DE2623744A1 - HYDROPHOBIC STARCH PRODUCT, PROCESS FOR ITS MANUFACTURING AND MIXTURES CONTAINING THE STARCH PRODUCT - Google Patents

Description

HULLER-BORE GROENING DEOTEL SCHÖN HERTEL

PATEJiTAX RULE

CPC International Inc. International Plaza

Englewood Cliffs, Hew Jersey 07632

UNITED STATES.

2 MAY 6, 1976

DR. WOLFGANG MÜLLER-BORE (PATENT ADVOCATE FROM 1927 - 197S) HANS W. GROENING. DIPL.-1NG. DR. PAUL DEUFEL. DIPL.-CHEM. DR. ALFRED SCHÖN, DIPL.-CHEM. WERNER HERTEL. DIPL.-PHYS.

C 2959

"Hydrophobic starch product, process for its manufacture and mixtures containing the starch product "

The invention relates to a mobile or free-flowing, hydrophobic starch product and a process for its production. In particular, the invention relates to a starch product which is used instead of talc in body powders and powder-aerosol mixtures can be used.

There is currently a need for a material that can be used as a basis can be used in body powders. A component of such mixtures that has been widely used up to now has was generally talc. However, talc is being monitored and checked more and more critically by medicine, as it is Contains a potentially carcinogenic substance, namely asbestos. It has been claimed that commercial talc is made from certain Sources can be contaminated with asbestos. Pure mineral talc consists of a group of water-containing ones Magnesium silicates. In contrast to pure talc mineral, it has

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commercial talc, depending on its origin and the method of extraction different compositions. In the description and the claims, the term denotes "Talc" this commercially available talc with a fluctuating composition ·

Recently it was strongly recommended or suggested to use commercially available, native corn starch instead of talc in products such as baby powder. Native corn starch has had limited use in this area for many years. However, unmodified corn starch is not entirely satisfactory for these purposes because as the starch absorbs moisture in use, the starch granules become sticky and adhere to one another. This leads to the fact that the starch causes a slimy, sticky feeling on the skin and forms from the starch "sausages" and "caterpillars ^11. Native corn starch is particularly unsatisfactory for use in aerosol mixtures because it does so tends to settle in the container and the particles or starch granules can agglomerate into agglomerates so large that they clog the aerosol valve.

Attempts have already been made to produce starch-based materials that have the desired properties. For example, it is known to produce a reaction product of starch with a water-soluble soap such as sodium stearate and a water-soluble aluminum salt to thereby obtain a free-flowing, hydrophobic powder (US Pat. No. 2,852 kok).

Furthermore, the production of a water-resistant starch by forming a Werner-type complex of trivalent Chromium has been described with a number of water-soluble organic acids (US Pat. No. 2,359,858). Other hydrophobic Starch-based powders or powders were prepared using a water-soluble inorganic salt (US Pat

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2 6i4 9 ^ 5) »using alkali metal siliconates (U.S. Patents 2,961,339 and 3,071,492) by encapsulation with wax (U.S. Patent 3,740,248), through the formation of formaldehyde-starch condensation products (US patent 2 864 7 ^ 3) »by depositing a hydrophobic film former in combination with an insolubilizing agent (U.S. Patent 3,272,640) and by making various Starch esters (U.S. Patent Nos. 3,281,411 and 2,613,206). A product made by the process of US Pat. No. 2,613,206 has been made under the trademark "Dry-Flo" sold by National Starch Products, Inc.

Also in U.S. Patents 3,377,171 and 3,467 describes the production of free-flowing, dusty starches, which are intended for dusting or flourishing dough during baking are.

However, all of these known starch products are suitable not as a full substitute for talc in powders and similar cosmetic-medicinal products. The invention lay therefore the underlying task is to provide a starch product to provide a full substitute for health in the application fields in question Talc is questionable reasons, as well as a process for the production of such starch products create.

This object is achieved according to the invention by a starch product which is characterized in that it is a granular Contains starch material with or from starch material granules, on the surface of which at least one aluminum resinate in one Amount deposited is sufficient to make the coated starch material granules hydrophobic.

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This free flowing, hydrophobic starch product of the present invention is made in accordance with the present invention by treating a slurry of starch with a water soluble rosin material and a water soluble aluminum salt. The resulting product is then dried under controlled conditions to give a free flowing granular product. According to a preferred embodiment of the process of the invention, an aqueous starch slurry is first prepared to which about 0.5 to h parts by weight of a water-dispersible rosin material and about 3 moles of aluminum ions in the form of a water-soluble aluminum salt are added to 100 parts by weight of dry starch substance, and about 3 moles of aluminum ions per mole of rosin material are added, whereupon the pH The value is adjusted to a value in the range from about 4.5 to 5 »5 and the reaction product obtained is dried.

