JP2013201999A - Gardenia red composition - Google Patents

Abstract

The present invention provides a gardenia red pigment composition that suppresses the generation and insolubilization of pigment aggregates when heated at a high temperature for a long time at a high temperature.
A gardenia red pigment composition containing polyoxyethylene sorbitan monolaurate, which is a nonionic surfactant obtained by adding ethylene oxide to sorbitan monolaurate.
[Selection figure] None

Description

  The present invention relates to gardenia red pigment compositions.

  Gardenia red pigments are red in the neutral range (pH 6.0 or more and 8.0 or less), and the red pigments derived from natural products are relatively stable to heat and light. It is mainly used as a red colorant for liquid foods. Gardenia red pigment is generally produced by enzymatic treatment of ester hydrolysates of iridoid glycosides contained in gardenia fruit extracts, etc., with β-glucosidase, which inactivates β-glucosidase after the enzyme treatment. Therefore, heat treatment may be performed. In addition, when the manufactured gardenia red pigment is used by adding it to foods, etc., heat treatment is often performed, and there are several methods for suppressing color change of gardenia red pigment due to such heat treatment. Proposed.

  For example, a method of producing a red pigment by reacting an iridoid compound having a carboxyl group at the 4-position of an iridoid skeleton with a protein hydrolyzate, wherein the amino acid relative to the dry weight of the hydrolyzate in the protein hydrolyzate When the content is 35% by weight or more and when measured by the ninhydrin method, 50% by weight or more of the amino acids are glutamic acid and aspartic acid, and the weight of leucine relative to the total weight of the glutamic acid and aspartic acid. The method (Patent Document 1) characterized in that the ratio is 8% or less, an iridoid compound having a carboxyl group at the 4-position of the iridoid skeleton, a protein hydrolyzate and taurine or a taurine-containing substance to react with the red pigment A method for producing a protein hydrolyzate. The amino acid content relative to the dry weight of the hydrolyzate is 35% by weight or more, and when measured by the ninhydrin method, 50% by weight or more of the amino acids are glutamic acid and aspartic acid, and the glutamic acid and asparagine The ratio of the weight of leucine to the total weight with the acid is 8% or less, and the amount of taurine or the amount of taurine contained in the taurine-containing substance is the amino acid content in the protein hydrolyzate The above-mentioned method (Patent Document 2) and the like characterized in that it is more than 0% by weight to 35% by weight is proposed.

  However, when the gardenia red pigment produced in this way is further formulated or added to foods, etc., and heated for a long time at a high temperature, the pigment may aggregate and insolubilize, which is a problem. For this reason, the method of suppressing generation | occurrence | production of the pigment | dye aggregate at the time of heating gardenia red pigment | dye is calculated | required.

Japanese Patent No. 4526600 Japanese Patent No. 4605824

  An object of the present invention is to provide a gardenia red pigment composition in which generation of pigment aggregates due to heating is suppressed.

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by selecting and using a specific one of polyoxyethylene sorbitan fatty acid esters. The present invention has been completed.
That is, the present invention provides a gardenia red pigment composition comprising polyoxyethylene sorbitan monolaurate.

  The gardenia red pigment composition of the present invention is one in which generation of pigment aggregates due to heating is suppressed.

  The gardenia red pigment composition of the present invention contains at least gardenia red pigment and polyoxyethylene sorbitan monolaurate.

  The gardenia red pigment used in the present invention is not particularly limited as long as it is produced as gardenia red pigment and distributed in the market. Gardenia red pigment is usually produced by treating a substance having a carboxyl group at the 4-position of the iridoid skeleton in the iridoid glycoside with β-glucosidase in the presence of a protein hydrolysate. A substance having a carboxyl group at the 4-position of the iridoid skeleton in the iridoid glycoside (hereinafter also referred to as “substance A”) is a compound represented by the following formula (1).

