TWI505023B - Coloring composition, color filter, and display element - Google Patents

Coloring composition, color filter, and display element Download PDF

Info

Publication number
TWI505023B
TWI505023B TW100146682A TW100146682A TWI505023B TW I505023 B TWI505023 B TW I505023B TW 100146682 A TW100146682 A TW 100146682A TW 100146682 A TW100146682 A TW 100146682A TW I505023 B TWI505023 B TW I505023B
Authority
TW
Taiwan
Prior art keywords
group
acid
compound
ring
salt
Prior art date
Application number
TW100146682A
Other languages
Chinese (zh)
Other versions
TW201232170A (en
Inventor
Hiroyuki Komatsu
Hiroshi Uehara
Yuka Miyashita
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW201232170A publication Critical patent/TW201232170A/en
Application granted granted Critical
Publication of TWI505023B publication Critical patent/TWI505023B/en

Links

Classifications

    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Description

著色組成物、彩色濾光片及顯示元件Coloring composition, color filter, and display element

本發明係有關著色組成物、彩色濾光片及顯示元件，詳言之，係有關形成有用於透過型或反射型之彩色液晶顯示元件、固態影像元件、有機EL顯示元件、電子紙等所使用之彩色濾光片的著色層時所使用的著色組成物、具備使用該著色性組成物所形成之著色層的彩色濾光片、以及具備該彩色濾光片的顯示元件。The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to a color liquid crystal display element, a solid-state image element, an organic EL display element, an electronic paper, or the like formed for a transmissive or reflective type. A coloring composition used for the coloring layer of the color filter, a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

當使用著色感放射線性組成物製造彩色濾光片之際，已知有於基板上塗布著色感放射線性組成物並將其乾燥後，對乾燥塗膜照射放射線(以下稱為「曝光」)形成所要的圖案形狀並進行顯影，而製得各色畫素的方法(專利文獻1~2)。又已知有利用分散有碳黑的光聚合性組成物來形成黑色矩陣的方法(專利文獻3)。更已知有使用著色熱硬化性樹脂組成物並以噴墨方式來製得各色畫素的方法(專利文獻4)。When a color filter is produced using a coloring sensitizing radiation composition, it is known that a colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation (hereinafter referred to as "exposure"). A method of producing a desired color pattern by performing a desired pattern shape (Patent Documents 1 to 2). A method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (Patent Document 3). A method of producing a color photographic element by using an inkjet method using a coloring thermosetting resin composition is known (Patent Document 4).

此外，顏料分散型或溶有染料之彩色濾光片用著色組成物中，其保存穩定性常發生問題。對此，例如專利文獻5中提出使用芳香族羧酸系化合物。Further, in the pigment-dispersed or dye-coated color filter coloring composition, storage stability often causes problems. On the other hand, for example, Patent Document 5 proposes the use of an aromatic carboxylic acid compound.

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

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

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

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

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

[專利文獻5]日本特開2010-14961號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2010-14961

然而，已知含有專利文獻5中所提出之芳香族羧酸系化合物的著色組成物在使用以金屬酞菁素為代表的金屬錯合物作為著色劑時，隨著時間經過會容易發生凝集雜質的產生、對比比率的降低。However, it is known that when a colored composition containing an aromatic carboxylic acid-based compound proposed in Patent Document 5 is used as a colorant represented by a metal phthalocyanine, aggregation impurities are likely to occur over time. The production and the reduction of the contrast ratio.

因此，本發明之課題在於提供一種可抑制經時性之凝集雜質的產生及對比比率的降低之著色組成物。本發明之課題在於進一步提供具備含有該著色組成物之著色層而成之彩色濾光片、及具備該彩色濾光片之顯示元件。Accordingly, an object of the present invention is to provide a colored composition which can suppress generation of agglomerated impurities and decrease in contrast ratio over time. An object of the present invention is to provide a color filter including a coloring layer containing the colored composition, and a display element including the color filter.

本發明人等戮力進行研究的結果發現，使其含有具備對金屬具有配位能力之官能基與特定酸性官能基之化合物，便可解決上述課題。As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by including a compound having a functional group having a coordinating ability for a metal and a specific acidic functional group.

即，本發明係提供一種著色組成物，其特徵為含有(A)著色劑、(B)黏著劑樹脂、(C)交聯劑、及(D)選自包含下述(d-1)~(d-8)之群組的至少1種化合物(以下亦稱為「(D)特定化合物」)，(d-1)具有選自包含-OR1 基及-SR2 基之群組的至少1種之脂肪族羧酸或其鹽(以下亦稱為「化合物(d-1)」)(d-2)具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之脂肪族磺酸或其鹽(以下亦稱為「化合物(d-2)」)(d-3)具有選自包含-OR1 基及-SR2 基之群組的至少1種之脂環式羧酸或其鹽(以下亦稱為「化合物(d-3)」)(d-4)具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之脂環式磺酸或其鹽(以下亦稱為「化合物(d-4)」)(d-5)由具有-SR2 基之基團與具有羧基之基團取代之芳香族烴或其鹽(以下亦稱為「化合物(d-5)」)(d-6)由選自包含具有-OR1 基之基團、具有-SR2 基之基團及具有-Q-NR3 R4 基之基團之群組的至少1種、與具有磺酸基之基團取代之芳香族烴或其鹽(以下亦稱為「化合物(d-6)」)(d-7)具有羧基及雜環基，且氫原子與羧基除外之總原子數為3~20之化合物或其鹽(以下亦稱為「化合物(d-7)」)(d-8)具有磺酸基及雜環基，且氫原子與磺酸基除外之總原子數為3~20之化合物或其鹽(以下亦稱為「化合物(d-8)」)[惟，R1 ~R4 彼此獨立表示氫原子或取代或未取代之1價烴基，Q表示單鍵或羰基]。That is, the present invention provides a colored composition comprising (A) a colorant, (B) an adhesive resin, (C) a crosslinking agent, and (D) selected from the group consisting of the following (d-1)~ At least one compound of the group (d-8) (hereinafter also referred to as "(D) specific compound"), (d-1) having at least one selected from the group consisting of -OR 1 group and -SR 2 group One type of aliphatic carboxylic acid or a salt thereof (hereinafter also referred to as "compound (d-1)") (d-2) has a group selected from the group consisting of -OR 1 group, -SR 2 group and -Q-NR 3 R 4 At least one aliphatic sulfonic acid or a salt thereof (hereinafter also referred to as "compound (d-2)") (d-3) having a group selected from the group consisting of -OR 1 group and -SR 2 group The at least one alicyclic carboxylic acid or a salt thereof (hereinafter also referred to as "compound (d-3)") (d-4) has a group selected from the group consisting of -OR 1 group, -SR 2 group and -Q- At least one alicyclic sulfonic acid or a salt thereof (hereinafter also referred to as "compound (d-4)") (d-5) of the group of NR 3 R 4 groups is composed of a group having a -SR 2 group and the substituted carboxyl group having an aromatic hydrocarbon group or a salt thereof (hereinafter, also referred to as "compound (d-5)") (d-6) having selected from the group comprising a group of -OR 1, -SR 2 group with and the group having a group of -Q-NR 3 R 4 group of At least one of the group, an aromatic hydrocarbon substituted with a group having a sulfonic acid group or a salt thereof (hereinafter also referred to as "compound (d-6)") (d-7) has a carboxyl group and a heterocyclic group, and hydrogen a compound having a total atomic number of 3 to 20 excluding an atom and a carboxyl group or a salt thereof (hereinafter also referred to as "compound (d-7)") (d-8) having a sulfonic acid group and a heterocyclic group, and a hydrogen atom and a sulfonate a compound having a total atomic number of 3 to 20 excluding an acid group or a salt thereof (hereinafter also referred to as "compound (d-8)") [except that R 1 to R 4 independently of each other represent a hydrogen atom or a substituted or unsubstituted one A valent hydrocarbon group, Q represents a single bond or a carbonyl group].

此外，本發明係提供具備使用上述著色組成物所形成之著色層而成之彩色濾光片、及具備該彩色濾光片之顯示元件。此處「著色層」係指彩色濾光片所使用之各色畫素、黑色矩陣、黑色間隔件等。Further, the present invention provides a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter. Here, the "colored layer" refers to each color pixel, black matrix, black spacer, and the like used in the color filter.

本發明著色組成物其保存穩定性優良，可抑制經時性之凝集雜質的產生、對比比率的降低。The colored composition of the present invention is excellent in storage stability, and can suppress generation of agglomerated impurities over time and decrease in contrast ratio.

因此，本發明著色組成物可極佳地使用於以彩色液晶顯示元件用彩色濾光片、固態影像元件之色分解用彩色濾光片、有機EL顯示元件用彩色濾光片、電子紙用彩色濾光片為首的各種彩色濾光片的製作。Therefore, the colored composition of the present invention can be excellently used for color filters for color liquid crystal display elements, color filters for color separation of solid-state image elements, color filters for organic EL display elements, and color for electronic paper. The production of various color filters led by filters.

[實施發明之形態][Formation of the Invention]

以下，對本發明詳細進行說明。Hereinafter, the present invention will be described in detail.

[著色組成物][Coloring composition]

以下，對本發明著色組成物的構成成分進行說明。Hereinafter, the constituent components of the colored composition of the present invention will be described.

-(A)著色劑-- (A) colorant -

作為本發明中的(A)著色劑只要具有著色性則未特別限定，可依據彩色濾光片的用途來適當選擇色彩或材質。具體而言，作為著色劑均可使用顏料、染料及天然色素的任一種，惟因彩色濾光片係要求高色純度、高輝度、高對比等，故較佳為顏料及/或染料。本發明著色組成物特別在使用錯合物作為著色劑時，可抑制經時性之凝集雜質的產生、對比比率的降低而屬有用。作為上述錯合物，可例舉如錯合物顏料、錯合物染料等。The coloring agent (A) in the present invention is not particularly limited as long as it has coloring properties, and the color or material can be appropriately selected depending on the use of the color filter. Specifically, any of a pigment, a dye, and a natural coloring matter can be used as the coloring agent. However, since the color filter is required to have high color purity, high luminance, high contrast, and the like, it is preferably a pigment and/or a dye. In particular, when the coloring composition of the present invention is used as a coloring agent, it is useful to suppress the generation of agglomerated impurities over time and to reduce the contrast ratio. The complex compound may, for example, be a complex pigment or a complex dye.

作為上述錯合物顏料並未特別限定，惟可例舉如金屬酞菁素顏料、金屬偶氮顏料等。The complex pigment is not particularly limited, and examples thereof include a metal phthalocyanine pigment and a metal azo pigment.

作為金屬酞菁素顏料之具體實例，可例舉充作藍色顏料之銅酞菁素、充作綠色顏料之鹵化鋅酞菁素、鹵化銅酞菁素、鹵化鎂酞菁素、鹵化鋁酞菁素、鹵化鈦酞菁素、鹵化釩酞菁素、鹵化錳酞菁素、鹵化鐵酞菁素、鹵化鈷酞菁素、鹵化鎳酞菁素、鹵化錫酞菁素、鹵化鍺酞菁素、鹵化銦酞菁素等。Specific examples of the metal phthalocyanine pigment include copper phthalocyanine which is used as a blue pigment, a zinc halide phthalocyanine which is used as a green pigment, a copper phthalocyanine, a magnesium halide phthalocyanine, and an aluminum halide. Cyanine, titanium halide phthalocyanine, vanadium oxychloride phthalocyanine, manganese halide phthalocyanine, iron halide phthalocyanine, cobalt phthalocyanine, nickel halide phthalocyanine, tin phthalocyanine, halogenated phthalocyanine , indium phthalocyanine and the like.

此外，作為金屬偶氮顏料之具體實例，可例舉充作黃色顏料之偶氮巴比妥酸之鎳錯合物、日本特開2001-354869號公報所揭示之偶氮巴比妥酸之金屬錯合物、日本特開2006-16506號公報所揭示之偶氮巴比妥酸之金屬錯合物等。Further, as a specific example of the metal azo pigment, a nickel complex of azo barbituric acid which is used as a yellow pigment, and a metal of azo barbituric acid disclosed in Japanese Laid-Open Patent Publication No. 2001-354869 can be exemplified. The complex compound, a metal complex of azo barbituric acid disclosed in Japanese Laid-Open Patent Publication No. 2006-16506, and the like.

作為上述錯合物染料並未特別限定，惟可例舉如國際公開第06/043442號小冊所揭示之鈷染料、日本特開2008-83416號公報、日本特開2008-292970號公報所揭示之亞甲基二吡咯(dipyrromethene)系錯合物染料、日本特開2009-51896號公報所揭示之金屬酞菁素染料、日本特開2009-163226號公報所揭示之偶氮金屬染料，此外還可例舉C.I.溶劑橙56、C.I.溶劑黃82(皆為色指數(C.I.)名)等。The above-mentioned complex dye is not particularly limited, and it is disclosed in, for example, the cobalt dye disclosed in the pamphlet of International Publication No. 06/043442, JP-A-2008-83416, and JP-A-2008-292970. a dipyrromethene complex dye, a metal phthalocyanine dye disclosed in JP-A-2009-51896, and an azo metal dye disclosed in JP-A-2009-163226, in addition to For example, CI Solvent Orange 56, CI Solvent Yellow 82 (all of which are color index (CI) names), and the like can be exemplified.

此等著色劑當中，構成錯合物之中心原子為Cu、Zn、Ni、Cr、Al、Co、Mg、In、Fe或B的著色劑可與(D)特定化合物良好地搭配而較佳。又金屬酞菁素可與(D)特定化合物良好地搭配而較佳。金屬酞菁素當中，鹵化鋅酞菁素，特別是含有溴化鋅酞菁素、溴化氯化鋅酞菁素的著色組成物會有較高之隨時間經過凝集雜質生成、對比比率降低的趨勢，而藉由使其含有(D)特定化合物即可解決所述問題。溴化氯化鋅酞菁素係分類為色指數(C.I.)名中C.I.顏料綠58之顏料，較佳為下述式(1)所示之結構：Among these colorants, a coloring agent constituting a complex atom of Cu, Zn, Ni, Cr, Al, Co, Mg, In, Fe or B can be preferably used in combination with (D) a specific compound. Further, the metal phthalocyanine is preferably used in combination with (D) a specific compound. Among the metal phthalocyanins, the zinc halide phthalocyanine, especially the colored composition containing zinc bromide phthalocyanine and zinc bromide phthalocyanine, has a higher concentration of aggregated impurities over time, and the contrast ratio is lowered. The trend is solved by making it contain (D) a specific compound. The zinc bromide phthalocyanine is classified into a pigment of C.I. Pigment Green 58 in the color index (C.I.) name, and is preferably a structure represented by the following formula (1):

[式(1)中，X彼此獨立表示氫原子、氯原子或溴原子，全部X中的10~15個為溴原子、1~6個為氯原子]。In the formula (1), X independently represents a hydrogen atom, a chlorine atom or a bromine atom, and 10 to 15 of all X are bromine atoms and 1 to 6 are chlorine atoms.

本發明中可與上述錯合物共同使用週知之有機顏料、無機顏料、油溶性染料、直接染料、酸性染料、鹼性染料等。In the present invention, well-known organic pigments, inorganic pigments, oil-soluble dyes, direct dyes, acid dyes, basic dyes and the like can be used together with the above-mentioned complex.

本發明中，著色劑可單獨或2種以上混合使用。In the present invention, the coloring agents may be used singly or in combination of two or more kinds.

本發明中，當使用顏料作為著色劑時，亦可視需求對顏料以再結晶法、再沉澱法、溶劑清洗法、昇華法、真空加熱法或此等之組合進行精製後使用。又，顏料亦可視需求以樹脂將其粒子表面改質後使用。作為將顏料的粒子表面改質的樹脂可例舉如日本特開2001-108817號公報所述之載色基樹脂(vehicle resins)、或市售的各種顏料分散用樹脂。又，顏料係較佳以所謂的鹽磨(salt milling)將一次粒子微小化後使用。鹽磨方法可採用例如日本特開平08-179111號公報所揭示之方法。In the present invention, when a pigment is used as the colorant, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or the like, as needed. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. The resin which modifies the surface of the particle of the pigment may, for example, be a vehicle resin as described in JP-A-2001-108817 or a commercially available resin for dispersion of various pigments. Further, the pigment is preferably used by miniaturizing the primary particles by so-called salt milling. The salt milling method can be carried out, for example, by the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111.

