JP2007325540A - Oil and fat-containing instant processed food - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide oil and fat-containing instant processed food suppressed in oil separation or blooming during storage, or precipitation of ingredients other than oil and fat falling in oil and fat-containing instant food such as solid roux, and maintaining shine and luster at its surface. <P>SOLUTION: The oil and fat-containing instant processed food contains the following: (a) at least two kinds selected from glycerine fatty acid ester, diglycerol fatty acid ester and triglycerol fatty acid ester; (b) sorbitan fatty acid ester having ≥50 mass% of ≥22C saturated fatty acid based on 100 mass% of constituent fatty acid; and/or (c) polyglyceryl fatty acid ester having ≥50 mass% of ≥22C saturated fatty acid based on 100 mass% of constituent fatty acid and having an average polymerization degree of 4-10. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a roux such as curry, stew or coconut rice, which prevents oil separation and blooming during long-term storage or sedimentation of components other than fats and oils contained in instant processed foods containing fats and oils. The present invention relates to a fat-containing instant processed food having a solid property at room temperature (about 1 to 30 ° C.).

As for the instant processed foods containing fats and oils, many products have been developed and widely used for household use. Among them, instant processed foods containing fats and oils such as solid roux, which is a raw material such as curry, stew or coconut rice, are easily used for cooking at home. However, these processed foods originally have a number of improvements due to problems such as oil separation and blooming over time, and the gloss or luster of the surface of instant processed foods containing fats and oils such as solid roux are lost. Has been carried out.
For example, a method of adding monoglycerin fatty acid ester to roux and cooling and solidifying in a specific temperature range to prevent roux oil floating, whitening, dew condensation water, etc. (Patent Document 1), fats and oils, starch raw materials, flavor At least 5% or more of milk raw materials and milk processing raw materials are blended in the raw materials, and in the production process of instant roux including the step of heat-treating these raw materials, diglycerin fatty acid ester having HLB of 6-9 is 0.1-3 0.0% addition of instant roux (Patent Document 2), roux plastic oil composition characterized by containing an emulsifier having an HLB of 10 or more (Patent Document 3), low HLB A method for producing paste-like roux using an emulsifier of HLB 1 to 3 as an emulsifier and an emulsifier of HLB 11 to 16 as an emulsifier of high HLB (Patent Document 4), presenting a solid state in the temperature range, It is obtained by dispersing alpha starch and flavor ingredients in oils and fats that are fluidized by receiving (glycerin stearic acid ester and propylene glycol fatty acid ester added to liquid oil and fat at room temperature and heat-treated). Rou (Patent Document 5), oils and fats and emulsifiers (sucrose fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester and propylene glycol fatty acid ester) 2 or more) water-containing solid roux oil composition (Patent Document 6), polyglycerin composition, at least one polyglycerin selected from tri, tetra, penta, hexa, hepta, octa, nona, decaglycerin Oil containing polyglycerol fatty acid ester having a content of 35% or more Food (Patent Document 7), the average degree of polymerization of glycerin is 4 or more, the average degree of esterification of fatty acid is 6 or more, and 35% or more of the constituent fatty acid is 1 to 50% by weight of polyglycerin fatty acid ester made of behenic acid And 25 to 99% by weight of fat and oil consisting of at least one of hardened beef tallow, hardened lard, hardened palm oil, hardened palm fractionated oil, hardened rapeseed oil and hardened rapeseed oil, and 0 to 25% by weight of lecithin The solid roux whitening preventive agent (Patent Document 8), the edible solid fat and oil crystal regulator (Patent Document 9) characterized by containing polyglycerin fatty acid ester as an active ingredient.

However, since none of the above is sufficiently dispersible, such as fats and oils, it cannot be said that the above-mentioned problems have been solved to a satisfactory degree by the methods disclosed so far, and it is said that sufficient effects are not obtained. Currently. For this reason, there is a demand for the development of instant processed foods containing fats and oils that can maintain the gloss and gloss of the surface during long-term storage with less oil separation and blooming.
Japanese Patent No. 2816282 Japanese Patent No. 3737066 JP 2003-310155 A JP 2002-125634 A JP 2001-197872 A JP 2001-029050 A JP-A-11-235156 Japanese Patent Laid-Open No. 10-313783 JP-A-10-140180

  The present invention provides oil-containing instants such as solid roux that can suppress oil separation and blooming during storage and settling of components other than fats and oils contained in the instant processed foods containing fats and oils and maintain the gloss and gloss of the surface. To provide processed foods.

  As a result of intensive studies on the above problems, the present inventors have found that at least two types of glycerin fatty acid ester, diglycerin fatty acid ester and triglycerin fatty acid ester and a saturated fatty acid having 22 or more carbon atoms are 50% by mass of the fatty acid. By adding a polyglycerin fatty acid ester in which the sorbitan fatty acid ester and the saturated fatty acid having 22 or more carbon atoms are 50% by mass or more of the fatty acid and the average degree of polymerization of glycerin is about 4 to 10 It was found that an instant processed food containing fats and oils was obtained, and further research was carried out based on this finding, leading to the present invention.

