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GB2227021A - Phosphate-and silicate-free cleaning compositions - Google Patents

Phosphate-and silicate-free cleaning compositions Download PDF

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Publication number
GB2227021A
GB2227021A GB9000224A GB9000224A GB2227021A GB 2227021 A GB2227021 A GB 2227021A GB 9000224 A GB9000224 A GB 9000224A GB 9000224 A GB9000224 A GB 9000224A GB 2227021 A GB2227021 A GB 2227021A
Authority
GB
United Kingdom
Prior art keywords
acid
composition according
polycarboxylate
alkali
phosphonate
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.)
Granted
Application number
GB9000224A
Other versions
GB9000224D0 (en
GB2227021B (en
Inventor
Jean-Pierre Chavannes
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.)
Sandoz AG
Original Assignee
Sandoz AG
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 Sandoz AG filed Critical Sandoz AG
Publication of GB9000224D0 publication Critical patent/GB9000224D0/en
Publication of GB2227021A publication Critical patent/GB2227021A/en
Application granted granted Critical
Publication of GB2227021B publication Critical patent/GB2227021B/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/06Hydroxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • C11D7/12Carbonates bicarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/265Carboxylic acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/36Organic compounds containing phosphorus

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Description

9 i 1 1 A 1 j- PHOSPHATE- AND SILICATE-FREE LAUNDRY DETERGENT COMPOSITIONS
The invention relates to phosphate and silicate free aqueous washing compositions that contain alkali and a combination of a polycarboxylate and a phosphonate.
It is desirable to avoid having washing compositions containing phosphates and/or silicates. Phosphates are well known to be ecologically undesirable and indeed in certain countries are no longer permitted. Silicates have the disadvantage that they tend to form deposits in the particular washing machine in which they are used.
According to the invention there is provided a phosphate and silicate free aqueous washing composition comprising (i) 5-45% of alkali, (ii) 0.5-20% of polycarboxylate and (iii) 0.1-107. of phosphonate, the balance comprising water.
When preparing compositions according to the invention, the polycarboxylate and/ or the phosphonate can be formed in situ by adding the corresponding free acid which on contact with the alkali forms the salt or by adding the salt form per se.
All percentages given in the compositions according to the invention are by weight of the active compound or material and relate to the total composition.
Further, compositions according to the invention may contain further additives for example other sequestering agents and/or corrosion inhibitors.
Preferably in compositions according to the invention, the ratio Case 150-5302 of polycarboxylate to phosphonate is 1:1 to 30:1, more preferably 1.5:1 to 12:1.
Compositions according to the invention may be used as alkali donors in industrial washing processes. Preferably such a composition according to the invention comprises (i) 15-35%, more preferably 18-30% of alkali, (ii) 3-10%, more preferably 4-7% of polycarboxylate and (iii) 0.2-1.5%, more preferably 0.5-1.2% of phosphonate, the balance being water and one or more compounds selected from sequestering agents and corrosion inhibitors.
Compositions according to the invention may also be used as washing liquids for use in a dish washer. Such compositions must be free of any chlorine containing compounds. Preferably such a composition according to the invention comprises:
(i) 10-35%, more preferably 13-20% of alkali, (ii) 0.5-15%, more preferably 0.5-10.5% of polycarboxylate and (M) 0.2-5%, more preferably 0. 4-3% of phosphonate, the balance comprising water.
The pH of these compositions is preferably over 10.
Preferred alkali used in the aqueous compositions according to the invention are alkali metal -hydroxide or -carbonate, more preferably sodium or potassium hydroxide or carbonate. The alkali can be used in solid form or as a very strongly concentrated aqueous solution.
