JP2003026951A - Acetanilidobenzimidazolone azo pigment and method for producing the same - Google Patents
Acetanilidobenzimidazolone azo pigment and method for producing the sameInfo
- Publication number
- JP2003026951A JP2003026951A JP2001212061A JP2001212061A JP2003026951A JP 2003026951 A JP2003026951 A JP 2003026951A JP 2001212061 A JP2001212061 A JP 2001212061A JP 2001212061 A JP2001212061 A JP 2001212061A JP 2003026951 A JP2003026951 A JP 2003026951A
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- pigment
- azo pigment
- acetanilide
- formula
- represented
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｘ線回折角２θ
が、１２．3°、１２．７°、１５．３°、および２
６．７°に、その他の角度に現れるピークよりも大きい
強度のピークを示す結晶構造を有する式（Ｉ）で示され
るアセトアニリドベンツイミダゾロン系アゾ顔料、およ
びその製造方法に関する。TECHNICAL FIELD The present invention relates to an X-ray diffraction angle 2θ.
But 12.3 °, 12.7 °, 15.3 °, and 2
The present invention relates to an acetanilide benzimidazolone-based azo pigment represented by the formula (I) having a crystal structure showing a peak at 6.7 ° which has a larger intensity than peaks appearing at other angles, and a method for producing the same.
【０００２】[0002]
【化２】 （式Ｉ）[Chemical 2] (Formula I)
【０００３】[0003]
【従来の技術】Industrial Oraganic Chemistry, Secon
d, Completely Revised Ed.,Willy Herbst, Klaus Hung
er, (1997), VCH, A Wiley companyには、１）３４６〜
３４７ページに、式（ＩＩ）の一般式で表されるアセト
アニリドベンツイミダゾロン系アゾ顔料は、耐溶剤性・
耐光性に優れた顔料であり、その色域が黄色ないしオレ
ンジであることが、２）３６０〜３６１ページに、式
（Ｉ）で示されるアセトアニリドベンツイミダゾロン系
アゾ顔料が、Pigment Orange 36として自動車塗料用顔
料などに用いられ、その色相がオレンジ色であること、
赤色色相用途には、Pigment Orange 36の他に赤色顔料
キナクリドンが併用されることが、３）また４３４〜４
３５ページおよび４６１〜４６２ページには、同一化学
構造の顔料が、結晶型の違いにより異なる色相を発現す
る現象は、一般に結晶多形または、結晶変態と呼ばれて
いること、および銅フタロシアニン顔料には５種類の、
またキナクリドン顔料には３種類の結晶型が存在するこ
とが記載されている。さらに、Journal of Material Sc
ience, 27, p5101-5107 (1992).には、キナクリドン顔
料に７つの結晶型が存在することが記載されている。[Prior Art] Industrial Oraganic Chemistry, Secon
d, Completely Revised Ed., Willy Herbst, Klaus Hung
er, (1997), VCH, A Wiley company, 1) 346 ~
On page 347, acetanilide benzimidazolone-based azo pigments represented by the general formula (II) have solvent resistance
2) The acetanilide benzimidazolone azo pigment represented by the formula (I) is a pigment having excellent light fastness and a color gamut of yellow to orange. It is used for paint pigments, and its hue is orange,
In addition to Pigment Orange 36, the red pigment quinacridone may be used in combination for red hues. 3) Also 434-4
On pages 35 and 461 to 462, the phenomenon in which pigments having the same chemical structure develop different hues depending on the difference in crystal type is generally called crystal polymorphism or crystal modification, and copper phthalocyanine pigments There are 5 types,
Further, it is described that the quinacridone pigment has three types of crystal forms. In addition, the Journal of Material Sc
ience, 27, p5101-5107 (1992)., describes that the quinacridone pigment has seven crystal forms.
