JPH101619A - Copper phthalocyanine pigment composition for publishing gravure ink - Google Patents
Copper phthalocyanine pigment composition for publishing gravure inkInfo
- Publication number
- JPH101619A JPH101619A JP15391696A JP15391696A JPH101619A JP H101619 A JPH101619 A JP H101619A JP 15391696 A JP15391696 A JP 15391696A JP 15391696 A JP15391696 A JP 15391696A JP H101619 A JPH101619 A JP H101619A
- Authority
- JP
- Japan
- Prior art keywords
- copper phthalocyanine
- type
- pigment composition
- parts
- dry
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、出版グラビアイン
キ中において、銅フタロシアニン顔料の濃度、流動性、
貯蔵安定性を著しく改善し得る銅フタロシアニン顔料組
成物に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a gravure ink for publishing, wherein the concentration, flowability,
The present invention relates to a copper phthalocyanine pigment composition capable of significantly improving storage stability.
【０００２】[0002]
【従来の技術】従来、出版グラビアインキ用に使用され
るβ型銅フタロシアニン顔料としては、（１）特開昭５
１−２８１１９号公報には、銅フタロシアニンのクルー
ドを、塩化ナトリウムのような水溶性無機塩から成る磨
砕助剤及びジエチレングリコール、エチレングリコール
等のポリオール類、アルコール又はアミン等の有機液体
と共に、ニーダー又はシンプソンミックスマーラー等の
磨砕機を用いて湿式磨砕する、いわゆるソルベントソル
トミリング法によって顔料化して得た混練物を、水に解
膠して水洗、ろ過することによって水溶性無機塩である
磨砕助剤と有機液体を除去して顔料を得る方法が開示さ
れている。また、（２）特開昭５０−１５７４１９号公
報及び特開昭５２−６９４３５号公報には、磨砕助剤及
び有機液体の不存在下に銅フタロシアニンのクルード
を、ボールミル、アトライターのような磨砕機を使用し
て乾式磨砕する、いわゆるドライミリング法によって、
クルード銅フタロシアニンの乾式磨砕物を得た後、この
銅フタロシアニンのクルードの乾式磨砕物が微細化に伴
って結晶型が一部β型からα型へ転移して、強く凝集し
ているので、このα型とβ型が混在した乾式磨砕物を水
とキシレンの混合溶液、又は水とアルコールの混合溶液
等の結晶化溶剤と加熱することによって、α型をβ型に
転移させると共に、結晶粒子を大きくして分散させた
後、結晶化溶剤を蒸留によって留去して顔料を得る方法
が開示されている。これらの方法等によって得られたβ
型銅フタロシアニン顔料は、銅フタロシアニン誘導体を
用いて処理された上で、実用に供されていた。2. Description of the Related Art Conventionally, β-type copper phthalocyanine pigments used for publication gravure inks are disclosed in (1)
No. 1-28119 discloses that a crude copper phthalocyanine is kneaded with a grinding aid consisting of a water-soluble inorganic salt such as sodium chloride and a polyol such as diethylene glycol and ethylene glycol, and an organic liquid such as an alcohol or an amine. A kneaded material obtained by pigmentation by a so-called solvent salt milling method, which is wet-milled using a grinder such as Simpson mix muller, is pulverized into water, washed with water, and filtered to obtain a water-soluble inorganic salt. A method for removing an auxiliary agent and an organic liquid to obtain a pigment is disclosed. (2) JP-A-50-157419 and JP-A-52-69435 disclose the use of copper phthalocyanine crude in the absence of a grinding aid and an organic liquid, such as a ball mill and an attritor. By the so-called dry milling method of dry grinding using a grinding machine,
After obtaining the dry milled product of crude copper phthalocyanine, the dry milled product of the crude copper phthalocyanine partially transitions from β-type to α-type with refinement and is strongly aggregated. By heating the dry milled material in which α-type and β-type are mixed with a crystallization solvent such as a mixed solution of water and xylene, or a mixed solution of water and alcohol, the α-type is transferred to β-type, and the crystal particles are converted. A method is disclosed in which a pigment is obtained by dispersing the crystallization solvent in a large size and then distilling off a crystallization solvent by distillation. Β obtained by these methods, etc.
The type copper phthalocyanine pigment has been practically used after being treated with a copper phthalocyanine derivative.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、（１）
特開昭５１−２８１１９号公報に記載された方法では、
β型銅フタロシアニンのクルードに対して、多量の水溶
性無機塩である磨砕助剤と、その磨砕物を良好なウエッ
ティング状態に保つ為に、多量の有機液体である湿潤剤
を使用するため、生産コストが増大し、また、長時間磨
砕したり、ウエットケーキを乾燥するのに多大なエネル
ギーを必要とするなどの問題点があった。また、この方
法では、大量の排水を処理する必要があり、多大な排水
処理費用と手間がかかる、あるいは、この排水から磨砕
助剤と湿潤剤を回収するには、溶剤回収設備と多大なエ
ネルギーが必要であるという問題点もあった。However, (1)
In the method described in JP-A-51-28119,
To use a large amount of a grinding aid, which is a water-soluble inorganic salt, for the crude of β-type copper phthalocyanine, and a large amount of a wetting agent, which is an organic liquid, in order to keep the ground material in a good wet state. However, there are problems that the production cost increases, that grinding is performed for a long time, and that a large amount of energy is required to dry the wet cake. In addition, this method requires a large amount of wastewater to be treated, which requires a great deal of wastewater treatment cost and labor. In order to recover the grinding aid and the wetting agent from the wastewater, a large amount of solvent recovery equipment is required. There was also a problem that energy was required.
【０００４】また、（２）特開昭５０−１５７４１９号
公報及び特開昭５２−６９４３５号公報に記載された方
法では、多量の有機溶剤を使用するために、作業環境の
溶剤による汚染があること、溶剤回収設備と多大なエネ
ルギーが必要であるほか、ウエットケーキを乾燥するの
に多大なエネルギーを必要とするなどの問題点があっ
た。Further, (2) In the methods described in JP-A-50-157419 and JP-A-52-69435, since a large amount of an organic solvent is used, there is contamination of the working environment by the solvent. In addition, there are problems that a solvent recovery facility and a large amount of energy are required, and a large amount of energy is required to dry a wet cake.
【０００５】本発明が解決しようとする課題は、磨砕助
剤、湿潤剤、有機溶剤、水を使用することなく、出版グ
ラビアインキに使用した場合に、濃度、流動性、貯蔵安
定性に優れた銅フタロシアニン顔料組成物を提供するこ
とにある。[0005] The problem to be solved by the present invention is that, when used in a gravure ink for publication without using a grinding aid, a wetting agent, an organic solvent or water, it is excellent in concentration, flowability and storage stability. To provide a copper phthalocyanine pigment composition.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、鋭意研究
を重ねた結果、上記のソルトミリング法に依って得られ
たβ型銅フタロシアニン顔料、又はドライミリング法に
よって得られたα型とβ型が混在した乾式磨砕物を結晶
化溶剤との加熱処理に依って得られたβ型銅フタロシア
ニン顔料に代えて、ドライミリング法によって得られた
α型とβ型が混在した乾式磨砕物を用いると共に、特定
の銅フタロシアニン誘導体を含有させた顔料組成物が上
記課題を解決し得ることを見い出し、本発明を完成する
に至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the β-type copper phthalocyanine pigment obtained by the above-described salt milling method or the α-type copper phthalocyanine pigment obtained by the dry milling method The dry milled material in which α-type and β-type mixed by dry milling method are used instead of the β-type copper phthalocyanine pigment obtained by the heat treatment with the crystallization solvent, The present inventors have found that a pigment composition containing a specific copper phthalocyanine derivative can solve the above problems, and have completed the present invention.
【０００７】即ち、本発明は上記課題を解決するため
に、（１）β型銅フタロシアニンのクルードを乾式磨砕
して得られるα型とβ型が混在した銅フタロシアニンの
乾式磨砕物と、（２）（ａ）一般式（Ｉ）That is, in order to solve the above-mentioned problems, the present invention provides (1) a dry-milled copper phthalocyanine mixture of α-type and β-type obtained by dry-milling the crude of β-type copper phthalocyanine; 2) (a) General formula (I)
【０００８】[0008]
【化３】 Embedded image
【０００９】（式中、ＣｕＰｃは銅フタロシアニン残基
を表わし、ｎは１〜３の整数を表わし、 Ｒ1は水素原子
又は炭素原子数１〜２のアルキル基を表わす。）で表わ
される銅フタロシアニン誘導体、及び（ｂ）一般式（I
I）Wherein CuPc represents a copper phthalocyanine residue, n represents an integer of 1 to 3, and R 1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. A derivative; and (b) a compound represented by the general formula (I
I)
【００１０】[0010]
【化４】 Embedded image
【００１１】（式中、ＣｕＰｃは銅フタロシアニン残基
を表わし、ｍは１〜３の整数を表わし、 Ｒ2は炭素原子
数１〜４のアルキル基を表わし、Ａは炭素原子数２〜４
の線状又は分岐状の飽和アルキレン基を表わす。）で表
わされる銅フタロシアニン誘導体から成る群から選ばれ
る銅フタロシアニン誘導体を含有する出版グラビアイン
キ用銅フタロシアニン顔料組成物を提供する。(Wherein, CuPc represents a copper phthalocyanine residue, m represents an integer of 1 to 3, R 2 represents an alkyl group having 1 to 4 carbon atoms, and A represents 2 to 4 carbon atoms.
Represents a linear or branched saturated alkylene group. The present invention provides a copper phthalocyanine pigment composition for gravure ink for publication, containing a copper phthalocyanine derivative selected from the group consisting of the copper phthalocyanine derivatives represented by the formula (1).
【００１２】本発明で用いるドライミリンミリング法に
よって得られたα型とβ型が混在した銅フタロシアニン
の乾式磨砕物は、銅フタロシアニンのクルードを無機塩
等の磨砕助剤を用いないで、例えば、アトライター又は
ボールミル等の磨砕機で乾式磨砕によって得ることがで
きるが、これらの例に限定されるものではない。The dry milled product of copper phthalocyanine mixed with α-type and β-type obtained by dry milling milling method used in the present invention can be prepared by using the crude copper phthalocyanine without using a grinding aid such as an inorganic salt. , An attritor, a ball mill or the like, but not limited to these examples.
【００１３】ドライミリンミリング法によって得られた
α型とβ型が混在した銅フタロシアニンの乾式磨砕物
は、その一次粒子の大きさ、その比表面積の程度、その
α型銅フタロシアニンの含有率の程度等に限定されず、
いずれもが使用できるが、一次粒子径が０．０１〜０．
０５μｍの範囲にあり、また、その比表面積が、５〜１
０ｍ2 ／ｇの範囲にあり、またα型銅フタロシアニンの
含有率が、４０〜７０重量％の範囲にある乾式磨砕物が
好ましい。The dry milled product of copper phthalocyanine mixed with α-type and β-type obtained by dry milling milling method has a primary particle size, a specific surface area, and a content of α-type copper phthalocyanine. Not limited to
Any of them can be used, but the primary particle diameter is 0.01 to 0.1.
And the specific surface area is 5 to 1 μm.
A dry milled material having a range of 0 m 2 / g and a content of α-type copper phthalocyanine in a range of 40 to 70% by weight is preferred.
【００１４】本発明で用いる一般式（Ｉ）で表わされる
銅フタロシアニン誘導体としては、公知の化合物が特に
制限なく使用することができる。そのような銅フタロシ
アニン誘導体としては、例えば、アミノメチル銅フタロ
シアニン、ジメチルアミノメチル銅フタロシアニン、ジ
エチルアミノメチル銅フタロシアニン等が挙げられる。
これらの化合物は、単独で用いることも、２種以上混合
して用いることもできる。As the copper phthalocyanine derivative represented by the general formula (I) used in the present invention, known compounds can be used without any particular limitation. Examples of such copper phthalocyanine derivatives include aminomethyl copper phthalocyanine, dimethylaminomethyl copper phthalocyanine, and diethylaminomethyl copper phthalocyanine.
These compounds can be used alone or in combination of two or more.
【００１５】また、本発明で用いる一般式（II）で表わ
される銅フタロシアニン誘導体は、例えば、一般式（II
I）The copper phthalocyanine derivative represented by the general formula (II) used in the present invention is, for example, a compound represented by the general formula (II)
I)
【００１６】[0016]
【化５】 Embedded image
【００１７】（式中、ＣｕＰｃ及びｍは一般式（II）に
おける場合と同じ定義である。）で表わされる銅フタロ
シアニンスルフォニルクロライド１モルと、一般式（I
V）(Wherein CuPc and m have the same definition as in formula (II)), and 1 mol of copper phthalocyanine sulfonyl chloride represented by formula (I)
V)
【００１８】[0018]
【化６】 Embedded image
【００１９】（式中、Ａ及びＲ2は一般式（II）におけ
る場合と同じ定義である。）で表わされるジアミン１〜
３モルを用いて、常法により水中、有機溶媒中又は水と
の混合溶媒中で反応させることにより容易に製造するこ
とができる。(Wherein A and R 2 have the same definitions as in the general formula (II)).
It can be easily produced by reacting with 3 moles in a conventional manner in water, an organic solvent or a mixed solvent with water.
【００２０】上記反応に用いるジアミンとしては、例え
ば、ジメチルアミノエチルアミン、ジエチルアミノエチ
ルアミン、ジプロピルアミノエチルアミン、ジブチルア
ミノエチルアミン、ジメチルアミノプロピルアミン、ジ
エチルアミノプロピルアミン、ジプロピルアミノプロピ
ルアミン、ジブチルアミノプロピルアミン、ジメチルア
ミノブチルアミン、ジエチルアミノブチルアミン、ジプ
ロピルアミノブチルアミン、ジブチルアミノブチルアミ
ンが挙げられる。これらのジアミンは、単独で用いるこ
とも、２種以上混合して用いることもできる。As the diamine used in the above reaction, for example, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine Examples include aminobutylamine, diethylaminobutylamine, dipropylaminobutylamine, and dibutylaminobutylamine. These diamines can be used alone or in combination of two or more.
【００２１】本発明で使用する一般式（Ｉ）及び一般式
（II）で表わされる銅フタロシアニン誘導体の使用量
は、銅フタロシアニンのクルードを乾式磨砕して得たα
型とβ型が混在した銅フタロシアニンの乾式磨砕物１０
０重量部に対して、０．５〜２０重量部の範囲が好まし
く、２〜１５重量部の範囲が特に好ましい。The amount of the copper phthalocyanine derivative represented by the general formulas (I) and (II) used in the present invention is determined by the dry grinding of the crude copper phthalocyanine.
Dry crushed product of copper phthalocyanine mixed with β-type and β-type 10
The range of 0.5 to 20 parts by weight is preferable, and the range of 2 to 15 parts by weight is particularly preferable with respect to 0 parts by weight.
【００２２】銅フタロシアニンのクルードを乾式磨砕し
て得たα型とβ型が混在した銅フタロシアニンの乾式磨
砕物と、一般式（Ｉ）及び一般式（II）で表わされる銅
フタロシアニン誘導体を混合して、本発明の顔料組成物
とする方法は、いかなる方法でもよく、例えば、一般
式（Ｉ）及び一般式（II）で表わされる銅フタロシアニ
ン誘導体を、銅フタロシアニンの乾式磨砕物に粉末の状
態で混合する方法、ないしは乾式磨砕機の中へ加える方
法；銅フタロシアニンのクルードに、一般式（Ｉ）及
び一般式（II）で表わされる銅フタロシアニン誘導体を
粉末の状態で混合した後、乾式磨砕を行なう方法；銅
フタロシアニンのクルードのスラリー中に一般式（Ｉ）
及び一般式（II）で表わされる銅フタロシアニン誘導体
を混合して、ろ過、水洗、乾燥してから乾式磨砕する方
法；銅フタロシアニンのクルードのウエットケーキと
一般式（Ｉ）及び一般式（II）で表わされる銅フタロシ
アニン誘導体のウエットケーキ同志を混合し、乾燥して
から乾式磨砕する方法；銅フタロシアニンのクルード
の存在下で一般式（Ｉ）及び一般式（II）で表わされる
銅フタロシアニン誘導体を形成させた後、ろ過、水洗、
乾燥してから乾式摩砕を行なう方法；銅フタロシアニ
ンのクルードを乾式磨砕して得たα型とβ型が混在した
銅フタロシアニンを含有する乾式磨砕物をベヒクルに分
散させる工程で一般式（Ｉ）及び一般式（II）で表わさ
れる銅フタロシアニン誘導体を加える方法；β型銅フ
タロシアニンのクルードを乾式磨砕して得たα型とβ型
が混在した銅フタロシアニンを含有する乾式磨砕物を分
散させたインキ中へ、一般式（Ｉ）及び一般式（II）で
表わされる銅フタロシアニン誘導体を分散させたインキ
を加える方法、等が挙げられるが、これらの例に限定さ
れるものではない。通常、上記及びの方法で十分な
効果が得られる。A dry milled copper phthalocyanine mixture of α-type and β-type obtained by dry milling of crude copper phthalocyanine is mixed with a copper phthalocyanine derivative represented by the general formula (I) or (II). The method for preparing the pigment composition of the present invention may be any method. For example, the copper phthalocyanine derivative represented by the general formula (I) and the general formula (II) may be added to a dry milled product of copper phthalocyanine in a powder state. Or a method of adding the mixture into a dry mill; mixing the copper phthalocyanine derivative represented by the general formula (I) and the general formula (II) in a powder state with the crude copper phthalocyanine, followed by dry milling In a slurry of crude copper phthalocyanine of the general formula (I)
And a method of mixing a copper phthalocyanine derivative represented by the general formula (II), filtering, washing with water, drying and then dry-milling; a wet cake of copper phthalocyanine crude and the general formulas (I) and (II) A wet cake of a copper phthalocyanine derivative represented by the following formula, and drying and dry-milling: a copper phthalocyanine derivative represented by the general formula (I) and the general formula (II) in the presence of copper phthalocyanine crude After forming, filtration, washing with water,
A method of performing dry milling after drying; a step of dispersing a dry milled material containing copper phthalocyanine mixed with α-type and β-type obtained by dry-milling the crude of copper phthalocyanine in a vehicle; ) And a method of adding a copper phthalocyanine derivative represented by the general formula (II); a dry milled material containing copper phthalocyanine mixed with α type and β type obtained by dry milling crude of β type copper phthalocyanine is dispersed. A method of adding an ink in which the copper phthalocyanine derivative represented by the general formula (I) or the general formula (II) is dispersed into the prepared ink, but is not limited to these examples. In general, the above method and the above method can provide a sufficient effect.
【００２３】[0023]
【実施例】以下、実施例及び比較例を用いて本発明を更
に詳細に説明する。以下の実施例及び比較例において、
「部」は『重量部』を表わす。The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples,
“Parts” represents “parts by weight”.
【００２４】＜合成例１＞撹拌機、温度計を備えた容量
１０００ｍｌの琺瑯容器にフタルイミドメチル銅フタロ
シアニンのウエットケーキ２４００部（フタルイミドメ
チル銅フタロシアニンの乾燥重量で６００部に相当）及
び水３８００部を加え、充分に分散させた後、２０％水
酸化ナトリウム水溶液８６０部を加え、撹拌下に８５℃
で２時間反応させた後、２０％塩酸１２００部を加え、
更に撹拌下に８５℃で２時間反応させた。反応終了後、
２０％水酸化ナトリウム水溶液５３０部を加えて反応混
合物を弱アルカリ性とした後、結晶を濾別し、濾別した
結晶を水洗してアミノメチル銅フタロシアニンウエット
ケーキ１４４０部（アミノメチル基を平均１．４個有す
るアミノメチル銅フタロシアニン；乾燥重量で４３２部
に相当）を得た。このウエットケーキ１００部を、７０
〜８０℃で乾燥させて、アミノメチル銅フタロシアニン
３０部を得た。<Synthesis Example 1> 2400 parts of a phthalimidomethyl copper phthalocyanine wet cake (equivalent to 600 parts by dry weight of phthalimidomethyl copper phthalocyanine) and 3800 parts of water were placed in a 1000 ml enamel container equipped with a stirrer and a thermometer. After sufficiently dispersing, 860 parts of a 20% aqueous sodium hydroxide solution was added, and the mixture was stirred at 85 ° C.
After reacting for 2 hours, 1200 parts of 20% hydrochloric acid was added,
The mixture was further reacted at 85 ° C. for 2 hours with stirring. After the reaction,
After adding 530 parts of a 20% aqueous sodium hydroxide solution to make the reaction mixture slightly alkaline, the crystals are separated by filtration, and the separated crystals are washed with water to obtain 1440 parts of an aminomethylcopper phthalocyanine wet cake (an average of aminomethyl groups is 1.40 parts). Aminomethylcopper phthalocyanine having four; equivalent to 432 parts by dry weight). 100 parts of this wet cake is 70
It was dried at -80 ° C to obtain 30 parts of aminomethyl copper phthalocyanine.
【００２５】＜合成例２＞撹拌機及び温度計を備えた容
量１０００ｍｌのオートクレーブに、合成例１で得たア
ミノメチル銅フタロシアニンのウエットケーキ１００部
（アミノメチル銅フタロシアニンの乾燥重量で３０部に
相当）、水４００部、８８％ギ酸２７部（アミノ基に対
して７．６倍モル）及び８０％パラホルムアルデヒド６
部（アミノ基に対して２．３倍モル）を仕込み、撹拌下
に１時間かけて１４０℃に昇温させた後、同温度で５時
間反応させた。反応中のオートクレーブ内は、圧力が上
昇し、５．０〜５．５kg／cm2 になっていた。反応終了
後、室温まで冷却し、脱ガスした後、反応混合物に２０
％水酸化ナトリウム水溶液７１部を加えて弱アルカリ性
とした後、結晶を濾別し、濾別した結晶を水洗してジメ
チルアミノメチル銅フタロシアニンのウエットケーキを
得た。このウエットケーキを、７０〜８０℃で乾燥させ
て、ジメチルアミノメチル銅フタロシアニン３０部を得
た。<Synthesis Example 2> In a 1000 ml autoclave equipped with a stirrer and a thermometer, 100 parts of the wet cake of aminomethyl copper phthalocyanine obtained in Synthesis Example 1 (corresponding to 30 parts by dry weight of aminomethyl copper phthalocyanine) ), 400 parts of water, 27 parts of 88% formic acid (7.6 times mol based on amino group) and 80% paraformaldehyde 6
Then, the mixture was heated to 140 ° C. over 1 hour with stirring, and then reacted at the same temperature for 5 hours. The pressure inside the autoclave during the reaction increased to 5.0 to 5.5 kg / cm 2 . After completion of the reaction, the reaction mixture was cooled to room temperature and degassed.
After adding 71 parts of a 70% aqueous sodium hydroxide solution to make the mixture weakly alkaline, the crystals were separated by filtration, and the separated crystals were washed with water to obtain a wet cake of dimethylaminomethylcopper phthalocyanine. The wet cake was dried at 70 to 80 ° C. to obtain 30 parts of dimethylaminomethyl copper phthalocyanine.
【００２６】＜合成例３＞撹拌機及び温度計を備えた容
量１０００ｍｌのガラス製反応容器にクロルスルホン酸
１０００部を仕込んだ後、撹拌しながら塩化チオニル２
００部を加えた。この混合物を撹拌しながら冷却し、４
０℃以下で、β型銅フタロシアニンのクルード（大日本
インキ化学工業(株)製の「Ｆａｓｔｏｇｅｎ Ｂｌｕｅ
ＡＣ」）２５０部を仕込んだ。更に、４０℃以下で１
時間撹拌した後、１時間かけて９０℃迄昇温した。反応
温度を９０±０．５℃に保ちながら７時間反応させた
後、内温を２０℃以下迄冷却した。撹拌機及び温度計を
備えた２０００ｍｌビーカーに水３００部及び砕氷７０
０部を入れ、氷水を撹拌しながら、５℃以下に保ちなが
ら上記反応液を徐々に取り出した後、析出した結晶を濾
別し、濾別した結晶を５℃以下の氷水で洗液のｐＨが３
以上となるまで水洗して銅フタロシアニンスルホニルク
ロライドウエットケーキ１５６８部（１分子中にスルホ
ニルクロライド基を平均１．３個有する銅フタロシアニ
ンスルホニルクロライド；乾燥重量で２９０部に相当）
を得た。<Synthesis Example 3> 1000 parts of chlorosulfonic acid was charged into a 1000 ml glass reaction vessel equipped with a stirrer and a thermometer, and then thionyl chloride 2 was stirred.
00 parts were added. The mixture is cooled with stirring and
At 0 ° C. or lower, crude β-type copper phthalocyanine (“Fastogen Blue” manufactured by Dainippon Ink and Chemicals, Inc.)
AC ") 250 parts were charged. Furthermore, at 40 ° C or less,
After stirring for one hour, the temperature was raised to 90 ° C. over one hour. After reacting for 7 hours while maintaining the reaction temperature at 90 ± 0.5 ° C., the internal temperature was cooled to 20 ° C. or less. 300 parts of water and 70 pieces of crushed ice are placed in a 2000 ml beaker equipped with a stirrer and a thermometer.
After adding 0 parts, the reaction solution was gradually taken out while keeping the temperature at 5 ° C. or lower while stirring the ice water, the precipitated crystals were separated by filtration, and the crystals separated by filtration were washed with ice water at 5 ° C. or lower to adjust the pH of the washing solution. Is 3
After washing with water until the above, 1568 parts of copper phthalocyanine sulfonyl chloride wet cake (copper phthalocyanine sulfonyl chloride having an average of 1.3 sulfonyl chloride groups in one molecule; equivalent to 290 parts by dry weight)
I got
【００２７】次に、撹拌機及び温度計を備えた容量２０
００ｍｌのガラス製反応容器に水１５０部及び砕氷３０
０部を入れ、氷水を撹拌しながら、ジメチルアミノプロ
ピルアミン２１０部を加えて、溶液の温度を５℃以下に
維持し、撹拌しながら、上記で得た銅フタロシアニンス
ルホニルクロライドウエットケーキ１５６８部（乾燥重
量で２９０部に相当）を少しずつ加えた後、０〜５℃で
１時間反応させた後、温度を徐々に上げ、２時間後に２
５℃とした。その後、２５℃で更に２時間撹拌を続け
た。Next, a capacity 20 equipped with a stirrer and a thermometer was used.
150 parts of water and 30 pieces of crushed ice are placed in a 00 ml glass reaction vessel.
0 parts, add 210 parts of dimethylaminopropylamine while stirring ice water, maintain the temperature of the solution at 5 ° C. or lower, and stir while stirring 1568 parts of the copper phthalocyanine sulfonyl chloride wet cake (dried). (Equivalent to 290 parts by weight) was added little by little, and the mixture was allowed to react at 0 to 5 ° C. for 1 hour.
5 ° C. Thereafter, stirring was continued at 25 ° C. for another 2 hours.
【００２８】撹拌機及び温度計を備えた容量１００００
ｍｌの琺瑯製の容器に、水５０００部を仕込み、撹拌し
ながら上記反応液を少しずつ取り出した。その後、水を
３５００部追加した後、温度を８０〜８５℃に昇温し
て、その後８０〜８５℃で６時間撹拌して結晶を成長さ
せた。その後、結晶を濾別し、濾別した結晶を水洗した
後、７０〜８０℃で乾燥させて、銅フタロシアニンジメ
チルアミノプロピルスルホアミド２９７部を得た。10000 capacity equipped with stirrer and thermometer
5,000 parts of water was charged into a 1 ml enamel container, and the reaction solution was taken out little by little with stirring. Then, after adding 3500 parts of water, the temperature was raised to 80 to 85 ° C, and then the mixture was stirred at 80 to 85 ° C for 6 hours to grow crystals. Thereafter, the crystals were separated by filtration, washed with water, and dried at 70 to 80 ° C. to obtain 297 parts of copper phthalocyanine dimethylaminopropylsulfonamide.
【００２９】＜合成例４＞合成例３において、ジメチル
アミノプロピルアミン２１０部に代えて、ジエチルアミ
ノエチルアミン２４０部を使用した以外は、合成例３と
同様にして銅フタロシアニンジエチルアミノエチルスル
ホアミド３１０部を得た。<Synthesis Example 4> 310 parts of copper phthalocyanine diethylaminoethylsulfonamide was obtained in the same manner as in Synthesis Example 3 except that 240 parts of diethylaminoethylamine was used instead of 210 parts of dimethylaminopropylamine. Was.
【００３０】＜合成例５＞合成例３において、ジメチル
アミノプロピルアミン２１０部に代えて、ジエチルアミ
ノプロピルアミン２６９部を使用した以外は合成例３と
同様にして、銅フタロシアニンジエチルアミノプロピル
スルホアミド３１３部を得た。<Synthesis Example 5> 313 parts of copper phthalocyanine diethylaminopropylsulfamide was prepared in the same manner as in Synthesis Example 3 except that 269 parts of diethylaminopropylamine were used instead of 210 parts of dimethylaminopropylamine. Obtained.
【００３１】＜合成例６＞合成例３において、ジメチル
アミノプロピルアミン２１０部に代えて、ジブチルアミ
ノプロピルアミン３８４部を使用した以外は合成例３と
同様にして、銅フタロシアニンジブチルアミノプロピル
スルホアミド３１９部を得た。Synthesis Example 6 Copper phthalocyanine dibutylaminopropylsulfonamide 319 was prepared in the same manner as in Synthesis Example 3 except that 384 parts of dibutylaminopropylamine were used instead of 210 parts of dimethylaminopropylamine. Got a part.
【００３２】＜実施例１＞容量５リットルのアトライタ
ー（三井鉱山株式会社製の「ＭＡ−１Ｄ型」）に、３／
８インチスチールボール１３５００部、及びβ型銅フタ
ロシアニンのクルード（大日本インキ化学工業(株)製の
「Ｆａｓｔｏｇｅｎ Ｂｌｕｅ Ｂ．８１」）５００部
を仕込み、温度８０℃、３００回転／分で８０分間乾式
磨砕して、α型とβ型が混在した銅フタロシアニンの乾
式摩砕物（αの含有率が６２％の乾式磨砕物）４９５部
を得た。この銅フタロシアニンの乾式摩砕物の平均一次
粒子径は０．０３μｍ、比表面積は７ｍ2／ｇであっ
た。Example 1 An attritor of 5 liter capacity ("MA-1D" manufactured by Mitsui Mining Co., Ltd.)
13500 parts of an 8-inch steel ball and 500 parts of β-type copper phthalocyanine crude (“Fastogen Blue B.81” manufactured by Dainippon Ink and Chemicals, Inc.) were charged and dried at a temperature of 80 ° C. and 300 rpm for 80 minutes. By milling, 495 parts of a dry milled product of copper phthalocyanine in which α-form and β-form were mixed (a dry milled product having a content of α of 62%) was obtained. The average primary particle diameter of the dry milled copper phthalocyanine was 0.03 μm, and the specific surface area was 7 m 2 / g.
【００３３】合成例１で得たアミノメチル銅フタロシア
ニン粉末７．５部と、α型とβ型が混在した銅フタロシ
アニンの乾式磨砕物９２．５部とを１０００ｍｌポリ瓶
を用いて混合して顔料組成物を得た。A mixture of 7.5 parts of the aminomethyl copper phthalocyanine powder obtained in Synthesis Example 1 and 92.5 parts of a dry milled copper phthalocyanine mixture of α-type and β-type was prepared by using a 1000 ml poly bottle to obtain a pigment. A composition was obtained.
【００３４】この顔料組成物２０部に、トルエン４５
部、出版グラビアインキ用ワニス（荒川化学工業(株)製
の「Ｗワニス」）１８５部を加え、ボールミリングして
出版グラビア用インキ２５０部を得た。To 20 parts of this pigment composition was added toluene 45
And 185 parts of a varnish for publication gravure ink ("W Varnish" manufactured by Arakawa Chemical Industries, Ltd.) were added, and ball milling was performed to obtain 250 parts of an ink for publication gravure.
【００３５】このようにして得た出版グラビア用インキ
について、以下の方法により、濃度、流動性及び貯蔵安
定性の評価を行ない、その結果を下記表１に示した。The gravure ink thus obtained was evaluated for concentration, fluidity and storage stability by the following methods. The results are shown in Table 1 below.
【００３６】＜濃度の評価方法＞出版グラビア用インキ
を０．１５ｍｍバーコーターを用いてヘンリーコート紙
に塗布した。この塗布膜を目視判定することによって、
濃度の高い方から◎、○、△、×、××の５段階に評価
した。<Evaluation Method of Concentration> An ink for gravure publication was applied to Henry coated paper using a 0.15 mm bar coater. By visually determining this coating film,
Evaluation was made in five stages of に, △, Δ, ×, XX from the higher concentration.
【００３７】＜流動性の評価方法＞ブルックフィールド
粘度計（No.２ローター又はNo.３ローター）を用いて、
２０℃、６０回転／分の条件でインキの粘度を測定し
た。<Evaluation method of fluidity> Using a Brookfield viscometer (No. 2 rotor or No. 3 rotor),
The viscosity of the ink was measured at 20 ° C. and 60 rpm.
【００３８】＜貯蔵安定性の評価方法＞５０℃で３日間
貯蔵したインキの粘度を、ブルックフィールド粘度計
（No. ２ローター又はNo. ３ローター）を用いて、２０
℃、６０回転／分の条件で測定した。<Evaluation Method of Storage Stability> The viscosity of the ink stored at 50 ° C. for 3 days was measured using a Brookfield viscometer (No. 2 rotor or No. 3 rotor).
The measurement was performed at 60 ° C. and 60 rpm.
【００３９】＜比較例１＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末を使用せず
に、実施例１で使用したα型とβ型が混在した銅フタロ
シアニンの乾式磨砕物２０部を用いた以外は、実施例１
と同様にして出版グラビア用インキを製造し、実施例１
と同様にして濃度、流動性及び貯蔵安定性の評価を行な
い、その結果を下記表１に示した。<Comparative Example 1> In Example 1, Synthesis Example 1
Example 1 was repeated except that 20 parts of a dry milled copper phthalocyanine mixture of α-type and β-type used in Example 1 was used without using the aminomethyl copper phthalocyanine powder obtained in Example 1.
A gravure ink was produced in the same manner as in Example 1.
The concentration, fluidity and storage stability were evaluated in the same manner as described above, and the results are shown in Table 1 below.
【００４０】＜比較例２＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末に代えて、銅
フタロシアニンスルフォン酸ステアリルアミン塩（１分
子中にスルフォン酸基を平均１．１個有する銅フタロシ
アニンスルフォン酸ステアリルアミン塩）を用いた以外
は、実施例１と同様にして顔料組成物を得た。<Comparative Example 2> In Example 1, Synthesis Example 1
Example 2 except that the copper methyl phthalocyanine sulfonate stearylamine salt (copper phthalocyanine sulfonate stearylamine salt having an average of 1.1 sulfonate groups per molecule) was used in place of the aminomethyl copper phthalocyanine powder obtained in the above step. In the same manner as in Example 1, a pigment composition was obtained.
【００４１】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００４２】＜比較例３＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末に代えて、銅
フタロシアニンジスルフォン酸ステアリルアミン塩（１
分子中にスルフォン酸基を平均２．３個有する銅フタロ
シアニンジスルフォン酸ステアリルアミン塩）を用いた
以外は、実施例１と同様にして顔料組成物を得た。Comparative Example 3 In Example 1, Synthesis Example 1
In place of the aminomethyl copper phthalocyanine powder obtained in the above, copper phthalocyanine disulfonate stearylamine salt (1.
A pigment composition was obtained in the same manner as in Example 1, except that copper phthalocyanine disulfonate stearylamine salt having an average of 2.3 sulfonic acid groups in the molecule was used.
【００４３】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００４４】＜実施例２＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末に代えて、合
成例２で得たジメチルアミノメチル銅フタロシアニン粉
末を用いた以外は、実施例１と同様にして顔料組成物を
得た。<Example 2> In Example 1, the synthesis example 1 was used.
A pigment composition was obtained in the same manner as in Example 1, except that the dimethylaminomethyl copper phthalocyanine powder obtained in Synthesis Example 2 was used instead of the aminomethyl copper phthalocyanine powder obtained in.
【００４５】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００４６】＜実施例３＞実施例２において、合成例２
で得たジメチルアミノメチル銅フタロシアニン粉末と、
実施例１で得たα型とβ型が混在した銅フタロシアニン
の乾式磨砕物との混合割合を７．５部：９２．５部から
３部：９７部に変更した以外は、実施例２と同様にして
顔料組成物を得た。<Example 3> In Example 2, Synthesis Example 2
Dimethylaminomethyl copper phthalocyanine powder obtained in
Example 2 was the same as Example 2 except that the mixing ratio of the copper phthalocyanine mixed with α-type and β-type obtained in Example 1 and the dry-ground product was changed from 7.5 parts: 92.5 parts to 3 parts: 97 parts. Similarly, a pigment composition was obtained.
【００４７】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００４８】＜実施例４＞実施例２において、合成例２
で得たジメチルアミノメチル銅フタロシアニン粉末と、
実施例１で得たα型とβ型が混在した銅フタロシアニン
の乾式磨砕物との混合割合を７．５部：９２．５部から
１２部：８８部に変更した以外は、実施例２と同様にし
て顔料組成物を得た。<Example 4> In Example 2, Synthesis Example 2
Dimethylaminomethyl copper phthalocyanine powder obtained in
Example 2 was the same as Example 2 except that the mixing ratio of the dry-ground material of copper phthalocyanine mixed with α-type and β-type obtained in Example 1 was changed from 7.5 parts: 92.5 parts to 12 parts: 88 parts. Similarly, a pigment composition was obtained.
【００４９】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００５０】＜実施例５＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末に代えて、合
成例３で得た銅フタロシアニンジメチルアミノプロピル
スルホアミド粉末を用いた以外は、実施例１と同様にし
て顔料組成物を得た。<Example 5> In Example 1, the synthesis example 1 was used.
A pigment composition was obtained in the same manner as in Example 1, except that the copper phthalocyanine dimethylaminopropylsulfonamide powder obtained in Synthesis Example 3 was used instead of the aminomethyl copper phthalocyanine powder obtained in.
【００５１】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００５２】＜実施例６＞容量５リットルのアトライタ
ー（三井鉱山株式会社製の「ＭＡ−１Ｄ型」）に、３／
８インチスチールボール１３５００部、β型銅フタロシ
アニンのクルード（大日本インキ化学工業(株)製の「Ｆ
ａｓｔｏｇｅｎ Ｂｌｕｅ Ｂ．８１」）４６２．５部
及び合成例３で得た銅フタロシアニンジメチルアミノプ
ロピルスルホアミド３７．５部を仕込み、温度８０℃、
３００回転／分で８０分間乾式磨砕して、α型とβ型が
混在した銅フタロシアニンの乾式摩砕物（αの含有率が
６６％の乾式磨砕物）４９５部を得た。この銅フタロシ
アニンの乾式摩砕物の平均一次粒子径は０．０３μｍ、
比表面積は７ｍ2／ｇであった。Example 6 A 5 liter attritor ("MA-1D" manufactured by Mitsui Mining Co., Ltd.)
13500 parts of 8-inch steel balls, crude of β-type copper phthalocyanine (“F” manufactured by Dainippon Ink and Chemicals, Inc.)
astogen Blue B. 81 ") 462.5 parts and the copper phthalocyanine dimethylaminopropylsulfamide 37.5 parts obtained in Synthesis Example 3 were charged at a temperature of 80 ° C.
Dry milling was performed at 300 rpm for 80 minutes to obtain 495 parts of a dry milled copper phthalocyanine mixed with α-type and β-type (a dry-milled material having an α content of 66%). The average primary particle diameter of the dry milled copper phthalocyanine is 0.03 μm,
The specific surface area was 7 m 2 / g.
【００５３】このようにして得た銅フタロシアニンの乾
式摩砕物を用いて実施例１と同様にして出版グラビア用
インキを製造し、実施例１と同様にして濃度、流動性及
び貯蔵安定性の評価を行ない、その結果を下記表１に示
した。Using the dry milled product of copper phthalocyanine thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. And the results are shown in Table 1 below.
【００５４】＜比較例４＞実施例６において、銅フタロ
シアニンジメチルアミノプロピルスルホアミド３７．５
部に代えて、銅フタロシアニンジスルフォン酸ステアリ
ルアミン塩（１分子中にスルフォン酸基を平均２．３個
有する銅フタロシアニンジスルフォン酸ステアリルアミ
ン塩）３７．５部を用いた以外は、実施例６と同様にし
て、α型とβ型が混在した銅フタロシアニンの乾式摩砕
物（αの含有率が６６％の乾式磨砕物）４９８部を得
た。Comparative Example 4 In Example 6, copper phthalocyanine dimethylaminopropylsulfamide 37.5
Example 6 except that 37.5 parts of copper phthalocyanine disulfonate stearylamine salt (copper phthalocyanine disulfonate stearylamine salt having an average of 2.3 sulfonate groups in one molecule) were used instead of 37.5 parts. In the same manner as in the above, 498 parts of a dry milled product of copper phthalocyanine in which α-form and β-form were mixed (a dry milled product having an α content of 66%) was obtained.
【００５５】このようにして得た銅フタロシアニンの乾
式摩砕物を用いて実施例１と同様にして出版グラビア用
インキを製造し、実施例１と同様にして濃度、流動性及
び貯蔵安定性の評価を行ない、その結果を下記表１に示
した。Using the dry milled product of copper phthalocyanine thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. And the results are shown in Table 1 below.
【００５６】＜実施例７＞実施例５において、銅フタロ
シアニンジメチルアミノプロピルスルホアミド粉末と、
実施例１で得たα型とβ型が混在した銅フタロシアニン
の粗顔料（乾式磨砕物）の粉末との混合割合を７．５
部：９２．５部から３部：９７部に変更した以外は、実
施例５と同様にして顔料組成物を得た。<Example 7> In Example 5, copper phthalocyanine dimethylaminopropylsulfonamide powder was used.
The mixing ratio of the powder of the crude pigment of copper phthalocyanine (dry-ground material) in which α-type and β-type were mixed in Example 1 was 7.5.
A pigment composition was obtained in the same manner as in Example 5, except that the amount was changed from 92.5 parts to 97 parts.
【００５７】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, a gravure printing ink was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００５８】＜実施例８＞実施例５において、銅フタロ
シアニンジメチルアミノプロピルスルホアミド粉末と、
実施例１で得たα型とβ型が混在した銅フタロシアニン
の粗顔料（乾式磨砕物）の粉末との混合割合を７．５
部：９２．５部から１２部：８８部に変更した以外は、
実施例５と同様にして顔料組成物を得た。<Example 8> In Example 5, copper phthalocyanine dimethylaminopropylsulfonamide powder was used.
The mixing ratio of the powder of the crude pigment of copper phthalocyanine (dry-ground material) in which α-type and β-type were mixed in Example 1 was 7.5.
Copy: 92.5 copies to 12 copies: 88 copies, except for
A pigment composition was obtained in the same manner as in Example 5.
【００５９】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００６０】＜実施例９＞実施例１において、合成例１
で得たアミノメチル銅フタロシアニン粉末に代えて、合
成例４で得た銅フタロシアニンジエチルアミノエチルス
ルホアミド粉末を用いた以外は、実施例１と同様にして
顔料組成物を得た。<Example 9> In Example 1, the synthesis example 1 was used.
A pigment composition was obtained in the same manner as in Example 1, except that the copper phthalocyanine diethylaminoethylsulfonamide powder obtained in Synthesis Example 4 was used instead of the aminomethyl copper phthalocyanine powder obtained in.
【００６１】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００６２】＜実施例１０＞実施例１において、合成例
１で得たアミノメチル銅フタロシアニン粉末に代えて、
合成例５で得た銅フタロシアニンジエチルアミノプロピ
ルスルホアミド粉末を用いた以外は、実施例１と同様に
して顔料組成物を得た。Example 10 In Example 1, the aminomethyl copper phthalocyanine powder obtained in Synthesis Example 1 was replaced with
A pigment composition was obtained in the same manner as in Example 1, except that the copper phthalocyanine diethylaminopropylsulfonamide powder obtained in Synthesis Example 5 was used.
【００６３】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００６４】＜実施例１１＞実施例１において、合成例
１で得たアミノメチル銅フタロシアニン粉末に代えて、
合成例６で得た銅フタロシアニンジブチルアミノプロピ
ルスルホアミド粉末を用いた以外は、実施例１と同様に
して顔料組成物を得た。<Example 11> In Example 1, the aminomethyl copper phthalocyanine powder obtained in Synthesis Example 1 was replaced with
A pigment composition was obtained in the same manner as in Example 1, except that the copper phthalocyanine dibutylaminopropylsulfonamide powder obtained in Synthesis Example 6 was used.
【００６５】このようにして得た顔料組成物を用いて実
施例１と同様にして出版グラビア用インキを製造し、実
施例１と同様にして濃度、流動性及び貯蔵安定性の評価
を行ない、その結果を下記表１に示した。Using the pigment composition thus obtained, an ink for publication gravure was produced in the same manner as in Example 1, and the concentration, fluidity and storage stability were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
【００６６】[0066]
【表１】 [Table 1]
【００６７】表１に示した結果から、本発明のフタロシ
アニン顔料組成物を用いた各実施例の出版グラビア用イ
ンキは、濃度が高く、流動性に優れ、貯蔵安定性の評価
においても、比較例のインキの粘度よりも極めて低く、
貯蔵安定性に優れていることが理解できる。From the results shown in Table 1, it can be seen that the gravure inks of the Examples using the phthalocyanine pigment composition of the present invention had a high concentration, excellent fluidity, and storage stability. Extremely lower than the viscosity of the ink
It can be understood that the storage stability is excellent.
【００６８】[0068]
【発明の効果】本発明の出版グラビアインキ用銅フタロ
シアニン顔料組成物は、出版グラビアインキに使用した
場合に、濃度、流動性、貯蔵安定性に優れたものであ
る。The copper phthalocyanine pigment composition for gravure ink of the present invention has excellent concentration, fluidity and storage stability when used in gravure ink for publishing.
【００６９】また、本発明の出版グラビアインキ用銅フ
タロシアニン顔料組成物は、磨砕助剤、湿潤剤、有機溶
剤及び水を使用しないで、高品位の顔料を製造すること
ができるので、従来技術のソルベントソルトミリング或
いはドライミリング法で得た乾式磨砕物を溶剤を用いて
顔料化して得られる銅フタロシアニン顔料組成物と比較
して、原料費、廃水処理に要する費用及び摩砕助剤、湿
潤剤、有機溶剤の回収に要する費用が削減でき、作業環
境の溶剤汚染がないという利点がある。The copper phthalocyanine pigment composition for gravure ink of the present invention can produce a high-quality pigment without using a grinding aid, a wetting agent, an organic solvent and water. Compared with the copper phthalocyanine pigment composition obtained by pigmenting a dry milled material obtained by the solvent salt milling or dry milling method using a solvent, the raw material cost, the cost required for wastewater treatment and the grinding aid, wetting agent In addition, there is an advantage that the cost required for recovering the organic solvent can be reduced, and there is no solvent contamination in the working environment.
【００７０】更に、本発明の出版グラビアインキ用銅フ
タロシアニン顔料組成物は、その製造に際し、顔料化工
程を必要としないので、設備化設備が不要で、顔料化に
要するエネルギーを低減でき、しかも生産量の増大が極
めて容易であるという利点がある。Furthermore, the copper phthalocyanine pigment composition for gravure ink for publication of the present invention does not require a pigmentation step in its production, so no equipment is required, the energy required for pigmentation can be reduced, and the production can be reduced. This has the advantage that the amount can be increased very easily.
【００７１】更にまた、本発明の出版グラビアインキ用
銅フタロシアニン顔料組成物は、従来技術のソルベント
ソルトミリング或いはドライミリング法で得た乾式磨砕
物を溶剤を用いて顔料化して得られる銅フタロシアニン
顔料組成物と比較して、カサが半減するので、単位容積
当たりの充填量が増す結果、容器費及び輸送費を削減で
きるという利点がある。Further, the copper phthalocyanine pigment composition for gravure printing ink of the present invention is a copper phthalocyanine pigment composition obtained by pigmentizing a dry milled material obtained by a conventional solvent salt milling or dry milling method using a solvent. Compared with a product, the amount of bulk is reduced by half, so that the amount of filling per unit volume is increased, so that there is an advantage that container costs and transportation costs can be reduced.
Claims (4)
を乾式磨砕して得られるα型とβ型が混在した銅フタロ
シアニンの乾式磨砕物と、 （２）（ａ）一般式（Ｉ） 【化１】 （式中、ＣｕＰｃは銅フタロシアニン残基を表わし、ｎ
は１〜３の整数を表わし、 Ｒ1は水素原子又は炭素原子
数１〜２のアルキル基を表わす。）で表わされる銅フタ
ロシアニン誘導体、及び（ｂ）一般式（II） 【化２】 （式中、ＣｕＰｃは銅フタロシアニン残基を表わし、ｍ
は１〜３の整数を表わし、 Ｒ2は炭素原子数１〜４のア
ルキル基を表わし、Ａは炭素原子数２〜４の線状又は分
岐状の飽和アルキレン基を表わす。）で表わされる銅フ
タロシアニン誘導体から成る群から選ばれる銅フタロシ
アニン誘導体を含有する出版グラビアインキ用銅フタロ
シアニン顔料組成物。(1) A dry milled product of copper phthalocyanine mixed with α type and β type obtained by dry milling the crude of β type copper phthalocyanine, and (2) (a) a general formula (I) Formula 1 (Wherein, CuPc represents a copper phthalocyanine residue;
Represents an integer of 1 to 3, and R 1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. A) a copper phthalocyanine derivative represented by the general formula (II): (Wherein, CuPc represents a copper phthalocyanine residue;
Represents an integer of 1 to 3, R 2 represents an alkyl group having 1 to 4 carbon atoms, and A represents a linear or branched saturated alkylene group having 2 to 4 carbon atoms. A copper phthalocyanine pigment composition for a gravure printing ink, comprising a copper phthalocyanine derivative selected from the group consisting of the copper phthalocyanine derivatives represented by the formula (1).
磨砕して得たα型とβ型が混在した銅フタロシアニンを
含有する銅フタロシアニンの乾式磨砕物が、その一次粒
子径が０．０１〜０．０５μｍの範囲にあり、その比表
面積が５〜１０ｍ2／ｇの範囲にあり、かつα型銅フタ
ロシアニンの含有率が４０〜７０重量％の範囲にある請
求項１記載の出版グラビアインキ用銅フタロシアニン顔
料組成物。2. A dry milled product of copper phthalocyanine containing copper phthalocyanine mixed with α type and β type obtained by dry milling the crude of β type copper phthalocyanine has a primary particle diameter of 0.01 to 0. The copper for gravure inks according to claim 1, wherein the specific surface area is in the range of 0.05 to 10 m 2 / g and the content of α-type copper phthalocyanine is in the range of 40 to 70% by weight. Phthalocyanine pigment composition.
１記載の銅フタロシアニン誘導体を０．５〜２０重量％
の範囲で含有する請求項１又は２記載の出版グラビアイ
ンキ用銅フタロシアニン顔料組成物。3. The copper phthalocyanine pigment composition according to claim 1, wherein said copper phthalocyanine derivative is present in an amount of 0.5 to 20% by weight.
The copper phthalocyanine pigment composition for a gravure ink for publication according to claim 1 or 2, which is contained in the range of 1 to 3.
１記載の銅フタロシアニン誘導体を２〜１５重量％の範
囲で含有する請求項１又は２記載の出版グラビアインキ
用銅フタロシアニン顔料組成物。4. The copper phthalocyanine pigment composition according to claim 1, wherein the copper phthalocyanine derivative according to claim 1 is contained in the copper phthalocyanine pigment composition in an amount of 2 to 15% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15391696A JPH101619A (en) | 1996-06-14 | 1996-06-14 | Copper phthalocyanine pigment composition for publishing gravure ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15391696A JPH101619A (en) | 1996-06-14 | 1996-06-14 | Copper phthalocyanine pigment composition for publishing gravure ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH101619A true JPH101619A (en) | 1998-01-06 |
Family
ID=15572908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15391696A Pending JPH101619A (en) | 1996-06-14 | 1996-06-14 | Copper phthalocyanine pigment composition for publishing gravure ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH101619A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2390095A (en) * | 2002-06-25 | 2003-12-31 | Riso Kagaku Corp | Ink for stencil printing |
| JP2007254628A (en) * | 2006-03-24 | 2007-10-04 | Toyo Ink Mfg Co Ltd | Oily liquid ink |
-
1996
- 1996-06-14 JP JP15391696A patent/JPH101619A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2390095A (en) * | 2002-06-25 | 2003-12-31 | Riso Kagaku Corp | Ink for stencil printing |
| JP2007254628A (en) * | 2006-03-24 | 2007-10-04 | Toyo Ink Mfg Co Ltd | Oily liquid ink |
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