DE2645880A1 - DETERGENTS AND THEIR PRODUCTION - Google Patents

Description

DR.A.VAN DERWERTH DR. FRANZ LEDERER REINERF MEYER

DlPU-ING. (1934-1974) D1PL.-CHEM. DlPL-ING.

8000 MUNICH 80

LUC1LE-GRAHN-STRASSE 22

TELEPHONE: (089) 472947 TELEX: 524624 LEATHER D TELEGR .: LEATHERPATgNT

Munich, October 11, 1976 C 799

UNILEVERN-V., Burgeineester s'Jacobplein 1, Rotterdam, Netherlands

Detergents and their manufacture

The invention relates to detergent-containing agents which are suitable as fabric washing agents / and in particular to such Agents that contain phosphates as builders.

The most commonly used builders are the condensed phosphates, especially sodium tripolyphosphate, but it was stated that the use of these Phosphates' can contribute to eutrophication problems. Alternatively, a great many suggestions have been made for mainly organic Materials that should be used as builders instead of the condensed phosphates, however, most of these materials are unsatisfactory for one reason or another, e.g. are they less effective or less effective biologically unacceptable, or they are just too expensive.

It has also been suggested to alleviate eutrophication problems by using lower amounts of condensed phosphates than Framework substances (builders) with or without others

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To alleviate builders, but few of these suggestions have been acceptable, so if lower amounts of sodium tripolyphosphate can be used without further builders, if the agent is used in hard water considerable Problems arise when there is not enough phosphate to bind all the calcium ions present, as this leads to the precipitation of insoluble calcium phosphate salts which collect on the washed fabrics can. When a condensed phosphate is used as a builder with other types of builders, it tends to these lead to an interaction, and often the former prevent it the latter in their effectiveness, especially in the case of other builders that work in such a way that they Precipitate calcium salt, e.g. sodium carbonate.

It has now been found that certain mixtures of synthetic, organic, anionic surfactant, Sodium tripolyphosphate and water-soluble soap show a cleaning effect, the agents with high phosphate content is equivalent. According to the invention is a highly effective Washing powder for fabrics or fabrics provided, which contains a surface-active system, which essentially a synthetic, organic, anionic surfactant and a water-soluble soap and a builder system comprising soap and a tripolyphosphate salt contains, where

(a) the synthetic, organic, anionic surface-active Agent in an amount of 5 to 50 percent by weight,

(b) the water-soluble soap in an amount of 10 to 30 percent by weight and

(c) the tripolyphosphate salt is present in an amount between 10 and 20 percent by weight

and the remainder are conventional ingredients of detergent powders. By suitable choice of the amounts of sodium tripolyphosphate

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and soap it is possible to formulate effective laundry detergents that have lower phosphorus levels than conventional ones Contains detergents of comparable performance. In so far as these two substances usually act differently, i.e. sodium tripolyphosphate as a complexing structural substance and the soap as a precipitation builder, it is surprising that a mixture of these substances is so effective. In particular, the inclination of the Sodium tripolyphosphate to cause inorganic deposits on washed fabrics or fabrics, though it is used in detergents in small proportions, decreases in the presence of the soap. That seems further Sodium tripolyphosphate does not inhibit the builder effect of the soaps, as it does with is the case with many other detergent manufacturers, and any soap that is not precipitated as calcium salt, e.g. if the Agents used in soft water or at higher product concentrations can be used as detergent-active Compound act, whereby the cleaning effect or washing power of the means is increased.

Instead of sodium tripolyphosphate, the potassium salt can be used, but this is more expensive and simplicity for the sake of this, the use of the sodium salt is described and illustrated in this specification.

The soaps used are the sodium or, less desirable, potassium salts of Cg-Cpp fatty acids, in particular natural fatty acids that are derived from nut oils, e.g. coconut oil or palm kernel oil, or fats of the tallow class, such as beef or shaft algae, palm oil, bacon, different vegetable butters and castor oil. It is essential to use some soaps from the class of tallow soaps, which are soaps made from predominantly C ₁ Jj-Cp ₀ (primarily C. «) Fatty acids, of which normally at least about 40 % are saturated fatty acids. The fats of the sebum class can

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if desired, hardened to reduce the content of unsaturated fatty acids, such as oleic acid and linoleic acid, and this is particularly beneficial when using some more polyunsaturated oils, such as soybean oil, than Substantial proportions of fats of the sebum class should be used.

