CA1299460C - Granular non-phosphorus-containing bleach activator compositions and use thereof in granular detergent bleach compositions - Google Patents
Granular non-phosphorus-containing bleach activator compositions and use thereof in granular detergent bleach compositionsInfo
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- CA1299460C CA1299460C CA000532482A CA532482A CA1299460C CA 1299460 C CA1299460 C CA 1299460C CA 000532482 A CA000532482 A CA 000532482A CA 532482 A CA532482 A CA 532482A CA 1299460 C CA1299460 C CA 1299460C
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- phosphorus
- bleach activator
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- weight
- bleach
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
C 7074 (R) ABSTRACT
Improved granular non-phosphorus-containing bleach activator composition and detergent bleach composition comprising said granular composition are disclosed.
The granular bleach activator composition comprises (i) a finely divided bleach activator; (ii) an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt; (iii) a water-soluble, film-forming polymeric material of average molecular weight of from about 500-1,000,000; and (iv) a smectite or alumino silicate clay material. The granular bleach activator composition can be stably and effectively used in substantially phosphorus-free granular detergent compositions.
Improved granular non-phosphorus-containing bleach activator composition and detergent bleach composition comprising said granular composition are disclosed.
The granular bleach activator composition comprises (i) a finely divided bleach activator; (ii) an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt; (iii) a water-soluble, film-forming polymeric material of average molecular weight of from about 500-1,000,000; and (iv) a smectite or alumino silicate clay material. The granular bleach activator composition can be stably and effectively used in substantially phosphorus-free granular detergent compositions.
Description
C 7074 (R) Granular non-~hosphorus-containing bleach activator compositions and use thereof in granular deter~ent .
bleach compositions This invention relates to granular nGn-phosphorus-containing bleach activator compositions, their manufacture and use in granular detergent compositions.
Particularly it pertains to qranular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursors usable in low phosphorus or phosphorus-free granular detergent bleach compositions.
Granular detergent compositions which contain organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and peroxygen bleaching agents are known in the art. The peroxygen bleaching agents comrnonly used are those which release hydrogen peroxide in aqueou~ solution, such as alkalimetal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persaltq". The most commonly used persalt in detergent compositions is alkalimetal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
The organic bleach activators re~erred to herein are generally organic N-acyl or 0-acyl compounds, or carbonic or pyrocarbonic ester3, which react with hydrogen peroxide ~e.g. from the persalt~) in solution ~orming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, is effective in bleaching at lo~er tempQratures, e.g. from ambient to , ' .
~2~ c 7074 (~) 5uch bleach activators ar~ amply described in literature, for example in a series of articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, pages 26, 27 and 67, and further in 8ritish Patent Specifications 836,988;
855,735: 907,356; 907,358: 970,950; 1,003,310 and 1,246,339; US Patent Specifications 3,332,882, 3,277,750, 4,128,494 and 4,412,939.
A repre~entative, but by no means comprehensive, list of activator~ which can be used in the present invention is given below:
(a) N-diacylated and N,N'-tetraacylated amines, such as N,N,N',N'-tetraacetyl methylene diamine or -ethylene diamine, N,N'-diacetyl aniline and N,N'-diacetyl-p-toluidine or 1,3-diacylated hydantoin~ aA, for example, the compounds l,3-diacetyl-~,5-dimethylhydantoin and 1,3-dipropionyl hydantoin;
(b) N-alkyl-N-suphonyl carbonamides, for example the compound~ N-methyl-N-mè~yl acetamide, N-methyl-N-mesyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide;
(c~ N-acylated cyclic hydraæides, acylated triazoles or urazoles, for example monoacetyl maleic acid hydrazide;
(d) 0,N,N-tri~ubstituted hydroxylamines, ~uch as 0-benzoyl-N,N-succinyl hydroxylamine, 0-acetyl-N,N-~uccinyl hydroxylamine, 0-p-methyoxybenzoyl, N,N-~uccinyl hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl hydroxylamine and 0,N,N-triacetyl hydroxylamine;
(e) N,NI-diacyl ~ulphurylamides, for example N,N'-dimethyl-N,N'--diacetyl sulphuryl amide and N,N'-diethyl-N,N'-dipropionyl sulphurylamide;
(f) Triacyl cyanurate~, for example triacetyl cyanurate and tribenzoyl cyanurate;
(g) Carboxylic acid anhydride~, such as benzoic anhydride, m-chlorobenzoic anhydride, phtalic anhydride and 4-chlorophtalic anhydride;
12~ c 7074 (R) (h) Sugar esters, for example glucose pentaacetate;
(i) 1,3-diacyl-4,5-diacyloxy-imidazolines, for e~ample l,3-diformyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-dipropionyloxy imidazoline;
(j) Tetraacetyl glycoluril and tetraproprionyl glycoluril, (k) Diacylated 2,5~diketopipera~ines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-10 diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine;
(1) Acylation products of propylene diurea and 2,2-dimethyl propylene diurea, especially the tetraacetyl or tetrapropionyl propylene diurea and their dimethyl derivatives;
(m) Carbonic acid esters, for example the sodium salts of p-(ethoxycarbonyloxy) benzonic acid and p-(propoxycarbonyloxy) benzene sulphonic acid;
(n) Alpha-acyloxy-(N,N')polyacyl malonamides, such as alpha-acetoxy-(N,N')-diacetyl malonamide.
Since these bleach activator compounds are generally hydrolysable materials, they need to be protected from the surrounding media when incorporated in detergent compositions. On the other hand, any proper method o protecting the bleach activator from the environment must allow a relatively quick release or dissolution o the activator in the wash liquor. Relea3e of the activator must be achieved at a period well before the end of the wash cycle 80 a~ to give time Por the activator to react with the persalt forming the peroxyacid. Preferably thls should occur as early a~
possible in the wash cycle for maximum bleaching to occur.
~he most common way of protecting bleach activator~ is by presenting them in the form of granuleq or agglomerates.
~2~ c 7074 (R) Various compositions and forms of bleach activator granules have been proposed in the art, most of them using a phosphate, par~icularly sodium triphosphate, A8 an es~ential component of the granulating agent because of it~ typical property of imparting good structure combined with quick dispersion to the granule. A
representative example of such bleach activator ~ranule compositions having good storage stability and satisfactory release is that which comprise3 a mixture of sodium triphosphate and potassium triphosphate as the granulating agent, currently used in the majority of commercial detergent powder formulations.
~or many years, phosphates, such as sodium triphosphate, have indeed been used as deterqency builders.
With the increasing trend of legislation in a number of countries to ban phosphoruq from detergent compositions, because of the general belief that phosphates and phosphorus-containing compounds can lead to environmental problems, it has become desirable and necessary to provide detergent composition~ which are free, or 3ubstantially free, of phosphorus.
Consequently, in formulating ~uch phosphorus-free detergent bleach compo3itions comprising a bleach activator, it ha~ also become nece~sary to look for a rea~onable alternative to bleach activator granule compositions which are free of phosphorus but which should have the phy~ical properties and performance characteristics comparable to phosphorus-containing bleach activator granule~ when used in detergent compositions under non-phosphorus conditions.
