DEP0007424MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: April 4, 1952. Advertised on May 24, 1956

GERMAN PATENT OFFICE

The invention relates to the production of soaps with a high water and salt content, which nevertheless possess the properties of pearled soap.

Pilated soaps have easily recognizable properties, which differentiate them from other commercially available soaps and are very suitable for many purposes do. These properties are. among other things a uniform structure, a firm consistency, a smooth, waxy handle, a smooth surface, one essentially in a single direction Occurring grain or crystal orientation, transparency (if no whitening agent is added would). These soaps won't shrink or warp as the bars age and dry out, they swell in water, but essentially resume their previous shape after drying and the earlier appearance, dissolve quickly in water, especially when rowing, and therefore possess a very high foaming capacity. Other properties discussed below are the presence of the soap in the / J crystal phase and the lowering of the "dew point" of the liquid in the soap bar.

Piled soaps are commonly made by making a soap with a low moisture content Electrolyte content (e.g. 10 to 15% water and 0.4 to 0.6% salt) "piled up", d. i.e. that one the largely solidified, but still plastic soap between a row of rotating rollers can pass through, with successive pairs of rollers of this series each with higher Speeds and with closer play around

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run so that the soap is machined, subjected to shear forces and solidified. The emerging soap bars or strips are then mechanically processed further, squeezed across and solidified by forcing them through one or more mouthpieces of decreasing size, by the pressure of a conveyor screw rotating in a closed drum. The compressive effect of the screw

ίο on the soap and expressing through that The mouthpiece is known as kneading and squeezing. The mechanical processing causes a temperature increase, which can be regulated depending on the supply or discharge of heat. The combined effect of temperature and squeezing out under pressure causes compaction of the soap and results in it emerges from the mouthpiece as a homogeneous, coherent, slightly plastic bar. This The bar is then cut into suitable lengths and embossed.

So far, pearly soaps have only been made from soaps with a low water and electrolyte content. The kettle soap, ie the so-called "kettle soap", which was obtained by settling over glue deposits during normal soap boiling, contains about 0.4% or more sodium chloride and up to about 0.1% sodium hydroxide or Na ₂ CO ₃ , However, it has an exceptionally high water content for pilier purposes, namely usually about 30 to 32% H ₂ O. Pilier of such soaps has proven to be inexpedient because the flakes stick together, the pressed bars are too soft and the soap does not have the favorable properties has piled soaps. Drying is therefore usually necessary before mushrooming, as a result of which the water content is reduced to about 10 to 15%. This of course makes soap production more expensive.

The subject of the invention is the production of a pearled soap with a high moisture content, by making soap flakes and bars high in moisture and electrolytes, which nevertheless have the properties of pearled soap. The invention also relates to filled Soaps with the properties of pearled soaps.

According to the invention, the above objects are achieved in that one has a plastic, solid mixture of soap, water and electrolyte is machined and made compact, d. H. by squeezing transversely under pressure (exposure to shear forces). The relative proportions the components and the temperature of the mixture are regulated as described below, that you get a product with the desired properties .. Generally speaking, it can the soap according to the invention can be referred to as a pied soap composition, which differs from Soaps known to date have a significantly higher water and salt content or another suitable electrolyte.

The invention opens up the production of soap products with very favorable properties a wide, new range of compositions.

Fig. Ι to 5 of the drawing show graphic representations from which the quantitative ratios of the water and electrolyte contained in the soaps according to the invention can be found. the The electrolyte in Fig. 1 is sodium chloride, in Fig. 2 tetrasodium pyrophosphate, in Fig. 3 pentasodium tripolyphosphate, in Fig. 4 trisodium orthophosphate and in Fig. 5 sodium silicate.

The invention will first be described in relation to a ternary mixture of soap, water and electrolyte described in which the soap is the sodium soap of a mixture of 80% tallow and 20% coconut oil and the electrolyte is sodium chloride. The invention then becomes more general then explained.

The soap used in the process according to the invention can be prepared according to the usual soap boiling process in the boiler with cleaning by settling and separating into immiscible ones Phases or prepared by warm or cold processes known to those skilled in the art will. It can also be achieved by continuous saponification of fatty acids under pressure, as in U.S. Patent 2,159,397, or any other method will. The soap can be adjusted to the desired water content or in any way may be used without regulating the water content if the same is used during manufacture the soap yields cheap. If water is to be removed, this can be done in a conventional manner happen, e.g. B. by partially drying flakes in a drying chamber or by spraying the melted soap at high temperature and pressure in one under lower pressure standing evaporation chamber, whereby water is evaporated. The conditions will be like this regulated so that the desired water content is achieved. Partially dried soap can also be used in a mixing device (crusher) in a suitable proportion with melted, Not dried soap can be mixed until it is uniform and homogeneous and the desired Has water content. On the other hand, if the water content of the original soap is too low this can be remedied by adding a water solution of the electrolyte, e.g. B. from Sodium silicate, mixed with the melted soap before cooling and setting. Electrolyte can be added to the soap either in dry form or in solution, if necessary will. Appropriately, but not necessarily, it is in one with the melted soap Mixing device mixed.

Treatment in the plastic, solid state

As stated above, there is the inventive Procedure in mechanical

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Treatment of a soap-salt-water system in a plastic, solid state that can be deformed under pressure, but essentially under the action of gravity alone is not flowable or without the application of considerable pressure after separation cannot reconnect when touched. The desired plasticity can be achieved in any way by one

ίο z. B. a thin film over a chill roll can run and it cools to flakes or tape form or by cooling with stirring z. B. in a continuously operating cooling device (e.g. a "votator") as described in the USA patent 2,295,596. In this case the soap is usually in the form of Ribbons, plates, threads or cylinders of small diameter, depending on the size and shape of the mouthpiece or mouthpieces.

