Title of Invention	SOLUBILIZATES OF PRESERVATIVES AND METHOD FOR PRODUCING THE SAME
Abstract	Described is a solubilizate of a preservative containing an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid that is free of stabilizing agents, as well as one or more emulsifiers with an HLB value between 9 and 18 with a concentration of about 50% and about 95% emulsifier with regard to the total quantity of the solubilizate, and a procedure for the production of such a solubilizate.

Title of Invention

SOLUBILIZATES OF PRESERVATIVES AND METHOD FOR PRODUCING THE SAME

Abstract

Described is a solubilizate of a preservative containing an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid that is free of stabilizing agents, as well as one or more emulsifiers with an HLB value between 9 and 18 with a concentration of about 50% and about 95% emulsifier with regard to the total quantity of the solubilizate, and a procedure for the production of such a solubilizate.

Full Text	The invention concerns a solubilizate of a preserving agent. In the German Patent Application Publication 26 23 682, a procedure for manufacturing a suspension and an emulsion from sorbic acid is described, in which a heated solution of sorbic acid is atomized in a solvent made from water, mixed with a water-soluble, organic solvent having a low boiling point; the resulting fluid is then cooled quickly and the excess solvent is removed. Because of the warming and atomization of the sorbic acid solution, this procedure is very complex. In the document DE 25 19 557, a disinfecting soap is described, which, besides the disinfectant and a non-ionic emulsifier, such as a polysorbate for example, contains a considerable amount of diluent as well as other additional substances as galenicals. This soap disinfects hands or 'other skin areas in the medical field. The document DE 601 03 023 T2 discloses acidic anti-microbial compositions for the treatment of foodstuffs, which comprise an organic acid, a likewise non-ionic surfactant and a stabilizing agent, for example a polysorbate. With considerable dilution, the mixture can be used for treating the surfaces of foodstuffs in order to reduce the microbial population settling on these surfaces. For the preservation of foodstuffs against microbial rotting, there is, in addition to the biological and chemical acidification as well as the heating process, the chemical preservation with bactericidal or bacteriostatic chemicals. The most common preservatives for beverages are sorbic acid (E200 and salts E201-3) and benzoic acid (E201 and salts 211-13). Benzoic acid (BS) acts mainly against yeast and molds; bacteria are only partially inhibited. Sorbic acid (SS) acts likewise against yeasts and molds, but somewhat better also against bacteria, primarily against catalase-positive and anaerobic bacteria. In practice, a mixed preservative of equal parts benzoic acid and sorbic acid proved to have a certain synergetic effect. It is also possible to reduce in this way the adverse effect on the taste of the foodstuff caused by high amounts of preservatives. Usual amounts are 150-200 ppm per preservative in the finished product. The maximum amounts for non-alcoholic drinks are limited to 300 ppm SS or 150 ppm BS; when mixed the maximum amounts are 250 ppm SS + 150 ppm BS. These preservatives are used for beverages and other fluid foodstuffs containing large amounts of water, generally in the form of their water-soluble sodium, calcium and potassium salts. The bactericidal effect, however, is developed exclusively by the undissociated acids. If the foodstuffs to be preserved with benzoic acid and/or sorbic acid contain ascorbic acid, then there exists the danger that, through a reaction of the ascorbic acid with the benzoic acid and/or the sorbic acid, undesired, because health hazardous, reaction products such as benzene, could result. The solubilities of the preservatives mentioned in water, ethanol and oil are: The dissociation of the weak acid SS (pKs = 4.8) and BS (pKs = 4.22) is highly dependent on the pH-value of the medium, in which they are used. For pH-values, as they are common for classic non-alcoholic drinks (pH = 2.8-3.5), 90-100% of SS or BS is undissociated and thereby effective as bactericide. However, due to the poor water-solubility of the acids, a relatively high dose is necessary. In products with low acidity, on the other hand, (pH-values 4.0-neutral), primarily for BS, considerable portions are dissociated that have no effect against microorganisms. The invention therefore has the object to better protect foodstuffs, primarily beverages, against the effects of microorganisms. In order to do so, the invention suggests a solubilizate of a preservative that is free of a stabilizing agent, which contains an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid as well a one or more emulsifiers with a HLB value between 9 and 18. The concentration of emulsifier can lie between 50% and 95% with respect to the total amount of the solubilizate. The sorbic or benzoic acid or the mixture of the two can be contained in the solubilizate in an amount between 5% and 50%. It is advisable to use a polysorbate as the emulsifier, preferably polysorbate 20 and/or polysorbate 80. The solubilizate according to the invention has an excellent bactericidal effect. For example, if, on the one hand 500 mg potassium sorbate and on the other hand in comparison 500 mg sorbic acid-solubilizate with polysorbate 20, are given to an agar nutrient solution, after about three weeks contact time with potassium sorbate there results a bacteria count of 1.6 x 1010, compared to a bacteria count of 3.5 x lO8 with a sorbic acid-solubilizate, in other words a bacteria count smaller by almost two orders of magnitude. The invention is based on the concept of slowing