A number of alternative non-pho~phorus builders have been proposed.
C 7074 (R) Examples of such non-phosphorus~containing detergency builders are the alkalimetal carbonates, such as ~odium carbonate; the alkalimetal silicates, such as sodium silicate; the alumino silicates, such as the various zeolite types of alumino silicates; the nitrilotriacetic acid compounds, such as ~odium nitrilotriacetate (NTA);
the carboxymethyloxy succinates; sodium citrate; the various polymeric carboxylate builders, such as the oxydisuccinates, hydrofuran tetracarboxylates, O-~ S-or N-linked sulphosuccinates, oxydiacetic acid, oxidised polysaccharides, polyacrylic acids, alkyl and alkenyl succinates; soaps and sulpho fatty acid soaps; and mixtures thereof.
Non phosphorus-containing bleach activator granule compositions are known in the art and various ~ethods o~ preparing such granules and their use in detergent compositions have been proposed.
In the majority of cases an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for exalnple nonionic compounds, fatty acids, fatty alcohols, waxes and polymeric materials with or without the optional use of inorganic salt~.
German DE-OS 2,657,042 disclose~ a detergent composition comprising tetraacetyl ethylene diamine ~TAED) in the form of granule~, which con~ist of ~aid TAED activator and a nonionic surfactant having a melting point of at least 351C as the binding agent.
European EP-B-0051987 (Procter C Gamble) di~close~
bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40C as binding agent.
~ C 7074 (~) A major disadvantage of nonionics is that they tend to bleed and cause stickiness, giving rise to caking problems, especially under hot summer temperature conditions. Migration of nonionics in the for~ulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach system~ Higher melting nonionics will have poor dispersing ability, resulting in a poor release of the bleach activator, with the deleterious con~equence of the granules ~edimenting and being lost in the dead spaces of the washing machines, known as mechanical loss. The same applies to fatty acids, fatty alcohols and waxes.
European Patent Specifications EP-007047~ and EP-0037026 (Henkel) disclose methods of using water-soluble cellulose ether, starch or starch ether aq granulation binder for preparing bleach activator granules having a bleach activator content of from 90-99% by weight. The methods a~ described here are only viable if coarce particle size bleach activator~ are used.
European Patent Application EP-0075818 (BASF) discloses water-free activator granules comprising a) 70-99.5 bleach activator and b) 0.5-30% of a swelling agent, prepared by compacting the compounds a) and b) without the addition of water, optionally ~ollowed by breaking into smaller particles.
As swelling agents are mentioned high molecular weight carbohydratec, 9uch a~ starch, powdered cellulose, wood pulp: croqs-linked polyvinyl pyrrolidone (P~P) and also starch ether and carboxymethyl cellulose.
All the~e proposalc have been made without the object of using such~bleach activator granule~ in non~
phosphoru3 detergent formulations.
~ ~ ~9 ~ ~ ~ C 7074 (R) It is an object of the present invention to provide an improved granular non-phosphorus-containing bleach activator composition which can be stably and effectlvely used in sub~tantially phosphorus-free granular detergent compositions.
This and other objects, which will be apparent from the further description of the invention. can be achieved if a finely divided particulate bleach activator is granulated with a mixture comprising an inert non-alkaline, non-phosphate inorganic or organic salt, a water-soluble, film-forming polymeric material of average molecular weight of from about 500-1,000,000, and a smectite or alumino silicate clay lS material, to form granules of a size of from about 0.2 to 2.0 mm.
Accordingly, the invention provides a granular bleach activator composition which is qubstantially free of phosphorus material~, the composition comprising:
(i) a finely divided bleach activator;
(ii) an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt;
(iii) a water-soluble, film-forming polymeric material of averaye molecular weight of from about 500-1,000,000: and (iv) a smectite or alumino silicate clay material Preferred bleach activators are the N-diacylated and N,N'-tetraacylated amines mentioned under a) above, particularly N,N,N',N'-tetraacetyl ethylene diamine, the ester~ of carbonic or pyrocarbonic acid~ mentioned under m) and the reactive pheno] e~ters a~ de~cribed in US Patent Specification 4,412,934.
One ~lngle activator or mixtures of two or more activators may be u~ed as desired.
4~ ~ C 7074 (R) ~he non-alkaline, non-phosphate inorganic salts which can be used in the invention are, for example, qodium ~ulphate, sodium nitr~te, ~odi~m citrate, sodium chloride, calcium sulphate and calcium chloride.
A preferred salt is 30dium sulphate.
Film-forming polymeric materials which can be u~ed in the invention are, for example, carbohydrates and derivatives, such a~ carbohydrate ethers: polymers or copolymer~ from vinyl monomers, such as vinylacetate (and its hydrolysate vinyl alcohol), vinyl pyrrolidone, methyl acrylate, acrylic acid, methacrylic acid, maleic acid (anhydride), styrene, styrene sulphonate or mixtures thereof. Specific examples of suitable polymeric materials are polyvinyl acetate, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol/polyvinyl acetate; carboxy methyl cellulose; dextrine modified vinylacetate polymers: and homo- or copolymeric polycarboxylic acids or salts thereof, such as the polyacrylic acids or polyacrylate~, copolymers of maleic acid (anhydride) and acrylic or methacrylic acid, and copolymers of maleic acid (anhydride) and vinyl-methyl ether.
The ~mectite clay materials usable in the present invention are preferably selected from the group consisting of alkali and alkaline earth metal montmorillonites, saponite~ and hectorites, and particularly those having an ion-exchange capacity of at leaqt about 50 meq/100 g. However, illite, attapulgite and kaollnite ciays can also be used in the instant invention~
The clay minerals used in the in~tant compositions can be deqcribed a~ expandable, three-layer clays, in which a sheet of aluminium/oxygen atoms or magnesium/oxygen atom~ lieq between two layerq of silicon/oxygen atoms, ~ C 7074 (~) i.e. alumino-slicates and magnesium silicates. The term "expandable" a~ used to describe clays ~elates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used the~ein are examples o~ the clay mine~als classified geologically as smectites.
There are two distinct classes of smectite clays that can be broadly differentiated on the basis of the numberq of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in the outer layers. The dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH)4Si8_yAly(A14 xMgx)020, nontronite (OH)4Si8_yA14_xFex)020 a volchonkoite (OH)4Si8_yAly(A14_xCrx)020, where x has a value of rom 0 to about 2,0.
The trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH)4Si8_yAly(Mg6 XLix)02o, saponite (oH)4(si8-yAly)(M96-xAlx) 20' sauconite (OH)4-si8_yAly(Zn6-xAlx) vermiculite (OH)4Si8_yAly(Mg6_xFex)020l wherein y has a value of 0 to about 2.0 and x has a value of 0 to about 6Ø
It is to be eecognized that the range of the water of hydration in the above Eormulas can vary with the processing to which the clay ha~ been subjected.
