AU714999B2 - Process for forming tableted high-caustic detergent - Google Patents

Process for forming tableted high-caustic detergent Download PDF

Info

Publication number
AU714999B2
AU714999B2 AU49340/96A AU4934096A AU714999B2 AU 714999 B2 AU714999 B2 AU 714999B2 AU 49340/96 A AU49340/96 A AU 49340/96A AU 4934096 A AU4934096 A AU 4934096A AU 714999 B2 AU714999 B2 AU 714999B2
Authority
AU
Australia
Prior art keywords
mixture
water
detergent
caustic
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU49340/96A
Other versions
AU4934096A (en
Inventor
Patricia Anderson
Kenneth James Roach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Diversey Inc
Original Assignee
Unilever PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23616685&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=AU714999(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of AU4934096A publication Critical patent/AU4934096A/en
Application granted granted Critical
Publication of AU714999B2 publication Critical patent/AU714999B2/en
Assigned to JOHNSONDIVERSEY, INC. reassignment JOHNSONDIVERSEY, INC. Alteration of Name(s) in Register under S187 Assignors: UNILEVER PLC
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides or bases
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/06Hydroxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • C11D7/16Phosphates including polyphosphates

Landscapes

  • 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)

Description

WO 96/29387 PCT/CA96/00153 -1- PROCESS FOR FORMING TABLETED HIGH-CAUSTIC DETERGENT Background of the Invention The institutional detergent market distributes a variety of products for washing silverware, pots and pans, dishes, floors, walls, stainless steel surfaces, tile and other areas.
Unlike products used in the home, institutional detergents are often sold in bulk and dispensed from mechanical dispensers. There are a variety of different physical forms these can take, including liquids, powders, solidified bricks, granules and tablets. Several factors enter into the determination of which particular physical form is most suitable for the desired application.
Feed rate is a very important consideration. With a liquid, where the product is directly injected for use, use concentration is easy to control. Unfortunately with liquids, the concentration of active components in the product is generally relatively low and therefore the container size can be prohibitively large. DE 3326459 discloses a liquid detergent for dishwashing which contains bicarbonate, metasilicates, phosphate, chlorine, tensides, acoustic source and water. EP 0297273 discloses a solid alkali cleaning material which contains alkali phosphate, silicates, carbonates and phosphoric partial ester. With solid forms, which are dissolved with water, the rate of dissolution will influence dispensing rate.
Delivering consistent feedstock is very important. With a brick formulation, the product consistency can be maintained to a certain extent, but dissolution rate can be slow and, as with many forms, there may also be problems with disposing of the container.
Another very important factor in distributing institutional detergents is packaging. For environment reasons, it is preferable to minimize packaging.
U.S. Patent 5,078,301 discloses a bag of detergent tablets wherein the bag is a water soluble material. This product is apparently designed to minimize packaging, but has several significant disadvantages, Primarily, with a water soluble bag, the water will act to dissolve the plastic bag. However, the undissolved residue of such bags tend to clog the dispenser. Also with a water soluble bag, there is the requirement of an exterior overwrap to prevent AMENDED SHEET -2ahumidity or extraneous water from destroying the water soluble bag during shipping and storage.
All of these problems are compounded with highly hygroscopic (highly caustic) and/or hydratable materials. Of course, with the caustic materials, the operators should never physically handle the detergent.
Powdered cleaning compounds are typically AMENDED
SH.ET
WO 96/29387 PCT/CA96/00153 -3dispensed with water. Given that premature exposure to water tends to increase the caking tendency of powders, clogging of the dispenser and uniform dispensing from powder systems, especially those prone to prolonged periods of inactivity, may be a problem.
Many detergents, particularly highly caustic detergents, dissolve in water and liberate a great deal of heat. It is therefore preferable to control the dissolution rate of these detergents to avoid temperature peaks in the dispensing equipment.
