JP7093193B2 - Vegetable oil saponified composition - Google Patents

Description

The present invention relates to a vegetable oil saponified composition for feed.

It is widely used to mix lipids such as triglyceride and fatty acid as an energy source in livestock feed. Among them, when a metal salt of fatty acid, which is a saponified product of vegetable oil, particularly fatty acid calcium is supplied as an energy source. It has been reported to be efficient, and Patent Document 1 reports that the survival rate of cultured fish and shellfish is improved by supplying a feed containing fatty acid calcium.
Among livestock animals, in ruminants such as cattle, goats, and sheep, the problem that high fat feeding adversely affects the rumen, reducing digestibility in the rumen and causing loss of appetite. There is. Therefore, so-called bypass fats and oils that are not dissolved or digested in the rumen but are digested in the abomasum and the small intestine thereafter are required, and fatty acid calcium is known as one of such bypass fats and oils. Has been done.
The lipid added to the feed is preferably in the form of granules or particles from the viewpoint of feeding work and mixing work with other feeds.
Further, although the structure of granular particles containing a metal salt of fatty acid is reported in Patent Document 2, it is said that the granular particles of fatty acid metal salt produced by the method described in this document are inferior in odor and palatability. There's a problem.
On the other hand, among lipids, polyunsaturated fatty acids have excellent nutritional functions, but have problems of poor oxidative stability and oxidative deterioration, and when oxidative deterioration occurs, the flavor becomes significantly worse and the odor of livestock feed In addition to deteriorating palatability, there is a problem of adversely affecting the health of livestock. Therefore, synthetic antioxidants such as ethoxyquin are used in feeds, but the acceptable daily intake is set based on the results of chronic toxicity and carcinogenicity tests (0.06 mg / kg body weight).
Patent Document 3 gives an example of adding an antioxidant caramel to a fatty acid calcium salt containing an unsaturated fatty acid, but adhesion of a fatty acid metal salt obtained by adding such a caramel at a certain concentration or more is given. There is a problem that the property is increased, and when crushed to be in the form of granules or particles, it adheres to the crusher and the yield is deteriorated.
Further, the calcium fatty acid containing palm oil, which is a solid fat at room temperature and has a high content of saturated fatty acid described in Patent Document 3, has a problem that the particles become too fine at the time of pulverization and scatter to deteriorate the working environment.

Japanese Patent Application Laid-Open No. 11-266793 Special table 2002-543806 JP-A-6-315350

An object of the present invention is to solve the above-mentioned problems of the prior art. That is, it is a vegetable oil saponified composition for feed that can be fed as an efficient energy source for livestock in general including ruminants, and has high storage stability without the addition of a highly toxic synthetic antioxidant such as ethoxyquin, and is crushed. It is an object of the present invention to provide a vegetable oil saponified composition for feed, which does not sometimes scatter, does not adhere to a grinder, and has a good yield.

The present inventors add fats and oils, calcium hydroxide, water, lipase, and a predetermined amount of caramel having an antioxidant property, and carry out a reaction at a predetermined temperature to achieve the above-mentioned problem. The present invention was completed by finding that it can be produced.
In particular, the present inventors change the hardness of the reaction mixture depending on the relationship between the amount of fat and oil B containing saturated fatty acid as a main component in the fat and oil and the content of (e) caramel having antioxidant property, and further the reaction. I noticed that the scattering situation of the particles when crushing the mixture was different. Although not bound by theory, this is because when the amount of fat B is large, most of the fatty acid portion of the produced vegetable oil saponified composition for feed becomes saturated fatty acid, so that the hardness becomes high and the particles become fine when crushed. However, by including a specific amount of caramel having antioxidant properties, the area around the fatty acid calcium is coated to lower the hardness, and the particles are bound to each other to suppress scattering. Conceivable.
It was also found that a certain level of oxidative stability can be achieved by including a specific amount of caramel having antioxidant properties with respect to the difficulty of oxidation calculated from the contents of various fatty acids.

That is, the present invention provides the following.
<1>
(A) One type of fat or oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and oil and fat B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil.
(B) Calcium hydroxide,
(C) Water,
(D) Lipase,
(E) Caramel having antioxidant properties and (f) other arbitrary components are mixed at a ratio satisfying the following conditions.
[Conditions: The content of fats and oils B in the total mass of (a) to (f) is X (mass%), and the following formula is used from the content of various fatty acids in the total mass of (a) to (f). When the degree of difficulty of oxidation represented by is Y, and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula ( Satisfy 1) and (2),
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3 ]
A vegetable oil saponified composition for feed containing a calcium salt of fatty acid, which is obtained by reacting at a temperature of 30 to 80 ° C.
<2>
The vegetable oil for feed according to <1>, wherein the mass ratio of the fat A containing an unsaturated fatty acid as a main component and the fat B containing a saturated fatty acid as a main component is 10: 0 to 2: 8 among the above (a). Compound composition.
<3>
The content of (a) fat and oil is 65 to 85% by mass, (b) the content of calcium hydroxide is 5 to 15% by mass, and (c) the content of water with respect to the total mass of (a) to (f). The forage vegetable oil saponified product according to any one of <1> to <2>, wherein the amount is 2 to 15% by mass, (a) the amount of lipase added is 20 to 10000 U with respect to 100 g of fat and oil. Composition.
<4>
The caramel (e) was reacted with 0.5 or more antioxidant (antioxidant: 0.5 mM 1,1-diphenyl-2-pcrylhydrazyl (DPPH) ethanol solution at 35 ° C. for 30 minutes. The vegetable oil saponified composition for feed according to any one of <1> to <3>, which is later defined as a decrease in absorbance at 517 nm per 1 mg of caramel).
<5>
The vegetable oil saponified composition for feed according to any one of <1> to <4>, which is in the form of powder or particles.
<6>
The vegetable oil saponified composition for feed according to <5>, wherein the particles having a diameter of 0.125 mm or less are 10% by mass or less, and the particles having a diameter exceeding 2.8 mm are 10% by mass or less.
<7>
The vegetable oil saponified composition for feed according to any one of <5> and <6>, wherein the peroxide value when stored at 50 ° C. for 1 week is 1 meq / kg or less.
<8>
(A) One type of fat or oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and oil and fat B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil.
(B) Calcium hydroxide,
(C) Water,
(D) Lipase,
(E) Caramel having antioxidant properties and (f) other arbitrary components are mixed at a ratio satisfying the following conditions.
[Conditions: The content of fats and oils B in the total mass of (a) to (f) is X (mass%), and the following formula is used from the content of various fatty acids in the total mass of (a) to (f). When the degree of difficulty of oxidation represented by is Y, and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula ( Satisfy 1) and (2),
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3 ]
A method for producing a vegetable oil saponified composition for feed containing a calcium fatty acid salt, which comprises reacting at a temperature of 30 to 80 ° C.
<9>
The production method according to <8>, wherein the hardness of the reaction product 48 hours after the start of the reaction at a temperature of 30 to 80 ° C. does not exceed 4000 gf or more and 11000 gf.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a vegetable oil saponified composition for feed, which has high storage stability, does not scatter during pulverization, and does not adhere to a pulverizer.

It is a graph which shows the effect that the content X of fats and oils B and the content Z of caramel having antioxidant property have on the scattering of a product. It is a graph which shows the effect which the oxidation difficulty Y and the content Z of caramel which has an antioxidant property have on the storage stability of a product.

The vegetable oil saponified composition for feed of the present invention is as follows.
(A) One type of fat or oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and oil and fat B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil.
(B) Calcium hydroxide,
(C) Water,
(D) Lipase,
(E) Caramel having antioxidant properties and (f) other arbitrary components are mixed at a ratio satisfying the following conditions.
[Conditions: The content of fats and oils B in the total mass of (a) to (f) is X (mass%), and the following formula is used from the content of various fatty acids in the total mass of (a) to (f). When the degree of difficulty of oxidation represented by is Y, and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula ( Satisfy 1) and (2),
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3 ]
A vegetable oil saponified composition for feed containing a fatty acid calcium salt obtained by reacting at a temperature of 30 to 80 ° C.

In the present specification, the "vegetable oil saponified composition for feed" is a vegetable oil saponified composition added to the feed of all livestock animals such as cattle, goats, sheep and other ruminants, poultry and other poultry, and pigs. .. Especially in ruminants, a large amount of fat has a problem that the rumen is adversely affected, the digestibility in the rumen is lowered, and the appetite is reduced. However, the feed of the present invention is a fatty acid. By containing a fatty acid metal salt such as calcium, it is not dissolved or digested in the rumen but is digested in the abomasum and the small intestine thereafter, so that it can be fed to ruminants without any problem. Further, when it is in the form of granules or particles, it is possible to provide a vegetable oil saponified composition for feed which can be uniformly mixed with feed, has good storage stability, and is excellent in odor and palatability. can.
The vegetable oil saponified composition for feed of the present invention can be used by adding it to a general livestock feed. A livestock feed composition containing the vegetable oil saponified composition for feed of the present invention may be produced by adding it to a feed production stage, or it may be added to a general livestock feed at the feeding stage for use. .. The vegetable oil saponified composition for feed is preferably in the form of granules or particles from the viewpoint that it can be uniformly mixed with the feed.
The raw materials and other additives of the vegetable oil saponified composition for feed are not particularly limited as long as they are generally used.