  As the substance A, geniposide acid is preferably used. Geniposide acid is usually prepared by hydrolyzing geniposide extracted from the fruit of Rubiaceae gardenia (Gardenia augusta MERRIL var. Grandiflora HORT., Gardenia jasminoides ELLIS).

  There is no restriction | limiting in the method of extracting geniposide from the fruit of said gardenia, For example, well-known methods, such as grind | pulverizing the dried fruit of gardenia and extracting using water, alcohol, or those mixed liquids, are used. For example, when the water / alcohol mixed solution (1: 1) is used, the extraction condition is preferably room temperature (about 0 to 30 ° C.) to 50 ° C. for about 1 to 18 hours, and about 30 to 40 ° C. for about 2 to 4 hours. Is more preferable. In order to further increase the extraction rate of geniposide from the pulverized dried fruit, the extraction operation is usually repeated several times. The extract containing geniposide is concentrated by a method known per se, and is usually refrigerated or frozen as a concentrated solution.

  This concentrated liquid is usually treated with an adsorbent resin in order to remove components other than crocin and other geniposide, which are yellowish components. The adsorption resin treatment is performed by the following method, for example.

  First, the concentrated solution is diluted to an appropriate concentration, and the diluted solution is supplied to a column packed with an adsorption resin. As the adsorbing resin, porous materials such as Amberlite XAD-4, Amberlite XAD-7 (product name: manufactured by Organo), Diaion HP-20, HP-21, HP-40 (product name: manufactured by Mitsubishi Chemical Corporation), etc. Amberlite XAD-7 is preferably used.

  Next, a fraction containing geniposide is obtained by passing a mixture of water or a low-concentration alcohol (for example, ethanol) and water through the column and collecting the non-adsorbed and eluted fractions. This fraction is concentrated by a method known per se and is usually refrigerated or frozen as a concentrated solution.

  The hydrolysis of geniposide may be carried out according to a conventional method, and is usually carried out using acid, alkali or a suitable hydrolase. Examples of the acid include hydrochloric acid, sulfuric acid, and phosphoric acid. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Examples of the hydrolase include esterase.

  Industrially, the hydrolysis of geniposide is usually carried out using alkali. For example, an excess amount of an aqueous sodium hydroxide solution is added to the concentrated solution of the fraction containing geniposide, and preferably at room temperature (about 0 to 30 ° C.) to 70 ° C. for about 1 to 24 hours with stirring, preferably The reaction is carried out at about 40-60 ° C. for about 3-5 hours.

  After completion of hydrolysis with an alkali, an appropriate amount of an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid or an organic acid such as citric acid is added to the reaction solution, and the liquidity is about pH 7.0 or less, preferably about pH 4.0. A geniposide acid solution containing geniposide acid is prepared as follows.

  The protein hydrolyzate is not particularly limited as long as it is a protein derived from a plant such as soybean or wheat, an animal derived protein such as casein or gelatin, or a protein hydrolyzate derived from a microorganism such as yeast. Pro-extract HVP-G (trade name; manufactured by Banshu Seasoning Co., Ltd.), Pro-extract G2 (trade name; manufactured by Banshu Seasoning Co., Ltd.) and EPS-C (trade name; manufactured by Banshu Seasoning Co., Ltd.) These are sold and can be used for the production of gardenia red pigment according to the present invention.

  The β-glucosidase is not particularly limited as long as it is an enzyme having β-glucosidase activity, and examples thereof include those derived from Aspergillus niger, Trichoderma reesei, Trichoderma violet, almonds, and the like. As β-glucosidase, Sumiteam C6000, Sumiteam AC, Sumiteam C, Sumiteam X, Sumiteam BGT, Sumiteam BGA (trade name; manufactured by Shinnippon Chemical Co., Ltd.), Cellulosin AC40, Cellulosin T3, Cellulosin AL (trade name; manufactured by HIBI) ) Onozuka 3S, Y-NC (trade name; manufactured by Yakult Yakuhin Kogyo Co., Ltd.), Cellulase A “Amano” 3, Cellulase T “Amano” 4 (trade name; manufactured by Amano Enzyme), etc. are commercially produced and sold. These can be used for the production of gardenia red pigment according to the present invention.

  The method for producing the gardenia red pigment of the present invention is not particularly limited as long as it includes a step of treating substance A with β-glucosidase in the presence of a protein hydrolyzate. Industrially, a method in which an aqueous solution containing substance A, a protein hydrolyzate, and an organic acid (for example, citric acid) is prepared, and β-glucosidase is added to the aqueous solution to perform an enzymatic hydrolysis reaction is preferable. Is called.

  In the above reaction, for example, the temperature condition is usually about 40 to 80 ° C., preferably about 50 to 60 ° C., the pH condition is usually pH 3 to 6, preferably pH 4 to 5, and the reaction time is usually about 24 to It can be carried out in the range of 96 hours, preferably about 48 to 72 hours.

  In the above reaction, an appropriate amount of alkaline agent (for example, sodium hydroxide, potassium hydroxide, sodium carbonate) is added to the aqueous solution before adding β-glucosidase to the aqueous solution containing the substance A or the like in order to adjust the pH condition. And potassium carbonate) are preferably added.

  Moreover, it is preferable to perform the said reaction on the anaerobic condition under inert gas, such as nitrogen gas, a carbon dioxide gas, and argon gas. Anaerobic conditions can be set, for example, by blowing an inert gas into the aqueous solution before adding β-glucosidase to the aqueous solution containing the substance A or the like.

  Although there is no restriction | limiting in particular in the addition method of (beta) -glucosidase, The method of preparing the aqueous solution of (beta) -glucosidase and adding this aqueous solution is preferable.

  In 100% by mass of the solution in which the above reaction is carried out, substance A is about 1 to 20% by mass, preferably about 4 to 15% by mass, and protein hydrolyzate is about 1 to 25% by mass, preferably about 4 to 15% by mass. The organic acid is preferably adjusted to about 1 to 20% by mass, preferably about 1 to 12% by mass. The addition amount of β-glucosidase is preferably 0.0028 to 0.07 g with respect to 1 g of substance A.

  The reaction solution obtained by the above reaction is heated at about 70 to 100 ° C., preferably about 80 to 90 ° C. for about 0.5 to 3 hours, preferably about 1 to 2 hours to deactivate the enzyme. The gardenia red pigment according to the present invention is obtained by performing purification treatment such as adsorption treatment, membrane treatment, and acid precipitation treatment.

  The polyoxyethylene sorbitan monolaurate used in the present invention is a nonionic surfactant obtained by adding ethylene oxide to sorbitan monolaurate, which is a partial ester of sorbitol or sorbitan and lauric acid, and “polysorbate 20”. Also called. As polyoxyethylene sorbitan monolaurate, Will Surf TF-20 (trade name; manufactured by Nippon Oil & Fats Co., Ltd.) and the like are commercially manufactured and sold, and can be used in the present invention.

  The gardenia red pigment composition of the present invention is not particularly limited in its form as long as it is a composition containing the gardenia red pigment and polyoxyethylene sorbitan monolaurate. For example, gardenia red pigment and polyoxyethylene sorbitan It can be a water and / or alcohol solution containing monolaurate. The preparation method is not particularly limited, but for example, it can be easily prepared by adding polyoxyethylene sorbitan monolaurate and water and / or alcohol to gardenia red pigment and stirring and dissolving.

  The content of gardenia red pigment, polyoxyethylene sorbitan monolaurate and water and / or alcohol in 100% by mass of the water and / or alcohol solution is not particularly limited, but gardenia red pigment (color value 59.6 conversion) Is usually 50 to 90% by mass, preferably 60 to 70% by mass, polyoxyethylene sorbitan monolaurate is usually 0.001 to 1% by mass, preferably 0.01 to 0.1% by mass, and the rest It is preferable to adjust so that becomes water and / or alcohol.