With tableted, high-caustic detergent, a further problem can be encountered. Anhydrous sodium hydroxide and potassium hydroxide are, of course, very hygroscopic. Typical detergent formulations generally include some free water, and certainly water of hydration from sources such as sodium tripolyphosphate hexahydrate. When tableting, the caustic comes into very close physical proximity to the water. The water is necessary for the tableting to occur at reasonable pressures. But once combined together, the caustic will exothermically react with the free water.
For tableted high caustic detergents, if this reaction occurs after compression, the mechanical strength of the tablet will be reduced.
WO 96/29387 PCTCA96/00153 -4- Summary of the Invention Accordingly, it is an object of the present invention to provide a method of forming a tableted detergent which includes phosphate sequestrants, free water, and high levels of caustic.
Further, it is an object of the present invention to provide such a product wherein the formed tablets do not deteriorate quickly after formation.
These objects and advantages of the present invention can be achieved by combining the individual components of the detergent, including the phosphate along with free water and caustic, in such a manner and/or order of addition that the overall temperature of the product at no time exceeds 750 C and preferably never exceeds 500 C and most preferably never exceeds 400 C. Careful blending, selection of raw materials and proper order of addition which factors in the hygroscopic nature of the materials and the lability of water, once absorbed, combine to achieve this result.
In one preferred embodiment of the present invention wherein fillers are included in the detergent formulation, the phosphate sequestrants, sodium tripolyphosphate, anhydrous and hexahydrate, are combined together with any liquid components including all free water. After the liquid components are absorbed into the sequestrants, caustic, filler and any bleaching agent are added. The product can then be compressed to form tablets. In this manner, the hydration reaction is adequately controlled, the free WO 96/29387 PCT/CA96/00153 water is absorbed by the species most capable of retaining it in the presence of caustic, thus reducing the potential for an exothermic reaction and subsequent deterioration of the tablet.
In an alternate embodiment of the present invention, cooling can be employed to physically control the temperature of the mixture, thereby preventing an undesirable excessively exothermic reaction. This, however, requires significant cooling time.
The objects and advantages of the present invention will be further appreciated in light of the following detailed description.
Detailed Descriotion The present invention is a method of making a high caustic tableted detergent, particularly a ware washing detergent.
This ware washing detergent will include a source of caustic, a hardness sequestering system including a hydrated phosphate, low molecular weight water-soluble polymers, non-ionic defoaming surfactants, processing aids and optionally bleaching sources.
The caustic source can be sodium or potassium hydroxide with sodium hydroxide preferred. Generally, for use in the present invention, this will include from about 20 to about caustic with about 45% to about 57% caustic being preferred. The caustic will be less than fully hydrated and is preferably substantially anhydrous.
The hardness sequestering system can be a variety of different chemical components. The primary sequestrants are alkali WO 96/29387 PCr/CA96/00153 -6metal salts of polyphosphates. Optional sequestrants include alkali metal salts of phosphonic acid and of gluconic acid, alkali metal salts of ethylene diamine tetraacetic acid (EDTA), alkali metal salts of nitrilotriacetic acid (NTA) and alkali metal salts of polycarboxylic acids such as polyacrylic acid, polymaleic acid and mixtures thereof.
Phosphates are commonly available in anhydrous or hexahydrate forms. For purposes of the present invention, a mixture of anhydrous and hydrated phosphates is preferred. The composition should include at least 10% hydrated phosphate sequestrant, based on total formulation.
Generally, the hardness sequestering system of the present invention will form 20 to about 80% of the overall mass of the detergent composition, and preferably about 35 to 40%. A mixture of hydrated (hexahydrate) and anhydrous sodium tripolyphosphate in the mass ratio of 3:1 to about 1:3, and preferably 1:1 to 2:1. In areas where the amount of phosphates is regulated, it may be necessary to supplement the water hardness control ability of the product by adding other sequestrants such as the alkali metal salts of NTA or EDTA.
The present invention can optionally include a chlorine source. One preferred chlorine source is dichloroisocyanurate. This is added in amounts of up to 7% by weight. Other bleaching aids including alkali metal perborates and percarbonates may also be used.
In addition to the above, the detergent composition may include defoaming surfactants. One typical class of anionic defoaming surfactants is the phosphate esters. The defoaming nonionic surfactant used herein is selected from the group consisting of alcohol alkoxylates, alkyl alkoxylates, block copolymers and mixtures thereof. Generally, these nonionic surfactants are prepared by the condensation reaction of a suitable amount of ethylene oxide and/or propylene oxide with a selected organic hydrophobic base under suitable oxyalkylation conditions. These reactions are well known and documented in the prior art. Generally, these will have a molecular weight of 900 to about 4,000. One such surfactant is an ethylene oxide propylene oxide block copolymer. Commercially available surfactants include Triton CF32, Triton DF12. Plurafac LF131 Plurafac LF132,XPlurafac LF231* Industrol N3 and Genapol .These can be included in an amount from about 0.5 to about with about 1.5% preferred.
In addition to this, low molecular weight (2,000-20,000), water-soluble polybasic acids such as polyacrylic acid, polymaleic or polymethacrylic acid or copolymeric acids can be used as sequestering aids, to inhibit growth of calcium carbonate crystals and to improve rinseability. Preferably the water-soluble polymer will be a polycarboxylic acid such as polyacrylic acid having a molecular weight of around 5000. Generally, the present invention should Trade Marks AENDED S tbi WO 96/29387 PCT/CA96/00153 -8include from about 1% to about 4% polyacrylic acid on an actives basis with about 2% preferred.
The detergent formulation may also include 1% to of a polyhydric water soluble alcohol. Suitable water soluble polyhydric alcohols include propylene glycol, ethylene glycol, polyethylene glycol, glycerine, pentaerythritol, trimethylol propane, triethanolamine, tri-isopropanol amine and the like. Propylene glycol is preferred. This acts as both a processing aid and a dissolution aid for the tablet, as is discussed below.
In order to provide a strong tablet the present invention will include from about 2 to 10% liquid components, preferably less than Generally, this can be provided for by the nonionic surfactant, the polyalcohols and/or free water. The formulation should also include 2% to 10% by weight of water of hydration. This also provides for a stronger tablet. Generally, there will be at least up to 5% free water in the composition. This can be the solvent for the polymer or surfactant. It is preferable to keep the free water less than 5% and the total liquid at less than 10% to keep the product flowable and non-tacky during the tableting.
In addition to the above, the detergent formulation can include optional ingredients commonly referred to as fillers such as soda ash, the silicates such as sodium and potassium silicate and polysilicate, and sodium metasilicate and hydrates thereof, alkali WO 96/29387 PCT/CA96/00153 -9metal chloride, alkali metal sulfates and alkali metal bicarbonate.
These can be present in an amount of 1% to 30% by weight.
A preferred formulation for use in the present invention includes the following: Table 1 Solid Components: 10.0% soda ash 21.0% sodium tripolyphosphate hexahydrate (18% water of hydration) 16.3% sodium tripolyphosphate powder 0.2% sodium dichloro-isocyanurate 45.0% caustic bead Liquid Components: 5000 molecular weight polyacrylic acid (48% active in water) ethylene oxide propylene oxide block copolymer non-ionic surfactant propylene glycol In this formulation, the sodium tripolyphosphate hexahydrate provides 3.8% water of hydration and the polyacrylic acid provides about 2.3% free water.
A very high caustic formula includes: WO 96/29387 PCT/CA96/00153 Table 2 Solid Components: 21.0% sodium tripolyphosphate hexahydrate (18% water of hydration) 16.3% sodium tripolyphosphate powder 56.7% caustic bead Liquid Components: 5000 molecular weight polyacrylic acid (48% active in water) ethylene oxide propylene oxide block copolymer non-ionic surfactant propylene glycol A third formulation which includes trisodium NTA is shown at Table 3.
Table 3 21.0% 16.3% 10.0% 1.7% 45.0% sodium tripolyphosphate hexahydrate (18% water of hydration) anhydrous sodium tripolyphosphate Trisodium NTA soda ash caustic 5000 mw acrylic acid (48% active) EOPO block copolymer propylene glycol In invention, the order to formulate the detergent of the present phosphates are combined together and mixed in a WO 96/29387 PCT/CA96/00153 -11ribbon or paddle blender. The fillers and other non-hygroscopic materials are not added at this time. Since a very low concentration of the liquid components is being added to the formulation, the liquid components should be combined prior to blending with the sequestrants. Normally, the ethylene oxide propylene oxide block copolymer will react with the polyacrylic acid to form a solid or gel.
However, mixing the propylene glycol with these two liquid components prevents this reaction.
Thus, any liquid components such as polyacrylic acid dissolved in water, the nonionic surfactant and the propylene glycol, are thoroughly mixed together and then sprayed evenly on the phosphate with mixing and allowed to soak into the phosphate. The caustic is added, then the fillers and finally the dichloroisocyanurate.
If NTA or EDTA are added, these should generally be added with the fillers, after the caustic.
It is very important that during all stages of mixing, and even after formulation, the temperature be kept at less than 750 C, preferably less than about 500 C and preferably less than 40° C. It is theorized that hydration of the caustic generates heat which, if excessive, will cause the STPP hexahydrate to liberate water, most likely accompanied by the decomposition of the tripolyphosphate anion, which will generate more heat, weakening the tablet.
However, by allowing the free water to be effectively completely absorbed by the phosphate, the hydration reaction is sufficiently WO 96/29387 PCT/CA96/00153 -12slowed and excessive heat is not generated and the hexahydrate does not give up water. The phosphate mixture strongly bonds with the free water.
As such when the caustic is combined with the mixture of phosphate and now bound water, hydration of the caustic is avoided. This prevention of caustic being hydrated in turns keeps the temperature down. Hence applicant's process provides a method of temperature control so as to maintain mixing temperature below 75°C by controlling or preventing the autocatalytic reaction.
If the free water is instead added to the fillers, or even to a mixture of filler and sequestrant, then that water which hydrates the filler is relatively easily accessed by the caustic and the resulting hydration is so rapid, generating so much heat, that the hydrated phosphate gives up water causing the formed tablets to crumble or weaken.
The detergent blend is then pressed to form tablets using a standard tableting machine. One such machine suitable for use in the present invention is the Stokes brand tableter. Generally, to form tablets, the powder is subjected to 4 to 10 tons pressure. Generally, the tablet will have a thickness of about 12 to 13 mm and a diameter of about 20 mm. The maximum diameter will be a function of the dispenser/feed water interface area.
The tablets of the end product after being produced do not weaken significantly over time. These can then be used in a typical ware washer apparatus equipped with a water spray detergent dispenser.
There are alternate methods to achieve this same result. An initial method of achieving this result is to omit fillers and form the detergent with anhydrous and hydrated sequestrants, along with the previously mentioned liquid components, as shown in Table 2. The phosphates are combined with the liquid component so that any free 747863.do-05/11/99 -13water present is adsorbed onto the sequestrants. The caustic is then added and the mixture tableted. Again, because the phosphates hold the water relatively tightly, the temperature at all times is maintained at less than 75'C and generally less than 50'C and therefore the hexahydrate will not liberate water which can react with the caustic. The formed tablets do not deteriorate rapidly after formation.
In a second alternate method of practicing the invention, the fillers can be combined with the phosphates and the water subsequently added. This can then be blended together with the caustic, provided sufficient cooling is provided so that the temperature is kept less than and preferably less than 40'C. This temperature is maintained for sufficient time to allow the caustic to react completely with any labile water prior to the tableting operation. Of course, this requires added processing time.
By employing the preferred method, the formed tablets have a drastically improved storage stability and shelf life. The end products are stronger, which means they are less likely during shipping to break apart and during use they will dissolve more slowly and evenly, providing for an even distribution of the detergent dissolved in water without creating an extreme exotherm. In all, this system provides many unique advantages and although several •embodiments of the present invention have been disclosed, the invention itself should be 20 defined only by the appended claims.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but 25 not the exclusion of any other integer or step or group of integers or steps.
0 0