In the present specification, (a) "fat / fat A containing unsaturated fatty acid as a main component" means fat / fat containing unsaturated saturated fatty acid as a main constituent fatty acid, and "fat / fat B containing saturated fatty acid as a main component" is used. , Means fats and oils containing saturated fatty acids as the main constituent fatty acids.
"Containing unsaturated fatty acids as a main component" or "containing unsaturated fatty acids as main constituent fatty acids" means that unsaturated fatty acids are contained in an amount exceeding 50% by mass with respect to the total amount of constituent fatty acids. Further, "having saturated fatty acid as a main component" or "containing saturated fatty acid as a main constituent fatty acid" means that saturated fatty acid is contained in an amount exceeding 50% by mass with respect to the total constituent fatty acid mass.
The fat and oil B containing saturated fatty acid as a main component contains preferably 55% by mass or more of saturated fatty acid, and more preferably 60% by mass or more, based on the total mass of constituent fatty acids. It may be 70% by mass or more, 75% by mass or more, or 80% by mass or more.
The fat A containing an unsaturated fatty acid as a main component contains preferably 55% by mass or more of unsaturated fatty acids, more preferably 60% by mass or more, still more preferably 70% by mass or more, based on the total mass of constituent fatty acids. , More preferably 80% by mass or more.

Unsaturated fatty acids are fatty acids that contain at least one unsaturated bond among the carbon bonds in the molecule. It is preferably a long-chain unsaturated fatty acid having 16 or more carbon atoms, more preferably 18 or more carbon atoms.
The valence of unsaturated fatty acids refers to the number of unsaturated bonds contained in one molecule, for example, monovalent unsaturated fatty acids have one unsaturated bond in one molecule. The main component of the unsaturated fatty acid is preferably a divalent or higher fatty acid, and more preferably a trivalent or higher fatty acid. Most preferably, n-3 fatty acid, docosahexaenoic acid and the like can be mentioned. Examples of fats and oils containing the above-mentioned unsaturated fatty acids as constituent fatty acids include rapeseed oil, soybean oil, corn oil, sunflower oil, flaxseed oil, perilla oil, palm olein, palm double olein, fish oil, beef fat, and pork fat.
Saturated fatty acids are fatty acids in which all carbon bonds in the molecule are composed of saturated bonds. It is preferably a long-chain saturated fatty acid having 12 or more carbon atoms, more preferably 16 or more carbon atoms. Examples of fats and oils containing the above-mentioned saturated fatty acids as constituent fatty acids include palm oil, palm midfraction, palm stea, palm oil, palm kernel oil, palm kernel olein, and various extremely hydrogenated oils.

The raw material fat and oil contains one kind of fat and oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and fat and oil B containing saturated fatty acid as a main component, or a mixture of two or more kinds of fat and oil. All you need is. For example, those having a blending ratio of fat A and fat B of 10: 0 to 2: 8, more preferably 9: 1 to 3: 7, and even more preferably 9: 1 to 7: 3.

(A) The total mass of the "mixture of fat A containing unsaturated fatty acid as a main component and fat B containing saturated fatty acid as a main component" is 65 to 65 with respect to the total mass of the above-mentioned components (a) to (f). It is preferably 85% by mass, more preferably 70 to 80% by mass.

(B) "Calcium hydroxide" (Ca (OH) ₂ ) (slaked lime) is added to the above (a) mixed fat and oil. Since "calcium oxide" (CaO) (quick lime) becomes calcium hydroxide due to the presence of water, "calcium oxide" may be added instead of "calcium hydroxide".
To the total mass of the above-mentioned components (a) to (f), preferably 5 to 15% by mass of (b) "calcium hydroxide" is added. It is more preferably 7 to 13% by mass, still more preferably 8 to 12% by mass. When "calcium oxide" is added instead of "calcium hydroxide", "calcium oxide" (molecular weight 56) is added so that the above amount is obtained by converting the molecular weight into "calcium hydroxide" (molecular weight 74). It is preferable to do so.

As used herein, (c) "water" also serves as a reaction solvent. When calcium oxide is used, it reacts with calcium oxide to provide calcium hydroxide. As "water", distilled water, deionized water, tap water and the like can be appropriately used. It is preferable to add 2 to 15% by mass with respect to the total mass of the above-mentioned components (a) to (f).

The product of the present invention is obtained by mixing the above-mentioned and later-described components (a) to (f) and then performing a saponification reaction. At this time, it is preferable to add 20 to 10000 U of lipase to 100 g of fats and oils. It depends on the reaction conditions, the activity of lipase, etc., but is more preferably 200 to 2000 U.
The saponification step can be carried out at 30 to 80 ° C., and the reaction is carried out by uniformly mixing and stirring while heating to 30 to 60 ° C., more preferably 30 to 45 ° C.
In the present specification, (d) "lipase" can be any lipase of animal, plant or microbial origin, and is not limited, but is preferably alkaline, having strong oil-decomposing ability and high heat resistance.

In the present specification, (e) "antioxidant caramel" is a caramel having antioxidant properties obtained by heat-treating a saccharide, and is representative of the caramel described in JP-A-10-150949. It can be mentioned as a good thing.
(E) The amount Z (mass%) of "caramel having antioxidant properties" can be added within a range satisfying the following conditions.
(conditions)
The content of fat and oil B in the total mass of (a) to (f) is expressed by the following formula from X (mass%) and the content of various fatty acids in the total mass of (a) to (f). When the degree of difficulty of oxidation is Y and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula (1) and Satisfy (2)
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3
(1) When the upper limit of Z represented by the formulas (i) to (iii) is exceeded (that is, when the caramel content exceeds 5% by mass), the adhesiveness of the product obtained by the saponification reaction increases. In the crushing process described later, it adheres to the crusher and causes a decrease in yield. Further, if the value is lower than the lower limit of Z represented by the equations (1), (i) to (iii), the particles become finer during pulverization and scatter to the surroundings, which causes deterioration of the environment at the manufacturing site and the handling site. .. Further, if the range is less than the range represented by the formulas (2) (i) to (iii), the storage stability of the obtained composition is lowered and oxidative deterioration is caused during storage.

The amount Z (mass%) of "caramel having antioxidant properties" is more preferably added within the range satisfying the following conditions from the viewpoint of the content X (mass%) of fat and oil B and the suppression of scattering in the pulverization step. ..
(1A) (i) When 0≤X <35: 0 <Z≤5
(ii) When 35 ≤ X <52.5: 1.5 ≤ Z ≤ 5
(iii) When 52.5 <X <100: 2.5 ≤ Z ≤ 5
Or (1B) (i) When 0≤X <22.5: -0.13X + 4≤Z≤5
(ii) When 22.5 ≤ X <37.5: 1 ≤ Z ≤ 5
(iii) When 37.5 ≤ X <52.5: 0.07X-1.5 ≤ Z ≤ 5
(iv) When 52.5 ≤ X <100: 0.04X-0.33 ≤ Z ≤ 5
Or (1C) (i) When 15≤X <22.5: -0.13X + 4≤Z≤0.4X-4
(ii) When 22.5 ≤ X <37.5: 1 ≤ Z ≤ 5
(iii) When 37.5 ≤ X <52.5: 0.07X-1.5 ≤ Z ≤ 5
(iv) When 52.5 ≤ X <100: 0.04X-0.33 ≤ Z ≤ 5
Or (1D) (i) When 22.5 ≤ X <37.5: -0.27X + 11 ≤ Z ≤ 5
(ii) When 37.5 ≤ X <52.5: 0.07X-1.5 ≤ Z ≤ 5
(iii) When X = 52.5: 2 ≦ Z ≦ 5

The amount Z (% by mass) of "caramel having antioxidant properties" is more preferably added within a range satisfying the following conditions from the viewpoint of oxidation difficulty Y and storage stability.
(2A) (i) When 0 ≦ Y <0.3: 0 <Z ≦ 5
(ii) When 0.3 ≤ Y <0.65: 1 ≤ Z ≤ 5
(iii) When 0.65 ≤ Y <1.2: 7.27Y-3.77 ≤ Z ≤ 5
(iv) When 1.2 ≤ Y <3.9: Z = 5
Or (2B) (i) When 0≤Y <0.43: -3.13Y + 3.34≤Z≤5
(ii) When 0.43 ≤ Y <0.64: -4.76Y + 4.05 ≤ Z ≤ 5
(iii) When 0.64 ≤ Y <0.85: 1 ≤ Z ≤ 5
(iv) When 0.85 ≤ Y <1.07: 4.55Y-2.86 ≤ Z ≤ 5
(v) When 1.07 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Or (2C) (i) When 0≤Y <0.43: -3.13Y + 3.34≤Z≤5
(ii) When 0.43 ≤ Y <0.64: -4.76Y + 4.05 ≤ Z ≤ 5
(iii) When 0.64 ≤ Y <0.85: 1 ≤ Z ≤ 5
(iv) When 0.85 ≤ Y <1.07: 4.55Y-2.86 ≤ Z ≤ -13.64Y + 16.59
Or (2D) (i) When 0.43 ≤ Y <0.64: -4.76Y + 4.05 ≤ Z ≤ 5
(ii) When 0.64 ≤ Y <0.85: 19.05Y-11.19 ≤ Z ≤ 5
(Iii) When Y = 0.85: Z = 5
The relationship between Z and X or Z and Y may be selected and combined from the above-mentioned equations.

In the present specification, each unsaturated fatty acid content of fats and oils contained in a vegetable oil saponified composition for feed has a specific coefficient (monovalent ... 0.89 × 10 ^-3 , divalent… 21 × 10 ^-3 , trivalent). The sum of the values multiplied by 39 × 10 ^-3 ) was taken as the oxidation difficulty level Y of the vegetable oil saponified composition for feed (references: Kenji Fukuzawa, Junji Terao, Lipid Peroxidation Experimental Method, Hirokawa Shoten).
The range of difficulty of oxidation Y is 0 when fats and oils containing no unsaturated fatty acid are used, and the higher the content of unsaturated fatty acid, the higher the value. However, in the present specification, the value is trivalent or higher. When the content of unsaturated fatty acid is 100% by mass (3.9), it is regarded as the theoretical maximum value of Y and is set as the upper limit thereof. The range of oxidation difficulty is 0.0 to 2.0, preferably 0.0 to 1.8.

In the present specification, the antioxidant property of caramel is evaluated by the reactivity (radical scavenging ability) between caramel and 1,1-diphenyl-2-pcrylhydrazyl (DPPH), that is, the reactivity with DPPH (radical). It means a radical (capturing ability). As a specific method for measuring the antioxidant property, different amounts of caramel were dissolved in ethanol, 0.5 mM DPPH ethanol solution was added to each, and the mixture was held at 35 ° C. for 30 minutes, and then the absorbance at 517 nm was measured. A regression line was created between the amount of caramel and the amount of decrease in absorbance due to the addition of caramel, and the amount of decrease in absorbance per 1 mg of caramel was determined and used as the antioxidant property of caramel. The larger this value is, the better the antioxidant property is, but if it is too high, the viscosity of the caramel becomes too high and the workability is lowered, so that it is preferably 0.5 to 1.0, more preferably 0.6 to 1. It is 0.0.

The "antioxidant caramel" can be produced, for example, as follows. It is heated at preferably 100 ° C. or higher, more preferably 120 to 150 ° C. in the presence of 1 to 10 parts by mass of the basic compound with respect to 100 parts by mass of the glucose aqueous solution having a concentration of 75 to 95% by mass. Then, by adding 30 to 50 parts by mass of water to 100 parts by mass of the initial glucose aqueous solution, the sugar content is 60 to 75, preferably 65 to 70, pH 3 to 5, preferably 3.5 to 4.5, and anti. Caramel with an oxidizing property of 0.5 to 1.0 can be obtained. The heating time is preferably 1 to 10 hours, more preferably 2 to 8 hours.

Basic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen salts such as sodium hydrogencarbonate and potassium hydrogencarbonate, acetic acid and citrus. Alkali metal salts of organic acids such as acids (eg, sodium salts, potassium salts), or ammonium salts, and ammonium hydroxide may be used, and one or more mixtures selected from these groups may be used. Can be done.

The pH of the aqueous solution before the heat treatment is preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. If the reaction temperature (heat treatment temperature) is lower than 120 ° C., the reaction does not proceed sufficiently. Further, if the temperature is higher than 150 ° C., not only the risk of solidification / carbonization of the reaction system increases, but also the antioxidant property of the obtained caramel decreases, which is not preferable. The preferred reaction temperature is 125 to 135 ° C, more preferably around 130 ° C. Further, if the amount of the basic compound is less than 1 part by mass, the reaction does not proceed sufficiently. That is, caramel having antioxidant properties cannot be obtained. On the other hand, if the amount is more than 10 parts by mass, the reaction proceeds violently, a large amount of bubbles are generated in a short time, and there is a risk that the bubbles may be blown out from the reaction vessel. If the heating time is less than 1 hour, the reaction does not proceed sufficiently. Further, as the heating time becomes longer, the reaction progresses and the viscosity gradually increases.

The product of the present invention can contain components other than (a) to (e), if necessary. For example, molasses is exemplified for the purpose of enhancing palatability, and antioxidants other than caramel having the above-mentioned antioxidant properties are exemplified for the purpose of enhancing storage stability. The content of the components other than (a) to (e) is preferably 0.5 to 10% by mass, more preferably 1 to 9% by mass, based on the total mass of the vegetable oil saponified composition for feed. ..

The method for producing the vegetable oil saponified composition for feed of the present invention is as follows.
Process I)
(A) One type of fat or oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and oil and fat B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil.
(B) Calcium hydroxide,
(C) Water,
(D) Lipase and (e) caramel having antioxidant properties are mixed at the ratio of the following conditions.
Process II)
The mixture obtained in step I) is reacted at a temperature of 30 to 80 ° C. to produce a composition containing a fatty acid calcium salt.
Process III)
If necessary, the composition containing the fatty acid calcium salt obtained in Step II) is stored at 5 to 35 ° C. for 24 to 48 hours and pulverized to obtain a granular or particulate composition.

The vegetable oil saponified composition for feed of the present invention is preferably in the form of granules or particles. Preferably, the particles having a diameter of 0.125 mm or less are 10% by mass or less, and the particles having a diameter exceeding 2.8 mm are 10% by mass or less. When the particle size is within the range, it does not scatter during crushing, does not adhere to the crusher, and has a good yield. In addition, the rumen bypass property is good in ruminants, and the digestibility in the abomasum is also good.

In preparing a composition containing fatty acid calcium, in order to form a block and further obtain particles having such a particle size, the hardness of the composition in the step of producing the composition containing fatty acid calcium is 4000 to 11000 gf. If the hardness is less than 4000 gf, the adhesiveness is high and it adheres to the wall surface of the crusher, and if it exceeds 11000 gf, it is too hard to be crushed. The composition having the indicated hardness is preferably pulverized by a crusher such as a hammer crusher. The production efficiency is that the hardness of the reaction product does not exceed 4000 gf or more and 11000 gf within 24 to 48 hours after the components including (a) to (f) are mixed and the reaction is started at a temperature of 30 to 80 ° C. It is preferable from the viewpoint of.

Hereinafter, embodiments of the present invention will be described with reference to examples. In the following examples, "%" means "mass%" unless otherwise specified.

(Caramel with antioxidant properties)
25 parts by mass of water, 80 parts by mass of saccharide (glucose), 5 parts by mass of basic compound (sodium citrate) are mixed, heated at 130 ° C. for 3 hours, 40 parts by mass of water is added, and 120 parts by mass of caramel is added. Manufactured. When the sugar content, pH and antioxidant property of the obtained caramel were measured as follows, the sugar content was 65, the pH was 3.7 and the antioxidant property was 0.63.
The sugar content was measured by adjusting the temperature of caramel to 20 ° C. and using a sugar content meter (manufactured by ATAGO, H-80).
The pH of the caramel was adjusted to 20 ° C. and measured using a pH meter (Seven2Go, manufactured by METTLER TOLEDPO).
For antioxidant properties, a caramel diluted solution (0.3 g of caramel dissolved in 5 ml of distilled water) was taken in an amount of 0 (blank), 2, 5, or 8 μl, respectively, and dissolved in 4 ml of ethanol, respectively. After adding 1 ml of .5 mM DPPH ethanol solution and reacting in a constant temperature bath at 35 ° C. for 30 minutes, the absorbance at 517 nm was measured, and a regression line was created for the amount of caramel and the amount of decrease in absorbance due to the addition of caramel. , Calculated as the amount of decrease in absorbance per 1 mg of caramel.

(Example 1)
<Mixing process>
10.1 g of slaked lime (calcium hydroxide) was added to 75 g of fat A (linseed oil), and the mixture was mixed and stirred in a mixing tank.
To the mixture was added 5 g of antioxidant caramel, 5 g of molasses and 4.9 g of water.
Further, 0.015 g (400 U) of lipase (Amano AK, 20000 U / g) was added to 100 g of the above mixture, the liquid temperature was heated to 50 ° C., and the mixture was further stirred for 30 minutes to react.
<Standing process>
The mixture obtained in the above mixing step was poured into a container having a length of 8 cm, a width of 22 cm, and a height of 8 cm, and allowed to stand at 25 ° C. for 48 hours to proceed with the reaction. The results of measuring the hardness of the mixture are shown in Table 2.
<Crushing process>
Further, the above mixture was taken out from the container and finely pulverized using a hand mixer. When the particle size of the obtained granules was measured by the sieving method, the particle size distribution in Table 3 was shown.

(Examples 2 to 11)
Granules were prepared in the same manner as in Example 1 except that the amounts of fat A, fat B, antioxidant caramel, and water were changed as shown in Table 1.
(Comparative Examples 1 to 18)
Granules were prepared in the same manner as in Example 1 except that the amounts of fat A, fat B, antioxidant caramel, and water were changed as shown in Table 1.
The amount of unsaturated fatty acids (relative to the total amount of constituent fatty acids) of "linseed oil" used as fats and oils A in the above Examples and Comparative Examples was 91% by mass, the amount of unsaturated fatty acids of "rapeseed oil" was 93% by mass, and used as fats and oils B. The amount of saturated fatty acid in the "palm stea" was 67% by mass.

<Hardness>
In the above-mentioned standing step, a mixture that has been allowed to stand at 25 ° C. for 48 hours is introduced into a piercing needle jig (φ5) by 15 mm by a leometer (manufactured by Shimadzu Corporation, EZTest / CE), and the stress at that time is used as hardness. It was measured and evaluated as follows.
◯: 4000 gf or more and 11000 gf or less Δ: 3000 gf or more and less than 4000 gf, 11000 gf excess <adhesion>
The state of the solidified mixture after pulverization was measured according to the following criteria, and the adhesion of particles was evaluated.
◯: After crushing, the particle size exceeding 2.8 mm is 10% by mass or less Δ: After crushing, the particle size exceeding 2.8 mm exceeds 10% by mass, 20% by mass or less ×: After crushing, the particle size exceeding 2.8 mm is 20 Those that exceed the mass% or that the crushed substances bind to each other during crushing and do not form particles <scattering>
The treatment state of the solidified mixture in the crusher was measured according to the following criteria, and the scattering of particles was evaluated.
◯: After crushing, the particle diameter of 0.125 mm or less is 10% by mass or less ×: After crushing, the particle diameter of 0.125 mm or less exceeds 10% by mass.

<Store stability test Peroxide value (POV)>
From the granules obtained in the above pulverization step, only the granules having a particle size of 0.5 to 1.0 mm were recovered by a sieving method, filled in a transparent pouch bag, and stored in a constant temperature bath at 50 ° C. .. After one week, the peroxide value (POV) was measured. The measurement was based on the standard oil and fat analysis test method edited by the Japan Oil Chemicals Association.
The storage stability was evaluated as follows using each POV value as an index.
◯: POV value is 0 meq / kg
Δ: POV value exceeds 0 meq / kg and less than 1 meq / kg ×: POV value is 1 meq / kg or more

<Comprehensive evaluation>
Based on the evaluation results of hardness, adhesion, scattering, and storage stability, the comprehensive evaluation was evaluated as follows.
A: All evaluations are ○
B: No evaluation of ×, 1 evaluation of △ C: No evaluation of ×, 2 or more evaluations of △ D: 1 evaluation of × E: 2 or more evaluations of ×, or cannot be crushed Things

The above evaluation results are shown in Tables 2-4. In addition, graphs showing the relationship between X and Z and the scattering evaluation of the product shown in Tables 2 to 4 and the relationship between Y and Z and the storage stability evaluation are shown in FIGS. 1 and 2.
Examples 1 to 11 in which the content X of the fat and oil B containing a saturated fatty acid as a main component, the difficulty of oxidation Y, and the content Z of the caramel having an antioxidant property satisfy the following formulas (1) and (2) are described. It did not scatter during crushing, did not adhere to the crusher, and was excellent in storage stability. In particular, Examples 4 to 9 in which the blending ratio of the fat A containing the unsaturated fatty acid as the main component and the fat B containing the saturated fatty acid as the main component is 9: 1 to 3: 7, and particularly 9: 1 to 7: 3 are carried out. Examples 4 to 6 had hardness suitable for pulverization and were free from scattering and adhesion.
On the other hand, among the following formulas (1) and (2), a comparative example in which the addition amount Z of caramel having antioxidant property exceeds the upper limit value (5% by mass) of the following formulas (1) (i) to (iii). In Nos. 5, 8, 11, 14, and 18, the pulverized substances were bound to each other during pulverization and did not form particles. In Comparative Examples 10, 12, 13, 15, 16 and 17, which are smaller than the lower limit of the formulas (1) (i) to (iii), the particles become finer and scatter during pulverization, and the formulas (2) (i) to (iii) are scattered. In Comparative Examples 1, 2, 3, 4, 6, 7, 9, 10 and 12, which do not satisfy the above conditions, the peroxide value exceeds 1 meq / kg after storage at 50 ° C. for 1 week, and the storage stability is poor. rice field.
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5

