NO134914B - - Google Patents

Abstract

Particulate detergent preparation and method for producing it.

Description

The invention relates to a non-sticky, rigid, breakable, non-

sprat, rapidly water soluble, extruded, particulate detergent composition containing a higher alkyl aryl sulfonate, a lower alkyl aryl sulfonate, inorganic salt and water.

It is known to produce extensive detergent preparations

a mixture of dry particles of alkyl aryl sulfonate together with dry particles of xylene sulfonate. Such preparations are in the US

patent document no.-2.63^.2^0 described as useful powder detergents. Such powdered detergents produced from mixed

ings of dry materials are affected by a number of different disadvantages, such as uneven composition for a given sample,

ning, segregation, flowability and stoking. The present invention provides a cleaning and washing preparation which is not affected by the known disadvantages.

The invention thus relates to a water-soluble, particulate

shaped detergent preparation containing a higher alkylaryl sulphonate,

a lower alkylaryl sulphonate, inorganic salt and water, and the detergent preparation is characterized by the fact that it is formed from separate,

mechanically processed, substantially homogeneous particles each comprising (a) 10-^fO wt% water-soluble, detergent-active higher alkylaryl sulfonate salt with an average of 12 or 13 carbori-

atoms in the alkyl group, (b) 10-^0% by weight of a lower-alkylbenzenesulfonate salt with 1-3 carbon atoms in the lower alkyl group, (c)

5-50% by weight of a; water-soluble, inorganic alkali metal builder salt and (d) 2-20 wt.^ water, the ratio between (a) and (b) being 1:h-

6:1, whereby the main part of each particle is of organic material

ale, and forms non-sticky, rigid, breakable and non-spro par-

ticklers, as the detergent preparation also optionally contains a coloring material or a detergent active agent that promotes foam formation.

It is well known that detergent-active alkylaryl sulphonates are 'very difficult' to extrude or otherwise process. mechanically because.they are sticky. Such detergent active compounds cannot be extruded for the production of the spaghetti-like particles according to the invention. The lower alkylaryl sulphonate materials cannot be extruded into the spaghetti-like particles according to the invention either. / However, it has been shown that together with the . herein described inorganic salts and water can be a composition of

detergent salts of Libyans, and lower alkylarylsulfonates'' are extruded to. continuous .needles with a. cross-section below 0.8:-mm and ... with those herein. described at-risk properties. •■... \ y. :- l' t:- •

The detergent-active, homogeneous preparations according to the invention can be used as such or in a mixture with other detergent-active, particulate, synthetic organic materials, and can be produced;..';

with the desired shape on a simple, economical and light feed" by mechanical processing, extrusion and granulation of a preparation

as indicated below with 10-20 parts by weight of a detergent-active higher alkylaryl sulphonate salt, 10-2.0 parts by weight of a lower alkylbenzene sulphonate salt and 5-50 parts by weight of a water-soluble inorganic ';:' alkali metal building salt. ' .The aggregate amount of. organic .material : ■ ■;'■.*.• in the preparation constitutes the main part of this, and for this f br measure •... the content of the salt of higher and lower alkylarylsulfonabv.s.up-; mixed with other organic materials, such as the alkali and alkaline earth metal salts of alkyl sulphates, e.g. sodium lauryl sulfate,... '' the like, alkyl ether sulfate salts and nonionic compounds,, such as ethoxylated nonylphehol or ethoxylated fatty alcohol sulfates.

The amount of alkylarylsulfonates must, in each case, be within the ranges indicated above, and the ratio between the higher alkylarylsulfonate and the lower alkylbenzenesulfonate is preferably 1:h - 6:lr. - show 1:2 - 2:1, and the amount of higher alkylaryl sulfonate\bo^':''Kéist\.;' be approximately therein the same as' the amount of . the lower alkylbenzeri-. ;,...:?'' .',.

sulfonate. There is also some water present in the final product in an amount of 2-20% by weight. -; Such preparations consist of non-sticky, . • . breakable, non-spro; paTticles .-which - dissolve . or dispersed. on •■ ' ■;. ,'; r; under 120 s, preferably under 60 s. £-, J \, ,'; The invention also relates to a method for the production of the rigid, breakable, non-pro detergent preparations according to the invention and the method is characterized by those in claims. -'

characterizing-part specified features.

