JP2011241372A - Rhodamine dye - Google Patents
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- JP2011241372A JP2011241372A JP2010256746A JP2010256746A JP2011241372A JP 2011241372 A JP2011241372 A JP 2011241372A JP 2010256746 A JP2010256746 A JP 2010256746A JP 2010256746 A JP2010256746 A JP 2010256746A JP 2011241372 A JP2011241372 A JP 2011241372A
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- AOVWNTJDPGHPMD-UHFFFAOYSA-N CCN(CC)c(cc1)cc(O2)c1C(c(cccc1)c1C(OCc1ccccc1)=O)=C(C=C1)C2=CC1=C Chemical compound CCN(CC)c(cc1)cc(O2)c1C(c(cccc1)c1C(OCc1ccccc1)=O)=C(C=C1)C2=CC1=C AOVWNTJDPGHPMD-UHFFFAOYSA-N 0.000 description 1
- FHFWEOHHVTZQIL-UHFFFAOYSA-N CCN(CC)c(cc1O2)ccc1C(c1c(C)c(C)c(C)c(C)c1C(O)=O)=C(C=C1)C2=CC1=[NH+][O-] Chemical compound CCN(CC)c(cc1O2)ccc1C(c1c(C)c(C)c(C)c(C)c1C(O)=O)=C(C=C1)C2=CC1=[NH+][O-] FHFWEOHHVTZQIL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は新規なローダミン染料に関する。 The present invention relates to a novel rhodamine dye.
ローダミンＢ、ローダミン３Ｂ、ローダミン６Ｇ等のローダミン染料は、レッドあるいはバイオレットの染料として広く使用されており、各種塗料、水性インキ、油性インキ、インクジェット用インキ、カラーフィルター用、染色用など幅広い用途での応用がなされている。一般に色材に要求される特性は用途によって異なるものの、着色物が光や熱等に対し堅牢である事が特に強く要求される。 Rhodamine dyes such as rhodamine B, rhodamine 3B, and rhodamine 6G are widely used as red or violet dyes, and are used in a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, color filters, and dyes. Application has been made. In general, the characteristics required of a color material vary depending on the application, but it is particularly strongly required that the colored material is robust against light, heat, and the like.
一般にローダミン染料は鮮明で発色性が優れる反面、耐光性、耐熱性、耐湿熱性、耐水性などの堅牢性が劣るという欠点がある。このため、ローダミン染料の鮮明性及び発色性を有し、且つ高堅牢な染料が要望されているが、これらの性能を兼ね備えたローダミン染料は見出されていない。特許文献１にはローダミン化合物のカチオン部位と塩素イオンやさらに塩化亜鉛とから成るローダミン染料が記載されているが、本発明者らの検討の結果、特許文献１に記載されているローダミン染料は耐光性、耐熱性、耐水性、耐湿熱性等の堅牢性が不十分であった。また特許文献２にはフッ素化アルキルスルホニル対イオンを有するローダミン染料についての記載はあるが、具体的な化合物の例示は無く、また染料組成物の耐光性、耐熱性、耐湿熱性、耐水性などの堅牢性に関する記載もなされていない。 In general, rhodamine dyes are clear and have excellent color developability, but have the disadvantage of poor fastness such as light resistance, heat resistance, moist heat resistance, and water resistance. For this reason, there is a demand for dyes having the sharpness and color development of rhodamine dyes and having high fastness, but no rhodamine dyes having these properties have been found. Patent Document 1 describes a rhodamine dye composed of a cation moiety of a rhodamine compound, chloride ion, and further zinc chloride. As a result of the study by the present inventors, the rhodamine dye described in Patent Document 1 is light-resistant. Fastness such as heat resistance, heat resistance, water resistance, and moist heat resistance was insufficient. Further, Patent Document 2 describes a rhodamine dye having a fluorinated alkylsulfonyl counter ion, but no specific compound is exemplified, and the light resistance, heat resistance, moist heat resistance, water resistance, etc. of the dye composition are not described. There is no mention of robustness.
本発明は、耐光性、耐熱性、耐湿熱性及び耐水性等の堅牢性に優れる新規なローダミン染料並びに該染料を用いた染料組成物を提供する事を目的とする。 An object of this invention is to provide the novel rhodamine dye excellent in fastness, such as light resistance, heat resistance, heat-and-moisture resistance, and water resistance, and the dye composition using this dye.
本発明者らは前記課題を解決すべく、鋭意研究を行った結果、特定の構造を有するローダミン染料が、従来に比べ飛躍的に耐熱性等の堅牢性が向上する事を見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that rhodamine dyes having a specific structure dramatically improve fastness such as heat resistance as compared with the conventional ones. It came to complete.
即ち、本発明は、
（１）下記一般式（１）で表されるローダミン染料
（２）一般式（１）が下記一般式（２）で表される（１）に記載のローダミン染料
（３）一般式（１）のＲ８がカルボアミド基及びその誘導体である（１）に記載のローダミン染料、
（４）Ｘ−がトリストリフルオロメタンスルホニルメチドアニオンである（１）乃至（３）のいずれか一つに記載のローダミン染料、
（５）（１）乃至（４）のいずれか一つに記載のローダミン染料と少なくとも１種以上の油性溶媒を含有する油性染料組成物、
（６）（１）乃至（４）のいずれか一つに記載のローダミン染料及び水性媒体を含有する水性染料組成物、
に関する。
That is, the present invention
(1) Rhodamine dye represented by the following general formula (1)
(2) The rhodamine dye according to (1), wherein the general formula (1) is represented by the following general formula (2)
(3) The rhodamine dye according to (1), wherein R 8 in the general formula (1) is a carboamide group or a derivative thereof,
(4) The rhodamine dye according to any one of (1) to (3), wherein X − is a tristrifluoromethanesulfonylmethide anion,
(5) An oily dye composition comprising the rhodamine dye according to any one of (1) to (4) and at least one oily solvent,
(6) An aqueous dye composition comprising the rhodamine dye according to any one of (1) to (4) and an aqueous medium,
About.
