JPS634448B2 - - Google Patents
Info
- Publication number
- JPS634448B2 JPS634448B2 JP57165000A JP16500082A JPS634448B2 JP S634448 B2 JPS634448 B2 JP S634448B2 JP 57165000 A JP57165000 A JP 57165000A JP 16500082 A JP16500082 A JP 16500082A JP S634448 B2 JPS634448 B2 JP S634448B2
- Authority
- JP
- Japan
- Prior art keywords
- microcapsules
- dissolved
- mol
- solution
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003094 microcapsule Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 21
- 230000002209 hydrophobic effect Effects 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000002775 capsule Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000012643 polycondensation polymerization Methods 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- -1 alkali metal salt Chemical class 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 6
- 229960001553 phloroglucinol Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- B01J13/14—Polymerisation; cross-linking
Description
【発明の詳細な説明】
本発明はマイクロカプセルの製造方法に関し、
詳しくは架橋した縮合ポリマーよりなる強度の大
きいマイクロカプセルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing microcapsules,
Specifically, the present invention relates to a method for producing strong microcapsules made of crosslinked condensation polymers.
従来から高分子物質によるマイクロカプセル
は、包含する内容物の種類により、感圧紙、医
薬、農薬など多方面に広く利用されている。なか
でも、ポリエステル系のマイクロカプセルはすぐ
れた強度を有するものとして良く知られている。 Conventionally, microcapsules made of polymeric substances have been widely used in various fields such as pressure-sensitive paper, medicines, and agricultural chemicals, depending on the type of content they contain. Among these, polyester microcapsules are well known as having excellent strength.
一般にこれらのポリエステル系マイクロカプセ
ルを製造する方法としては、(1)ポリエステルの有
機溶剤溶液をエチレングリコールなどの液中に乳
化して微細滴を形成し、その後有機溶剤を除々に
蒸発する方法、あるいは(2)反応性単量体を溶解し
た疎水性有機溶剤溶液とアルカリ水溶液とを用い
て界面重合法により製造する方法などが知られて
いる。しかし、上記(1)の方法では溶剤の蒸発、洗
浄が困難であるなど操作上の問題が多く、一方(2)
の方法では生成するマイクロカプセルが有機溶剤
に溶剤しやすいため、製造が非常に困難であると
共に、得られるマイクロカプセルの強度ならびに
耐溶剤性が十分でなく、その利用分野は大きく制
限されていた。 Generally, these polyester microcapsules are produced by (1) emulsifying a polyester solution in an organic solvent in a liquid such as ethylene glycol to form fine droplets, and then gradually evaporating the organic solvent; (2) A method of producing by interfacial polymerization using a hydrophobic organic solvent solution in which a reactive monomer is dissolved and an alkaline aqueous solution is known. However, method (1) above has many operational problems such as evaporation of the solvent and difficulty in cleaning, while method (2)
In this method, the microcapsules produced are easily dissolved in organic solvents, making it very difficult to manufacture, and the resulting microcapsules lack sufficient strength and solvent resistance, greatly limiting their field of use.
そこで本発明者らは上記従来技術の欠点を克服
して、強度の大きいマイクロカプセルを製造すべ
く鋭意研究を重ねた。その結果、一官能性化合
物、二官能性化合物および三官能性化合物を所定
割合で含有する疎水性溶液および水溶液を用いて
界面重合を行なうと、強度のすぐれた架橋した縮
合ポリマーよりなるマイクロカプセルが簡単な工
程で効率よく製造できることを見出し、本発明を
完成するに至つた。 Therefore, the present inventors have conducted intensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and produce microcapsules with high strength. As a result, when interfacial polymerization is carried out using hydrophobic and aqueous solutions containing monofunctional, difunctional, and trifunctional compounds in predetermined proportions, microcapsules made of crosslinked condensation polymers with excellent strength are formed. They discovered that it can be manufactured efficiently through a simple process and completed the present invention.
