EP0609303B1 - Liquid detergent concentrate for hard surfaces - Google Patents

Abstract

The cleaning power of liquid detergent concentrates for hard surfaces based on aqueous solutions of non-ionic surface-active agents is improved by adding thereto the alkoxylation products of OH-groups-containing carboxylic acids (polyolalkoxylates) or their derivates, or mixtures thereof with other anionic or non-ionic surface-active agents. The preparation of polyolalkoxylates with preferably 30-85 (30-65) ethylene or propylene oxide units is carried out from the epoxides of unsaturated oils. This detergent preferably further contains anionic surface-active agents of the sulphonate or sulphate type, fatty alkyl glucosides, sulphosuccinates and glycerin monoalkylethers, the weight ratio between the alkoxylation products and the other surface-active agents lying between 1:100 and 100:1 approximately, preferably between 1:10 and 10:1.

Description

Liquid all-purpose detergents for household and commercial use have taken their place in the past decade because they are easy and straightforward to use. The agents are usually marketed as preferably aqueous concentrates. They can already be identified as such, i.e. Apply undiluted, on a damp absorbent cloth of any texture or a sponge, with which the hard surfaces made of metal, painted wood, plastic, ceramic products such as porcelain, tiles, tiles and the like, are wiped away, thereby removing dust, greasy dirt and stains. It is desired that this surface treatment in turn does not leave any detergent stains and strips behind and does not require any aftertreatment, for example with a cloth soaked in clear water, that is to say moist.

Such liquid all-purpose cleaning agents generally consist of concentrated solutions of various anionic surfactant mixtures, but mixtures of anionic and nonionic surfactants are also known. Among other things, you will described in DE 28 40 463, EP 71 411 and DE 39 43 070.

From Kirk-Othmer, "Encyclopedia of Chemical Technology", ^3rd Ed. (1979), Vol. 5, page 9, it is known that highly ethoxylated castor oils can be used as constituents in cleaning agents.

Surprisingly, it has now been found that an unpredictable excellent cleaning performance of liquid detergent concentrates for hard surfaces is achieved if alkoxylation products of carboxylic acids containing OH groups and / or their derivatives or mixtures of these compounds with other known anionic or nonionic surfactants are used as surfactants.

The cleaning performance of these concentrates reaches the level of known, good alkylbenzenesulfonate-containing formulations with a cleaning-enhancing polymer component, as they are e.g. fall under the scope of protection of DE 28 40 463.

The present invention thus relates to a liquid detergent concentrate for hard surfaces based on aqueous solutions of nonionic surfactants, optionally together with other anionic and / or nonionic surfactants, organic and / or inorganic builders, water-soluble solvents or solubilizers, and other usual constituents of such detergents, which thereby characterized in that it is a nonionic surfactant of about 1.0 to 30, preferably about 2.0 to 15,% by weight, based on the total concentrate, of an alkoxylation product of carboxylic acids containing OH groups and / or their derivatives (polyol alkoxylates) contains, with 30 - 85 wt .-%, preferably 30 - 65 wt .-% ethylene oxide or propylene oxide.

The preparation of these polyol alkoxylates is described in German patent application P 39 23 394.4. It takes place via the epoxides of unsaturated oils.

The epoxides of unsaturated oils and fats, such as soybean oil, linseed oil, sunflower oil or rapeseed oil, have been known for a long time and are inexpensive to produce on an industrial scale. Their reaction with hydrogen or protic compounds such as water, alcohols or carboxylic acids leads to polyols which, depending on the fatty acid composition of the starting materials, carry a hydroxy group in the 9- or 10-position of the fatty alkyl chain. With polyunsaturated fatty acids, several hydroxyl groups per fatty acid chain are obtained depending on the number and position of the double bonds. These can then be reacted with ethylene oxide and / or propylene oxide to give mostly liquid alkoxylates (polyol alkoxylates).

In the field of cleaning hard surfaces, the polyol alkoxylates can preferably be used as the sole active ingredient, but also in combination with any other known surfactants of the sulfonate and / or sulfate type, and preferably with fatty alkyl glucosides, dialkyl sulfosuccinates and Glycerol monoalkyl ethers can be used. Their share in the total mixture can be about 50 to 80, preferably 50 to 65% by weight.

The surfactants of the sulfonate type are alkylbenzenesulfonates (C₉₋₁₅-alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating group, into consideration. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other useful sulfonate type surfactants are the esters of α-sulfo fatty acids, e.g. the α-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.

The preferred surfactants of the sulfate type for ecological reasons are the sulfuric acid monoesters of primary C₁₂-C₁₈, preferably C₁₂-C₁₄ fatty alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of corresponding secondary alcohols. Sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1-5 moles of ethylene oxide with primary or secondary fatty alcohols are also suitable.

The fatty alkyl glucosides that can be used here are understood to mean compounds with an average of less than two glucose units per fatty alkyl radical, in particular those with 1 to 1.4 glucose units. The fatty alkyl radical has 10 to 18, in particular essentially 12 to 14, carbon atoms. “Fatty alkyl” is understood to mean the rest of the fatty alcohols which are produced by hydrogenation of natural fatty acids and which are wholly or predominantly saturated or which also comprise unsaturated portions.

The dialkyl sulfosuccinates are alkali metal, ammonium or substituted ammonium salts and can be derived from a C₇, C₈ or C₉ alcohol, which can be linear or branched, or from any mixture thereof. The preferred material is the straight chain and branched Di-octylsulfosuccinate. The dialkyl sulfosuccinates were prepared by customary methods, for example by esterification of maleic acid and subsequent sulfonation with bisulfite.

All anionic surfactants can be present in the form of their alkali, alkaline earth and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The sodium salts are mostly preferred for reasons of cost.

in der R für einen Alkylrest mit 1 - 22, vorzugsweise 8 - 18 C-Atomen, n für eine Zahl im Bereich 0 - 20, vorzugsweise 0 - 10 und x + y für eine Zahl im Bereich 0 - 60, vorzugsweise 0 - 30 stehen, sowie von Mischungen mehrerer derartiger Verbindungen.The glycerol monoalkyl ethers are compounds of the general formula

in which R stands for an alkyl radical with 1 to 22, preferably 8 to 18, carbon atoms, n for a number in the range 0 to 20, preferably 0 to 10 and x + y for a number in the range 0 to 60, preferably 0 to 30 stand, as well as mixtures of several such compounds.

These glycerol monoalkyl ethers can advantageously be prepared by combining excess glycerol in a reaction kettle with sodium hydroxide solution and heating under a nitrogen atmosphere, with water being distilled off. The batch is stirred for several hours. Then this reaction product is reacted with fatty alcohol sulfate, sodium salt or fatty alcohol polyethylene glycol ether sulfate, sodium salt, and the reaction mixture is heated for a few more hours. The raw product is washed several times with water. Residual water in the organic phase is removed under reduced pressure. The glycerol monoalkyl ethers (GE) thus obtained can then, if appropriate in the presence of a catalyst (e.g. Na methylate), be reacted with ethylene oxide in a pressure vessel under a nitrogen atmosphere at elevated temperature.

For the cleaning agent concentrates according to the invention, about 0.5 to 10, preferably 1.5 to 5% by weight, based on the concentrate as a whole, can furthermore act as alkalis in their entirety inorganic or organic compounds, as well as inorganic or organic complexing agents are used, which are preferably in the form of their alkali or amine salts, in particular the sodium and potassium salts. The alkali hydroxides also belong to the framework substances here.

Further usable inorganic substances which can optionally be added to the agents according to the invention are, for example, bicarbonates, carbonates, borates, silicates or polyphosphates such as pentasodium triphosphate, pyrophosphates or orthophosphates. The latter salts containing phosphorus ions should not be used for ecological reasons.

The organic complexing agents of the aminopolycarboxylic acid type include, among others, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylene diamine triacetic acid. The following may be mentioned as polyphosphonic acids: methylene diphosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid, propane-1,1,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane-1 , 2, dicarboxy-1,2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphonosuccinic acid, 1-aminoethane-1,2-diphosphonic acid, aminotri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediaminetetra (methylenephosphonic acid).

Compounds containing carboxyl groups are often, if not exclusively, proposed as examples of N- or P-free and therefore preferred mono- or polyvalent carboxylic acids or their salts as builder substances. A large number of these carboxylic acids have a complexing ability for calcium. These include e.g. As citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, gluconic acid, glutaric acid, succinic acid, adipic acid, polyacrylic acids and copolymers or mixtures thereof.

Since household cleaning agents are generally neutral to slightly alkaline, ie their aqueous use solutions at application concentrations of usually about 1 to 20, preferably about 5-15 g / l water or aqueous solution have a pH in the range of 7.0-10.5, preferably 7.0-9.5, can be added to regulate the pH by adding small amounts of acidic and / or or alkaline components, also as a buffer.

Suitable acidic substances are conventional inorganic or organic acids or acidic salts, such as hydrochloric acid or sulfuric acid, lactic acid, polycarboxylic acids, such as. B. citric acid, tartaric acid, glutaric acid, succinic acid, adipic acid or mixtures thereof and the like.

If the content of alkaline builders is not sufficient to regulate the pH, organic or inorganic compounds such as z. B. sodium hydroxide, alkanolamines, namely mono-, di- or triethanolamine or ammonia.

In addition, known solubilizers, individually or as a mixture with one another, can be incorporated, for which purpose, in addition to the water-soluble organic solvents, such as, in particular, low molecular weight aliphatic alcohols having 1-4 carbon atoms, also the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or Cumene sulfonates or short chain alkyl sulfates such as octyl sulfate belong. They can also be in the form of their sodium and / or potassium and / or alkylamino salts. Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1 to 6 carbon atoms in the molecule.

Other suitable water-soluble or water-emulsifiable organic solvents are ketones, such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic and aromatic hydrocarbons, and also the terpene alcohols.

The weight ratio of surfactant to solvent or solubilizer can be 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1.

To regulate the viscosity, it may be advisable to add small amounts of higher polyglycol ethers with molecular weights up to about 600 or polyglycerol. It is also advisable to add sodium chloride and / or urea to regulate the viscosity.

In addition, the claimed agents may contain additives to colorants, fragrances and preservatives as other usual constituents.

A frame formulation of the concentrates according to the invention can thus have a total of approximately the following basic composition: Components % By weight Polyol alkoxylates: 1.0 to 30, preferably 2.0 to 15 Other surfactants: 0 to 80, preferably 50 to 80 Framework substances: 0 to 10, preferably 1.5 to 5 Surfactants: Solvents / Solubilizers: 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1 Dyes / fragrances / preservatives: small quantities Water: Rest of 100 each

tries

To demonstrate the advantages of the cleaning agents according to the invention compared to the known cleaning agents for hard surfaces, comparisons were made with regard to their cleaning ability.

Testing the cleaning effect

The test method described below was used to test the cleaning ability and provides very reproducible results. The detachment of dirt from hard surfaces was assessed according to the cleaning ability test described in Soap-Oil-Fat-Waxes 112 , 371 (1986).

The cleaning agent to be tested was placed on an artificially soiled plastic surface. When using a detergent with 10 wt .-% surfactant, a mixture of petroleum jelly ^(R) , fatty acid glycerol esters and pigments was used as test soiling. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater. The test area was coated with 10 ml of the cleaning agent solution. After ten wiping movements with a plastic sponge, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the whiteness of the plastic surface cleaned in this way, was determined using a Microcolor color difference measuring device from Dr. Measured for a long time. The clean white plastic surface served as the white standard. Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage of cleaning ability (% RV). In the experiments below, the values RL rel. (%) the values determined by this method for the cleaning ability of the investigated cleaning agents, based on the cleaning performance of the comparison recipe according to DE 28 40 463 (RL = 100%). They represent mean values from triplicate determinations.

Examples Example 1: Polyolethoxylate from soybean oil epoxide, pre-fatty acid and 61% by weight EO

1225 g (7.9 mol) of preliminary fatty acid (60% C₈, 35% C₁₀, SZ = 361.9) were placed, heated to 150 ° C with stirring and within 1 h with 1770 g (7.5 mol on Ep. -O related) soybean oil epoxide (Ep.-O = 6.78) added. After the addition had ended, the temperature was slowly increased to 170 ° C. and after 2 h (Ep.-O <0.15%) in a vacuum (approx. 0.02 mbar) to 200 ° C. (469 g distillate). The end product is a yellow, clear polyol (viscosity = 5550 mPas (Höppler, 20 ° C), OHZ = 105, VZ = 236, SZ = 3.1).

423 g (39 parts) of the reaction product of soybean oil epoxide with starter fatty acid were mixed with 6.9 g of a 30% solution of potassium hydroxide in methanol and heated to 100 ° C. in an autoclave. At this temperature, the traces of methanol were removed by evacuating 5 times and venting with nitrogen as a protective gas. After the reaction temperature had been raised to 150 ° C., a total of 660 g (61 parts) of ethylene oxide were metered in in portions so that the pressure in the reactor did not exceed 5 bar. After the reaction had ended, the mixture was cooled to 80-100 ° C., evacuated for about 15 minutes to remove traces of ethylene oxide and neutralized with lactic acid. The crude product is a clear, yellow liquid (OHZ = 54.7).

Example 2: Polyolethoxylate from soybean oil epoxide, pre-fatty acid and 55% by weight EO

428 g (45 parts) of the ring opening product of soybean oil epoxide with forerun fatty acid were mixed with 2.8 g of a 30% strength methanolic potassium hydroxide solution and reacted with 528 g (55 parts) of ethylene oxide at 150 ° C. under the conditions specified in Example 1. After removing the traces of ethylene oxide in vacuo and neutralization with lactic acid, a dark yellow liquid was obtained (OHZ = 54.5).

Example 3: Polyolethoxylate from hydrogenated soybean oil epoxide and 65% by weight EO

20 kg of epoxidized soybean oil (Ep.-O = 6.78%) and 0.2 kg of a nickel catalyst were placed in an autoclave, the air present in the reactor was displaced by nitrogen flushing and at 150-170 ° C. with a hydrogen pressure of 20 bar, hydrogenated until the end of the hydrogen uptake (approx. 6 h). After cooling and separating off the catalyst, a colorless solid was obtained (OHZ = 165.8, VZ = 181.4, JZ = 8.3).

371 g (35 parts) of hydrogenated soybean oil epoxide were mixed with 2.5 g of a 30% solution of potassium hydroxide in methanol and reacted with 704 g (65 parts) of ethylene oxide in accordance with Example 1. The crude product is a clear, yellow liquid (OHZ = 62.9).

Example 4: Polyolethoxylate from soybean oil epoxide, methanol and 52% by weight EO

2360 g (10 mol) of epoxidized soybean oil (EP.-O = 6.78%) were concentrated with intensive cooling to the refluxing solution of 9 g (o, 9 g / mol epoxy). Drops of sulfuric acid in 960 g (30 mol) of methanol. After the epoxy had been added and the epoxide had reacted, the reaction mixture was neutralized with diethylethanolamine and the excess methanol was removed in vacuo. This gave a clear yellow liquid (OHZ = 185, VZ = 163, JZ = 19.4, SZ = 1.6).

480 g (48 parts) of the ring opening product of soybean oil epoxide with methanol were mixed with 8.0 g of a 30% strength methanolic sodium methylate solution and reacted with 520 g (52 parts) of ethylene oxide at 160 ° C. under the conditions specified in Example 1. After removing the traces of ethylene oxide in vacuo, a red-brown liquid (OHZ = 106.1) was obtained.

Example 5: Polyolethoxylate from soybean oil epoxide, EDENOR K8 / 18 and 61% by weight EO

As in Example 1, 2353 g of epoxidized soybean oil were ring-opened with 2099 g EDENOR K8 / 18. The product is a dark yellow liquid (OHZ = 69.5, VZ = 215, JZ = 8.4, SZ = 0.6).

390 g (39 parts) of the ring opening product of soybean oil epoxide with EDENOR K8 / 18 were mixed with 9.7 g of a 30% strength methanolic sodium methylate solution and reacted with 610 g (61 parts) of ethylene oxide at 160 ° C. under the conditions specified in Example 1. After removing the traces of ethylene oxide in vacuo and neutralizing with lactic acid, a dark yellow liquid was obtained (OHZ = 53.4).

Example 6:

All-purpose cleaner base formulations with polyol alkoxylates were tested. The active substance content of the concentrates was 10% by weight.

A powerful standard formulation, which falls under the scope of protection of the patent specification DE 28 40 463, served as a comparison:
8% by weight of alkylbenzenesulfonate, Na salt
2% by weight adduct of C _12/14 alkyl epoxide + ethylene glycol + 10 mol ethylene oxide
2% by weight Na gluconate
0.1% by weight of polyethylene glycol with a molecular weight of approx. 600,000 (Polyox WSR 205 ^(R) from UCC)
Rest of water
The cleaning performance of the formulations given in the following examples was based on the cleaning performance of the above standard formulations, this being set to 100%. The pH of the formulations was adjusted to about 7.0 either with sodium hydroxide solution or with citric acid as required.

Recipes:

Formula No. 1 2nd Compound from example 1 10% - Compound from example 2 - 10% Na gluconate 2% 2% water Rest → Cleaning performance 131% 123%

Example 7:

The compounds according to the invention from Examples 1 and 2 were also tested in combination with C _12/14 alkyl glucoside (DP = 1.4) by the method mentioned in Example 6.

Recipes:

Formula No. 4th 5 6 7 8th 9 10th 11 Verb from Example 1 8th % 6% 4% 2% - - - - Verb from example 2 - - - - 8th % 6% 4% 2% C _12/14 alkyl glucoside (DP = 1.4) 2% 4% 6% 8th % 2% 4% 6% 8th % Na gluconate 2% 2% 2% 2% 2% 2% 2% 2% water Rest → Cleaning performance in% 129 129 132 128 124 123 126 103

It can be seen from formulations 4-7 and 8-11 that the cleaning performance depends on the degree of ethoxylation of the polyethoxylates. After this, the recipes with the lower ethoxylated polyol ethoxylate from the Example 2 a lower cleaning performance than the corresponding recipes with the higher ethoxylated polyolethoxylates.

Example 8:

A high cleaning performance is also obtained if, instead of sodium gluconate, a polycarboxylate with an average molecular weight of approx. 3000 (Sokalan ES 9911 ^(R) , from BASF) is used as a builder. This is illustrated by the recipes below.

Recipes:

Formula No. 12th 13 14 15 16 Verb from Example 1 8th % 8th % 8th % 8th % 8th % C _12/14 alkyl glucoside, (DP = 1.4) 2% 2% 2% 2% 2% Polycarboxylate MG approx. 3000 - 1 % 2% 3% 5% water Rest → Cleaning performance in% 124 132 128 129 124

Example 9:

A higher cleaning performance compared to the prior art is also obtained with binary surfactant combinations of the compounds according to the invention with various anionic surfactants.

Recipes:

Formula No. 17th 18th 19th 20th Connection 1 8th % 6% 4% 2% Gluconate 2% 2% 2% 2% READ 2% 4% 6% 8th % SAS - - - - SBSE - - - - water Rest → Cleaning performance in% 119 113 120 117

The abbreviations used in the tables have the following meanings:
Compound 1: Compound from example 1
Gluconate: sodium gluconate
LAS: C _10/13 alkylbenzenesulfonate, Na salt
FAES: C _12/14 fatty alcohol ether sulfate with approx. 2 EO, Na salt
SAS: secondary C _13/17 alkanesulfonate, Na salt

Example 10:

In combination with the glycerol monoalkyl ethers described in German patent application P 39 43 070.7, the compounds according to the invention also show a high cleaning performance.

Recipes:

Formula No. 27 28 29 Compound from example 1 8th % 6% 4% Na gluconate 2% 2% 2% C _12/14 monoalkylglycerol ether + 8 EO 2% 4% 6% water Rest → Cleaning performance in% 123 124 115

Claims (3)

1. A liquid concentrate for cleaning hard surfaces based on aqueous solutions of nonionic surfactants, optionally together with other anionic and/or nonionic surfactants, organic and/or inorganic builders, water-soluble solvents or solubilizers and other typical constituents of such concentrates, characterized in that it contains 1.0 to 30% by weight and preferably 2.0 to 15% by weight, based on the concentrate as a whole, of an alkoxylation product of OH-functional carboxylic acids and/or derivatives thereof with 30 to 85% by weight and preferably 30 to 65% by weight of ethylene oxide or propylene oxide as the nonionic surfactant.
2. A concentrate as claimed in claim 1, characterized in that it contains anionic surfactants of the sulfonate and/or sulfate type, fatty alkyl glucosides, sulfosuccinates and glycerol monoalkylethers as the other anionic and/or nonionic surfactants.
3. A concentrate as claimed in claims 1 and 2, characterized in that the ratio by weight of alkoxylation products of OH-functional carboxylic acids and/or derivatives thereof to the other anionic and/or nonionic surfactants optionally present is about 1:100 to about 100:1 and preferably about 1:10 to about 10:1.