MXPA99011430A - Method for manufacturing pure guar meal - Google Patents

Abstract

La invención se relaciona con un proceso para producir harina pura de semillas de guar y con el empleo de la harina de semillas de guar de cloruro de hidroxipropiltrimetilamonio obtenida de la harina de semillas de guar producida según este proceso en formulaciones cosméticas acuosas transparentes destinadas para ser empleadas sobre los cabellos y/o la piel, y que deberán volver a quitarse enjuagando, como agente acondicionador y/o agente auxiliar de la deposición para otros agentes acondicionadores al diluirse las formulaciones cosméticas.

Description

PROCESS FOR PRODUCING PURE FERDER SEEDS OF GUAR Description of the invention The object of the present invention is a process for producing guar seed flour which, when dissolved in water, results in a transparent solution of varied viscosity, that is to say of very low to very high viscosity, being that despite an extensive purification obtained with the process good yields of pure flour. Transparent solutions of high viscosity of pure flour of guar seeds have great significance, first of all in the food industry. The guar seed flour is used as a thickener in the textile and explosives sector, as a binder in the paper industry, as a flocculating agent in the extraction of minerals and an auxiliary agent in the extraction of natural gas and petroleum, in the pharmaceutical and cosmetic area, and as a thickener, emulsifier and co-stabilizer in the area of the food industry and food technology. In the pharmacy low-viscosity guar seed flour is used to incorporate by spraying, for example vitamins, in order to increase its storage stability. In addition, the use of guar seed meal in the sprays guarantees an approximately monomolecular distribution of the active substances, and consequently an improved uniformity of the resorption, which is desirable in the case of anti-asthma products and various antiallergics. Due to the extremely low protein content of pure guar seed meal there is no danger of an allergic reaction to a drug containing this substance. Other applications in this field are the formulation of delayed-action tablets and as an agent for reducing the level of cholesterol. In the area of medicine, high viscosity guar seed flour is also used as a stabilizer in contrast agents. Among other things, guar seed meal has also proved to be an ideal dietary agent, because its components, which are known as galactomannans, are not attacked by human enzymes of the stomach and small intestine. This is to be expected because there are no ß-mannans, or ß-mannosidases or a-galactosidases, which would be necessary for the cleavage of these components, in the resorbent part of the human digestive system. Since the components of guar seed meal do not penetrate human metabolism, guar seed meal can not be considered as a carrier or supplier of calories in any way. In view of the fact that the guar seed meal consists of completely neutral polysaccharides, more precisely galactomannans which have neither uronic acid nor other ionogenic groups in the physiological sense represent a perfectly harmless material. Another advantage in regard to its use as an additional substance in food products is its absolute taste neutrality. Find - application in food products or reduced calorie or fat drinks that in consumers frequently cause the sensation of being "lazy". The addition of pure flour from guar seeds to these products gives them a more "creamy" consistency. In the manufacture of fruit juices the flour of the guar seeds is used to uniformly resuspend the pulp of the fruit, in puddings and creams it serves as a thickener, in ice creams (shortcakes), altered milks, muses and similar products as a stabilizer. With conventional flour seed meal preparations, only a reduced reciprocal mol- lular action could be observed with the xanthan biopolymer. It is true that when mixing these two colloids there was a synergistic increase in viscosity, however there was no specific formation of gel as in the case of the carob, the seed flour of the "carob tree", and the xanthan. If mixtures are heated together in the 1: 1 ratio of the guar seed meal obtained according to the invention and xanthan and allowed to cool to 4 ° C (domestic refrigerator temperatures) a soft gel is formed. An advantage of this combination of guar and xanthan seed flour is that the gel of these two components melts at body temperature, and therefore is excellently suited for the preparation of food products of the jelly type, as a vehicle in the administration of medications in the form of suppositories and the like. In addition, flour from guar seeds and xanthan are used together as co-stabilizers in the manufacture of salad dressings, since this combination, contrary to guar seed meal when used alone, is more resistant to acids. The guar seed meal is obtained from the endosperm of guar grain (Cyamopsis tetragonobulus). The guar seed meal consists largely of galactomannans, specifically polysaccharides whose main chain is linked by ß-glucosidic bonds in the 1-4 direction, and is composed of mannose, which is partially bound to the galactose through primary OH groups. The proportion of unsubstituted mannose with respect to that substituted with galactose is approximately 2: 1, with the substituted units not being arranged in a strictly alternating manner in the polygalactomannan molecules, but in groups of two or three. Already at low concentrations, guar galactomannans form high viscosity solutions with water. Solutions of 1 percent by weight of commercial gura seed meal in water result in viscosities of approximately 3,000 to 2,000,000 mPa.s. By virtue of chemical and physical differences, guar galactomannans were subdivided into galactomannans soluble in hot water, soluble in cold water and insoluble. To obtain and purify the guar seed meal, the guar seed is treated mechanically, with approximately 35 parts halves of doped guar endosperm and approximately 60 parts of guar flour being obtained. The guar flour is constituted mainly by the germ of the seed, the excoriated shell of the seed and small parts of the endosperm. The endosperm completely envelops the seed and is wrapped in turn by the shell of the seed. At the points of contact between the endosperm and the shell of the seed is a cell layer similar to aleurone, rich in proteins, whose cells are closely linked to the endosperm.