The starch product obtained is a free-flowing, hydrophobic one Starch-based material that can be pulverized into a powder that comes in a variety of different cosmetic mixtures such as body powder, baby powder, shaving powder, powder aerosols, powder-based lotions and others Powder-based mixtures can be used instead of talc.

The only figure of the accompanying drawing (Figure 1) gives represents a typical titration curve obtained by mixing a starch-rosin slurry with an aqueous Solution of an aluminum salt titrated.

In the method of the invention, a reaction product is made from a starch material, a water soluble rosin material and a water-soluble aluminum salt, forming a deposit on the surface of the starch granules separates or precipitates an aluminum resinate. The aluminum resinate is deposited in an amount sufficient to to envelop the starch granules, so that prevents

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is that these can be wetted or moistened, making the starch product obtained in this way hydrophobic and mobile or becomes pourable. The aluminum resinate is created in situ on the starch granules by adding a water soluble rosin material dispersed in an aqueous starch slurry and then a water-soluble one in the reaction medium Aluminum salt dissolves. The mixture is then filtered, whereupon the filter cake is kept at room temperature or under moderate conditions Allowing heating to dry, thereby producing the starch product of the invention receives.

All types of starch are suitable as starting material for the purposes of the invention. For example, both grain and as well as tuber starches such as corn, milo, wheat, rice, maranta, potato, tapioca, wax corn and waxy milk starch etc. A modified starch material can also be used as the starch starting material. Suitable modified Starch materials include cationic starches, oxidized starches, hydroxyalkyl starches, cross-linked starches, Starch esters and starch ethers.

While the type of starch used is not critical, it is essential that a non-gelatinized starch material be used and that the starch material retain its granular shape during all operations. As is well known, native starch is in the form of granules that exhibit birefringence when viewed under a polarizing microscope. When starch granules are heated in the presence of water, they swell considerably and lose their characteristic birefringence. This process is known as gelatinization or gelatinization. The gelatinization temperature is the temperature above which the starch granules gelatinize in water. Thus, during the process of the invention, the temperature of the starch slurry must be kept below the gelatinization temperature of the particular starch material or modified starch material used. _{6O9851 / 1O} 6

An aqueous starch slurry is made by the starch suspended in an appropriate amount of water. The amount of water is not critical, but is preferably used enough water to make the slurry easy to handle in conventional mixing equipment. It was found that it is appropriate to use starch slurries whose content of starch (HB), i.e. starch with a Water content of about 12 ^, ranging from about 5 to 40 wt. It should be noted that the amount of Strength in the slurry the properties of the hydrophobic Product does not affect or affect, but only in terms of the ease with which the slurry is can handle is important.

Then the rosin material becomes the starch material slurry incorporated. The rosin material can be added directly to the slurry or, for convenience, initially added to the slurry a small amount of water and the starch material- slurry can then be added in the form of this predispersion.

The rosin material useful for the purposes of the invention must be water dispersible or water soluble. The foregoing Terms are used interchangeably in the description and the claims and each mean that a high percentage, i.e. at least about 75% by weight based on Dry matter, the rosin material must be soluble in water. As the rosin material, tall oil, gum or Wood rosins can be used. Generally, a significant portion of the water-dispersible rosins reside or rosin materials in the form of alkali metal salts of the various acids of rosin. These acids will referred to as resin acids. Such substances or materials are generally referred to as rosin or resin glue (rosin sizesX They are readily available substances that are widely used in the paper industry. Of the Resin glue can be in any conventional form, e.g. as a dry powder, paste or emulsion, and can be

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substantial amounts of free resin acids, as well as fatty acids and neutral ones Contain substances that are often found in commercially available resin glue products.

As "resinates" in the description and claims, the salts of resin acids referred · Thus, the term "NatriumresinatJ ¹ to the sodium salts of the respective resin acid mixture and" aluminum resinate "on the aluminum salts of these acids.

