JP5683909B2 - Decorative edible metal foil and method for producing the same - Google Patents
Decorative edible metal foil and method for producing the same Download PDFInfo
- Publication number
- JP5683909B2 JP5683909B2 JP2010250524A JP2010250524A JP5683909B2 JP 5683909 B2 JP5683909 B2 JP 5683909B2 JP 2010250524 A JP2010250524 A JP 2010250524A JP 2010250524 A JP2010250524 A JP 2010250524A JP 5683909 B2 JP5683909 B2 JP 5683909B2
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- Prior art keywords
- metal foil
- edible
- foil
- resin
- film
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- General Preparation And Processing Of Foods (AREA)
Description
本発明は、飲食物を加飾するための食用金属箔及びその製造方法に関する。より詳しくは、長期保存を求められる液体飲食物以外のほとんどの飲食物の加飾に適した、金属光輝性を示す食用金属箔に関する。 The present invention relates to an edible metal foil for decorating food and drink and a method for producing the same. More specifically, the present invention relates to an edible metal foil that exhibits metal glitter and is suitable for decorating most foods and drinks other than liquid foods that require long-term storage.
従来から、調理された食材に対し、加飾、高級感の付与、または健康増進を目的として、金、銀等の貴金属が利用されて来たが、高価なため、１μｍ以下の薄膜で利用されることが多く、取り扱いに高度の技術が必要である。具体的には、金箔では通常、０．１μｍ、銀箔では、０．３μｍと非常に薄く柔軟で、特に粉末での利用が困難であるという問題がある。
また、近年では、バリエーション豊かに食材を加飾するために、貴金属としての特徴、すなわち金属光輝性を保ちつつ、多彩な色合い有する食用貴金属箔やその粉末が求められている。
Conventionally, precious metals such as gold and silver have been used for the purpose of decorating, imparting a sense of quality, or promoting health for cooked foods, but they are expensive and used in thin films of 1 μm or less. In many cases, advanced techniques are required for handling. Specifically, there is a problem that gold foil is usually 0.1 μm and silver foil is 0.3 μm, which is very thin and flexible, and particularly difficult to use in powder form.
In recent years, there has been a demand for edible precious metal foils and powders having various colors while maintaining the characteristics as a precious metal, that is, the metallic luster, in order to decorate foods with a wide variety.
このように、加飾目的での食用金属箔の需要の増加に伴い、食用金属箔について様々な考案がなされてきた。
例えば、特許文献１では、食用可能な金箔もしくは銀箔からなる文字、模様、絵柄等を、可食物に、箔押し印刷法を用いて形成することができる、箔押し材が開示されている。また、箔の着色についても開示されており、離型層と貴金属層との間、あるいは、接着層と、貴金属層との間の少なくとも一方に、可食性のインクを塗布して着色層を形成して、種々の色彩からなる箔押し印刷をすることが開示されている。
特許文献２では、食品と任意の形状・模様を持つ食用箔を混合するか、貼付けする方法で菓子・食品を美しく装飾する食用箔及びその使用法が開示されており、具体的には、離型性のあるベース、その上に任意の形状に形成した食用できる接着剤層、及びその食用接着剤層に接着した金属箔よりなる食用箔が記載されている。
特許文献３では、生菓子やチョコレートなどに振りかけて使用される食用装飾素材について、高級脂肪酸や油脂素材の浸透可能な層等を必要とせずに、様々な素材に振りかけ、接着させることが可能である装飾用素材が開示されており、具体的には、金属箔表面を、アラビアガム、キサンタンガム及び／又はジェランガムの一種又は二種を溶解してなる増粘多糖類水溶液で被覆し、その後乾燥し、乾燥した前記金属箔を粉砕機で粉砕するか、あるいは型で打ち抜く等の工程を行う方法が開示されている。
特許文献４では、可食性膜に金箔又は銀箔を積層させた飲食品用金銀箔において、この飲食品用金銀箔と食品との密着力を適性にすると共にブロッキングを防止することを課題とした食用金銀箔が開示されており、具体的には、プルラン等の可食性膜の片面を粗面にし、可食性膜の両面に金銀箔を貼着した食用金銀箔が開示されている。
特許文献５では、粒状食品の略全表面に満遍なく金属箔を被覆した金属箔被覆粒状食品を提供する方法が開示されている。また、これに着色を施すことも開示されており、具体的には、銀箔で被覆されたグラニュー糖に、赤色３号を添加したエタノールを噴霧して着色させる方法が開示されている。
特許文献６は、本願の出願人自身による出願であり、耐候性、耐摩耗性、耐溶剤性に優れ、且つ意匠性にも優れた光輝性銀箔及び銀粉末に関するものである。
Thus, with the increasing demand for edible metal foils for decoration purposes, various ideas have been made for edible metal foils.
For example, Patent Document 1 discloses a foil-pressing material that can form edible characters, patterns, patterns, etc. made of edible gold foil or silver foil in an edible manner using a foil-press printing method. Moreover, the coloring of the foil is also disclosed, and a colored layer is formed by applying an edible ink between at least one of the release layer and the noble metal layer or between the adhesive layer and the noble metal layer. Thus, it is disclosed to perform foil stamp printing composed of various colors.
Patent Document 2 discloses an edible foil that decorates confectionery and food beautifully by mixing or pasting food and an edible foil having an arbitrary shape and pattern, and its usage. There is described an edible foil comprising a moldable base, an edible adhesive layer formed in an arbitrary shape thereon, and a metal foil adhered to the edible adhesive layer.
In patent document 3, it is possible to sprinkle and adhere to various materials, without requiring a layer capable of penetrating high-grade fatty acids or oils and fats, for edible decoration materials used by sprinkling on raw confectionery or chocolate. A decorative material is disclosed, specifically, a metal foil surface is coated with a thickening polysaccharide aqueous solution obtained by dissolving one or two kinds of gum arabic, xanthan gum and / or gellan gum, and then dried. A method is disclosed in which the dried metal foil is pulverized with a pulverizer or punched with a mold.
In patent document 4, in the gold-and-silver foil for food / beverage products which laminated | stacked gold foil or silver foil on the edible film, it was made into the subject which made the adhesion power of this gold / silver foil for food-drinks and foods suitable, and prevented blocking Gold-silver foil is disclosed, and specifically, an edible gold-silver foil in which one side of an edible film such as pullulan is roughened and gold-silver foil is adhered to both sides of the edible film is disclosed.
Patent Document 5 discloses a method for providing a metal foil-coated granular food in which a metal foil is uniformly coated on almost the entire surface of the granular food. In addition, it is also disclosed that coloring is performed, and specifically, a method of spraying ethanol added with red No. 3 to granulated sugar coated with silver foil is disclosed.
Patent Document 6 is an application by the applicant of the present application, and relates to a glittering silver foil and a silver powder that are excellent in weather resistance, wear resistance, solvent resistance, and excellent in design.
上記特許文献１および２に係る発明は、ベースから離型して使用する箔に関するものであり、金属箔や金属箔粉そのものの状態で取り扱えるものではない。特許文献３の方法で製造された金属箔粉や金属箔片は、増粘多糖類で被覆されているため、水分、アルコール類を含んだ食材に触れると皮膜が軟化、溶解、消失して、加飾性が不十分という問題がある。特許文献４は、可食性膜の両面に金属箔を貼り付けたものであり、２枚の金属箔が必要であり、さらに可食性膜の片面を粗面に形成する必要があるため、コストがかかるという問題がある。特許文献５は、金属箔被覆粒状食品を提供する方法であって、取り扱いに優れた金属箔や金属箔粉自体を提供するものではない。特許文献６の銀箔や銀粉末は、食用を目的として開発されたものではないため、食用に不向きであるという問題がある。
また、上記特許文献のいくつかには、着色に関する記述があるが、食品の加飾に使用された際に、着色色素のにじみ等が生じない食用の着色金属箔や箔粉については開示されていない。
The inventions according to Patent Documents 1 and 2 relate to a foil that is used after being released from a base, and cannot be handled in a state of a metal foil or a metal foil powder itself. Since the metal foil powder and metal foil pieces produced by the method of Patent Document 3 are coated with thickening polysaccharides, the film softens, dissolves and disappears when it comes into contact with ingredients containing moisture and alcohol, There is a problem that the decorating property is insufficient. In Patent Document 4, metal foil is pasted on both sides of an edible film, two metal foils are required, and further, one side of the edible film needs to be formed on a rough surface. There is a problem that it takes. Patent Document 5 is a method for providing a metal foil-coated granular food, and does not provide a metal foil or metal foil powder that is excellent in handling. Since the silver foil and silver powder of Patent Document 6 are not developed for edible purposes, there is a problem that they are not suitable for edible use.
In addition, some of the above-mentioned patent documents have descriptions relating to coloring, but edible colored metal foils and foil powders that do not cause bleeding of colored pigments when used for decorating foods are disclosed. Absent.
したがって、本発明は、金属箔または金属箔片や金属箔粉の状態で食品の加飾に使用することができ、水分を含む食品や、水、アルコールといった液体に添加した際も形状保持が可能で、且つ金属箔本来の光輝性を発揮することができる金属箔を提供することを課題とする。さらに本発明は、着色色素のにじみ出しが生じない着色金属箔を提供することを課題とする。 Therefore, the present invention can be used for decorating food in the form of metal foil or metal foil pieces or metal foil powder, and can retain its shape when added to water-containing foods or liquids such as water and alcohol. It is another object of the present invention to provide a metal foil that can exhibit the original brightness of the metal foil. Furthermore, this invention makes it a subject to provide the colored metal foil which does not bleed out of a coloring pigment | dye.
本発明者は、上記課題を解決するために鋭意研究した結果、食用金属箔の両面を無色もしくは有色の皮膜で被覆し、さらに、前記皮膜として、食用可能な樹脂を架橋させることによって形成された、水不溶性の透明または半透明の樹脂皮膜を用いることによって、前記課題を解決することに成功し、本発明を完成した。 As a result of earnest research to solve the above-mentioned problems, the present inventor was formed by coating both surfaces of an edible metal foil with a colorless or colored film, and further crosslinking an edible resin as the film. By using a water-insoluble transparent or translucent resin film, the present inventors have succeeded in solving the above problems and completed the present invention.
すなわち、本発明は、食用金属箔の両面を無色もしくは有色の皮膜で被覆してなる、金属光輝性を示す加飾用食用金属箔であって、前記皮膜が、シェラック樹脂を架橋させることによって形成された、熱硬化性または軟化点６０℃以上の樹脂被膜であり、水に不溶性で透明または半透明であることを特徴とする。 That is, the present invention is a decorative edible metal foil having a metallic glitter, which is formed by coating both surfaces of an edible metal foil with a colorless or colored film, and the film is formed by crosslinking a shellac resin. has been a thermosetting or softening point 60 ° C. above the resin film, characterized in that it is a transparent or semitransparent light insoluble in water.
本発明の加飾用食用金属箔は、両面が皮膜で被覆されているため、皮膜がない場合と比べて、加工性に優れ、任意の形状に加工した際も、形状保持性に優れる。また、皮膜が透明もしくは半透明であるため、金属箔特有の光輝性が保たれ、金属箔本来の意匠性を利用出来る。さらに、この皮膜は食用可能な樹脂を架橋させることによって形成された、水不溶性の樹脂皮膜であるため、水分を含んだ食材や飲料に使用しても、保持材が軟化、溶解、消失する恐れがなく、加飾効果を維持できる。 Since the decorative edible metal foil of the present invention is coated on both sides with a film, it is excellent in workability as compared to the case where there is no film, and is excellent in shape retention even when processed into an arbitrary shape. In addition, since the film is transparent or translucent, the glitter characteristic of the metal foil is maintained, and the original design of the metal foil can be used. Furthermore, since this film is a water-insoluble resin film formed by crosslinking an edible resin, the holding material may be softened, dissolved, or disappeared even when used for moisture-containing foods and beverages. The decoration effect can be maintained.
また、前記樹脂皮膜として、食用可能な着色色素を含む樹脂皮膜を使用すれば、任意の色彩に着色された金属箔を得ることができる。食用可能な着色色素は、水溶性かアルコール可溶性を示すものが多く、水に不溶の皮膜に含有させても、アルコールや水に接すると色素が溶出し、着色金属箔の周囲に色素がにじみだすが、本発明では樹脂の架橋構造により、色素の溶出を防ぐことができるため、色のにじみが抑制される。 Moreover, if the resin film containing an edible coloring pigment | dye is used as said resin film, the metal foil colored by arbitrary colors can be obtained. Many edible coloring pigments are water-soluble or alcohol-soluble, and even if they are contained in a water-insoluble film, the pigments elute when in contact with alcohol or water, and the pigments ooze around the colored metal foil. However, in the present invention, since the elution of the dye can be prevented by the crosslinked structure of the resin, color bleeding is suppressed.
前記皮膜としては、シェラック樹脂を架橋させることによって形成された皮膜が好ましい。シェラック樹脂は、常温で容易にアルコール類に溶解し、加熱するとエステル化による架橋反応が進行、所謂、熱硬化性を示す性質を有し、このようにして得られた皮膜は加熱しても軟化しない。また、シェラック樹脂は、２価以上の金属塩、例えばカルシウム、マグネシウムの塩を添加すると、イオン結合による架橋構造を形成し、ゲル化して、水、アルコールに溶けなくなる性質を有する。
したがって、食用可能な金属箔の両面に、シェラック樹脂を含むアルコール溶液を塗布し、加熱により、シェラック樹脂を架橋させて、金属箔の両面に熱硬化性の樹脂皮膜を形成するか、又は、食用可能な金属箔の両面に、シェラック樹脂と２価以上の金属塩とを含むアルコール溶液を塗布し、溶液を乾燥することで、シェラック樹脂をイオン結合により架橋させて、金属箔の両面に樹脂皮膜を形成することにより、本発明に係る加飾用食用金属箔を製造することができる。なお、上記２つの方法を組合せてもよい。すなわち、シェラック樹脂と２価以上の金属塩とを含むアルコール溶液を塗布し、加熱乾燥または乾燥後に加熱して、エステル化による架橋と、イオン結合による架橋の両方を有する皮膜を形成してもよい。
The film is preferably a film formed by crosslinking a shellac resin. Shellac resin dissolves easily in alcohols at room temperature, and when heated, the crosslinking reaction by esterification proceeds, so-called thermosetting properties. The film thus obtained is softened even when heated. do not do. Further, the shellac resin has a property that when a divalent or higher-valent metal salt such as calcium or magnesium salt is added, it forms a cross-linked structure by ionic bond and gels, so that it does not dissolve in water or alcohol.
Therefore, an alcohol solution containing shellac resin is applied to both surfaces of the edible metal foil, and the shellac resin is crosslinked by heating to form a thermosetting resin film on both surfaces of the metal foil, or edible An alcohol solution containing shellac resin and a divalent or higher metal salt is applied to both sides of a possible metal foil, and the solution is dried to crosslink the shellac resin by ionic bonding, and a resin film on both sides of the metal foil. By forming the edible metal foil for decoration according to the present invention can be produced. Note that the above two methods may be combined. That is, an alcohol solution containing shellac resin and a metal salt having a valence of 2 or more may be applied, and heated or dried or dried to form a film having both crosslinking by esterification and crosslinking by ionic bonds. .
着色箔を製造する場合は、前記シェラック樹脂のアルコール溶液に着色色素を添加すればよい。 When manufacturing a colored foil, a coloring pigment may be added to the alcohol solution of the shellac resin.
前記加飾用食用金属箔を裁断または粉砕することによって得られた金属箔片または金属箔粉も、上述した効果を有するため、飲食物の加飾に好適である。 Since the metal foil piece or metal foil powder obtained by cutting or crushing the edible metal foil for decoration also has the effects described above, it is suitable for decorating food and drink.
前記金属箔としては、金、銀、白金からなる群から選択される貴金属箔が好ましく、これらの貴金属の純度が９９．９％以上の箔が特に好ましい。 As the metal foil, a noble metal foil selected from the group consisting of gold, silver and platinum is preferable, and a foil having a purity of 99.9% or more is particularly preferable.
本発明によれば、食用金属箔の欠点であった、食材への飾り付け、取り扱いの不便を改善することができ、金属特有の光輝性と高級感を持ち、且つ、任意の形状に加工しやすく、水分やアルコールを含む食品に使用した際も、優れた形状維持性を発揮する加飾用食用金属箔を得ることができる。また、任意の色彩に着色することができ、水分やアルコールを含む食品に使用した際も、色のにじみが生じにくく、食材への加飾性が高く、安定な意匠を保つ着色金属箔を得ることができる。したがって、食材の内部や飲料にも利用できる実用性に優れた金属箔を提供することができる。
更に、本発明では、構成材料全てを天然素材から選択することが可能であるため、安全な食用金属箔を提供することが出来る。
また、本発明によれば、従来、食材に適用しにくかった銀箔であっても、安定で豊富な色彩の食用箔として提供することが可能である。
According to the present invention, it is possible to improve the inconvenience of decorating and handling foodstuffs, which was a drawback of edible metal foils, having a unique luster and high-class feeling of metal, and easy to process into any shape Even when used in foods containing moisture and alcohol, a decorative edible metal foil that exhibits excellent shape maintenance can be obtained. In addition, it can be colored in any color, and when used in foods containing moisture or alcohol, a colored metal foil is obtained that is less likely to cause color bleeding, has high decorating properties, and maintains a stable design. be able to. Therefore, the metal foil excellent in practical use which can be utilized also for the inside of a foodstuff, or a drink can be provided.
Furthermore, in the present invention, since all the constituent materials can be selected from natural materials, a safe edible metal foil can be provided.
Further, according to the present invention, even a silver foil that has been difficult to apply to foods can be provided as a stable and abundant edible foil.
本明細書において、食用又は食用可能として記載された材料は、食品安全基本法及び食品安全衛生法記載の食品並びに食品添加物であればよい。特に天然の材料が好ましいが、これに限定されない。 In the present specification, the material described as edible or edible may be a food and a food additive described in the Food Safety Basic Law and the Food Safety and Hygiene Law. Natural materials are particularly preferred, but are not limited thereto.
本発明に係る食用金属箔とは、金、銀、白金等の光輝性金属の１種からなる箔、又はこれら２種以上からなる合金の箔、及びこれらに、食用の銅、アルミニウム、鉄等食品添加剤として認められている金属を添加してなる金属箔である。これらの金属を、古来から知られている定法の箔打ち手段により、厚み、５μｍ以下、好ましくは０.０５μｍ〜１μｍとした箔が好ましい。薄すぎると取り扱いに不便であり、且つ、金属光輝性が劣る。他方、厚すぎると高価であり、且つ、食感も良くない。尚、上記の打ち箔以外に、蒸着、スパタリング等により製膜された金属箔を用いてもよい。 The edible metal foil according to the present invention is a foil made of one of glittering metals such as gold, silver and platinum, or an alloy foil made of two or more of these, and edible copper, aluminum, iron, etc. It is a metal foil formed by adding a metal recognized as a food additive. A foil having a thickness of 5 μm or less, preferably 0.05 μm to 1 μm, is preferably used for these metals by a conventional foil punching means that has been known since ancient times. If it is too thin, it is inconvenient to handle and the metallic glitter is inferior. On the other hand, if it is too thick, it is expensive and the texture is not good. In addition to the above punched foil, a metal foil formed by vapor deposition, sputtering, or the like may be used.
本発明に係る食用金属箔として、好ましい銀箔または白金箔は、純度９９．９％以上の箔であり、純度９９.９９％以上の箔が特に好ましい。
本発明に係る食用金属箔として、実用的な合金箔は、表１−１に示す、金をベースとする合金箔及びこれらから銅成分を除去したものであるが、これに限定されるものではない。
尚、銅の一日の平均摂取及び排出量は２〜５ｍｇ程度で、４０ｍｇ以上摂取すると肝臓や脳に蓄積され過剰症になるとされているので、銅成分を含まない箔がより好ましい。
銅を含まない合金として、例えば、表１−２に示す、金と銀の２成分からなる合金が挙げられる。これらは仲色、三歩色、水色、定色を示す。
As the edible metal foil according to the present invention, a preferable silver foil or platinum foil is a foil having a purity of 99.9% or more, and a foil having a purity of 99.99% or more is particularly preferable.
As an edible metal foil according to the present invention, a practical alloy foil is a gold-based alloy foil shown in Table 1-1 and a copper component removed therefrom, but is not limited thereto. Absent.
The average daily intake and excretion amount of copper is about 2 to 5 mg, and when 40 mg or more is ingested, it is considered to accumulate in the liver and brain, resulting in excessive disease. Therefore, a foil containing no copper component is more preferable.
As an alloy which does not contain copper, the alloy which consists of two components of gold and silver shown in Table 1-2 is mentioned, for example. These indicate a neutral color, a three-step color, a light blue, and a constant color.
なお、銅を含まない箔では、表１−１に示すような多彩な色は得られない。しかし、本発明では、箔表面を、着色色素を含む皮膜で被覆することにより、所望の色を有する着色箔を得ることができる。
一般に金属箔は、プラズモンと呼ばれる、金属独特の表面現象で、金箔表面は赤色に、銀箔表面は黄色（金色）に帯色する傾向があり、さらに、フリップフロップと呼ばれる現象（金属表面で角度をかえて見ると違う色に見える現象）により、色の表現、表示が困難である。本発明の食用金属箔では、理由は解明されていないが、透明樹脂皮膜の形成により、プラズモンが強調され、例えば銀では、金色に帯色しやすくなるが、逆にフリップフロップ性が抑制される傾向が認められ、金属箔色の調整が容易になる。
そのため、着色した樹脂皮膜により、金属箔を多彩な色に着色することが可能である。
In addition, in the foil which does not contain copper, the various colors as shown in Table 1-1 cannot be obtained. However, in the present invention, a colored foil having a desired color can be obtained by coating the foil surface with a film containing a coloring pigment.
In general, metal foil is a surface phenomenon unique to metal called plasmon, and the gold foil surface tends to be red, the silver foil surface tends to yellow (golden), and the phenomenon called flip-flop (the angle on the metal surface It is difficult to express and display colors due to the phenomenon that looks different when viewed in different ways. In the edible metal foil of the present invention, the reason has not been elucidated, but plasmon is emphasized by the formation of the transparent resin film. For example, silver tends to be colored in gold, but flip-flop properties are suppressed. A tendency is recognized, and the metal foil color can be easily adjusted.
Therefore, the colored foil can be used to color the metal foil in various colors.
本発明に係る食用可能な樹脂として、天然材料である、シェラック、白シェラック、精製シェラック等のシェラック類が代表例として示される。
本発明に係る、水不溶性の樹脂皮膜は、食用可能な樹脂を架橋させることによって形成されたものであり、特に好ましいのは、熱硬化性樹脂皮膜である。この例として、シェラックを加熱してエステル化により架橋結合させてなる皮膜が挙げられる。
また、シェラックをカルシウム、マグネシウム等の２価の金属塩で処理することにより、シェラック中のカルボン酸をイオン結合で架橋させた皮膜を用いることもできる。
Typical examples of the edible resin according to the present invention include shellacs such as shellac, white shellac, and refined shellac, which are natural materials.
The water-insoluble resin film according to the present invention is formed by crosslinking an edible resin, and a thermosetting resin film is particularly preferable. An example of this is a film formed by crosslinking shellac by heating shellac.
In addition, by treating shellac with a divalent metal salt such as calcium or magnesium, a film obtained by crosslinking the carboxylic acid in shellac with an ionic bond can be used.
本発明では、樹脂を架橋させて皮膜を形成することが重要である。一般に架橋構造を有する樹脂は、架橋密度により軟化点を示すこともあるが、溶剤に対し、膨潤するが溶解しない。したがって、水分を含む食品や飲料に添加しても消失せず、金属箔の形状を維持することができる。尚、軟化点が室温に近いと取り扱いが不自由であるため、本発明に係る皮膜の軟化点は６０℃以上が好ましい。軟化点が高いほど、温かい食材に接した時、軟化せず、取り扱いが容易である。軟化点が１００℃以上であれば、たいていの飲食物に使用できる。使用する樹脂がシェラック樹脂の場合、加熱硬化させれば熱硬化性となり、軟化点を示さないものが得られる。イオン架橋によって硬化させた場合も、架橋の程度を調節することにより、軟化点１００℃以上の皮膜を形成することができる。
さらに、皮膜中に着色色素が含まれる場合、樹脂皮膜中の架橋構造は、着色色素を保持する役目を果たす。樹脂皮膜は、水に不溶なので、食材に接しても変化しないが、着色色素には水溶性色素が多い。したがって、樹脂皮膜が水不溶性というだけでは、水分を多く含む食材に接した際、水溶性色素がにじんで食材に色移りする。しかし、架橋結合が形成されている樹脂皮膜の場合、理由は解明されていないが、着色色素は金属箔の外縁から大きくにじみ出ず、金属箔の形状に捺染された状態にとどまる。このため、にじみ部分が少なく、また、箔の色も維持され、加飾用として非常に優れる。この現象は、架橋構造が、着色色素の水溶液成分を、スポンジ類似のゲル体として包接した状態で保持することによって、箔の外縁からの着色色素のはみ出しを抑制するためと推定される。
In the present invention, it is important to form a film by crosslinking the resin. In general, a resin having a crosslinked structure may exhibit a softening point depending on the crosslinking density, but it swells but does not dissolve in a solvent. Therefore, even if it adds to the food and drink containing a water | moisture content, it does not lose | disappear, but the shape of metal foil can be maintained. In addition, since the handling is inconvenient when the softening point is close to room temperature, the softening point of the film according to the present invention is preferably 60 ° C. or higher. The higher the softening point, the easier it is to handle when it comes into contact with a warm food and it does not soften. If a softening point is 100 degreeC or more, it can be used for most food and drink. When the resin to be used is a shellac resin, if it is heat-cured, it becomes thermosetting and does not show a softening point. Even when cured by ionic crosslinking, a film having a softening point of 100 ° C. or higher can be formed by adjusting the degree of crosslinking.
Furthermore, when a coloring pigment | dye is contained in a film | membrane, the crosslinked structure in a resin film plays the role which hold | maintains a coloring pigment | dye. Since the resin film is insoluble in water, it does not change even when it comes into contact with foodstuffs, but the coloring pigments are often water-soluble pigments. Therefore, if the resin film is merely water-insoluble, when it comes into contact with a food containing a lot of water, the water-soluble pigment is blurred and transferred to the food. However, in the case of a resin film in which a cross-linked bond is formed, the reason is not elucidated, but the coloring pigment does not ooze out from the outer edge of the metal foil and remains in the state of being printed in the shape of the metal foil. For this reason, there are few blurring parts, the color of foil is also maintained, and it is very excellent for decorating. This phenomenon is presumed to be because the cross-linked structure keeps the aqueous solution component of the coloring dye in a state of being included as a sponge-like gel body, thereby suppressing the protrusion of the coloring dye from the outer edge of the foil.
本発明において特に好ましい樹脂であるシェラック(shellac)は、セラックとも呼ばれ、ラックカイガラムシと呼ばれる昆虫が分泌する物質を精製して得られる天然樹脂であり、食品衛生法や日本薬局方にも記載されている安全性の高い樹脂である。
シェラック樹脂の主成分は、ヒドロキシ脂肪酸（Aleuritic Acid）とセスキテルペン酸(Shellolic Acid)のエステルを基本単位構造とした分子量３００〜３０００程度の混合物である。
シェラックは所定の温度以上で加熱すると、高分子量の三次元架橋構造を形成して硬化する。加熱硬化により引き起こされる架橋反応は、シェラック分子内のカルボン酸と水酸基間のエステル反応及びカルボン酸同士の酸無水物結合の生成によると推定される。白シェラックは、１４０℃で５分〜１８０℃で１分、精製シェラックは、１８０℃で５分〜２００℃で１分程度加熱することによって架橋反応を進行させることができる。
シェラックは加熱硬化する前は、常温で容易にアルコール類に溶解するため、シェラックのアルコール溶液、好ましくは食添グレードのエタノール溶液を、金属箔の両面に塗布し、上記条件で加熱することによって、金属箔の両面に熱硬化性の皮膜を形成させることができる。
Shellac, which is a particularly preferred resin in the present invention, is also called shellac and is a natural resin obtained by purifying a substance secreted by insects called rack insects, and is also described in the Food Sanitation Law and the Japanese Pharmacopoeia. It is a highly safe resin.
The main component of the shellac resin is a mixture having a molecular weight of about 300 to 3000 having an ester of hydroxy fatty acid (Aleuritic Acid) and sesquiterpenic acid (Shellolic Acid) as a basic unit structure.
When shellac is heated above a predetermined temperature, a high molecular weight three-dimensional crosslinked structure is formed and cured. The crosslinking reaction caused by heat curing is presumed to be due to ester reaction between carboxylic acid and hydroxyl group in shellac molecule and generation of acid anhydride bond between carboxylic acids. The white shellac can proceed to the crosslinking reaction by heating at 140 ° C. for 5 minutes to 180 ° C. for 1 minute, and the purified shellac can be heated at 180 ° C. for 5 minutes to 200 ° C. for about 1 minute.
Since shellac is easily dissolved in alcohols at room temperature before being heat-cured, shellac alcohol solution, preferably food grade ethanol solution, is applied to both sides of the metal foil and heated under the above conditions, A thermosetting film can be formed on both sides of the metal foil.
また、イオン結合性の架橋により水不溶性の皮膜を形成することも可能である。この場合は、２価以上の金属塩（例えば、リン酸カルシウム類、乳酸カルシウム類等）を含む水溶液又は含水アルコール溶液をシェラックのアルコール溶液に加え、金属箔の両面に塗布し、乾燥させることで、イオン架橋反応が進行し、皮膜が形成される。この反応は、常温乾燥で生じるが、乾燥時または乾燥後に加熱すると、エステル化による架橋反応も進行するため、皮膜の熱硬化性を更に向上させることができる。
カルシウム、マグネシウム等２価のアルカリ土類化合物の使用アルカリ当量は、樹脂中のカルボキシ当量の５〜３０％が適量である。多量に加えるとアルコール樹脂溶液がゲル化するため、金属箔表面に塗布しにくくなる。少なすぎると架橋密度が小さく、色素保持効果が不足する。
尚、樹脂のカルボキシ当量（Ｅｑ．ａｃ）とは、樹脂中に含まれるカルボキシル基一個に対する重量割合に相当し、酸価（ＡＶ，樹脂１００ｇを中和するに必要なＫＯＨのｍｇ）から、下記の式Ｉ
（式Ｉ） Ｅｑ．ａｃ ＝ ５６１００／ＡＶ
で求められる。
It is also possible to form a water-insoluble film by ionic bond crosslinking. In this case, an aqueous solution or a hydrous alcohol solution containing a divalent or higher metal salt (for example, calcium phosphates, calcium lactate, etc.) is added to the shellac alcohol solution, applied to both sides of the metal foil, and dried. A crosslinking reaction proceeds and a film is formed. This reaction occurs at room temperature, but when heated at the time of drying or after drying, the crosslinking reaction by esterification also proceeds, so that the thermosetting property of the film can be further improved.
The alkali equivalent used for the divalent alkaline earth compound such as calcium and magnesium is an appropriate amount of 5 to 30% of the carboxy equivalent in the resin. If added in a large amount, the alcohol resin solution gels, making it difficult to apply to the surface of the metal foil. If the amount is too small, the crosslinking density is small and the pigment retention effect is insufficient.
The carboxy equivalent (Eq.ac) of the resin corresponds to the weight ratio with respect to one carboxyl group contained in the resin. From the acid value (AV, mg of KOH required to neutralize 100 g of resin), Formula I
(Formula I) Eq. ac = 56100 / AV
Is required.
本発明に係る樹脂としては、熱硬化性樹脂が好ましいが、製膜性、着色樹脂液の粘度、乾燥性、樹脂皮膜の柔軟性や粉砕性等を調整するために、ロジン等の熱可塑性樹脂成分を併用しても良い。
天然樹脂の代表例であるロジンの主成分は、アビエチン酸（融点１７５℃）であり、ロジン単独ではアルコールに溶ける。該アルコール溶液に、乳酸カルシウムを加え、乾燥して製膜された樹脂皮膜は、イオン結合で２分子が結合してアルコールに難溶になるが、架橋構造を有しない。従って、ロジンのカルシウム変性物やロジンとグリセリンのエステル化物（エステルガム）は、水及びアルコール中での着色色素の保持力が劣る。したがって、ロジン単独では用いることができないが、特性の改善を図るために、上述したシェラック等の樹脂と併用して用いてもよい。
As the resin according to the present invention, a thermosetting resin is preferable, but a thermoplastic resin such as rosin is used to adjust the film forming property, the viscosity of the colored resin liquid, the drying property, the flexibility and grindability of the resin film, and the like. You may use an ingredient together.
The main component of rosin, which is a typical example of natural resin, is abietic acid (melting point: 175 ° C.), and rosin alone is soluble in alcohol. A resin film formed by adding calcium lactate to the alcohol solution and drying to form a film is hardly soluble in alcohol because two molecules are bonded by ionic bonds, but does not have a crosslinked structure. Therefore, the calcium modified product of rosin and the esterified product (ester gum) of rosin and glycerin are inferior in retention of colored pigments in water and alcohol. Therefore, rosin cannot be used alone, but may be used in combination with the aforementioned resin such as shellac in order to improve the characteristics.
本発明に係る皮膜は、金属の光輝性を損なわない程度の透明性を有するものであればよく、完全な透明のみならず半透明であってもよい。このような皮膜は、塗料および塗膜の分野において、いわゆるクリヤー塗膜もしくはカラークリヤー塗膜として認識されている。 The film according to the present invention may be any film as long as it has transparency that does not impair the glitter of the metal, and may be not only completely transparent but also translucent. Such a coating is recognized as a so-called clear coating or color clear coating in the field of paints and coatings.
本発明に係る食用可能な着色色素とは、既存食品添加剤として認められている天然色素又は指定添加剤を意味する。天然色素がより好ましい。
天然色素として、例えば、ウコン色素、クチナシ黄色色素、ベニバナ黄色色素、カロテン色素、アナトー色素、トウガラシ色素、紅コウジ色素、コチニ―ル色素、ラック色素、クチナシ赤色素、ピートレッド、赤キャベツ色素、ブドウ果樹色素、ブドウ果皮色素、シソ色素、ベリー類色素、紫トウモロコシ色素、クロロフィル、クチナシ青色素、カカオ色素、イカスミ色素等が代表例として示され、これらは、好ましい形態として、粉末状、水、アルコール、含水アルコールの溶液又は分散液の１種又は２種以上の混合物として提供され、通常用いられている食用油、グリコール類等の分散剤、その他、分散助剤、酸化防止剤、更には酢酸エチル等の溶解助剤等、任意の食品添加剤を加えても良い。
指定添加剤として、食用赤色２号、食用赤色２号アルミニウムレーキ、食用赤色３号、食用赤色３号アルミニウムレーキ、食用赤色４０号、食用赤色４０号アルミニウムレーキ、食用赤色１０２号、食用赤色１０４号、食用赤色１０５号、食用赤色１０６号、食用黄色４号、食用黄色４号アルミニウムレーキ、食用黄色５号、食用黄色５号アルミニウムレーキ、食用緑色３号、食用緑色３号アルミニウムレーキ、食用青色１号、食用青色１号アルミニウムレーキ、食用青色２号、食用青色２号アルミニウムレーキ等の１種又は２種以上の色素の混合物を使用することができ、前述の天然色素と併用しても良い。
The edible colored pigment according to the present invention means a natural pigment or a designated additive that is recognized as an existing food additive. Natural pigments are more preferred.
Natural pigments include, for example, turmeric pigments, gardenia yellow pigments, safflower yellow pigments, carotene pigments, anato pigments, red pepper pigments, red koj pigments, cochineal pigments, lac pigments, gardenia red pigments, peat reds, red cabbage pigments, grapes Fruit tree pigments, grape skin pigments, perilla pigments, berry pigments, purple corn pigments, chlorophylls, gardenia blue pigments, cacao pigments, squid pigments, etc. are shown as representative examples, and these are preferably in the form of powder, water, alcohol Provided as a solution or a mixture of two or more hydrous alcohol solutions, and commonly used edible oils, glycols and other dispersants, other dispersion aids, antioxidants, and ethyl acetate You may add arbitrary food additives, such as dissolution aids.
