JPH07216273A - Oil-based coating liquid containing microcapsules and its production - Google Patents
Oil-based coating liquid containing microcapsules and its productionInfo
- Publication number
- JPH07216273A JPH07216273A JP6040290A JP4029094A JPH07216273A JP H07216273 A JPH07216273 A JP H07216273A JP 6040290 A JP6040290 A JP 6040290A JP 4029094 A JP4029094 A JP 4029094A JP H07216273 A JPH07216273 A JP H07216273A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- varnish
- microcapsule
- coating liquid
- wall material
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水糸に分散状態で生成
されたマイクロカプセルを、個々のカプセル粒子同志が
互いに凝集していない状態のまま油性インキあるいは油
性塗料に置換させ、含有させる技術に関するものであ
る。さらに詳しくは、マイクロカプセル水系分散液に、
ワニスあるいは塗料用樹脂及びカプセル壁材の表層の両
方に親和する溶剤、例えば、グリセリンと、インキ用油
性のワニスあるいは塗料用樹脂からなる油性塗液、例え
ば、メタクリル酸誘導体、アクリル酸誘導体、不飽和脂
肪酸の混合グリセリド等を混合し、これを真空蒸留を用
いて水分を気化し除去することにより、マイクロカプセ
ル同志を互いに凝集させることなく、１次粒子のまま水
系から油系に置換し、マイクロカプセルを含有した油性
塗液を作成する技術に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique in which microcapsules produced in a dispersed state in a water thread are replaced with an oil-based ink or oil-based paint in a state where individual capsule particles are not aggregated with each other. It is about. More specifically, in the microcapsule aqueous dispersion,
A solvent compatible with both varnish or paint resin and the surface layer of the capsule wall material, such as glycerin, and an oil-based coating liquid consisting of an oil-based varnish for ink or paint resin, such as a methacrylic acid derivative, an acrylic acid derivative, and unsaturated. By mixing a mixed glyceride of fatty acids, etc. and evaporating and removing water using vacuum distillation, the microcapsules can be replaced from an aqueous system to an oil system as primary particles without aggregating the microcapsules. The present invention relates to a technique for producing an oil-based coating liquid containing
【０００２】[0002]
【従来の技術】従来からマイクロカプセル化技術は、染
料、香料、液晶、顔料、薬剤、溶剤、接着剤等の封入に
巾広く応用され、これら芯物質封入物の取り扱いを容易
にし、機能を長期間保持できるものである。そして、こ
れらは通常、水系でカプセル化されるため、ワニスある
いは塗料用樹脂への直接的な置換は不可能であった。し
たがって、マイクロカプセルの水系から油系への置換技
術を確立すれば、例えば、塩化ビニル等のプラスチック
への練り込みが容易になる等、様々な分野で活用できる
ものである。とりわけ、印刷分野では、例えば、感圧複
写紙あるいは自己発色紙において、部分的に発色を阻害
させるような場合、あるいは、部分的に発色させる場
合、従来では、複写紙あるいは自己発色紙に発色を阻害
する特殊なインキを用いて部分的に減感印刷を施すが、
発色染料マイクロカプセルを含有した油性印刷インキを
用いれば、減感印刷ユニットをそのまま利用して、通常
の上質紙の他、従来では不適であったような薄紙。サン
ドイッチ紙、合成紙へも、直接、発色に必要な箇所に部
分的に塗布できる等、その有用性は非常に高い。2. Description of the Related Art Conventionally, the microencapsulation technology has been widely applied to the encapsulation of dyes, fragrances, liquid crystals, pigments, drugs, solvents, adhesives, etc. to facilitate the handling of these core substance encapsulations and to improve the function. It can be held for a period of time. Since these are usually encapsulated in a water system, direct substitution with a varnish or a coating resin is impossible. Therefore, if a technique for substituting the microcapsules from an aqueous system to an oil system is established, the microcapsules can be utilized in various fields such as easy kneading into a plastic such as vinyl chloride. In particular, in the field of printing, for example, in the case of pressure-sensitive copying paper or self-coloring paper, when the color development is partially obstructed or when the color is partially developed, conventionally, the copy paper or the self-coloring paper is colored. Desensitizing printing is partially performed using a special ink that inhibits
By using the oil-based printing ink containing the color-forming dye microcapsules, the desensitizing printing unit can be used as it is for ordinary high-quality paper and thin paper that has been unsuitable in the past. It can be applied to sandwich paper and synthetic paper directly and partially on the areas necessary for color development, and is very useful.
【０００３】従来においては、水系に分散しているマイ
クロカプセルを、油性インキあるいは油性塗料からなる
油性塗液に含有させる場合、得られたマイクロカプセル
の水糸分散液を一旦、公知の調製法、すなわち、噴霧乾
燥法により乾燥させ、流動性の良いマイクロカプセル粉
末を得た後、これを油性のワニスあるいは塗料用樹脂中
に練肉させる方法が採られていた。Conventionally, when microcapsules dispersed in an aqueous system are contained in an oil-based coating liquid consisting of an oil-based ink or oil-based paint, the water-dispersed liquid of the obtained microcapsules is once prepared by a known preparation method, That is, there has been adopted a method in which a microcapsule powder having good fluidity is obtained by drying by a spray drying method and then this is kneaded in an oily varnish or a coating resin.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな噴霧乾燥法では、マイクロカプセルを粉末状でイン
キ溶媒と混合するため、流動性を得るためには、分散に
使用するインキ量を多くする必要があり、この結果、相
対的にカプセル含有量が少なくなり、カプセル含有濃度
の高いインキを調製することは難しく、印刷後の発色が
薄いといった問題が生じている。しかも、乾燥の過程に
おいて、カプセル化の際に使用した高分子の乳化剤成分
から水分が取り除かれ、この乳化剤成分が接着剤となっ
てカプセルの１次粒子同志が凝集して２次粒子となり、
さらに、この２次粒子表面には乾燥フィルムが形成され
る。すなわち、複数のカプセル粒子が乾燥フィルムによ
ってラッピングされるためその粒子径は１次粒子径の数
倍から数十倍にもなり、よって、印刷適性を得るために
は、粉砕ロールにより平均粒径２μｍ以下、さらに好ま
しくは１μｍ以下に粉砕しなければならない。また、加
熱乾燥することでカプセル壁材が乾燥熱により硬化して
もろくなり、粉砕時に２次粒子は容易に破壊される。こ
の結果、例えば、表裏面に発色染料と顕色剤を塗布した
感圧複写中葉紙を製造した場合、破壊により遊離したカ
プセル芯物質の発色染料が紙に染み込むため、顕色剤塗
布面が発色し、使用に耐えないものとなる。また、この
ような方法では、噴霧乾燥機、混合撹拌機、粉砕ロール
等の多くの設備を必要とするだけでなく、限りなく１次
粒子に近づけるため、粉末にするカプセル分散液を５％
程度の希釈液にすると、噴霧乾燥中にカプセルの相当量
が失われ歩留まりが低く生産性は非常に悪い。However, in such a spray drying method, since the microcapsules are mixed in powder form with the ink solvent, it is necessary to increase the amount of ink used for dispersion in order to obtain fluidity. As a result, the capsule content is relatively small, it is difficult to prepare an ink having a high capsule content concentration, and there is a problem that the color development after printing is weak. Moreover, in the process of drying, water is removed from the polymeric emulsifier component used during encapsulation, and this emulsifier component serves as an adhesive to agglomerate the primary particles of the capsule into secondary particles.
Further, a dry film is formed on the surface of the secondary particles. That is, since a plurality of capsule particles are wrapped by a dry film, the particle size thereof is several times to several tens of times the primary particle size. Therefore, in order to obtain printability, an average particle size of 2 μm is obtained by a pulverizing roll. Hereafter, it should be pulverized to 1 μm or less. Also, by heating and drying, the capsule wall material becomes brittle even when cured by the heat of drying, and the secondary particles are easily broken during pulverization. As a result, for example, when pressure-sensitive copying mid-leaf paper with a coloring dye and a developer coated on the front and back sides is manufactured, the coloring dye of the capsule core substance that is released by destruction penetrates into the paper, so that the surface coated with the developer is colored. However, it cannot be used. Further, such a method not only requires a lot of equipment such as a spray dryer, a mixing and agitating machine, and a pulverizing roll, but in order to bring the particles closer to the primary particles as much as possible, the capsule dispersion liquid to be powdered is 5%.
