JP4419186B2 - Release oil - Google Patents
Release oil Download PDFInfo
- Publication number
- JP4419186B2 JP4419186B2 JP2003014106A JP2003014106A JP4419186B2 JP 4419186 B2 JP4419186 B2 JP 4419186B2 JP 2003014106 A JP2003014106 A JP 2003014106A JP 2003014106 A JP2003014106 A JP 2003014106A JP 4419186 B2 JP4419186 B2 JP 4419186B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- fatty acid
- release oil
- ester
- water
- 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 - Lifetime
Links
Landscapes
- Edible Oils And Fats (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、離型油に関する。更に詳しくは、特に食品分野の鉄板や容器に噴霧して使用される離型油に関する。更に前記離型油を用いる使用方法に関する。
【0002】
【従来の技術】
従来、食品分野において、パンや菓子を焼成する場合に生地が鉄板や容器に付着しないように離型油を塗布して型離れをよくすることが行われている。
離型油は固形状離型油と液状離型油に大別され、更に液状離型油は液状油脂に活性剤等の離型促進剤を添加した全油タイプの離型油と、液状油脂と水を混合した乳化型離型油に大別できる。
固形状離型油は様々な固体油脂を単独、若しくは組み合わせで使用し、そこに活性剤等を配合したタイプが多く見られる。固形状離型油は一般的に離型性、コゲ付き防止に優れるが、天板や焼型に塗布する場合、刷毛やモップ等で手塗りを行う必要があり、また機械等で塗布する場合でも設備が大掛かりなる欠点がある。
【0003】
一方、液状離型油は流動状のためスプレー機械を用いた簡便な噴霧方法が利用できる。しかしながら液状離型油は固形状離型油と比較して離型性が劣る上に、離型油がスプレーされた際、天板や焼型に付着できなかった離型油が霧化して、離型油のミストとなって空中に飛散し、周辺設備を汚染する欠点がある。
乳化型離型油は全油タイプの離型油と比較してミストの発生を抑制することができる反面、乳化状態を長期間安定に保つことが困難であり、またミスト抑制効果も十分とは言いがたい。離型性に関しても全油タイプの液状離型油に比較して劣る上に液ダレも発生する欠点がある。
また焼型上に均一に離型油がスプレーされた場合でも、凹凸のある焼型では付着した離型油が自重により底部に移動し、離型油の油膜に濃淡が発生するいわゆる液ダレが発生する。液ダレにより焼型表面の離型油が薄くなった部分は離型性が低下し、離型油が厚くなった部分は油で揚げたような表面状態になり、焼成品の表面状態を損なう欠点がある。
【0004】
一方、乳化型離型油は油脂と活性剤と水からなり、分散相が油脂である水中油滴型(O/W型)のエマルジョンと、分散相が水である油中水滴(W/O)型のエマルションに大別できる。
O/W型のエマルションはW/O型のエマルションと比較して機械によるスプレー時に発生するミストは少ないが、安定なエマルションを得る為に水分が多くなり油分が減少する場合が多く、また親水性の大きなHLB値の大きい活性剤を使用する場合が多い。その結果、離型性が劣る欠点がある。また連続相が水相であることから液ダレ防止が困難であり、粘性を調節するための添加剤は焼型上でのコゲの原因になる。
一方、W/O型のエマルションは、O/W型のエマルションと比較して長期間安定なエマルションを維持することが困難であり、また従来より油水分離を防止する目的と液ダレを防止する目的で高融点の油脂や固形状の活性剤を添加することが行われるが、このような場合、保管温度による粘性変化が大きいために液ダレ防止性能が十分でなく、また保管期間中に添加した固体脂や活性剤が析出して離型油中に沈殿、または浮遊して不均一な状態となる欠点がある。更に析出したこれら固体脂や活性剤がスプレーされた際、スプレー機械中のポンプや配管、スプレーノズル内の細かな間隙に次第に蓄積され、間隙を閉塞する結果、良好な離型油の輸送やスプレー状態を悪化する欠点がある。
【0005】
例えば、特開2000−184849号公報(特許文献1)には、常温で液状の油脂にレシチンまたはレシチンと油溶性乳化剤混合物を溶解させた離型油を静電塗油装置のノズルから噴霧して離型油微細粒子をマイナスに帯電させて噴霧塗布する焼き洋菓子用離型膜の形成方法が開示されている。しかし、この技術では、特殊な装置が必要であり、一般的でないなど問題がある。
また、特開2001−275566号(特許文献2)には、食用油脂中にでんぷん類13〜35重量%、動植物ワックス1〜10重量%、レシチン0.6%〜5重量%を含む離型油が開示されている。しかし、この技術では、でんぷんや、ワックスを使用するために離型油を冷蔵所等に保管した場合に固体となり噴霧ノズルで詰まりを生じるなどの問題がある。
また、特開平7−39304号公報(特許文献3)には、食用油脂100重量部にショ糖脂肪酸エステルを0.1〜30重量部配合する離型油が開示されている。またさらに、ポリグリセリン脂肪酸等の乳化剤を配合する技術が開示されている。しかし、この技術では、油脂と活性剤のみの系であり離型性は優れるもののミストが多く発生する問題がある。
また、特開平7−170910号公報(特許文献4)には、ポリグリセリン中鎖脂肪酸エステルを含有している組成物100重量部に、レシチン、モノグリセリド、有機酸モノグリセリド、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ショ糖エステル、ポリグリセリン脂肪酸エステル等の分散剤を0.1〜10重量部配合してなる離型油が開示されている。しかし、この技術では、離型性や、液ダレ抑制、ミスト抑制等の性能が不十分である。
【0006】
さらに、特開平7−21322号公報(特許文献5)には、ポリグリセリン結合リシノレイン酸エステル(以下縮合リシノレイン酸ポリグリセリンエステルという場合もある)及び、平均エステル化度3以上のショ糖脂肪酸エステル、又は、グリセリンコハク酸脂肪酸エステルを含有する食品用液状離型油の流動性改良剤であって、該ショ糖脂肪酸エステル又は、グリセリンコハク酸脂肪酸エステルを30重量%以下含有させる離型油の流動性改良剤が開示されている。しかし、この技術では、W/O型エマルションの離型剤の記載も示唆もなく、油脂と活性剤のみであり、噴霧時のミストの発生を十分抑制できないなど問題がある。
