Bread of detergent.

AS AFRICAN AND MALAGASY

INDUSTRIAL PROPERTY

P. 887 in Yaounde (Cameroon)

Patent International Patent Classification: 11 no. 02422 C.

the m / - VBE1 O A>e. 1 request 3 May 1967 to 17 hr 00 min

to ro.A.M.P. 1. (G.P. no. 52,919) by

the company said: aogtao Research Company analysis, residing in the United States of America.

5 May 1970 delivered

Published at official ballot № 1 of 1970

Priority: Patent application filed in the United States of America under the trade name no. 548825 10 May 1966 dentatorubral RUBINFELD Fomign lian Gwan orW, Dr. Raymond Dr Camillus ODIOSO.

A detergent bar.

The present invention concerns glass © detergent bars .,

Although the soaps made with fatty acids are relatively easy to process of

5 breads farms, for example toilet soap bars, there are considerable difficulties when trying preparing these breads from detergents sulfonated .SYn *' thetic. Despite the advantages that these synthetic detergents should offer, e.g. behavior

remarkable in hard water along with the lack of

10 precipitate insoluble soap, is the soap which retains far the greater part of the market for detergent bars. Synthetic detergents are relatively inexpensive, such as alcoylbenzônesulfonates currents, which are sold in very large quantities in granular compositions or liquid and have largely replaced the soap in these latter types of detergent compositions, have a satisfactory behavior (like most detergents sulfonated synthetic) when trying to cut them off in the form of cakes. These detergents do not have good flow characteristics and tend to stick to the walls of the extruder (which is a type of extrusion apparatus screw used in soap) cause serious processing difficulties and, in general, giving bread having a satisfactory appearance. Further, the users of the breads made with such aleoylbenzene sulphonates report, in the assembly, they undergo uncomfortable feeling on the skin after use, usually an undesirable sticky feeling.

According to one embodiment of the present invention, detergent bars prepared from alkenyl (- Work) sulfonate. It has been found, at present, it can be readily extruding an alkenyl (Work) sulfonate to obtain breads farms, having good foaming, using standard equipment in soap, such as the conventional extruders.

This substance flows well and slides easily on the inner walls of steel rod machine, sticking, present the cohesion without crumbling into after extrusion, and gives breads hard, solid, good appearance, which retain their integrity after hydration and dehydration, retain a smooth appearance without substantial presence of crystals visible aging, and have satisfactory odor qualities and preservation, although the active is insaturô. Further, toilet bars made from alkenyl (Work) sulfonates are slippery, such as soap, and have pleasant skin, leaving it smooth and sticky nor, nor dry and leathery. They have been found to little near non-irritating to the eyes, by comparison with other detergents which, in general, tend to have an irritant effect.

It is particularly surprising that it is possible to obtain all these qualities from a detergent having olefinic unsaturation, particularly because the soaps olefinically unsaturated give breads quite unsatisfactory, it thereby, while sodium stearate gives a very hard bread that can hold (or Laddie request) a considerable moisture, the soap monoolefinically unsaturated corresponding, sodium oleate, gives breads extremely soft, undesirable, even at very low moisture contents.

The breads alkenyl sulfonates are hard; for example, a bread showed penetration (penetrability, as measured by a penetrometer) of 2.2 mm even at a moisture content of 6 to 7%; the penetration of commercial soap bars are typically between 2 and 7 mm, approximately.

An alkenyl sulfonate can be obtained by sulfonation of mono-olefins, for example using s0₃ as sulfonating agent, and this to a well-known, and it is within the scope of invention that the olefin product known for the preparation of sulfonated detergent bars. One of these reported procedures (has) includes continuously introducing, at a rate approximately uniformly, a gaseous mixture of 0.1 to 10 parts SO ^ (by volume) and, correspondingly, to 90 parts of s9, 3, by volume, of an inert carrier gas (such as air, for example) in a liquid feed of a substantially linear olefin 12 to 20 carbon atoms maintained at a temperature not higher than 50 °c, until not more than 1.1 moles (for example, 0.8 to 1.1 moles of) of s0₃ has reacted per mole of olefin; (d) and (e) hydrolyzing and neutralizing the reaction product resulting therefrom, using a water-soluble base (e.g. HaQH aqueous, at a temperature of 70 to 140 °c); and (d-) collecting, as surfactant composition, the sulfonate contained in the resulting mixture. In other of these reported procedures, 1' olefin is sulfonated in two stages, using a lower concentration of s0₃ , but a rate of addition of the s0₃ larger at the second stage, or by using acid chxorosulfonic and far more sulfonating agent at the second stage. According to the preferred embodiment of the invention, the olefins suifonées, containing alkenyl sulfonate, are those obtained by treating the product of the reaction, SGs ^ - olefin ("mixed acid") by concentrated sulfuric acid, under conditions substantially uncontrolled hydrolyzing, prior to neutralization.

3Rd as we will see, based on the examples below, the olefin sulfonate salt, containing an alkenyl sulfonate compounds, can be used as the sole detergent into the bread, or can be mixed with other detergents, e.g. with soaps or alkyl (Work) benzene sulfonate (having, for example, about 8 to 16 and, preferably, 11 to 15 carbon atoms in the alkyl group), in variable proportions, the salt of the sulfonated olefin constituting at least about 5%, preferably at least 20% and, mléux, at least about 50% (for example, more than 70%) of the total detergent. This is how the use of a major amount of the salt of the sulfonated olefin can make good bread containing detergents, alkyl benzene sulfonate such as, in compositions which, typically, give products unsatisfactory. May, in associations with soap (for example, in mixtures where the ratio soap/olefine sulphate is 3/7 to 7/3 of about) to obtain rolls having surprising sudsing and resistance to transformation in a viscous slurry, said bars providing persistent and relatively solid foams.

Among other detergents which can be mixed with salt of I ' sulfonated olefin, include not only soaps and alkylbenzene sulfonate, but also the alkanesulfonates (such as sulfonates paraffinic primary, containing about, for example, 10 to 20 and, preferably, 15 to 20 carbon atoms), or the salts of alkyl esters of acidescsulxo VBE1 - (including, for example, about 10 to 20 carbon atoms such as methyl acid ^ - sulfomyristic acid or methyl the O { - sulfosuif). One may add sulfates of higher alcohols. As examples thereof, include of sodium lauryl sulfate, Turkey red oil or other oils sulfated, or sulfates or mono - or diglycerides of fatty acids (by " such as a monosulfate stearic acid monoglyceride, sulfates of poly (oxyethylene) dlôthersaicoyl, such as the sulfates of the condensation products (usually containing from 1 to 5 oxyethylene groups per molecule) of ethylene oxide and of a higher fatty alcohol such as, for example, lauryl alcohol; sulfonates laurylic ethers or other ethers aicoyl (Work) glyceryl;

polyoxyethylene sulfates, such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually containing from 1 to s oxyethylene groups per molecule).

When using soaps, the acid portion of the soap can be comprised of a fatty acid, such as lauric acid, myristic, stearic, oleic, eilaidic, isostearic, palmitic, undecylenic, tridecylenic, peniadecylenic or other saturated or unsaturated fatty acid of 11 to 13 carbon muted. Also suitable are soaps of dicarboxylic acids, such as soaps dimerized linoleic acid. Also suitable are soaps other higher molecular weight acids, acids such as rosin or tall oil as, for example, the acicle abietic. As other suitable anionic surfactants, include of amide containing carboxyl groups of fatty acids and amino acids (for example, 1' amide lauric acid amino acids such as sarcosine, acid beta-amino propionic acid, the polypeptides can be produced by hydrolysis of proteins, isethionic acid or acid H-methyl tauric) as well as the soluble salts of these amides containing carboxyl groups.

It is preferable that the hydrocarbon radicals of any substance détergen-Fe-anionic added contain at least 10 carbon atoms approximately, the long chain hydrophobic aliphatic radicals of it to 13 carbon atoms being particularly suitable, and cations anionic detergents added are advantageously such that they communicate water solubility characteristics to the acid portion of the molecule or maintain its water solubility, these cations being, for example, sodium cations,, K, triethanolammonium, diethanolammonium or other alcaneamàonium, the calcium, magnesium (when the agent tensioactiî forms a salt of water-soluble calcium or magnesium) or ammonium. Also useful are salts of groin and aluminum, in desired amounts.

The added detergent, contained in the bread, may be an amphoteric or non-ionic detergent.

Among the nonionic detergents, include of condensation products of lower alcoyienes oxides of hydrophobic compounds as, for example, condensation products of ethylene oxide and higher fatty acids, higher fatty alcohols or hydrocarbons alcoylarylic, containing at least 5 and, usually, about 5 to 30. subgroups. oxyethylenated per molecule, may also be used to react with (Work) corresponding mercaptan thioalcohol, or polyoxypropylene glycols, having a molecular weight of at least 900 condensed, with a sufficient number of groups * vlc thylene oxide, as is well known in the technique. As further useful nonionic, include of alcoylolamines with condensation products of higher fatty acids such as myristic and lauric diethanolamide, fatty acid diethanol amide of coconut, and so on. among the detergents amphotëres, alkylated typically includes a group of 10 to 18 carbon atoms, and examples of fatty imidazolines or higher alkyl such as, for example, L-coco 5-hydroxyethyl 5-carboxymethyl imidazoline derivatives known as "lesser inhibition was cm.", and the TI-alkyl (Work) beta-alanine such as dodecyl beta-alanine or n-dodecyl lucid isiinodipropionic (for example, the substances known as "Deriphats"); the group carfooxylic araphotère detergent can be in the acid form or in the form the flu soluble salt (salt of Na, for example). As further examples, examples of the disodium salt of L-lauryl cycloimidium and 2 a-éthoHy-to-ethionic acid 2 a-ethionic and its corresponding derivative 2 to-or lauryl sulfate.

The moisture content of the bread is advantageously between 1 and 30%, approximately. Poufc any composition given, it is often appropriate to adjust the moisture content (e.g. by preliminary tests with varying amounts of moisture) to provide the best possible operative in the extruder, and for obtaining the bread which, after extrusion, the surface the more uniform; LC ' in general, the moisture content, in order to produce the best behavior can be roving, is between 3 and 15% approximately.

