WO2018164202A1 - Emulsifying powdered oil or fat composition, and emulsified composition - Google Patents

Abstract

An objective of the present invention is to provide an emulsifying powdered oil or fat composition with which an emulsified composition can be produced, not only if an emulsifying agent is used, but also without using an emulsifying agent.　The present invention is an emulsifying powdered oil or fat composition that contains a powder-form oil or fat composition that satisfies the following condition (a). (a) A powder-form oil or fat composition containing an oil or fat component including at least one type of XXX triglyceride having a fatty acid residue X having a carbon number x at the 1-3 positions of the glycerol, wherein the carbon number x is an integer selected from 10-22, the oil or fat component contains a β-type oil or fat, the particles of the powder-form oil or fat composition are plate-shaped, and the loose bulk density of the powder-form oil or fat composition is 0.05-0.6g/cm3.

Description

Emulsified powder and fat composition and emulsified composition

The present invention is not limited to the case where an emulsifier is used, and an emulsified composition can be produced without using an emulsifier. The emulsified powder and fat composition for emulsification, the emulsified composition produced using the powder and fat composition, and It is related with the manufacturing method of the said emulsion composition, and the emulsification adjuvant containing the said powdered oil-fat composition.
This application claims priority on March 8, 2017 based on Japanese Patent Application No. 2017-43433 filed in Japan, the contents of which are incorporated herein by reference.

Conventionally, in the confectionery bakery field, emulsifiers have been widely used for the purpose of increasing volume, improving texture and preventing aging. However, when the emulsifier is used, there is a problem that the unique flavor and smell derived from the emulsifier itself remain in the confectionery / bread and the flavor as a food is impaired. And an emulsifier may have an unfavorable influence on food texture, such as making a mouth melt worse. Furthermore, due to the recent increase in health consciousness, some foods have a social demand to reduce the amount of emulsifier used as much as possible, and a material that can produce an emulsified composition without using an emulsifier as much as possible has been demanded.

In the prior art, there are some techniques that use proteins (enzymes) or starches instead of emulsifiers. For example, a pre-plasticized shortening oil composition for bread making comprising pregelatinized cross-linked starch (except when the water content exceeds 15% by weight), saccharide-degrading enzyme and edible oil / fat, An oil composition for breadmaking containing 1 to 20 parts by weight of starch with respect to 100 parts by weight of the edible oil and fat is known (Patent Document 1). This technique uses pregelatinized cross-linked starch and a saccharide-degrading enzyme as essential components and is not a technique that anyone can easily use. In addition, an emulsified composition is produced using a natural emulsifying aid such as lecithin and protein, and an emulsified composition cannot be produced only with powdered oil and fat as in the present invention.
An oil / fat composition containing 70 to 99% by weight of an oil / fat, containing an amylolytic enzyme that is substantially inactive at 95 ° C. or higher and containing no synthetic emulsifier is also known ( Patent Document 2). This technique uses an amylolytic enzyme that is substantially inactive at 95 ° C. or higher as an essential component, and does not produce an emulsified composition with powdered fats and oils as in the present invention.
Furthermore, a plastic water-in-oil emulsion containing enzyme-treated egg yolk obtained by treating fats and oils, and egg yolk with phospholipase A and protease is known (Patent Document 3). This technique uses enzyme-treated egg yolk as an essential component and does not form an emulsified composition with powdered oil and fat as in the present invention.
Thus, the technique which manufactures an emulsified composition by powdered fats and oils until now is not known.

Japanese Patent No. 3632280 JP-A-10-248480 Japanese Patent No. 4093689

The object of the present invention is not only to use an emulsifier, but also to provide a powder oil composition for emulsification that can produce an emulsified composition without using an emulsifier.

As a result of intensive studies on the above problems, the present inventors have surprisingly realized that the emulsified composition is not only in the case of using an emulsifier, but also in the case of using an emulsifier as long as it is a powdered fat composition satisfying specific conditions. The present invention has been completed by finding that the product can be manufactured. That is, the present invention can include the following aspects.

[1] A powdered oil / fat composition for emulsification containing a powdered oil / fat composition satisfying the following condition (a).
(A) A powdery oil / fat composition containing an oil / fat component containing one or more XXX-type triglycerides having a fatty acid residue X having carbon number x at positions 1 to 3 of glycerin, wherein the carbon number x is Is an integer selected from 10 to 22, wherein the fat and oil component includes β-type fat and oil, the particles of the powdery fat composition have a plate shape, and the loose bulk density of the powdery fat and oil composition is 0.05 to 0.6 g / cm ³ .
[2] The powdered fat composition for emulsification according to [1], wherein the fat component is a β-type fat.
[3] The powdered fat / oil composition for emulsification according to [1] or [2], wherein the XXX type triglyceride contains 50% by mass or more when the total mass of the oil / fat component is 100% by mass.
[4] The emulsified powder oil and fat composition according to any one of [1] to [3], wherein the carbon number x is an integer selected from 16 to 18.
[5] The powdered oil and fat composition contains a β-type oil and fat obtained by keeping the oil and fat composition raw material containing the XXX-type triglyceride at or above the cooling temperature obtained from the following formula, and cooling and solidifying. [1] The powdered oil composition for emulsification according to any one of [4] to [4].
Cooling temperature (° C.) = Carbon number ×× 6.6−68
[6] β-type obtained by cooling and solidifying the powdered fat / oil composition at a temperature equal to or higher than the melting point of α-type oil / fat corresponding to β-type oil / fat. The powder oil composition for emulsification according to any one of [1] to [5], comprising an oil and fat.
[7] The powdered fat composition for emulsification according to any one of [1] to [6], wherein the powdery fat composition has an average particle diameter of 20 μm or less.
[8] An emulsified composition comprising the emulsified powder oil-fat composition according to any one of [1] to [7].
[9] The emulsified composition according to [8], comprising 0.5 to 20 parts by mass of the emulsified powder / fat composition with respect to 100 parts by mass of the oil phase of the emulsified composition.
[10] The emulsion composition according to [8] or [9], wherein the emulsion composition is a water-in-oil emulsion composition.
[11] The emulsion composition according to any one of [8] to [10], wherein the emulsion composition does not contain an emulsifier.
[12] When producing an emulsified composition by mixing an aqueous phase and an oil phase, the emulsified powder oil-fat composition according to any one of [1] to [7] is blended in the oil phase. A method for producing the composition.
[13] The method for producing an emulsified composition according to [12], wherein 0.5 to 20 parts by mass of the emulsified powder oil and fat composition is blended with 100 parts by mass of the oil phase of the emulsified composition.
[14] The method for producing an emulsion composition according to [12] or [13], wherein the emulsion composition is a water-in-oil emulsion composition.
[15] The method for producing an emulsified composition according to any one of [12] to [14], which is produced without using an emulsifier.
[16] An emulsifier substitute or an emulsification auxiliary comprising the emulsified powder oil-fat composition according to any one of [1] to [7] as an active ingredient.

According to the present invention, by incorporating a powder oil composition for emulsification that satisfies a specific condition, not only when an emulsifier is used, but also when an emulsifier is not used, anyone can easily produce an emulsified composition. it can. Furthermore, since the powder oil composition for emulsification is not an emulsifier, it is safer than the case where an emulsifier is used, and the amount added can be used without limitation. In addition, the emulsified powder / fat composition does not have a unique flavor or odor, and therefore hardly adversely affects the finished emulsified composition. Therefore, it can be widely used for various foods.
On the other hand, since an emulsifier (surfactant) can cause rough hands, rough skin, allergies, and the like, there is a problem that it is desired to limit the amount of the emulsifier used in cosmetics and pharmaceuticals other than food as much as possible. Therefore, the emulsified powder / fat composition of the present invention can be suitably used for cosmetics, pharmaceuticals, and the like for which the amount of the emulsifier is desired to be limited as much as possible.
Furthermore, since the said powdery fat composition has an emulsification power uniquely, it can be used also as a substitute of an emulsifier, or an emulsification auxiliary agent with respect to the existing various emulsifiers. For example, if the emulsified powder / fat composition of the present invention is added under conditions where oil-water separation is likely to occur, the oil-water separation can be suppressed by the emulsifying power. If such emulsification assisting power is utilized, the emulsification stability in various foods, cosmetics, pharmaceuticals and the like can be further improved.

Emulsification when the powder oil composition for emulsification of the present invention is added to 0.01% by weight, 1.0% by weight, and 5.0% by weight of the oil and stored at 50 ° C. overnight and then mixed and emulsified. It is the figure (photograph) which showed the state immediately after and 72 hours afterward. It is the figure (photograph) which showed the state immediately after emulsification, after 5 hours, and 24 hours after adding and emulsifying the powder oil-fat composition for emulsification of this invention by 5.0 mass% with respect to oil. It is the figure (photograph) which showed the state immediately after emulsification, after 5 hours, and 24 hours after mixing emulsification without adding the powdered oil-fat composition for emulsification of this invention. It is the figure (photograph) which showed the state after 5 hours and 24 hours after adding commercially available powdered fats and oils without adding the emulsified powdery fats composition of this invention. FIG. 2 is a diagram showing the degree of oil / water separation that occurs when a mayonnaise-like food to which the emulsified powder oil composition of the present invention is added is stored at −20 ° C. FIG. It is an external appearance photograph of the powdered oil-fat composition (beta type fats and oils) of Production Example 7 of the present invention. It is an external appearance photograph of the powdered oil-fat composition (beta type fats and oils) of Production Example 7 of the present invention. It is an external appearance photograph of the fats and oils composition (alpha-type fat and oil) of the manufacture comparative example 3 of this invention. It is a microscope picture of the powdered fats-and-oil composition (beta type fats and oils) of manufacture Example 7 of this invention. It is a microscope picture of the oil-fat composition (alpha type fat) of the manufacture comparative example 3 of this invention. It is a X-ray-diffraction figure of the powdered fats-and-oil composition (beta type fats and oils) of manufacture Example 7 of this invention. It is a X-ray-diffraction figure of the oil-fat composition (alpha-type fat) of the manufacture comparative example 3 of this invention. In the photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 18 and Comparative Example 5 of the present invention, in order from the left, (1) Example 18, 20 ° C., 10 minutes later, (2) Example 18, 80 ° C., 10 minutes later, (3) Comparative Example 5, 20 ° C., 10 minutes later, (4) Comparative Example 5, 80 ° C., 10 minutes later. 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 18 and Comparative Example 5, (1) Example 18, 20 ° C., 14 hours later, (2) Example 18, after 14 hours at 80 ° C. (3) After Comparative Example 5, 20 ° C., 14 hours, (4) After Comparative Example 5, 80 ° C., 14 hours. In the photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 19 and Comparative Example 6, (1) Example 19, 20 ° C., 10 minutes later, (2) Example 19, after 10 minutes at 80 ° C. (3) After Comparative Example 6, 20 ° C., 10 minutes later (4) After Comparative Example 6, 80 ° C., 10 minutes later. In the photograph 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 19 and Comparative Example 6, in order from the left, (1) Example 19, 20 ° C., 14 hours later, (2) Example 19, after 14 hours at 80 ° C, (3) after Comparative Example 6, 20 ° C, 14 hours, (4) after Comparative Example 6, 80 ° C, 14 hours. In the photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsified compositions of Example 20 and Comparative Example 7, (1) Example 20, 20 ° C., 10 minutes later, (2) Example 20, 80 ° C., 10 minutes later, (3) Comparative Example 7, 20 ° C., 10 minutes later, (4) Comparative Example 7, 80 ° C., 10 minutes later. 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 20 and Comparative Example 7, (1) Example 20, 20 ° C., 14 hours later, (2) Example 20, after 14 hours at 80 ° C., (3) after Comparative Example 7, 20 ° C., 14 hours, and (4) after Comparative Example 7, 80 ° C., 14 hours. 3 is a photomicrograph (100 times) of the powdered oil / fat composition A used in Tests 1 to 3. 3 is a photomicrograph (300 times) of the powdered fat / oil composition A used in Tests 1 to 3. 3 is a photomicrograph (100 ×) of powdered fats and oils B used in tests 1 to 3. 3 is a photomicrograph (300 times) of powdered fats and oils B used in Tests 1 to 3.

Hereinafter, the emulsion composition of the present invention will be described in order.
<Emulsified composition>
The emulsified composition of the present invention refers to an emulsion containing an oil phase, an aqueous phase, and an emulsified powder fat composition. The emulsion composition of the present invention may be a water-in-oil emulsion composition (a so-called W / O emulsion in which a water phase is dispersed in an oil phase that is a continuous phase), or an oil-in-water type. It may be an emulsified composition (so-called O / W emulsion in which an oil phase is dispersed in an aqueous phase that is a continuous phase). As will be described later, since the powdered fat composition for emulsification of the present invention has good compatibility with the oil phase, the emulsified composition of the present invention tends to form a water-in-oil emulsion composition. A water-type emulsion composition is preferred. Furthermore, since the emulsifying power of the emulsified powder / fat composition of the present invention itself, the emulsified composition of the present invention preferably does not contain an emulsifier. Moreover, since the emulsified powder oil-fat composition of this invention can also assist the emulsifying power of the existing emulsifier, it is also preferable to set it as the emulsified composition which does not contain an emulsifier as much as possible.
The emulsified composition of the present invention may include not only foods but also cosmetics and pharmaceuticals. Specific examples of foods include margarine, fat spread, whipped cream, butter cream, ganache and the like, milk, fresh cream, ice Cream, mayonnaise, coffee whitener, white sauce, dressing, cream stew, custard cream, soup and the like. Specific examples of cosmetics and pharmaceuticals include skin creams, sun creams, hand creams, hair creams, hair treatments, massage creams, ointment bases, skin lotions, emulsions, serums, massage cosmetics, body lotions. , Body creams, makeup cosmetics, external preparations, external gels, creams, ointments, liniments, lotions, haps, plasters, sprays, aerosols and the like.
When the mass of the emulsified composition (oil phase + water phase) excluding the emulsified powder oil composition of the present invention is 100% by mass, the content of the oil phase is preferably 48 to 98% by mass, more preferably Is from 60 to 98% by mass, more preferably from 75 to 98% by mass. The content of the aqueous phase is preferably 2 to 52% by mass, more preferably 2 to 40% by mass, and still more preferably 2 to 25% by mass.

<Oil phase>
When the emulsified composition is a food, the oil phase of the emulsified composition of the present invention includes, for example, ordinary edible fats and oils. Specific examples of edible oils include soybean oil, rapeseed oil, cottonseed oil, safflower oil, sunflower oil, rice oil, corn oil, sesame oil, olive oil, palm oil, palm fractionated oil (palm fractionated soft oil (palm olein, palm super olein) Etc.), palm middle melting point, palm fractionated hard oil (palm stearin, etc.), shea fat, shea fractionated oil, monkey fat, monkey fractionated oil, iripe fat, cocoa butter, coconut oil, palm kernel oil, milk fat, butter And mixed oils thereof, processed oils and fats (hydrogenated oil, transesterified oil, fractionated oil, etc.) and the like. These edible fats and oils can be used alone or in combination. The oil phase of the emulsified composition of the present invention contains the edible fat / oil preferably at 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass ( That is, it is preferable that all of the oil phase is edible fats and oils).

In addition, the oil phase of the emulsified composition of the present invention includes, for example, an oil normally used in cosmetics or pharmaceuticals when the emulsified composition of the present invention is a cosmetic or pharmaceutical product. For example, hydrocarbons such as liquid paraphfin, squalane, isostearyl alcohol, vegetable oils such as olive squalane, jojoba oil, macadamia nut oil, cottonseed oil, ester oils such as isostearyl isostearate and cetyl isostearate, higher fatty acids such as isostearic acid, Triglycerides such as 2-ethylhexanoic acid triglyceride, ether oils such as dioctyl ether, silicone oils such as methylpolysiloxane and cyclic silicone can be used, and one or more of these can be used in combination. . Further, the oil phase of the emulsion composition of the present invention preferably contains the above oil component at 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass (ie, , All of the oil phase is preferably oil).

<Water phase>
In the aqueous phase of the emulsified composition of the present invention, normal water can be used regardless of whether the emulsified composition of the present invention is a food, cosmetic or pharmaceutical product. The aqueous phase may contain only water, and may contain other substances that dissolve in water other than water. The water is preferably ion exchange water, distilled water, tap water, sterilized water or the like. Further, the above-mentioned other substances that dissolve in water are not particularly limited as long as they are substances that are usually contained in the aqueous phase of an emulsified composition used as a food, cosmetic, or pharmaceutical product. For example, in the case of food, salty agents such as sodium chloride and potassium chloride, acidulants such as acetic acid, lactic acid and gluconic acid, sweeteners such as saccharides and sugar alcohols, stevia and aspartame can be blended. In the case of cosmetics and pharmaceuticals, drugs such as vitamin C, E, A and derivatives thereof, citric acid and citrate, lactic acid and lactate, amino acids and amino acid salts, chelating agents, and the like can be blended. The aqueous phase of the emulsified composition of the present invention contains the above water preferably at 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass (ie, water). Preferably all of the phases are water).

<Other components contained in the emulsified composition>
The emulsified composition of the present invention may optionally contain “other components” in addition to the above-described components in the oil phase or the aqueous phase. In the case of a food, components used in the food can be blended as necessary within a range that does not extremely impair the effects of the present invention. For example, as the “other components”, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polysorbate, polyglycerin condensed ricinolein fatty acid ester, glycerin fatty acid ester, soybean lecithin, egg yolk lecithin, soybean lysolecithin, egg yolk lysolecithin, Enzyme-treated egg yolk, saponin, plant sterols, emulsifiers such as milk fat globule film, flavoring, coloring agents such as β-carotene, caramel, red yeast rice pigment, flavoring ingredients, thickening stabilizer, tocopherol, rutin and other antioxidants Agents, plant proteins such as wheat protein and soybean protein, eggs and various processed eggs, dairy products such as skim milk powder, whole milk powder, and whey protein, flavoring materials, seasonings, flavor enhancers, pH adjusters, food preservatives , Fruit, fruit juice, coffee, nut paste, spices, cacao mass, cocoa powder, cereal , Legumes, vegetables, meat, food materials and food additives such as seafood and the like.
Moreover, also in the case of cosmetics and pharmaceuticals, the components used in cosmetics and pharmaceuticals can be blended as necessary within a range that does not extremely impair the effects of the present invention. Examples of the “other components” include surfactants, thickeners, preservatives, antioxidants, various powders, pH adjusters, ultraviolet absorbers, antifading agents, antifoaming agents, inorganic pigments and organic Examples thereof include coloring materials such as pigments.
The “other components” described above are blended in the oil phase if oil-soluble and in the water phase if water-soluble.

<Emulsified powder / fat composition>
The present invention relates to a powdered oil / fat composition for emulsification containing a powdery oil / fat composition satisfying the following condition (a) (hereinafter also simply referred to as “powdered oil / fat composition”).
(A) A powdered fat composition containing one or more XXX-type triglycerides having a fatty acid residue X having carbon number x at positions 1 to 3 of glycerin, wherein the carbon number x is 10 to 22 is an integer selected from the above, wherein the oil / fat component contains β-type oil / fat, the particles of the powder / fat composition have a plate shape, and the loose bulk density of the powder / fat composition is 0.05 to 0.00. 6 g / cm ³ .
The emulsified powder / fat composition of the present invention may optionally contain an emulsifier, a fragrance, a colorant, skim milk powder, whole fat milk powder, cocoa powder, sugar, dextrin and the like in addition to the powder oil composition described above.
The content of the powder fat composition satisfying the above condition (a) in the emulsified powder fat composition is, for example, 50% by mass or more, preferably 100% by mass when the total mass of the emulsified powder fat composition is 100% by mass. Is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less. Is an upper limit. 100 mass% of the powdered oil / fat composition for emulsification may be the powdered oil / fat composition satisfying the condition (a). The said powder fat composition can be used 1 type or 2 or more types, Preferably it is 1 type or 2 types, More preferably, 1 type is used.

<Oil component>
The powdered oil / fat composition of the present invention contains an oil / fat component. The fat component contains at least XXX type triglyceride, and optionally other triglycerides.
The fat component includes β-type fat. Here, the β-type fats and oils are fats and oils composed only of β-type crystals, which is one of crystal polymorphs of fats and oils. Other crystalline polymorphic fats and oils include β ′ type fats and oils and α type fats and oils, and β ′ type fats and oils are fats and oils composed only of β ′ type crystals that are one of the polymorphic forms of fats and oils. α-type fats and oils are fats and oils composed only of α-type crystals, which is one of crystal polymorphs of fats and oils. Some fats and oils crystals have the same composition but have different sublattice structures (crystal structures) and are called crystal polymorphs. Typically, there are a hexagonal type, an orthorhombic vertical type, and a triclinic parallel type, which are called α type, β ′ type, and β type, respectively. In addition, the melting points of each polymorph increase in the order of α, β ′, β, and the melting point of each polymorph varies depending on the type of fatty acid residue X having carbon number x. , Trilaurin, trimyristin, tripalmitin, tristearin, triarachidin, and tribehenine, the melting point (° C.) of each polymorph is shown. Table 1 was prepared based on Nissim Garti et al., “Crystallization and Polymorphism of Fats and Fatty Acids”, Marcel Dekker Inc., 1988, pp. 32-33. In preparing Table 1, the melting point temperature (° C.) was rounded to the first decimal place. Further, if the composition of the oil and fat and the melting point of each polymorph are known, it can be detected whether or not β-type oil or fat is present in the oil or fat.

A general method for identifying these polymorphs is an X-ray diffraction method, and diffraction conditions are given by the following Bragg equation.
2 d sin θ = nλ (n = 1, 2, 3,...)
A diffraction peak appears at a position satisfying this equation. Here, d is a lattice constant, θ is a diffraction (incident) angle, λ is an X-ray wavelength, and n is a natural number. From the diffraction peak 2θ = 16 to 27 ° corresponding to the short face spacing, information on the side packing (sublattice) in the crystal can be obtained, and polymorphism can be identified. In particular, in the case of triacylglycerol, a characteristic peak of β-type is observed at 2θ = 19, 23, 24 ° (near 4.6 °, 3.9 °, near 3.8 °), and α at 21 ° (4.2 °). A characteristic peak of the mold appears. The X-ray diffraction measurement is performed using, for example, an X-ray diffractometer (Rigaku Corporation, sample horizontal X-ray diffractometer UItimaIV) maintained at 20 ° C. As the X-ray light source, CuKα ray (1.54 mm) is most often used.

Furthermore, the crystal polymorphism of the above fats and oils can also be predicted by a differential scanning calorimetry (DSC method). For example, the prediction of β-type fats and oils is based on a DSC curve obtained by heating up to 100 ° C. at a rate of temperature increase of 10 ° C./min with a differential scanning calorimeter (product number, BSC 6220, manufactured by SII Nano Technology Co., Ltd.). This is done by predicting the crystal structure of the oil.

Here, the fat and oil component only needs to contain β-type fat or oil, or contains β-type fat and oil as a main component (greater than 50% by mass). As a preferable aspect, the fat and oil component is substantially from β-type fat and oil. In a more preferred embodiment, the oil and fat component is composed of β-type oil and fat, and in a particularly preferred embodiment, the oil and fat component is composed only of β-type oil and fat. The case where all of the oil and fat components are β-type oils and fats is a case where α-type oils and / or β′-type oils and fats are not detected by differential scanning calorimetry. As another preferred embodiment, the above fat component (or powdered fat composition containing the fat component) has a diffraction peak in the vicinity of 4.5 to 4.7 mm, preferably in the vicinity of 4.6 mm in the X-ray diffraction measurement. In Table 1, there is no X-ray diffraction peak of the short face spacing of the α-type fat and / or β′-type fat and oil, in particular, there is no diffraction peak in the vicinity of 4.2 mm. It can be judged that all are β-type oils and fats. As a further aspect of the present invention, it is preferable that all the fat components are β-type fats and oils, but other α-type fats and β′-type fats and oils may be contained. Here, the fat component in the present invention includes “β-type fat” and an index of the relative amount of β-type fat with respect to α-type fat and β-type fat is the β-type characteristic peak among the X-ray diffraction peaks. Intensity ratio between [alpha] -type characteristic peak and [[beta] -type characteristic peak intensity / [[alpha] -type characteristic peak intensity + [beta] -type characteristic peak intensity)] (hereinafter also referred to as peak intensity ratio). ). Specifically, based on the knowledge about the X-ray diffraction measurement described above, the peak intensity of 2θ = 19 ° (4.6 °) which is a characteristic peak of β type and 2θ = 21 which is a characteristic peak of α type. The ratio of the peak intensity at ° (4.2 mm): 19 ° / (19 ° + 21 °) [4.6 mm / (4.6 mm + 4.2 mm)] It can be understood that “including β-type fats and oils” as an index representing the abundance. In the present invention, it is preferable that all of the oil and fat components are β-type oils and fats (that is, peak intensity ratio = 1). For example, the lower limit value of the peak intensity ratio is, for example, 0.4 or more, preferably 0. 5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, particularly preferably 0.75 or more, and even more preferably 0.8 or more is appropriate. If the peak intensity is 0.4 or more, the β-type oil can be regarded as having a main component of more than 50% by mass. The upper limit of the peak intensity ratio is preferably 1, but 0.99 or less, 0.98 or less, 0.95 or less, 0.93 or less, 0.90 or less, 0.85 or less, 0.80 or less Etc. The peak intensity ratio may be any one or any combination of the above lower limit value and upper limit value.

<XXX type triglyceride>
The oil and fat component of the present invention contains one or more XXX type triglycerides having a fatty acid residue X having x carbon atoms at the 1st to 3rd positions of glycerin. The XXX type triglyceride is a triglyceride having a fatty acid residue X having x carbon atoms at the 1st to 3rd positions of glycerin, and each fatty acid residue X is the same as each other. Here, the carbon number x is an integer selected from 10 to 22, preferably an integer selected from 12 to 22, more preferably an integer selected from 14 to 20, and still more preferably selected from 16 to 18 Is an integer.
The fatty acid residue X may be a saturated or unsaturated fatty acid residue. Specific examples of the fatty acid residue X include residues such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, but are not limited thereto. More preferred as fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, more preferred are myristic acid, palmitic acid, stearic acid and arachidic acid, and even more preferred is palmitic acid. Acids and stearic acid.
The content of the XXX type triglyceride is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass when the total mass of the fat and oil component is 100% by mass. The lower limit is, for example, 100% by mass or less, preferably 99% by mass or less, and more preferably 95% by mass or less. XXX type triglycerides can be used singly or in combination of two or more, preferably one or two, more preferably one. When there are two or more types of XXX type triglycerides, the total value is the content of XXX type triglycerides.

<Other triglycerides>
The oil and fat component of the present invention may contain other triglycerides other than the XXX type triglyceride as long as the effects of the present invention are not impaired. The other triglycerides may be a plurality of types of triglycerides, and may be synthetic fats and oils or natural fats and oils. Examples of synthetic fats and oils include glyceryl tricaprylate. Examples of natural fats and oils include cocoa butter, sunflower oil, rapeseed oil, soybean oil, and cottonseed oil. When the total triglyceride in the oil and fat component of the present invention is 100% by mass, there is no problem even if other triglycerides are contained in an amount of 1% by mass or more, for example, about 5 to 50% by mass. The content of other triglycerides is, for example, 0 to 30% by mass, preferably 0 to 18% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 8% by mass.

<Other ingredients>
The powdered fat composition of the present invention may optionally contain other components such as emulsifiers, fragrances, coloring agents, skim milk powder, whole milk powder, cocoa powder, sugar, dextrin, etc., in addition to the above oil and fat components such as triglycerides. Good. The amount of these other components may be any amount as long as the effects of the present invention are not impaired. For example, when the total mass of the powdered oil and fat composition is 100% by mass, 0 to 70% by mass, preferably Is 0 to 65% by mass, more preferably 0 to 30% by mass. 90% by mass or more of the other components are preferably a powder having an average particle size of 1000 μm or less, and more preferably a powder having an average particle size of 500 μm or less. The average particle diameter here is a value (d50) measured by a laser diffraction scattering method (ISO133201 and ISO9276-1).
However, it is preferable that the preferred powdered fat composition of the present invention consists essentially of the above fat component, and the fat component preferably consists essentially of triglyceride. In addition, “substantially” means that the component other than the fat component contained in the fat composition or the component other than the triglyceride contained in the fat component is 100% by mass of the powdered fat composition or fat component, For example, it means 0 to 15% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass.

<Characteristics of powdered oil and fat composition>
The powdery fat composition of the present invention is a powdery solid at ordinary temperature (20 ° C.).
Loose bulk density of the powder fat and oil composition of the present invention, for example, be comprised of substantially only the oil component, 0.05 ~ 0.6g / cm ^3, preferably 0.1 ~ 0.5g / cm ^3, More preferably, it is 0.1 to 0.4 g / cm ³ or 0.15 to 0.4 g / cm ³ , and further preferably 0.2 to 0.3 g / cm ³ . Here, the “loosened bulk density” is a packing density in a state where the powder is naturally dropped. The loose bulk density (g / cm ³ ) is measured by, for example, dropping an appropriate amount of the powdered fat composition from about 2 cm above the upper opening end of the graduated cylinder into a graduated cylinder with an inner diameter of 15 mm × 25 mL, It can be determined by measuring the filled mass (g) and reading the volume (mL), and calculating the mass (g) of the powdered oil / fat composition per mL. The loose bulk density can also be calculated from the bulk specific gravity measured based on JIS K-6720 (or ISO 1060-1 and 2) using a bulk density measuring instrument of Kuramochi Scientific Instruments. Specifically, 120 mL of a sample is dropped into the receiver from a position 38 mm high from the upper opening of the receiver (100 mL cylindrical container having an inner diameter of 40 mm and a height of 85 mm). The sample swelled from the receiver is scraped off, the mass (Ag) of the sample corresponding to the internal volume (100 mL) of the receiver is weighed, and the loose bulk density can be obtained from the following equation.
Loose bulk density (g / mL) = A (g) / 100 (mL)
The measurement is preferably performed three times and the average value is taken.

In addition, the powdered fat composition of the present invention usually has a plate-like particle shape, for example, 0.5 to 200 μm, preferably 1 to 100 μm, more preferably 1 to 60 μm, and still more preferably, It has an average particle size (effective diameter) of 1 to 30 μm, particularly preferably 1 to 20 μm. Here, the average particle diameter (effective diameter) is a value (d50) measured by a laser diffraction scattering method (ISO133201, ISO9276-1) with a particle size distribution measuring device (for example, Microtrac MT3300ExII manufactured by Nikkiso Co., Ltd.).
The effective diameter means the particle diameter of the spherical shape when the actually measured diffraction pattern of the crystal to be measured matches the theoretical diffraction pattern obtained on the assumption that it is spherical. Thus, in the case of the laser diffraction scattering method, the effective diameter is calculated by fitting the theoretical diffraction pattern obtained on the assumption of a sphere and the actual diffraction pattern, so even if the measurement target is a plate shape Even a spherical shape can be measured by the same principle. Here, the plate-like shape preferably has an aspect ratio of 1.1 or more, more preferably an aspect ratio of 1.2 or more, still more preferably 1.2 to 3.0, particularly preferably The aspect ratio is 1.3 to 2.5, particularly preferably 1.4 to 2.0. The aspect ratio here is defined as the ratio of the length of the long side to the length of the short side of the particle figure surrounded by a rectangle circumscribing so as to minimize the area. Further, when the particles are spherical, the aspect ratio is smaller than 1.1. In the conventional method, in which oils with a high solid fat content such as extremely hardened oil are dissolved and sprayed directly, the particles of the powdered oil composition become spherical due to surface tension, and the aspect ratio is less than 1.1. Become. The aspect ratio is measured, for example, by measuring the length in the major axis direction and the length in the minor axis direction of the arbitrarily selected particles by direct observation with an optical microscope, a scanning electron microscope, or the like. It can obtain | require as an average value of the obtained number.

<The manufacturing method of a powder oil-fat composition>
The powdered oil and fat composition of the present invention is prepared by melting an oil and fat composition raw material containing one or more XXX type triglycerides having a fatty acid residue X having a carbon number of x at the 1st to 3rd positions of glycerin at a specific cooling temperature. By maintaining and solidifying by cooling, a powdery oil / fat composition (powder / fat composition) can be obtained without taking special processing means such as mechanical pulverization by a pulverizer such as spray or mill. More specifically, (a) preparing an oil and fat composition raw material containing the XXX type triglyceride, optionally heating the oil and fat composition raw material obtained in step (a) as step (b), The oil and fat composition raw material in a molten state is obtained by dissolving the triglyceride contained in the raw material, and (d) the oil and fat composition raw material is cooled and solidified to contain β-type oil and fat, and the particle shape is plate-like Is obtained. The powder oil composition can also be produced by applying known pulverization processing means such as a hammer mill and a cutter mill to the solid obtained after cooling.

The cooling in the step (d) is, for example, the temperature of the molten fat composition raw material at a temperature lower than the melting point of the β-type fat of the fat component contained in the fat composition raw material, and the following formula:
Cooling temperature (° C.) = Carbon number ×× 6.6−68
It is performed at a temperature higher than the cooling temperature required from If it cools in such a temperature range, since a beta type oil and fat can be produced | generated efficiently and a fine crystal | crystallization is made, a powdered oil and fat composition can be obtained easily. The term “fine” refers to the case where the primary particles (smallest size crystals) are, for example, 20 μm or less, preferably 15 μm or less, more preferably 10 μm. Moreover, if it does not cool in such a temperature range, (beta) type fats and oils will not produce | generate, but the solid substance which has the space | gap which increased the volume rather than the fats and oils composition raw material may be impossible. Furthermore, in the present invention, by cooling in such a temperature range, β-type fats and oils are produced in a stationary state, and the particles of the powdered fats and oils composition are formed into a plate shape. This is useful for specifying the powdered fat composition of the present invention. As a preferable average particle diameter of the emulsified powder oil-fat composition of this invention, the average particle diameter of 20 micrometers or less can be mentioned, for example. The method for measuring the average particle diameter is as described above. Furthermore, since fine particles of 20 μm or less are difficult to be sensed by human senses, using a particle of 20 μm or less adds a powder oil composition having a high melting point without giving a rough texture or touch. be able to.

The reason why the powdered fat composition of the present invention has an emulsifying power is not clear, but the particles having a small average particle size and a plate shape tend to gather at the interface between the oil phase and the water phase, thereby reducing the interfacial energy, Moreover, by dispersing in the system, the viscosity is increased, and thus the emulsified state may be stabilized. In addition, since the powdered oil / fat composition of the present invention is an oil / fat, it seems to have a high affinity with the oil phase, and therefore, a water-in-oil type emulsion composition tends to be easily formed. It seems that an oil-in-water emulsion composition is also formed by the combined use. This is for the purpose of making the principle of the present invention easier to understand, and the present invention is not restricted by this principle.

In more detail, the manufacturing method of a powder oil-fat composition is demonstrated.
The powdered fat composition of the present invention comprises the following steps:
(A) a step of preparing an oil and fat composition raw material containing XXX type triglyceride,
(B) The optional step of heating the fat composition raw material obtained in step (a) arbitrarily to obtain the molten fat composition raw material by dissolving the triglyceride contained in the fat composition raw material, (D) a step of cooling and solidifying the oil-and-fat composition raw material to obtain a powdered oil-and-fat composition containing β-type oil and fat and having a plate-like particle shape;
It can manufacture by the method containing.
Moreover, between the said process (b) and (d), the arbitrary processes for accelerating | stimulating powder production as a process (c), for example, (c1) Seeding process, (c2) Tempering process, and / or (c3) A pre-cooling step may be included. Further, the powdered fat composition obtained in the step (d) may be obtained by the step (e) of obtaining a powdery fat composition by grinding the solid obtained after cooling in the step (d). Good. Hereinafter, the steps (a) to (e) will be described.

(A) Raw material preparation step The oil and fat composition raw material containing XXX type triglyceride prepared in step (a) is one or more XXX type triglycerides having a fatty acid residue X of carbon number x at the 1st to 3rd positions of glycerin. It is manufactured based on the manufacturing method of fats and oils, such as normal XXX type triglyceride containing, or can be easily obtained from the market. Here, the XXX-type triglyceride specified by the carbon number x and the fatty acid residue X is the same as that of the finally obtained fat component except for the crystal polymorph. The raw material may contain β-type fats and oils, for example, the β-type fats and oils may contain 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less. . However, since the β-type fats and oils disappear when the raw material is brought into a molten state by heating or the like, the raw material may be a raw material in a molten state. For example, when the raw material is in a molten state, the fact that β-type fats and oils are substantially not included is not limited to XXX type triglycerides, but also means that substantially all of the fat and oil components are not β-type fats and oils. Presence of the type fat / oil can be confirmed by confirming the diffraction peak due to the β type fat / oil by the above-mentioned X-ray diffraction measurement, the β type fat / oil by the differential scanning calorimetry, and the like. The amount of β-type oil / fat in the case of “substantially free of β-type oil / fat” is the intensity ratio between the characteristic peak of β-type and the characteristic peak of α-type among the X-ray diffraction peaks [characteristic of β-type It can be assumed from the following: intensity of target peak / (intensity of characteristic peak of α type + intensity of characteristic peak of β type)] (peak intensity ratio) The said peak intensity ratio of the said fat-and-oil composition raw material is 0.2 or less, for example, Preferably, it is 0.15 or less, More preferably, it is 0.10 or less. The oil and fat composition raw material may contain one or more XXX triglycerides as described above, preferably one or two, more preferably one.
Specifically, for example, the XXX type triglyceride can be produced by direct synthesis using a fatty acid or a fatty acid derivative and glycerin. As a method of directly synthesizing XXX type triglyceride, (i) a method of directly esterifying a fatty acid having X carbon atoms and glycerin (direct ester synthesis), (ii) a carboxyl group of fatty acid X having x carbon number is an alkoxyl group A method of reacting fatty acid alkyl (for example, fatty acid methyl and fatty acid ethyl) and glycerin under basic or acidic catalytic conditions (transesterification synthesis using fatty acid alkyl), (iii) a fatty acid having x carbon number The method (acid halide synthesis | combination) with which the fatty acid halide (for example, fatty acid chloride and fatty acid bromide) by which the hydroxyl group of the carboxyl group of X was substituted with halogen and glycerol is made to react in a basic catalyst is mentioned.
XXX type triglycerides can be produced by any of the above-mentioned methods (i) to (iii), but from the viewpoint of ease of production, (i) direct ester synthesis or (ii) transesterification synthesis using fatty acid alkyl is Preferably, (i) direct ester synthesis is more preferred.

In order to produce XXX type triglycerides by (i) direct ester synthesis, from the viewpoint of production efficiency, it is preferable to use 3 to 5 moles of fatty acid X or fatty acid Y with respect to 1 mole of glycerin. It is more preferable.
The reaction temperature in the (i) direct ester synthesis of the XXX type triglyceride may be a temperature at which the water produced by the esterification reaction can be removed from the system, and is preferably 120 ° C. to 300 ° C., for example, 150 ° C. to 270 ° C. More preferably, 180 ° C. to 250 ° C. is even more preferable. By carrying out the reaction at 180 to 250 ° C., XXX type triglyceride can be produced particularly efficiently.

In the (i) direct ester synthesis of the XXX type triglyceride, a catalyst for promoting the esterification reaction may be used. Examples of the catalyst include an acid catalyst and an alkaline earth metal alkoxide. The amount of the catalyst used is preferably about 0.001 to 1% by mass relative to the total mass of the reaction raw materials.
In (i) direct ester synthesis of XXX type triglycerides, after the reaction, the catalyst and raw material unreacted substances are removed by performing known purification treatments such as washing with water, alkaline deoxidation and / or vacuum deoxidation, and adsorption treatment. can do. Furthermore, the obtained reaction product can be further purified by performing decolorization / deodorization treatment.

The amount of the XXX type triglyceride contained in the oil and fat composition raw material is, for example, 100 to 50% by mass, preferably 95 to 55% by mass, when the total mass of all triglycerides contained in the raw material is 100% by mass. More preferably, it is 90 to 60% by mass. Even more preferably, it is 85 to 65% by mass.

<Other triglycerides>
As the other triglyceride serving as the raw material for the oil and fat composition containing XXX type triglyceride, various triglycerides may be included in addition to the above XXX type triglyceride, as long as the effects of the present invention are not impaired. As other triglycerides, for example, an X2Y type triglyceride in which one fatty acid residue X of the XXX type triglyceride is substituted with a fatty acid residue Y, and two fatty acid residues X in the XXX type triglyceride are substituted with a fatty acid residue Y. XY2 type triglyceride etc. can be mentioned.
The amount of the other triglycerides is, for example, 0 to 100% by mass, preferably 0 to 70% by mass, more preferably 1 to 40% by mass, when the total mass of the XXX type triglyceride is 100% by mass.

In addition, as the oil and fat composition raw material of the present invention, instead of directly synthesizing the XXX type triglyceride, a natural triglyceride composition obtained by hydrogenation, transesterification or fractionation may be used. Examples of naturally occurring triglyceride compositions include rapeseed oil, soybean oil, sunflower oil, high oleic sunflower oil, safflower oil, palm stearin, and mixtures thereof. Particularly preferred are hardened oils, partially hardened oils and extremely hardened oils of these naturally derived triglyceride compositions. More preferred are hard palm stearin, high oleic sunflower oil extremely hardened oil, rapeseed extremely hardened oil, and soybean extremely hardened oil.

Furthermore, as the oil and fat composition raw material of the present invention, a commercially available triglyceride composition or synthetic oil and fat can be mentioned. For example, as a triglyceride composition, hard palm stearin (manufactured by Nisshin Oillio Group Co., Ltd.), rapeseed extremely hardened oil (manufactured by Yokoseki Yushi Kogyo Co., Ltd.), soybean super hardened oil (manufactured by Yokoseki Yushi Kogyo Co., Ltd.) can be mentioned. it can. Synthetic fats and oils include tripalmitin (manufactured by Tokyo Chemical Industry Co., Ltd.), tristearin (manufactured by Sigma Aldrich), tristearin (manufactured by Tokyo Chemical Industry Co., Ltd.), triarachidin (manufactured by Tokyo Chemical Industry Co., Ltd.) and tribehenine (manufactured by Tokyo Chemical Industry Co., Ltd.). Manufactured by Kogyo Co., Ltd.).
In addition, palm extremely hardened oil has a low content of XXX type triglyceride, and therefore can be used as a dilute component of triglyceride.

<Other ingredients>
In addition to the triglyceride, the oil and fat composition raw material may optionally contain other components such as a partial glyceride, a fatty acid, an antioxidant, an emulsifier, and a solvent such as water. The amount of these other components may be any amount as long as the effects of the present invention are not impaired. For example, when the total mass of the XXX triglyceride is 100% by mass, 0 to 5% by mass, preferably It is 0-2% by mass, more preferably 0-1% by mass.

When the said fat-and-oil composition raw material contains two or more components, you may mix arbitrarily. Any known mixing method may be used for mixing as long as a homogeneous reaction substrate can be obtained. For example, a paddle mixer, an adihomo mixer, a disper mixer, or the like can be used.
You may mix the said heating under a heating as needed. The heating is preferably at the same level as the heating temperature in the step (b) described later, for example, 50 to 120 ° C., preferably 60 to 100 ° C., more preferably 70 to 90 ° C., more preferably 80 ° C. Is called.

(B) The process of obtaining the said fat-and-oil composition of a molten state Before the said (d) process, when the fat-and-oil composition raw material prepared by the said process (a) is in a molten state at the time of preparation, please heat. Although it is cooled as it is, when it is not in a molten state at the time of preparation, it is arbitrarily heated to melt the triglyceride contained in the oil composition raw material to obtain a molten oil composition raw material.
Here, the heating of the oil / fat composition raw material is performed at a temperature equal to or higher than the melting point of the triglyceride contained in the oil / fat composition raw material, particularly at a temperature at which the XXX type triglyceride can be melted, for example, 70 to 200 ° C., preferably 75 to 150 ° C. More preferably, the temperature is 80 to 100 ° C. In addition, the heating is suitably continued, for example, for 0.1 to 3 hours, preferably 0.3 to 2 hours, more preferably 0.5 to 1 hour.