Claims (8)

(A) One type of fat or oil selected from the group consisting of fat and oil A containing 60% by mass or more of unsaturated fatty acid and fat and oil B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil. ,
(B) Calcium hydroxide,
(C) Water,
(D) Lipase,
(E) Caramel having antioxidant properties (f) and other arbitrary components are mixed at a ratio satisfying the following conditions.
[Conditions: The total mass of the fat A and the fat B is 65 to 85% by mass with respect to the total mass of the above (a) to (f), and the mass ratio of the fat A and the fat B is 10: 0 to 7: 3. The following formula is used from the content of fats and oils B in the total mass of the above (a) to (f) being X (mass%) and the content of various fatty acids in the total mass of the above (a) to (f). When the degree of difficulty of oxidation represented by is Y, and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula ( Satisfy 1) and (2),
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3 ]
A vegetable oil saponified composition for feed containing a fatty acid calcium salt obtained by reacting at a temperature of 30 to 80 ° C. The vegetable oil saponified composition for feed according to claim 1, wherein the mass ratio of the fat A and the fat B is 9 : 1 to 7: 3 in the above (a). The content of (a) fat and oil is 65 to 85% by mass, (b) the content of calcium hydroxide is 5 to 15% by mass, and (c) the content of water with respect to the total mass of (a) to (f). The feed vegetable oil saponified product according to any one of claims 1 or 2, wherein the amount is 2 to 15% by mass, and (a) the amount of lipase added is 20 to 10000 U with respect to 100 g of fat and oil. Composition. The caramel (e) was reacted with 0.5 or more antioxidant (antioxidant: 0.5 mM 1,1-diphenyl-2-pcrylhydrazyl (DPPH) ethanol solution at 35 ° C. for 30 minutes. The vegetable oil saponified composition for feed according to any one of claims 1 to 3, further defined as a reduction in absorbance at 517 nm per 1 mg of caramel). The vegetable oil saponified composition for feed according to any one of claims 1 to 4, which is in the form of powder or particles. The vegetable oil saponified composition for feed according to claim 5, wherein the particles having a diameter of 0.125 mm or less are 10% by mass or less, and the particles having a diameter exceeding 2.8 mm are 10% by mass or less. The vegetable oil saponified composition for feed according to any one of claims 5 or 6, wherein the peroxide value when stored at 50 ° C. for 1 week is 1 meq / kg or less. (A) One type of fat or oil selected from the group consisting of fat and oil A containing unsaturated fatty acid as a main component and oil and fat B containing saturated fatty acid as a main component, or a mixture of two or more types of fat and oil.
(B) Calcium hydroxide,
(C) Water,
(D) Lipase,
(E) Caramel having antioxidant properties and (f) other arbitrary components are mixed at a ratio satisfying the following conditions.
[Conditions: The content of fats and oils B in the total mass of (a) to (f) is X (mass%), and the following formula is used from the content of various fatty acids in the total mass of (a) to (f). When the degree of difficulty of oxidation represented by is Y, and the content of (e) antioxidant caramel in the total mass of the above (a) to (f) is Z (mass%), Z is the following formula ( Satisfy 1) and (2),
(1) (i) When 0 ≤ X <35: 0 <Z ≤ 5
(ii) When 35 ≤ X <60: 0.004 (X-35) ² ≤ Z ≤ 5
(iii) When 60 ≤ X <100: 2.5 ≤ Z ≤ 5
(2) (i) When 0 ≤ Y <0.3: 0 <Z ≤ 5
(ii) When 0.3 ≤ Y <1.05: 1.8Y-0.54 ≤ Z ≤ 5
(iii) When 1.05 ≤ Y <3.9: -1 / (4 (Y-0.95)) + 2Y + 1.75 ≤ Z ≤ 5
Oxidation difficulty Y = content of monovalent unsaturated fatty acid (% by mass) x 0.89 x 10 ^-3
Content of +2 valent unsaturated fatty acids (% by mass) x 21 x 10 ^-3
Content of unsaturated fatty acids with +3 valence or higher (% by mass) x 39 x 10 ^-3 ]
A method for producing a vegetable oil saponified composition for feed, which comprises reacting at a temperature of 30 to 80 ° C. and having a hardness of a reaction product of 4000 gf or more and not exceeding 11000 gf.

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