【０００４】[0004]
【化３】
（式ＩＩ）
（ただし、RはＣｌ、Ｂｒ、Ｆ、ＣＦ３、ＣＨ３、ＮＯ
２、ＯＣＨ３、ＯＣ２Ｈ ５、ＣＯＯＨ、ＣＯＯAlkyl、
ＣＯＮＨ２、ＣＯＮＨＣ６Ｈ５、ＳＯ２ＮＨAlkyl、Ｓ
Ｏ２ＮＨＣ６Ｈ５、 ｍ＝１〜４）[Chemical 3]
(Formula II)
(However, R is Cl, Br, F, CFThree, CHThree, NO
Two, OCHThree, OCTwoH 5, COOH, COOAlkyl,
CONHTwo, CONHC6H5, SOTwoNHAlkyl, S
OTwoNHC6H5, M = 1 to 4)
【０００５】式（Ｉ）で示されるアセトアニリドベンツ
イミダゾロン系アゾ顔料の結晶多形については、特開昭
５７−１４１４５７号公報に、１）ジアゾカップリング
反応後の粗顔料がα−変態型の結晶構造であること、
２）ジアゾカップリング反応後の粗顔料を乾燥したまた
は湿った状態で、水と全く混和できないかまたは制限的
にしか混和できない溶剤中で、特開昭４９−１１６１３
１号公報に開示された１００〜１５０℃の温度に加熱
後、顔料を単離する粗顔料の後処理法により、あるい
は、ジアゾカップリング反応後の粗顔料の水性懸濁液を
７０〜１００℃で１〜５時間加熱することにより、β−
変態型の結晶構造が得られることが記載されている。Regarding the crystal polymorphism of the acetanilide benzimidazolone type azo pigment represented by the formula (I), JP-A-57-141457 discloses that the crude pigment after the 1) diazo coupling reaction is in the α-modification type. Have a crystalline structure,
2) The crude pigment after the diazo coupling reaction, in a dry or wet state, in a solvent which is completely or only immiscible with water, is disclosed in JP-A-49-11613.
After heating to a temperature of 100 to 150 ° C. disclosed in Japanese Patent Publication No. 1), a crude pigment post-treatment method for isolating the pigment or an aqueous suspension of the crude pigment after the diazo coupling reaction is performed at 70 to 100 ° C. By heating for 1-5 hours at
It is described that a modified crystal structure is obtained.
【０００６】また、特開昭５７−１４１４５７号公報に
は、式（Ｉ）で示されるアセトアニリドベンツイミダゾ
ロン系アゾ顔料のα−変態型が、X線回折角2θ２７．３
°に大きな強度のピークを、１１．８°、１２．８°、
２３．７°に中程度の強度のピークを、１４．５°、１
６．６°、１７．５°、２０．９°に小さい強度のピー
クを有すること、β−変態型が、X線回折角2θ２７．２
°に非常に大きな強度のピークを、１２．０°、１４．
３°、１７．８°、２２．４°に中程度の強度のピーク
を、１０．１°、２０．７°、２３．２°、２４．０
°、２５．３°、２８．６°、２９．１°、２９．７°
に小さい強度のピークを有することが記載されている。
しかしながら、式（Ｉ）で示されるアセトアニリドベン
ツイミダゾロン系アゾ顔料のα−変態型顔料または、β
−変態型顔料は、いずれも色相が黄色からオレンジ色で
あるため、これを赤色色相の用途に使用する場合は、他
の赤色顔料を使用して調色する必要があった。Further, in JP-A-57-141457, the α-transformation type of the acetanilide benzimidazolone type azo pigment represented by the formula (I) has an X-ray diffraction angle of 2θ27.3.
A large intensity peak at 11.8 °, 12.8 °,
Medium intensity peaks at 23.7 °, 14.5 °, 1
It has small intensity peaks at 6.6 °, 17.5 °, and 20.9 °, and the β-transformation type has an X-ray diffraction angle of 2θ27.2.
A very large intensity peak at 12.0 °, 14.
Medium intensity peaks at 3 °, 17.8 °, 22.4 °, 10.1 °, 20.7 °, 23.2 °, 24.0.
°, 25.3 °, 28.6 °, 29.1 °, 29.7 °
Has a small intensity peak.
However, an acetanilide benzimidazolone-based azo pigment represented by the formula (I) in an α-modification type pigment or β
Since all of the modified pigments have a hue of yellow to orange, when they are used for red hues, it is necessary to use other red pigments for toning.
【０００７】[0007]
【発明が解決しようとする課題】一般に、所望の色相を
得る目的で異種顔料を混合して調色した場合、顔料の凝
集により色別れし、しばしば目的の色相が得られないこ
とがある。本発明の課題は、赤色色相用途においても異
種顔料を使用する必要のない、赤色の色相を有する、式
（Ｉ）で示されるアセトアニリドベンツイミダゾロン系
アゾ顔料、およびその製造方法を提供することである。In general, when different kinds of pigments are mixed and toned for the purpose of obtaining a desired hue, the pigments are often separated due to agglomeration of pigments, and the desired hue is often not obtained. An object of the present invention is to provide an acetanilide benzimidazolone azo pigment represented by the formula (I), which has a red hue and does not require the use of a different pigment even in a red hue application, and a method for producing the same. is there.
【０００８】[0008]
【課題を解決するための手段】本発明者は、式（Ｉ）で
示されるアセトアニリドベンツイミダゾロン系アゾ顔料
であっても、新規な変態型の結晶構造を形成させること
により、新規な赤色色相を呈することを見出した。すな
わち、本発明は、（１）Ｘ線回折角２θが、１２．3
°、１２．７°、１５．３°、および２６．７°に、そ
の他の角度に現れるピークよりも大きい強度のピークを
示す結晶構造を有する、式（Ｉ）で示されるアセトアニ
リドベンツイミダゾロン系アゾ顔料を提供し、（２）式
（Ｉ）で示されるアセトアニリドベンツイミダゾロン系
アゾ顔料の粗顔料を硫酸に溶解後、該溶液を、撹拌しな
がら水中に注ぐことによって、Ｘ線回折角２θが、１
２．3°、１２．７°、１５．３°、２６．７°に、そ
の他の角度に現れるピークよりも大きい強度のピークを
示す結晶構造を有する前記アセトアニリドベンツイミダ
ゾロン系アゾ顔料を析出させる、式（Ｉ）で示されるア
セトアニリドベンツイミダゾロン系アゾ顔料の製造方法
を提供し、さらには、（３）Ｘ線回折角２θが、２７．
４°に大きい強度のピークを示し、１０．３°、１２．
２°、１４．５°、１８．４°、２２．７°に小さい強
度のピークを示す結晶構造を有する式（Ｉ）で示される
アセトアニリドベンツイミダゾロン系アゾ顔料を硫酸に
溶解後、該溶液を、撹拌しながら水中に注ぐことによっ
て、Ｘ線回折角２θが、１２．3°、１２．７°、１
５．３°、２６．７°に、その他の角度に現れるピーク
よりも大きい強度のピークを示す結晶構造を有する前記
アセトアニリドベンツイミダゾロン系アゾ顔料を析出さ
せる、式（Ｉ）で示されるアセトアニリドベンツイミダ
ゾロン系アゾ顔料の製造方法を提供する。The inventors of the present invention have found that even with the acetanilidebenzimidazolone azo pigment represented by the formula (I), a novel red hue can be obtained by forming a new modified crystal structure. It was found that That is, according to the present invention, (1) the X-ray diffraction angle 2θ is 12.3.
Acetanilide benzimidazolone system represented by formula (I) having a crystal structure showing peaks at °, 12.7 °, 15.3 °, and 26.7 ° that are greater in intensity than peaks appearing at other angles. An azo pigment is provided, and the crude pigment of (2) acetanilidebenzimidazolone-based azo pigment represented by the formula (I) is dissolved in sulfuric acid, and then the solution is poured into water with stirring to obtain an X-ray diffraction angle of 2θ. But 1
Precipitating the acetanilide benzimidazolone azo pigment having a crystal structure showing a peak at 2.3 °, 12.7 °, 15.3 °, and 26.7 ° which has a higher intensity than the peaks appearing at other angles. And a method for producing an acetanilide benzimidazolone azo pigment represented by the formula (I), and further, (3) X-ray diffraction angle 2θ is 27.
Shows a large intensity peak at 4 °, 10.3 °, 12.
The acetanilide benzimidazolone azo pigment represented by the formula (I) having a crystal structure showing small intensity peaks at 2 °, 14.5 °, 18.4 ° and 22.7 ° is dissolved in sulfuric acid, and then the solution is prepared. X-ray diffraction angle 2θ is 12.3 °, 12.7 °, 1 by pouring into water with stirring.
An acetanilide benzine represented by the formula (I) for precipitating the acetanilide benzimidazolone azo pigment having a crystal structure showing a peak at 5.3 ° and 26.7 ° which has a higher intensity than the peaks appearing at other angles. A method for producing an imidazolone azo pigment is provided.
【０００９】[0009]
【発明の実施の形態】以下の説明において、Ｘ線回折角
２θが、１２．3°、１２．７°、１５．３°、２６．
７°に、その他の角度に現れるピークよりも大きい強度
のピークを示す、本発明の式（Ｉ）で示されるアセトア
ニリドベンツイミダゾロン系アゾ顔料の新規な結晶変態
型を「γ−変態型」と定義し、以下、特に断らない限
り、γ−変態型結晶構造を有する式（Ｉ）で示されるア
セトアニリドベンツイミダゾロン系アゾ顔料を、単に
「γ−変態型顔料」という。BEST MODE FOR CARRYING OUT THE INVENTION In the following description, the X-ray diffraction angle 2θ is 12.3 °, 12.7 °, 15.3 °, 26.
A novel crystal modification type of the acetanilidebenzimidazolone-based azo pigment represented by the formula (I) of the present invention, which shows a peak having an intensity larger than the peaks appearing at other angles at 7 °, is referred to as “γ-modification type”. Unless otherwise specified, the acetanilidebenzimidazolone-based azo pigment represented by the formula (I) having a γ-modified crystal structure will be simply referred to as “γ-modified pigment” hereinafter.
【００１０】本発明のγ−変態型顔料は、Ｘ線回折角２
θが、１２．3°、１２．７°、１５．３°、および２
６．７°に、その他の角度に現れるピークよりも大きい
強度のピークを示す結晶構造を有する式（Ｉ）で示され
るアセトアニリドベンツイミダゾロン系アゾ顔料であ
り、赤色色相を有する。上記の大きい強度の４ピーク以
外にも、１３．７°、１６．２°、および２７．７°に
中程度の強度のピークを有する。The γ-modified pigment of the present invention has an X-ray diffraction angle of 2
θ is 12.3 °, 12.7 °, 15.3 °, and 2
It is an acetanilidebenzimidazolone-based azo pigment represented by the formula (I) having a crystal structure showing a peak having an intensity larger than the peaks appearing at other angles at 6.7 °, and has a red hue. In addition to the above four peaks of high intensity, there are peaks of medium intensity at 13.7 °, 16.2 °, and 27.7 °.
【００１１】本発明のγ−変態型顔料は、α−変態型顔
料あるいは、β−変態型顔料にはない、マゼンタ色の赤
色色相を有しており、他の赤色顔料を使用することこと
なく、該γ−変態型顔料単独で、自動車用塗料や印刷イ
ンキなどに赤色顔料として使用することができる。γ−
変態型顔料は、γ−変態型以外の結晶構造を有する、式
（Ｉ）で示されるアセトアニリドベンツイミダゾロン系
アゾ顔料を原料とし、以下の方法により製造することが
できる。The γ-modification pigment of the present invention has a magenta red hue which is not found in the α-modification pigment or the β-modification pigment, and without using any other red pigment. The γ-transformed pigment alone can be used as a red pigment in automobile paints, printing inks and the like. γ-
The modified pigment can be produced by using the acetanilidebenzimidazolone-based azo pigment represented by the formula (I) as a raw material and having a crystal structure other than the γ-modified type by the following method.
【００１２】特定の結晶変態型をもたない、あるいは、
α−変態型の結晶構造を有する、式（Ｉ）で示されるア
セトアニリドベンツイミダゾロン系アゾ顔料の粗顔料、
または、Ｘ線回折角２θが、２７．４°に大きい強度の
ピークを示し、１０．３°、１２．２°、１４．５°、
１８．４°、２２．７°に小さい強度のピークを示す、
β−変態型の結晶構造を有する式（Ｉ）で示されるアセ
トアニリドベンツイミダゾロン系アゾ顔料を硫酸に溶解
後、該溶液を、撹拌しながら水中に注ぎ、析出させるこ
とにより、γ−変態型顔料を製造することができる。Does not have a specific crystal modification type, or
A crude pigment of an acetanilide benzimidazolone azo pigment represented by the formula (I), which has an α-modification type crystal structure,
Alternatively, the X-ray diffraction angle 2θ shows a large intensity peak at 27.4 °, 10.3 °, 12.2 °, 14.5 °,
Shows small intensity peaks at 18.4 ° and 22.7 °,
After the acetanilide benzimidazolone azo pigment represented by the formula (I) having a β-modification type crystal structure is dissolved in sulfuric acid, the solution is poured into water with stirring to precipitate the γ-modification type pigment. Can be manufactured.
【００１３】γ−変態型顔料の原料である、式（Ｉ）で
示されるアセトアニリドベンツイミダゾロン系アゾ顔料
の粗顔料が、２−ニトロ−４−クロロアニリンジアゾニ
ウム塩と、５−アセトアセチルアミノベンズイミダゾロ
ンとのカップリング反応によって製造できることは特開
昭５７−１４１４５７号公報の実施例１に記載されてお
り、また、β−変態型の結晶構造を有する式（Ｉ）で示
されるアセトアニリドベンツイミダゾロン系アゾ顔料
が、２−ニトロ−４−クロロアニリンジアゾニウム塩
と、５−アセトアセチルアミノベンズイミダゾロンとの
カップリング反応によって生成した粗顔料を、イソブタ
ノールおよび水中で、または、水性懸濁液の状態で加熱
することによって製造できることが、特開昭４９−１１
６１３１号公報の実施例、および、特開昭５７−１４１
４５７号公報の実施例１または実施例２に記載されてい
る。A crude pigment of an acetanilidebenzimidazolone azo pigment represented by the formula (I), which is a raw material for a γ-modification type pigment, is a 2-nitro-4-chloroaniline diazonium salt and 5-acetoacetylaminobenz. The fact that it can be produced by a coupling reaction with imidazolone is described in Example 1 of JP-A-57-141457, and the acetanilide benzimidazo represented by the formula (I) having a β-modification type crystal structure. A lone azo pigment is a crude pigment produced by a coupling reaction of 2-nitro-4-chloroaniline diazonium salt and 5-acetoacetylaminobenzimidazolone in isobutanol and water, or an aqueous suspension. It can be produced by heating in the state described in JP-A-49-11.