(D) Step of cooling the molten fat composition to obtain a powdered fat composition The molten fat composition raw material prepared in the above step (a) or (b) is further cooled and solidified to form β-type A powdery fat composition containing fats and oils and having a plate-like particle shape is formed.
Here, in order to “cool and solidify a molten fat composition raw material”, the upper limit value of the cooling temperature is obtained by using the molten fat composition raw material as a β-type fat of the fat component contained in the fat composition raw material. It is necessary to keep the temperature lower than the melting point of. For example, in the case of XXX type triglyceride having 3 stearic acid residues having 18 carbon atoms, the melting point of β type fat is: Since it is 74 ° C. (Table 1), it is 1-30 ° C. lower than the melting point (ie, 44-73 ° C.), preferably 1-20 ° C. lower than the melting point (ie, 54-73 ° C.), more preferably 1-15 ° C. below the melting point (ie 59-73 ° C.), particularly preferably 1 ° C., 2 ° C., 3 ° C., 4 ° C., 5 ° C., 6 ° C., 7 ° C., 8 ° C., 9 ° C. or 10 ° C. Temperature.
More preferably, in order to obtain the β-type oil and fat, it is appropriate to keep the cooling temperature lower than the cooling temperature obtained from the following formula as the lower limit value of the cooling temperature.
Cooling temperature (° C.) = Carbon number ×× 6.6−68
(In the formula, carbon number x is carbon number x of XXX type triglyceride contained in the oil and fat composition raw material)
In order to obtain β-type fats and oils containing XXX type triglycerides, the cooling temperature is set to α-type fats other than β-type fats and β′-type fats and oils other than β-type fats. This is because it is necessary to set a temperature at which crystallization does not occur. Since the cooling temperature mainly depends on the molecular size of the XXX type triglyceride, it can be understood that there is a certain correlation between the carbon number x and the lower limit of the optimum cooling temperature.
For example, when the XXX type triglyceride contained in the oil and fat composition raw material is XXX type triglyceride having 3 stearic acid residues having 18 carbon atoms, the lower limit of the cooling temperature is 50.8 ° C. or more. Therefore, in the case of the XXX type triglyceride having 3 stearic acid residues having 18 carbon atoms, the temperature for “cooling and solidifying the molten oil composition raw material” is more preferably 50.8 ° C. or more and 72 ° C. or less. Become.
Moreover, when XXX type | mold triglyceride is a 2 or more types of mixture, the lower limit can be determined according to the cooling temperature with the smaller carbon number x. For example, the XXX type triglyceride contained in the oil and fat composition raw material is a mixture of XXX type triglyceride having 3 palmitic acid residues having 16 carbon atoms and XXX type triglyceride having 3 stearic acid residues having 18 carbon atoms. In this case, the lower limit of the cooling temperature is 37.6 ° C. or higher in accordance with the smaller carbon number of 16.

As another aspect, the lower limit value of the cooling temperature is suitably a temperature equal to or higher than the melting point of the α-type oil or fat corresponding to the β-type oil or fat of the oil or fat composition raw material containing XXX type triglyceride. For example, when the XXX-type triglyceride contained in the oil-and-fat composition raw material is a XXX-type triglyceride having 3 stearic acid residues having 18 carbon atoms, an α-type oil and fat of the XXX-type triglyceride having 3 stearic acid residues Since the melting point is 55 ° C. (Table 1), the temperature for “cooling and solidifying the molten oil and fat composition raw material” in this case is preferably 55 ° C. or more and 72 ° C. or less.

In still another embodiment, the cooling of the raw material for the fat and oil composition in the molten state is, for example, when x is 10 to 12, the final temperature is preferably −2 to 46 ° C., more preferably 12 to 44 ° C., and still more preferably. It is performed by cooling to a temperature of 14 to 42 ° C. For example, when x is 13 or 14, the final temperature in cooling is preferably 24 to 56 ° C., more preferably 32 to 54 ° C., still more preferably 40 to 52 ° C., and when x is 15 or 16, Preferably it is 36 to 66 ° C., more preferably 44 to 64 ° C., further preferably 52 to 62 ° C., and when x is 17 or 18, it is preferably 50 to 72 ° C., more preferably 54 to 70 ° C. Preferably, it is 58 to 68 ° C. When x is 19 or 20, it is preferably 62 to 80 ° C, more preferably 66 to 78 ° C, still more preferably 70 to 77 ° C, and when x is 21 or 22. Is preferably 66 to 84 ° C, more preferably 70 to 82 ° C, still more preferably 74 to 80 ° C. At the final temperature, for example, preferably 2 hours or more, more preferably 4 hours or more, still more preferably 6 hours or more, preferably 2 days or less, more preferably 24 hours or less, still more preferably 12 hours or less, It is appropriate to stand still.

(C) Powder production promotion step Further, before the step (d), between the above steps (a) or (b) and (d), (c) As an optional step for promoting powder production, You may perform the process by the seeding method (c1), the tempering method (c2), and / or the (c3) precooling method with respect to the oil-fat composition raw material of the molten state used by d). Any of these optional steps (c1) to (c3) may be performed alone, or a plurality of steps may be combined. Here, between step (a) or (b) and step (d) is after step (a) or (b) in step (a) or (b) and in step (d). It means to include the previous step (d).
The seeding method (c1) and the tempering method (c2) are carried out before the cooling to the final temperature in order to make the oil and fat composition raw material in a molten state more reliable in the production of the oil and fat composition of the present invention. And a method for accelerating the production of powder for treating a raw material of an oil and fat composition in a molten state. Here, the seeding method (c1) is a method in which a small amount of a component that becomes a powder core (seed) is added at the time of cooling the oil and fat composition raw material in a molten state to promote powdering. Specifically, for example, the XXX type triglyceride having the same carbon number as that of the XXX type triglyceride in the fat and oil composition raw material is preferably 80% by mass or more to the fat and oil composition raw material in the molten state obtained in the step (b). More preferably, an oil and fat powder containing 90% by mass or more is prepared as a core (seed) component. When the fat composition is cooled, the temperature of the fat composition raw material reaches, for example, the final cooling temperature ± 0 to + 10 ° C., preferably +5 to + 10 ° C. At this point, 0.1 to 1 part by weight, preferably 0.2 to 0.8 parts by weight, is added to 100 parts by weight of the oil and fat composition raw material in the molten state, thereby pulverizing the oil and fat composition. It is a way to promote.
The tempering method (c2) is a temperature lower than the cooling temperature in the step (d), for example, 5 to 20 ° C., before cooling at the final cooling temperature in the cooling of the fat and oil composition raw material in a molten state. The pulverization of the oil and fat composition is promoted by cooling to a low temperature, preferably 7 to 15 ° C., more preferably about 10 ° C., preferably for 10 to 120 minutes, more preferably about 30 to 90 minutes. It is a method to do.
Furthermore, the preliminary cooling method (c3) includes the XXX type triglyceride before the molten oil composition raw material obtained in the step (a) or (b) is cooled in the step (d). A method of once cooling at a temperature between the temperature at which the oil / fat composition raw material is prepared and the cooling temperature at the time of cooling the oil / fat composition raw material, in other words, from the molten state temperature in the step (a) or (b) Is preliminarily cooled at a temperature higher than the cooling temperature of step (d). (C3) Subsequent to the pre-cooling method, cooling is performed at the cooling temperature at the time of cooling the fat composition raw material in the step (d). The temperature higher than the cooling temperature of step (d) is, for example, a temperature 2 to 40 ° C. higher than the cooling temperature of step (d), preferably a temperature higher by 3 to 30 ° C., more preferably a temperature higher by 4 to 30 ° C., More preferably, the temperature may be as high as 5 to 10 ° C. The lower the temperature for the preliminary cooling, the shorter the main cooling time at the cooling temperature in the step (d). That is, unlike the seeding method or the tempering method, the pre-cooling method is a method that can promote the pulverization of the oil / fat composition by simply lowering the cooling temperature stepwise, and has a great advantage in industrial production.

(E) Step of obtaining a powdered fat composition by pulverizing a solid matter More specifically, the step of obtaining a powdered fat composition by cooling in the step (d) is more specifically a solid matter obtained by cooling in the step (d). It may be performed by the process (e) which grind | pulverizes and obtains a powdery oil-fat composition.
More specifically, first, the oil composition raw material is melted to obtain a molten oil composition, and then cooled to form a solid having voids whose volume is increased as compared with the molten oil composition raw material. . The fat and oil composition that has become a solid having voids can be pulverized by applying a light impact, and the solid is easily disintegrated into a powder form.
Here, a means for applying a light impact is not particularly specified, but a method of lightly applying vibration (impact) and pulverizing (raising) by shaking, sieving, etc. is simple and preferable.
The solid material may be pulverized by a known pulverization means. Examples of such pulverization means include a hammer mill and a cutter mill.

<Content of emulsified powder / fat composition in emulsified composition>
The emulsified powder / fat composition of the present invention is contained on the basis of the amount of the “oil phase” in the above-described emulsified composition. That is, it is contained at 0.5 to 20 parts by mass with respect to 100 parts by mass of the oil phase in the emulsion composition. The amount is more preferably 1 to 18 parts by mass, further preferably 3 to 15 parts by mass, and still more preferably 5 to 10 parts by mass.
The desired emulsification effect of the present invention can be obtained by adding at least 0.5 parts by mass of the emulsified powder oil-fat composition of the present invention to 100 parts by mass of the oil phase in the emulsified composition of the present invention. Moreover, when the emulsified composition of the present invention contains 20 parts by mass or less of the emulsified powder / fat composition, it is preferable because the influence on physical properties and the like is small.

<Method for producing emulsified composition>
The production method of the emulsion composition of the present invention is not particularly limited, and can be produced by a general method such as a physical method, an inversion emulsification method, a liquid crystal emulsification method, a D-phase emulsification method, or a three-phase emulsification method. That is, when the aqueous phase and the oil phase are mixed to produce an emulsified composition, the emulsified powder / fat composition may be added to the oil phase. For example, a water phase in which the emulsified powder fat composition of the present invention is added to an oil phase containing fat and oil and other oil-soluble components as necessary, and the water-soluble components of other components are dissolved or dispersed in water. Is added, and both are mixed and emulsified. As described above, since the emulsion composition of the present invention tends to form a water-in-oil emulsion composition, it is a method for producing a water-in-oil emulsion composition (so-called W / O emulsion). Is preferred. Furthermore, since the emulsifying power of the emulsified powder / fat composition of the present invention is itself, the emulsified composition of the present invention is preferably produced without using an emulsifier. The temperature during mixing and emulsification is preferably normal temperature (20 ° C.). When mixing and emulsifying at a temperature higher than normal temperature, the temperature at which all of the emulsified powder / fat composition of the present invention does not dissolve ( For example, it is preferable to carry out at the cooling temperature or lower in the step of obtaining the above-described powdered fat composition. Examples of the equipment for mixing and emulsifying include emulsifiers such as homogenizers, dispersers such as colloid mills, and stirring devices such as homomixers and now mixers. Next, it is desirable to sterilize the emulsion composition of the present invention. The sterilization method may be a batch type in a tank, or a continuous type using a plate type heat exchanger or a scraping type heat exchanger. Furthermore, it is preferable to cool and crystallize the emulsion composition of the present invention. More preferably, it is cooled and plasticized. The cooling condition is preferably −0.5 ° C./min or more, more preferably −5 ° C./min or more. At this time, rapid cooling is preferable to slow cooling. As a device for cooling, a closed continuous tube cooler, for example, a rapid kneader such as a botator, a comminator, and a perfector can be cited. Moreover, the combination of an open-type diacooler and a compressor is mentioned.

<Emulsifier substitute or emulsifier>
By the way, as described above, the emulsified powder / fat composition used in the present invention can produce an emulsified composition without using an emulsifier. It can be used as (an agent in place of an emulsifier) or an emulsification aid (an agent for supplementing the emulsifying action of the emulsifier). That is, the present invention also relates to an emulsifier substitute or an emulsification auxiliary agent containing the emulsified powder / fat composition as an active ingredient.
The emulsifier substitute or emulsification auxiliary of the present invention contains the above-described emulsified powder oil composition as an active ingredient. The emulsifier substitute or emulsification auxiliary of the present invention preferably contains 60% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass or more of the above-described emulsified powder oil composition. To do.
Moreover, the alternative agent or emulsifier of the emulsifier of the present invention only needs to contain the above-described emulsified powder oil and fat composition as an active ingredient, and in the range not impairing the effects of the present invention, Oils and fats such as soybean oil and rapeseed oil, excipients such as dextrin and starch, and the like may be included.
However, the preferable emulsifier substitute or emulsification aid of the present invention preferably consists essentially of the emulsified powder / fat composition. Here, “substantially” means that the ingredients other than the emulsifier substitute or emulsification auxiliary contained in the emulsifier substitute or emulsification auxiliary are 100% by mass of the emulsifier substitute or emulsification auxiliary. 0 to 15% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited to these at all. Also. In the following, “%” indicates mass% unless otherwise specified, and “part” indicates mass part.
[Analysis method]
・ Triglyceride composition gas chromatography analysis conditions
DB1-ht (0.32mm × 0.1μm × 5m) Agilent Technologies (123-1131)
Injection volume: 1.0 μL
Inlet: 370 ° C
Detector: 370 ° C
Split ratio: 50/1 35.1kPa Constant pressure column CT: 200 ℃ (0min hold) to (15 ℃ / min) to 370 ℃ (4min hold)
-X-ray diffraction measurement Using an X-ray diffractometer Ultima IV (manufactured by Rigaku Corporation), using CuKα (λ = 1.542 mm) as a radiation source, using a filter for Cu, output 1.6 kW, operating angle 0.96 ~ The measurement was performed under the conditions of 30.0 ° and a measurement speed of 2 ° / min. By this measurement, the presence of α-type oil and fat, β′-type oil and fat, and β-type oil and fat in the oil and fat component containing XXX type triglyceride was confirmed. When it had only a peak around 4.6 有 し and no peak around 4.1 to 4.2 Å, it was judged that all of the oil and fat components were β-type oils and fats.
From the results of the X-ray diffraction measurement, the peak intensity ratio = [intensity of the β-type characteristic peak (2θ = 19 ° (4.6 （)) / (intensity of the α-type characteristic peak (2θ = 21 °]). (4.2 Å)) + β-type characteristic peak intensity (2θ = 19 ° (4.6 Å)))] was measured as an index representing the abundance of β-type fats and oils.

Loose bulk density The loose bulk density (g / cm ³ ) of the powdered fat composition obtained in the examples and the like is measured in a measuring cylinder having an inner diameter of 15 mm × 25 mL from about 2 cm above the upper opening end of the measuring cylinder. The composition was dropped and loosely filled, the filled mass (g) was measured and the capacity (mL) was read, and the mass (g) of the powdered oil / fat composition per mL was calculated.
・ Crystal (micrograph)
The crystals of the powdered oil / fat composition obtained with a 3D real surface view microscope VE-8800 (manufactured by Keyence Corporation) were photographed. The obtained micrographs are shown in FIG. 4 (Production Example 7) and FIG. 5 (Production Comparative Example 3).
-Aspect ratio For particles that were directly observed with a scanning electron microscope S-3400N (manufactured by Hitachi High-Technologies Corporation) and arbitrarily selected using image analysis particle size distribution measurement software (Mac-View, manufactured by Mountec Co., Ltd.) The length in the major axis direction and the length in the minor axis direction were measured and measured as an average value of the measured number.
・ Average particle size (d50)
It measured based on the laser diffraction scattering method (ISO133201, ISO9276-1) with the particle size distribution measuring apparatus (Microtrac MT3300ExII by Nikkiso Co., Ltd.). In addition, the measured average particle diameter is the value of d50.

<Raw material>
(1) Powdered fat composition A (powdered fat composition for emulsification)
25 g of triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) at 80 ° C. for 0.5 hour It was maintained and completely melted, cooled in a thermostatic bath at 60 ° C. for 12 hours to form a solid having voids with increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. The obtained solid is mechanically pulverized to obtain a powdered oil composition that is a powdery crystalline composition (loose bulk density: 0.2 g / cm ³ , aspect ratio 1.6, average particle size 8.0 μm, X-ray Diffraction measurement Diffraction peak: 4.6 Å, peak intensity ratio: 0.89). In the following Test Examples 1 to 3, this powdery fat composition A was used.
Moreover, the micrograph of the powdery fat composition A is shown in FIG. 19 (100 times) and FIG. 20 (300 times).
(2) Powdered fats and oils B
As the powdered fats and oils B, commercially available powdered fats and oils (manufactured by Riken Vitamin Co., Ltd .: Spray Fat NR100) were used.
This powdered fat / oil B is a bead-shaped spherical powder, and is easily dispersed in water in which the fat / oil is trapped. The average particle diameter is 86 μm. The ratio was 0.91.
Moreover, the micrograph of the powdery fats and oils B is shown in FIG. 21 (100 times) and FIG. 22 (300 times).
(3) Oil phase Canola oil (Nisshin Oillio Group Co., Ltd.)
(4) Water phase Ion-exchanged water (Ion-exchanged water produced with a cylinder type cartridge type pure water device manufactured by Organo Corporation)

[Test Example 1] Emulsifying effect of powdered fat composition of the present invention <Production of emulsified composition>
The emulsified compositions of Examples 1 and 2 and the composition of Comparative Example 1 were produced according to the formulation shown in Table 2 below. More specifically, in a 100 ml sample bottle, the powdered fat composition A is 0.01 parts by mass (Comparative Example 1) and 1.0 part by mass (Example 1) with respect to 100 parts by mass of the oil phase. , 5.0 parts by mass (Example 2), in addition to canola oil, an aqueous phase (ion-exchanged water) was further added thereto, and stored at 50 ° C. overnight (confirmation of solubility). Next, the oil phase and the aqueous phase were emulsified and mixed at 10000 rpm for 2 minutes at 20 ° C. using a homomixer (manufactured by PRIMIX Corporation). And the emulsified state immediately after emulsification and the emulsified state after 72 hours were observed (confirmation of emulsification stability). The state when stored overnight at 50 ° C., the state immediately after emulsification, and the state after 72 hours are shown in FIG.

<Emulsifying effect of powdered oil and fat composition>
As is clear from FIG. 1, the powdered fat / oil composition A showed a tendency to gather at the interface between the oil phase and the aqueous phase (present in the oil phase). In particular, in Example 2, the interface appeared white, and the solubility of the powdered fat composition A in the oil phase seemed to be low. Next, when the oil phase and the aqueous phase were emulsified with a homomixer, in Comparative Example 1 immediately after the emulsification, the oil phase only became cloudy and no emulsification occurred with the aqueous phase. On the other hand, in Examples 1 and 2 immediately after emulsification, the interface between the oil phase and the water phase becomes invisible, and when dropped into water, the continuous phase is oil, so it does not mix with water and floats in a separated state on the water surface. The water-in-oil emulsion composition (so-called W / O emulsion) was confirmed. Next, looking at the state after 72 hours, Comparative Example 1 was not changed from the state immediately after emulsification, and there was an interface between the oil phase and the water phase, and no emulsification was performed. On the other hand, in Examples 1 and 2 as well, it was confirmed that an interface between the oil phase and the water phase was generated and demulsification occurred.

[Test Example 2] Emulsification stability of powdered oil / fat composition In order to examine the emulsification stability of the powdered oil / fat composition A in more detail, various values (50, 60, 70, 80) of the oil ratio (ratio of the oil phase) were used. , 90% by mass), and the same experiment as in Test Example 1 was performed. The remaining oil ratio (100% by mass−oil ratio) is the ratio of the aqueous phase. The results are summarized in Tables 3-4. More specifically, canola oil (oil phase) and ion-exchanged water (aqueous phase) were mixed in a 100 ml sample bottle at the blending ratios shown in Tables 3-4. In each oil phase, 5.0 parts by weight of powdered oil / fat composition A is added in advance to 100 parts by weight of oil phase (Examples 3 to 7), and as a comparative example, the above-mentioned powdered oil / fat composition A is added. Those that did not (Comparative Examples 2 to 6) were prepared. Moreover, what added the powder fats and oils B of 5 mass parts with respect to 100 mass parts of oil phases as oil ratio 50 mass% (comparative example 7) was prepared. These were mixed and emulsified at 10000 rpm for 2 minutes at 20 ° C. using a homomixer (manufactured by PRIMIX Corporation). The state immediately after emulsification, the state after 5 hours and / or the state after 24 hours are shown in FIGS. 2 shows the case where the powdered oil / fat composition A of Examples 3-7 was added, and FIG. 3 shows the case where the powdered oil / fat composition A of Comparative Examples 2-6 was not added. Moreover, FIG. 4 shows the case where the powder fats and oils B of the comparative example 7 are added.

As is apparent from Table 3 and FIG. 2, in Examples 3 to 7, when the powdered fat composition A was added at all oil ratios, the emulsification and separation were not performed even after 5 hours from emulsification. It did not occur and it was found that the emulsified state was maintained. Thus, even if the oil ratio is changed, the emulsified state is not affected. Therefore, it was found that when the oil ratio is at least 50% by mass to 90% by mass, a stable emulsion composition can be produced. However, in Examples 3 to 7, since the occurrence of the interface can be confirmed after 24 hours (for example, “62” in the table indicates that the interface occurred at 62 mm from the bottom of the sample bottle. ), It was found that demulsification occurred.
In addition, as is clear from Table 4 and FIG. 3, in Comparative Examples 2 to 6, when the powdered fat / oil composition A was not added at all oil ratios, separation had already occurred 5 hours after emulsification. It was confirmed that a stable emulsified state could not be maintained. Further, after 24 hours, two interfaces are generated (for example, “60/6” in the table indicates that the interfaces are generated at both 60 mm and 6 mm from the bottom of the sample bottle), and thus demulsification. Was confirmed to be more advanced.
Furthermore, as is clear from Table 4 and FIG. 4, in Comparative Example 7, when commercially available powdered fats and oils B were added, the interface became visible after 5 hours from emulsification (“40” in the table). "" Indicates that an interface was generated 40 mm from the bottom of the sample bottle.) It was found that a stable emulsified state could not be maintained. Further, after 24 hours, the separation further progressed and the interface became clearer (in the table, “30” indicates that the interface was generated 30 mm from the bottom of the sample bottle), and the demulsification further progressed. It was confirmed that

[Test Example 3] Oil-water separation test of mayonnaise-like food Since the emulsifying capacity of the powdered oil / fat composition A itself was confirmed as described above, the effect as an emulsification aid (emulsification stability on the existing emulsion composition). A test was conducted to confirm whether or not there was an effect of enhancing.
First, a mayonnaise-like food was produced with the composition shown in Table 5 using commercially available egg yolk, vinegar, salt, mustard, and salad oil (Nisshin Oillio Group, Nisshin Salad Oil). More specifically, the mayonnaise-like food was produced according to the following production procedure. Put egg yolk, vinegar, salt, mustard and powdered oil composition A (1 part by mass with respect to 100 parts by mass of salad oil corresponding to the oil phase) in the container shown in Table 5 (however, in Comparative Example 8) The powdered oil / fat composition A was not added but salad oil was added), and the mixture was stirred for 10 seconds with a commercially available blender. The amount of salad oil shown in Table 5 was gradually added over 1 minute and 30 seconds with stirring. The mayonnaise-like food product (oil-in-water emulsion composition) was produced by stirring for 1 minute as it was.

