TWI618488B - Silica formulation including cashew nut shell liquid or the like,and manufacturing method thereof - Google Patents
Silica formulation including cashew nut shell liquid or the like,and manufacturing method thereof Download PDFInfo
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Abstract
一種含有腰果殼油、檟如子酸、腰果二酚或腰果酚、以及二氧化矽粒子的二氧化矽製劑，其特徵係：其二氧化矽粒子吸附腰果殼油、檟如子酸、腰果二酚或腰果酚，二氧化矽粒子的平均粒徑為150μm以上。 A cerium oxide preparation containing cashew nut shell liquid, scorpion acid, cardanol or cardanol, and cerium oxide particles, characterized in that the cerium oxide particles adsorb cashew nut shell liquid, scorpion acid, cashew nut The average particle diameter of the phenol or cardanol and the cerium oxide particles is 150 μm or more.
Description
本發明與使腰果殼油(CNSL)、檟如子酸、腰果二酚或腰果酚吸附於二氧化矽粒子上的二氧化矽製劑有關。而且，本發明與包覆各個吸附了腰果殼油、檟如子酸、腰果二酚或腰果酚的二氧化矽粒子的表面而成之包覆粒劑及其製造方法有關。 The present invention relates to a cerium oxide preparation which adsorbs cashew nut shell liquid (CNSL), ruthenium acid, cardanol or cardanol to cerium oxide particles. Further, the present invention relates to a coated granule obtained by coating the surfaces of cerium oxide particles each adsorbing cashew nut shell liquid, such as citron, cardanol or cardanol, and a method for producing the same.
腰果殼油為蘊含於腰果樹(Anacardium occidentale L.)果實的殼中的油狀液體。腰果殼油的成分主要包括有檟如子酸、腰果酚、腰果二酚與甲基腰果二酚。 Cashew nut shell liquid is an oily liquid contained in the shell of the fruit of the cashew tree (Anacardium occidentale L.). The components of cashew nut shell liquid mainly include scorpion acid, cardanol, cardanol and methyl cardanol.
腰果殼油的調製法有加熱法與溶劑萃取法，但是在腰果的產地，腰果殼油通常被加熱處理，將檟如子酸轉換成腰果酚使用。 The preparation method of the cashew nut shell liquid has a heating method and a solvent extraction method, but in the place where the cashew nut is produced, the cashew nut shell liquid is usually heat-treated, and the like is converted into a cardanol.
腰果殼油會引起皮疹，所以需要小心操作。皮疹症狀可因其主要成分之檟如子酸、腰果酚與腰果二酚之中的任何一項所引起，所以需要開發出安全的操作方法。 Cashew nut shell oil can cause a rash, so you need to be careful. Symptoms of rash can be caused by any of its main components such as citric acid, cardanol and cardanol, so it is necessary to develop safe methods of operation.
專利文獻1中記載一種家畜飼料添加劑：將源自辣椒 與胡椒之類辛香料的揮發性物質混入賦形劑中，且為了防止揮發而進行包覆。專利文獻1中使用的賦形劑為鋸木屑，凝固劑為蛋白質與明礬。 Patent Document 1 describes a livestock feed additive: will be derived from chili A volatile substance such as pepper is mixed with an excipient and coated to prevent volatilization. The excipient used in Patent Document 1 is sawdust, and the coagulant is protein and alum.
專利文獻2中記載一種以保留液態油為目的的製劑：製備油中水型乳液，並以多孔性吸油物質吸收之。專利文獻2中記載，為防止液態油滲漏有先將硬化油與液態油混合均勻，不過考量到添加量其效果並不令人滿意。 Patent Document 2 describes a preparation for the purpose of retaining a liquid oil: preparing an aqueous emulsion in oil and absorbing it with a porous oil absorbing material. Patent Document 2 discloses that in order to prevent liquid oil from leaking, the hardened oil and the liquid oil are first uniformly mixed, but the effect is not satisfactory in consideration of the added amount.
專利文獻3中記載一種吸油製劑的製作：在減壓條件下使機能性油脂吸附於二氧化矽之類的載體。專利文獻3中記載其缺點為：為了達到加快吸油速度的效果，不得不使用平均粒徑如5.0~10.0μm般微小的二氧化矽粒子。 Patent Document 3 describes an oil-absorbing preparation in which a functional fat or oil is adsorbed to a carrier such as cerium oxide under reduced pressure. Patent Document 3 describes a disadvantage in that, in order to achieve an effect of speeding up the oil absorption rate, it is necessary to use cerium oxide particles having an average particle diameter of, for example, 5.0 to 10.0 μm.
專利文獻4中記載成功製造出一種改善皮疹問題與操作性的二氧化矽原體：使腰果殼油等吸附於二氧化矽之類的無機載體。然而專利文獻4中的實施例採用平均粒徑為100μm之二氧化矽粒子，並無使腰果殼油吸附於平均粒徑為150μm以上之二氧化矽粒子的二氧化矽製劑之實施例。而且專利文獻4中吸附了腰果殼油的二氧化矽粒子並沒有被包覆。 Patent Document 4 describes that a cerium oxide precursor which improves the rash problem and handling property is successfully produced: an inorganic carrier which adsorbs cashew nut shell liquid or the like to cerium oxide. However, the examples in Patent Document 4 employ cerium oxide particles having an average particle diameter of 100 μm, and do not have an embodiment in which the cashew nut shell oil is adsorbed to the cerium oxide preparation having cerium oxide particles having an average particle diameter of 150 μm or more. Further, in the patent document 4, the ceria particles in which the cashew nut shell oil is adsorbed are not coated.
專利文獻5中記載：使腰果殼油吸附於二氧化矽載體，之後經過製粒與包覆步驟可得操作性與安全性提升的製劑。然而專利文獻5中的實施例採用平均粒徑為100μm之二氧化矽粒子，吸附腰果殼油後被製粒成直徑約3.0mm，並無使腰果殼油吸附於平均粒徑為150μm以上之二氧化矽粒子的二氧化矽製劑之實施例。 Patent Document 5 discloses that a cashew nut shell oil is adsorbed to a ceria carrier, and then a granulation and coating step is carried out to obtain a formulation having improved workability and safety. However, the example in Patent Document 5 uses cerium oxide particles having an average particle diameter of 100 μm, and is granulated to a diameter of about 3.0 mm after adsorbing cashew nut shell liquid, and does not adsorb cashew nut shell oil to an average particle diameter of 150 μm or more. An example of a cerium oxide formulation of cerium oxide particles.
專利文獻4與5中的二氧化矽原體或二氧化矽製劑經長時間靜置後有可能會析出腰果殼油等。且腰果殼油為黏稠的液體，由於會在20℃左右固化所以非常難以操作。因此需要改善操作性的技術。此外，因腰果殼油接觸水份等可能會溶離，因此需要防止溶離的技術。 The ceria precursor or the ceria formulation in Patent Documents 4 and 5 may precipitate cashew nut shell liquid or the like after standing for a long period of time. And the cashew nut shell liquid is a viscous liquid, which is very difficult to handle because it will cure at about 20 °C. Therefore, there is a need for a technique for improving operability. In addition, since the cashew nut shell oil may be dissolved in contact with moisture or the like, a technique for preventing elution is required.