The resin acids present in rosin and rosin glue are generally diterpenoid monocarboxylic acid derivatives more allylated Hydrophenanthrenes. A distinction can be made between two basic types, namely the abietic acid type and the following has a typical structural formula,

COOH

and the pimaric acid type with the following typical structure:

CH = CH _n

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There are a number of isomers of each of these two structure types. Turpentine resins are usually obtained from three sources, namely oleoresin from living conifers or pines, so-called gum rosin, by extraction aged or seasoned softwood sticks, so-called wood turpentine resin and as a by-product of alkaline pulping or cellulose production process, so-called tall oil rosin. These contain raw rosins besides a mixture of resin acids, some fatty acids and a small amount (about 10 9 ^) of a neutral material which is different Esters of resin and fatty acids, sterols, hydrocarbons, ketones and alcohols included, of which so far many have not yet been further identified.

Gum rosin and wood rosin generally contain from about 90 ° / o resin acids and about 10 "fo neutral substances. Crude tall oil rosin also contains considerable amounts of fatty acids, of which a great percentage is usually removed by fractional distillation. The ratio of the percentages, in which the different resin acids are present in the rosins is usually the same for the different types of rosins.

Free resin acids, especially those of the abietic acid type, readily succumb, especially when dry the oxidation by air. It is common practice for this oxidation to be the easiest and most rapid on the conjugated Double bonds of the resin acids of the abietic acid type takes place to inhibit or retard by a Diels-Alder Addittonsreaktionsprodukt which produces resin acid with maleic anhydride, fumaric acid or the like. Usually just about half of the resin acids present in such an addition reaction product converted. Turpentine resins treated in this way are called "fortified" or stabilized rosins designated.

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The oxidation of the free resin acids can also be delayed by hydrogenating the rosin. Examples of such Commercially available products are hydrogenated turpentine resins sold under the trademark "Stabelite Resin" by the company Hercules Inc., Wilmington, Delaware, and the sodium salt of hydrogenated wood — rosin sold by by the same company under the trademark "Stabelite Size".

In principle, any type of rosin or rosin glue can be used for the purposes of the invention, however it is preferable to use a reinforced or stabilized rosin glue because it is easier and more convenient to use. An example of a commercially available fortified rosin glue suitable for the purposes of the invention is that from Hercules Ine., Wilmington, Delaware, product sold under the trademark "Pale Fluid Pexol".

The rosin material is incorporated into the starch material slurry mixed in with sufficient agitation to evenly disperse the rosin throughout the slurry. If a rosin resin material that has been previously dissolved in water is used, the required Mixing time should be fairly short, i.e. only up to about 15 minutes. If the rosin material doesn't, however was pre-dissolved in water, it may take half an hour or more for the rosin material to be in the Slurry is dispersed. After adding the rosin material the mixture is stirred to completely mix the components together and prevent them from occurring the strength settles.

The amount of rosin material (dry basis) added should be in the range of about 1.5 to about k, and preferably about 2 to about 2.5 parts per 100 parts of starch material (commercial basis). The use of less rosin

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material as indicated above would have an adverse effect on the hydrophobicity of the final product. The use of excess or more rosin would not adversely affect the end product, but would be a waste of the rosin material. In other words, leads. the use of excess or more rosin does not increase the hydrophobicity of the end product.

Then the slurry becomes a water soluble aluminum salt added. Typical suitable water-soluble aluminum salts include aluminum sulfate, aluminum chloride, aluminum nitrate, Aluminum acetate, potassium aluminum sulfate, sodium aluminum sulfate and the same. These and other water-soluble aluminum salts can be in anhydrous form or in any form of the numerous hydrates used. When using a hydrate it must be the weight of the water present be taken into account when calculating the aluminum ions present.

Sufficient water-soluble aluminum salt should be added to the starch material / rosin slurry that there are present in the slurry for about 2.5 hours ± a about 8 and preferably about 3 to about k moles of aluminum or aluminum ions per mole of rosin, calculated as sodium abietate, where the parts refer to the dry weight. The addition of an amount of aluminum salt within this range results in a hydrophobic product. The amount of aluminum salt to be added can be optimized by titrating the starch material / rosin slurry with an aqueous solution of the aluminum salt. As can be seen from FIG. 1, the initial pH value of the starch material / rosin slurry is about 8. The titration curve shown in FIG. 1 reproduces the titration of wheat starch according to Example 9 below. The titration curve shown is to be understood as a representative example. With everyone in the

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Exercise and the claims mentioned materials are obtained similar curves. The addition of an aqueous aluminum sulfate solution initially leads to a rapid drop in the pH. In this area, area 1, the titration curve is usually linear or straight. After adding a The pH value decreases with a certain amount of aluminum salt solution likewise linearly, but much more slowly (cf. area 2 in FIG. 1). The intersection 3 of lines 1 and 2 indicates the optimal amount of water soluble aluminum salt added to the starch material / rosin slurry must be in order to produce a completely hydrophobic product. This optimal amount of aluminum salt fluctuates somewhat in Depending on the starch used or modified starch, it is usually around 3 moles of aluminum per mole of rosin (calculated as sodium abietate). However, when using derivatized starch materials containing exchangeable hydrogen or metal ions, such as starch phosphate, larger amounts of aluminum ions can be used to be required.