【0007】
【特許文献1】
特開2000−184849号公報(第2頁)
【特許文献2】
特開2001−275566号公報(第2頁)
【特許文献3】
特開平7−39304号公報(第2頁)
【特許文献4】
特開平7−170910号公報(第2頁)
【特許文献5】
特開平7−213228号公報(第2頁)
【0008】
さらに、最近ではパンや菓子等の高級化が進み、卵、糖分等の比較的こげつき易い成分を多く配合する食品が多くなり、従来の離型油では十分満足できる性能が得られていないのが現状である。
したがって、機械による噴霧においてミスト発生を抑制し、離型性や液ダレ抑制に対して十分満足できる離型油がない状況である。
そのため、製造現場では、ミスト発生に対しては作業環境の点からクローズドな仕切の中で行うなどの対策をとらざるを得ない。
【0009】
【発明が解決しようとする課題】
以上のような背景のもとで本発明はなされたものであり、本発明の第1の目的は、離型性に優れ、前記のように機械噴霧においてノズルの詰まりがなく連続運転でき、ミストの発生が少なく、噴霧後液ダレしない離型油を提供することにある。
本発明の第2の目的は、前記の離型油の使用方法を提供することにある。
【0010】
【課題を解決するための手段】
本発明者らは、前記問題に鑑み鋭意検討した結果、W/O型の離型剤とすることでミストの発生を抑制し、かつ、特定の油脂、活性剤を組み合わせることにより、前記の問題点を解決できる知見を得て、本発明を完成するに至った。
すなわち本発明は、
(1)ナタネ油、大豆油、コーン油およびMCT油からなる群より選択される1種または2種以上の油脂(A)活性剤(B)水(C)からなり、かつ、水と、油脂と活性剤の合計量との配合比(水/油脂と活性剤の合計量)が重量比10/90〜45/55である油中水滴型(W/O型)のエマルションであって、油脂(A)が融点0℃以下であり、活性剤(B)がポリグリセリン縮合リシノレイン(b1)0.5〜20.0重量%と構成脂肪酸が飽和酸である飽和酸型ショ糖脂肪酸エステル(b21)と構成脂肪酸が不飽和酸である不飽和型ショ糖脂肪酸エステル(b22)とを混合したHLB4以下のショ糖エステル(b2)0.5〜10.0重量%を組合せ用いてなることを特徴とする離型油、
(2)HLB4以下のショ糖脂肪酸エステル(b2)の構成脂肪酸が飽和酸である飽和酸型ショ糖脂肪酸エステル(b21)と、構成脂肪酸が不飽和酸である不飽和型ショ糖脂肪酸エステル(b22)の2種の重量比(b21/b22)が20/80〜80/20で用いる前記の(1)記載の離型油、
(3)前記の(1)〜(2)のいずれか1項に記載の離型油が食品分野のノズル噴霧用である離型油、
(4)前記の(1)〜(3)のいずれか1項に記載の離型油を用いてノズル噴霧させて、食品用容器の面に塗布してなる離型油の使用方法、及び
(5)前記の(1)〜(4)のいずれか1項に記載の離型油をノズル噴霧させて、食品容器の面に塗布し、次いで食品生地をその容器に充填し焼成した後、食品を離型する方法、
を提供するものである。
【0011】
【発明実施の形態】
本発明のW/O型離型油は、油脂(A)活性剤(B)水(C)からなり、かつ、水と、油脂と活性剤の合計量との配合比(水/油脂と活性剤の合計量)が10/90〜45/55である油中水滴型(W/O型)のエマルションであって、油脂(A)が融点5℃以下であり、活性剤(B)がポリグリセリン縮合リシノレイン(b1)0.5〜20.0重量%とHLB4以下のショ糖エステル(b2)0.5〜10.0重量%を組合せ用いてなることを特徴とする。
本発明で用いる油脂(A)としては、融点5℃の以下の動植物油あるいは合成油が挙げられ、常温液体の食用油脂が挙げられる。具体的には例えば、ナタネ油、大豆油、米油、ごま油、オリーブ油、パームオレイン油、綿実油、ひまわり油、コーン油、MCT油(中鎖脂肪酸トリグリセリド)が挙げられる。好ましくはナタネ油、大豆油、コーン油、MCT油等である。前記の融点5℃より高い動植物油脂であっても、前記の融点5℃以下の動植物油脂に配合しても固体脂の析出など問題がない程度の量であれば配合しても問題ない
融点が高いと結晶を生成しやすく、固体脂が噴霧ノズルで詰まりが発生する。
【0012】
本発明で用いる活性剤(B)としては、ポリグリセリン縮合リシノレイン酸エステル(b1)と、HLB4以下のショ糖脂肪酸エステル(b2)を組合せ用いる。
ポリグリセリン縮合リシノレイン酸エステル(b1)は、ポリグリセリンと縮合リシノレイン酸とのエステル化物であって、ポリグリセリン部分は平均重合度が3〜6のポリグリセリンで、平均縮合度が3〜6のリシノレイン酸部分とのエステル化物である。
例えば具体的には、トリグリセリン縮合シリノレイン酸エステル、テトラグリセリン縮合リシノレイン酸エステル、ペンタグリセリン縮合リシノレイン酸エステル、ヘキサグリセリン縮合リシノレイン酸エステル、デカグリセリン縮合リシノレイン酸エステル等が挙げられる。
中でも特に好ましくは、縮合リシノレイン酸ヘキサグリセリンエステル、縮合リシノレイン酸ペンタグリセリンエステルが挙げられる。
【0013】
本発明で用いるHLB4以下のショ糖脂肪酸エステル(b2)としては、ショ糖と炭素数8〜22の飽和、不飽和の脂肪酸とのエステルであり、具体的に例えば、カプリル酸ショ糖エステル、カプリン酸ショ糖エステル、ラウリン酸ショ糖エステル、ミリスチン酸ショ糖エステル、パルミチン酸ショ糖エステル、ステアリン酸ショ糖エステル、オレイン酸ショ糖エステル、ベヘン酸ショ糖エステル、エライジン酸ショ糖エステル、リノール酸ショ糖エステル、リノレイン酸ショ糖エステル等が挙げられる。中でも、パルミチン酸ショ糖エステル、ステアリン酸ショ糖エステル、オレイン酸ショ糖エステルが好ましく挙げられる。
さらにショ糖エステルの中でも、飽和脂肪酸のショ糖エステル(b21)と、不飽和脂肪酸のショ糖エステル(b22)とを二種組合せて使用すると更に好ましい。また飽和脂肪酸のショ糖エステル(b21)と飽和脂肪酸、不飽和脂肪酸の混合脂肪酸のショ糖エステルの組み合わせも好ましく挙げられる
また構成脂肪酸が飽和酸、不飽和酸に関わらずHLBが4より大きいショ脂肪酸エステルを使用すると離型性が悪化する。
【0014】
本発明で使用する水(C)としては、精製水、イオン交換水、蒸留水等の通常食品に使用できる水が挙げられる。
【0015】
前記の水(C)と[油脂(A)+活性剤(B)]との配合比率は、W/O型エマルションとするために、[(C)/[(A)+(B)]]の重量比で10/90〜45/55である。より好ましくは、噴霧時のミストの抑制がより十分にできる点から、20/80〜40/60である。
前記比率が10/90より水(C)の量が少なくなると、噴霧時のミスト発生が多くなる。一方、前記比率が45/55より水(C)の量が多くなるとW/O型エマルションの形態をとりにくくなり、O/W型のエマルションの形態となると、噴霧時のミストは少なくなるものの離型性が低下し、液ダレの抑制がしにくくなる。
【0016】
前記の縮合リシノレイン酸ポリグリセリンエステル(b1)の配合量は離型油全体中に対して、0.5〜20重量%であり、好ましくは、1〜10重量%であり、HLB4以下のショ糖エステル(b2)0.5〜10重量%、好ましくは1〜5重量%である。
縮合リシノレイン酸ポリグリセリンエステル(b1)の量が0.5重量%より少ないと乳化が不十分であり、20重量%より多いと系の粘性が高くなり、ノズルに詰まりやすくなる。また風味も悪化する。HLB4以下のショ糖エステル(b2)の配合量が0.5重量%より少ないと十分な粘性が付与されず、液ダレしやすくなる。ショ糖エステル(b2)が10重量%より多いと系の粘性が高くなりスプレーノズルに詰まりやすくなる。
【0017】
HLB4以下のショ糖エステル(b2)が、飽和脂肪酸のショ糖エステル(b21)と、不飽和脂肪酸のショ糖エステル(b22)の2種を配合して用いることが、凝固点の高いものの結晶生成抑制、製品の安定性の観点からより好ましい。前記のb21/b22の配合比率は、20/80〜80/20重量比がより好ましい。前記のb21/b22の配合比率は、40/60〜60/40重量比がさらに好ましい。また不飽和脂肪酸のショ糖エステル(b22)には飽和脂肪酸と不飽和脂肪酸が混合された飽和、不飽和混酸のショ糖脂肪酸エステルを用いても好ましい。
【0018】
本発明の離型油には、本発明の効果を損なわない範囲において、その他の成分を配合しても差しつかえない。その他の成分としては、香料、着色料、防腐剤、防黴剤、等が挙げられる。
【0019】
次に本発明の離型油の製造方法について説明する。
本発明の離型油の製造方法は、W/O型のエマルションが得られればよく、特に限定されないが、例えば、次の方法が挙げられる。
所定量の前記油脂と活性剤を容器にはかり取り、加温溶解させる。次いで、その配合油に予め加温した水相を所定量かき混ぜながら加えてW/O型エマルションを得る。その後室温まで冷却する。このようにして得られたW/Oエマルションの水滴の平均粒径は、特に限定されないが、通常0.1μm〜50μm程度、さらに好ましくは、製品の安定性の点から、1μm〜10μm程度である。
前記のW/O型エマルションを製造する際のかき混ぜ機としては、特に限定されないが、例えば、ホモミキサー、ディスパー、プロペラかき混ぜ機、高圧ホモジナイザー、ボテーター、その他の急冷捏和機等が挙げられる。
配合系にもよるが、処理温度、時間は、製品の安定性等を考慮して適宜条件を選定することが望ましい。あまり強烈なせん断力をあたえるとかえって乳化破壊を起こすので好ましくない。このようにして得られた離型油は、通常、粘度が200cSt〜5000cStの範囲であり、より好ましくは、500cSt〜2000cStの範囲である。
【0020】
次に本発明の離型油の使用方法について説明する。
本発明の離型油は、食品分野のスプレーノズル噴霧用に使用できる。特に噴霧スプレーノズルにより霧状にして食品等の容器に塗布して使用される。噴霧機械の機種としては、例えば、旭サナック社製 ピークベア・ホット、AP1224H、アネスト岩田社製、エアレス噴霧装置、マルチ・アルファとスプレー装置を組あわせたもの、若林工業(株)社製、SG−2、TG−2グリーサースプレーなどを挙げることができる。
随時機械の性能と離型油の粘度調整等により適宜好ましい条件を設定することが望ましい。
【0021】
【発明の効果】
本発明の離型油は、油脂と活性剤と水とからなり、W/O型のエマルションであるので、油性成分と活性剤のみからなる全油タイプの離型油に比べて、機械噴霧時のミストが少なく、ノズルの詰まりがなく連続運転が可能であり優れた離型性を示す。また、本発明の離型油は、O/W型のエマルションに比べて、離型性に優れ、液ダレも抑制される。さらに、特に圧力で噴霧する際にミストが少ないので環境の汚染に対して優れた効果を示す。
【0022】
【実施例】
以下、本発明を実施例に基づいて、さらに詳細に説明する。
次に用いた試験方法、評価方法を示す。
<1.状態安定性(乳化状態)試験>
離型油を調製した後、その離型油をサンプルビンにとり、30℃の恒温槽中で静置保管し、経日変化を目視より油水分離を観察した。評価は次の記号として表中に示す。
◎;油水の分離が全くなく、全体的に均一で滑らかである。
○;液面にわずかに透明相あり、滑らか感がある。
△;油水分離が確認される。
×;油水の分離が激しく、完全に2層に分離する。
<2、スプレー状態>
スプレー状態は加圧式のスプレー(スプレーイングシステムジャパン(株)社製、スプレーカートII)を用いて、実施例、比較例の離型油を試験試料として、空気圧力5kg/cm2、にてスプレーを行った。
◎;スプレー状態が均一で細かい。長期間良好なスプレー状態が維持する。
○;スプレー状態が細かいが、やや噴霧状態に偏りがある。
△;スプレー状態に偏りがあり、噴霧がやや不均一である。
×;スプレー状態が細かくならず、噴霧不良である。
<3.液ダレ抑制性>
液ダレ抑制性は上記加圧式のスプレー機で12cm×11cm×25cmの2斤型に約5.0g均一にスプレーした後、壁面部分の液ダレの有無を確認した。
評価は次の記号として表中に示す。
◎;液ダレがなく良好である。
○;液ダレがほとんどなく良好である。
△;液ダレがわずかに発生する。
×;液ダレが発生し、壁面の油膜が薄くなり、底部に離型油がたまる。
<4.ミスト抑制性試験>
ミストの抑制性試験は、上記加圧式のスプレー機でスプレーした後、離型油が霧化して空中に浮遊するミストの程度を観察した。
評価は次の記号として表中に示す。
◎;ミストが十分に抑制されている。
○;ミストが抑制されている。
△;ミストの抑制がやや不十分である。
×;ミストの抑制が不十分である。
【0023】
<4.離型性>
離型性の試験は、食パン用焼型(2斤型)に一定量の離型油(4.0g)を塗布し、次に記載の同配合、同製法により食パン生地を焼成した後、その型からの抜け具合を目視で観察した。
評価は次の記号として表中に示す。
◎;離型が非常に良好である。
○;離型が良好である。
△;離型がやや不十分である。
×;離型不良である。
<食パン生地配合>
生地製法は中種法で行った。中種は強力粉70重量部にイーストを予め分散させた水42重量部を混合し、ミキサーにて捏ねる。28℃で4時間醗酵した後、強力粉30重量部、上白糖8重量部、食塩1.83重量部、水25重量部の本捏生地と中種生地をミキサーにて混合する。その後フロアタイムを20分取り、生地分割を行なった。その後ベンチタイム15分後、成形を行い、38℃湿度85%にて約35分ホイロを行った。
<焼成条件>
ホイロ後生地は2斤型に充填し、約210℃で約35分焼成した。
【0024】
<6.総合評価>
上記評価方法により離型油としての総合評価を示す。
◎;非常に良好(◎が3つ以上あり、それ以外が○であるもの)
○;良好(評価が◎、○、△のみであり、×を含まないもの)
×;不良(1〜5の評価項目において×を含むもの)
【0025】
次に実施例および比較例に用いた材料を示す。
<油脂>
ナタネ油; 融点−12〜0℃、
ナタネ極度硬化油;融点69℃、
魚油硬化油;融点43℃、
ライスワックス;融点70〜77℃、
<活性剤>
縮合リシノレインポリグリセリンエステル;縮合リシノレイン酸ヘキサグリセリンエステル;
【0026】
実施例1;
油脂(A)としてナタネ油、65重量部、活性剤としてポリグリセリン縮合リシノレイン酸エステル(b1)(三菱化学フーズ(株)社製、商品名S−170(HLB1)2重量部、飽和酸系ショ糖エステル(b21)(三菱化学フーズ(株)社製、商品名O−170(HLB1)1.5重量部、及び不飽和酸系ショ糖エステル(b22)(三菱(株)社製、商品名O−170)1.5重量部を容器にはかりとり、撹拌を行いながら温度70℃迄加熱し、活性剤を完全に溶解させる。そこに予め加温してある70℃の水30重量部を徐々に加えてW/O型乳化物を調製する。
その後、室温まで急冷してW/O乳化型離型油を得た。
この離型油を用いて、前記の評価方法に従い、評価試験を行った。結果を表1に示す。
【0027】
実施例2、3、6、7、8、参考例4、5、及び比較例1〜10
実施例1と同様にして表1に示した材料組成で、離型油を配合した。同様に評価した結果を表1、2および3に示す。
【0028】
【表1】
【0029】
【表2】
【0030】
【表3】
【0031】
以上の結果から、本発明の実施例1〜3、6〜8、及び参考例4、5は、油脂の融点が高いものを配合した本発明の範囲外である比較例1〜4、HLBが範囲外である活性剤を用いた全油系の比較例5、他の界面活性剤を配合している比較例6〜10に比べて、液ダレ抑制性、離型性、ミスト抑制性等に優れていることがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a release oil. More specifically, the present invention relates to a release oil used by spraying on iron plates and containers in the food field. Furthermore, it is related with the usage method using the said mold release oil.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, in the food field, when baking bread or confectionery, mold release oil is applied to improve the mold release so that dough does not adhere to an iron plate or a container.
Mold release oil is roughly divided into solid mold release oil and liquid mold release oil, and liquid mold release oil is liquid oil and oil, and all oil type mold release oil and activator such as activator are added to liquid oil and fat. And emulsified release oil mixed with water.
As the solid release oil, there are many types in which various solid fats and oils are used alone or in combination, and an activator or the like is blended therein. Solid release oil is generally excellent in releasability and prevention of kogation, but when applied to the top plate or baking mold, it must be hand-painted with a brush, mop, etc. However, there is a drawback that the equipment is large.
[0003]
On the other hand, since the liquid release oil is fluid, a simple spraying method using a spray machine can be used. However, liquid mold release oil is inferior to mold release oil as compared with solid mold release oil, and when the mold release oil is sprayed, the mold release oil that could not adhere to the top plate or baking mold atomized, There is a drawback that it becomes a mist of release oil and scatters in the air, polluting the surrounding equipment.
The emulsification type release oil can suppress the generation of mist compared to the whole oil type release oil, but it is difficult to keep the emulsified state stable for a long period of time, and the mist suppression effect is sufficient. It's hard to say. The mold releasability is inferior to that of an all-oil type liquid mold release oil, and there is a drawback that liquid sag occurs.
In addition, even when mold release oil is sprayed uniformly on the mold, the mold release oil attached to the mold moves to the bottom due to its own weight, and so-called sag is generated that causes the oil film of the mold release oil to become dark and light. appear. The part where the mold release oil on the surface of the mold becomes thin due to liquid dripping deteriorates the releasability, and the part where the mold release oil becomes thick becomes a surface condition as if fried with oil, which impairs the surface condition of the fired product. There are drawbacks.
[0004]
On the other hand, an emulsification type release oil is composed of an oil and fat, an activator and water, and an oil-in-water emulsion (O / W type) emulsion in which the dispersed phase is oil and fat, and a water-in-oil droplet (W / O) in which the dispersed phase is water. ) Type emulsions.
O / W-type emulsions produce less mist when sprayed by machine than W / O-type emulsions. However, in order to obtain a stable emulsion, the amount of water is increased and oil content is often reduced. In many cases, an active agent having a large HLB value is used. As a result, there is a drawback that the releasability is inferior. Further, since the continuous phase is an aqueous phase, it is difficult to prevent dripping, and the additive for adjusting the viscosity causes burning on the baking mold.
On the other hand, it is difficult for a W / O type emulsion to maintain a stable emulsion for a long period of time compared to an O / W type emulsion, and the purpose of preventing oil-water separation and the purpose of preventing dripping from the conventional ones. In this case, the dripping prevention performance is not sufficient due to the large viscosity change due to storage temperature, and it was added during the storage period. There is a drawback that solid fat or activator is precipitated and settles in the release oil or floats and becomes non-uniform. Furthermore, when these precipitated solid fats and activators are sprayed, they are gradually accumulated in fine gaps in the pumps and piping and spray nozzles in the spray machine, and as a result of closing the gaps, good release oil transportation and spraying are possible. There are drawbacks that worsen the condition.
[0005]
For example, in Japanese Patent Laid-Open No. 2000-184849 (Patent Document 1), a release oil in which lecithin or a mixture of lecithin and an oil-soluble emulsifier is dissolved in a liquid oil at room temperature is sprayed from a nozzle of an electrostatic oil coating apparatus. A method for forming a release film for baked confectionery in which release oil fine particles are negatively charged and spray-coated is disclosed. However, this technique requires a special device and is not common.
Japanese Patent Application Laid-Open No. 2001-275566 (Patent Document 2) discloses a release oil containing 13 to 35% by weight starch, 1 to 10% by weight animal and plant waxes, and 0.6% to 5% by weight lecithin in edible oils and fats. Is disclosed. However, this technique has a problem in that when the release oil is stored in a refrigerator or the like because starch or wax is used, it becomes a solid when clogged with a spray nozzle.
Japanese Patent Application Laid-Open No. 7-39304 (Patent Document 3) discloses a release oil in which 0.1 to 30 parts by weight of a sucrose fatty acid ester is blended with 100 parts by weight of edible fats and oils. Furthermore, the technique of mix | blending emulsifiers, such as a polyglycerol fatty acid, is disclosed. However, this technique has a problem that a lot of mist is generated although it is a system of only oil and fat and an activator and has excellent releasability.
Japanese Patent Application Laid-Open No. 7-170910 (Patent Document 4) discloses that 100 parts by weight of a composition containing polyglycerin medium chain fatty acid ester, lecithin, monoglyceride, organic acid monoglyceride, sorbitan fatty acid ester, propylene glycol fatty acid. A release oil comprising 0.1 to 10 parts by weight of a dispersant such as an ester, sucrose ester or polyglycerin fatty acid ester is disclosed. However, this technique has insufficient performance such as releasability, liquid dripping suppression, and mist suppression.
[0006]
Further, JP-A-7-21322 (Patent Document 5) discloses polyglycerin-bound ricinoleic acid ester (hereinafter sometimes referred to as condensed ricinoleic acid polyglycerin ester) and sucrose fatty acid ester having an average degree of esterification of 3 or more, Or the fluidity improver of liquid release oil for foods containing glycerin succinic acid fatty acid ester, the fluidity of the release oil containing 30% by weight or less of the sucrose fatty acid ester or glycerin succinic acid fatty acid ester An improving agent is disclosed. However, this technique has a problem that there is no description of a release agent for a W / O emulsion, only oils and fats and an activator, and mist generation during spraying cannot be sufficiently suppressed.
[0007]
[Patent Document 1]
JP 2000-184849 A (page 2)
[Patent Document 2]
Japanese Patent Laid-Open No. 2001-275566 (2nd page)
[Patent Document 3]
JP-A-7-39304 (2nd page)
[Patent Document 4]
JP-A-7-170910 (2nd page)
[Patent Document 5]
JP-A-7-213228 (2nd page)
[0008]
Furthermore, recently, as foods such as bread and confectionery have been upgraded, there are many foods that contain a lot of ingredients that are relatively easy to burn, such as eggs and sugar, and the conventional release oil has not been able to achieve satisfactory performance. Currently.
Accordingly, there is no release oil that suppresses the generation of mist in spraying by a machine and is sufficiently satisfied with respect to releasability and liquid dripping suppression.
For this reason, at the manufacturing site, countermeasures such as performing in a closed partition from the viewpoint of the working environment must be taken against the occurrence of mist.
[0009]
[Problems to be solved by the invention]
The present invention has been made under the background as described above, and the first object of the present invention is to provide excellent releasability, and as described above, nozzles are not clogged during mechanical spraying and can be operated continuously. An object of the present invention is to provide a release oil that is less likely to cause dripping after spraying.
The second object of the present invention is to provide a method for using the release oil.
[0010]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have suppressed the generation of mist by using a W / O type release agent, and combining the specific oils and fats and activators, the above problems. The knowledge which can solve a point was acquired, and it came to complete this invention.