Preferably in a composition according to the invention the polycarboxylate is one that is preferably derived from medium to high molecular weight polymers (preferably having a molecular weight of 800 1 4 b c - 3 - Case 150-5302 to 500,000, more preferably 1,000-250,000, especially 4,000-120,000); more preferably it is derived from one of the following acids:
methacrylic acid, acrylic acid, a-hydroxyacrylic acid, maleic acid or copolymers thereof.
Such polycarboxylic acids are in aqueous solution. Preferably the polycarboxylic acid is in the form of an alkali metal salt, preferably sodium or potassium salts. Preferably the polymer is a polyaerylate polymer.
Preferred phosphonates are those derived from hydroxy Cl-4alkylene phosphonic acid or aminomethylene phosphonic acid or phosphonic Cl4alkylene carboxylic acid. More preferably the phosphonic acid is one derived from:
1-hydroxyethane-l,l-disphosphonic acid (HEDP), aminotri(methylenephosphonic acid) (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP), Diethylene triamine penta(methylene phosphonic acid) (DETPMP), hexamethylene diamine tetra(methylene phosphonic acid), amine oxide tri(methylene phosphonic acid) and 2-phosphono butane -1,2,4-tricarboxylic acid (PBTC).
Preferably compositions according to the invention contain one or more sequestering agents selected from salts of nitrilotriacetic acid and citric acid. Preferably the amount of sequester ing agent used is from 320%, based on the weight of the composition Preferred salt forms are those derived from the alkali metals, e.g. sodium and potassium.
Where a composition according to the invention is to be used as dish washing machine liquid (and therefore does not contain any chlorine containing compounds), then it optionally includes one or more corrosion inhibitors. Preferred corrosion inhibitors are selected 4 a from sodium nitrite, benzotriazoles or tolyltriazoles. Preferably when a corrosion inhibitor is present it is preferably present in an amount selected from 0.5-1% of sodium nitrite and 0.2-0.4 of benzotriazole or tolyltriazole.
Compositions according to the invention when used as dish washing machine liquids (i.e. without the chlorine containing compounds) have extremely good wash and cleaning properties and also do not have the abovementioned disadvantages associated with phosphate and silicate containing washing liquids.
Compositions according to the invention when used as alkali donors in industrial washing liquids produce stable, strong alkali concentrates, which through the addition of anionic or nonionic surface active agents make up useful industrial washing liquids.
a D The invention will now be illustrated by the following examples in which all amounts are given in percent by weight of the composition.
Polyacrylic acid A has a molecular weight of 100,000 and is used as 29% solution of the half neutralised acid (sodium salt form), polyacrylic acid B has a molecular weight of 4,500 and is used as 49X solution, the sodium salt of nitrilo triacetic acid (NTA) is used as 40% solution, the diethylenetriamine penta(methylene phosphonic acid) (DETPMP) is used as 50% solution and the 1-hydroxyethane-l,l-diphosphonic acid (HEDP) is used as 60% solution, all solutions being in water.
Examples 1-8:
The following compositions were made up as follows:
Table 1
1 2 3 4 6 7 8 Demineralised water 58 39 58 54 36 55 46 56.2 Sodium hydroxide 98% 20 30 10 22 15 21 15 24.8 Potassium hydroxide 95% -- --- 20 -- 15 - Polyacrylic acid B 13 20 10 7 5 9.5 Polyacrylic acid A -- --- is 15 7 5 -- NTA 8 10 10 8 12 9 12 8.5 DEMP 0.5 0.5 1 0.5 1 0.5 1 0.5 HEDP 0.5 0.5 1 0.5 1 0.5 1 0.5 100 100 100 100 100100 This compositions are useful as alkali donors in industrial washing systems.
4 Examples 9-14:
Demineralised water sodium nitrite NTA sodium hydroxide 98% potassium hydroxide 95X Polyacrylic acid B Polyacrylic acid A DEMP HEDP Tolyltriazole The following compositions were made up as follows Table 2
9 10 11 12 13 14 39 33 26 0.7 0.7 0.7 12 12 12 14 16 18 15 17 35 2 3 3 5 5 1.0 2 3 5 5 6 0.3 0.3 0.3 0.3 0.3 27 0.7 12 15 15 20 23 43.7 0.7 -- 12 38.0 is 15.3 17 -- 2.0 100 100 100 100 100 The compositions of examples 9-14 are useful as dish washing machine liquids.