Modifying agents such as plasticizers may also be present, ûû.v in bread, preferably in small amounts, for example in an amount of less than about 25%, of 1 to 20% for example and, preferably, 5 to 15% of about. These include ingredients such as higher alcohols, e.g. alcohols having a monovalent hydrocarbon radical containing 10 to 18 carbon atoms, hydroxyl fixed directly to an alcoholic (as in the alcohol cétyiiqqer or stearyl alcohol) is indirectly fixed to 1' alcoholic hydroxyl, as is the case with the partial higher fatty esters of polyalcohols (such as the mono - and diesters of glycerin and fatty acids of coconut oil or tallow, or lesr corresponding glycol esters).

Fats and oils such as, for example, hydrogenated tallow, may also be present as modifiers, as well as substances such as lanolin and the fatty amides, including higher fatty alkanolamides exhilarating lather, such as lauric diethanolamide or monoethanolamide or myristyl, alkyl or oxide (Work) tertiary amine, such as oxide mvristyldimêthyl lauryl or amino.

The olefin sulfonate salt is preferably an alkali metal salt (ha or K, for example), the sodium salts being preferable for reasons, although the potassium salts often provides breads harder or better erosion resistant. May also be used salts of calcium and magnesium (particularly when present in small amounts, for example from 20 to 30%, as a mixture with the corresponding sodium salts);

may also be used ammonium salts and amine; as well as the heavy metal salts, such as salts of zinc and aluminum.

The varying of the length of the chain of alkenyl sulfonate groups. The number of carbon atoms of the molecule is advantageously between 10 and 30 about, best results, particularly for the bars toiletta, being obtained when the average number of carbon atoms of 1' alkenyl sulfonate is between 15 and 20, approximately. In general, a number of carbon atoms lower provides a bread more soluble, and a higher number gives lower sudsing.

Olefin sulfonate may also be used for the preparation of detergent bars high auxiliaries, containing, for example, 40% or more, for example up to 90? 4, preferably 50 to 00% about builder salt solids. These bars are particularly useful as breads laundry detergents. The sêsê.ls soluble mineral admixture are, in the assembly, it is common knowledge, and can be any alkali metal salt, alkaline earth metal, heavy metal, or any mixture thereof. One may add an ammonium salt or of ethanolammonium, in a suitable amount but, in general, the sodium and potassium are preferred. As examples, examples of phosphates, silicates, carbonates, bicarbonates, borates, sulfates and chlorides water soluble sodium and potassium. The builder salts are particularly preferred alkaline salts such as polyphosphates, - silicates, borates, and c...

In mixtures of water-soluble additives mineral salts used in the compositions for] 5àins laundry detergent-based, it is often preferable to the presence of a mixture of sodium tripolyphosphate and sodium bicarbonate or potassium, for example an association or a salt mixture in which the ratio of bicarbonate to 3/1 to 1/1 of tripolyphosphate is about.

Can be used successfully, in the compositions, tripolyphosphate both phase I and phase IX, as well as mixtures thereof.

The tripolyphosphate commercially available is mostly made by the substance in phase II. The tripolyphosphate of commerce is H§w: btèllêmemt ' a-.essentiellement tripolyphosphate, C." i.e. to 87 - 95 %, associated with small amounts of phosphates (from 4 - to 13%, for example), such as pyrophosphate and orthophosphate. Can also be used sodium tripolyphosphate in its hydrated form. May be used sodium orthophosphate in the indicated amounts.

Sodium bicarbonate or potassium is a buffering agent effective for the pH. The bicarbonate can be incorporated directly in bicarbonate form anhydrous, or as sesquicarbonate, hydrate contains both bicarbonate and carbonate.

As other salts suitable adjuvants which may be incorporated into the compositions for detergent bars synthetic adjuvants include of silicates, carbonates, borates (e.g. sodium tetraborate), chlorides and sulfates (e.g. magnesium sulfate) water soluble sodium and potassium.

In general, the overall proportion of these builder salts represents from 0.5 to 24% additional weight of the bread made. The potassium and sodium silicates having a ratio fa^ 0/SiCj, between 1/1 and 3,5/1 about, are particularly effective as corrosion inhibitors, in proportions of about 1 to 8% of the weight of the finished bread. The sodium sulfate content is advantageously kept low, for example to less than one third of the weight of the phosphate (calculated by weight bag).

In general, toilet bars contain little or salts of alkaline builders, usually much less than 5% of these salts, and their total content salts minerals (e.g. Na_? S0 ^) is, in general, well below 15%, and usually less than 10? 4, the total content of detergent representing in general more than 50% of the weight of the bar.

The breads can contain ingredients having a germicidal activity, which can be incorporated in an effective amount up to about 10%, from and, preferably, between 0.1 and 5%, for example. These

ingredients include halogens such as halogenated salicylanilides hâldgénêstridilorocarbanilide

as, for example, the tribromosalicylanilide, bis-phenols such as, for example, hexachlorophene; the trifluorométhyldiphényl urea halogenated;

the zinc salt of L-hydroxy 2 pyridinethione;

c..., as well as suitable mixtures of these compounds.

In some examples below, we indâqué content "oil free" bread.

We have made satisfactory breads, having the desirable properties, sulfonated products from short oil free, for example having oil level between 1 and 12% free about, preferably between about 1 to 8%, by weight of the anionic surfactant contained in the sulfonated olefin. It is preferable to lower the content of free oil, and it is desirable to alter it by a heat treatment of L ^ aqueous neutralized sulfonated olefin, by bringing the aqueous mixture into contact with a substance having a heat exchange temperature of at least about 126 °c, to raise the temperature of the reaction product to at least about 110 °c, said heat treatment being carried out at substantially atmospheric pressure, while expelling water vapor of said reaction product such that the water content of the product, after said heat treatment, is between 1 and 12%, approximately.

Salts of sulfonated olofines products are often chafhois or brown color.

To obtain!? âes loaves of lighter color, can discolor the substance, for example by treatment with 1' aqueous sodium hypochlorite, hydrogen peroxide or other suitable decolorizing agent.

The fact that the little alccnyl sulphonates?~wind being formed into the detergent bars using normal installations for making soap bars currently used is very important. In general, these devices consist of a "amalgamating apparatus" to mix the ingredients, a roller mill for homogenizing the mixture and place it in the form of chips crushed, an extruder for extruding the tamping and crushed chips in the form of a continuous bar, a cutting apparatus for subdividing the continuous extruded bread loaves separate, and a urged to print a pattern on each of the dice or sirmes breads and into their final configuration. In the conventional extruder, with a screw rotating continuously in a cylinder, this product is heated (by frictional heat generated by the work of the substance supplemented, if desired, by heat from a heating jacket) to communicate appropriate plasticity to the substance, the substance in the cup and the screw action, by being caused to pass through an orifice plate multiple continuously scanned by a multiple blade knife, rotating with the screw, and, thence, through a die and in which the outlet port is in accordance

->ITs

to the cross-section of the desired bread, (whose opening has, for example, a surface of 1.5 to 25.8 cm2 about, and a height of about 1.27 cm, or more) and whose walls can be heated or cooled.

According to another embodiment of the invention, the breads obtainable without any separate extrusion pressing or extrusion. In this way, according to one procedure, the breads prepared by casting in a suitable mold, e.g. in a frame to soap, a molten composition, hot, for obtaining a roll and having a solidification temperature higher than ambient temperature (from, for example, between 37 and 60 °c about, and, preferably, between about 43 and 54 °c). As shown in the example 7, the molten composition may contain soap (or other detergent added) that may form in in situ. The soap may be a superfatted soap, containing a fat or fatty oil unreacted.

The following examples are given as an illustration of the invention.

Example 1

A tube reactor is used jacketed having an inner diameter of 20.9 mm and a length of 5.89 m for performing the first stage of sulfonation, and by sulphonating a mixture of alkenes, continuously, with a gas mixture containing 4% (by volume) of sulfur trioxide in air. The mixture of alkenes contains about 88 ¾ straight chain olefins;: and having a poic Peppers tarminalement unsaturated molecular means 230 and a length. average chain length of 15 to 18 carbon atoms approximately (24% in c_15# 29% in c ^, 30% in C. ^, 18% in c. ^, about), and boiling, at atmospheric pressure, between 265 and about 360 °c (with 11% of residues).

In the sulfonation reaction, the alkene is spread in a falling film on the inner wall of the tubular reactor, at the upper part thereof, and the sulfonating agent gas is injected from top to bottom, at a high speed volumetric, toward the center of the tubular reactor, at the upper part thereof. The reaction temperature is adjusted hr About 65 °c, using water cooling to 26 °c in the cooling jacket surrounding the engine, and gage pressure, in L-O-reaction medium, about 0.7 kg/cm2 is Da. Is reacted about 10.4 kg/hour of alkene 6;35 kg/hour with about sulfuric anhydride (molar ratio OS ^ / alkene of 1/1) dispersed in 0.85 m3/minute of air having a dew point of about -73 °c (1 ppm water).

Separating the mixed "mixed acid" starting from the tubular reactor in a two gas separator to the base of the reactor, and then continuously injects in a recirculation loop, together with an amount of 2.95 kg/hour of oleum to 20%, the "acidic mixture" and oleum being both added continuously by a pump located at the inlet of the recirculation circuit R in the circuit, the recycle mixture is maintained at a temperature of about 35 °c. The average residence time, recycling, is 2 to 5 minutes and gage pressure is of the order of 0.35 kg/cm2; the substance continuously emerging from the circuit the DS rscvclage is deactivated immediately by a dilute aqueous solution of sodium hydroxide, at a temperature of about 93 °c, until a pH of 9 to 10. The analysis of the aqueous product syrupy neutralized indicates that it contains VBE1 by dry weight) of 34% anionic detergent active, 6.5% mineral salt and 9.4? of £'d * "hùile ': free" (substance obtained by extraction by pentane from aqueous ethanol solution).

(has) the aqueous product containing about 47.1% of syrupy neutralized "solid" (it is say substances substantially non-volatile at ambient temperature and pressure) and, for the remainder, water, is subjected to a heat treatment and is dried to a moisture content of about 7 to 8%, by passing the product into a film evaporator, in which the product is spread rapidly in thin film on the faces of metal walls are maintained at a temperature of about 1833c, using a chemiBage circulating steam under a gauge pressure of 10.5 kg/cm2, while passing a stream of air, at atmospheric pressure, on the surface of the film. The residence time of the substance in 1' 5 to 10 is Rh evaporator seconds to about its temperature, its output 1¹évaporatour, sulfo of 121 °c, or more. During this processing, the content of "oil free" (calculated year CMS) decreases appreciably (up to a value of around half its value before treatment). The substance; that is then solid, is then carefully mixed with small amounts of ti0 pigement₂ and perfume, and then into a mill soap where it passes between a set of three rollers steel very close together, so as to produce a thin compressed sheet material which is cut into narrow strips when leaving the mill. The ribbons is charged in a boudineuso to standard soap, wherein the substance is packed extradited continuously in the form of a continuous bar, under the action of the screw-shaped over; Archimedean screw of the extruder, through a narrow orifice and a die with the outlet in the form of desired cross-section bread extradited (for example, about 2, 54 x 5, 08 cm). The bread extradited is then cut - in personal cleansing bars having about distinct 7.62 cm in length.

The die of the extruder is maintained at a temperature of about 43 °c. The pH of the bread (measured on a dispersion to 1% in deionized water) is 7.3. There is obtained a satisfactory bread, having remarkable sudsing.

b) repeating the to ECYF near added, before grinding, an equal amount of soap, the weight, the weight of the composition neutralizes a thermally treated and that the die of the extruder is at a temperature of 37 °c. The soap is a sodium soap ··℮ prepared from 75 degrees' fatty acids of tallow and 25 ¾ of fatty acids of coconut oil, and it contains 12% of aau. There is obtained a satisfactory bread, which does ρ ¾ ¾ ' easily in a viscous slurry.

(d) repeating the example lbs, except that the amount of water is 13 times the amount of the neutralized product heat-treated. There is obtained a good with bread even better resistance to the transformation into a viscous slurry.

(d.) repeated the example the, to this the PR ^ e is added, before crushing, cctylic representing an amount of alcohol in the amount of about 16% neutralized product heat-treated.

There is obtained a satisfactory bread having remarkably sudsing.

(i) the example the repeated, except that the composition, before crushing, contains 75 parts of the neutralized product heat-treated, 11 parts 6' cetyl alcohol, 3 parts of hydrogenated tallow (üî *. triglyceride), 1 part of trichlorocarbanilide (a germicide) and 1 part lecithin (quality Staley "LF"). There is obtained a satisfactory bread, having. sudsing remarkable and unexpected resistance to erosion.

Example 2

Using the procedure described in the example the. to prepare the syrup neutralized, the PR-to-Peppers following exceptions %

The charge of alkene is a fraction of

to c " containing 90% of monoolefins, the olefins 15 20

being distributed roughly as follows;

1% in c_1yl , 2 1/2% c,_/c.20% in C.._{the R} , 18% in C-_,

14, 15/lo and 1

17% c, 18% in c, _ and 15% CH, the range

19 4u lo and

D.¹ boiling, at atmospheric pressure, being O ', between 275 and about 320 °c (with 6% this residues). The proportion SO ^ is 0.35 kg per kg load. Sulfuric acid (to 97% that the n ^ OS) is injected into the ol-sulfonated year&thin spot a height of about, 3.93 m from the bottom of the tubular reactor and is used in an amount of about 0,125 ha through kg of olefin charged. The neutralization is effected on the admixture••batch: ;, to 93 °c, 2 hours during.

Film after heat treatment, the neutralized product contains 94.7% solids, the anionic active ingredient content (dry weight) being 76.2% and the free oil content (dry weight) being 5%. Then treats the substance as to the example lbs and obtained a bread containing roughly equal weight sulfonated detergent and soap. There is obtained a satisfactory bread before a remarkable formation of a viscous slurry.

Example 3

(has) neutralized the syrup is prepared according to the described procedure all circuit ' example 1, except

that the olefin feed is a fraction of Ch to

the containing about 89% of mono-olefin, 83% * d-alpha monoolêfine, the average molecular weight of olefins is C! e of about 271, the olêfines being roughly distributed as follows:

21% in c₁₀ , 35/6 in c, 32% in CH and 11? 4 c " _.

18, 13 20, 21

After the heat treatment, the neutralized product contains 96.9? 6/solids? the content of anionic active inqrêcient (dry weight) is 90.3%.

Then, mixed, ground and coiled the substance heat-treated, as illustrated here? before crushing, about 3% water is added to the chips. There is obtained a satisfactory bread, having a remarkable formation of a slurry and erosion.

(d) mixing the substance heat-treated in the example 3 _a to one-equal weight of the substance ayaàt:: undergone " 1 a heat treatment of the example lja and minor amounts of pigment - TiOg and perfume, as well as with 5% (by total weight of the mixture) of water, at room temperature.

And then grinding the mixture, it is cut into ribbons, is strapped to the extruder (as well as for the example the) and it is cut into bars that have a moisture content of

- 6 $about. The trials on the loaves, with C'_has therein_year t a hardness of 125 ppm, show that the breads have a foaming speed of 8 strokes and a viscous slurrifying index representing a loss of 10.7 gï, bread has a pH of 7.0 (measured on a dispersion of 1% in deionized water).

Feed efficiency in viscous sludge is measured leaving a cake of known weight having a surface 77 mm x 49 mm and a thickness of at least 12 mm, to lie flat, during 17 hours, at room temperature, in an ordinary petri dish lid (of 100 mm in diameter and 15 mm high) with 35 ml of water; then removes the bread and water, with the side face of the index, is removed from the pulp sludge at the bottom face and along the edges of the bread. Then, at the end of 48 hours of air desiccant, edgewise, weighing the bread.

The index of slurrification is the difference between the weight of the dry cake before and after soaking and removal of the sludge, expressed as grams lost.

The "foaming speed" is a well-known measurement of the ease of obtaining the foam.

(c.) is mixed 46.1 parts of the substance heat-treated in the example 3a with 20.5 parts of n-lauryl dimethylamine - β - iminodipropionate sodium acid ("Deriphat 150"), 17.7 parts of hydrogenated tallow, 5.1 parts fariue tapioca, 5.1 parts of phosphoric acid aqueous g5 degrees and £5.1 parts of sodium tridecyl benzene sulfonate linear OD, as well as minor amounts of ti0₂ and fragrance, and is ground and coiled the mixture to obtain a bread having an acidic pH.

Example 4

(has) proceeds as to the example 3<I to this par^: ~- o that discolors the aqueous product neutralized, before heat treatment, as suits 90.7 kg of the neutralized product is mixed with an aqueous solution of 11.3 kg HaOCl to 33% and allowed to stand still for 1/2 hour at a temperature of 43 °c. about.

Then added a sufficient amount (about 0.9 kg) sodium sulfite, in aqueous solution, to react with the excess IJaOCl (it is to say, until the tests at paper starch-tiodure show absence of HaOCl). After one night rest, mixture is worked by a small amount (about 50 ml) of concentrated sulfuric acid, to adjust its pH to 7.

The aqueous suspension contains 34% solids decolorized, 86.5% (by dry weight) of ingredient before activity anionic and 5.9% (by dry weight) of free oil. The product is subjected to heat treatment and pressurizes the όη· formed. breads, as exemplified by the. There is obtained a satisfactory bread having a remarkable transformation into pulp sludge and unexpected resistance to erosion.

(d) repeating the example 4ci, except rívetted * is mixed thoroughly with the neutralized product undergoes heat treatment before an amount of cetyl alcohol is about 13% OD thereto. A cake obtained a remarkable good with the slurrification.

(i) the example 4 A is repeated, except that the neutralized product is mixed thoroughly, heat-treated with the third of its weight of the neutralized product, having undergone a heat treatment, OD the example 1.

Example 5.

(has) procedure used similar to that of the example 1 for making a syrup neutralized. The mixture of alkenes used consists of a crude feed olefins from to obtained in crispness OD paraffin wax and having, according to the manufacturer, the following analytical characteristics;

monoolefins and diolefins olodines aeyelic 84% 5% 5% paraffins and napthenes naphthenic cyclic olefins and diolefins bicyclic aromatic compounds 1% 1% 92% of acyclic monoolefins are alpha-monoolefins. The average molecular weight of the portion olefin is about 240, and the distribution of olefins is the following: 2% in c. ^, 1s %

c_1F , 20% in 21% in Cl,, 18% in ch, 16% in

15, 16/lo and 1

^C 19'⁵ *">^C 20

The neutralized slurry resulting R contains 44.1% solids, 78.9% (year dry weight) of active ingredient anionic and 12.3% (by dry weight) of free oil. 68 Kg of the suspension is mixed with 14.5 kg of a 50% aqueous slurry of sodium linear tridêcyl sealing devices and the mixture is stirred, at a temperature of 60 °c, while adding 2.87 kg of molten stearic acid and stearic diethanolamide 1.92 kg of molten. And subjecting the mixture to heat treatment, 1 film state, as in the example 1, until a moisture content of about 10.1%, thereafter adding the pigment and fragrance, and continues processing the substance as has the example the, and there is obtained a satisfactory bread, before a good resistance to transformation is mud and erosion.

The alkyl substituent of the alkyl benzene sulfonate sodium contains on average 13 carbon atoms (about 15 mole %. ^ c, 55 mole % in

C and 30 mole % in c, .); the substituent alcovli-a 13 14

that contains about 20% of alkyl groups that bond to the benzene ring by the carbon atom 2 of the alkyl group, the alkyl group thereof remaining bonds to the benzene ring by the carbon atom at the 3 (or more)/(for example, 45% on the carbon atom at the 5 or 6).

(d) mixing the substance heat-treated in the example 5a, and while the milling as illustrated ., with a TiN equal that of soap chips, and then coiled bars as to the example 1. The soap is a sodium soap prepared from 75? confectioneries fatty acid 25% fat and fatty acid

~ 2 j. the coconut oil, and contains 12% water.

Satisfactory bread is obtained, with improved resistance to transformation hoe and erosion than the example 5a.

(d) repeating the example 5a, except is input, in the mixture the slurry, 14? 4 of îtf-to-feurylthe Li~ - iminodipropionate sodium acid and supplemental water of 33%.

(to) Is repeated the example 5ç, has this near which comprises mixing the substance heat-treated with 50% soap chips of the example 5b.

(has) is tratra.ïte a load key unfair, similar to that of the example 5çv, by OS ^, ^ ^ OS-H and I-TaOF. , as exemplified by the. Obtaining a suspension containing neutralized 47.5% solids and 37.5% of anionic active ingredient; its oil content free (relative to the amount of anionic active ingredient) is 10.5%. To this slurry is added an aqueous suspension (having a solids content of about 54%) containing a alcoylbenzèns sodium sulfonate (having the same composition as that described in the example 5a), and stearic acid, the proportions being such that there is 53.3 parts of the anionic substance obtained by sulfonating 1' define syntax, 20 parts of the alcoylhenzene sulfonate and 7.5 parts of stearic acid. After mixing the suspension, is treated by heat treatment at atmospheric pressure, on a drum having a temperature of about 149 °c, so 1 form chips having a moisture content of about 3% to 2. Chips are mixed with 0.5% of their dry weight of pigment of TIQ ^ and 0.8% perfume, are phase-rotated in 3 passes in a mill 3 cylinders, so as to obtain ribbons, and subsequent passage to the extruder so as to obtain a continuous cut in bread loaves distinct toilet having a moisture content of 2.5%.

(d) repeating the example its ., except that is added to the slurry molten hydrogenated tallow, instead of stearic acid, the proportions are the following; 55 parts of the active substance of the anionic alkylbenzene sulfonate, and 15 parts of hydrogenated tallow. The processing conditions are the same as in the example 6a _.

(d) using the same olefinic fraction than the example 6ji, and replacing HaOH Pal of KOH at neutralization stage, obtaining a suspension of a potassium salt olefin sulfonate.

Put into the form of cakes by subjecting the substance to heat treatment, as in the example 6a, and passing SAL chips resulting therefrom, as well as. 1% of TIQ ^ and 0.5% perfume, in the mill and the extruder, as to the example 6a, stamped into bars having a moisture content of about 7%.

Example 7

written, in this example, breads prepared from mixtures of soap and 1' sulfonated olefin, the soap being formed in in situ , the presence of the sulfonated olefin.

(has) suspension is faded the example 4a to a film evaporation, at atmospheric pressure, as in the example, so as to form chips having a moisture content of 1 to 2%, approximately. Added 115 parts of these chips to 200 parts of coconut oil, 5 parts of an aqueous solution of a blue dye to 1%, TDC 3 parts of perfume. After thoroughly mixed, this product is heated up to about 60 °c, SAM^{; ii} - e being added 67 parts of an aqueous solution that is ' 50% sodium hydroxide while continuing mixing until a smooth mixture. The heated mixture is poured (before a temperature of 71 °c, due to the exothermic reaction forming soap) in shapes (cadcad.res soap) and letting it cool down? then by pulling apart the shapes and cut the product loaves distinct.

The breads have good hardness, are silky and smooth to the touch, and have good foaming properties? their solids content is about 27% of moisture, and their content of the sulfonate anionic activity is about 24%.

(d) in a manner similar to that described in the example " 7a, prepared breads containing about 32% of the sulfonate anion activity and about 30% to moisture.

(c.) is pat ' Te of the instance 7a, except that the substance sulfonated used is that described described example the (modified by bleaching using an aqueous solution of tii 0 to 35% prior to neutralization), and shavings are produced containing 87% (by dry weight) of anionic substance having an activity, 5.6% (by dry weight) of free oil and about 1 to 2% of moisture. The proportions used in the preparation process of the soap are as follows: 125 parts of these chips, 200 parts of the coconut oil, 60 parts water and 67.5 parts of the solution to 50% NaOEï. The breads contain about 27% of substance sulfonated anionic activity? about 20% of water? they are hard, are agrc % bdenoting touch and provide a foam somewhat faster and copier that those examples 7a and 7b.

Example 8

This example is illustrative of the use of the sulfonated olefin in a loaf laundry detergent containing high proportions (of 40 to about 05%, for example) of builder salts.

a) by sulphonating and neutralizing a mixture of aieInès, as described in the example the, proceeding generally as described in this example, then through a treatment.

thermal drums internal heating up to a temperature of 149 to 176 °c, to form chips containing anionic active ingredient 72.8%, 3.1% and 1.2% oil free moisture.

Then mixed carefully 38.5 parts of these chips, in a mixer "in Hobart", with 20 parts of pentasodium tripolyphosphate (phase-II, anhydrous) powder, 11 parts of tapioca flour, 30.4 parts of sodium bicarbonate powder (anhydrous) and small amounts of perfume and colorant. Then incorporates 10 parts of water to the mixture that is then passed twice in a mill soap the Lehman to three cylinders, and is then coiled in a vacuum of 63.5 cm of mercury absolute, to a temperature of between about 60 and 76 °c, and there is obtained a continuous extruded rod that is cut into appropriate lengths to form distinct breads that is then passed to the press.

(b.) sulfone and is neutralized (as described generally to the example 3aj a mixture of alkenes, as described in the example 3 A, then through a heat treatment in an evaporator, as a film, as in the example 1, to form chips containing 96.9? 4 solids and 90,3% (dry weight) of anionic active ingredient. Then thoroughly mixes 27.8 parts of these chips, in a mixer in Hobart, with 20 parts of pentasodium tripolyphosphate powder (step IX, anhydrous), 11 parts of tapioca flour, 30 parts of sodium bicarbonate powder (anhydrous) and small amounts of colorant and perfume. Then adding 10.7 parts of water, followed by treating the mixture as the exemole 8a.

(d) repeating the example 8b, . except that when using soap and sodium sesquicarbonate (rather than bicarbonate) and that modifies the amounts of ingredients, which become: 16.5 parts chips, 20 parts of sodium sesquicarbonate, 30 parts of soap chips (soap of the example 1b), 20 parts of sodium tripolyphosphate, 11 parts of tapioca flour, 2 parts of water added *

(d.) sulfone and is neutralized by a mixture of alkenes, as described in the example 3 A, (by performing, in general; as described in this example), then through a heat treatment, as in the example 1, to form chips containing 89.5% solids, 79.2% (by dry weight) of active ingredient anionic and (dry weight) 2,l?o of free oil.

Then mixed carefully 27.2 parts of these chips, in a mixer in Hobart, with 20 parts of pentasodium tripolyphosphate powder (phase II which anhydrous), 11 parts of tapioca flour, 38 parts of sodium bicarbonate powder (anhydrous) and small amounts of colorant and perfume.

Then adding 3.51 parts water, and continuing processing the mixture as to the example 8a, .

(i) are mixed carefully 16.3 parts of chips of the example 8d _, in a mixer in Hobart, with 20 parts of pentasodium tripolyphosphate powder (phase II which anhydrous), 11 parts of tapioca flour, 20 parts of powdered sodium sesquicarbonate, 30 parts of the same of soap chips than those used to the example 8c;, and small quantities of colorant and perfume. Then added 2.2 parts water, and continues processing the NR Ca_ diaper as illustrated.

(f.) is mixed carefully 27.2 portions of chips of the example 8 £, in a mixer in Hobart, with 20 parts of pentasodium tripolyphosphate powder (phase II which anhydrous), 11 parts of tapioca flour, 37.5 parts of fine crystals of sodium sesquicarbonate and small quantities of colorant and perfume. Then adding 3.55 parts of water, followed by treating the mixture as to the example 8a.

As shown by the foregoing examples, when the process for preparing the alkenyl sulfonate surfactant comprises processing the "acidic mixture" by 1' ^ sulfuriqua acid, the concentration H ^ ^ OS sulfuric added is at least 50% and, preferably, much higher, e.g. 90%, 91% or 100% H ^ ^ OS, or oleum 20%, and the amount of water provided by the acid added is, generally, less than 10% of the weight of the "acidic mixture", preferably less than 5% and, most typically, less than 3%. The temperature of the treatment may, for example, be between about 10 and about 10cv.c, preferably between 25 and 60 °c about, and duration is advantageously relatively short, preferably less than 1 hour and, for the best results, less than 20 min, about, for example of 5 minute, or less.

It is preferable that the treated substance is loaded directly in contact with a basic substance.

for neutralizing, but it may be an intermediate process, preferably a heat treatment (for example), in an aqueous medium at a temperature of 100 to 200 °c), prior to neutralize it.

The neutralization can be accomplished by carefully mixing the substance with a basic material and water (for example with an aqueous solution of ïîaOH of îo to 50%, preferably in an amount such that it causes the pH to 10 about, or to a higher value) and maintaining the mixture at an elevated temperature, preferably greater than 60 °c, for example at a temperature from about 200 °c to 65 dd.e.

The treatment with sulfuric acid provides a product which, in some cases, contains a proportion much raise-th alkenyl sulfonate and a minor proportion (which may, for example represent less than one third of total sulfonates), or not at all, hydroxyalkane sulfonate; its content alccny 1 sulfonate is often made, a substantial portion, by a ΐ, Λ - 3.4 to-alcênyl sulphonate. The olefinic sulfonate detergents may also contain minor amounts of Sisulfonates, presumably forms during the sulfonation treatment by reacting the excess of SC>₃ with the alkenyl sulfonate groups formed during the sulfonation.

Sulfonating the olefin feed may contain - for example, olefins having from 10 to 30 carbon atoms RIE process, preferably from 15 to 20 carbon atoms approximately, as previously indicated, the alpha olefins being preferable. The feed may contain minor amounts of other constituents, such as olefins secondary or internal, diolefins, cyclic olefins, aromatics, naphthenes and alkanes, and may be obtained by cracking petroleum wax, by catalytic polymerization of ethylene, by dehydration of long-chain alcohols, andc...

The reaction can be performed initial OS ^ - olefin in a manner known in the technique, for example by charging a current SO ^ highly diluted with air or an-other gâz ' îâteite (in a~molar ratio inert gas/OS ^ of, for example, 5/1 to 100/1, preferably greater than 10/1 about, for example ranging from 50/1 and 20/1) in contact with a current (for example with a thin falling film) of the olefin feed. The molar ratio 50 ^ / olefin is typically range between 0,5/1 and 1,3/1, and is preferably about 1/1. It is preferable to use an SO ^ non-complex for reaction with 1' olefin.

Of course, the invention is not limited to the embodiments disclosed which was just as examples.