すなわち本発明は、重合性物質を溶解した疎水
性溶液(A)および前記物質と縮重合しうる重合性物
質を溶解した水溶液(B)であり、かつ前記両溶液
(A)、(B)中に存在する重合性物質の合計割合を二官
能性化合物に対して一官能性化合物4.0モル％以
上および三官能性化合物3.5モル％以上に調節し
た溶液(A)、(B)を用いて界面縮重合を行なうことを
特徴とするカプセル壁が架橋した縮合ポリマーよ
りなるマイクロカプセルの製造方法を提供するも
のである。 That is, the present invention provides a hydrophobic solution (A) in which a polymerizable substance is dissolved and an aqueous solution (B) in which a polymerizable substance capable of condensation polymerization with the substance is dissolved;
A solution (A) in which the total proportion of polymerizable substances present in (A) and (B) is adjusted to 4.0 mol% or more of a monofunctional compound and 3.5 mol% or more of a trifunctional compound to the difunctional compound; The present invention provides a method for producing microcapsules whose capsule walls are made of a crosslinked condensation polymer, which is characterized by carrying out interfacial condensation polymerization using (B).
本発明により得られるマイクロカプセルは前述
した如く、従来のカプセルと異なり、カプセル壁
が架橋した縮合ポリマーより構成されており、機
械的強度ならびに耐溶剤性にすぐれたものであ
る。この架橋した縮合ポリマーは各種のものがあ
り、例えば架橋したポリカーボネート、架橋した
ポリエステル、架橋したポリエステルポリカーボ
ネート、架橋したポリアミドなどをあげることが
できる。 As mentioned above, the microcapsules obtained according to the present invention are different from conventional capsules in that the capsule walls are composed of a crosslinked condensation polymer and have excellent mechanical strength and solvent resistance. There are various types of crosslinked condensation polymers, such as crosslinked polycarbonate, crosslinked polyester, crosslinked polyester polycarbonate, and crosslinked polyamide.
このようなマイクロカプセルは従来のものとは
全く異なり、新規なものである。またこのマイク
ロカプセルを製造するにあたつても通常の方法で
は困難であり、重合操作の条件などを工夫する必
要があり、例えば前述した本発明の方法などによ
つてはじめて製造することができる。 Such microcapsules are completely different from conventional ones and are new. In addition, it is difficult to produce these microcapsules using conventional methods, and it is necessary to devise conditions for polymerization. For example, they can only be produced by the method of the present invention described above.
本発明の方法によれば、重合性物質を溶解した
疎水性溶液(A)およびこの重合性物質と縮重合しう
る重合性物質を溶解した水溶液(B)を用い、これら
を混合撹拌していずれか一方の溶液を微細粒子と
して乳濁あるいは懸濁させ、両溶液の界面にて縮
重合を行なつてマイクロカプセル壁を形成する。
ここで両溶液(A)、(B)中に溶解せしめる重合性物質
は一官能性化合物、二官能性化合物および三官能
性化合物よりなるが、このうち二官能性化合物は
界面縮重合の主要成分として作用し、また三官能
性化合物は架橋反応を推進し、一方、一官能性化
合物は過度の縮重合を抑制する作用を示す。従つ
て、これらの一、二、三官能性化合物の溶解量は
一定の範囲に定めることが必要である。この点に
ついて本発明者らは特に詳細に検討を重ねた結
果、上記両溶液(A)、(B)中に存在する重合性物質の
合計割合を、二官能性化合物に対して一官能性化
合物を４モル％以上、好ましくは4.5〜15モル％
とし、三官能性化合物を3.5モル％以上、好まし
くは４〜15モル％の範囲に選定すべきであること
が判明した。ここで一官能性化合物を４モル％未
満とすると縮重合が過度に進行して重合系がゲル
化し、逆に15モル％を超えると縮重合が十分に進
行せず、生成物がカプセル壁を形成しない。ま
た、三官能性化合物を3.5モル％未満とすると、
マイクロカプセルが生成せず、４モル％以上でな
いと架橋反応が十分に進行せず、得られるポリマ
ーの架橋が十分でなく、その結果、形成されるカ
プセル壁は強度や耐溶剤性において不十分なもの
となる。 According to the method of the present invention, a hydrophobic solution (A) in which a polymerizable substance is dissolved and an aqueous solution (B) in which a polymerizable substance capable of condensation polymerization with this polymerizable substance is dissolved are mixed and stirred. One of the solutions is emulsified or suspended as fine particles, and condensation polymerization is performed at the interface of both solutions to form microcapsule walls.
