WO2011152532A1 - 安定性が向上したカシューナッツ殻油 - Google Patents
安定性が向上したカシューナッツ殻油 Download PDFInfo
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- WO2011152532A1 WO2011152532A1 PCT/JP2011/062829 JP2011062829W WO2011152532A1 WO 2011152532 A1 WO2011152532 A1 WO 2011152532A1 JP 2011062829 W JP2011062829 W JP 2011062829W WO 2011152532 A1 WO2011152532 A1 WO 2011152532A1
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- Prior art keywords
- cashew nut
- acid
- nut shell
- shell liquid
- unheated cashew
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
- C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/111—Aromatic compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/26—Compounds containing phosphorus
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K40/00—Shaping or working-up of animal feeding-stuffs
- A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/10—Feeding-stuffs specially adapted for particular animals for ruminants
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/20—Feeding-stuffs specially adapted for particular animals for horses
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/30—Feeding-stuffs specially adapted for particular animals for swines
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/60—Feeding-stuffs specially adapted for particular animals for weanlings
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- 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
- C11B5/0028—Carboxylic acids; Their derivates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Definitions
- the present invention is a composition comprising an acid and unheated cashew nut shell liquid, wherein the decarboxylation of anacardic acid contained in unheated cashew nut (CNSL) is suppressed by the acid, and unheated using the same
- the present invention relates to cashew nut shell liquid formulation and feed.
- the present invention also relates to a method for inhibiting the decarboxylation reaction of anacardic acid in unheated cashew nut shell liquid, wherein an acid is added to the unheated cashew nut shell liquid.
- Cashew nut shell oil is an oily liquid contained in the shell of the cashew nut tree ( Anacardium occidentale L.).
- Cashew nut shell oil mainly contains anacardic acid, cardanol, cardol, and methyl cardol as its components.
- As a method for preparing cashew nut shell liquid there are a heating method and a solvent extraction method.
- cashew nut shell oil is used by converting anacardic acid into cardanol by heat treatment in a cashew nut production place. This is because in uncooked cashew nut shell liquid, the component anacardic acid is easily decarboxylated and there is a concern of foaming during transportation.
- Unheated cashew nut shell liquid solidifies at about 20 ° C. and loses fluidity, and is difficult to transport. For these reasons, there are significant restrictions on the transport of unheated cashew nut shell liquid, hindering further industrial use.
- Patent Documents 1-3 examples of applications to industrial products include Patent Documents 1-3, and all of the cashew nut shell liquids used are heat-treated.
- Patent Documents 4-6 mention the use of unheated cashew nut shell liquid and its component anacardic acid for feed applications. There are high hurdles to realize such challenges.
- Patent Documents 4-6 recognize the description of the utilization of unheated cashew nut shell liquid, but there is no knowledge to improve the stability by focusing on the improvement of stability and handleability. Therefore, the advent of a method for stabilizing unheated cashew nut shell liquid so that it can be easily transported has been desired.
- Patent Document 7 describes a method of stabilizing anacardic acid by adding and mixing an alkali with cashew nut shell liquid containing anacardic acid. However, adding acid to cashew nut shell liquid to stabilize anacardic acid is not described. Moreover, it is not described that it is possible to prevent solidification around 20 ° C. by blending an excipient with unheated cashew nut shell liquid to which an acid has been added.
- the present inventors have found that decarboxylation of anacardic acid is suppressed by adding an acid to unheated cashew nut shell liquid.
- the present inventors can also solidify even at a low temperature of about 20 ° C. or less by blending an unheated cashew nut shell oil whose decarboxylation is suppressed by adding an acid with an excipient such as cereal flour or silica. And found that unheated cashew nut shell liquid can be transported. The inventors have thus completed the present invention.
- the present invention is as follows. (1) A composition comprising one or more acids and unheated cashew nut shell oil, wherein the decarboxylation of anacardic acid contained in the unheated cashew nuts is suppressed by the one or more acids. . (2) The composition according to (1), wherein the acid has a pKa of 4.5 or less. (3) The composition according to (1) or (2), wherein the amount of the acid is 0.5% by weight or more of the unheated cashew nut shell liquid ratio. (4) An unheated cashew nut shell liquid formulation comprising the composition according to any one of (1) to (3) and one or more excipients.
- Deacidification of anacardic acid which is a component of unheated cashew nut shell liquid, can be suppressed by adding an acid to the unheated cashew nut shell liquid. Moreover, it can prevent solidifying around 20 degreeC by mix
- FIG. 1 shows the inhibition of decarboxylation of unheated cashew nut shell oil when 1% by weight of various acids is used.
- the bar graph shows, in order from the top, cardanol 15: 1, 15: 2, 15: 3, anacardic acid 15: 1, 15: 2, 15: 3.
- FIG. 2 shows the inhibition of decarboxylation of unheated cashew nut shell oil using 10 wt% of various acids.
