FR2721616A1 - Compositions of anionic surfactants in powder, pearls or granules, process for their preparation and their use in cleaning and maintenance products - Google Patents

Abstract

Compositions in powder, granules or beads containing one or more anionic surfactants, and one or more absorbent fillers containing by weight on a dry basis: - x% of at least one anionic surfactant, with 60% <= x <= 75% - ( 100 - x)% of at least one absorbent filler having a total absorption capacity A, the particles of which have an average diameter less than or equal to 100 mum, which is chosen from the group consisting of silica, metal silicates alkali metals or alkaline earth metals, clays, aluminosilicates, silicates and aluminosilicates of alkali metals and / or lamellar alkaline earth metals, and whose total absorption capacity A, expressed in grams, is greater than or equal to 100 g for 100 g of the filler or fillers used, method of preparation and application to the preparation of powders for cleaning products.

Description

i

  The present invention relates to composi-

  anionic surfactants in powder, pearls or granules, their method of preparation and their application,

  particularly in cleaning and / or maintenance products.

  Anionic surfactants are frequently

  obtained in the form of aqueous solutions whose concentration

  in active ingredients is between 25 and 70%.

  Now, it exists for many applications,

  particularly in detergency, a need for tensio-

  anionic agents in solid form, in particular as powder, pearls or granules, having a high concentration of active, non-dusty and non-irritating substances during handling, flowing easily, rapidly soluble in

  water, high apparent density and a cost of

moderation.

  It is known to manufacture surfactants in the form of granules, using an atomization technique

  which has the disadvantage of consuming a lot of energy.

  It is also known to prepare surfactant granules

  by absorption on charges and possibly by chipping.

  But these techniques are difficult to use in the case of strongly hydrophilic surfactants such as alkyl sulfates or sulfonates, which, because of their high hygroscopicity tend to resume very easily

  moisture and reagglomerate. This is particularly the case

  bind, secondary sodium alkanesulfonates, which, thanks to their excellent solubility in water, are used mainly in liquid detergents. These products

  are of great interest because of their good biodegradability.

  their excellent wetting power and their

  good detergent properties. But, on the one hand, they present

  disadvantage, when they are manufactured in the form of concentrated wax, flakes or pellets, to dissolve only rather slowly in cold water, on the other hand, because of their high hygroscopicity, they tend, when prepared in the form of powders, to rapidly agglomerate by absorption of water from moist air or water

  crystallization of the compounds to which they are mixed.

  Several recent processes describe preparations for

  anionic surfactants in the form of powders or granules.

  French Patent No. 2,265,852 proposes atomizing

  alkanesulfonates, in admixture with a mineral filler and silicic acid. In this process, the amounts of mineral fillers required are greater than those of the active ingredient, so that the atomized product obtained has a reduced concentration of active ingredients. EP-A-349 200 and EP-A-349 201 propose a

  a technique similar to cryoscopic grinding: the tendency

  concentrated, pasty anionic surfactant, is very strongly cooled with dry ice and dispersed

  using a propeller rotating at high speed.

  EP-A-345 090 discloses a process for the preparation of sodium alkylbenzenesulphonate surfactants (ABSNa)

  in the form of granules from alkylbenzene sulphonyl

  than neutralized in situ, and absorbed on bentonite. The report

  ABSNa / Bentonite is between 1/3 and 1/8, the concentration

  The active material used for the powder obtained is weak.

  In general, granulation techniques

  known as WA Ritschez Der Pharmazeutische Betrieb / Band 7 Die Tablet - Chap.4: das Granulieren, Ed cantor KG) consist essentially of agglomerating powders with a liquid, serving as a binder, forming a homogeneous mixture in proportions sufficient to

allow granulation.

  In this case, as in the techniques for absorbing liquids on pulverulent fillers, it is necessary to spray or disperse the liquid in a sufficiently fine way to prevent the formation of clumps and not to exceed the maximum capacity of absorption of loads. These processes have several drawbacks: the need to use low-viscosity liquids and the limited power absorption of the charges lead to powders with low concentration of active ingredients. On the other hand, it is essential to have an effective spraying, mixing and dispersing equipment. It is therefore with astonishment that the Applicant has discovered compositions of anionic surfactants, in powder form, in beads or in granules, which are not dusty, of high concentration of active matter, fluids, not reagglomerate by moisture uptake and quickly

soluble in cold water.

