CN116583190A - New formulation with reduced antioxidant content, its manufacture and use - Google Patents

New formulation with reduced antioxidant content, its manufacture and use Download PDF

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Publication number
CN116583190A
CN116583190A CN202180079741.1A CN202180079741A CN116583190A CN 116583190 A CN116583190 A CN 116583190A CN 202180079741 A CN202180079741 A CN 202180079741A CN 116583190 A CN116583190 A CN 116583190A
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formulation
vitamin
amount
soluble
weight
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约亨·亚历山大·布茨
托马斯·林德曼
克里斯托斯·茨口
凯·尔本
克利斯汀·舍弗尔
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DSM IP Assets BV
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/15—Vitamins
    • A23L33/155—Vitamins A or D
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
    • A23K10/32—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from hydrolysates of wood or straw
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/174—Vitamins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/275—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of animal origin, e.g. chitin
    • A23L29/281—Proteins, e.g. gelatin or collagen
    • A23L29/284—Gelatin; Collagen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
    • A23L33/11—Plant sterols or derivatives thereof, e.g. phytosterols

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
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  • Health & Medical Sciences (AREA)
  • Animal Husbandry (AREA)
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  • Biotechnology (AREA)
  • Molecular Biology (AREA)
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  • Inorganic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention relates to microcapsules with an autothermal temperature of greater than or equal to 120 ℃, comprising gelatin, lignosulfonate, a small amount of an antioxidant, and vitamin A or a derivative thereof, and optionally vitamin D or a derivative thereof; and to a container comprising such microcapsules having a volume in the range of 450 liters to 3000 liters. The invention further relates to a method for manufacturing such microcapsules; the use of said microcapsules as additives for feeds and premix; and feed additives, premix and feeds comprising such microcapsules.

Description

New formulation with reduced antioxidant content, its manufacture and use
Disclosure of Invention
The invention relates to a preparation, in particular a solid preparation, with an autothermal temperature of greater than or equal to 120 ℃, comprising a major amount of gelatin, a minor amount of antioxidants, vitamin A or derivatives thereof and optionally vitamin D or derivatives thereof; and to a container containing such a formulation in a volume of up to 3000 l. The invention further relates to a method for producing such a formulation; the use of said formulation as an additive to feeds and premixes; and feed additives, premix and feeds comprising such formulations.
When the formulation is prepared according to the method disclosed below, it is also referred to as "microcapsule (loadlet)". Surprisingly, such formulations/microcapsules having advantageous properties as described below can be prepared with such low amounts of antioxidants.
It is particularly surprising that such formulations/microcapsules have an elevated autothermal temperature despite their reduced antioxidant content compared to the formulations of the prior art. Heretofore, it has been expected that an amount of at least 10 wt.% of an antioxidant (e.g., BHT) is required to ensure an autothermal temperature of at least 120 ℃.
Background
Formulations containing oxidation-sensitive compounds (e.g., fat-soluble vitamins, especially vitamin a, vitamin D, and any derivatives and mixtures thereof) may already undergo oxidation processes at ambient conditions when such formulations are stored or transported. Depending on the reaction rate, storage or transport temperature, and volume of the stored or transported formulation of such exothermic degradation processes, heat accumulation may result, which may lead to self-heating or even spontaneous combustion of such formulations.
In order to minimize the degradation process and thus also reduce the autothermal effect, the oxidation-sensitive compound must be protected in a suitable matrix and form.
Formulations containing vitamin a, vitamin D and any derivatives thereof and mixtures thereof having an autothermal temperature of > 100 ℃ but below 120 ℃ must be stored and transported in flexible intermediate containers having a volume of <450 liters. Furthermore, they must be classified as "class 4.2 hazards" and special equipment must be used for their storage and transportation, which increases the overall cost of such formulations.
Formulations containing vitamin a, vitamin D and any derivatives and mixtures thereof with an autothermal temperature ∈120 ℃ (measured as described below) allow a volume of up to 3000l (=3m) 3 ) Is especially flexible medium bulk containerflexible intermediate bulk containers, "FIBC"), preferably stored and transported in containers, especially FIBCs, having a volume in the range of 450 liters to 3000 liters. In addition, it need not be classified as a "hazard". For sustainability reasons, it is highly desirable to use such containers, especially such FIBCs, i.e. with volume<Smaller bags of 450 litres compare to such larger bags of up to 3000 litres in volume: first, because of their larger size, fewer bags are required to store and transport the same amount of formulation. Second, since no container, especially FIBC, has been reusable so far, fewer bags must be discarded.
It is therefore desirable to provide a formulation containing vitamin a, vitamin a derivatives and any mixtures thereof with vitamin D with an autothermal temperature of ∈120 ℃, such that the formulation can be stored and transported in containers up to 3000 litres in volume, especially FIBCs, preferably in FIBCs ranging from 450 litres to 3000 litres in volume, more preferably in FIBCs ranging from 480 litres to 2000 litres in volume, even more preferably in FIBCs ranging from 500 litres to 1500 litres and 500 litres to 1000 litres in volume, most preferably in FIBCs ranging from 600 litres to 800 litres in volume.
Detailed Description
The present invention thus meets this need and relates to a formulation with an autothermal temperature of ≡120 ℃, comprising
a) A fat-soluble vitamin in an amount of at least 25% by weight, wherein the fat-soluble vitamin is vitamin a or a derivative thereof and optionally vitamin D or a derivative thereof;
b) Gelatin in an amount of at least 40% by weight;
c) Lignin sulfonate in an amount of at least 1 wt%;
d) At least one antioxidant in an amount of 7% by weight or less;
e) An anti-caking agent;
f) Optionally an oil;
g) Optionally reducing sugar;
h) An optional polyol;
i) Optionally residual moisture;
Wherein all amounts of a) to h) add up to 100 wt.%, and are based on the total weight of the amounts of a), b), c), d), e), f), g) and h) together.
The amount of residual moisture is preferably at most 6 wt%, more preferably at most 5 wt%, even more preferably at most 3.5 wt%, most preferably at most 2 wt%, based on the total weight of the formulation, i.e. a) to i). The minimum amount of moisture in the formulation is preferably 0.1 wt%, based on the total weight of the formulation.
When step E) of the method according to the invention is performed, the moisture content is lower than if step E) were not performed.
Despite the low amount of antioxidants in these formulations, they exhibit autothermal temperatures of ≡120 ℃. In addition, they exhibit good stability and good homogeneity in the premix, as well as high stability under feed pelleting conditions. Since the formulations according to the invention exhibit an autothermal temperature of ≡120 ℃ and a Δt of <60K, they can be transported in containers up to 3000l in volume, in particular FIBCs ("flexible intermediate bulk containers"), preferably in containers ranging from 450l to 3000l in volume, in particular FIBCs.
Determination of self-heating temperature
Testing was performed according to specification E-15188 and VDI 2263 part 1.
The samples were placed in a wire basket (16 ml or 1000 ml) of cubic shape in the center of the oven. The temperature of the oven was measured at two points and remained constant during the test period (24 hours), the so-called "isothermal test".
A temperature probe for the sample was placed in the center of the sample. The sample temperature was then brought to a temperature 2K below the oven temperature 24 hours after the start of the test period.
When the temperature difference between the sample and the oven was "Δt" <60K, the test standard according to the united states orange paper "Manual of Tests and Criteria, 6 th revision, volume 33.3, 4.2 no division" was passed, and the sample was considered to be self-heat stable according to the present invention.
