[go: up one dir, main page]

EP0002293A1 - Detergent tablet having a hydrated salt coating and process for preparing the tablet - Google Patents

Detergent tablet having a hydrated salt coating and process for preparing the tablet Download PDF

Info

Publication number
EP0002293A1
EP0002293A1 EP78200307A EP78200307A EP0002293A1 EP 0002293 A1 EP0002293 A1 EP 0002293A1 EP 78200307 A EP78200307 A EP 78200307A EP 78200307 A EP78200307 A EP 78200307A EP 0002293 A1 EP0002293 A1 EP 0002293A1
Authority
EP
European Patent Office
Prior art keywords
tablet
salt
coating
sodium
melt
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.)
Withdrawn
Application number
EP78200307A
Other languages
German (de)
English (en)
French (fr)
Inventor
Daniel Biard
Gérard Jean Lichtfus
Hans Joachim Pracht
Wolfgang Kleeman
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0002293A1 publication Critical patent/EP0002293A1/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C11D17/0082—Coated 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to detergent tablets and, in particular, to coated detergent tablets, especially those adapted for use in automatic dishwashing machines.
  • tablets without a coating are entirely effective in use, they usually lack the necessary surface hardness to withstand the abrasion that is a part of normal manufacture, packaging and handling. The result is that uncoated tablets suffer from abrasion during these processes, resulting in chipped tablets and loss of active material. Also, especially in the case of highly alkaline tablets such as are useful for use in automatic dishwashing machines, the outer surface of an uncoated tablet may be aggressive to the skin and even somewhat hazardous to handle. In such cases, tablet coating is highly desirable. Finally, coating of tablets is often desired for aesthetic reasons, to improve the outer appearance of the tablet cr to achieve some particular aesthetic effect.
  • Polymeric coatings for detergent tablets have been proposed in, for example, U.K. Patent No. 989,683, No. 1,013,686 and No. 1,031,831. Although such coatings can provide excellent surface appearance and resistance to abrasicn, they tend to have a lower solubility than is desirable, resulting in the presence of undissolyed polyner in the wash solution. Also, polymeric coatings are difficult to apply ; frequently it is necessary to use organic solvents with the resultant difficulty and inconvenience of removing these solvents. Where the polymer can be applied from aqueous solution there is again a problem of drying, the removal of excess water requiring prolonged heating of the tablet.
  • Inorganic salt coatings have also been proposed in U.K. Patent No. 1,031,831.
  • the preferred coating material is podium silicate solution.
  • an aqueous solution is applied to the tablet and this of course requires a drying step to remove the water before the coating is formed.
  • a drying step Apart from the added complexity of a drying step, there is the further disadvantage that migration of excess water into the table may adversely affect the properties, especially solubility and storage stability, of the tablet.
  • a detergent tablet having a core comprising an alkaline builder salt and provided with a coating of a hydrated salt having a melting point in the range of from 30°C to 95° C, said coating having been applied to the tablet in the form of a melt.
  • detergent does not necessarily imply the presence of a surfactant material. Tablets which exert their cleaning power solely by the presence of inorganic salts (such as phosphate and silicate) are encompassed within the present invention:
  • inorganic salts such as phosphate and silicate
  • the present invention also provide a process for coating a detergent tablet comprising applying to the tablet a hydrated salt in the form of a melt, said hydrated salt having a melting point in the range from 30°C to 95°C.
  • a particulate, absorbent carrier material is dispersed in the coating of the tablet.
  • the carrier material has previously been loaded with a liquid, organic material, preferred organic materials being either nonionic surfactant or silicone suds suppressor. This allows incorporation of small amounts of liquid organic materials into the tablet without adversely affecting the strength/solubility characteristics of the tablet.
  • the detergent tablet which is to be provided with a coating according to the present invention can be of any type and can, for example, be adapted for laundry washing, dishwashing or.any other type of cleaning operation which involves dissolution of the table in an aqueous medium.
  • an alkaline salt preferably a water-soluble builder salt which normally provides a substantial part of the cleaning power of the tablet.
  • builder salt is intended to mean all materials which tend to remove calcium ion from solution, either by ion exchange, complexation, sequestration or precipitation.
  • salts for the purpose of providing alkalinity are water-soluble silicate salts.
  • silicates examples include those having the general formula nSiO 2 .M 2 O where n is from 0.5 to 4.0 and Mis a cation imparting water-solubility to the salt, preferably an alkali metal such as sodium or potassium.
  • Such silicates can contain up to 50 % by weight of water in the form of water of hydration.
  • Preferred materials are sodium metasilicate and sodium sesquisilicate.
  • Sodium orthosilicate may be used where very high alkalinity is desired.
  • Sodium metasilicate is very highly preferred.
  • the silicate salt (inclusive of any water of hydration) makes up more than 50 % of the tablet, preferably from 60 % to 80 %. In compositions designed for laundry use, there is usually much less silicate, for example 5 % to 15 %.
  • a water-soluble phosphate is a water-soluble phosphate.
  • Any water-soluble phosphate salt can be employed in the present invention, for example, sodium orthophosphate, pyrophosphate, tripolyphosphate or more condensed phosphates such as hexametaphosphate. Condensed phosphates are preferred, especially sodium tripolyphosphate.
  • the phosphate salt can be in at least partially hydrated form, particular examples being pentasodium tripolyphesphate hexahydrate and tetrasodium pyrophosphate decahydrate.
  • the phosphate salt (inclusive of any hydrated water) makes up from 10 % to 40 %, preferably from 20 % to 30 % of the tablet.
  • silicate and phosphate salts include water-soluble carbonates, bicarbonates and borates.
  • Water-soluble organic builder components may also be employed.
  • suitable organic detergency builder salts are : (1) water-soluble amino polyacetates, e.g., sodium and potassium ethylene-diamine tetra-acetates, nitrilotriacetates, and N-(2-hydroxyethyl) nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates; and (3) water-soluble polyphosphonates, including alkali metal salts of ethane-1-hydroxy-1,1-diphosphonic acid ; methylenediphosphonic acid, ethylene diamine tetramethylene phosphonic acid, nitrilotrimethyl- ene phosphonic acid and the like.
  • Additional organic builder salts useful herein include the polycarboxylate materials described in U.S. Patent No. 2,264,103, including the water-soluble alkali metal salts of mellitic acid.
  • the water-soluble salts of polycarboxylate polymers and copolymers such as are described in U.S. Patent No. 3,308,067, incorporated herein by reference, are also suitable herein.
  • a further class of builder salts useful herein is the water-insoluble silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Na z (AlO 2 ) z (SiO 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 of from about 15 to about 264.
  • Compositions incorporating builder salts of this type form the subject of British Patent No. 1,429,143 published March 24., 1976, German Offenlegungsschrift No. 2,433,485 published February 6, 1975 and "Offentechnischsschrift No. 2,525,778 published January 2, 1976, the disclosures of which are incorporated herein by reference.
  • Detergent tablets for use in the present invention can contain a water-soluble surfactant selected from anionic, nonionic, zwitterionic, amphoteric and cationic surfactants.
  • a water-soluble surfactant selected from anionic, nonionic, zwitterionic, amphoteric and cationic surfactants.
  • Surfactants of these types are described in U.S. Patent No. 3,929,678 the disclosure of which is incorporated herein by reference.
  • Laundry detergent tablets normally contain up to 15 % of an anionic surfactant such as C 8 -C 18 alkyl benzene sulphonates, C 8 -C 18 alcohol sulphates, C 8 -C 18 alcohol ethoxylate sulphates and fatty acid soaps.
  • Tablets designed for use in automatic dishwashing machines can contain no surfactant, but frequently contain up to 10 % of a nonionic surfactant.
  • Nonionic surfactants which are advantageously employed in the composition of this invention include, but are not limited to, the following polyoxyalkylene nonionic detergents : Cg-C22 normal fatty alcohol-ethylene oxide condensates, i.e., condensation products of one mole of a fatty alcohol containing from 8 to 22 carbon atoms with from 2 to 20 moles of ethylene oxide, polyoxypropylenepolyoxyethylene condensates having the formula HO(C 2 H 4 O) x (C 3 H 6 O) y (C 2 H 4 O) x1 H where y equals at least 15 and (C 2 H 4 O) x+x1 , equals 20-90 % of the total weight of the compound ; and alkyl polyoxypropylenepolyoxyethylene condensates having the formula RO-(C 3 H 6 O) x (C 2 H 4 O) y H where R is a C 1 -C 15 alkyl group and x and y each represent an integer of from 2 to 98
  • Preferred nonionic surfactants for automatic dishwashing machine detergent tablets have very low sudsing ability.
  • the afore-mentioned polyoxyethylene-polyoxypropylene surfactants are especially suitable in this respect.
  • Specific surfactant materials which are preferred include Pluronic L-61, Lutensol LF-700 and the Plurafac series, especially Plurafac RA-40, RA-43 and RA-343.
  • polyethylene glycols for example those of molecular weight from 1,000 to 20,000, especially about 10,000. While these materials are not normally considered as surfactant materials, they do assist in improving the wetting ability of the compositions and they are also useful as processing aids in the tablet manufacture.
  • Detergent tablets of the present invention also preferably include a bleach component, preferably a chlorine bleach when a dishwashing composition is desired and an oxygen bleach when a laundry tablet is intended.
