JPWO2007114304A1 - Benzene production inhibitor and method for inhibiting benzene production - Google Patents

Abstract

The present invention provides a safe benzene production inhibitor that suppresses the production of harmful benzene from benzoic acid-containing products. The benzene production inhibitor of the present invention is used as an active ingredient of a benzene production inhibitor by combining flavonol and / or flavonol glycoside, or ascorbic acid, ascorbate, an ester compound of ascorbic acid or ascorbic acid glycoside with flavonol and / or flavonol glycoside. . Moreover, the production | generation of benzene from the benzoic acid in the composition containing the said benzoic acid is suppressed by making the composition containing benzoic acid coexist with the said benzene production | generation inhibitor.

Description

  The present invention relates to a benzene production inhibitor and a benzene production inhibition method. More specifically, the present invention relates to a benzene production inhibitor and a benzene production inhibition method capable of significantly suppressing benzene produced from benzoic acid and its derivatives.

  Conventionally, benzoic acid and salts thereof have been used as preservatives in various products such as foods and drinks, cosmetics and pharmaceuticals in order to improve the preservability of the materials themselves or the materials contained therein.

  However, it has been pointed out that such benzoic acids generate benzene, which is a carcinogenic substance, by hydroxy radicals generated by the reduction reaction of oxygen or hydrogen peroxide (see Non-Patent Document 1, etc.).

  For this reason, for various products such as foods and drinks, cosmetics, and pharmaceuticals containing benzoic acids, benzene is produced under general conditions such as manufacturing processes including heat treatment and storage with light irradiation. There is concern about the possibility of mixing.

In particular, foods and drinks are easily affected by heat and light irradiation during storage and display of products with the spread of heated beverages by hot vendors in recent years and the spread of beverages in transparent containers such as plastic bottles. For this reason, especially in the field of foods and beverages, it is necessary to prevent the formation of benzene due to benzoic acids and to solve the problem of benzene mixing in products at an early stage.
J Agr Food Chem. (1993), 41 (5): 693-695

  The objective of this invention is providing the benzene production | generation inhibitor and the benzene production | generation suppression method which can suppress significantly the benzene production | generation which uses benzoic acid as a causative substance. In particular, an object of the present invention is to provide a benzene production inhibitor that is highly safe and water-soluble and can be suitably used for foods and the like, and a benzene production inhibition method widely used in many products.

The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and have found that flavonol and its glycoside have an effect of significantly suppressing benzene production caused by benzoic acids. The present invention has been completed based on such findings, and includes the following aspects.
(1) Benzene production inhibitor (1-1) A benzene production inhibitor comprising as an active ingredient at least one selected from the group consisting of flavonols and flavonol glycosides.

  (1-2) The benzene production inhibitor according to (1-1), wherein the flavonol and the flavonol glycoside are quercetin, isoquercitrin, enzyme-treated isoquercitrin, enzyme-treated rutin, rutin and myricitrin.

  (1-3) The benzene production inhibitor according to (1-1), wherein the flavonol and the flavonol glycoside are enzyme-treated isoquercitrin, enzyme-treated rutin, rutin and myricitrin.

  (1-4) The benzene production inhibitor according to (1-1), wherein the flavonol and the flavonol glycoside are enzyme-treated isoquercitrin and myricitrin.

  (1-5) A group consisting of an enju extract, tartary buckwheat extract, dokudami extract, bayberry extract, buckwheat whole plant extract, red bean whole plant extract, onion extract, and rabu extract as the above active ingredients The benzene production inhibitor according to any one of (1-1) to (1-4), which comprises at least one plant extract selected from:

  (1-6) The active ingredient contains at least one plant extract selected from the group consisting of Enju extract and bayberry extract as described in any one of (1-1) to (1-4) Benzene formation inhibitor.

  (1-7) The benzene production inhibitor according to any one of (1-1) to (1-4), which contains a bayberry extract as the active ingredient.

  (1-8) The method according to any one of (1-1) to (1-7), further comprising at least one selected from ascorbic acid, ascorbate, an ester compound of ascorbic acid, and an ascorbic acid glycoside Benzene production inhibitor.

  (1-9) The ratio of the total amount of ascorbic acid, ascorbate, an ester compound of ascorbic acid and ascorbic acid glycoside with respect to 100 parts by weight of the total amount of flavonol and flavonol glycoside is 1 to 100000 parts by weight. The benzene production inhibitor according to any one of (1-1) to (1-8).

  (1-10) A benzene formation inhibitor used for a benzoic acid-containing composition, wherein the flavonol and flavonol distribution are based on 100 parts by weight of the total amount of benzoic acid converted to benzoic acid in the composition. The benzene production inhibitor according to any one of (1-1) to (1-9), which is used in a ratio such that the total amount of saccharide is 1 to 100,000 parts by weight.

  (1-11) The benzene production inhibitor according to any one of (1-1) to (1-10), which is particularly used for inhibiting the production of benzene by light irradiation.

(2) Method for inhibiting benzene production of benzoic acid-containing composition (2-1) Adding the benzene production inhibitor described in any of (1-1) to (1-10) to a benzoic acid-containing composition A method for inhibiting benzene production of a benzoic acid-containing composition, which is characterized by the following.

  (2-2) The benzoic acid-containing composition is a composition containing at least one selected from the group consisting of benzoic acid, a salt of benzoic acid, a benzoic acid ester, and a hydroxyl form thereof (2-1 Benzene production suppression method described in the above.

  (2-3) Described in (2-1) or (2-2), the benzoic acid-containing composition contains benzoic acids in a total amount of 1 to 2500 ppm in terms of the amount of benzoic acid. Benzene production suppression method.

  (2-4) A benzene production inhibitor is added to the benzoic acid-containing composition at a ratio such that the total amount of flavonols and flavonol glycosides is 0.1 to 10000 ppm, (2-1) to (2-3) The benzene production | generation suppression method described in any one of these.

  (2-5) The total amount of flavonol and flavonol glycoside added to the benzoic acid-containing composition is 1 to 100,000 with respect to 100 parts by weight of the total amount of benzoic acid in the benzoic acid in the composition. The method for inhibiting benzene production according to any one of (2-1) to (2-4), wherein a benzene production inhibitor is added at a ratio of parts by weight.

  (2-6) The method for inhibiting benzene production according to any one of (2-1) to (2-5), wherein the benzoic acid-containing composition is a food, drink, pharmaceutical product, quasi-drug, cosmetic product, or feed.

(3) Benzoic acid-containing composition (3-1) A benzoic acid-containing composition containing the benzene production inhibitor according to any one of (1-1) to (1-10).

  (3-2) The benzoic acid-containing composition is a composition containing at least one selected from the group consisting of benzoic acid, a salt of benzoic acid, a benzoic acid ester, and a hydroxyl form thereof (3- A benzoic acid-containing composition described in 1).

  (3-3) The benzoic acid-containing composition contains benzoic acid in terms of the amount of benzoic acid and contains 1 to 2500 ppm in total, as described in (3-1) or (3-2) Benzoic acid-containing composition.

  (3-4) The benzoic acid-containing composition contains a benzene formation inhibitor in a proportion such that the total amount of flavonols and flavonol glycosides is 0.1 to 10,000 ppm, (3-1) to (3-3) A benzoic acid-containing composition as described in any of the above.

  (3-5) The total amount of flavonol and flavonol glycoside in the benzoic acid-containing composition is 1 to 100000 parts by weight with respect to 100 parts by weight of the total amount of benzoic acid in the benzoic acid in the composition A benzoic acid-containing composition according to any one of (3-1) to (3-4), which contains a benzene formation inhibitor at a ratio of

  (3-6) The benzoic acid-containing composition according to any one of (3-1) to (3-5), which is a food, drink, pharmaceutical product, quasi-drug, cosmetic product, or feed.

(4) Use for production of benzene production inhibitor (4-1) Use for production of at least one benzene production inhibitor selected from the group consisting of flavonols and flavonol glycosides.

  (4-2) Contains at least one selected from the group consisting of flavonols and flavonol glycosides, and at least one selected from ascorbic acid, ascorbate, ester compounds of ascorbic acid and ascorbic acid glycosides Use of the composition for the production of a benzene formation inhibitor.

