JP4199528B2 - Phthalocyanine compounds - Google Patents
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- JP4199528B2 JP4199528B2 JP2002354885A JP2002354885A JP4199528B2 JP 4199528 B2 JP4199528 B2 JP 4199528B2 JP 2002354885 A JP2002354885 A JP 2002354885A JP 2002354885 A JP2002354885 A JP 2002354885A JP 4199528 B2 JP4199528 B2 JP 4199528B2
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【０００１】
【発明の属する技術分野】
本発明は、溶解性に優れるフタロシアニン化合物であり、電子写真トナーやインクジェット用インクに用いられる。
【０００２】
【従来の技術】
従来、トナーを製造するに際し、通常着色剤として顔料を用い、これをバインダー樹脂と溶融、混練して得る方法が一般的であった。しかし、顔料分散では透明性が劣るため、例えば、オーバーヘッドプロジェクターの透明シートの着色に使用した場合には、投影画像が薄暗くなってしまい、色調が濁るという問題がある。
【０００３】
また、インクジェット用インクにおいても、溶解性を向上させる目的で、金属フタロシアニンスルホン酸アミドのＮ原子にモノ置換基を結合する方法が検討されている。例えば、特開平３−１９５７８３号公報では、第一級のアルコキシアルキル基をＮ原子に結合させているが、未だ溶解性が十分であるとは言えない。印字された像が水に濡れてもぼやけて流れないように、従来の水溶性型ではなく、有機溶媒可溶型の着色剤に対する要望が強くなってきている。
【発明が解決しようとする課題】
本発明の課題は、溶解性に優れる新規なフタロシアニン化合物を提供することである。即ち、より具体的には、透明性の高いトナーや水なきしないインクジェット用インクに使用できる有機溶媒や樹脂への溶解性が高いフタロシアニン化合物を提供することである。
【０００４】
【課題を解決するための手段】
本発明者等は、前記の課題を解決するために鋭意検討した。その結果、
フタロシアニン骨格の置換基として、第２級アルキル基がＮ原子に結合したスルホン酸アミド基であり、当該第２級アルキル基中に、酸素原子をエーテル結合、カルボニル結合、エステル結合の形で有するものを用いることにより所期の目的を達し得るとの知見を得て本発明を完成した。
【０００５】
すなわち、本発明は下記一般式(１)：
【化２】
で表されるフタロシアニン化合物を提供するものである。
【０００６】
本発明のフタロシアニン化合物は、前記式(１)においてＲ１及びＲ２が、炭素数１〜８のアルキル基；酸素原子をエーテル結合、カルボニル結合、エステル結合の形で１〜４個含む炭素数１〜１２のアルキル基；炭素数２〜１２のアルキルカルボニル基；又は炭素数２〜１２のアルコキシカルボニル基であるであるのが好ましい。さらに、一般式(１)において、ｎが３または４であるのが好ましく、中心金属ＭがＣｕ、Ｃｏ、Ｐｄ、ＶＯ、ＡｌＣｌ、ＡｌＯＨであるのが好ましい。
【０００７】
【発明の実施の形態】
本発明のフタロシアニン化合物は、下記一般式(１)
【０００８】
【化３】
で表される。
【０００９】
前記式(１)において、Ｒ１、Ｒ２が非置換のアルキル基であるものとしては、炭素数１〜８のアルキル基が好ましい。例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基などが挙げられる。
【００１０】
また、Ｒ１、Ｒ２が酸素原子をエーテル結合、カルボニル結合、エステル結合の形で含むアルキル基、アルキルカルボニル基、又はアルコキシカルボニル基であるものとしては、メトキシエチル基、エトキシエチル基、メトキシエトキシエチル基、エトキシエトキシエチル基、アセチル基、アセチルメチル基、アセチルエチル基、プロピオニル基、プロピオニルメチル基、プロピオニルエチル基、プロピルカルボニル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、ペントキシカルボニル基、アセチルオキシ基、プロピオニルオキシ基、ブチルカルボニルオキシ基、ヘキシルカルボニルオキシ基、ヘプチルカルボニルオキシ基、テトラヒドロフルフリルオキシメチル基、２，２−ジメチル−１，３−ジオキソラン−４−メトキシメチル基、２−(１，３−ジオキソラン)エトキシメチル基、２−(１，３−ジオキサン)エトキシメチル基などが挙げられる。
