WO2013172348A1 - 食用油脂及びそれを含有する食品並びにその製造方法 - Google Patents
食用油脂及びそれを含有する食品並びにその製造方法 Download PDFInfo
- Publication number
- WO2013172348A1 WO2013172348A1 PCT/JP2013/063428 JP2013063428W WO2013172348A1 WO 2013172348 A1 WO2013172348 A1 WO 2013172348A1 JP 2013063428 W JP2013063428 W JP 2013063428W WO 2013172348 A1 WO2013172348 A1 WO 2013172348A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fats
- oil
- water
- edible
- oils
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
- C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
- C11B5/0035—Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
- A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
- A23D7/0053—Compositions other than spreads
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
- A23D9/013—Other fatty acid esters, e.g. phosphatides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B5/00—Preserving by using additives, e.g. anti-oxidants
- C11B5/0085—Substances of natural origin of unknown constitution, f.i. plant extracts
Definitions
- the present invention relates to an edible oil and fat, a food containing the same, and a method for producing the same. More specifically, the present invention relates to edible fats and oils that have been improved in oxidative stability, required for foods containing oils and fats, foods containing the same, and methods for producing the same.
- Oxidation stability of food is one of important functions because there are foods that directly or indirectly affect the setting of the shelf life, and attempts have been made to improve oxidation stability by various methods.
- fats and oils are one of the important compositions in foods.
- improvement in the oxidation stability of fats and oils is particularly important in foods containing fats and oils.
- an antioxidant In order to improve the oxidative stability of fats and oils and foods containing fats, an antioxidant is generally added. Oil-soluble antioxidants that are easy to disperse in fats and oils are used, but their antioxidant capacity is relatively low compared to water-soluble antioxidants, and water-soluble antioxidants are dispersed in fats and oils. There are many uses. Several methods have been disclosed in which a water-soluble antioxidant substance is dispersed in fats and oils to improve the oxidative stability of fats or foods containing a large amount of fats and oils.
- An example is a method in which an aqueous phase containing a water-soluble antioxidant substance is added to fats and oils as an oil-soluble substance water-in-water emulsion using an emulsifier.
- a water-soluble antioxidant substance one or two or more lipophilic emulsifiers together with 100 parts by weight of an aqueous solution containing one or more water-soluble antioxidant active substances, if necessary, with a synergist
- a water-in-oil type lipophilic antioxidant emulsified with 1 to 500 parts by weight is disclosed.
- Patent Document 2 1 to 40 parts by weight of a water-soluble compound excluding catechins and 1 to 35 parts by weight of an emulsifier having an HLB of 6 to 14 are dissolved in 1 to 40 parts by weight of water or alcohol as water-soluble antioxidants. Then, 5 to 70 parts by weight of polyglycerol condensed ricinoleic acid ester is added to the obtained solution to prepare a water-in-poly emulsion of polyglycerin condensed ricinoleic acid ester, and 0.5 to 30 wt.
- An oil-solubilized preparation of a water-soluble compound that is soluble in fats and oils, obtained by adding parts and thoroughly mixing is disclosed.
- Patent Document 3 as a water-soluble antioxidant, ascorbic acid, erythorbic acid, kojic acid, gallic acid, malic acid and other antioxidants that are sparingly soluble in fats and oils are dissolved in a lower alkyl alcohol such as ethanol, and then citrated.
- An antioxidant composition having good solubility in fats and oils by dissolving in an organic acid monoglyceride such as acid monoglyceride and further dissolving the mixed solution in a polyglycerin condensed ricinoleate is disclosed.
- Patent Document 4 tea leaves pulverized to an average particle size of about 1-5 microns in a dry state are added to edible oil, and the mixture is further refined with a wet ultrafine mill until the tea leaves have a particle size of 1 -1 0 microns.
- a process for obtaining an oily solution by performing a chemical treatment to promote the transfer of tea leaf components to edible oil and then removing fine tea leaf powder is disclosed.
- Patent Document 5 discloses a method of stably dispersing a water-soluble polyphenol in an oily solution for a long time as a preparation and a production method capable of effectively exerting a bactericidal action against both gram positive bacteria and gram negative bacteria. ing. Specifically, after mixing a polyphenol extract in an oily solution containing medium chain fatty acid triglyceride, the polyphenol extract is made into nanoparticles by wet pulverization, and the polyphenol extract is stably dissolved in the oily solution. It is.
- Patent Document 6 has a problem of suppressing heating odor and deterioration odor of fats and oils, and adding a fat-and-oil-insoluble organic acid to the fats and oils in an aqueous solution, under reduced pressure conditions of 50 to 180 ° C. and 0.5 to 100 torr.
- a method for producing fats and oils characterized by dehydration is disclosed.
- Patent Document 7 discloses a method for stabilizing hot cooking oil, which includes the step of periodically introducing an aqueous composition containing at least one antioxidant into hot cooking oil.
- Patent Documents 1 to 3 require the addition of a relatively large amount of an emulsifier in order to solubilize the water-soluble antioxidant.
- the present inventors have conducted research on the assumption that the cause of an unfavorable flavor is derived from an emulsifier.
- Patent Document 4 there is a problem that the process is considerably complicated because a process of removing the tea leaves by pulverizing, filtering and centrifuging is necessary.