That is, the present invention
[1] a) Two or more kinds selected from glycerin fatty acid ester, diglycerin fatty acid ester and triglycerin fatty acid ester;
b) Saturated fatty acids having 22 or more carbon atoms among the constituent fatty acids are sorbitan fatty acid esters having 50% by mass or more in 100% by mass of the constituent fatty acids and / or c) Saturated fatty acids having 22 or more carbon atoms among the constituent fatty acids. An oil-containing instant processed food containing a polyglycerin fatty acid ester having an average degree of polymerization of glycerin of 4 to 10 in 100% by mass of fatty acid and [2] diglycerin fatty acid The fat or oil-containing composition according to claim 1, wherein the content of the monoester is 50% by mass or more in 100% by mass of the ester or triglycerin fatty acid ester, and the hydroxyl value of the diglycerin fatty acid ester or triglycerin fatty acid ester is 200 or more. Instant processed foods,
About.

  The instant processed food containing fats and oils such as solid roux in the present invention suppresses oil separation and blooming during storage, or sedimentation of components other than fats and oils contained in the instant processed food containing fats and oils, and the gloss of the surface even during long-term storage. , Can maintain gloss. Examples of the blooming include a phenomenon in which the fats and oils of instant processed foods containing fats such as solid roux float on the surface and solidify.For example, the surface of the instant processed foods containing fats and oils such as solid roux is white or curry powder dissolved in fats and oils. The phenomenon which looks yellowish green by a component, for example, turmeric etc. is mentioned.

  Examples of instant processed foods containing fats and oils according to the present invention include raw materials such as curry, stew or coconut rice, such as stew ingredients such as roux and curry powder, roux and white sauce and demiglace sauce (hereinafter referred to as solid roux). And the like are preferred. Examples of the roux include those obtained by heating and mixing cereal flour such as wheat flour and fats and oils such as butter. The instant processed food containing fats and oils such as solid roux according to the present invention is based on edible fats and oils, cereal flours such as wheat flour, etc. Two or more types selected from glycerin fatty acid ester, diglycerin fatty acid ester and triglycerin fatty acid ester as components composed of paste or extract (liquid, paste-like or powder) and the like, and among the constituent fatty acids, 22 or more carbon atoms The average polymerization degree of sorbitan fatty acid ester and / or glycerin in which saturated fatty acid is about 50% by mass or more in 100% by mass of constituent fatty acid is about 4 to 10, and saturated fatty acid having 22 or more carbon atoms among constituent fatty acids, An emulsifier such as polyglycerin fatty acid ester of about 50% by mass or more in 100% by mass of the constituent fatty acid is blended. In the present invention, the instant processed food containing fats and oils such as solid roux can be further added with food hygiene acceptable food additives such as antioxidants, surfactants or fragrances as desired. The instant processed food containing fats and oils such as solid roux according to the present invention may be solid or powdered at room temperature (about 1 to 30 ° C.). The solid form includes a fluid or non-fluid paste.

Examples of the glycerin fatty acid ester used in the present invention include esterified products of glycerin and fatty acids, or products obtained by transesterification of glycerin and fats and oils, and the content of monoester in 100% by mass of glycerin fatty acid ester. Is about 70% by weight or more, preferably about 90% by weight or more.
The glycerin fatty acid ester having the above characteristics is usually added to a mixture of fat and glycerin with an alkali (for example, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, etc.) as a catalyst. Under an active gas atmosphere, for example, in the range of about 180 to 260 ° C., preferably at about 200 to 250 ° C., for about 0.5 to 5 hours, preferably about 1 to 3 hours for transesterification or fatty acid Acid or alkali is added to the mixture of glycerin and glycerol as a catalyst, and in any inert gas atmosphere such as nitrogen or carbon dioxide, for example in the range of about 180-260 ° C, preferably about 0.5 at about 200-250 ° C. ~ 5 hours, preferably about 1 to 3 hours of heating to carry out the esterification reaction, neutralize the catalyst after completion of the reaction, and from the resulting reaction mixture unreacted Glycerin, can be obtained by as much as possible remove diglyceride and triglyceride. Examples of the method for removing the unreacted glycerin, diglyceride and triglyceride include known methods such as vacuum distillation, molecular distillation, column chromatography or liquid-liquid extraction. After removing glycerin, diglyceride and triglyceride, treatment such as decolorization and deodorization may be performed as desired.

The diglycerin fatty acid ester used in the present invention is a product of an esterification reaction of diglycerin and a fatty acid, and the esterification reaction can be performed by a known method. The diglycerin used as a raw material for the diglycerin fatty acid ester is usually a small amount of acid (for example, concentrated sulfuric acid, p-toluenesulfonic acid, etc.) or alkali (for example, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate). Etc.) as a catalyst and heated at a temperature of, for example, about 180 ° C. or higher in an inert gas atmosphere such as nitrogen or carbon dioxide, and the average degree of polymerization of glycerin obtained by polycondensation reaction is about 1. A diglycerin mixture of 5 to 2.4, preferably an average degree of polymerization of about 2.0 is mentioned. Diglycerin 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.
As the diglycerin that is a raw material for producing the diglycerin fatty acid ester used in the present invention, the diglycerin mixture is purified by a known method such as distillation or column chromatography, and diglycerin composed of two molecules of glycerin. High-purity diglycerin having a high concentration of about 50% by mass or more, preferably about 85% by mass or more is preferably used.

  The fatty acid used as a raw material for the diglycerin fatty acid ester is not particularly limited as long as it is a fatty acid derived from edible animal and vegetable oils and fats. For example, a straight-chain saturated fatty acid having 6 to 24 carbon atoms (for example, caproic acid, capryl). Acids, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) or unsaturated fatty acids (eg palmitooleic acid, oleic acid, elaidic acid, linoleic acid, γ- Linolenic acid, α-linolenic acid, arachidonic acid, ricinoleic acid, condensed ricinoleic acid, etc.). In particular, it is preferable to use a saturated fatty acid containing about 70% by mass or more, more preferably about 90% by mass or more of palmitic acid and / or stearic acid.

Preferable examples of the diglycerin fatty acid ester include diglycerin fatty acid esters having a monoester content of about 50% by mass or more, preferably about 70% by mass or more and a hydroxyl value of about 200 or more.
Here, the hydroxyl value is measured according to [ _2.3.6-1996 Hydroxyl Number] of “Standard Oil Analysis Test Method (I)” (edited by Japan Oil Chemists' Society).

The outline of the production method of the diglycerin fatty acid ester having such a composition is as follows.
For example, a normal reaction vessel equipped with a stirrer, a heating jacket or a baffle plate is charged with diglycerin and a fatty acid (eg, palmitic acid) at a molar ratio of about 1: 1, and sodium hydroxide is added as a normal catalyst. The mixture is stirred and mixed, and heated at a predetermined temperature in a nitrogen gas atmosphere while removing water produced by the esterification reaction out of the system. The predetermined temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. Moreover, the pressure conditions in the reaction are under reduced pressure or normal pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 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 12 or less. The obtained reaction liquid is a mixture containing unreacted fatty acid, unreacted diglycerin, diglycerin monofatty acid ester, diglycerin difatty acid ester, diglycerin trifatty acid ester, diglycerin tetrafatty acid ester and the like.

  After completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized. At that time, when the temperature of the esterification reaction is about 200 ° C. or higher, it is preferable to perform the neutralization after cooling the liquid temperature to about 180 to 200 ° C. Moreover, when reaction temperature is about 200 degrees C or less, you may neutralize at the same temperature. After neutralization, the reaction mixture is optionally cooled and maintained at about 100-180 ° C., preferably about 130-150 ° C., preferably about 0.5 hours or longer, more preferably about 1-10 hours. Is preferred. When unreacted diglycerin is separated into the lower layer, it is preferably removed.

  The diglycerin fatty acid ester obtained by the above treatment is preferably further distilled under reduced pressure to distill off the remaining unreacted diglycerin. Subsequently, for example, a falling film molecular distillation apparatus or a centrifugal molecular distillation apparatus A diglycerin fatty acid ester containing about 70% by mass or more of a monoester can be obtained by performing molecular distillation using a method such as column chromatography or purification using a method known per se such as column chromatography or liquid-liquid extraction.

  The triglycerin fatty acid ester used in the present invention is an esterification reaction product of triglycerin and a fatty acid, and the esterification reaction can be produced by a known method.

  The triglycerin used as a raw material for the triglycerin fatty acid ester used in the present invention is usually a small amount of acid (for example, concentrated sulfuric acid, p-toluenesulfonic acid, etc.) or alkali (for example, potassium hydroxide, sodium hydroxide). , Potassium carbonate, sodium carbonate, etc.) added as a catalyst and heated under a temperature of about 180 ° C. or higher under any inert gas atmosphere such as nitrogen or carbon dioxide, and the average of glycerin obtained by polycondensation reaction A triglycerin mixture having a degree of polymerization of about 2.5 to 3.4, preferably an average degree of polymerization of about 3.0 is mentioned. Triglycerin 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.

  In the triglycerin which is a raw material for producing the triglycerin fatty acid ester used in the present invention, the triglycerin mixture is purified by a method known per se such as distillation or column chromatography, and triglycerin composed of three molecules of glycerin. High-purity triglycerin having a concentration of about 50% by mass or more, preferably about 85% by mass or more is preferably used.

  The fatty acid used as a raw material for the triglycerin fatty acid ester is not particularly limited as long as it is a fatty acid derived from edible animal and vegetable oils and fats. For example, a straight-chain saturated fatty acid having 6 to 24 carbon atoms (for example, caproic acid, capryl). Acids, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) or unsaturated fatty acids (eg palmitooleic acid, oleic acid, elaidic acid, linoleic acid, γ- Linolenic acid, α-linolenic acid, arachidonic acid, ricinoleic acid, condensed ricinoleic acid, etc.).

  Preferable examples of the triglycerin fatty acid ester include triglycerin fatty acid esters having a monoester content of about 50% by mass or more, preferably about 70% by mass or more and a hydroxyl value of about 200 or more.

Here, the hydroxyl value is measured according to [ _2.3.6-1996 Hydroxyl Number] of “Standard Oil Analysis Test Method (I)” (edited by Japan Oil Chemists' Society).