If desired, aluminum salt can be used in excess use above the optimal amounts given above, but this only increases the manufacturing cost without sacrificing the properties of the starch product to a significant extent.

The water-soluble aluminum salt can be the starch material / rosin-based slurry can be added directly in solid form, but it is preferably dissolved in a small amount of water, before adding the starch material / rosin slurry clogging as the aluminum salt is in the slurry disperses faster if it has been pre-dissolved.

The order in which the rosin material and the water soluble Adding aluminum salt to the starch material slurry is not critical. So you can do this

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both additives of the slurry in any order add one after the other or at the same time.

The pH can optionally be adjusted to a value in the range from about 3.5 to about 9.0. The pH of the slurry is not in itself critical and the range mentioned is therefore only suggested to avoid any undesirable To exclude side reactions that can take place under strongly acidic or strongly basic conditions.

To increase the pH value, any common base, such as alkali metal and ammonium carbonate (s) and hydroxide (s), organic Amines or the like can be used. If carbonates are used, it may be necessary to add them slowly, to prevent excessive foaming.

Any common acidic material such as acetic, sulfuric or hydrochloric acid can be used to lower the pH and the like, can be added. The special acid used in each individual case should, however, be compatible with the no aluminum cations present in the slurry Form precipitation.

After adjusting the pH, if necessary, the reaction product is removed, for example by filtration or centrifugation, dehydrated. It can then if desired getting washed.

The starch product is then dried. The drying speed is in the starch products according to the invention critical. Rapid drying processes, such as evaporative drying or spray drying, do not allow the starch product to to become completely hydrophobic. The causes of this effect are currently unknown. It is therefore necessary that Dry the product in a controlled manner, e.g. using a belt dryer. The drying temperature is

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on the other hand not critical. There were obtained completely hydrophobic products, both by the fact that the product was allowed to dry in air at room temperature, as well as by drying in drying ovens or belt dryers at temperatures of up to about 1 50 ° C (300 ⁰ F).

The dried product can then be pulverized to the desired grain size. A starch aluminum according to the invention The mineral resinate complex is extremely hydrophobic and is difficult to wet under normal conditions. If such a If the product is placed in water, it will float on the surface without being wetted. Before the starch wets or moisturizes it is therefore necessary to have either one Add a small amount of a water-miscible solvent or a wetting agent or the complex extremely intensively to stir with the water. The dry starch complex is also extremely mobile or flowable or free-flowing and is similar regarding the flowability of water. When it is ground to a grain size of 44 µm (325 mesh), it can easily can be sprayed through a nozzle. The starch products of the invention are further characterized by a rubble or Angle of repose of less than about 20 when the grain size is 74 µm (200 mesh). The treated starch can gelatinized or boiled if it is wetted or moistened beforehand with a water-miscible solvent.

The so-called rubble or slope angle is according to the following Method measured. A graduated cylinder is filled to the 100 ml mark with the powdered product, whereby one lets the product fall or trickle freely into the cylinder. The product is then polished to a 11.43 cm (4.5 inch) high Metal funnel with an inner diameter of 8.255 cm (3.25 inch) at the top and 9 »53 mm (3/8 inch) at the lower end is transferred. The funnel is placed vertically 5 »O8 cm (2 inches) above a flat surface on which the product is placed free to fall or trickle out of the funnel. If in that

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If some product gets stuck in the funnel, it is gently loosened with the tip of a glass rod. The angle of inclination to the right of the façade is measured on k sides of the product pile by means of a protractor and the average value from the four measured values is given as the angle of repose.

The flowable or free-flowing hydrophobic starch products according to the invention can be used as a substitute for talc in body powders and aerosol mixtures are used and are also suitable as a release powder in printing and as a release agent for Dusting core boxes, for dusting container walls to prevent viscous substances from sticking, as well as anti-adhesive in the rubber industry.

