Deprecated: The each() function is deprecated. This message will be suppressed on further calls in /home/zhenxiangba/zhenxiangba.com/public_html/phproxy-improved-master/index.php on line 456
AU713088B2 - Nta/edta-containing detergent composition - Google Patents
[go: Go Back, main page]

AU713088B2 - Nta/edta-containing detergent composition - Google Patents

Nta/edta-containing detergent composition Download PDF

Info

Publication number
AU713088B2
AU713088B2 AU17232/97A AU1723297A AU713088B2 AU 713088 B2 AU713088 B2 AU 713088B2 AU 17232/97 A AU17232/97 A AU 17232/97A AU 1723297 A AU1723297 A AU 1723297A AU 713088 B2 AU713088 B2 AU 713088B2
Authority
AU
Australia
Prior art keywords
detergent composition
nta
tableted
edta
alkali metal
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
AU17232/97A
Other versions
AU1723297A (en
Inventor
Patricia Anderson
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.)
Unilever PLC
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
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of AU1723297A publication Critical patent/AU1723297A/en
Application granted granted Critical
Publication of AU713088B2 publication Critical patent/AU713088B2/en
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
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets

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)

Description

WO 97/29175 PCT/EP97/00594 NTA EDTA-CONTAINING DETERGENT COMPOSITION Field of the invention The present invention relates to a detergent composition which incorporates sodium salts of nitrilotriacetic acid and/or ethylenediaminetetraacetic acid, as sequestering agents and detergent builders.
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 the like.
Unlike products used in the home, institutional detergents are often sold in bulk and dispensed from mechanical dispensers. There are a variety of different 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.
One particularly beneficial detergent form is the tablet.
Large compressed tablets of detergent formulation can be formed and held in bulk. These can be dispensed by spraying water against the tablets, causing the detergent to dissolve, and collecting this dissolved, concentrated detergent solution for use. These tableted detergent compositions can take a variety of different forms and include many different detergent compositions, as desired. Powders are also widely used. These are also dispensed from spray dispensers.
However, because of their form, care must be taken to assure that they do not cake up in the dispensers. Further, components of powdered detergents must be uniformly mixed.
The physical properties of the components can affect this.
CONFIRMATION COPY WO 97/29175 PCT/EP97/00594 2 Typical detergent compositions will include a source of alkalinity, a sequestering agent and/or builders, surfactants, antiredeposition aids and the like. Typically, phosphates are used as sequestering agents and detergent builders. However, in some applications it is desirable to replace the phosphates with other sequestrants and builders such as the alkali metal (preferably sodium) salts of nitrilotriacetic acid and ethylenediaminetetraacetic acid, also referred to as "NTA" or "EDTA." Unfortunately, these particular products are extremely fine powders. In powdered detergent formulations, these tend to cake up and clog the S dispenser. These are also difficult to process and, due to S* their particle size, are almost impossible to blend and compress to form tablets. Accordingly, it is very difficult to replace all of the phosphates with NTA or EDTA in either a *powdered detergent or in a tableted detergent.
DE-A-2 141 280 discloses coated particulate EDTA prepared by Sagglomerating EDTA powder with liquid fatty acid, as well as several fully-formulated cleaning compositions comprising said i coated EDTA granules. GB-A-1 240 798 discloses a process for the production of disodium nitrilotriacetate from the corresponding trisodium salt, said trisodium salt being neutralised during an r agglomeration process by spraying an aqueous solution of an acid thereon.
WO-A-95/15369 relates to a process for preparing highly absorptive Ire NTA-containing granules, in which NTA powder is contacted with a S* pertially neutralising amount of an acidic solution.
DE-A-3 604 223 refers to a process wherein aqueaous solutions of both NTA and polyacrylic acid are contacted, the resulting mixture being subsequently dried to powders or granules.
0 0 0 :0 00: 0 S: 06 0 0 0 0 00 000 •o •f WO 97/29175 PCT/EP97/00594 Summary of the Invention c
S
0 0* r 0 i
S.
9* 9. 91r~ 9 Accordingly, it is object of the present invention to provide a detergent composition which incorporates NTA and/or EDTA as the builder replacing the phosphates. Further, it is an object of the present invention to provide an NTA/EDTA product which can be easily compacted to form a tableted detergent.
The objects and advantages of the present invention are achieved through the use of an agglomerated NTA/EDTA Accordingly, the present invention provides a chemical composition comprising an alkali metal salt selected from the group consisting of alkali metal salts of nitrilotriacetic acid and alkali metal salts of ethyleenediaminetetraa acid, wherein said alkali metal salt is agglomerated with a liquid active detergent composition to form an agglomerated alkali metal salt.
6e.S 'S 0e j090iS 9 5* 0
I.
0055 00 .500 5 000 0 S S S 0 0 0 0 S 0 0 0 6 0 00 0650 OS 0000 0 00 SO @5 5 0e *S OS 0000 000 00 0 0 0 0 0 500 05. S 005 000 WO 97/29175 PCTI/EP97/00594 3 Hereinafter, the reference to NTA/EDTA will specifically include NTA, EDTA and mixtures of NTA and EDTA. More specifically, the NTA/EDTA is combined with a liquid in a mixing apparatus to cause the NTA/EDTA to form agglomerated particles. These agglomerated particles can then be mixed and compacted to form a tableted detergent composition.
