JP2010185083A - Antidegradant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antidegradant excellent in performance of preventing foods, cosmetics, etc., from being degraded. <P>SOLUTION: The antidegradant includes a compound of a dynamic hydration number of 25 or larger such as maltotriose. Desirably, the antidegradant further contains a water-soluble antioxidant such as rosmarinic acid, vitamin C, ascorbic acid, isoascorbic acid, or a salt thereof (for example, an alkali metal salt or an alkaline earth metal salt), a catechin, or a catechin-containing natural extract. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a deterioration preventing agent, and more particularly to a deterioration preventing agent that is also effective as a shelf life improving agent for products including foods and cosmetics.

  Changes in quality in the process of material degradation and reactions between the material components involved are very diverse, and many of them occur simultaneously and in a chain. Recent research clearly shows that oxidation and photodegradation are involved in most degradation processes. Oxidation and photodegradation are also known to occur in air, water, air / water interface, water / oil interface, and air / oil interface. In addition, enzymes, metals, sensitizers, and the like are known as factors that enhance oxidative degradation, and oxidative degradation occurs in these combinations. On the other hand, photodegradation occurs when a substance absorbs ultraviolet light, visible light, or near infrared light.

  Food and beverage products and cosmetics are usually oxidized and deteriorated during the production process or during storage, so the perfume, pigment, and other ingredients that are blended with them are usually deteriorated. Is important in maintaining. For this reason, for example, natural antioxidants, synthetic antioxidants, antioxidant preparations appropriately blended with them (hereinafter collectively referred to as antioxidants) and the like are used in foods and cosmetics.

  For example, antioxidants based on rosmarinic acid, degradation inhibitors based on carnosic acid, herbal antioxidants such as rosemary, and antioxidants containing vitamin C and vitamin E are generally known. However, these antioxidants are not satisfactory in terms of the stability of the antioxidant ability to the external environment.

  In particular, an antioxidant that can be used even in a small amount and that does not deteriorate even when heated is strongly desired in the food and cosmetic fields, but no satisfactory one has been known yet. In addition, photodegradation may cause degradation due to photoreaction, but oxidation degradation and its mechanism are often different, and even an antioxidant does not have a sufficient effect as a photodegradation inhibitor, In addition, the antioxidant itself may cause photodegradation, and there is no satisfactory photodegradation agent.

  On the other hand, attempts to prevent oxidation in a packaging form without using an antioxidant are also active. For example, a vacuum-cooked food that is vacuum-packed with raw food materials and cooked at a low temperature together with the bag has little fragrance and flavor, and is hardly oxidized. It is attracting attention because it can be preserved. However, this method has a limit in the application range of materials, and there are many unsolved problems such as a problem of remaining bacteria, and it has not yet been widely used.

  In the field of cosmetics, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), etc. are conventionally used in order to prevent deterioration of fragrances and other materials, since these are synthetic chemical substances. There is a tendency to be avoided.

On the other hand, pigments are used for coloring foods and drinks, cosmetics, and the like. Particularly in foods and beverages, it is desired to use pigments derived from natural products, but natural pigments are easily discolored. Several proposals have been made regarding the prevention of discoloration such as fading or browning of pigments. For example, an anthocyanin pigment fading prevention agent (for example, patents) that uses the antioxidant properties of chlorogenic acid, caffeic acid, etc. Reference 1), anthocyanin pigment-containing foods and beverages (see, for example, Patent Document 2) and paprika pigments, for example, a fading prevention method (see, for example, Patent Document 3), a method for preventing sugar browning by caffeic acid, ferulic acid, chlorogenic acid, etc. Patent Document 4), a method for producing a candy without browning utilizing the effect of preventing browning of sugars (see, for example, Patent Document 5) and the like have been proposed. In addition, in order to prevent deterioration of foods, pharmaceuticals, cosmetics and the like due to oxidation, an antioxidant containing a proanthocyanidin minor body collected from a plant body such as grape fruit juice or seeds has been proposed. (For example, refer to Patent Documents 6 and 7).

