EP0799886A2 - Tablettes de détergent pour du linge - Google Patents
Tablettes de détergent pour du linge Download PDFInfo
- Publication number
- EP0799886A2 EP0799886A2 EP97610007A EP97610007A EP0799886A2 EP 0799886 A2 EP0799886 A2 EP 0799886A2 EP 97610007 A EP97610007 A EP 97610007A EP 97610007 A EP97610007 A EP 97610007A EP 0799886 A2 EP0799886 A2 EP 0799886A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- laundry detergent
- detergent tablets
- weight
- agents
- tenside
- 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.)
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Classifications
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- 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
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- 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
- C11D17/0086—Laundry tablets
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- 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
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/002—Surface-active compounds containing sulfur
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the present invention relates to laundry detergent tablets which are advantageous in having a good washing effect, and which are simultaneously very good storage stability and easily soluble in the washing water.
- Conventionally used laundry detergent compositions can be divided into two main types, viz. liquid and powder washing compositions.
- laundry detergent tablets have, however, been increasingly focused on because they present the advantage of being easy to handle and to dose correctly.
- laundry detergent tablets must ideally meet the following requirements:
- a sufficient tablet strength can be obtained by increasing the pressure used for compressing the laundry detergent tablets.
- An increase of the pressure has, however, a negative effect on the solubility of the laundry detergent tablets, and accordingly these properties are very difficult to combine.
- the demand for a quick dissolving of the laundry detergent tablets in the washing water is further sharpened by the growing tendency of performing the machine-wash using a decreasing amount of water, lower temperatures and shorter washing periods for environmental and financial reasons and in order to obtain consumer acceptance.
- the demand for a good washing effect involves as mentioned above a requirement for a high content of active washing substances having a tendency to extend the disintegration period of the cloth detergent tablets and to reduce their shelf life.
- JP No. 6279799 (LION CORP.) describes detergent tablets based on 1 to 50% by weight of an anionic tenside in form of an alpha--sulpho-fatty acid derivative as well as 5 to 60% by weight of an alkali carbonate, said tablets being described as being easily soluble in water.
- the alkali carbonate is potassium carbonate or a mixture of potassium carbonate and sodium carbonate in a weight ratio of from 100:0 to 40:60 and has preferably an average particle size of less than 300 ⁇ m, especially less than 150 ⁇ m.
- JP No. 6108099 (LION CORP.) describes easily soluble detergent tablets with a high washing effect and containing 5 to 50% by weight of one or more surfactants, including nonionic surfactants, 10 to 70% by weight of potassium carbonate as well as 0.5 to 5% by weight of pulverulent perfume.
- JP No. 6017099 (LION CORP.) describes easily soluble detergent tablets with a high washing effect and containing (A) 1 to 50% by weight of an anionic surfactant, (B) 0.1 to 4% by weight of a nonionic surfactant, as well as (C) potassium carbonate in a weight ratio of (B):(A) of up to 0.5 and a weight ratio of (B):(C) of up to 0.25.
- JP No. 4239100 (LION CORP.) describes easily soluble detergent tablets containing 5 to 50% by weight of one or more surfactants, including nonionic surfactants, as well as 10 to 70% by weight of potassium carbonate.
- the potassium carbonate used has preferably an average particle size of up to 150 ⁇ m.
- EP No. 0 482 627 A1 discloses laundry detergent tablets containing potassium carbonate and a nonionic surfactant with an HLB value of from 8.0 to 16.0 in a weight ratio of from 5:1 to 1:5.
- All the recipes indicated in the publication contain relatively high amounts of zeolite and are based on a nonionic surfactant as well as optionally an anionic surfactant unlike the present laundry detergent tablets.
- the present laundry detergent tablets are based on a combination of a nonionic tenside and an amphoteric tenside as well as a zeolite-poor or -free builder system of a polyfunctional carboxylic acid and/or a salt thereof, such as citrate, and layered silicate and/or alkali metal silicate and/or zeolite.
- Example 1 and Example 2 in the publication the preparation of tablets is described by way of melt kneading followed by a moulding in pressurized cylinders, and in Example 1 the pressurized moulding is indicated to last 1 minute where the production speed at conventional tabletting by way of comparison is from 25,000 to 90,000 tablets per hour.
- Such a moulding process is therefore highly disadvantageous and uneconomic for the preparation of tablets on an industrial scale.
- the object of the present invention is to provide easily soluble laundry detergent tablets having a high washing effect and a good storage stability.
- laundry detergent tablets according to the invention which are characterized in that in addition to the optional, conventional adjuvants and additives they comprise:
- the laundry detergent tablets comprises furthermore one or more ingredients selected from sodium carbonate/bicarbonate and/or potassium carbonate/bicarbonate, disintegrating agents, binders, enzymes, antifoaming agents, agents preventing the running of colour, antiredepositing agents, such as cellulose colloids, such as carboxymethyl cellulose, polymers and complex-binding agents, such as phosphonates.