As designated additives, Food Red No. 2, Food Red No. 2 Aluminum Lake, Food Red No. 3, Food Red No. 3 Aluminum Lake, Food Red No. 40, Food Red No. 40 Aluminum Lake, Food Red No. 102, Food Red No. 104 Edible red No. 105, edible red No. 106, edible yellow No. 4, edible yellow No. 4 aluminum rake, edible yellow No. 5, edible yellow No. 5 aluminum rake, edible green No. 3, edible green No. 3 aluminum rake, edible blue 1 No. 1, edible blue No. 1 aluminum lake, edible blue No. 2 and edible blue No. 2 aluminum lake can be used, or a mixture of two or more kinds of pigments can be used, and may be used in combination with the aforementioned natural pigments.
樹脂皮膜が上記着色色素を含む場合、銀箔、白金箔に適用すると、着色された、光輝性金属箔が得られる。金箔に適用すると、フリップフロップ性により、金箔本来の色と、着色による色を帯び、干渉色が見る角度で多彩に変化するため、意匠性、加飾性の優れた食用箔が提供出来る。 When the resin film contains the coloring pigment, a colored glittering metal foil is obtained when applied to silver foil or platinum foil. When applied to a gold foil, an edible foil having excellent design and decorating properties can be provided because of the flip-flop properties, the original color of the gold foil and the color resulting from the coloring change, and the interference color changes in various ways depending on the viewing angle.
本発明に係る製造方法として、上述の樹脂のアルコール溶液を、金属箔表面に塗布し、乾燥する方法が挙げられる。好ましい形態は、樹脂として熱硬化性樹脂を用い、乾燥時または乾燥後に加熱を行い、熱硬化性の皮膜を形成する方法である。
また、着色金属箔を形成する場合は、樹脂のアルコール溶液に、着色色素の粉末、あるいは着色色素のアルコール溶液、アルコール分散液、水溶液、水分散液から選択される着色剤溶液を添加し、溶解又は分散させることで、着色されたアルコール樹脂溶液とし、この溶液を、金属箔表面に塗布すればよい。
例えば、シェラックのアルコール溶液に、着色色素の粉末あるいは分散液を、ボールミル等の常用の分散手段で分散させてマスターバッチを調整し、適時、シェラック溶液に再分散して所望の着色シェラック溶液を得てもよい。
Examples of the production method according to the present invention include a method in which an alcohol solution of the above resin is applied to the surface of a metal foil and dried. A preferred embodiment is a method in which a thermosetting resin is used as the resin, and heating is performed during or after drying to form a thermosetting film.
In addition, when forming a colored metal foil, a colorant powder selected from a powder of a colorant or an alcohol solution, an alcohol dispersion, an aqueous solution, or an aqueous dispersion of a colorant is added to a resin alcohol solution and dissolved. Alternatively, a colored alcohol resin solution may be formed by dispersing, and this solution may be applied to the surface of the metal foil.
For example, a powder or dispersion of a coloring pigment is dispersed in an alcohol solution of shellac using a conventional dispersing means such as a ball mill to prepare a master batch, and redispersed in a shellac solution at appropriate times to obtain a desired colored shellac solution. May be.
金属箔の両面に樹脂皮膜を塗布する方法は、特に限定されないが、金属箔は非常に薄く破れやすいので、金属型枠に澱粉糊等食用可能な糊剤で貼り合わせ、浸漬塗布、乾燥（必要に応じて加熱）することで意匠性の優れた加飾用金属箔を得ることができる。
樹脂皮膜の厚みは、金属箔の種類、利用目的によって適宜調節すればよいが、通常、金属箔の厚みと同じ程度から１００倍程度迄の０．１μｍ〜５０μｍ程度、好ましくは、０．５μｍ〜１０μｍの範囲の厚みを金属箔の両面に設けることが好ましい。皮膜が薄すぎると、樹脂被覆の効果が得にくく、厚すぎると、食感や金属光輝性が悪くなる。
金属箔粉に加工して粉末として利用する場合は、皮膜の厚みを３μｍ以下にすると、金属光輝性の優れた加飾用金属箔粉が得られて好ましい。
The method of applying the resin film on both sides of the metal foil is not particularly limited, but the metal foil is very thin and easy to tear, so it is bonded to the metal mold with edible glue such as starch paste, dip coated, and dried (necessary) The metal foil for decoration which was excellent in the designability can be obtained by heating according to.
The thickness of the resin film may be appropriately adjusted depending on the type of metal foil and the purpose of use, but is usually about 0.1 μm to 50 μm, preferably about 0.5 μm to about 100 times the thickness of the metal foil. It is preferable to provide a thickness in the range of 10 μm on both sides of the metal foil. When the film is too thin, it is difficult to obtain the effect of resin coating, and when it is too thick, the texture and the metallic glitter are deteriorated.
When processing into metal foil powder and using it as a powder, it is preferable that the thickness of the film be 3 μm or less because a metal foil powder for decorating with excellent metal glitter can be obtained.
加熱により樹脂を硬化させる工程としては、通常利用される任意の加熱乾燥法が適用出来るが、熱風加熱乾燥方式が汎用されて便利である。更に、本発明では、金属箔に樹脂のアルコール溶液を塗布し、室温で乾燥させた後、誘導加熱（Induction Heating）装置で、後加熱硬化させても良い。尚、加熱温度は、雰囲気温度で設定できるが、赤外線放射温度計等で金属膜の表面温度を測定して補正するのが好ましい。 As the step of curing the resin by heating, any commonly used drying method can be applied, but a hot air heating drying method is widely used and convenient. Furthermore, in the present invention, an alcohol solution of a resin is applied to a metal foil, dried at room temperature, and then post-heat cured with an induction heating apparatus. In addition, although heating temperature can be set with atmospheric temperature, it is preferable to correct | amend by measuring the surface temperature of a metal film with an infrared radiation thermometer etc.
又、樹脂のアルコール溶液に、食用可能な防腐剤、酸化防止剤、分散安定剤、消泡剤等の常用されている助剤を加えても良い。
金属箔に塗布する、樹脂のアルコール溶液における樹脂濃度は、樹脂の種類、金属箔の種類、着色目的、着色する食材等の利用目的によって異なるが、通常、シェラック樹脂の場合は、７５重量％以下、好ましくは１０〜５０重量％である。樹脂の濃度が低すぎると、製膜性が乏しく、樹脂被覆効果が劣る。又、濃度が高すぎると、乾燥が早すぎ、均質な樹脂膜、平滑な樹脂膜が得にくく、又厚みの制御が困難となる。
In addition, auxiliaries such as edible preservatives, antioxidants, dispersion stabilizers and antifoaming agents may be added to the resin alcohol solution.
The resin concentration in the alcohol solution of the resin applied to the metal foil varies depending on the type of the resin, the type of the metal foil, the purpose of coloring, the purpose of use of the food to be colored, etc. , Preferably 10 to 50% by weight. If the resin concentration is too low, the film-forming property is poor and the resin coating effect is poor. On the other hand, if the concentration is too high, drying is too early, it is difficult to obtain a homogeneous resin film and a smooth resin film, and it becomes difficult to control the thickness.
樹脂に着色色素を添加して、金属箔の両面を着色樹脂皮膜で被覆する場合、着色色素は、樹脂１００部（重量部）に対し２００部以下、好ましくは１５０部以下、より好ましくは１００部〜２０部の量で用いる。樹脂に対して着色色素が多すぎると、金属箔の光輝性が乏しくなり、意匠性が劣るとともに、樹脂皮膜が脆くなりやすく、剥がれの原因になりやすい。
逆に、低濃度領域には、下限が無く、着色効果に乏しい超微量であっても、プラズモン色の干渉に対しては有効である。十分な着色効果を得るためには、樹脂１００部に対して着色色素を２０部以上とすることが好ましい。
When a coloring pigment is added to the resin and both surfaces of the metal foil are coated with a colored resin film, the coloring pigment is 200 parts or less, preferably 150 parts or less, more preferably 100 parts, relative to 100 parts (parts by weight) of the resin. Use in an amount of ~ 20 parts. When there are too many coloring pigment | dyes with respect to resin, while the brightness of metal foil becomes scarce and the design property is inferior, a resin film tends to become weak and it is easy to cause peeling.
On the other hand, there is no lower limit in the low density region, and even a very small amount having a poor coloring effect is effective for plasmon color interference. In order to obtain a sufficient coloring effect, the coloring pigment is preferably 20 parts or more with respect to 100 parts of the resin.
本発明に係る金属箔は、通常、１２ｃｍ角程度の正方形で得られる。本発明の加飾用金属箔は、箔そのままの形状でも使用できるが、飲食物の加飾には、通常、この金属箔を裁断または粉砕することによって得られた金属箔片（金属箔の小片）または金属箔粉を使用する。これらの金属箔片または金属箔粉も、上述した効果を有する。
金属箔片や金属箔粉の例として、上記金属箔を粗粉砕した切りまわし、篩等で粉砕、分級した粉末状の金属箔粉が挙げられ、切りまわし、金属粉では、色の異なる２種以上を混合することにより、意匠性、加飾性を高めることができる。
The metal foil according to the present invention is usually obtained in a square of about 12 cm square. Although the metal foil for decoration of the present invention can be used in the shape of the foil as it is, the metal foil piece obtained by cutting or crushing the metal foil is usually used for decoration of food and drink (small piece of metal foil). ) Or metal foil powder. These metal foil pieces or metal foil powders also have the effects described above.
Examples of metal foil pieces and metal foil powders include powdered metal foil powder obtained by roughly pulverizing the above metal foil, pulverized and classified with a sieve, etc. By mixing the above, the designability and decorating properties can be enhanced.
以下、実施例により本発明をより詳細に説明する。なお、「％」および「部」は特に記載しない限り、「重量％」および「重量部」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. “%” And “parts” mean “% by weight” and “parts by weight” unless otherwise specified.
［実施例１］
透明白ラック（漂白した透明のシェラック樹脂：軟化点７０℃、ＡＶ[酸価]６８、
Ｅｑ．ａｃ＝８２５）の２５％アルコール溶液（ラックグレース２５Ｅ、日本シェラック工業株式会社製）１００部に対し、ベニコウジ系赤色色素（モナスレッドＬＡ、５０％アルコール溶液、保土谷化学工業株式会社製）１０部を攪拌下で添加し、混合して着色樹脂溶液を得た。当該着色樹脂溶液におけるシェラック樹脂の濃度は２２．７％であり、着色色素の濃度は４．５％、シェラック樹脂と着色色素の固形分比（重量比）は１００：２０である。
次いで、金属製型枠（内のり１２０ｍｍ）に澱粉糊を塗布後、食用金箔（仲色：金／銀＝９０．９０／９．０９ 厚さ：０．１μｍ）を貼着、乾燥させた後、前述の着色樹脂溶液に浸漬することにより、金属箔の表面に着色樹脂溶液を塗布した後、１５０℃で５分間、加熱硬化させて、両面が熱硬化性の赤色の透明樹脂皮膜で被覆された、厚み２μｍの光輝性に優れた加飾用金属箔を得た。
[Example 1]
Transparent white rack (bleached transparent shellac resin: softening point 70 ° C., AV [acid value] 68,
Eq. ac = 825) 100 parts of 25% alcohol solution (Lac Grace 25E, manufactured by Nippon Shellac Industrial Co., Ltd.) 10 parts Benikouji red pigment (Mona Red LA, 50% alcohol solution, manufactured by Hodogaya Chemical Co., Ltd.) Were added with stirring and mixed to obtain a colored resin solution. The concentration of the shellac resin in the colored resin solution is 22.7%, the concentration of the colored pigment is 4.5%, and the solid content ratio (weight ratio) between the shellac resin and the colored pigment is 100: 20.
Next, after applying starch paste to a metal formwork (inner paste 120 mm), after sticking and drying edible gold foil (middle color: gold / silver = 90.90 / 9.09 thickness: 0.1 μm), After immersing in the colored resin solution described above, the colored resin solution was applied to the surface of the metal foil, and then heated and cured at 150 ° C. for 5 minutes, so that both surfaces were covered with a thermosetting red transparent resin film. A decorative metal foil having a thickness of 2 μm and excellent luster was obtained.
［実施例２］
ベニコウジ系赤色色素を添加しないアルコール溶液（すなわち、ラックグレース２５Ｅのみ）を使用した以外は、実施例１と同じ工程により、厚み２μｍの加飾用金属箔を得た。
[Example 2]
A decorative metal foil having a thickness of 2 μm was obtained by the same process as in Example 1 except that an alcohol solution (that is, only Rack Grace 25E) to which no red beige red pigment was added was used.
［比較例１，２］
加熱硬化を行わず、金属箔に塗布した樹脂溶液を室温で乾燥することによって、金属箔表面に皮膜を形成した以外は、実施例１、２と同じ工程により、厚み２μｍの金属箔を得た。
[Comparative Examples 1 and 2]
A metal foil having a thickness of 2 μm was obtained by the same process as in Examples 1 and 2 except that a film was formed on the surface of the metal foil by drying the resin solution applied to the metal foil at room temperature without performing heat curing. .
実施例１、２および比較例１、２によって製造した金属箔は、何れも原料の金属箔の仲色より赤味があった。
ベニコウジ系赤色色素を添加していない実施例２、比較例２の赤味は、金のプラズモン効果によるものと考えられ、実施例１、比較例１は、赤色色素の添加により、さらに赤味がかり、同じ金属箔から、色相の異なる赤色系金属箔が得られた。又、原料金属箔と比べて、粉砕及び手作業での取り扱いが容易であった。
The metal foils produced according to Examples 1 and 2 and Comparative Examples 1 and 2 were reddish than the neutral color of the starting metal foil.
The redness of Example 2 and Comparative Example 2 to which no red beige red pigment is added is considered to be due to the gold plasmon effect, and Example 1 and Comparative Example 1 are further reddish by the addition of the red pigment. From the same metal foil, a red metal foil having a different hue was obtained. Moreover, compared with raw material metal foil, it was easy to grind and handle by hand.
ただし、比較例１の金属箔は、実施例１の金属箔と異なり、室温で水に浸漬した際、赤色のにじみが観察された。製造した金属箔で実際に食品を加飾した場合の効果を調べるために、以下の実験を行った。
実施例１と比較例１の金属箔それぞれを星型に切り抜き、コーヒーゼリーの上にのせて冷蔵庫で保存した。１日後、実施例１の金属箔は、僅かに、星型の赤味がコーヒーゼリー表面に色移りしていたが、星形の外縁からのはみ出しは認められなかった。比較例１の金属箔は、星型の廻り約１ｍｍに赤色のにじみが認められた。
赤色色素を含まない実施例２と比較例２の金属箔について同じ実験を行ったところ、実施例２の金属箔は１日後も何ら変化しなかったが、比較例２の金属箔は若干軟化し、形状に若干の崩れが見られた。
However, the metal foil of Comparative Example 1 was different from the metal foil of Example 1 in that red bleeding was observed when immersed in water at room temperature. In order to investigate the effect of actually decorating food with the manufactured metal foil, the following experiment was conducted.
Each metal foil of Example 1 and Comparative Example 1 was cut into a star shape, placed on a coffee jelly, and stored in a refrigerator. One day later, in the metal foil of Example 1, the star-shaped redness was slightly transferred to the surface of the coffee jelly, but no protrusion from the outer periphery of the star shape was observed. In the metal foil of Comparative Example 1, red bleeding was observed about 1 mm around the star shape.
When the same experiment was performed on the metal foil of Example 2 and Comparative Example 2 that did not contain a red pigment, the metal foil of Example 2 did not change at all even after one day, but the metal foil of Comparative Example 2 was slightly softened. The shape was slightly collapsed.
色のにじみ、形状保持に関する効果の差は、加熱硬化させて形成したシェラック樹脂皮膜は架橋構造を有するが、室温で自然乾燥させて形成したシェラック樹脂皮膜は架橋構造を有さないことに起因すると考えられる。 The difference in the effects of color bleeding and shape retention is that the shellac resin film formed by heat curing has a crosslinked structure, but the shellac resin film formed by natural drying at room temperature does not have a crosslinked structure. Conceivable.
［実施例３］
実施例１のベニコウジ系赤色色素をクチナシ系青色色素（クリアーブルー７ＳＦ、８０％アルコール溶液、保土谷化学工業株式会社）２５部に変更して、着色樹脂溶液を調製し、仲色食用金箔を、水色食用金箔（金５９．７４／銀４０．２５ 厚さ０．１μｍ）に変えた以外は、実施例１と同じ工程により、厚さ、２．２μｍの光輝性に優れた食用金属箔を得た。
[Example 3]
By changing the red beige red pigment of Example 1 to 25 parts of gardenia blue pigment (Clear Blue 7SF, 80% alcohol solution, Hodogaya Chemical Co., Ltd.) to prepare a colored resin solution, Except for changing to a light blue edible gold foil (gold 59.74 / silver 40.25 thickness 0.1 μm), an edible metal foil having a thickness of 2.2 μm and excellent luster is obtained by the same process as in Example 1. It was.
得られた食用金属箔は正面から見ると光輝性の青色を呈したが、フリップフロップ性の効果で、箔を折り曲げたり、見る角度を変えると、水色食用金箔自体の金色が発現することがあり、多彩な色を示す金属箔が得られた。 The resulting edible metal foil had a glittering blue color when viewed from the front, but the effect of flip-flop could cause the gold color of the light blue edible gold foil to appear when the foil was folded or the viewing angle changed. A metal foil showing various colors was obtained.
［比較例３］
加熱硬化を行わず、金属箔に塗布した樹脂溶液を室温乾燥することによって、金属箔表面に皮膜を形成した以外は、実施例３と同じ方法により、青色の食用金属箔を得た。
[Comparative Example 3]
A blue edible metal foil was obtained by the same method as in Example 3 except that the resin solution applied to the metal foil was dried at room temperature without performing heat curing, thereby forming a film on the surface of the metal foil.
実施例３、比較例３で製造した食用金属箔を各々、３ｍｍの篩に通し、２〜４ｍｍの切り落とし食用金箔片を得た。
これらの食用金箔片を爪楊枝を用いてシャンペングラスに各々数片入れた。その後、グラスに、シャンペンを注いだ。
実施例３の食用金属箔は、シャンデリアに映え、青色を主体とした多彩な光輝性を示し、３時間程度放置した後も変化がなかったが、比較例３の食用金属箔では、青色色素が溶出し、原料の水色食用金箔が露出し、加飾効果を著しく毀損した。
Each of the edible metal foils produced in Example 3 and Comparative Example 3 was passed through a 3 mm sieve to obtain 2 to 4 mm cut-off edible gold foil pieces.
Several pieces of these edible gold foil pieces were put in champagne glasses using toothpicks. After that, champagne was poured into the glass.
The edible metal foil of Example 3 reflected on the chandelier and showed various glitters mainly composed of blue, and remained unchanged after being left for about 3 hours. However, in the edible metal foil of Comparative Example 3, the blue pigment was The gold-colored edible gold foil as a raw material was exposed, and the decorative effect was remarkably impaired.
［実施例４］
食用金属箔として食用銀箔（純度９９．９９％、厚み０．３μｍ）を用いた以外は、実施例３と同じ方法により、青色樹脂皮膜で両面が被覆された厚さ３μｍの光輝性を示す青色の加飾用食用銀箔を得た。
[Example 4]
A blue color having a brightness of 3 μm and coated on both sides with a blue resin film in the same manner as in Example 3 except that an edible silver foil (purity 99.99%, thickness 0.3 μm) was used as the edible metal foil. An edible silver foil for decoration was obtained.
［実施例５］
食用金属箔として実施例４と同じ食用銀箔を用いた他は、実施例２と同じ方法により、無着色の樹脂皮膜で両面が被覆された食用銀箔を得た。得られた食用銀箔はプラズモンにより、僅かに金色を感じさせる光輝性を示した。
[Example 5]
Except for using the same edible silver foil as in Example 4 as the edible metal foil, an edible silver foil having both surfaces coated with an uncolored resin film was obtained by the same method as in Example 2. The obtained edible silver foil showed a glittering sensation that made it feel slightly golden due to plasmons.
［比較例４、５］
加熱硬化を行わず、銀箔に塗布した樹脂溶液を室温乾燥することによって、銀箔表面に皮膜を形成した以外は、実施例４、５と同じ方法により、食用銀箔を得た。
ただし、比較例４の銀箔は、実施例４の銀箔と異なり、室温で水に浸漬した際、青色のにじみが観察された。
実施例４と比較例４の銀箔それぞれを星型に切り抜き、シャンペンジェリーの上にのせて冷蔵庫で保存した。１日後、実施例４の銀箔は、僅かに、星型の青味がシャンペンジェリー表面に色移りしていたが、はみ出しは認められなかった。比較例４の銀箔は、星型の廻り約１ｍｍに青色のにじみが認められた。
青色色素を含まない実施例５と比較例５の銀箔について同じ実験を行ったところ、実施例５の銀箔は１日後も何ら変化しなかったが、比較例５の銀箔は若干軟化し、形状に若干の崩れが見られた。
[Comparative Examples 4 and 5]
An edible silver foil was obtained by the same method as in Examples 4 and 5, except that the resin solution applied to the silver foil was dried at room temperature without performing heat curing, thereby forming a film on the surface of the silver foil.
However, unlike the silver foil of Example 4, the silver foil of Comparative Example 4 was observed to have blue bleeding when immersed in water at room temperature.
Each of the silver foils of Example 4 and Comparative Example 4 was cut into a star shape, placed on a champagne jelly, and stored in a refrigerator. One day later, in the silver foil of Example 4, the star-shaped bluish color was slightly transferred to the surface of the champagne jelly, but no protrusion was observed. In the silver foil of Comparative Example 4, blue bleeding was observed about 1 mm around the star shape.
When the same experiment was performed on the silver foils of Example 5 and Comparative Example 5 that did not contain a blue pigment, the silver foil of Example 5 did not change at all even after one day, but the silver foil of Comparative Example 5 was slightly softened into a shape. Some collapse was observed.
［実施例６］
実施例１で作成した着色樹脂溶液１１０ｇ（溶液中のシェラックの量：２５ｇ、カルボキシ当量０．０３当量）に、１０．４％乳酸カルシウム・５水和物（ＬＡＣと示す；分子量３０８、アルカリ当量数１５４）の３５％含水エタノール溶液を攪拌下、種々の割合で加え、以下、比較例１と同じ方法（室温乾燥）により、光輝性金属箔を得た。
このようにして得られた着色金属箔では、乳酸カルシウムのような金属塩を加えることにより、シェラック樹脂中にイオン結合による架橋構造が形成される。
なお、１０．４％乳酸カルシウム含水エタノール溶液（１００ｇ中ＬＡＣ、０．０６７５当量）１５部（０．０１０１当量[樹脂中のカルボキシ当量の３３％］）より高濃度の溶液を用いた場合は、着色樹脂溶液が凝集、ゲル化して、再分散不能であった。
[Example 6]
To 110 g of the colored resin solution prepared in Example 1 (the amount of shellac in the solution: 25 g, carboxy equivalent 0.03 equivalent), 10.4% calcium lactate pentahydrate (denoted LAC; molecular weight 308, alkali equivalent) A 35% hydrous ethanol solution of Formula 154) was added at various ratios with stirring, and thereafter, a glittering metal foil was obtained by the same method as in Comparative Example 1 (room temperature drying).
In the colored metal foil thus obtained, by adding a metal salt such as calcium lactate, a crosslinked structure due to ionic bonds is formed in the shellac resin.
In addition, when a higher concentration solution than 15 parts (0.0101 equivalent [33% of carboxy equivalent in the resin]) of 10.4% calcium lactate aqueous ethanol solution (LAC in 100 g, 0.0675 equivalent) was used, The colored resin solution was agglomerated and gelled and could not be redispersed.
得られた各種の金属箔について、実施例１同様の赤色色素の溶出試験を行ったところ、１０．４％の乳酸カルシウム含水エタノール溶液１部（０．６７５ミリ当量［樹脂中のカルボキシ当量の２．２％］）以下ではＬＡＣの添加効果は認められず、赤色色素の溶出を有意に抑制するためには、２．２部（０．００１５当量［樹脂中のカルボキシ当量の５％）以上必要であった。 The various metal foils thus obtained were subjected to the same red dye elution test as in Example 1. As a result, 1 part of a 10.4% calcium lactate-containing ethanol solution (0.675 milliequivalent [carboxy equivalent 2 in resin) .2%]) or less, the effect of adding LAC is not observed, and in order to significantly suppress the elution of the red pigment, 2.2 parts (0.0015 equivalent [5% of the carboxy equivalent in the resin) or more is required) Met.
［実施例７］
実施例６で調製した、乳酸カルシウムを添加した着色樹脂溶液について、実施例１同様、加熱硬化による皮膜形成を行ったところ、得られた金属箔は何れも耐水性に優れており、実施例１で製造した金属箔と同様、着色色素のにじみ出しを抑制した。
[Example 7]
About the colored resin solution which added calcium lactate prepared in Example 6, when the film formation by heat-hardening was performed like Example 1, all obtained metal foil was excellent in water resistance, and Example 1 As in the case of the metal foil produced in step 1, the bleeding out of the coloring pigment was suppressed.
［比較例６］
透明白ラックの２５％アルコール溶液を、ロジン（酸価１７０、軟化点７０℃）の２５％エタノール溶液（１００ｇ中、ロジン２５ｇ、カルボキシ当量０．０７５当量）に変更した以外は、実施例１と同様の方法で、着色樹脂溶液を調製し、以下、実施例６と同様の方法（乳酸カルシウム添加・室温乾燥）により、光輝性金属箔を得た。
実施例６と同様に、１０.４％乳酸カルシウム含水エタノール溶液（１００ｇ中ＬＡＣ、０．０６７５当量）４０部（０．０２７当量、樹脂中のカルボキシ当量の３６％）より高濃度の含水エタノール溶液を用いた場合は、着色樹脂溶液が凝集、ゲル化して、再分散不能であった。
得られた金属箔は、何れも着色色素の耐水固定性が悪かった。これは、ロジンが、金属塩を加えても、架橋構造を形成する性質を有していないためと考えられる。
[Comparative Example 6]
Example 1 with the exception that the 25% alcohol solution of the transparent white rack was changed to a 25% ethanol solution of rosin (acid number 170, softening point 70 ° C.) (in 100 g, rosin 25 g, carboxy equivalent 0.075 equivalent). A colored resin solution was prepared in the same manner, and thereafter a glittering metal foil was obtained by the same method as in Example 6 (calcium lactate addition and room temperature drying).
Similar to Example 6, a 10.4% calcium lactate aqueous ethanol solution (LAC in 100 g, 0.0675 equivalent) 40 parts (0.027 equivalent, 36% of the carboxy equivalent in the resin) higher concentration aqueous ethanol solution When was used, the colored resin solution was aggregated and gelled and could not be redispersed.
Each of the obtained metal foils had poor water-fixing resistance of the coloring pigment. This is considered because rosin does not have a property of forming a crosslinked structure even when a metal salt is added.
［比較例７］
比較例６で調製した着色樹脂溶液（乳酸カルシウムを添加したロジン溶液）を塗布、室温乾燥させた金属箔を更に、１５０℃で５分間、加熱したが、着色色素の耐水固定性は改善されなかった。これは、ロジンが加熱しても、架橋構造を形成する性質を有さないためと考えられ、架橋構造の有意性が確認された。
[Comparative Example 7]
The metal foil coated with the colored resin solution prepared in Comparative Example 6 (rosin solution added with calcium lactate) and dried at room temperature was further heated at 150 ° C. for 5 minutes, but the water-fixing resistance of the colored pigment was not improved. It was. This is considered to be because the rosin does not have the property of forming a crosslinked structure even when heated, and the significance of the crosslinked structure was confirmed.
実施例１〜７および比較例１〜７の製造条件と特性を表２にまとめる。
［実施例８〜１１および比較例８〜１１］
食用銀箔（純度９９．９９％、厚み０．３μｍ）を用い、着色色素、シェラック濃度、加熱硬化条件を変化して食用金属箔を製造し、特性を調べた。製造条件と特性を表３に示す。なお、表３において、皮膜の厚みは、箔両面の皮膜の厚みの合計ではなく、箔片面の皮膜の厚みを示す。
[Examples 8 to 11 and Comparative Examples 8 to 11]
Using edible silver foil (purity 99.99%, thickness 0.3 μm), edible metal foil was produced by changing the coloring pigment, shellac concentration, and heat curing conditions, and the characteristics were examined. Table 3 shows the manufacturing conditions and characteristics. In Table 3, the thickness of the coating indicates not the total thickness of the coating on both sides of the foil but the thickness of the coating on one side of the foil.
比較例８〜１１は着色樹脂溶液を加熱せず、室温乾燥した以外は、実施例８〜１１と同じ条件で製造したものである。また、表中の着色剤/樹脂は固形分比（重量比）である。
尚、耐水性、耐ワイン性、光輝性、加飾性は、以下に示す方法で評価した。
耐水性は、０．１ｇの試料を１０ｍｌのイオン交換水に浸漬した際、３時間以内で色素が溶出したものを耐水性「なし」、２４時間以上変化しなかったものを耐水性「良好」と評価した。
耐ワイン性は、０．１ｇの試料を１０ｍｌの白ワインに浸漬した際、１時間以内で色素が溶出したものを耐ワイン性「なし」、２４時間以上変化しなかったものを耐ワイン性「良好」と評価した。
光輝性は試料を目視した際の金属光輝性（銀箔特有の意匠性）、加飾性は試料を食材に加えた時の意匠性について評価した。
Comparative Examples 8 to 11 were produced under the same conditions as in Examples 8 to 11 except that the colored resin solution was not heated and dried at room temperature. The colorant / resin in the table is a solid content ratio (weight ratio).
In addition, water resistance, wine resistance, luster, and decorating property were evaluated by the following methods.
As for water resistance, when 0.1 g of sample was immersed in 10 ml of ion-exchanged water, the dye eluted within 3 hours was “None”, and the sample that was not changed over 24 hours was “Good”. It was evaluated.
As for the wine resistance, when 0.1 g of sample is immersed in 10 ml of white wine, the colorant eluted within 1 hour is “none”, and the sample that has not changed for more than 24 hours is “wine resistance”. It was evaluated as “good”.
The glitter was evaluated with respect to the metallic glitter when the sample was visually observed (design property peculiar to silver foil), and the decorativeness was evaluated with respect to the design when the sample was added to the foodstuff.
［実施例１２］
実施例８〜１１の食用銀箔各々を、先ず５０メッシュの篩を通過させたのち、１００メッシュの篩残で篩分けすることにより、０．５〜２ｍｍの光輝性の銀箔粉末を得た。
各々の粉末及び、任意に混合した混合粉末は優れた光輝性を示した。
[Example 12]
Each of the edible silver foils of Examples 8 to 11 was first passed through a 50-mesh sieve and then sieved with a 100-mesh sieve residue to obtain a glittering silver foil powder of 0.5 to 2 mm.
Each powder and the mixed powder arbitrarily mixed showed excellent glitter.
［比較例１２］
比較例８〜１１の食用銀箔を実施例１２と同様の方法で篩処理した。比較例の銀箔を使用した場合、最初の５０メッシュの篩処理でダマになりやすく、続く、１００メッシュの篩処理でも分級出来ず、熱可塑性皮膜の欠点を示し、意匠性、加飾性が劣っていた。
[Comparative Example 12]
The edible silver foils of Comparative Examples 8 to 11 were sieved by the same method as in Example 12. When the silver foil of the comparative example is used, the initial 50 mesh sieving process is likely to become lumpy, and the subsequent 100 mesh sieving process cannot be classified, showing the defects of the thermoplastic film, and the design and decorating properties are inferior. It was.
［実施例１３］
定法の葛きりの製法に従い、市販の葛粉を水に溶かしてから加熱した段階で、実施例１２で得られた各種の食用銀箔粉を添加、分散後、容器に流し込み冷却、固化した。
次いで、固化したゲルを熱湯にくぐらせ、透明な葛きりを得た。
これらの葛きりは、内部に光輝性の銀箔粉が散らばった外観を有し、意匠性に優れていた。また、この葛きりを、３日間冷蔵保存したが、食用銀箔粉の色の変化は認められなかった。
[Example 13]
According to a conventional kuzukuri manufacturing method, commercially available kuzu powder was dissolved in water and heated, and then various edible silver foil powders obtained in Example 12 were added, dispersed, poured into a container, cooled and solidified.
Next, the solidified gel was passed through hot water to obtain a clear knot.
These twists had an appearance in which glittering silver foil powder was scattered inside, and were excellent in design. Moreover, although this kudari was refrigerated for 3 days, no change in the color of the edible silver foil powder was observed.
［比較例１３］
比較例１２で得られた各種の銀箔粉を用いた以外は、実施例１３と同じ方法で葛きりを製造した。比較例１２の銀箔粉は、葛液の冷却、固化の段階から、色素のにじみが認められ、出来あがった葛きりは、全体に着色色素が広がり、意匠性が劣っていた。
[Comparative Example 13]
Kazukuri was produced in the same manner as in Example 13 except that various silver foil powders obtained in Comparative Example 12 were used. In the silver foil powder of Comparative Example 12, bleeding of the pigment was observed from the stage of cooling and solidification of the kudzu liquid, and the finished krush was inferior in design properties because the colored pigment spread throughout.
［実施例１４］
実施例１２で得られた各種の銀箔粉をワイングラスに少量入れ、白ワインを注いだ。注がれた白ワインは、銀箔粉により多彩な光輝性の雰囲気を醸し出し、３時間経過後も意匠性に変化は見られなかった。
[Example 14]
A small amount of the various silver foil powders obtained in Example 12 was placed in a wine glass, and white wine was poured. The poured white wine produced a variety of glittering atmosphere with silver foil powder, and no change in design was observed after 3 hours.
［比較例１４］
比較例１２で得られた各種の銀箔粉をワイングラスに少量入れ、白ワインを注いだ。しばらくすると、ワインに着色が見られ、シェラック皮膜が溶解し、原料銀箔粉がグラスの底に沈着し、加飾効果は認められなかった。
[Comparative Example 14]
A small amount of the various silver foil powders obtained in Comparative Example 12 was placed in a wine glass, and white wine was poured. After a while, the wine was colored, the shellac film dissolved, the raw silver foil powder was deposited on the bottom of the glass, and no decorative effect was observed.
Claims (9)
前記皮膜が、シェラック樹脂を架橋させることによって形成された、熱硬化性または軟化点６０℃以上の樹脂被膜であり、水に不溶性で透明または半透明であることを特徴とする、加飾用食用金属箔。 An edible metal foil for decorating that exhibits metallic glitter, which is formed by coating both sides of an edible metal foil with a colorless or colored film,
The coating was formed by crosslinking a shellac resin, a thermosetting or softening point 60 ° C. above the resin film, characterized in that it is a transparent or semitransparent light insoluble in water, decorative Edible metal foil.
食用可能な金属箔の両面に、シェラック樹脂を含むアルコール溶液を塗布する工程、及び
加熱により、前記シェラック樹脂を架橋させて、前記金属箔の両面に熱硬化性の樹脂皮膜を形成する工程
を含むことを特徴とする、加飾用食用金属箔の製造方法。 A method for producing a decorative edible metal foil exhibiting metallic glitter,
A step of applying an alcohol solution containing shellac resin on both surfaces of the edible metal foil, and a step of crosslinking the shellac resin by heating to form a thermosetting resin film on both surfaces of the metal foil. The manufacturing method of the edible metal foil for decoration characterized by the above-mentioned.
食用可能な金属箔の両面に、シェラック樹脂と２価以上の金属塩とを含むアルコール溶液を塗布する工程、及び
前記溶液を乾燥することにより、前記シェラック樹脂をイオン結合により架橋させて、前記金属箔の両面に、軟化点６０℃以上の樹脂皮膜を形成する工程
を含むことを特徴とする、加飾用食用金属箔の製造方法。 A method for producing a decorative edible metal foil exhibiting metallic glitter,
A step of applying an alcohol solution containing shellac resin and a divalent or higher metal salt on both surfaces of the edible metal foil, and drying the solution to crosslink the shellac resin by ionic bonding, thereby The manufacturing method of the edible metal foil for decorating characterized by including the process of forming the resin film of the softening point 60 degreeC or more on both surfaces of foil.
Wherein the metal foil, gold, characterized in that it is a noble metal foil is selected from the group consisting of silver and platinum A process according to any one of claims 6-8.
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