In a preferred embodiment of the present invention, the liquid used to agglomerate the NTA/EDTA is a functionally active material which contributes to the detergency of the final blend, such as an aqueous dispersion of antiredeopsition polymer, a surfactant, a defoaming agent, or S other liquid active detergent composition. This enables the functional liquid components or composition to be thoroughly 00 mixed with the NTA/EDTA and subsequently uniformly mixed with the detergent composition. This facilitates uniform blending :i of low concentration liquid components. Further, the S agglomerate NTA/EDTA will not cake as easily as untreated S NTA/EDTA. This also enables the NTA/EDTA to be compacted easily to achieve a strong, nonfriable tablet, which is not possible on a commercial scale with powdered NTA/EDTA.
Other objects and advantages of the present invention will be further appreciated in light of the following detailed description.
Detailed Description The present invention is a compressed tebleted detergent composition which incorporates NTA/EDTA in an agglomerated form. The detergent formulations of the present invention can include a variety of different compositions for use in institutional or industrial cleaning applications. These compositions would include, but not be limited to, blends Ssuitable for use as See T• o o o oo WO 97/29175 PCT/EP97/00594 4 ware washing detergents, cutlery presoaks, all purpose cleaners, floor cleaners, sanitizers, disinfectants, descalers, oven/grill cleaners, degreasers and rinse aids.
Although these vary widely in composition, they can all incorporate the agglomerated NTA/EDTA of the present invention. One example of the present invention will be a tableted ware washing detergent. Such ware washing detergents preferably include a source of alkalinity (typically caustic, silicates or soda ash), a hardness sequestering system, low molecular weight water-soluble polymers, nonionic and/or defoaming surfactants, processing aids and optionally i bleaching sources.
The hardness sequestering system of the present invention will primarily be formed from alkali metal salts of nitrilotriacetic acid and ethylenedinitrilotetraacetic acid.
optionally, the detergent composition can also include alkali metal salts of gluconic acid, the alkali metal salts of citric acid, and even the phosphates. However, phosphates would generally not be incorporated with the detergent composition of the present invention in combination with NTA/EDTA. Generally, the hardness sequestering system will form from 10% to 50% by weight of the overall tableted detergent composition and preferably 25% to 50% by weight.
As discussed below, the NTA/EDTA is agglomerated using a liquid component functionally active in the final detergent **c formulation. The NTA/EDTA is agglomerated using well-known chemical mixers which disperse a spray of liquid over the NTA/EDTA as it is being agitated. This eventually forms an agglomerated mass of the NTA/EDTA. The liquid used to agglomerate the NTA/EDTA will be an active detergent composition. This can, for example, include a surfactant, a Sdefoaming agent, an aqueous solution of 09* &0 0 0000 00 0060 0 0 0 0 WO 97/29175 PCTEP97/00594 polycarboxylic acid and/or other detergent compositions which are dissolved in water such as polysilicates and the like.
Suitable liquids also include functionally active components which are liquid at an application temperature. Functionally active components which can be melted and applied (such as waxy materials) can also be included.
The most preferred liquid active detergent composition is selected from the group consisting of an aqueous solution of a polycarboxylic acid, surfactants, defoaming agents and mixtures thereof. An aqueous solution of a polycarboxylic acid being an especially preferred liquid for agglomerating the alkali metal salt of the present invention.
These liquids are combined onto the NTA/EDTA in an amount sufficient to agglomerate the NTA/EDTA and, at the same time, avoid the formation of a sticky mass. The rate of addition is typically controlled to allow any water or other solvent to evaporate off and/or be absorbed with the remaining liquid as it is mixed with the NTA/EDTA.
Generally from about 1% to about 40% by weight of liquid component relative to the weight of the NTA/EDTA is combined to agglomerate the NTA/EDTA. Preferably, about 10% to 30% by weight of liquid component will be added and ideally about This will, of course, vary depending upon the liquid employed. Further, generally at least a portion will be removed by evaporation. An apparatus suitable for agglomeration is disclosed US Patent 4,182,683. Other blending equipment which permits the liquid component to be uniformly mixed with NTA/EDTA powder will, of course, work.
In formulating a detergent, it is possible to either combine all of the liquid components together and add this mixture to the NTA/EDTA, or selectively add different liquid components.
WO 97/29175 PCT/EP97/00594 6 One preferred component which forms an agglomerated NTA/EDTA is the aqueous solution of polycarboxylic acid. This, when combined with the NTA/EDTA, forms an excellent agglomerate.
The NTA/EDTA is preferably agglomerated to form particles having a size of 300 to 1500 microns or larger, and preferably 800-1500 microns. This will provide a freeflowing material which can be used as is or admixed with other similar active materials to form detergent blends having desirable properties and can be easily dispensed and/or further processed.
Industrial and commercial tableted ware washing detergents generally include a caustic source such as sodium or i..t potassium hydroxide, with sodium hydroxide being preferred.
Generally, these may be included at a level from about 0 to 70% by weight, with 30% to 55% being preferred. For a high caustic detergent composition, the caustic content will generally be from about 45% to 55% by weight. The present invention can optionally include a bleaching agent such as alkali metal perborates and percarbonates. This is added in SS*' amounts up to 20% by weight.