Here, the polymerizable substances dissolved in both solutions (A) and (B) consist of monofunctional compounds, difunctional compounds, and trifunctional compounds, among which the difunctional compounds are the main components of interfacial condensation polymerization. In addition, trifunctional compounds promote the crosslinking reaction, while monofunctional compounds exhibit the effect of suppressing excessive polycondensation. Therefore, it is necessary to set the amount of these mono-, di-, and trifunctional compounds dissolved within a certain range. As a result of particularly detailed studies by the present inventors regarding this point, we have determined that the total ratio of polymerizable substances present in both solutions (A) and (B) is higher than that of the monofunctional compound relative to the difunctional compound. 4 mol% or more, preferably 4.5 to 15 mol%
It has been found that the trifunctional compound should be selected in an amount of 3.5 mol % or more, preferably in the range of 4 to 15 mol %. If the monofunctional compound content is less than 4 mol%, the condensation polymerization will proceed excessively and the polymerization system will turn into a gel.On the other hand, if the monofunctional compound content exceeds 15 mol%, the condensation polymerization will not proceed sufficiently and the product will adhere to the capsule wall. Not formed. Also, if the trifunctional compound is less than 3.5 mol%,
If microcapsules are not produced and the crosslinking reaction is not 4 mol% or more, the crosslinking reaction of the resulting polymer is not sufficient, and as a result, the capsule walls formed are insufficient in strength and solvent resistance. Become something.
本発明の方法において、疎水性溶液(A)および水
溶液(B)に溶解せしめるべき重合性物質は、特に制
限はなく、生成すべき架橋した縮合ポリマーの種
類により適宜選定すればよい。この架橋した縮合
ポリマーとしては、前述した如く、様々なものが
あげられるが、特に好ましくは架橋したポリカー
ボネートである。この架橋したポリカーボネート
をカプセル壁として形成する場合、疎水性溶液(A)
には二官能性化合物として二価フエノールのビス
クロロホーメート（クロロホーメート基含有ポリ
カーボネートオリゴマーを含む）を溶解させてお
く。またこの溶液(A)には上記の二官能性化合物と
共に、フロロゲルシノール、トリメリト酸などの
三官能性化合物を適量溶解しておき、さらに必要
により、トリメチルアミン、トリエチルアミンな
どの一官能性化合物を溶解あるいは予備処理して
おく。なお、ここで、二価フエノールのビスクロ
ロホーメートの種類ならびに調製法は、特開昭58
−147423号公報に詳述されており、また、クロロ
ホーメート基含有ポリカーボネートオリゴマーの
製造法および三官能性化合物の詳細については特
開昭58−185619号公報に記載されているとおりで
ある。一方、前記疎水性溶液(A)に対して、水溶液
(B)には、二官能性化合物として、二価フエノール
のアルカリ金属塩を溶解させておき、また必要に
応じてフエノール、Ｐ−tert−ブチルフエノール
等の一官能性化合物を溶解しておくこともでき
る。このような重合性物質を溶解した疎水性溶液
(A)と水溶液(B)を用いて両液を混合して乳濁させ界
面重合を行なえば、カプセル壁が架橋したポリカ
ーボネートよりなるマイクロカプセルが得られ
る。 In the method of the present invention, the polymerizable substances to be dissolved in the hydrophobic solution (A) and the aqueous solution (B) are not particularly limited, and may be appropriately selected depending on the type of crosslinked condensation polymer to be produced. As described above, various types of crosslinked condensation polymers can be used, but crosslinked polycarbonate is particularly preferred. When forming this cross-linked polycarbonate as a capsule wall, a hydrophobic solution (A)
A bischloroformate of divalent phenol (including a chloroformate group-containing polycarbonate oligomer) is dissolved in the solution as a difunctional compound. In addition, in this solution (A), an appropriate amount of trifunctional compounds such as phlorogelsinol and trimellitic acid are dissolved in addition to the above bifunctional compounds, and if necessary, monofunctional compounds such as trimethylamine and triethylamine are dissolved. Or pre-process it. The type and preparation method of bischloroformate of dihydric phenol are described in Japanese Patent Application Laid-open No. 1983
The method for producing the chloroformate group-containing polycarbonate oligomer and the details of the trifunctional compound are described in Japanese Patent Application Laid-Open No. 185619/1983. On the other hand, for the hydrophobic solution (A), the aqueous solution
In (B), an alkali metal salt of divalent phenol is dissolved as a difunctional compound, and if necessary, a monofunctional compound such as phenol or P-tert-butylphenol is dissolved. You can also do it. A hydrophobic solution containing such polymerizable substances
By mixing (A) and an aqueous solution (B), emulsifying the two solutions, and performing interfacial polymerization, microcapsules with capsule walls made of crosslinked polycarbonate can be obtained.
本発明の製造方法にあつては、前述の二官能性
化合物と三官能性化合物の反応生成物を含有する
疎水性溶液に対して二官能性化合物のアルカリ水
溶液を加え、重縮合反応する方法が最も一般的で
あり、一官能性化合物も通常は疎水性溶液に加え
て予め反応を行なつておくとよい。このような方
法によつてマイクロカプセルを製造した後の疎水
性溶液中には、反応性生成物が残つているので、
引きつづき二官能性化合物のアルカリ水溶液を加
えることにより順次マイクロカプセルを得ること
ができる。 In the production method of the present invention, an aqueous alkaline solution of a difunctional compound is added to the hydrophobic solution containing the reaction product of the aforementioned difunctional compound and trifunctional compound, and a polycondensation reaction is carried out. The most common type of compound is a monofunctional compound, which is usually added to a hydrophobic solution and reacted in advance. Since reactive products remain in the hydrophobic solution after producing microcapsules by such a method,
By subsequently adding an alkaline aqueous solution of a difunctional compound, microcapsules can be obtained one after another.
上記マイクロカプセルのカプセル壁を架橋した
ポリエステルポリカーボネートで形成したい場合
は、疎水性溶液(A)中に、前述した二価フエノール
のビスクロロホーメートと共にジカルボン酸の酸
ハロゲン化物を溶解しておき、水溶液(B)中に二価
フエノールのアルカリ金属塩を溶解しておくこと
が好ましい。またこの際、一官能性化合物、三官
能性化合物は適宜、疎水性溶液(A)および／あるい
は水溶液(B)に溶解しておけばよい。 If you want to form the capsule wall of the above microcapsules with cross-linked polyester polycarbonate, dissolve the acid halide of dicarboxylic acid together with the bischloroformate of dihydric phenol mentioned above in the hydrophobic solution (A), and then dissolve the aqueous solution. It is preferable to dissolve an alkali metal salt of divalent phenol in (B). Further, at this time, the monofunctional compound and the trifunctional compound may be dissolved in the hydrophobic solution (A) and/or the aqueous solution (B) as appropriate.
そのほか、カプセル壁を架橋したポリアミドで
形成する場合には、疎水性溶液(A)中にジ酸または
ポリ酸ハライドを溶解させ、一方、水溶液(B)中に
はジアミンまたはポリアミンを溶解させておけば
よく、またカプセル壁を架橋したポリエステルで
形成する場合には、疎水性溶液(A)中にはジ酸また
はポリ酸ハライドを溶解させ、一方、水溶液(B)中
にはジオールまたはポリオールを溶解させておけ
ばよい。 In addition, if the capsule wall is made of cross-linked polyamide, the diacid or polyacid halide should be dissolved in the hydrophobic solution (A), while the diamine or polyamine should be dissolved in the aqueous solution (B). If the capsule wall is made of cross-linked polyester, the diacid or polyacid halide is dissolved in the hydrophobic solution (A), while the diol or polyol is dissolved in the aqueous solution (B). Just let it happen.
本発明の方法では、上述の如く目的に応じて選
定した所定の重合性物質を溶解した疎水性溶液(A)
と水溶液(B)を混合していずれか一方を微細な粒子
として乳濁ないし懸濁させ、界面にて縮重合反応
を行なう。ここで、疎水性溶液(A)の溶媒は水を相
溶せず、しかも用いる重合性物質を十分に溶解し
うるものであればよく、目的に応じて適宜定めれ
ばよい。具体的には、メチレンクロライド、クロ
ロホルム、クロルベンゼンなどをあげることがで
きる。また、製造するマイクロカプセルの内部に
医薬、農薬、染料等の有用成分を包含させたいと
きは、予めこれらの有用成分を疎水性溶液(A)また
は水溶液(B)に溶解せしめておき、この有用成分を
含む溶液が微細粒子を形成するように両溶液(A)、
(B)を混合し、界面重合を行なえば、内部に有用成
分が包含された状態でカプセル壁が形成され、目
的とするマイクロカプセルが得られる。このマイ
クロカプセルは必要に応じて洗浄した後、各種用
途に供することができる。 In the method of the present invention, a hydrophobic solution (A) in which a predetermined polymerizable substance selected according to the purpose as described above is dissolved.
and the aqueous solution (B), one of them is emulsified or suspended as fine particles, and a polycondensation reaction is carried out at the interface. Here, the solvent of the hydrophobic solution (A) may be any solvent that is not compatible with water and can sufficiently dissolve the polymerizable substance used, and may be appropriately determined depending on the purpose. Specifically, methylene chloride, chloroform, chlorobenzene, etc. can be mentioned. In addition, when it is desired to incorporate useful ingredients such as medicines, agricultural chemicals, and dyes into the microcapsules to be manufactured, these useful ingredients are dissolved in a hydrophobic solution (A) or an aqueous solution (B) in advance. Both solutions (A) so that the solution containing the components forms fine particles,
When (B) is mixed and interfacial polymerization is performed, the capsule wall is formed with the useful components contained therein, and the desired microcapsules are obtained. After washing the microcapsules as necessary, they can be used for various purposes.
かくして得られるマイクロカプセルは、両溶液
(A)、(B)の混合の際の乳濁の状態により10〜2000μ
の大きさのものとなり、カプセル壁が架橋した縮
合ポリマーより形成されているため、強度が大き
く、また耐溶剤性も大きい。 The microcapsules thus obtained are
10~2000μ depending on the emulsion state when mixing (A) and (B)
The capsule wall is made of crosslinked condensation polymer, so it has high strength and solvent resistance.
従つて、本発明のマイクロカプセルは、内包す
る有用成分の種類に応じて、様々な産業分野に幅
広くかつ有効に利用することができる。例えば、
内包する有用成分としてインクや染料を用いれば
感圧紙に塗布して使用でき、また農薬、医薬が内
包する有用成分であれば、それぞれの分野で有効
のに利用することができる。 Therefore, the microcapsules of the present invention can be widely and effectively utilized in various industrial fields depending on the type of useful ingredients contained therein. for example,
If ink or dye is used as the useful ingredient contained therein, it can be applied to pressure-sensitive paper and used, and if it is a useful ingredient contained in agricultural chemicals or medicines, it can be effectively used in the respective fields.
特に本発明のマイクロカプセルは、従来のマイ
クロカプセルでは包含することができなかつた有
機溶剤溶液をも包含することができるため、まつ
たく新たな分野に使用することが可能である。ま
た包含された水または有機溶剤を乾燥除去するこ
とにより、耐熱性、耐薬品性にすぐれた中空体を
得ることができ、これらは軽量充てん剤などとし
て軽量構造材（たとえば浮力材）などに利用する
ことができる。 In particular, the microcapsules of the present invention can contain organic solvent solutions that conventional microcapsules cannot contain, and therefore can be used in new fields. In addition, by drying and removing the water or organic solvent contained in it, it is possible to obtain a hollow body with excellent heat resistance and chemical resistance, which can be used as a lightweight filler in lightweight structural materials (for example, buoyancy materials), etc. can do.
次に本発明を実施例によりさらに詳しく説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
ビスフエノールＡポリカーボネートオリゴマー
のメチレンクロライド溶液（濃度320ｇ／、ク
ロロホーメート基濃度0.706規定）300mlに、フロ
ログルシノール5.0ｇ（ビスフエノールＡに対し
て7.8モル％）および苛性ソーダ4.76ｇを溶解し
た水20mlを加え、さらにトリエチルアミン0.7mg
を含む水溶液0.4mlを添加し、300r.p.m.で50分間
撹拌した。次に、上記処理して得られたオリゴマ
ー溶液に、メチレンクロライド150mlを添加し、
さらにＰ−tert−ブチルフエノール３ｇ（ビスフ
エノールＡに対して5.1モル％）、ビスフエノール
A7.6ｇを溶解した２規定苛性ソーダ水溶液130ml
およびトリエチルアミン1.05mgを含む水溶液0.6
mlを加えて撹拌し、乳濁状態にした後、600r.p.
m.で20分間撹拌して縮重合反応を行なつた。Example 1 5.0 g of phloroglucinol (7.8 mol% based on bisphenol A) and 4.76 g of caustic soda were dissolved in 300 ml of a methylene chloride solution of bisphenol A polycarbonate oligomer (concentration 320 g/, chloroformate group concentration 0.706 normal). Add 20ml of water and add 0.7mg of triethylamine.
0.4 ml of an aqueous solution containing was added and stirred at 300 rpm for 50 minutes. Next, 150 ml of methylene chloride was added to the oligomer solution obtained by the above treatment,
In addition, 3 g of P-tert-butylphenol (5.1 mol% based on bisphenol A), bisphenol
130ml of 2N caustic soda aqueous solution containing 7.6g of A
and 0.6 aqueous solution containing 1.05 mg of triethylamine
ml and stir to make an emulsion, then add 600r.p.
The condensation polymerization reaction was carried out by stirring at m. for 20 minutes.
反応終了後、２のメチレンクロライドを加え
て数分間撹拌後、水相および有機相に分離した。
その結果、両相の界面にマイクロカプセルが生成
していた。このマイクロカプセルを分取し、500
mlの水、２規定の塩酸で洗浄し、目的とするマイ
クロカプセルを97ｇ（乾燥重量収率13.8％）得
た。このマイクロカプセルは粒径30〜100μで、
カプセル内にはおよそ700wt％（カプセル壁に対
して）の内包物を含有していた。 After the reaction was completed, methylene chloride (2) was added, and after stirring for several minutes, the mixture was separated into an aqueous phase and an organic phase.
As a result, microcapsules were formed at the interface between both phases. Separate this microcapsule and collect 500
The microcapsules were washed with 1 ml of water and 2N hydrochloric acid to obtain 97 g (dry weight yield: 13.8%) of the desired microcapsules. This microcapsule has a particle size of 30 to 100μ,
The capsule contained approximately 700 wt% (based on the capsule wall) of inclusions.
実施例 ２
乳濁状態後の撹拌を400r.p.m.としたこと以外
は、実施例１と同様の操作を行ないマイクロカプ
セルを得た。このものの粒径は500〜700μであつ
た。Example 2 Microcapsules were obtained by carrying out the same operation as in Example 1, except that the stirring after the emulsion was changed to 400 rpm. The particle size of this material was 500-700μ.
実施例 ３
ｐ−tert−ブチルフエノールの添加量を５ｇ
（ビスフエノールＡに対して8.5モル％）としたこ
と以外は、実施例２と同様の操作を行ないマイク
ロカプセルを得た。このものの粒径は100μであ
つた。Example 3 Addition amount of p-tert-butylphenol was 5g
(8.5 mol % based on bisphenol A) The same operation as in Example 2 was performed to obtain microcapsules. The particle size of this material was 100μ.
比較例 １
フロログルシノールの使用量を１ｇ（ビスフエ
ノールＡに対して1.6モル％）としたこと以外は、
実施例１と同様の操作を行なつたが生成物は液状
であつてマイクロカプセルは得られなかつた。Comparative Example 1 Except that the amount of phloroglucinol used was 1 g (1.6 mol% based on bisphenol A),
The same operation as in Example 1 was carried out, but the product was liquid and no microcapsules were obtained.
比較例 ２
ｐ−tert−ブチルフエノールを用いなかつたこ
と以外は、実施例１と同様の操作を行なつたとこ
ろ、有機相がゲル化して、所望するマイクロカプ
セルは得られなかつた。Comparative Example 2 The same operation as in Example 1 was carried out except that p-tert-butylphenol was not used, but the organic phase gelled and the desired microcapsules could not be obtained.
実施例 ４
フロログルシノールを４ｇ（ビスフエノールＡ
に対して6.3モル％）およびｐ−tert−ブチルフエ
ノールを４ｇ（ビスフエノールＡに対して6.8モ
ル％）にしたこと以外は、実施例１と同様の操作
を行ないマイクロカプセルを得た。このものの収
量は33ｇであり、また粒径は100〜170μであつ
た。Example 4 4 g of phloroglucinol (bisphenol A
Microcapsules were obtained by carrying out the same operation as in Example 1, except that the amount of p-tert-butylphenol was changed to 4 g (6.8 mol% relative to bisphenol A). The yield of this product was 33g, and the particle size was 100-170μ.
実施例 ５
フロログルシノールを３ｇ（ビスフエノールＡ
に対して4.7モル％）およびｐ−tert−ブチルフエ
ノールを３ｇ（ビスフエノールＡに対して5.1モ
ル％）にしたこと以外は、実施例１と同様の操作
を行ないマイクロカプセルを得た。このものの収
量は38ｇであり、また粒径は70〜100μであつた。Example 5 3 g of phloroglucinol (bisphenol A
Microcapsules were obtained by carrying out the same operation as in Example 1, except that the amount of p-tert-butylphenol was changed to 3 g (5.1 mol% relative to bisphenol A). The yield of this product was 38g, and the particle size was 70-100μ.
比較例 ３
ｐ−tert−ブチルフエノールを2.0ｇ（ビスフエ
ノールＡに対して3.9モル％）にしたこと以外は、
実施例５と同様に行なつたところ、有機相がゲル
化して、所望するマイクロカプセルは得られなか
つた。Comparative Example 3 Except that p-tert-butylphenol was 2.0g (3.9 mol% based on bisphenol A),
When the same procedure as in Example 5 was carried out, the organic phase gelled and the desired microcapsules could not be obtained.
比較例 ４
フロログルシノールを2.0ｇ（ビスフエノール
Ａに対して3.1モル％）、ｐ−tert−ブチルフエノ
ールを2.0ｇ（ビスフエノールＡに対して3.4モル
％）にして実施例１と同様に行なつたが、ゲル化
して所望するマイクロカプセルは得られなかつ
た。Comparative Example 4 The same procedure as in Example 1 was carried out using 2.0 g of phloroglucinol (3.1 mol% relative to bisphenol A) and 2.0 g of p-tert-butylphenol (3.4 mol% relative to bisphenol A). However, the desired microcapsules were not obtained due to gelation.
比較例 ５
ｐ−tert−ブチルフエノールの添加量を9.2ｇ
（ビスフエノールＡに対して18モル％）としたこ
と以外は、実施例５と同様に行なつた。この結
果、有機相と水相はそれぞれ均一となり、所望す
るマイクロカプセルは得られなかつた。Comparative Example 5 The amount of p-tert-butylphenol added was 9.2g.
The same procedure as in Example 5 was carried out except that the amount was changed to (18 mol % based on bisphenol A). As a result, the organic phase and the aqueous phase each became uniform, and the desired microcapsules could not be obtained.
比較例 ６
フロログルシノールの添加量を11.3ｇ（ビスフ
エノールＡに対して18モル％）としたこと以外
は、実施例１と同様に行なつた。この結果、有機
相がゲル化して所望するマイクロカプセルは得ら
れなつた。Comparative Example 6 The same procedure as in Example 1 was carried out except that the amount of phloroglucinol added was 11.3 g (18 mol % based on bisphenol A). As a result, the organic phase gelled and the desired microcapsules could not be obtained.
Claims (1)
記物質と縮重合しうる重合性物質を溶解した水溶
液(B)であり、かつ前記両溶液(A)、(B)中に存在する
重合性物質の合計割合を二官能性化合物に対して
一官能性化合物４〜15モル％および三官能性化合
物3.5〜15モル％に調節した溶液(A)、(B)を用いて
界面縮重合を行なうことを特徴とするカプセル壁
が架橋した縮合ポリマーよりなるマイクロカプセ
ルの製造方法。 ２ 疎水性溶液(A)中の重合性物質として、二価フ
エノールのビスクロロホーメートおよび／または
ジカルボン酸の酸ハロゲン化物を含有する特許請
求の範囲第１項記載の方法。 ３ 水溶液(B)中の重合性物質として、二価フエノ
ールのアルカリ金属塩を含有する特許請求の範囲
第１項記載の方法。[Scope of Claims] 1 A hydrophobic solution (A) in which a polymerizable substance is dissolved; and an aqueous solution (B) in which a polymerizable substance capable of condensation polymerization with the substance is dissolved; solutions (A) and (B) in which the total proportion of polymerizable substances present in (A) and (B) were adjusted to 4 to 15 mol% of monofunctional compounds and 3.5 to 15 mol% of trifunctional compounds to the difunctional compounds. 1. A method for producing microcapsules whose capsule walls are made of a crosslinked condensation polymer, the method comprising carrying out interfacial condensation polymerization using a polymer. 2. The method according to claim 1, wherein the hydrophobic solution (A) contains a bischloroformate of dihydric phenol and/or an acid halide of dicarboxylic acid as the polymerizable substance. 3. The method according to claim 1, wherein the aqueous solution (B) contains an alkali metal salt of divalent phenol as the polymerizable substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57165000A JPS5955342A (en) | 1982-09-24 | 1982-09-24 | Microcapsule and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57165000A JPS5955342A (en) | 1982-09-24 | 1982-09-24 | Microcapsule and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5955342A JPS5955342A (en) | 1984-03-30 |
| JPS634448B2 true JPS634448B2 (en) | 1988-01-29 |
Family
ID=15803937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57165000A Granted JPS5955342A (en) | 1982-09-24 | 1982-09-24 | Microcapsule and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5955342A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236643U (en) * | 1988-09-03 | 1990-03-09 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6187734A (en) * | 1984-10-03 | 1986-05-06 | Japan Synthetic Rubber Co Ltd | Production of hollow polymer particle |
| JP2006199903A (en) * | 2004-03-11 | 2006-08-03 | Sanyo Chem Ind Ltd | Heat expansible microcapsule and hollow resin particle |
| JP2006199904A (en) * | 2004-03-11 | 2006-08-03 | Sanyo Chem Ind Ltd | Method for producing heat expansible microcapsule and method for producing hollow resin particle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440771A (en) * | 1977-06-13 | 1979-03-30 | Sonoco Products Co | Partition for box* and container fitted with said partition |
-
1982
- 1982-09-24 JP JP57165000A patent/JPS5955342A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5440771A (en) * | 1977-06-13 | 1979-03-30 | Sonoco Products Co | Partition for box* and container fitted with said partition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236643U (en) * | 1988-09-03 | 1990-03-09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5955342A (en) | 1984-03-30 |
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