6131, and JP-A-57-141
It is described in Example 1 or Example 2 of Japanese Patent No. 457.
【００１４】γ−変態型顔料の製造に用いる硫酸の濃度
は、原料となる式（Ｉ）で示されるアセトアニリドベン
ツイミダゾロン系アゾ顔料の粗顔料または、β−変態型
の結晶構造を有する式（Ｉ）で示されるアセトアニリド
ベンツイミダゾロン系アゾ顔料を、部分的に、あるいは
完全に溶解できるものであれば、特に制限されないが、
溶解性の点で３０質量％以上であることが好ましい。γ
−変態型顔料の原料である、式（Ｉ）で示されるアセト
アニリドベンツイミダゾロン系アゾ顔料の粗顔料、また
はβ−変態型の結晶構造を有する式（Ｉ）で示されるア
セトアニリドベンツイミダゾロン系アゾ顔料を硫酸に溶
解後、該溶液を、撹拌しながら水中に注いでγ−変態型
顔料を析出させるときの温度は、発熱が制御しやすい点
で、１５℃以下であることが好ましい。上記の方法によ
って析出させたγ−変態型顔料を、濾別し、洗浄液が中
性になるまで水洗した後乾燥させる。The concentration of sulfuric acid used in the production of the γ-modified pigment is the crude pigment of the acetanilidebenzimidazolone azo pigment represented by the formula (I) as a raw material or the formula (1) having a β-modified crystal structure. The acetanilide benzimidazolone azo pigment represented by I) is not particularly limited as long as it can be partially or completely dissolved.
From the viewpoint of solubility, it is preferably 30% by mass or more. γ
A crude pigment of an acetanilide benzimidazolone azo pigment represented by the formula (I), which is a raw material of a modified pigment, or an acetanilide benzimidazolone azo represented by the formula (I) having a β-modified crystal structure. After the pigment is dissolved in sulfuric acid, the temperature at which the solution is poured into water with stirring to precipitate the γ-transformed pigment is preferably 15 ° C. or lower in order to easily control heat generation. The γ-transformed pigment deposited by the above method is filtered, washed with water until the washing liquid becomes neutral, and then dried.
【００１５】また、本発明のγ−変態型顔料は、用途に
適した粒子径、あるいは粒子形状にするため、有機溶
剤、水、または有機溶剤を含む水中などの媒体中で加熱
処理してもよい。加熱処理に使用する有機溶剤として
は、たとえば、メタノール、エタノール、イソプロパノ
ール、イソブタノール、エチレングリコールモノブチル
エーテルなどのアルコール類、トルエン、キシレン、ニ
トロベンゼンなどの芳香族溶剤、酢酸エチル、酢酸ブチ
ル、２−エトキシエチルアセテートなどのエステル類、
ジメチルフォルムアミド、ジメチルスルフォキシド、N-
メチルピロリドンなどの非プロトン性極性溶剤などが挙
げられる。The γ-modified pigment of the present invention may be heat-treated in a medium such as an organic solvent, water, or water containing an organic solvent in order to obtain a particle size or particle shape suitable for the purpose. Good. Examples of the organic solvent used for the heat treatment include alcohols such as methanol, ethanol, isopropanol, isobutanol, and ethylene glycol monobutyl ether, aromatic solvents such as toluene, xylene, and nitrobenzene, ethyl acetate, butyl acetate, and 2-ethoxy. Esters such as ethyl acetate,
Dimethylformamide, dimethylsulfoxide, N-
Examples include aprotic polar solvents such as methylpyrrolidone.
【００１６】上記のようにして得られた本発明の式
（Ｉ）で示されるアセトアニリドベンツイミダゾロン型
アゾ顔料は、自動車用塗料、印刷インキなどの用途に使
用することができる。The acetanilide benzimidazolone type azo pigment represented by the formula (I) of the present invention obtained as described above can be used for applications such as automobile coatings and printing inks.
【００１７】[0017]
【実施例】以下、実施例により本発明をさらに詳しく説
明する。なお、特に断らない限り、「部」および「％」
は、それぞれ「質量部」および「質量％」を表す。The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, "part" and "%"
Represents "parts by mass" and "% by mass", respectively.
【００１８】（実施例）式（Ｉ）で示されるアセトアニ
リドベンツイミダゾロン系アゾ顔料のβ−結晶変態（大
日本インキ化学工業社製「Symuler Fast Orange 4183
H」）（C.I.Pigment Orange 36）１２．５重量部を、９
５％濃硫酸３００ｍｌに、５℃以下の温度で溶解した。
該溶液を、１０００部の氷水中に攪拌しながら滴下し、
γ−変態型顔料を析出させた。析出したγ−結晶変態型
顔料を吸引濾過し、洗浄液が中性になるまで水洗した。
得られた含水圧搾ケーキを、３０００部の水に分散し、
室温で２時間攪拌した。吸引濾過、水洗後、１３０℃２
時間加熱し乾燥した。さらに、ジメチルフォルムアミド
２００ｍｌ中で２時間攪拌しながら還流し加熱処理し
た。放冷後、γ−変態型顔料を吸引濾過し、メタノー
ル、水の順に洗浄し、得られた含水圧搾ケーキを、１３
０℃２時間加熱し乾燥し、マゼンタ色のγ−変態型顔料
９．１部を得た。(Example) β-crystal modification of acetanilide benzimidazolone azo pigment represented by the formula (I) (“Symuler Fast Orange 4183 manufactured by Dainippon Ink and Chemicals, Inc.”)
H ”) (CIPigment Orange 36) 12.5 parts by weight
It was dissolved in 300 ml of 5% concentrated sulfuric acid at a temperature of 5 ° C or lower.
The solution was added dropwise to 1000 parts of ice water while stirring,
The γ-modification type pigment was deposited. The precipitated γ-crystal modification pigment was suction filtered and washed with water until the washing liquid became neutral.
Disperse the obtained water-containing pressed cake in 3000 parts of water,
The mixture was stirred at room temperature for 2 hours. After suction filtration and washing with water, 130 ℃ 2
Heated and dried for hours. Further, the mixture was refluxed in 200 ml of dimethylformamide with stirring for 2 hours and heat-treated. After cooling, the γ-transformed pigment was suction filtered, washed with methanol and water in this order, and the obtained water-containing pressed cake was washed with 13
The mixture was heated at 0 ° C. for 2 hours and dried to obtain 9.1 parts of magenta-colored γ-transformed pigment.
【００１９】得られたγ−変態型顔料の元素分析測定結
果を以下に示す。なおカッコ内の数値は、式（Ｉ）で示
されるアセトアニリドベンツイミダゾロン系アゾ顔料の
元素分析理論値を示す。元素分析測定値は、理論値に対
して±０．３％であり、測定誤差の範囲内にあった。
C ： ４８．９％ （４８．９％）
H ： ３．２％ （ ３．４％）
N ： １９．９％ （２０．１％）
また、得られたγ−変態型顔料、および式（Ｉ）で示さ
れるアセトアニリドベンツイミダゾロン系アゾ顔料のβ
−結晶変態（前記「Symuler Fast Orange 4183H」）の
質量分析測定結果を、以下に示す。ただし、質量分析測
定のイオン化法はＥＩ法であり、カッコ内の数値は各イ
オンの相対強度を表す。The results of elemental analysis of the resulting γ-transformed pigment are shown below. The numerical value in parentheses indicates the theoretical value of elemental analysis of the acetanilidebenzimidazolone azo pigment represented by the formula (I). The elemental analysis measurement value was ± 0.3% of the theoretical value, which was within the range of measurement error. C: 48.9% (48.9%) H: 3.2% (3.4%) N: 19.9% (20.1%) Further, the obtained γ-transformed pigment and the formula ( Β) of the acetanilide benzimidazolone azo pigment represented by I)
The results of mass spectrometric measurement of the crystal modification (the above-mentioned "Symuler Fast Orange 4183H") are shown below. However, the ionization method for mass spectrometry is the EI method, and the numerical value in parentheses indicates the relative intensity of each ion.
【００２０】＜γ−変態型顔料の質量分析測定結果＞
M+：４１６（１０），３４０（１１），１７５（８
４），１４９（６６），６３（１６），５２（１１），
４３（１００）
＜「Symuler Fast Orange 4183H」の質量分析測定結果
＞
M+：４１６（６），３４０（１０），１７５（８７），
１４９（５９），６３（１５），５２（１２），４３
（１００）
以上の分析結果によって、得られたγ−変態型顔料の化
学構造が、式（Ｉ）で示されるアセトアニリドベンツイ
ミダゾロン系アゾ顔料であることを確認した。<Results of Mass Spectrometric Measurement of γ-Modification Pigment> M +: 416 (10), 340 (11), 175 (8)
4), 149 (66), 63 (16), 52 (11),
43 (100) <Mass spectrometry measurement result of "Symuler Fast Orange 4183H"> M +: 416 (6), 340 (10), 175 (87),
149 (59), 63 (15), 52 (12), 43
(100) From the above analysis results, it was confirmed that the chemical structure of the obtained γ-modified pigment was the acetanilidebenzimidazolone azo pigment represented by the formula (I).
