CH631205A5 - Homogeneous, liquid detergent based on water - Google Patents

Abstract

The homogeneous, liquid detergent based on water contains a) 2 to 20 per cent by weight of a synthetic detergent compound which is not a soap or a fatty acid alkylolamide, b) at least 4 per cent by weight of sodium tripolyphosphate, c) at least 2 per cent by weight of sodium orthophosphate or potassium orthophosphate, the sum of b) and c) being 6 to 35 per cent by weight, and the weight ratio of b) : c) being from 10 : 1 to 1 : 10, d) 1 to 15 per cent by weight of a hydrotropic constituent from the group consisting of alkali metal or ammonium toluene-, -xylene- or -cumenesulphonate, urea, lower aliphatic alcohols and mixtures thereof and e) 1 to 15 per cent by weight of a hydrotropic constituent from the group consisting of C8-C18-fatty acid alkylolamide, calcium soap of C10-C22-fatty acids and calcium soap of dimerised C10-C22-fatty acids in an aqeuous medium which optionally contains further customary detergent constituents.

Description

The invention relates to a homogeneous, liquid, aqueous-based detergent containing phosphate builder.

Aqueous based liquid detergents are well known in the art. Although they offer several advantages over other forms of detergents, such as powders, e.g. B. better solubility and easier dosage, their composition is very difficult because they are in a wide range of storage conditions, e.g. B. from about -4 to +37 ° C, should be physically stable. In addition, they should have satisfactory pouring properties, even though they contain relatively high concentrations of detergent constituents, in particular builder salts, so that their performance is ideally equivalent to that of conventional powder detergents.

The prior art mainly teaches the use of more water-soluble ingredients such as tetrapotassium pyrophosphate, usually with expensive stabilizers, but even then the amount that can be used is less than desirable compared to powder detergents. While such previous liquid compositions may provide acceptable agents as far as their physical properties are concerned, their washing effectiveness and other washing properties are unsatisfactory. For example, with alkali metal pyrophosphates, deposits often formed on the garments, especially when the products were used in unusually low product concentrations or at high temperatures.

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If attempts were made to improve the washing effect, stability and pourability became unsatisfactory. In particular, it was not possible to incorporate sufficiently high amounts of conventional builders, such as sodium tripolyphosphate, into the liquid detergents without causing serious problems in the separation or solidification or solidification of the liquid detergents.

It has now been found that homogeneous, clear, built-up, liquid detergents can be obtained by using certain mixtures of sodium tripolyphosphate and sodium or potassium orthophosphate as a builder and using a hydrotropic system which comprises at least two hydrotropic agents, which are defined below .

As far as these two builder substances normally work in different ways, i. H. With sodium tripolyphosphate as the complexing or sequestering builder and the alkali metal orthophosphate as the precipitating builder, it is somewhat surprising that a mixture of these substances works so effectively. Especially when sodium orthophosphate is used alone as a builder, it easily leads to inorganic deposits on the washed textiles accompanied by redeposition of dirt, but in the presence of sodium tripolyphosphate the dirt redeposition is considerably reduced, while the washing power is obviously very much increased. In addition, compared to using sodium tripolyphosphate alone as a builder, the same amount of the mixture of sodium tripolyphosphate and alkali metal orthophosphate builder shows improved detergency and soil redeposition properties, particularly in hard water.

In the past, numerous proposals have been made for using mixed phosphate builders, e.g. B. Mixtures of sodium pyrophosphate and sodium tripolyphosphate, in liquid agents, especially those for cleaning hard surfaces. It is also well known that the condensed phosphates, such as. B. tripolyphosphate, tend to degrade or decompose under aqueous alkaline conditions at high temperatures, which often occur under detergent processing conditions, so in the formation of other phosphates; Sodium tripolyphosphate e.g. B. tends to decay to form a mixture of sodium pyrophosphate and sodium atrium orthophosphate.