本発明のローダミン染料は、油性または水性染料組成物を形成して染料着色体に加工すると、従来品よりも堅牢性に優れた特性を示すものである。すなわち、本発明のローダミン染料は染料着色体に好適に利用でき、カラーフィルターやインクジェット用インキ等の幅広い用途に応用できる。 When the rhodamine dye of the present invention is formed into an oil-based or aqueous dye composition to be processed into a dye-colored product, the rhodamine dye exhibits characteristics superior in fastness to conventional products. That is, the rhodamine dye of the present invention can be suitably used for a dye-colored product, and can be applied to a wide range of uses such as a color filter and an inkjet ink.
本発明のローダミン染料は、前記一般式（１）または式（２）で表される。 The rhodamine dye of the present invention is represented by the general formula (1) or (2).
一般式（１）及び式（２）においてＸ−はビストリフルオロメタンスルホニルイミドアニオンまたはトリストリフルオロメタンスルホニルメチドアニオンを表し、特にトリストリフルオロメタンスルホニルメチドアニオンが好ましい。 In the general formulas (1) and (2), X − represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion, and a tristrifluoromethanesulfonylmethide anion is particularly preferable.
一般式（１）においてＲ１〜Ｒ４はそれぞれ独立に水素原子、アルキル基またはアリール基を表す。 In the general formula (1), R 1 to R 4 each independently represents a hydrogen atom, an alkyl group, or an aryl group.
一般式（１）のＲ１〜Ｒ４においてアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、等が挙げられる。これらのアルキル基は置換基を有してもよく、該置換基としては特に制限は無いが、例えばヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基、カルバモイル基、カルボキシル基等が挙げられる。 Examples of the alkyl group in R 1 to R 4 of the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited. For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, Examples include methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.
一般式（１）のＲ１〜Ｒ４においてアリール基としては、例えばフェニル基、ナフチル基、アンスリル基、フェナンスリル基、ピレニル基、ベンゾピレニル基等の芳香族炭化水素残基；ピリジル基、ピラジル基、ピリミジル基、キノリル基、イソキノリル基、ピロリル基、インドレニル基、イミダゾリル基、カルバゾリル基、チエニル基、フリル基等の芳香族複素環残基、等が挙げられる。 In R 1 to R 4 of the general formula (1), examples of the aryl group include aromatic hydrocarbon residues such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group; a pyridyl group, a pyrazyl group, Examples thereof include an aromatic heterocyclic residue such as a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, an indolenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group.
一般式（１）のＲ１〜Ｒ４において、アリール基はさらに置換基を有してもよく、該置換基としては特に制限はないが、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基、ペンチル基等のアルキル基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ−ブトキシ基、ヘキシルオキシ基等のアルコキシ基；ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシアルキル基；メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等のアルコキシアルキル基；２―ヒドロキシエトキシ基等のヒドロキシアルコキシ基；２−メトキシエトキシ基、２−エトキシエトキシ基等のアルコキシアルコキシ基；２−スルホエチル基、カルボキシエチル基、シアノエチル基、スルホン酸基、等が挙げられる。 In R 1 to R 4 of the general formula (1), the aryl group may further have a substituent, and the substituent is not particularly limited. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl, t-butyl and pentyl; halogen atoms such as fluorine, chlorine, bromine and iodine; methoxy, ethoxy, propoxy, butoxy, t-butoxy and hexyloxy Alkoxy groups such as hydroxy groups; hydroxyalkyl groups such as hydroxyethyl groups and hydroxypropyl groups; alkoxyalkyl groups such as methoxyethyl groups, ethoxyethyl groups, ethoxypropyl groups and butoxyethyl groups; hydroxyalkoxy groups such as 2-hydroxyethoxy groups Alkoxyalkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group; 2 Sulfoethyl, carboxyethyl group, a cyanoethyl group, a sulfonic acid group, and the like.
一般式（１）のＲ５、Ｒ６及びＲ８はそれぞれ独立に水素原子または置換基を表す。Ｒ５、Ｒ６及びＲ８の置換基としては、例えば、脂肪族基、アリール基、ヘテロ環基、アシル基、アシルオキシ基、アシルアミノ基、カルボアミド基、アルキル置換カルボアミド基、アリール置換カルボアミド基、脂肪族オキシ基、アリールオキシ基、ヘテロ環オキシ基、脂肪族オキシカルボニル基、アリールオキシカルボニル基、ヘテロ環オキシカルボニル基、カルバモイル基、脂肪族スルホニル基、アリールスルホニル基、ヘテロ環スルホニル基、脂肪族スルホニルオキシ基、アリールスルホニルオキシ基、ヘテロ環スルホニルオキシ基、スルファモイル基、脂肪族スルホンアミド基、アリールスルホンアミド基、ヘテロ環スルホンアミド基、アミノ基、脂肪族アミノ基、アリールアミノ基、ヘテロ環アミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、ヘテロ環オキシカルボニルアミノ基、脂肪族スルフィニル基、アリールスルフィニル基、脂肪族チオ基、アリールチオ基、ヒドロキシ基、シアノ基、スルホ基、カルボキシル基、脂肪族オキシアミノ基、アリールオキシアミノ基、カルバモイルアミノ基、スルファモイルアミノ基、ハロゲン原子、スルファモイルカルバモイル基、カルバモイルスルファモイル基、ジ脂肪族オキシフォスフィニル基、ジアリールオキシフォスフィニル基、等が挙げられる。 R 5 , R 6 and R 8 in the general formula (1) each independently represent a hydrogen atom or a substituent. Examples of the substituent for R 5 , R 6 and R 8 include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, a carboamido group, an alkyl-substituted carboamido group, an aryl-substituted carboamido group, and an aliphatic group. Group oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyl Oxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group , Aliphatic oxycarboni Ruamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group , Aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, etc. It is done.
一般式（２）のＲ１〜Ｒ６は一般式（１）におけるのと同じ意味を表し、Ｒ７は水素原子またはアルキル基を表す。 R 1 to R 6 in the general formula (2) represent the same meaning as in the general formula (1), and R 7 represents a hydrogen atom or an alkyl group.
一般式（２）のＲ７におけるアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、等が挙げられる。これらのアルキル基は置換基を有してもよく、該置換基としては特に制限は無いが、例えばヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基、カルバモイル基、カルボキシル基等が挙げられる。 Examples of the alkyl group for R 7 in the general formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. These alkyl groups may have a substituent, and the substituent is not particularly limited. For example, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, Examples include methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.
