JP3553126B2 - Feed with good oxidation stability - Google Patents
Feed with good oxidation stability Download PDFInfo
- Publication number
- JP3553126B2 JP3553126B2 JP08794694A JP8794694A JP3553126B2 JP 3553126 B2 JP3553126 B2 JP 3553126B2 JP 08794694 A JP08794694 A JP 08794694A JP 8794694 A JP8794694 A JP 8794694A JP 3553126 B2 JP3553126 B2 JP 3553126B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- feed
- spermine
- fat
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
- Y02A40/818—Alternative feeds for fish, e.g. in aquacultures
Landscapes
- Feed For Specific Animals (AREA)
- Fodder In General (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、水産用または畜産用飼料であって、ポリアミン類の１種であるスペルミン、スペルミジンおよびプトレスシンの一部もしくは全部を含有してなる製剤を飼料原材料に添加して得られる酸化安定性の良い前記飼料に関する。
【０００２】
【従来の技術】
水産用および畜産用飼料には、原材料として魚粉、フィッシュミール、魚油等が配合されることが多く、保存中に空気中の酸素により容易に酸化劣化し、品質低下をまねく。このため数多くの抗酸化剤が該飼料に添加され、その酸化防止効果が試されてきたが、実用的観点から該飼料の酸化劣化を抑制するものがほとんどなかった。現状では、化学合成品であり安全性も疑問視されているエトキシキン（６−エトキシ−１，２−ジヒドロ−２，２，４−トリメチルキノリン）やＢＨＴ（ｐ−ヒドロキシ安息香酸ブチル）等が使用制限付きで添加剤として使われている。したがって、安全性が高く、飼料に対して酸化防止力が強い抗酸化剤の開発が望まれている。
【０００３】
一方、酸化防止効果が比較的高い抗酸化剤としてポリアミン類の１種であるプトレスシン〔ＮＨ２ （ＣＨ２ ）４ ＮＨ２ 〕、スペルミジン〔ＮＨ２ （ＣＨ２ ）３ ＮＨ（ＣＨ２ ）４ ＮＨ２ 〕およびスペルミン〔ＮＨ２ （ＣＨ２ ）３ ＮＨ（ＣＨ２ ）４ ＮＨ（ＣＨ２ ）３ ＮＨ２ 〕が知られている。サケ等の魚類の白子、動物の精液等に極く微量に含まれるこれらのポリアミン類は、例えばジャーナル オブジ アメリカン オイル ケミスツ ソサエティ（ＪＡＯＣＳ）、Ｖｏｌ．６８、Ｎｏ．６、第３５３〜３５８頁、１９９１年によれば、高度不飽和脂肪酸を含む魚油等に直接添加し、ランシマット法により７０〜１００℃における抗酸化効果をα−トコフェロール、エトキシキン、ＢＨＡ（２，（３）−ｔｅｒ−ブチル−４−ヒドロキシアニソール）等と比較した結果、スペルミンはエトキシキンの約３倍強、スペルミジンは同じく約２倍、プトレスシンは同じくほぼ同等の抗酸化力を示すとしている。
【０００４】
しかしながら、前記ポリアミン類はそれ自体が化学的に不安定であり、二酸化炭素や酸素により急速に分解され、抗酸化力を失なう。これを防ぐため、前記ポリアミン類を塩酸塩等の塩型に変換すれば、化学的安定性は増すが、これらのものはもはや抗酸化力やその他の種々の活性をもたない。したがってスペルミン、スペルミジンおよびプトレスシンは、エトキシキンと同程度もしくはそれ以上の強力な抗酸化力を有しているにもかかわらず、これを水産用または畜産用飼料に有効に活用する技術は未だ開発されていない。
【０００５】
【発明が解決しようとする課題】
これまでの水産用および畜産用飼料には前述のような問題点があり、安全性が高くかつ酸化安定性が良い飼料を作り出すことができなかった。また油脂類の抗酸化剤としてポリアミン類をはじめ種々のものが知られているが、これを前記飼料に効果的に適用する技術は開発されていない。
したがって本発明は、安全性の点で懸念がなく、酸化安定性に優れ、また長期間にわたり抗酸化効果が持続する水産用または畜産用飼料を提供することを目的とした。
【０００６】
【課題を解決するための手段】
本発明者らは、上記の目的を達成すべく鋭意研究を行ったところ、いわば生体内成分であり安全性の点で問題のないスペルミン、スペルミジンおよびプトレスシンの一部ないし全部を油脂組成物または乳化組成物に加工した製剤が、魚粉、フィッシュミール、魚油、植物系油粕等を原材料とする飼料に対して高活性かつ持続性のある抗酸化力をもち、該製剤を添加した飼料は長期間の保存が可能になることを見出した。本発明はかかる知見に基づいて完成されたものである。
【０００７】
すなわち本発明の要旨は、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上を含有してなる製剤（以下、スペルミン等製剤という）を飼料原材料に添加してなる酸化安定性の良い水産用または畜産用飼料である。そして、本発明の要旨の第１のタイプは、スペルミン等製剤がスペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂とを含有してなる油脂組成物、あるいは該油脂組成物がさらにトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルを含むものであることにある。要旨の第２のタイプは、スペルミン等製剤が前記油脂組成物と水相とを乳化せしめてなる乳化組成物、あるいは該乳化組成物がさらにＬ−アスコルビン酸、その塩、蛋白質およびペプチドからなる群より選ばれる少なくとも１種を含むものであることにある。以下、本発明について詳述する。
【０００８】
まず本発明で用いるポリアミン類すなわちスペルミン、スペルミジンおよびプトレスシンは、さけ等の魚類の白子や牛、豚等の動物の精子より抽出するか、化学合成するか、あるいは酵素や微生物を用いた生化学的合成等の手段により作成することができる。なお、これらのポリアミン類には試薬グレードの市販品（例えばＳＩＧＭＡ社製）がある。
【０００９】
本発明の特徴であるスペルミン等製剤は、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上を公知の材料とともに加工してなる製剤であり、水溶液、エタノールやブタノール溶液、リポソーム製剤、マイクロスクエア製剤、錠剤等が可能であるが、以下に述べるような油脂組成物（油剤）または乳化組成物（乳剤）が好ましい。
【００１０】
本発明のスペルミン等製剤の第１のタイプは、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂とを含有してなる油脂組成物、あるいは該油脂組成物がさらにトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルを含むものである。
【００１１】
ここで油脂の種類は、とくに限定されるものではないが、常温にて液状を呈する油脂が使用にあたって簡便である。本発明に適用できる油脂の具体例として大豆油、菜種油、コーン油、サフラワー油、綿実油、ヒマワリ油、パーム油、アマニ油、カカオ脂、シア脂、オリーブ油等の植物性油脂や牛脂、ラード等の動物性油脂、炭素数６〜１０の中鎖脂肪酸の単酸基または混酸基トリグリセリド（例えば日清製油（株）製、商品名：ＯＤＯ）、アセチンファット（酢酸トリグリセリド）、オレイン酸トリグリセリド等をあげることができる。このうち大豆油、菜種油、コーン油、中鎖脂肪酸トリグリセリドが好ましい。なおイワシ、サンマ、サバ等の魚油、イカ、スケトウダラ等の肝油、アザラシ、トド等の海獣油等の高度不飽和脂肪酸含有油脂を用いることも可能である。
【００１２】