or preventing a dissociation of the organic aids primarily in media that are only weakly acidic through micellation, with the consequence that more undissociated acid is available for the elimination of microorganisms. Therefore, the dose of the micellated organic acids can be lowered considerably. Since the micelles only open upon contact with cell membranes or similar biological material, the acid released from the micelles can act directly on the microorganisms to eliminate them. The invention can be used for foodstuffs of all kinds, in particular in non-alcoholic beverages with high pH values from about 4.0 to 7.0, such as tea, coffee, cocoa and milk beverages. The preservative solubilizates are added to the relevant tea, coffee, cocoa and milk drinks. The dosing occurs individually by the producer of the end product between 100 ppm and 500 ppm, which means, assuming a twenty percent benzoic acid solubilizate between 500 ppm and 1000 ppm per liter of end product. The invention can furthermore be used for the preservation of milk products such as milk, cheese and yogurt. The solubilizates are applied primarily to the cheese rind. The sorbic acid solubilizate may also be used in small amounts in cheese. Moreover, vegetables, fruits and herbs can be submerged in an aqueous solution of the solubilizate according to the invention and thereby be better protected against mold, fungi and yeasts and also made longer-lasting. Finally, the invention also allows for the preservation of surfaces of wood or other artificial materials, so that, for example, furniture or the surfaces of medical apparatus and devices can be treated for preservation with solubilizates in diluted watery solution. The bactericidal effect of a benzoic acid solubilizate, for example, is demonstrated by an investigation of a publically ordered and sworn expert for foodstuff chemistry. Test materials: 1) Benzoic acid: raw material benzoic acid, company Merck Art. No. 1.00136 2) Benzoic acid solubilizate solution: raw material 20% solution of benzoic acid solubilizate, company AQUANOVA Lot- No. L096.06.LM.01.01 3) Nutrient solution: Yeast Malt Broth, company Sigma Art. No. Y 3752 4) Nutrient Agar: see 3) with addition of agar, company Fluka Art. No. 05040, 20 g per liter nutrient solution 5) Yeast culture: saccharomyces cerevisae, company DSMZ Art. No. 7044 The composition of the 20% solution of benzoic acid solubilizate according to 2) is given in the following examples under EW0108/8. The following table 1 shows the influence of benzoic acid on the yeast growth and table 2 gives the inhibition of the yeast growth achieved, each at pH 6.2 and room temperature. Table 1 shows that even with a benzoic acid concentration of 500 ppm, there is still a high yeast growth after 29 days of contact time. In comparison, Table 2 shows that with a benzoic acid concentration of 500 ppm in solubilizate, the yeast growth is considerably slowed down starting right at the beginning of the addition of the solubilizate, and that after 29 days of contact time the yeast is completely eliminated. Even after the third day of contact, a benzoic acid concentration in solubilizate of 300 ppm leads to a continuous growth reduction of the yeast. Preferred forms of implementation of the invented solubilizate are given in the subclaims. It is recommended when the sorbic acid solubilizate exhibits about 5% by weight sorbic acid and 95% by weight polysorbate 20. For the benzoic acid, a solubilizate that contains about 20% by weight benzoic acid and about 80% by weight polysorbate 20 is advisable. Furthermore, it is advisable for many applications, for example for an addition to acidified beverages, if the benzoic acid solubilizate contains a portion of a wetting agent, which binds the micellated benzoic acid to such a degree that free benzoic acid is practically non-existent in the beverage. If the beverage is, for instance, mixed with ascorbic acid, then the effect of the ascorbic acid on the benzoic acid can easily cause the formation of benzoene which is damaging for foodstuffs. The benzoic acid solubilizate according to the present invention prevents the formation of benzoene in acidified beverages. The wetting agent advisably includes a mixture of an oil containing primarily middle-chain triglycerides with a small portion of wax, Cera alba, for example. The wetting agent can be represented in the benzoic acid solubilizate with a concentration of about 2% by weight to 10% by weight, whereby about 3% by weight to 10% by weight could fall upon the oil and about 1% by weight to about 2% by weight could fall upon the wax. In detail, a benzoic solubilizate proves to be especially favorable in its bactericidal effect, when it contains about 21% by weight benzoic acid, about 5% by weight of a primarily middle-chain triglyceride oil, about 73% by weight polysorbate 20 and about 1% by weight of a wax, such as beeswax (Cera alba). Instead of polysorbate 20, polysorbate 80 can be used in about the same amount in the benzoic acid solubilizate. Finally, a solubilizate comes into consideration, which consists of about 5% by weight sorbic acid, about 5% by weight benzoic acid about 90% by weight polysorbate 20. Subsequently, without limiting the generality of the patent claims, five special formulations will be given, which also contain information about the corresponding method of production of the individual solubilizates. In the simplest form of the manufacturing process, this is designed so that the emulsifier is warmed to about 70°C up to about 90°C, in the case of the polysorbate 20 to about 72°C up to about 85°C, preferably warmed to about 80°C up to about 85°C, the aliphatic and/or the aromatic acid is slowly, that means without considerable (max. 5°C) cooling of the emulsifier, while being stirred, incorporated in