【００２１】得られたγ−変態型顔料と「Symuler Fast
Orange 4183H」の粉末X線回折による分析の結果を、図
１および図２に示す。ただし、粉末X線回折による分析
は、CuKα放射線を使用し、リガク（株）製「広角X線測
定装置RINT型」を用いて行った。なお、２θ測定誤差は
±０．２°である。図１および図２から、γ−変態型顔
料は、Ｘ線回折２θが、１２．３°、１２．７°、１
５．３°、および２６．７°に、「Symuler Fast Orang
e 4183H」には見られないピークが現れていることがわ
かる。The resulting γ-modified pigment and “Symuler Fast
The results of the powder X-ray diffraction analysis of "Orange 4183H" are shown in FIGS. However, the powder X-ray diffraction analysis was performed using CuKα radiation and using a “wide-angle X-ray measuring device RINT type” manufactured by Rigaku Corporation. The 2θ measurement error is ± 0.2 °. From FIG. 1 and FIG. 2, the γ-modified pigment has an X-ray diffraction 2θ of 12.3 °, 12.7 °, 1
At 5.3 ° and 26.7 °, “Symuler Fast Orang
It can be seen that a peak that cannot be seen in "e 4183H" appears.
【００２２】また、得られたγ−変態型顔料、および
「Symuler Fast Orange 4183H」の顔料分散塗膜の透過
スペクトル測定結果を、それぞれ図３および図４に示
す。ただし、透過スペクトル測定は、日立（株）製「紫
外・可視分光光度計U-3000型」を用い、ビヒクル用の結
着樹脂としてアルキド・メラミン樹脂を使用して上記顔
料分散塗膜を作製した。図３および図４から、γ−変態
型顔料は、「Symuler Fast Orange 4183H」に比べ、５
５０ｎｍ付近の透過率が高いことがわかる。The measurement results of the transmission spectra of the obtained γ-modified pigment and the pigment dispersion coating film of "Symuler Fast Orange 4183H" are shown in FIGS. 3 and 4, respectively. However, the transmission spectrum was measured using "Ultraviolet / visible spectrophotometer U-3000 type" manufactured by Hitachi, Ltd., and the above-mentioned pigment-dispersed coating film was prepared by using alkyd / melamine resin as a binder resin for vehicle. . From FIG. 3 and FIG. 4, the γ-modification type pigment was 5% less than “Symuler Fast Orange 4183H”.
It can be seen that the transmittance is high near 50 nm.
【００２３】[0023]
【発明の効果】本発明のγ−変態型顔料は、粗顔料、あ
るいはα−変態型もしくはβ−変態型の結晶構造を有す
る式（Ｉ）で示されるアセトアニリドベンツイミダゾロ
ン型アゾ顔料の硫酸溶液を、撹拌しながら水中に注いで
析出させるという簡便な方法で製造でき、マゼンタ色の
赤色色相を有するので、他の赤色顔料を使用して調色す
ることなく、単独で赤色用途に使用することができる。The γ-modified pigment of the present invention is a sulfuric acid solution of a crude pigment or an acetanilidebenzimidazolone type azo pigment represented by formula (I) having an α-modified or β-modified crystal structure. Can be produced by a simple method of pouring into water while stirring to cause precipitation, and since it has a magenta red hue, it can be used alone for red applications without toning using other red pigments. You can
【図１】γ−変態型顔料の粉末X線回折図である。FIG. 1 is a powder X-ray diffraction pattern of a γ-modified pigment.
【図２】「Symuler Fast Orange 4183H」の粉末X線回折
図である。FIG. 2 is a powder X-ray diffraction pattern of “Symuler Fast Orange 4183H”.
【図３】γ−変態型顔料分散塗膜の透過スペクトル図で
ある。FIG. 3 is a transmission spectrum diagram of a γ-modification type pigment dispersion coating film.
【図４】「Symuler Fast Orange 4183H」顔料分散塗膜
の透過スペクトル図である。FIG. 4 is a transmission spectrum diagram of a “Symuler Fast Orange 4183H” pigment dispersion coating film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference)
Claims (3)
７°、１５．３°、および２６．７°に、その他の角度
に現れるピークよりも大きい強度のピークを示す結晶構
造を有することを特徴とする式（Ｉ）で示されるアセト
アニリドベンツイミダゾロン系アゾ顔料。 【化１】 式（Ｉ）1. An X-ray diffraction angle 2θ of 12.3 °, 12.
An acetanilide benzimidazolone system represented by the formula (I), which has a crystal structure showing peaks at 7 °, 15.3 °, and 26.7 °, which have higher intensity than peaks appearing at other angles. Azo pigment. [Chemical 1] Formula (I)
ベンツイミダゾロン系アゾ顔料の粗顔料を硫酸に溶解
後、該溶液を、撹拌しながら水中に注ぐことによって、
Ｘ線回折角２θが、１２．３°、１２．７°、１５．３
°、２６．７°に、その他の角度に現れるピークよりも
大きい強度のピークを示す結晶構造を有するアセトアニ
リドベンツイミダゾロン系アゾ顔料を析出させることを
特徴とする上記式（Ｉ）で示されるアセトアニリドベン
ツイミダゾロン系アゾ顔料の製造方法。2. A crude pigment of the acetanilide benzimidazolone azo pigment represented by the above formula (I) is dissolved in sulfuric acid, and then the solution is poured into water with stirring,
X-ray diffraction angle 2θ is 12.3 °, 12.7 °, 15.3
The acetanilide represented by the above formula (I) is characterized by depositing acetanilide benzimidazolone-based azo pigment having a crystal structure showing a peak having an intensity larger than the peaks appearing at other angles at 90 ° and 26.7 °. A method for producing a benzimidazolone azo pigment.
強度のピークを示し、１０．３°、１２．２°、１４．
５°、１８．４°、２２．７°に小さい強度のピークを
示す結晶構造を有する上記式（Ｉ）で示されるアセトア
ニリドベンツイミダゾロン系アゾ顔料を硫酸に溶解後、
該溶液を、撹拌しながら水中に注ぐことによって、Ｘ線
回折角２θが、１２．3°、１２．７°、１５．３°、
２６．７°に、その他の角度に現れるピークよりも大き
い強度のピークを示す結晶構造を有するアセトアニリド
ベンツイミダゾロン系アゾ顔料を析出させることを特徴
とする上記式（Ｉ）で示されるアセトアニリドベンツイ
ミダゾロン系アゾ顔料の製造方法。3. An X-ray diffraction angle 2θ shows a large intensity peak at 27.4 °, 10.3 °, 12.2 °, 14.
After dissolving the acetanilide benzimidazolone azo pigment represented by the above formula (I) having a crystal structure showing small intensity peaks at 5 °, 18.4 ° and 22.7 ° in sulfuric acid,
By pouring the solution into water with stirring, the X-ray diffraction angles 2θ were 12.3 °, 12.7 °, 15.3 °,
At 26.7 °, acetanilidebenzimidazolone-based azo pigment having a crystal structure showing a peak with a higher intensity than peaks appearing at other angles is deposited, and the acetanilidebenzimidazo represented by the above formula (I) is deposited. Method for producing ron azo pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001212061A JP2003026951A (en) | 2001-07-12 | 2001-07-12 | Acetanilidobenzimidazolone azo pigment and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001212061A JP2003026951A (en) | 2001-07-12 | 2001-07-12 | Acetanilidobenzimidazolone azo pigment and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003026951A true JP2003026951A (en) | 2003-01-29 |
Family
ID=19047283
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001212061A Pending JP2003026951A (en) | 2001-07-12 | 2001-07-12 | Acetanilidobenzimidazolone azo pigment and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP2003026951A (en) |
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|---|---|---|---|---|
| JP2013032411A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and inkjet recording ink |
| JP2013032415A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| JP2013032412A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| JP2013032413A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and inkjet recording ink |
| JP2013032410A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| CN103923480A (en) * | 2014-04-21 | 2014-07-16 | 南通市争妍颜料化工有限公司 | Preparation method of orange benzimidazolone azo pigment |
| US9359503B2 (en) | 2011-07-29 | 2016-06-07 | Fujifilm Corporation | Azo pigment, method for preparing azo pigment, dispersion including azo pigment, coloring composition, and inkjet recording ink |
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2001
- 2001-07-12 JP JP2001212061A patent/JP2003026951A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013032411A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and inkjet recording ink |
| JP2013032415A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| JP2013032412A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| JP2013032413A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and inkjet recording ink |
| JP2013032410A (en) * | 2011-07-29 | 2013-02-14 | Fujifilm Corp | Azo pigment, method for producing azo pigment, dispersion containing azo pigment, tinting composition and ink for inkjet recording |
| US9359503B2 (en) | 2011-07-29 | 2016-06-07 | Fujifilm Corporation | Azo pigment, method for preparing azo pigment, dispersion including azo pigment, coloring composition, and inkjet recording ink |
| CN103923480A (en) * | 2014-04-21 | 2014-07-16 | 南通市争妍颜料化工有限公司 | Preparation method of orange benzimidazolone azo pigment |
| JP2020059844A (en) * | 2014-11-04 | 2020-04-16 | クラリアント・インターナシヨナル・リミテツド | C.i. pigment yellow 155 and method for producing the same, pigment composition and colorant composition including the pigment, and use of them as colorant |
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