The mixture is extruded with a temperature at the outlet of the extruder of 10-ifO°G forming a series of thin strands

with a cross-section of 0.0^ - 0.8 mm <2>, after which the strings, immediately after they have been extruded, are brought into contact with an air

current at a temperature of 5 - ^5°C, -preferably 20-30°C, to harden their surface- and the strands are then placed on a

. conveyor belts under continuous conduction of air over them until -

they become non-sticky, rigid and breakable, after which the strands are divided into 1 lengths of 0.5 - 10 mm. The extruded strands are divided into lengths by being fed through a sieve or other suitable equipment. This procedure can be carried out with a reasonably low-capacity

control without it being necessary to remove large amounts of water. In addition, the preparation's particle size can be easily regulated.

The non-sticky, stiff, breakable, water-soluble, particulate detergent preparation according to the invention can be

used for gentle washing of clothes, service or similar. Due to the fact that the separated particles., which the preparation according to up-

the invention consists of, are non-sticky, will not segregate and are substantially free of caking. Such particles are highly free-flowing and very fresh replacements for the powdery hand sanitizers that are usually dispensed from containers in toilet rooms. The present preparation is also

very useful as an additive to spray-dried or other particulate detergent preparations or as a carrier

material for an additive, ...such as colouring, whitening agent,

enzyme or other material. Such a carrier material with e.g. a bleaching agent is useful as a bleaching agent in the second rinse-

ling after washing.

It is important that the preparation is mixed until it is in it

substantially homogeneous for the strings are formed. Each final particle dan-

net from the strings is essentially plastic. This is surprising

due to the presence of crystalline materials, such as the inorganic salts. The plasticity can be demonstrated by microscopy of the individual particles and shows that each particle has an essentially smooth surface and is free of crystalline components. Moreover, the strands are easily breakable despite their plasticity which facilitates extrusion, and at the same time they are essentially non-pro. An easy breakability is not a common property of plastic materials, and non-brittleness is not, as a rule, typical of breakable materials. The special combination of properties that the particles in the detergent preparations according to the invention have must therefore be considered to be very unusual.

The non-pro, breakable alkyl aryl sulfonate preparation is prepared using a simple, low capacity mechanical processing equipment. Sufficient mechanical processing and a correct choice of the salts used and the relative quantities of these will produce particles with the desired physical properties. During the mechanical processing, the preparation becomes homogeneous, and. thereby achieving a physical structure in the mixture that leads to the desired surface and internal properties. The mechanical processing includes tearing and extrusion, i.e. a. compressing the plastic mixture under pressure and forcing it through one or more openings with limited movement, and preferably also includes subjecting the preparation to shear forces, such as e.g. by feeding the plastic mixture between a series of rollers rotating at different speeds and having different clearances. The mechanical processing usually leads to an increase in temperature which can be regulated by adding or removing heat during the processing. The final product has the shape of spaghetti-like noodles with a cross-section which depends on the size of the extrusion opening and which is > 0.0^- - 0.8 mm-, preferably

0.06 - 0.3 mm<2>.

As they are formed, the extruded noodles are exposed to an air stream which is kept in contact with them for a short time. In this zone, the noodles' temperature is regulated to 15 - 25°C. The air treatment of the extruded noodles means that free moisture, e.g. 1-5% by weight, is removed and that a hardened surface is formed. The material is then broken up into short lengths in a suitable manner, e.g. by forcing the material through a granulation screen with 0.177 - 10.0 mm, preferably 0.25 - 3.36 mm, apertures. The particulate material formed is free-flowing, non-buoyant and rigid. It has a bulk density that varies inversely with the length of the noodles and is usually 0.5 - 0.9 g/cm^. The product can be used as such or in a mixture with particulate detergent preparations containing a synthetic, organic, detergent-active compound. The particles in the detergent or cleaning agent preparation can e.g. mixed with particulate, spray-dried preparations containing a major part of particles with a diameter of 0.3 - 2.0 mm.

The hard, non-spro, detergent-active particles formed in the manner described herein contain at least one higher alkylaryl sulphonate salt with 9-18, preferably 10-15, carbon atoms in the higher alkyl group. This can be straight chain or branched. These detergent-active compounds are used in the form of their water-soluble salts, such as the sodium, potassium, ammonium, alkylolammonium and magnesium salts. Suitable detergent active compounds include higher alkyl benzene sulfonates, higher alkyl toluene sulfonates, higher alkyl phenol sulfonates and higher alkyl naphthalene sulfonates. Preferred sulfonates are the dodecyl and tridecylbenzene sulfonates.

A particularly preferred sulfonate is the linear alkylbenzenesulfonate with 12 - 1<*>+ carbon atoms in the alkyl group and with a high content of 3- (or higher) phenyl isomers and a correspondingly low content (below about 30%) of 2- (or lower ) phenyl isomers, i.e.

where the benzene ring is preferably for a large part fused to the 3_ (or higher e.g. k-, 5, 6, or 7) position in the alkyl group, and the content of isomers where the benzene ring is bound to the 2- or 1-position is correspondingly low. The particularly preferred sulfonates are described in US Patent No. 3,320,17^.

The detergent-active higher alkylaryl sulphonates can be added as particles such as e.g. formed by solidification drying or drum drying. The detergent-active alkylaryl sulphonate can also be formed in situ by adding to mixing containers - in a liquid, acidic state, e.g.

in the form of a liquid containing 88% by weight of alkylarylsulfonic acid, 7.5% sulfuric acid, and ^t-.5% water, to then be neutralized with an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate.

The lower alkylbenzene sulfonate salts have 1-3 carbon atoms in the alkyl group. Suitable lower alkylbenzenesulfonate salts include the sodium and potassium salts of xylene, toluene, isopropylbenzene and ethylbenzenesulfonates. Commercially available xylene and toluene sulfonates are mixtures of isomers. Analyzes of commercially available xylene sulfonates show, for example, ^-0-58% by weight meta-xylene sulfonate, 10-35% by weight ortho-xylene sulfonate, 15-30% by weight para-xylene sulfonate and 0-20 % by weight ethylbenzenesulfonate, and analyzes of commercially available toluenesulfonates show 70-80% by weight para-toluenesulfonate and 20-30% by weight ortho-toluenesulfonate. Other water-soluble, sulphonated salts, such as the ammonium, alkylolammonium and magnesium salts, can also be used. These materials can be added either in solid or liquid form. Commercially available sodium xylene sulphonate is e.g. available as a 90-95% active powder or as a 30-<!>+5% active, .aqueous liquid. If it is available in the form of an aqueous liquid, the form in which it is added usually depends on the form and water content of the other essential ingredients in the preparation.

At least one water-soluble, inorganic salt: used in an amount not exceeding the amount of organic material in the preparation. Such salts include a water-soluble, hydratable or hydrated, inorganic, alkaline alkali metal builder salt. The preferred salt is sodium tripolyphosphate. Such inorganic, hydratable, alkaline building salts are well known, and large amounts of these are often used together with detergent-active sulfonates or sulfates to increase their detergent effect. Others satisfactorily hydratable

■.or hydrated alkaline building salts are the alkali metal pyrophosphates, the orthophosphates, the carbonates, such as sodium carbonate, the silicates, such as sodium metasilicate, the borates, such as sodium tetraborate, and mixtures thereof. Sodium tripolyphosphate of both phase I and phase II and mixtures thereof can be used.

The building salts specified above are preferably supplied in the form of anhydrous particles. These building salts act according to the invention and in the prescribed amounts to harden the extruded noodles so that they become non-sticky and retain their separated form. This hardening effect also facilitates the extrusion of the noodles by changing the surface of the noodles so that the tendency of the noodles to stick together is reduced. In addition, the building salts help to strengthen the preparation's washing effect.

A part of the building salts preferably consists of salts which make the preparation more soluble and which can be introduced together with the organic alkylaryl sulphonate material. Such salts are usually inorganic alkali metal sulfate salts and are usually present as sodium or potassium salts. Other salts that are strongly water-soluble, can also be used. These include the bicarbonates, such as sodium or potassium bicarbonate, the sesquicarbonates, such as sodium sesquicarbonate, and the halogen salts, such as sodium chloride.

The anions specified in connection with the sulfate salts can also be used together with the cations specified immediately above.