That is, the present invention
(1) One or more oils and fats selected from the group consisting of rapeseed oil, soybean oil, corn oil and MCT oil (A) active agent (B) water (C), and water and fat Is a water-in-oil type (W / O type) emulsion having a weight ratio of 10/90 to 45/55 (the total amount of water / oil and fat and activator) of Saturated acid type sucrose fatty acid ester (b21) in which (A) has a melting point of 0 ° C. or less, activator (B) is 0.5 to 20.0% by weight of polyglycerin condensed ricinolein (b1) and the constituent fatty acid is a saturated acid ) And unsaturated sucrose fatty acid ester (b22) whose constituent fatty acid is an unsaturated acid, and a combination of 0.5 to 10.0% by weight of sucrose ester (b2) of HLB 4 or less. Release oil,
(2) A saturated acid sucrose fatty acid ester (b21) in which the constituent fatty acid of the sucrose fatty acid ester (b2) having an HLB of 4 or less is a saturated acid, and an unsaturated sucrose fatty acid ester (b22 in which the constituent fatty acid is an unsaturated acid) The release oil according to (1) above, wherein the two weight ratios (b21 / b22) are 20/80 to 80/20,
(3) A release oil according to any one of (1) to (2), wherein the release oil is for nozzle spraying in the food field,
(4) A method of using a release oil obtained by spraying a nozzle using the release oil according to any one of (1) to (3) above and applying it to the surface of a food container; 5) The release oil according to any one of the above (1) to (4) is sprayed with a nozzle and applied to the surface of the food container, and then the food dough is filled into the container and baked, and then the food How to release,
Is to provide.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The W / O type release oil of the present invention comprises an oil and fat (A) activator (B) and water (C), and a mixing ratio of water and the total amount of oil and fat and activator (water / oil and fat and activity). Water-in-oil type (W / O type) emulsion having a total amount of the agent of 10/90 to 45/55, wherein the fat (A) has a melting point of 5 ° C. or less, and the activator (B) is poly It is characterized by using a combination of 0.5 to 20.0% by weight of glycerin condensed ricinolein (b1) and 0.5 to 10.0% by weight of sucrose ester (b2) having an HLB of 4 or less.
Examples of the fats and oils (A) used in the present invention include the following animal and vegetable oils or synthetic oils having a melting point of 5 ° C., and edible fats and oils that are room temperature liquids. Specific examples include rapeseed oil, soybean oil, rice oil, sesame oil, olive oil, palm olein oil, cottonseed oil, sunflower oil, corn oil, and MCT oil (medium chain fatty acid triglyceride). Rapeseed oil, soybean oil, corn oil, MCT oil and the like are preferable. Even if it is animal and vegetable fats and oils higher than the melting point of 5 ° C., the melting point is not problematic even if blended with the animal and vegetable fats and oils having a melting point of 5 ° C. or less as long as there is no problem such as precipitation of solid fat. If it is high, crystals are likely to be produced, and solid fat is clogged by the spray nozzle.
[0012]
As the activator (B) used in the present invention, a polyglycerin condensed ricinoleic acid ester (b1) and a sucrose fatty acid ester (b2) having an HLB of 4 or less are used in combination.
The polyglycerin condensed ricinoleic acid ester (b1) is an esterified product of polyglycerin and condensed ricinoleic acid, and the polyglycerin portion is a polyglycerin having an average degree of polymerization of 3 to 6, and an ricinolein having an average degree of condensation of 3 to 6. An esterified product with an acid moiety.
Specific examples include triglycerin condensed linolenic acid ester, tetraglycerin condensed ricinoleic acid ester, pentaglycerin condensed ricinoleic acid ester, hexaglycerin condensed ricinoleic acid ester, decaglycerin condensed ricinoleic acid ester and the like.
Among them, particularly preferred are condensed ricinoleic acid hexaglycerin ester and condensed ricinoleic acid pentaglycerin ester.
[0013]
The sucrose fatty acid ester (b2) having an HLB of 4 or less used in the present invention is an ester of sucrose and a saturated or unsaturated fatty acid having 8 to 22 carbon atoms. Specifically, for example, caprylic acid sucrose ester, caprin Acid sucrose ester, lauric acid sucrose ester, myristic acid sucrose ester, palmitic acid sucrose ester, stearic acid sucrose ester, oleic acid sucrose ester, behenic acid sucrose ester, elaidic acid sucrose ester, linoleic acid sucrose Examples thereof include sugar esters and linolenic acid sucrose esters. Of these, palmitic acid sucrose ester, stearic acid sucrose ester, and oleic acid sucrose ester are preferable.
Further, among sucrose esters, it is more preferable to use a combination of two types of sucrose ester of saturated fatty acid (b21) and sucrose ester of unsaturated fatty acid (b22). A combination of a sucrose ester of a saturated fatty acid (b21) and a sucrose ester of a mixed fatty acid of a saturated fatty acid and an unsaturated fatty acid is also preferred. A sucrose having a HLB greater than 4 regardless of whether the constituent fatty acid is a saturated acid or an unsaturated acid. If an ester is used, the releasability deteriorates.
[0014]
As water (C) used by this invention, the water which can be used for normal foods, such as purified water, ion-exchange water, and distilled water, is mentioned.
[0015]
The blending ratio of water (C) and [oil (A) + active agent (B)] is [(C) / [(A) + (B)]] in order to obtain a W / O emulsion. The weight ratio is 10/90 to 45/55. More preferably, it is 20 / 80-40 / 60 from the point which can fully suppress the mist at the time of spraying.
If the amount of water (C) is less than 10/90, the amount of mist generated during spraying increases. On the other hand, when the amount of water (C) is larger than 45/55, it becomes difficult to take the form of a W / O type emulsion. The moldability is lowered, and it becomes difficult to suppress dripping.
[0016]
The blending amount of the condensed ricinoleic acid polyglycerin ester (b1) is 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the whole mold release oil, and sucrose having an HLB of 4 or less. The ester (b2) is 0.5 to 10% by weight, preferably 1 to 5% by weight.
When the amount of the condensed ricinoleic acid polyglycerin ester (b1) is less than 0.5% by weight, emulsification is insufficient, and when it is more than 20% by weight, the viscosity of the system becomes high and the nozzle is easily clogged. The flavor is also deteriorated. When the blending amount of sucrose ester (b2) having an HLB of 4 or less is less than 0.5% by weight, sufficient viscosity is not imparted, and liquid dripping easily occurs. When the amount of sucrose ester (b2) is more than 10% by weight, the viscosity of the system becomes high and the spray nozzle is easily clogged.
[0017]
The use of sucrose ester (b2) of HLB4 or lower, which is a mixture of sucrose ester of saturated fatty acid (b21) and sucrose ester of unsaturated fatty acid (b22), suppresses the formation of crystals with a high freezing point. From the viewpoint of product stability, it is more preferable. The blending ratio of b21 / b22 is more preferably 20/80 to 80/20 weight ratio. The blending ratio of b21 / b22 is more preferably 40/60 to 60/40 weight ratio. It is also preferable to use a sucrose fatty acid ester of a saturated or unsaturated mixed acid in which a saturated fatty acid and an unsaturated fatty acid are mixed as the sucrose ester of unsaturated fatty acid (b22).
[0018]
The release oil of the present invention may be blended with other components as long as the effects of the present invention are not impaired. Examples of other components include fragrances, coloring agents, preservatives, and antifungal agents.
[0019]
Next, the manufacturing method of the mold release oil of this invention is demonstrated.
The method for producing the release oil of the present invention is not particularly limited as long as a W / O type emulsion is obtained, and examples thereof include the following methods.
A predetermined amount of the oil and fat and the activator are weighed in a container and dissolved by heating. Next, a pre-warmed aqueous phase is added to the blended oil while stirring in a predetermined amount to obtain a W / O type emulsion. Then cool to room temperature. The average particle size of the water droplets of the W / O emulsion thus obtained is not particularly limited, but is usually about 0.1 μm to 50 μm, more preferably about 1 μm to 10 μm from the viewpoint of product stability. .
The stirrer for producing the W / O type emulsion is not particularly limited, and examples thereof include a homomixer, a disper, a propeller stirrer, a high-pressure homogenizer, a botter, and other rapid kneaders.
Although depending on the blending system, it is desirable to appropriately select conditions for the processing temperature and time in consideration of the stability of the product. Applying a very strong shearing force is not preferable because it causes emulsion breakage. The release oil thus obtained usually has a viscosity in the range of 200 cSt to 5000 cSt, more preferably in the range of 500 cSt to 2000 cSt.
[0020]
Next, the usage method of the release oil of this invention is demonstrated.
The release oil of the present invention can be used for spray nozzle spraying in the food field. In particular, it is used by being sprayed with a spray nozzle and applied to a container such as food. As a model of the spray machine, for example, Asahi Sunac Co., Ltd. Peak Bear Hot, AP1224H, Anest Iwata Co., Ltd., airless spray device, a combination of Multi Alpha and spray device, Wakabayashi Kogyo Co., Ltd., SG- 2, TG-2 greaser spray, and the like.
It is desirable to set preferable conditions as appropriate depending on the machine performance and the viscosity adjustment of the release oil.
[0021]
【The invention's effect】
The release oil of the present invention is composed of fats and oils, an activator, and water, and is a W / O type emulsion. Therefore, compared with an all-oil type release oil consisting only of an oil component and an activator, the time of mechanical spraying The nozzles are not clogged, continuous operation is possible, and excellent releasability is exhibited. In addition, the release oil of the present invention is excellent in releasability and liquid dripping is suppressed as compared with the O / W type emulsion. Furthermore, since there is little mist especially when spraying by a pressure, the outstanding effect with respect to environmental pollution is shown.
[0022]
【Example】
Hereinafter, the present invention will be described in more detail based on examples.
Next, the test method and evaluation method used are shown.
<1. State stability (emulsification state) test>
After the release oil was prepared, the release oil was taken in a sample bottle and stored in a constant temperature bath at 30 ° C., and oil-water separation was observed visually for changes over time. The evaluation is shown in the table as the following symbol.
A: There is no separation of oil and water, and the whole is uniform and smooth.
○: There is a slightly transparent phase on the liquid surface, and there is a smooth feeling.
Δ: Oil-water separation is confirmed.
X: The oily water was severely separated and completely separated into two layers.
<2, spray state>
The spray state is a spray using a pressurized spray (spray cart II, manufactured by Spraying System Japan Co., Ltd.), using the release oil of Examples and Comparative Examples as a test sample, and an air pressure of 5 kg / cm 2 . Went.
A: The spray state is uniform and fine. Good spray condition is maintained for a long time.
○: The spray state is fine, but the spray state is slightly biased.
Δ: Spray state is uneven and spray is slightly non-uniform.
X: The spray state is not fine and spraying is poor.
<3. Liquid sag suppression>
The liquid dripping suppression property was confirmed by spraying about 5.0 g uniformly on a 12 cm × 11 cm × 25 cm 2cm mold with the above-mentioned pressure spraying machine, and then checking the presence or absence of liquid dripping on the wall surface portion.
The evaluation is shown in the table as the following symbol.
A: Good without dripping.
◯: Almost no dripping and good.
Δ: Slight dripping occurs.
X: Liquid dripping occurs, the oil film on the wall surface becomes thin, and release oil accumulates at the bottom.
<4. Mist suppression test>
The mist suppression test was performed by observing the degree of mist that was sprayed with the above-described pressurized sprayer and then the release oil atomized and floated in the air.
The evaluation is shown in the table as the following symbol.
A: Mist is sufficiently suppressed.
○: Mist is suppressed.
Δ: Slightly insufficient suppression of mist.
X: Mist suppression is insufficient.
[0023]
<4. Release properties>
The mold release test was conducted by applying a certain amount of release oil (4.0 g) to a baking bread mold (2 斤 type), baking the bread dough by the same composition and manufacturing method described below, The degree of removal from the mold was visually observed.
The evaluation is shown in the table as the following symbol.
(Double-circle); Mold release is very favorable.
○: Good mold release.
Δ: Slightly insufficient mold release
X: Demolding failure.
<Bread dough combination>
The dough manufacturing method was a medium seed method. Medium seeds are mixed with 70 parts by weight of strong powder and 42 parts by weight of water in which yeast is dispersed in advance, and kneaded with a mixer. After fermentation at 28 ° C. for 4 hours, 30 parts by weight of strong flour, 8 parts by weight of white sucrose, 1.83 parts by weight of sodium chloride and 25 parts by weight of water are mixed with a main dough and a medium seed dough using a mixer. After that, the floor time was taken for 20 minutes and the dough was divided. Thereafter, after 15 minutes of bench time, molding was performed, and proofing was performed at 38 ° C. and 85% humidity for about 35 minutes.
<Baking conditions>
After the proofing, the dough was filled in a 2cm mold and baked at about 210 ° C for about 35 minutes.
[0024]
<6. Overall evaluation>
The overall evaluation as a release oil is shown by the above evaluation method.
◎; Very good (Three or more ◎, others are ○)
○: Good (Evaluation is only ◎, ○, △, not including x)
X: Defect (including x in the evaluation items 1 to 5)
[0025]
Next, materials used in Examples and Comparative Examples are shown.
<Oil and fat>
Rapeseed oil;
Rapeseed extremely hardened oil; melting point 69 ° C,
Fish oil hardened oil; melting point 43 ° C,
Rice wax; melting point 70-77 ° C.
<Activator>
Condensed ricinolein polyglycerol ester; condensed ricinoleic acid hexaglycerol ester;
[0026]
Example 1;
Oil and fat (A), rapeseed oil, 65 parts by weight, polyglycerin condensed ricinoleic acid ester (b1) (Mitsubishi Chemical Foods, Inc., trade name S-170 (HLB1) as an activator, saturated acid type Sugar ester (b21) (Mitsubishi Chemical Foods, Inc., trade name O-170 (HLB1) 1.5 parts by weight, and unsaturated acid sucrose ester (b22) (Mitsubishi, Ltd., trade name) O-170) 1.5 parts by weight is weighed in a container and heated to a temperature of 70 ° C. while stirring to completely dissolve the activator. Slowly add to prepare a W / O emulsion.
Then, it cooled rapidly to room temperature and obtained the W / O emulsification type release oil.
Using this release oil, an evaluation test was performed according to the above evaluation method. The results are shown in Table 1.
[0027]
Examples 2 , 3, 6, 7, 8, Reference Examples 4, 5, and Comparative Examples 1-10
In the same manner as in Example 1, the release oil was blended with the material composition shown in Table 1. The results evaluated in the same manner are shown in Tables 1, 2 and 3.
[0028]
[Table 1]
[0029]
[Table 2]
[0030]
[Table 3]
[0031]
From the above results, Examples 1 to 3 , 6 to 8 and Reference Examples 4 and 5 of the present invention are comparative examples 1 to 4 and HLB which are outside the scope of the present invention in which oils with high melting points are blended. Compared to Comparative Example 5 of the whole oil system using an activator that is out of the range, and Comparative Examples 6 to 10 containing other surfactants, in terms of dripping suppression, releasability, mist suppression, etc. It turns out that it is excellent.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003014106A JP4419186B2 (en) | 2003-01-23 | 2003-01-23 | Release oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003014106A JP4419186B2 (en) | 2003-01-23 | 2003-01-23 | Release oil |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004222588A JP2004222588A (en) | 2004-08-12 |
JP4419186B2 true JP4419186B2 (en) | 2010-02-24 |
Family
ID=32902241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003014106A Expired - Lifetime JP4419186B2 (en) | 2003-01-23 | 2003-01-23 | Release oil |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4419186B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2419888B (en) * | 2004-11-06 | 2010-04-14 | St Giles Foods Ltd | Liquid edible products and methods of stabilising liquid edible products |
JP5601831B2 (en) * | 2009-12-25 | 2014-10-08 | ミヨシ油脂株式会社 | Release oil |
JP6274801B2 (en) * | 2013-09-27 | 2018-02-07 | 日清オイリオグループ株式会社 | Steamed cakes and method for producing the same |
US20220322857A1 (en) * | 2019-06-07 | 2022-10-13 | Lee & B Inc. | Paper straw |
-
2003
- 2003-01-23 JP JP2003014106A patent/JP4419186B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2004222588A (en) | 2004-08-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Orthoefer et al. | Applications of emulsifiers in baked foods | |
CA2184477C (en) | A non-aerosol foodstuffs parting composition | |
Norn | Polyglycerol esters | |
KR20150127065A (en) | Chocolate-like food for baking and method for producing same | |
JP6172899B2 (en) | Release oil | |
JP4419186B2 (en) | Release oil | |
JP2004016187A (en) | Food-foaming agent composition and method for producing the same | |
WO2007061372A1 (en) | Pumpable shortening comprising stably dispersed solid sheet like flakes of fat | |
JP2008022791A (en) | Mold release oil | |
KR20150129699A (en) | Chocolate-like food product for baking, and method for manufacturing same | |
EP1814400B1 (en) | Liquid edible products and methods of stabilising liquid edible products | |
JP4349617B2 (en) | Water-in-oil emulsion for spray | |
JPH05336884A (en) | Foamable oil-in-water type edible fat and oil composition and production of cake using the same | |
JP5601427B2 (en) | Emulsified oil and fat composition for roll-in | |
JP2013247881A (en) | Mold-releasing agent for bread making/confectionery making, and method for producing bread/confectionery | |
JP2008237188A (en) | Mold release oil | |
US3230090A (en) | Shortening composition | |
JP2017093310A (en) | Oil and fat composition for baked confectionery milling | |
US8158185B2 (en) | Controlled viscosity oil composition and method of making | |
JP4610072B2 (en) | Bread making method | |
JP2005110510A (en) | Powdery or granular emulsifier composition and food containing the same | |
JP6093992B2 (en) | Grease spray for food machine and method for producing grease spray for food machine | |
JP6347867B2 (en) | Release oil | |
JP2005046098A (en) | Mold releasing agent and mold releasing oil for confectionery and bread making | |
JPH06253738A (en) | Release oil composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060119 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081119 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081202 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090130 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090130 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20090130 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090707 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090724 |
|
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: 20091109 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091122 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121211 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4419186 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131211 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |