JP6956033B2 - A benzoazole compound and a pigment composition containing the same. - Google Patents
A benzoazole compound and a pigment composition containing the same. Download PDFInfo
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Description
本発明は、液晶ディスプレイや撮像素子などの製造に使用されるカラーフィルター用レジストやインクジェット用インクに用いられるベンゾアゾール化合物、並びに該化合物を含有する流動性や透明性に優れる顔料組成物に関する。 The present invention relates to a benzoazole compound used in a color filter resist and an inkjet ink used in the manufacture of a liquid crystal display, an image pickup device, and the like, and a pigment composition containing the compound and having excellent fluidity and transparency.
塗料や印刷インキ、近年ではカラーフィルター用レジストやインクジェット用インクの着色剤として、顔料が利用されている。顔料は、耐熱性、耐候性、耐マイグレーション等の諸特性で、染料と比較して堅牢性の面で優れるが、一方で組成物にした際の凝集、沈降、経時的な粘度の増加、異種顔料と混合した際の色分かれ等の潜在的な問題を有している。 Pigments have been used as colorants for paints and printing inks, and in recent years, resists for color filters and ink jet inks. Pigments have various properties such as heat resistance, weather resistance, and migration resistance, and are superior in terms of toughness compared to dyes. It has potential problems such as color coding when mixed with pigments.
また最近では、液晶ディスプレイの高コントラスト化や撮像素子の微細化、インクジェットインクの高着色や高鮮明化等を達成するために、顔料の微粒子化及び顔料組成物中における顔料の高濃度化の要求が高まっているが、粒子径の微細化に伴い、また顔料の高濃度化に伴い凝集が起こりやすくなり、安定な分散体を得ることが困難となっている。 Recently, in order to achieve high contrast of liquid crystal displays, miniaturization of image pickup elements, high coloring and high sharpening of inkjet inks, etc., there is a demand for finer pigments and higher pigment concentrations in pigment compositions. However, as the particle size becomes finer and the concentration of the pigment increases, aggregation tends to occur, making it difficult to obtain a stable dispersion.
こうした問題を解決するために、顔料自体の改良検討（顔料表面処理）や顔料に対して良好な吸着性を有する分散剤、界面活性剤の開発、及び顔料誘導体等の提案がこれまでに行われてきた。顔料誘導体とは微粒子化する顔料と同構造あるいは類似構造の顔料に、酸性や塩基性等の置換基を導入した化合物で、顔料との親和性や吸着性を有し、且つ酸・塩基相互作用により分散剤とも強い結合力を有する為、顔料の微粒子化・分散安定化を向上する性質があり、顔料の粉砕・分散微粒子化工程等において使用されている。カラーフィルターやインクジェットで用いられる顔料としては、フタロシアニン系顔料、ジケトピロロピロール系顔料、アンスラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリン系顔料、イソインドリノン系顔料、アゾ系顔料、染料レーキ顔料等が挙げられ、特にフタロシアニン系顔料、アンスラキノン系顔料、キナクリドン系顔料を中心に数々の顔料誘導体が報告されてきた。例えば、顔料のスルホン化物あるいはその金属塩を顔料と混和する方法（特許文献１乃至３）、置換アミノメチル誘導体を混和する方法（特許文献４）フタルイミドメチル誘導体を混和する方法（特許文献５）等が知られている。 In order to solve these problems, improvement studies of the pigment itself (pigment surface treatment), development of dispersants and surfactants having good adsorptivity to pigments, and proposals of pigment derivatives and the like have been made so far. I came. A pigment derivative is a compound in which a substituent such as acidity or basicity is introduced into a pigment having the same structure or a structure similar to that of a pigment to be atomized, and has affinity and adsorptivity with the pigment and acid-base interaction. Because it has a strong binding force with the dispersant, it has the property of improving the fine particle formation and dispersion stabilization of the pigment, and is used in the pigment pulverization / dispersion fine particle formation step and the like. Pigments used in color filters and inkjets include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthracinone pigments, quinacridone pigments, dioxazine pigments, isoindolin pigments, isoindolinone pigments, and azo pigments. Dye lake pigments and the like have been mentioned, and a number of pigment derivatives have been reported, especially phthalocyanine pigments, anthracinone pigments and quinacridone pigments. For example, a method of mixing a sulfonate of a pigment or a metal salt thereof with a pigment (Patent Documents 1 to 3), a method of mixing a substituted aminomethyl derivative (Patent Document 4), a method of mixing a phthalimide methyl derivative (Patent Document 5), and the like. It has been known.
これらの方法は、特定の骨格を有する顔料に対する効果は認められるものの、スルホン基、アミノメチル基、フタルイミドメチル基などを導入することが構造上難しい顔料に対しては、導入する置換基の数や位置の制御が難しく、結果として分散剤としての効果が不充分であり、しかも色調にも悪影響を及ぼす副生成物が多量に生成し、顔料分散液の品質が安定しない等の課題を有する。
また、これまでカラーフィルターのレッド用の顔料として広く使用されているピグメントレッド２５４を用いた顔料組成物は、透過率の向上が課題であった。
Although these methods are effective for pigments having a specific skeleton, the number of substituents to be introduced and the number of substituents to be introduced for pigments for which it is structurally difficult to introduce sulfone groups, aminomethyl groups, phthalimidemethyl groups, etc. It is difficult to control the position, and as a result, the effect as a dispersant is insufficient, and a large amount of by-products that adversely affect the color tone are generated, and the quality of the pigment dispersion is not stable.
Further, in a pigment composition using Pigment Red 254, which has been widely used as a pigment for red in a color filter, improvement in transmittance has been an issue.
本発明が解決しようとする課題は、Ｃ．Ｉ．ピグメントレッド２５４をはじめとするレッド系等の有機顔料を含む顔料組成物（顔料分散液）を、凝集、沈降、経時的な粘度の増加を引き起こすことなく顔料の微粒子化及び高濃度化することであり、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な組成物（分散体）を提供することにある。 The problem to be solved by the present invention is C.I. I. By making a pigment composition (pigment dispersion) containing organic pigments such as red pigments such as Pigment Red 254 into fine particles and increasing the concentration of the pigment without causing aggregation, precipitation, and increase in viscosity over time. An object of the present invention is to provide a stable composition (dispersion) as a colorant for a color filter resist or an ink for inkjet.