When the temperature difference between the sample and the oven, "Δt" >60K, the sample is considered to be experiencing spontaneous combustion or dangerous self-heating.
As shown by way of example, the formulations of the present invention exhibit an autothermal temperature of ≡120℃and a DeltaT of < 60K.
Container
Any type of container may be used having a volume up to 3000 liters, preferably having a volume in the range of 450 liters to 3000 liters, more preferably having a volume in the range of 480 liters to 2000 liters, even more preferably having a volume in the range of 500 liters to 1500 liters and 500 liters to 1000 liters, most preferably having a volume in the range of 600 liters to 800 liters.
"flexible intermediate bulk containers" ("FIBCs"), "big bags", "bulk bags", "super sacks", "tote bags" or "big bags" are industrial containers made of flexible fabric designed for storing and transporting dry, flowable products such as sand, fertilizer and feed additives.
FIBCs are typically made of thick woven polyethylene or polypropylene, coated or uncoated, and typically measure about 45-48 inches (114-122 cm) in diameter and vary in height from 100cm to 200cm (39-79 inches). Its capacity is typically about 1,000kg or 2,200lb, but larger units may store even more. The bulk bags designed to transport one metric ton (0.98 long ton; 1.1 short ton) of material will themselves weigh only 5-7lb (2.3-5.0 kg).
Transport and loading is done on pallets or by lifting them from the ring. The bag is made of one, two or four lifting loops. The single loop bag is suitable for one person to operate because a second person is not required to place the loop on the loader hook. Emptying can be easily done by a special opening in the bottom, such as a discharge chute, which has a number of options, or by cutting only this special opening.
In the present invention, a big bag with four lifting loops is preferably used. The volume thereof ranges preferably from 480l to 2000l, more preferably from 500l to 1500l, even more preferably from 500l to 1000l, most preferably from 600l to 800l. The loading of 200kg to 1500kg of the formulation according to the invention is preferred. More preferably 300kg to 1200kg of the formulation according to the invention. Most preferred is a 500kg to 900kg load of the formulation according to the invention.
The invention thus also relates to a big bag, in particular a big bag with 3 or more lifting loops (e.g. 4 lifting loops), the volume of which is in the range 480l to 2000l and contains a formulation according to the invention with the preferences given below.
It is particularly advantageous if the FIBC has a "liner" (which protects the contents of the FIBC from light, oxygen and water) and the FIBC is a C-type FIBC. An opening at the top for loading and at the bottom for unloading is convenient. Thus, such openings are preferably present. Such openings will be tightly closed during storage and transport.
Formulations
The formulation is described in more detail below. Further disclosed are the essential ingredients and amounts thereof, as well as ingredients not present in the formulation.
Basic ingredients
Fat-soluble vitamins
For the purposes of the present invention, the term "fat-soluble vitamins" includes vitamins A and/or D, the corresponding derivatives, such as esters, in particular C 1 -C 20 Alkyl esters, and any mixtures thereof.
"vitamin D" means vitamin D 3 (cholecalciferol) or vitamin D 2 (ergocalciferol) or both.
"vitamin D derivative" means any derivative of vitamin D, such as 25-hydroxyvitamin D 3 (so-called "HyD")1, 25-dihydroxyvitamin D 3 Or 24, 25-dihydroxyvitamin D 3 。
Particularly preferred examples of fat-soluble vitamins are vitamin A, vitamin A acetate, vitamin A propionate, vitamin A butyrate, vitamin A palmitate, vitamin D 3 And 25-hydroxy-vitamin D, and any mixtures thereof. More preferred are vitamin A acetate and vitamin D 3 And any mixtures thereof. Most preferably, the fat-soluble vitamin is vitamin a acetate or a mixture of vitamin a acetate and vitamin D3, preferably the weight ratio of vitamin a acetate to vitamin D3 is in the range of 1:1 to 100:1, more preferably in the range of 10:1 to 85:1.
The amount of vitamin a or a derivative thereof is selected in such a way that the final amount of said vitamin a or a derivative thereof in the formulation preferably ranges from 25 to 58 wt. -%, more preferably ranges from 28 to 55 wt. -%, even more preferably ranges from 30 to 50 wt. -% and 32 to 48 wt. -%, most preferably ranges from 33 to 46 wt. -%, based on the total weight of a) to h). By disclosing these ranges, any combination of any lower value with any other value within a range is also disclosed, namely 28-58 wt.%, 30-48 wt.%, 25-46 wt.%, etc.
If a mixture of vitamin a acetate and vitamin D3 is used, the amount of vitamin a acetate is as given above for vitamin a derivatives, and the amount of vitamin D3 is selected in such a way that its final amount in the formulation preferably ranges from 0.01 to 10 wt. -%, more preferably from 0.05 to 5 wt. -%, even more preferably from 0.1 to 3.5 wt. -%, most preferably from 0.3 to 2.5 wt. -%, based on the total weight of a) to h). By disclosing these ranges, any combination of any lower value with any higher value of a range, i.e., 0.01 to 5 weight percent, 0.05 to 10 weight percent, 0.1 to 5 weight percent, etc., is also disclosed.
When vitamin D, preferably vitaminElement D 3 When present in the formulation of the invention, an oil is advantageously also present.
Oil (oil)
The oil may be from any source. They may be natural, modified or synthetic. If the oils are natural, they may be vegetable or animal oils. Thus, the term "oil" encompasses any vegetable oil or fat, such as corn oil, sunflower oil, soybean oil, safflower oil, canola oil, peanut oil, palm kernel oil, cottonseed oil, olive oil, coconut oil, canola oil, sesame oil, hazelnut oil, almond oil, cashew oil, macadamia nut oil, mongolian Gong Guoshu (mongo) nut oil, bacon oil, pecan oil, pine nut oil, pistachio oil, merosal (Plukenetia volubilis) oil, walnut oil, and Sweet chainOil triesters ("MCTs") and any mixtures thereof. Preferably, corn oil, peanut oil, safflower oil or sunflower oil is used.
The weight ratio of vitamin D to oil ranges preferably from 1:1 to 1:10, more preferably from 1:2 to 1:5.
Gelatin
Suitable gelatins are poultry gelatin, porcine gelatin, bovine gelatin and any mixtures thereof, as well as fish gelatin and any mixtures with other gelatins. Gelatin is generally classified according to its Bloom value.
There are two types of gelatin: type a gelatin is obtained from acid treatment of collagen. Type B gelatin is obtained from alkali treatment of collagen.
Bloom (Bloom) is a test that measures the strength of gelatin gels. This test determines the weight (in grams) required for a probe (typically 0.5 inch in diameter) to deflect the surface of the gel by 4mm without breaking the gel. Results are expressed in units of bloom (grades). Gelatin in the range of 0 to 300 bloom can be generally used.
Low, medium and high bloom gelatins are gelatins having a strength of less than about 120 bloom (low bloom), between about 120 bloom and up to 200 bloom (medium bloom), or greater than about 200 bloom (high bloom).
Low bloom gelatin, preferably a range of bloom gelatin from 0 to <120, more preferably a gelatin with 60-110 bloom, even more preferably a gelatin with 70-90 bloom, most preferably a gelatin with 80 bloom, and medium bloom gelatin, preferably a gelatin with 120-160 bloom, more preferably a gelatin with 140 bloom, and high bloom gelatin, preferably a gelatin with 200-300 bloom, more preferably a gelatin with 200-270 bloom, even more preferably a gelatin with 200-250 bloom, most preferably a gelatin with 200 bloom may be used.
The amount of gelatin in the formulation of the invention is selected in such a way that its final amount in the formulation is preferably at least 41% by weight, based on the total weight of a) to h). The maximum amount of gelatin in the formulation may preferably be 70% by weight, based on the total weight of a) to h).
Compound c): lignin sulfonate
The lignosulfonates present in the formulations according to the invention are in particular industrially produced products containing lignosulfonates having the most widespread class of cations. Sodium lignin sulfonate, calcium lignin sulfonate, magnesium lignin sulfonate and ammonium lignin sulfonate are particularly preferred. The formulation according to the invention may contain as component c) a single lignosulfonate or a mixture of several lignosulfonates. Furthermore, the lignosulfonate present in the formulation according to the invention may be part of an industrially produced product which comprises other components in addition to lignosulfonate.
As is known, the biopolymer lignin is present in plants, in particular in wood, together with cellulose. Wood, depending on the type, contains about 16 to 37 wt.% lignin. Chemically, lignin consists of an irregular polymer of methoxylated phenylpropane monomers (p-coumaryl alcohol, coniferyl alcohol, sinapyl alcohol, etc.) having a molecular weight estimated to be at least 20 kD. In the first step of cellulose production, wood is decomposed, which in most cases is achieved by treatment with sulfite lye at 125-180 ℃. Thus, cellulose is released and lignin is converted to the water-soluble derivative lignin sulfonate (also known as "sulfite lignin"). On a smaller scale, wood decomposition is also achieved by treating wood with sodium hydroxide and disodium tetrasulfide ("kraft process"). The lignin obtained in this process is called "Kraft lignin/sulfate lignin" and is water insoluble at neutral pH. More recent methods for producing cellulose use organic solvents (e.g., alcohols) that are also mixed with water to decompose wood, and the lignin produced thereby is referred to as "organosolv lignin". Lignin in this form is likewise water insoluble. Currently, the primary lignosulfonates and kraft lignin are commercially available.
Typically, after wood decomposition, the cellulose is separated and the resulting lignosulfonate-containing solution is concentrated to about 50% solids content and sold in this form. Most manufacturers also offer powdered products obtained by spray drying the solution, and these solid forms contain considerable amounts of various sugars in addition to lignin. Some manufacturers produce lignin derivatives with relatively high lignin sulfonate content from primary (crude) lignin sulfonates by enzymatic removal of sugars and, if desired, purification, e.g., by ultracentrifugation. Kraft lignin also provided may be sulphonated to achieve water solubility and sulphonated products are suitable for use as lignosulphonates in the preparation according to the invention. Commercial lignosulfonate products typically consist of about 40-90% lignosulfonate and minor amounts of various sugars, ash, carbohydrates, acetates, formates, resins, etc., with the composition being largely dependent on the quality of the wood used.
Such water-soluble lignosulfonate products are also suitable for use in the feed additive of the present invention. In general, not only crude products with a relatively high content of sugar and additional by-products, but also the above-mentioned purified lignin derivatives can be used in the feed additive according to the present invention, provided that such lignin derivatives are water-soluble or at least water-dispersible.
Preferred examples of suitable lignin derivatives are: sodium lignin sulfonate, ammonium lignin sulfonate, magnesium lignin sulfonate, and calcium lignin sulfonate, and mixtures thereof. Sodium lignin sulfonate and calcium lignin sulfonate are particularly preferred. Most preferred is calcium lignosulfonate.
The suppliers of lignosulfonates are: borregaard Industries Limited, norway; burgo Group, rayonier Advanced Materials, wuhan New England chemical Co., ltd (Wuhan Xinyingda Chemicals), shenyang Xingzheng and chemical Co., ltd (Shenyang Xingzhenghe Chemical), abelin Polymers, GREENAGROCHEM, harbin Fecino Chemical, karjala Pulp, nippon Paper Industries, pacific Dust Control, sappi, the Dallas Group of America, venki Chem and New Yi City Feihuang chemical Co., ltd (Xinyi Feihuang Chemical).
Particularly suitable desugared calcium lignosulfonates are available from Borregaard Industries Limited, norway under the trade names Borrebright CY22P, borreperse Na220 and Borrement CA120, with Borrebright CY22P being particularly preferred. This is made by cutting spruce wood into pieces and feeding it to a digester with a digested calcium bisulphite solution. During cooking at high temperatures (130-140 ℃), lignin in the wood is depolymerized and sulphonated, which produces water-soluble lignosulphonates. At the end of the cooking, the sulfite solution contains calcium lignosulfonate and sugar. The sulfite solution (calcium lignosulfonate and sugar) is separated from the cellulose pulp by filtration. The sulfite lye is concentrated to about 53% in an evaporation plant. The concentrate is fed to a spray dryer to produce lignosulfonate powder (inlet temperature in the range of 200 ℃ to 250 ℃).
The amount of lignosulfonate is selected in such a way that its final amount in the formulation preferably ranges from 1 to 10 wt%, preferably ranges from 1.5 to 6 wt%, based on the total weight of a) to h).
Reducing sugar
Examples of suitable reducing sugars are aldohexoses and ketohexoses having a hydroxyl group in the alpha position.
Reducing disaccharides (e.g., lactose and maltose) and reducing oligosaccharides, as well as aldopentoses and ketopentoses having a hydroxyl group in the alpha position, may also be used.
Preferred examples of reducing sugars are glucose, fructose, galactose and any mixture thereof. Suitable mixtures of fructose and glucose are, for example, invert sugar. Another suitable reducing sugar mixture is high fructose corn syrup (high-fructose corn syrup, HFCS), also known as glucose-fructose, isoglucose and glucose-fructose syrups, a sweetener made from corn starch. "HFCS 42" and "HFCS 55" refer to 42% and 55% fructose composition, respectively, the balance being glucose and water.
The hydrolyzed starch products of DE >20, so-called "glucose syrups" or "dry glucose syrups" -depending on their water content, can also be used as reducing sugars. Glucose syrup 4280, i.e. glucose syrup having a DE in the range of 42-80, is particularly suitable.
"dextrose" is a synonym for "glucose". The term "dextrose equivalent" (dextrose equivalent, DE) denotes the degree of hydrolysis and is a measure of the amount of reducing sugar calculated as D-glucose on a dry weight basis; the scale is based on native starch with a DE close to 0 and glucose with a DE of 100.
The "glucose syrup" or "dry glucose syrup" may be used in the form of a powder, granules or particles. Glucose syrups are generally composed of a mixture of glucose, maltose, oligosaccharides and polysaccharides, wherein the amounts of these components are different.
When glucose syrup is used, the amount is calculated on the basis of dry glucose syrup.
More preferred examples are glucose, fructose and any mixtures thereof. Even more preferably, a single reducing sugar is used, in particular fructose or glucose syrup having a DE.gtoreq.50.
Most preferred is fructose.
The amount of reducing sugar in the formulation of the invention is selected in such a way that its final amount in the formulation preferably ranges from 0 to 5.0 wt. -%, more preferably its final amount ranges from 1.0 to 4.5 wt. -%, based on the total weight of a) to h).
Polyhydric alcohol
Examples of suitable polyols are glycerol, glycerol and C 1-5 Monoesters of monocarboxylic acids, glycerol monoethers, diglycerols, triglycerols, polyglycerols, propylene glycol, dipropylene glycol, 1, 3-butanediol, ethylene glycol, polyethylene glycol, sorbitol, xylitol, maltitol, erythritol, mannitol, and the like.
These polyols may be used alone or in combination of two or more. Preferred examples of the polyhydric alcohol include glycerin, sorbitol, xylitol, maltitol, erythritol and mannitol, with glycerin being particularly preferred.
The amount of polyol in the formulation of the invention is selected in such a way that its final amount in the formulation preferably ranges from 0 to 5.0 wt. -%, more preferably its final amount ranges from 0.1 to 2.5 wt. -%, based on the total weight of a) to h).
Antioxidant agent
The antioxidant may be a water-soluble antioxidant or a fat-soluble antioxidant, or any mixture thereof. Thus, mixtures of water-soluble antioxidants, mixtures of fat-soluble antioxidants, and mixtures of one or more water-soluble antioxidants with one or more fat-soluble antioxidants are also included in the term "antioxidants". Preferred are lipid-soluble antioxidants and mixtures thereof, and mixtures of water-soluble antioxidants and lipid-soluble antioxidants. Inorganic antioxidants may also be present.
An example of an inorganic antioxidant is NaBH 4 、Na 2 SO 3 And/or Na 2 S 2 O 3 。
Examples of fat-soluble antioxidants are ascorbyl palmitate, polyphenols, and antioxidants comprising one or more hydroxyl groupsFlavones substituted with one or more hydroxyl groups, isoflavones substituted with one or more hydroxyl groups, tocotrienols and analogues thereof, tocopherols and analogues thereof, phenols having bulky alkyl groups (e.g. butylated hydroxyanisole ]butylated hydroxyanisole, "BHA"), butylated hydroxytoluene ]butylated hydroxytolines, "BHT"), t-butylhydroquinone, thymol (=5-methyl-2- (prop-2-yl) phenol), eugenol (=2-methoxy-4- (prop-2-en-1-yl) phenol)), or any mixtures thereof.
Analogs of tocopherols and tocotrienols are especially compounds having a shorter side chain at the 2-position than tocopherols and tocotrienols.
Examples of flavonoids substituted today by one or more hydroxyl groups are: 6-hydroxyflavone, 5, 7-dihydroxyflavone (=chrysin), 4',5, 7-trihydroxyflavone (=apigenin), 3',4',5, 7-tetrahydroxyflavone (luteolin) and 4',5,6,7, 8-pentamethoxyflavone (citrus flavone).
Examples of isoflavones substituted with one or more hydroxyl groups and optionally methoxy groups are daidzein (=4 ', 7-dihydroxyisoflavone), genistein (=4', 5, 7-dihydroxyisoflavone), primetin (=4 ', 5-dihydroxy-7-methoxyisoflavone), biochanin a (=5, 7-dihydroxy-4' -methoxy-isoflavone), olobohr (=3 ',4',5, 7-tetrahydroxy isoflavone), santalen (=3 ',4', 5-trihydroxy-7-methoxy-isoflavone) and praline (=3 ',5, 7-trihydroxy-4' -methoxyisoflavone).
BHA is preferably a mixture of 2-tert-butyl-4-hydroxy-anisole and 3-tert-butyl-4-hydroxy-anisole. BHT is preferably 2, 6-di-tert-butyl-p-cresol (IUPAC name=2, 6-di-tert-butyl-4-methylphenol).
The use of BHA is limited; which is no longer allowed for use in cat food, for example. Thus, it is not a preferred antioxidant in the formulation of the present invention.
Examples of water-soluble antioxidants are ascorbic acid and salts thereof (e.g., sodium ascorbate), citric acid and salts thereof (e.g., sodium citrate), and any mixtures thereof.
Preferred examples of mixtures of water-soluble antioxidants with fat-soluble antioxidants are tocopherol and sodium ascorbate, tocopherol and ascorbic acid, wherein the tocopherol may be alpha-tocopherol, beta-tocopherol, gamma-tocopherol or delta-tocopherol, preferably wherein the tocopherol is alpha-tocopherol or delta-tocopherol, more preferably wherein the tocopherol is alpha-tocopherol, most preferably wherein the tocopherol is DL-alpha-tocopherol.
Tocopherols, tocotrienols and analogues thereof
Examples of suitable tocopherols and analogues thereof are, for example, compounds of formula (II)
Wherein R is 1a And R is 2a Independently of one another H or C 1-11 Alkyl or (CH) 2 ) n -OH, wherein n is an integer from 1 to 4, or R 1a And R is 2a Which together represent a keto group, A is CHR 3a Or C (=o), and wherein R 3a 、R 4a And R is 6a Independently of one another H or C 1-4 Alkyl, and wherein R 5a Is H or OH or C 1-4 Alkyl or C 1-4 Alkoxy as disclosed in WO 2019/185894.
Another suitable tocopherol is a compound of formula (II) wherein the two substituents R 1a And R is 2a One of them is C 12-21 Alkyl, and the two substituents R 1a And R is 2a The other of (a) is hydrogen or C 1-5 Alkyl or (CH) 2 ) n -OH, wherein n is an integer from 1 to 5, and wherein a is CH (R 3a ) And wherein R is 3a 、R 4a And R is 6a Independently of one another H or C 1-4 Alkyl, and wherein R 5a Is H or OH or C 1-4 Alkyl or C 1-4 Alkoxy as disclosed in WO 2019/185938.
Compounds of formula (II) wherein A is CH are also suitable antioxidants in the formulations of the invention 2 ，R 1a Is C 1-5 -alkyl, R 2a Is H or C 1-2 -alkyl, R 5a Is H or C 1-4 -alkoxy or C 1-4 -alkyl, and R 4a And R is 6a Independently of one another H or C 1-4 Alkyl, with preference as disclosed in WO 2019/185900.
Preferred examples of antioxidants of formula (II) as disclosed in WO 2019/185894 are compounds of the following formulae (1) to (11), wherein "Me" is methyl:
other examples of suitable antioxidants that can be used in the formulation of the present invention are compounds of formula (III) and formula (IV),
Wherein R is 1b And R is 2b Independently of one another H or C 1-11 Alkyl or CH 2 ) n -OH, wherein nn is an integer from 1 to 6, or R 1b And R is 2b Together represent a keto group, and wherein R 3b 、R 4b 、R 5b And R 6b Independently of one another H or C 1-6 Alkyl or C 1-6 Alkoxy, and R 7b Is H or C 1-6 Alkyl as disclosed in WO 2019/185898.
Thus, "alkyl" and "alkoxy" include straight chain alkyl and branched alkyl, and straight chain alkoxy and branched alkoxy, respectively.
Preferred examples of the compounds of formula (III) and formula (IV) are the following compounds (12) to (19):
further suitable antioxidants are compounds of the formula (V) in which R 1 、R 2 And R is 3 Independently of one another H or straight-chain C 1-6 Alkyl or branched C 3-8 Alkyl, wherein R is preferably 1 Is H or methyl or ethyl or n-propyl or isopropyl or tert-butyl, and R 2 And R is 3 Independently of each other, H or methyl or ethyl, with further preferences as disclosed in WO 2019/185940.
Furthermore, compounds of formula (VI) as disclosed in WO 2019/185904, wherein n is 1 or 2, r, may be used as antioxidants in the formulations of the invention 1b And R is 3b Independently of one another H or C 1-5 Alkyl, and R 2b Is H or C 1-5 Alkyl or C 1-5 Alkoxy, preferably with the proviso that R 1b 、R 2b And R is 3b At least one of which is H.
Thus, the following compounds of formulas (VI-1) and (VI-2) are particularly preferred:
asterisks mark each chiral/stereogenic center, i.e. all possible isomers having any configuration in said center, are covered by the terms "compound of formula (VI-1)" and "compound of formula (VI-2)" respectively.
Likewise suitable antioxidants are compounds of the following formulae (VII) and (VIII), wherein R is as disclosed in WO 2019/185942 and WO 2019/185888, respectively 1c 、R 2c And R is 3c Independently of one another H or C 1-4 -an alkyl group. Which is preferredExamples are tocotrienols and tocopherols of formulas (20) to (27) as shown below.
Asterisks mark each chiral/stereogenic center. The term "compound of formula (VII)/(VIII)" encompasses all possible isomers having any configuration at the center.
Examples of particularly preferred compounds of formula (VII) are compounds of the following formulae (20) (=α -tocotrienol), (21) (=β -tocotrienol), (22) (=γ -tocotrienol) and (23) (=δ -tocotrienol), wherein all possible diastereomers and enantiomers are included.
Examples of particularly preferred compounds of formula (VIII) are compounds of the following formulae (20) (=α -tocopherol), (21) (=β -tocopherol), (22) (=γ -tocopherol) and (23) (=δ -tocopherol), including all possible diastereomers and enantiomers.
Asterisks mark each chiral/stereogenic center. The term "compound of formula (20)/(21)/(22)/(23)/(24)/(25)/(26)/(27)" encompasses all possible isomers having any configuration at the center.
Polyphenols
Examples of suitable polyphenols are 2,4, 5-trihydroxybutyryl, epigallocatechin gallate (epigallocatechin gallate, "EGCG"), tableGallocatechin, hydroxytyrosol, resveratrol, carnosol, 2- (3, 4-dihydroxyphenyl) acetic acid and C thereof 1-6 Alkyl esters, and any mixtures thereof.
Further suitable polyphenols are derivatives of hydroxybenzoic acid, for example gallic acid (=3, 4, 5-trihydroxybenzoic acid) and syringic acid (=4-hydroxy-3, 5-dimethoxy-benzoic acid), preferably esters and alkali (earth) metal salts. Examples of preferred esters are C of gallic acid 1-20 Alkyl esters (e.g. propyl-, octyl-or dodecyl-gallate), and C of syringic acid 1-20 Alkyl esters.
Furthermore, cinnamic acid and hydroxycinnamic acids, such as derivatives of ferulic acid (=3- (4-hydroxy-3-methoxyphenol) prop-2-enoic acid), caffeic acid (=3, 4-dihydroxycinnamic acid), dihydrocaffeic acid (=3- (3, 4-dihydroxyphenyl) propionic acid), chlorogenic acid (=esters of caffeic acid and (-) -quinic acid), o-coumaric acid, m-coumaric acid, p-coumaric acid (=2-hydroxycinnamic acid/3-hydroxycinnamic acid/4-hydroxycinnamic acid), rosmarinic acid (=caffeic acid esters of 3- (3, 4-dihydroxyphenyl) lactic acid) or sinapic acid (=3, 5-dimethoxy-4-hydroxycinnamic acid), preferably esters and alkali (earth) metal salts, can be used as antioxidants in the present invention.
Examples of derivatives of cinnamic acid are Z-ethoxyethyl p-methoxycinnamate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4-methoxycinnamate and diethanolamine 4-methoxycinnamate.
The most preferred antioxidants for use in the formulations of the present invention areButylene oxide(= "BHT"), such as 2, 6-di-tert-butyl-p-cresol (IUPAC name = 2, 6-di-tert-butyl-4-methylphenol) and mixtures of DL- α -tocopherol with sodium ascorbate, mixtures of DL- α -tocopherol with ascorbic acid, and mixtures of DL- α -tocopherol with ascorbyl palmitate.
The weight ratio of DL-alpha-tocopherol to sodium ascorbate and DL-alpha-tocopherol to ascorbic acid ranges preferably from 5:1 to 1:5, more preferably from 3:1 to 1:3, even more preferably from 2:1 to 1:2, most preferably from 1.1:1 to 1:1.1.
Surprisingly, the total amount of antioxidants in the formulation of the invention is lower than in the existing gelatin-based formulations on the market.
Preferably, the total amount of antioxidants is selected in such a way that its/their final amount in the formulation is preferably +.4.0 wt%, more preferably its/their final amount ranges from 0.1 wt% to 3.0 wt% and from 0.2 wt% to 2.5 wt%, based on the total weight of a) to h).
Anti-caking agent
Suitable organic anticaking agents are corn starch, as well as starches and derivatives thereof from other plant sources (e.g., waxy corn, wheat, tapioca, pea and potato), such as pregelatinized starches, starch ethers (e.g., carboxymethyl starch), starch esters (e.g., mono-phosphate starch, alkenyl succinated starch, especially octenyl succinated starch), crosslinked starch and oxidized starch, and any mixtures thereof. Other suitable organic anti-caking agents are talc, cellulose, microcrystalline cellulose, cellulose derivatives or fibers, ferric ammonium citrate, sodium salts of fatty acids (e.g., sodium stearate), potassium salts of fatty acids (e.g., potassium stearate), calcium salts of fatty acids (e.g., calcium stearate), magnesium salts of fatty acids (e.g., magnesium stearate), aluminum salts of fatty acids (e.g., aluminum stearate), ammonium salts of fatty acids (e.g., ammonium stearate), and any mixtures of any of them.
Other suitable antiblocking agents are inorganic antiblocking agents, for example H silicate 2n+2 Si n O 3n+1 And alkali/alkaline earth metal salts thereof, precipitated silicic acid, silica (=silica), modified silica, hydrophobically modified silica, precipitated silica, magnesium oxide, dicalcium diphosphate, tricalcium phosphate, magnesium phosphate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, potassium silicate, calcium silicate, magnesium trisilicate, aluminum silicate, sodium aluminum silicate, potassium aluminum silicate, calcium aluminum silicate, zeolite (aluminosilicate), disodium sulfate, or mixtures thereof. Other suitable inorganic anti-caking agents are bentonite and kaolin.
Also, mixtures of organic and inorganic antiblocking agents may be used.
Preferred anti-caking agents for use in the formulations of the present invention are those having a particle size D (v, 50%) of 100nm to 10 μm, preferably 100nm to 9 μm, more preferably 150nm to 5 μm, measured as a dry dispersion with Malvern MasterSizer3000 (laser diffraction).
The particle size of the antiblocking agent can be determined using a laser diffraction system (e.g., malvern MasterSizer 3000) as a dry dispersion or a wet dispersion in oil or Volasil (a mixture of volatile and cyclic silicones, such as octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane). Particle size can also be determined by electron microscopy.
A more preferred anticaking agent is silicic acid H 2n+2 Si n O 3n+1 Silica, microcrystalline cellulose, and any mixtures thereof.
The most preferred anti-caking agent is hydrophilic precipitated silicic acid H 2n+2 Si n O 3n+1 Hydrophilic precipitated silica, and any mixtures thereof.
The amount of antiblocking agent is selected in such a way that its final amount in the formulation is preferably in the range of 1-10 wt. -%, more preferably in the range of 3 to 9 wt. -%, most preferably in the range of 4.5 to 7.5 wt. -%, based on the total weight of a) to g). By disclosing these ranges, any combination of any lower value with any higher value of a range, i.e., 1-7.5 weight percent, 4.5-10 weight percent, etc., is also disclosed.
Absent ingredients
In contrast to the formulation disclosed in EP 494 417 A2, the matrix of the formulation of the invention does not comprise any of the following salts: water-soluble carboxylates, sodium carbonate, potassium carbonate, calcium sulfate, and calcium phosphate. Examples of such water-soluble carboxylates which are not present in the matrix of the formulation of the invention are: basic aluminum acetate, sodium tartrate, sodium glutarate, sodium acetate, calcium acetate, sodium propionate, calcium propionate and sodium benzoate. However, some of these salts may be used as anti-caking agents during drying of the formulation, especially during the powder capture process step. Preferably, none of these salts is used to make the formulations of the present invention; thus, the formulation of the present invention does not comprise any of these salts; i.e. no water-soluble carboxylate, no sodium carbonate, no potassium carbonate, no calcium sulfate and no calcium phosphate.
In EP-A494 417, these salts are used to crosslink gelatin with reducing sugars at temperatures in the range 55℃to 85℃for 2-24 hours, which is considered necessary for stabilizing the formulation.
An advantage of the process of the invention is that no organic solvent other than water is used, so that the formulation according to the invention is substantially free of organic solvents. By "substantially free" is meant an amount of 5 wt.% or less, preferably 3 wt.% or less, more preferably 1 wt.% or less, even more preferably 0.5 wt.% or less, and most preferably 0.1 wt.% or less.
The formulation of the present invention preferably does not contain any non-reducing sugar (e.g. sucrose) instead of reducing sugar. However, mixtures of non-reducing sugars and reducing sugars may be used.
Furthermore, no crosslinking agents, such as acetaldehyde, glutaraldehyde or glyoxal, are present in the formulation of the invention.
Ethoxyquin, also known as "EMQ" (IUPAC name: 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline), is also not present in the formulations of the present invention; according to EP-A494417, the presence of ethoxyquin is necessary for obtaining stable formulations.
In a preferred embodiment of the invention, the formulation does not comprise ethoxyquin, and it does not comprise a water-soluble carboxylate, and it does not comprise sodium carbonate, and it does not comprise potassium carbonate, and it does not comprise calcium sulfate, and it does not comprise calcium phosphate.
In another preferred embodiment of the invention, the formulation does not comprise any of the compounds mentioned in the chapter "non-existent ingredients".
Properties of the formulations of the invention
The formulations of the present invention preferably exhibit a range of 0.55-0.67g/cm 3 More preferably in the range of 0.6 to 0.7g/cm 3 Is a bulk density of the polymer.
Furthermore, the formulations of the present invention preferably exhibit a range of 0.6-0.7g/cm 3 Is not limited, and the tap density of (a) is not limited.
Bulk and tap densities were measured as follows:
a 250ml glass cylinder was filled with sample. The volume and weight were measured. Bulk density is weight divided by volume.
To measure Tap density, samples were tapped with Stampfvolumeter JEL STAV II (j. Engelsmann AG) at 2000 Tap. The tapped volume is measured. Tap density is the weight divided by tap volume.
Preferably, in addition to the bulk and/or tap densities described above, the formulations of the invention also exhibit particle sizes and/or particle size distributions as described below, which result in very good homogeneity when mixed into feed.
Preferred embodiments of the formulations of the invention
Particularly preferred formulations of the invention are the following formulations a to C, wherein the amounts of the individual components are given in% by weight. The formulations preferably contain only the ingredients cited in the correspondence table and no further ingredients. Thus, the formulation preferably consists of only the ingredients cited in the correspondence table.
Instead of vitamin A acetate, another vitamin C can be used 1-20 Alkyl esters, preferably another vitamin A C 2-16 Alkyl esters.
Formulation a: all amounts are given in weight percent and are based on the total weight of the formulation
Any combination of the amount of one ingredient with the preferred amount of the other ingredient and/or the more preferred or most preferred amount of the other ingredient is also contemplated within the scope of such preferred formulation a.
If vitamin D3 is additionally present in formulation A, its amount is in the range of 2-3 wt.% based on the total weight of the ingredients cited in the above correspondence table. Furthermore, there is preferably also oil with the preferences given above. In this case, the amount of gelatin is correspondingly reduced.
Formulation B: all amounts are given in weight percent and are based on the total weight of all ingredients referenced in the table below. In addition, moisture may be present in the amounts given above.
Any combination of the amount of one ingredient with the preferred amount of the other ingredient and/or the more preferred or most preferred amount of the other ingredient is also contemplated within the scope of such preferred formulation B.
If vitamin D3 is additionally present in formulation B, its amount is in the range of 2-3 wt.% based on the total weight of the ingredients cited in the above correspondence table. Furthermore, there is preferably also oil with the preferences given above. In this case, the amount of gelatin is correspondingly reduced.
Formulation C: all amounts are given in weight percent and are based on the total weight of all ingredients referenced in the table below. In addition, moisture may be present in the amounts given above.
Any combination of the amount of one ingredient with the preferred amount of the other ingredient and/or the more preferred or most preferred amount of the other ingredient is also contemplated within the scope of such preferred formulation C.
If vitamin D3 is additionally present in formulation C, its amount is in the range of 2-3 wt.% based on the total weight of the ingredients cited in the above correspondence table. Furthermore, there is preferably also oil with the preferences given above. In this case, the amount of gelatin is correspondingly reduced.
Particle size and measurement
To determine the particle size of the solid formulation of the present invention, a sieving test can be performed with filters having 850 μm pores (mesh number 20), 425 μm pores (mesh number 40) and 150 μm pores (mesh number 100).
In addition, the particle size of the solid formulation can also be determined by laser diffraction analysis, wherein the dry dispersion of the sample is measured using Malvern Mastersizer or 3000 and Fraunhofer calculations.
The particle size of the formulation, when measured by laser diffraction using Malvern Mastersizer 3000 and Fraunhofer calculations, was as follows:
D(v,10％)＝130-210μm；
D(v,50％)＝220-300μm；
D(v,90％)＝340-430μm。
synonyms for "D (v, 10%)" are "D (v, 10%)", "D (v, 10)", "D (v, 0.1)", "D (v, 10)" and "D (v, 0.1)". This applies in a similar manner to "D (v, 50%)" and "D (v, 90%)".
Method for producing a formulation
The invention also relates to a method for manufacturing a formulation having the above preferences, said method comprising the steps of:
A) Dissolving gelatin b), lignosulfonate c) and water-soluble antioxidant d), if present, in water to obtain a matrix;
b) Heating the fat-soluble vitamin a), the fat-soluble antioxidant d) and the oil f), if present, to obtain an active phase;
c) Emulsifying the active phase obtained in step B) into the matrix obtained in step a) to obtain a dispersion;
d) Spray drying the dispersion obtained in step C) in the presence of an anti-caking agent to obtain said formulation;
wherein optionally reducing sugars g) and/or polyols h) may be added, preferably to the matrix in step A) or step C).
Preferably, the method for manufacturing the formulation according to the invention comprises neither a crosslinking step performed by exposure to radiation nor a crosslinking step performed by use of enzymes.
The formulation of the present invention is preferably manufactured according to a process comprising the steps of:
a) Dissolving gelatin b), lignosulfonate c), reducing sugar g), polyol h) and water-soluble antioxidant d), if present, in water to obtain a matrix;
b) Heating the fat-soluble vitamin a), the fat-soluble antioxidant d) and the oil f), if present, to obtain an active phase;
c) Emulsifying the active phase obtained in step B) into the matrix obtained in step a) to obtain a dispersion;
D) Spray drying the dispersion obtained in step C) in the presence of an anti-caking agent e) to obtain the formulation.
Alternatively, one or both of the two components of reducing sugar g) and polyol h) may not be added to the water or to the matrix formed in step a) from gelatin and lignosulfonate in water, but to the mixture in step C) before or during emulsification.
The individual steps are disclosed in more detail below. Additional details are given in the examples, which may also be generalized.
Step A)
The amounts of gelatin b), lignosulfonate c), reducing sugar g), polyol h) and water-soluble antioxidant D), if present, are selected such that the final amounts of these compounds in the solid formulation are as described above, respectively, after steps a) to D) and a) to E) have been performed.
Step a) is preferably performed at a temperature in the range of 40 ℃ to 80 ℃, more preferably in the range of 50 ℃ to 75 ℃, most preferably in the range of 55 ℃ to 70 ℃.
Step B)
The amounts of fat-soluble vitamin a), fat-soluble antioxidant D) and oil f), if present, are chosen such that the final amounts of these compounds in the solid formulation are as described above, respectively, after steps a) to D) and a) to E) have been performed.
Step B) is preferably carried out at a temperature at which components a) and c) become liquid.
When vitamin D, preferably vitamin D 3 When present in the formulation of the present invention, vitamin D is preferably added to other fat-soluble vitamins and fat-soluble antioxidants as an oil suspension, whereby the weight ratio of vitamin D to oil ranges preferably from 1:1 to 1:10, more preferably from 1:2 to 1:5.
If only vitamin D, preferably vitamin D, is present in the formulation of the present invention 3 Vitamin D is preferably added to the fat-soluble antioxidant as an oil suspension, whereby the weight ratio of vitamin D to oil is preferably in the range of 1:1 to 1:10, more preferably 1:2 to 1:5.
Step C)
Preferably, this step is performed at a mixing temperature in the range of 40 ℃ to 75 ℃, more preferably in the range of 50 ℃ to 70 ℃, even more preferably in the range of 55 ℃ to 65 ℃ to obtain the dispersion.
Homogenization may be achieved by using a rotor-stator device or a high pressure homogenizer or both. Other means known to those skilled in the art may also be used.
Step D)
The separation and drying of the mixture of oil-in-water preparations to produce the solid formulation according to the invention may be carried out in any conventional manner, for example spray cooling, modified spray cooling, spray drying, a combination of spray drying and fluid bed granulation, modified spray drying or sheet drying and crushing, see for example WO 91/06292 A1.
Preferably, the conversion to a solid formulation is achieved by a powder capture technique whereby the ejected dispersion droplets are captured by an anti-caking agent (so-called "capture medium") and dried.
Step E)
It is advantageous to heat treat the powder obtained after step D) has been performed. Therefore, it is preferable to apply a temperature of up to 125 ℃, more preferably to perform the heat treatment at a temperature in the range of 80-120 ℃, even more preferably to perform the heat treatment at a temperature in the range of 100-120 ℃, most preferably to perform the heat treatment at a temperature in the range of 110-120 ℃. Thereby reducing the amount of moisture in the formulation.
Further embodiments of the invention
Use of the same
The invention also relates to the use of the formulation according to the invention with the preferences given above as an additive for feed or premix.
Feed additive, premix and feed according to the invention
The invention also relates to a feed additive, premix and feed comprising the formulation of the invention with the above-mentioned preferences. Feed (feed/feedstuff) refers to any substance or product intended for oral feeding of animals, including additives, whether processed, partially processed or unprocessed.
The feed in the context of the present invention is in particular a feed for: broiler chickens, including chicks, growing chickens, raising chickens; broiler breeder chickens, including chicks, growing chickens (hens), laying hens and breeder chickens; laying hens and other poultry such as hens and ducks, laying breeder's, ducks and geese, partridge, quail and pheasant, ostrich and emu; turkeys, including laying hens, growing chickens, raising chickens; turkey breeder chickens, including chicks, growing chickens, laying hens and breeder chickens; ruminants, including calves, milk replacers, heifers, beef cattle, breeding bull, sheep, and goats; horses, especially foal, recreational horses, racehorses, mares and horses; a rabbit; mink and fox; pigs, including finishing pigs: pre-weaning pigs, weaned pigs, growing pigs and bred pigs; pig breeding: backup sows, sows and boars; feed for companion animals, particularly dogs and cats.
The amounts of the formulation and the fat-soluble vitamins are in accordance with the guidelines of the regulations in this area, respectively, depending on the particular animal species and its age.
In the supplementation guide, vitamins A and D 3 The amounts of (a) are given in international units ("i.u.").
In order to ensure that the active ingredient in the feed is delivered in a systemic manner, "i.u." is used as a universal unit of fat-soluble vitamins, as there are different forms of vitamins with different amounts of fat-soluble vitamins.
The formulation according to the invention is usually added to the feed in the form of a premix, i.e. a mixture with other micronutrients such as other vitamins or formulations and minerals thereof. For many species, the premix in the feed comprises a content of <1 wt%.
The amount of formulation according to the invention that needs to be included in the feed is calculated based on the active content of the feed and taking into account the target dose of fat-soluble vitamins in the final feed at said inclusion level.
The conversion coefficients of the fat-soluble vitamins are as follows:
vitamin a corresponds to 0.344 μg vitamin a acetate;
1 I.U. vitamin D 3 Equivalent to 0.025. Mu.g vitamin D 3 ；
Table IV below shows the amount of fat-soluble vitamins added per kg of air dried feed. The exact amount depends on several factors, such as the stage/age of the animal, the animal species and local legal restrictions.
Table IV
Non-limiting examples of feeds to which the formulations of the present invention may be added are given below.
Feed for poultry
The feed for poultry varies from region to region. In tables V and VI below, typical examples of diets in europe and latin america are given. These diets include cereals (e.g., wheat, rye, maize/corn), minerals (e.g., naCl), vegetable oils (e.g., soybean oil), amino acids and proteins.
The invention therefore also relates to a feed for poultry, comprising a formulation according to the invention; preferably to a feed for poultry comprising a formulation according to the invention and cereals, minerals, vegetable oils, amino acids and proteins.
Table V:european ration
Table VI:latin American ration
Pet food
Pet foods are formulated to meet nutritional specifications using a combination of ingredients to meet target nutritional specifications.
The nutritional specifications for complete and balanced dog foods or cat foods will meet or exceed guidelines provided by the american society for feed management (American Association of Feed Control Officials, AAFCO). The composition of the ingredients of the pet food may include any legal feed ingredients such that the number of combinations is not unlimited, but rather is closed. Some examples of ingredients used in dog foods and cat foods can be found in table VII below:
table VII:
the invention therefore also relates to a pet food comprising the formulation according to the invention; preferably to pet food products comprising a formulation according to the invention and animal bone meal and/or raw meat, vegetable proteins, cereal grains, fibre sources, fats and/or oils, micronutrients, palatability agents and optionally other non-essential ingredients.
Feed for pigs
Reference is made herein to the national swine nutrition guidelines of 2010 (NATIONAL SWINE NUTRITION GUIDE, 2010), two non-limiting examples of which are given below.
Table VIII:daily ration of corn and soybean meal
Table IX: daily ration with high fiber content
The invention therefore also relates to a feed for pigs, comprising a formulation according to the invention; preferably to a feed for pigs comprising a formulation according to the invention and a premix of corn, soybean meal, minerals, vegetable oils, amino acids, further vitamins and trace minerals.
The invention will now be further illustrated in the following non-limiting examples.
Examples
The following examples 1 to 5 illustrate the manufacture of the formulations of the present invention.
Examples 1 to 5
General procedure I
The matrix components, i.e. the reducing sugar (if present), glycerol (if present), gelatin, lignin sulfonate and optionally water-soluble antioxidants, are dissolved in water at about 65 ℃ to obtain a "matrix".
Vitamin a acetate, vitamin D3 (if present), oil (if present) and the fat-soluble antioxidant are heated with stirring at about 65 ℃ until the vitamin a acetate ("active phase") is completely melted. They are then emulsified into a matrix.
Thus, the amounts of the ingredients are selected in such a way that their concentrations in the final formulation are as disclosed in tables 1, 2 and 3, respectively.
After thorough mixing, the resulting dispersion is sprayed into a spray tower in the presence of an anti-caking agent to form droplets of the desired size. The solidified droplets are then dried by means of drying air at different temperatures (5-75 ℃). The dried powder was separated from the bulk of the anti-caking agent and sieved through 150 μm and 600 μm filters.
The powder is further treated in a mixer or in a fluidised bed at a temperature of up to 120 c, thereby rendering it partially water insoluble.
The particle size of the dried and heat treated powder was determined using a laser diffraction analysis using Malvern Mastersizer 3000. The sample is thus dry dispersed. The particle size distribution of the samples was calculated by applying Fraunhofer theory.
Further, bulk density and tap density were measured as described above.
The autothermal temperature is measured according to the procedure described above.
TABLE 1: example 1
In the table, all amounts are given in weight percent and are based on the total weight of the formulation. The total amount of all ingredients add up to 100% by weight.
TABLE 2: example 2
In the table, all amounts are given in weight percent and are based on the total weight of the formulation that does not contain residual moisture. The total amount of all ingredients, except the residual moisture, is 100% by weight. The amount of residual moisture is based on the total weight of the formulation.
TABLE 3 Table 3: examples 3 to 5
In the table, all amounts are given in weight percent and are based on the total weight of the formulation that does not contain residual moisture. The total amount of all ingredients, except the residual moisture, is 100% by weight. The amount of residual moisture is based on the total weight of the formulation.
WDO = water dispersible oil

Claims (17)

1. A formulation having an autothermal temperature of greater than or equal to 120 ℃, wherein the formulation comprises
a) A fat-soluble vitamin in an amount of at least 25% by weight, wherein the fat-soluble vitamin is vitamin a or a derivative thereof and optionally vitamin D or a derivative thereof;
b) Gelatin in an amount of at least 40% by weight;
c) Lignin sulfonate in an amount of at least 1 wt%;
d) At least one antioxidant in an amount of 7% by weight or less;
e) An anti-caking agent;
f) Optionally an oil;
g) Optionally reducing sugar;
h) An optional polyol;
i) Optionally residual moisture;
wherein all amounts of a) to h) add up to 100% by weight and based on the total weight of a), b), c), d), e), f), g) and h) together, and
wherein preferably ethoxyquin is not present in the formulation.
2. The formulation of claim 1, wherein the formulation does not comprise the following salts: water-soluble carboxylates, sodium carbonate, potassium carbonate, calcium sulfate and calcium phosphate, wherein the water-soluble carboxylates not present in the formulation are preferably: basic aluminum acetate, sodium tartrate, sodium glutarate, sodium acetate, calcium acetate, sodium propionate, calcium propionate and sodium benzoate.
3. Formulation according to claim 1 and/or 2, wherein the amount of gelatin is at least 41% by weight, based on the total weight of a) to h).
4. The formulation of any one or more of the preceding claims, wherein the formulation has a bulk density in the range of 0.6g/cm 3 To 0.7g/cm 3 。
5. The formulation according to any one or more of the preceding claims, wherein the particle size D (v, 50%) of the formulation, measured as a dry dispersion with Malvern MasterSizer 3000 (laser diffraction), ranges from 200 μιη to 300 μιη.
6. The formulation according to any one or more of the preceding claims, wherein the anti-caking agent D) has a particle size D (v, 50%) ranging from 100nm to 10 μιη, measured as a dry dispersion with Malvern MasterSizer 3000 (laser diffraction).
7. Formulation according to any one or more of the preceding claims, wherein the fat-soluble vitamin a) is vitamin a acetate or a mixture of vitamin a acetate and vitamin D3, preferably in a weight ratio of 1:1 to 100:1, more preferably in a weight ratio of 10:1 to 85:1.
8. The formulation according to any one or more of the preceding claims, wherein the antioxidant c) is tocopherol or a mixture of tocopherol and a water-soluble antioxidant.
9. The formulation according to any one or more of the preceding claims, wherein the formulation comprises reducing sugar, preferably in an amount of 1.0 to 5.0 wt% and polyol, preferably in an amount of 0.1 to 5.0 wt%, all amounts being based on the total weight of a) to h).
10. The formulation of claim 9, wherein the reducing sugar is glucose, fructose, galactose, high fructose corn syrup, glucose syrup, dry glucose syrup, and any mixtures thereof, and/or wherein the polyol is glycerol, sorbitol, xylitol, maltitol, erythritol, mannitol, and any mixtures thereof.
11. A container having a volume in the range 450l to 3000l, the container comprising a formulation according to any one or more of the preceding claims.
12. A container according to claim 11, wherein the volume of the container ranges from 480 to 2000 litres, preferably from 500 to 1500 litres, more preferably from 500 to 1000 litres, most preferably from 600 to 800 litres.
13. The container according to claim 11 and/or 12, wherein the container is a flexible intermediate bulk container.
14. A method for manufacturing a formulation according to any one or more of claims 1-10, the method comprising the steps of:
A) Dissolving gelatin b), lignosulfonate c) and water-soluble antioxidant c) (if present) in water to obtain a matrix;
b) Heating the fat-soluble vitamin a), the fat-soluble antioxidant c) and the oil (if present) to obtain an active phase;
c) Emulsifying the active phase obtained in step B) into the matrix obtained in step a) to obtain a dispersion;
d) Spray drying the dispersion obtained in step C) in the presence of an anti-caking agent to obtain said formulation;
wherein optionally reducing sugars and/or polyols may be added.
15. The method of claim 14, further comprising the additional step of:
e) Heat treating the formulation obtained in step D).
16. Use of a formulation according to any one or more of claims 1-10 as an additive to a feed or premix.
17. A feed additive, premix or feed comprising a formulation according to any one or more of claims 1-10.
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