JP3475789B2 - Continuous production method of granular colored composition - Google Patents

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は新規な相転換方法に
よる粒状着色組成物の連続的製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous method for producing a granular coloring composition by a novel phase conversion method.

【０００２】[0002]

【従来の技術】従来印刷インキ用着色組成物を製造する
場合、粉末状乾燥顔料に油性ビヒクルを加え３本ロール
等の分散機で分散する方法、および水性顔料湿潤ケーキ
に油性ビヒクルを加えニーダーをはじめとする捏和機で
練り相転換させ、さらに水をデカンテーションによって
除去し、ついで加温しながら減圧脱水を行う方法とがあ
る。前者の製造方法は粉末状乾燥顔料粒子が強い力で凝
集体を形成し、３本ロール等の分散機で印刷インキ用着
色組成物中の顔料粒子を印刷インキとして許容される粒
径まで分散させるには多大な時間とエネルギーを要す
る。2. Description of the Related Art Conventionally, in the case of producing a coloring composition for a printing ink, a powdery dry pigment is added with an oily vehicle and dispersed with a disperser such as a three-roll mill, or an oily vehicle is added to a water-based pigment wet cake and a kneader is added. There is a method in which the kneading machine is used for kneading and phase conversion is performed, water is further removed by decantation, and then dehydration under reduced pressure is performed while heating. In the former production method, powdery dry pigment particles form an agglomerate with a strong force, and the pigment particles in the coloring composition for printing ink are dispersed by a dispersing machine such as a three-roll roller to a particle size acceptable as a printing ink. Takes a lot of time and energy.

【０００３】一方、後者の水性顔料湿潤ケーキを用いる
製造方法は、一般的にフラッシング法と呼ばれており、
水系の状態の顔料湿潤ケーキを油性ビヒクルにて油系へ
と置換を行う方法である。これは粉末状乾燥顔料粒子を
経ないために印刷インキ用着色組成物中の顔料粒子の凝
集力は前者ほど強い力ではない。また、この印刷インキ
用着色組成物から印刷インキを製造した場合、印刷イン
キの着色力、透明性が前者の製造方法より優れている。
以上の理由と製造コストの低減、省エネルギー等の観点
から印刷インキ製造業界では印刷インキ用着色組成物を
フラッシング法で製造する場合が多い。On the other hand, the latter production method using an aqueous pigment wet cake is generally called a flushing method,
In this method, the pigment wet cake in an aqueous state is replaced with an oil type vehicle using an oil vehicle. Since this does not pass through the powdery dry pigment particles, the cohesive force of the pigment particles in the coloring composition for printing ink is not as strong as the former. When a printing ink is produced from this coloring composition for printing ink, the coloring power and transparency of the printing ink are superior to those of the former production method.
In the printing ink manufacturing industry, the coloring composition for printing ink is often manufactured by the flushing method in view of the above reasons, reduction of manufacturing cost, and energy saving.

【０００４】また、従来のフラッシング法は主にバッチ
方式で行われている。これは、大型のニーダーをはじめ
とする捏和機に顔料濃度２０〜５０重量％程度の水性湿
潤顔料ケーキと油性ビヒクルを仕込み大きな動力で捏和
機の攪拌翼を回転させることにより、顔料を水相から油
相に相転換させる。さらに、水をデンカンテーションに
よって除去し、ついで加温しながら減圧脱水を行いイン
キ用着色組成物を得る方法が広く用いられている。しか
し、この製造方法では過大な装置が必要になり、また、
相転換、デカンテーション及び減圧脱水に多大な時間と
エネルギーを必要とする。相転換、デカンテーション及
び脱水を１台の装置でできるという利点はあるものの、
その工程の複雑さから自動化が難しい。またバッチ方式
であるために印刷インキ用着色組成物の品質にばらつき
が生じる等の問題点がある。Further, the conventional flushing method is mainly performed by a batch method. This is because a kneader such as a large kneader is charged with an aqueous wet pigment cake having a pigment concentration of about 20 to 50% by weight and an oily vehicle, and the stirring blades of the kneader are rotated with great power to remove the pigment from the water. Phase to oil phase. Further, a method is widely used in which water is removed by decantation, and then dehydration under reduced pressure is performed while heating to obtain a colored composition for ink. However, this manufacturing method requires excessive equipment, and
A great deal of time and energy are required for phase conversion, decantation and vacuum dehydration. Although there is an advantage that phase conversion, decantation and dehydration can be done with one device,
Automation is difficult because of the complexity of the process. Further, since it is a batch system, there is a problem that the quality of the coloring composition for printing ink varies.

