CH679311A5 - - Google Patents
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- CH679311A5 CH679311A5 CH27/90A CH2790A CH679311A5 CH 679311 A5 CH679311 A5 CH 679311A5 CH 27/90 A CH27/90 A CH 27/90A CH 2790 A CH2790 A CH 2790A CH 679311 A5 CH679311 A5 CH 679311A5
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- alkali
- contain
- polycarboxylic acids
- phosphonates
- Prior art date
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- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000004851 dishwashing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 17
- 150000007513 acids Chemical class 0.000 claims description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 13
- 239000003599 detergent Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 150000001447 alkali salts Chemical class 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 239000003352 sequestering agent Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000010412 laundry washing Methods 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular 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
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/12—Carbonates bicarbonates
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic 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)
Abstract
A phosphate and silicate-free aqueous composition comprising (i) 5-45% of alkali (ii) 0.5-20% of polycarboxylate and (iii) 0.1-10% of phosphate the balance comprising water. Such compositions are useful in dish or laundry washing or in industrial washing systems.
Description
Die Erfindung betrifft phosphat- und silikatfreie Wirkstoffgemische, die neben Alkali eine Kombination von Polycarbonsäuren und Phosphonaten enthalten und als Alkalispender für Industriewaschmittel bzw. als Geschirrwaschmittel eingesetzt werden können.
Kombinationen von Polycarbonsäuren und Phosphonaten sind in verschiedener Form bereits bekannt, sie wurden bisher als Gerüststoff-Zubereitung, als Entkalkungsmittel oder als Stabilisator für Peroxid-Lösungen eingesetzt. Diese bekannten Kombinationen wurden jedoch nicht als konzentrierte, stark alkalische Lösungen angeboten, sondern entweder als alkalifreie Konzentrate oder als verdünnte Lösungen beschrieben, die meistens noch andere Bestandteile und oft auch Phosphate und/oder Silikate enthalten. Es sollte aber aus verschiedenen Gründen allgemein vermieden werden, in Waschmitteln Phosphate und/oder Silikate einzusetzen. Phosphate sind wegen ihrer Umweltbelastung in verschiedenen Ländern nicht mehr zugelassen, Silikate verursachen Inkrustationen oder Ablagerungen in den Apparaturen.
Gegenstand der Erfindung sind phosphat- und silikatfreie Wirkstoffgemische, die in wässriger Lösung 5-45% Alkali, 0,5-20% Polycarbonsäuren in Form ihrer Alkalisalze und 0,1-10% Phosphonate enthalten, wobei alle Prozentangaben als Gewichtsprozente der reinen Wirkstoffe zu verstehen sind und sich auf die Gesamtlösung beziehen. In diesen Zubereitungen sind die Polycarbonsäuren in Form ihrer Alkalisalze und die Phosphonate bevorzugt im Gewichtsverhältnis von 1:1 bis 30:1, mehr bevorzugt im Verhältnis von 1,5:1 bis 12:1 enthalten. Gegebenenfalls können diese Zubereitungen noch weitere Sequestriermittel und/oder Korrosionsinhibitoren enthalten.
Solche Zubereitungen können entweder als
(a) sogenannte Alkalispender in der Industriewäscherei dienen und enthalten dann bevorzugt 15-35% Alkali, 3-10% Polycarbonsäuren und 0,2-1,5% Phosphonate; mehr bevorzugt 18-30% Alkali, 4-7% Polycarbonsäuren und 0,5-1,2% Phosphonate; oder sie werden tel quel als
(b) Geschirrwaschmittel ohne Chlor eingesetzt und enthalten dann bevorzugt 10-35% Alkali, 0,5-15% Polycarbonsäuren und 0,2-5% Phosphonate; mehr bevorzugt 13-20% Alkali, 0,5-10,5% Polycarbonsäuren und 0,4-3% Phosphonate.
Der pH-Wert dieser Zubereitungen sollte auf jeden Fall über 10 liegen.
Unter Alkali im Sinne dieser Erfindung sind hauptsächlich Natrium- und Kaliumhydroxid oder -carbonat zu verstehen, die als Feststoff oder als stark konzentrierte wässrige Lösungen eingesetzt werden.
Als Polycarbonsäuren werden bevorzugt Polymere bis hochmolekulare Polymere (MG 800-500 000) der (Meth)Acrylsäure, alpha -Hydroxyacrylsäure, Maleinsäure sowie deren Copolymere in Form ihrer wässrigen Lösungen eingesetzt. Soweit sie nicht vorher neutralisiert wurden, werden die Carbonsäuregruppen in Gegenwart des vorhandenen Alkali in die Alkalisalze übergeführt. Mehr bevorzugt werden Polyacrylate mit Molekulargewicht von 1000 bis 250 000 verwendet, insbesondere bevorzugt mit einem durchschnittlichen Molekulargewicht von 4000-120 000.
Als Phosphonsäuren werden vorzugsweise bekannte Hydroxyalkylen- oder Aminomethylenphosphonsäuren oder Phosphonoalkylencarbonsäuren in Form ihrer wässrigen Lösungen eingesetzt, die in Gegenwart des vorhandenen Alkali in Phosphonate umgesetzt werden. Beispiele sind 1-Hydroxyäthan-1,1-diphosphonsäure (HEDP), Aminotri(methylenphosphonsäure) (ATMP), Äthylendiamintetra(methylenphosphonsäure) (EDTMP), Diäthylentriaminpenta(methylenphosphonsäure) (DETPMP), Hexamethylendiamintetra(methylenphosphonsäure), Aminoxidtri(methylenphosphonsäure) und 2-Phosphonobutan-1,2,4-tricarbonsäure (PBTC).
Als weitere Sequestriermittel können Nitrilotriessigsäure und Zitronensäure in Mengen von 3-20% verwendet werden, wobei diese in Form ihrer Alkalisalze eingesetzt werden.
Für die Anwendung als Geschirrwaschmittel ohne Chlor können die erfindungsgemässen Zubereitungen gegebenenfalls auch Korrosionsinhibitoren enthalten. Als solche werden bevorzugt 0,5-1% Natriumnitrit und 0,2-0,4% Benzo- oder Tolyltriazol eingesetzt.
Diese Geschirrwaschmittel haben auch ohne Chlor abgebende Mittel eine ausgezeichnete Wasch- und Reinigungswirkung und weisen die o.e. Nachteile der sonst Phosphat und/oder Silikat enthaltenden Waschmittel nicht auf.
Als Additiv für die Industriewäscherei stellen die erfindungsgemässen Wirkstoffgemische stabile, stark alkalische Konzentrate von Gerüststoffen dar, die durch Zugabe von anionischen und/oder nicht-ionischen Tensiden zu wirksamen Industriewaschmitteln werden.
In den nachfolgenden Beispielen (Tabellen 1 und 2) erfolgen alle Angaben in Gewichtsprozenten und werden die Polyacrylsäure A (MG 100 000) als 29%ige Lösung der halbneutralisierten Säure (Natriumsalz), die Polyacrylsäure B (MG 4500) als 49%ige Lösung, das Natriumsalz der Nitrilotriessigsäure (NTA) als 40%ige Lösung, die Diäthylentriaminpenta(methylenphosphonsäure) (DETPMP) als 50%ige und die 1-Hydroxyäthan-1,1- diphosphonsäure (HEDP) als 60%ige Lösung eingesetzt.
Der Zusatz der einzelnen Komponenten erfolgt jeweils in der angegebenen Reihenfolge unter Rühren, bis eine klare homogene Lösung vorliegt.
<tb><TABLE> Columns=9
<tb>Title: Tabelle 1
(a) Alkalispender
<tb>Head Col 01 AL=L: Beispiel Nr.
<tb>Head Col 02 AL=L: 1
<tb>Head Col 03 AL=L: 2
<tb>Head Col 04 AL=L: 3
<tb>Head Col 05 AL=L: 4
<tb>Head Col 06 AL=L: 5
<tb>Head Col 07 AL=L: 6
<tb>Head Col 08 AL=L: 7
<tb>Head Col 09 AL=L:
8
<tb> <SEP>Wasser entmineralisiert <SEP>58 <SEP>39 <SEP>58 <SEP>54 <SEP>36 <SEP>55 <SEP>46 <SEP>56,2
<tb> <SEP>Natriumhydroxid 98% <SEP>20 <SEP>30 <SEP>10 <SEP>22 <SEP>15 <SEP>21 <SEP>15 <SEP>24,8
<tb> <SEP>Kaliumhydroxid 95% <SEP>- <SEP>- <SEP>10 <SEP>- <SEP>20 <SEP>- <SEP>15 <SEP>-
<tb> <SEP>Polyacrylsäure B <SEP>13 <SEP>20 <SEP>10 <SEP>- <SEP>- <SEP>7 <SEP>5 <SEP>9,5
<tb> <SEP>Polyacrylsäure A <SEP>- <SEP>- <SEP>- <SEP>15 <SEP>15 <SEP>7 <SEP>5 <SEP>-
<tb> <SEP>NTA <SEP>8 <SEP>10 <SEP>10 <SEP>8 <SEP>12 <SEP>9 <SEP>12 <SEP>8,5
<tb> <SEP>DETPMP <SEP>0,5 <SEP>0,5 <SEP>1 <SEP>0,5 <SEP>1 <SEP>0,5 <SEP>1 <SEP>0,5
<tb> <SEP>HEDP <SEP>0,5 <SEP>0,5 <SEP>1 <SEP>0,5 <SEP>1 <SEP>0,5 <SEP>1 <SEP>0,5
<tb> <SEP>Total <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100
<tb></TABLE>
<tb><TABLE> Columns=7
<tb>Title:
Tabelle 2
(b) Geschirrwaschmittel
<tb>Head Col 01 AL=L: Beispiel Nr.
<tb>Head Col 02 AL=L: 9
<tb>Head Col 03 AL=L: 10
<tb>Head Col 04 AL=L: 11
<tb>Head Col 05 AL=L: 12
<tb>Head Col 06 AL=L: 13
<tb>Head Col 07 AL=L: 14
<tb> <SEP>Wasser entmineralisiert <SEP>39 <SEP>33 <SEP>26 <SEP>27 <SEP>23 <SEP>43,7
<tb> <SEP>Natriumnitrit <SEP>0,7 <SEP>0,7 <SEP>0,7 <SEP>0,7 <SEP>0,7 <SEP>-
<tb> <SEP>NTA <SEP>12 <SEP>12 <SEP>12 <SEP>12 <SEP>12 <SEP>38,0
<tb> <SEP>Natriumhydroxid 98% <SEP>14 <SEP>16 <SEP>18 <SEP>15 <SEP>15 <SEP>15,3
<tb> <SEP>Kaliumhydroxid 95% <SEP>- <SEP>- <SEP>- <SEP>15 <SEP>17 <SEP>-
<tb> <SEP>Polyacrylsäure B <SEP>30 <SEP>15 <SEP>- <SEP>20 <SEP>15 <SEP>2,0
<tb> <SEP>Polyacrylsäure A <SEP>- <SEP>17 <SEP>35 <SEP>- <SEP>6 <SEP>-
<tb> <SEP>DETPMP <SEP>2 <SEP>3 <SEP>3 <SEP>5 <SEP>5 <SEP>1,0
<tb> <SEP>HEDP <SEP>2 <SEP>3 <SEP>5 <SEP>5 <SEP>6 <SEP>-
<tb> <SEP>Tolyltriazol
<SEP>0,3 <SEP>0,3 <SEP>0,3 <SEP>0,3 <SEP>0,3 <SEP>-
<tb> <SEP>Total <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100 <SEP>100
<tb></TABLE>
The invention relates to phosphate- and silicate-free active ingredient mixtures which, in addition to alkali, contain a combination of polycarboxylic acids and phosphonates and can be used as alkali dispensers for industrial detergents or as dishwashing detergents.
Combinations of polycarboxylic acids and phosphonates are already known in various forms; they have previously been used as builders, as decalcifying agents or as stabilizers for peroxide solutions. However, these known combinations were not offered as concentrated, strongly alkaline solutions, but rather were described either as alkali-free concentrates or as dilute solutions, which mostly also contain other constituents and often also phosphates and / or silicates. For various reasons, however, it should generally be avoided to use phosphates and / or silicates in detergents. Because of their environmental impact, phosphates are no longer permitted in various countries; silicates cause incrustations or deposits in the equipment.
The invention relates to phosphate- and silicate-free active ingredient mixtures which contain 5-45% alkali, 0.5-20% polycarboxylic acids in the form of their alkali salts and 0.1-10% phosphonates in aqueous solution, all percentages being percentages by weight of the pure active ingredients are understandable and refer to the overall solution. These preparations contain the polycarboxylic acids in the form of their alkali metal salts and the phosphonates preferably in a weight ratio of 1: 1 to 30: 1, more preferably in a ratio of 1.5: 1 to 12: 1. If appropriate, these preparations may also contain further sequestering agents and / or corrosion inhibitors.
Such preparations can either be used as
(a) So-called alkali dispensers are used in industrial laundering and then preferably contain 15-35% alkali, 3-10% polycarboxylic acids and 0.2-1.5% phosphonates; more preferably 18-30% alkali, 4-7% polycarboxylic acids and 0.5-1.2% phosphonates; or they will be tel quel as
(b) dishwashing detergents used without chlorine and then preferably contain 10-35% alkali, 0.5-15% polycarboxylic acids and 0.2-5% phosphonates; more preferably 13-20% alkali, 0.5-10.5% polycarboxylic acids and 0.4-3% phosphonates.
The pH of these preparations should definitely be over 10.
Alkali in the sense of this invention is to be understood primarily as sodium and potassium hydroxide or carbonate, which are used as a solid or as highly concentrated aqueous solutions.
Polymers to high molecular weight polymers (MW 800-500,000) of (meth) acrylic acid, alpha-hydroxyacrylic acid, maleic acid and their copolymers in the form of their aqueous solutions are preferably used as polycarboxylic acids. If they have not been neutralized beforehand, the carboxylic acid groups are converted into the alkali salts in the presence of the alkali present. Polyacrylates with a molecular weight of 1000 to 250,000 are more preferably used, particularly preferably with an average molecular weight of 4000-120,000.
Known hydroxyalkylene or aminomethylene phosphonic acids or phosphonoalkylene carboxylic acids are preferably used as phosphonic acids in the form of their aqueous solutions, which are converted into phosphonates in the presence of the alkali present. Examples are 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DETPMP), hexamethylenediamine tetra (methylenephosphonic acid), and aminoxidetronic acid (2) -Phosphonobutane-1,2,4-tricarboxylic acid (PBTC).
As a further sequestering agent, nitrilotriacetic acid and citric acid can be used in amounts of 3-20%, these being used in the form of their alkali salts.
For use as a dishwashing detergent without chlorine, the preparations according to the invention may also contain corrosion inhibitors. As such, 0.5-1% sodium nitrite and 0.2-0.4% benzo- or tolyltriazole are preferably used.
These dishwashing detergents have an excellent washing and cleaning effect even without chlorine-releasing agents and have the above-mentioned Disadvantages of the detergents which otherwise contain phosphate and / or silicate do not arise.
As an additive for industrial laundering, the active substance mixtures according to the invention represent stable, strongly alkaline concentrates of builders which, by adding anionic and / or non-ionic surfactants, become effective industrial detergents.
In the examples below (Tables 1 and 2), all data are given in percent by weight and the polyacrylic acid A (MW 100,000) is a 29% solution of the semi-neutralized acid (sodium salt), the polyacrylic acid B (MW 4500) is a 49% solution, the sodium salt of nitrilotriacetic acid (NTA) as a 40% solution, the diethylenetriaminepenta (methylenephosphonic acid) (DETPMP) as a 50% solution and the 1-hydroxyethane-1,1-diphosphonic acid (HEDP) as a 60% solution.
The individual components are added in the order given, with stirring, until a clear homogeneous solution is obtained.
<tb> <TABLE> Columns = 9
<tb> Title: Table 1
(a) Alkaline dispenser
<tb> Head Col 01 AL = L: Example no.
<tb> Head Col 02 AL = L: 1
<tb> Head Col 03 AL = L: 2
<tb> Head Col 04 AL = L: 3
<tb> Head Col 05 AL = L: 4
<tb> Head Col 06 AL = L: 5
<tb> Head Col 07 AL = L: 6
<tb> Head Col 08 AL = L: 7
<tb> Head Col 09 AL = L:
8th
<tb> <SEP> water demineralized <SEP> 58 <SEP> 39 <SEP> 58 <SEP> 54 <SEP> 36 <SEP> 55 <SEP> 46 <SEP> 56.2
<tb> <SEP> sodium hydroxide 98% <SEP> 20 <SEP> 30 <SEP> 10 <SEP> 22 <SEP> 15 <SEP> 21 <SEP> 15 <SEP> 24.8
<tb> <SEP> potassium hydroxide 95% <SEP> - <SEP> - <SEP> 10 <SEP> - <SEP> 20 <SEP> - <SEP> 15 <SEP> -
<tb> <SEP> polyacrylic acid B <SEP> 13 <SEP> 20 <SEP> 10 <SEP> - <SEP> - <SEP> 7 <SEP> 5 <SEP> 9.5
<tb> <SEP> polyacrylic acid A <SEP> - <SEP> - <SEP> - <SEP> 15 <SEP> 15 <SEP> 7 <SEP> 5 <SEP> -
<tb> <SEP> NTA <SEP> 8 <SEP> 10 <SEP> 10 <SEP> 8 <SEP> 12 <SEP> 9 <SEP> 12 <SEP> 8.5
<tb> <SEP> DETPMP <SEP> 0.5 <SEP> 0.5 <SEP> 1 <SEP> 0.5 <SEP> 1 <SEP> 0.5 <SEP> 1 <SEP> 0.5
<tb> <SEP> HEDP <SEP> 0.5 <SEP> 0.5 <SEP> 1 <SEP> 0.5 <SEP> 1 <SEP> 0.5 <SEP> 1 <SEP> 0.5
<tb> <SEP> Total <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> </TABLE>
<tb> <TABLE> Columns = 7
<tb> Title:
Table 2
(b) Dishwashing detergent
<tb> Head Col 01 AL = L: Example no.
<tb> Head Col 02 AL = L: 9
<tb> Head Col 03 AL = L: 10
<tb> Head Col 04 AL = L: 11
<tb> Head Col 05 AL = L: 12
<tb> Head Col 06 AL = L: 13
<tb> Head Col 07 AL = L: 14
<tb> <SEP> water demineralized <SEP> 39 <SEP> 33 <SEP> 26 <SEP> 27 <SEP> 23 <SEP> 43.7
<tb> <SEP> sodium nitrite <SEP> 0.7 <SEP> 0.7 <SEP> 0.7 <SEP> 0.7 <SEP> 0.7 <SEP> -
<tb> <SEP> NTA <SEP> 12 <SEP> 12 <SEP> 12 <SEP> 12 <SEP> 12 <SEP> 38.0
<tb> <SEP> sodium hydroxide 98% <SEP> 14 <SEP> 16 <SEP> 18 <SEP> 15 <SEP> 15 <SEP> 15.3
<tb> <SEP> potassium hydroxide 95% <SEP> - <SEP> - <SEP> - <SEP> 15 <SEP> 17 <SEP> -
<tb> <SEP> polyacrylic acid B <SEP> 30 <SEP> 15 <SEP> - <SEP> 20 <SEP> 15 <SEP> 2.0
<tb> <SEP> polyacrylic acid A <SEP> - <SEP> 17 <SEP> 35 <SEP> - <SEP> 6 <SEP> -
<tb> <SEP> DETPMP <SEP> 2 <SEP> 3 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 1.0
<tb> <SEP> HEDP <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 5 <SEP> 6 <SEP> -
<tb> <SEP> tolyltriazole
<SEP> 0.3 <SEP> 0.3 <SEP> 0.3 <SEP> 0.3 <SEP> 0.3 <SEP> -
<tb> <SEP> Total <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> </TABLE>
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3900310 | 1989-01-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH679311A5 true CH679311A5 (en) | 1992-01-31 |
Family
ID=6371680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH27/90A CH679311A5 (en) | 1989-01-07 | 1990-01-03 |
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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016159A1 (en) * | 1994-11-21 | 1996-05-30 | Unilever N.V. | Cleaning method |
| WO2001053446A2 (en) * | 2000-01-22 | 2001-07-26 | Henkel Ecolab Gmbh & Co. Ohg | Production of an alkaline aqueous detergent creme containing a complexing agent |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285052A (en) * | 1993-12-23 | 1995-06-28 | Procter & Gamble | Detergent composition |
| GB2285051A (en) * | 1993-12-23 | 1995-06-28 | Procter & Gamble | Rinse aid composition |
| US5928384A (en) * | 1994-11-10 | 1999-07-27 | The Procter & Gamble Company | Method of cleaning carpets |
| MX9703486A (en) * | 1994-11-10 | 1997-08-30 | Procter & Gamble | Method of cleaning carpets. |
| US5905065A (en) * | 1995-06-27 | 1999-05-18 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
| DE69708064T2 (en) * | 1996-02-29 | 2002-03-14 | Unilever N.V., Rotterdam | GEL-SHAPED MACHINE DISHWASHER |
| JP3566015B2 (en) * | 1997-02-17 | 2004-09-15 | 花王株式会社 | Detergent composition for dishwashers |
| US20020183220A1 (en) * | 2001-04-23 | 2002-12-05 | Francesco Falsina | Anti-scuffing treatment for alkaline bottle washing systems |
| ES2373300B1 (en) * | 2011-12-14 | 2012-12-20 | Soro Internacional, S.A. | DETERGENT FOR DISHWASHERS. |
| 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 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1252838B (en) * | 1965-04-01 | |||
| DE1806594C3 (en) * | 1968-11-02 | 1979-05-03 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Use of a mixture of aminoalkylenephosphonic acid and polymeric compounds to prevent stone-forming deposits in aqueous systems |
| DE2057008C3 (en) * | 1970-11-20 | 1979-05-10 | Benckiser Gmbh Joh A | Agent for preventing stone-forming deposits in aqueous systems |
| 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 |
| US4230592A (en) * | 1979-05-31 | 1980-10-28 | Chemed Corporation | Controlled foam detergent additive |
| FR2613378A1 (en) * | 1987-04-03 | 1988-10-07 | Sandoz Sa | DETERGENT COMPOSITIONS FOR DISHWASHER |
| DE3717227A1 (en) * | 1987-05-21 | 1988-12-01 | Henkel Kgaa | PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY |
-
1990
- 1990-01-03 CH CH27/90A patent/CH679311A5/de not_active IP Right Cessation
- 1990-01-05 JP JP2000135A patent/JPH02228399A/en active Pending
- 1990-01-05 BE BE9000017A patent/BE1003581A5/en not_active IP Right Cessation
- 1990-01-05 FR FR9000103A patent/FR2641544A1/en active Granted
- 1990-01-05 GB GB9000224A patent/GB2227021B/en not_active Expired - Lifetime
- 1990-01-08 IT IT47510A patent/IT1239740B/en active IP Right Grant
- 1990-01-08 NL NL9000040A patent/NL9000040A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996016159A1 (en) * | 1994-11-21 | 1996-05-30 | Unilever N.V. | Cleaning method |
| WO2001053446A2 (en) * | 2000-01-22 | 2001-07-26 | Henkel Ecolab Gmbh & Co. Ohg | Production of an alkaline aqueous detergent creme containing a complexing agent |
| WO2001053446A3 (en) * | 2000-01-22 | 2002-03-14 | Henkel Ecolab Gmbh & Co Ohg | Production of an alkaline aqueous detergent creme containing a complexing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2227021A (en) | 1990-07-18 |
| GB9000224D0 (en) | 1990-03-07 |
| NL9000040A (en) | 1990-08-01 |
| FR2641544B1 (en) | 1994-07-13 |
| JPH02228399A (en) | 1990-09-11 |
| GB2227021B (en) | 1992-08-05 |
| IT9047510A0 (en) | 1990-01-08 |
| IT9047510A1 (en) | 1990-07-08 |
| IT1239740B (en) | 1993-11-15 |
| BE1003581A5 (en) | 1992-04-28 |
| FR2641544A1 (en) | 1990-07-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| NV | New agent |
Representative=s name: SANDOZ TECHNOLOGIE AG |
|
| PUE | Assignment |
Owner name: SANDOZ AG TRANSFER- CLARIANT FINANCE (BVI) LIMITED |
|
| NV | New agent |
Representative=s name: CLARIANT INTERNATIONAL LTD. |
|
| PL | Patent ceased |