JPS621452A - Preparation of microcapsule having heat accumulating material sealed therein - Google Patents
Preparation of microcapsule having heat accumulating material sealed thereinInfo
- Publication number
- JPS621452A JPS621452A JP13782685A JP13782685A JPS621452A JP S621452 A JPS621452 A JP S621452A JP 13782685 A JP13782685 A JP 13782685A JP 13782685 A JP13782685 A JP 13782685A JP S621452 A JPS621452 A JP S621452A
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- storage material
- organic solvent
- boiling point
- heated
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/12—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution
- B01J13/125—Making microcapsules or microballoons by phase separation removing solvent from the wall-forming material solution by evaporation of the solvent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、蓄熱材封入マイクロカプセルの製造。[Detailed description of the invention] [Industrial application field] The present invention relates to the production of microcapsules encapsulating a heat storage material.
法に関する。更に詳しくは、化学反応を伴わすに蓄熱材
を高分子腹材料でマイクロカプセル化した蓄熱材封入マ
イクロカプセルの製造法に関する。Regarding the law. More specifically, the present invention relates to a method for producing heat storage material-encapsulated microcapsules in which a heat storage material is microencapsulated with a polymeric material through a chemical reaction.
〔従来の技術〕および〔発明が解決しようとする問題点
〕蓄熱材と熱媒体との熱交換手段としては、直接接触に
よる方法が最も効率がよいが、蓄熱材と熱媒体とが物理
的、化学的に相互作用を生ずる場合が多く、そのため間
接接触を行わざるを得ない。[Prior art] and [Problems to be solved by the invention] Direct contact is the most efficient means of heat exchange between the heat storage material and the heat medium, but if the heat storage material and the heat medium are physically In many cases, chemical interactions occur, so indirect contact must be made.
この間接熱交換手段としては、蓄熱材をカプセル化し、
カプセル膜を介して熱媒体と熱交換する方法が蓄熱材の
単位体積当シの表面積が大きくなるため有効であり、こ
の単位体積当りの表面積を大きくして伝熱促進をより有
効ならしめるために１カプセルのマイクロ化が望まれて
いる。As this indirect heat exchange means, the heat storage material is encapsulated,
The method of exchanging heat with a heat medium through a capsule membrane is effective because it increases the surface area per unit volume of the heat storage material, and in order to increase the surface area per unit volume and make heat transfer more effective. It is desired to miniaturize one capsule.
しかしながら、カプセルに蓄熱材を封入する工程でカプ
セルをマイクロ化することは、それだけ高度な技術が必
要であシ、製造コストの増加を招くため、実際上それの
マイクロ化には限界がみられた。また、一般のカプセル
化方法では、カプセル膜が化学反応によって形成される
ため、膜形成材料と反応性を有する場合の多い蓄熱材を
カプセル化させることは困難であった。However, making the capsule micro in the process of enclosing the heat storage material into the capsule requires advanced technology and increases manufacturing costs, so there is a practical limit to making the capsule micro. . In addition, in general encapsulation methods, since the capsule membrane is formed by a chemical reaction, it is difficult to encapsulate a heat storage material that is often reactive with the membrane-forming material.
本発明者らは、このような問題点を有する蓄熱材のマイ
クロカプセル化方法について検討を重ねた結果、（水相
／有機相）／水相よりなる二次エマルジョン液を用いる
ことにより、かがる課題が効果的に解決されることを見
出した。As a result of repeated studies on microencapsulation methods for heat storage materials that have such problems, the present inventors found that by using a secondary emulsion liquid consisting of (aqueous phase/organic phase)/aqueous phase, We have found that the problems faced can be effectively solved.
〔問題点を解決するための手段〕および〔作用〕従って
、本発明は蓄熱材封入マイクロカプセルの製造法に係シ
、蓄熱材封入マイクロカプセルの製造は、蓄熱材の融解
温度より高いｄβ点を有しかつ蓄熱材と相互作用を示さ
ない有機溶媒にカプセル形成性高分子材料および油溶性
界面活性剤を溶解させた溶液を、蓄熱材の融解温度乃至
有機溶媒の沸点の間の温度に加熱し、この加熱溶液中に
有機溶媒の沸点以下の温度に加熱された蓄熱材融解液を
滴下し、そこに形成された一次エマルジョン液を、蓄熱
材の融解湿度乃至有機溶媒の沸点の間の温度て加熱され
た保護コロイド溶液または水溶性界面活性剤の水溶液中
に滴下して二次エマルジョン液を形成させ、該二次エマ
ルジョン液を有機溶媒の沸点以上に加熱して有機溶媒を
蒸発させ、高分子材料のカプセル膜を形成させることに
より行われる。[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a method for producing microcapsules encapsulating a heat storage material, and the production of microcapsules encapsulating a heat storage material requires a dβ point higher than the melting temperature of the heat storage material. A solution in which a capsule-forming polymeric material and an oil-soluble surfactant are dissolved in an organic solvent that does not interact with the heat storage material is heated to a temperature between the melting temperature of the heat storage material and the boiling point of the organic solvent. A melted heat storage material heated to a temperature below the boiling point of the organic solvent is dropped into this heated solution, and the primary emulsion liquid formed there is heated to a temperature between the melting humidity of the heat storage material and the boiling point of the organic solvent. It is dropped into a heated protective colloid solution or an aqueous solution of a water-soluble surfactant to form a secondary emulsion, and the secondary emulsion is heated to a temperature higher than the boiling point of the organic solvent to evaporate the organic solvent. This is done by forming an encapsulating membrane of the material.
例えば、蓄熱材として無機水和物を用いてそれをマイク
ロカプセル化するには、次に示されるような蓄熱材の融
解温度（融点）、即ち
塩化カルシウム・６水和物 ２９℃
炭酸ナトリウム・１０水和物 ３２℃硫酸ナトリウム
・１０水和物 〃
リン酸水素２ナトリウム・１２水和物 ３６℃
′硝酸亜鉛・６水和物 ｒ
硝酸カルシウム・６水和物４５℃
チオ硫酸ナトリウム・５水和物 ４８℃硝酸ニッケル
・６水和物 ５４℃
酢酸ナトリウム・３水和物 ５８℃
より高い沸点を有しかつ蓄熱材と相互作用を示ざない有
機溶媒、例えばペンタン（沸点３６℃）、シクロペンク
ン（同４９℃）、ヘキサン（同６９℃）、シクロヘキサ
ン（同８０℃）などの飽和炭化水素、ベンゼン（同８０
℃）などの芳香族炭化水素、塩化メチレン（同４０℃）
、１−クロルプロパン（同４７℃）、ジクロルエタン（
同５７℃）、クロロホルム（同６１℃）、四塩化炭素（
同７７℃）、１−クロルブタン（同７８℃）などのハロ
ゲン化炭化水素などの有機溶媒、好ましくは用いられる
蓄熱材の融解温度より約５〜３０℃高い沸点を有する有
機溶媒に、カプセル形成性高分子材料および油溶性界面
活性剤を溶解させた溶液がまず調製される。For example, in order to microcapsule an inorganic hydrate as a heat storage material, the following melting temperatures (melting points) of the heat storage material are required: Calcium chloride hexahydrate 29°C Sodium carbonate 10°C Hydrate 32℃ Sodium sulfate decahydrate Disodium hydrogen phosphate decahydrate 36℃
'Zinc nitrate hexahydrate r Calcium nitrate hexahydrate 45℃ Sodium thiosulfate pentahydrate 48℃ Nickel nitrate hexahydrate 54℃ Sodium acetate trihydrate 58℃ Higher boiling point Organic solvents that contain organic solvents and do not interact with the heat storage material, such as saturated hydrocarbons such as pentane (boiling point: 36°C), cyclopenkune (boiling point: 49°C), hexane (boiling point: 69°C), cyclohexane (boiling point: 80°C), and benzene. (80
Aromatic hydrocarbons such as methylene chloride (40℃)
, 1-chloropropane (47℃), dichloroethane (
57℃), chloroform (61℃), carbon tetrachloride (
77℃), halogenated hydrocarbons such as 1-chlorobutane (78℃), and preferably an organic solvent having a boiling point about 5 to 30℃ higher than the melting temperature of the heat storage material used. A solution containing a polymeric material and an oil-soluble surfactant is first prepared.
カプセル形成性高分子材料としては、例えばポリスチレ
ン、ポリエチレン、ポリ塩化ビニルなど、蓄熱材と相互
作用のない任意の熱可塑性樹脂が、濃度約２〜１０雷恰
％の有機溶媒溶液として用いられる。また、油溶性界面
活性剤としては、一般に非イオン界面活性剤が、濃度約
２〜１０雷恰％の有機溶媒溶液として用いられる。As the capsule-forming polymer material, any thermoplastic resin that does not interact with the heat storage material, such as polystyrene, polyethylene, and polyvinyl chloride, can be used in the form of an organic solvent solution having a concentration of about 2 to 10%. Furthermore, as the oil-soluble surfactant, a nonionic surfactant is generally used as a solution in an organic solvent at a concentration of about 2 to 10%.
このような有機溶媒溶液は、それぞれ用いられた蓄熱材
の融解温度乃至有機溶媒の沸点の間の温度に加熱され、
このＪＪＯ熱溶液中に有機溶媒の沸点以下に加熱された
蓄熱材融解液を、一般には撹拌下に滴下し、水相／有機
相′よりなる一次エマルジョン液を形成させる。形成さ
れる一次エマルジョン液の粒径は、用いられる油溶性界
面活性剤の種類および量、攪拌速度などにより調節する
ことができる。Such an organic solvent solution is heated to a temperature between the melting temperature of the heat storage material used and the boiling point of the organic solvent,
A molten heat storage material heated to a temperature below the boiling point of the organic solvent is added dropwise into the JJO hot solution, generally under stirring, to form a primary emulsion consisting of an aqueous phase/organic phase. The particle size of the primary emulsion liquid to be formed can be adjusted by the type and amount of the oil-soluble surfactant used, the stirring speed, etc.
次に、蓄熱材の融解温度乃至有機溶媒の沸点の間の温度
に加熱された保護コロイド溶液、例えばゼラチンの約１
〜５重量％水溶液または水溶性界面活性剤、例えばイオ
ン性界面活性剤の約１〜５重量％水溶液中に、一般に攪
拌しながら、前記−次エマルジョン液を滴下し、（水相
／有機相）／水相よりなシ、即ち微小蓄熱材水滴を含む
有機溶媒溶液の小滴が水中に分散した状態の°二次エマ
ルジョン液を形成させる。Next, a protective colloid solution heated to a temperature between the melting temperature of the heat storage material and the boiling point of the organic solvent, for example, about 1 ml of gelatin, is added.
The above-mentioned emulsion liquid is added dropwise, generally with stirring, into a ~5% by weight aqueous solution or a ~1-5% by weight aqueous solution of a water-soluble surfactant, e.g. an ionic surfactant (aqueous phase/organic phase). A secondary emulsion liquid is formed in which small droplets of an organic solvent solution containing minute heat storage material water droplets are dispersed in water rather than an aqueous phase.
形成された二次エマルジョン液の温度を徐々に上昇させ
、用いられた有機溶媒の沸点以上に加熱すると、有機溶
媒は水相を介して徐々に蒸発Ｕ′！！ｉ→〒高分子材料
のカプセル膜が形成され、蓄熱材はカプセル内に封入さ
れる。なお、有機溶媒の蒸発に際し、その沸点が蓄熱材
の耐熱温度より高い場合には、無機水和物の融解温度以
上でかつ耐熱温度以下の温度で有機溶媒が蒸発するよう
に、この操作を減圧下で行なうようにすればよい。When the temperature of the formed secondary emulsion liquid is gradually increased and heated above the boiling point of the organic solvent used, the organic solvent gradually evaporates through the aqueous phase U'! ! i→〒A capsule film of a polymeric material is formed, and a heat storage material is encapsulated within the capsule. When evaporating the organic solvent, if its boiling point is higher than the heat-resistant temperature of the heat storage material, this operation is performed under reduced pressure so that the organic solvent evaporates at a temperature above the melting temperature of the inorganic hydrate and below the heat-resistant temperature. You can do it below.
本発明の二次エマルジョン法による蓄熱材のカプセル化
は、カプセル膜の形成に際し化学反応が伴わないため、
反応性のある蓄熱材も容易にカプセル化することができ
る。The encapsulation of the heat storage material by the secondary emulsion method of the present invention does not involve any chemical reaction when forming the capsule membrane.
Reactive heat storage materials can also be easily encapsulated.
しかも、この蓄熱材カプセルをマイクロ化させることに
より、蓄熱材の単位体積当シの表面積が大きくなシ、蓄
熱材と熱媒体との間の熱交換性能も大幅に改善される。Furthermore, by micronizing the heat storage material capsule, the surface area per unit volume of the heat storage material is increased, and the heat exchange performance between the heat storage material and the heat medium is also significantly improved.
次だ、実施例について本発明を説明する。 The invention will now be described with reference to examples.
実施例
酢酸す） ＩＪウム・３水和物５０りを７０℃に加熱し
、完全に融解させた。この融解液を、ポリスチレン１０
重量％およびポリオキシエチレンオレイルエステル５重
量％を溶解させた７０℃の四塩化炭素溶液２０〇−中に
撹拌しながら滴下し、水相／有機相の一次エマルジミン
液を形成させた。EXAMPLE Acetic acid 50 g of IJium trihydrate was heated to 70° C. and completely melted. This melted liquid was mixed with polystyrene 10
% by weight and 5% by weight of polyoxyethylene oleyl ester were added dropwise to a 70° C. carbon tetrachloride solution with stirring to form a primary emuldimine liquid having an aqueous phase/organic phase.
この−次エマルジョン液を、７０℃に加熱させた２重量
％ゼラチン水溶液中に攪拌しながら滴下し、（水相／有
機相）／水相の二次エマルジョン液を形成させた。次に
、全体の温度を８０℃になる迄徐々に上昇させ、四塩化
炭素を蒸発させることにより、ポリスチレンのカプセル
壁を形成させた。その後液温を室温迄下げ、カプセル内
に封入された酢酸ナトリウム・３水和物を固化させ、こ
れを口過することによってゼラチン水溶液から直径約０
．０５〜２ツの蓄熱材封入マイクロカプセルを得た。This secondary emulsion liquid was added dropwise to a 2% by weight aqueous gelatin solution heated to 70°C while stirring to form a secondary emulsion liquid of (aqueous phase/organic phase)/aqueous phase. Next, the overall temperature was gradually raised to 80° C. to evaporate carbon tetrachloride, thereby forming a polystyrene capsule wall. After that, the liquid temperature is lowered to room temperature, the sodium acetate trihydrate encapsulated in the capsule is solidified, and this is passed through the mouth to form a gelatin solution with a diameter of about 0.0 mm.
．． Two heat storage material-encapsulated microcapsules were obtained.
Claims (1)
相互作用を示さない有機溶媒にカプセル形成性高分子材
料および油溶性界面活性剤を溶解させた溶液を、蓄熱材
の融解温度乃至有機溶媒の沸点の間の温度に加熱し、こ
の加熱溶液中に有機溶媒の沸点以下の温度に加熱された
蓄熱材融解液を滴下し、そこに形成された一次エマルジ
ョン液を、蓄熱材の融解温度乃至有機溶媒の沸点の間の
温度に加熱された保護コロイド溶液または水溶性界面活
性剤の水溶液中に滴下して二次エマルジョン液を形成さ
せ、該二次エマルジョン液を有機溶媒の沸点以上に加熱
して有機溶媒を蒸発させ、高分子材料のカプセル膜を形
成させることを特徴とする蓄熱材封入マイクロカプセル
の製造法。 ２、蓄熱材の融解温度より約５〜３０℃高い沸点を有す
る有機溶媒が用いられる特許請求の範囲第１項記載の蓄
熱材封入マイクロカプセルの製造法。 ３、エマルジョン液を形成させる滴下が撹拌下に行われ
る特許請求の範囲第１項記載の蓄熱材封入マイクロカプ
セルの製造法。[Claims] 1. A solution in which a capsule-forming polymer material and an oil-soluble surfactant are dissolved in an organic solvent that has a boiling point higher than the melting temperature of the heat storage material and does not interact with the heat storage material, A primary emulsion liquid is formed by heating the heat storage material to a temperature between the melting temperature of the heat storage material and the boiling point of the organic solvent, and dropping the heat storage material molten liquid heated to a temperature below the boiling point of the organic solvent into the heated solution. is dropped into a protective colloid solution or an aqueous solution of a water-soluble surfactant heated to a temperature between the melting temperature of the heat storage material and the boiling point of the organic solvent to form a secondary emulsion liquid, and the secondary emulsion liquid is 1. A method for producing microcapsules encapsulating a heat storage material, which comprises heating above the boiling point of the organic solvent to evaporate the organic solvent to form a capsule film of a polymeric material. 2. The method for producing microcapsules encapsulating a heat storage material according to claim 1, wherein an organic solvent having a boiling point higher than the melting temperature of the heat storage material by about 5 to 30° C. is used. 3. The method for producing microcapsules encapsulating a heat storage material according to claim 1, wherein the dropping to form an emulsion liquid is carried out under stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13782685A JPS621452A (en) | 1985-06-26 | 1985-06-26 | Preparation of microcapsule having heat accumulating material sealed therein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13782685A JPS621452A (en) | 1985-06-26 | 1985-06-26 | Preparation of microcapsule having heat accumulating material sealed therein |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS621452A true JPS621452A (en) | 1987-01-07 |
Family
ID=15207749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13782685A Pending JPS621452A (en) | 1985-06-26 | 1985-06-26 | Preparation of microcapsule having heat accumulating material sealed therein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS621452A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH055127U (en) * | 1990-12-25 | 1993-01-26 | 誠二 川崎 | Excretion treatment device |
| WO2014208401A1 (en) * | 2013-06-27 | 2014-12-31 | シャープ株式会社 | Heat storage capsule and heat storage member produced using same |
| US9028965B2 (en) | 2010-12-13 | 2015-05-12 | Konica Minolta Business Technologies, Inc. | Heat storage microcapsules and manufacturing method thereof |
| US9265144B2 (en) | 2011-11-21 | 2016-02-16 | Panasonic Intellectual Property Management Co., Ltd. | Electrical component resin, semiconductor device, and substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442380A (en) * | 1978-08-15 | 1979-04-04 | Matsushita Electric Works Ltd | Regenerative capsule |
-
1985
- 1985-06-26 JP JP13782685A patent/JPS621452A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442380A (en) * | 1978-08-15 | 1979-04-04 | Matsushita Electric Works Ltd | Regenerative capsule |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH055127U (en) * | 1990-12-25 | 1993-01-26 | 誠二 川崎 | Excretion treatment device |
| US9028965B2 (en) | 2010-12-13 | 2015-05-12 | Konica Minolta Business Technologies, Inc. | Heat storage microcapsules and manufacturing method thereof |
| US9265144B2 (en) | 2011-11-21 | 2016-02-16 | Panasonic Intellectual Property Management Co., Ltd. | Electrical component resin, semiconductor device, and substrate |
| WO2014208401A1 (en) * | 2013-06-27 | 2014-12-31 | シャープ株式会社 | Heat storage capsule and heat storage member produced using same |
| US10101095B2 (en) | 2013-06-27 | 2018-10-16 | Sharp Kabushiki Kaisha | Heat storage capsule and heat storage member using the same |
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