【０００５】さらに、上記フラッシング法に用いる水性
湿潤顔料ケーキは顔料の水性懸濁液をフィルタープレス
等により濾過、水性懸濁液中の塩類を水洗及び圧搾し顔
料濃度を増加させたものを用いなければならず、合成し
た顔料の水性懸濁液のままで相転換させることは塩類の
水洗による精製が不十分となることから一般的に行わな
い。ここで得られた印刷インキ用着色組成物の顔料濃度
を高めることもハンドリング性が悪くなる等のことから
難しい。一般的に上記フラッシング法で製造した印刷イ
ンキ用着色組成物の顔料濃度は１０〜４５重量％程度で
あり顔料に対して油性ビヒクル量が多く多品種に展開す
ることが難しい。よって上記フラッシング法で製造した
印刷インキ用着色組成物は汎用性があるとは言えない。Further, the aqueous wet pigment cake used in the above flushing method must be one in which an aqueous suspension of pigment is filtered by a filter press or the like, and salts in the aqueous suspension are washed with water and pressed to increase the pigment concentration. In general, the phase transformation of the synthesized aqueous suspension of the pigment is not performed because the salt is insufficiently purified by washing with water. It is also difficult to increase the pigment concentration of the coloring composition for printing inks obtained here, because the handling property is deteriorated. Generally, the pigment concentration of the coloring composition for printing ink produced by the above-mentioned flushing method is about 10 to 45% by weight, and the amount of the oily vehicle relative to the pigment is large, and it is difficult to develop it in various kinds. Therefore, it cannot be said that the coloring composition for printing ink produced by the flushing method is versatile.

【０００６】連続方式でのフラッシング法に関しては特
開昭５０−５１５３２号公報及び特公昭６０−３１８５
７号公報等に示されている。特開昭５０−５１５３２号
公報には、ラインミキサーを用いた例が示されている。
この方法によれば、従来のバッチ式特有の問題点は解決
できるもののラインミキサーは、管路攪拌装置であるた
めフラッシングの連続化はできても、脱水操作は回分式
となり、ロール、加熱ロールで脱水を行っているもので
あり、完全な連続フラッシング方法とは言えないもので
あった。またラインミキサーは、流動物をその輸送ライ
ン中で連続的に攪拌混合するための装置であるため、流
動性を有することが必要であり、顔料水性湿潤ケーキを
特別に希釈調整すること、あるいは流動性を与えるため
に特別な添加剤、例えば活性剤の添加を余儀なくされる
ものであり、作業効率上及び製品の品質上において問題
を有するものであった。該ケーキは、通常顔料含有率１
５〜３５％の湿潤ケーキであり、顔料合成直後の水懸濁
液を濾過、水洗し、含有塩分等の除去精製する工程の
後、希釈調整することとなり生産効率上において問題と
なる。Regarding the continuous flushing method, Japanese Patent Application Laid-Open No. 50-51532 and Japanese Patent Publication No. 60-3185.
No. 7, for example. Japanese Patent Application Laid-Open No. 50-51532 discloses an example using a line mixer.
According to this method, although the problems peculiar to the conventional batch system can be solved, the line mixer is a pipe line stirring device, so continuous flushing can be performed, but the dehydration operation is a batch system, and rolls and heating rolls are used. It was dehydrated and could not be said to be a complete continuous flushing method. In addition, since the line mixer is a device for continuously stirring and mixing the fluid in the transportation line, it needs to have fluidity. In order to impart the property, it is necessary to add a special additive such as an activator, which causes a problem in work efficiency and product quality. The cake usually has a pigment content of 1
It is a wet cake of 5 to 35%, and after the steps of filtering and washing the water suspension immediately after the pigment synthesis to remove the salt content and the like for purification, the dilution is adjusted, which is a problem in terms of production efficiency.

【０００７】さらに特公昭６０−３１８５７号公報に
は、疎水性液状有機媒体と顔料水性湿潤ケーキとの定量
ずつを、Ｌ／Ｄ値が２５以上である２軸同方向回転スク
リュー押出機に供給し、相転換工程、脱水工程、必要に
応じて後処理工程を同一押出機内で連続的に行う方程が
開示されている。この方法によれば、顔料水性湿潤ケー
キは顔料合成直後の水懸濁液を濾過、水洗し、含有塩分
等の除去精製する必要があり、更にこのケーキを顔料含
有率が３５％以上で外観は乾燥顔料的形状となるよう
に、穏やかな条件下で乾燥調整工程が必要であり、生産
効率上及び製品の品質上において問題であった。Further, in Japanese Patent Publication No. 60-31857, a fixed amount of a hydrophobic liquid organic medium and a pigment aqueous wet cake are fed to a twin-screw co-rotating screw extruder having an L / D value of 25 or more. , A phase conversion step, a dehydration step, and a post-treatment step if necessary, are continuously performed in the same extruder. According to this method, it is necessary for the pigment aqueous wet cake to filter and wash the water suspension immediately after the pigment synthesis to remove the salt content, etc., and further purify this cake. In order to obtain a dry pigmentary form, a drying adjustment step is required under mild conditions, which is a problem in terms of production efficiency and product quality.

【０００８】一方、顔料合成直後の水懸濁液を用いたフ
ラッシング法に関しては、特公平５−６９１４７、特開
昭５３−１３４０３２、特公昭４９−８４９５の各号報
等に示されているが、これらは何れもバッチ方式の高速
攪拌装置を用いるもので連続方式では生産できない問題
点があった。On the other hand, the flushing method using an aqueous suspension immediately after the pigment synthesis is shown in Japanese Patent Publication No. 5-69147, Japanese Patent Publication No. 53-134032, Japanese Patent Publication No. 49-8495, and the like. However, all of them use a batch type high-speed agitator and cannot be produced by a continuous system.

【０００９】[0009]

【発明が解決しようとする課題】本発明は、前述したフ
ラッシング法の問題点を解決するために、顔料の水懸濁
液と油性ビヒクルとを、攪拌翼を有する流通型の攪拌装
置の内部に気相を形成させながら相転換方法を連続方式
とし、高顔料濃度の粒状着色組成物を連続的に生産する
方法を提供するものである。DISCLOSURE OF THE INVENTION In order to solve the above-mentioned problems of the flushing method, the present invention provides a pigment suspension in water and an oil vehicle inside a circulation type stirring device having stirring blades. It is intended to provide a method for continuously producing a granular coloring composition having a high pigment concentration by making a phase conversion method a continuous method while forming a gas phase.

【００１０】[0010]

【課題を解決するための手段】本発明は、顔料の水懸濁
液と油性ビヒクルとを、攪拌翼を有する流通型の攪拌装
置の内部に気相を形成させながら連続的に供給し、上記
攪拌翼を回転し水中の上記顔料を上記油性ビヒクル中に
相転換して粒状着色組成物を形成し、該粒状着色組成物
と水とを上記攪拌装置から連続的に取り出すことを特徴
とする粒状着色剤の連続製造方法である。更に本発明
は、攪拌装置内部の気相が容積率で２０〜８０％となる
ように形成させることを特徴とする上記製造方法であ
る。According to the present invention, an aqueous suspension of a pigment and an oily vehicle are continuously supplied to a flow-type stirring device having stirring blades while forming a gas phase, Granules characterized by continuously rotating the stirring blade to form a granular coloring composition by phase conversion of the pigment in water into the oil vehicle, and continuously extracting the granular coloring composition and water from the stirring device. It is a method for continuously producing a colorant. Furthermore, the present invention is the above-mentioned manufacturing method, characterized in that the gas phase inside the stirrer is formed so as to have a volume ratio of 20 to 80%.

【００１１】更に本発明は顔料の水懸濁液が顔料合成直
後の水懸濁液であることを特徴とする上記製造方法であ
る。更に本発明は粒状着色組成物が重量比で顔料：油性
ビヒクルが１：０．５〜３である上記製造方法である。Further, the present invention is the above-mentioned production method, wherein the water suspension of the pigment is a water suspension immediately after the pigment synthesis. Further, the present invention is the above production method, wherein the weight ratio of the granular coloring composition is 1: 0.5 to 3 of pigment: oil vehicle.

【００１２】[0012]

【発明の実施の形態】本発明の粒状着色組成物の製造方
法は、原料となる顔料の水懸濁液と油性ビヒクルと気相
の３者の比率、攪拌装置内原料充填率及び攪拌翼の回転
速度及び原料の装置内滞留時間が極めて重要となる。即
ち装置内原料充填率を下げると生産効率が低下し好まし
くないが、充填率を上げると顔料の水懸濁液及び油性ビ
ヒクルは攪拌翼と共に攪拌装置ベッセル内の内周に沿っ
て回ってしまうため攪拌効率が低下する。即ち相転換に
かかる時間が長くなってしまい生産効率が低下する。従
って相転換後良好な粒状着色組成物を得るためには、攪
拌装置内部の気相が容積率で２０〜８０％となるように
充填率を決定し、さらには攪拌翼の攪拌速度を適切な値
に合わせる必要がある。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a granular coloring composition of the present invention comprises a three-part ratio of an aqueous suspension of a pigment as a raw material, an oily vehicle and a gas phase, a raw material filling rate in a stirrer and a stirring blade. The rotation speed and the residence time of the raw material in the apparatus are extremely important. That is, if the filling rate of the raw material in the apparatus is lowered, the production efficiency is lowered, which is not preferable, but if the filling rate is increased, the water suspension of the pigment and the oily vehicle will be rotated along with the stirring blade along the inner circumference of the vessel of the stirring apparatus. Stirring efficiency decreases. That is, the time required for the phase conversion becomes long and the production efficiency is reduced. Therefore, in order to obtain a good granular colored composition after phase conversion, the filling rate is determined so that the gas phase inside the stirring device has a volume ratio of 20 to 80%, and the stirring speed of the stirring blade is set to an appropriate value. Must be adjusted to the value.

【００１３】顔料の水懸濁液の顔料濃度については合成
された濃度のままのものが使用できる。このときの顔料
濃度は１〜２０重量％で良好に相転換した粒状着色組成
物が得られる。顔料の水懸濁液の顔料濃度が１重量％未
満であると相転換までの時間が長くなるため生産性が悪
くなるとともに、相転換の所要エネルギーも大きくな
る。一方、２０重量％を超えると顔料の水懸濁液の粘度
が高く、相転換の所要エネルギーが大きくなり、また攪
拌装置の能力も大きくなるため消費電力もかかる。With respect to the pigment concentration of the aqueous suspension of pigment, it is possible to use the pigment having the same synthetic concentration. At this time, the pigment concentration is 1 to 20% by weight, and a finely colored granular coloring composition can be obtained. If the pigment concentration of the aqueous pigment suspension is less than 1% by weight, the time required for phase conversion becomes long, resulting in poor productivity and a large amount of energy required for phase conversion. On the other hand, when it exceeds 20% by weight, the viscosity of the aqueous suspension of the pigment is high, the energy required for the phase conversion is large, and the capacity of the stirrer is large, so that power consumption is also required.

【００１４】本発明は、合成直後の水懸濁液を相転換し
て粒状着色組成物を形成させることで、従来フィルター
プレス等の過大な濾過機により行われていた水懸濁液の
含有塩分等の除去精製工程を簡便化し短縮できる。すな
わち、相転換と同時に塩分等を含む水相が分離でき含有
塩分が除去でき、粒状であるため濾過性が向上し精製工
程が短縮できる。本発明に関わる顔料は、特に制限はな
く、具体例としてアゾ、フタロシアニン、キナクリド
ン、イソインドリノン、ジオキサジン、スレン、チオイ
ンジゴ、アントラキノン、ペリノン、ジケトロピロール
等が挙げられる。According to the present invention, the water suspension immediately after the synthesis is phase-converted to form a granular coloring composition, so that the salt content of the water suspension which has been conventionally carried out by an excessive filter such as a filter press. It is possible to simplify and shorten the removal and purification process such as. That is, the aqueous phase containing salt and the like can be separated at the same time as the phase inversion, and the salt content can be removed. The pigment relating to the present invention is not particularly limited, and specific examples thereof include azo, phthalocyanine, quinacridone, isoindolinone, dioxazine, threne, thioindigo, anthraquinone, perinone and diketropyrrole.

【００１５】本発明に関わる油性ビヒクルについては、
得られた粒状着色組成物が印刷インキとして汎用性とな
るような樹脂等を使用するのが好ましい。即ち、粒状着
色組成物からさらに高濃度顔料分散体を得るに際し、種
々の印刷インキ等の油性ビヒクルと混合できるものが好
ましい。また、さらには最終の印刷インキ、塗料とする
に際し、種々の油性ビヒクルと混合できることが望まし
い。本発明の油性ビヒクルは樹脂、油及び溶剤を含む。
樹脂としては、例えばポリエステル樹脂、アルキッド樹
脂、石油樹脂、フェノール樹脂、ロジン変性フェノール
樹脂、エポキシ樹脂、ケトン樹脂、ロジン、ロジン誘導
体、ロジン変性マレイン酸樹脂等が挙げられる。乾性油
としては大豆油、桐油、アマニ油等があり、これらの乾
性油を変性したものでも良い。勿論半乾性油または不乾
性油も使用することができる。溶剤としてはノルマルパ
ラフィン、イソパラフィン、ナフテン（シクロパラフィ
ン）、α−オレフィン、その他の脂肪族炭化水素等の有
機溶剤がある。溶剤としては沸点２００℃以上の高沸点
溶剤が好ましい。油性ビヒクルの組成としては、全油性
ビヒクルを基準として重量比（重量％）で樹脂／油／溶
剤として１０〜５０／０〜６０／１０〜７０である。こ
のときの油性ビヒクルの粘度は常温（２５℃、Ｂ型粘度
計）で１〜１０００ポイズである。さらに必要に応じて
従来公知の顔料分散剤、乾燥抑制剤等の添加物も使用で
きる。Regarding the oil vehicle related to the present invention,
It is preferable to use a resin or the like that makes the obtained granular coloring composition versatile as a printing ink. That is, in obtaining a higher concentration pigment dispersion from the granular coloring composition, those which can be mixed with an oil vehicle such as various printing inks are preferable. Further, it is desirable that various oily vehicles can be mixed in the final printing ink or paint. The oil vehicle of the present invention comprises a resin, an oil and a solvent.
Examples of the resin include polyester resin, alkyd resin, petroleum resin, phenol resin, rosin-modified phenol resin, epoxy resin, ketone resin, rosin, rosin derivative, and rosin-modified maleic acid resin. Examples of the drying oil include soybean oil, tung oil, linseed oil and the like, and these drying oils may be modified. Of course semi-drying or non-drying oils can also be used. Examples of the solvent include organic solvents such as normal paraffin, isoparaffin, naphthene (cycloparaffin), α-olefin, and other aliphatic hydrocarbons. As the solvent, a high boiling point solvent having a boiling point of 200 ° C. or higher is preferable. The composition of the oil vehicle is from 10 to 50/0 to 60/10 to 70 as resin / oil / solvent in a weight ratio (% by weight) based on the total oil vehicle. The viscosity of the oily vehicle at this time is 1 to 1000 poises at room temperature (25 ° C., B-type viscometer). Further, if necessary, conventionally known additives such as a pigment dispersant and a drying inhibitor can be used.

【００１６】装置に供給する顔料の水懸濁液中の顔料分
と油性ビヒクルの重量比については、汎用性をもたせる
場合にはできるだけ顔料分を多くすることが好ましい
が、顔料比率を多くすると相転換の効率が悪くなるた
め、必要な攪拌翼回転数の増加による消費動力の増加、
または滞留時間の延長により生産効率が低下する。また
油性ビヒクル比率を多くすると相転換の効率が向上する
が、多すぎると相転換した粒子状着色組成物同志が付着
し最後には攪拌翼に絡みついてしまう。重量比で顔料：
油性ビヒクル＝１：０．５〜３の範囲で可能であるが、
好ましくは１：０．６〜２である。本発明で得られる粒
状着色剤の平均粒径は１５〜１００μｍ、好ましくは２
０〜７５μｍである。Regarding the weight ratio of the pigment content in the water suspension of the pigment supplied to the apparatus and the oil vehicle, it is preferable to increase the pigment content as much as possible in order to provide versatility. Since the efficiency of conversion becomes poor, the power consumption increases due to the increase in the required stirring blade rotation speed,
Alternatively, the extension of the residence time reduces the production efficiency. If the oil vehicle ratio is increased, the phase conversion efficiency is improved, but if the oil vehicle ratio is too high, the phase-converted particulate coloring compositions adhere to each other and finally get entangled with the stirring blade. Pigments by weight ratio:
Oil vehicle = 1: It is possible in the range of 0.5 to 3,
It is preferably 1: 0.6 to 2. The average particle size of the granular colorant obtained in the present invention is 15 to 100 μm, preferably 2
It is 0 to 75 μm.

【００１７】相転換を行う温度としては１０〜８０℃で
行う。相転換に要する時間は高温の方が短いが、耐熱性
の弱い有機顔料に関しては３０〜５０℃にて行うことが
好ましい。攪拌翼の回転数に関しては翼形状により必要
な回転数は異なるが、相転換に必要なせん断力を与える
回転数以上で行うことが不可欠である。回転数が大きい
程相転換に要する時間が短くなるが、後工程の処理や最
終製品である印刷インキの品質に問題が出てくることも
あるため適度な回転数が好ましい。攪拌翼はその一部が
攪拌装置内部に形成された気相領域を通過するように回
転させることが好ましい。The temperature at which the phase conversion is carried out is 10 to 80 ° C. Although the time required for phase conversion is shorter at high temperature, it is preferable to carry out at 30 to 50 ° C. for organic pigments having weak heat resistance. Regarding the rotational speed of the stirring blade, the required rotational speed varies depending on the blade shape, but it is essential to perform the rotational speed above the rotational speed that gives the shearing force necessary for phase conversion. The higher the number of rotations, the shorter the time required for phase conversion, but there is a problem in the quality of the printing ink as a final process and the final product, so an appropriate number of rotations is preferable. The stirring blade is preferably rotated so that a part thereof passes through a gas phase region formed inside the stirring device.

【００１８】原料の攪拌装置内に於ける滞留時間に関し
ては、相転換を行う温度、攪拌翼の回転速度、顔料と油
性ビヒクルの重量比、顔料の組成等により異なる。滞留
時間が短いと、相転換が不完全で空気を抱き込んだ顔料
の水懸濁液と油性ビヒクルの混合物が排出され、これを
デカントしその後脱水したものを用いて印刷インキを製
造してもインキの物性が非常に悪くなり実用的ではな
い。以下本発明の製造方法を図面を用いて説明する。図
１及び図３に本発明に使用した攪拌装置の断面図を示
す。図１に於いて攪拌装置は水平な（横置きした）円筒
形の容器と攪拌翼及びそれを回転させるためのモーター
から成る。攪拌翼は軸の回転方向と軸方向にピンが配置
されている。図３では、図１に於けるピンを有する攪拌
翼に変えてコーン状のディスクを配して行ったものであ
る。円筒容器はジャケットがついており恒温水を流すこ
とにより温度コントロールができるようになっている。
攪拌装置内部の温度は１０〜８０℃にコントロールされ
る。上記円筒形の容器中には全容積の２０〜８０％の原
料が満たされ、残りの部分が気相になるようにする。こ
の状態で攪拌翼を回転することにより攪拌時には空気の
巻き込みを伴う。この空気の巻き込みを伴う攪拌によ
り、容器中全てが原料で満たされた場合と比較して攪拌
効率が上がり相転換が速やかに進行する。原料である顔
料の水懸濁液と油性ビヒクルは原料タンクよりポンプを
介し図中左上部の供給口よりそれぞれ定量供給される。
容器内に供給された顔料の水懸濁液の顔料は攪拌翼の回
転により混合され出口に近くなるに従い相転換される。
相転換された顔料と油性ビヒクルは図中右側の出口より
粒状着色組成物として排出される。図中右側の出口より
排出された生成物は、この後濾過、精製及び乾燥工程を
経た後粒状着色組成物として得られる。The residence time of the raw material in the stirrer varies depending on the temperature at which the phase is changed, the rotation speed of the stirring blade, the weight ratio of the pigment to the oily vehicle, the composition of the pigment, and the like. If the residence time is short, a mixture of an aqueous suspension of pigment and an oily vehicle, which has incomplete phase conversion and entraps air, is discharged, and decanted and then dehydrated to produce a printing ink. The physical properties of the ink are so bad that it is not practical. The manufacturing method of the present invention will be described below with reference to the drawings. 1 and 3 are cross-sectional views of the stirrer used in the present invention. In FIG. 1, the stirring device comprises a horizontal (horizontal) cylindrical container, a stirring blade, and a motor for rotating the stirring blade. The stirring blade has pins arranged in the rotational direction of the shaft and in the axial direction. In FIG. 3, a cone-shaped disk is arranged instead of the stirring blade having the pin in FIG. The cylindrical container has a jacket so that the temperature can be controlled by flowing constant temperature water.
The temperature inside the stirrer is controlled at 10 to 80 ° C. The cylindrical container is filled with 20 to 80% of the total volume of the raw material, and the remaining portion is in the vapor phase. By rotating the stirring blade in this state, air is entrained during stirring. By the stirring accompanied by the entrainment of air, the stirring efficiency is improved and the phase conversion proceeds promptly as compared with the case where the entire container is filled with the raw material. The water suspension of the pigment, which is the raw material, and the oily vehicle are quantitatively supplied from the raw material tank through the pump through the supply ports at the upper left part of the figure.
The pigment in the aqueous suspension of the pigment supplied into the container is mixed by the rotation of the stirring blade and undergoes phase conversion as it approaches the outlet.
The phase-converted pigment and the oily vehicle are discharged as a granular coloring composition from the outlet on the right side in the figure. The product discharged from the outlet on the right side of the figure is obtained as a granular coloring composition after the subsequent filtration, purification and drying steps.

【００１９】[0019]

【実施例】実施例１ 図１に記載した装置（円筒容器の内径１１０ｃｍ、攪拌
翼経１００ｃｍ）を用い、顔料の水懸濁液として未精製
の不溶性アゾ顔料（Ｙｅｌｌｏｗ．１２）の４重量％
液、油性ビヒクルとしてロジン変性フェノール樹脂／ア
マニ油／石油系高沸点溶剤（日本石油（株）製０号ソル
ベントＨ）（３０／５／６５重量％）の組成で粘度１０
ポイズ（２５℃、Ｂ型粘度計）のものを用いた。重量比
で顔料の水懸濁液中の顔料と油性ビヒクルが１：１で、
かつ装置内平均滞留時間（装置容積÷流量）が約１０分
となるように攪拌装置に顔料の水懸濁液１９２．３ｇ／
分、油性ビヒクル７．７ｇ／分の割合（重量比で顔料：
油性ビヒクル＝１：１）で２台のポンプで定量的に供給
した。攪拌装置の攪拌翼は１０００回転／分で回転し、
攪拌装置内部の温度はジャケットに恒温水を流すことに
より４０℃に保った。攪拌装置内充填率を約５０％と
し、顔料濃度５０重量％の粒状着色組成物を含む液が得
られた。この粒状着色組成物をレーザー回折式の粒度分
布測定装置で計測したところ平均粒径は３４μｍであっ
た。この得られた粒状着色組成物を含む液を濾過、精製
し箱型乾燥機にて４０℃、２４時間乾燥し粒状着色組成
物を得た。これに印刷インキ用油性ビヒクルと補助剤等
を添加し３本ロールを用いて分散し、顔料濃度７％の印
刷用インキを得た。得られたインキの分散度（グライン
ドメーター リーディング、以下ＧＲと記す）は２．５
（６．２５μｍ）であり、またその他の色相、乳化適性
などのインキ性状も従来のフラッシング法から得られた
印刷インキのそれと同等であった。Example 1 Using the apparatus described in FIG. 1 (inside diameter of cylindrical container 110 cm, stirring blade 100 cm), 4% by weight of crude insoluble azo pigment (Yellow. 12) was prepared as an aqueous suspension of pigment.
As a liquid or oily vehicle, a composition of rosin-modified phenolic resin / linseed oil / petroleum-based high-boiling solvent (No. 0 solvent H manufactured by Nippon Oil Co., Ltd.) (30/5/65% by weight) has a viscosity of 10
A poise (25 ° C., B-type viscometer) was used. 1: 1 pigment-oil vehicle in water suspension of pigment by weight ratio,
In addition, a pigment aqueous suspension of 192.3 g / is added to the stirring device so that the average residence time in the device (device volume / flow rate) is about 10 minutes.
Min, oil vehicle 7.7 g / min (pigment weight ratio:
Oily vehicle = 1: 1) was quantitatively supplied by two pumps. The stirring blade of the stirring device rotates at 1000 rpm,
The temperature inside the stirrer was kept at 40 ° C. by flowing constant temperature water through the jacket. The filling rate in the stirrer was set to about 50%, and a liquid containing the granular coloring composition having a pigment concentration of 50% by weight was obtained. When this granular colored composition was measured with a laser diffraction type particle size distribution measuring device, the average particle size was 34 μm. The liquid containing the obtained granular coloring composition was filtered, purified, and dried in a box dryer at 40 ° C. for 24 hours to obtain a granular coloring composition. An oily vehicle for printing ink, an auxiliary agent and the like were added thereto and dispersed using a three-roll mill to obtain a printing ink having a pigment concentration of 7%. The degree of dispersion of the obtained ink (grindometer reading, hereinafter referred to as GR) is 2.5.
(6.25 μm), and other ink properties such as hue and emulsification suitability were similar to those of the printing ink obtained by the conventional flushing method.

【００２０】実施例２ 実施例１に於いて重量比で顔料：油性ビヒクル＝１：
０．８となるように供給した他は全く同様にして顔料濃
度５５．６重量％の粒状着色組成物を含む液を得た。実
施例１と同様に得られた印刷インキの物性は従来のフラ
ッシング法から得られた印刷インキのそれと同等であっ
た。 実施例３ 実施例１に於いて攪拌装置の攪拌翼回転数を８００回転
／分とし、顔料の水懸濁液中の顔料と油性ビヒクルが
１：１でかつ装置内平均滞留時間が約１５分となるよう
に攪拌装置に前者１２８．２ｇ／分、後者５．１ｇ／分
の割合で２台のポンプで定量的に供給した。それ以外は
全く同様にして実施した結果、顔料濃度５０重量％の粒
状着色組成物を含む液を得た。実施例１と同様に得られ
た印刷インキの物性は従来のフラッシング法から得られ
た印刷インキのそれと同等であった。Example 2 Pigment: oil vehicle = 1: 1 in weight ratio in Example 1.
A liquid containing the granular coloring composition having a pigment concentration of 55.6% by weight was obtained in exactly the same manner except that the amount was supplied so as to be 0.8. The physical properties of the printing ink obtained in the same manner as in Example 1 were similar to those of the printing ink obtained by the conventional flushing method. Example 3 The stirring blade rotation speed of the stirring apparatus in Example 1 was 800 rpm, the pigment and oil vehicle in the pigment aqueous suspension were 1: 1 and the average residence time in the apparatus was about 15 minutes. In such a manner, the former was supplied quantitatively at a rate of 128.2 g / min and the latter at a rate of 5.1 g / min by two pumps. Other than that was carried out in exactly the same manner to obtain a liquid containing the granular coloring composition having a pigment concentration of 50% by weight. The physical properties of the printing ink obtained in the same manner as in Example 1 were similar to those of the printing ink obtained by the conventional flushing method.

【００２１】実施例４ 第２図に記載した装置を用い、顔料の水懸濁液として未
精製のアゾレーキ顔料（カーミン６Ｂ）の４重量％液、
油性ビヒクルとして、ロジン変性フェノール樹脂／アマ
ニ油／石油系高沸点溶剤（日本石油（株）製０号ソルベ
ントＨ）（３０／５／６５重量％）の組成で粘度１２ポ
イズ（２５℃、Ｂ型粘度計）のものを用いた。重量比で
顔料の水懸濁液中の顔料と油性ビヒクルが１：１で、か
つ装置内平均滞留時間が約１５分となるように攪拌装置
に顔料の水懸濁液１２８．２ｇ／分、油性ビヒクル５．
１ｇ／分の割合（重量比で顔料：油性ビヒクル＝１：
１）で２台のポンプで定量的に供給した。攪拌装置の攪
拌翼は１２００回転／分で回転し、攪拌装置内部の温度
はジャケットに恒温水を流すことにより８０℃に保っ
た。顔料の水懸濁液と油性ビヒクルの攪拌装置内充填率
を約６０％とし、顔料濃度５０重量％の粒状着色組成物
を含む液が得られた。この粒状着色組成物をレーザー回
折式の粒度分布測定装置で計測したところ平均粒径は２
５μｍであった。この得られた粒状着色組成物を含む液
を濾過、精製し箱型乾燥機にて４０℃、２４時間乾燥し
粒状着色組成物を得た。これに印刷インキ用油性ビヒク
ルと補助剤等を添加し３本ロールを用いて分散し、顔料
濃度１０％の印刷用インキを得た。得られたインキのＧ
Ｒは２．０（５．０μｍ）であり、またその他の色相、
乳化適性などのインキ性状も従来のフラッシング法から
得られた印刷インキのそれと同等であった。 比較例１ 実施例１に於いて、排出口を円筒容器上部に設け、顔料
の水懸濁液と油性ビヒクルの装置内充填率をほぼ１００
％となるようにした。顔料と油性ビヒクルの比率は変え
ずに流量を調整し、滞留時間を延長することで滞留時間
を最大３０分としたが、攪拌効率が著しく低下してお
り、相転換は起こらず、空気を抱き込んだ顔料の水懸濁
液と油性ビヒクルの混合物が出口から排出され粒状着色
組成物は得られなかった。Example 4 Using the apparatus described in FIG. 2, a 4% by weight solution of an unpurified azo lake pigment (Carmine 6B) as an aqueous suspension of pigment,
As an oily vehicle, a composition of rosin-modified phenolic resin / linseed oil / petroleum-based high-boiling solvent (No. 0 solvent H manufactured by Nippon Oil Co., Ltd.) (30/5/65% by weight) and a viscosity of 12 poise (25 ° C., B type) A viscometer) was used. 128.2 g / min of the pigment aqueous suspension in the stirring device such that the pigment and the oily vehicle in the pigment aqueous suspension are 1: 1 by weight and the average residence time in the device is about 15 minutes. Oily vehicle 5.
Percentage of 1 g / min (by weight: pigment: oil vehicle = 1:
In 1), two pumps quantitatively supplied. The stirring blade of the stirrer was rotated at 1200 rpm, and the temperature inside the stirrer was kept at 80 ° C. by flowing constant temperature water through the jacket. A liquid containing the granular coloring composition having a pigment concentration of 50% by weight was obtained by setting the filling rate of the aqueous suspension of the pigment and the oily vehicle in the stirrer to be about 60%. When this granular colored composition was measured with a laser diffraction type particle size distribution measuring device, the average particle size was 2
It was 5 μm. The liquid containing the obtained granular coloring composition was filtered, purified, and dried in a box dryer at 40 ° C. for 24 hours to obtain a granular coloring composition. An oily vehicle for printing ink, an auxiliary agent and the like were added thereto and dispersed using a three-roll mill to obtain a printing ink having a pigment concentration of 10%. G of the obtained ink
R is 2.0 (5.0 μm), and other hues,
Ink properties such as emulsification suitability were similar to those of the printing ink obtained from the conventional flushing method. Comparative Example 1 In Example 1, the discharge port was provided in the upper part of the cylindrical container, and the filling ratio of the water suspension of pigment and the oil vehicle in the apparatus was about 100.
It became to be%. The retention time was set to a maximum of 30 minutes by adjusting the flow rate and extending the retention time without changing the ratio of the pigment and the oily vehicle, but the stirring efficiency was remarkably reduced, and phase conversion did not occur, and air was retained. A mixture of the aqueous suspension of the incorporated pigment and the oily vehicle was discharged from the outlet, and no granular coloring composition was obtained.

【００２２】各実施例における条件および結果のまとめ
て表１に示した。The conditions and results of each example are summarized in Table 1.

【００２３】[0023]

【表１】 [Table 1]

【図面の簡単な説明】[Brief description of drawings]

【図１】攪拌装置の断面図FIG. 1 is a sectional view of a stirring device.

【図２】図１の攪拌装置の攪拌翼の正面断面図FIG. 2 is a front sectional view of a stirring blade of the stirring device of FIG.

【図３】別の攪拌装置の断面図FIG. 3 is a sectional view of another stirring device.

【図４】図３の攪拌装置の攪拌翼の正面断面図FIG. 4 is a front sectional view of a stirring blade of the stirring device shown in FIG.

【符号の説明】[Explanation of symbols]

１ ステーター ２ 攪拌翼軸 ３ 攪拌翼 ４ モーター ５ 顔料の水懸濁液用貯蔵タンク ６ 油性ビヒクル用貯蔵タンク ７ 顔料の水懸濁液用ポンプ ８ 油性ビヒクル用ポンプ ９ ジャケット １０ 原料入口 １１ 循環恒温水入口 １２ 排出口 １３ 循環恒温水出口 1 stator 2 stirring impeller 3 stirring blades 4 motor 5 Storage tank for pigment water suspension Storage tank for 6 oily vehicles 7 Pigment water suspension pump 8 Oil vehicle pump 9 jacket 10 Raw material inlet 11 Circulating constant temperature water inlet 12 outlet 13 Circulating constant temperature water outlet

フロントページの続き (72)発明者 巣鴨 等 東京都中央区京橋二丁目３番13号 東洋 インキ製造株式会社内 (56)参考文献 特開 平２−175770（ＪＰ，Ａ) (58)調査した分野(Int.Cl.⁷，ＤＢ名) C08J 3/20 Front Page Continuation (72) Inventor Sugamo et al. 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Mfg. Co., Ltd. (56) Reference JP-A-2-175770 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/20

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】顔料の水懸濁液と油性ビヒクルとを、攪拌
翼を有する流通型の攪拌装置の内部に気相を形成させな
がら連続的に供給し、上記攪拌翼を回転し水中の上記顔
料を上記油性ビヒクル中に相転換して粒状着色組成物を
形成し、該粒状着色組成物と水とを上記攪拌装置から連
続的に取り出すことを特徴とする粒状着色組成物の連続
製造方法。1. An aqueous suspension of a pigment and an oily vehicle are continuously fed into a flow-type stirring apparatus having a stirring blade while forming a gas phase, and the stirring blade is rotated to make the above-mentioned submersion in water. A method for continuously producing a granular coloring composition, which comprises phase-converting a pigment into the oil vehicle to form a granular coloring composition, and continuously removing the granular coloring composition and water from the stirring device. 【請求項２】攪拌装置内部の気相が容積率で２０〜８０
％となるように形成させることを特徴とする請求項１記
載の製造方法。2. The gas phase inside the stirrer has a volume ratio of 20 to 80.
The manufacturing method according to claim 1, characterized in that it is formed so as to be%. 【請求項３】顔料合成直後の水懸濁液であることを特徴
とする請求項１または２記載の製造方法。3. The method according to claim 1, which is an aqueous suspension immediately after the pigment synthesis. 【請求項４】粒状着色組成物が重量比で顔料：油性ビヒ
クルが１：０．５〜３である請求項１ないし３何れか記
載の製造方法。4. The method according to any one of claims 1 to 3, wherein the weight ratio of the granular coloring composition is 1: 0.5 to 3: pigment: oil vehicle.