Composition for inhibiting discoloration due to heating

Abstract

To prevent the discoloration of antioxidants that are difficult to dissolve in oils and fats, and metal ions, due to heating in the oils and fats.SOLUTION: The present invention provides a composition for preventing the discoloration of antioxidants that are difficult to dissolve in oils and fats, and metal ions, due to heating. The composition contains an organic acid monoglyceride.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for suppressing heat discoloration of poorly soluble oil and fat antioxidants by metal ions, a method for producing the composition, or a method for using the composition. [Background technology]

[0002] In food manufacturing, antioxidants are often added to oils and fats to extend their shelf life. Natural antioxidants usable in food include, for example, gallic acid and polyphenols. However, these antioxidants have multiple hydroxyl and carboxyl groups in their molecules, making them poorly soluble in oils and fats, and thus difficult to incorporate in high concentrations. Various methods have been explored to incorporate poorly soluble antioxidants into oils and fats (Patent Documents 1 and 2).

[0003] Furthermore, gallic acid and polyphenols have the problem of turning bluish-black when they come into contact with iron or copper equipment during the manufacturing process, due to reactions with metal ions. The inventors of this invention have discovered that organic acid monoglycerides, known as emulsifiers, have a previously unknown novel effect of capturing (chelating) metal ions. They then found that organic acid monoglycerides can suppress the heating-induced discoloration of oil-poorly soluble antioxidants caused by metal ions, thus completing the present invention. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. WO01 / 96506 [Patent Document 2] Japanese Patent Application Publication No. 9-235584 [Overview of the project] [Problems that the invention aims to solve]

[0005] To solve the above-mentioned problems, the present invention provides a composition for suppressing heat discoloration of oil-poorly soluble antioxidants by metal ions, which includes an organic acid monoglyceride, a method for producing the composition, and its use. [Means for solving the problem]

[0006] To solve the above problems, the present invention includes the following inventions. [1] A composition for suppressing heat discoloration between an oil-poorly soluble antioxidant and a metal ion, characterized by containing an organic acid monoglyceride. [2] The composition according to [1], further comprising oils and fats. [3] The composition according to [1] or [2], wherein the organic acid monoglyceride is one or more selected from the group consisting of citrate monoglyceride and diacetyltartrate monoglyceride. [4] The oil-insoluble antioxidants include polyphenols and gallic acid or its C 1-12 The composition according to any one of [1] to [3] above, comprising one or more selected from the group consisting of alkyl esters. [5] The composition according to any one of [1] to [4], further comprising one or more emulsifiers selected from the group consisting of lecithin, glycerin fatty acid esters other than organic acid monoglycerides, sucrose fatty acid esters, sorbitan fatty acid esters, and propylene glycol fatty acid esters. [6] A food containing any of the compositions described in [1] to [5] above. [7] The food items described in [6] above, which include noodles, rice dishes, bread, or confectionery. [8] A method for suppressing the discoloration reaction between metal ions and oil-poorly soluble antioxidants during heating using organic acid monoglycerides. [9] Use of organic acid monoglycerides for the production of inhibitors of the discoloration reaction between metal ions and poorly soluble antioxidants during heating.

[10] A method for producing a composition for suppressing discoloration when heated with metal ions, characterized by mixing an organic acid monoglyceride, a lipid-poorly soluble antioxidant, and a lipid.

[11] The method for producing the product according to

[10] , further characterized by mixing in one or more emulsifiers selected from the group consisting of lecithin, glycerin fatty acid esters other than organic acid monoglycerides, sucrose fatty acid esters, sorbitan fatty acid esters and propylene glycol fatty acid esters. [Effects of the Invention]

[0007] According to the present invention, a composition for suppressing heat discoloration of oil-poorly soluble antioxidants by metal ions, comprising an organic acid monoglyceride, can be provided. Furthermore, according to the present invention, a sufficient amount of oil-poorly soluble antioxidant can be incorporated into the composition. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 shows photographs of the samples after the compositions of Examples 1 and 5 and Comparative Example 1 were subjected to a heat discoloration test. [Figure 2] Figure 2 shows photographs of the samples after the compositions of Examples 8 and 9 and Comparative Example 2 were subjected to a heat discoloration test. [Figure 3] Figure 3 shows photographs of the samples after the compositions of Example 10, Comparative Example 3, and Reference Example 3 were subjected to a heat discoloration test. [Modes for carrying out the invention]

[0009] [Composition for inhibiting discoloration during heating using poorly soluble antioxidants and metal ions] [Organic acid monoglycerides] The composition of the present invention contains an organic acid monoglyceride. The organic acid monoglyceride used in the present invention is preferably citrate monoglyceride and / or diacetyltartrate monoglyceride, and more preferably citrate monoglyceride, but is not limited to these. For example, other organic acid monoglycerides such as succinate monoglyceride can also be used.

[0010] Monoglyceryl citrate, which is a preferred organic acid monoglyceride, is a compound in which citric acid is ester-bonded to the hydroxyl group of monoglyceride. Also, diacetyl tartaric acid monoglyceride, which is another preferred organic acid monoglyceride, refers to a compound in which a compound in which the hydroxyl group of tartaric acid is acetylated is ester-bonded to the hydroxyl group of monoglyceride. In the following structural formula, R represents a constituent fatty acid (hereinafter, may also be simply referred to as "fatty acid"). [Chemical formula]

[0011] The amount of the organic acid monoglyceride in the composition is not particularly limited. For example, 0.001% by mass to 99.999% by mass is preferable, 0.01% by mass to 99.99% by mass is more preferable, and 0.1% by mass to 99.9% by mass is even more preferable.