The impure endosperm halves can be further purified mechanically and "spiits" of different qualities are obtained as regards their protein content, their non-hydrolysable components by acid (A.I.R.) as well as the shell content. The term "spiit" usual in the competent media should be equated to the term "endosperm halves". Although guar seed flour is already widely used as a thickener, it is desirable to improve its degree of purity and, in addition, its physical and physiological properties. In particular for its use in the area of foodstuffs, the purity of the guar seed meal is of great importance. It is also desirable to make better use of the neutral, non-ionogenic main components of the endosperm, so that they can be used to a greater extent in the corresponding industrial branches instead of the cellulose derivatives or other polysaccharides transparently soluble in water, or of the polymers Synthetics transparently soluble in water. If the products processed into flour consisting of pure flour of guar seeds currently commercially available are dissolved in water for 10 minutes at 25 ° C or at 86 to 89 ° C, turbid solutions are obtained. If the insoluble material of these solutions is centrifuged with high centrifugal forces (> 35,000 x g), it turns out that 23-35% of the guar seed meal is constituted by centrifuged material. Microscopic investigations have shown that the centrifuged material is composed mainly of shell fragments, protein bodies, insoluble peripheral cells, intact intact cells of the internal endosperm and other impurities of the seed or spiit. A known chemical derivation of guar seed flour by etherification, carboxymethylation, hydroxypropylation, the combination of these as well as cationization allows the elaboration of products with a remarkably improved solubility behavior in water and, added to this, a greater transparency of the solutions One of the processes applied hitherto to obtain pure flour from guar seeds employs chlorinated solvents, such as for example trichlorethylene (cf. EP 0 130 946, Meyhall Chemical AG). The suspension was fractionated simply by allowing it to stand or centrifuge, as a protein-rich fraction was formed (floating fraction) and a fraction was separated in proteins (submerged fraction). It was possible to demonstrate that the upper floating fraction of endosperm transformed into flour as Guar CSA 200/50 can contain up to 25% of proteins, and that the submerged fraction that constitutes 75% of the pure flour, contains approximately 1.5 to 1.6% of proteins . The submerged fraction is, for example, suitable for the preparation of cationic derivatives, which after dissolution result in diaphanous aqueous solutions. The disadvantage of this process is that finely ground pieces of shell are also found in the submerged fraction. Another disadvantage is the use of halogenated solvents, by virtue of which a specific weight of 1.47 to 1.48 kg / l is required. The proteins have a density of 1.3 kg / l and the galactomannans have a density of 1.5 to 1.55 kg / l, depending on the moisture content. The guar seed meal produced with the described process is only suitable for technical applications, for the area of foodstuffs this guar seed meal is not adequate because residues remain in the finished product, 10 ppb in the fractions extracted with methanol, of the halogenated solvent used. Halogenated solvents are toxic and caustic in varying degrees, and often have allergenic properties. Also for ecological reasons should be dispensed with this process.

Another process for the manufacture of pure flour from guar seeds was proposed as early as 1969. It consisted of an alkaline treatment of spiits pre-impregnated at high temperatures., being that 100 parts of SPS absorbed 100 parts of alkali. The large amount of alkali, specifically NaOH, had to be separated by washing. This was done with cold water in a proportion of one part of SPS (single purified spiits) by 80 parts of H20, and a dehydration stage with isopropanol (IPA) in which the residual NaOH of the spiits was simultaneously neutralized by acetic acid. purified. After the milling, a pure flour of high quality guar seeds was obtained with a yield of 60-70%, based on the raw material SPS (purified simple spiits) .In 1969 this process was developed until the industrial maturity by Stein, Hall &; Co., Long Island City, New York. The current washing process with water of the carboxymethylated, hydroxypropylated or cyanized guar guar (guar ether) flour, or combinations thereof, is based on that process. The purpose of this purification of the guar derivatives is to separate shell fragments and peripheral cell layers, as well as to eliminate the by-products of the various etherization reactions (hydroxypropylation, carboxymethylation and cationization and / or their combinations).

Another known process for producing pure flour from guar seeds is the treatment of guar spiits with acid. This process yields a product of excellent quality, that is, the resulting material, when dissolved in water, gives highly transparent solutions that simultaneously have a high viscosity. However, a disadvantage of this process lies in the relatively complex method of the process, with several stages of washing and neutralization. In addition, special devices are required for an acid treatment, which makes the process very expensive. Despite the extensive purification processes described above, to date it has not been possible to obtain an inexpensive and non-polluting environment, a pure, non-derived guar seed meal, which results in a high diaphanous aqueous solution. viscosity, and simultaneously good yields. The disadvantages of the above process methods for purifying and obtaining pure flour from guar seeds are: 1. large losses of valuable parts of the endosperm during mechanical purification, and due to this reduced yields of pure guar seed meal with respect to the Starting material; 2. fragments of shell that are still found in the various qualities of spiits, and which greatly disturb the functionality of the modified finished products; 3. peripheral cells, rich in proteins of the aleurone layer that barely sponge in water and also negatively influence the functionality of the finished product; 4. the existence of other impurities of guar seeds, such as wood particles, which should not be found; 5. a high load for the environment. Therefore, it was urgently desirable to develop a process for the manufacture of pure flour of guar seeds that eliminates the disadvantages mentioned above and produces pure flour of guar seeds with good yields, which after dispersion in water results in a diaphanous solution of high viscosity that finds its application above all, for example, in the food industry, the pharmaceutical industry, the dyes and spreads, as well as in the extraction of oils. The object of the present invention is to satisfy the previously mentioned requirements, specifically to obtain by a new method of production good yields of pure guar seed flour, in particular suitable for the food industry, which results in diaphanous aqueous solutions with viscosities from low to high. The process according to the invention for the production of pure flour from guar seeds is defined in claim 1 of the patent, and comprises the following steps: (a) treating the guar spiit with a base in the presence of small amounts of hydrogen peroxide, (b) partially neutralize the alkaline spiit with an acid, * (c) mechanically separate the peripheral cells, (d) evetually wash twice with water (e) treat the spiit with an aqueous alcoholic solution. A first condition for obtaining pure flour from guar seeds is the improvement of the starting material, the spiit. Spiits covered with husk represent up to 42.5 percent by weight of the seed. The overlapping shell-endosperm parts, which represent 13.5 percent by weight of the seed are substantially insoluble in water. The embryo of the seed represents the remaining 44%. These quantitative indications show that the theoretical yield of spiits without shells and without overlapping parts, useful for the invention, is 32%.