The detergent preparation also contains 2-20% water. The water facilitates the formation of a rheologically extrudable mixture and also promotes the neutralization if the alkylaryl sulphonate salt is formed in situ, and can be used as a carrier material for small amounts of additives, e.g. dye, bleaching agent and bactericide etc. It should be noted that the total amount of water present is the sum of the directly added amount of water and the water contained in the other components. Evaporation-dried alkylarylsulfonate contains e.g. usually 1-3% water and can contain up to 10% water.

Various additives can be introduced into the noodle-like preparations, because the components in these are processed mechanically. Such additives may include 0.01-2% coloring materials,

as water-soluble dyes and water-dispersible pigments, 0.01-2% perfumes, 0.1-5% activators for oxygen bleaches, such as the activators described in US patent application no. 726571 of May 3, 1968, 0.01-10% fluorescent whitening agents , such as the derivatives and analogs of coumarin, diaminostilbene, diaminobenzofuran and the pale stable whitening agents described in US Patent No. 3-3^6,502, 2-50% enzymes,

such as proteases (Alcalase) and amylases, 0.01-3% bactericides, such as hexachlorophene, halogenated carbanilides and halogenated salicylanilides etc, and 0.5-20% foaming agents, such as alkanols with 10-18 carbon atoms, alkanolamides with 10-18 carbon atoms and trialkylamine oxides. Other ingredients can, if desired, also be used, such as starches, including corn starch, tapioca starch and potato starch. These added components can improve the processing and mechanical processing or the physical properties of the product.

The quantity and choice of higher alkylarylsulfonates in the mechanically processed, noodle-like preparation is chosen so that a product with the desired physical and use properties is obtained. This contributes to the foaming and cleaning effect of the finished detergent preparation, and, if an additive as indicated above is used, the noodle preparation acts as a dispersing or stabilizing agent for this. The relative amount of the detergent-active higher alkylaryl sulfonate is 10 - ^0 parts by weight,

preferably 10-32 parts by weight, of the carrier material.

In the mechanically processed preparation, the hardening agents of builder's salt make up a smaller part and are usually present in a sufficient amount to achieve the desired hardness, i.e. at least 2, but not more than 20% by weight, preferably 5-15% by weight, of the builder's salts . It is preferred that* a tripolyphosphate curing agent is present in such an amount that the weight ratio between tripolyphosphate salt and organic sulfonate salt is 1:2 - 1:12.

As indicated above, the spaghetti-like noodles can be advantageously mixed with a particulate detergent composition containing a synthetic, organic detergent active compound (such as spray-dried hollow spheres or low density spongy grains) to produce a detergent composition. The relative amount of the spaghetti-like. detergent preparation in the finished detergent preparation is 0.01-50% by weight, preferably 0.5-20% by weight, of the total detergent preparation. The finished detergent preparation usually also contains inorganic alkaline or neutral building salts which, as is well known, give an enhanced washing effect. The synthetic detergent active ingredient in the particulate detergent preparation used in the finished detergent products can be an anionic, non-ionic or amphoteric surfactant, detergent active compound or a mixture of two or more of the detergent active compounds specified above. Any of these anionic, cationic, non-ionic, ampholytic or amphoteric detergent compounds can also be used as part of the organic part of the spaghetti-like preparation although, as described above, the mixture of detergents of lower and higher -alkylaryl sulphonate salts must make up at least 20% of the total noodle preparation.

Water-soluble building salts are usually used in the production of full-washing products. Suitable builder salts are the phosphates, the condensed phosphates (eg, pyrophosphates or tripolyphosphates), the silicates, borates and carbonates (including the bicarbonates), and organic builders, such as salts of nitrile triacetic acid or ethylenediaminetetraacetic acid.

Other materials may be present in the washing products. Materials such as the higher fatty acid amides can be added to improve detergency and to modify the foaming properties as desired.

These materials are usually added in smaller amounts, usually 0.5-10%, preferably 1-6%, based on the total solids content.

Various other components can be introduced into the particulate detergent component in the finished detergent preparation. The preparation can thus contain special chelating agents, such as salts of ethylenediaminetetraacetic acid. Other common auxiliaries include dirt suspending agents, e.g. sodium carboxymethyl cellulose, anti-discolouration agents, e.g. melamine, fluorescent whitening agents, coloring materials, bactericides and skin conditioning agents, e.g. lanolin, etc. These materials are usually mixed with the aqueous, detergent-active, synthetic organic compound and the other ingredients in the preparation for the drying step if this is used.

Example 1

A green-colored, fast-dissolving, particulate ingredient for washing clothes was prepared with the following composition:

The powdered Viscofil-gront 2 GL was dispersed in water in the presence of small amounts of sodium tripolyphosphate and sodium toluene sulphonate to produce a color dispersion with the following composition:

An application of the color dispersion facilitates the speed with which a homogeneously colored, wash-active mixture can be obtained.

The indicated amounts of toluenesulfonate and the inorganic salts were mixed in a powder mixer and passed through a grinding mill to remove all particles larger than 60 mesh (U.S. standard sieve size). The ground mixture and the indicated amount of sodium tridecylbenzenesulfonate were charged into a belt-type amalgamator. 12 parts by weight of the color dispersion specified above were mixed with 88 parts by weight of the powder mixture specified above, and the mixture continued for approx. 8 minutes for the production of an essentially evenly colored paste.

The resulting paste was milled on a standard 3-roll mill with a clearance of 0.5 mm between the rolls. The temperature of the rollers was kept at approx. 20°C, and the product was removed from the mold in the form of homogeneous, green-coloured bands. These were emptied onto an endless belt which was used for feeding into the hopper of a standard soap extruder

of the screw type.

The soap extruder was provided with a wire cloth with 0.5 mm openings and a perforated plate with a series of tapered holes. These holes had a diameter that varied from 12 to 16 mm, the largest diameter being at the outlet. In the soap extruder, the milled material was continuously conglomerated and extruded through the perforated plate due to the action of the rotating screw. The final product was extruded on an endless belt in the form of strands of spaghetti-like noodles. The extrusion temperature in the extruder cylinder was maintained at 20°C by circulating water through a jacket surrounding the cylinder, and the outlet temperature was maintained at 100°C.

To prevent the spaghetti-like noodles from sticking together after extrusion, the noodles were immediately cooled with an air stream as they came out of the extruder. The noodles were then placed on an endless belt where they were held while air at a temperature of 20°C was passed over them until they became non-sticky, hard and breakable, and they were then emptied into a granulator equipped with a 8 -mesh sieve and crushed as they were forced through the sieve. The product formed consisted of particles each with a cross section of approx. 0.25 mm and a length of 3-^ mm. The specific gravity of the product was 1.5 g/cm and the room weight approx. 0.75 g/cm .

The solubility of the particulate product was determined by measuring the time in seconds required to dissolve 1 g of product in 300 ml of water at 20°C under agitation with a 50 µm diameter propeller rotated at 180 rpm. All the green-coloured particles were dissolved in the course of ^0 s. Such a particulate product is characterized by the fact that it is fast-dissolving or fast-dissolving, as the usual dissolution rate for atomisation-used detergents in this experiment is 100-600 s.

About. 1.5% moisture was lost during treatment and cooling with air. The newly extruded noodles contained e.g. about. 12.9% water, and the particulate, green colored product obtained contained 11.5% water by weight. 1 part by weight of the noodles formed in example 1 was mixed with 99 parts by weight of an uncoloured, i.e. white, atomised detergent containing 15% by weight sodium soap, 8% by weight non-ionic detergent active compound, k- 5% by weight sodium tripolyphosphate, 12% by weight sodium sulfate, 12% by weight sodium silicate and 8% by weight water. An attractive green stained full wash product was obtained.

Example 2

The preparation according to example 1 was again prepared, but with

with the exception that sodium xylene sulfonate was used instead of sodium toluene sulfonate. The green-coloured, particulate product obtained was dissolved in the course of h0 s in the solubility test according to example 1 and had a bulk density of 0.7 g/cm- > and a specific gravity of 1.^2.

Example 3

The following preparation was prepared using the method and equipment according to example 1.

The product obtained had a homogeneous green color, a bulk density of 0.65 g/crn^, a specific gravity of 1.<*>+5 °g until dissolved in the course of approx. h0 s. When the moisture after extrusion was 1^.2% by weight, the moisture loss during cooling and granulation amounted to approx. 5.8% by weight.

Example k -

The following preparation was prepared by the method in example 1, but with the exception that the mixture for the amalgamation was mechanically processed on a 5-roller mblle with a gap of 0.5 mm between the rolls for it was extruded at a temperature of h0-h5°C.

The homogenously green colored particles obtained were dissolved in the course of 80 s in the test according to example 1 and had a bulk density of 0.67 g/cm'^ °§ a specific gravity of 1.^. By adding 0.5 parts by weight of the product to 99.6 parts by weight of the white, undyed detergent according to example 1, a green-stained product with a very distinctive appearance was obtained.

Example 5

A green-coloured, particulate product was produced with the following composition:'"'-'''-■ <?>'"' -'."'' ."'

The above-mentioned preparation was prepared by adding 0.5 kg of tap water and 0.7 kg of anhydrous, powdered sodium carbonate to 3.0 kg of dodecylbenzenesulfonic acid in a leak-proof amalgamator while stirring. The analysis of dodecylbenzenesulfonic acid was 88% sulfonic acid, 7.5% sulfuric acid and h:5% water. The sodium carbonate powder was added in small portions to facilitate the neutralization of the sulphonic acid. ^The mixture was esterified during the neutralization of the sulphonic acid due to the evolution of gaseous CO^-After the addition of the sodium carbonate was complete, the mixture was continued until a homogeneous-appearing mixture was obtained. Then 0.9 kg of anhydrous, powdered sodium sulfate and 0.9 kg of powdered pentasodium tripolyphosphate were added and stirring was continued until a homogeneous mixture was obtained. At this stage, 0.35 kg of a 3.56% by weight solution of Vi scofil-gront 2 GL was added and a green homogeneous paste was formed.

The obtained green-coloured, homogenous paste was mechanically processed on a 3-roll mill with a clearance of 0.5 mm between the rolls^-and the product was removed from the mill in the form of flakes which were emptied into the feed funnel of the soap extruder which was used according to example 1. The paste was extruded at a temperature of 20-<!>+0°C in the form of noodles with a thickness of 0.5 mm. After further dressing, the noodles were passed through an 8-mesh sieve to produce a product with a length of 3-<1>+ mm.

The green colored product formed was dissolved in the course of

30 s in the solubility test and had a specific gravity of 1.5 and a bulk density of 0.65 g/cm. By mixing 0.5 parts of the formed green-coloured, particulate product with 99.5 parts of the white or uncoloured 'detergent preparation; if pigé' example .1 was"" det-Mpp-'-'' reached a clearly colored product with. an attractive appearance.

Example 6

The preparation according to example 1 was again prepared, but with

the exception that the commercially available enzyme material Alcalase was added in an amount of 20%, based on the weight of the overall ■ preparation, because it was ground in the mole. The resulting noodle preparation was particularly useful for removing protein stains in addition to its usual cleaning effect.

Claims (2)

1.. A water-soluble, particulate detergent preparation containing a higher alkyl aryl sulfonate, a lower alkyl aryl sulfonate, inorganic salt and water, characterized by the fact that it is formed from separated, mechanically processed, essentially homogeneous particles, each comprising ( a) 10-^0 by weight of a water-soluble, detergent-active higher-alkylarylsulfonate salt with an average of 12 or 13 carbon atoms in the alkyl group, (b) 10-^0 by weight of a lower-alkylbenzenesulfonate salt with 1-3 carbon atoms in the lower alkyl group, (c) 5 - and does not form sticky, stiff, breakable and non-sprouting particles, as the detergent preparation also possibly contains a coloring material or a washing-active agent that promotes foam formation, 2. Procedure for the production of a water-soluble, particulate detergent preparation according to claim 1, characterized in that a water-soluble, detergent-active higher alkylarylsulfonate salt with an average of 12 or 13 carbon atoms in the alkyl group, a water-soluble lower alkylbenzenesulfonate salt with 1-3 carbon atoms in the lower alkyl group, a water-soluble, hydratable, alkaline building salt consisting of orthophosphate, pyrophosphab, tripolyphosphate, silicate, carbonate , sulfate or mixtures thereof, and water are mixed to form a substantially homogeneous, rheologically extrudable mixture which is mechanically processed to make it homogeneous by compaction and extrusion into strands with a cross-sectional area of 0.0<*>+ - 0.8 mm which is brought into contact with straining air to form breakable, non-spro strands. which is divided into lengths of 0.5 - 10.0 mm.