JP4807762B2 - Chitin emulsion and method for producing the same - Google Patents
Chitin emulsion and method for producing the same Download PDFInfo
- Publication number
- JP4807762B2 JP4807762B2 JP2010540258A JP2010540258A JP4807762B2 JP 4807762 B2 JP4807762 B2 JP 4807762B2 JP 2010540258 A JP2010540258 A JP 2010540258A JP 2010540258 A JP2010540258 A JP 2010540258A JP 4807762 B2 JP4807762 B2 JP 4807762B2
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- Prior art keywords
- chitin
- oil
- slurry
- emulsion
- solvent
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は、キチン乳化物、より詳細には、アセチル化度が高く、かつ、高分子量のキチンを含有する乳化物およびその製造方法に関する。 The present invention relates to a chitin emulsion, more specifically, an emulsion containing a high degree of acetylation and high molecular weight chitin and a method for producing the same.
キチンは、カニやエビ等の甲殻類の殻、昆虫の表皮、キノコ等の細菌細胞壁から得られる天然ムコ多糖類であって、地球上に大量に存在する生物資源である。このようなキチンは、保湿性、生理活性、生体適合性等、様々な優れた特性を有することが明らかとなってきた。このため、キチンの優れた特性を、繊維、フィルム、化粧品、食品、医薬、医用材料等の分野に利用するために、多くの研究がなされている。 Chitin is a natural mucopolysaccharide obtained from crustacean shells such as crabs and shrimp, insect epidermis, and bacterial cell walls such as mushrooms, and is a biological resource that exists in large quantities on the earth. Such chitin has been found to have various excellent properties such as moisture retention, physiological activity, and biocompatibility. For this reason, many studies have been made in order to utilize the excellent characteristics of chitin in the fields of fibers, films, cosmetics, foods, medicines, medical materials and the like.
しかしながら、キチンは、その化学構造に由来する強固な水素結合によって、硬い結晶構造を形成しているため、難溶性を示すことが知られている。この難溶性のため、キチンを溶解または良分散させた溶液または分散体を形成することができず、その利用分野は、キチンの粉体を基材中へ物理的に練り込んで成形体とすることによる用途等、極めて限定されたものであった。 However, chitin is known to exhibit poor solubility because it forms a hard crystal structure due to a strong hydrogen bond derived from its chemical structure. Due to this poor solubility, it is impossible to form a solution or dispersion in which chitin is dissolved or well dispersed, and the application field thereof is to physically knead chitin powder into a substrate to form a molded body. It was extremely limited in use.
本発明者らは、上記のように難溶性であるキチンを溶媒中に溶解または良分散させることができれば、キチンの上記優れた特性の利用が容易となることに着眼して鋭意検討を行ったところ、アルコール（特にメタノール）とハロゲン化カルシウム塩またはハロゲン化マグネシウム塩（特に塩化カルシウム二水塩）とを含んでなる特定の溶媒を用いると、キチンを溶解させることができることを見出した（特許文献１および非特許文献１）。 The inventors of the present invention have made extensive studies by paying attention to the fact that the above-mentioned excellent characteristics of chitin can be easily used if chitin, which is hardly soluble as described above, can be dissolved or well dispersed in a solvent. However, it has been found that chitin can be dissolved by using a specific solvent comprising alcohol (particularly methanol) and a calcium halide salt or magnesium halide salt (particularly calcium chloride dihydrate) (Patent Literature). 1 and Non-Patent Document 1).
その一方、これまでキチンは、その難溶性のため、キチンを脱アセチル化してアセチル化度を７０％未満にするか、キチンを分子量２,０００未満のオリゴマーまたはＮ−アセチルグルコサミンまで加水分解するか、およびキチンを修飾しなければ、乳化することができなかった（特許文献１〜４）。すなわち、これまでは、アセチル化度が高く（例えば、７０％以上）、かつ、高分子量（例えば、重量平均分子量２．３×１０３以上）のキチンをそのままで乳化することはできなかった。
したがって、アセチル化度が高く、かつ、高分子量のキチンをそのままで簡便に乳化する方法およびその乳化物が必要とされていた。
Therefore, a method for easily emulsifying high molecular weight chitin with a high degree of acetylation as it is and an emulsion thereof have been required.
本発明の課題は、アセチル化度が高く、かつ、高分子量のキチンを含有する乳化物、および該乳化物を簡便に製造する方法を提供することである。 An object of the present invention is to provide an emulsion having a high degree of acetylation and containing high molecular weight chitin, and a method for easily producing the emulsion.
本発明者らは、上記課題を解決するために鋭意検討した結果、アセチル化度が高く、かつ、高分子量のキチンを特定の溶媒を用いて溶解させて溶液とした後、次いで、必要に応じて該溶媒を他の溶媒に置換して懸濁物（スラリー）とした後、これらの溶媒に溶解しない溶媒と界面活性剤とを混合することにより、キチンを脱アセチル化、加水分解および修飾することなく、キチンを含有する乳化物を簡便に製造することができることを見出し、本発明を完成させるに至った。
すなわち、本発明には以下のものが含まれる。
〔１〕（ａ）アセチル化度７０％以上、かつ、重量平均分子量２．３×１０３以上であるキチンと、（ｂ）水性溶媒と、（ｃ）油性溶媒と、（ｄ）界面活性剤とを含んでなる、乳化物。
〔２〕界面活性剤の配合量が、水性溶媒１重量部に対して０．０００５重量部〜０．０５重量部である、上記〔１〕に記載の乳化物。
〔３〕油性溶媒の配合量が、水性溶媒１重量部に対して０．１重量部〜１０重量部である、上記〔１〕または〔２〕に記載の乳化物。
〔４〕乳化物中の分散体の粒径が５０ｎｍ〜５００μｍである、上記〔１〕に記載の乳化物。
〔５〕界面活性剤が、モノグリセリド、有機酸モノグリセリド、レシチン、キラヤサポニンおよびラウリル硫酸ナトリウムから選択される、上記〔１〕に記載の乳化物。
〔６〕有機酸モノグリセリドがジアセチル酒石酸モノグリセリドである、上記〔５〕に記載の乳化物。
〔７〕油性溶媒が、月見草油、杏仁油、スイートアーモンド油、ココナッツオイルおよび大豆油から選択される、上記〔１〕に記載の乳化物。
〔８〕（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液に、界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法。
〔９〕（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法。
〔１０〕（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに、親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
（４）親水性溶媒和キチンスラリーに界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法。
〔１１〕（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに、親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
（４）親水性溶媒和キチンスラリーに、親水性溶媒に溶解する油性溶媒を添加し、親水性溶媒和キチンスラリーに含まれる親水性溶媒を該油性溶媒で置換して、油性溶媒和キチンスラリーを得る工程と、
（５）油性溶媒和キチンスラリーに界面活性剤および水性溶媒を混合する工程と
を含む、キチン乳化物の製造方法。As a result of intensive studies to solve the above problems, the present inventors have found that a high degree of acetylation and high molecular weight chitin is dissolved in a specific solvent to form a solution, and then as necessary. The solvent is replaced with another solvent to form a suspension (slurry), and then the chitin is deacetylated, hydrolyzed and modified by mixing a solvent that does not dissolve in these solvents and a surfactant. Without finding out, it was found that an emulsion containing chitin can be easily produced, and the present invention has been completed.
That is, the present invention includes the following.
[1] (a) Chitin having a degree of acetylation of 70% or more and a weight average molecular weight of 2.3 × 10 3 or more, (b) an aqueous solvent, (c) an oily solvent, and (d) a surfactant. An emulsion comprising
[2] The emulsion according to [1], wherein the amount of the surfactant is 0.0005 parts by weight to 0.05 parts by weight with respect to 1 part by weight of the aqueous solvent.
[3] The emulsion according to [1] or [2], wherein the amount of the oily solvent is 0.1 to 10 parts by weight with respect to 1 part by weight of the aqueous solvent.
[4] The emulsion according to [1] above, wherein the particle size of the dispersion in the emulsion is 50 nm to 500 μm.
[5] The emulsion according to [1] above, wherein the surfactant is selected from monoglyceride, organic acid monoglyceride, lecithin, quillajasaponin and sodium lauryl sulfate.
[6] The emulsion according to [5], wherein the organic acid monoglyceride is diacetyltartaric acid monoglyceride.
[7] The emulsion according to [1] above, wherein the oily solvent is selected from evening primrose oil, apricot kernel oil, sweet almond oil, coconut oil, and soybean oil.
[8] (1) A step of dissolving chitin in a solvent comprising an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) A method for producing a chitin emulsion, comprising a step of mixing a surfactant and an oily solvent with a chitin solution.
[9] (1) A step of dissolving chitin in a solvent comprising an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) A method for producing a chitin emulsion, comprising a step of mixing a surfactant and an oily solvent with a hydrated chitin slurry.
[10] (1) A step of dissolving chitin in a solvent comprising an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) adding a hydrophilic solvent to the hydrated chitin slurry, replacing water molecules contained in the hydrated chitin slurry with the hydrophilic solvent, and obtaining a hydrophilic solvated chitin slurry;
(4) A method for producing a chitin emulsion, comprising a step of mixing a surfactant and an oily solvent with a hydrophilic solvated chitin slurry.
[11] (1) A step of dissolving chitin in a solvent comprising an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) adding a hydrophilic solvent to the hydrated chitin slurry, replacing water molecules contained in the hydrated chitin slurry with the hydrophilic solvent, and obtaining a hydrophilic solvated chitin slurry;
(4) An oily solvent that dissolves in the hydrophilic solvent is added to the hydrophilic solvated chitin slurry, and the hydrophilic solvent contained in the hydrophilic solvated chitin slurry is replaced with the oily solvent to obtain an oily solvated chitin slurry. Obtaining a step;
(5) A method for producing a chitin emulsion, comprising a step of mixing a surfactant and an aqueous solvent in an oily solvated chitin slurry.