  The subject of the present invention is therefore powder, pearlescent or granular compositions containing one or more anionic surfactants and one or more absorbent fillers characterized by the fact that they contain, by dry weight,: - x% of at least one anionic surfactant, with 60% <x <75% (Rel.l) - (100 - x)% of at least one absorbent filler, designated C, having a total absorption capacity A, the particles of which have an average diameter less than or equal to gm, which is selected from the group consisting of

  silica, alkali or alkali metal silicates

  earthy, clays, aluminosilicates, silicates

  and alkali metal and / or alkaline aluminosilicates

  lamellar earth, also called phyllosilicates, and whose total absorption capacity A, expressed in grams, determined according to the standard NFT 30-022, is greater than or equal to 100 g per 100 g of the load or

loads used.

  In the case where the compositions according to the invention contain more than one absorbent charge C, the capacity

  Absorption A of this mixture of charges, C1, C2, C3 ...

  with respectively an absorption capacity A1, A2, A3 ... is equal to: A = A1y1 + A2y2 + A3y3 ... (Rel.2) or y1, Y2, y3 '' 'respectively represent the weight percentage of the charges C1, C2, C3 ... in this mixture with: Y1 + Y2 + Y3 + ... = 100 (Rel.3) By "anionic surfactant" is meant a surfactant having one or more anionic functions of the sulphate, sulphonate type, carboxylate or phosphate as

  those cited in particular in Ullman's Encyclopaedia of Indus-

  Trial Chemistry, 5th edition, volume A9, page 312 and

  VCH GmbH - Weinheim - Germany 1991.

  The expression "alkali or alkaline

  earthy "may refer to sodium, potassium, lithium,

calcium, magnesium.

  The subject of the invention is more particularly the surfactant compositions as defined above, characterized in that the anionic surfactant (s) is (are) chosen from the group of alkane sulphonates.

  C13-C17 and C10-alkylpolyglycol sulphates.

  C18 and that the absorbing load (s) is or are chosen

  in the group consisting of silica, alkali or alkaline earth metal silicates, and alkali metal and / or alkaline earth metal silicates and aluminosilicates. Among these last surfactant compositions, the invention particularly relates to the compositions as defined above, characterized in that x satisfies the relationship 4:% <x <72% (Rel.4) and that the charge or charges absorbent is or are selected from the group consisting of silica, magnesium silicate, sodium silicate 2 silicate SiO 2, NaO 2, designated SKS 6. Surfactant compositions granules, powder or pearls according to the invention may contain water or a mixture of water and an alkanol and conventional additives to improve or modify

  appearance, flow properties or any other

  of the product, for example: additional silicic load

  dyes, dyes, perfumes, polymers, alkali silicates, etc., and they can also be mixed with fillers or other powdered products in order to obtain products intended for various applications: washing powders,

  cleaning products, phytosanitary products, disinfection

tants, etc.

  According to the invention, the surfactant compositions in granules, in powder form or in beads may be prepared by a process characterized in that the surfactant or surfactants are mixed in an aqueous or aqueous-alcoholic paste having a concentration by weight greater than or equal to 60% with the absorbent filler (s) avoiding any kneading to obtain a corresponding wet surfactant composition in powder form, in granules or in corresponding beads which, if desired, are dried according to processes known per se such as drying in

  fluidized bed at a temperature less than or equal to 100 C.

  Under preferred conditions of implementation of the invention, the process described above is carried out from one or more surfactants in aqueous or aqueous-alcoholic paste with a weight concentration greater than or equal to 60% and having a Brookfield viscosity of between 100 and 10,000 Pa.s determined at C with a Brookfield LVT viscometer at the rate of

0.6 rpm.

  The anionic surfactants in powder, granules or pearls of the invention, because of their high concentration of surfactants, have very interesting properties in the fields of detergency, hygiene, agriculture, etc. .. They allow the easy preparation of various formulations of powder products such as washing powder, various maintenance products, phytosanitary products, disinfectants. They are easily dispersible or soluble in water, they give powders flowing quickly and not giving clods resistant. The following examples illustrate the present invention without however reducing its scope. The products used in the examples are defined below: HOSTAPUR SAS 60 denotes a mixture of secondary C13-C17 sodium alkanesulfonates in aqueous 60% solution.

  weight, marketed by the plaintiff.

  HOSTAPUR SAS 93 denotes a mixture of 93% by weight waxy C13-C17 secondary sodium alkanesulfonates and 7% of a mixture of sodium sulphate, C13-C17 alkanes and

  of water, marketed by the plaintiff.

  AMBOSOL C denotes a magnesium silicate marketed

by the plaintiff.

  SKS 6 denotes a lamellar sodium silicate, 2 SiO 2,

  NaO2, marketed by the applicant.

  GENAPOL LRO denotes a mixture of sodium salts of poly (oxy-1,2-ethanediyl) α-sulfo-dodecyloxy-dough

  69% in water, marketed by the plaintiff.

  The following products are precipitated silicas

  - SIPERNAT 22 marketed by the company DEGUSSA AG - MICROSIL GP marketed by the company CROSFIELD - TIXOSIL 38 marketed by RHONE POULENC The blends were carried out with a laboratory mixer SPRAY MIXER RSM6-60 marketed by the company TELSCHIG and of which the spray system has been removed. The absorption capacity of the absorbent fillers used, determined according to standard NF-T-30-022 is given

in Table I below.

TABLE I

  MAXIMUM ABSORPTION CAPACITY

  certified according to standard NF-T-30-022 (g per 100 g of charges) TIXOSIL 280

AMBOSOL 100

  SKS 6 85 SIPERNAT 22 260 MICROSIL GP 320

EXAMPLES 1-8

  In the mixer tank, successively

  The absorbent fillers and, if appropriate, additives such as urea, anhydrous sodium carbonate, sodium sulphate and then the anionic surfactant (s) chosen in the form of a branch or in the form of aqueous pastes with a concentration by weight greater than or equal to 60%. in the proportions by weight (expressed in grams) given in

Table II.

  After closing, the device is rotated

  until the dust disappears.

  The resulting product is collected and examined. We note: - the general appearance of the mixture - its flowability

  - the possible presence of clumps or agglomerates.

  A fraction of the wet product is dried in a fluid bed dryer at 80 ° C. for 30 minutes, then the dry product is sieved and optionally ground below 2 mm. On the product thus obtained, the following checks

  are then carried out and the values found are

  Table II: - hygroscopicity (determined according to note 1) active substance content (2-phase titration according to NFT)

73 258)

  - dry extract (determined by drying for 4 hours at 105 ° C.), - bulk density, (determined according to the standard

NFT 73-405),

  - flowability measured according to the standard NF-T 73.008, and it corresponds to the angle of the talus of the slope determined on a

  conical pile whose base is 100 mm in diameter.

  The absorptive capacity is also determined.

  total contribution to introduced charges. For this purpose, the values measured according to the method described previously and given in Table I are used. The ratio R 1 between the quantity of commercial anionic surfactants actually introduced expressed in grams and the value A indicates, if it is greater than 1, an excess of surfactant relative to the maximum amount

  likely to be absorbed by the loads.

  Tables II and III show that it is possible to obtain in a simple manner granular, powder or pearl compositions having a high content of anionic active ingredients, which are easy to dry and flowing.

  and dissolving or dispersing easily (note 2).

  NOTES 1) Hygroscopicity is determined by placing in

  crystallizers 230 mm in diameter, 200 g of

  according to the invention previously dried in a fluid bed dryer at 80 C for 30 minutes, and then abandoning these crystallizers for 96 hours at 23 ° C in an atmosphere at 50% relative humidity and finally in

  determining by weight the weight of water absorbed. We have

  the dry compositions are hygroscopic but they do not lose their flow properties.

  (2) The rate of dissolution or dispersion of

  The compositions according to the invention are determined as follows: In a 2 1 beaker containing 1 liter of distilled water at C, P g of the composition according to the invention corresponding to 5 g of anionic active materials is poured with stirring. then the resulting suspension is kept under constant stirring. After 1 and 2 minutes, the stirring is stopped, 20 ml of the supernatant are removed and filtered on Buchner, and then the amount of anionic surfactants dissolved according to standard NF-T-73-258 is measured in the filtrate. The values found are given in Table III in comparison with 60% <x <75% (rel.l) HOSTAPUR SAS 93, HOSTAPUR SAS 60 and GENAPOL

LRO paste.

  Table III shows the considerable improvement in dissolution rate obtained with the compositions according to

  invention in relation to the usual commercial qualities

the.

TABLE II

N-EXAMPLES 1 2 3 4 5 6 7 8

COMPOSITIONS (in g):

  MICROSIL GP 200 200 200 200 200 200 171.5 200

AMBOSOLC 100 - 85.7

SKS6 - - 100

  HOSTAPUR SAS 60 800 900 800 800 800 800 600

GENAPOL LRO 151.5 800

  Anhydrous Na Sulfate 100 100 Anhydrous Na Carbonate 100 Urea 100

CONDITIONS OF MIXING

  Ambient temperature Ambient Ambient Ambient Ambient Ambient Ramping Speed 60 RPM 60 RPM 60 RPM 60 RPM 60 RPM 60 RPM 60 RPM 60 RPM Total Time 4min . 6 min. 4 min. 6 min. 12 min. 5 min. 8 min. 6 min.

WET ASPECT OF PELLETS

  General appearance sequins sequins sequins sequins sequins sequins granules granules Coulablilté good good very good good average good good good O Presence of agglomerates minimal weak minimal low oul falble falble falble

CHARACTERISTICS OF THE COMPOSITIONS

  A m total absorption capacity of 640 740 640 640 640 725 635 640 charges (year g)

  R1 1.25 1.22 1.25 1, 25 1.25 1.1 1.15 1.25

  R2 = Active Ingredients 2.4 1.8 2.4 2,4 2,4 2,4 1,80 2,76 Silicone Loads Hygroscopicity (Note 1),% 5.9% - 1.7% Material Content active anaesthetic 71.8% 63.6% 61.7% 59.8% 61.4% 60.4% 60.6% (assay according to NFT 73-258) _ __ ___ ___ Dry extract (4 H to 1 05 'C) 99.8% 99.1% 99.0% 99.4% 99.3% 98.1% 98.1% Apparent Density (as per NFT 73-405) 0.42 0.63 0.45 0 , 50 0.50 0.59 Flowability (according to NFT 73-008) 0.586 0.562 0.605 0.585 0.592 0.637 Fine content (less than 0.1 mm)% 0.2 ll 3.6 2.8 2.5 0.1

TABLE III

  PRODUCT HOSTAPUR SAS 93 HOSTAPUR SAS 6 (Example 1 Example 3 GENAPOL LRO Example 8 (in pellets) (paste) granulate 1 (paste) dry dry granular granules Content of anionic active ingredients 93% 60% 71.8% 43.65% 69 % 60, 6% (%) Dissolution time: 1 minute 20% 29% 90% 98% 18% 97% 2 minutes 39% 52% 94% 100% 25% 100% _ The values indicated correspond to the percentages of dissolved surfactants after 1 minute and 2 minutes of agitation

Claims (6)

  1. Compositions in powder, granules or beads containing one or more anionic surfactants, and one or more absorbent fillers characterized by the fact that they contain, by weight, in dry form: - x% of at least one anionic surfactant, with 60% x <75% (Rel.1) - (100 x)% of at least one absorbent filler, designated C, having a total absorption capacity A, the particles of which have an average diameter less than or equal to 100 μm, which is chosen from the group consisting of   silica, alkali or alkali metal silicates   earthy, clays, aluminosilicates, silicates   and alkali metal and / or alkaline aluminosilicates   lamellar earth, also called phyllosilicates, and whose total absorption capacity A, expressed in grams, determined according to the standard NFT 30-022, is greater than or equal to 100 g per 100 g of the load or loads used.   2. Compositions according to claim 1, characterized in that they contain at least one   anionic surfactant selected from the group consisting of   C13-C17 secondary stocks and C10-C18 alkylpolyglycol sulfates and at least one absorbent filler selected from the group consisting of silica, metal silicates   alkaline or alkaline-earth metals, and silicates and aluminosi-   alkali metal and / or alkaline-earth metal   res. 3. Compositions according to claim 2, characterized in that they contain by weight in dry: - x% of at least one anionic surfactant selected from the group of C13-C17 secondary alkanesulfonates and C1-C18 alkylpolyglycolsulfates with% <x <72% (Rel.4) - (100-x)% of at least one absorbent filler in the group consisting of silica, magnesium silicate, lamellar sodium silicate. 4. Process for preparing a composition according to   any of claims 1 to 3 characterized by the   the surfactant or surfactants are mixed in an aqueous or aqueous-alcoholic paste having a concentration by weight greater than or equal to 60% with the absorbing charge (s)   avoiding any mixing to obtain the surfactant composition   active wet powder, granules or pearls correspon-   that if desired, it is dried according to the known methods.   5. Process according to claim 4, characterized in that the surfactant (s) in aqueous or aqueous-alcoholic paste have a concentration by weight greater than or equal to 60% and a Brookfield viscosity of between 100 and 10,000 Pa.s determined at 20 ° C. with a   Brookfield LVT viscometer at a speed of 0.6 rpm.   6. Application of a composition according to one   any of claims 1 to 3 as a surfactant   anionic compound for the preparation of various powders for cleaning products.