JPH07238231A - Azo compound and its production - Google Patents
Azo compound and its productionInfo
- Publication number
- JPH07238231A JPH07238231A JP3233294A JP3233294A JPH07238231A JP H07238231 A JPH07238231 A JP H07238231A JP 3233294 A JP3233294 A JP 3233294A JP 3233294 A JP3233294 A JP 3233294A JP H07238231 A JPH07238231 A JP H07238231A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- general formula
- compound represented
- parts
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/32—Preparation of azo dyes from other azo compounds by reacting carboxylic or sulfonic groups, or derivatives thereof, with amines; by reacting keto-groups with amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、新規なアゾ化合物、そ
れを含む着色剤およびその製造法に関する。さらに詳し
くは優れた耐光性や耐熱性を持つ不溶性アゾ顔料、その
製造法およびその使用法に関する。TECHNICAL FIELD The present invention relates to a novel azo compound, a colorant containing the same, and a method for producing the same. More specifically, it relates to an insoluble azo pigment having excellent light resistance and heat resistance, a method for producing the same, and a method for using the same.
【０００２】[0002]
【従来の技術】アゾ顔料はジアゾ化合物とカプラーとの
カップリング反応で合成される。それらに使用されるカ
プラーの中で特に２−ヒドロキシ−３−ナフトエ酸ある
いはその誘導体がよく知られている。２−ヒドロキシ−
３−ナフトエ酸から合成されるブリリアント・カーミン
６Ｂ(Ｐigment Ｒed ５７)やウォチャングレッド(Ｐi
gment Ｒed ４８)は最も重要な赤色溶性アゾ顔料とし
て知られている。2. Description of the Related Art Azo pigments are synthesized by a coupling reaction between a diazo compound and a coupler. Among the couplers used therein, 2-hydroxy-3-naphthoic acid or its derivatives are well known. 2-hydroxy-
Brilliant Carmine 6B (Pigment Red 57) and Watching Red (Pi) synthesized from 3-naphthoic acid
gment Red 48) is known as the most important red-soluble azo pigment.
【０００３】さらに２−ヒドロキシ−３−ナフトエ酸と
アニリン類との縮合で合成される２−ヒドロキシ−３−
ナフトアニリド(ナフトールＡＳ)をカプラーとして不溶
性アゾ顔料が合成されることも知られている。この様に
２−ヒドロキシ−３−ナフトエ酸から誘導されるアゾ化
合物は古くから重要な顔料として知られている。また、
近年、２−ヒドロキシ−３−ナフトエ酸の異性体である
２−ヒドロキシ−６−ナフトエ酸から誘導されるナフト
ール系顔料およびその特性も明らかにされている(特開
平２−３０２４７１号公報)。Further, 2-hydroxy-3-synthesized by condensation of 2-hydroxy-3-naphthoic acid and anilines.
It is also known that an insoluble azo pigment is synthesized by using naphthanilide (naphthol AS) as a coupler. Thus, azo compounds derived from 2-hydroxy-3-naphthoic acid have long been known as important pigments. Also,
In recent years, a naphthol-based pigment derived from 2-hydroxy-6-naphthoic acid, which is an isomer of 2-hydroxy-3-naphthoic acid, and its characteristics have been clarified (Japanese Patent Laid-Open No. 302471/1990).
【０００４】これらの化合物は、２−ヒドロキシ−３−
ナフトエ酸から誘導されるナフトール系顔料に比べ優れ
た耐熱、耐水および耐溶剤性を有することが記載されて
いる。These compounds are 2-hydroxy-3-
It is described that it has excellent heat resistance, water resistance and solvent resistance as compared with naphthol pigments derived from naphthoic acid.
【０００５】[0005]
【発明が解決しようとする課題】２−ヒドロキシ−６−
ナフトエ酸から誘導されたナフトール系顔料は優秀な顔
料であるが、色材に対してますます多様な性能が要求さ
れる現代においては、このナフトール系顔料もまた充分
に要求に対応できる性能を持つとは言い難い。本発明の
目的は、アゾ化合物の基本骨格として２−ヒドロキシ−
６−ナフトエ酸を用い、従来知られている２−ヒドロキ
シ−６−ナフトエ酸から誘導されたナフトール系顔料に
対して、特に耐光性および耐熱性において優れた新規な
アゾ化合物およびそれを含む着色剤を提供することにあ
る。Problem to be Solved by the Invention 2-Hydroxy-6-
Naphthol-based pigments derived from naphthoic acid are excellent pigments, but in today's era when more and more diverse performances are required for coloring materials, these naphthol-based pigments also have sufficient performance to meet the demands. It is hard to say. The object of the present invention is to provide 2-hydroxy- as a basic skeleton of an azo compound.
A novel azo compound excellent in light resistance and heat resistance, and a colorant containing the same, with respect to a naphthol-based pigment derived from conventionally known 2-hydroxy-6-naphthoic acid using 6-naphthoic acid To provide.
