JP3264057B2 - Anthraquinone dyes - Google Patents
Anthraquinone dyesInfo
- Publication number
- JP3264057B2 JP3264057B2 JP26508193A JP26508193A JP3264057B2 JP 3264057 B2 JP3264057 B2 JP 3264057B2 JP 26508193 A JP26508193 A JP 26508193A JP 26508193 A JP26508193 A JP 26508193A JP 3264057 B2 JP3264057 B2 JP 3264057B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- dye
- coloring
- atom
- 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 - Fee Related
Links
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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/54—Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
- C09B1/547—Anthraquinones with aromatic ether groups
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な色素に関し、更に
詳しくはポリエステル系、アセテート系などの合成ない
し半合成高分子材料からなる繊維などの成型物の着色お
よび液晶、油性インク、鉱油等の着色に有用な赤色の色
素に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coloring matter, and more particularly, to coloring of molded articles such as fibers made of synthetic or semi-synthetic polymer materials such as polyesters and acetates, and liquid crystals, oil-based inks and mineral oils. It relates to a red pigment useful for coloring.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】ポリ
エステル系、アセテート系などの合成ないし半合成高分
子材料からなる繊維などの成型物の着色および液晶、油
性インク、鉱油等の着色においては、一般に着色力が大
きく、鮮明度の高い色素が好ましい。従来、非水溶性色
素の場合は、カチオン染料や酸性染料などの水溶性色素
にみられる鮮明な色素は少なく、また非水溶性色素の場
合はカチオン染料などに比べ着色力が低い場合が多いた
め、大きい着色力と高い鮮明度を有する色素は概して少
ない。本発明は、着色力が大きく、鮮明度の高い、疎水
性の高められた新規な非水溶性色素を提供するものであ
る。2. Description of the Related Art In the coloring of molded products such as fibers made of synthetic or semi-synthetic polymer materials such as polyesters and acetates, and in the coloring of liquid crystals, oil-based inks, mineral oils, etc. Dyes having high coloring power and high sharpness are preferred. Conventionally, in the case of water-insoluble dyes, there are few clear dyes found in water-soluble dyes such as cationic dyes and acid dyes, and in the case of water-insoluble dyes, the coloring power is often lower than that of cationic dyes. Pigments with high tinctorial strength and high sharpness are generally low. The present invention provides a novel water-insoluble dye having high coloring power, high definition, and enhanced hydrophobicity.
【０００３】[0003]
【課題を解決するための手段】本発明は、下記一般式
〔Ｉ〕According to the present invention, there is provided a compound represented by the following general formula [I]:
【０００４】[0004]
【化２】 Embedded image
【０００５】（式中、Ｒｆは３個以上のフッ素原子で置
換されたアルキル基を示し、これらは更にパーフルオロ
アルコキシ基、塩素原子置換パーフルオロアルコキシ
基、または、塩素原子で置換されていてもよい。Ｚはハ
ロゲン原子で置換されていてもよい−（ＣＨ2 ）n −ま
たは−ＣＨ2 ＣＨ＝ＣＨ−を示し、ｎは１〜８の数を示
す。Ｒｆ−Ｚ−Ｏ−ＣＯ−基の置換位置は６位または７
位であり、Ｘは水素原子、アルキル基、アルコキシ基、
アルコキシアルキル基、またはハロゲン原子を示す。）
で表される水溶性基を有しないアントラキノン系色素を
要旨とする。本発明のアントラキノン系色素は例えば、
下記一般式〔II〕で示されるアントラキノンカルボン酸
類(In the formula, Rf represents an alkyl group substituted with three or more fluorine atoms, and these may be further substituted with a perfluoroalkoxy group, a chlorine-substituted perfluoroalkoxy group, or a chlorine atom.) good .Z may be substituted by a halogen atom - (CH 2) n - or -CH 2 CH = CH- indicates, n represents .Rf-Z-O-CO- group indicating the number of 1 to 8 Is substituted at position 6 or 7
X is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an alkoxyalkyl group or a halogen atom. )
The gist is an anthraquinone dye having no water-soluble group. The anthraquinone dye of the present invention is, for example,
Anthraquinonecarboxylic acids represented by the following general formula [II]
【０００６】[0006]
【化３】 Embedded image
【０００７】（式中、Ｘは前記一般式〔Ｉ〕と同一の意
義を有し、カルボキシル基は６位または７位に置換して
いる。通常は両置換体の等量混合物である。）とＲｆ−
Ｚ−ＯＨで示される（式中、Ｒｆ，Ｚは前記一般式
〔Ｉ〕と同一の意義を有する。）フッ素原子で置換され
たアルコール類を酸触媒の存在下でエステル化反応させ
るか、または上記のアントラキノンカルボン酸類の酸ハ
ロゲン化物と上記のフッ素原子で置換されたアルコール
類を通常の反応条件下で反応させることにより得られ
る。(In the formula, X has the same meaning as in the above formula [I], and the carboxyl group is substituted at the 6-position or the 7-position. Usually, an equimolar mixture of both substituted products.) And Rf-
An alcohol represented by Z-OH (wherein Rf and Z have the same meanings as in the general formula [I]) are subjected to an esterification reaction in the presence of an acid catalyst, or It can be obtained by reacting the above-mentioned acid halide of anthraquinonecarboxylic acid with the above-mentioned alcohol substituted with a fluorine atom under ordinary reaction conditions.