本発明のキチン乳化物は、アセチル化度が高く、かつ、高分子量のキチンを含有するため、キチンが適用される化粧品分野、食品分野、医療分野等に直接的かつ好適に適用することができる。さらに、本発明のキチン乳化物によれば、低粘度であるため、スプレー成形により多孔性フィルム等のキチン成形品を製造することができ、或いは直接患部にスプレーして治癒効果を得ることができる。
また、本発明のキチン乳化物の製造方法によれば、これまで得ることができなかった、アセチル化度が高く、かつ、高分子量のキチンを含有する乳化物を、様々な溶媒中に溶解または懸濁したキチンから簡便に製造することができる。Since the chitin emulsion of the present invention has a high degree of acetylation and contains high molecular weight chitin, it can be directly and suitably applied to the cosmetics field, food field, medical field, etc. to which chitin is applied. . Furthermore, according to the chitin emulsion of the present invention, since it has a low viscosity, a chitin molded product such as a porous film can be produced by spray molding, or a healing effect can be obtained by spraying directly on the affected area. .
In addition, according to the method for producing a chitin emulsion of the present invention, an emulsion having a high degree of acetylation and containing high molecular weight chitin, which has not been obtained so far, is dissolved or dissolved in various solvents. It can be easily produced from suspended chitin.
本発明における「乳化」とは、互いに溶け合わない２種類の液体を激しくかき混ぜた際に、一方の液体がもう一方の液体中に細かい粒子となって分散している状態を意味し、および本発明における「乳化物」とは、乳化状態を室温（２０℃〜３０℃）、静置条件下、少なくとも３０日間保持できるものを意味する。 “Emulsification” in the present invention means a state in which one liquid is dispersed as fine particles in the other liquid when two kinds of liquids that do not dissolve each other are vigorously stirred. The “emulsion” in the invention means an emulsion that can be kept at room temperature (20 ° C. to 30 ° C.) and at rest for at least 30 days.
本発明におけるキチンは、一般に、カニやエビ等の甲殻類の殻、昆虫の表皮、イカ等の骨格、キノコ等の細菌細胞壁から得られる多糖類（ポリＮ−アセチル−Ｄ−グルコサミン）であって、通常は、粉体の性状を有している。本発明では、市販されている任意のキチンを使用することができ、微生物を利用して製造されたものであってもよい。また、キトサンをＮ−アセチル化した再生キチンであってもよい。さらに、α型およびβ型を含むいかなる立体構造を有するものであってもよい。 The chitin in the present invention is generally a polysaccharide (poly N-acetyl-D-glucosamine) obtained from shells of crustaceans such as crabs and shrimps, insect epidermis, skeletons such as squid, and bacterial cell walls such as mushrooms. Usually, it has powder properties. In the present invention, any commercially available chitin can be used, and it may be produced using a microorganism. Moreover, the reproduction | regeneration chitin which carried out N-acetylation of chitosan may be sufficient. Further, it may have any three-dimensional structure including α type and β type.
本発明におけるキチンのアセチル化度は、７０％以上、好ましくは８５％以上、より好ましくは９５％以上、特に好ましくは９８％以上である。当該アセチル化度は、最終生成物の用途に応じて適宜選択すればよい。
上記キチンのアセチル化度の値は、２ｍｏｌ／ｌの塩酸にて処理されたキチンを、０．１ｍｏｌ／ｌのＮａＯＨにて中和滴定することによって決定される値である。The acetylation degree of chitin in the present invention is 70% or more, preferably 85% or more, more preferably 95% or more, and particularly preferably 98% or more. What is necessary is just to select the said acetylation degree suitably according to the use of a final product.
The value of the degree of acetylation of chitin is a value determined by neutralizing and titrating chitin treated with 2 mol / l hydrochloric acid with 0.1 mol / l NaOH.
本発明におけるキチンの重量平均分子量は、２．３×１０３以上、好ましくは５×１０３以上、より好ましくは１×１０４〜５×１０６、特に好ましくは５×１０４〜５×１０５である。当該重量平均分子量は、最終生成物の用途に応じて適宜選択すればよい。
上記キチンの重量平均分子量の値は、後述する粘度法によって決定される値である。The weight average molecular weight of chitin in the present invention is 2.3 × 10 3 or more, preferably 5 × 10 3 or more, more preferably 1 × 10 4 to 5 × 10 6 , and particularly preferably 5 × 10 4 to 5 × 10. 5 . What is necessary is just to select the said weight average molecular weight suitably according to the use of a final product.
The value of the weight average molecular weight of the chitin is a value determined by a viscosity method described later.
本発明におけるキチンは、タンパク質に起因する抗原抗体反応等の問題を避けることにより安全性を向上させる観点から、原料由来のタンパク質ができるだけ除去されているものが好ましい。具体的には、キチン中のタンパク質含量（アミノ酸含量として算出）が０．４重量％以下、好適には０．１重量％以下、より好適には０．０１重量％以下であることが好ましい。
上記キチン中のタンパク質含量（アミノ酸含量）の値は、アミノ酸１８種（リジン、ヒスチジン、フェニルアラニン、ロイシン、イソロイシン、メチオニン、バリン、スレオニン、トリプトファン、アルギニン、チロシン、アラニン、グリシン、プロリン、グルタミン酸、セリン、アスパラギン酸、シスチン）をアミノ酸自動分析法および高速液体クロマトグラフ法によって測定することによって決定される値である。From the viewpoint of improving safety by avoiding problems such as antigen-antibody reaction caused by proteins, chitin in the present invention is preferably one from which raw material-derived proteins are removed as much as possible. Specifically, the protein content (calculated as amino acid content) in chitin is 0.4% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less.
The protein content (amino acid content) in the chitin is 18 amino acids (lysine, histidine, phenylalanine, leucine, isoleucine, methionine, valine, threonine, tryptophan, arginine, tyrosine, alanine, glycine, proline, glutamic acid, serine, Aspartic acid, cystine) is a value determined by measuring by an amino acid automatic analysis method and a high performance liquid chromatograph method.
本発明における水性溶媒は、キチン、界面活性剤および油性溶媒と組み合わさって、本願発明の乳化物を形成できるものであり、例えば、水、親水性溶媒等が挙げられる。
上記親水性溶媒としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、イソブチルアルコール、２−ブタノール、ｔ−ブタノール、アリルアルコール等の一価アルコール、エチレングリコール、プロピレングリコール、グリセリン、ブチレングリコール、ジプロピレングリコール等の多価アルコール、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルアセトアミド（ＤＭＡｃ）等が挙げられるが、これらに限定されない。
なかでも、コストの点から、水、一価アルコール（特にメタノール、エタノール）等が好ましい。The aqueous solvent in the present invention can form the emulsion of the present invention in combination with chitin, a surfactant and an oily solvent, and examples thereof include water and hydrophilic solvents.
Examples of the hydrophilic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, t-butanol, monohydric alcohol such as allyl alcohol, ethylene glycol, propylene glycol, Examples include, but are not limited to, polyhydric alcohols such as glycerin, butylene glycol, and dipropylene glycol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide (DMAc).
Of these, water, monohydric alcohol (particularly methanol, ethanol) and the like are preferable from the viewpoint of cost.
本発明における界面活性剤は、特に限定されず、乳化物に使用される他の材料（キチン、水性溶媒、油性溶媒等）の種類および量、得られる乳化物の用途等に応じて既知の界面活性剤から適宜選択することができ、その例としては、モノグリセリド（１分子のグリセリンに対して１分子の脂肪酸がエステル結合したもの、グリセリンモノ脂肪酸エステル）、有機酸モノグリセリド（上記モノグリセリドに有機酸が１〜２個エステル結合したもの、例えばジアセチル酒石酸モノグリセリド）、レシチン、キラヤサポニン、ラウリル硫酸ナトリウム（ドデシル硫酸ナトリウム、ＳＤＳ）、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレン脂肪酸エステル、ポリグリセリン脂肪酸エステル、分子鎖アルキルベンゼン・スルホン酸塩、アルキル硫酸塩、油脂硫酸エステル塩、ポリオキシエチレン・アルキルエーテル・リン酸塩、ポリオキシエチレン・アルキルフェニルエーテル・リン酸塩、グリセリン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸ポリエチレングリコール、脂肪酸ポリオキシエチレンソルビタン、脂肪酸アルカノールアミド、芳香族ポリグリコールエーテル等が挙げられる。
なかでも、最終生成物の用途が人に対するものが想定されること、および汎用性の観点から、モノグリセリド、有機酸モノグリセリド、レシチン、キラヤサポニン、ラウリル硫酸ナトリウム（ＳＤＳ）等を使用することが好ましい。The surfactant in the present invention is not particularly limited, and is a known interface depending on the type and amount of other materials (chitin, aqueous solvent, oily solvent, etc.) used in the emulsion, use of the obtained emulsion, and the like. The active agent can be appropriately selected, and examples thereof include monoglycerides (one molecule of fatty acid ester-bonded to one molecule of glycerin, glycerin monofatty acid ester), organic acid monoglyceride (the above monoglyceride has an organic acid) One or two ester-linked ones such as diacetyl tartaric acid monoglyceride, lecithin, quillajasaponin, sodium lauryl sulfate (sodium dodecyl sulfate, SDS), sucrose fatty acid ester, sorbitan fatty acid ester, propylene fatty acid ester, polyglycerin fatty acid ester, molecule Chain alkylbenzene sulfonate, Rulkisulfate, Fatty acid sulfate ester salt, Polyoxyethylene / alkyl ether / phosphate, Polyoxyethylene / alkylphenyl ether / phosphate, Glycerin fatty acid ester, Polyoxyethylene alkyl ether, Polyoxyethylene alkylphenyl ether, Fatty acid Examples include polyethylene glycol, fatty acid polyoxyethylene sorbitan, fatty acid alkanolamide, and aromatic polyglycol ether.
Among these, it is preferable to use monoglyceride, organic acid monoglyceride, lecithin, quillajasaponin, sodium lauryl sulfate (SDS), etc. from the viewpoint that the use of the final product is assumed for humans and versatility.
本発明の乳化物における界面活性剤の配合量は、水性溶媒（本発明の乳化物中に含まれる全てのもの）１重量部に対して、好ましくは０．０００５重量部〜０．０５重量部、より好ましくは０．０１重量部〜０．０３重量部である。界面活性剤の配合量が水性溶媒１重量部に対して０．０００５重量部未満の場合、乳化が生じず、溶液が分離するおそれがある。その一方、本来、界面活性剤は乳化物の不純物であるため、その量は少ない方がよく、水性溶媒１重量部に対して、０．０５重量部を超えると乳化物に対する不純物の許容量を超えるおそれがある。 The blending amount of the surfactant in the emulsion of the present invention is preferably 0.0005 parts by weight to 0.05 parts by weight with respect to 1 part by weight of the aqueous solvent (all of those contained in the emulsion of the present invention). More preferably, it is 0.01 part by weight to 0.03 part by weight. When the blending amount of the surfactant is less than 0.0005 parts by weight relative to 1 part by weight of the aqueous solvent, emulsification does not occur and the solution may be separated. On the other hand, since surfactants are inherently impurities in emulsions, it is better that the amount is small. If the amount exceeds 0.05 parts by weight with respect to 1 part by weight of the aqueous solvent, the allowable amount of impurities in the emulsion is increased. There is a risk of exceeding.
本発明における油性溶媒は、特に限定されず、乳化物に使用される他の材料（キチン、界面活性剤等）の種類および量、得られる乳化物の用途等に応じて既知の油性溶媒、例えば、油、親油性溶媒等から適宜選択することができる。
上記油としては、例えば、月見草油、杏仁油、スイートアーモンド油、ココナッツオイル、大豆油、ラノリン、ワセリン、ラード、液体ラノリン、ひまし油、ミネラルオイル（３５０、２４０、７０）、ＰＥＧ４００、オリーブ油、落花生油、ごま油、米油、アプリコット・カーネル油、とうもろこし油、スクワラン、鯨油、ミリスチン酸ブチル、ミリスチン酸イソプロピル、サフラワー油、棉実油、シリコン油、パルミチ酸イソプロピル、オレイルアルコール、アーモンド油、ひまわり油、アボガド油、小麦胚芽油、小麦ふすま油、アラキス油、菜種油、からし種子油、大麦胚芽油、ライ麦胚芽油、米胚芽油、カロブ胚芽油、ホホバ油、卵黄油、ミンク油、シリコーンオイル等が挙げられる。
上記親油性溶媒としては、トルエン、ニトロベンゼン等が挙げられる。
なかでも、最終生成物の化粧品、食料品、医薬品等としての人体への使用を考えた場合の安全性および入手の容易さの観点から、油、特に月見草油、杏仁油、スイートアーモンド油、ココナッツオイル、大豆油等を使用することが好ましい。The oily solvent in the present invention is not particularly limited, and is known oily solvent depending on the type and amount of other materials (chitin, surfactant, etc.) used in the emulsion, the use of the obtained emulsion, and the like, for example, , Oil, lipophilic solvent and the like.
Examples of the oil include evening primrose oil, apricot oil, sweet almond oil, coconut oil, soybean oil, lanolin, petrolatum, lard, liquid lanolin, castor oil, mineral oil (350, 240, 70), PEG 400, olive oil, peanut oil , Sesame oil, rice oil, apricot kernel oil, corn oil, squalane, whale oil, butyl myristate, isopropyl myristate, safflower oil, coconut oil, silicon oil, isopropyl palmitate, oleyl alcohol, almond oil, sunflower oil, Avocado oil, wheat germ oil, wheat bran oil, arachis oil, rapeseed oil, mustard seed oil, barley germ oil, rye germ oil, rice germ oil, carob germ oil, jojoba oil, egg yolk oil, mink oil, silicone oil, etc. Can be mentioned.
Examples of the lipophilic solvent include toluene and nitrobenzene.
Above all, oils, especially evening primrose oil, apricot oil oil, sweet almond oil, coconut, from the viewpoint of safety and availability when considering use of the final product as cosmetics, foodstuffs, pharmaceuticals, etc. It is preferable to use oil, soybean oil or the like.
本発明の乳化物における油性溶媒の配合量は、水性溶媒（本発明の乳化物中に含まれる全てのもの）１重量部に対して、好ましくは０．１重量部〜１０重量部、より好ましくは０．１重量部〜０．５重量部の下限、かつ、２重量部〜１０重量部の上限の範囲内にある量である。油性溶媒の配合量が水性溶媒１重量部に対して０．１重量部未満の場合、乳化が均一でなくなるおそれがあり、その一方、水性溶媒１重量部に対して１０重量部を超える場合、溶液が混合せずに分離するおそれがある。 The blending amount of the oily solvent in the emulsion of the present invention is preferably 0.1 to 10 parts by weight, more preferably 1 part by weight of an aqueous solvent (all of those contained in the emulsion of the present invention). Is an amount within the lower limit of 0.1 to 0.5 parts by weight and the upper limit of 2 to 10 parts by weight. If the blending amount of the oily solvent is less than 0.1 parts by weight with respect to 1 part by weight of the aqueous solvent, the emulsification may not be uniform, whereas if it exceeds 10 parts by weight with respect to 1 part by weight of the aqueous solvent, There is a risk of the solution separating without mixing.
本発明の乳化物におけるキチン含量は、水性溶媒、油性溶媒および界面活性剤の種類および配合量、乳化物の製造方法、乳化物の用途等に応じて適宜設定することができる。
例えば、後述するように、キチンを水性溶媒または油性溶媒に溶媒和させた後、乳化物を製造する場合、本発明の乳化物におけるキチン含量は、キチンが溶媒和した水性溶媒または油性溶媒に対して、好ましくは０．１〜１５重量％、より好ましくは１〜６重量％、特に好ましくは２〜４重量％である。これは、キチン含量が０．１重量％未満の場合、溶媒と溶媒和キチンが分離するおそれがあり、その一方、１５重量％を超える場合、キチンが溶媒和の状態を解消して固体として析出するおそれがあるためである。The chitin content in the emulsion of the present invention can be appropriately set according to the type and blending amount of the aqueous solvent, the oily solvent and the surfactant, the production method of the emulsion, the use of the emulsion and the like.
For example, as described later, when chitin is solvated in an aqueous solvent or oily solvent and then an emulsion is produced, the chitin content in the emulsion of the present invention is based on the aqueous solvent or oily solvent in which chitin is solvated. The content is preferably 0.1 to 15% by weight, more preferably 1 to 6% by weight, and particularly preferably 2 to 4% by weight. This is because when the chitin content is less than 0.1% by weight, the solvent and the solvated chitin may be separated. On the other hand, when the chitin content exceeds 15% by weight, the chitin is dissolved in a solvated state and precipitated as a solid. It is because there is a possibility of doing.
本発明の乳化物は、その製造方法等に応じて、各種の金属塩等を含有し得る。例えば、後記キチン溶液を使用して乳化物を製造した場合、ハロゲン化カルシウム塩、ハロゲン化マグネシウム塩等を含有し得る。 The emulsion of this invention can contain various metal salts etc. according to the manufacturing method. For example, when an emulsion is produced using a chitin solution described below, it may contain a calcium halide salt, a magnesium halide salt, or the like.
また、本発明の乳化物には、必要に応じて、甘味料、着色料、保存料、増粘安定剤、酸化防止剤、漂白剤、調味料、苦味料等、酸味料、強化剤、香料、香辛料、製造用剤、酵素、ガムベース、光沢剤、乳化剤、増粘剤、皮膜形成剤、金属イオン封鎖剤、アルカリ剤、油性原料、保湿剤、薬剤、植物抽出エキス等の添加物を配合させることができる。この場合の添加物の添加量は、目的に応じて適宜選択することができる。 In addition, the emulsion of the present invention includes, as necessary, sweeteners, coloring agents, preservatives, thickening stabilizers, antioxidants, bleaching agents, seasonings, bittering agents, sour agents, fortifying agents, and flavoring agents. , Spices, manufacturing agents, enzymes, gum bases, brighteners, emulsifiers, thickeners, film formers, sequestering agents, alkaline agents, oily ingredients, moisturizers, drugs, plant extract extracts, etc. be able to. The addition amount of the additive in this case can be appropriately selected according to the purpose.
本発明の乳化物中の分散体の粒径は、好ましくは５０ｎｍ〜５００μｍ、より好ましくは５００ｎｍ〜５０μｍである。
上記粒径の値は、顕微鏡観察法（倍率：約１００〜約８００倍）によって決定される値である。The particle size of the dispersion in the emulsion of the present invention is preferably 50 nm to 500 μm, more preferably 500 nm to 50 μm.
The value of the particle size is a value determined by a microscopic observation method (magnification: about 100 to about 800 times).
また、本発明は、
（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液に、界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法を提供する。The present invention also provides:
(1) A step of dissolving chitin in a solvent containing an alcohol consisting of methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) A method for producing a chitin emulsion comprising a step of mixing a surfactant and an oily solvent with a chitin solution.
また、本発明は、
（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法を提供する。The present invention also provides:
(1) A step of dissolving chitin in a solvent containing an alcohol consisting of methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) A method for producing a chitin emulsion comprising a step of mixing a surfactant and an oily solvent with a hydrated chitin slurry.
また、本発明は、
（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに、親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
（４）親水性溶媒和キチンスラリーに界面活性剤および油性溶媒を混合する工程と
を含む、キチン乳化物の製造方法を提供する。The present invention also provides:
(1) A step of dissolving chitin in a solvent containing an alcohol consisting of methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) adding a hydrophilic solvent to the hydrated chitin slurry, replacing water molecules contained in the hydrated chitin slurry with the hydrophilic solvent, and obtaining a hydrophilic solvated chitin slurry;
(4) A method for producing a chitin emulsion comprising a step of mixing a surfactant and an oily solvent with a hydrophilic solvated chitin slurry.