  ADVANTAGE OF THE INVENTION According to this invention, the benzene production | generation inhibitor which can be conveniently used for the method for significantly suppressing the benzene production | generation from benzoic acid produced by light irradiation, a heat | fever, etc. and the said method can be provided. According to the benzene production inhibitor and the benzene production inhibition method of the present invention, it is possible to significantly inhibit the production of benzene produced gradually from benzoic acids at each stage of production, distribution, and storage period, and to stabilize benzoa for a long period of time. The quality and safety of acids-containing products can be maintained.

(I) Benzene Production Inhibitor The benzene production inhibitor of the present invention is characterized by containing at least one selected from the group consisting of flavonols and flavonol glycosides as an active ingredient. In the present specification, these flavonols and flavonol glycosides are also collectively referred to as “flavonols”.

  Examples of the flavonol used in the present invention include compounds having a hydroxyl group at the 3-position of the flavonoid, and examples of the flavonol glycoside include glycosides having the flavonol in the aglycone part. As flavonols, specifically quercetin, kaempferol, rhamnetin, gosipetin, myricetin, morin, and isorhamnetin, and as flavonol glycosides, specifically quercitrin, hyperoside, rutin, isoquercitrin and myricitrin, and These can be exemplified by those subjected to various treatments such as enzyme treatment or hydrolysis (for example, enzyme-treated rutin and enzyme-treated isoquercitrin). In addition, these may be refined | purified or a crude refined | purified product regardless of the presence or absence of refinement | purification. Preferably, rutin, quercetin, isoquercitrin, enzyme-treated rutin, myricitrin and enzyme-treated isoquercitrin, more preferably rutin, myricitrin, enzyme-treated rutin and enzyme-treated isoquercitrin, more preferably myristitrin and Enzyme-treated isoquercitrin. These flavonols may be used alone or in any combination of two or more.

  Moreover, in this invention, it can replace with the said flavonol itself, or can use the plant extract containing various flavonols raise | lifted above as it is with the said flavonol itself as it is. Such extracts include Enju extract (Enju cocoon or flower extract), Tartary buckwheat extract, Dokudami extract, Yam extract, Whole buckwheat extract, Whole red bean extract, Onion extract, and Rafu hemp extract A thing etc. can be illustrated.

  Such a plant extract can be obtained by extracting a corresponding part of a plant containing a relatively large amount of flavonols with water, alcohol or other organic solvent, and can be used as it is or further by enzyme treatment. Can also be used.

  Examples of plant extracts containing flavonols preferably used in the present invention include red bean extract, Enju extract, buckwheat extract, bayberry extract and the like. Particularly preferred are bayberry extract and enju extract, and more preferred are bayberry extract.

  These plant extracts contain active ingredients of flavonol and flavonol glycoside, respectively. Specifically, rutin for enthusi extract, rutin and quercetin for tartary buckwheat extract, quercitrin and isoquercitrin for dokudami extract, myricitrin for bayberry extract, rutin for buckwheat whole plant extract, The whole red bean extract contains rutin, the onion extract contains quercetin, and the rabu extract contains isoquercitrin and hyperoside as the main components of flavonols.

  “Enzyme-treated isoquercitrin” is obtained by acting a glycosyltransferase on isoquercitrin in the presence of a sugar donor, and is glycosylated to various degrees with isoquercitrin as shown in the following formula. And a mixture with α-glucosyl isoquercitrin.

  Specifically, in the above formula, “enzyme-treated isoquercitrin” is an isoquercitrin in which the number of α-1,4-bonded glucose residues (n) is 0 and the number of glucose residues in an α-1,4-bond. (N) is a mixture of 1 or more, usually 1 to 15, preferably 1 to 10 α-glucosyl isoquercitrin. That is, the enzyme-treated isoquercitrin is a mixture of isoquercitrin (n = 0) and α-glucosylisoquercitrin (n is 1 or more) in which glucose is further bound to the glucose residue of the isoquercitrin. It is.

  The enzyme-treated isoquercitrin used in the present invention may be a mixture of various enzyme-treated isoquercitrins having different glucose group bond numbers (n), but the glucose group bond number (n) is single. It may be a kind of enzyme-treated isoquercitrin.

  Such enzyme-treated isoquercitrin can be prepared by treating isoquercitrin with a glucose residue transferase. Although not limited, enzyme-treated isoquercitrin is usually produced by glycosylation using a glucose residue transfer enzyme such as glucosidase or transglucosidase by transferring equimolar amounts of glucose residues to isoquercitrin. Can do.

  The glucose source used for glycosylation may be any glucose source as long as one or more of its glucose residues can be transferred to one molecule of isoquercitrin, such as glucose, maltose, amylose, amylopectin, starch, and starch. Liquefied products, starch saccharified products, cyclodextrins, and the like can be used. The amount of the glucose source used is usually 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight per 1 part by weight of isoquercitrin present in the reaction system. The ratio of parts can be mentioned.

  As glucosidase, for example, α-amylase (EC 3.2.1.1), α-glucosidase (EC 3.2.1.20) and the like can be used, and as transglucosidase, for example, cyclodextrin glucanotransferase (EC 2.4.1.19) ( (Hereinafter abbreviated as CGTase) or the like can be used.

  CGTase is known to be produced by bacteria such as Bacillus circulans, Bacillus macerans, Bacillus stearothermophilus, Bacillus megaterium, Bacillus polymixer etc., Bacillus genus such as Klebsiella pneumoniae, etc. Any of these can be used freely in the present invention.

  All of these glucose residue transferases are commercially available enzymes, and such commercially available enzyme agents (for example, trade name: Contiszyme manufactured by Amano Enzyme Co., Ltd.) can also be used. The enzyme is not necessarily purified and may be a crude product. For example, an enzyme-treated isoquercitrin may be produced by inoculating the glucose residue transferase-producing bacterium in a medium to which isoquercitrin has been added, and performing a reaction by fermentation. Alternatively, an enzyme-treated isoquercitrin may be produced by immobilizing a glucosyltransferase producing bacterium and reacting it with isoquercitrin in a batch or continuous manner. In addition, glucose residue transferase can also be performed using each of glucosidase or transglucosidase, and can also be used in combination (simultaneously or sequentially).

  The reaction conditions for glucose residue transferase may be any conditions that allow glucose residue transferase to act in a mixed water system of isoquercitrin, glucose residue transferase and the above glucose source. The amount of glucose residue transfer enzyme used is 1 part by weight of isoquercitrin. When glucose residue transfer enzyme is CGTase, the enzyme specific activity is about 100 units (an enzyme that produces 1 mg of β-cyclodextrin per minute from soluble starch). The amount can be selected from the range of 0.001 to 20 parts by weight. Preferably, it is about 0.005 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight.

  The amount of isoquercitrin in the reaction system is not particularly limited, but for the purpose of efficiently carrying out glycosylation, it is usually 0.1 to 30% by weight, preferably 0.5 to 100% by weight of the reaction system. It is desirable that it is contained at a ratio of ˜20 wt%, more preferably 1 to 10 wt%.

  The temperature of this reaction system varies depending on the type of enzyme used, but a range of about 80 ° C. or lower can be appropriately selected and used. Within this range, industrially advantageous is about 20-80 ° C, preferably about 40-75 ° C. The pH condition is usually about pH 3 to 11 or less, preferably pH 4 to 8.

  The reaction can be performed with standing or stirring or shaking. In order to prevent oxidation during the reaction, the head space of the reaction system may be replaced with an inert gas such as nitrogen, and an antioxidant such as ascorbic acid may be added to the reaction system.

  Thus, the glucose group binds to the glucose residue of isoquercitrin to produce the target enzyme-treated isoquercitrin.

  The number of glucose groups bonded to the glucose residue of isoquercitrin (the number of n in the above formula (1)) is not particularly limited, but is usually 1 to 15, preferably 1 to 10 as described above. It can be arbitrarily adjusted to be within the range. Examples of such adjustment methods include a method of treating various amylases (α-amylase, β-amylase, glucoamylase, α-glucosidase, maltase, etc.) alone or in combination after producing enzyme-treated isoquercitrin. Can do. By carrying out like this, the number of glucose sugar chains in the enzyme-treated isoquercitrin molecule obtained by the above-mentioned method can be decreased to obtain enzyme-treated isoquercitrin having an arbitrary glucose sugar chain length.