Claims (13)

  1. Claims:
    Case 150-5302 1. A phosphate and silicate free aqueous composition comprising (i) 5-45X of alkali, (ii) 0.5-20% of polycarboxylate and (iii) 0.1-10X.of phosphonate, the balance comprising water.
  2. 2. A composition according to Claim 1 in which the ratio of polycarboxylate to phosphonate is 1:1 to 30:1.
  3. 3. A composition according to Claim 1 or Claim 2 comprising (i) 15-35% of alkali, (ii) 3-10% of polycarboxylate and (M) 0.2-1.5% of phosphonate, the balance being water and one or more compounds selected sequestering agents and corrosion inhibitors.
  4. 4. A composition according to any one of Claims 1 to 3 comprising (i) 1035% of alkali, (ii) 0.5-15% of polycarboxylate and (M) 0.2-5% of phosphonate, the balance comprising water.
  5. 5. A composition according to any one of the preceding claims in which the alkali used is an alkali metal -hydroxide or -carbonate.
  6. 6. A composition according to any one of the preceding claims in which the polycarboxylate has a molecular weight of 1,000 to 250,000.
  7. 7. A composition according to Claim 6 in which the carboxylate is a salt derived from those selected from one of the following acids:
    i Case 150-5302 methacrylic acid, acrylic acid, cc-hydroxyacrylic acid, maleic acid or copolymers thereof.
  8. 8. A composition according to any one of the preceding claims in which the phosphonates are salts of one of the following acids: hydroxy Cl4alkylene phosphonic acid or aminomethylene phosphonic acid or phosphonic Cl-4alkylene carboxylic acid.
  9. 9. A composition according to any one of the preceding claims in which the phosphonate is a salt of one or more of the following phosphonic acids: 1-hydroxyethane-l,l-disphosphonic acid (HEDP), aminotri(methylene phosphonic acid) (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP), diethylene triamine penta(methylene phosphonic acid) (DETPMP), hexamethylene diamine tetra(methylene phosphonic acid), amine oxide tri(methylene phosphonic acid) and 2-phosphono butane -1,2,4tricarboxylic acid (PBTC).
  10. 10. A composition according to any one of the preceding claims containing one or more sequestering agents selected from salts of nitrilotriacetic acid and citric acid.
  11. 11. A composition substantially as herein described with reference to any one of Examples 1 to 14.
  12. 12. A detergent composition containing a composition according to any one of the preceding claims and one or more surface active agents.
  13. 13. A detergent composition according to Claim 12 in which the surface active agents are selected from anionic or nonionic surface active agents.
    Published 1990 at The Patent Office, State House, 6"1 Holborn, London WC1R4TP. Further copies maybe obtainedfrom The Patent 0Mce. Sales Branch, St Mary Cray, Orpington, Kent BR5 3ED. Printed by Multiplex tecbxuques ltd, St Mary Cray, Kent, Con. 1187 Sales Branch, St Mary Gray, Orpington, lient Bitb;jkw. kTinteci oy mxutipiex tecnxuques mi, bT, jaury ur&Ly, jr!, unL, vv" &,..
GB9000224A 1989-01-07 1990-01-05 Phosphate-and silicate-free detergent compositions Expired - Lifetime GB2227021B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3900310 1989-01-07

Publications (3)

Publication Number Publication Date
GB9000224D0 GB9000224D0 (en) 1990-03-07
GB2227021A true GB2227021A (en) 1990-07-18
GB2227021B GB2227021B (en) 1992-08-05

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ID=6371680

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9000224A Expired - Lifetime GB2227021B (en) 1989-01-07 1990-01-05 Phosphate-and silicate-free detergent compositions

Country Status (7)

Country Link
JP (1) JPH02228399A (en)
BE (1) BE1003581A5 (en)
CH (1) CH679311A5 (en)
FR (1) FR2641544A1 (en)
GB (1) GB2227021B (en)
IT (1) IT1239740B (en)
NL (1) NL9000040A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659872A1 (en) * 1993-12-23 1995-06-28 The Procter & Gamble Company Rinsing compositions
EP0659873A1 (en) * 1993-12-23 1995-06-28 The Procter & Gamble Company Rinsing compositions
EP0791095A1 (en) * 1994-11-10 1997-08-27 The Procter & Gamble Company Method of cleaning carpets
WO1997031996A1 (en) * 1996-02-29 1997-09-04 Unilever N.V. Machine dishwashing gel compositions
US5801137A (en) * 1993-12-23 1998-09-01 The Procter & Gamble Company Detergent compositions containing (poly)carboxylates, organo diphosphonic and acrylic acid derived components, and silicate
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US5928384A (en) * 1994-11-10 1999-07-27 The Procter & Gamble Company Method of cleaning carpets
EP1253192A1 (en) * 2001-04-23 2002-10-30 BetzDearborn Inc Anti-scuffing treatment for alkaline bottle washing systems
EP2604677A1 (en) * 2011-12-14 2013-06-19 Soro Internacional S.A. Detergent for dishwashing machine

