TWI774657B - Colored curable resin composition, color filter and display device containing the same - Google Patents

Colored curable resin composition, color filter and display device containing the same Download PDF

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TWI774657B
TWI774657B TW106104734A TW106104734A TWI774657B TW I774657 B TWI774657 B TW I774657B TW 106104734 A TW106104734 A TW 106104734A TW 106104734 A TW106104734 A TW 106104734A TW I774657 B TWI774657 B TW I774657B
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acrylate
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acid
resin composition
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TW201741767A (en
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太田喜之
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日商住友化學股份有限公司
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    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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    • 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
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
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    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

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Abstract

The present invention provides a colored curable resin composition, a color filter and a display device containing the same. The colored curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein, the colorant (A) is C.I. I. Pigment Green 59, and the polymerizable compound (C) comprises a (meth) acrylate (c1) which is at least one selected from the group consisting of ethylene oxide modified dipentaerythritol penta (meth) acrylate and ethylene oxide modified dipentaerythritol hexa (meth) acrylate.

Description

著色硬化性樹脂組成物、彩色濾光片及含有該濾光片之顯示裝置 Colored curable resin composition, color filter, and display device containing the same

本發明係有關著色硬化性樹脂組成物、彩色濾光片及含有該濾光片之顯示裝置。 The present invention relates to a colored curable resin composition, a color filter, and a display device including the filter.

近年來，液晶顯示裝置正在進行用以擴展可顯示的顏色重現範圍之開發，其中一環係尋求更深色的彩色濾光片。彩色濾光片之深色化的方法可列舉如提高彩色濾光片中之著色劑濃度之方法。然而，若提高著色劑濃度，則圖案形狀會變差等，作為著色硬化性樹脂組成物之性能會變差。另一方面，係有藉由使用著色力高的著色劑而到更深色的彩色濾光片之方法。然而，若使用著色力高的著色劑，則所得彩色濾光片的亮度會降低。其它可列舉如：使彩色濾光片為厚膜而顯現出深色的方法。然而，若將加厚的彩色濾光片應用在液晶顯示裝置，則在該彩色濾光片與相鄰像素之間會發生光的混色。 In recent years, liquid crystal display devices are being developed to expand the range of color reproduction that can be displayed, one part of which is the search for darker color filters. As a method of darkening the color filter, for example, a method of increasing the concentration of the colorant in the color filter can be mentioned. However, when the colorant concentration is increased, the pattern shape is deteriorated, and the performance as a colorable curable resin composition is deteriorated. On the other hand, there is a method of obtaining a darker color filter by using a colorant with high tinting power. However, when a colorant with high tinting strength is used, the brightness of the obtained color filter will decrease. Others include, for example, a method of making the color filter thick and expressing a dark color. However, if a thicker color filter is applied to a liquid crystal display device, color mixing of light occurs between the color filter and adjacent pixels.

日本特開2011-084726號公報中記載一種彩 色濾光片用著色硬化性樹脂組成物，其包含具有為多鹵化鋅酞青素顏料之C.I.顏料綠58與經環氧乙烷改質乙烯性不飽和化合物之聚合性化合物。 Japanese Patent Application Laid-Open No. 2011-084726 describes a color A colored curable resin composition for a color filter comprising a polymerizable compound having C.I. Pigment Green 58, which is a polyhalogenated zinc phthalocyanine pigment, and an ethylene oxide-modified ethylenically unsaturated compound.

本發明係提供以下表示之著色硬化性樹脂組成物、彩色濾光片及顯示裝置。 The present invention provides a colored curable resin composition, a color filter, and a display device shown below.

[1]一種著色硬化性樹脂組成物，其包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)，其中，上述著色劑(A)含有C.I.顏料綠59，上述聚合性化合物(C)含有由環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯及環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的(甲基)丙烯酸酯(c1)。 [1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) contains a C.I. pigment Green 59, the above-mentioned polymerizable compound (C) contains ethylene oxide-modified dipivalerythritol penta(meth)acrylate and ethylene oxide-modified dipivalerythritol hexa(meth)acrylate. At least one (meth)acrylate (c1) selected from the group.

[2]如[1]所述之著色硬化性樹脂組成物，其中，上述聚合性化合物(C)進一步含有上述(甲基)丙烯酸酯(c1)以外之含(甲基)丙烯醯基的化合物(c2)。 [2] The colored curable resin composition according to [1], wherein the polymerizable compound (C) further contains a (meth)acryloyl group-containing compound other than the (meth)acrylate (c1) (c2).

[3]如[1]或[2]所述之著色硬化性樹脂組成物，其中，含(甲基)丙烯醯基的化合物(c2)係由三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、參(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯、乙二醇改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質二 新戊四醇六(甲基)丙烯酸酯、己內酯改質新戊四醇四(甲基)丙烯酸酯及己內酯改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的化合物。 [3] The colored curable resin composition according to [1] or [2], wherein the (meth)acryloyl group-containing compound (c2) is composed of trimethylolpropane tri(meth)acrylate , Neotaerythritol tri(meth)acrylate, Neotaerythritol tetra(meth)acrylate, Dipivalerythritol penta(meth)acrylate, Dipivalerythritol hexa(meth)acrylate , Trinepentaerythritol octa (meth)acrylate, Trinepentaerythritol hepta (meth)acrylate, Tetranepentaerythritol ten (meth)acrylate, Tetranepentaerythritol nine (meth)acrylate Acrylate, ginseng (2-(meth)acryloyloxyethyl) isocyanate, ethylene glycol modified neotaerythritol tetra(meth)acrylate, propylene oxide modified neotaerythritol tetra( Meth)acrylate, propylene oxide modified two Among the group consisting of neopentaerythritol hexa(meth)acrylate, caprolactone-modified neotaerythritol tetra(meth)acrylate and caprolactone-modified dipeoerythritol hexa(meth)acrylate Select at least one compound.

[4]如[1]至[3]中任一項所述之著色硬化性樹脂組成物，其中，在上述聚合性化合物(C)100質量%中，上述(甲基)丙烯酸酯(c1)之含量為20質量%以上。 [4] The colored curable resin composition according to any one of [1] to [3], wherein in 100% by mass of the polymerizable compound (C), the (meth)acrylate (c1) The content is 20% by mass or more.

[5]一種彩色濾光片，係由[1]至[4]中任一項所述之著色硬化性樹脂組成物所形成。 [5] A color filter comprising the colorable curable resin composition according to any one of [1] to [4].

[6]一種顯示裝置，其包含[5]所述之彩色濾光片。 [6] A display device comprising the color filter of [5].

第1圖係表示具有正錐形狀之著色圖案的簡略剖面圖。 Fig. 1 is a schematic cross-sectional view showing a coloring pattern having a forward cone shape.

第2圖係表示具有倒錐形狀之著色圖案的簡略剖面圖。 Fig. 2 is a schematic cross-sectional view showing a colored pattern having an inverted tapered shape.

<著色硬化性樹脂組成物> <Colored curable resin composition>

本發明之著色硬化性樹脂組成物係包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)，著色劑(A)含有C.I.顏料綠59，聚合性化合物(C)含有由環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯及環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的(甲基)丙烯酸酯(c1)。依據本發明之著色硬化性樹脂組成物，可形成兼具高亮度及優異之圖案形狀的彩色濾光片。 The coloring curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) contains C.I. Pigment Green 59, polymerizable The compound (C) contains at least one selected from the group consisting of ethylene oxide-modified dipivalerythritol penta(meth)acrylate and ethylene oxide-modified dipivalerythritol hexa(meth)acrylate One kind of (meth)acrylate (c1). According to the colored curable resin composition of the present invention, a color filter having both high brightness and an excellent pattern shape can be formed.

以下，對於各成分詳加說明，惟本說明書中例示作為各成分的化合物，如無特別說明，係可單獨使用或將複數種組合使用。 Hereinafter, each component will be described in detail, but the compounds exemplified as each component in this specification may be used alone or in combination of plural types unless otherwise specified.

[1]著色劑(A) [1] Colorant (A)

本發明之著色硬化性樹脂組成物係包含作為著色劑(A)之C.I.顏料綠59。 The colorable curable resin composition of the present invention contains C.I. Pigment Green 59 as a colorant (A).

著色劑(A)100質量%中，著色劑(A)中之C.I.顏料綠59的含量通常為10至100質量%，從有效地兼具高亮度與優異之圖案形狀的觀點來看，係以30質量%以上為佳，以40質量%以上更佳，以45質量%以上又更佳。 The content of C.I. Pigment Green 59 in the colorant (A) is usually 10 to 100% by mass in 100% by mass of the colorant (A), and from the viewpoint of effectively combining high brightness and excellent pattern shape, it is 30 mass % or more is preferable, 40 mass % or more is more preferable, and 45 mass % or more is still more preferable.

本發明之著色硬化性樹脂組成物，著色劑(A)係可進一步包含C.I.顏料綠59以外之其它著色劑。在此情況下，著色劑(A)100質量%中，C.I.顏料綠59之含量可為90質量%以下，可為80質量%以下，可為70質量%以下，亦可為60質量%以下。 In the colorable curable resin composition of the present invention, the colorant (A) may further contain other colorants than C.I. Pigment Green 59. In this case, the content of C.I. Pigment Green 59 in 100 mass % of the colorant (A) may be 90 mass % or less, 80 mass % or less, 70 mass % or less, or 60 mass % or less.

C.I.顏料綠59以外之其它著色劑，可為C.I.顏料綠59以外之其它顏料，也可為染料，亦可為該等之兩者。 Colorants other than C.I. Pigment Green 59 may be pigments other than C.I. Pigment Green 59, dyes, or both.

其它著色劑可僅使用1種，亦可併用2者以上。其它顏料係可列舉如：有機顏料及無機顏料，可列舉以色料索引(the society of dyers and colourists出版)分類之顏料的化合物。 As for other colorants, only one type may be used, or two or more types may be used in combination. Examples of other pigments include organic pigments and inorganic pigments, and compounds of pigments classified by the Color Index (published by the society of dyers and colourists) can be cited.

C.I.顏料綠59以外之其它顏料，可列舉如：C.I.顏料藍15、15：3、15：4、15：6、16、60等藍色顏料； C.I.顏料綠7、36、58等C.I.顏料綠59以外的綠色顏料；C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、129、137、138、139、147、148、150、153、154、166、173、185、194、214等黃色顏料；C.I.顏料紫1、19、23、29、32、36、38等紫色顏料等。 Other pigments other than C.I. Pigment Green 59, such as: C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Pigment Green 7, 36, 58, etc. Green pigments other than C.I. Pigment Green 59; C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93 , 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Violet 1, 19 , 23, 29, 32, 36, 38 and other purple pigments.

其中，C.I.顏料綠59以外之其它顏料係以黃色顏料為佳。黃色顏料中，以包含C.I.顏料黃138、139、150、185等為佳，以包含C.I.顏料黃138更佳。 Among them, other pigments other than C.I. Pigment Green 59 are preferably yellow pigments. Among the yellow pigments, it is preferable to contain C.I. Pigment Yellow 138, 139, 150, 185, etc., and it is more preferable to contain C.I. Pigment Yellow 138.

本發明之著色硬化性樹脂組成物包含上述較佳之黃色顏料與C.I.顏料綠59時，可得到呈現更佳亮度的彩色濾光片。 When the colorable curable resin composition of the present invention contains the above-mentioned preferred yellow pigment and C.I. Pigment Green 59, a color filter with better brightness can be obtained.

從有效地兼具高亮度與優異之圖案形狀的觀點來看，以提高綠色著色劑中之C.I.顏料綠59的含量為佳。在綠色著色劑100質量%中，綠色著色劑中之C.I.顏料綠59的含量係以50質量%以上為佳，以80質量%以上更佳，以90質量%以上又更佳，以95質量%以上又再更佳，以100質量%為最佳。 From the viewpoint of effectively combining high brightness and excellent pattern shape, it is preferable to increase the content of C.I. Pigment Green 59 in the green colorant. In 100% by mass of the green colorant, the content of C.I. Pigment Green 59 in the green colorant is preferably at least 50% by mass, more preferably at least 80% by mass, still more preferably at least 90% by mass, and more preferably at least 95% by mass The above is still more preferable, and 100% by mass is the best.

上述其它的著色劑可為染料。染料係可使用習知的染料，可列舉如：溶劑染料、酸性染料、直接染料及媒染染料等。染料可列舉例如：以色料索引(colour index)(染料及色彩協會(The Society of Dyers and Colourists)出版)分類為顏料以外之具有色相者的化合物、和染色筆記(染色

Figure 106104734-A0202-12-0005-1
)(色染公司)所記載之習知的染料。而且，依據 化學構造，可列舉如：偶氮染料、花青染料、三苯基甲烷染料、二苯并吡喃(xanthene)染料、酞青素染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基(methine)染料、次甲基偶氮(azomethine)染料、方酸菁染料、吖啶染料、苯乙烯染料、香豆素染料、喹啉染料、硝基染料等。該等之中，以有機溶劑可溶性染料為佳。 The other colorants described above may be dyes. As the dye system, conventional dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. The dyes include, for example, compounds having hues other than pigments classified by the colour index (published by The Society of Dyers and Colourists), and dyeing notes (dyeing notes).
Figure 106104734-A0202-12-0005-1
) (Dyeing Company) as a conventional dye. Further, depending on the chemical structure, for example, azo dyes, cyanine dyes, triphenylmethane dyes, dibenzopyran (xanthene) dyes, phthalocyanin dyes, anthraquinone dyes, naphthoquinone dyes, and quinoneimine can be exemplified. Dyes, methine dyes, azomethine dyes, squaraine dyes, acridine dyes, styrene dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among these, organic solvent-soluble dyes are preferred.

著色劑(A)包含C.I.顏料綠59以外之其它著色劑時，從有效地兼具高亮度與優異之圖案形狀的觀點來看，在著色劑(A)100質量%中，該其它著色劑之含量係以10質量%以上為佳，以20質量%以上更佳，以30質量%以上又更佳，亦可為40質量%以上。 When the colorant (A) contains other colorants other than C.I. Pigment Green 59, from the viewpoint of effectively combining high brightness and excellent pattern shape, in the colorant (A) 100 mass %, the other colorant is The content is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and may be 40% by mass or more.

著色硬化性樹脂組成物中之著色劑(A)的合計含量，在著色硬化性樹脂組成物之固形物成分100質量%中，通常為10至60質量%，惟從兼具高亮度與優異之圖案形狀的觀點來看，在著色硬化性樹脂組成物之固形物成分100質量%中，以15至50質量%為佳，以20至50質量%更佳。 The total content of the colorant (A) in the colorable curable resin composition is usually 10 to 60% by mass in 100% by mass of the solid content of the colorable curable resin composition, but from the combination of high brightness and excellent From the viewpoint of the pattern shape, it is preferably 15 to 50 mass %, more preferably 20 to 50 mass %, in 100 mass % of the solid content of the colored curable resin composition.

另外，本說明書中，「著色硬化性樹脂組成物之固形物成分」係指著色硬化性樹脂組成物中所含的成分中除了溶劑(E)以外的全部成分。 In addition, in this specification, "solid content of a coloring curable resin composition" means all components other than a solvent (E) among the components contained in a coloring curable resin composition.

著色硬化性樹脂組成物之調製中使用的各種顏料，係以均勻地分散在溶劑中之分散液的狀態為佳。而且，顏料係以粒徑均勻者為佳。上述分散液係可藉由混合顏料與溶劑而得者。亦可視需要而混合顏料分散劑。藉 由使含有顏料分散劑並進行分散處理，可得到顏料均勻地分散在溶劑中之狀態的顏料分散液。 The various pigments used in the preparation of the colored curable resin composition are preferably in the state of a dispersion liquid uniformly dispersed in a solvent. Furthermore, the pigment is preferably one with a uniform particle size. The above-mentioned dispersion system can be obtained by mixing a pigment and a solvent. Pigment dispersants can also be mixed as desired. borrow By containing a pigment dispersant and performing dispersion treatment, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solvent can be obtained.

作為顏料分散劑，可使用市售之界面活性劑，可列舉如：聚矽氧系、氟系、酯系(包含聚酯系)、陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等界面活性劑。 As the pigment dispersant, commercially available surfactants can be used, such as polysiloxane-based, fluorine-based, ester-based (including polyester-based), cationic, anionic, nonionic, amphoteric, and polyester-based , polyamine, acrylic and other surfactants.

界面活性劑之具體例，除了聚氧伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚乙二醇二酯、山梨醇酐脂肪酸酯、脂肪酸改質聚酯、第三胺改質聚胺甲酸酯、聚伸乙亞胺等之外，可列舉如：商品名稱為KP(信越化學工業股份有限公司製造)、Floren(共榮社化學股份有限公司製造)、Solsperse(Zeneca股份有限公司製造)、EFKA(BASF JAPAN股份有限公司製造)、Ajisper(註冊商標)(Ajinomoto Fine-Techno股份有限公司製造)、Disperbyk(BYK Chemie股份有限公司製造)等。顏料分散劑可僅使用1種，亦可併用2種以上。 Specific examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and third In addition to amine-modified polyurethane, polyethyleneimine, etc., for example, trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Shin-Etsu Chemical Co., Ltd.) Zeneca Co., Ltd.), EFKA (BASF JAPAN Co., Ltd.), Ajisper (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (BYK Chemie Co., Ltd.), etc. Only one type of pigment dispersant may be used, or two or more types may be used in combination.

在使用顏料分散劑時，相對於顏料100質量份，其使用量係以100質量份以下為佳，以5至50質量份更佳。顏料分散劑之使用量在上述範圍時，會有容易得到均勻之分散狀態的顏料分散液之傾向。 When a pigment dispersant is used, the usage amount is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment. When the usage-amount of the pigment dispersant is within the above-mentioned range, there is a tendency to easily obtain a pigment dispersion liquid in a uniformly dispersed state.

構成顏料分散液之溶劑並無特別限定，可列舉與可含在著色硬化性樹脂組成物中之後述的溶劑(E)為相同之溶劑。 The solvent constituting the pigment dispersion liquid is not particularly limited, and examples thereof include the same solvent as the solvent (E) which can be contained in the colored curable resin composition to be described later.

其中，溶劑以丙二醇單甲基醚乙酸酯、乳 酸乙酯、丙二醇單甲基醚、3-乙氧基丙酸乙酯、乙二醇單甲基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺等為佳，以丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、二丙二醇單甲基醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯等為佳。亦可併用2種以上之溶劑。 Among them, the solvent is propylene glycol monomethyl ether acetate, milk Ethyl Acetate, Propylene Glycol Monomethyl Ether, Ethyl 3-Ethoxypropionate, Ethylene Glycol Monomethyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, 3-Methoxy Ethyl butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferred, and propylene glycol monomethyl Ethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3- Ethoxy propionate and the like are preferred. Two or more solvents may be used in combination.

溶劑之使用量並無特別限定，惟顏料分散液中之固形物成分的濃度，以成為3至20質量%之量為佳，以成為5至18質量%之量更佳。 The amount of the solvent used is not particularly limited, but the concentration of the solid content in the pigment dispersion liquid is preferably 3 to 20% by mass, more preferably 5 to 18% by mass.

著色硬化性樹脂組成物之調製中使用的各種顏料，可視需要而施行下列處理：松香處理、使用導入有酸性基或鹼性基之顏料衍生物和顏料分散劑等之表面處理、藉由高分子化合物等在顏料表面進行之接枝處理、藉由硫酸微粒化法等進行之微粒化處理、或藉由用以去除不純物之有機溶劑和水等進行之洗滌處理、將離子性雜質藉由離子交換法等而進行去除之去除處理等。 Various pigments used in the preparation of the colored curable resin composition may be subjected to the following treatments as necessary: rosin treatment, surface treatment with pigment derivatives introduced with acid or basic groups and pigment dispersants, etc. Grafting of compounds, etc. on the surface of pigments, micronization by sulfuric acid micronization, etc., or washing by organic solvents and water to remove impurities, ion exchange of ionic impurities Removal treatment, etc., for removal by method, etc.

[2]樹脂(B) [2] Resin (B)

本發明之著色硬化性樹脂組成物係含有樹脂(B)。著色硬化性樹脂組成物可含有1種或2種以上之樹脂作為樹脂(B)。樹脂(B)係以鹼可溶性樹脂為佳。鹼可溶性係指溶解於作為鹼化合物之水溶液的顯影液之性質。樹脂(B)可列舉如以下之樹脂[K1]至[K6]等。 The coloring curable resin composition of this invention contains resin (B). The colored curable resin composition may contain one kind or two or more kinds of resins as resin (B). The resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound. As resin (B), the following resins [K1] to [K6] etc. are mentioned.

樹脂[K1]：由不飽和羧酸及不飽和羧酸酐所成群中選 出之至少1種(a)[以下亦有稱為「(a)」之情形]與具有碳數2至4之環狀醚構造及乙烯性不飽和鍵之單體(b)[以下亦有稱為「(b)」之情形]的共聚物。 Resin [K1]: selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride At least one of (a) [hereinafter also referred to as "(a)"] and monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(a)") The case referred to as "(b)"].

樹脂[K2]：(a)及(b)，及可與(a)共聚合之單體(c)(惟，與(a)及(b)係相異)[以下亦有稱為「(c)」之情形]之共聚物。 Resin [K2]: (a) and (b), and monomer (c) which can be copolymerized with (a) (but, different from (a) and (b)) [also referred to as "( c)" case].

樹脂[K3]：(a)及(c)之共聚物。 Resin [K3]: a copolymer of (a) and (c).

樹脂[K4]：使(a)及(c)之共聚物與(b)反應而得的樹脂。 Resin [K4]: A resin obtained by reacting the copolymer of (a) and (c) with (b).

樹脂[K5]：使(b)及(c)之共聚物與(a)反應而得的樹脂。 Resin [K5]: A resin obtained by reacting the copolymer of (b) and (c) with (a).

樹脂[K6]：使(b)及(c)之共聚物與(a)反應，再與羧酸酐反應而得的樹脂。 Resin [K6]: A resin obtained by reacting the copolymer of (b) and (c) with (a) and then reacting with a carboxylic acid anhydride.

作為(a)，具體而言係可列舉：(甲基)丙烯酸、巴豆酸、鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸；順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸；甲基-5-降莰烯-2,3-二羧酸、5-羧基聯環[2.2.1]庚-2-烯、5,6-二羧基聯環[2.2.1]庚-2-烯、5-羧基-5-甲基聯環[2.2.1]庚-2-烯、5-羧基-5-乙基聯環[2.2.1]庚-2-烯、5-羧基-6-甲基聯環[2.2.1]庚-2-烯、5-羧基-6-乙基聯環[2.2.1]庚-2-烯等含羧基的聯環不飽和化合物；順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲 酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、脫氫5,6-二羧基聯環[2.2.1]庚-2-烯(海米酸酐)等不飽和二羧酸酐類；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2價以上的多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯；如α-(羥基甲基)(甲基)丙烯酸之於同一分子中含有羥基及羧基的不飽和(甲基)丙烯酸等。 Specific examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid; maleic acid, fumaric acid, etc. acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2 ,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-norbornene-2, 3-Dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo Cyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept- 2-ene, 5-carboxy-6-ethyl bicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3- Vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydro5,6-dicarboxybicyclo[2.2.1]hept-2-ene ( Unsaturated dicarboxylic anhydrides such as hemic acid anhydride); mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate Unsaturated mono[(meth)acrylooxyalkyl]esters of polycarboxylic acids with more than 2 valences such as esters; such as α-(hydroxymethyl)(meth)acrylic acid containing hydroxyl and carboxyl groups in the same molecule Unsaturated (meth)acrylic acid, etc.

其中，從共聚反應性之觀點、對鹼性水溶液之溶解性之觀點來看，(a)係以(甲基)丙烯酸、順丁烯二酸酐等為佳。 Among them, the (a) system is preferably (meth)acrylic acid, maleic anhydride, or the like from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution.

而且，本說明書中，「(甲基)丙烯酸」表示由丙烯酸及甲基丙烯酸所成群中選出之至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之註記亦同。 In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group of acrylic acid and methacrylic acid. The same applies to the notations such as "(meth)acryloyl" and "(meth)acrylate".

(b)係指具有碳數2至4之環狀醚構造(例如由氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環所成群中選出之至少1種)與乙烯性不飽和鍵之聚合性化合物。(b)係以具有碳數2至4之環狀醚構造與甲基丙烯醯氧基之單體為佳。 (b) means having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond of polymeric compounds. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a methacryloyloxy group.

(b)可列舉例如：具有氧雜環丙烷基與乙烯性不飽和鍵之單體(b1)[以下亦有稱為「(b1)」之情形]、具有氧雜環丁烷基與乙烯性不飽和鍵之單體(b2)[以下亦有稱為「(b2)」之情形]及具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)[以下亦有稱為「(b3)」之情形]等。 (b) Examples of monomers (b1) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenic unsaturated bond, Unsaturated bond monomer (b2) [hereinafter also referred to as "(b2)"] and monomer (b3) having tetrahydrofuran group and ethylenically unsaturated bond [hereinafter also referred to as "(b3)" situation] etc.

(b1)係可列舉如：具有不飽和脂肪族烴經環氧化之構造的單體(b1-1)[以下亦有稱為「(b1-1)」之情形]、具有不飽和脂環烴經環氧化之構造的單體(b1-2)[以下亦有稱為「(b1-2)」之情形]。 Examples of (b1) include: a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized [hereinafter also referred to as "(b1-1)"], a monomer having an unsaturated alicyclic hydrocarbon Monomer (b1-2) having an epoxidized structure [hereinafter also referred to as "(b1-2)"].

(b1-1)可列舉如：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油乙烯基醚、鄰-乙烯基苯甲基縮水甘油醚、間-乙烯基苯甲基縮水甘油醚、對-乙烯基苯甲基縮水甘油醚、α-甲基-鄰-乙烯基苯甲基縮水甘油醚、α-甲基-間-乙烯基苯甲基縮水甘油醚、α-甲基-對-乙烯基苯甲基縮水甘油醚、2,3-雙(縮水甘油基氧基甲基)苯乙烯、2,4-雙(縮水甘油基氧基甲基)苯乙烯、2,5-雙(縮水甘油基氧基甲基)苯乙烯、2,6-雙(縮水甘油基氧基甲基)苯乙烯、2,3,4-參(縮水甘油基氧基甲基)苯乙烯、2,3,5-參(縮水甘油基氧基甲基)苯乙烯、2,3,6-參(縮水甘油基氧基甲基)苯乙烯、3,4,5-參(縮水甘油基氧基甲基)苯乙烯、2,4,6-參(縮水甘油基氧基甲基)苯乙烯等。 (b1-1) For example, glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, alpha-methyl-o-vinylbenzyl glycidyl ether, alpha -Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,3 4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2 , 3,4-Sham(glycidyloxymethyl)styrene, 2,3,5-Sham(glycidyloxymethyl)styrene, methyl)styrene, 3,4,5-paras(glycidyloxymethyl)styrene, 2,4,6-paras(glycidyloxymethyl)styrene and the like.

(b1-2)可列舉如：乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如：Celloxide 2000；Daicel化學工業股份有限公司製造)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如：Cyclomer A400；Daicel化學工業股份有限公司製造)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如：Cyclomer M100；Daicel化學工業股份有限公司製造)、式(I)表示之化合物、式(II)表示之化合物等。 (b1-2) Examples include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example: Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl) base) 3,4-epoxycyclohexylmethyl acrylate (for example: Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example: Cyclomer M100 ; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

Figure 106104734-A0202-12-0012-2
Figure 106104734-A0202-12-0012-2

式(I)及式(II)中，Ra及Rb係互相獨立地表示氫原子或碳數1至4之烷基，該烷基中所含的氫原子可經羥基取代。X1及X2係互相獨立地表示單鍵、*-RC-、*-RC-O-、*-RC-S-或*-RC-NH-。RC表示碳數1至6之烷烴二基。*表示與O之鍵結鍵。 In formula (I) and formula (II), R a and R b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X 1 and X 2 independently represent a single bond, *-R C- , *-R C -O-, *-R C -S- or *-R C- NH-. R C represents an alkanediyl group having 1 to 6 carbon atoms. * indicates a bond with O.

碳數1至4之烷基可列舉如：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.

氫原子經羥基取代之烷基可列舉如：羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxyl group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy- 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like.

Ra及Rb係以氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基為佳，以氫原子、甲基更佳。 R a and R b are preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.

構成RC之烷烴二基可列舉如：亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl constituting R C include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl, hexane-1,6-diyl, etc.

X1及X2係以單鍵、亞甲基、伸乙基、*-CH2-O-(*表示與O之鍵結鍵)基、*-CH2CH2-O-基為佳，以單鍵、*-CH2CH2-O-基為更佳。 X 1 and X 2 are preferably single bond, methylene group, ethylidene group, *-CH 2 -O- (* represents a bond with O) group, *-CH 2 CH 2 -O- group, A single bond, *-CH 2 CH 2 -O- group is more preferred.

式(1)表示之化合物的具體例，可列舉如：式(I-1)至式(I-15)表示之化合物。以式(I-1)、式(I-3)、式 (I-5)、式(I-7)、式(I-9)及式(I-11)至式(I-15)表示之化合物為佳，以式(I-1)、式(I-7)、式(I-9)及式(I-15)表示之化合物更佳。 Specific examples of the compound represented by formula (1) include compounds represented by formula (I-1) to formula (I-15). With formula (I-1), formula (I-3), formula Compounds represented by (I-5), formula (I-7), formula (I-9) and formula (I-11) to formula (I-15) are preferred, with formula (I-1), formula (I) Compounds represented by -7), formula (I-9) and formula (I-15) are more preferable.

Figure 106104734-A0202-12-0013-3
Figure 106104734-A0202-12-0013-3

式(II)表示之化合物的具體例，可列舉如：式(II-1)至式(II-15)表示之化合物。以式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)及式(II-11)至式(II-15)表示之化合物為佳，以式(II-1)、式(II-7)、式(II-9)及式(II-15)表示之化合物更佳。 Specific examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15). Represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15) The compounds are preferred, and the compounds represented by formula (II-1), formula (II-7), formula (II-9) and formula (II-15) are more preferred.

Figure 106104734-A0202-12-0014-4
Figure 106104734-A0202-12-0014-4

式(I)表示之化合物及式(II)表示之化合物係可分別單獨使用。而且，該等可以任意之比率混合。在混合時，該混合比率以式(I)表示之化合物：式(II)表示之化合物[莫耳比]計係以5：95至95：5為佳，以10：90至90：10更佳，以20：80至80：20又更佳。 The compound represented by the formula (I) and the compound represented by the formula (II) can be used independently, respectively. Also, these may be mixed in any ratio. When mixing, the mixing ratio is preferably 5:95 to 95:5, preferably 10:90 to 90:10 in terms of the compound represented by the formula (I): the compound represented by the formula (II) [mol ratio] Best, 20:80 to 80:20 is even better.

具有氧雜環丁烷基與乙烯性不飽和鍵之單體(b2)，係以具有氧雜環丁烷基與(甲基)丙烯醯氧基之單體為佳。(b2)之較佳例可列舉如：3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷。 The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Preferred examples of (b2) include: 3-methyl-3-(meth)acryloyloxymethyl oxetane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane Butane.

具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)，係以具有四氫呋喃基與(甲基)丙烯醯氧基之單體為佳。(b3)之較佳例，可列舉如：丙烯酸四氫糠酯(例如：Viscoat V#150；大阪有機化學工業股份有限公司製造)、甲基丙烯酸四氫糠酯等。 The monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150; manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(c)之具體例係可列舉如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、三環[5.2.1.02.6]癸烷-8-基(甲基)丙烯酸酯[在該技術領域中，慣用名稱為「(甲基)丙烯酸二環戊酯」。亦稱為「(甲基)丙烯酸三環癸酯」]、三環[5.2.1.02.6]癸烯-8-基(甲基)丙烯酸酯[在該技術領域中，慣用名稱為「(甲基)丙烯酸二環戊烯酯」]、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基的(甲基)丙烯酸酯；順丁烯二酸二乙酯、反丁烯二酸二乙酯、、伊康酸二乙酯等二羧酸二酯；聯環[2.2.1]庚-2-烯、5-甲基聯環[2.2.1]庚-2-烯、5-乙 基聯環[2.2.1]庚-2-烯、5-羥基聯環[2.2.1]庚-2-烯、5-羥基甲基聯環[2.2.1]庚-2-烯、5-(2'-羥基乙基)聯環[2.2.1]庚-2-烯、5-甲氧基聯環[2.2.1]庚-2-烯、5-乙氧基聯環[2.2.1]庚-2-烯、5,6-二羥基聯環[2.2.1]庚-2-烯、5,6-二(羥基甲基)聯環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)聯環[2.2.1]庚-2-烯、5,6-二甲氧基聯環[2.2.1]庚-2-烯、5,6-二乙氧基聯環[2.2.1]庚-2-烯、5-羥基-5-甲基聯環[2.2.1]庚-2-烯、5-羥基-5-乙基聯環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基聯環[2.2.1]庚-2-烯、5-第三丁氧基羰基聯環[2.2.1]庚-2-烯、5-環己基氧基羰基聯環[2.2.1]庚-2-烯、5-苯氧基羰基聯環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)聯環[2.2.1]庚-2-烯、5,6-雙(環己基氧基羰基)聯環[2.2.1]庚-2-烯等聯環不飽和化合物；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順丁烯二醯亞胺等二羰基亞胺衍生物；苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、氯化亞乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Specific examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, (meth)acrylate 3-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclo(meth)acrylate Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2.6 ]decan-8-yl (meth)acrylate [in this technical field Among them, the common name is "dicyclopentyl (meth)acrylate". Also known as "(meth)acrylate tricyclodecyl"], tricyclo[ 5.2.1.02.6 ]decen-8-yl (meth)acrylate [in this technical field, the common name is "(methyl) ) Dicyclopentenyl acrylate”], Dicyclopentyloxyethyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate , (meth)acrylates such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; 2-hydroxy (meth)acrylate Hydroxy-containing (meth)acrylates such as ethyl ester and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, diethyl itconate, etc. Dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2 -ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[ 2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6- Dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl) ) bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene Cyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1 ] Hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl) bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimide Imido-4-maleimidobutyrate, N-succinimidino-6-maleimidohexanoate, N-succinimidino-3-cis Dicarbonyl imine derivatives such as butenediimide propionate, N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methylstyrene , p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-Butadiene, Isoprene, 2,3-Dimethyl- 1,3-butadiene, etc.

其中，從共聚合反應性及耐熱性之觀點來 看，(c)係以(甲基)丙烯酸苯甲酯、(甲基)丙烯酸三環癸酯、苯乙烯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、聯環[2.2.1]庚-2-烯等為佳。而且，就圖案形成時之顯影性優異而言，(c)係以(甲基)丙烯酸苯甲酯及(甲基)丙烯酸三環癸酯為更佳。 Among them, from the viewpoint of copolymerization reactivity and heat resistance, Look, (c) is based on benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide Imine, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred. Moreover, since the developability at the time of pattern formation is excellent, (c) system is more preferably benzyl (meth)acrylate and tricyclodecyl (meth)acrylate.

在構成樹脂[K1]之全部構造單元中，樹脂[K1]中各來源之構造單元的比率，以在下述範圍為佳。 Among all the structural units constituting the resin [K1], the ratio of the structural units of each origin in the resin [K1] is preferably within the following range.

來源為(a)之構造單元：2至50莫耳%(以10至45莫耳%為佳)、 來源為(b)之構造單元，尤其是來源為(b1)之構造單元：50至98莫耳%(以55至90莫耳%更佳)。 The source is the structural unit of (a): 2 to 50 mol% (preferably 10 to 45 mol%), The source is the structural unit of (b), especially the structural unit of the source (b1): 50 to 98 mol % (55 to 90 mol % is better).

樹脂[K1]之構造單元的比率在上述範圍時，則有保存安定性、顯影性、所得圖案之耐溶劑性優異之傾向。 When the ratio of the structural unit of resin [K1] is in the said range, there exists a tendency for the storage stability, developability, and the solvent resistance of the obtained pattern to be excellent.

樹脂[K1]係可參考文獻「高分子合成之實驗法」(大津隆行著，出版社 化學同人股份有限公司，第1版第1刷，1972年3月1日發行)所記載之方法及該文獻中記載之引用文獻進行製造。 Resin [K1] can refer to the method described in the document "Experimental Method for Polymer Synthesis" (written by Takashi Otsu, Publishing House Chemical Doujin Co., Ltd., 1st edition, 1st edition, issued on March 1, 1972) and the method described in this article. Manufactured from references cited in the literature.

具體而言，可列舉如：將預定量的(a)及(b)(尤其是(b1))、聚合起始劑及溶劑等饋入至反應容器中，在無氧氣體環境下進行攪拌、加熱、保溫之方法。另外，此處所使用之聚合起始劑及溶劑等並無特別限定，通常使用於該技術領域者均可使用。聚合起始劑可列舉如：偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊 腈)等、有機過氧化物(過氧化苯甲醯等)。溶劑只要是溶解各單體者即可，可使用後述之溶劑(E)等作為著色硬化性樹脂組成物之溶劑。 Specifically, for example, a predetermined amount of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, and the like are fed into a reaction vessel, and stirring is performed in an oxygen-free gas environment, Methods of heating and heat preservation. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Those generally used in this technical field can be used. Examples of polymerization initiators include: azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentane) nitrile), etc., organic peroxides (benzyl peroxide, etc.). The solvent should just dissolve each monomer, and the solvent (E) etc. mentioned later can be used as a solvent of a coloring curable resin composition.

另外，所得共聚物可直接使用反應後之溶液，亦可使用經濃縮或經稀釋之溶液，亦可使用以再沉澱等方法取出為固體(粉體)者。尤其是藉由使用後述之溶劑(E)作為該聚合時之溶劑，可直接使用反應後之溶液，而可簡化製造步驟。 In addition, the obtained copolymer can use the solution after reaction as it is, and can also use the solution which was concentrated or diluted, and can also use what was taken out as a solid (powder) by methods, such as reprecipitation. In particular, by using the solvent (E) described later as the solvent at the time of the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

在構成樹脂[K2]之全部構造單元中，樹脂[K2]中各來源之構造單元的比率，以在下述範圍為佳。 Among all the structural units constituting the resin [K2], the ratio of the structural units of each origin in the resin [K2] is preferably within the following range.