  The method for isolating and purifying the enzyme-treated isoquercitrin from the reaction system is not particularly limited. For example, as an isolation method, the method of isolating using gel filtration resin by a conventional method can be mentioned. Purification of enzyme-treated isoquercitrin is not particularly limited, and can be performed by arbitrarily combining conventional methods. Specifically, various resin treatment methods (adsorption method, ion exchange method, gel filtration method, etc.), membrane treatment methods (ultrafiltration membrane treatment method, reverse osmosis membrane treatment method, ion exchange membrane treatment method, zeta potential membrane treatment) Method), electrodialysis, salting out, aciding out, recrystallization, solvent fractionation, activated carbon treatment, and the like.

  The enzyme-treated isoquercitrin thus obtained is mainly composed of α-glucosylisoquercitrin in which equimolar amounts of glucose are further bound to the glucose residue of isoquercitrin (quercetin 3-0-monoglucoside). It is easy to dissolve in water.

  “Enzyme-treated rutin” is obtained by adding α-1,4 glucose to a glucose residue of rutin using cyclodextrin glucanotransferase to a mixture of rutin and starch or dextrin, and the main component is α -Glucosyl rutin.

  The “Yamamomochi extract” can be prepared by extracting a plant of the family Lantaceae using, for example, the method of patent application by the present applicant (JP-A-5-156249, JP-A-9-87619). The bayberry extract obtained by such an operation contains a large amount of myricitrin (myricetin-3-O-rhamnoside), which is a flavonol glycoside, and serves as a source of the glycoside. The bayberry extract can be used as it is, but can also be subjected to a glycosyltransferase treatment according to the method described in JP-A-9-95672, which is used as a readily water-soluble bayberry extract. be able to.

  The ratio of the flavonols contained in the benzene production inhibitor is not particularly limited as long as it has an effect of inhibiting the production of benzene from benzoic acids. For example, the ratio of flavonols in 100% by weight of the benzene production inhibitor may be in the range of 0.1 to 100% by weight, preferably 0.5 to 80% by weight.

  In addition to the flavonols, the benzene production inhibitor of the present invention can also contain ascorbic acid, ascorbate, an ester compound of ascorbic acid, or an ascorbic acid glycoside. In the present specification, these ascorbic acid, ascorbate, an ester compound of ascorbic acid and an ascorbic acid glycoside are collectively referred to as “ascorbic acids”.

  For example, as the ascorbic acid, L-ascorbic acid; as the salt of L-ascorbic acid, alkali metal salts such as sodium and potassium of L-ascorbic acid can be preferably exemplified. Further, as the ester compound of ascorbic acid, ascorbic acid stearic acid ester or ascorbic acid palmitic acid ester can be preferably mentioned, and as ascorbic acid glycoside, L-ascorbic acid-2-glucoside is preferably mentioned. Can do.

  In the present invention, fruits such as lemon, tangerine, navel orange, grapefruit, acerola, strawberry, oyster, kiwifruit, guava, papaya, and camcam; instead of the ascorbic acid itself or together with the ascorbic acid; Foods containing ascorbic acids, such as vegetables such as sweet potato and potatoes; and vegetables such as sweet potatoes and potatoes; and vegetables such as sweet potatoes and potatoes; Can also be used.

  When flavonols and these ascorbic acids are used in combination, the blending ratio of both is not limited, but the ratio of ascorbic acids (total amount) to 100 parts by weight of flavonols (total amount) is usually 1 to 100,000 parts by weight, preferably 1 to 50000 parts by weight, more preferably 2 to 30000 parts by weight.

  The benzene production inhibitor of the present invention is not particularly limited as long as it contains ascorbic acids in addition to the above flavonols or flavonols. May be.

  Such a carrier is not particularly limited as long as it does not interfere with the effects of the present invention. For example, sugars such as sucrose, glucose, dextrin, starches, cyclodextrin, trehalose, lactose, maltose, starch syrup, and liquid sugar; ethanol And alcohols such as propylene glycol and glycerine; sugar alcohols such as sorbitol, mannitol, xylitol, erythritol and maltitol; polysaccharides such as gum arabic, xanthan gum, carrageenan, guar gum and gellan gum; and water.

  In addition, since flavonols are poorly water-soluble and difficult to handle, flavonols may be dissolved in a lower alcohol such as ethanol or a polyhydric alcohol such as glycerin or propylene glycol as necessary.

  Examples of the additive include antioxidants, auxiliaries such as chelating agents, fragrances, spice extracts, preservatives, and the like.

  In addition, as an antioxidant used as an additive here, what is used as a food additive can be illustrated widely. For example, but not limited to, erythorbic acids such as erythorbic acid and its salts (eg sodium erythorbate); chlorogenic acids such as chlorogenic acid, isochlorogenic acid and its salts; sodium sulfite, sodium hyposulfite, sodium pyrosulfite or pyrosulfite Sulfites such as potassium; tocopherols such as α-tocopherol and mixed tocopherol; dibutylhydroxytoluene (BHT) and butylhydroxyanisole (BHA); ethylenediaminetetraacetates such as disodium calcium ethylenediaminetetraacetate and disodium ethylenediaminetetraacetate Gallic acids such as gallic acid and propyl gallate; γ-oryzanol, ellagic acid, guaiac fat, sesamorin, sesamol, melaroika essential oil, monosaccharide amino complex, ferula Acid, tocotrienol, rapeseed oil extract, sesame oil unsaponifiable, mallow flower extract, Aspergillus terreus extract, licorice oil extract, clove extract, essential oil-removed fennel extract, horseradish extract, sage extract, seri extract , Tea extract, tempeh extract, green coffee bean extract, sunflower seed extract, pimenta extract, grape seed extract, blueberry leaf extract, propolis extract, hego ginkgo biloba extract, pepper extract, spinach An extract, an eucalyptus leaf extract, a gentian root extract, an enzyme-decomposed apple extract, a sesame oil extract, a rapeseed oil extract, a rice bran oil extract, a rice bran enzyme digest, and the like can be mentioned.

  The form of the benzene production inhibitor of the present invention is not particularly limited. For example, the benzene production inhibitor is a solid such as powder, granule, or tablet; a liquid such as liquid or emulsion; or a semisolid such as paste. Can be prepared in any form.

  The benzene production inhibitor of the present invention can be widely applied to compositions containing benzoic acids for the purpose of inhibiting benzene production from benzoic acids. Examples of such compositions include foods and drinks, cosmetics, pharmaceuticals, quasi drugs, and feeds. Although these forms are not particularly limited, those containing water as a preferred form, in particular, in the form of solutions such as beverages, skin lotions, cosmetic liquids, liquids, drinks, injections and infusions, especially in the form of aqueous solutions Things can be mentioned.

  Examples of the benzoic acids include benzoic acid, benzoic acid salts, benzoic acid esters, and hydroxyl groups thereof. For example, benzoic acid salts include alkali metal salts of benzoic acid such as sodium and potassium; alkaline earth metal salts of benzoic acid such as calcium and magnesium. As the hydroxyl form of benzoic acid, 2-hydroxybenzoic acid (2-Hydroxybenzoic acid = salicylic acid), 4-hydroxybenzoic acid (4-Hydroxybenzoic acid), 3,4-dihydroxybenzoic acid (= protocatechuic acid), 2,3-dihydroxybenzoic acid (= o-pyrocatechuic acid), 2,4-dihydroxybenzoic acid (= β-resorcylic acid), 2,5-dihydroxybenzoic acid (= gentisic acid), 2,6-dihydroxybenzoic acid (= Γ-resorcylic acid) and 3,5-dihydroxybenzoic acid (= α-resorcylic acid). Benzoic acid esters include methyl benzoate, ethyl benzoate, butyl benzoate, propyl benzoate, and benzyl benzoate, and hydroxyl forms thereof include isobutyl parahydroxybenzoate, isopropyl parahydroxybenzoate, and ethyl parahydroxybenzoate. And butyl parahydroxybenzoate and propyl parahydroxybenzoate.

  In addition, the benzene production inhibitor of the present invention is added to and blended with products containing the above-mentioned benzoic acids for the purpose of preserving products such as antiseptics, and products originally containing benzoic acids derived from raw materials. By being used, the production of benzene from benzoic acids in the product can be suppressed.

  The benzene production inhibitor of the present invention is used by being added to a composition containing benzoic acids, and the blending ratio thereof is 100 parts by weight based on the total amount of benzoic acid in the benzoic acid in the composition. The ratio of the total amount of flavonol and flavonol glycoside is usually 1 to 100000 parts by weight, preferably 1 to 50000 parts by weight, and more preferably 1 to 10000 parts by weight.

  In addition, benzene formation from benzoic acids in the product can occur by light irradiation or heating at each stage of production, distribution, and storage period. However, according to the benzene formation inhibitor of the present invention, benzene generation by light irradiation is particularly important. Can be significantly suppressed.

  The usage of the benzene production inhibitor of the present invention for these products will be described in detail in (II) and (III) below.

(II) Benzoic acid-containing composition containing a benzene production inhibitor The present invention provides a benzoic acid-containing composition containing the above-described flavonols or flavonols and ascorbic acid as a benzene production inhibitor. The said benzoic acid containing composition has an effect that the production | generation of benzene resulting from a benzoic acid is significantly suppressed by containing a flavonol or a flavonol and ascorbic acid.

  Here, the benzoic acid-containing composition means a composition containing at least one benzoic acid such as benzoic acid, benzoic acid salt, benzoic acid ester and hydroxyl group thereof. Benzoic acid compositions include not only compositions (products) with artificially added benzoic acids for the purpose of preservation (preservation), but also spices such as cinnamon, thyme or fennel; leek, large leaf, broccoli or shiitake Vegetables such as benzoin (benzoic acid), which is a fragrance-based raw material, and compositions (products) containing benzoic acids derived from ingredients originally contained in the material used for preparing the composition are also included.

  Although it does not restrict | limit as an amount of benzoic acid contained in this benzoic acid content containing composition, When converted into the ratio of a benzoic acid, 1-2500 ppm normally, Preferably it is 1-1000 ppm, More preferably, 1-600 ppm can be mentioned. .

  Examples of the benzoic acid-containing composition include products that can be applied to humans and animals and can be taken into the living body, in particular, foods and drinks, cosmetics, pharmaceuticals, quasi drugs, and feeds. Preferably it is food and drink. Beverages, preferably soft drinks; cosmetics, preferably lotions, emulsions; quasi drugs, preferably drinks, gargles, mouthwashes, liquid polishes, eyewashes; and pharmaceuticals, preferably drinks Examples include water-containing products such as preparations, liquid medicines, syrups, eye drops, injection solutions, and infusion solutions.

  The foods and drinks targeted by the present invention are not particularly limited as long as they contain benzoic acids added for the purpose of storage or the like, or have benzoic acids derived from ingredients originally contained in the material. Examples of such foods and drinks include milk beverages, lactic acid bacteria beverages, fruit juice soft drinks, soft drinks, carbonated drinks, fruit juice drinks, vegetable drinks, vegetable / fruit drinks, alcoholic drinks, powdered drinks, coffee drinks, tea drinks, sports drinks, nutrition Beverages such as drinks; custard pudding, milk pudding, souffle pudding, puddings such as pudding with fruit juice, desserts such as jelly, bavaroa and yogurt; ice cream, ice milk, lacto ice, milk ice cream, ice cream with fruit juice and Frozen confectionery such as soft ice cream, ice candy, sherbet, ice confectionery; gums such as chewing gum and bubble gum (board gum, sugar-coated granule gum); strawberry chocolate, blueberry chocolate and melon chocolate in addition to coated chocolate such as marble chocolate Chocolates such as chocolate with flavors such as salt; hard candy (including bonbon, butterball, marble, etc.), soft candy (including caramel, nougat, gummy candy, marshmallow, etc.), caramel such as drop, toffee Baked confectionery such as hard biscuits, cookies, rice crackers, rice crackers (and above); soups such as consomme soup and potage soup; pickled in soy sauce, pickled in soy sauce, pickled in salt, miso pickled, pickled in pickles, pickled in pickles, pickled in pickles, Pickles such as pickled vinegar, pickled eggplant, pickled moromi, pickled ume, pickled Fukujin pickled, shiba pickled, ginger pickled, pickled ume vinegar; sauces such as soy sauce, ponzu, separate dressing, non-oil dressing, emulsified dressing, ketchup, sauce, sauce; strawberry Jam, blueberry jam, marmalade, Jams such as Ngojam, apricot jam, presabu; syrups; fruit wine such as red wine; processed fruits such as syrup pickled cherries, apricots, apples, strawberries, peaches; processed meat products such as ham, sausage, grilled pork; fish meat Ham, fish sausage, fish surimi, salmon, bamboo rings, hampen, fried Satsuma, Date roll, whale bacon and other dairy and fat products such as butter, margarine, cheese, whipped cream; udon, cold wheat, somen, buckwheat Noodles such as Chinese noodles, spaghetti, macaroni, rice noodles, harsame and wonton; and other various prepared foods and various processed foods such as rice cakes and rice cakes. Beverages and confectionery are preferred.

  The food and drink of the present invention can be produced according to conventional production methods for various foods and drinks, except that the benzene production inhibitor of the present invention is blended in any step of production. Although there is no restriction | limiting in particular in the mixing | blending method and order of a benzene production | generation inhibitor, It is preferable to add a benzene production | generation inhibitor in the initial stage of a manufacturing process. Preferably, the benzene formation inhibitor of the present invention is included when the benzoic acid is added, or a benzene formation inhibitor is added before the heat treatment step or exposure to light.

  Cosmetics targeted by the present invention include skin cosmetics containing benzoic acids (lotions (skin lotions), milky lotions, creams, etc.), lipsticks, sunscreen cosmetics, makeup cosmetics, etc .; as pharmaceuticals, various tablets containing benzoic acids , Capsules, drinks, lozenges, gargles, eye drops, injections, drops, etc .; quasi-drugs containing benzoic acids (especially liquid brushes), mouthwashes, mouth fresheners, bad breath Examples of preventive agents, eyewashes, and the like; and feeds include various pet foods such as cat foods and dog foods containing benzoic acids, food for aquarium fish or cultured fish, but are not limited thereto.

  These benzoic acid-containing compositions such as cosmetics, pharmaceuticals, quasi-drugs, and feeds are commonly used in various products except that the benzene formation inhibitor of the present invention is blended in any step of their production. It can be manufactured according to the method. There are no particular restrictions on the blending time of the benzene production inhibitor in cosmetics, pharmaceuticals, quasi drugs or feeds, but it is desirable to blend with various materials at the beginning of the manufacturing process, preferably before the heat treatment process or before exposure to light.

  The amount of the benzene formation inhibitor of the present invention added to various benzoic acid-containing compositions such as foods, cosmetics, pharmaceuticals, quasi-drugs, and feeds is particularly limited as long as the amount of benzene formation from benzoic acids can be suppressed. Not. The content of benzoic acids contained in each composition (product) can be appropriately selected and determined in consideration of the type / use of the object and the components contained therein. For example, it is sufficient that a benzene formation inhibitor is added to the benzoic acid-containing composition so as to be contained in a proportion of at least 0.1 ppm as the total amount of flavonols. The total amount of flavonols is preferably 1 to 10,000 ppm, more preferably 1 to 5000 ppm. More preferably, the benzoic acid-containing composition may include a blending ratio such that the benzene formation inhibitor is contained in a total amount of flavonols of at least 0.1 ppm, preferably 1 to 1000 ppm.

  Further, the total amount of flavonol and flavonol glycoside is preferably 1 to 100000 parts by weight, more preferably, relative to 100 parts by weight of the total amount of benzoic acid contained in the benzoic acid-containing composition. You may add a benzene production | generation inhibitor in the ratio which becomes 1-50000 weight part, More preferably, it is 1-10000 weight part.

  In the benzoic acid-containing composition, the ratio of ascorbic acids (total amount) to 100 parts by weight of flavonols (total amount) is usually 1 to 100000 parts by weight, preferably 1 to 50000 parts by weight, more preferably 2 to 30000 parts by weight. A benzene formation inhibitor can be blended so that

(III) Method for inhibiting benzene production of benzoic acid-containing composition The present invention also provides a method for inhibiting benzene production of a benzoic acid-containing composition.

  The benzoic acid-containing composition targeted by the present invention is a composition obtained by artificially adding benzoic acids for the purpose of storage or the like, or has benzoic acids derived from components originally contained in the materials used. If it is the composition which is, there will be no restriction | limiting in particular. Specific examples include various benzoic acid-containing products such as foods and drinks, cosmetics, pharmaceuticals, quasi drugs, and feeds described above.

  The method of the present invention can be carried out by allowing these benzoic acid-containing compositions to coexist with the benzene production inhibitor of the present invention. Here, the coexistence mode is not particularly limited as long as a state in which both are in contact with each other is formed. For example, such a coexistence state can be formed by blending the benzoic acid-containing composition with the benzene production inhibitor of the present invention. For example, when the benzoic acid-containing composition is a food or drink, the coexistence state can be formed by blending the benzene formation inhibitor of the present invention as one of the material components during the production of the food or drink. The same applies to other products such as cosmetics, pharmaceuticals, quasi drugs, and feeds.

  The use ratio of the benzene formation inhibitor of the present invention with respect to the benzoic acid-containing composition is not particularly limited as long as the effect of the present invention is exhibited, and can be adjusted as appropriate according to the type of the target composition. it can. Although not particularly limited, the blending ratio of the benzene formation inhibitor to the benzoic acid-containing composition is at least 0.1 ppm, preferably 1 to 10,000 ppm, more preferably 1 to 5000 ppm in terms of the total amount of flavonols. be able to. As a blending ratio of the benzene formation inhibitor in the benzoic acid-containing composition, more preferably, a ratio of at least 0.1 ppm, preferably 1-1000 ppm in terms of the total amount of flavonols can be mentioned.

  Furthermore, the total amount of flavonols and flavonol glycosides is 1 to 100000 parts by weight, preferably 1 to 50000 parts by weight with respect to 100 parts by weight of the total amount of benzoic acid in the benzoic acid-containing composition. Benzene formation inhibitor may be added in such a proportion that it becomes 1 part by weight, more preferably 1 to 10,000 parts by weight.

  In the benzoic acid-containing composition, the ratio of ascorbic acids (total amount) to 100 parts by weight of flavonols (total amount) is usually 1 to 100,000 parts by weight, preferably 1 to 50000 parts by weight, more preferably 2 to 30000 parts by weight. As a guide, a benzene formation inhibitor can be blended.

  According to the method for inhibiting the production of benzene of the present invention, the production of benzene caused by benzoic acids in the benzoic acid-containing composition can be significantly suppressed, and mixing of benzene in the composition can be prevented.

  Hereinafter, the present invention will be described with reference to experimental examples and formulation examples, but the present invention is not limited to these experimental examples. The bayberry extract, rutin, enzyme-treated isoquercitrin (hereinafter referred to as EMIQ), and enzyme-treated rutin used those prepared in Preparation Example 1, Preparation Example 2, Preparation Example 3, and Preparation Example 4, respectively. did.

Preparation Example 1 Preparation of bayberry extract 200 g of dried bayberry leaves (including a little twig) are pulverized and extracted by stirring for 4 hours while adding 1 L of methanol and maintaining at 60 ° C. The mixture is cooled to room temperature and filtered with suction. The residue is washed with 150 mL of methanol, and the filtrate and the washing solution are combined. The solution is concentrated under reduced pressure to 100 mL using a rotary evaporator. The concentrated solution exhibiting a blackish green color is transferred to a separatory funnel, and 150 mL of water is added, followed by washing with ethyl ether three times. The aqueous layer was concentrated under reduced pressure, and methanol was added to the concentrate for crystallization to obtain a yellowish brown precipitate. By recrystallizing this from methanol, 2.5 g of bayberry extract was obtained.

  The obtained bayberry extract was subjected to HPLC analysis under the following conditions to calculate the content (% by weight) of myricitrin contained in the bayberry extract.

<HPLC conditions>
Column: Inertsil ODS-3 Φ4.6 × 250mm (GL Science)
Eluent: Water / acetonitrile / TFA = 850/150/1
Detection: Absorbance measurement flow rate at a wavelength of 343 nm: 1.0 ml / min.

  As a result of the measurement, the prepared bayberry extract contained 98.2% by weight of myricitrin.

Preparation Example 2 Preparation of Rutin After 250 g of Enju bud, which is a leguminous plant, was immersed in 2500 mL of hot water (95 ° C. or higher) for 2 hours, the filtrate obtained by filtration was obtained as a “first extract”. On the other hand, the residue separated by filtration was further immersed in hot water and extracted to obtain a “second extract”. These first and second extracts are combined, cooled to 30 ° C. or lower and the precipitated components are filtered off, and the precipitate is washed with water, recrystallized and dried to obtain 22.8 g of rutin having a purity of 95% or more. Obtained.

Preparation Example 3 Preparation of EMIQ (enzyme-treated isoquercitrin) (1) Preparation of isoquercitrin 20 g of rutin prepared in Preparation Example 2 was dispersed in 400 mL of water and adjusted to pH 4.9 using a pH adjuster. To this was added 0.12 g of Naringinase (Amano Enzyme Co., Ltd., trade name Naringinase “Amano”, 3,000 U / g) to start the reaction, which was kept at 72 ° C. for 24 hours. Thereafter, the reaction solution was cooled to 20 ° C., and the precipitate produced by cooling was separated by filtration. The obtained precipitate (solid content) was washed with water and dried to recover 13.4 g of isoquercitrin.

(2) Preparation of EMIQ (enzyme-treated isoquercitrin) To 10 g of isoquercitrin obtained above, 500 mL of water was added and 40 g of corn starch was added and dispersed. To this was added 15 g of cyclodextrin glucanotransferase (CGTase: Amano Enzyme Co., Ltd., trade name Contizyme, 600 U / mL) to start the reaction, and this was maintained at pH 7.25, 60 ° C. for 24 hours. did. After cooling the obtained reaction solution, it was added to a column (Φ3.0 × 40 cm) of Diaion HP-20 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) and washed with 1000 mL of water. Next, 600 mL of a 50% by volume ethanol aqueous solution was applied to the column, and the obtained eluate was concentrated under reduced pressure and then lyophilized to obtain 12.8 g of enzyme-treated isoquercitrin (EMIQ).

  The obtained EMIQ was subjected to HPLC analysis under the following conditions to calculate the molar ratio (%) of various α-glucosyl isoquercitrins contained in EMIQ.

<HPLC conditions>
Column: Inertsil ODS-2 Φ4.6 × 250mm (GL Science)
Eluent: water / acetonitrile / TFA = 850/150/2
Detection: Absorbance measurement flow rate at a wavelength of 351 nm: 0.8 ml / min.

  The molar composition ratio (%) of enzyme-treated isoquercitrin (EMIQ) is shown below. The molar composition ratio is a composition ratio converted from isoquercitrin (hereinafter referred to as IQC) to IQC + Glc7 in which seven glucoses are bound to IQC by seven α-1,4 bonds as 100%. . In the description such as “IQC + Glc1” in Table 1, the number after “Glc” means the number of glucose α-1,4 linked to isoquercitrin. Specifically, for example, “IQC + Glc1” is α-glucosylisoquercitrin in which glucose is bound to isoquercitrin by one α-1,4 bond, and “IQC + Glc7” is glucose to isoquercitrin. Means α-glucosyl isoquercitrin in which seven α-1,4 bonds are linked, respectively. In addition to these components, EMIQ contained trace amounts of 8 or more glucoses bound to IQC (IQC + Glc8 or more).

Preparation Example 4 Preparation of enzyme-treated rutin To 10 g of rutin prepared in Preparation Example 2, 500 mL of water was added and 40 g of corn starch was added and dispersed. To this, 20 g of cyclodextrin glucanotransferase (CGTase: Amano Enzyme Co., Ltd., trade name Contizyme, 600 U / mL) was added to start the reaction, and this was maintained at pH 7.25 and 60 ° C. for 30 hours. did. After cooling the obtained reaction solution, it was added to a column (Φ3.0 × 40 cm) of Diaion HP-20 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) and washed with 1000 mL of water. Next, 600 mL of a 50% by volume ethanol aqueous solution was applied to the column, and the obtained eluate was concentrated under reduced pressure and then freeze-dried to obtain 13.4 g of enzyme-treated rutin.

  The obtained enzyme-treated rutin was subjected to HPLC analysis under the following conditions, and the molar ratio (%) of various α-glucosylrutin contained in the enzyme-treated rutin was calculated.

<HPLC conditions>
Column: Inertsil ODS-2 Φ4.6 × 250mm (GL Science)
Eluent: water / acetonitrile / TFA = 850/150/2
Detection: Absorbance measurement flow rate at a wavelength of 351 nm: 0.8 ml / min
Table 2 shows the molar composition ratio (%) of the enzyme-treated rutin. The molar composition ratio is a composition ratio converted to 100% of rutin (RTN) and a total of 8 components in which 1-7 glucoses are bound to rutin by α-1,4 bonds. In descriptions such as “RTN + Glc1” in Table 2, the number after “Glc” means the number of glucose α-1,4 bonded to rutin. Specifically, for example, “RTN + Glc1” is α-glucosylrutin in which one glucose is bonded to rutin by α-1,4 bonds, and “RTN + Glc7” is glucose, α-1,4 in rutin. Each α-glucosylrutin linked by 7 bonds is meant.

  In addition to these components, enzyme-treated rutin contained trace amounts of 8 or more glucose bound to rutin (RTN + Glc8 or more).

Experimental example 1
The components described in each formulation in Table 3 were mixed to prepare 6 types of beverages for light irradiation test (Formulation Examples 1 to 6), filled into clean 200 mL transparent glass bottles and sealed. This was subjected to a light irradiation test, and after a predetermined time, the benzene content was measured to evaluate the amount of benzene produced by light irradiation.

  1) Test prescription

2) Light irradiation test The light irradiation test beverages prepared above (Prescription Examples 1 to 6) were irradiated with light using a fade meter under the following conditions.

Equipment: Carbon Arc Long Life Fade Meter FAL-3 (manufactured by Suga Test Instruments Co., Ltd.)
Irradiation time: 2, 4 and 6 hours Irradiation energy: 33 Langley / hr.

3) Measurement of benzene content To a 300-mL separatory funnel, add 200 mL of test beverage after light irradiation and 10 mL of n-heptane (for high-performance liquid chromatograph, Wako Pure Chemicals), and shaker (KM-SHAKER: IWAKI) And shaken for 5 minutes. After standing for 10 minutes, the organic layer was recovered and subjected to GC / MS under the following conditions to measure the benzene content.

<GC / MS measurement conditions>
GC / MS: Agilent Technologies 5973N
Column: DB-Wax (0.25mm x 60m, J & W Scientific.)
Injection volume: 3uL
Inlet temperature: 250 ° C
Split ratio: 20: 1.

4) Test results The results are shown in Table 4.

  As shown in Table 4, the beverage of Formulation Example 1 containing sodium benzoate had a benzene content that increased with time due to light irradiation, but beverages containing EMIQ or bayberry extract (prescriptions 2 and 3). ) Has an extremely low benzene content, and EMIQ and bayberry extracts were found to have the effect of suppressing benzene formation caused by sodium benzoate. In addition, from the results of Formulation Example 4, ascorbic acid was also found to have an effect of suppressing benzene formation caused by sodium benzoate, but by further using EMIQ and bayberry extract in combination, Generation could be suppressed.

Experimental example 2
The ingredients described in each formulation of Table 5 were mixed to prepare 8 types of beverages for light irradiation test (Prescription Examples 7 to 14), and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a light irradiation test (irradiation time: 6 hours) in the same manner as in Experimental Example 1, and then the benzene content was measured to evaluate the amount of benzene produced by light irradiation.
1) Test prescription

2) Measurement of benzene content The test beverage after light irradiation was treated in the same manner as in Experimental Example 1 to recover the organic layer, which was subjected to GC / MS under the following conditions to measure the benzene content.
<GC / MS measurement conditions>
GC: Agilent Technologies 6890N
MS: JEOL K-9
Column: DB-5MS (0.25mm x 60m) (J & W Scientific)
Injection volume: 3uL
Inlet temperature: 250 ° C
Split ratio: 30: 1.

3) Test results The results are shown in Table 6.

  As shown in Table 6, the amount of benzene produced by irradiating a sodium benzoate-containing beverage with light was kept low in beverages to which EMIQ was added (Prescription Examples 8 to 10). L-ascorbic acid was also found to have an effect of suppressing the formation of benzene (Prescription Example 11), and the beverage containing EMIQ further had a low benzene content depending on the concentration of EMIQ. From these, it can be seen that EMIQ has an excellent effect of suppressing the production of benzene caused by sodium benzoate.

Experimental example 3
8 kinds of beverages for light irradiation test (Prescription Examples 15 to 22) are prepared by mixing the components described in each formulation of Table 7, and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a light irradiation test (irradiation time: 6 hours) in the same manner as in Experimental Example 2, the benzene content was measured, and the amount of benzene produced by light irradiation was evaluated.
1) Test prescription

2) Test results The results are shown in Table 8.

  As shown in Table 8, the amount of benzene produced by irradiating the sodium benzoate-containing beverage with light decreased depending on the concentration of L-ascorbic acid added to the beverage. Furthermore, the beverage with EMIQ added had a lower benzene content than the beverage without EMIQ. From these results, it can be seen that L-ascorbic acid and EMIQ have an action of suppressing the production of benzene caused by light irradiation and caused by sodium benzoate, and the action is enhanced by combining them.

Experimental Example 4
Ingredients described in each formulation of Table 9 were mixed to prepare 3 types of beverages for thermal abuse test (Prescription Examples 23 to 25), and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a heat abuse test (60 ° C., 1 to 14 days), and then the benzene content was measured to evaluate the amount of benzene produced by heat treatment.
1) Test prescription

2) Thermal abuse test The thermal abuse test beverages prepared above (Prescription Examples 23 to 25) were stored under the following high temperature conditions and subjected to thermal abuse tests.

Constant temperature machine: EYDYA WINDY OVEN WFO-600D
Storage period: 1, 3, 7 and 14 days Storage temperature: 60 ° C.

3) Measurement of benzene content The test beverage after the thermal abuse test was treated in the same manner as in Experimental Example 1 to recover the organic layer and subjected to GC / MS under the same conditions as in Experimental Example 2 to measure the benzene content. .

4) Test results Table 10 shows the results.

  As shown in Table 10, it was observed that benzene was produced and increased over time by heat abuse (high temperature storage) of a sodium benzoate-containing beverage. However, this benzene formation could be significantly suppressed by adding EMIQ or L-ascorbic acid to the sodium benzoate-containing beverage. From this result, it can be seen that L-ascorbic acid and EMIQ have an action of suppressing the formation of benzene caused by sodium benzoate generated by heat treatment.

Experimental Example 5
The ingredients described in each formulation of Table 11 are mixed to prepare 4 types of beverages for thermal abuse test (Prescription Examples 26 to 29). After sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a thermal abuse test (60 ° C., 7 days) in the same manner as in Experimental Example 4 to measure the benzene content, and the amount of benzene produced by heat treatment was evaluated.
1) Test prescription

2) Test results The results are shown in Table 12.

  As shown in Table 12, it was recognized that benzene was produced by heat abuse (high temperature storage) of a sodium benzoate-containing beverage. This benzene production was achieved by adding EMIQ to a sodium benzoate-containing beverage. It was possible to suppress significantly. This result shows that EMIQ has the effect | action which suppresses the production | generation of benzene resulting from the sodium benzoate which arises by heat processing.

Experimental Example 6
The ingredients described in each formulation of Table 13 were mixed to prepare 6 types of beverages for light irradiation test (Prescription Examples 30 to 35), and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a light irradiation test (irradiation time: 6 hours) in the same manner as in Experimental Example 1, and then the benzene content was measured to evaluate the amount of benzene produced by light irradiation.
1) Test prescription

2) Measurement of benzene content To a 300 mL separatory funnel, add 200 mL of test beverage after light irradiation and 10 mL of n-heptane (for high performance liquid chromatograph, Wako Pure Chemicals), shaker (KM-SHAKER: IWAKI) And shaken for 5 minutes. After standing for 10 minutes, the organic layer was recovered and subjected to GC / MS under the following conditions to measure the benzene content.

<GC / MS measurement conditions>
GC: Agilent Technologies 6890N
MS: JEOL K-9
Column: DB-5MS (0.25mm x 30m) (J & W Scientific)
Injection volume: 1uL
Inlet temperature: 250 ° C
Split ratio: 15: 1.

3) Test results The results are shown in Table 14.

  In addition, when the sodium benzoate-containing beverage having the same formulation as the above-mentioned Formulation Example 30 was allowed to stand for 6 hours under a condition where light was not irradiated (light-shielding condition), benzene was not detected (below the detection limit). On the other hand, as shown in Table 14, benzene was produced by irradiating light to a sodium benzoate-containing beverage comprising the prescription (prescription example 30), but the bayberry extract was added to produce the benzene. It was kept low in beverages (Prescription Examples 31 to 32). Moreover, the effect which suppresses the production | generation of the said benzene was recognized also to L-ascorbic acid (prescription example 33). Furthermore, in the beverage containing the bayberry extract, the benzene content was kept low depending on the concentration of the bayberry extract (Formulation Examples 34 to 35). These facts indicate that the bayberry extract has an excellent effect of suppressing the production of benzene caused by sodium benzoate.

Experimental Example 7
Ingredients described in each formulation of Table 15 were mixed to prepare three types of beverages for thermal abuse testing (Prescription Examples 36 to 38), and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a thermal abuse test (60 ° C., 7 days) in the same manner as in Experimental Example 5, the benzene content was measured by the same method as in Experimental Example 6, and the amount of benzene produced by heat treatment was evaluated.
1) Test prescription

2) Test results Table 16 shows the results.

  In addition, when the sodium benzoate-containing beverage having the same formulation as the above-mentioned Formulation Example 36 was stored at 5 ° C. for 7 days without being stored at high temperature, benzene was not detected (below the detection limit). On the other hand, as shown in Table 16, it was confirmed that benzene was produced by heat abuse (high temperature storage) of a sodium benzoate-containing beverage (Prescription Example 36). It could be significantly suppressed by blending a sodium-containing beverage with a bayberry extract containing myricitrin, a flavonol glycoside. From this result, it is understood that the bayberry extract has an action of suppressing the production of benzene due to sodium benzoate generated by heat treatment.

Experimental Example 8
Nine kinds of beverages for light irradiation test (Prescription Examples 39 to 47) were prepared by mixing the components described in each formulation of Table 17, and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a light irradiation test (irradiation time: 6 hours) in the same manner as in Experimental Example 1, and then the benzene content was measured to evaluate the amount of benzene produced by light irradiation.
1) Test prescription

2) Measurement of benzene content In the same manner as in Experimental Example 6, the test beverage after light irradiation was treated to recover the organic layer, and the benzene content was measured.

3) Test results The results are shown in Table 18.

  As shown in Table 18, the beverages of Formulation Examples 39 and 43 containing sodium benzoate had an increased benzene content by light irradiation, and flavonols (EMIQ, rutin, bayberry extract, enzyme-treated rutin) The benzene content of the beverages (prescriptions 40 to 42, 44 to 47) added with benzene was extremely low, and these flavonols had the effect of suppressing the production of benzene caused by sodium benzoate. Moreover, as can be seen from the results of Formulation Examples 43 to 47, ascorbic acid was also found to have an action of suppressing the production of benzene due to sodium benzoate, but by further using flavonols in combination, It was possible to further suppress the formation of benzene.

Experimental Example 9
Nine kinds of beverages for light irradiation test (Prescription Examples 48 to 57) were prepared by mixing the components described in each formulation of Table 19, and after sterilization at 93 ° C., filling a clean 200 mL transparent glass bottle, Sealed. This was subjected to a thermal abuse test (60 ° C., 7 days) in the same manner as in Experimental Example 4 to measure the benzene content, and the amount of benzene produced by heat treatment was evaluated.
(1) Test prescription

2) Measurement of benzene content In the same manner as in Experimental Example 6, the test beverage after heat abuse was treated to recover the organic layer, and the benzene content was measured.

3) Test results The results are shown in Table 20.

  As shown in Table 20, the beverages of Formulation Examples 48 and 53 containing sodium benzoate had an increased benzene content due to thermal abuse, and flavonols (EMIQ, rutin, bayberry extract, enzyme-treated rutin) The benzene content of the beverages (prescription 49-52, 54-57) added with flavonol was significantly lower than that without the addition of flavonols (prescription examples 48, 53), and the benzene produced by sodium benzoate in these flavonols It was recognized that there was an action to suppress the production. Further, as can be seen from the results of Formulation Examples 53 to 57, ascorbic acid was also found to have an effect of suppressing benzene formation due to sodium benzoate, but by further using flavonols in combination therewith, it was further improved. The production of benzene could be suppressed.

Example 1: Beverage containing lemon juice Among the formulation examples listed in Table 21 below, after adding raw materials other than fruit juice and fragrance to ion-exchanged water and heating and stirring to 90 ° C, the fruit juice and fragrance were added, mixed and stirred, and then the container And cooled to obtain a beverage containing lemon juice. The resulting beverage was able to significantly suppress benzene production compared to the comparative beverage to which no flavonols were added.

Example 2: Acid milk beverage Among the formulation examples listed in Table 22 below, raw materials other than citric acid and fragrance are added to ion-exchanged water, and after stirring and dissolving, the pH is adjusted to 3.8 with citric acid, and the mixture is heated to 70 ° C. Warm and homogenize (150 kg / cm ² ). After stirring and heating to 90 ° C., a fragrance was added and mixed, and then filled in a container and cooled to obtain an acidic milk beverage. The resulting beverage was able to significantly suppress benzene production compared to the comparative beverage to which no flavonols were added.

Example 3 : Carbonated beverage with grape juice In the formulation examples listed in Table 23 below, raw materials other than fruit juice, fragrance, and carbonated water were added to ion-exchanged water, and the mixture was heated and stirred to 90 ° C., and then juice and fragrance were added. A syrup was prepared by heating to 10 ° C. and then cooling to 10 ° C. or lower. The carbonated beverage containing grape juice was obtained by adding and mixing the syrup cooled to 10 ° C. or less with carbonated water. The resulting beverage was able to significantly suppress benzene production compared to the comparative beverage to which no flavonols were added.

Example 4 : Peach flavored beverage Among the formulation examples listed in Table 24 below, after adding raw materials other than fragrance to ion-exchanged water, heating and stirring to 90 ° C., cooling, and then adding fragrance, The container was filled to obtain a peach flavored beverage. The obtained beverage was stored for 1 month under fluorescent lamp irradiation (1200 lux) on the display shelf, but no benzene was produced.

Example 5: Vegetable / fruit mix beverage Among the formulation examples listed in Table 25 below, after adding ingredients other than fruit juice, vegetable juice and fragrance and mixing and stirring, vegetable juice (carrot juice, spinach juice, parsley juice) and apple Fruit juice was added and heated to 80 ° C. with stirring. Lemon juice and fragrance were added to this, filled into a container, and then cooled to obtain a vegetable / fruit mixed drink. The resulting beverage was able to significantly suppress benzene production compared to the comparative beverage to which no flavonols were added.

Example 6: Vitamin jelly Among the formulation examples listed in Table 26 below, fructose-glucose liquid sugar, trisodium citrate, and a gelling agent are added to ion-exchanged water, and heated and stirred at 80 ° C. for 10 minutes, and then the remaining raw materials The mixture was further stirred and mixed. This was filled in a container, sterilized by heating at 85 ° C. for 30 minutes, and then cooled to obtain vitamin jelly. The obtained jelly was able to remarkably suppress the production of benzene as compared with the comparative beverage to which no flavonols were added.

Example 7: Nutrition drink Among the formulation examples listed in Table 27 below, raw materials other than the fragrance were added to ion-exchanged water, and after heating and stirring to 90 ° C, the fragrance was added and heating and stirring to 93 ° C. This was filled in a container and then cooled to obtain an energy drink. The obtained energy drink was stored for 1 month under fluorescent lamp irradiation (1200 lux) on the display shelf, but no benzene was produced.

Example 8: Sports drink Among the formulations listed in Table 28 below, raw materials other than fragrance were added to ion-exchanged water, and after heating and stirring to 90 ° C, the fragrance was added and further mixed and stirred. This was filled in a container and then cooled to obtain a sports drink. The resulting sports drink was able to significantly suppress benzene production as compared to the comparative beverage in which no flavonols were added.

Example 9: Lime syrup (for dilution)
Among the formulation examples listed in Table 29 below, raw materials other than fruit juice and fragrance were added to ion-exchanged water, and after heating and stirring to 70 ° C., fruit juice and fragrance were added. After mixing and stirring this, the container was filled and cooled to obtain lime syrup (for dilution). The obtained syrup was able to remarkably suppress the production of benzene as compared with the beverage of the comparative example in which no flavonols were added.

Example 10: Ponzu vinegar Among the formulation examples listed in the following Table 30, raw materials other than fruit juice, fragrance, and vinegar were mixed in ion-exchanged water and dissolved by heating until reaching a temperature of 80 ° C. Subsequently, fruit juice, a fragrance | flavor, and vinegar were added to this, and it stirred and melt | dissolved, after filling the container, it cooled and obtained ponzu. The obtained ponzu vinegar was able to significantly suppress benzene production as compared with the comparative beverage in which no flavonols were added.

Example 11: Thousand Island Dressing Among the formulation examples listed in Table 31 below, Component 1 was added to Component 16, and the mixture was heated and stirred at 80 ° C. for 10 minutes. Components 2 to 11 were added thereto and dissolved by stirring, cooled to 60 ° C. or lower, and components 12 and 13 were added and stirred. Furthermore, the component 14 was added little by little, it emulsified with the homomixer, the component 15 was added and mixed with this, and it filled with the container, and obtained the Thousand Island dressing. The obtained dressing was able to remarkably suppress the production of benzene as compared with the comparative beverage in which no flavonols were added.

Example 12: Toner lotion Among the formulation examples listed in Table 32 below, components 1 to 6 were added to component 11 and stirred to dissolve, and components 8 to 10 were added to component 7 in advance and stirred to dissolve. The product was solubilized by mixing and stirring. This was filtered and filled into a container to obtain a skin lotion. The obtained lotion was able to remarkably suppress the production of benzene as compared with the comparative beverage in which no flavonols were added.

Example 13: Emulsion Among the formulation examples listed in Table 33 below, components 1 to 7 are added to component 16 and dissolved by heating, maintained at 70 ° C, and components 8 to 15 are separately mixed and heated to dissolve. What was maintained at 70 degreeC was added, pre-emulsification was performed, and it emulsified uniformly with the homomixer. This was cooled with stirring to obtain an emulsion. The obtained emulsion was able to remarkably suppress the production of benzene as compared with the comparative beverage in which no flavonols were added.

Example 14: Liquid tooth brushing Among the following formulation examples, components 2 to 4 are added to component 1 and mixed well, and then components 5 to 8 are added to component 10 and mixed well, To this, component 9 was added and further mixed. Ingredient 10 was added to this and mixed to obtain a liquid toothpaste. The obtained liquid toothpaste was stored for 1 month under fluorescent lamp irradiation (1200 lux) on the display shelf, but no benzene was produced.

  The benzene production inhibitor of the present invention can significantly inhibit the production of benzene by heat or light in products containing benzoic acids such as benzoic acid, salts thereof or esters thereof. In recent years, beverages and the like are often sold while being packaged in a transparent container such as a PET bottle. The present invention is a product to which benzoic acids are added for the purpose of preserving and preserving products such as antiseptics, and in particular, products that are housed and packaged in a transparent container as described above, due to the influence of fluorescent lamps on display shelves. Production of benzene in the (benzoic acid-containing product) can be suppressed, and as a result, a product that stably maintains quality and safety for a long period of time can be provided.

Claims (20)

  A benzene production inhibitor comprising as an active ingredient at least one selected from the group consisting of flavonols and flavonol glycosides.   The benzene production inhibitor according to claim 1, wherein the flavonol and the flavonol glycoside are quercetin, isoquercitrin, enzyme-treated isoquercitrin, enzyme-treated rutin, rutin and myricitrin.   The active ingredient is at least selected from the group consisting of Enju extract, tartary buckwheat extract, dokudami extract, bayberry extract, buckwheat whole plant extract, red bean whole plant extract, onion extract, and rabu extract The benzene formation inhibitor of Claim 1 containing one plant extract.   The benzene production inhibitor according to claim 1, further comprising at least one selected from ascorbic acid, ascorbate, an ester compound of ascorbic acid, and an ascorbic acid glycoside.   The ratio of the total amount of ascorbic acid, ascorbate, an ester compound of ascorbic acid and ascorbic acid glycoside with respect to 100 parts by weight of the total amount of flavonol and flavonol glycoside is 1 to 100000 parts by weight. Benzene production inhibitor.   The benzene production inhibitor according to claim 1, which is used for suppressing the production of benzene by light irradiation.   A method for inhibiting benzene production of a benzoic acid-containing composition, comprising adding the benzene production inhibitor according to any one of claims 1 to 6 to the benzoic acid-containing composition.   The benzoic acid-containing composition is a composition containing at least one selected from the group consisting of benzoic acid, a salt of benzoic acid, a benzoic acid ester, and a hydroxyl form thereof, The benzene production suppression according to claim 7 Method.   The method for inhibiting benzene production according to claim 7, wherein the benzoic acid-containing composition contains benzoic acids in a total amount of 1 to 2500 ppm in terms of the amount of benzoic acid.   The method for inhibiting benzene production according to claim 7, wherein a benzene production inhibitor is added to the benzoic acid-containing composition at a ratio such that the total amount of flavonol and flavonol glycoside is 0.1 to 10,000 ppm.   The method for inhibiting benzene production according to claim 7, wherein the benzoic acid-containing composition is a food, drink, pharmaceutical product, quasi-drug, cosmetic product or feed.   The ratio that the total amount of flavonol and flavonol glycoside added to the benzoic acid-containing composition is 1 to 100000 parts by weight with respect to 100 parts by weight of the total amount of benzoic acid in the benzoic acid in the composition The method for inhibiting benzene production according to claim 7, wherein a benzene production inhibitor is added.   A benzoic acid-containing composition containing the benzene production inhibitor according to any one of claims 1 to 6.   The benzoic acid compound according to claim 13, wherein the benzoic acid-containing composition is a composition containing at least one selected from the group consisting of benzoic acid, a salt of benzoic acid, a benzoic acid ester, and a hydroxyl form thereof. Containing composition.   The benzoic acid-containing composition according to claim 13, wherein the benzoic acid-containing composition contains benzoic acid in a total amount of 1 to 2500 ppm in terms of the amount of benzoic acid.   The benzoic acid containing composition of Claim 13 which contains a benzene production | generation inhibitor in the ratio from which the total amount of the flavonol and flavonol glycoside in a benzoic acid containing composition becomes 0.1-10000 ppm.   The total amount of flavonols and flavonol glycosides in the benzoic acid-containing composition is 1 to 100,000 parts by weight with respect to 100 parts by weight of the total amount of benzoic acid in the benzoic acid in the composition, The benzoic acid-containing composition according to claim 13, comprising a benzene production inhibitor.   The benzoic acid-containing composition according to claim 13, which is a food or drink, a pharmaceutical product, a quasi-drug, a cosmetic product, or a feed. Use for the manufacture of at least one benzene production inhibitor selected from the group consisting of flavonols and flavonol glycosides.   Benzene of a composition containing at least one selected from the group consisting of flavonol and flavonol glycoside, and at least one selected from ascorbic acid, ascorbate, an ester compound of ascorbic acid and ascorbic acid glycoside Use for the production of production inhibitors.