To date, however, to the best of our knowledge, it has not been proposed to use the special mixtures of sodium tripolyphosphate and alkali metal orthophosphate in the ratios specified below in liquid textile detergents which contain a suspended solid phase according to the invention. The formation of clear, liquid detergents with much higher builder contents than was previously possible is particularly advantageous. In addition to the advantages of lower viscosity and better storage properties than heterogeneous liquid suspending agents for the consumer, they are generally easier to manufacture.

The ratio of sodium tripolyphosphate to sodium or potassium orthophosphate in the detergent is between 10: 1 to 1:10, in particular 5: 1 to 1: 2 parts by weight, preferably 4: 1 to 2: 3 and in particular 3: 1 to 1: 1 parts by weight. These ratios of sodium tripolyphosphate to sodium or potassium orthophosphate are chosen to achieve optimal builder properties and other washing properties relative to the maximum amount of these components that can be tolerated in the liquid compositions without loss of stability.

The actual amounts of sodium tripolyphosphate and sodium or potassium orthophosphate are preferably chosen according to the total content of phosphate builder that is desired or permitted in the liquid detergents.

The total amount of sodium tripolyphosphate plus sodium or potassium orthophosphate is in the range from 6 to 35 percent by weight of the composition, preferably 10 to 25, in particular 15 to 25 percent by weight. The individual amount of sodium tripolyphosphate and sodium or potassium orthophosphate is at least 4 or 2%, the latter preferably being at least 4% by weight of the composition.

If higher levels of sodium tripolyphosphate are used, i. H. more than about 12% by weight of the composition, it is advantageous to use a type of sodium tripolyphosphate that hydrates rapidly since this promotes solubility, especially when used in compositions that have higher levels of sodium tripolyphosphate. Suitable types of sodium tripolyphosphate have a high, i.e. H. Phase I content above 50% is commercially available, and they can also be partially or completely prehydrated. The processing conditions, including mixing temperatures, are of course generally set in accordance with the type of sodium tripolyphosphate used.

In addition to the mixed phosphate builders, the liquid detergents according to the invention contain a synthetic detergent compound, which can be an anionic, nonionic, amphoteric or zwitterionic detergent compound or a mixture thereof. Many suitable detersive compounds are usually commercially available and have been extensively described in the literature, e.g. B. in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent compounds that can be used are synthetic anionic compounds. They are usually water-soluble alkali metal salts of organic sulfates and sulfonates with alkyl radicals with about 8 to about 22 carbon atoms, the term alkyl including the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium primary or secondary arylalkyl sulfates, in particular those obtained by sulfating the higher (Cs-Cis) alcohols, which are obtained by reducing the glycerides of tallow or Coconut oil was obtained; Sodium and potassium alkyl (Co-C2o) -benzenesulfonates, especially sodium lin.-sec.-alkyl (Cio-Ci5) -benzenesulfonates; sodium alkylglyceryl ether sulfates, especially those ethers of the higher alcohols, which are derived from tallow or derive coconut oil and synthetic petroleum alcohols, sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium and potassium salts of sulfuric acid esters of higher (C9-Ci8) fatty alcohol alkylene oxide, in particular ethylene oxide reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; Sodium and potassium salts of fatty acid amides of methyl taurine; primary or secondary alkane monosulfonates, such as those from the reaction of alpha-01efinen (C8-C2o) with sodium bisulfite and those from the reaction of paraffins with SO2 and CI2 and subsequent hydrolysis with a base to a statistical sulfonate; and olefin sulfonates, a term that describes a material made by reacting olefins, especially alpha olefins, with SO3 and then neutralizing and hydrolyzing the reaction product.

Although the sodium salts of the anionic detergent compounds are generally preferred for reasons of cost, the potassium salts can occasionally be used with advantage, especially in agents with high levels of other sodium salts such as sodium tripolyphosphate and sodium orthophosphate.

