JPS59199033A - Production of microcapsule - Google Patents

Abstract

PURPOSE:To produce easily microcapsules having superior holding property or a core substance and superior durability and heat resistance of the capsules by allowing to cause a net-forming three dimensional polymer reaction between a curing agent, high molecular polyvalent amine and ahydrophilic substance. CONSTITUTION:After emulsifying and dispersing a hydrophobic core substance (e.g fish oil) contg. a curing agent in a liquid contg. a hydrophilic substance (e.g. polyvinyl alcohol), a high molecular polyvalent amine (e.g. polyethyleneimine) is added thereto, and a net-forming three dimensional polymer reaction is caused on the boundary of liquid drops between the curing agent, high molecular polyvalent amine and the hydrophilic substance to cover the core substance. One kind or a combination of >=two kinds of compds. are selected from compds. expressed by formulas I -IV as the curing agent. These compds. are triazine compds., pyrimidine compds., or pyridazine compds. wherein at least two among A, B, D or A, B, D, E are reactive halogen atoms (F, Cl, Br).

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は疎水性芯物質を被接するマイクロカプセルの新
規な製造法に関する。特に硬化剤、高分子量多価アミン
、乳化剤との間に網目三次元化高分子反応を起こさせる
ことにより、疎水性芯物質の保持性、カプセルの耐久性
、耐熱性に優れたマイクロカプセルを極めて容易に製造
し得る方法に関１−るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel method for producing microcapsules coated with a hydrophobic core material. In particular, by causing a three-dimensional network polymer reaction between a curing agent, a high molecular weight polyvalent amine, and an emulsifier, microcapsules with excellent retention of hydrophobic core substances, capsule durability, and heat resistance are produced. The present invention relates to a method that can be easily manufactured.

近年マイクロカプセル化技術の進歩はめさましいものが
ありその応用分野も感圧記録紙をはじめとして、医薬品
、化粧品、染を１、インク、香料、ポリビニルアルコー
ル（以下ＰＶＡと略記）を壁材又は壁材形成促進剤とし
て用いるものとして特開昭５５−１５６８１号、特開昭
５６−１００６３０号に曇点を有するＰＶＡをカプセル
芯物質の周囲に出現せしめ、有機又は無機チタン化合物
、グリオキず−ル、グルタルアルデヒド等の硬化剤を用
いて硬化させる方法、特開昭５７−１１０３３２号、特
開昭５７−１１６０１０号にカチオン性ＰＶＡの存在下
でアミン化合物とアルデヒド類の重縮合反応により壁材
を形成させる方法等が開示されている。In recent years, there has been remarkable progress in microencapsulation technology, and its application fields include pressure-sensitive recording paper, pharmaceuticals, cosmetics, dyes, inks, fragrances, polyvinyl alcohol (hereinafter abbreviated as PVA), and wall materials. In JP-A-55-15681 and JP-A-56-100630, PVA having a cloud point is made to appear around the capsule core material as a material formation accelerator, and organic or inorganic titanium compounds, glyoxol, A method of curing using a curing agent such as glutaraldehyde, JP-A-57-110332 and JP-A-57-116010 describes the formation of wall materials by polycondensation reaction of amine compounds and aldehydes in the presence of cationic PVA. A method for doing so is disclosed.

これらの方法においてもやはり操作が複雑であること、
ＰＶＡと硬化成分との反応による硬化方法では壁形成に
関与しないフリーのＰＶＡも不溶化するためにマイクロ
カプセルの凝集やマイクロカプセル分散液の著しい増粘
、ひいてはゲル化を生じやすくなるために合成カプセル
の特長である高濃度カプセル化が困難であること、さら
にマイクロカプセルとしての耐久性としても未だ満足な
ものか得られていないということかあげられる。These methods are also complicated to operate;
In the curing method based on the reaction between PVA and the curing component, free PVA that does not participate in wall formation is also insolubilized, which tends to cause aggregation of microcapsules, significant thickening of the microcapsule dispersion, and gelation. This may be due to the fact that it is difficult to encapsulate at a high concentration, which is a characteristic of microcapsules, and the durability of microcapsules is still unsatisfactory.