【００１１】
つぎに、フタロシアニン骨格の置換基であるスルホン酸アミド基の置換位置は、フタロシアニン骨格のα位、β位のいずれであってもよいが、α位がより好ましい。フタロシアニン骨格に結合するスルホン酸アミド基の個数ｎは１〜４であるが、３〜４が好ましい。
【００１２】
また、Ｍとしては、反応中あるいは反応後の処理中に脱離しない金属であればいずの金属も用いうるが、Ｃｕ、Ｃｏ、Ｐｄ、ＶＯ、ＡｌＣｌ及びＡｌＯＨが好ましく、とりわけＣｕが好ましい。
【００１３】
以下に、一般式(１)で表される本発明フタロシアニン化合物の具体例を示す。なお、これらの具体例は本発明化合物の範囲を限定するものではない。
【００１４】
【表１】
【表２】
このように一般式(１)で表される本発明のフタロシアニン化合物は、
(１)第２級アルキル基がＮ原子に結合したスルホン酸アミド基を有すること
(２)上記第２級アルキル基中に、酸素原子をエーテル結合、カルボニル結合、エステル結合の形で有すること
が構造上の特徴である。
【００１７】
なお、フタロシアニン化合物の置換基であるスルホン酸アミド基を修飾する置換基が第２級アルキル基でなく第１級アルキル基であると、酸素原子を含む場合においてもなおフタロシアニン化合物の溶解性が不充分である。また、該置換基が、第３級アルキル基であると、溶解性が不充分であるばかりでなく、フタロシアニン化合物の熱安定性が低下する。また、このアルキル基が酸素原子を水酸基の形で有する場合は、フタロシアニン化合物の溶解性が低下する。
【００１８】
(本発明フタロシアニン化合物の製造法)
前記一般式(１)にて表される本発明のフタロシアニン化合物は、例えば、以下のようにして製造することができる。
【００１９】
本発明化合物の原料である無置換金属フタロシアニン化合物については、市販品の購入あるいは、例えば、特開平５−１７７９４７号公報等において開示の公知の方法で製造することができる。
【００２０】
まず、無置換金属フタロシアニン化合物を、５〜１０倍重量のクロロスルホン酸中に２０℃以下を保つように少量ずつ添加する。同温で１時間攪拌後、０.５〜１℃／分の割合で昇温し、１３０〜１３５℃で４時間反応させる。８０℃まで冷却し、無置換金属フタロシアニン化合物の２〜５倍重量の塩化チオニルを７０〜８０℃に保ちながら１〜２時間かけて滴下する。同温で４〜１０時間攪拌後、１５〜２０℃まで冷却し、同温で１２時間攪拌する。反応混合物をフタロシアニン化合物の５０〜２００倍重量の氷水中に少量ずつ排出後、析出物を濾別し、氷水で中性になるまで洗浄、乾燥して、金属フタロシアニンスルホニルクロリドを得る。
【００２１】
上記の反応条件は主として金属フタロシアニンテトラスルホニルクロリドを得る条件であるが、モノ、ジあるいはトリ置換スルホニルクロリドを得たい場合には、クロロスルホン酸中での反応条件をより穏和にしていくことで可能となる。即ち、反応温度を下げるまたは反応時間を短縮することにより達成される。
【００２２】
次に、上記で得た金属フタロシアニンスルホニルクロリドを、その２倍重量の含酸素有機アミン化合物を、１５℃以下を保つよう滴下する。滴下後、２０〜３０℃で１５〜２４時間攪拌し、濾別、水洗、乾燥することにより、目的とする前記一般式(１)のフタロシアニン化合物が得られる。
【００２３】
【実施例】
以下に、本発明を実施例、比較例により更に具体的に説明するが、本発明はこれらにより限定されるものではない。なお、下記の表３には実施例１〜３及び比較例１〜４で合成した化合物の構造式を示し、後記の表４には得られた化合物の各々の溶解度測定の結果を示した。
【００２４】
【表３】
［実施例１］
銅フタロシアニン(東京化成株式会社製)１２０.０ｇをクロロスルホン酸８８０.０ｇに２０℃以下にて少量ずつ３０分をかけて装入した。次に７０〜８０℃に昇温し、同温度で１時間撹拌後、２時間かけて１３０〜１３５℃に昇温し、同温度で４時間反応した後、８０℃に冷却した。さらに塩化チオニル３５２.０ｇを７０〜８０℃に保ちながら１時間かけて滴下した後、７０〜８０℃にて４.５時間撹拌後、１５〜２０℃まで冷却し、同温度で１２時間撹拌した。
【００２６】
反応液を氷水９０００ｇに少量づつ排出した後、析出物を濾過分離し、氷水で中性になるまで洗浄して、中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ５９１.２ｇを得た。
【００２７】
得られた青色濾過ケーキ５０.１ｇに氷水１５０ｇを装入し、１０℃以下にて３０分間分散撹拌後、２−アミノ−１−メトキシブタン(東京化成株式会社製)１６.１ｇを２０分かけて１５℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水２００ｇにて分散、濾過を２回行った後、６０℃で１６時間乾燥し、青色粉末１８.６ｇを得た。さらに酢酸エチルで再結晶し、青色粉末１２.６ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ５２Ｈ６０ＣｕＮ１２Ｏ１２Ｓ４)：ＭＷ＝１２３６.９２
理論値(％)：Ｃ ５０.４９ Ｈ ４.８９ Ｎ １３.５９
実測値(％)：Ｃ ５０.４４ Ｈ ４.７８ Ｎ １３.６１
得られた化合物０.３ｇとアクリル系樹脂(デルペット８０Ｎ：旭化成株式会社製)０.５ｇ及び酢酸エチル９.５ｇの色素樹脂溶液を調製し、ガラス板にスピンコート法で塗布し、６０℃にて１時間乾燥させた後、透過スペクトルの測定を行った。この透過スペクトルを図１に示す。
【００２８】
［実施例２］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ２５.１ｇに氷水１５０ｇを装入し、１０℃以下で３０分間分散撹拌後、２−アミノ−１(２−エトキシエトキシ)ブタン９.３ｇとトリエチルアミン４.４ｇの混合溶液を２０分かけて１０℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水１５０ｇにて分散、濾過を２回行った後、６０℃にて１６時間乾燥し、青色粉末７.３ｇを得た。さらに酢酸エチルで再結晶し、青色粉末４.７ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ６４Ｈ８４ＣｕＮ１２Ｏ１６Ｓ４)：ＭＷ＝１４６９.２３
理論値(％)：Ｃ ５２.３２ Ｈ ５.７６ Ｎ １１.４４
実測値(％)：Ｃ ５２.４７ Ｈ ５.８８ Ｎ １１.３３
得られた化合物の透過スペクトルの測定を実施例１と同様に行った。この透過スペクトルを図２に示す。
【００２９】
［実施例３］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ５０.１ｇに氷水２００ｇを装入し、１０℃以下で３０分間分散撹拌後、Ｌ−バリンメチル塩酸塩(東京化成株式会社製)２９.１ｇを装入し、次にトリエチルアミン１５.８ｇを２０分かけて１０℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水２５０ｇにて分散、濾過を２回行った後、６０℃で１６時間乾燥し、青色粉末１９.９ｇを得た。さらに酢酸エチルで再結晶し、青色粉末１２.９ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ５６Ｈ６０ＣｕＮ１２Ｏ１６Ｓ４)：ＭＷ＝１３４８.９６
理論値(％)：Ｃ ４９.８６ Ｈ ４.４８ Ｎ １２.４６
実測値(％)：Ｃ ４９.７９ Ｈ ４.３５ Ｎ １２.６５
得られた化合物の透過スペクトルの測定を実施例１と同様に行った。この透過スペクトルを図３に示す。
【００３０】
［比較例１］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ７３.９ｇに氷水１５０ｇを装入し、１０℃以下で３０分間分散撹拌後、２−エトキシエチルアミン(東京化成株式会社製)２０.９ｇを２０分かけて１５℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水３００ｇにて分散、濾過を２回行った後、６０℃にて１６時間乾燥し、青色粉末２７.８ｇを得た。さらに酢酸エチルで再結晶し、青色粉末２０.１ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ４８Ｈ５２ＣｕＮ１２Ｏ１２Ｓ４)：ＭＷ＝１１８０.８１