【０００８】前記一般式〔Ｉ〕におけるＲｆの具体例と
してはトリフルオロメチル基、ペンタフルオロエチル
基、ヘプタフルオロプロピル基、ノナフルオロブチル
基、ウンデカフルオロペンチル基、ヘプタデカフルオロ
オクチル基などの炭素数１〜１８のパーフルオロアルキ
ル基；２Ｈ−パーフルオロプロピル基、４Ｈ−パーフル
オロブチル基、８Ｈ−パーフルオロオクチル基などの水
素原子を部分的に含み３個以上のフッ素原子を有するア
ルキル基；２−クロロテトラフルオロエチル基などの塩
素原子で置換された３個以上のフッ素原子を有するアル
キル基；パーフルオロプロピルオキシパーフルオロエチ
ル基などのパーフルオロアルコキシ基で置換され、３個
以上のフッ素原子を有するアルキル基；５−クロロパー
フルオロプロピルオキシパーフルオロエチル基などの塩
素原子を有するパーフルオロアルコキシ基で置換され、
３個以上のフッ素原子を有するアルキル基が挙げられ
る。Specific examples of Rf in the general formula [I] include carbon atoms such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, and heptadecafluorooctyl. An alkyl group partially containing a hydrogen atom and having three or more fluorine atoms, such as a 2H-perfluoropropyl group, a 4H-perfluorobutyl group, and an 8H-perfluorooctyl group; An alkyl group having three or more fluorine atoms substituted with a chlorine atom such as a 2-chlorotetrafluoroethyl group; three or more fluorine atoms substituted with a perfluoroalkoxy group such as a perfluoropropyloxyperfluoroethyl group An alkyl group having the formula: 5-chloroperfluoropropyloxy Substituted by perfluoroalkoxy group having a chlorine atom such as perfluoroethyl group,
Examples include an alkyl group having three or more fluorine atoms.
【０００９】Ｚは具体例としてはメチレン、エチレン、
トリメチレン、テトラメチレンなどの炭素数１〜８のポ
リメチレン基；２−ヨードトリメチレンなどのハロゲン
原子で置換されたポリメチレン基；あるいは−ＣＨ2 Ｃ
Ｈ＝ＣＨ−が挙げられる。Ｘの具体例としては水素原子
のほか、メチル基、エチル基、直鎖状または分枝状のプ
ロピル基、ブチル基、オクチル基などの、例えば炭素数
１〜１８のアルキル基、メトキシ基、エトキシ基、プロ
ポキシ基、ブトキシ基、オクチルオキシ基等の例えば炭
素数１〜１８のアルコキシ基、プロポキシメチル基、ブ
トキシエチル基などのアルコキシアルキル基、塩素原
子、臭素原子などのハロゲン原子が挙げられる。Z is a specific example of methylene, ethylene,
Polymethylene group substituted with a halogen atom such as 2-iodo trimethylene; trimethylene, polymethylene group having 1 to 8 carbon atoms such as tetramethylene or -CH 2 C
H = CH-. Specific examples of X include a hydrogen atom, an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, and an octyl group, a methoxy group, and an ethoxy group. Examples thereof include an alkoxy group having 1 to 18 carbon atoms such as a group, a propoxy group, a butoxy group, and an octyloxy group; an alkoxyalkyl group such as a propoxymethyl group and a butoxyethyl group; and a halogen atom such as a chlorine atom and a bromine atom.
【００１０】本発明の色素の特徴としては、従来の同種
の色素に比べて疎水性が高められている点が挙げられ、
一般に疎水性の高い材料の着色に好適である。本発明の
色素は合成ないし半合成もしくは天然高分子材料からな
るか、またはこれらの材料を含む繊維状あるいはシート
状、板状などの成型物、更にはこれらの材料をコーティ
ングした紙などの成型物を公知の種々の方法により着色
することができる。A feature of the dye of the present invention is that it has an enhanced hydrophobicity as compared with conventional dyes of the same kind.