〔発明の目的〕[Purpose of the invention]

本発明者は効率よく被捺、不俗化し、かつ上記のような
欠点のない、しかも疎水性芯物質の保持性、耐久性、耐
熱性の優れたマイクロカプセルを極めて容易な操作によ
り提供することを目的とする。It is an object of the present inventor to provide microcapsules that can be efficiently printed and made obscene, are free from the above-mentioned drawbacks, and have excellent hydrophobic core material retention, durability, and heat resistance, using extremely easy operations. With the goal.

〔発明の構成〕[Structure of the invention]

本発明を概説すれは、硬゛化剤を含有する疎水性芯物質
な親水性物質貧有液体中に乳化分散した後、高分子化合
物アミンを添加し、液筒界面で該硬化剤、高分子量多価
アミン及び親水性物質との間で網目三次元化高分子反応
を匙こさせろことにより、疎水性、８．物質を破缶させ
ることを特徴とするマイクロカプセルの製造法である。To summarize the present invention, after emulsifying and dispersing a hydrophobic core substance in a liquid containing a hydrophilic substance containing a hardening agent, a high molecular compound amine is added, and the hardening agent and high molecular weight 8. Hydrophobicity is achieved by conducting a three-dimensional network polymer reaction between a polyvalent amine and a hydrophilic substance. This is a method for producing microcapsules, which is characterized by breaking the can of a substance.

硬化剤 硬化剤としては次の一般式で表わされる化合物を１棟以
上併用して用いられる。Curing Agent As the curing agent, one or more compounds represented by the following general formula may be used in combination.

（Ｉ）　　　、　　　（ＩＩ）　　　　　（１）　　　
　　　（ＩＶ）具体的には塩化シアヌル（２，４，６−
）リフ００−１．３．５−トリアジン）、臭化シアヌル
、フッ化シアヌル、２．４−シクロロー６−アルキル−
１，３，５−）リアジン、２，４−ジフルオロ−６−了
り−ルー１．３．５−）リアジン、２゜４−シクロロー
６−アルコキシ−１，３，５−トリアゾン、３，５．６
−ドリクロロー１．２．４−トリアジン、テトラクロロ
ピリミジン、　２，４゜５−トリクロロ−６−アルキル
−ピリミジン、テトラブロモビリＳジン、テトラクロロ
ピリダジン等かあげられる。(I), (II) (1)
(IV) Specifically, cyanuric chloride (2,4,6-
) rif00-1.3.5-triazine), cyanuric bromide, cyanuric fluoride, 2,4-cyclo6-alkyl-
1,3,5-) riazine, 2,4-difluoro-6-ori-ru-1.3.5-) riazine, 2゜4-cyclo6-alkoxy-1,3,5-triazone, 3,5 .6
Examples include -dolichloro1.2.4-triazine, tetrachloropyrimidine, 2,4°5-trichloro-6-alkyl-pyrimidine, tetrabromobiliS dine, and tetrachloropyridazine.

尚分子量多価アミン 旨分子量多４曲アミンとしてはホリエチレンイミン、ア
ミノ基変性ポリビニルアルコール等があげられるか分子
中に一１１１Ｈ−又は−Ｎｌ２基を冶し連続相を形成す
る親水性液体中に溶解あるいは分散わ］能な高分子化合
物であれは全てオＩＪ用可能である。分子量は特に限定
されないか３００〜１２万、特に１８０Ｕ〜７万か好適
である。Polyhydric amines with molecular weights such as polyvalent amines include polyethyleneimine, amino group-modified polyvinyl alcohol, etc., and hydrophilic liquids containing -111H- or -Nl2 groups in the molecule to form a continuous phase. Any polymer compound that can be dissolved or dispersed can be used for IJ. The molecular weight is not particularly limited or is suitably from 300 to 120,000, particularly from 180 U to 70,000.