The outline of the method for producing the triglycerin fatty acid ester having such a composition is as follows.
For example, an ordinary reaction vessel equipped with a stirrer, a heating jacket, a baffle plate, etc. is charged with triglycerin and a fatty acid (eg, palmitic acid) at a molar ratio of about 1: 1, and sodium hydroxide is added as a normal catalyst. The mixture is stirred and mixed, and heated at a predetermined temperature in a nitrogen gas atmosphere while removing water produced by the esterification reaction out of the system. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. Moreover, the pressure conditions in the reaction are under reduced pressure or normal pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 hours. The end point of the reaction is preferably measured by measuring the acid value of the reaction mixture and using an oxidation of about 12 or less as a guide. The obtained reaction liquid is a mixture containing unreacted fatty acid, unreacted triglycerin, triglycerin monofatty acid ester, triglycerin difatty acid ester, triglycerin trifatty acid ester, triglycerin tetrafatty acid ester, triglycerin pentafatty acid and the like. It is.

  After completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized. At that time, when the temperature of the esterification reaction is about 200 ° C. or higher, it is preferable to perform the neutralization after cooling the liquid temperature to about 180 to 200 ° C. Moreover, when reaction temperature is about 200 degrees C or less, you may neutralize at the same temperature. After neutralization, the reaction mixture is optionally cooled and maintained at about 100-180 ° C., preferably about 130-150 ° C., preferably about 0.5 hours or longer, more preferably about 1-10 hours. Is preferred. When unreacted triglycerin is separated into the lower layer, it is preferably removed.

  The triglycerin fatty acid ester obtained by the above treatment is preferably further distilled under reduced pressure to distill off the remaining unreacted triglycerin. Subsequently, for example, a falling film molecular distillation apparatus or a centrifugal molecular distillation apparatus The triglycerin fatty acid ester containing about 70% by mass or more of the monoester can be obtained by performing molecular distillation using a method such as column chromatography or purification using a method known per se such as column chromatography or liquid-liquid extraction.

  Two or more combinations of the glycerin fatty acid ester, diglycerin fatty acid ester, and triglycerin fatty acid ester used in the present invention are suitable. As the two or more types of combinations, a combination of glycerin fatty acid ester and diglycerin fatty acid ester, a combination of glycerin fatty acid ester and triglycerin fatty acid ester, a combination of diglycerin fatty acid ester and triglycerin fatty acid ester, or a glycerin fatty acid ester Examples include combinations of diglycerin fatty acid esters and triglycerin fatty acid esters. The added amount of glycerin fatty acid ester, diglycerin fatty acid ester or triglycerin fatty acid ester (total amount of two or more combinations; the same applies hereinafter) is about 0.05 to 5.0% by mass in the instant processed food , Preferably about 0.3 to 3.0% by mass. The addition amount of glycerin fatty acid ester, diglycerin fatty acid ester or triglycerin fatty acid ester is in the range of about 0.05 to 5.0 mass%, oil separation and blooming during storage of the fat-containing instant processed food according to the present invention, Alternatively, it is advantageous to suppress sedimentation of components other than fats and oils contained in instant processed foods containing fats and oils, to maintain the gloss and gloss of the surface, and to suppress the phenomenon that the taste and flavor are deteriorated or the properties are hardened. .

  The sorbitan fatty acid ester used in the present invention is a sorbitan fatty acid ester in which the saturated fatty acid having 22 carbon atoms is about 50% by mass or more in 100% by mass of the constituent fatty acid. Specific examples thereof include sorbitan monobehenate and sorbitan dibe. Examples include henate or sorbitan tribehenate.

  The sorbitan fatty acid ester used in the present invention can be obtained by a direct esterification reaction between a sorbitol or sorbitol intramolecular condensate and a fatty acid in the presence of an acid or an alkali catalyst.

  Examples of sorbitol used in the esterification reaction include white powder or granular D-sorbitol, or D-sorbitol liquid containing about 50.0 to 70.0% by mass of D-sorbitol.

Examples of the sorbitol intramolecular condensate used in the esterification reaction include compounds obtained by intramolecular dehydration of sorbitol. For example, 1,5-sorbitan, 1,4-sorbitan, 2,5-sorbitan, 3,6 -Sorbitan or 1,4,3,6-sorbide etc. are mentioned. These sorbitol intramolecular condensates can be used alone or in combination of two or more. The sorbitol intramolecular condensate used in the present invention may contain unreacted sorbitol in addition to the above compounds.
The intramolecular dehydration reaction of sorbitol is carried out by heating sorbitol at about 110 to 150 ° C., preferably about 120 ° C. in the presence of an acid catalyst (for example, concentrated sulfuric acid, p-toluenesulfonic acid, etc.), for example, about 1 It is preferably carried out by removing the generated water at .3 kPa. The end point of the reaction can be determined by measuring the hydroxyl value of the dehydrated condensate. After completion of the reaction, it is preferable to neutralize the acid catalyst by adding, for example, an aqueous sodium hydroxide solution to the dehydrated condensate, and further filter by adding a filter aid such as diatomaceous earth.

  Examples of the fatty acid used in the esterification reaction include, for example, a mixture of saturated fatty acid having 6 to 24 carbon atoms and containing about 50% by mass or more of saturated fatty acid (behenic acid) having 22 carbon atoms, preferably 16 to 16 carbon atoms. It is a mixture of 24 linear saturated fatty acids. Specific examples of preferred saturated fatty acids include palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and the like. These fatty acids may be used alone or in any combination of two or more if behenic acid is included in an amount of about 50% by mass or more.

  In the esterification reaction, the amount of fatty acid charged to sorbitol or sorbitol intramolecular condensate is preferably about 3 to 4 moles relative to about 1 mole of sorbitol or sorbitol intramolecular condensate.

  The esterification reaction between sorbitol or sorbitol intramolecular condensate 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 is preferably carried out in the presence of an alkali catalyst. 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. As the usage-amount of an alkaline catalyst, about 0.01-1.0 mass% of the total preparation amount (dry matter conversion), Preferably about 0.05-0.5 mass% is mentioned.

  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 and a water separator with a cooler, etc., sorbitol or sorbitol intramolecular condensate, Supply fatty acid and catalyst, stir and mix, and heat at a predetermined temperature for a certain time while removing water generated by esterification reaction outside the system in any inert gas atmosphere such as nitrogen or carbon dioxide Done. The reaction temperature is usually in the range of about 180 to 260 ° C, preferably in the range of about 200 to 250 ° C. Moreover, the pressure conditions in the reaction are under reduced pressure or normal pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 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 10 or less.

  When a catalyst is used after completion of the esterification reaction, it is preferable to neutralize the catalyst remaining in the reaction mixture. At that time, when the temperature of the esterification reaction is about 200 ° C. or higher, it is preferable to perform the neutralization after cooling the liquid temperature to about 180 to 200 ° C. When the reaction temperature is about 200 ° C. or lower, the neutralization treatment may be performed at the same temperature. After neutralization, it is preferably left 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.

  In the method of the present invention, the sorbitan saturated fatty acid ester added to the fat or oil is preferably one having an esterification rate in the range of about 50% to 100%. The esterification rate (%) is expressed by the following formula:

により算出される。ここでエステル価及び水酸基価は、「基準油脂分析試験法（Ｉ）」（社団法人 日本油化学会編）の［２．３．３_-1996 エステル価］及び［２．３．６_-1996 ヒドロキシル価］に従って測定される。

Is calculated by Here, the ester value and the hydroxyl value are determined in accordance with [ _2.3.3-1996 Ester Value] and [ _2.3.6-1996 Hydroxyl] of “Standard Oil and Fat Analysis Test Method (I)” (edited by Japan Oil Chemists' Society). Value].

  The polyglycerin fatty acid ester used in the present invention is a polyglycerin in which the saturated fatty acid having 22 carbon atoms is about 50% by mass or more and the average degree of polymerization of glycerin is about 4 to 10 in 100% by mass of the constituent fatty acid. Examples include fatty acid esters. Specific examples thereof include tetraglycerin hexabehenate and hexaglycerin octabehenate.

  The polyglycerin fatty acid ester (excluding diglycerin fatty acid ester and triglycerin fatty acid ester) used in the present invention is an esterification reaction product of polyglycerin (excluding diglycerin and triglycerin) and fatty acid, and is esterified. The reaction can be produced by a method known per se.

  As a polyglycerin used as a raw material for the production of polyglycerin fatty acid ester used in the present invention, a small amount of acid or alkali is usually added to glycerin as a catalyst, and under any inert gas atmosphere such as nitrogen or carbon dioxide. For example, a mixture of polyglycerols having different degrees of polymerization obtained by heating at a temperature of about 180 ° C. or more and causing a polycondensation reaction can be mentioned. 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. Examples of the polyglycerin include polyglycerin compositions having an average degree of polymerization of glycerin of about 4 to 20, preferably about 4 to 10, such as tetraglycerin (average degree of polymerization 4) and hexaglycerin (average degree of polymerization 6). , Octaglycerin (average polymerization degree 8), decaglycerin (average polymerization degree 10), and the like.

  The fatty acid used as a raw material for producing the polyglycerin fatty acid ester used in the present invention contains about 50% by mass or more of a saturated fatty acid having 22 carbon atoms (behenic acid), for example, a mixture of saturated fatty acids having 6 to 24 carbon atoms. Preferably, a mixture of a linear saturated fatty acid having 20 to 24 carbon atoms is used. Specific examples of preferable saturated fatty acids include arachidic acid, behenic acid, lignoceric acid and the like. These fatty acids may be used alone or in any combination of two or more.

  In the present invention, the amount of fatty acid charged to polyglycerin varies depending on the target degree of esterification and is not uniform, but is preferably in the range of about 0.1 to 1 mol per mol of polyglycerin. If the amount of fatty acid charged to polyglycerin is too small, the amount of polyglycerin fatty acid ester itself is reduced, which is not economically advantageous.

In the present invention, the esterification reaction of polyglycerin and fatty acid may be performed without a catalyst, or may be performed using an acid catalyst or an alkali catalyst, but is preferably performed in the presence of an alkali catalyst. 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 amount of the alkali catalyst used is about 5 × 10 ⁻⁷ to 1 mol times, preferably about 5 × 10 ^{−6 to} 0.1 mol times the amount of polyglycerol.