,Speciic non-limiting examples o~ smectite clay minerals are:
29946C13 C 7 0 7 4 ( R ) Sodium Montmorillonite Volclay sc~
Gelwhite GP
Thixo-Jel 1 Ben-A-Gel ~
Sodlum Hectorite Veegum F
Laponite SP~
Sodium Saponite Barasym NAS 100 ~
Calcium Montmorillonite Soft Clark Gel White L
Lithium Hectorite Barasym LIH 200-Most of the smectite clays useful in the compositions herein are commercially available under various trade-names, for example, Thixo-Jel 1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay ~C
and Volclay 325, from American Colloid Co., Skokie, Illinois; and Veegum F, from R.T.Vanderbilt. It is to be recognized that such srnectite minerals obtained under the foregoing tradename~ can comprise mixtures of the variou3 discrete mineral entities. Such mixtures of the ~mectite minerals are suitable for use herein.
Within the classes of montmorlllonite, hectorite, and saponite clay minerals, certain clay~ are preferred.
For example, Gelwhite GP, Volclay BC and certain smectite clays rnarketed under the name "bentonite'~
3~ ~en~ r~e ~
~ 99~ ~ C 7074 (R) Bentonite, in fact, is a rock type originating from volcanic ash and contains montmorillonite ~one of the smectite clays) as its principal clay component. The Table shows that materials commercially available under the name bentonite can have a wide range of cation exchange capacities. Each of these bentonites can in principle be used in the present invention without problems arising.
10 Rentonite Supplier Exchange capacity _ _ meq/100 g Brock ~ ~Georgia Kaolin Co, USA 63 Soft Clark Georgia Kaolin Co, USA 84 Bentonite L Georgia Kaolin Co, USA68 ~v, 15 Clarolite ~
T-60 ~ Georgia Raolin Co, USA61 Granulare~
Naturale ~
Bianco ~ Seven C. Milan Italy 23 20 Thixo-Jel 4 Georgia Kaolin Co, USA 55 Granular Naturale Normale Seven C. Milan Italy 19 Clar~ol ~
25 FB 5 Ceca Paris France 12 PDL 1740 Georgia Kaolin Co, USA 26 Versuchs Product FFI Sud-Chemie Munich Germany 26 ....
Low colloid content (~ 50%) The alumino silicate clay materials usable in the present invention are normally commercially available and can be naturally occurring or synthetically derived.
Preferred ~ynthetic crystalline alurnino silicate ion-exchange materials useful herein are available under 61 ~ h~S t~C~G~
C 7074 (R) the deslgnations Zeolite A, Zeolite ~, Zeolite X, Zeolite HS~and mixtures thereof.
The level of such clay materials for use as binder component in the granular bleach activator composition may be as low as about 0.5% and can be increased up to about 15% by weight.
Not only will the presence of small amounts of clay enhance the dispersibility, but it is also economically attractive as a partial replacement of the polymeric material without affecting the overall physical properties of the bleach activator granules.
Effectively, the granular bleach activator compositions will comprise:
(a) from 55-90% by weight of the finely divided bleach activator:
20(b) from 3-20% by weight of the inorganic or organic salt;
(c) from 1-10% by weight of the film-forming polymeric material; and (d) frorn 0.5-15% by weight of the smectite or alumino 25~ilicate clay material.
Water may be present in an amount of up to about 4.5%, preferably up to 3~.
As explained hereinbefore, the invention has particular ~pplicability to non-phosphorus detergent compositions, although it ~hould be appreciated that its use in other detergent compositions is no~ excluded.
Accordingly, in one other aspect the invention provides a detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
~ ~hot~$ ~ Vk C 7074 (R) (i) a detergent active material;
(ii) a non~phosphorus-containing detergency builder;
(iii~ a peroxygen bleaching agent; and (iv) a non-pho~phorus gran~lar bleach activator composition a~ hereinbefore defined;
The preferred detergent active compounds are fully described in Ga 1,437,950 referred to above.
The effective amount of the detergent active compound or compounds used in the composition is generally in the range from 5 to 40% by weight, preferably not more than 30~ by weight of the composition.
A second es3ential ingredient of the composition i9 a non-phosphorus-containing detergency builder which may be present in an amount of from 5-80~ by weight of the compo~ition. Preferred non-phosphorus-containing detergency builders are:
i) the alumino silicate cation exchange materials, both crystalline and amorphous, having the general formula:
(Cat2/nO)x-Al2o3 ~sio2)y~z 2 wherein ~at i~ a cation having valency n that is exchangeable with calcium ~e.g. Na~ or K~); x i9 a number from 0.7-1.5; y is a number from 1.3-4; and z i5 such that the bound water content i~ ~rom 10~ to 28% by weight.
Preferred alumino~ilicates are the crystalline material~
of the zeolite type of the following general formula:
Nax(Alo2)x:(sio2)y~z~H2o i2~9 6 C 7074 (R) wherein x and y are integers of at least 6, the ratio of x to y being in the range of l:l to 1:2; and z is such that the bound water content is from 10~ to 28% by weight.
Particularly preferred materials of the zeolite class are the A-type zeolites;
ii) Nitrilotriacetetic acid compounds, particularly sodium nitrilotriacetate (NTA), and iii) Polycarboxylate polymers as described in EP A-0137669; and mixtures of ~ (iii); or (i) + (ii) + iii).
In addition thereto, it is possible to include minor amounts of other non-phosphorus detergency builders, provided that the total amount of the detergency builders does not exceed 80% by weight, 90 as to leave room in the detergent composition for other desirable ingredients.
Groups of other non-phosphorus detergency builders are known in the art and described in a number of patent publications, such as the sodium carboxy methyloxy disuccinates; citric acid; ~ellitic acid; benzene polycarboxylic acids; and the polyacetalcarboxylates as disclosed in US Patent Specification 4,l44,226.
Where a soap i9 u~ed as a detergent active material, it may be present in such a quantity that it will also contribute as an additional builder.
The amount of ,oeroxygen bleaching agent used in the composi~ions of the invention will generally be from 5 to 30~ by weight, preferably from 7~ to 25~ by weight.
C 7074 (R) The amount of non-phosphorus bleach activator granules incorporated in the compositions will depend on the bleach activator content of the granule composition and should be from 0.5~ to 15~ by weight~ more preferably from 1.5~ to 10% by weight, calculated as pure bleach activator.
With regard to the bleach activator as used in preparing the granular bleach activator compositions, it i~
preferred that its particle size should be le~s than 200 micrometre, more preferably 150 micrometre. aleach activators having a major proportion of particle size of between 50 micrometre to 150 micrometre as de~cribed in Ga Patent Specification 2,053,998 are particularly suitable.
The detergent compositions in which the granular non-phosphorus bleach activator compositions are incor-porated can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
One such optional ingredient is an alkalimetal silicate, particularly ~odium, neutral, alkaline, ~eta-or orthosilicate. A low level of silicate, ~or example 2-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machine~
and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30~, for example from 10~ to 20~ by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water-soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor i9 used in water with appreciable levels of magnesium hardnes~. The amount of silicate can also be used to some extent to control the C 7079 (R) equilibrium pH of the wash liquor, which is generally within the range of 9-11, preferably 10-11, for an aqueous solution of the composition at the recommended concentration. It should be noted tha~ a higher pH
(i.e. over pH 10.5) tends to be more efficient as regards detergency, but it may be less desirable for domestic safety. Sodium silicate is commonly supplied in concentrated aqueous ~olution or in concentrated powder form, but the amounts are calculated on an anhydrouæ basis.
Examples of other optional ingredients include the lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acid3, lather depressants, fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes, such as proteases and amylases, germicides and colourants.
Particularly when the composition does not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the deposition of calcium carbonate on to fabrics.
The detergent compsitions may be produced by any of the techniqueM commonly employed in the manufacture of fabric washing detergent compositions, including particularly slurry-making and spray-drying processes for the manufacture of detergent powders.
The invention will now be Purther illustrated by reference to the following non-limiting Examples.
~2~ 7074 (R) Example I
The following granular non-phosphorus bleach activato~
composi~ion was prepared:
Composition I ~ by weight TAE~ (bleach activator) 84.g Sodi~m sulphate 10.4 Polymer* 1.1 10 Kaolin clay 2.2 Water 1.4 *Gantre ~ AN 119, a copolymer of maleic anhydride and vinyl methyl ether. (Gantrez is a registered Trade Mark).
A solid feed consisting of a mixture of 90~ TAED and 10% sodium sulphate was sprayed with the proper amount of an aqueous mixture consisting of 5% Gantrez AN 119, 10% kaolin and 85~ water in a Schugi Flexomix 160 Apparatus. The product was aerated to dry and obtain a product of the above composition with the following properties:
Comp. IControl Comp. A B
Bulk density g/l 404 500-640 458 Dynamic flow rate ml/s 120 80 114 Compre3sibLlity % 12.9 20 12.4 Granulometry:
30 Mean particle size micrometre 721 600-800 848 1700 mlcrometre nil 1 nil ~ 250 micrometre 8.8 S 9.4 % 125 micrometre 2.9 2 3.8 Storage properties in NTA/zeolite detergent powder containing sodium perborate monohydrate ~tored in wax laminated cartons at 37C/70RH.
C 7074 ( R ) Detergent Powder Com ~ lon% by wei~ht Sodium C12 alkylbenzene sulphonate 9-0 5 Primary C13-C15 alcohol/
7 ethylene oxide 4.0 Zeolite 30.0 Na-nitrilotriacetate (NTA)4.0 Alkaline sodium silicate 5.7 10 Sodium succinate 4.4 Sodium carbonate 5.0 Sodium carboxymethyl cellulose 0.5 Sodium sulphate 15.4 Water 8.0 15 Anti-foam granule 5.0 Sodium perborate monohydrate5.5 TAED granules 3.5 Control Comp. I Comp. A B
TAED decomposition ~:
after 4 weeks 15.613-27 13.5 after 8 weeks 18.520-38 51.3 25 Perborate decomposition ~:
after 4 weeks 16.358-63 8.5 after 8 weeks 34.755-89 36.2 TAED delivery:
Peracid yield, peak value m-mole/1 0.961.20 0.94 Peracid yield, peak time minutes 11.512.5 20.0 1299460 C 7074 (R) Control granule Com~ _ B
% by weight TAED (bleach activator)58-62 85.0 Sodium triphosphate 18-22 Potassium triphosphate 13-15 Water 5-7 1.5 Sodium sulphate - 7.6 Polymer* ~ 5 9 * Copolymer of maleic anhydride and acrylic acid (Sokalan CP 5 ex BASF).
Examples II and III
Similar good results were obtained with the following ~ranular non-phosphorus bleach activator (TAED) compositions:
Compositions _(% by weiqht) II III
TAED 80.5 87.3 Sodium sulphate 4.8 8.4 Polymer 1) 3.7 1.0 Clay 2) 8.5 1.9 Water 2.5 1.4 1) Polymer in II is Sokalan ~ CP 5 ex BASF/ a maleic acid/acrylic acid copolymer; Polymer in III is Gantrez ~ AN 119.
2) Clay in II and III is calcium bentonite.
bleach compositions This invention relates to granular nGn-phosphorus-containing bleach activator compositions, their manufacture and use in granular detergent compositions.
Particularly it pertains to qranular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursors usable in low phosphorus or phosphorus-free granular detergent bleach compositions.
Granular detergent compositions which contain organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and peroxygen bleaching agents are known in the art. The peroxygen bleaching agents comrnonly used are those which release hydrogen peroxide in aqueou~ solution, such as alkalimetal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persaltq". The most commonly used persalt in detergent compositions is alkalimetal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
The organic bleach activators re~erred to herein are generally organic N-acyl or 0-acyl compounds, or carbonic or pyrocarbonic ester3, which react with hydrogen peroxide ~e.g. from the persalt~) in solution ~orming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, is effective in bleaching at lo~er tempQratures, e.g. from ambient to , ' .
~2~ c 7074 (~) 5uch bleach activators ar~ amply described in literature, for example in a series of articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, pages 26, 27 and 67, and further in 8ritish Patent Specifications 836,988;
855,735: 907,356; 907,358: 970,950; 1,003,310 and 1,246,339; US Patent Specifications 3,332,882, 3,277,750, 4,128,494 and 4,412,939.
A repre~entative, but by no means comprehensive, list of activator~ which can be used in the present invention is given below:
(a) N-diacylated and N,N'-tetraacylated amines, such as N,N,N',N'-tetraacetyl methylene diamine or -ethylene diamine, N,N'-diacetyl aniline and N,N'-diacetyl-p-toluidine or 1,3-diacylated hydantoin~ aA, for example, the compounds l,3-diacetyl-~,5-dimethylhydantoin and 1,3-dipropionyl hydantoin;
(b) N-alkyl-N-suphonyl carbonamides, for example the compound~ N-methyl-N-mè~yl acetamide, N-methyl-N-mesyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide;
(c~ N-acylated cyclic hydraæides, acylated triazoles or urazoles, for example monoacetyl maleic acid hydrazide;
(d) 0,N,N-tri~ubstituted hydroxylamines, ~uch as 0-benzoyl-N,N-succinyl hydroxylamine, 0-acetyl-N,N-~uccinyl hydroxylamine, 0-p-methyoxybenzoyl, N,N-~uccinyl hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl hydroxylamine and 0,N,N-triacetyl hydroxylamine;
(e) N,NI-diacyl ~ulphurylamides, for example N,N'-dimethyl-N,N'--diacetyl sulphuryl amide and N,N'-diethyl-N,N'-dipropionyl sulphurylamide;
(f) Triacyl cyanurate~, for example triacetyl cyanurate and tribenzoyl cyanurate;
(g) Carboxylic acid anhydride~, such as benzoic anhydride, m-chlorobenzoic anhydride, phtalic anhydride and 4-chlorophtalic anhydride;
12~ c 7074 (R) (h) Sugar esters, for example glucose pentaacetate;
(i) 1,3-diacyl-4,5-diacyloxy-imidazolines, for e~ample l,3-diformyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-dipropionyloxy imidazoline;
(j) Tetraacetyl glycoluril and tetraproprionyl glycoluril, (k) Diacylated 2,5~diketopipera~ines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-10 diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine;
(1) Acylation products of propylene diurea and 2,2-dimethyl propylene diurea, especially the tetraacetyl or tetrapropionyl propylene diurea and their dimethyl derivatives;
(m) Carbonic acid esters, for example the sodium salts of p-(ethoxycarbonyloxy) benzonic acid and p-(propoxycarbonyloxy) benzene sulphonic acid;
(n) Alpha-acyloxy-(N,N')polyacyl malonamides, such as alpha-acetoxy-(N,N')-diacetyl malonamide.