油脂組成物に配合するスペルミン、スペルミジンまたは／およびプトレスシンの総量は油脂組成物全量に対して０．０１〜７０重量％、より好ましくは０．１〜５０重量％、最も好ましくは２〜１０重量％である。０．０１重量％未満では本発明の油脂組成物を飼料に添加しても酸化防止効果は小さく、逆に７０重量％を超えて配合しても均一な溶解ないし分散状態の油脂組成物が得られず、配合量に見合う抗酸化力を発揮しにくくなり、不経済である。スペルミン、スペルミジンおよびプトレスシンのうち２種もしくは３種を併用する場合のこれらの割合は特に限定されるものではなく、スペルミン＞スペルミジン＞プトレスシンの順に抗酸化力が強い点を考慮すれば種々の混合比率のものが利用できるが、実用的な抗酸化製剤を得るためにはこれら２種もしくは３種の混合物中のスペルミン含量を３０重量％以上、またはスペルミンとスペルミジンとの合計含量が５０重量％以上とすることが望ましい。
【００１３】
なおこの油脂組成物にトコフェロールを０．０１〜３０重量％、好ましくは０．１〜１０重量％または／およびＬ−アスコルビン酸脂肪酸エステルを０．００１〜５０重量％、好ましくは０．１〜１０重量％添加すると該油脂組成物の抗酸化力はさらに高まる。ここにトコフェロールは、Ｄ体、Ｌ体またはＤＬ体の、α，β，γおよびδ−トコフェロールの単独もしくは任意の混合物でよく、天然物由来のものまたは合成品を使用できる。δ−トコフェロール含量の高いものが望ましいが、実用的には大豆油、小麦胚芽油、菜種油等の植物油脂を脱臭精製する際の副産物から濃縮されるＤ体のα，β，γおよびδ−混合トコフェロールが好適であり、あるいはこれらの分画物、合成フィトールから調製されるＤＬ体のα−トコフェロール等でもさしつかえない。かかるトコフェロールが油脂との混合物であっても支障はない。また、Ｌ−アスコルビン酸脂肪酸エステルとしては、Ｌ−アスコルビン酸のパルミチン酸あるいはステアリン酸エステルが市販させており、これらが好適である。
【００１４】
本発明の油脂組成物を調製するには、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上を、あるいはこれらとトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルとを、そのままもしくはエタノール、イソプロパノール、ブタノール、エーテル等の溶媒に予め溶解させた後に前記油脂に添加し、常温にてもしくは約５０℃に加温し、ミキサーやブレンダー等の適当な攪拌機あるいは混合機を用いて、５０〜４０００ｒｐｍ の回転数で攪拌して均一に溶解ないし分散させ、必要に応じて減圧にて脱溶媒すればよい。なお油脂組成物の性状を調整するため、要すれば油溶性の１２−ヒドロキシステアリン酸等の増粘剤、キャンデリラワックス、カルナウバワックス、パラフィンワックス等のワックス類、着色剤、香料等を配合してもよい。
かくして本発明のスペルミン等製剤の第１のタイプ、すなわちスペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂とを含有してなる油脂組成物、あるいは該油脂組成物がさらにトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルを含むものが得られる。
【００１５】
次に、本発明のスペルミン等製剤の第２のタイプは、前記第１のタイプ（油脂組成物）を油相とし、これと水相とを乳化せしめてなる乳化組成物、あるいは該乳化組成物がさらにＬ−アスコルビン酸、その塩、蛋白質およびペプチドからなる群より選ばれる少なくとも１種を含むものである。ここで、Ｌ−アスコルビン酸、その塩、蛋白質およびペプチドからなる群より選択される少なくとも１種のものは前記水相に含有せしめ、乳化処理にあたっては乳化剤を使用することが好ましい。また、乳化組成物は水中油型もしくは油中水型乳化組成物である。
【００１６】
乳化剤は公知のもの、例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リシノール酸、１２−ヒドロキシステアリン酸、アラキン酸、ベヘン酸、牛脂分解脂肪酸、ヤシ油分解脂肪酸、菜種油分解脂肪酸等の脂肪酸残基を有するプロピレングリコールモノ脂肪酸エステル、脂肪酸モノまたはジグリセリド、ショ糖モノ、ジまたはトリ脂肪酸エステル、ソルビタンモノ、セスキまたはジ脂肪酸エステル、前記脂肪酸または脂肪酸エステルのエチレンオキサイドまたは／およびプロピレンオキサイド２〜４０モル付加物、平均重合度２〜１５とくに６または１０のポリグリセリンモノ、ジまたはトリ脂肪酸エステル等のエステル系乳化剤を用いることができる。
【００１７】
また大豆レシチン、菜種レシチン、卵黄レシチン、該レシチン等から分画、濃縮されるあるいは化学合成されるホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルイノシトール、該リン脂質のリゾ体等のレシチン系乳化剤、前記脂肪酸のカリウム塩またはナトリウム塩等の脂肪酸石鹸系乳化剤、ラウリルアルコール、テトラデシルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール、アラキルアルコール、ベヘニルアルコール、オクチルフェノール、ノニルフェノール等のエチレンオキサイドまたは／およびプロピレンオキサイド２〜３０モル付加物等のエーテル系乳化剤も使用できる。本発明ではこれらの乳化剤の１種もしくは２種以上を適宜に利用できるが、とりわけ脂肪酸グリセリド、ソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステルおよびレシチンのうちの１つまたは２つ以上が好ましい。
【００１８】
かかる乳化剤を乳化組成物全量に対して約０．１〜５重量％用い、前記油脂組成物を油相として、油相と水相との比率を油相／水相＝５／９５〜９５／５（重量比、以下同じ）、なお水中油型乳化組成物の場合には好ましくは油相／水相＝５／９５〜約６０／４０とし、また油中水型乳化組成物の場合には好ましくは油相／水相＝約４０／６０〜９５／５とし、順相または転相乳化法により乳化せしめる。本発明の乳化組成物では、分散液滴（水中油型乳化組成物における油滴、油中水型乳化組成物における水滴）の平均粒径は約５０μｍ以下、好ましくは約５〜３０μｍ、さらに望ましくは約５〜２０μｍにしておくとよい。約５０μｍを超え６０μｍ程度以上の平均粒径になると安定な乳化状態を維持しにくくなる。
【００１９】
なおこの乳化組成物を調製するにあたり、水相にＬ−アスコルビン酸、その塩、蛋白質およびペプチドからなる群より選ばれる少なくとも１種の水性成分を含有せしめることにより、該乳化組成物の抗酸化力をさらに増強させることができる。とくに蛋白質の併用は、抗酸化力の増強とともに乳化状態の安定化にも有効である。乳化組成物全体として、Ｌ−アスコルビン酸およびその塩は各０．０１〜３０重量％、好ましくは０．０５〜１０重量％用いればよく、また蛋白質は０．１〜３０重量％、好ましくは０．５〜２０重量％であり、ペプチドは０．１〜３０重量％、好ましくは０．５〜１０重量％を配合する。これらの水性成分の添加量はいずれも、前記の範囲を外れて少ないと、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上の抗酸化力を増強させることができず、逆に前記範囲を超えて添加量を増やしてもさらなる抗酸化力の増大は期待できない。
【００２０】
これらの水性成分のうち、Ｌ−アスコルビン酸およびその塩は市販品を用いればよい。また蛋白質およびペプチドは動物または植物由来のどちらでも構わない。動物由来のものとしては卵白、卵黄、蓄乳、肉エキス、魚粉、カニミール、エビミール、フェザーミール等の蛋白質およびペプチドがあげられ、植物由来のものとしては大豆、小麦、菜種、綿実、アマニ、サフラワー、ヒマワリ、ゴマ、落花生、ヤシ、カポック、アーモンド、クルミ等から抽出した蛋白質およびペプチドがあげられるが、本発明はこれらに限定されるものではない。
【００２１】
ペプチドは、前記動植物由来の蛋白質を公知の方法すなわち酸、アルカリまたはプロテアーゼ等により加水分解し、中和、加熱、酸性沈澱、凝集、分離、濃縮等の処理を施し得られるもので、その分子量は５００〜５００００であり、好ましくは１０００〜１００００である。分子量が５００より小さいペプチドでは本発明の所望の効果が得られず、また乳化組成物に呈味を付与する傾向が大きくなり、製品の用途を制限しかねない。また分子量が５００００を超えると効果の点で前記蛋白質を配合する場合と差がなくなる。蛋白質およびペプチドの好ましいものとして、卵白、カゼイン、濃縮大豆蛋白、分離大豆蛋白、ツエイン、グルテンおよびこれらのペプチドを例示できる。
【００２２】
本発明の乳化組成物は次のようにして調製する。すなわち前記方法により調製した、スペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂とを、要すればさらにトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルを含有せしめてなる油脂組成物を油相とし、一方、水、あるいは水にＬ−アスコルビン酸、その塩、蛋白質、およびペプチドからなる群より選択される１種以上の水性成分を溶解ないし分散させた水溶液を水相とし、好ましくは前記乳化剤の一部もしくは全部を該油相または該水相に添加する。このとき親油性乳化剤は油相に、親水性乳化剤は水相に、また親油性および親水性乳化剤を併用する場合には同様に各相にそれぞれ溶解させておくのがよい。
【００２３】
かかる油相および水相を各々、常温で、あるいは要すれば約７０℃程度に加温し、ホモミキサー、ホモジナイザー、ヒスコトロン、アジホモミキサー等の攪拌、混合機を用いて例えば回転数１０００〜１００００ｒｐｍ で１０〜３０分間攪拌しながら、好ましくは水中油型乳化組成物のときは水相に油相を添加し、また油中水型乳化組成物のときは油相に水相を添加してそれぞれ乳化せしめる。
【００２４】
なお本発明の乳化組成物は、前記油脂組成物の必須構成成分すなわちスペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂、あるいは該成分とトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルとを予め混合して溶解ないし分散させることなく、これらを水、水性成分、乳化剤等と直接混合、乳化させても調製することができる。また前記のほかの水相成分として、必要に応じてカルボキシメチルセルロース、グアーガム、キサンタンガム、アルギン酸ソーダ、カラギーナン等の増粘ないしゲル化剤、着色剤、香料等を配合してもよい。
【００２５】
かくして本発明のスペルミン等製剤の第２のタイプ、すなわちスペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上と油脂と水、あるいはさらにトコフェロールまたは／およびＬ−アスコルビン酸脂肪酸エステルを含む該成分を乳化せしめてなる水中油型もしくは油中水型乳化組成物、さらにまたこれにＬ−アスコルビン酸、その塩、蛋白質およびペプチドからなる群より選ばれる少なくとも１種を含む該乳化組成物が得られる。
【００２６】
本発明では、以上に述べたようなスペルミン等製剤、すなわちスペルミン、スペルミジンおよびプトレスシンのうちの１種または２種以上を含有する油脂組成物（油剤）あるいは乳化組成物（乳剤）と飼料原材料とを用いて、酸化安定性の良い水産用または畜産用飼料が製造される。乳化物は、魚粉やフィッシュミールなど魚油を含有している飼料組成物に対して２〜５０重量％添加することが好ましい。また、スペルミン等の油剤は魚油等の高度不飽和脂肪酸含有油脂に対して０．０１〜５０重量％添加することが好ましい。
【００２７】
本発明の飼料は、前記スペルミン等製剤以外は公知の飼料用原材料を用いて調製することができる。すなわち水産用飼料は、穀類、そうこう類、植物油粕類、動物性飼料原料、その他原料等から構成される組成物である。穀類としては、とうもろこし、グレインソルガム、小麦、大麦、えん麦、ライ麦、玄米、小麦粉、きな粉等が利用できる。そうこう類としては、米ぬか、米ぬか油粕、麦ぬか、ふすま等が含まれる。植物油粕類としては、大豆油粕、アマニ油粕、綿実油粕、落花生油粕、サフラワー油粕、ヤシ油粕、パーム核油粕、ゴマ油粕、ヒマワリ油粕、菜種油粕、カポック油粕等が例示できる。また、動物性飼料原料としては、魚粉、フィッシュソリュブル、フィッシュソリュブル吸着飼料、肉粉、肉骨粉、血粉、カニミール、エビミール、フェザーミール、蚕よう、蚕よう油粕、脱脂粉乳、乾燥ホエー等があげられる。その他、淡水産および海産クロレラ、各種藻類、ワカメ、コンブ等の海草類、セルロースパウダー、カルボキシメチルセルロース等も使用可能である。
【００２８】
畜産用飼料は、穀類、イモ類・カブ類、そうこう類、植物油粕類、その他の粕類、油脂類、草類、動物性飼料原料、細胞蛋白質および非蛋白態窒素化合物、ミネラル、ビタミン、その他原料等からなる。穀類としては、前記水産用飼料の穀類のほかアワ、ヒエ、キビ等が使用される。イモ類・カブ類では、サツマイモ、キャッサバ、バレイショ、カブ、ビート等が含まれる。そうこう類としては、前記水産用飼料と同様のものが利用できる。
また、植物油粕類としては、前記水産用飼料に用いるもののほか麻実粕、アーモンド粕、クルミ粕、カラシ粕、ニガー粕等を例示できる。その他の粕類として、コーングルテンミール、ビール粕、アルコール発酵粕、豆腐粕、蒸留酒粕、醤油粕、トマト搾り粕、コーヒー残渣、ココア残渣等も利用できる。油脂類としては、大豆油、菜種油、コーン油、綿実油、サフラワー油、ヒマワリ油、アマニ油、シソ油、ヤシ油、パーム油、パーム核油、カポック油、ゴマ油、エゴマ油、カカオ脂、シア脂、サル脂、牛脂、ラード、バター、魚油等を例としてあげることができる。草類として、イネ科牧草、マメ科牧草、青がり飼料作物等がある。動物性飼料原料としては、前記水産用飼料における動物性飼料原料のほか鯨肉粉、乳製品副産物（脱脂乳、バターミルク、ホエー）、肉加工副産物（骨粉、羽毛粉）等が利用できる。細胞蛋白質としては、クロレラをはじめとする各種藻類、ワカメ、コンブ、糸状菌、酵母、バクテリア等がある。なお本発明の原材料はこれらの例示に何ら制限されるものではなく、また適宜に選択して配合できる。
【００２９】
本発明の飼料は、前記各種原材料を適宜に選択し、スペルミン等製剤とともに粉砕、混合、成型等の処理を施して得られるものであり、基本的には水産用飼料と畜産用飼料とで異なるところはほとんどない。例えば水産用配合飼料は、形態的には粉末状、粒状および塊状（クランブル、ペレット、多孔質ペレット、線香型、多孔質ペレットのクランブル、気流造粒クランブル、フレーク状）に分けられるが、それらの製法の一例を以下に示す。
【００３０】
主原料、副原料、雑原料および液状原料を各原料タンクに入れ、主原料、副原料および雑原料をそれぞれ適当な粉砕機で粉末化する。また、雑原料（例えばビタミン、ミネラル、ホルモン等）の一部に微量成分やスペルミン等製剤を添加しプレミックスする。この場合、スペルミン等製剤は魚粉やフィッシュミール等の油分を含有する原料に直接添加するか、魚油等の油脂類に添加し、他の原料に混合して粉砕機にかけてもよい。作業性の点では、スペルミン等製剤を魚粉または／および魚油に添加することが好ましい。粉末化したスペルミン等製剤の混合物を配合タンクに入れ、他の粉末原材料と混合した後、さらに液状原料を加えてミキサーで混合する。なおこの時はじめて、スペルミン等製剤を添加し、配合タンク中で混合してもかまわない。このようにして粉末状飼料を製造することができる。
【００３１】
また前記粉末状飼料を一軸または二軸型エスクトルーダー、ペレットミル、ペレッター、クランブラー等の成型機に送り、加水度５〜１０重量％になるまで水蒸気を吹き込んで原材料の澱粉質を糊化させたり、ＣＭＣ（カルボキシメチルセルロース）、リグニンスルホン酸ソーダ等のバインダーをさらに添加して硬度を調節し、混練した後、厚さ２〜１０ｃｍの穴のあいた板にロールで飼料を押し込み、１００〜１０００ｋｇ／ｃｍ２ の高圧下から大気圧下に押し出す。押し出された塊状飼料混合物は、これを適当な長さに切断し、冷却、乾燥処理してペレット状飼料を製造する。多孔質ペレット飼料は、この工程中において高圧状態にある押出機から大気圧状態に押し出すことにより作成される。なおこの多孔質飼料にスペルミン等製剤の例えば乳化組成物等を吸収させると、油分を１０〜２０％程度含んだソフトタイプの飼料ができる。またクランブル飼料は、ペレットや多孔質ペレットをローラーとシフターを用いて砕き、所定の粒径の粒子にふるい分けしたものである。
【００３２】
かくして得られるスペルミン等製剤を配合した飼料は、抗酸化作用を有するスペルミン、スペルミジンおよびプトレスシンの１種または２種以上の効力が維持され、また高められるため、長期間にわたり酸化安定性の良い、品質の良好なものとなる。
【００３３】
【実施例】
参考例１
大豆白絞油１００ｇに、スペルミン（シグマ社製、試薬）２重量％またはスペルミン（同試薬）２重量％と大豆油を含むＤ−α，β，γおよびδ−ミックストコフェロール（シグマ社製、試薬ＴＹＰＥ Ｖ）０．２重量％とをエタノール１０ｍｌに溶解したものを加え、パドルミキサーを用いて５０００ｒｐｍ の回転数で３分間混合し、スペルミンを溶解させた。エタノールを減圧留去して得たスペルミン油脂組成物とスペルミン単品とをそれぞれ褐色サンプル瓶に入れ、キャップをして、４０℃の恒温槽で３ヵ月、６ヵ月および１２ヵ月間保存した。その後、各所定期間保存した該油脂組成物とスペルミンとを用い、スケトウダラ肝油に対する抗酸化力を比較した。すなわちスペルミン含量がスケトウダラ肝油に対して２００ｐｐｍ になるようにそれぞれを添加し、なおスペルミンの場合にはその１／５重量の前記トコフェロールをさらに混合して、強制劣化試験（ＡＯＭ試験）を行った。９７．８±０．２℃で空気を２．３ｍｌ／秒の流速で吹き込み、一定時間毎にサンプリングし、その過酸化物価（ＰＯＶ）を測定して、ＰＯＶが１００になるまでの時間を求めた。その結果を表１に示す。
【００３４】
【表１】
表１のデータから、本発明に係るスペルミン製剤はスケトウダラ肝油に対して長期間保存後に使用しても抗酸化力を高く維持しており、またスペルミンとトコフェロールとを併用した場合には抗酸化力が増強されていることが明らかになった。
【００３６】
実施例１
まずスペルミン（シグマ社製、試薬）２．０ｋｇおよびＤ−α−トコフェロール（シグマ社製、試薬）０．２ｋｇをエタノール１リットルに溶解し、これをスケトウダラ肝油１００ｋｇに添加した後、十分に混合、エタノールを減圧留去してスペルミン等製剤（油脂組成物、実験Ｎｏ．１−２）を作成した。一方、北洋魚粉と沿岸魚粉との１：１（重量比）混合物７８重量％、α−デンプン４重量％、ビタミン（塩化コリン：５０％、アスコルビン酸：１５％、イノシット：２０％、ニコチン酸：１５％）混合物３重量％、ミネラル（リン酸１水素カルシウム：７６％、リン酸２水素カリウム：８％、硫酸カリウム：７％、塩化ナトリウム：４％、酸化マグネシウム：５％）混合物１重量％、前記スペルミン等製剤１０重量％、ソルビン酸カリウム０．１重量％、カルボキシメチルセルロース３重量％および被覆Ｂ１（上野製剤（株）製、商品名：サイアコート）０．９重量％の組成比率で合計１００ｋｇになるように各原材料を用意した。魚粉を粉砕機にかけた後、配合タンク中にデンプン、ビタミン混合物およびミネラル混合物とともに入れ、これらを混合した。さらに、これとスペルミン等製剤とをミキサーで十分に混合し、スペルミン等製剤の混合物を得た。そして、これを加水度５重量％に調節し成型機にかけ、ついで厚さ１０ｃｍの穴のあいた板にロールで押し込み、１０００ｋｇ／ｃｍ２ の高圧下で押し出し、乾燥機およびクーラーにより乾燥させ、水産用ペレット飼料（収量：９４ｋｇ）とした。
なおこれを同時に、同様の方法で表２に示したような組成の各種添加剤（本発明のスペルミン等製剤ほかの油脂組成物）を配合した水産用ペレット飼料を調製した。
【００３７】
以上の各ペレット飼料を６０℃の恒温室に入れ、１０日間保存した後、各々の飼料サンプルをｎ−ヘキサンで抽出して油分を得、この過酸化物価（ＰＯＶ）を測定した。この結果を表２にまとめて示した。これにより、本発明に係わるスペルミン等製剤を添加した飼料は酸化劣化が抑制されていることを認めた。
【００３８】
【表２】
注）※１ 本発明のスペルミン等製剤および比較のための油脂組成物。
※２ 各飼料を６０℃で１０日間保存した後の飼料中油分の過酸化物価。
※３ カプリル酸とカプリン酸との混合脂肪酸のトリグリセリド（日清製油（株）製、商品名：ＯＤＯ）
（ ）内の数値は、添加剤全量に対する各成分の重量％。またスペルミン、スペルミジン、プトレスシン、Ｄ−α−トコフェロール、Ｄ−δ−トコフェロール、Ｄ−混合トコフェロール（大豆油を含むα、β、γおよびδ体の混合物、ＴＹＰＥ Ｖ）、Ｌ−アスコルビン酸パルミテートおよびエトキシキンはいずれもシグマ社製試薬。
【００４０】
実施例２
スペルミジン（シグマ社製、試薬）０．８ｋｇおよびＤ−混合トコフェロール（シグマ社製、試薬）０．２ｋｇをスケトウダラ肝油１００ｋｇに添加し、十分に攪拌、混合しスペルミン等製剤（油脂組成物）を作成した。これに、水道水にＬ−アスコルビン酸（関東化学（株）製、試薬）２．０重量％および卵白ペプチド（キユーピー（株）製、商品名：卵白ペプタイドＥＰ−１、平均分子量：１１００）５重量％を添加した水溶液１００リットルとヘキサグリセリン縮合リシノール酸エステル（阪本薬品（株）製、商品名：ＳＹグリスタ−ＣＲ−５００）とを２．０重量％添加し、ホモジナイザーで十分に攪拌してスペルミジン製剤（Ｗ／Ｏ型乳化組成物、実験ＮＯ． ２−５）を作成した。魚粉４５重量％、大豆油粕８．４重量％、トウモロコシ粕１２重量％、ビタミン（塩化コリン：５０％、アスコルビン酸：１５％、イノシット：２０％、ニコチン酸：１５％）混合物３．０重量％、ミネラル（リン酸１水素カルシウム：７６％、リン酸２水素カリウム：８％、硫酸カリウム：７％、塩化ナトリウム：４％、酸化マグネシウム：５％）混合物２．０重量％、小麦粉１９．６重量％、前記スペルミン等製剤２０重量％の組成比率で合計１００ｋｇとなるように各原材料を用意した。魚粉、大豆油粕、トウモロコシ粕および小麦粉はそれぞれ粉砕機にかけた後に配合タンクに入れ、さらにビタミン混合物、ミネラル混合物を添加し、混合した。その後、これをスペルミン等製剤とともにミキサーに入れ、十分に混合してスペルミン等製剤の混合物を得た。次に、これに水蒸気を吹込み加水度を３重量％に調節してから成型機に入れ、厚さ３ｃｍの穴のあいた板にロールで該混合物を押し込み、２０００ｋｇ／ｃｍ２ の高圧下で押し出した。これをナイフで適当な長さに切断し、油分１５重量％のソフトタイプの畜産用ペレット飼料（収量：８５ｋｇ）を作成した。
【００４１】
なおこれと同時に、同様の方法で表３に示すような組成の各種添加剤（乳化組成物）を配合した畜産用ペレット飼料を調製した。これらのペレット飼料サンプルを６０℃の恒温室で１０日間保存した後、実施例１と同様にＰＯＶを測定した。この結果を表３にまとめた。実施例１と同様に、本発明に係るスペルミン等製剤（乳化組成物）を添加した飼料は酸化劣化が抑制されることが明らかになった。
【００４２】
【表３】
注）※１ 本発明のスペルミン等製剤および比較のための乳化組成物の成分。
※２ 阪本薬品（株）製、商品名：ＳＹグリスタ−ＣＲ−５００。
※３ 理研ビタミン（株）製、商品名：ポエムＪ−２００１。
※４ 日清製油（株）製、商品名：ソルピー５０００。
※５ キユーピー（株）製、商品名：卵白ペプタイドＥＰ−１。
※６ Ｏ／Ｗ：水中油型、Ｗ／Ｏ：油中水型。
※７ 各飼料を６０℃で１０日間保存した後の飼料中油分の過酸化物価。
（ ）内の数値は、添加剤全量に対する各成分の重量％、またスペルミン、スペルミジン、プトレスシン、Ｄ−混合トコフェロール、Ｌ−アスコルビン酸ステアレート、ＢＨＴおよびＬ−アスコルビン酸はいずれもシグマ社製試薬。
【００４４】
【発明の効果】
本発明の飼料は、従来の抗酸化剤であるエトキシキンやＢＨＴを添加したものよりも酸化安定性が優れる。本発明では、スペルミン、スペルミジンおよびプトレスシンから選ばれる１種または２種以上のポリアミンを油剤や乳剤等の製剤に加工した安定性および活性の高い前記ポリアミンを添加するので、長期間にわたり酸化劣化を受けにくい飼料となる。また、飼料製造時における前記ポリアミンの飼料原材料中への分散性も改善される。
本発明で得られる酸化安定性の良い飼料は、水産養殖用、畜産用、ペット動物用、等幅広く使用できる。[0001]
[Industrial applications]
The present invention relates to a feed for fisheries or livestock, which is obtained by adding a preparation containing part or all of spermine, spermidine and putrescine, one of polyamines, to a feed raw material. Good for the feed.