如以上所述，目前為止已知使腰果殼油吸附於二氧化矽的技術以及將製粒後的粒子包覆起來的技術；但使腰果殼油吸附於平均粒徑為150μm以上之二氧化矽粒子的二氧化矽製劑仍不為所知。而且，不經過二氧化矽粒子團粒化或製粒，而將各個二氧化矽粒子以硬化油等塗覆劑包覆之含腰果殼油二氧化矽製劑與其製造方法仍不為所知。 As described above, a technique of adsorbing cashew nut shell liquid to cerium oxide and a technique of coating particles after granulation have been known so far; however, the cashew nut shell oil is adsorbed to cerium oxide having an average particle diameter of 150 μm or more. Particle cerium dioxide formulations are still not known. Further, a preparation containing a cashew nut shell liquid cerium oxide coated with a coating agent such as a hardened oil without oxidizing or granulating the cerium oxide particles is not known.
[專利文獻1]日本特開平7-184561號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-184661
[專利文獻2]國際公開號WO2006/137289小冊子 [Patent Document 2] International Publication No. WO2006/137289 Brochure
[專利文獻3]日本特開2007-209224號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-209224
[專利文獻4]國際公開號WO2009/151048小冊子 [Patent Document 4] International Publication No. WO2009/151048 Booklet
[專利文獻5]國際公開號WO2011/013592小冊子 [Patent Document 5] International Publication No. WO2011/013592 Brochure
本發明以下列事項為課題：防止腰果殼油、檟如子酸、腰果二酚或腰果酚(以下有時候以腰果殼油等稱之)在低溫下自吸油載體(即，二氧化矽)析出與固著，改善腰果 殼油等的流動性，並防止腰果殼油等自吸油載體溶離致使製劑的操作性低下。 The present invention is directed to the following matters: prevention of cashew nut shell liquid, ruthenium acid, cardanol or cardanol (hereinafter sometimes referred to as cashew nut shell oil), self-priming (ie, cerium oxide) at low temperature And fixing, improving cashews The fluidity of shell oil and the like, and the prevention of the dissolution of the self-priming carrier such as cashew nut shell liquid, renders the operability of the preparation low.
換言之，本發明以防止製劑中的腰果殼油等因析出與溶離而與皮膚接觸(安全性)以及改善操作性為課題。 In other words, the present invention has an object of preventing contact with the skin (safety) and improving workability due to precipitation and dissolution of the cashew nut shell liquid in the preparation.
又，本發明亦以簡化製劑步驟為課題。 Moreover, the present invention also aims to simplify the formulation steps.
本發明者群為解決上述課題，經過專注研討後有以下發現：讓腰果殼油吸附於平均粒徑150μm以上的二氧化矽可減少腰果殼油的析出。 In order to solve the above problems, the inventors of the present invention have found out that the adsorption of cashew nut shell liquid to cerium oxide having an average particle diameter of 150 μm or more can reduce the precipitation of cashew nut shell liquid.
此外本發明者群還有以下發現：讓腰果殼油吸附於平均粒徑150μm以上的二氧化矽(二氧化矽原體)後，進一步進行包覆處理可以解決析出、溶離和皮疹等等問題。 Further, the present inventors have found that the cashew nut shell oil is adsorbed to cerium oxide (cerium dioxide precursor) having an average particle diameter of 150 μm or more, and further coating treatment can solve problems such as precipitation, dissolution, and rash.
而且本發明者群還有以下發現：在30℃上讓腰果殼油吸覆於二氧化矽並製劑，可減少腰果殼油的溶離。 Further, the present inventors have found that the cashew nut shell oil is adsorbed on the ceria at 30 ° C and formulated to reduce the dissolution of the cashew nut shell liquid.
本發明者群如上所述終於完成本項發明。 The inventors have finally completed the present invention as described above.
換句話說，本發明如下所述： In other words, the invention is as follows:
(1)一種含有腰果殼油、檟如子酸、腰果二酚或腰果酚、以及二氧化矽粒子的二氧化矽製劑，其特徵係：其二氧化矽粒子吸附腰果殼油、檟如子酸、腰果二酚或腰果酚，二氧化矽粒子的平均粒徑為150μm以上。 (1) A cerium oxide preparation containing cashew nut shell liquid, ruthenium acid, cardanol or cardanol, and cerium oxide particles, characterized in that the cerium oxide particles adsorb cashew nut shell liquid, such as citron acid The cardanol diphenol or cardanol has an average particle diameter of 150 μm or more.
(2)如(1)所述之製劑，其中，上述二氧化矽粒子的表面各被塗覆劑包覆。 (2) The preparation according to (1), wherein the surfaces of the above cerium oxide particles are each coated with a coating agent.
(3)如(2)所述之製劑，其中，上述塗覆劑為脂肪酸 類、硬化油、棕櫚油或源自這些油類之油脂。 (3) The preparation according to (2), wherein the coating agent is a fatty acid Classes, hardened oils, palm oil or oils derived from these oils.
(4)如(3)所述之製劑，其中，上述塗覆劑的融點高於50℃。 (4) The preparation according to (3), wherein the coating agent has a melting point higher than 50 °C.
(5)如(2)~(4)所述之任一製劑，其中，上述塗覆劑以及含塗覆劑之二氧化矽製劑的質量比為0.1~30：100。 (5) The preparation according to any one of (2) to (4), wherein the coating agent and the coating agent-containing cerium oxide preparation have a mass ratio of 0.1 to 30:100.
(6)如(1)~(5)所述之任一製劑，其中，上述二氧化矽的特徵係每100g二氧化矽的吸油能力為200g以上。 (6) The preparation according to any one of (1) to (5) wherein the cerium oxide is characterized in that the oil absorption capacity per 100 g of cerium oxide is 200 g or more.
(7)如(1)~(6)所述之任一製劑，係飼料用。 (7) The preparation according to any one of (1) to (6) for use in feed.
(8)一種含有腰果殼油、檟如子酸、腰果二酚或腰果酚、以及二氧化矽粒子的製劑的製造方法，其特徵係包括使腰果殼油、檟如子酸、腰果二酚或腰果酚吸附於平均粒徑為150μm以上之二氧化矽粒子的步驟，以及將吸附了腰果殼油、檟如子酸、腰果二酚或腰果酚的二氧化矽粒子與塗覆劑在加溫下攪拌混合的步驟。 (8) A method for producing a preparation comprising cashew nut shell liquid, a formic acid, cardanol or cardanol, and ceria particles, characterized by comprising cashew nut shell liquid, berry acid, cardanol or a step of adsorbing cardanol to cerium oxide particles having an average particle diameter of 150 μm or more, and cerium oxide particles adsorbing cashew nut shell liquid, ruthenium acid, cardanol or cardanol with a coating agent under heating Stir the mixing step.
(9)一種含有腰果殼油、檟如子酸、腰果二酚或腰果酚、以及二氧化矽粒子的製劑的製造方法，其特徵係包括在30℃以上使腰果殼油、檟如子酸、腰果二酚或腰果酚吸附於二氧化矽粒子的步驟。 (9) A method for producing a preparation comprising a cashew nut shell liquid, a ruthenium acid, a cardanol or a cardanol, and a cerium oxide particle, which comprises a cashew nut shell liquid, a ruthenium acid, or the like at 30 ° C or higher. The step of adsorbing cashew nutdiol or cardanol to cerium oxide particles.
(10)如(9)所述之方法，其中，上述之二氧化矽粒子的平均粒徑為150μm以上。 (10) The method according to (9), wherein the cerium oxide particles have an average particle diameter of 150 μm or more.
(11)如(9)或(10)所述之方法，其中，進一步包括將吸附了腰果殼油、檟如子酸、腰果二酚或腰果酚的二氧化矽粒子與塗覆劑在加溫下攪拌混合的步驟。 (11) The method according to (9) or (10), further comprising heating the cerium oxide particles and the coating agent which adsorb the cashew nut shell liquid, the ruthenium acid, the cardanol or the cardanol The step of stirring and mixing is carried out.