  • a bleach component preferably a chlorine bleach when a dishwashing composition is desired and an oxygen bleach when a laundry tablet is intended.
  • Any of many known chlorine bleaches can be used in the present tablet.
  • bleach compounds are: chlorinated trisodium phosphate, dichloroisocyanuric acid, salts of chlorine substituted isocyanuric acid, 1,3-dichloro-5,5-di- methylhycantoin, N,N'-dichlorobenzoylene urea, paratoluene sulphodichloroamide, trichloromelamine, N-chloroammeline, N-chlorcsuccinimide, N, N'-dichloroazodicarbonamide, N-chloroacetyl urea,N,N'-dichlor
  • Useful oxygen bleaches include sodium perborate, sodium percarbonate and sodium persulphate.
  • Neutral fillers such as sodium sulphate and sodium chloride can be present and various other components can be included for various purposes.
  • additional components are enzymes, especially proteases and amylases, (which are useful in the absence of chlorine bleach), suds- suppressing agents, tarnish inhibitors such as benzotriazole, bactericidal agents, soil-suspending agents, dyes, brighteners and perfumes.
  • Tablets to be coated in 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.
  • Any liquid ingredients for example the surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
  • the principal ingredients, silicate and phosphate are used in granular form.
  • the ingredients such as builder salt and surfactant can be spray-dried in a conventional manner and then compacted at a suitable pressure.
  • the present invention is particularly applicable to the automatic dishwashing machine tablets described in the copending European patent application No. 78. 200014.5.
  • the tablets are highly alkaline and have a high density of at least 1.4g/cc and preferably about 1.5g/cc, for example 1.6-1.7.
  • the compressed tablet itself is free of liquid organic materials such as nonionic surfactant and suds suppressor (e.g. silicone suds suppressor) and that these organic materials are incorporated into the coating as hereinafter described.
  • the detergent tablets can be made in any size or shape and can, if desired, be surface treated before coating according to the present invention. For example, it may be desired to water-spray the surface as described in U.S. Patent No. 3,081,267 to provide added surface integrity during subsequent handling steps.
  • detergent tablets are prepared and in whatever form they are, they are then coated according to the present invention with a hydrated salt having a melting point of from 30°C to 95°C.
  • the'coating is applied in a state wherein it essentially solidifies on the tablet rather than dries on to it. It is therefore essential that the salt be applied at a temperature in excess of its melting point.
  • the salts having a melting point below 30°C are not sufficiently solid at ambient temperatures and it has been found that salts having a melting point above about 95°C lose their water of hydration so quickly after melting that it is not practicable to use these materials.
  • the salts melt in the range from 35°C to 75°C, more preferably from 45°C to 70°C.
  • melting point is meant the temperature at which the salt when heated slowly in, for example, a capillary tube becomes a clear liquid. It will be understocd that this is the point at which the salt dissolves in its own water of crystallisation. Solidification of this salt does not involve any loss of water, as the crystalline hydrate is again formed.
  • Any salt having a melting point in the required range and forming a hydrated species can be employed. This includes both inorganic and organic salts.
  • Suitable materials include sodium acetate trihydrate, sodium metaborate tetrahydrate, or octahydrate, scdium orthophosphate dodecahydrate, sodium dihydrogen phosphate dihydrate, the di-, depta-, or dodeca-hydrate of disodium hydrogen phosphate, sodium potassium tartrate tetrahydrate, potassium aluminium sulphate dodecahydrate, calcium bromide hexahydrate and calcium nitrate tetrahydrate.
  • Highly preferred materials are the sodium acetate and the sodium metaborate tetrahydrate. Mixtures of these two materials is proportions of metaborate:acetate by weight of from 3:1 to 1:3, preferably 2:1 to 1:2, are still more preferred.
  • the above mentioned hydrated salts When the above mentioned hydrated salts are heated to an appropriate temperature, they form a clear liquid phase and detergent tablets of the type described above are coated with the molten hydrated salt.
  • the molten salt can be applied to the tablet in any convenient way, for example by spraying or dipping. Normally, when the molten salt is sprayed on to the tablets, it will solidify almost instantaneously to form a coherent coating. When tablets are dipped into the molten salt and then removed, the rapid cooling again causes almost instantaneous solidification of the coating material.