【０００６】[0006]
【課題を解決するための手段】本発明は下記一般式
(Ｉ):The present invention has the following general formula:
(I):
【化９】 [式中、Ａは炭素数６〜１２の芳香族基;Ｒ1、Ｒ1'、
Ｒ2、Ｒ2'、Ｒ3およびＲ3'はそれぞれ独立して水素原
子、アルキル基、アルコキシ基、ニトロ基またはハロゲ
ン原子を示す。]で表わされるアゾ化合物、それを含む
着色剤およびその製法を提供する。[Chemical 9] [In the formula, A is an aromatic group having 6 to 12 carbon atoms; R 1 , R 1 ′,
R 2 , R 2 ′, R 3 and R 3 ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom. ] The azo compound represented by these, the coloring agent containing it, and its manufacturing method are provided.
【０００７】本発明のアゾ化合物は新規化合物であり、
本発明のアゾ化合物から、耐光、耐熱、耐水、耐溶剤お
よび耐薬品性等に優れたアゾ顔料を得ることが可能とな
る。The azo compound of the present invention is a novel compound,
From the azo compound of the present invention, it becomes possible to obtain an azo pigment excellent in light resistance, heat resistance, water resistance, solvent resistance, chemical resistance and the like.
【０００８】本発明において、炭素数６〜１２の芳香族
基としては、例えばフェニル基、ナフタレン基、ビフェ
ニル基などがあげられる。具体的には例えば、In the present invention, examples of the aromatic group having 6 to 12 carbon atoms include phenyl group, naphthalene group and biphenyl group. Specifically, for example,
【化１０】 などが具体的に例示される。これらの芳香族基上には置
換基を有していてもよい。置換基としては、アルキル
基、アルコキシ基、ハロゲン原子などがあげられる。ア
ルキル置換基としては、例えば炭素数１〜６の低級アル
キル基、具体的にはメチル、エチル、プロピル、イソプ
ロピル、ブチル、t−ブチル、ヘキシルなどがあげられ
る。特にメチル、エチルなどが好ましい。アルコキシ基
は−Ｏ−アルキルで表され、特にメトキシ、エトキシな
どが好ましい。ハロゲン原子としては、フッ素、塩素、
臭素またはヨウ素などがあげられる。置換基は複数個ま
たは複数種であってもよい。[Chemical 10] Etc. are specifically illustrated. These aromatic groups may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and the like. Examples of the alkyl substituent include a lower alkyl group having 1 to 6 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl and the like. Methyl and ethyl are particularly preferable. The alkoxy group is represented by -O-alkyl, and methoxy and ethoxy are particularly preferable. Halogen atoms include fluorine, chlorine,
Examples include bromine and iodine. There may be plural or plural kinds of substituents.
【０００９】本発明において、Ｒ1、Ｒ2、Ｒ3などで示
されるアルキル基としては、例えば炭素数１〜６の低級
アルキル基、具体的にはメチル、エチル、プロピル、イ
ソプロピル、ブチル、t−ブチル、ヘキシルなどがあげ
られる。特にメチル、エチルなどが好ましい。アルコキ
シ基は−Ｏ−アルキルで表され、特にメトキシ、エトキ
シなどが好ましい。ハロゲン原子としては、フッ素、塩
素、臭素またはヨウ素などがあげられる。In the present invention, the alkyl group represented by R 1 , R 2 , R 3 and the like is, for example, a lower alkyl group having 1 to 6 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, butyl, t -Butyl, hexyl and the like can be mentioned. Methyl and ethyl are particularly preferable. The alkoxy group is represented by -O-alkyl, and methoxy and ethoxy are particularly preferable. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
【００１０】本発明のアゾ化合物は、着色剤、特に塗
料、印刷インキ、クレヨン、プラスチック練り込み用着
色剤として有用である。これらの用法は、従来のアゾ系
顔料と同様に行えばよい。ただし、本発明のアゾ化合物
は耐光性および耐熱性が従来の２−ヒドロキシ−６−ナ
フトエ酸から誘導されたものより優れているので、その
適用範囲をさらに広げることを可能とした。The azo compound of the present invention is useful as a colorant, especially as a colorant for paints, printing inks, crayons and plastics. These usages may be performed in the same manner as the conventional azo pigments. However, since the azo compound of the present invention is superior in light resistance and heat resistance to those derived from conventional 2-hydroxy-6-naphthoic acid, it was possible to further broaden its application range.
【００１１】耐光性が向上したことによって、太陽光線
等の光源にさらされた状態でも色あせが起きにくいの
で、外装用の塗料や高級印刷用のインキ等に有効であ
る。また、耐熱性が向上したことによって、プラスチッ
クの融点以上での高い耐熱性が要求されるプラスチック
練り込み用着色剤としても有効である。Since the light resistance is improved, fading is less likely to occur even when exposed to a light source such as sunlight, and it is effective as a paint for exterior packaging or ink for high-grade printing. Further, since the heat resistance is improved, it is also effective as a colorant for kneading plastics, which requires high heat resistance above the melting point of the plastic.
【００１２】本発明のアゾ化合物は、２−ヒドロキシ−
３−ナフトエ酸等から誘導される公知のアゾ化合物と同
様の方法により合成し得るが、例えば、一般式(ＩＩ)お
よび(ＩＩＩ):The azo compound of the present invention comprises 2-hydroxy-
Although it can be synthesized by the same method as a known azo compound derived from 3-naphthoic acid or the like, for example, general formulas (II) and (III):
【化１１】 [Chemical 11]
【化１２】 [式中、Ｒ1、Ｒ1'、Ｒ2、Ｒ2'、Ｒ3およびＲ3'は前記の
意味を有する。]で示される化合物と、一般式(ＩＶ) Ｈ2Ｎ−Ａ−ＮＨ2 (ＩＶ) [式中、Ａは前記の意味を有する。]で示される化合物と
を脱水縮合することにより製造される。[Chemical 12] [Wherein R 1 , R 1 ′, R 2 , R 2 ′, R 3 and R 3 ′ have the above-mentioned meanings. And a compound represented by the general formula (IV) H 2 N—A—NH 2 (IV) [wherein A has the above-mentioned meaning. ] The compound shown by these is manufactured by dehydrating condensation.
【００１３】脱水縮合反応は例えば、一般式(ＩＩ)およ
び(ＩＩＩ)で示されるジアゾニウム化合物と一般式(Ｉ
Ｖ)で示されるジアミン化合物をジクロルベンゼン等の
溶媒中に溶解し、加熱攪拌するとにより行われる。溶媒
としては、例えばキシレン、メシチレン等の芳香族炭化
水素類、モノクロルベンゼン、ジクロルベンゼン、トリ
クロルベンゼン、クロルナフタレン等のハロゲン化芳香
族炭化水素類、クロルニトロベンゼン、ニトロトルエン
等のニトロ化芳香族炭化水素類等を用いることができ
る。通常、反応温度は１００〜２００℃、反応時間は３
〜１０時間程度である。The dehydration condensation reaction is carried out, for example, by using the diazonium compounds represented by the general formulas (II) and (III) and the general formula (I).
It is carried out by dissolving the diamine compound represented by V) in a solvent such as dichlorobenzene and stirring with heating. Examples of the solvent include aromatic hydrocarbons such as xylene and mesitylene, halogenated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene, trichlorobenzene, and chloronaphthalene, and nitrated aromatic hydrocarbons such as chloronitrobenzene and nitrotoluene. A class etc. can be used. Usually, the reaction temperature is 100 to 200 ° C., and the reaction time is 3
It is about 10 hours.
【００１４】一般式(ＩＩ)で示されるジアゾニウム化合
物は、一般式(Ｖ):The diazonium compound represented by the general formula (II) has the general formula (V):
【化１３】 [式中、Ｒ1、Ｒ2およびＲ3は前記の意味を有する。]で
示されるアニリン化合物をジアゾ化し、得られたジアゾ
ニウム化合物を２−ヒドロキシ−６−ナフトエ酸とカッ
プリングすることにより製造される。[Chemical 13] [Wherein R 1 , R 2 and R 3 have the above-mentioned meanings. ] The aniline compound shown by these is diazotized, and it is manufactured by coupling the obtained diazonium compound with 2-hydroxy-6-naphthoic acid.
【００１５】ジアゾ化反応は例えば、一般式(Ｖ)で示さ
れるアニリン化合物塩酸水溶液に氷冷下、亜硝酸ナトリ
ウム水溶液を加えて行われる。このように調製されたジ
アゾニウム塩水溶液を２−ヒドロキシ−６−ナフトエ酸
のアルカリ水溶液に加えてカップリングが行われる。通
常、反応温度は０〜４０℃程度である。カップリング反
応の最適pＨは適宜選択されるが、２−ヒドロキシ−６
−ナフトエ酸を溶かすためのアルカリ量は最少にとどめ
ることが好ましい。The diazotization reaction is carried out, for example, by adding an aqueous sodium nitrite solution to an aqueous solution of hydrochloric acid of the aniline compound represented by the general formula (V) under ice cooling. The diazonium salt aqueous solution thus prepared is added to an alkaline aqueous solution of 2-hydroxy-6-naphthoic acid for coupling. Usually, the reaction temperature is about 0 to 40 ° C. The optimum pH of the coupling reaction is appropriately selected, but 2-hydroxy-6
-The amount of alkali for dissolving naphthoic acid is preferably kept to a minimum.
【００１６】本発明において、一般式(ＩＶ)で示される
ジアミン化合物としては、例えば次のようなものがあげ
られる。p−フェニレンジアミン、o−フェニレンジアミ
ン、m−フェニレンジアミン、２−メチル−１,４−ジア
ミノベンゼン、２−メトキシ−１,４−ジアミノベンゼ
ン、３−ブロモ−１,４−ジアミノベンゼン、１,５−ジ
アミノナフタレン、２,３−ジアミノナフタレン、１,８
−ジアミノナフタレン、４,４'−ジアミノビフェニル、
３,３'−ジアミノビフェニル、３,３'−ジクロロ−４,
４'−ジアミノビフェニルなど。In the present invention, examples of the diamine compound represented by the general formula (IV) are as follows. p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 2-methyl-1,4-diaminobenzene, 2-methoxy-1,4-diaminobenzene, 3-bromo-1,4-diaminobenzene, 1, 5-diaminonaphthalene, 2,3-diaminonaphthalene, 1,8
-Diaminonaphthalene, 4,4'-diaminobiphenyl,
3,3'-diaminobiphenyl, 3,3'-dichloro-4,
4'-diaminobiphenyl and the like.
【００１７】また、一般式(Ｖ)で示されるアニリン化合
物としては、例えば次のようなものがあげられる。アニ
リン、トルイジン(o−，m−，p−)、アニシジン(o−，m
−，p−)、フェネチジン(o−，m−，p−)、２,４−キシ
リジン、２,５−ジクロロアニリン、２−メチル−５−
ニトロアニリンなどがあげられる。上記に記載されるよ
うな一般式(ＩＶ)で示されるジアミン化合物、一般式
(Ｖ)で示されるアニリン化合物を適宜選択することによ
り、所望の一般式(Ｉ)で表されるアゾ化合物を得ること
ができる。Examples of the aniline compound represented by the general formula (V) include the followings. Aniline, toluidine (o-, m-, p-), anisidine (o-, m
-, P-), phenetidine (o-, m-, p-), 2,4-xylidine, 2,5-dichloroaniline, 2-methyl-5-
Examples include nitroaniline. A diamine compound represented by the general formula (IV) as described above, a general formula
By appropriately selecting the aniline compound represented by (V), a desired azo compound represented by the general formula (I) can be obtained.
【００１８】また、本発明のアゾ化合物は、以下の工程
で合成することもできる。２−ヒドロキシ−６−ナフト
エ酸と一般式(ＩＶ) Ｈ2Ｎ−Ａ−ＮＨ2 (IＶ) で示される化合物とを脱水縮合することにより、一般式
(ＶＩ）The azo compound of the present invention can also be synthesized in the following steps. By dehydration condensation of a compound represented by the 2-hydroxy-6-naphthoic acid and the general formula (IV) H 2 N-A -NH 2 (IV), the general formula
(VI)
【化１４】 で示される化合物を製造する。次いで一般式（Ｖ)[Chemical 14] A compound represented by Then the general formula (V)
【化１５】 で示される化合物をジアゾ化し、得られたジアゾニウム
化合物を一般式(ＶＩ)で示される化合物とカップリング
することにより、本発明のアゾ化合物を得ることができ
る。なお、脱水縮合反応、ジアゾ化反応およびカップリ
ング反応は、前記と同様の条件で反応を行えばよい。[Chemical 15] The azo compound of the present invention can be obtained by diazotizing the compound represented by the formula (1) and coupling the obtained diazonium compound with the compound represented by the general formula (VI). The dehydration condensation reaction, diazotization reaction and coupling reaction may be carried out under the same conditions as described above.
【００１９】以下に本発明を実施例により、更に具体的
に説明する。実施例中、部は重量部を示す。なお、本発
明はこれら実施例のみに限定されるものではない。The present invention will be described in more detail below with reference to examples. In the examples, “part” means “part by weight”. The present invention is not limited to these examples.
【００２０】[0020]
【実施例１】p−フェニレンビスアミド(ＶII)の合成 Example 1 Synthesis of p-phenylene bisamide (VII)
【化１６】 [Chemical 16]
【化１７】 [Chemical 17]
【００２１】２,５−ジクロルアニリン９.４部を、水５
００部及び３５％塩酸１８.２部中に加え２℃まで冷却
した０〜２℃に保ちながら亜硝酸ナトリウム４.３部を
水２０部に溶解した溶液を滴下してジアゾ化を行なっ
た。他方、２−ヒドロキシ−６−ナフトエ酸１３.８部
を、水酸化ナトリウム８.４部を含む水１０００部に溶
解し、１７℃に保った。2,5-Dichloroaniline (9.4 parts) and water (5 parts)
A solution of 4.3 parts of sodium nitrite dissolved in 20 parts of water was added dropwise to 00 parts and 18.2 parts of 35% hydrochloric acid and cooled to 2 ° C. to carry out diazotization. On the other hand, 13.8 parts of 2-hydroxy-6-naphthoic acid was dissolved in 1000 parts of water containing 8.4 parts of sodium hydroxide and kept at 17 ° C.
【００２２】これに上述のジアゾ溶液を約３０分で滴下
しカップリング反応を行った。２時間攪拌後、５％塩酸
でpＨを３.０に調整した。次いで７０℃に昇温して３０
分攪拌したのち反応物を濾過した。ケーキを水洗、乾燥
して２０.２gの２−ヒドロキシ−６−ナフトエ酸−１−
アゾ(２',５'−ジクロルベンゼン)を得た(対理論収率＝
８３.５％)The above-mentioned diazo solution was added dropwise to this for about 30 minutes to carry out a coupling reaction. After stirring for 2 hours, the pH was adjusted to 3.0 with 5% hydrochloric acid. Then, raise the temperature to 70 ° C. and raise to 30
After stirring for a minute, the reaction was filtered. The cake is washed with water and dried to give 20.2 g of 2-hydroxy-6-naphthoic acid-1-
Azo (2 ', 5'-dichlorobenzene) was obtained (vs. theoretical yield =
(83.5%)
【００２３】このアゾ化合物１６.９部をo−ジクロルベ
ンゼン１３５.２倍にケンダクしジメチルホルムアミド
０.２部次いで塩化チオニル１５.０部を３０分かけて滴
下した。その後３hrを要して１１０℃まで昇温する。反
応終了後２０℃まで冷却し、濾過、o−ジクロルベンゼ
ン１００部及び石油エーテル５０部で洗浄し、乾燥して
１４.３部の２−ヒドロキシ−６−ナフトエ酸クロライ
ド−１−アゾ(２',５'−ジクロルベンゼン)を得た。16.9 parts of this azo compound was added to 135.2 times the amount of o-dichlorobenzene, 0.2 parts of dimethylformamide and 15.0 parts of thionyl chloride were added dropwise over 30 minutes. After that, the temperature is raised to 110 ° C. over 3 hours. After completion of the reaction, the mixture was cooled to 20 ° C., filtered, washed with 100 parts of o-dichlorobenzene and 50 parts of petroleum ether, dried, and 14.3 parts of 2-hydroxy-6-naphthoic acid chloride-1-azo (2 ', 5'-dichlorobenzene) was obtained.
【００２４】次にこの酸クロライド１３.３部とo−ジク
ロルベンゼン１８６部及びp−フェニレンジアミン１.６
部を室温で加え０.５hr保持した。その後２hrを要して
１４５℃まで昇温し、同温度で４hr反応した。反応液を
８０℃まで冷却し、濾過、o−ジクロルベンゼン１００
部及びメタノール１００部で順次洗浄、乾燥して粗生成
物１２.６gを得た。Next, 13.3 parts of this acid chloride, 186 parts of o-dichlorobenzene and 1.6 of p-phenylenediamine.
Part was added at room temperature and kept for 0.5 hr. After that, the temperature was raised to 145 ° C. over 2 hours, and the reaction was performed for 4 hours at the same temperature. The reaction solution was cooled to 80 ° C., filtered, and o-dichlorobenzene 100 was added.
Parts and 100 parts of methanol and then dried to obtain 12.6 g of a crude product.
【００２５】次にこの粗生成物１２.６部をo−ジクロル
ベンゼン２００部と共に１７０℃で洗浄して濾過後、o
−ジクロルベンゼン１００部及びメタノールで順次洗浄
乾燥して下記目的化合物１０.８gを得た。赤外線吸収ス
ペクトル(ＫＢr法)を図１に示す。分解点は３４３.３℃
であった。Next, 12.6 parts of this crude product was washed with 200 parts of o-dichlorobenzene at 170 ° C., filtered, and
-Washing and drying with 100 parts of dichlorobenzene and methanol successively to obtain 10.8 g of the following target compound. The infrared absorption spectrum (KBr method) is shown in FIG. Decomposition point is 343.3 ° C
Met.
【００２６】[0026]
【実施例２】p−フェニレンビスアミド化合物(ＶIII)の合成 Example 2 Synthesis of p-phenylene bisamide compound (VIII)
【化１８】 [Chemical 18]
【００２７】２,５−ジクロルアニリンの代りに２−メ
チル−５−ニトロアニリン９.１部を用いた以外は実施
例１と同様の操作を行い、目的化合物を得た。赤外線吸
収スペクトル(ＫＢr法)を図２に示す。分解点は３７０.
５℃であった。The same procedure as in Example 1 was repeated except that 9.1 parts of 2-methyl-5-nitroaniline was used in place of 2,5-dichloroaniline to obtain the desired compound. The infrared absorption spectrum (KBr method) is shown in FIG. The decomposition point is 370.
It was 5 ° C.
【００２８】[0028]
【実施例３】４,４'−ビフェニルビスアミド(IＸ)の合成 Example 3 Synthesis of 4,4′-biphenylbisamide (IX)
【化１９】 [Chemical 19]
【００２９】p−フェニレンジアミン１.６部の代わりに
３,３'−ジクロロ−４,４'−ジアミノビフェニル３.７
部を使用した以外は実施例１と同様の操作を行い、下記
目的化合物を得た。赤外線吸収スペクトル(ＫＢr法)を
図３に示す。分解点は３６４.７℃であった。3,3'-dichloro-4,4'-diaminobiphenyl 3.7 in place of 1.6 parts of p-phenylenediamine
The same operation as in Example 1 was carried out except that parts were used to obtain the following target compound. The infrared absorption spectrum (KBr method) is shown in FIG. The decomposition point was 364.7 ° C.
【００３０】[0030]
【実施例４】実施例１で用いた２.５−ジクロルアニリ
ンの代わりに３−クロル−４−メトキシアニリン９.５
部を、またＰ−フェニレンジアミンの代わりに１.５−
ジアミノナフタレン２.３部を使用した以外は実施例１
と同様の操作を行い、下記目的化合物を得た。Example 4 In place of the 2.5-dichloroaniline used in Example 1, 3-chloro-4-methoxyaniline 9.5
Parts in place of P-phenylenediamine and 1.5-
Example 1 except 2.3 parts of diaminonaphthalene were used
The same operation as above was performed to obtain the following target compound.
【化２０】 [Chemical 20]
【００３１】[0031]
【実施例５】２.５−ジクロルアニリン８.１部をニトロ
ベンゼン１５０部に溶解し、３５％塩酸１５.６部を加
え撹拌すると白色の塩酸塩が析出する。その後冷却して
温度を０〜５℃に保ち、これに亜硝酸ソーダ３.５部を
水１０部に溶かした液を滴下してジアゾ化を行い、ジア
ゾニウム塩の溶液を得た。一方、１.４−ビス−(２'−
ヒドロキシ−６'−ナフトイルアミノ)ベンゼン１２.１
部を２４０部の０−ニトロトルエンに懸濁し、これに苛
性ソーダ８.０部をメタノール４５部に溶解した液を加
える。次に撹拌しながらこれに前記のジアゾニウム塩の
溶液を滴下して１５〜２０℃にて３時間カップリング反
応を行う。反応終了後は、昇温してメタノール及び水を
溜去し、次いで２１０℃にて２時間撹拌還流し、精製結
晶化を行う。９０℃まで冷却し、濾過、温トルエンにて
洗浄後、メタノール洗浄、水洗、乾燥、粉砕して目的化
合物を得た。Example 5 8.5 parts of 2.5-dichloroaniline was dissolved in 150 parts of nitrobenzene, and 15.6 parts of 35% hydrochloric acid was added and stirred to precipitate a white hydrochloride. Thereafter, the mixture was cooled to maintain the temperature at 0 to 5 ° C., and a solution of 3.5 parts of sodium nitrite dissolved in 10 parts of water was added dropwise to the mixture for diazotization to obtain a solution of a diazonium salt. On the other hand, 1.4-bis- (2'-
Hydroxy-6'-naphthoylamino) benzene 12.1
Parts are suspended in 240 parts of 0-nitrotoluene, and a solution of 8.0 parts of sodium hydroxide in 45 parts of methanol is added thereto. Next, the solution of the diazonium salt is added dropwise to this while stirring, and a coupling reaction is carried out at 15 to 20 ° C. for 3 hours. After completion of the reaction, the temperature is raised to distill off methanol and water, and then the mixture is stirred and refluxed at 210 ° C. for 2 hours to carry out purification and crystallization. After cooling to 90 ° C., filtration, washing with warm toluene, washing with methanol, washing with water, drying and pulverization, the target compound was obtained.
【化２１】 [Chemical 21]
【００３２】試験例 表１に示す各種アゾ化合物の耐光性、耐熱性、耐水性、
耐溶剤性、耐薬品性等の諸性質、色調並びに分解点を表
１に示す。耐熱性、耐水性、耐溶剤性、耐薬品性は次の
ようにして評価した。Test Example Light resistance, heat resistance, water resistance of various azo compounds shown in Table 1,
Table 1 shows various properties such as solvent resistance and chemical resistance, color tone and decomposition point. The heat resistance, water resistance, solvent resistance, and chemical resistance were evaluated as follows.
【００３３】なお比較のため、従来のアニリド型アゾ化
合物の評価を同時に記載した。使用したアニリド型アゾ
化合物は比較例１では(Ｘ）：For comparison, the evaluation of the conventional anilide type azo compound is described at the same time. The anilide type azo compound used was (X) in Comparative Example 1:
【化２２】 比較例２では（ＸI):[Chemical formula 22] In Comparative Example 2, (XI):
【化２３】 である。[Chemical formula 23] Is.
【００３４】〈耐熱性評価〉顔料１部を軟質ポリ塩化ビ
ニルコンパウンド(ポリ塩化ビニル:フタル酸ジオクチ
ル:スズマレート:カルシウムステアレート:バリウムス
テアレート＝１００:５０:２:０.４:０.６)１００部を
２本ロールで十分混練してシート状に引き伸ばし、評価
用塩ビ成形体を作成した。この塩ビ成形体を４mm四方に
各３枚づつ切り、１６０℃の恒温器に入れて、６０分後
に取り出し、その着色度を測色計(東京電色、ＴＣ−３
６０)を用いて測定した。また熱をかけていない成形体
も同様にその着色度を測定した。<Heat Resistance Evaluation> One part of the pigment was mixed with a soft polyvinyl chloride compound (polyvinyl chloride: dioctyl phthalate: spumarate: calcium stearate: barium stearate = 100: 50: 2: 0.4: 0.6). 100 parts of the mixture was sufficiently kneaded with two rolls and stretched into a sheet to prepare a PVC molded article for evaluation. This PVC molded product is cut into 3 pieces of 4 mm each, placed in a thermostat at 160 ° C., taken out after 60 minutes, and the degree of coloring is measured by a colorimeter (Tokyo Denshoku, TC-3).
60). Further, the degree of coloring of the molded article which was not heated was measured in the same manner.
【００３５】測定はＬ＊(エルスター)、a＊(エースタ
ー)およびb＊(ビースター)色差式により、スタンダード
シートと試験区シートとの間の色差(△Ｅ)を算出するこ
とにより求めた。評価は色差式で求めた△Ｅで(Ａ〜Ｅ)
の５段階評価とした △Ｅ＝１以下 Ａ △Ｅ＝２〜３ Ｂ △Ｅ＝３〜５ Ｃ △Ｅ＝５〜８ Ｄ △Ｅ＝８以上 ＥThe measurement was carried out by calculating the color difference (ΔE) between the standard sheet and the test section sheet by the L * (Elster), a * (Aster) and b * (Bester) color difference formulas. . The evaluation is ΔE obtained by the color difference formula (A to E)
The following five-level evaluation was used: ΔE = 1 or less A ΔE = 2 to 3 B ΔE = 3 to 5 C ΔE = 5 to 8 D ΔE = 8 or more E
【００３６】〈耐光性評価〉 i) 耐熱性評価で作成した各塩ビ成形体を３５mm×１１
０mmに切る。 ii) この塩ビ成形体を半分マスクし、フェザーメータ
ー(サンテスタＸＦ−１８０・キセノンランプ)で１００
時間照射する。 iii) 照射後塩ビ成形体のマスクをした部分と、してい
ない部分をそれぞれ測定し、両者の色差(△Ｅ)を見る。 測色計、測色法、評価については、耐熱性評価に同じ。<Evaluation of light resistance> i) Each vinyl chloride molded body prepared in the heat resistance evaluation is 35 mm × 11.
Cut to 0 mm. ii) Half-mask this PVC molded body, and use a feather meter (Santesta XF-180 / xenon lamp) to 100
Irradiate for hours. iii) After irradiation, measure the masked portion and the non-masked portion of the PVC molded article, and check the color difference (ΔE) between the two. The colorimeter, colorimetric method, and evaluation are the same as the heat resistance evaluation.
【００３７】〈耐水、耐溶剤、耐薬品性評価〉 １) 耐水性評価 耐熱性評価で作成した各塩ビ成形体１.８g及び蒸留水１
０mlを試験管に取り、室温で２０分間超音波洗浄を行
う。その後昇温し、１分間リフラックスした後室温まで
冷却し、塩ビ成形体を取り出す。残液の着色割合を目視
して評価する 評価 Ａ 全く着色が認められないもの Ｂ 着色が極めて僅かであるもの Ｃ 着色が少しあるもの Ｄ 着色があるもの Ｅ 着色が著しいもの<Water resistance, solvent resistance, chemical resistance evaluation> 1) Water resistance evaluation 1.8 g of each PVC molded body prepared by heat resistance evaluation and 1 distilled water
Transfer 0 ml to a test tube and perform ultrasonic cleaning for 20 minutes at room temperature. After that, the temperature is raised, and after refluxing for 1 minute, it is cooled to room temperature, and the vinyl chloride molded body is taken out. Evaluation by visually observing the coloring ratio of the residual liquid A: No coloring is observed at all B: Very little coloring C: Some coloring D: Some coloring E: Significant coloring
【００３８】２) 耐溶剤及び耐薬品性 耐水性評価で使用した蒸留水のかわりに各試験液を１０
ml使用した以外は耐水性評価に同じ。2) Solvent resistance and chemical resistance In place of the distilled water used for water resistance evaluation, each test solution was replaced with 10 parts.
Same as water resistance evaluation except that ml was used.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【発明の効果】本発明の新規なジアゾ化合物は耐光性お
よび耐熱性が従来の２−ヒドロキシ−６−ナフトエ酸か
ら誘導されたアゾ化合物より優れており、外装用塗料プ
ラスチック練込み用着色剤として特に有用である。The novel diazo compound of the present invention is superior in light resistance and heat resistance to the conventional azo compounds derived from 2-hydroxy-6-naphthoic acid, and is useful as a coloring agent for kneading plastics for exterior coatings. Especially useful.
【図面の簡単な説明】[Brief description of drawings]
【図１】 実施例１のp−フェニレンビスアミド系アゾ
化合物(ＶII)の赤外線吸収スペクトルFIG. 1 is an infrared absorption spectrum of the p-phenylenebisamide azo compound (VII) of Example 1.
【図２】 実施例２のp−フェニレンビスアミド系アゾ
化合物(ＶIII)の赤外線吸収スペクトルFIG. 2 Infrared absorption spectrum of p-phenylenebisamide azo compound (VIII) of Example 2.
【図３】 実施例３のビフェニルビスアミド系アゾ化合
物(ＩＸ)の赤外線吸収スペクトルFIG. 3 Infrared absorption spectrum of biphenylbisamide-based azo compound (IX) of Example 3
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 11/02 ＰＴＦ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C09D 11/02 PTF
Claims (9)
Ｒ2、Ｒ2'、Ｒ3およびＲ3'はそれぞれ独立して水素原
子、アルキル基、アルコキシ基、ニトロ基またはハロゲ
ン原子を示す。]で表わされるアゾ化合物。1. General formula (I): [In the formula, A is an aromatic group having 6 to 12 carbon atoms; R 1 , R 1 ′,
R 2 , R 2 ′, R 3 and R 3 ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom. ] The azo compound represented by.
意味を有する。]で示される化合物と一般式(ＩＶ): Ｈ2Ｎ−Ａ−ＮＨ2 (ＩＶ) [式中、Ａは前記の意味を有する]で示される化合物とを
脱水縮合することを特徴とする請求項１に記載のアゾ化
合物の製法。2. General formulas (II) and (III): [Chemical 3] [Wherein R 1 , R 1 ′, R 2 , R 2 ′, R 3 and R 3 ′ have the above-mentioned meanings. ] The compound of the formula [IV]: H 2 N-A-NH 2 (IV) [wherein A has the above-mentioned meaning] is dehydrated and condensed. Item 2. A method for producing an azo compound according to Item 1.
示される化合物をジアゾ化し、得られたジアゾニウム化
合物を２−ヒドロキシ−６−ナフトエ酸とカップリング
することを特徴とする、一般式(ＩＩ): 【化５】 [式中、Ｒ1、Ｒ2およびＲ3は前記の意味を有する。]で
表される化合物の製法。3. General formula (V): [Wherein R 1 , R 2 and R 3 have the above-mentioned meanings. ] The compound represented by the formula] is diazotized, and the obtained diazonium compound is coupled with 2-hydroxy-6-naphthoic acid. The compound represented by the general formula (II): [Wherein R 1 , R 2 and R 3 have the above-mentioned meanings. ] The manufacturing method of the compound represented by.
示される化合物をジアゾ化し、得られたジアゾニウム化
合物を、一般式(ＶI) 【化７】 [式中、Ａは前記の意味を有する。]で示される化合物と
カップリングすることを特徴とする、請求項１に記載の
アゾ化合物の製法。4. A compound represented by the general formula (V): [Wherein R 1 , R 2 and R 3 have the above-mentioned meanings. ] The compound represented by the formula [9] is diazotized, and the obtained diazonium compound is represented by the general formula (VI): [In the formula, A has the above-mentioned meaning. ] The compound shown by these is coupled, The manufacturing method of the azo compound of Claim 1 characterized by the above-mentioned.
式(IＶ) Ｈ2Ｎ−Ａ−ＮＨ2 (IＶ) [式中、Ａは前記の意味を有する]で示される化合物とを
脱水縮合することを特徴とする、一般式(ＶI) 【化８】 [式中、Ａは前記の意味を有する]で表される化合物の製
法。5. Dehydration condensation of 2-hydroxy-6-naphthoic acid with a compound represented by the general formula (IV) H 2 N—A—NH 2 (IV) [wherein A has the above-mentioned meaning]. The general formula (VI) is characterized in that A process for producing a compound represented by the formula: wherein A has the above-mentioned meaning.
料。6. A pigment containing the azo compound according to claim 1.
料用練込み着色剤。9. A kneading colorant for polymer materials, which comprises the compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3233294A JP3608813B2 (en) | 1994-03-02 | 1994-03-02 | Azo compound and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3233294A JP3608813B2 (en) | 1994-03-02 | 1994-03-02 | Azo compound and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07238231A true JPH07238231A (en) | 1995-09-12 |
| JP3608813B2 JP3608813B2 (en) | 2005-01-12 |
Family
ID=12356000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3233294A Expired - Fee Related JP3608813B2 (en) | 1994-03-02 | 1994-03-02 | Azo compound and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3608813B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016498A1 (en) * | 1996-10-14 | 1998-04-23 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Bis(aminocarbonylnaphthol) derivative |
| US6005085A (en) * | 1997-03-19 | 1999-12-21 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Condensed azo compounds and process for preparing the same |
| US6548703B1 (en) | 1998-10-16 | 2003-04-15 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Toning agent |
| KR100671401B1 (en) * | 2004-04-30 | 2007-01-18 | 주식회사 에이스 디지텍 | Dye for display |
| TWI392708B (en) * | 2005-04-19 | 2013-04-11 | Dainichiseika Color Chem | Pigment dispersants and their use |
-
1994
- 1994-03-02 JP JP3233294A patent/JP3608813B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016498A1 (en) * | 1996-10-14 | 1998-04-23 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Bis(aminocarbonylnaphthol) derivative |
| US6072042A (en) * | 1996-10-14 | 2000-06-06 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Bis(aminocarbonylnaphthol) derivative |
| US6005085A (en) * | 1997-03-19 | 1999-12-21 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Condensed azo compounds and process for preparing the same |
| US6548703B1 (en) | 1998-10-16 | 2003-04-15 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Toning agent |
| KR100671401B1 (en) * | 2004-04-30 | 2007-01-18 | 주식회사 에이스 디지텍 | Dye for display |
| TWI392708B (en) * | 2005-04-19 | 2013-04-11 | Dainichiseika Color Chem | Pigment dispersants and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3608813B2 (en) | 2005-01-12 |
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