[0012] As the fatty acids constituting monoglyceryl citrate and diacetyl tartaric acid monoglyceride, preferably, for example, one or more mixtures of saturated or unsaturated fatty acids having 8 to 22 carbon atoms such as caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, etc. are used, and one or more mixtures of fatty acids may be used. In addition, the organic acid monoglyceride used in the present invention preferably contains an unsaturated fatty acid in the constituent fatty acids, but those not containing it are also preferable. The ratio of the unsaturated fatty acid in all the constituent fatty acids of the monoglyceryl citrate used in the present invention is not particularly limited. Examples of such unsaturated fatty acids include, but are not limited to, oleic acid, linoleic acid, linolenic acid, elaidic acid, or erucic acid. Also, commercially available products can be used as monoglyceryl citrate and diacetyl tartaric acid monoglyceride. As such commercially available products, for example, Pome K-37V (Riken Vitamin Co., Ltd.), Pome W-60 (Riken Vitamin Co., Ltd.), etc. can be used, but are not limited thereto.

[0013] [Temperature] The temperature at which the composition or method of the present invention is used is within the range of temperatures at which poorly soluble antioxidants in oils may be discolored by metal ions upon heating, for example, preferably 30°C to 250°C, more preferably 100°C to 200°C, and even more preferably 130°C to 180°C, but not limited to these ranges. Within these temperature ranges, the heat discoloration suppression effect of the present invention can be confirmed more efficiently.

[0014] [Antioxidants that are poorly soluble in oils and fats] The composition of the present invention preferably further contains an oil-poorly soluble antioxidant. The oil-poorly soluble antioxidant is characterized by discoloration (particularly to black or a color close to black) when heated with metal ions. The metal ions preferably include iron, copper, silver, gold, aluminum, lead, titanium, and alloys such as stainless steel, and more preferably iron or copper, but are not limited to these. In addition, while indicators of "poor solubility of fats and oils" for antioxidants include, for example, being "difficult to dissolve" or less as described in the Ministry of Health, Labour and Welfare's "Commentary on the Official Compendium of Food Additives," any antioxidant that is generally known to be poorly soluble in fats and oils within the field of food to which this invention belongs can be used in this invention. Preferably, the poorly soluble antioxidants for fats and oils are polyphenols, gallic acid, or their esters. In the present invention, polyphenols are preferably a general term for a group of compounds having multiple phenolic hydroxyl groups (hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings) in the same molecule, and more preferably a general term for a group of compounds in which two or more hydroxyl groups are bonded to a benzene ring. However, even if they do not fit any of the above definitions, compounds that are usually classified as polyphenols in the food industry, such as flavones and isoflavones, are also included. Furthermore, the polyphenols of the present invention do not contain gallic acid or its esters. The polyphenols of the present invention include both natural and synthetic products. Preferably, the polyphenols include, but are not limited to, flavonoids, tannins, chlorogenic acids (e.g., caffeic acid, ferulic acid, etc.), and ellagic acids. Flavonoids include, but are not limited to, catechins, flavones, isoflavones, flavonols, flavanones, anthocyanidins, flavanols, stilbenoids, and chalcones. Tannins include, but are not limited to, condensed tannins (e.g., catechin, epicatechin, gallocatechin, epigallocatechin, etc.) and hydrolyzable tannins (gallotannins, ellagitannins). Preferred sources of polyphenols include, but are not limited to, tea extracts (e.g., green tea, black tea, Chinese tea, etc.), rosemary extract, coffee extract, turmeric extract, blueberry extract, grape extract, grape seed extract, and soybean extract.

[0015] Regarding gallic acid or its esters, gallic acid can be used in monohydrate or anhydrous form. Preferably, it is the monohydrate, but not limited to this. The gallic acid ester preferably has a linear or branched carbon chain. 1-12 It is an alkyl ester, more preferably propyl gallate, octyl gallate, dodecyl gallate, and even more preferably C of gallic acid. 1-6 Alkyl esters, particularly preferably propyl gallate, are used, but are not limited to these. The alkyl ester may also optionally contain halogens, linear or branched C 1-12 It may be substituted with alkyl, amino, or hydroxyl groups. Gallic acid or its esters may be commercially available, but are not limited to commercially available products. Furthermore, in the present invention, gallic acid or its C 1-12 In addition to alkyl esters, analogs and derivatives thereof may also be included. Linear or branched C 1-12 Alkyloxy ester, C 1-12 Alkylthioester or C 2-12Alkenyl esters are included. These esters may further optionally be substituted with halogen, linear or branched C 1-12 alkyl, amino group, hydroxyl group and the like. Also, in the present invention, another preferred oil-insoluble antioxidant is catechin derived from green tea extract and / or propyl gallate. In the composition of the present invention, for example, oil-soluble antioxidants such as vitamin C palmitate, tocopherol, rosemary extract and the like may further be included.

[0016] In the composition or method of the present invention, the ratio of the organic acid monoglyceride used to the oil-insoluble antioxidant is preferably about 1:1 to about 1000:1, more preferably about 1:1 to about 500:1, still more preferably about 1:1 to about 100:1, but is not limited thereto. Within the above ratio range, the desired effects of the present invention can be obtained more efficiently. Note that the above preferred ratio can be appropriately changed according to the types and amounts of the organic acid monoglyceride and the oil-insoluble antioxidant used and the like.

[0017] In the composition or method of the present invention, the ratio of the organic acid monoglyceride used to the metal ion is preferably about 2:1 to about 10000:1, more preferably about 5:1 to about 5000:1, still more preferably about 10:1 to about 2000:1, but is not limited thereto. Within the above ratio range, the desired effects of the present invention can be obtained more efficiently. Note that the above preferred ratio can be appropriately changed according to the types and amounts of the organic acid monoglyceride and the oil-insoluble antioxidant used and the like.