本発明のローダミン染料は、例えば、特許文献１に記載された公知の方法で合成することができる。また、一般式（１）及び式（２）のＸ−が塩素アニオン等である市販品を購入し、対応する塩または酸を加え塩交換する事でも合成できる。 The rhodamine dye of the present invention can be synthesized by, for example, a known method described in Patent Document 1. Moreover, it can synthesize | combine by purchasing the commercial item whose X < - > of General formula (1) and Formula (2) is a chlorine anion, etc., adding a corresponding salt or acid, and carrying out salt exchange.
本発明のローダミン染料を塩交換により合成する場合は、例えば、Ｘ−が塩素アニオンである染料を反応溶媒（例えば、水、またはメタノール、エタノール、イソプロパノール、アセトン、Ｎ，Ｎ−ジメチルホルアミド（以下ＤＭＦと略記）、Ｎ−メチル−２−ピロリドン（以下ＮＭＰと略記）等の水溶性極性溶媒が挙げられ、これらの溶媒は単独、または混合してもよい。）に溶解し、対応する塩または酸を０．５〜３等量程度加え、所定温度（例えば０〜１００℃）で攪拌し、析出した結晶をろ取する事により容易に得られる。 In the case of synthesizing the rhodamine dye of the present invention by salt exchange, for example, a dye in which X − is a chlorine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide (hereinafter referred to as “a”). And a water-soluble polar solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents may be used alone or in combination. The acid can be easily obtained by adding about 0.5 to 3 equivalents of acid, stirring at a predetermined temperature (for example, 0 to 100 ° C.), and collecting the precipitated crystals by filtration.
上記式（１）で表される具体例を、以下の表１−１〜表１−３に示すが、本発明はこれらに限定されない。 Specific examples represented by the above formula (1) are shown in the following Tables 1-1 to 1-3, but the present invention is not limited to these.
表１−１
本発明の油性または水性染料組成物は、本発明のローダミン染料及び、油性染料組成物の場合は油溶性有機溶媒を、水性染料の場合は水性媒体を含有する。本発明の油性または水性染料組成物においては、本発明のローダミン染料を０．２〜４０質量％含有させるのが好ましく、さらには０．５〜２０質量％含有させるのがより好ましい。また本発明の油性または水性染料組成物において、色相の調整などの目的で必要に応じて一般式（１）または式（２）以外の色材を添加してもよい。添加できる色材としては、例えば酸性染料、反応性染料、直接性染料、カチオン染料、塩基性染料等の水溶性染料、分散染料、ソルベント染料等の油溶性染料、有機顔料、カーボンブラック等が挙げられ、溶媒に溶解した状態あるいは分散した状態で添加される。 The oily or aqueous dye composition of the present invention contains the rhodamine dye of the present invention and an oil-soluble organic solvent in the case of an oily dye composition, and an aqueous medium in the case of an aqueous dye. In the oily or aqueous dye composition of the present invention, the rhodamine dye of the present invention is preferably contained in an amount of 0.2 to 40% by mass, and more preferably 0.5 to 20% by mass. Further, in the oily or aqueous dye composition of the present invention, a coloring material other than the general formula (1) or the formula (2) may be added as necessary for the purpose of adjusting the hue. Examples of colorants that can be added include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes, and basic dyes, oil-soluble dyes such as disperse dyes and solvent dyes, organic pigments, and carbon black. And added in a dissolved or dispersed state in a solvent.
本発明の水性染料組成物は、水性媒体に本発明のローダミン染料を分散させて調製する事ができる。水性媒体としては、水または水溶性有機溶媒が挙げられる。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｔ−ブタノール、ペンタノール、ベンジルアルコール等のアルコール類；エチレンエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、トリメチロールプロパン、１，３−ペンタンジオール、１，５−ペンタンジオール等の多価アルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコール誘導体；エタノールアミン、ジエタノールアミン、トリエタノールアミン、モルホリン等のアミン類；２−ピロリドン、ＮＭＰ、１，３−ジメチル−イミダゾリジノン、等が挙げられる。 The aqueous dye composition of the present invention can be prepared by dispersing the rhodamine dye of the present invention in an aqueous medium. Examples of the aqueous medium include water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, benzyl alcohol; ethylene ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene Polyhydric alcohols such as glycol, polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, Triethylene glycol monoethyl ether, triethylene glycol monobutyl Ether, dipropylene glycol monomethyl ether of glycol derivatives; ethanolamine, diethanolamine, triethanolamine, amines morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone, and the like.
本発明の油性染料組成物は、少なくとも１種の油溶性有機溶媒に本発明のローダミン染料を溶解または分散させて調製する事ができる。用いられる油溶性有機溶媒としては、例えば、エタノール、ペンタノール、オクタノール、シクロヘキサノール、ベンジルアルコール、テトラフルオロプロパノール等のアルコール類；エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、エチレングリコールジアセテート、エチレングリコールジアセテート、プロピレングリコールジアセテート等のグリコール誘導体；メチルエチルケトン、シクロヘキサノン等のケトン類；ブチルフェニルエーテル、ベンジルエーテル、ヘキシルエーテル等のエーテル類；酢酸エチル、酢酸ブチル、安息香酸エチル、安息香酸ブチル、ラウリン酸エチル、ラウリン酸ブチル等のエステル類；アセトニトリル、ＤＭＦ、ジメチルスルホキシド、スルホラン、ＮＭＰ、２−ピロリドン等の極性有機溶媒、等が挙げられ、これらの溶媒は単独で使用してもよいし、２種以上を混合して用いてもよい。 The oil-based dye composition of the present invention can be prepared by dissolving or dispersing the rhodamine dye of the present invention in at least one oil-soluble organic solvent. Examples of the oil-soluble organic solvent used include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, and tetrafluoropropanol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Glycol derivatives such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol diacetate, propylene glycol diacetate; ketones such as methyl ethyl ketone and cyclohexanone; Butyl phenyl ether, benzyl ether, hex Ethers such as ether; Esters such as ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate; polar organics such as acetonitrile, DMF, dimethyl sulfoxide, sulfolane, NMP, 2-pyrrolidone A solvent etc. are mentioned, These solvents may be used independently and may mix and use 2 or more types.
油性染料組成物に用いられる分散剤としては、ドデシルベンゼンスルホン酸ナトリウム、ラウリル酸ナトリウム、ナフタレンスルホン酸のホルマリン縮合物、アルキルナフタレンスルホン酸のホルマリン縮合物、クレオソート油スルホン酸のホルマリン縮合物、ポリオキシエチレンアルキルエーテルサルフェートのアンモニウム塩、ポリオキシエチレンアルキルフェニルエーテルサルフェートのアンモニウム、ポリオキシアルキルエーテル燐酸エステル塩等公知のアニオン界面活性剤、ビニルナフタレン誘導体、α、β−エチレン性不飽和カルボン酸の脂肪族アルコールエステル等、スチレン、スチレン誘導体、アクリル酸、アクリル酸誘導体、メタクリル酸、メタクリル酸誘導体、マレイン酸、マレイン酸誘導体、無水マレイン酸、無水マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマール酸、フマール酸誘導体等から選ばれた少なくとも２つ以上の単量体からなるブロック共重合体、或いはランダム共重合体、またはこれらの塩等の高分子分散剤等が挙げられ、これらの１種以上を分散する色素化合物に対して１０〜１００質量％で使用するのが好ましい。またこれらの分散剤と併せて、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、エチレンオキサイドとプロピレンオキサイドの共重合物等の公知のノニオン系の界面活性剤やシリコーン系、アセチレン系の公知の消泡剤を必要に応じ、顔料分散時及び／または顔料分散化後に添加する事ができる。 Dispersants used in oil dye compositions include sodium dodecylbenzenesulfonate, sodium laurate, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkyl naphthalene sulfonic acid, formalin condensate of creosote oil sulfonic acid, poly Known anionic surfactants such as ammonium salts of oxyethylene alkyl ether sulfates, ammonium of polyoxyethylene alkyl phenyl ether sulfates, polyoxyalkyl ether phosphate esters, vinyl naphthalene derivatives, fats of α, β-ethylenically unsaturated carboxylic acids Aromatic alcohol esters, etc., styrene, styrene derivatives, acrylic acid, acrylic acid derivatives, methacrylic acid, methacrylic acid derivatives, maleic acid, maleic acid derivatives, maleic anhydride, maleic anhydride A block copolymer consisting of at least two monomers selected from inic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, etc., or a random copolymer, or a high salt thereof. Examples thereof include molecular dispersants, and it is preferably used in an amount of 10 to 100% by mass with respect to the dye compound in which one or more of these are dispersed. In addition to these dispersants, known nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, copolymers of ethylene oxide and propylene oxide, and silicones A known acetylene-based antifoaming agent can be added at the time of pigment dispersion and / or after the pigment dispersion.
顔料を微粒子に分散する方法としては、サンドミル（ビーズミル）、ロールミル、ボールミル、ペイントシェーカー、超音波分散機、マイクロフルイダイザー等を用いるが、中でもサンドミル（ビーズミル）が一般に用いられる。サンドミル（ビーズミル）における顔料の粉砕には、小粒径のビーズを使用し、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理する必要があり、また粉砕処理後に濾過、遠心分離などで素粒子を除去する必要がある。 As a method for dispersing the pigment into the fine particles, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like is used. Among them, a sand mill (bead mill) is generally used. For the grinding of pigments in sand mills (bead mills), it is necessary to use beads with small particle diameters and to process them under conditions that increase the grinding efficiency by increasing the filling rate of the beads. It is necessary to remove elementary particles by separation or the like.
本発明の染料組成物はその他の添加剤として表面調整剤、防腐剤、防黴剤、ｐＨ調整剤等を添加しても良い。表面調整剤としては、ポリシロキサン系あるいはポリジメチルシロキサン系の界面活性剤、防腐や防黴剤としてはデヒドロ酢酸ナトリウム、安息香酸ナトリウム、ソジウムピリジンチオン−１−オキサイド、ジンクピリジンチオン−１−オキサイド、１，２−ベンズイソチアゾリン−３−オン、１−ベンズイソチアゾリン−３−オンのアミン塩等が挙げられ、ｐＨ調整剤としては水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の水酸化アルカリ金属類、トリエタノールアミン、ジエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン等の３級アミン類等が挙げられる。 The dye composition of the present invention may contain a surface conditioner, preservative, antifungal agent, pH adjuster, etc. as other additives. As surface conditioning agents, polysiloxane or polydimethylsiloxane surfactants, and as antiseptic and mildewproofing agents, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide 1, 2-benzisothiazolin-3-one, amine salts of 1-benzisothiazolin-3-one, etc., and pH adjusters include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide And tertiary amines such as triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine.
また本発明の油性または水性染料組成物中には被着色体への色素の定着性を向上させる目的で、必要な範囲内で組成中の媒体と相溶性のあるポリアミド系、ポリウレタン系、ポリエステル系、エポキシ系又はポリアクリル系樹脂を含有させる事が好ましい。また定着性を向上させる目的で、必要な範囲内でエチレン性不飽和基を有するモノマー、オリゴマーや重合開始剤等を含有させてもよい。本発明の油性または水性染料組成物は上記各成分を溶媒に溶解あるいは分散及び混合する事によって調製することができる。 In addition, in the oily or aqueous dye composition of the present invention, a polyamide system, a polyurethane system, or a polyester system that is compatible with the medium in the composition within a necessary range for the purpose of improving the fixability of the pigment to the object to be colored. It is preferable to contain an epoxy or polyacrylic resin. Further, for the purpose of improving the fixability, a monomer, an oligomer, a polymerization initiator or the like having an ethylenically unsaturated group may be contained within a necessary range. The oily or aqueous dye composition of the present invention can be prepared by dissolving or dispersing and mixing the above components in a solvent.
本発明のローダミン染料は、油性染料組成物、または水性染料組成物として各種塗料、水性インキ、油性インキ、インクジェット用インキ、カラーフィルター用着色組成物に用いられる。油性染料組成物および水性染料組成物は、例えば普通紙、コート紙、プラスチックフィルム、プラスチック基板などの被着色材料に用いられる。また、本発明の染料組成物を被着色材料に付与する方法としては、オフセット印刷、凸版印刷、フレキソ印刷、インクジェット印刷などの各種印刷方法あるいはスピンコーター、ロールコーターなどによる塗工方法が挙げられる。 The rhodamine dye of the present invention is used as an oil-based dye composition or an aqueous dye composition in various paints, water-based inks, oil-based inks, inkjet inks, and color filter coloring compositions. The oil-based dye composition and the aqueous dye composition are used for materials to be colored such as plain paper, coated paper, plastic film, and plastic substrate. Examples of a method for applying the dye composition of the present invention to a material to be colored include various printing methods such as offset printing, letterpress printing, flexographic printing, and ink jet printing, and coating methods using a spin coater, a roll coater, and the like.