It is also not always necessary for the soap-salt-water system is homogeneous already at the beginning of the mechanical processing, as in many cases by such. Treatment a heterogeneous System can be made homogeneous. The following description is intended to indicate the conditions that apply according to the invention for the plastic, solid systems, explain.

It used to be assumed that the usual Soap bars used in the household are completely solid, with the water content as Water of hydration is built into the crystal structure. In contrast, recent studies have shown that at normal use temperatures soap bars, if they are not extremely dry, usually consist of solid soap crystals containing a small amount of a diluted, liquid solution of soap in water, known as glue deposit, and that only when Cooling down to a few degrees below zero this liquid freezes to ice and the bar is completely frozen becomes solid. At sufficiently low temperatures that are even above the melting point of ice Such bars are brittle and crumbly, while at higher temperatures they are partially as a result Conversion of the soap crystals in glue deposit are more plastic. With further heating . well above room temperature the crystals become progressively fewer, and so does the deposit of glue is replaced by another non-solid phase, which (depending on the soap composition and the temperature) either from the pure soap core with low viscosity or as Glue soap with high viscosity can exist. When the temperature of this two-phase solid-liquid system if it increases still further, more and more solid crystals become in liquid converted, and under certain circumstances the solid phase disappears completely.

The invention does not relate to an entirely liquid system, nor is it practiced at temperatures at which the soap is syrupy in nature, e.g. B. a mixture described in US Pat. No. 2,295,594 of essentially soap crystals and the soap cake formed in the kettle. The invention is also not practiced at temperatures at which the soap is soft enough to be able to operate at low pressure, e.g. About 0.35 to 1.75 kg / cm ² as in U.S. Patent 2,377,424 to be expressed. In such systems the flowability is too great to allow application of the required shear forces. The received. Soaps which have not been subjected to any transverse squeezing and which have no internal gap surfaces, which is characteristic of the piling, kneading and pressing of plastic, solid soaps, also do not have important properties of the pied soaps. In order to achieve these properties in the compositions according to the invention with a high moisture and salt content, the same shear forces must be exposed as they occur with different movements in the plastic, solid state under high pressure. These pressures can e.g. B. be exercised by roller rolling or by kneading and pressing and are about 7 kg or more per square centimeter. It is preferable to work at a temperature at which the soap-water-electrolyte system consists to a large extent of soap crystals and only a small portion of dilute glue, since the properties of pearled soap are easiest and best to achieve in such systems. In some systems, however, which contain a large amount of crystals and a small amount of soap glue, the viscosity or plasticity is such that the shear forces and pressures according to the invention and thus the achievement of the properties of puffed soap are negated. As a rule, the process according to the invention is therefore carried out at temperatures at which the soap core is not in stable equilibrium, i.e. at temperatures below the solidification temperature of the system, but above the temperature at which it becomes crumbly and at which the system, however, i ° 5 is in a plastic, solid state. It essentially consists of a mixture of a large proportion of solid soap crystals with a small proportion of a non-solid soap phase, which is stable at these temperatures and can either consist of nigre or soap glue.

The minimum temperature at which the pure soap kernel can exist stably can be for a certain soap composition can be determined in different ways. A possibility offers the well-known dilatometric method, as both occurrence and disappearance of pure soap is accompanied by a change in the slope of the volume temperature curve of the system is.

According to the invention, the soap can only be mechanically processed and compacted satisfactorily when it is substantially in the plastic, solid state described above. The method according to the invention exists

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in the fact that the soap can be used mechanically in this state kneaded, squeezed across and compressed, which z. B. when going through between usual Roller rolling takes place. However, this mechanical processing can also be applied to any other Way to be carried out. The effect of the roller rollers can be completed by that the soap is further compressed and processed by kneading and pressing. Actually results

ίο often repeated squeezing under high pressure mechanical processing, transverse squeezing and compression that in their nature and effect the results obtained when passing through a series of rollers same. The reason for this lies in the linear flow of the soap under pressure, whereby adjacent layers likely to flow at different relative velocities. According to the invention is therefore soap in flake form,

2.0 which has the properties of pearled soap, made by putting it over and between Rolling rollers run or by repeatedly pressing them through a narrow slot. Soap in bar form is according to the invention by rolling, kneading and pressing or in other forms, such as B. threads or spaghetti-like structures, by a suitable choice of size and the shape of the mouthpiece through which it is pressed.

Crystalline phases in soaps

A brief discussion of the phase relationships in soaps is necessary to understand the results achieved by machining and compaction according to the invention. It is known that the solid commercially available soap occurs in at least three different crystalline phases, which are designated with β, δ and ω and can be converted into one another. These phases occur either in the final product or at certain stages in the manufacturing process

■ on, sometimes alone and sometimes mixed with each other. In general it can be said that the ß-phase by mechanical processing of soaps of ordinary composition with a relatively low moisture content at a suitable temperature, the co-phase by continuous cooling without stirring from the molten state and the <3-phase by high molecular weight, high Water content and low temperatures, such as B. when solidifying glue deposit is favored.
Differences in the crystal structure are expressed in differences in the physical properties of the phases. Ferguson, Rosevear and Stillman (Ind. Eng. Chem., 35, p. 1005 [1943]) give data explaining this for three samples of the same soap, each sample being processed differently to obtain a different crystal phase to obtain. Their results show that soap which is in the / S phase after rolling and kneading is much stronger and more soluble and also foams more easily than a soap which is in one of the other two phases mentioned above. It also differs in its greater tendency to swell when soaked in water. During rolling and kneading, the authors mentioned received the /? Phase under conditions which brought about an orientation and a compression of the crystals. If the conditions for achieving the /? Phase are such that the crystals are not compressed, connected to one another or oriented parallel (e.g. when quenching and mechanically working the semi-molten, viscous soap), the soap foams less easily , Optical irregularities appear, the transparency and characteristic properties of the waxy, pied soaps are lost, and the bars are easily disintegrated in water and are generally much softer.

The different crystalline phases of the soap can be identified by their characteristic X-ray diffraction rings, that for a given phase even if the composition of the fat component, the water or the electrolyte content changes remain practically the same, be distinguished from one another and identified, although the named Changes can determine the phase that is forming. A simple identification system is based on the characteristic short grid spacings shown in Table I, taken from the above-referenced work by Ferguson, Rosevear, and Stillman.

Table I.

Used for identification
X-ray diffraction rings

ß
δ

Ring diameter

6.35

6.05 and 4.65

5.85

Grid spacing
d / n ° A

2.75

2.85 and 3.55

2.95

The identification rings for the α-phase have been omitted, as this phase is rarely found in a commercially available one Soap was found. no

Not only is the presence or absence of a phase indicated by the presence or absence of its corresponding one Identification ring or their rings displayed. The relative proportions of the in two or more coexistent phases present in the soap can be obtained from an unknown sample relative intensity of the identification rings can be estimated. If z. B. the ω-phase progressing is converted into the / 9 phase, the relative Intensity of the 5.85 cm ring decreases and the relative intensity of the 6.35 cm ring increases. To such estimates with a certain. To perform degree of accuracy, known mixtures are first used of the phases, each as pure as possible, tested as "standard samples" and the relative intensity

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sities of the characteristic rings noted. The relative intensities of the rings of the diffraction patterns of the unknown sample are then compared with these standard samples. For example, a mixture of the β and ω phases that gives approximately equal intensities of the 6.35 cm and 5.85 cm rings actually contains about 75 % of the β and 2 ^% of the ω phase. A soap containing predominantly the / J phase but less than 5% of the ω phase clearly shows the / J ring, while the ω ring can hardly be perceived. On the other hand, in order to obtain perceptible /? - rings in a soap consisting predominantly of the ω-phase, about 15 or 20% /? - soap must be added. A progressive transformation of one phase into another is expressed in a progressive change in certain physical properties, as shown in Table II. Here a soap kernel or cake was made from 80% tallow and 20% coconut oil in a soap boiler. It was dried to a water content of ⁰ Zo 1S, whereupon the resulting particles were in the ω-phase. A progressive conversion to the / S-phase through an increasing degree of working and compaction was achieved by squeezing equal parts of the above soap several times at room temperature and under pressure through a slit-shaped mouthpiece, so that soap bars were obtained: The strength of these bars or their breaking strength was determined with a Mullen tester (a device used in papermaking for strength testing). The rate of wear of the bars was determined by mechanical treatment using a rotating brush under running water.

Table II

Phase composition X-ray analysis) Wear and tear (Strength number of (determined by speed Mullen) Squeezes % <». (rotating brush) kg / cm ² . ⁰ U ß 85 (Arbitrary units) 2.0 ■ ■ 1 ² 15th ■ 70 2.2 3, i 12th 30th 30th 3.5 4.8 24 70 0 4.6 6.4 8O IOO 0 5.2 7, o TOO 100 5.4

Although the mechanical working and pressure treatment according to the invention convert the soaps with high moisture and electrolyte content under consideration predominantly to the /? Phase and although the presence of these soaps mainly in this phase is essential for them to have the properties pilierter have soap in signifier dimensions means of course is not that a mechanical machining any soap necessarily the same ^one as in the / - converts phase?. For example, a soap containing only 6 to 7% water and predominantly in the /? Phase was converted to the ω-phase under suitable extrusion conditions, whereby the strength, the wear rate, the foaming ability etc. decreased. On the other hand, a bar which is present in the /? Phase and has solidified in a form and has a high moisture content in the absence of added electrolyte can be converted into a soft cS bar by pressing or kneading. In addition, mechanical processing as such does not noticeably increase the foaming capacity of a soap present in the ω-phase. An improvement can only be achieved if such processing results in a conversion to the /? Phase. However, this depends on the composition of the soap as well as on the temperature, the duration and the degree of processing and compaction.

Basics for the egg sequence of the. Soaps, among the piled ones. Soap.

As emphasized above, in order to obtain the properties of pyrolized soap it is essential that a part of the soap is present in the /? - Ph, ase. Although in some cases commercial piled soaps have so far contained less than 50% of the /? Phase, probably as a result of incomplete piling, about 50% or more of the soap according to the invention must be present in the / J phase for the soap has the properties of piled soaps to the desired extent and can be clearly identified as piled soap. The typical strength, transparency, gloss, waxiness, reversible swelling in water, etc., which are peculiar to pied soaps, can, however, also be lacking in a soap that is predominantly in the /? Phase, for example one according to the USA. -Patentschrift 2 29s 594 soap produced largely in the, (S-phase, but despite its high foaming capacity and its high, /? - content does not have the properties of pearled soap. In this process, melted soap is rapidly cooled while stirring while it is still in a doughy, tough state. The product obtained according to this process is softer and more opaque than a mushroomed soap.
In some cases, the soaps according to the invention can only be difficult with regard to the properties

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ρiüerter soap exactly with other methods Manufactured soaps of the same composition can be compared, as in some cases; impossible is, according to other processes, coherent, homogeneous bars with a high moisture and produce salinity. From certain Other compositions with high moisture and salt content can be made by other methods (e.g. by solidifying in a mold

ίο or according to the "USA.-Patent 2 377 424) related, homogeneous bars can be obtained, but these lack the properties of more pure Soap, like shine, transparency, firmness! and reversible swelling in water. In case of Compositions, with a high moisture and salt content, which according to other than that according to the invention Processes that can be shaped into bars is shown by a direct comparison of those produced in this way Bars with the Rie according to the invention?

2 eyes in terms of gloss, transparency, strength and reversible swelling capacity in. Water the effectiveness of the cross-squeezing according to the invention and pressure treatment to achieve pearled soap properties.

^a 5 The method described in US Pat. No. 2,295,594 is suitable for determining the transparency, the opacity being measured instead of the transparency for the sake of simplicity. The method is carried out in such a way that a slice about 1.5 mm thick is cut from the soap and the amount of light reflected under standard exposure conditions is measured with a reflectometer, a) when the disk is on a black background, and b) when it is on a white background. The first reading, multiplied by 100 and divided by the second reading, is called the opacity value of the soap and is the reciprocal of the transparency. In the example cited in the above patent, the product obtained there has an opacity value of 89 compared with that of. 70 for the same pied soap, despite the fact that an X-ray diffraction diagram showed that both soap samples had the same /? Content. Opacity values as low as 27 have been obtained in accordance with the invention, with values usually being between this general range and the range of about 70 given in the above patent for a low moisture and low electrolyte pearled soap.

The firmness of soap bars can be easily achieved with a Mullen test device can be measured.

By way of illustration, Table III shows opacity and strength values of two samples of the same soap (So ⁰ / »tallow, 20% coconut oil) with one sample solidified in a mold (ie, the sample was let through, slowly cooling from the molten state without stirring solidify) and the other sample had been squeezed out until it possessed the properties of piled soap to a noticeable extent.

Table IH

solidified

% NaCl 3.2-3.2

% H ₂ 0 ........; 27.2 25.6

Strength (Mullen),,

kg / cm ² 0.63 1.05.

Opacity,% ..... 85.4 55.2

To determine the speed of solution, a. Bars of the soap in question evenly rubbed with a wet sponge and determine the amount of soap rubbed off with each stroke ' will. In the same way one can measure the ease of foaming by measuring the The number of rubs with a wet sponge is one that is necessary to maintain the soap concentration in a given, volume of water of certain hardness to increase to the point, at which can form stable soapy water,

Investigations of the behavior of the liquid present in the soaps during freezing and melting show useful correlations with the properties of piled soap. If an opaque, non-pied soap, regardless of whether it is originally in the ω-, <5 or ß- phase, is subjected to shear forces and high pressure so that properties of pied soap are produced, the state changes at least part of the liquid present in the system. This change is interpreted in such a way that the liquid, which is present at normal temperatures as an isotropic, dilute soap solution, is brought into a more intimate connection with the existing solid soap crystals through mechanical processing and compression , is "bound" more closely to it. The vapor pressure of the liquid is lowered, and its behavior when it solidifies changes. The foregoing changes can most easily be sensed and followed by dilatometric measurements, which show the volume changes that occur as such systems are gradually warmed up. The soap is first made by, placing, in a bath of alcohol and. Dry ice, frozen with, a temperature of approximately -70 ⁰ C, the phase of the soap crystals is not affected by this treatment. X-ray diffraction diagrams of such frozen systems show not only those characteristic of the soap phase, but also those characteristic of ice. Rings indicating that water in the system is frozen. As the frozen system gradually warms up, an almost linear expansion is observed (due to the expansion of both the ice and the soap crystals), which gradually gives way to a resulting contraction as the ice melts. After melting has ended (which is accompanied by the disappearance of the X-ray diffraction lines characteristic of ice), a kink suddenly appears in the dilatometric curve, which at

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a further rise in temperature of, a resumption of linear expansion Reason of the expansion of the now side by side. lying soap solution and soap crystals followed is. The sharp kink in the curve as a result of the change in sign of the volume change denotes the disappearance of the last sense of. Ice cream. The temperature at which this occurs will be the Called "dew point".

ίο In solid soaps that contain more than about 40% water, the dew point approaches the freezing point of water. With decreasing water content, however, the dew point also decreases, and the deviation from 0 ° C becomes easily measurable. A mere transformation of one phase into the other, such as e.g. B. from the ω phase to the opaque / f phase is not accompanied by a change in the dew point. The pressure and cross-squeezing treatment according to the invention, on the basis of which the properties

Ao pied soap achieved, however, causes a slight noticeable, lowering of the dew point. The amount of this change shows the effectiveness of the Treatment.

The crystals of piled soaps are predominantly oriented in the direction of pressing, as if microscopically can be shown with polarized light. One examines one between crossed Nicolae, Thin soap bar arranged in prisms (the broad surfaces of which are essentially parallel to the Squeezing direction are), with the soap cut, only in the position of maximum light extinction brought and then rotated 45 ° from this position will.

The increase in light transmission in the second position shows the orientation of the Particles, the sample and distinguishes piled and squeezed soaps from solidified in a mold Soap.

Methods for measuring certain properties of fused soap have been described above. Other such properties that are less easily measured quantitatively are: One uniform: structure, a smooth, waxy handle, gloss, the inclination when introducing, in

+5 water to. swell, but after drying in essential to regain its original shape and appearance, and the absence of, warpage, in aging. These are properties when comparing the product according to the invention with froze. Soaps of the same composition are easily identifiable.

Most, observations used as criteria for presence or absence Characteristic properties of pearled soap can apply, can, easier to use soap in. Bar form than made on soap in flakes or in some other comminuted form. Meanwhile can comparisons of the speed of dissolution, the transparency and the firmness also with soap flakes, and x-ray examinations to determine the phase as well dilatoinetric series of measurements to determine the dew point are independent of the shape of the Soap. The. Invention primarily relates to soap, with the properties of pearled soap, which, however, can be found in special shape, such as B. flakes, grains, powder, larger pieces, threads, etc., do just as well as can be found in the bar shape customary for piled soap.

Electrolyte and water content of the compositions according to the invention

In contrast to the, previous, processes in which, soaps made less than about 20% Water and less than about 1% sodium chloride containing. Soaps are made, one gets according to the invention, soaps made from mushrooms with up to 35 or 40% water and a high salt content. the The essential point of the invention lies in the relationship between water, salt and soap content. The invention is therefore based on the possible ratio range of the above. Components, within 'which, pied soaps can be made according to the invention. If with one high water content the salt content is too low, the result is usually a soft, opaque one Soap in the cS phase, which swells only slightly and, when it is placed in water, cracks appear that do not dissolve easily and hardly foam Soap is difficult to rub off the damp bar. If on the other hand the salinity is too high, the result is an opaque "bar that shrinks slightly when soaked absorbs little water or hardly swells, is not easily soluble, is, foams poorly and usually, is predominantly in the ω-phase. The limit levels of salt and water in soaps, according to of the invention can be converted into a mushroom type of soap are discussed in more detail below discussed.

Adjustment of the salt and water content of the soaps according to the invention to a suitable ratio and mechanical processing and compression of the system thus set for conversion into the / 5 phase are not sufficient on their own to achieve a pearled soap. The temperature must also be kept in an optimal range. It has been shown that the invention is difficult below about 27 ⁰ C or above about. 52 ° C is feasible. These are the approximate limits within which soaps can be produced with the plastic, solid consistency which allows piling, kneading, pressing and similar treatments using shear forces. If the soap is too hard during mechanical processing, the pressure will not compress it into a coherent mass. If it is too soft (e.g. if it is flexible or if the shape can be influenced by the action of gravity or by light pressure), the end product lacks important properties of pied soap, e.g. Transparency, gloss, waxiness, an essential orientation of the particles or crystals: in one direction, strength and

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a noticeable ability when soaked in water: to soak up the same. The boundary peratures as well the optimal temperature depend in each individual case on the salt and water content as well on the composition of the fat component of the soap. Usually the one to achieve a ρ liaten, soap with high moisture content, the higher the higher the required temperature The fatty acid titer of the soap is.

ίο In the compositions according to the invention, the sodium chloride can be replaced by a corresponding amount of any other soap-compatible sodium salt. "Soap-compatible" salt is to be understood as meaning one which does not convert the soap into fatty acid or an acidic soap. Sodium acid sulfate and primary sodium orthophosphate are examples of salts that are incompatible with soap, while soap-compatible salts include: sodium chloride, sodium carbonate, tertiary sodium orthophosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, borax and the various types of commercially available SiO _{2, sodium silicate} Na ₂ O is between about 2: 1 and about 4: 1. Many of these soap-compatible sodium salts are widely used as soap fillers, which facilitate water softening, increase leaching action and detergency, or have other beneficial properties. It is therefore an object of the invention to provide filled soaps which to a significant extent have the typical properties of pied soaps. ,

These soap-compatible salts make a difference! It has the ability to salt out melted soap in the kettle, which in turn does so required absolute. Quantities for different salts and different soaps are different. The amounts, however, of each salt are in proportion to one another, regardless of the particular one used Soap, practically the same. In much the same way, these salts affect those Properties of plastic solid soaps, with a high moisture content, which are responsible for this are whether the properties of piled soap are imparted by cross-squeezing and pressure treatment of the soap be, may or not,

To carry out the invention with. As a rule, it is soaps containing 20 to 40 per cent of water necessary to set the salinity to about. 1 to 12 percent by weight to adjust. The rest is essentially soap. Possess the various salts a different effectiveness in relation to the Properties of piled soap. For each there is a certain range of ratios of salt to soap to Water, within which, through cross-squeezing and pressure, the properties of pied soap are obtained can be. These areas can be shown through graphs in which the salinity as the ordinate against the Water content is plotted as the abscissa. By subtracting the sum of the salt and water content 100% results in the approximate percentage of pure soap, the even smaller corrections of fractions of percent for glycerine, unsortable materials, carbonate alkali, etc., whatever else may be contained in the soap is needed.

Figures i, 2, 3, 4 and 5 are such graphs for five common salts, namely sodium chloride, pentasodium tripolyphosphate, tetrasodium pyrophosphate, tertiary sodium orthophosphate and sodium silicate. 5 can be used quite generally for sodium silicates ¹ in which the ratio of SiO ₂ to Na ₂ O is between ~ 2.5: 1 and about 3.5: ι. In each of the graphic representations, an area A can be seen, within which the scope of the invention lies. In the case of higher salt or water contents, the invention can only be carried out with difficulty or not at all, since. the products obtained by the transverse squeezing and the pressure treatment lack the characteristic properties of pied soap. The use of the graph is explained below with reference to FIG. If a pearled soap is to be made with a moisture content of, for example, 35%, the salt content should be set to 1.6 to 4.35%.

These graphs are intended as a guide serve for the treatment of the typical soap according to the invention, with the optimal values easily judged in each individual case according to the above-mentioned properties of the products can be. Generally speaking, for any, moisture levels are in accordance with the invention the appropriate salinity levels on and close to a straight line coming from the origin (20% moisture, ι ° / V salt) leads to the diagonally opposite corner of the surface, salinity levels that continue away from this line should be with a some caution should be exercised

Suitable fat starting products for the
soaps of the invention

Although reference has been made above to a sodium soap made from 80% tallow and 20% coconut oil and a high moisture bar with particularly beneficial properties is obtained with this composition, compositions of about 70 to 85% tallow and about 15 to 30% are also suitable. Coconut oil is well suited for such soap bars. These soaps are expediently pressed out or piled at about 38 to 52 ⁰¹ C and, if they are mechanically processed and compacted at these temperatures, can mainly be converted into the / 3 phase (ie more than 50%, as by X-ray analysis was determined), and you can achieve the typical properties of pearled soap. With increasing amounts of coconut oil, about one third of the fat composition is es- ¹ increasingly difficult ^ mononitrogen convert the soap in a soap-milled ,, although still compositions may be used with up to 50% coconut oil. When the percentage of coconut oil in the starting fat

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The soaps so obtained are far above 50% in many cases no longer predominantly in the /? phase or no longer have the described ones Properties of piled soap.

Coconut oil is mentioned in the specification as a specific example, but the same considerations generally apply to other oils of the coconut oil group. Under oils, the coconut oil group, all vegetable seed oils or fats are to be understood, in which at least 50 percent by weight of the total fatty acids, from lauric. and / or myristic acid. These oils (many examples of which are given in Hilditch's The Chemical Constitution of Naturel Fats, 2nd Edition [1947], pp. 198 to 205) are usually obtained from the seeds of members of the botanical families, the Lauraceae ( e.g. Tangkallakkernöl), the Myristiceen (e.g. Ucuhubanusöl), the Vochysiaeeen (e.g. Jabotykernöl), the Salvadaraceen (e.g. Khakankernöl), the Simarubacen (e.g. Dikanussöl) and especially the family won the palm trees. Coconut oil is the best example of an oil extracted from the seed of a member of the Paiknen family. However, other non-limiting examples of such oils include murumuru oil. Tucuma oil, cohune oil, urikury oil, babassu oil and palm kernel oil.

, The factor responsible for determining whether a particular fat makes a soap that is light predominantly can be converted into the /? phase and has the typical properties of pearled soap, is not the special origin of the fat, but rather the composition of the totality of the fatty acids it contains. While it is thus possible to practice the invention with soaps which are greater than 50 percent by weight of starting blends containing oils of the coconut oil group in general there are difficulties in carrying out the invention, if more than about 40 percent by weight of the fatty acids of the .Seife saturated fatty acids with less than 16 carbon atoms were. Sebum, soft fats and palm oil are examples of fats which either alone or in a mixture with one another or with coconut oil for the preparation of the invention Soap can be used. Highly unsaturated vegetable or fish oils are partially hydrogenated if they are to be used in substantial quantities in the starting fat product, since, without hydrogenation, the soap obtained from them is too soft for the treatment according to the invention. However, they can also be mixed in limited quantities with other more saturated fats

will. As a rule, the soap suitable for carrying out the invention should be made from fats with a Iodine number over 25 can be obtained, which does not contain more than 40% saturated fatty acids with less than 16 carbon atoms and at least 20 percent by weight Contain saturated fatty acids with 16 to 22 carbon atoms.

As with the production of the usual pearled soaps, according to the invention, too, is a limited one Replacement of sodium by potassium as a cation in soap is permissible as long as this replacement is not so is largely that this gives the product the characteristic properties of pearled soap get lost. In the same way, some of the sodium salts can be replaced by potassium salts. The same considerations apply to other soap-forming cations, e.g. B. for the ammonium ion or substituted ammonium ions (e.g. triethanolamine soaps).

Examples

The following examples explain the process according to the invention and the cleaning agents produced therefrom. In the examples, the transverse squeezing and the pressure were achieved by pressing, to be precise during the same. With this type of treatment, the temperature, the moisture content and the pressure can be regulated and measured more precisely within the given possibilities. Of course, other means of applying shear forces under pressure are also possible, such as, for. B. Pilieren and kneading. Unless otherwise stated, in the examples the extrusion took place through a narrow, cylindrical mouthpiece which led from a _{chamber filled with soap q 0} into another chamber, one wall of each chamber being movable and consisting of the surface of a hydraulic piston. The two pistons moved synchronously, but the pressure on each piston was regulated independently. The soap is therefore pressed out of one chamber under high pressure into another chamber with a lower pressure which, however, is sufficient to form the soap into a coherent bar which can then be embossed in the usual way. If such a soap is heated to melt and is then allowed to solidify by cooling to room temperature without stirring, it is called a "solidified soap". ■

example 1

Using the usual settling boiling process, soap became a starting material made of the following composition:

23.0 coconut oil

20.0% fish oil, hydrogenated to an iodine number of 70 22.8% tallow 1 The mixture was ^L1 5

28.5% pork fat \ to an iodine number of
5.7% palm oil j 49 hydrogenated.

To the molten boiler soap, which contained 0.4% sodium chloride and about 30% water, sodium chloride was added in a mixer so that the salt content was 2.75%. The hot mixture was allowed to cool to room temperature and solidify. Then the Mix twenty-four times through a slot-shaped mouthpiece with a diameter of 37.50 - 0.78 mm.

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knife pressed from one chamber to another and back. The pressure on the high pressure side of the mouthpiece was between 40.6 and 44.8 kg / cm ² and on the low pressure side 14.7 kg / cm ² . The chambers, the plunger surface, the sides of the mouthpiece and the soap were kept at a temperature of 43.5 ° C by a water cooling jacket. The obtained soap bar, formed under pressure in the extrusion chamber, was smooth, firm, homogeneous, waxy and transparent. It foamed readily on the hands, swelled considerably when placed in water, but returned to essentially its original shape and appearance after drying. Its breaking strength, measured with the Mullen tester, was 2.03 kg / cm ² . An X-ray analysis showed that it was in the /? Form, while a corresponding solidified sample consisted of about 50% of the β and about 50% of the co phase. The pressed bar was mechanically tested for its wear rate and its foaming capacity by subjecting it to the mechanical action of a motor-driven brush and a stream of water under controlled conditions, whereupon the foam formed by this treatment was contained for a certain time Certain amount of soap. This amount was one and a half times that of another bar of the same soap, which contained 2.75% NaCl and had been poured into a mold while molten and allowed to slowly cool to room temperature without stirring. The amount was 92.5% greater than the amount obtained in a parallel test with a commercially available pearled, kneaded and embossed soap of the same fat composition, where "with this soap 14 ⁰ A) water,

- 0.38% VoNaCl, 0.12% Na ₂ CO ₃ - and 0.2% sodium silicate.

Example 2

Another sample of the molten boiler soap from Example 1 was partially dried and adjusted in a mixer to a sodium chloride content of 1.5% and a water content of 22.2%. This soap was cooled in a mold and then extruded under the same conditions as in Example 1 except that the pressure on the hollow pressure side was 47.25 to 58.8 kg / cm ² and on the lower pressure side Was 13.16 kg / cm ² . The soap bar obtained was more waxy and more transparent than that of Example 1 and also held together more firmly (Mullent test 4.8 kg / cm ² ). It was in the / J phase, while the corresponding, only frozen bar was in the ω phase. The rate of wear was 220% greater than that of the commercially available piled bar. The pressed bar possessed the properties of pil.ierter soap such. B. swells in water without cracking or disintegration and, when dry, essentially returned to its original shape and appearance.

Example 3

A mixture of 80 ^fl / o tallow and soft fat mixed and 20% coconut oil was saponified with caustic soda according to the usual settling boiling process. The fat mixture had an iodine number of 47.5, a saponification number of 23.4 and a titer of 38. Salt and water were added to the molten soap in a mixer so that the mixture was 32.4% water and 3.8% % Sodium chloride. They were allowed to solidify in a mold and then pressed them forty times at 32 to 38 ⁰ C by 122 round mouth pieces having a diameter of 0.8 mm. The soap bar obtained was smooth, homogeneous, transparent, looked waxy, foamed heavily, was firm and was in the /? Phase.

Example 4

Another sample of the kettle soap from Example 3 was partially dried and then adjusted to 26.4% HpO and 3.8% NaCl in the mixer. It was then treated as in Example 3, with the exception that it was pressed out at 54 ° C., a pressure of 875 kg / cm ² and through a single mouthpiece with a diameter of 0.8 mm. The soap bar obtained was similar to that of Example 3 in that it was in the /? Phase and possessed similar properties of pearled soap.

Example 5

Made from 80% a mixture of tallow and an inedible pork fat and 20% coconut oil a soap was made by standard boiling with settling. The mixed ones Starting fats for the soap had an iodine number of 42.6, a saponification number of 213.2 and a titer of 38.7. Salt was added to the melted soap in a mixer so that that the water content of the mixture was 29.5% and the NaCl content was 1.6%. After bringing in The soap was put into a mold and cooled forty times at 29.5 to 35 ° C through 122 mouthpieces with a diameter of 0.8 mm pressed out.

A transparent soap bar was obtained which was smooth and waxy to the touch and looked solid was and foamed heavily, was in the /? phase and was clearly a piled soap.

Example 6

According to the usual boiling process, a mixture of tallow became inedible pork fat and coconut oil made a soap. The starting mixed fats had an iodine value of 41.4, a saponification number of 213.8 and a titre of 39.3. The melted soap was in a mixing device set to a water content of 3i, 2% and a salt content of 2.43%. They were solidified in a mold and pressed

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they then about forty times at 27 to 32 ⁰ C and a pressure of about 875 kg / cm ² through a mouthpiece of 0.8 mm diameter. The soap obtained was in the /? Phase and possessed the properties characteristic of pearled soap, such as transparency, strength; strong foaming capacity, easy solubility in water, water binding capacity, etc.

Example 7
10

Tallow kettle soap was mixed with water and tertiary sodium orthophosphate in the mixer, whereupon the mixture was allowed to cool and solidify _{to a final content of 33.5% water, 7.5% Na 3} PO _{4 and 0.58% NaCl.} It was then pressed forty times mm at 27 ⁰ C under a forward pressure of 105 kg / cm ² and a pressure at Zurückpressen- of 5.25 kg / cm ² through a die having a diameter of 0.4. The bar obtained was smooth, homogeneous, firm, transparent and easily soluble in water and was in the / 3 phase.

, Example 8

Tallow soap produced according to the usual boiling process was mixed in a mixer with commercially available nitrium silicate with an Si O ₂ : Na ₂ O ratio of 2.58: 1. This mixture was solidified by rapid cooling with little exudation of liquid and the solid soap was then pressed forty times through a mouthpiece with a diameter of 0.4 mm ^{at 27 ° C. to form a bar.} The forward pressure was 17.6 kg / cm ² and the back pressure in the chamber in which the soap bar was molded was 7 kg / cm ² . The bar obtained contained 8.5% solid silicate, 0.43% NaCl and 36.2VoH ₂ O, was in the /? Phase and had the characteristic

. see properties of piled soap.

Example 9

The kettle soap from Example 8 was in the mixer with tetrasodium pyrophosphate, mixed more sodium chloride and water.

This mixture was rapidly solidified by cooling, whereby only a little liquid separated out, and was then ^{pressed out forty times at 44 °} C. through a mouthpiece 0.4 mm in diameter, the forward ^{pressure 7.35 kg / cm 2} and the reverse pressure Was 0.7 kg / cm ² . The bar obtained contained 10% Na ₄ P ₂ O ₇ , 3.48% NaCl and 37.2% H ₂ O. It was in the /? Phase and had the characteristic properties of puffed soap.

Example 10

Another sample of the kettle soap from Example 1 was heat dried and then _{mixed with tetrasodium pyrophosphate and water to a final composition of 5% Na 4} P ₂ O ₇ , 0.48% NaCl and 22.2% H ₂ O in a blender . The mixture was then allowed to solidify in a mold and pressed to forty times out at a temperature of 47 ⁰ C by a slit-shaped nozzle, wherein the pressure on the side of the high pressure from 34.3 to 44.8 kg / cm ² and at the side of the low pressure was 8.5 kg / cm ² . The bar obtained had the typical properties of pied soap.

Example 11

Another amount of the melted kettle soap from Example 1 was mixed in a blender with pentasodium tripolyphosphate to form a composition containing ^{5% tripolyphosphate and 27.2 fl} / o H _{2 O.} This was cooled and poured into a mold until solidification vieründzwanzigmal then pressed at 38 ⁰ C by a slit-shaped mouth piece, namely at a high pressure from 39.6 to 42.3 kg / cm ² and a lower pressure of 10 kg / cm ² . The soap bar obtained was in the / J phase. It was transparent, firm (Mullen breaking strength test 3.2 kg / cm ² ), waxy, etc., so that a typical pearled soap resulted.

Example 12

This example corresponds to Example 11 except that the final composition is 10%> Sodium tripolyphosphate and 28.4% water. The soap obtained at the end was in the /? - phase and had the characteristic properties described in Example 11 pearled soap, although it was a little softer than the soap from example 11.

In the above examples, one can also advantageously replace the repeated description Put a piling and kneading treatment into the pressing process. However, it aims to provide adequate editing the soap and ensure that there is not too great a loss of moisture.

Claims (10)

PATENT CLAIMS: i. Process for the production of pied soaps with a high water and salt content from a mixture of soap, water and a soap-compatible sodium salt as electrolyte, the soap being waxy and translucent and predominantly in the /? Phase, characterized in that the salt content is one in any Sodium soap obtained in a manner whose fat content is a fatty oil with an iodine number of over 25 and which has at least 20% saturated fatty acids with 16 to 22 carbon atoms and not more than 40% saturated fatty acids with less than 16 carbon atoms, to 1 to 12 percent by weight and the water content to 20 to 40 percent by weight, a higher salt content being set at a higher water content and a lower salt content being set at a lower water content, and that this mixture is in the plastic solid state at a temperature between about 27 and about 52 ⁰ C, namely below the solidification temperature and below the temperature at w elcher clear soap in stable 609 527/513 P 7424 IVa / 23 e Equilibrium can exist in the system, but above the temperature at which the soap becomes brittle under the pressure of a kneading and compacting treatment and shear forces suspends. 2. The method according to claim i, characterized in that the sodium salt sodium chloride), Tetranatpiumpyrophosphat, tertiary sodium orthophosphate, pentasodium tripolyphosphate, Natri.umsilikat with a Si O ₂ -: Na ₂ O ratio of 2: ι to 4: 1 and expediently 2, 5: 1 to 3.5: 1 or mixtures thereof; be used. 3. The method according to claim 1, characterized in that that when using sodium chloride the appropriate amounts of salt and water lie within an area, which in a two-component diagram by straight-line Combination of 1 ° / o salt and 20 ° / o Water, 4% salt and 20% water, 4.5% salt and 40% water and 1% salt and 34% water corresponding points are formed (Fig. I). 4. The method according to claim 1, characterized in that that when using tetrasodium pyrophosphate the corresponding Salt and water amounts are within an area, which is shown in a two-component diagram the straight line connection of 1% salt and 20%> Water, 8 per cent salt and 20 per cent water, 8.5 per cent salt and 27.5 per cent water and ι% / o salt and 31% water corresponding points are formed (Fig. 2). 5. The method according to claim 1, characterized in that that when using pentasodium tripolyphosphate, the corresponding Salt and water amounts are within the area of a two-component diagram, which through straight connection of 1% salt and 20% water, 10% salt and 20% water, 12% salt and 28% water and 1% »salt and Points corresponding to 31.5% water are formed (Fig. 3). 6. The method according to claim i, characterized in that that when using trisodium orthophosphate the corresponding amounts of salt and water within the area of a two-component diagram, which by connecting the 1% salt in a straight line and 20% water, 10% salt and 20% water, 10.5% salt and 36% water and 1 ° A> Salt and 31.5% water resulting in dots (Fig. 4). 7. The method according to claim 1, characterized in that that when using sodium silicate the corresponding salt and water contents are within the area of a two-component diagram lie, which by straight connection of 1% salt and 20% water, 11% salt and 20% water, 12% salt and 40% water and 1% salt and 35% water corresponding points are formed becomes (Fig. 5). 8. The method according to claim 1, characterized in that that the mechanical treatment of the mixture is carried out at a temperature at which the mixture is plastically solid and im consists essentially of solid soap crystals and glue deposits or soap glue. 9. The method according to claim 1 and 2 and 8, characterized in that the mechanical treatment of the mixture at a temperature between about 27 and 52 ⁰ C is carried out. 10. The method according to claim 1 to 3 and 8, characterized in that the soap consists of a mixture of about 15 to 30% coconut oil and made up to 70% · tallow about 85 and that the mechanical treatment of the mixture between about 37 and 52 ⁰ C. is carried out. 80 Referred publications:
Hefter-Schönfeld, Chemistry and Technology der Fette und Fettprodukte, Vol. IV, pp. 208, 209, 365, 246, 247; Ubbelohder Handbook of Oils and Fats, Vol. 3, Dept. 2, p. 638. 1 sheet of drawings © 609 '527/513 5. 56