JP2014152264A - Fat solidification agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fat solidification agent which can solidify a fat although constituent fatty acids of an emulsifier contains practically no 20C or higher fatty acid.SOLUTION: A fat solidification agent contains an ingredient A consisting of a sorbitan fatty acid ester of an esterification ratio of 25-50% and an ingredient B consisting of a polyglyceryl fatty acid ester of an esterification ratio of 15% or higher.

Description

  The present invention relates to an oil and fat solidifying agent.

  Conventionally, a method for increasing the melting point of fats and oils by hydrogenation or the like to solidify the fats and oils has been known. However, since the fats and oils produced by this method usually contain trans fatty acids, there is a concern about the use of the fats and oils for edible health effects. Therefore, various methods for solidifying fats and oils without producing trans fatty acids by using an emulsifier as a fat and oil solidifying agent have been proposed.

  These contain, for example, an oil-solidifying agent which is an ester of a fatty acid having 20 or more carbon atoms, and margarine according to claim 1, wherein the oil-solidifying agent is an ester of a fatty acid having 20 or more carbon atoms. A shortening according to claim 1, characterized in that it contains an oil solidifying agent (Patent Document 2), an ester of a fatty acid having 20 or more carbon atoms, and a polyglycerol fatty acid ester and / or a sucrose fatty acid ester having an HLB of 3 or less. The fat and oil solidifying agent containing the fat and oil solidifying agent to be used together (Patent Document 3), the average degree of polymerization of polyglycerol is 20 to 40-mer, and the constituent fatty acid is behenic acid in which 60% or more of all the constituent fatty acids are behenic acid, And (A) at least one linear saturated fatty acid having 16 to 22 carbon atoms, (B) a linear saturated fatty acid having 8 to 14 carbon atoms, a branched fatty acid having 18 to 22 carbon atoms, and It contains at least one or more selected from the group consisting of unsaturated fatty acids having a prime number of 18-22, and the molar ratio of (A) :( B) is 0.91: 0.09-0.99: 0.01 And an oil and fat solidifying agent characterized by containing a polyglycerol fatty acid ester having an esterification rate of 70% or more (Patent Document 4).

  However, since the constituent fatty acids of the emulsifier used in the above method are mainly fatty acids having 20 or more carbon atoms such as behenic acid, when the fats and oils to which such an emulsifier is added are edible, These methods are not always satisfactory because the texture may be deteriorated.

JP 2000-116322 A (Claim 2) JP 2000-116323 A (Claim 2) JP 2000-119687 A (Claim 2) JP 2012-082236 A (Claim 1)

  An object of the present invention is to provide an oil and fat solidifying agent capable of solidifying an oil and fat even when the constituent fatty acid of the emulsifier does not substantially contain a fatty acid having 20 or more carbon atoms.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using two types of emulsifiers having an esterification rate within a specific range, and based on this finding. The present invention has been achieved.

That is, the present invention
(1) An oil and fat solidifying agent characterized by containing the following A component and B component;
A component: Sorbitan fatty acid ester having an esterification rate of 25 to 50%;
Component B: polyglycerol fatty acid ester having an esterification rate of 15% or more,
(2) An edible oil / fat composition comprising the oil / fat solidifying agent according to (1),
It is made up of.

The edible oil / fat composition to which the oil / fat solidifying agent of the present invention is added is imparted with sufficient hardness and also has an excellent effect of suppressing the exudation of liquid oil / fat during storage.
According to the fat-and-oil solidifying agent of the present invention, the above effect can be obtained even if the constituent fatty acid of the emulsifier does not substantially contain a fatty acid having 20 or more carbon atoms.

  The sorbitan fatty acid ester used as the component A in the present invention is produced by a direct esterification reaction between sorbitol and a fatty acid, and has an esterification rate of 25 to 50%, preferably 25 to 45%. . When the esterification rate is less than 25% or exceeds 50%, the effect of the oil solidifying agent of the present invention cannot be sufficiently obtained, which is not preferable. Here, the esterification rate (%) is calculated by the following formula. In addition, the ester value and the hydroxyl value in the following formula are shown in [2.3.3-1996 Ester Value] and [2.3. 6-1996 hydroxyl number].

  Examples of the sorbitol used as the raw material for the component A include D-sorbitol liquid containing about 50.0 to 70.0% by mass of D-sorbitol, white powder, or granular D-sorbitol.

  The fatty acid used as a raw material for the component A is not particularly limited as long as it is a fatty acid derived from edible animal and vegetable oils and fats. For example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid And saturated fatty acids such as linoleic acid and unsaturated fatty acids. These fatty acids may be used alone or in any combination of two or more. From the viewpoint of enhancing the effect of the oil and fat solidifying agent of the present invention, saturated fatty acids are preferred, and palmitic acid and stearic acid are more preferred.

  In addition, these fatty acids are substantially free of fatty acids having 20 or more carbon atoms as constituent A fatty acids from the viewpoint of the effect on the texture of the edible oil / fat composition to which the oil / fat solidifying agent of the present invention is added. Is preferably selected. Here, substantially not containing a fatty acid having 20 or more carbon atoms means that the content of the fatty acid having 20 or more carbon atoms in 100% by mass of the constituent fatty acid of component A is less than about 5%, preferably less than about 1%. It points to something.

Here, the content of the fatty acid having 20 or more carbon atoms in 100% by mass of the constituent fatty acid of the A component refers to the content in 100% by mass of the fatty acid that is a raw material for the production of the A component. The following steps (1) to (3) may be carried out for the produced A component and measured.
(1) Preparation of sample In “2.4.1.2-1996 methyl esterification method (boron trifluoride methanol method)” of “Standard oil analysis test method (I)” (edited by the Japan Oil Chemists' Society). Prepare a sample according to the procedure.
(2) Measuring method Measured according to [2.4.2.2-1996 Fatty acid composition (FID temperature rising gas chromatograph method)] of "Standard oil analysis test method (I)" (edited by the Japan Oil Chemists' Society). To do.
(3) Quantification The percentage of each peak area with respect to the total peak area recorded by the data processing apparatus is taken as the content of constituent fatty acids.

  In the production of component A (esterification reaction), the amount of fatty acid charged relative to sorbitol is preferably about 1.3 to 2.3 mol per 1 mol of sorbitol.

  The production method of component A is not particularly limited. For example, the esterification reaction between sorbitol and a fatty acid may be carried out without a catalyst, or may be carried out using an acid catalyst or an alkali catalyst, but in the presence of an alkali catalyst. Are preferred. Examples of the acid catalyst include concentrated sulfuric acid and p-toluenesulfonic acid. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like. The usage-amount of an alkali catalyst is about 0.01-1.0 mass% of the total preparation amount (dry matter conversion), Preferably it is about 0.05-0.5 mass%.

  Although it does not specifically limit as a manufacturing apparatus of A component, For example, the said esterification reaction, for example, usually provided with a stirrer, a heating jacket, a baffle plate, an inert gas blowing tube, a thermometer, a moisture separator with a cooler, etc. While supplying sorbitol, fatty acid, and catalyst to the reaction vessel of, stirring and mixing the mixture, the water generated by the esterification reaction is removed from the system under an arbitrary inert gas atmosphere such as nitrogen or carbon dioxide. It is performed by heating at a temperature for a certain time. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. The reaction pressure is under reduced pressure or normal pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 4 hours. The end point of the reaction is usually determined by measuring the acid value of the reaction mixture and about 10 or less.

  When a catalyst is used after completion of the esterification reaction, the catalyst remaining in the reaction mixture may be neutralized. In that case, when the temperature of esterification reaction is 200 degreeC or more, it is preferable to neutralize after cooling liquid temperature to about 180-200 degreeC. Moreover, when reaction temperature is 200 degrees C or less, you may neutralize at the same temperature. After neutralization, it is allowed to stand at that temperature for about 0.5 hours or more, more preferably for about 1 to 10 hours. When unreacted sorbitol or sorbitol intramolecular condensate is separated into the lower layer, it is preferably removed.

  The polyglycerin fatty acid ester used as the component B in the present invention is an esterification product produced by an esterification reaction of polyglycerin and a fatty acid, and the esterification rate is 15% or more, preferably 40% or more. Is. If the esterification rate is less than 15%, the effect of the oil solidifying agent of the present invention cannot be sufficiently obtained, which is not preferable. The upper limit of the esterification rate is usually about 95%. The esterification rate of the B component is calculated based on the formula described above for the A component.

  As polyglycerin used as a raw material for component B, usually a small amount of acid or alkali is added to glycerin as a catalyst and heated at a temperature of, for example, about 180 ° C. or higher in any inert gas atmosphere such as nitrogen or carbon dioxide. And a mixture of polyglycerols having different degrees of polymerization obtained by polycondensation reaction. Polyglycerin may be obtained using glycidol or epichlorohydrin as a raw material. After completion of the reaction, treatments such as neutralization, desalting and decolorization may be performed as desired. The polyglycerin has an average degree of polymerization of 2 or more, for example, diglycerin (average degree of polymerization 2), triglycerin (average degree of polymerization 3), tetraglycerin (average degree of polymerization 4), pentaglycerin (average degree of polymerization 5). ), Hexaglycerin (average degree of polymerization 6), heptaglycerin (average degree of polymerization 7), octaglycerin (average degree of polymerization 8), decaglycerin (average degree of polymerization 10) and the like. In order to sufficiently exhibit the effect of solidification, it is preferable that the average degree of polymerization is 3 or more.

  The polyglycerin is a high-purity polyglycerin obtained by purifying a mixture of polyglycerins having different degrees of polymerization using a method known per se, such as distillation or column chromatography, and increasing the concentration of a single component. Are preferably used. As such an example, for example, a triglycerin mixture in which the content of triglycerin composed of three molecules of glycerin is about 50% by mass or more, preferably about 85% by mass or more.

Here, the average degree of polymerization (n) of the polyglycerol before the addition of glycerol can be calculated based on the following formulas (1) and (2).

Molecular weight = 74n + 18 (1)
Hydroxyl value = 56110 (n + 2) / Molecular weight (2)

The hydroxyl value in the above formula (2) is measured in accordance with [2.3.6-1996 Hydroxyl Number] of “Reference Oil Analysis Test Method (I)” (edited by Japan Oil Chemists' Society).

  The fatty acid used as a raw material for the component B is not particularly limited as long as it is a fatty acid derived from edible animal and vegetable oils and fats. For example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid And saturated fatty acids such as linoleic acid and unsaturated fatty acids. These fatty acids may be used alone or in any combination of two or more. From the viewpoint of enhancing the effect of fat and oil solidification of the fat and oil solidifying agent of the present invention, saturated fatty acids are preferred, and palmitic acid and stearic acid are more preferred.

  In addition, these fatty acids are substantially free of fatty acids having 20 or more carbon atoms in the component B, from the viewpoint of the effect on the texture of the edible fat composition to which the fat solidifying agent of the present invention is added. Is preferably selected. Here, “substantially free of fatty acids having 20 or more carbon atoms” means that the content of fatty acids having 20 or more carbon atoms in 100% by mass of the constituent fatty acids of component B is less than about 5%, preferably less than about 1%. It points to something.

  Here, the content of the fatty acid having 20 or more carbon atoms in 100% by mass of the constituent fatty acid of the B component refers to the content in 100% by mass of the fatty acid used as a raw material for the production of the B component. The above-described steps (1) to (3) may be performed for the component A and measured.

  In the above esterification reaction, the amount of fatty acid charged to polyglycerin varies depending on the target esterification rate and the average degree of polymerization of polyglycerin, etc., and is not uniform.For example, decaglycerin is used as polyglycerin, and esterification is performed. When a polyglycerol fatty acid ester having a rate of 80% is produced, the amount is about 9.6 mol per 1 mol of decaglycerol.

  In the esterification reaction, the esterification reaction between polyglycerol and fatty acid is usually performed using an alkali as a catalyst. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like. The amount of the alkali catalyst used is about 0.01 to 1.0% by mass, preferably about 0.05 to 0.5% by mass, in 100% by mass of the total charged amount (in terms of dry matter).

  The esterification reaction is carried out in a normal reaction vessel equipped with, for example, a stirrer, a heating jacket, a baffle plate, an inert gas blowing tube, a thermometer, a water separator with a condenser, etc. The catalyst is supplied and stirred and mixed, and heated at a predetermined temperature for a certain period of time while removing water generated by the esterification reaction outside the system in any inert gas atmosphere such as nitrogen or carbon dioxide. Is preferred. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. The pressure conditions in the reaction are under reduced pressure or normal pressure, and the reaction time is about 0.5 to 20 hours, preferably about 1 to 10 hours. As the end point of the reaction, it is preferable that the acid value of the reaction mixture is usually measured and the acid value is about 8 or less.

  After completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized as necessary. At that time, when the temperature of the esterification reaction is about 200 ° C. or higher, it is preferable to carry out the neutralization treatment after cooling the liquid temperature to about 150 to 200 ° C. Moreover, when reaction temperature is about 200 degrees C or less, you may neutralize at the same temperature. For neutralization of the catalyst, for example, when sodium hydroxide is used as an alkali catalyst and neutralized with phosphoric acid (85% by mass), the neutralization reaction formula (3) shown below:

_{3NaOH + H 3 PO 4 → Na} 3 PO 4 + 3H 2 O ··· (3)
More phosphoric acid (85% by mass) than the amount obtained by dividing the amount of phosphoric acid calculated by the above by 0.85 (approx. 0.96 g when the amount of sodium hydroxide used is 1.0 g), preferably About 2-3 times the amount of phosphoric acid calculated by the neutralization reaction formula (1) divided by 0.85 was added to the reaction mixture (85% by mass), and the neutralization reaction mixture was It is preferable to carry out by mixing well. After neutralization, it is preferably left at that temperature for about 0.5 hours or more, more preferably for about 1 to 10 hours. If unreacted polyglycerin separates into the lower layer, it is removed. Moreover, you may perform processes, such as decoloring and deodorizing, according to a conventional method as needed.

  The fat and oil solidifying agent of the present invention may be used by directly adding the component A and the component B during the production of the edible fat or oil composition, or may be prepared by mixing them in advance. Moreover, the edible oil-fat composition containing A component and B component obtained by adding these is also contained in this invention.

  Although there is no restriction | limiting in particular in the form of the edible oil-fat composition of this invention, For example, plastic oil-fat compositions, such as margarine which is a water-in-oil emulsion composition, fat spread, and shortening which hardly contains a water | moisture content, are mentioned. Here, margarine refers to those having a fat content of 80% by weight or more, and fat spread refers to those having a fat content of less than 80% by weight.

  There is no particular limitation on the fat and oil used as the raw material of the edible fat and oil composition of the present invention (that is, the fat and oil targeted by the fat and oil solidifying agent of the present invention), but the fat or oil can be solidified or thickened by the fat and oil solidifying agent of the present invention. Therefore, fats and oils that are liquid at 20 ° C. are preferable. Examples of such fats and oils include soybean oil, rapeseed oil (including rapeseed white squeezed oil), corn oil, sesame oil, perilla oil, linseed oil, peanut oil, safflower oil, safflower oil with high oleic acid, cottonseed oil, grape seed oil, Macadamia nut oil, hazelnut oil, pumpkin seed oil, walnut oil, coconut oil, tea seed oil, sesame oil, olive oil, mustard oil, rice oil, rice bran oil, wheat germ oil, safflower oil, sunflower oil and these oils and fats Or those subjected to transesterification. These fats and oils may be used alone or in any combination of two or more.

  Moreover, as fats and oils used as a raw material of the edible fat and oil composition of this invention, fats and oils other than fats and oils which are liquid at 20 degreeC can be used suitably. As such fats and oils, for example, palm oil (including refined palm oil), palm kernel oil, cocoa butter, coconut oil, lard, milk fat, chicken fat, beef tallow and those fats or oils or a transesterification treatment Among them, the raw material for the plastic fat composition is a vegetable fat suitable for the plastic fat composition because the slope of the solid fat content (SFC) curve as a function of temperature does not become too large. From the viewpoint, palm oil is preferred. As palm oil and fat, refined palm oil obtained by refining natural palm oil or palm olein or palm stearin obtained by fractionating natural palm oil is preferable.

  The above fats and oils specifically listed as fats and oils that are liquid at 20 ° C. and fats and oils that are liquid at 20 ° C. are preferably oils and fats in the present invention because they are all fats and oils that do not substantially contain trans fatty acids. Used. The edible oil / fat composition of the present invention is preferably produced using only the oil / fat which does not substantially contain such a trans fatty acid as a raw oil / fat. Here, fats and oils substantially free of trans fatty acids refer to fats and oils having a trans fatty acid content of less than 5%, preferably less than about 1%, in 100% of fatty acids constituting the fats and oils.

  The manufacturing method of the edible fat composition of the present invention is not particularly limited, and a method known per se can be used. Below, the manufacturing method of a margarine is illustrated. For example, the oil and fat and the fat solidifying agent of the present invention are mixed and heated to dissolve at about 50 to 80 ° C., preferably about 60 to 70 ° C., and optionally an antioxidant (for example, extracted tocopherol etc.) β-carotene, etc.), flavor (eg, milk flavor, etc.), emulsifier (eg, lecithin, glycerin fatty acid ester, etc.) and the like are added to obtain an oil phase. On the other hand, milk or dairy products (eg, whole milk powder, skim milk powder, etc.), salt, sugars, acidulants (eg, citric acid, etc.), etc. are added to purified water as desired, and heated to about 50-70 ° C. to dissolve. Let it be an aqueous phase. Next, the oil phase and the aqueous phase are mixed using a normal stirring / mixing tank, and the resulting mixture is fed to a quenching kneader with a feed pump to continuously crystallization and kneading of fats and oils. Go to and get margarine. Further, without taking the emulsification step, the oil phase and the water phase can be sent to a quenching kneader with a metering pump, respectively, and then treated in the same manner to obtain margarine.

  The content of component A and component B in the edible oil / fat composition of the present invention is the form of the edible oil / fat composition, the content of oil / fat that is liquid at 20 ° C. in the edible oil / fat composition, and the intended edible oil / fat composition. The content of the component A is usually about 0.05 to 1.0 part by mass, preferably about 0 with respect to 100 parts by mass of the oil and fat contained in the edible oil and fat composition. 0.1 to 0.6 parts by mass, and the content of component B can be adjusted to be usually about 0.05 to 1.0 parts by mass, preferably about 0.1 to 0.6 parts by mass. .

  Moreover, the edible fat composition of this invention can make content of the fats and oils which are liquid at 20 degreeC into 30 mass% or more. In particular, when the edible oil / fat composition is a plastic oil / fat composition, the effect of the oil / fat solidifying agent of the present invention is exhibited even if the content of the oil / fat which is liquid at 20 ° C. is such a high value. By this, sufficient hardness as a plastic fat composition is provided.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Production Example 1]
[Production of sorbitan fatty acid ester]
A 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 260 g of sorbitol (trade name: sorbitol S; manufactured by Nikken Kasei Co., Ltd.), and then stearic acid and palmitic acid. 274 g of fatty acid composition (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) is added as a main component, 0.80 g of sodium hydroxide is added as a catalyst, and nitrogen is added under normal pressure. The esterification reaction was performed in a gas stream for about 1.5 hours at 235 ° C. until the acid value was 10 or less. The obtained reaction product was cooled to obtain about 412 g of sorbitan fatty acid ester (prototype A; esterification rate: 24%).

[Production Example 2]
[Production of sorbitan fatty acid ester]
A 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 260 g of sorbitol (trade name: sorbitol S; manufactured by Nikken Kasei Co., Ltd.), and then stearic acid and palmitic acid. 356 g of main fatty acid composition (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) was added, 0.92 g of sodium hydroxide was added as a catalyst, and nitrogen was added under normal pressure. The esterification reaction was performed in a gas stream for about 1.5 hours at 235 ° C. until the acid value was 10 or less. The obtained reaction product was cooled to obtain about 487 g of sorbitan fatty acid ester (prototype B; esterification rate: 28%).

[Production Example 3]
[Production of sorbitan fatty acid ester]
A 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 260 g of sorbitol (trade name: sorbitol S; manufactured by Nikken Kasei Co., Ltd.), and then stearic acid and palmitic acid. 521 g of fatty acid composition (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) is added as a main component, 1.17 g of sodium hydroxide is added as a catalyst, and nitrogen is added under normal pressure. The esterification reaction was carried out in a gas stream for about 2.0 hours at 235 ° C. until the acid value was 10 or less. The obtained reaction product was cooled to obtain about 632 g of sorbitan fatty acid ester (prototype C; esterification rate 40%).

[Production Example 4]
[Production of sorbitan fatty acid ester]
A 2 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 260 g of sorbitol (trade name: sorbitol S; manufactured by Nikken Kasei Co., Ltd.), and then stearic acid and palmitic acid. 712 g of fatty acid composition (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Yushi Co., Ltd.) is added as a main component, 0.48 g of sodium hydroxide is added as a catalyst, and nitrogen is added under normal pressure. The esterification reaction was performed in a gas stream for about 2.5 hours at 235 ° C. until the acid value became 10 or less. The obtained reaction product was cooled to obtain about 797 g of sorbitan fatty acid ester (prototype D; esterification rate 60%).

[Production Example 5]
[Production of sorbitan fatty acid ester]
A 2 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 260 g of sorbitol (trade name: sorbitol S; manufactured by Nikken Kasei Co., Ltd.), and then stearic acid and palmitic acid. The main fatty acid composition (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) was charged with 822 g, 0.54 g of sodium hydroxide was added as a catalyst, and nitrogen was added under normal pressure. The esterification reaction was carried out in a gas stream for about 3.0 hours at 235 ° C. until the acid value was 10 or less. The obtained reaction product was cooled to obtain about 888 g of sorbitan fatty acid ester (prototype E; esterification rate 70%).

  Here, the esterification rate of the sorbitan fatty acid esters (prototypes A to E) produced in Production Examples 1 to 5 and the content of saturated fatty acids having 16 to 18 carbon atoms and 20 or more carbon atoms in 100% constituent fatty acids. (%) Is shown in Table 1.

[Production Example 6]
[Production of polyglycerol fatty acid ester]
20 kg of glycerin was added to a reaction kettle equipped with a stirrer, thermometer, gas blowing tube and water separator, 100 mL of 20% aqueous sodium hydroxide solution was added as a catalyst, and glycerin condensation reaction was performed at 250 ° C. for 4 hours in a nitrogen gas stream It was. The obtained reaction product was cooled to about 90 ° C., neutralized by adding about 20 g of phosphoric acid (85%), filtered, and the filtrate was distilled under reduced pressure at 160 ° C. and 250 Pa to obtain glycerin. Next, molecular distillation was performed under high vacuum conditions of 200 ° C. and 20 Pa, and a fraction containing 0.2% glycerin, 5% diglycerin, 88% triglycerin and 6% tetraglycerin, and 0.8% cyclic glycerin. 1.5% was obtained. Next, 1% activated carbon was added to the fraction, decolorized under reduced pressure, and then filtered. The obtained high purity triglycerin had a hydroxyl value of about 1170 and an average degree of polymerization of about 3.0.
Subsequently, in a 1 L four-necked flask equipped with a stirrer, a thermometer, a gas blowing tube and a water separator, 472 g of the obtained high-purity triglycerin, stearic acid, and a fatty acid composition mainly composed of palmitic acid (product) Name: Stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 328 g, 1.2 g of sodium hydroxide as a catalyst, and ester at 240 ° C. for about 3 hours in a nitrogen gas stream The reaction was carried out. After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 680 g of a polyglycerol fatty acid ester (prototype F; esterification rate 12%).

[Production Example 7]
[Production of polyglycerol fatty acid ester]
A fatty acid composition comprising 394 g of the obtained high-purity triglycerin, stearic acid and palmitic acid (trade name: stearin) in a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator Acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 406 g, sodium hydroxide 1.2 g was added as a catalyst, and esterification reaction was performed at 240 ° C. for about 3 hours in a nitrogen gas stream. went.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 715 g of a polyglycerol fatty acid ester (prototype G; esterification rate: 18%).

[Production Example 8]
[Production of polyglycerol fatty acid ester]
Fatty acid composition (trade name: stearin) mainly composed of 240 g of the obtained high-purity triglycerin, stearic acid and palmitic acid in a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator Acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 560 g, sodium hydroxide 1.2 g was added as a catalyst, and the esterification reaction was carried out at 240 ° C. for about 5 hours in a nitrogen gas stream. went.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 725 g of a polyglycerol fatty acid ester (prototype H; esterification rate 40%).

[Production Example 9]
[Production of polyglycerol fatty acid ester]
A fatty acid composition mainly composed of 144 g of the obtained high-purity triglycerin, stearic acid and palmitic acid in a 1 L four-necked flask equipped with a stirrer, a thermometer, a gas blowing tube and a water separator (trade name: stearin Acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 656 g, 1.2 g of sodium hydroxide was added as a catalyst, and esterification was carried out at 240 ° C. for about 8 hours in a nitrogen gas stream. went.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 1.6 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 740 g of a polyglycerol fatty acid ester (prototype I; esterification rate 80%).

[Production Example 10]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 568 g of polyglycerin (trade name: glycerin # 500; average polymerization degree 6; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 288 g was charged, 1.2 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 3 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 690 g of a polyglycerol fatty acid ester (prototype J; esterification rate 12%).

[Production Example 11]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 455 g of polyglycerin (trade name: glycerin # 500; average polymerization degree 6; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and 390 g of a fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) was added, and 1.2 g of sodium hydroxide was added as a catalyst. The esterification reaction was carried out at 240 ° C. for about 3 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 725 g of a polyglycerol fatty acid ester (prototype K; esterification rate 20%).

[Production Example 12]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 306 g of polyglycerin (trade name: glycerin # 500; average polymerization degree 6; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 524 g was charged, 1.2 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 5 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 730 g of a polyglycerol fatty acid ester (prototype L; esterification rate 40%).

[Production Example 13]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 187 g of polyglycerin (trade name: glycerin # 500; average polymerization degree 6; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 632 g was added, 0.8 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 8 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 1.6 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 740 g of a polyglycerol fatty acid ester (prototype M; esterification rate 80%).

[Production Example 14]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 577 g of polyglycerin (trade name: glycerin # 750; average polymerization degree 10; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 280 g was charged, 1.2 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 3 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 690 g of a polyglycerol fatty acid ester (prototype N; esterification rate 12%).

[Production Example 15]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 476 g of polyglycerin (trade name: glycerin # 750; average polymerization degree 10; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 372 g was added, 1.2 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 3 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerol was removed to obtain about 725 g of a polyglycerol fatty acid ester (prototype O; esterification rate 20%).

[Production Example 16]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 326 g of polyglycerin (trade name: glycerin # 750; average polymerization degree 10; manufactured by Sakamoto Pharmaceutical Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 507 g was added, 1.2 g of sodium hydroxide was added as a catalyst, and nitrogen was added. The esterification reaction was carried out at 240 ° C. for about 5 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 2.4 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerin was removed to obtain about 730 g of a polyglycerin fatty acid ester (prototype P; stealth rate: 40%).

[Production Example 17]
[Production of polyglycerol fatty acid ester]
In a 1 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 199 g of polyglycerin (trade name: glycerin # 750; average polymerization degree 10; manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), stearic acid and A fatty acid composition mainly composed of palmitic acid (trade name: stearic acid 65; stearic acid and palmitic acid content 99.4%; manufactured by Miyoshi Oil & Fats Co., Ltd.) 621 g, charged with 0.8 g of sodium hydroxide as a catalyst, nitrogen The esterification reaction was carried out at 240 ° C. for about 8 hours in a gas stream.
After confirming that the acid value of the reaction solution is 8 or less, the reaction solution is cooled to about 150 ° C., and 1.6 g of phosphoric acid (85% by mass) is added to neutralize the catalyst. After leaving for 1 hour, the separated unreacted polyglycerin was removed to obtain about 740 g of a polyglycerin fatty acid ester (prototype Q; stealization rate 80%).

  Here, the esterification rate of the polyglycerin fatty acid esters (prototypes F to Q) produced in Production Examples 6 to 17, the average degree of polymerization of polyglycerin constituting them, and 100% of the constituent fatty acids have 16 to 18 carbon atoms. Table 2 shows the content (%) of saturated fatty acids having 20 or more carbon atoms.

  Moreover, these combinations and blending ratios (parts by mass) and combinations thereof when using sorbitan fatty acid esters (prototypes A to E) and polyglycerin fatty acid esters (prototypes F to Q) in combination as fat and oil solidifying agents 1 to 18 Table 3 shows the average degree of polymerization of polyglycerol for the esterification rate (%) and the polyglycerol fatty acid ester. In addition, the fat-and-oil solidifying agents 1-10 are the examples which concern on this invention, and the fat-and-oil solidifying agents 11-18 are comparative examples with respect to these.

[Production and Evaluation of Margarine Containing Oil Solidifying Agent]
(1) Raw material of margarine 1) Purified water 2) Salt 3) Rapeseed white squeezed oil (trade name; Sarasara canola oil; manufactured by J-Oil Mills)
4) Refined palm oil (trade name: RPO; Ueda Oil Co., Ltd.)
5) Oil solidifying agent 1-18
6) Glycerin fatty acid ester (trade name: Poem S-95; esterification rate 70%; manufactured by Riken Vitamin Co., Ltd.)
7) Lecithin (trade name: lecithin A; manufactured by Nisshin Oilio Co., Ltd.)

(2) Blending of margarine The blending composition of margarine (sample Nos. 1 to 18) produced using the above raw materials is shown in Tables 4 and 5. Among these, sample No. 1 to 10 are examples according to the present invention. Reference numerals 11 to 18 are comparative examples for these.

(3) Production method of margarine Margarine (sample Nos. 1 to 19) was prepared according to the blending ratio of raw materials shown in Tables 4 and 5 and the following steps 1) to 4). The production amount of margarine was 3000 g each.
1) Salt was added to purified water to dissolve, and the mixture was heated to about 60 ° C. to obtain an aqueous phase.
2) The fat-and-oil solidifying agents 1-18, glycerin fatty acid ester, and lecithin were added and melt | dissolved in the compounding oil consisting of rapeseed white squeezed oil and refined palm oil, and it heated to about 70 degreeC, and was set as the oil phase.
3) While stirring the oil phase of 2) at a low speed with a TK homomixer (model: MARKII; manufactured by Primix), gradually add the water phase of 1), add all, and then stir at a high speed. Emulsified.
4) After quenching and kneading the obtained emulsion in a conventional manner, a cylindrical plastic container (65 mm in diameter, 40 mm in height) was tempered at 25 ° C. for 24 hours and then at 5 ° C. for 48 hours. It preserve | saved and margarine (sample No. 1-18) was obtained.
5) As a control, the above 1) to 4) were carried out in the same manner without using the oil solidifying agents 1 to 18, and margarine (sample No. 19) containing no oil solidifying agent was obtained.

(4) Measurement of hardness About margarine (sample Nos. 1 to 19) filled at 5 ° C. in a plastic container, using a texture analyzer (product name: Ez Test; manufactured by Shimadzu Corporation) under an environment of 25 ° C. Hardness was measured. In the measurement of hardness, a cylindrical plunger having a diameter of 14 mm was used, and the stress (N) when the plunger was pushed 8 mm from the margarine surface was measured.

(5) Measurement of oil and oil seepage suppression effect Filter paper (trade name: No. 5C; manufactured by Advantech Toyo Co., Ltd., width 10 mm, height on the surface of margarine (sample No. 1 to 19) filled in a plastic container. (200 mm strip) was vertically contacted with one of the short side surfaces and allowed to stand in a thermostat at 25 ° C. for 24 hours. After leaving still for 24 hours, the moving distance (mm) of the fats and oils which soaked into the filter paper was measured.

(6) Evaluation of storage stability at 25 ° C. A liquid separated from the surface of margarine (sample Nos. 1 to 19) filled in a plastic container in a thermostat at 25 ° C. for 1 week. The state of the oil and fat (liquid oil) was visually observed and evaluated. The results were symbolized according to the following evaluation criteria.
○: No liquid oil is seen on the surface △: A little liquid oil is seen on the surface ×: The separated liquid oil is layered on the surface

(7) Results Table 6 shows the results of (4) to (6).

  By exhibiting the effects of the oil solidifying agents 1 to 10 of the present invention, the margarine (sample Nos. 1 to 10) to which this has been added contains 30% by mass or more of the oil and fat that is liquid at 20 ° C. Sufficient hardness was imparted as the plastic fat composition, and the exudation suppressing effect and storage stability were also excellent. On the other hand, the margarine (sample No. 11-18) to which the fat and oil solidifying agent 11-18 was added and the control margarine (sample No. 19) were inferior to those of the present invention in any of the evaluation items. . Moreover, such an effect of the present invention is realized by using only an emulsifier substantially free of a fatty acid having 20 or more carbon atoms, and the present invention is excellent also in this respect.

Claims (2)

The fat-and-oil solidifying agent characterized by containing the following A component and B component.
A component: Sorbitan fatty acid ester having an esterification rate of 25 to 50%;
Component B: Polyglycerin fatty acid ester having an esterification rate of 15% or more.   An edible oil / fat composition comprising the oil / fat solidifying agent according to claim 1.