According to the following evaluation criteria, the freezing tolerance of the obtained mayonnaise-like food was evaluated. Evaluation of freezing tolerance was performed as follows. First, the obtained mayonnaise-like food was put into a 100 mL glass vial and prepared seven each of those containing the powdered fat composition A and those not blended. Glass vials containing a total of 14 mayonnaise-like foods were placed in a −20 ° C. freezer and stored for up to one week. Each glass vial containing one mayonnaise-like food was transferred to a constant temperature bath at 20 ° C. and thawed, and the presence or absence of oil-water separation was visually confirmed. The results are summarized in Table 6 and FIG. In FIG. 5, “−20 ° C. Control” indicates that the powdered oil / fat composition A is not blended, and “−20 ° C. Powder” indicates that the powdered fat / oil composition A is blended.
<Evaluation criteria for freezing tolerance>
○: Oil-water separation is not observed ×: Oil-water separation is observed Note that the “number” in the table indicates the degree of separation (unit: mm), that is, how much separation has occurred (the larger the number, the greater the value) , Indicating separation is progressing).
Emulsified composition

As is apparent from Table 6 and FIG. 5, the powdered fat composition A has an effect of suppressing the occurrence of oil-water separation of mayonnaise-like food (oil-in-water emulsion composition) when stored at −20 ° C. I understood it. Therefore, it was confirmed that the powdered fat composition for emulsification of the present invention has an effect of assisting the emulsifying power of an existing emulsifier (in Test Example 3, lecithin in egg yolk corresponds to an emulsifier). It is expected that the emulsification assisting power of such emulsified powder / fat composition can contribute to the emulsion stability of various foods, cosmetics, and pharmaceuticals.

Furthermore, the manufacture example of the powder oil-fat composition of this invention is shown below. The powdery composition obtained by these production examples can also be used as a powdered oil composition for emulsification, as in the above examples.
(Production Example 1): x = 16
25 g of a triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions is maintained at 80 ° C. for 0.5 hour. The mixture was completely melted and cooled in a constant temperature bath at 50 ° C. for 12 hours to form a solid having voids with increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size: 119 μm, X-ray diffraction measurement) Diffraction peak: 4.6 Å, peak intensity ratio: 0.90).

(Production Example 2): x = 16
25 g of a triglyceride (XXX type: 69.9% by mass, hard palm stearin, Nisshin Oilio Group Co., Ltd.) having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions at 80 ° C. for 0.5 hour It was maintained and completely melted, and cooled in a thermostatic bath at 50 ° C. for 12 hours to form a solid having voids with an increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.3 g / cm ³ , aspect ratio: 1.4, average particle size 99 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.88).

(Production Example 3): x = 16, (c2) Tempering method Triglyceride having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions (XXX type: 89.7% by mass, tripalmitin, Tokyo Chemical Industry) 15g) was melted completely by maintaining at 80 ° C for 0.5 hours, cooled in a 30 ° C constant temperature bath for 0.01 hours, and then allowed to stand in a 60 ° C constant temperature bath for 2 hours. A solid with increased voids was formed and after crystallization was completed, it was cooled to room temperature (25 ° C.). A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 87 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 4): x = 16, (c1) Seeding method Triglyceride having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions (XXX type: 89.7% by mass, tripalmitin, Tokyo Kasei) Kogyo Co., Ltd.) 15 g at 80 ° C. for 0.5 hours, completely melted and cooled in a 60 ° C. thermostatic bath until the product temperature reaches 60 ° C. 0.1% by mass, left in a thermostatic bath at 60 ° C. for 2 hours to form a solid having voids with increased volume, and after completing crystallization, to room temperature (25 ° C.) state Cooled down. A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 92 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 5): x = 18
Maintain 3 g of triglyceride having a stearic acid residue (carbon number 18) at positions 1 to 3 (XXX type: 99.6 mass%, tristearin, manufactured by Sigma-Aldrich) at 80 ° C. for 0.5 hour to completely After melting and cooling in a 60 ° C. constant temperature bath for 12 hours to form a solid having voids with an increased volume and completing crystallization, it was cooled to room temperature (25 ° C.). A powdered oil composition which is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 30 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.93).

(Production Example 6): x = 18
25 g of a triglyceride (XXX type: 96.0% by mass, tristearin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a stearic acid residue (carbon number 18) at the 1st to 3rd positions is maintained at 80 ° C. for 0.5 hour. The mixture was completely melted and cooled in a constant temperature bath at 55 ° C. for 12 hours to form a solid having voids with an increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. A powdered oil composition that is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 31 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.88).

(Production Example 7): x = 18
25 g of triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) at 80 ° C. for 0.5 hour It was maintained and completely melted, and cooled in a constant temperature bath at 55 ° C. for 12 hours to form a solid having voids with an increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. A powdered oil composition that is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 54 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 8): x = 18
25 g of a triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 66.7% by mass, soybean hardened oil, produced by Yokoseki Oil & Fat Co., Ltd.) at 80 ° C. for 0.5 hour This was maintained and completely melted, and cooled in a constant temperature bath at 55 ° C. for 12 hours to form a solid having voids with an increased volume to complete crystallization, and then cooled to a room temperature (25 ° C.) state. A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.3 g / cm ³ , aspect ratio: 1.4, average particle size 60 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.91).

(Production Example 9): x = 18
Triglycerides having a stearic acid residue (18 carbon atoms) at the 1st to 3rd positions (XXX type: 84.1% by mass, Nisshin Sunflower Oil (S) (High Orac Sunflower Oil), manufactured by Nisshin Oillio Group, Inc. ) Was subjected to a complete hydrogenation treatment by a conventional method to obtain a hydrogenated product (XXX type: 83.9% by mass). 25 g of the resulting high oleic sunflower oil extremely hardened oil was completely melted by maintaining at 80 ° C. for 0.5 hours, cooled in a constant temperature bath at 55 ° C. for 12 hours, and a solid having voids with increased volume. After forming and completing crystallization, it was cooled to room temperature (25 ° C.). A powdered oil composition that is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 48 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 10): x = 18
Triglycerides having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 66.7% by mass, soybean hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.), 18.75 g, Triglyceride having a stearic acid residue (carbon number 18) at the 3rd position (XXX type: 11.1% by mass, palm extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) 6.25 g was mixed to obtain a raw material fat (XXX Type: 53.6% by mass). After the raw fat / oil is completely melted by maintaining at 80 ° C. for 0.5 hours, cooled in a constant temperature bath at 55 ° C. for 12 hours to form solids having voids with increased volume, and crystallization is completed And cooled to room temperature (25 ° C.). A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.3 g / cm ³ , aspect ratio: 1.4, average particle size 63 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.78). Palm extremely hardened oil had a very low content of XXX type triglyceride and was used as a diluent component (hereinafter the same).

(Production Example 11): x = 18, (c1) Seeding method Triglyceride having stearic acid residue (18 carbon atoms) at 1st to 3rd positions (XXX type: 96.0% by mass, Tristearin, Tokyo Chemical Industry) Kogyo Co., Ltd.) 25 g at 80 ° C. for 0.5 hours, completely melted and cooled in a 70 ° C. constant temperature bath until the product temperature reaches 70 ° C. 0.1% by mass, left in a constant temperature bath at 70 ° C. for 12 hours to form a solid having voids with increased volume, and after completing crystallization, to room temperature (25 ° C.) state Cooled down. A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 36 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.88).

(Production Example 12): x = 18, (c2) Tempering method Triglyceride having a stearic acid residue (carbon number 18) at 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, Yokoseki) 15 g of oil and fat industry) was completely melted by maintaining at 80 ° C. for 0.5 hour, cooled in a thermostatic bath at 50 ° C. for 0.1 hour, and then allowed to stand in a thermostatic bath at 65 ° C. for 6 hours. A solid having voids with an increased volume was formed, and after crystallization was completed, the mixture was cooled to room temperature (25 ° C.). A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 50 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.90).

(Production Example 13): x = 18, (c2) Tempering method Triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, Yokoseki) 15 g of oil and fat industry) was completely melted by maintaining at 80 ° C. for 0.5 hours, cooled in a 40 ° C. constant temperature bath for 0.01 hours, and then allowed to stand in a 65 ° C. constant temperature bath for 2 hours. A solid having voids with an increased volume was formed, and after crystallization was completed, the mixture was cooled to room temperature (25 ° C.). A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 52 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 14): x = 18, (c3) Precooling method Triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, 25 g of Yokoseki Yushi Kogyo Co., Ltd.) is maintained at 80 ° C. for 0.5 hours to completely melt, and the raw oil and fat is held in a 70 ° C. constant temperature bath until it reaches 70 ° C., and then in a 65 ° C. constant temperature bath for 8 hours. After cooling, a solid having voids with an increased volume was formed, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 60 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.89).

(Production Example 15): x = 20
10 g of a triglyceride having an arachidic acid residue (carbon number 20) at positions 1 to 3 (XXX type: 99.5% by mass, triarachidin, manufactured by Tokyo Chemical Industry Co., Ltd.) is maintained at 90 ° C. for 0.5 hour. It melt | dissolved completely, it cooled in a 72 degreeC thermostat for 12 hours, the solid substance which has the space | gap which increased in volume was formed, and after crystallization was completed, it cooled to the room temperature (25 degreeC) state. A powdered oil composition which is a powdery crystal composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 42 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.92).

(Production Example 16): x = 22
10 g of triglyceride (XXX type: 97.4% by mass, tribehenine, manufactured by Tokyo Chemical Industry Co., Ltd.) having a behenic acid residue (carbon number 22) at the 1st to 3rd positions was maintained at 90 ° C. for 0.5 hour. It melt | dissolved completely, it cooled in the 79 degreeC thermostat for 12 hours, the solid substance which has the space | gap which increased in volume was formed, and after completing crystallization, it cooled to the room temperature (25 degreeC) state. A powdered oil composition that is a powdery crystalline composition by loosening the obtained solid (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 2.0, average particle size 52 μm, X-ray diffraction measurement diffraction) Peak: 4.6 Å, peak intensity ratio: 0.93).

(Production Example 17): x = 16, 18
12.5 g of a triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions and stearin at the 1st to 3rd positions Triglyceride having an acid residue (18 carbon atoms) (XXX type: 96.0% by mass, Tristearin, Tokyo Chemical Industry Co., Ltd.) 12.5 g was mixed to obtain a raw oil (XXX type: 93.8%) . The raw oil / fat is completely melted by maintaining at 80 ° C. for 0.5 hour, cooled in a constant temperature bath at 55 ° C. for 16 hours to form a solid having voids with increased volume, and then loosened to form powder Powdered fat composition (relaxed bulk density: 0.2 g / cm ³ , aspect ratio: 1.6, average particle size 74 μm, X-ray diffraction measurement diffraction peak: 4.6 Å, peak intensity ratio: 0) .90).

(Production Example 18): x = 16, 18
Triglycerides having a palmitic acid residue (16 carbon atoms) at positions 1 to 3 (XXX type: 69.9% by mass, hard palm stearin, Nisshin Oilio Group Co., Ltd.) 12.5 g and positions 1 to 3 12.5 g of a triglyceride having a stearic acid residue (18 carbon atoms) (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokoseki Yushi Kogyo Co., Ltd.) was used as a raw material fat (XXX type: 75.3%). The raw oil / fat is completely melted by maintaining at 80 ° C. for 0.5 hour, cooled in a constant temperature bath at 55 ° C. for 16 hours to form a solid having voids with increased volume, and then loosened to form powder Powdered fat composition (relaxed bulk density: 0.3 g / cm ³ , aspect ratio: 1.4, average particle size 77 μm, X-ray diffraction measurement diffraction peak: 4.6 Å, peak intensity ratio: 0) .88) was obtained.

(Production Comparative Example 1): x = 16
25 g of a triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions is maintained at 80 ° C. for 0.5 hour. When it is completely melted and cooled in a thermostatic bath at 25 ° C. for 4 hours, it completely solidifies (X-ray diffraction measurement diffraction peak: 4.1 ピ ー ク, peak intensity ratio: 0.10). It did not arrive at a certain powdery fat composition.

(Production Comparative Example 2): x = 16, 18
Triglycerides having a palmitic acid residue (carbon number 16) at the 1st to 3rd positions (XXX type: 69.9% by mass, hard palm stearin, Nisshin Oilio Group Co., Ltd.) 12.5g, 1st to 3rd positions And 12.5 g of triglyceride having a stearic acid residue (18 carbon atoms) (XXX type: 11.1% by mass, palm extremely hardened oil, manufactured by Yokoseki Yushi Kogyo Co., Ltd.) were used as raw material fats and oils (XXX type: 39.6% by mass). The raw oil and fat was completely melted by maintaining at 80 ° C. for 0.5 hours, and then cooled in a constant temperature bath at 40 ° C. for 12 hours to be completely solidified (X-ray diffraction measurement diffraction peak: 4.2 kg, peak intensity ratio) : 0.12), it did not reach the powdered fat composition which is a powdery crystal composition.

(Production Comparative Example 3): x = 18
25 g of triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) at 80 ° C. for 0.5 hour When maintained and completely melted and cooled in a constant temperature bath at 40 ° C. for 3 hours, it completely solidifies (X-ray diffraction measurement diffraction peak: 4.1 Å, peak intensity ratio: 0.11), and powdery crystal composition It did not arrive at the powdery fat composition which is a thing.

(Production Comparative Example 4): x = 18
12.5 g of a triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 66.7% by mass, soybean hardened oil, produced by Yokoseki Yushi Kogyo Co., Ltd.) Triglyceride having a stearic acid residue (carbon number 18) at the 3-position (XXX type: 11.1% by mass, palm extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) 12.5 g was mixed to obtain a raw material fat (XXX Type: 39.7% by mass). The raw oil and fat was completely melted by maintaining at 80 ° C. for 0.5 hours and cooled in a constant temperature bath at 55 ° C. for 12 hours to be completely solidified (X-ray diffraction measurement diffraction peak: 4.2 kg, peak intensity ratio) : 0.12), it did not reach the powdered fat composition which is a powdery crystal composition.

The results of the production examples and production comparative examples are summarized in Tables 7 and 8.

・ Powder oil and fat composition C (powder oil and fat composition for emulsification)
25 g of triglyceride having a stearic acid residue (carbon number 18) at the 1st to 3rd positions (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokoseki Oil & Fat Co., Ltd.) at 80 ° C. for 0.5 hour It was maintained and completely melted, cooled in a thermostatic bath at 60 ° C. for 12 hours to form a solid having voids with increased volume, and after crystallization was completed, it was cooled to a room temperature (25 ° C.) state. The obtained solid is mechanically pulverized to obtain a powdered oil composition that is a powdery crystalline composition (loose bulk density: 0.2 g / cm ³ , aspect ratio 1.51, average particle size 7.4 μm, X-ray Diffraction measurement Diffraction peak: 4.6 Å, peak intensity ratio: 0.89). In Test Example 4 below, this powdery fat composition C was used.

[Test Example 4] Emulsification characteristics of powdered oil and fat composition of the present invention <Production of W / O type emulsion composition (oil phase 40 mass%)>
In a constant temperature room at 20 ° C., the W / O emulsion composition of Example 18 having the composition shown in Table 9 was produced by the following procedures 1 to 7.
1. Canola oil was weighed into a 200 mL glass beaker.
2. Powdered fat composition C was added to canola oil.
3. The canola oil to which the powdery fat composition C was added was stirred for 1 minute at a rotation speed of 5000 rpm using a homomixer.
4). While stirring the canola oil to which the powdered fat and oil composition C was added at a rotational speed of 5000 rpm, ion-exchanged water measured in a separate container was added dropwise with a dropper.
5). After all the ion-exchanged water was added, the number of revolutions of the homomixer was increased to 10000 rpm and stirred for 1 minute to prepare a W / O type emulsion composition.
6). The obtained W / O emulsion composition was dispensed in 10 g portions into two test tubes, one test tube was placed in a constant temperature bath at 20 ° C., and the other test tube was heated with an 80 ° C. heat block. did.
7. After 10 minutes from the start of storage at 20 ° C. and heating at 80 ° C., two test tubes containing the W / O emulsion composition were taken out and photographed side by side.
8). Subsequently, one test tube was placed in a constant temperature bath at 20 ° C., and the other test tube was heated with an 80 ° C. heat block.
9. After 14 hours from the start of storage at 20 ° C. and heating at 80 ° C., two test tubes containing the W / O emulsion composition were taken out and photographed side by side.
As a comparison, the W / O type emulsion composition of Comparative Example 5 not blended with the powdered fat composition C shown in Table 8 was the same as the above procedure (however, the procedure 2 was not carried out). Manufactured.
Table 11 shows the appearance of the obtained emulsified composition at 20 ° C. and after 10 minutes from the start of heating at 80 ° C. and after 14 hours.
FIG. 13 is a photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsified compositions of Example 18 and Comparative Example 5, and (1) Example 18, 20 ° C., 10 ° C. in order from the left. (2) Example 18, 80 ° C., 10 minutes later, (3) Comparative Example 5, 20 ° C., 10 minutes later, (4) Comparative Example 5, 80 ° C., 10 minutes later.
And FIG. 14 is a photograph 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsified compositions of Example 18 and Comparative Example 5, in order from the left: (1) Examples 18, 20 ° C., 14 After 2 hours, (2) Example 18, 80 ° C., 14 hours later, (3) Comparative Example 5, 20 ° C., 14 hours later, (4) Comparative Example 5, 80 ° C., 14 hours later.

<Manufacture of W / O type emulsion composition (oil phase 60% by mass, oil phase 80% by mass)>
In the same manner as in Example 18 and Comparative Example 5, the W / O type emulsion compositions of Example 19 and Comparative Example 6 and the W / O type emulsion compositions of Example 20 and Comparative Example 7 shown in Table 10 were mixed. A thing was prepared and each photograph was taken.
Tables 12 and 13 show the appearance of the obtained emulsified composition after 20 minutes of storage at 20 ° C. and 10 minutes after the start of heating at 80 ° C. and after 14 hours.
FIG. 15 is a photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 19 and Comparative Example 6, and (1) Example 19, 20 ° C., 10 ° C. in order from the left. (2) Example 19, 80 ° C., 10 minutes later, (3) Comparative Example 6, 20 ° C., 10 minutes later, (4) Comparative Example 6, 80 ° C., 10 minutes later.
FIG. 16 is a photograph 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsified compositions of Example 19 and Comparative Example 6, and (1) Example 19, 20 ° C., 14 in order from the left. After 2 hours, (2) Example 19, 80 ° C., 14 hours later, (3) Comparative Example 6, 20 ° C., 14 hours later, (4) Comparative Example 6, 80 ° C., 14 hours later.
FIG. 17 is a photograph 10 minutes after the start of 20 ° C. storage and 80 ° C. heating of the emulsion compositions of Example 20 and Comparative Example 7, and (1) Example 20, 20 ° C., 10 ° C. in order from the left. (2) Example 20, 80 ° C., 10 minutes later, (3) Comparative Example 7, 20 ° C., 10 minutes later, (4) Comparative Example 7, 80 ° C., 10 minutes later.
And FIG. 18 is a photograph 14 hours after the start of 20 ° C. storage and 80 ° C. heating of the emulsified compositions of Example 20 and Comparative Example 7, in order from the left: (1) Examples 20, 20 ° C., 14 After 2 hours, (2) Example 20, 80 ° C., 14 hours later, (3) Comparative Example 7, 20 ° C., 14 hours later, (4) Comparative Example 7, 80 ° C., 14 hours later.

From the results of Tables 11 to 13, the emulsion composition containing the emulsified powder oil-fat composition of the present invention is an emulsion composition that is stable at 20 ° C. only by temperature control of heating the emulsion composition to 80 ° C. It was found that there was a characteristic that it was possible to break the emulsion.
By utilizing this characteristic, for example, after using the emulsified composition blended with the emulsified powder oil and fat composition of the present invention for washing machines and devices, the recovered emulsified composition is heated to 80 ° C. or higher. By demulsifying and separating into an aqueous phase and an oil phase, the oil phase or the aqueous phase is recovered and reused, or the separated oil phase is treated as oil waste, or the separated aqueous phase is treated as water waste. It becomes possible to do.

Claims (16)

1. A powdered oil / fat composition for emulsification containing a powdery oil / fat composition satisfying the following condition (a).
   (A) A powdery oil / fat composition containing an oil / fat component containing one or more XXX-type triglycerides having a fatty acid residue X having carbon number x at positions 1 to 3 of glycerin, wherein the carbon number x is Is an integer selected from 10 to 22, wherein the fat and oil component includes β-type fat and oil, the particles of the powdery fat composition have a plate shape, and the loose bulk density of the powdery fat and oil composition is 0.05 to 0.6 g / cm ³ .
2. The powdered fat composition for emulsification according to claim 1, wherein the fat component comprises β-type fat.
3. The powdered fat composition for emulsification according to claim 1 or 2, wherein the XXX type triglyceride contains 50 mass% or more when the total mass of the fat component is 100 mass%.
4. The emulsified powder fat composition according to any one of claims 1 to 3, wherein the carbon number x is an integer selected from 16 to 18.
5. The powdery fat composition contains a β-type fat obtained by cooling and solidifying an oil or fat composition raw material containing a XXX type triglyceride at a cooling temperature or higher obtained by the following formula: The powder oil-fat composition for emulsification according to any one of the above.
   Cooling temperature (° C.) = Carbon number ×× 6.6−68
6. The powdery fat composition contains a β-type fat obtained by cooling and solidifying an oil-fat composition raw material containing XXX-type triglyceride at a temperature equal to or higher than the melting point of the α-type fat corresponding to the β-type fat. The powder oil composition for emulsification according to any one of claims 1 to 5.
7. The powdered oil / fat composition for emulsification according to any one of claims 1 to 6, wherein an average particle size of the powdered oil / fat composition is 20 µm or less.
8. An emulsified composition comprising the emulsified powder oil-fat composition according to any one of claims 1 to 7.
9. The emulsified composition according to claim 8, comprising 0.5 to 20 parts by mass of the emulsified powder fat composition with respect to 100 parts by mass of the oil phase of the emulsified composition.
10. The emulsion composition according to claim 8 or 9, wherein the emulsion composition is a water-in-oil emulsion composition.
11. The emulsified composition according to any one of claims 8 to 10, wherein the emulsified composition does not contain an emulsifier.
12. A method for producing an emulsified composition, comprising mixing an aqueous phase and an oil phase to produce the emulsified composition according to any one of claims 1 to 7 in the oil phase. .
13. The method for producing an emulsified composition according to claim 12, wherein 0.5 to 20 parts by mass of the emulsified powder / fat composition is added to 100 parts by mass of the oil phase of the emulsified composition.
14. The method for producing an emulsion composition according to claim 12 or 13, wherein the emulsion composition is a water-in-oil emulsion composition.
15. The method for producing an emulsified composition according to any one of claims 12 to 14, wherein the emulsion composition is produced without using an emulsifier.
16. An emulsifier substitute or an emulsification aid comprising the emulsified powder oil composition according to any one of claims 1 to 7 as an active ingredient.

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