(A)著色劑的含有比例，由形成輝度高、色純度優良的畫素，或形成遮光性優良的黑色矩陣的觀點而言，通常在著色性組成物的固體含量中為5~70質量%，較佳為5~60質量%。此處所謂「固體含量」係指後述之溶劑以外的成分。(A) The content ratio of the coloring agent is usually from 5 to 70% by mass in the solid content of the coloring composition from the viewpoint of forming a pixel having high luminance and excellent color purity or forming a black matrix having excellent light shielding properties. Preferably, it is 5 to 60% by mass. Here, the "solid content" means a component other than the solvent described later.

-(B)黏著劑樹脂-- (B) Adhesive Resin -

作為本發明著色組成物中的(B)黏著劑樹脂並未特別限定，惟較佳為具有羧基、酚性羥基等酸性官能基的樹脂。其中較佳為具有羧基之聚合物(以下稱為「含有羧基之聚合物」)，可例舉如具有1個以上羧基的乙烯性不飽和單體(以下稱為「不飽和單體(b1)」)與其他可共聚合的乙烯性不飽和單體(以下稱為「不飽和單體(b2)」)的共聚物。The (B) adhesive resin in the colored composition of the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as "a polymer having a carboxyl group") is preferable, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)" is exemplified. ") Copolymer with other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

作為上述不飽和單體(b1)可例舉如(甲基)丙烯酸、馬來酸、馬來酸酐、單[2-(甲基)丙烯酸乙基]琥珀酸酯、ω-羧基聚己內酯單(甲基)丙烯酸酯、對乙烯基苯甲酸等。The unsaturated monomer (b1) may, for example, be (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acrylic acid ethyl]succinate or ω-carboxypolycaprolactone. Mono (meth) acrylate, p-vinyl benzoic acid, and the like.

此等不飽和單體(b1)可單獨或混合兩種以上使用。These unsaturated monomers (b1) may be used alone or in combination of two or more.

又，作為上述不飽和單體(b2)可例舉如N-苯基馬來亞醯胺、N-環己基馬來亞醯胺之N-位取代馬來亞醯胺；如苯乙烯、α-甲基苯乙烯、對-羥基苯乙烯、對-羥基-α-甲基苯乙烯、對-乙烯苄基縮水甘油酯、苊烯(acenaphthylene)之芳香族乙烯基化合物；如(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、聚乙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚乙二醇(聚合度2~10)單(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)單(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、三環[5.2.1.02,6 ]癸烷-8-基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸4-羥苯酯、對酚之環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、3-[(甲基)丙烯醯氧基甲基]環氧丙烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基環氧丙烷之(甲基)丙烯酸酯；環己基乙烯醚、異莰基乙烯醚、三環[5.2.1.02,6 ]癸烷-8-基乙烯醚、五環十五基乙烯醚、3-(乙烯基環氧甲基)-3-乙基環氧丙烷之乙烯醚；如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之聚合物分子鏈末端具有單(甲基)丙烯醯基之巨單體等。Further, the unsaturated monomer (b2) may, for example, be an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; for example, styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ester, aromatic vinyl compound of acenaphthylene; such as (meth)acrylic acid Methyl ester, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate Ester, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2~10) ) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ]decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) propylene oxime Oxymethylmethyl propylene oxide, (meth) acrylate of 3-[(methyl) propylene methoxymethyl]-3-ethyl propylene oxide; cyclohexyl vinyl ether, isodecyl vinyl ether, Tricyclo[5.2.1.0 2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3-(vinyl epoxymethyl)-3-ethyl propylene oxide; Polystyrene, polymethyl (meth) acrylate, poly(methyl methacrylate), polysiloxane, a macromonomer having a mono (meth) acrylonitrile group at the end of the polymer molecular chain.

此等不飽和單體(b2)可單獨或混合兩種以上使用。These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

不飽和單體(b1)與不飽和單體(b2)的共聚物中，該共聚物中的不飽和單體(b1)的共聚合比例較佳為5~70質量%，更佳為10~60質量%。於此範圍使不飽和單體(b1)共聚合便可製得鹼性顯影性及保存穩定性優良的著色性組成物。In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 70% by mass, more preferably from 10%. 60% by mass. In this range, the unsaturated monomer (b1) is copolymerized to obtain a color-developing composition excellent in alkali developability and storage stability.

不飽和單體(b1)與不飽和單體(b2)的共聚物的具體實例可例舉如日本特開平7-140654號公報、日本特開平8-259876號公報、日本特開平10-31308號公報、日本特開平10-300922號公報、日本特開平11-174224號公報、日本特開平11-258415號公報、日本特開2000-56118號公報、日本特開2002-296778號公報、日本特開2004-101728號公報等所揭示的共聚物。Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) are exemplified by Japanese Laid-Open Patent Publication No. Hei. 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. A copolymer disclosed in, for example, Japanese Patent Publication No. 2004-101728.

又，本發明中亦可如日本特開平5-19467號公報、日本特開平6-230212號公報、日本特開平7-207211號公報、日本特開平09-325494號公報、日本特開平11-140144號公報、日本特開2008-181095號公報等所揭示般，將側鏈上具有(甲基)丙烯醯基等聚合性不飽和鍵之含有羧基之聚合物用作黏著劑樹脂。In the present invention, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acrylonyl group in a side chain is used as an adhesive resin, as disclosed in Japanese Laid-Open Patent Publication No. 2008-181095.

本發明中的(B)黏著劑樹脂，其以GPC(溶出溶劑：四氫呋喃)測定之換算成聚苯乙烯的重量平均分子量(Mw)通常為1,000~100,000，較佳為3,000~50,000。Mw若過小，會有所得之被膜的殘膜率等降低、圖案形狀、耐熱性等受損，或電特性惡化之虞，另一方面若過大，則有解析度降低、圖案形狀受損，或以狹縫噴嘴方式進行塗布時容易產生乾燥雜質之虞。In the (B) adhesive resin of the present invention, the weight average molecular weight (Mw) converted to polystyrene by GPC (solution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. When the Mw is too small, the residual film ratio of the obtained film may be lowered, the pattern shape, heat resistance, and the like may be impaired, or the electrical properties may be deteriorated. On the other hand, if the thickness is too large, the resolution may be lowered and the pattern shape may be impaired. When coating is performed by a slit nozzle method, it is easy to generate dry impurities.

又，本發明中的(B)黏著劑樹脂的重量平均分子量與以GPC(溶出溶劑：四氫呋喃)測定之換算成聚苯乙烯的數量平均分子量(以下稱為「Mn」)的比(Mw/Mn)較佳為1.0~5.0，更佳為1.0~3.0。In addition, the ratio of the weight average molecular weight of the (B) adhesive resin to the number average molecular weight (hereinafter referred to as "Mn") of polystyrene measured by GPC (solution solvent: tetrahydrofuran) in the present invention (Mw/Mn) It is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

本發明中的(B)黏著劑樹脂能以習知方法來製造，亦能以例如日本特開2003-222717號公報、日本特開2006-259680號公報、國際公開第07/029871號小冊等所揭露之方法來控制其構造或Mw、Mw/Mn。The (B) adhesive resin in the present invention can be produced by a known method, and can be, for example, Japanese Laid-Open Patent Publication No. 2003-222717, Japanese Laid-Open Patent Publication No. 2006-259680, and International Publication No. 07/029871. The disclosed method controls its structure or Mw, Mw/Mn.

本發明中(B)黏著劑樹脂可單獨或混合兩種以上使用。In the present invention, (B) the adhesive resin may be used singly or in combination of two or more.

本發明中(B)黏著劑樹脂的含量相對(A)著色劑100質量份，較佳為10~1,000質量份，特佳為20~500質量份。黏著劑樹脂的含量若過少，會有例如鹼性顯影性降低、所得之著色性組成物的保存穩定性降低之虞，另一方面若過多，則因著色劑濃度相對降低，而有難以達成作為薄膜的目標色濃度之虞。In the present invention, the content of the (B) adhesive resin is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, per 100 parts by mass of the colorant (A). When the content of the adhesive resin is too small, for example, the alkali developability is lowered, and the storage stability of the obtained color-developing composition is lowered. On the other hand, if the amount is too large, the concentration of the colorant is relatively lowered, which makes it difficult to achieve The target color density of the film.

-(C)交聯劑--(C) Crosslinker -

本發明中(C)交聯劑係指具有2個以上可聚合基團的化合物。可聚合基團可例舉如乙烯性不飽和基團、環氧乙烷基(oxiranyl)、氧環丁烷基(oxetanyl)、N-烷氧基甲胺基等。本發明中，作為(C)交聯劑較佳為具有2個以上(甲基)丙烯醯基的化合物、或具有2個以上N-烷氧基甲胺基的化合物。In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. The polymerizable group may, for example, be an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxymethylamino group or the like. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

作為上述「具有2個以上(甲基)丙烯醯基的化合物」的具體實例，可例舉脂肪族多羥基化合物與(甲基)丙烯酸反應所得之多官能(甲基)丙烯酸酯、經己內酯改性之多官能(甲基)丙烯酸酯、經環氧烷改性之多官能(甲基)丙烯酸酯、使具有羥基之(甲基)丙烯酸酯與多官能異氰酸酯反應所得之多官能胺基甲酸酯(甲基)丙烯酸酯、使具有羥基之(甲基)丙烯酸酯與酸酐反應所得之具羧基之多官能(甲基)丙烯酸酯等。Specific examples of the above-mentioned "compound having two or more (meth)acryl fluorenyl groups" include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and An ester-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional amine group obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate a formate (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, and the like.

於此，作為上述脂肪族多羥基化合物可例舉諸如，如乙二醇、丙二醇、聚乙二醇、聚乙二醇之二元脂肪族多羥基化合物；甘油、三羥甲基丙烷、新戊四醇、二新戊四醇之三元以上的脂肪族多羥基化合物。上述具有羥基之(甲基)丙烯酸酯可例舉如(甲基)丙烯酸2-羥甲酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、丙三醇二甲基丙烯酸酯等。上述多官能異氰酸酯可例舉如甲苯二異氰酸酯、六亞甲基二異氰酸酯、二苯基亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等。酸酐可例舉諸如，如琥珀酸酐、馬來酸酐、戊二酸酐、伊康酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐之雙質子酸酐；苯均四酸酐、二苯基四羧酸二酐、二苯甲酮四羧酸二酐之四質子酸二酐。Here, as the above aliphatic polyhydroxy compound, for example, a dihydric aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polyethylene glycol; glycerin, trimethylolpropane, and neopentyl can be exemplified; A trihydric or higher aliphatic polyhydroxy compound of tetraol or dipentaerythritol. The (meth) acrylate having a hydroxyl group may, for example, be 2-hydroxymethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, or neopentyltriol tri(meth)acrylate. Dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. The polyfunctional isocyanate may, for example, be toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate or isophorone diisocyanate. The acid anhydride may, for example, be a bis-protic anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride; pyromellitic anhydride, diphenyltetracarboxylic acid Tetraprotonic acid dianhydride of acid dianhydride and benzophenone tetracarboxylic dianhydride.

又，上述經己內酯改性之多官能(甲基)丙烯酸酯，可例舉如日本特開平11-44955號公報之段落[0015]~[0018]所記載的化合物。上述經環氧烷改性之多官能(甲基)丙烯酸酯可例舉雙酚A之環氧乙烷及/或環氧丙烷改性二(甲基)丙烯酸酯、異三聚氰酸脂環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、三羥甲基丙烷之環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、新戊四醇之環氧乙烷及/或環氧丙烷改性三(甲基)丙烯酸酯、新戊四醇之環氧乙烷及/或環氧丙烷改性四(甲基)丙烯酸酯、二新戊四醇之環氧乙烷及/或環氧丙烷改性五(甲基)丙烯酸酯、二新戊四醇之環氧乙烷及/或環氧丙烷改性六(甲基)丙烯酸酯等。Further, the above-mentioned caprolactone-modified polyfunctional (meth) acrylate may, for example, be a compound described in paragraphs [0015] to [0018] of JP-A-11-44955. The above polyalkylene oxide-modified polyfunctional (meth) acrylate may, for example, be an ethylene oxide and/or propylene oxide-modified di(meth)acrylate or an iso-cyanate ring of bisphenol A. Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide and/or propylene oxide modified tri(meth)acrylate, neopentyl alcohol Ethylene oxide and/or propylene oxide modified tri(meth)acrylate, neopentyl alcohol ethylene oxide and/or propylene oxide modified tetra(meth)acrylate, dipentaerythritol Ethylene oxide and/or propylene oxide modified penta (meth) acrylate, dipentaerythritol ethylene oxide and/or propylene oxide modified hexa (meth) acrylate, and the like.

此外，作為上述「具有2個以上N-烷氧基甲胺基的化合物」，可例舉如具有三聚氰胺構造、苯并胍胺(benzoguanamine)構造、尿素構造的化合物等。此外，三聚氰胺構造、苯并胍胺構造係指具有1個以上三環或苯基取代三環作為基本骨架的化學構造，係為亦包含三聚氰胺、苯并胍胺或其等之縮合物的概念。作為具有2個以上N-烷氧基甲胺基之化合物的具體實例，可例舉N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺、N,N,N’,N’-四(烷氧基甲基)乙炔脲等。In addition, the "compound having two or more N-alkoxymethylamino groups" may, for example, be a compound having a melamine structure, a benzoguanamine structure or a urea structure. In addition, the melamine structure and the benzoguanamine structure mean one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is a concept including a condensate of melamine, benzoguanamine or the like. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N, N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)acetylene urea, and the like.

此等(C)交聯劑當中，較佳為3價以上之脂肪族多羥基化合物與(甲基)丙烯酸反應所得之多官能(甲基)丙烯酸酯、經己內酯改性之多官能(甲基)丙烯酸酯、多官能胺基甲酸酯(甲基)丙烯酸酯、具有羧基之多官能(甲基)丙烯酸酯、N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺。以著色層的強度高、著色層的表面平滑性優良，且未曝光部分的基板上及遮光層上難以發生浮汙(scumming)、膜殘留等觀點而言，3價以上之脂肪族多羥基化合物與(甲基)丙烯酸反應所得之多官能(甲基)丙烯酸酯當中，特佳為三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、二新戊四醇五丙烯酸酯、二新戊四醇六丙烯酸酯；具有羧基之多官能(甲基)丙烯酸酯當中，特佳為新戊四醇三丙烯酸酯與琥珀酸酐反應所得之化合物、二新戊四醇五丙烯酸酯與琥珀酸酐反應所得之化合物。Among these (C) crosslinking agents, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a valence of 3 or more with (meth)acrylic acid, and a polyfunctional modified by caprolactone are preferred ( Methyl) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N" - six ( Alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. The trivalent or higher aliphatic polyhydroxy compound is excellent in the strength of the colored layer, the surface smoothness of the colored layer, and the fact that the unexposed portion of the substrate and the light-shielding layer are less likely to cause scumming or film retention. Among the polyfunctional (meth) acrylates obtained by the reaction with (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and new are particularly preferred. Pentaerythritol hexaacrylate; among the polyfunctional (meth) acrylates having a carboxyl group, particularly a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, dipentaerythritol pentaacrylate and succinic anhydride The resulting compound.

本發明中，(C)交聯劑可單獨或2種以上混合使用。In the present invention, the (C) crosslinking agent may be used singly or in combination of two or more kinds.

本發明中的(C)交聯劑的含量係相對(A)著色劑100質量份，較佳為10~1,000質量份，特佳為20~500質量份。此時，交聯劑的含量若過少，會有無法獲得充分的硬化性之虞。另一方面，交聯劑的含量若過多，當賦予本發明著色性組成物鹼性顯影性時，則鹼性顯影性會降低，而有未曝光部分的基板上或遮光層上容易發生浮汙、膜殘留等的傾向。The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. At this time, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability of the coloring composition of the present invention is imparted, the alkali developability is lowered, and the surface of the unexposed portion or the light shielding layer is liable to be smeared. And the tendency of film residue and the like.

-(D)特定化合物-- (D) specific compounds -

(D)特定化合物係分類成上述(d-1)~(d-8)的任一種的化合物，本發明中只要含有此等當中的至少1種即可。(D) The specific compound is classified into the compound of any one of the above (d-1) to (d-8), and the present invention may contain at least one of these.

化合物(d-1)~(d-6)係具有-OR1 基、-SR2 基及-Q-NR3 R4 基當中的任一取代基作為對金屬具有配位能力之官能基，特別由對金屬之配位能力之觀點而言，係以具有-SR2 基、-Q-NR3 R4 基為佳。The compounds (d-1) to (d-6) have any one of a -OR 1 group, a -SR 2 group and a -Q-NR 3 R 4 group as a functional group having a coordinating ability to a metal, particularly from the viewpoint of capability of complexing metals, the system having -SR 2 group, -Q-NR 3 R 4 group is preferred.

