FR2613378A1 - DETERGENT COMPOSITIONS FOR DISHWASHER - Google Patents

Abstract

THE SUBJECT OF THE PRESENT INVENTION IS A LIQUID, AQUEOUS AND STABLE DETERGENT COMPOSITION FOR USE IN MECHANICAL DISHWASHERS AND CONTAINING A POLYACRYLIC ACID, A PHOSPHONATE OR AN ORGANIC PHOSPHATE RESISTANT TO CHLORINE, SODIUM HYPOCHLORITE AND AN ALKALI. A PH VALUE GREATER THAN 13.

Description

The present invention relates to liquid detergent compositions

  containing a bleaching agent, which are stable and which can be

  used as a single detergent in washing machines

mechanical dishes.

  In particular, the invention relates to an aqueous and stable liquid detergent composition containing: a) from 0.5 to 7% by weight of a polyacrylic acid, a polyhydroxyacrylic acid or a mixture of these compounds (the percentage referring to the free acid form), b) from 0.4 to 6% by weight of a chlorine-resistant organic phosphonate or phosphate, and c) from 3 to 15% by weight of sodium hypochlorite. sodium, the pH of the composition being adjusted to pH 13 or higher with sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate, and the weight ratio of sodium ions to potassium ions

  in the composition not to be greater than 1: 1.

  The detergent composition may also contain: d) from 0 to 12% of a sodium or potassium polyphosphate, e) from 0 to 1.5% of a sodium or potassium tolylsulfonate, f) from 0 to 10% potassium carbonate, and g) from 0 to 1.5% of a surfactant

foam and chlorine resistant.

  All percentages shown in the

  description are by weight unless indicated otherwise

contrary cation.

  To adjust the pH to 13 or above, it is generally necessary to add 10 to 22% of sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate. The total solids content of the

  the aqueous solution is then between 20 and 60%.

  Preferred amounts of the various compounds

  components are: Component a): 1-4% Component b): 1-3% Component c): 4-8% Component d) 4-9% Component e) 0.5-1.5% Component f): 1-6% Component g): 0.2-1% and 12-18% sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate. The total solids content is preferably

between 25 and 40%.

  The polymeric acids of component a) comprise homopolymers of acrylic acid, methacrylic acid and hydroxyacrylic acid,

  as well as the copolymers of these mers between them.

  Preferred materials are commercially available acrylic acid and α-hydroxyacrylic acid homopolymers having a molecular weight (measured by exclusion chromatography) of from 500 to 1,000,000, preferably from 1,000 to 500,000. , more preferably between 2500 and 150 000. Polyacrylic acids having a molecular weight between

  3000 and 6000 or between 80 000 and 120 000 are partic-

  highly preferred. These polyacrylic acids are used

  They are preferably in the form of their aqueous solutions, and are neutralized by the caustic alkali present in the composition, so that they are present in the detergent composition in salt form. The phosphonate or phoshate of component b) is present as a sequestering agent. It must be resistant to chlorine, that is to say when it is present in the detergent composition containing

  hypochlorite, the active chlorine content of the compound

  sition, measured by titration, should not decrease significantly during storage at room temperature. In other words, the active chlorine should not be absorbed by reaction with component b). The same definition applies to surfactant g)

chlorine resistant.

  The preferred components b) correspond to the following formulas I, II or III:

O <N- "CH20POH) 3 I

CH3 I (HO) 1-C-P (OH) 2 II

O OH 0

CH 2 COOH

(HO) 2 - C- COOH III

O CH2-CH2COOH

  The aminotris (methylenephosphoric acid) of formula (I) is sold by Bozzeto S.p.A., Bergamo, Italy, under the trademark Sequion OA; the compound

  of the formula III, 2-phosphonobutane-1,2,4-tri-

  carboxylic acid, is sold by Bayer AG,

  Leverkusen, West Germany, under the name Bayhibit AM.

  The sodium hypochlorite of component c) is preferably added in the form of a 30% aqueous solution, for example as a bleaching agent.

  trade containing 14% of active chlorine.

  Sodium or potassium polyphosphate

  component d) is preferably one of the polyphosphoric

  phates commonly used in detergents, by

  for example, sodium tripolyphosphate.

  The low foaming and chlorine-resistant surfactant of component g) is, for example, a surfactant amine oxide or, preferably, a completely carboxymethyl polyglycolic ether. A suitable product of this type is sold by the company Sandoz S.A., Basel, Switzerland, under the trademark

Sandopan D-PC.

  When using sodium polyphosphate or sodium tolylsulfonate, or when using sodium hydroxide to neutralize component a) or to adjust the pH of the composition, it must be verified that the weight ratio of sodium ions to potassium ions is not greater than 1: 1, to ensure the solubility of the various components and

  to avoid the crystallization of the solution.

  Preferably, in the absence of metasilicate or polyphosphate, the Na: K ratio is between 1: 2 and 1: 3; in the presence of metasilicate and in the absence of polyphosphate, the Na: K ratio is between 1: 3 and 1:20; in the absence of metasilicate and in the presence of polyphosphate, the Na: K ratio is between 1: 1.5

  and 1: 2, and in the presence of metasilicate and poly-

  phosphate, the Na: K ratio is between 1: 1 and 1: 2.

  The detergent composition of the invention can be used as a single detergent in mechanical dishwashers at all normal washing temperatures, for example between 20 and 100 C. The amount of detergent composition to be used will depend on

  dirty dishes, but is normally

  between 1 and 5 g per liter of wash water. The selected amount of components provides excellent stability to the composition in the concentrated state and after dilution. The detergent composition has excellent cleaning ability on stubborn dirt, for example proteins, fats and oils. It is suitable for use in all types of dishwashers and can be used in industrial and domestic machinery. It is biodegradable,

  low foaming and resistant to hard water.

  The detergent composition is preferably prepared by stirring the components in an aqueous solution of metasilicate or sodium or potassium hydroxide, the order of addition being identical to that indicated in the examples. At the end of the demineralized water is added to obtain the desired concentration, and

  the mixture is stirred to make it homogeneous.

  The following examples illustrate the present invention without limiting its scope. In these examples, the parts and percentages are by weight and the temperatures are indicated in degrees Celsius.

EXAMPLES 1 TO 10:

  Components 1. Potassium metasilicate (40% aqueous solution) 2. Potassium hydroxide (50% aqueous solution) 3. Semi-neutralized polyacrylic acid (molecular weight 100,000) (sodium salt) as an aqueous solution 29% (component a) 4. Polyacrylic acid (molecular weight 4500) in the form of a 49% aqueous solution (component a) 5. Compound of formula I (Sequion OA) in the form of a - 43% aqueous solution (component b) 6. Compound of formula III (Bayhibit AM) in the form of a 50% aqueous solution (component b)

  7. Compound of formula II (1-hydroxyethane-1, 1-

  di-phosphonic acid) as a 60% aqueous solution (component b) 8. Sodium tolylsulfonate (33% aqueous solution) (component e) 9. Potassium tolylsulfonate (% aqueous solution) (component e) 10 Sodium tripolyphosphate (component d) 11. Sodium hypochlorite (30% aqueous solution) (component c) 12. Sodium hydroxide (30% aqueous solution) 13. Potassium carbonate (component f) 14. Sandopan D- PC (25% aqueous solution) (component g). The components are mixed according to the amount indicated in the following Table I and in the order in which they are presented. In all cases we obtain a fluid solution, yellow battery, stable at a temperature between 0 and 50,. : possessed of excellent washing power at 20 and boiling. Excellent results in equipment

  industrial dishwashers (restaurants).

BOARD,

EX E M P L ES

Components 1 2 3 4 5 6 7 8 9 10

  1. 40 38.0 30.0 - 20.0 - 45.0 32.0 - 39.0

  2. 5 5.0 5.5 27.5 17.0 30.0 5.0 15.0 30.0 5.0

3. 6 5.0 10.0 - - - 6.0 5.0 - 5.0

4. - - - 6.0 6.0 6.0 - - 6.0 -

5. 4 3.0 - - - - 4.0 4.0 - 3.0

6. - - 4.0 4.0 4.0 4.0 - - - -

7. - - - - - - 3.0 -

8. 2 - - - - - 2,0 - - -

9. - - - - - 3.0 -

10. - 7.0 7.0 7.0 7.0 - - - 7.0 7.0

  11. 25 19.0 19.0 18.0 15.0 19.0 20.0 22.0 19.0 20.0

12. - - 8.0 3.5 9.0 - - - - -

13. 3 - - - - 3,0 3,0 - -

14. - - 1, - - - - -

  Water 15 23.0 16.5 34.0 22.0 41.0 15.0 15.0 35.0 21.0 dom. d i. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ _ Total 100% 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% U4 -4 -4 The corresponding percentages of the ag components in Examples 1-10 are indicated

in the following Table II.

TABLE II

EX E M P L ES

1 2 3 4 5 6 7 8 9 10

  Component at 1.74 1.45 2.9 3.0 3.0 3.0 1.74 1.45 3.0 1.45 b 1.72 1.29 2.0 2.0 2.0 2, 0 1.72 1.72 1t8 1.29 c 7.5 5.7 5.7 5.4 4.5 517 6.0 6.6 5.7 6.0 d-7.0 7.0 7, 0 7.0 - - - 7.0 7.0

e 0.66 - - - - - 0.66 1.2 - -

f 3.0 - - - 3.0 3.0 - -

9 - - - - - - - 0,25 - -

  alkali 18.5 1 /, 7 17.15 14.8 19.2 15.0 20.5 20.3 15.0 1811 Total nights 33.1 33.1 34.8 32.2 35, / 25, 7 33.6 34.5 32.5 33.8 solid o

Claims (15)

  1. A liquid, aqueous and stable detergent composition, characterized in that it contains a) 0.5 to 7% by weight of a polyacrylic acid, a polyhydroxyacrylic acid or a mixture of these compounds (the percentage referring to the free acid form), b) from 0.4 to 6% by weight of a chlorine-resistant phosphonate or organic phosphate, and c) from 3 to 15% by weight of hypochlorite of sodium, the pH of the composition being adjusted to pH 13 or higher with sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate, and the weight ratio of sodium ions to potassium ions   in the composition not to be greater than 1: 1.   2. A composition according to claim 1, characterized in that it contains 10 to 22% sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate and has a total content of solid substances between and 60%.   3. A composition according to claim 1, characterized in that it may also contain d) from 0 to 12% of a sodium or potassium polyphosphate, e) from 0 to 1.5% of a sodium tolylsulfonate or potassium, f) 0 to 10% potassium carbonate, and g) 0 to 1.5% of a surfactant foam and chlorine resistant.   4. A composition according to claim 3, characterized in that it contains: from 1 to 4% of component a) from 1 to 3% of component b) i1 from 4 to 8% of component c) from 12 to 18% sodium hydroxide and / or potassium hydroxide and / or potassium metasilicate and at least one of the following components: from 4 to 9% of the component d) from 0.5 to 1.5% of the component e) from 1 to 6% of component f) from 0.2 to 1% of component g).   5. A composition according to any one   Claims 1 to 4, characterized in that the   component a) is a homopolymer of acrylic or hydroxyacrylic acid, having a molecular weight of between 1000 and 500 000.   6. A composition according to claim 5, characterized in that component a) is a polyacrylic acid having a molecular weight between   3000 and 6000 or between 80 000 and 120 000.   7. A composition according to any one   Claims 1 to 6, characterized in that the   component b) is selected from aminotris acid (methyl   lenephoshoric acid), 1-hydroxyethane-1,1-di-   phosphoric acid and 2-phosphonobutane-1,2,4-tri-   carboxylic acid. 8. A composition according to any one   Claims 3 to 7, characterized in that the   component d) is sodium tripolyphosphate.   9. A composition according to any one   Claims 3 to 8, characterized in that the   component g) is an amine oxide or a polyether ether   completely carboxymethylated glycolic.   10. A composition according to any one   Claims 1 to 9, characterized in that it   contains no metasilicate or polyphosphate and that the   Na: K ratio is between 1: 2 and 1: 3 by weight.   11. A composition according to any one   Claims 1 to 9, characterized in that   contains a metasilicate and does not contain polyphosphate, and that the Na: K ratio is between 1: 3 and 1:20 by weight. \ 12. A composition according to any one   Claims 1 to 9, characterized in that it   contains no metasilicate and contains a poly-   phosphate, and that the Na: K ratio is between 1: 1.5 and 1: 2 by weight.   13. A composition according to any one   Claims 1 to 9, characterized in that   contains a metasilicate and a polyphosphate and that the   Na: K ratio is between 1: 1 and 1: 2 by weight.   14. The use of a composition according to   any one of claims 1 to 13, as de-   unique tergent for meacanic dishwashers.   15. The use according to claim 14, characterized in that pa: liter of wash water, from 1 to 5 g of a composition specified in one   any of claims 1 to 13.