JPS5851976B2 - Production method of unstable copper phthalocyanine for intaglio printing ink - Google Patents

Description

【発明の詳細な説明】 本発明は凹版印刷インキに多量に配合してもインキの拭
き特性を損うことのない不安定型銅フタロシアニンの製
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing unstable copper phthalocyanine, which does not impair the wiping properties of the ink even when incorporated in a large amount in an intaglio printing ink.

凹版印刷にあっては版材の表面よりも凹になっている版
面の画線構造からして、他の印刷版式のように画線部の
みに印刷インキをつけることが困難であるところから、
はじめ版全面、少なくとも画線部周辺を含めて印刷イン
キを塗着し、つぎに種々の方法で不必要な非画線部のイ
ンキを拭き去ってから印刷する。In intaglio printing, due to the line structure of the plate surface, which is concave than the surface of the plate material, it is difficult to apply printing ink only to the line area as in other printing plate types.
First, printing ink is applied to the entire surface of the plate, including at least the periphery of the image area, and then unnecessary ink in the non-image area is wiped off using various methods before printing.

この凹版印刷は主として銀行券その他の有価証券等の印
刷に用いられる。This intaglio printing is mainly used for printing bank notes and other securities.

このような理由で、凹版印刷インキとして要望される事
項に拭き特性のよいものであるということがあり、また
、製品の性格上、各種耐性の優れた着色顔料を必要とす
ること、改めていう迄もない。For these reasons, one of the requirements for an intaglio printing ink is that it has good wiping properties, and due to the nature of the product, color pigments with excellent resistance to various types are required. Nor.

銅フタロシアニンは耐光、耐熱、耐酸、耐アルカリとい
った各種の耐性に優れた顔料であるが、残念なことＯこ
、凹版印刷インキ用の着色顔料として多量に配合すると
インキの拭き特性を損い、このことは特に赤味の色調を
有する不安定型銅フタロシアニン（こその傾向が著しか
った。Copper phthalocyanine is a pigment with excellent resistance to light, heat, acid, and alkali, but unfortunately, when added in large amounts as a coloring pigment for intaglio printing inks, it impairs the wiping properties of the ink. This is especially true for unstable copper phthalocyanine, which has a reddish hue.

そこで、従来、この欠点を改良するために種々の表面処
理方法が提案され、工業的にも実施され、それなりの改
善による効果もあげられたのであるが、依然として多量
配合時のインキの拭き特性は必ずしも十分ではなく、未
だ改善しなければならない余地があった。Therefore, in the past, various surface treatment methods have been proposed to improve this drawback, have been implemented industrially, and some improvement has been achieved, but the wiping characteristics of the ink when blended in large quantities are still poor. It was not necessarily sufficient, and there was still room for improvement.

ところで、不安定型銅フタロシアニンの工業的製法とし
ては、９５φ以上の濃硫酸に粗製銅フタロシアニンを溶
解し、これを多量の水に注入して微細な顔料を生成させ
るアシドペースティング法、また６５〜８．０係の硫酸
中で生成させた硫酸塩のスラリーを水に注いで顔料化す
るアシドスラリー法があるが、着色力を重視するために
処理温度は４０℃を超えることはなかったし、また得ら
れた不安定型銅フタロシアニンは、上記した製法の別を
問わず、その粒径が０．１μｍ以下といった極めて微細
で、着色力は高いが粒子間の凝集性の強い、従って凹版
印刷インキに使用したときには流動性の悪い、また多量
に配合するとインキの拭き特性を損うような結果を招来
していた訳である。By the way, as an industrial method for producing unstable copper phthalocyanine, there is an acid pasting method in which crude copper phthalocyanine is dissolved in concentrated sulfuric acid with a diameter of 95 mm or more, and this is poured into a large amount of water to produce a fine pigment. There is an acid slurry method in which a slurry of sulfate produced in 0.0% sulfuric acid is poured into water to form a pigment, but in order to emphasize coloring power, the processing temperature did not exceed 40°C, and Regardless of the manufacturing method described above, the obtained unstable copper phthalocyanine has an extremely fine particle size of 0.1 μm or less, has high coloring power, but has strong cohesiveness between particles, and therefore cannot be used in intaglio printing inks. When mixed, the fluidity was poor, and when added in large amounts, the wiping properties of the ink were impaired.