Claims (7)

1. A method of forming a tableted detergent from a formulation comprising a partially hydrated phosphate mixture including at least 10% hydrated phosphate based on the formulation, anhydrous caustic, 0.5 to 5% free water and 0 to 40% filler, said formulation including from 2 to 10% liquid components and from 2 to 10% by weight water of hydration, the method comprising the steps of: adding said free water to said phosphate mixture without adding said filler, and allowing said water to be absorbed by said phosphate mixture; and subsequently adding 20% to 70% caustic to said phosphate mixture to form a second mixture whereby the temperature of said second mixture is maintained at less than 75 0 C; and compressing said second mixture to form tablets.
2. The method claimed in claim 1 wherein at least 5 filler is added to said phosphate mixture after said caustic added to said phosphate mixture.
3. The method claimed in claim 1 wherein said temperature of said second mixture is maintained at less than 20
4. The method claimed in claim 2 wherein said partially hydrated phosphate mixture comprises a mixture of STPP and STPP hexahydrate.
5. The method claimed in claim 3 comprising adding fillers to said phosphate mixture i after said water has been absorbed by said phosphate.
6 The method claimed in claim 3 comprising 1% to 3% free water.
7. The method claimed in claim 2 wherein said filler is selected from the group consisting of soda ash, alkali metal silicates, alkali metal polysilicates, alkali metal metasilicates, alkali metal chloride, alkali metal sulfates, and alkali metal bicarbonates. The method claimed in claim 2 comprising 40 to 70% caustic.
747863.doc4.5/I /99 9. The method claimed in claim 3 wherein the temperature of said second mixture is maintained at less than 40 0 C. 10. A method of forming a compressed detergent tablet, said tablet comprising: from 20% to 70% by weight of anhydrous caustic; from 20% to 80% by weight of a sequestering agent consisting of a combination of sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, said agent including at least 10% hydrated phosphate based on the formulation; from 0 to 4% by weight of polycarboxylated acid having a molecular weight of 2000 to 20,000; from 0 to 5% by weight of a defoaming agent, and from 0 to 4% by weight propylene glycol and from 5% to 40% filler; and free water, wherein said tablet includes from 2 to 10% liquid components and from 2 to 10% by weight water of hydration, said method comprising the steps of: combining said propylene glycol, said polycarboxylic acid and said free water to form a liquid mixture, combining said liquid mixture with said sequestering agent, and permitting said liquid mixture to be absorbed by said sequestering agent to form a first detergent mixture; and subsequently combining said filler and said caustic to said first detergent mixture to form a second detergent mixture and compacting said second detergent mixture to form tablets whereby the order of addition of the detergent components prevents the second detergent mixture from reaching a temperature in excess of 0 C. 9 6*9* 9 99 S S* 11. A method of forming a compressed tablet product comprising from 40% to 70% non- hydrated caustic; from 20% to 80% of a sequestering agent consisting of a mixture of sodium tripolyphoxphate and sodium tripolyphosphate hexahydrate, said mixture including at least 10% hydrated phosphate based on the formulation; from 5% to filler, and from 1% to 5% free water, wherein said tablet product includes from 2 to 10% liquid components and from 2 to 10% by weight of water of hydration, said method comprising the steps of: {1 T C) -o% 747863 doc4-5/11/99 -16- combining said water with said sequestering agent and allowing said water to be absorbed into said sequestering agent to form a detergent mixture; subsequently combining said caustic and said filler with said sequestering agent, thereby preventing the temperature of said detergent mixture from reaching 500 C; and compressing said detergent mixture to form tablets. Dated this 4th day of November, 1999 UNILEVER PLC By Its Patent Attorneys DAVIES COLLISON CAVE 8 p pp p ft pp.. p p 7,
AU49340/96A 1995-03-22 1996-03-14 Process for forming tableted high-caustic detergent Ceased AU714999B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US40853895A 1995-03-22 1995-03-22
US08/408538 1995-03-22
PCT/CA1996/000153 WO1996029387A1 (en) 1995-03-22 1996-03-14 Process for forming tableted high-caustic detergent

Publications (2)

Publication Number Publication Date
AU4934096A AU4934096A (en) 1996-10-08
AU714999B2 true AU714999B2 (en) 2000-01-13

Family

ID=23616685

Family Applications (1)

Application Number Title Priority Date Filing Date
AU49340/96A Ceased AU714999B2 (en) 1995-03-22 1996-03-14 Process for forming tableted high-caustic detergent

Country Status (10)

Country Link
EP (1) EP0815195B1 (en)
AR (1) AR001372A1 (en)
AU (1) AU714999B2 (en)
BR (1) BR9607840A (en)
CA (1) CA2215206C (en)
DE (1) DE69602591T2 (en)
ES (1) ES2132895T3 (en)
TR (1) TR199701002T1 (en)
WO (1) WO1996029387A1 (en)
ZA (1) ZA962339B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6177393B1 (en) * 1996-12-12 2001-01-23 The Procter & Gamble Company Process for making tabletted detergent compositions
GB2320254A (en) * 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions
GB2320255A (en) * 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions
US6177398B1 (en) 1996-12-12 2001-01-23 The Procter & Gamble Company Process for making tabletted detergent compositions
GB2321466A (en) * 1997-01-25 1998-07-29 Procter & Gamble Process for making tabletted detergent compositions
GB2340841A (en) * 1998-08-28 2000-03-01 Procter & Gamble Detergent Tablet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0375022A2 (en) * 1988-12-22 1990-06-27 Unilever N.V. Solid detergent block
WO1993001266A1 (en) * 1991-07-03 1993-01-21 Winbro Group, Ltd. Cake-like detergent and method of manufacture
WO1995007976A2 (en) * 1993-09-13 1995-03-23 Diversey Corporation Tableted detergent, method of manufacture and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3326459A1 (en) * 1983-07-22 1985-01-31 Etol-Werk GmbH & Co KG Chemische Fabrik, 7603 Oppenau Process for the production of a dishwashing composition and device for the processing of the latter
DE3721461A1 (en) * 1987-06-30 1989-01-12 Hoechst Ag STABLE AND SPECIFICALLY LIGHT ALKALINE CLEANING AGENTS AND A METHOD FOR THEIR PRODUCTION

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0375022A2 (en) * 1988-12-22 1990-06-27 Unilever N.V. Solid detergent block
WO1993001266A1 (en) * 1991-07-03 1993-01-21 Winbro Group, Ltd. Cake-like detergent and method of manufacture
WO1995007976A2 (en) * 1993-09-13 1995-03-23 Diversey Corporation Tableted detergent, method of manufacture and use

Also Published As

Publication number Publication date
CA2215206A1 (en) 1996-09-26
AU4934096A (en) 1996-10-08
EP0815195A1 (en) 1998-01-07
TR199701002T1 (en) 1998-02-21
AR001372A1 (en) 1997-10-22
ES2132895T3 (en) 1999-08-16
BR9607840A (en) 1998-06-16
ZA962339B (en) 1996-09-16
DE69602591T2 (en) 1999-10-07
DE69602591D1 (en) 1999-07-01
WO1996029387A1 (en) 1996-09-26
EP0815195B1 (en) 1999-05-26
CA2215206C (en) 2008-02-12

Similar Documents

Publication Publication Date Title
US5759976A (en) Process for forming tableted high-caustic detergent
EP0719325B1 (en) Tableted detergent, method of manufacture and use
US20210355416A1 (en) Pressed, self-solidifying, solid cleaning compositions and methods of making them
JP5571575B2 (en) Solidification matrix using polycarboxylic acid polymer
JP3727654B2 (en) Method for producing solid alkaline cleaning composition
JP5997314B2 (en) Solidification substrate comprising linear saturated mono-, di-, or tri-carboxylic acid salts
JP5801555B2 (en) Coagulation matrix using aminocarboxylate
AU727115B2 (en) A surfactant-containing compact detergent
US5674831A (en) Method of making urea-based solid cleaning compositions
JP3147901B2 (en) How to make detergent tablets for dishwashers
EA037068B1 (en) Detergent composition in the form of an effervescent tablet
JP6404809B2 (en) Use of sugars in stabilizing matrices and solid compositions
US20030216279A1 (en) Stable solid block detergent composition
JP2014507545A (en) Solidified matrix using carboxymethyl carbohydrate polymer binder
EP2206767B2 (en) Solid cleaning compositions
EP0569445B1 (en) Process for manufacturing cast silicate-based detergent
AU714999B2 (en) Process for forming tableted high-caustic detergent
AU713088B2 (en) Nta/edta-containing detergent composition
OA18490A (en) Detergent composition in the form of an effervescent tablet.

Legal Events

Date Code Title Description
FGA Letters patent sealed or granted (standard patent)
PC Assignment registered

Owner name: JOHNSONDIVERSEY, INC.

Free format text: FORMER OWNER WAS: UNILEVER PLC