The following examples serve to illustrate and better understand the invention, but are by no means to be understood as a limitation.

example 1

HOO g of unmodified corn starch (moisture content $ 11) are suspended in 600 g of water. This suspension is mixed with 8 g (dry basis) of a fortified rosin glue (Pale Fluid Pexol), which is dispersed in a small amount of water. Tale Fluid Pexol is a registered trademark of Hercules Inc., Wilmington, Delaware. The resulting slurry is stirred for 15 minutes, after which 16 g of Al ₂ (SO.) · 14.5HpO dissolved in a small amount of water are added. The mixture obtained in this way is stirred for a further 15 minutes and then filtered. The filter cake is dried at 118 ° C. (245 ° F.) for 1 1/2 hours. The dried residue is pulverized and the powder is sieved onto the surface of water placed in a beaker. The starch product is not moistened or wetted. If one dips a finger into the water through the powder layer and then pulls it out again, the finger remains dry. Then that will

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Powder dusted on the hands of a test person, whereupon * water droplets are dripped onto the powdered hands. The water rolls off the skin without wetting or moistening the hands.

Example 2

^ 00 g of corn starch are slurried in 600 g of water, whereupon 8 g (dry basis) of fortified rosin glue (Pale Fluid Pexol) are added and the mixture is stirred for 15 minutes. 16 g papermakers alum are placed on top of this. and stir the mixture for 15 minutes. The solid product is drained by filtration and kept at 121 ° C (250 ° F) for 1 1/2 hours dried to give an excellent hydrophobic starch product.

Example 3

7,000 g of unmodified corn starch are slurried in 12,000 g of water, whereupon the slurry is reinforced with 150 g Turpentine resin glue (dry Pexol) is added and the mixture is stirred for 15 minutes. The mixture is then incorporated Add 280 grams of dry papermaker's alain and stir the slurry another 15 minutes. The pH of the slurry is then adjusted to 6.0 with sodium carbonate and the slurry is treated filtered, the filter cake 1.5 hours at 121 ° C

F) dries and then to a grain fineness of 7 ^ pm (200 mesh size.) * Powdered. The dried starch product has a pH of 6.5, a moisture content of 11 and an angle of repose of 17.

EXAMPLE k

In 5540 g (12.5 lbs.) Of water, k 540 g (10 lbs.) Of unmodified corn starch are slurried. Then add 91 grams (0.2 lbs.) Of fortified rosin glue (Pale Fluid Pexol) and

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mix for 45 minutes.

Then add 182 g (0.4 lbs.) Of papermaker's alum in 300 ml Dissolved in water. This solution then gradually becomes the strength- Add rosin mixture and mix for 15 minutes.

The mixture obtained in this way is divided into 14 samples. at 7 samples the pH is adjusted with sodium carbonate. Then the samples are filtered, the filter cakes are washed and Dried for 30 minutes at 121 ° C (250 ° F). Then the Filter cake each ground in a "Waring mixer" and then through a sieve with a mesh size of 74 µm sifted. The pourability of each of these samples is tested. The results are shown in Table I below.

Tabel

Pourability 4 ° (Slope angle) 3 ° 1 4 ° 1 2 ° 1 2 ° 1 3 ° 1 5 ° 1 1

Sample pH

1 3.7

2 4.5

3 4.9

4 5.5

5 6.0

6 6.5

7 7.2

example

The remaining 7 samples from Example 4 are each adjusted to a pH of 6.0 with sodium carbonate. then the samples are filtered and the filter cakes are washed. The filter cakes are then left to air dry overnight « The samples are then dried for different lengths of time, but in each case at 121 C (250 F) in a drying cabinet. After this

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Drying is allowed to adjust the normal moisture content in each of the samples and then the samples are ground in this way fine that she. pass a sieve with a mesh size of 7 ^ pn. As shown in Table II below As can be seen, all samples have excellent hydrophobicity.

Table II

dry season 3 at 1 Pourability 6th sample 121 ° C (250 ° 6th F) (min) (Slope angle) 8th 0 9 12 ° 9 12th 12 ° 10 15th 13 ° 11 30th 12 ° 12th B e 12 ° 13th - ■ \ k i s ρ i e

k 000 g of corn starch are slurried in 6 000 g of water. The pH of the slurry is adjusted to 5.0 with dilute hydrochloric acid and 150 g of rosin dispersed in a small amount of water is added to the slurry

man

let the mixture stand for 30 minutes. Then add 180 g of Al (SO.) «Ito 0 to the mixture. This mixture comes in two Samples divided.

The first sample is left to stand for 30 minutes and then given sufficiently Add 2 percent sodium hydroxide solution to adjust the pH to 5.0. The slurry is then filtered and the Filter cake divided into three samples.

The first sample is allowed to dry in air at a temperature of 27 ° C (80 ° f) for 2k hours. The second sample is in one

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Drying cabinet for two hours at 66 C (150 F) and the third sample also dried in a drying cabinet, but for 30 minutes at 149 ° C (300 ° F).

All three samples show excellent hydrophobicity.

The second portion of the slurry is allowed to stand for 60 minutes and then separated into two samples. One sample is mixed with 1 g of a defoamer (Mazu I305). Then, the pH of both samples with sodium carbonate solution, which has a density of 9.5 ° Be at 26.7 ⁰ C (80 ° F) is adjusted to 5.0, filtered Then both samples and the filter cake 2 hours dried in a drying cabinet at 66 ° C (150 ° f). Both samples show excellent hydrophobicity.

Example 7

In 308.4 kg (680 lbs.) Of water, 226.8 kg (500 lbs.) Of corn starch, corresponding to 201.85 kg (kk $ lbs.) Of dry matter, are slurried. The pH of the slurry is adjusted to 5.1 with dilute hydrochloric acid. Then 8.1 kg (17.85 lbs.) (Dry weight) rosin is added and the resulting mixture is allowed to stand for 107 minutes. _{Then 16.15 kg (35 t} 6 lbs.) Al ₂ (SO ₂ K * lh H ₃ O) are added to the mixture in the course of 15 minutes and the mixture is then left to stand for 37 minutes, whereupon the pH value becomes 10 It can be observed that a small amount of a gel-like material, possibly aluminum hydroxide, separates out of the suspension »2 lowered.

Then the product is dehydrated in a basket centrifuge and separated into two subsets or samples. The first rehearsal

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is dried in a drying cabinet at 51 »7 ° C (125 ° F). This starch product has excellent hydrophobicity. The second sample is subjected to comparison of a flash drying at 162.8 ° C (325 ⁰ F). This starch product is not hydrophobic.

Example 8

By mixing 867 g of unmodified corn starch with Be a moisture content of $ 10 with 1133 roles of water three slurries were made. These slurries are then a certain amount of rosin was added and then stirred for 30 minutes. You bet each of them on this Mix 31 »2 g of alum and stir the slurries in each case 30 minutes to loosen the alum. The pH is then adjusted to 6.0 with sodium carbonate and the filter is filtered Then slurries to recover the starch product. The filter cakes are then left overnight at room temperature in each case Stand and then dry them in a drying cabinet for 5 minutes at 121 ° C (250 ° F). Eventually be the samples each ground in a Waring mixer and checked for their hydrophobicity. The results obtained can be seen in Table XIX below.

Table III Sample turpentine (g) hydrophobicity

1 15.6 complete

2 11.7 partially

3 7.8 weak

Example 9

Three 500 g slurries of unmodified starch with a solids content of 5, 20 or k0% (commercial basis) are produced.

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posed. Reinforced rosin (59.1% TS) (Pale Fluid Pexol) in an amount corresponding to 2% dry matter basis, based on starch solids, is then added to each of these suspensions while stirring. If the rosin is completely mixed, it is, based on starch solids, 2.2 ° / o of a 10 percent KAl (SO.) · 12H O solution. The pH is then increased with 2 percent sodium hydroxide solution
5.0 set. The starch products are then filtered off, washed with water and dried under ambient conditions
Let air dry. The three starch products thus obtained are respectively pulverized and sieved through a sieve with a mesh size of "century to (200 mesh). All three starch products are completely hydrophobic.

Example 10

Using the following starch starting materials, 500 g slurries with a dry starch content of k0 $ each are produced «

oxidized corn starch

cationic corn starch

Hydroxyethyl corn starch

Corn starch phosphate

Starch acetate succinate

cross-linked waxy maize starch

Rice starch

Potato starch

Wheat starch

Tapioca starch

Maranta starch

Waxy maize starch

Fortified rosin is then put into each of these slurries (Pale Fluid Pexol) in a 2 # based on starch solids, Mix in the appropriate amount thoroughly. On that the slurries are each mixed with 100 ml of one

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10 percent Al ₂ (SO.) · XH ₂ O solution, which is added in portions. A commercially available product is used as the aluminum sulfate hydrate, which contains 56.0 ° fo in the form of Al ₂ (SO.) ~ Bonded Al ₉ O-. Based on the titration curves according to FIG. 1, the amount of aluminum sulfate added corresponds to a large excess of aluminum ions. The pH of the slurries is then adjusted to 50 with 2 percent aqueous sodium hydroxide solution and the starch products are then separated off, washed, air-dried and pulverized as in Example 6. All starch products are completely hydrophobic.