本発明者は、上記の課題を解決するために鋭意検討した結果、ベンゾアゾール誘導体からなる化合物を用いることにより、上記課題を解決し得ることを見出し、本発明を完成させたものである。
すなわち、本発明は、
（１）下記式（１）
As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by using a compound composed of a benzoazole derivative, and has completed the present invention.
That is, the present invention
(1) The following formula (1)
（式（２）中、Ｒ１０は、水素原子又は炭素数１乃至４のアルキル基を、Ｒ１１及びＲ１２はそれぞれ独立に炭素数１乃至４のアルキル基を表す。また、Ｒ１０とＲ１１が互いに結合して環を形成してもよく、Ｒ１１とＲ１２が互いに結合して環を形成してもよい。Ｙは二価の連結基−ＳＯ２−又は−ＣＯ−を表す。Ｚは炭素数１乃至６のアルキレン基又はアリーレン基を表す。）で表される置換基を、残りの７つは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ニトロ基又はハロゲン原子を表す。Ｘは酸素原子、硫黄原子又は二価の連結基−ＮＲ9−を表す。Ｒ９は水素原子又は炭素数１乃至４のアルキル基を表す。）で表される構造を有するベンゾアゾール化合物、
（２）Ｙが二価の連結基−ＳＯ２−であり、かつＺが炭素数１乃至６のアルキレン基である前項（１）に記載のベンゾアゾール化合物、
（３）Ｒ1乃至Ｒ８のいずれか１つが式（２）で表される置換基で、残りの７つが水素原子であり、かつＸが硫黄原子又は二価の連結基−ＮＨ−である前項（１）又は（２）に記載のベンゾアゾール化合物、
（４）前項（１）乃至（３）のいずれか一項に記載のベンゾアゾール化合物、有機顔料及び樹脂分散剤を含有する顔料組成物、
（５）樹脂分散剤が酸性基を有する樹脂分散剤である前項（４）に記載の顔料組成物、
（６）有機顔料１００質量部に対するベンゾアゾール化合物の添加量が１乃至５０質量部である前項（４）又は（５）に記載の顔料組成物、
（７）有機顔料がジケトピロロピロール骨格を有する顔料である前項（４）乃至（６）のいずれか一項に記載の顔料組成物、
（８）前項（４）乃至（７）のいずれか一項に記載の顔料組成物及び重合性化合物を含有するカラーレジスト、
（９）前項（１）乃至（３）のいずれか一項に記載のベンゾアゾール化合物を含有するインクジェット用インク組成物、及び
（１０）少なくとも一種以上の有機溶剤を含有する前項（９）に記載のインクジェット用インク組成物、
に関する。
(In the formula (2), R 10 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, represents an alkyl group of R 11 and R 12 carbon atoms are each independently 1 to 4. Further, R 10 and R 11 may be bonded to each other to form a ring, or R 11 and R 12 may be bonded to each other to form a ring. Y represents a divalent linking group -SO 2- or -CO-. Z represents an alkylene group having 1 to 6 carbon atoms or an arylene group), and the remaining 7 are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms. , Nitro group or halogen atom. X is an oxygen atom, a sulfur atom or a divalent linking group -NR 9 - represents a. R 9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ), A benzoazole compound having a structure represented by).
(2) Y is a divalent linking group -SO 2 - and is, and Z is benzo azole compound according to item (1) is an alkylene group having 1 to 6 carbon atoms,
(3) Any one of R 1 to R 8 is a substituent represented by the formula (2), the remaining seven are hydrogen atoms, and X is a sulfur atom or a divalent linking group -NH-. The benzoazole compound according to the preceding paragraph (1) or (2),
(4) A pigment composition containing the benzoazole compound, the organic pigment and the resin dispersant according to any one of the preceding items (1) to (3).
(5) The pigment composition according to (4) above, wherein the resin dispersant is a resin dispersant having an acidic group.
(6) The pigment composition according to (4) or (5) above, wherein the amount of the benzoazole compound added to 100 parts by mass of the organic pigment is 1 to 50 parts by mass.
(7) The pigment composition according to any one of (4) to (6) above, wherein the organic pigment is a pigment having a diketopyrrolopyrrole skeleton.
(8) A color resist containing the pigment composition and the polymerizable compound according to any one of (4) to (7) above.
(9) The inkjet ink composition containing the benzoazole compound according to any one of (1) to (3) above, and (10) the above item (9) containing at least one or more organic solvents. Inkjet ink composition,
Regarding.
本発明の式（１）で示されるベンゾアゾール化合物は製造が極めて容易であり、該化合物を使用することにより、Ｃ．Ｉ．ピグメントレッド２５４等の顔料を含む顔料組成物を、凝集、沈降、経時的な粘度の増加を引き起こすことなく微粒子化・高濃度化することが可能となり、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な分散体を得ることができる。 The benzoazole compound represented by the formula (1) of the present invention is extremely easy to produce, and by using the compound, C.I. I. Pigment composition containing pigments such as Pigment Red 254 can be made into fine particles and have a high concentration without causing aggregation, precipitation, and increase in viscosity over time, and is a colorant for color filter resists and inkjet inks. As a result, a stable dispersion can be obtained.
以下に本発明を詳細に説明する。
本発明のベンゾアゾール化合物は下記式（１）で表される構造を有する。
The present invention will be described in detail below.
The benzoazole compound of the present invention has a structure represented by the following formula (1).
本発明のベンゾアゾール化合物は、カラーフィルター用レジストやインクジェット用インクの着色剤として好適に用いることができる。以下、便宜上、「本発明のベンゾアゾール化合物」を含めて、単に「本発明の化合物」と簡略して記載することもある。 The benzoazole compound of the present invention can be suitably used as a colorant for a resist for a color filter and an ink for inkjet. Hereinafter, for convenience, the term "compound of the present invention" may be simply referred to as "compound of the present invention" including the "benzoazole compound of the present invention".
式（１）中、Ｒ１乃至Ｒ８のいずれか１つは下記式（２）で表される置換基を、残りの７つは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ニトロ基又はハロゲン原子を表す。 In the formula (1), any one of R 1 to R 8 is a substituent represented by the following formula (2), and the remaining seven are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon number. Represents 4 to 4 alkoxy groups, nitro groups or halogen atoms.
式（１）のＲ１乃至Ｒ８が表す炭素数１乃至４のアルキル基は、直鎖、分岐鎖のいずれでもよく、その具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基及びｔｅｒｔ−ブチル基等が挙げられる。
式（１）のＲ１乃至Ｒ８が表す炭素数１乃至４のアルコキシ基は、直鎖、分岐鎖のいずれでもよく、その具体例としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉｓｏ−プロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基及びｔｅｒｔ−ブトキシ基等が挙げられる。
式（１）のＲ1乃至Ｒ8が表すハロゲン原子の具体例としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、好ましくは臭素原子又は塩素原子である。
式（１）におけるＲ１乃至Ｒ８としては、Ｒ1乃至Ｒ8のいずれか１つが式（２）で表される置換基であって、残りの７つが水素原子、炭素数１乃至４のアルキル基、ニトロ基又はハロゲン原子であることが好ましく、Ｒ１乃至Ｒ８のいずれか１つが式（２）で表される置換基であって、残りの７つが水素原子であることがより好ましい。
The alkyl group having 1 to 4 carbon atoms represented by R 1 to R 8 in the formula (1) may be a straight chain or a branched chain, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and iso. -Propyl group, n-butyl group, sec-butyl group, tert-butyl group and the like can be mentioned.
The alkoxy group having 1 to 4 carbon atoms represented by R 1 to R 8 in the formula (1) may be a linear group or a branched chain, and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an iso. -Propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like can be mentioned.
Specific examples of the halogen atom represented by R 1 to R 8 of the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a bromine atom or a chlorine atom is preferable.
As R 1 to R 8 in the formula (1), any one of R 1 to R 8 is a substituent represented by the formula (2), and the remaining seven are hydrogen atoms and have 1 to 4 carbon atoms. It is preferably an alkyl group, a nitro group or a halogen atom, and it is more preferable that any one of R 1 to R 8 is a substituent represented by the formula (2) and the remaining seven are hydrogen atoms. ..
式（１）中、Ｘは酸素原子、硫黄原子又は二価の連結基−ＮＲ９−を表す。Ｒ９は水素原子又は炭素数１乃至４のアルキル基を表す。
式（１）中のＲ９が表す炭素数１乃至４のアルキル基の具体例としては、式（１）中のＲ１乃至Ｒ８が表す炭素数１乃至４のアルキル基の具体例と同じものが挙げられる。
式（１）におけるＸとしては酸素原子、硫黄原子又は二価の連結基−ＮＲ９−であって、Ｒ９が水素原子又はメチル基であることが好ましく、硫黄原子又は二価の連結基−ＮＲ９−であって、Ｒ９が水素原子であることがより好ましい。
In the formula (1), X represents an oxygen atom, a sulfur atom or a divalent linking group -NR 9 - represents a. R 9 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R 9 in the formula (1) are the same as the specific examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 to R 8 in the formula (1). Things can be mentioned.
X in the formula (1) is an oxygen atom, a sulfur atom or a divalent linking group −NR 9 −, and R 9 is preferably a hydrogen atom or a methyl group, preferably a sulfur atom or a divalent linking group −. It is more preferable that the NR is 9 − and R 9 is a hydrogen atom.
式（２）中、Ｒ１０は、水素又は炭素数１乃至４のアルキル基を表す。
式（２）中のＲ１０が表す炭素数１乃至４のアルキル基の具体例としては、式（１）中のＲ１乃至Ｒ８が表す炭素数１乃至４のアルキル基の具体例と同じものが挙げられる。
式（２）におけるＲ１０としては、水素原子であるか又はＲ１０と後述するＲ１１が結合して環を形成することが好ましく、該形成する環はピペラジン環であることが好ましい。
In formula (2), R 10 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R 10 in the formula (2) are the same as the specific examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 to R 8 in the formula (1). Things can be mentioned.
The R 10 in the formula (2) is preferably a hydrogen atom or R 10 and R 11 described later are bonded to form a ring, and the formed ring is preferably a piperazine ring.
式（２）中、Ｒ１１及びＲ１２はそれぞれ独立に炭素数１乃至４のアルキル基を表す。
式（２）中のＲ１１及びＲ１２が表す炭素数１乃至４のアルキル基の具体例としては、式（１）中のＲ１乃至Ｒ８が表す炭素数１乃至４のアルキル基の具体例と同じものが挙げられる。
式（２）におけるＲ１１及びＲ１２としては、炭素数１乃至３のアルキル基が好ましい。
In formula (2), R 11 and R 12 each independently represent an alkyl group having 1 to 4 carbon atoms.
Specific examples of the alkyl groups having 1 to 4 carbon atoms represented by R 11 and R 12 in the formula (2) include the alkyl groups having 1 to 4 carbon atoms represented by R 1 to R 8 in the formula (1). The same as the example can be mentioned.
As R 11 and R 12 in the formula (2), an alkyl group having 1 to 3 carbon atoms is preferable.
式（２）中、Ｙは二価の連結基−ＳＯ２−又は−ＣＯ−を表す。
式（２）におけるＹとしては、二価の連結基−ＳＯ２−であることが好ましい。
In formula (2), Y represents a divalent linking group -SO 2- or -CO-.
As Y in the formula (2), the divalent linking group -SO 2 - is preferably.
式（２）中、Ｚは炭素数１乃至６のアルキレン基又はアリーレン基を表す。
式（２）中のＺが表す炭素数１乃至６のアルキレン基は、直鎖、分岐鎖のいずれでもよく、その具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、２−メチルプロピレン基等が挙げられる。
式（２）中のＺが表すアリーレン基の具体例としては、フェニル基、ナフチル基、ビフェニル基、ピリジル基等が挙げられる。
式（２）におけるＺとしては、炭素数１乃至６のアルキレン基が好ましく、炭素数１乃至６の直鎖のアルキレン基がより好ましい。
In the formula (2), Z represents an alkylene group or an arylene group having 1 to 6 carbon atoms.
The alkylene group having 1 to 6 carbon atoms represented by Z in the formula (2) may be a linear group or a branched chain, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group. Examples thereof include a hexylene group and a 2-methylpropylene group.
Specific examples of the arylene group represented by Z in the formula (2) include a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group and the like.
As Z in the formula (2), an alkylene group having 1 to 6 carbon atoms is preferable, and a linear alkylene group having 1 to 6 carbon atoms is more preferable.
式（２）のＲ１０とＲ１１が互いに結合して形成する環は、窒素原子を少なくとも二つ含む複素環であれば特に限定されないが、例えばイミダゾリジン環及びピペラジン環等が挙げられる。
式（２）のＲ１１とＲ１２が互いに結合して形成する環は、窒素原子を少なくとも一つ含む複素環であれば特に限定されないが、例えばピロリジン環、ピペリジン環及びモルホリン環等が挙げられる。
尚、式（２）におけるＺが側鎖を有するアルキレン基の場合には、該側鎖とＲ１０又はＲ１１が互いに結合して環を形成してもよく、またＺがアリーレン基の場合には、該アリーレン基が有する芳香環上の水素原子とＲ１０又はＲ１１が互いに結合して環を形成してもよい。これらＺとＲ１０又はＲ１１が互いに結合して形成する環は、窒素原子を少なくとも一つ含む複素環であれば特に限定されないが、例えばピロリジン環及びピペリジン環等が挙げられる。
The ring formed by bonding R 10 and R 11 of the formula (2) to each other is not particularly limited as long as it is a heterocycle containing at least two nitrogen atoms, and examples thereof include an imidazolidine ring and a piperazine ring.
The ring formed by bonding R 11 and R 12 of the formula (2) to each other is not particularly limited as long as it is a heterocycle containing at least one nitrogen atom, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. ..
When Z in the formula (2) is an alkylene group having a side chain, the side chain and R 10 or R 11 may be bonded to each other to form a ring, and when Z is an arylene group. May form a ring by bonding the hydrogen atom on the aromatic ring of the arylene group and R 10 or R 11 to each other. The ring formed by bonding Z and R 10 or R 11 to each other is not particularly limited as long as it is a heterocycle containing at least one nitrogen atom, and examples thereof include a pyrrolidine ring and a piperidine ring.
式（１）で示される本発明のベンゾアゾール化合物は、例えば次のような方法で合成することができる。
すなわち、まずは下記式（３）で示される化合物と下記式（４）で表される化合物を縮合反応させることにより、下記式（５）で表される化合物が得られる。下記式（３）乃至（５）において、Ｒ１乃至Ｒ８は水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ニトロ基又はハロゲン原子を表し、Ｘは上記式（１）におけるＸと同じ意味を表す。
次に前記で得られた式（５）で表される化合物をクロロスルホン酸等でクロロスルホン化し、その後アミノ化によりスルファモイル基を形成することにより一般式（１）に表される所望の化合物を合成することが出来る。
The benzoazole compound of the present invention represented by the formula (1) can be synthesized by, for example, the following method.
That is, first, the compound represented by the following formula (3) is obtained by subjecting the compound represented by the following formula (3) to the compound represented by the following formula (4) by a condensation reaction. In the following formulas (3) to (5), R 1 to R 8 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a halogen atom, and X represents the above formula. It has the same meaning as X in (1).
Next, the compound represented by the formula (5) obtained above is chlorosulfonated with chlorosulfonic acid or the like, and then asulfamoyl group is formed by amination to obtain a desired compound represented by the general formula (1). Can be synthesized.
本発明の化合物の具体例を以下に示す。 Specific examples of the compound of the present invention are shown below.
本発明の顔料組成物は、本発明の化合物、有機顔料及び樹脂分散剤を含有する。
本発明の顔料組成物が含有する有機顔料は、カラーインデックスに記載されたものなど従来公知のものであれば特に限定されない。例えば、アゾ系、アンサンスロン系、アントラキノン系、イソインドリノン系、イソインドリン系、インダンスロン系、キナクリドン系、キノフタロン系、ジオキサジン系、ジケトピロロピロール系、チオインジゴ系、フタロシアニン系、ペリレン系及びベンズイミダゾロン系等の顔料が挙げられ、ジケトピロロピロール系の顔料（ジケトピロロピロール骨格を有する顔料）が好ましい。
本発明の顔料組成物における本発明の化合物の含有量は、有機顔料１００質量部に対して通常０．１乃至７０質量部であり、好ましくは０．５乃至６０質量部、より好ましくは１乃至５０質量部である。有機顔料に対する本発明の化合物の添加量を前記の範囲とすることにより、顔料組成物の分散安定性及び有機顔料の微粒子化が達成される。
The pigment composition of the present invention contains the compound of the present invention, an organic pigment and a resin dispersant.
The organic pigment contained in the pigment composition of the present invention is not particularly limited as long as it is conventionally known, such as those described in the color index. For example, azo, anthanthrone, anthraquinone, isoindolinone, isoindoline, indanslon, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole, thioindigo, phthalocyanine, perylene and Examples thereof include benzimidazolone-based pigments, and diketopyrrolopyrrole-based pigments (pigments having a diketopyrrolopyrrole skeleton) are preferable.
The content of the compound of the present invention in the pigment composition of the present invention is usually 0.1 to 70 parts by mass, preferably 0.5 to 60 parts by mass, and more preferably 1 to 1 to 70 parts by mass with respect to 100 parts by mass of the organic pigment. 50 parts by mass. By setting the amount of the compound of the present invention added to the organic pigment within the above range, dispersion stability of the pigment composition and fine particle formation of the organic pigment are achieved.
本発明の顔料組成物が含有する樹脂分散剤は、公知の樹脂分散剤であれば特に限定されないが、例えば、スチレン系（共）重合体、（メタ）アクリル酸エステル系（共）重合体、スチレン−マレイン酸エステル系共重合体、セルロースアセテート系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂などが挙げられる。これらの樹脂分散剤は酸性基を有するものが好ましい。
樹脂分散剤の市販品としては、例えば、ビッグケミージャパン株式会社のＢＹＫ１０２、１０６、１１１、１１８、１７０、１７４、ＢＡＳＦジャパン社のジョンクリル５８６、６１１、８０４、８１９などが挙げられるが、これらに限定されない。樹脂分散剤の添加量は、有機顔料１００質量部に対して通常５乃至１００質量部、好ましくは１０乃至５０質量部である。有機顔料に対する樹脂分散剤の添加量を前記の範囲とすることにより、分散安定性の良好な顔料組成物が得られる。
The resin dispersant contained in the pigment composition of the present invention is not particularly limited as long as it is a known resin dispersant, and for example, a styrene-based (co) polymer, a (meth) acrylic acid ester-based (co) polymer, and the like. Examples thereof include styrene-maleic acid ester-based copolymers, cellulose acetate-based resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, and polyimide-based resins. These resin dispersants preferably have an acidic group.
Examples of commercially available resin dispersants include BYK102, 106, 111, 118, 170, 174 of BASF Japan Ltd., John Krill 586, 611, 804, 819 of BASF Japan Ltd., and the like. Not limited. The amount of the resin dispersant added is usually 5 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the organic pigment. By setting the amount of the resin dispersant added to the organic pigment within the above range, a pigment composition having good dispersion stability can be obtained.
本発明の顔料組成物には、必要により有機溶剤を加えることができる。用い得る有機溶剤は特に限定されないが、例えば、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチルセロソルブアセテート、ブチルセロソルブアセテート、エチルセロソルブ、シクロヘキサノン、シクロペンタノン、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、酢酸エチル、酢酸ブチル、メタノール、エタノール、イソプロピルアルコールなどが挙げられる。これらは単独で用いても２種以上を混合して用いてもよい。有機溶剤は顔料組成物中に好ましくは９０質量％以下を占める量が用いられる。 An organic solvent can be added to the pigment composition of the present invention, if necessary. The organic solvent that can be used is not particularly limited, and for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve, cyclohexanone, cyclopentanone, ethylene glycol diethyl ether, Examples thereof include diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, methanol, ethanol and isopropyl alcohol. These may be used alone or in combination of two or more. The amount of the organic solvent used is preferably 90% by mass or less in the pigment composition.
本発明のカラーレジストは、前記本発明の顔料組成物及び重合性化合物を含有する。
本発明のカラーフィルターレジストに用い得る重合性化合物としては、光重合モノマー、エポキシ化合物及びメラミン系化合物等が挙げられる。これらの重合性化合物の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコー（メタ）アクリレート、テトラエチレングリコール（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセロール（メタ）アクリレート、ビスフェノール−Ａ型エポキシジ（メタ）アクリレート、ビスフェノール−Ｆ型エポキシジ（メタ）アクリレート、ビスフェノール−フルオレン型エポキシジ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化グリセリントリ（メタ）アクリレート、エトキシ化イソシアヌル酸トリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、９,９−ビス〔４−（２−アクリロイルオキシエトキシ）フェニル〕フルオレン、カヤラッドＲＰ−１０４０（日本化薬製）、カヤラッドＤＰＣＡ−３０（日本化薬製）、ＵＡ−３３Ｈ（新中村化学製)、ＵＡ−５３Ｈ（新中村化学製)及びＭ−８０６０（東亞合成製)等の（メタ）アクリレートモノマー；ＴＥＭＰＩＣ（堺化学製)、ＴＭＭＰ（堺化学製)、ＰＥＭＰ（堺化学製）及びＤＰＭＰ（堺化学製）等のチオール系重合モノマー；日本化薬製品のＮＣ−６０００、ＮＣ−６３００、ＮＣ−６３００Ｈ、ＮＣ−３０００、ＥＯＣＮ−１０２０、ＸＤ−１０００、ＥＰＰＮ−５０１Ｈ、ＢＲＥＮ−Ｓ、ＮＣ−７３００Ｌ、ダイセル化学製品のセロキサイト２０２１Ｐ、ＥＨＰＥ３１５０、サイクロマーＭ１００、エポリードＰＢ３６００、ジャパンエポキシレジン製品のエピコート８２８、エピコートＹＸ８０００、エピコートＹＸ４０００、プリンテック製品のＶＧ−３１０１Ｌ、サイラエースＳ５１０（チッソ）、ＴＥＰＩＣ（日産化学工業）等のエポキシ化合物；並びにメチロール化メラミン及びＭｗ−３０（三和ケミカル）等のメラミン系化合物が挙げられるが、これらに限定されるものではない。
これらの重合性化合物には、必要により重合開始剤や硬化促進剤等を併用することが好ましい。
重合性化合物は本発明のカラーレジスト中に１乃至５０質量％を占める量が用いられる。
The color resist of the present invention contains the pigment composition of the present invention and a polymerizable compound.
Examples of the polymerizable compound that can be used in the color filter resist of the present invention include photopolymerizable monomers, epoxy compounds, and melamine compounds. Specific examples of these polymerizable compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, Triethylene Glyco (Meta) Acrylate, Tetraethylene Glycol (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate , Dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, trimethyl ethoxylated Propanetri (meth) acrylate, propoxylated trimetyl propanetri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, ethoxylated pentaerythritol Tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayarad RP-1040 (manufactured by Nippon Kayaku), Kayarad DPCA-30 (manufactured by Nihon Kayaku), UA-33H (Meta) acrylate monomers such as (Shin-Nakamura Kagaku), UA-53H (Shin-Nakamura Kagaku) and M-8060 (Toa Synthetic); TEMPIC (Sakai Kagaku), TMMP (Sakai Kagaku), PEMP (Sakai) Thiol-based polymerized monomers such as (manufactured by Chemical) and DPMP (manufactured by Sakai Chemical); NC-6000, NC-6300, NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, Nippon Kayaku products. BREN-S, NC-7300L, Celokisite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin Products Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec Products VG-3101L, Cyra Ace S510 (Chisso) ), TEPIC (Nissan Chemical Industry), etc.; and methylolated melamine And melamine compounds such as Mw-30 (Sanwa Chemical), but are not limited thereto.
It is preferable to use a polymerization initiator, a curing accelerator, or the like in combination with these polymerizable compounds, if necessary.
The polymerizable compound is used in an amount that occupies 1 to 50% by mass in the color resist of the present invention.
本発明のカラーレジストに必要により加えることのできるその他の添加剤としては、例えばチクソ付与剤、重合開始剤や硬化剤、硬化促進剤、重合禁止剤、有機又は無機フィラー、カップリング剤等が挙げられるが、これらはカラーレジストの具体的な目的用途や用法によって選択すればよく上記に限定されない。また、その添加量も、具体的な目的用途に合わせて選択すれば良い。
尚、これらの添加剤のうち、チクソ付与剤、有機又は無機フィラー及びカップリング剤等は、必要により本発明の顔料組成物に加えることも出来る。
Other additives that can be added to the color resist of the present invention as needed include, for example, thixo-imparting agents, polymerization initiators and curing agents, curing accelerators, polymerization inhibitors, organic or inorganic fillers, coupling agents and the like. However, these may be selected depending on the specific purpose and usage of the color resist, and are not limited to the above. In addition, the amount of the addition may be selected according to the specific purpose and application.
Among these additives, a thixo-imparting agent, an organic or inorganic filler, a coupling agent and the like can be added to the pigment composition of the present invention, if necessary.
本発明の顔料組成物は、例えば次のような方法で調整することができる。すなわち、有機顔料及び本発明の化合物の配合方法としては、従来公知の種々の方法、例えば、それぞれの乾燥粉末やプレスケーキを単に混合する方法やニーダー、ビーズミル、ディゾルバー、アトライター等の各種分散機により機械的に混合する方法、水又は有機溶剤中に有機顔料を懸濁させ、その中に本発明の化合物を添加混合して有機顔料の表面に均一に沈着する方法などが挙げられる。次に、得られた有機顔料及び本発明の化合物の混合物に、樹脂分散剤と必要に応じて各種有機溶剤や各種添加剤等を配合して、サンドミル、アニュラー型ビーズミル、アトライター等で分散することにより、所望の顔料組成物を製造することができる。或いは簡便的には、有機顔料、本発明の化合物及び樹脂分散剤と必要に応じてその他の成分を、一括で混合及び分散しても構わない。
また本発明のカラーレジストは、前記で得られた顔料組成物にさらに重合性化合物及び各種添加剤等を配合して、サンドミル、アニュラー型ビーズミル、アトライター等で分散することにより製造することができる。或いは簡便的には、有機顔料、本発明の化合物及び樹脂分散剤と必要に応じてその他の成分を、一括で混合及び分散しても構わない。
The pigment composition of the present invention can be prepared, for example, by the following method. That is, as a method for blending the organic pigment and the compound of the present invention, various conventionally known methods, for example, a method of simply mixing the respective dry powders and press cakes, and various dispersers such as a kneader, a bead mill, a dissolver, and an attritor. Examples thereof include a method of mechanically mixing with water or a method of suspending an organic pigment in water or an organic solvent, adding and mixing the compound of the present invention into the suspension, and uniformly depositing the compound on the surface of the organic pigment. Next, the obtained mixture of the organic pigment and the compound of the present invention is mixed with a resin dispersant and various organic solvents and various additives as necessary, and dispersed by a sand mill, an annual bead mill, an attritor or the like. This makes it possible to produce a desired pigment composition. Alternatively, for convenience, the organic pigment, the compound of the present invention, the resin dispersant and, if necessary, other components may be mixed and dispersed all at once.
Further, the color resist of the present invention can be produced by further blending a polymerizable compound, various additives and the like with the pigment composition obtained above and dispersing them with a sand mill, an annual bead mill, an attritor or the like. .. Alternatively, for convenience, the organic pigment, the compound of the present invention, the resin dispersant and, if necessary, other components may be mixed and dispersed all at once.
本発明のインクジェット用インク組成物は、本発明の化合物と本発明の化合物以外の少なくとも一成分を含有する。本発明の化合物以外の成分は、一般的にインクジェット用インクに用いられる成分であれば特に限定されず、その添加量もインクジェット記録時の妨げとならない限り特に限定されない。本発明の化合物以外の成分として最も典型的なものは有機溶剤である。本発明のインクジェット用インク組成物が含有し得る有機溶剤としては、本発明の顔料組成物に必要により加えることのできる有機溶剤と同じものが挙げられ、その含有量はインクジェット用インク組成物中に好ましくは９０質量％以下を占める量である。 The inkjet ink composition of the present invention contains at least one component other than the compound of the present invention and the compound of the present invention. The components other than the compound of the present invention are not particularly limited as long as they are components generally used for inkjet inks, and the amount of the components added is not particularly limited as long as they do not interfere with inkjet recording. The most typical component other than the compound of the present invention is an organic solvent. Examples of the organic solvent that can be contained in the inkjet ink composition of the present invention include the same organic solvents that can be added to the pigment composition of the present invention as needed, and the content thereof is contained in the inkjet ink composition. The amount is preferably 90% by mass or less.
本発明の顔料組成物の用途は特に限定されず、例えばグラビア印刷インキなどの各種印刷インキ、塗料、電子写真用乾式トナー又は湿式トナー、インクジェット記録用インキ、カラーフィルター用レジスト（カラーレジスト）の着色剤などの種々の用途が挙げられる。特に、本発明の顔料組成物は、顔料の微粒子化及び高い安定性が要求されるカラーフィルター用レジスト着色剤、インクジェット記録用インキとして有用である。 The application of the pigment composition of the present invention is not particularly limited, and for example, coloring of various printing inks such as gravure printing inks, paints, dry toners or wet toners for electrophotographic, ink jet recording inks, and resists (color resists) for color filters. Various uses such as agents can be mentioned. In particular, the pigment composition of the present invention is useful as a resist colorant for a color filter and an ink for inkjet recording, which require fine particle formation and high stability of the pigment.
以下に本発明を実施例により具体的に説明する。尚、本文中「部」及び「％」とあるのは、特別の記載のない限り質量基準である。実施例における極大吸収波長は分光光度計「（株）島津製作所製ＵＶ−３１５０」で測定した値であり、酸価はＪＩＳ Ｋ−００７０：１９９２に準拠した測定方法で測定した値である。また、重量平均分子量はゲルパーミエイションクロマトグラフィーの測定結果に基づいて、ポリスチレン換算で算出した値である。 Hereinafter, the present invention will be specifically described with reference to Examples. In addition, "part" and "%" in the text are based on mass unless otherwise specified. The maximum absorption wavelength in the examples is a value measured by a spectrophotometer "UV-3150 manufactured by Shimadzu Corporation", and the acid value is a value measured by a measuring method based on JIS K-0070: 1992. The weight average molecular weight is a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography.
実施例１（上記具体例化合物のＮｏ．１で示される化合物の合成）
（工程１）
反応容器に２−メチルベンゾイミダゾール５０部、無水フタル酸１２６部、安息香酸１４部及びスルホラン７５０部を加え、１８０℃で１４時間反応させた後、４０℃まで冷却し、この反応液をメタノール２０００部中に加え、「懸濁液１」を得た。「懸濁液１」をろ過して得られた「ウェットケーキ１」１１１部を８０℃の熱風乾燥機で乾燥させることにより、下記式（１１）で表される化合物を８４部得た。
Example 1 (Synthesis of the compound represented by No. 1 of the above-mentioned specific example compound)
(Step 1)
50 parts of 2-methylbenzimidazole, 126 parts of phthalic anhydride, 14 parts of benzoic acid and 750 parts of sulfolane were added to the reaction vessel, reacted at 180 ° C. for 14 hours, cooled to 40 ° C., and the reaction solution was methanol 2000. In addition to the part, "Suspension 1" was obtained. By drying 111 parts of "wet cake 1" obtained by filtering "suspension 1" with a hot air dryer at 80 ° C., 84 parts of a compound represented by the following formula (11) was obtained.
（工程２）
クロロスルホン酸２００部中に、工程１で得られた式（１１）で表される化合物４０部を５乃至１０℃でゆっくり添加した後、室温で２４時間反応させた。この反応液を２０００部の氷中に約２０分間で滴下し、析出した固体をろ過分離した。さらに得られた固体を氷２００部、水８００部中で懸濁洗浄し、ろ過分離することにより、下記式（１２）で表される化合物を含む「ウェットケーキ２」２０１部を得た。
(Step 2)
To 200 parts of chlorosulfonic acid, 40 parts of the compound represented by the formula (11) obtained in Step 1 was slowly added at 5 to 10 ° C., and then reacted at room temperature for 24 hours. This reaction solution was added dropwise to 2000 parts of ice for about 20 minutes, and the precipitated solid was separated by filtration. Further, the obtained solid was suspended and washed in 200 parts of ice and 800 parts of water, and filtered and separated to obtain 201 parts of "wet cake 2" containing the compound represented by the following formula (12).
（工程３）
工程２で得られた式（１２）で表される化合物を含む「ウェットケーキ２」２０１部を水５２０部に懸濁させた後、Ｎ，Ｎ−ジエチルエチレンジアミンを８９部加え室温で三時間撹拌した。懸濁液をろ過して得られた固体を水５００部で懸濁洗浄し、「懸濁液２」を得た。「懸濁液２」をろ過分離することにより得た「ウェットケーキ３」１９３部を８０℃の熱風乾燥機で乾燥させることにより、具体例化合物Ｎｏ．１で示される化合物５４部を得た。該化合物の極大吸収波長λｍａｘは３５４ｎｍ（ＮＭＰ）であった。
(Step 3)
After suspending 201 parts of "wet cake 2" containing the compound represented by the formula (12) obtained in step 2 in 520 parts of water, 89 parts of N, N-diethylethylenediamine was added and stirred at room temperature for 3 hours. bottom. The solid obtained by filtering the suspension was suspended and washed with 500 parts of water to obtain "Suspension 2". Specific Example Compound No. was obtained by drying 193 parts of "Wet Cake 3" obtained by filtering and separating "Suspension 2" with a hot air dryer at 80 ° C. 54 parts of the compound represented by 1 was obtained. The maximum absorption wavelength λmax of the compound was 354 nm (NMP).
合成例１（下記式（１５）で表される比較用化合物の合成）
（工程４）
クロロスルホン酸１００部中に、下記式（１３）で表される化合物１０部を５乃至１０℃でゆっくり添加した後、チオニルクロリド２１部を加え、室温で２２時間反応させた。その後５０℃でさらに１２時間反応させ、この反応液を５２０部の氷中に約１５分間で滴下し、析出した固体をろ過分離し、下記式（１４）で表される化合物を含む「ウェットケーキ４」５６．４部を得た。
Synthesis Example 1 (Synthesis of comparative compound represented by the following formula (15))
(Step 4)
To 100 parts of chlorosulfonic acid, 10 parts of the compound represented by the following formula (13) was slowly added at 5 to 10 ° C., then 21 parts of thionyl chloride was added, and the mixture was reacted at room temperature for 22 hours. After that, the reaction was carried out at 50 ° C. for another 12 hours, the reaction solution was added dropwise to 520 parts of ice for about 15 minutes, the precipitated solid was filtered and separated, and a "wet cake" containing the compound represented by the following formula (14) was contained. 4 ”56.4 copies were obtained.
（工程５）
工程４で得られた式（１４）で表される化合物を含む「ウェットケーキ４」５６．４部を水２００部に懸濁させた後、Ｎ，Ｎ−ジエチルエチレンジアミンを２０部加え室温で２時間撹拌した。懸濁液をろ過して得られた固体を水２００部で懸濁洗浄し、「懸濁液２」を得た。「懸濁液３」をろ過分離することにより得た「ウェットケーキ５」５４部を８０℃の熱風乾燥機で乾燥させることにより、下記式（１５）で表される比較用化合物（特許文献７の式（１）に包含される化合物）１０．７部を得た。
(Step 5)
After suspending 56.4 parts of "wet cake 4" containing the compound represented by the formula (14) obtained in step 4 in 200 parts of water, 20 parts of N, N-diethylethylenediamine was added and 2 at room temperature. Stirred for hours. The solid obtained by filtering the suspension was suspended and washed with 200 parts of water to obtain "Suspension 2". By drying 54 parts of "wet cake 5" obtained by filtering and separating "suspension 3" with a hot air dryer at 80 ° C., a comparative compound represented by the following formula (15) (Patent Document 7). 10.7 parts of the compound included in the formula (1) of (1) was obtained.
合成例２（樹脂分散剤溶液Ａの調整）
１Ｌの四つ口フラスコにシクロペンタノン２３５部、メタクリル酸１４．７部、メタクリル酸２−ヒドロキシエチル１３．３部、メタクリル酸ベンジル７２部、パーブチルＲＴＭＯ（日本油脂株式会社製）３部を仕込み、窒素ガス注入下８０℃まで昇温し、７８乃至８０℃でそのまま４時間攪拌した。反応終了後、室温まで冷却し、無色透明で均一な樹脂分散剤溶液Ａを得た。得られた樹脂分散剤のポリスチレン換算重量平均分子量は１８６００であり、酸価は９８であった。尚、本明細書において上付きのＲＴＭは登録商標を意味する。
Synthesis Example 2 (Preparation of Resin Dispersant Solution A)
235 parts of cyclopentanone, 14.7 parts of methacrylic acid, 13.3 parts of 2-hydroxyethyl methacrylate, 72 parts of benzyl methacrylate, and 3 parts of perbutyl RTM (manufactured by Nippon Oil & Fats Co., Ltd.) are placed in a 1 L four-necked flask. The temperature was raised to 80 ° C. under the injection of nitrogen gas, and the mixture was stirred as it was at 78 to 80 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature to obtain a colorless, transparent and uniform resin dispersant solution A. The polystyrene-equivalent weight average molecular weight of the obtained resin dispersant was 18,600, and the acid value was 98. In this specification, the superscript RTM means a registered trademark.
実施例２（本発明の顔料組成物の調製）
有機顔料としてＣ．Ｉ．ピグメントレッド２５４ ２．０部、本発明の化合物として実施例１で得られたＮｏ．１で示される化合物０．３部、樹脂分散剤として合成例２で得られた樹脂分散剤溶液Ａ２．７部、溶剤としてシクロヘキサノン１５部を配合し、プレミキシングの後、０．３ｍｍのジルコニアビーズを用いて、ペイントシェーカーで６０分間分散した。
Example 2 (Preparation of the pigment composition of the present invention)
As an organic pigment, C.I. I. Pigment Red 254 2.0 parts, No. 1 obtained in Example 1 as the compound of the present invention. 0.3 parts of the compound shown in 1, 2.7 parts of the resin dispersant solution A obtained in Synthesis Example 2 as a resin dispersant, and 15 parts of cyclohexanone as a solvent were mixed, and after premixing, 0.3 mm zirconia beads were mixed. Was dispersed in a paint shaker for 60 minutes.
比較例１（比較用の顔料組成物の調製）
実施例１で得られたＮｏ．１で示される化合物の代わりに合成例１で得られた式（１５）で表される比較用化合物を用いたこと以外は実施例２と同じ方法で顔料組成物を調製した。
Comparative Example 1 (Preparation of Pigment Composition for Comparison)
No. obtained in Example 1. A pigment composition was prepared in the same manner as in Example 2 except that the comparative compound represented by the formula (15) obtained in Synthesis Example 1 was used instead of the compound represented by 1.
比較例２（比較用の顔料組成物の調製）
実施例１で得られたＮｏ．１で示される化合物を用いず、かつシクロヘキサノンの量を１５．３部に変更したこと以外は実施例２と同じ方法で顔料組成物を調製した。
Comparative Example 2 (Preparation of Pigment Composition for Comparison)
No. obtained in Example 1. A pigment composition was prepared in the same manner as in Example 2 except that the compound shown in 1 was not used and the amount of cyclohexanone was changed to 15.3 parts.
（顔料組成物の微細化評価）
上記実施例２及び比較例１、２の顔料組成物について、得られた分散液２０部をシクロヘキサノン２０部で希釈し、２５０μｍのポリプロピレン製のメッシュでろ過して、下記の評価基準で顔料組成物の微細化度合いを評価した。結果を表１に示した。
・評価基準
ろ過完結まで５分未満：○
ろ過完結まで５分以上３０分以下：△
３０分経ってもろ過完結せず：×
(Evaluation of refinement of pigment composition)
With respect to the pigment compositions of Examples 2 and Comparative Examples 1 and 2, 20 parts of the obtained dispersion was diluted with 20 parts of cyclohexanone, filtered through a 250 μm polypropylene mesh, and the pigment composition was evaluated according to the following evaluation criteria. The degree of miniaturization of was evaluated. The results are shown in Table 1.
・ Evaluation criteria Less than 5 minutes to complete filtration: ○
5 minutes or more and 30 minutes or less until filtration is completed: △
Filtration is not completed even after 30 minutes: ×
表１から明らかなように、実施例２の顔料組成物は、本顔料誘導体を添加しない比較例２や特許文献７の式（１）に包含される比較用の化合物を添加した比較例１と比べてろ過性が良い。すなわち、実施例２は比較例１，２よりも顔料が微細化できているものと考えられ、実際に使用する際の作業性並びにレジストやインクの品質を損なわないものである。 As is clear from Table 1, the pigment composition of Example 2 is different from Comparative Example 2 to which the present pigment derivative is not added and Comparative Example 1 to which the comparative compound included in the formula (1) of Patent Document 7 is added. Good filterability in comparison. That is, it is considered that the pigment of Example 2 is finer than that of Comparative Examples 1 and 2, and the workability in actual use and the quality of the resist and ink are not impaired.
本発明のベンゾアゾール化合物用いることにより、凝集、沈降することなく、微粒子化・高濃度化することが可能であり、顔料誘導体は、カラーフィルター用レジストやインクジェット用インクの着色剤として、安定な分散体を得るために非常に有用である。
By using the benzoazole compound of the present invention, it is possible to make fine particles and increase the concentration without agglomeration and precipitation, and the pigment derivative is stably dispersed as a colorant for a color filter resist or an inkjet ink. Very useful for getting a body.
Claims (10)
で表される置換基を、残りの７つはそれぞれ独立に、水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基又はニトロ基を表す。Ｘは−ＮＲ ９ −を表す。Ｒ９は水素原子を表す。）で表されるベンゾアゾール化合物。 The following formula (1)
The remaining seven independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group . X is -NR 9 - represents a. R 9 represents a hydrogen atom. Benzazole compound represented by).
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