來源為(a)之構造單元：4至45莫耳%(以10至30莫耳%為佳)、 來源為(b)之構造單元，尤其是來源為(b1)之構造單元：2至95莫耳%(以5至80莫耳%更佳)、 來源為(c)之構造單元：1至65莫耳%(以5至60莫耳%更佳)。 The source is the structural unit of (a): 4 to 45 mol% (preferably 10 to 30 mol%), Structural units derived from (b), especially those derived from (b1): 2 to 95 mol% (preferably 5 to 80 mol%), The source is the building block of (c): 1 to 65 mol% (preferably 5 to 60 mol%).

樹脂[K2]之構造單元的比率在上述範圍時，有保存安定性、顯影性、所得圖案之耐溶劑性、耐熱性及機械強度優異之傾向。 When the ratio of the structural unit of resin [K2] is in the said range, there exists a tendency to be excellent in storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the obtained pattern.

樹脂[K2]可與樹脂[K1]之製造方法所記載之相同方法進行製造。具體而言，可列舉如：在將預定量的(a)、(b)(尤其是(b1))及(c)、聚合起始劑及溶劑饋入至反應容器中，在無氧氣體環境下進行攪拌、加熱、保溫之方法。所得共聚物，可直接使用反應後之溶液，亦可使用經 濃縮或經稀釋之溶液，亦可使用以再沉澱等方法取出為固體(粉體)者。 Resin [K2] can be manufactured by the same method as described in the manufacturing method of resin [K1]. Specifically, for example, after feeding predetermined amounts of (a), (b) (especially (b1)) and (c), the polymerization initiator and the solvent into the reaction vessel, in an oxygen-free gas environment The methods of stirring, heating, and heat preservation are described below. The obtained copolymer can directly use the solution after the reaction, or can also use the Concentrated or diluted solutions can also be used as solids (powders) taken out by methods such as reprecipitation.

在構成樹脂[K3]之全部構造單元中，樹脂[K3]中各來源之構造單元的比率，以在下述範圍為佳。 Among all the structural units constituting the resin [K3], the ratio of the structural units of each origin in the resin [K3] is preferably within the following range.

來源為(a)之構造單元：2至55莫耳%(以10至50莫耳%為佳)、 來源為(c)之構造單元：45至98莫耳%(以50至90莫耳%更佳)。 The source is the structural unit of (a): 2 to 55 mol% (preferably 10 to 50 mol%), The source is the building block of (c): 45 to 98 mol% (preferably 50 to 90 mol%).

樹脂[K3]係可與樹脂[K1]之製造方法所記載之相同方法進行製造。 Resin [K3] can be manufactured by the same method as described in the manufacturing method of resin [K1].

樹脂[K4]係可藉由得到(a)與(c)之共聚物，並將(b)所具有之碳數2至4之環狀醚構造，尤其是(b1)所具有之氧雜環丙烷環加成至(a)所具有之羧酸及/或羧酸酐而製造。具體而言，首先以與樹脂[K1]之製造方法所記載之相同方法製造(a)與(c)之共聚物。此時，在構成(a)與(c)之共聚物的全部構造單元中，各來源之構造單元的比率以在下述範圍為佳。 Resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and forming a cyclic ether having 2 to 4 carbon atoms in (b), especially an oxygen heterocyclic ring in (b1). It is produced by cycloaddition of propane to the carboxylic acid and/or carboxylic acid anhydride which (a) has. Specifically, first, the copolymer of (a) and (c) is produced by the same method as described in the production method of resin [K1]. In this case, it is preferable that the ratio of the structural unit of each origin is in the following range among all structural units which comprise the copolymer of (a) and (c).

來源為(a)之構造單元：5至50莫耳%(以10至45莫耳%為佳)、 來源為(c)之構造單元：50至95莫耳%(以55至90莫耳%更佳)。 The source is the structural unit of (a): 5 to 50 mol% (preferably 10 to 45 mol%), The source is the building block of (c): 50 to 95 mol% (preferably 55 to 90 mol%).

接著，使上述共聚物中來源為(a)的羧酸及/或羧酸酐之一部分與(b)所具有之碳數2至4的環狀醚構造，尤其是與(b1)所具有之氧雜環丙烷環反應。具體而言， 在(a)與(c)之共聚物的製造後，將燒瓶內的氣體環境由氮取代為空氣，將(b)(尤其是(b1))、羧酸或羧酸酐與環狀醚構造之反應觸媒(例如：參(二甲基胺基甲基)酚等)及聚合抑制劑(例如：氫醌等)等饋入燒瓶內，在60至130℃反應1至10小時，藉此可得到樹脂[K4]。 Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) and the cyclic ether structure having 2 to 4 carbon atoms possessed by (b), especially the oxygen possessed by (b1), are formed in the above-mentioned copolymer. Propane ring reaction. in particular, After the production of the copolymer of (a) and (c), the gas atmosphere in the flask is replaced by nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic acid anhydride and cyclic ether are constructed into Reaction catalysts (such as ginseng (dimethylaminomethyl)phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are fed into the flask, and the reaction is carried out at 60 to 130 ° C for 1 to 10 hours. Resin [K4] is obtained.

相對於(a)100莫耳，(b)之使用量，尤其是(b1)之使用量，係以5至80莫耳為佳，以10至75莫耳更佳。藉由設於此範圍內，有保存安定性、顯影性、耐溶劑性、耐熱性、機械強度、靈敏度之平衡變佳之傾向。因為環狀醚構造之反應性高，不易殘留未反應之(b)，因此，樹脂[K4]中使用的(b)係以(b1)為佳，以(b1-1)更佳。 Relative to (a) 100 moles, the usage amount of (b), especially the usage amount of (b1), is preferably 5 to 80 moles, more preferably 10 to 75 moles. By setting it within this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be improved. Since the cyclic ether structure has high reactivity, unreacted (b) is unlikely to remain. Therefore, (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

相對於(a)、(b)(尤其是(b1))及(c)之合計量，上述反應觸媒之使用量係以0.001至5質量%為佳。相對於(a)、(b)及(c)之合計量，上述聚合抑制劑之使用量係以0.001至5質量%為佳。 It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass % with respect to the total amount of (a), (b) (especially (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass relative to the total amount of (a), (b) and (c).

饋入方法、反應溫度及時間等反應條件，可考量製造設備、聚合所造成之發熱量等而適當地調整。另外，可與聚合條件相同地考量製造設備、聚合所造成之發熱量等而適當地調整饋入方法、反應溫度。 The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization, and the like. In addition, the feeding method and the reaction temperature can be appropriately adjusted in the same manner as the polymerization conditions in consideration of the production facility, the calorific value due to the polymerization, and the like.

樹脂[K5]就第一段階而言，係以與上述樹脂[K1]之製造方法相同方式得到(b)(尤其是(b1))與(c)之共聚物。與上述相同，所得共聚物可直接使用反應後之溶液，也可使用經濃縮或經稀釋之溶液，亦可使用以再沉澱等之方法取出為固體(粉體)者。 In the first stage, the resin [K5] is obtained by obtaining the copolymer of (b) (especially (b1)) and (c) in the same manner as in the production method of the above-mentioned resin [K1]. In the same manner as above, the obtained copolymer can be directly used as a solution after the reaction, can also be used as a concentrated or diluted solution, and can also be used as a solid (powder) extracted by a method such as reprecipitation.

相對於構成上述共聚物之全部構造單元之合計莫耳數，來源為(b)(尤其是(b1))及(c)之構造單元的比率，係以在下述範圍內為佳。 The ratio of the structural units derived from (b) (especially (b1)) and (c) is preferably within the following range with respect to the total molar number of all the structural units constituting the copolymer.

來源為(b)之構造單元，尤其是來源為(b1)之構造單元：5至95莫耳%(以10至90莫耳%更佳)、 來源為(c)之構造單元：5至95莫耳%(以10至90莫耳%更佳)。 Structural units derived from (b), especially those derived from (b1): 5 to 95 mol% (preferably 10 to 90 mol%), The source is the building block of (c): 5 to 95 mol% (preferably 10 to 90 mol%).

再者，以與樹脂[K4]之製造方法的相同條件，藉由使(b)(尤其是(b1))與(c)之共聚物所具有之來源為(b)的環狀醚構造、與(a)所具有之羧酸或羧酸酐反應，藉此可得到樹脂[K5]。相對於(b)(尤其是(b1))100莫耳，在上述共聚物中反應之(a)的使用量係以5至80莫耳為佳。由於環狀醚構造之反應性高，不易殘留未反應之(b)，因此，樹脂[K5]中使用的(b)係以(b1)為佳，以(b1-1)更佳。 Furthermore, under the same conditions as in the production method of resin [K4], by making the source of the copolymer of (b) (especially (b1)) and (c) to be the cyclic ether structure of (b), Resin [K5] can be obtained by reacting with the carboxylic acid or carboxylic acid anhydride which (a) has. The amount of (a) reacted in the above copolymer is preferably 5 to 80 mol relative to 100 mol of (b) (especially (b1)). Since the cyclic ether structure has high reactivity, unreacted (b) hardly remains. Therefore, (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

樹脂[K6]係進一步使羧酸酐與樹脂[K5]反應而成之樹脂。使藉由環狀醚構造與羧酸或羧酸酐之反應所產生的羥基，與羧酸酐反應。 Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. The hydroxyl group generated by the reaction of the cyclic ether structure with the carboxylic acid or the carboxylic acid anhydride is reacted with the carboxylic acid anhydride.

羧酸酐可列舉如：順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基聯環[2.2.1]庚-2-烯酐(海米酸酐)等。 Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2- Alkenic anhydride (hemic acid anhydride), etc.

樹脂[K1]至[K6]中，作為樹脂(B)之較佳樹脂為[K1]或[K2]。樹脂(B)可包含1種樹脂，亦可包含2種以 上之樹脂。 Among resins [K1] to [K6], preferable resins as resin (B) are [K1] or [K2]. Resin (B) may contain one kind of resin or two or more kinds resin on top.

樹脂(B)之聚苯乙烯換算之重量平均分子量係以3,000至100,000為佳，以5,000至50,000更佳，以5,000至30,000又更佳。分子量在上述範圍時，有未曝光部對顯影液之溶解性高，所得圖案之殘膜率、硬度亦高之傾向。樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]係以1.1至6為佳，以1.2至4更佳。 The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the solubility of the unexposed portion to the developing solution is high, and the residual film ratio and hardness of the obtained pattern tend to be high. The molecular weight distribution of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

樹脂(B)之溶液酸值係以5至180mg-KOH/g為佳，以10至100mg-KOH/g更佳，以12至50mg-KOH/g又更佳。酸值係測定用以中和樹脂1g所需的氫氧化鉀之量(mg)之值，例如可使用氫氧化鉀水溶液進行滴定而求得。 The acid value of the resin (B) is preferably 5 to 180 mg-KOH/g, more preferably 10 to 100 mg-KOH/g, and still more preferably 12 to 50 mg-KOH/g. The acid value is a value for measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

在著色硬化性樹脂組成物之固形物成分100質量%中，樹脂(B)之含量係以5至50質量%為佳，以10至40質量%更佳，以15至30質量%又更佳。樹脂(B)之含量在上述範圍時，有未曝光部對顯影液之溶解性高的傾向。 The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass in 100% by mass of the solid content of the colorable curable resin composition . When content of resin (B) is the said range, there exists a tendency for the solubility with respect to a developing solution of an unexposed part to be high.

[3]聚合性化合物(C) [3] Polymerizable compound (C)

聚合性化合物(C)係可藉由經光照射等從聚合起始劑(D)產生之活性自由基等而聚合的化合物。 The polymerizable compound (C) is a compound that can be polymerized by active radicals or the like generated from the polymerization initiator (D) by light irradiation or the like.

本發明之著色硬化性樹脂組成物中，聚合性化合物(C)係含有由環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯及環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的(甲基)丙烯酸酯(c1)。 In the coloring curable resin composition of the present invention, the polymerizable compound (C) contains ethylene oxide-modified dipeotaerythritol penta(meth)acrylate and ethylene oxide-modified dipeoerythritol At least one (meth)acrylate (c1) selected from the group of hexa(meth)acrylates.

(甲基)丙烯酸酯(c1)係下述式表示之(甲基) 丙烯酸酯化合物：

Figure 106104734-A0202-12-0023-5
(Meth)acrylate (c1) is a (meth)acrylate compound represented by the following formula:
Figure 106104734-A0202-12-0023-5

上述式中，X分別獨立地表示丙烯醯基或甲基丙烯醯基。Y表示氫原子、丙烯醯基或甲基丙烯醯基。a至f為1以上之整數，a至f之合計的a+b+c+d+e+f+g(以下，該合計量亦稱為「EO改質量」)為6至24之整數。a至f之合計以6至18為佳。 In the above formula, X independently represents an acryl group or a methacryl group. Y represents a hydrogen atom, an acryl group or a methacryl group. a to f are integers of 1 or more, and a+b+c+d+e+f+g of the total of a to f (hereinafter, the total amount is also referred to as "EO modified mass") is an integer of 6 to 24. The sum of a to f is preferably 6 to 18.

環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯係上述式中之Y為氫原子的化合物，環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯係上述式中之Y為丙烯醯基或甲基丙烯醯基的化合物。 The ethylene oxide-modified dipivalerythritol penta(meth)acrylate is a compound in which Y in the above formula is a hydrogen atom, and the ethylene oxide-modified dipivalerythritol hexa(meth)acrylate is the above-mentioned compound Y in the formula is a compound of acryl or methacryloyl.

作為聚合性化合物(C)之(甲基)丙烯酸酯(c1)，可僅含有上述式中之Y為氫原子的化合物，亦可僅含有上述式中之Y為丙烯醯基或甲基丙烯醯基的化合物，也可同時含有兩者。 The (meth)acrylate (c1) of the polymerizable compound (C) may contain only a compound in which Y in the above formula is a hydrogen atom, or only a compound in which Y in the above formula is acryl or methacryloyl A base compound may contain both.

藉由含有C.I.顏料綠59作為著色劑(A)且聚合性化合物(C)包含(甲基)丙烯酸酯(c1)之本發明的著色硬化性樹脂組成物，即可形成兼具高亮度與優異圖案形狀之彩色濾光片。 The colored curable resin composition of the present invention containing C.I. Pigment Green 59 as the colorant (A) and the polymerizable compound (C) containing the (meth)acrylate (c1) can form both high brightness and excellent Patterned color filters.

(甲基)丙烯酸酯(c1)係可藉由下述方法製造：包含在二新戊四醇使環氧乙烷開環加成之步驟、使源 自開環加成而導入之環氧乙烷的末端羥基與(甲基)丙烯醯氯或(甲基)丙烯酸反應而導入(甲基)丙烯醯基的步驟之方法；在(甲基)丙烯酸使環氧乙烷開環加成而合成環氧乙烷改質(甲基)丙烯酸之後，使與二新戊四醇進行酯化反應之方法；等。 (Meth)acrylate (c1) can be produced by a method including a step of ring-opening addition of ethylene oxide to dipivalerythritol, a source of A method for the step of introducing a (meth)acryloyl group by reacting the terminal hydroxyl group of ethylene oxide introduced by ring-opening addition with (meth)acryloyl chloride or (meth)acrylic acid; in (meth)acrylic acid After ethylene oxide is added to ring-opening to synthesize ethylene oxide-modified (meth)acrylic acid, the esterification reaction is carried out with dipeptaerythritol; etc.

作為環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯，亦可使用市售品(例如：商品名稱「M-DPH-6E」(新中村化學工業股份有限公司製造))。 As the ethylene oxide-modified dipovaerythritol penta(meth)acrylate, a commercial item (for example, trade name "M-DPH-6E" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)) can also be used.

本發明之著色硬化性樹脂組成物，可進一步含有(甲基)丙烯酸酯(c1)以外的其它聚合性化合物。 The colored curable resin composition of the present invention may further contain other polymerizable compounds other than the (meth)acrylate (c1).

本說明書中，將(甲基)丙烯酸酯(c1)與其它聚合性化合物統稱為「聚合性化合物(C)」。 In this specification, the (meth)acrylate (c1) and other polymerizable compounds are collectively referred to as "polymerizable compounds (C)".

其它聚合性化合物之重量平均分子量係以3000以下為佳。 The weight average molecular weight of other polymerizable compounds is preferably 3,000 or less.

本發明之著色硬化性樹脂組成物，除了(甲基)丙烯酸酯(c1)以外，可含有1種或2種以上之其它聚合性化合物。 In addition to the (meth)acrylate (c1), the colored curable resin composition of the present invention may contain one or two or more other polymerizable compounds.

其它聚合性化合物係以包含具有聚合性之乙烯性不飽和鍵的化合物為佳，以包含具有作為聚合性之乙烯性不飽和鍵的(甲基)丙烯醯基(例如：(甲基)丙烯醯氧基)之含(甲基)丙烯醯基的化合物(c2)為更佳。 The other polymerizable compound is preferably a compound containing a polymerizable ethylenically unsaturated bond, and preferably contains a (meth)acryloyl group having a polymerizable ethylenically unsaturated bond (for example: (meth)acryloyl group) The (meth)acryloyl group-containing compound (c2) of oxy) is more preferable.

其中，含有(甲基)丙烯醯基之化合物(c2)係以於分子內具有3個以上之(甲基)丙烯醯基的聚合性化合物為佳。其具體例可列舉如：三羥甲基丙烷三(甲基)丙烯 酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、參(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯、環氧乙烷改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質二新戊四醇六(甲基)丙烯酸酯、己內酯改質新戊四醇四(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等。 Among them, the (meth)acryloyl group-containing compound (c2) is preferably a polymerizable compound having three or more (meth)acryloyl groups in the molecule. Specific examples thereof include trimethylolpropane tri(meth)propylene Acid esters, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, dipeutaerythritol penta(meth)acrylate, dipeutaerythritol hexa(meth)acrylate Acrylates, Trinepentaerythritol Octa (meth)acrylate, Tripivalerythritol Hepta (meth)acrylate, Tetranepentaerythritol ten (meth)acrylate, Tetranepentaerythritol nona (meth)acrylate base) acrylate, ginseng (2-(meth)acryloyloxyethyl)trimeric isocyanate, ethylene oxide modified neopentylerythritol tetra(meth)acrylate, propylene oxide modified neopentyltetrakis Alcohol tetra (meth) acrylate, propylene oxide modified dipivoerythritol hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified two Neotaerythritol hexa(meth)acrylate, etc.

其中，以二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等為佳。 Among them, dipeotaerythritol penta(meth)acrylate, dipeotaerythritol hexa(meth)acrylate, etc. are preferable.

相對於著色硬化性樹脂組成物中之樹脂(B)100質量份，聚合性化合物(C)之含量係以10至150質量份為佳，以50至120質量份更佳。 The content of the polymerizable compound (C) is preferably 10 to 150 parts by mass, more preferably 50 to 120 parts by mass, relative to 100 parts by mass of the resin (B) in the colored curable resin composition.

從有效地兼具高亮度與優異之圖案形狀之觀點來看，聚合性化合物(C)中之(甲基)丙烯酸酯(c1)係以含量高者為佳。具體而言，在聚合性化合物(C)100質量%中，(甲基)丙烯酸酯(c1)之含量通常為20質量%，以50質量%為佳，以70質量%以上更佳，以80質量%以上又更佳，以90質量%以上再更佳，以95質量%以上又再更佳，以100質量%為最佳。 The (meth)acrylate (c1) in the polymerizable compound (C) preferably has a high content from the viewpoint of effectively combining high brightness and an excellent pattern shape. Specifically, in 100 mass % of the polymerizable compound (C), the content of the (meth)acrylate (c1) is usually 20 mass %, preferably 50 mass %, more preferably 70 mass % or more, and 80 mass % or more. More preferably, it is more than 90% by mass, more preferably more than 90% by mass, more preferably more than 95% by mass, and more preferably more than 100% by mass.

[4]聚合起始劑(D) [4] Polymerization initiator (D)

本發明之著色硬化性樹脂組成物係含有聚合起始劑(D)。著色硬化性樹脂組成物係可含有1種或2種以上之聚 合起始劑作為聚合起始劑(D)。 The colored curable resin composition of the present invention contains a polymerization initiator (D). The colored curable resin composition may contain one or two or more kinds of polymers. A co-initiator is used as the polymerization initiator (D).

作為聚合起始劑(D)，只要為藉由光、熱的作用而產生活性自由基、酸等而可使聚合開始化合物即可，無特別限定，可使用習知的聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, and the like by the action of light and heat, and conventional polymerization initiators can be used.

聚合起始劑(D)可列舉如：O-醯基肟化合物等肟化合物、烷基苯酮化合物、聯咪唑化合物、三

Figure 106104734-A0202-12-0026-35
化合物、醯基膦氧化物化合物等。聚合起始劑(D)亦可考量靈敏度、精密的圖案形狀之形成性等而併用2種以上。 Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, tris
Figure 106104734-A0202-12-0026-35
compounds, acylphosphine oxide compounds, etc. The polymerization initiator (D) may be used in combination of two or more in consideration of sensitivity, formability of precise pattern shapes, and the like.

因為有利於精密地製作出靈敏度及具有所要的線寬之圖案形狀，聚合起始劑(D)，係以包含O-醯基肟化合物等肟化合物為佳。 The polymerization initiator (D) is preferably composed of an oxime compound such as an O-acyl oxime compound because it is advantageous to precisely produce a pattern shape having a desired sensitivity and a desired line width.

本發明之著色硬化性樹脂組成物包含肟化合物時，以進一步包含聯咪唑化合物為佳。 When the colored curable resin composition of the present invention contains an oxime compound, it is preferable to further contain a biimidazole compound.

O-醯基肟化合物係具有式(d)表示之構造的化合物。以下，*表示鍵結鍵。 The O-acyl oxime compound is a compound having the structure represented by the formula (d). Hereinafter, * represents a bond key.

Figure 106104734-A0202-12-0026-6
Figure 106104734-A0202-12-0026-6

O-醯基肟化合物係例如：以由式(d1)表示之化合物(以下，亦稱為「化合物(d1)」)、式(d2)表示之化合物(以下，亦稱為「化合物(d2)」)、式(d3)表示之化合物(以下，亦稱為「化合物(d3)」)所成群中選出之至少1種者為佳。 The O-acyl oxime compound is, for example, a compound represented by formula (d1) (hereinafter, also referred to as "compound (d1)"), a compound represented by formula (d2) (hereinafter, also referred to as "compound (d2)" ") and at least one compound selected from the group of compounds represented by formula (d3) (hereinafter, also referred to as "compound (d3)") are preferred.

Figure 106104734-A0202-12-0027-7
Figure 106104734-A0202-12-0027-7

式(d1)至式(d3)中，Rd1表示可具有取代基之碳數6至18之芳香族烴基、可具有取代基之碳數3至36之雜環基、可具有取代基之碳數1至15之烷基、或芳香族烴基與由該烷基所衍生之烷烴二基組合之可具有取代基之基，上述烷基中所含的亞甲基(-CH2-)可經-O-、-CO-、-S-、-SO2-或-NRd5-置換；Rd2表示碳數6至18之芳香族烴基、碳數3至36之雜環基或碳數1至10之烷基；Rd3表示可具有取代基之碳數6至18之芳香族烴基、或可具有取代基之碳數3至36之雜環基；Rd4表示可具有取代基之碳數6至18之芳香族烴基、或可具有取代基之碳數1至15之脂肪族烴基，上述脂肪族烴基中所含的亞甲基(-CH2-)可經-O-、-CO-或-S-置換，上述脂肪族烴基中所含的次甲基(-CH<)可經-PO3<置換，上述脂肪族烴基中所含的氫原子可經OH基取代；Rd5表示碳數1至10之烷基，該烷基中所含的亞甲基(-CH2-)可經-O-或-CO-置換。 In formulas (d1) to (d3), R d1 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and an optionally substituted carbon group An alkyl group of numbers 1 to 15, or an aromatic hydrocarbon group combined with an alkanediyl group derived from the alkyl group may have a substituent, and the methylene group (-CH 2 -) contained in the above alkyl group may be -O-, -CO-, -S-, -SO 2 - or -NR d5 - substitution; R d2 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms, a heterocyclic group with 3 to 36 carbon atoms, or a heterocyclic group with 1 to 36 carbon atoms Alkyl of 10; R d3 represents an aromatic hydrocarbon group with a carbon number of 6 to 18 that may have a substituent, or a heterocyclic group with a carbon number of 3 to 36 that may have a substituent; R d4 Represents a carbon number 6 that may have a substituent group Aromatic hydrocarbon group to 18, or aliphatic hydrocarbon group with 1 to 15 carbon atoms which may have substituents, the methylene group (-CH 2 -) contained in the aliphatic hydrocarbon group may be replaced by -O-, -CO- or -S-replacement, the methine group (-CH<) contained in the above-mentioned aliphatic hydrocarbon group can be replaced by -PO 3 <, the hydrogen atom contained in the above-mentioned aliphatic hydrocarbon group can be replaced by OH group; R d5 represents carbon number The alkyl group of 1 to 10, the methylene group (-CH 2 -) contained in the alkyl group can be replaced by -O- or -CO-.

Rd1表示之芳香族烴基的碳數係以6至15為佳，以6至12更佳，以6至10又更佳。該芳香族烴基可列舉如：苯基、萘基、蒽基、菲基、聯苯基、聯三苯基等， 以苯基、萘基為佳，以苯基更佳。 The carbon number of the aromatic hydrocarbon group represented by R d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. The aromatic hydrocarbon group includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a triphenyl group, and the like, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

Rd1表示之芳香族烴基係可具有1個或2個以上之取代基。 The aromatic hydrocarbon group represented by R d1 may have one or two or more substituents.

取代基以在芳香族烴基之α位或γ位取代為佳，以在γ位取代更佳。該取代基可列舉如：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基等碳數1至15之烷基；氟原子、氯原子、碘原子、溴原子等鹵原子等。 The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, more preferably at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl Alkyl groups having 1 to 15 carbon atoms, such as radicals and pentadecyl radicals; halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms; and the like.

作為上述取代基之烷基的碳數，以1至10為佳，以1至7更佳。作為該取代基之烷基可為直鏈狀、分枝鏈狀、環狀之任一者，亦可為鏈狀之基與環狀之基組合而成之基。作為該取代基之烷基中所含的亞甲基(-CH2-)可經-O-或-S-置換。該烷基中所含的氫原子可經氟原子、氯原子、碘原子、溴原子等鹵原子取代，以經氟原子取代為佳。 The number of carbon atoms in the alkyl group as the substituent is preferably 1 to 10, more preferably 1 to 7. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a group formed by combining a chain group and a cyclic group. The methylene group (-CH 2 -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms, and are preferably substituted with fluorine atoms.

Rd1表示之芳香族烴基中，作為取代基之烷基可列舉下述式表示之基等。式中，*表示鍵結鍵。 In the aromatic hydrocarbon group represented by R d1 , the alkyl group represented by the following formula etc. is mentioned as a substituent. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0028-8
Figure 106104734-A0202-12-0028-8
Figure 106104734-A0202-12-0029-9
Figure 106104734-A0202-12-0029-9

可具有Rd1表示之取代基的芳香族烴基可列舉下述式表示之基等。式中，*表示鍵結鍵。 The aromatic hydrocarbon group which may have a substituent represented by R d1 includes a group represented by the following formula, and the like. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0029-10
Figure 106104734-A0202-12-0029-10

可具有Rd1表示之取代基的芳香族烴基係以下述式表示之基為佳。 The aromatic hydrocarbon group which may have a substituent represented by R d1 is preferably a group represented by the following formula.

Figure 106104734-A0202-12-0030-11
Figure 106104734-A0202-12-0030-11

式中，Rd6表示可經鹵原子取代之碳數1至10之烷基，Rd6中所含的氫原子可經鹵原子取代。m2表示1至5之整數。 In the formula, R d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, and the hydrogen atom contained in R d6 may be substituted by a halogen atom. m2 represents an integer from 1 to 5.

Rd6表示之烷基可列舉與例示作為Rd1表示之芳香族烴基的取代基之烷基相同的基。 The alkyl group represented by R d6 includes the same groups as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R d1 .

Rd6之碳數係以2至7為佳，以2至5更佳。而且，Rd6表示之烷基可為直鏈狀、分枝鏈狀及環狀之任一者，以鏈狀為佳。 The carbon number of R d6 is preferably 2 to 7, more preferably 2 to 5. In addition, the alkyl group represented by R d6 may be any of linear, branched and cyclic, preferably chain.

可取代Rd6中所含的氫原子之鹵原子可列舉如：氟原子、氯原子、碘原子、溴原子，以氟為特佳。而且，以Rd6中所含的氫原子之2個以上、10個以下經鹵原子取代者為佳，以3個以上、6個以下經鹵原子取代者更佳。Rd6O-基之取代位置係以鄰位、對位為佳，以對位為特佳。而且，m2係以1至2為佳，以1更佳。 The halogen atom that can replace the hydrogen atom contained in R d6 includes, for example, a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and fluorine is particularly preferred. Furthermore, the hydrogen atoms contained in R d6 are preferably substituted by halogen atoms at 2 or more and 10 or less, and more preferably 3 or more and 6 or less by halogen atoms. The substitution positions of the R d6 O- group are preferably ortho position and para position, and the para position is particularly preferred. Also, the m2 series is preferably 1 to 2, more preferably 1.

Rd1表示之雜環基的碳數係以3至20為佳，以3至10更佳，以3至5又更佳。該雜環基可列舉如：吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基及咔唑基等。 The carbon number of the heterocyclic group represented by R d1 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuranyl, and carbazolyl.

Rd1表示之雜環基可具有1個或2個以上之取代基。該取代基可列舉與例示作為Rd1表示之芳香族烴基可具有的取代基之基為相同的基。 The heterocyclic group represented by R d1 may have one or more substituents. Examples of the substituent include the same groups as exemplified as the substituent which the aromatic hydrocarbon group represented by R d1 may have.

Rd1表示之烷基的碳數係以1至12為佳。Rd1表示之烷基可列舉如：甲基、乙基、丙基、丁基、戊基、 己基、庚基、辛基、壬基、癸基、十一烷基、十二基、十三烷基、十四烷基、十五烷基等。該等烷基可為直鏈狀、分枝鏈狀及環狀之任一者，亦可為鏈狀之基與環狀之基組合而成之基。而且，Rd1表示之烷基中，亞甲基(-CH2-)可經-O-、-CO-、-S-、-SO2-或-NRd5-置換，氫原子可經OH基或SH基取代。 The carbon number of the alkyl group represented by R d1 is preferably 1 to 12. Examples of the alkyl group represented by R d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl. Alkyl, tetradecyl, pentadecyl, etc. These alkyl groups may be linear, branched, or cyclic, or may be a combination of a chain-like group and a cyclic group. Furthermore, in the alkyl group represented by R d1 , the methylene group (-CH 2 -) may be replaced by -O-, -CO-, -S-, -SO 2 - or -NR d5 -, and the hydrogen atom may be replaced by an OH group or SH group substitution.

Rd5表示碳數1至10之烷基，以碳數1至5之烷基為佳，以碳數1至3之烷基更佳。該烷基可為鏈狀(直鏈狀或分枝鏈狀)、可為環狀，也可為直鏈狀、分枝鏈狀及環狀之任一者，亦可為鏈狀之基與環狀之基組合而成之基。Rd5之烷基中，亞甲基(-CH2-)可經-O-或-CO-置換。 R d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be chain (straight or branched), cyclic, linear, branched and cyclic, or may be a chain-like group with A base formed by combining cyclic bases. In the alkyl group of R d5 , the methylene group (-CH 2 -) can be replaced by -O- or -CO-.

Rd1表示之基中，作為可具有取代基之烷基具體而言可列舉下述式表示之基等。*表示鍵結鍵。 Among the groups represented by R d1 , specific examples of the alkyl group which may have a substituent include groups represented by the following formulae, and the like. * Indicates a bond key.

Figure 106104734-A0202-12-0031-12
Figure 106104734-A0202-12-0031-12

再者，Rd1表示之芳香族烴基與由上述Rd1表示之烷基所衍生的烷烴二基組合而成之基的碳數係以7至33為佳，以7至18更佳，以7至12又更佳。該組合而成之基可具有1個或2個以上之取代基，該取代基可列舉 如：與例示作為芳香族烴、烷基可具有之取代基之基為相同的基。該Rd1表示之芳香族烴基與上述Rd1表示之烷基所衍生的烷烴二基組合而成之基，可列舉如芳烷基，具體而言，係可列舉下述式所示之基。式中，*表示鍵結鍵。 Furthermore, the carbon number of the group formed by the combination of the aromatic hydrocarbon group represented by R d1 and the alkanediyl group derived from the alkyl group represented by the above R d1 is preferably 7 to 33, more preferably 7 to 18, and 7 12 is even better. The combined group may have one or two or more substituents, and examples of the substituents include the same groups as those exemplified as the substituents which the aromatic hydrocarbons and the alkyl groups may have. A group formed by combining the aromatic hydrocarbon group represented by this R d1 and an alkanediyl group derived from the alkyl group represented by the above R d1 includes, for example, an aralkyl group, and specifically, a group represented by the following formula. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0032-13
Figure 106104734-A0202-12-0032-13

其中，Rd1係以可具有取代基之芳香族烴基或可具有取代基之烷基為佳，以可具有取代基之芳香族烴基更佳。 Among them, R d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

Rd2表示之芳香族烴基的碳數係以6至15為佳，以6至12更佳，以6至10又更佳。該芳香族烴基可列舉如：苯基、萘基、蒽基、菲基、聯苯基及聯三苯基等。 The carbon number of the aromatic hydrocarbon group represented by R d2 is preferably 6 to 15, more preferably 6 to 12, and more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a triphenyl group.

Rd2表示之雜環基的碳數係以3至20為佳，以3至10更佳，以3至5又更佳。雜環基可列舉如：吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基及咔唑基等。 The carbon number of the heterocyclic group represented by R d2 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuranyl, and carbazolyl.

Rd2表示之烷基的碳數係以1至7為佳，以1至5更佳，以1至3又更佳。該烷基可列舉如：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基及癸基等。該烷基可為直鏈狀、分枝鏈狀及環狀之任一者，亦可為鏈狀之基與環狀之基組合而成之基。 The carbon number of the alkyl group represented by R d2 is preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group may be any of linear, branched, and cyclic, or may be a group formed by combining a chain-like group and a cyclic group.

Rd2係以鏈狀烷基為佳，以碳數1至5之鏈狀烷基更佳，以碳數1至3之鏈狀烷基又更佳，以甲基為特佳。 R d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, even more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Rd3表示之芳香族烴基的碳數係以6至15為佳，以6至12更佳，以6至10又更佳。該芳香族烴基可 列舉如：苯基、萘基、蒽基、菲基、聯苯基及聯三苯基等，以苯基、萘基為更佳。 The carbon number of the aromatic hydrocarbon group represented by R d3 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a triphenyl group, and a phenyl group and a naphthyl group are more preferred.

Rd3表示之芳香族烴基可具有1個或2個以上之取代基。取代基係以在芳香族烴基之α位、γ位取代為佳。該取代基係以碳數1至15之脂肪族烴基為佳，具體而言可列舉如：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基及癸基等碳數1至15的烷基；乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、壬烯基及癸烯基等碳數1至15的烯基；等。 The aromatic hydrocarbon group represented by R d3 may have one or more substituents. The substituents are preferably substituted at the α-position and the γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and Alkyl with 1 to 15 carbon atoms such as decyl; alkenyl with 1 to 15 carbon such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl ;Wait.

關於Rd3表示之芳香族烴基中的取代基，脂肪族烴基係以碳數1至7者更佳。該脂肪族烴基可為直鏈狀、分枝鏈狀及環狀之任一者，亦可為鏈狀之基與環狀之基組合而成之基。該脂肪族烴基中所含的亞甲基(-CH2-)可經-O-、-CO-或-S-置換，次甲基(-CH<)可經-N<置換。 Regarding the substituent in the aromatic hydrocarbon group represented by R d3 , the aliphatic hydrocarbon group is more preferably one having 1 to 7 carbon atoms. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and may be a combination of a chain-like group and a cyclic group. The methylene group (-CH 2 -) contained in the aliphatic hydrocarbon group may be replaced by -O-, -CO- or -S-, and the methine group (-CH<) may be replaced by -N<.

Rd3表示之基中，作為芳香族烴基可具有之脂肪族烴基，可列舉下述式表示之基等。式中，*表示鍵結鍵。 Among the groups represented by R d3 , examples of the aliphatic hydrocarbon group which the aromatic hydrocarbon group may have include groups represented by the following formulae, and the like. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0033-14
Figure 106104734-A0202-12-0033-14

Rd3表示之基中，作為可具有取代基之芳香 族烴基，可列舉下述式表示之基等。式中，*表示鍵結鍵。 Among the groups represented by R d3 , examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae, and the like. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0034-15
Figure 106104734-A0202-12-0034-15

Rd3表示之雜環基的碳數係以3至20為佳，以3至10更佳，以3至5又更佳。該雜環基可列舉如：吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基及咔唑基等。而且，Rd3表示之雜環基可具有1個或2個以上之取代基。該取代基可列舉與例示作為Rd1表示之芳香族烴基可具有的取代基之基為相同的基。 The carbon number of the heterocyclic group represented by R d3 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuranyl, and carbazolyl. Furthermore, the heterocyclic group represented by R d3 may have one or more substituents. Examples of the substituent include the same groups as exemplified as the substituent which the aromatic hydrocarbon group represented by R d1 may have.

其中，Rd3係以具有取代基之芳香族烴基為佳，該取代基以碳數1至7(更佳為碳數1至3)之鏈狀烷基為佳，取代基之個數係以2個以上、5個以下為佳。 Among them, R d3 is preferably an aromatic hydrocarbon group with a substituent, and the substituent is preferably a chain alkyl group with a carbon number of 1 to 7 (more preferably a carbon number of 1 to 3), and the number of the substituent is 2 or more and 5 or less are preferable.

Rd4表示之芳香族烴基的碳數係以6至15為佳，以6至12更佳，以6至10又更佳。該芳香族烴基可列舉如：苯基、萘基、蒽基、菲基、聯苯基及聯三苯基等，以苯基及萘基更佳，以苯基又更佳。而且，Rd4表示之芳香族烴基可具有1個或2個以上之取代基。該取代基可列舉與Rd1之芳香族烴基可具有的取代基相同之基。 The carbon number of the aromatic hydrocarbon group represented by R d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. The aromatic hydrocarbon group includes, for example, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a triphenyl group, and the phenyl group and the naphthyl group are more preferable, and the phenyl group is even more preferable. Furthermore, the aromatic hydrocarbon group represented by R d4 may have one or two or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group of R d1 may have.

Rd4表示之脂肪族烴基的碳數係以1至13為佳，以2至10更佳，以4至9又更佳。Rd4表示之脂肪族 烴基可列舉如：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二基、十三基、十四基及十五基等烷基；乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基、十二烯基、十三烯基、十四烯基及十五烯基等烯基；等。該等脂肪族烴基可為鏈狀(直鏈狀或分枝鏈狀)，可為環狀，亦可為鏈狀之基與環狀之基組合而成之基。Rd4之脂肪族烴基中，亞甲基(-CH2-)可經-O-、-CO-或-S-置換，次甲基(-CH<)可經-PO3<置換，上述脂肪族烴基中所含的氫原子可經OH基取代。 The carbon number of the aliphatic hydrocarbon group represented by R d4 is preferably 1 to 13, more preferably 2 to 10, and still more preferably 4 to 9. The aliphatic hydrocarbon group represented by R d4 includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tenyl Alkyl such as triyl, tetradecyl and pentadecyl; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl Alkenyl groups such as alkenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl; etc. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a group formed by combining a chain group and a cyclic group. In the aliphatic hydrocarbon group of R d4 , the methylene group (-CH 2 -) can be replaced by -O-, -CO- or -S-, the methine group (-CH<) can be replaced by -PO 3 <, the above aliphatic group The hydrogen atom contained in the hydrocarbon group may be substituted with an OH group.

Rd4表示之基中，可具有取代基之脂肪族烴基可列舉下述式表示之基等。式中，*表示鍵結鍵。 Among the groups represented by R d4 , the aliphatic hydrocarbon groups which may have a substituent include groups represented by the following formulae, and the like. In the formula, * represents a bond bond.

Figure 106104734-A0202-12-0035-16
Figure 106104734-A0202-12-0035-16

Rd4係以可具有取代基之鏈狀脂肪族烴基為佳，以不具有取代基之鏈狀烷基更佳，以不具有取代基之分枝鏈狀烷基又更佳。 R d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group without a substituent, and even more preferably a branched chain alkyl group without a substituent.

作為化合物(d1)，可列舉如式(d1)表示之化合物，具體而言為具有(d1-1)欄中記載之各取代基的化合物 至具有(d1-7)欄中記載之各取代基之化合物。表1至7中，*表示鍵結鍵。 Examples of the compound (d1) include compounds represented by the formula (d1), and specifically, compounds having each of the substituents described in the column (d1-1) to compounds having each of the substituents described in the column (d1-7). In Tables 1 to 7, * represents a bonding bond.

Figure 106104734-A0202-12-0036-17
Figure 106104734-A0202-12-0036-17

Figure 106104734-A0202-12-0036-18
Figure 106104734-A0202-12-0036-18

Figure 106104734-A0202-12-0037-19
Figure 106104734-A0202-12-0037-19

Figure 106104734-A0202-12-0038-20
Figure 106104734-A0202-12-0038-20

Figure 106104734-A0202-12-0039-21
Figure 106104734-A0202-12-0039-21

Figure 106104734-A0202-12-0040-22
Figure 106104734-A0202-12-0040-22

Figure 106104734-A0202-12-0041-23
Figure 106104734-A0202-12-0041-23

Figure 106104734-A0202-12-0042-24
Figure 106104734-A0202-12-0042-24

其中，以具有(d1-3)欄中記載之各取代基的化合物至具有(d1-6)欄中記載之各取代基的化合物、具有(d1-18)欄中記載之各取代基的化合物至具有(d1-52)欄中記載之各取代基的化合物、具有(d1-55)欄中記載之各取代基的化合物、具有(d1-56)欄中記載之各取代基的化合物、具有(d1-60)欄中記載之各取代基的化合物、具有(d1-61)欄中記載之各取代基的化合物為佳，更佳為具有(d1-3)欄中記載之各取代基的化合物至具有(d1-6)欄中記載之各取代基的化合物、具有(d1-18)欄中記載之各取代基的化合物至具有(d1-41)欄中記載之各取代基的化合物，有更佳為具有(d1-24)欄中記載之各取代基的化合物、 具有(d1-36)欄中記載之各取代基的化合物至具有(d1-40)欄中記載之各取代基的化合物，特佳為具有(d1-24)欄中記載之各取代基的化合物。 Among them, the compound having each substituent described in the column (d1-3), the compound having each substituent described in the (d1-6) column, and the compound having each substituent described in the (d1-18) column To the compound having each substituent described in the column (d1-52), the compound having each substituent described in the column (d1-55), the compound having each substituent described in the column (d1-56), the compound having Compounds having each of the substituents described in the column (d1-60), compounds having each of the substituents described in the column (d1-61) are preferred, and compounds having each of the substituents described in the column (d1-3) are more preferred. Compounds to compounds having each substituent described in column (d1-6), compounds having each substituent described in column (d1-18) to compounds having each substituent described in column (d1-41), There are more preferably compounds having each of the substituents described in the column (d1-24), Compounds having each of the substituents described in the column (d1-36) to compounds having each of the substituents described in the column (d1-40), particularly preferably compounds having each of the substituents described in the column (d1-24) .

化合物(d1)，例如可藉由日本特表2014-500852號公報所記載之製造方法製造。 The compound (d1) can be produced, for example, by the production method described in JP 2014-500852 A.

化合物(d2)，較佳為：Rd1為可具有取代基之碳數1至15之烷基，Rd2為碳數1至10之烷基，Rd3為可具有取代基之碳數6至18之芳香族烴基，Rd4為可具有取代基之碳數1至15之脂肪族烴基的化合物；更佳為：Rd1表示甲基、乙基或丙基，Rd2表示甲基、乙基或丙基，Rd3表示經甲基取代之苯基，Rd4表示甲基、乙基或丙基的化合物，又更佳為：Rd1及Rd2為甲基，Rd3為鄰-甲苯基及Rd3為乙基之化合物。 Compound (d2), preferably: R d1 is an alkyl group with 1 to 15 carbon atoms which may have a substituent, R d2 is an alkyl group with 1 to 10 carbon atoms, and R d3 is an alkyl group with 6 to 15 carbon atoms which may have a substituent Aromatic hydrocarbon group of 18, R d4 is a compound of aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have substituents; more preferably: R d1 represents methyl, ethyl or propyl, R d2 represents methyl, ethyl or propyl group, R d3 represents a phenyl group substituted with methyl, R d4 represents a compound of methyl, ethyl or propyl group, and more preferably: R d1 and R d2 are methyl groups, and R d3 is o-tolyl and R d3 is a compound of ethyl.

化合物(d3)，較佳為：Rd1為可具有取代基之碳數1至15之烷基；Rd2為碳數6至18之芳香族烴基的化合物；更佳為：Rd1為己基及Rd2為苯基之化合物。 Compound (d3), preferably: R d1 is an alkyl group with 1 to 15 carbon atoms that may have a substituent; R d2 is a compound of an aromatic hydrocarbon group with 6 to 18 carbon atoms; more preferably: R d1 is a hexyl group and Compounds in which R d2 is phenyl.

此種O-醯基肟化合物可列舉如：N-苯甲醯基氧基-1-(4-苯基氫硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基氫硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基氫硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3- 二甲基-2,4-二

Figure 106104734-A0202-12-0044-36
環戊甲基氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯基氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用IRGACURE OXE01、OXE02、OXE03(以上為BASF公司製造)、N-1919(ADEKA公司製造)等市售品。如為該等O-醯基肟化合物，則有可得到蝕刻(litho)性能優異之彩色濾光片的傾向。 Examples of such O-acyl oxime compounds include: N-benzyloxy-1-(4-phenylhydrothiophenyl)butane-1-one-2-imine, N-benzyl Acryloyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylbenzene) base)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbohydrate Azol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2, 4-two
Figure 106104734-A0202-12-0044-36
Cyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-( 2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01, OXE02, OXE03 (the above are manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) can also be used. In the case of these O-acyl oxime compounds, there is a tendency that a color filter excellent in etching (litho) performance can be obtained.

烷基苯酮化合物係具有式(d4)表示之構造或式(d5)表示之構造的化合物。該等之構造中，苯環可具有取代基。 The alkylphenone compound is a compound having a structure represented by formula (d4) or a structure represented by formula (d5). In these structures, the benzene ring may have a substituent.

Figure 106104734-A0202-12-0044-25
Figure 106104734-A0202-12-0044-25

作為具有式(d4)表示之構造的化合物，可列舉如：2-甲基-2-嗎林基-1-(4-甲基氫硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎林基苯基)-2-苯甲基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎林基)苯基]丁烷-1-酮等。亦可使用IRGACURE 369、907、379(以上為BASF公司製造)等市售品。 Examples of compounds having a structure represented by the formula (d4) include 2-methyl-2-morpholinyl-1-(4-methylhydrogenthiophenyl)propan-1-one, 2-dimethylformyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl base]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF) can also be used.

具有式(d5)表示之構造的化合物，可列舉如：2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之低聚物、α,α-二乙氧基苯乙酮、苯甲基二甲基縮酮等。 Compounds having a structure represented by formula (d5) include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2 -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc.

就靈敏度之點而言，烷基苯酮化合物係以具有式(d4)表示之構造的化合物為佳。 In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

聯咪唑化合物可列舉如：2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(參照日本特開平6-75372號公報、日本特開平6-75373號公報等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(參照日本特公昭48-38403號公報、日本特開昭62-174204號公報等)、4,4',5,5'-位之苯基經烷氧羰基取代之咪唑化合物(參照日本特開平7-10913號公報等)等。 Examples of biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) Phenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), An imidazole compound in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (refer to Japanese Patent Laid-Open No. 7-10913, etc.) and the like.

其中，以下述式表示之化合物或該等之混合物為佳。 Among them, a compound represented by the following formula or a mixture thereof is preferable.

Figure 106104734-A0202-12-0045-26
Figure 106104734-A0202-12-0045-26

三

Figure 106104734-A0202-12-0045-37
化合物可列舉如：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三
Figure 106104734-A0202-12-0045-38
、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三
Figure 106104734-A0202-12-0045-39
、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三
Figure 106104734-A0202-12-0045-40
、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三
Figure 106104734-A0202-12-0045-41
、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三
Figure 106104734-A0202-12-0045-42
、 2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三
Figure 106104734-A0202-12-0046-43
、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基乙烯基]-1,3,5-三
Figure 106104734-A0202-12-0046-44
、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三
Figure 106104734-A0202-12-0046-46
等。 three
Figure 106104734-A0202-12-0045-37
Compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris
Figure 106104734-A0202-12-0045-38
, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris
Figure 106104734-A0202-12-0045-39
, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri
Figure 106104734-A0202-12-0045-40
, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri
Figure 106104734-A0202-12-0045-41
, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tri
Figure 106104734-A0202-12-0045-42
, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri
Figure 106104734-A0202-12-0046-43
, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenylvinyl]-1,3,5-tri
Figure 106104734-A0202-12-0046-44
, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri
Figure 106104734-A0202-12-0046-46
Wait.

醯基膦氧化物化合物可列舉如：2,4,6-三甲基苯甲醯基二苯基膦氧化物等。 As an acylphosphine oxide compound, 2,4,6- trimethylbenzyldiphenylphosphine oxide etc. are mentioned, for example.

作為進一步之聚合起始劑(D)，可列舉如：苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等苯偶姻化合物；二苯基酮、鄰-苯甲醯基苯甲酸甲酯、4-苯基二苯基酮、4-苯甲醯基-4'-甲基二苯基硫醚、3,3',4,4'-四(過氧化第三丁基羰基)二苯基酮、2,4,6-三甲基二苯基酮等二苯基酮化合物；9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、二苯甲醯(benzil)、苯甲醯甲酸甲酯、鈦莘化合物等。該等係以與後述之聚合起始助劑(D1)(尤其是胺類)組合而使用為佳。 As a further polymerization initiator (D), for example, benzene such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be mentioned. Azoin compounds; diphenyl ketone, methyl o-benzyl benzoate, 4-phenyl diphenyl ketone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3 ',4,4'-tetrakis(tert-butylcarbonyl peroxide) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2 -Quinone compounds such as ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzylcarboxylate, titanium cinnamon compounds, etc. These are preferably used in combination with a polymerization initiator (D1) (especially, amines) to be described later.

相對於樹脂(B)及聚合性化合物(C)之合計量100質量份，聚合起始劑(D)之含量係以0.1至30質量份為佳，以5至25質量份更佳，以10至20質量份又更佳。聚合起始劑(D)之含量在上述範圍內時，有提高靈敏度且縮短曝光時間之傾向，因此會有提高彩色濾光片之生產性的傾向。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and more preferably 10 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Even more preferably, it is 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be improved and the exposure time tends to be shortened, so that the productivity of the color filter tends to be improved.

(5)聚合起始助劑(D1) (5) Polymerization Initiating Auxiliary (D1)

聚合起始助劑(D1)係用以促進藉由聚合起始劑(D)使聚合開始之聚合性化合物(C)的聚合所使用之化合物或增 敏劑。在包含聚合起始助劑(D1)時，可與聚合起始劑(D)組合使用。 A polymerization initiator (D1) is a compound or an additive used for accelerating the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D). Sensitizer. When the polymerization initiator (D1) is contained, it can be used in combination with the polymerization initiator (D).

聚合起始助劑(D1)可列舉如：胺化合物、烷氧基蒽化合物、硫雜蒽酮化合物及羧酸化合物等。其中，以硫雜蒽酮化合物為佳。亦可將2種以上之聚合起始助劑(D1)合併使用。 Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, thioxanthone compounds are preferred. Two or more kinds of polymerization initiators (D1) may be used in combination.

胺化合物可列舉如：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯基酮(俗稱米奇勒酮)、4,4'-雙(二乙基胺基)二苯基酮、4,4'-雙(乙基甲基胺基)二苯基酮等，其中，以4,4'-雙(二乙基胺基)二苯基酮為佳。可使用EAB-F(保土谷化學工業股份有限公司製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4' -Bis(dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino) benzophenone, 4,4'-bis(ethylmethylamine) group) diphenyl ketone etc., among them, 4,4'-bis(diethylamino) diphenyl ketone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

烷氧基蒽化合物可列舉如：9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 Examples of alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

硫雜蒽酮化合物可列舉如：2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮等。 The thioxanthone compounds include, for example: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothoxanthene ketone, 1-chloro-4-propoxythioxanthone, etc.

羧酸化合物可列舉如：苯基氫硫基乙酸、甲基苯基氫硫基乙酸、乙基苯基氫硫基乙酸、甲基乙基苯 基氫硫基乙酸、二甲基苯基氫硫基乙酸、甲氧基苯基氫硫基乙酸、二甲氧基苯基氫硫基乙酸、氯苯基氫硫基乙酸、二氯苯基氫硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘硫代乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include: phenyl mercaptoacetic acid, methylphenyl mercaptoacetic acid, ethylphenyl mercaptoacetic acid, methylethylbenzene sulfhydryl acetic acid, dimethylphenyl sulfhydryl acetic acid, methoxyphenyl sulfhydryl acetic acid, dimethoxyphenyl sulfhydryl acetic acid, chlorophenyl sulfhydryl acetic acid, dichlorophenyl hydrogen Thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

相對於樹脂(B)及聚合性化合物(C)之合計量100質量份，聚合起始助劑(D1)之含量係以0.1至30質量份為佳，以1至20質量份更佳。聚合起始助劑(D1)之含量在上述範圍內時，有可進一步以高靈敏度形成著色圖案，且彩色濾光片之生產性提高之傾向。 The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D1) is within the above-mentioned range, a colored pattern can be formed with further high sensitivity, and the productivity of the color filter tends to be improved.

[6]硫醇化合物(T) [6] Thiol compound (T)

本發明之著色硬化性樹脂組成物可含有硫醇化合物(T)。著色硬化性樹脂組成物係可含有作為硫醇化合物(T)之1種或2種以上之硫醇化合物。當聚合起始劑(D)為O-醯基肟化合物等肟系化合物及/或聯咪唑化合物時，特別適合使用硫醇化合物(T)。硫醇化合物(T)係分子內至少具有1個氫硫基(-SH)之化合物。硫醇化合物(T)係以分子內具有1個氫硫基之化合物為佳。 The colored curable resin composition of the present invention may contain a thiol compound (T). The colored curable resin composition may contain one or more thiol compounds as the thiol compound (T). When the polymerization initiator (D) is an oxime-based compound such as an O-acyl oxime compound and/or a biimidazole compound, the thiol compound (T) is particularly suitably used. The thiol compound (T) is a compound having at least one thiol group (-SH) in the molecule. The thiol compound (T) is preferably a compound having one hydrogen thiol group in the molecule.

分子內具有1個氫硫基之化合物可列舉如：2-氫硫基

Figure 106104734-A0202-12-0048-47
唑、2-氫硫基噻唑、2-氫硫基苯并咪唑、2-氫硫基苯并噻唑、2-氫硫基苯并
Figure 106104734-A0202-12-0048-48
唑、2-氫硫基菸鹼酸、2-氫硫基吡啶、2-氫硫基吡啶-3-醇、2-氫硫基吡啶-N-氧化物、4-胺基-6-羥基-2-氫硫基嘧啶、4-胺基-2-氫硫基嘧啶、6-胺基-5-亞硝基-2-硫脲嘧啶、4,5-二胺基-6-羥基-2-氫硫基嘧啶、4,6-二胺基-2-氫硫基嘧啶、2,4-二胺基-6-氫硫基嘧 啶、4,6-二羥基-2-氫硫基嘧啶、4,6-二甲基-2-氫硫基嘧啶、4-羥基-2-氫硫基-6-甲基嘧啶、4-羥基-2-氫硫基-6-丙基嘧啶、2-氫硫基-4-甲基嘧啶、2-氫硫基嘧啶、2-硫脲嘧啶、3,4,5,6-四氫嘧啶-2-硫醇、4,5-二苯基咪唑-2-硫醇、2-氫硫基咪唑、2-氫硫基-1-甲基咪唑、4-胺基-3-肼基-5-氫硫基-1,2,4-三唑、3-胺基-5-氫硫基-1,2,4-三唑、2-甲基-4H-1,2,4-三唑-3-硫醇、4-甲基-4H-1,2,4-三唑-3-硫醇、3-氫硫基-1H-1,2,4-三唑-3-硫醇、2-胺基-5-氫硫基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2-硫醇、2,5-二氫硫基-1,3,4-噻二唑、(呋喃-2-基)甲硫醇、2-氫硫基-5-噻唑酮、2-氫硫基噻唑啉、2-氫硫基-4(3H)-喹唑啉酮、1-苯基-1H-四唑-5-硫醇、2-喹啉硫醇、2-氫硫基-5-甲基苯并咪唑、2-氫硫基-5-硝基苯并咪唑、6-胺基-2-氫硫基苯并噻唑、5-氯-2-氫硫基苯并噻唑、6-乙氧基-2-氫硫基苯并噻唑、6-硝基-2-氫硫基苯并噻唑、2-氫硫基萘并咪唑、2-氫硫基萘并
Figure 106104734-A0202-12-0049-49
唑、3-氫硫基-1,2,4-三唑、4-胺基-6-氫硫基吡唑并[2,4-d]吡啶、2-胺基-6-嘌呤硫醇、6-氫硫基嘌呤及4-氫硫基-1H-吡唑并[2,4-d]嘧啶等。 Compounds with one hydrogen thiol group in the molecule include: 2-hydrogen thiol group
Figure 106104734-A0202-12-0048-47
azole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzo
Figure 106104734-A0202-12-0048-48
azole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy- 2-Sulfanyl pyrimidine, 4-amino-2-hydrosulfanyl pyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2- Sulfanyl pyrimidine, 4,6-diamino-2-hydrosulfanyl pyrimidine, 2,4-diamino-6-hydrosulfanyl pyrimidine, 4,6-dihydroxy-2-hydrosulfanyl pyrimidine, 4 ,6-Dimethyl-2-hydrosulfanyl pyrimidine, 4-hydroxy-2-hydrosulfanyl-6-methylpyrimidine, 4-hydroxy-2-hydrosulfanyl-6-propylpyrimidine, 2-hydrosulfanyl yl-4-methylpyrimidine, 2-hydrothiopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol Alcohol, 2-Sulfanyl imidazole, 2-Sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino -5-Sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4- Triazole-3-thiol, 3-mercapto-1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3,4-thiadiazole , 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dihydrothio-1,3,4-thiadiazole, (furan-2-yl)methanethiol , 2-Sulfanyl-5-thiazolone, 2-Sulfanyl thiazoline, 2-Sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol , 2-quinoline thiol, 2-hydrosulfanyl-5-methylbenzimidazole, 2-hydrosulfanyl-5-nitrobenzimidazole, 6-amino-2-hydrosulfanylbenzothiazole, 5-Chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercapto-naphthimidazole , 2-hydrothionaphtho
Figure 106104734-A0202-12-0049-49
azole, 3-mercapto-1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-hydrosulfanyl purine and 4-hydrosulfanyl-1H-pyrazolo[2,4-d]pyrimidine, etc.

分子內具有2個以上的氫硫基之化合物，可列舉如：己烷二硫醇、癸烷二硫醇、1,4-雙(甲基氫硫基)苯、丁烷二醇雙(3-氫硫基丙酸酯)、丁烷二醇雙(3-氫硫基乙酸酯)、乙二醇雙(3-氫硫基乙酸酯)、三羥甲基丙烷參(3-氫硫基乙酸酯)、三羥甲基丙烷參(3-氫硫基丙酸酯)、新戊四醇肆(3-氫硫基丙酸酯)、新戊四醇肆(3-氫硫基乙酸酯)、參羥基乙基參(3-氫硫基丙酸酯)、新戊四醇肆(3-氫硫基丁 酸酯)及1,4-雙(3-氫硫基丁基氧基)丁烷等。 Compounds having two or more thiol groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylthiothio)benzene, butanediol bis(3) - Hydrogen thiopropionate), butanediol bis(3-hydrogen thioacetate), ethylene glycol bis(3-hydrogen thioacetate), trimethylolpropane(3-hydrogen thioacetate) thioacetate), trimethylolpropane ginseng (3-hydrogen thiopropionate), neotaerythritol tetra (3-hydrogen thiopropionate), neotaerythritol tetra (3-hydrogen thiopropionate) glycerol acetate), 3-hydroxyethyl ginseng (3-mercaptopropionate), neopentaerythritol (3-mercaptobutylene) acid ester) and 1,4-bis(3-hydrothiobutyloxy)butane, etc.

相對於聚合起始劑(D)100質量份，硫醇化合物(T)之含量係以0.5至50質量份為佳，以5至45質量份更佳，以10至40質量份又更佳。硫醇化合物(T)之含量在上述範圍內時，會有靈敏度變高，且顯影性變佳之傾向。 The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass relative to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within the above range, the sensitivity tends to be high and the developability tends to be good.

[7]溶劑(E) [7] Solvent (E)

本發明之著色硬化性樹脂組成物以含有溶劑(E)為佳。著色硬化性樹脂組成物可包含1種或2種以上之溶劑作為溶劑(E)。溶劑(E)可列舉如：酯溶劑(包含-COO-之溶劑)、酯溶劑以外之醚溶劑(包含-O-之溶劑)、醚酯溶劑(包含-COO-與-O-之溶劑)、酯溶劑以外之酮溶劑(包含-CO-之溶劑)、醇溶劑、芳香族烴溶劑、醯胺溶劑及二甲基亞碸等。 The colored curable resin composition of the present invention preferably contains a solvent (E). The colored curable resin composition may contain one or two or more kinds of solvents as the solvent (E). Examples of the solvent (E) include: ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), Ketone solvents (solvents including -CO-) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

酯溶劑可列舉如：乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯及γ-丁內酯等。 Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Cyclohexyl Alcohol acetate and γ-butyrolactone, etc.

醚溶劑可列舉如：乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二

Figure 106104734-A0202-12-0050-52
烷、二乙二醇二甲基醚、二 乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、苯甲醚、苯乙醚及甲基苯甲醚等。 Examples of ether solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-diol
Figure 106104734-A0202-12-0050-52
Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzyl ether, phenethyl ether and methyl anisole, etc.

醚酯溶劑可列舉如：甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、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、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯及二丙二醇甲基醚乙酸酯等。 Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate Ester, Ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Methyl 2-methoxypropionate, Ethyl 2-methoxypropionate ester, 2-methoxypropionate propyl, 2-ethoxypropionate methyl ester, 2-ethoxypropionate ethyl ester, 2-methoxy-2-methyl propionate methyl ester, 2-ethyl propionate Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

酮溶劑可列舉如：4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮及異佛酮等。 Examples of the ketone solvent include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone ketone, cyclopentanone, cyclohexanone and isophorone, etc.

醇溶劑可列舉如：甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及丙三醇等。芳香族烴溶劑可列舉如：苯、甲苯、二甲苯及均三甲苯等。醯胺溶劑可列舉如：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene. As an amide solvent, N,N- dimethylformamide, N,N- dimethylacetamide, N-methylpyrrolidone, etc. are mentioned, for example.

從塗佈性及乾燥性之觀點來看，溶劑(E)係以包含在1atm之沸點為120℃以上180以下的有機溶劑為佳。其中，溶劑(E)係以包含由丙二醇單甲基醚乙酸酯、乳 酸乙酯、丙二醇單甲基醚、3-乙氧基丙酸乙酯、乙二醇單甲基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮及N,N-二甲基甲醯胺所成群中選出之至少1種為佳，以包含由丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、二丙二醇甲基醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇及3-乙氧基丙酸乙酯所成群中選出之至少1種為更佳。 From the viewpoints of coatability and drying properties, the solvent (E) is preferably an organic solvent whose boiling point at 1 atm is 120° C. or higher and 180 or lower. Among them, the solvent (E) is composed of propylene glycol monomethyl ether acetate, emulsion Ethyl Acetate, Propylene Glycol Monomethyl Ether, Ethyl 3-Ethoxypropionate, Ethylene Glycol Monomethyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, 3-Methoxy At least 1 selected from the group consisting of butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide It is better to include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxybutyl acetate More preferably, at least one selected from the group consisting of 1-butanol and ethyl 3-ethoxypropionate.

著色硬化性樹脂組成物中，溶劑(E)之含量係以70至95質量%為佳，以75至92質量%更佳。換言之，著色硬化性樹脂組成物之固形物成分係以5至30質量%為佳，以8至25質量%更佳。溶劑(E)之含量在上述範圍時，塗佈時之平坦性變佳，且在形成彩色濾光片時之色濃度無不足，故有顯示特性變佳之傾向。 In the colored curable resin composition, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above-mentioned range, the flatness at the time of coating is improved, and the color density at the time of forming a color filter is not insufficient, so that the display characteristics tend to be improved.

[8]調平劑(F) [8] Leveler (F)

本發明之著色硬化性樹脂組成物可包含調平劑(F)。著色硬化性樹脂組成物係可包含1種或2種以上之調平劑作為調平劑(F)。作為調平劑(F)，可列舉如：聚矽氧系界面活性劑(惟不具有氟)、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。該等可在側鏈具有聚合性基。 The colored curable resin composition of the present invention may contain a leveling agent (F). The colored curable resin composition may contain one or two or more types of leveling agents as leveling agents (F). As the leveling agent (F), for example, polysiloxane-based surfactants (but not having fluorine), fluorine-based surfactants, and polysiloxane-based surfactants having fluorine atoms, etc. can be mentioned. These may have a polymerizable group in the side chain.

聚矽氧系界面活性劑(惟不具有氟)可列舉於分子內具有矽氧烷鍵之界面活性劑等。具體而言，可列舉如：Toray silicone DC3PA、Toray silicone SH7PA、Toray silicone DC11PA、Toray silicone SH21PA、Toray silicone SH28PA、Toray silicone SH29PA、Toray silicone SH30PA、Toray silicone SH8400(商品名稱：Toray Dow Corning股份有限公司製造)；KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製造)；TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452及TSF4460(Momentive Performance Materials Japan合同公司製造)等。 Polysiloxane-based surfactants (but not having fluorine) include those having siloxane bonds in the molecule, and the like. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400 , TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Contract Co., Ltd.).

氟系界面活性劑可列舉如：分子內具有氟碳鏈之界面活性劑等。具體而言可列舉如：Fluorad(註冊商標)FC430、Fluorad FC431(住友3M股份有限公司製造)；Megafac(註冊商標)F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac F554、Megafac R30、Megafac RS-718-K(DIC股份有限公司製造)；F-top(註冊商標)EF301、F-top EF303、F-top EF351、F-top EF352(三菱Materials電子化成股份有限公司製造)；Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子股份有限公司製造)；以及E5844(Daikin Fine Chemical Laboratory股份有限公司製造)等。 The fluorine-based surfactant includes, for example, a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation); F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.) ; Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.); and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

具有氟原子之聚矽氧系界面活性劑，可列舉如：於分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體而言可列舉如：Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477及Megafac F443(DIC股份有限公司製造)等。 The polysiloxane-based surfactant having a fluorine atom includes, for example, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.), etc. are mentioned.

在著色硬化性樹脂組成物中，調平劑(F)之 含量通常為0.001質量%以上、0.2質量%以下，以0.002質量%以上0.1質量%以下為佳，以0.005質量%以上0.05質量%以下更佳。又，該含量中，不包含上述顏料分散劑之含量。 In the coloring curable resin composition, one of the leveling agent (F) is The content is usually 0.001 mass % or more and 0.2 mass % or less, preferably 0.002 mass % or more and 0.1 mass % or less, more preferably 0.005 mass % or more and 0.05 mass % or less. In addition, the content of the said pigment dispersing agent is not included in this content.

[9]抗氧化劑(G) [9] Antioxidant (G)

從提高著色劑(A)之耐熱性及耐光性之觀點來看，著色硬化性樹脂組成物以含有抗氧化劑為佳。抗氧化劑如為工業上一般所使用的抗氧化劑，則無特別限定，可使用酚系抗氧化劑、磷系抗氧化劑及硫系抗氧化劑等。亦可使用2種以上的抗氧化劑。 From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the colorable curable resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used. Two or more antioxidants may also be used.

酚系抗氧化劑可列舉如：Irganox 1010(新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]，BASF股份有限公司製造)；Irganox 1076(十八基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯，BASF股份有限公司製造)；Irganox 1330(3,3',3",5,5',5"-六-第三丁基-a,a',a"-(均三甲苯-2,4,6-三基)-三-對-甲酚，BASF股份有限公司製造)；Irganox 3114(1,3,5-參(3,5-二-第三丁基-4-羥基苯甲基)-1,3,5-三

Figure 106104734-A0202-12-0054-53
-2,4,6(1H,3H,5H)-三酮、BASF股份有限公司製造)；Irganox 3790(1,3,5-參((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三
Figure 106104734-A0202-12-0054-54
-2,4,6(1H,3H,5H)-三酮、BASF股份有限公司製造)；Irganox 1035(硫代二乙烯雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]，BASF股份有限公司製造)；Irganox 1135(苯丙烷酸、3,5-雙(1,1-二甲基乙基)-4-羥基、C7-C9側鏈烷基酯，BASF股份有限公司製造)；Irganox 1520L(4,6-雙(辛 基硫甲基)-鄰-甲酚，BASF股份有限公司製造)；Irganox 3125(BASF股份有限公司製造)；Irganox 565(2,4-雙(正辛基硫基)-6-(4-羥基-3',5'-二-第三丁基苯胺基)-1,3,5-三
Figure 106104734-A0202-12-0055-55
，BASF股份有限公司製造)；ADKSTAB AO-80(3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯基氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、ADEKA股份有限公司製造)；Sumilizer BHT(住友化學股份有限公司製造)；Sumilizer GA-80(住友化學股份有限公司製造)；Sumilizer GS(住友化學股份有限公司製造)；Cyanox 1790(Cyanox 1790、Saitech股份有限公司製造)以及Vitamin E(Eisai股份有限公司製造)等。 Examples of phenolic antioxidants include: Irganox 1010 (neopentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.); Irganox 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Co., Ltd.); Irganox 1330(3,3',3",5, 5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)-tris-p-cresol, manufactured by BASF Co., Ltd.); Irganox 3114(1,3,5-para(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri
Figure 106104734-A0202-12-0054-53
-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.); Irganox 3790 (1,3,5-sam((4-tert-butyl-3-hydroxy-2,6 -Xylyl)methyl)-1,3,5-tris
Figure 106104734-A0202-12-0054-54
-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.); Irganox 1035 (thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyl) Phenyl) propionate], manufactured by BASF Co., Ltd.); Irganox 1135 (phenylpropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7-C9 side chain alkyl group ester, manufactured by BASF Co., Ltd.); Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.); Irganox 3125 (manufactured by BASF Co., Ltd.); Irganox 565 ( 2,4-Bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-tris
Figure 106104734-A0202-12-0055-55
, manufactured by BASF Co., Ltd.); ADKSTAB AO-80 (3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)- 1,1-Dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.); Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.); Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.); Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.); Cyanox 1790 (Cyanox 1790, manufactured by Saitech Co., Ltd.) and Vitamin E (manufactured by Eisai Co., Ltd.).

磷系抗氧化劑可列舉如：Irgafos 168(參(2,4-二-第三丁基苯基)亞磷酸酯、BASF股份有限公司製造)；Irgafos 12(參[2-[[2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二

Figure 106104734-A0202-12-0055-56
膦-6-基]氧基]乙基]胺，BASF股份有限公司製造)；Irgafos 38(雙(2,4-雙(1,1-二甲基乙基)-6-甲基苯基)乙基酯亞磷酸、BASF股份有限公司製造)；ADKSTAB 329K(ADEKA股份有限公司製造)；ADKSTAB PEP36(ADEKA股份有限公司製造)；ADKSTAB PEP-8(ADEKA股份有限公司製造)；Sandstab P-EPQ(Clariant公司製造)；Weston 618(GE公司製造)；Weston 619G(GE公司製造)；Ultranox 626(GE公司製造)以及Sumilizer GP(6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烷)住友化學股份有限公司製造)等。 Phosphorus-based antioxidants include, for example: Irgafos 168 (refer to (2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Co., Ltd.); Irgafos 12 (refer to [2-[[2,4, 8,10-Tetra-tert-butyldibenzo[d,f][1,3,2]di
Figure 106104734-A0202-12-0055-56
Phosphon-6-yl]oxy]ethyl]amine, manufactured by BASF Co., Ltd.); Irgafos 38 (bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Co., Ltd.); ADKSTAB 329K (manufactured by ADEKA Co., Ltd.); ADKSTAB PEP36 (manufactured by ADEKA Co., Ltd.); ADKSTAB PEP-8 (manufactured by ADEKA Co., Ltd.); Sandstab P-EPQ ( Weston 618 (manufactured by GE); Weston 619G (manufactured by GE); Ultranox 626 (manufactured by GE) and Sumilizer GP (6-[3-(3-tert-butyl-4-hydroxy-5 -Methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphospepane) Sumitomo Chemical Co., Ltd.) and so on.

硫系抗氧化劑可列舉如：硫二丙酸二月桂酯、二肉豆蔻酯或二硬脂酯等之硫二丙酸二烷酯化合物及肆[亞甲基(3-十二基硫)丙酸酯]甲烷等多元醇的β-烷基巰基丙酸酯化合物等。 Sulfur-based antioxidants include, for example, dilauryl thiodipropionate, dimyristyl, or distearyl dialkyl thiodipropionate, and tetra[methylene(3-dodecylthio)propane] β-Alkyl mercaptopropionate compounds of polyhydric alcohols such as methane, etc.

[10]其它成分 [10] Other ingredients

本發明之著色硬化性樹脂組成物中，可視需要而含有1種或2種以上之填充劑、樹脂(B)以外之高分子化合物、密合促進劑、紫外線吸收劑、抗凝集劑、有機酸、有機胺化合物、硬化劑等添加劑。 The colored curable resin composition of the present invention may optionally contain one or more fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-aggregation agents, organic Additives such as acids, organic amine compounds, hardeners, etc.

填充劑可列舉如：玻璃、氧化矽、氧化鋁等。樹脂(B)以外之高分子化合物可列舉如：聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚及聚氟烷基丙烯酸酯等。 As a filler, glass, silicon oxide, aluminum oxide, etc. are mentioned, for example. Examples of polymer compounds other than resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

密合促進劑可列舉如：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油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及3-巰基丙基三甲氧基矽烷等。 Adhesion accelerators include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyl Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, etc.

紫外線吸收劑可列舉如：2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑等苯并三唑化合物；2-羥基-4-辛基氧基二苯基酮等二苯基酮化合物；2,4-二-第三丁 基苯基-3,5-二-第三丁基-4-羥基苯甲酸酯等苯甲酸酯化合物；2-(4,6-二苯基-1,3,5-三

Figure 106104734-A0202-12-0057-57
-2-基)-5-己基氧基酚等三
Figure 106104734-A0202-12-0057-59
化合物等。 Examples of ultraviolet absorbers include: benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-octane Diphenyl ketone compounds such as oxydiphenyl ketone; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzoates Compound; 2-(4,6-diphenyl-1,3,5-tris
Figure 106104734-A0202-12-0057-57
-2-yl)-5-hexyloxyphenol, etc.
Figure 106104734-A0202-12-0057-59
compounds, etc.

抗凝集劑可列舉如：聚丙烯酸鈉等。 As an anti-agglutinating agent, sodium polyacrylate etc. are mentioned, for example.

有機酸係使用在顯影性之調整，具體而言可列舉如下：甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、二乙基乙酸、庚酸、辛酸等脂肪族單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十三烷二酸(brassylic acid)、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、環己烷二羧酸、伊康酸、檸康酸、順丁烯二酸、反丁烯二酸、中康酸等脂肪族二羧酸；1,2,3-丙三甲酸、烏頭酸、降莰三酸(camohoronic acid)等脂肪族三羧酸；苯甲酸、甲基苯甲酸、對異丙苯甲酸、3,4-二甲苯甲酸(hemellitic acid)、均三甲苯酸等芳香族單羧酸；鄰苯二甲酸、間苯二甲酸、對苯二甲酸等芳香族二羧酸；苯偏三酸、1,3,5-苯三甲酸、苯偏四甲酸、1,2,4,5-苯四甲酸等芳香族多元羧酸；等。 Organic acids are used for the adjustment of developability, and specific examples include aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid. Monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methyl propylene Diacid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid Aliphatic dicarboxylic acids such as enedioic acid and mesaconic acid; aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid, aconitic acid, and camohoronic acid; benzoic acid, toluic acid, Aromatic monocarboxylic acids such as p-isopropylbenzoic acid, 3,4-xylene carboxylic acid (hemellitic acid), and mesityl acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; Aromatic polycarboxylic acids such as trimellitic acid, 1,3,5-mellitic acid, trimellitic acid, 1,2,4,5-mellitic acid; etc.

有機胺可列舉如下：正丙基胺、異丙基胺、正丁基胺、異丁基胺、第二丁基胺、第三丁基胺、正戊基胺、正己基胺、正庚基胺、正 辛基胺、正壬基胺、正癸基胺、正十一基胺、正十二基胺等單烷基胺；環己基胺、2-甲基環己基胺、3-甲基環己基胺、4-甲基環己基胺等單環烷基胺；甲基乙基胺、二乙基胺、甲基正丙基胺、乙基正丙基胺、二-正丙基胺、二異丙基胺、二-正丁基胺、二異丁基胺、二-第二丁基胺、二-第三丁基胺、二-正戊基胺、二-正己基胺等二烷基胺；甲基環己基胺、乙基環己基胺等單烷基單環烷基胺；二環己基胺等二環烷基胺；二甲基乙基胺、甲基二乙基胺、三乙基胺、二甲基-正丙基胺、二乙基-正丙基胺、甲基二-正丙基胺、乙基二-正丙基胺、三-正丙基胺、三異丙基胺、三-正丁基胺、三異丁基胺、三-第二丁基胺、三-第三丁基胺、三-正戊基胺、三-正己基胺等三烷基胺；二甲基環己基胺、二乙基環己基胺等二烷基單環烷基胺；甲基二環己基胺、乙基二環己基胺、三環己基胺等單烷基二環烷基胺；2-胺基乙醇、3-胺基-1-丙醇、1-胺基-2-丙醇、4-胺基-1-丁醇、5-胺基-1-戊醇、6-胺基-1-己醇等單烷醇胺；4-胺基-1-環己醇等單環烷醇胺；二乙醇胺、二-正丙醇胺、二異丙醇胺、二-正丁醇胺、二異丁醇胺、二-正戊醇胺、二-正己醇胺等二烷醇胺； 二(4-環己醇)胺等二環烷醇胺；三乙醇胺、三-正丙醇胺、三異丙醇胺、三-正丁醇胺、三異丁醇胺、三-正戊醇胺、三-正己醇胺等三烷醇胺；三(4-環己醇)胺等三環烷醇胺；3-胺基-1,2-丙烷二醇、2-胺基-1,3-丙烷二醇、4-胺基-1,2-丁烷二醇、4-胺基-1,3-丁烷二醇、3-二甲基胺基-1,2-丙烷二醇、3-二乙基胺基-1,2-丙烷二醇、2-二甲基胺基-1,3-丙烷二醇、2-二乙基胺基-1,3-丙烷二醇等胺基烷烴二醇；4-胺基-1,2-環己烷二醇、4-胺基-1,3-環己烷二醇等胺基環烷烴二醇；1-胺基環戊酮甲醇、4-胺基環戊酮甲醇等含胺基之環烷酮甲醇；1-胺基環己酮甲醇、4-胺基環己酮甲醇、4-二甲基胺基環戊烷甲醇、4-二乙基胺基環戊烷甲醇、4-二甲基胺基環己烷甲醇、4-二乙基胺基環己烷甲醇等含胺基之環烷烴甲醇；β-丙胺酸、2-胺基丁酸、3-胺基丁酸、4-胺基丁酸、2-胺基異丁酸、3-胺基異丁酸、2-胺基戊酸、5-胺基戊酸、6-胺基己酸、1-胺基環丙烷羧酸、1-胺基環己烷羧酸、4-胺基環己烷羧酸等胺基羧酸；苯胺、鄰-甲基苯胺、間-甲基苯胺、對-甲基苯胺、對-乙基苯胺、對-正丙基苯胺、對-異丙基苯胺、對-正丁基苯胺、對-第三丁基苯胺、1-萘基胺、2-萘基胺、N,N-二甲基苯胺、N,N-二乙基苯胺、對-甲基-N,N-二甲基苯胺等芳香 族胺；鄰-胺基苯甲基醇、間-胺基苯甲基醇、對-胺基苯甲基醇、對-二甲基胺基苯甲基醇、對-二乙基胺基苯甲基醇等胺基苯甲基醇；鄰-胺基酚、間-胺基酚、對-胺基酚、對-二甲基胺基酚、對-二乙基胺基酚等胺基酚；間-胺基苯甲酸、對-胺基苯甲酸、對-二甲基胺基苯甲酸、對-二乙基胺基苯甲酸等胺基苯甲酸等。 The organic amines include n-propylamine, isopropylamine, n-butylamine, isobutylamine, 2-butylamine, 3-butylamine, n-pentylamine, n-hexylamine, n-heptylamine Amine, positive Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine; cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine , 4-methylcyclohexylamine and other monocyclic alkylamines; methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine Dialkylamines such as base amine, di-n-butylamine, diisobutylamine, di-2-butylamine, di-tert-butylamine, di-n-pentylamine, and di-n-hexylamine; Monoalkyl monocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; dicycloalkylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine , dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, Tri-n-butylamine, triisobutylamine, tri-2-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine and other trialkylamines; dimethyl Dialkyl monocycloalkylamines such as cyclohexylamine and diethylcyclohexylamine; monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine; 2- Aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1 -Monoalkanolamines such as hexanol; monocycloalkanolamines such as 4-amino-1-cyclohexanol; diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diethanolamine Isobutanolamine, di-n-pentanolamine, di-n-hexanolamine and other dialkanolamines; Dicycloalkanolamines such as bis(4-cyclohexanol)amine; triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanol Tri-alkanolamines such as amines, tri-n-hexanolamine; tricycloalkanolamines such as tris(4-cyclohexanol)amine; 3-amino-1,2-propanediol, 2-amino-1,3 -Propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2-propanediol, 3 - Diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol and other aminoalkanes Diols; 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol and other aminocycloalkanediols; 1-aminocyclopentanone methanol, 4-aminocyclopentanone - Aminocyclopentanone methanol and other amino-containing cycloalkanone methanol; 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4-diaminocyclopentane methanol Ethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol and other amino-containing cycloalkanemethanol; β-alanine, 2-amino Butyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-amine Amine carboxylic acids such as aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid; aniline, o-methylaniline, m-methyl aniline Aniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-isopropylaniline, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2 -Naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, p-methyl-N,N-dimethylaniline and other aromatics Family amines; o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzene Methyl alcohol and other aminobenzyl alcohols; o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol and other aminophenols ; M-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and other aminobenzoic acids, etc.

硬化劑可列舉如：可藉由加熱而與樹脂(B)中的羧基反應而使樹脂(B)交聯之化合物、可單獨聚合而使著色圖案硬化之化合物等。其具體例可列舉如：環氧化合物、氧雜環丁烷化合物等。硬化劑可僅使用1種，亦可併用2種以上。 As a hardening agent, the compound which can react with the carboxyl group in resin (B) by heating, and can bridge|crosslink resin (B), the compound which can be polymerized independently and can harden a colored pattern, etc. are mentioned, for example. Specific examples thereof include epoxy compounds, oxetane compounds, and the like. Only one type of curing agent may be used, or two or more types may be used in combination.

環氧化合物可列舉如：雙酚A系環氧樹脂、氫化雙酚A系環氧樹脂、雙酚F系環氧樹脂、氫化雙酚F系環氧樹脂、酚醛清漆型環氧樹脂、其它的芳香族系環氧樹脂、脂環族系環氧樹脂、雜環式環氧樹脂、縮水甘油酯系樹脂、縮水甘油基胺系樹脂、環氧化油等環氧樹脂和該等環氧樹脂之溴化衍生物、環氧樹脂及其溴化衍生物以外之脂肪族、脂環族或芳香族之環氧化合物、丁二烯的(共)聚合物之環氧化物、異戊二烯的(共)聚合物之環氧化物、(甲基)丙烯酸縮水甘油酯之(共)聚合物、三聚異氰酸三縮水甘油酯等。環氧樹脂之市售品可列舉：鄰甲酚酚醛清漆型環氧樹脂、「Sumiepoxy(註冊商標)ESCN-195XL-80」(住友 化學股份有限公司製)等。 Examples of epoxy compounds include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolak-type epoxy resins, and others. Aromatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, and bromines of these epoxy resins Aliphatic, alicyclic or aromatic epoxy compounds other than brominated derivatives, epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, (co)polymers of isoprene ) epoxide of polymer, (co)polymer of glycidyl (meth)acrylate, triglycidyl triisocyanate, etc. Commercially available epoxy resins include: o-cresol novolak epoxy resin, "Sumiepoxy (registered trademark) ESCN-195XL-80" (Sumitomo Chemical Co., Ltd.), etc.

氧雜環丁烷化合物可列舉如：雙氧雜環丁烷碳酸酯、伸苯二甲基雙氧雜環丁烷、雙氧雜環丁烷己二酸酯、雙氧雜環丁烷對苯二甲酸酯、環己烷二羧酸雙氧雜環丁烷等。 Examples of the oxetane compound include: dioxetane carbonate, xylylene dioxetane, dioxetane adipate, dioxetane p-benzene Diformate, cyclohexanedicarboxylic acid dioxetane, etc.

本發明之著色硬化性樹脂組成物，在含有環氧化合物、氧雜環丁烷化合物等作為硬化劑時，亦可包含能使環氧化合物之環氧基、氧雜環丁烷化合物之氧雜環丁烷骨架開環聚合之化合物。該化合物可列舉如：多元羧酸、多元羧酸酐、酸產生劑等。 When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may also contain an epoxy group capable of making an epoxy compound and an oxetane compound of an oxetane compound. The compound of ring-opening polymerization of cyclobutane skeleton. As such a compound, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, an acid generator, etc. are mentioned, for example.

多元羧酸可列舉如：3,4-二甲基鄰苯二甲酸、1,2,4,5-苯四甲酸、苯偏三酸、1,4,5,8-萘四羧酸、3,3',4,4'-二苯基酮四羧酸等芳香族多元羧酸；1,2,3,4-丁烷四羧酸等脂肪族多元羧酸；六氫鄰苯二甲酸、3,4-二甲基四氫鄰苯二甲酸、六氫間苯二甲酸、六氫對苯二甲酸、1,2,4-環戊烷三羧酸、1,2,4-環己烷三羧酸、環戊烷四羧酸、1,2,4,5-環己烷四羧酸等脂環式多元羧酸；等。 Examples of polycarboxylic acids include: 3,4-dimethylphthalic acid, 1,2,4,5-mellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 ,3',4,4'-Aromatic polycarboxylic acids such as diphenylketone tetracarboxylic acid; Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid; Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexane Alicyclic polycarboxylic acids such as tricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid; etc.

多元羧酸酐可列舉如：鄰苯二甲酸酐、1,2,4,5-苯四甲酸酐、苯偏三酸酐、3,3',4,4'-二苯基酮四羧酸二酐等芳香族多元羧酸酐；伊康酸酐、琥珀酸酐、檸康酸酐、十二烯琥珀酸酐、1,2,3-丙三甲酸酐、順丁烯二酸酐、1,2,3,4-丁烷四羧酸二 酐等脂肪族多元羧酸酐；六氫鄰苯二甲酸酐、3,4-二甲基四氫鄰苯二甲酸酐、1,2,4-環戊烷三羧酸酐、1,2,4-環己烷三羧酸酐、環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、海米酸酐、納迪克酸酐(nadic acid anhydride)等脂環式多元羧酸酐；乙二醇雙(三苯六甲酸)、丙三醇參(三苯六甲酸酐)等含酯基之羧酸酐；等。 Examples of polyvalent carboxylic anhydrides include: phthalic anhydride, 1,2,4,5-mellitic anhydride, trimellitic anhydride, 3,3',4,4'-diphenylketone tetracarboxylic dianhydride Aromatic polycarboxylic acid anhydrides such as Iconic anhydride, succinic anhydride, citraconic anhydride, dodecylsuccinic anhydride, 1,2,3-propanetricarboxylic anhydride, maleic anhydride, 1,2,3,4-butane Tetracarboxylate Aliphatic polycarboxylic acid anhydrides such as anhydrides; hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic acid anhydride, 1,2,4- Cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hemic anhydride, nadic acid anhydride and other alicyclic polybasic Carboxylic acid anhydrides; carboxylic acid anhydrides containing ester groups such as ethylene glycol bis(trimellitic acid), glycerol ginseng (trimellitic acid anhydride), etc.

羧酸酐係可使用市售者作為環氧樹脂硬化劑。環氧樹脂硬化劑可列舉如：商品名稱「Adeka Hardener(註冊商標)EH-700」(ADEKA股份有限公司製造)、商品名稱「Rikacid(註冊商標)HH」(新日本理化股份有限公司製造)、商品名稱「MH-700」(新日本理化股份有限公司製造)等。 As the carboxylic acid anhydride type, a commercially available one can be used as the epoxy resin hardener. Examples of epoxy resin hardeners include: trade name "Adeka Hardener (registered trademark) EH-700" (manufactured by ADEKA Co., Ltd.), trade name "Rikacid (registered trademark) HH" (manufactured by Nippon Chemical Co., Ltd.), Brand name "MH-700" (manufactured by Nippon Chemical Co., Ltd.), etc.

酸產生劑可列舉如：4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基/甲基/苯甲基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪鎓對甲苯磺酸鹽、二苯基錪鎓六氟銻酸酯等鎓鹽和甲苯磺酸硝基苯甲酯、苯偶姻甲苯磺酸酯等。 Examples of acid generators include: 4-hydroxyphenyldimethyl perionate p-toluenesulfonate, 4-hydroxyphenyldimethyl perionate hexafluoroantimonate, 4-acetyloxyphenyldimethyl perionate para-toluene Tosylate, 4-Acetyloxyphenyl/methyl/benzyl perylene hexafluoroantimonate, triphenyl perylene p-toluenesulfonate, triphenyl perylene hexafluoroantimonate, diphenyl Onium salts such as iodonium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

<著色硬化性樹脂組成物之製造方法> <Manufacturing method of colored curable resin composition>

本發明之著色硬化性樹脂組成物係可藉由混合著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)，以及視需要之溶劑(E)、硫醇化合物(T)、調平劑(F)、聚合起始助劑(D1)、抗氧化劑(G)及其它成分而調製。 The coloring curable resin composition of the present invention can be prepared by mixing colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D), and optionally solvent (E), sulfur The alcohol compound (T), the leveling agent (F), the polymerization initiation adjuvant (D1), the antioxidant (G), and other components are prepared.

<彩色濾光片及其製造方法、彩色濾光片以及顯示裝置> <Color filter and its manufacturing method, color filter, and display device>

本發明之著色硬化性樹脂組成物係作為彩色濾光片之材料為有用。由本發明之著色硬化性樹脂組成物所形成之彩色濾光片亦屬於本願發明之範疇。彩色濾光片亦可形成著色圖案。 The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also belongs to the scope of the present invention. Color filters can also form colored patterns.

由本發明之著色硬化性樹脂組成物製造著色圖案之方法，可列舉如：光蝕刻法、噴墨法、印刷法等。其中，以光蝕刻法為佳。光蝕刻法，係將著色硬化性樹脂組成物塗佈於基板，使之乾燥而形成著色組成物層，並經由光罩將該著色組成物層曝光、進行顯影之方法。光蝕刻法中，可藉由於曝光時不使用光罩、及/或不進行顯影，而形成上述著色組成物層的硬化物之著色塗膜。如此所形成之著色圖案、著色塗膜係本發明之彩色濾光片。 The method of producing a colored pattern from the colored curable resin composition of the present invention includes, for example, a photoetching method, an inkjet method, a printing method, and the like. Among them, the photo-etching method is preferred. The photolithography method is a method of applying a coloring curable resin composition to a substrate, drying it to form a coloring composition layer, exposing the coloring composition layer through a mask, and developing the coloring composition layer. In the photolithography method, a colored coating film of the cured product of the colored composition layer can be formed by not using a mask and/or without performing development during exposure. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

本發明之彩色濾光片，典型者係使用作為綠色像素。 The color filter of the present invention is typically used as a green pixel.

基板係可使用石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、表面經二氧化矽塗覆之鈉鈣玻璃等之玻璃板，聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板，矽，於上述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。在該等基板上，亦可形成其它的彩色濾光片層、樹脂層、電晶體、電路等。 The substrates can be glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica, polycarbonate, polymethyl methacrylate, polyterephthalate, etc. Resin plates such as ethylene formate, silicon, aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may also be formed.

藉由光蝕刻法之各色像素的形成，係可以習知或常用的裝置、條件下進行，例如可以後述方式進行 製作。首先，將著色硬化性樹脂組成物塗佈於基板上，藉由加熱乾燥(預烘烤)及/或減壓乾燥以去除溶劑等揮發成分而使其乾燥，得到平滑之著色組成物層。塗佈方法可列舉如：旋塗法、狹縫塗佈法、狹縫及旋塗法等。 The formation of each color pixel by photolithography can be carried out under conventional or commonly used devices and conditions, for example, it can be carried out in the following manner. make. First, the colored curable resin composition is coated on a substrate, and dried by heating and drying (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned, for example.

進行加熱乾燥時之溫度，係以30至120℃為佳，以50至110℃更佳。而且，加熱時間係以10秒鐘至5分鐘者為佳，以30秒鐘至3分鐘者更佳。進行減壓乾燥時，以在50至150Pa之壓力下、20至25℃之溫度範圍進行為佳。著色組成物層之膜厚並無特別限定，只要因應目的之彩色濾光片的膜厚而適當地選擇即可。 The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. Moreover, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When drying under reduced pressure, it is better to carry out under the pressure of 50 to 150Pa and the temperature range of 20 to 25°C. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the intended color filter.

繼而，著色組成物層係經由用以形成目的之著色圖案的光罩而曝光。該光罩上之圖案並無特別限定，可使用依目的用途之圖案。曝光所使用之光源係以產生波長250至450nm的光之光源為佳。例如：可將未達350nm之光，使用阻隔波長區域未達350nm之光之濾光片而截斷未達350nm之光、或亦可使用取出436nm附近、408nm附近、365nm附近之光的波長之帶通濾光片，而選擇性地取出436nm附近、408nm附近、365nm附近的光。 Then, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the purpose can be used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, the light below 350nm can be cut off by a filter that blocks the light below 350nm, or the wavelength band of light near 436nm, near 408nm, and near 365nm can be used. Through the filter, light around 436nm, around 408nm, and around 365nm can be selectively extracted.

具體而言，光源可列舉如：水銀燈、發光二極體、金屬鹵素燈、鹵素燈等。 Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned, for example.

曝光係可於曝光面整體均勻地照射平行光線、或將光罩與形成有著色組成物層之基板進行正確的對位，故以使用光罩對準機及步進機等曝光裝置為佳。 The exposure system can uniformly irradiate the entire exposure surface with parallel light or accurately align the mask and the substrate on which the coloring composition layer is formed. Therefore, it is preferable to use an exposure device such as a mask aligner and a stepper.

藉由使曝光後之著色組成物層接觸顯影液 進行顯影，可於基板上形成著色圖案。藉由顯影，著色組成物層之未曝光部會溶解於顯影液而被去除。 By contacting the exposed coloring composition layer with the developer After developing, a colored pattern can be formed on the substrate. By developing, the unexposed portion of the coloring composition layer is dissolved in the developing solution and removed.

顯影液係例如以氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液為佳。該等鹼性化合物之水溶液中之濃度，以0.01至10質量%為佳，以0.03至5質量%更佳。再者，顯影液亦可包含界面活性劑。 The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

顯影方法可為覆液(puddle)法、浸漬法及噴霧法等之任一者。進一步顯影時亦可將基板傾斜成任意的角度。顯影後，以進行水洗為佳。 The development method may be any of a puddle method, a dipping method, a spray method, and the like. During further development, the substrate may be inclined at an arbitrary angle. After developing, it is preferable to wash with water.

再者，以對所得之著色圖案進行後烘者為佳。後烘的溫度係以150至250℃為佳，以160至235℃更佳。後烘時間係以1至120分鐘為佳，以10至60分鐘更佳。 Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

由於所得彩色濾光片之膜厚會影響相隣的像素，故以盡可能地薄為佳。尤其，如為厚膜，在製作液晶面板時，光源的光會有通過2色以上的像素而漏出之情形，由斜向看面板時，會有顏色失去彩度之疑慮。彩色濾光片之膜厚，係以3μm以下為佳，以2.8μm以下更佳。彩色濾光片之膜厚的下限並無特別限定，惟通常為1μm以上，亦可為1.5μm以上。 Since the film thickness of the obtained color filter affects adjacent pixels, it is preferable to be as thin as possible. In particular, if the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is produced, and the color may lose its chromaticity when the panel is viewed obliquely. The film thickness of the color filter is preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the color filter is not particularly limited, but is usually 1 μm or more, and may be 1.5 μm or more.

本發明之彩色濾光片，係可使用作為顯示裝置(液晶顯示裝置、有機EL裝置、電子紙等)及固體攝影元件所使用之彩色濾光片。 The color filter of the present invention can be used as a color filter used for display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[實施例] [Example]

以下係表示實施例及比較例以進一步具體地說明本發明，惟本發明不受限於該等例。例中，表示含量乃至使用量之%及份，若無特別記載，則為質量基準。 The following are examples and comparative examples to further specifically illustrate the present invention, but the present invention is not limited to these examples. In the example, the % and the part indicating the content and the usage amount are the quality standards unless otherwise specified.

<合成例1：樹脂溶液(B1)之調製> <Synthesis Example 1: Preparation of Resin Solution (B1)>

於具備回流冷卻器、滴液漏斗及攪拌機之1L燒瓶內流通適量的氮以取代為氮氣環境，饋入丙二醇單甲基醚乙酸酯280份，進行攪拌同時加熱至80℃。繼而，耗時5小時將混合有丙烯酸38份、3,4-環氧基三環[5.2.1.02,6]癸烷-8-基丙烯酸酯及3,4-環氧基三環[5.2.1.02,6]癸烷-9-基丙烯酸酯之混合物289份、丙二醇單甲基醚乙酸酯125份之混合溶液滴入。另一方面，耗時6小時滴入將2,2-偶氮雙(2,4-二甲基戊腈)33份溶解於丙二醇單甲基醚乙酸酯235份之混合溶液。結束滴入後，以同樣溫度保持4小時之後，冷卻至室溫，得到包含B型黏度(23℃)125mPas、固形物成分37.0質量%、溶液酸值27mg-KOH/g之樹脂的樹脂溶液(B1)。樹脂溶液(B1)中所含樹脂之重量平均分子量Mw為9200、分子量分佈為2.08。 A proper amount of nitrogen was circulated in a 1 L flask equipped with a reflux cooler, dropping funnel and agitator to replace the nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was fed, and heated to 80° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate, and 3,4-epoxytricyclo[5.2 289 parts of a mixture of 1.0 2,6 ] decane-9-yl acrylate and a mixed solution of 125 parts of propylene glycol monomethyl ether acetate were added dropwise. On the other hand, a mixed solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the same temperature was maintained for 4 hours, and then cooled to room temperature to obtain a resin solution ( B1). The weight average molecular weight Mw of the resin contained in the resin solution (B1) was 9200, and the molecular weight distribution was 2.08.

樹脂溶液(B1)中所含的樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)之測定，係使用GPC法並依下述條件進行。將通過下述條件所得之以聚苯乙烯換算的重量平均分子量與數量平均分子量之比(Mw/Mn)作為分子量分佈。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin contained in the resin solution (B1) were measured using the GPC method under the following conditions. The ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene to the number average molecular weight obtained under the following conditions was used as the molecular weight distribution.

裝置：HLC-8120GPC(Tosoh股份有限公司製造)、 管柱：TSK-GELG2000HXL、管柱溫度：40℃、溶媒：THF、流速：1.0mL/分鐘、受檢液固形物成分濃度：0.001至0.01質量%、注入量：50μL、檢測器：RI、校正用標準物質：TSK STANDARD POLYSTYRENE Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.), Column: TSK-GELG2000HXL, column temperature: 40°C, solvent: THF, flow rate: 1.0 mL/min, test liquid solid content concentration: 0.001 to 0.01 mass %, injection volume: 50 μL, detector: RI, calibration Standard material used: TSK STANDARD POLYSTYRENE

F-40、F-4、F-288、A-2500、A-500(Tosoh股份有限公司製)。 F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.).

<合成例2：顏料分散液(A1)之調製> <Synthesis Example 2: Preparation of Pigment Dispersion Liquid (A1)>

Figure 106104734-A0202-12-0067-27
Figure 106104734-A0202-12-0067-27

將上述成分混合，並使用珠磨機使顏料充分地分散，藉此得到顏料分散液(A1)。 The above components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A1).

<合成例3：顏料分散液(A2)之調製> <Synthesis Example 3: Preparation of Pigment Dispersion Liquid (A2)>

Figure 106104734-A0202-12-0067-28
Figure 106104734-A0202-12-0067-28

將上述成分混合，並使用珠磨機使顏料充分地分散，藉此得到顏料分散液(A2)。 The above components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A2).

<合成例4：顏料分散液(A3)之調製> <Synthesis Example 4: Preparation of Pigment Dispersion Liquid (A3)>

Figure 106104734-A0202-12-0068-29
Figure 106104734-A0202-12-0068-29

將上述成分混合，並使用珠磨機使顏料充分地分散，藉此得到顏料分散液(A3)。 The above components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (A3).

<實施例1至5及比較例1至5> <Examples 1 to 5 and Comparative Examples 1 to 5>

(1)著色硬化性樹脂組成物之調製 (1) Preparation of colored curable resin composition

以成為表8所記載之調配量的方式，混合表8所記載之成分，得到著色硬化性樹脂組成物。表8中之各成分的調配量之單位係「質量份」。各成分的內容詳如下述。 The components shown in Table 8 were mixed so that the compounding quantity described in Table 8 might be obtained, and a colored curable resin composition was obtained. The unit of the compounding quantity of each component in Table 8 is "mass part". The content of each component is as follows.

[1]顏料分散液(A1)：合成例2所得之顏料分散液(A1)、[2]顏料分散液(A2)：合成例3所得之顏料分散液(A2)、[3]顏料分散液(A3)：合成例4所得之顏料分散液(A3)、[4]樹脂溶液(B1)：合成例1所得之樹脂溶液(B1)、[5]聚合性化合物(C1)：環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯(EO改質量6)(新中村化學工業股份有限公司製造之商品名稱「M-DPH-6E」)、[6]聚合性化合物(C2)：二新戊四醇六丙烯酸酯(新中村化學工業股份有限公司製造之商品名稱「A-9550」)、[7]聚合起始劑(D1)：下述式表示之化合物、

Figure 106104734-A0202-12-0069-30
[1] Pigment dispersion (A1): Pigment dispersion (A1) obtained in Synthesis Example 2, [2] Pigment dispersion (A2): Pigment dispersion (A2) obtained in Synthesis Example 3, [3] Pigment dispersion (A3): Pigment dispersion liquid (A3) obtained in Synthesis Example 4, [4] Resin solution (B1): Resin solution (B1) obtained in Synthesis Example 1, [5] Polymerizable compound (C1): Ethylene oxide Modified dipivalerythritol hexa(meth)acrylate (EO modified mass 6) (trade name "M-DPH-6E" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), [6] Polymerizable compound (C2) : Dipivalerythritol hexaacrylate (trade name "A-9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), [7] Polymerization initiator (D1): a compound represented by the following formula,
Figure 106104734-A0202-12-0069-30

[8]聚合起始劑(D2)：2,2',4-參(2-氯苯基)-5-(3,4-二甲氧基苯基)-4,5-二苯基-1,1'-聯咪唑(CHEMBRIDGE INTERNATIONAL公司製造之商品名稱「TCDM」)、[9]硫醇化合物(T1)：2-巰基苯并噻唑(三新化學工業股份有限公司製造之商品名稱「SANCELER M」)、[10]添加劑：3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越矽酮股份有限公司製造之商品名稱「KBM-503」)、[11]調平劑(F1)：聚醚改質聚矽氧油(Toray Dow Corning股份有限公司製造之商品名稱「Toray Silicone SH8400」)、[12]溶劑(E1)：丙二醇單甲基醚乙酸酯。 [8] Polymerization initiator (D2): 2,2',4-para(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl- 1,1'-biimidazole (trade name "TCDM" manufactured by CHEMBRIDGE INTERNATIONAL), [9]thiol compound (T1): 2-mercaptobenzothiazole (trade name "SANCELER" manufactured by Sanxin Chemical Industry Co., Ltd. M”), [10] Additives: 3-methacryloyloxypropyltrimethoxysilane (trade name “KBM-503” manufactured by Shin-Etsu Silicone Co., Ltd.), [11] Leveling agent (F1) : Polyether-modified polysiloxane oil (trade name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.), [12] Solvent (E1): propylene glycol monomethyl ether acetate.

Figure 106104734-A0202-12-0069-31
Figure 106104734-A0202-12-0069-31

(2)著色塗膜之製作 (2) Production of colored coating films

於2吋見方的玻璃基板(「EAGLE XG」；Corning公司製造)上，以旋塗法塗佈著色硬化性樹脂組成物之後，在100℃預烘烤3分鐘。冷卻後，對塗佈有該著色硬化性樹脂組成物之基板使用曝光機(TME-150RSK；TOPCON股份有限公司製造)，在大氣環境下，以80mJ/cm2之曝光量(365nm基準)進行光照射。然後在烘箱中，在230℃進行30分鐘之後烘佈，得到著色塗膜。 The colored curable resin composition was applied on a 2-inch square glass substrate (“EAGLE XG”; manufactured by Corning Corporation) by spin coating, and then prebaked at 100° C. for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used on the substrate coated with the colored curable resin composition, and light was exposed at an exposure amount of 80 mJ/cm 2 (365 nm reference) in an atmospheric environment. irradiate. Then, the cloth was baked at 230° C. for 30 minutes in an oven to obtain a colored coating film.

(3)膜厚測定 (3) Measurement of film thickness

對於上述(2)所得之著色塗膜，將膜厚使用膜厚度測定裝置(DEKTAK3；日本真空技術股份有限公司製造)測定。將結果呈示於表9。 The film thickness of the colored coating film obtained in the above (2) was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9.

(4)色度測定 (4) Chromaticity measurement

對於上述(2)所得之著色塗膜，使用比色計(OSP-SP-200；Olympus股份有限公司製造)測定分光，使用C光源之特性函數測定CIE(國際照明委員會)之XYZ表色系統中之xy色度座標(x,y)及刺激值(Y)。(Y)值越大表示亮度越高。將結果呈示於表9。 For the colored coating film obtained in the above (2), the spectrometer was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the XYZ colorimetric system of CIE (Commission Internationale des Illuminations) was measured using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and the stimulus value (Y). The larger the (Y) value, the higher the brightness. The results are shown in Table 9.

(5)著色圖案之製作及著色圖案之形狀評估 (5) Production of colored patterns and shape evaluation of colored patterns

於2吋見方的玻璃基板(「EAGLE XG」；Corning公司製造)上，以使後烘後之膜厚成為2.7μm之方式，以旋塗法塗佈著色硬化性樹脂組成物之後，在100℃預烘3分鐘形成組成物層。冷卻後，將形成有組成物層之基板與石英 玻璃製光罩作成80μm之間隔，使用曝光機(TME-150RSK；TOPCON股份有限公司製造)，在大氣環境下，以50mJ/cm2之曝光量(365nm基準)進行光照射。另外，光罩係使用形成有50μm之線寬/間距(Line/Space)圖案的光罩。將光照射後之組成物層，在包含非離子系界面活性劑0.12%與氫氧化鉀0.04%之水溶液中，於25℃浸漬60秒鐘使顯影，水洗後，在烘箱中，於230℃進行30分鐘之後烘，藉此得到著色圖案。對於所得之著色圖案使用膜厚度測定裝置(DEKTAK3；日本真空技術股份有限公司製造)測定膜厚，確認膜厚為2.7μm。 On a 2-inch-square glass substrate (“EAGLE XG”; manufactured by Corning Corporation), the coloring curable resin composition was spin-coated so that the film thickness after post-baking was 2.7 μm, and then the coloring curable resin composition was applied at 100°C. The composition layer was formed by prebaking for 3 minutes. After cooling, the substrate on which the composition layer was formed and the mask made of quartz glass were made at an interval of 80 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to expose an exposure amount of 50 mJ/cm 2 in an atmospheric environment. (365 nm reference) was irradiated with light. In addition, the photomask in which the line/space (Line/Space) pattern of 50 micrometers was formed was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 60 seconds for development, washed with water, and then carried out in an oven at 230°C It was baked after 30 minutes, whereby a colored pattern was obtained. The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was confirmed that the film thickness was 2.7 μm.

對於所得著色圖案，使用掃描電子顯微鏡(S-4000；Hitachi High-Technologies股份有限公司製造)觀察形狀，依據下述之評估基準評估，將結果呈示於表9。 About the obtained coloring pattern, the shape was observed using a scanning electron microscope (S-4000; Hitachi High-Technologies Co., Ltd. make), and it evaluated based on the following evaluation criteria, and the result is shown in Table 9.

A：著色圖案形狀係如第1圖所示之正錐形狀。 A: The shape of the coloring pattern is a straight cone shape as shown in FIG. 1 .

B：著色圖案形狀係如第2圖所示之倒錐形狀。 B: The shape of the coloring pattern is an inverted tapered shape as shown in FIG. 2 .

Figure 106104734-A0202-12-0072-32
Figure 106104734-A0202-12-0072-32

實施例1至5及比較例1至5中，著色塗膜之色度座標(x,y)為統一。於實施例1至5，係可兼具高亮度與良好的著色圖案之形狀。相對於此，於比較例1至2為亮度不足，於比較例1至5中，著色圖案成為倒錐形狀。 In Examples 1 to 5 and Comparative Examples 1 to 5, the chromaticity coordinates (x, y) of the colored coating films were unified. In Examples 1 to 5, it is a shape that can have both high brightness and a good coloring pattern. On the other hand, in Comparative Examples 1 to 2, the brightness was insufficient, and in Comparative Examples 1 to 5, the colored pattern had a reverse tapered shape.

[產業上之可利用性] [Industrial Availability]

依據本發明之著色硬化性樹脂組成物，可提供亮度高且圖案形狀優異之彩色濾光片及含有該濾光片之顯示裝置 According to the colored curable resin composition of the present invention, a color filter with high brightness and excellent pattern shape and a display device including the filter can be provided

由於本案的圖為著色圖案的概略剖視圖，並非本案的代表圖。故本案無指定代表圖。 Since the figure of this case is a schematic cross-sectional view of a coloring pattern, it is not a representative figure of this case. Therefore, there is no designated representative map in this case.

Claims (6)

一種著色硬化性樹脂組成物，其包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)；上述著色劑(A)含有C.I.顏料綠59；上述著色劑(A)100質量%中，上述C.I.顏料綠59的含量為30質量%以上；上述聚合性化合物(C)含有由環氧乙烷改質二新戊四醇五(甲基)丙烯酸酯及環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的(甲基)丙烯酸酯(c1)。 A coloring curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D); the above-mentioned colorant (A) contains C.I. Pigment Green 59; the above-mentioned coloring In 100 mass % of agent (A), the content of C.I. Pigment Green 59 is 30 mass % or more; At least one (meth)acrylate (c1) selected from the group of ethylene oxide-modified dipivalerythritol hexa(meth)acrylates. 如申請專利範圍第1項所述之著色硬化性樹脂組成物，其中，上述聚合性化合物(C)進一步含有上述(甲基)丙烯酸酯(c1)以外之含(甲基)丙烯醯基的化合物(c2)。 The colored curable resin composition according to claim 1, wherein the polymerizable compound (C) further contains a (meth)acryloyl group-containing compound other than the (meth)acrylate (c1) (c2). 如申請專利範圍第2項所述之著色硬化性樹脂組成物，其中，含(甲基)丙烯醯基的化合物(c2)係由三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、參(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯、環氧乙烷改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質新戊四醇四(甲基)丙烯酸酯、環氧丙烷改質二新戊四醇六(甲基)丙烯酸酯、己內酯改質新戊四醇四(甲基)丙烯 酸酯及己內酯改質二新戊四醇六(甲基)丙烯酸酯所成群中選出之至少1種的化合物。 The colored curable resin composition according to claim 2, wherein the (meth)acryloyl group-containing compound (c2) is composed of trimethylolpropane tri(meth)acrylate, neopentyltetrakis Alcohol Tri(meth)acrylate, Neotaerythritol Tetra(meth)acrylate, Dipivalerythritol Penta(meth)acrylate, Dipivalerythritol Hex(meth)acrylate, Tripivale Tetraol octa(meth)acrylate, Tripivalerythritol hepta(meth)acrylate, Tetrapentaerythritol ten(meth)acrylate, Tetranetaerythritol nona(meth)acrylate, Ref. (2-(meth)acryloyloxyethyl) isocyanurate, ethylene oxide-modified neotaerythritol tetrakis(meth)acrylate, propylene oxide-modified neotaerythritol tetrakis(methyl) Acrylates, Propylene oxide modified dipivoerythritol hexa(meth)acrylate, caprolactone modified neotaerythritol tetra(meth)propylene A compound of at least one selected from the group consisting of acid esters and caprolactone-modified dipivoerythritol hexa(meth)acrylates. 如申請專利範圍第1項或第2項所述之著色硬化性樹脂組成物，其中，在上述聚合性化合物(C)100質量%中，上述(甲基)丙烯酸酯(c1)之含量為20質量%以上。 The coloring curable resin composition according to claim 1 or claim 2, wherein the content of the (meth)acrylate (c1) is 20% in 100% by mass of the polymerizable compound (C) mass % or more. 一種彩色濾光片，係由申請專利範圍第1至3項中任一項所述之著色硬化性樹脂組成物所形成。 A color filter is formed of the coloring curable resin composition described in any one of claims 1 to 3 of the patent application scope. 一種顯示裝置，其包含申請專利範圍第5項所述之彩色濾光片。 A display device comprising the color filter described in item 5 of the patent application scope.
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