親水性物質 疎水性数体を乳化分散させるための親水性物質としては
ＰＶＡ　、変性ＰＶＡ　（カルボキシル羞変１１゜ＰＶ
Ａ　、アルキルビニルエーテル変性ＰＶＡ　、アクリ＼ ルアミド変性ＰＶＡ、カチオン基変性ＰＶＡ等）アラビ
アゴム、セゝラチン、カルボキシメチルセルロース、カ
ゼイン、アルギン酸ナトリウム、レシチン、澱粉、ホリ
ビニルビロリドン、ショ糖脂肪にエステル、ポリアクリ
ルアミド、スチレン、エチレンのような疎水性ビニルモ
ノマーとマレイン酸、アクリル酸、メタクリル酸の一種
以上との共重合体及びポリアクリル酸等が使用される。Hydrophilic Substances Hydrophilic substances for emulsifying and dispersing hydrophobic molecules include PVA, modified PVA (carboxyl photochromic 11°PV
A, alkyl vinyl ether-modified PVA, acrylamide-modified PVA, cationic group-modified PVA, etc.) gum arabic, seratin, carboxymethyl cellulose, casein, sodium alginate, lecithin, starch, phoribinyl pyrrolidone, sucrose fat and ester, Copolymers of hydrophobic vinyl monomers such as polyacrylamide, styrene, and ethylene with one or more of maleic acid, acrylic acid, and methacrylic acid, polyacrylic acid, and the like are used.

これらの親水性物質でも水酸基を有するものではさきに
あげた硬化剤と反応しうるので乳化剤兼カプセル壁形成
材料としても利用できる。しかしこの場合水酸基はアミ
ノ晶相高反応性でない為Ｋ　）　ＩＪメチルアミン、炭
酸カルシウム、水酸化ナトリウム等の塩基性物質を併用
しなければ効果か薄い。塩基性物質の使用量は硬化剤の
モル数の１〜６倍匍の範囲から選ばれる。水酸基を有す
る乳化剤のうち壁を形成しなかったフリーの乳化剤は未
反応のまま残るので生成したマイクロカプセルを水中に
安定に分散させ、マイクロカプセルの凝集を防ぐ働きを
するので高濃度でのマイクロカプセル化か可能である。Among these hydrophilic substances, those having a hydroxyl group can react with the above-mentioned curing agent, and therefore can be used as both an emulsifier and a capsule wall forming material. However, in this case, since the hydroxyl group is not highly reactive in the amino crystal phase, it is not very effective unless a basic substance such as IJ methylamine, calcium carbonate, or sodium hydroxide is used in combination. The amount of the basic substance to be used is selected from a range of 1 to 6 times the number of moles of the curing agent. Among emulsifiers with hydroxyl groups, free emulsifiers that have not formed a wall remain unreacted, allowing the formed microcapsules to be stably dispersed in water and preventing microcapsules from agglomerating. It is possible.

水酸基を有する乳化剤は高分子量多価アミンよりも反応
性か低い為にカプセル様形成比率は高分子鍬多愉アミン
よりも低いと予想されろが、乳化剤単独でもカプセル壁
を形成しうろことが顕微鏡により確認できる。さきにあ
げた乳化剤のうちＰＶＡ、変成ＰＶＡは乳化力、硬化剤
との反応性も優れており好適である。重合度は３００〜
３０００ケン化度６０モル係以上のものが選ばれるが、
変成ＰＴＡについては［Ｊ、０１〜６０モル係の変性度
のものが製造のし易さ、性能の面からも好ましい。Emulsifiers with hydroxyl groups are less reactive than high-molecular-weight polyvalent amines, so the capsule-like formation ratio is expected to be lower than that of high-molecular-weight polyvalent amines, but the emulsifiers alone can also form capsule walls. This can be confirmed by Among the emulsifiers mentioned above, PVA and modified PVA are suitable because they have excellent emulsifying power and reactivity with hardening agents. The degree of polymerization is 300~
Those with a saponification degree of 3000 and a mole ratio of 60 or more are selected,
Regarding modified PTA, those having a degree of modification of [J, 01 to 60 molar ratio are preferred from the viewpoint of ease of production and performance.

マイクロカプセル中に被覆される疎水性芯物質としては
特に限定されるものではないか、魚油、ラード油のごと
き動物性油、オリーブ油・落花生油・大豆油・亜麻仁油
・ひまし油・とうもろこし油等の植物注油、石油・ナフ
サ・ケロシン・トルエン・キシレン・アルキルナフタレ
ン・アルキル置換ジフェニルアルカン・フタルｒ＞２エ
ステルのような、私物油、合成油、肩粉・溶媒のような
水不溶性の成体で硬化剤を壁形成に十分な良度で溶解さ
せることかできるものなうは何でもよい。またこれを溶
解又は分散させて用いることもできる。The hydrophobic core substance coated in the microcapsules is not particularly limited, and may include animal oils such as fish oil and lard oil, vegetable oils such as olive oil, peanut oil, soybean oil, linseed oil, castor oil, and corn oil. Lubricating, hardening agents with water-insoluble compounds such as petroleum, naphtha, kerosene, toluene, xylene, alkylnaphthalenes, alkyl-substituted diphenylalkanes, phthalate r>2 esters, private oils, synthetic oils, shoulder powder, and solvents. Anything that can be dissolved to a sufficient degree for wall formation may be used. It can also be used after being dissolved or dispersed.