理論値(％)：Ｃ ４８.８２ Ｈ ４.４４ Ｎ １４.２３
実測値(％)：Ｃ ４８.９２ Ｈ ４.５２ Ｎ １４.３７
【００３１】
［比較例２］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ８４.５ｇに氷水１５０ｇを装入し、１０℃以下で３０分間分散撹拌後、ＤＬ−２−アミノ−１−ブタノール(東京化成株式会社製)２０.９ｇを２０分かけて１５℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１７時間撹拌後、生成物を濾過分離し、水３００ｇにて分散、濾過を２回行った後、６０℃で１６時間乾燥し、青色粉末２７.２ｇを得た。さらにメタノールで再結晶し、青色粉末１９.２ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ４８Ｈ５２ＣｕＮ１２Ｏ１２Ｓ４)：ＭＷ＝１１８０.８１
理論値(％)：Ｃ ４８.８２ Ｈ ４.４４ Ｎ １４.２３
実測値(％)：Ｃ ４８.８８ Ｈ ４.３９ Ｎ １４.２６
【００３２】
［比較例３］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ７３.９ｇに氷水１５０ｇを装入し、１０℃以下で３０分間分散撹拌後、イソブチルアミン(東京化成株式会社製)１７.１ｇを２０分かけて１５℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水３００ｇにて分散、濾過を2回行った後、６０℃で１６時間乾燥し、青色粉末２５.９ｇを得た。トルエンで再結晶し、青色粉末１８.１ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ４８Ｈ５２ＣｕＮ１２Ｏ８Ｓ４)：ＭＷ＝１１１６.８１
理論値(％)：Ｃ ５１.６２ Ｈ ４.６９ Ｎ １５.０５
実測値(％)：Ｃ ５１.５２ Ｈ ４.７４ Ｎ １５.１３
【００３３】
［比較例４］
実施例１で得られた中間体の銅フタロシアニンテトラスルホニルクロリドの青色濾過ケーキ７３.９ｇに氷水１５０ｇを装入し、１０℃以下で３０分間分散撹拌後、tert−ブチルアミン(東京化成株式会社製)１７.１ｇを２０分かけて１５℃以下を保つように滴下した。次に、２０〜３０℃まで昇温し、同温度で１８時間撹拌後、生成物を濾過分離し、水３００ｇにて分散、濾過を２回行った後、６０℃で１６時間乾燥し、青色粉末２５.６ｇを得た。トルエンで再結晶し、青色粉末１６.３ｇを得た。この化合物の元素分析値は以下の通りであった。
元素分析値(Ｃ４８Ｈ５２ＣｕＮ１２Ｏ８Ｓ４)：ＭＷ＝１１１６.８１
理論値(％)：Ｃ ５１.６２ Ｈ ４.６９ Ｎ １５.０５
実測値(％)：Ｃ ５１.５７ Ｈ ４.７５ Ｎ １５.１４
【００３４】
(溶解度の測定)
実施例１〜３及び比較例１〜４で合成した化合物の酢酸エチルに対する溶解度の測定を行った。溶解度は、２５℃におけ酢酸エチル１００ｇに対して溶解した量(ｇ)である。結果を下記表４に示す。
【００３５】
【表４】
【発明の効果】
本発明のフタロシアニン化合物は、有機溶媒や樹脂に対する溶解性が高く、熱安定性等の耐久性に優れ、鮮明な青色〜緑色を呈するので、電子写真トナーやインクジェット用に用いる色素として好適である。
【図面の簡単な説明】
【図１】 実施例１で得られた化合物の透過スペクトルである。
【図２】 実施例２で得られた化合物の透過スペクトルである。
【図３】 実施例３で得られた化合物の透過スペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention is a phthalocyanine compound having excellent solubility, and is used for electrophotographic toners and inkjet inks.