  • the hydrated salts form melts which tend to be too viscous for easy spraying. Also, the heating of the salt tends to drive off part of the water of hydration, thus also increasing viscosity and tending to cause premature crystallisation of the salt. This can be avoided by adding a small amount of water to the molten salt and, in the context of the present invention, the term'"melt" is intended to mean both the true molten hydrated salt and the molten salt when diluted with water. However, it should be understood that the diluted molten salt will still behave as a molten phase,i.e. it will, on cooling, solidify without the need for substantial drying or removal of excess'water.
  • any water added to the melt should not exceed 30% by weight of the melt, preferably not more than 20%, for example from 5% to 15%.
  • the presence of a slight excess of water can provide a further advantage in that migration of this water into the tablet results in an increase in tablet strength.
  • 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 of the present invention are very hard and yet still highly soluble, are more stable than many organic coatings and are neutral to tablet solubility and performance.
  • the coating melt can contain minor quantities of other ingredients, for example, dyestuffs, perfume, opacifier, suds suppressor, surfactant(especially nonionic surfactant), etc.
  • the surfactant and/ or suds suppressor is incorporated into the coating in the following manner.
  • an organic, liquid material can be incorporated into the tablet of the present invention by (a) sorbing the liquid material into a solid, particulate carrier material, (b) dispersing the loaded carrier material in the molten coating material and (c) applying the coating material in the manner described above.
  • This method can be used for the incorporation of any organic, liquid material but is especially preferred for incorporating either a liquid, nonionic surfactant or a liquid suds suppressor, especially an emulsifiable silicone suds suppressor as described in German Offenlegungsschrift No. 26 46 127, the disclosure of which is incorporated herein by reference. It has been found that direct incorporation of such organic materials into the tablet itself can adversely affect the strength/solubility characteristics of the tablet, especially if high-density tablets are desired.
  • any suitable carrier material can be used.
  • aluminosilicates for example the synthetic material known as zeolite A and having the formula
  • the aluminosilicate materials described in U.K. Patent Specification No. 1,429,143 can be employed, as can the aluminosilicate material sold by Sifrance under the trade name DG-12.
  • the carrier material can absorb from about 10% to 40% by weight of silicone suds suppressor or nonionic surfactant.
  • the loaded carrier material can be suspended in the coating melt at a level of up to about 50% by weight of the mixture.
  • Another method of incorporating surfactant and/or suds suppressor into the inorganic melt coating is to emulsify the organic liquid into the inorganic melt with the help of a hydrotrope material such as sodium cumene sulphonate, sodium toluene sulphonate, sodium or potassium xylene sulphonate or a phosphate ester as described in British Patent No. 1,485,316.
  • a hydrotrope material such as sodium cumene sulphonate, sodium toluene sulphonate, sodium or potassium xylene sulphonate or a phosphate ester as described in British Patent No. 1,485,316.
  • Granular sodium metasilicate 34,0g,
  • granular sodium tripolyphosphate (12.0g.)
  • sodium aluminate (0.08g.)
  • sodium dichloroisocyanurate 1.1g.
  • About 23 g. of this mixture were introduced into a mould of triangular shape with equilateral triangle sides of 3.3 cm and were compressed in this mould under a pressure of about 470Kg/sq. cm to give a tablet,of about 1.9 cm tickness and a density of about 1.7 g/cc.
  • Example 2 Following the procedure of Example 1, a tablet was prepared and the melt of sodium metaborate and sodium acetate was made. To this melt (100 parts) was added 5 parts of water and the diluted melt was sprayed as before to give a coating of 5% of the tablet weight.
  • coated tablets of Examples 1 and 2 are especially suitable for use in automatic dishwashing machines and have an excellent, strong, water-soluble coating.
  • a spray-dried granular detergent composition has the following composition:
  • the tablet is then coated with a mixture of sodium metaborate and sodium acetate according to the procedures of Examples 1 or 2.
  • the coated tablet is suitable for use as a laundry detergent tablet.
  • Example 1 The procedure of Example 1 is repeated except that the tablet was dipped into the melt of sodium tetraborate and sodium acetate and then removed. The melt solidified quickly at ambient temperature and a coated tablet was obtained having a coating weight of about 5% of the total tablet weight.
  • a silicone suds suppressor (0.3 parts) was sorbed on to 1.2 parts of a zeolite A having a particle size of 5 microns and the loaded carrier material was then suspended in 3 parts of a coating melt as described in Example 1. The melt containing the suspended particulate carrier material was then sprayed on to the tablet of Example 1 to give a tablet with a 4.5% weight of coating.
  • a coated tablet containing 0.3% of a nonionic surfactant can be prepared.

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)
  • Detergent Compositions (AREA)
EP78200307A 1977-11-29 1978-11-16 Detergent tablet having a hydrated salt coating and process for preparing the tablet Withdrawn EP0002293A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB4961477 1977-11-29
GB4961477 1977-11-29
GB600478 1978-02-15
GB600478 1978-02-15

Publications (1)

Publication Number Publication Date
EP0002293A1 true EP0002293A1 (en) 1979-06-13

Family

ID=26240312

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200307A Withdrawn EP0002293A1 (en) 1977-11-29 1978-11-16 Detergent tablet having a hydrated salt coating and process for preparing the tablet

Country Status (6)

Country Link
EP (1) EP0002293A1 (it)
BE (1) BE56T1 (it)
DE (1) DE2857472A1 (it)
FR (1) FR2443502A1 (it)
IT (1) IT1101296B (it)
NL (1) NL7815064A (it)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057088A1 (en) * 1981-01-24 1982-08-04 THE PROCTER & GAMBLE COMPANY Detergent compositions
EP0126963A1 (de) * 1983-05-02 1984-12-05 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung von Reinigungsmitteltabletten
EP0181651A2 (en) * 1984-10-02 1986-05-21 Unilever N.V. Enzymatic detergent composition
WO1995018215A1 (en) * 1993-12-30 1995-07-06 Ecolab Inc. Stable hygroscopic detergent article
DE19637606A1 (de) * 1996-09-16 1998-03-26 Henkel Kgaa Bruchfeste Wasch- oder Reinigungsmittelformkörper
EP0838519A1 (en) * 1996-10-22 1998-04-29 Unilever Plc Water-softening and detergent compositions
EP0846755A1 (en) * 1996-12-06 1998-06-10 The Procter & Gamble Company Coated detergent tablet
WO1998040550A1 (en) * 1997-03-07 1998-09-17 Unilever Plc Process and dispensing device for washing laundry in a washing machine
WO1998055582A1 (en) * 1997-06-06 1998-12-10 Unilever Plc Cleaning compositions in tablet form
WO1999053014A1 (en) * 1998-04-15 1999-10-21 Unilever Plc Water-softening and detergent compositions
WO2000022088A1 (en) * 1998-10-09 2000-04-20 Unilever Plc Water-softening and detergent compositions
WO2000022089A1 (en) * 1998-10-09 2000-04-20 Unilever Plc Water-softening and detergent compositions
EP1026229A1 (en) * 1999-02-03 2000-08-09 The Procter & Gamble Company Coated detergent tablet
EP1099751A2 (en) * 1999-11-02 2001-05-16 Smiths Industries Public Limited Company Disposal means
KR100374935B1 (ko) * 1999-12-21 2003-03-06 주식회사 엘지생활건강 정제형 세제 조성물
EP1293556A1 (en) * 2001-09-14 2003-03-19 Rent-a-Scientist GmbH Detergent tablet having a coating comprising carbamide
EP0881282B2 (en) † 1997-05-27 2009-06-03 The Procter & Gamble Company Tablets, and process for making tablets
WO2012069895A1 (en) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
WO2024224386A1 (en) * 2023-04-25 2024-10-31 Bubl-Revolutionary Toilets Solution Ltd Composition and method to prevent or reduce splashing on use of a toilet and/or facilitate toilet cleanliness