  Here, the color value of gardenia red pigment can be measured based on the following method.

[Measurement method of color value]
1) A sample is accurately weighed so that the absorbance to be measured is in the range of 0.3 to 0.7, and dissolved in an acetate buffer (pH 4.0) to make exactly 100 ml.
2) Using the acetate buffer as a control, the absorbance A at the maximum absorption part near 530 nm is measured with the length of the liquid layer being 1 cm, and the color value E ( ^10% _{1 cm} 2) is obtained by the following formula (2).

  The gardenia red pigment composition of the present invention can also be provided by blending a diluent, carrier or other additive and formulating it. There are no particular limitations on the components to be blended in the formulation as long as they do not impair the purpose and effect of the present invention. For example, alcohols such as ethanol, propylene glycol, glycerin, dextrin, sugar, lactose, glucose, fructose , Sugars such as maltose, xylitol, erythritol, maltitol, sorbitol, starch syrup, reduced starch syrup, starch from corn, waxy corn, potato, sweet potato, wheat, rice, glutinous rice, tapioca, agar, ferceleran, locust bean gum, Tamarind gum, tara gum, arabinogalactan, scleroglucan, pullulan, dextran, gellan gum, curdlan, gatham, konjac mannan, xylan and other thickening polysaccharides, chitin, carboxymethylcellulose, methylcellulose, etc. And the like. Examples of the form of the preparation include liquid preparations, powder preparations, granule preparations, tablets, microcapsules, soft capsules, hard capsules, and W / O type emulsions.

  In addition, the gardenia red pigment composition of the present invention is preferably used in formulation involving a heating step (for example, preparation of a powder formulation by spray drying, etc.) since generation of pigment aggregates by heating is suppressed. it can.

  Further, the gardenia red pigment composition of the present invention can be used for coloring foods and drinks, for example, ice cream, ice milk, lacto ice, sherbet, frozen desserts such as ice confectionery, milk beverage, lactic acid bacteria beverage, soft drink, carbonated beverage Beverages, fruit juice beverages, vegetable beverages, sports beverages, powdered beverages, beverages such as alcoholic beverages, coffee beverages, tea beverages, desserts such as pudding, jelly, yogurt, chewing gum, chocolate, drop, candy, cookies, rice crackers, gummi Can be used for coloring confectionery such as jams, soups, pickles, seasonings such as dressing and sauce, processed meat products such as ham and sausage, fish paste products such as fish sausage and kamaboko.

[Preparation of gardenia red pigment]
(1) Preparation of Geniposide Acid Solution 7.2 L of 40 vol% ethanol / water mixture was added to 1.8 kg of dried fruit of ground gardenia and stirred at room temperature for 3 hours, followed by suction filtration. An operation of adding 3.3 L of 40 vol% ethanol / water mixture to the residue and stirring and filtering at room temperature for 30 minutes was repeated twice to obtain 10.5 L of extract as a filtrate. This extract was concentrated using a rotary evaporator under the conditions of 60 ° C. and 4 kPa to obtain about 500 mL of a concentrated solution containing geniposide.
Water was added to the obtained concentrated solution to 1.0 L, and the solution was passed through a column packed with 3.0 L of Amberlite XAD-7 (product name; manufactured by Organo) at a flow rate of SV = 0.5. Thereafter, 24.0 L of water was passed through the column at a flow rate SV = 0.5, and the discharged liquid was recovered. The collected liquid was concentrated using a rotary evaporator at 60 ° C. and 4 kPa, thereby obtaining 90 g of a concentrated liquid containing 47.1% of geniposide.
After 90 g of the obtained concentrated liquid and 34.8 g of water were mixed, 11.8 g of a 48% by mass aqueous sodium hydroxide solution was added and hydrolyzed at 60 ° C. for 3 hours. After the treatment, 48.9 g of 50% by mass citric acid aqueous solution was added to obtain 180 g of geniposide acid solution having a geniposide acid content of 19.25% by mass.

(2) Hydrolysis by β-glucosidase 168.4 g of geniposide acid solution obtained in (1), 31.9 g of wheat protein hydrolyzate (trade name: Proex HVP-G; manufactured by Banshu Seasoning Co., Ltd.) and citric acid 4 After mixing and dissolving 9 g, the pH was adjusted to 4.5 with sodium hydroxide, and water was further added to prepare an aqueous solution having a total amount of 237.4 g. Nitrogen gas was introduced into the obtained aqueous solution to reduce dissolved oxygen in the liquid, and then kept at 60 ° C. Subsequently, 22.6 g of a 2% by mass aqueous solution of β-glucosidase (trade name: Sumiteam C6000; manufactured by Shin Nippon Chemical Co., Ltd.) was added to this aqueous solution, and an enzymatic hydrolysis reaction was performed at 60 ° C. for 60 hours. After the reaction, the obtained reaction liquid was heated at 90 ° C. for 1 hour to obtain 260 g of gardenia red pigment (prototype) having a color value E ( ^10% _{1 cm 2} ) = 59.6.

[Preparation of gardenia red pigment composition]
(1) Raw materials 1) Gardenia red pigment (prototype)
2) Polyoxyethylene sorbitan monolaurate (trade name: Willsurf TF-20; manufactured by NOF Corporation)
3) Polyoxyethylene sorbitan monooleate (trade name: Willsurf TF-80; manufactured by NOF Corporation)
4) Polyoxyethylene sorbitan monostearate (trade name: Willsurf TF-60; manufactured by NOF Corporation)
5) Sucrose fatty acid ester (trade name: DK Ester SS; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
6) Diacetyltartaric acid monoglyceride (trade name: Poem W-60; manufactured by Riken Vitamin Co., Ltd.)
7) Kirayasaponin (trade name: Kirayanin P-20; manufactured by Maruzen Pharmaceutical Co., Ltd.)
8) Diglycerin monomyristate (trade name: Poem DM-100; manufactured by Riken Vitamin Co., Ltd.)
9) Decaglycerin fatty acid ester (trade name: Poem J-0381V; manufactured by Riken Vitamin Co., Ltd.)
10) Filtration water

(2) Formulation of gardenia red pigment composition Table 1 shows the formulation of gardenia red pigment compositions 1-8 prepared using the above raw materials. Among these, the composition 1 is an Example which concerns on this invention, and the compositions 2-8 are comparative examples with respect to them.

(3) Preparation method of gardenia red pigment composition Based on the mixing ratio of the raw materials shown in Table 1, all the raw materials are uniformly stirred and dissolved by a stirrer, and the color value E ( ^10% _{1 cm} ) = 40.0 100 g of each of Gardenia red pigment compositions 1-8 were prepared.

[Heat resistance test]
About Gardenia red pigment | dye compositions 1-8, after heating 30g at 90 degreeC for 60 minutes, respectively, filtered water was added and 100 g of each aqueous solution of color value E ( ^10% _1cm ) = 10 was prepared. The resulting aqueous solution was thoroughly stirred with a stirrer, and then the whole amount was filtered with a cellulose mixed ester type membrane filter (A100A047A; manufactured by Advantech Toyo Co., Ltd.) having a pore size of 1 μm. The heat resistance was evaluated. The results are shown in Table 2.

  From the results in Table 2, it is clear that the gardenia red pigment composition 1 of the present invention has no heat-resistant pigment aggregates and is imparted with heat resistance. In contrast, in the gardenia red pigment compositions 2 to 8 of the comparative examples, pigment aggregates due to heating were all confirmed.

Claims (1)

  A gardenia red pigment composition comprising polyoxyethylene sorbitan monolaurate.