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
  • C11D3/3942—Inorganic per-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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0078—Multilayered tablets
• • 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
  • C11D3/39—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
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the present invention relates to detergent tablets which contain bleach and bleach activator together with detergent ingredients such as surfactant and builder.
• Detergent compositions often contain bleach and bleach activator.
• EP-A-481 ,792 it was proposed to provide tablets containing bleach and bleach-activator in which reaction occurred within the tablet, when the tablet first comes into contact with wash liquor, due to the tablet being porous.
• the tablet consisted only of bleach and bleach activator but there were also examples of dual layer tablets having a bleach-activator composition in one layer and surfactant and builder in another layer.
• the only detailed description of tableting conditions involved the application of relatively high tableting pressures and it was shown that when the pressure was not sufficiently high the alleged advantages were not obtained. Our attempts at obtaining beneficial results using a dual layer system under the tableting conditions indicated in EP-A-481 ,792 failed.
• a detergent tablet which is a compressed body of particulate material comprising bleach, bleach-activator, surfactant and builder and which has a first layer formed of a first particulate material and a second layer formed of a second particulate material and wherein the first particulate material comprises bleach and bleach-activator and is substantially free of surfactant and film forming binder and the second particulate material comprises surfactant and builder and is substantially free of bleach, and the tablet has a tensile strength of between 8 and 22kPa.
• the invention is of particular value when the second particulate material provides the majority of the mass of the tablet.
• the amount of second particulate material is usually at least 1.5 parts, and preferably at least 2 or 3 parts, per part per weight of the first particulate material and is often up to 4 or even 8 parts per part per weight of first particulate material.
• the first layer may be coextensive with the second layer or may extend over only a part of the second layer, for instance as a dimple formed in the second layer.
• the first layer is usually on an exposed surface of the second layer.
• the bleach is usually a persalt. It may be perborate but is preferably percarbonate.
• the bleach-activator can be any of the activators which are conventionally used, for instance with the chosen persalt, but is preferably TAED. Preferably substantially all the bleach and substantially all the activator are in the first layer.
• the first layer is preferably alkaline and so may include sodium carbonate, for instance spray dried sodium carbonate or other source of alkalinity.
• the first layer is preferably porous and so it should be substantially free of materials which would tend to reduce porosity significantly, such as surfactant and film forming binders.
• substantially free we mean that the amounts of such materials, if present, are sufficiently low that they do not deleteriously reduce porosity. For instance the amount of each is normally below 10%, and usually below 5%, of the first layer.
• the second layer comprises most or all of the surfactant and builder and may also include other optional detergent components.
• DFS diametrical fracture stress
• the tablets of the invention are of a size which is convenient for dosing in a washing machine.
• the preferred size is 10 to 150g and the size can be selected in accordance with the intended wash load and the design of the washing machine which is to be used.
• Detergent tablets of the present invention can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry.
• the principal ingredients in particular gelling surfactants, are used in particulate form.
• Any liquid ingredients, for example surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
• the ingredients such as builder and surfactant can be spray-dried in a conventional manner and then compacted at a suitable pressure.
• the tablets according to the invention are compressed using a force of less than 100000N, more preferably of less than 50000N, even more preferably of less than 5000N and most preferably of less than 3000 N.
• the most preferred embodiment is a tablet compressed using a force of less than 2500N.
• the particulate material used for making the tablet of this invention can be made by any particulation or granulation process.
• An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
• Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige(R) CB and/or Lodige(R) KM mixers).
• Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
• Individual particles can also be any other particle, granule, sphere or grain.
• the components of the particulate material may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s).
• Non-gelling binder can be sprayed on to the mix of some, or all of, the components of the particulate material.
• Other liquid ingredients may also be sprayed on to the mix of components either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed.
• a finely divided flow aid dustting agent such as zeolites, carbonates, silicas
• the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting. Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy(R), Korch(R), Manesty(R), or Bonals(R)).
• the tablets prepared according to this invention preferably have a diameter of between 20mm and 60mm, preferably of at least 35 and up to 55 mm, and a weight between 25 and 100 g.
• the ratio of height to diameter (or width) of the tablets is preferably greater than 1 :3, more preferably greater than 1 :2.
• the compaction pressure used for preparing these tablets need not exceed 100000 kN/m2, preferably not exceed 30000 kN/m2, more preferably not exceed 5000 kN/m2, even more preferably not exceed 3000kN/m2 and most preferably not exceed 1000kN/m2.
• the tablet has a density of at least 0.9 g/cc, more preferably of at least 1.0 g/cc, and preferably of less than 2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably of less than 1.25 g/cc and most preferably of less than 1.1 g/cc.
• Multi-layer tablets can be made by known techniques. Coating
• Solidity of the tablet according to the invention may be further improved by making a coated tablet, the coating covering a non-coated tablet according to the invention, thereby further improving the mechanical characteristics of the tablet while maintaining or further improving dissolution.
• the tablets may then be coated so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
• the coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition.
• the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock.
• the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This contributes to avoiding the problem of visible residue in the window of a front-loading washing machine during the wash cycle, and also avoids deposition of undissolved particles or lumps of coating material on the laundry load.
• Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
• Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.
• the coating material has a melting point preferably of from 40yC to 200yC.
• the coating can be applied in a number of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.
• the coating material is applied at a temperature above its melting point, and solidifies on the tablet.
• the coating is applied as a solution, the solvent being dried to leave a coherent coating.
• the substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating. When tablets are dipped into the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material.
• substantially insoluble materials having a melting point below 40yC are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 200yC are not practicable to use.
• the materials melt in the range from 60yC to 160yC, more preferably from 70yC to 120yC.
• melting point is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.
• a coating of any desired thickness can be applied according to the present invention.
• the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight.
• the tablet coatings are preferably very hard and provide extra strength to the tablet.
• the fracture of the coating in the wash is improved by adding a disintegrant in the coating.
• This disintegrant will swell once in contact with water and break the coating in small pieces. This will improve the dissolution of the coating in the wash solution.
• the disintegrant is suspended in the coating melt at a level of up to 30%, preferably between 5% and 20%, most preferably between 5 and 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
• Suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures thereof.
• the used compacting force may be adjusted to not affect the tensile strength, and the disintegration time in the washing machine. This process may be used to prepare homogenous or layered tablets of any size or shape.
• the tensile strength corresponds to the diametrical fracture stress (DFS) which is a way to express the strength of a tablet, and is determined by the following equation :
• F 2 F y Dt
• F the maximum force (Newton) to cause tensile failure (fracture) measured by a VK 200 tablet hardness tester supplied by Van Kell industries, Inc.
• D is the diameter of the tablet, and t the thickness of the tablet.
• a tablet having a diametral fracture stress of less than 20 kPa is considered to be fragile and is likely to result in some broken tablets being delivered to the consumer.
• a diametral fracture stress of at least 25 kPa is preferred.
• the tablets further comprises an effervescent.
• Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C6H8O7 + 3NaHCO3 Na3C 6 H 5 O 7 + 3CO2 + 3H 2 O
• An effervescent may be added to the tablet mix in addition to the detergent ingredients.
• the addition of this effervescent to the detergent tablet improves the disintegration time of the tablet.
• the amount will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.
• the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles.
• the tablet Due to the gas created by the effervescency in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescency. When the D.F.S. of the tablet with effervescency is kept the same as a tablet without, the disintegration of the tablet with effervescency will be faster.
• Further dissolution aid could be provided by using compounds such as sodium acetate or urea. A list of suitable dissolution aid may also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1 , Second edition, Edited by H.A. Lieberman et all, ISBN 0-8247-8044-2.
• Non gelling binders can be integrated to the particles forming the tablet in order to further facilitate dissolution.
• suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers.
• binders classification Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein.
• binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
• cationic polymers i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
• Non-gelling binder materials are preferably sprayed on and hence have an appropriate melting point temperature below 90yC, preferably below 70yC and even more preferably below 50°C so as not to damage or degrade the other active ingredients in the matrix.
• non-aqueous liquid binders i.e. not in aqueous solution
• they may also be solid binders incorporated into the matrix by dry addition but which have binding properties within the tablet.
• Non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet.
• gelling binders such as nonionic surfactants are avoided in their liquid or molten form.
• Nonionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids.
• Clays are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids.
• the clay minerals used to provide the softening properties of the instant compositions can be described as expandable, three-layer clays, i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100g. of clay.
• expandable as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
• the three-layer expandable clays used herein are those materials classified geologically as smectites.
• smectite-type clays There are two distinct classes of smectite-type clays; in the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
• the general formulas of these smectites are Al2(Si2 ⁇ 5)2(OH)2 and Mg3(Si2 ⁇ 5) (OH)2 for the aluminum and magnesium oxide type clay, respectively. It is to be recognised that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected.
• the three-layer, expandable alumino-silicates useful herein are further characterised by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.
• the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ion, and the like. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed.
• a sodium clay is one in which the absorbed cation is predominantly sodium.
• Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
• a typical exchange reaction involving a smectite-type clay is expressed by the following equation: smectite clay (Na) + NH4OH y smectite clay (NH4) + NaOH.
• cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq./100 g.).
• base exchange capacity cation exchange capacity
• the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971 ).
• the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure, and the like.
• the ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain clays of the montmorillonite variety.
• Illite clays have an ion exchange capacity somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an average illite clay.
• Illite and kaolinite clays are preferably not used as the clay in the instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions.
• smectites such as nontonite, having an ion exchange capacity of around 70 meq/100 g.
• montmorillonite which has an ion exchange capacity greater than 70 meq/100 g.
• clay minerals useful herein can be characterised as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g.
• the smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
• the clays herein are available under various tradenames, for example, Thixogel #1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay #325, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH450, from
• Vanderbilt It is to be recognised that such smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
• smectite-type clays having a cation exchange capacity of at least about 50 meq/100 g. are useful herein, certain clays are preferred.
• Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
• Volclay BC which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe2 ⁇ 3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred from the standpoint of product performance.
• Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites exhibit a true 14A x-ray diffraction pattern. This characteristic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the granular detergent compositions disclosed herein.
• the clay is preferably mainly in the form of granules, with at least 50% (and preferably at least 75% or at least 90%) being in the form of granules having a size of at least 100ym up to 1800ym, preferably up to 1180ym, preferably 150-850ym.
• the amount of clay in the granules is at least 50%, usually at least 70% or 90%, of the weight of the granules.
• Non-limiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, anionics such as sulphonates, sulphates and ether sulphates. These include the conventional C11-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS”), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOSO3_M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO3_M+) CH 2 CH 3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates ("AExS"; especially EO 1-7 e
• the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
• the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 92/06154.
• sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
• the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
• C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used.
• Mixtures of anionic and nonionic surfactants are especially useful.
• Other conventional useful anionic, amphoteric, nonionic or cationic surfactants are listed in standard texts.
• the tablet comprises at least 5% by weight of surfactant, more preferably at least 15% by weight, even more preferably at least 25% by weight, and most preferably between 35% and 55% by weight of surfactant.
• the amount of anionic is preferably at least 1.5 times, generally at least 2 or 3 times, the total amount of other surfactants.
• Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
• the level of builder can vary widely depending upon the end use of the composition.
• Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
• non-phosphate builders are required in some locales.
• compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
• silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued
• NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and
• SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix ⁇ 2X+1.yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to
• layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
• NaSKS-11 as the alpha, beta and gamma forms.
• delta-Na2Si ⁇ 5 NaSKS-6 form
• Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
• carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
• Aluminosilicate builders are useful in the present invention.
• Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
• Aluminosilicate builders include those having the empirical formula: Mz(zAIO 2 )y].xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
• aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
• This material is known as Zeolite A.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
• polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
• Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
• polycarboxylate builders include a variety of categories of useful materials.
• One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al, on May 5, 1987.
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
• ether hydroxypolycarboxylat.es copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
• various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
• polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
• succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
• a particularly preferred compound of this type is dodecenylsuccinic acid.
• succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
• Fatty acids e.g., C12-C18 monocarboxylic acids
• the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
• Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
• the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
• Phosphonate builders such as ethane-1-hydroxy-1 ,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used.
• the detergent compositions herein may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
• bleaching agents will typically be at levels of from about 1 % to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
• the amount of bleach activators will typically be from about 0.1 % to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
• the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
• Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
• bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1 , 1983.
• Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.
• Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
• a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1 ,250 micrometers.
• the percarbonate can be coated with silicate, borate or water-soluble surfactants.
• Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
• Mixtures of bleaching agents can also be used.
• Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
• bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
• NOBS nonanoyloxybenzene sulfonate
• TAED tetraacetyl ethylene diamine
• Rl N(R5)C(O)R 2 2C(O)L or R 1 C(0)N(R5)R2c(O)L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
• a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
• a preferred leaving group is phenyl sulfonate.
• bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate,
• bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
• a highly preferred activator of the benzoxazin-type is:
• Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: O y
• R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
• Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium per
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
• the bleaching compounds can be catalyzed by means of a manganese compound.
• a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in US-A-5,246,621 , US-A-5,244,594; US-A-5,194,416; US-A-5,114,606; and EP-A-549,271 , EP-A-549,272, EP-A-544,440, and EP-A-544,490; Preferred examples of these catalysts include MnlV2(u-O)3(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2(PF6)2, Mnlll2(u-O)1 (u-OAc)2(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2-(CIO4)2, MnlV4(u-O)6(1 ,4,7-triazacyclononane)4(CIO
• MnlllMnlV4(u-O)1 (u-OAc)2-(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2(CIO4)3, MnlV(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
• Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
• compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
• Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
• the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
• Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
• Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001 % to about 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
• AU Anson units
• proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1 ,243,784 of Novo.
• protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
• proteases include Protease A (see EP-A-130,756, published January 9, 1985) and Protease B (see European Patent Application 87303761.8, filed April 28, 1987, and EP-A-130,756, Bott et al, published January 9, 1985).
• Amylases include, for example, -amylases described in GB-A-1 ,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
• the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
• Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
• suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
• Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
• lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
• the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
• Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
• Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
• Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A S.
• Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
• clay flocculating polymers are fairly long chained polymers and co-polymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imine. Gums, like guar gum, are suitable as well.
• polymers of ethylene oxide, acrylamide or acrylic acid are preferred. These polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights are in the range of from 100 000 to 10 million. Preferred are such polymers having a weight average molecular weight of from 150000 to 5 million.
• the most preferred polymer is poly (ethylene oxide).
• Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
• the amount of flocculant is preferably 0.5-10% by weight of the tablet, most preferably about 2 to 6%.
• the flocculant is preferably mainly in the form of granules, with at least 50% by weight (and preferably at least 75% and most preferably at least 90%) being in the form of granules having a size of at least 100ym up to 1800ym, preferably up to 1180ym and most preferably 150-850ym
• the amount of flocculant in the granules is at least 50%, generally at least 70% or 90%, of the weight of the granules.
• compositions which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
• a first particulate material was formed from, in parts by weight,
• a second particulate material was formed from, in parts by weight,
• Zeolite 4A (anhydrous basis) 30.38
• the hardness i.e. tensile strength
• the stain removal index was recorded.
• Example 1 was repeated using the same materials and the same procedures except that the TAED was replaced by (6-nonanamidocaproyl) oxybenezene sulphonate.

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