  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. Moreover, the pressure conditions in the reaction are under reduced pressure or normal pressure, and the reaction time is about 0.5 to 15 hours, preferably about 1 to 3 hours. The end point of the reaction is preferably measured by measuring the acid value of the reaction mixture and using an oxidation of about 12 or less as a guide.

  When a catalyst is used after completion of the esterification reaction, the catalyst remaining in the reaction mixture is neutralized. At that time, when the temperature of the esterification reaction is about 200 ° C. or higher, it is preferable to perform the neutralization after cooling the liquid temperature to about 180 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 the alkali catalyst and neutralized with phosphoric acid (85% by mass), the neutralization reaction formula (1) shown below:

で計算されるリン酸量を０．８５で除した量（水酸化ナトリウムの使用量を１．０ｇとすると、約０．９６ｇとなる。）以上のリン酸（８５質量％）を、好ましくは中和反応式（１）で計算されるリン酸量を０．８５で除した量の約２〜３倍量のリン酸（８５質量％）を反応混合物に添加して、中和反応混合物を良く混合することにより行われるのが好ましい。中和後、その温度で好ましくは約０．５時間以上、更に好ましくは約１〜１０時間放置するのが好ましい。
未反応のポリグリセリンが下層に分離した場合はそれを除去する。

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.

  The sorbitan fatty acid ester and / or polyglycerol fatty acid ester in the present invention can be added singly or in combination of two or more. The added amount (total amount of sorbitan fatty acid ester and / or polyglycerin fatty acid ester) is about 0.05 to 3.0% by mass, preferably about 0.1 to 1.% by weight based on the oil and fat content in the instant processed food. 0% by mass. If the added amount of sorbitan fatty acid ester and / or polyglycerin fatty acid ester is in the range of about 0.05 to 3.0% by mass, oil separation and blooming or fat during storage of the oil-containing instant processed food according to the present invention It is advantageous to suppress the sedimentation of components other than fats and oils contained in the contained accelerated processed food, to maintain the gloss and gloss of the surface, and to suppress the phenomenon that the taste and flavor are deteriorated or the properties are hardened.

  The sorbitan fatty acid ester and / or polyglycerin fatty acid ester dosage form in the present invention includes powders, pastes, solids, and the like, but any form may be used. Moreover, there is no restriction | limiting in particular also about the addition time of the sorbitan fatty acid ester and / or polyglycerol fatty acid ester at the time of manufacture, However It is desirable to add to fats and oils or to add simultaneously with fats and oils.

The instant processed food containing fats and oils such as solid roux according to the present invention can be produced, for example, by a method including the following steps (1) to (4).
Step (1):
Two or more types selected from glycerin fatty acid ester, diglycerin fatty acid ester and triglycerin fatty acid ester, and saturated fatty acid having 22 or more carbon atoms among the constituent fatty acids are about 50% by mass in 100% by mass of the constituent fatty acids. Of the above sorbitan fatty acid esters and / or constituent fatty acids, the saturated fatty acid having 22 or more carbon atoms is about 50% by mass or more in 100% by mass of the constituent fatty acids, and the average degree of polymerization of glycerin is about 4 to 10. A step of mixing a certain polyglycerin fatty acid ester (hereinafter referred to as an emulsifier) and heating the mixture to dissolve the emulsifier.
Step (2):
A step of preparing roux by adding cereal powder to the edible fat and oil mixture in which the emulsifier obtained in step (1) is dissolved and heating and mixing.
Step (3):
The process which mix | blends a seasoning and / or a paste, or an extract with the roux obtained at the process (2), and also adds the food additive etc. accept | permitted by food sanitation as needed, and it cools.
Step (4):
A step of filling the mold cooled in step (3) into a mold and solidifying by cooling.

  Examples of the edible oils and fats include, for example, vegetable oils such as rapeseed oil, soybean oil, olive oil, palm oil, and salad oil; animal oils such as butter and lard; or hardening of the vegetable oils and animal oils. Oil etc. are mentioned. The dissolution of the emulsifier in the step (1) is preferably performed, for example, at about 80 to 110 ° C. for about 10 minutes to 1 hour.

  As said grain flour, wheat flour, rice flour, potato starch, wheat starch etc. are mentioned, for example. The addition ratio of cereal flour to edible oil / fat varies depending on the edible oil / fat, cereal flour, etc., but is about 70-200 parts by mass, preferably about 80-150 parts by mass, per 100 parts by mass of edible oil / fat. The roux in the step (2) can be prepared by heating at about 80 to 150 ° C., preferably about 90 to 130 ° C. for about 5 to 60 minutes while mixing the edible oil and fat and the cereal flour.

  Examples of the seasoning include salt; for example, sugar, honey, fructose, maltose, erythritol, trehalose, maltose, licorice extract, stevia, saccharin, aspartame, acesulfame K, sucralose, xylitol, sorbitol, etc .; , Flavoring agents such as sodium glutamate, L-tricolominic acid, L-ipotenoic acid, sodium 5'-inosinate, sodium 5'-guanylate; or, for example, curry powder, pepper, turmeric, allspice, oregano, cardamom, Examples include spices such as cumin, cloves, coriander, saffron, cinnamon, ginger, star anise, sage, chili, nutmeg, garlic, paprika, mustard, rosemary, bay leaf, wasabi, savory powder, chili powder, etc.Although there is no restriction | limiting in particular in the shape of a seasoning, The powder seasoning which pulverized the said seasoning is preferable.

  Examples of the material used for the paste or extract include, for example, livestock such as beef, beef bone, pork, pork bone, chicken, chicken breast, etc .; for example, shrimp, crab, salmon, salmon, salmon, clams, clams, clams, Seafoods such as bandits, sea breams; algae such as kelp and seaweed; fruits such as apples and pears; dairy products such as milk, fresh cream and cheese; or potatoes, pumpkins, onions, carrots And vegetables such as celery. The materials used for these pastes or extracts can be used alone or in combination of two or more. For example, the paste is a combination of one or more of the above materials and boiled in water or the like, and the boiled material is crushed or ground (hereinafter referred to as crushed or the like) with, for example, a grinder and the above crushed. It can be produced by a process including a concentration process for concentrating the material solution crushed in the process. The extract is obtained by separating the material filtered from the filtration step and the filtration step of filtering the boiled material and the broth by combining one or two or more of the above materials with water or the like, and obtaining the extract. It may be produced by a process including a concentration process for concentrating the obtained filtrate. The above-described seasoning may be added to the paste or extract. If desired, the concentrated paste or extract may be dried by hot drying, freeze drying, drum drying, or the like, and the dried paste may be crushed with a grinder or the like to obtain a powder.

  Examples of the food additive include antioxidants such as dibutylhydroxytoluene, dibutylhydroxyanisole, tocopherol and L-ascorbic acid; for example, preservatives such as potassium sorbate, sodium dehydracetate and hinokitiol; for example, caramel, β- Colorants such as carotene and gardenia yellow pigments; surfactants such as polysorbate; or fragrances such as vanilla fragrance.

The cooling temperature in the step (3) is preferably about 50 to 60 ° C. If it is the said cooling temperature, in a process (4), a mold can be easily filled with a roux and can be cooled and solidified uniformly.
The cooling and solidification temperature in the step (4) is not particularly limited as long as it is a temperature at which roux solidifies. For example, about 0 to 25 ° C. is preferable.

  Hereinafter, the present invention will be described more specifically based on production examples, test examples, and examples, but the present invention is not limited thereto.

[Production Example 1]
Triglycerin mixture A reactor equipped with a stirrer, thermometer, gas blowing tube and water separator was charged with 20 kg of glycerin, and 100 mL of a 20 W / V% aqueous solution of sodium hydroxide was added as a catalyst. A glycerin condensation reaction was performed. The obtained reaction product was cooled to 90 ° C. and neutralized by adding about 20 g of phosphoric acid (85% by mass). The neutralized reaction product is filtered, and the filtrate is distilled under reduced pressure at 160 ° C. and 400 Pa to remove glycerin, followed by molecular distillation under high vacuum conditions at 200 ° C. and 20 Pa to mainly produce diglycerin. Excluding about 3.7 Kg of the fraction as a component, further molecular distillation under high vacuum conditions of 240 ° C. and 20 Pa, glycerin 1% by mass, diglycerin 4% by mass, triglycerin 88% by mass, tetraglycerin 3% by mass About 1.5 kg of a fraction containing 4% by mass of cyclic polyglycerin was obtained. Next, 1% by mass of activated carbon was added to the fraction, decolorized under reduced pressure, and then filtered. The obtained triglycerin mixture had a hydroxyl value of about 1164 and an average degree of polymerization of about 3.0.

[Production Example 2]
Triglycerin monopalmitate ester In a 2 L four-necked flask equipped with a stirrer, thermometer, gas blowing tube and water separator, 480 g (about 2.0 mol) of the triglycerin mixture obtained in Production Example 1, and palmitic acid Acid (trade name: LUNAC P-95; manufactured by Kao Corporation) is charged with 512 g (about 2.0 mol), and 20 mL of a 10 w / v sodium hydroxide solution is added as a catalyst, and the acid value is 12 or less at 240 ° C. in a nitrogen gas stream. The esterification reaction was allowed to proceed for about 2 hours until The obtained reaction mixture was cooled to about 130 ° C., 4 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and the mixture was allowed to stand at that temperature for about 1 hour, and about 80 g of unreacted triglycerin separated was removed. Removal of about 950 g of triglycerol palmitate was obtained. Next, the triglycerin palmitate is distilled using a centrifugal molecular distillation apparatus (experimental machine; CEH-300II; manufactured by ULVAC), and unreacted triglycerin and the like under a vacuum condition of about 240 ° C. and 20 Pa. Of low boiling point compound, followed by molecular distillation under a high vacuum condition of about 250 ° C. and 1 Pa, and as a fraction, triglycerin monopalmitate (prototype A: monoester content of about 85% by weight) , Hydroxyl value 440) about 200 g was obtained.