Since these bleach activator compounds are generally hydrolysable materials, they need to be protected from the surrounding media when incorporated in detergent compositions. On the other hand, any proper method o protecting the bleach activator from the environment must allow a relatively quick release or dissolution o the activator in the wash liquor. Relea3e of the activator must be achieved at a period well before the end of the wash cycle 80 a~ to give time Por the activator to react with the persalt forming the peroxyacid. Preferably thls should occur as early a~
possible in the wash cycle for maximum bleaching to occur.
~he most common way of protecting bleach activator~ is by presenting them in the form of granuleq or agglomerates.
~2~ c 7074 (R) Various compositions and forms of bleach activator granules have been proposed in the art, most of them using a phosphate, par~icularly sodium triphosphate, A8 an es~ential component of the granulating agent because of it~ typical property of imparting good structure combined with quick dispersion to the granule. A
representative example of such bleach activator ~ranule compositions having good storage stability and satisfactory release is that which comprise3 a mixture of sodium triphosphate and potassium triphosphate as the granulating agent, currently used in the majority of commercial detergent powder formulations.
~or many years, phosphates, such as sodium triphosphate, have indeed been used as deterqency builders.
With the increasing trend of legislation in a number of countries to ban phosphoruq from detergent compositions, because of the general belief that phosphates and phosphorus-containing compounds can lead to environmental problems, it has become desirable and necessary to provide detergent composition~ which are free, or 3ubstantially free, of phosphorus.
Consequently, in formulating ~uch phosphorus-free detergent bleach compo3itions comprising a bleach activator, it ha~ also become nece~sary to look for a rea~onable alternative to bleach activator granule compositions which are free of phosphorus but which should have the phy~ical properties and performance characteristics comparable to phosphorus-containing bleach activator granule~ when used in detergent compositions under non-phosphorus conditions.
A number of alternative non-pho~phorus builders have been proposed.
C 7074 (R) Examples of such non-phosphorus~containing detergency builders are the alkalimetal carbonates, such as ~odium carbonate; the alkalimetal silicates, such as sodium silicate; the alumino silicates, such as the various zeolite types of alumino silicates; the nitrilotriacetic acid compounds, such as ~odium nitrilotriacetate (NTA);
the carboxymethyloxy succinates; sodium citrate; the various polymeric carboxylate builders, such as the oxydisuccinates, hydrofuran tetracarboxylates, O-~ S-or N-linked sulphosuccinates, oxydiacetic acid, oxidised polysaccharides, polyacrylic acids, alkyl and alkenyl succinates; soaps and sulpho fatty acid soaps; and mixtures thereof.
Non phosphorus-containing bleach activator granule compositions are known in the art and various ~ethods o~ preparing such granules and their use in detergent compositions have been proposed.
In the majority of cases an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for exalnple nonionic compounds, fatty acids, fatty alcohols, waxes and polymeric materials with or without the optional use of inorganic salt~.
German DE-OS 2,657,042 disclose~ a detergent composition comprising tetraacetyl ethylene diamine ~TAED) in the form of granule~, which con~ist of ~aid TAED activator and a nonionic surfactant having a melting point of at least 351C as the binding agent.
European EP-B-0051987 (Procter C Gamble) di~close~
bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40C as binding agent.
~ C 7074 (~) A major disadvantage of nonionics is that they tend to bleed and cause stickiness, giving rise to caking problems, especially under hot summer temperature conditions. Migration of nonionics in the for~ulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach system~ Higher melting nonionics will have poor dispersing ability, resulting in a poor release of the bleach activator, with the deleterious con~equence of the granules ~edimenting and being lost in the dead spaces of the washing machines, known as mechanical loss. The same applies to fatty acids, fatty alcohols and waxes.
European Patent Specifications EP-007047~ and EP-0037026 (Henkel) disclose methods of using water-soluble cellulose ether, starch or starch ether aq granulation binder for preparing bleach activator granules having a bleach activator content of from 90-99% by weight. The methods a~ described here are only viable if coarce particle size bleach activator~ are used.
European Patent Application EP-0075818 (BASF) discloses water-free activator granules comprising a) 70-99.5 bleach activator and b) 0.5-30% of a swelling agent, prepared by compacting the compounds a) and b) without the addition of water, optionally ~ollowed by breaking into smaller particles.
As swelling agents are mentioned high molecular weight carbohydratec, 9uch a~ starch, powdered cellulose, wood pulp: croqs-linked polyvinyl pyrrolidone (P~P) and also starch ether and carboxymethyl cellulose.
All the~e proposalc have been made without the object of using such~bleach activator granule~ in non~
phosphoru3 detergent formulations.
~ ~ ~9 ~ ~ ~ C 7074 (R) It is an object of the present invention to provide an improved granular non-phosphorus-containing bleach activator composition which can be stably and effectlvely used in sub~tantially phosphorus-free granular detergent compositions.
This and other objects, which will be apparent from the further description of the invention. can be achieved if a finely divided particulate bleach activator is granulated with a mixture comprising an inert non-alkaline, non-phosphate inorganic or organic salt, a water-soluble, film-forming polymeric material of average molecular weight of from about 500-1,000,000, and a smectite or alumino silicate clay lS material, to form granules of a size of from about 0.2 to 2.0 mm.
Accordingly, the invention provides a granular bleach activator composition which is qubstantially free of phosphorus material~, the composition comprising:
(i) a finely divided bleach activator;
(ii) an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt;
(iii) a water-soluble, film-forming polymeric material of averaye molecular weight of from about 500-1,000,000: and (iv) a smectite or alumino silicate clay material Preferred bleach activators are the N-diacylated and N,N'-tetraacylated amines mentioned under a) above, particularly N,N,N',N'-tetraacetyl ethylene diamine, the ester~ of carbonic or pyrocarbonic acid~ mentioned under m) and the reactive pheno] e~ters a~ de~cribed in US Patent Specification 4,412,934.
One ~lngle activator or mixtures of two or more activators may be u~ed as desired.
4~ ~ C 7074 (R) ~he non-alkaline, non-phosphate inorganic salts which can be used in the invention are, for example, qodium ~ulphate, sodium nitr~te, ~odi~m citrate, sodium chloride, calcium sulphate and calcium chloride.
A preferred salt is 30dium sulphate.
Film-forming polymeric materials which can be u~ed in the invention are, for example, carbohydrates and derivatives, such a~ carbohydrate ethers: polymers or copolymer~ from vinyl monomers, such as vinylacetate (and its hydrolysate vinyl alcohol), vinyl pyrrolidone, methyl acrylate, acrylic acid, methacrylic acid, maleic acid (anhydride), styrene, styrene sulphonate or mixtures thereof. Specific examples of suitable polymeric materials are polyvinyl acetate, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol/polyvinyl acetate; carboxy methyl cellulose; dextrine modified vinylacetate polymers: and homo- or copolymeric polycarboxylic acids or salts thereof, such as the polyacrylic acids or polyacrylate~, copolymers of maleic acid (anhydride) and acrylic or methacrylic acid, and copolymers of maleic acid (anhydride) and vinyl-methyl ether.
The ~mectite clay materials usable in the present invention are preferably selected from the group consisting of alkali and alkaline earth metal montmorillonites, saponite~ and hectorites, and particularly those having an ion-exchange capacity of at leaqt about 50 meq/100 g. However, illite, attapulgite and kaollnite ciays can also be used in the instant invention~
The clay minerals used in the in~tant compositions can be deqcribed a~ expandable, three-layer clays, in which a sheet of aluminium/oxygen atoms or magnesium/oxygen atom~ lieq between two layerq of silicon/oxygen atoms, ~ C 7074 (~) i.e. alumino-slicates and magnesium silicates. The term "expandable" a~ used to describe clays ~elates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used the~ein are examples o~ the clay mine~als classified geologically as smectites.
There are two distinct classes of smectite clays that can be broadly differentiated on the basis of the numberq of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in the outer layers. The dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH)4Si8_yAly(A14 xMgx)020, nontronite (OH)4Si8_yA14_xFex)020 a volchonkoite (OH)4Si8_yAly(A14_xCrx)020, where x has a value of rom 0 to about 2,0.
The trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH)4Si8_yAly(Mg6 XLix)02o, saponite (oH)4(si8-yAly)(M96-xAlx) 20' sauconite (OH)4-si8_yAly(Zn6-xAlx) vermiculite (OH)4Si8_yAly(Mg6_xFex)020l wherein y has a value of 0 to about 2.0 and x has a value of 0 to about 6Ø
It is to be eecognized that the range of the water of hydration in the above Eormulas can vary with the processing to which the clay ha~ been subjected.
,Speciic non-limiting examples o~ smectite clay minerals are:
29946C13 C 7 0 7 4 ( R ) Sodium Montmorillonite Volclay sc~
Gelwhite GP
Thixo-Jel 1 Ben-A-Gel ~
Sodlum Hectorite Veegum F
Laponite SP~
Sodium Saponite Barasym NAS 100 ~
Calcium Montmorillonite Soft Clark Gel White L
Lithium Hectorite Barasym LIH 200-Most of the smectite clays useful in the compositions herein are commercially available under various trade-names, for example, Thixo-Jel 1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay ~C
and Volclay 325, from American Colloid Co., Skokie, Illinois; and Veegum F, from R.T.Vanderbilt. It is to be recognized that such srnectite minerals obtained under the foregoing tradename~ can comprise mixtures of the variou3 discrete mineral entities. Such mixtures of the ~mectite minerals are suitable for use herein.
Within the classes of montmorlllonite, hectorite, and saponite clay minerals, certain clay~ are preferred.
For example, Gelwhite GP, Volclay BC and certain smectite clays rnarketed under the name "bentonite'~
3~ ~en~ r~e ~
~ 99~ ~ C 7074 (R) Bentonite, in fact, is a rock type originating from volcanic ash and contains montmorillonite ~one of the smectite clays) as its principal clay component. The Table shows that materials commercially available under the name bentonite can have a wide range of cation exchange capacities. Each of these bentonites can in principle be used in the present invention without problems arising.
10 Rentonite Supplier Exchange capacity _ _ meq/100 g Brock ~ ~Georgia Kaolin Co, USA 63 Soft Clark Georgia Kaolin Co, USA 84 Bentonite L Georgia Kaolin Co, USA68 ~v, 15 Clarolite ~
T-60 ~ Georgia Raolin Co, USA61 Granulare~
Naturale ~
Bianco ~ Seven C. Milan Italy 23 20 Thixo-Jel 4 Georgia Kaolin Co, USA 55 Granular Naturale Normale Seven C. Milan Italy 19 Clar~ol ~
25 FB 5 Ceca Paris France 12 PDL 1740 Georgia Kaolin Co, USA 26 Versuchs Product FFI Sud-Chemie Munich Germany 26 ....
Low colloid content (~ 50%) The alumino silicate clay materials usable in the present invention are normally commercially available and can be naturally occurring or synthetically derived.
Preferred ~ynthetic crystalline alurnino silicate ion-exchange materials useful herein are available under 61 ~ h~S t~C~G~
C 7074 (R) the deslgnations Zeolite A, Zeolite ~, Zeolite X, Zeolite HS~and mixtures thereof.
The level of such clay materials for use as binder component in the granular bleach activator composition may be as low as about 0.5% and can be increased up to about 15% by weight.
Not only will the presence of small amounts of clay enhance the dispersibility, but it is also economically attractive as a partial replacement of the polymeric material without affecting the overall physical properties of the bleach activator granules.
Effectively, the granular bleach activator compositions will comprise:
(a) from 55-90% by weight of the finely divided bleach activator:
20(b) from 3-20% by weight of the inorganic or organic salt;
(c) from 1-10% by weight of the film-forming polymeric material; and (d) frorn 0.5-15% by weight of the smectite or alumino 25~ilicate clay material.
Water may be present in an amount of up to about 4.5%, preferably up to 3~.
As explained hereinbefore, the invention has particular ~pplicability to non-phosphorus detergent compositions, although it ~hould be appreciated that its use in other detergent compositions is no~ excluded.
Accordingly, in one other aspect the invention provides a detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
~ ~hot~$ ~ Vk C 7074 (R) (i) a detergent active material;
(ii) a non~phosphorus-containing detergency builder;
(iii~ a peroxygen bleaching agent; and (iv) a non-pho~phorus gran~lar bleach activator composition a~ hereinbefore defined;
The preferred detergent active compounds are fully described in Ga 1,437,950 referred to above.
The effective amount of the detergent active compound or compounds used in the composition is generally in the range from 5 to 40% by weight, preferably not more than 30~ by weight of the composition.
A second es3ential ingredient of the composition i9 a non-phosphorus-containing detergency builder which may be present in an amount of from 5-80~ by weight of the compo~ition. Preferred non-phosphorus-containing detergency builders are:
i) the alumino silicate cation exchange materials, both crystalline and amorphous, having the general formula:
(Cat2/nO)x-Al2o3 ~sio2)y~z 2 wherein ~at i~ a cation having valency n that is exchangeable with calcium ~e.g. Na~ or K~); x i9 a number from 0.7-1.5; y is a number from 1.3-4; and z i5 such that the bound water content i~ ~rom 10~ to 28% by weight.
Preferred alumino~ilicates are the crystalline material~
of the zeolite type of the following general formula:
Nax(Alo2)x:(sio2)y~z~H2o i2~9 6 C 7074 (R) wherein x and y are integers of at least 6, the ratio of x to y being in the range of l:l to 1:2; and z is such that the bound water content is from 10~ to 28% by weight.
Particularly preferred materials of the zeolite class are the A-type zeolites;
ii) Nitrilotriacetetic acid compounds, particularly sodium nitrilotriacetate (NTA), and iii) Polycarboxylate polymers as described in EP A-0137669; and mixtures of ~ (iii); or (i) + (ii) + iii).
In addition thereto, it is possible to include minor amounts of other non-phosphorus detergency builders, provided that the total amount of the detergency builders does not exceed 80% by weight, 90 as to leave room in the detergent composition for other desirable ingredients.
Groups of other non-phosphorus detergency builders are known in the art and described in a number of patent publications, such as the sodium carboxy methyloxy disuccinates; citric acid; ~ellitic acid; benzene polycarboxylic acids; and the polyacetalcarboxylates as disclosed in US Patent Specification 4,l44,226.
Where a soap i9 u~ed as a detergent active material, it may be present in such a quantity that it will also contribute as an additional builder.
The amount of ,oeroxygen bleaching agent used in the composi~ions of the invention will generally be from 5 to 30~ by weight, preferably from 7~ to 25~ by weight.
C 7074 (R) The amount of non-phosphorus bleach activator granules incorporated in the compositions will depend on the bleach activator content of the granule composition and should be from 0.5~ to 15~ by weight~ more preferably from 1.5~ to 10% by weight, calculated as pure bleach activator.
With regard to the bleach activator as used in preparing the granular bleach activator compositions, it i~
preferred that its particle size should be le~s than 200 micrometre, more preferably 150 micrometre. aleach activators having a major proportion of particle size of between 50 micrometre to 150 micrometre as de~cribed in Ga Patent Specification 2,053,998 are particularly suitable.
The detergent compositions in which the granular non-phosphorus bleach activator compositions are incor-porated can optionally contain any of the conventional ingredients in the amounts in which such ingredients are normally employed in fabric washing detergent compositions.
One such optional ingredient is an alkalimetal silicate, particularly ~odium, neutral, alkaline, ~eta-or orthosilicate. A low level of silicate, ~or example 2-10% by weight, is usually advantageous in decreasing the corrosion of metal parts in fabric washing machine~
and it may give processing benefits. If higher levels of silicate are used up to a practical maximum of 30~, for example from 10~ to 20~ by weight, there can be a more noticeable improvement in detergency, which may permit some decrease in the water-soluble carbonate material content. This effect appears to be particularly beneficial when the wash liquor i9 used in water with appreciable levels of magnesium hardnes~. The amount of silicate can also be used to some extent to control the C 7079 (R) equilibrium pH of the wash liquor, which is generally within the range of 9-11, preferably 10-11, for an aqueous solution of the composition at the recommended concentration. It should be noted tha~ a higher pH
(i.e. over pH 10.5) tends to be more efficient as regards detergency, but it may be less desirable for domestic safety. Sodium silicate is commonly supplied in concentrated aqueous ~olution or in concentrated powder form, but the amounts are calculated on an anhydrouæ basis.
Examples of other optional ingredients include the lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acid3, lather depressants, fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes, such as proteases and amylases, germicides and colourants.
Particularly when the composition does not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the deposition of calcium carbonate on to fabrics.
The detergent compsitions may be produced by any of the techniqueM commonly employed in the manufacture of fabric washing detergent compositions, including particularly slurry-making and spray-drying processes for the manufacture of detergent powders.
The invention will now be Purther illustrated by reference to the following non-limiting Examples.
~2~ 7074 (R) Example I
The following granular non-phosphorus bleach activato~
composi~ion was prepared:
Composition I ~ by weight TAE~ (bleach activator) 84.g Sodi~m sulphate 10.4 Polymer* 1.1 10 Kaolin clay 2.2 Water 1.4 *Gantre ~ AN 119, a copolymer of maleic anhydride and vinyl methyl ether. (Gantrez is a registered Trade Mark).
A solid feed consisting of a mixture of 90~ TAED and 10% sodium sulphate was sprayed with the proper amount of an aqueous mixture consisting of 5% Gantrez AN 119, 10% kaolin and 85~ water in a Schugi Flexomix 160 Apparatus. The product was aerated to dry and obtain a product of the above composition with the following properties:
Comp. IControl Comp. A B
Bulk density g/l 404 500-640 458 Dynamic flow rate ml/s 120 80 114 Compre3sibLlity % 12.9 20 12.4 Granulometry:
30 Mean particle size micrometre 721 600-800 848 1700 mlcrometre nil 1 nil ~ 250 micrometre 8.8 S 9.4 % 125 micrometre 2.9 2 3.8 Storage properties in NTA/zeolite detergent powder containing sodium perborate monohydrate ~tored in wax laminated cartons at 37C/70RH.
C 7074 ( R ) Detergent Powder Com ~ lon% by wei~ht Sodium C12 alkylbenzene sulphonate 9-0 5 Primary C13-C15 alcohol/
7 ethylene oxide 4.0 Zeolite 30.0 Na-nitrilotriacetate (NTA)4.0 Alkaline sodium silicate 5.7 10 Sodium succinate 4.4 Sodium carbonate 5.0 Sodium carboxymethyl cellulose 0.5 Sodium sulphate 15.4 Water 8.0 15 Anti-foam granule 5.0 Sodium perborate monohydrate5.5 TAED granules 3.5 Control Comp. I Comp. A B
TAED decomposition ~:
after 4 weeks 15.613-27 13.5 after 8 weeks 18.520-38 51.3 25 Perborate decomposition ~:
after 4 weeks 16.358-63 8.5 after 8 weeks 34.755-89 36.2 TAED delivery:
Peracid yield, peak value m-mole/1 0.961.20 0.94 Peracid yield, peak time minutes 11.512.5 20.0 1299460 C 7074 (R) Control granule Com~ _ B
% by weight TAED (bleach activator)58-62 85.0 Sodium triphosphate 18-22 Potassium triphosphate 13-15 Water 5-7 1.5 Sodium sulphate - 7.6 Polymer* ~ 5 9 * Copolymer of maleic anhydride and acrylic acid (Sokalan CP 5 ex BASF).
Examples II and III
Similar good results were obtained with the following ~ranular non-phosphorus bleach activator (TAED) compositions:
Compositions _(% by weiqht) II III
TAED 80.5 87.3 Sodium sulphate 4.8 8.4 Polymer 1) 3.7 1.0 Clay 2) 8.5 1.9 Water 2.5 1.4 1) Polymer in II is Sokalan ~ CP 5 ex BASF/ a maleic acid/acrylic acid copolymer; Polymer in III is Gantrez ~ AN 119.
2) Clay in II and III is calcium bentonite.
Claims (5)
1. Granular non-phosphorus-containing bleach activator composition comprising:
(i) from 55-90% by weight of a finely divided bleach activator;
(ii) from 3-20% by weight of an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt;
(iii) from 1-10% by weight of a water-soluble, film-forming polymeric material of average molecular weight of from about 500-l,000,000; and (iv) from 0.5-15% by weight of a smectite or alumino silicate clay material.
(i) from 55-90% by weight of a finely divided bleach activator;
(ii) from 3-20% by weight of an inert, non-alkaline, non-phosphate, water-soluble inorganic or organic salt;
(iii) from 1-10% by weight of a water-soluble, film-forming polymeric material of average molecular weight of from about 500-l,000,000; and (iv) from 0.5-15% by weight of a smectite or alumino silicate clay material.
2. Granular bleach activator composition according to Claim 1, wherein said salt is sodium sulphate.
3. Granular bleach activator composition according to Claim 1, wherein said clay material is bentonite.
4. A detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
(a) from 5-40% by weight of a detergent active material;
(b) from 5-80% by weight of a non-phosphorus-containing detergency builder;
(c) from 5-30% by weight of a peroxygen bleaching agent; and (d) from 0.5-15% by weight of a granul.ar non-phosphorus-containing bleach activator composition according to any of the above Claims 13.
(a) from 5-40% by weight of a detergent active material;
(b) from 5-80% by weight of a non-phosphorus-containing detergency builder;
(c) from 5-30% by weight of a peroxygen bleaching agent; and (d) from 0.5-15% by weight of a granul.ar non-phosphorus-containing bleach activator composition according to any of the above Claims 13.
5. A detergent bleach composition according to Claim 4, wherein said non-phosphorus detergency builder is selected from the group consisting of 1) alumino silicate cation-exchange materials, 2) nitrilotriacetic acid compounds, 3) polycarboxylate polymers, and 4) mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8607388 | 1986-03-25 | ||
| GB868607388A GB8607388D0 (en) | 1986-03-25 | 1986-03-25 | Activator compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299460C true CA1299460C (en) | 1992-04-28 |
Family
ID=10595210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000532482A Expired - Fee Related CA1299460C (en) | 1986-03-25 | 1987-03-19 | Granular non-phosphorus-containing bleach activator compositions and use thereof in granular detergent bleach compositions |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0240057B2 (en) |
| JP (1) | JPH0645800B2 (en) |
| AU (1) | AU587315B2 (en) |
| CA (1) | CA1299460C (en) |
| DE (1) | DE3760055D1 (en) |
| ES (1) | ES2008046T5 (en) |
| GB (1) | GB8607388D0 (en) |
| TR (1) | TR24553A (en) |
| ZA (1) | ZA872199B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8607387D0 (en) * | 1986-03-25 | 1986-04-30 | Unilever Plc | Activator compositions |
| US5002691A (en) * | 1986-11-06 | 1991-03-26 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
| DE3639115A1 (en) * | 1986-11-15 | 1988-05-19 | Henkel Kgaa | STORAGE BLENDER MIXTURE WITH IMPROVED SOLUTION |
| EP0299575B1 (en) * | 1987-07-14 | 1994-01-12 | The Procter & Gamble Company | Detergent compositions |
| GB8810630D0 (en) * | 1988-05-05 | 1988-06-08 | Unilever Plc | Process for preparing bodies containing peroxyacid & compositions comprising said bodies |
| US5269962A (en) * | 1988-10-14 | 1993-12-14 | The Clorox Company | Oxidant composition containing stable bleach activator granules |
| GB8919006D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Granulated bleach activator particles |
| DE3938526A1 (en) * | 1989-11-21 | 1991-05-23 | Basf Ag | USE OF HETEROCYCLIC COMPOUNDS AS BLEACH ACTIVATORS OR OPTICAL BRIGHTENERS IN DETERGENT AND CLEANING AGENTS |
| GB9022999D0 (en) * | 1990-10-23 | 1990-12-05 | Bp Chem Int Ltd | Bleach activators |
| WO1993025651A1 (en) * | 1992-06-18 | 1993-12-23 | Unilever N.V. | Machine dishwashing composition |
| DE4439039A1 (en) | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulated bleach activators and their manufacture |
| GB9422369D0 (en) * | 1994-11-05 | 1995-01-04 | Procter & Gamble | Detergent compositions |
| GB2294707A (en) * | 1994-11-05 | 1996-05-08 | Procter & Gamble | Bleaching composition |
| GB9424009D0 (en) * | 1994-11-29 | 1995-01-18 | Procter And Gamble The Company | Peroxyacid bleach precursor compositions |
| DE19605526A1 (en) | 1996-02-15 | 1997-08-21 | Hoechst Ag | Ammonium nitriles and their use as bleach activators |
| DE19719397A1 (en) * | 1997-05-07 | 1998-11-12 | Clariant Gmbh | Bleach-active metal complexes |
| DE19728021A1 (en) * | 1997-07-01 | 1999-01-07 | Clariant Gmbh | Metal complexes as bleach activators |
| DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
| DE19740668A1 (en) | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Storage-stable bleach activator granulate obtained using acid-modified layered silicate as binder |
| DE19841184A1 (en) | 1998-09-09 | 2000-03-16 | Clariant Gmbh | bleach activator |
| DE19943254A1 (en) | 1999-09-10 | 2001-03-15 | Clariant Gmbh | Bleach-active metal complexes |
| DE10019877A1 (en) | 2000-04-20 | 2001-10-25 | Clariant Gmbh | Detergents and cleaning agents containing bleach-active dendrimer ligands and their metal complexes |
| EP1894993A1 (en) * | 2006-08-28 | 2008-03-05 | Süd-Chemie Ag | Detergent additive based on clay minerals and copolymers containing PVP |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE51848B1 (en) * | 1980-11-06 | 1987-04-15 | Procter & Gamble | Bleach activator compositions,preparation thereof and use in granular detergent compositions |
| AU549000B2 (en) * | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
| EP0075818B2 (en) * | 1981-09-28 | 1990-03-14 | BASF Aktiengesellschaft | Granular bleach activator |
| US4539131B1 (en) * | 1982-06-25 | 1990-09-04 | Lever Brothers Ltd | Solid detergent composition containing sodium perborate monohydrate having specified surface area |
| GB8328017D0 (en) * | 1983-10-19 | 1983-11-23 | Unilever Plc | Detergent powders |
| CA1275019A (en) * | 1985-10-09 | 1990-10-09 | The Procter & Gamble Company | Granular detergent compositions having improved solubility |
-
1986
- 1986-03-25 GB GB868607388A patent/GB8607388D0/en active Pending
-
1987
- 1987-03-12 ES ES87200466T patent/ES2008046T5/en not_active Expired
- 1987-03-12 EP EP87200466A patent/EP0240057B2/en not_active Expired - Lifetime
- 1987-03-12 DE DE8787200466T patent/DE3760055D1/en not_active Expired
- 1987-03-19 CA CA000532482A patent/CA1299460C/en not_active Expired - Fee Related
- 1987-03-20 AU AU70507/87A patent/AU587315B2/en not_active Ceased
- 1987-03-25 JP JP62071315A patent/JPH0645800B2/en not_active Expired - Lifetime
- 1987-03-25 TR TR87/0202A patent/TR24553A/en unknown
- 1987-03-25 ZA ZA872199A patent/ZA872199B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA872199B (en) | 1988-11-30 |
| ES2008046B3 (en) | 1989-07-01 |
| GB8607388D0 (en) | 1986-04-30 |
| EP0240057A1 (en) | 1987-10-07 |
| JPS62240395A (en) | 1987-10-21 |
| JPH0645800B2 (en) | 1994-06-15 |
| ES2008046T5 (en) | 1995-08-01 |
| AU587315B2 (en) | 1989-08-10 |
| DE3760055D1 (en) | 1989-04-06 |
| EP0240057B2 (en) | 1993-09-22 |
| EP0240057B1 (en) | 1989-03-01 |
| TR24553A (en) | 1991-11-21 |
| AU7050787A (en) | 1987-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |