TW201943412A - Manufacturing method of microcapsule characterized in that the manufacturing method does not use organic solvent and can easily obtain carboxymethyl cellulose having excellent storage stability under dry state to be film wall regardless of the type of core structure - Google Patents
Manufacturing method of microcapsule characterized in that the manufacturing method does not use organic solvent and can easily obtain carboxymethyl cellulose having excellent storage stability under dry state to be film wall regardless of the type of core structure Download PDFInfo
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本發明是有關於一種微膠囊的製造方法，更詳細而言，是有關於一種將羧甲基纖維素作為膜壁的微膠囊的製造方法。The present invention relates to a method for manufacturing a microcapsule, and more specifically, to a method for manufacturing a microcapsule using carboxymethyl cellulose as a film wall.
於微膠囊的製法中有藉由縮合聚合的化學方法、與凝聚（coacervation）法·液中乾燥法·熔化分散冷卻法等物理化學方法、及盤式塗佈法·空氣中懸浮化法·噴霧乾燥法等機械方法。The microcapsule production methods include chemical methods such as condensation polymerization, physical and chemical methods such as coacervation, in-liquid drying, and melt-dispersion cooling, and disk coating, air suspension, and spraying. Mechanical methods such as drying.
所謂所述藉由縮合聚合的化學方法（以下稱作縮合聚合法），為例如如專利文獻1所示般的製造將以多官能性異氰酸酯為原料的聚胺基甲酸酯樹脂或聚脲樹脂、以羥甲基三聚氰胺為原料的三聚氰胺樹脂等作為膜壁的微膠囊的方法。但是該方法中存在如下問題：於聚胺基甲酸酯膜壁或聚脲膜壁的生成中產生碳酸氣體，另外，於三聚氰胺樹脂膜壁的生成中產生甲醛。The chemical method by condensation polymerization (hereinafter referred to as condensation polymerization method) is, for example, the production of a polyurethane resin or a polyurea resin using a polyfunctional isocyanate as a raw material, as shown in Patent Document 1. A method of using a melamine resin such as methylolmelamine as a raw material as a microcapsule of a film wall. However, this method has the following problems: carbon dioxide gas is generated during the formation of a polyurethane film wall or a polyurea film wall, and formaldehyde is generated during the formation of a melamine resin film wall.
另外，所謂複合凝聚法，是指作為高分子溶液，將聚陽離子溶液與聚陰離子溶液組合使用，將於已將該些溶液混合時因電相互作用而引起相分離並產生的濃厚膠體層用於膠囊化皮膜（非專利文獻1）。作為將羧甲基纖維素及/或其鈉鹽作為膜壁的微膠囊的製造方法，使用於該複合凝聚法中併用明膠的方法。作為於複合凝聚中使用的羧甲基纖維素以外的聚陰離子，已知有***膠、褐藻酸鈉、卡拉膠（carrageenan）、瓊脂（agar）等多醣類。In addition, the so-called composite coacervation method refers to a combination of a polycation solution and a polyanion solution as a polymer solution. The thick colloidal layer that is caused by phase separation due to electrical interaction when these solutions are mixed is used for Encapsulated film (non-patent document 1). As a method for producing microcapsules using carboxymethyl cellulose and / or its sodium salt as a membrane wall, a method in which gelatin is used in combination with this composite aggregation method. As polyanions other than carboxymethyl cellulose used for complex aggregation, polysaccharides such as acacia gum, sodium alginate, carrageenan, and agar are known.
於所述複合凝聚法中，不會如於所述縮合聚合法中般產生氣體，但為了引起相分離而進行pH的調整，進而為了使濃厚膠體層硬化而添加有機溶媒（甲醛或乙醇等）後，需要對pH進行再調整等，作業變得繁雜，而且亦需要考慮有機溶媒的殘留或環境污染等問題。In the complex coacervation method, no gas is generated as in the condensation polymerization method, but an organic solvent (formaldehyde, ethanol, etc.) is added to adjust the pH to cause phase separation and further harden the thick colloid layer. Later, the pH needs to be readjusted, etc., the operation becomes complicated, and the problems of residual organic solvents or environmental pollution also need to be considered.
相對於此，專利文獻2及專利文獻3中，作為使用纖維素類的微膠囊化方法、且有機溶媒與明膠均不使用的方法，揭示出將無相容性的纖維素類的水溶液與共聚物的水溶液混合，並加入作為分離劑的氯化鈉、氯化鈣、氯化鎂、或硫酸鈉，從而生成微膠囊的製造方法。On the other hand, in Patent Literature 2 and Patent Literature 3, as a method of using cellulose-based microencapsulation and using neither organic solvents nor gelatin, it has been disclosed that an incompatible cellulose-based aqueous solution is copolymerized. An aqueous solution of the substances is mixed, and sodium chloride, calcium chloride, magnesium chloride, or sodium sulfate is added as a separating agent to produce a microcapsule manufacturing method.
但是，於該些專利文獻2及專利文獻3中示出的方法中，為了獲得穩定的微膠囊，需要將特定的纖維素類與特定的共聚物組合，對於用以使用羧甲基纖維素來獲得微膠囊的具體方法，並未作任何揭示。However, in the methods shown in these Patent Documents 2 and 3, in order to obtain stable microcapsules, it is necessary to combine specific celluloses and specific copolymers, and to obtain the carboxymethyl cellulose by using The specific method of the microcapsules has not been disclosed.
針對此種課題，於專利文獻4中揭示出使用羧甲基纖維素或其鈉鹽，不會如所述縮合聚合法般產生氣體、且亦不使用有機溶媒而容易地獲得結實的微膠囊的製造方法。In response to such a problem, Patent Document 4 discloses that the use of carboxymethyl cellulose or its sodium salt does not generate gas like the condensation polymerization method described above, and it is easy to obtain strong microcapsules without using an organic solvent. Production method.
於專利文獻4的實施例中記載有製造將扁柏油作為芯物質、將羧甲基纖維素或其鈉鹽作為膜壁的微膠囊，但根據其他香料或油脂等芯物質的種類，有時發生當微膠囊已乾燥時膜壁破裂、香料氣散、餘香消失等不良狀況、或者油脂滲出等不良狀況。
[現有技術文獻]
[專利文獻]The example of Patent Document 4 describes the production of microcapsules using cypress oil as a core substance and carboxymethyl cellulose or its sodium salt as a film wall. However, it may occur depending on the type of core substance such as other flavors or oils. When the microcapsules have been dried, the film wall is broken, the fragrance gas is scattered, and the after-flavor disappears, or the oil is exuded.
[Prior Art Literature]
[Patent Literature]
[專利文獻1]日本專利特開平11-188257號公報
[專利文獻2]日本專利特開2000-033259號公報
[專利文獻3]日本專利特開2001-205075號公報
[專利文獻4]日本專利特開2012-217960號公報
[非專利文獻][Patent Document 1] Japanese Patent Laid-Open No. 11-188257
[Patent Document 2] Japanese Patent Laid-Open No. 2000-033259
[Patent Document 3] Japanese Patent Laid-Open No. 2001-205075
[Patent Document 4] Japanese Patent Laid-Open No. 2012-217960
[Non-patent literature]
[非專利文獻1]「微膠囊-其製法·性質·應用」，三共出版，近藤保·小石真純合著，1977年10月15日，第49-55頁[Non-Patent Document 1] "Microcapsules-Its Manufacturing Method, Properties and Applications", Sankyo Publishing Co., Ltd., Kondo Hiroshi Koishi, Pure Co-author, October 15, 1977, pages 49-55
[發明所欲解決之課題]
本發明是鑒於以上而形成，目的在於提供一種不使用有機溶媒且無論芯物質的種類如何，容易地獲得乾燥下的保存穩定性優異的將羧甲基纖維素作為膜壁的微膠囊的微膠囊的製造方法。[Problems to be Solved by the Invention]
The present invention has been made in view of the above, and an object thereof is to provide a microcapsule that uses carboxymethyl cellulose as a membrane wall and has excellent storage stability under drying without using an organic solvent and regardless of the type of core substance. Manufacturing method.
[解決課題之手段]
為了解決所述課題，本發明的微膠囊的製造方法設為包含以下步驟者：將羧甲基纖維素及/或其鈉鹽進而與一種以上的除此以外的水溶性高分子混合而製備水溶液的步驟；向所述水溶液中加入藉由B型黏度計所得的25℃下的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物、或者將藉由B型黏度計所得的25℃下的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物與熔點為25℃～80℃的疏水性物質熔融混合而成的混合物而製備乳化懸浮液的步驟；以及向所述乳化懸浮液中添加二價以上的金屬鹽的步驟。[Means for solving problems]
In order to solve the problem, the method for producing a microcapsule of the present invention includes a step of preparing an aqueous solution by mixing carboxymethyl cellulose and / or its sodium salt with one or more other water-soluble polymers. A step of adding a hydrophobic substance or a hydrophobic composition having a viscosity at 25 ° C. of 100 mPa · s to 10000 mPa · s obtained by a B-type viscometer to the aqueous solution, or using a B-type viscometer The obtained mixture obtained by melting and mixing a hydrophobic substance or a hydrophobic composition having a viscosity at 25 ° C of 100 mPa · s to 10000 mPa · s and a hydrophobic substance having a melting point of 25 ° C to 80 ° C to prepare an emulsion suspension A step; and a step of adding a divalent or more metal salt to the emulsified suspension.
所述製造方法中可設為，所述羧甲基纖維素及/或其鈉鹽的醚化度為0.5～0.8，印染黏性指數（Printing Viscosity Index，PVI）值為0.5以下，結構黏性為50以上。In the manufacturing method, the degree of etherification of the carboxymethyl cellulose and / or its sodium salt may be 0.5 to 0.8, the printing viscosity index (PVI) value is 0.5 or less, and the structural viscosity It is 50 or more.
另外可設為，所述羧甲基纖維素及/或其鈉鹽的藉由B型黏度計所得的25℃下的2質量%水溶液黏度為1 mPa·s～1000 mPa·s。In addition, the viscosity of a 2 mass% aqueous solution of the carboxymethyl cellulose and / or its sodium salt at 25 ° C. obtained by a B-type viscometer may be 1 mPa · s to 1000 mPa · s.
可將所述水溶性高分子設為選自由萘磺酸鈉甲醛縮合物、烷基萘磺酸鈉甲醛縮合物、聚乙烯醇、聚苯乙烯磺酸、及該些的鹽所組成的群組中的一種或兩種以上的混合物。The water-soluble polymer may be selected from the group consisting of sodium naphthalenesulfonate formaldehyde condensate, sodium alkylnaphthalenesulfonate formaldehyde condensate, polyvinyl alcohol, polystyrenesulfonic acid, and salts thereof. One or a mixture of two or more of them.
可將二價以上的金屬鹽設為選自由鈣鹽、鐵鹽、銀鹽、鋅鹽、鋇鹽、鋁鹽、銅鹽所組成的群組中的一種或兩種以上的混合物。The divalent or higher metal salt may be one or a mixture of two or more selected from the group consisting of a calcium salt, an iron salt, a silver salt, a zinc salt, a barium salt, an aluminum salt, and a copper salt.
[發明的效果]
根據本發明的製造方法，能夠於完全不使用有機溶媒的情況下簡便地製造無論芯物質的種類如何，於乾燥下保存安定性亦優異的將羧甲基纖維素作為膜壁的微膠囊。[Effect of the invention]
According to the production method of the present invention, it is possible to easily produce microcapsules using carboxymethyl cellulose as a film wall, regardless of the type of core substance, and having excellent storage stability under drying, without using an organic solvent at all.
本發明中使用的羧甲基纖維素（carboxymethyl cellulose，以下有時記載為CMC）及/或其鈉鹽（以下，有時記載為CMC-Na）的醚化度較佳為0.5～0.8。若醚化度未滿0.5，則擔心水溶性不充分，無法成為均勻的液狀，微膠囊的粒度分佈變得不均勻等，性能發生偏差。另外，若醚化度超過0.8，則擔心微膠囊的強度降低。The degree of etherification of carboxymethyl cellulose (hereinafter sometimes referred to as CMC) and / or its sodium salt (hereinafter sometimes referred to as CMC-Na) used in the present invention is preferably 0.5 to 0.8. If the degree of etherification is less than 0.5, there is a concern that the water solubility is insufficient, and a uniform liquid state cannot be obtained, and the particle size distribution of the microcapsules becomes non-uniform. If the degree of etherification exceeds 0.8, the strength of the microcapsules may be reduced.
另外，CMC及/或CMC-Na的藉由B型黏度計並以轉子轉速60 rpm、25℃測定的2質量%水溶液的黏度較佳為1 mPa·s～1000 mPa·s，更佳為1 mPa·s～100 mPa·s，進而佳為4 mPa·s～40 mPa·s。所述黏度越為高黏度，乳化時越發生凝膠化，從而有難以實現均勻乳化的傾向，所獲得的微膠囊水分散液的黏度亦變高，缺乏流動性，因此於實用方面不利。另一方面，若所述黏度為低黏度，則可提高水溶液中的CMC的濃度，因此，可增加CMC膜壁的厚度。In addition, the viscosity of the 2% by mass aqueous solution of CMC and / or CMC-Na measured by a B-type viscometer at a rotor speed of 60 rpm and 25 ° C is preferably 1 mPa · s to 1000 mPa · s, more preferably 1 mPa · s to 100 mPa · s, and more preferably 4 mPa · s to 40 mPa · s. The higher the viscosity is, the more gelation occurs during emulsification, which makes it difficult to achieve uniform emulsification. The obtained microcapsule aqueous dispersion also has a higher viscosity and lacks fluidity, which is disadvantageous in terms of practicality. On the other hand, if the viscosity is low, the CMC concentration in the aqueous solution can be increased, and therefore, the thickness of the CMC film wall can be increased.
CMC及/或CMC-Na的PVI值較佳為0.5以下，另外，結構黏性較佳為50以上，更佳為60以上。若PVI值為0.5以下、且結構黏性為50以上，則容易獲得乾燥下的保存安定性優異的微膠囊。The PVI value of CMC and / or CMC-Na is preferably 0.5 or less, and the structural viscosity is preferably 50 or more, and more preferably 60 or more. When the PVI value is 0.5 or less and the structural viscosity is 50 or more, it is easy to obtain microcapsules having excellent storage stability under dry conditions.
再者，本說明書中，醚化度、PVI值、結構黏性於後述實施例中表示所定義及測定的數值。In addition, in this specification, the degree of etherification, PVI value, and structural viscosity are the values defined and measured in the Example mentioned later.
此種CMC及CMC-Na的製造方法並無特別限定，可藉由在進行了使纖維素與鹼發生反應的鹼纖維素化反應後，向所獲得的鹼纖維素中添加醚化劑並進行醚化反應而製造。The method for producing such CMC and CMC-Na is not particularly limited, and it can be carried out by adding an etherifying agent to the obtained alkali cellulose after performing an alkali cellulose reaction for reacting cellulose with an alkali. It is produced by etherification reaction.
具體而言，較佳為具備以下的（步驟1）鹼纖維素化反應步驟、（步驟2）醚化反應步驟、（步驟3）減黏步驟，根據此種製造方法，容易獲得醚化度、PVI值、結構黏性處於所述較佳範圍內的CMC及CMC-Na。Specifically, it is preferable to have the following (step 1) alkali cellulose reaction step, (step 2) etherification reaction step, (step 3) viscosity reduction step, and according to this manufacturing method, the degree of etherification, CMC and CMC-Na whose PVI value and structural viscosity are within the preferred ranges.
（步驟1）鹼纖維素化反應步驟
鹼纖維素化反應步驟可於包含10質量%以上且15質量%以下的鹼金屬氫氧化物的含水有機溶媒（總量100質量%）中，可使用相對於纖維素質原料的葡萄糖單元1莫耳而為1.0莫耳以上且5.0莫耳以下的鹼金屬氫氧化物來進行，例如可於25℃以上且45℃以下的液溫下以50分鐘以上且80分鐘以下的時間進行反應。(Step 1) Alkali-cellulose reaction step The alkali-cellulose reaction step may be used in an aqueous organic solvent (total 100% by mass) containing an alkali metal hydroxide of 10% by mass or more and 15% by mass or less. The glucose unit in the cellulosic raw material is 1 mol and is 1.0 mol or more and 5.0 mol or less of the alkali metal hydroxide. For example, it can be performed at a liquid temperature of 25 ° C or higher and 45 ° C or lower for 50 minutes or longer and 80 minutes or longer. The reaction takes place in less than minutes.
所述鹼金屬氫氧化物例如可列舉氫氧化鋰、氫氧化鈉、氫氧化鉀等，可使用任一種或組合使用兩種以上。所述鹼金屬氫氧化物的添加量為1.0莫耳以上，藉此容易獲得醚化度0.5以上的CMC及CMC-Na。進而，纖維素質原料的結晶化區域被充分地破壞，從而容易促進羧甲基醚化反應。另一方面，若鹼金屬氫氧化物的添加量相對於葡萄糖單元1莫耳而為5莫耳以下，則於醚化反應中過剩的鹼金屬鹽對醚化劑進行分解的情況得到抑制，且醚化劑的有效利用率提升。Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and any one of them may be used or two or more thereof may be used in combination. The addition amount of the alkali metal hydroxide is 1.0 mol or more, whereby CMC and CMC-Na having an etherification degree of 0.5 or more can be easily obtained. Furthermore, the crystallization region of the cellulosic raw material is sufficiently destroyed, and the carboxymethyl etherification reaction is easily promoted. On the other hand, if the addition amount of the alkali metal hydroxide is 5 mol or less relative to 1 mol of the glucose unit, the excessive decomposition of the etherifying agent by the alkali metal salt in the etherification reaction is suppressed, and The effective utilization of the etherifying agent is improved.
所述含水有機溶媒為既定的有機溶媒與水的混合溶媒。作為所述有機溶媒，可使用在CMC及CMC-Na的製造中通常所使用的有機溶媒。雖無特別限制，但具體而言可列舉：乙醇、甲醇、正丙醇、異丙醇、正丁醇及異丁醇等醇溶媒；丙酮、二乙基酮及甲基乙基酮等酮溶媒；二噁烷、二***等。該些有機溶媒可單獨使用，亦可以兩種以上的混合物的形式使用。該些中，就與水的相容性優異而言，較佳為碳數1～4的一元醇，進而佳為碳數1～3的一元醇。The aqueous organic solvent is a predetermined mixed solvent of water and water. As the organic solvent, an organic solvent generally used in the production of CMC and CMC-Na can be used. Although not particularly limited, specific examples include alcohol solvents such as ethanol, methanol, n-propanol, isopropanol, n-butanol, and isobutanol; ketone solvents such as acetone, diethyl ketone, and methyl ethyl ketone ; Dioxane, diethyl ether, etc .; These organic solvents may be used alone or in the form of a mixture of two or more. Among these, a monohydric alcohol having 1 to 4 carbon atoms is preferred, and a monohydric alcohol having 1 to 3 carbon atoms is more preferred in terms of excellent compatibility with water.
所述含水有機溶媒的相對於有機溶媒100質量份而言的水的含有比例並無特別限制，較佳為20質量份以上且60質量份以下。The content ratio of the water-containing organic solvent to 100 parts by mass of the organic solvent is not particularly limited, but it is preferably 20 parts by mass or more and 60 parts by mass or less.
（步驟2）醚化反應步驟
醚化反應步驟中，於20℃以上且40℃以下的液溫下以50分鐘以上且80分鐘以下的時間進行醚化劑的添加，較佳為於70℃以上且100℃以下的液溫下以30分鐘以上且120分鐘以下的時間進行醚化反應。(Step 2) Etherification step In the etherification reaction step, the etherification agent is added at a liquid temperature of 20 ° C or higher and 40 ° C or lower for 50 minutes or longer and 80 minutes or shorter, preferably 70 ° C or higher. The etherification reaction is performed at a liquid temperature of 100 ° C. or lower for a period of 30 minutes to 120 minutes.
作為所述醚化劑，可列舉一氯乙酸等。Examples of the etherifying agent include monochloroacetic acid.
所述醚化劑的添加量是根據CMC及CMC-Na的設定醚化度而適宜設定。The amount of the etherification agent to be added is appropriately set according to the etherification degree of the CMC and CMC-Na.
（步驟3）減黏步驟
較佳為於pH7.0以上的反應體系中向所述醚化步驟後的羧甲基纖維素及/或其鹽中添加過氧化氫並進行減黏，減黏並無特別限定，例如可於40℃以上且70℃以下的液溫下以30分鐘以上且60分鐘以下的時間進行。(Step 3) The step of reducing viscosity is preferably to add hydrogen peroxide to the carboxymethyl cellulose and / or its salt after the etherification step in a reaction system having a pH of 7.0 or higher, and reduce the viscosity. It does not specifically limit, For example, it can carry out at the liquid temperature of 40 degreeC or more and 70 degreeC or less, for 30 minutes or more and 60 minutes or less.
所述減黏步驟中的過氧化氫的添加量較佳為相對於作為原料的羧甲基纖維素鈉鹽而添加0.1質量%以上且10質量%以下。The addition amount of hydrogen peroxide in the viscosity reduction step is preferably 0.1% by mass or more and 10% by mass or less based on the carboxymethyl cellulose sodium salt as a raw material.
利用酸將所述減黏步驟後的CMC及CMC-Na中所含的過剩的鹼中和後，經過含水有機溶媒的去除、清洗及乾燥，並進行粉碎，藉此能夠製造可適宜地用於本發明的微膠囊的製造方法中的CMC及CMC-Na。The excess alkali contained in the CMC and CMC-Na after the viscosity reduction step is neutralized with an acid, and then removed, washed, and dried by an aqueous organic solvent, and pulverized, thereby being able to be manufactured and used suitably. CMC and CMC-Na in the method for producing a microcapsule of the present invention.
本發明中使用的CMC及/或CMC-Na以外的水溶性高分子並無特別限制，可為源自天然者，亦可為藉由化學合成所得者。作為例子，可例示：三仙膠（xanthan gum）、結蘭膠（gellan gum）、聚麩胺酸、***膠、瓜爾膠（guar gum）、刺槐豆膠（Locust bean gum）、卡拉膠、澱粉、幾丁聚醣（chitosan）、果膠（pectin）、及該些的衍生物；以及作為合成系有機高分子的聚乙二醇、聚乙烯醇、聚乙烯吡咯啶酮、聚丙烯酸、聚丙烯醯胺、萘磺酸鈉或烷基萘磺酸鈉的甲醛縮合物或該些的鹽、聚苯乙烯磺酸或其鹽等。另外，亦能夠使用CMC及CMC-Na以外的羥乙基纖維素、羥基丙基甲基纖維素、羥基丙基纖維素、乙基纖維素等纖維素衍生物。該些中較佳為萘磺酸鈉或烷基萘磺酸鈉的甲醛縮合物、聚乙烯醇、聚苯乙烯磺酸、以及該些的鹽。該些水溶性高分子既能夠單獨使用一種，亦能夠組合使用兩種以上。The water-soluble polymer other than CMC and / or CMC-Na used in the present invention is not particularly limited, and may be one derived from nature or one obtained by chemical synthesis. As examples, xanthan gum, gellan gum, polyglutamic acid, acacia gum, guar gum, Locust bean gum, carrageenan, Starch, chitosan, pectin, and derivatives thereof; and polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid as synthetic organic polymers Formaldehyde condensate of acrylamide, sodium naphthalenesulfonate or sodium alkylnaphthalenesulfonate, or a salt thereof, polystyrenesulfonic acid or a salt thereof, and the like. In addition, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, and ethyl cellulose other than CMC and CMC-Na can also be used. Among these, formaldehyde condensates of sodium naphthalenesulfonate or sodium alkylnaphthalenesulfonate, polyvinyl alcohol, polystyrenesulfonic acid, and salts thereof are preferred. These water-soluble polymers can be used alone or in combination of two or more.
另外，該些水溶性高分子的分子量以重量平均分子量（Mｗ）計較佳為3000～100萬，更佳為1萬～10萬。若分子量過低，則難以形成CMC膜壁，若分子量過高，則乳化狀態容易變得不穩定。In addition, the molecular weight of these water-soluble polymers is preferably from 30 to 1 million, more preferably from 10,000 to 100,000 in terms of weight average molecular weight (Mw). If the molecular weight is too low, it is difficult to form a CMC film wall, and if the molecular weight is too high, the emulsified state tends to become unstable.
繼而，作為本發明中使用的二價以上的金屬鹽的例子，可列舉：鈣鹽、鐵鹽、銀鹽、鋅鹽、鋇鹽、鋁鹽、銅鹽等。作為較佳的具體例，可列舉：氯化鐵、硫酸鐵、硫酸鋁、乙酸鋁、明礬、硝酸銀、氫氧化鈣、硫酸鋅、硫酸銅、硫酸鋇等。該些二價以上的金屬鹽亦既能夠單獨使用一種，亦能夠組合使用兩種以上。Examples of the divalent or higher metal salt used in the present invention include calcium salts, iron salts, silver salts, zinc salts, barium salts, aluminum salts, and copper salts. Preferred examples include ferric chloride, ferric sulfate, aluminum sulfate, aluminum acetate, alum, silver nitrate, calcium hydroxide, zinc sulfate, copper sulfate, and barium sulfate. These two or more valent metal salts can be used alone or in combination of two or more.
本發明中，藉由使用該些二價以上的金屬鹽而獲得微膠囊的芯物質保持性優異、對釋放的控制亦容易的微膠囊。認為其原因在於：藉由在該些二價以上的金屬鹽與CMC的羧基的氫離子或鈉離子之間進行離子交換而於CMC分子間發生交聯，藉此，藉由結實的CMC壁而形成微膠囊。如所述般，藉由先前的縮合聚合法來製造包含聚胺基甲酸酯膜壁或聚脲膜壁的微膠囊時產生碳酸氣體，另外，生成包含三聚氰胺樹脂的微膠囊時產生甲醛，但本發明中不產生此種氣體，因此，無需進行氣體去除或未反應物去除，能夠於短時間內結束微膠囊化。In the present invention, microcapsules having excellent core substance retention and easy release control are obtained by using these bivalent or higher metal salts. The reason for this is considered to be that the cross-linking between the CMC molecules occurs by ion exchange between the divalent or higher metal salt and the hydrogen ions or sodium ions of the carboxyl group of the CMC. Formation of microcapsules. As described above, carbon dioxide gas is generated when microcapsules containing a polyurethane film wall or a polyurea film wall are produced by the previous condensation polymerization method, and formaldehyde is generated when microcapsules containing a melamine resin are produced, but Since no such gas is generated in the present invention, it is not necessary to perform gas removal or unreacted matter removal, and the microencapsulation can be completed in a short time.
作為本發明的膠囊中所使用的芯物質，若為藉由B型黏度計並以轉子轉速60 rpm、25℃測定的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物、或者將藉由B型黏度計並以轉子轉速60 rpm、25℃測定的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物與熔點為25℃～80℃的疏水性物質熔融混合而成的混合物，則無特別限定（以下，亦將該些彙總而稱作「疏水性物質等」）。疏水性物質可列舉香料（天然香料、合成香料、植物精油等）、農藥、生理活性物質、驅避劑、除臭劑、著色料等，於黏度未處於既定範圍內的情況下，可使用藉由與高黏度或低黏度的疏水性物質或者不揮發性的油等液體進行混合而調整為所述既定範圍內的黏度的疏水性組成物。作為用於此種黏度調整的液體的例子，可列舉植物油脂或所述香料等。另外，將於25℃下測定的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物與熔點為25℃～80℃的疏水性物質熔融混合而成的混合物於25℃下亦可為固體，但較佳為藉由B型黏度計並以轉子轉速60 rpm、熔融混合的溫度所測定的黏度為100 mPa·s以上。再者，所謂「固體」，是指無流動性的狀態。As the core substance used in the capsule of the present invention, if it is a hydrophobic substance or a hydrophobic composition having a viscosity of 100 mPa · s to 10000 mPa · s as measured by a B-type viscometer at a rotor speed of 60 rpm and 25 ° C, Or a hydrophobic substance or composition having a viscosity of 100 mPa · s to 10000 mPa · s as measured by a B-type viscometer at a rotor speed of 60 rpm and 25 ° C and a melting point of 25 ° C to 80 ° C The mixture obtained by melt-mixing the hydrophobic substances is not particularly limited (hereinafter, these are also collectively referred to as "hydrophobic substances"). Examples of the hydrophobic substance include perfumes (natural flavors, synthetic flavors, plant essential oils, etc.), pesticides, physiologically active substances, repellents, deodorants, colorants, etc. When the viscosity is not within a predetermined range, borrowing A hydrophobic composition having a viscosity within the predetermined range is adjusted by mixing with a high viscosity or low viscosity hydrophobic substance or a liquid such as non-volatile oil. Examples of the liquid used for such viscosity adjustment include vegetable oils and fats, and the like. In addition, a mixture of a hydrophobic substance or a hydrophobic composition having a viscosity of 100 mPa · s to 10000 mPa · s measured at 25 ° C and a hydrophobic substance having a melting point of 25 ° C to 80 ° C is melt-mixed at 25 ° C. The solid may also be solid, but the viscosity is preferably 100 mPa · s or more as measured by a B-type viscometer at a rotor speed of 60 rpm and a temperature of melt mixing. The term "solid" refers to a state without fluidity.
本發明的微膠囊的製造方法至少包含：（1）將CMC及/或CMC-Na進而與一種以上的除此以外的水溶性高分子混合而製備水溶液的步驟；（2）向所述水溶液中加入25℃下的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物、或者將藉由B型黏度計並於25℃下測定的黏度為100 mPa·s～10000 mPa·s的疏水性物質或疏水性組成物與熔點為25℃～80℃的疏水性物質熔融混合而成的混合物而製備乳化懸浮液的步驟；以及（3）向所述乳化懸浮液中添加二價以上的金屬鹽的步驟。The method for producing a microcapsule of the present invention includes at least: (1) a step of preparing an aqueous solution by mixing CMC and / or CMC-Na with one or more other water-soluble polymers; (2) adding the aqueous solution to the aqueous solution; Adding a hydrophobic substance or composition with a viscosity of 100 mPa · s to 10000 mPa · s at 25 ° C, or a viscosity of 100 mPa · s to 10000 mPa measured at 25 ° C with a B-type viscometer A step of preparing an emulsion suspension by melt-mixing a hydrophobic substance or a hydrophobic composition with a hydrophobic substance having a melting point of 25 ° C to 80 ° C; and (3) adding two to said emulsion suspension Valence of a metal salt.
於製備所述CMC等的水溶液的步驟（1）中，水溶液中的CMC及/或CMC-Na的濃度較佳為0.1質量%～10質量%，更佳為1質量%～5質量%。另外，所述水溶液中的CMC及/或CMC-Na以外的水溶性高分子的濃度較佳為0.1質量%～10質量%，更佳為1質量%～5質量%。所述水溶液可依據公知的方法來製備，為了容易溶解於水中，視需要若為至60℃左右為止，則亦可進行加熱。若加熱至超過60℃的溫度為止，則擔心所述CMC等的水溶液的黏度變得過低，且微膠囊的粒徑產生偏差。In step (1) of preparing the aqueous solution of CMC and the like, the concentration of CMC and / or CMC-Na in the aqueous solution is preferably 0.1% to 10% by mass, and more preferably 1% to 5% by mass. The concentration of water-soluble polymers other than CMC and / or CMC-Na in the aqueous solution is preferably 0.1% to 10% by mass, and more preferably 1% to 5% by mass. The said aqueous solution can be prepared according to a well-known method, and in order to melt | dissolve in water easily, if necessary, it can also heat if it is about 60 degreeC. When heated to a temperature exceeding 60 ° C., the viscosity of an aqueous solution such as the CMC may become too low, and there may be variations in the particle size of the microcapsules.
繼而，於向所述水溶液中加入疏水性物質等而製備乳化懸浮液的步驟中，疏水性物質等的濃度較佳為以成為最終所得的包含水性介質的微膠囊水分散液中的0.1質量%～50質量%的方式進行調整。若濃度高於50質量%，則擔心乳化變得困難、或者微膠囊水分散液的黏度增大。另一方面，於未滿0.1質量%的情況下，雖然可不存在問題地製備微膠囊，但目標芯物質的濃度變得過低，就經濟方面而言並不現實。再者，乳化懸浮可使用均質分散器等並藉由公知的方法來進行。Next, in the step of preparing an emulsion suspension by adding a hydrophobic substance or the like to the aqueous solution, the concentration of the hydrophobic substance or the like is preferably 0.1% by mass in the microcapsule aqueous dispersion containing the aqueous medium finally obtained. ～ 50% by mass. If the concentration is higher than 50% by mass, there is a concern that emulsification becomes difficult or the viscosity of the microcapsule aqueous dispersion increases. On the other hand, in the case of less than 0.1% by mass, although the microcapsules can be prepared without problems, the concentration of the target core substance becomes too low, which is not economically realistic. The emulsification and suspension can be performed by a known method using a homogeneous disperser or the like.
進而，於向所述乳化懸浮液中添加二價以上的金屬鹽的步驟中，該二價以上的金屬鹽的濃度於作為目標物的水分散液中較佳為0.0001質量%～0.01質量%，更佳為0.001質量%～0.005質量%。作為金屬鹽的添加時機，較佳為估計乳化狀態穩定的時間來添加。若藉由目視確認到所獲得的乳化懸浮液變得充分均勻，則結束乳化懸浮操作。Furthermore, in the step of adding a divalent or higher metal salt to the emulsified suspension, the concentration of the divalent or higher metal salt is preferably 0.0001% to 0.01% by mass in the target aqueous dispersion. More preferably, it is 0.001 to 0.005 mass%. As the timing of adding the metal salt, it is preferred to add the metal salt in an estimated time when the emulsified state is stable. When it is visually confirmed that the obtained emulsion suspension becomes sufficiently uniform, the emulsion suspension operation is terminated.
於所述乳化懸浮操作結束後，較佳為於18℃～80℃左右下熟化1小時～24小時左右。藉由以此種方式進行熟化而充分地進行交聯，因此可使CMC膜壁更加結實。After the emulsification and suspension operation is completed, it is preferably aged at about 18 ° C. to 80 ° C. for about 1 hour to about 24 hours. Since the crosslinking is sufficiently performed by curing in this manner, the CMC film wall can be made stronger.
藉由所述本發明的製造方法，獲得使微膠囊穩定地分散於水中而成的水分散液（包含漿料）。藉由本發明的製造方法所得的微膠囊是平均粒徑通常為1 μm～1000 μm的大致球形的粒子，其平均粒徑根據用途而適宜選擇，可藉由對乳化時的均質分散器等的攪拌速度進行調整等而加以調整。According to the production method of the present invention, an aqueous dispersion (including a slurry) obtained by stably dispersing the microcapsules in water is obtained. The microcapsules obtained by the production method of the present invention are generally spherical particles having an average particle diameter of usually 1 μm to 1000 μm. The average particle diameter is appropriately selected according to the application, and it can be stirred by a homogeneous disperser or the like during emulsification. Adjust the speed and so on.
所獲得的微膠囊水分散液可直接使用，亦可視需要利用水等進行稀釋而使用。例如，若為將香料作為芯物質的微膠囊水分散液，則對其適當進行稀釋等並藉由噴霧、浸漬等方法將其賦予至布製品且使其乾燥，藉此，可使微膠囊附著於布製品，並獲得香味得到長期保持的布製品。The obtained microcapsule aqueous dispersion can be used directly, or it can be diluted with water or the like as needed. For example, in the case of an aqueous microcapsule dispersion containing a fragrance as a core substance, the microcapsules can be adhered by appropriately diluting the microcapsules, spraying, dipping, or the like to a cloth product and drying the microcapsules. In cloth products, and obtain the cloth products with long-lasting fragrance.
於所述本發明的製造方法中，若為不偏離發明目的的範圍，則亦能夠將於微膠囊的製造方法中通常所使用的界面活性劑、防腐劑、pH調整劑、增稠劑等添加劑添加於所述水溶液或乳化懸浮液中。
[實施例]In the manufacturing method of the present invention, additives such as a surfactant, a preservative, a pH adjuster, and a thickener that are generally used in a method for manufacturing a microcapsule can be used as long as the range does not deviate from the purpose of the invention. Add to the aqueous solution or emulsion suspension.
[Example]
以下，藉由實施例來進一步對本發明進行具體說明，但本發明並不限定於以下的實施例。再者，以下的實施例中，於並未特別記載的情況下將「%」設為表示「質量%」者。另外，疏水性物質等的黏度表示藉由B型黏度計所得的轉子轉速60 rpm、25℃下的黏度，CMC-Na的黏度表示藉由B型黏度計所得的轉子轉速60 rpm、25℃下的2質量%水溶液的黏度。Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to the following examples. It should be noted that in the following examples, "%" is used to indicate "mass%" unless otherwise specified. In addition, the viscosity of a hydrophobic substance and the like indicates the viscosity at a rotor speed of 60 rpm and 25 ° C obtained by a B-type viscometer, and the viscosity of CMC-Na indicates the rotor speed at 60 rpm and 25 ° C obtained by a B-type viscometer. Viscosity of 2% by mass aqueous solution.
[羧甲基纖維素鈉鹽的製造]
[製造例1]
於具備雙軸攪拌翼的容量3 L的捏合機型反應機中裝入利用家用混合機粉碎的低密度紙漿（pulp）100 g。使氫氧化鈉60 g溶解於以異丙醇（isopropyl alcohol，IPA）：水為80：20的質量比混合而成的含水有機溶媒500 g後，投入至裝有紙漿的所述反應機內，於35℃下攪拌60分鐘而進行鹼纖維素化反應，獲得鹼纖維素。繼而，使一氯乙酸55 g溶解於所述含水有機溶媒33 g中並調整為25℃後，將所述鹼纖維素維持為35℃並花60分鐘進行添加後，花30分鐘升溫至80℃，於80℃下進行60分鐘醚化反應。[Manufacture of carboxymethyl cellulose sodium salt]
[Manufacturing example 1]
100 g of low-density pulp (pulp) pulverized with a household mixer was charged into a 3 L kneading-type reactor equipped with a biaxial stirring blade. After dissolving 60 g of sodium hydroxide in 500 g of an aqueous organic solvent mixed with a mass ratio of isopropyl alcohol (IPA): 80: 20, and putting it into the reactor equipped with pulp, The mixture was stirred at 35 ° C. for 60 minutes to perform an alkali cellulose reaction to obtain alkali cellulose. Next, after dissolving 55 g of monochloroacetic acid in 33 g of the aqueous organic solvent and adjusting the temperature to 25 ° C., the alkali cellulose was maintained at 35 ° C. and added for 60 minutes, and then the temperature was raised to 80 ° C. in 30 minutes. The etherification reaction was carried out at 80 ° C for 60 minutes.
醚化反應後，添加20%過氧化氫水溶液5 g，於50℃下進行60分鐘減黏反應。所述反應後，利用50質量%的乙酸將未反應的過剩的氫氧化鈉中和，從而成為pH6.5～7.5。將成為漿料狀的所述中和物自反應機中取出，並藉由離心分離來去除IPA，獲得粗羧甲基纖維素鈉鹽。利用70質量%甲醇水溶液來清洗該粗羧甲基纖維素鈉鹽，將作為副產物的食鹽、甘醇酸鈉及乙酸鈉去除。重覆進行兩次該清洗操作後，於80℃下乾燥4小時並加以粉碎，獲得羧甲基纖維素鈉鹽。After the etherification reaction, 5 g of a 20% hydrogen peroxide aqueous solution was added, and a viscosity reduction reaction was performed at 50 ° C for 60 minutes. After the reaction, the unreacted excess sodium hydroxide was neutralized with 50% by mass of acetic acid to have a pH of 6.5 to 7.5. The neutralized substance in the form of a slurry was taken out of the reactor, and IPA was removed by centrifugation to obtain crude carboxymethyl cellulose sodium salt. This crude carboxymethyl cellulose sodium salt was washed with a 70% by mass methanol aqueous solution, and common salt, sodium glycolate, and sodium acetate were removed as by-products. After repeating this washing operation twice, it was dried at 80 ° C. for 4 hours and pulverized to obtain carboxymethyl cellulose sodium salt.
藉由後述測定方法對所獲得的羧甲基纖維素鈉鹽的各種物性進行測定的結果是，醚化度為0.75，2質量%水溶液黏度為15 mPa·s，PVI值為0.42，結構黏性為64。As a result of measuring various physical properties of the obtained carboxymethyl cellulose sodium salt by a measurement method described below, the degree of etherification was 0.75, the viscosity of a 2% by mass aqueous solution was 15 mPa · s, the PVI value was 0.42, and the structural viscosity Is 64.
[製造例2]
將一氯乙酸的裝入量、溶解一氯乙酸的含水有機溶媒量如下述表1所示般變更，除此以外，與製造例1同樣地進行製造，獲得製造例2的羧甲基纖維素鈉鹽。[Manufacturing example 2]
Except that the amount of monochloroacetic acid and the amount of the aqueous organic solvent in which monochloroacetic acid was dissolved were changed as shown in Table 1 below, production was performed in the same manner as in Production Example 1 to obtain carboxymethyl cellulose in Production Example 2. Sodium salt.
藉由所述測定方法對所獲得的羧甲基纖維素鈉鹽的各種物性進行測定的結果是，醚化度為0.66，2質量%水溶液黏度為80 mPa·s，PVI值為0.46，結構黏性為70。As a result of measuring various physical properties of the obtained carboxymethyl cellulose sodium salt by the measurement method, the degree of etherification was 0.66, the viscosity of the 2% by mass aqueous solution was 80 mPa · s, the PVI value was 0.46, and the structure was viscous. Sex is 70.
[羧甲基纖維素鈉鹽的物性測定]
＜醚化度＞
將羧甲基纖維素鈉鹽0.6 g於105℃下乾燥4小時。精秤乾燥物的質量之後用濾紙包住並於磁製坩堝中灰化。將灰化物移至500 ml燒杯中，加入水250 ml及0.05 mol/l的硫酸水溶液35 ml並煮沸30分鐘。冷卻後，利用0.1 mol/l的氫氧化鉀水溶液對過剩的酸進行反滴定。再者，指示劑使用酚酞。使用測定結果並根據下述式（1）來算出醚化度。[Measurement of physical properties of carboxymethyl cellulose sodium salt]
<Etherification degree>
0.6 g of carboxymethyl cellulose sodium salt was dried at 105 ° C for 4 hours. The mass of the dried matter was fine-scaled, then covered with filter paper and ashed in a magnetic crucible. Transfer the ash to a 500 ml beaker, add 250 ml of water and 35 ml of a 0.05 mol / l sulfuric acid aqueous solution and boil for 30 minutes. After cooling, the excess acid was back-titrated with a 0.1 mol / l potassium hydroxide aqueous solution. The indicator is phenolphthalein. Using the measurement results, the degree of etherification was calculated according to the following formula (1).
（醚化度）=162×A/（10000-80A）…（1）
A=（af-bf1）/乾燥物的重量（g）
A：試樣1 g中的結合鹼所消耗的0.05 mol/l的硫酸水溶液的量（ml）
a：0.05 mol/l的硫酸水溶液的使用量（ml）
f：0.05 mol/l的硫酸水溶液的力價
b：0.1 mol/l的氫氧化鉀水溶液的滴定量（ml）
f1：0.1 mol/l的氫氧化鉀水溶液的力價(Etherification degree) = 162 × A / (10000-80A) ... (1)
A = （af-bf1） / weight of dry matter (g)
A: The amount of the 0.05 mol / l sulfuric acid aqueous solution consumed by the binding base in 1 g of the sample (ml)
a: The amount of 0.05 mol / l sulfuric acid solution used (ml)
f: power value of 0.05 mol / l sulfuric acid aqueous solution
b: titration of 0.1 mol / l potassium hydroxide aqueous solution (ml)
f1: power value of 0.1 mol / l potassium hydroxide aqueous solution
＜2質量%水溶液黏度＞
將羧甲基纖維素鈉鹽（約4.4 g）放入至300 ml具塞三角燒瓶中並進行精秤。向其中加入根據計算公式「試樣（g）×（99-水分量（質量%））」所算出的量的水並靜置12小時，進而混合5分鐘。使用所獲得的溶液，依據日本工業標準（Japanese Industrial Standards，JIS）Z8803並使用BM型黏度計（單一圓筒型旋轉黏度計）測定25℃下的黏度。此時，（a）將轉子轉速設為60 rpm來測定，（b）於所述（a）中的測定值為8000 mPa·s以上的情況下將轉子轉速變更為30 rpm來測定，（c）於所述（b）中的測定值為16000 mPa·s以上的情況下將轉子轉速變更為12 rpm來測定。<2% by mass aqueous solution viscosity>
Carboxymethylcellulose sodium salt (about 4.4 g) was put into a 300 ml stoppered Erlenmeyer flask and finely weighed. Water was added thereto in an amount calculated according to the calculation formula “Sample (g) × (99-Moisture (mass%))”, and it was left to stand for 12 hours, and further mixed for 5 minutes. Using the obtained solution, the viscosity at 25 ° C was measured in accordance with Japanese Industrial Standards (JIS) Z8803 using a BM-type viscometer (single-cylinder rotary viscometer). At this time, (a) the rotor speed is measured at 60 rpm, (b) when the measured value in (a) is 8000 mPa · s or more, the rotor speed is changed to 30 rpm, and (c ) When the measured value in (b) is 16000 mPa · s or more, the rotor speed is changed to 12 rpm for measurement.
＜PVI值＞
使用羧甲基纖維素鈉鹽來調整黏度為10000±500 mPa·s的水溶液並充分攪拌後，利用包覆材料（wrap）進行覆蓋並於25℃恆溫器中放置一晚。繼而，自恆溫器中取出並利用玻璃棒充分地攪拌。繼而，使用BH型黏度計，轉子NO.5以轉速2 rpm測定黏度（η2）。繼而，以轉速20 rpm測定黏度（η20）。根據該些測定值並利用下述式（2）算出PVI值。PVI值越接近1.0，表示牛頓性越強，越接近0，表示非牛頓性越強。
PVI*=η20/η2…（2）
*P
rintingV
iscosityI
ndex（印染黏性指數）＜ PVI value ＞
After using carboxymethyl cellulose sodium salt to adjust the aqueous solution with a viscosity of 10000 ± 500 mPa · s and stir well, it was covered with a wrap and left in a 25 ° C thermostat overnight. Then, it was taken out from the thermostat and stirred sufficiently with a glass rod. Then, using a BH-type viscometer, the viscosity (η2) of the rotor No. 5 was measured at a rotation speed of 2 rpm. Then, the viscosity (η20) was measured at a rotation speed of 20 rpm. From these measured values, the PVI value was calculated by the following formula (2). The closer the PVI value is to 1.0, the stronger the Newtonianness, and the closer to 0, the stronger the non-Newtonianity.
PVI * = η20 / η2… (2)
* P rinting V iscosity I ndex (printing and dyeing viscosity index)
＜結構黏性＞
使用羧甲基纖維素鈉鹽來調整黏度為10000±500 mPa·s的水溶液並充分攪拌後，利用包覆材料進行覆蓋並於25℃恆溫器中放置一晚。繼而，自恆溫器中取出並使用BH型黏度計，轉子NO.5測定20 rpm的黏度（ηM）。繼而，使用三一馬達以400 rpm攪拌10分鐘後，使用BH型黏度計，轉子NO.5測定20 rpm的黏度（ηm）。使用所測定的各黏度並利用下述式（3）來算出結構黏性。
結構黏性（%）=（ηM-ηm）/ηM …（3）＜ Structural viscosity ＞
After the carboxymethyl cellulose sodium salt was used to adjust the aqueous solution with a viscosity of 10000 ± 500 mPa · s and fully stirred, it was covered with a covering material and left in a thermostat at 25 ° C. for one night. Then, the viscosity was measured at 20 rpm (ηM) using a BH viscometer and a rotor No. 5 taken out of the thermostat. Next, after stirring at 400 rpm for 10 minutes using a Trinity motor, the viscosity (ηm) of 20 rpm was measured using a BH-type viscometer and a rotor No.5. Using the measured viscosity, the structural viscosity was calculated by the following formula (3).
Structural viscosity (%) = (ηM-ηm) / ηM… (3)
[表1]
＜微膠囊的製造＞
[實施例1]
將所述製造例1中所得的CMC-Na與聚乙烯醇（商品名：歌賽諾（Gohsenol）GL-05、日本合成化學（股）製造、皂化度88%、4%黏度5.0 mPa·s）以表2所記載的調配比例分散於水中，並加溫至80℃以使其溶解，從而獲得水溶液。＜ Manufacture of microcapsules ＞
[Example 1]
CMC-Na and polyvinyl alcohol (trade name: Gohsenol GL-05, manufactured by Nippon Synthetic Chemical Co., Ltd.) obtained in Production Example 1, saponification degree 88%, 4% viscosity 5.0 mPa · s ) Dispersed in water at the compounding ratio described in Table 2, and heated to 80 ° C. to dissolve it to obtain an aqueous solution.
於溶解後，將冷卻至室溫的所述水溶液60 g放入至300 mL的高型燒杯中，進而添加以表2所示的比例混合的疏水性物質（油相），藉由均質分散器（葉片的直徑f40 mm、攪拌速度1000 rpm）使其乳化10分鐘。乳化開始5分鐘後，逐次少量地添加製備成0.1%的氯化鈣的水溶液5 g。再者，疏水性物質等的黏度是與所述羧甲基纖維素鈉鹽的2質量%水溶液的黏度的測定同樣地，使用BM型黏度計（單一圓筒型旋轉黏度計）並將轉子轉速設為60 rpm來測定。After dissolving, 60 g of the aqueous solution cooled to room temperature was placed in a 300 mL tall beaker, and a hydrophobic substance (oil phase) mixed at a ratio shown in Table 2 was added, and the mixture was dispersed by a homogenizer. (The diameter of the blade is f40 mm and the stirring speed is 1000 rpm.) It is emulsified for 10 minutes. Five minutes after the start of the emulsification, 5 g of an aqueous solution of 0.1% calcium chloride prepared in small amounts was added successively. The viscosity of the hydrophobic substance and the like is the same as the measurement of the viscosity of the 2% by mass aqueous solution of the carboxymethylcellulose sodium salt, using a BM-type viscometer (single-cylinder rotary viscometer) and rotating the rotor. The measurement was performed at 60 rpm.
乳化結束後，將均質分散器的葉片變更為錨型的攪拌葉片，以200 rpm於室溫下攪拌1小時而進行熟化，藉此獲得具有表2所示的組成的微膠囊水分散液（漿料，以下相同）。After the emulsification was completed, the blades of the homogeneous disperser were changed to anchor-type stirring blades, and they were aged by stirring at 200 rpm at room temperature for 1 hour to obtain a microcapsule aqueous dispersion (slurry) having a composition shown in Table 2. Materials, the same below).
[實施例2～實施例7、比較例1、比較例2]
將實施例1的疏水性物質等（油相）、及CMC-Na變更為表2所記載的調配，除此以外，以與實施例1同樣的方法製備水溶液後進行乳化。乳化結束後，將葉片變更為錨型的攪拌葉片，進而加溫至60℃為止，於該溫度下攪拌1小時而進行熟化，藉此獲得表2所示的組成的微膠囊水分散液。[Example 2 to Example 7, Comparative Example 1, Comparative Example 2]
Except that the hydrophobic substance and the like (oil phase) and CMC-Na of Example 1 were changed to the formulations described in Table 2, an aqueous solution was prepared in the same manner as in Example 1 and emulsified. After the emulsification was completed, the blade was changed to an anchor-type stirring blade, and further heated to 60 ° C., and the mixture was stirred at this temperature for 1 hour to be aged, thereby obtaining a microcapsule aqueous dispersion having a composition shown in Table 2.
再者，實施例5的疏水性物質等是使用將蓖麻油與硬脂酸加熱至80℃並熔融混合而成者。藉由B型黏度計所得的轉子轉速60 rpm、80℃下的黏度為20 mPa·s，但若溫度下降至25℃，則發生固化。In addition, the hydrophobic substance and the like of Example 5 were obtained by heating castor oil and stearic acid to 80 ° C. and melt-mixing them. The viscosity of the rotor at 60 rpm and 80 ° C obtained by a B-type viscometer was 20 mPa · s. However, if the temperature dropped to 25 ° C, curing occurred.
利用雷射繞射式粒度分佈測定裝置（島津製作所（股）製造的SALD-2200）對藉由所述各實施例及比較例而獲得的微膠囊的平均粒徑進行測定。將結果示於表2。The average particle diameter of the microcapsules obtained by the respective examples and comparative examples was measured using a laser diffraction type particle size distribution measuring device (SALD-2200 manufactured by Shimadzu Corporation). The results are shown in Table 2.
如表2所示般，實施例1～實施例7及比較例1、比較例2中均獲得了平均粒徑20 μm以下的微膠囊。As shown in Table 2, in Examples 1 to 7 and Comparative Examples 1 and 2, microcapsules having an average particle diameter of 20 μm or less were obtained.
＜乾燥評價＞
於掃描式電子顯微鏡（scanning electron microscope，SEM）的試樣台上放置1滴上文中所得的微膠囊水分散液並加以風乾後，利用掃描式電子顯微鏡觀察，確認微膠囊的膜壁有無裂紋。＜ Dry evaluation ＞
One drop of the microcapsule aqueous dispersion obtained above was placed on a sample stage of a scanning electron microscope (SEM) and air-dried, and then observed with a scanning electron microscope to confirm the presence or absence of cracks in the microcapsule film wall.
[表2]
如表2所示般，根據實施例1～實施例7與比較例1、比較例2的對比，於使用既定的疏水性物質等作為微膠囊的芯物質的情況下，未看到乾燥裂紋。
[產業上之可利用性]As shown in Table 2, according to the comparison between Example 1 to Example 7 and Comparative Example 1 and Comparative Example 2, when a predetermined hydrophobic substance or the like was used as the core substance of the microcapsule, no dry crack was observed.
[Industrial availability]
藉由本發明的製造方法而獲得的微膠囊可用於香料（天然香料、合成香料、植物精油等）、農藥、生理活性物質、驅避劑、除臭劑、著色料等的釋放的持續及控制。The microcapsules obtained by the production method of the present invention can be used for sustaining and controlling the release of flavors (natural flavors, synthetic flavors, plant essential oils, etc.), pesticides, physiologically active substances, repellents, deodorants, colorants and the like.
無no
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| CN112716911A (en) * | 2021-02-04 | 2021-04-30 | 吉林省吴太感康药业有限公司 | Caffeine microcapsule, preparation method thereof and compound paracetamol and alkyl amine preparation |
| CN115287277A (en) * | 2022-08-19 | 2022-11-04 | 安徽国祯环卫科技有限公司 | Complex enzyme microcapsule and kitchen waste composting method based on same |
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| JPS5814253B2 (en) * | 1974-04-10 | 1983-03-18 | カンザキセイシ カブシキガイシヤ | Bisyou capsule no Seizouhouhou |
| JPS61254243A (en) * | 1985-05-08 | 1986-11-12 | Lion Corp | Production of microcapsule |
| JPS61254245A (en) * | 1985-05-08 | 1986-11-12 | Lion Corp | Microcapsule-containing hydrous composition |
| CA2107253C (en) * | 1992-12-15 | 1998-04-21 | Anthony Castrogiovanni | Cosmetic compositions with improved transfer resistance |
| JP2908226B2 (en) * | 1993-12-28 | 1999-06-21 | 日本製紙株式会社 | Method for selecting carboxymethylcellulose sodium salt to be used as base material for cataplasm |
| JP4330091B2 (en) * | 1999-04-07 | 2009-09-09 | 第一工業製薬株式会社 | Method for producing low viscosity sodium carboxymethylcellulose |
| US20050276831A1 (en) * | 2004-06-10 | 2005-12-15 | Dihora Jiten O | Benefit agent containing delivery particle |
| JP2012217960A (en) * | 2011-04-12 | 2012-11-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Method of manufacturing microcapsule |
| CN106795373B (en) * | 2014-07-23 | 2020-06-05 | 美国陶氏有机硅公司 | Silicone elastomer composition |
| US11424439B2 (en) * | 2016-11-25 | 2022-08-23 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Negative electrode of nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
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| CN112716911A (en) * | 2021-02-04 | 2021-04-30 | 吉林省吴太感康药业有限公司 | Caffeine microcapsule, preparation method thereof and compound paracetamol and alkyl amine preparation |
| CN115287277A (en) * | 2022-08-19 | 2022-11-04 | 安徽国祯环卫科技有限公司 | Complex enzyme microcapsule and kitchen waste composting method based on same |
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