- laundry detergent tablets according to the invention comprise in addition to optional, usual adjuvants and additives
- the laundry detergent tablets according to the invention are primarily intended for use in ordinary household washing machines, including both washing machines of the toploader-type, where the laundry and the detergent are introduced in the top of the washing machines in a vertically arranged drum, and the frontloader-type, where the laundry and the detergent are introduced in a horizontally arranged drum through a front door.
- Washing machines of the toploader-type are preferably used in Asia, Australia and USA, where low washing temperatures are traditionally used, often in the range of from 15 to 20°C, which presents particular requirements to the disintegration period of the laundry detergent tablets.
- Washing machines of the frontloader-type are especially used in Europe. As mentioned above, the trend is towards the use of a decreasing consumption of water combined with shorter and shorter washing periods as well as lower and lower temperatures (on the average 30 to 60°C compared to 60 to 90°C previously), which also presents high requirements to the disintegration period of the laundry detergent tablets.
- Laundry detergent tablets according to the invention to be used in soft cold water are advantageously composed as follows: nonionic tenside 0.1 to 6% by weight amphoteric tenside 0.1 to 5% by weight polyfunctional carboxylic acid and/or a salt thereof calculated as trisodium citrate dihydrate 20 to 50% by weight layered silicate and/or alkali metal silicate, and/or zeolite 1 to 10% by weight potassium carbonate 20 to 70% by weight disintegrating agent 0.5 to 5% by weight binder 1 to 5% by weight enzyme 0.25 to 10% by weight antiredepositing agent 0.25 to 3% by weight antifoaming agent 0 to 1 % by weight agent preventing the running of colour 0 to 3% by weight complex-binding agent 0 to 10% by weight
- Laundry detergent tablets according to the invention to be used in hard hot water such as water of a hardness of 10 - 20°dH and a temperature of 30 - 60°C, are advantageously composed as follows:
- the laundry detergent tablets according to the invention are based on a builder system of a polyfunctional carboxylic acid and/or a salt thereof, and layered silicate and/or alkali metal silicate and/or zeolite.
- the laundry detergent tablets are preferably zeolite-poor or zeolite-free, but if desired, they may contain a small amount of zeolite, such as 0.1 to 10% by weight, said zeolite beyond having a builder effect also having a liquid-absorbing effect and thereby being active in providing a free-flowing powder.
- zeolite has on account of its good builder properties dominated the market as builder ingredient in compact detergents, but during recent years attempts have been made at reducing or avoiding the use thereof due to problems applying especially to cleaning plants due to accumulation of mud. Moreover high concentrations of zeolite may cause problems of discolorations of for instance dark textiles, where the white zeolite particles are clearly visible.
- the laundry detergent tablets are based on a particular tenside system comprising both nonionic tenside and amphoteric tenside, preferably in a weight ratio of 0.1:1 - 10:1, such as 0.2:1 - 5:1, for instance 1:1 - 2:1.
- This particular tenside system in combination with the zeolite-poor or -free builder system results surprisingly in a high washing effect combined with a good storage stability as well as a rapid solubility.
- the washing effect of the laundry detergent tablets according to the invention is fully abreast of and in some cases even superior to the washing effect of the best products in the market.
- the nonionic tenside is advantageously included in an amount of from 2.5 - 10.0, such as from 3.5 - 8.0, for instance from 4.5 - 6.0% by weight, and may in principle be selected from all the conventional nonionic tensides usually produced by condensation of a hydrophilic alkylene oxide with a hydrophobic compound.
- alkylene oxides are ethylene oxide, propylene oxide and/or butylene oxide
- hydrophobic compounds are alcohols, thioalcohols, dioles, fatty acids, fatty acid amides, alkane sulphonamides, alkylamines as well as alkylphenoles.
- nonionic tensides especially ethoxylated compounds of primary and secondary fatty alcohols are preferred, said compounds being selected from linear fatty alcohols, oxoalcohols and alcohols prepared by the Ziegler-process, i.e. fatty alcohols with an even number of carbon atoms.
- Particularly preferred are condensation products having 2 to 40 moles of ethylene oxide (EO), preferably 3 to 16 moles of EO per mole of fatty alcohol selected from linear fatty alcohols, such as for instance C 12-18 coco alcohols, C 16-18 tallow alcohols, oleyl alcohol or other native alcohols as well as mixtures thereof.
- EO ethylene oxide
- nonionic tensides are oleyl monoethanol amide + 4 EO and ethoxylated C 12 - C 14 fatty alcohol + 7 EO as well as the lower C 8-12 alkyl polyglycosides of the so-called APG-types which are of a vegetable origin.
- Such compounds are very friendly to the skin and furthermore environmentally acceptable as they are completely biodegradable.
- Petrochemically based tensides may, however, also be used, said tensides being very inexpensive as well as available in many different types and variants.
- amphoteric tenside used is advantageously included in an amount of from 0.5 - 7.0, such as from 1.5 - 6.0, for instance from 2.5 -5.0% by weight, and may in principle be selected from all conventional amphoteric tensides.