  However, the conventionally proposed antioxidant substances such as chlorogenic acid, caffeic acid, and ferulic acid have a relatively large effect of suppressing the deterioration of food by heating, but the effect of preventing the deterioration of food by light irradiation is not always sufficient. Absent. In addition, proanthocyanidin minors used for the same purpose have the effect of suppressing the deterioration of food caused by light, but the effect of preventing food alteration by heating is not necessarily sufficient, and further improvement methods have not been developed. It has been demanded.

  Further, at least one antioxidant (a) selected from chlorogenic acid, caffeic acid, ferulic acid and green coffee bean extract, and at least one component (b) selected from amino acids, Maillard reactants and peptides. When an antioxidant composition comprising the following is added to, for example, foods and beverages, cosmetics, and the like, a dramatic synergistic effect that cannot be achieved by the individual action of each of them causes deterioration of the fragrance in the food, modulation of the fragrance In addition, there is a report that the deterioration of the quality of the product due to the fading of the pigment, the generation of a strange odor and the like is remarkably suppressed (for example, see Patent Document 8). However, such an antioxidant composition is not sufficiently satisfactory as in the prior art.

Japanese Patent Publication No. 1-222872 Japanese Patent Laid-Open No. 1-132344 Japanese Patent Publication No.59-50265 JP 57-115147 A Japanese Patent Publication No.58-32855 Japanese Patent Publication No. 3-7232 JP-A-3-2000078 JP-A-9-221667

  The present invention has been made for the purpose of solving the above-described problems, and an object of the present invention is to provide an anti-degradation agent having excellent anti-deterioration performance for foods, cosmetics and the like.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a deterioration inhibitor containing maltotriose, which is a compound having a dynamic hydration number of 25 or more, has an excellent effect in preventing deterioration of a substance. As a result, the inventors have reached the present invention described below.

(1) A compound having a dynamic hydration number of 25 or more and an antioxidant having a solubility in 1 L in hexane at 30 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of 0.1 g or more (addition) Component-2) and an antioxidant (additive component-3) having a solubility in 1 L in hexane at 30 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of less than 0.1 g, A deterioration inhibitor, wherein the content of additive component-2 is 0.01 to 50% by weight, and the content of additive component-3 is 0.05 to 10% by weight.

(2) A food comprising the above-described deterioration inhibitor.

(3) A cosmetic comprising the above-described degradation inhibitor.

(4) A glaze agent comprising the above-mentioned deterioration inhibitor.

(5) A plastic product comprising the above-mentioned deterioration inhibitor.

  The deterioration preventing agent of the present invention has high safety and is excellent in preventing deterioration of food, cosmetics and the like.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents.

(Dynamic hydration number)
First, the concept of “dynamic hydration number” used in the present invention will be described. The initial reaction of deterioration is considered to occur at the “interface”, that is, the gas-liquid interface, the liquid-solid interface, or the liquid-liquid interface, but in the case of most foods, the initial reaction of deterioration occurs at the oil-water interface. It is done. Here, considering mainly foods that are water-based, there are two types of water: free water and combined water. Among these, it is considered that free water often becomes a factor related to the initial reaction of deterioration.

  Control of free water can be realized by constraining the free movement of water molecules. The “dynamic hydration number” of a compound is an index of the degree of restraint of free movement of water when the compound is dissolved in water. In physical terms, dynamic hydration number refers to the relative change in “thermal motion of the same number of water molecules in bulk water” relative to “thermal motion of all water molecules in the hydrated phase”. (Reference: Uedaira, H., Bull. Chem. Soc., Jpn., Vol. 62, No. 1 (1989)). And the dynamic hydration number of a compound can be easily measured by the following methods, for example.