[0002]
[Prior art]
Conventionally, when a toner is manufactured, a method is generally used in which a pigment is usually used as a colorant and is obtained by melting and kneading it with a binder resin. However, since pigment dispersion is inferior in transparency, for example, when used for coloring a transparent sheet of an overhead projector, there is a problem that a projected image becomes dim and the color tone becomes cloudy.
[0003]
In addition, in inkjet inks, a method of bonding a mono substituent to the N atom of a metal phthalocyanine sulfonic acid amide has been studied for the purpose of improving solubility. For example, in Japanese Patent Laid-Open No. 3-195783, a primary alkoxyalkyl group is bonded to an N atom, but it cannot be said that the solubility is still sufficient. In order to prevent the printed image from blurring even when it gets wet, there is an increasing demand for a colorant of an organic solvent soluble type rather than a conventional water soluble type.
[Problems to be solved by the invention]
An object of the present invention is to provide a novel phthalocyanine compound having excellent solubility. That is, more specifically, it is to provide a phthalocyanine compound having a high solubility in an organic solvent or a resin that can be used for a highly transparent toner or a water-free inkjet ink.
[0004]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above-described problems. as a result,
As a substituent of the phthalocyanine skeleton, a sulfonic acid amide group in which a secondary alkyl group is bonded to an N atom, and having an oxygen atom in the form of an ether bond, a carbonyl bond, or an ester bond in the secondary alkyl group The present invention was completed by obtaining the knowledge that the intended purpose can be achieved by using.
[0005]
That is, the present invention provides the following general formula (1):
[Chemical 2]
The phthalocyanine compound represented by these is provided.
[0006]
In the phthalocyanine compound of the present invention, R 1 and R 2 in the formula (1) are alkyl groups having 1 to 8 carbon atoms; the number of carbon atoms containing 1 to 4 oxygen atoms in the form of an ether bond, a carbonyl bond or an ester bond It is preferably an alkyl group having 1 to 12 carbon atoms; an alkylcarbonyl group having 2 to 12 carbon atoms; or an alkoxycarbonyl group having 2 to 12 carbon atoms. Furthermore, in the general formula (1), n is preferably 3 or 4, and the central metal M is preferably Cu, Co, Pd, VO, AlCl, or AlOH.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The phthalocyanine compound of the present invention has the following general formula (1)
[0008]
[Chemical 3]
It is represented by
[0009]
In the formula (1), as R 1 and R 2 are unsubstituted alkyl groups, alkyl groups having 1 to 8 carbon atoms are preferable. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group and the like.
[0010]
Examples of the alkyl group, alkylcarbonyl group, or alkoxycarbonyl group in which R 1 and R 2 contain an oxygen atom in the form of an ether bond, a carbonyl bond, or an ester bond include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxy group Ethyl group, ethoxyethoxyethyl group, acetyl group, acetylmethyl group, acetylethyl group, propionyl group, propionylmethyl group, propionylethyl group, propylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, Pentooxycarbonyl group, acetyloxy group, propionyloxy group, butylcarbonyloxy group, hexylcarbonyloxy group, heptylcarbonyloxy group, tetrahydrofurfuryloxymethyl group, 2,2-dimethyl Le-1,3-dioxolan-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group.
[0011]
Next, the substitution position of the sulfonic acid amide group which is a substituent of the phthalocyanine skeleton may be either the α-position or the β-position of the phthalocyanine skeleton, but the α-position is more preferable. The number n of sulfonic acid amide groups bonded to the phthalocyanine skeleton is 1 to 4, but 3 to 4 is preferable.
[0012]
As M, any metal can be used as long as it is a metal that does not desorb during the reaction or after the reaction, but Cu, Co, Pd, VO, AlCl, and AlOH are preferable, and Cu is particularly preferable.
[0013]
Specific examples of the phthalocyanine compound of the present invention represented by the general formula (1) are shown below. These specific examples do not limit the scope of the compounds of the present invention.
[0014]
[Table 1]
[Table 2]
Thus, the phthalocyanine compound of the present invention represented by the general formula (1) is
(1) The secondary alkyl group has a sulfonic acid amide group bonded to the N atom.
(2) A structural feature is that the secondary alkyl group has an oxygen atom in the form of an ether bond, a carbonyl bond or an ester bond.
[0017]
If the substituent that modifies the sulfonic acid amide group that is a substituent of the phthalocyanine compound is not a secondary alkyl group but a primary alkyl group, the solubility of the phthalocyanine compound is still poor even when it contains an oxygen atom. It is enough. Moreover, when the substituent is a tertiary alkyl group, not only the solubility is insufficient, but also the thermal stability of the phthalocyanine compound is lowered. Moreover, when this alkyl group has an oxygen atom in the form of a hydroxyl group, the solubility of the phthalocyanine compound is lowered.
[0018]
(Method for producing phthalocyanine compound of the present invention)
The phthalocyanine compound of the present invention represented by the general formula (1) can be produced, for example, as follows.
[0019]
The unsubstituted metal phthalocyanine compound, which is a raw material of the compound of the present invention, can be purchased commercially or by a known method disclosed in, for example, JP-A-5-177947.
[0020]
First, an unsubstituted metal phthalocyanine compound is added little by little so as to keep 20 ° C. or less in 5 to 10 times weight of chlorosulfonic acid. After stirring at the same temperature for 1 hour, the temperature is raised at a rate of 0.5 to 1 ° C./min and reacted at 130 to 135 ° C. for 4 hours. The mixture is cooled to 80 ° C., and 2 to 5 times the weight of thionyl chloride of the unsubstituted metal phthalocyanine compound is added dropwise over 1 to 2 hours while maintaining the temperature at 70 to 80 ° C. After stirring at the same temperature for 4 to 10 hours, the mixture is cooled to 15 to 20 ° C. and stirred at the same temperature for 12 hours. The reaction mixture is discharged little by little into ice water having a weight of 50 to 200 times that of the phthalocyanine compound, and the precipitate is filtered off, washed with ice water until neutral, and dried to obtain metal phthalocyanine sulfonyl chloride.
[0021]
The above reaction conditions are mainly those for obtaining metal phthalocyanine tetrasulfonyl chloride, but if you want to obtain mono-, di- or tri-substituted sulfonyl chlorides, it is possible to make the reaction conditions in chlorosulfonic acid milder It becomes. That is, it is achieved by lowering the reaction temperature or shortening the reaction time.
[0022]
Next, the metal phthalocyanine sulfonyl chloride obtained above is dropped in such a manner that an oxygen-containing organic amine compound having twice the weight thereof is kept at 15 ° C. or lower. After the dropwise addition, the mixture is stirred at 20 to 30 ° C. for 15 to 24 hours, filtered, washed with water and dried to obtain the target phthalocyanine compound of the general formula (1).
[0023]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Table 3 below shows the structural formulas of the compounds synthesized in Examples 1 to 3 and Comparative Examples 1 to 4, and Table 4 below shows the results of solubility measurement of each of the obtained compounds.
[0024]
[Table 3]
[Example 1]
Copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) 120.0 g was charged into 880.0 g of chlorosulfonic acid at 20 ° C. or less over 30 minutes. Next, the temperature was raised to 70 to 80 ° C., stirred at the same temperature for 1 hour, heated to 130 to 135 ° C. over 2 hours, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 352.0 g of thionyl chloride was added dropwise over 1 hour while maintaining at 70 to 80 ° C., then stirred at 70 to 80 ° C. for 4.5 hours, cooled to 15 to 20 ° C., and stirred at the same temperature for 12 hours. .