於此，R1 ~R4 彼此獨立表示氫原子或取代或未取代之1價烴基，而作為所述烴基，可例舉碳數1~20(較佳為碳數1~8)之脂肪族烴基、碳數3~20(較佳為碳數3~6)之脂環式烴基、碳數6~20(較佳為碳數6~14)之芳基、碳數7~20(較佳為碳數7~14)之芳烷基等。作為碳數1~20之脂肪族烴基，可列舉碳數1~20之烷基、碳數2~20之烯基、碳數2~20之炔基等，具體而言，可例舉甲基、乙基、丙基、乙烯基、烯丙基、乙炔基、2-丙炔基等。作為碳數3~20之脂環式烴基，可列舉碳數3~8之環烷基、碳數3~8之環烯基等，具體而言，可例舉環丙基、環戊基、環己基、環丙烯基、環戊烯基、環己烯基等。此外，烷基、烯基及炔基可呈直鏈狀或支鏈狀，烯基及炔基可於分子內及末端之任一者具有不飽和鍵。又，作為碳數6~20之芳基，可例舉苯基、萘基、蒽基、菲基、聯苯基等。作為碳數7~20之芳烷基，則可例舉苯甲基、苯乙基、三苯甲基等。Here, R 1 to R 4 each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and as the hydrocarbon group, an aliphatic group having 1 to 20 carbon atoms (preferably, carbon number 1 to 8) may be mentioned. a hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms), an aryl group having 6 to 20 carbon atoms (preferably having 6 to 14 carbon atoms), and a carbon number of 7 to 20 (preferably It is an aralkyl group having a carbon number of 7 to 14). Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Specifically, a methyl group is exemplified. , ethyl, propyl, vinyl, allyl, ethynyl, 2-propynyl and the like. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cycloalkyl group having 3 to 8 carbon atoms and a cycloalkenyl group having 3 to 8 carbon atoms. Specific examples thereof include a cyclopropyl group and a cyclopentyl group. Cyclohexyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and the like. Further, the alkyl group, the alkenyl group and the alkynyl group may be linear or branched, and the alkenyl group and the alkynyl group may have an unsaturated bond in either the molecule or the terminal. Further, examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and a biphenyl group. The aralkyl group having 7 to 20 carbon atoms may, for example, be a benzyl group, a phenethyl group or a trityl group.

又，此等烴基可具有取代基，作為所述取代基，可例舉如羥基、烷氧基、鹵素基、硝基、氰基、醯胺基、磺酸基、烷基(較佳為C1-6 烷基)-羰基、芳基(較佳為C6-14 芳基)-羰基等。再者，此等取代基之位置及數目係任意者，當具有2個以上取代基時，該取代基可相同或相異。Further, these hydrocarbon groups may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxy group, a halogen group, a nitro group, a cyano group, a decylamino group, a sulfonic acid group, and an alkyl group (preferably C). 1-6 alkyl)-carbonyl, aryl (preferably C 6-14 aryl)-carbonyl, and the like. Further, the positions and numbers of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

此等當中，作為R1 ~R4 ，特佳為氫原子、碳數1~8之烷基、碳數3~8之環烷基、碳數6~14之芳基、碳數7~14之芳烷基。Among them, R 1 to R 4 are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a carbon number of 7 to 14 Aralkyl group.

Q係表示單鍵或羰基，惟可依據化合物的種類而適當選擇。The Q system represents a single bond or a carbonyl group, and may be appropriately selected depending on the kind of the compound.

另一方面，化合物(d-7)~(d-8)係具備雜環基作為對金屬具有配位能力之官能基，並具備羧基或磺酸基作為酸性官能基。On the other hand, the compounds (d-7) to (d-8) have a heterocyclic group as a functional group having a coordinating ability to a metal, and have a carboxyl group or a sulfonic acid group as an acidic functional group.

作為雜環，可列舉碳原子與選自氮原子、氧原子及硫原子的至少1種原子鍵結所形成的單環式雜環或多環式雜環，可為脂環式雜環或芳香族雜環。作為單環式雜環，較佳為3~8元環，更佳為5~6元環，具體實例可例舉環氧乙烷環、氮丙環等之具有一個雜原子之3元雜環；呋喃環、噻吩環、吡咯環、2H-吡咯環、二氫吡咯環、2-二氫吡咯環、咯啶環等之具有一個雜原子之5元雜環；1,3-二氧戊環、唑環、異唑環、1,3-唑環、噻唑環、異噻唑環、1,3-噻唑環、咪唑環、咪唑啉環、2-咪唑啉環、咪唑啶環、吡唑環、吡唑啉環、3-吡唑啉環、吡唑啶環等之具有兩個雜原子之5元雜環；呋呫(furazan)環、***環、噻二唑環、二唑環等之具有三個雜原子5元雜環；吡喃環、2H-吡喃環、吡啶環、哌啶環等之具有一個雜原子之6元雜環；硫代吡喃環、嗒環、嘧啶環、吡環、哌環、福啉環等之具有兩個雜原子之6元雜環；1,2,4-三環等之具有三個雜原子之6元雜環等。此外，作為多環式雜環，可例舉2~3個單環式雜環彼此稠合者、或單環式雜環與1~2個芳香族環(例如苯環、萘環等)稠合而成之二環系雜環、三環系雜環等。作為二環系雜環，可例舉苯并呋喃環、異苯并呋喃環、1-苯并噻吩環、2-苯并噻吩環、吲哚環、3-吲哚環、異吲哚環、吲環、吲哚啉環、異吲哚啉環、2H-唍烯環、唍(chromane)環、異唍環、1H-2-苯并吡喃環、喹啉環、異喹啉環、4H-喹環等具有一個雜原子之雜環；苯并咪唑環、苯并噻唑環、1H-吲唑環、1,8-啶環、喹啉環、喹唑啉環、喹唑啉啶環、啉環、呔環等之具有兩個雜原子之雜環；嘌呤環、蝶啶環等之具有四個雜原子之雜環等。又作為三環系雜環，可例舉咔唑環、二苯并哌喃環、啡啶環、吖啶環等之具有一個雜原子之雜環；β-咔啉環、嘧啶環、1,7-啡啉環、1,10-啡啉環、噻蒽環、啡噻環、啡環、啡噻環、啡環等之具有兩個雜原子之雜環等。The heterocyclic ring may, for example, be a monocyclic heterocyclic ring or a polycyclic heterocyclic ring formed by bonding a carbon atom to at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and may be an alicyclic heterocyclic ring or an aromatic group. Family heterocycle. The monocyclic heterocyclic ring is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Specific examples thereof include a 3-membered heterocyclic ring having a hetero atom such as an oxirane ring or an aziridine ring. a 5-membered heterocyclic ring having a hetero atom; a 1,3-dioxolane; a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyrrole ring, a dihydropyrrole ring, a 2-dihydropyrrole ring, a pyridinium ring, or the like; , Oxazole ring, different Oxazole ring, 1,3- An azole ring, a thiazole ring, an isothiazole ring, a 1,3-thiazole ring, an imidazole ring, an imidazoline ring, a 2-imidazoline ring, an imidazolidinium ring, a pyrazole ring, a pyrazoline ring, a 3-pyrazoline ring, a 5-membered heterocyclic ring having two heteroatoms such as a pyrazolidine ring; a furazan ring, a triazole ring, a thiadiazole ring, a 5-membered heterocyclic ring having three heteroatoms; a 6-membered heterocyclic ring having a hetero atom such as a pyran ring, a 2H-pyran ring, a pyridine ring or a piperidine ring; a thiopyran ring; Ring, pyrimidine ring, pyridyl Ring, piperazine ring, a 6-membered heterocyclic ring having two heteroatoms such as a porphyrin ring; 1,2,4-tri A 6-membered heterocyclic ring having three hetero atoms, and the like. Further, the polycyclic heterocyclic ring may be one in which two or three monocyclic heterocyclic rings are fused to each other, or a monocyclic heterocyclic ring is bonded to one or two aromatic rings (for example, a benzene ring or a naphthalene ring). A bicyclic heterocycle, a tricyclic heterocycle, and the like. The bicyclic heterocyclic ring may, for example, be a benzofuran ring, an isobenzofuran ring, a 1-benzothiophene ring, a 2-benzothiophene ring, an anthracene ring, a 3-fluorene ring or an isoindole ring.吲 Ring, porphyrin ring, isoporphyrin ring, 2H- Terpene ring, Chrom (chromane) ring, different Anthracycline, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quin a heterocyclic ring having a hetero atom; a benzimidazole ring, a benzothiazole ring, a 1H-carbazole ring, 1,8- Acridine ring a porphyrin ring, a quinazoline ring, a quinazolinidine ring, Porphyrin ring, hydrazine a heterocyclic ring having two hetero atoms; a heterocyclic ring having four hetero atoms such as an anthracene ring or a pteridine ring; and the like. Further, the tricyclic ring heterocyclic ring may, for example, be a heterocyclic ring having a hetero atom such as a carbazole ring, a dibenzopyran ring, a pyridine ring or an acridine ring; a β-carboline ring, a pyrimidine ring, and 1, 7-morpholine ring, 1,10-morpholine ring, thiophene ring, brown Thiocyclic, brown Ring, thiophene Ring, brown a heterocyclic ring having two hetero atoms, and the like.

此外，化合物(d-1)~(d-8)可為鹽之形態。鹽可例舉銨鹽、有機銨鹽等，特佳為有機銨鹽。Further, the compounds (d-1) to (d-8) may be in the form of a salt. The salt may, for example, be an ammonium salt or an organic ammonium salt, and particularly preferably an organic ammonium salt.

作為有機銨離子並未特別限定，較佳為單、二、三或四烷基銨離子，特佳為四烷基銨離子。再者，與氮原子鍵結之烷基可相同或相異，較佳為碳數1~20之直鏈狀、支鏈狀或環狀烷基，更佳為碳數1~12之直鏈烷基。具體而言，可例舉四乙基銨、四丁基銨、二甲基(雙十八基)銨、四己基銨、三丁基(甲基)銨、四(十二基)銨、四辛基銨、三甲基(十六基)銨、三辛基(甲基)銨、四異戊基銨、三乙基銨、三丁基銨、三己基銨、三辛基銨等。The organic ammonium ion is not particularly limited, and is preferably a mono-, di-, tri- or tetraalkylammonium ion, particularly preferably a tetraalkylammonium ion. Further, the alkyl group bonded to the nitrogen atom may be the same or different, and is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, more preferably a linear chain having 1 to 12 carbon atoms. alkyl. Specifically, it may, for example, be tetraethylammonium, tetrabutylammonium, dimethyl(bisoctadecyl)ammonium, tetrahexylammonium, tributyl(methyl)ammonium, tetrakis(dodecyl)ammonium or tetra. Octyl ammonium, trimethyl (hexadecyl) ammonium, trioctyl (methyl) ammonium, tetraisoamylammonium, triethyl ammonium, tributyl ammonium, trihexylammonium, trioctyl ammonium, and the like.

以下，對化合物(d-1)~(d-8)具體進行說明。Hereinafter, the compounds (d-1) to (d-8) will be specifically described.

[化合物(d-1)及(d-3)][Compounds (d-1) and (d-3)]

化合物(d-1)及(d-3)係具有選自包含-OR1 基及-SR2 基之群組的至少1種之脂肪族羧酸或脂環式羧酸或其等之鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點而言，較佳為下述式(2)所示之化合物或其鹽：The compounds (d-1) and (d-3) have at least one aliphatic carboxylic acid or alicyclic carboxylic acid or a salt thereof selected from the group consisting of -OR 1 group and -SR 2 group. Further, from the viewpoint of further suppressing generation of aggregated impurities and lowering of the contrast ratio, a compound represented by the following formula (2) or a salt thereof is preferred:

Y1 -COOH　(2)Y 1 -COOH (2)

[上述式(2)中，Y1 表示經-OR1 或-SR2 取代之碳數1~20之烷基或經-OR1 或-SR2 取代之碳數3~8之環烷基]。[In the formula (2), Y 1 represents -OR 1 or -SR 2 via the carbon atoms substituted by an alkyl group having 1 to 20 or -OR 1 or -SR 2 of the substituted carbocyclic group of 3 to 8] .

作為具有-OR1 基之化合物(d-1)，可例舉如乙醇酸、乳酸、甘油酸、羥基丁酸、甲羥戊酸、泛解酸、2-甲氧基丙酸、甲氧基丁酸、甲氧基戊酸、2-苯氧基丙酸、苯氧基丁酸、苯氧基戊酸、2-苯甲氧基丙酸、苯甲氧基丁酸、苯甲氧基戊酸。The compound (d-1) having a -OR 1 group may, for example, be glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, mevalonic acid, pantoic acid, 2-methoxypropionic acid or methoxy group. Butyric acid, methoxy valeric acid, 2-phenoxypropionic acid, phenoxybutyric acid, phenoxyvaleric acid, 2-benzyloxypropionic acid, benzyloxybutyric acid, benzyloxypenta acid.

又作為具有-SR2 基之化合物(d-1)，可例舉如2-甲硫基丙酸、2-甲硫基丁酸、3-甲硫基丁酸、2-甲硫基戊酸、3-甲硫基戊酸、4-甲硫基戊酸、2-苯硫基丙酸、2-苯硫基戊酸、3-苯硫基戊酸、4-苯硫基戊酸、2-苯甲硫基丙酸、2-苯甲硫基丁酸、3-苯甲硫基丁酸、2-苯甲硫基戊酸、3-苯甲硫基戊酸、4-苯甲硫基戊酸、2-氫硫基丁酸、下述化合物群a所示之化合物。Further, the compound (d-1) having a -SR 2 group may, for example, be 2-methylthiopropionic acid, 2-methylthiobutyric acid, 3-methylthiobutyric acid or 2-methylthiovaleric acid. , 3-methylthiovaleric acid, 4-methylthiovaleric acid, 2-phenylthiopropionic acid, 2-phenylthiovaleric acid, 3-phenylthiovaleric acid, 4-phenylthiovaleric acid, 2 - Benzylthiopropionic acid, 2-benzylthiobutyric acid, 3-benzylthiobutyric acid, 2-benzylthiopentanoic acid, 3-benzylthiopentanoic acid, 4-benzylthio group Valeric acid, 2-hydrogenthiobutyric acid, and a compound represented by the following compound group a.

作為具有-OR1 基之化合物(d-3)，可例舉如2-羥基環己烷羧酸、3-羥基環己烷羧酸、4-羥基環己烷羧酸、莽草酸(環己烯環三羥基酸)、奎尼酸(quinic acid,環己烷環四羥基酸)、2-甲氧基環己烷羧酸、3-甲氧基環己烷羧酸、4-甲氧基環己烷羧酸、2-苯氧基環己烷羧酸、3-苯氧基環己烷羧酸、4-苯氧基環己烷羧酸、2-苯甲氧基環己烷羧酸、3-苯甲氧基環己烷羧酸、4-苯甲氧基環己烷羧酸。As the compound having a -OR 1 group of (d-3), may, for example such as 2-hydroxy-cyclohexanecarboxylic acid, 3-hydroxy-cyclohexanecarboxylic acid, 4-hydroxy-cyclohexanecarboxylic acid, shikimic acid (cyclohexyl An olefinic trihydroxy acid), quinic acid (cyclohexane ring tetrahydroxy acid), 2-methoxycyclohexanecarboxylic acid, 3-methoxycyclohexanecarboxylic acid, 4-methoxyl Cyclohexanecarboxylic acid, 2-phenoxycyclohexanecarboxylic acid, 3-phenoxycyclohexanecarboxylic acid, 4-phenoxycyclohexanecarboxylic acid, 2-benzyloxycyclohexanecarboxylic acid , 3-benzyloxycyclohexanecarboxylic acid, 4-benzyloxycyclohexanecarboxylic acid.

又作為具有-SR2 基之化合物(d-3)，可例舉如2-氫硫基環己烷羧酸、3-氫硫基環己烷羧酸、4-氫硫基環己烷羧酸、2-甲硫基環己烷羧酸、3-甲硫基環己烷羧酸、4-甲硫基環己烷羧酸、2-苯硫基環己烷羧酸、3-苯硫基環己烷羧酸、4-苯硫基環己烷羧酸、2-苯甲硫基環己烷羧酸、3-苯甲硫基環己烷羧酸、4-苯甲硫基環己烷羧酸。And as -SR 2 group of the compound (d-3), may, for example such as 2-mercapto cyclohexanecarboxylic acid, 3-mercapto acid, 4-cyclohexane carboxylic group hydrogen with Acid, 2-methylthiocyclohexanecarboxylic acid, 3-methylthiocyclohexanecarboxylic acid, 4-methylthiocyclohexanecarboxylic acid, 2-phenylthiocyclohexanecarboxylic acid, 3-phenylsulfuric acid Cyclohexanecarboxylic acid, 4-phenylthiocyclohexanecarboxylic acid, 2-benzylthiocyclohexanecarboxylic acid, 3-benzylthiocyclohexanecarboxylic acid, 4-benzylthiocyclohexane Alkanoic acid.

[化合物(d-2)及(d-4)][Compounds (d-2) and (d-4)]

化合物(d-2)及(d-4)係具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之脂肪族磺酸或脂環式磺酸或其等之鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點而言，較佳為下述式(3)所示之化合物或其鹽：The compounds (d-2) and (d-4) have at least one aliphatic sulfonic acid or alicyclic ring selected from the group consisting of a -OR 1 group, a -SR 2 group and a -Q-NR 3 R 4 group. The sulfonic acid or a salt thereof is preferably a compound represented by the following formula (3) or a salt thereof from the viewpoint of further suppressing generation of aggregated impurities and lowering the contrast ratio:

Y2 -SO3 H　(3)Y 2 -SO 3 H (3)

[上述式(3)中，Y2 表示由選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種取代之碳數1~20之烷基、由選自包含或-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種取代之碳數3~20之飽和脂環式烴基]。[In the above formula (3), Y 2 represents an alkyl group having 1 to 20 carbon atoms substituted by at least one selected from the group consisting of -OR 1 group, -SR 2 group and -Q-NR 3 R 4 group; And a saturated alicyclic hydrocarbon group having 3 to 20 carbon atoms which is substituted with at least one selected from the group consisting of -OR 1 group, -SR 2 group and -Q-NR 3 R 4 group.

作為化合物(d-2)，可例舉如下述化合物群b所示之化合物。The compound (d-2) may, for example, be a compound represented by the following compound group b.

作為化合物(d-4)，可例舉如4-胺基環己烷磺酸、2,5-二胺基環己烷磺酸、2-氫硫基環己烷磺酸、3-氫硫基環己烷磺酸、2-氫硫基環戊烷磺酸、3-氫硫基環戊烷磺酸、下述化合物群c所示之化合物。The compound (d-4) may, for example, be 4-aminocyclohexanesulfonic acid, 2,5-diaminocyclohexanesulfonic acid, 2-hydrothiocyclohexanesulfonic acid or 3-hydrogen sulfur. A compound represented by the following compound group c is cyclohexanesulfonic acid, 2-hydrothiocyclopentanesulfonic acid, 3-hydrothiocyclopentanesulfonic acid.

[化合物(d-5)][Compound (d-5)]

化合物(d-5)係由具有-SR2 基之基團與具有羧基之基團取代之芳香族烴或其鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點，較佳為下述式(4)所示之化合物或其鹽：The compound (d-5) is an aromatic hydrocarbon or a salt thereof substituted with a group having a -SR 2 group and a group having a carboxyl group, and from the viewpoint of further suppressing generation of aggregated impurities and lowering of a contrast ratio, it is preferably the following a compound of the formula (4) or a salt thereof:

(上述式(4)中，Z表示單鍵、伸甲基或碳數2~3之伸烷基，A表示羥基、鹵素基、烷基或烷氧基，n表示0~4之整數，R2 係與前述同義)。(In the above formula (4), Z represents a single bond, a methyl group or a C 2 to 3 alkyl group, A represents a hydroxyl group, a halogen group, an alkyl group or an alkoxy group, and n represents an integer of 0 to 4, R 2 is synonymous with the foregoing).

作為上述式(4)所示之化合物，可例舉如2-氫硫基-2-苯基乙酸、2-氫硫基-3-苯基丙酸、2-氫硫基-3-苯基丁酸、3-氫硫基-3-苯基丁酸、2-甲硫基-2-苯基乙酸、2-甲硫基-3-苯基丙酸、2-甲硫基-3-苯基丁酸、3-甲硫基-3-苯基丁酸、2-苯硫基-2-苯基乙酸、2-苯硫基-3-苯基丙酸、2-苯硫基丁酸、3-苯硫基丁酸、2-苯硫基-3-苯基丁酸、3-苯硫基-3-苯基丁酸、2-苯甲硫基-2-苯基乙酸、2-苯甲硫基-3-苯基丙酸、2-苯甲硫基-3-苯基丁酸、3-苯甲硫基-3-苯基丁酸、下述化合物群d所示之化合物。The compound represented by the above formula (4) may, for example, be 2-hydrothio-2-phenylacetic acid, 2-hydrothio-3-phenylpropionic acid or 2-hydrothio-3-phenyl group. Butyric acid, 3-hydrothio-3-phenylbutyric acid, 2-methylthio-2-phenylacetic acid, 2-methylthio-3-phenylpropionic acid, 2-methylthio-3-benzene Butyric acid, 3-methylthio-3-phenylbutyric acid, 2-phenylthio-2-phenylacetic acid, 2-phenylthio-3-phenylpropionic acid, 2-phenylthiobutyric acid, 3-phenylthiobutyric acid, 2-phenylthio-3-phenylbutyric acid, 3-phenylthio-3-phenylbutyric acid, 2-benzylthio-2-phenylacetic acid, 2-benzene Methylthio-3-phenylpropionic acid, 2-benzylthio-3-phenylbutanoic acid, 3-benzylthio-3-phenylbutyric acid, a compound represented by the following compound group d.

[化合物(d-6)][compound (d-6)]

化合物(d-6)係由選自包含具有-OR1 基之基團、具有-SR2 基之基團及具有-Q-NR3 R4 基之基團之群組的至少1種與具有磺酸基之基團取代之芳香族烴或其鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點而言，較佳為具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之芳基磺酸或其鹽。The compound (d-6) is at least one selected from the group consisting of a group having a group having an -OR 1 group, a group having a -SR 2 group, and a group having a -Q-NR 3 R 4 group. The aromatic hydrocarbon or a salt thereof substituted with a group of a sulfonic acid group preferably has a selected from the group consisting of -OR 1 group, -SR 2 group and -Q from the viewpoint of further suppressing generation of aggregated impurities and lowering of contrast ratio. At least one arylsulfonic acid or a salt thereof of the group of -NR 3 R 4 groups.

作為化合物(d-6)，可例舉如鄰酚磺酸、間酚磺酸、對酚磺酸、4-羥基-3-甲氧基苯磺酸、3,5-二氯-2-羥基苯磺酸、4-羥基-1,3-苯二磺酸、5-羥基-1,3-苯二磺酸、2-羥基-7-萘磺酸、6-羥基-2-萘磺酸、4-羥基-1-萘磺酸、7-羥基-1-萘磺酸、1-羥基-2-萘磺酸、2-羥基-1-萘磺酸、5-羥基-1-萘磺酸、4-羥基-2-萘磺酸、5-羥基-2-萘磺酸、8-羥基-2-萘磺酸、8-羥基-1-萘磺酸、3-羥基-2-萘磺酸、3-羥基-1-萘磺酸、6-羥基-1-萘磺酸、7-苯胺基-1-萘酚-3-磺酸、苯基J酸(J-acid,2-胺-5-萘酚-7-磺酸)、2,4-二硝基-1-萘酚-7-磺酸、2,4-二硝基-1-萘酚-7-磺酸、2-羥基-4-甲氧基二苯甲酮-5-磺酸、2,4-二硝基-1-萘酚-7-磺酸、4-羥基-1,5-萘二磺酸、7-羥基-1,3-萘二磺酸、2-羥基-3,6-萘二磺酸、1-羥基-2,3-萘二磺酸、4-羥基-1,3-萘二磺酸、1-羥基-2,5-萘二磺酸、1-羥基-2,6-萘二磺酸、1-羥基-2,7-萘二磺酸、8-羥基-1,7-萘二磺酸、4-羥基-1,2-萘二磺酸、5-羥基-1,7-萘二磺酸、1-羥基-3,6-萘二磺酸、4-羥基-2,6-萘二磺酸、1-羥基-3,8-萘二磺酸、4-羥基-1,8-萘二磺酸、4-羥基-1,7-萘二磺酸、4-羥基-1,6-萘二磺酸、5-羥基-1,2-萘二磺酸、8-羥基-2,4-萘二磺酸、5-羥基-1,4-萘二磺酸、5-羥基-2,3-萘二磺酸、8-羥基-1,3-萘二磺酸、8-羥基-1,2-萘二磺酸、2-羥基-1,3-萘二磺酸、2-羥基-1,4-萘二磺酸、2-羥基-1,5-萘二磺酸、2-羥基-1,6-萘二磺酸、2-羥基-1,7-萘二磺酸、2-羥基-1,8-萘二磺酸、3-羥基-1,2-萘二磺酸、6-羥基-1,7-萘二磺酸、3-羥基-2,6-萘二磺酸、7-羥基-1,6-萘二磺酸、3-羥基-1,8-萘二磺酸、3-羥基-1,7-萘二磺酸、3-羥基-1,6-萘二磺酸、3-羥基-1,5-萘二磺酸、6-羥基-1,2-萘二磺酸、6-羥基-1,3-萘二磺酸、6-羥基-1,4-萘二磺酸、6-羥基-2,3-萘二磺酸、7-羥基-1,2-萘二磺酸、鄰胺基苯磺酸、間胺基苯磺酸、對胺基苯磺酸、鄰甲苯胺-4-磺酸、間甲苯胺-4-磺酸、對甲苯胺-2-磺酸、鄰甲氧苯胺-5-磺酸、3-胺基-6-甲氧基苯磺酸、2-胺基-5-甲氧基苯磺酸、4-胺基-3-甲氧基苯磺酸、2-胺基-4-甲氧基苯磺酸、3-硝基苯胺-4-磺酸、4-氯苯胺-3-磺酸、2,5-二氯對胺基苯磺酸、4,5-二氯苯胺-2-磺酸、4-乙醯胺-2-胺基苯磺酸、4-胺基-2-氯甲苯-5-磺酸、5-胺基-2-氯甲苯-4-磺酸、3-胺基-6-氯-4-磺酸基安息香酸、2-胺基-1,4-苯二磺酸、2-胺基-1,5-苯二磺酸、3-胺基-1,2-苯二磺酸、4-胺基-1,2-苯二磺酸、2-胺基-1,3-苯二磺酸、5-胺基-1,3-苯二磺酸、2-胺基-1-萘磺酸、6-胺基-1-萘磺酸、1-胺基-2-萘磺酸、8-胺基-1-萘磺酸、6-胺基-2-萘磺酸、4-胺基-1-萘磺酸、5-胺基-1-萘磺酸、8-胺基-2-萘磺酸、5-胺基-2-萘磺酸、2-胺基-7-萘磺酸、2-胺基-8-萘磺酸、4-胺基-2-萘磺酸、3-胺基-2-萘磺酸、3-胺基-1-萘磺酸、2-胺基-1,5-萘二磺酸、4-胺基-1,7-萘二磺酸、4-胺基-1,6-萘二磺酸、1-胺基-2,7-萘二磺酸、3-胺基-1,5-萘二磺酸、7-胺基-1,3-萘二磺酸、4-胺基-2,5-萘二磺酸、1-胺基-3,6-萘二磺酸、3-胺基-2,7-萘二磺酸、6-胺基-1,3-萘二磺酸、4-胺基-1,5-萘二磺酸、1-胺基-2,3-萘二磺酸、4-胺基-1,3-萘二磺酸、1-胺基-2,5-萘二磺酸、1-胺基-2,6-萘二磺酸、8-胺基-1,7-萘二磺酸、4-胺基-1,2-萘二磺酸、4-胺基-2,8-萘二磺酸、4-胺基-2,6-萘二磺酸、4-胺基-1,8-萘二磺酸、5-胺基-1,2-萘二磺酸、5-胺基-1,3-萘二磺酸、5-胺基-1,4-萘二磺酸、5-胺基-2,3-萘二磺酸、8-胺基-1,3-萘二磺酸、8-胺基-1,2-萘二磺酸、2-胺基-1,3-萘二磺酸、2-胺基-1,4-萘二磺酸、2-胺基-1,6-萘二磺酸、2-胺基-1,7-萘二磺酸、2-胺基-1,8-萘二磺酸、3-胺基-1,2-萘二磺酸、6-胺基-1,7-萘二磺酸、3-胺基-2,6-萘二磺酸、3-胺基-2,5-萘二磺酸、3-胺基-1,8-萘二磺酸、3-胺基-1,7-萘二磺酸、3-胺基-1,6-萘二磺酸、6-胺基-1,2-萘二磺酸、6-胺基-1,4-萘二磺酸、6-胺基-2,3-萘二磺酸、7-胺基-1,2-萘二磺酸、4-(胺基甲基)苯磺酸、4-(胺基甲基)-2-甲基苯磺酸、4-氫硫基苯磺酸、4-甲硫基苯磺酸。The compound (d-6) may, for example, be o-phenolsulfonic acid, m-phenolsulfonic acid, p-phenolsulfonic acid, 4-hydroxy-3-methoxybenzenesulfonic acid or 3,5-dichloro-2-hydroxyl group. Benzenesulfonic acid, 4-hydroxy-1,3-benzenedisulfonic acid, 5-hydroxy-1,3-benzenedisulfonic acid, 2-hydroxy-7-naphthalenesulfonic acid, 6-hydroxy-2-naphthalenesulfonic acid, 4-hydroxy-1-naphthalenesulfonic acid, 7-hydroxy-1-naphthalenesulfonic acid, 1-hydroxy-2-naphthalenesulfonic acid, 2-hydroxy-1-naphthalenesulfonic acid, 5-hydroxy-1-naphthalenesulfonic acid, 4-hydroxy-2-naphthalenesulfonic acid, 5-hydroxy-2-naphthalenesulfonic acid, 8-hydroxy-2-naphthalenesulfonic acid, 8-hydroxy-1-naphthalenesulfonic acid, 3-hydroxy-2-naphthalenesulfonic acid, 3-hydroxy-1-naphthalenesulfonic acid, 6-hydroxy-1-naphthalenesulfonic acid, 7-anilino-1-naphthol-3-sulfonic acid, phenyl J acid (J-acid, 2-amine-5- Naphthol-7-sulfonic acid), 2,4-dinitro-1-naphthol-7-sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid, 4-hydroxy-1,5-naphthalene disulfonic acid, 7-hydroxy-1 , 3-naphthalene disulfonic acid, 2-hydroxy-3,6-naphthalene disulfonic acid, 1-hydroxy-2,3-naphthalene disulfonic acid, 4-hydroxy-1,3-naphthalenedisulfonic acid, 1-hydroxyl -2,5-naphthalene disulfonic acid, 1-hydroxy-2,6-naphthalene disulfonic acid, 1-hydroxy-2,7-naphthalene disulfonic acid, 8-hydroxy-1,7-naphthalene disulfonic acid, 4 - 1,2-naphthalene disulfonic acid, 5-hydroxy-1,7-naphthalene disulfonic acid, 1-hydroxy-3,6-naphthalene disulfonic acid, 4-hydroxy-2,6-naphthalene disulfonic acid, 1-hydroxy-3,8-naphthalene disulfonic acid, 4-hydroxy-1,8-naphthalene disulfonic acid, 4-hydroxy-1,7-naphthalene disulfonic acid, 4-hydroxy-1,6-naphthalene disulfonate Acid, 5-hydroxy-1,2-naphthalene disulfonic acid, 8-hydroxy-2,4-naphthalene disulfonic acid, 5-hydroxy-1,4-naphthalene disulfonic acid, 5-hydroxy-2,3-naphthalene Disulfonic acid, 8-hydroxy-1,3-naphthalenedisulfonic acid, 8-hydroxy-1,2-naphthalenedisulfonic acid, 2-hydroxy-1,3-naphthalenedisulfonic acid, 2-hydroxy-1,4 -naphthalene disulfonic acid, 2-hydroxy-1,5-naphthalene disulfonic acid, 2-hydroxy-1,6-naphthalene disulfonic acid, 2-hydroxy-1,7-naphthalene disulfonic acid, 2-hydroxy-1 , 8-naphthalene disulfonic acid, 3-hydroxy-1,2-naphthalenedisulfonic acid, 6-hydroxy-1,7-naphthalene disulfonic acid, 3-hydroxy-2,6-naphthalenedisulfonic acid, 7-hydroxyl -1,6-naphthalene disulfonic acid, 3-hydroxy-1,8-naphthalene disulfonic acid, 3-hydroxy-1,7-naphthalene disulfonic acid, 3-hydroxy-1,6-naphthalene disulfonic acid, 3 -hydroxy-1,5-naphthalene disulfonic acid, 6-hydroxy-1,2-naphthalene disulfonic acid, 6-hydroxy-1,3-naphthalene disulfonic acid, 6-hydroxy-1,4-naphthalene disulfonic acid , 6-hydroxy-2,3-naphthalene disulfonic acid, 7-hydroxy-1,2-naphthalene disulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, ortho Aniline-4- Acid, m-toluidine-4-sulfonic acid, p-toluidine-2-sulfonic acid, o-methoxyaniline-5-sulfonic acid, 3-amino-6-methoxybenzenesulfonic acid, 2-amino-5 -methoxybenzenesulfonic acid, 4-amino-3-methoxybenzenesulfonic acid, 2-amino-4-methoxybenzenesulfonic acid, 3-nitroaniline-4-sulfonic acid, 4-chloro Aniline-3-sulfonic acid, 2,5-dichloro-p-aminobenzenesulfonic acid, 4,5-dichloroaniline-2-sulfonic acid, 4-acetamido-2-aminobenzenesulfonic acid, 4-amine Benzyl-2-chlorotoluene-5-sulfonic acid, 5-amino-2-chlorotoluene-4-sulfonic acid, 3-amino-6-chloro-4-sulfonic acid benzoic acid, 2-amino-1 , 4-benzenedisulfonic acid, 2-amino-1,5-benzenedisulfonic acid, 3-amino-1,2-benzenedisulfonic acid, 4-amino-1,2-benzenedisulfonic acid, 2-amino-1,3-benzenedisulfonic acid, 5-amino-1,3-benzenedisulfonic acid, 2-amino-1-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 1-amino-2-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 6-amino-2-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 5-amino-1 -naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 2-amino-7-naphthalenesulfonic acid, 2-amino-8-naphthalenesulfonic acid, 4 -Amino-2-naphthalenesulfonic acid, 3-amino-2-naphthalenesulfonic acid, 3-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalene disulfonic acid, 4-amino group -1,7-naphthalene disulfonic acid 4-amino-1,6-naphthalene disulfonic acid, 1-amino-2,7-naphthalene disulfonic acid, 3-amino-1,5-naphthalene disulfonic acid, 7-amino-1,3 -naphthalene disulfonic acid, 4-amino-2,5-naphthalene disulfonic acid, 1-amino-3,6-naphthalene disulfonic acid, 3-amino-2,7-naphthalene disulfonic acid, 6- Amino-1,3-naphthalene disulfonic acid, 4-amino-1,5-naphthalene disulfonic acid, 1-amino-2,3-naphthalene disulfonic acid, 4-amino-1,3-naphthalene Disulfonic acid, 1-amino-2,5-naphthalene disulfonic acid, 1-amino-2,6-naphthalene disulfonic acid, 8-amino-1,7-naphthalene disulfonic acid, 4-amino group -1,2-naphthalene disulfonic acid, 4-amino-2,8-naphthalene disulfonic acid, 4-amino-2,6-naphthalene disulfonic acid, 4-amino-1,8-naphthalene disulfonate Acid, 5-amino-1,2-naphthalene disulfonic acid, 5-amino-1,3-naphthalene disulfonic acid, 5-amino-1,4-naphthalene disulfonic acid, 5-amino-2 , 3-naphthalene disulfonic acid, 8-amino-1,3-naphthalene disulfonic acid, 8-amino-1,2-naphthalene disulfonic acid, 2-amino-1,3-naphthalene disulfonic acid, 2-Amino-1,4-naphthalene disulfonic acid, 2-amino-1,6-naphthalene disulfonic acid, 2-amino-1,7-naphthalene disulfonic acid, 2-amino-1,8 -naphthalene disulfonic acid, 3-amino-1,2-naphthalene disulfonic acid, 6-amino-1,7-naphthalene disulfonic acid, 3-amino-2,6-naphthalene disulfonic acid, 3- Amino-2,5-naphthalene disulfonic acid, 3-amino-1,8-naphthalene disulfonic acid, 3-amino-1,7-naphthalene disulfonic acid, 3-amino-1,6-naphthalene two Sulfonic acid, 6-amino-1,2-naphthalene disulfonic acid, 6-amino-1,4-naphthalene disulfonic acid, 6-amino-2,3-naphthalene disulfonic acid, 7-amino group- 1,2-naphthalene disulfonic acid, 4-(aminomethyl)benzenesulfonic acid, 4-(aminomethyl)-2-methylbenzenesulfonic acid, 4-hydrothiobenzenesulfonic acid, 4-methyl Thiobenzenesulfonic acid.

[化合物(d-7)][compound (d-7)]

化合物(d-7)係具有羧基及雜環基，且氫原子與羧基除外之總原子數為3~20之化合物或其鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點而言，較佳為具有羧基，且氫原子與羧基除外之總原子數為3~20(較佳為5~15)之單環式雜環化合物或其鹽。The compound (d-7) is a compound having a carboxyl group and a heterocyclic group and having a total atomic number of 3 to 20 excluding a hydrogen atom and a carboxyl group, or a salt thereof, and further suppressing the generation of agglomerated impurities and lowering the contrast ratio. A monocyclic heterocyclic compound having a carboxyl group and having a total atomic number of 3 to 20 (preferably 5 to 15) excluding a hydrogen atom and a carboxyl group is preferred, or a salt thereof.

作為化合物(d-7)，可例舉如2-呋喃羧酸、3-呋喃羧酸、四氫-2-呋喃羧酸、四氫-3-呋喃羧酸、噻吩-2-羧酸、噻吩-3-羧酸、四氫噻吩-2-羧酸、四氫噻吩-3-羧酸、菸鹼酸、異菸鹼酸、下述化合物。The compound (d-7) may, for example, be 2-furancarboxylic acid, 3-furancarboxylic acid, tetrahydro-2-furancarboxylic acid, tetrahydro-3-furancarboxylic acid, thiophene-2-carboxylic acid or thiophene. 3-carboxylic acid, tetrahydrothiophene-2-carboxylic acid, tetrahydrothiophene-3-carboxylic acid, nicotinic acid, isonicotinic acid, the following compounds.

[化合物(d-8)][compound (d-8)]

化合物(d-8)係具有磺酸基及雜環基，且氫原子與磺酸基除外之總原子數為3~20之化合物或其鹽，而由進一步抑制凝集雜質產生及對比比率降低之觀點而言，較佳為具有磺酸基，且氫原子與磺酸基除外之總原子數為3~20(較佳為5~15)之單環式雜環化合物或其鹽。The compound (d-8) is a compound having a sulfonic acid group and a heterocyclic group and having a total atomic number of 3 to 20 excluding a hydrogen atom and a sulfonic acid group, or a salt thereof, and further suppresses generation of agglomerated impurities and lowers a contrast ratio. In view of the above, a monocyclic heterocyclic compound having a sulfonic acid group and having a total atomic number of 3 to 20 (preferably 5 to 15) excluding a hydrogen atom and a sulfonic acid group is preferred.

作為化合物(d-8)，可例舉如2-呋喃磺酸、3-呋喃磺酸、四氫-2-呋喃磺酸、四氫-3-呋喃磺酸、噻吩-2-磺酸、噻吩-3-磺酸、四氫噻吩-2-磺酸、四氫噻吩-3-磺酸、吡啶-3-磺酸、吡啶-4-磺酸、下述化合物。The compound (d-8) may, for example, be 2-furansulfonic acid, 3-furansulfonic acid, tetrahydro-2-furansulfonic acid, tetrahydro-3-furansulfonic acid, thiophene-2-sulfonic acid or thiophene. 3-sulfonic acid, tetrahydrothiophene-2-sulfonic acid, tetrahydrothiophene-3-sulfonic acid, pyridine-3-sulfonic acid, pyridine-4-sulfonic acid, the following compounds.

本發明中，(D)特定化合物可單獨或2種以上混合使用。In the present invention, the (D) specific compounds may be used singly or in combination of two or more kinds.

本發明中，(D)特定化合物的含量相對(A)著色劑100質量，較佳為0.1~30質量份，特佳為1~10質量份。此時，(D)特定化合物的含量若過少，會有無法獲得所要之效果之虞，另一方面若過多，則有形成之著色層在鹼性顯影時容易由基板脫落之傾向。In the present invention, the content of the specific compound (D) is preferably 0.1 to 30 parts by mass, particularly preferably 1 to 10 parts by mass, per 100 parts by mass of the colorant (A). In this case, if the content of the specific compound (D) is too small, the desired effect may not be obtained. On the other hand, if the content is too large, the colored layer formed tends to fall off from the substrate during alkaline development.

-(E)分散劑-- (E) Dispersant -

本發明中使用顏料作為著色劑時，可視需求使用(E)分散劑。作為(E)分散劑可使用陽離子系、陰離子系、非離子系等的適當分散劑，惟以含有胺價(單位mgKOH/g，下同)為5以上之分散劑(以下有稱為「特定分散劑」)為佳。此因茲認為使(D)特定化合物中的羧基、磺酸基等與特定分散劑互相作用，可提高著色組成物的保存穩定性。於此，胺價係表示中和分散劑固體含量1g所需之酸與當量之KOH的mg數。When a pigment is used as the colorant in the present invention, (E) a dispersant may be used as needed. As the (E) dispersing agent, a suitable dispersing agent such as a cationic type, an anionic type, or a nonionic type may be used, but a dispersing agent containing an amine valence (unit: mgKOH/g, the same applies hereinafter) of 5 or more (hereinafter referred to as "specific" Dispersant") is preferred. This is considered to improve the storage stability of the coloring composition by allowing a carboxyl group, a sulfonic acid group or the like in the specific compound (D) to interact with a specific dispersing agent. Here, the amine value means the number of mg of the acid and the equivalent amount of KOH required to neutralize the solid content of the dispersant by 1 g.

特定分散劑之胺價在使微粒化金屬錯合物顏料穩定分散之意義上，較佳為10mgKOH/g以上，特佳為70mg KOH/g以上。另一方面，特定分散劑之胺價在確保著色組成物之鹼性顯影性之意義上，則較佳為200mgKOH/g以下，特佳為150mgKOH/g以下。The amine valence of the specific dispersant is preferably 10 mgKOH/g or more, and particularly preferably 70 mgKOH/g or more in the sense of stably dispersing the microparticulate metal complex pigment. On the other hand, the amine valence of the specific dispersing agent is preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less in the sense of ensuring the alkali developability of the colored composition.

特定分散劑更佳為含有具有表現胺價之鹼性基團的聚合物鏈、與不具有鹼性基團之聚合物鏈的共聚物。作為所述特定分散劑，可例舉如嵌段共聚物型分散劑、接枝共聚物型分散劑等。作為嵌段共聚物型分散劑，較佳為由嵌段A與嵌段B構成的AB嵌段共聚物或BAB嵌段共聚物，該嵌段A係具備來自(二烷基)胺基烷基(甲基)丙烯酸酯等具有鹼性基團之(甲基)丙烯酸酯的重複單位，該嵌段B則具備來自具有烷基、芳基、芳烷基、聚己內酯構造、聚醚構造等之(甲基)丙烯酸酯的重複單位。且，作為接枝共聚物型分散劑較佳為以聚(伸烷基醯亞胺)、聚(烯丙基胺)等為聚合物主鏈，且由所述聚合物主鏈的一或多處分支有聚己內酯鏈、聚醚鏈等的接枝共聚物。The specific dispersant is more preferably a copolymer containing a polymer chain having a basic group exhibiting an amine value and a polymer chain having no basic group. The specific dispersant may, for example, be a block copolymer type dispersant or a graft copolymer type dispersant. As the block copolymer type dispersant, an AB block copolymer or a BAB block copolymer composed of a block A and a block B having a (dialkyl)aminoalkyl group is preferable. a repeating unit of a (meth) acrylate having a basic group such as (meth) acrylate, the block B having a structure derived from an alkyl group, an aryl group, an aralkyl group, a polycaprolactone, or a polyether structure The repeating unit of the (meth) acrylate. Further, as the graft copolymer type dispersing agent, poly(alkyleneimine), poly(allylamine) or the like is preferably used as a polymer main chain, and one or more of the polymer main chain is used. A graft copolymer of a polycaprolactone chain, a polyether chain or the like is branched at the branch.

此種嵌段共聚物型或接枝共聚物型特定分散劑可於市面上購得，可例舉如Disperbyk-2000(不揮發成分=40%，胺價=4mgKOH/g，BYK公司製)、Disperbyk-2001(不揮發成分=46%，胺價=19mgKOH/g，BYK公司製)、BYK-LPN 6919(不揮發成分=60%，胺價=72mgKOH/g，BYK公司製)、BYK-LPN21116(不揮發成分=40%，胺價=29mgKOH/g，BYK公司製)等。Such a block copolymer type or graft copolymer type specific dispersant is commercially available, and may, for example, be Disperbyk-2000 (nonvolatile content = 40%, amine price = 4 mgKOH/g, manufactured by BYK), Disperbyk-2001 (nonvolatile content = 46%, amine price = 19 mg KOH / g, manufactured by BYK), BYK-LPN 6919 (nonvolatile content = 60%, amine price = 72 mg KOH / g, manufactured by BYK), BYK-LPN 21116 (nonvolatile content = 40%, amine price = 29 mgKOH/g, manufactured by BYK Corporation).

特定分散劑可單獨或2種以上混合使用。The specific dispersing agents may be used singly or in combination of two or more kinds.

本發明中，可與分散劑共同使用分散助劑。作為分散助劑可例舉如顏料衍生物，具體可例舉銅酞菁素、吡咯并吡咯二酮、喹啉黃之磺酸衍生物等。In the present invention, a dispersing aid can be used together with the dispersing agent. The dispersing aid may, for example, be a pigment derivative, and specific examples thereof include copper phthalocyanine, pyrrolopyrroledione, and quinoline yellow sulfonic acid derivatives.

(E)分散劑的含量相對(A)著色劑100質量份，較佳為0.5~100質量份，更佳為1~70質量份，特佳為10~50質量份。此時，分散劑的含量若過多，則有損及鹼性顯影性之虞。The content of the (E) dispersant is preferably 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass, even more preferably 10 to 50 parts by mass, per 100 parts by mass of the coloring agent. At this time, if the content of the dispersant is too large, the alkali developability is impaired.

-(F)光聚合起始劑--(F) Photopolymerization initiator -

本發明著色性組成物中可使之含有(F)光聚合起始劑。由此，便可賦予著色組成物感放射線性。本發明所使用的(F)光聚合起始劑為一化合物，其可透過可見光線、紫外線、遠紫外線、電子線、X線等放射線的曝光而產生可起始上述(C)交聯劑之聚合的活性物種。The coloring composition of the present invention may contain (F) a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation linearity. The (F) photopolymerization initiator used in the present invention is a compound which can be exposed to radiation of visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays or the like to generate the above-mentioned (C) crosslinking agent. Aggregated active species.

作為此種光聚合起始劑，可例舉如噻噸酮系化合物、苯乙酮系化合物、雙咪唑系化合物、三系化合物、O-醯肟系化合物、鎓鹽系化合物、安息香系化合物、二苯甲酮系化合物、α-二酮系化合物、多核醌系化合物、二偶氮系化合物、醯亞胺磺酸鹽系化合物、鎓鹽系化合物等。The photopolymerization initiator may, for example, be a thioxanthone compound, an acetophenone compound, a bisimidazole compound or the like. Compound, O-antimony compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfhydrazine sulfonate A compound, a phosphonium salt compound, or the like.

本發明中，光聚合起始劑可單獨或2種以上混合使用。作為光聚合起始劑，較佳為選自噻噸酮系化合物、苯乙酮系化合物、雙咪唑系化合物、三系化合物、O-醯肟系化合物之群組的至少1種。In the present invention, the photopolymerization initiators may be used singly or in combination of two or more kinds. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a group of a compound and an O-lanthanoid compound.

本發明之較佳光聚合起始劑當中，作為噻噸酮系化合物之具體實例，可例舉噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthiophene. Tons of ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diiso Propyl thioxanthone and the like.

又作為上述苯乙酮系化合物之具體實例，可例舉2-甲基-1-[4-(甲硫基)苯基]-2-福啉丙烷-1-酮、2-苯甲基-2-二甲胺基-1-(4-福啉苯基)丁烷-1-酮、2-(4-甲基苯甲基)-2-(二甲胺基)-1-(4-福啉苯基)丁烷-1-酮等。Further, as a specific example of the above acetophenone-based compound, 2-methyl-1-[4-(methylthio)phenyl]-2- Phenanthroline propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenanthroline phenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenanthroline phenyl) butan-1-one and the like.

再作為上述雙咪唑系化合物之具體實例，可例舉2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-雙咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-雙咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-雙咪唑等。Further, as a specific example of the above bisimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4, 6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole and the like.

此外，使用雙咪唑系化合物作為光聚合起始劑時可併用氫供體，如此，由可改良感度之觀點而言係較佳。此處所謂「氫供體」係指可對經曝光而由雙咪唑系化合物產生之自由基提供氫原子之化合物。作為氫供體可例舉如2-氫硫基苯并噻唑、2-氫硫基苯并唑等硫醇系氫供體、4,4’-雙(二甲胺基)二苯甲酮、4,4’-雙(二乙胺基)二苯甲酮等胺系氫供體。本發明中，氫供體可單獨或2種以上混合使用，惟組合使用1種以上硫醇系氫供體與1種以上胺系氫供體時，由可進一步改良感度之觀點而言係較佳。Further, when a diimidazole-based compound is used as a photopolymerization initiator, a hydrogen donor can be used in combination, and therefore, it is preferable from the viewpoint of improving sensitivity. Here, the "hydrogen donor" means a compound which can supply a hydrogen atom to a radical generated by a bisimidazole compound upon exposure. As the hydrogen donor, for example, 2-hydrothiobenzothiazole or 2-hydrothiobenzophenone can be exemplified. An amine-based hydrogen donor such as a thiol-based hydrogen donor such as azole or 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, and when one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogen donors are used in combination, it is possible to further improve the sensitivity. good.

再者，作為上述三系化合物之具體實例，可例舉2,4,6-三(三氯甲基)-s-三、2-甲基-4,6-雙(三氯甲基)-s-三、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(4-二乙胺基-2-甲苯基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三等具有鹵代甲基之三系化合物。Again, as the above three Specific examples of the compound can be exemplified by 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halogenated methyl groups a compound.

又作為O-醯肟系化合物之具體實例，可例舉1,2-辛二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)、乙酮,1-[9-乙基-6-(2-甲基-4-四氫呋喃甲氧基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)、乙酮,1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二草烷基)甲氧基苯甲醯基}-9H-咔唑-3-基-],1-(O-乙醯肟)等。Further, as a specific example of the O-lanthanoid compound, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzamide), and B can be exemplified. Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[ 9-Ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1 -[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxalyl)methoxybenzylidene}-9H-indazole-3 -yl-], 1-(O-acetamidine) and the like.

本發明中，當使用苯乙酮系化合物等雙咪唑系化合物以外之光聚合起始劑時，可併用敏化劑。作為此種敏化劑，可例舉如4,4’-雙(二甲胺基)二苯甲酮、4,4’-雙(二乙胺基)二苯甲酮、4-二乙胺基苯乙酮、4-二甲胺基苯丙酮、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙胺基亞苄基)環己酮、7-二乙胺基-3-(4-二乙胺基苯甲醯基)香豆素、4-(二乙胺基)查耳酮等。In the present invention, when a photopolymerization initiator other than a bisimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylamine can be exemplified. Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

本發明中，光聚合起始劑的含量相對(C)交聯劑100質量份，較佳為0.01~120質量份，特佳為1~100質量份。此時，光聚合起始劑的含量若過少，會有曝光所致之硬化不完全之虞，另一方面若過多，則有形成之著色層在顯影時容易由基板脫落之傾向。In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing due to exposure may be incomplete. On the other hand, if the amount is too large, the formed color layer tends to fall off from the substrate during development.

-(G)溶劑--(G) solvent -

本發明著色組成物係含有上述(A)~(D)成分、及任意添加的其他成分，但通常係摻混溶劑而調製為液狀組成物。The colored composition of the present invention contains the above components (A) to (D) and other components added arbitrarily, but is usually prepared by mixing a solvent to prepare a liquid composition.

作為上述溶劑只要可分散或溶解構成著色組成物的(A)~(D)成分或其他成分、不與此等成分並具有適度的揮發性，則可適當選擇使用。The solvent can be appropriately selected and used as long as it can disperse or dissolve the components (A) to (D) constituting the colored composition or other components, and does not have moderate volatility with these components.

作為此種溶劑可例舉如乙二醇單甲醚、乙二醇單***、乙二醇單正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單***等之(聚)伸烷基二醇單烷基醚類；乳酸甲酯、乳酸乙酯等之乳酸烷基酯類；甲醇、乙醇、丙醇、丁醇、異丙醇、異丁醇、三級丁醇、辛醇、2-乙基己醇、環己醇等之(環)烷醇類；二丙酮醇等之酮醇類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單正丙醚乙酸酯、乙二醇單正丁醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單正丙醚乙酸酯、二乙二醇單正丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等之(聚)伸烷基二醇單烷基醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基***、二乙二醇二***、四氫呋喃等之其他醚類；甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類；丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等之二乙酸酯類；3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯等之烷氧基羧酸酯類；乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙酸正丁酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、乙基乙二醇酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-羥基-2-甲基丙酸乙酯、2-羥基-3-甲基丁酸甲酯、2-氧代丁酸乙酯等之其他酯類；甲苯、二甲苯等之芳香族烴類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮等之醯胺或內醯胺類等。The solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether or diethylene glycol alone. Ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alcohol monoalkyl ethers; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2- (cyclo)alkanols such as ethylhexanol and cyclohexanol; ketols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol single positive Propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, two Glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate (poly)alkyl diol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone a ketone such as cyclohexanone, 2-heptanone or 3-heptanone; propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate or the like Diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Alkoxycarboxylates such as esters, 3-methyl-3-methoxybutylpropionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate , n-amyl formate, isoamyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl N-butyl ester, ethyl glycol ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, 2 Other esters such as methyl hydroxy-3-methylbutanoate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N, A decylamine such as N-dimethylacetamide or N-methylpyrrolidone or an indoleamine.

此等溶劑中，由溶解性、顏料分散性、塗布性等觀點而言，係以丙二醇單甲醚、丙二醇單***、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、3-甲氧基丁基乙酸酯、二乙二醇二甲醚、二乙二醇甲基***、環己酮、2-庚酮、3-庚酮、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯、乳酸乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯等為佳。Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are used from the viewpoints of solubility, pigment dispersibility, and coating properties. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3 - Butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyl Ethyl propionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyrate B Ester, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc. are preferred.

本發明中溶劑可單獨或混合兩種以上使用。In the present invention, the solvent may be used singly or in combination of two or more.

溶劑的含量並未特別限定，但由所得之著色性組成物的塗布性、穩定性等觀點而言，除該著色性組成物的溶劑以外的各成分的總濃度較佳為5~50質量%的量，特佳為10~40質量%的量。The content of the solvent is not particularly limited, but the total concentration of each component other than the solvent of the coloring composition is preferably from 5 to 50% by mass from the viewpoints of coatability and stability of the coloring composition obtained. The amount is particularly preferably 10 to 40% by mass.

-添加劑--additive-

本發明著色組成物可視需求含有各種添加劑。The colored composition of the present invention may contain various additives as needed.

作為添加劑，可例舉如玻璃、氧化鋁等之填充劑；聚乙烯醇、聚(氟烷基丙烯酸酯)類等高分子化合物；氟系界面活性劑、矽系界面活性劑等之界面活性劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷等之密著促進劑；2,2-硫基雙(4-甲基-6-三級丁基酚)、2,6-二-三級丁基酚等之抗氧化劑；2-(3-三級丁基-5-甲基-2-羥苯基)-5-氯苯并***、烷氧基二苯甲酮類等之紫外線吸收劑；聚丙烯酸鈉等之抗凝集劑；丙二酸、己二酸、伊康酸、檸康酸、富馬酸、中康酸、2-胺基乙醇、3-胺基-1-丙醇、5-胺基-1-戊醇、3-胺基-1,2-丙二醇、2-胺基-1,3-丙二醇、4-胺基-1,2-丁二醇等之殘渣改善劑等；單[2-(甲基)丙烯醯氧基乙基]琥珀酸酯、單[2-(甲基)丙烯醯氧基乙基]鄰苯二甲酸酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等之顯影性改善劑；日本特開2008-242078號公報等所揭示之具有反應性官能基之矽氧烷寡聚物等。The additive may, for example, be a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or a lanthanoid surfactant; Vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , a adhesion promoter such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane; 2,2-thio An antioxidant such as bis(4-methyl-6-tertiary butyl phenol) or 2,6-di-tertiary butyl phenol; 2-(3-tert-butyl-5-methyl-2-hydroxyl) Ultraviolet absorbers such as phenyl)-5-chlorobenzotriazole and alkoxybenzophenone; anticoagulation of sodium polyacrylate and the like Malonate, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-lan a residue improving agent such as an alcohol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc.; single [2-(methyl) ) propylene methoxyethyl] succinate, mono [2-(methyl) propylene methoxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate, etc. A developer improving agent; a siloxane oligomer having a reactive functional group disclosed in JP-A-2008-242078 or the like.

本發明著色組成物可由適當方法來調製，作為其調製方法，例如可將(A)~(D)成分與(G)溶劑、任意添加的其他成分共同混合來調製。當使用顏料作為(A)著色劑時，較佳為將顏料在(G)溶劑中、(E)分散劑的存在下，視情況與(B)成分的一部分，利用例如珠磨機、輥磨機等粉碎並混合、分散而製成顏料分散液，次之對該顏料分散液添加(B)~(C)成分、及視需求而進一步追加之溶劑、其他成分並予以混合來調製之方法。此時，(D)特定化合物可於調製顏料分散液時添加、或在調製顏料分散液後，混合顏料分散液與剩餘成分時添加。The colored composition of the present invention can be prepared by an appropriate method, and as a preparation method, for example, (A) to (D) components and (G) a solvent and optionally added other components may be mixed and prepared. When a pigment is used as the (A) colorant, it is preferred to use the pigment in the presence of (G) solvent, (E) a dispersant, and optionally, a part of the component (B), for example, using a bead mill or a roll mill. A method of preparing a pigment dispersion liquid by pulverizing, mixing, and dispersing, and then adding the components (B) to (C), and further adding a solvent and other components as needed to the pigment dispersion liquid, and preparing the same. At this time, the (D) specific compound may be added at the time of preparing the pigment dispersion liquid or after mixing the pigment dispersion liquid and the remaining components after preparing the pigment dispersion liquid.

[彩色濾光片及其製造方法][Color filter and method of manufacturing the same]

本發明彩色濾光片係具備使用本發明著色組成物所形成之著色層。The color filter of the present invention is provided with a coloring layer formed using the colored composition of the present invention.

作為製造彩色濾光片之方法第一可例舉以下方法。首先，於基板表面上，視需求以劃分形成有畫素之部分的方式形成遮光層(黑色矩陣)。次之，於該基板上塗布含有例如紅色著色劑的本發明感放射線性組成物之液狀組成物後，進行預烘烤使溶劑蒸發而形成塗膜。其次，對該塗膜隔著光罩進行曝光後，使用鹼性顯影液進行顯影，再溶解除去塗膜的未曝光部分。其後，進行後烘烤，由此便形成以既定排列配置有紅色畫素圖案的畫素陣列。As a method of manufacturing a color filter, the following method can be exemplified. First, on the surface of the substrate, a light shielding layer (black matrix) is formed in such a manner as to divide the portion in which the pixels are formed. Next, a liquid composition of the radiation sensitive composition of the present invention containing, for example, a red coloring agent is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, after the coating film was exposed through a photomask, development was carried out using an alkaline developing solution, and the unexposed portion of the coating film was dissolved and removed. Thereafter, post-baking is performed, whereby a pixel array in which a red pixel pattern is arranged in a predetermined arrangement is formed.

次之，使用綠色或藍色的各著色性組成物，與上述同樣地進行各著色感放射線性組成物的塗布、預烘烤、曝光、顯影及後烘烤，而在同一基板上依序形成綠色的畫素陣列及藍色的畫素陣列。由此，便製得紅色、綠色及藍色之三原色的畫素陣列配置於基板上的彩色濾光片。惟，本發明中形成各色畫素的順序並未限於上述者。Next, each of the green or blue coloring compositions is applied, and the coating, prebaking, exposing, developing, and post-baking of each coloring radiation composition are performed in the same manner as described above, and sequentially formed on the same substrate. Green pixel array and blue pixel array. As a result, a pixel array of three primary colors of red, green, and blue is disposed on the color filter on the substrate. However, the order in which the respective color pixels are formed in the present invention is not limited to the above.

又，黑色矩陣可藉由將以濺鍍或蒸鍍而成膜的鉻等金屬薄膜，利用光微影法製成所要的圖案來形成，惟亦可使用含有黑色著色劑的著色感放射線性組成物，以與形成上述畫素時同樣的方式來形成。本發明著色組成物亦可適用於所述黑色矩陣的形成。Further, the black matrix can be formed by forming a desired pattern by a photolithography method using a metal thin film such as chromium which is formed by sputtering or vapor deposition, but it is also possible to use a coloring linear composition containing a black coloring agent. The object is formed in the same manner as when the above-described pixels are formed. The colored composition of the present invention can also be applied to the formation of the black matrix.

作為形成彩色濾光片之際所使用的基板可例舉如玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。The substrate used for forming the color filter may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide or polyimine.

又，此等基板上亦可視需求預先實施採用矽烷偶合劑等的藥品處理、電漿處理、離子鍍敷、濺鍍、氣相反應法、真空蒸鍍等適當的前處理。Further, such pretreatments such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum vapor deposition using a decane coupling agent or the like may be performed in advance on such substrates.

將著色性組成物塗布於基板之際可採用噴霧法、滾筒塗布法、旋轉塗布法(旋塗法)、狹縫模具塗布法、桿塗布法等適當的塗布法，惟特佳採用旋轉塗布法、狹縫模具塗布法。When the coloring composition is applied to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a rod coating method may be employed, but a spin coating method is particularly preferred. , slit die coating method.

預烘烤通常係組合減壓乾燥與加熱乾燥來進行。減壓乾燥通常係進行至達到50~200Pa為止。又，加熱乾燥之條件通常為70~110℃下1~10分鐘左右。Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Further, the conditions for heating and drying are usually about 1 to 10 minutes at 70 to 110 °C.

塗布厚度為乾燥後的膜厚，其通常為0.6~8.0μm，較佳為1.2~5.0μm。The coating thickness is a film thickness after drying, and it is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm.

作為形成畫素及/或黑色矩陣之際所使用之放射線的光源可例舉如氙燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈等之燈光源或氬離子雷射、YAG雷射、XeCl準分子雷射、氮氣雷射等之雷射光源等，而較佳為波長處於190~450nm之範圍的放射線。The light source used for forming the pixels and/or the black matrix may be, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or the like. A light source or a laser source such as an argon ion laser, a YAG laser, a XeCl excimer laser, a nitrogen laser, or the like, and preferably a radiation having a wavelength in the range of 190 to 450 nm.

放射線的曝光量一般而言較佳為10~10,000J/m2 。The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m 2 .

又，上述鹼性顯影液較佳為例如碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲銨、膽鹼、1,8-二雜氮雙環-[5.4.0]-7-十一烯、1,5-二雜氮雙環-[4.3.0]-5-壬烯等的水溶液。Further, the above alkaline developing solution is preferably, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- eleven. An aqueous solution of an alkene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

上述鹼性顯影液中亦可適量添加例如甲醇、乙醇等水溶性有機溶劑或界面活性劑等。此外，鹼性顯影後通常進行水洗。A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developing solution in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

作為顯影處理法可應用噴淋(shower)顯影法、噴霧顯影法、浸漬(dip)顯影法、浸置(paddle；液池法)顯影法等。顯影條件較佳為常溫下5~300秒。As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping (liquid pool method) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at normal temperature.

後烘烤之條件通常為120~280℃下10~60分鐘左右。The post-baking conditions are usually about 10 to 60 minutes at 120 to 280 °C.

如此形成之畫素的膜厚通常為0.5~5.0μm，較佳為1.0~3.0μm。The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

又，作為製造彩色濾光片的第二方法可採用日本特開平7-318723號公報、日本特開2000-310706號公報等所揭露之以噴墨方式來製得各色畫素的方法。該方法中，係首先於基板表面上形成同時兼具遮光功能的間壁(partition)。次之，在所形成的間壁內以噴墨裝置噴出含有例如紅色著色劑之本發明熱固性組成物之液狀組成物後，進行預烘烤使溶媒蒸發。次之，對該塗膜視需求進行曝光，隨後進行後烘烤使之硬化，便形成紅色的畫素圖案。Moreover, as a second method of producing a color filter, a method of producing each color pixel by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, a partition having a light-shielding function at the same time is first formed on the surface of the substrate. Next, a liquid composition containing the thermosetting composition of the present invention containing, for example, a red coloring agent is ejected by an inkjet device in the formed partition, and then prebaked to evaporate the solvent. Secondly, the coating film is exposed as needed, and then post-baked to harden to form a red pixel pattern.

次之，使用綠色或藍色的各著色熱固性組成物，與上述同樣地在同一基板上依序形成綠色的畫素圖案及藍色的畫素圖案。由此，便製得紅色、綠色及藍色之三原色的畫素圖案配置於基板上的彩色濾光片。惟，本發明中形成各色畫素的順序並未限於上述者。Next, using a green or blue colored thermosetting composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which the pixel patterns of the three primary colors of red, green, and blue are arranged on the substrate is obtained. However, the order in which the respective color pixels are formed in the present invention is not limited to the above.

此外，上述間壁不僅發揮遮光功能，還發揮不使噴出至劃分區域內的各色著色組成物混色用的功能，故相較於上述第一方法中所使用的黑色矩陣，其膜厚較厚。因此，間壁通常使用黑色感放射線性組成物而形成。Further, the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the coloring compositions discharged into the divided regions, so that the film thickness is thicker than that of the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

形成彩色濾光片之際所使用的基板或放射線的光源，及預烘烤、後烘烤的方法或條件係與上述第一方法相同。如此一來，由噴墨方式形成之畫素的膜厚便與間壁的高度為相同程度。The light source of the substrate or radiation used for forming the color filter, and the method or conditions for prebaking and postbaking are the same as those of the first method described above. As a result, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

於如此所得之畫素圖案上視需求形成保護膜後，再以濺鍍形成透明導電膜。形成透明導電膜後，可進一步形成間隔件而製成彩色濾光片。間隔件通常係使用感放射線性組成物而形成，惟亦可製成具有遮光性的間隔件(黑色間隔件)。此時係使用含有黑色著色劑的著色感放射線性組成物，惟本發明著色組成物亦可適用於所述黑色間隔件的形成。After forming a protective film on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be formed into a light-shielding spacer (black spacer). In this case, a color-sensitive radiation composition containing a black colorant is used, but the coloring composition of the present invention can also be applied to the formation of the black spacer.

如此所得之本發明彩色濾光片其輝度及色純度極高，因此極有用於彩色液晶顯示元件、彩色攝像管元件、色澤感應器、有機EL顯示元件、電子紙等。The color filter of the present invention thus obtained is extremely useful for color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like because of its extremely high luminance and color purity.

[顯示元件][display component]

本發明顯示元件係具備本發明彩色濾光片。作為顯示元件可例舉彩色液晶顯示元件、有機EL顯示元件、電子紙等。The display element of the present invention is provided with the color filter of the present invention. As the display element, a color liquid crystal display element, an organic EL display element, electronic paper, or the like can be exemplified.

具備本發明彩色濾光片的彩色液晶顯示元件可採用適當的構造。例如可採用將彩色濾光片形成於除配置有薄膜電晶體(TFT)之驅動用基板以外的基板上，且驅動用基板與形成有彩色濾光片的基板隔著液晶層對向的構造，更且亦可採用配置有薄膜電晶體(TFT)之驅動用基板的表面上形成有彩色濾光片的基板、與形成有ITO(摻有錫之氧化銦)電極的基板隔著液晶層對向的構造。後者的構造具有可格外提高開口率，並可獲得明亮、高精細的液晶顯示元件的優點。The color liquid crystal display element having the color filter of the present invention can be suitably constructed. For example, a color filter may be formed on a substrate other than the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may be opposed to each other via the liquid crystal layer. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be opposed to each other via a liquid crystal layer. Construction. The latter configuration has an advantage that the aperture ratio can be particularly increased, and a bright, high-definition liquid crystal display element can be obtained.

具備本發明彩色濾光片之彩色液晶顯示元件除冷陰極螢光管(CCFL：Cold Cathode Fluorescent Lamp)之外，還可具備以白色LED為光源之背光單元。作為白色LED，可例舉如將紅色LED、綠色LED與藍色LED組合、混色而獲得白色光之白色LED、將藍色LED、紅色LED與綠色螢光體組合、混色而獲得白色光之白色LED、將藍色LED、紅色發光螢光體與綠色發光螢光體組合、混色而獲得白色光之白色LED、經藍色LED與YAG系螢光體混色而獲得白色光之白色LED、將藍色LED、橙色發光螢光體與綠色發光螢光體組合、混色而獲得白色光之白色LED、將紫外線LED、紅色發光螢光體、綠色發光螢光體與藍色發光螢光體組合、混色而獲得白色光之白色LED等。A color liquid crystal display element having the color filter of the present invention may be provided with a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, a white LED in which a red LED, a green LED, and a blue LED are combined and mixed to obtain white light, a blue LED, a red LED, and a green phosphor are combined and mixed to obtain white light. LED, blue LED, red illuminating phosphor and green illuminating phosphor are combined, mixed to obtain white light white LED, blue LED and YAG fluorescent body mixed to obtain white light white LED, blue Combination of color LED, orange illuminating phosphor and green illuminating phosphor, color mixing to obtain white LED of white light, combination of ultraviolet LED, red illuminating phosphor, green illuminating phosphor and blue illuminating phosphor, color mixing And white LEDs such as white light are obtained.

具備本發明彩色濾光片的彩色液晶顯示元件可適用TN(Twisted Nematic)型、STN(Super Twisted Nematic)型、IPS(In-Planes Switching)型、VA(Vertical Alignment)型、OCB(Optically Compensated Birefringence)型等適當的液晶模式。The color liquid crystal display element having the color filter of the present invention can be applied to TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence). A suitable liquid crystal mode such as a type.

此外，具備本發明彩色濾光片的有機EL顯示元件可採用適當構造，可例舉如日本特開平11-307242號公報所揭露的構造。In addition, the organic EL display element having the color filter of the present invention can be suitably configured, and the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242 can be exemplified.

又，具備本發明彩色濾光片的電子紙可採用適當構造，可例舉如日本特開2007-41169號公報所揭露的構造。Moreover, the electronic paper provided with the color filter of the present invention can be suitably configured, and the structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be exemplified.

[實施例][Examples]

以下舉出實施例，對本發明的實施方式更具體地進行說明。惟，本發明並未限於下述實施例。Embodiments of the present invention will be described more specifically below by way of examples. However, the invention is not limited to the following examples.

<黏著劑樹脂之合成><Synthesis of Adhesive Resin>

合成例1Synthesis Example 1

對具備冷卻管與攪拌機之燒瓶加入丙二醇單甲醚乙酸酯100質量份並進行氮氣置換。加熱至80℃，於同一溫度下以1小時滴入丙二醇單甲醚乙酸酯100質量份、甲基丙烯酸20質量份、苯乙烯10質量份、甲基丙烯酸苯甲酯5質量份、甲基丙烯酸2-羥乙酯15質量份、甲基丙烯酸2-乙基己酯23質量份、N-苯基馬來醯亞胺12質量份、單[2-(甲基)丙烯酸乙基]琥珀酸酯15質量份及2,2'-偶氮雙(2,4-二甲基戊腈)6質量份之混合溶液，保持該溫度進行聚合2小時。其後，將反應溶液溫度升溫至100℃並進一步進行聚合1小時，即得黏著劑樹脂溶液(固體含量濃度=33質量%)。所得之黏著劑樹脂其Mw=12,200、Mn=6,500。以該黏著劑樹脂作為「黏著劑樹脂(B1)」。100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, mono [2-(meth)acrylic acid ethyl]succinic acid A mixed solution of 15 parts by mass of an ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C and further polymerization was carried out for 1 hour to obtain an adhesive resin solution (solid content concentration = 33% by mass). The obtained adhesive resin had Mw = 12,200 and Mn = 6,500. This adhesive resin was used as the "adhesive resin (B1)".

合成例2Synthesis Example 2

對具備冷卻管與攪拌機之燒瓶加入丙二醇單甲醚乙酸酯100質量份並進行氮氣置換。加熱至80℃，於同一溫度下以1小時滴入丙二醇單甲醚乙酸酯100質量份、甲基丙烯酸20質量份、苯乙烯10質量份、甲基丙烯酸苯甲酯5質量份、甲基丙烯酸2-羥乙酯15質量份、甲基丙烯酸2-乙基己酯38質量份、N-苯基馬來醯亞胺12質量份、及2,2'-偶氮雙(2,4-二甲基戊腈)6質量份之混合溶液，保持該溫度進行聚合2小時。其後，將反應溶液溫度升溫至100℃並進一步進行聚合1小時，即得黏著劑樹脂溶液(固體含量濃度=33質量%)。所得之黏著劑樹脂其Mw=11,000、Mn=6000。以該黏著劑樹脂作為「黏著劑樹脂(B2)」。100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. The mixture was heated to 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methyl group were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 38 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and 2,2'-azobis (2,4- A mixed solution of 6 parts by mass of dimethyl valeronitrile was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C and further polymerization was carried out for 1 hour to obtain an adhesive resin solution (solid content concentration = 33% by mass). The obtained adhesive resin had Mw = 11,000 and Mn = 6000. This adhesive resin is used as the "adhesive resin (B2)".

<顏料分散液之調製><Preparation of Pigment Dispersion>

調製例1Modulation example 1

使用作為(A)著色劑之C.I.顏料綠58/C.I.顏料黃150=80/20(質量比)混合物15質量份、作為(E)分散劑之BYK-LPN21116(BYK公司製)12質量份(固體含量濃度=40質量%)、作為(B)黏著劑樹脂之黏著劑樹脂(B1)溶液16質量份、作為(G)溶劑之丙二醇單甲醚乙酸酯57質量份，以珠磨機予以混合、分散12小時來調製顏料分散液(A-1)。此外，換算成固體含量之分散劑BYK-LPN21116的胺價為72.5mgKOH/g。15 parts by mass of a mixture of CI pigment green 58/CI pigment yellow 150=80/20 (mass ratio) as a coloring agent (A), and 12 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersing agent (E) (solid) Content concentration = 40% by mass), 16 parts by mass of the adhesive resin (B1) solution of (B) adhesive resin, 57 parts by mass of propylene glycol monomethyl ether acetate as (G) solvent, and mixed by a bead mill The pigment dispersion (A-1) was prepared by dispersing for 12 hours. Further, the amine valence of the dispersant BYK-LPN21116 converted to a solid content was 72.5 mgKOH/g.

調製例2Modulation example 2

使用作為(A)著色劑之C.I.顏料綠58 15質量份、作為(E)分散劑之BYK-LPN21116(BYK公司製)12質量份、作為(B)黏著劑樹脂之黏著劑樹脂(B1)溶液16質量份、作為(D)特定化合物之2-氫硫基安息香酸1質量份、作為(G)溶劑之丙二醇單甲醚乙酸酯56質量份，以珠磨機予以混合、分散12小時來調製顏料分散液(A-2)。15 parts by mass of CI Pigment Green 58 as a coloring agent (A), 12 parts by mass of BYK-LPN 21116 (manufactured by BYK Co., Ltd.) as (E) dispersing agent, and an adhesive resin (B1) solution as (B) adhesive resin 16 parts by mass, 1 part by mass of 2-hydrothio benzoic acid as the (D) specific compound, and 56 parts by mass of propylene glycol monomethyl ether acetate as the solvent (G), mixed and dispersed in a bead mill for 12 hours. The pigment dispersion (A-2) was prepared.

調製例3Modulation example 3

使用作為(A)著色劑之C.I.顏料綠58/C.I.顏料黃150=60/40(質量比)混合物15質量份、作為(E)分散劑之BYK-LPN21116(BYK公司製)12質量份、作為(B)黏著劑樹脂之黏著劑樹脂(B1)溶液16質量份、作為(D)特定化合物之2-氫硫基安息香酸1質量份、作為(G)溶劑之丙二醇單甲醚乙酸酯56質量份，以珠磨機予以混合、分散12小時來調製顏料分散液(A-3)。Using 15 parts by mass of a mixture of CI Pigment Green 58/CI Pigment Yellow 150=60/40 (mass ratio) as the (A) colorant, and 12 parts by mass of BYK-LPN21116 (manufactured by BYK Co., Ltd.) as the (E) dispersant, (B) 16 parts by mass of the adhesive resin (B1) solution of the adhesive resin, 1 part by mass of 2-hydrothio benzoic acid as the (D) specific compound, and propylene glycol monomethyl ether acetate 56 as the solvent (G) The mass fraction was mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-3).

<著色組成物之調製及評定><Modulation and evaluation of coloring composition>

實施例1Example 1

[著色組成物之調製][Modulation of coloring composition]

將顏料分散液(A-1)200質量份、作為(B)黏著劑樹脂之黏著劑樹脂(B2)溶液45質量份、作為(C)交聯劑之東亞合成股份有限公司製M-402(二新戊四醇六丙烯酸酯與二新戊四醇五丙烯酸酯之混合物)15質量份、作為(D)特定化合物之2-氫硫基安息香酸1質量份、作為(F)光聚合起始劑之2-苯甲基-2-二甲胺基-1-(4-福啉苯基)丁烷-1-酮20質量份、作為氟系界面活性劑之DIC股份有限公司製Megafac F-5541質量份、作為(G)溶劑之丙二醇單甲醚乙酸酯混合成固體含量濃度為20質量%，以調製液狀組成物(S-1)。200 parts by mass of the pigment dispersion liquid (A-1), 45 parts by mass of the adhesive resin (B2) solution of the (B) adhesive resin, and M-402 (manufactured by Toagosei Co., Ltd. as a (C) crosslinking agent ( 15 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, 1 part by mass of 2-hydrothio benzoic acid as a specific compound of (D), as (F) photopolymerization initiation 2-Benzyl-2-dimethylamino-1-(4- 20 parts by mass of porphyrin phenyl)butan-1-one, Megafac F-5541 parts by mass of DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate as a solvent (G) The content concentration was 20% by mass to prepare a liquid composition (S-1).

[黏度之評定][Assessment of viscosity]

利用E型黏度計(東京計器製)來量測調製後即刻之液狀組成物(S-1)的黏度。此外，將所得之液狀組成物(S-1)填充於遮光玻璃容器中，以密閉狀態於40℃下靜置7日後，再次利用E型黏度計(東京計器製)量測黏度。其後，算出保存7日後之黏度相對調製後即刻之黏度的增加率，當增加率小於5%時評為「A」，5%以上小於10%時評為「B」，10%以上時則評為「C」。評定結果係示於表1。The viscosity of the liquid composition (S-1) immediately after the modulation was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). In addition, the obtained liquid composition (S-1) was filled in a light-shielding glass container, and it was allowed to stand in a sealed state at 40 ° C for 7 days, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Thereafter, the increase rate of the viscosity after the storage for 7 days is calculated as the viscosity immediately after the preparation, and is evaluated as "A" when the increase rate is less than 5%, "B" when the increase rate is less than 10%, and "B" when the increase rate is less than 10%. "C". The results of the evaluation are shown in Table 1.

[雜質之評定][Evaluation of impurities]

將保存於40℃下7日後的液狀組成物(S-1)利用旋轉塗布機塗布於玻璃基板上後，以90℃之加熱板進行預烘烤1分鐘即形成膜厚2.5μm之塗膜。次之，將基板冷卻至室溫後，利用高壓水銀燈，在未隔著光罩下對塗膜以600J/m2 之曝光量曝光含365nm、405nm及436nm之各波長的放射線。對所得之綠色硬化膜以偏光顯微鏡(倍率200倍)進行觀察，當一視野中可確認之雜質為零時判定為A，一視野中可確認之雜質為1~9個時判定為B，而一視野中可確認之雜質為10個以上時則判定為C。評定結果係示於表1。The liquid composition (S-1) stored at 40 ° C for 7 days was applied onto a glass substrate by a spin coater, and then prebaked for 1 minute on a hot plate at 90 ° C to form a coating film having a film thickness of 2.5 μm. . Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the coating film at a JJ/m 2 exposure without using a high-pressure mercury lamp. The obtained green cured film was observed by a polarizing microscope (magnification: 200 times), and it was judged as A when the impurity which can be confirmed in one field of view was zero, and was judged as B when the impurity which can be confirmed in one field of view was 1 to 9. When 10 or more impurities can be confirmed in one field of view, it is judged as C. The results of the evaluation are shown in Table 1.

[對比之評定][comparison evaluation]

將調製後即刻之液狀組成物(S-1)利用旋轉塗布機塗布於玻璃基板上後，以90℃之加熱板進行預烘烤1分鐘即形成膜厚2.5μm之塗膜。次之，將基板冷卻至室溫後，利用高壓水銀燈，在未隔著光罩下對塗膜以600J/m2 之曝光量曝光含365nm、405nm及436nm之各波長的放射線。其後，對塗膜以顯影壓力1kgf/cm2 (噴嘴直徑1mm)排出包含23℃、0.04質量%氫氧化鉀水溶液之顯影液，藉以進行噴淋顯影。其後，以超純水清洗該基板並加以風乾後，進一步在230℃之潔淨烘箱內進行後烘烤20分鐘，即形成綠色硬化膜。The liquid composition (S-1) immediately after preparation was applied onto a glass substrate by a spin coater, and then prebaked for 1 minute on a hot plate at 90 ° C to form a coating film having a film thickness of 2.5 μm. Followed, after the substrate was cooled to room temperature, high pressure mercury lamp at 365nm, 405nm radiation and the coating film to 600J / m 2 exposure amount of the exposure wavelength is 436nm containing each of the mask is not interposed therebetween. Thereafter, a developing solution containing a 23 ° C, 0.04% by mass aqueous potassium hydroxide solution was discharged to the coating film at a developing pressure of 1 kgf/cm 2 (nozzle diameter: 1 mm) to carry out shower development. Thereafter, the substrate was washed with ultrapure water and air-dried, and further post-baked in a clean oven at 230 ° C for 20 minutes to form a green cured film.

以2片偏向板夾持形成有硬化膜之基板，由背面側照射螢光燈(波長範圍380~780nm)同時旋轉前側之偏向板，利用輝度計LS-100(Minolta(股)製)量測所穿透之光強度的最大值與最小值。爾後，以最大值除以最小值所得之值作為對比。評定結果係示於表1。The substrate on which the cured film is formed is sandwiched between two deflecting plates, and the fluorescent lamp (wavelength range 380 to 780 nm) is irradiated from the back side while rotating the deflecting plate on the front side, and measured by a luminance meter LS-100 (manufactured by Minolta Co., Ltd.) The maximum and minimum values of the transmitted light intensity. After that, the value obtained by dividing the maximum value by the minimum value is used as a comparison. The results of the evaluation are shown in Table 1.

對40℃下保存7日後之液狀組成物(S-1)同樣進行對比的量測。評定結果係示於表1。The liquid composition (S-1) after 7 days of storage at 40 ° C was also subjected to comparative measurement. The results of the evaluation are shown in Table 1.

實施例2~8及比較例1~3Examples 2 to 8 and Comparative Examples 1 to 3

除將實施例1中顏料分散液的種類及(D)成分的種類改為如表1所示者以外，係以與實施例1同樣的方式來調製液狀組成物(S-2)~(S-8)及(S-10)~(S-12)。此外，在調製液狀組成物(S-5)及(S-6)時，作為溶劑係使用丙二醇單甲醚乙酸酯/丙二醇單甲醚=85/15(質量比)混合溶劑。又，實施例7及8中，(D)成分係於調製顏料分散液時添加，而未於調製著色組成物時添加。The liquid composition (S-2) was prepared in the same manner as in Example 1 except that the type of the pigment dispersion liquid and the type of the component (D) in the first embodiment were changed as shown in Table 1. S-8) and (S-10)~(S-12). Further, in the preparation of the liquid compositions (S-5) and (S-6), a solvent mixture of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether = 85/15 (mass ratio) was used as a solvent. Further, in Examples 7 and 8, the component (D) was added when the pigment dispersion liquid was prepared, and was not added when the coloring composition was prepared.

次之，除使用各個液狀組成物(S-2)~(S-8)或(S-10)~(S-12)來取代液狀組成物(S-1)以外，係以與實施例1同樣的方式進行評定。評定結果係示於表1。Secondly, in addition to using the liquid compositions (S-2) to (S-8) or (S-10) to (S-12) instead of the liquid composition (S-1), Example 1 was evaluated in the same manner. The results of the evaluation are shown in Table 1.

實施例9Example 9

將作為(A)著色劑之C.I.溶劑橙56(Cr錯合物)25質量份、作為(B)黏著劑樹脂之黏著劑樹脂(B2)溶液45質量份15質量份、作為(C)交聯劑之東亞合成股份有限公司製M-402(二新戊四醇六丙烯酸酯與二新戊四醇五丙烯酸酯之混合物)15質量份、作為(D)特定化合物之2-氫硫基安息香酸0.8質量份、作為(F)光聚合起始劑之2-苯甲基-2-二甲胺基-1-(4-福啉苯基)丁烷-1-酮20質量份、作為氟系界面活性劑之DIC股份有限公司製Megafac F-554 1質量份、作為(G)溶劑之乳酸乙酯混合成固體含量濃度為20質量%來調製液狀組成物(S-9)。25 parts by mass of CI Solvent Orange 56 (Cr complex) as the coloring agent (A), and 45 parts by mass of the adhesive resin (B2) solution of (B) the adhesive resin, as (C) cross-linking M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) prepared by East Asia Synthetic Co., Ltd., 15 parts by mass of 2-hydrothio benzoic acid as (D) specific compound 0.8 parts by mass of 2-benzyl-2-dimethylamino-1-(4-) as (F) photopolymerization initiator 20 parts by mass of porphyrin phenyl)butan-1-one, 1 part by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and a solid content concentration of ethyl lactate as a solvent (G) 20% by mass to prepare a liquid composition (S-9).

對40℃下保存7日後的液狀組成物(S-9)以與實施例1同樣的方式進行雜質之評定。評定結果係示於表1。The liquid composition (S-9) after storage for 7 days at 40 ° C was evaluated for impurities in the same manner as in Example 1. The results of the evaluation are shown in Table 1.

比較例4Comparative example 4

除使用鄰苯二甲酸單甲酯來取代實施例9中之2-氫硫基安息香酸以外，係以與實施例9同樣的方式來調製液狀組成物(S-13)。對40℃下保存7日後的液狀組成物(S-9)以與實施例1同樣的方式進行雜質之評定。評定結果係示於表1。The liquid composition (S-13) was prepared in the same manner as in Example 9 except that the monomethyl phthalate was used instead of the 2-hydrothio benzoic acid in Example 9. The liquid composition (S-9) after storage for 7 days at 40 ° C was evaluated for impurities in the same manner as in Example 1. The results of the evaluation are shown in Table 1.

表1中，各成分係如下述：In Table 1, the components are as follows:

D1：2-氫硫基安息香酸(d-5)D1: 2-Hetylthiobenzoic acid (d-5)

D2：11-氫硫基十一酸(d-1)D2: 11-Hexylthioundecanoic acid (d-1)

D3：4-氫硫基菸鹼酸(d-7)D3: 4-Hexylthionicotinic acid (d-7)

D4：10-羥基癸酸(d-1)D4: 10-hydroxydecanoic acid (d-1)

D5：吡啶-3-磺酸三丁基銨(d-8)D5: tributylammonium pyridine-3-sulfonate (d-8)

D6：下式所示之化合物之三丁基銨鹽(d-4)D6: a tributylammonium salt of the compound represented by the following formula (d-4)

Claims (6)

一種著色組成物，其特徵為含有(A)著色劑、(B)黏著劑樹脂、(C)交聯劑、及(D)選自包含下述(d-1)~(d-8)之群組的至少1種化合物，並含有錯合物作為(A)著色劑，(d-1)具有-SR2 基之脂肪族羧酸或其鹽；(d-2)具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之脂肪族磺酸或其鹽；(d-3)具有選自包含-OR1 基及-SR2 基之群組的至少1種之脂環式羧酸或其鹽；(d-4)具有選自包含-OR1 基、-SR2 基及-Q-NR3 R4 基之群組的至少1種之脂環式磺酸或其鹽；(d-5)由具有-SR2 基之基團與具有羧基之基團取代之芳香族烴或其鹽；(d-6)經選自包含具有-OR1 基之基團、具有-SR2 基之基團及具有-Q-NR3 R4 基之基團之群組的至少1種、與具有磺酸基之基團取代之芳香族烴或其鹽；(d-7)具有羧基及雜環基，且氫原子與羧基除外之總原子數為3~20之化合物或其鹽；(d-8)具有磺酸基及雜環基，且氫原子與磺酸基除外之總原子數為3~20之化合物或其鹽，[惟，R1 ~R4 彼此獨立表示氫原子或取代或未取代之1價烴基，Q表示單鍵或羰基]。A colored composition comprising (A) a colorant, (B) an adhesive resin, (C) a crosslinking agent, and (D) selected from the group consisting of (d-1) to (d-8) a group of at least one compound containing a complex as (A) a colorant, (d-1) an aliphatic carboxylic acid having a -SR 2 group or a salt thereof; (d-2) having a selected from -OR At least one aliphatic sulfonic acid or a salt thereof of the group of 1 group, -SR 2 group and -Q-NR 3 R 4 group; (d-3) having a group selected from the group consisting of -OR 1 group and -SR 2 group a group of at least one alicyclic carboxylic acid or a salt thereof; (d-4) having at least 1 selected from the group consisting of -OR 1 group, -SR 2 group, and -Q-NR 3 R 4 group An alicyclic sulfonic acid or a salt thereof; (d-5) an aromatic hydrocarbon substituted by a group having a -SR 2 group and a group having a carboxyl group or a salt thereof; (d-6) selected from the group consisting of At least one of a group of -OR 1 group, a group having -SR 2 group, and a group having a -Q-NR 3 R 4 group, and an aromatic hydrocarbon substituted with a group having a sulfonic acid group Or a salt thereof; (d-7) a compound having a carboxyl group and a heterocyclic group and having a total atomic number of 3 to 20 excluding a hydrogen atom and a carboxyl group, or a salt thereof; (d-8) having a sulfonic acid group and a heterocyclic group; Hydrogen atom and sulfonate The total number of atoms except for the group 3 to 20 or a salt thereof, [but, R 1 ~ R 4 independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group of 1, Q represents a single bond or a carbonyl group]. 如申請專利範圍第1項之著色組成物，其中構成前述錯合物之中心原子為Cu、Zn、Ni、Cr、Al、Co、Mg、In、Fe或B。 The colored composition of claim 1, wherein the central atom constituting the complex is Cu, Zn, Ni, Cr, Al, Co, Mg, In, Fe or B. 如申請專利範圍第1項之著色組成物，其中前述錯合物為金屬酞菁素。 The colored composition of claim 1, wherein the complex is a metal phthalocyanine. 如申請專利範圍第1至3項中任一項之著色組成物，其進一步含有(E)胺價為5mgKOH/g以上之分散劑。 The coloring composition according to any one of claims 1 to 3, further comprising (E) a dispersing agent having an amine value of 5 mgKOH/g or more. 一種彩色濾光片，其具備使用如申請專利範圍第1至3項中任一項之著色組成物所形成之著色層。 A color filter comprising a coloring layer formed using the colored composition according to any one of claims 1 to 3. 一種顯示元件，其具備如申請專利範圍第5項之彩色濾光片。 A display element comprising a color filter as in item 5 of the patent application.
TW100146682A 2010-12-24 2011-12-16 Coloring composition, color filter, and display element TWI505023B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010288130A JP5655551B2 (en) 2010-12-24 2010-12-24 Coloring composition, color filter and display element

Publications (2)

Publication Number Publication Date
TW201232170A TW201232170A (en) 2012-08-01
TWI505023B true TWI505023B (en) 2015-10-21

Family

ID=46411999

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100146682A TWI505023B (en) 2010-12-24 2011-12-16 Coloring composition, color filter, and display element

Country Status (4)

Country Link
JP (1) JP5655551B2 (en)
KR (1) KR101767685B1 (en)
CN (1) CN102566269B (en)
TW (1) TWI505023B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102028479B1 (en) * 2013-07-18 2019-10-04 동우 화인켐 주식회사 A colored photosensitive resin composition, color filter and display device comprising the same
JP6162084B2 (en) 2013-09-06 2017-07-12 富士フイルム株式会社 Colored composition, cured film, color filter, method for producing color filter, solid-state imaging device, image display device, polymer, xanthene dye
KR102134138B1 (en) 2016-03-14 2020-07-15 후지필름 가부시키가이샤 Composition, film, cured film, optical sensor and method for manufacturing film
JP6954031B2 (en) * 2017-11-15 2021-10-27 Dic株式会社 Pigment dispersion for color filters and color filters
CN111801604B (en) * 2018-03-05 2022-04-01 住友化学株式会社 Colored curable resin composition, color filter, and display device
JP7230480B2 (en) * 2018-12-14 2023-03-01 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition for color filter and color filter
TW202112837A (en) 2019-09-26 2021-04-01 日商富士軟片股份有限公司 Heat-conducting layer production method, laminate production method, and semiconductor device production method
JP7322753B2 (en) * 2020-03-03 2023-08-08 東レ株式会社 Photosensitive resin composition, light shielding layer and touch sensor panel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006058788A (en) * 2004-08-23 2006-03-02 Mitsubishi Chemicals Corp Coloring composition for color filter, color filter and liquid crystal display apparatus

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE68922470T2 (en) * 1988-11-26 1995-09-07 Toppan Printing Co Ltd Color filter for a multi-color liquid crystal display panel.
JPH04369653A (en) * 1991-06-18 1992-12-22 Ube Ind Ltd Coloring photosensitive resin composition
JP3293171B2 (en) * 1992-06-11 2002-06-17 ジェイエスアール株式会社 Radiation-sensitive composition for color filter and color filter
JPH0635188A (en) * 1992-07-15 1994-02-10 Nippon Kayaku Co Ltd Photopolymerizable composition for color filter and color filter
JP3940523B2 (en) * 1999-04-27 2007-07-04 セイコーエプソン株式会社 Resin composition for inkjet color filter, color filter, and method for producing color filter
US6641653B2 (en) * 2001-07-19 2003-11-04 Cabot Corporation Ink compositions comprising modified colored pigments and methods for preparing the same
JP5407199B2 (en) * 2008-07-03 2014-02-05 三菱化学株式会社 Pigment dispersion, coloring composition, color filter, liquid crystal display device and organic EL display

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006058788A (en) * 2004-08-23 2006-03-02 Mitsubishi Chemicals Corp Coloring composition for color filter, color filter and liquid crystal display apparatus

Also Published As

Publication number Publication date
KR101767685B1 (en) 2017-08-11
TW201232170A (en) 2012-08-01
CN102566269A (en) 2012-07-11
KR20120073102A (en) 2012-07-04
JP5655551B2 (en) 2015-01-21
JP2012137531A (en) 2012-07-19
CN102566269B (en) 2016-06-15

Similar Documents

Publication Publication Date Title
TWI505023B (en) Coloring composition, color filter, and display element
TWI501034B (en) Coloring composition, color filter and color liquid crystal display element
TWI542646B (en) Coloring composition, color filter and display device
TWI704413B (en) Colored composition, colored cured film and display element
JP5994775B2 (en) Coloring composition, color filter and display element
TWI510564B (en) Coloring composition for color filter, color filter, display element, and pigment dispersion for color filter
TWI650380B (en) Coloring composition, coloring cured film, and display element
TW201543153A (en) Radiation-sensitive composition, cured film, display device and colorant dispersion liquid
TWI624505B (en) Colored composition, color filter and color liquid crystal display element
TWI605308B (en) Coloring composition, color filter and display device
TWI472517B (en) Coloring composition, color filter, and color liquid crystal display element
TWI570193B (en) Coloring composition, color filter, display device and pigment dispersion liquid
JP2018188488A (en) Colored composition, colored cured film, and display element and solid-state image sensor
KR20110065348A (en) Coloring composition, color filter and display device
TWI626508B (en) Coloring composition for color filter, color filter and display element
JP5842463B2 (en) Basic colorant, coloring composition, color filter and display element
TWI594076B (en) Coloring composition, color filter, and display element
TW201544552A (en) Colorant, curable composition, cured film, display device and solid-state image pickup element
TW201502700A (en) Coloring composition, coloring cured film, and display element
TWI568802B (en) Colored composition, color filter, and display element
TWI534189B (en) Colored composition, color filter and display element
TW201300464A (en) Coloring agent, coloring composition, color filter, and display component
JP6160618B2 (en) Coloring composition, color filter and display element
TWI607061B (en) Colored composition, colored cured film and display element
JP6123509B2 (en) Coloring composition for color filter, color filter and display element