the warm emulsifier, after complete mixing, the mixture is further warmed to about 83°C up to about 90°C, while being constantly stirred, and is well homogenized. Then the solubilizate is allowed to cool for bottling to under 35°C, whereby it is recommended that the mixture be cooled quickly to 40°C. It is advisable to introduce an emulsifier of about 50 % by weight to about 95 % by weight, such as polysorbate 20 and/or polysorbate 80, into the production procedure. For the aliphatic and/or aromatic acid it is recommended that about 5% by weight to about 50% by weight be used. If the benzoic acid solubilizate contains a wetting agent, one should proceed so that, first, the wetting agent is warmed to about 55°C up to about 65°C, preferably 58°C up to about 62°C, and homogenized, that the benzoic acid is added to the warm wetting agent and homogenized again while being stirred, that then about one fifth of the polysorbate amount, so about 150 g per kg solubilizate, is added to the benzoic acid / wetting agent mixture and the mass thereby obtained is warmed while being stirred to about 80°C up to about 90°C and homogenized and that, then, the rest of the polysorbate, so four fifths of it, is added slowly, stirred well and the temperature is held at about 80°C to 90°C for at least 5 minutes. Then if necessary, it can be cooled quickly to 40°C and bottled at about 35°C. In this procedure about 2% by weight to about 10% by weight wetting agent can be used. If in the preferred design of the procedure, a mixture of an oil containing predominantly middle-chain triglyceride and a wax is used as wetting agent, it is advisable to incorporate about 1% to 1.5% by weight of the wax in about 5% by weight of the oil warmed as described, and to homogenize the mixture and finally add about 20% by weight benzoic acid and then add, as described above, the polysorbate. Otherwise, the preferred methods for the procedure according to the present invention are given in the procedure claims. For the solubilizate according to the present invention, the radius distributions of the micelles formed have been measured. The result is shown in the attached figures 1 and 2. The measurements were conducted according to the field-flow method of the Wyatt Technologie Europe GmbH. Figure 1 refers to the 5% sorbic acid solubilizate and figure 2 applies for the 20% benzoic acid solubilizate. Recognizable is that the middle micelle radius for the sorbic acid solubilizate lies under 10 nm and the middle micelle radius for the benzoic acid solubilizate lies under 20 nm. In the formulations MCT means medium chain triglyceride. The weight information in percent refer to the total weight of the solubilizate = 100% by weight. EW-No.: EW0108/8 Label: Water and Fat Soluble 20% Benzoic Acid Solubilizate Ingredients: 200 g Benzoic acid; AppliChem (AGT-Material No.: 10080/079) 800 g Polysorbate 20; Lamesorb SML 20; Cognis AGT-Material No.: 10520/016) Procedure: - Heat polysorbate 20 to 80-85°C. Incorporate benzoic acid slowly while stirring Stir continuously, heat to max. 90°C and homogenize well - Allow to cool to Appearance: Light yellow, viscous, transparent Storage Conditions: Dark, at room temperature ( [watermark:] EW EW-No.: EW0108/80/CA Label: NovaSol® Benzoic Water and fat soluble 20% Benzoic Acid Solubilizate Ingredients: 210 g Benzoic acid, AppliChem (AGT-Material No.: 10080/079) 50 g Delios VK kosher (MCT-oil); Cognis (AGT-Material No. : 10.460/016) 739 g Polysorbate 80; Lamesorb SMO 20; Cognis (AGT-Material No.: 10530/016) 1 g Cera alba (beeswax); Roeper (AGT-Material No.: 10741/075) Procedure: - Warm MCT-oil (58-62°C) and Cera alba slowly; stir to mix homogenously. To the mixture, add benzoic acid and homogenize well by stirring (58-62°C) Add about 20% of the polysorbate 80 quantity (approx. 150g/kg) and stir while heating to 83-87°C until the mixture is homogenous. Slowly add the rest of the polysorbate 80 quantity, stir well and hold the temperature at 83-87°C for at least 5 minutes. Stir constantly while lowering the temperature as quickly as possible to 40°C Bottle at 40°C or cooler. Appearance: Light yellow/white, viscous Storage Conditions: Dark, at room temperature ( [watermark:] EW EW-No.: EW0109/12 Label: Water and Fat Soluble 5% Sorbic Acid/ 5% Benzoic Acid Solubilizate (Combination) Ingredients: 50 g Sorbic acid; Kramer & Martin (AGT-Material No.: 10642/88) 50 g Benzoic acid; AppliChem (AGT-Material No.: 10080/079) 900 g Polysorbate 20; Lamesorb SML 20; Cognis (AGT-Material No.: 10520/016) Procedure: - Mix sorbic and benzoic acid. - Warm polysorbate 20 to 80-85°C. - Mix powder mixture and polysorbate (83-87%) while stirring. - Heat everything, while stirring, to about 88-92°C and homogenize well. - Cool to Appearance: Yellow, viscous, transparent Storage Conditions: Dark, at room temperature ( [watermark:] EW EW-No.: EW0108/CA/1 Label: NovaSOL® Benzoic Water and fat soluble 20% Benzoic Acid Solubilizate Ingredients: 210 g Benzoic acid, AppliChem (AGT-Material No.: 10080/079) 50 g Delios VK kosher (MCT-oil); Cognis (AGT-Material No.: 1Q460/016) 738.5 g Polysorbate 20; Lamesorb SML 20; Cognis (AGT-Material No.: 10520/016) 1.5 g Cera alba (beeswax); Roeper (AGT-Material No.: 10741/075) Procedure: - Warm MCT-oil (58-61°C) and incorporate Cera alba slowly while stirring and mix homogenously. To the mixture, add benzoic acid and homogenize well by stirring (58-62°C) . - Add about 20% of the polysorbate 20 quantity (approx. 150g/kg) and stir while heating to 83-87°C until the mixture is homogenous.. Slowly add the rest of the polysorbate 20 quantity, stir well and hold the temperature at 83-87°C for at least 5 minutes. Stir constantly while lowering the temperature as quickly as possible to 40°C - Bottle at 40°C or cooler. Appearance: Light yellow/white, viscous Storage Conditions: Dark, at room temperature ( [watermark:] EW EW-No.: EW0107/5 Label: Water and Fat Soluble 5% Sorbic Acid Solubilizate Ingredients: 50 g Sorbic acid; AppliChem (AGT-Material No.: 10641/079) 950 g Polysorbate 20; Lamesorb SML 20; Cognis AGT-Material No.: 10520/016) Procedure: - Heat polysorbate 20 to 72-77°C. - Oncorporate sorbic acid slowly while stirring. Stir continuously, heat to max. 90°C and homogenize well - Allow to cool to Appearance: Light yellow, viscous, transparent Storage Conditions: Dark, at room temperature ( WE CLAIM 1. Solubilizate of a preservative containing an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid that is free of stabilizing agents, as well as one or more emulsifiers with an HLB value between 9 and 18 with a concentration of about 50% by weight and about 95% by weight emulsifier with regard to the total quantity of the solubilizate. 2. Solubilizate according to claim 1 with a concentration between 5% by weight and 50% by weight aliphatic and/or aromatic acid. 3. Solubilizate according to claim 1 or 2, in which the emulsifier is a polysorbate, preferably polysorbate 20 and/or polysorbate 80. 4. Solubilizate according to one of the previously mentioned claims consisting of about 5% by weight sorbic acid and about 95% by weight polysorbate 20. 5. Solubilizate according to one of the claims 1 through 4 consisting of about 20% by weight benzoic acid and about 80% by weight polysorbate 20. 6. Solubilizate according to one of the claims 1 through 4 consisting of about 20% by weight benzoic acid, about 5% by weight of an oil containing predominately medium chain triglycerides, about 73.5% by weight polysorbate 20 and about 1.5% by weight' of a wax. 7. Solubilizate according to claim 6 in which the wax is beeswax for example in the form of Cera alba. 8. Solubilizate according to claim 6 or 7, in which the polysorbate 20 is replaced by polysorbate 80. 9. Solubilizate according to one of the claims 1 through 3 consisting of about 5% by weight sorbic acid, about 5% by weight benzoic acid and about 90% by weight polysorbate 20. 10. Procedure for production of a solubilizate according to one or more of the previous claims, in which an emulsifier with an HLB value of 9-18 is heated to about 70°C up to 90°C, the aliphatic and/or aromatic acid is mixed without considerable cooling of the emulsifier with the warm emulsifier while stirring, after complete mixing, the mixture, while continuously being stirred, is heated to about 83°C up to about 90°C and well homogenized and finally cooled. 11. Procedure according to claim 10, in which about 50% by weight to about 95% by weight of emulsifier is heated. 12. Procedure according to claim 10 or 11, in which a polysorbate, preferably polysorbate 20 and/or polysorbate 80 is used as the emulsifier. 13. Procedure according to claim 12, in which the polysorbate in heated to about 72°C up to about 85°C, preferably to 80°C up to 85°C. 14. Procedure according to one of the claims 10 through 13, in which about 5% ny weight to about 50% by weight of aliphatic and/or aromatic acid is mixed into the warm emulsifier. 15. Procedure according to one of the claims 10 through 14, in which it is quickly cooled to 40°C. 16. Procedure according to one of the claims 10 through 15, in which benzoic acid is added to a heated and homogenized wetting agent and the mixture is homogenized, that then about a fifth of the polysorbate quantity is added to the benzoic acid / wetting agent mixture and the resultant mass is stirred and heated and homogenized and finally the rest of the polysorbate quantity is slowly added and stirred at a higher temperature. 17. Procedure according to claim 16, in which the wetting agent is heated to about 55°C to about 65°C, preferably 58°C to about 62°C. 18. Procedure according to claim 15 or 16, in which the increased temperature is selected at about 80°C up to about 90°C. 19. Procedure according to one of the claims 16 through 19, in which a wetting agent is selected that consists of a mixture of an oil containing predominately medium chain triglyceride and a wax, preferably Cera alba. 20. Procedure according to claim 19, in which the surfactant is mixed from about 5% by weight of the oil and about 1% by weight to about 1.5% by weight of the wax. 21. Use of a solubilizate free of stabilizing agents according to one of the claims 1 through 9, as preservative additive to foodstuffs, in particular non-alcoholic beverages with a high pH value from about 4.0 to about 7.0, for example, such as tea, coffee, cocoa and milk drinks. 22. Use according to claim 21 with a dosage between 500 ppm and 1000 ppm per liter end product. 23. Use of a solubilizate free of stabilizing agents according to one of the claims 1 through 9 as preservative additive to milk products such as milk, cheese and yogurt, whereby the solubilizate is applied mainly to the cheese rind. 24. Use of a solubilizate free of stabilizing agents according to one of the claims 1 through 9 as preservative additive to vegetables, fruits and herbs, advisably by submersion of vegetables or fruits or herbs in an aqueous solution of the solubilizate. 25. Use of a solubilizate free of stabilizing agents according to one of the claims 1 through 9 for the preservation of wood surfaces or other artificial materials such as furniture, or of medical apparatus and devices through treatment with a diluted aqueous solution of the solubilizate. Described is a solubilizate of a preservative containing an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid that is free of stabilizing agents, as well as one or more emulsifiers with an HLB value between 9 and 18 with a concentration of about 50% and about 95% emulsifier with regard to the total quantity of the solubilizate, and a procedure for the production of such a solubilizate.

Full Text

The invention concerns a solubilizate of a preserving agent.
In the German Patent Application Publication 26 23 682, a procedure for manufacturing a suspension and an emulsion from sorbic acid is described, in which a heated solution of sorbic acid is atomized in a solvent made from water, mixed with a water-soluble, organic solvent having a low boiling point; the resulting fluid is then cooled quickly and the excess solvent is removed. Because of the warming and atomization of the sorbic acid solution, this procedure is very complex.
In the document DE 25 19 557, a disinfecting soap is described, which, besides the disinfectant and a non-ionic emulsifier, such as a polysorbate for example, contains a considerable amount of diluent as well as other additional substances as galenicals. This soap disinfects hands or 'other skin areas in the medical field.
The document DE 601 03 023 T2 discloses acidic anti-microbial compositions for the treatment of foodstuffs, which comprise an organic acid, a likewise non-ionic surfactant and a stabilizing agent, for example a polysorbate. With considerable dilution, the mixture can be used for treating the surfaces of foodstuffs in order to reduce the microbial population settling on these surfaces.
For the preservation of foodstuffs against microbial rotting, there is, in addition to the biological and chemical acidification as well as the heating process, the chemical preservation with bactericidal or bacteriostatic chemicals.

The most common preservatives for beverages are sorbic acid (E200 and salts E201-3) and benzoic acid (E201 and salts 211-13).
Benzoic acid (BS) acts mainly against yeast and molds; bacteria are only partially inhibited. Sorbic acid (SS) acts likewise against yeasts and molds, but somewhat better also against bacteria, primarily against catalase-positive and anaerobic bacteria. In practice, a mixed preservative of equal parts benzoic acid and sorbic acid proved to have a certain synergetic effect. It is also possible to reduce in this way the adverse effect on the taste of the foodstuff caused by high amounts of preservatives. Usual amounts are 150-200 ppm per preservative in the finished product. The maximum amounts for non-alcoholic drinks are limited to 300 ppm SS or 150 ppm BS; when mixed the maximum amounts are 250 ppm SS + 150 ppm BS.
These preservatives are used for beverages and other fluid foodstuffs containing large amounts of water, generally in the form of their water-soluble sodium, calcium and potassium salts. The bactericidal effect, however, is developed exclusively by the undissociated acids. If the foodstuffs to be preserved with benzoic acid and/or sorbic acid contain ascorbic acid, then there exists the danger that, through a reaction of the ascorbic acid with the benzoic acid and/or the sorbic acid, undesired, because health hazardous, reaction products such as benzene, could result.
The solubilities of the preservatives mentioned in water, ethanol and oil are:

The dissociation of the weak acid SS (pKs = 4.8) and BS (pKs = 4.22) is highly dependent on the pH-value of the medium, in which they are used. For pH-values, as they are common for classic non-alcoholic drinks (pH = 2.8-3.5), 90-100% of SS or BS is undissociated and thereby effective as bactericide. However, due to the poor water-solubility of the acids, a relatively high dose is necessary.
In products with low acidity, on the other hand, (pH-values 4.0-neutral), primarily for BS, considerable portions are dissociated that have no effect against microorganisms.

The invention therefore has the object to better protect foodstuffs, primarily beverages, against the effects of microorganisms.
In order to do so, the invention suggests a solubilizate of a preservative that is free of a stabilizing agent, which contains an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid as well a one or more emulsifiers with a HLB value

between 9 and 18. The concentration of emulsifier can lie between 50% and 95% with respect to the total amount of the solubilizate. The sorbic or benzoic acid or the mixture of the two can be contained in the solubilizate in an amount between 5% and 50%. It is advisable to use a polysorbate as the emulsifier, preferably polysorbate 20 and/or polysorbate 80.
The solubilizate according to the invention has an excellent bactericidal effect. For example, if, on the one hand 500 mg potassium sorbate and on the other hand in comparison 500 mg sorbic acid-solubilizate with polysorbate 20, are given to an agar nutrient solution, after about three weeks contact time with potassium sorbate there results a bacteria count of 1.6 x 1010, compared to a bacteria count of 3.5 x lO8 with a sorbic acid-solubilizate, in other words a bacteria count smaller by almost two orders of magnitude.
The invention is based on the concept of slowing or preventing a dissociation of the organic aids primarily in media that are only weakly acidic through micellation, with the consequence that more undissociated acid is available for the elimination of microorganisms. Therefore, the dose of the micellated organic acids can be lowered considerably. Since the micelles only open upon contact with cell membranes or similar biological material, the acid released from the micelles can act directly on the microorganisms to eliminate them.
The invention can be used for foodstuffs of all kinds, in particular in non-alcoholic beverages with high pH values from about 4.0 to 7.0, such as tea, coffee, cocoa and milk beverages. The preservative solubilizates are added to the relevant tea,

coffee, cocoa and milk drinks. The dosing occurs individually by the producer of the end product between 100 ppm and 500 ppm, which means, assuming a twenty percent benzoic acid solubilizate between 500 ppm and 1000 ppm per liter of end product.
The invention can furthermore be used for the preservation of milk products such as milk, cheese and yogurt. The solubilizates are applied primarily to the cheese rind. The sorbic acid solubilizate may also be used in small amounts in cheese. Moreover, vegetables, fruits and herbs can be submerged in an aqueous solution of the solubilizate according to the invention and thereby be better protected against mold, fungi and yeasts and also made longer-lasting. Finally, the invention also allows for the preservation of surfaces of wood or other artificial materials, so that, for example, furniture or the surfaces of medical apparatus and devices can be treated for preservation with solubilizates in diluted watery solution.
The bactericidal effect of a benzoic acid solubilizate, for example, is demonstrated by an investigation of a publically ordered and sworn expert for foodstuff chemistry.
Test materials:
1) Benzoic acid: raw material benzoic acid, company Merck Art.
No. 1.00136
2) Benzoic acid solubilizate solution: raw material 20%
solution of benzoic acid solubilizate, company AQUANOVA Lot-
No. L096.06.LM.01.01
3) Nutrient solution: Yeast Malt Broth, company Sigma Art. No.
Y 3752

4) Nutrient Agar: see 3) with addition of agar, company Fluka
Art. No. 05040, 20 g per liter nutrient solution
5) Yeast culture: saccharomyces cerevisae, company DSMZ Art.
No. 7044
The composition of the 20% solution of benzoic acid solubilizate according to 2) is given in the following examples under EW0108/8.
The following table 1 shows the influence of benzoic acid on the yeast growth and table 2 gives the inhibition of the yeast growth achieved, each at pH 6.2 and room temperature. Table 1 shows that even with a benzoic acid concentration of 500 ppm, there is still a high yeast growth after 29 days of contact time. In comparison, Table 2 shows that with a benzoic acid concentration of 500 ppm in solubilizate, the yeast growth is considerably slowed down starting right at the beginning of the addition of the solubilizate, and that after 29 days of contact time the yeast is completely eliminated. Even after the third day of contact, a benzoic acid concentration in solubilizate of 300 ppm leads to a continuous growth reduction of the yeast.
Preferred forms of implementation of the invented solubilizate are given in the subclaims. It is recommended when the sorbic acid solubilizate exhibits about 5% by weight sorbic acid and 95% by weight polysorbate 20. For the benzoic acid, a solubilizate that contains about 20% by weight benzoic acid and about 80% by weight polysorbate 20 is advisable. Furthermore, it is advisable for many applications, for example for an addition to acidified beverages, if the benzoic acid solubilizate contains a portion of a wetting agent, which binds the micellated benzoic acid to such a degree that free benzoic acid is practically non-existent in

the beverage. If the beverage is, for instance, mixed with ascorbic acid, then the effect of the ascorbic acid on the benzoic acid can easily cause the formation of benzoene which is damaging for foodstuffs. The benzoic acid solubilizate according to the present invention prevents the formation of benzoene in acidified beverages. The wetting agent advisably includes a mixture of an oil containing primarily middle-chain triglycerides with a small portion of wax, Cera alba, for example.
The wetting agent can be represented in the benzoic acid solubilizate with a concentration of about 2% by weight to 10% by weight, whereby about 3% by weight to 10% by weight could fall upon the oil and about 1% by weight to about 2% by weight could fall upon the wax.
In detail, a benzoic solubilizate proves to be especially favorable in its bactericidal effect, when it contains about 21% by weight benzoic acid, about 5% by weight of a primarily middle-chain triglyceride oil, about 73% by weight polysorbate 20 and about 1% by weight of a wax, such as beeswax (Cera alba). Instead of polysorbate 20, polysorbate 80 can be used in about the same amount in the benzoic acid solubilizate. Finally, a solubilizate comes into consideration, which consists of about 5% by weight sorbic acid, about 5% by weight benzoic acid about 90% by weight polysorbate 20.

Subsequently, without limiting the generality of the patent claims, five special formulations will be given, which also contain information about the corresponding method of production of the individual solubilizates. In the simplest form of the manufacturing process, this is designed so that the emulsifier is warmed to about 70°C up to about 90°C, in the case of the polysorbate 20 to about 72°C up to about 85°C, preferably warmed to about 80°C up to about 85°C, the aliphatic and/or the aromatic acid is slowly, that means without considerable (max. 5°C) cooling of the emulsifier, while being stirred, incorporated in the warm emulsifier, after complete mixing, the mixture is further warmed to about 83°C up to about 90°C, while being constantly stirred, and is well homogenized. Then the solubilizate is allowed to cool for bottling to under 35°C, whereby it is recommended that the mixture be cooled quickly to 40°C. It is advisable to introduce an emulsifier of about 50 % by weight to about 95 % by weight, such as polysorbate 20 and/or polysorbate 80, into the production procedure. For the aliphatic and/or aromatic acid it is recommended that about 5% by weight to about 50% by weight be used.
If the benzoic acid solubilizate contains a wetting agent, one should proceed so that, first, the wetting agent is warmed to about 55°C up to about 65°C, preferably 58°C up to about 62°C, and homogenized, that the benzoic acid is added to the warm wetting agent and homogenized again while being stirred, that then about one fifth of the polysorbate amount, so about 150 g per kg solubilizate, is added to the benzoic acid / wetting agent mixture and the mass thereby obtained is warmed while being stirred to about 80°C up to about 90°C and homogenized and that, then, the rest of the polysorbate, so four fifths of it, is added slowly, stirred well and the temperature is held at about 80°C to 90°C for at least 5

minutes. Then if necessary, it can be cooled quickly to 40°C and bottled at about 35°C. In this procedure about 2% by weight to about 10% by weight wetting agent can be used. If in the preferred design of the procedure, a mixture of an oil containing predominantly middle-chain triglyceride and a wax is used as wetting agent, it is advisable to incorporate about 1% to 1.5% by weight of the wax in about 5% by weight of the oil warmed as described, and to homogenize the mixture and finally add about 20% by weight benzoic acid and then add, as described above, the polysorbate. Otherwise, the preferred methods for the procedure according to the present invention are given in the procedure claims.
For the solubilizate according to the present invention, the radius distributions of the micelles formed have been measured. The result is shown in the attached figures 1 and 2. The measurements were conducted according to the field-flow method of the Wyatt Technologie Europe GmbH. Figure 1 refers to the 5% sorbic acid solubilizate and figure 2 applies for the 20% benzoic acid solubilizate. Recognizable is that the middle micelle radius for the sorbic acid solubilizate lies under 10 nm and the middle micelle radius for the benzoic acid solubilizate lies under 20 nm.
In the formulations MCT means medium chain triglyceride. The weight information in percent refer to the total weight of the solubilizate = 100% by weight.
EW-No.: EW0108/8
Label: Water and Fat Soluble
20% Benzoic Acid Solubilizate

Ingredients:
200 g Benzoic acid; AppliChem (AGT-Material No.: 10080/079)
800 g Polysorbate 20; Lamesorb SML 20; Cognis AGT-Material No.: 10520/016)
Procedure:
- Heat polysorbate 20 to 80-85°C.
Incorporate benzoic acid slowly while stirring
Stir continuously, heat to max. 90°C and homogenize well
- Allow to cool to Appearance:
Light yellow, viscous, transparent
Storage Conditions:
Dark, at room temperature ( [watermark:] EW
EW-No.: EW0108/80/CA
Label: NovaSol® Benzoic
Water and fat soluble
20% Benzoic Acid Solubilizate
Ingredients:
210 g Benzoic acid, AppliChem (AGT-Material No.: 10080/079)
50 g Delios VK kosher (MCT-oil); Cognis (AGT-Material No. : 10.460/016)

739 g Polysorbate 80; Lamesorb SMO 20; Cognis (AGT-Material No.: 10530/016)
1 g Cera alba (beeswax); Roeper (AGT-Material No.: 10741/075)
Procedure:
- Warm MCT-oil (58-62°C) and Cera alba slowly; stir to mix homogenously.
To the mixture, add benzoic acid and homogenize well by stirring (58-62°C)
Add about 20% of the polysorbate 80 quantity (approx. 150g/kg) and stir while heating to 83-87°C until the mixture is homogenous.
Slowly add the rest of the polysorbate 80 quantity, stir well and hold the temperature at 83-87°C for at least 5 minutes.
Stir constantly while lowering the temperature as quickly as possible to 40°C Bottle at 40°C or cooler.
Appearance:
Light yellow/white, viscous
Storage Conditions:
Dark, at room temperature ( [watermark:] EW
EW-No.: EW0109/12
Label: Water and Fat Soluble
5% Sorbic Acid/ 5% Benzoic Acid Solubilizate (Combination)

Ingredients:
50 g Sorbic acid; Kramer & Martin (AGT-Material No.: 10642/88)
50 g Benzoic acid; AppliChem (AGT-Material No.: 10080/079)
900 g Polysorbate 20; Lamesorb SML 20; Cognis (AGT-Material No.: 10520/016)
Procedure:
- Mix sorbic and benzoic acid.
- Warm polysorbate 20 to 80-85°C.
- Mix powder mixture and polysorbate (83-87%) while
stirring.
- Heat everything, while stirring, to about 88-92°C and
homogenize well.
- Cool to Appearance:
Yellow, viscous, transparent
Storage Conditions:
Dark, at room temperature ( [watermark:] EW
EW-No.: EW0108/CA/1
Label: NovaSOL® Benzoic
Water and fat soluble
20% Benzoic Acid Solubilizate
Ingredients:
210 g Benzoic acid, AppliChem (AGT-Material No.: 10080/079)

50 g Delios VK kosher (MCT-oil); Cognis (AGT-Material No.: 1Q460/016)
738.5 g Polysorbate 20; Lamesorb SML 20; Cognis (AGT-Material No.: 10520/016)
1.5 g Cera alba (beeswax); Roeper (AGT-Material No.: 10741/075)
Procedure:
- Warm MCT-oil (58-61°C) and incorporate Cera alba slowly
while stirring and mix homogenously.
To the mixture, add benzoic acid and homogenize well by stirring (58-62°C) .
- Add about 20% of the polysorbate 20 quantity (approx.
150g/kg) and stir while heating to 83-87°C until the
mixture is homogenous..
Slowly add the rest of the polysorbate 20 quantity, stir
well and hold the temperature at 83-87°C for at least 5
minutes.
Stir constantly while lowering the temperature as quickly
as possible to 40°C
- Bottle at 40°C or cooler.
Appearance:
Light yellow/white, viscous
Storage Conditions:
Dark, at room temperature ( [watermark:] EW

EW-No.: EW0107/5
Label: Water and Fat Soluble
5% Sorbic Acid Solubilizate
Ingredients:
50 g Sorbic acid; AppliChem (AGT-Material No.:
10641/079)
950 g Polysorbate 20; Lamesorb SML 20; Cognis
AGT-Material No.: 10520/016)
Procedure:
- Heat polysorbate 20 to 72-77°C.
- Oncorporate sorbic acid slowly while stirring.
Stir continuously, heat to max. 90°C and homogenize well
- Allow to cool to Appearance:
Light yellow, viscous, transparent
Storage Conditions:
Dark, at room temperature (
WE CLAIM
1. Solubilizate of a preservative containing an aliphatic
and/or aromatic acid such as sorbic acid and/or benzoic acid
that is free of stabilizing agents, as well as one or more
emulsifiers with an HLB value between 9 and 18 with a
concentration of about 50% by weight and about 95% by weight
emulsifier with regard to the total quantity of the
solubilizate.
2. Solubilizate according to claim 1 with a concentration
between 5% by weight and 50% by weight aliphatic and/or
aromatic acid.
3. Solubilizate according to claim 1 or 2, in which the
emulsifier is a polysorbate, preferably polysorbate 20
and/or polysorbate 80.
4. Solubilizate according to one of the previously mentioned
claims consisting of about 5% by weight sorbic acid and
about 95% by weight polysorbate 20.
5. Solubilizate according to one of the claims 1 through 4
consisting of about 20% by weight benzoic acid and about 80%
by weight polysorbate 20.
6. Solubilizate according to one of the claims 1 through 4
consisting of about 20% by weight benzoic acid, about 5% by
weight of an oil containing predominately medium chain
triglycerides, about 73.5% by weight polysorbate 20 and
about 1.5% by weight' of a wax.

7. Solubilizate according to claim 6 in which the wax is
beeswax for example in the form of Cera alba.
8. Solubilizate according to claim 6 or 7, in which the
polysorbate 20 is replaced by polysorbate 80.
9. Solubilizate according to one of the claims 1 through 3
consisting of about 5% by weight sorbic acid, about 5% by
weight benzoic acid and about 90% by weight polysorbate 20.

10. Procedure for production of a solubilizate according to one
or more of the previous claims, in which an emulsifier with
an HLB value of 9-18 is heated to about 70°C up to 90°C, the
aliphatic and/or aromatic acid is mixed without considerable
cooling of the emulsifier with the warm emulsifier while
stirring, after complete mixing, the mixture, while
continuously being stirred, is heated to about 83°C up to
about 90°C and well homogenized and finally cooled.
11. Procedure according to claim 10, in which about 50% by
weight to about 95% by weight of emulsifier is heated.
12. Procedure according to claim 10 or 11, in which a
polysorbate, preferably polysorbate 20 and/or polysorbate 80
is used as the emulsifier.
13. Procedure according to claim 12, in which the polysorbate
in heated to about 72°C up to about 85°C, preferably to 80°C
up to 85°C.
14. Procedure according to one of the claims 10 through 13, in
which about 5% ny weight to about 50% by weight of aliphatic
and/or aromatic acid is mixed into the warm emulsifier.

15. Procedure according to one of the claims 10 through 14, in
which it is quickly cooled to 40°C.
16. Procedure according to one of the claims 10 through 15, in
which benzoic acid is added to a heated and homogenized
wetting agent and the mixture is homogenized, that then
about a fifth of the polysorbate quantity is added to the
benzoic acid / wetting agent mixture and the resultant mass
is stirred and heated and homogenized and finally the rest
of the polysorbate quantity is slowly added and stirred at a
higher temperature.
17. Procedure according to claim 16, in which the wetting agent
is heated to about 55°C to about 65°C, preferably 58°C to
about 62°C.
18. Procedure according to claim 15 or 16, in which the
increased temperature is selected at about 80°C up to about
90°C.
19. Procedure according to one of the claims 16 through 19, in
which a wetting agent is selected that consists of a mixture
of an oil containing predominately medium chain triglyceride
and a wax, preferably Cera alba.
20. Procedure according to claim 19, in which the surfactant is
mixed from about 5% by weight of the oil and about 1% by
weight to about 1.5% by weight of the wax.
21. Use of a solubilizate free of stabilizing agents according
to one of the claims 1 through 9, as preservative additive
to foodstuffs, in particular non-alcoholic beverages with a

high pH value from about 4.0 to about 7.0, for example, such as tea, coffee, cocoa and milk drinks.
22. Use according to claim 21 with a dosage between 500 ppm and
1000 ppm per liter end product.
23. Use of a solubilizate free of stabilizing agents according
to one of the claims 1 through 9 as preservative additive to
milk products such as milk, cheese and yogurt, whereby the
solubilizate is applied mainly to the cheese rind.

24. Use of a solubilizate free of stabilizing agents according
to one of the claims 1 through 9 as preservative additive to
vegetables, fruits and herbs, advisably by submersion of
vegetables or fruits or herbs in an aqueous solution of the
solubilizate.
25. Use of a solubilizate free of stabilizing agents according
to one of the claims 1 through 9 for the preservation of
wood surfaces or other artificial materials such as
furniture, or of medical apparatus and devices through
treatment with a diluted aqueous solution of the
solubilizate.

Described is a solubilizate of a preservative containing an aliphatic and/or aromatic acid such as sorbic acid and/or benzoic acid that is free of stabilizing agents, as well as one or more emulsifiers with an HLB value between 9 and 18 with a concentration of about 50% and about 95% emulsifier with regard to the total quantity of the solubilizate, and a procedure for the production of such a solubilizate.

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Patent Number

268403

Indian Patent Application Number

3587/KOLNP/2008

PG Journal Number

36/2015

Publication Date

04-Sep-2015

Grant Date

28-Aug-2015

Date of Filing

03-Sep-2008

Name of Patentee

DRITTE PATENTPORTFOLIO BETEILIGUNGSGESELLSCHAFT mbH & Co. KG

Applicant Address

BERLINER STRASSE 1 12529 SCHONEFELD/WALTERSDORF, GERMANY.

Inventors:

#	Inventor's Name	Inventor's Address
1	BEHNAM, DARIUSH	SCHWALBENWEG 9, 64380 ROSSDORF

PCT International Classification Number

A23L 3/3463

PCT International Application Number

PCT/EP2007/000094

PCT International Filing date

2007-01-08

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	PCT/EP2006/010568	2006-11-03	Germany
2	10 2006 010 809.4	2006-03-07	Germany