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9423495D0 (en) * 1994-11-21 1995-01-11 Unilever Plc Cleaning method
JP3566015B2 (en) * 1997-02-17 2004-09-15 花王株式会社 Detergent composition for dishwashers
DE10002710A1 (en) * 2000-01-22 2001-08-02 Henkel Ecolab Gmbh & Co Ohg Production of creamy alkaline-aqueous cleaning agents containing complexing agents
JP6232246B2 (en) * 2013-09-26 2017-11-15 シーバイエス株式会社 Cleaning composition for automatic dishwasher and method of using the same
JP6444245B2 (en) * 2015-04-06 2018-12-26 株式会社Adeka Concentrated liquid detergent composition for automatic dishwasher and method for washing dishes with automatic dishwasher
JP6490292B2 (en) * 2018-11-27 2019-03-27 株式会社Adeka Concentrated liquid detergent composition for automatic dishwasher and method for washing dishes with automatic dishwasher

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1234320A (en) * 1968-11-02 1971-06-03
GB1314790A (en) * 1970-11-20 1973-04-26 Benckiser Gmbh Joh A Prevention of scale-forming deposits in aqueous systems containing hard water
GB2051115A (en) * 1979-05-31 1981-01-14 Chemed Corp Detergent additive
GB2203163A (en) * 1987-04-03 1988-10-12 Sandoz Ltd Dishwasher detergents

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1252838B (en) * 1965-04-01
GB1443570A (en) * 1973-09-17 1976-07-21 Diversey Ltd Detergent compositions
AU7353874A (en) * 1973-09-26 1976-03-25 Diversey Australasia Hard water scale control
DE3717227A1 (en) * 1987-05-21 1988-12-01 Henkel Kgaa PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1234320A (en) * 1968-11-02 1971-06-03
GB1314790A (en) * 1970-11-20 1973-04-26 Benckiser Gmbh Joh A Prevention of scale-forming deposits in aqueous systems containing hard water
GB2051115A (en) * 1979-05-31 1981-01-14 Chemed Corp Detergent additive
GB2203163A (en) * 1987-04-03 1988-10-12 Sandoz Ltd Dishwasher detergents

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659872A1 (en) * 1993-12-23 1995-06-28 The Procter & Gamble Company Rinsing compositions
EP0659873A1 (en) * 1993-12-23 1995-06-28 The Procter & Gamble Company Rinsing compositions
US5712244A (en) * 1993-12-23 1998-01-27 Proctor & Gamble Company Rinse aid compositions comprising non-nitrogen-containing organs diphosphonic acid, salt or complex thereof
US5801137A (en) * 1993-12-23 1998-09-01 The Procter & Gamble Company Detergent compositions containing (poly)carboxylates, organo diphosphonic and acrylic acid derived components, and silicate
EP0659874B1 (en) * 1993-12-23 2002-10-09 The Procter & Gamble Company Detergent compositions
EP0791095A1 (en) * 1994-11-10 1997-08-27 The Procter & Gamble Company Method of cleaning carpets
EP0791095A4 (en) * 1994-11-10 1997-10-15 Procter & Gamble Method of cleaning carpets
US5928384A (en) * 1994-11-10 1999-07-27 The Procter & Gamble Company Method of cleaning carpets
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
WO1997031996A1 (en) * 1996-02-29 1997-09-04 Unilever N.V. Machine dishwashing gel compositions
EP1253192A1 (en) * 2001-04-23 2002-10-30 BetzDearborn Inc Anti-scuffing treatment for alkaline bottle washing systems
EP2604677A1 (en) * 2011-12-14 2013-06-19 Soro Internacional S.A. Detergent for dishwashing machine

Also Published As

Publication number Publication date
JPH02228399A (en) 1990-09-11
GB9000224D0 (en) 1990-03-07
GB2227021B (en) 1992-08-05
BE1003581A5 (en) 1992-04-28
IT9047510A0 (en) 1990-01-08
NL9000040A (en) 1990-08-01
IT9047510A1 (en) 1990-07-08
IT1239740B (en) 1993-11-15
FR2641544A1 (en) 1990-07-13
CH679311A5 (en) 1992-01-31
FR2641544B1 (en) 1994-07-13

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19960105