JPS62153364A - Particulate coloring material for lithographic ink and pigment concentrate obtained by using same - Google Patents
Particulate coloring material for lithographic ink and pigment concentrate obtained by using sameInfo
- Publication number
- JPS62153364A JPS62153364A JP60292483A JP29248385A JPS62153364A JP S62153364 A JPS62153364 A JP S62153364A JP 60292483 A JP60292483 A JP 60292483A JP 29248385 A JP29248385 A JP 29248385A JP S62153364 A JPS62153364 A JP S62153364A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- lithographic ink
- varnish
- ink
- oil
- 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
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
「発明の目的」
（産業上の利用分野）
本発明は有機顔料および樹脂、さらには乾性油およびま
たは高沸点溶剤を含み、顔料濃度３０〜７０重量％、平
均粒径２ｍｍ以下の平版インキ用粒状着色剤に関し、ま
た顔料の水性懸濁液と油性ワニスとからブラッシング方
法により得られる平均粒径２ｍｍ以下で、顔料濃度３０
〜７０重量％の平版インキ用粒状着色剤およびこれを用
いた顔料濃縮物に関する。Detailed Description of the Invention "Object of the Invention" (Industrial Field of Application) The present invention comprises an organic pigment and a resin, as well as a drying oil and/or a high boiling point solvent, with a pigment concentration of 30-70% by weight and an average particle size. Regarding granular colorants for lithographic inks of 2 mm or less, and with an average particle size of 2 mm or less obtained by a brushing method from an aqueous suspension of pigment and an oil-based varnish, and a pigment concentration of 30
-70% by weight of a granular colorant for lithographic ink and a pigment concentrate using the same.
（従来の技術）
従来、印刷インキ等を製造するには、ワニス、樹脂等の
有機媒体中に顔料を十分分散させることにより、顔料の
着色効果を高めることが要求される。顔料の分散方法に
は、乾燥顔料を有機媒体中で練肉する方法と、顔料の水
性懸濁液から水分を一部除去し、顔料濃度２５〜４５重
量％としてなる水性ペーストおよび油性ワニスをフラッ
シャ−に仕込み、顔料を水相から油性相に転相した後、
水をデカンテーションによって除去するフラッシング法
と、が知られている。(Prior Art) Conventionally, in order to manufacture printing inks and the like, it is required to enhance the coloring effect of the pigment by sufficiently dispersing the pigment in an organic medium such as varnish or resin. Pigment dispersion methods include kneading dry pigments in an organic medium, and flashing an aqueous paste and oil-based varnish by removing part of the water from an aqueous pigment suspension to obtain a pigment concentration of 25 to 45% by weight. - After inverting the phase of the pigment from the aqueous phase to the oily phase,
A flushing method in which water is removed by decantation is known.
乾燥顔料を使用する方法では、顔料がその乾燥工程中に
強い凝集を生じ、その後の有機媒体との強力な練肉工程
によっても十分微細で均一な状態にまでさせることは難
しい。一方、フラッシング法は顔料の乾燥工程を経ない
ため、顔料分散体の顔料粒子は均一微細であり２着色力
９色相、透明性等の着色効果において優れた製品が得ら
れる。In the method using dried pigments, the pigments undergo strong agglomeration during the drying process, and it is difficult to make them into a sufficiently fine and uniform state even by a subsequent intensive grinding process with an organic medium. On the other hand, since the flushing method does not involve a pigment drying process, the pigment particles of the pigment dispersion are uniform and fine, and a product with excellent coloring effects such as 2 coloring power 9 hue and transparency can be obtained.
しかしながら、フラッシング法では、フラッシングさせ
る顔料として顔料濃度を高めた水性ペーストを用いるこ
とが必要であり、有機顔料の水性懸濁液を用いることは
難しい。すなわち１合成された顔料の水性懸濁液をフィ
ルタープレス等により、水分を減少させた水性ペースト
を使用する。However, in the flushing method, it is necessary to use an aqueous paste with a high pigment concentration as the pigment to be flushed, and it is difficult to use an aqueous suspension of an organic pigment. That is, an aqueous paste is used, which is obtained by reducing the water content of an aqueous suspension of the synthesized pigment using a filter press or the like.
さらに従来のフラッシング法で得られた顔料分散体（液
状または半液状）は、顔料濃度の高いものは作りに＜＜
、またハンドリング性も顔料濃度を高めると悪ろくなる
。Furthermore, pigment dispersions (liquid or semi-liquid) obtained by conventional flushing methods have a high pigment concentration.
Moreover, the handling property becomes worse as the pigment concentration increases.
従来のフラッシング法では、乾燥工程を経ることな（顔
料分散体が得られるため、顔料の凝集という問題はない
が、フラッシングさせた後、そのまま印刷インキの製造
に使用されるため、フラッシング時のワニスおよび最終
製品となるワニスとの組み合わせ等から、印刷インキの
種類として一般に何でもよいというわけにはいかない。In the conventional flushing method, there is no drying process (because a pigment dispersion is obtained, there is no problem of pigment agglomeration). In general, any type of printing ink cannot be used because of the combination with the varnish that becomes the final product, etc.
つまり、汎用性があるとは言い難い。In other words, it is hard to say that it is versatile.
さらに、特公昭３６−２０２１５号公報には、フラッシ
ングした後、乾燥する方法が示されている。Furthermore, Japanese Patent Publication No. 36-20215 discloses a method of drying after flushing.
しかし、ここに示されている方法は、顔料の水性ペース
トを使用したり、またはフラッシング前に顔料に添加剤
を添加する方法である。しかも、フラッシングし、乾燥
後、チップ、フレーク等に成形するものであり、かなり
大きな平均粒径を有するものである。However, the method shown here is to use an aqueous paste of the pigment or to add additives to the pigment before flushing. Moreover, after flashing and drying, it is formed into chips, flakes, etc., and has a fairly large average particle size.