以下、本発明を実施例により具体的に説明するが、本発明は、これらの実施例に限定されるものでは無い。尚、実施例中、「部」は特定しない限り「質量部」を表す。また、耐湿熱性や耐水性等の評価は染料着色体の色度（Ｌ値、ａ値、ｂ値）を分光光度計「（株）島津製作所製商品名ＵＶ−３１５０」により測定し評価した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In Examples, “part” means “part by mass” unless otherwise specified. In addition, evaluation of wet heat resistance, water resistance and the like was evaluated by measuring the chromaticity (L value, a value, b value) of the dyed colored body with a spectrophotometer “trade name UV-3150 manufactured by Shimadzu Corporation”.
実施例１
１００ｍｌビーカーに、下記式（１００）のローダミン６Ｇ（東京化成工業製）１部、水２０部を仕込み、常温で３０分間攪拌した。これにＤＭＦ１部にトリストリフルオロメタンスルホニウムメチドのセシウム塩（セントラル硝子製）１部を溶解させた溶液を滴下し、３時間攪拌した。析出した染料をろ取、水洗、乾燥し、染料（表１−１の化合物Ｎｏ．１）０．８部を得た。極大吸収波長：５３１ｎｍ（シクロヘキサノン）
Example 1
In a 100 ml beaker, 1 part of rhodamine 6G (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (100) and 20 parts of water were charged and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1 part of a cesium salt of tristrifluoromethanesulfonium methide (manufactured by Central Glass) was added dropwise to 1 part of DMF, and the mixture was stirred for 3 hours. The precipitated dye was collected by filtration, washed with water, and dried to obtain 0.8 part of a dye (Compound No. 1 in Table 1-1). Maximum absorption wavelength: 531 nm (cyclohexanone)
実施例２
ローダミン染料を下記式（１０１）のローダミンＢ（東京化成工業製）に変更した以外は実施例１と同様にして、染料（表１−１の化合物Ｎｏ．３）０．７部を得た。極大吸収波長：５６０ｎｍ（シクロヘキサノン）
Example 2
0.7 parts of the dye (Compound No. 3 in Table 1-1) was obtained in the same manner as in Example 1 except that the rhodamine dye was changed to rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (101). Maximum absorption wavelength: 560 nm (cyclohexanone)
実施例３
（工程３−１）
２００ｍｌフラスコに水７５部、２８％水酸化ナトリウム水溶液４．３部、上記式（１０１）のローダミンＢを１４．４部仕込み、常温で攪拌した。これに反応液のｐＨが７付近になるまで２８％水酸化ナトリウム水溶液を加え、更に炭酸ナトリウム１．６部を加えて、反応液のｐＨを１０．３に調整した。ここに硫酸ジメチル７．５部を加え、３０℃で２時間攪拌した後、この反応液を１Ｌビーカーに移した。これに５０℃の湯３５０部、９８％硫酸１部を加え、反応液のｐＨを２．７〜３．０に調整し、反応液を６０℃で２時間攪拌した。加熱を止め、これに水３００部、塩化亜鉛４．２部を加え、塩化ナトリウム７．５部を少しずつ加え、そのまま１時間攪拌、更に塩化ナトリウム４５部を追加し、３０分攪拌した。析出した染料をろ取、乾燥することにより、下記式（１０２）の中間体１６部を得た。極大吸収波長：５６１ｎｍ（シクロヘキサノン）
Example 3
(Step 3-1)
A 200 ml flask was charged with 75 parts of water, 4.3 parts of a 28% aqueous sodium hydroxide solution, and 14.4 parts of rhodamine B of the above formula (101) and stirred at room temperature. To this, 28% aqueous sodium hydroxide solution was added until the pH of the reaction solution reached around 7, and 1.6 parts of sodium carbonate was further added to adjust the pH of the reaction solution to 10.3. 7.5 parts of dimethyl sulfate was added thereto and stirred at 30 ° C. for 2 hours, and then the reaction solution was transferred to a 1 L beaker. 350 parts of 50 ° C. hot water and 1 part of 98% sulfuric acid were added thereto, the pH of the reaction solution was adjusted to 2.7 to 3.0, and the reaction solution was stirred at 60 ° C. for 2 hours. Heating was stopped, 300 parts of water and 4.2 parts of zinc chloride were added thereto, 7.5 parts of sodium chloride was added little by little, and the mixture was stirred for 1 hour, 45 parts of sodium chloride was further added, and the mixture was stirred for 30 minutes. The precipitated dye was collected by filtration and dried to obtain 16 parts of an intermediate of the following formula (102). Maximum absorption wavelength: 561 nm (cyclohexanone)
（工程３−２）
実施例１におけるローダミン６Ｇを、中間体（１０２）に変更した以外は実施例１と同様にして、染料（表１−１の化合物Ｎｏ．７）１．４部を得た。極大吸収波長：５６１ｎｍ（シクロヘキサノン）
(Step 3-2)
1.4 parts of a dye (Compound No. 7 in Table 1-1) were obtained in the same manner as in Example 1 except that Rhodamine 6G in Example 1 was changed to the intermediate (102). Maximum absorption wavelength: 561 nm (cyclohexanone)
実施例４
（工程４−１）
５０ｍｌフラスコに、上記式（１０１）のローダミンＢを１．２部、（Ｒ）−（−）−２−アミノ−１−プロパノール（東京化成工業製）５部を仕込み、１６０℃で６時間攪拌した。これに常温で飽和食塩水１５０部を加えて、ジクロロメタンで抽出、５％塩酸、水、飽和食塩水で洗浄した後、有機層を減圧下で濃縮した。得られた残渣を必要最小量のジクロロメタンに溶解させ、過剰量のヘキサンを加えた後、０℃で一晩静置させた。析出した赤紫色結晶をろ取、乾燥することにより、下記式（１０３）の中間体０．６部を得た。
Example 4
(Step 4-1)
In a 50 ml flask, 1.2 parts of rhodamine B of the above formula (101) and 5 parts of (R)-(−)-2-amino-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and stirred at 160 ° C. for 6 hours. did. To this was added 150 parts of saturated brine at room temperature, extracted with dichloromethane, washed with 5% hydrochloric acid, water, and saturated brine, and then the organic layer was concentrated under reduced pressure. The obtained residue was dissolved in a minimum amount of dichloromethane, an excess amount of hexane was added, and the mixture was allowed to stand at 0 ° C. overnight. The precipitated reddish purple crystals were collected by filtration and dried to obtain 0.6 parts of an intermediate of the following formula (103).
（工程４−２）
５００ｍｌビーカーに、中間体（１０３）の０．４部、酢酸７０部、水７０部を仕込み、常温で１０分攪拌した。これにＤＭＦ３部にトリストリフルオロメタンスルホニウムメチドのセシウム塩０．５部を溶解させた溶液を滴下し、２時間常温で攪拌した。この反応液に飽和重曹水３００部を少しずつ加え、析出した染料をろ取した。得られたウェットケーキを一晩水洗、ろ取、乾燥することにより、染料（表１−２の化合物Ｎｏ．１３）０．４部を得た。極大吸収波長：５５８ｎｍ（シクロヘキサノン）
(Step 4-2)
In a 500 ml beaker, 0.4 part of the intermediate (103), 70 parts of acetic acid and 70 parts of water were charged and stirred at room temperature for 10 minutes. A solution prepared by dissolving 0.5 part of a cesium salt of tristrifluoromethanesulfonium methide in 3 parts of DMF was added dropwise thereto, and stirred at room temperature for 2 hours. To this reaction solution, 300 parts of saturated aqueous sodium hydrogen carbonate was added little by little, and the precipitated dye was collected by filtration. The obtained wet cake was washed with water overnight, filtered and dried to obtain 0.4 parts of a dye (Compound No. 13 in Table 1-2). Maximum absorption wavelength: 558 nm (cyclohexanone)
実施例５
３００ｍｌビーカーに、中間体（１０２）１．５部、水１２５部を仕込み、常温で３０分攪拌した。これにＤＭＦ２部にビストリフルオロメタンスルホニルイミドのカリウム塩（森田化学工業製）０．９部を溶解させた溶液を滴下し、３時間攪拌した。析出した染料をろ取、水洗、乾燥し、染料（表１−２の化合物Ｎｏ．１４）１．７部を得た。極大吸収波長：５６０ｎｍ（シクロヘキサノン）
Example 5
A 300 ml beaker was charged with 1.5 parts of intermediate (102) and 125 parts of water and stirred at room temperature for 30 minutes. A solution in which 0.9 part of potassium salt of bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Co., Ltd.) was dissolved in 2 parts of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water, and dried to obtain 1.7 parts of a dye (Compound No. 14 in Table 1-2). Maximum absorption wavelength: 560 nm (cyclohexanone)
実施例６
（工程６−１）
実施例４の工程４−１における（Ｒ）−（−）−２−アミノ−１−プロパノールをベンジルアミンに変更した以外は、実施例４の工程４−１と同様にして、下記式（１０４）の中間体２部を得た。
Example 6
(Step 6-1)
Except that (R)-(−)-2-amino-1-propanol in Step 4-1 of Example 4 was changed to benzylamine, the same formula (104) was used as in Step 4-1 of Example 4. ) 2 parts of the intermediate was obtained.
（工程６−２）
実施例４の工程４−２における中間体（１０３）を上記式（１０４）に変更した以外は、実施例４の工程４−２と同様にして、染料（表１−３の化合物Ｎｏ．１５）１．３部を得た。極大吸収波長：５５９ｎｍ（シクロヘキサノン）
(Step 6-2)
A dye (compound No. 15 in Table 1-3) was prepared in the same manner as in Step 4-2 of Example 4 except that the intermediate (103) in Step 4-2 of Example 4 was changed to the above formula (104). ) 1.3 parts were obtained. Maximum absorption wavelength: 559 nm (cyclohexanone)
実施例７
３００ｍｌビーカーに、非特許文献（Ｏｒｇａｎｉｃ Ｌｅｔｔｅｒｓ、２００３、Ｖｏｌ．５、３２４５−３２４８）に記載の方法で合成した下記式（１０５）の中間体６部、水１７０部を仕込み、常温で１０分攪拌した。これにＤＭＦ５．５部にトリストリフルオロメタンスルホニウムメチドのセシウム塩５．５部を溶解させた溶液を滴下し、１時間室温で攪拌した。析出した染料をろ取、水洗、乾燥することにより、染料（表１−３の化合物Ｎｏ．１６）７部を得た。極大吸収波長：５８５ｎｍ（シクロヘキサノン）
Example 7
A 300 ml beaker was charged with 6 parts of an intermediate of the following formula (105) synthesized by the method described in non-patent literature (Organic Letters, 2003, Vol. 5, 3245-3248) and 170 parts of water, and stirred at room temperature for 10 minutes. did. A solution obtained by dissolving 5.5 parts of a cesium salt of tristrifluoromethanesulfonium methide in 5.5 parts of DMF was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. The precipitated dye was collected by filtration, washed with water, and dried to obtain 7 parts of a dye (Compound No. 16 in Table 1-3). Maximum absorption wavelength: 585 nm (cyclohexanone)
実施例８
（工程８―１）
１００ｍｌフラスコに、Ｎ，Ｎ−ジエチル−３−アミノフェノール（東京化成工業製）５部、テトラクロロ無水フタル酸（東京化成工業製）１０．６部、ｐ−トルエンスルホン酸一水和物０．６部、プロピオン酸１８部を仕込み、遮光して１２時間還流した。この反応溶液にトルエンを加え、８０℃の０．１Ｍ塩酸で洗浄し、有機層を減圧下で濃縮した後、１８％アンモニア水３００部を加え、常温で一晩攪拌した。再び、反応溶液中の染料をトルエンで抽出し、水層が透明になるまで水で洗浄、更に８０℃の０．１Ｍ塩酸で数回洗浄し、有機層を減圧下で濃縮することにより、下記式（１０６）の中間体１部を得た。
Example 8
(Process 8-1)
In a 100 ml flask, 5 parts of N, N-diethyl-3-aminophenol (manufactured by Tokyo Chemical Industry), 10.6 parts of tetrachlorophthalic anhydride (manufactured by Tokyo Chemical Industry), p-toluenesulfonic acid monohydrate 6 parts and 18 parts of propionic acid were added, and the mixture was refluxed for 12 hours while being protected from light. Toluene was added to the reaction solution, washed with 0.1 M hydrochloric acid at 80 ° C., the organic layer was concentrated under reduced pressure, 300 parts of 18% aqueous ammonia was added, and the mixture was stirred overnight at room temperature. Again, the dye in the reaction solution was extracted with toluene, washed with water until the aqueous layer became transparent, further washed several times with 0.1 M hydrochloric acid at 80 ° C., and the organic layer was concentrated under reduced pressure to obtain the following: 1 part of an intermediate of formula (106) was obtained.
（工程８−２）
１Ｌビーカーに中間体（１０６）０．６部、水２００部、メタノール３６０部を仕込み、４０℃で３０分攪拌した。加熱を止め、これにＤＭＦ２．１部にトリストリフルオロメタンスルホニウムメチドのセシウム塩０．６部を溶解させた溶液を滴下し、４時間室温で攪拌した。染料が析出してくるまでメタノールを減圧下で蒸発させた後、析出した染料をろ取、水洗、乾燥することにより染料（表１−３の化合物Ｎｏ．１７）０．４部を得た。極大吸収波長：５８７ｎｍ（シクロヘキサノン）
(Step 8-2)
A 1 L beaker was charged with 0.6 part of the intermediate (106), 200 parts of water and 360 parts of methanol, and stirred at 40 ° C. for 30 minutes. The heating was stopped, and a solution obtained by dissolving 0.6 parts of a cesium salt of tristrifluoromethanesulfonium methide in 2.1 parts of DMF was added dropwise thereto, followed by stirring at room temperature for 4 hours. Methanol was evaporated under reduced pressure until the dye was precipitated, and then the deposited dye was collected by filtration, washed with water, and dried to obtain 0.4 parts of the dye (Compound No. 17 in Table 1-3). Maximum absorption wavelength: 587 nm (cyclohexanone)
実施例９
（工程９−１）
５０ｍｌフラスコに、中間体（１０６）０．７部、２−アミノ−１−プロパノール５部を仕込み、１６０℃で４時間攪拌した。これに常温で飽和食塩水１５０部を加えて、ジクロロメタンで抽出、５％塩酸、水、飽和食塩水で洗浄した後、有機層を減圧下で濃縮した。得られた残渣を必要最小量のジクロロメタンに溶解させ、過剰量のヘキサンを加えた後、０℃で一晩静置させた。析出した赤紫色結晶をろ取、乾燥することにより、下記式（１０７）の中間体０．６部を得た。
Example 9
(Step 9-1)
A 50 ml flask was charged with 0.7 part of the intermediate (106) and 5 parts of 2-amino-1-propanol and stirred at 160 ° C. for 4 hours. To this was added 150 parts of saturated brine at room temperature, extracted with dichloromethane, washed with 5% hydrochloric acid, water, and saturated brine, and then the organic layer was concentrated under reduced pressure. The obtained residue was dissolved in a minimum amount of dichloromethane, an excess amount of hexane was added, and the mixture was allowed to stand at 0 ° C. overnight. The precipitated reddish purple crystals were collected by filtration and dried to obtain 0.6 parts of an intermediate of the following formula (107).
（工程９−２）
実施例４の工程４−２における中間体（１０３）を中間体（１０７）に変更した以外は、実施例４の工程４−２と同様にして、染料（表１−３の化合物Ｎｏ．１８）０．３部を得た。極大吸収波長：５６９ｎｍ（シクロヘキサノン）
(Step 9-2)
A dye (Compound No. 18 in Table 1-3) was prepared in the same manner as in Step 4-2 of Example 4 except that the intermediate (103) in Step 4-2 of Example 4 was changed to the intermediate (107). ) 0.3 parts were obtained. Maximum absorption wavelength: 569 nm (cyclohexanone)
実施例１０
（工程１０−１）
四つ口フラスコにＤＭＦ３０部、ベンジルブロミド（東京化成工業製）６．８部、炭酸カリウム３．０部、１，８−ジアザビシクロ[５，４，０]−７−ウンデセン（サンアプロ製）４．３部、上記式（１０１）のローダミンＢ９．６部を仕込み、９０℃で６時間攪拌した。反応液を濾過後、濾液に水を加え５００部に調整した。この液に、塩化亜鉛５部、さらに塩化ナトリウム１０部を少しずつ加え、そのまま１時間攪拌した。析出した染料をろ取、することにより、下記式（１０８）の中間体８部を得た。
Example 10
(Step 10-1)
In a four-necked flask, 30 parts of DMF, 6.8 parts of benzyl bromide (manufactured by Tokyo Chemical Industry), 3.0 parts of potassium carbonate, 1,8-diazabicyclo [5,4,0] -7-undecene (manufactured by San Apro) 3 parts, 9.6 parts of rhodamine B of the above formula (101) were charged and stirred at 90 ° C. for 6 hours. After the reaction solution was filtered, water was added to the filtrate to adjust to 500 parts. To this solution, 5 parts of zinc chloride and 10 parts of sodium chloride were added little by little and stirred as it was for 1 hour. The precipitated dye was collected by filtration to obtain 8 parts of an intermediate of the following formula (108).
（工程１０−２）
実施例１におけるローダミンＢを、中間体（１０８）に変更した以外は実施例１と同様にして、染料（表１−３の化合物Ｎｏ．１９）１．４部を得た。極大吸収波長：５６２ｎｍ（シクロヘキサノン）
(Step 10-2)
1.4 parts of a dye (Compound No. 19 in Table 1-3) were obtained in the same manner as in Example 1 except that Rhodamine B in Example 1 was changed to the intermediate (108). Maximum absorption wavelength: 562 nm (cyclohexanone)
実施例１１
油性染料組成物及び染料着色体の作成
前記の実施例１〜３で得られた化合物Ｎｏ．１、３及び７の０．５部をテトラフルオロプロパノール１０部にそれぞれ溶解し、油性染料組成物を作成した。得られた油性染料組成物をポリカーボネート基盤にスピンコートし、８０℃で３０分乾燥し、染料着色体を調製した。
Example 11
Preparation of oil-based dye composition and dye-colored product Compound No. 1 obtained in Examples 1 to 3 above. 0.5 parts of 1, 3 and 7 were dissolved in 10 parts of tetrafluoropropanol, respectively, to prepare an oily dye composition. The obtained oil dye composition was spin-coated on a polycarbonate substrate and dried at 80 ° C. for 30 minutes to prepare a dye-colored product.
以下の各表中における比較例１は上記式（１００）のローダミンＢを、比較例２は上記式（１０１）のローダミン６Ｇを使用し、同様に調製した染料着色体の評価結果である。 In the following tables, Comparative Example 1 is an evaluation result of a dye-colored product prepared in the same manner using Rhodamine B of the above formula (100) and Comparative Example 2 using Rhodamine 6G of the above formula (101).
耐湿熱性試験
上記の方法で得られた染料着色体を、８５℃、８５％ＲＨの条件の恒温恒湿機中４０時間放置した。試験前後の染料着色体を分光光度計でＬ値、ａ値、ｂ値を、標準光としてＣ光源、２度視野角で測色し、下記式より色差を求めた。尚、色差が小さいほど、色相の変化が少ないため優れている事を示す。
色差＝［（試験前Ｌ値−試験後Ｌ値）２＋（試験前ａ値−試験後ａ値）２＋（試験前ｂ値−試験後ｂ値）２］１／２
耐湿熱性試験における測色の測定値および色差を以下の表２〜表７に示す。
Humidity and heat resistance test The dyed colored body obtained by the above method was left in a constant temperature and humidity chamber under conditions of 85 ° C. and 85% RH for 40 hours. The dye-colored product before and after the test was measured with a spectrophotometer for the L value, a value, and b value as standard light using a C light source and a viewing angle of 2 degrees, and the color difference was determined from the following formula. In addition, it shows that it is excellent because there is little change of a hue, so that a color difference is small.
Color difference = [(L value before test−L value after test) 2 + (a value before test−a value after test) 2 + (b value before test−b value after test) 2 ] 1/2
Tables 2 to 7 below show the color measurement values and color differences in the wet heat resistance test.
化合物Ｎｏ．１の測色結果を以下の表２に示す。
表２
Ｌ値 ａ値 ｂ値
試験前 ８７．４９ ２５．８０ −１３．４８
試験後 ８８．４３ ２３．６２ −１２．２２
試験前後差 −０．９４ ２．１８ −１．２６
Compound No. The color measurement results of 1 are shown in Table 2 below.
Table 2
L value a value b value Before test 87.49 25.80-13.48
After the test 88.43 23.62-12.22
Difference before and after test -0.94 2.18 -1.26
化合物Ｎｏ．３の測色結果を以下の表３に示す。
表３
Ｌ値 ａ値 ｂ値
試験前 ６４．５７ ５０．００ −５７．９０
試験後 ６５．１８ ５０．６４ −５６．１２
試験前後差 −０．９４ −０．６４ −１．７８
Compound No. The color measurement results of 3 are shown in Table 3 below.
Table 3
L value a value b value Before test 64.57 50.00 -57.90
After the test 65.18 50.64 -56.12
Difference before and after test -0.94 -0.64 -1.78
化合物Ｎｏ．７の測色結果を以下の表４に示す。
表４
Ｌ値 ａ値 ｂ値
試験前 ８１．６ ２２．７３ −２８．９３
試験後 ８２．０２ ２２．１３ −２８．３３
試験前後差 −０．４２ −０．６ −０．６
Compound No. The color measurement results of 7 are shown in Table 4 below.
Table 4
L value a value b value before test 81.6 22.73 -28.93
After the test 82.02 22.13 -28.33
Difference before and after test -0.42 -0.6 -0.6
比較例１の測色結果を以下の表５に示す。
表５
Ｌ値 ａ値 ｂ値
試験前 ７８．４３ ３４．９８ −２６．８４
試験後 ９８．３５ １．３６ −１．０７
試験前後差 −１９．９２ ３３．６２ −２５．７７
The color measurement results of Comparative Example 1 are shown in Table 5 below.
Table 5
L value a value b value Before test 78.43 34.98 -26.84
After the test 98.35 1.36 -1.07
Difference before and after test -19.92 33.62 -25.77
比較例２の測色結果を以下の表６に示す。
表６
Ｌ値 ａ値 ｂ値
試験前 ８９．０６ １２．２９ −１４．５４
試験後 ９５．７０ ５．５５ −４．０６
試験前後差 −６．６４ ６．７４ −１０．４８
The color measurement results of Comparative Example 2 are shown in Table 6 below.
Table 6
L value a value b value Before test 89.06 12.29 -14.54
After the test 95.70 5.55 -4.06
Difference before and after test -6.64 6.74-10.48
上記の表２〜表６の化合物Ｎｏ．１、３、７及び表５と表６の比較例１、２の色差を求めた結果を以下の表７に示す。
表７
色 差
化合物Ｎｏ．１ ２．６９
化合物Ｎｏ．３ １．９９
化合物Ｎｏ．７ ４．８
比較例１ ４６．８１
比較例２ １４．１２
Compound Nos. Table 7 below shows the results of obtaining the color differences of Comparative Examples 1 and 2 in Tables 1, 3, and 7 and Tables 5 and 6.
Table 7
Color difference compound no. 1 2.69
Compound No. 3 1.99
Compound No. 7 4.8
Comparative Example 1 46.81
Comparative Example 2 14.12
上記の結果から明らかなように、比較例の染料着色体の試験前後における色差が１０以上と高い値を示すのに対し、本発明の染料着色体の色差は５以下の低い値を示し、耐湿熱性にきわめて優れていることがわかる。
以上のように本発明のローダミン染料及び、その染料着色体は耐湿熱性に優れ、高い堅牢性を有するものであり、本発明のローダミン染料はカラーフィルター用インキやインクジェット用インキ等、アプリケーションの幅が広がるなどの産業的な価値が高い事が明らかとなった。
As apparent from the above results, the color difference before and after the test of the dyed colored body of the comparative example showed a high value of 10 or more, whereas the color difference of the dyed colored body of the present invention showed a low value of 5 or less, and was resistant to moisture. It turns out that it is extremely excellent in heat property.
As described above, the rhodamine dye of the present invention and the dye-colored product thereof are excellent in moisture and heat resistance and have high fastness, and the rhodamine dye of the present invention has a wide range of applications such as color filter ink and ink jet ink. It became clear that industrial value such as spreading was high.
Claims (6)
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