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460490A (en) * 1980-12-18 1984-07-17 Jeyes Group Limited Lavatory cleansing blocks
GB8907100D0 (en) * 1989-03-29 1989-05-10 Unilever Plc Particulate detergent additive product,preparation and use thereof in detergent compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB989683A (en) * 1961-04-03 1965-04-22 Colgate Palmolive Co Detergent tablets and processes for manufacturing them
AT239943B (de) * 1960-11-07 1965-05-10 Unilever Nv Verfahren zum Aufbringen eines Überzuges auf Seifentabletten
GB1080066A (en) * 1965-03-09 1967-08-23 Procter & Gamble Detergent tablets
GB1191356A (en) * 1967-12-28 1970-05-13 Henkel & Cie Gmbh Improvements in Washing Agents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT239943B (de) * 1960-11-07 1965-05-10 Unilever Nv Verfahren zum Aufbringen eines Überzuges auf Seifentabletten
GB989683A (en) * 1961-04-03 1965-04-22 Colgate Palmolive Co Detergent tablets and processes for manufacturing them
GB1080066A (en) * 1965-03-09 1967-08-23 Procter & Gamble Detergent tablets
US3503889A (en) * 1965-03-09 1970-03-31 Procter & Gamble Detergent tablets
GB1191356A (en) * 1967-12-28 1970-05-13 Henkel & Cie Gmbh Improvements in Washing Agents

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057088A1 (en) * 1981-01-24 1982-08-04 THE PROCTER & GAMBLE COMPANY Detergent compositions
EP0126963A1 (de) * 1983-05-02 1984-12-05 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung von Reinigungsmitteltabletten
EP0181651A2 (en) * 1984-10-02 1986-05-21 Unilever N.V. Enzymatic detergent composition
EP0181651A3 (en) * 1984-10-02 1988-02-10 Unilever N.V. Enzymatic detergent composition
KR100342848B1 (ko) * 1993-12-30 2002-11-23 이코랍 인코퍼레이티드 안정한 흡습성 세제 용품
WO1995018215A1 (en) * 1993-12-30 1995-07-06 Ecolab Inc. Stable hygroscopic detergent article
AU684596B2 (en) * 1993-12-30 1997-12-18 Ecolab Inc. Stable hygroscopic detergent article
US5759988A (en) * 1993-12-30 1998-06-02 Ecolab Inc. Stable hygroscopic detergent article
DE19637606A1 (de) * 1996-09-16 1998-03-26 Henkel Kgaa Bruchfeste Wasch- oder Reinigungsmittelformkörper
EP0972824A2 (en) * 1996-10-22 2000-01-19 Unilever Plc Water-softening and detergent compositions
EP0838519A1 (en) * 1996-10-22 1998-04-29 Unilever Plc Water-softening and detergent compositions
GB2318575A (en) * 1996-10-22 1998-04-29 Unilever Plc Detergent tablet
EP0972824A3 (en) * 1996-10-22 2000-03-15 Unilever Plc Water-softening and detergent compositions
EP0846755A1 (en) * 1996-12-06 1998-06-10 The Procter & Gamble Company Coated detergent tablet
WO1998040550A1 (en) * 1997-03-07 1998-09-17 Unilever Plc Process and dispensing device for washing laundry in a washing machine
US6174848B1 (en) 1997-03-07 2001-01-16 Lever Brothers Company, Div. Of Conopco Inc. Process and dispensing device for washing laundry in a washing machine
EP0881282B2 (en) † 1997-05-27 2009-06-03 The Procter & Gamble Company Tablets, and process for making tablets
US6372707B1 (en) 1997-06-06 2002-04-16 Lever Brothers Company, Division Of Conopco, Inc. Cleaning compositions
WO1998055582A1 (en) * 1997-06-06 1998-12-10 Unilever Plc Cleaning compositions in tablet form
WO1999053014A1 (en) * 1998-04-15 1999-10-21 Unilever Plc Water-softening and detergent compositions
US6093688A (en) * 1998-04-15 2000-07-25 Unilever Home & Personal Care Usa Water softening and detergent compositions
US6380141B1 (en) 1998-04-15 2002-04-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Water-softening and detergent compositions
US6153574A (en) * 1998-10-09 2000-11-28 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Water-softening and detergent compositions
WO2000022088A1 (en) * 1998-10-09 2000-04-20 Unilever Plc Water-softening and detergent compositions
WO2000022089A1 (en) * 1998-10-09 2000-04-20 Unilever Plc Water-softening and detergent compositions
WO2000046340A1 (en) * 1999-02-03 2000-08-10 The Procter & Gamble Company Coated detergent tablet
EP1026229A1 (en) * 1999-02-03 2000-08-09 The Procter & Gamble Company Coated detergent tablet
EP1099751A3 (en) * 1999-11-02 2001-08-01 Smiths Industries Public Limited Company Disposal means
EP1099751A2 (en) * 1999-11-02 2001-05-16 Smiths Industries Public Limited Company Disposal means
KR100374935B1 (ko) * 1999-12-21 2003-03-06 주식회사 엘지생활건강 정제형 세제 조성물
EP1293556A1 (en) * 2001-09-14 2003-03-19 Rent-a-Scientist GmbH Detergent tablet having a coating comprising carbamide
WO2012069895A1 (en) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
DE102010051226A1 (de) 2010-11-12 2012-05-31 Dental Care Innovation Gmbh Ausspültablete mit abrasiven Bestandteilen
US9493731B2 (en) 2010-11-12 2016-11-15 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
US11596587B2 (en) 2017-02-02 2023-03-07 Water Pik, Inc. Tablet including abrasive for dental cleaning
WO2024224386A1 (en) * 2023-04-25 2024-10-31 Bubl-Revolutionary Toilets Solution Ltd Composition and method to prevent or reduce splashing on use of a toilet and/or facilitate toilet cleanliness

Also Published As

Publication number Publication date
FR2443502A1 (fr) 1980-07-04
NL7815064A (nl) 1980-05-30
BE56T1 (fr) 1980-04-18
DE2857472A1 (de) 1980-07-17
IT1101296B (it) 1985-09-28
IT7830328A0 (it) 1978-11-29

Similar Documents

Publication Publication Date Title
US4219435A (en) Detergent tablet coating
EP0002293A1 (en) Detergent tablet having a hydrated salt coating and process for preparing the tablet
US4219436A (en) High density, high alkalinity dishwashing detergent tablet
US4933102A (en) Solid cast warewashing composition; encapsulated bleach source
US5670473A (en) Solid cleaning compositions based on hydrated salts
CA1259543A (en) Method for forming solid detergent compositions
US5080819A (en) Low temperature cast detergent-containing article and method of making and using
US5665694A (en) Block detergent containing nitrilotriacetic acid
US6730653B1 (en) Method for manufacturing a molded detergent composition
CA2266068A1 (en) A surfactant-containing compact detergent
CA1304649C (en) Solid cast warewashing composition
EP0569445B1 (en) Process for manufacturing cast silicate-based detergent
US5205954A (en) Automatic dishwasher powder detergent composition
JP2000509093A (ja) 業務用食器洗浄機のための圧縮洗剤
US5419850A (en) Block detergent containing nitrilotriacetic acid
EP0804538B1 (en) Block detergent containing nitrilotriacetic acid
CA1318565C (en) Low temperature cast detergent-containing article and method of making and using
US6162777A (en) Automatic dishwashing tablets
NZ228002A (en) Automatic dishwashing detergent powder containing alkali silicate
US5425895A (en) Block detergent containing nitrilotriacetic acid
CZ20001052A3 (cs) Čistící prostředek
EP0430818A2 (en) Automatic dishwasher powder detergent composition
JPH02120384A (ja) 増粘された液体

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB NL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

110E Request filed for conversion into a national patent application [according to art. 135 epc]
18D Application deemed to be withdrawn
RIN1 Information on inventor provided before grant (corrected)

Inventor name: KLEEMAN, WOLFGANG

Inventor name: LICHTFUS, GERARD JEAN

Inventor name: BIARD, DANIEL

Inventor name: PRACHT, HANS JOACHIM