Preference is given to using mixtures of soaps derived from fats of the tallow class and from nut oils which are soaps with predominantly ^c ^ Q ~ ^c ^ h ~ * - fatty acids, of which at least about 75 % are normally saturated fatty acids; again, the nut oils can be hardened as desired. Such mixtures have slightly better solubilities than tallow soaps alone, coupled with sufficiently low calcium soap solubilities for satisfactory builder activity and sufficiently low critical micelle concentrations approaching that of tallow soap alone to remove any excess soap The preferred mixtures range from about 9: 1 to 3: 1 parts by weight of tallow soap to nut oil soap. In general, higher levels of soaps of the tallow class in such mixtures impart better builder properties, while higher levels provide Nut oil soaps produce better solubility properties ht, a sebum class soap can be used alone.

In addition to tallow class soap and optionally any nut oil soap, longer carbon chain soap can be used if desired, particularly Cp _{0 -Cp 1} soaps, e.g., rapeseed soaps, which are useful for suds suppressing properties, or synthetic fatty acid soaps. Unlike naturally occurring or derived fatty acids, which have linear carbon chains with an even carbon number, synthetic fatty acids can be both odd and even

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Have numbers and be both linear and branched chain. Synthetic fatty acids with a length of the carbon chain predominantly of C ₁ Ji-Cp ₀ , which are preferably at least about ^ O % saturated and at least about 75 % linear, can be used to partially or fully replace natural tallow soaps, and synthetic fatty acids with a length of the carbon chain predominantly of C-fQ-C-jC, preferably at least about 75 % saturated and at least about 50 % linear, can be used to partially or fully replace natural nut oil soaps. If branched-chain fatty acids are used, they are preferably -alkyl-, for example trf-methyl-branched, less highly branched.

There have been many suggestions for its use in the past of sodium tripolyphosphate as detergent ballder'in detergents with soap as a detergent material. For example, it is for use in so-called ternary active mixtures common in low-foaming agents, a little soap, in a small amount of up to about 8 percent by weight to have available. Usually such soaps are sebum soaps or soaps of longer chain fatty acids. Laundry detergent too soap based contained small amounts of sodium tripolyphosphate. However, according to previous Previously not known to have suggested the special mixtures of detergent components, sodium tripolyphosphate and to use soap in the proportions given below for use in detergents according to the invention.

The ratio of the soap to the hiatrium tripolyphosphate in the detergent is preferably less than 1: 1, generally about 0.75: 1 to about 0.9: 1 parts by weight. The total amount of sodium tripolyphosphate and soap is preferably about 25 to about 50 % and especially about 30 to about 50% by weight of the composition. Lower levels of sodium tripolyphosphate are intended either for use in higher product concentrations or in soft water.

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The amount of sodium tripolyphosphate is determined according to the
Total content of phosphate builder selected in the
Detergents is desired, or according to the maximum
permissible phosphorus content. Sodium tripolyphosphate is used

usually in an amount within the range of.,

about 15 to 20 percent by weight of the agent used, e.g. \

about 16 percent by weight. Should the means according to the invention '

but for reasons of environmental protection with lower Phos!

phate contents are used, smaller amounts I used. A value less than 20 percent by weight

Sodium tripolyphosphate on average corresponds to less than et-;

wa 5 percent by weight phosphorus, and it is a feature of the!

Invention that detergents with these low phosphate values i

can be produced and still have good detergent properties

i have shafts.

The minimum level of soap that should be present is 10 Ge j

weight percent of the agent, and the maximum content is 30 Ge j

weight percent, preferably less than about 25 weight percent '

of the means and in particular about 15 to about 20 weight j

percent. \

The amounts of sodium tripolyphosphate and soap to use j

in a certain detergent will be according to the expected!

Washing conditions selected. For example, it has been found that I.

that amounts of about ίβ or 14 % (with 4 % phosphorus content) to;

good performance for funds that are relatively '

high product concentrations are to be used, i.e. .. |

about 0.3 to about 0.8 percent by weight, as in Europe | common practice is, especially in from the front
loaded automatic washing machines. In the case of means, however,
which are to be used at relatively low product concentrations, ie about 0.1 to 0.3 % » as in the
Washing is common practice in North America, especially at
automatic washing machines loaded from above
found levels of about 16 % sodium tripolyphosphate
and about 30 % soap is required.

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The detergents according to the invention necessarily contain an amount of a synthetic, organic ^ anionic surface-active Means. Many suitable detergent-active compounds of this type are commercially available and in US Pat Literature described in detail, e.g. by Schwartz, Perry and Berch, "Surface Active Agents and Detergents", Volumes I and II.

The preferred compounds are water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups of 8 to 22 carbon atoms, the term alkyl being used herein to include the alkyl group of higher acyl groups. Examples of suitable synthetic anionic detergents are sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher (Cn-C ^ o) alcohols such as those made by reducing the glycerides of tallow or coconut oil, and especially the C ^ .g-primary alkyl sulfate; Sodium and potassium alkyl (CgCp ₀ ) -benzenesulfonate, in particular sodium-lin.-sec-alkyl (C ₁ QC .. c \ -benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols, which are derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (Cg-Cg) fatty alcohol-alkylene oxide, in particular ethylene oxide reaction products Coconut fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulfonates, such as derivatives from the reaction of alpha-olefins (Cn-Cp ₀ ) with sodium bisulfite and from the reaction of paraffin-s with SO ₂ and Cl ₂ and subsequent hydrolysis with a base to give any sulfonate; and olefin sulfonates, with which the reaction product of olefins, in particular alpha-olefins, with SO, after neutralization and hydrolysis of the reaction product

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If desired, small amounts of non-ionic surfactants can additionally be used to facilitate soap scum distribution and to inhibit its deposition on washing machine parts. Preferably, however, nonionic surfactants are absent entirely. Examples of suitable nonionic surfactants are the reaction products of alkylene oxides, usually ethylene oxide, with alkyl-CCG-C ^ p ^ phenols, i · ^m generally 5 to 25 EO; ie

5 to 25 ethylene oxide units per molecule; the condensation products of aliphatic (Co-C-iq) primary or secondary alcohols with ethylene oxide, in general

6 to 30 AO, and condensation products of ethylene oxide

with the reaction products of propylene oxide and ethylene diamine. Other so-called non-ionic detergent compounds are e.g. long-chain tertiary amine oxides, long-chain tertiary Phosphine oxides and dialkyl sulfoxides, which are actually semi-polar compounds.

Amphoteric or zwitterionic detergent compounds can also be used in agents according to the invention, but this is usually because of their relatively high levels Costs not wanted. If amphoteric or zwitterionic detergent compounds are used at all, then generally only in very small amounts. However, some zwitterionic or amphoteric compounds, in particular Sulfobetaines, such as hexadecyldimethylammoniopropanesulfonate, have useful properties in terms of soap scum distribution.

The amount of the synthetic, organic detergent-active compound (s) used is generally in the range from about 5 to about 50 %, preferably from about 7 to about 15 %, based on the weight of the agent, depending on the properties desired. Part of the added soap can also be used as a detergent compound under so-called

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"excessive" circumstances act, i.e. at higher product concentrations or when using soft water. The ratio of the total detergent compounds to the total amount Sodium tripolyphosphate and soap should generally range from about 10: 1 to 1:10, especially about 3: 1 to 1: 5 parts by weight.

Apart from the detergent compounds and detergency builders A fabric washing powder according to the present invention can be any of the conventional ones Contain additives in amounts in which such additives normally be used in such detergent powders. Examples of these additives are foam boosters, such as e.g. Alkanolamides in particular the monoethanolamides, the are derived from palm kernel fatty acids and coconut fatty acids, which promote the flowability or pourability of the powder Agents such as silicas and aluminosilicates, foaming suppressing agents, redeposition agents counteract such as sodium carboxymethyl cellulose, oxygen-releasing bleaches such as sodium perborate and sodium percarbonate, peracid precursors for bleaching, chlorine-releasing bleaching agents, e.g. Trichloroisocyanuric acid and alkali metal salts of dichloro. isocyanuric acid, fabric softening agents such as e.g. Clays of the smectite and illite type, aids counteracting incineration, starches, distributing soap scum residues Agents, inorganic salts such as sodium sulphate and, usually present in very small amounts, Fluorescent agents, perfumes, enzymes such as proteases and Amylases, germicides and dyes. Additionally it may be desirable to use slurry stabilizers add such as polyethylene / maleic anhydride copolymer and polyvinyl methyl ether / maleic anhydride copolymer, usually in salt form.

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It is also possible to use smaller amounts in the detergents according to the invention, e.g. not more than 25 percent by weight, other detergent oullder that either the so-called precipitation builders or complexing ones Can be a builder. This can be of particular benefit where it is desired to increase the detergency in use To increase particularly low levels of sodium tripolyphosphate, so as to increase particularly low levels of phosphorus in detergents. Examples of such further detergency builders are amine carboxylates such as e.g. sodium nitrilotriacetate and sodium carbonate. It can also be noted that minor proportions of sodium pyrophosphate and sodium orthophosphate normally by hydrolysis of sodium tripolyphosphate during atomization or spray drying to make the detergent powders are formed, low levels of these further phosphate builders can be present in the detergents.

It is desirable to have a lot of one in the funds as well Incorporate alkali metal silicates, in particular sodium-o-, -m- or preferably a neutral or alkaline silicate. Such alkali metal silicate is present in amounts of, e.g., about 5 to about 15 weight percent normally beneficial for reducing corrosion of metal parts in washing machines, in addition to that it offers processing advantages and generally improved powder properties. In addition, the amount of silicate can be used to some extent to control the pH of the agents, which is generally in the range of about 9 to about 11, preferably about 9.5 to about 10.5, in the aqueous solution of the agents at the recommended concentrations should lie. A higher pH value, i.e. above about pH 10.5, is in terms of the cleaning effect more effective. but is less desirable for household security reasons.

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The detergent can be any of the conventional techniques used to manufacture detergents for fabrics or fabrics, including in particular slurry preparation and "spray drying. However, it has been found that the presence of substantial amounts of soap in the detergent slurries creates problems in spray drying, particularly in manufacture of powders with a low bulk density and with a high proportion of small particles (fines).

In a further embodiment of the invention, it has proven to be advantageous to manufacture the detergents a slurry and spray drying, with the slurry either no soap at all or just a portion, preferably no more than about 8 percent by weight, is added and all of the soap or the remainder of the Soap is subsequently added to the spray-dried powder in particle form, e.g. as "noodles", granules, Pellets, ribbons, shavings, flakes, globules or "marumes". In this case it can be advantageous to add minor ingredients, e.g. perfumes, to the detergents in the topped up To supply soap particles. Such soap particles can be prepared by the usual methods in Depending on the final shape and size desired, and the soap is preferably grinded thoroughly before the Particles are formed as this leads to improved solubility, especially for particles with a higher Content of sebum soap.

On the other hand, it is possible to spray-dry two separate slurries, either in the same or in the same way in different spray drying towers to then mix to form the final composition. In this case, a slurry preferably contains all of the main components, but no more than about 8 percent by weight

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Soap, and the other slurry contains the soap with other minor ingredients as a major part. Of the The term "atomization or spray drying" as used above includes processes in which detergent slurries be injected into a relatively hot gas, usually air, either in countercurrent or in cocurrent, and processes where hotter slurries are in proportionately cool air can be sprayed in, i.e. in the so-called atomization cooling or flash drying processes. Conventional drying and drying gas temperatures are used in such spray drying processes for the production of detergents according to the invention.

Further advantages, features and embodiments of the invention result from the following description of examples illustrating the invention, in which Parts and percentages are by weight unless otherwise specified.

example 1

A detergent was prepared to the following formulation:

Component £

Sodium alkylbenzenesulfonate 7

nonionic detergent compound 3

Soap ¹ 6

Soap "noodles" ² 12

Sodium tripolyphosphate 19

Sodium sulfate 9

Sodium silicate 8

Sodium perborate 25

Sodium carboxymethyl cellulose l moisture + minor components au 100

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. 1 Sodium soap, made from tallow fatty acids and hardened rapeseed fatty acids (1: 1 mixture), added to the detergent slurry.

2 "noodles" of sodium soap, made from one Tallow soap and coconut soap mixture (70:30).

The above composition was prepared by spray drying an aqueous slurry of the ingredients, with the exception of the soap noodles and the sodium perborate, which were added to the spray-dried powder ¹ . The agent had a higher bulk density and better powder properties than a powder of the same formulation, prepared by spray-drying the entire composition with the exception of the sodium perborate.

In terms of cleaning properties, this agent performed favorably in comparison with a commercially available, low-foaming agent which contained 35 % sodium tripolyphosphate instead of the mixture of sodium tripolyphosphate and soap builders with otherwise similar ingredients.

Example 2

A spray dried laundry detergent was used Parts following Formulation made: 16.0 Weight percent component 16.0 of the finished 6.0 Means Sodium alkylbenzenesulfonate 20.0 13.9 Sodium tripolyphosphate OK 13.9 alkaline sodium silicate 11.6 5.2 Sodium 70.0 17. ¹ y Sodium carboxymethyl cellulose 0.3 Water and fluorescent agents 10.1

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This agent then became one at 45 parts by weight separately spray-dried agent mixed together with the following formulation:

component Parts Weight percent
of the finished
Means Sodium soap (tallow coconut 74 : 26) 7/29 25.8 Coconut fatty acid ethanolamide 1.6 1.4 alkaline sodium silicate 6.0 5.2 Sodium ethylenediamine
totra acetate 0.2 0.2 Fluorescent agents 0.4 0.3 humidity Rest too 100 45.0

The resulting agent proved to be favorable in terms of cleaning properties in comparison with commercially available detergents on a nonionic and anionic basis with a content of 33 % sodium tripolyphosphate,

Example 3

The procedure of Example 2 was repeated with the Exception that instead of the 45 parts of the spray-dried soap-based agent, 30 parts of potassium tallow soap in Pasta form were added to the spray-dried powder. This resulted in similarly favorable cleaning properties achieved.

Example 4

A detergent was prepared to the following formulation:

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component

Alkylbenzenesulfonate 7.0

Tallow alcohol - 18 AO 1.5

Sodium sebum soap 15.0

Hardened Sodium Soap

Fish oil · ■ * ---- 3.0

Sodium tripolyphosphate 19.0 alkaline sodium silicate 5.0 sodium carboxymethyl cellulose 1.5

Fluorescent agents and preservatives 0.4

Sodium perborate 30.0

Water (and minor additives) 18.6

100.0

This product was made by making a slurry and spray drying with all ingredients, excluding the perborate which were combined in the slurry, and the perborate was mixed with the resulting powder mixed together.

It was found that this washing powder had good cleaning properties in comparison with commercially available washing powder with a higher phosphate content (30 %) .

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Claims (6)

PATENT CLAIMS [Ij. High-performance washing powder for fabrics with a surface-active system, essentially consisting of a synthetic, organic, anionic, surface-active agent, a water-soluble soap and a detergent builder system with a soap and a tripolyphosphate salt, characterized in that a) the synthetic, organic, .anionic, surface-active Medium 5 to 50 percent by weight, b) the water-soluble soap 10 to 30 percent by weight and c) the tripolyphosphate salt 10 to 20 percent by weight and the rest are conventional detergent components. 2. Washing powder according to claim!, Characterized in that that the soap makes up 15 to 25 percent by weight .. 3. Washing powder according to claim!, Characterized in that that the soap makes up 10 to 15 percent by weight. 4. Washing powder according to one of claims 1 to 3, characterized characterized in that the soap is a mixture of soaps of the class of the tallow fats and of soaps of coconut oil is in a weight ratio of 9: 1 to 3: 1. 709816/1162 5. washing powder according to one of claims 1 to 4, characterized in that the soap / tripolyphosphate salt ratio is less than 1: 1. 6. Washing powder according to one of claims 1 to 5j characterized in that the synthetic, organic, surface-active agent contains an alkyl sulfate salt. "7. Washing powder according to claim 6, characterized in that the alkyl sulfate salt is the primary sodium salt contains. 709818/1162