疎水性芯物質の使用量は水に対して７Ｕチ以下好ましく
は１０〜６ｏ％である。７０％を超えると乳化工程にお
いて疎水性芯ｗＪ貴の乳化が困腿になるうえ、できたマ
イクロカプセルが高粘度すぎて取扱いかめんどうである
。１０％未満では実用的でなくなる。The amount of the hydrophobic core substance used is 7 U or less, preferably 10 to 6%, based on water. If it exceeds 70%, it becomes difficult to emulsify the hydrophobic core during the emulsification process, and the resulting microcapsules have too high a viscosity and are troublesome to handle. If it is less than 10%, it is not practical.

用いる硬化剤の童は疎水性芯物質に対して２〜２０％、
好ましくは５〜１５％である。２０％を超えると反応中
に三次元化か進みすきでデル化がおこりやすい。２％未
満では硬化反応が十分でなくしたがって耐久性も弱い。The amount of curing agent used is 2 to 20% based on the hydrophobic core material.
Preferably it is 5 to 15%. If it exceeds 20%, three-dimensional formation tends to proceed during the reaction, and del formation tends to occur. If it is less than 2%, the curing reaction will not be sufficient and therefore the durability will be poor.

壁材としての高分子量多価アミンの使用量は疎水性芯物
質に対して５〜６５％、好ましくは１０〜２５％の範囲
から選ばれる。５％未満では壁の耐久性が弱く、６５％
を越えると硬化剤と未反応のものがフリーで糸に存在す
る量か増えるだけで実用的でない。The amount of high molecular weight polyvalent amine used as a wall material is selected from the range of 5 to 65%, preferably 10 to 25%, based on the hydrophobic core material. If it is less than 5%, the durability of the wall will be weak, and it will be 65%.
Exceeding the hardening agent will simply increase the amount of unreacted material in the yarn, making it impractical.

親水性物質の１更用量は疎水性芯物質に対して５条以上
かよい。乳化させる場合の乳化剤の濃ル：はＵ、１〜６
０％、好ましくは１〜１５％である。One additional dose of hydrophilic material may be 5 or more strips for the hydrophobic core material. Concentration of emulsifier when emulsifying: U, 1 to 6
0%, preferably 1-15%.

６０％以上では高粘度すきて乳化時の攪拌が不良で、Ｄ
、１％未満ではやはり乳化に問題が生じる。If it exceeds 60%, the viscosity will be high and stirring during emulsification will be poor, resulting in D.
, if it is less than 1%, problems will still occur in emulsification.

マイクロカプセル化工程は乳化工程及び反応工程の２工
程からなる。まず疎水性芯物質に前記硬化剤（１）、（
Ｉｔ）、（１）、（ＩＶ）から選ばれる１種以上のもの
を溶解、分散させ乳化剤を加えて室温で乳化させる。次
に高分子量多価アミンの水浴液を前記の乳化液に室温で
滴下させる。高分子量多価アミンの水浴液は滴下させる
のに不都合な程の粘度でなければ如何なる濃度であって
も滴下終了後のマイクロカプセルスラリー（乳化液）の
濃度が１０〜４０％の範囲にはいるならばさしつかえな
い。滴下反応温度は室温でも十分であるが反応を完結ま
で行なわせる為に滴下終了後６０〜７０℃の範囲で加熱
してもさしつかえない。この時の反応時間は滴下に６０
分〜４時間好ましくは６０分〜２時［１１」、滴下終了
後３０分〜６時間、好ましくは３０り〜ｌ萌１１Ｊ１の
終１引万・ｊヱ１ば゛わ」。The microencapsulation process consists of two steps: an emulsification process and a reaction process. First, the curing agent (1), (
It), (1), and (IV) are dissolved and dispersed, an emulsifier is added, and the mixture is emulsified at room temperature. Next, a water bath solution of a high molecular weight polyvalent amine is added dropwise to the emulsion at room temperature. The water bath solution of high molecular weight polyvalent amine has any concentration unless the viscosity is inconvenient for dropping, and the concentration of the microcapsule slurry (emulsion) after dropping is in the range of 10 to 40%. If so, no problem. As for the dropping reaction temperature, room temperature is sufficient, but in order to carry out the reaction to completion, it may be heated in the range of 60 to 70°C after the dropping is completed. The reaction time at this time was 60 minutes for dropping.
minutes to 4 hours, preferably 60 minutes to 2 o'clock, and 30 minutes to 6 hours, preferably 30 minutes to 11 hours after the completion of the dropping.

本発明によれは例えはホモジナイザー、伎拌機、超音波
等を用いて１〜５０００μの粒径を有するマイクロカプ
セルを任意に′ｖＪ＠整１゛ることかできる。According to the present invention, microcapsules having a particle size of 1 to 5000 .mu. can be arbitrarily prepared using, for example, a homogenizer, a stirrer, an ultrasonic wave, or the like.

加えて親水性液体中に添加する高分子量多価アミン、乳
化剤の種類、童さらには高分子量多価アミンの添加時期
を適宜稠節することにより所望の硬度のカプセル壁を形
成させ得ることができる。In addition, by appropriately controlling the type of high-molecular-weight polyvalent amine and emulsifier added to the hydrophilic liquid, and the timing of addition of the high-molecular-weight polyvalent amine, it is possible to form a capsule wall with a desired hardness. .

本発明において壁材を形成する組み合わせで特に好適な
のは硬化剤に塩化シアヌル、高分子量多価アミンにポリ
エチレンイミン、乳化剤にＰＶＡを用いる方法である。In the present invention, a particularly preferred combination for forming a wall material is a method in which cyanuric chloride is used as a hardening agent, polyethyleneimine is used as a high molecular weight polyvalent amine, and PVA is used as an emulsifier.

〔発明の実施例〕[Embodiments of the invention]

次に実施例及び比較例をもって本発明をさらに詳しく説
明するが、本発明はこれら実施例に限定されるものでは
ない。尚これまでに述べてきたチ及び実施例に示す係は
特にことわらないかきり重量係を示す。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. It should be noted that the parts described above and shown in the examples refer to the cutting weight parts, which are not particularly specified.

実施例１ トルエン６２．５＆に塩化シアヌル６．２５．９を溶解
したものに、重合度１７２０、ケン化度８８．２モル係
の部分ケン化ＰＶＡ　（電気化学工業（株）製Ｂ−１７
）の７％水溶欣１０５ｇを添加し、室温で激しく攪拌し
て平均粒径５０μの乳化液を調整＝０１８、分子量１８
００）の１８．５％の水浴液後さらに６０分その筐ま反
応させた。得られたマイクロカプセル乳化液は凝集のな
い球状のものであり流動性も良好であった。これをテフ
ロンフィルム上にマイクロカプセル乳化液の量で６０９
７ｍ２になる様に塗布し、１ｔＪ５℃で２日間加熱した
時の重量損失を表に示す。Example 1 Partially saponified PVA (manufactured by Denki Kagaku Kogyo Co., Ltd. B-17) with a polymerization degree of 1720 and a saponification degree of 88.2 molar was added to a solution of cyanuric chloride 6.25.9 in toluene 62.5.
) and stirred vigorously at room temperature to prepare an emulsion with an average particle size of 50μ = 018, molecular weight 18
After the 18.5% water bath solution of 00) was added, the reaction was allowed to proceed for an additional 60 minutes. The obtained microcapsule emulsion was spherical without agglomeration and had good fluidity. Place this on a Teflon film in an amount of 609 microcapsules emulsion.
The table shows the weight loss when the coating was applied to an area of 7m2 and heated at 1tJ5°C for 2 days.

実施例２ ジフェニルエタン５０ｇにテトラクロロピリダジン４．
５ｇを溶解したものに、実施例１と同様にＰＶＡ水浴液
を添加し室温で激しく撹拌して平均粒径１０μの乳化液
を調整した。この後４１１０　ｒｐｍで撹拌しなから酢
酸ビニルとＮ−（３−アリルオキシ−２−ヒドロキシ７
０ロビル）モノメチルアミン塩酸塩を共重合、ケン化し
て合成したアミノ基ｆＩＪｙ、ＰＶＡ　（変成率９．８
モル％、ケン化＆９７．９モルチ、４％ブルックフィー
ルド粘７ｉ２４ｃｐｓ）の２０％水溶ｉ６０．９と３０
％トリメチルアミン水浴−液１０ｇを室温で２時間かけ
て滴下させ、滴下終了後さらに２時間反応させた。得ら
れたマイクロカプセル乳化液は凝集もなく、球状であり
流動性も良好であった。実施例１と同様に１０５°Ｃで
２日間加熱した時のＮ量損失を表に示す。Example 2 4. Tetrachloropyridazine was added to 50 g of diphenylethane.
A PVA water bath solution was added to a solution of 5 g in the same manner as in Example 1, and the mixture was vigorously stirred at room temperature to prepare an emulsion having an average particle size of 10 μm. After this, while stirring at 4110 rpm, vinyl acetate and N-(3-allyloxy-2-hydroxy 7
amino group fIJy synthesized by copolymerizing and saponifying monomethylamine hydrochloride, PVA (modification rate 9.8
Mol%, saponified & 97.9molti, 4% Brookfield Viscosity 7i24cps) of 20% aqueous i60.9 and 30
% trimethylamine water bath solution was added dropwise over 2 hours at room temperature, and after the addition was completed, the reaction was continued for another 2 hours. The obtained microcapsule emulsion had no aggregation, was spherical, and had good fluidity. The table shows the loss of N amount when heated at 105°C for 2 days in the same manner as in Example 1.

実施例６ ゾプチルフタレート８０．９にテトラクロロピリダジン
５ｇを溶解させた以外は実施例１と同様の操作を行なっ
た。得られたマイクロカプセル乳化液は凝集もなく、流
動性も良好であった。実施例１と同様に１０５°Ｃで２
日間加熱した時の重量損失を表に示す。Example 6 The same operation as in Example 1 was performed except that 5 g of tetrachloropyridazine was dissolved in 80.9 g of zoptylphthalate. The obtained microcapsule emulsion had no aggregation and had good fluidity. 2 at 105°C as in Example 1.
The weight loss when heated for 1 day is shown in the table.

実施例４ ジイソゾロビルナフタレン４５５’と酢酸エチル１０、
？を混合したものにクリスタルバイオレットラクトン０
．９．＆、塩化シアヌル６．４ｇを溶解させ、実施例１
のＰＶＡの６チ水浴液１０５ｇを添加し室温で激しく攪
拌して平均粒径８μの乳化液を調整した。この後室温、
４００　ｒｐｍで攪拌しながらポリエチレンイミン（日
本触媒化学工業（株）製エポミンＰ−１０００分子量７
万）の１４％水溶液６０．９及び塩化シアヌルが反応し
た時に副成する塩酸を捕捉する試薬兼乳化剤との反応促
進剤として６０％トリメチルアミン水浴＆１５．？を混
合したものを１時間６０分かけて滴下させ、さらに７０
°０１１時間加熱して反応させた。得られたマイクロカ
プセル乳化液は凝婁もなく、流動性も良好であった。実
施例１と同様に１０５°Ｃで２日間加熱した時の重量損
失を表に示す。次にマイクロカプセル乳化液を坪量４Ｄ
ｇ／ｍ２の下葉紙に６＆／ｍ２（固形分）になるように
塗布乾燥後クレーを一色剤としてコーティングしである
下葉紙への感圧比記性でもにじ入のない鮮明な光色マー
クか得られた。Example 4 Diisozolobylnaphthalene 455' and ethyl acetate 10,
? crystal violet lactone 0
．． 9. &, 6.4 g of cyanuric chloride was dissolved, Example 1
105 g of PVA 6-T water bath solution was added and vigorously stirred at room temperature to prepare an emulsion having an average particle size of 8 μm. After this, room temperature
While stirring at 400 rpm, polyethyleneimine (Epomin P-1000, molecular weight 7, manufactured by Nippon Shokubai Chemical Co., Ltd.) was added.
14% aqueous solution 60.9 of cyanuric chloride and 60% trimethylamine water bath as a reaction promoter with a reagent and emulsifier that captures the hydrochloric acid by-produced when cyanuric chloride reacts &15. ? The mixture was added dropwise over 1 hour and 60 minutes, and then
The reaction mixture was heated for 11 hours. The obtained microcapsule emulsion had no curdling and had good fluidity. The table shows the weight loss when heated at 105°C for 2 days in the same manner as in Example 1. Next, add the microcapsule emulsion with a basis weight of 4D.
g/m2 of the lower paper, applied to the lower paper to a solid content of 6&/m2 (solid content), dried, and then coated with clay as a monochromatic agent. Clear light color with no bleeding even with pressure-sensitive recording properties on the lower paper. I got a mark.

比較例１ 実施例１でポリエチレンイミンのかわりにエチレンシア
ミンを用いた以外はまったく同様の操作を行なった、１
０５℃で２日間加熱した時の重量損失を表に示′１−ｏ
高分子多価アミンを用いた場合に比較して重量損失はか
なり大きく耐久性が劣った。Comparative Example 1 The same procedure as in Example 1 was performed except that ethylenecyamine was used instead of polyethyleneimine.
The table shows the weight loss when heated at 05℃ for 2 days'1-o
Compared to the case where a polymeric polyvalent amine was used, the weight loss was considerably large and the durability was inferior.

比較例２ 実施例２でポリエチレンイミンのかわりにトリエチレン
テトラミンを用いた以外はまったく同様な操作を行なっ
た。１０５°Ｃで２日間加熱した時の重量損失を表に示
す。Comparative Example 2 The same operation as in Example 2 was performed except that triethylenetetramine was used instead of polyethyleneimine. The weight loss upon heating at 105°C for 2 days is shown in the table.

〔発明の効果〕〔Effect of the invention〕

このように本発明では従来性なわれていた一重部度、冷
却等の複雑な工程を必要とせず疎水性芯物質の室温乳化
、壁形成物質の室温滴下反応たけという極めて容易な操
作により疎水性芯物質の保持性、耐久性の優れたマイク
ロカプセルを製造しうる。In this way, the present invention does not require complicated steps such as single-part processing and cooling, which were conventionally used, and can achieve hydrophobic properties by extremely simple operations such as room-temperature emulsification of a hydrophobic core material and room-temperature dropwise reaction of a wall-forming material. Microcapsules with excellent core substance retention and durability can be produced.

特許出願人　電気化学工業株式会社Patent applicant Denki Kagaku Kogyo Co., Ltd.

Claims (1)

【特許請求の範囲】 （１）硬化剤を含有プる疎水性芯物質を親水性物質含有
液体中に乳化分散した後、高分子量多価アミンを添加し
、液滴界面で該硬化剤、高分子量多価アミン及び親水性
物質との間で網目三次元化高分子反応を起こさせること
により、疎水性芯物質を被覆させることを特徴とするマ
イクロカプセルの製造法。 （２）　　硬化沖」が下記の（Ｉ）〜（１ｖ）より１種
又は２種以上併用して選ばれる特許請求の範囲第（１）
項記載の方法。 （１）　　　　　（Ｉｆ）　　　　　（１）　　　　（
ＩＶ）（３）　　高分子量多価アミンがポリエチレンイ
ミンである特許請求の範囲第（１）項記載の方法。 （４）　　親水性物質がポリビニルアルコールである特
許請求の範囲第（１）項記載の方法。[Claims] (1) After emulsifying and dispersing a hydrophobic core material containing a hardening agent in a liquid containing a hydrophilic substance, a high molecular weight polyvalent amine is added, and the hardening agent and high A method for producing microcapsules, which comprises coating a hydrophobic core material by causing a three-dimensional network polymer reaction between a molecular weight polyvalent amine and a hydrophilic substance. (2) Claim No. (1) in which “Hyaku-Oki” is selected from one or more of the following (I) to (1v) in combination.
The method described in section. (1) (If) (1) (
IV) (3) The method according to claim (1), wherein the high molecular weight polyvalent amine is polyethyleneimine. (4) The method according to claim (1), wherein the hydrophilic substance is polyvinyl alcohol.