[0002]
[Prior art]
Fish feed, fish meal, fish oil, and the like are often blended in fish and animal feeds as raw materials, and are easily oxidized and degraded by oxygen in the air during storage, resulting in quality deterioration. For this reason, a number of antioxidants have been added to the feed and its antioxidant effect has been tried, but from the practical point of view, there was hardly any that suppressed the oxidative deterioration of the feed. At present, ethoxyquin (6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline) and BHT (butyl p-hydroxybenzoate), which are chemically synthesized products and whose safety is questioned, are used. It is used as an additive with some restrictions. Therefore, there is a demand for the development of an antioxidant which is highly safe and has a strong antioxidant effect on feed.
[0003]
On the other hand, putrescine [NH], a kind of polyamines, is used as an antioxidant having a relatively high antioxidant effect. 2 (CH 2 ) 4 NH 2 ], Spermidine [NH 2 (CH 2 ) 3 NH (CH 2 ) 4 NH 2 ] And spermine [NH 2 (CH 2 ) 3 NH (CH 2 ) 4 NH (CH 2 ) 3 NH 2 〕It has been known. These polyamines contained in trace amounts in fish milts such as salmon, animal semen and the like are described in, for example, Journal of the American Oil Chemistry Society (JAOCS), Vol. 68, no. 6, pp. 353-358, 1991, directly added to fish oil containing polyunsaturated fatty acids and the like, and have an antioxidant effect at 70-100 ° C by α-tocopherol, ethoxyquin, BHA (2, ( 3) -ter-butyl-4-hydroxyanisole) and the like. As a result, spermine is about three times as strong as ethoxyquin, spermidine is about twice as much, and putrescine also shows almost the same antioxidant power.
[0004]
However, the polyamines themselves are chemically unstable, are rapidly decomposed by carbon dioxide and oxygen, and lose their antioxidant power. To prevent this, if the polyamines are converted to a salt form such as hydrochloride, the chemical stability is increased, but these compounds no longer have antioxidant activity and other various activities. Therefore, although spermine, spermidine and putrescine have the same or higher antioxidant activity as ethoxyquin, a technique for effectively utilizing them for feed for marine or livestock has not yet been developed. Absent.
[0005]
[Problems to be solved by the invention]
Conventional marine and livestock feeds have the above-mentioned problems, and it has not been possible to produce feeds with high safety and good oxidative stability. Also, various antioxidants for fats and oils, including polyamines, are known, but no technique has been developed for effectively applying them to the feed.
Therefore, an object of the present invention is to provide a feed for fishery or livestock which has no concern in terms of safety, has excellent oxidative stability, and has a long-lasting antioxidant effect.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result, a part or all of spermine, spermidine and putrescine, which are so-called in-vivo components and have no problem in terms of safety, were subjected to an oil or fat composition or emulsification. The formulation processed into the composition has a high activity and a long lasting antioxidant activity against feeds made from fish meal, fish meal, fish oil, vegetable oil cake, etc. We found that it became possible to save. The present invention has been completed based on such findings.
[0007]
That is, the gist of the present invention is to provide a oxidatively stable fishery product obtained by adding a preparation containing one or more of spermine, spermidine and putrescine (hereinafter referred to as a preparation such as spermine) to a feed raw material. Or feed for livestock. The first type of the gist of the present invention is a fat or oil composition in which a preparation such as spermine contains one or more of spermine, spermidine and putrescine and fat and oil, or the fat or oil composition further comprises It is to contain tocopherol or / and L-ascorbic acid fatty acid ester. The second type of the gist is an emulsified composition in which a preparation such as spermine emulsifies the oil / fat composition and an aqueous phase, or a group wherein the emulsified composition further comprises L-ascorbic acid, a salt thereof, a protein and a peptide. At least one selected from the group consisting of: Hereinafter, the present invention will be described in detail.
[0008]
First, the polyamines used in the present invention, i.e., spermine, spermidine and putrescine, are extracted from the milt of fish such as salmon or sperm of animals such as cattle and pigs, chemically synthesized, or biochemically using enzymes or microorganisms. It can be created by means such as synthesis. These polyamines include reagent grade commercial products (for example, manufactured by SIGMA).
[0009]
A preparation such as spermine which is a feature of the present invention is a preparation obtained by processing one or more of spermine, spermidine and putrescine together with a known material, and includes an aqueous solution, an ethanol or butanol solution, a liposome preparation, and microsquare. Formulations, tablets and the like are possible, but an oil or fat composition (oil) or an emulsion composition (emulsion) as described below is preferable.
[0010]
The first type of the preparation such as spermine of the present invention is a fat or oil composition comprising one or more of spermine, spermidine and putrescine and a fat or oil, or the fat or oil composition further comprises tocopherol or / and It contains L-ascorbic acid fatty acid ester.
[0011]
Here, the type of the fat or oil is not particularly limited, but a fat or oil that exhibits a liquid state at normal temperature is convenient for use. Specific examples of fats and oils applicable to the present invention include vegetable oils such as soybean oil, rapeseed oil, corn oil, safflower oil, cottonseed oil, sunflower oil, palm oil, linseed oil, cocoa butter, shea butter, olive oil, tallow, lard, etc. Animal fats and oils, mono- or mixed-acid triglycerides of medium-chain fatty acids having 6 to 10 carbon atoms (eg, Nisshin Oil Co., Ltd., trade name: ODO), acetin fat (triglyceride acetate), triglyceride oleate, etc. Can be given. Of these, soybean oil, rapeseed oil, corn oil, and medium-chain fatty acid triglycerides are preferred. It is also possible to use oils and fats containing highly unsaturated fatty acids such as fish oils such as sardines, saury and mackerel, liver oils such as squid and walleye pollack, and sea animal oils such as seals and sea lions.
[0012]
The total amount of spermine, spermidine and / or putrescine mixed into the fat or oil composition is 0.01 to 70% by weight, more preferably 0.1 to 50% by weight, and most preferably 2 to 10% by weight based on the total weight of the fat or oil composition. It is. If the amount is less than 0.01% by weight, the antioxidant effect is small even when the oil and fat composition of the present invention is added to feed, and even if the oil and fat composition exceeds 70% by weight, a uniformly dissolved or dispersed oil and fat composition can be obtained. It is difficult to exhibit the antioxidant power corresponding to the compounding amount, which is uneconomical. When two or three of spermine, spermidine and putrescine are used in combination, their ratio is not particularly limited, and various mixing ratios are considered in view of the fact that the antioxidant power is strong in the order of spermine>spermidine> putrescine. However, in order to obtain a practical antioxidant preparation, in order to obtain a practical antioxidant preparation, the spermine content in the mixture of these two or three kinds should be 30% by weight or more, or the total content of spermine and spermidine should be 50% by weight or more. It is desirable to do.
[0013]
In addition, 0.01 to 30% by weight of tocopherol, preferably 0.1 to 10% by weight or / and 0.001 to 50% by weight of L-ascorbic acid fatty acid ester, and preferably 0.1 to 10% by weight of this oil and fat composition. When added by weight%, the antioxidant power of the oil / fat composition further increases. Here, the tocopherol may be a D-form, an L-form or a DL-form of α, β, γ and δ-tocopherol alone or in an arbitrary mixture, and a natural product or a synthetic product may be used. It is desirable to have a high δ-tocopherol content, but practically, α-, β-, γ- and δ-mixed D-forms which are concentrated from by-products when deodorizing and purifying vegetable oils such as soybean oil, wheat germ oil, rapeseed oil, etc. Tocopherol is preferred, or a fraction thereof, or DL-form α-tocopherol prepared from synthetic phytol may be used. There is no problem even if such tocopherol is a mixture with fats and oils. As L-ascorbic acid fatty acid ester, palmitic acid or stearic acid ester of L-ascorbic acid is commercially available, and these are preferable.
[0014]
In order to prepare the oil or fat composition of the present invention, one or more of spermine, spermidine and putrescine, or these and tocopherol and / or L-ascorbic acid fatty acid ester, as they are, or ethanol, isopropanol, After previously dissolving in a solvent such as butanol or ether, the solution is added to the fat or oil, heated at room temperature or about 50 ° C., and rotated at 50 to 4000 rpm using a suitable stirrer or mixer such as a mixer or a blender. The mixture may be stirred to dissolve or disperse uniformly, and if necessary, the solvent may be removed under reduced pressure. In order to adjust the properties of the fat or oil composition, if necessary, a thickening agent such as oil-soluble 12-hydroxystearic acid, a wax such as candelilla wax, carnauba wax, paraffin wax, a coloring agent, a fragrance, etc. are blended. May be.