In addition to the above, the tableted detergent composition can include defoaming agents, typically nonionic surfactants.
The nonionic surfactant used herein is selected from the 3 group including alcohol ethoxylates, block copolymers and mixtures thereof. Generally, these will have a molecular i* weight of 900 to about 4000. One such surfactant is an ethylene oxide, propylene oxide block copolymer.
Commercially available surfactants include Tritan CF32 Tritan DF12®, Plurafac LF131®, Plurafac LF132®, Plurafac LF231®, Industrol N3®, and Genepal PN30®. These can be included in n 0 0. 0. 5 5 S C -S L O° WO 97/29175 PCT/EP97/00594 7 amount from about 0.5% to about 5% with about 1.5% by weight preferred.
The detergent formulation can also include other surfactants, generally anionic surfactants. Particular anionic surfactants include alkyl aryl sulfonate and alkyl aryl sulfate. The ether sulfates in particular could act as the agglomerating agents. These are present in an amount of 1 to 20% by weight.
SThe tableted detergent composition of the present invention S* can also include low molecular weight (2,000-20,000), water soluble, polymeric acid such as polyacrylic acid, polymethacrylic acid or polymaleic acid or copolymers thereof. These are used as sequestering aids, to inhibit growth of calcium carbonate crystals and to improve rinsability Preferably, the water soluble polymer will be a polycarboxylic acid such as polyacrylic acid having a molecular weight of around 5000. Generally, the composition of the present invention should include 1% to 10% by weight polyacrylic acid on an actives basis, with 2-5% preferred.
These are generally available in a 50% aqueous solution.
The agglomerated NTA/EDTA can be dry mixed with other usually applied detergent components in amounts which meet the desired performance characteristics. These constituents are mixed to form effective powdered detergent formulations preferably including from 1% to 50% by weight of the invention agglomerated NTA/EDTA and a detergent builder.
These powdered detergent formulations are to form a tableted detergent. To form a 14 s 0 0 0 r r o ii__n: 1I__ _IIIDil;__i__liJ__1__ WO 97/29175 PCT/EP97/00594 il 0 j .1 00 0 0:04 i 0 to 00.0 00 E0/ 0 0 3f 0 tableted detergent, the agglomerated NTA/EDTA is blended with the other solid detergent compositions and any remaining liquid components are separately combined and then sprayed onto this mixture of solid detergent components. With a highly caustic detergent, the caustic is added last after the liquid has been sprayed onto the remaining blend.
This formed detergent blend which preferably comprises a detergent builder and from about 1 to about 5011 by weight of the chemical composition according to the invention, is then compressed to form tablets using a standard tableting machine. One such machine suitable for use in the present invention is a 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 6 to 7 mm and a diameter of about 20 mm. The maximum diameter will be a function of the dispenser/feed water interface area. Tablets must be able to fall down upon the dispenser interface.
Test Method To test the formulation of the present invention, granularized NTA was formed by granularizing NTA crystals with an aqueous solution of Accusol 445®, a water-soluble polyacrylate. The Accusol 445 was combined with sufficient water to make it easily sprayable and was then added to NTA crystals using a granulator. The granularized product was then dried and ready for use. The granularized NTA included NTA and 10% polyacrylate solids. These were then formulated into the following detergents: a machine dishwashing detergent, a powdered presoak detergent, and an all-purpose powder detergent.
It was noted when these were formulated that the granular NTA was signficantly easier to blend than crystalline NTA.
Srther, these powdered detergents using the granulated NTA s0 o* 0 .0 o0 0 *S 00* @o 00 6• 0o 0 gD 00 *So o 00 _0111 WO 97/29175 PCT/EP97/00594 9 were less likely to cake as a result of the presence of the NTA. However, the presoak and all-purpose did cake due to the high concentration of soda ash. But again, these were easier to formulate than detergent compositions including only crystalline, non-agglomerated
NTA.
Machine Dishwashing Detergent Powder To a clean, dry mixer, add the following: Granular NTA (10% polyacrylate) 44.5% Soda Ash 9.50 mix 2 minutes, then slowly add: Nonionic surfactant [Industrol N3] 1.00 mix 5 minutes, then add: Caustic Bead 45.00 mix 5 minutes, then pack out into capsules.
Presoak Powder To a clean, dry mixer, add the following: Granular NTA (10% polyacrylate) 22.00% Soda Ash 50.00 Sodium Metasilicate Pentahydrate 5.00 Sodium Sulfate 18.00 mix 2 minutes, then slowly add: LAS Acid 2.75 mix 2 minutes, then slowly add: Nonionic Surfactant [Neodol 91-6] 2.25 mix 5 minutes, then pack out into a capsule.
All Purpose Powder To a clean, dry mixer, add the following: Granular NTA (10% polyacrylate) 27.70% Soda Ash 39.30 Sodium Metasilicate Pentahydrate 9.00 Sodium LAS 6.00 Boric Acid 10.00 mix 2 minutes, then slowly add: Neodol 91-6 8.00 WO 97/29175 PCT/EP97/00594 mix 5 minutes, then pack out in a capsule.
Tableted Detergent Granular NTA (10% polyacrylate) 42.0% Soda Ash 11.5 Nonionic Surfactant [Pluronic 25R8] Caustic Bead 45.0 The detergents of the present invention can be placed in a container and dispensed. The optimum shape and configuration of the container will obviously vary, depending upon the particular dispenser. The agglomerated NTA/EDTA of the present invention can be used in a wide variety of tableted detergent compositions.
Other advantages of the present invention will be readily apparent to one of ordinary skill in the art.

Claims (7)

1. A compressed tableted detergent composition, comprising a detergent builder characterised in that the said composition further comprises 1% to 50 by weight of an agglomerated alkali metal salt selected from the group consisting of alkali metal salts of nitrilotriacetic acid and alkali metal salts of ethylene- diaminetetraacetic acid, wherein said alkali metal salt is agglomerated with a liquid active detergent composition. S,
2. The tableted detergent composition claimed in claim 1, wherein said liquid active detergent composition is selected from the group consisting of an aqueous solution of a S polycarboxylic acid, surfactants, defoaming agents and mixtures I thereof.
3. The tableted detergent composition claimed in claim 2, wherein said liquid active detergent composition comprises an aqueous solution of a polycarboxylic acid. i 0
4. The tableted detergent composition, claimed in claim 3 wherein said polycarboxylic acid is polyacrylic. *4
5. The tableted detergent composition claimed in claim 1, S* comprising 10 to 50% of a hardness sequestering system primarily consiting of said agglomerated alkali metal salt.
6. The tableted detergent composition claimed in claim 4, comprising 1-10% by weight polyacrylic acid on an actives basis. *t f o 6t 41 000 00 04 0 *1 0* 41" 0 4 1 0 4 0 6 *1 *0 ft ft ftftftf ftC ftf ftftftf ft ft f WO 97/29175 PCT/EP97/00594
7. The tableted detergent composition claimed in claim 1, further comprising about 0.5 to about 50% nonionic surfactant selected from the group consisting of alcohol ethoxylates, block copolymers and mixtures thereof. The tableted detergent composition claimed in claim 1, i'I further comprising 1 to 20% by weight of an anionic surfactant. DATED ~\Y ~~Signed for and on behlf ofUIEEPL U r Australia Limited B. ONES, y Secretary. 6O CO S S 0* S 00 5* S ceo. ~55* 0 SOS. @0 OS 00 0@ 0 0 ROSS 50 SOSS S SOC 0 C S S 0 5 C 5 0 0 S OS c c Oc *S OS ScOS 0 cc go S. S S cc co cc ccc... eec cc S 0 0 cc *0 @00 0 0e 050
AU17232/97A 1996-02-12 1997-02-10 Nta/edta-containing detergent composition Ceased AU713088B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1150296P 1996-02-12 1996-02-12
US60/011502 1996-02-12
PCT/EP1997/000594 WO1997029175A1 (en) 1996-02-12 1997-02-10 Nta/edta-containing detergent composition

Publications (2)

Publication Number Publication Date
AU1723297A AU1723297A (en) 1997-08-28
AU713088B2 true AU713088B2 (en) 1999-11-25

Family

ID=21750667

Family Applications (1)

Application Number Title Priority Date Filing Date
AU17232/97A Ceased AU713088B2 (en) 1996-02-12 1997-02-10 Nta/edta-containing detergent composition

Country Status (6)

Country Link
EP (1) EP0880577A1 (en)
AU (1) AU713088B2 (en)
BR (1) BR9707279A (en)
CA (1) CA2243472A1 (en)
WO (1) WO1997029175A1 (en)
ZA (1) ZA971163B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19651072A1 (en) * 1996-12-09 1998-06-10 Henkel Kgaa Additive for detergents or cleaning agents
DE19937428A1 (en) * 1999-08-07 2001-02-08 Henkel Kgaa Detergent tablets
CN118974225A (en) 2022-04-15 2024-11-15 埃科莱布美国股份有限公司 PPE-free tablet degreaser and multi-purpose cleaner

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE374762B (en) * 1968-03-04 1975-03-17 Monsanto Co
DE2141280A1 (en) * 1971-08-18 1973-03-01 Henkel & Cie Gmbh Tetrasodium edta particles coated with fatty acids - - for use in bleaching and washing compsns
DE3604223A1 (en) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Additive for detergents and cleaners
US4687592A (en) * 1985-02-19 1987-08-18 The Procter & Gamble Company Detergency builder system
GB8608148D0 (en) * 1986-04-03 1986-05-08 Procter & Gamble Liquid cleaner
WO1995015370A1 (en) * 1993-12-03 1995-06-08 Monsanto Company Granular alkali metal nitrilotriacetate

Also Published As

Publication number Publication date
EP0880577A1 (en) 1998-12-02
CA2243472A1 (en) 1997-08-14
BR9707279A (en) 1999-04-13
AU1723297A (en) 1997-08-28
ZA971163B (en) 1998-08-12
WO1997029175A1 (en) 1997-08-14

Similar Documents

Publication Publication Date Title
EP0719325B1 (en) Tableted detergent, method of manufacture and use
JP5270055B2 (en) Cleaning composition and method for removing dirt
TW200524B (en)
JP3147901B2 (en) How to make detergent tablets for dishwashers
CA2368428C (en) Solid pot and pan detergent
AU2024201683B2 (en) Stable anhydrous dish soap and method of making same
US5759976A (en) Process for forming tableted high-caustic detergent
JPH05202398A (en) Detergent powder and its preparation
EP0569445B1 (en) Process for manufacturing cast silicate-based detergent
CN118647703A (en) Granular Additives
TWI592481B (en) Solid detergent composition
AU713088B2 (en) Nta/edta-containing detergent composition
AU714999B2 (en) Process for forming tableted high-caustic detergent
US4111853A (en) Particulate composition of sodium alpha olefin sulfonate and sodium silicate
EP1953217B1 (en) A cogranule for use in solid detergent compositions
HU216096B (en) Lower-buildup dish-washing detergents
US6586386B2 (en) Tablet of compacted particulate cleaning composition
JPH04239100A (en) Tabletted detergent composition
SU952952A1 (en) Process for producing granulated enzyme detergent
MXPA04005922A (en) Shaped bodies having detergent or cleaning action for use in a household.
JP2003193091A (en) Hydrous inorganic particles and detergent composition containing the same
WO2001053446A2 (en) Production of an alkaline aqueous detergent creme containing a complexing agent

Legal Events

Date Code Title Description
MK14 Patent ceased section 143(a) (annual fees not paid) or expired