- the bar graph shows, in order from the top, cardanol 15: 1, 15: 2, 15: 3, anacardic acid 15: 1, 15: 2, 15: 3.
- FIG. 3 shows the inhibition of decarboxylation of unheated cashew nut shell oil when various concentrations of sulfuric acid are used.
- FIG. 3A shows cardanol 15: 1 and anacardic acid 15: 1 in order from the top
- the bar graph in FIG. 3B shows cardanol 15: 3 and anacardic acid 15: 3 in order from the top
- FIG. 4 shows the suppression of the decarboxylation reaction in the unheated cashew nut shell liquid formulation using 10 wt% phosphoric acid (acid addition to the unheated cashew nut shell liquid in advance).
- the bar graph shows, in order from the top, cardanol 15: 3 and anacardic acid 15: 3.
- FIG. 5 shows the suppression of decarboxylation in an unheated cashew nut shell liquid formulation using 10 wt% phosphoric acid (acid addition to excipient in advance).
- FIG. 6 shows suppression of decarboxylation reaction in feed when 10 wt% phosphoric acid is used.
- the bar graph shows, in order from the top, cardanol 15: 3 and anacardic acid 15: 3.
- composition of the present invention includes one or more acids and unheated cashew nut shell liquid, and the decarboxylation of anacardic acid contained in the unheated cashew nuts is suppressed by the one or more acids. To do.
- the cashew nut shell liquid used in the present invention is an oily liquid contained in the shell of the cashew nut tree ( Anacardium occidentale L.).
- Cashew nut shell oil contains anacardic acid, cardanol, cardol, and methyl cardol as its components.
- Non-heated cashew nut shell oil extracted by squeezing cashew nut shell (hereinafter referred to as cashew nut shell oil) is anacardic acid as described in J. Agric. Food Chem. 2001, 49, 2548-2551. Is 55 to 80% by mass, cardanol is 5 to 20% by mass, and cardol is 5 to 30% by mass.
- Anacardic acid has three double bonds at the 8,11,14 positions (hereinafter, 15: 3), has two double bonds at the 8,11 positions (hereinafter, 15: 2), And those having one double bond at the 8-position (hereinafter referred to as 15: 1).
- the present invention also includes a method for inhibiting the decarboxylation reaction of anacardic acid, which comprises adding one or more acids to anacardic acid.
- the cashew nut shell oil used in the present invention can be obtained as a vegetable oil extracted by pressing the cashew nut shell.
- the cashew nut shell oil used in the present invention can also be obtained by extraction, for example, solvent extraction of cashew nut shell.
- the cashew nut shell liquid used in the present invention can be obtained by a method described in JP-A-8-231410, for example, a solvent extraction method.
- the cashew nut shell oil used in the present invention may be obtained by pulverizing and crushing cashew nut shells. A commercial item can also be used for the cashew nut shell liquid used in this invention.
- the acid used in the present invention is preferably an acid having a pKa of 4.5 or less, and more preferably 4.0 or less.
- Specific acids include, for example, formic acid, malic acid, citric acid, succinic acid, tartaric acid, phosphoric acid, nitric acid, hydrochloric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, phthalic acid, Examples include, but are not limited to, isophthalic acid, phytic acid, sulfuric acid, terephthalic acid, lactic acid, sulfamic acid, hydroxyacetic acid, phosphonic acid, and gluconic acid.
- the value of pKa refers to a value calculated at 25 ° C. using water as a solvent.
- the amount of acid used is preferably 0.5% by weight or more, more preferably 1 to 20% by weight, based on cashew nut shell liquid (CNSL).
- CNSL cashew nut shell liquid
- the pKa of the acid is higher than 2, it is necessary to increase the amount of acid to be added, for example, about 5 to 10% by weight.
- the composition of the present invention can be produced by adding one or more acids to unheated cashew nuts.
- the unheated cashew nut shell liquid formulation of the present invention is preferably a formulation comprising the composition of the present invention and one or more excipients, for example, the composition of the present invention and one or more excipients. It can mix and can be set as an unheated cashew nut shell liquid formulation.
- Inorganic excipients include, but are not limited to, silicic acid and its salts (eg, silica), vermiculite, diatomaceous earth, talc, kaolin, and bentonite.
- silicic acid and its salts are used as the inorganic excipient, the specific surface area is preferably 500 m 3 / g or less so that the oxidation reaction does not become remarkable.
- the same specific surface area and blending ratio may be used when other inorganic excipients are used.
- the specific surface area of silica can be measured by the BET method.
- cereal flour, corn grains, corn flour, milo, soybean meal, oats, wheat short, wheat coarse powder, alfalfa, clover, defatted rice bran, northern meal, coastal meal, yeast, molasses, meat pieces, bone Feed ingredients such as meal may be used as organic excipients.
- the unheated cashew nut shell liquid formulation of the present invention is not particularly limited as long as it contains unheated cashew nut shell liquid, one or more excipients, and one or more acid components. Therefore, the acid component and the excipient may be mixed in advance, and the excipient mixed with the acid component may be further mixed with unheated cashew nut shell liquid. Due to the influence of the acid component in the excipient, decarboxylation of the unheated cashew nut shell liquid can be suppressed while the acid is mixed with the excipient.
- the unheated cashew nut shell liquid formulation of the present invention may contain one or more antioxidants in addition to the unheated cashew nut shell oil, excipients and acid components, for example, ethoxyquin, t-butylhydroxy Toluene, t-butylhydroxyanisole, t-butylhydroquinone, ascorbic acid and its ester, vitamin E, gallic acid and its ester, erythorbic acid, chlorogenic acid, sulfite, thiosulfate, phosphite, hypophosphorous acid Examples include, but are not limited to, salts and phosphates.
- the unheated cashew nut shell liquid formulation of the present invention may use one or more antibiotics in addition to unheated cashew nut shell oil, excipients and acid components, and may include zinc bacitracin, aviramycin, alkyltrimethylammonium.
- the dosage form of the unheated cashew nut shell liquid formulation of the present invention can be formulated as a powder by containing excipients such as cereal flour and silica. That is, the unheated cashew nut shell liquid formulation of the present invention comprises unheated cashew nut shell oil, one or more excipients, one or two or more acid components, and optionally one or two or more optional components. However, it can be manufactured by formulating into a powder. Such a powdery preparation of the present invention can be used as a feed without being mixed with other optional components.
- the unheated cashew nut shell liquid formulation of the present invention can be made into granules such as pellets in addition to powders.
- one or more hardened oils may be used.
- the hardened oil oil obtained by hardening palm oil, soybean oil, rapeseed oil or the like is used.
- the melting point of the hardened oil is preferably 45 to 65 ° C.
- it can manufacture using a normal extrusion granulator.
- the unheated cashew nut shell liquid formulation of the present invention may also be coated, for example, selected from zein, shellac, HPMC (hydroxypropylmethylcellulose), pullulan, hemirose, glucose, lactose, trehalose and starch after granulation. It can be coated with one or more coating agents. Moreover, you may coat
- the present invention includes a feed comprising the composition of the present invention and / or an unheated cashew nut shell liquid formulation.
- the unheated cashew nut shell liquid contained in the feed is decarboxylated by one or more acid components.
- the type and blending ratio of the feed components blended with the composition of the present invention and / or cashew nut shell liquid preparation are not particularly limited, and any feed that has been conventionally fed to each animal can be used.
- any feed that has been conventionally fed to each animal can be used.
- corn grain, corn flour, milo, soybean meal, oat wheat, wheat flour short, wheat flour, alfalfa, clover, defatted rice bran, northern meal, coastal meal, yeast, molasses, meat pieces, bone meal, calcium carbonate It can be prepared using one or more feed ingredients such as dicalcium phosphate, yellow grease, vitamins and minerals.
- the feed of the present invention can be produced by adding an unheated cashew nut shell liquid formulation as it is to the feed ingredients and mixing them.
- the formulation may be in a liquid or gel form for easy mixing.
- one or more water-soluble polymer compounds such as water, vegetable oil such as soybean oil, rapeseed oil and corn oil, liquid animal oil, polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid can be used as the liquid carrier.
- water-soluble polysaccharides such as alginic acid, sodium alginate, xanthan gum, sodium caseinate, gum arabic, guar gum, tamarind seed polysaccharide should be added. Is also preferable.
- the feed of the present invention is suitable for raising livestock such as cattle, pigs, chickens, sheep, horses, goats and the like.
- the amount of feed to be ingested can be adjusted as appropriate according to the kind of animal, body weight, age, sex, health condition, ingredients of the feed, etc.
- the cashew nut nut shell liquid contained in the feed is preferably 0.005 to 500 g / head. -Day, more preferably 0.05 to 100 g / head / day.
- a method for ingesting and rearing a feed a commonly used method can be employed depending on the type of animal.
- Example 1 Sample Preparation 500 kg of cashew nut shell was obtained from Cashew Trading Co., Ltd., and pressed to produce 158 kg of cashew nut shell oil (unheated cashew nut shell oil). Moreover, the following two grades were used for the silica used as an excipient. Sipernat 22 (pH 6.5) (Evonik Degussa Japan Co., Ltd.) Carplex # 1120 (pH 10.6) (Evonik Degussa Japan Co., Ltd.)
- the pKa of the acid used is as follows. Sulfuric acid (-3) Nitric acid (-1.6) Phosphoric acid (2.1) Formic acid (3.8) Acetic acid (4.8)
- Example 2 HPLC measurement equipment HPLC (Waters600, Nihon Waters), detector (Waters490E, Nihon Waters), printer (Chromatopack C-R6A, Shimadzu Corporation), column (SUPELCOSIL LC18, SUPELCO) was used.