The most convenient way to produce the guar seed meal that is obtained according to the invention is from spiits having a protein content of 4.2% and a proportion of A.l.R. of 1.8%. These spiits can be produced at room temperature, but preferably at elevated temperatures, after an alkaline treatment with sodium hydroxide at 10 to 40%, preferably at 33%. The difference of this new process in comparison with the processes known up to now, which also include an alkaline treatment of the starting material, consists in the addition of small amounts of hydrogen peroxide during the alkaline treatment. By means of this chemical "peeling" (splintering), spiits are obtained from which it is possible to separate the cells of the casing by mechanical means, simply and almost completely. By treating the spiits with, for example, 8-10 parts of 33% sodium hydroxide and 1.1 parts of 35% hydrogen peroxide, the peripheral cells of the spiit are attacked and it is possible to separate them by mechanical abrasion. The polysaccharides of the cell layers below the peripheral cells are not oxidized because the concentration of the hydrogen peroxide used is too low.

The spiits purified in this way, which optionally are washed with water or can also be processed without washing, can still be significantly improved for the purposes of the invention when desolving the phospholipids and other "non-polar" substances. This results in a greater transparency of the product dissolved in water and is achieved by treating the depurated product with an aqueous alcoholic solution, preferably aqueous isopropanol (IPA) at elevated temperatures. In the case of products that were not washed with water, it is not necessary to add more bleach before the isopropanol treatment, since the product still contains approximately 4-7% NaOH. If the product was washed, the addition of an alkaline solution is necessary. After the treatment with isopropanol the alkaline spiits are washed with water and milled when they have a desired moisture content. The degree of wetting during grinding significantly influences the properties of the final mealy product. The higher the technically feasible moisture content, the greater the amount of soluble polysaccharides, that is, the higher the yield of active galactomannans. This can be explained by the increase in cell volume due to the high degree of humidification. During grinding, the foamed cells are forced through a defined opening or slit, during which the cell membrane can tear off, as long as the sponge particles are significantly larger than the openings (the elasticity of the cells also plays an important role). cells). When manufacturing water solutions galactomannans are thus released from the destroyed cells, which does not happen in the case of non-destroyed cells. In these cases the galactomannans remain inside the intact cells and do not effectively contribute to the viscosity of the solution. A moisture content of approximately 82%, preferably from 72 to 75% is acceptable during milling for practical and technical reasons. Moisture contents less than 72% when grinding impairs the quality of guar seed meal. A content higher than 82% causes technical problems. A great advantage of the present invention resides in the recovery of 25% of the excoriated peripheral cellular layers, that is to say that the ecological load is extremely reduced. Another advantage of the present invention resides in the simplification of the process. Only a few steps are required to obtain a purified product with high solubility and viscosity.