[0026]
The reaction solution was discharged into 9000 g of ice water little by little, and then the precipitate was separated by filtration and washed with ice water until neutral, to obtain 591.2 g of an intermediate copper phthalocyanine tetrasulfonyl chloride blue filter cake.
[0027]
To 50.1 g of the obtained blue filter cake, 150 g of ice water was charged, and after 30 minutes of dispersion and stirring at 10 ° C. or less, 16.1 g of 2-amino-1-methoxybutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was taken over 20 minutes. The solution was added dropwise so as to keep the temperature at 15 ° C. Next, the temperature was raised to 20 to 30 ° C. and stirred at the same temperature for 18 hours, and then the product was separated by filtration, dispersed in 200 g of water and filtered twice, then dried at 60 ° C. for 16 hours, and blue 18.6 g of powder was obtained. Furthermore, recrystallization was performed with ethyl acetate to obtain 12.6 g of a blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 52 H 60 CuN 12 O 12 S 4): MW = 1236.92
Theoretical value (%): C 50.49 H 4.89 N 13.59
Found (%): C 50.44 H 4.78 N 13.61
A pigment resin solution of 0.3 g of the obtained compound, 0.5 g of an acrylic resin (Delpet 80N: manufactured by Asahi Kasei Co., Ltd.) and 9.5 g of ethyl acetate was prepared, and applied to a glass plate by a spin coat method. After drying for 1 hour, the transmission spectrum was measured. This transmission spectrum is shown in FIG.
[0028]
[Example 2]
150 g of ice water was charged into 25.1 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Example 1 and dispersed and stirred at 10 ° C. or lower for 30 minutes, and then 2-amino-1 (2-ethoxyethoxy). ) A mixed solution of 9.3 g of butane and 4.4 g of triethylamine was added dropwise so as to keep the temperature at 10 ° C. or less over 20 minutes. Next, the temperature was raised to 20-30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 150 g of water and filtered twice, and then dried at 60 ° C. for 16 hours. 7.3 g of blue powder was obtained. Further, recrystallization with ethyl acetate gave 4.7 g of a blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 64 H 84 CuN 12 O 16 S 4): MW = 1469.23
Theoretical value (%): C 52.32 H 5.76 N 11.44
Found (%): C 52.47 H 5.88 N 11.33
The transmission spectrum of the obtained compound was measured in the same manner as in Example 1. This transmission spectrum is shown in FIG.
[0029]
[Example 3]
200 g of ice water was charged into 50.1 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Example 1 and dispersed and stirred at 10 ° C. or lower for 30 minutes, and then L-valine methyl hydrochloride (Tokyo Chemical Co., Ltd.). 29.1 g) was added, and then 15.8 g of triethylamine was added dropwise over 20 minutes so as to keep the temperature at 10 ° C. or lower. Next, the temperature was raised to 20 to 30 ° C., and stirred for 18 hours at the same temperature. The product was separated by filtration, dispersed in 250 g of water, filtered twice, dried at 60 ° C. for 16 hours, and blue. 19.9 g of powder was obtained. Further, recrystallization with ethyl acetate gave 12.9 g of blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 56 H 60 CuN 12 O 16 S 4): MW = 1348.96
Theoretical value (%): C 49.86 H 4.48 N 12.46
Found (%): C 49.79 H 4.35 N 12.65
The transmission spectrum of the obtained compound was measured in the same manner as in Example 1. This transmission spectrum is shown in FIG.
[0030]
[Comparative Example 1]
150 g of ice water was charged into 73.9 g of the blue copper phthalocyanine tetrasulfonyl chloride cake obtained in Example 1 and dispersed and stirred at 10 ° C. or lower for 30 minutes, and then 2-ethoxyethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). 20.9 g was added dropwise over 20 minutes so as to keep the temperature at 15 ° C. or lower. Next, the temperature was raised to 20-30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water, filtered twice, and then dried at 60 ° C. for 16 hours. 27.8 g of blue powder was obtained. Further, recrystallization with ethyl acetate gave 20.1 g of blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 48 H 52 CuN 12 O 12 S 4): MW = 1180.81
Theoretical value (%): C 48.82 H 4.44 N 14.23
Found (%): C 48.92 H 4.52 N 14.37
[0031]
[Comparative Example 2]
Into an intermediate copper phthalocyanine tetrasulfonyl chloride 84.5 g obtained in Example 1 was charged with 150 g of ice water, dispersed and stirred at 10 ° C. or lower for 30 minutes, DL-2-amino-1-butanol ( 20.9 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise so as to keep the temperature at 15 ° C. or lower over 20 minutes. Next, the temperature was raised to 20 to 30 ° C., and after stirring for 17 hours at the same temperature, the product was separated by filtration, dispersed in 300 g of water and filtered twice, then dried at 60 ° C. for 16 hours, and blue 27.2 g of powder was obtained. Further, recrystallization from methanol gave 19.2 g of a blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 48 H 52 CuN 12 O 12 S 4): MW = 1180.81
Theoretical value (%): C 48.82 H 4.44 N 14.23
Found (%): C 48.88 H 4.39 N 14.26
[0032]
[Comparative Example 3]
150 g of ice water was charged into 73.9 g of the blue filter cake of the intermediate copper phthalocyanine tetrasulfonyl chloride obtained in Example 1, and dispersed and stirred at 10 ° C. or lower for 30 minutes, and then isobutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 17 0.1 g was added dropwise over 20 minutes so as to keep the temperature at 15 ° C. or lower. Next, the temperature was raised to 20 to 30 ° C. and stirred at the same temperature for 18 hours. The product was separated by filtration, dispersed in 300 g of water, filtered twice, dried at 60 ° C. for 16 hours, and blue. 25.9 g of powder was obtained. Recrystallization from toluene gave 18.1 g of blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 48 H 52 CuN 12 O 8 S 4): MW = 1116.81
Theoretical value (%): C 51.62 H 4.69 N 15.05
Found (%): C 51.52 H 4.74 N 15.13
[0033]
[Comparative Example 4]
150 g of ice water was charged into 73.9 g of the blue copper phthalocyanine tetrasulfonyl chloride cake obtained in Example 1 and dispersed and stirred at 10 ° C. or lower for 30 minutes, and then tert-butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.). 17.1g was dripped so that 15 degrees C or less might be maintained over 20 minutes. Next, the temperature was raised to 20 to 30 ° C. and stirred at the same temperature for 18 hours, and then the product was separated by filtration, dispersed in 300 g of water and filtered twice, then dried at 60 ° C. for 16 hours, and blue 25.6 g of powder was obtained. Recrystallization from toluene gave 16.3 g of blue powder. The elemental analysis values of this compound were as follows.
Elemental analysis (C 48 H 52 CuN 12 O 8 S 4): MW = 1116.81
Theoretical value (%): C 51.62 H 4.69 N 15.05
Found (%): C 51.57 H 4.75 N 15.14
[0034]
(Measurement of solubility)
The solubility with respect to the ethyl acetate of the compound synthesize | combined in Examples 1-3 and Comparative Examples 1-4 was measured. The solubility is the amount (g) dissolved in 100 g of ethyl acetate at 25 ° C. The results are shown in Table 4 below.
[0035]
[Table 4]
【The invention's effect】
The phthalocyanine compound of the present invention has high solubility in organic solvents and resins, is excellent in durability such as thermal stability, and exhibits a clear blue to green color. Therefore, it is suitable as a dye used for electrophotographic toners and inkjets.
[Brief description of the drawings]
1 is a transmission spectrum of the compound obtained in Example 1. FIG.
2 is a transmission spectrum of the compound obtained in Example 2. FIG.
3 is a transmission spectrum of the compound obtained in Example 3. FIG.
Claims (4)
で表されるフタロシアニン化合物。The following general formula (1)
A phthalocyanine compound represented by:
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