JP2920400B2 - Azine colorants - Google Patents
Azine colorantsInfo
- Publication number
- JP2920400B2 JP2920400B2 JP2077683A JP7768390A JP2920400B2 JP 2920400 B2 JP2920400 B2 JP 2920400B2 JP 2077683 A JP2077683 A JP 2077683A JP 7768390 A JP7768390 A JP 7768390A JP 2920400 B2 JP2920400 B2 JP 2920400B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- unsubstituted
- alkyl group
- azine
- 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.)
- Expired - Lifetime
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- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Filters (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は鮮明なマゼンタ色〜青色の色調を有する色材
に関し、特に写真、感熱転写記録方式を初めとする各種
画像及び記録材料用、又、各種フィルター材料用、更に
は各種合成繊維用として有用な色材に関する。The present invention relates to a color material having a vivid magenta to blue color tone, and more particularly to various images and recording materials including photographic and thermal transfer recording systems, and The present invention relates to a coloring material useful for various filter materials and further for various synthetic fibers.
従来より写真用のマゼンタ色材としては、ｐ−フェニ
レンジアミン誘導体又はｐ−アミノフェノール誘導体等
の芳香族第１級アミン現像主薬の酸化体と１−アリール
−５−ピラゾロン誘導体のカップリングによって生ずる
アゾメチン色素が用いられてきた。Conventionally, magenta coloring materials for photography include azomethine formed by coupling of an oxidized aromatic primary amine developing agent such as a p-phenylenediamine derivative or a p-aminophenol derivative with a 1-aryl-5-pyrazolone derivative. Dyes have been used.
しかしながら、これらの色素は分光吸収の裾切れが悪
く、改良が望まれている。例えばカラーフィルターの赤
画素用染料として用いようとすると、長波側の裾切れが
悪いため色再現上好ましくなかった。However, these dyes have a poor spectral absorption tail, and improvement is desired. For example, when it is used as a dye for a red pixel of a color filter, it is not preferable from the viewpoint of color reproduction because the bottom on the long wave side is poor.
本発明の目的は、写真感光材料、感熱転写記録料、フ
ィルター材料、合成繊維用として有用な色材を提供する
ことにある。An object of the present invention is to provide a color material useful for a photographic light-sensitive material, a thermal transfer recording material, a filter material, and a synthetic fiber.
本発明者らは鋭意検討の結果、下記一般式〔Ｉ〕で示
されるアジン系色材によって上記目的が達成されること
を見い出した。As a result of intensive studies, the present inventors have found that the above object can be achieved by an azine-based coloring material represented by the following general formula [I].
式中、R1は水素原子、置換もしくは無置換のアルキル
基又は置換もしくは無置換のフェニル基を表し、R2は置
換もしくは無置換のアルキル基、置換もしくは無置換の
アリール基又は置換もしくは無置換のヘテロ環基を表
し、R3はアルキル基、ハロゲン原子、アルコキシ基、ス
ルホンアミド基又はアシルアミノ基を表す。ｎは０〜３
の整数を表し、ｎが２以上のとき複数のR3は同じでも異
なってもよい。ｍは０又は１を表し、Ｘはヒドロキシル
基又は置換もしくは無置換のアミノ基を表す。 In the formula, R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group, and R 2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group And R 3 represents an alkyl group, a halogen atom, an alkoxy group, a sulfonamide group or an acylamino group. n is 0-3
And when n is 2 or more, a plurality of R 3 may be the same or different. m represents 0 or 1, and X represents a hydroxyl group or a substituted or unsubstituted amino group.
以下、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
一般式〔Ｉ〕において、R1で示される基がアルキル基
の場合、各種置換基を有していてもよく、又、直鎖状で
も分岐していてもよい。更には環を形成していてもよ
い。具体的にはメチル、エチル、ｉ−プロピル、２−エ
チルヘキシル、シクロヘキシル、ベンジル、２−メトキ
シエチル、２−アセトキシエチル等の各基が挙げられ
る。好ましくは炭素数３〜18の分岐アルキル基である。In the general formula [I], when the group represented by R 1 is an alkyl group, it may have various substituents, and may be linear or branched. Further, a ring may be formed. Specific examples include groups such as methyl, ethyl, i-propyl, 2-ethylhexyl, cyclohexyl, benzyl, 2-methoxyethyl, and 2-acetoxyethyl. It is preferably a branched alkyl group having 3 to 18 carbon atoms.
R1で示される基がフェニル基の場合、各種置換基を有
していてもよい。R1が置換フェニル基の場合、フェニル
基への置換基は何でもよく、置換基の数１〜５である。
置換基の数が２以上の場合、その各々は同じでも異なっ
てもよい。好ましい置換基としては、アミド基、スルホ
ンアミド基、アルコキシ基、アリールオキシ基、カルバ
モイル基、スルファモイル基、スルホニル基である。特
に好ましくは、これらの基が更に分岐アルキル基を有し
ている場合である。When the group represented by R 1 is a phenyl group, it may have various substituents. When R 1 is a substituted phenyl group, the substituent on the phenyl group may be any, and the number of substituents is 1 to 5.
When the number of substituents is 2 or more, each of them may be the same or different. Preferred substituents are an amide group, a sulfonamide group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, and a sulfonyl group. Particularly preferably, these groups further have a branched alkyl group.
R1が水素原子の場合、一般式〔Ｉ〕は下記一般式〔I
a〕のみならず、その互変異性体である〔I a〕をも含
む。When R 1 is a hydrogen atom, the general formula [I] is represented by the following general formula [I
a) as well as its tautomer [Ia].
式中、R2,R3,X,m及びｎは一般式〔Ｉ〕と同義であ
る。 In the formula, R 2 , R 3 , X, m and n have the same meanings as in the general formula [I].
R2で示される基がアルキル基の場合、各種置換基を有
していてもよく、又、直鎖状でも分岐していてもよい。
更には環を形成していてもよい。具体的にはｉ−プロピ
ル、ｎ−ブチル、シクロヘキシル、１−フェノキシプロ
ピル等の各基が挙げられる。好ましくはアルキル基に置
換した基の炭素数も含めて、総炭素数３〜32の置換アル
キル基がよい。When the group represented by R 2 is an alkyl group, it may have various substituents, and may be linear or branched.
Further, a ring may be formed. Specific examples include i-propyl, n-butyl, cyclohexyl, and 1-phenoxypropyl. Preferably, a substituted alkyl group having 3 to 32 carbon atoms in total, including the carbon number of the group substituted with the alkyl group, is preferred.
R2で示される基がアリール基の場合、フェニル基、ナ
フチル基等の無置換アリール基の他、ハロゲン原子、シ
アノ基、スルホ基、ニトロ基、カルボキシル基等、種々
の置換基で置換されたアリール基でもよい。特に好まし
くは置換フェニル基であり、例えばペンタフルオロフェ
ニル、ｐ−シアノフェニル、４−クロロ−３−シアノフ
ェニル、４−メチルスルホニルフェニル等の各基が挙げ
られる。When the group represented by R 2 is an aryl group, it is substituted with various substituents such as a phenyl group, an unsubstituted aryl group such as a naphthyl group, a halogen atom, a cyano group, a sulfo group, a nitro group, and a carboxyl group. It may be an aryl group. Particularly preferred is a substituted phenyl group, such as pentafluorophenyl, p-cyanophenyl, 4-chloro-3-cyanophenyl, and 4-methylsulfonylphenyl.
R2で示される基がヘテロ環基の場合、各種置換基を有
していてもよく、例えば２−ピリジル、２−チアゾリ
ル、２−フリル、ベンゾイミダゾルリ、ベゾチアゾリル
等の基が挙げられる。When the group represented by R 2 is a heterocyclic group, it may have various substituents, and examples thereof include groups such as 2-pyridyl, 2-thiazolyl, 2-furyl, benzimidazole, bezothiazolyl and the like.
R2として好ましくは、置換アルキル基（特に2,5−ジ
−ｔ−アミルフェノキシ基が置換されたアルキル基）、
置換フェニル基（特にペンタフルオロフェニル、ｐ−シ
アノフェニル、４−クロロ−３−シアノフェニル、４−
メチルスルホニルフェニル）である。R 2 is preferably a substituted alkyl group (particularly an alkyl group substituted with a 2,5-di-t-amylphenoxy group),
Substituted phenyl groups (particularly pentafluorophenyl, p-cyanophenyl, 4-chloro-3-cyanophenyl, 4-
Methylsulfonylphenyl).