Yet another advantage of the present invention consists in the possibility of manufacturing products for solutions with, for example, viscosities as low as 35 mPa.s, and those with up to 6000 to 9000 mPa.s at a concentration of 1% in water measured at 25. C. Another additional advantage of the invention lies in the production of pure guar products whose protein content is as low as 0.2 to 0.5%. The major advantage of the present invention, however, lies in the fact that the purification processes hitherto conventional are simplified and substantially shortened, whereby the manufacture of the pure flour of guar seeds becomes substantially more economical. In addition, the new process is manifestly ecological, since it allows recovering approximately 25% of the excoriated peripheral cell layers. The product of the resulting abrasion with the process described in this document can also be used as a thickener in textile printing. This means that the starting material is used optimally. A derivation of the galactomannans from guar seed meal has significance for its solubility in water. By derivatization (for example carboxymethylation, hydroxypropylation, cationization and the like), one or more non-ionic, anionic or cationic groups are added., whereby hard-to-access etherized galactomannans already dissolve at 25 ° C. Commonly the derivation is carried out after the purification. However, in the food industry the use of derived guar seed flour is not allowed. But the derived guar seed flour, in particular that with cationic activity, finds its application in cosmetic products such as hair conditioners, body lotions and the like. Among the cationic derivatives of guar seed meal that can be prepared from a pure guar seed meal obtained according to the process according to the invention, the guar seed meal of hydroxypropyltrimethylammonium chloride is very particularly counted. These may be obtained by the etherification of a pure guar seed meal under alkaline conditions and under an inert gas atmosphere with 2,3-epoxypropyltrimethylammonium chloride as a cationic etherification agent, and subsequent purification and separation. Preferably, the etherization can be carried out in two main steps: a first step in which the cationic etherification agent diffuses into the guar seed meal under alkaline conditions and under an inert gas atmosphere at a temperature of about 20 to 25 ° C, preferably about 30 to about 50 ° C, and then suspended in an aqueous alcoholic solution, in particular a solution of water-isopropanol containing from 25 to 70% by weight of isopropanol, and a second stage, the etherification stage itself under an inert gas atmosphere at a temperature of about 50 to about 70 ° C, with a temperature of about 60 to about 65 ° C being particularly preferred. The first step (diffusion) can be carried out particularly in the presence of sodium hydroxide, being that 100 parts of guar seed flour correspond approximately 1 to 4 parts by weight of sodium hydroxide; This stage can be prolonged for approximately 15 to 60 minutes. The second stage (the etherification itself) can be extended for approximately 45 to 120 minutes. The resulting cationic product is brought back into contact with the air under the same temperature conditions, in order to bring the product to its desired final viscosity. The product is then refined once or several times by washing with an aqueous alcoholic solution, in particular water / isopropanol. After adjusting the pH with an acid, such as, for example, acetic acid in particular, the cationic guar seed flour is separated, for example, by filtration or centrifugation, and then dried. The amount of the etherifying agents that can be used is chosen so as to obtain a cationic flour of guar seeds with a degree of substitution (SG) in the range of 0.01 to 0.4. The degree of substitution (SG) can be defined as the number of moles of 2,3-epoxypropyltrimethylammonium chloride that is added per hexose unit of the guar seed meal. The cationic derivatives of the guar seed meal obtained in accordance with the process of the invention, in particular the guar seed flours of hydroxypropyltrimethylammonium chloride, can be used in particular for the preparation of cosmetic formulations. Accordingly, the invention is further related to the use of a guar seed meal of hydroxypropyltrimethylammonium chloride made by the etherization of a guar seed meal obtained according to the process according to the invention in transparent aqueous cosmetic formulations intended for to be used on the hair and / or the skin, and to be removed again by rinsing, as a conditioning agent and / or deposition aid for other conditioning agents when these cosmetic formulations are diluted. By "tansparent aqueous cosmetic formulation" is meant any cosmetic formulation containing at least 60% by weight of water, and at 600 nanometers it has a transparency of at least 92%. These transparent cosmetic formulations can be present in particular in the form of a conditioning shampoo, shower gel or liquid soap. For an advantageous embodiment of the invention, this guar seed meal of hydroxypropyltrimethylammonium chloride has a degree of substitution (SG) of from about 0.01 to about 0.4, preferably from about 0.05 to about 0.25, and an average molecular weight of about 50000 to about 3 x 106. It can be used in an amount corresponding to approximately 0.05 to 0.5%, preferably 0.1 to 0.3% of the weight of these cosmetic formulations. In addition to the guar seed meal of hydroxypropyltrimethylammonium chloride, other conditioning agents may still be present. These are in particular non-volatile silicones (polyorganosiloxanes) with a viscosity of 10000 to 10d mPa.s in the form of particles with a diameter below nanometers, preferably from about 20 to about 25 nanometers. These silicones are preferably used in the form of a prefabricated aqueous dispersion which can have a concentration of from about 20 to about 60% by weight, preferably from about 30 to about 50% by weight. They can also be used in cosmetic formulations in an amount of from about 0.1 to about 1% by weight, preferably from about 0.5 to about 1% by weight of active substance with respect to the weight of the cosmetic formulation. As silicones, mention may be made of polydimethylsiloxane oils, phenylated silicone oils (diphenyldimethicones) and amino silicone oils (amodimethicones). Finally, the invention relates to transparent aqueous cosmetic formulations intended to be used on the hair and / or the skin, and which must be removed again by rinsing, these formulations containing the following in relation to their weight: approximately 8 to approximately 30% by weight, preferably about 10 to about 20% by weight of at least one nonionic, anionic, amphoteric or hybrid ionically active surfactant, expressed as active substance, about 0.05 to about 0.5% by weight, preferably about 0.1 to about 0.3 % by weight of a guar seed meal derivative of hydroxypropyltrimethylammonium chloride of a guar seed meal produced according to the process of the invention, optionally from about 0.1 to about 1% by weight, preferably about 0.5 to about 1% by weight of at least one non-volatile silicone in an aqueous mulsion, whose particle size is less than 35 nanometers, preferably from about 20 to about 25 nanometers, expressed as active substance, and at least 60% by weight of water, preferably at least 75% by weight of water. Aqueous transparent cosmetic formulations have a transparency of at least 92% at 600 nanometers. Among the nonionic, anionic, amphoteric or hybrid ionic surfactants that may be present, the following may be mentioned: anionic surfactants such as alkyl sulfates of the formula ROS03M, where R represents an alkyl or hydroxyalkyl radical with 10 to 24 carbon atoms, preferably 12 to 20 carbon atoms and most preferably with 12 to 18 carbon atoms, M represents a hydrogen atom or a cation as defined above, as well as its ethylene oxide (EO) derivatives and / or propylene oxide (PO) with on average 0.5 to 6, preferably 0.5 to 3 units of EO and / or PO; salts of saturated or unsaturated fatty acids with 8 to 24 carbon atoms, preferably 14 to 20 carbon atoms, alkylbenzenesulfonates with 9 to 20 carbon atoms, primary or secondary alkylsulfonates with 8 to 22 carbon atoms, alkylglycerin sulfonates, sulfonated polycarboxylic acids as described in GB-A-1 082 179, paraffin sulphonates, N-acyl-N-alkyl taurates, esters of alkyl phosphoric acid, and / or alkyl ether phosphoric acid and / or arylalkyl phosphoric acid, isethionates, alkyl succinamates, sulfosuccinates of alkyl, monoester or diester of sulfosuccinate, N-acyl sarcosinates, alkyl glycosidic sulphates, alkylpolyethoxy carboxylates; wherein the cation is an alkali metal or alkaline earth metal (sodium, potassium, lithium, magnesium), an optionally substituted ammonium radical (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium and others) or an alkanolamine derivative (monoethanolamine , diethanolamine, triethanolamine and others); esters of the alkylsulfonic acid of the formula R-CH (S03M) -COOR ', where R represents an alkyl radical with 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms, R' represents an alkyl radical having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, M represents an alkali metal cation (sodium, potassium, lithium), an optionally substituted ammonium radical (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium and others) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine and others). The methyl esters of sulfonic acid with an R radical of 14 to 16 carbon atoms are especially preferred; alkylamide sulfates of the formula RCONHR 'OSO3M, in which R represents an alkyl radical with 2 to 22 carbon atoms, preferably 6 to 20 carbon atoms, R' represents an alkyl radical with 2 to 3 carbon atoms, M represents a hydrogen atom or a cation as defined above, as well as its derivatives of ethylene oxide (EO) and / or propylene oxide (PO) with on average 0.5 to 60 units of EO and / or PO; phosphates and alkyl and dialkyl phosphate ethers; nonionic surfactants such as polyalkoxylated aliphatic alcohols of 8 to 22 carbon atoms with 1 to 25 units of alkylene oxide (ethylene oxide, propylene oxide); exemplary we will mention TERGITOL 15-S-9, TERGITOL 24-L-6 NMW, marketed by: Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4, marketed by: SHELL CHEMICAL Company, KYRO EOB, marketed by: THE PROCTER & GAMBLE Company; glucosamides, glucamides; The alkyl polyglycosides described in US-A-4 565 647 and their polyalkylene oxide derivatives; polyalkoxylated alkylphenols (polyethoxylated, polypropyloxylated, polybutoxylated), which alkyl substituent is alkyl of 6 to 12 carbon atoms and containing from 5 to 25 units of alkylene oxide; we will mention exemplary TRITÓN X-45, X-114, X-100 or X-102, marketed by ROHM & HAAS Company; glycerinamide derivatives of N-alkylamines (US-A-5,223,179 and FR-A-1 585 966); the condensation products of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol and / or glycerin, such as the PLURONIC group, marketed by: BASF; the condensation products of ethylene oxide or propylene oxide with ethylenediamine, such as the TETRONIC group, marketed by: BASF; amine oxides such as alkyldimethyl amine oxides with 10 to 18 carbon atoms, alkoxyethyldihydroxyethyl amine oxides with 8 to 22 carbon atoms; fatty acid amides with 8 to 20 carbon atoms; ethoxylated fatty acids; ethoxylated fatty acid amides; ethoxylated amines; ethoxylated amidoamines, in particular those derived from N-hydroxyethyl-N '-alkylamidoethylenediamines; amphoteric and hybrid surfactants, such as alkylbetaines, alkyldimethylbetaines, alkyl-amidopropylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, imidazoline derivatives, such as alkyl amphoacetates, alkyl amphodiacetates, alkyl amphopropionates, alkyl amphipipropionates, alkylamines or alkylamidopropylhydroxysultaines, products of condensation of fatty acids and protein hydrolysates, amphoteric derivatives of alkyl polyamines such as AMPHOLIC XL, marketed by: RHONE-POULENC, AMPHOLAC 7T / X and AMPHOLAC 7C / X, marketed by BEROL NOBEL. These surfactants are preferably selected from the group of anionic surfactants, such as alkyl sulfates and / or alkyl sulfate ethers, preferably in combination with at least one amphoteric surface active agent, such as alkylamidopropyl betaines and / or amphoacetates or alkyl amphodiacetates, and optionally in combination with at least one nonionic surfactant, such as polyalkoxylated aliphatic alcohols and / or glucamides and / or alkyl glucosides. Very particularly these cosmetic formulations comprise a mixture of surfactants which is constituted by approximately 5 to approximately 20%, preferably about 10 to about 15% of at least one anionic surfactant, in particular of an alkyl sulfate and / or alkyl ether sulfate, about 0.1 to about 15%, preferably about 1 to about 5% at least an amphoteric surface active agent, in particular alkylamidopropylbetaine and / or alkyl amphoacetate or amphodiacetate, and about 0 to about 5%, preferably about 1 to about 3%, of at least one nonionic surfactant, in particular of a polyalkoxylated aliphatic alcohol and / o of a glucamide and / or of an alkyl glucoside, where the percentage indications refer to the weight percent of the surfactant active substance in the cosmetic formulations. These transparent aqueous cosmetic formulations may also contain other additional substances, which are chosen so as not to reduce the transparency of these formulations. The cosmetic formulations according to the invention may also contain the following: up to 10%, preferably up to 5% of polymeric derivatives which exert a protective or moisture-giving effect on the skin, or a conditioning effect, such as modified celluloses (eg example hydroxyethylcellulose, carboxymethylcellulose), or nonionic derivatives (eg, hydroxypropyl guar seed flour), anionic derivatives (carboxymethyl guar seed flour), or mixtures of nonionic / anionic derivatives such as carboxyhydroxypropyl guar seed flours; however, synthetic polymers such as polyacrylates, or synthetic cationic polymers, which are known under the generic name CTFA of "polyquaternium", for example the polymers MIRAPOL Al5 or MIRAPOL 550 of RHONE-POULENC, can be added instead of this or additionally. or polymers that confer characteristics to facilitate styling, such as vinylpyrrolidone copolymers; up to 5% moisture retention agents or humectants, as in particular glycerin; - up to 5% of calcium complexing agents, such as citrate ions; up to 1% sunscreen filters such as octylmethoxycinnamate (PARSOL LCX from GIVAUDAN); up to 0.3% of bactericides such as triclosan, chlorophenesin; up to 1% preservative agents such as methyl ester, ethyl ester, propyl ester and p-hydroxybenzoic acid butyl ester, sodium benzoate, GERMABEN (tradename); - up to 0.5% thickeners, gelling agents or stabilizers such as the crosslinked polyacrylates CARBOPOL marketed by GOODRICH, xanthan gum, succinoglycan derivatives; perfumes, dyes. The material resulting from the present invention is particularly advantageous in that, when dissolved in water, it results in highly transparent solutions. A 1% solution (0.9% anhydrous substance) of the pure guar seed meal produced with this process shows a viscosity of 6000 to 9000 mPa.s at 25 ° C. A transparency of the aqueous solution of up to 100% can be achieved. 95% The viscosity was determined in a Brookfield RTV viscometer, the transparency of the solutions in a photospectrometer. The invention is explained below based on some examples. As starting material for the described examples, spiits of the highest quality were used. It can be seen from these examples that already a treatment of the periphery of the guar spiit with an optimized concentration of sodium hydroxide in the presence of small amounts of hydrogen peroxide leads to pure guar products. These pure products show viscosities of 5000 to 9000 mPa.s at a concentration of 1%, as well as transparencies of more than 80% at a concentration of 0.5% and 1 cm of light path at 500 nm, while conventional guar products in aqueous solution show transmissions of light from 45 to 48%.

This transparency to light can be achieved even without the treatment with isopropanol. With isopropanol they achieve transparencies of up to 98%, by virtue of the fact that isopropanol eliminates phospholipids that can not be separated by washing with water. After this first stage of purification, alkaline spiits have a water content of 12 to 15%. The spiits are washed twice with water in a ratio of 1: 7 and 1: 6 for 6 and 8 minutes. In this the spiits absorb water up to 70% and can either be ground after adding additional water to a moisture content of 76 to 78%, or can be further modified. However, it is possible to continue treating the spiits without the washing stage. The milled products have a protein content of 1.0 to 1.2%, and a proportion of A.I.R. of approximately 0.8%. The yield of these products is 75 to 79%, depending on the quality of the starting material. Example I 370 guar spiits with a galactomannan content of at least 84% are treated, for example, in a Sigma mixer preheated with 10% NaOH (84 ml of a 33% NaOH solution), and then after a minute, still additionally with 4 ml of a 35% H202 solution which had been diluted with 20 ml of isopropanol. The temperature of the reaction is increased indirectly by hot water of 90 ° C to 70 ° C and then kept constant for 30 minutes. Subsequently, a part of the present liquor is neutralized by means of 21 g of 96% H2SO4 diluted with 8 g of water. Continue for 16 minutes at 70 ° C with the mixing process. Subsequently, 70 g of water are rapidly added in order to separate the treated peripheral cell layers more easily during the mixing process. The mixing process is carried out for 30 minutes at 70 ° C. The reaction mixture is screened through an M20 screen, which results in 95 g -M20 (H20: 16.2%), and 360 g + M20 (H20: 12.9%). The + M20 fraction shows a NaOH content of -6% and washed twice with tap water, where in each case 6 parts of tap water are used for 1 part of the unwashed fraction of + M20. The washing process was carried out 5 and 6 minutes under intense agitation.

The washed, sponged spiits are recovered by simple sieving. (The alkaline treatments mentioned in the literature and patent literature using 20-32% NaOH require a quantity of wash water of more than 40 parts of tap water per 1 part of spiits not washed). 916 g of sponge spiits with a water content of 73.3% were recovered after purification with water. A viscosity of 7000 mPa.s was measured at 20 rpm and 25 ° C, after the homogeneous solution of the spiked spiits obtained by disintegration had cooled overnight. The 1% aqueous solution was made in a homemade mixer at the highest speed up to about 90 ° C. The amount of fluted spiits to be dissolved was calculated for a water content of 10%. A 1: 1 dilution of this 1% solution results in a light transmission of 81.3% at 500 nm in a 1 cm cuvette. N.B. If 40% less NaOH and 40% less than H2S0 (under otherwise equal conditions) less galling is obtained (approximately 12%) and light transmission significantly less than about 75%. Example II These products obtained according to Example I can be significantly improved with regard to their quality (viscosity, transparency), by further reducing their protein content and of A.I.R. Products that are not washed with water can be treated for 30-60 minutes with 25 percent by weight of isopropanol at 65 to 70 ° C without the addition of additional bleach., since the spiits still contain approximately 5-6% NaOH. If washed spiits are used, the addition of 2-5% bleach, preferably sodium hydroxide, is required. Following the aqueous treatment with isopropanol the alkaline spiits are washed, brought to the required moisture content by the addition of more water, and milled. The transparency of the aqueous solutions of these products is from 93 to 95%. The viscosity of a 1% aqueous solution can be adjusted to 6000 to 7000 mPas depending on the reaction conditions. The product designated as -M20 purified in the above-described manner is a guar seed flour with a viscosity of 1000 to 1500 mPas at a concentration of 1%, which can serve as a base for significantly improved guar products or derivatives. Also the -M20 fraction can be elaborated for applications that use alkaline oxidized guar products or derivatives. A field of application would be, for example, the printing of polyesters. By using the -M20 fraction the material to be printed obtains a feeling of softness after the dispersion dyes used are set at extremely high temperatures. Example III 8522 g of guar spiits with a galactomannose content of at least 84% are contacted, for example, with 2850 g of a 33% NaOH solution that was preheated to 74 ° C in a Drais heating mixer indirect. After 3 minutes, 230 g of a 14% H202 solution are slowly added. The temperature of the heterogeneous reaction mixture is increased to 70 ° C and maintained for 30 minutes. The reaction mixture is then cooled to 55 ° C with 668 g of a 69.5% sulfuric acid for better control of the partial neutralization. The reaction is continued for 30 minutes at 70 ° C. The treated guar spiits are then washed with cold water from the tap for 5 minutes, with 12 parts of tap water being used for 1 part of unwashed spiits. . During the reaction in the aforementioned mixer practically no abrasion occurs, so that a sieving process before washing can be dispensed with. The washed spiits have a water content of 72% and are milled in the usual way to a fineness greater than M150 in a hammer mill in a stream of hot air The ground product still contains about 2% NaOH and shows a viscosity of 4200 mPas at a concentration of 1%, based on 10% water at a pH of 6.8. The transparency of a 0.5% solution that was measured as described is 82.4%. Example IV 25 kg of guar of the same quality used in examples I and II are treated for a half hour at 70 ° C in a Sigma mixer with 9% NaOH in the presence of 0.67 kg of a H202 solution at 14.1% . A 33% NaOH solution was used. Subsequently, the peripheral cell layers were excised for 15 minutes at 70 ° C and open reactor. It was possible to remove 6.5 weight percent of -M20.

The + M20 fraction was washed with tap water as described, obtaining a product with a viscosity of 5700 mPas (1% concentration) and a transparency (0.5%) of 81.3%. The treated peripheral cell layers that still remained adhered could be excised mechanically by intensive abrasion of the + M20 fraction in a home coffee mill, at the lowest milling speed. By repetition of the "milling" it was still possible to remove approximately 12% of the peripheral cell layers, so that in total approximately 18-19% of the + M20 fraction was recovered. These peripheral cell layers can also be excised in aqueous alcohols under intense agitation. If you intensively shake, for example, 1 part of the + M20 fraction for 5 minutes in 1.2 parts of methyl alcohol to 35 percent by weight, and this process is repeated 3 times, you can recover 13.5% of the + M20 fraction, so that a total of 20% of this fraction is conserved. EXAMPLE V Cationic derivative The product of Example III was milled, and 400 g of this ground product was resuspended in 1600 g of a 25 weight percent aqueous isopropanol solution. 100 ml of a 30 weight percent NaOH solution was added. The suspension was heated for 30 minutes in a nitrogen atmosphere with constant stirring. This reaction temperature was maintained for 1 hour, then the suspension was cooled to 55 ° C. The stirring was stopped, and after the settlement of the product it was removed by pouring the excess. The product of the reaction was washed with 1000 ml of a 50 weight percent isopropanol solution, and then treated with 10 ml of glacial acetic acid, in order to neutralize a stoichiometric amount of NaOH. The surplus was eliminated by pouring after the settlement of the product. In this way, 7.8 g of NaOH were removed. 225 g of a 40 weight percent 2, 3-epoxypropyltrimethylammonium chloride solution were added and allowed to penetrate for 1 hour at 30 ° C in the alkaline-treated product. After this, 1100 ml of an 85 weight percent isopropanol solution was used as suspending agent. The nitrogen atmosphere was restored, and the suspension was heated to 65 ° C. This temperature was kept constant for 40 minutes. The supply of nitrogen was then stopped to bring the reaction product into contact with the oxygen in the air and thus adjust the final viscosity of the cationic product of guar. The reaction was carried out for 45 minutes at 65 ° C. The product was then washed with 800 ml of a 85 weight percent isopropanol solution, then with 1000 ml of the same solution. During the washing process, 25 ml of 99% by weight glacial acetic acid were added, whereby the lye was neutralized. The product was recovered by filtration and dried with hot air at 70 ° C. At a concentration of 1% in water, this cationic guar had a viscosity of 880 mPas (based on 10% humidity) and a light transmission ( transparency) of 94.2%. Example VI Carboxymethylation 350 g of a + M20 fraction with a moisture content of 7.5% were moistened with 100 ml of cold water. After 15 minutes, the majority of the sodium monochloroacetate solution consisting of 79 g of sodium monochloroacetate and 184 g of water was added for 24 minutes with stirring. The remaining 100 ml of this solution was added rapidly for 5 minutes. The addition of the reagents was carried out at room temperature. After another 16 minutes of incubation with stirring, the temperature was increased to 50 ° C. Now 27 g of NaOH tablets were added. By virtue of the exothermic reaction of the NaOH pellets, the temperature rose rapidly to 65-66 ° C and was maintained for 36 minutes. The product of the reaction was removed from the reactor and washed twice with water in a ratio of 1: 6. Due to the very rapid absorption of water from the purified carboxymethyl spiits, which were not treated with borax, their time in the water was limited in each case to 2 minutes.

The weight of the strongly fluted spiits was 2640 g.

Therefore, a dehydration process with isopropanol was necessary (1500 g was used). 3261 g of the filtrate were recovered. The weight of the carboxymethylated spiits moistened with alcohol was 879 g with a volatile amount of 66.8%. Since during the reaction no precautionary measures were taken by means of an inert nitrogen bell, the spiits were in contact with the air during the entire reaction interval, which caused a considerable depolymerization. The viscosity of a 1% solution of the carboxylated spiits was 1720 mPas with a transparency of 92.7%. These values were obtained at a temperature of 25 ° C. Example VII 400 g of the preferred quality of guar spiits, with a content of galactomannans of at least 84% were first diluted in a Sigma mixer preheated with 4 ml of a 35% H202 solution were treated with 21 ml of demineralized water for 9 minutes, after which 40 g of NaOH dissolved in 61 ml of demineralized water were added hot. Within 3 minutes the reaction mixture reached the desired temperature of 68 ° C. The reaction temperature of 68-72 ° C was maintained for 20 minutes. The majority of the water was then extracted to the reaction mixture by indirect heating and ventilation for 23 minutes. The reaction mixture was sieved over M20, whereby 30 g of -M20 and 437 g of + M20 (content of H20 10.1%) were obtained. The fraction + M20 was washed twice with water, and in each case 6 parts of tap water were used for 1 part of the unwashed fraction of + M20. The respective washing times were 4 and 5 minutes. The washed, sponged spiits were recovered by simple sieving. 892 g of fluffy spiits were obtained that had a water content of 67.8%. These spiits were dissolved as usual, and this solution produced a viscosity of 2300 mPas and a light transmission of 86.4% (measurements according to the description of example I). Figure 1: The flow diagram shows the treatment of the spiits with bleach and hydrogen peroxide according to the invention, and the possibilities of subsequent processing following the alkaline treatment. EXAMPLE VIII Transparent Conditioning Shampoo A conditioning shampoo of the following composition is made according to processes known to the person skilled in the art: This formulation is adjusted to a viscosity of 3000 mPas by the addition of sodium chloride. The transparency measured at 600 nm is 97%.

E x IX Transparent shower gel for shower bath A transparent gel for shower bath according to processes known to the expert (addition of aminomodified silicone microemulsion to the rest of the mixture): This formulation is adjusted to a viscosity of 2500 mPas by the addition of sodium chloride. The transparency measured at 600 nm is 96%.

Claims (1)

1. CLAIMS Process for the manufacture of pure flour of guar seeds, characterized in that it comprises the following steps: (a) treating the guar spiit with an alkaline solution in the presence of small amounts of hydrogen peroxide, (b) neutralizing partially the alkaline spiit with an organic or inorganic acid (c) mechanical separation of the peripheral cell layers of the guar spiit, (d) treat the spiit with an alcoholic solution (e) grind the spiit to flour Process according to claim 1, characterized in that the alkaline solution used in step (a) is sodium hydroxide, preferably in a concentration of 25 to 50 weight percent, most preferably in a concentration of 33 percent by weight and in an amount of 6 - 10% based on the starting material. Process according to claim 1 or 2, characterized in that the amount of hydrogen peroxide used in step (a) is 0.175 to 0.35 weight percent, most preferably it comprises 0.175 weight percent, being that a 35 weight percent hydrogen peroxide solution is employed. Process according to one of the preceding claims, characterized in that the acid of step (b) sulfuric acid, phosphoric acid or other suitable organic acid, preferably acetic acid. Process according to claim 4, characterized in that the sulfuric acid used in step (b) is used in a concentration of 60 to 80 weight percent, preferably 70 weight percent. Process according to claim 4, characterized in that the phosphoric acid used in step (b) is used in a concentration of 60 to 85 weight percent, preferably 75 weight percent. Process according to one of the preceding claims, characterized in that the alcohol solution used in step (d) is an aqueous solution of ethanol, methanol or preferably isopropanol. Process according to claim 7, characterized in that the aqueous alcohol solution of preferably 20 to 40 weight percent is very preferably a 25 weight percent isopropanol solution. Process according to claim 7 or 8, characterized in that after the removal of the peripheral cell layers in step (c) and before the treatment with an aqueous solution of isopropanol, the spiits are washed in the step ( d) twice with water at 60 to 70 ° C in the presence of a lye, preferably sodium hydroxide. Pure guar seed meal according to one of the preceding claims, characterized in that the guar seed meal in question is derivatized by carboxymethylation, hydroxypropylation or cationization or combinations thereof. Guar seed flour, which as a 1% aqueous solution has a viscosity of up to 9000 mPas, which has a joint content of proteins and non-hydrolysable substances by acids of 0.8 to 1.2%, and which as a 0.5% aqueous solution shows a transparency of at least 80% measured at a wavelength of 500 nm, made according to the process according to one of the preceding claims. Guarseed meal according to claim 10, characterized in that the measured transparency of a 0.5% solution of these derivatives is up to 98% at a wavelength of 500 nm. Guar seed flour according to one of claims 10, 11 and 12, to be used as a thickener for food, cosmetics, pharmaceuticals, for paints and lacquers, for textile dyes, for the extraction of oil as well as for explosive substances . Guar seed meal of hydroxypropyltrimethylammonium chloride which is obtained by the etherification of a guar seed meal obtained with the process according to one of claims 1 to 9 with 2-hydrochloride chloride., 3-epoxypropyltrimethylammonium as the cationic etherifying agent, under alkaline conditions and under an inert gas atmosphere, and the subsequent purification and separation. Guar seed meal of hydroxypropyltrimethylammonium chloride according to claim 14, characterized in that the etherification is carried out in two main steps: a first step in which the cationic etherification agent diffuses into the guar seed meal under alkaline conditions and under an atmosphere of inert gas at a temperature of about 20 to 55 ° C, preferably about 30 to about 50 ° C, and then suspended in an aqueous alcoholic solution, in particular a solution of water-isopropanol containing from 25 to 70% by weight of isopropanol, and a second stage, the actual etherization step under an inert gas atmosphere at a temperature of from about 50 to about 70 ° C, with a temperature from about 60 to about 65 ° being particularly preferred. C. Use of a guar seed meal of hydroxypropyltrimethylammonium chloride in accordance with claim 14 or 15 in transparent aqueous cosmetic formulations intended for use on the hair and / or the skin, and which should be removed again by rinsing, as conditioning agent and / or deposition aid for other conditioning agents upon dilution of the formulations cosmetic 7. Use according to claim 16, characterized in that these cosmetic formulations contain from 0.05 to 0.5%, preferably from 0.1 to 0.3% of guar seed meal of hydroxypropyltrimethylammonium chloride, and at least 60% by weight of water, and have a transparency of at least 92% measured at 600 nanometers. Use according to claim 16 or 17, characterized in that these transparent cosmetic formulations also contain at least one non-volatile silicone in the form of particles with a diameter of less than 35 nanometers, preferably of 20 to 25 nanometers. 19. Use according to claim 18, characterized in that the silicone is present in an amount of 0.1 to 1% by weight, preferably 0.5 to 1% by weight, expressed as active substance with respect to weight of the cosmetic formulation. 20. Aqueous transparent cosmetic formulations intended to be used on the hair and / or the skin, and which must be removed again by rinsing, and which, based on their weight, contain the following: 8 to 30% by weight, preferably 10 to 20% by weight of at least one nonionic, anionic, amphoteric or hybrid ionically active surfactant, expressed as active substance, 0.05 to 0.5% by weight, preferably 0.1 to 0.3% by weight of guar seed meal of hydroxypropyltrimethylammonium chloride in accordance with with claim 14 or 15, optionally 0.1 to 1% by weight, preferably 0.5 to 1% by weight of at least one non-volatile silicone in an aqueous emulsion, whose particle size is less than 35 nanometers, preferably about 20 about 25 nanometers, expressed as active substance, and at least 60% by weight of water, preferably at least 75% by weight of water. 21. Use according to one of claims 16 to 19, or of cosmetic formulations according to claim 20, characterized in that the guar seed flour of hydroxypropyltrimethylammonium chloride has a degree of substitution of about 0.01 to about 0.4, preferably 0.05 to 0.25, and a molecular weight of 50000 to 3 x 106. Use according to one of claims 16 to 19 as well as 20, or of cosmetic formulations according to claim 20 or 21, characterized by the fact that these transparent aqueous cosmetic formulations have a transparency of at least 92% measured at 600 nanometers. Use according to one of claims 16 to 19, or 22, or of cosmetic formulations according to one of claims 20 to 22, characterized in that these transparent cosmetic formulations are in the form of a conditioning shampoo, shower gel or liquid soap.