また、本発明は、
（１）キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る工程と、
（２）キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
（３）水和キチンスラリーに、親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
（４）親水性溶媒和キチンスラリーに、親水性溶媒に溶解する油性溶媒を添加し、親水性溶媒和キチンスラリーに含まれる親水性溶媒を該油性溶媒で置換して、油性溶媒和キチンスラリーを得る工程と、
（５）油性溶媒和キチンスラリーに界面活性剤および水性溶媒を混合する工程と
を含む、キチン乳化物の製造方法を提供する。
本発明のキチン乳化物は、好ましくは上記のいずれかの方法により製造することができる。The present invention also provides:
(1) A step of dissolving chitin in a solvent containing an alcohol consisting of methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the produced chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) adding a hydrophilic solvent to the hydrated chitin slurry, replacing water molecules contained in the hydrated chitin slurry with the hydrophilic solvent, and obtaining a hydrophilic solvated chitin slurry;
(4) An oily solvent that dissolves in the hydrophilic solvent is added to the hydrophilic solvated chitin slurry, and the hydrophilic solvent contained in the hydrophilic solvated chitin slurry is replaced with the oily solvent to obtain an oily solvated chitin slurry. Obtaining a step;
(5) A method for producing a chitin emulsion comprising a step of mixing a surfactant and an aqueous solvent in an oily solvated chitin slurry.
The chitin emulsion of the present invention can be preferably produced by any of the methods described above.
上記キチン溶液を得る工程では、キチンを、メチルアルコールまたはエチルアルコールからなるアルコールと、ハロゲン化カルシウム塩またはハロゲン化マグネシウム塩とを含んでなる溶媒に溶解して、キチン溶液を得る。このような溶媒を用いることにより、難溶性を示すキチンの硬い結晶構造を崩して溶媒をキチン分子内部まで浸透させることが可能となり、その結果、溶媒和が生じて拡がった分子構造になり、溶解状態のキチンを得ることができる。当該工程は、例えば特開平06-179702号公報に記載されるように行うことができる。
当該工程に使用するキチンは、本発明におけるキチンとして、キチン乳化物について前述したキチンである。
上記溶媒におけるハロゲン化カルシウム塩としては、塩化カルシウム・2水塩、臭化カルシウム・2水塩、ヨウ化カルシウム・2水塩等が挙げられる。
上記溶媒におけるハロゲン化マグネシウム塩としては、塩化マグネシウム・6水塩等が挙げられる。
また、上記溶媒におけるアルコール中のハロゲン化カルシウム塩またはハロゲン化マグネシウム塩の濃度は、キチン溶解量の点から、飽和濃度であることが好ましい。
ある実施形態においては、キチンを上記の溶媒中に、好ましくは０．１〜５％（w／v）、より好ましくは０．５〜２％（w／v)となるような濃度で添加し、好ましくは２０〜７０℃、より好ましくは４０℃〜６０℃の温度で、還流下充分撹拌しながら溶解させる。使用するキチンの分子量の大きさに応じて、溶媒中のキチン濃度を調節することが好ましい。
In the step of obtaining the chitin solution, chitin is dissolved in a solvent comprising an alcohol composed of methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution. By using such a solvent, it becomes possible to break down the hard crystalline structure of chitin, which is hardly soluble, and to allow the solvent to penetrate into the chitin molecule. As a result, solvation occurs and the molecular structure is expanded and dissolved. The state chitin can be obtained. This step can be performed, for example, as described in JP-A No. 06-179702.
The chitin used for the said process is a chitin mentioned above about the chitin emulsion as the chitin in this invention.
Examples of the calcium halide salt in the solvent include calcium chloride dihydrate, calcium bromide dihydrate, calcium iodide dihydrate, and the like.
Examples of the magnesium halide salt in the solvent include magnesium chloride and hexahydrate.
Moreover, it is preferable that the density | concentration of the calcium halide salt or magnesium halide salt in alcohol in the said solvent is a saturated density | concentration from the point of chitin dissolution amount.
In certain embodiments, chitin is added to the above solvent at a concentration that is preferably 0.1-5% (w / v), more preferably 0.5-2% (w / v). The solution is preferably dissolved at a temperature of 20 to 70 ° C., more preferably 40 to 60 ° C. with sufficient stirring under reflux. It is preferable to adjust the chitin concentration in the solvent according to the molecular weight of the chitin used.
上記キチン溶液を水で希釈し、必要に応じて生成したキチンの沈殿を水洗し、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換することにより、水和キチンスラリーを得ることができる。
ある実施形態においては、キチン溶液を室温に冷却後、濾布（ネル）で不溶部を除去する。その後、蒸留水で希釈する。その際の希釈濃度は、好ましくは７５％(ｖ／ｖ)〜１０％(ｖ／ｖ)、より好ましくは５０％(ｖ／ｖ)〜２５％(ｖ／ｖ)である。蒸留水で希釈すると通常キチンが沈澱するので、これを十分水洗をして、アルコールとカルシウムイオンまたはマグネシウムイオンを除去する。また、水で希釈後、アルコールとカルシウムイオンまたはマグネシウムイオンを除去するために、透析を行ってもよい。さらに、水洗および透析は繰り返し行ってもよい。さらに、遠心法等によって水分を調節して、所望のキチン含量の水和キチンスラリーを得ることができる。Diluting the chitin solution with water, washing the generated chitin precipitate with water as necessary, and replacing the calcium ions or magnesium ions and alcohol contained in the solution with water molecules to obtain a hydrated chitin slurry Can do.
In one embodiment, the chitin solution is cooled to room temperature, and then the insoluble portion is removed with a filter cloth (nel). Then, dilute with distilled water. The dilution concentration at that time is preferably 75% (v / v) to 10% (v / v), more preferably 50% (v / v) to 25% (v / v). When diluted with distilled water, chitin usually precipitates, and this is thoroughly washed to remove alcohol and calcium ions or magnesium ions. Further, after dilution with water, dialysis may be performed in order to remove alcohol and calcium ions or magnesium ions. Further, washing with water and dialysis may be repeated. Furthermore, a hydrated chitin slurry having a desired chitin content can be obtained by adjusting the water content by a centrifugal method or the like.
上記水和キチンスラリーに、親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換することにより、親水性溶媒和キチンスラリーを得ることができる。
上記親水性溶媒としては、例えば、キチン乳化物について説明したものが挙げられ、好ましくはメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、イソブチルアルコール、２−ブタノール、ｔ−ブタノール、アリルアルコール等の一価アルコールが挙げられるが、これらに限定されない。特にメタノールおよびエタノールからなる群から選択されるアルコールを使用すると、水和キチンスラリー中に含まれる水分子との置換を好適に完結させることができる。
ある実施形態においては、水和キチンスラリーに好ましくは１０〜１００％（ｖ／ｖ）、より好ましくは９０〜１００％（ｖ／ｖ）となるような濃度でアルコールを添加して充分に撹拌し、３０分〜１時間静置した後、遠心分離して、所定容量のスラリーに調節する。この操作を数回、好ましくは２〜４回繰り返して、水和キチンスラリー中に含まれる水分子との置換を完結させることにより、アルコール溶媒和キチンスラリーを得ることができる。A hydrophilic solvated chitin slurry can be obtained by adding a hydrophilic solvent to the hydrated chitin slurry and replacing the water molecules contained in the hydrated chitin slurry with the hydrophilic solvent.
Examples of the hydrophilic solvent include those described for chitin emulsions, preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, t-butanol, allyl. Although monohydric alcohol, such as alcohol, is mentioned, it is not limited to these. In particular, when an alcohol selected from the group consisting of methanol and ethanol is used, substitution with water molecules contained in the hydrated chitin slurry can be suitably completed.
In certain embodiments, alcohol is added to the hydrated chitin slurry at a concentration that is preferably 10 to 100% (v / v), more preferably 90 to 100% (v / v), and is sufficiently stirred. After standing for 30 minutes to 1 hour, the mixture is centrifuged and adjusted to a predetermined volume of slurry. By repeating this operation several times, preferably 2 to 4 times, to complete substitution with water molecules contained in the hydrated chitin slurry, an alcohol solvated chitin slurry can be obtained.
また、上記親水性溶媒和キチンスラリーに、親水性溶媒に溶解する別の溶媒（例えば、別の親水性溶媒、油性溶媒（親油性溶媒等）、酸およびアルカリ水溶液等）を添加することにより、親水性溶媒和キチンスラリー中に含まれる親水性溶媒を該別の溶媒で置換した溶媒和キチンスラリーを得ることができる。したがって、別の溶媒として、油性溶媒を使用した場合、油性溶媒和キチンスラリーを得ることができる。
当該工程は、水和キチンスラリーから親水性溶媒和キチンスラリーを得る工程と同様に行うことができる。Moreover, by adding another solvent (for example, another hydrophilic solvent, an oily solvent (lipophilic solvent, etc.), an acid and an alkaline aqueous solution, etc.) that dissolves in the hydrophilic solvent to the hydrophilic solvated chitin slurry, A solvated chitin slurry in which the hydrophilic solvent contained in the hydrophilic solvated chitin slurry is replaced with the other solvent can be obtained. Therefore, when an oily solvent is used as another solvent, an oily solvated chitin slurry can be obtained.
The said process can be performed similarly to the process of obtaining a hydrophilic solvation chitin slurry from a hydration chitin slurry.
上記溶媒における酸としては、アシル化、アルキル化等、触媒反応の目的等で使用されるものであって、例えば、過塩素酸、塩酸、硫酸、メタンスルホン酸等が挙げられるが、これらに限定されない。
上記溶媒におけるアルカリとしては、アシル化、アルキル化反応中間体合成の目的等で使用されるものであって、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化アルミニウム、水酸化リチウム、水酸化バリウム等が挙げられるが、これらに限定されない。
上記溶媒における油性溶媒としては、例えば、シリコーンオイル、親油性溶媒（トルエン、ニトロベンゼン等）等が挙げられるが、これらに限定されない。Examples of the acid in the solvent include those used for the purpose of catalytic reaction such as acylation and alkylation, and examples thereof include perchloric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and the like. Not.
Examples of the alkali in the solvent include those used for the purpose of acylation and alkylation reaction intermediate synthesis, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, Although barium hydroxide etc. are mentioned, it is not limited to these.
Examples of the oily solvent in the above solvent include, but are not limited to, silicone oil and lipophilic solvents (toluene, nitrobenzene, etc.).