Of the anionic wash-active compounds, alkali metal (Cio-Ci5) alkylbenzenesulfates are particularly preferred, both because of their easy accessibility and cost

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found as well as due to their advantageous solubility properties.

If desired, nonionic detergent compounds can be used as the only detergent compounds or preferably in a mixture with anionic detergent compounds, in particular the alkylbenzenesulfonates. Examples include the reaction products of alkylene oxides, ordinary ethylene oxide, with (C6-C22) phenols, generally 5 to 25 ÄO, i.e. H. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic primary or secondary (Cs-Cis-alcohols with ethylene oxide, usually 2 to 30 EO, for example 6 to 20 EO), and products produced by condensing ethylene oxide with the reaction products of propylene oxide and ethylenediamine. For example, it is also possible to use them to use nonionic agents which were first prepared by ethoxylation and then propoxylation of the hydroxyl-containing organic radical, for example of Cs-Cis-Alko-hol, with ÄO and PO. Other so-called nonionic detergent compounds include, for example, long-chain tertiary Amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Mixtures of active washing compounds, e.g. B. mixed anionic or mixed anionic and nonionic compounds can be used in the detergents, especially to give them controlled low-foaming properties. Mixtures of amine oxides and ethoxylated anionic compounds can also be advantageous.

Amounts of amphoteric or zwitterionic detergent compounds can also be used in the liquid detergents according to the invention, this is normally not desirable because of their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, this is generally done in small amounts, on average, based on the much more commonly used anionic and / or nonionic detergent compounds.

The amount of synthetic detergent compound or compounds is in the range of 2.0 to 20, preferably 5 to 15 percent by weight of the composition, depending on the desired properties. Lower levels of nonionic detergent compounds should be used within this range since they tend to tend to form their own liquid phase when used in higher levels, i. H. over about 5 weight percent. The ratio of total detergent compounds to the total amount of sodium tripolyphosphate and sodium or potassium orthophosphate should generally range from about 2: 1 to about 1: 5, preferably from about 1: 1 to about 1: 3 parts by weight.

In order to facilitate the production of the homogeneous liquid detergents with relatively high levels of builders, potassium orthophosphate is preferably used instead. The potassium orthophosphate can be added as such, or orthophosphoric acid can be neutralized with a potassium salt such as potassium hydroxide during the preparation of the compositions. It should be noted that the term sodium or potassium orthophosphate includes the mono-, di- and tri-orthophosphates. The potassium salt can be used instead of the sodium tripolyphosphate, but this is more expensive.

It is important to have a hydrotropic system in the media, preferably to reduce any tendency to separate into different liquid phases. The hydrotropic system which has been found to be effective for use in the homogeneous liquid detergents comprises a hydrotropic agent from the group of the alkali metal or ammonium toluene, cumene and xylene sulfonates, urea, lower aliphatic

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see alcohols, such as ethanol, which is commonly supplied as industrial alcohol denatured with methanol (IMS), and a hydro-tropical agent of the group of lower (Cs-Ci8) fatty acid alkanol amides, such as coconut ethanol amide, and easily water-soluble soaps of Cio-C22 fatty acids , including such polymerized fatty acids, such as Potassium coconut soap and potassium oleate, potassium soap dimerized oleic acid and mixtures thereof. The presence of such soaps as hydrotropes is normally of particular advantage in the case of homogeneous liquid agents with higher levels of sodium tripolyphosphates, i.e. H. over about 15 weight percent. The fatty acid alkylolamides also act as foam improvers and should therefore normally not be used in low-foaming agents.

The amount of each hydrotropic agent forming the hydrotropic system is in the range of 1 to 15, preferably 5 to 10 percent by weight of the agent. It should be noted that an excess of these hydrotropic agents can be just as harmful as too little material for optimal properties of the liquid agent, but satisfactory levels can easily be found within the range described.

It is generally desirable to incorporate one or more redeposition prevention agents into the liquid detergents of the invention to reduce any tendency to form inorganic deposits on laundered fabrics, particularly under low product concentration conditions. Examples of preferred agents for preventing redeposition are homo- and copolyacrylates, e.g. B. sodium polyacrylate, the sodium salt of copolymethacrylamide / acrylic acid and sodium poly-alpha-hydroxyacrylate, salts of copolymers of maleic anhydride with ethylene, methyl vinyl ether or styrene, in particular 1: 1 copolymers, optionally with partial esterification of the carboxyl groups, and the sodium salts of polymaleic acid and polyitaconic acid. Such copolymers usually have relatively low molecular weights, e.g. B. in the range of about 2000 to 50,000. The maleic anhydride copolymers can also have certain stabilizing properties, especially when nonionic detergent compounds are used. Further, less preferred anti-redeposition agents include phosphate esters of ethoxylated aliphatic alcohols, polyethylene glycol phosphate esters and certain phosphonates such as sodium ethane-l-hydroxy-l, l-diphosphonate, ethylene diamine tetramethylene phosphonic acid and sodium 2-phosphonobutane tricarboxylate. The most preferred anti-redeposition agent is sodium polyacrylate with a molecular weight of about 2,000 to about 30,000, e.g. B. about 15,000 to 25,000. The amount of such anti-redeposition agents is generally between about 0.1 and about 5, preferably about 0.2 and about 2 percent by weight of the agents.

Small amounts, e.g. B. up to about 10 percent by weight of other builders, which can be either so-called precipitation builders or complexation builders. This can be of particular advantage where the washing power is to be increased, while particularly small amounts of the necessary sodium tripolyphosphate and the sodium or potassium orthophosphate are used as builders in order to achieve particularly low phosphorus contents in the detergents for reasons of environmental protection. Examples of such other builders are amine carboxylates, such as sodium nitrilotriacetate. In general, however, it is desirable to have no other phosphate builders apart from sodium tripolyphosphate and sodium or potassium orthophosphate, and it is particularly desirable to exclude pyrophosphate from the agents, since they remove inorganic deposits and contaminants.

Reinforce redeposition slightly. Some pyrophosphate can e.g. B. present as an impurity in the sodium tripolyphosphate or by hydrolysis of the sodium tripolyphosphate in the production of detergents, especially under alkaline conditions at higher temperatures, therefore small amounts of sodium pyrophosphate may be unavoidable, but they should preferably be less than about 5, particularly preferably less than about 2 percent by weight Make up funds.

The liquid detergents of the present invention may contain any of the conventional additives in the amounts in which such additives are normally used in liquid laundry detergents. Examples of these additives are foam suppressants, anti-redeposition agents such as carboxymethyl cellulose (CMC), alkaline salts such as alkali metal carbonate or alkali metal hydroxides and, usually present in very small amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and dyes. If CMC is used, it has usually proven advantageous to also incorporate a stabilizing agent for this material, e.g. B. a hydrogenated castor oil (castor wax), carnauba wax, beeswax, etc.

The addition amount of the agents is water, which is usually present in an amount from about 40 to about 75, preferably from about 45 to about 65 percent by weight.

To ensure high detergency, the liquid detergents should usually be alkaline, and preferably they should have a pH in the range of about 9 to 12, preferably about 9.5 to about 11 when used in aqueous solution of the detergent at the recommended concentration will. To meet this requirement, the undiluted liquid agent should preferably also be of high pH, e.g. B. about pH 12 to 13, preferably about pH 12.5. It should be noted that an extremely high pH, e.g. B. about pH 13, is generally less desirable for reasons of household security. The constituents in such highly alkaline detergents should of course generally be selected in accordance with their alkali stability, this applies in particular to pH-sensitive substances such as enzymes, and a proteolytic enzyme which is particularly suitable in this regard is commercially available under the name “Esperase”.

An alkali buffer, e.g. B. alkali metal carbonate to keep the pH at use at least 9, especially under operating conditions, e.g. B. in hard water or at low product concentrations when the sodium or potassium orthophosphate is precipitated in the form of its calcium salt and then cannot act as an alkaline buffer itself. Alkali metal silicates, e.g. B. sodium ortho-, meta or preferably neutral or alkaline silicates, which are usually used as alkaline buffers, are more difficult to incorporate into the homogeneous liquid agents, especially at higher sodium tripolyphosphate contents. An alkali metal hydroxide, preferably potassium hydroxide, may alternatively or additionally be used to create an initially high pH.

The liquid detergents can be easily produced by adding the ingredients to water in a conventional detergent manufacturing facility. For higher levels of phosphate builders, the water is preferably first heated, e.g. B. to about 60 to 80 ° C, and then the inorganic builders are added, followed by the detergent compound or compounds and then other organic materials. On the other hand, if desired, the heat of reaction between acidic and alkaline components can be used to raise the temperature and to facilitate the mixing of the components.

The agents obtained generally have viscosities

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5 631205

in the range of about 20 to 2000, in particular about 50 to about, unless otherwise stated.

1000 cP, measured at room temperature in a Brookfield

Viscometer (spindle no.3.30 rpm). Examples I to X

Further advantages, features and embodiments of the A series of stable, homogeneous, liquid detergents

Invention result from the following description of the following recipes were prepared:

Examples where parts and percentages are by weight

Percentages

Example 1 23456789 10

component

Sodium alkylbenzenesulfonate 1

6

6

6

6

6

6

7.5

7.5

6

6

Tallow fatty amide - 11 ÄO

2nd

2nd

2nd

2nd

2nd

-

-

-

2nd

2nd

Sodium tripolyphosphate

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13

15

Potassium orthophosphate

10th

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10th

10th

7.5

7.5

6

7.5

Coconut fatty acid 2

-

-

2nd

5

5

5

11

11

-

-

Potassium hydroxide

2nd

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2nd

2nd

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1

1

dimerized oleic acid3

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-

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5

5

Sodium xylene sulfonate

5

5

5

5

5

5

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5

5

5

Ethanol

-

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2.0

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water

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58

54

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'In Examples 1 to 8 the alkylbenzenesulfonate had a (Cn-Ci5) alkyl group and in Examples 9 and 10 a (Ci i-Ci2) alkylbenzenesulfonate was used.

Neutralize with a little KOH to form the potassium coconut soap in the agent.

3 Received as EMPOL for foam control, neutralized by the KOH in the agent.

All of these compositions showed good washing properties due to the relatively high building properties of sodium tripolyphosphate and potassium orthophosphate.

Example XI

A clear, homogeneous, low-foaming, liquid detergent of the following formulation was produced:

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component

%

Potassium alkylbenzenesulfonate

7.50

(Ci6-Cis) alkyl-25 ÄO

1.45

(Ci3-Ci5) alkyl-IIEO

0.80

dimerized oleic acid

5.50

Sodium tripolyphosphate

13.00

Potassium orthophosphate 1

7.70

Sodium xylene sulfonate

6.10

Fluorescent agent

0.15

water

57.80

component

%

'Made by reaction between orthophosphoric acid and potassium hydroxide during the preparation of the product.

This agent had a low viscosity and was found to be stable down to -4 ° C.

Sodium (Cn-Ci2) alkylbenzenesulfonate

Tallow fatty amide - 11 ÄO

dimerized oleic acid

Sodium tripolyphosphate

Potassium orthophosphate

Sodium xylene sulfonate

Potassium hydroxide

Potassium carbonate

water

6.0 2.0 5.0 10.0 6.0 5.0 1.0 5.0 60.0

45 Example XIII

A clear, isotropic, highly foaming, liquid detergent with base materials of the following composition was produced:

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component

This liquid agent was easy to pour and stable when stored down to -10 ° C. Replacing the potassium carbonate with sodium carbonate also resulted in a clear, stable liquid,

but of higher viscosity. In both cases the alkaline buffering effect of the carbonate improved the washing properties of the agent.

Potassium alkylbenzenesulfonate1 (Cs-CiOalkanol - 8 ÄO potassium hydroxide sodium atrium tripolyphosphate potassium orthophosphate2 coconut fat diethanolamide potassium coconut soap1 sodium atrium xylene sulfonate / toluenesulfonate (4: 1)

water

%

8.0 2.0 4.5

16.5 5.0 2.0 1.0 6.0

55.9

65

Example XII 'Calculated as acid form.

A homogeneous, clear, liquid agent with builders 2 from dipotassium hydrogen orthophosphate was prepared by reacting the following composition: with the potassium hydroxide.

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6

This product showed good stability (-5 ° C to 52 ° C) component%

and a low viscosity of about 100 to 200 cP at room

temperature (Brookfield spindle No. 3.30 rpm) at pH 12.5.

Replacement of the nonionic detergent compound with potassium alkylbenzenesulfonate (C11-C12; as acid) 6 other similar materials, e.g. B. (C9-Cn) alkanol - 6 ÄO, (C12- 5 linear primary Cu-Cis alcohol, condensed with

Cis) alkanol - 7 ÄO or (Ci2-Cis) alkanol - 3 ÄO turned out to be 7 moles of ethylene / propylene oxide (mole ratio 88:12) 2.5

as equally satisfactory. Oleic acid • 5.0

Sodium tripolyphosphate 16.5

Example XIV Potassium Orthophosphate 6.0

A homogeneous, clear, liquid medium with builders 10 KOH 4.0

of the following composition was prepared: sodium toluenesulfonate 6.0

CMC (sodium salt) 0.25

Castor wax 0.25

Fluorescent, dyes, perfume, etc. 0.3

15 water 53.2

The viscosity was 300 cP, the pH was 12.5, and the product was stable at -5 and +37 CC for long periods.

Claims (8)

631205 PATENT CLAIMS 1. Homogeneous, liquid detergent on an aqueous basis, containing a) 2 to 20 percent by weight of a synthetic detergent compound which is not a soap or a fatty acid alkylol amide, b) at least 4 percent by weight sodium tripolyphosphate, c) at least 2 percent by weight sodium or potassium orthophosphate, the sum of b) and c) being 6 to 35 percent by weight, and the weight ratio of b): c) being from 10: 1 to 1:10, d) 1 to 15 percent by weight of a hydrotropic constituent from the group alkali metal or ammonium toluene, xylene, cumene sulfonate, urea, lower aliphatic alcohols and their mixtures and e) 1 to 15 percent by weight of a hydrotropic constituent from the group Cs-Cis- Fatty acid alkylolamide, potassium soap from Cio-C22 fatty acids and potassium soap from dimerized C10-C22 fatty acids in an aqueous medium. 2. Composition according to claim 1 with a content of 5 to 15 percent by weight of a synthetic detergent compound which is not a soap or a fatty acid alkylolamide. 3. Composition according to claim 1 or 2, wherein the sum of b) and c) is 15 to 25 weight percent. 4. Composition according to one of claims 1 to 3 with a weight ratio of b) to c) of 4: 1 to 2: 3. 5. Composition according to one of claims 1 to 4 with a weight ratio of b) to c) from 3: 1 to 1: 1. 6. Composition according to one of claims 1 to 5 with a content of the hydrotropic component d) in an amount of 5 to 10 weight percent. 7. Composition according to one of claims 1 to 6 with a content of at least 12 weight percent sodium tripolyphosphate. 8. Composition according to one of claims 1 to 7, the sodium tripolyphosphate contains more than 50 percent by weight of phase I. 20th 40