WO1991000901A1

WO1991000901A1 - Phosphateless liquid washing and cleaning agents

Info

Publication number: WO1991000901A1
Application number: PCT/EP1990/001058
Authority: WO
Inventors: Walter Schwizer; Vincenzo Violante
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1989-07-10
Filing date: 1990-07-02
Publication date: 1991-01-24
Also published as: DK1692A; PT94637A; DK1692D0; EP0407626A1

Abstract

The phosphate and chlorineless washing and cleaning agents contain 5 - 60 % wt. potassium carbonate, 1 - 40 % wt. alkaline silicate, 1 - 30 % wt. of an organic builder substance, 1 - 20 % wt. of a polymeric complex former, 30 - 80 % wt. water and 0 - 5 % wt. free alkaline hydroxide. The agents are usable anywhere, completely non-toxic and do not corrode metal surfaces like steel or aluminium.

Description

Phosphate-free, liquid detergent and cleaning agent

The invention relates to a liquid washing and cleaning agent which contains neither phosphate nor chlorine and which can be used universally in particular in commercial and institutional facilities for washing and cleaning textiles and objects with hard surfaces.

It is known that alkaline solutions with a pH above 10 and with a high content of free alkali hydroxide are effective cleaning agents. For example, German patent application 18 06 206 describes a liquid dishwashing detergent which contains 10-50% by weight of alkali metal hydroxide, preferably potassium hydroxide, 5-30% by weight of alkali metal salts of nitrilotriacetic acid (NTA) and 5-30% by weight of alkali metal pyro- contains phosphate.

From British patent application 1287887, alkaline cleaning agents are known which are used as automatic dishwashing detergents and contain alkali metal hydroxide, alkali metal carbonate or alkali metal silicate, and as complexing agents the salts of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid or organic phosphonic acids and optionally water.

Japanese patent application 59/227 997 describes liquid cleaning agents for hard surfaces which contain 5-40% by weight of sodium or potassium hydroxide and 2-40% by weight of one Alkali salt of nitrilotriacetic acid, 2 to 40% by weight of a copolymer of isoptenes and maleic anhydride and optionally up to 5% by weight sodium metasilicate and up to 5% by weight of surfactants.

US Pat. No. 4,521,332 discloses liquid, alkaline cleaning agent dispersions which contain 10-45% by weight sodium hydroxide, 0.04% by weight of an acrylic polymer as a dispersing agent, 0.5-20% by weight sodium or potassium carbonate, containing 0.25-3% by weight of a complexing agent such as, for example, NTA salts and 0-15% by weight of an alkali metal phosphate former.

Due to the high amount of free alkali hydroxide, these agents are only used in certain areas of application. Thus, these agents cannot be used as degreasing and cleaning agents for alkali-sensitive surfaces such as aluminum or in the food industry.

Known cleaning agents for alkali-sensitive surfaces, especially for aluminum, therefore preferably do not contain any free alkali hydroxide. For example, European patent application 282 921 describes liquid, phosphate-free single-phase degreasing agents for aluminum surfaces which contain mixtures of alkali metal carbonates and alkali metal bicarbonates, one or more complexing agents, which include acrylic polymers, EDTA, NTA, citric acid, gluconic acid and their salts.

On the other hand, US Pat. No. 4,528,039 discloses aqueous alkaline cleaning agents, especially for cleaning aluminum surfaces, which contain mixtures of carbonate and Metasilicate, preferably in the form of their sodium salts, in a weight ratio of 20: 1 to 1: 2 and optionally further constituents such as, for example, surfactants, thickeners, organic solvents, colorants and fragrances.

The object of the invention was to provide a washing and cleaning agent which can be used universally and which is toxic-free and contains a maximum of 5% by weight of free alkali metal hydroxide.

The invention relates to a phosphate-free, liquid washing and cleaning agent containing (A) 5-60% by weight potassium carbonate,

(B) 1-40% by weight alkali silicate with a molar ratio of M2O: SiO 2 from 1: 2 to 1: 4, where M is sodium or potassium,

(C) 1-30% by weight of an organic builder, (D) 1-20% by weight of a polymeric complexing agent and (E) 30-80% by weight of water, with the proviso that the components (A) to (D) are calculated as anhydrous substances.

The constituents contained in the compositions, which are used in the form of their salts, can be present with the exception of (A) as sodium and / or potassium salts. The potassium to sodium weight ratio in the agents according to the invention is preferably at least 3: 1. Potassium to sodium weight ratios between 5: 1 and 60: 1, in particular between 7: 1 and 50: 1 are particularly preferred is also the use of all salt-like components in the form of the potassium salts.