Thus, the first type of the preparation such as spermine of the present invention, that is, an oil or fat composition comprising one or more of spermine, spermidine and putrescine and an oil or fat, or the oil or fat composition further comprises tocopherol or / And L-ascorbic acid fatty acid esters.
[0015]
Next, the second type of the preparation such as spermine of the present invention is an emulsified composition obtained by emulsifying the first type (oil / fat composition) with an oil phase and an aqueous phase, or the emulsified composition. Further contains at least one selected from the group consisting of L-ascorbic acid, salts thereof, proteins and peptides. Here, at least one selected from the group consisting of L-ascorbic acid, salts thereof, proteins and peptides is contained in the aqueous phase, and it is preferable to use an emulsifier in the emulsification treatment. The emulsion composition is an oil-in-water or water-in-oil emulsion composition.
[0016]
Emulsifiers are known, for example, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, 12-hydroxystearic acid, arachinic acid, behenic acid, tallow-decomposed fatty acid, coconut-decomposed fatty acid, rapeseed oil Propylene glycol monofatty acid esters having fatty acid residues such as decomposed fatty acids, fatty acid mono- or diglycerides, sucrose mono-, di- or tri-fatty acid esters, sorbitan mono-, sesqui- or di-fatty acid esters, ethylene oxide of said fatty acids or fatty acid esters and / or Ester emulsifiers such as polyglycerol mono-, di- or tri-fatty acid esters having 2 to 40 moles of propylene oxide adduct and an average degree of polymerization of 2 to 15, especially 6 or 10 can be used.
[0017]
Also, soybean lecithin, rapeseed lecithin, egg yolk lecithin, fractionated from the lecithin, concentrated or chemically synthesized phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, a lecithin emulsifier such as a lyso form of the phospholipid, potassium of the fatty acid Fatty acid soap emulsifier such as salt or sodium salt, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, aralkyl alcohol, behenyl alcohol, octylphenol, nonylphenol, etc. 2 to 30 mol of ethylene oxide or / and propylene oxide added An ether emulsifier such as a product can also be used. In the present invention, one or more of these emulsifiers can be appropriately used, and one or more of fatty acid glyceride, sorbitan fatty acid ester, polyglycerin fatty acid ester and lecithin are particularly preferable.
[0018]
The emulsifier is used in an amount of about 0.1 to 5% by weight based on the total weight of the emulsified composition, and the oil / fat composition is used as an oil phase. 5 (weight ratio, the same applies hereinafter), preferably oil / water phase = 5/95 to about 60/40 in the case of an oil-in-water emulsion composition, and in the case of a water-in-oil emulsion composition Preferably, the oil phase / water phase is about 40/60 to 95/5, and the emulsion is emulsified by normal phase or phase inversion emulsification. In the emulsion composition of the present invention, the average particle size of the dispersed droplets (oil droplets in an oil-in-water emulsion composition, water droplets in a water-in-oil emulsion composition) is about 50 μm or less, preferably about 5 to 30 μm, and more desirably. Is preferably set to about 5 to 20 μm. When the average particle size exceeds about 50 μm and is about 60 μm or more, it is difficult to maintain a stable emulsified state.
[0019]
In preparing the emulsified composition, the aqueous phase contains at least one aqueous component selected from the group consisting of L-ascorbic acid, a salt thereof, a protein and a peptide. Can be further enhanced. In particular, the combined use of proteins is effective in enhancing the antioxidant power and stabilizing the emulsified state. In the whole emulsified composition, L-ascorbic acid and its salt may be used in an amount of 0.01 to 30% by weight, preferably 0.05 to 10% by weight, and the protein is 0.1 to 30% by weight, preferably 0 to 30% by weight. 0.5 to 20% by weight, and the peptide is incorporated in an amount of 0.1 to 30% by weight, preferably 0.5 to 10% by weight. If the addition amount of any of these aqueous components is small outside the above range, the antioxidant power of one or more of spermine, spermidine and putrescine cannot be enhanced, and conversely, Further increase in the antioxidant power cannot be expected even if the addition amount is exceeded.
[0020]
Among these aqueous components, commercially available L-ascorbic acid and salts thereof may be used. In addition, proteins and peptides may be derived from animals or plants. Proteins and peptides such as egg white, egg yolk, milk storage, meat extract, fish meal, crab meal, shrimp meal, and feather meal are examples of animal-derived substances, and soybean, wheat, rapeseed, cottonseed, linseed, and plant-derived substances. Examples include proteins and peptides extracted from safflower, sunflower, sesame, peanut, palm, kapok, almond, walnut, and the like, but the present invention is not limited thereto.
[0021]
The peptide can be obtained by hydrolyzing the animal or plant-derived protein by a known method, that is, an acid, an alkali or a protease, and subjecting it to a treatment such as neutralization, heating, acidic precipitation, aggregation, separation, and concentration. It is 500 to 50,000, preferably 1,000 to 10,000. If the peptide has a molecular weight of less than 500, the desired effects of the present invention cannot be obtained, and the tendency of imparting taste to the emulsified composition increases, which may limit the use of the product. When the molecular weight exceeds 50,000, there is no difference in effect from the case where the protein is blended. Preferred examples of proteins and peptides include egg white, casein, concentrated soy protein, isolated soy protein, twain, gluten, and these peptides.
[0022]
The emulsion composition of the present invention is prepared as follows. That is, an oil or fat composition prepared by the above method, which further comprises one or more of spermine, spermidine and putrescine and an oil and fat, and if necessary, a tocopherol and / or L-ascorbic acid fatty acid ester, is used as an oil. On the other hand, water or an aqueous solution obtained by dissolving or dispersing one or more aqueous components selected from the group consisting of L-ascorbic acid, a salt thereof, a protein, and a peptide in water is preferably used as the aqueous phase, Part or all of the emulsifier is added to the oil phase or the aqueous phase. At this time, it is preferable that the lipophilic emulsifier is dissolved in the oil phase, the hydrophilic emulsifier is dissolved in the aqueous phase, and when the lipophilic and hydrophilic emulsifiers are used in combination, the respective phases are similarly dissolved.
[0023]
The oil phase and the aqueous phase are each heated at room temperature or about 70 ° C., if necessary, and stirred using a homomixer, a homogenizer, a Hiscotron, an azihomomixer, or the like. While stirring for 10 to 30 minutes, preferably adding the oil phase to the aqueous phase for an oil-in-water emulsion composition, and adding the aqueous phase to the oil phase for a water-in-oil emulsion composition. Emulsify.
[0024]
The emulsified composition of the present invention comprises an essential constituent of the oil or fat composition, namely, one or more of spermine, spermidine and putrescine, and an oil or fat, or the component and tocopherol or / and L-ascorbic acid fatty acid ester. Can be prepared by directly mixing and emulsifying these with water, an aqueous component, an emulsifier and the like without previously mixing and dissolving or dispersing them. Further, as other aqueous phase components, thickening or gelling agents such as carboxymethylcellulose, guar gum, xanthan gum, sodium alginate, carrageenan, etc., coloring agents, fragrances and the like may be added as necessary.
[0025]
Thus, the second type of the preparation such as spermine of the present invention, that is, one or more of spermine, spermidine and putrescine and an oil or fat and water, or the above-mentioned component containing tocopherol and / or L-ascorbic acid fatty acid ester is further used. An emulsified oil-in-water or water-in-oil type emulsified composition, and an emulsified composition containing at least one selected from the group consisting of L-ascorbic acid, a salt thereof, a protein and a peptide are obtained.
[0026]
In the present invention, a preparation such as spermine as described above, that is, an oil or fat composition (oil) or an emulsion composition (emulsion) containing one or more of spermine, spermidine and putrescine, and a feed raw material are used. This is used to produce a marine or livestock feed with good oxidative stability. The emulsion is preferably added in an amount of 2 to 50% by weight based on a feed composition containing fish oil such as fish meal or fish meal. In addition, it is preferable that an oil agent such as spermine is added in an amount of 0.01 to 50% by weight based on a highly unsaturated fatty acid-containing oil such as fish oil.
[0027]
The feed of the present invention can be prepared using known feed ingredients other than the above-mentioned preparations such as spermine. That is, the marine feed is a composition composed of cereals, algae, vegetable oil cake, animal feed raw materials, other raw materials, and the like. As cereals, corn, grain sorghum, wheat, barley, oats, rye, brown rice, flour, kinako and the like can be used. Algae include rice bran, rice bran oil cake, wheat bran, bran and the like. Examples of vegetable oil cakes include soybean oil cake, linseed oil cake, cottonseed oil cake, peanut oil cake, safflower oil cake, coconut oil cake, palm kernel oil cake, sesame oil cake, sunflower oil cake, rapeseed oil cake, kapok oil cake and the like. Examples of animal feed raw materials include fish meal, fish soluble, fish soluble adsorbed feed, meat meal, meat-and-bone meal, blood meal, crab meal, shrimp meal, feather meal, silkworm, silkworm oil cake, skim milk powder, dried whey, and the like. In addition, freshwater and marine chlorella, various algae, seaweeds such as seaweed and kelp, cellulose powder, carboxymethylcellulose and the like can also be used.
[0028]
Livestock feed includes cereals, potatoes and turnips, alga, vegetable oil cakes, other cakes, oils and fats, grasses, animal feed materials, cellular proteins and non-protein nitrogen compounds, minerals, vitamins, etc. It consists of raw materials and the like. As the cereals, millet, millet, millet, etc. are used in addition to the cereals of the above-mentioned fishery feed. The potatoes and turnips include sweet potato, cassava, potato, turnip, beet and the like. As the alga, the same as the above-mentioned fishery feed can be used.
Examples of the vegetable oil cakes include those used in the above-mentioned fishery feed, as well as hemp meal, almond cake, walnut cake, mustard cake, niger cake and the like. As other lees, corn gluten meal, beer lees, alcoholic fermented lees, tofu lees, distilled liquor lees, soy sauce lees, tomato squeeze lees, coffee residues, cocoa residues and the like can also be used. As fats and oils, soybean oil, rapeseed oil, corn oil, cottonseed oil, safflower oil, sunflower oil, linseed oil, perilla oil, coconut oil, palm oil, palm kernel oil, kapok oil, sesame oil, perilla oil, cocoa oil, shea Fat, monkey fat, beef tallow, lard, butter, fish oil and the like can be mentioned as examples. As grasses, there are grasses, legumes, greening forage crops and the like. As animal feed raw materials, besides animal feed raw materials in the above-mentioned fishery feed, whale meat meal, dairy by-products (skim milk, buttermilk, whey), meat processing by-products (bone meal, feather meal) and the like can be used. Cell proteins include various algae including chlorella, seaweed, kelp, filamentous fungi, yeast, bacteria and the like. The raw materials of the present invention are not limited to these examples at all, and can be appropriately selected and blended.
[0029]
The feed of the present invention is obtained by appropriately selecting the above-mentioned various raw materials and performing a treatment such as pulverization, mixing and molding together with a preparation such as spermine, and is basically different between a marine feed and a livestock feed. There are few places. For example, compounded feed for marine products is morphologically divided into powder, granular and bulk (crumble, pellet, porous pellet, incense type, porous pellet crumble, air granulation crumble, flake). An example of the production method is shown below.
[0030]
The main raw material, auxiliary raw material, miscellaneous raw material and liquid raw material are put into each raw material tank, and the main raw material, auxiliary raw material and miscellaneous raw material are each pulverized by a suitable crusher. Also, a trace component or a preparation such as spermine is added to a part of miscellaneous raw materials (for example, vitamins, minerals, hormones, etc.) and premixed. In this case, the preparation such as spermine may be added directly to a raw material containing an oil component such as fish meal or fish meal, or may be added to a fat or oil such as fish oil, mixed with other raw materials and crushed. From the viewpoint of workability, it is preferable to add a preparation such as spermine to fish meal and / or fish oil. A mixture of powdered preparations such as spermine is put into a mixing tank, mixed with other powder raw materials, and then a liquid material is further added and mixed with a mixer. At this time, for the first time, a preparation such as spermine may be added and mixed in the mixing tank. In this way, a powdery feed can be produced.
[0031]
The powdery feed is fed to a molding machine such as a single-screw or twin-screw extruder, a pellet mill, a pelletizer, a crumbler, etc., and steam is blown until the water content reaches 5 to 10% by weight to gelatinize the starchy raw material. After adjusting the hardness by further adding a binder such as CMC (carboxymethylcellulose) or sodium ligninsulfonate, kneading the mixture, pressing the feed with a roll on a plate having a hole having a thickness of 2 to 10 cm, and 100 to 1000 kg. / Cm 2 From high pressure to atmospheric pressure. The extruded bulk feed mixture is cut into appropriate lengths, cooled and dried to produce pelleted feed. The porous pellet feed is made during this process by extruding from a high pressure extruder to atmospheric pressure. When this porous feed absorbs, for example, an emulsified composition of a preparation such as spermine, a soft-type feed containing about 10 to 20% of oil can be obtained. The crumble feed is obtained by crushing pellets or porous pellets using a roller and a shifter, and sieving the particles into particles having a predetermined particle size.
[0032]
The feed containing the thus-prepared preparations such as spermine maintains and enhances the efficacy of one or more of spermine, spermidine and putrescine, which have antioxidant activity, so that they have good oxidative stability over a long period of time. Is good.
[0033]
【Example】
Reference Example 1
D-α, β, γ, and δ-mixed tocopherol (manufactured by Sigma) containing 2% by weight of spermine (reagent, manufactured by Sigma) and 2% by weight of spermine (the same reagent) and 100% of soybean oil A solution prepared by dissolving 0.2% by weight of TYPE V) in 10 ml of ethanol was added, and mixed with a paddle mixer at a rotation speed of 5000 rpm for 3 minutes to dissolve spermine. The spermine oil composition obtained by evaporating ethanol under reduced pressure and spermine alone were each placed in a brown sample bottle, capped, and stored in a thermostat at 40 ° C. for 3, 6, and 12 months. Thereafter, the antioxidant activity against Alaska pollack liver oil was compared using the oil / fat composition and spermine stored for each predetermined period. That is, each was added so that the spermine content became 200 ppm with respect to Alaska pollack liver oil. In the case of spermine, 1/5 weight of the tocopherol was further mixed, and a forced deterioration test (AOM test) was performed. Air is blown at a flow rate of 2.3 ml / sec at 97.8 ± 0.2 ° C., sampled at regular intervals, and its peroxide value (POV) is measured to determine the time until the POV reaches 100. Was. Table 1 shows the results.
[0034]
[Table 1]
From the data in Table 1, it can be seen that the spermine preparation according to the present invention maintains a high antioxidant activity even after long-term storage against Alaska pollack liver oil, and the antioxidant activity when spermine and tocopherol are used in combination. Was found to be enhanced.
[0036]
Example 1
First, 2.0 kg of spermine (manufactured by Sigma) and 0.2 kg of D-α-tocopherol (manufactured by Sigma) are dissolved in 1 liter of ethanol, and this is added to 100 kg of Alaska pollack liver oil. Ethanol was distilled off under reduced pressure to prepare a preparation such as spermine (oil composition, Experiment No. 1-2). On the other hand, 78% by weight of a 1: 1 (weight ratio) mixture of northern fish meal and coastal fish meal, 4% by weight of α-starch, vitamins (choline chloride: 50%, ascorbic acid: 15%, inosit: 20%, nicotinic acid: 15%) mixture 3% by weight, mineral (calcium hydrogen phosphate: 76%, potassium dihydrogen phosphate: 8%, potassium sulfate: 7%, sodium chloride: 4%, magnesium oxide: 5%) mixture 1% by weight , 10% by weight of the above-mentioned spermine preparation, 0.1% by weight of potassium sorbate, 3% by weight of carboxymethylcellulose and 0.9% by weight of coating B1 (trade name: Siacoat, manufactured by Ueno Pharmaceutical Co., Ltd.) Each raw material was prepared so that it might become 100 kg. After the fish meal was crushed, it was placed in a compounding tank along with the starch, vitamin mixture and mineral mixture and mixed. Further, this and a preparation such as spermine were sufficiently mixed by a mixer to obtain a mixture of preparations such as spermine. Then, this was adjusted to a water content of 5% by weight and set on a molding machine, and then pressed into a 10 cm-thick perforated plate with a roll to obtain 1000 kg / cm. 2 The mixture was extruded under high pressure and dried with a dryer and a cooler to obtain a pellet feed for fishery (yield: 94 kg).
At the same time, a pellet feed for marine products was prepared in the same manner as described above, in which various additives having the composition shown in Table 2 (the oil and fat composition other than the preparation of the present invention such as spermine) were blended.
[0037]
Each of the above pellet feeds was placed in a constant temperature room at 60 ° C. and stored for 10 days. After that, each feed sample was extracted with n-hexane to obtain an oil content, and the peroxide value (POV) was measured. The results are summarized in Table 2. Thereby, it was recognized that the oxidative deterioration of the feed to which the formulation such as spermine according to the present invention was added was suppressed.
[0038]
[Table 2]
Note) * 1 Formulations such as spermine of the present invention and oil / fat compositions for comparison.
* 2 Peroxide value of oil in feed after storing each feed at 60 ° C for 10 days.
* 3 Triglyceride of mixed fatty acid of caprylic acid and capric acid (Nisshin Oil Co., Ltd., trade name: ODO)
The figures in parentheses are the percentages by weight of each component based on the total amount of additives. Also, spermine, spermidine, putrescine, D-α-tocopherol, D-δ-tocopherol, D-mixed tocopherol (mixture of α, β, γ and δ forms including soybean oil, TYPE V), L-ascorbic acid palmitate and ethoxyquin Are reagents manufactured by Sigma.
[0040]
Example 2
0.8 kg of spermidine (manufactured by Sigma, reagent) and 0.2 kg of D-mixed tocopherol (manufactured by Sigma) are added to 100 kg of walleye pollock liver oil, and sufficiently stirred and mixed to prepare a preparation (oil composition) such as spermine. did. To this, 2.0% by weight of L-ascorbic acid (manufactured by Kanto Kagaku Co., Ltd., reagent) and egg white peptide (made by Kewpie Co., Ltd., trade name: egg white peptide EP-1, average molecular weight: 1100) 5 in tap water 100 liters of an aqueous solution containing 2.0% by weight of a glycerin-condensed ricinoleate (manufactured by Sakamoto Yakuhin Co., Ltd., trade name: SY Glister-CR-500) was added thereto, followed by sufficiently stirring with a homogenizer. A spermidine preparation (W / O emulsion composition, Experiment No. 2-5) was prepared. 45% by weight of fish meal, 8.4% by weight of soybean oil cake, 12% by weight of corn meal, 3.0% by weight of a mixture of vitamins (choline chloride: 50%, ascorbic acid: 15%, inosit: 20%, nicotinic acid: 15%) , Mineral (calcium monohydrogen phosphate: 76%, potassium dihydrogen phosphate: 8%, potassium sulfate: 7%, sodium chloride: 4%, magnesium oxide: 5%) mixture 2.0% by weight, flour 19.6 Each raw material was prepared so that a total of 100 kg would be obtained at a composition ratio of 20% by weight of the above-mentioned preparation such as spermine. The fish meal, soybean oil cake, corn meal and wheat flour were each crushed and put into a compounding tank, and a vitamin mixture and a mineral mixture were further added and mixed. Thereafter, this was put into a mixer together with a preparation such as spermine, and thoroughly mixed to obtain a mixture of preparations such as spermine. Next, water vapor was blown into the mixture to adjust the degree of water addition to 3% by weight, and then the mixture was put into a molding machine. The mixture was pushed into a plate having a hole having a thickness of 3 cm by a roll and 2,000 kg / cm. 2 Extruded under high pressure. This was cut into a suitable length with a knife to prepare a soft livestock pellet feed (yield: 85 kg) having an oil content of 15% by weight.
[0041]
At the same time, a pellet feed for livestock containing various additives (emulsified compositions) having compositions shown in Table 3 was prepared in the same manner. After storing these pellet feed samples in a 60 ° C. constant temperature room for 10 days, the POV was measured in the same manner as in Example 1. Table 3 summarizes the results. As in Example 1, it was revealed that the feed to which the formulation (emulsion composition) such as spermine according to the present invention was added was inhibited from oxidative deterioration.
[0042]
[Table 3]
Note) * 1 Components of the spermine preparation of the present invention and an emulsified composition for comparison.
* 2 Product name: SY Glister-CR-500, manufactured by Sakamoto Yakuhin Co., Ltd.
* 3 Product name: Poem J-2001, manufactured by Riken Vitamin Co., Ltd.
* 4 Nisshin Oil Co., Ltd., trade name: Solpy 5000.
* 5 Made by Kewpie Co., Ltd., trade name: egg white peptide EP-1.
* 6 O / W: oil-in-water type, W / O: water-in-oil type.
* 7 Peroxide value of oil in feed after storing each feed at 60 ° C for 10 days.
The figures in parentheses indicate the weight% of each component relative to the total amount of the additives, and spermine, spermidine, putrescine, D-mixed tocopherol, L-ascorbic acid stearate, BHT and L-ascorbic acid are all reagents manufactured by Sigma.
[0044]
【The invention's effect】
The feed of the present invention has better oxidative stability than those to which conventional antioxidants such as ethoxyquin and BHT are added. In the present invention, since one or more polyamines selected from spermine, spermidine and putrescine are processed into formulations such as oils and emulsions and the above-mentioned polyamines having high stability and activity are added, the polyamines are subject to oxidative deterioration for a long period of time. It becomes a difficult feed. In addition, the dispersibility of the polyamine in feed raw materials during feed production is also improved.
The feed with good oxidative stability obtained by the present invention can be widely used for aquaculture, livestock, pet animals, and the like.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08794694A JP3553126B2 (en) | 1994-04-01 | 1994-04-01 | Feed with good oxidation stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08794694A JP3553126B2 (en) | 1994-04-01 | 1994-04-01 | Feed with good oxidation stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07274842A JPH07274842A (en) | 1995-10-24 |
| JP3553126B2 true JP3553126B2 (en) | 2004-08-11 |
Family
ID=13929063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08794694A Expired - Fee Related JP3553126B2 (en) | 1994-04-01 | 1994-04-01 | Feed with good oxidation stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3553126B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008147214A1 (en) * | 2007-05-29 | 2008-12-04 | Nofima Akvaforsk-Fiskeriforskning As | Food article with improved shelf life |
| KR101318335B1 (en) * | 2011-10-10 | 2013-10-16 | 대구대학교 산학협력단 | Composition for livestock feed comprising polyamines as effective component |
| KR101691364B1 (en) * | 2014-05-26 | 2016-12-30 | 일진에프앤피 주식회사 | Bee subsidiary feeder composition comprising rice bran and manufacturing method thereof |
| CN105815757A (en) * | 2016-03-24 | 2016-08-03 | 李�杰 | Stabilizer for lowering leaching toxicity of heavy metal in food, food product and traditional Chinese medicine and improving food safety and environmental protection and preparation method of stabilizer |
| PE20200663A1 (en) * | 2017-08-25 | 2020-06-11 | Dsm Ip Assets Bv | NEW FORMULATION |
| KR102455033B1 (en) * | 2022-01-12 | 2022-10-14 | 박영주 | feed additives for livestock using seaweeds and manufacturing method thereof |
| CN116172128B (en) * | 2022-09-08 | 2024-03-15 | 南京农业大学 | Composite feed additive for improving and protecting fertility of middle-aged and old male animals |
-
1994
- 1994-04-01 JP JP08794694A patent/JP3553126B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07274842A (en) | 1995-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3664258B2 (en) | High nutritive animal feed, process for its production and use of polyethylene glycol compounds | |
| AU671652B2 (en) | A microencapsulated oil or fat product | |
| US4216234A (en) | Lipid encapsulated feed supplement and process for producing same | |
| JPH0659164B2 (en) | Sterin-containing composition | |
| JPS647754B2 (en) | ||
| JP3553126B2 (en) | Feed with good oxidation stability | |
| JP4326153B2 (en) | Method for preparing dry animal feed | |
| WO2010139292A1 (en) | Emulsion or gel as a supplement in food based on ground raw ingredients such as sausage meat or ground meat | |
| JPH10215786A (en) | Feed having good oxidation stability | |
| JP4703388B2 (en) | Thioctic acid composition and method for producing the same | |
| JP3096224B2 (en) | Retort sauce | |
| US20060240165A1 (en) | Gel feed | |
| EP0923309B1 (en) | Dry fish feed and method of preparing same | |
| JPH07277917A (en) | Cosmetic good in oxidation stability | |
| JPH07268323A (en) | Antioxidation preparation | |
| JP7130908B2 (en) | novel formulation | |
| JPH0525042A (en) | Composition containing water-soluble vitamins | |
| JP2515680B2 (en) | Freshwater fish feed | |
| GB970363A (en) | Improvements in vitamin preparations and process for producing them | |
| JP3229842B2 (en) | Oily composition and feed to which it is added | |
| JP3662121B2 (en) | Oil and fat composition for processed fish food and processed fish food | |
| JPH07133491A (en) | Solid material containing oil-soluble substance | |
| JP2004337003A (en) | Solid feed for cultured fish | |
| KR950004425B1 (en) | Feeding stuffs | |
| JP3198270B2 (en) | Feed and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040427 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040428 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |