Emulsifiable concentrate comprising vitamin d and uses thereof

Abstract

An emulsifiable concentrate comprises an oil, from 20 to 250 mg / L of a vitamin D and from 5 to 25 weight% of an emulsifier. Also disclosed is an aqueous emulsion comprising the emulsifiable concentrate and water or an aqueous solution, a method for producing the emulsifiable concentrate, and a method for producing an aqueous emulsion using the emulsifiable concentrate. An aqueous composition comprising the emulsifiable concentrate may be used as a foliar fertilizer, in particular for improving the calcium absorption from the roots of a plant.

Description

[0001] Emulsifiable concentrate comprising vitamin D and uses thereof

[0002] Field of the disclosure

[0003] The present disclosure is related to the field of agriculture, in particular emulsifiable concentrates comprising vitamins.

[0004] Background information

[0005] Vitamins are one of the essential nutrients that are essential for human organisms to function properly. Vitamins are organic molecules or classes of organic molecules, also called vitamers. Major health organizations list 13 vitamins: A, Bi, B2, B3, B5, B6, B7, Bg, Bi2, C, D, E, and K.

[0006] The B vitamins and vitamin C are water-soluble, and the remaining ones are soluble in oil. It has been known for some years that some vitamins can also be used in agriculture to improve crop conditions and growth.

[0007] It is highly preferred that agricultural products to be distributed to crops are aqueous solutions as they are easier to handle by farmers and can be further diluted with water. For oilsoluble vitamins, a practical solution is to create an emulsion of the vitamins in water using additives.

[0008] There is a constant need for producers of agricultural products to provide products that are easier to use and more stable.

[0009] CN115887379A (Li, 2023) discloses oil-in-water emulsions containing vitamin D. A mixture containing vitamin D, polysorbate 80, peppermint oil, medium chain triglycerides and other components is mixed with water under high-speed shear conditions to obtain a water-in-oil emulsion.

[0010] US20150045333A1 (Hayes 2015) discloses a composition containing cholecalciferol (vitamin D3), gum Arabic, rice bran oil and water. The cholecalciferol is dissolved in the rice bran oil, and this mixture is mixed in an in-line homogenizer with the other components, including gum Arabic and water to obtain an emulsion.

[0011] US20020001601A1 (Dillon, 2002) discloses gels containing vitamin D3 in oil-in-oil emulsions in the presence of emulsifiers such as stearic acid and stearates.

[0012] WO0224165A1 (Schlyter, 2002) discloses emulsions containing cholecalciferol. An oil phase containing cholecalciferol, lecithin and medium chain triglycerides is prepared and mixed with water in two high-intensity mixers to obtain an emulsion.

[0013] TWI805999 (Liu, 2023) discloses oil-in-water emulsions containing fat soluble vitamins. Fat soluble vitamins are dissolved in oil and mixed with water and a surfactant to obtain an emulsion. Summary of the disclosure

[0014] It has now been shown that a foliar application, i.e., an application to the leaves of a plant, of a composition containing vitamin D increased the plant absorption of calcium via its roots and increased the growth of the plant.

[0015] In a first aspect, the present disclosure provides an emulsifiable concentrate comprising an oil, from 20 to 250 mg / L of a vitamin D, and from 5 to 25 weight% of an emulsifier.

[0016] In another aspect, the present disclosure provides a method for producing an emulsifiable concentrate, for example according to the first aspect, comprising the steps of: a) providing an oil, in particular a mineral oil or a vegetable oil; b) adding a vitamin D to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 20 to 250 mg / L of the vitamin D; and c) adding an emulsifier to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 5 to 25 weight% of the emulsifier.

[0017] Detailed description of the disclosure

[0018] Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.

[0019] All references cited in this description are hereby deemed to be incorporated in their entirety by way of reference.

[0020] As used herein, the following terms have the following meanings:

[0021] "A", "an", and "the" as used herein refers to both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a component" refers to one or more than one component.

[0022] "About" as used herein referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of + / -20 % or less, in particular + / - 10 % or less, more in particular + / -5 % or less, even more in particular + / -1 % or less, and still more in particular + / -0.1 % or less of and from the specified value, in so far such variations are appropriate to perform in the disclosed invention. However, it is to be understood that the value to which the modifier "about" refers is itself also specifically disclosed.

[0023] "Comprise", "comprising", and "comprises" and "comprised of" as used herein are synonymous with "include", "including", "includes" or "contain", "containing", "contains" and are inclusive or open-ended terms that specifies the presence of what follows e.g. component and do not exclude or preclude the presence of additional, non-recited components, features, element, members, steps, known in the art or disclosed therein.

[0024] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints.

[0025] The expression "weight percent", "%wt" or "weight%", here and throughout the description unless otherwise defined, refers to the relative weight of the respective component based on the overall weight of the formulation.

[0026] As used herein, an emulsifiable concentrate is an oil-based composition that is able to form a spontaneous and stable emulsion when diluted with water. It is not necessary to use a mixing device, such as a high-intensity mixer, to obtain an emulsion when adding an emulsifiable concentrate to water or an aqueous solution. An emulsifiable concentrate is thermodynamically stable, meaning that it has excellent storage stability and shelf-life. An emulsifiable concentrate is a homogeneous, single phase, liquid formulation comprising a lipophilic active ingredient, here a vitamin D, dissolved in a water-immiscible solvent.

[0027] There are other methods to prepare emulsions of an oil-soluble compound in water: for example, an oil solution of the compound may be mixed with an aqueous solution comprising an emulsifier to form an emulsion in water that is further diluted to the desired concentration in a tank. Alternatively, the oil, the compound, and the emulsifier, can be added to a water tank and mixed to form the emulsion. This method usually requires high intensity mixing to achieve a stable and well- disperse emulsion.

[0028] An advantage of an emulsifiable concentrate is that it contains as a single product all the elements required for creating an emulsion, except the water contained in the main dilution tank. So, this is a very practical solution for farmers that is very easy to use. The emulsion comprising the emulsifiable concentrate and water may comprise emulsion droplets with an average size of from 0.1 to 1.0 pm.

[0029] Vitamin D is a group of molecules comprising vitamin Di, D2, D3, D4, and D5(which may be referred to individually or in any combination as "vitamin D" or as the "D vitamins"). Vitamin Di is a mixture of ergocalciferol (CAS number: 50-14-6) and lumisterol (CAS number: 474-69-1) (molar ratio= 1:1). Vitamin D2is the molecule ergocalciferol. Vitamin D3is the molecule cholecalciferol (CAS number: 67-97-0). Vitamin D4is the molecule 22-dihydroergocalciferol (CAS number: 511-28-4). Vitamin D5is the molecule sitocalciferol (CAS number: 71761-06-3).

[0030] In a first aspect, the present disclosure provides an emulsifiable concentrate comprising an oil, from 20 to 250 mg / L of a vitamin D, from 5 to 25 weight% of an emulsifier.

[0031] In some embodiments, the present disclosure provides an emulsifiable concentrate comprising an oil, from 20 to 250 mg / L of a vitamin D, from 5.0 to 25 weight% of an emulsifier.

[0032] The emulsifiable concentrate comprises an oil that acts as the solvent for the vitamin D and the emulsifier.

[0033] The vitamin D provides beneficial effects to the crops. In particular, it has been shown that foliar application of an aqueous solution comprising vitamin D increases calcium absorption of the crop by its roots. It was previously thought that foliar application of vitamin D did not have any effect on the nutrient absorption due to the long distance between the leaves and roots.

[0034] The application of vitamin D can also increase the growth of a plant, for example its leaves and / or its tubers, compared to plant that receives the same amount of nutrients but no vitamin D.

[0035] The emulsifier is soluble in oil, and when the emulsifiable concentrate is mixed with water, the emulsifier creates droplets containing the oil and vitamin D, the droplets being in suspension in the aqueous solution.

[0036] It was found that it was possible to prepare an emulsifiable concentrate with a concentration of vitamin D ranging from 20 to 250 mg / L. Vitamins D, such as vitamin D3, have been shown to be toxic at high concentration, so it may be preferred for the emulsifiable concentrate to not contain more than 250 mg / L to lower the toxicity risks for the users manipulating the concentrate and emulsions comprising the concentrate.

[0037] In some embodiments, the concentration of vitamin D in the emulsifiable concentrate ranges from 30 to 70 mg / L.

[0038] In some embodiments, the emulsifiable concentrate comprises from 75 to 95 weight% of an oil.

[0039] In some embodiments, the oil comprised in the emulsifiable concentrate is a vegetable oil, a processed vegetable oil, or a mineral oil. It was observed that the emulsifiable concentrate could be prepared with a wide variety of oils. Vegetable oils may be preferred due to their biodegradability and lower environmental footprint. Examples of suitable vegetable oils include sunflower oil and rapeseed oil.

[0040] A processed vegetable oil is a product obtained by subjecting a vegetable oil to a chemical process. The chemical process may comprise one or several steps. An example of suitable processed vegetable oil is methylated seed oil.

[0041] In some embodiments, the vitamin D comprised in the emulsifiable concentrate comprises cholecalciferol. It was observed that the foliar application of an aqueous solution comprising cholecalciferol, also called vitamin D3, increased the calcium absorption of the plant.

[0042] In some embodiments, the emulsifier comprised in the emulsifiable concentrate is a non-ionic emulsifier. It was observed that an emulsifiable concentrate of vitamin D could be obtained with different emulsifiers, in particular non-ionic emulsifiers. The emulsifiable concentrates containing an emulsifier and vitamin D can be easily mixed with water or an aqueous solution and produces stable emulsions without having to use mixing devices.

[0043] In some embodiments, the emulsifier comprised in the emulsifiable concentrate is selected from the group consisting of castor oil ethoxylates, polyethoxylated esters, and mixtures thereof. It was found that using a castor oil ethoxylates and / or polyethoxylated esters as emulsifier provided a very stable emulsion when the emulsifiable concentrate was added to water.

[0044] In some embodiments, the emulsifier is the compound castor oil, ethoxylated, oleate with the CAS number: 220037-02-5.

[0045] In some embodiments, the emulsifier comprised in the emulsifiable concentrate is a non-ionic polymer with a hydrophilic-lipophilic balance of from 4 to 10. For an emulsifiable concentrate comprising vitamin D in an oil, it was found that non-ionic polymers with a hydrophilic-lipophilic balance of from 4 to 10 were particularly suitable and provided stable emulsions when mixed with water.

[0046] In some embodiments, the emulsifier is an anionic surfactant.

[0047] In some embodiments, the emulsifiable concentrate comprises a first emulsifier being an anionic surfactant and a second emulsifier being a non-ionic surfactant.

[0048] In some embodiments, the emulsifiable concentrate comprises a first emulsifier being an anionic surfactant and a second emulsifier selected from the group consisting of castor oil ethoxylates, polyethoxylated esters, and mixtures thereof.

[0049] In some embodiments, the emulsifiable concentrate comprises from 10 to 25 weight% of an emulsifier.

[0050] In some embodiments, the emulsifiable concentrate comprises from 0 to 1.0 weight%, from 0 to

[0051] 0.5 weight%, from O to 0.1 weight%, or from O to 0.01 weight% of water. It may be preferred that the emulsifiable concentrate is anhydrous or contains as little water as possible. Some commercial forms of the components comprised in the emulsifiable concentrate may comprise some traces of water.

[0052] In some embodiments, the emulsifiable concentrate comprises an antioxidant, in particular wherein the antioxidant is tocopherol. Vitamin D is known to be susceptible to oxidation, so it may be an advantage for the emulsifiable concentrate to comprise an antioxidant to increase the shelf-life thereof. Some commercial oil solutions of vitamin D comprises tocopherol, also called vitamin E, as an antioxidant.

[0053] In another aspect, the present disclosure provides an aqueous emulsion comprising the emulsifiable concentrate according to the present disclosure and water. The emulsifiable concentrate described above is not meant to be directly spread on crops in a field, but rather added to water or an aqueous solution, for example an aqueous solution comprising agricultural products, such as fertilizers, pesticides, herbicides, and biostimulants. One advantage of the present emulsifiable concentrate is that minimal mixing of the solution is needed to obtain a homogeneous composition (meaning that the emulsion is evenly distributed in the solution), after adding the emulsifiable concentrate.

[0054] In some embodiments, the aqueous emulsion comprises from 0.1 to 1.0 weight% of the emulsifiable concentrate according to the present disclosure. The amount of the emulsifiable concentrate in the aqueous emulsion may depend on a number of factors, such as the concentration of vitamin D in the emulsifiable concentrate, the crop that the aqueous emulsion is being applied to, the size of the field, the composition of the aqueous emulsion that may comprise other components in addition to the emulsifiable concentrate, such as fertilizers, or crop protection products.

[0055] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of a vegetable oil, from 20 to 250 mg / L of vitamin D3, and from 5 to 25 weight% of an emulsifier.

[0056] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of rapeseed oil, from 20 to 250 mg / L of vitamin D3, and from 5 to 25 weight% of an emulsifier.

[0057] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of sunflower oil, from 20 to 250 mg / L of vitamin D3, and from 5 to 25 weight% of an emulsifier.

[0058] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of a vegetable oil, from 20 to 250 mg / L of vitamin D3, and from 5.0 to 25 weight% of an emulsifier.

[0059] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of rapeseed oil, from 20 to 250 mg / L of vitamin D3, and from 5.0 to 25 weight% of an emulsifier.

[0060] In some embodiments, the emulsifiable concentrate comprises from 70 to 90 weight% of sunflower oil, from 20 to 250 mg / L of vitamin D3, and from 5.0 to 25 weight% of an emulsifier. In another aspect, the present disclosure provides a method for producing the emulsifiable concentrate according to the present disclosure, comprising the steps of: a) providing an oil, in particular a mineral oil, a processed vegetable oil, or a vegetable oil; b) adding a vitamin D to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 30 to 70 mg / L of the vitamin D; and c) adding an emulsifier to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 10 to 30 weight% of the emulsifier.

[0061] The emulsifiable concentrate is prepared by mixing the components thereof in the solvent, the oil.

[0062] In another aspect, the present disclosure provides a method for applying the emulsifiable concentrate according to the present disclosure to a field, the method comprising the steps of: a) providing an aqueous solution; b) adding the emulsifiable concentrate according to the present disclosure to the aqueous solution; and c) applying the aqueous solution comprising the emulsifiable concentrate to the field.

[0063] The aqueous solution that receives the emulsifiable concentrate may comprise other useful agrochemicals, such as fertilizers, biostimulants, herbicides, pesticides, or fungicides. It may be an advantage to add the emulsifiable concentrate as the final component to the aqueous solution, such that no excessive mixing is required to dissolve further components.

[0064] The aqueous solution comprising the emulsifiable concentrate may be mixed gently to homogenize the solution. The amount of emulsifiable concentrate added to the aqueous solution may be low, for example from 0.1 to 1.0 weight%, so adding the emulsifiable concentrate may not create a homogenous emulsion upon addition due to the inherent viscosity of the aqueous solution. A gentle mixing may be required to make sure that the emulsion is dispersed throughout the aqueous solution. Mixing is not required to emulsify the oil-phase with the aqueous phase.

[0065] Once the aqueous solution comprising the emulsifiable concentrate is ready, it can be applied in a field using standard means known to the skilled person.

[0066] In another aspect, the present disclosure provides the use of an aqueous composition comprising the emulsifiable concentrate according to the present disclosure as a foliar fertilizer.

[0067] In another aspect, the present disclosure provides the use of an aqueous composition comprising the emulsifiable concentrate according to the present disclosure as a foliar fertilizer for increasing the calcium absorption from the roots of the plant. Example 1:

[0068] An emulsifiable concentrate was prepared with the following components: 80 weight% of rapeseed oil, and 20 weight% of castor oil, ethoxylated, oleate (CAS number: 220037-02-5). Vitamin D3was added to the concentrate to reach a concentration of 50 mg / L. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed.

[0069] Example 2:

[0070] An emulsifiable concentrate was prepared with the following components: 80 weight% of sunflower oil, and 20 weight% of castor oil, ethoxylated, oleate (CAS number: 220037-02-5). Vitamin D3was added to the concentrate to reach a concentration of 50 mg / L. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed.

[0071] Example 3:

[0072] An emulsifiable concentrate was prepared with the following components: 85 weight% of rapeseed oil, and 15 weight% of polyethoxylated ester. Vitamin D3was added to the concentrate to reach a concentration of 50 mg / L. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed.

[0073] Example 4:

[0074] An emulsifiable concentrate was prepared with the following components: 85 weight% of rapeseed oil, and 15 weight% of castor oil, ethoxylated, oleate (CAS number: 220037-02-5). Vitamin D3was added to the concentrate to reach a concentration of 50 mg / L. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed.

[0075] Example 5:

[0076] Radish seeds were germinated in pots containing quartz sand and the seedlings were thinned out to 5 seedlings per pots, which were grown further under glasshouse conditions until harvesting.

[0077] Seedlings were supplied with a Hoagland solution containing all the required nutrients including calcium. When plants reached the growth stage of 4-5 fully expanded leaves, the plants received a foliar application of the solution prepared in example 1 or plain water as a control. The application rate mentioned in table 1 in l / ha describes the application rate of the emulsifiable concentrate, which is applied as an emulsion in water. During the foliar spray, the soil was completely covered with cotton wool, to prevent any uptake by roots. Plants were harvested 20 days after the foliar spray. Plants were separated into old leaves, new leaves, and tubers, and dried in a drying oven for 5 days. Thereafter, their dry weights were recorded, and the material was analysed for tissue nutrient concentrations. The results for the calcium concentration of the tubers are presented below in table

[0078] Table 1 It can be seen that the plants that received vitamin D3show a significant increase in the calcium tuber concentration compared to the control.

[0079] Example 6:

[0080] The same experiment as described in Example 5 was repeated using the emulsion prepared in example 4, which was applied at different rates (in terms of l / ha of emulsifiable concentrate). After harvest, the tubers and leaves in each pots were weighted. The results are present in table 2 below.

[0081] Table 2

[0082] It can be seen that the application of vitamin D3increased the weight of the tubers and of the leaves when the radishes received 100% of the recommended calcium nutrition. Example 7:

[0083] An emulsifiable concentrate was prepared with the following components: 84.8 weight% of rapeseed oil, 15 weight% of castor oil, ethoxylated, oleate (CAS number: 220037-02-5), and 0.2 weight% of a solution containing 25 mg / g of vitamin D3in alpha-tocopherol (vitamin E). The concentration in vitamin D3of the emulsifiable concentrate was 50 mg / kg based on the total weight of the emulsifiable concentrate. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed without the need of any mechanical stirring.

[0084] Example 8:

[0085] An emulsifiable concentrate was prepared with the following components: 84 weight% of rapeseed oil, 15 weight% of castor oil, ethoxylated, oleate (CAS number: 220037-02-5), and 1 weight% of a solution containing 25 mg / g of vitamin D3in alpha-tocopherol (vitamin E). The concentration in vitamin D3of the emulsifiable concentrate was 250 mg / kg based on the total weight of the emulsifiable concentrate. This emulsifiable concentrate was added to water (0.5% by volume) and a stable emulsion was formed without the need of any mechanical stirring.

[0086] Example 9:

[0087] The same experiment as described in Example 5 was repeated using the emulsion prepared in example 7 and 8, which was applied at different rates (in terms of l / ha of emulsifiable concentrate). After harvest, the tubers and leaves in each pot were weighed. The results are present in table 3 below.

[0088] Table 3

[0089] It can be seen that the application of an emulsion prepared from an emulsifiable concentrate having a higher concentration (250 mg / kg) also provides beneficial agronomic effects. An emulsifiable concentrate with a higher vitamin D concentration decreases the amount of water that needs to be applied to the field.

Claims

Claims1. An emulsifiable concentrate comprising an oil, from 20 to 250 mg / L of a vitamin D, from 5 to 25 weight% of an emulsifier, and from 0 to 1.0 weight% of water.

2. The emulsifiable concentrate according to claim 1, wherein the emulsifiable concentrate comprises from 75 to 95 weight% of an oil.

3. The emulsifiable concentrate according to claim 1 or 2, wherein the oil is a vegetable oil, a processed vegetable oil, or a mineral oil.

4. The emulsifiable concentrate according to any one of claims 1 to 3, wherein the vitamin D is cholecalciferol.

5. The emulsifiable concentrate according to any one of claims 1 to 4, wherein the emulsifier is a non-ionic emulsifier, an anionic emulsifier, or a mixture of a non-ionic emulsifier and an anionic emulsifier.

6. The emulsifiable concentrate according to claim 5, wherein the non-ionic emulsifier is a non- ionic polymer with a hydrophilic-lipophilic balance of from 4 to 10.

7. The emulsifiable concentrate according to any one of claims 1 to 6, wherein the emulsifier is selected from the group consisting of castor oil ethoxylates, polyethoxylated esters, and mixtures thereof.

8. The emulsifiable concentrate according to any one of claims 1 to 7, wherein the emulsifiable concentrate comprises an antioxidant, in particular wherein the antioxidant is tocopherol.

9. The emulsifiable concentrate according to any one of claims 1 to 8, wherein the concentration of vitamin D in the emulsifiable concentrate ranges from 30 to 70 mg / L.

10. An aqueous emulsion comprising the emulsifiable concentrate according to any one of claims 1 to 9 and water.

11. The aqueous emulsion according to claim 10, wherein the aqueous emulsion comprises from 0.1 to 1.0 weight% of the emulsifiable concentrate according to any one of claims 1 to 9.

12. A method for producing an emulsifiable concentrate, comprising the steps of: a) providing an oil; b) adding a vitamin D to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 20 to 250 mg / L of the vitamin D; and c) adding an emulsifier to the oil provided in step a), such that the emulsifiable concentrate obtained by the method comprises from 5 to 25 weight% of the emulsifier.

13. A method for producing an aqueous emulsion, comprising: providing an emulsifiable concentrate according any of claims 1 to 9; andadding the emulsifiable concentrate to water or an aqueous solution to produce the aqueous emulsion.

14. The use of an aqueous composition comprising the emulsifiable concentrate according to any one of claims 1 to 9 as a foliar fertilizer.

15. The use of an aqueous composition comprising the emulsifiable concentrate according to any one of claims 1 to 9 as a foliar fertilizer for improving the calcium absorption from the roots of a plant.

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