[Production Example 3]
Triglycerin monostearate ester In a 2 L four-necked flask equipped with a stirrer, a thermometer, a gas blowing tube and a water separator, 480 g (about 2.0 mol) of the triglycerin mixture obtained in <Production Example 1> And 456 g (about 2.0 mol) of stearic acid (trade name: stearic acid 90; manufactured by Miyoshi Oil & Fats Co., Ltd.), 20 mL of a 10 w / v% sodium hydroxide solution as a catalyst, and acid value at 240 ° C. in a nitrogen gas stream The esterification reaction was carried out for about 2 hours until 12 or less. The obtained reaction mixture was cooled to about 130 ° C., 4 g of phosphoric acid (85% by mass) was added to neutralize the catalyst, and the mixture was allowed to stand at that temperature for about 1 hour, and about 80 g of unreacted triglycerin separated was removed. Removal of about 970 g of triglycerin palmitate was obtained. Next, the triglycerin stearate is distilled using a centrifugal molecular distillation apparatus (experimental machine; CEH-300II; manufactured by ULVAC), and unreacted triglycerin and the like under a vacuum condition of about 240 ° C. and 20 Pa. Of low boiling point compounds, followed by molecular distillation under high vacuum conditions at a temperature of about 255 ° C. and 1 Pa. As fractions, triglycerin monostearate (prototype B: monoester content of about 84% by weight) , Hydroxyl value 440) about 210 g was obtained.

The ester composition analysis was performed by high performance liquid chromatography (HPLC). The analysis conditions are shown below.
<HPLC analysis conditions>
Apparatus High performance liquid chromatograph (Model: LC-10AS; manufactured by Shimadzu Corporation)
Detector RI detector (model: RID-6A; manufactured by Shimadzu Corporation)
Column GPC column (Model: SHODEX KF-802; Showa Denko)
2 links
Temperature 40 ° C, mobile phase THF flow rate 1.0mL / min
Sample injection volume 15μL

[Example]
1. Trial manufacture of curry roux After using 175 g of hardened palm oil to dissolve the emulsifiers listed in Table 1 by heating at 90 ° C. for 30 minutes, 160 g of flour was added and heated to 128 ° C. over 10 minutes. Next, 50 g of curry powder, 45 g of salt, 50 g of sugar, 7.5 g of powder seasoning and 7.5 g of paste seasoning are added to the hardened palm oil heated and mixed with the emulsifier, once cooled to 55 ° C., and 100 g each in a tray. It was filled and cooled and solidified at 10 ° C. to produce Karelau of Examples 1 to 4 and Comparative Examples 1 to 7. The curry roux filling tray was then stored at 10 ° C and 25 ° C. In addition, except for not adding the emulsifier shown in Table 1, curry ro produced in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 7 was used as a control.

2. Evaluation of Caraleu The Caraleu produced in 1 above and stored at 10 ° C. and 25 ° C. for 14 days was evaluated for the following three items: blooming, oil separation, and gloss. As a result, after the storage for 14 days at 10 ° C. and 25 ° C., the blooms of Examples 1 to 4 were both prevented from blooming and oil separation and had good gloss.

[Evaluation method for blooming]
The lightness (L value) on the surface of the roux was measured using a color reader CR-10 manufactured by MINOLTA, and the difference from the L value of the control with no added emulsifier was calculated. Evaluation was made according to the evaluation criteria in Table 2 from the difference from the L value of the obtained control. The results are shown in Tables 5 and 6.

[Evaluation method of oil separation]
Evaluation was performed by 10 panelists according to the evaluation criteria shown in Table 3. The result was obtained as an average value of the scores of 10 people and was symbolized according to the following criteria for preventing oil separation. The results are similarly shown in Tables 5 and 6.

Criteria for preventing oil separation Average score of 2.5 points or more: ○: Good Average score of 1.5 points or more and less than 2.5 points △: Slightly bad Average score of less than 1.5 points ... ×: Bad

[Gloss evaluation method]
A digital image is taken by applying a certain direction and a certain amount of light to the surface of the luu, and the image is analyzed using Adobe Photoshop Elements 2.0 (manufactured by Adobe Systems Incorporated), and the brightness level is expressed in number of pixels and graphed. It was expressed as a histogram. From the histogram, the gloss was quantified with the ratio of the brightness level of 180 or more as the gloss number. It evaluated according to the evaluation criteria of Table 4 from the glossiness number. The results are similarly shown in Tables 5 and 6.

The instant processed food containing fats and oils in the present invention is useful as an instant solid roux such as curry or stew.

Claims (2)

a) two or more kinds selected from glycerin fatty acid ester, diglycerin fatty acid ester and triglycerin fatty acid ester;
b) Saturated fatty acids having 22 or more carbon atoms among the constituent fatty acids are sorbitan fatty acid esters having 50% by mass or more in 100% by mass of the constituent fatty acids and / or c) Saturated fatty acids having 22 or more carbon atoms among the constituent fatty acids. An oil-containing instant processed food comprising a polyglycerin fatty acid ester having an average degree of polymerization of glycerin of 4 to 10 in 50% by mass or more in 100% by mass of fatty acid. The content of monoester is 50% by mass or more in 100% by mass of diglycerol fatty acid ester or triglycerol fatty acid ester, and the hydroxyl value of diglycerol fatty acid ester or triglycerol fatty acid ester is 200 or more. Instant processed food containing oil and fat.