WO2011152533A1 - Cashew nut shell oil with improved stability - Google Patents

Cashew nut shell oil with improved stability Download PDF

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Publication number
WO2011152533A1
WO2011152533A1 PCT/JP2011/062830 JP2011062830W WO2011152533A1 WO 2011152533 A1 WO2011152533 A1 WO 2011152533A1 JP 2011062830 W JP2011062830 W JP 2011062830W WO 2011152533 A1 WO2011152533 A1 WO 2011152533A1
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Prior art keywords
cashew nut
nut shell
shell liquid
unheated
oil
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PCT/JP2011/062830
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French (fr)
Japanese (ja)
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真治 伊藤
協 長嶋
正己 望月
聖佳 大岩
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出光興産株式会社
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Publication of WO2011152533A1 publication Critical patent/WO2011152533A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B1/00Production of fats or fatty oils from raw materials
    • C11B1/06Production of fats or fatty oils from raw materials by pressing
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23DEDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00Other edible oils or fats, e.g. shortenings, cooking oils
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/158Fatty acids; Fats; Products containing oils or fats
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/28Silicates, e.g. perlites, zeolites or bentonites
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/10Feeding-stuffs specially adapted for particular animals for ruminants
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/60Feeding-stuffs specially adapted for particular animals for weanlings
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/80Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
    • Y02P60/87Re-use of by-products of food processing for fodder production

Definitions

  • the present invention is a composition comprising at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid
  • the present invention relates to a composition in which polymerizability is suppressed, and a cashew nut shell liquid formulation and feed using the composition.
  • the present invention also relates to a method for inhibiting the polymerization of cashew nut shell liquid, comprising adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid. .
  • Cashew nut shell liquid is an oily liquid contained in the shell of 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. Examples of applications to industrial products include Patent Documents 1-3. In all cases, the cashew nut shell liquid used is heat-treated.
  • Patent Documents 4-6 mention the utilization of unheated cashew nut shell liquid and its component anacardic acid for feed applications.
  • cashew nut shell liquid has a high viscosity.
  • an unheated product is very difficult to handle because it loses its fluidity at about 20 ° C. and solidifies.
  • cashew nut shell liquid has a problem that its components are unstable and the side chain portion (unsaturated fatty acid) of the aromatic ring is polymerized.
  • Non-patent Document 1 a method of absorbing the oily substance in silica to form a powder and adding it to the feed.
  • vitamin E Non-patent Document 1
  • the stability is lower than that in the liquid state, polymerization occurs, and the stability is lowered.
  • Patent Document 7 describes a method of stabilizing anacardic acid by adding and mixing calcium hydroxide to cashew nut shell liquid containing anacardic acid.
  • Patent Document 7 only describes that calcium hydroxide reacts with anacardic acid to form an insoluble metal salt, and does not convert anacardic acid to cardanol, which is unheated or heated cashew nut shell.
  • suppressing the polymerizability of cashew nut shell liquid by adding an alkali that generates a soluble salt such as sodium hydroxide or potassium hydroxide to the oil Further, Patent Document 7 does not mention any problem as to the suppression of the polymerizability of cashew nut shell liquid.
  • Patent Document 7 does not describe that solidification at around 20 ° C. can be prevented by mixing an unheated or heated cashew nut shell oil added with alkali with an excipient.
  • An object of the present invention is to suppress and stabilize the polymerization of unheated or heated cashew nut shell liquid. Another object of the present invention is to make it easy to carry unheated cashew nut shell oil that solidifies at about 20 ° C. even at low temperatures.
  • the inventors of the present invention can suppress the polymerization of cashew nut shell oil by adding an alkali that generates a soluble salt to unheated or heated cashew nut shell oil.
  • the present inventors also provide a cashew nut shell liquid formulation having improved stability by incorporating silica having a specific surface area of 500 m 3 / g or less or a pH of 6 or more into unheated and heat-treated cashew nut shell liquid. It was found that it can be obtained. Further, the present inventors have found that unheated cashew nut shell oil can be stabilized without solidifying even at a low temperature of about 20 ° C. or less by using excipients such as cereal flour and silica. The inventors have thus completed the present invention.
  • the present invention is as follows.
  • a composition comprising at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, polymerization of unheated or heated cashew nut shell oil with the alkali
  • the composition in which the property is suppressed (2)
  • a cashew nut shell liquid formulation comprising the composition according to (1) or (2) and an excipient.
  • Polymerization can be suppressed by adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid.
  • stability can be improved by mix
  • solidification around 20 ° C. can be prevented. Therefore, industrial use of cashew nut shell liquid becomes easy.
  • FIG. 1 shows changes in the composition of unheated cashew nut shell oil when four types of silica having different pH values are used.
  • the bar graph shows cardol C15: 1, C15: 2, C15: 3, cardanol C15: 1, C15: 2, C15: 3, anacardic acid C15: 1, C15: 2, C15: 3 in order from the top.
  • FIG. 2 shows the correlation between the pH or specific surface area of nine types of silica and the amount (concentration) of cardanol or cardol after 8 hours.
  • FIG. 3 shows the change in the composition of unheated or heated cashew nut shell liquid (day 0 and day 3) when no alkali is added. The bar graph indicates that the substances shown are included in order from the top.
  • FIG. 1 shows changes in the composition of unheated cashew nut shell oil when four types of silica having different pH values are used.
  • the bar graph shows cardol C15: 1, C15: 2, C15: 3, cardanol C15:
  • FIG. 4 shows the change in composition of unheated or heated cashew nut shell liquid (day 0 and day 3) when 2% by weight of alkali is added.
  • the bar graph shows cardol C15: 1, C15: 2, C15: 3 in order from the top.
  • FIG. 5 shows suppression of the polymerization reaction in feed when alkaline silica is used.
  • the bar graph shows cardol C15: 1, C15: 2, C15: 3 in order from the top.
  • composition of the present invention comprises at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, and the polymerization property of the unheated or heated cashew nut shell oil by the alkali. Is suppressed.
  • 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.
  • the heated cashew nut shell oil obtained by heat-treating non-heated cashew nut shell oil at 130 ° C. or higher is converted to cardanol by decarboxylation of anacardic acid, which is the main component of non-heated cashew nut shell oil, and anacardic acid is converted to 0-10. % By mass, 55 to 80% by mass of cardanol, and 5 to 30% by mass of cardol.
  • 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 (15: 1, 15: 2). 15: 3).
  • the polymerization of cashew nut shell oil means that its components, anacardic acid, cardanol, and cardol, are polymerized and the insoluble portion in the organic solvent increases.
  • the polymerization of cashew nut shell liquid is evaluated by reducing the concentration of cardol by composition analysis by HPLC using ethyl acetate.
  • 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, for example, dry distillation or solvent extraction of the cashew nut shell by heating or extraction.
  • 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 or a heating method.
  • the cashew nut shell oil used in the present invention may be obtained by pulverizing and crushing heat sterilized oil or cashew nut shell. A commercial item can also be used for the cashew nut shell liquid used in this invention.
  • the cashew nut shell liquid of the present invention may be a heated cashew nut shell oil obtained by heating the non-heated cashew nut shell oil obtained as described above to 70 ° C or higher, preferably 130 ° C or higher.
  • the cashew nut shell oil of the present invention may be obtained by press-extracting cashew nut shell (non-heated cashew nut shell oil) and heat treating it at 130 ° C.
  • the alkali used in the present invention is, for example, at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia.
  • Sodium hydroxide and potassium hydroxide are alkalis that produce soluble metal salts such as sodium salts and potassium salts. Two or more of these alkalis may be combined and added to cashew nut shell liquid.
  • the amount of the alkali used is preferably 2% by weight or more, more preferably 5% by weight to 10% by weight, based on cashew nut shell liquid (CNSL).
  • the composition of the present invention can be produced by adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid.
  • the cashew nut shell liquid formulation of the present invention comprises unheated or heated cashew nut shell liquid, one or more excipients, and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia. If there is no particular limitation.
  • the 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 is mixed with one or more excipients. , A cashew nut shell liquid formulation.
  • the cashew nut shell liquid formulation of the present invention may be prepared by previously mixing an alkali component and an excipient, and further mixing the excipient mixed with the alkali component with unheated or heated cashew nut shell liquid. Good. Under the influence of the alkali component in the excipient, polymerization of unheated or heated cashew nut shell liquid can be suppressed in a state where the alkali component is mixed with the excipient. Further, in the cashew nut shell liquid formulation of the present invention, an alkali component may be added by spraying or the like after mixing unheated or heated cashew nut shell oil and an excipient.
  • 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 eg, silica
  • the pH is preferably 6 or more and / or the specific surface area is preferably 500 m 3 / g or less. More preferably, the pH is 7 to 12, and / or the specific surface area is 400 m 3 / g or less.
  • the specific surface area can be measured by the BET method.
  • the same pH, specific surface area, and blending ratio may be used.
  • 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 cashew nut shell liquid formulation of the present invention comprises one or two or more in addition to unheated or heated cashew nut shell liquid, excipients and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia.
  • Antioxidants may be included, such as ethoxyquin, t-butylhydroxytoluene, t-butylhydroxyanisole, t-butylhydroquinone, ascorbic acid and its esters, vitamin E, gallic acid and its esters, erythorbic acid, chlorogen Examples include, but are not limited to, acids, sulfites, thiosulfates, phosphites, hypophosphites, and phosphates.
  • the cashew nut shell liquid formulation of the present invention comprises one or two or more in addition to unheated or heated cashew nut shell liquid, excipients and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia.
  • Antibiotics may be used, such as zinc bacitracin, aviramycin, alkyltrimethylammonium calcium oxytetracycline, efrotomycin, enramycin, chlortetracycline, cedecamycin, senduramycin, narasin, nociheptide, virginiamycin, bicozamycin, flavophospho Paul, Polynactin, Monensin, Salinomycin, Rasaroside, Laisoserine, Ronomycin, Avoparcin, Collistin sulfate, Tyrosin phosphate, Amprolium etopabate Amprolium, Etopabeto-sulfaquinoxaline, morantel citrate, Dekokineto, Naikarubajin, halo Fujinon polystyrene sulfonic acid, kitasamycin, Chiopeputon, destructors mycin A, hygromycin B and its salts, and the like as examples.
  • the dosage form of the 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 cashew nut shell liquid formulation of the present invention is prepared by mixing unheated or heated cashew nut shell oil, one or more excipients, an alkaline component, and optionally one or two or more optional components. Can be manufactured. Such a powdery preparation of the present invention can be used as a feed without being mixed with other optional components.
  • the cashew nut shell liquid formulation of the present invention can be made into granules such as pellets in addition to powders.
  • one or two or more hardened oils may be used in addition to adding excipients and alkali components to unheated or heated cashew nut shell liquid.
  • 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 cashew nut shell liquid formulation of the present invention may also be coated, for example after granulation, selected from zein, shellac, HPMC (hydroxypropylmethylcellulose), pullulan, hemirose, glucose, lactose, trehalose and starch. Or it can coat with two or more coating agents. Moreover, you may coat
  • the present invention includes a feed containing the composition of the present invention and / or cashew nut shell liquid formulation.
  • the polymerization of cashew nut shell liquid is suppressed in the unheated or heated cashew nut shell liquid contained in the feed.
  • 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, this unheated cashew nut shell liquid was heated at 150 ° C. for 10 hours to obtain a heated cashew nut shell liquid in which the anacardic acid in the component was converted to cardanol by a decarboxylation reaction. A list of silicas (9 types) used as excipients is shown in Table 1. All silica was obtained from Evonik Degussa Japan.
  • 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 10 g of unheated cashew nut shell oil was dispensed into each beaker, 5 g of various silicas were added thereto, and the mixture was stirred uniformly. Each was sealed and then placed in a constant temperature bath at 80 ° C., and sampling was performed after 8 hours and 1 day. The composition was adjusted to 5000 ppm (including silica) using ethyl acetate, and composition analysis was performed by HPLC. FIG. 1 shows the composition change when four types of silica having different pHs are used. The composition change data (concentration: nmol / L) is shown in Table 2 below.
  • FIG. 2 shows the correlation between the pH and specific surface area of silica and the amount (concentration) of cardanol and cardol after 8 hours in the nine types of silica used.
  • the amounts of cardanol and cardol are shown in Table 3 below.
  • Example 4 10g of unheated cashew nut shell oil and 10g of heated cashew nut shell oil are dispensed into each beaker, and various alkali components (NaOH solution (53.6%), KOH solution (56.5%) so as to be 2% by weight with respect to each cashew nut shell oil) , NH 3 (28%)) was added in aqueous solution. There, Sipernat 22 5g was added, and it stirred so that it might become uniform. Each was sealed and then placed in a constant temperature bath at 80 ° C. and sampled after 3 days. The composition was adjusted to 500 ppm (including silica) using ethyl acetate, and composition analysis was performed by HPLC.
  • FIG. 3 shows a change in the case of carrying out without adding alkali (comparative example). The data (concentration: ppm) about the change is shown in Table 4 below.
  • Example 5 Add 1% by weight of two silica preparations (Carplex BS306 and Carplex # 1120) prepared in Example 3 to 100 g of feed (standard feed for raising young cattle: SDC No. 2 Japan Formula Feed Co., Ltd.) A feed containing unheated cashew nut shell liquid was prepared. 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 are shown as the concentration (ppm) at the time of analysis for cardol (FIG. 5). From this, it can be seen that those using Carplex # 1120 (pH 10.6) exist stably in feed without polymerization proceeding. The data (concentration: ppm) for FIG. 5 is shown in Table 6 below.
  • Example 6 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 oil (2 wt% NaOH) 0.05 wt% By mixing, it becomes powder and can be prevented from solidifying around 20 ° C.
  • Polymerization can be suppressed by adding sodium hydroxide, potassium hydroxide, or ammonia to unheated or heated cashew nut shell liquid.
  • stability can be improved by mixing an unheated or heated cashew nut shell oil to which sodium hydroxide, potassium hydroxide, or ammonia is added with an excipient.
  • an excipient with unheated cashew nut shell liquid to which sodium hydroxide, potassium hydroxide, or ammonia is added, solidification around 20 ° C. can be prevented. Therefore, industrial use of cashew nut shell liquid becomes easy.

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Abstract

Provided is a composition containing at least one type of alkali selected from among sodium hydroxide, potassium hydroxide and ammonia, and heated or unheated cashew nut shell oil. Polymerization of the heated or unheated cashew nut shell oil is minimized by the alkali.

Description

安定性が向上したカシューナッツ殻油Cashew nut shell oil with improved stability
 本発明は、水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリと未加熱または加熱カシューナッツ殻油を含む組成物であって、前記アルカリにより未加熱または加熱カシューナッツ殻油の重合性が抑制されている組成物、並びにこれを用いたカシューナッツ殻油製剤及び飼料に関する。本発明はまた、未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加することを特徴とする、カシューナッツ殻油の重合性抑制方法に関する。 The present invention is a composition comprising at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, The present invention relates to a composition in which polymerizability is suppressed, and a cashew nut shell liquid formulation and feed using the composition. The present invention also relates to a method for inhibiting the polymerization of cashew nut shell liquid, comprising adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid. .
 カシューナッツ殻油(CNSL)は、カシューナッツ ツリー(Anacardium occidentale L.)の実の殻に含まれる油状の液体である。カシューナッツ殻油は、その成分として、アナカルド酸、カルダノール、カルドール、メチルカルドールを主に含む。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。
 工業製品への応用例としては特許文献1-3があるが、いずれも、使用されているカシューナッツ殻油は加熱処理されたものである。また、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、具体的なカシューナッツ殻油の飼料への添加方法については記載されていない。実際、カシューナッツ殻油は粘度が高く、特に未加熱品は約20℃にて流動性が消失し、固化するなど非常に取り扱い難い。また、カシューナッツ殻油はその成分が不安定であり、芳香環の側鎖部分(不飽和脂肪酸)が重合するという問題もあった。
 油状物質の飼料への添加方法としては、シリカに油状物質を吸収させ粉体状とし、飼料に添加する方法がビタミンEで知られている(非特許文献1)。しかし、同様の方法をこのカシューナッツ殻油に適用すると、液体状態よりも安定性が低く、重合し、安定性が低下するという問題点があった。
Cashew nut shell liquid (CNSL) is an oily liquid contained in the shell of 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. Usually, cashew nut shell oil is used by converting anacardic acid into cardanol by heat treatment in a cashew nut production place.
Examples of applications to industrial products include Patent Documents 1-3. In all cases, the cashew nut shell liquid used is heat-treated. Patent Documents 4-6 mention the utilization of unheated cashew nut shell liquid and its component anacardic acid for feed applications. For specific methods of adding cashew nut shell liquid to feed, Not listed. Actually, cashew nut shell liquid has a high viscosity. Particularly, an unheated product is very difficult to handle because it loses its fluidity at about 20 ° C. and solidifies. In addition, cashew nut shell liquid has a problem that its components are unstable and the side chain portion (unsaturated fatty acid) of the aromatic ring is polymerized.
As a method for adding an oily substance to a feed, a method of absorbing the oily substance in silica to form a powder and adding it to the feed is known as vitamin E (Non-patent Document 1). However, when the same method is applied to this cashew nut shell liquid, there is a problem that the stability is lower than that in the liquid state, polymerization occurs, and the stability is lowered.
 特許文献7には、アナカルド酸を含有したカシューナッツ殻液に水酸化カルシウムを添加混合し、アナカルド酸を安定化させる方法が記載されている。しかしながら、特許文献7には、水酸化カルシウムはアナカルド酸と反応して溶解性のない金属塩を生じ、アナカルド酸をカルダノールに変換させないことが記載されているのみであり、未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウムのような溶解性のある塩を生じるアルカリを添加して、カシューナッツ殻油の重合性を抑制することは記載されていない。また、特許文献7には、カシューナッツ殻油の重合性を抑制することについては課題として何ら言及されていない。
 なお、未加熱または加熱カシューナッツ殻油について、安定性および取り扱い性の向上の両面から粉体化した例は今までにない。また、アルカリを添加した未加熱または加熱カシューナッツ殻油を賦形剤と混合することにより、20℃近辺で固化することを防止できることも特許文献7に記載されていない。
Patent Document 7 describes a method of stabilizing anacardic acid by adding and mixing calcium hydroxide to cashew nut shell liquid containing anacardic acid. However, Patent Document 7 only describes that calcium hydroxide reacts with anacardic acid to form an insoluble metal salt, and does not convert anacardic acid to cardanol, which is unheated or heated cashew nut shell. There is no description of suppressing the polymerizability of cashew nut shell liquid by adding an alkali that generates a soluble salt such as sodium hydroxide or potassium hydroxide to the oil. Further, Patent Document 7 does not mention any problem as to the suppression of the polymerizability of cashew nut shell liquid.
Heretofore, there has been no example of pulverizing unheated or heated cashew nut shell oil from the viewpoint of improving stability and handleability. Further, Patent Document 7 does not describe that solidification at around 20 ° C. can be prevented by mixing an unheated or heated cashew nut shell oil added with alkali with an excipient.
特開2008-144171号公報JP 2008-144171 A 特開2006-111839号公報JP 2006-1111839 A 特開2003-252893号公報JP 2003-252893 A 特開2003-238400号公報JP 2003-238400 A 特開2001-151675号公報JP 2001-151675 A 特開平8-231410号公報JP-A-8-231410 特開2010-88363号公報JP 2010-88363 A
 本発明は、未加熱または加熱カシューナッツ殻油の重合を抑制して安定化することを課題とする。本発明はまた、約20℃で固化する未加熱のカシューナッツ殻油を、低温でも運び易くすることを課題とする。 An object of the present invention is to suppress and stabilize the polymerization of unheated or heated cashew nut shell liquid. Another object of the present invention is to make it easy to carry unheated cashew nut shell oil that solidifies at about 20 ° C. even at low temperatures.
 本発明者らは、上記課題を解決すべく鋭意研究を行った結果、溶解性のある塩を生じるアルカリを未加熱または加熱カシューナッツ殻油に加えることにより、カシューナッツ殻油の重合が抑制されることを見出した。
 本発明者らはまた、未加熱・加熱処理したカシューナッツ殻油に、比表面積が500m3/g以下またはpHが6以上のシリカを配合することにより、安定性を向上させたカシューナッツ殻油製剤が得られることを見出した。
 本発明者らはさらに、穀物粉、シリカ等の賦形剤を用いることにより、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安定化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。
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention can suppress the polymerization of cashew nut shell oil by adding an alkali that generates a soluble salt to unheated or heated cashew nut shell oil. I found.
The present inventors also provide a cashew nut shell liquid formulation having improved stability by incorporating silica having a specific surface area of 500 m 3 / g or less or a pH of 6 or more into unheated and heat-treated cashew nut shell liquid. It was found that it can be obtained.
Further, the present inventors have found that unheated cashew nut shell oil can be stabilized without solidifying even at a low temperature of about 20 ° C. or less by using excipients such as cereal flour and silica.
The inventors have thus completed the present invention.
 すなわち、本発明は以下のとおりである。
(1)水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリと未加熱または加熱カシューナッツ殻油を含む組成物であって、前記アルカリにより未加熱または加熱カシューナッツ殻油の重合性が抑制されている、組成物。
(2)アルカリの量がカシューナッツ殻油比2重量%以上である(1)に記載の組成物。
(3)(1)または(2)に記載の組成物と賦形剤とを含むカシューナッツ殻油製剤。
(4)前記賦形剤がシリカであることを特徴とする(3)に記載のカシューナッツ殻油製剤。
(5)前記シリカの比表面積が500m3/g以下であることを特徴とする(4)に記載のカシューナッツ殻油製剤。
(6)前記シリカのpHが6以上であることを特徴とする(4)または(5)に記載のカシューナッツ殻油製剤。
(7)(1)または(2)に記載の組成物および/あるいは(3)~(6)のいずれか1項に記載のカシューナッツ殻油製剤を含むことを特徴とする飼料。
(8)未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加することを特徴とする、カシューナッツ殻油の重合性抑制方法。
That is, the present invention is as follows.
(1) A composition comprising at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, polymerization of unheated or heated cashew nut shell oil with the alkali The composition in which the property is suppressed.
(2) The composition according to (1), wherein the amount of alkali is 2% by weight or more of the cashew nut shell liquid ratio.
(3) A cashew nut shell liquid formulation comprising the composition according to (1) or (2) and an excipient.
(4) The cashew nut shell liquid formulation according to (3), wherein the excipient is silica.
(5) The cashew nut shell liquid formulation according to (4), wherein the silica has a specific surface area of 500 m 3 / g or less.
(6) The cashew nut shell liquid formulation according to (4) or (5), wherein the silica has a pH of 6 or more.
(7) A feed comprising the composition according to (1) or (2) and / or the cashew nut shell liquid formulation according to any one of (3) to (6).
(8) A method for suppressing the polymerization of cashew nut shell liquid, comprising adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell oil.
 未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加することにより、重合を抑制することができる。また、水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加した未加熱または加熱カシューナッツ殻油に賦形剤を配合することにより、安定性を向上させることができる。さらに、水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加した未加熱カシューナッツ殻油に賦形剤を配合することにより、20℃近辺で固化することを防止できる。従って、カシューナッツ殻油の工業的利用が容易になる。 Polymerization can be suppressed by adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid. Moreover, stability can be improved by mix | blending an excipient | filler with the unheated or heated cashew nut shell liquid which added the at least 1 sort (s) of alkali selected from sodium hydroxide, potassium hydroxide, and ammonia. Further, by blending an excipient with unheated cashew nut shell liquid to which at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia is added, solidification around 20 ° C. can be prevented. Therefore, industrial use of cashew nut shell liquid becomes easy.
図1は、pHの異なる4種のシリカを用いた場合の未加熱カシューナッツ殻油の組成変化を示す。棒グラフは、上から順に、カルドールC15:1、C15:2、C15:3、カルダノールC15:1、C15:2、C15:3、アナカルド酸C15:1、C15:2、C15:3を示す。FIG. 1 shows changes in the composition of unheated cashew nut shell oil when four types of silica having different pH values are used. The bar graph shows cardol C15: 1, C15: 2, C15: 3, cardanol C15: 1, C15: 2, C15: 3, anacardic acid C15: 1, C15: 2, C15: 3 in order from the top. 図2は、9種類のシリカの、pHまたは比表面積と8時間後のカルダノールまたはカルドール量(濃度)との相関を示す。FIG. 2 shows the correlation between the pH or specific surface area of nine types of silica and the amount (concentration) of cardanol or cardol after 8 hours. 図3は、アルカリを添加しない場合の、未加熱または加熱カシューナッツ殻油の組成の変化(0日目および3日目)を示す。棒グラフは、上から順に、示される物質が含まれることを示す。FIG. 3 shows the change in the composition of unheated or heated cashew nut shell liquid (day 0 and day 3) when no alkali is added. The bar graph indicates that the substances shown are included in order from the top. 図4は、2重量%のアルカリを添加する場合の、未加熱または加熱カシューナッツ殻油の組成の変化(0日目および3日目)を示す。棒グラフは、上から順に、カルドールC15:1、C15:2、C15:3を示す。FIG. 4 shows the change in composition of unheated or heated cashew nut shell liquid (day 0 and day 3) when 2% by weight of alkali is added. The bar graph shows cardol C15: 1, C15: 2, C15: 3 in order from the top. 図5は、アルカリ性シリカを用いた場合の飼料における重合反応の抑制を示す。棒グラフは、上から順に、カルドールC15:1、C15:2、C15:3を示す。FIG. 5 shows suppression of the polymerization reaction in feed when alkaline silica is used. The bar graph shows cardol C15: 1, C15: 2, C15: 3 in order from the top.
 本発明の組成物は、水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリと未加熱または加熱カシューナッツ殻油を含み、前記アルカリにより未加熱または加熱カシューナッツ殻油の重合性が抑制されていることを特徴とする。 The composition of the present invention comprises at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, and the polymerization property of the unheated or heated cashew nut shell oil by the alkali. Is suppressed.
 本発明に用いるカシューナッツ殻油は、カシューナッツ ツリー(Anacardium occidentale L.)の実の殻に含まれる油状の液体である。カシューナッツ殻油は、その成分として、アナカルド酸、カルダノール、カルドール、メチルカルドールを含むものである。
 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。また、非加熱カシューナッツ殻油を130℃以上で加熱処理して得られる加熱カシューナッツ殻油は、非加熱カシューナッツ殻油の主成分のアナカルド酸が脱炭酸しカルダノールに変換され、アナカルド酸を0~10質量%、カルダノールを55~80質量%、カルドールを5~30質量%含むものとなる。
 なお、アナカルド酸、カルダノール、およびカルドールは、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(15:1,15:2,15:3)。
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. The heated cashew nut shell oil obtained by heat-treating non-heated cashew nut shell oil at 130 ° C. or higher is converted to cardanol by decarboxylation of anacardic acid, which is the main component of non-heated cashew nut shell oil, and anacardic acid is converted to 0-10. % By mass, 55 to 80% by mass of cardanol, and 5 to 30% by mass of cardol.
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 (15: 1, 15: 2). 15: 3).
 本発明において、カシューナッツ殻油の重合とは、その成分であるアナカルド酸、カルダノール、カルドールが重合し、有機溶媒に不溶の部分が増大することをいう。本発明において、カシューナッツ殻油の重合は、酢酸エチルを使用するHPLCによる組成分析により、カルドールの濃度の減少により評価する。 In the present invention, the polymerization of cashew nut shell oil means that its components, anacardic acid, cardanol, and cardol, are polymerized and the insoluble portion in the organic solvent increases. In the present invention, the polymerization of cashew nut shell liquid is evaluated by reducing the concentration of cardol by composition analysis by HPLC using ethyl acetate.
 本発明において使用されるカシューナッツ殻油は、カシューナッツの殻を圧搾することにより抽出した植物油として得ることができる。また、本発明において使用されるカシューナッツ殻油は、加熱または抽出により、例えば、カシューナッツ殻を乾留又は溶剤抽出して得ることもできる。さらに、本発明において使用されるカシューナッツ殻油は、特開平8-231410号公報に記載されている方法によって、例えば、溶剤抽出法や加熱法によって得ることができる。
 本発明において使用されるカシューナッツ殻油は、その他にも加熱殺菌処理油、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。
 本発明のカシューナッツ殻油は、上記のようにして得られた非加熱カシューナッツ殻油を、70℃以上、好ましくは130℃以上に加熱することによって得た加熱カシューナッツ殻油であってもよい。
 本発明のカシューナッツ殻油は、カシューナッツの殻から圧搾抽出(非加熱カシューナッツ殻油)し、これを130℃に加熱処理して得たものでもよい。
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, for example, dry distillation or solvent extraction of the cashew nut shell by heating or extraction. Furthermore, 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 or a heating method.
The cashew nut shell oil used in the present invention may be obtained by pulverizing and crushing heat sterilized oil or cashew nut shell.
A commercial item can also be used for the cashew nut shell liquid used in this invention.
The cashew nut shell liquid of the present invention may be a heated cashew nut shell oil obtained by heating the non-heated cashew nut shell oil obtained as described above to 70 ° C or higher, preferably 130 ° C or higher.
The cashew nut shell oil of the present invention may be obtained by press-extracting cashew nut shell (non-heated cashew nut shell oil) and heat treating it at 130 ° C.
 本発明において使用されるアルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリである。水酸化ナトリウム、水酸化カリウムは、ナトリウム塩、カリウム塩のような溶解性のある金属塩を生じるアルカリである。これらのアルカリは、2種類以上組み合わせてカシューナッツ殻油に添加されてもよい。
 使用されるアルカリの量としては、カシューナッツ殻油(CNSL)比2重量%以上であることが好ましく、より好ましくは、5重量%~10重量%である。
 本発明の組成物は、未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加することにより製造することができる。
The alkali used in the present invention is, for example, at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia. Sodium hydroxide and potassium hydroxide are alkalis that produce soluble metal salts such as sodium salts and potassium salts. Two or more of these alkalis may be combined and added to cashew nut shell liquid.
The amount of the alkali used is preferably 2% by weight or more, more preferably 5% by weight to 10% by weight, based on cashew nut shell liquid (CNSL).
The composition of the present invention can be produced by adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell liquid.
 本発明のカシューナッツ殻油製剤は、未加熱または加熱カシューナッツ殻油、1または2以上の賦形剤ならびに水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリ成分を含むものであれば特に限定されない。
 本発明のカシューナッツ殻油製剤は、本発明の組成物と1または2以上の賦形剤とを含む製剤が好ましく、例えば、本発明の組成物と1または2以上の賦形剤とを混合し、カシューナッツ殻油製剤とすることができる。
 また、本発明のカシューナッツ殻油製剤は、アルカリ成分と賦形剤とをあらかじめ混合し、アルカリ成分と混合された賦形剤をさらに未加熱または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。賦形剤中のアルカリ成分の影響により、アルカリ成分が賦形剤と混合された状態で、未加熱または加熱カシューナッツ殻油の重合を抑制することができる。
 さらに、本発明のカシューナッツ殻油製剤は、未加熱または加熱カシューナッツ殻油と賦形剤とを混合した後、吹き付け処理等によりアルカリ成分を添加しても良い。
The cashew nut shell liquid formulation of the present invention comprises unheated or heated cashew nut shell liquid, one or more excipients, and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia. If there is no particular limitation.
The 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 is mixed with one or more excipients. , A cashew nut shell liquid formulation.
The cashew nut shell liquid formulation of the present invention may be prepared by previously mixing an alkali component and an excipient, and further mixing the excipient mixed with the alkali component with unheated or heated cashew nut shell liquid. Good. Under the influence of the alkali component in the excipient, polymerization of unheated or heated cashew nut shell liquid can be suppressed in a state where the alkali component is mixed with the excipient.
Further, in the cashew nut shell liquid formulation of the present invention, an alkali component may be added by spraying or the like after mixing unheated or heated cashew nut shell oil and an excipient.
 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、pHが6以上であることが好ましく、そして/またはその比表面積が500m3/g以下であることが好ましい。より好ましくは、pH7~12、そして/またはその比表面積が、400m3/g以下である。なお、比表面積は、BET法によって測定することができる。
 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/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pH、比表面積、配合比とすればよい。
 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。
Inorganic excipients include, but are not limited to, silicic acid and its salts (eg, silica), vermiculite, diatomaceous earth, talc, kaolin, and bentonite.
When silicic acid and its salts are used as the inorganic excipient, the pH is preferably 6 or more and / or the specific surface area is preferably 500 m 3 / g or less. More preferably, the pH is 7 to 12, and / or the specific surface area is 400 m 3 / g or less. The specific surface area can be measured by the BET method.
When silica is used as the inorganic excipient, the blending ratio (weight ratio) is preferably silica / cashew nut shell liquid = 1 / 3.0 to 1 / 0.1. When other inorganic excipients are used, the same pH, specific surface area, and blending ratio may be used.
In addition, 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.
 本発明のカシューナッツ殻油製剤は、未加熱または加熱カシューナッツ殻油、賦形剤ならびに水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリ成分に加えて、1または2以上の酸化防止剤を含んでいてもよく、例えば、エトキシキン、t-ブチルヒドロキシトルエン、t-ブチルヒドロキシアニソール、t-ブチルヒドロキノン、アスコルビン酸およびそのエステル、ビタミンE、没食子酸およびそのエステル、エリソルビン酸、クロロゲン酸、亜硫酸塩、チオ硫酸塩、亜リン酸塩、次亜リン酸塩、リン酸塩が挙げられるが、これらに限定されない。
 本発明のカシューナッツ殻油製剤は、未加熱または加熱カシューナッツ殻油、賦形剤ならびに水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリ成分に加えて、1または2以上の抗生物質を使用してもよく、亜鉛バシトラシン、アビラマイシン、アルキルトリメチルアンモニウムカルシウムオキシテトラサイクリン、エフロトマイシン、エンラマイシン、クロルテトラサイクリン、セデカマイシン、センデュラマイシン、ナラシン、ノシヘプタイド、バージニアマイシン、ビコザマイシン、フラボフォスフォリポール、ポリナクチン、モネンシン、サリノマイシン、ラサロシド、ライソセリン、ロノマイシン、アボパルシン、硫酸コリスチン、リン酸タイロシン、アンプロリウム・エトパベート、アンプロリウム・エトパベート・スルファキノキサリン、クエン酸モランテル、デコキネート、ナイカルバジン、ハロフジノンポリスチレンスルホン酸、キタサマイシン、チオペプトン、デストマイシンA、ハイグロマイシンBとその塩類等が例として挙げられる。
The cashew nut shell liquid formulation of the present invention comprises one or two or more in addition to unheated or heated cashew nut shell liquid, excipients and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia. Antioxidants may be included, such as ethoxyquin, t-butylhydroxytoluene, t-butylhydroxyanisole, t-butylhydroquinone, ascorbic acid and its esters, vitamin E, gallic acid and its esters, erythorbic acid, chlorogen Examples include, but are not limited to, acids, sulfites, thiosulfates, phosphites, hypophosphites, and phosphates.
The cashew nut shell liquid formulation of the present invention comprises one or two or more in addition to unheated or heated cashew nut shell liquid, excipients and at least one alkaline component selected from sodium hydroxide, potassium hydroxide, and ammonia. Antibiotics may be used, such as zinc bacitracin, aviramycin, alkyltrimethylammonium calcium oxytetracycline, efrotomycin, enramycin, chlortetracycline, cedecamycin, senduramycin, narasin, nociheptide, virginiamycin, bicozamycin, flavophospho Paul, Polynactin, Monensin, Salinomycin, Rasaroside, Laisoserine, Ronomycin, Avoparcin, Collistin sulfate, Tyrosin phosphate, Amprolium etopabate Amprolium, Etopabeto-sulfaquinoxaline, morantel citrate, Dekokineto, Naikarubajin, halo Fujinon polystyrene sulfonic acid, kitasamycin, Chiopeputon, destructors mycin A, hygromycin B and its salts, and the like as examples.
 本発明のカシューナッツ殻油製剤の剤形は、穀物粉、シリカなどの賦形剤を含有することにより、粉剤として製剤化することができる。すなわち、本発明のカシューナッツ殻油製剤は、未加熱または加熱カシューナッツ殻油、1または2以上の賦形剤、アルカリ成分、および必要に応じて1または2以上の任意成分を混合し、粉剤に製剤化することにより製造することができる。このような本発明の粉末状の製剤は、他の任意成分と混合させず飼料とすることができる。 The dosage form of the 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 cashew nut shell liquid formulation of the present invention is prepared by mixing unheated or heated cashew nut shell oil, one or more excipients, an alkaline component, and optionally one or two or more optional components. Can be manufactured. Such a powdery preparation of the present invention can be used as a feed without being mixed with other optional components.
 本発明のカシューナッツ殻油製剤は、粉剤以外にもペレット剤などの粒剤にすることができる。この場合、未加熱または加熱カシューナッツ殻油に賦形剤およびアルカリ成分を加えるほかに1または2以上の硬化油を使用してもよい。硬化油としては、パーム油、ダイズ油、ナタネ油などを硬化した油が用いられる。硬化油の融点は45~65℃となっているのが好ましい。なお、ペレット化とするには、通常の押し出し造粒機を用いて製造することができる。 The cashew nut shell liquid formulation of the present invention can be made into granules such as pellets in addition to powders. In this case, one or two or more hardened oils may be used in addition to adding excipients and alkali components to unheated or heated cashew nut shell liquid. As 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. In addition, in order to pelletize, it can manufacture using a normal extrusion granulator.
 本発明のカシューナッツ殻油製剤はまた、コーティングされていてもよく、例えば、造粒後、ゼイン、セラック、HPMC(ヒドロキシプロピルメチルセルロース)、プルラン、ヘミロース、グルコース、乳糖、トレハロースおよびデンプンから選択される1または2以上のコート剤によりコーティングすることができる。また、それらを成分とするシートにより被覆されていても良い。 The cashew nut shell liquid formulation of the present invention may also be coated, for example after granulation, selected from zein, shellac, HPMC (hydroxypropylmethylcellulose), pullulan, hemirose, glucose, lactose, trehalose and starch. Or it can coat with two or more coating agents. Moreover, you may coat | cover with the sheet | seat which uses them as a component.
 本発明には、本発明の組成物および/またはカシューナッツ殻油製剤を含む飼料が含まれる。本発明において、飼料に含まれる未加熱または加熱カシューナッツ殻油は、カシューナッツ殻油の重合が抑制されている。 The present invention includes a feed containing the composition of the present invention and / or cashew nut shell liquid formulation. In the present invention, the polymerization of cashew nut shell liquid is suppressed in the unheated or heated cashew nut shell liquid contained in the feed.
 本発明の飼料において本発明の組成物および/またはカシューナッツ殻油製剤と配合される飼料成分の種類や配合割合などは特に制限されず、それぞれの動物に対して従来から給与されている飼料であればよく、例えば、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、炭酸カルシウム、第2リン酸カルシウム、イエログリース、ビタミン類、ミネラル類などの1または2以上の飼料成分を用いて調製することができる。 In the feed of the present invention, 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. For example, 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.
 本発明の飼料は、未加熱カシューナッツ殻油製剤をそのまま飼料成分に添加し、混合して製造することができる。この際、粉末状、固形状の未加熱カシューナッツ殻油製剤を用いる場合は、混合を容易にするために製剤を液状又はゲル状の形態にしてもよい。この場合は、水、大豆油、菜種油、コーン油などの植物油、液体動物油、ポリビニルアルコールやポリビニルピロリドン、ポリアクリル酸などの水溶性高分子化合物の1または2以上を液体担体として用いることができる。また、飼料中におけるカシューナッツ殻油の均一性を保つために、アルギン酸、アルギン酸ナトリウム、キサンタンガム、カゼインナトリウム、アラビアゴム、グアーガム、タマリンド種子多糖類などの水溶性多糖類の1または2以上を配合することも好ましい。 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. At this time, when a powdered or solid unheated cashew nut shell liquid formulation is used, the formulation may be in a liquid or gel form for easy mixing. In this case, 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. In addition, in order to maintain the uniformity of cashew nut shell liquid in the feed, one or more of 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.
 本発明の飼料は、牛、豚、鶏、羊、馬、ヤギなどの家畜の飼育に好適である。摂取させる飼料の量は、動物の種類、体重、年齢、性別、健康状態、飼料の成分などにより適宜調節することができ、このとき飼料に含まれるカシューナッツナッツ殻油が好ましくは0.005~500g/頭・日、より好ましくは0.05~100g/頭・日である。
 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。
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. At this time, 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.
As a method for ingesting and rearing a feed, a commonly used method can be employed depending on the type of animal.
実施例1.試料調製
 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、この未加熱カシューナッツ殻油を150℃にて10時間加熱することにより、成分中のアナカルド酸が脱炭酸反応によりカルダノールに変換した加熱カシューナッツ殻油を得た。賦形剤として使用したシリカ(9種類)は一覧を表1に示した。シリカは全てエボニック デグサ ジャパン(株)より入手した。
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, this unheated cashew nut shell liquid was heated at 150 ° C. for 10 hours to obtain a heated cashew nut shell liquid in which the anacardic acid in the component was converted to cardanol by a decarboxylation reaction. A list of silicas (9 types) used as excipients is shown in Table 1. All silica was obtained from Evonik Degussa Japan.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
実施例2.HPLC測定
(1)図1,2,5について
 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。
(2)図3,4について
 PU-2089 Plus(日本分光(株))、検出器(MD-2010 plus、日本分光(株))を使用した。分析条件は、上記(1)と同様に実施した。
Example 2 HPLC Measurement (1) About FIGS. 1, 2 and 5 Waters600 (Nippon Waters), Detector (Waters490E, Nihon Waters), Printer (Chromatopack C-R6A, Shimadzu), Column (SUPELCOSIL) LC18, SUPELCO) was used. The conditions were solvent acetonitrile: water: acetic acid = 80: 20: 1 (volume ratio), flow rate 2 ml / ml, temperature 25 ° C., absorbance 280 nm.
(2) About FIGS. 3 and 4 PU-2089 Plus (JASCO Corporation) and detector (MD-2010 plus, JASCO Corporation) were used. The analysis conditions were the same as (1) above.
pH測定
 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。
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.
実施例3
 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、各種シリカ 5g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、8時間、1日後にサンプリングを行った。酢酸エチルを使用して5000ppm(シリカ込み)に調整し、HPLCによる組成分析を実施した。
 pHの異なる4種のシリカを用いた場合の組成変化を図1に示した。なお、組成変化のデータ(濃度:nmol/L)を以下の表2に示す。
Example 3
10 g of unheated cashew nut shell oil was dispensed into each beaker, 5 g of various silicas were added thereto, and the mixture was stirred uniformly. Each was sealed and then placed in a constant temperature bath at 80 ° C., and sampling was performed after 8 hours and 1 day. The composition was adjusted to 5000 ppm (including silica) using ethyl acetate, and composition analysis was performed by HPLC.
FIG. 1 shows the composition change when four types of silica having different pHs are used. The composition change data (concentration: nmol / L) is shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 シリカのpHが酸性側に行くに従い、回収された未加熱カシューナッツ殻油成分の量(濃度)が小さくなる事が分かる。これは80℃に静置した間に重合が進行し、酢酸エチルに不溶の部分が増大した為である。特に、カルドールに於いてピークの減少が顕著であり、カルドールが特に重合し易いことが分かる。
 図2には、使用した9種類のシリカに於いて、シリカのpHおよび比表面積と8時間後のカルダノールおよびカルドール量(濃度)との相関を図示した。なお、カルダノールおよびカルドール量(濃度:nmol/L)を以下の表3に示す。
It can be seen that the amount (concentration) of the recovered unheated cashew nut shell liquid component decreases as the pH of the silica goes to the acidic side. This is because the polymerization progressed while being allowed to stand at 80 ° C., and the insoluble portion in ethyl acetate increased. In particular, the reduction of the peak is significant in cardol, and it can be seen that cardol is particularly easily polymerized.
FIG. 2 shows the correlation between the pH and specific surface area of silica and the amount (concentration) of cardanol and cardol after 8 hours in the nine types of silica used. The amounts of cardanol and cardol (concentration: nmol / L) are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 カルダノール、カルドール供にpHとの相関が確認され、アルカリ性になるに従い回収されたカルダノール、カルドール量が増加している(重合が生じ難くなっている)ことが確認された。また、比表面積との関係においても、pHほど相関は強くないが、比表面積が小さくなるに従い、回収されたカルダノール、カルドール量が増加している(重合が生じ難くなっている)ことが確認された。 Correlation with pH was confirmed for cardanol and cardol, and it was confirmed that the amount of recovered cardanol and cardol increased as it became alkaline (polymerization hardly occurred). In addition, the correlation with the specific surface area is not as strong as the pH, but it was confirmed that the amount of recovered cardanol and cardol increased as the specific surface area decreased (polymerization hardly occurred). It was.
実施例4
 未加熱カシューナッツ殻油 10gおよび加熱カシューナッツ殻油 10gを各ビーカーに分取し、それぞれのカシューナッツ殻油に関して2重量%となるように各種アルカリ成分(NaOH溶液(53.6 %),KOH溶液(56.5 %),NH3(28 %))を水溶液にて添加した。そこに、Sipernat 22  5g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った。酢酸エチルを使用して500ppm(シリカ込み)に調整し、HPLCによる組成分析を実施した。
 図3にアルカリを加えないで実施した場合(比較例)の変化を図示した。なお、その変化についてのデータ(濃度:ppm)を以下の表4に示した。
Example 4
10g of unheated cashew nut shell oil and 10g of heated cashew nut shell oil are dispensed into each beaker, and various alkali components (NaOH solution (53.6%), KOH solution (56.5%) so as to be 2% by weight with respect to each cashew nut shell oil) , NH 3 (28%)) was added in aqueous solution. There, Sipernat 22 5g was added, and it stirred so that it might become uniform. Each was sealed and then placed in a constant temperature bath at 80 ° C. and sampled after 3 days. The composition was adjusted to 500 ppm (including silica) using ethyl acetate, and composition analysis was performed by HPLC.
FIG. 3 shows a change in the case of carrying out without adding alkali (comparative example). The data (concentration: ppm) about the change is shown in Table 4 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 同時に最も重合し易い成分であるカルドールを取り上げて併記した。これによると、カルドールに於ける未加熱カシューナッツ殻油および加熱カシューナッツ殻油の3日後の減少量はそれぞれ20%、23%であった。これに対して各種アルカリを2重量%添加した場合は回収率の上昇(重合の低下)が確認された(図4)。これにより、アルカリ添加が重合の抑制に効果的に効いている事が判明した。
 なお、図4についてのデータ(濃度:ppm)を以下の表5に示す。
At the same time, cardol, which is the most easily polymerized component, was taken up and described. According to this, the reduction amounts of unheated cashew nut shell liquid and heated cashew nut shell oil in Cardol after 3 days were 20% and 23%, respectively. On the other hand, when 2% by weight of various alkalis were added, an increase in the recovery rate (decrease in polymerization) was confirmed (FIG. 4). Thereby, it became clear that alkali addition was effective in suppressing superposition | polymerization.
The data (concentration: ppm) for FIG. 4 is shown in Table 5 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
実施例5
 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3にて作成したシリカ剤2種(Carplex BS306およびCarplex #1120)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。分析結果はカルドールについて、分析時の濃度(ppm)として記した(図5)。
 これより、Carplex #1120(pH10.6)を使用した方は、飼料中に於いても重合が進行することなく、安定に存在することがわかる。
 なお、図5についてのデータ(濃度:ppm)を以下の表6に示す。
Example 5
Add 1% by weight of two silica preparations (Carplex BS306 and Carplex # 1120) prepared in Example 3 to 100 g of feed (standard feed for raising young cattle: SDC No. 2 Japan Formula Feed Co., Ltd.) A feed containing unheated cashew nut shell liquid was prepared.
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 are shown as the concentration (ppm) at the time of analysis for cardol (FIG. 5).
From this, it can be seen that those using Carplex # 1120 (pH 10.6) exist stably in feed without polymerization proceeding.
The data (concentration: ppm) for FIG. 5 is shown in Table 6 below.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
実施例6
未加熱カシューナッツ殻油を添加した飼料の作成(有機賦形剤の使用)
 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(2重量%NaOH)             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(2重量%NaOH)             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。
Example 6
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.
(1) Broiler feed preparation Broiler fattening standard feed: SDB No. 1 Japan Formula Feed Co., Ltd. 99.5% by weight
Unheated cashew nut shell oil (2 wt% NaOH) 0.05 wt%
By mixing, it becomes powder and can be prevented from solidifying around 20 ° C.
(2) Preparation of cattle feed Standard feed for raising young cattle: SDC No. 2 Japan Formula Feed Co., Ltd. 99.5% by weight
Unheated cashew nut shell oil (2 wt% NaOH) 0.05 wt%
By mixing, it becomes powder and can be prevented from solidifying around 20 ° C.
 未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、またはアンモニアを添加することにより、重合を抑制することができる。また、水酸化ナトリウム、水酸化カリウム、またはアンモニアを添加した未加熱または加熱カシューナッツ殻油を賦形剤と混合することにより、安定性を向上させることができる。さらに、水酸化ナトリウム、水酸化カリウム、またはアンモニアを添加した未加熱カシューナッツ殻油に賦形剤を配合することにより、20℃近辺で固化することを防止できる。従って、カシューナッツ殻油の工業的利用が容易になる。 Polymerization can be suppressed by adding sodium hydroxide, potassium hydroxide, or ammonia to unheated or heated cashew nut shell liquid. In addition, stability can be improved by mixing an unheated or heated cashew nut shell oil to which sodium hydroxide, potassium hydroxide, or ammonia is added with an excipient. Further, by blending an excipient with unheated cashew nut shell liquid to which sodium hydroxide, potassium hydroxide, or ammonia is added, solidification around 20 ° C. can be prevented. Therefore, industrial use of cashew nut shell liquid becomes easy.

Claims (8)

  1. 水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリと未加熱または加熱カシューナッツ殻油を含む組成物であって、前記アルカリにより未加熱または加熱カシューナッツ殻油の重合性が抑制されている、組成物。 A composition comprising at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia and unheated or heated cashew nut shell liquid, wherein the alkali suppresses polymerization of unheated or heated cashew nut shell oil A composition.
  2. アルカリの量がカシューナッツ殻油比2重量%以上である請求項1に記載の組成物。 The composition according to claim 1, wherein the amount of alkali is 2% by weight or more of cashew nut shell liquid.
  3. 請求項1または2に記載の組成物と賦形剤とを含むカシューナッツ殻油製剤。 A cashew nut shell liquid formulation comprising the composition according to claim 1 or 2 and an excipient.
  4. 前記賦形剤がシリカであることを特徴とする請求項3に記載のカシューナッツ殻油製剤。 The cashew nut shell liquid formulation according to claim 3, wherein the excipient is silica.
  5. 前記シリカの比表面積が500m3/g以下であることを特徴とする請求項4に記載のカシューナッツ殻油製剤。 The cashew nut shell liquid formulation according to claim 4, wherein the silica has a specific surface area of 500 m 3 / g or less.
  6. 前記シリカのpHが6以上であることを特徴とする請求項4または5に記載のカシューナッツ殻油製剤。 The cashew nut shell liquid formulation according to claim 4 or 5, wherein the silica has a pH of 6 or more.
  7. 請求項1または2に記載の組成物および/あるいは請求項3~6のいずれか1項に記載のカシューナッツ殻油製剤を含むことを特徴とする飼料。 A feed comprising the composition according to claim 1 and / or the cashew nut shell liquid formulation according to any one of claims 3 to 6.
  8. 未加熱または加熱カシューナッツ殻油に水酸化ナトリウム、水酸化カリウム、およびアンモニアから選択される少なくとも1種のアルカリを添加することを特徴とする、カシューナッツ殻油の重合性抑制方法。 A method for suppressing the polymerization of cashew nut shell liquid, comprising adding at least one alkali selected from sodium hydroxide, potassium hydroxide, and ammonia to unheated or heated cashew nut shell oil.
PCT/JP2011/062830 2010-06-03 2011-06-03 Cashew nut shell oil with improved stability WO2011152533A1 (en)

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Publication number Priority date Publication date Assignee Title
EP3251522A4 (en) * 2015-01-30 2018-08-01 Idemitsu Kosan Co., Ltd Functional feed
US11377395B2 (en) 2017-09-13 2022-07-05 Lg Chem, Ltd. Controlled-release type fertilizer with decreased floating property comprising polyoxyethylene alky(-aryl) ether and method for preparing the same
US20220356325A1 (en) * 2021-05-04 2022-11-10 Kaco Gmbh + Co. Kg Fluoroelastomer Mixture, Seal Made of Such a Fluoroelastomer Mixture, and Shaft Seal with a Seal Body

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JPH0436238A (en) * 1990-06-01 1992-02-06 Takasago Internatl Corp External skin drug for acne vulgaris
JPH1076504A (en) * 1996-08-07 1998-03-24 Panjaringamu Sotk Pirurai Manufacture of rice hull particle board
JP2010043045A (en) * 2008-08-18 2010-02-25 Tohoku Kako Kk Transportation method of cashew nutshell liquid
JP2010059070A (en) * 2008-09-02 2010-03-18 Tohoku Kako Kk Cashew nut shell liquid being reduced or having been eliminated in rash and method for reducing or eliminating rash of cashew nutshell liquid
JP2010088363A (en) * 2008-10-09 2010-04-22 Tohoku Kako Kk Animal feed additive

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0436238A (en) * 1990-06-01 1992-02-06 Takasago Internatl Corp External skin drug for acne vulgaris
JPH1076504A (en) * 1996-08-07 1998-03-24 Panjaringamu Sotk Pirurai Manufacture of rice hull particle board
JP2010043045A (en) * 2008-08-18 2010-02-25 Tohoku Kako Kk Transportation method of cashew nutshell liquid
JP2010059070A (en) * 2008-09-02 2010-03-18 Tohoku Kako Kk Cashew nut shell liquid being reduced or having been eliminated in rash and method for reducing or eliminating rash of cashew nutshell liquid
JP2010088363A (en) * 2008-10-09 2010-04-22 Tohoku Kako Kk Animal feed additive

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3251522A4 (en) * 2015-01-30 2018-08-01 Idemitsu Kosan Co., Ltd Functional feed
US10953057B2 (en) 2015-01-30 2021-03-23 Idemitsu Kosan Co., Ltd. Functional feed
US11377395B2 (en) 2017-09-13 2022-07-05 Lg Chem, Ltd. Controlled-release type fertilizer with decreased floating property comprising polyoxyethylene alky(-aryl) ether and method for preparing the same
US20220356325A1 (en) * 2021-05-04 2022-11-10 Kaco Gmbh + Co. Kg Fluoroelastomer Mixture, Seal Made of Such a Fluoroelastomer Mixture, and Shaft Seal with a Seal Body

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