- Patent Document 5 the oil and fat for dispersing the water-soluble polyphenol is limited to a medium-chain fatty acid triglyceride, and there is a problem that a very special wet pulverization apparatus for forming nanoparticles is essential.
- Patent Document 6 is an invention for the purpose of suppressing heating odor and deterioration odor of fats and oils, and does not describe antioxidant substances and water-soluble polyphenols.
- Patent Document 7 an aqueous composition containing an antioxidant that is inherently insoluble in fats and oils is directly put into hot cooking oil, and uniform dispersibility of the antioxidant cannot be expected.
- An object of the present invention is to disperse a water-soluble antioxidant substance in an edible oil and fat by a simple method to provide an edible oil and fat having excellent oxidation stability and good flavor.
- the present inventors have conducted extensive research, and as a result, by adding a water-soluble antioxidant substance, which is inherently poorly soluble in fats and oils, to the fats and oils in a solution state using an aqueous medium, It was found that edible fats and oils having excellent oxidation stability and good flavor could be obtained without containing an emulsifier as much as possible, and the present invention was completed.
- the present invention (1) Edible fats and oils containing 5 to 1000 ppm by weight of water-soluble antioxidants in the total amount of fats and oils, and the emulsifier content in the fats and oils is not more than twice the water-soluble antioxidants content, (2) Edible oil and fat according to (1), wherein the water-soluble antioxidant is tea polyphenol, (3) Edible fats and oils mainly made from palm oil, wherein the content of the water-soluble antioxidant is 5 to 50 ppm by weight, and the emulsifier is not contained (1) or (2) (4) Edible fats and oils mainly made from palm oil, the content of water-soluble antioxidants is 30 to 1000 ppm by weight, and the A / N value obtained by the following method is 1.6 or more Any edible oil or fat according to any one of (1) to (3), A: CDM stability time of edible oils and fats containing 30 to 1000 ppm by weight of water-soluble antioxidants N: CDM stability time of base oils and fats of the above-mentioned A containing no antioxidants (5)
- an oxidative stability is improved by a simple method, and an edible fat with good flavor is obtained.
- an edible fat according to the present invention excellent oxidative stability can be obtained. It is possible to provide a food product having a good flavor.
- Oils and oils that can be used include soybean oil, rapeseed oil, corn oil, cottonseed oil, peanut oil, sunflower oil, rice bran oil, safflower oil, safflower oil, olive oil, sesame oil, palm oil, palm oil, palm kernel oil, etc.
- vegetable fats and oils such as beef tallow and pork tallow, processed fats and oils subjected to fractionation, hydrogenation, transesterification and the like, and mixed fats and oils thereof. The effect of the present invention can be obtained regardless of the type of oil.
- Water-soluble antioxidant means a compound used as a water-soluble antioxidant.
- water-soluble polyphenols can be used.
- water-soluble polyphenols include tea extract, rosemary extract, and bayberry extract. Such water-soluble antioxidants may be used alone or in combination.
- water-soluble antioxidants may be used alone or in combination.
- preferable water-soluble polyphenols include tea polyphenols contained in tea extracts. Even when combined with an oil-soluble antioxidant such as tocopherol, the function of the water-soluble antioxidant can be used without being impaired.
- tea polyphenols examples include water-soluble polyphenols obtained by extraction from tea leaves using an aqueous medium such as hot water and alcohol. Tea polyphenols are mainly composed of catechins, and it is known that there are eight types of typical catechins. Examples of gallate-type catechin lees include epigallocatechin gallate, epicatechin gallate, catechin gallate, and gallocatechin gallate. . Examples of free catechins include epigallocatechin, epicatechin, catechin, and gallocatechin. In addition to such catechins, tea polyphenols include oxidized polyphenols generated by the fermentation state of tea leaves. In the present invention, it is preferable to use tea polyphenol containing one or more of such catechins and polyphenols.
- a commercially available tea polyphenol-containing composition having a polyphenol concentration adjusted to a certain concentration range is preferably used, and most preferably a water-soluble product not adjusted with an emulsifier or the like.
- preferable tea polyphenol-containing compositions include those manufactured by Taiyo Kagaku Co., Ltd., trade names: Sunphenon, Mitsubishi Chemical Foods, Inc., trade names: Sunfood, and the like. Since it can be efficiently dispersed in fats and oils at a high concentration, the higher the polyphenol content in the tea polyphenol-containing composition, the better.
- the tea polyphenol-containing composition preferably contains at least 50% tea polyphenol. .
- the edible oil / fat of the present invention contains 5 wt ppm to 1000 wt ppm of a water-soluble antioxidant in the total amount of the fat.
- the water-soluble antioxidant is 15 wt ppm to 1000 wt ppm, such as 15 wt ppm to 600 wt ppm, and more preferably the water soluble antioxidant is 30 wt ppm to 1000 wt ppm, such as 30 wt ppm to 600 ppm by weight, more preferably 150 ppm to 1000 ppm by weight of water-soluble antioxidants, such as 150 ppm to 600 ppm by weight, most preferably 300 ppm to 1000 ppm of water-soluble antioxidants.
- Weight ppm such as 300 ppm to 600 ppm by weight. If the content of the water-soluble antioxidant in the edible fat is less than 5 ppm by weight, a sufficient effect of improving the oxidative stability cannot be obtained, and if it exceeds 1000 ppm by weight, a homogeneous dispersion state cannot be obtained.
- the emulsifier content is 2 times or less, preferably 1.5 times or less, more preferably 1.2 times or less, and still more preferably 1.0 times or less of the water-soluble antioxidant content. If the emulsifier content exceeds twice the content of the water-soluble antioxidant substance, an unfavorable flavor derived from the emulsifier comes to be felt, and the original good flavor of food cannot be obtained.
- the edible oil / fat of the present invention is an edible oil / fat preferably made of palm oil as a main raw material, and is an edible oil / fat containing a water-soluble antioxidant substance in an amount of 5 to 50 ppm by weight and containing no emulsifier. More preferably, the content of the water-soluble antioxidant is 5 to 40 ppm by weight, and the edible oil does not contain an emulsifier, and more preferably the content of the water-soluble antioxidant is 5 to 30 ppm. It is an edible fat and oil containing no weight ppm and an emulsifier.
- CDM stability is a value indicating the oxidation stability of fats and oils.
- the value obtained by the CDM stability test is referred to as “CDM stability time” and is used as an index for evaluating oxidation stability. The longer the CDM stability time, the better the oxidation stability.
- the CDM stability test method is in accordance with the standard oil analysis method 2.5.1.2-1996. Specifically, clean air is fed while heating the fats and oils to 120 ° C. in a reaction vessel, and volatile decomposition products generated by oxidation are collected in water, and the conductivity of water is continuously measured. The time until the bending point at which the value changes abruptly indicates the “CDM stability time”.
- the edible oil / fat of the present invention preferably comprises palm oil as a main raw material, the content of the water-soluble antioxidant is 150 wt ppm to 400 wt ppm, such as 150 wt ppm to 300 wt ppm, and the emulsifier content is 500 wt ppm or less.
- the content of the emulsifier in the oil and fat is 1.5 times or less the content of the water-soluble antioxidant, and the A / N value obtained by the following method is 1.9 or more.
- N CDM stability time of the base oil and fats of A above that do not contain an antioxidant substance
- the edible oil / fat of the present invention is more preferably made of palm oil as a main raw material, and the content of the water-soluble antioxidant is 300 wt ppm to 1000 wt ppm, for example, 300 wt ppm to 600 wt ppm, and the emulsifier content in the fat / oil Is 1.5 times or less the water-soluble antioxidant content, and the A / N value obtained by the following method is 2.9 or more.
- N CDM stability time of the base fat and oils of the above-mentioned A containing no antioxidant substance
- the emulsifier used in the present invention is not particularly limited as long as it is an emulsifier having a W / O type emulsifying action, and polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester and the like can be used.
- polyglycerin condensed ricinoleic acid ester can be used.
- the method for obtaining the edible oil / fat of the present invention is not particularly limited as long as a water-soluble antioxidant can be dispersed in the oil / fat.
- a water-soluble antioxidant can be dispersed in the oil / fat.
- an edible oil / fat containing tea polyphenol is obtained, the tea polyphenol is obtained.
- An aqueous solution in which 1% by weight of the contained composition is dissolved is prepared, and a prescribed amount is added to the oil and fat, and then treated for 15 minutes to 1 hour with stirring under reduced pressure at 50 to 180 ° C. and 0.5 to 100 torr
- edible fats and oils containing tea polyphenol and having a water content of 0.1% by weight or less can be obtained.
- the concentration of the aqueous solution for dissolving the tea polyphenol-containing composition is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight. If it is less than 1% by weight, when such an aqueous solution is added to fats and oils, the amount of water with respect to the fats and oils increases, and it takes a long time to remove the water, which is not preferable. Moreover, when it exceeds 50 weight%, since the tea polyphenol contained in a tea polyphenol containing composition precipitates and the content to fats and oils falls, it is unpreferable.
- the temperature is preferably 50 to 180 ° C., and if it is lower than 50 ° C., it takes a long time to remove moisture, which is not preferable.
- the decompression condition is preferably 0.5 to 100 torr, and is preferably as low as possible.
- the edible oil / fat of the present invention can be used in combination with other edible fat / oil. It is preferable to mix 20% by weight or more of the edible oil / fat of the present invention, more preferably 50% by weight or more, and more preferably use of the edible oil / fat of the present invention alone provides excellent oxidative stability. This is preferable.
- the edible oil / fat of the present invention can be used for foods generally containing edible oil / fat.
- Preferable uses include foods in which oils and fats are exposed on the surface of foods, fries, sprays, coatings, powders and oils, and the like.
- the common functions required of edible fats and oils in such foods are to improve the texture, impart flavor, improve oxidative stability that affects the shelf life of the food, and maintain the flavor of the food.
- the fats and oils for heat cooking represented by the frying etc. can be illustrated. This is because edible fats and oils are exposed to oxygen in the air at high temperatures, and therefore edible fats and oils having excellent oxidation stability are required.
- the edible oil / fat of the present invention for such food, a food having excellent oxidation stability and good flavor can be obtained, and a remarkable effect can be obtained.
- unprocessed palm oil such as fractionation, palm stearin, palm olein, palm middle melting point oil and fat, and processed oil and fat subjected to further separation, hydrogenation, transesterification, and the like, and mixed oils and fats thereof Etc. can be illustrated.
- edible fats and oils of the present invention may contain additives that can be used for edible fats and oils, such as fragrances, pigments, and silicones, in addition to antioxidants.
- a tea polyphenol-containing composition (manufactured by Taiyo Kagaku Co., Ltd .: trade name: Sanphenon 90S) is added to water to prepare an aqueous solution in which the 10 wt% tea polyphenol-containing composition is dissolved. Next, low-melting palm oil heated to 50 ° C.
- a tea polyphenol-containing composition (manufactured by Taiyo Kagaku Co., Ltd .: trade name: Sanphenon 90S) is added to water to prepare an aqueous solution in which the 1 wt% tea polyphenol-containing composition is dissolved.
- an aqueous solution in which a 1% by weight tea polyphenol-containing composition is dissolved in 1 kg of low-melting palm oil heated to 50 ° C. palm oil low-melting fraction, manufactured by Fuji Oil Co., Ltd., trade name: Palm Ace iodine value 67).
- a tea polyphenol-containing composition (manufactured by Taiyo Kagaku Co., Ltd .: trade name: Sanphenon 90S) is added to water to prepare an aqueous solution in which the 1 wt% tea polyphenol-containing composition is dissolved.
- an aqueous solution in which a 1% by weight tea polyphenol-containing composition is dissolved in 1 kg of low-melting palm oil heated to 50 ° C. (palm oil low-melting fraction, manufactured by Fuji Oil Co., Ltd., trade name: Palm Ace iodine value 67).
- Flavor evaluation method of edible fats and oils Flavor evaluation of edible fats and oils after temperature adjustment is performed at 20 ° C. 10 panelists evaluated in five levels, “5”, “4”, “3”, “2”, “1”, in the order of superior taste by smell and taste, and evaluated the average evaluation score As a result. A score of 4 or more was accepted.
- Flavor evaluation method of corn puffs 50 parts by weight of edible oils and fats are sprayed on 100 parts by weight of spherical corn puffs (manufactured by Kinoshita Co., Ltd.) having a diameter of about 10 mm, and the taste is evaluated by eating.
- Example 1 The edible fat / oil A was used as the edible fat / oil as it was. This edible fat was evaluated according to the above method. The results are summarized in Table 1.
- Example 2 50 parts by weight of low melting point palm oil (palm oil low melting point fraction, manufactured by Fuji Oil Co., Ltd., trade name: palm ace iodine value 67) is added to 50 parts by weight of edible fat and oil A tea polyphenol 300 weight ppm, emulsifier An edible fat containing 400 ppm by weight was obtained. This edible fat was evaluated according to the above method. The results are summarized in Table 1.
- Example 3 75 parts by weight of low melting point palm oil (palm oil low melting point fraction, manufactured by Fuji Oil Co., Ltd., trade name: Palm Ace iodine number 67) is added to 25 parts by weight of edible fat and oil A tea polyphenol 150 weight ppm, emulsifier An edible fat containing 200 ppm by weight was obtained. This edible fat was evaluated according to the above method. The results are summarized in Table 1.
- Example 5 The edible oil / fat C was used as the edible oil / fat as it was. This edible fat was evaluated according to the above method. The results are summarized in Table 1.
- an edible fat and oil that has improved the oxidative stability required for a food containing fats and oils, a food containing the same, and a method for producing the same.
Abstract
Description
すなわち、本発明は、
(1) 油脂全量に水溶性抗酸化物質を5重量ppm~1000重量ppm含有し、かつ該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の2倍以下である食用油脂、
(2) 水溶性抗酸化物質が、茶ポリフェノールである(1)の食用油脂、
(3) パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が5重量ppm~50重量ppm、および乳化剤を含有しない(1)または(2)の食用油脂、
(4) パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が30重量ppm~1000重量ppm、および下記方法で得られるA/Nの値が1.6以上である(1)~(3)のいずれかの食用油脂、
A:水溶性抗酸化物質を30重量ppm~1000重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間
(5) パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が30重量ppm~600重量ppm、乳化剤含有量が800重量ppm以下、該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の1.5倍以下、および下記方法で得られるA/Nの値が1.6以上である(1)~(3)のいずれかの食用油脂、
A:水溶性抗酸化物質を30重量ppm~600重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間
(6) パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が150重量ppm~400重量ppm、乳化剤含有量が500重量ppm以下、該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の1.5倍以下、および下記方法で得られるA/Nの値が1.9以上である(1)または(2)の食用油脂、
A:水溶性抗酸化物質を150重量ppm~400重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間
(7) (1)~(6)のいずれかの食用油脂を使用した食品、
(8) (1)~(6)のいずれかの食用油脂を使用した食品の酸化安定性を向上させる方法、
(9) (1)~(6)のいずれかの食用油脂を、加熱調理用油脂または、スプレー用油脂として用いる事によって得られる食品、
(10) 水溶性抗酸化物質を水性媒体に加えて、溶液状態で油脂に添加することを特徴とする(1)~(6)のいずれかの食用油脂の製造方法、
(11) 水溶性抗酸化物質を水性媒体に加えて、溶液状態で油脂に添加後、減圧下で水分除去することを特徴とする(10)の食用油脂の製造方法、である。
A:水溶性抗酸化物質を150重量ppm~400重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間
A:水溶性抗酸化物質を300重量ppm~1000重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間
茶ポリフェノールを含有する食用油脂の作製において、太陽化学株式会社製サンフェノン90Sを、茶ポリフェノール含有組成物として使用する。かかる茶ポリフェノール含有組成物中のポリフェノール含有量が80重量%以上であることより、茶ポリフェノール含有組成物中の茶ポリフェノール含有量は80重量%として、食用油脂中の茶ポリフェノール含有量を算出した。
茶ポリフェノール含有組成物(太陽化学株式会社製:商品名:サンフェノン90S)を水に加え、10重量%茶ポリフェノール含有組成物が溶解した水溶液を作製する。次いで50℃に加温した低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)1kgに、乳化剤(理研ビタミン株式会社製 ポエムPR-100)を0.8g加えて溶解し、さらに10重量%茶ポリフェノール含有組成物が溶解した水溶液を7.5g加えた後、ホモミキサー(TK ROBO MIX:特殊機化工業株式会社製)にて10000rpmx10分の撹拌を行った。その後、50℃、10torrの減圧条件下で、攪拌しながら30分間脱水処理を行い、茶ポリフェノール600重量ppm、乳化剤800重量ppmを含有する低融点パーム油(食用油脂A)を得た。
茶ポリフェノール含有組成物(太陽化学株式会社製:商品名:サンフェノン90S)を水に加え、1重量%茶ポリフェノール含有組成物が溶解した水溶液を作製する。次いで50℃に加温した低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)1kgに、1重量%茶ポリフェノール含有組成物が溶解した水溶液を3.75g加えた後、ホモミキサー(TK ROBO MIX:特殊機化工業株式会社製)にて10000rpmx10分の撹拌を行った。その後、50℃、10torrの減圧条件下で、攪拌しながら30分間脱水処理を行い、茶ポリフェノール30重量ppm含有する低融点パーム油(食用油脂B)を得た。
茶ポリフェノール含有組成物(太陽化学株式会社製:商品名:サンフェノン90S)を水に加え、1重量%茶ポリフェノール含有組成物が溶解した水溶液を作製する。次いで50℃に加温した低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)1kgに、1重量%茶ポリフェノール含有組成物が溶解した水溶液を1.9g加えた後、ホモミキサー(TK ROBO MIX:特殊機化工業株式会社製)にて10000rpmx10分の撹拌を行った。その後、50℃、10torrの減圧条件下で、攪拌しながら30分間脱水処理を行い、茶ポリフェノール15重量ppm含有する低融点パーム油(食用油脂C)を得た。
(1)食用油脂の風味評価方法
20℃に温度調整後の食用油脂の風味評価を行う。パネラー10名により、嗅覚と味覚により風味が優れている順に「5 」、「4 」、「3 」、「2 」、「1 」の五段階にて評価を行い、平均化した評価点数を評価結果とした。4点以上を合格とした。
(2)コーンパフの風味評価方法
直径約10mmの球状コーンパフ(株式会社きのした製)100重量部に対し、食用油脂を各50重量部スプレーし、喫食し風味評価を行う。パネラー10名により、嗅覚と味覚により風味が優れている順に「5 」、「4 」、「3 」、「2 」、「1 」の五段階にて評価を行い、平均化した評価点数を評価結果とした。4点以上を合格とした。
(3)CDM安定性時間
メトローム社製CDM試験機ランシマットを使用して食用油脂の酸化安定性を評価する。各食用油脂の酸化安定性の判定は、食用油脂の酸化安定性の増加に相関してCDM安定性時間が延びることによる時間差の比較により行った。測定条件:測定温度120℃、空気吹き込み量20L/h、油脂検体3g仕込み。
食用油脂Aをそのまま食用油脂として用いた。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
食用油脂A 50重量部に対して 低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)を50重量部加え 茶ポリフェノール300重量ppm、乳化剤を400重量ppm含有する食用油脂を得た。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
食用油脂A 25重量部に対して 低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)を75重量部加え 茶ポリフェノール150重量ppm、乳化剤を200重量ppm含有する食用油脂を得た。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
食用油脂Bをそのまま食用油脂として用いた。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
食用油脂Cをそのまま食用油脂として用いた。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)に、油溶性の茶ポリフェノール含有製剤(太陽化学株式会社製、商品名:サンカトールM97、茶ポリフェノール10%含有、ミックストコフェロール9%含有、グリセリン脂肪酸エステル64%、食品素材17%)を1500重量ppm添加し食用油脂を得た。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。茶ポリフェノール含有製剤に含まれるグリセリン脂肪酸エステル64%を乳化剤含有量として算出し、表1に記載した。
低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)にミックストコフェロール135重量ppm加え、食用油脂を得た。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
低融点パーム油(パーム油低融点画分、不二製油株式会社製、商品名:パームエース ヨウ素価67)をそのまま食用油脂として用いた。この食用油脂を上記の方法に従って評価した。結果を表1 に纏めた。
表1 において、実施例1~5の風味評価結果は、(1)食用油脂(2)コーンパフ 何れの風味評価も良好な結果が得られた。比較例1では、(1)食用油脂(2)コーンパフ 何れも異風味が強く、コーンパフの風味を著しく害する結果であった。
表1 において、実施例5の (3)CDM安定性時間は、比較例2、3 と対比して、優位に延長された結果が得られた。実施例1~4では茶ポリフェノール含有量の増加に伴いさらに(3)CDM安定性時間が延長された。
上記結果から明らかなように本発明により得られる実施例1~5では、(1)食用油脂の風味評価(2)コーンパフの風味評価(3)CDM安定性時間、何れも良好な結果が得られた。
下記方法でA/Nの値を算出して、CDM安定性時間を指標として酸化安定性を対比し評価した。評価結果を表2に示す。
A:実施例1~実施例5で得られたCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂、比較例3のCDM安定性時間
Claims (11)
- 油脂全量に水溶性抗酸化物質を5重量ppm~1000重量ppm含有し、かつ該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の2倍以下である食用油脂。
- 水溶性抗酸化物質が、茶ポリフェノールである請求項1に記載の食用油脂。
- パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が5重量ppm~50重量ppm、及び乳化剤を含有しない請求項1又は請求項2に記載の食用油脂。
- パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が30重量ppm~1000重量ppm、及び下記方法で得られるA/Nの値が1.6以上である請求項1~請求項3のいずれか1項に記載の食用油脂。
A:水溶性抗酸化物質を30重量ppm~1000重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間 - パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が30重量ppm~600重量ppm、乳化剤含有量が800重量ppm以下、該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の1.5倍以下、及び下記方法で得られるA/Nの値が1.6以上である請求項1~請求項3のいずれか1項に記載の食用油脂。
A:水溶性抗酸化物質を30重量ppm~600重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間 - パーム油を主要原料とする食用油脂であって、水溶性抗酸化物質の含有量が150重量ppm~400重量ppm、乳化剤含有量が500重量ppm以下、該油脂中の乳化剤含有量が水溶性抗酸化物質含有量の1.5倍以下、及び下記方法で得られるA/Nの値が1.9以上である請求項1又は請求項2に記載の食用油脂。
A:水溶性抗酸化物質を150重量ppm~400重量ppm含有する食用油脂のCDM安定性時間
N:抗酸化物質を含まない前記Aのベース油脂のCDM安定性時間 - 請求項1~請求項6のいずれか1項に記載の食用油脂を使用した食品。
- 請求項1~請求項6のいずれか1項に記載の食用油脂を使用した食品の酸化安定性を向上させる方法。
- 請求項1~請求項6のいずれか1項に記載の食用油脂を、加熱調理用油脂又は、スプレー用油脂として用いる事によって得られる食品。
- 水溶性抗酸化物質を水性媒体に加えて、溶液状態で油脂に添加することを特徴とする請求項1~請求項6のいずれか1項に記載の食用油脂の製造方法。
- 水溶性抗酸化物質を水性媒体に加えて、溶液状態で油脂に添加後、減圧下で水分除去することを特徴とする請求項10に記載の食用油脂の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013546522A JP5652557B2 (ja) | 2012-05-16 | 2013-05-14 | 食用油脂及びそれを含有する食品並びにその製造方法 |
US14/400,107 US20150159117A1 (en) | 2012-05-16 | 2013-05-14 | Edible fat or oil, food containing same, and process for producing same |
EP13789984.5A EP2850949B1 (en) | 2012-05-16 | 2013-05-14 | Edible fat or oil and process for producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-112460 | 2012-05-16 | ||
JP2012112460 | 2012-05-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013172348A1 true WO2013172348A1 (ja) | 2013-11-21 |
Family
ID=49583753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/063428 WO2013172348A1 (ja) | 2012-05-16 | 2013-05-14 | 食用油脂及びそれを含有する食品並びにその製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20150159117A1 (ja) |
EP (1) | EP2850949B1 (ja) |
JP (1) | JP5652557B2 (ja) |
TW (1) | TWI604795B (ja) |
WO (1) | WO2013172348A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015005128A1 (ja) * | 2013-07-09 | 2015-01-15 | 不二製油株式会社 | 冷菓及び製菓用油脂 |
JP2015015907A (ja) * | 2013-07-09 | 2015-01-29 | 不二製油株式会社 | 冷菓用油脂 |
WO2015072406A1 (ja) * | 2013-11-13 | 2015-05-21 | 不二製油株式会社 | 多価不飽和脂肪酸含有油脂 |
WO2017150558A1 (ja) | 2016-03-02 | 2017-09-08 | 不二製油グループ本社株式会社 | 抗酸化油脂組成物 |
WO2017183651A1 (ja) * | 2016-04-20 | 2017-10-26 | 花王株式会社 | 分離型液体調味料 |
WO2017183650A1 (ja) * | 2016-04-20 | 2017-10-26 | 花王株式会社 | 乳化液状調味料 |
JP2018016776A (ja) * | 2016-07-29 | 2018-02-01 | ミヨシ油脂株式会社 | 抗酸化剤、抗酸化剤を含有する油脂組成物およびこれを含有する油性食品 |
EP3213639A4 (en) * | 2014-10-31 | 2018-04-04 | Cj Cheiljedang Corporation | Extract emulsified oil comprising antioxidant, edible oil containing same, and preparation method therefor |
WO2021044945A1 (ja) | 2019-09-02 | 2021-03-11 | 不二製油グループ本社株式会社 | 油脂組成物 |
US11957135B2 (en) | 2016-03-02 | 2024-04-16 | Fuji Oil Holdings Inc. | Chocolate-like food containing polyunsaturated fatty acid |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10501705B2 (en) * | 2015-06-13 | 2019-12-10 | Jiangsu DEHE Biotechnology Co., Ltd | Method of processing edible oil |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135483A (ja) | 1986-11-26 | 1988-06-07 | Sankyo Co Ltd | 抗酸化剤 |
JPH06254378A (ja) | 1993-03-02 | 1994-09-13 | Nippon Oil & Fats Co Ltd | 水溶性化合物油溶化製剤およびその製造方法 |
WO2000077133A1 (fr) * | 1999-06-16 | 2000-12-21 | Kao Corporation | Compositions de matieres grasses |
JP2001131572A (ja) | 1999-10-29 | 2001-05-15 | Riken Vitamin Co Ltd | 酸化防止剤組成物及び油脂組成物 |
WO2001096506A1 (fr) | 2000-06-12 | 2001-12-20 | Fuji Oil Company, Limited | Procede servant a produire de la graisse |
JP2003092988A (ja) | 2001-09-21 | 2003-04-02 | Pure Green Kk | 茶葉成分を含有する食用油の製法 |
JP2005520565A (ja) | 2002-03-22 | 2005-07-14 | オイル・プロセス・システムズ,インコーポレイテッド | 料理用油酸化防止剤組成物、調製方法および使用 |
JP2005204511A (ja) * | 2004-01-20 | 2005-08-04 | Fuji Oil Co Ltd | 油脂及びその製造法並びにこれを用いた製品 |
JP2007240123A (ja) | 2006-03-13 | 2007-09-20 | Matsushita Electric Ind Co Ltd | 空気調和機 |
JP2008163202A (ja) * | 2006-12-28 | 2008-07-17 | Mitsui Norin Co Ltd | カテキン類が添加された油脂の着色抑制方法 |
JP2009291107A (ja) * | 2008-06-04 | 2009-12-17 | Kao Corp | ポリフェノールを高濃度に含有するオリーブオイル |
JP2010041965A (ja) * | 2008-08-13 | 2010-02-25 | Ito En Ltd | カテキン分散油脂及びその製造方法 |
WO2010050449A1 (ja) * | 2008-10-28 | 2010-05-06 | 日清オイリオグループ株式会社 | パーム油、脱臭留出物及びそれらの製造方法 |
WO2011121865A1 (ja) * | 2010-03-30 | 2011-10-06 | 不二製油株式会社 | 加熱調理用油脂及びその製造方法 |
WO2011122339A1 (ja) * | 2010-03-29 | 2011-10-06 | 株式会社J-オイルミルズ | 揚げ物用油脂組成物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3463308B2 (ja) * | 1993-03-02 | 2003-11-05 | 日本油脂株式会社 | 抗酸化剤組成物およびその製造方法 |
ES2255864B1 (es) * | 2004-12-23 | 2007-08-01 | Natraceutical, S.A. | Proceso de microemulsion de antioxidantes polares en aceites comestibles. |
WO2010033034A1 (en) * | 2008-09-19 | 2010-03-25 | Epax As | Antioxidant composition for marine oils comprising tocopherol, rosemary extract, ascorbic acid and green tea extract |
-
2013
- 2013-05-14 EP EP13789984.5A patent/EP2850949B1/en active Active
- 2013-05-14 WO PCT/JP2013/063428 patent/WO2013172348A1/ja active Application Filing
- 2013-05-14 JP JP2013546522A patent/JP5652557B2/ja active Active
- 2013-05-14 US US14/400,107 patent/US20150159117A1/en not_active Abandoned
- 2013-05-16 TW TW102117335A patent/TWI604795B/zh active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135483A (ja) | 1986-11-26 | 1988-06-07 | Sankyo Co Ltd | 抗酸化剤 |
JPH06254378A (ja) | 1993-03-02 | 1994-09-13 | Nippon Oil & Fats Co Ltd | 水溶性化合物油溶化製剤およびその製造方法 |
WO2000077133A1 (fr) * | 1999-06-16 | 2000-12-21 | Kao Corporation | Compositions de matieres grasses |
JP2001131572A (ja) | 1999-10-29 | 2001-05-15 | Riken Vitamin Co Ltd | 酸化防止剤組成物及び油脂組成物 |
WO2001096506A1 (fr) | 2000-06-12 | 2001-12-20 | Fuji Oil Company, Limited | Procede servant a produire de la graisse |
JP2003092988A (ja) | 2001-09-21 | 2003-04-02 | Pure Green Kk | 茶葉成分を含有する食用油の製法 |
JP2005520565A (ja) | 2002-03-22 | 2005-07-14 | オイル・プロセス・システムズ,インコーポレイテッド | 料理用油酸化防止剤組成物、調製方法および使用 |
JP2005204511A (ja) * | 2004-01-20 | 2005-08-04 | Fuji Oil Co Ltd | 油脂及びその製造法並びにこれを用いた製品 |
JP2007240123A (ja) | 2006-03-13 | 2007-09-20 | Matsushita Electric Ind Co Ltd | 空気調和機 |
JP2008163202A (ja) * | 2006-12-28 | 2008-07-17 | Mitsui Norin Co Ltd | カテキン類が添加された油脂の着色抑制方法 |
JP2009291107A (ja) * | 2008-06-04 | 2009-12-17 | Kao Corp | ポリフェノールを高濃度に含有するオリーブオイル |
JP2010041965A (ja) * | 2008-08-13 | 2010-02-25 | Ito En Ltd | カテキン分散油脂及びその製造方法 |
WO2010050449A1 (ja) * | 2008-10-28 | 2010-05-06 | 日清オイリオグループ株式会社 | パーム油、脱臭留出物及びそれらの製造方法 |
WO2011122339A1 (ja) * | 2010-03-29 | 2011-10-06 | 株式会社J-オイルミルズ | 揚げ物用油脂組成物 |
WO2011121865A1 (ja) * | 2010-03-30 | 2011-10-06 | 不二製油株式会社 | 加熱調理用油脂及びその製造方法 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015005128A1 (ja) * | 2013-07-09 | 2015-01-15 | 不二製油株式会社 | 冷菓及び製菓用油脂 |
JP2015015907A (ja) * | 2013-07-09 | 2015-01-29 | 不二製油株式会社 | 冷菓用油脂 |
WO2015072406A1 (ja) * | 2013-11-13 | 2015-05-21 | 不二製油株式会社 | 多価不飽和脂肪酸含有油脂 |
EP3213639A4 (en) * | 2014-10-31 | 2018-04-04 | Cj Cheiljedang Corporation | Extract emulsified oil comprising antioxidant, edible oil containing same, and preparation method therefor |
US11957135B2 (en) | 2016-03-02 | 2024-04-16 | Fuji Oil Holdings Inc. | Chocolate-like food containing polyunsaturated fatty acid |
WO2017150558A1 (ja) | 2016-03-02 | 2017-09-08 | 不二製油グループ本社株式会社 | 抗酸化油脂組成物 |
JPWO2017150558A1 (ja) * | 2016-03-02 | 2019-01-17 | 不二製油株式会社 | 抗酸化油脂組成物 |
JP7103216B2 (ja) | 2016-03-02 | 2022-07-20 | 不二製油株式会社 | 抗酸化油脂組成物 |
JP7343001B2 (ja) | 2016-03-02 | 2023-09-12 | 不二製油株式会社 | 抗酸化油脂組成物 |
WO2017183650A1 (ja) * | 2016-04-20 | 2017-10-26 | 花王株式会社 | 乳化液状調味料 |
JP2017195880A (ja) * | 2016-04-20 | 2017-11-02 | 花王株式会社 | 分離型液体調味料 |
JP2017195879A (ja) * | 2016-04-20 | 2017-11-02 | 花王株式会社 | 乳化液状調味料 |
WO2017183651A1 (ja) * | 2016-04-20 | 2017-10-26 | 花王株式会社 | 分離型液体調味料 |
TWI720184B (zh) * | 2016-04-20 | 2021-03-01 | 日商花王股份有限公司 | 分離型液體調味料、及分離型液體調味料之製造方法 |
US11206858B2 (en) | 2016-04-20 | 2021-12-28 | Kao Corporation | Separated liquid seasoning |
US11297863B2 (en) | 2016-04-20 | 2022-04-12 | Kao Corporation | Emulsified seasoning |
JP2018016776A (ja) * | 2016-07-29 | 2018-02-01 | ミヨシ油脂株式会社 | 抗酸化剤、抗酸化剤を含有する油脂組成物およびこれを含有する油性食品 |
KR20220053573A (ko) | 2019-09-02 | 2022-04-29 | 후지세유 그룹 혼샤 가부시키가이샤 | 유지 조성물 |
WO2021044945A1 (ja) | 2019-09-02 | 2021-03-11 | 不二製油グループ本社株式会社 | 油脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
TWI604795B (zh) | 2017-11-11 |
JP5652557B2 (ja) | 2015-01-14 |
EP2850949A1 (en) | 2015-03-25 |
JPWO2013172348A1 (ja) | 2016-01-12 |
US20150159117A1 (en) | 2015-06-11 |
EP2850949B1 (en) | 2019-02-06 |
EP2850949A4 (en) | 2016-05-11 |
TW201402012A (zh) | 2014-01-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5652557B2 (ja) | 食用油脂及びそれを含有する食品並びにその製造方法 | |
AU2018202247B2 (en) | Fat containing polyunsaturated fatty acid | |
JP5765477B2 (ja) | 高度多価不飽和脂肪酸含有油脂およびそれを含有する食品ならびにその製造法 | |
JP5765476B2 (ja) | 多価不飽和脂肪酸含有食用植物油脂 | |
WO2015064569A1 (ja) | 加熱調理用油脂 | |
JP6471405B2 (ja) | 加熱調理用油脂 | |
WO2016129611A1 (ja) | 抗酸化剤組成物およびそれを添加した油脂 | |
JP6774045B1 (ja) | 油脂組成物 | |
JP6304451B2 (ja) | コーヒークリーム用油脂組成物 | |
JP2019176788A (ja) | フライ麺臭のマスキング剤、フライ麺臭のマスキング方法及び即席フライ麺製品。 | |
KR20220053573A (ko) | 유지 조성물 | |
JP7151979B1 (ja) | 酸化防止剤組成物及び食用油脂 | |
KR20210009954A (ko) | 유지 조성물 및 이의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013546522 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13789984 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013789984 Country of ref document: EP Ref document number: 14400107 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |