TWI558692B - Colored curable composition, color filter and method of producing the same, and display apparatus - Google Patents

Colored curable composition, color filter and method of producing the same, and display apparatus Download PDF

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TWI558692B
TWI558692B TW101135352A TW101135352A TWI558692B TW I558692 B TWI558692 B TW I558692B TW 101135352 A TW101135352 A TW 101135352A TW 101135352 A TW101135352 A TW 101135352A TW I558692 B TWI558692 B TW I558692B
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TW201319039A (en
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片山晃男
兩角一真
八木一成
新居一巳
福重裕一
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富士軟片股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
    • C09B55/004—Monoazomethine dyes with the -C=N- group attached to an heteroring with the -C=N- group between two heterorings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Description

著色硬化性組成物、彩色濾光片、彩色濾光片的製造方法及顯示裝置 Colored curable composition, color filter, method for producing color filter, and display device

本發明是有關於一種包含染料作為著色化合物之著色硬化性組成物、彩色濾光片、彩色濾光片的製造方法及顯示裝置。 The present invention relates to a color hardening composition containing a dye as a coloring compound, a color filter, a method for producing a color filter, and a display device.

作為製作液晶顯示裝置或固體攝影元件等中所使用之彩色濾光片的方法之一，廣泛利用顏料分散法。顏料分散法存在有使用顏料分散於各種感光性組成物中而成之著色硬化性組成物，藉由光微影法而製作彩色濾光片之方法。該方法由於含有顏料而對光或熱穩定，且藉由光微影法而進行圖案化，因此充分確保位置精度，成為適於液晶顯示裝置、EL(electroluminescent，電致發光)顯示裝置等中所使用之彩色顯示器用彩色濾光片等之製作的方法。 As one of methods for producing a color filter used in a liquid crystal display device or a solid-state imaging device, a pigment dispersion method is widely used. In the pigment dispersion method, there is a method in which a color filter is formed by dispersing a pigment in various photosensitive compositions, and a color filter is produced by photolithography. Since this method is stable to light or heat by containing a pigment, and is patterned by photolithography, it is sufficiently suitable for liquid crystal display devices, EL (electroluminescent) devices, and the like. A method of producing a color filter or the like for a color display.

作為彩色濾光片之製作中所使用之著色化合物，不僅僅是顏料，亦廣泛研究了染料等顏料以外之色素化合物。其中，染料已知有具有吡咯亞甲基系染料、嘧啶偶氮系染料、吡唑偶氮系染料、二苯并哌喃系染料等各種各樣色素母體之化合物(例如參照日本專利特開2008-292970號公報、日本專利特開2007-039478號公報、及日本專利第3387541號公報)。其中，於日本專利特開2008-292970號公報中介紹了如下之技術：藉由併用多種染料，例如將吡咯亞甲基系染料與具有酞菁結構之染料併用而獲得高的色純度。 As a coloring compound used in the production of a color filter, not only a pigment but also a pigment compound other than a pigment such as a dye has been extensively studied. Among them, various dye precursors such as a pyrrolethymidine dye, a pyrimidine azo dye, a pyrazole azo dye, and a dibenzopyran dye are known as dyes (for example, refer to Japanese Patent Laid-Open Publication No. 2008). Japanese Patent Publication No. 2007-039478, Japanese Patent No. 2007-039478, and Japanese Patent No. 3,875,451. Among them, Japanese Patent Laid-Open Publication No. 2008-292970 discloses a technique in which a high color purity is obtained by using a plurality of dyes in combination, for example, a pyrromethylene-based dye and a dye having a phthalocyanine structure.

若使用染料作為著色化合物，則雖然於可由於染料自身之色純度或其色調之鮮豔度而提高影像顯示時之顯示影像之色調或亮度之方面而言有用，然而現狀是於使用染料之彩色濾光片之影像特性中尚且存在改良之餘地，且於對比度、亮度性能中要求更進一步之改良。 When a dye is used as the coloring compound, it is useful in terms of improving the color tone or brightness of the display image at the time of image display due to the color purity of the dye itself or the vividness of the color tone thereof, but the current state is the color filter using the dye. There is still room for improvement in the image characteristics of the light sheet, and further improvement is required in contrast and brightness performance.

本發明是鑒於上述之先前技術而成者。亦即，本發明之一個態樣之課題在於提供使亮度提高、獲得高的對比度的用以形成彩色濾光片之著色圖案的著色硬化性組成物。 The present invention has been made in view of the above prior art. That is, an object of one aspect of the present invention is to provide a color-curable composition for forming a color pattern of a color filter which improves brightness and obtains high contrast.

而且，本發明之其他態樣之課題在於提供使用所述本發明的著色硬化性組成物而能夠以高亮度顯示對比度高的影像的彩色濾光片、及其製造方法、以及使用該彩色濾光片而成的可進行良好畫質之顯示的顯示裝置。 Further, another object of the present invention is to provide a color filter capable of displaying a high-contrast image with high luminance by using the colored curable composition of the present invention, a method for producing the same, and a color filter using the color filter. A display device that can display a good image quality.

本發明者等人為了達成所述課題而進行銳意研究，結果發現藉由將吡咯亞甲基系染料與特定染料組合，可同時實現非常高的亮度與高的對比度，從而完成本發明。 The inventors of the present invention conducted intensive studies to achieve the above problems, and as a result, it has been found that by combining a pyrromethene dye with a specific dye, it is possible to achieve very high brightness and high contrast at the same time, and the present invention has been completed.

本發明之具體態樣如下所述。 Specific aspects of the invention are as follows.

<1>一種著色硬化性組成物，其含有：選自由(A-1)下述通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲基(dipyrromethene)金屬錯合物化合物及(A-2)下述通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基(azapyrromethene)金屬錯合物化合物所構成之群組的1種以上的色素化合物、(B)下述通式(III)所表示之卟啉(porphyrin)化合物。 <1> A colored curable composition comprising: a dipyrromethene metal selected from the group consisting of (A-1) a structure represented by the following formula (I) and a metal or a metal compound; a complex compound and (A-2) a group of azapyyrromethene metal complex compounds in which the structure represented by the following formula (II) is bonded to a metal or a metal compound. One or more kinds of pigment compounds and (B) a porphyrin compound represented by the following formula (III).

所述通式(I)中，R1、R2、R3、R4、R5、及R6各自獨立地表示氫原子或1價取代基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基。 In the above formula (I), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a monovalent substituent, and R 7 represents a hydrogen atom, a halogen atom or an alkyl group. , aryl, or heterocyclic group.

所述通式(II)中，R21、R22、R23、R24、R25及R26各自獨立地表示氫原子或1價取代基。 In the above formula (II), R 21 , R 22 , R 23 , R 24 , R 25 and R 26 each independently represent a hydrogen atom or a monovalent substituent.

[化3] [Chemical 3]

所述通式(III)中，Z1、Z2、Z3及Z4均表示N，或者Z1及Z3、以及Z2及Z4之任意一組之雙方均表示N，另一組表示C-R，R分別獨立地表示氫原子、烷基、或芳基。A1、A2、A3、A4、A5、A6、A7及A8各自獨立地表示烷基、烯基、芳基、烷氧基、烷硫基、芳氧基、芳硫基、鹵素原子、羥基、烷氧基羰基、芳氧基羰基、胺基、胺甲醯基、胺磺醯基、醯基、矽烷氧基、氰基、硝基、或雜環基。A1與A2、A3與A4、A5與A6、或A7與A8亦可各自相互鍵結而形成環結構，但該些中的至少一組並不形成環結構。M表示2價金屬原子、或經取代之2價金屬原子或包含金屬原子之2價原子團。 In the general formula (III), Z 1 , Z 2 , Z 3 and Z 4 each represent N, or Z 1 and Z 3 , and any one of Z 2 and Z 4 represents N, and the other group Represents CR, and R independently represents a hydrogen atom, an alkyl group, or an aryl group. A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 each independently represent an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, or an aromatic sulfur. a group, a halogen atom, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine group, an aminecarbamyl group, an aminesulfonyl group, a decyl group, a decyloxy group, a cyano group, a nitro group, or a heterocyclic group. A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , or A 7 and A 8 may each be bonded to each other to form a ring structure, but at least one of the groups does not form a ring structure. M represents a divalent metal atom, or a substituted divalent metal atom or a divalent atomic group containing a metal atom.

<2>如<1>所述之著色硬化性組成物，其中所述(B)通式(III)所表示之卟啉化合物是下述通式(III-2)所表示之卟啉化合物。 <2> The colored curable composition according to the above (1), wherein the porphyrin compound represented by the formula (III) is a porphyrin compound represented by the following formula (III-2).

[化4] [Chemical 4]

所述通式(III-2)中，A1、A2、A3、A4、A5、A6、A7、A8及M與通式(III)中之A1、A2、A3、A4、A5、A6、A7、A8及M各自同義。 In the above formula (III-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M and A 1 and A 2 in the formula (III), A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are each synonymous.

<3>如<1>或<2>所述之著色硬化性組成物，其更含有(C)聚合性化合物及(D)光聚合起始劑，且為感光性。 <3> The colored curable composition according to <1> or <2> which further contains (C) a polymerizable compound and (D) a photopolymerization initiator, and is photosensitive.

<4>如<1>~<3>中任一項所述之著色硬化性組成物，其中相對於著色硬化性組成物中所含之著色化合物之總量而言，所述(B)通式(III)所表示之卟啉化合物之含量為0.1質量%以上50質量%以下。 The colored hardening composition according to any one of <1> to <3> wherein the (B) pass is relative to the total amount of the coloring compound contained in the colored curable composition. The content of the porphyrin compound represented by the formula (III) is 0.1% by mass or more and 50% by mass or less.

<5>如<1>~<4>中任一項所述之著色硬化性組成物，其中所述(B)通式(III)所表示之卟啉化合物是通式(III)中之A1與A2、A3與A4、A5與A6、及A7與A8之組的任意者均未形成環結構之化合物。 The colored hardening composition according to any one of <1> to <4> wherein the porphyrin compound represented by the formula (III) is A in the formula (III) A compound having no ring structure formed by any of 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 .

<6>如<1>~<5>中任一項所述之著色硬化性組成物，其中相對於所述著色硬化性組成物之總固形物而 言，包含所述(A-1)通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲基金屬錯合物化合物、所述(A-2)通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基金屬錯合物化合物及所述(B)通式(III)所表示之卟啉化合物的著色化合物的總含量為0.2質量%以上50質量%以下。 The colored hardening composition according to any one of <1> to <5>, wherein the total solid matter of the colored curable composition is In the above, (A-1) a dipyrromethene metal complex compound obtained by disposing the structure represented by the formula (I) on a metal or a metal compound, the (A-2) formula ( II) The total content of the azapyrromethene metal complex compound in which the structure is represented by a metal or a metal compound and the coloring compound of the (B) porphyrin compound represented by the formula (III) It is 0.2% by mass or more and 50% by mass or less.

<7>一種彩色濾光片，其是使用如<1>~<6>中任一項所述之著色硬化性組成物而成者。 <7> A color filter comprising the color hardening composition according to any one of <1> to <6>.

<8>一種彩色濾光片的製造方法，其包含：著色層形成步驟，將如<1>~<6>中任一項所述之著色硬化性組成物賦予至支撐體上而形成著色層；曝光步驟，將所形成之著色層曝光為圖案模樣；顯影步驟，對曝光後之著色層進行顯影而形成著色圖案。 (8) A method of producing a color filter, comprising: a colored layer forming step, wherein the colored curable composition according to any one of <1> to <6> is applied to a support to form a colored layer And an exposure step of exposing the formed color layer to a pattern; and developing a step of developing the exposed color layer to form a colored pattern.

<9>一種顯示裝置，其包含如<7>所述之彩色濾光片或者藉由如<8>所述之製造方法而得之彩色濾光片。 <9> A display device comprising the color filter according to <7> or a color filter obtained by the manufacturing method according to <8>.

藉由本發明之一個態樣，可提供使亮度提高、獲得高的對比度的用以形成彩色濾光片之著色圖案的著色硬化性組成物。 According to an aspect of the present invention, it is possible to provide a color hardening composition for forming a coloring pattern of a color filter which improves brightness and obtains high contrast.

而且，藉由本發明之其他態樣，可提供使用所述本發明的著色硬化性組成物的能夠以高亮度顯示對比度高的影像的彩色濾光片、及其製造方法、以及使用該彩色濾光片而成的可進行良好畫質之顯示的顯示裝置。 Further, according to another aspect of the present invention, it is possible to provide a color filter capable of displaying a high-contrast image with high luminance using the color hardening composition of the present invention, a method for producing the same, and a color filter using the color filter A display device that can display a good image quality.

以下，對本發明之著色硬化性組成物加以詳細說明， 且對使用該著色硬化性組成物的本發明之彩色濾光片及其製造方法、以及顯示裝置加以詳細說明。 Hereinafter, the color hardening composition of the present invention will be described in detail. Further, the color filter of the present invention using the colored curable composition, a method for producing the same, and a display device will be described in detail.

著色硬化性組成物 Colored hardening composition

本發明之著色硬化性組成物是至少含有以下所示的選自(A-1)下述通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲基金屬錯合物化合物及(A-2)下述通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基金屬錯合物化合物的1種以上的色素化合物、(B)下述通式(III)所表示之卟啉化合物作為著色化合物的組成物，較佳的是進一步含有(C)聚合性化合物及(D)光聚合起始劑，具有感光性之硬化性組成物。 The color hardening composition of the present invention contains at least a dipyrromethene metal which is selected from the group consisting of (A-1) represented by the following formula (I) and which is bonded to a metal or a metal compound. (A-2) one or more dye compounds of the azapyrrolidinium metal complex compound in which the structure represented by the following formula (II) is bonded to a metal or a metal compound, ( B) The porphyrin compound represented by the following formula (III), as a composition of the coloring compound, preferably further contains (C) a polymerizable compound and (D) a photopolymerization initiator, and has photosensitive curability. Composition.

只要不損及本發明之效果，則本發明之著色硬化性組成物亦可視需要進一步含有鹼可溶性樹脂等黏合樹脂、有機溶劑、及各種添加劑。 The colored curable composition of the present invention may further contain a binder resin such as an alkali-soluble resin, an organic solvent, and various additives as needed, as long as the effects of the present invention are not impaired.

以下，對構成本發明之著色硬化性組成物的各成分加以詳細說明。另外，於以下中，有時將本發明之著色硬化性組成物簡稱為「本發明之著色組成物」或「著色組成物」。 Hereinafter, each component constituting the colored curable composition of the present invention will be described in detail. In addition, in the following, the color hardening composition of the present invention may be simply referred to as "coloring composition of the present invention" or "coloring composition".

另外，於本說明書中，使用「~」而表示的數值範圍表示包含「~」之前後所記載的數值作為下限值及上限值的範圍。而且，作為組成物中之各成分之量，於組成物中存在多種與各成分相當之物質之情形時，只要無特別說明，則表示組成物中所存在的該多種物質的合計量。 In addition, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Further, when a plurality of substances corresponding to the respective components are present in the composition as the amount of each component in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is indicated.

於本說明書中，「烷基」是「直鏈、分支及環狀」之烷 基之總稱。而且，本說明書中之取代基(原子團)以包含未經取代者及進一步具有取代基者之含義而使用。亦即，於本說明書中，所謂「烷基」以包含未經取代之烷基及經取代之烷基之含義而使用，其他取代基亦同樣。 In the present specification, "alkyl" is a "linear, branched and cyclic" alkane. The general name of the base. Moreover, the substituent (atomic group) in the present specification is used in the meaning of including an unsubstituted person and a further substituent. That is, in the present specification, the "alkyl group" is used in the meaning of an unsubstituted alkyl group and a substituted alkyl group, and the other substituents are also the same.

本發明之著色硬化性組成物含有選自(A-1)下述通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲基金屬錯合物化合物及(A-2)下述通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基金屬錯合物化合物的1種以上的色素化合物。以下，順次對該色素化合物加以說明。 The color hardening composition of the present invention contains a dipyrromethene metal complex compound (A) selected from the group consisting of (A-1) having a structure represented by the following formula (I), which is bonded to a metal or a metal compound, and (A) -2) One or more kinds of dye compounds of the azapyrrole methylene metal complex compound in which the structure represented by the following formula (II) is bonded to a metal or a metal compound. Hereinafter, the dye compound will be described in order.

(A-1)通式(I)所表示之結構配位於金屬或金屬化合物上而成的金屬錯合物化合物 (A-1) A metal complex compound in which the structure represented by the formula (I) is bonded to a metal or a metal compound

首先，對通式(I)所表示之結構配位於金屬或金屬化合物上而成之二吡咯亞甲基金屬錯合物化合物(以下適宜稱為「二吡咯亞甲基金屬錯合物化合物」或「特定染料(A-1)」)加以說明。 First, a dipyrromethene metal complex compound obtained by disposing a structure represented by the formula (I) on a metal or a metal compound (hereinafter referred to as "dipyrromethene metal complex compound" or "Specific dye (A-1)") will be described.

所述通式(I)中，R1、R2、R3、R4、R5、及R6各自 獨立地表示氫原子或1價取代基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基。 In the above formula (I), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or a monovalent substituent, and R 7 represents a hydrogen atom, a halogen atom or an alkyl group. , aryl, or heterocyclic group.

通式(I)中，R1~R6所各自表示之1價取代基可列舉鹵素原子(例如可列舉氟原子、氯原子、溴原子)、烷基(較佳的是碳數為1~48之直鏈、分支鏈、或環狀之烷基，更佳的是碳數為1~24之直鏈、分支鏈、或環狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基、庚基、辛基、2-乙基己基、十二烷基、十六烷基、環丙基、環戊基、環己基、1-降莰基、及1-金剛烷基)、烯基(較佳的是碳數為2~48之烯基，更佳的是碳數為2~18之烯基，例如可列舉乙烯基、烯丙基、及3-丁烯-1-基)、芳基(較佳的是碳數為6~48之芳基，更佳的是碳數為6~24之芳基，例如可列舉苯基、及萘基)、雜環基(較佳的是碳數為1~32之雜環基，更佳的是碳數為1~18之雜環基，例如可列舉2-噻吩基、4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、及苯并***-1-基)、矽烷基(較佳的是碳數為3~38之矽烷基，更佳的是碳數為3~18之矽烷基，例如可列舉三甲基矽烷基、三乙基矽烷基、三丁基矽烷基、第三丁基二甲基矽烷基、及第三己基二甲基矽烷基)、羥基、氰基、硝基、烷氧基(較佳的是碳數為1~48之烷氧基，更佳的是碳數為1~24之烷氧基，例如可列舉甲氧基、乙氧基、1-丁氧基、2-丁氧基、異丙氧基、第三丁氧基、及十二烷氧基、以及例如環戊氧基、或環己氧基等環烷氧基)、 芳氧基(較佳的是碳數為6~48之芳氧基，更佳的是碳數為6~24之芳氧基，例如可列舉苯氧基、及1-萘氧基)、雜環氧基(較佳的是碳數為1~32之雜環氧基，更佳的是碳數為1~18之雜環氧基，例如可列舉1-苯基四唑-5-氧基、及2-四氫吡喃基氧基)、矽烷氧基(較佳的是碳數為1~32之矽烷氧基，更佳的是碳數為1~18之矽烷氧基，例如可列舉三甲基矽烷基氧基、第三丁基二甲基矽烷氧基、及二苯基甲基矽烷氧基)、醯氧基(較佳的是碳數為2~48之醯氧基，更佳的是碳數為2~24之醯氧基，例如可列舉乙醯氧基、特戊醯氧基、苯甲醯氧基、及十二醯氧基)、烷氧基羰氧基(較佳的是碳數為2~48之烷氧基羰氧基，更佳的是碳數為2~24之烷氧基羰氧基，例如可列舉乙氧基羰氧基、及第三丁氧基羰氧基、以及例如環己氧基羰氧基等環烷氧基羰氧基)、芳氧基羰氧基(較佳的是碳數為7~32之芳氧基羰氧基，更佳的是碳數為7~24之芳氧基羰氧基，例如可列舉苯氧基羰氧基)、胺甲醯基氧基(較佳的是碳數為1~48之胺甲醯基氧基，更佳的是碳數為1~24之胺甲醯基氧基，例如可列舉N,N-二甲基胺甲醯基氧基、N-丁基胺甲醯基氧基、N-苯基胺甲醯基氧基、及N-乙基-N-苯基胺甲醯基氧基)、胺磺醯基氧基(較佳的是碳數為1~32之胺磺醯基氧基，更佳的是碳數為1~24之胺磺醯基氧基，例如可列舉N,N-二乙基胺磺醯基氧基、及N-丙基胺磺醯基氧基)、烷基磺醯氧基(較佳的是碳數為1~38之烷基磺醯氧 基，更佳的是碳數為1~24之烷基磺醯氧基，例如可列舉甲基磺醯氧基、十六烷基磺醯氧基、及環己基磺醯氧基)、芳基磺醯氧基(較佳的是碳數為6~32之芳基磺醯氧基，更佳的是碳數為6~24之芳基磺醯氧基，例如可列舉苯基磺醯氧基)、醯基(較佳的是碳數為1~48之醯基，更佳的是碳數為1~24之醯基，例如可列舉甲醯基、乙醯基、特戊醯基、苯甲醯基、十四醯基、及環己醯基)、烷氧基羰基(較佳的是碳數為2~48之烷氧基羰基，更佳的是碳數為2~24之烷氧基羰基，例如可列舉甲氧基羰基、乙氧基羰基、十八烷氧基羰基、環己氧基羰基、及2,6-二-第三丁基-4-甲基環己氧基羰基)、芳氧基羰基(較佳的是碳數為7~32之芳氧基羰基，更佳的是碳數為7~24之芳氧基羰基，例如可列舉苯氧基羰基)、胺甲醯基(較佳的是碳數為1~48之胺甲醯基，更佳的是碳數為1~24之胺甲醯基，例如可列舉胺甲醯基、N,N-二乙基胺甲醯基、N-乙基-N-辛基胺甲醯基、N,N-二丁基胺甲醯基、N-丙基胺甲醯基、N-苯基胺甲醯基、N-甲基-N-苯基胺甲醯基、及N,N-二環己基胺甲醯基)、胺基(較佳的是碳數為32以下之胺基，更佳的是碳數為24以下之胺基，例如可列舉胺基、甲基胺基、N,N-二丁基胺基、十四烷基胺基、2-乙基己基胺基、及環己基胺基)、苯胺基(較佳的是碳數為6~32之苯胺基，更佳的是6~24之苯胺基，例如可列舉苯胺基、及N-甲基苯胺基)、雜環胺基(較佳的是碳數為1~32之雜環胺基，更佳的是 1~18之雜環胺基，例如可列舉4-吡啶基胺基)、羧醯胺基(較佳的是碳數為2~48之羧醯胺基，更佳的是2~24之羧醯胺基，例如可列舉乙醯胺基、苯甲醯胺基、十四烷基醯胺基、特戊醯基醯胺基、及環己基醯胺基)、脲基(較佳的是碳數為1~32之脲基，更佳的是碳數為1~24之脲基，例如可列舉脲基、N,N-二甲基脲基、及N-苯基脲基)、醯亞胺基(較佳的是碳數為36以下之醯亞胺基，更佳的是碳數為24以下之醯亞胺基，例如可列舉N-琥珀醯亞胺基及N-鄰苯二甲醯亞胺基)、烷氧基羰基胺基(較佳的是碳數為2~48之烷氧基羰基胺基，更佳的是碳數為2~24之烷氧基羰基胺基，例如可列舉甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、十八烷氧基羰基胺基、及環己氧基羰基胺基)、芳氧基羰基胺基(較佳的是碳數為7~32之芳氧基羰基胺基，更佳的是碳數為7~24之芳氧基羰基胺基，例如可列舉苯氧基羰基胺基)、磺醯胺基(較佳的是碳數為1~48之磺醯胺基，更佳的是碳數為1~24之磺醯胺基，例如可列舉甲基磺醯胺基、丁基磺醯胺基、苯磺醯胺基、十六烷基磺醯胺基、及環己基磺醯胺基)、胺磺醯胺基(較佳的是碳數為1~48之胺磺醯胺基，更佳的是碳數為1~24之胺磺醯胺基，例如可列舉N,N-二丙基胺磺醯胺基、及N-乙基-N-十二烷基胺磺醯胺基)、偶氮基(較佳的是碳數為1~32之偶氮基，更佳的是碳數為1~24之偶氮基，例如可列舉苯基偶氮基、及3-吡唑基偶氮基)、烷硫基(較佳 的是碳數為1~48之烷硫基，更佳的是碳數為1~24之烷硫基，例如可列舉甲硫基、乙硫基、辛硫基、及環己硫基)、芳硫基(較佳的是碳數為6~48之芳硫基，更佳的是碳數為6~24之芳硫基，例如可列舉苯硫基)、雜環硫基(較佳的是碳數為1~32之雜環硫基，更佳的是碳數為1~18之雜環硫基，例如可列舉2-苯并噻唑基硫基、2-吡啶基硫基、及1-苯基四唑基硫基)、烷基亞磺醯基(較佳的是碳數為1~32之烷基亞磺醯基，更佳的是碳數為1~24之烷基亞磺醯基，例如可列舉十二烷基亞磺醯基)、芳基亞磺醯基(較佳的是碳數為6~32之芳基亞磺醯基，更佳的是碳數為6~24之芳基亞磺醯基，例如可列舉苯基亞磺醯基)、烷基磺醯基(較佳的是碳數為1~48之烷基磺醯基，更佳的是碳數為1~24之烷基磺醯基，例如可列舉甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、異丙基磺醯基、2-乙基己基磺醯基、十六烷基磺醯基、辛基磺醯基、及環己基磺醯基)、芳基磺醯基(較佳的是碳數為6~48之芳基磺醯基，更佳的是碳數為6~24之芳基磺醯基，例如可列舉苯基磺醯基、及1-萘基磺醯基)、胺磺醯基(較佳的是碳數為32以下之胺磺醯基，更佳的是碳數為24以下之胺磺醯基，例如可列舉胺磺醯基、N,N-二丙基胺磺醯基、N-乙基-N-十二烷基胺磺醯基、N-乙基-N-苯基胺磺醯基、及N-環己基胺磺醯基)、磺基、膦醯基(較佳的是碳數為1~32之膦醯基，更佳的是碳數為1~24之膦醯基，例如可列舉苯氧基膦醯基、辛氧基膦醯基、及苯基膦醯基)、膦醯基胺 基(較佳的是碳數為1~32之膦醯基胺基，更佳的是碳數為1~24之膦醯基胺基，例如可列舉二乙氧基膦醯基胺基、及二辛氧基膦醯基胺基)。以下，有時將該些取代基稱為「取代基R」。 In the general formula (I), the monovalent substituent represented by each of R 1 to R 6 may, for example, be a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group (preferably, the carbon number is 1~). a straight chain, a branched chain, or a cyclic alkyl group of 48, more preferably a linear, branched, or cyclic alkyl group having a carbon number of 1 to 24, and examples thereof include a methyl group, an ethyl group, and a propyl group. , isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl , 1-norbornyl, and 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, for example, ethylene a group, an allyl group, and a 3-buten-1-yl group, an aryl group (preferably an aryl group having a carbon number of 6 to 48, more preferably an aryl group having a carbon number of 6 to 24, for example, The phenyl group and the naphthyl group and the heterocyclic group are preferred (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, and examples thereof include 2-thienyl group. , 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, and benzo Zyridin-1-yl), decylalkyl (preferably a decyl group having a carbon number of 3 to 38, more preferably a decyl group having a carbon number of 3 to 18, and examples thereof include a trimethyldecyl group and a triethyl group. a decyl group, a tributyl decyl group, a tert-butyldimethyl decyl group, and a third hexyl dimethyl decyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably having a carbon number of 1) Alkoxy group of ~48, more preferably an alkoxy group having 1 to 24 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, and the like. a third butoxy group, a dodecyloxy group, and a cycloalkoxy group such as a cyclopentyloxy group or a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having a carbon number of 6 to 48) More preferably, it is an aryloxy group having a carbon number of 6 to 24, and examples thereof include a phenoxy group and a 1-naphthyloxy group, and a heterocyclic oxy group (preferably a hetero epoxide having a carbon number of 1 to 32). More preferably, it is a heterocyclic oxy group having 1 to 18 carbon atoms, and examples thereof include 1-phenyltetrazole-5-oxy group and 2-tetrahydropyranyloxy group, and decyloxy group. Preferred is a decyloxy group having a carbon number of from 1 to 32, more preferably a decyloxy group having a carbon number of from 1 to 18, and examples thereof include a trimethyldecyloxy group. Tributyl dimethyl decyloxy, and diphenylmethyl decyloxy), decyloxy (preferably a decyloxy group having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24) Examples of the methoxy group include an ethoxycarbonyl group, a p-pentyloxy group, a benzamethyleneoxy group, and a dodecyloxy group, and an alkoxycarbonyloxy group (preferably, the carbon number is 2 to 48). The alkoxycarbonyloxy group is more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, and examples thereof include an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and, for example, a cyclohexane. a cycloalkoxycarbonyloxy group such as an oxycarbonyloxy group, or an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24) The aryloxycarbonyloxy group may, for example, be a phenoxycarbonyloxy group or an amine mercaptooxy group (preferably an aminomethylcarbonyl group having a carbon number of 1 to 48, more preferably a carbon number). Examples of the amine mercaptooxy group of 1 to 24 include N,N-dimethylamine-methylcarbonyloxy group, N-butylamine-methylcarbonyloxy group, and N-phenylamine-methyl fluorenyloxy group. And N-ethyl-N-phenylamine-mercaptooxy), sulfonyloxy (preferably sulfonyloxy having 1 to 32 carbon atoms, more preferably carbon number) For 1 Examples of the aminesulfonyloxy group of ~24 include N,N-diethylaminesulfonyloxy, and N-propylaminesulfonyloxy), alkylsulfonyloxy (preferred) It is an alkylsulfonyloxy group having a carbon number of 1 to 38, more preferably an alkylsulfonyloxy group having a carbon number of 1 to 24, and examples thereof include a methylsulfonyloxy group and a hexadecylsulfonyloxy group. a group, and a cyclohexylsulfonyloxy group, an arylsulfonyloxy group (preferably an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably an arylsulfonyl group having a carbon number of 6 to 24) Examples of the decyloxy group include a phenylsulfonyloxy group and a fluorenyl group (preferably a fluorenyl group having a carbon number of 1 to 48, more preferably a fluorenyl group having a carbon number of 1 to 24, and for example, a An alkoxycarbonyl group having a carbon number of 2 to 48, an alkoxycarbonyl group having a carbon number of 2 to 48, an alkoxycarbonyl group, preferably an alkyloxy group having a carbon number of 2 to 48, More preferably, it is an alkoxycarbonyl group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a 2,6-di- Tributyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24) The aryloxycarbonyl group may, for example, be a phenoxycarbonyl group or an amine formamidine group (preferably an aminocarbenyl group having a carbon number of 1 to 48, more preferably an amine formazan having a carbon number of 1 to 24). Examples of the group include an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, an N-ethyl-N-octylamine methyl fluorenyl group, an N,N-dibutylamine carbhydryl group, and an N- Propylamine methyl sulfonyl, N-phenylamine methyl sulfhydryl, N-methyl-N-phenylamine methyl sulfhydryl, and N,N-dicyclohexylamine carbhydryl), amine group (preferred It is an amine group having a carbon number of 32 or less, more preferably an amine group having a carbon number of 24 or less, and examples thereof include an amine group, a methylamino group, an N,N-dibutylamino group, and a tetradecylamino group. , 2-ethylhexylamino group, and cyclohexylamino group), anilino group (preferably an anilino group having a carbon number of 6 to 32, more preferably an anilino group of 6 to 24, and examples thereof include an anilino group, And N-methylanilino), a heterocyclic amine group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably a heterocyclic amino group of 1 to 18, and examples thereof include 4-pyridyl group Amino), carboxylamido group (preferably a carboguanamine group having a carbon number of 2 to 48, more preferably a carboxamide group of 2 to 24, and examples thereof include an ethenamine group and a benzamide Base, ten a tetraalkylammonium group, a pentylene sulfonylamino group, and a cyclohexylguanidinium group, a urea group (preferably a ureido group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24) Examples of the ureido group include a ureido group, an N,N-dimethylureido group, and an N-phenylureido group, and a quinone imine group (preferably a ruthenium group having a carbon number of 36 or less, more Preferred are quinone imine groups having a carbon number of 24 or less, and examples thereof include N-succinimide group and N-phthalimido group, and alkoxycarbonylamino group (preferably carbon number). The alkoxycarbonylamino group of 2 to 48 is more preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, and a third group. An oxycarbonylamino group, an octadecyloxycarbonylamino group, and a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having a carbon number of 7 to 32, More preferably, it is an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group, a sulfonylamino group (preferably a sulfonylamino group having 1 to 48 carbon atoms). More preferred are sulfonamide groups having a carbon number of 1 to 24, and examples thereof include methylsulfonylamino group, butylsulfonylamino group, and benzene. An amidino group, a hexadecylsulfonylamino group, and a cyclohexylsulfonylamino group, an aminesulfonylamino group (preferably a sulfonamide group having a carbon number of 1 to 48, more preferably a carbon) The sulfonamide group having a number of 1 to 24, for example, N,N-dipropylamine sulfonamide, and N-ethyl-N-dodecylamine sulfonamide, and azo group (A preferred is an azo group having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, and examples thereof include a phenylazo group and a 3-pyrazolylazo group) And an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, and an octylthio group. And cyclohexylthio), arylthio (preferably an arylthio group having a carbon number of 6 to 48, more preferably an arylthio group having a carbon number of 6 to 24, for example, a phenylthio group), An episulfide group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, and examples thereof include a 2-benzothiazolylthio group, 2 a pyridylthio group, and a 1-phenyltetrazolylthio group, an alkylsulfinyl group (preferably an alkylsulfinyl group having a carbon number of 1 to 32, more preferably a carbon number of 1) ~24 alkyl sulfinyl For example, a dodecylsulfinyl group, an arylsulfinyl group (preferably an arylsulfinylene group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24) The sulfinyl group may, for example, be a phenylsulfinyl group or an alkylsulfonyl group (preferably an alkylsulfonyl group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24). Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, and a 2-ethylhexylsulfonyl group. a hexadecylsulfonyl group, an octylsulfonyl group, and a cyclohexylsulfonyl group, an arylsulfonyl group (preferably an arylsulfonyl group having a carbon number of 6 to 48, more preferably a carbon) The arylsulfonyl group having a number of 6 to 24, for example, a phenylsulfonyl group and a 1-naphthylsulfonyl group, an aminesulfonyl group (preferably an aminesulfonyl group having a carbon number of 32 or less) More preferably, it is a sulfonyl group having a carbon number of 24 or less, and examples thereof include an amine sulfonyl group, an N,N-dipropylamine sulfonyl group, and an N-ethyl-N-dodecylamine sulfonate. a group, a N-ethyl-N-phenylamine sulfonyl group, and an N-cyclohexylamine sulfonyl group, a sulfo group, a phosphinium group (preferably a phosphino group having a carbon number of 1 to 32, more Preferred are a phosphonium group having a carbon number of 1 to 24, and examples thereof include a phenoxyphosphonium group, an octyloxyphosphonium group, and a phenylphosphinium group, and a phosphinium group (preferably a carbon). The number is a phosphinylamino group of 1 to 32, more preferably a phosphinylamino group having a carbon number of 1 to 24, and examples thereof include a diethoxyphosphinylamino group and a dioctyloxyphosphonium group. Amine). Hereinafter, these substituents may be referred to as "substituent R".

上述1價取代基為可進一步被取代之基之情形時，亦可被上述各基之任意者所進一步取代。另外，於上述1價取代基具有2個以上進一步之取代基之情形時，該些取代基可相同亦可不同。 When the above monovalent substituent is a group which may be further substituted, it may be further substituted by any of the above groups. Further, when the above monovalent substituent has two or more further substituents, the substituents may be the same or different.

於通式(I)中，R1與R2亦可各自獨立地相互鍵結而形成5員、6員、或7員之環，R2與R3亦可各自獨立地相互鍵結而形成5員、6員、或7員之環，R4與R5亦可各自獨立地相互鍵結而形成5員、6員、或7員之環，R5與R6亦可各自獨立地相互鍵結而形成5員、6員、或7員之環。另外，所形成之環可為飽和環或不飽和環之任意者。該5員、6員、或7員之飽和環或不飽和環例如可列舉吡咯環、呋喃環、噻吩環、吡唑環、咪唑環、***環、噁唑環、噻唑環、吡咯啶環、哌啶環、環戊烯環、環己烯環、苯環、吡啶環、吡嗪環、噠嗪環，較佳的是列舉苯環、吡啶環。 In the formula (I), R 1 and R 2 may each independently bond to each other to form a ring of 5 members, 6 members, or 7 members, and R 2 and R 3 may be independently bonded to each other to form a ring. Rings of 5, 6 or 7 members, R 4 and R 5 may also be independently bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 5 and R 6 may also independently of each other. Bonding to form a ring of 5 members, 6 members, or 7 members. Further, the ring formed may be any of a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5-, 6-, or 7-membered compounds include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrolidine ring. The piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

另外，於所形成之5員、6員、及7員之環可被進一步取代之情形時，可被作為所述通式(I)中之1價取代基而例示之基(亦即取代基R)之任意者取代，於被2個以上取代基(亦即取代基R)取代之情形時，該些取代基可相同亦可不同。 Further, in the case where the formed ring of 5 members, 6 members, and 7 members may be further substituted, it may be exemplified as the monovalent substituent in the above formula (I) (ie, a substituent) Any of R) may be substituted or substituted with two or more substituents (i.e., substituent R), and the substituents may be the same or different.

另外，較佳的是R1與R6並不形成環。 Further, it is preferred that R 1 and R 6 do not form a ring.

而且，於通式(I)中，於R7為鹵素原子、烷基、芳基、或雜環基之情形時，該些基之較佳範圍(包括較佳例)與作為前述之R1~R6之鹵素原子、烷基、芳基、或雜環基之較佳範圍相同。 Further, in the case of the formula (I), when R 7 is a halogen atom, an alkyl group, an aryl group or a heterocyclic group, preferred ranges of the groups (including preferred examples) and R 1 as the foregoing The preferred range of the halogen atom, alkyl group, aryl group or heterocyclic group of ~R 6 is the same.

於通式(I)中，所述R1及R6於上述中各自獨立地較佳的是烷基胺基、芳基胺基、羧醯胺基、脲基、醯亞胺基、烷氧基羰基胺基、或磺醯胺基，更佳的是羧醯胺基、脲基、烷氧基羰基胺基、或磺醯胺基，進一步更佳的是羧醯胺基、脲基、烷氧基羰基胺基、或磺醯胺基，特佳的是羧醯胺基、或脲基。 In the formula (I), R 1 and R 6 are each independently preferably an alkylamine group, an arylamine group, a carboxamide group, a ureido group, a quinone imine group or an alkoxy group. More preferably a carbonylamino group, or a sulfonylamino group, more preferably a carboxylammonium group, a ureido group, an alkoxycarbonylamino group, or a sulfonylamino group, still more preferably a carboxamide group, a urea group, or an alkane group. The oxycarbonylamino group or the sulfonylamino group is particularly preferably a carboxy oxime group or a ureido group.

於通式(I)中，所述R2及R5於上述中各自獨立地較佳的是烷氧基羰基、芳氧基羰基、胺甲醯基、烷基磺醯基、芳基磺醯基、腈基、醯亞胺基、或胺甲醯基磺醯基，更佳的是烷氧基羰基、芳氧基羰基、胺甲醯基、烷基磺醯基、腈基、醯亞胺基、或胺甲醯基磺醯基，進一步更佳的是烷氧基羰基、芳氧基羰基、胺甲醯基、腈基、醯亞胺基、或胺甲醯基磺醯基，特佳的是烷氧基羰基、芳氧基羰基、或胺甲醯基。 In the formula (I), R 2 and R 5 are each independently preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkylsulfonyl group or an arylsulfonyl group. More preferably, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, alkylsulfonyl, nitrile, quinone imine Further, more preferably an alkoxy sulfonyl group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a nitrile group, a quinone imine group, or an amine mercaptosulfonyl group, particularly preferred It is an alkoxycarbonyl group, an aryloxycarbonyl group, or an amine carbenyl group.

於通式(I)中，所述R3及R4於上述中各自獨立地較佳的是經取代或未經取代之烷基、經取代或未經取代之芳基、或經取代或未經取代之雜環基，更佳的是經取代或未經取代之烷基、或經取代或未經取代之芳基。 In the formula (I), R 3 and R 4 are each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. The substituted heterocyclic group is more preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

於通式(I)中，R3及R4所表示之烷基較佳的是碳數為1~12之直鏈、分支鏈、或環狀之經取代或未經取代之 烷基，更具體而言例如可列舉甲基、乙基、正丙基、異丙基、環丙基、正丁基、異丁基、第三丁基、環丁基、環戊基、環己基、及苄基。R3及R4所表示之烷基更佳的是碳數為1~12之分支鏈、或環狀之經取代或未經取代之烷基，更具體而言例如可列舉異丙基、環丙基、異丁基、第三丁基、環丁基、環戊基、及環己基。R3及R4所表示之烷基進一步更佳的是碳數為1~12之二級或三級之經取代或未經取代之烷基，更具體而言例如可列舉異丙基、環丙基、異丁基、第三丁基、環丁基、及環己基。 In the formula (I), the alkyl group represented by R 3 and R 4 is preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having a carbon number of 1 to 12, more preferably Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, and benzyl. base. More preferably, the alkyl group represented by R 3 and R 4 is a branched chain having a carbon number of 1 to 12 or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group or a ring. Propyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, and cyclohexyl. Further, the alkyl group represented by R 3 and R 4 is more preferably a substituted or unsubstituted alkyl group having a carbon number of from 1 to 12, more specifically, for example, an isopropyl group or a ring. Propyl, isobutyl, tert-butyl, cyclobutyl, and cyclohexyl.

於通式(I)中，R3及R4所表示之芳基可較佳地列舉經取代或未經取代之苯基、及經取代或未經取代之萘基。R3及R4所表示之芳基更佳的是經取代或未經取代之苯基。 In the formula (I), the aryl group represented by R 3 and R 4 may preferably be a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group. More preferably, the aryl group represented by R 3 and R 4 is a substituted or unsubstituted phenyl group.

於R3及R4表示雜環基之情形時的該雜環基可較佳地列舉經取代或未經取代之2-噻吩基、經取代或未經取代之4-吡啶基、經取代或未經取代之3-吡啶基、經取代或未經取代之2-吡啶基、經取代或未經取代之2-呋喃基、經取代或未經取代之2-嘧啶基、經取代或未經取代之2-苯并噻唑基、經取代或未經取代之1-咪唑基、經取代或未經取代之1-吡唑基、及經取代或未經取代之苯并***-1-基。上述雜環基可更佳地列舉經取代或未經取代之2-噻吩基、經取代或未經取代之4-吡啶基、經取代或未經取代之2-呋喃基、經取代或未經取代之2-嘧啶基、及經取代或未經取代之1-吡啶基。 The heterocyclic group in the case where R 3 and R 4 represent a heterocyclic group may preferably be a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, substituted or Unsubstituted 3-pyridyl, substituted or unsubstituted 2-pyridyl, substituted or unsubstituted 2-furyl, substituted or unsubstituted 2-pyrimidinyl, substituted or unsubstituted Substituted 2-benzothiazolyl, substituted or unsubstituted 1-imidazolyl, substituted or unsubstituted 1-pyrazolyl, and substituted or unsubstituted benzotriazol-1-yl . The above heterocyclic group may more preferably be a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 2-furyl group, substituted or unsubstituted. Substituted 2-pyrimidinyl, and substituted or unsubstituted 1-pyridyl.

其次，對形成二吡咯亞甲基金屬錯合物化合物之金屬 或金屬化合物加以說明。 Second, the metal forming the dipyrromethene metal complex compound Or metal compounds are described.

作為金屬或金屬化合物，若為可形成錯合物之金屬或金屬化合物則可為任意者，包括2價金屬原子、2價金屬氧化物、2價金屬氫氧化物、或2價金屬氯化物。例如除了Zn、Mg、Si、Sn、Rh、Pt、Pd、Mo、Mn、Pb、Cu、Ni、Co、Fe、B等以外，亦包括AlCl、InCl、FeCl、TiCl2、SnCl2、SiCl2、GeCl2等金屬氯化物，TiO、VO等金屬氧化物，Si(OH)2等金屬氫氧化物。 The metal or metal compound may be any metal or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., also includes AlCl, InCl, FeCl, TiCl 2 , SnCl 2 , SiCl 2 a metal chloride such as GeCl 2 , a metal oxide such as TiO or VO, or a metal hydroxide such as Si(OH) 2 .

該些金屬或金屬化合物中，自錯合物之穩定性、分光特性、耐熱性、耐光性、及製造適合性等觀點考慮，較佳的是Fe、Zn、Mg、Si、Pt、Pd、Mo、Mn、Cu、Ni、Co、TiO、B、或VO，更佳的是Fe、Zn、Mg、Si、Pt、Pd、Cu、Ni、Co、B、或VO，最佳的是Fe、Zn、Cu、Co、B、或VO。該些金屬或金屬化合物中最佳的是Zn。 Among these metals or metal compounds, Fe, Zn, Mg, Si, Pt, Pd, Mo are preferred from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and suitability of the self-aligned compound. , Mn, Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, most preferably Fe, Zn , Cu, Co, B, or VO. The most preferred of these metals or metal compounds is Zn.

所述通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲基金屬錯合物化合物中較佳之態樣如下所示。 Preferred aspects of the dipyrromethene metal complex compound in which the structure represented by the above formula (I) is bonded to a metal or a metal compound are shown below.

亦即，可列舉如下之態樣：於通式(I)中，R1及R6各自獨立地表示氫原子、烷基、烯基、芳基、雜環基、矽烷基、羥基、氰基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰基、胺甲醯基、胺基、苯胺基、雜環胺基、羧醯胺基、脲基、醯亞胺基、烷氧基羰基胺基、芳氧基羰基胺基、磺醯胺基、偶氮基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、芳基磺醯基、或膦醯基胺基，R2及R5各自獨 立地表示氫原子、鹵素原子、烷基、烯基、芳基、雜環基、羥基、氰基、硝基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰基、芳氧基羰基、胺甲醯基、醯亞胺基、烷氧基羰基胺基、磺醯胺基、偶氮基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、芳基磺醯基、或胺磺醯基，R3及R4各自獨立地表示氫原子、鹵素原子、烷基、烯基、芳基、雜環基、矽烷基、羥基、氰基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰基、胺甲醯基、苯胺基、羧醯胺基、脲基、醯亞胺基、烷氧基羰基胺基、磺醯胺基、偶氮基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、芳基磺醯基、胺磺醯基、或膦醯基胺基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基，金屬或金屬化合物以Zn、Mg、Si、Pt、Pd、Mo、Mn、Cu、Ni、Co、TiO、B、或VO而表示。 That is, in the general formula (I), R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, or a cyano group. , alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, aminecarbamyl, amine, anilino, heterocyclic amine, carboxy oxime, ureido, ruthenium , alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, arylsulfonyl, or A phosphinylamino group, R 2 and R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, Heterocyclicoxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminecarboxamido, oximeimido, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, aromatic sulfur a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group, and R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or a hetero Ring group, decyl group, hydroxyl group, cyano group, Oxyl, aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, amine methionyl, anilino, carboxy oxime, ureido, quinone, alkoxycarbonyl, sulfonium An amine group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an amine sulfonyl group, or a phosphinium group, and R 7 represents a hydrogen atom, A halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a metal or a metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO.

二吡咯亞甲基金屬錯合物化合物之更佳之態樣如下所示。 A more preferred aspect of the dipyrromethene metal complex compound is shown below.

亦即，可列舉如下之態樣：於所述通式(I)中，R1及R6各自獨立地表示氫原子、烷基、烯基、芳基、雜環基、氰基、醯基、烷氧基羰基、胺甲醯基、胺基、雜環胺基、羧醯胺基、脲基、醯亞胺基、烷氧基羰基胺基、芳氧基羰基胺基、磺醯胺基、偶氮基、烷基磺醯基、芳基磺醯基、或膦醯基胺基，R2及R5各自獨立地表示烷基、烯基、芳基、雜環基、氰基、硝基、醯基、烷氧基羰基、芳氧基羰基、胺甲醯基、醯亞胺基、烷基磺醯基、芳基磺醯基、或胺磺醯基，R3及R4各自獨立地表示氫原子、烷基、烯基、 芳基、雜環基、氰基、醯基、烷氧基羰基、胺甲醯基、羧醯胺基、脲基、醯亞胺基、烷氧基羰基胺基、磺醯胺基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、芳基磺醯基、或胺磺醯基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基，金屬或金屬化合物以Zn、Mg、Si、Pt、Pd、Cu、Ni、Co、B或VO而表示。 That is, in the above formula (I), R 1 and R 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group or a fluorenyl group. , alkoxycarbonyl, amine mercapto, amine, heterocyclic amine, carboxylamido, ureido, oxime imido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino , azo, alkylsulfonyl, arylsulfonyl, or phosphiniumamino, R 2 and R 5 each independently represent alkyl, alkenyl, aryl, heterocyclyl, cyano, nitrate a group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a quinone imine group, an alkyl sulfonyl group, an aryl sulfonyl group, or an amine sulfonyl group, and R 3 and R 4 are each independently Ground represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a carbamoylamino group, a ureido group, a quinone group, an alkoxy group. a carbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and R 7 represents a hydrogen atom, a halogen atom, or an alkane Base, aryl, or heterocyclic group, metal or metal compound It is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

所述通式(I)所表示之二吡咯亞甲基金屬錯合物化合物之較佳態樣可列舉選自下述通式(I-2)所表示之化合物、通式(I-3)所表示之化合物、及通式(I-4)所表示之化合物之化合物。 Preferred examples of the dipyrromethene metal complex compound represented by the above formula (I) include a compound represented by the following formula (I-2), and a formula (I-3). A compound represented by the compound and a compound represented by the formula (I-4).

所述通式(I-2)中，R1、R2、R3、R4、R5、R6及R7與通式(I)中之R1、R2、R3、R4、R5、R6及R7各自同義。Ma表示金屬或金屬化合物，X1表示可與Ma鍵結之基，X2表示用以中和Ma之電荷所必需之基。另外，X1與X2 亦可相互鍵結而與Ma一同形成5員、6員、或7員之環。 In the above formula (I-2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 and R 1 , R 2 , R 3 and R 4 in the formula (I) R 5 , R 6 and R 7 are each synonymous. Ma represents a metal or a metal compound, X 1 represents a group which can be bonded to Ma, and X 2 represents a group necessary for neutralizing the charge of Ma. Further, X 1 and X 2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members together with Ma.

通式(I-2)中，R1~R7與通式(I)中之R1~R7分別同義，較佳態樣亦相同。 In the formula (I-2), R 1 to R 7 are synonymous with R 1 to R 7 in the formula (I), and preferred embodiments are also the same.

通式(I-2)中，Ma表示金屬或金屬化合物，與所述「通式(I)所表示之化合物配位於金屬或金屬化合物上而成的二吡咯亞甲基金屬錯合物化合物」中之金屬或金屬化合物同義，其較佳之範圍亦相同。 In the formula (I-2), Ma represents a metal or a metal compound, and a dipyrromethene metal complex compound in which the compound represented by the formula (I) is bonded to a metal or a metal compound. The metal or metal compound is synonymous and its preferred range is also the same.

通式(I-2)中之X1若為可與Ma鍵結之基則可為任意者，可列舉源自水、醇類(例如甲醇、乙醇、丙醇)等、以及「金屬螯合物」[1]阪口武一．上野景平著(1995年 南江堂)、「金屬螯合物」[2](1996年)、「金屬螯合物」[3](1997年)等中所記載之化合物的基。其中，自製造適合性之觀點考慮，較佳的是源自水、羧酸化合物、醇類、胺化合物、或醯胺化合物之基，更佳的是源自水、羧酸化合物、醯胺化合物之基。 X 1 in the formula (I-2) may be any one which may be bonded to the Ma, and may be derived from water, alcohols (for example, methanol, ethanol, propanol), and the like, and metal chelate.物"[1]Sakaguchi Takeshi. The base of the compound described in Ueno Hiroshi (1995 Nanjiang Hall), "Metal Chelate" [2] (1996), "Metal Chelate" [3] (1997), etc. Among them, from the viewpoint of production suitability, it is preferably derived from water, a carboxylic acid compound, an alcohol, an amine compound, or a guanamine compound, and more preferably derived from water, a carboxylic acid compound, or a guanamine compound. The basis.

通式(I-2)中之X2表示用以中和Ma之電荷所必需的基，例如可列舉鹵素原子、羥基、羧酸基、磷酸基、磺酸基、源自R-CONHCO-R(R各自獨立地表示烷基、芳基、或雜環基)之基、及源自R-CONHSO2-R(R各自獨立地表示烷基、芳基、或雜環基)之基等，其中於製造之方面而言，較佳的是鹵素原子、羥基、羧酸基、磺酸基、源自R-CONHCO-R之基、及源自R-CONHSO2-R之基，更佳的是羥基、羧酸基、及源自R-CONHCO-R之基。另外，所謂源自R-CONHCO-R之基是指自R-CONHCO-R除去1個 氫原子而形成之1價基，除去氫原子之位置並無特別限制。 X 2 in the formula (I-2) represents a group necessary for neutralizing the charge of Ma, and examples thereof include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a source derived from R-CONHCO-R. (R each independently represents an alkyl group, an aryl group or a heterocyclic group), and a group derived from R-CONHSO 2 -R (R each independently represents an alkyl group, an aryl group or a heterocyclic group), In terms of manufacturing, preferred are a halogen atom, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a group derived from R-CONHCO-R, and a group derived from R-CONHSO 2 -R, more preferably It is a hydroxyl group, a carboxylic acid group, and a group derived from R-CONHCO-R. In addition, the group derived from R-CONHCO-R means a monovalent group formed by removing one hydrogen atom from R-CONHCO-R, and the position at which a hydrogen atom is removed is not particularly limited.

通式(I-2)中之X1與X2亦可相互鍵結而與Ma一同形成5員、6員、或7員之環。所形成之5員、6員、及7員之環可為飽和環亦可為不飽和環。而且，5員、6員、及7員之環可僅僅包含碳原子及氫原子，或者亦可為具有至少1個選自氮原子、氧原子、及硫原子之原子的雜環。 X 1 and X 2 in the formula (I-2) may be bonded to each other to form a ring of 5 members, 6 members, or 7 members together with Ma. The ring of the 5 members, 6 members, and 7 members formed may be a saturated ring or an unsaturated ring. Further, the ring of 5 members, 6 members, and 7 members may contain only a carbon atom and a hydrogen atom, or may be a hetero ring having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.

所述通式(I-3)中，R1、R2、R3、R4、R5、及R6與通式(I)中之R1、R2、R3、R4、R5、及R6各自同義。所述通式(I-3)中，R8、R9、R10、R11、R12及R13各自獨立地表示氫原子、或1價取代基。Ma表示金屬或金屬化合物。 In the above formula (I-3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 and R 1 , R 2 , R 3 , R 4 and R in the formula (I) 5 and R 6 are synonymous. In the above formula (I-3), R 8 , R 9 , R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom or a monovalent substituent. Ma represents a metal or a metal compound.

通式(I-3)中，R1~R6與通式(I)中之R1~R6同義， 較佳態樣亦相同。 In the formula (I-3), R 1 to R 6 are synonymous with R 1 to R 6 in the formula (I), and preferred embodiments are also the same.

通式(I-3)中，R8~R13所表示之1價取代基與通式(I)所表示之化合物之R1~R6所表示之1價取代基各自同義，其較佳態樣亦相同。 In the formula (I-3), the monovalent substituent represented by R 8 to R 13 is synonymous with the monovalent substituent represented by R 1 to R 6 of the compound represented by the formula (I), and preferably. The same is true.

通式(I-3)所表示之化合物之R8~R13所表示之1價取代基可被進一步取代之情形時，可被前述取代基R之任意者所取代，於被2個以上取代基R取代之情形時，該些取代基R可相同亦可不同。 When the monovalent substituent represented by R 8 to R 13 of the compound represented by the formula (I-3) may be further substituted, it may be substituted by any of the substituents R and substituted by two or more. In the case where the group R is substituted, the substituents R may be the same or different.

通式(I-3)中之R7與通式(I)中之R7同義，較佳態樣亦相同。 Formula (I-3) R 7 in the general formula (I), the same meaning as R 7, preferred aspects are also the same.

通式(I-3)中之R14表示氫原子、鹵素原子、烷基、芳基、或雜環基，R14之較佳範圍與所述R7之較佳範圍相同。於R14為可進一步被取代之基之情形時，亦可被前述取代基R之任意者所取代，於被2個以上取代基R取代之情形時，該些取代基R可相同亦可不同。 R 14 in the formula (I-3) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and a preferred range of R 14 is the same as the preferred range of the R 7 . In the case where R 14 is a group which may be further substituted, it may be substituted by any of the substituents R, and when substituted by two or more substituents R, the substituents R may be the same or different. .

通式(I-3)中，Ma表示金屬或金屬化合物，與所述「通式(I)所表示之化合物配位於金屬或金屬化合物上而成之錯合物」中之金屬或金屬化合物同義，其較佳之範圍亦相同。 In the formula (I-3), Ma represents a metal or a metal compound, and is synonymous with a metal or a metal compound in the "compound compound in which the compound represented by the formula (I) is bonded to a metal or a metal compound". The preferred range is also the same.

通式(I-3)中，R8與R9亦可各自獨立地相互鍵結而形成5員、6員、或7員之飽和環或不飽和環，R9與R10亦可各自獨立地相互鍵結而形成5員、6員、或7員之飽和環或不飽和環，R11與R12亦可各自獨立地相互鍵結而形成5員、6員、或7員之飽和環或不飽和環，R12與R13亦 可各自獨立地相互鍵結而形成5員、6員、或7員之飽和環或不飽和環。所形成之飽和環、或不飽和環與由R1與R2、R2與R3、R4與R5、或R5與R6所形成之飽和環或不飽和環同義，較佳例亦相同。 In the formula (I-3), R 8 and R 9 may each independently bond to each other to form a saturated or unsaturated ring of 5 members, 6 members, or 7 members, and R 9 and R 10 may each independently. The grounds are bonded to each other to form a saturated or unsaturated ring of 5 members, 6 members, or 7 members, and R 11 and R 12 may be independently bonded to each other to form a saturated ring of 5 members, 6 members, or 7 members. Or an unsaturated ring, R 12 and R 13 may each independently bond to each other to form a saturated ring or an unsaturated ring of 5 members, 6 members, or 7 members. The saturated ring or unsaturated ring formed is synonymous with a saturated or unsaturated ring formed by R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , or R 5 and R 6 , preferably. The same is true.

而且，通式(I-3)中，較佳的是R1並不與R8或R13形成環，且較佳的是R6並不與R8或R13形成環。 Further, in the formula (I-3), it is preferred that R 1 does not form a ring with R 8 or R 13 , and it is preferred that R 6 does not form a ring with R 8 or R 13 .

所述通式(I-4)中，R2、R3、R4、及R5各自獨立地表示氫原子、或取代基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基。R8及R9各自獨立地表示烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基。Ma表示金屬或金屬化合物。X3及X4各自獨立地表示NRa(Ra表示氫原子、烷基、烯基、芳基、雜環 基、醯基、烷基磺醯基、或芳基磺醯基)、氧原子、或硫原子。Y1及Y2各自獨立地表示NRb(Rb表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氧原子、硫原子、或碳原子。 In the above formula (I-4), R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or a substituent, and R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or Heterocyclic group. R 8 and R 9 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal or a metal compound. X 3 and X 4 each independently represent NR a (R a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom Or a sulfur atom. Y 1 and Y 2 each independently represent NR b (R b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom , sulfur atom, or carbon atom.

X5表示可與Ma鍵結之基，a表示0、1、或2。R8與Y1亦可相互鍵結而形成5員、6員、或7員之環，R9與Y2亦可相互鍵結而形成5員、6員、或7員之環。 X 5 represents a group which can be bonded to Ma, and a represents 0, 1, or 2. R 8 and Y 1 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 9 and Y 2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

通式(I-4)中之R2~R5、及R7與通式(I)中之R2~R5、及R7同義，較佳態樣亦相同。 General formula R (I-4) in the 2 ~ R 5, and R 7 in the general formula (I), the R 2 ~ R 5, and R 7 is synonymous, preferred aspects are also the same.

通式(I-4)中之Ma表示金屬或金屬化合物，與所述通式(I)所表示之化合物配位於金屬或金屬化合物上而成的錯合物中之金屬或金屬化合物同義，其較佳之範圍亦相同。 In the formula (I-4), Ma represents a metal or a metal compound, and the metal or metal compound in the complex compound in which the compound represented by the formula (I) is coordinated to a metal or a metal compound is synonymous. The preferred range is also the same.

通式(I-4)中，R8及R9各自獨立地表示烷基(較佳的是碳數為1~36之直鏈、分支鏈、或環狀之烷基，更佳的是碳數為1~12之直鏈、分支鏈、或環狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、己基、2-乙基己基、十二烷基、環丙基、環戊基、環己基、及1-金剛烷基)、烯基(較佳的是碳數為2~24之烯基，更佳的是碳數為2~12之烯基，例如可列舉乙烯基、烯丙基、及3-丁烯-1-基)、芳基(較佳的是碳數為6~36之芳基，更佳的是碳數為6~18之芳基，例如可列舉苯基、及萘基)、雜環基(較佳的是碳數為1~24之雜環基，更佳的是碳數為1~12之雜環基，例如可列舉2-噻吩基、 4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、及苯并***-1-基)、烷氧基(較佳的是碳數為1~36之烷氧基，更佳的是碳數為1~18之烷氧基，例如可列舉甲氧基、乙氧基、丙氧基、丁氧基、己氧基、2-乙基己氧基、十二烷氧基、及環己氧基)、芳氧基(較佳的是碳數為6~24之芳氧基，更佳的是碳數為1~18之芳氧基，例如可列舉苯氧基、及萘氧基)、烷基胺基(較佳的是碳數為1~36之烷基胺基，更佳的是碳數為1~18之烷基胺基，例如可列舉甲基胺基、乙基胺基、丙基胺基、丁基胺基、己基胺基、2-乙基己基胺基、異丙基胺基、第三丁基胺基、第三辛基胺基、環己基胺基、N,N-二乙基胺基、N,N-二丙基胺基、N,N-二丁基胺基、及N-甲基-N-乙基胺基)、芳基胺基(較佳的是碳數為6~36之芳基胺基，更佳的是碳數為6~18之芳基胺基，例如可列舉苯基胺基、萘基胺基、N,N-二苯基胺基、及N-乙基-N-苯基胺基)、或雜環胺基(較佳的是碳數為1~24之雜環胺基，更佳的是碳數為1~12之雜環胺基，例如可列舉2-胺基吡咯基、3-胺基吡唑基、2-胺基吡啶基、及3-胺基吡啶基)。 In the formula (I-4), R 8 and R 9 each independently represent an alkyl group (preferably a linear, branched, or cyclic alkyl group having a carbon number of 1 to 36, more preferably carbon). The linear, branched or cyclic alkyl group of 1 to 12, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2 -ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, and 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably The alkenyl group having 2 to 12 carbon atoms may, for example, be a vinyl group, an allyl group, and a 3-buten-1-yl group, or an aryl group (preferably an aryl group having a carbon number of 6 to 36), more preferably The aryl group having a carbon number of 6 to 18, for example, a phenyl group and a naphthyl group, and a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a carbon number of 1) Examples of the heterocyclic group of ~12 include 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyridyl. An azole group, and a benzotriazol-1-yl group, an alkoxy group (preferably an alkoxy group having a carbon number of 1 to 36, more preferably an alkoxy group having a carbon number of 1 to 18, for example, List A a group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group, and a cyclohexyloxy group, an aryloxy group (preferably, the carbon number is The aryloxy group of 6 to 24 is more preferably an aryloxy group having 1 to 18 carbon atoms, and examples thereof include a phenoxy group and a naphthyloxy group, and an alkylamine group (preferably, the carbon number is 1~). The alkylamino group of 36 is more preferably an alkylamine group having 1 to 18 carbon atoms, and examples thereof include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and a hexylamino group. 2-ethylhexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N,N-dipropyl Amino, N,N-dibutylamino, and N-methyl-N-ethylamino), arylamine (preferably an arylamine having 6 to 36 carbon atoms, more preferably The arylamino group having a carbon number of 6 to 18, and examples thereof include a phenylamino group, a naphthylamino group, an N,N-diphenylamino group, and an N-ethyl-N-phenylamino group. Or a heterocyclic amine group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably a heterocyclic amino group having 1 to 12 carbon atoms, and examples thereof include 2-aminopyrrolyl group, 3 -aminopyrazolyl, 2-aminopyridine And 3-amino-pyridyl).

通式(I-4)中，R8及R9所表示之烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基可進一步被取代之情形時，可被所述取代基R之任意者所取代，於被2個以上取代基R取代之情形時，該些取代基R可相同亦可不同。 In the formula (I-4), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a hetero group represented by R 8 and R 9 . When the cyclic amino group may be further substituted, it may be substituted by any of the substituents R, and when substituted by two or more substituents R, the substituents R may be the same or different.

通式(I-4)中，X3及X4各自獨立地表示NRa、氧原 子、或硫原子。Ra表示氫原子、烷基(較佳的是碳數為1~36之直鏈、分支鏈、或環狀之烷基，更佳的是碳數為1~12之直鏈、分支鏈、或環狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、己基、2-乙基己基、十二烷基、環丙基、環戊基、環己基、及1-金剛烷基)、烯基(較佳的是碳數為2~24之烯基，更佳的是碳數為2~12之烯基，例如可列舉乙烯基、烯丙基、及3-丁烯-1-基)、芳基(較佳的是碳數為6~36之芳基，更佳的是碳數為6~18之芳基，例如可列舉苯基、及萘基)、雜環基(較佳的是碳數為1~24之雜環基，更佳的是碳數為1~12之雜環基，例如可列舉2-噻吩基、4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、及苯并***-1-基)、醯基(較佳的是碳數為1~24之醯基，更佳的是碳數為2~18之醯基，例如可列舉乙醯基、特戊醯基、2-乙基己醯基、苯甲醯基、及環己醯基)、烷基磺醯基(較佳的是碳數為1~24之烷基磺醯基，更佳的是碳數為1~18之烷基磺醯基，例如可列舉甲基磺醯基、乙基磺醯基、異丙基磺醯基、及環己基磺醯基)、芳基磺醯基(較佳的是碳數為6~24之芳基磺醯基，更佳的是碳數為6~18之芳基磺醯基，例如可列舉苯基磺醯基、及萘基磺醯基)。 In the formula (I-4), X 3 and X 4 each independently represent NR a , an oxygen atom or a sulfur atom. R a represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 36, more preferably a linear or branched chain having a carbon number of 1 to 12, Or a cyclic alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl a group, a cyclopentyl group, a cyclohexyl group, and a 1-adamantyl group, an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, for example, Listed as a vinyl group, an allyl group, and a 3-buten-1-yl group, an aryl group (preferably an aryl group having a carbon number of 6 to 36, more preferably an aryl group having a carbon number of 6 to 18, For example, a phenyl group and a naphthyl group, a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms), for example, 2- Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, and benzotriazol-1-yl ), fluorenyl group (preferably a fluorenyl group having a carbon number of 1 to 24, more preferably a fluorenyl group having a carbon number of 2 to 18, and examples thereof include an ethyl group, a pentylene group, and a 2-ethyl group.醯Base, benzamidine, and cyclohexyl), alkylsulfonyl (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms) Examples of the sulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, and a cyclohexylsulfonyl group, and an arylsulfonyl group (preferably, the carbon number is 6 to 24). The arylsulfonyl group is more preferably an arylsulfonyl group having 6 to 18 carbon atoms, and examples thereof include a phenylsulfonyl group and a naphthylsulfonyl group.

而且，於Ra可被取代之情形時，可進一步被取代基所取代，於被多個取代基取代之情形時，該些取代基可相同亦可不同。於Ra可被取代之情形時的進一步之取代基可 列舉：鹵素原子(例如可列舉氟原子、氯原子、溴原子)、烷基(較佳的是碳數為1~48之直鏈、分支鏈、或環狀之烷基，更佳的是碳數為1~24之直鏈、分支鏈、或環狀之烷基，例如可列舉甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基、庚基、辛基、2-乙基己基、十二烷基、十六烷基、環丙基、環戊基、環己基、1-降莰基、及1-金剛烷基)、烯基(較佳的是碳數為2~48之烯基，更佳的是碳數為2~18之烯基，例如可列舉乙烯基、烯丙基、及3-丁烯-1-基)、芳基(較佳的是碳數為6~48之芳基，更佳的是碳數為6~24之芳基，例如可列舉苯基、及萘基)、雜環基(較佳的是碳數為1~32之雜環基，更佳的是碳數為1~18之雜環基，例如可列舉2-噻吩基、4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、及苯并***-1-基)、矽烷基(較佳的是碳數為3~38之矽烷基，更佳的是碳數為3~18之矽烷基，例如可列舉三甲基矽烷基、三乙基矽烷基、三丁基矽烷基、第三丁基二甲基矽烷基、及第三己基二甲基矽烷基)、羥基、氰基、硝基、烷氧基(較佳的是碳數為1~48之烷氧基，更佳的是碳數為1~24之烷氧基，例如可列舉甲氧基、乙氧基、1-丁氧基、2-丁氧基、異丙氧基、第三丁氧基、及十二烷基氧基，以及例如環戊氧基、或環己氧基等環烷氧基)、芳氧基(較佳的是碳數為6~48之芳氧基，更佳的是碳數為6~24之芳氧基，例如可列舉苯氧基、及1-萘氧基)、雜環氧基(較佳的是碳數為1~32之雜環氧基，更佳 的是碳數為1~18之雜環氧基，例如可列舉1-苯基四唑-5-氧基、及2-四氫吡喃基氧基)、矽烷氧基(較佳的是碳數為1~32之矽烷氧基，更佳的是碳數為1~18之矽烷氧基，例如可列舉三甲基矽烷基氧基、第三丁基二甲基矽烷氧基、及二苯基甲基矽烷氧基)、醯氧基(較佳的是碳數為2~48之醯氧基，更佳的是碳數為2~24之醯氧基，例如可列舉乙醯氧基、特戊醯氧基、苯甲醯氧基、及十二醯基氧基)、烷氧基羰氧基(較佳的是碳數為2~48之烷氧基羰氧基，更佳的是碳數為2~24之烷氧基羰氧基，例如可列舉乙氧基羰氧基、及第三丁氧基羰氧基，以及例如環己氧基羰氧基等環烷氧基羰氧基)、芳氧基羰氧基(較佳的是碳數為7~32之芳氧基羰氧基，更佳的是碳數為7~24之芳氧基羰氧基，例如可列舉苯氧基羰氧基)、胺甲醯基氧基(較佳的是碳數為1~48之胺甲醯基氧基，更佳的是碳數為1~24之胺甲醯基氧基，例如可列舉N,N-二甲基胺甲醯基氧基、N-丁基胺甲醯基氧基、N-苯基胺甲醯基氧基、及N-乙基-N-苯基胺甲醯基氧基)、胺磺醯基氧基(較佳的是碳數為1~32之胺磺醯基氧基，更佳的是碳數為1~24之胺磺醯基氧基，例如可列舉N,N-二乙基胺磺醯基氧基、及N-丙基胺磺醯基氧基)、烷基磺醯氧基(較佳的是碳數為1~38之烷基磺醯氧基，更佳的是碳數為1~24之烷基磺醯氧基，例如可列舉甲基磺醯氧基、十六烷基磺醯氧基、及環己基磺醯氧基)、芳基磺醯氧基(較佳的是碳數為6~32之芳基磺醯氧基，更佳的是碳數為6~24之芳基磺醯氧 基，例如可列舉苯基磺醯氧基)、醯基(較佳的是碳數為1~48之醯基，更佳的是碳數為1~24之醯基，例如可列舉甲醯基、乙醯基、特戊醯基、苯甲醯基、十四醯基、及環己醯基)、烷氧基羰基(較佳的是碳數為2~48之烷氧基羰基，更佳的是碳數為2~24之烷氧基羰基，例如可列舉甲氧基羰基、乙氧基羰基、十八烷氧基羰基、環己氧基羰基、及2,6-二-第三丁基-4-甲基環己氧基羰基)、芳氧基羰基(較佳的是碳數為7~32之芳氧基羰基，更佳的是碳數為7~24之芳氧基羰基，例如可列舉苯氧基羰基)、胺甲醯基(較佳的是碳數為1~48之胺甲醯基，更佳的是碳數為1~24之胺甲醯基，例如可列舉胺甲醯基、N,N-二乙基胺甲醯基、N-乙基-N-辛基胺甲醯基、N,N-二丁基胺甲醯基、N-丙基胺甲醯基、N-苯基胺甲醯基、N-甲基-N-苯基胺甲醯基、及N,N-二環己基胺甲醯基)。 Further, in the case where R a may be substituted, it may be further substituted by a substituent, and in the case of being substituted by a plurality of substituents, the substituents may be the same or different. Further examples of the substituent in the case where Ra can be substituted include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a linear chain having a carbon number of 1 to 48, and a branch). a chain or a cyclic alkyl group, more preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 24, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Base, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl And 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, for example, a vinyl group, an allyl group, And 3-buten-1-yl), aryl (preferably an aryl group having a carbon number of 6 to 48, more preferably an aryl group having a carbon number of 6 to 24, and examples thereof include a phenyl group and a naphthalene group. a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, and examples thereof include a 2-thienyl group and a 4-pyridyl group. 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, and benzo Triazol-1-yl), decylalkyl (preferably a decyl group having a carbon number of 3 to 38, more preferably an alkylene group having a carbon number of 3 to 18, and examples thereof include a trimethyldecyl group and a triethyl group. Base alkyl, tributyl decyl, tert-butyldimethyl decyl, and hexyl dimethyl decyl), hydroxy, cyano, nitro, alkoxy (preferably, carbon number is The alkoxy group of 1 to 48 is more preferably an alkoxy group having 1 to 24 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, and an isopropoxy group. , a third butoxy group, and a dodecyloxy group, and a cycloalkoxy group such as a cyclopentyloxy group or a cyclohexyloxy group, an aryloxy group (preferably a carbon number of 6 to 48) The oxy group is more preferably an aryloxy group having a carbon number of 6 to 24, and examples thereof include a phenoxy group and a 1-naphthyloxy group, and a heterocyclic oxy group (preferably a carbon number of 1 to 32). The epoxy group is more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, and examples thereof include 1-phenyltetrazole-5-oxy group and 2-tetrahydropyranyloxy group, and decyloxy group. (preferably a decyloxy group having a carbon number of 1 to 32, more preferably a decyloxy group having a carbon number of 1 to 18, and examples thereof include a trimethyldecyloxy group. a third butyl dimethyl decyloxy group, a diphenylmethyl decyloxy group, a decyloxy group (preferably a decyloxy group having a carbon number of 2 to 48, more preferably a carbon number of 2 Å) Examples of the alkoxy group of 24 may, for example, be an ethoxycarbonyl group, a p-pentyloxy group, a benzamethyleneoxy group, and a dodecyloxy group, and an alkoxycarbonyloxy group (preferably, the carbon number is 2). The alkoxycarbonyloxy group of ~48 is more preferably an alkoxycarbonyloxy group having a carbon number of 2 to 24, and examples thereof include an ethoxycarbonyloxy group and a third butoxycarbonyloxy group, and, for example, a cycloalkoxycarbonyloxy group such as a cyclohexyloxycarbonyloxy group or an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having a carbon number of 7 to 32, more preferably a carbon number of 7) The aryloxycarbonyloxy group of ~24 may, for example, be a phenoxycarbonyloxy group or an amine carbaryloxy group (preferably an amine carbaryloxy group having a carbon number of 1 to 48, more preferably Examples of the amine mercaptooxy group having a carbon number of 1 to 24, and examples thereof include N,N-dimethylamine-methylcarbonyloxy group, N-butylamine-methylcarbonyloxy group, and N-phenylamine-methyl fluorenyl group. An oxy group, and an N-ethyl-N-phenylamine methyl decyloxy group, an amine sulfonyloxy group (preferably an amine sulfonyloxy group having a carbon number of 1 to 32, more preferably carbon The number of the aminesulfonyloxy group of 1 to 24 may, for example, be N,N-diethylaminesulfonyloxy, and N-propylaminesulfonyloxy), alkylsulfonyloxy ( Preferred are alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably alkylsulfonyloxy groups having 1 to 24 carbon atoms, and examples thereof include methylsulfonyloxy group and cetyl group. a sulfonyloxy group, and a cyclohexylsulfonyloxy group, an arylsulfonyloxy group (preferably an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24) Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a mercapto group (preferably a mercapto group having a carbon number of 1 to 48, more preferably a mercapto group having a carbon number of 1 to 24, for example, There may be mentioned a decyl group, an ethyl fluorenyl group, a pentylene group, a benzamidine group, a tetradecyl group, and a cyclohexyl group, and an alkoxycarbonyl group (preferably an alkoxy group having a carbon number of 2 to 48). The carbonyl group is more preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, and 2,6-. Di-t-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably a carbon number) The aryloxycarbonyl group of 7 to 24 may, for example, be a phenoxycarbonyl group or an amine carbenyl group (preferably an amine carbenyl group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24). Examples of the amine carbenyl group include an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, an N-ethyl-N-octylamine methyl fluorenyl group, and an N,N-dibutylamine formazan group. Base, N-propylaminecarbamyl, N-phenylaminecarbamyl, N-methyl-N-phenylaminecarbamyl, and N,N-dicyclohexylaminecarbamyl).

X3及X4較佳的是各自獨立為氧原子或硫原子，X3及X4特佳的是均為氧原子。 X 3 and X 4 are preferably each independently an oxygen atom or a sulfur atom, and X 3 and X 4 are particularly preferably oxygen atoms.

通式(I-4)中，Y1及Y2各自獨立地表示NRb、硫原子、或碳原子，Rb與所述X3或X4中之Ra同義。 In the formula (I-4), Y 1 and Y 2 each independently represent NR b , a sulfur atom or a carbon atom, and R b has the same meaning as R a in the X 3 or X 4 .

Y1及Y2較佳的是各自獨立為NRb(Rb為氫原子或碳數為1~8之烷基)，Y1及Y2特佳的是均為NH。 Y 1 and Y 2 are preferably each independently NR b (R b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y 1 and Y 2 are particularly preferably all NH.

通式(I-4)中，R8與Y1亦可相互鍵結而使R8、Y1、及鄰接之碳原子一同形成5員環(例如環戊烷、吡咯啶、四氫呋喃、二氧雜環戊烷、四氫噻吩、吡咯、呋喃、噻吩、吲哚、苯并呋喃、或苯并噻吩)、6員環(例如環己烷、哌 啶、哌嗪、嗎啉、四氫吡喃、二噁烷、硫化環戊烷、二噻烷、苯、哌啶、哌嗪、噠嗪、喹啉、或喹唑啉)、或7員環(例如環庚烷、或六亞甲基亞胺)。 In the formula (I-4), R 8 and Y 1 may be bonded to each other such that R 8 , Y 1 and adjacent carbon atoms form a 5-membered ring together (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxane). Heterocyclic pentane, tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran, or benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran) , dioxane, cyclopentane sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, or quinazoline), or a 7-membered ring (eg, cycloheptane, or hexamethylene) amine).

通式(I-4)中，R9與Y2亦可相互鍵結而使R9、Y2、及鄰接之碳原子一同形成5員、6員、或7員之環。所形成之5員、6員、及7員之環之例可列舉使所述由R8與Y1及碳原子所形成之環中之1個鍵變化為雙鍵之環。 In the formula (I-4), R 9 and Y 2 may be bonded to each other such that R 9 , Y 2 and the adjacent carbon atoms form a ring of 5 members, 6 members, or 7 members. Examples of the ring of the five members, the six members, and the seven members formed include a ring in which one of the bonds formed by R 8 and Y 1 and a carbon atom is changed to a double bond.

通式(I-4)中，R8與Y1、或R9與Y2鍵結而形成的5員、6員、及7員之環可被進一步取代之情形時，可被所述取代基R之任意者所說明之基取代，於被2個以上取代基R取代之情形時，該些取代基R可相同亦可不同。 In the general formula (I-4), when R 8 and Y 1 or R 9 and Y 2 are bonded to form a ring of 5 members, 6 members, and 7 members, the ring may be further substituted. When the base substitution described in any of the groups R is substituted by two or more substituents R, the substituents R may be the same or different.

通式(I-4)中，X5表示可與Ma鍵結之基，可列舉與所述通式(I-1)中之X2相同之基。a表示0、1、或2。 In the formula (I-4), X 5 represents a group which can be bonded to Ma, and examples thereof are the same as those of X 2 in the above formula (I-1). a represents 0, 1, or 2.

以下表示通式(I-4)所表示之化合物之較佳態樣。亦即如下之態樣：R2~R5、R7、及Ma分別與包含通式(I)所表示之化合物與金屬或金屬化合物之錯合物之較佳態樣相同，X3及X4各自獨立為NRa(Ra表示氫原子、烷基、或雜環基)、或氧原子，Y1及Y2各自獨立為NRb(Rb表示氫原子或烷基)、氮原子、或碳原子，X5為經由氧原子或氮原子而鍵結之基，R8及R9分別獨立地表示烷基、芳基、雜環基、烷氧基、或烷基胺基，或者R8與Y1相互鍵結而形成5員或6員環，R9與Y2相互鍵結而形成5員、6員環，a表示0或1。 Preferred embodiments of the compound represented by the formula (I-4) are shown below. That is, the following aspects: R 2 to R 5 , R 7 , and Ma are respectively the same as the preferred embodiment of the complex containing the compound represented by the general formula (I) and the metal or metal compound, X 3 and X. 4 is independently NR a (R a represents a hydrogen atom, an alkyl group or a heterocyclic group), or an oxygen atom, and each of Y 1 and Y 2 is independently NR b (R b represents a hydrogen atom or an alkyl group), a nitrogen atom, Or a carbon atom, X 5 is a group bonded via an oxygen atom or a nitrogen atom, and R 8 and R 9 each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R 8 and Y 1 are bonded to each other to form a 5-member or 6-membered ring, and R 9 and Y 2 are bonded to each other to form a 5-membered, 6-membered ring, and a represents 0 or 1.

以下表示通式(I-4)所表示之化合物之更佳態樣。亦 即如下之態樣：R2~R5、R7、Ma分別與包含通式(I)所表示之化合物與金屬或金屬化合物的錯合物之較佳態樣相同，X3及X4為氧原子，Y1為NH，Y2為氮原子，X5為經由氧原子或氮原子而鍵結之基，R8及R9分別獨立地表示烷基、芳基、雜環基、烷氧基、或烷基胺基，或者R8與Y1相互鍵結而形成5員或6員環，R9與Y2相互鍵結而形成5員、6員環，a表示0或1。 The above shows a more preferable aspect of the compound represented by the formula (I-4). That is, the following aspects: R 2 to R 5 , R 7 , and Ma are respectively the same as the preferred embodiment of the complex containing the compound represented by the general formula (I) and the metal or metal compound, X 3 and X 4 . Is an oxygen atom, Y 1 is NH, Y 2 is a nitrogen atom, X 5 is a group bonded via an oxygen atom or a nitrogen atom, and R 8 and R 9 each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkane An oxy group, or an alkylamino group, or R 8 and Y 1 are bonded to each other to form a 5- or 6-membered ring, and R 9 and Y 2 are bonded to each other to form a 5-membered, 6-membered ring, and a represents 0 or 1.

所述通式(I-2)至通式(I-4)所表示之錯合化合物(亦即，作為所述通式(I)所表示之結構配位於金屬或金屬化合物上而成的金屬錯合物化合物的染料之較佳態樣)中的所述通式(I-4)所表示之化合物是特佳之樣態。 a compound represented by the above formula (I-2) to formula (I-4) (that is, a metal obtained by disposing the structure represented by the above formula (I) on a metal or a metal compound The compound represented by the above formula (I-4) in the preferred aspect of the dye of the complex compound is a particularly preferable form.

以下，表示本發明中所使用之所述通式(I)所表示之特定染料(A-1)的具體例。其中，本發明並不限定於該些具體例。 Specific examples of the specific dye (A-1) represented by the above formula (I) used in the present invention are shown below. However, the present invention is not limited to these specific examples.

另外，如以下具體例所示那樣，本發明之特定染料(A-1)不僅僅是所述通式(I)所表示之二吡咯亞甲基金屬錯合物化合物(單體)，亦包含含有該結構作為部分結構之多聚體。 Further, as shown in the following specific examples, the specific dye (A-1) of the present invention is not limited to the dipyrromethene metal complex compound (monomer) represented by the above formula (I), and includes A polymer containing the structure as a partial structure.

另外，於下述之例示化合物43~例示化合物45中，a/b及a/b/c表示各個構成成分之質量比。 Further, in the exemplified compound 43 to the exemplified compound 45 described below, a/b and a/b/c represent the mass ratio of each constituent component.

[化9] [Chemistry 9]

[化10] [化10]

[化11] [11]

[化12] [化12]

[化13] [Chemistry 13]

[化14] [Chemistry 14]

[化15] [化15]

該些二吡咯亞甲基金屬錯合物化合物之例示化合物中，例示化合物(46)~例示化合物(50)亦為通式(I-2)之例示化合物，例示化合物(51)亦為通式(I-3)之例示化合物，例示化合物(1)~例示化合物(45)亦為通式(I-4)之例示化合物。 In the exemplified compounds of the dipyrromethene metal complex compounds, the exemplified compound (46) to the exemplified compound (50) are also exemplified compounds of the formula (I-2), and the exemplified compound (51) is also a general formula. The exemplified compound of (I-3), the exemplified compound (1) to the exemplified compound (45) are also exemplified compounds of the formula (I-4).

而且，除了上述例示化合物以外，亦可列舉日本專利特開2008-292970號公報中所記載之例示化合物(Ia-3)~例示化合物(Ia-83)、例示化合物(Ia-1)~例示化合物(IIa-20)、例示化合物(I-1)~例示化合物(I-36)、例示 化合物(II-1)~例示化合物(II-11)、及例示化合物(III-1)~例示化合物(III-103)、日本專利第3324279號公報中所記載之例示化合物(I-1)~例示化合物(I-35)、日本專利第3279035號公報中所記載之例示化合物(I-1)~例示化合物(I-13)、日本專利特開平11-256057號公報中所記載之例示化合物(2-1)~例示化合物(2-32)、例示化合物(3-1)~例示化合物(3-32)、例示化合物(4-1)~例示化合物(4-26)、及例示化合物(5-1)~例示化合物(5-26)、日本專利特開2005-77953號公報中所記載之例示化合物(I-1)~例示化合物(I-6)、及例示化合物(VII-1)~例示化合物(VII-8)、日本專利特開平11-352686號公報中所記載之例示化合物(1-1)~例示化合物(1-45)、日本專利特開2000-19729號公報中所記載之例示化合物(1-1)~例示化合物(1-50)、及日本專利特開平11-352685號公報中所記載之例示化合物(1-1)~例示化合物(1-45)等作為通式(I)所表示之結構配位於金屬或金屬化合物上而成的金屬錯合物化合物的染料(二吡咯亞甲基金屬錯合物化合物)之例。 Further, in addition to the above-exemplified compounds, the exemplified compounds (Ia-3) to exemplified compounds (Ia-83) and the exemplified compounds (Ia-1) to exemplified compounds described in JP-A-2008-292970 may be mentioned. (IIa-20), exemplified compound (I-1) to exemplified compound (I-36), exemplified Compound (II-1) to exemplified compound (II-1), and exemplified compound (III-1) to exemplified compound (III-103), and exemplified compound (I-1) described in Japanese Patent No. 3324279 The exemplified compound (I-35), the exemplified compound (I-1) to the exemplified compound (I-13), and the exemplified compound described in JP-A-H11-256057 (Japanese Patent No. Hei. 2-1) to exemplified compound (2-32), exemplified compound (3-1) to exemplified compound (3-32), exemplified compound (4-1) to exemplified compound (4-26), and exemplified compound (5) -1) - exemplified compound (5-26), and exemplified compound (I-1) - exemplified compound (I-6) and exemplified compound (VII-1) described in JP-A-2005-77953 Illustrative compound (VII-8), and the exemplified compounds (1-1) to exemplified compounds (1-45) described in JP-A-H09-352686, and JP-A-2000-19729 The exemplified compound (1-1) to the exemplified compound (1-50), and the exemplified compound (1-1) to the exemplified compound (1-45) described in JP-A-H11-352685, etc. I) is represented by the structure An example of a dye (dipyrromethene metal complex compound) of a metal complex compound formed on a metal or a metal compound.

(A-2)通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基金屬錯合物化合物 (A-2) Azapyrrolemethylene metal complex compound in which the structure represented by the formula (II) is bonded to a metal or a metal compound

其次，對通式(II)所表示之氮雜吡咯亞甲基金屬錯合物化合物(以下適宜稱為「氮雜吡咯亞甲基金屬錯合物化合物」或「特定染料(A-2)」)加以說明。 Next, the azapyrrolemethylene metal complex compound represented by the formula (II) (hereinafter referred to as "azapyrrolemethylene metal complex compound" or "specific dye (A-2)" ) to explain.

[化16] [Chemistry 16]

所述通式(II)中，R21、R22、R23、R24、R25及R26分別獨立地表示氫原子或1價取代基。 In the above formula (II), R 21 , R 22 , R 23 , R 24 , R 25 and R 26 each independently represent a hydrogen atom or a monovalent substituent.

上述R21~R26表示1價取代基之情形時的1價取代基可列舉所述通式(I)中之R1~R6中所例示的1價取代基，較佳例亦相同。 The monovalent substituent in the case where R 21 to R 26 are a monovalent substituent, and the monovalent substituent exemplified in R 1 to R 6 in the above formula (I) is preferred, and preferred examples are also the same.

另外，R21與R22、R22與R23、R24與R25、及R25與R26之至少一組亦可分別相互鍵結而形成5員、6員、或7員之飽和環或不飽和環。所形成之5員、6員、及7員之環可被進一步取代之情形時，可被所述通式(I)中之R1~R6中所說明之取代基(取代基R)所進一步取代，於被2個以上取代基(取代基R)取代之情形時，該些取代基(取代基R)可相同亦可不同。 Further, at least one of R 21 and R 22 , R 22 and R 23 , R 24 and R 25 , and R 25 and R 26 may be bonded to each other to form a saturated ring of 5 members, 6 members, or 7 members. Or an unsaturated ring. When the formed ring of 5 members, 6 members, and 7 members can be further substituted, it can be represented by the substituent (substituent R) described in R 1 to R 6 in the above formula (I). Further, when substituted by two or more substituents (substituent R), the substituents (substituent R) may be the same or different.

所述通式(II)所表示之化合物較佳的是下述通式(II-1)或通式(II-2)所表示之化合物。 The compound represented by the above formula (II) is preferably a compound represented by the following formula (II-1) or formula (II-2).

[化17] [化17]

所述通式(II-1)及通式(II-2)中，Ra分別獨立地表示芳基或烷基。Rb分別獨立地表示2,6-二-第三丁基-4-甲基環己氧基羰基或氰基，Rd分別獨立地表示烷基、芳基、雜芳基或烯基。 In the above formula (II-1) and formula (II-2), R a each independently represents an aryl group or an alkyl group. R b each independently represents 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl or cyano, and R d each independently represents an alkyl group, an aryl group, a heteroaryl group or an alkenyl group.

所述通式(II)所表示之氮雜吡咯亞甲基金屬錯合物化合物之其他較佳態樣可列舉下述通式(II-3)所表示之金屬錯合物。 Other preferred examples of the azapyrrolemethylene metal complex compound represented by the above formula (II) include metal complexes represented by the following formula (II-3).

[化19] [Chemistry 19]

所述通式(II-3)中，R21、R22、R23、R24、R25及R26分別獨立地表示氫原子或取代基。Ma表示金屬原子或金屬化合物，X分別獨立地表示取代基。Ma與X之間為共價鍵、配位鍵或離子鍵。n為2~4之整數。 In the above formula (II-3), R 21 , R 22 , R 23 , R 24 , R 25 and R 26 each independently represent a hydrogen atom or a substituent. Ma represents a metal atom or a metal compound, and X each independently represents a substituent. A covalent bond, a coordinate bond or an ionic bond is between Ma and X. n is an integer from 2 to 4.

於所述通式(II-3)中，虛線表示配位鍵。以下，關於通式(II-4)~通式(II-9)及例示化合物亦表示同樣之含義。 In the above formula (II-3), a broken line indicates a coordinate bond. Hereinafter, the same meanings are also given to the general formula (II-4) to the general formula (II-9) and the exemplified compounds.

通式(II-3)中之R21、R22、R23、R24、R25及R26分別與通式(II)中之R21、R22、R23、R24、R25及R26同義，較佳之範圍亦相同。 Formula (II-3) in the R 21, R 22, R 23 , R 24, R 25 and R 26 are of the general formula R (II) in the 21, R 22, R 23, R 24, R 25 , and R 26 is synonymous, and the preferred range is also the same.

此處，R21與X亦可相互鍵結而與Ma一同形成5員、6員、或7員之環，R26與X亦可相互鍵結而與Ma一同形成5員、6員、或7員之環。 Here, R 21 and X may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members together with Ma, and R 26 and X may also be bonded to each other to form 5 members, 6 members, or together with Ma. Ring of 7 members.

Ma與X較佳的是至少1個藉由配位鍵而進行鍵結。n為2~4之整數，較佳的是3。於分子內多個存在之X可相互相同亦可不同。 Preferably, Ma and X are at least one bonded by a coordinate bond. n is an integer of 2 to 4, preferably 3. The plurality of Xs present in the molecule may be the same or different from each other.

Ma較佳的是Zn、Mg、Sc、Fe、Al、Cr、Si、Pt、Pd、 Mo、Mn、Cu、Ni、Co、TiO、或VO，更佳的是Zn、Mg、Sc、Fe、Al、Mn、Cu、Ni、Co、TiO、或VO，特佳的是Zn、Cu或Co。 Ma is preferably Zn, Mg, Sc, Fe, Al, Cr, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO, more preferably Zn, Mg, Sc, Fe, Al, Mn, Cu, Ni, Co, TiO, or VO, particularly preferably Zn, Cu or Co.

通式(II)所表示之金屬錯合物化合物為通式(II-4)所表示之金屬錯合物化合物亦是較佳態樣。 The metal complex compound represented by the formula (II) is also a metal complex compound represented by the formula (II-4).

所述通式(II-4)中，R22、R23、R24、R25及R26分別獨立地表示氫原子或取代基。R27表示烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基。Ma表示金屬原子或金屬化合物，X分別獨立地表示取代基。X11表示NR、氮原子、氧原子或硫原子，R表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基。Y1表示NRc、氮原子、或碳原子，Rc表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基。Ma與X之間藉由共價鍵、配位鍵 或離子鍵進行鍵結。n1為2~4之整數，於分子內多個存在之X可相互相同亦可不同。 In the above formula (II-4), R 22 , R 23 , R 24 , R 25 and R 26 each independently represent a hydrogen atom or a substituent. R 27 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound, and X each independently represents a substituent. X 11 represents NR, a nitrogen atom, an oxygen atom or a sulfur atom, and R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group. Y 1 represents NRc, a nitrogen atom, or a carbon atom, and Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group. The bond between Ma and X is carried out by a covalent bond, a coordinate bond or an ionic bond. N1 is an integer of 2 to 4, and a plurality of X existing in the molecule may be the same or different.

R27與Y1亦可相互鍵結而形成5員、6員、或7員之環，R27與X11亦可相互鍵結而形成5員、6員、或7員之環，X11與X亦可相互鍵結而形成5員、6員、或7員之環。 R 27 and Y 1 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 27 and X 11 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, X 11 And X can also be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

通式(II-4)中之R22、R23、R24、R25及R26分別與通式(II)中之R22、R23、R24、R25及R26同義，較佳之範圍亦相同。 Formula (II-4) in the R 22, R 23, R 24 , R 25 and R 26 are synonymous with the general formula 26 R (II) in the 22, R 23, R 24, R 25 , and R, the preferred The scope is also the same.

通式(II-4)中之R27較佳的是烷基或芳基，更佳的是芳基，進一步更佳的是苯基。該些基亦可進一步具有取代基。進一步之取代基較佳的是烷基，更佳的是碳數為1~3之烷基。 R 27 in the formula (II-4) is preferably an alkyl group or an aryl group, more preferably an aryl group, still more preferably a phenyl group. These groups may further have a substituent. Further, the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.

通式(II-4)中之Ma與通式(II-3)中之Ma同義，較佳之範圍亦相同。 Ma in the formula (II-4) is synonymous with Ma in the formula (II-3), and the preferred range is also the same.

通式(II-4)中之X11較佳的是氧原子。 X 11 in the formula (II-4) is preferably an oxygen atom.

通式(II-4)中之Y1較佳的是NRc。Rc較佳的是氫原子。 Y 1 in the formula (II-4) is preferably NRc. Rc is preferably a hydrogen atom.

通式(II)所表示之金屬錯合物化合物可列舉通式(II-5)所表示之金屬錯合物化合物作為更佳態樣。 The metal complex compound represented by the formula (II) can be exemplified as the metal complex compound represented by the formula (II-5).

[化21] [Chem. 21]

通式(II-5)中，R22、R23、R24及R25分別獨立地表示氫原子或取代基。R27及R28分別獨立地表示烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基。Ma表示金屬原子或金屬化合物。X11、X12分別獨立地表示NR(R表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氮原子、氧原子或硫原子。Y1、Y2分別獨立地表示NRc(Rc表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氮原子、或碳原子。Z1表示可與Ma鍵結之基，a表示0、1或2。 In the formula (II-5), R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom or a substituent. R 27 and R 28 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X 11 and X 12 each independently represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or an oxygen. Atom or sulfur atom. Y 1 and Y 2 each independently represent NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or carbon atom. Z 1 represents a group which can be bonded to Ma, and a represents 0, 1, or 2.

R27與Y1亦可相互鍵結而形成5員、6員、或7員之環，R28與Y2亦可相互鍵結而形成5員、6員、或7員之環。而且，R27與X11亦可相互鍵結而形成5員、6員、或7員之環，R28與X12亦可相互鍵結而形成5員、6員、或7員之環，R27與Z1亦可相互鍵結而形成5員、6員、或7員之環，R28與Z1亦可相互鍵結而形成5員、6員、或7 員之環。 R 27 and Y 1 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and Y 2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members. Moreover, R 27 and X 11 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and X 12 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members. R 27 and Z 1 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and Z 1 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

通式(II-5)中之R22、R23、R24及R25分別與通式(II)中之R22、R23、R24及R25同義，較佳之範圍亦相同。 R 22 , R 23 , R 24 and R 25 in the formula (II-5) have the same meanings as R 22 , R 23 , R 24 and R 25 in the formula (II), and preferably have the same range.

通式(II-5)中之R27及R28分別獨立地較佳的是烷基或芳基，更佳的是芳基，進一步更佳的是苯基。該些基亦可進一步具有取代基。進一步之取代基較佳的是烷基，更佳的是碳數為1~3之烷基。 R 27 and R 28 in the formula (II-5) are each independently preferably an alkyl group or an aryl group, more preferably an aryl group, still more preferably a phenyl group. These groups may further have a substituent. Further, the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.

通式(II-5)中之Ma與通式(II-2)中之Ma同義，較佳之範圍亦相同。 Ma in the formula (II-5) is synonymous with Ma in the formula (II-2), and the preferred range is also the same.

通式(II-5)中之X11、X12分別較佳的是氧原子。 X 11 and X 12 in the formula (II-5) are each preferably an oxygen atom.

通式(II-5)中之Y1、Y2分別獨立地較佳的是NRc。Rc較佳的是氫原子。 Y 1 and Y 2 in the formula (II-5) are each independently preferably NRc. Rc is preferably a hydrogen atom.

Z1表示可與Ma離子鍵結或共價鍵結之基。Z1較佳的是可列舉四氟硼離子、六氟磷離子、六氟銻離子、三(三氟甲磺酸)甲基化物離子、過氯酸離子、氰基、鹵基(較佳的是氯)、烷基羧酸基(較佳的是碳數為2~20之烷基羧酸基，更佳的是碳數為2~12之烷基羧酸基，特佳的是碳數為2~8之烷基羧酸基。例如可列舉乙酸基、乳酸基、癸烷羧酸基等)、芳基羧酸基(較佳的是碳數為2~20之芳基羧酸基，更佳的是碳數為2~11之芳基羧酸基，特佳的是碳數為2~7之芳基羧酸基。例如可列舉苯甲酸基、蒽醌羧酸基、萘羧酸基等)、烷基磺酸基(較佳的是碳數為2~20之烷基磺酸基，更佳的是碳數為2~12之烷基磺酸基，特佳的是碳數為2~8之烷基磺酸基。例如可列舉甲基磺酸 基、三氟甲基磺酸基)、芳基磺酸基(較佳的是碳數為2~20之芳基磺酸基，更佳的是碳數為2~11之芳基磺酸基，特佳的是碳數為2~7之芳基磺酸基。例如可列舉苯磺酸基、對甲苯磺酸基、萘磺酸基)、羥基、醯亞胺基(較佳的是碳數為2~20之醯亞胺基，更佳的是碳數為2~12之醯亞胺基，特佳的是碳數為2~8之醯亞胺基。例如可列舉鄰苯二甲醯亞胺基、二乙醯醯亞胺基、雙三氟甲磺醯亞胺基等)、芳氧基(較佳的是碳數為2~20之芳氧基，更佳的是碳數為2~12之芳氧基，特佳的是碳數為2~8之芳氧基。例如可列舉苯氧基等)、烷硫基(較佳的是碳數為2~20之烷硫基，更佳的是碳數為2~12之烷硫基，特佳的是碳數為2~8之烷硫基。例如可列舉十二烷硫基等)、芳硫基(較佳的是碳數為2~20之芳硫基，更佳的是碳數為2~12之芳硫基，特佳的是碳數為2~8之芳硫基。例如可列舉苯硫基)等。其中較佳的是烷基羧酸基、芳基羧酸基、芳基磺酸基、醯亞胺基，更佳的是烷基羧酸基、醯亞胺基，特佳的是烷基羧酸基。 Z 1 represents a group which can be bonded or covalently bonded to the Ma ion. Preferred examples of Z 1 include tetrafluoroboron ion, hexafluorophosphorus ion, hexafluoroantimonium ion, tris(trifluoromethanesulfonate) methide ion, perchloric acid ion, cyano group, and halogen group (preferably Is a chlorine), an alkyl carboxylic acid group (preferably an alkyl carboxylic acid group having a carbon number of 2 to 20, more preferably an alkyl carboxylic acid group having a carbon number of 2 to 12, particularly preferably a carbon number Examples of the alkyl carboxylic acid group of 2 to 8 include an acetate group, a lactic acid group, a decane carboxylic acid group, and the like, and an aryl carboxylic acid group (preferably an aryl carboxylic acid group having 2 to 20 carbon atoms). More preferably, it is an arylcarboxylic acid group having a carbon number of 2 to 11, and particularly preferably an arylcarboxylic acid group having a carbon number of 2 to 7. Examples thereof include a benzoic acid group, a hydrazinecarboxylic acid group, and a naphthyl carboxyl group. An acid group or the like, an alkylsulfonic acid group (preferably an alkylsulfonic acid group having 2 to 20 carbon atoms, more preferably an alkylsulfonic acid group having 2 to 12 carbon atoms, particularly preferably carbon) The number is an alkylsulfonate group of 2 to 8. For example, a methylsulfonate group, a trifluoromethylsulfonate group, an arylsulfonate group (preferably, an arylsulfonyl group having a carbon number of 2 to 20) The acid group is more preferably an arylsulfonic acid group having a carbon number of 2 to 11, and particularly preferably an arylsulfonic acid group having a carbon number of 2 to 7. Examples thereof include a benzenesulfonic acid group. P-toluenesulfonic acid group, naphthalenesulfonic acid group, hydroxyl group, quinone imine group (preferably a quinone imine group having a carbon number of 2 to 20, more preferably an anthranylene group having a carbon number of 2 to 12) Particularly preferred is an anthranylene group having a carbon number of 2 to 8. Examples thereof include a phthalimido group, a diethylene sulfoximine group, a bistrifluoromethanesulfonimide group, and the like. An oxy group (preferably an aryloxy group having 2 to 20 carbon atoms, more preferably an aryloxy group having 2 to 12 carbon atoms, particularly preferably an aryloxy group having 2 to 8 carbon atoms). A phenoxy group or the like, an alkylthio group (preferably an alkylthio group having 2 to 20 carbon atoms, more preferably an alkylthio group having 2 to 12 carbon atoms, and particularly preferably a carbon number of 2 to 2) An alkylthio group, for example, a dodecylthio group or the like, an arylthio group (preferably an arylthio group having 2 to 20 carbon atoms, more preferably an arylthio group having 2 to 12 carbon atoms). Particularly preferred is an arylthio group having 2 to 8 carbon atoms, and examples thereof include a phenylthio group. Preferred among them are an alkyl carboxylic acid group, an aryl carboxylic acid group, an aryl sulfonic acid group, an oxime imido group, more preferably an alkyl carboxylic acid group or a quinone imine group, and particularly preferably an alkyl carboxy group. Acid base.

a較佳的是1。 a is preferably 1.

而且，通式(II)所表示之金屬錯合物亦較佳的是通式(II-6)所表示之金屬錯合物。 Further, the metal complex represented by the formula (II) is also preferably a metal complex represented by the formula (II-6).

[化22] [化22]

通式(II-6)中，R22、R23、R24及R25分別獨立地表示氫原子或取代基。R27及R28分別獨立地表示烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基。Ma表示金屬原子或金屬化合物。X111表示NR(R表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氮原子、氧原子、或硫原子，X112表示NRa(Ra表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氧原子、或硫原子。Y11表示NRc(Rc表示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、或芳基磺醯基)、氮原子、或碳原子，Y12表示氮原子或碳原子。Z2表示可與Ma鍵結之基，a表示0、1或2。 In the formula (II-6), R 22 , R 23 , R 24 and R 25 each independently represent a hydrogen atom or a substituent. R 27 and R 28 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X 111 represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom, X 112 represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom. Y 11 represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom, and Y 12 represents A nitrogen atom or a carbon atom. Z 2 represents a group which can be bonded to Ma, and a represents 0, 1, or 2.

R27與Y11亦可相互鍵結而形成5員、6員、或7員之環，R28與Y12亦可相互鍵結而形成5員、6員、或7員之環。而且，R27與X111亦可相互鍵結而形成5員、6員、或 7員之環，R28與X112亦可相互鍵結而形成5員、6員、或7員之環，R27與Z2亦可相互鍵結而形成5員、6員、或7員之環，R28與Z2亦可相互鍵結而形成5員、6員、或7員之環。 R 27 and Y 11 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and Y 12 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members. Moreover, R 27 and X 111 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and X 112 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members. R 27 and Z 2 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R 28 and Z 2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

通式(II-6)中之R22、R23、R24及R25分別與通式(II)中之R22、R23、R24及R25同義，較佳之範圍亦相同。 R 22 , R 23 , R 24 and R 25 in the formula (II-6) have the same meanings as R 22 , R 23 , R 24 and R 25 in the formula (II), and the preferred ranges are also the same.

通式(II-6)中之R7及R8分別與通式(II-5)中之R7及R8同義，較佳之範圍亦相同。 R 7 and R 8 in the formula (II-6) are synonymous with R 7 and R 8 in the formula (II-5), respectively, and the preferred range is also the same.

通式(II-6)中之Y11較佳的是NRc或氮原子。Rc較佳的是氫原子。 Y 11 in the formula (II-6) is preferably NRc or a nitrogen atom. Rc is preferably a hydrogen atom.

通式(II-6)中之Y12較佳的是氮原子。 Y 12 in the formula (II-6) is preferably a nitrogen atom.

通式(II-6)中之X111及X112較佳的是氧原子。 X 111 and X 112 in the formula (II-6) are preferably an oxygen atom.

通式(II-6)中之Z2表示可與Ma配位鍵結之基。Z2可列舉醚(例如四氫呋喃、二***)、烷基羧酸(較佳的是碳數為2~20之烷基羧酸，更佳的是碳數為2~12之烷基羧酸，特佳的是碳數為2~8之烷基羧酸。例如可列舉乙酸、乳酸、癸烷羧酸等)、芳基羧酸(較佳的是碳數為6~20之芳基羧酸，更佳的是碳數為6~11之芳基羧酸，特佳的是碳數為6~7之芳基羧酸。例如可列舉苯甲酸、蒽醌羧酸、萘羧酸等)、烷基磺酸(較佳的是碳數為2~20之烷基磺酸，更佳的是碳數為2~12之烷基磺酸，特佳的是碳數為2~8之烷基磺酸。例如可列舉甲基磺酸、三氟甲基磺酸)、芳基磺酸(較佳的是碳數為6~20之芳基磺酸，更佳的是碳數為6~11之芳基磺酸，特佳的是碳數為6~7之芳 基磺酸。例如可列舉苯磺酸、對甲苯磺酸、萘磺酸)、水、醯亞胺(較佳的是碳數為2~20之醯亞胺，更佳的是碳數為2~12之醯亞胺，特佳的是碳數為2~8之醯亞胺。例如可列舉鄰苯二甲醯亞胺、二乙醯醯亞胺、雙三氟甲磺醯亞胺等)、烷基醇(較佳的是碳數為2~20之醇，更佳的是碳數為2~12之醇，特佳的是碳數為1~8之醇。例如甲醇、丁醇、異丙醇等)、芳基醇(較佳的是碳數為6~20之芳基醇，更佳的是碳數為6~12之芳基醇，特佳的是碳數為6~8之芳基醇。例如可列舉苯酚等)、芳基硫醇(較佳的是碳數為6~20之芳基硫醇，更佳的是碳數為6~12之芳基硫醇，特佳的是碳數為6~8之芳基硫醇。例如可列舉苯硫酚等)、烷基硫醇(較佳的是碳數為2~20之烷基硫醇，更佳的是碳數為2~12之烷基硫醇，特佳的是碳數為2~8之烷基硫醇。例如可列舉十二烷硫醇)等。其中，較佳的是水、烷基羧酸、芳基羧酸、芳基磺酸、醯亞胺，更佳的是烷基羧酸、水，特佳的是烷基羧酸。 Z 2 in the formula (II-6) represents a group which can be coordinately bonded to Ma. Z 2 may, for example, be an ether (for example, tetrahydrofuran or diethyl ether) or an alkyl carboxylic acid (preferably an alkyl carboxylic acid having 2 to 20 carbon atoms, more preferably an alkyl carboxylic acid having 2 to 12 carbon atoms). Particularly preferred are alkyl carboxylic acids having 2 to 8 carbon atoms, for example, acetic acid, lactic acid, decane carboxylic acid, etc., and aryl carboxylic acids (preferably aryl carboxylic acids having 6 to 20 carbon atoms). More preferably, it is an aryl carboxylic acid having a carbon number of 6 to 11, and particularly preferably an aryl carboxylic acid having a carbon number of 6 to 7. Examples thereof include benzoic acid, anthracene carboxylic acid, naphthalenecarboxylic acid, etc.) An alkyl sulfonic acid (preferably an alkyl sulfonic acid having 2 to 20 carbon atoms, more preferably an alkyl sulfonic acid having 2 to 12 carbon atoms, particularly preferably an alkyl group having 2 to 8 carbon atoms) Sulfonic acid, for example, methanesulfonic acid, trifluoromethanesulfonic acid, arylsulfonic acid (preferably, an arylsulfonic acid having a carbon number of 6 to 20, more preferably a carbon number of 6 to 11) The arylsulfonic acid is particularly preferably an arylsulfonic acid having a carbon number of 6 to 7. Examples thereof include benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, water, and quinone imine (preferably carbon). The number of the imines is 2 to 20, more preferably the imines having a carbon number of 2 to 12, and particularly preferably the imines having a carbon number of 2 to 8. For example, o-phthalazin An amine, a diethylimine, a bistrifluoromethanesulfonimide, or the like, an alkyl alcohol (preferably an alcohol having 2 to 20 carbon atoms, more preferably an alcohol having 2 to 12 carbon atoms). Particularly preferred are alcohols having a carbon number of 1 to 8, such as methanol, butanol, isopropanol, etc., aryl alcohols (preferably aryl alcohols having a carbon number of 6 to 20, more preferably carbon numbers) The aryl alcohol of 6 to 12 is particularly preferably an aryl alcohol having a carbon number of 6 to 8. For example, phenol or the like, an aryl thiol (preferably an aryl sulfide having a carbon number of 6 to 20) The alcohol is more preferably an aryl thiol having a carbon number of 6 to 12, particularly preferably an aryl thiol having a carbon number of 6 to 8. For example, thiophenol or the like, an alkyl mercaptan (preferably) The alkyl mercaptan having a carbon number of 2 to 20 is more preferably an alkyl mercaptan having a carbon number of 2 to 12, and particularly preferably an alkyl mercaptan having a carbon number of 2 to 8. For example, ten Dialkyl mercaptan) and the like. Among them, preferred are water, an alkyl carboxylic acid, an aryl carboxylic acid, an aryl sulfonic acid, a quinone imine, more preferably an alkyl carboxylic acid, water, and particularly preferably an alkyl carboxylic acid.

a較佳的是1。 a is preferably 1.

通式(II)所表示之化合物特佳的是通式(II-7)或通式(II-8)所表示之化合物。 The compound represented by the formula (II) is particularly preferably a compound represented by the formula (II-7) or the formula (II-8).

[化23] [化23]

通式(II-7)及通式(II-8)中之Ra、Rb及Rd與所述通式(II-1)及通式(II-2)中之Ra、Rb及Rd分別同義。Ma為金屬原子或金屬化合物，Z1表示可與Ma鍵結之基。 Formula (II-7) and formula (II-8) in the R a, R b, and R d and (II-1) in the general formula and the general formula (II-2) in the R a, R b And R d are synonymous respectively. Ma is a metal atom or a metal compound, and Z 1 represents a group which can be bonded to Ma.

上述通式(II-7)或通式(II-8)中，Ra分別獨立地較佳的是芳基。 In the above formula (II-7) or formula (II-8), R a is each independently preferably an aryl group.

由Ra所表示之亦可具有取代基之芳基較佳的是經取 代或未經取代之苯基、經取代或未經取代之甲苯基、經取代或未經取代之氯苯基、經取代或未經取代之溴苯基、經取代或未經取代之氰苯基，更佳的是經取代或未經取代之苯基、經取代或未經取代之甲苯基，進一步更佳的是經取代或未經取代之苯基。 The aryl group which may have a substituent represented by R a is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted chlorophenyl group, a substituted or unsubstituted bromophenyl group, a substituted or unsubstituted cyanophenyl group, more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted tolyl group, still more preferably Substituted or unsubstituted phenyl.

由Ra所表示之烷基較佳的是甲基、乙基、丁基、異丙基、第三丁基，更佳的是乙基、異丙基。 The alkyl group represented by R a is preferably a methyl group, an ethyl group, a butyl group, an isopropyl group or a tert-butyl group, more preferably an ethyl group or an isopropyl group.

於通式(II-7)或通式(II-8)中，Rb較佳的是2,6-二-第三丁基-4-甲基環己氧基羰基。 In the formula (II-7) or the formula (II-8), R b is preferably 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl.

於通式(II-7)或通式(II-8)中，Rd分別獨立地較佳的是烷基或芳基，更佳的是芳基。 In the formula (II-7) or the formula (II-8), R d is each independently preferably an alkyl group or an aryl group, more preferably an aryl group.

由Rd所表示之亦可具有取代基之烷基較佳的是二級烷基、三級烷基，更佳的是三級烷基，特佳的是第三丁基。由Rd所表示之芳基較佳的是苯基、甲苯基、二甲苯基或萘基，更佳的是甲苯基、苯基，特佳的是甲苯基。 The alkyl group which may have a substituent represented by R d is preferably a secondary alkyl group, a tertiary alkyl group, more preferably a tertiary alkyl group, and particularly preferably a tertiary butyl group. The aryl group represented by R d is preferably a phenyl group, a tolyl group, a xylyl group or a naphthyl group, more preferably a tolyl group or a phenyl group, and particularly preferably a tolyl group.

由Rd所表示之烯基較佳的是β-苯乙烯基。 The alkenyl group represented by R d is preferably a β-styryl group.

通式(II-7)或通式(II-8)中之Ma與通式(II-3)中之Ma同義，較佳之範圍亦相同。 Ma in the formula (II-7) or the formula (II-8) is synonymous with Ma in the formula (II-3), and the preferred range is also the same.

通式(II-7)或通式(II-8)中之Z1與通式(II-5)中之Z1同義，較佳之範圍亦相同。 Formula (II-7) or the general formula (II-8) Z 1 in the general formula (II-5) in the same meaning as Z 1, the preferred range is also the same.

通式(II)所表示之化合物特佳的是通式(II-9)所表示之化合物。 Particularly preferred of the compounds represented by the formula (II) are the compounds represented by the formula (II-9).

[化25] [化25]

通式(II-9)中，R30為包含氮原子之取代基，R31為取代基，R30與R31亦可相互鍵結而形成環。nd為0或1。另外，所述式中，「t-Bu」表示第三丁基。 In the formula (II-9), R 30 is a substituent containing a nitrogen atom, R 31 is a substituent, and R 30 and R 31 may be bonded to each other to form a ring. Nd is 0 or 1. Further, in the formula, "t-Bu" means a third butyl group.

以下表示本發明中所使用之通式(II)所表示之氮雜吡咯亞甲基金屬錯合物化合物之具體例，但不言而喻本申請發明並不限定於該些具體例。另外，下述化合物中之「t-Bu」表示第三丁基。 Specific examples of the azapyrrolemethylene metal complex compound represented by the formula (II) used in the present invention are shown below, but it is needless to say that the invention is not limited to the specific examples. Further, "t-Bu" in the following compounds means a third butyl group.

[化26] [Chem. 26]

[化27] [化27]

[化28] [化28]

[化29] [化29]

[化30] [化30]

[化31] [化31]

[化32] [化32]

[化33] [化33]

[化34] [化34]

[化35] [化35]

本發明之著色硬化性組成物可包含僅1種選自所述特定染料(A-1)及特定染料(A-2)之色素化合物，亦可包含2種以上。於包含2種以上之情形時，可包含2種以上特定染料(A-1)，亦可包含2種以上特定染料(A-2)，而且亦可包含特定染料(A-1)與特定染料(A-2)之雙方。 The colored curable composition of the present invention may contain only one kind of the dye compound selected from the specific dye (A-1) and the specific dye (A-2), and may contain two or more kinds. When two or more types are contained, two or more specific dyes (A-1) may be contained, or two or more specific dyes (A-2) may be contained, and a specific dye (A-1) and a specific dye may be contained. Both sides of (A-2).

作為本發明中所使用之選自(A-1)所述通式(I)所表示之結構配位於金屬或金屬化合物上而成的二吡咯亞甲 基金屬錯合物化合物及(A-2)所述通式(II)所表示之結構配位於金屬或金屬化合物上而成的氮雜吡咯亞甲基金屬錯合物化合物的色素化合物之含量，相對於著色硬化性組成物之總固形物而言，以質量基準計而言較佳的是0.2%~50%，更佳的是0.5%~30%。藉由設為該範圍，可獲得良好之色濃度(例如適於液晶顯示之色濃度)，特別是藉由設為30質量%以下，於畫素之圖案化變良好方面而言有利。 The dipyrromethene which is selected from (A-1), wherein the structure represented by the above formula (I) is bonded to a metal or a metal compound, which is used in the present invention. a base metal complex compound and (A-2) a content of a pigment compound of the azapyrrole methylene metal complex compound obtained by disposing the structure represented by the above formula (II) on a metal or a metal compound, The total solid content of the colored curable composition is preferably from 0.2% to 50%, more preferably from 0.5% to 30%, on a mass basis. By setting it as the range, a favorable color density (for example, a color density suitable for liquid crystal display) can be obtained, and it is advantageous in that the patterning of a pixel is favorable, especially when it is 30 mass % or less.

另外，於本發明中所謂著色硬化性組成物之總固形物是指自構成著色硬化性組成物之所有成分除去溶劑之成分的總合計量。 In addition, the total solid content of the coloring curable composition in the present invention means the total amount of components from which the solvent is removed from all the components constituting the colored curable composition.

(B)下述通式(III)所表示之卟啉化合物 (B) a porphyrin compound represented by the following formula (III)

本發明之著色硬化性組成物需要與特定染料(A)一同含有(B)下述通式(III)所表示之卟啉化合物(以下適宜稱為「卟啉化合物」或「特定染料(B)」)。 The colored curable composition of the present invention needs to contain (B) a porphyrin compound represented by the following formula (III) together with the specific dye (A) (hereinafter referred to as "porphyrin compound" or "specific dye (B)" ").

所述通式(III)中，Z1、Z2、Z3及Z4均表示N，或者Z1及Z3、以及Z2及Z4之任意一組均表示N，剩餘一組均表示C-R，R分別獨立地表示氫原子、烷基、或芳基。 In the general formula (III), Z 1 , Z 2 , Z 3 and Z 4 each represent N, or Z 1 and Z 3 , and any one of Z 2 and Z 4 represents N, and the remaining groups represent CR, R each independently represents a hydrogen atom, an alkyl group, or an aryl group.

A1、A2、A3、A4、A5、A6、A7及A8各自獨立地表示氫原子、烷基、烯基、芳基、烷氧基、烷硫基、芳氧基、芳硫基、鹵素原子、羥基、烷氧基羰基、芳氧基羰基、胺基、胺甲醯基、胺磺醯基、醯基、矽烷氧基、氰基、硝基、或雜環基。A1、A2、A3、A4、A5、A6、A7及A8亦可各自進一步具有取代基。 A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkylthio group or an aryloxy group. , arylthio group, halogen atom, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, amine group, amine mercapto group, amine sulfonyl group, decyl group, decyloxy group, cyano group, nitro group, or heterocyclic group . A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may each further have a substituent.

A1與A2、A3與A4、A5與A6、或A7與A8亦可各自相互鍵結而形成環結構，但至少一組為並不形成環結構之態樣。而且，於形成環結構之組中，較佳的是形成脂環結構而不形成芳香環結構，更佳的是A1與A2、A3與A4、A5與A6、及A7與A8之任意者均不形成環結構之態樣。 A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , or A 7 and A 8 may each be bonded to each other to form a ring structure, but at least one of them is a form which does not form a ring structure. Further, in the group forming the ring structure, it is preferred to form an alicyclic structure without forming an aromatic ring structure, and more preferably A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 Nothing with A 8 forms a ring structure.

M表示2價金屬原子、或者經取代之2價金屬原子或包含金屬原子之2價原子團。 M represents a divalent metal atom, or a substituted divalent metal atom or a divalent atomic group containing a metal atom.

本發明之著色硬化性組成物藉由含有所述特定染料(A-1)及特定染料(A-2)之至少1種與特定染料(B)，雖然理由尚不確定，但於使用所形成之著色硬化膜而構成彩色濾光片之情形時可有效地提高亮度與對比度。 The color hardening composition of the present invention contains at least one of the specific dye (A-1) and the specific dye (A-2) and the specific dye (B), although the reason is not certain, but is formed by use. When the color hardening film is formed to form a color filter, brightness and contrast can be effectively improved.

對通式(III)中之A1、A2、A3、A4、A5、A6、A7及A8所表示之取代基加以說明。 The substituents represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 in the formula (III) will be described.

通式(III)中之A1~A8之任意者獨立地表示的烷基可較佳地列舉碳數為1~48之直鏈、分支鏈、或環狀之烷 基，可更佳地列舉碳數為1~24之直鏈、分支鏈、或環狀之烷基。具體而言例如可列舉甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基、庚基、辛基、2-乙基己基、十二烷基、十六烷基、環丙基、環戊基、環己基、1-降莰基、1-金剛烷基等。烯基可較佳地列舉碳數為2~48之烯基，可更佳地列舉碳數為2~18之烯基。具體而言例如可列舉乙烯基、烯丙基、3-丁烯-1-基等。芳基可較佳地列舉碳數為6~48之芳基，可更佳地列舉碳數為6~24之芳基。具體而言例如可列舉苯基、萘基等。烷氧基可較佳地列舉碳數為1~48之烷氧基，可更佳地列舉碳數為1~24之烷氧基。具體而言例如可列舉甲氧基、乙氧基、1-丁氧基、2-丁氧基、異丙氧基、第三丁氧基、十二烷氧基等。而且，若為環烷氧基，例如可列舉環戊氧基、環己氧基等。烷硫基可較佳地列舉碳數為1~48之烷硫基，可更佳地列舉碳數為1~24之烷硫基。具體而言例如可列舉甲硫基、乙硫基、辛硫基、環己基硫基等。芳氧基可較佳地列舉碳數為6~48之芳氧基，可更佳地列舉碳數為6~24之芳氧基。具體而言例如可列舉苯氧基、1-萘氧基等。芳硫基可較佳地列舉碳數為6~48之芳硫基，可更佳地列舉碳數為6~24之芳硫基。具體而言例如可列舉苯硫基等。鹵素原子可較佳地列舉氟原子、氯原子、溴原子、碘原子。可較佳地列舉氟原子、氯原子、溴原子。烷氧基羰基可較佳地列舉碳數為2~48之烷氧基羰基，可更佳地列舉碳數為2~24之烷氧基羰基。具體而言例如可列舉甲氧基羰基、乙氧基 羰基、十八烷氧基羰基、環己氧基羰基、2,6-二-第三丁基-4-甲基環己氧基羰基等。 The alkyl group independently represented by any one of A 1 to A 8 in the formula (III) is preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 48, more preferably A straight chain, a branched chain, or a cyclic alkyl group having a carbon number of 1 to 24 is exemplified. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, and tenth Hexaalkyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl and the like. The alkenyl group is preferably an alkenyl group having 2 to 48 carbon atoms, and more preferably an alkenyl group having 2 to 18 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, and a 3-buten-1-yl group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, and more preferably an aryl group having 6 to 24 carbon atoms. Specific examples thereof include a phenyl group and a naphthyl group. The alkoxy group is preferably an alkoxy group having 1 to 48 carbon atoms, and more preferably an alkoxy group having 1 to 24 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a third butoxy group, and a dodecyloxy group. Further, examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. The alkylthio group is preferably an alkylthio group having 1 to 48 carbon atoms, and more preferably an alkylthio group having 1 to 24 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group. The aryloxy group is preferably an aryloxy group having 6 to 48 carbon atoms, and more preferably an aryloxy group having 6 to 24 carbon atoms. Specific examples thereof include a phenoxy group and a 1-naphthyloxy group. The arylthio group is preferably an arylthio group having 6 to 48 carbon atoms, and more preferably an arylthio group having 6 to 24 carbon atoms. Specific examples thereof include a phenylthio group and the like. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. A fluorine atom, a chlorine atom, and a bromine atom are preferably exemplified. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, and more preferably an alkoxycarbonyl group having 2 to 24 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, and the like. .

芳氧基羰基可較佳地列舉碳數為7~32之芳氧基羰基，可更佳地列舉碳數為7~24之芳氧基羰基。具體而言例如可列舉苯氧基羰基等。胺基可較佳地列舉碳數為32以下之胺基，可更佳地列舉碳數為24以下之胺基。具體而言例如可列舉胺基、甲基胺基、N,N-二丁基胺基、十四烷基胺基、2-乙基己基胺基、環己基胺基等。胺甲醯基可較佳地列舉碳數為1~48之胺甲醯基，可更佳地列舉碳數為1~24之胺甲醯基。具體而言例如可列舉胺甲醯基、N,N-二乙基胺甲醯基、N-乙基-N-辛基胺甲醯基、N,N-二丁基胺甲醯基、N-丙基胺甲醯基、N-苯基胺甲醯基、N-甲基-N-苯基胺甲醯基、N,N-二環己基胺甲醯基等。胺磺醯基可較佳地列舉碳數為32以下之胺磺醯基，可更佳地列舉碳數為24以下之胺磺醯基。具體而言例如可列舉胺磺醯基、N,N-二丙基胺磺醯基、N-乙基-N-十二烷基胺磺醯基、N-乙基-N-苯基胺磺醯基、N-環己基胺磺醯基等。醯基可較佳地列舉碳數為1~48之醯基，可更佳地列舉碳數為1~24之醯基。具體而言例如可列舉甲醯基、乙醯基、特戊醯基、苯甲醯基、十四醯基、環己醯基等。矽烷氧基可較佳地列舉碳數為1~32之矽烷氧基、可更佳地列舉碳數為1~18之矽烷氧基。具體而言例如可列舉三甲基矽烷基氧基、第三丁基二甲基矽烷氧基、二苯基甲基矽烷氧基等。雜環基可較佳地列舉碳數為1~32之雜環基，可更佳地列舉碳數為1~ 18之雜環基。具體而言例如可列舉2-噻吩基、4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、苯并***-1-基等。 The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, and more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms. Specific examples thereof include a phenoxycarbonyl group and the like. The amine group is preferably an amine group having a carbon number of 32 or less, and more preferably an amine group having a carbon number of 24 or less. Specific examples thereof include an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group, and the like. The amine formamidine group is preferably an amine formamidine group having 1 to 48 carbon atoms, and more preferably an amine formamidine group having 1 to 24 carbon atoms. Specific examples thereof include an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, an N-ethyl-N-octylamine methyl fluorenyl group, an N,N-dibutylamine methyl fluorenyl group, and N. - propylamine methyl sulfhydryl group, N-phenylamine methyl hydrazino group, N-methyl-N-phenylamine methyl hydrazino group, N,N-dicyclohexylamine carbaryl group, and the like. The aminesulfonyl group is preferably an aminesulfonyl group having a carbon number of 32 or less, and more preferably an aminesulfonyl group having a carbon number of 24 or less. Specific examples thereof include aminesulfonyl, N,N-dipropylaminesulfonyl, N-ethyl-N-dodecylaminesulfonyl, and N-ethyl-N-phenylaminesulfonate. Mercapto group, N-cyclohexylamine sulfonyl group, and the like. The mercapto group is preferably a mercapto group having a carbon number of from 1 to 48, and more preferably a mercapto group having a carbon number of from 1 to 24. Specific examples thereof include a methyl group, an ethenyl group, a pentylene group, a benzamidine group, a tetradecyl group, a cyclohexyl group, and the like. The decyloxy group is preferably a decyloxy group having 1 to 32 carbon atoms, more preferably a decyloxy group having 1 to 18 carbon atoms. Specific examples thereof include a trimethylsilyloxy group, a tert-butyldimethylstannoxy group, and a diphenylmethyldecyloxy group. The heterocyclic group is preferably a heterocyclic group having 1 to 32 carbon atoms, and more preferably a carbon number of 1~. 18 heterocyclic groups. Specific examples thereof include 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, and benzene. And triazol-1-yl and the like.

該些A1、A2、A3、A4、A5、A6、A7及A8所表示之取代基亦可各自被進一步取代。可導入之取代基例如可列舉鹵素原子(例如氟原子、氯原子、溴原子等)、烷基(可較佳地列舉碳數為1~48之直鏈、分支鏈、或環狀之烷基，可更佳地列舉碳數為1~24之直鏈、分支鏈、或環狀之烷基。具體而言例如可列舉甲基、乙基、丙基、異丙基、丁基、第三丁基、戊基、己基、庚基、辛基、2-乙基己基、十二烷基、十六烷基、環丙基、環戊基、環己基、1-降莰基、1-金剛烷基等)、烯基(可較佳地列舉碳數為2~48之烯基，可更佳地列舉碳數為2~18之烯基。具體而言例如可列舉乙烯基、烯丙基、3-丁烯-1-基等)、芳基(可較佳地列舉碳數為6~48之芳基，可更佳地列舉碳數為6~24之芳基。具體而言例如可列舉苯基、萘基等)、雜環基(可較佳地列舉碳數為1~32之雜環基，可更佳地列舉碳數為1~18之雜環基。具體而言例如可列舉2-噻吩基、4-吡啶基、2-呋喃基、2-嘧啶基、1-吡啶基、2-苯并噻唑基、1-咪唑基、1-吡唑基、苯并***-1-基等)、矽烷基(可較佳地列舉碳數為3~38之矽烷基，可更佳地列舉碳數為3~18之矽烷基。具體而言例如可列舉三甲基矽烷基、三乙基矽烷基、三丁基矽烷基、第三丁基二甲基矽烷基、第三己基二甲基矽烷基等)、羥基、氰基、硝基、 烷氧基(可較佳地列舉碳數為1~48之烷氧基，可更佳地列舉碳數為1~24之烷氧基。具體而言例如可列舉甲氧基、乙氧基、1-丁氧基、2-丁氧基、異丙氧基、第三丁氧基、十二烷氧基、及環戊氧基或環己氧基等環烷氧基)、芳氧基(可較佳地列舉碳數為6~48之芳氧基，可更佳地列舉碳數為6~24之芳氧基。具體而言例如可列舉苯氧基、1-萘氧基等)、雜環氧基(可較佳地列舉碳數為1~32之雜環氧基，可更佳地列舉碳數為1~18之雜環氧基。具體而言例如可列舉1-苯基四唑-5-氧基、2-四氫吡喃基氧基等)、矽烷氧基(可較佳地列舉碳數為1~32之矽烷氧基，可更佳地列舉碳數為1~18之矽烷氧基。具體而言例如可列舉三甲基矽烷基氧基、第三丁基二甲基矽烷氧基、二苯基甲基矽烷氧基等)、醯氧基(可較佳地列舉碳數為2~48之醯氧基，可更佳地列舉碳數為2~24之醯氧基。具體而言例如可列舉乙醯氧基、特戊醯氧基、苯甲醯氧基、十二醯氧基等)、烷氧基羰氧基(可較佳地列舉碳數為2~48之烷氧基羰氧基，可更佳地列舉碳數為2~24之烷氧基羰氧基。具體而言例如可列舉乙氧基羰氧基、第三丁氧基羰氧基、及環己氧基羰氧基等環烷氧基羰氧基)、芳氧基羰氧基(可較佳地列舉碳數為7~32之芳氧基羰氧基，可更佳地列舉碳數為7~24之芳氧基羰氧基。具體而言例如可列舉苯氧基羰氧基等)、胺甲醯基氧基(可較佳地列舉碳數為1~48之胺甲醯基氧基，更佳的是碳數為1~24之胺甲醯基氧基。具體而言例如可列舉N,N-二甲基胺甲醯基氧基、 N-丁基胺甲醯基氧基、N-苯基胺甲醯基氧基、N-乙基-N-苯基胺甲醯基氧基等)、胺磺醯基氧基(可較佳地列舉碳數為1~32之胺磺醯基氧基，可更佳地列舉碳數為1~24之胺磺醯基氧基。具體而言例如可列舉N,N-二乙基胺磺醯基氧基、N-丙基胺磺醯基氧基等)、烷基磺醯氧基(可較佳地列舉碳數為1~38之烷基磺醯氧基，可更佳地列舉碳數為1~24之烷基磺醯氧基，具體而言例如為甲基磺醯氧基、十六烷基磺醯氧基、環己基磺醯氧基等)、芳基磺醯氧基(可較佳地列舉碳數為6~32之芳基磺醯氧基，可更佳地列舉碳數為6~24之芳基磺醯氧基，具體而言例如為苯基磺醯氧基等)、醯基(較佳的是碳數為1~48之醯基，更佳的是碳數為1~24之醯基，例如可列舉甲醯基、乙醯基、特戊醯基、苯甲醯基、十四醯基、環己醯基)、烷氧基羰基(可較佳地列舉碳數為2~48之烷氧基羰基，可更佳地列舉碳數為2~24之烷氧基羰基。具體而言例如可列舉甲氧基羰基、乙氧基羰基、十八烷氧基羰基、環己氧基羰基、2,6-二-第三丁基-4-甲基環己氧基羰基等)、芳氧基羰基(可較佳地列舉碳數為7~32之芳氧基羰基，可更佳地列舉碳數為7~24之芳氧基羰基。具體而言例如可列舉苯氧基羰基等)、胺甲醯基(可較佳地列舉碳數為1~48之胺甲醯基，可更佳地列舉碳數為1~24之胺甲醯基。具體而言例如可列舉胺甲醯基、N,N-二乙基胺甲醯基、N-乙基-N-辛基胺甲醯基、N,N-二丁基胺甲醯基、N-丙基胺甲醯基、N-苯基胺 甲醯基、N-甲基-N-苯基胺甲醯基、N,N-二環己基胺甲醯基等)、胺基(可較佳地列舉碳數為32以下之胺基，可更佳地列舉碳數為24以下之胺基。具體而言例如可列舉胺基、甲基胺基、N,N-二丁基胺基、十四烷基胺基、2-乙基己基胺基、環己基胺基等)、苯胺基(可較佳地列舉碳數為6~32之苯胺基，可更佳地列舉碳數為6~24之苯胺基。具體而言例如可列舉苯胺基、N-甲基苯胺基等)、雜環胺基(可較佳地列舉碳數為1~32之雜環胺基，可更佳地列舉碳數為1~18之雜環胺基。具體而言例如可列舉4-吡啶基胺基等)、羧醯胺(可較佳地列舉碳數為2~48之羧醯胺，可更佳地列舉碳數為2~24之羧醯胺。具體而言例如可列舉乙醯胺基、苯甲醯胺基、十四烷醯胺基、特戊醯基醯胺基、環己醯胺基等)、脲基(可較佳地列舉碳數為1~32之脲基，可更佳地列舉碳數為1~24之脲基。具體而言例如可列舉脲基、N,N-二甲基脲基、N-苯基脲基等)、醯亞胺基(可較佳地列舉碳數為36以下之醯亞胺基，可更佳地列舉碳數為24以下之醯亞胺基。具體而言例如可列舉N-琥珀醯亞胺基、N-鄰苯二甲醯亞胺基等)、烷氧基羰基胺基(可較佳地列舉碳數為2~48之烷氧基羰基胺基，可更佳地列舉碳數為2~24之烷氧基羰基胺基。具體而言例如可列舉甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、十八烷氧基羰基胺基、環己氧基羰基胺基等)、芳氧基羰基胺基(可較佳地列舉碳數為7~32之芳氧基羰基胺基，可更佳地列舉碳數為7~24之芳氧基羰基胺基。具體而言例 如可列舉苯氧基羰基胺基等)、磺醯胺基(可較佳地列舉碳數為1~48之磺醯胺基，可更佳地列舉碳數為1~24之磺醯胺基。具體而言例如可列舉甲基磺醯胺基、丁基磺醯胺基、苯磺醯胺基、十六烷基磺醯胺基、環己基磺醯胺基等)、胺磺醯胺基(可較佳地列舉碳數為1~48之胺磺醯胺基，可更佳地列舉碳數為1~24之胺磺醯胺基。具體而言例如可列舉N,N-二丙基胺磺醯胺基、N-乙基-N-十二烷基胺磺醯胺基等)、偶氮基(可較佳地列舉碳數為1~32之偶氮基，可更佳地列舉碳數為1~24之偶氮基。具體而言例如可列舉苯基偶氮基、3-吡唑基偶氮基等)、烷硫基(可較佳地列舉碳數為1~48之烷硫基，可更佳地列舉碳數為1~24之烷硫基。具體而言例如可列舉甲硫基、乙硫基、辛硫基、環己硫基等)、芳硫基(可較佳地列舉碳數為6~48之芳硫基，可更佳地列舉碳數為6~24之芳硫基。具體而言例如可列舉苯硫基等)、雜環硫基(可較佳地列舉碳數為1~32之雜環硫基，可更佳地列舉碳數為1~18之雜環硫基。具體而言例如可列舉2-苯并噻唑基硫基、2-吡啶基硫基、1-苯基四唑基硫基等)、烷基亞磺醯基(可較佳地列舉碳數為1~32之烷基亞磺醯基，可更佳地列舉碳數為1~24之烷基亞磺醯基。具體而言例如可列舉十二烷基亞磺醯基等)、芳基亞磺醯基(可較佳地列舉碳數為6~32之芳基亞磺醯基，可更佳地列舉碳數為6~24之芳基亞磺醯基。具體而言例如可列舉苯基亞磺醯基等)、烷基磺醯基(可較佳地列舉碳數為1~48之烷基磺醯基， 可更佳地列舉碳數為1~24之烷基磺醯基。具體而言例如可列舉甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、異丙基磺醯基、2-乙基己基磺醯基、十六烷基磺醯基、辛基磺醯基、環己基磺醯基等)、芳基磺醯基(可較佳地列舉碳數為6~48之芳基磺醯基，可更佳地列舉碳數為6~24之芳基磺醯基。具體而言例如可列舉苯基磺醯基、1-萘基磺醯基等)、胺磺醯基(可較佳地列舉碳數為32以下之胺磺醯基，可更佳地列舉碳數為24以下之胺磺醯基。具體而言例如可列舉胺磺醯基、N,N-二丙基胺磺醯基、N-乙基-N-十二烷基胺磺醯基、N-乙基-N-苯基胺磺醯基、N-環己基胺磺醯基等)、磺基、膦醯基(可較佳地列舉碳數為1~32之膦醯基，可更佳地列舉碳數為1~24之膦醯基。具體而言例如可列舉苯氧基膦醯基、辛氧基膦醯基、苯基膦醯基等)、膦醯基胺基(可較佳地列舉碳數為1~32之膦醯基胺基，可更佳地列舉碳數為1~24之膦醯基胺基。具體而言例如可列舉二乙氧基膦醯基胺基、二辛氧基膦醯基胺基等)。 The substituents represented by these A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may each be further substituted. Examples of the substituent which can be introduced include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) and an alkyl group (a linear, branched or cyclic alkyl group having a carbon number of 1 to 48 is preferably used. More preferably, it is a linear, branched or cyclic alkyl group having a carbon number of 1 to 24. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a third group. Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-gold An alkyl group or the like, an alkenyl group (preferably, an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms. Specific examples thereof include a vinyl group and an allyl group. , 3-buten-1-yl, etc.), aryl (preferably, an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms. Specifically, for example, Examples thereof include a phenyl group, a naphthyl group, and the like, and a heterocyclic group (a heterocyclic group having 1 to 32 carbon atoms is preferable, and a heterocyclic group having 1 to 18 carbon atoms is more preferable. Specifically, for example, Listed 2-thiophenyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridine , 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl, etc., decylalkyl (preferably exemplified by a decyl group having a carbon number of 3 to 38) Preferred examples thereof include a decyl group having a carbon number of 3 to 18. Specific examples thereof include a trimethyl decyl group, a triethyl decyl group, a tributyl decyl group, a tert-butyl dimethyl decyl group, and a third hexyl group. a dimethyl group or the like, a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably, an alkoxy group having a carbon number of 1 to 48, more preferably an alkoxy group having a carbon number of 1 to 24) Specific examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a third butoxy group, a dodecyloxy group, and a cyclopentyloxy group. Or a cycloalkoxy group such as a cyclohexyloxy group or an aryloxy group (preferably, an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms. Examples thereof include a phenoxy group and a 1-naphthyloxy group, and a heterocyclic oxy group (preferably, a heterocyclic oxy group having 1 to 32 carbon atoms, and more preferably a carbon number of 1 to 18). Specific examples of the heterocyclic oxy group include a 1-phenyltetrazole-5-oxy group, a 2-tetrahydropyranyloxy group, and the like. The decyloxy group ( preferably a decyloxy group having 1 to 32 carbon atoms, more preferably a decyloxy group having 1 to 18 carbon atoms. Specific examples thereof include a trimethyl decyloxy group, a third butyl dimethyl decyloxy group, a diphenylmethyl decyloxy group or the like, or a decyloxy group (preferably, a decyloxy group having a carbon number of 2 to 48, more preferably a carbon number of Examples of the fluorenyloxy group of 2 to 24, and specific examples thereof include an ethoxycarbonyl group, a pentyleneoxy group, a benzamidineoxy group, a dodecyloxy group, and the like, and an alkoxycarbonyloxy group (preferably, The alkoxycarbonyloxy group having a carbon number of 2 to 48 is more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms. Specific examples thereof include an ethoxycarbonyloxy group and a third butyl group. An oxycarbonyloxy group, a cycloalkoxycarbonyloxy group such as a cyclohexyloxycarbonyloxy group, or an aryloxycarbonyloxy group (preferably, an aryloxycarbonyloxy group having a carbon number of 7 to 32, More preferably, an aryloxycarbonyloxy group having a carbon number of 7 to 24 can be cited. Specific examples thereof include an phenoxycarbonyloxy group and the like, and an aminomethylcarbonyloxy group (preferably, an amine carbenyloxy group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 2). An amine carbenyloxy group of 24, and specific examples thereof include N,N-dimethylamine-mercaptooxy group, N-butylamine-mercaptooxy group, and N-phenylamine-mercaptooxy group. , N-ethyl-N-phenylamine methyl decyloxy group, etc., and amine sulfonyloxy group (highly exemplified by the amine sulfonyloxy group having 1 to 32 carbon atoms, more preferably listed The sulfonyloxy group having 1 to 24 carbon atoms, and specific examples thereof include N,N-diethylamine sulfonyloxy group, N-propylamine sulfonyloxy group, and the like, and alkyl sulfonate. The decyloxy group (preferably, the alkylsulfonyloxy group having a carbon number of 1 to 38, more preferably an alkylsulfonyloxy group having a carbon number of 1 to 24, specifically, for example, methylsulfonate An alkoxysulfonyloxy group (an aryloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, etc.), and an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably Preferably, the arylsulfonyloxy group having a carbon number of 6 to 24, specifically, for example, a phenylsulfonyloxy group or the like, or a mercapto group (preferably having a carbon number of 1 to 48) More preferably, it is a fluorenyl group having a carbon number of 1 to 24, and examples thereof include a methyl group, an ethyl group, a pentylene group, a benzamidine group, a tetradecyl group, a cyclohexyl group, and an alkoxy group. The carbonyl group (preferably, the alkoxycarbonyl group having a carbon number of 2 to 48, more preferably an alkoxycarbonyl group having 2 to 24 carbon atoms. Specific examples thereof include a methoxycarbonyl group and an ethoxy group. a carbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, or the like), an aryloxycarbonyl group (a preferred number of carbon atoms) The aryloxycarbonyl group having 7 to 32 is more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms. Specific examples thereof include a phenoxycarbonyl group and the like, and an aminomethyl sulfonyl group (preferably, The amine carbenyl group having a carbon number of 1 to 48 may be more preferably an amine carbenyl group having a carbon number of 1 to 24. Specifically, for example, an aminomethyl group and an N,N-diethylamine formamidine may be mentioned. Base, N-ethyl-N-octylaminecarbamyl, N,N-dibutylaminecarbamyl, N-propylaminecarbamyl, N-phenylaminecarbamyl, N-methyl -N-phenylamine-methyl hydrazino group, N,N-dicyclohexylamine carbhydryl group, etc.), an amine group (it is preferable to exemplify an amine group having a carbon number of 32 or less) More preferably, an amine group having a carbon number of 24 or less can be cited. Specific examples thereof include an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, and a 2-ethylhexyl group. An amine group, a cyclohexylamino group, or the like, and an anilino group (an anilino group having a carbon number of 6 to 32 is preferable, and an anilino group having a carbon number of 6 to 24 is more preferable. Specific examples thereof include an aniline. A heterocyclic amino group having a carbon number of from 1 to 32, more preferably a heterocyclic amino group having a carbon number of from 1 to 18, more preferably a heterocyclic amino group. Specific examples thereof include a 4-pyridylamino group and the like, and a carboxamide (a carboxamide having a carbon number of 2 to 48 is preferable, and a carboxamide having a carbon number of 2 to 24 is more preferably used. Specific examples thereof include an acetamino group, a benzylideneamine group, a tetradecylguanidinium group, a pentyl decylamino group, a cyclohexylamino group, and the like, and a urea group (a carbon is preferably exemplified). The ureido group having a number of from 1 to 32, more preferably a ureido group having a carbon number of from 1 to 24. Specific examples thereof include a ureido group, an N,N-dimethylureido group, and an N-phenylureido group, and a quinone imine group (a quinone imine group having a carbon number of 36 or less is preferably used, and More preferably, the quinone imine group having a carbon number of 24 or less is specifically, for example, an N-succinimide group or an N-phthalimido group, or an alkoxycarbonylamino group. The alkoxycarbonylamino group having 2 to 48 carbon atoms is preferred, and the alkoxycarbonylamino group having 2 to 24 carbon atoms is more preferably used. Specific examples thereof include a methoxycarbonylamino group. Ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc.), aryloxycarbonylamino group (higher preferred is carbon number) The aryloxycarbonylamino group of 7 to 32 may more preferably be an aryloxycarbonylamino group having 7 to 24 carbon atoms. Specific examples thereof include a phenoxycarbonylamino group and the like, and a sulfonylamino group (for example) The sulfonamide group having a carbon number of 1 to 48 is preferably exemplified, and a sulfonylamino group having 1 to 24 carbon atoms is more preferable. Specific examples thereof include methylsulfonamide and butylsulfonate. Amidino, benzenesulfonamide, cetylsulfonamide , cyclohexylsulfonylamino group, etc.), sulfonamide group (highly exemplified by the amine sulfonamide group having a carbon number of 1 to 48, more preferably a sulfonamide having a carbon number of 1 to 24; Specific examples thereof include N,N-dipropylaminesulfonylamino group, N-ethyl-N-dodecylaminesulfonylamino group, and the like, and an azo group (preferably, carbon is mentioned). The azo group having a number of 1 to 32, more preferably an azo group having 1 to 24 carbon atoms, specifically, for example, a phenylazo group or a 3-pyrazolylazo group, or an alkane The thio group (preferably, an alkylthio group having a carbon number of 1 to 48, more preferably an alkylthio group having 1 to 24 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, and a octyl group. Sulfhydryl, cyclohexylthio, etc.), arylthio group (preferably, an arylthio group having a carbon number of 6 to 48, more preferably an arylthio group having a carbon number of 6 to 24. Specifically, for example The phenylthio group may, for example, be a heterocyclic thio group (preferably, a heterocyclic thio group having 1 to 32 carbon atoms, and more preferably a heterocyclic thio group having 1 to 18 carbon atoms. For example, a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group, etc., an alkylsulfinyl group may be mentioned. The alkylsulfinyl group having 1 to 32 carbon atoms is exemplified, and more preferably, the alkylsulfinyl group having 1 to 24 carbon atoms is used. Specific examples thereof include dodecylsulfinyl group and the like. An arylsulfinyl group (preferably, an arylsulfinyl group having a carbon number of 6 to 32, more preferably an arylsulfinyl group having a carbon number of 6 to 24. Specifically, for example Examples thereof include a phenylsulfinyl group and the like, and an alkylsulfonyl group ( preferably an alkylsulfonyl group having 1 to 48 carbon atoms, and more preferably an alkylsulfonate having 1 to 24 carbon atoms. The mercapto group. Specific examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, and ten. a hexaalkylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group, or the like, an arylsulfonyl group (preferably, an arylsulfonyl group having a carbon number of 6 to 48, more preferably listed An arylsulfonyl group having a carbon number of 6 to 24. Specific examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group, and an aminesulfonyl group (aminosulfonyl group having a carbon number of 32 or less is preferable, and a carbon number can be more preferably listed. It is an aminoxime group of 24 or less. Specific examples thereof include an amine sulfonyl group, an N,N-dipropylamine sulfonyl group, an N-ethyl-N-dodecylamamine sulfonyl group, and N- Ethyl-N-phenylamine sulfonyl group, N-cyclohexylamine sulfonyl group, etc.), sulfo group, phosphinium group (preferably, a phosphinium group having a carbon number of 1 to 32, more preferably Examples of the phosphinium group having a carbon number of 1 to 24, and specific examples thereof include a phenoxyphosphonium group, an octyloxyphosphonium group, a phenylphosphonium group, and the like, and a phosphinium group (preferably, The phosphinylamino group having a carbon number of 1 to 32 is more preferably a phosphinylamino group having 1 to 24 carbon atoms. Specific examples thereof include diethoxyphosphonium amide group and dioctyl group. Oxyphosphinoguanidinoamine, etc.).

Z1、Z2、Z3或Z4所表示之C-R中，R所表示之烷基及芳基與作為A1、A2、A3、A4、A5、A6、A7及A8所表示之取代基而說明的烷基及芳基同義。 In the CR represented by Z 1 , Z 2 , Z 3 or Z 4 , the alkyl group and the aryl group represented by R are as A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A The alkyl group and the aryl group described by the substituent represented by 8 are synonymous.

M所表示之金屬原子較佳的是表示Al、Si、Ca、Ti、V、Mn、Fe、Co、Ni、Cu、Zn、Ge、Mo、Ru、Rh、Pd、In、Sn、Pt、Pb、Mg，更佳的是表示Al、V、Mn、Fe、Co、Ni、Cu、Zn、Ru、Rh、Pd、Pt、Mg，進一步更佳的 是表示Al、V、Mn、Fe、Co、Ni、Cu、Zn、Mg，特佳的是表示V、Co、Ni、Cu、Zn。 The metal atom represented by M preferably represents Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb. And Mg, more preferably, represents Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Mg, and further preferably It is represented by Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Mg, and particularly preferably represents V, Co, Ni, Cu, and Zn.

M所表示之經取代之2價金屬原子或包含金屬原子之2價原子團之情形時的具體例可列舉鹵化金屬原子(例如Al-F、Al-Cl、Al-Br、Al-I、In-F、In-Cl、Fe-Cl、In-Br、In-I、SiF2、SiCl2、SiBr2、SiI2、TiF2、TiCl2、TiBr2、TiI2等)、M-B(B為烷基、芳基、萘基、烷氧基、羥基等取代基，具體而言例如為Si(CH3)3、Si(C2H5)3、Al-C6H5、In-C6H5、Al(OH)、Mn(OH)、Si(OH)2、Zr(OH)2、Al-OCH3、Al-O(C6H5)等)、金屬氧化物(例如TiO、MnO、VO等)。 Specific examples of the case of the substituted divalent metal atom represented by M or a divalent atomic group containing a metal atom include a halogenated metal atom (for example, Al-F, Al-Cl, Al-Br, Al-I, In-). F, In-Cl, Fe- Cl, In-Br, In-I, SiF 2, SiCl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 , etc.), MB (B is an alkyl group a substituent such as an aryl group, a naphthyl group, an alkoxy group or a hydroxyl group, and specifically, for example, Si(CH 3 ) 3 , Si(C 2 H 5 ) 3 , Al-C 6 H 5 , In-C 6 H 5 , Al(OH), Mn(OH), Si(OH) 2 , Zr(OH) 2 , Al-OCH 3 , Al-O(C 6 H 5 ), etc., metal oxides (eg TiO, MnO, VO) Wait).

本發明中所使用之卟啉化合物較佳的是Z1、Z2、Z3及Z4均表示N之四氮雜卟啉化合物，可較佳地列舉通式(III-2)所表示之化合物。 The porphyrin compound used in the present invention preferably has a nitrozaporphyrin compound in which Z 1 , Z 2 , Z 3 and Z 4 each represent N, and is preferably represented by the formula (III-2). Compound.

所述通式(III-2)中，A1、A2、A3、A4、A5、A6、A7、 A8及M與通式(III)中之A1、A2、A3、A4、A5、A6、A7、A8及M各自同義。 In the above formula (III-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M and A 1 and A 2 in the formula (III), A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are each synonymous.

作為本發明中所使用之通式(III)所表示之化合物之吸收光譜之最大值，自所形成之彩色濾光片之透射率之觀點考慮，較佳的是550nm至650nm，更佳的是570nm至630nm，特佳的是570nm至610nm。 The maximum value of the absorption spectrum of the compound represented by the formula (III) used in the present invention is preferably 550 nm to 650 nm from the viewpoint of the transmittance of the formed color filter, and more preferably 570 nm to 630 nm, particularly preferably 570 nm to 610 nm.

以下表示本發明中之特定染料(B)之具體例。但於本發明中並不限制於該些具體例。 Specific examples of the specific dye (B) in the present invention are shown below. However, the specific examples are not limited in the present invention.

另外，關於以下所例示之化合物的異構體，並未註明記述，但實際上如下所述地使二氰基乙烯化合物與金屬鹽反應而使其環化，因此如以下之流程所示那樣，於各個例示化合物中存在4種異構體，成為該些異構體之混合物。 Further, the isomers of the compounds exemplified below are not described, but actually, the dicyanoethene compound is reacted with a metal salt to cyclize as follows, as shown in the following scheme. Four isomers are present in each of the exemplified compounds to form a mixture of such isomers.

而且，於具體例中，R表示氫原子、烷基、烯基、芳基、烷氧基、烷硫基、芳氧基、芳硫基、鹵素原子、羥基、烷氧基羰基、芳氧基羰基、胺基、胺甲醯基、胺磺醯基、醯基、矽烷氧基、氰基、硝基、或雜環基，D1表示於卟啉骨架上之鍵結位置。 Further, in a specific example, R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a halogen atom, a hydroxyl group, an alkoxycarbonyl group, or an aryloxy group. A carbonyl group, an amine group, an amine carbenyl group, an amine sulfonyl group, a decyl group, a decyloxy group, a cyano group, a nitro group, or a heterocyclic group, and D1 represents a bonding position on a porphyrin skeleton.

而且，於下述具體例中，「t-Bu」表示第三丁基，「Me」表示甲基，「Et」表示乙基，「Pr」表示丙基，「Ph」表示苯基。 Further, in the following specific examples, "t-Bu" represents a third butyl group, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, and "Ph" represents a phenyl group.

[化38] [化38]

所述流程中之X1、X2、X3、X4、Y1、Y2、Y3、及Y4分別與通式(III)中之A1至A8中所說明之基同義，於X1與Y1、X2與Y2、X3與Y3、X4與Y4不同之情形時，可形成上述4種異構體。 X 1 , X 2 , X 3 , X 4 , Y 1 , Y 2 , Y 3 , and Y 4 in the scheme are synonymous with the groups described in A 1 to A 8 in the formula (III), respectively. When X 1 and Y 1 , X 2 and Y 2 , X 3 and Y 3 , and X 4 and Y 4 are different, the above four isomers can be formed.

[化39] [39]

[化40] [化40]

[化41] [化41]

[化42] [化42]

[化43] [化43]

[化44] [化44]

[化45] [化45]

[化46] [Chem. 46]

[化47] [化47]

[化48] [48]

[化49] [化49]

[化50] [化50]

[化51] [化51]

[化52] [化52]

[化53] [化53]

作為所述(B)通式(III)所表示之卟啉化合物之含量，較佳的是相對於著色硬化性組成物中所含之著色化合物之總量而言包含0.1質量%以上，更佳的是0.5質量%以上，特佳的是1質量%以上。本發明之卟啉化合物即使是微量使用亦可於製成彩色濾光片時獲得良好之色度、對比度，因此成本降低效果優異。所使用之濃度之上限若為適合製成彩色濾光片時之色度要求或抗蝕劑性能等用戶之要求者，則並無特別限定，若考慮與所述(A)二吡咯亞甲基金屬錯合物化合物及氮雜吡咯亞甲基金屬錯合物化合物之平衡，則較佳的是相對於著色化合物之總量而言為50質量%以下。 The content of the porphyrin compound represented by the above formula (B) is preferably 0.1% by mass or more, more preferably the total amount of the coloring compound contained in the colored curable composition. It is 0.5% by mass or more, and particularly preferably 1% by mass or more. The porphyrin compound of the present invention can obtain good chromaticity and contrast even when used in a small amount of a color filter, and therefore has an excellent cost reduction effect. The upper limit of the concentration to be used is not particularly limited as long as it is suitable for the user of the color filter or the resist performance when the color filter is formed, and the (A) dipyrromethene is considered. The balance between the metal complex compound and the azapyrrole methylene metal complex compound is preferably 50% by mass or less based on the total amount of the coloring compound.

其他染料 Other dyes

於本發明之著色硬化性組成物中亦可包含所述二吡咯亞甲基金屬錯合物化合物及氮雜吡咯亞甲基金屬錯合物化 合物以外之公知之染料。 The dipyrromethene metal complex compound and the azapyrromethene metal complex compound may also be contained in the color hardening composition of the present invention. A well-known dye other than the compound.

本發明之著色硬化性組成物中所亦可包含之其他染料是吡唑偶氮系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、蒽吡啶酮系、苯亞甲基系、氧喏系、吡唑并***偶氮系、吡啶酮偶氮系、花菁系、啡噻嗪系、吡咯并吡唑次甲基偶氮系、二苯并哌喃系、方酸菁系、酞菁系、苯並吡喃系、靛藍系等染料。 Other dyes which may be contained in the colored curable composition of the present invention are pyrazo azo type, anilino azo type, triphenylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, Oxygen oxime, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole methine, dibenzopyran, squaraine , phthalocyanine, benzopyran, indigo and other dyes.

作為本發明之著色硬化性組成物中所亦可包含之其他染料之具體例，例如為日本專利特開昭64-90403號公報、日本專利特開昭64-91102號公報、日本專利特開平1-94301號公報、日本專利特開平6-11614號公報、日本專利特登2592207號、美國專利第4,808,501號說明書、美國專利第5,667,920號說明書、美國專利第5,059,500號說明書、日本專利特開平5-333207號公報、日本專利特開平6-35183號公報、日本專利特開平6-51115號公報、日本專利特開平6-194828號公報、日本專利特開平8-211599號公報、日本專利特開平4-249549號公報、日本專利特開平10-123316號公報、日本專利特開平11-302283號公報、日本專利特開平7-286107號公報、日本專利特開2001-4823號公報、日本專利特開平8-15522號公報、日本專利特開平8-29771號公報、日本專利特開平8-146215號公報、日本專利特開平11-343437號公報、日本專利特開平8-62416號公報、日本專利特開2002-14220號公報、日本專利特開2002-14221號公報、日本專利特開2002-14222號公報、日 本專利特開2002-14223號公報、日本專利特開平8-302224號公報、日本專利特開平8-73758號公報、日本專利特開平8-179120號公報、日本專利特開平8-151531號公報、日本專利特開平6-230210號公報等中所記載之染料。 Specific examples of other dyes which may be included in the colored curable composition of the present invention are disclosed in Japanese Laid-Open Patent Publication No. SHO-64-90403, Japanese Patent Laid-Open No. Hei 64-91102, and Japanese Patent Laid-Open No. Hei. 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. No. Hei. Japanese Laid-Open Patent Publication No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115, Japanese Patent Laid-Open No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Hei. Hei. Hei. Japanese Patent Laid-Open No. Hei 8--29771, Japanese Patent Laid-Open No. Hei 8-146215, Japanese Patent Laid-Open No. Hei 11-343437, Japanese Patent Laid-Open No. 8-62416 and Japanese Unexamined Patent Publication No. 2002-14220, Japanese Unexamined Patent Publication No. 2002-14221, Japanese Unexamined Patent Publication No. 2002-14222 Gazette, Japan Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 8-. A dye described in Japanese Laid-Open Patent Publication No. Hei 6-230210 or the like.

(顏料) (pigment)

本發明之著色硬化性組成物中亦可併用顏料作為著色化合物。 In the color hardening composition of the present invention, a pigment may be used in combination as a coloring compound.

顏料較佳的是平均一次粒徑為10nm以上30nm以下之顏料。若為上述態樣，則獲得可構成亮度與對比度優異之彩色濾光片的著色硬化性組成物。 The pigment is preferably a pigment having an average primary particle diameter of 10 nm or more and 30 nm or less. In the above aspect, a color hardening composition which can constitute a color filter excellent in brightness and contrast is obtained.

顏料可使用先前公知之各自無機顏料或有機顏料，但於可靠性之觀點考慮，較佳的是使用有機顏料。於本發明中，有機顏料例如可列舉日本專利特開2009-256572號公報之段落[0093]中所記載之有機顏料。 As the pigment, each of the previously known respective inorganic pigments or organic pigments can be used, but from the viewpoint of reliability, it is preferred to use an organic pigment. In the present invention, the organic pigment is exemplified by the organic pigment described in paragraph [0093] of JP-A-2009-256572.

而且，特別是以下所示之顏料於顏色再現性之觀點而言適宜，但於本發明中並不限定於該些顏料。該些有機顏料可單獨使用，或者亦可為了提高色純度而加以各自組合而使用。 Further, in particular, the pigments shown below are suitable from the viewpoint of color reproducibility, but are not limited to the pigments in the present invention. These organic pigments may be used singly or in combination for the purpose of improving the color purity.

C.I.顏料紅177、224、242、254、255、264 C.I. Pigment Red 177, 224, 242, 254, 255, 264

C.I.顏料黃138、139、150、180、185 C.I. Pigment Yellow 138, 139, 150, 180, 185

C.I.顏料橙36、38、71、 C.I. Pigment Orange 36, 38, 71,

C.I.顏料綠7、36、58、 C.I. Pigment Green 7, 36, 58,

C.I.顏料藍15：6、 C.I. Pigment Blue 15:6,

C.I.顏料紫23 C.I. Pigment Violet 23

於使用顏料之情形時，作為本發明之著色硬化性組成物中之顏料之含量，相對於該組成物之總固形物而言，較佳的是0.5質量%~50質量%，更佳的是1質量%~30質量%。若顏料之含量為所述範圍內，則可有效地確保優異之顏色特性。 In the case of using a pigment, the content of the pigment in the color hardening composition of the present invention is preferably from 0.5% by mass to 50% by mass based on the total solid matter of the composition, more preferably 1% by mass to 30% by mass. When the content of the pigment is within the above range, excellent color characteristics can be effectively ensured.

作為本發明之著色硬化性組成物中所含之二吡咯亞甲基金屬錯合物化合物、氮雜吡咯亞甲基金屬錯合物化合物、及卟啉化合物之總含量，相對於著色硬化性組成物所包含之所有著色化合物(亦即包含二吡咯亞甲基金屬錯合物化合物、氮雜吡咯亞甲基金屬錯合物化合物、及卟啉化合物、以及使用其他顏料或染料之情形時的其他顏料或染料)而言，較佳的是1質量%~90質量%，更佳的是10質量%~70質量%。 The total content of the dipyrromethene metal complex compound, the azapyrrolidinium metal complex compound, and the porphyrin compound contained in the color hardening composition of the present invention, relative to the color hardening composition All coloring compounds contained in the article (that is, including a dipyrromethene metal complex compound, azapyrrolemethylene metal complex compound, and a porphyrin compound, and other cases where other pigments or dyes are used) The pigment or dye) is preferably from 1% by mass to 90% by mass, more preferably from 10% by mass to 70% by mass.

(C)聚合性化合物 (C) polymerizable compound

本發明之著色硬化性組成物較佳的是含有至少1種聚合性化合物。 The color hardening composition of the present invention preferably contains at least one polymerizable compound.

聚合性化合物例如若為具有至少1個乙烯性不飽和雙鍵之聚合性化合物則並無特別限制，可自公知之構成著色硬化性組成物的成分中選擇而使用。例如可列舉日本專利特開2006-23696號公報之段落編號[0010]~段落編號[0020]中所記載之成分或日本專利特開2006-64921號公報之段落編號[0027]~段落編號[0053]中所記載之成分。 The polymerizable compound is not particularly limited as long as it is a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from known components constituting the colored curable composition. For example, the component described in Paragraph No. [0010] to Paragraph No. [0020] of Japanese Patent Laid-Open Publication No. 2006-23696 or the paragraph number [0027] to paragraph number [0053] of JP-A-2006-64921 The ingredients described in the article.

而且，加成有使用異氰酸酯與羥基之加成反應而製造的胺基甲酸酯之聚合性化合物亦適宜，日本專利特開昭 51-37193號公報、日本專利特公平2-32293號公報、日本專利特公平2-16765號公報中所記載的丙烯酸胺基甲酸酯類或者日本專利特公昭58-49860號公報、日本專利特公昭56-17654號公報、日本專利特公昭62-39417號公報、日本專利特公昭62-39418號公報中所記載之具有環氧乙烷骨架的胺基甲酸酯化合物類亦適宜。 Further, it is also suitable to add a polymerizable compound of a urethane which is produced by an addition reaction of an isocyanate and a hydroxyl group, and Japanese Patent Laid-Open The urethane urethanes described in Japanese Patent Publication No. Hei 2-16765, Japanese Patent Publication No. Hei 2-16765, Japanese Patent Publication No. SHO 58-49860, and Japanese Patent Publication No. Sho. A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also suitable.

其他例可列舉日本專利特開昭48-64183號公報、日本專利特公昭49-43191號公報、日本專利特公昭52-30490號公報之各公報中所記載之聚酯丙烯酸酯類、環氧樹脂與(甲基)丙烯酸反應而得之環氧丙烯酸酯類等多官能之丙烯酸酯或甲基丙烯酸酯。另外亦可使用日本接著協會雜誌第20卷、No.7、第300頁~第308頁(1984年)中作為光硬化性單體及寡聚物而介紹者。 Other examples include polyester acrylates and epoxy resins described in each of the publications of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting with (meth)acrylic acid. In addition, it can also be introduced as a photocurable monomer and oligomer in the Journal of Japan Association Association, Vol. 20, No. 7, and pages 300 to 308 (1984).

聚合性化合物之具體例可列舉季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三((甲基)丙烯醯氧基乙基)異三聚氰酸酯、季戊四醇四(甲基)丙烯酸酯EO改性物、二季戊四醇六(甲基)丙烯酸酯EO改性物等，以及作為市售品之NK Ester A-TMMT、NK Ester A-TMM-3、NK Oligo UA-32P、NK Oligo UA-7200(以上為商品名、新中村化學工業股份有限公司製造)、Aronix M-305、Aronix M-306、Aronix M-309、Aronix M-450、Aronix M-402、TO-1382、TO-2349(以上為商品名、東亞合成股份有限公司製造)、V#802(商品名、大阪有機化學工業股 份有限公司製造)作為較佳例。 Specific examples of the polymerizable compound include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((A). Base) propylene methoxyethyl) isomeric cyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like, and as a commercial product NK Ester A-TMMT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (above trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306 , Aronix M-309, Aronix M-450, Aronix M-402, TO-1382, TO-2349 (above, trade name, manufactured by Toagosei Co., Ltd.), V#802 (trade name, Osaka Organic Chemical Industry Co., Ltd.) A manufacturing company is a preferred example.

該些聚合性化合物可單獨使用，或者將2種以上併用而使用。 These polymerizable compounds may be used singly or in combination of two or more kinds.

於著色硬化性組成物中使用聚合性化合物之情形時，總固形物中之聚合性化合物之含量(2種以上之情形時為總含量)較佳的是10質量%~80質量%，更佳的是15質量%~75質量%，特佳的是20質量%~60質量%。 When a polymerizable compound is used for the coloring-curable composition, the content of the polymerizable compound in the total solid content (the total content in the case of two or more kinds) is preferably 10% by mass to 80% by mass, more preferably It is 15% by mass to 75% by mass, and particularly preferably 20% by mass to 60% by mass.

(D)光聚合起始劑 (D) Photopolymerization initiator

本發明之著色硬化性組成物較佳的是含有至少1種光聚合起始劑。 The color hardening composition of the present invention preferably contains at least one photopolymerization initiator.

光聚合起始劑若為使所述聚合性化合物聚合而得者，則並無特別限制，較佳的是於特性、起始效率、吸收波長、獲得性、成本等觀點而選擇。 The photopolymerization initiator is not particularly limited as long as it is obtained by polymerizing the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

光聚合起始劑是藉由曝光之光而感光，起始、促進聚合性化合物之聚合的化合物。光聚合起始劑較佳的是感應波長為300nm以上之光化射線，起始、促進聚合性化合物之聚合的化合物。而且，關於並不直接感應波長為300nm以上之光化射線的光聚合起始劑，可與增感劑組合而較佳地使用。 The photopolymerization initiator is a compound which is photosensitive by exposure light to initiate polymerization of a polymerizable compound. The photopolymerization initiator is preferably a compound that induces polymerization of a polymerizable compound by inducing an actinic ray having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce an actinic ray having a wavelength of 300 nm or more can be preferably used in combination with a sensitizer.

光聚合起始劑具體而言例如可列舉肟酯化合物、有機鹵化化合物、噁二唑化合物、羰基化合物、縮酮化合物、安息香化合物、吖啶化合物、有機過氧化物、偶氮化合物、香豆素化合物、疊氮化物、茂金屬化合物、六芳基聯咪唑化合物、有機硼酸化合物、二磺酸化合物、鎓鹽化合物、 醯基膦(氧化物)、二苯甲酮化合物、苯乙酮化合物及其衍生物等。 Specific examples of the photopolymerization initiator include an oxime ester compound, an organic halogenated compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide, an azo compound, and a coumarin. a compound, an azide, a metallocene compound, a hexaarylbiimidazole compound, an organoboronic acid compound, a disulfonic acid compound, a phosphonium salt compound, Mercaptophosphine (oxide), benzophenone compound, acetophenone compound and its derivatives, and the like.

該些化合物中，自感光度之方面考慮，較佳的是肟酯化合物、六芳基聯咪唑化合物。 Among these compounds, an oxime ester compound or a hexaarylbiimidazole compound is preferred from the viewpoint of sensitivity.

肟酯化合物可使用日本專利特開2000-80068號公報、日本專利特開2001-233842號公報、日本專利特表2004-534797號公報、國際公開第2005/080337號、國際公開第2006/018973號說明書、日本專利特開2007-210991號公報、日本專利特開2007-231000號公報、日本專利特開2007-269779號公報、日本專利特開2009-191061號公報、國際公開第2009/131189號說明書中所記載之化合物。 The oxime ester compound can be used in JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, International Publication No. 2005/080337, and International Publication No. 2006/018973. The specification, Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. Hei. No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, and International Publication No. 2009/131189 The compound described in the above.

具體例可列舉2-(O-苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-戊二酮、2-(O-苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-己二酮、2-(O-苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-庚二酮、2-(O-苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、2-(O-苯甲醯肟)-1-[4-(甲基苯硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯肟)-1-[4-(乙基苯硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯肟)-1-[4-(丁基苯硫基)苯基]-1,2-丁二酮、1-(O-乙醯肟)-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-甲基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯肟)-1-[9-丙基-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-乙基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯肟)-1-[9-乙基-6-(2-丁基 苯甲醯基)-9H-咔唑-3-基]乙酮等。但並不限定於該些化合物。 Specific examples include 2-(O-benzhydrazin)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-benzamide)-1- [4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzamide)-1-[4-(phenylthio)phenyl]-1,2-hexyl Diketone, 2-(O-benzhydrazin)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O-benzamide)-1-[ 4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzamide)-1-[4-(methylphenylthio)phenyl]-1,2- Butanedione, 2-(O-benzylidene)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzamide)- 1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-acetamidine)-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl]ethanone, 1-(O-acetamidine)-1-[9-methyl-6-(2-methylbenzhydryl)-9H- Oxazol-3-yl]ethanone, 1-(O-acetamidine)-1-[9-propyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl] Ethyl ketone, 1-(O-acetamidine)-1-[9-ethyl-6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]ethanone, 1-(O -acetamidine)-1-[9-ethyl-6-(2-butyl Benzomethylene)-9H-indazol-3-yl]ethanone. However, it is not limited to these compounds.

而且，於本發明中，自感光度、經時穩定性、後期加熱時之著色之觀點考慮，至於作為光聚合起始劑之肟酯化合物，下述通式(A)所表示之化合物亦適宜。 Further, in the present invention, from the viewpoints of sensitivity, temporal stability, and coloring at the time of post-heating, as for the oxime ester compound as a photopolymerization initiator, a compound represented by the following formula (A) is also suitable. .

通式(A)中，X1、X2、及X3分別獨立地表示氫原子、鹵素原子、或烷基，R1表示-R、-OR、-COR、-SR、-CONRR'、或-CN，R2及R3分別獨立地表示-R、-OR、-COR、-SR、或-NRR'。R及R'分別獨立地表示烷基、芳基、芳烷基、或雜環基。該些基可被選自由鹵素原子及雜環基所構成之群組的1個以上取代，該烷基及芳烷基中之構成烷基鏈之碳原子之1個以上亦可被置換為不飽和鍵、醚鍵、或酯鍵，R及R'亦可相互鍵結而形成環。 In the formula (A), X 1 , X 2 and X 3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R 1 represents -R, -OR, -COR, -SR, -CONRR', or -CN, R 2 and R 3 each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic group. These groups may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, and one or more of the carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be substituted with no A saturated bond, an ether bond, or an ester bond, and R and R' may be bonded to each other to form a ring.

通式(A)中，X1、X2、或X3表示鹵素原子之情形時的鹵素原子可列舉氟、氯、溴、碘，X1、X2、或X3表示烷基之情形時的烷基例如可列舉甲基、乙基、丙基、異丙 基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并噁唑-2'-基)乙烯基等。 In the general formula (A), when the halogen atom in the case where X 1 , X 2 or X 3 represents a halogen atom, fluorine, chlorine, bromine or iodine may be mentioned, and when X 1 , X 2 or X 3 represents an alkyl group, Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a third pentyl group, and a hexyl group. Heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, C Alkynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxy A propyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a 2-(benzoxazole-2'-yl)vinyl group, and the like.

其中較佳的是X1、X2、及X3均表示氫原子，或者X1表示烷基，X2及X3均表示氫原子。 It is preferred that X 1 , X 2 and X 3 each represent a hydrogen atom, or X 1 represents an alkyl group, and both X 2 and X 3 represent a hydrogen atom.

通式(A)中，R或R'所表示之烷基例如可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并噁唑-2'-基)乙烯基等。 In the formula (A), the alkyl group represented by R or R' may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group or a butyl group. Base, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl , allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy , propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole- 2'-based) vinyl and the like.

R或R'所表示之芳基例如可列舉苯基、甲苯基、二甲苯基、乙基苯基、氯苯基、萘基、蒽基、菲基等。 Examples of the aryl group represented by R or R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group and the like.

R或R'所表示之芳烷基例如可列舉苄基、氯苄基、α-甲基苄基、α,α-二甲基苄基、苯基乙基、苯基乙烯基等。 Examples of the aralkyl group represented by R or R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group.

R或R'所表示之雜環基例如可列舉吡啶基、嘧啶基、呋喃基、噻吩基等。 Examples of the heterocyclic group represented by R or R' include a pyridyl group, a pyrimidinyl group, a furyl group, a thienyl group and the like.

而且，R及R'相互鍵結而形成之環例如可列舉哌啶環、嗎啉環等。 Further, examples of the ring formed by bonding R and R' to each other include a piperidine ring and a morpholine ring.

包含上述R及R'而構成的R2及R3分別獨立為甲基、己基、環己基、-S-Ph、-S-Ph-Cl、及-S-Ph-Br是特佳之樣態。 R 2 and R 3 each including R and R' described above are each independently a methyl group, a hexyl group, a cyclohexyl group, -S-Ph, -S-Ph-Cl, and -S-Ph-Br.

光聚合起始劑中，於通式(A)中，X1、X2及X3均為氫原子者；R1為烷基、特別是甲基者；R2為烷基、特別是甲基者；R3為烷基、特別是乙基者作為光聚合起始劑特別適宜。 In the photopolymerization initiator, in the general formula (A), X 1 , X 2 and X 3 are each a hydrogen atom; R 1 is an alkyl group, particularly a methyl group; and R 2 is an alkyl group, particularly A. It is particularly suitable as a photopolymerization initiator for the case where R 3 is an alkyl group, particularly an ethyl group.

因此，上述通式(A)所表示之光聚合起始劑之較佳之具體例可列舉以下所例示之化合物A~化合物F。但本發明並不受以下化合物任何限制。 Therefore, preferred examples of the photopolymerization initiator represented by the above formula (A) include the compounds A to F exemplified below. However, the present invention is not limited by any of the following compounds.

[化55] [化55]

[化56] [化56]

[化57] [化57]

通式(A)所表示之光聚合起始劑例如可藉由日本專利特開2005-220097號公報中所記載之方法而合成。 The photopolymerization initiator represented by the formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

本發明中所適宜使用之通式(A)所表示之化合物於250nm~500nm之波長區域中具有吸收波長。可更佳地列舉於300nm~380nm之波長區域中具有吸收波長的化合 物。特佳的是308nm及355nm之吸光度高的化合物。 The compound represented by the formula (A) suitably used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a combination of absorption wavelengths in a wavelength region of 300 nm to 380 nm. Things. Particularly preferred are compounds having a high absorbance at 308 nm and 355 nm.

而且，於本發明中，自感光度、經時穩定性、後期加熱時之著色之觀點考慮，至於作為光聚合起始劑之肟酯化合物，下述通式(B)所表示之化合物亦適宜。 Further, in the present invention, from the viewpoints of sensitivity, temporal stability, and coloring at the time of post-heating, as for the oxime ester compound as a photopolymerization initiator, a compound represented by the following formula (B) is also suitable. .

通式(B)中，R22表示1價取代基。A22表示2價連結基，Ar表示芳基。n為0~5之整數。X22表示1價取代基，於n為2~4之整數之情形時，多個存在之X22可相同亦可不同。 In the formula (B), R 22 represents a monovalent substituent. A 22 represents a divalent linking group, and Ar represents an aryl group. n is an integer from 0 to 5. X 22 represents a monovalent substituent. When n is an integer of 2 to 4, a plurality of X 22 existing may be the same or different.

所述R22所表示之1價取代基較佳的是以下所示之1價非金屬原子團。 The monovalent substituent represented by R 22 is preferably a monovalent non-metal atom group shown below.

亦即，R22所表示之1價之非金屬原子團可列舉亦可具有取代基之烷基、亦可具有取代基之芳基、亦可具有取代基之烷基磺醯基、亦可具有取代基之芳基磺醯基、亦可具有取代基之醯基、亦可具有取代基之雜環基等。 In other words, the monovalent non-metal atom group represented by R 22 may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, or a substitution. The arylsulfonyl group, a fluorenyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

亦可具有取代基之烷基較佳的是碳數為1~30之烷基，例如可列舉甲基、乙基、丙基、丁基、己基、環戊基、環己基、三氟甲基等。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and a trifluoromethyl group. Wait.

亦可具有取代基之芳基較佳的是碳數為6~30之芳 基，例如可列舉苯基、聯苯基、1-萘基、2-萘基等。 The aryl group which may have a substituent is preferably a carbon number of 6 to 30. Examples of the group include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

亦可具有取代基之烷基磺醯基較佳的是碳數為1~20之烷基磺醯基，例如可列舉甲基磺醯基、乙基磺醯基等。 The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

亦可具有取代基之芳基磺醯基較佳的是碳數為6~30之芳基磺醯基，例如可列舉苯基磺醯基、1-萘基磺醯基等。 The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

亦可具有取代基之醯基較佳的是碳數為2~20之醯基，例如可列舉乙醯基、丙醯基、丁醯基、三氟甲基羰基、戊醯基、苯甲醯基、1-萘甲醯基、2-萘甲醯基、4-甲基硫基苯甲醯基、4-苯基硫基苯甲醯基、4-二甲基胺基苯甲醯基、4-二乙基胺基苯甲醯基、2-氯苯甲醯基、2-甲基苯甲醯基、2-甲氧基苯甲醯基、2-丁氧基苯甲醯基、3-氯苯甲醯基、3-三氟甲基苯甲醯基、3-氰基苯甲醯基、3-硝基苯甲醯基、4-氟苯甲醯基、4-氰基苯甲醯基、4-甲氧基苯甲醯基等。 The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, and a benzamidine group. 1-naphthomethyl fluorenyl, 2-naphthylmethyl fluorenyl, 4-methylthiobenzimidyl, 4-phenylthiobenzimidyl, 4-dimethylaminobenzimidyl, 4- Diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzylidene, 3-chloro Benzopyridyl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene , 4-methoxybenzhydryl and the like.

亦可具有取代基之雜環基較佳的是包含氮原子、氧原子、硫原子、磷原子之芳香族或脂肪族之雜環。例如可列舉噻吩基、呋喃基、吡喃基等。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

作為所述R22，自高感光度化之方面而言，更佳的是未經取代之或具有取代基之醯基，具體而言較佳的是未經取代之或具有取代基之乙醯基、丙醯基、苯甲醯基、甲苯甲醯基。 As the R 22 , from the viewpoint of high sensitivity, an unsubstituted or substituted fluorenyl group is preferred, and specifically, an unsubstituted or substituted oxime is preferred. Base, propyl thiol, benzamidine, toluylcarbenyl.

所述R22具有取代基之情形時的取代基例如可列舉下述結構式所表示之基。其中較佳的是(d-1)、(d-4)及(d-5)之任意者。 Examples of the substituent in the case where R 22 has a substituent include a group represented by the following structural formula. Of these, any of (d-1), (d-4) and (d-5) is preferred.

所述A22所表示之2價連結基可列舉亦可具有取代基之碳數為1~12之伸烷基、亦可具有取代基之伸環己基、亦可具有取代基之伸炔基。 The divalent linking group represented by the above A 22 may be an alkylene group having a substituent of 1 to 12, a cyclohexylene group which may have a substituent, or an alkynyl group which may have a substituent.

可導入至該些基之取代基例如可列舉氟原子、氯原子、溴原子、碘原子等鹵素原子，甲氧基、乙氧基、第三丁氧基等烷氧基，苯氧基、對甲苯氧基等芳氧基，甲氧基羰基、丁氧基羰基、苯氧基羰基等烷氧基羰基等。 Examples of the substituent which can be introduced into these groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, and a phenoxy group. An aryloxy group such as a tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; and the like.

其中，作為所述A22，自提高感光度、抑制加熱隨時間經過所造成之著色之方面考慮，較佳的是未經取代之伸烷基、經烷基(例如甲基、乙基、第三丁基、十二烷基)取代之伸烷基、經烯基(例如乙烯基、烯丙基)取代之伸烷基、經芳基(例如苯基、對甲苯基、二甲苯基、異丙苯基、萘基、蒽基、菲基、苯乙烯基)取代之伸烷基。 Wherein, as the A 22 , from the viewpoint of improving the sensitivity and suppressing the coloring caused by the heating over time, an unsubstituted alkyl group or an alkyl group (for example, a methyl group, an ethyl group, or the like) is preferred. Tributyl, dodecyl) substituted alkylene, alkenyl (eg, vinyl, allyl) substituted alkyl, aryl (eg phenyl, p-tolyl, xylyl, iso) a propylphenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkyl group.

所述Ar所表示之芳基較佳的是碳數為6~30之芳 基，而且亦可具有取代基。 The aryl group represented by Ar is preferably a carbon number of 6 to 30. And may also have a substituent.

Ar具體而言可列舉苯基、聯苯基、1-萘基、2-萘基、聯三苯基、聯四苯基、鄰甲苯基、間甲苯基、及對甲苯基、二甲苯基、鄰異丙苯基、間異丙苯基、及對異丙苯基、均三甲苯基等。其中，自提高感光度、抑制加熱隨時間經過所造成之著色之方面而言，較佳的是經取代或未經取代之苯基。 Specific examples of Ar include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a tetraphenylene group, an o-tolyl group, a m-tolyl group, and a p-tolyl group, a xylyl group, and O-isopropylphenyl, m-isopropylphenyl, and p-cumyl, mesityl and the like. Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloring caused by heating over time.

上述苯基具有取代基之情形時，該取代基例如可列舉氟原子、氯原子、溴原子、碘原子等鹵素原子；甲氧基、乙氧基、第三丁氧基等烷氧基；苯氧基、對甲苯氧基等芳氧基；甲氧基羰基、丁氧基羰基、苯氧基羰基等烷氧基羰基；乙醯氧基、丙醯氧基、苯甲醯氧基等醯氧基；乙醯基、苯甲醯基、異丁醯基、丙烯醯基、甲基丙烯醯基、甲氧草醯基等醯基；甲基胺基、環己基胺基等烷基胺基；二甲基胺基、二乙基胺基、N-嗎啉基、N-哌啶基等二烷基胺基；苯基胺基；甲基、乙基、第三丁基、十二烷基等烷基；羥基、羧基等。 When the phenyl group has a substituent, the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group; An aryloxy group such as an oxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an oxirane group such as an ethoxy group, a propenyloxy group or a benzamidine group; Base; ethyl fluorenyl, benzhydryl, isobutyl fluorenyl, acryl fluorenyl, methacryl fluorenyl, methoxyindolyl, etc.; alkylamino, cyclohexylamine, etc.; a dialkylamino group such as an amino group, a diethylamino group, an N-morpholinyl group or an N-piperidinyl group; a phenylamino group; an alkyl group such as a methyl group, an ethyl group, a tributyl group or a dodecyl group; Base; hydroxyl group, carboxyl group, and the like.

於通式(B)中，若由所述Ar與鄰接之S所形成之「SAr」之結構為以下所示之結構，則於感光度之方面而言較佳。 In the general formula (B), the structure of "SAr" formed by the Ar and the adjacent S is preferably the following, and is preferable in terms of sensitivity.

[化60] [60]

所述X22所表示之1價取代基可列舉亦可具有取代基之烷基、亦可具有取代基之芳基、亦可具有取代基之烯基、亦可具有取代基之炔基、亦可具有取代基之烷氧基、亦可具有取代基之芳氧基、亦可具有取代基之烷硫基氧基、亦可具有取代基之芳硫基氧基、鹵素原子等。 The monovalent substituent represented by X 22 may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogen atom, or the like.

亦可具有取代基之烷基較佳的是碳數為1~30之烷基，例如可列舉甲基、乙基、丙基、丁基、己基、環戊基、環己基、三氟甲基、2-乙基己基、苯甲醯甲基等。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and a trifluoromethyl group. , 2-ethylhexyl, benzamidine methyl, and the like.

亦可具有取代基之芳基較佳的是碳數為6~30之芳基，例如可列舉苯基、聯苯基、1-萘基、2-萘基、聯三苯基、聯四苯基、鄰甲苯基、間甲苯基、及對甲苯基、二甲苯基等。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a triphenylene group, and a tetracene group. Base, o-tolyl, m-tolyl, p-tolyl, xylyl and the like.

亦可具有取代基之烯基較佳的是碳數為2~10之烯基，例如可列舉乙烯基、烯丙基、苯乙烯基等。 The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

亦可具有取代基之炔基較佳的是碳數為2~10之炔基，例如可列舉乙炔基、丙炔基、炔丙基等。 The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, a propargyl group and the like.

亦可具有取代基之烷氧基較佳的是碳數為1~30之烷氧基，例如可列舉甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、苄氧基等。 The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a benzyloxy group. Base.

亦可具有取代基之芳氧基較佳的是碳數為6~30之芳氧基，例如可列舉苯氧基、1-萘氧基、2-萘氧基、2-氯苯氧基、2-甲基苯氧基、2-甲氧基苯氧基等。 The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 2-chlorophenoxy group. 2-methylphenoxy, 2-methoxyphenoxy, and the like.

亦可具有取代基之烷硫基氧基較佳的是碳數為1~30之烷硫基氧基，例如可列舉甲硫基氧基、乙硫基氧基、丙硫基氧基、異丙硫基氧基、丁硫基氧基、異丁硫基氧基、第二丁硫基氧基、第三丁硫基氧基、戊硫基氧基、異戊硫基氧基、己硫基氧基、庚硫基氧基、辛硫基氧基、2-乙基己硫基氧基、癸硫基氧基、十二烷硫基氧基、十八烷硫基氧基、苄硫基氧基等。 The alkylthiooxy group which may have a substituent is preferably an alkylthiooxy group having 1 to 30 carbon atoms, and examples thereof include a methylthiooxy group, an ethylthio group, a propylthio group, and a different group. Propylthiooxy, butylthiooxy, isobutylthiooxy, second butylthiooxy, tert-butylthiooxy, pentylthiooxy, isopentylthiooxy, hexylsulfide Baseoxy, heptylthiooxy, octylthiooxy, 2-ethylhexylthiooxy, sulfonyloxy, dodecylthiooxy, octadecylthiooxy, benzyl sulfide Baseoxy and the like.

亦可具有取代基之芳硫基氧基較佳的是碳數為6~30之芳硫基氧基，例如存在有苯硫基氧基、1-萘硫基氧基、2-萘硫基氧基、2-氯苯硫基氧基、2-甲基苯硫基氧基、2-甲氧基苯硫基氧基、2-丁氧基苯硫基氧基、3-氯苯硫基氧基、3-三氟甲基苯硫基氧基、3-氰基苯硫基氧基、3-硝基苯硫基氧基、4-氟苯硫基氧基、4-氰基苯硫基氧基、4-甲氧基苯硫基氧基、4-二甲基胺基苯硫基氧基、4-甲基硫基苯硫基氧基、4-苯基硫基苯硫基氧基等。 The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, for example, a phenylthiooxy group, a 1-naphthylthiooxy group, or a 2-naphthylthio group. Oxyl, 2-chlorophenylthiooxy, 2-methylphenylthiooxy, 2-methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorophenylthio Oxyl, 3-trifluoromethylphenylthiooxy, 3-cyanophenylthiooxy, 3-nitrophenylthiooxy, 4-fluorophenylthiooxy, 4-cyanophenylsulfide Alkoxy, 4-methoxyphenylthiooxy, 4-dimethylaminophenylthiooxy, 4-methylthiophenylthiooxy, 4-phenylthiophenylthiooxy Base.

鹵素原子存在有氟原子、氯原子、溴原子、碘原子等。 A halogen atom, a chlorine atom, a bromine atom, an iodine atom, etc. exist in a halogen atom.

亦可具有取代基之鹵化烷基可列舉單氟甲基、二氟甲基、三氟甲基、二氯甲基、三氯甲基、單溴甲基、二溴甲基、三溴甲基等。 The halogenated alkyl group which may have a substituent may, for example, be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group or a tribromomethyl group. Wait.

N上亦可具有取代基之醯胺基可列舉N,N-二甲基醯胺基、N,N-二乙基醯胺基等。 Examples of the mercapto group which may have a substituent on N include N,N-dimethylammonium group, N,N-diethylguanamine group and the like.

該些取代基中，作為X22，自溶劑溶解性與長波長區域之吸收效率提高之方面考慮，較佳的是亦可具有取代基之烷基、亦可具有取代基之芳基、亦可具有取代基之烯基、亦可具有取代基之炔基、亦可具有取代基之烷氧基、亦可具有取代基之芳氧基、亦可具有取代基之烷硫基氧基、亦可具有取代基之芳硫基氧基、亦可具有取代基之鹵化烷基、亦可具有取代基之胺基、或於N上亦可具有取代基之醯胺基，其中更佳的是亦可具有取代基之烷基。 Among these substituents, as X 22 , from the viewpoint of improvement in solvent solubility and absorption efficiency in a long wavelength region, an alkyl group which may have a substituent, an aryl group which may have a substituent, or Alkenyl group having a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or An arylthiooxy group having a substituent, a halogenated alkyl group which may have a substituent, an amine group which may have a substituent, or an amine group which may have a substituent on N, and more preferably An alkyl group having a substituent.

而且，通式(B)中之n表示0~5之整數，自合成之容易性之觀點考慮，較佳的是0~3之整數，更佳的是0~ 2之整數。 Further, n in the general formula (B) represents an integer of 0 to 5, and from the viewpoint of easiness of synthesis, an integer of 0 to 3 is preferable, and more preferably 0 to An integer of 2.

於通式(B)中存在多個X22之情形時，多個X22可相同亦可不同。 In the case where a plurality of X 22 are present in the formula (B), the plurality of X 22 may be the same or different.

以下表示上述通式(B)所表示之肟光聚合起始劑之具體例。 Specific examples of the photopolymerization initiator represented by the above formula (B) are shown below.

[化61] [化61]

[化62] [化62]

本發明中適宜使用的通式(B)所表示之化合物是於250nm~500nm之波長區域具有吸收波長者。可更佳地列 舉於300nm~380nm之波長區域具有吸收波長之化合物。特佳的是308nm及355nm之吸光度高之化合物。 The compound represented by the formula (B) which is suitably used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. Better place A compound having an absorption wavelength in a wavelength region of 300 nm to 380 nm. Particularly preferred are compounds having a high absorbance at 308 nm and 355 nm.

作為有機鹵化化合物之例，具體而言可列舉若林等、「日本化學學會通報(Bull Chem.Soc.Japan)」42、2924(1969)、美國專利第3,905,815號說明書、日本專利特公昭46-4605號公報、日本專利特開昭48-36281號公報、日本專利特開昭55-32070號公報、日本專利特開昭60-239736號公報、日本專利特開昭61-169835號公報、日本專利特開昭61-169837號公報、日本專利特開昭62-58241號公報、日本專利特開昭62-212401號公報、日本專利特開昭63-70243號公報、日本專利特開昭63-298339號公報、M.P.Hutt「雜環化學雜誌(Journal of Heterocyclic Chemistry)」1(No3),(1970)等中所記載之化合物，特別是可列舉經三鹵甲基取代之噁唑化合物、均三嗪化合物。 Specific examples of the organic halogenated compound include, for example, "National Chemical Society Bulletin (Bull Chem. Soc. Japan)" 42, 2924 (1969), U.S. Patent No. 3,905,815, and Japanese Patent Publication No. Sho 46-4605. Japanese Patent Laid-Open Publication No. SHO-48-36281, Japanese Patent Laid-Open Publication No. Sho 55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent Laid-Open No. 61-169835 Japanese Laid-Open Patent Publication No. SHO-62- 582 837, Japanese Patent Laid-Open No. Hei. The compound described in the publication of the Journal of Heterocyclic Chemistry 1 (No. 3), (1970), etc., particularly includes a trihalomethyl substituted oxazole compound and a s-triazine compound. .

作為六芳基聯咪唑化合物之例，例如可列舉日本專利特公平6-29285號公報、美國專利第3,479,185號、美國專利第4,311,783號、美國專利第4,622,286號等之各說明書中所記載之各種化合物，具體而言為2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰溴苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰，對二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰氯苯基)-4,4',5,5'-四(間甲氧基苯基)聯咪唑、2,2'-雙(鄰，鄰'-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰硝基苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰甲苯 基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰三氟苯基)-4,4',5,5'-四苯基聯咪唑等。 Examples of the hexaarylbiimidazole compound include various compounds described in the respective specifications of Japanese Patent Publication No. Hei 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Specifically, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4 ',5,5'-Tetraphenylbiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-o-o-dichlorophenyl)-4, 4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (o-toluene Base)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and the like.

光聚合起始劑可使用1種或將2種以上組合使用。於使用2種以上之情形時，可使用多種通式(B)所表示之化合物，亦可使用多種通式(A)所表示之化合物。而且，亦可自通式(A)及通式(B)所表示之化合物中分別使用至少1種。而且，亦可使用通式(A)及通式(B)所表示之化合物之分別至少1種與通式(A)及通式(B)所表示之化合物以外之肟化合物或肟化合物以外之光聚合起始劑。而且，亦可併用增感劑。 The photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used, a plurality of compounds represented by the formula (B) may be used, and a plurality of compounds represented by the formula (A) may also be used. Further, at least one of the compounds represented by the general formula (A) and the general formula (B) may be used. Further, at least one of the compounds represented by the general formula (A) and the general formula (B) and the ruthenium compound or ruthenium compound other than the compound represented by the general formula (A) and the general formula (B) may be used. Photopolymerization initiator. Moreover, a sensitizer can also be used in combination.

光聚合起始劑之總含量較佳的是於著色硬化性組成物中之總固形物中為0.1質量%~20質量%，更佳的是0.5質量%~10質量%，最佳的是1質量%~5質量%。若為該範圍內，則曝光時之感光度高、且顏色特性亦良好。 The total content of the photopolymerization initiator is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 10% by mass, based on the total solid content of the colored curable composition, and most preferably 1 Mass%~5 mass%. If it is in this range, the sensitivity at the time of exposure is high, and the color characteristic is also favorable.

(E)黏合樹脂 (E) Adhesive resin

於本發明之著色硬化性組成物中，為了使覆膜形成性提高，亦可使用黏合樹脂。作為黏合樹脂，自圖案形成性之觀點考慮，較佳的是使用鹼可溶性黏合劑。 In the color hardening composition of the present invention, a binder resin may be used in order to improve the film formability. As the binder resin, it is preferred to use an alkali-soluble binder from the viewpoint of pattern formability.

鹼可溶性黏合劑 Alkali soluble binder

鹼可溶性黏合劑除了具有鹼可溶性以外，並無特別限定，較佳的是可根據耐熱性、顯影性、獲得性等觀點而選擇。 The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

鹼可溶性黏合劑是線狀有機高分子聚合物，且較佳的是可溶於有機溶劑中，可藉由弱鹼性水溶液而顯影者。此 種線狀有機高分子聚合物可列舉於側鏈具有羧酸之聚合物，例如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號、日本專利特開昭59-71048號之各公報中所記載之甲基丙烯酸共聚物、丙烯酸共聚物、伊康酸共聚物、巴豆酸共聚物、馬來酸共聚物、部分酯化馬來酸共聚物等，於側鏈具有羧酸之酸性纖維素衍生物亦同樣地有用。 The alkali-soluble binder is a linear organic high molecular polymer, and is preferably soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution. this The linear organic polymer may be exemplified by a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japan A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a methacrylic acid copolymer described in each of the publications of Japanese Patent Laid-Open Publication No. SHO-59-53836 A crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer or the like is also useful in the case of an acidic cellulose derivative having a carboxylic acid in a side chain.

除了上述者以外，鹼可溶性黏合劑亦可使用於具有羥基之聚合物上加成酸酐而成者等或者聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、聚((甲基)丙烯酸-2-羥基乙酯)、聚乙烯吡咯啶酮或聚環氧乙烷、聚乙烯醇等。而且，線狀有機高分子聚合物亦可為具有親水性之單體共聚而成者。其例可列舉(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸羥基烷基酯、丙三醇(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、二級或三級之烷基丙烯醯胺、(甲基)丙烯酸二烷基胺基烷基酯、嗎啉(甲基)丙烯酸酯、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、乙烯基咪唑、乙烯基***、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、分支或直鏈之(甲基)丙烯酸丙酯、分支或直鏈之(甲基)丙烯酸丁酯、或(甲基)丙烯酸苯氧基羥基丙酯等。另外，具有親水性之單體亦可使用包含四氫呋喃甲基、磷酸基、磷酸酯基、四級銨鹽基、伸乙基氧基鏈、伸丙基氧基鏈、磺酸基及源自其鹽之基、嗎啉基乙基等而成之單體等。 In addition to the above, the alkali-soluble binder may be used in the addition of an acid anhydride to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly((meth)acrylic acid-2). - hydroxyethyl ester), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. Further, the linear organic high molecular polymer may be a copolymer of a hydrophilic monomer. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N-methylolpropene. Indoleamine, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-vinyl Caprolactam, vinyl imidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear (A) Base) butyl acrylate, or phenoxy hydroxypropyl (meth)acrylate, and the like. In addition, the hydrophilic monomer may also include tetrahydrofuranmethyl, phosphate, phosphate, quaternary ammonium, ethyl ethoxy, propyloxy, sulfonic acid and derived therefrom. a monomer such as a salt base or a morpholinoethyl group.

而且，鹼可溶性黏合劑為了提高交聯效率，亦可於側鏈具有聚合性基，例如亦可使用於側鏈含有烯丙基、(甲基)丙烯基、或烯丙氧基烷基等之聚合物等。含有上述聚合性基之聚合物之例可列舉Dianal NR系列(商品名、三菱麗陽股份有限公司製造)、Photomer 6173(含有COOH之聚氨酯丙烯酸寡聚物(polyurethane acrylic oligomer)、商品名、鑽石三葉草股份有限公司(Diamond Shamrock Co.Ltd.,)製造)、Viscoat R-264、KS resist 106(均為商品名、大阪有機化學工業股份有限公司製造)、Cyclomer P系列、PLACCEL CF200系列(均為商品名、大賽璐化學工業股份有限公司製造)、Ebecryl 3800(商品名、大賽璐-UCB股份有限公司製造)等。而且，為了提高硬化皮膜之強度，亦可使用醇可溶性尼龍或2,2-雙-(4-羥基苯基)-丙烷與表氯醇之聚醚等。 Further, the alkali-soluble binder may have a polymerizable group in the side chain in order to increase the crosslinking efficiency, and for example, it may be used in the side chain containing an allyl group, a (meth)acryl group, or an allyloxyalkyl group. Polymers, etc. Examples of the polymer containing the above polymerizable group include Dianal NR series (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, trade name, diamond clover) Co., Ltd. (manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, and PLACCEL CF200 series (all products) Name, manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (trade name, Daicel 璐-UCB Co., Ltd.). Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

於該些各種鹼可溶性黏合劑中，自耐熱性之觀點考慮，較佳的是聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯醯基/丙烯醯胺共聚物樹脂，自控制顯影性之觀點考慮，較佳的是丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯醯基/丙烯醯胺共聚物樹脂。 Among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylonitrile/propylene are preferred from the viewpoint of heat resistance. The guanamine copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylonitrile/acrylamide copolymer resin from the viewpoint of controlling developability.

所述丙烯酸系樹脂較佳的是包含選自(甲基)丙烯酸苄基酯、(甲基)丙烯酸、羥基(甲基)丙烯酸乙酯、(甲基)丙烯醯胺等之單體的共聚物或者所述之Photomer 6173、KS resist-106、Cyclomer P系列等。 The acrylic resin is preferably a copolymer comprising a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, ethyl hydroxy(meth)acrylate, and (meth)acrylamide. Or the Photomer 6173, KS resist-106, Cyclomer P series, and the like.

自顯影性、液體黏度等觀點考慮，鹼可溶性黏合劑較 佳的是重量平均分子量(藉由GPC(Gel Permeation Chromatography，凝膠滲透層析)法而測定之聚苯乙烯換算值)為1000~2×105之聚合物，更佳的是2000~1×105之聚合物，特佳的是5000~5×104之聚合物。可單獨使用亦可併用2種以上。 The alkali-soluble binder is preferably a weight average molecular weight (polystyrene equivalent value measured by GPC (Gel Permeation Chromatography) method) of 1000 to 2 from the viewpoints of self-developability, liquid viscosity, and the like. The polymer of ×10 5 is more preferably a polymer of 2000 to 1 × 10 5 , and particularly preferably a polymer of 5000 to 5 × 10 4 . They may be used alone or in combination of two or more.

其他成分 Other ingredients

本發明之著色硬化性組成物亦可進一步視需要而於不損及本發明之效果之範圍內含有公知之添加劑，例如多官能硫醇化合物、鏈轉移劑、聚合抑制劑、有機溶劑、界面活性劑、密接改良劑、交聯劑、顯影促進劑、及其他添加劑。 The color hardening composition of the present invention may further contain a known additive, such as a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, and an interfacial activity, as needed, without damaging the effects of the present invention. Agent, adhesion improver, crosslinking agent, development accelerator, and other additives.

以下，對該些成分加以說明。 Hereinafter, the components will be described.

多官能硫醇化合物 Polyfunctional thiol compound

本發明之著色硬化性組成物亦可含有多官能硫醇化合物。 The color hardening composition of the present invention may also contain a polyfunctional thiol compound.

本發明之著色硬化性組成物藉由含有多官能硫醇化合物可提高感光度，抑制由染料等有色材料所引起之離子溶出等，於液晶顯示裝置之彩色濾光片之製作中使用本發明之著色硬化性組成物時，可防止串擾(crosstalk)等畫質之劣化，從而變得可顯示鮮明之高畫質。 The colored curable composition of the present invention can improve the sensitivity by containing a polyfunctional thiol compound, suppress ion elution caused by a coloring material such as a dye, and the like, and use the present invention in the production of a color filter of a liquid crystal display device. When the curable composition is colored, deterioration of image quality such as crosstalk can be prevented, and a high image quality can be displayed.

於本發明中，所謂「多官能硫醇化合物」是表示於分子內具有2個以上巰基之化合物。上述多官能硫醇化合物較佳的是分子量100以上之低分子化合物，具體而言較佳的是分子量為100~1500，更佳的是150~1000。上述多官 能硫醇化合物較佳的是於分子內具有2個~10個巰基，更佳的是具有2個~6個，特佳的是具有2個~4個。而且，該些化合物較佳的是設為於上述自由基聚合性單體聚合時所輔助地使用之系統。具體而言，較佳的是使多官能硫醇化合物之添加量於組成物之總固形物中為1質量%~20質量%，或者設為比同時含有之上述自由基聚合性單體之添加量更少之添加量。 In the present invention, the "polyfunctional thiol compound" is a compound having two or more thiol groups in the molecule. The above polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more, and specifically preferably has a molecular weight of from 100 to 1,500, more preferably from 150 to 1,000. Above The thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6 groups, and particularly preferably 2 to 4 groups. Further, these compounds are preferably used in a system which is used in the case of polymerization of the above-mentioned radical polymerizable monomer. Specifically, it is preferred that the amount of the polyfunctional thiol compound added is from 1% by mass to 20% by mass based on the total solid content of the composition, or the addition of the above-mentioned radical polymerizable monomer is also contained. A smaller amount of addition.

作為本發明中所可使用之多官能硫醇化合物之具體例，例如可列舉三羥甲基丙烷三(3-巰基丙酸)酯、季戊四醇四(3-巰基丙酸)酯、四乙二醇雙(3-巰基丙酸)酯、二季戊四醇六(3-巰基丙酸)酯、季戊四醇四(巰基乙酸)酯、季戊四醇四(3-巰基丁酸)酯、丁二醇雙(3-巰基丁酸)酯、1,4-雙(3-巰基丁氧基)丁烷、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮等作為適宜之多官能硫醇化合物。特佳的是包含二級SH基(巰基)之化合物。而且，自液體穩定性之觀點考慮，較佳的是具有三嗪骨架。具體而言可列舉Karenz MT系列(商品名、昭和電工股份有限公司製造)等。 Specific examples of the polyfunctional thiol compound which can be used in the present invention include trimethylolpropane tris(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, and tetraethylene glycol. Bis(3-mercaptopropionic acid) ester, dipentaerythritol hexa(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(mercaptoacetic acid) ester, pentaerythritol tetrakis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyl) Acid) ester, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4 , 6(1H, 3H, 5H)-trione or the like as a suitable polyfunctional thiol compound. Particularly preferred are compounds comprising a secondary SH group (fluorenyl). Further, from the viewpoint of liquid stability, it is preferred to have a triazine skeleton. Specifically, the Karenz MT series (trade name, manufactured by Showa Denko Co., Ltd.) and the like can be mentioned.

多官能硫醇化合物之含量較佳的是於著色硬化性組成物中之總固形物中為0.01質量%~20質量%，更佳的是0.1質量%~10質量%。若多官能硫醇化合物之含量為該範圍內，則可提供著色硬化性組成物之感光度良好，且保存穩定性良好，所獲得之彩色濾光片中之畫素之密接性良好而無圖案缺陷，於液晶顯示裝置中使用之情形時電氣特性良 好之著色硬化性組成物。 The content of the polyfunctional thiol compound is preferably from 0.01% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass, based on the total solid content of the colored curable composition. When the content of the polyfunctional thiol compound is within this range, the coloring curable composition can be provided with good sensitivity and good storage stability, and the obtained color filter has good adhesion to the pixel without pattern. Defect, good electrical characteristics when used in a liquid crystal display device Good color hardening composition.

增感劑 Sensitizer

本發明之著色硬化性組成物亦可含有增感劑。本發明中所適宜使用之典型的增感劑可列舉於Crivello[J.V.Crivello，聚合物科學進展(Adv.in Polymer Sci),62,1(1984)]中所揭示之增感劑。具體而言可列舉芘、苝、吖啶、噻噸酮、2-氯噻噸酮、苯并黃素、N-乙烯基咔唑、9,10-二丁氧基蒽、蒽醌、二苯甲酮、香豆素、酮香豆素、菲、樟腦醌、啡噻嗪衍生物等。作為增感劑，較佳的是以相對於光聚合起始劑而言為50質量%~200質量%之比例進行添加。 The color hardening composition of the present invention may further contain a sensitizer. Typical sensitizers suitable for use in the present invention are exemplified by Crivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples thereof include ruthenium, osmium, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthracene, and diphenyl. Ketone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives, and the like. The sensitizer is preferably added in a proportion of 50% by mass to 200% by mass based on the photopolymerization initiator.

鏈轉移劑 Chain transfer agent

本發明之著色硬化性組成物亦可含有鏈轉移劑。本發明中適宜使用之鏈轉移劑例如可列舉N,N-二甲基胺基苯甲酸乙酯等N,N-二烷基胺基苯甲酸烷基酯，2-巰基苯并噻唑、2-巰基苯并噁唑、2-巰基苯并咪唑、N-苯基巰基苯并咪唑等具有雜環之巰基化合物等。 The color hardening composition of the present invention may also contain a chain transfer agent. The chain transfer agent to be suitably used in the invention may, for example, be an N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2- A mercapto compound having a heterocyclic ring such as mercaptobenzoxazole, 2-mercaptobenzimidazole or N-phenylmercaptobenzimidazole.

鏈轉移劑可單獨使用1種，亦可併用2種以上。 The chain transfer agent may be used singly or in combination of two or more.

作為鏈轉移劑之含量(總量)，自減低感光度不均一等觀點考慮，較佳的是於本發明之著色硬化性組成物之總固形物中為0.01質量%~15質量%之範圍，更佳的是0.1質量%~10質量%，特佳的是0.5質量%~5質量%。 The content (total amount) of the chain transfer agent is preferably in the range of 0.01% by mass to 15% by mass in the total solid content of the color hardening composition of the present invention from the viewpoint of reducing the sensitivity unevenness. More preferably, it is 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.

聚合抑制劑 Polymerization inhibitor

本發明之著色硬化性組成物亦可含有聚合抑制劑。 The color hardening composition of the present invention may also contain a polymerization inhibitor.

所謂聚合抑制劑是起到如下作用之物質：藉由光或熱而對著色硬化性組成物中所產生之自由基等聚合起始種實施供給氫(或授予氫)、供給能量(或授予能量)、供給電子(或授予電子)等，使聚合起始種失活而抑制聚合意外地起始。可使用日本專利特開2007-334322號公報之段落0154~段落0173中所記載之聚合抑制劑等。 The polymerization inhibitor is a substance that supplies hydrogen (or imparts hydrogen), supplies energy (or grants energy) to a polymerization starting species such as a radical generated in a colored curable composition by light or heat. ), supplying electrons (or electron donating), etc., inactivating the polymerization starting species and inhibiting the polymerization from starting unexpectedly. A polymerization inhibitor or the like described in paragraphs 0154 to 0173 of JP-A-2007-334322 can be used.

該些化合物中，聚合抑制劑可較佳地列舉對甲氧基苯酚。 Among these compounds, a polymerization inhibitor is preferably exemplified by p-methoxyphenol.

作為本發明之著色硬化性組成物中之聚合抑制劑之含量(總量)，較佳的是於聚合性化合物之總質量中為0.0001質量%~5質量%，更佳的是0.001質量%~5質量%，特佳的是0.001質量%~1質量%。 The content (total amount) of the polymerization inhibitor in the color hardening composition of the present invention is preferably 0.0001% by mass to 5% by mass, and more preferably 0.001% by mass based on the total mass of the polymerizable compound. 5% by mass, particularly preferably 0.001% by mass to 1% by mass.

有機溶劑 Organic solvents

本發明之著色硬化性組成物可含有有機溶劑。 The color hardening composition of the present invention may contain an organic solvent.

有機溶劑若為可滿足所並存之各成分的溶解性或製成著色硬化性組成物時之塗佈性者，則基本上並無特別限制，特佳的是考慮固形物之溶解性、塗佈性、安全性而進行選擇。 The organic solvent is not particularly limited as long as it satisfies the solubility of each component to be coherent or the coloring curable composition, and it is particularly preferable to consider the solubility of the solid matter and the coating. Choose sex and safety.

有機溶劑可列舉酯類、醚類、酮類、芳香族烴類等。 Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons.

酯類例如可列舉乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、氧化乙酸烷基酯類(例如氧化乙酸甲酯、氧化乙酸乙酯、氧化乙酸丁酯(具體而言可列舉甲氧基乙酸甲酯、甲氧基乙酸 乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等))、3-氧基丙酸烷基酯類、2-氧基丙酸烷基酯類、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸甲酯、2-側氧丁酸乙酯等。 Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl. Butyl acrylate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example, methyl acetate, ethyl acetate, butyl acetate) (specifically, methyl methoxyacetate, methoxy group) Acetic acid Ethyl ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate, alkyl 2-oxypropionate, 2 Methyl 2-oxo-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl hydrazine Ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

而且，醚類例如可列舉二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、二乙二醇甲***、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等。 Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl stilbene acetate, ethyl stilbene acetate, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single Propyl ether acetate and the like.

酮類例如可列舉丁酮、環己酮、2-庚酮、3-庚酮等。 Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

芳香族烴類例如可適宜列舉甲苯、二甲苯等。 Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

作為該些有機溶劑，自前述各成分之溶解性、以及於包含鹼溶性黏合劑之情形時其溶解性、塗佈面狀之改良等觀點考慮，亦較佳的是混合2種以上。於此情形時，特佳的是包含選自由如下溶劑所構成之群組之2種以上的混合溶液：3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基賽路蘇乙酸酯、乳酸乙酯、二乙二醇二甲醚、二乙二醇甲***、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚、及丙二醇甲醚乙酸酯。 In view of the solubility of the above-mentioned respective components and the solubility in the case of containing an alkali-soluble binder, and the improvement of the coating surface shape, it is preferable to mix two or more types. In this case, it is particularly preferable to contain a mixed solution of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl group. Luce acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

作為有機溶劑於著色硬化性組成物中之含量，較佳的是著色硬化性組成物中之總固形物濃度成為10質量%~ 80質量%之量，更佳的是成為15質量%~60質量%之量。 The content of the organic solvent in the coloring curable composition is preferably such that the total solid content in the color hardening composition is 10% by mass. The amount of 80% by mass is more preferably 15% by mass to 60% by mass.

界面活性劑 Surfactant

本發明之著色硬化性組成物亦可含有界面活性劑。 The color hardening composition of the present invention may also contain a surfactant.

界面活性劑可使用陰離子系、陽離子系、非離子系、或兩性之任意者，較佳之界面活性劑是非離子系界面活性劑。具體而言可列舉日本專利特開2009-098616號公報之段落0058中所記載之非離子系界面活性劑，其中較佳的是氟系界面活性劑。 As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant may be used, and a preferred surfactant is a nonionic surfactant. Specifically, a nonionic surfactant described in paragraph 0058 of JP-A-2009-098616 is preferred, and a fluorine-based surfactant is preferred.

本發明中所可使用之界面活性劑例如可列舉作為市售品之Megafac F142D、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F183、Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781、Megafac F781-F、Megafac R30、Megafac R08、Megafac F-472SF、Megafac BL20、Megafac R-61、Megafac R-90(商品名、DIC股份有限公司製造)、Fluorad FC-135、Fluorad FC-170C、Fluorad FC-430、Fluorad FC-431、Novec FC-4430(商品名、住友3M股份有限公司製造)、Asahi Guard AG7105、7000、950、7600、Surflon S-112、Surflon S-113、Surflon S-131、Surflon S-141、Surflon S-145、Surflon S-382、Surflon SC-101、Surflon SC-102、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-106(商品名、旭硝子股份有限公司製造)、Eftop EF351、Eftop 352、Eftop 801、Eftop 802(商品名、三菱綜合材料電子化成股份有限公司製造)、Ftergent 250(那奧斯(Neos)股份有限公司 製造)等。 The surfactant which can be used in the present invention is, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 which are commercially available products. , Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (trade name, manufactured by DIC Corporation), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, Surflon S-113, Surflon S-131 , Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (trade name, Asahi Glass) Co., Ltd.), Eftop EF351, Eftop 352, Eftop 801, Eftop 802 (trade name, manufactured by Mitsubishi Materials Corporation), Ftergent 250 (Neos) Manufacturing) and so on.

而且，界面活性劑可列舉下述共聚物作為較佳例：所述共聚物包含下述式(W)所表示之結構單元A及結構單元B，將四氫呋喃作為溶劑，藉由凝膠滲透層析法而測定的聚苯乙烯換算之重量平均分子量(Mw)為1,000以上10,000以下。 Further, examples of the surfactant include a copolymer comprising a structural unit A and a structural unit B represented by the following formula (W), and a tetrahydrofuran as a solvent by gel permeation chromatography. The polystyrene-equivalent weight average molecular weight (Mw) measured by the method is 1,000 or more and 10,000 or less.

式(W)中，R1及R3分別獨立地表示氫原子或甲基，R2表示碳數為1以上4以下之直鏈伸烷基，R4表示氫原子或碳數為1以上4以下之烷基，L表示碳數為3以上6以下之伸烷基，p及q是表示聚合比之質量百分率，p表示10質量%以上80質量%以下之數值，q表示20質量%以上90質量%以下之數值，r表示1以上18以下之整數，n表示1以上10以下之整數。 In the formula (W), R 1 and R 3 each independently represent a hydrogen atom or a methyl group, R 2 represents a linear alkyl group having 1 or more and 4 or less carbon atoms, and R 4 represents a hydrogen atom or a carbon number of 1 or more. In the following alkyl group, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q are mass percentages of a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more and 90%. A numerical value of the mass % or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.

所述L較佳的是下述式(W-2)所表示之分支伸烷基。式(W-2)中之R5表示碳數為1以上4以下之烷基，於相溶性與對被塗佈面之濕潤性之方面而言，較佳的是碳數為1以上3以下之烷基，更佳的是碳數為2或3之烷基。 The L is preferably a branched alkyl group represented by the following formula (W-2). R 5 in the formula (W-2) represents an alkyl group having a carbon number of 1 or more and 4 or less, and preferably has a carbon number of 1 or more and 3 or less in terms of compatibility and wettability to a surface to be coated. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms.

式(W)中之p與q之和(p+q)較佳的是p+q=100，亦即100質量%。 The sum of p and q (p+q) in the formula (W) is preferably p + q = 100, that is, 100% by mass.

所述共聚物之重量平均分子量(Mw)更佳的是1,500以上5,000以下。 The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

該些界面活性劑可單獨使用1種或者使用2種以上。 These surfactants may be used alone or in combination of two or more.

作為本發明之著色硬化性組成物中之界面活性劑之添加量(總量)，較佳的是於著色硬化性組成物之總固形物中為0.01質量%~2.0質量%，特佳的是0.02質量%~1.0質量%。若添加量為該範圍，則塗佈性及硬化膜之均一性變得更良好。 The addition amount (total amount) of the surfactant in the color hardening composition of the present invention is preferably 0.01% by mass to 2.0% by mass based on the total solid content of the colored curable composition, and particularly preferably 0.02% by mass to 1.0% by mass. When the amount added is in this range, the uniformity of coatability and cured film becomes more favorable.

密接改良劑 Adhesive improver

本發明之著色硬化性組成物亦可含有密接改良劑。 The color hardening composition of the present invention may further contain a adhesion improving agent.

密接改良劑是用以使成為支撐體之無機物(例如玻璃、矽、氧化矽、氮化矽等矽化合物、金、銅、鋁等)與著色硬化性組成物之硬化膜的密接性提高的化合物。具體而言可列舉矽烷偶合劑等。作為密接改良劑之矽烷偶合劑是以界面之改質為目的者，並無特別限定，可使用公知者。 The adhesion improving agent is a compound for improving the adhesion between an inorganic substance (for example, a ruthenium compound such as glass, ruthenium, iridium oxide or tantalum nitride, gold, copper, aluminum, etc.) as a support and a cured film of a colored curable composition. . Specific examples thereof include a decane coupling agent and the like. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known one can be used.

矽烷偶合劑較佳的是日本專利特開2009-98616號公 報之段落0048中所記載之矽烷偶合劑，其中更佳的是γ-縮水甘油氧基丙基三烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷。該些矽烷偶合劑可單獨使用1種或者併用2種以上。 The decane coupling agent is preferably Japanese Patent Laid-Open No. 2009-98616 Further, the decane coupling agent described in the paragraph 0048 is more preferably γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxydecane. These decane coupling agents may be used alone or in combination of two or more.

作為本發明之著色硬化性組成物中之密接改良劑之含量(總量)，相對於著色硬化性組成物之總固形物量而言，較佳的是0.1質量%~20質量%，更佳的是0.2質量%~5質量%。 The content (total amount) of the adhesion improving agent in the colored curable composition of the present invention is preferably 0.1% by mass to 20% by mass based on the total solid content of the colored curable composition, more preferably It is 0.2% by mass to 5% by mass.

交聯劑 Crosslinker

於本發明之著色硬化性組成物中亦可補足性地使用交聯劑，從而進一步提高使著色硬化性組成物硬化而成的著色硬化膜之硬度。 In the color hardening composition of the present invention, the crosslinking agent may be used in a complementary manner to further increase the hardness of the colored cured film obtained by curing the colored curable composition.

交聯劑若為藉由交聯反應而進行膜硬化者，則並無特別限定，例如可列舉：(a)環氧樹脂、(b)經選自羥甲基、烷氧基甲基、及醯氧基甲基之至少1個取代基取代之三聚氰胺化合物、胍胺化合物、甘脲化合物或脲化合物、(c)經選自羥甲基、烷氧基甲基、及醯氧基甲基之至少1個取代基取代之酚化合物、萘酚化合物或羥基蒽化合物。 The crosslinking agent is not particularly limited as long as it is cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin and (b) a methyl group selected from a methyl group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of a methoxymethyl group, (c) selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group A phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted with at least one substituent.

其中，(a)環氧樹脂可藉由與可作為硬化劑而存在於著色硬化性組成物中之酸性成分(例如樹脂、單體等)或SH化合物(巰基化合物)之反應而形成更鞏固之著色硬化膜，因此特佳。另外，於環氧樹脂中，自低黏度、耐熱性、穩定性之觀點考慮，較佳的是脂環族環氧樹脂。 Among them, (a) the epoxy resin can be formed by reacting with an acidic component (for example, a resin, a monomer, etc.) or an SH compound (sulfonium compound) which can be present as a hardener in the colored curable composition. Coloring the cured film is therefore particularly good. Further, in the epoxy resin, an alicyclic epoxy resin is preferred from the viewpoint of low viscosity, heat resistance and stability.

關於交聯劑之具體例等詳細內容，可參照日本專利特 開2004-295116號公報之段落[0134]~段落[0147]之記載。 For details of specific examples of the crosslinking agent, etc., refer to Japanese Patent Special. The description of paragraphs [0134] to [0147] of the publication No. 2004-295116 is issued.

顯影促進劑 Development accelerator

於為了促進對著色硬化性組成物層進行曝光之情形時的非曝光區域的鹼溶解性，實現著色硬化性組成物之顯影性之更進一步提高之情形時，亦可於本發明之著色硬化性組成物中添加顯影促進劑。顯影促進劑較佳的是分子量為1000以下之低分子量有機羧酸化合物、或分子量為1000以下之低分子量酚化合物。 When the alkali solubility in the non-exposed region in the case of exposing the coloring-curable composition layer is promoted, and the developability of the colored curable composition is further improved, the color hardening property of the present invention can also be achieved. A development accelerator is added to the composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less or a low molecular weight phenol compound having a molecular weight of 1,000 or less.

具體而言，例如可列舉甲酸、乙酸、丙酸、丁酸、戊酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸等脂肪族單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、軟木酸、壬二酸、癸二酸、十三烷二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、檸康酸等脂肪族二羧酸；丙三甲酸、烏頭酸、降樟腦三酸等脂肪族三羧酸；苯甲酸、甲苯甲酸、小茴香酸、二甲基苯甲酸、二甲苯甲酸等芳香族單羧酸；鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三甲酸、均苯三甲酸、苯偏四甲酸、苯均四酸等芳香族多羧酸；苯乙酸、氫化阿托酸、氫化肉桂酸、苦杏仁酸、苯基琥珀酸、阿托酸、肉桂酸、肉桂酸甲酯、肉桂酸苄基酯、次肉桂基乙酸、香豆酸、傘形酸(umbellic acid)等。 Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid; oxalic acid, malonic acid, and amber. Acid, glutaric acid, adipic acid, pimelic acid, softwood acid, sebacic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, An aliphatic dicarboxylic acid such as methyl succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as propylene tricarboxylic acid, aconitic acid or camphoric acid; benzoic acid, toluic acid, fennel acid, and An aromatic monocarboxylic acid such as methylbenzoic acid or xylenecarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, benzoic acid, pyromellitic acid, etc. Aromatic polycarboxylic acid; phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, hypo-cinnamic acid, Coumaric acid, umbellic acid, and the like.

其他添加物 Other additives

本發明之著色硬化性組成物亦可視需要而含有各種添加物，例如填充劑、上述以外之高分子化合物、紫外線吸 收劑、抗氧化劑等。該些添加物可列舉日本專利特開2004-295116號公報之段落[0155]~段落[0156]中所記載者。 The colored curable composition of the present invention may contain various additives as needed, such as a filler, a polymer compound other than the above, and ultraviolet absorption. Recipients, antioxidants, etc. Examples of such additives include those described in paragraphs [0155] to [0156] of JP-A-2004-295116.

於本發明之著色硬化性組成物中可含有日本專利特開2004-295116號公報之段落[0078]中所記載之光穩定劑、日本專利特開2004-295116號公報之段落[0081]中所記載之熱聚合抑制劑。 The color-curable composition of the present invention may contain a light stabilizer described in paragraph [0078] of JP-A-2004-295116, and paragraph [0081] of JP-A-2004-295116. A thermal polymerization inhibitor as described.

著色硬化性組成物之調製方法 Method for preparing colored hardening composition

本發明之著色硬化性組成物可藉由將前述之各必須成分與視需要的任意成分加以混合而調製。 The colored curable composition of the present invention can be prepared by mixing the above-mentioned essential components with any optional components as needed.

另外，於調製著色硬化性組成物時，可將構成著色硬化性組成物之各成分總括調配，亦可將各成分溶解、分散於溶劑中之後進行逐次調配。而且，調配時之投入順序或作業條件並不受到特別制約。例如可將所有成分同時溶解、分散於溶劑而調製組成物，亦可視需要將各成分適宜地預先製成2種以上溶液、分散液，於使用時(塗佈時)對該些溶液、分散液進行混合而調製為著色硬化性組成物。 In addition, when the coloring curable composition is prepared, the components constituting the colored curable composition may be formulated in a total amount, or each component may be dissolved and dispersed in a solvent, and then successively formulated. Moreover, the order of input or the working conditions at the time of deployment are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and the solutions and dispersions may be used (at the time of application). The mixture was mixed to prepare a colored curable composition.

如上所述而調製之著色硬化性組成物較佳的是可使用孔徑為0.01μm~3.0μm左右之過濾器等而進行過濾分離後，供至使用。 The colored curable composition prepared as described above is preferably filtered and separated using a filter having a pore diameter of about 0.01 μm to 3.0 μm, and then used.

本發明之著色硬化性組成物能夠形成可構成亮度及對比度優異之彩色濾光片的著色硬化膜，因此可適宜地用作液晶顯示裝置中所使用之彩色濾光片等著色畫素形成用途，而且可適宜用作印刷墨水、噴墨墨水、及塗料等之製 作用途。 The colored curable composition of the present invention can form a colored cured film which can form a color filter excellent in brightness and contrast, and therefore can be suitably used as a coloring element for forming a color filter used in a liquid crystal display device. Moreover, it can be suitably used as a printing ink, an inkjet ink, a paint, etc. For use.

彩色濾光片及其製造方法 Color filter and manufacturing method thereof

本發明之彩色濾光片是包含基板、該基板上所設的由本發明之著色硬化性組成物所形成之著色區域而構成者。基板上之著色區域由形成彩色濾光片之各畫素的例如紅(R)、綠(G)、藍(B)等著色層而構成。 The color filter of the present invention comprises a substrate and a colored region formed by the colored curable composition of the present invention provided on the substrate. The colored region on the substrate is composed of a colored layer such as red (R), green (G), or blue (B) which forms each pixel of the color filter.

本發明之彩色濾光片的製造方法包含如下步驟：著色層形成步驟(A)，將所述的著色硬化性組成物賦予至支撐體上而形成著色層(著色硬化性組成物層)；曝光步驟(B)，對藉由步驟(A)而形成之著色層進行圖案模樣之曝光；顯影步驟(C)，對所述曝光後之著色層進行顯影而形成圖案。 The method for producing a color filter of the present invention comprises the steps of: a colored layer forming step (A), applying the colored curable composition to a support to form a colored layer (colored curable composition layer); and exposing In the step (B), the coloring layer formed by the step (A) is subjected to patterning exposure; in the developing step (C), the exposed coloring layer is developed to form a pattern.

而且，於本發明之彩色濾光片的製造方法中，特佳的是進一步設置步驟(D)的態樣，所述步驟(D)是對步驟(C)中所得之著色圖案進行加熱處理。 Further, in the method of producing a color filter of the present invention, it is particularly preferable to further provide the aspect of the step (D) of heat-treating the colored pattern obtained in the step (C).

以下，對本發明之彩色濾光片的製造方法進行更具體的說明。另外，除了先前所主要使用的製造方法以外，對自提高亮度及良率之觀點考慮有效的陣列上的彩色濾光片(Color Filter on Array，COA)方式之彩色濾光片製造方法亦加以說明。 Hereinafter, a method of producing the color filter of the present invention will be described more specifically. In addition, in addition to the manufacturing method mainly used previously, the color filter on Array (COA) color filter manufacturing method on the array is also considered from the viewpoint of improving brightness and yield. .

先前型之彩色濾光片製造方法 Prior type color filter manufacturing method

步驟(A) Step (A)

於本發明之彩色濾光片的製造方法中，首先藉由旋轉塗佈、狹縫塗佈、流延塗佈、輥塗、棒塗、或噴墨等塗佈 方法將所述之本發明之著色硬化性組成物賦予至支撐體上而形成著色層，其後對該著色層進行加熱(預烤)或真空乾燥等而使其乾燥。 In the method for producing a color filter of the present invention, first, coating by spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet Method The coloring composition of the present invention described above is applied to a support to form a colored layer, and then the colored layer is heated (prebaked) or vacuum dried to dry it.

支撐體例如可列舉液晶顯示裝置中所使用之鈉玻璃、無鹼玻璃、硼矽玻璃、石英玻璃、矽基板、樹脂基板等。而且，於該些支撐體上亦可視需要設置下塗層而用以改良與上部之層之密接、防止物質之擴散、或表面之平坦化。另外，所述支撐體亦可為於支撐體上形成有薄膜電晶體(thin-film transistor，TFT)膜之TFT基板。 Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a liquid crystal display device. Further, an undercoat layer may be provided on the support bodies to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface. Further, the support may be a TFT substrate on which a thin-film transistor (TFT) film is formed on a support.

預烤之條件可列舉使用加熱板(hot plate)或烘箱(oven)，於70℃~130℃下加熱0.5分鐘~15分鐘左右之條件。 The prebaking conditions may be a condition of heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

而且，由著色硬化性組成物所形成之著色層之厚度可根據目的而適宜選擇。於液晶顯示裝置用彩色濾光片中，較佳的是0.2μm~5.0μm之範圍，更佳的是1.0μm~4.0μm之範圍。另外，著色層之厚度是乾燥後之膜厚。 Further, the thickness of the coloring layer formed of the colored curable composition can be appropriately selected depending on the purpose. The color filter for a liquid crystal display device preferably has a range of 0.2 μm to 5.0 μm, more preferably 1.0 μm to 4.0 μm. Further, the thickness of the colored layer is the film thickness after drying.

步驟(B) Step (B)

繼而，於本發明之彩色濾光片的製造方法中，對支撐體上所形成之著色層進行圖案模樣之曝光。可適用於曝光之光或放射線較佳的是g線、h線、i線、各種雷射光，特佳的是i線。於照射光使用i線之情形時，較佳的是藉由5mJ/cm2~500mJ/cm2之曝光量進行照射。 Then, in the method of producing a color filter of the present invention, the coloring layer formed on the support is subjected to patterning exposure. The light or radiation that can be applied to the exposure is preferably a g-line, an h-line, an i-line, or various kinds of laser light, and particularly preferably an i-line. In the case where the i-line is used for the irradiation light, it is preferable to irradiate with an exposure amount of 5 mJ/cm 2 to 500 mJ/cm 2 .

而且，其他曝光光源可使用超高壓、高壓、中壓、低壓之各水銀燈、化學燈、碳弧燈、氙氣燈、金屬鹵素燈、 各種雷射光源等。 Moreover, other exposure light sources can use ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, Various laser sources, etc.

使用雷射光源之曝光步驟 Exposure step using a laser source

於使用雷射光源之曝光方式中，照射光較佳的是波長為300nm~410nm之範圍的波長範圍之紫外光雷射，更佳的是300nm~360nm之範圍的波長。具體而言，特別是可適宜使用輸出功率大、比較廉價之固體雷射之Nd：YAG雷射之第三諧波(355nm)或準分子雷射之XeCl(308nm)、XeF(353nm)。作為圖案之曝光量，自生產性之觀點考慮，較佳的是1mJ/cm2~100mJ/cm2之範圍，更佳的是1mJ/cm2~50mJ/cm2之範圍。 In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, more preferably a wavelength in the range of 300 nm to 360 nm. Specifically, in particular, it is preferable to use a third harmonic (355 nm) of a Nd:YAG laser having a large output power and a relatively inexpensive solid laser, or XeCl (308 nm) and XeF (353 nm) of a pseudo-molecular laser. The exposure amount of the pattern is preferably in the range of 1 mJ/cm 2 to 100 mJ/cm 2 from the viewpoint of productivity, and more preferably in the range of 1 mJ/cm 2 to 50 mJ/cm 2 .

曝光裝置並無特別限制，市售之曝光裝置可使用Callisto(商品名、V Technology Co.,Ltd.製造)或EGIS(商品名、V Technology Co.,Ltd.製造)或DF2200G(商品名、大日本網屏(Dainippon Screen)股份有限公司製造)等。而且，亦可適宜使用上述以外之裝置。 The exposure apparatus is not particularly limited, and a commercially available exposure apparatus may use Callisto (trade name, manufactured by V Technology Co., Ltd.) or EGIS (trade name, manufactured by V Technology Co., Ltd.) or DF2200G (trade name, large Japan's screen (made by Dainippon Screen Co., Ltd.) and so on. Further, it is also possible to suitably use a device other than the above.

步驟(C) Step (C)

繼而，對曝光後之著色層用顯影液進行顯影。由此可形成著色圖案。顯影液若為溶解著色層之未硬化部且並不溶解硬化部者，則可使用各種有機溶劑之組合或鹼性水溶液。於顯影液為鹼性水溶液之情形時，可將鹼濃度調整為較佳的是pH成為10~13。所述鹼性水溶液例如可列舉氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、二乙基胺、二甲基乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、膽鹼、吡咯、哌啶、1,8-二氮 雜雙環-[5.4.0]-7-十一碳烯等之鹼性水溶液。 Then, the exposed color layer is developed with a developer. Thereby, a colored pattern can be formed. When the developer is a uncured portion in which the colored layer is dissolved and the hardened portion is not dissolved, a combination of various organic solvents or an aqueous alkaline solution can be used. In the case where the developer is an alkaline aqueous solution, the alkali concentration can be adjusted so that the pH becomes 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethyl. Ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diaza An alkaline aqueous solution of heterobicyclo-[5.4.0]-7-undecene.

顯影時間較佳的是30秒~300秒，更佳的是30秒~120秒。顯影溫度較佳的是20℃~40℃，更佳的是23℃。 The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, more preferably 23 ° C.

顯影可藉由覆液方式、噴淋方式、噴霧方式等而進行。 Development can be carried out by a liquid coating method, a shower method, a spray method, or the like.

而且，於使用鹼性水溶液進行顯影後，較佳的是藉由水進行清洗。 Further, after development using an aqueous alkaline solution, it is preferred to wash by water.

於本發明之彩色濾光片的製造方法中，特別是對使用著色硬化性組成物而形成之著色圖案(畫素)進行利用紫外線照射之後曝光亦較佳。 In the method for producing a color filter of the present invention, in particular, exposure to a colored pattern (pixel) formed using a colored curable composition is preferably performed after exposure to ultraviolet rays.

步驟(D) Step (D)

較佳的是對顯影後之著色圖案進一步進行加熱處理，或者對進行了如上所述之利用紫外線照射之後曝光的著色圖案進一步進行加熱處理。藉由對所形成之著色圖案進行加熱處理(所謂之後烘烤處理)，可進一步使著色圖案硬化。該加熱處理例如可藉由加熱板、各種加熱器、烘箱等而進行。 It is preferable to further heat-treat the coloring pattern after development or to further heat-treat the coloring pattern which has been exposed by ultraviolet irradiation as described above. The colored pattern can be further hardened by subjecting the formed color pattern to heat treatment (so-called post-baking treatment). This heat treatment can be performed, for example, by a heating plate, various heaters, an oven, or the like.

加熱處理時之溫度較佳的是100℃~300℃，更佳的是150℃~250℃。而且，加熱時間較佳的是10分鐘~120分鐘左右。 The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. Moreover, the heating time is preferably about 10 minutes to 120 minutes.

如上所述而得之著色圖案構成彩色濾光片中之畫素。於具有多種色調之畫素的彩色濾光片之製作中，根據所期望之顏色數而反覆進行上述步驟(A)、步驟(B)、步驟(C)、及視需要之步驟(D)即可。 The colored pattern obtained as described above constitutes a pixel in the color filter. In the production of a color filter having a plurality of hues of pixels, the above steps (A), (B), (C), and optionally (D) are performed in accordance with the desired number of colors. can.

另外，可於每一單色之著色層之形成、曝光、顯影結 束(每1色)後進行所述步驟(D)，亦可於所期望之顏色數之所有著色層之形成、曝光、顯影結束後，總括進行所述步驟(D)。 In addition, the formation, exposure, and development of each color layer can be formed The step (D) is carried out after the bundle (per color), and the step (D) may be collectively performed after the formation, exposure, and development of all the colored layers of the desired number of colors are completed.

COA方式彩色濾光片的製造方法 Method for manufacturing COA color filter

本發明之COA方式之彩色濾光片的製造方法包含如下步驟：著色層形成步驟(A)，使用TFT基板作為支撐體，將所述之著色硬化性組成物賦予至作為支撐體之TFT基板上而形成著色層(著色硬化性組成物層)；曝光步驟(B)，對藉由步驟(A)而形成之著色層進行圖案模樣之曝光；顯影步驟(C)，對所述曝光後之著色層進行顯影而形成著色圖案。而且，特佳的是進一步設置步驟(D)之態樣，所述步驟(D)是對步驟(C)中所得之著色圖案進行加熱處理。 The method for producing a COA color filter of the present invention comprises the steps of: a colored layer forming step (A), using the TFT substrate as a support, and applying the colored hardenable composition to a TFT substrate as a support. Forming a coloring layer (coloring hardenable composition layer); exposing step (B), performing patterning exposure on the coloring layer formed by the step (A); developing step (C), coloring after the exposure The layer is developed to form a colored pattern. Moreover, it is particularly preferable to further set the aspect of the step (D) of heat-treating the colored pattern obtained in the step (C).

於COA方式之彩色濾光片的製造方法中，於如上所述地於TFT基板上形成所期望之著色圖案(畫素)後更包含如下步驟：步驟(E)，於所形成之畫素上形成透明電極膜；步驟(F)，對所述透明電極膜進行圖案化處理而形成畫素電極。 In the COA method for manufacturing a color filter, after forming a desired color pattern (pixel) on the TFT substrate as described above, the method further includes the following step: step (E), on the formed pixel A transparent electrode film is formed; in step (F), the transparent electrode film is patterned to form a pixel electrode.

於著色層形成步驟(A)中，於TFT基板上賦予著色硬化性組成物而形成著色層。著色層之形成例如可藉由如下方式而進行：塗佈著色硬化性組成物，視需要進行乾燥(預烤)處理而形成塗佈膜。著色硬化性組成物之塗佈可直接或介隔其他層而藉由旋轉塗佈(旋塗)、狹縫塗佈、流延塗佈、或輥塗等於TFT基板上進行。 In the colored layer forming step (A), a colored curable composition is applied onto the TFT substrate to form a colored layer. The formation of the colored layer can be carried out, for example, by applying a colored curable composition, and drying (pre-baking) treatment as necessary to form a coating film. The application of the colored curable composition can be carried out by spin coating (spin coating), slit coating, cast coating, or roll coating directly or via other layers, on the TFT substrate.

於進行乾燥(預烤)處理之情形時，其條件可根據著色硬化性組成物之構成而適宜選擇。例如可藉由加熱板、烘箱等而於50℃~140℃之溫度下進行10秒~300秒。而且，於近年來，基板之大型化不斷發展，因此作為塗佈膜之形成方法，狹縫塗佈亦有效，該塗佈方法逐漸成為一般的方法。 In the case of performing the drying (pre-baking) treatment, the conditions can be appropriately selected depending on the constitution of the colored curable composition. For example, it can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds by means of a hot plate, an oven or the like. Further, in recent years, the size of the substrate has been increasing. Therefore, as a method of forming the coating film, slit coating is also effective, and the coating method is gradually becoming a general method.

COA方式之彩色濾光片的製造方法中的著色層形成步驟(A)可參照所述之先前型之彩色濾光片製造方法中之步驟(A)之記載。 The coloring layer forming step (A) in the method for producing a COA color filter can be referred to the description of the step (A) in the above-described color filter manufacturing method.

於曝光步驟(B)中，對所述著色層進行圖案曝光。著色層之圖案曝光例如為負型之情形時，可介隔規定之遮罩圖案而進行曝光，使僅僅進行了光照射之著色層部分硬化而進行。作為曝光時所可使用的放射線，特別是可較佳地使用g線、i線等紫外線。 In the exposure step (B), the colored layer is subjected to pattern exposure. When the pattern exposure of the colored layer is, for example, a negative type, exposure can be performed by interposing a predetermined mask pattern, and the coloring layer which is only irradiated with light is partially cured. As the radiation which can be used at the time of exposure, in particular, ultraviolet rays such as g-line or i-line can be preferably used.

COA方式之彩色濾光片的製造方法中之曝光步驟(B)可參照所述之先前型之彩色濾光片製造方法中的步驟(B)之記載。 The exposure step (B) in the method for producing a COA color filter can be referred to the description of the step (B) in the above-described color filter manufacturing method.

於顯影步驟(C)中，使所述曝光步驟後之非硬化部溶出至顯影液(例如鹼性水溶液)中，形成包含硬化部之著色圖案。於所述著色硬化性組成物為負型之情形時，未進行所述曝光之非硬化部溶出至顯影液中，僅僅殘存進行了光硬化之部分。顯影液理想的是不對基底之電路等造成損傷之有機鹼性顯影液。有機鹼性顯影液例如可使用以純水將如下之有機鹼性化合物稀釋至濃度成為0.001質量% ~10質量%、較佳的是0.01質量%~1質量%的鹼性水溶液：氨水、乙基胺、二乙基胺、二甲基乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、膽鹼、吡咯、哌啶、1,8-二氮雜雙環-[5.4.0]-7-十一碳烯等。另外，於使用包含此種鹼性水溶液之顯影液之情形時，一般情況下於顯影處理後，藉由純水進行清洗(沖洗)。 In the developing step (C), the non-hardened portion after the exposure step is eluted into a developing solution (for example, an alkaline aqueous solution) to form a colored pattern including a cured portion. When the coloring curable composition is in a negative form, the non-hardened portion not subjected to the exposure is eluted into the developing solution, and only the portion where the light curing is performed remains. The developer is desirably an organic alkaline developer which does not cause damage to the circuit of the substrate or the like. For the organic alkaline developing solution, for example, the following organic basic compound can be diluted to a concentration of 0.001% by mass with pure water. ~10% by mass, preferably 0.01% by mass to 1% by mass of an aqueous alkaline solution: ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene and the like. Further, in the case of using a developer containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after the development treatment.

顯影溫度通常為20℃~30℃，顯影時間為20秒~90秒。 The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

COA方式之彩色濾光片的製造方法中之顯影步驟(C)可參照所述之先前型之彩色濾光片製造方法中之步驟(C)之記載。 The development step (C) in the method for producing a COA color filter can be referred to the description of the step (C) in the above-described color filter manufacturing method.

於進行加熱處理之步驟(D)中，對顯影步驟(C)中所形成之著色圖案進行加熱處理(後烘烤)。後烘烤是用以使著色圖案之硬化完全的顯影後之加熱處理，通常進行200℃~240℃之熱硬化處理。該後烘烤處理可以成為所述條件之方式使用加熱板或對流烘箱(熱風循環式乾燥機)、高頻波加熱機等加熱機構，以連續式或分批式對顯影後之塗佈膜進行。 In the step (D) of performing the heat treatment, the colored pattern formed in the developing step (C) is subjected to heat treatment (post-baking). The post-baking is a heat treatment after development for completely curing the colored pattern, and is usually subjected to a heat hardening treatment at 200 ° C to 240 ° C. This post-baking treatment can be carried out by using a heating plate, a convection oven (hot air circulation dryer), a heating mechanism such as a high-frequency wave heater, or the like, and the developed coating film can be continuously or batch-wise.

COA方式之彩色濾光片的製造方法中的顯影步驟(C)可參照所述之先前型之彩色濾光片製造方法中的步驟(C)之記載。 The development step (C) in the method for producing a COA color filter can be referred to the description of the step (C) in the above-described color filter manufacturing method.

關於構成彩色濾光片之各顏色，可如上所述地順次反覆進行步驟(A)~步驟(C)、及視需要之步驟(D)而製造具有所期望之著色圖案的著色硬化膜。藉此而獲得彩 色濾光片。 With respect to each of the colors constituting the color filter, the steps (A) to (C) and, if necessary, the step (D) can be sequentially performed as described above to produce a colored cured film having a desired color pattern. Get the color Color filter.

於形成透明電極膜之步驟(E)中，如上所述地進行而於TFT基板上所形成的所期望之著色圖案(畫素)上形成透明電極膜。構成透明電極膜之材料例如可列舉ITO。由ITO等所形成之透明電極膜例如可藉由濺鍍而形成。濺鍍之條件可根據通常所使用之條件而適宜選擇。 In the step (E) of forming the transparent electrode film, a transparent electrode film is formed on the desired color pattern (pixel) formed on the TFT substrate as described above. The material constituting the transparent electrode film is exemplified by ITO. The transparent electrode film formed of ITO or the like can be formed, for example, by sputtering. The conditions of the sputtering can be appropriately selected depending on the conditions generally used.

於形成畫素電極之步驟(F)中，對畫素上所形成之透明電極膜進行圖案化處理而形成畫素電極。透明電極層之圖案化處理例如可如下所述地進行。於透明電極膜上形成正型光阻塗佈膜，對該光阻膜實施圖案曝光、顯影處理後，進一步使用氫氟酸等化學品對必要的透明電極膜(較佳的是ITO)進行蝕刻處理而形成畫素電極圖案。其後，藉由剝離液將該畫素電極圖案上所殘存之光阻膜除去，由此可形成畫素電極。 In the step (F) of forming the pixel electrode, the transparent electrode film formed on the pixel is patterned to form a pixel electrode. The patterning treatment of the transparent electrode layer can be performed, for example, as follows. Forming a positive photoresist coating film on the transparent electrode film, patterning and developing the photoresist film, and further etching the necessary transparent electrode film (preferably ITO) using a chemical such as hydrofluoric acid. The process forms a pixel electrode pattern. Thereafter, the photoresist film remaining on the pixel electrode pattern is removed by a stripping liquid, whereby a pixel electrode can be formed.

形成畫素電極之步驟中所使用的光阻劑較佳的是具有耐蝕刻性之正型光阻劑。而且，圖案曝光或顯影、蝕刻可並無限制地使用通常公知之手法。 The photoresist used in the step of forming the pixel electrode is preferably a positive photoresist having etching resistance. Further, pattern exposure or development, etching, and the like, which are generally known, can be used without limitation.

藉由剝離液將所形成之畫素電極上所殘留之光阻膜剝離除去。該剝離液可並無特別限制地使用先前公知之剝離液。例如可使用日本專利特開昭51-72503號、日本專利特開昭57-84456號、日本專利特開平6-222573號等之各公報或者美國專利第4165294號及歐洲專利第0119337號之各說明書中所揭示之各種有機溶劑。代表性的剝離液可列舉單乙醇胺(MEA)與二甲基亞碸(DMSO)之混合溶劑。 而且，藉由使用加熱至60℃以上之有機溶劑作為剝離液，可將剝離步驟設為短時間，而且亦可進一步消除顯影殘渣之問題。 The photoresist film remaining on the formed pixel electrode was peeled off by a stripper. The peeling liquid can be a previously known peeling liquid without any particular limitation. For example, each of the publications of Japanese Patent Laid-Open No. Hei 51-72503, Japanese Patent Laid-Open No. Hei 57-84456, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei. Various organic solvents disclosed in the above. A typical stripping solution is a mixed solvent of monoethanolamine (MEA) and dimethylarylene (DMSO). Further, by using an organic solvent heated to 60 ° C or higher as a peeling liquid, the peeling step can be set to a short time, and the problem of development residue can be further eliminated.

所述著色硬化性組成物特別是耐剝離液性優異，因此即使使用加熱至60℃以上之有機溶劑，亦可並不產生彩色濾光片之塗膜剝落、膨潤、膨脹地將光阻膜除去。 Since the colored curable composition is particularly excellent in peeling resistance, even if an organic solvent heated to 60° C. or higher is used, the photoresist film can be removed without peeling, swelling, or swelling of the coating film of the color filter. .

如上所述而製造之COA方式之彩色濾光片通常以如日本專利特開平9-311347號公報之圖式所揭示之結構而用於TFT液晶顯示裝置等各種顯示裝置中。所述彩色濾光片適於COA方式，因此容易對準，可提高數值孔徑。而且，使用所述著色硬化性組成物而形成畫素，因此耐剝離液性高，因此良率高，生產效率亦高。而且，彩色濾光片所通常要求的耐熱變色性、低介電常數性、膜厚均一性、解析性、電壓保持率、耐光性等亦良好。 The color filter of the COA system manufactured as described above is generally used in various display devices such as a TFT liquid crystal display device, as disclosed in the drawings disclosed in Japanese Laid-Open Patent Publication No. Hei 9-311347. The color filter is suitable for the COA mode, so that it is easy to align and the numerical aperture can be improved. Further, since the coloring curable composition is used to form a pixel, the peeling resistance is high, so the yield is high and the production efficiency is high. Further, the color filter generally has excellent heat discoloration resistance, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance, and the like.

彩色濾光片之結構可為如上所述地僅僅包含1層畫素之形態，而且亦可於基板與畫素電極之間包含如下2層：由畫素用著色硬化性組成物所形成之著色圖案，與該著色圖案上所形成之包含畫素保護膜用光熱聚合性組成物的畫素保護膜。 The color filter may have a structure including only one layer of pixels as described above, and may also include two layers between the substrate and the pixel electrode: coloring formed by the coloring hardenable composition for the pixel A pattern and a pixel protective film comprising the photothermal polymerizable composition for a pixel protective film formed on the colored pattern.

構成所述COA方式之彩色濾光片的著色圖案之膜厚較佳的是0.3μm~5.0μm，更佳的是0.5μm~3.5μm。塗佈厚度較厚者可達成高色度，但若塗佈厚度較厚，則接觸孔之解析性變差，因此必須平衡。而且，所述畫素保護膜之膜厚較佳的是0.2μm~5.0μm，更佳的是0.2μm~3.0 μm。而且，理想的是使成為基底之著色圖案之凹凸平坦化，表面平滑。 The film thickness of the colored pattern constituting the color filter of the COA method is preferably 0.3 μm to 5.0 μm, more preferably 0.5 μm to 3.5 μm. A high chromaticity can be achieved if the coating thickness is thick, but if the coating thickness is thick, the resolution of the contact hole is deteriorated, so it is necessary to balance. Further, the film thickness of the pixel protective film is preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3.0. Mm. Further, it is desirable to flatten the unevenness of the colored pattern to be the base and to smooth the surface.

顯示裝置 Display device

由本發明之彩色濾光片的製造方法而得的彩色濾光片(本發明之彩色濾光片)使用本發明之著色硬化性組成物，因此亮度及對比度優異。 Since the color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention uses the color hardening composition of the present invention, it is excellent in brightness and contrast.

本發明之顯示裝置包含本發明之彩色濾光片。 The display device of the present invention comprises the color filter of the present invention.

作為本發明之顯示裝置，具體而言適宜的是液晶顯示器(液晶顯示裝置；LCD)、有機EL顯示器(有機EL顯示裝置)、液晶投影儀、遊戲機用顯示裝置、行動電話等移動終端用顯示裝置、數位相機用顯示裝置、汽車導航用顯示裝置等之顯示裝置，特別適宜的是彩色顯示裝置。 Specific examples of the display device of the present invention are liquid crystal display (liquid crystal display device; LCD), organic EL display (organic EL display device), liquid crystal projector, display device for game machine, and display for mobile terminals such as mobile phones. A display device such as a display device, a display device for a digital camera, or a display device for a car navigation is particularly preferably a color display device.

於將本發明之彩色濾光片用於有機EL顯示裝置或液晶顯示裝置等中之情形時，可達成良好之色調，且變得可顯示分光特性及對比度優異之影像。 When the color filter of the present invention is used in an organic EL display device or a liquid crystal display device or the like, a good color tone can be achieved, and an image excellent in spectral characteristics and contrast can be displayed.

液晶顯示裝置 Liquid crystal display device

對使用本發明之彩色濾光片的液晶顯示裝置加以說明。關於有機EL顯示裝置或液晶顯示裝置之定義或各顯示裝置之詳細，例如於「電子顯示裝置(佐佐木 昭夫著、工業調查會股份有限公司1990年發行)」、「顯示裝置(伊吹 順章著、產業圖書股份有限公司 平成元年(1989年)發行)」等中有所記載。而且，關於液晶顯示裝置，例如於「下一代液晶顯示器技術(內田 龍男編集、工業調查會股份有限公司1994年發行)」中有所記載。可適用本發明 之液晶顯示裝置並無特別限制，例如可使用於上述「下一代液晶顯示器技術」中所記載之各種方式之液晶顯示裝置中。 A liquid crystal display device using the color filter of the present invention will be described. The definition of the organic EL display device or the liquid crystal display device or the details of each display device are, for example, "electronic display device (sasaki Sasaki, Industrial Research Association, Inc., 1990)", "display device (Ibuki Shunzhang, Industrial Book Co., Ltd. was issued in the first year of Heisei (1989). In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (issued by Uchida Natsuo, Industrial Research Association, 1994)". Applicable to the present invention The liquid crystal display device is not particularly limited, and can be used, for example, in various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

其中，本發明之彩色濾光片對於彩色TFT方式之液晶顯示裝置而言特別有效。關於彩色TFT方式之液晶顯示裝置，例如於「彩色TFT液晶顯示器(共立出版股份有限公司1996年發行)」中有所記載。另外，本發明亦適用於共平面切換(In-plane Switching，IPS)等橫電場驅動方式、多區域垂直配向(Multi-domain Vertical Alignment，MVA)等畫素分割方式等視角得到擴大之液晶顯示裝置，或者超扭轉向列(Super Twisted Nematic，STN)、扭轉向列(Twisted Nematic，TN)、垂直配向(Vertical Alignment，VA)、光學補償擴散(Optically Compensated Splay，OCS)、邊緣場切換(Fringe Field Switching，FFS)、及反射式光學補償彎曲(Reflective Optically Compensated Bend，R-OCB)等中。而且，本發明之彩色濾光片亦可供至陣列上的彩色濾光片(Color-filter On Array，COA)方式中。 Among them, the color filter of the present invention is particularly effective for a color TFT type liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field driving method such as In-plane Switching (IPS) or a multi-domain vertical alignment (MVA) is expanded. , or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field (Fringe Field) Switching, FFS), and Reflective Optically Compensated Bend (R-OCB). Moreover, the color filter of the present invention is also available in a color-filter on Array (COA) mode on the array.

若將本發明之彩色濾光片用於液晶顯示裝置中，則與先前公知之冷陰極管之三波長管組合時可實現高的對比度，另外藉由將紅、綠、藍之LED(Light Emitting Diode，發光二極體)光源(RGB-LED)作為背光源而可提供亮度高、而且色純度高之顏色再現性良好的液晶顯示裝置。 When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventionally known three-wavelength tube of a cold cathode tube, and LEDs of red, green and blue are additionally used (Light Emitting) As a backlight, a Diode (light-emitting diode) light source (RGB-LED) can provide a liquid crystal display device having high luminance and high color reproducibility.

[實例] [Example]

以下，藉由實例對本發明加以更具體的說明，但本發 明只要不超過其主旨，則並不限定於以下實例。另外，若無特別說明，則「份」、「%」是質量基準。 Hereinafter, the present invention will be more specifically described by way of examples, but the present invention As long as it does not exceed its subject matter, it is not limited to the following examples. In addition, "parts" and "%" are quality standards unless otherwise specified.

實例1-1 Example 1-1

著色硬化性組成物之調製 Modulation of colored hardening composition

將下述各成分加以混合、溶解而調製著色硬化性組成物。 The following components were mixed and dissolved to prepare a colored curable composition.

另外，所述藍色顏料分散液可如下所述地調製。 Further, the blue pigment dispersion can be prepared as described below.

將C.I.顏料藍15：6 12.8份與分散劑(日本路博潤(Lubrizol)公司製造、商品名：Solsperse 5500) 7.2份，與丙二醇單甲醚乙酸酯80.0份混合，使用珠磨機而使顏料充分分散，製備藍色顏料分散液。 7.2 parts of CI Pigment Blue 15:6 12.8 parts with a dispersing agent (manufactured by Lubrizol Co., Ltd., trade name: Solsperse 5500), and 80.0 parts of propylene glycol monomethyl ether acetate were mixed with a bead mill. The pigment was sufficiently dispersed to prepare a blue pigment dispersion.

染料溶液1是將下述各成分加以混合、溶解而製作。於實例1中，染料溶液1之染料濃度相對於著色硬化性組成物中之有色材料而言為0.1%。 The dye solution 1 is prepared by mixing and dissolving each of the following components. In Example 1, the dye concentration of the dye solution 1 was 0.1% with respect to the colored material in the colored hardenable composition.

染料溶液2是將下述各成分加以混合、溶解而製作。 The dye solution 2 is prepared by mixing and dissolving each of the following components.

於染料溶液1中包含作為(B)卟啉化合物之(P-26)，於染料溶液2中包含作為(A-1)二吡咯亞甲基金屬錯合物化合物之通式(I)之例示化合物(11)。另外，於下述表1中，例如將屬於通式(I)之例示化合物(x)記載為 「(I-x)」。 The dye solution 1 contains (P-26) as the (B) porphyrin compound, and the exemplified formula (I) containing the (A-1) dipyrromethene metal complex compound in the dye solution 2 Compound (11). Further, in the following Table 1, for example, the exemplified compound (x) belonging to the formula (I) is described as "(I-x)".

著色硬化性組成物層(著色層)之形成 Formation of a colored curable composition layer (colored layer)

藉由旋塗法而於玻璃(#1737；康寧公司製造)基板上塗佈上述所調製之著色硬化性組成物後，於室溫下乾燥30分鐘而使揮發成分揮發，形成著色層A。對該著色層A照射i線(波長為365nm)而形成潛影。i線之光源使用超高壓水銀燈，設為平行光後進行照射。此時，照射光量為40mJ/cm2。其次，對於該形成有潛影之著色層，使用碳酸鈉/碳酸氫鈉之水溶液(濃度為2.4%)而於26℃下進行45秒之顯影，其次藉由流水進行20秒之沖洗後，進行噴霧後使其乾燥，獲得細線圖案影像。將所得之細線圖案影像於230℃下進行20分鐘之後烘烤處理，獲得膜厚為2μm之著色層(著色硬化膜)B。 The above-described colored color-curable composition was applied onto a glass (#1737; manufactured by Corning) substrate by a spin coating method, and then dried at room temperature for 30 minutes to volatilize volatile components to form a colored layer A. The colored layer A was irradiated with an i-line (wavelength: 365 nm) to form a latent image. The light source of the i-line is an ultra-high pressure mercury lamp, and is irradiated with parallel light. At this time, the amount of irradiation light was 40 mJ/cm 2 . Next, the coloring layer forming the latent image was developed using an aqueous solution of sodium carbonate/sodium hydrogencarbonate (concentration: 2.4%) at 26 ° C for 45 seconds, followed by rinsing with running water for 20 seconds. After spraying, it was dried to obtain a fine line image. The obtained fine line pattern image was baked at 230 ° C for 20 minutes, and then baked to obtain a color layer (colored cured film) B having a film thickness of 2 μm.

評價 Evaluation

關於上述所得之著色層之對比度及分光特性，藉由以下所示之方法而進行評價。將評價結果示於下述表2中。 The contrast and spectral characteristics of the coloring layer obtained above were evaluated by the method shown below. The evaluation results are shown in Table 2 below.

(1)對比度 (1) Contrast

而且，將所得之具有各著色層B的基板夾持於2枚偏光膜之間，使用色彩亮度計(拓普康(TOPCON)股份有限公司製造、型號：BM-5A)而測定，2枚偏光膜之偏光軸平行之情形及垂直之情形的亮度值，2枚偏光膜之偏光軸平行之情形的亮度除以垂直之情形的亮度，求出所得之值作為對比度。對比度越高，則作為液晶顯示裝置用彩色濾光片而越顯示良好之性能。 Further, the obtained substrate having each colored layer B was sandwiched between two polarizing films, and measured by a color luminance meter (manufactured by TOPCON Co., Ltd., model: BM-5A), and two polarized lights were used. When the polarization axes of the films are parallel and the luminance values in the case of vertical, the luminance of the case where the polarization axes of the two polarizing films are parallel are divided by the luminance in the vertical direction, and the obtained value is obtained as the contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(2)分光特性(亮度) (2) Spectral characteristics (brightness)

使用奧林巴司股份有限公司製造之顯微分光測定裝置OSP-SP200(商品名)而測定上述所得之著色層B之透射光譜。藉由所得之透射光譜，求出CIE1931表色系統中之色度座標x值、y值、Y值。 The transmission spectrum of the coloring layer B obtained above was measured using the microscopic spectrometry apparatus OSP-SP200 (trade name) manufactured by Olympus Co., Ltd. The chromaticity coordinates x, y, and Y values in the CIE1931 color system were obtained from the obtained transmission spectra.

作為分光特性，於(x,y)=(0.138,0.085)中之Y值(亮度)高之情形時，可以說具有優異之分光特性，於將此種著色層適用於彩色濾光片時獲得良好之影像。 As a spectral characteristic, when the Y value (brightness) in (x, y) = (0.138, 0.085) is high, it can be said that it has excellent spectral characteristics, and is obtained when the coloring layer is applied to a color filter. Good image.

實例1-2~實例1-4 Example 1-2~Example 1-4

於實例1中，如表1中所記載那樣變更染料溶液1之使用量，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層，並且進行評價。將評價結果一併記載於表2中。 In the same manner as in Example 1-1 except that the amount of the dye solution 1 was changed as described in Table 1, the colored curable composition was prepared to form a colored layer, and the evaluation was carried out. The evaluation results are collectively shown in Table 2.

實例1-5 Example 1-5

著色硬化性組成物之調製 Modulation of colored hardening composition

將下述各成分混合、溶解而調製著色硬化性組成物。 The following components were mixed and dissolved to prepare a colored curable composition.

與實例1同樣地進行所得之著色硬化性組成物之評價。將評價結果示於表2中。 The evaluation of the obtained color hardening composition was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

染料溶液3是將下述各成分混合、溶解而製作。於實例1中，染料溶液1之染料濃度是相對於著色硬化性組成物中之有色材料而言為0.1%。 The dye solution 3 is produced by mixing and dissolving each of the following components. In Example 1, the dye concentration of the dye solution 1 was 0.1% with respect to the colored material in the colored hardenable composition.

而且，染料溶液2是與實例1中所使用者相同之染料溶液。 Further, the dye solution 2 was the same dye solution as that of the user of Example 1.

於染料溶液3中包含作為(B)卟啉化合物之(P-32)，於染料溶液2中包含作為(A-1)二吡咯亞甲基金屬錯合物化合物之(例示化合物(I-11))。 (P-32) as the (B) porphyrin compound in the dye solution 3, and as the (A-1) dipyrromethene metal complex compound in the dye solution 2 (exemplified compound (I-11) )).

實例1-6~實例1-8 Example 1-6~ Example 1-8

於實例1-5中，如表1中所記載那樣變更染料溶液1中之特定染料(B)之使用量，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層且進行評價。將評價結果示於下述表2中。 In Example 1-5, the coloring curable composition was prepared in the same manner as in Example 1-1 except that the amount of the specific dye (B) in the dye solution 1 was changed as described in Table 1, and coloring was formed to form a color. The layers were evaluated. The evaluation results are shown in Table 2 below.

實例1-9~實例1-12 Example 1-9~Example 1-12

於實例1-3中，如表1中所記載那樣變更染料溶液1中之特定染料(B)之種類與使用量，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層且進行評價。將評價結果示於下述表2中。 In Example 1-3, the coloring curable composition was prepared in the same manner as in Example 1-1 except that the type and amount of the specific dye (B) in the dye solution 1 were changed as described in Table 1. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.

實例1-13~實例1-18 Example 1-13~Example 1-18

於實例1-3中，如表1中所記載那樣變更染料溶液2中之特定染料(A-1)、特定染料(A-2)，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層且進行評價。將評價結果示於下述表2中。 In Example 1-3, the specific dye (A-1) and the specific dye (A-2) in the dye solution 2 were changed as described in Table 1, and the coloring was carried out in the same manner as in Example 1-1. The curable composition was formed into a colored layer and evaluated. The evaluation results are shown in Table 2 below.

實例1-19~實例1-24 Example 1-19~Example 1-24

於實例1-7中，如表1中所記載那樣變更染料溶液2 中之特定染料(A-1)、特定染料(A-2)，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層且進行評價。將評價結果示於下述表2中。 In Examples 1-7, the dye solution 2 was changed as described in Table 1. In the same manner as in Example 1-1 except that the specific dye (A-1) and the specific dye (A-2) were used, the colored curable composition was prepared to form a colored layer and evaluated. The evaluation results are shown in Table 2 below.

實例1-25~實例1-33 Example 1-25~Example 1-33

於實例1-3中，如表1中所記載那樣變更染料溶液2中之特定染料(A-1)、特定染料(A-2)，除此以外與實例1-1同樣地進行而調製著色硬化性組成物，形成著色層且進行評價。另外，於併用2種染料時之染料的混合比為1：1。將評價結果示於下述表2中。 In Example 1-3, the specific dye (A-1) and the specific dye (A-2) in the dye solution 2 were changed as described in Table 1, and the coloring was carried out in the same manner as in Example 1-1. The curable composition was formed into a colored layer and evaluated. Further, the mixing ratio of the dyes when the two dyes were used in combination was 1:1. The evaluation results are shown in Table 2 below.

比較例1-1 Comparative Example 1-1

將下述各成分混合、溶解而調製著色硬化性組成物。 The following components were mixed and dissolved to prepare a colored curable composition.

於調製後，與實例1-1同樣地進行評價。將評價結果示於下述表2中。 After the preparation, evaluation was carried out in the same manner as in Example 1-1. The evaluation results are shown in Table 2 below.

比較例1-2 Comparative Example 1-2

將下述各成分混合、溶解而調製著色硬化性組成物。 The following components were mixed and dissolved to prepare a colored curable composition.

調製後，與實例1-1同樣地進行評價。將評價結果示於下述表2中。 After the preparation, evaluation was carried out in the same manner as in Example 1-1. The evaluation results are shown in Table 2 below.

比較例1-3 Comparative Example 1-3

將下述各成分混合、溶解而調製著色硬化性組成物。 The following components were mixed and dissolved to prepare a colored curable composition.

另外，染料溶液4是將下述各成分混合、溶解而製作。 Further, the dye solution 4 is produced by mixing and dissolving each of the following components.

製備後，與實例1-1同樣地進行評價。將結果示於表2中。 After the preparation, evaluation was carried out in the same manner as in Example 1-1. The results are shown in Table 2.

另外，染料溶液4中所含之卟啉化合物是通式(III)中之A1與A2、A3與A4、A5與A6、及A7與A8之全部形成芳香環結構的本發明之範圍外之染料。 Further, the porphyrin compound contained in the dye solution 4 is an aromatic ring structure in which all of A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 in the general formula (III) are formed. Dyes outside the scope of the invention.

根據表2之評價結果可知如下者。 The following results are known from the evaluation results of Table 2.

可知由實例1-1~實例1-33之二吡咯亞甲基金屬錯合物及/或雜吡咯亞甲基金屬錯合物與卟啉化合物組合而成之著色硬化性組成物所形成的著色硬化膜可同時實現高的對比度與分光特性，如實例1-1或實例1-5所示那樣，即使特定染料(A)之含量為微量，與未使用特定染料(A)的比較例1-1相比而言，亦具有高的對比度與亮度提高效果。 It is known that the coloring hardening composition formed by the combination of the dipyrromethene metal complex and/or the heteropyrromethene metal complex of Example 1-1 to Example 1-33 and the porphyrin compound is colored. The cured film can simultaneously achieve high contrast and spectral characteristics, as shown in Example 1-1 or Example 1-5, even if the content of the specific dye (A) is a trace amount, and Comparative Example 1 without using the specific dye (A) 1 In comparison, it also has a high contrast and brightness enhancement effect.

根據比較例1-1，於未使用卟啉化合物之情形時，著色硬化性組成物之對比度低，性能並不充分。而且，根據比較例1-2，於未使用二吡咯亞甲基金屬錯合物化合物之情形時，分光特性(Y值)低。 According to Comparative Example 1-1, when the porphyrin compound was not used, the contrast of the colored curable composition was low, and the performance was insufficient. Further, according to Comparative Example 1-2, when the dipyrromethene metal complex compound was not used, the spectral characteristics (Y value) were low.

如所述各實例所示，藉由併用吡咯亞甲基系染料與通式(III)所表示之卟啉化合物而可獲得具有良好之色度、對比度的著色硬化性組成物，但於如比較例1-3所示那樣併用卟啉化合物之類似化合物的酞菁系化合物、亦即通式(III)中之A1與A2、A3與A4、A5與A6、及A7與A8之全部相互鍵結而形成環結構之化合物之情形時，亮度、對比度相對於實例群而言稍低，性能並不充分。其理由尚不明確，推測是由於本發明之具有通式(III)所表示之卟啉結構的化合物與具有酞菁結構的比較染料相比而言分子結構小，移動性高，因此抑制染料分子彼此之間、顏料粒子彼此之間凝聚的效果高。 As shown in the above examples, a coloring curable composition having good chroma and contrast can be obtained by using a pyrrolemethylene dye in combination with a porphyrin compound represented by the formula (III), but for example, a phthalocyanine-based compound of a similar compound of a porphyrin compound, as shown in Examples 1-3, that is, A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 in the formula (III) In the case where all of A 8 are bonded to each other to form a compound having a ring structure, the brightness and contrast are slightly lower than those of the example group, and the performance is not sufficient. The reason for this is not clear, and it is presumed that the compound having the porphyrin structure represented by the general formula (III) of the present invention has a small molecular structure and high mobility as compared with a comparative dye having a phthalocyanine structure, thereby suppressing dye molecules. The effect of agglomerating between the pigment particles is high.

實例1-34 Example 1-34

液晶顯示裝置之製作 Production of liquid crystal display device

藉由以下手法而製作彩色濾光片、及包含該彩色濾光片之液晶顯示裝置而進行評價。 The color filter and the liquid crystal display device including the color filter were produced by the following methods and evaluated.

紅色著色感光性樹脂組成物R之製作 Production of red colored photosensitive resin composition R

將下述組成之顏料分散組成物加以混合，使用均質器而以3,000r.p.m.之轉速進行3小時之攪拌。將如上所述而得之混合溶液進一步於使用0.3mmφ之氧化鋯顆粒的顆粒分散機Dispermat(商品名、GETZMANN公司製造)中進行12小時之分散處理，其後進一步使用附有減壓機構的高壓分散機NANO-3000-10(商品名、日本BEE股份有限公司製造)而於2000kg/cm3之壓力下以500g/min之流量進行分散處理。重複該分散處理10次而獲得顏料分散組成物。 The pigment dispersion composition of the following composition was mixed, and the mixture was stirred at 3,000 rpm for 3 hours using a homogenizer. The mixed solution obtained as described above was further subjected to a dispersion treatment for 12 hours in a particle disperser Dispermat (trade name, manufactured by GETZMANN) using 0.3 mmφ of zirconium oxide particles, and thereafter, a high pressure with a pressure reducing mechanism was further used. The dispersing machine NANO-3000-10 (trade name, manufactured by Japan BEE Co., Ltd.) was subjected to dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

紅色顏料分散物之組成 Composition of red pigment dispersion

於所得之顏料分散物中進一步添加下述組成之成分，製作紅色著色感光性樹脂組成物R。 Further, a component having the following composition was further added to the obtained pigment dispersion to prepare a red colored photosensitive resin composition R.

紅色著色感光性樹脂組成物R之組成 Composition of red colored photosensitive resin composition R

綠色著色感光性樹脂組成物G之製作 Production of green colored photosensitive resin composition G

於紅色著色感光性樹脂組成物R之製作中，使用103份之顏料綠58代替顏料紅254，使用19份之顏料黃150代替顏料紅177，除此以外同樣地進行而製作綠色著色感光性樹脂組成物G。 In the preparation of the red colored photosensitive resin composition R, 103 parts of pigment green 58 was used instead of the pigment red 254, and 19 parts of the pigment yellow 150 was used instead of the pigment red 177, and the green colored photosensitive resin was produced in the same manner. Composition G.

黑色著色感光性樹脂組成物K之製作 Production of black colored photosensitive resin composition K

製備下述組成之顏料分散組成物，與紅色顏料分散物製作時同樣地進行分散處理而製作黑色顏料分散物。 A pigment dispersion composition having the following composition was prepared, and dispersion treatment was carried out in the same manner as in the preparation of the red pigment dispersion to prepare a black pigment dispersion.

黑色顏料分散物之組成 Composition of black pigment dispersion

使用所得之黑色顏料分散組成物，藉由以下之組成而製備黑色著色感光性樹脂組成物K。 Using the obtained black pigment dispersion composition, a black colored photosensitive resin composition K was prepared by the following composition.

黑色著色感光性樹脂組成物K之組成 Composition of black colored photosensitive resin composition K

(n=6、x=55、y=5、Mw=33940 Mw/Mn=2.55 PO：環氧丙烷、EO：環氧乙烷) (n=6, x=55, y=5, Mw=33940 Mw/Mn=2.55 PO: propylene oxide, EO: ethylene oxide)

彩色濾光片之形成 Color filter formation

黑色矩陣之形成 Black matrix formation

將無鹼玻璃基板於UV清洗裝置中進行清洗後，使用清洗劑用刷子加以清洗，進一步於超純水中進行超音波清洗。將該基板於120℃下進行3分鐘之熱處理而使表面狀態穩定化後，使該基板冷卻而將溫度調節為23℃。 The alkali-free glass substrate was washed in a UV cleaning device, washed with a brush using a cleaning agent, and further ultrasonically cleaned in ultrapure water. After the substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state, the substrate was cooled to adjust the temperature to 23 ° C.

藉由具有狹縫狀管嘴之玻璃基板用塗佈機(F.A.S.Asia公司製造、商品名：MH-1600)，將所述黑色著色感光性樹脂組成物K塗佈於該基板上。繼而藉由VCD(真空乾燥裝置；東京應化工業股份有限公司製造)以30秒使溶劑之一部分乾燥而使塗佈層無流動性之後，於120℃下進行3分鐘之預烤而獲得膜厚為2.4μm之黑色感光性樹脂層。 The black colored photosensitive resin composition K was applied onto the substrate by a glass substrate coating machine (manufactured by F.A.S. Asia, trade name: MH-1600) having a slit-shaped nozzle. Then, a portion of the solvent was partially dried by VCD (Vacuum Drying Apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) to make the coating layer have no fluidity, and then pre-baked at 120 ° C for 3 minutes to obtain a film thickness. It is a 2.4 μm black photosensitive resin layer.

藉由具有超高壓水銀燈之近接型曝光機(日立高新電子工程股份有限公司製造)，於使基板與遮罩(具有影像圖案之石英曝光遮罩)垂直地豎立之狀態下，將曝光遮罩面與該感光性樹脂層之間的距離設定為200μm，藉由300mJ/cm2之曝光量進行圖案曝光。 The exposure mask surface is exposed in a state in which the substrate and the mask (the quartz exposure mask having the image pattern) are vertically erected by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp. The distance from the photosensitive resin layer was set to 200 μm, and pattern exposure was performed by an exposure amount of 300 mJ/cm 2 .

其次，藉由噴淋管嘴而噴霧純水，使該黑色感光性樹脂層之表面均一地潮濕後，藉由KOH系顯影液(KOH、含有非離子界面活性劑、商品名：CDK-1、富士電子材料股份有限公司(FUJIFILM Electronic materials Co.,Ltd.)製造)而於23℃下，以扁型噴嘴(flat nozzle)壓力為0.04MPa下進行80秒之噴淋顯影而獲得圖案化影像。繼而，藉由超高壓清洗管嘴，以9.8MPa之壓力噴射超純水而進行殘渣除去，獲得黑色(K)之影像K。最後於220℃下進行30分鐘之熱處理，形成黑色矩陣。 Next, pure water is sprayed by spraying the nozzle to uniformly wet the surface of the black photosensitive resin layer, and then a KOH-based developing solution (KOH, containing a nonionic surfactant, trade name: CDK-1, A patterned image was obtained by performing shower development at a pressure of 0.04 MPa at a pressure of 0.04 MPa at 23 ° C under the condition of 23 ° C by FUJIFILM Electronic Materials Co., Ltd. Then, the ultrapure water was sprayed at a pressure of 9.8 MPa by an ultrahigh pressure cleaning nozzle to remove the residue, and a black (K) image K was obtained. Finally, heat treatment was carried out at 220 ° C for 30 minutes to form a black matrix.

RGB畫素之形成 RGB pixel formation

於所述形成有黑色矩陣之玻璃基板上，分別順次藉由與黑色矩陣形成時同樣之步驟積層紅色著色感光性樹脂組成物R、綠色著色感光性樹脂組成物G、實例1中所製成的藍色著色硬化性組成物且進行圖案化，獲得RGB 3色畫素之彩色濾光片。此時，RGB各色之著色部膜厚為1.6μm。 On the glass substrate on which the black matrix was formed, the red colored photosensitive resin composition R, the green colored photosensitive resin composition G, and the example 1 were laminated in the same manner as in the case of forming the black matrix. The blue coloring curable composition was patterned and patterned to obtain a color filter of RGB 3 color pixels. At this time, the thickness of the color portion of each of the RGB colors was 1.6 μm.

ITO電極之形成 Formation of ITO electrode

將形成有彩色濾光片之玻璃基板放入至濺鍍裝置中，於100℃下整個面真空蒸鍍厚度為1300Å之ITO後，於240℃下進行90分鐘之退火使ITO結晶化，形成ITO透明 電極。 The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and ITO having a thickness of 1300 Å was vacuum-deposited on the entire surface at 100 ° C, and then annealed at 240 ° C for 90 minutes to crystallize the ITO to form ITO. Transparent electrode.

間隔物之形成 Spacer formation

藉由與日本專利特開2004-240335號公報之[實例1]中所記載之間隔物形成方法同樣的方法，於上述所製作之ITO透明電極上形成間隔物。 A spacer was formed on the ITO transparent electrode produced as described above by the same method as the spacer formation method described in [Example 1] of JP-A-2004-240335.

液晶配向控制用突起之形成 Formation of protrusions for liquid crystal alignment control

使用下述之正型感光性樹脂層用塗佈液，於所述形成有間隔物之ITO透明電極上形成液晶配向控制用突起。 A liquid crystal alignment control projection is formed on the ITO transparent electrode on which the spacer is formed by using the coating liquid for a positive photosensitive resin layer described below.

其中，曝光、顯影及烘烤步驟使用以下之方法。 Among them, the exposure, development and baking steps use the following methods.

以規定之光罩自感光性樹脂層之表面起成為100μm之距離的方式配置近接式曝光機(商品名、日立高新電子工程股份有限公司(Hitachi High-Tech Electronics Engineering Co.,Ltd.)製造)，介隔該光罩藉由超高壓水銀燈以150mJ/cm2之照射能量進行近接式曝光。 A proximity exposure machine (trade name, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is disposed so as to have a distance of 100 μm from the surface of the photosensitive resin layer. The photomask is closely exposed by an ultrahigh pressure mercury lamp with an irradiation energy of 150 mJ/cm 2 .

繼而，一面藉由噴淋式顯影裝置於33℃下將2.38%四甲基氫氧化銨水溶液噴霧於基板上30秒一面進行顯影。如上所述地將感光性樹脂層之不需要部分(曝光部)顯影除去，由此而獲得於彩色濾光片側基板上形成有包含圖案化為所期望之形狀的感光性樹脂層的液晶配向控制用突起的液晶顯示裝置用基板。 Then, development was carried out by spraying a 2.38% aqueous solution of tetramethylammonium hydroxide on the substrate at 33 ° C for 30 seconds by means of a shower type developing device. The unnecessary portion (exposure portion) of the photosensitive resin layer is developed and removed as described above, whereby a liquid crystal alignment including a photosensitive resin layer patterned into a desired shape is formed on the color filter side substrate. A substrate for a liquid crystal display device for controlling protrusions.

其次，將該形成有液晶配向控制用突起之液晶顯示裝置用基板於230℃下進行30分鐘之烘烤，由此而於液晶顯示裝置用基板上形成硬化之液晶配向控制用突起。 Then, the substrate for a liquid crystal display device in which the liquid crystal alignment control projections were formed was baked at 230 ° C for 30 minutes to form a cured liquid crystal alignment control projection on the substrate for a liquid crystal display device.

正型感光性樹脂層用塗佈液配方 Formulation solution for positive photosensitive resin layer

液晶顯示裝置之製作 Production of liquid crystal display device

於上述所得之液晶顯示裝置用基板上進一步設置包含聚醯亞胺之配向膜。其後，於以包圍彩色濾光片之畫素群之方式設於周圍的、相當於黑色矩陣外框的位置，印刷環氧樹脂密封劑，且滴加MVA模式用液晶，將對向基板貼合後，對所貼合之基板進行熱處理而使密封劑硬化。 An alignment film containing polyimine is further provided on the substrate for a liquid crystal display device obtained above. Thereafter, the epoxy resin sealant is printed at a position corresponding to the surrounding area of the black matrix so as to surround the pixel group surrounding the color filter, and the liquid crystal for MVA mode is dropped, and the opposite substrate is pasted. After the bonding, the bonded substrate is heat-treated to harden the sealing agent.

於如上所述而得的液晶單元之兩個面貼附三立股份有限公司製造之偏光板HLC2-2518(商品名)。其次，將作為光源之LED光源(索尼(Sony)公司製造之液晶電視、商品名、KDL-40ZX1之背光光源)配置於成為設有所述偏光板之液晶單元之背面之側，製成液晶顯示裝置(LCD)。 A polarizing plate HLC2-2518 (trade name) manufactured by Sanli Co., Ltd. was attached to both surfaces of the liquid crystal cell as described above. Next, an LED light source (a liquid crystal TV manufactured by Sony Corporation, a product name, and a backlight source of KDL-40ZX1) as a light source is disposed on the side of the back surface of the liquid crystal cell in which the polarizing plate is provided to form a liquid crystal display. Device (LCD).

如上所述而製成的液晶顯示裝置具有高的對比度與亮度，適於作為顯示裝置。另外，於本實例中進行了於MVA模式液晶顯示裝置中之評價，認為若於其他模式之液晶顯示裝置或有機EL顯示器之彩色濾光片中使用本發明之著色硬化性組成物，亦可同樣地獲得良好之畫質。 The liquid crystal display device produced as described above has high contrast and brightness and is suitable as a display device. Further, in the present example, evaluation was performed in an MVA mode liquid crystal display device, and it is considered that the same color hardening composition of the present invention can be used for a color filter of another mode liquid crystal display device or organic EL display. Get a good picture quality.

實例2-1 Example 2-1

將下述各成分混合、溶解而調製著色硬化性組成物2-1並進行評價。 The following components were mixed and dissolved to prepare a colored curable composition 2-1, and the evaluation was carried out.

．有機溶劑(丙二醇單甲醚乙酸酯) 21份 . Organic solvent (propylene glycol monomethyl ether acetate) 21 parts

染料溶液1是將下述各成分混合、溶解而調製。 The dye solution 1 is prepared by mixing and dissolving each of the following components.

染料溶液2是將下述各成分混合、溶解而製作染料溶液。 In the dye solution 2, the following components are mixed and dissolved to prepare a dye solution.

於染料溶液1中包含作為(B)卟啉化合物之(P-26)，於染料溶液2中包含作為(A-1)二吡咯亞甲基金屬錯合物化合物之通式(I)之例示化合物(11)。 The dye solution 1 contains (P-26) as the (B) porphyrin compound, and the exemplified formula (I) containing the (A-1) dipyrromethene metal complex compound in the dye solution 2 Compound (11).

著色硬化性組成物層(著色層)之形成 Formation of a colored curable composition layer (colored layer)

於鉻包覆玻璃基板(1邊為75mm、鉻膜之厚度為0.3μm)上，藉由以加熱硬化後(後烘烤後)之膜厚成為3.0μm之方式調整轉速的旋塗機塗佈上述所得之著色硬化性組成物2-1而形成塗佈膜。 On a chrome-coated glass substrate (75 mm on one side and 0.3 μm on the chrome film), a spin coater was used to adjust the rotation speed by a film thickness of 3.0 μm after heat curing (after baking). The colored curing composition 2-1 obtained above was formed to form a coating film.

其次，將形成有塗佈膜之鉻包覆玻璃基板於加熱板上、100℃、120秒之條件下進行預烤，除去溶劑而使其乾燥。 Next, the chromium-coated glass substrate on which the coating film was formed was prebaked on a hot plate at 100 ° C for 120 seconds to remove the solvent and dried.

於預烤後，使用2.5kW之超高壓水銀燈，以200mJ/cm2之曝光量對塗佈膜之整個面進行光照射。 After prebaking, the entire surface of the coating film was irradiated with light at a exposure amount of 200 mJ/cm 2 using a 2.5 kW ultrahigh pressure mercury lamp.

其次，藉由熱風循環式乾燥機，將曝光後之形成有塗佈膜之鉻包覆玻璃基板於220℃、60分鐘之條件下進行加熱硬化(後烘烤)，製作形成有著色層之試片。 Next, the chrome-coated glass substrate on which the coating film was formed after exposure was subjected to heat curing (post-baking) at 220 ° C for 60 minutes by a hot air circulation dryer to prepare a colored layer. sheet.

評價 Evaluation

相對介電常數之測定 Determination of relative dielectric constant

削掉上述所得之後烘烤後之形成有著色層的試片之一處角落之著色層，使鉻膜表面露出。其次，於試片之背面 旋塗銀漿料而將其風乾。其後，藉由所述銀漿料將表面之鉻露出面與背面之銀漿料塗佈面導通(連接)。於所得之試片之表塗膜面，使用真空蒸鍍裝置(商品名：離子濺鍍E1030、日立製作所股份有限公司製造)，藉由Pt/Pd靶材，如圖1所示那樣於試片(基板)1上製作蒸鍍厚度為約50nm之主電極2(內圓)及屏蔽電極(guard electrode)3(外圓)。另外，於試片1上露出削掉之鉻膜表面4。 The colored layer at the corner of one of the test pieces on which the colored layer was formed after baking as described above was scraped off to expose the surface of the chromium film. Second, on the back of the test piece The silver paste was spin coated and air dried. Thereafter, the silver exposed surface of the surface is electrically connected (connected) to the silver paste coated surface on the back surface by the silver paste. On the surface of the obtained test piece, a vacuum vapor deposition apparatus (trade name: ion sputter E1030, manufactured by Hitachi, Ltd.) was used, and a Pt/Pd target was used as shown in FIG. On the (substrate) 1, a main electrode 2 (inner circle) having a vapor deposition thickness of about 50 nm and a guard electrode 3 (outer circle) were formed. Further, the chrome film surface 4 which was cut off was exposed on the test piece 1.

於電極製作後，藉由觸針式表面形狀測定器(商品名：DEKTAK3、愛發科(ULVAC)股份有限公司製造)而測定試片之未附有電極之部分的著色層之厚度。 After the electrode was produced, the thickness of the coloring layer of the portion of the test piece to which the electrode was not attached was measured by a stylus type surface shape measuring device (trade name: DEKTAK3, manufactured by ULVAC).

其次，於靜電容測定器(精密阻抗分析器4294A、商品名、安捷倫(agilent)科技股份有限公司製造)上安裝介電測試夾具16451B及電極，進一步安裝上述所得之試片1，測定施加1kHz、0.5V之交流電壓時的相對介電常數ε'，依照下述評價基準進行評價。將評價結果示於下述表3中。 Next, a dielectric test jig 16451B and electrodes were mounted on a static capacitance measuring device (Precision Impedance Analyzer 4294A, trade name, manufactured by Agilent Technologies Co., Ltd.), and the obtained test piece 1 was further attached, and the measurement was performed at 1 kHz. The relative dielectric constant ε' at an alternating voltage of 0.5 V was evaluated in accordance with the following evaluation criteria. The evaluation results are shown in Table 3 below.

評價基準 Evaluation basis

A：相對介電常數ε'<3.0 A: Relative dielectric constant ε'<3.0

B：相對介電常數ε'=3.0~5.0 B: Relative dielectric constant ε'=3.0~5.0

C：相對介電常數ε'>5.0 C: Relative dielectric constant ε'>5.0

耐剝離液性 Peel-resistant liquid

藉由以下順序a)~e)測定於試片上所形成的著色層之厚度而算出膨潤率，將該算出值作為評價耐剝離液性之指標。其中，於耐剝離液性差之情形時存在如下現象：於 浸漬於剝離液中時，塗膜溶解於剝離液中、或自基板上剝離而無法測定膜厚。將此種情形評價為「C」。將評價結果示於下述表3中。 The swelling ratio was calculated by measuring the thickness of the colored layer formed on the test piece by the following procedures a) to e), and the calculated value was used as an index for evaluating the peeling resistance. Among them, in the case of poor peeling liquidity, there are the following phenomena: When immersed in the peeling liquid, the coating film was dissolved in the peeling liquid or peeled off from the substrate, and the film thickness could not be measured. This case was evaluated as "C". The evaluation results are shown in Table 3 below.

a)使用觸針式表面形狀測定器(商品名：DEKTAK3、愛發科(ULVAC)股份有限公司製造)而測定上述所得之形成有著色層的試片之著色層之膜厚(FT0)。 a) The film thickness (FT0) of the coloring layer of the test piece on which the colored layer was formed obtained above was measured using a stylus type surface shape measuring device (trade name: DEKTAK3, manufactured by ULVAC Co., Ltd.).

b)於測定後，使用單乙醇胺(MEA)與二甲基亞碸(DMSO)之混合物(MEA/DMSO=7/3質量比)作為剝離液，於80℃下將上述試片於剝離液中浸漬120秒。 b) After the measurement, a mixture of monoethanolamine (MEA) and dimethyl hydrazine (DMSO) (MEA/DMSO = 7/3 by mass) was used as a stripping solution, and the test piece was placed in a stripping solution at 80 ° C. Dip for 120 seconds.

c)於槽中充滿MEA/DMSO=7/3之液體，進一步浸漬所述b)之浸漬後的試片。其後，於觸針式表面形狀測定器(商品名：DEKTAK3、愛發科(ULVAC)股份有限公司製造)之試片支撐台上放置以剝離液覆蓋表面之狀態的試片，測定著色層之膜厚(FT1)(測定由於剝離液所引起之膨潤狀態的膜厚)。 c) The tank was filled with a liquid of MEA/DMSO = 7/3, and the impregnated test piece of the b) was further immersed. Then, a test piece in a state in which the surface was covered with a peeling liquid was placed on a test piece support stand of a stylus type surface shape measuring device (trade name: DEKTAK3, manufactured by ULVAC Co., Ltd.), and the colored layer was measured. Film thickness (FT1) (measurement of the film thickness due to the swelling state caused by the peeling liquid).

d)於其他槽中充滿純水，浸漬於所述c)中膨潤之試片，靜置1晚而將塗膜中所含之剝離液與水置換後，將試片於200℃下乾燥30分鐘，再次測定著色層之膜厚(FT2)。 d) filling the other tank with pure water, immersing in the test piece swollen in the above c), leaving it for 1 night, replacing the stripping liquid contained in the coating film with water, and drying the test piece at 200 ° C. The film thickness (FT2) of the colored layer was measured again in minutes.

e)使用藉由上述而測定之FT0、FT1、FT2，根據下述式分別算出試片之膨潤率及膜減少率，基於下述評價基準而評價耐剝離液性。另外，(FT1-FT0)是測定由於剝離液所造成之表觀之膨潤，因此藉由被剝離液侵蝕之膜減少部分(FT2-FT0)而進行校正，算出真正的膨潤率。 e) Using the FT0, FT1, and FT2 measured by the above, the swelling ratio and the film reduction rate of the test piece were respectively calculated according to the following formula, and the peeling resistance was evaluated based on the following evaluation criteria. Further, (FT1-FT0) measures the apparent swelling due to the peeling liquid, and is corrected by the film reducing portion (FT2-FT0) which is eroded by the peeling liquid, thereby calculating the true swelling ratio.

真正的膨潤率(%)=100×(FT1-FT2)/FT0 The true swelling rate (%) = 100 × (FT1-FT2) / FT0

膜減少率(%)=100×(FT2-FT0)/FT0 Membrane reduction rate (%) = 100 × (FT2-FT0) / FT0

評價基準 Evaluation basis

A：真正的膨潤率≦40%、膜減少率≦5%，耐剝離液性良好。 A: The true swelling ratio is 40%, the film reduction rate is 5%, and the peeling resistance is good.

B：真正的膨潤率≦40%、膜減少率>5%，耐剝離液性為許可之範圍內。 B: The true swelling ratio is 40%, the film reduction rate is >5%, and the peeling resistance is within the allowable range.

C：塗膜溶解或剝離，耐剝離液性差。 C: The coating film is dissolved or peeled off, and the peeling resistance is poor.

[實例2-2~實例2-6] [Example 2-2~Example 2-6]

於實例2-1中，如表3中所記載那樣變更染料溶液1中之特定染料(B)之種類，除此以外與實例2-1同樣地進行而調製著色感光性組成物，形成著色層且進行評價。將評價結果示於下述表3中。 In the same manner as in Example 2-1, except that the type of the specific dye (B) in the dye solution 1 was changed as described in Table 3, the coloring photosensitive composition was prepared to form a coloring layer. And evaluation. The evaluation results are shown in Table 3 below.

[實例2-7~實例2-12] [Example 2-7~Example 2-12]

於實例2-1中，如表3中所記載那樣變更染料溶液2中之特定染料(A-1)、特定染料(A-2)，除此以外與實例2-1同樣地進行而調製著色感光性組成物，形成著色層且進行評價。將評價結果示於下述表3中。 In Example 2-1, the specific dye (A-1) and the specific dye (A-2) in the dye solution 2 were changed as described in Table 3, and the coloring was carried out in the same manner as in Example 2-1. The photosensitive composition was formed into a colored layer and evaluated. The evaluation results are shown in Table 3 below.

根據表3可知：包含本發明之特定染料之組合的著色硬化性組成物即使於COA方式之彩色濾光片之製作中使用亦可顯示適宜之性能。 According to Table 3, it is understood that the color-curable composition containing the combination of the specific dyes of the present invention exhibits suitable properties even when used in the production of COA-type color filters.

作為日本專利申請2011-218598號及日本專利申請2012-077759號之揭示，藉由參照而將其全體併入至本說明書中。 The disclosures of Japanese Patent Application No. 2011-218598 and Japanese Patent Application No. 2012-077759, the entire contents of

作為本說明書中所記載之所有文獻、專利申請及技術規格，與具體且各個地記載藉由參照而併入各個文獻、專利申請及技術規格之情形同等程度地，藉由參照而併入至本說明書中。 All the documents, patent applications, and technical specifications described in the present specification are incorporated by reference to the same extent as the individual documents, patent applications, and technical specifications. In the manual.

1‧‧‧試片 1‧‧‧ test piece

2‧‧‧主電極 2‧‧‧Main electrode

3‧‧‧屏蔽電極 3‧‧‧Shield electrode

4‧‧‧鉻膜表面 4‧‧‧Chromium film surface

圖1是表示本發明之實例中之相對介電常數之測定中所製作的主電極及屏蔽電極之概略平面圖。 Fig. 1 is a schematic plan view showing a main electrode and a shield electrode which are produced in the measurement of the relative dielectric constant in the example of the present invention.

1‧‧‧試片 1‧‧‧ test piece

2‧‧‧主電極 2‧‧‧Main electrode

3‧‧‧屏蔽電極 3‧‧‧Shield electrode

4‧‧‧鉻膜表面 4‧‧‧Chromium film surface

Claims (8)

一種著色硬化性組成物，其含有：選自由(A-1)下述通式(I-4)所表示的二吡咯亞甲基金屬錯合物化合物及(A-2)下述通式(II-7)或通式(II-8)所表示的氮雜吡咯亞甲基金屬錯合物化合物所構成之群組的1種以上的色素化合物；以及(B)下述通式(III-2)所表示之卟啉化合物， 所述通式(I-4)中，R2、R3、R4、及R5各自獨立地表示氫原子、或取代基，R7表示氫原子、鹵素原子、烷基、芳基、或雜環基；R8及R9各自獨立地表示烷基、烯基、芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、或雜環胺基；Ma表示金屬或金屬化合物；X3及X4表示氧原子；Y1及Y2表示NH；X5表示可與Ma鍵結之基；a表 示0、1、或2；R8與Y1可相互鍵結而形成5員環、6員環或7員環，R9與Y2可相互鍵結而形成5員環、6員環或7員環； 所述通式(II-7)及所述通式(II-8)中，Ra分別獨立地表示芳基或烷基；Rb分別獨立地表示2,6-二-第三丁基-4-甲基環己氧基羰基或氰基；Rd分別獨立地表示烷基、芳基、雜芳基或烯基；Ma為金屬原子或金屬化合物；Z1表 示可與Ma鍵結之基； 所述通式(III-2)中，A1、A2、A3、A4、A5、A6、A7及A8各自獨立地表示烷基、烯基、芳基、烷氧基、烷硫基、芳氧基、芳硫基、鹵素原子、羥基、烷氧基羰基、芳氧基羰基、胺基、胺甲醯基、胺磺醯基、醯基、矽烷氧基、氰基、硝基、或雜環基；A1與A2、A3與A4、A5與A6、及A7與A8之任意者均未相互鍵結而均未形成環結構；M表示2價金屬原子、或選自鹵化金屬原子、具有取代基的金屬原子及金屬氧化物之2價原子團。 A colored hardening composition comprising: a dipyrromethene metal complex compound represented by (A-1) the following general formula (I-4) and (A-2) a general formula (A-2) II-7) or one or more kinds of pigment compounds of the group consisting of the azapyrrolidinium metal complex compounds represented by the formula (II-8); and (B) the following formula (III- 2) the porphyrin compound represented, In the above formula (I-4), R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or a substituent, and R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; R 8 and R 9 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amine group; Ma represents a metal or a metal compound; X 3 and X 4 represent an oxygen atom; Y 1 and Y 2 represent NH; X 5 represents a group bondable to Ma; a represents 0, 1, or 2; and R 8 and Y 1 may Bonding to each other to form a 5-member ring, a 6-member ring or a 7-member ring, and R 9 and Y 2 may be bonded to each other to form a 5-member ring, a 6-member ring or a 7-member ring; In the above formula (II-7) and the formula (II-8), R a each independently represents an aryl group or an alkyl group; and R b independently represents 2,6-di-t-butyl group- 4-methylcyclohexyloxycarbonyl or cyano; R d each independently represents an alkyl group, an aryl group, a heteroaryl group or an alkenyl group; Ma is a metal atom or a metal compound; and Z 1 represents a group which can be bonded to Ma. ; In the above formula (III-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 each independently represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group. An alkylthio group, an aryloxy group, an arylthio group, a halogen atom, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine group, an amine methyl group, an amine sulfonyl group, a decyl group, a decyloxy group, a cyano group , nitro, or heterocyclic group; A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and any of A 7 and A 8 are not bonded to each other and neither form a ring structure; M represents A divalent metal atom or a divalent atomic group selected from a halogenated metal atom, a metal atom having a substituent, and a metal oxide. 如申請專利範圍第1項所述之著色硬化性組成物，其更含有(C)聚合性化合物及(D)光聚合起始劑，且為感光性。 The colored curable composition according to claim 1, which further comprises (C) a polymerizable compound and (D) a photopolymerization initiator, and is photosensitive. 如申請專利範圍第1項所述之著色硬化性組成物，其中相對於所述著色硬化性組成物中所含之著色化合物之總量而言，所述(B)通式(III-2)所表示之卟啉化合物 之含量為0.1質量%以上50質量%以下。 The color hardening composition according to claim 1, wherein the (B) formula (III-2) is relative to the total amount of the coloring compound contained in the colored curable composition. Porphyrin compound The content is 0.1% by mass or more and 50% by mass or less. 如申請專利範圍第1項所述之著色硬化性組成物，其中，其中相對於所述著色硬化性組成物之總固形物而言，包含所述(A-1)通式(I-4)所表示的二吡咯亞甲基金屬錯合物化合物、所述(A-2)通式(II-7)或通式(II-8)所表示的氮雜吡咯亞甲基金屬錯合物化合物及所述(B)通式(III-2)所表示之卟啉化合物的著色化合物的總含量為0.2質量%以上50質量%以下。 The color hardening composition according to claim 1, wherein the (A-1) formula (I-4) is contained in relation to the total solid matter of the colored curable composition. The dipyrromethene metal complex compound represented by the above, (A-2) the azapyrrolemethylene metal complex compound represented by the formula (II-7) or the formula (II-8) The total content of the coloring compound of the porphyrin compound represented by the above formula (III-2) is 0.2% by mass or more and 50% by mass or less. 一種彩色濾光片，其是使用如申請專利範圍第1項至第4項中任一項所述之著色硬化性組成物而成者。 A color filter which is obtained by using the color hardening composition according to any one of claims 1 to 4. 一種彩色濾光片的製造方法，其包含：著色層形成步驟，將如申請專利範圍第1項至第4項中任一項所述之著色硬化性組成物賦予至支撐體上而形成著色層；曝光步驟，將所形成之所述著色層曝光為圖案模樣；以及顯影步驟，對曝光後之所述著色層進行顯影而形成著色圖案。 A method of producing a color filter, comprising: a colored layer forming step of applying a color hardening composition according to any one of claims 1 to 4 to a support to form a colored layer And an exposing step of exposing the formed colored layer to a pattern; and developing a step of developing the colored layer after exposure to form a colored pattern. 一種顯示裝置，其包含如申請專利範圍第5項所述之彩色濾光片。 A display device comprising the color filter of claim 5 of the patent application. 一種顯示裝置，其包含藉由如申請專利範圍第6項所述之彩色濾光片的製造方法而得之彩色濾光片。 A display device comprising a color filter obtained by the method of manufacturing a color filter according to claim 6 of the patent application.
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