The proportion of potassium carbonate (A) in the agents according to the invention is 5-60% by weight. Potassium carbonate is preferably used in amounts of 10-55% by weight and in particular 20-50% by weight. The alkali silicates (B) used are sodium or potassium silicates or mixtures thereof with a molar ratio of M2O to SiO 2 of 1: 2 to 1: 4, where M represents the alkali metal cation. Potassium silicates are preferably used. The proportion of alkali silicates (B) in the agents according to the invention is 1-40% by weight, preferably 1.5-20% by weight and in particular 2-10% by weight.

The organic builder substances (C) are the alkali metal salts of polycarboxylic acids such as citric acid, tartaric acid and succinic acid, of nitrilotriacetic acid (NTA) and of polyphosphonic acids such as l-hydroxyethane-l, l-diphosphonic acid (HEDP) and diethylenetriamine-pentamethylenephosphonic acid (DTP ). NTA and HEDP are preferably used in the form of their sodium or potassium salts. The proportion of organic builder substances (C) in the agents according to the invention is 1 to 30% by weight, preferably 1 to 20% by weight, polycarboxylates 0 to 100% by weight and phosphonates 0 to 20% by weight. - Based on the total amount of organic builder substance used. In particular, when using nitrilotriacetic acid in the form of the sodium salt, amounts of 2-10% by weight are preferred. It is also advantageous to use mixtures, for example consisting of 0-15% by weight of salts of citric acid, 2-10% by weight of salts of nitrilotriacetic acid and 0.5-2% by weight of salts of l-hydroxyethane-1 , l-diphosphonic acid.

Suitable polymeric complexing agents (D) are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates, polymaleinates and, in particular, copolymeric alkali metal salts of acrylic acid with maleic acid, preferably those with 10 to 50% maleic acid, sodium and potassium salts being equally preferred . The molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 and 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Compounds of this class which are advantageously used are also salts of copolymers of acrylic acid, methacrylic acid or maleic acid or maleic anhydride with vinyl ethers, in which the proportion of the acid is at least 50% by weight. The use of copolymers of maleic anhydride and methyl vinyl ether in the form of their sodium and / or potassium salts has proven to be particularly favorable. The content of polymeric complexing agents (D) in the agents according to the invention is between 1 and 20% by weight. The agents according to the invention preferably contain 1.5-20% by weight and in particular 2-5% by weight (D).

The water content of the agents according to the invention is between 30 and 80% by weight, preferably between 30 and 60% by weight and in particular between 35 and 55% by weight.

The inventive compositions are preferably clear aqueous Lö¬ solutions with a pH 11 to 14 The viscosity of the compositions is 20 ^β C under 200 Pa, preferably the Vis¬ is viscosity by less than 150 mPa. The agents also have the advantage that they are stable in storage even under extreme temperature conditions such as -20 ° C., ie no settling of essential components is observed and remain pourable. In addition, they are free from organic solvents and show no corrosive effects on metallic devices and hard surfaces made of steel or light metals such as aluminum.

As a further constituent, the agents can contain 0-5% by weight of alkali hydroxide. The use of potassium hydroxide is preferred in amounts of 0.5-4% by weight, in particular in amounts of 0.5-3% by weight.

It can also be advantageous in some cases to add low-foaming, alkali-resistant, customary anionic, nonionic or amphoteric surfactants in amounts of up to 10% by weight, preferably from 0.5 to 5% by weight and in particular from 0.5 to Add 3 wt .-%.

Furthermore, the agents can contain additional ingredients such as colorants and fragrances. optical brighteners, graying inhibitors, such as water-soluble salts of ether carboxylic acids or ether sulfonic acids, cellulose or starch, and bleaching agents. The total content of these additional constituents in the agents is 0-10% by weight, preferably 0.5-5% by weight.

In a preferred embodiment, the compositions consist of 20-55% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: SiO2 of 1: 2 to 1: 4, 3-10% by weight. an organic builder in the form of the sodium salts, preferably sodium salts of nitrilotriacetic acid, 1.5-10% by weight of a copolymer in the form of the sodium salt, preferably copolymers of acrylic acid and maleic acid or of maleic anhydride and methyl vinyl ether, and 30-60% by weight .-% Water. The weight ratio of potassium to sodium is between 7: 1 and 50: 1.

In a further preferred embodiment, the agents consist of 20-50% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: SiO2 of 1: 2 to 1: 4, 2-10% by weight. % Sodium salts of nitrilotriacetic acid, 1.5-5% by weight of a copolymer in the form of the sodium salt of acrylic acid and maleic acid or of maleic anhydride and methyl vinyl ether, 0.5-4 % By weight sodium or potassium hydroxide and 35-60% by weight water. The weight ratio of potassium to sodium is between 5: 1 and 50: 1.

Likewise preferred are compositions consisting of 22-50% by weight of potassium carbonate, 1.5-20% by weight of potassium silicate with a molar ratio of K2O: S1O2 of 1: 2 to 1: 4, 2-10% by weight. * Sodium salt of nitrilotriacetic acid, 0.5-1.5% by weight * sodium salt of l-hydroxyethane-l, l-diphosphonic acid, 1.5-5% by weight of a copolymer in the form of the sodium salt, preferably a copolymer of acrylic acid and maleic acid or from maleic anhydride and methyl vinyl ether, 0-15% by weight sodium citrate, 0-4% by weight potassium hydroxide and 35-55% by weight water. The potassium to sodium weight ratio is greater than 5: 1.

Further preferred embodiments are agents in which all of the constituents are present in the amounts specified above in the form of the potassium salts.

Embodiments are also preferred in which the agents contain the above-described constituents in the above amounts and additionally 1-10% by weight of further constituents such as surfactants, colorants and fragrances and bleaches.

The invention further relates to a method for producing the detergents and cleaning agents described above, in which the components are mixed with one another in a manner known per se. The alkali metal hydroxide, the alkali metal silicate (both components if provided) and the organic builder substance are preferably dissolved in demineralized water with stirring. A temperature of between 30 is achieved by means of external cooling and set at 60 ° C. The addition of the other constituents such as potassium carbonate, polymeric complexing agent, optionally surfactants, colorants and fragrances, optical brighteners, graying inhibitors and bleaching agents can be carried out in any order. After cooling to 25 - 40 ° C, the solution is filtered. For this purpose, it is advantageous to use a fabric or paper filter that has a pore size between 80-120 μm.

The agents according to the invention can be used both as detergents for textiles and as cleaning agents for hard surfaces. The use as a phosphate-free dishwashing detergent in plants which have a liquid dosage is preferred, as is the use as a non-corrosive leaching, degreasing and cleaning agent for devices with metal surfaces, which contain steel or aluminum, for example, and in the dyeing , Food and metal industries are used. The agents can also be used as immersion cleaners or low-foaming spray cleaners for smaller devices.

Examples

Example 1:

The example describes the production of a detergent and cleaning agent which contains no free alkali metal hydroxide. 90 kg of potassium water glass (30 * active substance), 48 kg of nitrilotriacetic acid in the form of the trisodium salt (92% of active substance), 383 kg of potassium carbonate powder and 69 kg of a 35% strength aqueous solution of Sokalan CP2 (sodium salt of a copolymer from maleic anhydride and methyl vinyl ether; brand name of BASF) dissolved in 410 kg of deionized water with stirring and external cooling. The solution was then filtered through a cloth filter (pore size 100 μm).

Example 2:

Further agents according to the invention were obtained by replacing potassium water glass with sodium water glass in Example 1 and simultaneously the sodium salt of nitrilotriacetic acid with the potassium salt and / or the sodium salt of the copolymer with the potassium salt.

Further agents according to the invention were also obtained by completely replacing the sodium salt of nitrilotriacetic acid used in Example 1 with citrates, succinates or tartrates, or by adding 1% by weight, based on the total, of the sodium salt of nitrilotriacetic acid used in Example 1 Agent replaced by the sodium salt of l-hydroxyethane-l, l-diphosphonic acid.

Likewise, further agents according to the invention were obtained in that in Example 1 the 35% solution of Sokalan CP2 by a 35% solution of Sokalan CP5 or by Sokalan CP 7 or Sokalan CP 8 (copoly ere sodium salts from acrylic acid and maleic acid, brand name of BASF AG) was replaced.

Other agents according to the invention were also obtained by adding the salts used in the above examples in the form of the potassium salts.

Example 3:

The example describes the production of a detergent and cleaning agent which contains free potassium hydroxide. 8.5 kg of potassium hydroxide (90 * active substance) were dissolved in 410 kg of demineralized water with stirring and external cooling at 55 ° C. Then, as in Example 1, 85 kg of Kauai water glass (30 * active substance), 48 kg of sodium salt of nitrilotriacetic acid (92 * active substance), 380 kg of potassium carbonate powder and 68.5 kg of a 35% aqueous solution of Sokalan CP2 were added in succession added with stirring, dissolved and filtered.

Example 4:

Further agents according to the invention were obtained by replacing potassium hydroxide and potassium water glass with the corresponding sodium salts in Example 3 and at the same time the sodium salt of nitrilotriacetic acid and the sodium salt of the copolymer with the corresponding potassium salts and by adding all the salts in the form of the potassium salts.

Further agents according to the invention were also obtained by partially (at 15% by weight, based on the amount of sodium salt of nitrilotriacetic acid used in Example 3), using sodium citrate or potassium citrate or by the sodium salt of 1- Hydroxyethane-l, l-di- phosphonic acid or replaced by diethylenetriaminepentamethylπphosphonic acid.

Likewise, further agents according to the invention were obtained by replacing the 35% solution of Sokalan CP 2 in Example 3 with a 35% solution of Sokalan CP 5 or with Sokalan CP 7 or So¬ kalan CP 8.

Example 5:

This example describes the application test carried out in a household washing machine with a horizontally arranged washing drum (type: Adora 4) under the following conditions:

Washing temperature: 40 ° C, 60 ° C and 95 ^β C single eye process

Water hardness: 14 ^β d (140 mg CaO per liter)

Detergent dosage: 40 g

Textile samples: 2 test strips each with the same soiling and 2 kg clean filling laundry, 4-fold determination

The tested textile detergent W according to the invention had the following composition:

38% by weight * potassium carbonate 9% by weight * potassium water glass (30 * active substance) 0.5% by weight * potassium hydroxide (90 * active substance) 5% by weight * nitrilotriacetic acid trisodium salt (92% active substance) 7% by weight * Sokalan CP 5 (acrylic acid-maleic acid copolymer,

Na salt; 35% active substance) balance water 12 - ^~

The composition of the comparison formula V, a conventional commercial textile detergent with a high alkali hydroxide content, was as follows:

9.5% by weight * potassium water glass (30 * active substance) 23.5% by weight * potassium hydroxide (90 * active substance)

5% by weight * nitrilotriacetic acid trisodium salt (92% active substance) 8.5% by weight * Sokalan CP 5 (35 * active substance) balance water

Soiling:

I dust / wool grease on cotton

II Dust / skin fat on refined cotton

III Dust / skin oil on polyester / finished cotton

IV dust / skin oil on polyester

V Lipstick on polyester / finished cotton

VI make-up on polyester / refined cotton

VII mineral oil on polyester / finished cotton

VIII red wine on refined cotton

IX tea on refined cotton

X Coffee on refined cotton

XI milk / cocoa on cotton

When evaluating Tables 1 to 3, it must be taken into account that remission differences of 2 * and more can be directly understood by the consumer. The optical evaluation of the washing results was carried out using a Zeiss reflectometer at 460 nm. It can be seen that the washing agent W according to the invention delivered comparable to better results than the conventional comparative washing agent V across all temperatures. Table 1: Temperature 40 ^β C

Table 3: Temperature 95 ^β C

The application test of further agents according to the invention gave comparable results.

Claims

1. Phosphate-free, liquid washing and cleaning agent containing (A) 5-60% by weight * potassium carbonate, (B) 1-40% by weight * alkali silicate with a molar ratio of M2O: SiO 2 of 1: 2 to 1: 4, where M is sodium or potassium, (C) 1-30% by weight of an organic builder substance, (D) 1-20% by weight of a polymeric complexing agent and (E) 30-80% by weight of water , with the proviso that the components (A) to (D) are calculated as anhydrous substances.

2. Composition according to claim 1, characterized in that the weight ratio of potassium ions to sodium ions is at least 3: 1 and is preferably between 5: 1 and 60: 1.

3. Agent according to claim 1 or 2, characterized in that the agents contain 10-55% by weight, preferably 20-50% by weight potassium carbonate.

4. Composition according to one of claims 1-3, characterized in that the alkali silicate (B) contains potassium silicate in the amounts of 1.5-20% by weight *, preferably 2-10% by weight *.

5. Composition according to one of claims 1-4, characterized gekennzeich¬ net that they contain as an organic builder Nitrilotriessig¬ acid in the form of the trisodium salt in amounts of 1 - 20 wt .- *, preferably 2 - 10 wt .- *.

6. Composition according to one of claims 1-5, characterized gekenn¬ characterized in that they are polymeric complexing agents (D) copolymers of acrylic acid and maleic acid or of maleic anhydride and methyl vinyl ether, preferably in the form of the sodium salts, in amounts of 1.5-20 wt .- *, preferably contain 2 - 5 wt .- *.

7. Composition according to one of claims 1-6, characterized gekennzeich¬ net that they contain potassium hydroxide in amounts of 0.5 - 4 wt .- *, preferably 0.5 - 3 wt .- *.

8. Composition according to one of claims 1-7, characterized gekennzeich¬ net that they contain surfactants in amounts of 0.5 - 5 wt .- *, preferably 0.5-3 wt .- *.

9. Composition according to one of claims 1-8, characterized gekennzeich¬ net that all salt-like components are in the form of potassium salts.

10. A process for the preparation of a phosphate-free liquid washing and cleaning agent containing (A) 5-60% by weight * potassium carbonate, (B) 1-40% by weight * alkali silicate with a molar ratio of M: SiO 2 of 1: 2 to 1 : 4, where M is sodium or potassium, (C) 1-30% by weight of an organic builder, (D) 1-20% by weight of a polymeric complexing agent and (E) 30-80% by weight. Water, with the proviso that the components (A) to (D) are calculated as anhydrous substances, characterized in that the agent is produced in a manner known per se.