Generally, it is suitable for coloring highly hydrophobic materials. The coloring matter of the present invention is composed of synthetic or semi-synthetic or natural polymer materials, or a fibrous or sheet-like or plate-like molded product containing these materials, or a molded product such as paper coated with these materials. Can be colored by various known methods.
【００１１】すなわち、成型物がポリエステル繊維、ポ
リアミド繊維、セルローストリアセテート繊維などの繊
維状である場合には、公知の方法により調製した水性分
散液を用いて、公知の染色法または捺染法を適用するこ
とにより着色することができる。本発明の色素は耐熱性
にも優れているため、スチロール樹脂、ＡＳ樹脂、ＡＢ
Ｓ樹脂、アクリル樹脂などの着色成型に用いることがで
きる。また、本発明の色素は従来色素に比べて疎水性が
高いため、上記の高分子材料に限らず、液晶、油性イン
ク、鉱油等の着色に好適に使用することができ、感熱転
写記録等にも用いることができる。That is, when the molded product is a fibrous material such as polyester fiber, polyamide fiber, cellulose triacetate fiber, a known dyeing method or a printing method is applied using an aqueous dispersion prepared by a known method. Can be colored. Since the dye of the present invention is also excellent in heat resistance, styrene resin, AS resin, AB
It can be used for coloring molding of S resin, acrylic resin and the like. Further, since the dye of the present invention has a higher hydrophobicity than conventional dyes, it can be suitably used for coloring liquid crystals, oil-based inks, mineral oils, etc., without being limited to the above-mentioned polymer materials, and is used for thermal transfer recording and the like. Can also be used.
【００１２】[0012]
【実施例】以下の実施例により本発明をさらに具体的に
説明するが、本発明はこれら実施例により何ら限定され
るものではない。 実施例１ 下記構造式で示されるアントラキノンカルボン酸〔III
〕（Ｒ1 ＝Ｈ、Ｒ2 ＝−ＣＯＯＨとＲ1 ＝−ＣＯＯ
Ｈ、Ｒ2 ＝Ｈの等量混合物）The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Anthraquinonecarboxylic acid represented by the following structural formula [III
(R 1 = H, R 2 = —COOH and R 1 = —COO
H, an equal mixture of R 2 = H)
【００１３】[0013]
【化４】 Embedded image
【００１４】０．２４ｇ（０．５０ｍｍｏｌ）をモレキ
ュラーシーブにより乾燥させたｏ−ジクロロベンゼン８
ｍｌに懸濁し、ｐ−トルエンスルホン酸４４ｍｇを添加
し、１２０℃に昇温させ、Ｆ（ＣＨ2 ）6 −ＣＨ2 −Ｃ
Ｈ2 −ＯＨという構造式で示されるフッ素含有アルコー
ル０．５７ｇ（１．５ｍｍｏｌ）を滴下し、１２時間反
応させた。溶液を放冷後、メタノール添加により結晶を
析出させ、濾過後、カラムクロマトにより精製し、目的
の下記構造式0.24 g (0.50 mmol) of o-dichlorobenzene 8 dried by molecular sieve
The suspension was added to 44 mg of p-toluenesulfonic acid, and the temperature was raised to 120 ° C. to obtain F (CH 2 ) 6 —CH 2 —C
0.57 g (1.5 mmol) of a fluorine-containing alcohol represented by a structural formula of H 2 —OH was added dropwise and reacted for 12 hours. After allowing the solution to cool, crystals are precipitated by adding methanol, filtered, and purified by column chromatography to obtain the target compound of the following structural formula
【００１５】[0015]
【化５】 Embedded image
【００１６】で示される融点１８１℃のアントラキノン
系色素を得た。本色素のクロロホルム溶液は５６５ｎｍ
に吸収ピークを示した。本色素を用いて水性分散液を調
製し、常法によりポリエステル繊維を染色処理して黄色
の染色布を得た。また、本色素を商品名ＺＬＩ−４７９
２（Ｅ．ＭＥＲＣＫ社製）として市販されているフッ素
液晶混合物に溶解して吸収スペクトルを測定した結果、
５６９ｎｍに吸収ピークを示した。An anthraquinone dye having a melting point of 181 ° C. was obtained. The chloroform solution of this dye is 565 nm
Shows the absorption peak. An aqueous dispersion was prepared using this dye, and a polyester fiber was dyed by a conventional method to obtain a yellow dyed cloth. In addition, this dye was used under the trade name of ZLI-479.
2 (manufactured by MERCK) dissolved in a fluorine liquid crystal mixture, and the absorption spectrum was measured.
It showed an absorption peak at 569 nm.
【００１７】実施例２ 実施例１と同様にして得られた色素と、そのクロロホル
ム溶液中での最大吸収波長（λmax ）を後記表１に示
す。尚、以下の色素はそれぞれポリエステル繊維を常法
により染色した場合にいずれも鮮明な赤紫色の染色物が
得られた。Example 2 The dye obtained in the same manner as in Example 1 and its maximum absorption wavelength (λmax) in a chloroform solution are shown in Table 1 below. In addition, when the following pigment | dye respectively dye | stained the polyester fiber by the conventional method, the clear red purple dyed material was obtained in all cases.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】本発明の新規な色素は、従来の同種の色
素に比べて疎水性が高く、疎水性の高い合成繊維及び合
成樹脂の着色の他、液晶、油性インク、鉱油の着色や感
熱転写記録用途等に好適な色素である。The novel dye of the present invention has higher hydrophobicity than conventional dyes of the same kind, and can be used for coloring synthetic fibers and synthetic resins having high hydrophobicity, as well as for coloring and feeling of liquid crystals, oil-based inks and mineral oils. It is a dye suitable for thermal transfer recording and the like.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−246933（ＪＰ，Ａ) 特開 平３−21693（ＪＰ，Ａ) 特開 平２−173090（ＪＰ，Ａ) 特開 平２−163191（ＪＰ，Ａ) 特開 平２−151686（ＪＰ，Ａ) 特開 昭59−172549（ＪＰ，Ａ) 特開 昭59−109559（ＪＰ，Ａ) 特開 昭59−74159（ＪＰ，Ａ) 特開 昭56−135554（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09B 1/54 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-246933 (JP, A) JP-A-3-21693 (JP, A) JP-A-2-173090 (JP, A) JP-A-2- 163191 (JP, A) JP-A-2-151686 (JP, A) JP-A-59-172549 (JP, A) JP-A-59-109559 (JP, A) JP-A-59-74159 (JP, A) JP-A-56-135554 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09B 1/54 CA (STN) REGISTRY (STN)
Claims (2)
を有しないアントラキノン系色素。 【化１】 （式中、Ｒｆは３個以上のフッ素原子で置換されたアル
キル基を示し、これらは更にパーフルオロアルコキシ
基、塩素原子置換パーフルオロアルコキシ基、または、
塩素原子で置換されていてもよい。Ｚはハロゲン原子で
置換されていてもよい−（ＣＨ2 ）n −または−ＣＨ2
ＣＨ＝ＣＨ−を示し、ｎは１〜８の数を示す。Ｒｆ−Ｚ
−Ｏ−ＣＯ−基の置換位置は６位または７位であり、Ｘ
は水素原子、アルキル基、アルコキシ基、アルコキシア
ルキル基、またはハロゲン原子を示す。）1. An anthraquinone dye having no water-soluble group represented by the following general formula [I]. Embedded image (In the formula, Rf represents an alkyl group substituted with three or more fluorine atoms, and these further include a perfluoroalkoxy group, a chlorine atom-substituted perfluoroalkoxy group, or
It may be substituted with a chlorine atom. Z may be substituted with a halogen atom - (CH 2) n - or -CH 2
CH = CH-, and n represents a number of 1 to 8. Rf-Z
The -O-CO- group is substituted at the 6-position or the 7-position,
Represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, or a halogen atom. )
位の化合物と７位の化合物との混合物である請求項１記
載のアントラキノン系色素。2. The substitution position of the Rf-ZO-CO- group is 6
The anthraquinone dye according to claim 1, which is a mixture of a compound at the 7-position and a compound at the 7-position.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26508193A JP3264057B2 (en) | 1993-10-22 | 1993-10-22 | Anthraquinone dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26508193A JP3264057B2 (en) | 1993-10-22 | 1993-10-22 | Anthraquinone dyes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07118550A JPH07118550A (en) | 1995-05-09 |
| JP3264057B2 true JP3264057B2 (en) | 2002-03-11 |
Family
ID=17412339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26508193A Expired - Fee Related JP3264057B2 (en) | 1993-10-22 | 1993-10-22 | Anthraquinone dyes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3264057B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5097405B2 (en) * | 2007-01-15 | 2012-12-12 | 日本電産株式会社 | Hydrodynamic bearing device and spindle motor |
| WO2012152584A1 (en) * | 2011-05-06 | 2012-11-15 | Basf Se | Chromophores with perfluoroalkyl substituents |
-
1993
- 1993-10-22 JP JP26508193A patent/JP3264057B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118550A (en) | 1995-05-09 |
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