- examples are betaine derivatives, imidazoline derivatives, alkyl polyamine carboxylates, alkyl iminodipropionates etc.
- Specific examples are for instance oleoamphopolycarboxy glycinate, lauramidopropyl betaine and coco amidopropyl betain.
- anionic tenside it is, if desired, possible to include a small amount of an anionic tenside in the laundry detergent tablets according to the invention.
- anionic tenside it is possible to use any anionic tenside conventionally included in laundry detergents and not having a disadvantageous influence on the laundry detergent tablets.
- a too high amount of anionic tenside may result in formation of insoluble compounds at higher degrees of the water hardness, which results in a reduced washing effect.
- the polyfunctional carboxylic acid and/or the salt thereof used is advantageously included in an amount of from 20.0 - 40.0, such as from 21.0 - 37.0, for instance from 22.5 - 35.0% by weight.
- Polyfunctional carboxylic acids may as a general rule be defined as such acids which beyond the one obligatory carboxylic acid group also contain at least one further functional group selected from carboxyl and hydroxy.
- the polyfunctional acids may furthermore also contain nitrogen.
- Non-limiting examples of such polyfunctional carboxylic acids are citric acid, nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA) and isoserine diacetic acid (ISDA), of which citric acid is preferred.
- Citric acid is available in form of trisodium citrate dihydrate, anhydrous trisodium citrate as well as anhydrous monosodium citrate. Trisodium citrate dihydrate is particularly preferred.
- Layered silicate and/or alkali metal silicate and/or zeolite are furthermore included as obligatory ingredient in the laundry detergent tablets according to the invention.
- Layered silicate and/or alkali metal silicate and/or zeolite are advantageously included in an amount of from 2.0 - 25.0, such as from 5.0 - 22.5, for instance from 10.0 - 20.0% by weight.
- Layered silicate or a combination of layered silicate and a small amount of alkali metal silicate are preferably used.
- zeolite aluminosilicate
- aluminosilicate all known types of aluminosilicates may in principle be used. Examples of such types are mentioned in Danish printed accepted publication No. 151,231, Danish printed accepted publication No. 154,827 and EP Offenlegungsschrift No. 289,767.
- the potassium carbonate used is advantageously included in an amount of from 10.0 - 50.0, such as from 15.0 - 40.0, for instance from 20.0 - 35.0% by weight.
- a small amount of sodium bicarbonate and/or potassium bicarbonate or alternatively sodium carbonate and/or potassium carbonate or a mixture thereof may advantageously be included, such as in an amount of from 2.5 -10.0, for instance from 4.0 - 7.0% by weight.
- ingredients are advantageously included in the laundry detergent tablets according to the invention, said ingredients being selected from disintegrating agents, binders, enzymes, antifoaming agents, agents preventing the running of colour, antiredepositing agents, polymers and complex-binding agents. Such agents are completely conventional.
- Disintegrating agents swell at contact with water thereby accelerating the disintegration of the tablets.
- examples of disintegrating agents are starch derivatives, cellulose compounds, polyvinyl pyrrolidone compounds, polyvinyl polypyrrolidone compounds, bentonite compounds, alginates, gelatine and pectines.
- the amount of disintegrating agent is typically in the range of 1.5 - 4.0, such as 1.8 -3.2, for instance 2.0 - 3.0% by weight.
- an organic carboxylic acid preferably a polyfunctional organic carboxylic acid, such as for instance maleic acid and the hydroxy carboxylic acids malic acid, citric acid and tartaric acid, which together with the carbonate and/or bicarbonate used result in an effervescent effect when the tablets come into contact with water.
- binders are polyethylene glycol, preferably of a molecular weight in the range of 200 - 10,000, glycerol, natural gums, for instance acacie and gacanth, as well as sugars, such as glucose and sucrose. These compounds are described in greater detail in "Die Tablette” by Dr. W.A. Ritschel, published by Cantor KG/Aulendorf, Württ, Germany.
- the amount of binder is typically in the range of 2.0 - 6.0, such as 3.0 - 5.0% by weight.
- enzymes are mixtures of specifically acting types, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases, which are described further inter alia in US-PS Nos.3,519,570 and 3,533,139.
- T-granulates are proteolytic enzymes sold under the trade names ESPERASE®, SAVINASE® and ALCALASE®, amylolytic enzymes sold under the trade name TERMAMYL®, lipolytic enzymes sold under the trade name "LIPOLASE” and “LIPOLASE ULTRA” and cellulytic enzymes sold under the trade name CELLUZYME®, as well as mixtures thereof.
- proteolytic enzymes sold under the trade names ESPERASE®, SAVINASE® and ALCALASE® amylolytic enzymes sold under the trade name TERMAMYL®
- lipolytic enzymes sold under the trade name "LIPOLASE” and “LIPOLASE ULTRA”
- cellulytic enzymes sold under the trade name CELLUZYME® as well as mixtures thereof.
- Durazym which is a proteolytic enzyme
- Duramyl which is an amylolytic enzyme
- the total amount of enzymes is advantageously in the range of 0.5 -8.0, such as 1.0 - 6.5% by weight.
- antifoaming agents are both silicone-free and silicone-based compounds.
- silicone-based compounds organo polysiloxane compounds are preferred.
- An example of a silicone-based organo polysiloxane product is SP 30, which is a powder product sold by Wacker Chemie GmbH, Germany.
- DC2-3485 can be mentioned which is a silicone compound sold by N.V. Dow Corning Europe S.A., Brussels, Belgium.
- the amount thereof is advantageously in the range of 0.15 - 0.60, such as 0.20 - 0.55% by weight.
- agents preventing the running of colour are polyvinyl pyrrolidone (PVP), for instance in form of the product SOKALAN® HP 50 sold by BASF AG, Ludwigshafen, Germany.
- PVP polyvinyl pyrrolidone
- the amount thereof is typically in the range of 0.01 - 1.5, such as 0.01 - 1.0, for instance 0.1 - 0.5% by weight.
- Antiredepositing agents are advantageously included in the laundry detergent tablets according to the invention for preventing a redepositing of soil particles.
- examples thereof are cellulose colloids, such as carboxy methyl cellulose and methyl hydroxy cellulose.
- the amount of antiredepositing agent is typically in the range of 0.5 - 2.5, such as 1.0 - 2.0% by weight.
- polymers advantageously forming part of laundry detergent tablets for washing in hard and/or hot water are polyanionic polymers, such as the ones described in the US-PS Nos. 3,308,067, 3,723,322, 4,144,226 and 4,146,495 as well as GB-PS No. 1,596,756.
- polyanionic polymers such as the ones described in the US-PS Nos. 3,308,067, 3,723,322, 4,144,226 and 4,146,495 as well as GB-PS No. 1,596,756.
- homo- and/or copolymeric carboxylic acids are preferred, as well as the sodium or potassium salts thereof.
- the amount of polymer used is typically in the range of 1.0 - 9.0, such as 3.0 - 7.0, for instance 4.0 - 6.0% by weight.
- Non-limiting examples are polymerisates of acrylic acid, hydroxy acrylic acid, maleic acid, itaconic acid, mesaconic acid, acotinic acid, methylene malonic acid, citraconic acid and the like as well as copolymerisates of the above carboxylic acids together or copolymerisates thereof with other ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl alcohol, vinyl methylether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid and crotonic acid.
- the molecular weight of the homo- and copolymers is in the range of about 1,000 - 1,000,000, preferably 2,000 - 250,000 and most preferred 5,000 - 100,000.
- polycarboxylate especially the sodium salt of acrylic/maleic acid copolymer of a molecular weight of about 70,000 is preferred.
- SOKALAN® CP 5 sold by BASF AG, Ludwigshafen, Germany is an example of a commercial product of such a composition.
- Norasol® products can be mentioned, which are sold by NorsoHaas, France, such as Norasol WL 2B, which is a co-granulate of about 30% polyacrylate of a molecular weight of 4,500 and bicarbonate.
- complex-binding agents and precipitation inhibitors such as EDTA (ethylene diamine tetraacetic acid), DETPA (diethylene triamine pentaacetic acid), HEEDTA (hydroxy ethylethylene diamine triacetic acid), ISDA (isoserine diacetic acid) and phosphonates, i.e. phosphonic acids or salts thereof.
- EDTA ethylene diamine tetraacetic acid
- DETPA diethylene triamine pentaacetic acid
- HEEDTA hydroxy ethylethylene diamine triacetic acid
- ISDA isoserine diacetic acid
- phosphonates i.e. phosphonic acids or salts thereof.
- a particular example of a phosphonate is Dequest 2016 D, which is tetrasodium-1-hydroxyethylene-(1,1-diphosphonate) with a content of active acid of about 60%, and which is sold by Monsanto S.A., Brussels, Belgium.
- ingredients which, if desired, may be included in the laundry detergent tablets according to the invention, are further conventional tablet adjuvants, optical brightener, bleaching agents, bleaching agent activators, agents making the textiles soil-repelling, antiagglutinants, rinsing aids, dyes, deodorising agents, antioxidants and perfume.
- the laundry detergent tablets according to the invention are prepared in a completely conventional manner.
- a basic powder fraction which contains a polyfunctional carboxylic acid and/or a salt thereof, layered silicate and/or alkali metal silicate and/or zeolite, potassium carbonate and optionally sodium carbonate/bicarbonate and/or potassium carbonate/bicarbonate, binder, agents preventing the running of colour, antiredepositing agent, complex-binding agent, and polymer as well as other optinal pulverulent ingredients.
- liquid nonionic tenside is provided, whereby - in case the tenside exists in solid form - heating is performed to above the melting point, for instance to about 40 - 60°C, such as 45 - 55°C.
- a residue fraction is mixed, said fraction containing an amphoteric, pulverulent tenside and optionally a disintegrating agent, an enzyme as well as other ingredients, such as an antifoaming agent which should be subjected to the least possible heat effect and load during the processing in order not to harm the stability of the components.
- the tenside fraction is sprayed onto the basic powder fraction in a suitable mixer while it is continuously stirred for about 5 - 18 minutes depending on to the mixer used, whereafter the residue fraction is added while stirring for about additionally 2 - 10 minutes.
- a free-flowing, slightly granulated powder is obtained of a bulk density of about 600 - 900 g/l.
- the pulverulent mixture is compressed in a tabletting machine, such as KORSCH EK III-type, into tablets of the desired weight and size.
- laundry detergent tablets according to the invention were produced with the compositions CL1 - CL11 stated below in Table 1.
- the laundry detergent tablets were compressed on a tabletting machine of the KORSCH EK III-type by means of a pressure of 50 - 60 kN.
- the tablets had a circular cross section of a diameter of 40 mm, a height of 12 - 14 mm and a weight of 25 g.
- the tablet strength, the disintegration period as well as the increase in volume during storage were measured for each of the prepared laundry detergent tablets and are also indicated in Table 1 below.
- the tablet strength was measured by way of a vertical downward penetration in the middle of the tablet at a speed of 50 mm/min by means of a flat 8 mm ⁇ steel piston on a Holland CT5-tablet strength testing apparatus, and both the initial tablet strength as well as the tablet strength after storage under accelerated aging conditions at 35°C and 75% RH for one week, two weeks and four weeks were measured.
- the disintegration period was measured by placing the tablet in a wire basket of stainless steel and of a circular cross section of a diameter of 50 mm.
- the steel basket was placed in a 1000 ml beaker, into which 900 ml of 20°C thermostat water (11 °dH) was filled. Stirring was carried out at 1000 rpm.
- the tablets have disintegrated when tablet residues can no longer be observed in the wire basket. Both the initial disintegration period as well as the disintegration period after storage for one, two and four weeks under accelerated aging conditions at 35°C and 75% RH were measured. The disintegration period should not be considerably increased during storage.
- the percentage increase in volume of the laundry detergent tablets should be as small as possible, because a small percentage increase in volume indicates a good storage stability.
- the present example illustrates a test carried out at an independent institute, CTTN-IREN INSTITUTE, Ecully Cedex, France, for comparing the washing effect between the present laundry detergent tablets and one of the best products in the market, Persil Megaperls Color supplied by Henkel.
- the latter product is available in form of pearls and has a zeolite content of more than 30%, a content of anionic tensides of from 5 to 15%, a content of nonionic tensides of from 5 to 15% and a content of polycarboxylate and soap of less than 5% (according to the label on the packing).
- the reflection values indicated in the table indicate the efficiency of the laundry detergents used for removing the impregnated stains.
- a high value means a good efficiency, the theoretically highest possible value being 100 corresponding to a completely white surface.
- the degree of brightness was spectrophotometrically measured at repeated washings of a swatch of white fabric. The higher the measured value is, the higher the degree of brightness.
- the laundry detergent tablets according to the invention show a washing effect which is completely abreast of and even slightly better than Persil Megaperls Color. This is even more surprising as a considerably smaller amount of tenside is included in the laundry detergent tablets according to the invention compared to Persil Megaperls Color. Thus a total of 5.0 g of tenside is included in the amount of CL9 used, whereas a total of 8 to 24 g of tenside is included in the amount of Persil Megaperls Color used (according to the label on the packing). The degree of brightness is almost the same for both products, and a tendency towards a higher degree of brightness applies when increasing the washing temperature.
- the present example illustrates a test carried out for a comparison of the washing effect between the laundry detergent tablets according to the invention and two of the best products in the market Persil Megaperls Color sold by Henkel and Ariel Futur Color sold by Procter & Gamble.
- Ariel Futur Color is a pulverulent product and contains 5 to 15% of anionic tensides, 5 to 15% of nonionic tensides, 5 to 15% polycarboxylates, 15 to 30% zeolites and less than 5% phosphonates (according to the label on the packing).
- the effect of the laundry detergent tablets according to the invention is almost abreast of the known products for the tested types of soil. This is a surprisingly good result, as a considerable lower amount of tenside is used in the laundry detergent tablets according to the invention compared to the known products.
- 5.0 g of tenside is included in CL9 and 5.1 g of tenside in CL10
- Ariel Futur Color includes a total of from 8 to 24 g and Persil Megaperls Color of from 8.4 to 25.2 g (according to the labels on the respective packings).
- Table 4 Type of soil Before washing KAO 1.1 50 g powder CL 8 50 g powder Standard soil on cotton 38.50 55.89 54.18 Standard soil on mixed fibres 50.66 70.20 66.81 Sebum on cotton 38.31 61.57 57.85 Blood, milk, ink on cotton 12.80 35.38 37.00 Blood on cotton 21.64 66.36 62.22 Cocoa on mixed fibres 51.88 70.60 68.21 Pigment/oil 50.51 68.18 66.82 Oil/Pigment/Milk 50.84 65.63 64.98 Average 39.39 61.73 59.76
- the detergent according to EP No. 0 482 627 showed a slightly better washing effect in connection with the tested types of soil compared to the laundry detergent tablets according to the invention.
- a total amount of tenside of 9.7 g is included in the KAO 1.1, whereas only a total of 5.0 g of tenside is included in CL8.
- Table 5 Type of soil Before washing KAO 1.1 50 g powder CL 8 2 x 25 g tablets Standard soil on cotton 38.50 57.56 51.70 Standard soil on mixed fibres 50.66 66.06 64.73 Sebum on cotton 38.31 73.46 62.10 Blood, milk, ink on cotton 12.80 43.71 47.77 Blood on cotton 21.64 67.82 72.03 Cocoa on mixed fibres 51.88 68.77 63.52 Pigment/oil 50.51 67.01 65.84 Oil/Pigment/Milk 50.84 79.75 78.23 Average 39.39 65.52 63.24
- the detergent according to EP No. 0 482 627 showed a slightly better washing effect in connection with the tested types of soil compared to the laundry detergent tablets according to the invention.
- a total amount of tenside of 9.7 g is included in KAO 1.1, whereas only a total of 5.0 g of tenside is included in CL8.
- washing machine Bauknecht ⁇ ko-matic WA 1200 Temperature: 60°C Programme: Standard (without prewash) Water hardness: 18°dH Amount of fabric: 2 kg of normally soiled laundry + 1.5 kg of clean terry towels. Number of washings: 3, i.e. each numerical value indicated is an average of 27 measurements, each test swatch being measured on 3 x 3 areas.
- Spectrophotometer for measuring reflection values Minolta CR 200
- the detergent according to EP No. 0 482 627 displayed a washing effect in connection with the tested types of soil comparable with the laundry detergent tablets according to the invention. This is a surprisingly good result, as the total amount of tenside in KAO 1.1 is considerably higher than the total amount of tenside in the inventive laundry detergent tablets.
- the present example illustrates a test carried out for a comparison of the dissolving period for the laundry detergent tablets according to the invention (CL 8) with the detergent according to EP No. 0 482 627 (KAO 1.1).
- test used 2x25 g of CL 8-tablets as well as 2 x 25 g KAO 1.1-tablets.
- the dissolving period was measured at a washing in a washing machine of the type Bauknecht ⁇ ko-matic WA 1200 using a standard washing programme at 40°C and an amount of water of about 10 l in the main wash.
- the tablets were at the dissolving test placed in a wide-meshed washing bag of 18 x 10 cm in order to prevent the tablets from depositing in the door of the washing machine.
- the washing was carried out on 3.5 kg clean terry towels.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK39996A DK173111B1 (da) | 1996-04-03 | 1996-04-03 | Tøjvasketabletter |
DK39996 | 1996-04-03 | ||
DK399/96 | 1996-04-03 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0799886A2 true EP0799886A2 (fr) | 1997-10-08 |
EP0799886A3 EP0799886A3 (fr) | 1998-11-18 |
EP0799886B1 EP0799886B1 (fr) | 2002-11-27 |
Family
ID=8093095
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19970610007 Expired - Lifetime EP0799886B1 (fr) | 1996-04-03 | 1997-04-02 | Tablettes de détergent pour du linge |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0799886B1 (fr) |
DE (1) | DE69717336T2 (fr) |
DK (1) | DK173111B1 (fr) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999029826A1 (fr) * | 1997-12-08 | 1999-06-17 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de detergent a desintegration amelioree |
WO1999042556A1 (fr) * | 1998-02-20 | 1999-08-26 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules dont les proprietes presentent un profil renforce |
WO1999063045A1 (fr) * | 1998-06-03 | 1999-12-09 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules detergents stables a la rupture et se dissolvant rapidement |
WO2000029541A1 (fr) * | 1998-11-12 | 2000-05-25 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules nettoyants et detergents exempts de parfums |
WO2000039261A1 (fr) * | 1998-12-23 | 2000-07-06 | Henkel Kommanditgesellschaft Auf Aktien | Adjuvant de lavage soluble et de faible dosage |
WO2000043488A1 (fr) * | 1999-01-23 | 2000-07-27 | The Procter & Gamble Company | Comprime detergent |
EP1035196A1 (fr) * | 1999-03-05 | 2000-09-13 | Rohm And Haas Company | Compositions améliorés en forme boulettes |
EP1048717A1 (fr) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Compositions détergentes |
EP1048716A1 (fr) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Composition détergente |
WO2001009278A1 (fr) * | 1999-07-30 | 2001-02-08 | Unilever N.V. | Compositions detergentes |
US6221832B1 (en) | 1998-11-11 | 2001-04-24 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets |
WO2001038476A1 (fr) * | 1999-11-25 | 2001-05-31 | Cognis Deutschland Gmbh & Co.Kg | Pastilles de detergent |
US6313080B1 (en) | 1998-02-04 | 2001-11-06 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc. | Detergent compositions |
GB2362161A (en) * | 2000-03-11 | 2001-11-14 | Mcbride Robert Ltd | Detergent tablets |
WO2002024848A2 (fr) * | 2000-09-20 | 2002-03-28 | Reckitt Benckiser Inc | Ameliorations apportees a des pastilles contenant une enzyme |
WO2002102948A2 (fr) * | 2001-05-31 | 2002-12-27 | Huntsman International Llc A Limited Liability Company Formed Under The Laws Of Delaware, Usa | Poudres compactables |
WO2003076362A2 (fr) * | 2002-03-12 | 2003-09-18 | Huntsman International Llc | Poudres compressibles |
US6974789B1 (en) | 1999-01-23 | 2005-12-13 | The Procter & Gamble Company | Detergent tablet |
WO2006061957A1 (fr) * | 2004-12-09 | 2006-06-15 | Kao Corporation | Agent desincrustant |
US7138139B2 (en) | 2002-10-22 | 2006-11-21 | Rohm And Haas Company | Tablet coating |
EP1953217A1 (fr) | 2007-02-02 | 2008-08-06 | Kemira Agro Oy | Additif granulé utilisé dans les compositions détergentes |
EP2446955B1 (fr) * | 2003-09-30 | 2015-03-25 | Nalco Company | Système d'alimentation de matériaux solides dans un pipeline pressurisé |
EP3227419B1 (fr) | 2014-12-05 | 2019-08-14 | Dalli-Werke GmbH & Co. KG. | Compositions effervescentes comprenant de la pectine |
WO2020214916A1 (fr) * | 2019-04-19 | 2020-10-22 | One Home Brands, Inc. | Production de comprimés |
WO2022263172A1 (fr) * | 2021-06-15 | 2022-12-22 | Unilever Ip Holdings B.V. | Composition en comprimé monodose |
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US7550156B2 (en) | 2001-11-23 | 2009-06-23 | Rohm And Haas Company | Optimised pellet formulations |
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EP0482627A1 (fr) * | 1990-10-24 | 1992-04-29 | Kao Corporation | Composition détergente en comprimé |
EP0504091A1 (fr) * | 1991-03-15 | 1992-09-16 | Cleantabs A/S | Composition pour le lavage machinal de la vaisselle sans phosphate |
WO1995020030A1 (fr) * | 1994-01-25 | 1995-07-27 | Unilever N.V. | Co-granules et pastilles detergentes produites a l'aide desdits co-granules |
EP0737738A2 (fr) * | 1995-04-12 | 1996-10-16 | Cleantabs A/S | Comprimés d'agent de blanchiment |
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JPH04239100A (ja) * | 1991-01-11 | 1992-08-26 | Lion Corp | タブレット洗剤組成物 |
JPH06108099A (ja) * | 1992-09-30 | 1994-04-19 | Lion Corp | タブレット洗剤組成物 |
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1996
- 1996-04-03 DK DK39996A patent/DK173111B1/da not_active IP Right Cessation
-
1997
- 1997-04-02 EP EP19970610007 patent/EP0799886B1/fr not_active Expired - Lifetime
- 1997-04-02 DE DE1997617336 patent/DE69717336T2/de not_active Expired - Fee Related
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EP0482627A1 (fr) * | 1990-10-24 | 1992-04-29 | Kao Corporation | Composition détergente en comprimé |
EP0504091A1 (fr) * | 1991-03-15 | 1992-09-16 | Cleantabs A/S | Composition pour le lavage machinal de la vaisselle sans phosphate |
WO1995020030A1 (fr) * | 1994-01-25 | 1995-07-27 | Unilever N.V. | Co-granules et pastilles detergentes produites a l'aide desdits co-granules |
EP0737738A2 (fr) * | 1995-04-12 | 1996-10-16 | Cleantabs A/S | Comprimés d'agent de blanchiment |
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DATABASE WPI Week 9241 Derwent Publications Ltd., London, GB; AN 92-335478 XP002078351 & JP 04 239100 A (LION CORP.) , 26 August 1992 & JP 04 239100 A (...) * |
DATABASE WPI Week 9420 Derwent Publications Ltd., London, GB; AN 94-164283 XP002078352 & JP 06 108099 A (LION CORP.) , 19 April 1994 & JP 06 108099 A (...) * |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999029826A1 (fr) * | 1997-12-08 | 1999-06-17 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de detergent a desintegration amelioree |
US6313080B1 (en) | 1998-02-04 | 2001-11-06 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc. | Detergent compositions |
WO1999042556A1 (fr) * | 1998-02-20 | 1999-08-26 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules dont les proprietes presentent un profil renforce |
WO1999063045A1 (fr) * | 1998-06-03 | 1999-12-09 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules detergents stables a la rupture et se dissolvant rapidement |
US6221832B1 (en) | 1998-11-11 | 2001-04-24 | Stockhausen Gmbh & Co. Kg | Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets |
WO2000029541A1 (fr) * | 1998-11-12 | 2000-05-25 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules nettoyants et detergents exempts de parfums |
WO2000039261A1 (fr) * | 1998-12-23 | 2000-07-06 | Henkel Kommanditgesellschaft Auf Aktien | Adjuvant de lavage soluble et de faible dosage |
US6974789B1 (en) | 1999-01-23 | 2005-12-13 | The Procter & Gamble Company | Detergent tablet |
WO2000043488A1 (fr) * | 1999-01-23 | 2000-07-27 | The Procter & Gamble Company | Comprime detergent |
AU771479B2 (en) * | 1999-01-23 | 2004-03-25 | Procter & Gamble Company, The | Detergent tablet |
EP1035196A1 (fr) * | 1999-03-05 | 2000-09-13 | Rohm And Haas Company | Compositions améliorés en forme boulettes |
US6254892B1 (en) | 1999-03-05 | 2001-07-03 | Rohm And Haas Company | Pellet formulations |
WO2000066690A1 (fr) * | 1999-04-30 | 2000-11-09 | The Procter & Gamble Company | Compositions detergentes |
EP1048716A1 (fr) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Composition détergente |
EP1048717A1 (fr) * | 1999-04-30 | 2000-11-02 | The Procter & Gamble Company | Compositions détergentes |
US6436889B1 (en) | 1999-07-30 | 2002-08-20 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions |
WO2001009278A1 (fr) * | 1999-07-30 | 2001-02-08 | Unilever N.V. | Compositions detergentes |
WO2001038476A1 (fr) * | 1999-11-25 | 2001-05-31 | Cognis Deutschland Gmbh & Co.Kg | Pastilles de detergent |
US6977239B1 (en) | 1999-11-25 | 2005-12-20 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
GB2362161A (en) * | 2000-03-11 | 2001-11-14 | Mcbride Robert Ltd | Detergent tablets |
WO2002024848A3 (fr) * | 2000-09-20 | 2002-08-08 | Reckitt Benckiser Inc | Ameliorations apportees a des pastilles contenant une enzyme |
WO2002024848A2 (fr) * | 2000-09-20 | 2002-03-28 | Reckitt Benckiser Inc | Ameliorations apportees a des pastilles contenant une enzyme |
WO2002102948A2 (fr) * | 2001-05-31 | 2002-12-27 | Huntsman International Llc A Limited Liability Company Formed Under The Laws Of Delaware, Usa | Poudres compactables |
WO2002102948A3 (fr) * | 2001-05-31 | 2003-04-24 | Huntsman Internat Llc A Ltd Li | Poudres compactables |
WO2003076362A2 (fr) * | 2002-03-12 | 2003-09-18 | Huntsman International Llc | Poudres compressibles |
WO2003076362A3 (fr) * | 2002-03-12 | 2004-02-05 | Huntsman Int Llc | Poudres compressibles |
US7138139B2 (en) | 2002-10-22 | 2006-11-21 | Rohm And Haas Company | Tablet coating |
EP2446955B1 (fr) * | 2003-09-30 | 2015-03-25 | Nalco Company | Système d'alimentation de matériaux solides dans un pipeline pressurisé |
JP2006160956A (ja) * | 2004-12-09 | 2006-06-22 | Kao Corp | 洗浄剤 |
WO2006061957A1 (fr) * | 2004-12-09 | 2006-06-15 | Kao Corporation | Agent desincrustant |
EP1953217A1 (fr) | 2007-02-02 | 2008-08-06 | Kemira Agro Oy | Additif granulé utilisé dans les compositions détergentes |
EP1956076A1 (fr) * | 2007-02-02 | 2008-08-13 | Kemira Oyj | Additif granulé utilisé dans les compositions détergentes |
EP3227419B1 (fr) | 2014-12-05 | 2019-08-14 | Dalli-Werke GmbH & Co. KG. | Compositions effervescentes comprenant de la pectine |
WO2020214916A1 (fr) * | 2019-04-19 | 2020-10-22 | One Home Brands, Inc. | Production de comprimés |
CN114096652A (zh) * | 2019-04-19 | 2022-02-25 | 仅一居家品牌有限公司 | 片剂制备 |
US11261409B2 (en) | 2019-04-19 | 2022-03-01 | One Home Brands, Inc. | Tablet production |
WO2022263172A1 (fr) * | 2021-06-15 | 2022-12-22 | Unilever Ip Holdings B.V. | Composition en comprimé monodose |
Also Published As
Publication number | Publication date |
---|---|
DK39996A (da) | 1997-10-04 |
DK173111B1 (da) | 2000-01-31 |
DE69717336D1 (de) | 2003-01-09 |
EP0799886A3 (fr) | 1998-11-18 |
DE69717336T2 (de) | 2003-03-27 |
EP0799886B1 (fr) | 2002-11-27 |
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