また、特公昭４９−８４９５号、特公昭６０−３５３７
５号、特開昭５３−１３４０３２号公報には、予め添加
剤を添加した後、フラッシングする方法、あるいは高速
攪拌機を使用する方法、が示されている。界面活性剤等
の添加剤を添加することは、フラッシング工程には有利
に働くことはあるかもしれないが、得られた着色剤とし
ては添加剤が、一般にかなり添加されており１例えばオ
フセットインキに使用した場合、オフセット適正で問題
となり、汎用性がない。Also, Special Publication No. 49-8495, Special Publication No. 60-3537
No. 5, JP-A-53-134032 discloses a method in which additives are added in advance and then flushed, or a method in which a high-speed stirrer is used. Adding additives such as surfactants may have an advantageous effect on the flushing process, but the resulting colorants generally contain a significant amount of additives1, for example in offset inks. When used, there is a problem with proper offset, and there is no versatility.
また、平版インキにおいて、顔料濃度が比較的高い濃度
のペースト状のベースインキを作成し、該ベースインキ
にワニスを混合し、希釈して最終の平版インキを製造し
ている。しかしながら、ペースト状のため、ハンドリン
グが悪く、印刷適性のある高濃度のベースインキを得る
ことが難しく、従って希釈能力の高い、すなわちベース
インキの顔料濃度が高く、添加する平版インキ用ワニス
の配合比率の高いものを得ることが難しい。ひいては汎
用性、多目的に使用できるベースインキは存在しない。Furthermore, in the case of lithographic ink, a paste-like base ink having a relatively high pigment concentration is prepared, and a varnish is mixed with the base ink and diluted to produce the final lithographic ink. However, because it is paste-like, it is difficult to handle and it is difficult to obtain a high-concentration base ink suitable for printing. It is difficult to obtain a high value. Furthermore, there is no base ink that is versatile and can be used for multiple purposes.
（発明が解決しようとする問題点）
顔料の凝集が少なく、かつ汎用性の高い着色剤であり、
しかも製造方法において、工程が簡略化された着色剤が
望まれていた。さらに、汎用性に関し。(Problems to be solved by the invention) A highly versatile coloring agent with less pigment aggregation,
Furthermore, there has been a desire for a colorant that has a simplified manufacturing process. Furthermore, regarding versatility.
着色剤として種々の平版インキへの展開が可能であるこ
とは勿論１着色剤として顔料濃度が高く９種々の濃度に
希釈することができることが望ましい。It is desirable that the pigment can be used as a coloring agent in various lithographic inks, and that it can be diluted to various concentrations with a high pigment concentration as a single colorant.
「発明の構成」
（問題点を解決するための手段）
本発明は、有機顔料および樹脂、さらには乾性油および
または高沸点溶剤を含み、有機顔料の濃度３０〜７０重
量％、平均粒径２ｍｍ以下の平版インキ用粒状着色剤で
あり、また顔料濃度３０重量％以下の有機顔料の水性懸
濁液を、実質的に予め添加剤を加えることなく、油性ワ
ニスと混合し、フラッシングせしめ、単離してなる顔料
濃度３０〜７０重量％、平均粒径２ｍｍ以下である平版
インキ用粒状着色剤であり、さらには顔料濃度５〜２５
重量％の有機顔料の水性懸濁液を使用する。または温度
５０〜７０°Ｃでフラッシングしてなる平版インキ用粒
状着色剤である。"Structure of the Invention" (Means for Solving the Problems) The present invention comprises an organic pigment and a resin, and further includes a drying oil and/or a high boiling point solvent, the concentration of the organic pigment is 30 to 70% by weight, and the average particle size is 2 mm. The following particulate coloring agent for lithographic ink is prepared by mixing an aqueous suspension of an organic pigment with a pigment concentration of 30% by weight or less with an oil-based varnish, flashing it, and isolating it. It is a granular colorant for lithographic ink having a pigment concentration of 30 to 70% by weight and an average particle size of 2 mm or less, and furthermore, a pigment concentration of 5 to 25%.
An aqueous suspension of % by weight organic pigment is used. Alternatively, it is a granular coloring agent for lithographic ink which is obtained by flashing at a temperature of 50 to 70°C.
本発明の平版インキ用粒状着色剤としては、樹脂を含み
、さらに乾性油、高沸点溶剤、水等を含む。The granular colorant for lithographic ink of the present invention contains a resin, and further contains a drying oil, a high boiling point solvent, water, and the like.
ただし水分は２０重量％程度以下であり、最終の平版イ
ンキとする。または顔料濃縮物とするに際しては、水分
は通常２重量％以下とする。However, the water content is about 20% by weight or less, and the final lithographic ink is used. Alternatively, when preparing a pigment concentrate, the water content is usually 2% by weight or less.
また、上記平版インキ用粒状着色剤をワニスに。In addition, the above granular colorant for lithographic ink can be used in varnish.
顔料濃度１５〜５０重量％となるよう添加してなる平版
インキの着色に適した顔料濃縮物に関する。The present invention relates to a pigment concentrate suitable for coloring lithographic ink, which is added to a pigment concentration of 15 to 50% by weight.
本発明者等は２粒状で、ハンドリング性がよく。The inventors of the present invention have two grains and are easy to handle.
希釈能力が高く、汎用性のあり、かつ通常コンクベース
と称されている顔料濃縮物への展開も可能な平版インキ
用粒状着色剤を得るため以下のような条件を検討した。In order to obtain a granular colorant for lithographic ink that has high dilution ability, is versatile, and can be developed into a pigment concentrate commonly referred to as a conch base, the following conditions were investigated.
（１）顔料の水性懸濁液の顔料濃度
（２）油性ワニスの組成（樹脂、乾性油、溶剤等の種類
１組成比）
（３）油性ワニスの粘度
（４）顔料の水性懸濁液の顔料骨と油性ワニスとの比率
（５）フラッシングの温度等
上記（１）の顔料水性懸濁液の顔料濃度については１合
成されたままの顔料水性懸濁液をそのまま使用すること
ができる場合には、そのまま使用するが、水性ペースト
はどの脱水は必要ではないが、３０重量％以下、好まし
くは５〜２５重量％重量％間整する。一般に水性スラリ
ーと称されている顔料濃度前後である。合成されたまま
の顔料水性懸濁液をそのまま使用できる場合、製造工程
の上から有利であり、５〜２５重量％重量％間度では、
水性ペーストに比べ脱水工程上優位である。なお、顔料
水性懸濁液の顔料濃度があまりに小さい、またはあまり
に大きいと、フラッシング工程の労力または時間が大き
くなるため、好ましくない。従って１合成されたままの
顔料水性懸濁液の顔料濃度が、余りに小さい。(1) Pigment concentration of the aqueous pigment suspension (2) Composition of the oil-based varnish (composition ratio of resin, drying oil, solvent, etc.) (3) Viscosity of the oil-based varnish (4) Pigment aqueous suspension Ratio of pigment bone to oil-based varnish (5) Flushing temperature etc. Concerning the pigment concentration of the aqueous pigment suspension in (1) above, 1. If the aqueous pigment suspension as synthesized can be used as it is. is used as is, but the aqueous paste does not require any dehydration, but is adjusted to less than 30% by weight, preferably between 5 and 25% by weight. The pigment concentration is generally around what is called an aqueous slurry. If the aqueous pigment suspension as synthesized can be used as it is, it is advantageous from the viewpoint of the manufacturing process;
It is superior to water-based pastes in terms of dehydration process. It should be noted that if the pigment concentration of the aqueous pigment suspension is too low or too high, the effort and time required for the flushing step will increase, which is not preferable. Therefore, the pigment concentration of the as-synthesized pigment aqueous suspension is too low.
または大きいときは、必要に応じて顔料濃度を調整する
ことができる。Or when it is large, the pigment concentration can be adjusted as necessary.
顔料の種類によって、顔料水性懸濁液における顔料濃度
が変わる。有機顔料では５〜２５重量％である。顔料水
性懸濁液における好ましい顔料濃度とするため、脱水す
ることができる。Depending on the type of pigment, the pigment concentration in the aqueous pigment suspension will vary. For organic pigments it is 5 to 25% by weight. To obtain the preferred pigment concentration in the pigment aqueous suspension, it can be dehydrated.
また２本発明では、顔料水性懸濁液には、実質的に界面
活性剤等の添加剤を添加しない。なお、顔料の合成時に
すでに含まれている添加剤については。Further, in the present invention, substantially no additives such as surfactants are added to the pigment aqueous suspension. Regarding additives that are already included during pigment synthesis.
通常そのままとする。必要に応じてすでに含まれている
添加剤を除去することも可能であり、水洗、脱水等をし
た顔料水性懸濁液を使用することもできる上記（２）の
油性ワニスの組成については、得られた平版インキ用粒
状着色剤が汎用性となるような樹脂等を使用することが
好ましい。すなわち、平版インキ用粒状着色剤から顔料
濃縮物を得るに際し。Usually leave as is. Regarding the composition of the oil-based varnish described in (2) above, it is possible to remove the additives already contained as necessary, and it is also possible to use an aqueous pigment suspension that has been washed with water, dehydrated, etc. It is preferable to use a resin or the like that makes the granular colorant for lithographic ink versatile. That is, when obtaining a pigment concentrate from a granular colorant for lithographic ink.
種々の平版インキ用ワニスと混合できるものが好ましい
。また、顔料濃縮物とせず、最終の平版インキとするに
際し９種々のワニス、ベヒクルと混合できることが望ま
しい。Those that can be mixed with various lithographic ink varnishes are preferred. In addition, it is desirable that the pigment can be mixed with 9 different varnishes and vehicles when preparing the final lithographic ink without using it as a pigment concentrate.
フラッシングに使用する油性ワニスの樹脂としては２例
えばポリエステル樹脂（アルキッド樹脂も）、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である。乾性油としては大豆油、桐
油、アマニ油等であり、その地変性した乾性油でもよい
。勿論半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
ロノぐラフイン）、α−オレフィン、その他の脂肪族炭
化水素等の有機１溶剤である。溶剤としては沸点２００
℃以上の高沸点溶剤が好ましい。油性ワニスの組成とし
ては、重量比で樹脂／油／溶剤として１０〜５０１０〜
６０／１０〜７０である。Resins for oil-based varnishes used for flushing include polyester resins (also alkyd resins), petroleum resins, phenolic resins, rosin-modified phenolic resins, epoxy resins, ketone resins, rosins, rosin derivatives, rosin-modified maleic acid resins, etc. . Drying oils include soybean oil, tung oil, linseed oil, etc., and drying oils obtained by denaturing these oils may also be used. Of course, semi-drying oils can also be used. Examples of the solvent include organic solvents such as normal paraffin, isoparaffin, naphthene (cyclographin), α-olefin, and other aliphatic hydrocarbons. As a solvent, the boiling point is 200
A high boiling point solvent of ℃ or higher is preferred. The composition of the oil-based varnish is resin/oil/solvent in a weight ratio of 10 to 5010.
It is 60/10-70.
平版インキでの油性ワニスの組成の１例を挙げると、ロ
ジン変性フェノール樹脂／アマニ油／石油系高沸点溶剤
であり、４０／１０１５０ （重量比）である。なお５
本発明の平版インキ用粒状着色剤としては、乾性油を含
まず、樹脂および溶剤によって得られる平版インキ用粒
状着色剤であってもよい。また、樹脂および乾性油、樹
脂および高沸点溶剤によって得られるものでもよい。例
えばロジン変性フェノール樹脂／アマニ油（重量比４０
／６０）やロジン変性フェノール樹脂／石油系高沸点溶
剤（重量比５０１５０）である。An example of the composition of an oil-based varnish for lithographic ink is rosin-modified phenolic resin/linseed oil/petroleum-based high boiling point solvent, with a weight ratio of 40/10150. Note 5
The granular colorant for lithographic ink of the present invention may be a granular colorant for lithographic ink that does not contain a drying oil and is obtained from a resin and a solvent. It may also be obtained from a resin and a drying oil, a resin and a high boiling point solvent. For example, rosin modified phenolic resin/linseed oil (weight ratio 40
/60) and rosin-modified phenolic resin/petroleum-based high boiling point solvent (weight ratio 50150).
上記（３）の油性ワニスの粘度としては、常温（２５℃
）で、１００〜１０００ｐｓ、好ましくは３００〜７０
０ｐＳの範囲である。The viscosity of the oil-based varnish in (3) above is at room temperature (25℃
), 100 to 1000 ps, preferably 300 to 70 ps
It is in the range of 0 pS.
上記（４）の顔料水性懸濁液の顔料分と油性ワニスとの
比率としては、フラッシングし、単離（乾燥）した平版
インキ用粒状着色剤としての顔料濃度として３０〜７０
重量％となるような割合で、フラッシングする。すなわ
ち、顔料水性懸濁液の顔料分と油性ワニスの固形分とで
決まる。平版インキ用粒状着色剤としての顔料濃度は、
高いほうが希釈能力では有利であるが、あまりに高いと
、最終インキにする場合、平版インキ用ワニスとの混合
性が劣る。また低すぎると、希釈能力が劣る。なお２本
発明の平版インキ用粒状着色剤と平版インキ用ワニスと
の混合は、顔料粒子の練肉を必要とせず、単にミキサー
により平版インキ用粒状着色剤および平版インキ用ワニ
スを均一に混合し、最終インキにできる。The ratio of the pigment content of the pigment aqueous suspension in the above (4) to the oil-based varnish is 30 to 70 as the pigment concentration as a granular colorant for lithographic ink that has been flushed and isolated (dried).
Flushing is carried out in proportions such as weight %. That is, it is determined by the pigment content of the pigment aqueous suspension and the solid content of the oil-based varnish. The pigment concentration as a granular colorant for lithographic ink is
A higher value is advantageous in terms of dilution ability, but if it is too high, the mixability with a lithographic ink varnish will be poor when used as a final ink. Moreover, if it is too low, the dilution ability will be poor. In addition, the mixing of the granular colorant for lithographic ink and the varnish for lithographic ink of the present invention does not require grinding of pigment particles, and the granular colorant for lithographic ink and the varnish for lithographic ink of the present invention are simply mixed uniformly using a mixer. , can be made into final ink.
上記（５）のフラッシングの温度等としては、常温ない
し８０℃で行われるが、高温度のほうが、短時間でフラ
ッシングが可能なため、好ましくは、５０〜７０℃で行
う。The temperature of the flushing in (5) above is carried out at room temperature to 80°C, but it is preferably carried out at a temperature of 50 to 70°C because flushing can be carried out in a shorter time at a higher temperature.
フラッシングとしては、フラッシャ−を使用することも
可能であるが、顔料の合成に使用された反応釜（タンク
）をそのまま使用し、または合成された顔料の水性懸濁
液を顔料濃度５〜３０重量％となるように脱水した顔料
水性懸濁液を入れたタンクに油性ワニスを添加し、攪拌
しながら混合させ、Ｏ／ＷからＷｌｏへの相転換をし、
脱水（吸引、真空脱水等）シ、平版インキ用粒状着色剤
を製造する。Although it is possible to use a flasher for flushing, it is also possible to use the reaction vessel (tank) used for pigment synthesis as is, or to prepare an aqueous suspension of the synthesized pigment at a pigment concentration of 5 to 30% by weight. Add oil-based varnish to a tank containing an aqueous pigment suspension that has been dehydrated to give
Manufactures dehydration (suction, vacuum dehydration, etc.) and granular colorants for lithographic inks.
フラッシングにおいては、顔料水性懸濁液中に。In flushing, the pigment is in an aqueous suspension.
なるべ（汎用性の高い樹脂を使用したワニスを少量ずつ
添加し、０／ＷからＷｌｏへの転換直後に急速に常温付
近まで冷却し、脱水後、取り出し平版インキ用粒状着色
剤を得ることが好ましい。なお、平版インキ用粒状着色
剤の粒径は、ワニス量、温度等によって調整できる。Narube (a varnish using a highly versatile resin is added little by little, and immediately after converting from 0/W to Wlo, it is rapidly cooled to around room temperature, and after dehydration, it can be taken out to obtain a granular colorant for lithographic ink. Preferably.The particle size of the granular colorant for lithographic ink can be adjusted by adjusting the amount of varnish, temperature, etc.
平版インキ用粒状着色剤の粒径（直径）は２ｍｍ以下１
通常０．１〜１．８ｍｍである。あまりに大きいと添加
する平版インキ用ワニスとの混合性が悪い。The particle size (diameter) of the granular colorant for lithographic ink is 2 mm or less1
It is usually 0.1 to 1.8 mm. If it is too large, miscibility with the lithographic ink varnish to be added will be poor.
本発明の平版インキ用粒状着色剤はそのままでベースイ
ンキとすることもできるが、さらに該平版インキ用粒状
着色剤をワニスと混合し、ペースト状の顔料濃縮物もベ
ースインキとすることもできる。この顔料濃縮物を製造
するには９例えば平版インキ用粒状着色剤に平版インキ
用ワニスを、顔料濃度１０〜５０重量％となるように添
加し、プラネタリ−ミキサー等で３０分間ないし１時間
程度混合することにより、均一なペースト状のベースイ
ンキを得ることができる。なお、顔料粒子を細かくする
練肉分散工程は一切不要である。また、顔料濃縮物を製
造するときのワニスとしてはフラッシング時のワニスと
同じまたは異なるワニスが使用できる。The granular colorant for lithographic ink of the present invention can be used as a base ink as it is, but the granular colorant for lithographic ink can also be mixed with a varnish and a paste-like pigment concentrate can also be used as a base ink. To produce this pigment concentrate, 9 For example, add lithographic ink varnish to a granular colorant for lithographic ink to a pigment concentration of 10 to 50% by weight, and mix with a planetary mixer for about 30 minutes to 1 hour. By doing so, a uniform paste-like base ink can be obtained. Note that the kneading and dispersing step for finely dividing the pigment particles is not necessary at all. Furthermore, the varnish used for producing the pigment concentrate can be the same as or different from the varnish used for flushing.
次に実施例により２本発明を説明する。例中「部」、「
％」とは１重量部１重量％を示す。Next, two embodiments of the present invention will be explained with reference to examples. In the examples, "part", "
%" means 1 part by weight and 1% by weight.
実施例１
フタロシアニン顔料（東洋インキ製造■（，１ｏｎｏＩ
Ｂｌｕｅ ＳＭ−Ａ）の顔料濃度２５％の顔料水
性懸濁液８０部と、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＠製０号ソルベントＨ
）である重量比４０／１０１５０ノ油性ワニス２０部と
、を常温でディスパー（特殊機化工業製２回転数的３５
Ｏｒｐｍ）に仕込み、６０℃に昇温してから、その温度
で常圧下１時間フラッシング（水中油滴型０／Ｗより油
中水滴型Ｗ１０への相変換）を行った。Example 1 Phthalocyanine pigment (Toyo Ink Manufacturing ■(,1onoI)
Blue SM-A), 80 parts of a pigment aqueous suspension with a pigment concentration of 25%, and rosin-modified phenolic resin/linseed oil/petroleum-based high boiling point solvent (No. 0 Solvent H manufactured by Nippon Oil).
) with a weight ratio of 40/10150 and 20 parts of oil-based varnish at room temperature.
After raising the temperature to 60° C., flushing (phase conversion from oil-in-water type 0/W to water-in-oil type W10) was performed at that temperature for 1 hour under normal pressure.
分離析出した遊離の水をデカントして取り去った後、６
０℃、減圧下で３０分間を要し残存する水分をほぼ完全
に除去した。その結果、顔料濃度５０％の平版インキ用
粒状着色剤を得た。After decanting and removing the separated and precipitated free water, 6
It took 30 minutes at 0°C under reduced pressure to almost completely remove the remaining moisture. As a result, a granular colorant for lithographic ink having a pigment concentration of 50% was obtained.
この平版インキ用粒状着色剤の平均粒径は１．５ｍｍで
あった。この平版インキ用粒状着色剤の、顔料そのもの
の練和度（グラインドメーター リーディング、ＧＲ）
は２．０（５μｍ）であった。なお、ＧＲの測定では顔
料濃縮物を石油系溶剤で希釈して行った。The average particle size of this granular colorant for lithographic ink was 1.5 mm. The degree of kneading of the pigment itself of this granular colorant for lithographic ink (Grindmeter reading, GR)
was 2.0 (5 μm). Incidentally, in the measurement of GR, the pigment concentrate was diluted with a petroleum solvent.
得られた平版インキ用粒状着色剤１００部および平版イ
ンキ用ワニス（フラッシング時のワニスと同じ）１００
部をプラネタリ−ミキサー（５０ｒｐｍ）にて３０分間
混合し、顔料濃度３３％の顔料濃縮物（コンクベース）
を作った。100 parts of the obtained granular colorant for lithographic ink and 100 parts of varnish for lithographic ink (same as the varnish for flushing)
A pigment concentrate (conch base) with a pigment concentration of 33% was obtained by mixing the parts in a planetary mixer (50 rpm) for 30 minutes.
made.
実施例２〜８．比較例１〜３ 実施例１において、顔料水性懸濁液の顔料濃度。Examples 2-8. Comparative examples 1 to 3 In Example 1, pigment concentration of the pigment aqueous suspension.
顔料水性懸濁液と油性ワニスとの組成比を変えた各実施
例を表−１に示す。Table 1 shows examples in which the composition ratio of the pigment aqueous suspension and the oil-based varnish was changed.
表−１
実施例２〜８につき、実施例１と同様に測定した平版イ
ンキ用着色剤の平均粒径はいずれも０．１〜２ｍｍの範
囲内であり、顔料粒子そのもののＧＲはいずれも３．０
（７，５μｍ）以下であった。なお、実施例２では実施
例１に比ベフラッシングに時間がかかった。Table 1 For Examples 2 to 8, the average particle size of the lithographic ink colorant measured in the same manner as in Example 1 was all within the range of 0.1 to 2 mm, and the GR of the pigment particles themselves was 3. .0
(7.5 μm) or less. In addition, in Example 2, it took more time for flushing than in Example 1.
一方、比較例１および３は大きな塊となり、比較例２で
は粒状とならず、液状を呈した。On the other hand, Comparative Examples 1 and 3 formed large lumps, and Comparative Example 2 did not form granules but appeared liquid.
実施例９
アブ顔料（東洋インキ製造ｎＬｉｏｎｏｌ Ｒｅｄ
６Ｂ４２０６）の顔料濃度２０％の顔料水性懸濁液（
脱水、洗浄した顔料のプレスケーキに水を添加した）
８０部と、実施例１の油性ワニス２０部と、を常温でデ
ィスパーに仕込み、７０℃に昇温してから、その温度で
常圧下３０分間フラッシングを行った。分離析出した遊
離の水をデカントして取り去った後、７０°Ｃ９減圧下
で３０分間を要し残存する水分をほぼ完全に除去した。Example 9 Abu pigment (Toyo Ink Manufacturing Co., Ltd. Lionol Red)
6B4206) with a pigment concentration of 20% (
water was added to the dehydrated and washed pigment press cake)
80 parts and 20 parts of the oil-based varnish of Example 1 were charged into a disper at room temperature, heated to 70°C, and then flushed at that temperature under normal pressure for 30 minutes. After the separated and precipitated free water was removed by decantation, the remaining water was almost completely removed at 70° C. under reduced pressure for 30 minutes.
その結果、顔料濃度４４．５％の平版インキ用粒状着色
剤を得た。As a result, a granular colorant for lithographic ink having a pigment concentration of 44.5% was obtained.
この平版インキ用粒状着色剤の平均粒径は１．８ｍｍで
あった。この平版インキ用粒伏着色剤を使用し、実施例
１と同様に測定した顔料粒子そのもののＧＲは２．５（
５μｍ）であった。The average particle size of this granular colorant for lithographic ink was 1.8 mm. Using this grain set coloring agent for lithographic ink, the GR of the pigment particles themselves measured in the same manner as in Example 1 was 2.5 (
5 μm).
得られた平版インキ用粒状着色剤１００部および平版イ
ンキ用ワニス（フラッシングのワニスと同じ）４０部を
プラネタリ−ミキサーにて混合し、顔料濃度３８％の顔
料濃縮物（コンクベース）を作った実施例１０〜１２
実施例９において、平版インキ用粒状着色剤の作成条件
（フラッシングの時間、温度、顔料水性懸濁液と油性ワ
ニスとの比等）を変え、各種顔料濃度。100 parts of the obtained granular colorant for lithographic ink and 40 parts of varnish for lithographic ink (same as the varnish for flushing) were mixed in a planetary mixer to make a pigment concentrate (conc base) with a pigment concentration of 38%. Examples 10 to 12 In Example 9, the conditions for preparing the granular colorant for lithographic ink (flushing time, temperature, ratio of pigment aqueous suspension to oil-based varnish, etc.) were changed to produce various pigment concentrations.
平均粒径を持った平版インキ用粒状着色剤を作成し、平
版インキ用ワニスと混合し、最終のインキとするための
混合性について実験した。A granular colorant for lithographic ink with an average particle size was prepared, mixed with a varnish for lithographic ink, and experiments were conducted to examine the mixability of the final ink.
その結果９表−２に示すとおり、顔料濃度７０％以下、
平均粒径２ｍｍ以下の実施例については、その混合性が
良好で実用性に優れているが、顔料濃度７０％を超え、
または平均粒径２ｍｍを超えた比較例では混合性悪（、
単なるミキサーでのインキ化は不可能であった。As shown in Table 9-2, the pigment concentration was 70% or less.
Examples with an average particle size of 2 mm or less have good mixability and are excellent in practicality, but when the pigment concentration exceeds 70%,
Or, in comparative examples with average particle diameters exceeding 2 mm, the mixing property was poor (,
It was impossible to make ink using a simple mixer.
（以下余白）
表−２
なお、混合性は２００／プラネタリ−ミキサーで平版イ
ンキ用ワニスと１時間攪拌し、その状態を目視で判定し
た。(The following is a margin) Table 2 The miscibility was determined by stirring with a lithographic ink varnish for 1 hour using a 200/planetary mixer, and visually judging the state.
実施例１３ アゾ顔料（東洋インキ製造■Ｎｏ１２０７Ｌｉ。Example 13 Azo pigment (Toyo Ink Manufacturing ■No1207Li.
ｎｏｌ Ｙｅｌｌｏｗ）の顔料濃度１５％の顔料水性
懸濁液（脱水、洗浄した顔料のプレスケーキに水を添加
した）８０部と、実施例１の油性ワニス２゜部と、を常
温でニーグーに仕込み、５０℃に昇温してから、その温
度で密圧下１時間フラッシングを行った。分離析出した
ＭＲの水をデカントして取り去った後、５０°Ｃ９減圧
下で３０分間を要し残存する水分をほぼ完全に除去した
。その結果、顔料濃度３７．５％の平版インキ用粒状着
色剤を得た。80 parts of an aqueous pigment suspension with a pigment concentration of 15% (water was added to a press cake of dehydrated and washed pigment) and 2 parts of the oil-based varnish of Example 1 were charged into a Nigu at room temperature. After raising the temperature to 50° C., flushing was performed at that temperature for 1 hour under pressure. After the separated and precipitated MR water was removed by decantation, the remaining water was almost completely removed at 50° C. under reduced pressure for 30 minutes. As a result, a granular colorant for lithographic ink having a pigment concentration of 37.5% was obtained.
この平版インキ用粒状着色剤の平均粒径は０．５ｍｍで
あった。 この平版インキ用粒状着色剤を使用し、実施
例１と同様に測定した顔料粒子そのもののＯＲは１．０
（２，５μｍ）であった。The average particle diameter of this granular colorant for lithographic ink was 0.5 mm. Using this granular colorant for lithographic ink, the OR of the pigment particles themselves measured in the same manner as in Example 1 was 1.0.
(2.5 μm).
得られた平版インキ用粒状着色剤１００部および平版イ
ンキ用ワニス（フラッシングのワニスと同じ）８０部を
混合し、顔料濃度２８％の均一な顔料濃縮物（コンクベ
ース）を得た。100 parts of the obtained granular colorant for lithographic ink and 80 parts of varnish for lithographic ink (same as the varnish for flushing) were mixed to obtain a uniform pigment concentrate (conch base) with a pigment concentration of 28%.
実施例１４
実施例■において油性ワニスをロジン変性アルキッド樹
脂／アマニ油／石油系高沸点溶剤（重量比３０／２０１
５０）に変え、他は実施例１と同様にして平版インキ用
粒状着色剤および顔料濃縮物を製造した。実施例１とほ
ぼ同様な結果が得られた。Example 14 In Example 2, the oil-based varnish was mixed with rosin-modified alkyd resin/linseed oil/petroleum-based high boiling point solvent (weight ratio 30/201).
A granular colorant for lithographic ink and a pigment concentrate were produced in the same manner as in Example 1, except that 50) was changed. Almost the same results as in Example 1 were obtained.
実施例１５
実施例９において油性ワニスをロジン変性フェノール樹
脂／アマニ油（重量比４０／６０）に変え。Example 15 The oil-based varnish in Example 9 was changed to rosin-modified phenolic resin/linseed oil (weight ratio 40/60).
他は実施例９と同様にして平版インキ用粒状着色剤およ
び顔料濃縮物を製造した。実施例９とほぼ同様な結果が
得られた。Otherwise, a granular colorant for lithographic ink and a pigment concentrate were produced in the same manner as in Example 9. Almost the same results as in Example 9 were obtained.
実施例１６
実施例１３において油性ワニスをロジン変性フェノール
樹脂１０号ソルベントＨ（重量比５０１５０）に変え、
他は実施例１３と同様にして平版インキ用粒状着色剤お
よび顔料濃縮物を製造した。実施例１３とほぼ同様な結
果が得られた。Example 16 In Example 13, the oil-based varnish was changed to rosin-modified phenolic resin No. 10 Solvent H (weight ratio 50150),
Otherwise, a granular colorant for lithographic ink and a pigment concentrate were produced in the same manner as in Example 13. Almost the same results as in Example 13 were obtained.
実施例１７
実施例９において、フラッシング時の温度を常温にて行
ったところ、約１．５時間を要したが、フラッシングが
できた。得られた平版インキ用粒状着色剤は実施例９と
ほぼ同様な結果を示した。Example 17 In Example 9, when flushing was carried out at room temperature, flushing was completed although it took about 1.5 hours. The obtained granular colorant for lithographic ink showed almost the same results as in Example 9.
以上のようにして得られた平版インキ用粒状着色剤また
は顔料濃縮物を使用した着色例（応用例）を以下に示す
。Coloring examples (application examples) using the granular colorant for lithographic ink or pigment concentrate obtained as described above are shown below.
応用例１ （オフセット枚葉インキ）
実施例１〜１７で得られたそれぞれの平版インキ用粒状
着色剤１００部または顔料濃縮物２００邪に一般枚葉薄
紙用インキのレノトダウンワニス（ロジン変性フェノー
ル樹脂／アマニ油／石油系高沸点溶剤２重量比４０／２
０／４０） １８０部と、ドライヤー、乾燥抑制剤、
コンパウンド類等の補助剤２０部と、を添加し、プラネ
タリ−ミキサーで単に混合、均一にしただけで、それぞ
れのオフセントインキを作成した。それぞれの平版イン
キ用粒状着色剤または顔料濃縮物を使用して得られたオ
フセットインキのフロー値（スプレッドメーターリーデ
ィング。Application Example 1 (Offset sheet-fed ink) 100 parts of each of the granular colorants for lithographic inks obtained in Examples 1 to 17 or 200 parts of the pigment concentrate and Lenotdown varnish (rosin-modified phenolic resin) for general sheet-fed tissue paper inks. /linseed oil/petroleum-based high boiling point solvent 2 weight ratio 40/2
0/40) 180 parts, a dryer, a drying inhibitor,
Each offset ink was prepared by simply adding 20 parts of auxiliary agents such as compounds, and mixing and homogenizing with a planetary mixer. Offset ink flow values (spread meter readings) obtained using each lithographic ink granular colorant or pigment concentrate.
ＳＲ）はいずれも１６〜１８ｍｍＺ分・２５℃（半径値
）であり、タンク値（インコメ−ターリ−ディング、Ｉ
Ｒ）はいずれも１０〜１２であった。SR) are all 16-18mmZ min.25℃ (radius value), tank value (incometer reading, I
R) were all 10-12.
得られたオフセットインキでオフセット枚葉印刷をした
ところ、光沢、プラン残り１版残りについても、良好で
あり、良好な印刷物が得られた。なお。When offset sheet-fed printing was carried out using the obtained offset ink, good printed matter was obtained, with good gloss and one remaining plate remaining on the plan. In addition.
印刷は三菱重工製ＤＡＩＹＡ−Ｉ、４色印刷機を使用し
た。For printing, a Mitsubishi Heavy Industries DAIYA-I four-color printing machine was used.
応用例２ （オフセント輪転インキ）
実施例１〜１７で得られた平版インキ用粒状着色剤１０
０部または顔料濃縮物２００部にオフセット輪転コート
紙用インキのレノトダウンワニス（ロジン変性フェノー
ル樹脂／アマニ油／石油系高沸点溶剤１重量比４５／１
０／４５）１８０部と、ドライヤー、乾燥抑制剤、コン
パウンド類等の補助剤２０部と、を添加し、プラネタリ
−ミキサーで単に混合、均一にしただけで、それぞれの
オフセットインキを作成した。それぞれの平版インキ用
粒状着色剤または顔料濃縮物を使用して得られたオフセ
ットインキのフロー値（ＳＲ）はいずれも１９〜２０
ｍ ｍ ７分・２５°Ｃ（半径値）であり、タック値（
ＩＲ）はいずれも５〜６であった。Application example 2 (Offcent rotary ink) Granular colorant 10 for lithographic ink obtained in Examples 1 to 17
0 parts or 200 parts of pigment concentrate and Renotdown varnish, an ink for offset rotary coated paper (rosin-modified phenolic resin/linseed oil/petroleum-based high-boiling solvent 1 weight ratio 45/1)
0/45) and 20 parts of auxiliary agents such as dryers, drying inhibitors, compounds, etc. were added and simply mixed and homogenized using a planetary mixer to prepare each offset ink. The flow values (SR) of offset inks obtained using each lithographic ink granular colorant or pigment concentrate were all 19 to 20.
m m 7 minutes・25°C (radius value), tack value (
IR) were all 5-6.
得られたオフセットインキでオフセット輪転印刷をした
ところ、良好な印刷物が得られた。なお、印刷は三菱重
工製Ｌ−５００４色印刷機および弁上金属！！ＴＥＣド
ライヤー装置を使用した。When offset rotary printing was performed using the obtained offset ink, good printed matter was obtained. In addition, the printing was done by Mitsubishi Heavy Industries L-5004 color printing machine and Benjo Metal! ! A TEC dryer device was used.
比較応用例１
実施例１において、フラッシング時間を変え３時間とし
、平均粒径４ｍｍの粒状着色剤を得た。Comparative Application Example 1 In Example 1, the flushing time was changed to 3 hours to obtain a granular colorant with an average particle size of 4 mm.
得られた粒状着色剤１００部を平版インキ用ワニスと混
合したところ、プラネタリ−ミキサーによる混合では、
均一な混合ができず１粒径２ｍｍ以上の粒子がそのまま
残る傾向が見られた。When 100 parts of the obtained granular colorant was mixed with a lithographic ink varnish, mixing with a planetary mixer resulted in:
There was a tendency that uniform mixing could not be achieved and particles with a particle diameter of 2 mm or more remained as they were.
この顔料濃縮物２００部に応用例１と同じレソトダウン
ワニス１８０部、補助剤２０部を添加し、練肉せずに三
本ロール２回通しで混合した。そのフロー値は１７ｍｍ
／分、タック値は１１であった。To 200 parts of this pigment concentrate, 180 parts of the same Lesotho down varnish as in Application Example 1 and 20 parts of an adjuvant were added and mixed by passing through three rolls twice without kneading. Its flow value is 17mm
/min, and the tack value was 11.
このインキを用いて応用例１と同様にして印刷したとこ
ろ、応用例１と比較して印刷物の着色力、光沢いずれも
劣る結果となった。When this ink was used for printing in the same manner as Application Example 1, the printed matter was inferior in coloring strength and gloss compared to Application Example 1.
比較応用例２
実施例１で用いた顔料水性懸濁液１００部と油性ワニス
８部とを常温でディスパーに仕込み、温度を６０℃に上
げ、１時間攪拌した。次に減圧脱水し。Comparative Application Example 2 100 parts of the aqueous pigment suspension used in Example 1 and 8 parts of the oil-based varnish were charged into a disper at room temperature, the temperature was raised to 60°C, and the mixture was stirred for 1 hour. Next, dehydrate under reduced pressure.
顔料濃度７５％の粒状着色剤を得た。A granular colorant with a pigment concentration of 75% was obtained.
この粒状着色剤の平均粒径１．５ｍｍであった。The average particle size of this granular colorant was 1.5 mm.
この粒状着色剤１００部に平版インキ用ワニス１００部
を加え、プラネタリ−ミキサーで攪拌混合した。しかし
、長時間攪拌したが、均一な状態にならず、インキ化が
不良であった。応用例２と同様にオフセント輪転印刷を
したところ、印刷物の着色力。100 parts of lithographic ink varnish was added to 100 parts of this granular colorant, and the mixture was stirred and mixed using a planetary mixer. However, although it was stirred for a long time, it did not become uniform and the ink formation was poor. When off-cent rotary printing was performed in the same manner as Application Example 2, the coloring strength of the printed matter was
光沢いずれも明らかに劣っていた。Both glosses were clearly inferior.
Claims (1)
７０重量％、平均粒径２ｍｍ以下であることを特徴とす
る平版インキ用粒状着色剤。 ２、有機顔料、樹脂および乾性油を含む特許請求の範囲
第１項記載の平版インキ用粒状着色剤。 ３、有機顔料、樹脂および高沸点溶剤を含む特許請求の
範囲第１項記載の平版インキ用粒状着色剤。 ４、平均粒径０．１〜１．８ｍｍである特許請求の範囲
第１項ないし第３項いずれか記載の平版インキ用粒状着
色剤。 ５、顔料濃度３０重量％以下の有機顔料の水性懸濁液を
、実質的に予め添加剤を加えることなく、油性ワニスと
混合し、フラッシングせしめ、単離してなる顔料濃度３
０〜７０重量％、平均粒径２ｍｍ以下であることを特徴
とする平版インキ用粒状着色剤。 ６、顔料濃度５〜２５重量％の有機顔料の水性懸濁液を
使用する特許請求の範囲第５項記載の平版インキ用粒状
着色剤。 ７、温度５０〜７０℃でフラッシングしてなる特許請求
の範囲第５項または第６項記載の平版インキ用粒状着色
剤。 ８、顔料濃度３０重量％以下の有機顔料の水性懸濁液を
、実質的に予め添加剤を加えることなく、油性ワニスと
混合し、フラッシングせしめ、単離してなる顔料濃度３
０〜７０重量％、平均粒径２ｍｍ以下である平版インキ
用粒状着色剤を平版インキ用ワニスに、顔料濃度１５〜
５０重量％となるよう添加してなることを特徴とする平
版インキ用顔料濃縮物。[Claims] 1. Contains an organic pigment and a resin, and the concentration of the organic pigment is 30 to 30.
A granular colorant for lithographic ink, characterized in that it contains 70% by weight and an average particle size of 2 mm or less. 2. The granular colorant for lithographic ink according to claim 1, which contains an organic pigment, a resin, and a drying oil. 3. The granular colorant for lithographic ink according to claim 1, which contains an organic pigment, a resin, and a high-boiling solvent. 4. The granular colorant for lithographic ink according to any one of claims 1 to 3, which has an average particle size of 0.1 to 1.8 mm. 5. Pigment concentration 3 obtained by mixing an aqueous suspension of an organic pigment with a pigment concentration of 30% by weight or less with an oil-based varnish, flashing it, and isolating it without adding any additives in advance.
A granular colorant for lithographic ink, characterized in that it contains 0 to 70% by weight and has an average particle size of 2 mm or less. 6. The granular colorant for lithographic ink according to claim 5, which uses an aqueous suspension of an organic pigment with a pigment concentration of 5 to 25% by weight. 7. The granular colorant for lithographic ink according to claim 5 or 6, which is obtained by flashing at a temperature of 50 to 70°C. 8. Pigment concentration 3 obtained by mixing an aqueous suspension of an organic pigment with a pigment concentration of 30% by weight or less with an oil-based varnish, flashing it, and isolating it without adding any additives in advance.
A lithographic ink varnish containing 0 to 70% by weight of a granular colorant with an average particle size of 2 mm or less is added to a lithographic ink varnish at a pigment concentration of 15 to 70% by weight.
A pigment concentrate for lithographic ink, characterized in that the pigment concentrate is added in an amount of 50% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292483A JPS62153364A (en) | 1985-12-27 | 1985-12-27 | Particulate coloring material for lithographic ink and pigment concentrate obtained by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292483A JPS62153364A (en) | 1985-12-27 | 1985-12-27 | Particulate coloring material for lithographic ink and pigment concentrate obtained by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62153364A true JPS62153364A (en) | 1987-07-08 |
| JPH0569147B2 JPH0569147B2 (en) | 1993-09-30 |
Family
ID=17782395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60292483A Granted JPS62153364A (en) | 1985-12-27 | 1985-12-27 | Particulate coloring material for lithographic ink and pigment concentrate obtained by using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62153364A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6440084B1 (en) * | 2018-03-27 | 2018-12-19 | 下村 恭一 | A water-based printing ink used for gravure printing that reduces doctor wear and a film laminate using the ink. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5798564A (en) * | 1980-10-21 | 1982-06-18 | Hoechst Ag | Manufacture of pigment granule and use |
-
1985
- 1985-12-27 JP JP60292483A patent/JPS62153364A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5798564A (en) * | 1980-10-21 | 1982-06-18 | Hoechst Ag | Manufacture of pigment granule and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6440084B1 (en) * | 2018-03-27 | 2018-12-19 | 下村 恭一 | A water-based printing ink used for gravure printing that reduces doctor wear and a film laminate using the ink. |
| JP2019172728A (en) * | 2018-03-27 | 2019-10-10 | 下村 恭一 | Water based printing ink capable of reducing doctor wear and used for gravure printing and film laminated material using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0569147B2 (en) | 1993-09-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |