TW201538641A - Coloring composition, coloring cured film and display element - Google Patents

Abstract

To provide a coloring composition suitable for forming coloring curable film with excellent heat resistance and high contrast. A coloring composition, which comprises a colorant (A) and a polymerizable compound (B), wherein the colorant (A) is a combination of at least one elected from monomer (<alpha>3) and polymer (<alpha>4 ) and at least one selected from monomer (<beta>3) and polymer (<beta>4), wherein the monomer (<alpha>3) has at least one chromophore selected from chromophores and spontaneous cyanine chromophore and a polymerizable group, the polymer (<alpha>4) contains the monomer (<alpha>3) as a structural unit, the monomer (<beta>3) has at least one chromophore selected from triarylmethane chromophores and anthraquinone chromophore and a polymerizable group, the polymer (<beta>4) contains the monomer (<beta>3) as a structural unit (which does not include the case of colorant (A) being a combination of said monomer (<alpha>3) and said monomer (<beta>3).

Description

著色組成物、著色硬化膜及顯示元件 Coloring composition, coloring cured film, and display element

本發明關於著色組成物、著色硬化膜和顯示元件，更詳細而言，關於用於形成著色硬化膜的著色組成物、使用該著色組成物形成的著色硬化膜、以及具備該著色硬化膜的顯示元件，該著色硬化膜適用於透射型或反射型的彩色液晶顯示元件、固體攝像元件、有機EL顯示元件、電子紙等。 The present invention relates to a colored composition, a colored cured film, and a display element, and more particularly, to a colored composition for forming a colored cured film, a colored cured film formed using the colored composition, and a display including the colored cured film. The coloring cured film is suitable for a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, or the like.

使用著色感放射線性組成物製造濾色器時，已知有如下方法：在基板上塗布顏料分散型的著色感放射線性組成物並乾燥後，對乾燥塗膜以所希望的圖案形狀照射放射線(以下，稱為「曝光」)，進行顯影，由此得到各色像素(例如，參照專利文獻1~2)。另外，還已知有利用分散有炭黑的光聚合性組成物來形成黑矩陣的方法(例如，參照專利文獻3)。此外，還已知有使用顏料分散型的著色樹脂組成物，採用噴墨方式得到各色像素的方法(例如，參照專利文獻4)。 When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment dispersion type color sensitizing radiation composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape ( Hereinafter, it is referred to as "exposure", and development is performed to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, see Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed color-forming resin composition is known (for example, see Patent Document 4).

近年來，迫切需求液晶顯示元件的高對比度化、固體攝像元件的高精細化，為了實現這些需求，研究了使用染料作為著色劑的技術。但是，一般而言，與使用顏料作為著色劑的情況相比，在使用染料時，耐熱 性大多出現問題。在這樣的背景的下，作為能夠形成耐熱性等優異的著色圖案的著色組成物，例如專利文獻5中提出一種含有色素多聚體作為著色劑的著色組成物。 In recent years, there has been a demand for high contrast of liquid crystal display elements and high definition of solid-state imaging elements. In order to achieve these demands, techniques using dyes as colorants have been studied. However, in general, heat resistance is used when dyes are used as compared with the case of using a pigment as a colorant. Most of the problems occur. Under the above-described background, as a coloring composition capable of forming a coloring pattern excellent in heat resistance and the like, for example, Patent Document 5 proposes a coloring composition containing a dye multimer as a coloring agent.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本特開平2-144502號公報 Patent Document 1: Japanese Patent Laid-Open No. 2-144502

專利文獻2：日本特開平3-53201號公報 Patent Document 2: Japanese Patent Laid-Open No. 3-53201

專利文獻3：日本特開平6-35188號公報 Patent Document 3: Japanese Patent Laid-Open No. Hei 6-35188

專利文獻4：日本特開2000-310706號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2000-310706

專利文獻5：日本特開2013-28764號公報 Patent Document 5: Japanese Patent Laid-Open Publication No. 2013-28764

然而，根據本發明人等的研究，發現使用專利文獻5中記載的著色組成物形成的著色圖案的對比度極低，不適合濾色器等所使用的各色像素。 However, according to the study by the inventors of the present invention, it has been found that the coloring pattern formed using the coloring composition described in Patent Document 5 has an extremely low contrast and is not suitable for each color pixel used in a color filter or the like.

因此，本發明的課題在於提供一種適合形成耐熱性優異且對比度高的著色硬化膜的著色組成物。另外，本發明的課題在於提供使用該著色組成物形成的著色硬化膜和具備該著色硬化膜的顯示元件。 Therefore, an object of the present invention is to provide a colored composition suitable for forming a colored cured film having excellent heat resistance and high contrast. Further, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the colored cured film.

本發明人等經過深入研究，結果發現通過併用具有發出螢光的部位的特定化合物和具有吸收上述螢光的部位的特定化合物作為著色劑，能夠解決解決上述課題。 As a result of intensive studies, the present inventors have found that it is possible to solve the above problems by using a specific compound having a site emitting fluorescence and a specific compound having a site for absorbing the above-mentioned fluorescence as a coloring agent.

即，本發明提供一種著色組成物，其係含有(A)著色劑和(B)聚合性化合物的著色組成物，其中(A)著色劑包含選自單體(α1)和聚合物(α2)(以下，也稱為「化合物群α¹」)中的至少1種與選自單體(β1)和聚合物(β2)(以下，也稱為「化合物群β¹」)中的至少1種的組合，該單體(α1)具有發出螢光的部位和聚合性基團，該聚合物(α2)含有上述單體(α1)作為結構單元，該單體(β1)具有吸收上述螢光的部位和聚合性基團，該聚合物(β2)含有上述單體(β1)作為結構單元，其中，不包括(A)著色劑為上述單體(α1)與上述單體(β1)的組合的情況。 That is, the present invention provides a coloring composition comprising a colored composition of (A) a colorant and (B) a polymerizable compound, wherein (A) the colorant comprises a monomer (α1) and a polymer (α2). At least one of (hereinafter, also referred to as "compound group α ¹ ") and at least one selected from the group consisting of a monomer (β1) and a polymer (β2) (hereinafter also referred to as "compound group β ¹ ") In combination, the monomer (α1) has a fluorescent moiety and a polymerizable group, and the polymer (α2) contains the above monomer (α1) as a structural unit, and the monomer (β1) has absorption of the above fluorescent light. a site and a polymerizable group, the polymer (β2) containing the above monomer (β1) as a structural unit, wherein the coloring agent not including (A) is a combination of the above monomer (α1) and the above monomer (β1) Happening.

另外，本發明提供一種著色組成物，其係含有(A)著色劑和(B)聚合性化合物的著色組成物，其中(A)著色劑包含選自單體(α3)和聚合物(α4)(以下，也稱為「化合物群α²」)中的至少1種與選自單體(β3)和聚合物(β4)(以下，也稱為「化合物群β²」)中的至少1種的組合，該單體(α3)具有選自發色團和花青發色團中的至少1種發色團和聚合性基團，該聚合物(α4)含有該單體(α3)作為結構單元，該單體(β3)具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團和聚合性基團，該聚合物(β4)含有 該單體(β3)作為結構單元，其中，不包括(A)著色劑為上述單體(α3)與上述單體(β3)的組合的情況。 Further, the present invention provides a coloring composition comprising a coloring composition of (A) a coloring agent and (B) a polymerizable compound, wherein (A) the coloring agent comprises a monomer (α3) and a polymer (α4) selected from the group consisting of At least one of (hereinafter, also referred to as "compound group α ² ") and at least one selected from the group consisting of a monomer (β3) and a polymer (β4) (hereinafter also referred to as "compound group β ² ") Combination of the monomer (α3) having a selected from At least one chromophore and a polymerizable group in the chromophore and the cyanine chromophore, the polymer (α4) containing the monomer (α3) as a structural unit, the monomer (β3) having a selected from the group consisting of At least one chromophore and a polymerizable group in the methacrylic chromophore and the chromophore, the polymer (β4) containing the monomer (β3) as a structural unit, wherein (A) coloring is not included The agent is a combination of the above monomer (α3) and the above monomer (β3).

這裡，含有單體作為結構單元的聚合物，只要具有該單體作為必需的結構單元，則可以是均聚物也可以是共聚物。以下，有時將「化合物群α¹和化合物群α²」稱為「化合物群α」，將「化合物群β¹和化合物群β²」稱為「化合物群β」，將「單體(α1)和單體(α3)」稱為「單體α」，將「單體(β1)和單體(β3)」稱為「單體β」，將「聚合物(α2)和聚合物(α4)」稱為「聚合物α」，將「聚合物(β2)和聚合物(β4)」稱為「聚合物β」。 Here, the polymer containing a monomer as a structural unit may be a homopolymer or a copolymer as long as it has the monomer as an essential structural unit. Hereinafter, "compound group α ¹ and compound group α ² " will be referred to as "compound group α", and "compound group β ¹ and compound group β ² " will be referred to as "compound group β", and "monomer (α1) And monomer (α3) are called "monomer α", "monomer (β1) and monomer (β3)" are called "monomer β", and "polymer (α2) and polymer (α4) ") is called "polymer alpha", and "polymer (β2) and polymer (β4)" is called "polymer beta".

此外，本發明提供使用上述著色組成物形成的著色硬化膜和具備該著色硬化膜的顯示元件。這裡，「著色硬化膜」是指用於顯示元件、固體攝像元件的各色像素、黑矩陣、黑間隔物等。 Further, the present invention provides a colored cured film formed using the above colored composition and a display element comprising the colored cured film. Here, the "coloring cured film" means a pixel for each color of a display element or a solid-state image sensor, a black matrix, a black spacer, or the like.

如果使用本發明的著色組成物，則能夠形成耐熱性優異且對比度高的著色硬化膜。 When the colored composition of the present invention is used, a colored cured film having excellent heat resistance and high contrast can be formed.

因此，本發明的著色組成物極其適用於製作彩色液晶顯示元件、有機EL顯示元件、電子紙等的顯示元件、CMOS圖像傳感器等的固體攝像元件。 Therefore, the coloring composition of the present invention is extremely suitable for producing a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.

[實施發明之形態] [Formation of the Invention]

以下，對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.

[著色組成物] [Coloring composition]

以下，對本發明的著色組成物的構成成分進行詳細說明。 Hereinafter, the constituent components of the colored composition of the present invention will be described in detail.

-(A)著色劑- - (A) colorant -

本發明的著色組成物係含有選自化合物群α中的至少1種與選自化合物群β中的至少1種的組合作為著色劑者。 The coloring composition of the present invention contains a combination of at least one selected from the group of compounds α and at least one selected from the group of compounds β as a colorant.

化合物群α中的化合物群α¹是：具有發出螢光的部位和聚合性基團的單體(α1)、以及含有上述單體(α1)作為結構單元的聚合物(α2)。作為發出螢光的部位，例如可舉出發色團、花青發色團。作為化合物群α¹的較佳態樣，可舉出：具有選自發色團和花青發色團中的至少1種發色團和聚合性基團的單體(α3)、以及含有該單體(α3)作為結構單元的聚合物(α4)(化合物群α²)。另外，作為聚合性基團，例如可舉出烯性不飽和基團、環氧乙烷基、氧雜環丁烷基、N-烷氧基甲基胺基等。其中，較佳為烯性不飽和基團。作為單體(α1)的較佳態樣，可舉出具有發出螢光的部位的烯性不飽和單體，更佳為具有選自發色團和花青發色團中的至少1種發色團的烯性不飽和單體，例如可由下述式(1-1)表示。 The compound group α ¹ in the compound group α is a monomer (α1) having a site in which fluorescence is emitted and a polymerizable group, and a polymer (α2) containing the monomer (α1) as a structural unit. As a part that emits fluorescence, for example, Hair color group, flower blue hair color group. Preferred examples of the compound group α ¹ include: having a selected one selected from the group consisting of a monomer (α3) of at least one chromophore and a polymerizable group in a chromophore and a cyanine chromophore, and a polymer (α4) containing the monomer (α3) as a structural unit (compound group α) ² ). Further, examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among them, an ethylenically unsaturated group is preferred. Preferred examples of the monomer (α1) include an ethylenically unsaturated monomer having a site emitting fluorescence, and more preferably selected from the group consisting of olefinic unsaturated monomers. The ethylenically unsaturated monomer of at least one chromophore in the chromophore and the cyanine chromophore can be represented, for example, by the following formula (1-1).

[式(1-1)中，R¹各自獨立地表示氫原子或甲基。 In the formula (1-1), R ¹ each independently represents a hydrogen atom or a methyl group.

X¹各自獨立地表示直接鍵結、取代或非取代的2價烴基、或者將該2價烴基與1個以上的含有除碳原子和氫原子以外的原子的連結基組合而成的2價基團。 X ¹ each independently represents a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group obtained by combining the divalent hydrocarbon group with one or more linking groups containing an atom other than a carbon atom and a hydrogen atom. group.

P表示發出螢光的部位。 P indicates the part where the fluorescence is emitted.

g表示1以上的整數。] g represents an integer of 1 or more. ]

另外，化合物群β中的化合物群β¹是：具有吸收單體(α1)發出的螢光的部位和聚合性基團的單體(β1)、以及含有上述單體(β1)作為結構單元的聚合物(β2)。作為吸收單體(α1)發出的螢光的部位，例如可舉出三芳基甲烷發色團、蒽醌發色團。作為化合物群β¹的較佳態樣，可舉出：具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團和聚合性基團的單體(β3)、以及含有該單體(β3)作為結構單元的聚合物(β4)(化合物群β²)。另外，作為聚合性基團，可舉出與上述化合物群α中例示的基團相同的基團，其中較佳為烯性不飽和基團。作為單體(β1)的較佳態樣，可舉出具有吸收單體(α1)發出的螢光的部位的烯性不飽和單體，更佳為具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團的烯性不飽和單體，例如可由下述式(1-2)表示。 Further, the compound group β ¹ in the compound group β is a monomer (β1) having a site for absorbing fluorescence emitted from the monomer (α1) and a polymerizable group, and a monomer (β1) as a structural unit. Polymer (β2). Examples of the site of the fluorescent light emitted from the monomer (α1) include a triarylmethane chromophore and a quinone chromophore. Preferred examples of the compound group β ¹ include a monomer (β3) having at least one chromophore and a polymerizable group selected from the group consisting of a triarylmethane chromophore and a fluorene chromophore, And a polymer (β4) (compound group β ² ) containing the monomer (β3) as a structural unit. In addition, examples of the polymerizable group include the same groups as those exemplified in the above-mentioned compound group α, and among them, an ethylenically unsaturated group is preferred. Preferred examples of the monomer (β1) include an ethylenically unsaturated monomer having a site which absorbs fluorescence emitted from the monomer (α1), and more preferably have a chromophore selected from the group consisting of triarylmethane and ruthenium. The ethylenically unsaturated monomer of at least one chromophore in the chromophore can be represented, for example, by the following formula (1-2).

[式(1-2)中，R²表示氫原子或甲基。 In the formula (1-2), R ² represents a hydrogen atom or a methyl group.

X²表示直接鍵結、取代或非取代的2價烴基、或者將該2價烴基與1個以上的含有除碳原子和氫原子以外的原子的連結基組合而成的2價基團。 X ² represents a direct bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group in which the divalent hydrocarbon group is combined with one or more linking groups containing an atom other than a carbon atom and a hydrogen atom.

Q表示吸收螢光的部位。 Q indicates the portion where the fluorescence is absorbed.

h表示1以上的整數。] h represents an integer of 1 or more. ]

以下，對上述式(1-1)和(1-2)中的符號進行說明。 Hereinafter, the symbols in the above formulae (1-1) and (1-2) will be described.

R¹和R²可適當地選擇氫原子或甲基。 R ¹ and R ² may be appropriately selected from a hydrogen atom or a methyl group.

作為X¹和X²涉及的2價烴基，例如可舉出2價脂肪族烴基、2價脂環式烴基、2價芳香族烴基。應予說明，在本說明書中，「脂環式烴基」是將不具有環狀結構的脂肪族烴基排除在外的概念。2價脂肪族烴基可以是直鏈和支鏈中的任一形態，另外2價脂肪族烴基和2價脂環式烴基可以是飽和烴基也可以是不飽和烴基。另外，在本說明書中，「脂環式烴基」、「芳香族烴基」是不僅包含僅由環結構構成的基團，還包含該環結構進一步取代2價脂肪族烴基而成的基團的概念，該結構中至少含有脂環式烴或芳香族烴即可。 Examples of the divalent hydrocarbon group of X ¹ and X ² include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In the present specification, the "alicyclic hydrocarbon group" is a concept in which an aliphatic hydrocarbon group having no cyclic structure is excluded. The divalent aliphatic hydrocarbon group may be in any of a straight chain and a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, in the present specification, the "alicyclic hydrocarbon group" and the "aromatic hydrocarbon group" are not only a group including a ring structure but also a group in which the ring structure further replaces a divalent aliphatic hydrocarbon group. This structure may contain at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

作為2價脂肪族烴基，例如可舉出鏈烷二基、鏈烯二基，其碳原子數較佳為1~20、更佳為2~12、進一步更佳為2~6。作為具體例，例如可舉出亞甲基、乙烷-1,1-二基、乙烷-1,2-二基、丙烷-1,1-二基、丙烷-1,2-二基、丙烷-1,3-二基、丙烷-2,2-二基、丁烷-1,2-二基、 丁烷-1,3-二基、丁烷-1,4-二基、戊烷-1,4-二基、戊烷-1,5-二基、己烷-1,5-二基、己烷-1,6-二基、2-甲基丙烷-1,2-二基、2,2-二甲基丙烷-1,3-二基、乙烯-1,1-二基、乙烯-1,2-二基、丙烯-1,2-二基、丙烯-1,3-二基、丙烯-2,3-二基、1-丁烯-1,2-二基、1-丁烯-1,3-二基、1-丁烯-1,4-二基、2-戊烯-1,5-二基、3-己烯-1,6-二基等。 Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the number of carbon atoms is preferably from 1 to 20, more preferably from 2 to 12, still more preferably from 2 to 6. Specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, and a propane-1,2-diyl group. Propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, Butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, Hexane-1,6-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, ethylene-1,1-diyl, ethylene- 1,2-diyl, propylene-1,2-diyl, propylene-1,3-diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene -1,3-diyl, 1-butene-1,4-diyl, 2-pentene-1,5-diyl, 3-hexene-1,6-diyl and the like.

作為2價脂環式烴基，例如可舉出伸環烷基、伸環烯基，其中碳原子數較佳為3~20，進一步更佳為3~12。作為具體例，例如可舉出伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環丁烯基、伸環戊烯基、伸環己烯基等單環式烴環基，1,4-伸降基(1,4-norbornylene)、2,5-伸降基等伸降基，1,5-伸金剛烷基、2,6-伸金剛烷基等橋環烴基等。 The divalent alicyclic hydrocarbon group may, for example, be a cycloalkyl group or a cycloalkenyl group, and the number of carbon atoms is preferably from 3 to 20, and more preferably from 3 to 12. Specific examples thereof include a monocyclic hydrocarbon ring such as a cyclopropyl group, a cyclobutene butyl group, a cyclopentylene group, a cyclohexylene group, a cyclobutenyl group, a cyclopentenyl group, or a cyclohexene group. Base, 1,4-extension 1,4-norbornylene, 2,5-dip Base extension A bridged hydrocarbon group such as a 1,5-adamantyl group or a 2,6-adamantyl group.

作為2價芳香族烴基，例如可舉出伸芳基，較佳為碳原子數6~14的單環~3環的伸芳基。作為具體例，例如可舉出伸苯基、伸聯苯基、伸萘基、伸菲基、伸蒽基等。 The divalent aromatic hydrocarbon group may, for example, be an extended aryl group, and is preferably a monocyclic to 3-ring extended aryl group having 6 to 14 carbon atoms. Specific examples thereof include a stretched phenyl group, a stretched biphenyl group, an extended naphthyl group, a phenanthrene group, and a fluorene group.

另外，在將2價烴基與1個以上的含有除碳原子和氫原子以外的原子的連結基組合而成的2價基團中，作為連結基，例如可舉出-O-、-S-、-SO₂-、-CO-、-COO-、-OCO-、-CONR³-(R³表示氫原子或碳原子數1~6的烷基)、-NR³-(R³與上述含義相同)，可以具有1種或2種以上。連結基的鍵結位置為任意，例如可存在於2價烴基的末端或C-C鍵之間，其中，較佳為存在於一個末端或C-C鍵之間。另外，2價烴基與上述連結基也可以鍵結形成環結構。應予說明，第[0020]段中提到的碳原子數是指除構 成該連結基的碳原子以外的部分的總碳原子數。 In the divalent group in which a divalent hydrocarbon group and one or more linking groups containing an atom other than a carbon atom and a hydrogen atom are combined, examples of the linking group include -O- and -S-. , -SO ₂ -, -CO-, -COO-, -OCO-, -CONR ³ - (R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR ³ - (R ³ has the above meaning The same may be used alone or in combination of two or more. The bonding position of the linking group is arbitrary, and may exist, for example, between the terminal of the divalent hydrocarbon group or the CC bond, and preferably exists between one terminal or a CC bond. Further, the divalent hydrocarbon group may be bonded to the above-mentioned linking group to form a ring structure. Incidentally, the number of carbon atoms mentioned in the paragraph [0020] means the total number of carbon atoms of a portion other than the carbon atom constituting the linking group.

作為C-C鍵之間具有上述連結基的2價烴基的具體例，例如可舉出-CH₂-CH₂-CH₂-COO-CH₂-CH₂-、-CH₂-CH(-CH₃)-CH₂-COO-CH₂-CH₂-、-CH₂-CH₂-CH₂-OCO-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-COO-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-(CH₂)₅-COO-(CH₂)₁₁-CH₂-、-CH₂-CH₂-CH₂-C-(COO-CH₂-CH₃)₂-、-CH₂-CH₂-O-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CH₂-CH₂-、-(CH₂-CH₂-O)_n-CH₂-(n是1~8的整數)、-(CH₂-CH₂-CH₂-O)_m-CH₂-(m是1~5的整數)、-CH₂-CH(CH₃)-O-CH₂-CH₂-、-CH₂-CH-(OCH₃)-、-CH₂-CH₂-COO-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-O-CO-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-COO-CH₂-CH₂-O-CH₂-CH₂-O-CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-NH-COO-CH₂-CH₂-、-CH₂-CH₂-OCO-CH₂-等，但並不限定於這些基團。 Specific examples of the divalent hydrocarbon group having the above-mentioned linking group between the CC bonds include -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH(-CH ₃ ) -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ - CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -(CH ₂ ) ₅ -COO-(CH ₂ ) ₁₁ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -C-(COO-CH ₂ -CH ₃ ) ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -(CH ₂ -CH ₂ -O) _n -CH ₂ - (n is an integer from 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₂ - (m is an integer from 1 to 5), -CH ₂ -CH(CH ₃ )- O-CH ₂ -CH ₂ -, -CH ₂ -CH-(OCH ₃ )-, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )- CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CO-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OCO-CH ₂ -, etc., but is not limited to these groups.

另外，作為具有2價烴基與上述連結基鍵結而形成的環結構的基團的具體例，例如可舉出以下基團，但並不限定於這些基團。 In addition, specific examples of the group having a ring structure in which a divalent hydrocarbon group and the above-mentioned linking group are bonded to each other include, for example, the following groups, but are not limited thereto.

作為2價烴基所具有的取代基，可舉出鹵素原子、硝基、羥基、取代或非取代的烷氧基、取代或非取代的芳氧基等。作為鹵素原子，可舉出氟原子、氯原子、溴原子、碘原子。烷氧基可以是直鏈和支鏈中的任一形態，碳原子數較佳為1~6。作為具體例，例如可舉出甲氧基、乙氧基、丙氧基、丁氧基等。作為芳氧基，較佳為碳原子數6~14的芳氧基，例如可舉出苯氧基、苄氧基等。另外，作為烷氧基和芳氧基的取代基，可舉出鹵素原子、硝基、羥基、胺基、羧基、硫烷基等。此外，2價烴基為2價芳香族烴基時，可以被取代或非取代的烷基、取代或非取代的烯基所取代。烷基和烯基的碳原子數較佳為1~6，作為烷基的具體例，例如可舉出甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、己基等，另外，作為烯基的具體例，例如可舉出乙烯基、1-丙烯基、1-丁烯基、1-戊烯基、1-己烯基、2- 乙基-2-丁烯基等。應予說明，作為烷基和烯基的取代基，可舉出與上述2價烴基的取代基相同的基團。 Examples of the substituent of the divalent hydrocarbon group include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 6. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. Further, examples of the substituent of the alkoxy group and the aryloxy group include a halogen atom, a nitro group, a hydroxyl group, an amine group, a carboxyl group, and a sulfanyl group. Further, when the divalent hydrocarbon group is a divalent aromatic hydrocarbon group, it may be substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. The alkyl group and the alkenyl group preferably have 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a secondary butyl group. Further, examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, and 2, as a specific example of the alkenyl group. - Ethyl-2-butenyl and the like. In addition, examples of the substituent of the alkyl group and the alkenyl group include the same groups as the substituent of the above divalent hydrocarbon group.

作為P，只要是來源於發出螢光的化合物的基團就沒有特別限定，較佳為發色團或花青發色團。應予說明，發色團或花青發色團是從化合物或花青化合物去掉g個氫原子而成的殘基，是能夠與上述式(1-1)的g個X¹連接的殘基。 The P is not particularly limited as long as it is a group derived from a compound that emits fluorescence, and is preferably A chromophore or a cyan chromophore. It should be noted that The chromophore or the cyan chromophore is from The residue obtained by removing the g hydrogen atoms from the compound or the cyanine compound is a residue which can be bonded to g X ^{1 of the} above formula (1-1).

作為Q，只要是來源於吸收螢光的化合物的基團就沒有特別限定，較佳為三芳基甲烷發色團或蒽醌發色團。應予說明，三芳基甲烷發色團或蒽醌發色團是從三芳基甲烷化合物或蒽醌化合物去掉h個氫原子而成的殘基，是能夠與上述式(1-2)的h個X²連接的殘基。 The Q is not particularly limited as long as it is a group derived from a compound that absorbs fluorescence, and is preferably a triarylmethane chromophore or a chromophore. In addition, the triarylmethane chromophore or the chromophore is a residue obtained by removing h hydrogen atoms from a triarylmethane compound or a hydrazine compound, and is capable of being h with the above formula (1-2). X ² linked residues.

g和h各自獨立地表示1以上的整數，較佳為1或2。 g and h each independently represent an integer of 1 or more, preferably 1 or 2.

作為化合物、花青化合物、三芳基甲烷化合物、蒽醌化合物，可舉出在顏色索引(C.I.；The Society of Dyers and Colourists公司發行)中被分類為染料(Dye)的公知染料。作為這些染料，酸性染料、直接染料、鹼性染料、造鹽染料、油溶性染料、分散染料、反應染料、媒染染料、還原染料、硫化染料等均可使用，但從反應性優異，能夠容易生成上述式(1-1)表示的化合物、上述式(1-2)表示的化合物的方面考慮，較佳為使用酸性染料、油溶性染料、鹼性染料。 As The compound, the cyanine compound, the triarylmethane compound, and the hydrazine compound are exemplified by a known dye classified as a dye (Dye) in a color index (CI; issued by The Society of Dyers and Colourists). As such dyes, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mord dyes, vat dyes, sulfur dyes, and the like can be used, but they are excellent in reactivity and can be easily produced. The acid dye, the oil-soluble dye, and the basic dye are preferably used in view of the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2).

作為酸性染料，是在顏色索引中被分類為C.I.酸性染料的染料，作為直接染料，是在顏色索引中被分類為C.I.直接染料的染料。作為油溶性染料，是在顏色 索引中被分類為C.I.溶劑染料的染料，作為鹼性染料，是在顏色索引中被分類為C.I.鹼性染料的染料。 As the acid dye, it is a dye classified as a C.I. acid dye in a color index, and as a direct dye, a dye classified as a C.I. direct dye in a color index. As an oil-soluble dye, it is in color Dyes classified as C.I. solvent dyes in the index, as basic dyes, are dyes classified as C.I. basic dyes in the color index.

以下，對化合物、花青化合物、三芳基甲烷化合物、蒽醌化合物進行說明。 Following, right The compound, the cyanine compound, the triarylmethane compound, and the hydrazine compound will be described.

作為化合物，較佳為具有下述式(2)表示的結構的化合物，作為具體例，例如可舉出C.I.鹼性紫10(羅丹明B)等系鹼性染料。 As The compound is preferably a compound having a structure represented by the following formula (2), and specific examples thereof include CI basic violet 10 (rhodamine B) and the like. Is a basic dye.

[式(2)中，R¹¹、R¹²、R¹³和R¹⁴各自獨立地表示氫原子、取代或非取代的烴基、該烴基的C-C鍵之間具有含有除碳原子和氫原子以外的原子的連結基的基團、或者取代或非取代的雜環基。 [In the formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and the CC bond of the hydrocarbon group has an atom other than a carbon atom and a hydrogen atom. a group of a linking group, or a substituted or unsubstituted heterocyclic group.

R¹⁵和R¹⁶各自獨立地表示氫原子或者取代或非取代的烴基。 R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R¹⁷表示-SO₃ ^-、-SO₃H、-SO₃M、-SO₃R¹⁸、-CO₂ ^-、-CO₂H、-CO₂M、-CO₂R¹⁹、-SO₂NHR²⁰或-SO₂NR²¹R²²。 R ¹⁷ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -SO ₃ R ¹⁸ , -CO ₂ ^- , -CO ₂ H, -CO ₂ M, -CO ₂ R ¹⁹ , -SO ₂ NHR ²⁰ Or -SO ₂ NR ²¹ R ²² .

r表示0~5的整數，r為2以上的整數時，多個R¹⁷可以 相同也可以不同。 r represents an integer of 0 to 5, and when r is an integer of 2 or more, a plurality of R ¹⁷ may be the same or different.

R¹⁸、R¹⁹和R²⁰各自獨立地表示取代或非取代的烴基、或者該烴基的C-C鍵之間具有含有除碳原子和氫原子以外的原子的連結基的基團。 R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group.

R²¹和R²²各自獨立地表示取代或非取代的烴基、或者該烴基的C-C鍵之間具有含有除碳原子和氫原子以外的原子的連結基的基團、或者表示R²¹和R²²相互鍵結形成的取代或非取代的雜環基。 R ²¹ and R ²² each independently represent a substituted or unsubstituted hydrocarbon group, or a group having a linking group containing an atom other than a carbon atom and a hydrogen atom between CC bonds of the hydrocarbon group, or R ²¹ and R ²² are mutually represented A substituted or unsubstituted heterocyclic group formed by bonding.

M表示鈉原子或鉀原子。] M represents a sodium atom or a potassium atom. ]

作為R¹¹~R¹⁶和R¹⁸~R²²中的烴基，例如可舉出脂肪族烴基、脂環式烴基、芳香族烴基。 Examples of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

脂肪族烴基可以飽和也可以不飽和，例如可舉出烷基、烯基、炔基。脂肪族烴基的碳原子數較佳為1~30，更佳為1~15，特佳為1~8。另外，脂肪族烴基可以是直鏈狀也可以是支鏈狀。作為烷基，例如除上述具體例以外，還可舉出庚基、辛基、壬基、癸基、十一烷基、1-甲基癸基、十二烷基、1-甲基十一烷基、1-乙基癸基、十三烷基、十四烷基、三級十二烷基、十五烷基、1-庚基辛基、十六烷基、十八烷基等。作為烯基，例如除上述具體例以外，還可舉出2-辛烯基、(4-乙烯基)-5-己烯基、2-癸烯基等。另外，作為炔基，例如可舉出乙炔基、1-丙炔基、1-丁炔基、1-戊炔基、3-戊炔基、1-己炔基、2-乙基-2-丁炔基、2-辛炔基、(4-乙炔基)-5-己炔基、2-癸炔基等。 The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 15, and particularly preferably from 1 to 8. Further, the aliphatic hydrocarbon group may be linear or branched. The alkyl group may, for example, be a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a 1-methylindenyl group, a dodecyl group or a 1-methyl group, in addition to the above specific examples. Alkyl, 1-ethylindenyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, and the like. The alkenyl group may, for example, be 2-octenyl, (4-vinyl)-5-hexenyl or 2-decenyl, in addition to the above specific examples. Further, examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2- group. Butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like.

作為脂環式烴基，較佳為碳原子數3~30的脂 環式烴基。脂環式烴基可以飽和也可以不飽和，例如可舉出環烷基、環烯基、稠環烴基、橋環烴基、螺烴基、環狀萜烯烴基等。更具體而言，可舉出環丙基、環丁基、環戊基、環己基、三級丁基環己基、環庚基、環辛基等環烷基；1-環己烯基等環烯基；三環癸基、十氫-2-萘基、金剛烷基等稠環烴基；三環[5.2.1.0^2,6]癸烷-8-基、五環十五烷基、異基、二環戊烯基、三環戊烯基等橋環烴基；從螺[3,4]庚烷、螺[3,4]辛烷去掉1個氫原子而成的1價基團等螺烴基；從對蓋烷、側柏烷、蒈烷等去掉1個氫原子而成的1價基等環狀萜烯烴基等。上述環烷基和環烯基中，碳原子數更佳為3~12。 The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a fused ring hydrocarbon group, a bridged cyclic hydrocarbon group, a spirohydrocarbyl group, and a cyclic terpene group. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tert-butylcyclohexyl group, a cycloheptyl group or a cyclooctyl group; a ring such as a 1-cyclohexenyl group; Alkenyl; fused ring hydrocarbon group such as tricyclodecyl, decahydro-2-naphthyl, adamantyl; tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, pentacyclopentadecyl, hetero a bridged hydrocarbon group such as a dicyclopentenyl group or a tricyclopentenyl group; a monovalent group such as a monovalent group obtained by removing one hydrogen atom from spiro[3,4]heptane or spiro[3,4]octane; A hydrocarbon group; a cyclic decyl group such as a monovalent group obtained by removing one hydrogen atom from a captan, a side cedar or a decane. In the above cycloalkyl group and cycloalkenyl group, the number of carbon atoms is more preferably from 3 to 12.

作為芳香族烴基，較佳為碳原子數6~20的芳基，更佳為碳原子數6~10的芳基。這裡，「芳基」是指單環~3環式芳香族烴基，例如可舉出苯基、萘基、蒽基、菲基、薁基、9-茀基等，其中，較佳為苯基、萘基。 The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Here, the "aryl group" means a monocyclic to 3-ring aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, and a 9-fluorenyl group. Among them, a phenyl group is preferred. , naphthyl.

另外，R¹¹、R¹²、R¹³、R¹⁴、R¹⁸、R¹⁹、R²⁰、R²¹和R²²中的烴基可以在C-C鍵之間具有含有除碳原子和氫原子以外的原子的連結基，具有連結基時，較佳為在脂肪族烴基的C-C鍵之間具有上述連結基的基團。作為連結基的具體例，可舉出與上述相同的基團。 Further, the hydrocarbon group in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² may have a bond containing an atom other than a carbon atom and a hydrogen atom between CC bonds. When the group has a linking group, it is preferably a group having the above-mentioned linking group between the CC bonds of the aliphatic hydrocarbon group. Specific examples of the linking group include the same groups as described above.

雜環基可以是單環式雜環也可以是多環式雜環。雜環基可以是不飽和環也可以是飽和環，另外，環內可以具有同種或不同種類的2個以上的雜原子(例如，氮原子、氧原子、硫原子)。作為雜環基，較佳為碳原子數3~10的雜環基，例如可舉出吡咯啶基、咪唑啉基、吡 唑烷基、啉基、硫代啉基、哌啶基、哌啶子基、哌基、高哌基等含氮脂環式雜環基，1,3-二氧雜環戊烷-2-基等其它脂環式雜環基，吡啶基、吡基、嘧啶基、嗒基、喹啉基、異喹啉基、酞基、萘啶基、喹喔啉基、咪唑基、吡唑基、***基、四唑基、噻唑基、苯并噻唑基、唑基、吲哚基、吲唑基、苯并咪唑基、鄰苯二甲醯亞胺基等含氮芳香族雜環基，噻吩基、呋喃基、吡喃基、嘌呤基等其它芳香族雜環基。 The heterocyclic group may be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring. The heterocyclic group may be an unsaturated ring or a saturated ring, and may have two or more kinds of hetero atoms (for example, a nitrogen atom, an oxygen atom or a sulfur atom) of the same kind or different types in the ring. The heterocyclic group is preferably a heterocyclic group having 3 to 10 carbon atoms, and examples thereof include a pyrrolidinyl group, an imidazolinyl group, and a pyrazolidinyl group. Olinyl, thio Lolinyl, piperidinyl, piperidino, piperazine Base, high piper Other alicyclic heterocyclic groups such as a nitrogen-containing alicyclic heterocyclic group, a 1,3-dioxolan-2-yl group, a pyridyl group, and a pyridyl group Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene , naphthyridinyl, quinoxalinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, a nitrogen-containing aromatic heterocyclic group such as an azole group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group or a phthalimido group, a thiryl group, a furyl group, a pyranyl group, a fluorenyl group or the like Ring base.

作為R²¹與R²²相互鍵結形成的雜環基，可舉出與上述雜環基相同的基團。 Examples of the heterocyclic group in which R ²¹ and R ²² are bonded to each other include the same groups as the above heterocyclic group.

作為R¹¹~R¹⁶和R¹⁸~R²²中的烴基的取代基，可舉出鹵素原子、羥基、氰基、甲醯基、羧基、硝基、胺基、二(C_1-8烷基)胺基、二芳基胺基、C_1-8烷氧基、C_6-10芳氧基、C_2-8烷氧基羰基、C_1-8烷基硫基、C_6-10芳基硫基、三(C_1-8烷基)甲矽烷基、巰基、烯丙基、C_1-8烷基磺醯基、C_1-8烷基氨磺醯基、雜環基、芳香族烴基等，脂環式烴基、雜環基和芳香族烴基可以被脂肪族烴基取代。這些取代基可以進一步具有取代基。應予說明，取代基的位置和數量為任意，具有2個以上取代基時，該取代基可以相同也可以不同。應予說明，作為R¹¹~R¹⁴涉及的雜環基的取代基以及R²¹和R²²相互鍵結形成的雜環基的取代基，可舉出與R¹¹~R¹⁶和R¹⁸~R²²中的烴基的取代基相同的基團。 Examples of the substituent of the hydrocarbon group in R ¹¹ to R ¹⁶ and R ¹⁸ to R ²² include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, and a di(C _1-8 alkyl group). Amino, diarylamine, C _1-8 alkoxy, C _6-10 aryloxy, C _2-8 alkoxycarbonyl, C _1-8 alkylthio, C _6-10 aryl Thio group, tri(C _1-8 alkyl)carbamyl group, fluorenyl group, allyl group, C _1-8 alkylsulfonyl group, C _1-8 alkylsulfamoyl group, heterocyclic group, aromatic hydrocarbon group And, the alicyclic hydrocarbon group, the heterocyclic group, and the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group. These substituents may further have a substituent. In addition, when the position and the number of the substituent are arbitrary, and when it has two or more substituents, this substituent may be the same or different. In addition, examples of the substituent of the heterocyclic group in which R ¹¹ to R ^{14 are} involved and the substituent of the heterocyclic group in which R ²¹ and R ²² are bonded to each other include R ¹¹ to R ¹⁶ and R ¹⁸ to R. The substituent of the hydrocarbon group in ²² is the same group.

其中，作為R¹¹、R¹²、R¹³和R¹⁴，較佳為氫原子、碳原子數1~8的烷基或碳原子數6~10的芳基。 Among them, R ¹¹ , R ¹² , R ¹³ and R ^{14 are} preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms.

作為R¹⁵和R¹⁶，較佳為氫原子或碳原子數1~8的烷基。 R ¹⁵ and R ^{16 are} preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

作為R¹⁷，較佳為-SO₃H、-SO₃R¹⁸、-CO₂H、-CO₂R¹⁹、-SO₂NHR²⁰或-SO₂NR²¹R²²，另外，作為R¹⁸、R¹⁹、R²⁰、R²¹和R²²，較佳為碳原子數1~8的烷基。 R ^{17 is} preferably -SO ₃ H, -SO ₃ R ¹⁸ , -CO ₂ H, -CO ₂ R ¹⁹ , -SO ₂ NHR ²⁰ or -SO ₂ NR ²¹ R ²² , in addition, as R ¹⁸ and R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are} preferably an alkyl group having 1 to 8 carbon atoms.

r較佳為1或2。 r is preferably 1 or 2.

作為具有上述式(2)表示的結構的化合物的具體例，例如可舉出具有下述式表示的結構的化合物。 As the structure represented by the above formula (2) Specific examples of the compound include a compound having a structure represented by the following formula.

上述式(2)表示的結構為陽離子性時，具有該結構的化合物具有陰離子以成為電中性。作為陰離子，例如可舉出鹵素離子、硼陰離子、磷酸根陰離子、羧酸根陰離子、硫酸根陰離子、有機磺酸根陰離子、氮陰離子、甲基化物陰離子、氫氧化物離子等。 When the structure represented by the above formula (2) is cationic, the structure is The compound has an anion to become electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and a hydroxide ion.

另外，上述式(2)表示的結構為陰離子性時，具有該結構的化合物具有陽離子以成為電中性。作為陽離 子，例如可舉出質子、金屬陽離子、鎓陽離子等。作為金屬陽離子，例如可舉出鋰離子、鈉離子、鉀離子、銣離子、銫離子等1價金屬陽離子，鎂離子、鈣離子、鍶離子、鋇離子等2價金屬陽離子。作為鎓陽離子，可舉出銨陽離子、鏻陽離子等。作為銨陽離子的具體例，可舉出日本特開2011-138094號公報的第[0045]段中記載的化合物的陽離子等，作為鏻陽離子的具體例，可舉出日本特開2013-190776號公報的第[0038]~[0040]段等中記載的陽離子。 Further, when the structure represented by the above formula (2) is anionic, the structure is The compound has a cation to become electrically neutral. Examples of the cation include a proton, a metal cation, a phosphonium cation, and the like. Examples of the metal cation include monovalent metal cations such as lithium ions, sodium ions, potassium ions, cesium ions, and cesium ions, and divalent metal cations such as magnesium ions, calcium ions, barium ions, and cesium ions. Examples of the phosphonium cation include an ammonium cation, a phosphonium cation, and the like. Specific examples of the ammonium cation include a cation of the compound described in paragraph [0045] of JP-A-2011-138094, and a specific example of the phosphonium cation is disclosed in JP-A-2013-190776. The cations described in paragraphs [0038] to [0040] and the like.

作為花青化合物，較佳為具有下述式(3)表示的結構的化合物，作為具體例，例如可舉出C.I.鹼性紅12等花青系鹼性染料。 The cyanine compound is preferably a compound having a structure represented by the following formula (3), and specific examples thereof include a cyanine-based basic dye such as C.I. Basic Red 12.

[式(3)中，R³¹和R³²各自獨立地表示取代或非取代的烴基。 [In the formula (3), R ³¹ and R ³² each independently represent a substituted or unsubstituted hydrocarbon group.

R³³~R³⁵各自獨立地表示氫原子、鹵素原子、取代或非取代的烴基。多個存在的R³³和R³⁴可以相同也可以不同。 R ³³ to R ³⁵ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group. The plurality of R ³³ and R ^{34 present} may be the same or different.

環Z¹和環Z²各自獨立地表示取代或非取代的芳香族烴環。 Ring Z ¹ and ring Z ² each independently represent a substituted or unsubstituted aromatic hydrocarbon ring.

G¹和G²各自獨立地表示-O-、-S-或-CR³⁶R³⁷-。其中，R³⁶和R³⁷各自獨立地表示取代或非取代的烴基。 G ¹ and G ² each independently represent -O-, -S- or -CR ³⁶ R ³⁷ -. Wherein R ³⁶ and R ³⁷ each independently represent a substituted or unsubstituted hydrocarbon group.

s表示1~3的整數。] s represents an integer from 1 to 3. ]

作為R³¹~R³⁷中的烴基，例如可舉出脂肪族烴基、脂環式烴基、芳香族烴基。作為具體例，可舉出與式(2)中的烴基相同的基團，對於取代基，也可舉出相同的基團。 Examples of the hydrocarbon group in R ³¹ to R ³⁷ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same groups as those of the hydrocarbon group in the formula (2), and the same groups may be mentioned as the substituent.

環Z¹和環Z²的芳香族烴環可以是單環式芳香族烴環也可以是多環式芳香族烴環，碳原子數較佳為6~20，更佳為6~10。作為具體例，例如可舉出苯環、聯苯環、萘環、甘菊環、蒽環、菲環、芘環、萘并萘環、苯并菲環等。作為芳香族烴環的取代基，可舉出與式(2)中的烴基的取代基相同的基團。 The aromatic hydrocarbon ring of the ring Z ¹ and the ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring, and the number of carbon atoms is preferably from 6 to 20, more preferably from 6 to 10. Specific examples thereof include a benzene ring, a biphenyl ring, a naphthalene ring, a chamomile ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, and a triphenylene ring. The substituent of the aromatic hydrocarbon ring may be the same as the substituent of the hydrocarbon group in the formula (2).

其中，作為R³¹和R³²中的烴基，較佳為碳原子數1~12的烷基，更佳為碳原子數1~8的烷基，特佳為碳原子數1~6的烷基。 In particular, the hydrocarbon group in R ³¹ and R ³² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. .

作為R³³~R³⁵，較佳為氫原子。 R ³³ to R ^{35 are} preferably a hydrogen atom.

作為環Z¹和環Z²，較佳為苯環。 As the ring Z ¹ and the ring Z ² , a benzene ring is preferred.

作為G¹和G²，較佳為-O-、-CR³⁶R³⁷-，作為R³⁶和R³⁷，較佳為碳原子數1~8的烷基，更佳為碳原子數1~4的烷基，特佳為甲基、乙基。 As G ¹ and G ² , -O-, -CR ³⁶ R ³⁷ - is preferable, and R ³⁶ and R ^{37 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group or an ethyl group.

s較佳為1或2，更佳為1。 s is preferably 1 or 2, more preferably 1.

作為具有上述式(3)表示的結構的花青化合物的具體例，例如可舉出具有下述式表示的結構的化合物。 Specific examples of the cyanine compound having the structure represented by the above formula (3) include a compound having a structure represented by the following formula.

上述式(3)表示的結構為陽離子性時，具有該結構的花青化合物具有陰離子以成為電中性。另外，上述式(3)表示的結構為陰離子性時，具有該結構的花青化合物具有陽離子以成為電中性。作為這樣的陰離子和陽離子的具體例，例如可舉出與上述式(2)中例示的離子相同的離子。 When the structure represented by the above formula (3) is cationic, the cyanine compound having such a structure has an anion to be electrically neutral. Further, when the structure represented by the above formula (3) is anionic, the cyanine compound having such a structure has a cation to be electrically neutral. Specific examples of such anions and cations include the same ions as those exemplified in the above formula (2).

作為三芳基甲烷化合物，例如可舉出二胺基三芳基甲烷系染料、三胺基三芳基甲烷系染料、具有OH基的玫紅酸系染料等。其中，從色調優異、日光牢固性比其它染料優異的方面考慮，較佳為二胺基三芳基甲烷 系染料、三胺基三芳基甲烷系染料。作為更佳的三芳基甲烷化合物，可舉出具有下述式(4)表示的結構的化合物。應予說明，下述式(4)表示的結構中存在各種共振結構，但在本說明書中，對於這些共振結構，與下述式(4)表示的結構等效。 Examples of the triarylmethane compound include a diaminotriarylmethane dye, a triaminetriarylmethane dye, and a rose acid dye having an OH group. Among them, diaminotriarylmethane is preferred from the viewpoints of excellent color tone and excellent sunlight stability compared to other dyes. A dye, a triamine triarylmethane dye. The compound having a structure represented by the following formula (4) is exemplified as a more preferable triarylmethane compound. In the structure represented by the following formula (4), various resonance structures exist. However, in the present specification, the resonance structures are equivalent to the structures represented by the following formula (4).

[式(4)中，Y表示氫原子、取代或非取代的烴基或者-NR⁵⁹R⁶⁰。 [In the formula (4), Y represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group or -NR ⁵⁹ R ⁶⁰ .

R⁴¹~R⁴⁴和R⁵⁹~R⁶⁰各自獨立地表示氫原子、取代或非取代的烴基。 R ⁴¹ to R ⁴⁴ and R ⁵⁹ to R ⁶⁰ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group.

R⁴⁵~R⁵²表示氫原子、鹵素原子、取代或非取代的烴基或者-COOR'。其中，R'表示氫原子或者取代或非取代的烴基。 R ⁴⁵ to R ⁵² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted hydrocarbon group or -COOR ' . Wherein R ' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

Ar表示取代或非取代的芳香族烴基。] Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ]

作為Y、R⁴¹~R⁵²、R⁵⁹~R⁶⁰和R'涉及的烴基，例如可舉出脂肪族烴基、脂環式烴基、芳香族烴基。作為具體例，可舉出與式(2)中的烴基相同的基團，對於取代基，也可舉出相同的基團。 Examples of the hydrocarbon group of Y, R ⁴¹ to R ⁵² , R ⁵⁹ to R ⁶⁰ and R ' include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same groups as those of the hydrocarbon group in the formula (2), and the same groups may be mentioned as the substituent.

Ar涉及的芳香族烴基較佳為碳原子數為6~20，更佳 為碳原子數為6~10。作為具體例，例如可舉出伸苯基、伸萘基、伸聯苯基、伸蒽基等。作為芳香族烴基的取代基，例如可舉出與式(2)中的烴基的取代基相同的基團，其中，較佳為鹵素原子。 The aromatic hydrocarbon group involved in Ar preferably has a carbon number of 6 to 20, more preferably The number of carbon atoms is 6 to 10. Specific examples thereof include a phenylene group, an extended naphthyl group, a stretched biphenyl group, and a fluorene group. The substituent of the aromatic hydrocarbon group is, for example, the same as the substituent of the hydrocarbon group in the formula (2), and among them, a halogen atom is preferred.

其中，作為R⁴¹~R⁴⁴、R⁵⁹~R⁶⁰和R'，較佳為氫原子或碳原子數1~8的烷基。 Among them, R ⁴¹ to R ⁴⁴ , R ⁵⁹ to R ⁶⁰ and R ' are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

作為R⁴⁵~R⁵²，較佳為氫原子、鹵素原子或碳原子數1~8的烷基。 R ⁴⁵ to R ^{52 are} preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.

Ar較佳為伸苯基、伸萘基。 Ar is preferably a phenyl group or a naphthyl group.

Y較佳為氫原子或碳原子數1~8的烷基。 Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

在本發明中，上述式(4)表示的結構中，從耐熱性和耐溶劑性的觀點出發，特佳為下述式(4-1)或(4-2)表示的陽離子。 In the structure of the above formula (4), the cation represented by the following formula (4-1) or (4-2) is particularly preferable from the viewpoint of heat resistance and solvent resistance.

[式(4-1)和(4-2)中，Y¹各自獨立地表示氫原子、鹵素原子、碳原子數1 ~8的烷基或-NR⁶¹R⁶²。 In the formulae (4-1) and (4-2), Y ¹ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or -NR ⁶¹ R ⁶² .

R⁵³~R⁵⁶和R⁶¹~R⁶²各自獨立地表示氫原子或碳原子數1~8的烷基。 R ⁵³ to R ⁵⁶ and R ⁶¹ to R ⁶² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

R⁵⁷和R⁵⁸各自獨立地表示氫原子、鹵素原子或碳原子數1~8的烷基。] R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. ]

作為R⁵³~R⁵⁶，更佳為碳原子數1~4的烷基，特佳為甲基、乙基。 R ⁵³ to R ^{56 are more} preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group.

作為R⁵⁷和R⁵⁸，較佳為氫原子、鹵素原子或碳原子數1~4的烷基。 R ⁵⁷ and R ^{58 are} preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

作為R⁶¹~R⁶²，較佳為氫原子或碳原子數1~6的烷基。 R ⁶¹ to R ^{62 are} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

作為Y¹，較佳為氫原子或碳原子數1~4的烷基。 Y ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

作為具有上述式(4)表示的結構的三芳基甲烷化合物的具體例，例如可舉出具有下述式表示的結構的化合物。 Specific examples of the triarylmethane compound having a structure represented by the above formula (4) include a compound having a structure represented by the following formula.

上述式(4)表示的結構為陽離子性時，具有該結構的三芳基甲烷化合物具有陰離子以成為電中性。另外，上述式(4)表示的結構為陰離子性時，具有該結構的三芳基甲烷化合物具有陽離子以成為電中性。作為這樣的陰離子和陽離子的具體例，例如可舉出與上述式(2)中例示的離子相同的離子。 When the structure represented by the above formula (4) is cationic, the triarylmethane compound having such a structure has an anion to be electrically neutral. Further, when the structure represented by the above formula (4) is anionic, the triarylmethane compound having such a structure has a cation to be electrically neutral. Specific examples of such anions and cations include the same ions as those exemplified in the above formula (2).

作為蒽醌化合物，較佳為具有下述式(5-1)或(5-2)表示的結構的化合物，作為具體例，例如可舉出C.I. 溶劑綠3等蒽醌系油溶性染料。 The ruthenium compound is preferably a compound having a structure represented by the following formula (5-1) or (5-2), and specific examples thereof include C.I. Solvent Green 3 is an oil-soluble dye.

[式(5-1)中，R⁷¹和R⁷²各自獨立地表示氫原子或者取代或非取代的烴基。] [In the formula (5-1), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ]

[式(5-2)中，R⁸¹和R⁸²表示氫原子或者取代或非取代的烴基。 [In the formula (5-2), R ⁸¹ and R ⁸² represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

R⁸³表示取代或非取代的2價烴基。 R ⁸³ represents a substituted or unsubstituted divalent hydrocarbon group.

R⁸⁴、R⁸⁵和R⁸⁶各自獨立地表示取代或非取代的烴基。] R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a substituted or unsubstituted hydrocarbon group. ]

作為R⁷¹、R⁷²、R⁸¹、R⁸²和R⁸⁴~R⁸⁶中的烴基，例如可舉出脂肪族烴基、脂環式烴基、芳香族烴基。作為具體例，可舉出與式(2)中例示的基團相同的基團，對於取代基，也可舉出相同的基團。 Examples of the hydrocarbon group in R ⁷¹ , R ⁷² , R ⁸¹ , R ⁸² and R ⁸⁴ to R ⁸⁶ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include the same groups as those exemplified in the formula (2), and the same groups may be mentioned as the substituent.

作為R⁸³中的2價烴基，可舉出2價脂肪族烴基、2價脂環式烴基、2價芳香族烴基。作為具體例，可舉出與式(1-1)和(1-2)涉及的2價烴基中例示的基團相同的基團，對於取代基，也可舉出相同的基團。 ^Examples of the divalent hydrocarbon group in R ⁸³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. Specific examples thereof include the same groups as those exemplified in the divalent hydrocarbon group of the formulae (1-1) and (1-2), and the same groups may be mentioned as the substituent.

其中，作為R⁷¹和R⁷²，較佳為氫原子、取代或非取代的碳原子數1~6的烷基、或者取代或非取代的碳原子數6~10的芳基，更佳為氫原子或者取代或非取代 的苯基。作為烷基的取代基，可舉出鹵素原子、羥基、氰基等，另外，作為芳基、苯基的取代基，可舉出鹵素原子、羥基、氰基、碳原子數1~6的烷基等。 Wherein, as R ⁷¹ and R ⁷² , a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms is preferred, and hydrogen is more preferred. Atom or a substituted or unsubstituted phenyl group. Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, and a cyano group. Examples of the substituent of the aryl group and the phenyl group include a halogen atom, a hydroxyl group, a cyano group, and an alkyl group having 1 to 6 carbon atoms. Base.

作為R⁸¹、R⁸²、R⁸⁴、R⁸⁵和R⁸⁶，較佳為氫原子或者取代或非取代的碳原子數1~6的烷基，更佳為氫原子或者取代或非取代的碳原子數1~4的烷基。作為烷基的取代基，可舉出與上述相同的基團。 R ⁸¹ , R ⁸² , R ⁸⁴ , R ⁸⁵ and R ^{86 are} preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted carbon atom. A number of 1 to 4 alkyl groups. The substituent of the alkyl group is the same as the above.

作為R⁸³，較佳為碳原子數1~20的鏈烷二基，更佳為碳原子數2~8的鏈烷二基。作為鏈烷二基的取代基，例如可舉出與上述式(1-1)和(1-2)涉及的X¹和X²的取代基相同的基團。 R ^{83 is} preferably an alkanediyl group having 1 to 20 carbon atoms, more preferably an alkanediyl group having 2 to 8 carbon atoms. Examples of the substituent of the alkanediyl group include the same groups as the substituents of X ¹ and X ² in the above formulae (1-1) and (1-2).

作為具有上述式(5-1)或(5-2)表示的結構的蒽醌化合物的具體例，例如可舉出具有下述式表示的結構的化合物。 Specific examples of the ruthenium compound having a structure represented by the above formula (5-1) or (5-2) include a compound having a structure represented by the following formula.

除上述以外，作為化合物，例如也可使用下述染料：C.I.酸性紅51(赤蘚紅)、C.I.酸性紅52(酸性羅丹明)、C.I.酸性紅87(曙紅G)、C.I.酸性紅92(酸性螢光桃紅PB) 、C.I.酸性紅87(曙紅G)、C.I.酸性紅92(酸性螢光桃紅PB)、C.I.酸性紅289、C.I.酸性紅388、孟加拉紅B(食用紅5號)、酸性羅丹明G、C.I.酸性紫9等系酸性染料；C.I.溶劑紅35、C.I.溶劑紅36、C.I.溶劑紅42、C.I.溶劑紅43、C.I.溶劑紅44、C.I.溶劑紅45、C.I.溶劑紅46、C.I.溶劑紅47、C.I.溶劑紅48、C.I.溶劑紅49、C.I.溶劑紅72、C.I.溶劑紅73、C.I.溶劑紅109、C.I.溶劑紅140、C.I.溶劑紅141、C.I.溶劑紅237、C.I.溶劑紅246、C.I.溶劑紫2、C.I.溶劑紫10等系油溶性染料；C.I.鹼性紅1(羅丹明6GCP)、C.I.鹼性紅8(羅丹明G)等系鹼性染料等。 In addition to the above, as For the compound, for example, the following dyes can be used: CI Acid Red 51 (erythropurine), CI Acid Red 52 (acid rhodamine), CI Acid Red 87 (Eosin G), CI Acid Red 92 (Acid Fluorescent Pink PB) ), CI Acid Red 87 (Crimson G), CI Acid Red 92 (Acid Fluorescent Pink PB), CI Acid Red 289, CI Acid Red 388, Bengal Red B (Edible Red No. 5), Acid Rhodamine G, CI Acid violet 9, etc. Acid dye; CI solvent red 35, CI solvent red 36, CI solvent red 42, CI solvent red 43, CI solvent red 44, CI solvent red 45, CI solvent red 46, CI solvent red 47, CI solvent red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10, etc. Oil-soluble dye; CI basic red 1 (rhodamine 6GCP), CI alkaline red 8 (rhodamine G), etc. It is a basic dye or the like.

另外，作為花青化合物，例如也可使用C.I.鹼性紅13、C.I.鹼性紅14、C.I.鹼性紫7、C.I.鹼性黃11、C.I.鹼性黃13、C.I.鹼性黃21、C.I.鹼性黃28、C.I.鹼性黃51等花青系鹼性染料。 Further, as the cyanine compound, for example, CI basic red 13, CI basic red 14, CI basic purple 7, CI basic yellow 11, CI basic yellow 13, CI basic yellow 21, CI alkaline can also be used. Cyanine alkaline dyes such as yellow 28 and CI basic yellow 51.

此外，作為三芳基甲烷化合物，例如也可使用下述染料：C.I.酸性藍1、C.I.酸性藍3、C.I.酸性藍5、C.I.酸性藍7、C.I.酸性藍9、C.I.酸性藍11、C.I.酸性藍15、C.I.酸性藍17、C.I.酸性藍19、C.I.酸性藍22、C.I.酸性藍24、C.I.酸性藍38、C.I.酸性藍48、C.I.酸性藍75、C.I.酸性藍83、C.I.酸性藍90、C.I.酸性藍91、C.I.酸性藍93、C.I.酸性藍93：1、C.I.酸性藍100、C.I.酸性藍103、C.I.酸性藍104、C.I.酸性藍109、C.I.酸性藍110、C.I.酸性藍119、C.I.酸性藍147、C.I.酸性藍269、C.I.酸性藍123、C.I. 酸性藍213、C.I.直接藍41、C.I.酸性紫17、C.I.酸性紫19、C.I.酸性紫21、C.I.酸性紫23、C.I.酸性紫25、C.I.酸性紫38、C.I.酸性紫49、C.I.酸性紫72等三芳基甲烷系酸性染料；C.I.鹼性紫1(甲基紫)、C.I.鹼性紫3(結晶紫)、C.I.鹼性紫14(Magenta)、C.I.鹼性藍1(鹼性花青6G)、C.I.鹼性藍5(鹼性花青EX)、C.I.鹼性藍7(維多利亞純藍BO)、C.I.鹼性藍26(維多利亞藍B conc.)、C.I.鹼性綠1(亮綠GX)、C.I.鹼性綠4(孔雀綠)等三芳基甲烷系鹼性染料；C.I.直接藍41等三芳基甲烷系直接染料等。 Further, as the triarylmethane compound, for example, the following dyes may be used: CI Acid Blue 1, CI Acid Blue 3, CI Acid Blue 5, CI Acid Blue 7, CI Acid Blue 9, CI Acid Blue 11, CI Acid Blue 15 , CI Acid Blue 17, CI Acid Blue 19, CI Acid Blue 22, CI Acid Blue 24, CI Acid Blue 38, CI Acid Blue 48, CI Acid Blue 75, CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 91 , CI Acid Blue 93, CI Acid Blue 93:1, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104, CI Acid Blue 109, CI Acid Blue 110, CI Acid Blue 119, CI Acid Blue 147, CI Acidity Blue 269, CI Acid Blue 123, CI Acid blue 213, CI direct blue 41, CI acid violet 17, CI acid violet 19, CI acid violet 21, CI acid violet 23, CI acid violet 25, CI acid violet 38, CI acid violet 49, CI acid violet 72, etc. Methane-based acid dye; CI alkaline violet 1 (methyl violet), CI alkaline violet 3 (crystal violet), CI alkaline violet 14 (Magenta), CI alkaline blue 1 (alkaline cyanine 6G), CI Basic Blue 5 (Alkaline Cyanine EX), CI Basic Blue 7 (Victoria Pure Blue BO), CI Basic Blue 26 (Victoria Blue B conc.), CI Alkaline Green 1 (Bright Green GX), CI Base Triarylmethane-based basic dyes such as green 4 (malachite green); triarylmethane-based direct dyes such as CI Direct Blue 41.

另外，作為蒽醌化合物，例如也可使用下述染料：C.I.酸性藍23、C.I.酸性藍25、C.I.酸性藍27、C.I.酸性藍35、C.I.酸性藍40、C.I.酸性藍41、C.I.酸性藍43、C.I.酸性藍45、C.I.酸性藍47、C.I.酸性藍49、C.I.酸性藍51、C.I.酸性藍53、C.I.酸性藍55、C.I.酸性藍56、C.I.酸性藍62、C.I.酸性藍68、C.I.酸性藍69、C.I.酸性藍78、C.I.酸性藍80、C.I.酸性藍81：1、C.I.酸性藍11、C.I.酸性藍124、C.I.酸性藍127、C.I.酸性藍127：1、C.I.酸性藍140、C.I.酸性藍150、C.I.酸性藍175、C.I.酸性藍215、C.I.酸性藍230、C.I.酸性藍277、C.I.酸性藍344、C.I.酸性紫41、C.I.酸性紫42、C.I.酸性紫43、C.I.酸性綠25、C.I.酸性綠27等蒽醌系酸性染料；C.I.直接紫17等直接染料；C.I.溶劑紅172、C.I.溶劑紅222、C.I.溶劑紫60等蒽 醌系油溶性染料等。 Further, as the ruthenium compound, for example, the following dyes: CI Acid Blue 23, CI Acid Blue 25, CI Acid Blue 27, CI Acid Blue 35, CI Acid Blue 40, CI Acid Blue 41, CI Acid Blue 43, CI Acid Blue 45, CI Acid Blue 47, CI Acid Blue 49, CI Acid Blue 51, CI Acid Blue 53, CI Acid Blue 55, CI Acid Blue 56, CI Acid Blue 62, CI Acid Blue 68, CI Acid Blue 69, CI Acid Blue 78, CI Acid Blue 80, CI Acid Blue 81:1, CI Acid Blue 11, CI Acid Blue 124, CI Acid Blue 127, CI Acid Blue 127:1, CI Acid Blue 140, CI Acid Blue 150, CI Acid Blue 175, CI Acid Blue 215, CI Acid Blue 230, CI Acid Blue 277, CI Acid Blue 344, CI Acid Violet 41, CI Acid Violet 42, CI Acid Violet 43, CI Acid Green 25, CI Acid Green 27, etc. Lanthanide acid dye; CI direct violet 17 and other direct dyes; CI solvent red 172, CI solvent red 222, CI solvent violet 60, etc. Lanthanide oil-soluble dyes, etc.

作為單體α、單體β的合成方法，沒有特別限制，可使用以往公知的方法。例如上述式(1-1)表示的化合物、上述式(1-2)表示的化合物可通過如下方式得到：採用一般的有機合成方法對具有官能團的上述染料的基本骨架導入具有烯性不飽和基團的基團，或者對染料的合成原料導入具有烯性不飽和基團的基團後，合成染料。更具體而言，可參照日本特開2013-178478號公報、日本特開2013-173850號公報、日本特開2013-210621號公報、日本特開2013-028764號公報等的記載。 The method for synthesizing the monomer α and the monomer β is not particularly limited, and a conventionally known method can be used. For example, the compound represented by the above formula (1-1) and the compound represented by the above formula (1-2) can be obtained by introducing a basic skeleton having the above-mentioned dye having a functional group into an ethylenically unsaturated group by a general organic synthesis method. The group is synthesized, or a dye having a olefinic unsaturated group is introduced into the synthetic raw material of the dye to synthesize the dye. More specifically, the descriptions of Japanese Patent Laid-Open Publication No. 2013-178478, JP-A-2013-173850, JP-A-2013-210621, and JP-A-2013-028764.

而且，通過使單體α、單體β聚合，可分別製造聚合物α、聚合物β。聚合反應可使用以往公知的方法，例如可採用與後述的(C)黏結劑樹脂相同的方法。 Further, by polymerizing the monomer α and the monomer β, the polymer α and the polymer β can be produced separately. A conventionally known method can be used for the polymerization reaction, and for example, the same method as the (C) binder resin described later can be employed.

聚合物α和聚合物β也可以分別具有除單體α、單體β以外的其它可共聚的烯性不飽和單體(以下，也稱為「不飽和單體(a3)」)作為結構單元。 The polymer α and the polymer β may each have a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (a3)") other than the monomer α or the monomer β as a structural unit. .

作為這樣的不飽和單體(a3)的具體例，例如可舉出：(甲基)丙烯酸、馬來酸、馬來酸酐、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯、對乙烯基苯甲酸之類的具有羧基的烯性不飽和單體；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺之類的N-位取代馬來醯亞胺；苯乙烯、α-甲基苯乙烯、對羥基苯乙烯、對羥基-α- 甲基苯乙烯、對乙烯基苄基縮水甘油醚，苊烯之類的芳香族乙烯基化合物；(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、聚乙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚乙二醇(聚合度2~10)單(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)單(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異酯、(甲基)丙烯酸三環[5.2.1.0^2,6]癸烷-8-基酯、(甲基)丙烯酸二環戊烯酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸4-羥基苯酯、對枯基苯酚的環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、3-[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷之類的(甲基)丙烯酸酯；環己基乙烯基醚、異基乙烯基醚、三環[5.2.1.0^2,6]癸烷-8-基乙烯基醚、五環十五烷基乙烯基醚、3-(乙烯基氧基甲基)-3-乙基氧雜環丁烷之類的乙烯基醚；在聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之類的聚合物分子鏈的末端具有單(甲基)丙烯醯基的大分子單體。 Specific examples of such an unsaturated monomer (a3) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl)acryloxyethyl] Ester, ω-carboxypolycaprolactone mono(meth)acrylate, ethylenically unsaturated monomer having a carboxyl group such as p-vinylbenzoic acid; N-phenylmaleimide, N-cyclohexyl horse N-position substituted maleimine such as quinone imine; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether An aromatic vinyl compound such as terpene; methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate Ester, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (Meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, (meth) acrylate ring Ester, (meth)acrylic acid Ester, tricyclo [5.1.02 ^2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid Ethylene oxide modified (meth) acrylate of 4-hydroxyphenyl ester, p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 3 -((methyl)propenyloxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane (methyl) Acrylate; cyclohexyl vinyl ether, different Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyl a vinyl ether such as oxetane; having a terminal of a polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, or polyoxyalkylene Mono(methyl)acrylonitrile-based macromonomer.

其中，從耐熱性、耐溶劑性、遷移性抑制、分散性的觀點出發，作為不飽和單體(a3)，較佳為具有羧基的烯性不飽和單體、(甲基)丙烯酸酯。 In particular, the unsaturated monomer (a3) is preferably an ethylenically unsaturated monomer having a carboxyl group or a (meth) acrylate from the viewpoint of heat resistance, solvent resistance, migration resistance, and dispersibility.

聚合物α和聚合物β為含有不飽和單體(a3)作 為結構單元的共聚物時，聚合物α和聚合物β的所有結構單元中的不飽和單體(a3)的共聚比例較佳為以下態樣。即，不飽和單體(a3)的共聚比例在所有結構單元中，較佳為30~97質量%，進一步更佳為40~95質量%，特佳為50~90質量%。通過以這樣的範圍使不飽和單體(a3)共聚，容易得到耐熱性、耐溶劑性、遷移性抑制、分散性優異的著色組成物。 Polymer α and polymer β are contained in unsaturated monomer (a3) In the case of the copolymer of the structural unit, the copolymerization ratio of the unsaturated monomer (a3) in all the structural units of the polymer α and the polymer β is preferably as follows. That is, the copolymerization ratio of the unsaturated monomer (a3) is preferably from 30 to 97% by mass, still more preferably from 40 to 95% by mass, particularly preferably from 50 to 90% by mass, based on all the structural units. When the unsaturated monomer (a3) is copolymerized in such a range, a coloring composition excellent in heat resistance, solvent resistance, migration property, and dispersibility can be easily obtained.

聚合物α和聚合物β的由凝膠滲透色譜(以下，簡稱為GPC)(洗脫溶劑：四氫呋喃)測得的按聚苯乙烯換算的重均分子量(Mw)通常為1000~100000，較佳為3000~50000，進一步更佳為3000~10000。通過成為這種方式，能夠使對比度、耐熱性、耐溶劑性、遷移性抑制、被覆膜特性、電氣特性、圖案形狀、分辨率良好。 The polystyrene-equivalent weight average molecular weight (Mw) of the polymer α and the polymer β as measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually from 1,000 to 100,000, preferably. It is 3000~50000, and further preferably 3000~10000. In this manner, contrast, heat resistance, solvent resistance, migration resistance, coating film properties, electrical properties, pattern shape, and resolution can be improved.

另外，聚合物α和聚合物β的重均分子量(Mw)與數均分子量(Mn)之比(Mw/Mn)較佳為1.0~5.0，更佳為1.0~3.0。應予說明，這裡所說的Mn是由GPC(洗脫溶劑：四氫呋喃)測得的按聚苯乙烯換算的數均分子量。 Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer α and the polymer β is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn is a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

在本發明中，作為(A)著色劑，包含選自化合物群α中的至少1種與選自化合物群β中的至少1種的組合，但從對比度的觀點出發，較佳為化合物群α為聚合物α且化合物群β為單體β的態樣。另外，從耐熱性的觀點出發，較佳為化合物群α為聚合物α且化合物群β為單體β的態樣或化合物群α為聚合物α且化合物群β為聚合物β的態樣。此外，從耐溶劑性的觀點出發，較佳為化合物群α為聚合物α且化合物群β為聚合物β的態樣。其中，從平衡 良好地以高水準實現對比度、耐熱性和耐溶劑性的觀點出發，進一步更佳為化合物群α為聚合物α且化合物群β為聚合物β的態樣。 In the present invention, the (A) coloring agent contains at least one selected from the group consisting of compound α and at least one selected from the group of compounds β. However, from the viewpoint of contrast, the compound group α is preferred. It is a polymer α and the compound group β is a state of the monomer β. Further, from the viewpoint of heat resistance, it is preferred that the compound group α is a polymer α and the compound group β is a monomer β or the compound group α is a polymer α and the compound group β is a polymer β. Further, from the viewpoint of solvent resistance, it is preferred that the compound group α is a polymer α and the compound group β is a polymer β. Among them, from balance From the viewpoint of achieving high contrast, heat resistance and solvent resistance at a high level, it is more preferable that the compound group α is a polymer α and the compound group β is a polymer β.

化合物群α與化合物群β的含有比例(α/β)以莫耳比計，較佳為99/1~40/60，更佳為98/2~60/40，進一步更佳為97/3~70/30，特佳為96/4~80/20。 The content ratio of the compound group α to the compound group β (α/β) is preferably 99/1 to 40/60, more preferably 98/2 to 60/40, still more preferably 97/3, in terms of a molar ratio. ~70/30, especially good for 96/4~80/20.

尤其是在化合物群α為聚合物α且化合物群β為聚合物β的方式的情況下，從平衡良好地以高水準實現對比度、耐熱性和耐溶劑性的觀點出發，聚合物α與聚合物β的含有比例(α/β)以莫耳比計，較佳為93/7~75/25，更佳為92/8~80/20，進一步更佳為91/9~85/25。 In particular, when the compound group α is a polymer α and the compound group β is a polymer β, the polymer α and the polymer are obtained from the viewpoint of achieving high contrast, heat resistance and solvent resistance at a high level. The content ratio of β (α/β) is, in terms of a molar ratio, preferably 93/7 to 75/25, more preferably 92/8 to 80/20, still more preferably 91/9 to 85/25.

本發明的著色組成物也可以混合除化合物群α和化合物群β以外的其它著色劑來使用。作為其它著色劑，沒有特別限定，可根據用途適當地選擇色彩、材質。作為其它著色劑，可舉出除化合物群α和化合物群β以外的顏料、染料。當然可以含有具有發出螢光的部位且不具有聚合性基團的化合物，例如具有選自發色團和花青發色團中的至少1種發色團且不具有聚合性基團的化合物，也可以含有具有吸收螢光的部位且不具有聚合性基團的化合物，例如具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團且不具有聚合性基團的化合物。其中，從得到亮度、對比度和著色力高的像素的方面考慮，作為顏料，較佳為有機顏料，另外作為染料，較佳為有機染料。作為有機染料，例如可舉出本說明書第[0072]~[0075]段中記載的染料。 The coloring composition of the present invention may be used by mixing a coloring agent other than the compound group α and the compound group β. The other coloring agent is not particularly limited, and the color and material can be appropriately selected depending on the application. Examples of the other coloring agent include pigments and dyes other than the compound group α and the compound group β. It is of course possible to contain a compound having a site which emits fluorescence and which does not have a polymerizable group, for example, having a compound selected from a compound having at least one chromophore in the chromophore and the cyanine chromophore and having no polymerizable group, and may also contain a compound having a site that absorbs fluorescence and has no polymerizable group, for example, having a compound selected from the group consisting of A compound having at least one chromophore in the triarylmethane chromophore and the quinone chromophore and having no polymerizable group. Among them, from the viewpoint of obtaining pixels having high luminance, contrast, and coloring power, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye. Examples of the organic dye include the dyes described in paragraphs [0072] to [0075] of the present specification.

作為有機顏料，例如可舉出顏色索引中被分類為顏料的如下該的化合物。 Examples of the organic pigment include the following compounds classified as pigments in the color index.

C.I.顏料紅166、C.I.顏料紅177、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅264；C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58、C.I.顏料綠59；C.I.顏料藍15：6、C.I.顏料藍16、C.I.顏料藍80；C.I.顏料黃14、C.I.顏料黃83、C.I.顏料黃129、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃179、C.I.顏料黃180、C.I.顏料黃185、C.I.顏料黃211、C.I.顏料黃215；C.I.顏料橙38；C.I.顏料紫23。 CI pigment red 166, CI pigment red 177, CI pigment red 224, CI pigment red 242, CI pigment red 254, CI pigment red 264; CI pigment green 7, CI pigment green 36, CI pigment green 58, CI pigment green 59; CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 80; CI Pigment Yellow 14, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215; CI Pigment Orange 38; CI Pigment Violet 23.

此外，可舉出上述式表示的紅色顏料、日本特開2001-081348號公報、日本特開2010-026334號公報、日本特開2010-237384號公報、日本特開2010-237569 號公報、日本特開2011-006602號公報、日本特開2011-145346號公報等中記載的色澱顏料。 In addition, the red pigments of the above-mentioned formula, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, and JP-A-2010-237569 The lake pigment described in Japanese Laid-Open Patent Publication No. 2011-145346, and the like.

在本發明中，也可以利用重結晶法、再沉澱法、溶劑清洗法、昇華法、真空加熱法或它們的組合將任意混合的其它顏料加以精製而使用。另外，這些顏料也可以根據需要用樹脂對其粒子表面進行改性而使用。作為對顏料的粒子表面進行改性的樹脂，例如可舉出日本特開2001-108817號公報中記載的載色劑樹脂或者市售的各種用於顏料分散的樹脂。作為炭黑表面的樹脂被覆方法，例如可採用日本特開平9-71733號公報、日本特開平9-95625號公報、日本特開平9-124969號公報等中記載的方法。另外，有機顏料可以通過所謂的鹽磨使一次粒子微細化而使用。作為鹽磨的方法，例如可採用日本特開平8-179111號公報中公開的方法。 In the present invention, any of the other pigments which are mixed may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. Further, these pigments may be used by modifying the surface of the particles with a resin as needed. Examples of the resin that modifies the surface of the pigment particles include a vehicle resin described in JP-A-2001-108817 or a commercially available resin for pigment dispersion. For the method of coating the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969 can be used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.

另外，在本發明中，在含有任意混合的其它著色劑的同時，也可以進一步含有公知的分散劑和分散助劑。作為公知的分散劑，例如可舉出聚胺基甲酸酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙烯烷基苯基醚系分散劑、聚乙二醇二酯系分散劑，山梨糖醇酐脂肪酸酯系分散劑、聚酯系分散劑、丙烯酸系分散劑等，另外，作為分散助劑，可舉出顏料衍生物等。 Further, in the present invention, a known dispersant and a dispersing aid may be further contained together with other coloring agents which are arbitrarily mixed. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkylphenyl ether dispersant. A polyethylene glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, and the like, and a dispersing aid may, for example, be a pigment derivative.

這樣的分散劑可通過商業途徑得到，例如作為丙烯酸系分散劑，可舉出Disperbyk-2000、Disperbyk-2001、BYK-LPN6919、BYK-LPN21116(以上 ，BYK-Chemie(BYK)公司製)等，作為聚胺基甲酸酯系分散劑，可舉出Disperbyk-161、Disperbyk-162、Disperbyk-165、Disperbyk-167、Disperbyk-170、Disperbyk-182(以上，BYK-Chemie(BYK)公司製)、Solsperse76500(Lubrizol股份有限公司製)等，作為聚乙烯亞胺系分散劑，可舉出Solsperse24000(Lubrizol股份有限公司製)等，作為聚酯系分散劑，可舉出Adisper PB821、Adisper PB822、Adisper PB880、Adisper PB881(以上，Ajinomoto Fine-Techno股份有限公司製)等，以及BYK-LPN21324(BYK-Chemie(BYK)公司製)等。 Such a dispersing agent can be obtained commercially, for example, as an acrylic dispersing agent, and examples thereof include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above Examples of the polyurethane dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (available from BYK-Chemie (BYK)). In the above, as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., as a polyester-based dispersant, may be used as a dispersing agent for a polyethyleneimine-based dispersing agent, such as BYK-Chemie (BYK). Examples thereof include Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Ltd.), and BYK-LPN21324 (manufactured by BYK-Chemie (BYK) Co., Ltd.).

另外，作為顏料衍生物，具體而言，可舉出銅酞菁、二酮吡咯并吡咯、喹酞酮的磺酸衍生物等。 In addition, specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

在本發明中，其它著色劑可以單獨使用或者混合2種以上使用。 In the present invention, other colorants may be used singly or in combination of two or more.

含有其它著色劑時，其它著色劑的含有比例相對於著色劑的合計含量，較佳為70質量%以下，更佳為50質量份以下。下限值沒有特別限定，為0.01質量%以上即可。 When the other coloring agent is contained, the content ratio of the other coloring agent is preferably 70% by mass or less, and more preferably 50 parts by mass or less based on the total content of the coloring agent. The lower limit value is not particularly limited, and may be 0.01% by mass or more.

從形成耐熱性、耐溶劑性、遷移性抑制和亮度高且色純度優異的像素或者遮光性優異的黑矩陣、黑間隔物的方面考慮，(A)著色劑的含有比例通常在著色組成物的固體成分中為3~70質量%，較佳為5~60質量%，進一步更佳為5~30質量%。這裡，固體成分是除後述的溶劑以外的成分。 The content ratio of the (A) colorant is usually in the coloring composition, from the viewpoint of forming a black matrix or a black spacer having excellent heat resistance, solvent resistance, migration resistance, high brightness, and excellent color purity, or a black matrix excellent in light blocking properties. The solid content is 3 to 70% by mass, preferably 5 to 60% by mass, and more preferably 5 to 30% by mass. Here, the solid component is a component other than the solvent described later.

-(B)聚合性化合物- - (B) Polymeric Compound -

本發明中聚合性化合物是指具有2個以上可聚合的基團的化合物。作為可聚合的基團，例如可舉出烯性不飽和基團、環氧乙烷基、氧雜環丁烷基、N-烷氧基甲基胺基等。在本發明中，作為聚合性化合物，較佳為具有2個以上(甲基)丙烯醯基的化合物或具有2個以上N-烷氧基甲基胺基的化合物。 The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups.

作為具有2個以上(甲基)丙烯醯基的化合物的具體例，可舉出使脂肪族多羥基化合物與(甲基)丙烯酸反應得到的多官能(甲基)丙烯酸酯、被己內酯改性的多官能(甲基)丙烯酸酯、被環氧烷改性的多官能(甲基)丙烯酸酯、使具有羥基的(甲基)丙烯酸酯與多官能異氰酸酯反應得到的多官能聚胺基甲酸酯(甲基)丙烯酸酯、使具有羥基的(甲基)丙烯酸酯與酸酐反應得到的具有羧基的多官能(甲基)丙烯酸酯等。 Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and being modified by caprolactone. Polyfunctional (meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional polyamine group obtained by reacting (meth) acrylate having hydroxyl group with polyfunctional isocyanate An acid ester (meth) acrylate or a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

這裡，作為脂肪族多羥基化合物，例如可舉出乙二醇、丙二醇、聚乙二醇、聚丙二醇之類的2價脂肪族多羥基化合物；甘油、三羥甲基丙烷、季戊四醇、二季戊四醇之類的3價以上的脂肪族多羥基化合物。作為上述具有羥基的(甲基)丙烯酸酯，例如可舉出(甲基)丙烯酸2-羥基乙酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、甘油二甲基丙烯酸酯等。作為上述多官能異氰酸酯，例如可舉出甲苯二異氰酸酯、六亞甲基二異氰酸酯、二苯基亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等。作為酸酐， 例如可舉出琥珀酸酐、馬來酸酐、戊二酸酐、衣康酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐之類的二元酸的酸酐、均苯四甲酸二酐、聯苯四甲酸二酐、二苯甲酮四羧酸二酐之類的四元酸二酐。 Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol; A trivalent or higher aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. As an acid anhydride, Examples thereof include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic dianhydride, and biphenyl. A tetrabasic acid dianhydride such as tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

另外，作為被己內酯改性的多官能(甲基)丙烯酸酯，例如可舉出日本特開平11-44955號公報的第[0015]~[0018]段中記載的化合物。作為上述被環氧烷改性的多官能(甲基)丙烯酸酯，可舉出被選自環氧乙烷和環氧丙烷中的至少1種改性的雙酚A二(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的異氰脲酸三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的三羥甲基丙烷三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的季戊四醇三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的季戊四醇四(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的二季戊四醇五(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的二季戊四醇六(甲基)丙烯酸酯等。 In addition, as the polyfunctional (meth) acrylate which is modified by the caprolactone, for example, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified. The polyfunctional (meth) acrylate modified with the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. And at least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra(meth)acrylate in propylene oxide, dipentaerythritol penta(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide At least one modified dipentaerythritol hexa(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide.

另外，作為具有2個以上N-烷氧基甲基胺基的化合物，例如可舉出具有三聚氰胺結構、苯并胍胺結構、脲結構的化合物等。應予說明，三聚氰胺結構、苯并胍胺結構是指具有1個以上的三環或苯基取代三環作為基本骨架的化學結構，是也包含三聚氰胺、苯并胍胺或它們的縮合物在內的概念。作為具有2個以上N-烷氧基甲基胺基的化合物的具體例，可舉出N,N,N',N',N",N" -六(烷氧基甲基)三聚氰胺、N,N,N',N'-四(烷氧基甲基)苯并胍胺、N,N,N',N'-四(烷氧基甲基)甘脲等。 In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. It should be noted that the melamine structure and the benzoguanamine structure refer to having one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N ' ,N ' ,N " ,N " -hexa(alkoxymethyl)melamine, N , N, N ' , N ' - tetra (alkoxymethyl) benzoguanamine, N, N, N ' , N ' - tetra (alkoxymethyl) glycoluril and the like.

這些聚合性化合物中，較佳為使3元以上的脂肪族多羥基化合物與(甲基)丙烯酸反應得到的多官能(甲基)丙烯酸酯、被己內酯改性的多官能(甲基)丙烯酸酯、多官能聚胺基甲酸酯(甲基)丙烯酸酯、具有羧基的多官能(甲基)丙烯酸酯、N,N,N',N',N",N"-六(烷氧基甲基)三聚氰胺、N,N,N',N'-四(烷氧基甲基)苯并胍胺。從著色層的強度高、著色層的表面平滑性優且未曝光部在基板上和遮光層上不易產生污垢、膜殘留等方面考慮，在使3元以上的脂肪族多羥基化合物與(甲基)丙烯酸反應得到的多官能(甲基)丙烯酸酯中，特佳為三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯，在具有羧基的多官能(甲基)丙烯酸酯中，特佳為使季戊四醇三丙烯酸酯與琥珀酸酐反應得到的化合物、使二季戊四醇五丙烯酸酯與琥珀酸酐反應得到的化合物。 Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (methyl) modified by caprolactone is preferable. Acrylate, polyfunctional polyurethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N ' , N ' , N " , N " - hexa yl-methyl) melamine, N, N, N ', N' - tetra (alkoxymethyl) benzoguanamine. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of dirt and film residue on the substrate and the light-shielding layer in the unexposed portion, the aliphatic polyhydroxy compound having 3 or more elements and (methyl group) are used. Among the polyfunctional (meth) acrylates obtained by the reaction of acrylic acid, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyfunctional groups having a carboxyl group. Among the (meth) acrylates, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride or a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride is particularly preferred.

在本發明中，(B)聚合性化合物可以單獨使用或者混合2種以上使用。 In the present invention, the (B) polymerizable compound may be used singly or in combination of two or more.

本發明中的(B)聚合性化合物的含量相對於(A)著色劑100質量份，較佳為10~1000質量份，進一步更佳為20~800質量份，進一步更佳為100~700質量份。通過成為這樣的方式，能夠使硬化性、鹼性顯影性良好。 The content of the (B) polymerizable compound in the present invention is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, still more preferably 100 to 700 parts by mass based on 100 parts by mass of the (A) coloring agent. Share. In such a manner, the curability and the alkali developability can be improved.

-(C)黏結劑樹脂- -(C) Adhesive Resin -

本發明的著色組成物中可以含有黏結劑樹脂(其中，不包括聚合物α和β)。由此，能夠提高著色組成物的鹼可溶性、與基板的黏接性、保存穩定性等。作為黏結劑樹脂，只要不屬於聚合物α和β就沒有特別限定，但較佳為具有羧基、酚性羥基等酸性官能團的樹脂。其中，較佳為具有羧基的聚合物(以下，稱為「含羧基聚合物」)，例如可舉出具有1個以上羧基的烯性不飽和單體(以下，稱為「不飽和單體(c1)」)與其它可共聚的烯性不飽和單體(以下，稱為「不飽和單體(c2)」)的共聚物。 The coloring composition of the present invention may contain a binder resin (excluding polymers α and β). Thereby, the alkali solubility of the coloring composition, the adhesion to the substrate, the storage stability, and the like can be improved. The binder resin is not particularly limited as long as it does not belong to the polymers α and β, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer" (hereinafter referred to as "unsaturated monomer"). C1)") a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (c2)").

作為不飽和單體(c1)，例如可舉出(甲基)丙烯酸、馬來酸、馬來酸酐、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯、對乙烯基苯甲酸等。 Examples of the unsaturated monomer (c1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(methyl)acryloxyethyl ester, and ω-carboxyl polymerization. Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

這些不飽和單體(c1)可以單獨使用或者混合2種以上使用。 These unsaturated monomers (c1) can be used individually or in mixture of 2 or more types.

另外，作為不飽和單體(c2)，例如可舉出不飽和單體(a3)中例示的N-位取代馬來醯亞胺、芳香族乙烯基化合物、(甲基)丙烯酸酯、乙烯基醚、在聚合物分子鏈的末端具有單(甲基)丙烯醯基的大分子單體等，作為具體例，可舉出與上述相同的單體。 In addition, examples of the unsaturated monomer (c2) include an N-position substituted maleimide, an aromatic vinyl compound, a (meth) acrylate, and a vinyl group exemplified in the unsaturated monomer (a3). The ether is a macromonomer having a mono(meth)acryl fluorenyl group at the terminal of the polymer molecular chain, and specific examples thereof include the same monomers as described above.

不飽和單體(c2)可以單獨使用或者混合2種以上使用。 The unsaturated monomer (c2) may be used singly or in combination of two or more.

在不飽和單體(c1)與不飽和單體(c2)的共聚物中，該共聚物中的不飽和單體(c1)的共聚比例較佳為5~50質量%，進一步更佳為10~40質量%。通過以這樣的 範圍使不飽和單體(c1)共聚，能夠得到鹼性顯影性和保存穩定性優異的著色組成物。 In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably from 5 to 50% by mass, further preferably 10 ~40% by mass. By adopting such In the range, the unsaturated monomer (c1) is copolymerized, and a coloring composition excellent in alkali developability and storage stability can be obtained.

作為不飽和單體(c1)與不飽和單體(c2)的共聚物的具體例，例如可舉出日本特開平7-140654號公報、日本特開平8-259876號公報、日本特開平10-31308號公報、日本特開平10-300922號公報、日本特開平11-174224號公報、日本特開平11-258415號公報、日本特開2000-56118號公報、日本特開2004-101728號公報等中公開的共聚物。 Specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-10. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The disclosed copolymers.

另外，在本發明中，例如也可以像日本特開平5-19467號公報、日本特開平6-230212號公報、日本特開平7-207211號公報、日本特開平9-325494號公報、日本特開平11-140144號公報、日本特開2008-181095號公報等公開的那樣，使用側鏈具有(甲基)丙烯醯基等聚合性不飽和鍵的含羧基聚合物作為黏結劑樹脂。 In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain is used as a binder resin, as disclosed in JP-A-2008-181095, and the like.

本發明中的黏結劑樹脂的由凝膠滲透色譜(以下，簡稱為GPC)(洗脫溶劑：四氫呋喃)測得的按聚苯乙烯換算的重均分子量(Mw)通常為1000~100000，較佳為3000~50000。通過成為這樣的方式，被覆膜的殘膜率、圖案形狀、耐熱性、電氣特性、分辨率進一步提高，另外，能夠以高水準抑制塗布時的乾燥異物的產生。 The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter, abbreviated as GPC) (elution solvent: tetrahydrofuran) in the present invention is usually from 1,000 to 100,000, preferably from 1,000 to 100,000. It is 3000~50000. In such a manner, the residual film ratio, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the coating film are further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

另外，本發明中的黏結劑樹脂的重均分子量(Mw)與數均分子量(Mn)之比(Mw/Mn)較佳為1.0~5.0，更佳為1.0~3.0。應予說明，這裡所說的Mn是由GPC(洗脫溶劑：四氫呋喃)測得的按聚苯乙烯換算的數均分子量。 Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn is a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

本發明中的黏結劑樹脂可以利用公知的方法製造，例如，也可以利用日本特開2003-222717號公報、日本特開2006-259680號公報、國際公開第2007/029871號小冊子等中公開的方法控制其結構、Mw、Mw/Mn。 The binder resin in the present invention can be produced by a known method. For example, the method disclosed in JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 2007/029871 can be used. Control its structure, Mw, Mw / Mn.

在本發明中，(C)黏結劑樹脂可以單獨使用或者混合2種以上使用。 In the present invention, the (C) binder resin may be used singly or in combination of two or more.

在本發明中，(C)黏結劑樹脂的含量相對於(A)著色劑100質量份，通常為10~1000質量份，較佳為20~500質量份。通過成為這樣的方式，能夠使鹼性顯影性、著色組成物的保存穩定性、色度特性進一步提高。 In the present invention, the content of the (C) binder resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By such an aspect, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.

-光聚合起始劑- -Photopolymerization initiator -

本發明的著色組成物中可以含有光聚合起始劑。由此，能夠對著色組成物賦予感放射線性。本發明中使用的光聚合起始劑是通過可見光線、紫外線、遠紫外線、電子束、X射線等放射線的曝光，產生可引發上述聚合性化合物的聚合的活性物質的化合物。 The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the radiation-sensitive linearity can be imparted to the colored composition. The photopolymerization initiator used in the present invention is a compound which generates an active material capable of initiating polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

作為這樣的光聚合起始劑，例如可舉出噻噸酮系化合物、苯乙酮系化合物、聯咪唑系化合物、三系化合物，O-醯基肟系化合物、鎓鹽系化合物、苯偶姻系化合物、二苯甲酮系化合物、α-二酮系化合物、多環醌系化合物、重氮系化合物、醯亞胺磺酸酯系化合物等。 Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic guanidine compound, diazo compound, quinone a sulfonate compound or the like.

在本發明中，光聚合起始劑可以單獨使用或者混合2種以上使用。作為光聚合起始劑，較佳為選自噻噸酮系化合物、苯乙酮系化合物、聯咪唑系化合物、三系化合物、O-醯基肟系化合物中的至少1種。 In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-mercapto lanthanide compound.

本發明中的較佳的光聚合起始劑中，作為噻噸酮系化合物的具體例，可舉出噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。 In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl Thiophenone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropyl thioxanthone and the like.

另外，作為苯乙酮系化合物的具體例，可舉出2-甲基-1-[4-(甲硫基)苯基]-2-啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉代苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-啉代苯基)丁烷-1-酮等。 Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Olostinophenyl)butan-1-one and the like.

另外，作為聯咪唑系化合物的具體例，可舉出2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑等。 Further, specific examples of the biimidazole-based compound include 2,2 ' -bis(2-chlorophenyl)-4,4 ' ,5,5 ' -tetraphenyl-1,2 ' -biimidazole, 2,2 ' -bis(2,4-dichlorophenyl)-4,4 ' ,5,5 ' -tetraphenyl-1,2 ' -biimidazole, 2,2 ' -bis(2,4, 6-Trichlorophenyl)-4,4 ' ,5,5 ' -tetraphenyl-1,2 ' -biimidazole.

應予說明，使用聯咪唑系化合物作為光聚合起始劑時，從能夠改進靈敏度的方面考慮，較佳為併用供氫體。這裡所說的「供氫體」是指能夠對通過曝光而由聯咪唑系化合物產生的自由基供給氫原子的化合物。作為供氫體，例如可舉出2-巰基苯并噻唑、2-巰基苯并唑等硫醇系供氫體，4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮等胺系供氫體。在本發明中，供氫體可以單獨使用或者混合2種以上使用，但從能夠進一步改進靈敏度的方面考慮，較佳為組合1種以上的硫醇系供氫體和1種以上的胺系供氫體來使用。 When a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. Azoles mercaptan hydrogen donor, 4,4 '- bis (dimethylamino) benzophenone, 4,4' - bis (diethylamino) benzophenone amine-based hydrogen donor . In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, in view of further improving the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more amines. Use hydrogen to use.

另外，作為三系化合物的具體例，可舉出2,4,6-三(三氯甲基)-均三、2-甲基-4,6-雙(三氯甲基)- 均三、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三等具有鹵甲基的三系化合物。 In addition, as three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-all , 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halomethyl group a compound.

另外，作為O-醯基肟系化合物的具體例，可舉出1-[4-(苯硫基)苯基]-1,2-辛二酮2-(O-苯甲醯肟)、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)、1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)、1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜環戊烷基)甲氧基苯甲醯基}-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)等。作為O-醯基肟系化合物的市售品，也可使用NCI-831、NCI-930(以上，ADEKA股份有限公司製)等。 Further, specific examples of the O-indenyl lanthanide compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidenyl}-9H-carbazol-3-yl] - Ethylketone 1-(O-acetamidine) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, manufactured by ADEKA CORPORATION), or the like can be used.

在本發明中，使用苯乙酮系化合物等聯咪唑系化合物以外的光聚合起始劑時，也可以併用增敏劑。作為這樣的增敏劑，例如可舉出4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮、4-二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙基胺基亞苄基)環己酮、7-二乙基胺基-3-(4-二乙基胺基苯甲醯基)香豆素、4-(二乙基胺基)查耳酮等。 In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4 ' -bis(dimethylamino)benzophenone, 4,4 ' -bis(diethylamino)benzophenone, and 4-di Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethyl Amino) chalcone and the like.

在本發明中，光聚合起始劑的含量相對於(B)聚合性化合物100質量份，較佳為0.01~120質量份，特佳為1~100質量份。通過成為這樣的方式，能夠使硬化性、被覆膜特性良好。 In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (B) polymerizable compound. In such a manner, the curability and the film properties can be improved.

-溶劑- - solvent -

本發明的著色組成物含有上述(A)和(B)成分以及任意添加的其它成分，通常配合有機溶劑製備成液態組成物。 The colored composition of the present invention contains the above components (A) and (B) and optionally added other components, and is usually prepared into a liquid composition in combination with an organic solvent.

作為有機溶劑，只要將構成著色組成物的(A)和(B)成分、其它成分分散或溶解，且不與這些成分反應，具有適度的揮發性，就可以適當地選擇使用。 The organic solvent is appropriately selected and used as long as the components (A) and (B) constituting the colored composition and other components are dispersed or dissolved, and do not react with these components, and have moderate volatility.

這樣的有機溶劑中，例如可舉出：乙二醇單甲醚、乙二醇單***、乙二醇單正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單***等(聚)烷撐二醇單烷基醚；乳酸甲酯、乳酸乙酯等乳酸烷基酯；甲醇、乙醇、丙醇、丁醇、異丙醇、異丁醇、三級丁醇、辛醇、2-乙基己醇、環己醇等(環)烷基醇；二丙酮醇等酮醇； 乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、二丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯等(聚)烷撐二醇單烷基醚乙酸酯；二乙二醇二甲醚、二乙二醇甲***、二乙二醇二***等二元醇醚；四氫呋喃等環狀醚；甲乙酮、環己酮、2-庚酮、3-庚酮等酮；丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等二乙酸酯；3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯等烷氧基羧酸酯；乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯等脂肪酸烷基酯；甲苯、二甲苯等芳香族烴；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺或內醯胺等。 Examples of such an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single positive Propylene ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly)alkylene Glycol monoalkyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethyl a (cyclo)alkyl alcohol such as hexanol or cyclohexanol; a keto alcohol such as diacetone alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol single (poly)alkylene glycol monoalkyl ether acetate, such as diethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ester; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether and other glycol ethers; tetrahydrofuran and other cyclic ether; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Ketone; diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Equivalent alkoxy carboxylate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, C Fatty acid alkyl esters such as ethyl ketoate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N- A decylamine such as dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone or an indoleamine.

這些有機溶劑中，從溶解性、顏料分散性、塗布性等觀點出發，較佳為丙二醇單甲醚、丙二醇單***、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二 醇單***乙酸酯、乙酸3-甲氧基丁酯、二乙二醇二甲醚、二乙二醇甲***、環己酮、2-庚酮、3-庚酮、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯、乳酸乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯，乙酸異戊酯，丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯等。 Among these organic solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and C are preferable from the viewpoints of solubility, pigment dispersibility, and coating properties. two Alcohol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butyl Glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, Isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

在本發明中，有機溶劑可以單獨使用或者混合2種以上使用。 In the present invention, the organic solvent may be used singly or in combination of two or more.

有機溶劑的含量沒有特別限定，較佳為除著色組成物的有機溶劑以外的各成分的合計濃度成為5~50質量%的量，更佳為成為10~40質量%的量。通過成為這樣的方式，能夠得到分散性、穩定性良好的著色劑分散液，以及塗布性、穩定性良好的著色組成物。 The content of the organic solvent is not particularly limited, and the total concentration of each component other than the organic solvent of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In such a manner, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.

-添加劑- -additive-

本發明的著色組成物也可以根據需要含有各種添加劑。 The colored composition of the present invention may contain various additives as needed.

作為添加劑，例如可舉出玻璃、氧化鋁等填充劑；聚乙烯醇、聚(氟烷基丙烯酸酯)類等高分子化合物；氟系表面活性劑、矽系表面活性劑等表面活性劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽 烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等密合促進劑；2,2-硫代雙(4-甲基-6-三級丁基苯酚)、2,6-二(三級丁基)苯酚等抗氧化劑；2-(3-三級丁基-5-甲基-2-羥基苯基)-5-氯苯并***、烷氧基二苯甲酮類等紫外線吸收劑；聚丙烯酸鈉等防凝聚劑；丙二酸、己二酸、衣康酸、檸康酸、富馬酸、中康酸、2-胺基乙醇、3-胺基-1-丙醇、5-胺基-1-戊醇、3-胺基-1,2-丙二醇、2-胺基-1,3-丙二醇、4-胺基-1,2-丁二醇等殘渣改善劑；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等顯影性改善劑等。 Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine surfactant or a lanthanoid surfactant; and ethylene; Trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy矽 Alkane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy An adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis ( Antioxidant such as 4-methyl-6-tertiary butyl phenol) or 2,6-di(tributyl)phenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl) ) UV absorbers such as 5-chlorobenzotriazole and alkoxybenzophenone; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid , mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3 - residue improving agent such as propylene glycol or 4-amino-1,2-butanediol; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) A developability improving agent such as propylene methoxyethyl ester or ω-carboxy polycaprolactone mono (meth) acrylate.

[著色硬化膜及其形成方法] [Coloring cured film and method of forming the same]

本發明的著色硬化膜是使用本發明的著色組成物而形成的，具體而言，是指用於顯示元件、固體攝像元件的各色像素、黑矩陣、黑間隔物等。 The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to a pixel for each color of a display element or a solid-state image sensor, a black matrix, a black spacer, and the like.

以下，對構成顯示元件、固體攝像元件的濾色器中使用的著色硬化膜及其形成方法進行說明。 Hereinafter, a colored cured film used in a color filter constituting a display element or a solid-state image sensor and a method of forming the same will be described.

作為製造濾色器的方法，第一，可舉出下述方法。首先，在基板的表面上，根據需要，以劃分出形成像素的部分的方式形成遮光層(黑矩陣)。接著，在該基板上例如塗布藍色的本發明的感放射線性著色組成物的液態組成物，其後進行預烘焙使溶劑蒸發，形成塗膜。接著 ，隔著光罩對該塗膜進行曝光後，使用鹼性顯影液進行顯影，溶解除去塗膜的未曝光部。然後，通過後烘焙，形成以規定的排列配置有藍色的像素圖案(著色硬化膜)的像素陣列。 As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixel is formed, as needed. Next, a liquid composition of the blue radiation sensitive coloring composition of the present invention is applied onto the substrate, for example, and then prebaked to evaporate the solvent to form a coating film. then After exposing the coating film through a photomask, development was carried out using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film. Then, by post-baking, a pixel array in which a blue pixel pattern (colored cured film) is arranged in a predetermined array is formed.

接著，使用綠色或紅色的各感放射線性著色組成物，與上述同樣地進行各感放射線性著色組成物的塗布、預烘焙、曝光、顯影和後烘焙，在同一基板上依次形成綠色的像素陣列和紅色的像素陣列。由此，得到在基板上配置有藍色、綠色和紅色這三原色的像素陣列的濾色器。其中，在本發明中，形成各色像素的順序不限於上述順序。 Next, using each of the green or red radiation-sensitive coloring compositions, coating, prebaking, exposing, developing, and post-baking the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and green pixel arrays are sequentially formed on the same substrate. And a red pixel array. Thereby, a color filter in which a pixel array of three primary colors of blue, green, and red is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

上述黑矩陣可通過利用光刻法使採用濺射、蒸鍍成膜的鉻等金屬薄膜成為所希望的圖案來形成，也可以使用分散有黑色著色劑的感放射線性著色組成物，與形成上述像素的情況同樣地形成。 The black matrix may be formed by forming a metal thin film such as chromium by sputtering or vapor deposition into a desired pattern by photolithography, or using a radiation-sensitive coloring composition in which a black colorant is dispersed, and forming the above-mentioned The case of pixels is formed in the same manner.

作為形成濾色器時使用的基板，例如可舉出玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。 Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine.

另外，也可以根據需要預先對這些基板實施利用矽烷偶聯劑等進行的試劑處理、等離子體處理、離子鍍、濺射、氣相反應法、真空蒸鍍等適當的預處理。 In addition, as appropriate, these substrates may be subjected to appropriate pretreatment such as reagent treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition using a decane coupling agent or the like.

在基板上塗布感放射線性著色組成物時，可採用噴霧法、輥塗法、旋塗法(spin coat method)、狹縫模頭塗布法(狹縫塗布法)、棒塗法等適當的塗布法，特佳為採用旋塗法、狹縫模頭塗布法。 When the radiation sensitive coloring composition is applied onto the substrate, appropriate coating such as a spray method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), or a bar coating method may be employed. The method is particularly preferred to use a spin coating method or a slit die coating method.

預烘焙的條件通常為70~110℃、1~10分鐘左右。 The prebaking conditions are usually 70 to 110 ° C for about 1 to 10 minutes.

塗布厚度以乾燥後的膜厚計，通常為0.6~8μm，較佳為1.2~5μm。 The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

作為形成選自像素和黑矩陣中的至少1種時所使用的放射線的光源，例如可舉出氙燈、鹵素燈、鎢燈、高壓汞燈、超高壓汞燈、金屬鹵化物燈、中壓汞燈、低壓汞燈等燈光源或氬離子激光、YAG激光、XeCl准分子激光、氮激光等激光光源等。作為曝光用光源，也可以使用紫外線LED。較佳為波長在190~450nm的範圍的放射線。 Examples of the light source for forming radiation to be used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and medium pressure mercury. Lamp light source such as lamp or low-pressure mercury lamp or laser light source such as argon ion laser, YAG laser, XeCl excimer laser or nitrogen laser. As the light source for exposure, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

放射線的曝光量通常較佳為10~10000J/m²。 The exposure amount of the radiation is usually preferably from 10 to 10000 J/m ² .

另外，作為上述鹼性顯影液，例如較佳為碳酸鈉、碳酸氫鈉、氫氧化鈉、氫氧化鉀、四甲基氫氧化銨、膽鹼、1,8-二氮雜雙環-[5.4.0]-7-十一碳烯、1,5-二氮雜雙環-[4.3.0]-5-壬烯等的水溶液。 Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4. An aqueous solution of 0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene.

鹼性顯影液中例如也可以適量添加甲醇、乙醇等水溶性有機溶劑、表面活性劑等。應予說明，鹼性顯影後通常進行水洗。 In the alkaline developing solution, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. It should be noted that water washing is usually carried out after alkaline development.

作為顯影處理法，可應用噴淋顯影法、噴霧顯影法、浸漬(dip)顯影法、旋覆浸沒(水坑)顯影法等。顯影條件較佳為常溫、5~300秒。 As the development treatment method, a shower development method, a spray development method, a dip development method, a spin-on immersion (puddle) development method, or the like can be applied. The developing conditions are preferably normal temperature, 5 to 300 seconds.

後烘焙的條件通常為180~280℃、10~60分鐘左右。 The post-baking conditions are usually 180 to 280 ° C for about 10 to 60 minutes.

這樣形成的像素的膜厚通常為0.5~5μm，較佳為1.0 ~3μm。 The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0. ~3μm.

另外，作為製造濾色器的第二方法，可採用日本特開平7-318723號公報、日本特開2000-310706號公報等中公開的採用噴墨方式得到各色像素的方法。在該方法中，首先，在基板的表面上形成兼具遮光功能的隔壁。接著，利用噴墨裝置向形成的隔壁內噴出例如藍色的熱硬化性著色組成物的液態組成物，其後進行預烘焙使溶劑蒸發。接著，根據需要對該塗膜進行曝光後，通過後烘焙使其硬化，形成藍色的像素圖案。 In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, a liquid composition of, for example, a blue thermosetting coloring composition is ejected into the formed partition walls by an inkjet device, and then prebaking is performed to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

接著，使用綠色或紅色的各熱硬化性著色組成物，與上述同樣地在同一基板上依次形成綠色的像素圖案和紅色的像素圖案。由此，得到在基板上配置有藍色、綠色和紅色這三原色的像素圖案的濾色器。其中，在本發明中，形成各色像素的順序不限於上述順序。 Next, using a green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.

應予說明，隔壁不僅起到遮光功能，還起到使噴出到隔區內的各色熱硬化性著色組成物不發生混色的功能，因此膜厚比上述第一方法中使用的黑矩陣厚。因此，隔壁通常使用黑色感放射線性組成物形成。 In addition, the partition wall not only functions as a light-shielding function, but also functions to prevent color mixing of the thermosetting coloring compositions of the respective colors discharged into the partition, and therefore the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

形成濾色器時使用的基板、放射線的光源以及預烘焙、後烘焙的方法、條件與上述第一方法相同。這樣，採用噴墨方式形成的像素的膜厚與隔壁的高度為同等程度。 The substrate used for forming the color filter, the light source of the radiation, and the method and conditions of the prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet method is equivalent to the height of the partition wall.

在這樣得到的像素圖案上根據需要形成保護膜後，通過濺射形成透明導電膜。形成透明導電膜後，還可以進一步形成間隔物而製成濾色器。間隔物通常使 用感放射線性組成物形成，也可以製成具有遮光性的間隔物(黑間隔物)。此時，使用分散有黑色著色劑的感放射線性著色組成物，但本發明的著色組成物也能夠適用於上述黑間隔物的形成。 After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. Spacers usually make It can also be formed by a radiation sensitive composition, and can also be made into a light-shielding spacer (black spacer). At this time, a radiation sensitive coloring composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be applied to the formation of the above black spacer.

本發明的感放射線性著色組成物也能夠適用於形成上述濾色器中使用的各色像素、黑矩陣、黑間隔物等中的任一著色硬化膜。 The radiation sensitive coloring composition of the present invention can also be applied to any of the coloring cured films which are used for forming the color pixels, the black matrix, the black spacer, and the like used in the color filter.

含有這樣形成的本發明的著色硬化膜的濾色器的亮度和色純度極高，因此對於彩色液晶顯示元件、彩色攝影管元件、彩色傳感器、有機EL顯示元件、電子紙等極為有用。應予說明，後述的顯示元件具備至少1個以上使用本發明的感放射線性著色組成物形成的著色硬化膜即可。 Since the color filter containing the colored cured film of the present invention thus formed has extremely high luminance and color purity, it is extremely useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, electronic paper, or the like. In addition, the display element which will be described later may have at least one color-hardened film formed using the radiation sensitive coloring composition of this invention.

[顯示元件] [display component]

本發明的顯示元件具備本發明的著色硬化膜。作為顯示元件，可舉出彩色液晶顯示元件、有機EL顯示元件、電子紙等。 The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

具備本發明的著色硬化膜的彩色液晶顯示元件可以是透射型也可以是反射型，可採用適當的結構。例如可採用在與配置有薄膜晶體管(TFT)的驅動用基板不同的其它基板上形成濾色器，驅動用基板與形成有濾色器的基板隔著液晶層對置的結構。另外，還可以採用在配置有薄膜晶體管(TFT)的驅動用基板的表面上形成有濾色器的基板與形成有ITO(摻雜了錫的氧化銦)電極或IZO(氧化銦與氧化鋅的混合物)電極的基板隔著液晶 層對置的結構。後者的結構能夠顯著提高開口率，具有得到明亮且高精細的液晶顯示元件的優點。應予說明，採用後者的結構時，黑矩陣、黑間隔物可以形成於形成有濾色器的基板側和形成有ITO電極或IZO電極的基板側中的任一方。 The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a color filter may be formed on another substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed face each other with the liquid crystal layer interposed therebetween. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and zinc oxide) may be used. The substrate of the electrode) is separated by a liquid crystal Layer-opposed structure. The structure of the latter can significantly increase the aperture ratio, and has the advantage of obtaining a bright and high-definition liquid crystal display element. In the latter configuration, the black matrix or the black spacer may be formed on one of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.

具備本發明的著色硬化膜的彩色液晶顯示元件除了具備冷陰極螢光管(CCFL：Cold Cathode Fluorescent Lamp)之外，還可具備以白色LED為光源的背光燈單元。作為白色LED，例如可舉出組合紅色LED、綠色LED和藍色LED，通過混色得到白色光的白色LED；組合藍色LED、紅色LED和綠色螢光體，通過混色得到白色光的白色LED；組合藍色LED、紅色發光螢光體和綠色發光螢光體，通過混色得到白色光的白色LED；通過藍色LED與YAG系螢光體的混色得到白色光的白色LED；組合藍色LED、橙色發光螢光體和綠色發光螢光體，通過混色得到白色光的白色LED；組合紫外線LED、紅色發光螢光體、綠色發光螢光體和藍色發光螢光體，通過混色得到白色光的白色LED等。 The color liquid crystal display device including the colored cured film of the present invention may further include a backlight unit having a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). Examples of the white LED include a white LED in which a combination of a red LED, a green LED, and a blue LED is obtained, and white light is obtained by color mixing; a blue LED, a red LED, and a green phosphor are combined, and a white LED is obtained by color mixing; Combining a blue LED, a red illuminating phosphor and a green illuminating phosphor, and obtaining a white LED of white light by color mixing; obtaining a white LED of white light by color mixing of the blue LED and the YAG-based phosphor; combining the blue LED, An orange-emitting phosphor and a green-emitting phosphor, a white LED obtained by color mixing; a combination of an ultraviolet LED, a red-emitting phosphor, a green-emitting phosphor, and a blue-emitting phosphor, and white light by color mixing White LED, etc.

具備本發明的著色硬化膜的彩色液晶顯示元件中，可應用TN(扭曲向列(Twisted Nematic))型、STN(超扭曲向列(Super Twisted Nematic))型、IPS(平面轉換(In-Planes Switching))型、VA(垂直取向(Vertical Alignment))型、OCB(光學補償彎曲排列(Optically Compensated Birefringence))型等適當的液晶模式。 In the color liquid crystal display device having the colored cured film of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes) can be applied. A suitable liquid crystal mode such as a switching type, a VA (Vertical Alignment) type, or an OCB (Optically Compensated Birefringence) type.

另外，具備本發明的著色硬化膜的有機EL顯 示元件可採用適當的結構，例如可舉出日本特開平11-307242號公報中公開的結構。 In addition, the organic EL display having the colored cured film of the present invention The display element may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be cited.

另外，具備本發明的著色硬化膜的電子紙可採用適當的結構，例如可舉出日本特開2007-41169號公報中公開的結構。 In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in JP-A-2007-41169 can be cited.

[固體攝像元件] [Solid image sensor]

本發明的固體攝像元件具備本發明的著色硬化膜。另外，本發明的固體攝像元件可採用適當的結構。例如，作為一個實施方式，使用本發明的著色組成物，採用與上述相同的操作在CMOS基板等半導體基板上形成著色像素(著色硬化膜)，由此能夠製成色彩分離性、色彩再現性優異的固體攝像元件。 The solid-state imaging device of the present invention comprises the colored cured film of the present invention. Further, the solid-state image sensor of the present invention can adopt an appropriate structure. For example, in one embodiment, by using the coloring composition of the present invention, a colored pixel (coloring cured film) is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above, whereby color separation property and color reproducibility are excellent. Solid-state imaging element.

[實施例] [Examples]

以下，舉出實施例，進一步具體說明本發明的實施方式。但是，本發明並不限定於下述實施例。 Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

<著色劑的合成> <Synthesis of Colorants>

(合成例1) (Synthesis Example 1)

對放入了攪拌子並安裝有回流冷卻管和溫度計的100mL的三口燒瓶充分進行氮置換，加入環己酮15.0g，在氮氣流下加熱至內溫80±2℃。以保持內溫在80±2℃的方式，使用泵用2小時向其中滴加混合下述式表示的色素單體(A1)4.50g、甲基丙烯酸甲酯6.00g、甲基丙烯酸4.50g、作為聚合起始劑的2,2'-偶氮雙(2,4-二甲基戊腈)(和光純藥工業股份有限公司製，商品名V-65)2.18g、環己酮45.0g而製備成的溶液。滴加結束後，在該溫度下進一步 繼續攪拌1小時。其後，將反應液冷卻至室溫，滴加到大量己烷中。在50℃對所得著色固體進行減壓乾燥，得到聚合物(1)14.1g。所得聚合物(1)的Mw為4800。聚合物(1)相當於聚合物α。 A 100 mL three-necked flask equipped with a stirrer and a reflux cooling tube and a thermometer was thoroughly purged with nitrogen, and 15.0 g of cyclohexanone was added thereto, and the mixture was heated to an internal temperature of 80 ± 2 ° C under a nitrogen stream. In order to maintain the internal temperature at 80 ± 2 ° C, 4.50 g of the dye monomer (A1), 6.00 g of methyl methacrylate, and 4.50 g of methacrylic acid represented by the following formula were added dropwise thereto using a pump for 2 hours. 2,2 ' -azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) 2.18 g and cyclohexanone 45.0 g as a polymerization initiator Prepared solution. After the completion of the dropwise addition, stirring was further continued at this temperature for 1 hour. Thereafter, the reaction liquid was cooled to room temperature and added dropwise to a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50 ° C to obtain 14.1 g of the polymer (1). The Mw of the obtained polymer (1) was 4,800. The polymer (1) corresponds to the polymer α.

合成例2~4 Synthesis Example 2~4

在合成例1中，按表1所示變更聚合所使用的單體的種類和量，除此之外，與合成例1同樣地得到聚合物(2) ~(4)。色素單體(A1)~(A4)的結構如上該。聚合物(2)相當於聚合物α，聚合物(3)~(4)相當於聚合物β。 In the synthesis example 1, the polymer (2) was obtained in the same manner as in the synthesis example 1 except that the type and amount of the monomer used for the polymerization were changed as shown in Table 1. ~(4). The structure of the dye monomers (A1) to (A4) is as described above. The polymer (2) corresponds to the polymer α, and the polymers (3) to (4) correspond to the polymer β.

表1中使用的符號如下。 The symbols used in Table 1 are as follows.

MMA：甲基丙烯酸甲酯 MMA: Methyl methacrylate

MA：甲基丙烯酸 MA: methacrylic acid

另外，色素單體(A1)~(A4)分別參考以下公報進行合成。 Further, the dye monomers (A1) to (A4) were each synthesized by referring to the following publication.

色素單體(A1)：依照日本特開2013-178478號公報的第[0145]~[0146]段中記載的合成例2進行合成。相當於單體α。 The dye monomer (A1) is synthesized in accordance with Synthesis Example 2 described in paragraphs [0145] to [0146] of JP-A-2013-178478. It is equivalent to monomer α.

色素單體(A2)：依照日本特開2013-173850號公報的第[0096]~[0097]段中記載的實施例1-1進行合成。相當於單體α。 The dye monomer (A2) was synthesized in accordance with Example 1-1 described in paragraphs [0096] to [0097] of JP-A-2013-173850. It is equivalent to monomer α.

色素單體(A3)：依照日本特開2013-210621號公報的第[0149]~[0150]段中記載的染料單體(A1-1)的製造進行合成。相當於單體β。 The dye monomer (A3) is synthesized in accordance with the production of the dye monomer (A1-1) described in paragraphs [0149] to [0150] of JP-A-2013-210621. It is equivalent to monomer β.

色素單體(A4)：日本特開2013-028764號公報的第[0501]段中記載的「單體1」。相當於單體β。 Pigment monomer (A4): "Monomer 1" described in paragraph [0501] of JP-A-2013-028764. It is equivalent to monomer β.

<著色劑溶液的製備> <Preparation of colorant solution>

製備例1 Preparation Example 1

使所得聚合物(1)10重量份溶解於丙二醇單甲醚90重量份中，製成著色劑溶液(A-1)。 10 parts by weight of the obtained polymer (1) was dissolved in 90 parts by weight of propylene glycol monomethyl ether to prepare a colorant solution (A-1).

製備例2~10 Preparation Example 2~10

在製備例1中，按表2所示變更溶質、溶劑的種類和量，除此之外，與製備例1同樣地製備著色劑溶液(A-2)~(A-10)。應予說明，在表2中，色素(A5)為C.I.鹼性藍7(三芳基甲烷化合物)，色素(A6)為下述式表示的蒽醌化合物。另外，丙二醇單甲醚記載為「PGME」。 In the preparation example 1, the colorant solutions (A-2) to (A-10) were prepared in the same manner as in Production Example 1, except that the type and amount of the solute and the solvent were changed as shown in Table 2. In Table 2, the dye (A5) is C.I. Basic Blue 7 (triarylmethane compound), and the dye (A6) is an anthracene compound represented by the following formula. Further, propylene glycol monomethyl ether is described as "PGME".

<黏結劑樹脂的合成> <Synthesis of binder resin>

合成例5 Synthesis Example 5

在具備冷卻管和攪拌機的燒瓶中加入丙二醇單甲醚乙酸酯100質量份，進行氮置換。加熱至80℃，在該溫度 下，用1小時滴加丙二醇單甲醚乙酸酯100質量份、甲基丙烯酸20質量份、苯乙烯10質量份、甲基丙烯酸苄酯5質量份、甲基丙烯酸2-羥基乙酯15質量份、甲基丙烯酸2-乙基己酯23質量份、N-苯基馬來醯亞胺12質量份、琥珀酸單(2-丙烯醯氧基乙基)酯15質量份和2,2'-偶氮雙(2,4-二甲基戊腈)6質量份的混合溶液，保持該溫度聚合2小時。其後，使反應溶液的溫度升溫至100℃，再聚合1小時，由此得到黏結劑樹脂溶液(固體成分濃度33質量%)。所得黏結劑樹脂的Mw為12200，Mn為6500。將該黏結劑樹脂作為「黏結劑樹脂(C1)」。 100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at this temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate and 15 parts by mass of 2,2 '- 6 parts by mass of azobis (2,4-dimethylvaleronitrile) mixed solution, maintaining the temperature polymerization for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had an Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "adhesive resin (C1)".

<著色組成物的製備和評價> <Preparation and evaluation of coloring composition>

[著色組成物的製備] [Preparation of coloring composition]

實施例1 Example 1

混合作為(A)著色劑的著色劑溶液(A-1)16.5質量份和著色劑溶液(A-3)1.0質量份、作為(C)黏結劑樹脂的黏結劑樹脂(C1)溶液23.3質量份、作為(B)聚合性化合物的二季戊四醇六丙烯酸酯與二季戊四醇五丙烯酸酯的混合物(日本化藥股份有限公司製，商品名KAYARAD DPHA)9.9質量份、作為光聚合起始劑的2-苄基-2-二甲基胺基-1-(4-啉代苯基)丁烷-1-酮(商品名IRGACURE 369，Ciba Specialty Chemicals公司製)1.8質量份和NCI-930(ADEKA股份有限公司製)0.1質量份、作為氟系表面活性劑的MEGAFAC F-554(DIC股份有限公司製)0.05質量份、以及作為溶劑的丙二醇單甲醚乙酸酯，製 備固體成分濃度20質量%的著色組成物(S-1)。 16.5 parts by mass of the coloring agent solution (A-1) as the coloring agent (A) and 1.0 part by mass of the colorant solution (A-3), and 23.3 parts by mass of the binder resin (C1) solution as the (C) binder resin a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a (B) polymerizable compound, 9.9 parts by mass, 2-benzyl as a photopolymerization initiator Benz-2-dimethylamino-1-(4- 1.8 parts by mass of phenyl phenyl)butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION), MEGAFAC F as a fluorine-based surfactant 0.05 parts by mass of 554 (manufactured by DIC Co., Ltd.) and propylene glycol monomethyl ether acetate as a solvent, and a coloring composition (S-1) having a solid concentration of 20% by mass was prepared.

[對比度的評價] [Evaluation of contrast]

使用旋塗機在玻璃基板上塗布所得著色組成物後，用80℃的熱板進行10分鐘預烘焙，形成膜厚2.5μm的塗膜。 The obtained colored composition was applied onto a glass substrate by a spin coater, and then prebaked for 10 minutes using a hot plate at 80 ° C to form a coating film having a film thickness of 2.5 μm.

接著，將該基板冷卻至室溫後，使用高壓汞燈不隔著光罩以2000J/m²的曝光量對各塗膜曝光包含365nm、405nm和436nm各波長的放射線。其後，以顯影壓1kgf/cm²(噴嘴直徑1mm)對該基板噴出23℃的由0.04質量%氫氧化鉀水溶液構成的顯影液90秒。然後，用超純水清洗該基板，風乾後，進一步在200℃的潔淨烘箱內進行30分鐘後烘焙，由此形成評價用硬化膜。 Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each coating film using a high pressure mercury lamp at an exposure amount of 2000 J/m ² without interposing a photomask. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a cured film for evaluation.

用2片偏振片夾住形成有硬化膜的基板，邊從背面側用螢光燈(波長範圍380~780nm)照射邊使前面側的偏振片旋轉，利用亮度計LS-100(Minolta股份有限公司製)測定透射的光強度的最大值和最小值。然後，將用最大值除以最小值得到的值作為對比度比。將評價結果示於表3。應予說明，數值越大，意味著對比度比越良好。 The substrate on which the cured film was formed was sandwiched between two polarizing plates, and the polarizing plate on the front side was rotated by a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, using a luminance meter LS-100 (Minolta Co., Ltd.) The maximum and minimum values of the transmitted light intensity are measured. Then, the value obtained by dividing the maximum value by the minimum value is taken as the contrast ratio. The evaluation results are shown in Table 3. It should be noted that the larger the value, the better the contrast ratio.

[耐熱性的評價] [Evaluation of heat resistance]

使用旋塗機在表面形成有防止鈉離子溶出的SiO₂膜的鈉玻璃基板上塗布著色組成物(S-1)後，用90℃的熱板進行2分鐘預烘焙，形成膜厚2.5μm的塗膜。 The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface thereof by a spin coater, and then prebaked for 2 minutes on a hot plate at 90 ° C to form a film thickness of 2.5 μm. Coating film.

接著，將該基板冷卻至室溫後，使用高壓汞燈隔著光罩以400J/m²的曝光量對各塗膜曝光包含365nm、405nm和436nm各波長的放射線。其後，以顯影壓1kgf/cm²(噴嘴直徑1mm)對這些基板噴出23℃的由0.04 質量%氫氧化鉀水溶液構成的顯影液，由此進行90秒噴淋顯影。其後，用超純水清洗該基板，風乾後，進一步在200℃的潔淨烘箱內進行30分鐘後烘焙，由此在基板上形成點圖案。 Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each coating film with a high pressure mercury lamp through a mask at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern on the substrate.

對所得點圖案，使用色彩分析儀(大塚電子股份有限公司製MCPD2000)，以C光源、2度視場測定CIE表色系中的色度坐標值(x，y)和刺激值(Y)。 The color point analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system using a C light source and a 2 degree field of view.

接著，將上述基板在230℃追加烘焙90分鐘後，測定色度坐標值(x，y)和刺激值(Y)，評價追加烘焙前後的顏色變化即△E^* _ab。其結果，將△E^* _ab的值小於3.0的情況評價為「○」，將3.0以上且小於5.0的情況評價為「△」，將5.0以上的情況評價為「×」。將評價結果示於表3。應予說明，可以說△E^* _ab值越小耐熱性越良好。 Next, the substrate was additionally baked at 230 ° C for 90 minutes, and then the chromaticity coordinate value (x, y) and the stimulating value (Y) were measured, and ΔE ^* _ab which is a color change before and after the additional baking was evaluated. As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "Δ", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. Incidentally, it can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

[顏色變化的評價] [Evaluation of color change]

使用旋塗機在表面形成有防止鈉離子溶出的SiO₂膜的鈉玻璃基板上塗布著色組成物(S-1)後，用90℃的熱板進行2分鐘預烘焙，形成膜厚2.5μm的塗膜。 The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface thereof by a spin coater, and then prebaked for 2 minutes on a hot plate at 90 ° C to form a film thickness of 2.5 μm. Coating film.

接著，將該基板冷卻至室溫後，使用高壓汞燈隔著光罩以400J/m²的曝光量對塗膜曝光包含365nm、405nm和436nm各波長的放射線。其後，以顯影壓1kgf/cm²(噴嘴直徑1mm)對該基板噴出23℃的由0.04質量%氫氧化鉀水溶液構成的顯影液，由此進行90秒噴淋顯影。其後，用超純水清洗該基板，風乾後，進一步在230℃的潔淨烘箱內進行30分鐘後烘焙，由此在基板上形成點圖案。 Next, after the substrate was cooled to room temperature, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm with a high pressure mercury lamp through a mask at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 ° C for 30 minutes to form a dot pattern on the substrate.

將上述基板在80℃的丙二醇單甲醚乙酸酯中浸漬40 分鐘。測定浸漬前後的色度坐標值(x，y)和刺激值(Y)，評價浸漬前後的顏色變化即△E^* _ab。其結果，將△E^* _ab的值小於3.0的情況評價為「○」，將3.0以上且小於5.0的情況評價為「△」，將5.0以上的情況評價為「×」。將評價結果示於表3。應予說明，可以說△E^* _ab值越小耐溶劑性越良好。 The above substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C for 40 minutes. The chromaticity coordinate value (x, y) and the stimulating value (Y) before and after the immersion were measured, and the color change before and after the immersion, ΔE ^* _ab , was evaluated. As a result, the case where the value of ΔE ^* _ab was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "Δ", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. In addition, it can be said that the smaller the ΔE ^* _ab value is, the better the solvent resistance is.

[對比度變化率的評價] [Evaluation of contrast change rate]

使用旋塗機在表面形成有防止鈉離子溶出的SiO₂膜的鈉玻璃基板上塗布著色組成物(S-1)後，用90℃的熱板進行2分鐘預烘焙，形成膜厚2.5μm的塗膜。 The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface thereof by a spin coater, and then prebaked for 2 minutes on a hot plate at 90 ° C to form a film thickness of 2.5 μm. Coating film.

接著，將該基板冷卻至室溫後，使用使用高壓汞燈不隔著光罩以400J/m²的曝光量對塗膜整面曝光包含365nm、405nm和436nm各波長的放射線。其後，以顯影壓1kgf/cm²(噴嘴直徑1mm)對這些基板噴出23℃的由0.04質量%氫氧化鉀水溶液構成的顯影液，由此進行90秒噴淋顯影。其後，用超純水清洗該基板，風乾後，進一步在230℃的潔淨烘箱內進行30分鐘後烘焙，由此在基板上形成著色硬化膜。將其作為基板(T-1)。 Next, after the substrate was cooled to room temperature, radiation including respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the entire surface of the coating film by using a high pressure mercury lamp at a exposure amount of 400 J/m ² without interposing a photomask. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 ° C for 30 minutes to form a colored cured film on the substrate. This was used as a substrate (T-1).

接下來，使用旋塗機在基板(T-1)上塗布根據日本專利第4697423號說明書的實施例1得到的含有聚有機矽氧烷、偏苯三酸酐、2-乙基-4-甲基咪唑和丙二醇單甲醚乙酸酯的保護膜形成用樹脂組成物。其後，用90℃的熱板進行5分鐘預烘焙，進一步在230℃的潔淨烘箱內後烘焙30分鐘，由此在著色硬化膜的上表面形成膜厚為2.0μm的保護膜。將所得基板作為基板(T-2)。 Next, a polyorganosiloxane, trimellitic anhydride, 2-ethyl-4-methylimidazole, and propylene glycol obtained in Example 1 according to the specification of Japanese Patent No. 4,694,423 were coated on a substrate (T-1) using a spin coater. A resin composition for forming a protective film of monomethyl ether acetate. Thereafter, the film was prebaked in a hot plate at 90 ° C for 5 minutes, and further baked in a clean oven at 230 ° C for 30 minutes to form a protective film having a film thickness of 2.0 μm on the upper surface of the colored cured film. The obtained substrate was used as a substrate (T-2).

採用與上述相同的方法分別測定基板(T-1)和基板(T-2)的對比度，由下述式求出對比度變化率。其結果，將對比度變化率小於15%的情況評價為「○」，將15%以上且小於30%的情況評價為「△」，將30%以上的情況評價為「×」。將評價結果示於表3。應予說明，可以說對比度變化率越小越良好。 The contrast between the substrate (T-1) and the substrate (T-2) was measured in the same manner as above, and the contrast change rate was obtained by the following formula. As a result, the case where the contrast change rate was less than 15% was evaluated as "○", the case where 15% or more and less than 30% was evaluated as "Δ", and the case where 30% or more was evaluated as "x". The evaluation results are shown in Table 3. Incidentally, it can be said that the smaller the contrast change rate, the better.

對比度變化率=((基板(T-2)的對比度)-(基板(T-1)的對比度))×100/(基板(T-1)的對比度) Contrast change rate = ((contrast of substrate (T-2)) - (contrast of substrate (T-1))) × 100 / (contrast of substrate (T-1))

實施例2~11和比較例1~6 Examples 2 to 11 and Comparative Examples 1 to 6

在實施例1中，按表3所示變更各成分的種類和量，除此之外，與實施例1同樣地製備著色組成物(S-2)~(S-17)。接著，使用著色組成物(S-2)~(S-17)代替著色組成物(S-1)，除此之外，與實施例1同樣地進行評價。將結果示於表3。 In the first embodiment, the colored compositions (S-2) to (S-17) were prepared in the same manner as in Example 1 except that the types and amounts of the respective components were changed as shown in Table 3. Next, evaluation was performed in the same manner as in Example 1 except that the coloring compositions (S-2) to (S-17) were used instead of the coloring composition (S-1). The results are shown in Table 3.

在表3中，「α/β」表示化合物群α中的發出螢光的部位與化合物群β中的吸收螢光的部位的莫耳比。 In Table 3, "α/β" indicates the molar ratio of the portion where the fluorescence is emitted in the compound group α and the portion where the fluorescence is absorbed in the compound group β.

Claims (8)

一種著色組成物，其係含有(A)著色劑和(B)聚合性化合物的著色組成物，其中(A)著色劑包含選自單體(α3)和聚合物(α4)中的至少1種與選自單體(β3)和聚合物(β4)中的至少1種的組合，該單體(α3)具有選自發色團和花青發色團中的至少1種發色團和聚合性基團，該聚合物(α4)含有該單體(α3)作為結構單元，該單體(β3)具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團和聚合性基團，該聚合物(β4)含有該單體(β3)作為結構單元，其中，不包括(A)著色劑為該單體(α3)與該單體(β3)的組合的情況。 A coloring composition comprising (A) a coloring agent and (B) a coloring composition of a polymerizable compound, wherein (A) the coloring agent comprises at least one selected from the group consisting of a monomer (α3) and a polymer (α4) In combination with at least one selected from the group consisting of a monomer (β3) and a polymer (β4), the monomer (α3) has a selected from At least one chromophore and a polymerizable group in the chromophore and the cyanine chromophore, the polymer (α4) containing the monomer (α3) as a structural unit, the monomer (β3) having a selected from the group consisting of At least one chromophore and a polymerizable group in the methacrylic chromophore and the chromophore, the polymer (β4) containing the monomer (β3) as a structural unit, wherein (A) coloring is not included The agent is a combination of the monomer (α3) and the monomer (β3). 如請求項1之的著色組成物，其中，該單體(β3)是具有選自三芳基甲烷發色團和蒽醌發色團中的至少1種發色團的烯性不飽和單體。 The coloring composition of claim 1, wherein the monomer (β3) is an ethylenically unsaturated monomer having at least one chromophore selected from the group consisting of a triarylmethane chromophore and a chromophore. 如請求項1之的樹脂組成物，其中，該單體(α3)是具有選自發色團和花青發色團中的至少1種發色團的烯性不飽和單體。 The resin composition of claim 1, wherein the monomer (α3) is selected from the group consisting of An olefinic unsaturated monomer of at least one chromophore of a chromophore and a cyanine chromophore. 如請求項1之的著色組成物，其中，(A)著色劑包含該聚合物(α4)與該單體(β3)的組合。 The colored composition of claim 1, wherein the (A) colorant comprises a combination of the polymer (α4) and the monomer (β3). 一種著色組成物，含有(A)著色劑和(B)聚合性化合物，(A)著色劑包含選自單體(α1)和聚合物(α2)中的至少1種與選自單體(β1)和聚合物(β2)中的至少1種的組合， 該單體(α1)具有發出螢光的部位和聚合性基團，該聚合物(α2)含有該單體(α1)作為結構單元，該單體(β1)具有吸收該螢光的部位和聚合性基團，該聚合物(β2)含有該單體(β1)作為結構單元，其中，不包括(A)著色劑為該單體(α1)與該單體(β1)的組合的情況。 A colored composition comprising (A) a colorant and (B) a polymerizable compound, (A) a colorant comprising at least one selected from the group consisting of a monomer (α1) and a polymer (α2) and a monomer selected from the group consisting of a monomer (β1) And a combination of at least one of the polymers (β2), The monomer (α1) has a fluorescent moiety and a polymerizable group, and the polymer (α2) contains the monomer (α1) as a structural unit, and the monomer (β1) has a site for absorbing the fluorescent light and polymerization. The polymer (β2) contains the monomer (β1) as a structural unit, and the case where the (A) colorant is not a combination of the monomer (α1) and the monomer (β1) is not included. 如請求項1~5中任一項之著色組成物，其中，進一步含有(C)黏結劑樹脂。 The colored composition according to any one of claims 1 to 5, further comprising (C) a binder resin. 一種著色硬化膜，是使用如請求項1~6中任一項之著色組成物而形成的。 A colored cured film formed by using the colored composition according to any one of claims 1 to 6. 一種顯示元件，具備如請求項7之著色硬化膜。 A display element comprising the colored cured film of claim 7.