- pH measurement The pH of silica was measured as follows. A 5% by weight silica water suspension was prepared with ion-exchanged water, and the potential was measured with a glass electrode to obtain pH.
- Example 3 Inhibition of decarboxylation reaction when various acids of 1% by weight or 10% by weight were added Unheated cashew nut shell oil 10 g was dispensed into each beaker, and 1% by weight of sulfuric acid and 1% by weight of nitric acid there. Then, 1% by weight, 10% by weight of phosphoric acid, 1% by weight, 10% by weight of formic acid, 1% by weight and 10% by weight of acetic acid were added and stirred uniformly. Each was sealed and allowed to stand in a constant temperature bath at 80 ° C., sampled after 4 days, and subjected to composition analysis by HPLC.
- Tables 1 and 2 show the compositions of anacardic acid, cardanol and cardol before and after standing in a thermostatic bath.
- Anacardic acid, cardanol and cardol are mainly classified into the following three types depending on the number of unsaturated bonds of the aliphatic chain having 15 carbon atoms bonded to the aromatic ring (anacardic acid; AA15: 1, AA15: 2). , AA 15: 3, Cardanol; CD15: 1, CD15: 2, CD15: 3, Cardol; 15: 1, 15: 2, 15: 3).
- Embodiment 5 Suppression of decarboxylation in unheated cashew nut shell liquid formulation (addition of phosphoric acid to unheated cashew nut shell oil in advance) 10g each of silica (Sipernat 22, Carplex # 1120) is collected in a beaker, and then 20g of unheated cashew nut shell liquid or 20g of unheated cashew nut shell liquid containing 10wt% phosphoric acid is added and stirred uniformly. , Mixed. Each was sealed and then left in a constant temperature bath at 80 ° C., sampled after 3 days, and subjected to composition analysis by HPLC.
- silica Sipernat 22, Carplex # 1120
- the collected sample was adjusted to a concentration of 5 mg (including silica) / ml with ethyl acetate, centrifuged at 15,000 rpm for 5 min, and the supernatant was measured.
- the analysis result was described as the concentration at the time of analysis (nmol / L) for anacardic acid 15: 3 (Table 4, FIG. 4).
- silica is used as an excipient, the rate of decarboxylation is almost the same or lower in Sipernat 22 where the pH is near neutral than when no excipient is used.
- Carplex # 1120 was used as an excipient, it was confirmed that the rate of decarboxylation was clearly increased.
- Example 6 Suppression of decarboxylation in unheated cashew nut shell liquid formulation (addition of phosphoric acid to excipient in advance) Sipernat 22 150g was collected in a plastic bag, and 85% phosphoric acid was put in a spray bottle while stirring and 9ml was sprayed. It was pH 2.0 when pH of the produced phosphoric acid addition Sipernat 22 was measured. 10 g each of silica (Sipernat 22, phosphoric acid-added Sipernat 22, Carplex # 1120) was collected in a beaker, 20 g of unheated cashew nut shell liquid was added thereto, and the mixture was stirred and mixed so as to be uniform.
- silica Sipernat 22, phosphoric acid-added Sipernat 22, Carplex # 1120
- Example 7 Suppression of decarboxylation reaction in feed 2 types of silica preparations (Sipernat 22 10 g + unheated cashew nut shells) prepared in Example 5 on 100 g of feed (standard feed for raising young cows: SDC No. 2 Nippon Mixed Feed Co., Ltd.) 1 g of unheated cashew nut shell liquid containing 20 g of oil or 10 wt% phosphoric acid was added to prepare a feed containing unheated cashew nut shell liquid. Each was sealed and then left in a constant temperature bath at 80 ° C., sampled after 3 days, and subjected to composition analysis by HPLC.
- the HPLC analysis was performed by extracting the soluble part from the feed used in the test with ethyl acetate, filtering and drying, and adjusting the concentration to 5 mg / ml.
- the analysis results for anacardic acid 15: 3 are the compositions of anacardic acid and cardanol before and after standing in a thermostatic bath (Table 6, FIG. 6). The results are shown in Table 6 below.
- Example 8 Preparation of feed containing unheated cashew nut shell liquid (use of organic excipients)
- Chicken and cattle feed was prepared using standard feed as an excipient.
- the blending examples are not limited to the following.
- Broiler feed preparation Broiler fattening standard feed: SDB No. 1 Japan Formula Feed Co., Ltd. 99.5% by weight Unheated cashew nut shell liquid (10 wt% phosphoric acid) 0.05 wt% By mixing, it becomes powder and can be prevented from solidifying around 20 ° C.