藉由減少腰果殼油的析出、溶離與固著等，可改善製劑製造時、流通時、使用時的安全性與操作性。 By reducing the precipitation, dissolution, and fixation of the cashew nut shell liquid, it is possible to improve the safety and workability at the time of preparation, distribution, and use of the preparation.
又，若塗覆劑採用脂肪酸類、硬化油、棕櫚油或源自這些油類之油脂，進行包覆處理時可以不用到水與溶劑，由於可以省略乾燥步驟，故整體工程可被簡化，可望降低成本。 Further, if the coating agent is a fatty acid, a hardened oil, palm oil or a fat derived from these oils, water and a solvent may not be used for the coating treatment, and since the drying step can be omitted, the overall engineering can be simplified. Hope to reduce costs.
更進一步來說，因吸油步驟和包覆步驟可以在同一個反應容器中一連串地進行，因此工程被簡化，可實現成本的降低。 Further, since the oil absorbing step and the coating step can be carried out in series in the same reaction vessel, the engineering is simplified, and the cost can be reduced.
[圖1]為表示本發明的製劑於包覆前後的剖面圖(照片)。 Fig. 1 is a cross-sectional view (photograph) showing the preparation of the present invention before and after coating.
[圖2]為表示腰果殼油被平均粒徑110μm的二氧化矽吸收後的二氧化矽表面之圖(照片)。 Fig. 2 is a view (photograph) showing the surface of cerium oxide after the cashew nut shell liquid is absorbed by cerium oxide having an average particle diameter of 110 μm.
[圖3]為表示腰果殼油被平均粒徑320μm的二氧化矽吸收後的二氧化矽表面之圖(照片)。 Fig. 3 is a view (photograph) showing the surface of cerium oxide after the cashew nut shell liquid is absorbed by cerium oxide having an average particle diameter of 320 μm.
本發明之二氧化矽製劑含有腰果殼油、檟如子酸、腰果二酚或腰果酚、以及二氧化矽粒子；二氧化矽粒子吸附腰果殼油、檟如子酸、腰果二酚或腰果酚，二氧化矽粒子的平均粒徑為150μm以上，又以250μm以上為佳。平均 粒徑的上限雖無特殊限制，但可舉出500μm。二氧化矽的平均粒徑可依照ISO 13320-1法等測定。 The cerium oxide preparation of the present invention contains cashew nut shell liquid, ruthenium acid, cardanol or cardanol, and cerium oxide particles; cerium oxide particles adsorb cashew nut shell liquid, such as citron, cardanol or cardanol The cerium oxide particles have an average particle diameter of 150 μm or more, and more preferably 250 μm or more. average The upper limit of the particle diameter is not particularly limited, but may be 500 μm. The average particle diameter of cerium oxide can be measured in accordance with the ISO 13320-1 method or the like.
且，本發明之二氧化矽製劑之各粒二氧化矽粒子表面可用塗覆劑包覆。 Further, the surface of each of the cerium oxide particles of the cerium oxide preparation of the present invention may be coated with a coating agent.
而且，本發明之二氧化矽製劑可含腰果殼油的安定劑和/或抗氧化劑。 Moreover, the cerium oxide preparation of the present invention may contain a stabilizer and/or an antioxidant of cashew nut shell liquid.
又，在下列說明書中將吸付了腰果殼油等的二氧化矽粒子稱為二氧化矽原體，此二氧化矽原體被塗覆劑包覆後的製劑稱為包覆粒劑，有時將這些統稱為二氧化矽製劑。 Further, in the following description, the cerium oxide particles which have been absorbed by the cashew nut shell liquid or the like are referred to as cerium oxide precursors, and the preparation of the cerium cerium oxide precursor coated with the coating agent is called a coating granule, and These are collectively referred to as cerium oxide formulations.
腰果殼油為蘊含於腰果樹(Anacardium occidentale L.)果實的殼中的油狀液體。腰果殼油的成分包括有檟如子酸、腰果酚與腰果二酚。一般來說，檟如子酸經加熱處理會被轉換成腰果酚。 Cashew nut shell liquid is an oily liquid contained in the shell of the fruit of the cashew tree (Anacardium occidentale L.). The components of the cashew nut shell liquid include scorpion acids, cardanol and cardanol. In general, if the acid is heated, it will be converted into cardanol.
根據J.Agric.Food Chem.2001,49,2548-2551所記載，經壓榨腰果殼而被提取出來的未加熱腰果殼油含有檟如子酸55~80質量%、腰果酚5~20質量%與腰果二酚5~30質量%。 According to J. Agric. Food Chem. 2001, 49, 2548-2551, the unheated cashew nut shell oil extracted by pressing the cashew nut shell contains 55 to 80% by mass of cardioic acid and 5 to 20% by mass of cardanol. 5 to 30% by mass with cashew diphenol.
未加熱腰果殼油經70℃以上，更理想的是130℃以上，加熱處理後所得之加熱腰果殼油，因其中未加熱腰果殼油的主成分檟如子酸經脫羰而被轉換成腰果酚，所以成為含有檟如子酸0~10質量%、腰果酚55~80質量%與腰果二酚5~30質量%之物質。 The unheated cashew nut shell oil is 70° C. or higher, more preferably 130° C. or higher, and the heated cashew nut shell liquid obtained after the heat treatment is converted into cashew nuts by the main component of the unheated cashew nut shell oil such as deacidification. Phenol is a substance containing 0 to 10% by mass of a ruthenium acid, 55 to 80% by mass of cardanol, and 5 to 30% by mass of cardanol.
未加熱腰果殼油經常溫(20℃)保存約一年以上所得之腰果殼油，因其中未加熱腰果殼油的主成分檟如子酸經脫 羰而被轉換成腰果酚，所以成為含有檟如子酸0~10質量%、腰果酚55~80質量%與腰果二酚5~30質量%之物質。 Unheated cashew nut shell oil is often stored at a temperature (20 ° C) for about one year or more, because the main component of the unheated cashew nut shell oil, such as the acid Since carbonyl is converted into cardanol, it is a substance containing 0 to 10% by mass of a ruthenium acid, 55 to 80% by mass of cardanol, and 5 to 30% by mass of cardanol.
腰果殼油可藉由壓榨腰果的殼提取植物油取得。而且，腰果殼油也可藉由萃取法，例如腰果殼的溶劑萃取而取得。更進一步來說，腰果殼油可依日本特開平8-231410號公報所記載的方法，例如溶劑萃取法而取得。 Cashew nut shell oil can be obtained by extracting vegetable oil from the shell of pressed cashew nuts. Moreover, cashew nut shell liquid can also be obtained by extraction, such as solvent extraction of cashew nut shells. Further, the cashew nut shell liquid can be obtained by a method described in JP-A-8-231410, for example, a solvent extraction method.
腰果殼油也可選用市售品。 Cashew nut shell oil is also available as a commercial item.
本發明之腰果殼油，也可以是如上述所得之未加熱腰果殼油經70℃以上，更理想的是130℃以上，加熱處理後所得之加熱腰果殼油。也可以是未加熱腰果殼油經常溫(20℃)保存約一年而得之腰果殼油。 The cashew nut shell liquid of the present invention may be a heated cashew nut shell liquid obtained by heating the unheated cashew nut shell liquid obtained above, at 70 ° C or higher, more preferably at 130 ° C or higher. It may also be a cashew nut shell liquid which is not heated and stored at a temperature (20 ° C) for about one year.
本發明之腰果殼油，也可以是自腰果殼壓榨提取(未加熱腰果殼油)後經過130℃加熱處理所得的腰果殼油。 The cashew nut shell liquid of the present invention may also be a cashew nut shell liquid obtained by heat-treating at 130 ° C after being extracted from the cashew nut shell (unheated cashew nut shell liquid).
本發明之二氧化矽製劑，除了腰果殼油，還可含有檟如子酸、腰果酚或腰果二酚。 The cerium oxide preparation of the present invention may contain, for example, a cashew nut shell liquid, a cardanol or a cardanol.
本發明之二氧化矽製劑中腰果殼油的含量以二氧化矽製劑總量為基準，以10質量%~70質量%為宜，20質量%~65質量%較佳，30質量%~60質量%更佳。若含量達10質量%以上能有效率地達到以下效果：改善瘤胃發酵、預防鼓脹症、治療鼓脹症、治療酸中毒、梭菌屬所引起之疾病的預防、球菌目所引起之疾病的預防、提高乳牛產乳量、預防乳牛圍產期疾病、提高乳牛繁殖效率以及促進家畜體重增加等。若含量在70質量%以下則可在作業上防 止手產生皮疹，保持二氧化矽製劑的操作性，因此較佳。 The content of the cashew nut shell liquid in the cerium oxide preparation of the invention is preferably from 10% by mass to 70% by mass based on the total amount of the cerium oxide preparation, preferably from 20% by mass to 65% by mass, and from 30% by mass to 60% by mass. % is better. When the content is 10% by mass or more, the following effects can be efficiently achieved: improvement of rumen fermentation, prevention of bloating, treatment of bloating, treatment of acidosis, prevention of diseases caused by Clostridium, prevention of diseases caused by coccidioides, Improve the milk production of dairy cows, prevent perinatal diseases of dairy cows, improve the reproductive efficiency of dairy cows, and promote the weight gain of livestock. If the content is below 70% by mass, it can be prevented from working. It is preferred to form a rash on the hand and maintain the handleability of the cerium oxide preparation.
本發明中所使用的檟如子酸可舉例有天然檟如子酸、合成檟如子酸或是其衍生物。也可使用市售檟如子酸。檟如子酸可依日本特開平8-231410號公報所記載那樣，將腰果殼以有機溶劑做萃取處理，再將取得的腰果殼油，舉例來說，藉改變正己烷、醋酸乙酯及醋酸的混合溶劑比例以矽膠管柱層析法溶離得到檟如子酸(參見日本特開平3-240721號公報、日本特開平3-240716號公報等)。此檟如子酸可在二氧化矽製劑、飼料添加劑與飼料中存在和腰果殼油相同的含量。 As the acid used in the present invention, for example, a natural acid such as a sub-acid, a synthetic hydrazine such as a sub-acid or a derivative thereof can be exemplified. Commercially available hydrazine acids such as citric acid can also be used. For example, as described in JP-A-H08-231410, the cashew nut shell is extracted with an organic solvent, and the obtained cashew nut shell liquid, for example, by changing n-hexane, ethyl acetate, and acetic acid The ratio of the mixed solvent is lysed by a ruthenium column chromatography to obtain a ruthenium acid (see, for example, Japanese Laid-Open Patent Publication No. Hei-3-240721, Japanese Patent Application Laid-Open No. Hei No. Hei No. 3-240716, etc.). This ruthenium acid can be present in the same amount as the cashew nut shell liquid in the cerium oxide preparation, the feed additive and the feed.
本發明中所使用的腰果酚可舉例有天然腰果酚、合成腰果酚或是其衍生物。本發明中所使用的腰果酚也可藉由使腰果殼油主成分之檟如子酸脫羰後取得。此腰果酚可在二氧化矽製劑、飼料添加劑與飼料中存在和腰果殼油相同的含量。 The cardanol used in the present invention may, for example, be a natural cardanol, a synthetic cardanol or a derivative thereof. The cardanol used in the present invention can also be obtained by decarbonylating a main component of a cashew nut shell oil such as a sub-acid. This cardanol can be present in the same amount as the cashew nut shell liquid in the ceria formulation, feed additive and feed.
此外，若使用加熱腰果殼油，加熱腰果殼油中檟如子酸和腰果酚的質量比以0：100~20：80為宜。 In addition, if the heated cashew nut shell oil is used, the mass ratio of the such as the acid and the cardanol in the cashew nut shell liquid is preferably 0:100 to 20:80.
本發明中所使用的腰果二酚可舉例有天然腰果二酚、合成腰果二酚或是其衍生物。本發明中所使用的腰果二酚也可自精製腰果殼油而得。 The cardanol used in the present invention may, for example, be natural cardanol, synthetic cardanol or a derivative thereof. The cardanol diphenol used in the present invention can also be obtained by purifying cashew nut shell liquid.
本發明之二氧化矽製劑含有吸油劑，腰果殼油、檟如子酸、腰果二酚或腰果酚(以下有時候以腰果殼油等稱之)吸附且被包含在吸油劑中。本發明之二氧化矽製劑中，吸油劑為二氧化矽，其平均粒徑為150μm以上。且 本發明中的吸油劑，以每100g可吸附200g以上的油為宜。二氧化矽的吸油能力(油的吸附量、亦稱吸油量)可用ISO 787/5法等測定。 The cerium oxide preparation of the present invention contains an oil absorbing agent, which is adsorbed by cashew nut shell liquid, ruthenium acid, cardanol or cardanol (hereinafter sometimes referred to as cashew nut shell liquid, etc.) and is contained in the oil absorbing agent. In the cerium oxide preparation of the present invention, the oil absorbing agent is cerium oxide and has an average particle diameter of 150 μm or more. And The oil absorbing agent in the present invention preferably contains 200 g or more of oil per 100 g. The oil absorption capacity of the cerium oxide (the amount of oil adsorbed, also referred to as the oil absorption) can be measured by the ISO 787/5 method or the like.
本發明之二氧化矽製劑也可含有腰果殼油等的安定劑和/或抗氧化劑。本發明中所使用的腰果殼油等的安定劑指的是，和腰果殼油等內含的金屬離子配位形成螯合物，之多齒配位體螯合劑。 The cerium oxide preparation of the present invention may also contain a stabilizer and/or an antioxidant such as cashew nut shell liquid. The stabilizer of the cashew nut shell liquid or the like used in the present invention refers to a multidentate ligand chelating agent which forms a chelate compound with a metal ion contained in the cashew nut shell liquid or the like.
本發明中所使用的螯合劑舉例來說有：有機酸類、有機酸鹽類、磷酸類、磷酸鹽類、胺基多羰酸類、胺基多羰酸鹽類、中性胺基酸類、鋁矽酸鹽類、膦酸類、膦酸鹽類、聚合物類。 The chelating agent used in the present invention is exemplified by an organic acid, an organic acid salt, a phosphoric acid, a phosphate, an aminopolycarboxylic acid, an aminopolycarbonate, a neutral amino acid, and an aluminum hydrazine. Acid salts, phosphonic acids, phosphonates, polymers.
有機酸類與有機酸鹽類的螯合劑舉例來說有：檸檬酸及其鹽類、蘋果酸及其鹽類、酒石酸及其鹽類、琥珀酸及其鹽類、葡糖酸及其鹽類、草酸及其鹽類、乙醇酸及其鹽類以及丙酸及其鹽類。 Examples of chelating agents for organic acids and organic acid salts include: citric acid and its salts, malic acid and its salts, tartaric acid and its salts, succinic acid and its salts, gluconic acid and its salts, Oxalic acid and its salts, glycolic acid and its salts, and propionic acid and its salts.
磷酸類與磷酸鹽類的螯合劑舉例來說有：正磷酸及其鹽類、焦磷酸及其鹽類、三聚磷酸及其鹽類、四聚磷酸及其鹽類、六偏磷酸及其鹽類以及植酸及其鹽類。正磷酸鹽類舉例來說有：磷酸二氫鈉、磷酸二氫鉀、磷酸二氫銨、磷酸氫二鈉、磷酸氫二鉀以及磷酸氫二銨。胺基多羰酸類與胺基多羰酸鹽類的螯合劑舉例來說有：乙二胺四乙酸(EDTA)及其鹽類、乙二胺二乙酸及其鹽類、羥乙基乙二胺四乙酸及其鹽類、二乙撐三胺五乙酸及其鹽類、氮三醋酸及其鹽類、三乙撐四胺六乙酸及其鹽類、二羰甲基麩 醯胺六乙酸及其鹽類、二羰甲基麩胺酸四鈉鹽、二羥甲基甘胺酸、1,3-丙二胺四乙酸及其鹽類、1,3-二胺-2-羥丙烷四乙酸及其鹽類、膦酸丁烷三羧酸及其鹽類、麩胺酸及其鹽類、環己烷二胺四乙酸及其鹽類、亞胺二乙酸及其鹽類、N-(2-羥乙基)亞胺二乙酸及其鹽類、N-(2-羥乙基)乙二胺三乙酸及其鹽類、乙二醇***二胺四乙酸及其鹽類、麩胺酸二乙酸及其鹽類、天門冬胺酸二乙酸及其鹽類與二羥甲基甘胺酸。 Phosphates and phosphate chelating agents include, for example, orthophosphoric acid and salts thereof, pyrophosphoric acid and salts thereof, tripolyphosphoric acid and salts thereof, tetrapolyphosphoric acid and salts thereof, hexametaphosphoric acid and salts thereof. Classes as well as phytic acid and its salts. Examples of the orthophosphates include sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, and diammonium hydrogen phosphate. Examples of the chelating agent of the aminopolycarboxylic acid and the aminopolycarbonate are: ethylenediaminetetraacetic acid (EDTA) and salts thereof, ethylenediaminediacetic acid and salts thereof, and hydroxyethylethylenediamine. Tetraacetic acid and its salts, diethylenetriamine pentaacetic acid and its salts, nitrogen triacetic acid and its salts, triethylenetetramine hexaacetic acid and its salts, dicarbonyl methyl bran Amidamine hexaacetic acid and its salts, dicarbonylmethyl glutamic acid tetrasodium salt, dimethylol glycine acid, 1,3-propanediaminetetraacetic acid and its salts, 1,3-diamine-2 -Hydroxypropane tetraacetic acid and its salts, phosphonic acid butane tricarboxylic acid and its salts, glutamic acid and its salts, cyclohexanediaminetetraacetic acid and its salts, imine diacetic acid and its salts , N-(2-hydroxyethyl)imine diacetic acid and its salts, N-(2-hydroxyethyl)ethylenediaminetriacetic acid and its salts, ethylene glycol diethyl ether diamine tetraacetic acid and salts thereof , glutamic acid diacetic acid and its salts, aspartic acid diacetic acid and its salts and dimethylol glycine.
中性胺基酸類的螯合劑舉例來說有：甘胺酸、丙胺酸、亮胺酸、半胱胺酸、甲硫胺酸、天門冬胺酸與麩醯胺酸。 Examples of chelating agents for neutral amino acids include glycine, alanine, leucine, cysteine, methionine, aspartic acid and glutamic acid.
鋁矽酸鹽類的螯合劑舉例來說有沸石。 The chelating agent of the aluminosilicate is exemplified by zeolite.
膦酸類與膦酸鹽類的螯合劑舉例來說有：羥乙基二膦酸及其鹽類、氮基三亞甲基膦酸及其鹽類、次氮基及其鹽類。 Examples of the chelating agents of phosphonic acid and phosphonates include hydroxyethyl diphosphonic acid and salts thereof, nitrogen trimethylene phosphonic acid and salts thereof, nitrile groups and salts thereof.
聚合物類的螯合劑舉例來說有：聚丙烯酸、聚馬來酸以及馬來酸和丙烯酸的共聚物。而且也可能同時使用兩種以上的螯合劑。 Polymeric chelating agents are exemplified by polyacrylic acid, polymaleic acid, and copolymers of maleic acid and acrylic acid. It is also possible to use two or more chelating agents at the same time.
本發明中所使用的腰果殼油等的抗氧化劑舉例來說有：乙氧喹、t-丁基羥基甲苯、t-丁基羥基甲氧苯、第三丁氫醌、抗壞血酸與其酯類、維他命E、沒食子酸及其酯類、異抗壞血酸、綠原酸、亞硫酸鹽、硫代硫酸鹽、亞磷酸鹽、次磷酸鹽與磷酸鹽等。而且也可能同時使用兩種以上的抗氧化劑。 Examples of the antioxidants such as cashew nut shell liquid used in the present invention include: ethoxyquin, t-butylhydroxytoluene, t-butylhydroxymethoxybenzene, tributylhydroquinone, ascorbic acid and its esters, and vitamins. E, gallic acid and its esters, isoascorbic acid, chlorogenic acid, sulfite, thiosulfate, phosphite, hypophosphite and phosphate. It is also possible to use two or more antioxidants at the same time.
本發明之二氧化矽製劑可藉由將腰果殼油等吸附於平均粒徑150μm以上之二氧化矽(吸油步驟)而得；但本發明之二氧化矽製劑又以，將腰果殼油等吸附於平均粒徑150μm以上之二氧化矽後所得之二氧化矽原體，各用塗覆劑包覆(包覆步驟)所得之包覆粒劑為宜。 The cerium oxide preparation of the present invention can be obtained by adsorbing cashew nut shell liquid or the like to cerium oxide having an average particle diameter of 150 μm or more (oil absorption step); however, the cerium oxide preparation of the present invention adsorbs cashew nut shell oil or the like. Preferably, the cerium oxide precursor obtained after the cerium oxide having an average particle diameter of 150 μm or more is coated with a coating agent (coating step).
本發明之包覆粒劑舉例來說可依下述方式製得。 The coated granules of the present invention can be obtained, for example, in the following manner.
混合平均粒徑150μm以上之二氧化矽粒子(視需要用其他吸油劑)與腰果殼油等(視需要添加安定劑和/或抗氧化劑)。之後，將吸附了腰果殼油等的二氧化矽粒子(二氧化矽原體)視需要，在加溫下以塗覆劑包覆。 The cerium oxide particles having an average particle diameter of 150 μm or more (other oil absorbing agents as needed) and cashew nut shell liquid are mixed (and a stabilizer and/or an antioxidant are added as needed). Thereafter, cerium oxide particles (cerium dioxide precursor) to which cashew nut shell liquid or the like is adsorbed are coated with a coating agent under heating as needed.
於本發明中，吸油後不經造粒與製粒處理，視需要進行塗覆劑的包覆處理後即可成本發明之包覆粒劑。 In the present invention, after the oil absorption, the granulation and the granulation treatment are not carried out, and the coating agent may be coated as needed to obtain the coated granule of the invention.
本發明中所使用的塗覆劑舉例來說有：硬化油、棕櫚油、脂肪酸類、石蠟類以及蠟類等之油脂；上述塗覆劑可使用兩種以上，也可使用上述塗覆劑的混合物。 The coating agent to be used in the present invention is, for example, a fat or oil such as a hardened oil, palm oil, a fatty acid, a paraffin wax or a wax; and the above coating agent may be used in two or more types, and the above coating agent may also be used. mixture.
本發明中所使用的硬化油舉例來說有：大豆硬化油、棕櫚硬化油以及菜籽硬化油之類的植物性硬化油，只要能釋放腰果殼油、檟如子酸、腰果二酚和腰果酚，就沒有限制。 The hardening oil used in the present invention is exemplified by a vegetable hardening oil such as soybean hardening oil, palm hardening oil, and rapeseed hardened oil, as long as it can release cashew nut shell liquid, such as cranberry acid, cardanol and cashew nuts. There is no limit to phenol.
本發明中所使用的脂肪酸類，舉例來說有熔點高於50℃的飽和脂肪酸，更詳細地舉例來說有：肉荳蔻酸、棕櫚酸和硬脂酸之類的碳數超過14的飽和脂肪酸及其酯類，只要能釋放腰果殼油、檟如子酸、腰果二酚和腰果酚，就沒有限制。 The fatty acids used in the present invention are, for example, saturated fatty acids having a melting point higher than 50 ° C, and more particularly, for example, saturated fatty acids having more than 14 carbon atoms such as myristic acid, palmitic acid and stearic acid. And esters thereof, as long as they can release cashew nut shell liquid, such as acid, cardanol and cardanol, there is no limit.
本發明所使用的塗覆劑，其熔點以高於50℃為宜。又，本發明所使用的塗覆劑，以包覆粒劑的總量為基準，以0.01~50質量%為宜，0.05~40質量%較佳，0.1~30質量%更佳。 The coating agent used in the present invention preferably has a melting point of higher than 50 °C. Further, the coating agent used in the present invention is preferably 0.01 to 50% by mass, more preferably 0.05 to 40% by mass, even more preferably 0.1 to 30% by mass based on the total mass of the coating granule.
本發明之包覆粒劑中，二氧化矽粒子與包覆劑的質量比以80~99.9：20~0.1為宜。 In the coated granule of the present invention, the mass ratio of the cerium oxide particles to the coating agent is preferably from 80 to 99.9:20 to 0.1.
本發明中吸油處理與包覆處理時所使用的設備並無特殊限制，舉例來說有：槳式混合機、螺條混合機、搖擺混合機以及錐形混合機等混合機。而且，本發明中吸油步驟和包覆步驟可以在同一個容器中連續進行，也可以分開來進行。也就是說，只要將二氧化矽與腰果殼油混合，讓腰果殼油吸附於二氧化矽，吸附之後加入塗覆劑，吸附了腰果殼油的二氧化矽和塗覆劑在加溫下混合，包覆二氧化矽的表面即可。 The apparatus used in the oil absorption treatment and the coating treatment in the present invention is not particularly limited, and examples thereof include a mixer such as a paddle mixer, a ribbon blender, a rocking mixer, and a cone mixer. Further, in the present invention, the oil absorbing step and the coating step may be carried out continuously in the same vessel or separately. That is, as long as the cerium oxide is mixed with the cashew nut shell oil, the cashew nut shell oil is adsorbed to the cerium oxide, and after the adsorption, the coating agent is added, and the cerium oxide adsorbing the cashew nut shell liquid and the coating agent are mixed under heating. The surface of the cerium oxide may be coated.
此外，本發明的製造方法中，若使用加熱下熔解的油脂為塗覆劑，則不需要使用溶劑，也不需要乾燥步驟。 Further, in the production method of the present invention, when the oil or fat melted under heating is used as a coating agent, it is not necessary to use a solvent, and a drying step is not required.
本發明之製造方法，無論是在常壓或減壓的狀態下進行都可以。 The production method of the present invention may be carried out under normal pressure or reduced pressure.
又，本發明之製造方法中，吸油步驟雖然也可以在常溫下進行，但考量到吸油效率，建議加熱至20~100℃之間為宜、30~80℃之間較佳、40~80℃之間更佳。 Further, in the production method of the present invention, the oil absorption step may be carried out at a normal temperature, but in consideration of the oil absorption efficiency, it is recommended to heat to between 20 and 100 ° C, preferably between 30 and 80 ° C, and preferably between 40 and 80 ° C. Better between.
本發明中了解到，使腰果殼油、檟如子酸、腰果二酚和腰果酚在30℃以上的溫度下吸附於二氧化矽粒子並做成製劑，可以減少腰果殼油等的有效成分的溶離。這種效 果並不侷限於使用平均粒徑為150μm以上之二氧化矽的情況。 In the present invention, it is known that cashew nut shell liquid, ruthenium-like acid, cardanol and cardanol are adsorbed to cerium oxide particles at a temperature of 30 ° C or higher and formulated to reduce the active ingredients of cashew nut shell liquid and the like. Dissolution. This effect It is not limited to the case of using cerium oxide having an average particle diameter of 150 μm or more.
因此，本發明為製造含有腰果殼油、檟如子酸、腰果二酚和腰果酚與二氧化矽粒子之製劑的製造方法，而且也跟包含使腰果殼油、檟如子酸、腰果二酚和腰果酚在30℃以上(以30~80℃為宜，40~80℃較佳)吸附於二氧化矽粒子之步驟的製造方法有關。 Accordingly, the present invention is a process for producing a preparation containing cashew nut shell liquid, a nutrient acid, a cardanol, a cardanol and a ceria particle, and also comprises a cashew nut shell liquid, a nutrient acid, a cardanol It is related to the production method of the step of adsorbing to the ceria particles at a temperature above 30 ° C (preferably 30 to 80 ° C, preferably 40 to 80 ° C).
包覆步驟以配合塗覆劑的熔點調整加溫溫度為宜。加入塗覆劑時的加溫溫度只要超過熔點都可以，但以高於使用之塗覆劑的熔點5~50℃為宜。 The coating step is preferably adjusted to match the melting point of the coating agent. The heating temperature at the time of adding the coating agent may be as long as it exceeds the melting point, but it is preferably 5 to 50 ° C higher than the melting point of the coating agent to be used.
使用塗覆劑做包覆處理時，可利用上述設備進行，具體來說是執行以下步驟。 When the coating agent is used for the coating treatment, it can be carried out by using the above apparatus, specifically, the following steps.
‧使腰果殼油等吸附於平均粒徑150μm以上之二氧化矽粒子。 ‧ The cashew nut shell liquid or the like is adsorbed to the cerium oxide particles having an average particle diameter of 150 μm or more.
‧於吸附了腰果殼油等的二氧化矽粒子(二氧化矽原體)中添加適量的塗覆劑，在適當的溫度下攪拌混合。 ‧ Add an appropriate amount of coating agent to the cerium oxide particles (cerium dioxide precursor) to which cashew nut shell liquid or the like is adsorbed, and stir and mix at an appropriate temperature.
‧攪拌混合後，視需要冷卻被包覆好了的二氧化矽粒子。 ‧ After mixing and mixing, cool the coated cerium oxide particles as needed.
本發明之二氧化矽製劑適用於：反芻動物用瘤胃發酵改善劑、鼓脹症預防劑、鼓脹症治療劑、皺胃移位治療劑、酸中毒治療劑、梭菌屬所引起疾病的防除劑、球菌目所引起疾病的防除劑、提高乳牛產乳量的效果、預防乳牛圍產期疾病的效果、提高乳牛繁殖效率的效果以及家畜體重增加促進劑。而且，本二氧化矽製劑也可當做飼料添加 劑使用。 The cerium oxide preparation of the invention is suitable for: a rumen fermentation improving agent for ruminants, a bulging prophylactic agent, a bulging therapeutic agent, a gastric augmentation shifting therapeutic agent, a acid poisoning therapeutic agent, a control agent for diseases caused by Clostridium, The control agent for the disease caused by the bacterium, the effect of increasing the milk yield of the cow, the effect of preventing the perinatal disease of the cow, the effect of improving the reproductive efficiency of the cow, and the promoter of the weight gain of the livestock. Moreover, the cerium oxide preparation can also be added as a feed. Use of the agent.
本發明之飼料添加劑，只要含有本發明之二氧化矽製劑並無特殊限制。除此之外可進一步含有：促進反芻動物成長的有效成分、營養補給成分、提高保存安定性的成分等之任意成分。像這樣的任意成分舉例來說有：常球菌屬細菌、芽孢桿菌屬細菌、雙叉桿菌屬細菌之類的活菌劑；澱粉酶、脂肪酶之類的酵素；L-抗壞血酸、氯化膽鹼、肌醇、葉酸之類的維他命；氯化鉀、檸檬酸鐵、氧化鎂、磷酸鹽類之類的礦物質；DL-丙胺酸、DL-甲硫胺酸、L-離胺酸之類的胺基酸；富馬酸、丁酸、乳酸、醋酸之類的有機酸及其鹽類；乙氧喹、二丁基羥基甲苯、丁基羥基甲氧苯、阿魏酸、維他命C、維他命E之類的抗氧化劑；丙酸鈣等殺真菌劑；羧甲基織維素(CMC)、酪蛋白鈉、聚丙烯酸鈉之類的黏著劑；卵磷脂、甘油脂肪酸酯、山梨糖醇酐脂肪酸酯之類的乳化劑；蝦青素、斑螯黃質之類的色素；各種酯類、醚類、酮類等香味料。 The feed additive of the present invention is not particularly limited as long as it contains the cerium oxide preparation of the present invention. In addition to this, it may further contain an optional component which promotes the growth of the ruminant, the nutrient replenishing component, and the component which improves the preservation stability. Examples of any of such components include: bacteria of the genus Aspergillus, bacteria of the genus Bacillus, bacteria of the genus Bifidobacterium; enzymes such as amylase and lipase; L-ascorbic acid and choline chloride , vitamins such as inositol, folic acid; minerals such as potassium chloride, ferric citrate, magnesium oxide, phosphate; DL-alanine, DL-methionine, L-lysine, etc. Amino acid; organic acids such as fumaric acid, butyric acid, lactic acid, acetic acid and salts thereof; ethoxyquin, dibutylhydroxytoluene, butylhydroxymethoxybenzene, ferulic acid, vitamin C, vitamin E Antioxidants such as; fungicides such as calcium propionate; adhesives such as carboxymethyl averaverin (CMC), casein sodium, sodium polyacrylate; lecithin, glycerin fatty acid ester, sorbitan fat Emulsifiers such as acid esters; pigments such as astaxanthin and scutellaria; flavors such as various esters, ethers, and ketones.
又，本發明之飼料添加劑可以與通常被用來當做飼料的其他飼料成分混合，製成飼料。飼料的種類和二氧化矽製劑以外的成分並無特殊限制。 Further, the feed additive of the present invention can be mixed with other feed ingredients which are usually used as a feed to form a feed. The type of feed and the ingredients other than the ceria preparation are not particularly limited.
本發明之飼料，在以牛、山羊、羊等反芻動物為例的情況下，飼料餵食量可依動物的種類、體重、年齡、性別、健康狀況與飼料的成分等做適當的調整，此時飼料內所含腰果殼油以0.005~500g/頭‧天為宜，0.05~100g/頭‧天較佳，0.5~50g/頭‧天更佳。 In the case of the feed of the present invention, in the case of ruminants such as cows, goats, and sheep, the feed amount can be appropriately adjusted according to the animal's type, body weight, age, sex, health condition, and feed composition. The cashew nut shell liquid contained in the feed is preferably 0.005~500g/head ‧ days, 0.05~100g/head ‧ days is better, 0.5~50g/head ‧ days is better
飼料餵食的方法與飼養的方法，可依照動物種類採常用的方法。 The method of feeding and feeding methods can be carried out according to the commonly used methods of animal species.
自腰果交易股份有限公司取得腰果殼500kg，經壓榨製成腰果殼油(未加熱CNSL)158kg。 From Cashew Nut Co., Ltd., 500 kg of cashew nut shell was obtained, and 158 kg of cashew nut shell liquid (unheated CNSL) was pressed.
腰果殼油的成分用下述方法測定。即採用：HPLC(Waters 600，日本Waters股份有限公司)，檢測機(Waters 490E，日本Waters股份有限公司)，列印機(Chromatopac C-R6A、島津製作所)，管柱(Supelcosil LC 18,Supelco,Inc)。分析條件如下：使用溶劑為乙腈：水：醋酸為80：20：1(容量比)，流速為2ml/分鐘，檢測280nm的吸光度。 The composition of the cashew nut shell liquid was measured by the following method. That is, using: HPLC (Waters 600, Japan Waters Co., Ltd.), testing machine (Waters 490E, Japan Waters Co., Ltd.), printing machine (Chromatopac C-R6A, Shimadzu Corporation), pipe column (Supelcosil LC 18, Supelco, Inc). The analysis conditions were as follows: The solvent was acetonitrile: water: acetic acid was 80:20:1 (volume ratio), the flow rate was 2 ml/min, and the absorbance at 280 nm was measured.
未加熱腰果殼油中含有，檟如子酸61.8質量%、腰果酚8.2質量%和腰果二酚質量19.9%。 The unheated cashew nut shell liquid contains, for example, 61.8% by mass of the acid, 8.2% by mass of the cardanol, and 19.9% by weight of the cashew nut.
(1)二氧化矽採用下列Evonik、Rhodia與Oriental Silicas Corporation的產品。惟，平均粒徑的數值所記載的為各公司型錄上的數值。 (1) Cerium oxide uses the following products of Evonik, Rhodia and Oriental Silicas Corporation. However, the numerical values of the average particle diameters are the values on the company catalogues.
[表1]
(2)塗覆劑採用下列和光純藥與橫關油脂的產品。 (2) The coating agent is the following product of the pure pure drug and the cross-cut grease.
(3)腰果殼油 (3) Cashew nut shell oil
如上述自腰果交易股份有限公司取得腰果殼，經壓榨製成腰果殼油。 The cashew nut shell is obtained from the cashew nut trading company as described above, and is pressed into cashew nut shell liquid.
(4)吸油步驟 (4) Oil absorption step
設置配有滴下漏斗和槳狀攪拌葉片的300ml三口可分離式燒瓶。 A 300 ml three-neck separable flask equipped with a dropping funnel and paddle stirring blades was set.
將表1中所記載各粒徑之二氧化矽52g加入燒瓶中，以溫水浴加熱至預定的溫度。一邊攪拌，一邊將裝在漏斗中的68g腰果殼油以約40分鐘的時間滴下。滴完後的5分鐘內仍持續攪拌，吸油步驟結束(製造例1)。 52 g of cerium oxide of each particle diameter shown in Table 1 was placed in a flask and heated to a predetermined temperature in a warm water bath. While stirring, 68 g of cashew nut shell liquid contained in a funnel was dropped over a period of about 40 minutes. Stirring was continued for 5 minutes after the completion of the dropping, and the oil absorption step was completed (Production Example 1).
(5)一貫製造(包覆步驟) (5) Consistent manufacturing (coating step)
於上述(4)吸油步驟結束後的二氧化矽原體中，加入 24g打碎的棕櫚硬化油(橫關油脂製品)，一邊攪拌，一邊混合均勻。浸70℃溫水浴並攪拌10分鐘後，繼續同樣的攪拌並冷卻，包覆步驟結束(製造例2)。 Adding to the cerium oxide precursor after the end of the (4) oil absorption step 24g of crushed palm hardened oil (horizontal oil products), while mixing, mix well. After immersing in a warm water bath of 70 ° C and stirring for 10 minutes, the same stirring was continued and cooling, and the coating step was completed (Production Example 2).
(6)分開製造(包覆步驟) (6) Separate manufacturing (coating step)
使用在上述(4)吸油步驟所製造之含腰果殼油的二氧化矽，再用各種塗覆劑製造包覆粒劑。少量的包覆步驟則使用500ml燒瓶，藉由讓燒瓶在溫水浴中旋轉來進行。 The granules containing the cashew nut shell liquid produced in the above (4) oil absorbing step are used, and the coating granules are produced by using various coating agents. A small amount of the coating step was carried out using a 500 ml flask by rotating the flask in a warm water bath.
具體來說是將上述(4)吸油步驟所製造之含腰果殼油的二氧化矽10g，以及打碎了的各種塗覆劑2g，加入500ml燒瓶中，讓燒瓶旋轉以混合均勻。接著，設定溫水浴溫度至適於所加入的塗覆劑的熔點，讓燒瓶浸於溫水浴中旋轉約10分鐘進行包覆步驟。依此法製造用表2中所列6種塗覆劑(月桂酸、肉荳蔻酸、棕櫚酸、硬脂酸、棕櫚硬化油、大豆硬化油)進行包覆處理過的製劑(製造例3~8)。 Specifically, 10 g of cerium oxide-containing cerium oxide produced by the above (4) oil absorbing step, and 2 g of various coating agents which were pulverized were placed in a 500 ml flask, and the flask was rotated to be uniformly mixed. Next, the warm water bath temperature was set to a melting point suitable for the applied coating agent, and the flask was immersed in a warm water bath for about 10 minutes to carry out a coating step. According to this method, a preparation prepared by coating with six kinds of coating agents (lauric acid, myristic acid, palmitic acid, stearic acid, palm hardening oil, soybean hardening oil) listed in Table 2 was produced (manufacturing example 3~) 8).
圖1所示為製成之製劑的電子顯微鏡照片。由圖可確知，經塗覆劑包覆處理會形成包覆層。 Figure 1 shows an electron micrograph of the prepared preparation. It can be ascertained from the figure that the coating layer is formed by coating treatment.
將製造例1(吸油溫度40℃)的各種二氧化矽製劑(表1)在4℃下靜置4天。之後確認各二氧化矽表面是否有腰 果殼油析出(表3)。 Various cerium oxide preparations (Table 1) of Production Example 1 (oil absorption temperature: 40 ° C) were allowed to stand at 4 ° C for 4 days. After confirming whether the surface of each of the cerium oxide has a waist The shell oil was precipitated (Table 3).
根據圖2可確知，平均粒徑110μm之二氧化矽的表面有腰果殼油的析出。反之，平均粒徑170μm、250μm和320μm的二氧化矽則無(圖3)。 According to Fig. 2, it was confirmed that the surface of the ceria having an average particle diameter of 110 μm had precipitation of cashew nut shell liquid. On the contrary, cerium oxide having an average particle diameter of 170 μm, 250 μm and 320 μm was absent (Fig. 3).
取1g上述2.二氧化矽製劑的調製(4)和(6)中所製成的各種包覆粒劑(二氧化矽採用Sipernat2200)加入40ml的水中，在20℃下靜置1小時。接著回收包覆粒劑，用醋酸乙酯提取並回收粒劑中殘留的腰果殼油，計算出溶離量。其結果示於表4。 1 g of the above-mentioned 2. cerium oxide preparations The various coating granules prepared in the preparations (4) and (6) (cerium oxide using Sipernat 2200) were added to 40 ml of water, and allowed to stand at 20 ° C for 1 hour. Next, the coated granules were recovered, and the cashew nut shell liquid remaining in the granules was extracted with ethyl acetate, and the amount of dissolution was calculated. The results are shown in Table 4.
[表4]
表4顯示，比肉荳蔻酸熔點高的材料有優越的抑制溶離效果。塗覆劑的抑制溶離能力有可能與塗覆劑的熔點有關。 Table 4 shows that the material having a higher melting point than myristic acid has a superior effect of inhibiting the dissolution. The ability of the coating agent to inhibit the detachment may be related to the melting point of the coating agent.
依上述2.二氧化矽製劑的調製(4)和(5)同樣的方法用棕櫚硬化油製造包覆粒劑。 The coated granules were produced from palm hardened oil in the same manner as in the above preparations (2) and (5) of the above-mentioned 2. cerium oxide preparation.
將依此法製成的各種包覆粒劑，除了靜置時間設為15分鐘以外，其他依照上述3.性能評價(3)同樣的方法進行溶離性評估。其結果示於表5。 The various granules prepared by this method were subjected to the evaluation of the solvency in the same manner as in the above-mentioned 3. Performance Evaluation (3) except that the standing time was 15 minutes. The results are shown in Table 5.
[表5]
由表5可知，不管用哪種二氧化矽都可製造具有抑制溶離效果的二氧化矽製劑。 As is apparent from Table 5, a cerium oxide preparation having an effect of suppressing the dissolution can be produced regardless of which cerium oxide is used.
針對製造例1的各種二氧化矽製劑，除了溶離性評估的靜置時間設為15分鐘以外，其他依照上述3.性能評價(3)同樣的方法進行溶離性評估。其結果示於表6。惟，評估所進行的吸油溫度在20~80℃之間。 For the various cerium oxide preparations of Production Example 1, the solute evaluation was carried out in the same manner as in the above-mentioned 3. Performance Evaluation (3) except that the standing time for the evaluation of the solubility was 15 minutes. The results are shown in Table 6. However, the evaluation of the oil absorption temperature is between 20 and 80 °C.
[表6]
由表6可知，不管用哪種二氧化矽，只要吸油溫度設定在30℃以上都可明顯抑制腰果殼油自製劑溶離；增大添加使用之二氧化矽粒徑可進一步抑制溶離。 It can be seen from Table 6 that regardless of which cerium oxide is used, as long as the oil absorption temperature is set to 30 ° C or higher, the cashew nut shell oil can be significantly inhibited from the dissolution of the preparation; increasing the particle size of the added cerium oxide can further suppress the dissolution.
依上述2.二氧化矽製劑的調製(4)和(5)同樣的方法用棕櫚硬化油製造包覆粒劑。惟，吸油溫度在25℃及50℃之間。 The coated granules were produced from palm hardened oil in the same manner as in the above preparations (2) and (5) of the above-mentioned 2. cerium oxide preparation. However, the oil absorption temperature is between 25 ° C and 50 ° C.
將依此法製成的各種包覆粒劑，除了靜置時間設為15分鐘以外，其他依照上述3.性能評價(3)同樣的方法進行溶離性評估。其結果示於表7。 The various granules prepared by this method were subjected to the evaluation of the solvency in the same manner as in the above-mentioned 3. Performance Evaluation (3) except that the standing time was 15 minutes. The results are shown in Table 7.
由表7可知，提高吸油溫度，加上進行塗覆劑處理可進一步抑制溶離性。 As can be seen from Table 7, the increase in the oil absorption temperature and the treatment with the coating agent can further suppress the solubility.
藉由本發明可提供安全性與操作性得到改善的含腰果殼油等二氧化矽製劑。又，藉由本發明可提供簡易化了的包覆粒劑製造方法。本發明的製劑及其製造方法在畜牧領域是有用的。 According to the present invention, a cerium oxide preparation such as a cashew nut shell liquid having improved safety and workability can be provided. Further, according to the present invention, a simplified method for producing a coated granule can be provided. The formulations of the invention and methods for their manufacture are useful in the livestock sector.
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