本発明は上述した従来の欠点に鑑み、不安定型銅フタロ
シアニンの平均粒子径を上記０．１μｍ以下よりも遥か
に大きくすることによって拭き特性を顕著に改善すべく
鋭意研究の結果、遂に本発明の完成をみるに至ったもの
である。In view of the above-mentioned conventional drawbacks, the present invention has been developed as a result of intensive research aimed at significantly improving the wiping properties by making the average particle size of unstable copper phthalocyanine much larger than the above-mentioned 0.1 μm or less. It has now reached its completion.

本発明の目的は、従って、凹版印刷インキ用として、よ
り好適な不安定型銅フタロシアニンの製法を際供するこ
とにあるといえる。Therefore, it can be said that an object of the present invention is to provide a method for producing unstable copper phthalocyanine that is more suitable for use in intaglio printing ink.

本発明は二つの発明から成り、第１番目の発明は、銅フ
タロシアニンを濃度５５〜７０５〜７０重量部で加熱処
理を行ったのち、加水分解することを特徴とする凹版印
刷インキ用不安定型銅フタロシアニンの製法であり、ま
た、第２番目の発明は、第１番目の発明の構成に欠くこ
とができない事項の全部をその構成に欠くことができな
い事項の主要部としている発明であって、銅フタロシア
ニンを濃度５５〜７０５〜７０重量部で加熱処理を行っ
たのち、加水分解し、得られた沢滓の不安定型フタロシ
アニンの水分散液中で、水不溶性の微細なケイ酸を該不
安定型銅フタロシアニンの表面に沈着させることを、そ
の特徴とするものである。The present invention consists of two inventions. The first invention is an unstable copper for intaglio printing ink, which is characterized in that copper phthalocyanine is heat-treated at a concentration of 55 to 705 to 70 parts by weight and then hydrolyzed. The second invention is a method for producing phthalocyanine, and the second invention is an invention in which all of the essential features of the first invention are the main parts of the essential features of the first invention, and the second invention is an invention in which copper After heat-treating phthalocyanine at a concentration of 55 to 705 to 70 parts by weight, it is hydrolyzed, and in the resulting aqueous dispersion of unstable phthalocyanine, water-insoluble fine silicic acid is dissolved in the unstable copper. Its feature is that it is deposited on the surface of phthalocyanine.

以下に本発明を詳細すると、第１番目の発明において、
銅フタロシアニンを濃度５５〜７０５〜７０重量部で加
熱処理後、加水分解するのは、不安定型銅フタロシアニ
ンへの結晶転移を完全かつより迅速に行い、加水分解後
に平均粒子径が０．５〜２．０μ肌の不安定型銅フタロ
シアニンを得んがためである。Detailing the present invention below, in the first invention,
Copper phthalocyanine is heat-treated at a concentration of 55 to 705 to 70 parts by weight and then hydrolyzed to complete and more quickly crystallize the unstable copper phthalocyanine, resulting in an average particle size of 0.5 to 2 after hydrolysis. This is to obtain unstable copper phthalocyanine with a .0μ skin.

硫酸濃度は上記した５５〜７０５〜７０重量部くは６０
〜６５０〜６５重量部あるが、原料として安定型銅フタ
ロシアニンを使用する場合には６２〜６５２〜６５重量
部よい。The sulfuric acid concentration is 55 to 705 to 70 parts by weight or 60 parts by weight as described above.
The amount is 650 to 65 parts by weight, but if stable copper phthalocyanine is used as a raw material, the amount is preferably 62 to 652 to 65 parts by weight.

熱処理を行う際の銅フタロシアニンに対する硫酸水溶液
の液比については特にきびしい制限はないが、攪拌操作
を容易ならしめる点では銅フタロシアニン１重量部に対
して硫酸水溶液６〜１１重量部程度とするとよい。There is no particular strict limit on the liquid ratio of the aqueous sulfuric acid solution to the copper phthalocyanine during heat treatment, but in order to facilitate the stirring operation, it is preferably about 6 to 11 parts by weight of the aqueous sulfuric acid solution to 1 part by weight of the copper phthalocyanine.

熱処理温度は８０〜１１０℃の範囲が適当であり、それ
以下では結晶生成の速度が小さく処理時間が長くなって
適当でないし、それ以上に高温とすると、着色力の低下
が著しくなって不適当である。The appropriate heat treatment temperature is in the range of 80 to 110°C; if it is lower than that, the rate of crystal formation will be low and the treatment time will be long, which is not appropriate; if the temperature is higher than that, the coloring strength will drop significantly and it is not suitable. It is.

熱処理時間は処理温度によって異なるが、上記８０〜１
１０℃の温度範囲では０．５〜２．０μ扉の平均粒子径
を得るに要する時間は１〜３時間で十分である。The heat treatment time varies depending on the treatment temperature, but
In a temperature range of 10° C., 1 to 3 hours is sufficient to obtain an average particle diameter of 0.5 to 2.0 μm.

また加熱方法は外部加熱（こよってもよいこと勿論であ
るが、硫酸の希釈熱の有効利用を図ることが熱経済上有
益であって、これが為（こは、１重量部の銅フタロシア
ニンを７〜１１重量部の濃硫酸に溶解後、攪拌しながら
、硫酸濃度を６０〜６５優とするに必要な量を注入する
、或いはまた、この水中に硫酸溶液を注入する。The heating method can be external heating (of course, it is possible to use external heating), but it is thermoeconomically beneficial to effectively utilize the dilution heat of sulfuric acid. After dissolving in ~11 parts by weight of concentrated sulfuric acid, the amount necessary to bring the sulfuric acid concentration to 60-65% is poured while stirring, or alternatively, a sulfuric acid solution is poured into this water.

こうすることによって液温を１００〜１１０℃に上昇さ
せることが簡単にできる。By doing so, the liquid temperature can be easily raised to 100 to 110°C.

このように熱処理を行ってから、常法に従って多量の水
を加えて加熱加水分解を行うことにより、そのｐ滓とし
て平均粒子径０．５〜２．０μの不安定型鋼フタロシア
ニンを得ることができる。After performing the heat treatment in this manner, by adding a large amount of water and performing heating hydrolysis according to a conventional method, unstable type steel phthalocyanine with an average particle size of 0.5 to 2.0 μ can be obtained as the P slag. .

第２の発明は、第１の発明によって得られた不安定型銅
フタロシアニンを乾燥することなく水に分散し、その水
分散液中で極めて微細な水不溶性のケイ酸塩を該不安定
型鋼フタロシアニン粒子の表面に沈着させること（こよ
り、凹版インキ用ベヒクルに対する親和性を向上させる
ものであるが、ケイ酸塩の添加量はＳｉＯ２に換算して
不安定型銅フタロシアニンの重量の１．０〜ｌＯ重量φ
であることが適当である。The second invention is to disperse the unstable copper phthalocyanine obtained by the first invention in water without drying, and in the aqueous dispersion, extremely fine water-insoluble silicate is dispersed into the unstable steel phthalocyanine particles. (This improves the affinity for the intaglio ink vehicle. The amount of silicate added is 1.0 to 10% by weight φ of the unstable copper phthalocyanine in terms of SiO2.
It is appropriate that

微細な水不溶性のケイ酸塩を生成させるには、ｐＨをほ
ぼ６．５に調整した上記水分散液にアルカリ金属塩のケ
イ酸塩水溶液を加えたのち、アルミニウム、亜鉛、マグ
ネシウムの塩化物、硫酸塩、硝酸塩といった水可溶性塩
の水溶液を添加するか、或いはアルミン酸す） ＩＪウ
ムを加えたのち、アルカリ金属塩のケイ酸塩水溶液を添
加し、ついで酸を加えてｐＨを６程度に調整するといっ
た手段が採用できる。To generate fine water-insoluble silicates, an aqueous silicate solution of an alkali metal salt is added to the above aqueous dispersion whose pH is adjusted to approximately 6.5, and then chlorides of aluminum, zinc, and magnesium are added. Add an aqueous solution of water-soluble salts such as sulfates and nitrates, or add aluminic acid) After adding IJium, add an aqueous silicate solution of an alkali metal salt, and then add acid to adjust the pH to about 6. Methods such as doing this can be adopted.

本発明によって得られる不安定型銅フタロシアニンは従
来品が０．１μ扉以下の極めて微粒子であったのに対し
て、０．５〜２．０μ汎の範囲にある遥かに太きいもの
であるから、凹版印刷インキに多量に配合しても、イン
キの拭き特性を損うことがない。Whereas the unstable copper phthalocyanine obtained by the present invention is extremely fine particles of 0.1μ or less in the conventional product, it is much thicker in the range of 0.5 to 2.0μ. Even if a large amount is added to intaglio printing ink, the wiping properties of the ink will not be impaired.

また加熱処理によって多少の着色力の低下は避けられな
いが、はぼ従来品の８０係程度の着色力を有し、色の彩
かさも従来品に比べてほとんど遜色がない。Furthermore, although some reduction in coloring power is unavoidable due to heat treatment, the coloring power is approximately 80 times higher than that of conventional products, and the intensity of the color is almost comparable to that of conventional products.

更に表面（こ微細な水不溶性のケイ酸塩を沈着させたも
のでは、凹版インキ用ベヒクルに対する親和性を効果的
に向上せしめることができる。Furthermore, the surface (on which fine water-insoluble silicate is deposited) can effectively improve the affinity for the intaglio ink vehicle.

以下に実施例を示す。Examples are shown below.

実施例 １ 安定型銅フタロシアニン２０重重部を濃硫酸２２０重量
部に室温で２時間攪拌しながら溶解し、ついで水１２４
重量部を加えることによって液温は約１１０℃に上昇す
るがそのまま更に２時間攪拌を続けてから、水１０００
重量部中に注入し、加熱して９０〜９５℃で３０分間加
水分解したのち常法に従って水洗、を別した。Example 1 20 parts by weight of stable copper phthalocyanine was dissolved in 220 parts by weight of concentrated sulfuric acid with stirring at room temperature for 2 hours, and then 124 parts by weight of water was dissolved.
The temperature of the liquid rose to about 110°C by adding parts by weight, but after continuing stirring for another 2 hours,
The mixture was poured into parts by weight, heated and hydrolyzed at 90 to 95°C for 30 minutes, and washed with water according to a conventional method.

つぎにこの１滓を乾燥することなく３００重量部の水に
分散させ、５％水酸化ナトリウム水溶液でｐＨを６．５
Ｇこ調整ののち、これをケイ酸ナトリウム２重量部を２
０重量部の水Ｏこ溶解した水溶液を加え、液温を６０〜
７０’Ｃに保って３０分間攪拌した。Next, this slag was dispersed in 300 parts by weight of water without drying, and the pH was adjusted to 6.5 with a 5% aqueous sodium hydroxide solution.
After adjusting this, add 2 parts by weight of sodium silicate to 2 parts by weight.
Add an aqueous solution containing 0 parts by weight of water and reduce the temperature to 60~
The temperature was maintained at 70'C and stirred for 30 minutes.

ついで硝酸アルミニウム（結晶）３７重量部を水２０重
量部に溶解した溶液を徐々に添加すると共にさら（こ３
０分間攪拌後、常法に従って水洗、と過、乾燥、粉砕し
て平均粒子径約１μｍの不安定型銅フタロシアニンを得
た。Next, a solution of 37 parts by weight of aluminum nitrate (crystals) dissolved in 20 parts by weight of water was gradually added and further stirred.
After stirring for 0 minutes, the mixture was washed with water, filtered, dried, and pulverized according to a conventional method to obtain unstable copper phthalocyanine having an average particle size of about 1 μm.

実施例 ２ 安定型銅フタロシアニン３０重量部を濃硫酸２１０重量
部に室温で２時間攪拌しながら溶解し、ついで１５００
重量部の水中に注入し、９０〜９５℃で３０分間加水分
解したのち常法に従って水洗、ｐ別した。Example 2 30 parts by weight of stable copper phthalocyanine was dissolved in 210 parts by weight of concentrated sulfuric acid with stirring at room temperature for 2 hours, and then
The mixture was poured into parts by weight of water and hydrolyzed at 90 to 95° C. for 30 minutes, then washed with water and separated in a conventional manner.

このｐ滓を乾燥することなく ３００重量部の水に分散
させ、５φ水酸化すｌ−ＩＪウム水溶液でｐＨを６．５
に調整ののち、これをケイ酸すｌ−１，１ウム４．５重
量部を４５重量部の水に溶解した水溶液と、アルミン酸
すｌ−ＩＪウム３，８重量部を４０重量部の水に溶解し
た水溶液を順次加え、液温４０〜５０°Ｃで３０分間攪
拌した。This P slag was dispersed in 300 parts by weight of water without drying, and the pH was adjusted to 6.5 with a 5φ sulfur hydroxide solution.
This was mixed with an aqueous solution prepared by dissolving 4.5 parts by weight of sulfur silicate in 45 parts by weight of water, and 40 parts by weight of 3.8 parts by weight of sulfur aluminate. Aqueous solutions dissolved in water were added one after another and stirred for 30 minutes at a liquid temperature of 40 to 50°C.

ついで５％硫酸水溶液を用いてｐＨを６．０に調整した
のち、さらに１時間攪拌後、常法に従って水洗、沢別、
乾燥、粉砕して平均粒子径（長径）約１．２μ汎の不安
定型銅フタロシアニンを得た。Next, the pH was adjusted to 6.0 using a 5% aqueous sulfuric acid solution, and after further stirring for 1 hour, the mixture was washed with water according to a conventional method,
It was dried and pulverized to obtain an unstable copper phthalocyanine having an average particle diameter (major axis) of about 1.2 μm.

実施例 ３ 安定型銅フタロシアニン３０重量部を濃硫酸２２０重量
部Ｑこ室温で２時間攪拌しながら溶解し、ついで１２４
重量部の水を加え希釈熱による加熱下で２．５時間攪拌
を続けたのち、１５００重量部の水中ｔこ注入し、９０
〜９５℃で３０分間加水分解したのち常法に従って水洗
、沢別した。Example 3 30 parts by weight of stable copper phthalocyanine was dissolved in 220 parts by weight of concentrated sulfuric acid with stirring at room temperature for 2 hours.
After adding 1 part by weight of water and continuing stirring for 2.5 hours under heating due to the heat of dilution, 1500 parts by weight of water was poured into 90 g.
After hydrolyzing at ~95°C for 30 minutes, the mixture was washed with water and separated in a conventional manner.

このＰ滓を乾燥することなく４００重量部の水に分散さ
せ、５饅水酸化ナトリウム水溶液でｐＨを６．５に調整
ののち、ついでメタケイ酸ソーダ（モル比Ｎａ２Ｏ：
５ｉ０２ ＝＝ １ ： １、固形分４００重量部１０
重量部を水４０重量部に溶解した溶液を加え、液温５０
〜６０８Ｃで３０分間攪拌した。This P slag was dispersed in 400 parts by weight of water without drying, the pH was adjusted to 6.5 with a 50% aqueous sodium hydroxide solution, and then sodium metasilicate (molar ratio of Na2O:
5i02 == 1: 1, solid content 400 parts by weight 10
A solution of 40 parts by weight of water is added, and the liquid temperature is 50%.
Stirred at ~608C for 30 minutes.

ついで硫酸亜鉛５．４重量部を水２０重量部に溶解した
水溶液を徐々に添加すると共に、さらＱこ３０分間攪拌
後、常法に従って水洗、沢別、乾燥して平均粒子径約１
．５μ汎の不安定型銅フタロシアニンを得た。Next, an aqueous solution of 5.4 parts by weight of zinc sulfate dissolved in 20 parts by weight of water was gradually added, and after stirring for 30 minutes, the particles were washed with water, separated, and dried according to a conventional method to obtain an average particle size of about 1.
．． An unstable copper phthalocyanine with a 5μ range was obtained.

以上の実施例１〜３によって得られた不安定型銅フタロ
シアニンと、比較品として市販の不安定型銅フタロシア
ニン（こついて、表１の配合によって凹版印刷インキを
作成した。An intaglio printing ink was prepared using the unstable copper phthalocyanine obtained in Examples 1 to 3 above and a commercially available unstable copper phthalocyanine as a comparative product (using the formulations shown in Table 1).

つぎにインキの流動性と拭き特性について試験したとこ
ろ、その結果は表２に示すとおりで、拭き特性は市販品
に比して著しく改善されたことが確認できた。Next, the fluidity and wiping properties of the ink were tested, and the results are shown in Table 2, confirming that the wiping properties were significantly improved compared to commercially available products.

また流動性も概して優れているといえるに足りるもので
あった。In addition, the fluidity was generally excellent.

Claims (1)

【特許請求の範囲】 １ 銅フタロシアニンを濃度５５〜７０重量φの硫酸中
で加熱処理を行ったのち、加水分解することを特徴とす
る凹版印刷インキ用不安定型銅フタロシアニンの製法。 ２ 該加熱処理は８０〜１１０℃の温度範囲で行われる
特許請求の範囲第１項記載の凹版印刷インキ用不安定型
銅フタロシアニンの製法。 ３ 銅フクロシアニンを濃度５５〜７０重量φの硫酸中
で加熱処理を行ったのち、加水分解し、得られた沢滓の
不安定型銅フタロシアニンの水分散液中で、水不溶性の
微細なケイ酸塩を該不安定型銅フタロシアニンの表面に
沈着させることを特徴とする凹版印刷インキ用不安定型
銅フタロシアニンの製法。 ４ 該ケイ酸塩は５ｉ０２に換算して不安定型銅フタロ
シアニンの重量の１．０〜１０重量φである特許請求の
範囲第３項記載の凹版印刷インキ用不安定型銅フタロシ
アニンの製法。[Scope of Claims] 1. A method for producing unstable copper phthalocyanine for intaglio printing ink, which comprises heating copper phthalocyanine in sulfuric acid having a concentration of 55 to 70 weight φ and then hydrolyzing it. 2. The method for producing unstable copper phthalocyanine for intaglio printing ink according to claim 1, wherein the heat treatment is performed at a temperature range of 80 to 110°C. 3 Copper fucrocyanine was heat-treated in sulfuric acid with a concentration of 55 to 70 weight φ, and then hydrolyzed. A method for producing an unstable copper phthalocyanine for intaglio printing ink, which comprises depositing a salt on the surface of the unstable copper phthalocyanine. 4. The method for producing unstable copper phthalocyanine for intaglio printing ink according to claim 3, wherein the silicate has a weight φ of 1.0 to 10 of the weight of unstable copper phthalocyanine in terms of 5i02.