture of polydimethylsiloxane and silanate~ silic~
~'~x ~ ~licrocrys.alline wax -'~Jitodurl -272-~i.pt87C
Pcrphine : Trijtetra sulphonated 2inc phthalocyanin~

* Trad~mark *, -- 25 --V GantreZ ANll9~ l : Maleic anhydride/vinyl ~ethyl ~` '-,er copolymer, believed tc~ have an average molecular weight of 2~,00D, marketed by ~AP. This mater;al w~s . prehydrolysed with NaOH before addition.
Perborate : Anhydrous sodium perborate bleach of empirical formula NaB2 H22 MA/AA Maleic acid/acrylic acid copolymer, 1:4 m~le ratio, m.wt 80,000.
EDTA : Sodium ethylenediamine tetraacetate Bright~ner 1 : Disodium 4,4'-bis~2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'~disulpho~ate lS Brightener 2 : Disodium 4,4'-bis(2-sulphonato styryl)biphenyl DE~PMP : Diethylenetriamine pentatmethylene phospho~ic acid), marketed by ~ons~nto under the trademark 'Dequest EDTMP : Ethylenediamine tetra~methylene phosphonic acid), marketed by Monsanto, under th~ trademark 'Deguest 2~41' 25 Su~strate 1 Non--~oven fabric ~ormed of 1~0 unbleached crimped rayon ~ibres o~
1.5 denier ~onded with 23%
polyacrylate binder; basis weight 35 g~m~; 17 elliptical a~ertures~cm2; aperture width 0.9m,n; aperture length 2.5mm Su~strate 2 O ~lon-woven fabric formed of 100~
unbl~ached crimped rayon fibres of 1.5 denier bonded with 18%
polyacrylate binder; basis weigh~
. 35g/m~, 22 square-shaped apertures~cm~; side dimension l.lmm EXAMPLES 1 to 6 Laundry additive products according to the invention 40 are l)repared as follows. For each product, the c~mponents of the laundry additive co~position are mixed at a temperature o~ about 60~C and passed through ~'Fryma Colloid ~lill~3 Model MK95-R/MZ 80~ (made ~y l~.M. Process Equip~nt Ltd of M.M. House, Fro~ore Road, He~el Hempstead, * Trademark * * Trademark ~5 ~ertLor~ ir , ~nite~ Kingdom~ in ~hich the ~Jrindin~ faces are set to a separation of about 180 microns. The melt is then fed through a pair of counterrotatin9 rolls heated to 76C and ~avin~ a nip setting of 250 microns and is trans-ferred to substrate moving counter to one o-E the roll~rs by ~7iping. lhe coated substrate is finally passed bet~Jeen a pair of static plates having a spacing of 180 microns, air-cooled, and cut into sheets of si~e 35 X 23cm.
EXAMPLES
1 2 3 ~ 5 6 ~ _ _ _ _ _

- 3 3 _ 2 Dobanol 45E7 5 3 6 8 ~ 5 MAO ~ 3 PEG ~000 - 5 6 -~ 3 3 Silicone~Silica 0.3 0.3 - - 0.3 Gantrez ~Nll9 - 0,3 - _ ~,3 MA/AA - - 0.5 - - U.3 Perborate - 5 - - 4 7 EDTA 1 - - 0.5 0.~ -Aluminium Sulphate - ~ ,3 Bri~htener 1 0.1 0.3 - 0.2 Bri~hterler 2 - 0.1 0.2 0.2 - 0.2 Tetrasodium DETPMP - 1 - - n. 5 Tetrasodium EDT:~P - - 1 0.5 - - -~loisture 0.02 0.01 0.03 0O02 0.01 D.02 Substrate 1 2.8 - 2.8 - 2.8 --Substrate 2 - 2.8 - 2.8 - 2.8 Agglomerate 1 1 0.5 1 1.5 1 0.5 Agglomerate ~ - 3 - - - -Agglomerate 3 - - 1 1 - -~gglo~erate 4 ~gglomer~te 5 - _ _ _ 5 Agglo~erate 6 - - - - - 2 ~2~7~;

In the above Examples, the a~glomerates have the follo~ing composition:

AGGLO~I~RATE

- ~ 5_ Protease 9 Amylase 3 TAED - 86 - ~ 20 Silicone/silica - - 11 ~ ~ 10 Porphine - - - 0.2 Brightener 1 - - - 10 Bri~htener 2 Cu EDT~ complex (1:1 molar) ~ - 10 TiO2 10 - - --`
TAE~o -- 1~ 6 _ 27 10 C12 Amide ~ _ _ _ _ Polyvinylpyrrolidone 2~ Cl~y - - - - 42 Dext.rin 4 - - ~ ~ ~

Sodium sulp~late 13 ~ Sodiurn chloride 5~ - - - - -~odium tripolyphosphate - - 56 ~0 - 47 ~a~er - - 15 98 - 13 ;

7~

,~" ` i In the above, Agglomerate 1 is prepared by extrusion and has a protease activity of ~ Anson units~g and an amylase actiYity of 48,000 maltose units/g; Agglomerate 2 i5 ~repared by ex rusion in a radial extru~er as described in European Patent Ppplication No. 82301775, published Octc~ber ~:3, 1982;
Aggl~ates 3 and 6 are ~l~d by spray~on of stor~ge-sensi~ive ingredient and organic carrier onto a fluidized ~ed o~
granular so~ium ~ripolyphosphate ~hydrated); and Agglomerates 4 and 5 and prepared by spray-on of organic carrier and, where appropriate water, onto the remaining granular components in a drum agglomerator.
The compositions of Examples 1 to 6 have excellent storage-stability, convenience and reproducibility in use, and improved dust control.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A laundry additive product comprising:
(a) a solid laundry additive composition comprising discrete agglomerated particles of storage-sensitive detergency additive dispersed in a water-soluble or water-dispersible matrix of organic materials having a melting completion temperature of less than 85°C, wherein the storage-sensitive detergency additive has an average particle size of less than about 100 microns and wherein the agglomerated particles thereof have a particle size of from about 150 to about 2000 microns, wherein the organic matrix comprises at least 15% of an organic binding agent selected from the group consisting of polyethylene glycols of molecular weight greater than 1000, C12-C24 fatty acids and esters and amides thereof, polyvinyl pyrrolidone of molecular weight in the range of from about 40,000 to about 700,000, C12-C24 fatty alcohols ethoxylated with from about 14 to about 100 moles of ethylene oxide, and mixtures thereof, the laundry additive composition being in water-releasable combination with (b) a unitary water-insoluble carrier wherein said carrier is selected from the group consisting of (i) a flexible sheet-like substrate wherein the composition is coated onto or impregnated into said substrate, and (ii) a water-impermeable or water-frangible pouch having the composition incorporated therein.

2. A product according to claim 1 wherein the storage-sensitive detergency additive is selected from detergency enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, suds suppressors, perfumes, fabric conditioning agents, and hydrolysable surfactants, and mixtures thereof.

3. A product according to claim 2 incorporating therein an antagonist for the storage-sensitive detergency additive, and wherein the detergency additive/antagonist combination are selected from at least one of the following:

4. A product according to claim 2 wherein the storage-sensitive detergency. additive is an enzyme selected from proteases, amylases and mixtures thereof.

5. A product according to claim 1 wherein the additive composition has a softening temperature of at least 35°C, a 15 second penetrometer hardness of less than 10, and comprising at least 40% of said organic matrix materials.

6. A product according to claim 1 wherein the agglomerated particles comprise an agglomerating agent and optionally a solid inorganic diluent, the agglomerating agent being in the form of a water-soluble or water-dispersible organic carrier, an adhesive, or an encapsulating or coating agent.

7. A product according to claim 1 wherein the binding agent comprises at least about 40% of said composition and said binding agent is a polyethylene-glycol having a molecular weight greater than about 4000.

8. A product according to claim 1 wherein the additive composition is coated on or impregnated into a flexible, sheet-like substrate at a weight ratio of composition:substrate of at least 3:1.

9. A product according to claim 1 wherein the additive composition is in the form of an aggregate of physically discrete solid bodies having the agglomerated particles of storage-sensitive detergency additive dispersed therein, the aggregate being incorporated in a water-permeable or water-frangible pouch.

10. A product according to claim 1 wherein said product contains at least 5% of an organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof.

11. A product according to claim 10 wherein the organic detergent is selected from anionic sulphonate or sulphate surfactants and/or water-soluble cationic surfactants and mixtures of said anionic or cationic surfactants with water-soluble ethoxylated nonionic surfactants.

12. A product according to claim 1 wherein the additive composition is coated on or impregnated into a flexible, sheet-like substrate at a weight ratio of composition:substrate of at least 5:1.

13. A product according to claim 1 wherein said product contains at least 20% of an organic detergent selected from anionic, nonionic and cationic surfactants and mixtures thereof.