R3がアルキル基の場合、置換基を有していてもよく、
好ましくは炭素数８以下のアルキル基である。例えばメ
チル、エチル、ｉ−プロピル、２−メタンスルホンアミ
ドエチル及び２−メトキシエチル等の基が挙げられる。When R 3 is an alkyl group, it may have a substituent,
Preferably, it is an alkyl group having 8 or less carbon atoms. Examples include groups such as methyl, ethyl, i-propyl, 2-methanesulfonamidoethyl, and 2-methoxyethyl.
R3がハロゲン原子の場合、弗素原子又は塩素原子が好
ましい。When R 3 is a halogen atom, a fluorine atom or a chlorine atom is preferred.
R3がアルコキシ基の場合、置換基を有していてもよ
く、炭素数８以下が好ましく、例えばメトキシ、エトキ
シ、ｉ−プロポキシ、２−メトキシエトキシ等の基が挙
げられる。When R 3 is an alkoxy group, it may have a substituent and preferably has 8 or less carbon atoms, and examples thereof include groups such as methoxy, ethoxy, i-propoxy and 2-methoxyethoxy.
R3がスルホンアミド基の場合の、炭素数16以下の無置
換アルカンスルホンアミド基又は無置換ベンゼンスルホ
ンアミド基が好ましく、例えばメタンスルホンアミド、
ブタンスルホンアミド、ベンゼンスルホンアミド及びｐ
−トルエンスルホンアミド等の基が挙げられる。When R 3 is a sulfonamide group, an unsubstituted alkanesulfonamide group or an unsubstituted benzenesulfonamide group having 16 or less carbon atoms is preferable, for example, methanesulfonamide,
Butanesulfonamide, benzenesulfonamide and p
-Groups such as toluenesulfonamide.
R3がアシルアミノ基の場合、置換又は無置換の炭素数
22以下のアルカンアミド基、例えばアセトアミド、プロ
ピオンアミド、ペンタフルオロプロピオンアミド等の基
が好ましく、特に炭素数８以下の基が好ましい。又、置
換もしくは無置換のベンツアミド基、例えばベンツアミ
ド、ｍ−ニトロベンツアミド、ｐ−メトキシベンツアミ
ド等の基も好ましい。When R 3 is an acylamino group, the number of substituted or unsubstituted carbon atoms
Alkanamide groups having 22 or less, for example, groups such as acetamido, propionamide, and pentafluoropropionamide are preferable, and groups having 8 or less carbon atoms are particularly preferable. Also preferred are substituted or unsubstituted benzamide groups such as, for example, benzamide, m-nitrobenzamide, p-methoxybenzamide and the like.
Ｘで表される基が置換又は無置換アミノ基の場合、置
換基としては置換又は無置換のアルキル基、例えばメチ
ル、エチル、ｎ−ブチル、２−ヒドロキシエチル、２−
メタンスルホンアミドエチル等の基が挙げらる。Ｘとし
て特に好ましくは、炭素数８以下のジアルキルアミノ
基、例えばジエチルアミノ、Ｎ−エチル−Ｎ−（２−ヒ
ドロキシルエチル）アミノ及びＮ−エチル−Ｎ−（２−
メタンスルホンアミドエチル）アミノ等の基が挙げられ
る。When the group represented by X is a substituted or unsubstituted amino group, the substituent is a substituted or unsubstituted alkyl group such as methyl, ethyl, n-butyl, 2-hydroxyethyl,
And groups such as methanesulfonamidoethyl. X is particularly preferably a dialkylamino group having 8 or less carbon atoms, for example, diethylamino, N-ethyl-N- (2-hydroxylethyl) amino and N-ethyl-N- (2-
Groups such as methanesulfonamidoethyl) amino.
本発明のアジン系色材の具体例を以下に示すが、本発
明はこれらに限定されるものではない。Specific examples of the azine-based coloring material of the present invention are shown below, but the present invention is not limited thereto.
これら本発明の色材は、フェノール誘導体とアミノフ
ェノール誘導体もしくはｐ−フェニレンジアミン誘導体
との酸化カップリングによって容易に得ることができ
る。 These coloring materials of the present invention can be easily obtained by oxidative coupling of a phenol derivative with an aminophenol derivative or a p-phenylenediamine derivative.
〔実施例〕 以下、実施例により本発明を説明するが、本発明の実
施態様はこれに限定されない。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but embodiments of the present invention are not limited thereto.
実施例１ （例示化合物１の合成） 化合物（Ａ）13.5gを酢酸エチル200mlに溶かし、これ
に水300mlに溶かした化合物（Ｂ）13.1g、炭酸カリウム
15gを加えた。激しく撹拌しながら、が水200mlに溶かし
た赤血塩20gをゆっくり滴下した。１時間撹拌を継続し
た後、分液し、有機層に塩酸5mlを加えて室温で30分撹
拌した。水洗、乾燥、濃縮後、クロロホルム−メタノー
ルを展開液とするシリカゲルカラムクロマトグラフィー
により精製し、6.2gのマゼンタ色素を得た。NMR及びMAS
Sスペクトルより例示化合物１であることを確認した。Example 1 (Synthesis of Exemplified Compound 1) Compound (A) (13.5 g) was dissolved in ethyl acetate (200 ml), compound (B) (13.1 g) dissolved in water (300 ml), potassium carbonate
15 g were added. While stirring vigorously, 20 g of red blood salt dissolved in 200 ml of water was slowly dropped. After continuing stirring for 1 hour, liquid separation was performed, and 5 ml of hydrochloric acid was added to the organic layer, followed by stirring at room temperature for 30 minutes. After washing with water, drying and concentration, purification was performed by silica gel column chromatography using chloroform-methanol as a developing solution to obtain 6.2 g of a magenta dye. NMR and MAS
The compound was confirmed to be Exemplified Compound 1 from the S spectrum.
上記方法により得られたマゼンタ染料の吸収特性を、
別途合成したマゼンタ染料Ｍ−１と比較して以下に示
す。因みに、Ｍ−１は写真業界で一般に用いられている
代表的なアゾメチン染料である。The absorption characteristics of the magenta dye obtained by the above method,
The results are shown below in comparison with the separately synthesized magenta dye M-1. Incidentally, M-1 is a typical azomethine dye generally used in the photographic industry.
尚、ΔλL0.2は長波側の裾切れを表す数値で、最大吸
光度を与える波長と吸光度が長波側で20％に落ちる所で
の波長との差を表し、この数値が小さい程シャープカッ
トされていることを示す。 Note that Δλ L0.2 is a numerical value representing the skirt on the long wave side, and represents the difference between the wavelength giving the maximum absorbance and the wavelength where the absorbance drops to 20% on the long wave side. To indicate that
上記表から分かる様に、本発明の色材は長波側の裾切
れがシャープであり、カラーフィルターのＲ画素用染料
として好ましい。As can be seen from the above table, the coloring material of the present invention has a sharp skirt on the long wavelength side, and is preferable as a dye for R pixels of a color filter.
Claims (1)
材。 〔式中、R1は水素原子、置換もしくは無置換のアルキル
基又は置換もしくは無置換のフェニル基を表し、R2は置
換もしくは無置換のアルキル基、置換もしくは無置換の
アリール基又は置換もしくは無置換のへテロ環基を表
し、R3はアルキル基、ハロゲン原子、アルコキシ基、ス
ルホンアミド基又はアシルアミノ基を表す。ｎは０〜３
の整数を表し、ｎが２以上のとき複数のR3は同じでも異
なってもよい。ｍは０又は１を表し、Ｘはヒドロキシル
基又は置換もしくは無置換のアミノ基を表す。〕1. An azine-based coloring material represented by the following general formula [I]. [In the formula, R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group, and R 2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. Represents a substituted heterocyclic group, and R 3 represents an alkyl group, a halogen atom, an alkoxy group, a sulfonamide group or an acylamino group. n is 0-3
And when n is 2 or more, a plurality of R 3 may be the same or different. m represents 0 or 1, and X represents a hydroxyl group or a substituted or unsubstituted amino group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077683A JP2920400B2 (en) | 1990-03-26 | 1990-03-26 | Azine colorants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077683A JP2920400B2 (en) | 1990-03-26 | 1990-03-26 | Azine colorants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03275765A JPH03275765A (en) | 1991-12-06 |
| JP2920400B2 true JP2920400B2 (en) | 1999-07-19 |
Family
ID=13640694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2077683A Expired - Lifetime JP2920400B2 (en) | 1990-03-26 | 1990-03-26 | Azine colorants |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920400B2 (en) |
-
1990
- 1990-03-26 JP JP2077683A patent/JP2920400B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03275765A (en) | 1991-12-06 |
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