Example 11

A starch product according to the invention is made analogously to Example 10 made from unmodified corn starch, but notwithstanding the aluminum sulfate of the slurry before Addition of the rosin material is added. The starch product obtained in this way is also complete hydrophobic.

Example 12

Example 10 is repeated, except that a non-reinforced light rosin resin glue is used as a departure from this. This product is also completely hydrophobic.

Example 13

Example 10 is repeated using unmodified corn starch. The reacted slurry is then divided into five samples divided, the pH values of which are adjusted to 4.0, 5.0, 6.0, 7.0 and 8.0 with 2 percent aqueous sodium hydroxide solution. The starch products according to the invention obtained in this way are then obtained as described above. All so obtained Starch products are completely hydrophobic.

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The intended uses of the invention Starch products often require that the product be the presence of potentially pathogenic microorganisms satisfies strict requirements. The content of such microorganisms can be reduced to an acceptable level, for example, by using the slurry prior to dewatering an oxidizing agent such as diluted hydrogen peroxide, treated.

The starch products according to the invention are suitable as a substitute for talc and native starch in various mixtures or products, for example body powders, cosmetic lotions, aerosol antiperspirants and the like. The starch product is usually used in the form of a powder with a grain size of Jk µm (200 mesh) or finer. For use in aerosols, the grain size is preferably chosen so that the powder passes through a sieve with a mesh size of hh µm (325 mesh). The dried product can be pulverized in any conventional manner, for example in a ball, roller or impact mill or the like.

The free-flowing, hydrophobic starch product according to the invention can be used to add talc in areas of application or in products such as baby powder, shaving powder, face powder, body powder and the like, to be replaced in whole or in part. The starch product is used in place of the talc in a weight ratio of about 1: 1 used in order to obtain products that have or cause a body feeling that the corresponding talc-based products. Typical additional components for such products include opacifiers or covering pigments, such as titanium dioxide, zinc oxide, kaolin and the like, pigments, fragrances, metal soaps, such as magnesium and zinc stearate, and absorbents such as chalk or magnesium carbonate. It should be noted that the The hydrophobic starch product according to the invention is superior to talc in that it has a much higher absorption capacity

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for moisture vapor from perspiration as talc and under these conditions its superior mobility or does not lose flowability.

The hydrophobic starch product is also suitable as a substitute or Substitute for talc in lotions. These mixtures are usually the same as the powder mixtures described above, the suspended in an emulsion of water and oil, such as mineral oil, lanolin or low-viscosity esters such as isopropyl myristate are. Such lotions can also contain emulsifiers such as triethanolamine stearate and suspending agents such as cellulose gum , contain.

example "Ik

7.8 g according to the invention hydrophobic starch product are mixed with 3 ^, 4 g TiO mixed Rostfärbpigment 6.25 S and 1.55 g Umbrapigment to give a pink-beige powder is obtained.

From 10 fo the above powder mixture and $ 90 an ordinary lotion base is prepared a lotion. A light beige, heavy lotion is obtained.

A second lotion is prepared by mixing 75 $ lotion base, 15 i ° of the above powder mixture and mixed in 10 ji of the hydrophobic starch product. A light beige lotion is obtained.

The hydrophobic starch products of the invention are also useful to replace talc as the basis in powder and aerosol formulations. As a rule, aerosol mixtures contain a propellant, e.g., a gaseous fluorocarbon, a suspending agent and a carrier liquid, as well as the base material. An economic or commercial application is to use such mixtures as an astringent Antiperspirants, such as aluminum hydroxychloride,

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to get an aerosol powder antiperspirant pack.

Example 15

An aerosol mixture is prepared according to the following recipe: Hydrophobic starch product 10.0 $ aluminum oxychloride 2.0 %

Colloidal silicon oxide 0.75 ° / o residual blowing agent

This mixture is filled into an aerosol container and tested. The product can be smooth or free and uniform spray and has a good feeling and good adhesion to the skin.

Comparative experiment

Example 15 is repeated, but, as a departure from this, instead of the starch product according to the invention, a product prepared by the process of US Pat. No. 2,852 coke is used. This material does not spray and appears to become hydrophilic when placed in contact with the propellant.

Further possible uses of the hydrophobic starch product according to the invention are its use as a release powder in in the printing industry, as a powder in the rubber industry, as a pesticide or pesticide base, as a filler for paints in cement mixes and mild abrasives, e.g. for polishing rice.

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The invention also provides preferred embodiments Suspending agents containing powder-aerosol mixtures, a carrier liquid, a gaseous propellant and a powder, wherein this powder is a granular, free-flowing hydrophobic starch material with or from starch material granules the surface of which is deposited at least one aluminum resinate in an amount sufficient to cover the coated To hydrophobize starch material granules. Such powder-aerosol mixtures preferably also contain an astringent Antxtranspirationsmittel and / or additionally a perfume and optionally a metal salt of a fatty acid.

The invention further provides a cosmetic lotion containing an organic lotion base, an opacifier and a Powder, this powder also being the starch product mentioned above. The cosmetic lotion preferably also contains additionally a pigment material.

The invention also provides, as a preferred embodiment, a cosmetic lotion containing an organic lotion base, an opacifying agent and a powder, this powder also being the above-mentioned starch product. Preferably contains the cosmetic lotion also contains a pigment material.

Furthermore, as a preferred embodiment, the invention also provides a body powder containing a metal salt of a fatty acid and a powder powder as well as the starch product described herein.

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Claims (1)

Claims rly hydrophobic mobile starch product, characterized in that that it contains a granular starch material with or from starch material granules on its surface at least one aluminum resinate is deposited in an amount sufficient to cover the coated starch material granules to hydrophobize. 2 starch product according to claim 1, characterized in that that it is in the form of a powder that passes through a sieve with a mesh size of 0.075 ram (200 mesh) in bulk has an angle of repose of less than about 20 °. 3. Starch product according to claim 1 or 2, characterized in that it is used as a special starch · corn starch and / or a modified one Contains starch. ■ "—— - 4-. Process for the production of a movable or free-flowing, hydrophobic starch product, in particular according to one of claims 1 to 3 »characterized in that one a) an aqueous slurry of a non-gelatinized starch material manufactures, b) the slurry with 1) 1.5 to about 4 parts by weight of a water dispersible Serpentine resin material per 100 parts by weight of starch material and 2) about 2.5 to 8 moles of aluminum ions in the form of a water-soluble one Aluminum salt added per mole of rosin material and c) the product obtained is recovered and slowly dries. 609851/10 65 5. The method according to claim 4-, characterized in that the starch solids content of the slurry is adjusted to "up to 4-0% by weight. 6. The method according to claim 4 or 5 »characterized in that that corn starch and / or a modified starch are used as starch material 7. The method according to any one of claims 4- to 6, characterized in that that a fortified rosin is used as rosin material. 8. The method according to any one of claims 4- to 7j, characterized in that that the water-soluble aluminum salt is Hatriura aluminum sulfate, aluminum aluminum sulfate, aluminum sulfate, Aluminum chloride and / or aluminum nitrate and / or one or more hydrate (s) of these salts are used. 9. The method according to any one of claims 4 to 8, characterized in that adjusting the slurry to a pH in the range of about 3 »5" to 8.0 "before the product is separated therefrom. 10. The method according to any one of claims 4- "to 9, characterized in that that the product is recovered from the slurry by filtration. 11. The method according to any one of claims 4- "to 10, characterized in that that the product is dried in a belt dryer. 12. The method according to any one of claims 4 to 11, characterized in that the drying is carried out at a temperature in a range from about room temperature to 150 ⁰ C (30O ⁰ JP). 609851/1065 13 »Use of the starch powder according to claims 1 to 3 ₅ in particular of the starch product produced according to one of claims 4 to 12 in the form of a powder, the largest particles of which still pass through a sieve with a mesh size of 44 µm, in a powder-aerosol mixture Suspending agent, a carrier liquid, a gaseous propellant and this powder, or with a maximum particle size of 0.075 mm in a cosmetic lotion containing an organic lotion base, an opacifying agent and this powder or as a body powder containing a metal salt of a fatty acid, a powder powder and this powder . Use according to claim 13 in a powder-aerosol mixture, characterized in that this additional an astringent Contains antiperspirants 15. Use according to claim 13 or 14 in a powder-aerosol mixture, characterized in that it additionally contains a perfume and optionally a metal salt of a fatty acid. 16. Use according to claim 13 in a cosmetic lotion, characterized in that it additionally contains a pigment material. 609851/1065