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Abstract
Description
カシューナッツ殻油の調製法としては加熱法と溶剤抽出法があるが、通常、カシューナッツ殻油はカシューナッツ生産地にて加熱処理されることにより、アナカルド酸をカルダノールに変換して使用されている。
これは未加熱のカシューナッツ殻油においては、成分のアナカルド酸が脱炭酸し易く、運搬中に発泡する懸念があるからである。また、未加熱のカシューナッツ殻油は約20℃にて固化して流動性を消失し、運搬し難い。これらの理由から、未加熱のカシューナッツ殻油の輸送に関しては大きな制約があり、更なる工業的使用の妨げとなっていた。
特許文献4-6には未加熱のカシューナッツ殻油およびその成分であるアナカルド酸の飼料用途に向けた活用について言及されているが、上記した安定性・運搬上の制約から、物理的および経済的な課題も含め、その実現に向けたハードルは高い。また、特許文献4-6には未加熱のカシューナッツ殻油の活用についての記述は認められるが、安定性および取り扱い性の向上に着目し、その改善を図った知見はない。
そこで、未加熱のカシューナッツ殻油を容易に運搬できるように安定化する方法の出現が望まれていた。
本発明者らはまた、酸を加えることにより脱炭酸が抑制された未加熱カシューナッツ殻油に、穀物粉、シリカ等の賦形剤を配合することにより、約20℃以下の低温でも固化させることなく、未加熱のカシューナッツ殻油を運搬できることを見出した。
本発明者らは、このようにして、本発明を完成するに至った。
(1)1または2以上の酸と未加熱カシューナッツ殻油を含む組成物であって、前記1または2以上の酸により未加熱カシューナッツに含まれるアナカルド酸の脱炭酸が抑制されている、組成物。
(2)酸のpKaが4.5以下であることを特徴とする(1)に記載の組成物。
(3)酸の量が未加熱カシューナッツ殻油比0.5重量%以上である(1)または(2)に記載の組成物。
(4)(1)~(3)のいずれか1項に記載の組成物と1または2以上の賦形剤とを含む未加熱カシューナッツ殻油製剤。
(5)前記賦形剤がシリカであることを特徴とする(4)に記載の未加熱カシューナッツ殻油製剤。
(6)(1)~(3)のいずれか1項に記載の組成物および/もしくは(4)または(5)に記載の未加熱カシューナッツ殻油製剤を加えてなる、脱炭酸が抑制された未加熱カシューナッツ殻油を含む飼料。
(7)未加熱カシューナッツ殻油に1または2以上の酸を添加することを特徴とする、未加熱カシューナッツ殻油中のアナカルド酸の脱炭酸反応抑制方法。
(8)1または2以上の酸成分と1または2以上の賦形剤とを混合すること、および酸成分と混合された賦形剤をさらに未加熱カシューナッツ殻油と混合することを特徴とする、(4)または(5)に記載の未加熱カシューナッツ殻油製剤を製造する方法。
(9)アナカルド酸に1または2以上の酸を添加することを特徴とする、アナカルド酸の脱炭酸反応抑制方法。
カシューナッツの殻を圧搾することにより抽出された非加熱カシューナッツ殻油(以下、カシューナッツ殻油という。)は、J.Agric.Food Chem. 2001, 49, 2548-2551に記載されるように、アナカルド酸を55~80質量%、カルダノールを5~20質量%、カルドールを5~30質量%含むものである。
なお、アナカルド酸は8,11,14位に二重結合を3つ存在するもの(以下、15:3)、8,11位に二重結合が2つ有するもの(以下、15:2)、および8位に二重結合を1つ有するもの(以下、15:1)の3種類がある。
また、本発明には、アナカルド酸に1または2以上の酸を添加することを特徴とする、アナカルド酸の脱炭酸反応抑制方法も含まれる。
本発明において使用されるカシューナッツ殻油は、その他にも、カシューナッツの殻を粉砕・破砕して得られたものであってもよい。
本発明において使用されるカシューナッツ殻油は、市販品を用いることもできる。
使用される酸の量としては、カシューナッツ殻油(CNSL)比0.5重量%以上であることが好ましく、より好ましくは、1~20重量%である。なお、酸のpKaが2より高い場合には、添加する酸の量をより多くする必要があり、例えば5~10重量%程度とすればよい。
本発明の組成物は、未加熱カシューナッツに1または2以上の酸を添加することにより製造することができる。
無機賦形剤としては、珪酸およびその塩類(例えば、シリカ)、バーミキュライト、珪藻土、タルク、カオリン、ベントナイトが挙げられるが、これらに限定されない。
無機賦形剤として珪酸およびその塩類を用いる場合には、酸化反応が顕著にならないように、その比表面積が、500m3/g以下であることが好ましい。無機賦形剤としてシリカを用いる場合の、配合比(重量比)としては、シリカ/未加熱カシューナッツ殻油=1/3.0~1/0.1とすることが好ましい。他の無機賦形剤を使用する場合にも、同様の比表面積、配合比とすればよい。なお、シリカの比表面積は、BET法によって測定することができる。
なお、穀物粉類や、後述の、トウモロコシ粒、トウモロコシ粉、マイロ、大豆粕、カラスムギ、小麦粉ショート、小麦粗粉、アルファルファ、クローバー、脱脂米糠、北洋ミール、沿岸ミール、酵母、糖蜜、肉片、ボーンミールなどの飼料成分を有機賦形剤として用いてもよい。
