CA1288311C - Granular non-phosphorus detergent bleach compositions - Google Patents
Granular non-phosphorus detergent bleach compositionsInfo
- Publication number
- CA1288311C CA1288311C CA000532483A CA532483A CA1288311C CA 1288311 C CA1288311 C CA 1288311C CA 000532483 A CA000532483 A CA 000532483A CA 532483 A CA532483 A CA 532483A CA 1288311 C CA1288311 C CA 1288311C
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- weight
- water
- bleach activator
- carbonate
- 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
- C11D3/3907—Organic compounds
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/1233—Carbonates, e.g. calcite or dolomite
-
- 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
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
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- Chemical & Material Sciences (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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT
Granular detergent bleach compositions substantially free of phosphorus-containing material comprising as builder 1) a carbonate/calcite mixture, 2) an aluminosilicate cation exchange material, 3) a nitrilotriacetic acid compound or a mixture of 2) and 3); a peroxygen bleaching agent and a granular non-phosphorus bleach activator composition comprising:
(a) 50-90% by weight of a bleach activator;
(b) 5-45% by weight of an inert non-alkaline, non-phosphate water-soluble salt; and (c) 1-15% by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material of average molecular weight of from 500-1,000,000.
The granular non-phosphorus bleach activator composition has the advantage that it does not cause poisoning of calcite.
Granular detergent bleach compositions substantially free of phosphorus-containing material comprising as builder 1) a carbonate/calcite mixture, 2) an aluminosilicate cation exchange material, 3) a nitrilotriacetic acid compound or a mixture of 2) and 3); a peroxygen bleaching agent and a granular non-phosphorus bleach activator composition comprising:
(a) 50-90% by weight of a bleach activator;
(b) 5-45% by weight of an inert non-alkaline, non-phosphate water-soluble salt; and (c) 1-15% by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material of average molecular weight of from 500-1,000,000.
The granular non-phosphorus bleach activator composition has the advantage that it does not cause poisoning of calcite.
Description
~ 3.~ 31~ C 7073 (R) -GRANULAR NON-PHOSPHORUS DETERGENT BLEACH COMPOSITIONS
This invention relates ~o granular non-phosphorus bleach activator containing detergent bleach compositions. Particularly it pertains to granular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursor3 usable in 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 bleachinq agents are known in the art. The peroxygen bleaching agents commonly used are those which release hydrogen peroxide in aqueous solution, such as alkali metal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persalts". The most commonly u~ed persalt in detergent compositions is alkali metal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
The organic bleach activators referred to herein are generally organic N-acyl or 0-acyl compounds, or carbonic or pyrocarbonic esters, which react with hydrogen peroxide (e.g. from the persalts) in solution forming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, i~ effective in bleaching at lower temperatures, e.g. from ambient to 60C.
Such bleach activators are amply described in literature, ~or example in a serie~ o~ articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, page~ 26, 27 and 67, and ~ 3~ c 7073 (R) further in Briti~h Patent Specifications 836,988, 855,735: 907,356; 907,358: 970,950; 1,003,310 and 1,246,339; US Patent Specification4 3,332,882, 3,277,750, 4,128,494 and 4,412,934.
A representative, but by no means comprehensive, list of activators which can be u~ed in the present invention is given below:
(a) ~-diacylated and N,N'-tetraacylated amine~, ~uch 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 hydantoins as, for example, the compound~ 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionyl hydantoin:
(b) N-alkyl-N-suphonyl carbonamides, for example the compounds N-methyl-N-mesyl acetamide, N-methyl-N-meqyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide:
(c) N-acylated cyclic hydrazides, acylated triazoles or urazole4, for example monoacetyl maleic acid hydrazide:
~ d) 0,N,N-trisubstituted hydroxylamines, such as 0-benzoyl-~,N-succinyl hydroxylaminè, 0-acetyl-N,N-~uccinyl hydroxylamine, 0-p-methyoxybenzoyl, N,N-succinyl hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl hydroxylamine and 0,N,N-triacetyl hydroxylamine:
(e) N,N'-diacyl sulphurylamides, for example N,N'-dimethyl-N,N'-diacetyl 4ulphuryl amide and N,N'-diethyl-N,N'-dipropionyl sulphurylamide;
(f) Triacyl cyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate:
~ 9) Carboxylic acid anhydrides, such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride and 4-chlorophtalic anhydride, (h) Sugar esters, ~or example glucose pentaacetate:
(i) 1,3-diacyl-4,5-diacyloxy-imidazolines, ~or example l,3-diformyl-4,5-diacetoxy imidazoline, 1,3-~ C 7073 (R) diacetyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-dipropionyloxy imidazoline;
(j) Tetraacetyl glycoluril and tetraproprionyl glycoluril;
(k) Diacylated 2,5-diXetopiperazines, such a~ 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-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 tetraacetylor tetrapropionyl propylene diurea and their dimethyl derivatives;
(m) Carbonic acid esters, for example the sodium 3alts 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 compo~itions. On the other hand, any proper method of protecting the bleach activator from the environment must allow a relatively quick release or dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period well before the end of the wash cycle 30 as to give time for the activator to react with the persalt forming the peroxyacid. Preferably this should occur a~ early as pos~ible in the wash cycle for maximum bleaching to occur.
The moqt common way of protecting bleach activators i9 by presenting them in the form of granules or agglomerates.
Various compo~itions and form~ of bleach activator ~ C 7073 (R) granules have been proposed in the art, moqt of them u~ing a phoqphate, particularly ~odium tripho~phate, a~
an essential component of the granulating agent because of it~ typical property of imparting good structure combined with quick disper~ion to the granule. A
representative example of ~uch bleach activator granule compositions having good ~torage stability and satisfactory release i~ that which comprise~ a mixture of ~odium triphosphate and pota~sium tripho~phate a~
the granulating agent, currently used in the majority of commercial detergent powder formulations~
For many years, pho~phates, such a~ ~odium triphosphate, have indeed been used as detergency builders.
With the increaqing trend of legislation in a number of countries to ban phosphorus 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 compositions which are free, or es~entially free, of phosphoru~.
Consequently, in formulating such phosphorus-~ree detergent bleach compositions comprising a bleach activator, it has also become nece~sary to look for a rea~onable alternative to bleach activator granule compositions which are free o~ phr,~phorus but which should have the phy~ical properties and performance characteristics comparable to phosphoru~-containing bleach activator granules when used in detergent compositions under non-phosphorus conditions.
A number of alternative non-phosphorus builders have been proposed, especially a mixture o~ an alkali metal carbonate, such as sodium carbonate, with a water-in~oluble calcium carbonate ~eed material, such as ~ 831~ C 7073 (R) calcite, a~ disclosed for example in GB Patent Specifications 1,437,950 (Unilever), 1,481,516 (Vnilever) and 1,481,685 (Unilever), and it iq for use in compositions containing such builderq that the present non-phosphorus bleach activator granule composition i~ particularly de~igned.
Non-phosphorus-containing bleach activator granule composition~ are known in the art and various method3 of preparing such granuleQ and their use in detergent compositions have been proposed.
In the majority of ca~es an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for example nonionic compounds, fatty acids, fatty alcohols, waxeq and polymeric materials with or without the optional u~e of inorganic salts.
German DE-OS 2,657,042 discloses a detergent composition compri~ing tetraacetyl ethylene diamine (TAED) in the form of granules, which consist of said TAED activator and a nonionic surfactant having a melting point of at least 35C as the binding agent.
European EP-B-0051987 (Procter & Gamble) discloses bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40C a~ binding agent.
A major disadvantage of nonionic~ is that they tend to bleed and cause ~tickine~s, giving rise to caking problem~, e~pecially under hot ~ummer temperature conditions. Migration of nonionics in the formulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach ~ystem. Higher melting nonionicq will ~ .2~3~ C 7073 (R) have poor disper~ing ability, resulting in a poor release of the bleach activator, with the deleterious consequence of the granules sedimenting and being 108t in the dead spaces of the washing machine~, known as mechanical lo~s. The ~ame applieq to fatty acids, fatty alcohols and waxe~.
European Patent Specification EP-0070474 and EP-0037026 ~Henkel) disclose methods of using water-soluble cellulo~e ether, starch or Ytarch ether a~ granulation binder for preparing bleach activator granules having a bleach activator content of from 90-99~ by weight. The method~ as described here are only viable if coarse particle size bleach activatorq are used.
European Patent Application EP-0075818 (BASF) di~clo~es water-free activator granules comprising a) 70-9~.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 followed by breaking into smaller particles.
As swelling agents are mentioned high molecular weight carbohydrates, such as starch, powdered cellulose, wood pulp; cro~-linked polyvinyl pyrrolidone (PVP) and also ætarch ether and carboxymethyl cellulose.
All the~e proposal~ have been made without the object of using such bleach activator granules in non-pho~phorus detergent formulations, especially indetergent compositions containing an alkali metal carbonate and calcium carbonate seed material as the builder system.
Accordingly, it i8 an object of the present invention to provide an effective and ~table granular non-phosphorus-containing bleach activator composition ~ 311 C 7073 (R) which can be used in non-phosphoru~ granular detergent bleach compositions containing as builders a mixture of an alkali metal carbonate with a water-insoluble particulate carbonate material, which ic capable of acting a~ a seed crystal for the precipitate resulting from the reaction between the calcium hardne~ ions of the water and the water-~oluble carbonate, e.g. a mixture of sodium carbonate and calcite without poisoning the water-insoluble carbonate material, e~pecially calcite, whereby its seed activity iB
reduced.
This a~d other objects, which will be apparent from the further de~cription of the invention, can be achieved if a finely divided particulate bleach activator i3 granulated to a 3ize of from about 0.2-2.0 mm, using an inert non-alkaline, non-phosphate inorganic or organic salt and a water-soluble, low- to non-carboxylate containing film-forming polymeri`c material having average molecular weiyht o ~rom 500-l,000,000, as granulating agent.
It is known that calcite 19 ~en~itive to poisoning, which will re~ult in a marked detrimental effect on calcite precipitation. In this respect the type of polymeric material used in the invention is crucial.
Thus the granular bleach activator composition of the invention is es~entially free of phosphoru~ m~terial~
, /
.
3 ~r~ C 7073 ~R) and comprises:
(i) a finely divided particulate bleach activator;
(ii) an inert non-alkaline, non-phosphate, water-soluble inorganic or organic salt; and (iii) a water-soluble, low- to non-carboxylate containing film-forming polymeric material of average ~olecular weight of from 500-1,000,000.
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 esters of carbonic or pyrocarbonic acids mentioned under m~ and the reactive phenol esters as described in US Patent Specification 4,412,934 and Ga Patent Specifications 836,988 and 864,798.
The inert non-alkaline, non-phosphate inorganic or organic salts ~hich can be u~ed in the invention are, for example, sodium sulphate, sodium nitrate, sodium chloride, sodium citrate, calcium sulphate and calcium chloride. A preferred salt i5 sodiu~ sulphate.
The low- to non-carboxylate film-forming polymeric material usable in the invention will be any polymer, both homo- and co-polymers, which have a carboxyl group to polymer weight ratio of le~q than 1:5. They may be composed of monomer3 ~uch as vinyl acetate, vinyl pyrrolidone, methyl vinylether, styrene and styrene sulphonate, alkyl acrylates, etc. Examples of suitable polymeric materials include polyvinylpyrrolidone, polyvinyl alcohol, co-polymers of polyvinyl alcohol/
polyvinyl acetate, carbohydrates and carbohydrate ether~ such as carboxymethyl cellulose, and dextrin~
modified vinylacetate polymers. Polymers having average molecular weight of le3s than 500,000, particularly less than 100,000, are pre~erred.
Other polymeric ~aterial~ out~ide those as defined in the present invention are not suitable as they tend to cause serious poisoning of calcite.
Effectively, the granular bleach activator composition ~ill compri~e:
ta) from 50-90%, preferably from 55-85% by weight, of the bleach activator;
(b) fro~ 5-45~, preferably from 10-35% by weiqht, of the inorganic or organic salt; and (c) from 1-15~, pre~erably from 5-10~ by ~eight, of of the low- to non-carboxylate polymeric material.
Water may be present in an amount of up to about 5%, preferably up to 4%.
r As explained hereinbefore, the granular bleach 2~ activator composition has particular applicability to non-phosphorus detergent composition~ containing as builders a mixture of an alkali metal carbonate, such as sodium carbonate, with a ~ater-insoluble carbonate seed material, 3uch as calcium caebonate, e.g. calcite.
Accordingly, the invèntion provides a granular detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
(i) a detergent active material;
(ii) a water-soluble carbonate material which is a detergency builder;
(iii) a water-insolubl.e particula-te carbonate material which is a seed crystal for calcium carbonate;
1.~.
9a (iv) a peroxygen bleaching agent; and (v) a bleach activator, characterized in that the bleach activa-tor is present in the form of non-phosphorus granules of a size from 0.2 to 2.0 mm comprising:
(a) from 50-90% by weight of a finely divided particulate bleach activator (b) from 5-45~ by weight of an inert non-alkaline, non~phosphate, water-soluble inorganic or organic salt;
and (c) from 1-15~ by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material having a carboxyl group to polymer weight ratio of less than 1:5, of average molecular weight from 500-1,000,000.
.
//
PVp~, ~
C 7073 (R) The detergent-active material can be anionic, nonionic, cationic or zwitterionic or a mixture of such agents.
Nonionic ~urfactants suitable for use in the present invention include water-soluble sompounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, polypropoxy glycol or polypropoxy ethylene diamine. Al~o ~uitable are alkyl amine oxides, alkyl polyglucosides and alkyl methylsulphoxides. Preferred nonionic suractants are polyethoxy alcohols formed as the condensation products of 1 to 30 moleY of ethylene oxide with 1 mole of ethylene oxide with 1 mole of branched- or straight-chain, primary or secondary aliphatic alcohol~ having from about 8 to about 22 carbon atoms, more especially, 6 to 15 Moles of ethylene oxide are condensed with 1 mole of straight- or branched-chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms. Certain polyethoxy alcghols are A 20 ~ ommercially ava ~ able under the trade-names7~'Neodol", "Synperonic" and 'Tergitol".
Anionic surfactants suitable for use in ~ormulating the detergent bleach compo~itions o~ the invention include water-soluble alkali metal alkylbenzenesulphonates, alkyl ~ulphates, alkylpolyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their e~ters, alkylglycerylether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkylphenolpolyethoxy ethersulphates, 2-acyloxyalkane-1-sulphonates and beta-alkyloxyalkane sulphonates. Soap~ can also be u~ed as anionic surfactants. Preferred anionic surfactants are alkylbenzene~ulphonates with about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more especially about 11 to about 13 carbon atoms;
alkylsulphaSes with about 8 to about 22 carbon atoms in ~8 tra~ k ~.2~3~
7073 (R) the alkyl chain, more especially from about 12 to about 18 carbon atom~; alkylpolyethoxy ethersulphates with about 10 to about 18 carbon atoms in the alkyl chain and an average of about 1 to about 12 -CH2CH20-groups per molecule; linear paraffin sulphonate~ withabout 8 to about 24 carbon atoms, more especially from about 14 to about 18 carbon atoms and alpha-olefin sulphonate~ with about 10 to about 24 carbon atoms, more especially about 14 to about 16 carbon atoms; and soaps having from 8 to 24, especially 1~ to 18 carbon atoms.
Cationic surface-active agents suitable for use in the invention include the quaternary ammonium compounds, e.g. cetyltrimethylammonium bromide or chloride and distearyldimethylammonium bromide or chloride, and the fatty alkyl amines.
Zwitterionic surfactants that can be used in the present invention include water-soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium cationic compounds in which the aliphatic moieties can be ~traight or branched, and wherein one of the aliphatic sub~tituents contains from about 8 to 18 carbon atoms and one contain~ an anionic water-solubilizing group, especially alkyldimethylammonium propanesulphonates and carboxylates tbetaines) and alkyldimethylammoniohydroxy propane~ulphonates and carboxylates wherein the alkyl group in both types contain~ from about 8 to 18 carbon atoms.
Typical listings of the clasRes and ~pecies of surfactants useful in this invention appear in "Surface Active Agents", Vol. I, by Schwartz & Perry ~Interscience 1949) and "Surface Active Agents", Vol.
II, by Schwartz, Perry & Berch (Interscience 1958~.
C 7073 ~R) The preferred detergent active compounds are fully described in Gs 1,437,950 referred to above.
The effective amount of the detergent active compound or compounds used in the c'omposition is generally in the range from 5 to 40% by weight, preferably not more than 30% by weight of the composition.
A second es~ential ingredient of the composition is a water-soluble carbonate material as a buildex. This is preferably sodium or potassium carbonate or a mixture thereof, for reasons of cost and efficiency. The carbonate salt is preferably fully neutralised but it may be partially neutrali~ed, for example a sesquicarbonate may be used in partial replacement of the normal carbonate salt; the partial salts tend to be less alkaline and therefore less efficient. The amount of water-soluble carbonate material in the detergent composition can be varied widely, but the amount should be at least 5% by weight, such as from 10% to 40~, preferably 10% to 30~ by weight, though an amount of up to 75% could possibly be used, if desired, in special product~. The amount of the water-soluble carbonate material is determined on an anhydrous ba~is, though the ~alts may be hydrated either before or when incorporated in the detergent composition. It should be mentioned that within the preferred range the higher level~ tend to be required under conditions of use at low product concentration3, as i8 commonly the practice in North America, and the conver~e applies under conditions of use at higher product concentrations, as tends to occur in Europe. It should be noted that it may also be desirable to limit the carbonate content to a lowex level within the range mentioned, 80 as to decrease the risk of internal damage following any accidental inge~tion, for example by children.
--~ C 7073 ~) In addition to the water-soluble carbonate material it i5 possible to include minor amounts of other non-phosphorus detergency builders, provided that the total amount of the detergency builders does not exceed 85%
by weight, so as to leave room in the detergent composition for other desirable ingredients.
Where a soap is used as a detergent active material, it may be present in such a quantity that it will also contribute as an additional builder.
The composition further nece~sarily contains a ~ater-insoluble particulate carbonate material. This material must be capable of acting as a seed crystal for the precipitate which results from the reaction between the calcium hardness ionS of the water and the water-soluble carbonate. Thus this water-inQoluble particulate material is a seed cry~tal for calcium carbonate, such as calcium carbonate itself.
The water insoluble particulate carbonate material should be finely divided and should have a surface area of at least 10 m2/g, and preferably at least 15 m2/g.
The particularly preferred material has a surface area from 30-100 m2/g. Insoluble carbonate material with surface areas in exce~s of 100 m2/g may be used if such materials are economically available.
Surface area i9 measured by nitrogen absorption using the standard Bruauer, Emmet & Teller (BET) method. A
Quitable machine for carrying out this method i9 a Carlo Erba Sorpty 1750 instrument operated according to the manufacturer 1 8 instructions.
It is most preferred that the high surface area material be prepared in the absence of poisons, ~o as to retain itq ~eed activity.
C 7073 (R) The insoluble carbonate material will usually have an average particle size of le58 than 10 microns, as measured by sieve analy3is.
When the i~soluble carbonate material i~ calcium carbonate, any crystalline form thereof may be u~ed or a mixture thereof, but calcite i~ preferred as aragonite and vaterite are less readily available commercially, and calcite is a little less soluble than aragonite or vaterite at most usual wash temperatures. When any aragonite or vaterite is used, it i3 generally in admixture with calcite. In the following general de~cription, the term 'calcite' i~ used to mean either calcite itself or any other ~uitable water-insoluble calcium carbonate seed material.
The selected level of calcite in the overall composition depends on the specific surface area a~ described above. The amount of calcite u~ed in the composition~
should be from 5~ to 60%, more preferably from 5% to 30%.
The amount of peroxygen bleaching agent u~ed in the composition~ of the invention will generally be from 5 to 30% by weight, preferably from 7% to 25~ by weight.
¦ The amount of non-pho~phoru~ bleach activator granule~
incorporated in the compositions will depend on the bleach activator content of the granule composition and may be from 0.5~ to 15~ by weight, more preferably from 1.5% to 10~ by weight, calculated a~ pure bleach activator.
With re~ard to the bleach activator as u~ed in preparing the granular bleach activator composition~, it is pre~erred that it~ particle size should be less than 200 micrometre, more preferably up to 150 micrometre.
",~i,,~
~ ~3~3~311 C 7073 (R) . _ Suitable bleach activators are tho~e having a major proportion of particle ~ize of between 50 micrometre and 150 micrometre. Particle size di~tribution a9 described in US Patent Specification 4,283,302 are especially suitable.
The detergent compo~ltion~ in whlch the granular non-phosphoru~ bleach activator compositions are incor-porated can optionally contain any of the conventional ingredients in the amountq in which such ingredients are normally employed in fabric washing detergent com-positions.
One ~uch optional ingredient i8 an alkali metal silicate, particularly sodium, neutral, alkaline, meta-or ortho~ilicate. A low level of ~ilicate, for example from about 2-10~ by weight, i9 usually advantageous in decreasing the corrosion of metal parts in fabric wa~hing machines 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 decrea~e in the water-soluble carbonate material content. ~his effect appears to be particularly beneficial when thé wash liquor i~ used in water with appreciable levels of magnesium hardne~.
The amount of ~ilicate can also be used to some extent to control the equilibrium pH of the wash liquor, which i~ generally within the range of 9-11, preferably 10-11, for an aqueou~ ~olution of the composition at therecommended concentration. It should be noted that a higher pH ~i.e. over pH 10.5) tends to be more efflcient as regards detergency, but it may be less desirable for domestic qafety. Sodium ~ilicate i8 commonly ~upplied in concentrated aqueous solution or in concentrated powder ~orm, but the amountq are calculated on an anhydrous basis.
C 7073 (R) Example~ of other optional ingredients include the lather boo~ter~, such a~ alkanolamide~, particularly the monoethanolamide~ derived from palmkernel fatty acidq and coconut fatty acid~, lather depre~sants, fabric ~oftening agent~, inorganic ~alt~, such a~
sodium ~ulphate, and, u~ually present in very minor amount~, fluorescent agents, perfume~, enzymes, such a~
protea~e~ and amyla~e~, germicide~ and colourants.
Particularly when the composition doe~ not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the depo~ition of calcium carbonate on to fabric~.
The detergent composition~ may be produced by any of the technique~ commonly employed in the ~anufacture of fabric wa~hing detergent compositions, including particularly slurry-making and spray-drying proce~se~
for the manufacture of detergent powders.
The invention will now be further illu~trated by reference to the following non-limiting Exa ples ~ .
~r ? ~ C 7073 (R) Example I
The following granular non-phosphorus bleach activator composition wa~ prepared:
Composition I ~_by weight TAED (bleach activator) ~3.8 Sodium sulphate 9.4 Vinylacetate polymer 3.1 10 Water 3-7 A solid feed conqiqtin~ of a mixture of 90% TAED
(average particle ~ize of 50-150 micrometre) and 10%
sodium ~ulphate was sprayed in a Schugi~ Flexomix 160 apparatu~ with the proper amount of an aqueous solution consi~ting of 15~ polymer and 85~ water. The product wa~
aerated to dry and obtain a product of the above compo~ition with the following properties:
Comp. IControl Comp. A
Bulk density g/l 418 500-640 Dynamic flow rate mlts 120 80 Compre~ibility ~ 8.2 20 Granulometry:
Mean particle size micrometre 619 600~800 % ~1700 micrometre nil ~< 250 micrometre 5.2 5 % < 125 micrometre 1.2 2 30 Control ~ranule Comp. A ~ by weight TAED (bleach activator) 58-62 Sodium triphosphate 18-22 Pota~sium triphosphate 13-15 Water 5~7 ~ ~83~1 C 7073 ~R) ., Example II
The follow.ing granular non-phosphorus bleach activator (TAED) composition was prepared:
Composition of Granule II ~ by _eight TAED 67.8 Sodium sulphate 22.6 Vinyl Dextrin polymer 5.6 10 Water 4.0 A solid feed consisting of a mixture of 75~ TAED
(average particle size of 50-150 micrometre) and 25~
sodium sulphate ~as sprayed in a Schugi~ Flexomix 160 apparatus with the proper amount of an aqueous solution of polymer. The product was dried in a fluid bed to yield a product of the above compo~ition with the following propertieR:
Composition II
sulk density (9/1) 4~0 ~ynamic flow rate (ml/s) 89 Compressibility (~) 9 Gran~lometry:
Mean particle size (micrometre) 748 % ~1700 micrometrenil % < 250 micrometre1.0 ~ ~ 125 micrometre0.1 TAED Delivery Composition II
Peracid yield, peak value m mol/l 1.18 Peracid yield, peak time minuteq 15 Storage Resultq Storaqe properties o~ these granules in a calcite/
. ~.
. . .
~ 3~ ~ C 7073 (R) -carbonate base powder containing odium perborate monohydrate stored in non-laminated carton~ at 37C/70% RH:
Composition II
TAED decomposition %
after 2 week~ 40.4 after 4 weeks 59.6 Perborate decomposition ~
after 2 weeks 10.2 after 4 weeks 19.4 Poisoning of Calcite A test procedure wa~ adopted whereby to a solution containing 20H Ca (as CaC12) was added 1.5 g/l sodium carbonate and 0.5 g/l calcite (Socal U3) in the presence of 10 ppm STP to simulate poi~ons occurring in a practical wash liquor. The effect of TAED granules at 0.15 g/l (100% basis) was noted. The experiment was carried out at 25C u~ing Na2S04 to bring the ionic strength of the medium to 0.1.
H Ca at 15 minute~
(i) No TAED granule 0.31 (ii~ Granule II 0.35 (iii) Control granule A 1.96 It can be ~een that the granule made according to the invention haq no effect on water softening, wherea~ a granule containing a poison cau~e~ a drastic reduction in the water ~oftening achieved.
.~
31~
C 7073 (R) Washin~ Machine Performance Calcite/carbonate + Granule II vs. Commercially =
available Phosphate Powder and Control Granule A
rThe commercially available phoqphate powder u~ed wa~
German Omo base powder.]
Calcite/carbonate powder composition % by wei_ht 10 Sodium C12-alkyl benzene sulphonate 7.7 Nonionic ethoxyla~e 3.4 Sodium stearate 3.4 Sodium carbonate 30.0 Calcite 20.2 15 Sodium silicate 6.0 Enzyme 0-5 Sodium perborate monohydrate5.5 TAED (100~ basis) 2.3 Sodium sulphate/SCMC/water to 100 The two compoqitions were used to wash 2.5 kg of a soiled fabric load in washing machines having a capacity of 18 litres, the load including a number of bleach-sensitive test clo~hs. ~he reflectance of these cloths was mea~ured both before and after the wash and the difference (aR460*) calculated. The wash condition~ were a pre-wash followed by a 35 minute wash cycle heating up from 15C to 60C. The water hardne~s was 40FH ~Ca:Mg molar ratio 4:1). 80 g each composition was used in the pre-wash, 100 g for the main wash. The pH of the wash liquor was mea~ured both be~ore and after the wash. The results were as follows, being averaged over 6 washes:
~ 3~ C 7073 (R) Calcite/Carbonate Phosphate + Granule II + Control A
Initial pH10.6 10.1 Einal pH 10.4 9.4 5 ~R460* 17.8 13.0 Example III
Similar good results were obtained with the following granular non-phoæphoru~ bleach activator ~TAED) compo~ition:
Composition (~ by weight? II
TAED 83.4 Sodium sulphate 8.6 Vinyl acetate homopolymer 8.0 Water 20 The granular bleach activator granules were used in carbonate/calcite base powder compo~itionæ. No poisoning of calcite was ob~erved.
This invention relates ~o granular non-phosphorus bleach activator containing detergent bleach compositions. Particularly it pertains to granular compositions containing activators for peroxygen bleaching agents in the form of organic peroxyacid bleach precursor3 usable in 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 bleachinq agents are known in the art. The peroxygen bleaching agents commonly used are those which release hydrogen peroxide in aqueous solution, such as alkali metal perborates, persilicates, percarbonates, perphosphates and urea peroxide. These peroxygen bleaching agents will hereinafter also be referred to as "persalts". The most commonly u~ed persalt in detergent compositions is alkali metal perborate, particularly sodium perborate, tetrahydrate or monohydrate.
The organic bleach activators referred to herein are generally organic N-acyl or 0-acyl compounds, or carbonic or pyrocarbonic esters, which react with hydrogen peroxide (e.g. from the persalts) in solution forming a peroxy acid or percarbonic acid, a bleaching species which, unlike the persalts, i~ effective in bleaching at lower temperatures, e.g. from ambient to 60C.
Such bleach activators are amply described in literature, ~or example in a serie~ o~ articles by Allan H. Gilbert in Detergent Age, June 1967, pages 18-20, July 1967, pages 30-33, and August 1967, page~ 26, 27 and 67, and ~ 3~ c 7073 (R) further in Briti~h Patent Specifications 836,988, 855,735: 907,356; 907,358: 970,950; 1,003,310 and 1,246,339; US Patent Specification4 3,332,882, 3,277,750, 4,128,494 and 4,412,934.
A representative, but by no means comprehensive, list of activators which can be u~ed in the present invention is given below:
(a) ~-diacylated and N,N'-tetraacylated amine~, ~uch 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 hydantoins as, for example, the compound~ 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionyl hydantoin:
(b) N-alkyl-N-suphonyl carbonamides, for example the compounds N-methyl-N-mesyl acetamide, N-methyl-N-meqyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide:
(c) N-acylated cyclic hydrazides, acylated triazoles or urazole4, for example monoacetyl maleic acid hydrazide:
~ d) 0,N,N-trisubstituted hydroxylamines, such as 0-benzoyl-~,N-succinyl hydroxylaminè, 0-acetyl-N,N-~uccinyl hydroxylamine, 0-p-methyoxybenzoyl, N,N-succinyl hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl hydroxylamine and 0,N,N-triacetyl hydroxylamine:
(e) N,N'-diacyl sulphurylamides, for example N,N'-dimethyl-N,N'-diacetyl 4ulphuryl amide and N,N'-diethyl-N,N'-dipropionyl sulphurylamide;
(f) Triacyl cyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate:
~ 9) Carboxylic acid anhydrides, such as benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride and 4-chlorophtalic anhydride, (h) Sugar esters, ~or example glucose pentaacetate:
(i) 1,3-diacyl-4,5-diacyloxy-imidazolines, ~or example l,3-diformyl-4,5-diacetoxy imidazoline, 1,3-~ C 7073 (R) diacetyl-4,5-diacetoxy imidazoline, 1,3-diacetyl-4,5-dipropionyloxy imidazoline;
(j) Tetraacetyl glycoluril and tetraproprionyl glycoluril;
(k) Diacylated 2,5-diXetopiperazines, such a~ 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-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 tetraacetylor tetrapropionyl propylene diurea and their dimethyl derivatives;
(m) Carbonic acid esters, for example the sodium 3alts 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 compo~itions. On the other hand, any proper method of protecting the bleach activator from the environment must allow a relatively quick release or dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period well before the end of the wash cycle 30 as to give time for the activator to react with the persalt forming the peroxyacid. Preferably this should occur a~ early as pos~ible in the wash cycle for maximum bleaching to occur.
The moqt common way of protecting bleach activators i9 by presenting them in the form of granules or agglomerates.
Various compo~itions and form~ of bleach activator ~ C 7073 (R) granules have been proposed in the art, moqt of them u~ing a phoqphate, particularly ~odium tripho~phate, a~
an essential component of the granulating agent because of it~ typical property of imparting good structure combined with quick disper~ion to the granule. A
representative example of ~uch bleach activator granule compositions having good ~torage stability and satisfactory release i~ that which comprise~ a mixture of ~odium triphosphate and pota~sium tripho~phate a~
the granulating agent, currently used in the majority of commercial detergent powder formulations~
For many years, pho~phates, such a~ ~odium triphosphate, have indeed been used as detergency builders.
With the increaqing trend of legislation in a number of countries to ban phosphorus 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 compositions which are free, or es~entially free, of phosphoru~.
Consequently, in formulating such phosphorus-~ree detergent bleach compositions comprising a bleach activator, it has also become nece~sary to look for a rea~onable alternative to bleach activator granule compositions which are free o~ phr,~phorus but which should have the phy~ical properties and performance characteristics comparable to phosphoru~-containing bleach activator granules when used in detergent compositions under non-phosphorus conditions.
A number of alternative non-phosphorus builders have been proposed, especially a mixture o~ an alkali metal carbonate, such as sodium carbonate, with a water-in~oluble calcium carbonate ~eed material, such as ~ 831~ C 7073 (R) calcite, a~ disclosed for example in GB Patent Specifications 1,437,950 (Unilever), 1,481,516 (Vnilever) and 1,481,685 (Unilever), and it iq for use in compositions containing such builderq that the present non-phosphorus bleach activator granule composition i~ particularly de~igned.
Non-phosphorus-containing bleach activator granule composition~ are known in the art and various method3 of preparing such granuleQ and their use in detergent compositions have been proposed.
In the majority of ca~es an organic compound or a mixture of organic compounds were proposed as the binding or coating agent, such as for example nonionic compounds, fatty acids, fatty alcohols, waxeq and polymeric materials with or without the optional u~e of inorganic salts.
German DE-OS 2,657,042 discloses a detergent composition compri~ing tetraacetyl ethylene diamine (TAED) in the form of granules, which consist of said TAED activator and a nonionic surfactant having a melting point of at least 35C as the binding agent.
European EP-B-0051987 (Procter & Gamble) discloses bleach activator granule compositions comprising a bleach activator and a nonionic surfactant having a melting point of not more than 40C a~ binding agent.
A major disadvantage of nonionic~ is that they tend to bleed and cause ~tickine~s, giving rise to caking problem~, e~pecially under hot ~ummer temperature conditions. Migration of nonionics in the formulation would also tend to aid decomposition of bleach-sensitive ingredients owing to interaction with the oxidising bleach ~ystem. Higher melting nonionicq will ~ .2~3~ C 7073 (R) have poor disper~ing ability, resulting in a poor release of the bleach activator, with the deleterious consequence of the granules sedimenting and being 108t in the dead spaces of the washing machine~, known as mechanical lo~s. The ~ame applieq to fatty acids, fatty alcohols and waxe~.
European Patent Specification EP-0070474 and EP-0037026 ~Henkel) disclose methods of using water-soluble cellulo~e ether, starch or Ytarch ether a~ granulation binder for preparing bleach activator granules having a bleach activator content of from 90-99~ by weight. The method~ as described here are only viable if coarse particle size bleach activatorq are used.
European Patent Application EP-0075818 (BASF) di~clo~es water-free activator granules comprising a) 70-9~.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 followed by breaking into smaller particles.
As swelling agents are mentioned high molecular weight carbohydrates, such as starch, powdered cellulose, wood pulp; cro~-linked polyvinyl pyrrolidone (PVP) and also ætarch ether and carboxymethyl cellulose.
All the~e proposal~ have been made without the object of using such bleach activator granules in non-pho~phorus detergent formulations, especially indetergent compositions containing an alkali metal carbonate and calcium carbonate seed material as the builder system.
Accordingly, it i8 an object of the present invention to provide an effective and ~table granular non-phosphorus-containing bleach activator composition ~ 311 C 7073 (R) which can be used in non-phosphoru~ granular detergent bleach compositions containing as builders a mixture of an alkali metal carbonate with a water-insoluble particulate carbonate material, which ic capable of acting a~ a seed crystal for the precipitate resulting from the reaction between the calcium hardne~ ions of the water and the water-~oluble carbonate, e.g. a mixture of sodium carbonate and calcite without poisoning the water-insoluble carbonate material, e~pecially calcite, whereby its seed activity iB
reduced.
This a~d other objects, which will be apparent from the further de~cription of the invention, can be achieved if a finely divided particulate bleach activator i3 granulated to a 3ize of from about 0.2-2.0 mm, using an inert non-alkaline, non-phosphate inorganic or organic salt and a water-soluble, low- to non-carboxylate containing film-forming polymeri`c material having average molecular weiyht o ~rom 500-l,000,000, as granulating agent.
It is known that calcite 19 ~en~itive to poisoning, which will re~ult in a marked detrimental effect on calcite precipitation. In this respect the type of polymeric material used in the invention is crucial.
Thus the granular bleach activator composition of the invention is es~entially free of phosphoru~ m~terial~
, /
.
3 ~r~ C 7073 ~R) and comprises:
(i) a finely divided particulate bleach activator;
(ii) an inert non-alkaline, non-phosphate, water-soluble inorganic or organic salt; and (iii) a water-soluble, low- to non-carboxylate containing film-forming polymeric material of average ~olecular weight of from 500-1,000,000.
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 esters of carbonic or pyrocarbonic acids mentioned under m~ and the reactive phenol esters as described in US Patent Specification 4,412,934 and Ga Patent Specifications 836,988 and 864,798.
The inert non-alkaline, non-phosphate inorganic or organic salts ~hich can be u~ed in the invention are, for example, sodium sulphate, sodium nitrate, sodium chloride, sodium citrate, calcium sulphate and calcium chloride. A preferred salt i5 sodiu~ sulphate.
The low- to non-carboxylate film-forming polymeric material usable in the invention will be any polymer, both homo- and co-polymers, which have a carboxyl group to polymer weight ratio of le~q than 1:5. They may be composed of monomer3 ~uch as vinyl acetate, vinyl pyrrolidone, methyl vinylether, styrene and styrene sulphonate, alkyl acrylates, etc. Examples of suitable polymeric materials include polyvinylpyrrolidone, polyvinyl alcohol, co-polymers of polyvinyl alcohol/
polyvinyl acetate, carbohydrates and carbohydrate ether~ such as carboxymethyl cellulose, and dextrin~
modified vinylacetate polymers. Polymers having average molecular weight of le3s than 500,000, particularly less than 100,000, are pre~erred.
Other polymeric ~aterial~ out~ide those as defined in the present invention are not suitable as they tend to cause serious poisoning of calcite.
Effectively, the granular bleach activator composition ~ill compri~e:
ta) from 50-90%, preferably from 55-85% by weight, of the bleach activator;
(b) fro~ 5-45~, preferably from 10-35% by weiqht, of the inorganic or organic salt; and (c) from 1-15~, pre~erably from 5-10~ by ~eight, of of the low- to non-carboxylate polymeric material.
Water may be present in an amount of up to about 5%, preferably up to 4%.
r As explained hereinbefore, the granular bleach 2~ activator composition has particular applicability to non-phosphorus detergent composition~ containing as builders a mixture of an alkali metal carbonate, such as sodium carbonate, with a ~ater-insoluble carbonate seed material, 3uch as calcium caebonate, e.g. calcite.
Accordingly, the invèntion provides a granular detergent bleach composition which is substantially free of phosphorus-containing material, comprising:
(i) a detergent active material;
(ii) a water-soluble carbonate material which is a detergency builder;
(iii) a water-insolubl.e particula-te carbonate material which is a seed crystal for calcium carbonate;
1.~.
9a (iv) a peroxygen bleaching agent; and (v) a bleach activator, characterized in that the bleach activa-tor is present in the form of non-phosphorus granules of a size from 0.2 to 2.0 mm comprising:
(a) from 50-90% by weight of a finely divided particulate bleach activator (b) from 5-45~ by weight of an inert non-alkaline, non~phosphate, water-soluble inorganic or organic salt;
and (c) from 1-15~ by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material having a carboxyl group to polymer weight ratio of less than 1:5, of average molecular weight from 500-1,000,000.
.
//
PVp~, ~
C 7073 (R) The detergent-active material can be anionic, nonionic, cationic or zwitterionic or a mixture of such agents.
Nonionic ~urfactants suitable for use in the present invention include water-soluble sompounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, polypropoxy glycol or polypropoxy ethylene diamine. Al~o ~uitable are alkyl amine oxides, alkyl polyglucosides and alkyl methylsulphoxides. Preferred nonionic suractants are polyethoxy alcohols formed as the condensation products of 1 to 30 moleY of ethylene oxide with 1 mole of ethylene oxide with 1 mole of branched- or straight-chain, primary or secondary aliphatic alcohol~ having from about 8 to about 22 carbon atoms, more especially, 6 to 15 Moles of ethylene oxide are condensed with 1 mole of straight- or branched-chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms. Certain polyethoxy alcghols are A 20 ~ ommercially ava ~ able under the trade-names7~'Neodol", "Synperonic" and 'Tergitol".
Anionic surfactants suitable for use in ~ormulating the detergent bleach compo~itions o~ the invention include water-soluble alkali metal alkylbenzenesulphonates, alkyl ~ulphates, alkylpolyethoxyether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their e~ters, alkylglycerylether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkylphenolpolyethoxy ethersulphates, 2-acyloxyalkane-1-sulphonates and beta-alkyloxyalkane sulphonates. Soap~ can also be u~ed as anionic surfactants. Preferred anionic surfactants are alkylbenzene~ulphonates with about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more especially about 11 to about 13 carbon atoms;
alkylsulphaSes with about 8 to about 22 carbon atoms in ~8 tra~ k ~.2~3~
7073 (R) the alkyl chain, more especially from about 12 to about 18 carbon atom~; alkylpolyethoxy ethersulphates with about 10 to about 18 carbon atoms in the alkyl chain and an average of about 1 to about 12 -CH2CH20-groups per molecule; linear paraffin sulphonate~ withabout 8 to about 24 carbon atoms, more especially from about 14 to about 18 carbon atoms and alpha-olefin sulphonate~ with about 10 to about 24 carbon atoms, more especially about 14 to about 16 carbon atoms; and soaps having from 8 to 24, especially 1~ to 18 carbon atoms.
Cationic surface-active agents suitable for use in the invention include the quaternary ammonium compounds, e.g. cetyltrimethylammonium bromide or chloride and distearyldimethylammonium bromide or chloride, and the fatty alkyl amines.
Zwitterionic surfactants that can be used in the present invention include water-soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium cationic compounds in which the aliphatic moieties can be ~traight or branched, and wherein one of the aliphatic sub~tituents contains from about 8 to 18 carbon atoms and one contain~ an anionic water-solubilizing group, especially alkyldimethylammonium propanesulphonates and carboxylates tbetaines) and alkyldimethylammoniohydroxy propane~ulphonates and carboxylates wherein the alkyl group in both types contain~ from about 8 to 18 carbon atoms.
Typical listings of the clasRes and ~pecies of surfactants useful in this invention appear in "Surface Active Agents", Vol. I, by Schwartz & Perry ~Interscience 1949) and "Surface Active Agents", Vol.
II, by Schwartz, Perry & Berch (Interscience 1958~.
C 7073 ~R) The preferred detergent active compounds are fully described in Gs 1,437,950 referred to above.
The effective amount of the detergent active compound or compounds used in the c'omposition is generally in the range from 5 to 40% by weight, preferably not more than 30% by weight of the composition.
A second es~ential ingredient of the composition is a water-soluble carbonate material as a buildex. This is preferably sodium or potassium carbonate or a mixture thereof, for reasons of cost and efficiency. The carbonate salt is preferably fully neutralised but it may be partially neutrali~ed, for example a sesquicarbonate may be used in partial replacement of the normal carbonate salt; the partial salts tend to be less alkaline and therefore less efficient. The amount of water-soluble carbonate material in the detergent composition can be varied widely, but the amount should be at least 5% by weight, such as from 10% to 40~, preferably 10% to 30~ by weight, though an amount of up to 75% could possibly be used, if desired, in special product~. The amount of the water-soluble carbonate material is determined on an anhydrous ba~is, though the ~alts may be hydrated either before or when incorporated in the detergent composition. It should be mentioned that within the preferred range the higher level~ tend to be required under conditions of use at low product concentration3, as i8 commonly the practice in North America, and the conver~e applies under conditions of use at higher product concentrations, as tends to occur in Europe. It should be noted that it may also be desirable to limit the carbonate content to a lowex level within the range mentioned, 80 as to decrease the risk of internal damage following any accidental inge~tion, for example by children.
--~ C 7073 ~) In addition to the water-soluble carbonate material it i5 possible to include minor amounts of other non-phosphorus detergency builders, provided that the total amount of the detergency builders does not exceed 85%
by weight, so as to leave room in the detergent composition for other desirable ingredients.
Where a soap is used as a detergent active material, it may be present in such a quantity that it will also contribute as an additional builder.
The composition further nece~sarily contains a ~ater-insoluble particulate carbonate material. This material must be capable of acting as a seed crystal for the precipitate which results from the reaction between the calcium hardness ionS of the water and the water-soluble carbonate. Thus this water-inQoluble particulate material is a seed cry~tal for calcium carbonate, such as calcium carbonate itself.
The water insoluble particulate carbonate material should be finely divided and should have a surface area of at least 10 m2/g, and preferably at least 15 m2/g.
The particularly preferred material has a surface area from 30-100 m2/g. Insoluble carbonate material with surface areas in exce~s of 100 m2/g may be used if such materials are economically available.
Surface area i9 measured by nitrogen absorption using the standard Bruauer, Emmet & Teller (BET) method. A
Quitable machine for carrying out this method i9 a Carlo Erba Sorpty 1750 instrument operated according to the manufacturer 1 8 instructions.
It is most preferred that the high surface area material be prepared in the absence of poisons, ~o as to retain itq ~eed activity.
C 7073 (R) The insoluble carbonate material will usually have an average particle size of le58 than 10 microns, as measured by sieve analy3is.
When the i~soluble carbonate material i~ calcium carbonate, any crystalline form thereof may be u~ed or a mixture thereof, but calcite i~ preferred as aragonite and vaterite are less readily available commercially, and calcite is a little less soluble than aragonite or vaterite at most usual wash temperatures. When any aragonite or vaterite is used, it i3 generally in admixture with calcite. In the following general de~cription, the term 'calcite' i~ used to mean either calcite itself or any other ~uitable water-insoluble calcium carbonate seed material.
The selected level of calcite in the overall composition depends on the specific surface area a~ described above. The amount of calcite u~ed in the composition~
should be from 5~ to 60%, more preferably from 5% to 30%.
The amount of peroxygen bleaching agent u~ed in the composition~ of the invention will generally be from 5 to 30% by weight, preferably from 7% to 25~ by weight.
¦ The amount of non-pho~phoru~ bleach activator granule~
incorporated in the compositions will depend on the bleach activator content of the granule composition and may be from 0.5~ to 15~ by weight, more preferably from 1.5% to 10~ by weight, calculated a~ pure bleach activator.
With re~ard to the bleach activator as u~ed in preparing the granular bleach activator composition~, it is pre~erred that it~ particle size should be less than 200 micrometre, more preferably up to 150 micrometre.
",~i,,~
~ ~3~3~311 C 7073 (R) . _ Suitable bleach activators are tho~e having a major proportion of particle ~ize of between 50 micrometre and 150 micrometre. Particle size di~tribution a9 described in US Patent Specification 4,283,302 are especially suitable.
The detergent compo~ltion~ in whlch the granular non-phosphoru~ bleach activator compositions are incor-porated can optionally contain any of the conventional ingredients in the amountq in which such ingredients are normally employed in fabric washing detergent com-positions.
One ~uch optional ingredient i8 an alkali metal silicate, particularly sodium, neutral, alkaline, meta-or ortho~ilicate. A low level of ~ilicate, for example from about 2-10~ by weight, i9 usually advantageous in decreasing the corrosion of metal parts in fabric wa~hing machines 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 decrea~e in the water-soluble carbonate material content. ~his effect appears to be particularly beneficial when thé wash liquor i~ used in water with appreciable levels of magnesium hardne~.
The amount of ~ilicate can also be used to some extent to control the equilibrium pH of the wash liquor, which i~ generally within the range of 9-11, preferably 10-11, for an aqueou~ ~olution of the composition at therecommended concentration. It should be noted that a higher pH ~i.e. over pH 10.5) tends to be more efflcient as regards detergency, but it may be less desirable for domestic qafety. Sodium ~ilicate i8 commonly ~upplied in concentrated aqueous solution or in concentrated powder ~orm, but the amountq are calculated on an anhydrous basis.
C 7073 (R) Example~ of other optional ingredients include the lather boo~ter~, such a~ alkanolamide~, particularly the monoethanolamide~ derived from palmkernel fatty acidq and coconut fatty acid~, lather depre~sants, fabric ~oftening agent~, inorganic ~alt~, such a~
sodium ~ulphate, and, u~ually present in very minor amount~, fluorescent agents, perfume~, enzymes, such a~
protea~e~ and amyla~e~, germicide~ and colourants.
Particularly when the composition doe~ not contain an anionic detergent active material, it can be beneficial to include an anti-ashing material to reduce the depo~ition of calcium carbonate on to fabric~.
The detergent composition~ may be produced by any of the technique~ commonly employed in the ~anufacture of fabric wa~hing detergent compositions, including particularly slurry-making and spray-drying proce~se~
for the manufacture of detergent powders.
The invention will now be further illu~trated by reference to the following non-limiting Exa ples ~ .
~r ? ~ C 7073 (R) Example I
The following granular non-phosphorus bleach activator composition wa~ prepared:
Composition I ~_by weight TAED (bleach activator) ~3.8 Sodium sulphate 9.4 Vinylacetate polymer 3.1 10 Water 3-7 A solid feed conqiqtin~ of a mixture of 90% TAED
(average particle ~ize of 50-150 micrometre) and 10%
sodium ~ulphate was sprayed in a Schugi~ Flexomix 160 apparatu~ with the proper amount of an aqueous solution consi~ting of 15~ polymer and 85~ water. The product wa~
aerated to dry and obtain a product of the above compo~ition with the following properties:
Comp. IControl Comp. A
Bulk density g/l 418 500-640 Dynamic flow rate mlts 120 80 Compre~ibility ~ 8.2 20 Granulometry:
Mean particle size micrometre 619 600~800 % ~1700 micrometre nil ~< 250 micrometre 5.2 5 % < 125 micrometre 1.2 2 30 Control ~ranule Comp. A ~ by weight TAED (bleach activator) 58-62 Sodium triphosphate 18-22 Pota~sium triphosphate 13-15 Water 5~7 ~ ~83~1 C 7073 ~R) ., Example II
The follow.ing granular non-phosphorus bleach activator (TAED) composition was prepared:
Composition of Granule II ~ by _eight TAED 67.8 Sodium sulphate 22.6 Vinyl Dextrin polymer 5.6 10 Water 4.0 A solid feed consisting of a mixture of 75~ TAED
(average particle size of 50-150 micrometre) and 25~
sodium sulphate ~as sprayed in a Schugi~ Flexomix 160 apparatus with the proper amount of an aqueous solution of polymer. The product was dried in a fluid bed to yield a product of the above compo~ition with the following propertieR:
Composition II
sulk density (9/1) 4~0 ~ynamic flow rate (ml/s) 89 Compressibility (~) 9 Gran~lometry:
Mean particle size (micrometre) 748 % ~1700 micrometrenil % < 250 micrometre1.0 ~ ~ 125 micrometre0.1 TAED Delivery Composition II
Peracid yield, peak value m mol/l 1.18 Peracid yield, peak time minuteq 15 Storage Resultq Storaqe properties o~ these granules in a calcite/
. ~.
. . .
~ 3~ ~ C 7073 (R) -carbonate base powder containing odium perborate monohydrate stored in non-laminated carton~ at 37C/70% RH:
Composition II
TAED decomposition %
after 2 week~ 40.4 after 4 weeks 59.6 Perborate decomposition ~
after 2 weeks 10.2 after 4 weeks 19.4 Poisoning of Calcite A test procedure wa~ adopted whereby to a solution containing 20H Ca (as CaC12) was added 1.5 g/l sodium carbonate and 0.5 g/l calcite (Socal U3) in the presence of 10 ppm STP to simulate poi~ons occurring in a practical wash liquor. The effect of TAED granules at 0.15 g/l (100% basis) was noted. The experiment was carried out at 25C u~ing Na2S04 to bring the ionic strength of the medium to 0.1.
H Ca at 15 minute~
(i) No TAED granule 0.31 (ii~ Granule II 0.35 (iii) Control granule A 1.96 It can be ~een that the granule made according to the invention haq no effect on water softening, wherea~ a granule containing a poison cau~e~ a drastic reduction in the water ~oftening achieved.
.~
31~
C 7073 (R) Washin~ Machine Performance Calcite/carbonate + Granule II vs. Commercially =
available Phosphate Powder and Control Granule A
rThe commercially available phoqphate powder u~ed wa~
German Omo base powder.]
Calcite/carbonate powder composition % by wei_ht 10 Sodium C12-alkyl benzene sulphonate 7.7 Nonionic ethoxyla~e 3.4 Sodium stearate 3.4 Sodium carbonate 30.0 Calcite 20.2 15 Sodium silicate 6.0 Enzyme 0-5 Sodium perborate monohydrate5.5 TAED (100~ basis) 2.3 Sodium sulphate/SCMC/water to 100 The two compoqitions were used to wash 2.5 kg of a soiled fabric load in washing machines having a capacity of 18 litres, the load including a number of bleach-sensitive test clo~hs. ~he reflectance of these cloths was mea~ured both before and after the wash and the difference (aR460*) calculated. The wash condition~ were a pre-wash followed by a 35 minute wash cycle heating up from 15C to 60C. The water hardne~s was 40FH ~Ca:Mg molar ratio 4:1). 80 g each composition was used in the pre-wash, 100 g for the main wash. The pH of the wash liquor was mea~ured both be~ore and after the wash. The results were as follows, being averaged over 6 washes:
~ 3~ C 7073 (R) Calcite/Carbonate Phosphate + Granule II + Control A
Initial pH10.6 10.1 Einal pH 10.4 9.4 5 ~R460* 17.8 13.0 Example III
Similar good results were obtained with the following granular non-phoæphoru~ bleach activator ~TAED) compo~ition:
Composition (~ by weight? II
TAED 83.4 Sodium sulphate 8.6 Vinyl acetate homopolymer 8.0 Water 20 The granular bleach activator granules were used in carbonate/calcite base powder compo~itionæ. No poisoning of calcite was ob~erved.
Claims (4)
1. Granular detergent bleach composition substantially free of phosphorus-containing material comprising a detergent-active material, a water-soluble carbonate material which is a detergency builder, a water-insoluble particulate carbonate material which is a seed crystal for calcium-carbonate, a peroxygen bleaching agent and a bleach activator, characterised in that the bleach activator is present in the form of non-phosphorus granules of a size from o.2 - 2.0 mm comprising:
(a) from 50-90% by weight of finely divided particulate bleach activator;
(b) from 5-45% by weight of an inert non-alkaline, non-phosphate, water-soluble inorganic or organic salt; and (c) from 1-15% by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material, having a carboxylgroup to polymer weight ratio of less than 1:5, of average molecular weight from 500-1,000,000.
(a) from 50-90% by weight of finely divided particulate bleach activator;
(b) from 5-45% by weight of an inert non-alkaline, non-phosphate, water-soluble inorganic or organic salt; and (c) from 1-15% by weight of a water-soluble, low- to non-carboxylate containing film-forming polymeric material, having a carboxylgroup to polymer weight ratio of less than 1:5, of average molecular weight from 500-1,000,000.
2. Granular detergent bleach composition according to claim 1, characterised in that said water-soluble salt is sodium sulphate.
3. Granular detergent bleach composition according to claim 1 or 2, characterised in that said water-insoluble carbonate material is calcite.
4. Granular detergent bleach composition according to claim 3, characterised in that it comprises 5-40% by weight of detergent-active material, 5-75% by weight of water-soluble carbonate material, 5-60% by weight of calcite, 5-30% by weight of peroxygen bleaching agent, and from 0.5-15% by weight of bleach activator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8607387 | 1986-03-25 | ||
| GB868607387A GB8607387D0 (en) | 1986-03-25 | 1986-03-25 | Activator compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1288311C true CA1288311C (en) | 1991-09-03 |
Family
ID=10595209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000532483A Expired - Fee Related CA1288311C (en) | 1986-03-25 | 1987-03-19 | Granular non-phosphorus detergent bleach compositions |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0241962B1 (en) |
| JP (1) | JPH0645799B2 (en) |
| AU (1) | AU586326B2 (en) |
| CA (1) | CA1288311C (en) |
| DE (1) | DE3762753D1 (en) |
| ES (1) | ES2016615B3 (en) |
| GB (1) | GB8607387D0 (en) |
| TR (1) | TR24351A (en) |
| ZA (1) | ZA872198B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002691A (en) * | 1986-11-06 | 1991-03-26 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
| US5112514A (en) * | 1986-11-06 | 1992-05-12 | The Clorox Company | Oxidant detergent containing stable bleach activator granules |
| 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 |
| GB9016504D0 (en) * | 1990-07-27 | 1990-09-12 | Warwick Int Ltd | Granular bleach activator compositions |
| DE19605526A1 (en) | 1996-02-15 | 1997-08-21 | Hoechst Ag | Ammonium nitriles and their use as bleach activators |
| WO1998040457A1 (en) * | 1997-03-11 | 1998-09-17 | The Procter & Gamble Company | Builder mixture containing crystalline calcium carbonate builder for use in detergent compositions |
| 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 |
| 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 |
| CA2681676C (en) | 2007-05-04 | 2015-12-29 | Ecolab Inc. | Cleaning compositions containing water soluble magnesium compound and methods of using them |
| ATE482264T1 (en) * | 2008-08-14 | 2010-10-15 | Unilever Nv | BUILDING COMPOSITION |
| CA3016175C (en) | 2016-03-02 | 2024-05-28 | Harris Research, Inc. | Stain and odor treatment |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI763593A (en) * | 1975-12-18 | 1977-06-19 | Unilever Nv | |
| DE3011998C2 (en) * | 1980-03-28 | 1982-06-16 | Henkel KGaA, 4000 Düsseldorf | Process for the production of a storage-stable, easily soluble granulate with a content of bleach activators |
| ES8400768A1 (en) * | 1980-11-06 | 1983-11-01 | Procter & Gamble | Bleach activator compositions, preparation thereof and use in granular detergent compositions. |
| FI822428L (en) * | 1981-07-15 | 1983-01-16 | Unilever Nv | RENGOERINGSBLANDNING |
| DE3128336A1 (en) * | 1981-07-17 | 1983-01-27 | Henkel KGaA, 4000 Düsseldorf | "METHOD FOR PRODUCING COATED NUCLEAR BLEACHING ACTIVATORS" |
| DE3268039D1 (en) * | 1981-09-28 | 1986-01-30 | Basf Ag | Granular bleach activator |
| DE3138551A1 (en) * | 1981-09-28 | 1983-08-11 | Basf Ag, 6700 Ludwigshafen | 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 |
| JPS59135299A (en) * | 1982-10-08 | 1984-08-03 | ザ，プロクタ−，エンド，ギヤンブル，カンパニ− | Body containing bleaching agent activator |
| GB8311002D0 (en) * | 1983-04-22 | 1983-05-25 | Unilever Plc | Detergent compositions |
| DE3472571D1 (en) * | 1983-08-27 | 1988-08-11 | Procter & Gamble | Detergent compositions |
| GB8607388D0 (en) * | 1986-03-25 | 1986-04-30 | Unilever Plc | Activator compositions |
-
1986
- 1986-03-25 GB GB868607387A patent/GB8607387D0/en active Pending
-
1987
- 1987-03-12 EP EP87200469A patent/EP0241962B1/en not_active Expired - Lifetime
- 1987-03-12 ES ES87200469T patent/ES2016615B3/en not_active Expired - Lifetime
- 1987-03-12 DE DE8787200469T patent/DE3762753D1/en not_active Expired - Fee Related
- 1987-03-19 CA CA000532483A patent/CA1288311C/en not_active Expired - Fee Related
- 1987-03-20 AU AU70506/87A patent/AU586326B2/en not_active Ceased
- 1987-03-25 JP JP62071314A patent/JPH0645799B2/en not_active Expired - Lifetime
- 1987-03-25 TR TR87/0201A patent/TR24351A/en unknown
- 1987-03-25 ZA ZA872198A patent/ZA872198B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TR24351A (en) | 1991-09-16 |
| JPS62240394A (en) | 1987-10-21 |
| DE3762753D1 (en) | 1990-06-21 |
| GB8607387D0 (en) | 1986-04-30 |
| EP0241962A2 (en) | 1987-10-21 |
| EP0241962B1 (en) | 1990-05-16 |
| ZA872198B (en) | 1988-11-30 |
| EP0241962A3 (en) | 1988-06-22 |
| JPH0645799B2 (en) | 1994-06-15 |
| AU7050687A (en) | 1987-10-01 |
| ES2016615B3 (en) | 1990-11-16 |
| AU586326B2 (en) | 1989-07-06 |
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