When diluted to a certain degree, a considerable amount of capsules are lost during spray drying, resulting in low yield and very poor productivity.
【０００５】また、水系分散物を油系に置換し、分散さ
せる技術としては、例えば、印刷インキ製造において、
一般的に使用される方法として、ケーキ状態の着色剤を
油性のワニスに混合し、さらに、この混合液を加温し、
上澄み液として浮きでた水分をデカンテーションによっ
て取り除き、さらに、加温、真空引きを続け、残りの水
分を除去して着色剤を水系から油系に置換する方法、い
わゆる、フラッシング法が採られているが、着色剤の水
系分散液をそのまま用いることは、着色剤の固化、ワニ
スとの分離、蒸発時の泡、突沸等の問題により難しく、
したがって、着色剤の水系分散液をフィルタープレス等
により、一度水分を減少させた脱水ケーキを使用するも
のである。しかしながら、このケーキ状態でも大部分は
凝集して２次粒子状態にあり、インキの印刷適性を持た
せるためには、着色剤が十分に分散している必要があ
り、この場合でも、着色剤の凝集物を粉砕ロールにより
粉砕しなければならない。A technique for substituting an oil-based dispersion with an oil-based dispersion to disperse the dispersion is, for example, in the production of printing ink.
As a commonly used method, a colorant in a cake state is mixed with an oily varnish, and the mixture is heated,
A method of removing the water floating as a supernatant liquid by decantation, further heating and vacuuming to remove the remaining water and replacing the colorant with an oil-based colorant, a so-called flushing method has been adopted. However, it is difficult to use the aqueous dispersion of the colorant as it is due to problems such as solidification of the colorant, separation from the varnish, bubbles during evaporation, and bumping,
Therefore, the dehydrated cake whose water content has been once reduced by filtering the aqueous dispersion of the colorant with a filter press or the like is used. However, even in this cake state, most of them are agglomerated into a secondary particle state, and it is necessary for the colorant to be sufficiently dispersed in order to have printability of the ink. The agglomerates must be milled by mill rolls.
【０００６】したがって、本発明では、水系に分散生成
したマイクロカプセルを凝集させることなく１次粒子の
まま、かつ、カプセル壁材を乾燥熱により硬化させるこ
となく、壁材の弾性・強度を保持したまま、これを油系
に置換せしめ、前述の諸課題を解決することを目的とす
るものである。[0006] Therefore, in the present invention, the elasticity and strength of the wall material are maintained without agglomeration of the microcapsules dispersed and generated in the water system as primary particles and without curing the capsule wall material by the drying heat. As it is, the purpose is to replace it with an oil system and solve the above-mentioned various problems.
【０００７】[0007]
【課題を解決するための手段】本発明によれば、マイク
ロカプセル水系分散液中に、ワニスあるいは塗料用樹脂
及びカプセル壁材の表層の両方に親和する溶剤、好まし
くは、２価以上の低級アルコールを混合し、カプセル壁
材の表層に、この溶剤の親水基を親和させ、得られた溶
液に、油性インキ、油性塗料の主材である油性のワニス
あるいは塗料用樹脂、例えば、メタクリル酸誘導体、ア
クリル酸誘導体、不飽和脂肪酸の混合グリセリド等及
び、補助剤を混合し、カプセル壁材の表層に親和した溶
剤の疎水基を介して、マイクロカプセルを油性のワニス
あるいは塗料用樹脂に親和させ、さらに、真空蒸留によ
り、得られた混合液を固化、発泡、分離、突沸させるこ
となく、マイクロカプセル水系分散液の水分を気化し除
去することで、個々のカプセル粒子を凝集させることな
く水系から油系へと置換させるものである。According to the present invention, a solvent compatible with both the varnish or the coating resin and the surface layer of the capsule wall material, preferably a dihydric or higher valent lower alcohol, is added to the microcapsule aqueous dispersion. , The surface layer of the capsule wall material, the hydrophilic group of this solvent is made to be compatible, the resulting solution, oil-based ink, oil-based varnish or paint resin as the main material of the oil-based paint, for example, methacrylic acid derivative, Acrylic acid derivative, mixed glyceride of unsaturated fatty acid and the like, and an auxiliary agent are mixed, and the microcapsules are made to be compatible with the oily varnish or the coating resin through the hydrophobic group of the solvent that is compatible with the surface layer of the capsule wall material, and further. By vaporizing and removing the water content of the microcapsule aqueous dispersion without solidifying, foaming, separating, or bumping the resulting mixed solution by vacuum distillation, Is intended to replace from aqueous without the oil-based to agglutinate capsule particles.
【０００８】[0008]
【作用】このように、本発明においては、マイクロカプ
セルを分散状態で水系から油系へ、直接的に置換させる
ことから、カプセル同志は凝集せず一次粒子の状態で水
系から油系へと置換するものである。さらに、乾燥工程
を経ることがないため、カプセル壁材は乾燥熱により硬
化することなく、本来の壁材の柔軟性と強度が保持さ
れ、よって、塗液加工時の圧力破壊は生じず、塗工後に
適度な圧力で破壊されるものである。As described above, in the present invention, since the microcapsules are directly replaced from the water system to the oil system in the dispersed state, the capsules do not aggregate and are replaced from the water system to the oil system in the state of primary particles. To do. Furthermore, since the drying process is not performed, the capsule wall material is not cured by the heat of drying, and the original flexibility and strength of the wall material are retained. It is destroyed by moderate pressure after construction.
【０００９】[0009]
【実施例】以下、本発明を具体的に説明する。本発明に
おいては、疎水性芯物質及び、カプセル壁材については
特に限定はなく、疎水性芯物質では、染料、顔料、示温
剤、香料、殺菌剤等の固体微粒子、あるいは、乳化安定
性の良いものであれば液晶、薬剤、溶剤等の液体微粒子
でも良い。そして、カプセル壁材については、ゼラチ
ン、ポリアミド、ポリウレタン、ポリエステル、ポリ尿
素、ポリスルホンアミド、ポリスルホネート、ポリウレ
ア等である。また、カプセル生成手段においては、従来
から慣用されている方法、例えば、インサイチュ法、界
面重合法、コアセルベーション法、あるいは、オリフィ
ス法も用いることができる。例えば、本発明のマイクロ
カプセルの水系分散液としては、発色染料を芯物質と
し、酸触媒および乳化・分散剤的機能を有するスチレン
無水マレイン酸共重合体の部分加水分解物と、ポリマを
形成する反応成分としてメラミンまたは尿素とホルマリ
ン、あるいは、これらの初期重縮合物を用い、インサイ
チュ法によってメラミンまたは尿素−ホルマリン樹脂を
カプセル壁材として形成し、マイクロカプセルを水糸に
分散生成させたものが適当である。The present invention will be specifically described below. In the present invention, the hydrophobic core substance and the capsule wall material are not particularly limited, and the hydrophobic core substance is a solid fine particle such as a dye, a pigment, a temperature indicator, a fragrance, a bactericide, or has good emulsion stability. Liquid fine particles such as liquid crystals, chemicals, solvents, etc. may be used as long as they are used. The capsule wall material is gelatin, polyamide, polyurethane, polyester, polyurea, polysulfonamide, polysulfonate, polyurea, or the like. Further, in the capsule forming means, a conventionally used method, for example, an in situ method, an interfacial polymerization method, a coacervation method, or an orifice method can be used. For example, as an aqueous dispersion of microcapsules of the present invention, a color forming dye is used as a core substance, and an acid catalyst and a partial hydrolyzate of a styrene-maleic anhydride copolymer having an emulsifying / dispersing agent function are formed with a polymer. Melamine or urea and formalin as a reaction component, or using these initial polycondensates, melamine or urea-formalin resin is formed as a capsule wall material by an in situ method, and those obtained by dispersing and forming microcapsules in water thread are suitable. Is.
【００１０】次に、各作成工程について詳述する。先
ず、マイクロカプセル水系分散液に、インキ用油性のワ
ニスあるいは塗料用樹脂と、前記ワニスあるいは塗料用
樹脂及び前記カプセル壁材の表層の両方に親和する溶剤
とを混合する工程：ワニスあるいは塗料用樹脂及びカプ
セル壁材の表層の両方に親和する溶剤とは疎水性と親水
性を共有する溶剤であり、例えば、グリセリン、エチレ
ングリコール、ジエチレングリコール、モノエチルエー
テル、ブタンジオール、プロピレングリコール、プロピ
オン酸ペンタジオール等が挙げられ、これら溶剤は、分
子量が大き過ぎると水になじまず、あるいは、粘度が上
昇して混合できない。また、分子量に対して親水基の数
が多ければ多いほどカプセル壁材の表層との親和力が向
上するため、好ましくは、２価以上の多価アルコールが
良く、さらには、油系への効率的な置換のために、一定
数以上の疎水基と高い沸点が必要であり、したがって、
炭素原子数が２以上である低級アルコールを用いるのが
適当である。例えば、ＵＶ硬化型の印刷インキでは、好
ましくは、エチレングリコールが良く、さらに好ましく
は、グリセリンが良い。これは、エチレングリコール等
がアクリルポリマ、オリゴマ、モノマ等の出発物質とさ
れる原料であり、アクリルオリゴマ、アクリルエステ
ル、アクリルエステルオリゴマ等のアクリル酸誘導体か
らなるＵＶ硬化型の油性のワニスとの相性が良いためで
ある。Next, each production process will be described in detail. First, a step of mixing a microcapsule aqueous dispersion with an oil-based varnish for inks or a coating resin and a solvent that is compatible with both the varnish or coating resin and the surface layer of the capsule wall material: varnish or coating resin And the solvent having affinity with both the surface layer of the capsule wall material is a solvent which shares hydrophobicity and hydrophilicity, and for example, glycerin, ethylene glycol, diethylene glycol, monoethyl ether, butanediol, propylene glycol, pentadiol propionate, etc. If the molecular weight of these solvents is too large, they will not be compatible with water, or the viscosity will increase and they cannot be mixed. In addition, the greater the number of hydrophilic groups with respect to the molecular weight, the higher the affinity with the surface layer of the capsule wall material, and therefore, a polyhydric alcohol having a valence of 2 or more is preferable, and moreover, it is more efficient for oil systems. A certain number of hydrophobic groups and high boiling points are required for
It is suitable to use a lower alcohol having 2 or more carbon atoms. For example, in a UV-curable printing ink, ethylene glycol is preferable, and glycerin is more preferable. This is a raw material in which ethylene glycol or the like is a starting material such as an acrylic polymer, an oligomer or a monomer, and is compatible with a UV curable oily varnish made of an acrylic acid derivative such as an acrylic oligomer, an acrylic ester or an acrylic ester oligomer. Because it is good.
【００１１】マイクロカプセルにはカプセル壁材と、こ
れを覆うように、乳化・分散機能を有する酸触媒の層、
例えば、スチレン無水マレイン酸共重合体の部分加水分
解物等が表層を形成している場合、カプセル壁材の表層
面に表出している酸触媒の親水基例えば、スチレン無水
マレイン酸共重合体ならばカルボキシル基は、水系分散
状態では水分子と互いに水素結合しているが、この分散
液に、親水性と疎水性を共有する溶剤を混合すると、カ
プセル壁材の表層面が保水した状態で、この溶剤の親水
基が酸触媒の親水基と水素結合するため、この溶剤は酸
触媒を介してマイクロカプセル壁材の表層と親和するも
のである。また、この溶剤のマイクロカプセル水系分散
液への添加量は、マイクロカプセル粒子の表面積の総計
に対応して親和機能を維持できる最低量と、一方、添加
量過多による塗液適性の低下等を考慮すると、マイクロ
カプセル水系分散液の固形分量に対して５〜１００重量
％が適当であり、好ましくは、２０〜８５重量％、さら
に好ましくは、３０〜７０重量％が良い。The microcapsules include a capsule wall material and a layer of an acid catalyst having an emulsifying / dispersing function so as to cover it.
For example, when a partial hydrolyzate of a styrene maleic anhydride copolymer or the like forms a surface layer, a hydrophilic group of the acid catalyst exposed on the surface layer surface of the capsule wall material, for example, a styrene maleic anhydride copolymer For example, a carboxyl group is hydrogen-bonded to water molecules in an aqueous dispersion state, but when this dispersion is mixed with a solvent that shares hydrophilicity and hydrophobicity, the surface layer surface of the capsule wall material retains water, Since the hydrophilic group of this solvent hydrogen-bonds with the hydrophilic group of the acid catalyst, this solvent has an affinity for the surface layer of the microcapsule wall material through the acid catalyst. Further, the amount of this solvent added to the microcapsule aqueous dispersion is the minimum amount capable of maintaining the affinity function corresponding to the total surface area of the microcapsule particles, while considering the decrease in coating liquid suitability due to the excessive addition amount, etc. Then, 5 to 100% by weight is suitable for the solid content of the microcapsule aqueous dispersion, preferably 20 to 85% by weight, and more preferably 30 to 70% by weight.
【００１２】次に、インキ用油性のワニスあるいは塗料
用樹脂とは、油性インキあるいは油性塗料の主材として
調製されるもので、本発明では、真空蒸留により水分を
選択的に気化し除去するため、その沸点は、少なくとも
水よりも高いものである。例えば、ＵＶ硬化型のもので
はアクリル酸をエステル反応またはエーテル反応させ不
飽和基をもたせたもの、すなわち、アクリル酸メチル、
アクリル酸メチル、多価アルコールのアクリル酸エステ
ル、エポキシ系アクリレート、ウレタン系アクリレー
ト、ポリエステル系アクリレート、ポリエーテル系アク
リレート等のモノマまたはオリゴマ、あるいは、酸化重
合型のものでは、例えば、植物油では、オレイン酸、リ
ノレイン酸、リノール酸を主成分としたアマニ油とシナ
キリ油といった乾性油、あるいは、大豆油等の半乾性
油、または、ヒマシ油等の不乾性油等の不飽和脂肪酸の
混合グリセリドである。さらに、種々の油性インキある
いは油性塗料を得るための汎用性を考慮して、例えば、
フェノール樹脂、ポリエステル樹脂、ロジン変性フェノ
ール樹脂、ロジン変性マレイン酸樹脂、エポキシ樹脂、
ケトン樹脂、ウレタン樹脂等であっても良く、また、塗
料用樹脂の希釈溶剤としては、トルエン、キシレン、酢
酸正ブチル、酢酸イソブチル等でも良く、あるいは、高
沸点のものでは、ノルマルパラフィン、イソパラフィ
ン、シクロパラフィン、アルキルベンゼン、その他、高
沸点の脂肪族炭化水素でも良い。Next, the oil-based varnish for ink or the resin for paint is prepared as the main material of the oil-based ink or oil-based paint. In the present invention, water is selectively vaporized and removed by vacuum distillation. , Its boiling point is at least higher than that of water. For example, in the case of a UV-curable type, acrylic acid has an unsaturated group by an ester reaction or an ether reaction, that is, methyl acrylate,
Monomers or oligomers of methyl acrylate, acrylic acid esters of polyhydric alcohols, epoxy-based acrylates, urethane-based acrylates, polyester-based acrylates, polyether-based acrylates, etc., or oxidatively polymerized ones, such as vegetable oils, oleic acid , A dry oil such as linseed oil and cinnamon oil containing linoleic acid and linoleic acid as main components, a semi-dry oil such as soybean oil, or a mixed glyceride of unsaturated fatty acids such as non-drying oil such as castor oil. Furthermore, considering the versatility for obtaining various oil-based inks or oil-based paints, for example,
Phenol resin, polyester resin, rosin-modified phenol resin, rosin-modified maleic acid resin, epoxy resin,
It may be a ketone resin, a urethane resin, etc., and the diluent solvent for the coating resin may be toluene, xylene, pure butyl acetate, isobutyl acetate, etc. Cycloparaffin, alkylbenzene, or other high boiling aliphatic hydrocarbon may be used.
【００１３】そして、その混合液中では、親水性と疎水
性を共有する溶剤が、その親水基をもってカプセル壁材
の表層に親和している状態となり、一方、その疎水基を
もって、ワニスあるいは塗料用樹脂と親和する。すなわ
ち、マイクロカプセルは、その壁材の表層に親和した親
水性と疎水性を共有する溶剤を介し、さらに、油系へ親
和することにより置換が達成されるものである。In the mixed solution, the solvent sharing both hydrophilicity and hydrophobicity is in a state of having affinity for the surface layer of the capsule wall material with its hydrophilic group, while having the hydrophobic group for varnish or paint. Affinity with resin. That is, the microcapsules can be replaced by a solvent that shares hydrophilicity and hydrophobicity that is compatible with the surface layer of the wall material and further has affinity for an oil system.
【００１４】次に 混合液中の水分を真空蒸留により気
化し除去せしめ、前記個々のマイクロカプセル粒子が独
立した一次粒子の状態で、水系から油系へ置換させる工
程：真空蒸留により 混合液の水分を気化し除去させる
ための条件としては、ワニスあるいは塗料用樹脂及びカ
プセル壁材の表層の両方に親和する溶剤を、例えば、グ
リセリン（沸点２９０℃）とした場合、真空引きによる
減圧（１０Ｐａ程度）条件下で、混合液は３０〜９０℃
に加温するが、高温では油性塗液が分離し易くなるの
で、好ましくは、３０〜７０℃が良い。そして、最終的
には、混合液の水分量を５〜１５重量％、好ましくは、
８〜１２重量％程度とする。尚、グリセリンは、油中の
水分が気化する際、突沸するのを抑制する消泡効果や水
分蒸発時に発生する液面の乾燥被膜を防ぐ湿潤効果を有
するもので、効率的に水分が除去できるものである。Next, the step of vaporizing and removing the water content in the mixed solution by vacuum distillation, and replacing the individual microcapsule particles in the state of independent primary particles with an aqueous system to an oil system: water content of the mixed solution by vacuum distillation The conditions for vaporizing and removing the varnish are as follows: When the solvent that is compatible with both the varnish or the coating resin and the surface layer of the capsule wall material is glycerin (boiling point 290 ° C.), the pressure is reduced by vacuuming (about 10 Pa). Under the condition, the mixture is 30 ~ 90 ℃
Although the oily coating liquid is easily separated at high temperature, the temperature is preferably 30 to 70 ° C. And finally, the water content of the mixed solution is 5 to 15% by weight, preferably,
It is about 8 to 12% by weight. Glycerin has a defoaming effect that suppresses bumping when the water in the oil is vaporized and a wetting effect that prevents a dry film on the liquid surface that occurs during evaporation of the water, so that the water can be efficiently removed. It is a thing.
【００１５】このような工程により製造された本発明の
マイクロカプセル含有油性塗液を、図１に、油性塗液中
に、個々に独立して分散した状態で含有されたマイクロ
カプセル粒子の拡大断面図として示すものである。The microcapsule-containing oil-based coating liquid of the present invention produced by such a process is shown in FIG. 1 in an enlarged cross section of microcapsule particles contained in the oil-based coating liquid in the state of being dispersed independently. It is shown as a figure.
【００１６】[0016]
【図１】[Figure 1]
【００１７】以下、本発明を、さらに具体的に説明する
が、本発明はこれら実施例によって限定されるものでは
ない。The present invention will be described in more detail below, but the present invention is not limited to these examples.
【００１８】マイクロカプセル分散液Ａの調製（感圧複
写紙用発色染料マイクロカプセル） スチレン無水マレイン酸共重合体（商品名：Ｓｃｒｉｐ
ｓｅｔ−５２０／モンサント社）を少量の水酸化ナトリ
ウムと共に溶解し、これを５重量％、ｐＨ４．６に調製
した水溶液２００部中に、アルキルナフタレン（商品
名：ＫＭＣ−１１３／呉羽化学工業）１９４部にクリス
タルバイオレットラクトン６部を加熱・溶解し、これを
乳化・分散させて平均粒径２μｍの乳化物を得た。次
に、この乳化物にメラミン−ホルマリン初期重縮合物
（商品名：Ｓｕｍｉｒｅｚ Ｒｅｓｉｎ５１３／住友化
学）６０部を加え、系の温度を７５℃にて２時間撹拌
し、感圧複写紙用マイクロカプセル分散液Ａを得た。 Preparation of Microcapsule Dispersion Liquid A (Color Dye Microcapsules for Pressure Sensitive Copying Paper) Styrene Maleic Anhydride Copolymer (trade name: Script
set-520 / Monsanto Co., Ltd.) was dissolved with a small amount of sodium hydroxide, and this was added to 200 parts of an aqueous solution adjusted to 5% by weight and pH 4.6, and alkylnaphthalene (trade name: KMC-113 / Kureha Chemical Industry) 194 6 parts of crystal violet lactone was heated and dissolved in 1 part, and this was emulsified and dispersed to obtain an emulsion having an average particle size of 2 μm. Next, 60 parts of melamine-formalin initial polycondensate (trade name: Sumirez Resin 513 / Sumitomo Chemical Co., Ltd.) was added to this emulsion, and the mixture was stirred at a system temperature of 75 ° C. for 2 hours to disperse the microcapsules for pressure-sensitive copying paper. Liquid A was obtained.
【００１９】マイクロカプセル分散液Ｂの調製（感圧複
写紙用発色染料マイクロカプセル） スチレン無水マレイン酸共重合体（商品名：Ｓｃｒｉｐ
ｓｅｔ−５２０／モンサント社）を少量の水酸化ナトリ
ウムと共に溶解し、これを７重量％、ｐＨ４．６に調製
した水溶液２００部中に、アルキルナフタレン（商品
名：ＫＭＣ−１１３／呉羽化学工業）１９４部にクリス
タルバイオレットラクトン６部を加熱・溶解し、これを
乳化・分散させて平均粒径１．５μｍの乳化物を得た。
次に、マイクロカプセル分散液Ａと同様な操作により、
感圧複写紙用マイクロカプセル分散液Ｂを得た。 Preparation of Microcapsule Dispersion Liquid B (Microcapsules of color dye for pressure-sensitive copying paper) Styrene maleic anhydride copolymer (trade name: Script
set-520 / Monsanto Co., Ltd.) was dissolved with a small amount of sodium hydroxide, and this was added to 200 parts of an aqueous solution adjusted to 7% by weight and pH 4.6, and alkylnaphthalene (trade name: KMC-113 / Kureha Chemical Industry Co., Ltd.) 194 6 parts of crystal violet lactone was heated and dissolved in 1 part, and this was emulsified and dispersed to obtain an emulsion having an average particle size of 1.5 μm.
Next, by the same operation as the microcapsule dispersion A,
A microcapsule dispersion B for pressure-sensitive copying paper was obtained.
【００２０】マイクロカプセル分散液Ｃの調製（示温剤
マイクロカプセル） スチレン無水マレイン酸共重合体（商品名：Ｓｃｒｉｐ
ｓｅｔ−５２０／モンサント社）を少量の水酸化ナトリ
ウムと共に溶解し、これを５重量％、ｐＨ４．６に調製
した水溶液２５０部中に、クリスタルバイオレットラク
トン９．５部をビスフェノールＡ９．５部、さらに、ミ
リスチルアルコール２３１部を加熱・溶解し、５０℃に
した示温剤２５０部を平均粒径２μｍになるように乳化
・分散させて乳化物を得た。次に、この乳化物にメラミ
ン−ホルマリン初期重縮合物（商品名：Ｓｕｍｉｒｅｚ
Ｒｅｓｉｎ５１３／住友化学）７５部を加え、系の温
度を７０℃にて２時間撹拌し、示温剤マイクロカプセル
分散液Ｃを得た。 Preparation of Microcapsule Dispersion Solution C (Microcapsule with Temperature Indicator) Styrene Maleic Anhydride Copolymer (trade name: Script)
set-520 / Monsanto Co., Ltd.) together with a small amount of sodium hydroxide and dissolved in 250 parts of an aqueous solution adjusted to 5% by weight and having a pH of 4.6, 9.5 parts of crystal violet lactone and 9.5 parts of bisphenol A are further added. Then, 231 parts of myristyl alcohol was heated and dissolved, and 250 parts of the temperature indicator which was heated to 50 ° C. was emulsified and dispersed so as to have an average particle size of 2 μm to obtain an emulsion. Next, melamine-formalin initial polycondensate (trade name: Sumirez) was added to this emulsion.
Resin 513 / Sumitomo Chemical Co., Ltd.) (75 parts) was added, and the temperature of the system was stirred at 70 ° C. for 2 hours to obtain a temperature indicator microcapsule dispersion C.
【００２１】［実施例１］ ：真空ポンプを連結した３００ｍｌの密閉容器（撹拌
機付）に、５０重量％マイクロカプセル分散液Ａ８０部
と、グリセリン（和光純薬工業）２０部とを混合し十分
に撹拌する。 ：で得た混合液に、撹拌状態のまま、ＵＶ硬化型の
油性のワニス（商品名：ＦＤグロスＯＰニス−１／東洋
インキ製造）２０部を加えて混合する。 ：で得た混合液を４０℃に加温し、さらに、真空引
きを行ってフラスコ内の気圧を１０Ｐａ程度にまで減圧
し、１〜２時間程度この状態を保ちながら水分を除去
し、水分量を１０重量％程度に下げる。 ：で得た油性インキに、使用する印刷機に適応する
ように、印刷インキ用調製剤（商品名：ＦＤレジューサ
ーＯＰ／東洋インキ製造）３０部を加え、十分に撹拌す
る。 ：で調製された油性インキを、前記印刷機で、フォ
ーム上質紙（連量４０Ｋｇ）及び、複写下葉紙（連量４
０Ｋｇ；商品名：Ｃ４０／富士フイルム）裏面に２０ｍ
／ｍｉｎの印刷速度で、インキ盛量を３ｇ／ｍ２となる
様に、印刷・ＵＶ乾燥させ、感圧スポット印刷物を得
た。Example 1 In a 300 ml closed container (with a stirrer) connected to a vacuum pump, 80 parts of 50% by weight of microcapsule dispersion A and 20 parts of glycerin (Wako Pure Chemical Industries) were mixed sufficiently. Stir to. 20 parts of UV curable oily varnish (trade name: FD Gloss OP Varnish-1 / Toyo Ink Mfg. Co., Ltd.) is added to the mixed solution obtained in the step (1) under stirring. : The mixed solution obtained in: is heated to 40 ° C., and further, vacuuming is performed to reduce the atmospheric pressure in the flask to about 10 Pa, and moisture is removed while maintaining this state for about 1 to 2 hours. Is reduced to about 10% by weight. To the oil-based ink obtained in :, 30 parts of a printing ink preparation (trade name: FD Reducer OP / Toyo Ink Mfg. Co., Ltd.) is added so as to be compatible with the printing machine used, and the mixture is sufficiently stirred. In the above printing machine, the oil-based ink prepared in the above was used to print high-quality foam paper (continuous amount of 40 Kg) and copy bottom paper (continuous amount of 4
0kg; Product name: C40 / Fujifilm) 20m on the back
At a printing speed of / min, printing and UV drying were performed so that the ink amount was 3 g / m 2, and a pressure-sensitive spot printed matter was obtained.
【００２２】［実施例２］ ：［実施例１］で使用したグリセリン（和光純薬工
業）２０部を、３０部に変更し［実施例１］と同様な操
作を行なう。 〜：［実施例１］で使用した油性のワニス（商品
名：ＦＤグロスＯＰニス／東洋インキ製造）を、油性の
ワニス（商品名：レカートンＯＰニスＮｏ．６／Ｔ＆Ｋ
ＴＯＫＡ）に変更し、印刷インキ用調製剤（商品名：
ＦＤレジューサーＯＰ／東洋インキ製造）を印刷インキ
用調製剤（商品名：ＵＶ１６１レジューサー／Ｔ＆Ｋ
ＴＯＫＡ）に変更し、［実施例１］と同様な操作を行な
い、感圧スポット印刷物を得た。[Example 2]: 20 parts of glycerin (Wako Pure Chemical Industries, Ltd.) used in [Example 1] was changed to 30 parts and the same operation as in [Example 1] was performed. ~: The oil-based varnish (trade name: FD gloss OP varnish / Toyo Ink Mfg. Co., Ltd.) used in [Example 1] was replaced with the oil-based varnish (trade name: Recarton OP varnish No. 6 / T & K).
Change to TOKA, and prepare for printing ink (trade name:
FD reducer OP / Toyo Ink Mfg. Co., Ltd. for printing ink (Product name: UV161 reducer / T & K)
Then, the same operation as in [Example 1] was performed to obtain a pressure-sensitive spot printed matter.
【００２３】［実施例３］ ：［実施例１］と同様 〜：［実施例１］で使用した油性のワニス（商品
名：ＦＤグロスＯＰニスー１／東洋インキ製造）を、ロ
ジン変性フェノール樹脂と石油糸高沸点溶剤（商品名：
７号ソルベント／日本石油）の４：６の混合物からなる
油性のワニス（粘度；１００Ｐａ・ｓ／２５℃）に変更
し、［実施例１］と同様な操作を行ない、感圧スポット
印刷物を得た。[Example 3]: Same as [Example 1] ~: The oil-based varnish used in [Example 1] (trade name: FD Gloss OP Varnish-1 / Toyo Ink Co., Ltd.) was mixed with a rosin-modified phenol resin. Petroleum yarn high boiling point solvent (trade name:
The oil-based varnish (viscosity; 100 Pa · s / 25 ° C.) composed of a 4: 6 mixture of No. 7 solvent / Nippon Petroleum) was used, and the same operation as in [Example 1] was performed to obtain a pressure-sensitive spot printed matter. It was
【００２４】［実施例４］ ：［実施例１］で使用したグリセリン（和光純薬工
業）２０部を、３５部に変更し［実施例１］と同様な操
作を行なう。 ：［実施例１］で使用した油性のワニス（商品名：Ｆ
ＤグロスＯＰニス−１／東洋インキ製造）を油性のワニ
ス（商品名：ＫＯＰニス−２／東洋インキ製造）に変更
し［実施例１］と同様な操作を行なう。 〜：［実施例１］で使用した印刷インキ用調製剤
（商品名：ＦＤレジューサーＯＰ／東洋インキ製造）
を、００ニス（東洋インキ製造）２５部にジェリーコン
パウンド（東洋インキ製造）５部を加えたものに変更
し、［実施例１］と同様な操作を行ない、感圧スポット
印刷物を得た。[Example 4] 20 parts of glycerin (Wako Pure Chemical Industries, Ltd.) used in [Example 1] was changed to 35 parts and the same operation as in [Example 1] was performed. : Oily varnish used in [Example 1] (trade name: F
D Gloss OP Varnish-1 / Toyo Ink Manufacturing) is changed to an oil-based varnish (trade name: KOP Varnish-2 / Toyo Ink Manufacturing), and the same operation as in [Example 1] is performed. ~: Preparation agent for printing ink used in [Example 1] (trade name: FD Reducer OP / Toyo Ink Mfg. Co., Ltd.)
Was changed to 25 parts of 00 varnish (manufactured by Toyo Ink) and 5 parts of jelly compound (manufactured by Toyo Ink), and the same operation as in [Example 1] was performed to obtain a pressure-sensitive spot printed matter.
【００２５】［実施例５］ ：［実施例１］で使用したグリセリン（和光純薬工
業）２０部を、エチレングリコール（和光純薬工業）３
０部に変更し［実施例１］と同様な操作を行なう。 ：［実施例１］で使用した油性のワニス（商品名：Ｆ
ＤグロスＯＰニス−１／東洋インキ製造）を、００ニス
（東洋インキ製造）に変更し［実施例１］と同様な操作
を行なう。 〜：［実施例１］で使用した印刷インキ用調製剤
（商品名：ＦＤレジューサーＯＰ／東洋インキ製造）
を、ＫＯＰニス（東洋インキ製造）２５部にジェリーコ
ンパウンド（東洋インキ製造）５部を加えたものに変更
し［実施例１］と同様な操作を行ない、感圧スポット印
刷物を得た。 尚、［実施例４］と［実施例５］については、ＵＶ乾燥
を必要としない。[Example 5]: 20 parts of glycerin (Wako Pure Chemical Industries) used in [Example 1] was replaced with ethylene glycol (Wako Pure Chemical Industries) 3
Change to 0 part and perform the same operation as in [Example 1]. : Oily varnish used in [Example 1] (trade name: F
D Gloss OP Varnish-1 / Toyo Ink Manufacturing) is changed to 00 varnish (Toyo Ink Manufacturing), and the same operation as in [Example 1] is performed. ~: Preparation agent for printing ink used in [Example 1] (trade name: FD Reducer OP / Toyo Ink Mfg. Co., Ltd.)
Was changed to 25 parts of KOP varnish (manufactured by Toyo Ink Co., Ltd.) and 5 parts of jelly compound (manufactured by Toyo Ink Co., Ltd.) was used, and the same operation as in [Example 1] was performed to obtain a pressure-sensitive spot printed matter. Note that UV drying is not required for [Example 4] and [Example 5].
【００２６】［実施例６］ ：真空ポンプを連結した３００ｍｌの密閉容器（撹拌
機付）に、５０重量％マイクロカプセル分散液Ｂ８０部
と、グリセリン（和光純薬工業）２０部とを混合し十分
に撹拌する。 〜：［実施例１］と同様の操作を行い、感圧スポッ
ト印刷物を得た。Example 6 In a 300 ml closed container (with a stirrer) connected to a vacuum pump, 80 parts of 50% by weight of microcapsule dispersion B and 20 parts of glycerin (Wako Pure Chemical Industries) were mixed sufficiently. Stir to. ~: The same operation as in [Example 1] was performed to obtain a pressure-sensitive spot printed matter.
【００２７】［実施例７］ ：真空ポンプを連結した３００ｍｌの密封容器（撹拌
機付）に、５０重量％マイクロカプセル分散液Ｃ８０部
と、グリセリン（和光純薬工業）２０部とを混合し十分
に撹拌する。 ：で得た混合液に、撹拌状態のまま、塗料用樹脂
（商品名：アロニックスＭ−１５０／東亜合成化学）２
０部を加えて混合する。 ：で得た混合液を４０℃に加温し、さらに、真空引
きを行ってフラスコ内の気圧を１０Ｐａ程度に減圧し、
１〜２時間程度この状態を保ち、水分を除去し、水分量
を１０重量％程度に下げる。 ：で得た油性塗料のコーティング適性を向上させる
ため、塗料用調製剤（商品名：アロニックスＭ−１０１
／東亜合成化学）３０部を加え十分に撹拌する。 ：で調製された油性塗料を、表面に絵柄が描かれた
マグカップ表面に、１０ｇ／ｍ２の盛量で塗工し、ＵＶ
硬化装置にて硬化させ、感温発色カップを得た。Example 7: A 300 ml sealed container (with a stirrer) connected to a vacuum pump was mixed with 80 parts of 50% by weight of microcapsule dispersion C and 20 parts of glycerin (Wako Pure Chemical Industries, Ltd.) and mixed well. Stir to. In the mixed liquid obtained in :, as it is in a stirring state, coating resin (Product name: Aronix M-150 / Toa Gosei Kagaku) 2
Add 0 parts and mix. The mixture liquid obtained in: is heated to 40 ° C., and further vacuumed to reduce the atmospheric pressure in the flask to about 10 Pa,
This state is maintained for about 1 to 2 hours to remove water, and the water content is reduced to about 10% by weight. In order to improve the coating suitability of the oil-based paint obtained in :, a paint preparation (trade name: Aronix M-101
/ Toa Gosei Kagaku) 30 parts and stir well. The oil-based paint prepared in: was applied to the surface of the mug with a pattern drawn on it in a coating amount of 10 g / m 2 , and UV was applied.
It was cured by a curing device to obtain a temperature-sensitive color forming cup.
【００２８】［実施例８］ ：［実施例７］と同様。 ：［実施例７］で使用した塗料用樹脂（商品名：アロ
ニックスＭ−１５０／東亜合成化学）２０部を、塗料用
樹脂（商品名：ニューフロンティアＲ−１２００／第一
工業製薬）１０部、塗料用樹脂（商品名：ニューフロン
ティアＴＭＰＴ／第一工業製薬）５部、塗料用樹脂（商
品名：ニューフロンティアＰＥ−４００／第一工業製
薬）及び塗料用樹脂（商品名：イルガキュア６５１／チ
バガイギー）１部に変更し［実施例７］と同様な操作を
行なう。 〜：［実施例７］で使用した塗料用調製剤（商品
名：アロニックスＭ−１０１／東亜合成化学）３０部
を、塗料用調製剤（商品名：ニューフロンティアＨＤＤ
Ａ／第一工業製薬）３０部に変更し、［実施例７］と同
様な操作を行ない、感温発色カップを得た。[Embodiment 8]: Same as [Embodiment 7]. : 20 parts of the coating resin (product name: Aronix M-150 / Toagosei Kagaku) used in [Example 7], 10 parts of the coating resin (product name: New Frontier R-1200 / Daiichi Kogyo Seiyaku), Paint resin (Product name: New Frontier TMPT / Daiichi Kogyo Seiyaku) 5 parts, Paint resin (Product name: New Frontier PE-400 / Daiichi Kogyo Seiyaku) and paint resin (Product name: Irgacure 651 / Ciba Geigy) Change to 1 part and perform the same operation as in [Embodiment 7]. ~: 30 parts of the paint preparation (trade name: Aronix M-101 / Toagosei Kagaku) used in [Example 7] was added to the paint preparation (trade name: New Frontier HDD).
A / Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 30 parts and the same operation as in [Example 7] was performed to obtain a temperature-sensitive color forming cup.
【００２９】［実施例９］ ：［実施例７］と同様 ：［実施例７］で使用した塗料用樹脂（商品名：アロ
ニックスＭ−１５０／東亜合成化学）２０部を、塗料用
樹脂（商品名：ニューフロンティアＲ−１４００／第一
工業製薬）１０部、塗料用樹脂（商品名：ニューフロン
ティアＣ９Ａ／第一工業製薬）１０部及び、塗料用樹脂
（商品名：イルガキュア１８４／チバガイギー）１部に
変更し、［実施例７］と同様な操作を行なう。 〜：［実施例７］で使用した塗料用調製剤（商品
名：アロニックスＭ−１０１／東亜合成化学）３０部
を、塗料用調製剤（商品名：ニューフロンティアＣＥＡ
／第一工業製薬）３０部に変更し［実施例７］と同様な
操作を行ない、感温発色カップを得た。[Example 9]: Same as [Example 7]: 20 parts of the coating resin (trade name: Aronix M-150 / Toa Gosei Kagaku) used in [Example 7] was mixed with the coating resin (commercial product). Name: New Frontier R-1400 / Daiichi Kogyo Seiyaku Co., Ltd. 10 parts, coating resin (Product name: New Frontier C9A / Daiichi Kogyo Seiyaku) 10 parts, and coating resin (Product name: Irgacure 184 / Ciba Geigy) 1 part And perform the same operation as in [Embodiment 7]. ~: 30 parts of the paint preparation (trade name: Aronix M-101 / Toagosei Kagaku) used in [Example 7] was added to the paint preparation (trade name: New Frontier CEA).
/ Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 30 parts and the same operation as in [Example 7] was performed to obtain a temperature-sensitive color-developing cup.
【００３０】［実施例１０］ ：［実施例７］と同様。 ：［実施例７］で使用した塗料用樹脂（商品名：アロ
ニックスＭ−１５０／東亜合成化学）２０部を、塗料用
樹脂（商品名：Ｅ−４／Ｔ＆Ｋ ＴＯＫＡ）２０部に変
更し［実施例７］と同様な操作を行なう。 〜：［実施例７］で使用した塗料用調製剤（商品
名：アロニックスＭ−１０１／東亜合成化学）３０部
を、塗料用調製剤（商品名：シルバーワニス／Ｔ＆ＫＴ
ＯＫＡ）２５部と、塗料用調製剤（商品名：レジューサ
ー／Ｔ＆Ｋ ＴＯＫＡ）５部に変更し［実施例７］と同
様な操作を行ない、感温発色カップを得た。[Embodiment 10]: Same as [Embodiment 7]. : 20 parts of the coating resin (trade name: Aronix M-150 / Toagosei Kagaku) used in [Example 7] was changed to 20 parts of coating resin (trade name: E-4 / T & K TOKA) Perform the same operation as in [Example 7]. ~: 30 parts of the paint preparation (trade name: Aronix M-101 / Toagosei Kagaku) used in [Example 7] was added to the paint preparation (trade name: Silver varnish / T & KT).
25 parts of OKA) and 5 parts of a paint preparation (trade name: reducer / T & K TOKA) were changed, and the same operation as in [Example 7] was performed to obtain a temperature-sensitive color forming cup.
【００３１】［実施例１１］ ：［実施例７］で使用したグリセリン（和光純薬工
業）２０部を、エチレングリコール（和光純薬工業）３
０部に変更し［実施例１］と同様な操作を行なう。 ：［実施例７］で使用した塗料用樹脂（商品名：アロ
ニックスＭ−１５０／東亜合成化学）２０部を、塗料用
樹脂（商品名：コーポニールＰＡ−２４Ｔ／昭和高分
子）１５部と、キシレン（和光純薬工業）１０部に変更
し［実施例７］と同様な操作を行なう。 〜：［実施例７］で使用した塗料用調製剤（商品
名：アロニックスＭ−１０１／東亜合成化学）３０部
を、キシレン（和光純薬工業）２５部、ＭＩＢＫ（和光
純薬工業）１０部及び、酢酸ブチル（和光純薬工業）に
変更し、［実施例７］と同様な操作を行ない、感温発色
カップを得た。 尚、［実施例１１］については、ＵＶ乾燥を必要としな
い。[Example 11]: 20 parts of glycerin (Wako Pure Chemical Industries) used in [Example 7] was mixed with 3 parts of ethylene glycol (Wako Pure Chemical Industries).
Change to 0 part and perform the same operation as in [Example 1]. : 20 parts of the coating resin (trade name: Aronix M-150 / Toagosei Kagaku) used in [Example 7], 15 parts of the coating resin (trade name: COPONYL PA-24T / Showa High Polymer), Xylene (Wako Pure Chemical Industries) was changed to 10 parts and the same operation as in [Example 7] was performed. ~: 30 parts of the paint preparation (trade name: Aronix M-101 / Toagosei Kagaku) used in [Example 7], xylene (Wako Pure Chemical Industries) 25 parts, MIBK (Wako Pure Chemical Industries) 10 parts Then, butyl acetate (Wako Pure Chemical Industries, Ltd.) was used, and the same operation as in [Example 7] was performed to obtain a temperature-sensitive color-developing cup. Note that UV drying is not required for [Example 11].
【００３２】［比較例１］ ：スプレードライヤ（噴霧乾燥機）により、マイクロ
カプセル分散液Ａを噴霧乾燥させ、カプセル粉体を得
る。 ：で得た粉体４０部に、油性のワニス（商品名：Ｆ
ＤグロスＯＰニス−１／東洋インキ製造）８０部を加え
混合する。 ：で得た油性インキに、印刷インキ用調製剤（商品
名：ＦＤレジューサーＯＰ／東洋インキ製造）３０部を
加え、十分に撹拌する。 ：［実施例１］の手順と同様の操作で、感圧スポッ
ト印刷物を得た。[Comparative Example 1]: The microcapsule dispersion A is spray-dried by a spray dryer (spray dryer) to obtain capsule powder. To 40 parts of the powder obtained in
80 parts of D gloss OP varnish-1 / Toyo Ink Mfg. Co., Ltd. are added and mixed. Add 30 parts of a preparation for printing ink (trade name: FD Reducer OP / Toyo Ink Mfg. Co., Ltd.) to the oil-based ink obtained in: and stir sufficiently. A pressure-sensitive spot printed matter was obtained by the same procedure as in [Example 1].
【００３３】［比較例２］ ：スプレードライヤ（噴霧乾燥機）により、マイクロ
カプセル分散液Ｂを噴霧乾燥させ、カプセル粉体を得
る。 ：で得た粉体４０部に塗料用樹脂（商品名：アロニ
ックスＭ−１５０／東亜合成化学）８０部を加え混合す
る。 ：で得た混合物に、塗料用調製剤（商品名：アロニ
ックスＭ−１０１／東亜合成化学）３０部を加え十分に
撹拌する。 ：で得た油性塗料を［実施例７］と同様な操作で、
感温発色カップを得た。[Comparative Example 2]: The microcapsule dispersion liquid B is spray-dried by a spray dryer (spray dryer) to obtain capsule powder. To 40 parts of the powder obtained in :, 80 parts of a resin for coating (trade name: Aronix M-150 / Toagosei Kagaku) is added and mixed. To the mixture obtained in :, 30 parts of a paint preparation (trade name: Aronix M-101 / Toagosei Kagaku) is added and stirred sufficiently. In the same manner as in [Example 7], the oil-based paint obtained in
A temperature-sensitive coloring cup was obtained.
【００３４】［実施例１］〜［実施例６］と［比較例
１］について、以下に示す比較評価を行い、これらの結
果を第１表に示した。感圧スポット印刷物の発色評価 Ａ．印圧による発色テスト：タイプライターにより、中
圧で印字を行なう。感圧複写紙を５パーツまで重ね合わ
せて、各パーツの複写による発色濃度を測定し、その平
均値を求める。 Ｂ．カレンダーロールによる発色テスト：カレンダーロ
ール（ニップ圧：１ｋｇ／インチ）にて、２パーツの感
圧複写紙にニップ圧を付与し、発色濃度を測定する。 尚、第１表中の発色濃度は、［比較例１］を１００とし
た場合の、各実施例の相対値を示し、値が高い程発色濃
度も高い。The following comparative evaluations were carried out for [Example 1] to [Example 6] and [Comparative Example 1], and the results are shown in Table 1. Color development evaluation of pressure-sensitive spot printed matter A. Color development test by printing pressure: Printing with medium pressure by a typewriter. The pressure-sensitive copy papers are piled up to 5 parts, and the color density of each part is measured and the average value is obtained. B. Color development test using a calendar roll: A calender roll (nip pressure: 1 kg / inch) is used to apply a nip pressure to two-part pressure-sensitive copying paper to measure the color density. The color density in Table 1 is the relative value of each example when [Comparative Example 1] is 100, and the higher the value, the higher the color density.
【００３５】感圧スポット印刷物のカプセル破壊率評価 Ａ．印刷物中のフリーオイル（カプセル非封入油）を、
ＴＨＦ（テトラヒドロフラン）で抽出後、液温７０℃の
条件下で高圧液体クロマトグラフィーにて、フリーオイ
ルの定量により、カプセル破壊率を測定する。 Ｂ．顕色剤塗布用紙の塗布面にスポット印刷し、常温で
７日間放置した後、８０℃に加温し、発色濃度によりカ
プセル破壊率を測定する。 Evaluation of capsule breakage rate of pressure-sensitive spot prints A. Free oil (non-encapsulated oil) in printed matter
After extraction with THF (tetrahydrofuran), the capsule destruction rate is measured by high pressure liquid chromatography under the condition of a liquid temperature of 70 ° C. by quantitative determination of free oil. B. Spot printing is performed on the coated surface of the color developer-coated paper, left at room temperature for 7 days, then heated to 80 ° C., and the capsule destruction rate is measured by the color density.
【００３６】[0036]
【表１】 [Table 1]
【００３７】［実施例７］〜［実施例１１］と［比較例
２］について、以下に示す比較評価を行い、これらの結
果を第２表に示した。マグカップ塗工面の性能評価 Ａ．消色状態評価：マグカップに５０℃の湯を入れ、塗
工面下に、予め印刷されていた絵柄の表出状況を目視に
より観察する。 Ｂ．発色状態評価：マグカップの５０℃の湯を２０℃の
水に入れ代え、塗工面下に、予め印刷されていた絵柄の
隠蔽状況を目視により観察する。 Ｃ．塗工面外観評価：塗工面の平滑性、光沢度などを目
視により観察する。[Examples 7 to 11] and [Comparative Example 2] were subjected to the following comparative evaluations, and the results are shown in Table 2. Performance evaluation of mug coated surface A. Decolored state evaluation: Hot water at 50 ° C. is put in a mug, and the appearance of the pattern previously printed under the coated surface is visually observed. B. Coloring state evaluation: 50 ° C hot water of the mug is replaced with 20 ° C water, and the hiding state of the pattern previously printed under the coated surface is visually observed. C. Appearance evaluation of coated surface: The smoothness and glossiness of the coated surface are visually observed.
【００３８】[0038]
【表２】 [Table 2]
【００３９】［実施例１］〜［実施例１１］で得た油性
塗液中のマイクロカプセルの平均粒子径は、どの実施例
についてもカプセル水系分散液のそれと等しく、かつ、
カプセル壁材は本来の柔軟性と強度を維持するものであ
った。これに対し、［比較例１］と［比較例２］で得た
ものは、どちらも凝集によって２次粒子となり、平均粒
子径は３０μｍ程度（最大１００μｍ）に増大し、さら
に、カプセル壁材が乾燥熱により硬化し脆弱化された。
また、［実施例１］〜［実施例１１］におけるマイクロ
カプセルの歩留まりについては、どの実施例においても
１００％であり、一方、［比較例１］と［比較例２］に
おけるそれは、噴霧乾燥中に相当量失われたため、どち
らも７０％程度であった。The average particle size of the microcapsules in the oil-based coating liquids obtained in [Example 1] to [Example 11] was the same as that of the capsule aqueous dispersion in all Examples, and
The capsule wall material maintained its original flexibility and strength. On the other hand, both of the ones obtained in [Comparative Example 1] and [Comparative Example 2] became secondary particles due to aggregation, the average particle diameter increased to about 30 μm (maximum 100 μm), and It was hardened and weakened by the heat of drying.
In addition, the yield of the microcapsules in [Example 1] to [Example 11] was 100% in all Examples, while that in [Comparative Example 1] and [Comparative Example 2] was during spray drying. In both cases, it was about 70%.
【００４０】[0040]
【発明の効果】本発明により、水系中に分散生成された
マイクロカプセルであっても、カプセル同志を凝集させ
ることなく１次粒子状態のまま、かつ、カプセル壁材の
強度、柔軟性を失わせず、その特性を保持したまま容易
に油系に置換できるため、従来法におけるカプセルの凝
集、カプセルの劣化、カプセルの破壊、あるいは、歩留
まりの低さ、過剰設備等の諸問題を解決するものであ
る。とりわけ、印刷分野においては、本発明の油性イン
キは、通常の印刷方式をもって用紙の種類は問わずに印
刷でき、従来のような部分的に発色を阻害するための減
感印刷の必要はなく、また、使用する印刷インキについ
ては、ＵＶ硬化型、酸化重合型のどちらでも製造可能で
あり、そして、紙面に印刷された場合でも繊維内までイ
ンキが浸み込み難く、かつ、カプセル封入発色染料の顕
色剤塗布用紙への転移の阻害は全くない。さらに、表面
および側面はインキ材料で固くなっているため、保護剤
の使用が不要であり、発色が従来よりも鮮明になる等
々、その効果は広範囲におよぶ。EFFECTS OF THE INVENTION According to the present invention, even microcapsules dispersed and formed in an aqueous system are kept in a primary particle state without aggregating the capsules with each other and lose the strength and flexibility of the capsule wall material. Instead, since it can be easily replaced with an oil system while maintaining its characteristics, it can solve various problems in the conventional method such as capsule aggregation, capsule deterioration, capsule destruction, or low yield and excess equipment. is there. In particular, in the printing field, the oil-based ink of the present invention can be printed by a normal printing method regardless of the type of paper, and there is no need for desensitizing printing for partially inhibiting color development as in the related art, The printing ink used can be either a UV-curing type or an oxidative-polymerizing type, and even when printed on paper, it is difficult for the ink to penetrate into the fibers, and the encapsulation coloring dye There is no inhibition of transfer to the color developer coated paper. Further, since the surface and the side surface are hardened with the ink material, it is not necessary to use a protective agent, and the color development becomes clearer than in the past, and the effect is wide.
【図１】 本発明における油性塗液中に、個々に独立し
て分散した状態で含有されたマイクロカプセル粒子の拡
大断面図である。FIG. 1 is an enlarged cross-sectional view of microcapsule particles contained in an oil-based coating liquid according to the present invention in a state of being dispersed individually and independently.
１芯物質 ２壁材 ３壁材表層 ４ワニスあるいは塗料用樹脂及びカプセル壁材の表層の
両方に親和する溶剤 ５インキ用油性のワニスあるいは塗料用樹脂からなる油
性塗液1 core substance 2 wall material 3 wall material surface layer 4 varnish or solvent that is compatible with both resin for paint and surface layer of capsule wall material 5 oil coating liquid consisting of oil varnish for ink or resin for paint
Claims (6)
脂中に、疎水性芯物質を包含するマイクロカプセル粒子
が、個々に独立して分散されてなり、前記カプセル壁材
の表層には、前記ワニスあるいは塗料用樹脂及び前記カ
プセル壁材の表層の両方に親和する溶剤が親和されてな
ることを特徴とするマイクロカプセル含有油性塗液。1. A microcapsule particle containing a hydrophobic core substance is independently dispersed in an oil-based varnish for ink or a resin for paint, and the varnish is formed on a surface layer of the capsule wall material. Alternatively, a microcapsule-containing oil-based coating liquid is characterized in that a solvent that is compatible with both the coating resin and the surface layer of the capsule wall material is made compatible.
カプセル壁材の表層の両方に親和する溶剤が、２価以上
の低級アルコールであることを特徴とする特許請求の範
囲第１項記載のマイクロカプセル含有油性塗液。2. The microcapsule according to claim 1, wherein the solvent compatible with both the varnish or the coating resin and the surface layer of the capsule wall material is a dihydric or higher valent lower alcohol. Contains oily coating liquid.
を特徴とする特許請求の範囲第１項記載のマイクロカプ
セル含有油性塗液。3. The microcapsule-containing oil-based coating liquid according to claim 1, wherein the oil-based coating liquid is an oil-based ink.
特徴とする特許請求の範囲第１項記載のマイクロカプセ
ル含有油性塗液。4. The oil-based coating liquid containing microcapsules according to claim 1, wherein the oil-based coating liquid is an oil-based coating material.
用油性のワニスあるいは塗料用樹脂と、前記ワニスある
いは塗料用樹脂及び前記カプセル壁材の表層の両方に親
和する溶剤とを混合する工程と、前記混合液中の水分を
真空蒸留により気化し除去せしめ、前記マイクロカプセ
ル粒子を個々に独立した状態で水系から油系へ置換させ
る工程、からなることを特徴とするマイクロカプセル含
有油性塗液の製造方法5. A step of mixing an oil-based varnish for inks or a coating resin, and a solvent that is compatible with both the varnish or coating resin and the surface layer of the capsule wall material, with the microcapsule aqueous dispersion, A method for producing a microcapsule-containing oily coating liquid, which comprises a step of vaporizing and removing water in a mixed solution by vacuum distillation, and substituting the microcapsule particles individually from an aqueous system to an oil system.
カプセル壁材の表層の両方に親和する溶剤を、前記マイ
クロカプセル水系分散液の固形分量に対して５〜１００
重量％の添加量で、前記マイクロカプセル水系分散液に
混合し、真空蒸留することを特徴とする特許請求の範囲
第５項記載のマイクロカプセル含有油性塗液の製造方
去。6. A solvent compatible with both the varnish or the coating resin and the surface layer of the capsule wall material is added in an amount of 5 to 100 relative to the solid content of the microcapsule aqueous dispersion.
The method for producing an oil-based coating liquid containing microcapsules according to claim 5, characterized in that the microcapsule aqueous dispersion is mixed with the added amount of wt% and vacuum-distilled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04029094A JP3181463B2 (en) | 1994-01-31 | 1994-01-31 | Method for producing oil-based paint containing microcapsules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04029094A JP3181463B2 (en) | 1994-01-31 | 1994-01-31 | Method for producing oil-based paint containing microcapsules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07216273A true JPH07216273A (en) | 1995-08-15 |
| JP3181463B2 JP3181463B2 (en) | 2001-07-03 |
Family
ID=12576479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04029094A Expired - Fee Related JP3181463B2 (en) | 1994-01-31 | 1994-01-31 | Method for producing oil-based paint containing microcapsules |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3181463B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114946A (en) * | 2000-10-06 | 2002-04-16 | Takeda Chem Ind Ltd | Coating composition |
| JP2005131580A (en) * | 2003-10-31 | 2005-05-26 | Toppan Forms Co Ltd | Microcapsules and recovery method from its aqueous dispersion |
| DE102021000688A1 (en) | 2021-02-10 | 2022-08-11 | Giesecke+Devrient Currency Technology Gmbh | Value Document Substrate and Composition |
-
1994
- 1994-01-31 JP JP04029094A patent/JP3181463B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114946A (en) * | 2000-10-06 | 2002-04-16 | Takeda Chem Ind Ltd | Coating composition |
| JP2005131580A (en) * | 2003-10-31 | 2005-05-26 | Toppan Forms Co Ltd | Microcapsules and recovery method from its aqueous dispersion |
| JP4527962B2 (en) * | 2003-10-31 | 2010-08-18 | トッパン・フォームズ株式会社 | Method for producing microcapsule-containing oil-based ink |
| DE102021000688A1 (en) | 2021-02-10 | 2022-08-11 | Giesecke+Devrient Currency Technology Gmbh | Value Document Substrate and Composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3181463B2 (en) | 2001-07-03 |
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