[0018] [Oil (edible oil)] The composition of the present invention preferably further contains oils and fats. The oils and fats used in the present invention are preferably edible oils and fats, and more preferably oils and fats used for frying food, but are not limited to these. Frying is a cooking method that uses a relatively large amount of edible oils and fats as a heat medium and is widely used in the food industry. The oils and fats are not particularly limited, and commonly known edible vegetable oils and fats, animal oils and fats, aquatic animal oils and fats, microbial-derived oils and fats, etc., can be suitably used. In addition, medium-chain triglycerides, hydrogenated oils and fats, transesterified oils and fats, fractionated oils and fats, etc. can also be used as appropriate. Examples of vegetable oils include linseed oil, almond oil, perilla oil, olive oil, orange seed oil, pumpkin seed oil, conjugated linoleic acid-containing oils, wheat germ oil, rice oil, rice bran oil, corn oil, sesame oil, safflower oil, salad oil, shea butter, shiso oil, soybean oil, tea oil, camellia oil, rapeseed oil, palm oil, sunflower oil, peanut oil, grape seed oil, impatiens seed oil, macadamia nut oil, cottonseed oil, peanut oil, coconut oil, and rosehip oil. Examples of animal oils include beef tallow, pork tallow, and egg yolk oil. Examples of aquatic animal oils include fish oil obtained from sardines, salmon, mackerel, saury, herring, and tuna, squid and pollock liver oil, orbital oil from skipjack tuna and tuna, seal oil, and krill oil. Examples of oils derived from microorganisms include oils derived from Schizochytrium sp., Nitzschia sp., Nannochloris sp., and Mortierella sp. Blends of two or more of these oils, as well as medium-chain triglycerides, hydrogenated oils, fractionated oils, and transesterified oils can also be used.

[0019] [Emulsifiers other than organic acid monoglycerides] The composition of the present invention may optionally further contain one or more emulsifiers other than organic acid monoglycerides, selected from lecithin, glycerin fatty acid esters other than organic acid monoglycerides (e.g., diglycerin fatty acid esters, polyglycerin fatty acid esters, etc.), sucrose fatty acid esters, propylene glycol fatty acid esters, and sorbitan fatty acid esters, but the emulsifiers are not limited to these. Preferably, the composition contains any one of lecithin, glycerin fatty acid esters other than organic acid monoglycerides, or two or more of these, but is not limited to these. In addition, the composition of the present invention may further contain emulsifiers known or commonly used in the food industry.

[0020] Lecithin is a general term for mixtures mainly composed of phospholipids obtained from raw materials derived from plants, animals, and aquatic organisms. Examples of types include crude lecithin, purified lecithin, fractionated lecithin, enzymatically hydrolyzed lecithin, and enzymatically treated lecithin. Mixtures of these, or lecithin consisting of mixtures mainly composed of phospholipids, may also be used, but are not limited to these. Examples of plant-derived lecithin include lecithin obtained from by-products of vegetable oil refining, such as flaxseed, almond nuts, perilla, olive, orange seeds, pumpkin seeds, wheat germ, rice, rice bran, corn, sesame, cherry seeds, safflower, pomegranate seeds, shiso, soybeans, tea, camellia, rapeseed, palm, sunflower, peanuts, grape seeds, impatiens seeds, macadamia nuts, cottonseed, peanuts, coconut, and rosehip. Examples of animal-derived lecithin include egg yolk lecithin. Examples of aquatic organism-derived lecithin include lecithin obtained from sardines, salmon, mackerel, saury, herring, tuna, squid, Alaska pollock, skipjack tuna, seals, fish eggs, Euglena, and krill. The amount of lecithin in the composition of the present invention is not particularly limited, but is preferably 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 1% by mass, but is not limited to these amounts. Commercially available lecithin may be used, such as SLP-PC70 (Tsuji Oil Co., Ltd.), SLP-Paste (Tsuji Oil Co., Ltd.), etc., or a mixture of these commercial products may be used, but is not limited to these.

[0021] Glycerin fatty acid esters other than organic acid monoglycerides include, but are not limited to, diglycerin laurate, diglycerin stearate, diglycerin oleate, distilled monoglycerides (e.g., glycerin monostearate, glycerin monobehenate, glycerin monooleate, glycerin monocaprylate, glycerin monocaprate, glycerin monolaurate, etc.), tetraglycerin stearate, decaglycerin laurate, decaglycerin stearate, decaglycerin oleate, polyglycerin polyricinolate, etc. Commercially available glycerin fatty acid esters other than organic acid monoglycerides can also be used, for example, Poem DO-100V (Riken Vitamin Co., Ltd.), Rikemar JV-2681 (Riken Vitamin Co., Ltd.), etc., but are not limited to these.

[0022] Sucrose fatty acid esters (sucrose esters) include, but are not limited to, sucrose stearate ester, sucrose palmitate ester, sucrose myristicate ester, sucrose oleate ester, sucrose laurate ester, or mixtures thereof such as sucrose mixed fatty acid esters. Commercially available sucrose esters can also be used, such as Ryoto Sugar Ester ER-290 (Mitsubishi Chemical Corporation), but are not limited to these.

[0023] Sorbitan fatty acid esters (sorbitan esters) include, but are not limited to, sorbitan laurate, sorbitan stearate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate. Commercially available sorbitan esters can also be used, such as Poem S-65V (Riken Vitamin Co., Ltd.), but are not limited to these.

[0024] Propylene glycol fatty acid esters (PG esters) are usually monoesters and are classified into molecular distillate products (90% or more monoester) and reaction products (approximately 70% monoester) depending on the monoester content, but both can be used in the present invention. Mixtures of these may also be used. Examples of PG esters include propylene glycol monooleate, propylene glycol monolaurate, propylene glycol monostearate, and propylene glycol monobehenate, but are not limited to these. Commercially available PG esters can also be used, for example, Rikemar PO-100V (Riken Vitamin Co., Ltd.), but are not limited to these. Furthermore, in addition to those mentioned above, emulsifiers known or commonly used in the food industry may be included in the composition of the present invention. The amount of emulsifiers other than organic acid monoglycerides in the composition is not particularly limited, but for example, the total is preferably 1% to 90% by mass, more preferably 5% to 70% by mass, and even more preferably 5% to 50% by mass. If the composition contains emulsifiers other than organic acid monoglycerides, the HLB of the composition of the present invention, including the organic acid monoglycerides, is preferably in the range of 0 to 20, more preferably in the range of 0 to 15, and even more preferably in the range of 0 to 12, but is not limited to these ranges. If the composition contains multiple emulsifiers, the HLB of the entire composition can be calculated, for example, by a weighted average.

[0025] [Noodles, rice dishes, bread, sweets, etc.] Foods containing the composition of the present invention may include, but are not limited to, noodles, rice dishes, bread, and confectionery. Furthermore, the present invention may also include foods manufactured using oils and fats containing the composition of the present invention. Noodles include, but are not limited to, freshly made noodles, boiled noodles, steamed noodles, dried noodles, instant noodles, and frozen noodles. Examples include soba, udon, somen, hiyamugi, Chinese noodles, spaghetti, macaroni, and lasagna. Rice dishes include, but are not limited to, cooked white rice, red bean rice, mixed rice, barley rice, sticky rice (made by cooking or steaming glutinous rice), seasoned rice, vinegared rice, and cooked rice with ingredients such as chestnuts or beans (for example, pilaf, doria, fried rice, onigiri, sushi). Examples of bread include, but are not limited to, sliced ​​bread, rolls, sweet buns, savory buns, croissants, Danish pastries, brioche, French bread, rye bread, focaccia, and panettone (including dough and breadcrumbs). Confectionery includes, but is not limited to, baked goods such as scones, waffles, cookies, biscuits, shortbread, crackers, rice crackers, senbei, bolo, sponge cakes, chiffon cakes, castella, cheesecakes, pancakes, butter cakes, baumkuchen, muffins, donuts, cream puffs, and crepes; snack foods such as crunchy snacks, puff snacks, potato chips, corn chips, pretzels, and popcorn; biscuits; chocolate confectionery (coated chocolate, marble chocolate, etc.); Japanese sweets such as dorayaki and manju; nuts; and rice crackers such as fried rice crackers. Other foods include, but are not limited to, fried foods such as croquettes, karaage, tonkatsu, tempura, fried foods, and fritters, or their frozen versions (pre-fried frozen foods).

[0026] [Other additives, etc.] In addition to those mentioned above, the compositions of the present invention may contain, but are not limited to, food additives such as solvents, enzymes, yeast, pH adjusters, preservatives, disinfectants, oil-soluble antioxidants, fungicides, shelf-life extenders, colorants, color fixatives, bleaching agents, glazing agents, fragrances, spices, sweeteners, acidulants, seasonings, bittering agents, emulsifiers, thickeners, stabilizers, gelling agents, gelling agents, leavening agents, gum bases, yeast food, softeners, and nutritional fortifiers, as well as compounds (synthetic or natural) commonly used in the food industry, such as lipids, carbohydrates, modified starch, proteins, peptides, and water. Furthermore, one or more of these can be used in combination. The form of the composition is not particularly limited and may be in any form, such as liquid, solid, powder, or paste.

[0027] [Inhibition of discoloration (staining) and capture of metal ions] The present invention also provides a method for suppressing the discoloration (coloring) reaction between metal ions and poorly soluble antioxidants in oils and fats when heated, using organic acid monoglycerides. In the present invention, the discoloration (coloring) reaction of oil-poorly soluble antioxidants by capturing (chelating) metal ions and its suppression can be achieved, for example, by the method described in the Journal of the Japan Society for Food Science and Technology, Vol. 17, No. 6, 1970, pp. 231-236. Alternatively, as described in the examples below, methods include measuring the absorbance under standard conditions (25 degrees Celsius, atmospheric pressure) with and without the addition of organic acid monoglycerides to confirm the relationship between the color development rate and the organic acid monoglyceride concentration, or confirming the degree of discoloration by photograph or visual inspection. However, the method is not particularly limited, and methods known in the art can be used. The present invention also provides the use of organic acid monoglycerides for producing an inhibitor of the discoloration reaction between metal ions and oil-poorly soluble antioxidants during heating. As the discoloration reaction inhibitor, the same as the above-described composition for inhibiting heat discoloration between oil-poorly soluble antioxidants and metal ions can be used.

[0028] [Manufacturing method] The present invention also provides a method for producing a composition for suppressing discoloration when heated with metal ions, characterized by mixing an organic acid monoglyceride, a poorly soluble antioxidant for oils and fats, an oil or fat, and one or more emulsifiers. The order in which the antioxidant, organic acid monoglyceride, and oils and fats are mixed is not particularly limited, but it is more preferable to add the antioxidant after mixing the oils and fats and organic acid monoglyceride. The compositions of the present invention are preferably produced by mixing a poorly soluble antioxidant and an organic acid monoglyceride in an oil, and more preferably by uniformly dissolving or dispersing the poorly soluble antioxidant and the organic acid monoglyceride in an oil, but are not limited to these methods. The solvent used for the above dissolution can be any solvent that is suitable for use in food. Examples include organic solvents such as carboxylic acid esters, aliphatic compounds, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and alcohols. One or more of these can be used in combination, but are not limited to these. The dispersant used for the above dispersion can be any dispersant that can be used in food. Examples include edible oils and fats derived from plants, animals, aquatic plants and animals, microorganisms, etc., and one or more of these can be used in combination, but are not limited to these. Edible oils and fats are preferably frying oils and fats, and the above-mentioned types can be preferably used. Among solvents and dispersants, oils and fats are preferred from the viewpoint of use in food and cost. [Examples]

[0029] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. Various modifications are possible within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0030] (1) Experimental materials and equipment used The following materials were used in the experiment below. Organic acid monoglycerides: Poem K-37V (Monoglyceride Citric Acid, Riken Vitamin Co., Ltd.) Poem W-60 (Diacetyl tartrate monoglyceride, Riken Vitamin Co., Ltd.) Poem B-30 (Succinic acid monoglyceride, Riken Vitamin Co., Ltd.) Antioxidants that are poorly soluble in oils and fats: Propyl gallate (Fuji Chemical Industry Co., Ltd.) Gallic acid (Fuji Chemical Industries Co., Ltd.) PG-TP80C (Catechin (green tea extract), CHENGDU WAGOTT BIO-TECH CO., LTD) Oils and fats: Rapeseed oil (Tsuji Oil Co., Ltd.) Other emulsifiers: Poem DO-100V (Diglycerin fatty acid ester, Riken Vitamin Co., Ltd.) Ryoto Sugar Ester ER-290 (Sucrose Ester, Mitsubishi Chemical Corporation) Poem S-65V (Sorbitan ester, Riken Vitamin Co., Ltd.) Rikemar PO-100V (PG ester, Riken Vitamin Co., Ltd.) SLP-PC70, SLP-Paste (Lecithin, Tsuji Oil Co., Ltd.) others: Vitamin C palmitate (oil-soluble antioxidant, DSM Nutritional Products) Ferric chloride (Wako Pure Chemical Industries, Ltd.)

[0031] In the tests described below, the absorbance of the samples was measured using a Hitachi High-Tech Science U-1900 ratio beam spectrophotometer. Furthermore, a disperser (KINEMATICA, Polytron Homogenizer PT2100, 10,000 rpm) or a propeller-type stirrer (AS ONE, STIRRER P-1, 400 rpm) was used to stir the sample.

[0032] Test Example 1: Heat discoloration suppression effect of the organic acid monoglyceride-containing composition of the present invention The formulations of the compositions for Examples 1-5, Comparative Example 1, and Reference Example 1 are shown in Table 1 below. [Table 1]

[0033] Example 1: Composition containing citrate monoglyceride Experimental method (1) In a 30 mL bottle, 9.90 g of monoglyceride citrate and 0.10 g of propyl gallate were weighed, mixed, and heated to 80°C to dissolve and obtain the composition. (2) The composition from (1) (0.20 g) and rapeseed oil (9.80 g) were weighed into a 20 mL bottle and mixed to prepare the sample. (3) 0.10 g of ferric chloride and 0.90 g of purified water were weighed and mixed to prepare a 10% ferric chloride aqueous solution. (4) The 10% ferric chloride aqueous solution (0.001 g) from (3) and the sample (3.00 g) from (2) were added to a test tube and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.076, indicating that it had not turned black. The composition of the present invention was found to suppress the blackening of oil-poorly soluble antioxidants caused by metal ions (see also Figure 1).

[0034] Example 2: Composition further containing sucrose fatty acid ester The experiment was conducted by replacing a portion of the citrate monoglyceride in Example 1 with sucrose fatty acid ester. Experimental method (1) In a 30 mL bottle, citrate monoglyceride (9.80 g), sucrose fatty acid ester (0.10 g), and propyl gallate (0.10 g) were weighed, mixed, and heated to 80°C to dissolve and obtain the composition of Example 2. (2) The composition from (1) (0.20 g) and rapeseed oil (9.80 g) were weighed into a 20 mL bottle and mixed to prepare the sample. (3) The 10% ferric chloride aqueous solution (0.001 g) prepared in Example 1 and the sample from (2) (3.00 g) were added to a test tube and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.078, indicating that it had not turned black. In the composition of the present invention, even when sucrose fatty acid esters are included, the blackening of oil-poorly soluble antioxidants due to metal ions was suppressed.

[0035] Example 3: Composition further containing sorbitan fatty acid ester The experiment was conducted by replacing a portion of the citrate monoglyceride in Example 1 with sorbitan fatty acid ester. Experimental method (1) In a 30 mL bottle, citrate monoglyceride (9.80 g), sorbitan fatty acid ester (0.10 g), and propyl gallate (0.10 g) were weighed, mixed, and heated to 80°C to dissolve and obtain the composition. (2) The composition from (1) (0.20 g) and rapeseed oil (9.80 g) were weighed into a 20 mL bottle and mixed to prepare the sample. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 1 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.073, indicating that it had not turned black. In the composition of the present invention, even when sorbitan fatty acid ester is included, the blackening of oil-poorly soluble antioxidants due to metal ions was suppressed.

[0036] Example 4: Composition further containing propylene glycol fatty acid ester The experiment was conducted by replacing a portion of the citrate monoglyceride in Example 1 with propylene glycol fatty acid ester. Experimental method (1) In a 30 mL bottle, citrate monoglyceride (9.80 g), propylene glycol fatty acid ester (0.10 g), and propyl gallate (0.10 g) were weighed and then heated and dissolved at 80°C to obtain the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 1 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.075, indicating that it had not turned black. In the composition of the present invention, even when propylene glycol fatty acid ester is included, the blackening of poorly soluble antioxidants due to metal ions was suppressed.

[0037] Example 5: Composition with reduced content of organic acid monoglycerides In Example 5, the amount of citrate monoglyceride was reduced to about 1 / 20th of that in Examples 1-4, and oils and other emulsifiers were added to conduct the experiment with a composition closer to that of an actual product. Experimental Method (1) In a 70 mL bottle, citrate monoglyceride (1.00 g), rapeseed oil (10.55 g), diglycerin fatty acid ester (8.00 g), and lecithin (SLP-PC70, 0.05 g) were weighed and heated and dissolved at 80°C for 1 hour by propeller stirring. Then, propyl gallate (0.20 g) was added and heated and dissolved for 15 minutes, and vitamin C palmitate (0.20 g) was added and heated and dissolved for 30 minutes by propeller stirring at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 1 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.071, indicating that it had not turned black. In the composition of the present invention, even when the amount of citrate monoglyceride was reduced, the blackening of the oil-insoluble antioxidant due to metal ions was suppressed (see also Figure 1).

[0038] Comparative Example 1: Composition not containing organic acid monoglycerides In the composition of Example 5, the black color change of the poorly soluble antioxidant was investigated when no citrate monoglyceride was included. Experimental Method (1) In a 140 mL bottle, rapeseed oil (57.75 g), diglycerin fatty acid ester (40.00 g), and lecithin (SLP-PC70, 0.25 g) were weighed and heated to 80°C for 2 hours by propeller stirring to dissolve. Then, propyl gallate (1.00 g) was added and heated to 80°C for 1 hour, and vitamin C palmitate (1.00 g) was added and heated to 80°C for 30 minutes by propeller stirring to dissolve, thereby preparing the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 1 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.414, indicating that it had turned black. Without the addition of organic acid monoglycerides, the blackening of propyl gallate due to metal ions could not be suppressed (see also Figure 1).

[0039] Reference Example 1: Composition that does not contain ferric chloride (iron(III) ions) (in the case of propyl gallate) For reference to the above, the following experiment was conducted to demonstrate that, in the absence of ferric chloride, a poorly soluble antioxidant for fats and oils does not turn black when heated. Experimental Method (1) In a 140 mL bottle, rapeseed oil (57.75 g), diglycerin fatty acid ester (40.00 g), and lecithin (SLP-PC70, 0.25 g) were weighed and heated to 80°C for 2 hours by propeller stirring to dissolve. Then, propyl gallate (1.00 g) was added and heated to 80°C for 1 hour, and vitamin C palmitate (1.00 g) was added and heated to 80°C for 30 minutes by propeller stirring to dissolve, thereby preparing the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) The sample from (2) (3.00 g) was added to a test tube and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.063, indicating that it had not turned black.

[0040] Summary of Test Example 1: The results of the discoloration inhibition tests for the compositions of Examples 1-5 and Comparative Example 1 are summarized in Table 2 below. It was confirmed that organic acid monoglycerides can suppress the blackening caused by heating due to metal ions in poorly soluble antioxidants for oils and fats. [Table 2]

[0041] Test Example 2: Further investigation of the effect of suppressing discoloration by heating (1) In Test Example 2, we investigated the effects of varying the amount of citrate monoglyceride added, the ratio of poorly soluble antioxidants and metal ions (Examples 6 and 7). We also investigated the effects of using organic acid monoglycerides other than citrate monoglyceride (Example 8). The compositions of each of the compositions in Examples 6 to 8 are shown in Table 3 below. [Table 3]

[0042] Example 6: Investigation of the amounts of organic acid monoglycerides and metal ions In Example 6, the concentration of ferric chloride was increased by approximately 10 times in the discoloration test performed in Example 5 of Test Example 1, and the appropriate amount of organic acid monoglyceride was investigated to suppress discoloration. Experimental Method (1) In a 70 mL bottle, 10.35 g of rapeseed oil, 8.00 g of diglycerin fatty acid ester, 1.20 g of citrate monoglyceride, and 0.05 g of lecithin (SLP-PC70) were weighed and heated and dissolved at 80°C for 1 hour by propeller stirring. Then, 0.20 g of propyl gallate was added and heated and dissolved for 15 minutes, and 0.20 g of vitamin C palmitate was added and heated and dissolved for 30 minutes by propeller stirring at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) 0.10 g of ferric chloride and 0.90 g of purified water were weighed and mixed to prepare a 10% ferric chloride aqueous solution. (4) After weighing 0.01 g of the 10% ferric chloride aqueous solution from (3) into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.074, indicating that it had not turned black.

[0043] Example 7: Investigation of the amounts of organic acid monoglycerides and poorly soluble antioxidants for oils and fats. In Example 7, the discoloration test performed in Example 5 of Test Example 1 was reduced to about half the concentration of ferric chloride, and an appropriate amount of citrate monoglyceride was investigated to suppress discoloration. Experimental Method (1) In a 70 mL bottle, 11.274 g of rapeseed oil, 8.000 g of diglycerin fatty acid ester, 0.276 g of citrate monoglyceride, and 0.050 g of lecithin (SLP-PC70) were weighed and heated and dissolved at 80°C for 1 hour by propeller stirring. Then, 0.200 g of propyl gallate was added and dissolved for 15 minutes, and 0.200 g of vitamin C palmitate was added and dissolved for 30 minutes by propeller stirring at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.0006 g of the 10% ferric chloride aqueous solution prepared in Example 6 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.079, indicating that it had not turned black.

[0044] Example 8: Composition containing diacetyl tartrate monoglyceride In Example 8, diacetyl tartrate monoglyceride was used instead of citrate monoglyceride. Experimental Method (1) In a 70 mL bottle, rapeseed oil (7.55 g), diglycerin fatty acid ester (8.00 g), diacetyl tartrate monoglyceride (4.00 g), and lecithin (SLP-PC70, 0.05 g) were weighed and heated to 80°C for 1 hour by propeller stirring to dissolve. Then, propyl gallate (0.20 g) was added and heated to 80°C for 15 minutes by propeller stirring to dissolve, and vitamin C palmitate (0.20 g) was added and heated to 80°C for 30 minutes to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 6 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.079, indicating that it had not turned black (see also Figure 2).

[0045] The results of the discoloration inhibition tests for the compositions of Examples 6 to 8 are summarized in Table 4 below. [Table 4]

[0046] Summary of Test Example 2: In Examples 6 and 7, even with a small amount of organic acid monoglyceride relative to the poorly soluble antioxidant or metal ions, the blackening caused by heating due to metal ions in the antioxidant was suppressed. Furthermore, in Example 8, a similar effect was obtained when diacetyl tartaric acid monoglyceride was used instead of citrate monoglyceride as the organic acid monoglyceride.

[0047] Test Example 3: Further investigation of the effect of suppressing discoloration by heating (2) In Test Example 3, we investigated the case where the poorly soluble antioxidant for oils and fats is gallic acid (Example 9, Comparative Example 2, Reference Example 2), and the case where the poorly soluble antioxidant for oils and fats is catechin (Example 10, Comparative Example 3, Reference Example 3). The compositions of Examples 9-10, Comparative Examples 2-3, and Reference Examples 2-3 are shown in Table 5 below. [Table 5]

[0048] Example 9: Suppression of black color change in the case of gallic acid In Example 9, gallic acid was used instead of propyl gallate. Experimental Method (1) In a 140 mL bottle, 42.600 g of rapeseed oil, 15.750 g of diglycerin fatty acid ester, 40.000 g of citrate monoglyceride, 0.375 g of lecithin (SLP-paste), and 0.275 g of lecithin (SLP-PC70) were weighed and added, and the mixture was heated and dissolved at 80°C for 1 hour by propeller stirring. Then, 1.000 g of gallic acid was added and the mixture was heated and dissolved at 80°C for 15 minutes by propeller stirring to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) 0.10 g of ferric chloride and 0.90 g of purified water were weighed and mixed to prepare a 10% ferric chloride aqueous solution. (4) After weighing 0.001 g of the 10% ferric chloride aqueous solution from (3) into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.074, indicating that it had not turned black (see also Figure 2). Even when the poorly soluble antioxidant was gallic acid, similar to propyl gallate, the blackening of the poorly soluble antioxidant when heated with metal ions could be suppressed by using organic acid monoglycerides.

[0049] Comparative Example 2: Composition not containing organic acid monoglycerides In Example 9 described above, we investigated the case where organic acid monoglycerides were not included. Experimental Method (1) In a 140 mL bottle, 15.20 g of rapeseed oil, 31.50 g of diglycerin fatty acid ester, and 0.75 g of lecithin (SLP-paste and SLP-PC70) were weighed and added, and the mixture was heated and dissolved at 80°C for 1 hour by propeller stirring. Then, 2.00 g of gallic acid was added and the mixture was heated and dissolved at 80°C for 15 minutes by propeller stirring to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.05 g) and rapeseed oil (9.95 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 9 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.529, indicating that it had turned black (see also Figure 2).

[0050] Reference Example 2: Composition without ferric chloride (with gallic acid as the antioxidant) For reference to the above, the following experiment was conducted to demonstrate that gallic acid does not turn black when heated in the absence of ferric chloride. Experimental Method (1) In a 140 mL bottle, 15.20 g of rapeseed oil, 31.50 g of diglycerin fatty acid ester, and 0.75 g of lecithin (SLP-paste and SLP-PC70) were weighed and added, and the mixture was heated and dissolved at 80°C for 1 hour by propeller stirring. Then, 2.00 g of gallic acid was added and the mixture was heated and dissolved at 80°C for 15 minutes by propeller stirring to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.05 g) and rapeseed oil (9.95 g) into a 20 mL bottle. (3) The sample from (2) (3.00 g) was added to a test tube and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.066, indicating that it had not turned black.

[0051] Example 10: Suppression of black color change in the case of catechin In Example 10, catechin was used instead of propyl gallate. Experimental Method (1) Rapeseed oil (46.45 g), diglycerin fatty acid ester (12.00 g), citrate monoglyceride (40.00 g), and lecithin (SLP-paste, 0.30 g, SLP-PC70, 0.20 g) were weighed into a 140 mL bottle. After heating and dissolving in a disperser at 80°C for 15 minutes, vitamin C palmitate (0.05 g) was added and dissolved for 15 minutes, and catechin (1.00 g) was added and dissolved for 3 hours in a disperser at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.20 g) and rapeseed oil (9.80 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 9 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.312. Red discoloration was observed, but no black discoloration was observed (see also Figure 3). Even when the poorly soluble antioxidant used was catechin, the blackening that occurred when the poorly soluble antioxidant was heated with metal ions was suppressed by organic acid monoglycerides, similar to propyl gallate or gallic acid. The reason for the red discoloration that occurred when catechin was used is unclear, but it is likely that the colorless catechins oxidized, producing orange to red theaflavins or thearubigins.

[0052] Comparative Example 3: Composition not containing organic acid monoglycerides In Example 10 described above, we investigated the case where citrate monoglyceride was not included. Experimental Method (1) Rapeseed oil (32.25 g), diglycerin fatty acid ester (60.00 g), and lecithin (SLP-paste, 1.50 g, and SLP-PC70, 1.00 g) were weighed into a 140 mL bottle. After dissolving by heating in a disperser at 80°C for 15 minutes, vitamin C palmitate (0.25 g) was added and dissolved for 15 minutes, and catechin (5.00 g) was added and dissolved for 3 hours by heating in a disperser at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.04 g) and rapeseed oil (9.96 g) into a 20 mL bottle. (3) After weighing 0.001 g of the 10% ferric chloride aqueous solution prepared in Example 9 into a test tube, the sample from (2) (3.00 g) was added and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm, and the measured value was 0.828, indicating that it had turned black (see also Figure 3).

[0053] Reference Example 3: Composition without ferric chloride (with antioxidant: catechin) For reference to the above, the following experiment was conducted to demonstrate that catechin does not turn black when heated in the absence of ferric chloride. Experimental Method (1) Rapeseed oil (32.25 g), diglycerin fatty acid ester (60.00 g), and lecithin (SLP-paste, 1.50 g, SLP-PC70, 1.00 g) were weighed into a 140 mL bottle, heated and dissolved in a disperser at 80°C for 15 minutes, then vitamin C palmitate (0.25 g) was added and dissolved for 15 minutes, and catechin (5.00 g) was added and dissolved for 3 hours in a disperser at 80°C to prepare the composition. (2) A sample was prepared by weighing and mixing the composition from (1) (0.04 g) and rapeseed oil (9.96 g) into a 20 mL bottle. (3) The sample from (2) (3.00 g) was added to a test tube and heated at 150°C for 15 minutes. The absorbance of the sample after heating was measured at a wavelength of 570 nm and the measured value was 0.301. It turned red, but no blackening was observed (see also Figure 3).

[0054] The results of the discoloration inhibition tests for the compositions of Examples 9-10, Comparative Examples 2-3, and Reference Examples 2-3 are summarized in Table 6 below. [Table 6]

[0055] From the above, it can be seen that the desired discoloration suppression effect can be obtained even by changing the type of poorly soluble antioxidant used.

[0056] Reference Example 4: Composition containing succinic acid monoglyceride In addition to the above, we also investigated whether a similar effect could be obtained by substituting succinic acid monoglyceride for the organic acid monoglyceride (diacetyl tartrate monoglyceride) in Example 8. In this case, the sample turned black after heating, and the black discoloration could not be suppressed. Within the scope of this experiment, succinic acid monoglyceride could not suppress the heat discoloration caused by metal ions in poorly soluble antioxidants. Further investigations will be conducted in the future, such as adjusting the amount of metal ions and / or the amounts of organic acid monoglyceride and succinic acid monoglyceride.

Claims

1. A composition for suppressing heat discoloration between a poorly soluble antioxidant and metal ions, characterized by containing one or more organic acid monoglycerides selected from the group consisting of citrate monoglyceride and diacetyl tartaric acid monoglyceride, and oils and fats, A composition wherein the aforementioned oil-poorly soluble antioxidant is one or more selected from the group consisting of gallic acid, its monohydrate or C1-10 alkyl ester, and tannin.

2. The composition according to claim 1, further comprising one or more selected from the group consisting of flavonoids, chlorogenic acids, and ellagic acids as an oil-poorly soluble antioxidant.

3. The composition according to claim 1, further comprising one or more emulsifiers selected from the group consisting of lecithin, glycerin fatty acid esters other than organic acid monoglycerides, sucrose fatty acid esters, sorbitan fatty acid esters, and propylene glycol fatty acid esters.

4. A food product containing the composition described in any one of claims 1 to 3.

5. The food according to claim 4, which is noodles, rice dishes, bread, or confectionery.

6. A method for suppressing the discoloration reaction between metal ions and oil-soluble antioxidants during heating, comprising one or more organic acid monoglycerides selected from the group consisting of citrate monoglyceride and diacetyl tartaric acid monoglyceride, and oils and fats, A method wherein the oil-poorly soluble antioxidant is one or more selected from the group consisting of gallic acid, its monohydrate or its C1-10 alkyl ester, and tannin.

7. Use of one or more organic acid monoglycerides selected from the group consisting of citrate monoglyceride and diacetyl tartaric acid monoglyceride, and oils and fats, for the production of an agent for inhibiting the discoloration reaction between metal ions and oils and fats that are poorly soluble antioxidants during heating, The aforementioned oil-poorly soluble antioxidant is one or more selected from the group consisting of gallic acid, its monohydrate or C1-10 alkyl ester, and tannins.

8. A method for producing a composition for suppressing discoloration during heating with metal ions, characterized by mixing one or more organic acid monoglycerides selected from the group consisting of citrate monoglyceride and diacetyl tartaric acid monoglyceride, an antioxidant that is poorly soluble in oils and fats, and an oil or fat, A method wherein the oil-poorly soluble antioxidant is one or more selected from the group consisting of gallic acid, its monohydrate or its C1-10 alkyl ester, and tannin.

9. The manufacturing method according to claim 8, further comprising one or more selected from the group consisting of flavonoids, chlorogenic acids, and ellagic acids as an oil-poorly soluble antioxidant.

10. The manufacturing method according to claim 8, further characterized by mixing in one or more emulsifiers selected from the group consisting of lecithin, glycerin fatty acid esters other than organic acid monoglycerides, sucrose fatty acid esters, sorbitan fatty acid esters, and propylene glycol fatty acid esters.

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