上記別の溶媒としては、好適には、一価または多価アルコールおよび苛性アルカリ類からなる群から選択される。なかでも、中性で均一分散性を発現させる観点から、エチレングリコール、水酸化ナトリウムを使用することが好ましい。また、水酸化ナトリウム等のアルカリ類は、キチンのアシル化やアルキル化への中間体であるが、脱アセチル化を起こさないために、出来るだけ低濃度とすることが好ましい。 The other solvent is preferably selected from the group consisting of mono- or polyhydric alcohols and caustics. Especially, it is preferable to use ethylene glycol and sodium hydroxide from a viewpoint of expressing neutral and uniform dispersibility. Moreover, although alkalis, such as sodium hydroxide, are intermediates for acylation or alkylation of chitin, it is preferable to make the concentration as low as possible in order not to cause deacetylation.
上記親水性または油性溶媒和キチンスラリーは、好ましくは、可視域分光光度計によって測定される５５０ｎｍでの可視光線透過率が１０〜９０％であるという特徴を有する。好適には、親水性または油性溶媒和キチンスラリーの可視光線透過率は４０％以上であり、より好ましくは６０％以上である。また、親水性または油性溶媒和キチンスラリーの可視光線透過率は、通常９０％以下であるが、ある場合には８０％以下、別の場合には７０％以下であり得る。 The hydrophilic or oily solvated chitin slurry preferably has a characteristic that the visible light transmittance at 550 nm measured by a visible spectrophotometer is 10 to 90%. Suitably, the visible light transmittance of the hydrophilic or oily solvated chitin slurry is 40% or more, more preferably 60% or more. Further, the visible light transmittance of the hydrophilic or oily solvated chitin slurry is usually 90% or less, but may be 80% or less in some cases and 70% or less in other cases.
上記親水性または油性溶媒和キチンスラリー中に分散するキチンの粒径は、好ましくは１〜５００μｍ、より好ましくは５〜５０μｍである。スラリー中に分散するキチンの粒径は、例えば顕微鏡によって測定することができる。 The particle size of chitin dispersed in the hydrophilic or oily solvated chitin slurry is preferably 1 to 500 μm, more preferably 5 to 50 μm. The particle size of chitin dispersed in the slurry can be measured, for example, with a microscope.
上記のようにして得られるキチン溶液、水和キチンスラリーまたは親水性溶媒和キチンスラリーに、界面活性剤および油性溶媒を混合することにより、キチン乳化物を得ることができる。或いは、上記のようにして得られる油性溶媒和キチンスラリーに、界面活性剤および水性溶媒を混合することにより、キチン乳化物を得ることもできる。
当該混合工程における界面活性剤、水性溶媒、および油性溶媒としては、キチン乳化物について上述したものが挙げられ、当該工程により乳化物が得られる限り特に限定されない。
また、界面活性剤は、必要に応じて、水性溶媒および油性溶媒に溶解させた状態で混合させることもできる。A chitin emulsion can be obtained by mixing a surfactant and an oily solvent into the chitin solution, hydrated chitin slurry or hydrophilic solvated chitin slurry obtained as described above. Alternatively, a chitin emulsion can be obtained by mixing a surfactant and an aqueous solvent in the oily solvated chitin slurry obtained as described above.
Examples of the surfactant, the aqueous solvent, and the oily solvent in the mixing step include those described above for the chitin emulsion, and are not particularly limited as long as the emulsion is obtained in the step.
Moreover, surfactant can also be mixed in the state melt | dissolved in the aqueous solvent and the oil-based solvent as needed.
上記混合（乳化）工程は、特に限定されず、従来既知の方法を用いて行うことができる。例えば、スパチュラまたはガラス棒を用いて手で撹拌してもよく、また、混合時に撹拌機、ブレンダー、ホモジナイザー、コロイドミル、ジェットミキサー等の乳化機を使用することで、乳化物中のキチンの分散性、粒径の微小化および均一性を高めることもできる。また、転相乳化法、界面活性剤相乳化法、転相温度乳化法、液晶乳化、ゲル乳化等も行うことができ、この場合、キチンの分散性、粒径の微小化および均一性に優れた乳化物が得られる。 The said mixing (emulsification) process is not specifically limited, It can carry out using a conventionally well-known method. For example, it may be stirred manually with a spatula or glass rod, and the chitin in the emulsion may be dispersed by using an emulsifier such as a stirrer, blender, homogenizer, colloid mill, jet mixer during mixing. Property, particle size miniaturization, and uniformity can also be improved. In addition, phase inversion emulsification method, surfactant phase emulsification method, phase inversion temperature emulsification method, liquid crystal emulsification, gel emulsification, etc. can also be performed. An emulsion is obtained.
上記混合（乳化）工程に使用するキチン溶液、水和キチンスラリー、親水性溶媒和キチンスラリーまたは油性溶媒和キチンスラリーは、濃縮または希釈等の既知の方法により、そのキチン含量を、好ましくは０．１〜１５重量％、より好ましくは１〜６重量％、特に好ましくは２〜４重量％に予め調整しておくことが好ましい。これは、キチン含量が０．１重量％未満の場合、溶媒と溶媒和キチンが分離するおそれがあり、その一方、１５重量％を超える場合、キチンが溶媒和の状態を解消して固体として析出するおそれがあるためである。
また、上記工程において、界面活性剤が水性溶媒（本発明の乳化物中に含まれるすべてのもの）１重量部に対して、好ましくは０．０００５重量部〜０．０５重量部、より好ましくは０．０１重量部〜０．０３重量部、および油性溶媒が水性溶媒１重量部に対して、好ましくは０．１重量部〜１０重量部、より好ましくは０．１重量部〜０．５重量部の下限、かつ、２重量部〜１０重量部の上限の範囲内になるような量で各成分を使用することが好ましい。
このような量比で各成分を使用することにより、本発明のキチン乳化物を特に容易に得ることができる。すなわち、この場合、キチン乳化物を得るために特別な乳化装置を使用する必要はない。The chitin solution, hydrated chitin slurry, hydrophilic solvated chitin slurry, or oily solvated chitin slurry used in the mixing (emulsification) step is adjusted to have a chitin content of preferably 0. 0 by a known method such as concentration or dilution. It is preferable to adjust in advance to 1 to 15% by weight, more preferably 1 to 6% by weight, and particularly preferably 2 to 4% by weight. This is because when the chitin content is less than 0.1% by weight, the solvent and the solvated chitin may be separated. On the other hand, when the chitin content exceeds 15% by weight, the chitin is dissolved in a solvated state and precipitated as a solid. It is because there is a possibility of doing.
In the above step, the surfactant is preferably 0.0005 to 0.05 parts by weight, more preferably 1 part by weight based on 1 part by weight of the aqueous solvent (everything contained in the emulsion of the present invention). 0.01 part by weight to 0.03 part by weight, and the oily solvent is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.1 part by weight to 0.5 part by weight with respect to 1 part by weight of the aqueous solvent. It is preferable to use each component in such an amount that it falls within the lower limit of 2 parts and the upper limit of 2 to 10 parts by weight.
By using each component in such a quantitative ratio, the chitin emulsion of the present invention can be obtained particularly easily. That is, in this case, it is not necessary to use a special emulsification apparatus in order to obtain a chitin emulsion.
本発明のキチン乳化物は、キチンおよびキトサンの適用分野に適用することが可能である。すなわち、以下の適用分野に適用することができる。
（１）化粧品分野：ヘルスケア、スキンケア、ヘアケア、オーラルケア、アンチエイジング用等のクリーム、クレンジング等（保湿剤、増粘剤、炎症抑制、紫外線、ヘアダメージ抑制、皮膚ダメージ抑制、皮膚再生）、忌避剤等、
（２）食品分野：腸内代謝改善（乳酸菌増殖、乳糖の消化に必要なβガラクシトーゼの生産促進）、免疫力増強、パンのふくらみ向上、ヒアルロン酸産生促進、変形関節症の予防・改善用等の健康食品、機能性食品等、
（３）医療分野：創傷治癒剤（材）、不織布、人工皮膚、手術用縫合糸、クリーム、医薬品（薬、不織布形状でがん細胞増殖抑制、免疫増強作用（がん細胞増殖抑制や日和見感染菌−Lisera monocytogenesに対する防御効果）、乳酸菌増殖、乳糖の消化に必要なβガラクシトーゼの生産促進、ヒアルロン酸産生促進、変形関節症の予防・改善、炎症改善、治癒（口内炎、歯肉炎、歯槽膿漏等も含む）、鎮痛抑制剤、止血剤、殺菌剤）、生体材料（骨、歯等）等、
（４）植物分野：土壌改良材、植物防除材等、
（５）バイオ分野：細胞増殖用基材等、
（６）成形材料分野：プラスチック製品へのフィラー（増粘剤、生分解素材）、天然素材成形品、フィルム等、
（７）増粘剤等。The chitin emulsion of the present invention can be applied to the application fields of chitin and chitosan. That is, it can be applied to the following application fields.
(1) Cosmetics field: Health care, skin care, hair care, oral care, anti-aging cream, cleansing, etc. (humectant, thickener, inflammation suppression, ultraviolet light, hair damage suppression, skin damage suppression, skin regeneration), Repellents, etc.
(2) Food field: Improvement of intestinal metabolism (proliferation of lactic acid bacteria, promotion of production of β-galactose required for digestion of lactose), enhancement of immunity, improvement of bread bulge, promotion of hyaluronic acid production, prevention and improvement of osteoarthritis, etc. Health food, functional food, etc.
(3) Medical field: Wound healing agent (material), non-woven fabric, artificial skin, surgical suture, cream, pharmaceuticals (medicine, non-woven fabric shape cancer cell proliferation suppression, immune enhancement effect (cancer cell growth suppression and opportunistic infection) Fungus-protective effect against Lisera monocytogenes), lactic acid bacteria growth, β-galactose production necessary for lactose digestion, hyaluronic acid production promotion, prevention and improvement of osteoarthritis, inflammation improvement, healing (stomatitis, gingivitis, alveolar pyorrhea) Etc.), analgesic suppressants, hemostatic agents, bactericides), biomaterials (bones, teeth, etc.),
(4) Plant field: soil improvement material, plant control material, etc.
(5) Biotechnology field: Cell growth substrate, etc.
(6) Molding material field: Fillers for plastic products (thickeners, biodegradable materials), natural material molded products, films, etc.
(7) Thickener and the like.
以下、実施例を挙げて本発明を説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例および比較例に使用した材料を以下に示す。
〔キチン粉末〕
実施例および比較例には、以下のキチン粉末を使用した。
・甲陽ケミカル（株）製「キチンＴＣＬ」を使用した。当該キチン粉末におけるキチンのアセチル化度は９５％以上であり、重量平均分子量数十万であった。
・キトサン（（株）協和テクノス製「フローナックＣ」）を無水酢酸にてアセチル化した再生キチンを使用した。当該キチン粉末におけるアセチル化度は９７％以上であり、重量平均分子量は５０，０００〜１００，０００、タンパク質含量（アミノ酸含量）は、０．０１重量％であった。
〔界面活性剤〕
・ＳＤＳ：キシダ化学（株）製「ドデシル硫酸ナトリウム９８％」
・ジアセチル酒石酸モノグリセリド：太陽化学（株）製「サンソフトNo. 641D」
・ペーストレシチン：辻製油（株）製「SLP-ペーストリゾ」
・キラヤニン：キラヤサポニン、丸善製薬（株）製「キラヤニンP-20」
・粉末レシチン：辻製油（株）製「SLP-ホワイトリゾ」
〔オイル〕
・月見草オイル：サミット製油（株）製「月見草油」、ケン化価１８３〜１９５
・杏仁油：日光ケミカルズ（株）製「杏仁油」、ケン化価１８８〜２００、比重０．９１０〜０．９１８
・スイートアーモンドオイル：日光ケミカルズ（株）製「スイートアーモンド油」、ケン化価１８８〜２００、比重０．９１１〜０．９１８
・ココナッツオイル：日光ケミカルズ（株）製「TRIFAT C-24」、ケン化価２４６〜２６４、比重０．９１２〜０．９２２
・大豆油：シグマアルドリッチジャパン（株）製「大豆油」、Code No. 23-0510-5EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these. The materials used in the following examples and comparative examples are shown below.
[Chitin powder]
In the examples and comparative examples, the following chitin powder was used.
-“Chitin TCL” manufactured by Koyo Chemical Co., Ltd. was used. The chitin acetylation degree in the chitin powder was 95% or more, and the weight average molecular weight was several hundred thousand.
-Regenerated chitin obtained by acetylating chitosan ("Flownac C" manufactured by Kyowa Technos Co., Ltd.) with acetic anhydride was used. The chitin powder had an acetylation degree of 97% or more, a weight average molecular weight of 50,000 to 100,000, and a protein content (amino acid content) of 0.01% by weight.
[Surfactant]
SDS: “Sodium dodecyl sulfate 98%” manufactured by Kishida Chemical Co., Ltd.
・ Diacetyltartaric acid monoglyceride: "Sunsoft No. 641D" manufactured by Taiyo Chemical Co., Ltd.
・ Paste lecithin: “SLP-paste lyso” manufactured by Sakai Oil Co., Ltd.
・ Kirayanin: Kirayasaponin, “Kirayanin P-20” manufactured by Maruzen Pharmaceutical Co., Ltd.
・ Powder lecithin: “SLP-White Reso” manufactured by Sakai Oil Co., Ltd.
〔oil〕
・ Evening Primrose Oil: “Evening Primrose Oil” manufactured by Summit Oil Co., Ltd., saponification value 183 to 195
Apricot kernel oil: “Apricot kernel oil” manufactured by Nikko Chemicals Co., Ltd., saponification number 188 to 200, specific gravity 0.910 to 0.918
Sweet almond oil: “Sweet almond oil” manufactured by Nikko Chemicals Co., Ltd., saponification value of 188 to 200, specific gravity of 0.911 to 0.918
Coconut oil: “TRIFAT C-24” manufactured by Nikko Chemicals Co., Ltd., saponification value 246 to 264, specific gravity 0.912 to 0.922
・ Soybean oil: "Soybean oil" manufactured by Sigma-Aldrich Japan, Code No. 23-0510-5
また、以下の実施例および比較例における物性の評価方法は以下の通りである。
〔重量平均分子量〕
キチンの分子量は、以下の手順により決定した（粘度法）。
（１）複数の既知の濃度のキチン溶液を作成し、これらの粘度をコーンプレート型回転粘度計で測定する（機器：ブルックフィールド社製「DV-II+Pro」、温度：２５℃）。
（２）上記の粘度より対象キチンの固有粘度を計算する。
（３）算出した固有粘度より、以下の粘度式にしたがって重量平均分子量を算出する。
［η］＝２．５４×１０−２Ｍ０．４５
〔式中、［η］：固有粘度、Ｍ：重量平均分子量〕。Moreover, the evaluation methods of physical properties in the following examples and comparative examples are as follows.
(Weight average molecular weight)
The molecular weight of chitin was determined by the following procedure (viscosity method).
(1) A chitin solution having a plurality of known concentrations is prepared, and the viscosities thereof are measured with a cone plate type rotational viscometer (instrument: “DV-II + Pro” manufactured by Brookfield, temperature: 25 ° C.).
(2) The intrinsic viscosity of the target chitin is calculated from the above viscosity.
(3) A weight average molecular weight is calculated from the calculated intrinsic viscosity according to the following viscosity formula.
[Η] = 2.54 × 10 −2 M 0.45
[Wherein [η]: intrinsic viscosity, M: weight average molecular weight].
〔アセチル化度〕
キチンのアセチル化度は、以下の手順により決定した。
（前処理）
（１）２Ｍ−塩酸１００ｍｌとキチン２ｇを１００ｍｌビーカーに入れ、４００ｒｐｍで３０分間攪拌（マグネチックスターラー）する。
（２）混合物を、ろ紙（ADVANTEC製「QUALITVE FILTER PAPRE NO.1」）にてろ過後、ろ過残渣とメタノール１００ｍｌをビーカーに入れ、１５分間攪拌洗浄する。次いで、混合物を再びろ過する。
（３）上記（２）の操作を４回以上繰り返し行う。
（４）メタノールによる洗浄の終了後、得られた残渣（キチン）を約１時間風乾する。その後、５０℃で真空乾燥を１２時間行う。
（測定）
（１）前処理したキチンを０．５０００ｇ精秤する。
（２）蒸留水５０ｍｌ（メスシリンダーで計量）を加え、フェノールフタレインを３滴加え、４００ｒｐｍで攪拌しながら、０．１Ｎ水酸化ナトリウム水溶液で滴定する。液の着色（ピンク）が３０秒以上続いた点を終点とする。
（３）キチンの重量（ａ）と０．１Ｎ水酸化ナトリウム水溶液の滴定量（ｂ）から次式よりアセチル化度を算出する。
アセチル化度（％）＝（２．０３×ｂ）／［ａ＋（５．５×ｂ×１０−４）］[Degree of acetylation]
The degree of acetylation of chitin was determined by the following procedure.
(Preprocessing)
(1) Put 100 ml of 2M hydrochloric acid and 2 g of chitin into a 100 ml beaker, and stir (magnetic stirrer) at 400 rpm for 30 minutes.
(2) The mixture is filtered with a filter paper (“QUALITVE FILTER PAPRE NO.1” manufactured by ADVANTEC), and the filtration residue and 100 ml of methanol are put into a beaker and stirred and washed for 15 minutes. The mixture is then filtered again.
(3) Repeat the above operation (2) four or more times.
(4) After completion of washing with methanol, the obtained residue (chitin) is air-dried for about 1 hour. Thereafter, vacuum drying is performed at 50 ° C. for 12 hours.
(Measurement)
(1) Weigh precisely 0.5000 g of the pretreated chitin.
(2) Add 50 ml of distilled water (measured with a graduated cylinder), add 3 drops of phenolphthalein, and titrate with 0.1N aqueous sodium hydroxide while stirring at 400 rpm. The point at which the liquid color (pink) continues for 30 seconds or more is defined as the end point.
(3) The degree of acetylation is calculated from the following formula from the weight of chitin (a) and the titration amount (b) of 0.1N aqueous sodium hydroxide solution.
Degree of acetylation (%) = (2.03 × b) / [a + (5.5 × b × 10 −4 )]
〔タンパク質含量〕
キチンのタンパク質含量は、以下の手順によりアミノ酸１８種（リジン、ヒスチジン、フェニルアラニン、ロイシン、イソロイシン、メチオニン、バリン、スレオニン、トリプトファン、アルギニン、チロシン、アラニン、グリシン、プロリン、グルタミン酸、セリン、アスパラギン酸、シスチン）を分析して決定した（アミノ酸分析法）。
（１）キチンを加水分解する（塩酸加水分解；メチオニン、シスチンは過ギ酸酸化処理後、塩酸加水分解）。
（２）アミノ酸分析機（日立製高速アミノ酸分析計Ｌ８８００ｋ）によって各種アミノ酸量を測定する。
（３）トリプトファンのみ高速液体クロマトグラフ法（日本電子製株式会社製ＪＬＣ−５００ Ｖ）にて測定する。[Protein content]
The protein content of chitin was determined by the following procedure using 18 amino acids (lysine, histidine, phenylalanine, leucine, isoleucine, methionine, valine, threonine, tryptophan, arginine, tyrosine, alanine, glycine, proline, glutamic acid, serine, aspartic acid, cystine. ) Was analyzed (amino acid analysis method).
(1) Hydrolyze chitin (hydrochloric acid hydrolysis; methionine and cystine are hydrolyzed with hydrochloric acid after formic acid oxidation treatment).
(2) The amount of various amino acids is measured with an amino acid analyzer (Hitachi high-speed amino acid analyzer L8800k).
(3) Only tryptophan is measured by high performance liquid chromatography (JLC-500 V, manufactured by JEOL Ltd.).
〔乳化物中の分散体の粒径〕
乳化物をスライドガラス上に採取して、倒立顕微鏡（Nikon社製Eclipse TE-2000 U）にて４〜６０倍の対物レンズを用い、粒径を観察した。
〔乳化状態〕
乳化物を室温（２０℃〜３０℃）にて静置し、目視にて状態を観察し、３０日経過後まで溶液の分離等が発生していないことを確認した。[Particle size of dispersion in emulsion]
The emulsion was collected on a slide glass, and the particle size was observed with an inverted microscope (Eclipse TE-2000 U manufactured by Nikon) using an objective lens of 4 to 60 times.
[Emulsified state]
The emulsion was allowed to stand at room temperature (20 ° C. to 30 ° C.), the state was visually observed, and it was confirmed that no separation of the solution occurred until 30 days had elapsed.
〔製造例１〕
（１）メタノール（１０ｌ）に塩化カルシウム２水和物（８．５ｋｇ；和光純薬製「塩化カルシウム（２水）」）を溶解させて、塩化カルシウム２水和物飽和メタノール溶液を調製した。次いで、５５℃に温調されたウォーターバス中で、該溶液（１１ｌ）中にキチン粉末（８０ｇ）を、撹拌機（「FINE FL-105N」）を用いてダイヤル３〜７の撹拌条件下に溶解させ、キチン溶液を調製した。
（２）上記キチン溶液を、濾布（平均孔径約０．２ｍｍ、約４個／ｍｍ２）を用いて濾過し、不溶物等を除去した。次いで、濾過されたキチン溶液と、等量〜４倍量のイオン交換水を、ブレンダー（オスター製「オスターブレンダー ＳＴ−１」）を用いて１０，３００〜１５，７００ｒｐｍの撹拌条件下に混合し、次いで一晩静置してキチンを沈殿させた。その後、沈殿物を、遠心脱水機（（株）コクサン製「Ｈ−１２２」）を用いて５００〜１，０００ｒｐｍの分離条件下に分離し、次いで、分離された沈殿物を、さらに等量〜４倍量のイオン交換水にて洗浄し、同様に遠心分離することにより、水和キチンスラリーを得た。
（３）得られた水和キチンスラリーの一部を乾燥機（yamato社製「DN410H」）にて８０℃で一晩乾燥し、キチン濃度を測定した。その測定結果に基づいて蒸留水を添加し、混合することにより、所望のキチン濃度（２．４重量％（実施例１および２）、または５．９重量％（実施例３〜１２））を有する水和キチンスラリーを得た。[Production Example 1]
(1) Calcium chloride dihydrate (8.5 kg; “Calcium chloride (2 water)” manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in methanol (10 l) to prepare a calcium chloride dihydrate saturated methanol solution. Next, in a water bath adjusted to 55 ° C., the chitin powder (80 g) was put into the solution (11 l) under the stirring conditions of the dials 3 to 7 using a stirrer (“FINE FL-105N”). It was dissolved and a chitin solution was prepared.
(2) The chitin solution was filtered using a filter cloth (average pore size: about 0.2 mm, about 4 / mm 2 ) to remove insoluble matters and the like. Next, the filtered chitin solution and an equivalent amount to 4 times the amount of ion-exchanged water are mixed under a stirring condition of 10,300 to 15,700 rpm using a blender (Oster Blender ST-1 manufactured by Oster). Then, the mixture was allowed to stand overnight to precipitate chitin. Thereafter, the precipitate is separated under a separation condition of 500 to 1,000 rpm using a centrifugal dehydrator (“H-122” manufactured by Kokusan Co., Ltd.). The hydrated chitin slurry was obtained by washing with 4 times the amount of ion-exchanged water and similarly centrifuging.
(3) A portion of the obtained hydrated chitin slurry was dried overnight at 80 ° C. with a dryer (“DN410H” manufactured by Yamato), and the chitin concentration was measured. Based on the measurement results, distilled water was added and mixed to obtain a desired chitin concentration (2.4 wt% (Examples 1 and 2) or 5.9 wt% (Examples 3 to 12)). A hydrated chitin slurry was obtained.
〔製造例２〕
上記製造例１で得られた水和キチンスラリーを、１００ｍＬに５０ｍＬのエタノールを加えて充分撹拌し、３０〜６０分間静置後、遠心分離機（CN-820、アズワン株式会社製）を用いて遠心分離を行い、１００ｍＬのスラリーに容量を調節した。この操作を３〜５回繰り返して水分子との置換を完結させ、キチンが均一分散したキチンゲル（６．５重量％）を得た。さらに冷蔵庫内（５℃）で５ヶ月保存し、濃縮したことにより、所望のキチン濃度（１２．４重量％）を有するエタノール和キチンスラリーを得た。[Production Example 2]
The hydrated chitin slurry obtained in Production Example 1 above was added with 50 mL of ethanol to 100 mL and stirred sufficiently, allowed to stand for 30 to 60 minutes, and then centrifuged using a centrifuge (CN-820, manufactured by ASONE CORPORATION). Centrifugation was performed and the volume adjusted to 100 mL slurry. This operation was repeated 3 to 5 times to complete the substitution with water molecules to obtain a chitin gel (6.5% by weight) in which chitin was uniformly dispersed. Furthermore, it preserve | saved for five months in a refrigerator (5 degreeC), and the ethanol sum chitin slurry which has a desired chitin density | concentration (12.4 weight%) was obtained by concentrating.
〔実施例１〕
上記製造例１で得られた２．４重量％キチンスラリー（３０ｍｇ；キチン量０．７２ｍｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（１ｍｌ）を混合し、次いで、スイートアーモンドオイル（５ｍｌ）を滴下して乳化物を得た（分散体の粒径：１．８μｍ〜１３４μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。[Example 1]
1% (v / v) SDS aqueous solution (1 ml) was mixed with the 2.4 wt% chitin slurry (30 mg; chitin amount 0.72 mg) obtained in Production Example 1 while stirring with a glass stir bar. Subsequently, sweet almond oil (5 ml) was added dropwise to obtain an emulsion (particle size of dispersion: 1.8 μm to 134 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例２〕
上記製造例１で得られた２．４重量％キチンスラリー（３０ｍｇ；キチン量０．７２ｍｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（３ｍｌ）を混合し、次いで、スイートアーモンドオイル（５ｍｌ）を滴下して乳化物を得た（分散体の粒径：１．５μｍ〜８５μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。[Example 2]
The 2.4% by weight chitin slurry (30 mg; chitin amount 0.72 mg) obtained in Production Example 1 was mixed with a 1% (v / v) aqueous SDS solution (3 ml) while stirring with a glass stir bar. Next, sweet almond oil (5 ml) was added dropwise to obtain an emulsion (particle size of dispersion: 1.5 μm to 85 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例３〕
上記製造例１で得られた５．９重量％キチンスラリー（９．７６ｇ；キチン量０．５７６ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｗ／ｖ）ジアセチル酒石酸モノグリセリド水溶液（０．５ｍｌ）を混合し、次いで、ココナッツオイル（５ｍｌ）を混合して乳化物を得た（分散体の粒径：１．７μｍ〜１５７μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 3
A 1% (w / v) diacetyltartaric acid monoglyceride aqueous solution (0. 0%) was stirred into the 5.9 wt% chitin slurry (9.76 g; chitin amount 0.576 g) obtained in Production Example 1 with a glass stirring rod. 5 ml) and then coconut oil (5 ml) to obtain an emulsion (dispersion particle size: 1.7 μm to 157 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例４〕
上記製造例１で得られた５．９重量％キチンスラリー（４０．２ｇ；キチン量２．３７２ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（６ｍｌ）を混合し、次いで、月見草オイル（６ｍｌ）を混合して乳化物を得た（分散体の粒径：０．６μｍ〜９９μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 4
1% (v / v) SDS aqueous solution (6 ml) was mixed with 5.9 wt% chitin slurry (40.2 g; chitin amount 2.372 g) obtained in Production Example 1 while stirring with a glass stir bar. Then, evening primrose oil (6 ml) was mixed to obtain an emulsion (dispersion particle size: 0.6 μm to 99 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例５〕
上記製造例１で得られた５．９重量％キチンスラリー（４０．５ｇ；キチン量２．３９０ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｗ／ｖ）ジアセチル酒石酸モノグリセリド水溶液（１８ｍｌ）を混合し、次いで、月見草オイル（１８ｍｌ）を混合して乳化物を得た（分散体の粒径：０．５μｍ〜１００μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 5
1% (w / v) diacetyltartaric acid monoglyceride aqueous solution (18 ml) while stirring with a glass stir bar to the 5.9 wt% chitin slurry (40.5 g; chitin amount 2.390 g) obtained in Production Example 1 above. Then, evening primrose oil (18 ml) was mixed to obtain an emulsion (dispersion particle size: 0.5 μm to 100 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例６〕
上記製造例１で得られた５．９重量％キチンスラリー（２０．２７ｇ；キチン量１．１９６ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（３ｍｌ）を混合し、次いで、スイートアーモンドオイル（１０ｍｌ）を混合して乳化物を得た（分散体の粒径：１．３μｍ〜８０μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 6
1% (v / v) SDS aqueous solution (3 ml) was mixed with 5.9 wt% chitin slurry (20.27 g; chitin amount 1.196 g) obtained in Production Example 1 while stirring with a glass stir bar. Next, sweet almond oil (10 ml) was mixed to obtain an emulsion (particle size of dispersion: 1.3 μm to 80 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例７〕
上記製造例１で得られた５．９重量％キチンスラリー（２０．１８ｇ；キチン量１．１９１ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（３ｍｌ）を混合し、次いで、杏仁油（１０ｍｌ）を混合して乳化物を得た（分散体の粒径：１．８μｍ〜１６０μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 7
1% (v / v) SDS aqueous solution (3 ml) was mixed with the 5.9 wt% chitin slurry (20.18 g; chitin amount 1.191 g) obtained in Production Example 1 while stirring with a glass stir bar. Next, apricot kernel oil (10 ml) was mixed to obtain an emulsion (particle size of dispersion: 1.8 μm to 160 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例８〕
上記製造例１で得られた５．９重量％キチンスラリー（２０．２４ｇ；キチン量１．１９４ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（３ｍｌ）を混合し、次いで、ココナッツオイル（１０ｍｌ）を混合して乳化物を得た（分散体の粒径：１．２μｍ〜１３７μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 8
1% (v / v) SDS aqueous solution (3 ml) was mixed with 5.9 wt% chitin slurry (20.24 g; chitin amount 1.194 g) obtained in Production Example 1 while stirring with a glass stir bar. Then, coconut oil (10 ml) was mixed to obtain an emulsion (particle size of dispersion: 1.2 μm to 137 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例９〕
上記製造例１で得られた５．９重量％キチンスラリー（２０．２６ｇ；キチン量１．１９５ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｗ／ｖ）ジアセチル酒石酸モノグリセリド水溶液（１１ｍｌ）を混合し、次いで、ココナッツオイル（１０ｍｌ）を混合して乳化物を得た（分散体の粒径：１．５μｍ〜２２７μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 9
A 1% (w / v) diacetyltartaric acid monoglyceride aqueous solution (11 ml) while stirring with a glass stir bar to the 5.9 wt% chitin slurry (20.26 g; chitin amount 1.195 g) obtained in Production Example 1 above. Then, coconut oil (10 ml) was mixed to obtain an emulsion (dispersion particle size: 1.5 μm to 227 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例１０〕
上記製造例１で得られた５．９重量％キチンスラリー（１０．１７ｇ；キチン量０．６００ｇ）に、ガラス撹拌棒で撹拌しながら、ペーストレシチン（０．４２ｇ）を混合し、次いで、ココナッツオイル（５ｍｌ）を混合して乳化物を得た（分散体の粒径：１．０μｍ〜６５μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 10
Paste lecithin (0.42 g) was mixed with the 5.9 wt% chitin slurry (10.17 g; chitin amount 0.600 g) obtained in Production Example 1 while stirring with a glass stir bar, and then coconut Oil (5 ml) was mixed to obtain an emulsion (particle size of dispersion: 1.0 μm to 65 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例１１〕
上記製造例１で得られた５．９重量％キチンスラリー（１０．１３ｇ；キチン量０．５９８ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｗ／ｖ）キラヤサポニン水溶液（６ｍｌ）を混合し、次いで、ココナッツオイル（５ｍｌ）を混合して乳化物を得た（分散体の粒径：１．５μｍ〜１００μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 11
1% (w / v) Kirayasaponin aqueous solution (6 ml) was added to the 5.9 wt% chitin slurry (10.13 g; chitin amount 0.598 g) obtained in Production Example 1 while stirring with a glass stirring rod. Next, coconut oil (5 ml) was mixed to obtain an emulsion (dispersion particle size: 1.5 μm to 100 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例１２〕
上記製造例１で得られた５．９重量％キチンスラリー（１０．０１ｇ；キチン量０．５９１ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｗ／ｖ）粉末レシチン水溶液（３ｍｌ）を混合し、次いで、ココナッツオイル（５ｍｌ）を混合して乳化物を得た（分散体の粒径：１．３μｍ〜６５μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 12
1% (w / v) powdered lecithin aqueous solution (3 ml) was added to the 5.9 wt% chitin slurry (10.01 g; chitin amount 0.591 g) obtained in Production Example 1 while stirring with a glass stir bar. Next, coconut oil (5 ml) was mixed to obtain an emulsion (dispersion particle size: 1.3 μm to 65 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔実施例１３〕
上記製造例２で得られた１２．４重量％エタノール和キチンスラリー（４．９９３ｇ；キチン量０．５９９ｇ）に、ガラス撹拌棒で撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（１．７ｍｌ）を混合し、次いで、大豆油（４ｍｌ）を混合して乳化物を得た（分散体の粒径：２．４μｍ〜４２４μｍ）。得られた乳化物を室温、静置条件下、３０日間保存したところ、安定した乳化状態が保たれていた。Example 13
A 1% (v / v) SDS aqueous solution (1. v / v) was stirred into the 12.4 wt% ethanol-chitin slurry (4.993 g; chitin amount 0.599 g) obtained in Production Example 2 above with a glass stirring rod. 7 ml) and then soybean oil (4 ml) to obtain an emulsion (dispersion particle size: 2.4 μm to 424 μm). When the obtained emulsion was stored for 30 days at room temperature and standing, a stable emulsified state was maintained.
〔比較例１〕
キチン粉末（１．１９１ｇ）に蒸留水を加えて混合物（２０．１８ｇ）を得た。該混合物に、スパチュラで撹拌しながら、１％（ｖ／ｖ）ＳＤＳ水溶液（３ｍｌ）を混合し、次いで、ココナッツオイル（１０ｍｌ）を混合した。その後静置した。該混合物は、オイル加えて撹拌を停止したときから分離が始まり、１０分後には３層（油、水、キチン）に明確に分離した。[Comparative Example 1]
Distilled water was added to chitin powder (1.191 g) to obtain a mixture (20.18 g). The mixture was mixed with 1% (v / v) aqueous SDS (3 ml) with stirring with a spatula, and then with coconut oil (10 ml). Then it was left to stand. The mixture began to separate when the stirring was stopped by adding oil, and after 10 minutes, it was clearly separated into three layers (oil, water, chitin).
以上の実施例および比較例の結果を表１および２にまとめる。 The results of the above Examples and Comparative Examples are summarized in Tables 1 and 2.
表１および２中、
１）ＳＤＳ：キシダ化学（株）製「ドデシル硫酸ナトリウム９８％」
２）サンソフト641D：ジアセチル酒石酸モノグリセリド、太陽化学（株）製「サンソフトNo. 641D」
３）ペーストレシチン：辻製油（株）製「SLP-ペーストリゾ」
４）キラヤサポニン：丸善製薬（株）製「キラヤニンP-20」
５）粉末レシチン：辻製油（株）製「SLP-ホワイトリゾ」
６）月見草オイル：サミット製油（株）製「月見草油」
７）杏仁油：日光ケミカルズ（株）製「杏仁油」
８）スイートアーモンドオイル：日光ケミカルズ（株）製「スイートアーモンド油」
９）ココナッツオイル：日光ケミカルズ（株）製「TRIFAT C-24」
１０）大豆油：シグマアルドリッチジャパン（株）製「大豆油」、Code No. 23-0510-5In Tables 1 and 2,
1) SDS: “Sodium dodecyl sulfate 98%” manufactured by Kishida Chemical Co., Ltd.
2) Sunsoft 641D: Diacetyltartaric acid monoglyceride, "Sunsoft No. 641D" manufactured by Taiyo Kagaku Co., Ltd.
3) Paste lecithin: “SLP-paste lyso” manufactured by Sakai Oil Co., Ltd.
4) Kirayasaponin: “Kirayanin P-20” manufactured by Maruzen Pharmaceutical Co., Ltd.
5) Powdered lecithin: “SLP-White Reso” manufactured by Sakai Oil Co., Ltd.
6) Evening Primrose Oil: “Evening Primrose Oil” manufactured by Summit Oil Co., Ltd.
7) Apricot oil: “Apricot oil” manufactured by Nikko Chemicals
8) Sweet almond oil: “Sweet almond oil” manufactured by Nikko Chemicals
9) Coconut oil: “TRIFAT C-24” manufactured by Nikko Chemicals
10) Soybean oil: “Soybean oil” manufactured by Sigma-Aldrich Japan, Code No. 23-0510-5
Claims (10)
(２)キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
(３)水和キチンスラリーに界面活性剤および油を混合する工程と
を含む、請求項１に記載のキチン乳化物の製造方法。(1) A step of dissolving chitin in a solvent containing an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the generated chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) The manufacturing method of the chitin emulsion of Claim 1 including the process of mixing surfactant and oil with a hydration chitin slurry.
(２)キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
(３)水和キチンスラリーに、１価アルコールおよび多価アルコールからなる群から選択される親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
(４)親水性溶媒和キチンスラリーに界面活性剤および油を混合する工程と
を含む、請求項１に記載のキチン乳化物の製造方法。(1) A step of dissolving chitin in a solvent containing an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the generated chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) A hydrophilic solvent selected from the group consisting of monohydric alcohols and polyhydric alcohols is added to the hydrated chitin slurry, and water molecules contained in the hydrated chitin slurry are replaced with the hydrophilic solvent, Obtaining a hydrophilic solvated chitin slurry;
(4) The manufacturing method of the chitin emulsion of Claim 1 including the process of mixing surfactant and oil with a hydrophilic solvation chitin slurry.
(２)キチン溶液を水で希釈し、必要に応じて、生成したキチンの沈殿を水洗し、または透析を行い、溶液中に含まれるカルシウムイオンまたはマグネシウムイオンとアルコールを水分子で置換して、水和キチンスラリーを得る工程と、
(３)水和キチンスラリーに、１価アルコールおよび多価アルコールからなる群から選択される親水性溶媒を添加し、水和キチンスラリー中に含まれる水分子を該親水性溶媒で置換して、親水性溶媒和キチンスラリーを得る工程と、
(４)親水性溶媒和キチンスラリーに、親水性溶媒に溶解する油を添加し、親水性溶媒和キチンスラリーに含まれる親水性溶媒を該油で置換して、油溶媒和キチンスラリーを得る工程と、
(５)油溶媒和キチンスラリーに界面活性剤および１価アルコールおよび多価アルコールからなる群から選択される親水性溶媒または水を混合する工程とを含む、請求項１に記載のキチン乳化物の製造方法。(1) A step of dissolving chitin in a solvent containing an alcohol comprising methyl alcohol or ethyl alcohol and a calcium halide salt or a magnesium halide salt to obtain a chitin solution;
(2) The chitin solution is diluted with water, and if necessary, the generated chitin precipitate is washed with water or dialyzed, and calcium ions or magnesium ions and alcohol contained in the solution are replaced with water molecules, Obtaining a hydrated chitin slurry;
(3) A hydrophilic solvent selected from the group consisting of monohydric alcohols and polyhydric alcohols is added to the hydrated chitin slurry, and water molecules contained in the hydrated chitin slurry are replaced with the hydrophilic solvent, Obtaining a hydrophilic solvated chitin slurry;
(4) a hydrophilic solvation chitin slurry was added an oil which dissolves in the hydrophilic solvent, the hydrophilic solvent contained in the hydrophilic solvation chitin slurry was replaced with the oil, to obtain an oil soluble Nakadachiwa chitin slurry Process,
(5) oil soluble to Nakadachiwa chitin slurry and a step of mixing a hydrophilic solvent or water is selected from the group consisting of surfactant and monohydric alcohols and polyhydric alcohols, chitin emulsion according to claim 1 Manufacturing method.
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