本発明の未加熱カシューナッツ殻油製剤は、未加熱カシューナッツ殻油、1または2以上の賦形剤および1または2以上の酸成分を含むものであれば特に限定されない。従って、酸成分と賦形剤とをあらかじめ混合し、酸成分と混合された賦形剤をさらに未加熱カシューナッツ殻油と混合させたものであってもよい。賦形剤中の酸成分の影響により、酸が賦形剤と混合された状態で、未加熱カシューナッツ殻油の脱炭酸を抑制することができる。
飼料を摂取させる方法及び飼育する方法は、動物の種類に応じて、通常用いられる方法をとることができる。
カシュー・トレーディング(株)よりカシューナッツの殻500kgを入手し、圧搾する事によりカシューナッツ殻油(未加熱カシューナッツ殻油)158kgを製造した。
また、賦形剤として使用するシリカは以下の2つのグレードを使用した。
Sipernat 22(pH6.5)(エボニック デグサ ジャパン(株))
Carplex#1120(pH10.6)(エボニック デグサ ジャパン(株))
硫酸(-3)
硝酸(-1.6)
リン酸(2.1)
ギ酸(3.8)
酢酸(4.8)
機器は、HPLC(Waters600、日本ウォータース(株))、検出器(Waters490E、日本ウォータース(株))、プリンタ(クロマトパックC-R6A、島津製作所)、カラム(SUPELCOSIL LC18、SUPELCO社)を用いた。条件は、溶媒 アセトニトリル:水:酢酸=80:20:1(容量比)、流速2ml/ml、温度 25℃、吸光度 280nmにて測定した。
シリカのpHは下記要領にて測定した。
イオン交換水により5重量%のシリカ水懸濁液を作成し、ガラス電極にて電位測定し、pHとした。
未加熱カシューナッツ殻油 10gを各ビーカーに分取し、そこに、硫酸1重量%、硝酸1重量%、リン酸1重量%,10重量%、ギ酸1重量%,10重量%、酢酸1重量%,10重量%を加え、均一となるよう攪拌した。
それぞれ、密閉後80℃の恒温槽に静置し、4日後にサンプリングを行い、HPLCによる組成分析を行った。
アナカルド酸(AA)は脱炭酸反応によりカルダノール(CD)へと変換される為、表1,2には恒温槽静置前後におけるアナカルド酸とカルダノールとカルドールの組成を記した。アナカルド酸とカルダノールとカルドールは、芳香族環に結合する炭素数15の脂肪鎖が有する不飽和結合の数により、それぞれ主に以下の三種類が存在する(アナカルド酸;AA15:1,AA15:2,AA15:3、カルダノール;CD15:1,CD15:2,CD15:3、カルドール;15:1,15:2,15:3)。
各種酸を1重量%添加した場合(図1、表1)、4日後の脱炭酸(アナカルド酸 → カルダノール)の割合はpKaの強度に従い、少なくなっている事がわかる。pKa4.8の酢酸の場合、1重量%添加では無添加(Control)の場合と殆ど変わらない。
なお、カルドールについては、表のみに記載し、図には記載していない。
なお、カルドールについては、表のみに記載し、図には記載していない。
未加熱カシューナッツ殻油 10gを各ビーカーに分取し、そこに、硫酸0.1重量%、0.3重量%、0.6重量%、1重量%を加え、均一となるよう攪拌した。
それぞれ、密閉後80℃の恒温槽に静置し、3日後にサンプリングを行い、HPLCによる組成分析を行った。分析結果はアナカルド酸15:1とアナカルド酸15:3に分けて、分析時の濃度(nmol/L)として記した(表3左欄、右欄、図3A,B)。図より、硫酸添加量が0.6重量%になると脱炭酸反応の減少が確認され、1重量%添加ではかなり顕著となることがわかる。
シリカ(Sipernat 22、Carplex#1120)各10gをビーカーに採取し、そこに未加熱カシューナッツ殻油 20gまたは10重量%リン酸を含有する未加熱カシューナッツ殻油 20gを添加し、均一となるように攪拌、混合した。それぞれ、密閉後80℃の恒温槽に静置し、3日後にサンプリングを行い、HPLCによる組成分析を行った。HPLC分析は、採取試料を酢酸エチルにて5mg(シリカ含む)/mlとなるよう濃度調整後、15,000rpm,5minの条件にて遠心分離を行い、その上清を測定した。分析結果はアナカルド酸15:3について、分析時の濃度(nmol/L)として記した(表4、図4)。
シリカを賦形剤に用いた場合、pHが中性付近にあるSipernat 22では賦形剤を用いない場合と比較して脱炭酸の割合はほぼ同じまたは低下しているレベルであるが、アルカリ性であるCarplex#1120を賦形剤に用いた場合は、明らかに脱炭酸の割合が増加している事が確認された。
一方、10重量%リン酸を含有する未加熱カシューナッツ殻油を用いた場合は、賦形剤の使用の有無、賦形剤に用いたシリカのpHに関係なく、脱炭酸反応が抑制されている事が確認された。
結果を以下の表4に示す。
Sipernat 22 150gをビニール袋に採取し、攪拌しながら85%リン酸を霧吹きに入れ9mlを噴霧した。作製したリン酸添加Sipernat 22のpHを測定したところ、pH2.0であった。
シリカ(Sipernat 22、リン酸添加Sipernat 22、Carplex#1120)各10gをビーカーに採取し、そこに未加熱カシューナッツ殻油 20gを添加し、均一となるように攪拌、混合した。それぞれ、密閉後80℃の恒温槽に静置し、3日後にサンプリングを行い、HPLCによる組成分析を行った。HPLC分析は、採取試料を酢酸エチルにて5mg(シリカ含む)/mlとなるよう濃度調整後、15,000rpm,5minの条件にて遠心分離を行い、その上清を測定した。分析結果はアナカルド酸15:1およびアナカルド酸15:3について、分析時の濃度(nmol/L)として記した(表5、図5)。
結果を以下の表5に示す。
以上の事より、脱炭酸反応に使用される酸は、未加熱カシューナッツ殻油に予め添加されている必要はなく、事前に賦形剤に添加されていても良い事がわかる。
飼料(若齢牛育成用標準飼料:SDC No.2 日本配合飼料(株))100gに実施例5にて作成したシリカ剤2種(Sipernat 22 10g+未加熱カシューナッツ殻油 20gまたは10重量%リン酸を含有する未加熱カシューナッツ殻油 20g)を1重量%添加して、未加熱カシューナッツ殻油を含む飼料を作成した。
それぞれ、密閉後80℃の恒温槽に静置し、3日後にサンプリングを行い、HPLCによる組成分析を行った。
HPLC分析は、試験に用いた飼料から酢酸エチルにて可溶部を抽出後、ろ過、乾燥し、5mg/mlとなるよう濃度調整して測定した。分析結果はアナカルド酸15:3について、恒温槽静置前後におけるアナカルド酸とカルダノールの組成を記した(表6、図6)。
結果を以下の表6に示す。
標準飼料を賦形剤として利用し、鶏及び牛用飼料を作成した。配合例は以下に限定されない。
(1)ブロイラー用飼料作成
ブロイラー肥育前期用標準飼料:SDB No.1 日本配合飼料(株)
99.5 重量%
未加熱カシューナッツ殻油(10重量%リン酸) 0.05重量%
混合する事により粉体となり、20℃近辺で固化することを防止できる。
(2)牛用飼料作成
若齢牛育成用標準飼料:SDC No.2 日本配合飼料(株)
99.5 重量%
未加熱カシューナッツ殻油(10重量%リン酸) 0.05重量%
混合する事により粉体となり、20℃近辺で固化することを防止できる。
Claims (9)
- 1または2以上の酸と未加熱カシューナッツ殻油を含む組成物であって、前記1または2以上の酸により未加熱カシューナッツに含まれるアナカルド酸の脱炭酸が抑制されている、組成物。
- 酸のpKaが4.5以下であることを特徴とする請求項1に記載の組成物。
- 酸の量が未加熱カシューナッツ殻油比0.5重量%以上である請求項1または2に記載の組成物。
- 請求項1~3のいずれか1項に記載の組成物と1または2以上の賦形剤とを含む未加熱カシューナッツ殻油製剤。
- 前記賦形剤がシリカであることを特徴とする請求項4に記載の未加熱カシューナッツ殻油製剤。
- 請求項1~3のいずれか1項に記載の組成物および/もしくは請求項4または5に記載の未加熱カシューナッツ殻油製剤を加えてなる、脱炭酸が抑制された未加熱カシューナッツ殻油を含む飼料。
- 未加熱カシューナッツ殻油に1または2以上の酸を添加することを特徴とする、未加熱カシューナッツ殻油中のアナカルド酸の脱炭酸反応抑制方法。
- 1または2以上の酸成分と1または2以上の賦形剤とを混合すること、および酸成分と混合された賦形剤をさらに未加熱カシューナッツ殻油と混合することを特徴とする、請求項4または5に記載の未加熱カシューナッツ殻油製剤を製造する方法。
- アナカルド酸に1または2以上の酸を添加することを特徴とする、アナカルド酸の脱炭酸反応抑制方法。
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| KR20130099169A (ko) * | 2010-11-05 | 2013-09-05 | 이데미쓰 고산 가부시키가이샤 | 안정성이 향상된 캐슈 너트셸 오일 |
| TWI618488B (zh) * | 2013-10-30 | 2018-03-21 | 出光興產股份有限公司 | 含有腰果殼油等的二氧化矽製劑及其製造方法 |
| EP3251522B1 (en) * | 2015-01-30 | 2024-03-20 | Sds Biotech K.K. | Functional feed |
| EP3251737A1 (en) | 2016-05-31 | 2017-12-06 | Evonik Degussa GmbH | Membrane-based processes for purification of cashew nut shell liquid |
| KR101889822B1 (ko) * | 2017-03-21 | 2018-09-28 | 애경유화 주식회사 | 캐슈넛 껍질 오일 및 기타 조동식물성 유지의 정제방법 |
| CN111820217B (zh) * | 2019-04-22 | 2022-07-05 | 太平洋农业股份公司 | 用于植物保护的水包油乳液形式的组合物以及用于制备该组合物的方法 |
| CN113583357B (zh) * | 2021-09-10 | 2023-07-14 | 广州市朗凯科技有限公司 | 卫生安全环保食品包装盒及其生产方法 |
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| JP2001151675A (ja) | 1999-11-26 | 2001-06-05 | Nisshin Flour Milling Co Ltd | コクシジウム症の予防および/または治療用飼料 |
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| JP2003252893A (ja) | 2002-02-26 | 2003-09-10 | Japan Science & Technology Corp | 繊維状ナノ自己集合体 |
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| JP2010043045A (ja) * | 2008-08-18 | 2010-02-25 | Tohoku Kako Kk | カシューナッツ殻液の輸送方法 |
| JP2010059070A (ja) * | 2008-09-02 | 2010-03-18 | Tohoku Kako Kk | カブレ性を低減又は消失させたカシューナッツ殻液と、カシューナッツ殻液のカブレ性の低減又は消失方法。 |
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2011
- 2011-06-03 WO PCT/JP2011/062829 patent/WO2011152532A1/ja not_active Ceased
- 2011-06-03 KR KR1020127033654A patent/KR101704858B1/ko active Active
- 2011-06-03 CA CA2801286A patent/CA2801286C/en active Active
- 2011-06-03 AR ARP110101941A patent/AR083151A1/es active IP Right Grant
- 2011-06-03 JP JP2012518470A patent/JP5802662B2/ja active Active
- 2011-06-03 EP EP11789933.6A patent/EP2578670B1/en active Active
- 2011-06-03 BR BR112012030643-0A patent/BR112012030643B1/pt active IP Right Grant
- 2011-06-03 US US13/701,596 patent/US20130071530A1/en not_active Abandoned
- 2011-06-03 NZ NZ604839A patent/NZ604839A/en unknown
- 2011-06-03 CN CN2011800274650A patent/CN102933696A/zh active Pending
- 2011-06-03 PL PL11789933T patent/PL2578670T3/pl unknown
- 2011-06-03 ES ES11789933T patent/ES2757844T3/es active Active
- 2011-06-03 AU AU2011259858A patent/AU2011259858B2/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024075706A1 (ja) | 2022-10-03 | 2024-04-11 | 株式会社エス・ディー・エス バイオテック | 反芻動物のメタン産生抑制剤 |
| KR20250076551A (ko) | 2022-10-03 | 2025-05-29 | 가부시키가이샤 에스디에스 바이오텍크 | 반추 동물의 메탄 산생 억제제 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012030643A2 (pt) | 2016-08-16 |
| CN102933696A (zh) | 2013-02-13 |
| BR112012030643B1 (pt) | 2021-07-20 |
| PL2578670T3 (pl) | 2020-03-31 |
| AR083151A1 (es) | 2013-02-06 |
| JPWO2011152532A1 (ja) | 2013-08-01 |
| EP2578670A4 (en) | 2014-02-26 |
| EP2578670B1 (en) | 2019-09-25 |
| ES2757844T3 (es) | 2020-04-30 |
| CA2801286C (en) | 2018-05-15 |
| KR20130083390A (ko) | 2013-07-22 |
| JP5802662B2 (ja) | 2015-10-28 |
| AU2011259858B2 (en) | 2015-01-22 |
| CA2801286A1 (en) | 2011-12-08 |
| KR101704858B1 (ko) | 2017-02-08 |
| AU2011259858A1 (en) | 2013-01-10 |
| US20130071530A1 (en) | 2013-03-21 |
| NZ604839A (en) | 2014-07-25 |
| EP2578670A1 (en) | 2013-04-10 |
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