(Example of measurement test of dynamic hydration number)
25.0 mg of p-hydroxybenzoic acid was dissolved in pure water and diluted to 50 ml (blank). Sample solutions 1 and 2 were prepared by adding blanks to 1.008 g and 1.512 g, respectively, to give a total weight of 4.013 g and 3.001 g. The dynamic hydration number was determined by measuring the relaxation time (T1) of the sample solution at 25 ° C. using a spectrophotometer (“Inova 500” manufactured by Varian). An example of the results is as shown in Table 1 below.

  The larger the dynamic hydration number, the more the movement of water can be constrained, so it is predicted that it will be possible to control the free water that is a degradation factor. In other words, when a substance (compound) with a large dynamic hydration number is added to water, free water in the water is reduced, and degradation factors generated in the water are considered to be concentrated at the interface where the substance added in water cannot participate. It is done.

<Deterioration inhibitor (I)>
First, the deterioration inhibitor (I) according to the first invention will be described. The deterioration inhibitor (I) is characterized by comprising a compound having a dynamic hydration number of 25 or more.

  The first invention of the present application has been found based on the above knowledge, and it is possible to efficiently control the aggregation of deterioration factors at the interface by adding a compound having a dynamic hydration number of 25 or more to the product. It is a thing. Examples of the compound having a dynamic hydration number of 25 or more include sugars such as maltotriose, sugar alcohols such as maltotriol, proteins, peptides and the like.

<Deterioration inhibitor (II)>
Next, the deterioration inhibitor (II) according to the second invention will be described. The deterioration inhibitor (II) is characterized by comprising a trisaccharide or higher oligosaccharide, a polysaccharide or a derivative thereof.

  A combination of three monosaccharides is called a trisaccharide. A trisaccharide or higher oligosaccharide refers to a monosaccharide linked to about 3 to 20 molecules. Further, a combination of many monosaccharide molecules is called a polysaccharide. Oligosaccharides are easily soluble in water, but polysaccharides are difficult to dissolve in water. Oligosaccharides and polysaccharide derivatives of tri- or higher sugars include deoxy sugars in which the hydroxyl group of the sugar is replaced with hydrogen, uronic acid in which the carbon at the aldose end is replaced with a carboxyl group, amino sugars in which the hydroxyl group is replaced with an amino group, ketone groups, This refers to a sugar alcohol in which an aldehyde group is reduced to an alcohol.

  Examples of the oligosaccharide include isomaltoligosaccharide, fructooligosaccharide, xylo-oligosaccharide, soybean oligosaccharide, maltotriose and the like. Examples of the polysaccharide include starch, amylose, amylopectin, glycogen (generally animal starch), cellulose, chitin, agarose, carrageenan, pectin, heparin, hyaluronic acid and the like.

  Examples of low molecular weight sugar alcohols include xylitol, sorbitol, mannitol, maltitol, lactitol, and the like, and these can be structural units of trisaccharide or higher oligosaccharides and polysaccharide derivatives (sugar alcohols). Incidentally, the oligosaccharide alcohol obtained by reducing maltotriose, which is an oligosaccharide of trisaccharide or higher, is maltotriol.

  Of the above compounds, maltotriose is particularly preferred. Maltotriose is a linear oligosaccharide having a degree of polymerization of 3 or less, has the highest moisturizing power among oligosaccharides, and has a sweetness of about 1/4 that of sugar. For this reason, since the sugar content can be increased without increasing the sweetness, even if a large amount is added, it is safe and the sweetness is low. Furthermore, by adding a large amount, functions such as anti-corruption and suppression of starch aging can be exhibited. As an easily available maltotriose, there is a product “Oligotose” manufactured by Mitsubishi Chemical Foods. Incidentally, an oligosaccharide alcohol obtained by reducing “oligotose” is commercially available as a product “Oligotose H-70” manufactured by Mitsubishi Chemical Foods.

<Preferred embodiment of deterioration preventing agents (I) and (II)>
The deterioration preventing agents (I) and (II) of the present invention can enhance their deterioration preventing ability by adding an appropriate third component in an appropriate combination.

  In general, the non-oil-soluble compound is a compound that has almost no solubility in natural fats and oils such as vegetable oils, that is, a compound having a solubility in triglycerides of 0.1% or less. In the present invention, the oil-insoluble and the oil-soluble are defined by the solubility in hexane. The oil solubility (solubility in hexane) of main antioxidants is shown in Table 2 below.

  First, the types of additive components used in the deterioration inhibitors (I) and (II) of the present invention will be described.

(Additive component-1)
Additive Component-1 is a non-oil-soluble antioxidant having a solubility in 1 L of hexane at 30 ° C. of less than 50 g. Such non-oil-soluble antioxidants are classified into additive component-2 and additive component-3 described later.

  As described above, when a substance (compound) having a large dynamic hydration number is added to water, deterioration factors generated in the water are considered to be concentrated on the interface where the substance added in water cannot participate. Therefore, if the anti-degradation agent is placed at a position where deterioration factors tend to collect, that is, at the free water portion or interface that is not constrained by the additive substance, the function of the deterioration factors aggregated at the free water portion or interface is improved. It is thought that it can be inhibited.

  Since many foods are made of oil and water, they are hardly soluble in oil, that is, non-oil-soluble antioxidants are basically expected to be present in water or at the oil-water interface. When present in water, it works directly on uncontrolled free water. That is, such an antioxidant includes the following groups in which additive component-1 is divided into two from the viewpoint of water solubility.

(Additive component-2)
Additive Component-2 is a non-oil-soluble water-soluble antioxidant having a solubility in 1 L of hexane at 30 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of 0.1 g or more.

  Examples of the non-oil-soluble water-soluble antioxidant include rosmarinic acid, vitamin C (ascorbic acid), isoascorbic acid or a salt thereof (for example, alkali metal salt, alkaline earth metal salt, etc.), water-soluble Catechins to which is added (for example, glycosides, embedded with dextrin) and the like.

As said ascorbic acid and its salt, L-ascorbic acid, L-sodium ascorbate, erythorbic acid, sodium erythorbate, etc. are mentioned. Examples of the natural extract include water-soluble rosemary extracts (eg, trade name “RM21Abase” manufactured by Mitsubishi Chemical Foods) such as rutin, myricetin, myricitrin, chlorogenic acid, caffeic acid, ferulic acid, gallic acid, and the like. Tea extract (for example, trade name “Tiacaron” manufactured by Tokiwa Plant Science Laboratory Co., Ltd.), apple extract, grape seed extract (for example, product name “Binophenone” manufactured by Tokiwa Plant Science Laboratory Co., Ltd.), bayberry extract (for example, Sanei Gensha Co., Ltd., trade name “Sun Mary”), sunflower seed extract, rice bran extract and the like. Of these, rosmarinic acid and / or vitamin C are particularly preferable.

  Rosmarinic acid is one of the phenol carboxylic acids contained in herbs and is particularly contained in rosemary. Its structure is a form in which two phenolcarboxylic acids are bonded. Therefore, structurally and functionally, since there are more phenolic hydroxyl groups than phenol carboxylic acids, such as ferulic acid, caffeic acid, and chlorogenic acid, the antioxidant effect is high. Furthermore, an enzyme inhibitory activity effect such as SOD (superoxide desmutase) is also high. In addition, rosmarinic acid has a conjugated double bond in the structure, and therefore has a high effect of preventing photodegradation.

  The rosmarinic acid used in the present invention is preferably a natural extract from the viewpoint of safety. The rosmarinic acid used in the present invention includes rosmarinic acid glycosides. Any form of glycoside may be used. This natural product is extracted from herbs, particularly from Lamiaceae, but an extract from rosemary in which a large amount of rosmarinic acid is present is preferred.

  The general production method of rosmarinic acid is as follows. As the raw material, whole rosemary or any of its leaves, roots, stems, flowers, fruits and seeds may be used, but leaves are preferably used. Usually, it is used after chopping to improve the extraction efficiency. Rosmarinic acid is obtained as a water-soluble extract of rosemary. Therefore, it is obtained by extracting with water-containing ethanol, adding water to the extract to precipitate a water-insoluble component, and concentrating the solution from which the water-insoluble component has been separated under reduced pressure. Water-containing ethanol having a water content of 40 to 60% by weight is preferably used.

  Furthermore, when a water-insoluble degradation inhibitor is added, this agent aggregates at the interface, and it is possible to prevent degradation factors concentrated at the interface other than the aforementioned controlled free water and uncontrolled free water. It is. Such water-insoluble degradation inhibitors are classified into additive component-3 and additive component-4 described later.

(Additive component-3)
Additive Component-3 is a non-oil-soluble / water-insoluble antioxidant having a solubility in 1 L of hexane at 0 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of less than 0.1 g. The solubility of additive component-3 in water is preferably 0.05 g or less, more preferably 0.01 g or less.

  Examples of the water-insoluble / water-insoluble antioxidant include catechin, epicatechin, epigallocatechin, catechin gallate, epigallocatechin gallate, vitamin C fatty acid ester, water-insoluble rosemary extract (for example, Mitsubishi Chemical Foods, Inc. product name; RM21Bbase), carnosol, carnosic acid and the like. Of these, carnosol and / or carnosic acid are preferred.

  Carnosol and carnosic acid are abundant in herbal spices such as sage, thyme and oregano. The structure is different from other antioxidants, and has an isoprene skeleton apietan structure. Antioxidants such as fats and oils are much stronger than other antioxidants. In addition, it has a conjugated double bond in the structure, and further has a tautomeric structure even under the influence of radicals generated by light. high.

  The carnosol and carnosic acid used in the present invention are preferably natural extracts from the viewpoint of safety. This natural product is extracted from herb-based plants such as sage, thyme, oregano, and an extract from rosemary, which is present in large amounts, is preferred.

  Carnosol and carnosic acid are obtained as a water-insoluble extract of rosemary, and an example of the production method is as follows. First, as in the case of the water-soluble extract described above, extraction with hydrous ethanol, water is added to the extract to precipitate water-insoluble components, activated carbon is added and stirred, and water-insoluble components and The mixture with activated carbon is separated, the resulting mixture is extracted with ethanol, ethanol is distilled off from the resulting extract, and carnosol and carnosic acid are obtained as a powdery concentrate. The details can be referred to the description in Japanese Patent Publication No. 59-4469.

(Additive component-4)
Additive Component-4 is an oil-soluble antioxidant having a solubility in 1 L of hexane at 30 ° C. of 50 g or more. Examples of such oil-soluble antioxidants include tocotrienol, ubiquinone (coQ10), rice oil extract, vitamin E (α, β, γ, δ tocopherol), mixed tocopherol and the like. Among these, vitamin E (including mixed tocopherol) is preferable.

(Additive component-5)
In the present invention, as other components, polyglycerol fatty acid ester such as polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol stearate, polyglycerol oleate, sucrose laurate Esters, sucrose myristic acid esters, sucrose palmitic acid esters, sucrose stearic acid esters, sucrose fatty acid esters such as sucrose oleic acid esters, and the like may be used in combination.

  Next, the use ratio of the above-described additive component will be described.

(In the case of deterioration inhibitor (I))
When the above-mentioned additive component is used in combination with a compound having a dynamic hydration number of 25 or more, the content of the compound having a dynamic hydration number of 25 or more in the deterioration inhibitor (I) is usually 20 to 99 weights. %, Preferably 20 to 80% by weight, more preferably 20 to 60% by weight.

  For compounds having a dynamic hydration number of 25 or more, additive component-1 (non-oil-soluble antioxidant), particularly additive component-2 (non-oil-soluble water-soluble antioxidant) is used in combination. preferable. As mentioned above, rosmarinic acid and / or vitamin C is preferable as additive component-2. The content of additive component-2 in the deterioration inhibitor (I) varies depending on the type, but generally speaking, it is generally 0.01 to 50% by weight, preferably 0.05 to 30% by weight. More preferably, it is 0.1 to 30% by weight. In particular, in the case of rosmarinic acid, the content in the degradation inhibitor (I) is usually 0.1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. is there. If the content of rosmarinic acid is too low, the antioxidant capacity of the deterioration inhibitor tends to deteriorate at the water / oil interface. If the content of rosmarinic acid is too high, it is affected by the metal catalyzed by light. It becomes easy. The weight ratio of the non-oil-soluble / water-soluble antioxidant / the compound having a dynamic hydration number of 25 or more is usually 1/1000 to 1/1, preferably 1/500 to 1/5, more preferably 1. / 200 to 1/10.

  Furthermore, it is preferable to use a compound having a dynamic hydration number of 25 or more in combination with additive component-3 (non-oil-soluble / water-insoluble antioxidant). As described above, as additive component-3, carnosol and / or carnosic acid are preferable. The content of additive component-3 in the deterioration inhibitor (I) is usually 0.05 to 10% by weight, preferably 0.05 to 3% by weight, and more preferably 0.1 to 1% by weight. Non-oil-soluble / water-soluble antioxidant / compound having a dynamic hydration number of 25 or more / total weight ratio of carnosol and carnosic acid, usually 1/1000 / 0.1 / 1/10, preferably 1 / 500 / 0.1 to 1/5/10, more preferably 1/200 / 0.1 to 1/10/10.

  In the present invention, instead of additive component-3, additive component-4 can be used in combination. As additive component-4, vitamin E is preferred as described above. The content of additive component-4 and the weight ratio to other components are the same as in additive component-3.

  Moreover, since the usage rate of additive component-5 changes with kinds, it cannot unconditionally be prescribed | regulated. Therefore, the use ratio of the additive component-5 is appropriately selected from a range that does not impair the effect of the deterioration inhibitor (I).

(In the case of deterioration inhibitor (II))
When using the above-mentioned additive ingredients in combination with trisaccharide or higher oligosaccharides, polysaccharides or derivatives thereof (hereinafter these are represented by maltotriose), the content of maltotriose in the degradation inhibitor (II) is The amount is usually 20 to 99% by weight, preferably 20 to 80% by weight, and more preferably 20 to 60% by weight.

  The aforementioned additive components can be combined with maltotriose, and the modes thereof are all the same as those of the above-described mode in the case of the deterioration inhibitor (I).

  That is, the content of additive component-2 in the deterioration inhibitor (II) is usually 0.01 to 50% by weight, preferably 0.05 to 30% by weight, more preferably 0.1 to 30% by weight. However, in the case of rosmarinic acid, it is usually 0.1 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight. The weight ratio of non-oil-soluble / water-soluble antioxidant / maltotriose is usually 1/1000 to 1/1, preferably 1/500 to 1/5, more preferably 1/200 to 1/10. is there. The content of additive component-3 in the deterioration inhibitor (II) is usually 0.05 to 10% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 to 1% by weight. . Non-oil-soluble / water-soluble antioxidant / maltotriose / carnosol and carnosic acid in total weight ratio, usually 1/1000 / 0.1 / 1/10, preferably 1/500 / 0.1-1 / 5/10, more preferably 1/200 / 0.1 to 1/10/10.

  The deterioration inhibitor of the present invention is produced by mixing the above-described components. The mixing order is not particularly limited. The form of the deterioration preventing agent of the present invention is usually a solution in which each of the above components is dissolved in water or a mixed solvent of ethanol-water. When carsonol and carnosic acid are used in combination, they are usually dissolved in a mixed solvent of ethanol and water. This solution is usually prepared by mixing the above-mentioned components, adding ethanol thereto, and then adding water. The mixing ratio of water and ethanol is usually 1: 1 to 3: 1. The antioxidant of the present invention may be in the form of a powder and can be prepared by spray drying or freeze drying the above solution.

  The deterioration inhibitor of the present invention can be preferably used for foods and cosmetics that are easily deteriorated. The amount of addition at that time has an optimum range for each type of product, but in general, it is generally 0.001 to 30% by weight, preferably 0.01 to 10% by weight, more preferably based on the product. 0.05 to 5% by weight.

<Products using the deterioration inhibitor of the present invention>
(Food)
As the food of the present invention, a food that easily deteriorates can be preferably used. Specific examples include beverages, milk beverages, alcoholic beverages, cooked rice, beans (rice, wheat, barley, corn, awa, hie), bread, other flour products, noodles, curry, stew roux, retort products, seasonings Food, dairy products such as ice cream, feed (including pet food).

  Moreover, as fishery products, livestock meat, and processed fats and oils in foods, marine products, livestock meat, processed fats and oils that are easily deteriorated, and fishery products, livestock meat, and processed fats and oils that are stored for a long time can be preferably used. Specific examples include fresh fish, dried fish, dried overnight, dried mirin, shellfish, red fish, crustacean pigment preservation agent, surimi, fish paste product, delicacy, fish sausage, salted product, seaweed, seaweed food, α-linolenic acid, Unsaturated polyvalent fatty acids such as docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) and their triglycerides, foods containing them, chicken, pork, beef, lamb, sausage, ham, processed products, cornflakes , Instant noodles, oil confectionery using fats and oils, fast spread, margarine, etc.

  The use ratio of the deterioration inhibitor of the present invention is usually 0.001 to 30% by weight, preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the food.

(Cosmetics)
As the cosmetic of the present invention, a cosmetic that easily deteriorates can be preferably used. Specific examples thereof include humectants, whitening agents, cleansings, lotions, detergents, softeners, finishing agents, dishwashing detergents, vegetables, fruit cleaning agents, rinse agents and the like. The use ratio of the deterioration inhibitor of the present invention is usually 0.001 to 30% by weight, preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the cosmetic.

(Glaze agent)
Covering the fish surface with ice when freezing the landed fish is called glaze, and the agent that uniformly covers ice on the fish surface is called glaze agent. The use ratio of the deterioration inhibitor of the present invention is usually 0.001 to 30% by weight, preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the glaze agent.

(Plastic products)
By adding the deterioration preventing agent of the present invention to a plastic product, it is possible to indirectly prevent deterioration of food, drink, cosmetics and other products through the plastic product. Specific examples of such plastic products include food and beverage products, cosmetic plastic containers, baluns, food packaging materials such as prepared food storage packs, deodorants, sanitary packaging materials such as liquid detergents, refrigerators, air conditioners, Examples include white appliances such as air purifiers and washing and drying machines, air conditioners used in ships, automobiles, trains, airplanes, buildings, and the like. The use ratio of the deterioration inhibitor of the present invention is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the plastic product.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.

Production Example 1 (Production of rosemary water-soluble extract):
10 kg of 50% aqueous ethanol was added to 1 kg of rosemary, heated under reflux for 3 hours, and filtered while warm to obtain a filtrate. The operation of extracting the residue with 6 L of 50% aqueous ethanol in the same manner was repeated twice more to obtain a filtrate. These filtrates were combined, and 5 L of water was added to precipitate a precipitate. 100 g of activated carbon was added thereto, stirred for 1 hour, stored in a cold place overnight, and then filtered to obtain a filtrate. The filtrate was concentrated under reduced pressure to obtain 120 g of a rosemary water-soluble extract (rosmarinic acid content: 31.6 wt%).

Production Example 2 (Production of rosemary water-insoluble extract):
10 kg of 50% aqueous ethanol was added to 1 kg of rosemary, heated under reflux for 3 hours, and filtered while warm to obtain a filtrate. The operation of extracting the residue with 6 L of 50% aqueous ethanol in the same manner was repeated twice more to obtain a filtrate. These filtrates were combined, and 5 L of water was added to precipitate a precipitate. 100 g of activated carbon was added thereto, stirred for 1 hour, stored in a cold place overnight, and then filtered to obtain a mixture of precipitate and activated carbon. 4 L of ethanol was added to this mixture, and the mixture was heated to reflux for 3 hours and filtered while warm to obtain a filtrate. The operation of extracting the residue in the same manner with 2.4 L of ethanol was repeated twice more to obtain a filtrate. These filtrates were combined, concentrated under reduced pressure, and ethanol was distilled off to obtain a powdery rosemary water-insoluble extract (contents of carnosol and carnosic acid: 24.9 wt%).

Examples 1 to 13 and Comparative Examples 1 to 6 (Aji Deterioration Prevention Test):
Aji deterioration prevention test was conducted in the following manner. First, a horse mackerel was prepared, the horse mackerel was opened, the surface was washed with water, and immersed in 2 L of 10 wt% salt water to which 20 mL of a deterioration inhibitor sample was added for 1 hour. After immersion, the horse mackerel was washed and dried at 25 ° C. for 2 hours. After drying, it was stored at 5 ° C., and visual evaluation of the deterioration state of each horse mackerel after 8 days was performed according to the criteria shown in Table 3 below.

  The components shown in Table 4 below were mixed so that the weight ratios shown in the table were obtained, and 4 ml of ethanol and the remainder were dissolved using water to prepare a 20 ml deterioration preventing agent sample. A prevention test was performed. The results are shown in Table 4. Details of each component shown in Table 4 are shown in Table 5.

Example 13 and Comparative Example 5 (photodegradation prevention test for milk):
The following test was conducted to prevent the photodegradation of milk. That is, a product prepared by adding 1 ml of the deterioration inhibitor of Example 6 to 100 ml of milk (Example 13) and an additive-free product (Comparative Example 5) were irradiated with light having a total light amount of 20,000 lux for 48 hours (5 ° C. )did. Thereafter, the amount of hexanal, which is a volatile component, was measured by headspace gas chromatography (Agilent 6890GC), and the degree of milk degradation was evaluated by comparing the area component ratio of hexanal with that without addition. Conversion was made assuming that no additives were added. The results are shown in Table 6.

  From the results of the above Examples 1 to 13, it is clear that the degradation inhibitor of the present invention is effective against oxidative degradation and light degradation.

Claims (10)

  A compound having a dynamic hydration number of 25 or more and an antioxidant (additive component-2) having a solubility in 1 L of hexane at 30 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of 0.1 g or more. And an antioxidant (additive component-3) having a solubility in 1 L of hexane at 30 ° C. of less than 50 g and a solubility in 100 g of water at 25 ° C. of less than 0.1 g. 2. A deterioration inhibitor, wherein the content of 2 is 0.01 to 50% by weight, and the content of additive component-3 is 0.05 to 10% by weight.   The deterioration inhibitor according to claim 1, wherein the compound having a dynamic hydration number of 25 or more is one or more compounds selected from the group consisting of sugars, sugar alcohols, proteins, and peptides.   The deterioration inhibitor according to claim 1 or 2, wherein additive component-2 is rosmarinic acid and / or vitamin C.   The deterioration inhibitor according to any one of claims 1 to 3, wherein the additive component-3 is carnosol and / or carnosic acid.   The deterioration inhibitor according to any one of claims 1 to 4, further comprising an antioxidant having a solubility in 1 L of hexane at 30 ° C of 50 g or more.   6. The antioxidant according to claim 5, wherein the antioxidant is vitamin E.   A food comprising the deterioration inhibitor according to any one of claims 1 to 6.   Cosmetics containing the deterioration inhibitor according to any one of claims 1 to 6.   A glaze agent comprising the deterioration inhibitor according to any one of claims 1 to 6.   A plastic product comprising the deterioration preventing agent according to any one of claims 1 to 6.