TWI419905B - Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix - Google Patents

Black-colored photosensitive resin composition, black matrix prepared by using thereof and color filter comprising the black matrix Download PDF

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TWI419905B
TWI419905B TW100108441A TW100108441A TWI419905B TW I419905 B TWI419905 B TW I419905B TW 100108441 A TW100108441 A TW 100108441A TW 100108441 A TW100108441 A TW 100108441A TW I419905 B TWI419905 B TW I419905B
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compound
photosensitive resin
resin composition
black
black photosensitive
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TW100108441A
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TW201136955A (en
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Joo-Sung Kim
Kyu-Chul Shin
Sung-Hun Youk
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Description

黑色感光性樹脂組成物、使用其所製造之黑色矩陣及具備該黑色矩陣之彩色濾光片 Black photosensitive resin composition, black matrix manufactured using the same, and color filter having the black matrix

本發明係有關於一種黑色感光性樹脂組成物、使用其所製造之黑色矩陣(Black Matrix)及具備該黑色矩陣之彩色濾光片(Color Filter)，具體地，係有關於與基板間的密著性及儲藏安定性優異，藉由邊維持感度邊減少曝後烤處理時的熱流動性，而可改善微細圖型形成時，因位置所造成的光學密度差的一種黑色感光性樹脂組成物、使用其所製造之黑色矩陣及具備該黑色矩陣之彩色濾光片。 The present invention relates to a black photosensitive resin composition, a black matrix (Black Matrix) manufactured using the same, and a color filter having the black matrix, and specifically, a dense interface with the substrate. It is excellent in stability and storage stability, and it is possible to improve the thermal fluidity during the post-exposure treatment while maintaining the sensitivity, and to improve the black photosensitive resin composition due to the difference in optical density due to the position during formation of the fine pattern. A black matrix manufactured by the black matrix and a color filter having the black matrix are used.

於液晶顯示器的彩色濾光片中，黑色矩陣是擔任遮蔽透過透明化小電極外而未控制的光，進而提升對比度的角色，就材料而言，是以鉻或樹脂製造。於鉻的場合，雖然薄膜遮光性能及圖型直進性表現優異，但以環境問題、高反射率、工程面的高費用等問題考量，樹脂系的黑色矩陣較佳。 In the color filter of a liquid crystal display, the black matrix serves to shield the light that is not controlled by the transparent small electrode, thereby enhancing the contrast. In terms of material, it is made of chrome or resin. In the case of chromium, although the film has excellent light-shielding performance and pattern straightness, the resin-based black matrix is preferable in consideration of environmental problems, high reflectance, and high cost of the engineering surface.

但是，於樹脂黑色矩陣製造用的感光性樹脂組成物中，由於對感光性具有重大妨害的黑色顏料，因此無法高效率形成光致交聯，即所謂的「底切」，具有因顯影液過度侵蝕、顯現安定性不足與光感度下降等問題。南韓專利申請案第1995-0702313號中所揭露的發明，是使用一種為了提升感度，而將鎘系樹脂使用至黑色矩陣用感光性樹脂組成物，但其巨大的分子結構會造成黏著性下降。特別是於黑色矩陣的場合，為了達到所要求的光學密 度而將黑色顏料的含量提高，因而具有黏著性大幅下降的問題。於此，南韓專利申請案第2000-0055255號，雖然公開各式各樣的單體進行共聚合的鎘系樹脂及矽烷系偶聯劑，但儲藏安定性不佳，藉由曝後烤處理時的熱流形成微細圖型時，具有因位置所造成的光學密度差的問題。 However, in the photosensitive resin composition for producing a resin black matrix, since a black pigment having a significant hindrance to photosensitivity is formed, photocrosslinking cannot be efficiently formed, that is, a so-called "undercut", which is caused by excessive developer Erosion, lack of stability and lack of light sensitivity. In the invention disclosed in the Korean Patent Application No. 1995-0702313, a cadmium resin is used for the photosensitive resin composition for a black matrix in order to improve the sensitivity, but the large molecular structure causes a decrease in adhesiveness. Especially in the case of black matrices, in order to achieve the required optical density The content of the black pigment is increased to the extent that the adhesion is drastically lowered. In this regard, the Korean Patent Application No. 2000-0055255 discloses a cadmium-based resin and a decane-based coupling agent which are copolymerized with various monomers, but has poor storage stability and is subjected to post-exposure baking treatment. When the heat flow forms a fine pattern, there is a problem of a difference in optical density due to the position.

本發明的目的，係提供一種與基板間的密著性及儲藏安定性優異，藉由邊維持感度邊減少曝後烤處理時的熱流動性，而可改善微細圖型形成時，因位置所造成的光學密度差的黑色感光性樹脂組成物、使用其所製造之黑色矩陣及具備該黑色矩陣之彩色濾光片。 An object of the present invention is to provide an excellent adhesion between a substrate and a substrate, and to improve the thermal fluidity during the post-exposure treatment while maintaining the sensitivity, thereby improving the formation of the fine pattern and the position. A black photosensitive resin composition having a poor optical density, a black matrix produced using the same, and a color filter including the black matrix.

為達成上述目的，提供一種包含以含有下列化學式1中所記載之化合物之單體進行聚合反應而獲得之鹼可溶性樹脂(B)之黑色感光性樹脂組成物。 In order to achieve the above object, there is provided a black photosensitive resin composition comprising an alkali-soluble resin (B) obtained by subjecting a monomer having a compound described in the following Chemical Formula 1 to a polymerization reaction.

(化學式1中，n表示2~4的常數)。 (In Chemical Formula 1, n represents a constant of 2 to 4).

該單體，可更包含下列化學式2中所記載之化合物。 The monomer may further contain a compound described in the following Chemical Formula 2.

(化學式2) (Chemical Formula 2)

(化學式2中，m表示0~2的常數)。 (In Chemical Formula 2, m represents a constant of 0 to 2).

該化學式1中所記載之化合物相對於該單體，可含有10~40重量部。 The compound described in Chemical Formula 1 may contain 10 to 40 parts by weight based on the monomer.

該化學式2中所記載之化合物相對於該單體，可含有10~40重量部。 The compound described in Chemical Formula 2 may contain 10 to 40 parts by weight based on the monomer.

該鹼可溶性樹脂(B)相對於組成物之固形成分，可含有4~25重量部。 The alkali-soluble resin (B) may contain 4 to 25 parts by weight relative to the solid content of the composition.

該單體可更包含自(甲基)丙烯酸酯系化合物、芳香族乙烯基化合物、羧酸乙烯基酯化合物、氰化乙烯基化合物、馬來醯亞胺化合物、乙烯基羧酸酯化合物、不飽和環氧丙烷羧酸酯化合物、單羧酸化合物、二羧酸化合物及二末端具有羧基與羥基的化合物所組成群組所選出之單獨或複數種之混合物。 The monomer may further comprise a (meth) acrylate compound, an aromatic vinyl compound, a carboxylic acid vinyl ester compound, a vinyl cyanide compound, a maleic imine compound, a vinyl carboxylate compound, or A mixture of a single or plural selected from the group consisting of a saturated propylene oxide carboxylate compound, a monocarboxylic acid compound, a dicarboxylic acid compound, and a compound having a carboxyl group and a hydroxyl group at both terminals.

該黑色感光性樹脂組成物可更包含自著色劑(A)、光聚合性化合物(C)、光聚合開始劑(D)及溶劑(E)所組成群組所選出之單獨或複數種之混合物。 The black photosensitive resin composition may further comprise a mixture of a single or a plurality of selected from the group consisting of the coloring agent (A), the photopolymerizable compound (C), the photopolymerization initiator (D), and the solvent (E). .

為達成本發明之另一目的，本發明係提供一種將本發明之黑色感光性樹脂組成物進行塗布、曝光及顯影而獲得之黑色矩陣。 In order to achieve another object of the present invention, the present invention provides a black matrix obtained by coating, exposing and developing a black photosensitive resin composition of the present invention.

為達成本發明之再一目的，本發明係提供一種具備有該 黑色矩陣之彩色濾光片。 In order to achieve a further object of the present invention, the present invention provides a Black matrix color filter.

本發明的黑色感光性樹脂組成物，不僅與基板間的密著性，感度也很優異，且可形成微細圖型。 The black photosensitive resin composition of the present invention is excellent not only in adhesion to a substrate but also in sensitivity, and can form a fine pattern.

本發明的黑色感光性樹脂組成物，感度不會下降的同時，減少曝後烤處理時的熱流動性，而可改善微細圖型形成時，因位置所造成的光學密度差。藉此，可製造出可將強背光源均勻地遮蔽的黑色矩陣。 The black photosensitive resin composition of the present invention can reduce the thermal fluidity during the post-exposure baking treatment without reducing the sensitivity, and can improve the optical density difference due to the position when the fine pattern is formed. Thereby, a black matrix that can uniformly shield a strong backlight can be manufactured.

本發明的黑色感光性樹脂組成物，儲藏安定性優異，且不會因儲藏期間而有物性變化。 The black photosensitive resin composition of the present invention is excellent in storage stability and does not change in physical properties due to storage period.

以下，為使相關業者可容易實施本發明，對本發明進行詳細地說明。 Hereinafter, the present invention will be described in detail so that the related art can easily implement the present invention.

本發明的黑色感光性樹脂組成物，是包含以單體進行聚合反應而獲得之鹼可溶性樹脂(B)。該單體是含有下列化學式1中所記載之化合物。 The black photosensitive resin composition of the present invention is an alkali-soluble resin (B) obtained by carrying out a polymerization reaction with a monomer. This monomer is a compound containing the following Chemical Formula 1.

該化學式1中，n表示2~4的常數。 In the chemical formula 1, n represents a constant of 2 to 4.

本發明的黑色感光性樹脂組成物，包含含有下列該化學式1中所記載之化合物之單體的聚合體，而可提升與基板間的密著性，該聚合體因非反應性，所以可提升儲藏安定性，且不會因儲藏期間而發生線寬變化。此外，藉由 曝後烤處理之際，熱流動性較小，而可改善因位置所造成的光學密度差，故可製造出可將背光源均勻地遮蔽的黑色矩陣。 The black photosensitive resin composition of the present invention contains a polymer containing a monomer of the compound described in the following Chemical Formula 1, and the adhesion to the substrate can be improved, and the polymer can be improved due to non-reactivity. Storage stability and no change in line width due to storage. In addition, by At the time of the post-exposure baking treatment, the thermal fluidity is small, and the difference in optical density due to the position can be improved, so that a black matrix which can uniformly shield the backlight can be manufactured.

具體地，該化學式1中所記載之化合物，係可使用丙烯酰氧基乙基琥珀酸類等，較佳為可使用自4-(2-(丙烯酰氧基)乙氧基)-4-乙酰乙酸、5-(2-(丙烯酰氧基)乙氧基)-5-乙酰丙酸及6-(2-(丙烯酰氧基)乙氧基)-6-氧代己酸所組成群組所選出之單獨或複數種之混合物，但不以此為限。 Specifically, the compound described in Chemical Formula 1 may be acryloyloxyethyl succinic acid or the like, and is preferably used from 4-(2-(acryloyloxy)ethoxy)-4-acetyl. a group consisting of acetic acid, 5-(2-(acryloyloxy)ethoxy)-5-levulinic acid and 6-(2-(acryloyloxy)ethoxy)-6-oxohexanoic acid A single or multiple mixture selected, but not limited thereto.

該化學式1中所記載之化合物相對於該單體，可含有10~40重量部。亦即，相對於為了該鹼可溶性樹脂(B)的聚合所投入的單體的總量，投入10~40重量部而得以聚合。於該化學式1中所記載之化合物，含有未滿10重量部的場合，當圖型形成之際，減少曝後烤處理時的熱流動性的效果較微不足道，且於圖型形成時，因殘膜的形成而會導致直進性不良。於超過40重量部的場合，當圖型形成之際，因下沉現象則會發生直進行及膜均勻度方面的問題。 The compound described in Chemical Formula 1 may contain 10 to 40 parts by weight based on the monomer. In other words, 10 to 40 parts by weight is added to the total amount of the monomers charged for the polymerization of the alkali-soluble resin (B) to be polymerized. When the compound described in the chemical formula 1 contains less than 10 parts by weight, when the pattern is formed, the effect of reducing the thermal fluidity during the post-exposure baking treatment is insignificant, and when the pattern is formed, the residue is formed. The formation of a film may result in poor straightness. In the case of more than 40 parts by weight, when the pattern is formed, problems such as straightening and film uniformity occur due to the sinking phenomenon.

該單體更可含有下列化學式2中所記載之化合物。 The monomer may further contain a compound described in the following Chemical Formula 2.

該化學式2中，m表示0~2的常數。更含有該化學式2中所 記載之化合物作為單體，因為該化學式1及該化學式2的單體是含有於聚合反應中參與的共聚合體，藉由曝後烤處理時，熱流動性更加減少，而可於微細圖型形成時，減少因位置差所造成的光學密度的差。 In the chemical formula 2, m represents a constant of 0 to 2. More contained in the chemical formula 2 The compound described as a monomer, since the monomer of the chemical formula 1 and the chemical formula 2 is a copolymer which participates in a polymerization reaction, and the heat fluidity is further reduced by the post-exposure baking treatment, and can be formed in a fine pattern. When the difference in optical density due to the position difference is reduced.

具體地，該化學式2中所記載之化合物，係可使用異冰片甲基丙烯酸酯，較佳為可使用自1,7,7-三甲基雙環〔2.2.1〕庚-2-基甲基丙烯酸酯、7,7-二甲基-1-丙基雙環〔2.2.1〕庚-2-基甲基丙烯酸酯及1-乙基-7,7-二甲基雙環〔2.2.1〕庚-2-基甲基丙烯酸酯所組成群組所選出之單獨或複數種之混合物，但不以此為限。 Specifically, as the compound described in Chemical Formula 2, isobornyl methacrylate can be used, and it is preferred to use 1,7,7-trimethylbicyclo[2.2.1]hept-2-ylmethyl. Acrylate, 7,7-dimethyl-1-propylbicyclo[2.2.1]heptan-2-yl methacrylate and 1-ethyl-7,7-dimethylbicyclo[2.2.1]heptane A mixture of singly or plural selected from the group consisting of -2- methacrylate, but not limited thereto.

該化學式2中所記載之化合物相對於該單體，可含有10~40重量部。於含有未滿10重量部的場合，當圖型形成之際，密著性較弱，於超過40重量部的場合，顯影性降低及與基板間的密著性增加，而使微細圖型形成方面會具有困難。 The compound described in Chemical Formula 2 may contain 10 to 40 parts by weight based on the monomer. When the pattern is formed, when the pattern is formed, the adhesion is weak, and when it exceeds 40 parts by weight, the developability is lowered and the adhesion to the substrate is increased to form a fine pattern. There will be difficulties in terms.

附加地，該單體是可更含有可與前述化學式1或化學式2中所記載之化合物共聚合的具有不飽和結合的化合物。亦即，將前述化學式1或化學式2中所記載之化合物以外的其他單體，附加地投入而使其共聚合，而得以製造本發明的鹼可溶性樹脂(B)。具體地，可更包含自(甲基)丙烯酸酯系化合物(該(甲基)丙烯酸酯是包含甲基丙烯酸酯與丙烯酸酯二者)、芳香族乙烯基化合物、羧酸乙烯基酯化合物、氰化乙烯基化合物、馬來醯亞胺化合物、乙烯基羧酸酯化合物、不飽和環氧丙烷羧酸酯化合物、單羧酸化合物、二羧酸化合物及二末端具有羧基 與羥基的化合物所組成群組所選出之單獨或複數種之混合物，但不以此為限。具體地，該(甲基)丙烯酸酯系化合物，係有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸醯胺酯等不飽和羧酸的非置換或置換烷基酯化合物；甲基丙烯酸縮水甘油酯等不飽和羧酸縮水甘油酯化合物或(甲基)丙烯酸低聚乙二醇單烷酯等單羧酸乙二醇酯類化合物，但不以此為限。作為該芳香族乙烯基化合物的具體例，係有苯乙烯、α-甲基苯乙烯、乙烯基甲苯等，但不以此為限。作為該羧酸乙烯基酯化合物的具體例，係有醋酸乙烯酯或丙酸乙烯酯等，但不以此為限。作為該氰化乙烯基化合物的具體例，係有丙烯腈、甲基丙烯腈或α-氯丙烯腈等，但不以此為限。作為該馬來醯亞胺化合物的具體例，係有N-環己基馬來醯亞胺或N-苯基馬來醯亞胺等，但不以此為限。作為該乙烯基羧酸酯化合物的具體例，係有醋酸乙烯酯或丙酸乙烯酯等，但不以此為限。作為該不飽和環氧丙烷羧酸酯化合物的具體例，係有3-甲基-3-丙烯氧基甲基環氧丙烷、3-甲基-3-異丁烯氧基甲基環氧丙烷、3-乙基-3-丙烯氧基甲基環氧丙烷、3-乙基-3-異丁烯氧基甲基環氧丙烷、3-甲基-3-丙烯酰氧基乙基環氧丙烷、3-甲基-3-異丁烯氧基乙基環氧丙烷、3-甲基-3-丙烯酰氧基乙基環氧丙烷或3-甲基-3-異丁烯氧基乙基環氧丙烷等，但不以此為限。作為該單羧酸化合物的具體例，係有丙烯酸、甲基丙烯酸或巴豆酸等，但不以此為限。作為該二羧酸化合物的具體例，係有富馬酸、中 康酸或衣康酸等，但不以此為限。作為該二末端具有羧基與羥基的化合物的具體例，係有ω-羧基聚己內酯多元醇單(甲基)丙烯酸酯等，但不以此為限。 Additionally, the monomer may further contain a compound having an unsaturated bond which can be copolymerized with the compound described in the above Chemical Formula 1 or Chemical Formula 2. In other words, the monomer other than the compound described in the above Chemical Formula 1 or Chemical Formula 2 is additionally supplied and copolymerized to produce the alkali-soluble resin (B) of the present invention. Specifically, it may further comprise a (meth) acrylate-based compound (the (meth) acrylate is composed of both a methacrylate and an acrylate), an aromatic vinyl compound, a carboxylic acid vinyl ester compound, and cyanide. Vinyl compound, maleic imide compound, vinyl carboxylate compound, unsaturated propylene oxide carboxylate compound, monocarboxylic acid compound, dicarboxylic acid compound and carboxyl group at both ends A mixture of individual or plural selected from the group consisting of hydroxyl groups, but not limited thereto. Specifically, the (meth) acrylate-based compound is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or 2-hydroxyethyl (meth) acrylate. a non-substituted or substituted alkyl ester compound of an unsaturated carboxylic acid such as benzyl (meth)acrylate or decyl (meth)acrylate; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl methacrylate or The monocarboxylic acid glycol ester compound such as methyl methacrylate oligoethylene glycol monoalkyl ester is not limited thereto. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene, but are not limited thereto. Specific examples of the carboxylic acid vinyl ester compound include vinyl acetate or vinyl propionate, but are not limited thereto. Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, but are not limited thereto. Specific examples of the maleimide compound include N-cyclohexylmaleimide or N-phenylmaleimide, but are not limited thereto. Specific examples of the vinyl carboxylate compound include vinyl acetate or vinyl propionate, but are not limited thereto. Specific examples of the unsaturated propylene oxide carboxylate compound include 3-methyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-isobutenyloxymethyl propylene oxide, and 3 -ethyl-3-propenyloxymethyl propylene oxide, 3-ethyl-3-isobutenyloxymethyl propylene oxide, 3-methyl-3-acryloyloxyethyl propylene oxide, 3- Methyl-3-isobutoxyethyl propylene oxide, 3-methyl-3-acryloyloxyethyl propylene oxide or 3-methyl-3-isobutoxyethyl propylene oxide, but not This is limited to this. Specific examples of the monocarboxylic acid compound include acrylic acid, methacrylic acid, or crotonic acid, but are not limited thereto. Specific examples of the dicarboxylic acid compound include fumaric acid and medium Kang acid or itaconic acid, etc., but not limited to this. Specific examples of the compound having a carboxyl group and a hydroxyl group at the two terminals include ω-carboxypolycaprolactone polyol mono(meth)acrylate, and the like, but are not limited thereto.

該鹼可溶性樹脂(B)相對於組成物之固形成分，可含有4~25重量部，較佳為可含有5~20重量部。當該鹼可溶性樹脂(B)含有4~25重量部的場合，因相對於顯影液的溶解性充分，所以圖型形成變得較為容易，顯影之際，可防止曝光部的膜減少，所以像素部分的完整性變得較為良好。 The alkali-soluble resin (B) may contain 4 to 25 parts by weight, preferably 5 to 20 parts by weight, based on the solid content of the composition. When the alkali-soluble resin (B) contains 4 to 25 parts by weight, the solubility in the developer is sufficient, so that pattern formation is facilitated, and when the image is developed, the film in the exposed portion can be prevented from being reduced. Part of the integrity has become better.

該黑色感光性樹脂組成物，可更包含自著色劑(A)、光聚合性化合物(C)、光聚合開始劑(D)及溶劑(E)所組成群組所選出之單獨或複數種之混合物。 The black photosensitive resin composition may further comprise a single or plural selected from the group consisting of a coloring agent (A), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). mixture.

該著色劑(A)，係包含黑色顏料(A1)及有機顏料(A2)。 The colorant (A) contains a black pigment (A1) and an organic pigment (A2).

該黑色顏料(A1)，只要具有遮光性的顏料，並無特別限制皆可使用，但是具體地，可使用苯胺黑、苝黑、鈦黑、碳黑等。 The black pigment (A1) is not particularly limited as long as it has a light-shielding pigment, but specifically, nigrosine black, ruthenium black, titanium black, carbon black or the like can be used.

該有機顏料(A2)，係擔任顏色校正劑的角色，並無限制而可使用印刷油墨、噴墨油墨等相關業界公知的顏料，具體而言，係可使用水溶性偶氮顏料、不溶性偶氮顏料、酞菁顏料、喹吖啶酮顏料、異吲哚啉酮顏料、異二氫吲哚顏料、苝顏料、環酮顏料、二嗯嗪顏料、蒽醌顏料、二蒽醌顏料、蒽素嘧啶顏料、蒽嵌蒽(anthanthrone)顏料、陰丹酮(indanthrone)顏料、 黃士酮顏料、芘蒽酮(pyranthrone)顏料、二酮吡咯並吡咯顏料等，但不以此為限。 The organic pigment (A2) functions as a color correcting agent, and a pigment known in the art such as printing ink or inkjet ink can be used without limitation, and specifically, a water-soluble azo pigment or an insoluble azo can be used. Pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, anthraquinone pigments, cyclic ketone pigments, dioxazine pigments, anthraquinone pigments, diterpene pigments, alizarin Pigments, anthanthrone pigments, indanthrone pigments, Yellow ketone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment, etc., but not limited thereto.

該著色劑(A)相對於組成物之固形成分，係含有20~70重量部，較佳可含有30~65重量部。當該著色劑(A)含有20~70重量部的場合，薄膜形成之際，光學密度充分，顯影之時，像素部的殘渣發生會減少。於此，該「固形成分」，意義係指自黑色感光性樹脂組成物將溶劑除去後，殘存的成分的總量。 The coloring agent (A) is contained in an amount of 20 to 70 parts by weight, preferably 30 to 65 parts by weight, based on the solid content of the composition. When the colorant (A) contains 20 to 70 parts by weight, the optical density is sufficient when the film is formed, and the occurrence of residue in the pixel portion is reduced at the time of development. Here, the term "solid component" means the total amount of components remaining after removing the solvent from the black photosensitive resin composition.

該光聚合性化合物(C)是可藉由光聚合開始劑(D)的作用而得以聚合的化合物，可使用單官能單體、二官能單體或多宮能單體，較佳可使用二官能以上的多宮能單體。 The photopolymerizable compound (C) is a compound which can be polymerized by the action of a photopolymerization initiator (D), and a monofunctional monomer, a difunctional monomer or a polyfunctional monomer can be used, and preferably two can be used. More than the functional polynomial monomer.

作為該單官能單體的具體例，係有壬基苯酚卡必醇丙烯酸酯、2-羥基-3-苯氧基丙烯酸丙酯、2-乙基己基醚丙烯酰酸二甘醇、丙烯酸-2-羥基乙酯或N-乙烯基吡咯烷酮等，但不以此為限。 Specific examples of the monofunctional monomer include nonylphenol carbitol acrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-ethylhexyl acryl oxy diethylene glycol, and acrylic acid-2. - hydroxyethyl ester or N-vinyl pyrrolidone, etc., but not limited thereto.

作為該二官能單體的具體例，係有1,6-已二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯酰氧基乙基)醚或3-甲基戊二醇二(甲基)丙烯酸酯等，但不以此為限。 Specific examples of the difunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A or 3-methylpentanediol di(meth)acrylate, etc., but not limited thereto.

作為該多宮能單體的具體例，係有三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、季 戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙氧基化二季戊四醇六(甲基)丙烯酸酯、丙氧基化二季戊四醇六(甲基)丙烯酸酯或二季戊四醇六(甲基)丙烯酸酯等，但不以此為限。 Specific examples of the polyuterine monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylol Propane tri(meth)acrylate, season Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate or dipentaerythritol hexa (meth) acrylate, etc., but not limited thereto.

該光聚合性化合物(C)相對於組成物之固形成分，可含有3~40重量部，較佳為可含有5~30重量部。當該光聚合性化合物(C)含有3~40重量部的場合，曝光部的強度及平滑性良好。 The photopolymerizable compound (C) may contain 3 to 40 parts by weight, preferably 5 to 30 parts by weight, based on the solid content of the composition. When the photopolymerizable compound (C) contains 3 to 40 parts by weight, the strength and smoothness of the exposed portion are good.

該光聚合開始劑(D)，並無限制而可使用相關業界公知的光聚合開始劑，具體而言，係可使用三嗪系化合物、苯乙酮系化合物、二咪唑系化合物及肟化合所組成群組所選出之單獨或複數種之混合物。 The photopolymerization initiator (D) is not limited, and a photopolymerization initiator known in the related art can be used. Specifically, a triazine compound, an acetophenone compound, a diimidazole compound, and a bismuth compound can be used. A mixture of individual or plural selected from the group.

具體地，該三嗪系化合物，係有2,4-雙(三氯甲基)-6-(4-甲氧苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-〔2-(5-甲基呋喃-2-基)乙烯基〕-1,3,5-三嗪、2,4-雙(三氯甲基)-6-〔2-(呋喃-2-基)乙烯基〕-1,3,5-三嗪、2,4-雙(三氯甲基)-6-〔2-(4-二乙基氨基-2-甲基苯基)乙烯基〕-1,3,5-三嗪、2,4-雙(三氯甲基)-6-〔2-(3,4-二甲氧苯基)乙烯基〕-1,3,5-三嗪等，但不以此為限。 Specifically, the triazine compound is a 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis (three) Chloromethyl)-6-(4-methoxynaphthalene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyrene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc., but Not limited to this.

具體地，該苯乙酮系化合物，係有二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-1-〔4-(2-羥基乙氧基)苯基〕-2-甲基丙-1-酮、1-羥基環己基苯基甲酮、2-甲基-1-(4-甲基硫苯基)-2-嗎啉基丙-1-酮、2-苄基-2-二甲基氨基-1-(4-嗎啉基苯基)丁-1-酮、2-羥基-2-甲基-1-〔4-(1-甲基乙烯基)苯基〕丙-1-酮的低聚物等，但不以此為限。此外，該苯乙酮系化合物可為下列化學式3中所記載之化合物。 Specifically, the acetophenone-based compound is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxyl 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl Thiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2 - oligomer of methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc., but not limited thereto. Further, the acetophenone-based compound may be a compound described in the following Chemical Formula 3.

於該化學式3中，R1~R4表示各別獨立的氫原子、鹵素原子、羥基、可由碳數1~12的烷基置換的苯基、可由碳數1~12的烷基置換苄基或可由碳數1~12的烷基置換的萘基。作為該化學式3中所記載之化合物的具體例，係有2-甲基一2-氨基(4-嗎啉基苯基)乙-1-酮、2-乙基-氨基(4-嗎啉基苯基)乙-1-酮、2-丙基-2-氨基(4-嗎啉基苯基)乙-1-酮、2-丁基-2-氨基(4-嗎啉基苯基)乙-1-酮、2-甲基-2-氨基(4-嗎啉基苯基)丙-1-酮、2-甲基-2-氨基(4-嗎啉基苯基)丁-1-酮、2-乙基-2-氨基(4-嗎啉基苯基)丙-1-酮、2-乙基-2-氨基(4-嗎啉基苯基)丁-1-酮、2-甲基-2-甲基氨基(4-嗎啉基苯基)丙-1-酮、2-甲基-2-二甲基氨基(4-嗎啉基苯基)丙-1-酮、2-甲基-2-二乙基氨基(4-嗎啉基苯基)丙-1-酮 等，但不以此為限。 In the chemical formula 3, R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, and a benzyl group may be substituted by an alkyl group having 1 to 12 carbon atoms. Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms. Specific examples of the compound described in Chemical Formula 3 are 2-methyl-2-amino(4-morpholinylphenyl)ethan-1-one and 2-ethyl-amino(4-morpholinyl). Phenyl)ethan-1-one, 2-propyl-2-amino(4-morpholinylphenyl)ethan-1-one, 2-butyl-2-amino(4-morpholinylphenyl)B 1-ketone, 2-methyl-2-amino(4-morpholinylphenyl)propan-1-one, 2-methyl-2-amino(4-morpholinylphenyl)butan-1-one , 2-ethyl-2-amino(4-morpholinylphenyl)propan-1-one, 2-ethyl-2-amino(4-morpholinylphenyl)butan-1-one, 2-methyl 2-methylamino(4-morpholinylphenyl)propan-1-one, 2-methyl-2-dimethylamino(4-morpholinylphenyl)propan-1-one, 2- Methyl-2-diethylamino(4-morpholinylphenyl)propan-1-one, etc., but not limited thereto.

具體地，該二咪唑系化合物，係有2,2’-雙(2-氯苯基)-4，4’,5,5’-四苯基二咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)二咪唑、位於4,4’,5,5’位置的苯基由烷氧羰基置換成的咪唑化合物等，較佳為可使用2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基二咪唑等，但不以此為限。 Specifically, the diimidazole compound is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis (2, 3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5' -tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)diimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole, imidazole substituted by alkoxycarbonyl group at the 4,4',5,5' position For compounds and the like, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-di) can be preferably used. Chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, etc., but not limited thereto.

該肟化合物，可具體舉例如下列的化學式4~6中，任一者中所記載之化合物。 Specific examples of the ruthenium compound include the compounds described in any one of Chemical Formulas 4 to 6 below.

(化學式6) (Chemical Formula 6)

此外，上述光聚合開始劑以外，只要對本發明的效果不會造成損害的程度下，可追加併用於該技術領域中，通常使用的其他的光聚合開始劑等。作為其他的光聚合開始劑，例如可列舉安息香系化合物、苯甲酮系化合物、噻噸酮系化合物、精蒽系化合物、多宮能硫醇化合物等。這些化合物可各別單獨或組合二種以上使用。具體地，該安息香系化合物，係有安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等，但不以此為限。作為該苯甲酮系化合物，例如可列舉苯甲酮、0-苯甲酰苯酸甲基、4-苯基苯甲酮、4-苯甲酰-4’-甲基二苯基硫醚、3,3’,4,4’-四(叔丁過氧化碳酸基)苯甲酮、2,4,6-三甲基苯甲酮等。具體地，該噻噸酮系化合物，係有2-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯基-4-丙氧基噻噸酮等，但不以此為限。具體地，該精蒽系化合物，係有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-9,10-二乙氧基蒽等，但不以此為限。具體地，該多宮能硫醇化合物，係有三-(3-巰基丙酸基)-乙基-異氰脲酸、三羥甲基丙烷三-3-巰基丙酸、季戊四醇四-3-巰基丙酸、二季戊四醇四-3-巰基丙酸等，但不以此為限。 In addition to the above-mentioned photopolymerization initiator, other photopolymerization initiators and the like which are generally used in the technical field can be added to the extent that the effects of the present invention are not impaired. Examples of the other photopolymerization initiator include a benzoin compound, a benzophenone compound, a thioxanthone compound, a refined quinone compound, and a poly-functional thiol compound. These compounds may be used alone or in combination of two or more. Specifically, the benzoin-based compound is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., but is not limited thereto. Examples of the benzophenone-based compound include benzophenone, methyl 10-benzophenone, 4-phenylbenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide. 3,3',4,4'-tetra(tert-butylperoxycarbonate)benzophenone, 2,4,6-trimethylbenzophenone, and the like. Specifically, the thioxanthone compound is 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propyl Oxythioxanthone, etc., but not limited thereto. Specifically, the spermidine compound is 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, etc., but not limited thereto. Specifically, the poly-functional thiol compound is tris-(3-mercaptopropionic acid)-ethyl-isocyanuric acid, trimethylolpropane tri-3-mercaptopropionic acid, pentaerythritol tetrakis-yl fluorenyl Propionic acid, dipentaerythritol tetrakis-3-mercaptopropionic acid, etc., but not limited thereto.

另外，可將2,4,6-三甲基苯甲酰二苯基氧化膦、10-丁基-2-氯吖啶酮、2-乙基蒽醌、苄基、9,10-菲醌、樟腦醌、苯基乙醛酸甲基、二茂鈦化合物等，作為其他的光聚合開始劑使用。 In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone , camphorquinone, phenylglyoxylate methyl, titanocene compound, etc., used as other photopolymerization initiators.

該光聚合開始劑(D)相對於組成物之固形成分，可含有0.1~20重量部，較佳可含有0.5~10重量部。當該光聚合開始劑(D)含有0.1~20重量部的場合，黑色感光性樹脂組成物的感度優異，且因曝光時間縮短而生產性得以提升的同時，可維持高微細性，故曝光部的強度及平滑性良好，因此較為適宜。 The photopolymerization initiator (D) may be contained in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on the solid content of the composition. When the photopolymerization initiator (D) is contained in an amount of 0.1 to 20 parts by weight, the black photosensitive resin composition is excellent in sensitivity, and the productivity is improved by shortening the exposure time, and high fineness can be maintained. It is suitable for its strength and smoothness.

於該光聚合開始劑(D)中，可組合光聚合開始劑(D-1)使用。若光聚合開始劑(D)中併用光聚合開始劑(D-1)，含有這些光聚合開始劑的黑色感光性樹脂組成物，可變得更高感度，且形成黑色矩陣或黑柱間隔(Black Column Spacer)時的生產性得以提升。 In the photopolymerization initiator (D), a photopolymerization initiator (D-1) can be used in combination. When the photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D-1), the black photosensitive resin composition containing these photopolymerization initiators can be made higher in sensitivity and form a black matrix or black column interval ( The productivity of the Black Column Spacer) is improved.

作為該光聚合開始劑(D-1)，可使用胺化合物及羧酸化合物所組成群組所選出之單獨或複數種之混合物。 As the photopolymerization initiator (D-1), a single or a mixture of a plurality of selected ones selected from the group consisting of an amine compound and a carboxylic acid compound can be used.

具體地，該胺化合物係有三乙醇胺、甲基乙醇胺、三異丙醇胺等脂肪族胺化合物；或有4-二甲基氨基苯酸甲基、4-二甲基氨基苯酸乙基、4-二甲基氨基苯酸異戊基、4-二甲基氨基苯酸2-乙基已基、苯酸2-二甲基氨基乙基、N,N-二甲基對甲苯胺、4,4’-雙(二甲基氨基)苯甲酮(通稱：米其勒酮(Michler’sketone))、4,4’-雙(二乙基氨基)苯甲酮等的芳香族胺化合物，較佳可使 用芳香族胺化合物，但不以此為限。 Specifically, the amine compound is an aliphatic amine compound such as triethanolamine, methylethanolamine or triisopropanolamine; or methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -isomethyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4, Aromatic amine compounds such as 4'-bis(dimethylamino)benzophenone (commonly known as: Michler'sketone) and 4,4'-bis(diethylamino)benzophenone Good Aromatic amine compounds are used, but not limited thereto.

具體地，該羧酸化合物係有苯基硫代乙酸鹽、甲基苯基硫代乙酸鹽、乙基苯基硫代乙酸鹽、甲基乙基苯基硫代乙酸鹽、二甲基苯基硫代乙酸鹽、甲氧苯基硫代乙酸鹽、二甲氧苯基硫代乙酸鹽、氯苯基硫代乙酸鹽、二氯苯基硫代乙酸鹽、N-苯基氨基乙酸、苯氧基乙酸、萘基硫代乙酸鹽、N-萘氨基乙酸、萘氧基乙酸鹽等芳香族雜乙酸鹽類，但不以此為限。 Specifically, the carboxylic acid compound is a phenylthioacetate, a methylphenylthioacetate, an ethylphenylthioacetate, a methylethylphenylthioacetate, or a dimethylphenyl group. Thioacetate, methoxyphenylthioacetate, dimethoxyphenylthioacetate, chlorophenylthioacetate, dichlorophenylthioacetate, N-phenylglycine, phenoxy An aromatic heteroacetate such as a vinyl acetate, a naphthylthioacetate, an N-naphthylaminoacetic acid or a naphthyloxyacetate, but is not limited thereto.

該光聚合開始劑(D-1)相對於組成物之固形成分，可含有0.01~10重量部，較佳可含有0.01~5重量部。當該光聚合開始劑(D-1)含有0.01~10重量部的場合，黑色感光性樹脂組成物的感度增加，且隨之補僅所形成的著色層的強度及平滑性上升，彩色濾光片的生產性也得以提升。 The photopolymerization initiator (D-1) may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on the solid content of the composition. When the photopolymerization initiator (D-1) contains 0.01 to 10 parts by weight, the sensitivity of the black photosensitive resin composition increases, and the strength and smoothness of the colored layer formed by the addition are increased, and color filtering is performed. The productivity of the film has also been improved.

該溶劑(E)，並無限制而可使用相關業界公知的溶劑，具體而言，可使用乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚等乙二醇單烷醚類；二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚等二乙二醇二烷基醚類；甲基溶纖劑乙酸鹽、乙基溶纖劑乙酸鹽等乙二醇烷基醚乙酸鹽類；丙二醇甲醚醋酸酯、丙二醇單乙基醚乙酸鹽、丙二醇單丙基醚乙酸鹽等烯乙二醇烷基醚乙酸鹽類；甲氧基丁烷基乙酸鹽、甲氧基戊烷基乙酸鹽等烷氧基烷基乙酸鹽類；苯、甲苯、二甲苯、三甲苯等芳香族碳氫類；甲基乙基甲酮、丙酮、甲基戊烷基甲酮、甲基異丁烷基 甲酮、環己酮等甲酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙三醇等醇類；3-乙氧基苯丙酮酸乙基、3-甲氧基苯丙酮酸甲基等酯類；及γ-丁內酯等環狀酯類所組成群組所選出之單獨或複數種之混合物。 The solvent (E) is not limited, and a solvent known in the art can be used. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene can be used. Ethylene glycol monoalkyl ethers such as alcohol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc. Diethylene glycol dialkyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, etc., ethylene glycol alkyl ether acetate; propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Alkenyl glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutane acetate and methoxypentan acetate; benzene, toluene, Aromatic hydrocarbons such as xylene and trimethylbenzene; methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl Ketones such as ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; ethyl 3-ethoxyphenylpyruvate, 3- An ester such as methyl methoxyphenylpyruvate; or a mixture of a plurality of selected ones selected from the group consisting of cyclic esters such as γ-butyrolactone.

較佳為可使用從塗布性、乾燥性方面考量，沸點為100~200℃的有機溶劑，更佳為可使用烯乙二醇烷基醚乙酸鹽類、甲酮類、3-乙氧基苯丙酮酸乙基及3-甲氧基苯丙酮酸甲基等所組成群組所選出之單獨或二種以上之混合物，最佳為可使用丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸鹽、環己酮、3-乙氧基苯丙酮酸乙基及3-甲氧基苯丙酮酸甲基所組成群組所選出之單獨或複數種之混合物。 It is preferred to use an organic solvent having a boiling point of 100 to 200 ° C in consideration of coating properties and drying properties, and more preferably an alkylene glycol alkyl ether acetate, a ketone or a 3-ethoxybenzene. A mixture of two or more selected from the group consisting of ethyl pyruvate and methyl 3-methoxyphenylpyruvate, preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether A mixture of a single or a plurality of selected from the group consisting of acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

該溶劑(E)相對於黑色感光性樹脂組成物，係含有60~90重量部，較佳可含有70~88重量部。當該溶劑(E)含有60~90重量部的場合，以輥式塗布機、旋轉式塗布機、狹縫與旋轉式塗布機、狹縫式塗布機(口模式塗布機，Die Coater)、等塗布裝置進行塗布之際，塗布性良好。 The solvent (E) is contained in an amount of 60 to 90 parts by weight, preferably 70 to 88 parts by weight, based on the black photosensitive resin composition. When the solvent (E) contains 60 to 90 parts by weight, a roll coater, a rotary coater, a slit and a rotary coater, a slit coater (die coater, Die Coater), etc. When the coating device was applied, the coatability was good.

本發明的黑色感光性樹脂組成物，除前述成分以外，在不脫離本發明的目的範圍內，相關業者可應需要而得以併用充填劑、其他高分子化合物、硬化劑、顏料分散劑、密著促進劑、氧化防止劑、紫外線吸收劑、凝集防止劑等添加劑F。 In addition to the above-described components, the black photosensitive resin composition of the present invention can be used in combination with a filler, other polymer compound, a hardener, a pigment dispersant, and a seal, as needed within the scope of the object of the present invention. An additive F such as an accelerator, an oxidation preventive, an ultraviolet absorber, or an aggregation inhibitor.

具體地，該充填劑可使用玻璃、矽、氧化鋁等，但不以 此為限。 Specifically, the filler may use glass, ruthenium, alumina, etc., but not This is limited.

具體地，該其他高分子化合物可使用環氧樹脂、馬來醯亞胺樹脂等硬化性樹脂、聚乙二醇、聚丙烯酸、聚乙二醇單烷醚、全氟烷基丙烯酸酯、聚酯、聚氨酯等熱可塑性樹脂等，但不以此為限。 Specifically, as the other polymer compound, a curable resin such as an epoxy resin or a maleimide resin, polyethylene glycol, polyacrylic acid, polyethylene glycol monoalkyl ether, perfluoroalkyl acrylate or polyester can be used. , thermoplastic resins such as polyurethane, etc., but not limited to this.

該硬化劑，是為了提高芯部硬化及機械的強度而使用，具體地，可使用環氧化合物、多宮能異氰酸酯化合物、三聚氰胺化合物、環氧丙烷化合物等，但不以此為限。具體地，該環氧化合物可使用雙酚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、酚醛型環氧樹脂、其他的芳香族系環氧樹脂、脂環族系環氧樹脂、縮水甘油酯系樹脂、縮水甘油胺系樹脂或這種類型的環氧樹脂的溴化衍生物、環氧樹脂及其溴化衍生物以外的脂肪族、脂環族或芳香族環氧化合物、丁二烯(共)聚合體環氧化物、異戊二烯(共)聚合體環氧化物、縮水甘油(甲基)丙烯酸酯(共)聚合體、三縮水甘油異氰脲酸等，但不以此為限。具體地，該環氧丙烷化合物可使用碳酸酯雙環氧丙烷、二甲苯雙環氧丙烷、己二酸雙環氧丙烷、對苯二甲酸酯雙環氧丙烷、環已烷二羧酸雙環氧丙烷等，但不以此為限。 The curing agent is used to improve the strength of the core portion and the mechanical strength. Specifically, an epoxy compound, a poly-isocyanate compound, a melamine compound, a propylene oxide compound, or the like can be used, but not limited thereto. Specifically, as the epoxy compound, a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolac epoxy resin, or the like can be used. Aromatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine resin or brominated derivative of this type of epoxy resin, epoxy resin and brominated derivative thereof Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, glycidyl (meth) acrylates ) Polymer, triglycidyl isocyanuric acid, etc., but not limited thereto. Specifically, the propylene oxide compound may use carbonate dipropylene oxide, xylene dipropylene oxide, adipic acid dipropylene oxide, terephthalate dipropylene oxide, cyclohexane dicarboxylic acid double Propylene oxide, etc., but not limited to this.

該硬化劑可以併用，可將硬化劑與環氧化合物的環氧基、環氧丙烷化合物的環氧丙烷骨架進行開環聚合的硬化輔助化合物。具體地，該硬化輔助化合物可使用多價羧酸類、多價羧酸無水物類、酸發生劑等。該羧酸無水物類可以市販製品作為環氧樹脂硬化劑使用。例如，作為 市販的該環氧樹脂硬化劑，可列舉商品名(ADEKA HARDENER EH-700)(ADEKA股份公司製)、商品名(RIKACID HH)(新日本理化股份公司製)、商品名(MH-700)(新日本理化股份公司製)等。 The curing agent may be used in combination, and a hardening auxiliary compound which is a ring-opening polymerization of a curing agent and an epoxy group of an epoxy compound or a propylene oxide skeleton of a propylene oxide compound. Specifically, as the hardening auxiliary compound, a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydrate, an acid generator, or the like can be used. The carboxylic acid anhydrides can be used as an epoxy resin hardener in commercially available products. For example, as For the epoxy resin hardener to be sold, the product name (ADEKA HARDENER EH-700) (made by ADEKA AG), the trade name (RIKACID HH) (made by Shin-Nippon Chemical Co., Ltd.), and the trade name (MH-700) ( New Japan Physical and Chemical Co., Ltd.).

該硬化劑及硬化輔助化合物，可各別單獨或混合二種以上使用。 The curing agent and the hardening auxiliary compound may be used singly or in combination of two or more kinds.

該顏料分散劑，可使用市販的界面活性劑，具體地，可使用矽系、氟系、酯系、陽離子系、陰離子系、非離子系及兩性等界面活性劑所組成群組所選出之單獨或複數種之混合物。更具體地，可使用聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、山梨醇脂肪酸酯類、脂肪酸變性聚酯類、第3級胺變性聚氨酯類、聚乙烯亞胺類等，另外，以商品名而言，可使用KP(信越化學工業公司製)、Polyflow(共榮化學公司製)、F-Top(TOKEM Products公司製)、MEGAFAC(大日本油墨化學工業公司製)、Fluorad(住友3M公司製)、ASAHI CURD、Surflon(以上為旭玻璃公司製)、Solsperse(Lubrizol製)、EFKA(EFKA CHEMICALS公司製)、PB821(味之素公司製)、Disperbyk-series(BYK-chemi)等。 As the pigment dispersant, a commercially available surfactant can be used. Specifically, a separate group selected from the group consisting of a lanthanide, a fluorine-based, an ester-based, a cationic, an anionic, a nonionic, and an amphoteric surfactant can be used. Or a mixture of plural species. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes can be used. For the product name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by TOKEM Products), and MEGAFAC (large) can be used. Japan Ink Chemical Industry Co., Ltd., Fluorad (manufactured by Sumitomo 3M), ASAHI CURD, Surflon (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.) ), Disperbyk-series (BYK-chemi), etc.

具體地，該密著促進劑可使用乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-縮水甘油醚丙基三甲氧基矽烷、 3-縮水甘油醚丙基三甲基二甲氧基矽烷、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-甲基丙烯酸基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三甲氧基矽烷及3-異氰酸酯丙基三乙氧基矽烷所組成群組所選出之單獨或複數種之混合物。 Specifically, the adhesion promoter may use vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidyl ether Trimethoxy decane, 3-glycidyl ether propyl trimethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3- Chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and 3-isocyanatepropyltriethoxylate A mixture of individual or plural selected from the group consisting of decane.

該密著促進劑相對於組成物之固形成分，可含有0.01~10重量部，較佳可含有0.05~2重量部。 The adhesion promoter may contain 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on the solid content of the composition.

具體地，該氧化防止劑可使用2,2’-硫代雙(4-甲基-6-t-丁基苯酚)、2,6-二-t-丁基-4-甲基苯酚等，但不以此為限。 Specifically, as the oxidation preventing agent, 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol or the like can be used. But not limited to this.

具體地，該紫外線吸收劑可使用2-(3-叔-丁基-2-羥基-5-甲基苯基)-5-氯苯並三氮唑、烷氧基苯甲酮等，但不以此為限。 Specifically, the ultraviolet absorber may be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone or the like, but not This is limited to this.

具體地，該凝集防止劑可使用，聚丙烯酸鈉等，但不以此為限。 Specifically, the aggregation inhibitor may be used, but not limited to sodium polyacrylate.

本發明的黑色感光性樹脂組成物，可藉由以下所述方法製造。將著色劑(A)事先與溶劑(E)混和且著色劑的平均粒徑降至0.2μm左右為止，使用珠磨機使其分散而獲得分散液。此時，可應需要得以使用顏料分散劑，於鹼可溶性樹脂(B)可一部分被合成或全部皆被合成的場合中亦可。將所獲得的分散液(以下，也有研磨基料的場合)中鹼可溶性樹脂(B)的殘存、光聚合性化合物(C)及光聚合開始劑(D)等應需要添加劑F，進行添加後 ，應需要將追加的溶劑添加至達到預定濃度，而可以獲得作為目的代表的黑色感光性樹脂組成物。 The black photosensitive resin composition of the present invention can be produced by the method described below. The coloring agent (A) was previously mixed with the solvent (E), and the average particle diameter of the coloring agent was reduced to about 0.2 μm, and dispersed in a bead mill to obtain a dispersion. In this case, a pigment dispersant may be used as needed, and the alkali-soluble resin (B) may be partially synthesized or all synthesized. When the obtained dispersion (hereinafter, in the case of a polishing base), the residual of the alkali-soluble resin (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) are required to be added, and after the addition, the additive F is added. It is necessary to add an additional solvent to a predetermined concentration, and a black photosensitive resin composition represented by the purpose can be obtained.

以下，對本發明所相關之彩色濾光片進行說明。 Hereinafter, the color filter according to the present invention will be described.

本發明所述之彩色濾光片，係包含於基板上部塗布上述本發明所相關之黑色感光性樹脂組成物，以預定圖型加以曝光及顯影藉而可獲得黑色矩陣或黑柱間隔。 The color filter of the present invention comprises the above-mentioned black photosensitive resin composition according to the present invention coated on the upper portion of the substrate, and exposed and developed in a predetermined pattern to obtain a black matrix or black column interval.

更具體地，使用本發明所相關之黑色感光性樹脂組成物，形成黑色矩陣或黑柱間隔的圖型的方法，係包含將上述黑色感光性樹脂組成物塗布於基板上的塗布步驟、選擇性地將該黑色感光性樹脂組成物的一部分領域曝光的曝光步驟及將該黑色感光性樹脂組成物的曝光領域或非曝光領域除去的顯影步驟。 More specifically, a method of forming a pattern of a black matrix or a black pillar interval using the black photosensitive resin composition according to the present invention includes a coating step of applying the black photosensitive resin composition onto a substrate, and a selectivity An exposure step of exposing a part of the black photosensitive resin composition and a development step of removing the exposed or non-exposed areas of the black photosensitive resin composition.

該塗布步驟，係為藉由將本發明的黑色感光性樹脂組成物塗布於基板上且進行預備乾燥，而可除去溶劑等揮發成分而獲得平滑的塗膜的步驟。此時，塗膜的厚度約為0.5~5μm。該基板為玻璃、矽晶圓或聚醚砜(PES：polyethersulfone)、聚碳酸酯(PC：polycarbon-ate)等塑膠基材的板即可，但對其種類並無任何特別限制。 This coating step is a step of obtaining a smooth coating film by applying a black photosensitive resin composition of the present invention onto a substrate and performing preliminary drying to remove volatile components such as a solvent. At this time, the thickness of the coating film is about 0.5 to 5 μm. The substrate may be a plate of a plastic substrate such as glass, tantalum wafer or polyethersulfone (PES) or polycarbonate (PC: polycarbonate), but the kind thereof is not particularly limited.

該曝光步驟係為，於前述過程中所獲得之塗膜上，為獲得作為目的代表的圖型，透過遮罩，於特定領域照射紫外線的步驟。此時，於曝光部的全體平均地照射平行光線，為了遮罩與基板可正確地對準位置，使用遮罩校準器或步進器等裝置較佳。 This exposure step is a step of irradiating ultraviolet rays in a specific field through a mask in order to obtain a pattern represented by the object on the coating film obtained in the foregoing process. At this time, the entire surface of the exposure portion is uniformly irradiated with parallel rays, and a device such as a mask aligner or a stepper is preferably used in order to accurately align the position with the substrate.

該顯影步驟係為，藉由將於前述過程中硬化終了後的塗膜，使其與作為顯影液的鹼水溶液接觸，使非曝光領域溶解，進行顯影，而可製造作為目的代表的圖型的步驟。顯影之後，應需要可於150~230℃下，經過約10~60分鐘後，可進行乾燥。 In the development step, the coating film after hardening in the above-mentioned process is brought into contact with an aqueous alkali solution as a developing solution to dissolve the non-exposure field, and development is carried out, whereby a pattern represented by the object can be produced. step. After development, it may be dried at 150-230 ° C for about 10 to 60 minutes.

於該顯影步驟所使用的顯影液，通常為含有鹼性化合物與界面活性劑的水溶液。該鹼性化合物，可使用無機或有機鹼性化合物，具體地，該無機鹼性化合物可使用氫氧化鈉、氫氧化鉀、燐酸氫二鈉、燐酸二氫鈉、燐酸氫二銨、燐酸二氫銨、燐酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、氨等。此外，具體地，該有機鹼性化合物可列舉，四甲基氫氧化銨、2-羥基乙基三甲基氫氧化銨、單甲基胺、二甲基胺、三甲基胺、單乙基胺、二乙基胺、三乙基胺、單異丙基胺、二異丙基胺、乙醇胺等。這些無機及有機鹼性化合物，可各別單獨或組合二種以上使用。該鹼性化合物的較佳濃度係介於0.01~10重量部範圍，更佳為0.03~5重量部。 The developer used in the development step is usually an aqueous solution containing a basic compound and a surfactant. As the basic compound, an inorganic or organic basic compound can be used. Specifically, the inorganic basic compound can be sodium hydroxide, potassium hydroxide, disodium hydrogen citrate, sodium dihydrogen citrate, diammonium hydrogen citrate or dihydrogen citrate. Ammonium, potassium dihydrogen citrate, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, and the like. Further, specifically, the organic basic compound may, for example, be tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethyl Amine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic basic compounds may be used alone or in combination of two or more. The preferred concentration of the basic compound is in the range of 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight.

於該顯影液中，界面活性劑可使用非離子系界面活性劑、陰離子系界面活性劑及陽離子系界面活性劑所組成群組所選出之單獨或複數種之混合物。具體地，該非離子系界面活性劑可使用聚氧乙烯烷基醚、聚氧乙烯芳香族羥基醚、聚氧乙烯烷基芳香族羥基醚、其他的聚氧乙烯衍生物、氧乙烯/氧丙烯嵌段共聚合體、山梨醇脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、丙三醇脂肪酸酯、聚氧 乙烯脂肪酸酯、聚氧乙烯烷基胺等。具體地，該陰離子系界面活性劑可使用月桂醇硫酸酯鈉、油醇硫酸酯鈉等高級醇硫酸酯鹽類、月桂基硫酸鈉、月桂基硫酸銨等烷基硫酸鹽類、十二烷基苯砜酸鈉、十二烷基萘砜酸鈉等烷基丙烯基砜酸鹽類等。具體地，該陽離子系界面活性劑可使用硬脂醯基胺鹽酸鹽、月桂基三甲基氯化銨等胺鹽或第4級銨鹽等。該界面活性劑，可各別單獨或組合二種以上使用。該界面活性劑相對於鹼顯影液，含有0.01~10重量部，較佳為含有0.05~8重量部，更佳為含有0.1~5重量部。 In the developer, the surfactant may be a mixture of a single or a plurality of selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Specifically, the nonionic surfactant may be a polyoxyethylene alkyl ether, a polyoxyethylene aromatic hydroxy ether, a polyoxyethylene alkyl aromatic hydroxy ether, other polyoxyethylene derivatives, or an oxyethylene/oxypropylene intercalation. Segmental copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester, polyoxygen Ethylene fatty acid ester, polyoxyethylene alkylamine, and the like. Specifically, as the anionic surfactant, a higher alcohol sulfate salt such as sodium lauryl sulfate or sodium oleyl sulfate, an alkyl sulfate such as sodium lauryl sulfate or ammonium lauryl sulfate, or a dodecyl group can be used. An alkyl propylene sulfonate such as sodium phenyl sulfonate or sodium lauryl sulfone sulfonate. Specifically, as the cationic surfactant, an amine salt such as stearylamine hydrochloride or lauryl trimethylammonium chloride or a fourth-order ammonium salt or the like can be used. The surfactant may be used singly or in combination of two or more. The surfactant is contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, based on the alkali developer.

透過前述過程，而可獲得黑色矩陣或黑柱間隔。彩色濾光片的構成及製造方法，於本發明所屬領域中係為公知技術，故省略其詳細說明。 Through the foregoing process, a black matrix or black column spacing can be obtained. The configuration and manufacturing method of the color filter are well-known in the art to which the present invention pertains, and thus detailed description thereof will be omitted.

本發明，具備上述彩色濾光片的液晶顯示裝置亦包含於申請範圍內。 According to the present invention, a liquid crystal display device including the above color filter is also included in the scope of the application.

本發明的液晶顯示裝置，除具備上述彩色濾光片外，亦包含本發明的技術領域中，公知的構成。亦即，可適用本發明的彩色濾光片的液晶顯示裝置，皆包含於本發明中。作為一例，可列舉具備有薄膜電晶體(TFT元件)、像素電極及配向層的電極基板，將其設置成以預定間隔相間而相對向的狀態，再於此間隙部內注入液晶材料作為液晶層的透過型液晶顯示裝置。此外，也有於彩色濾光片的基板與著色層間，設置反射層的反射型液晶顯示裝置。 The liquid crystal display device of the present invention includes a known configuration in addition to the color filter described above in the technical field of the present invention. That is, a liquid crystal display device to which the color filter of the present invention is applicable is included in the present invention. An example of an electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is provided so as to be opposed to each other at a predetermined interval, and a liquid crystal material is injected into the gap portion as a liquid crystal layer. Transmissive liquid crystal display device. Further, there is also a reflective liquid crystal display device in which a reflective layer is provided between a substrate of a color filter and a coloring layer.

此外，作為另一例，可列舉包含結合於彩色濾光片的透明電極上的TFT(薄膜電晶體：Thin Film Transistor)基板；及固定在TFT基板與彩色濾光片相重疊的位置上的背光源的液晶顯示裝置。該TFT基板可具備由包圍彩色濾光片的周邊表面的光防止樹脂(light-proof resin)所構成的外部框架；由供給至外部框架內的向列液晶所構成的液晶層；分別提供至液晶層的各領域的複數像素電極；由像素電極所構成的透明玻璃基板；及形成於透明玻璃基板的露出表面上的偏光板。 Further, as another example, a TFT (Thin Film Transistor) substrate including a transparent electrode bonded to a color filter; and a backlight fixed at a position where the TFT substrate overlaps the color filter may be cited. Liquid crystal display device. The TFT substrate may include an outer frame composed of a light-proof resin surrounding a peripheral surface of the color filter, and a liquid crystal layer composed of nematic liquid crystal supplied to the outer frame; respectively provided to the liquid crystal a plurality of pixel electrodes of each layer of the layer; a transparent glass substrate composed of the pixel electrodes; and a polarizing plate formed on the exposed surface of the transparent glass substrate.

偏光板，具有垂直地透過的偏光方向，由與聚乙二醇相同的有機材料所構成。複數像素電極，與分別形成在TFT基板的玻璃基板上的複數薄膜電晶體相連接。如欲於特定像素電極上，施予預定電位差，則可將預定電壓施予至像素電極與透明電極間。因此，相應於電壓所形成的電場，可使與液晶層的特定像素電極相對應領域的配向發生變化。 The polarizing plate has a polarizing direction that is vertically transmitted, and is composed of the same organic material as polyethylene glycol. The plurality of pixel electrodes are connected to a plurality of thin film transistors respectively formed on the glass substrate of the TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage can be applied between the pixel electrode and the transparent electrode. Therefore, the alignment of the field corresponding to the specific pixel electrode of the liquid crystal layer can be changed corresponding to the electric field formed by the voltage.

以下，將透過實施例及比較例對本發明更詳細地進行說明。此些示例僅為用以說明本發明，並非用以限制本發明的範圍。 Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The examples are only intended to illustrate the invention and are not intended to limit the scope of the invention.

〔<製造例>顏料分散液M的製造〕 [Production Example: Production of Pigment Dispersion M]

將碳黑20.0g、作為分散劑的AJISPER PB821(味之素Fine-Techmo公司製)6g、作為溶媒的丙二醇甲醚醋酸酯74g，使用珠磨機經12小時的混合分散而製造出顏料分散液M。 20.0 g of carbon black, 6 g of AJISPER PB821 (manufactured by Ajinomoto Fine-Techmo Co., Ltd.) and 74 g of propylene glycol methyl ether acetate as a solvent were mixed and dispersed in a bead mill for 12 hours to produce a pigment dispersion liquid. M.

〔<合成例1~20>鹼可溶性樹脂的合成〕 [<Synthesis Example 1-20> Synthesis of Alkali Soluble Resin]

於具備攪拌機、溫度計、迴流冷卻管、滴液漏斗及氮導入管的1000ml燒瓶內，依照下列表2及表3的配合量投入丙二醇甲醚醋酸酯(PGMA)、AIBN、2-丙烯酰氧基乙基琥珀酸鹽類(B-1)、N-苯基馬來醯亞胺、苯乙烯、甲基丙烯酸、異冰片甲基丙烯酸酯類(B-2)，進行氮置換(下列表2及3的單位為g)。之後，邊攪拌邊使反應液的溫度上升至100℃，上升之後，再經7小時反應。如此所合成的鹼可溶性樹脂的最終固形成分、固形成分的酸價及以GPC所測定的重量平均分子量，列示於下列表2及3。於各合成例中所使用的(B-1)與(B-2)是與下列表1相同。 In a 1000 ml flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, propylene glycol methyl ether acetate (PGMA), AIBN, and 2-acryloyloxy group were placed in accordance with the amounts shown in Tables 2 and 3 below. Ethyl succinate (B-1), N-phenylmaleimide, styrene, methacrylic acid, isobornyl methacrylate (B-2), nitrogen substitution (Table 2 below) The unit of 3 is g). Thereafter, the temperature of the reaction liquid was raised to 100 ° C while stirring, and then the reaction was further carried out for 7 hours. The final solid content of the alkali-soluble resin thus synthesized, the acid value of the solid component, and the weight average molecular weight measured by GPC are shown in Tables 2 and 3 below. (B-1) and (B-2) used in each synthesis example are the same as in the following Table 1.

〔表2〕 〔Table 2〕

〔<實施例1~17>黑色感光性樹脂組成物的製造〕 [Examples 1 to 17> Production of Black Photosensitive Resin Composition]

以下列表4及5的組成，使用相關業界中公知的方法製造黑色感光性樹脂組成物。下列表4及5的單位為g。 In the compositions of the following Tables 4 and 5, a black photosensitive resin composition was produced by a method known in the art. The units in Tables 4 and 5 below are g.

〔表4〕 〔Table 4〕

1)KAYARAD DPHA(日本化藥公司製) 1) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

2)Ciba Specialty Chemical 2) Ciba Specialty Chemical

3)Ciba Specialty Chemical 3) Ciba Specialty Chemical

4)Ciba Specialty Chemical 4) Ciba Specialty Chemical

5)4,4’-二(N,N’-二甲基氨基)-苯甲酮(保土谷化學工業公司製) 5) 4,4'-bis(N,N'-dimethylamino)-benzophenone (manufactured by Hodogaya Chemical Industry Co., Ltd.)

〔<比較例1~4>黑色感光性樹脂組成物的製造〕 [<Comparative Examples 1 to 4> Production of Black Photosensitive Resin Composition]

以下列表6的組成，使用與前述實施例相同的方法製造黑色感光性樹脂組成物。下列表6的單位為g。 In the composition of the following Table 6, a black photosensitive resin composition was produced by the same method as the above Example. The unit of the following list 6 is g.

1)WR-101(ADEKA公司製) 1) WR-101 (made by Adeka)

2)KAYARAD DPHA(日本化藥公司製) 2) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

3)Ciba Specialty Chemical 3) Ciba Specialty Chemical

4)Ciba Specialty Chemical 4) Ciba Specialty Chemical

5)Ciba Specialty Chemical 5) Ciba Specialty Chemical

6)4,4’-二(N,N’-二甲基氨基)-苯甲酮(保土谷化學工業公司製) 6) 4,4'-bis(N,N'-dimethylamino)-benzophenone (manufactured by Hodogaya Chemical Industry Co., Ltd.)

〔<實驗例1>熱流動性的評價〕 [Experimental Example 1>Evaluation of Thermal Fluidity]

將於前述實施例1~17與比較例1~4中所製造的黑色感光性樹脂組成物，以旋轉塗布法塗布於玻璃基板上後，置於加熱板上於溫度100℃中，維持2分鐘使其形成薄膜。 接著，於該薄膜上，載置將透過率介於1~100%範圍內使其呈階段式變化的圖型；以及具有1μm~50μm線寬/線距的圖型的測試光罩，並與測試光罩設定間隔50μm，進行紫外線照射。此時，紫外線光源是使用含有g、h、i線全部的1KW的高壓水銀燈，以50mJ/cm2的照度進行照射，並無使用特別的光學濾光片。將照射過前述紫外線的薄膜沉入pH10.5的KOH水溶液顯影溶液中2分鐘，進行顯影。將貼附有此薄膜的玻璃板使用蒸餾水進行洗滌後，以氮氣進行吹煉後，進行乾燥，再經於230℃的加熱烤爐中加熱20分鐘後，製造出彩色濾光片。於前述過程中所製造的彩色濾光片的薄膜厚度為1.0μm。對顯影之後所殘存的曝光部的20μm圖型的膜厚度於曝後烤處理前、後進行測定，與下列相同地對熱流動性進行測定，並將其結果依下列所述基準進行評價後，列示於表7。 The black photosensitive resin compositions produced in the above Examples 1 to 17 and Comparative Examples 1 to 4 were applied onto a glass substrate by a spin coating method, and then placed on a hot plate at a temperature of 100 ° C for 2 minutes. It is formed into a film. Next, a pattern in which the transmittance is in the range of 1 to 100% in a stepwise manner is placed on the film; and a test mask having a pattern of 1 μm to 50 μm line width/line spacing is used, and The test mask was set at an interval of 50 μm to perform ultraviolet irradiation. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all of the g, h, and i lines, and no special optical filter was used. The film irradiated with the above ultraviolet rays was submerged in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to carry out development. The glass plate to which the film was attached was washed with distilled water, then blown with nitrogen, dried, and heated in a heating oven at 230 ° C for 20 minutes to produce a color filter. The color filter manufactured in the foregoing process had a film thickness of 1.0 μm. The film thickness of the 20 μm pattern of the exposed portion remaining after development was measured before and after the post-exposure baking treatment, and the thermal fluidity was measured in the same manner as described below, and the results were evaluated according to the following criteria. Listed in Table 7.

＊(曝後烤處理後的膜厚度/曝後烤處理前的膜厚度)×100 * (film thickness after baking after exposure / film thickness before baking after baking) × 100

○：97%以上、△：95~97%、×：95%以下 ○: 97% or more, △: 95 to 97%, ×: 95% or less

如前述表7所示，可得知實施例的黑色感光性樹脂組成物，熱流動性減少，且於曝後烤處理前、後的膜厚度方面，並無較大變化。另一方面，可得知比較例的黑色感光性樹脂組成物的場合，熱流動性較大，且於曝後烤處理 前、後，產生膜厚度的差。此外，化學式1及化學式2的單體的配合量呈少量的實施例10、11及13的組成物，其熱流動性的低下效果，並沒有與其他實施例相同程度地獲得改善。 As shown in the above Table 7, it was found that the black photosensitive resin composition of the examples had a small heat flow property and did not largely change in the film thickness before and after the post-exposure baking treatment. On the other hand, when the black photosensitive resin composition of the comparative example is known, the thermal fluidity is large, and it is baked after exposure. The difference in film thickness occurs before and after. Further, the amounts of the monomers of Chemical Formula 1 and Chemical Formula 2 were a small amount of the compositions of Examples 10, 11 and 13, and the effect of lowering the thermal fluidity was not improved to the same extent as the other examples.

〔<實驗例2>儲藏安定性的評價〕 [<Experiment 2> Evaluation of storage stability]

將於前述實施例1~17與比較例1~4中所製造的光遮蔽用黑色感光性樹脂組成物於25℃下，各別放置5日、3日、1日的組成物；以及依照標準資料，將最接近於各別相應組成物進行圖型評價實驗前所製造出的組成物，以旋轉塗布法塗布於玻璃基板上後，置於加熱板上於溫度100℃中，維持2分鐘使其形成薄膜。載置具有20μm的圖型的測試光罩，並與測試光罩設定間隔50μm，進行紫外線照射。此時，紫外線光源是使用含有g、h、i線全部的1KW的高壓水銀燈，以50mJ/cm2的照度進行照射，並無使用特別的光學濾光片。將照射過前述紫外線的薄膜沉入pH10.5的KOH水溶液顯影溶液中2分鐘，進行顯影。將貼附有此薄膜的玻璃板使用蒸餾水進行洗滌後，以氮氣進行吹煉後，進行乾燥，再經於230℃的加熱烤爐中加熱20分鐘後，製造出彩色濾光片。於前述過程中所製造的彩色濾光片中，對具有20μm線寬的遮罩上所形成的圖型的線寬，各別進行測定後，對基於放置時間所造成的線寬變化量(△CD)進行測定，並將其結果列示於下列表8。 The composition of the black photosensitive resin composition for light shielding manufactured in the above Examples 1 to 17 and Comparative Examples 1 to 4 was placed at 25 ° C for 5 days, 3 days, and 1 day, respectively; The data obtained by performing the pattern evaluation experiment closest to each respective composition was applied to a glass substrate by a spin coating method, and then placed on a hot plate at a temperature of 100 ° C for 2 minutes. It forms a film. A test reticle having a pattern of 20 μm was placed and set at a distance of 50 μm from the test reticle to perform ultraviolet ray irradiation. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all of the g, h, and i lines, and no special optical filter was used. The film irradiated with the above ultraviolet rays was submerged in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to carry out development. The glass plate to which the film was attached was washed with distilled water, then blown with nitrogen, dried, and heated in a heating oven at 230 ° C for 20 minutes to produce a color filter. In the color filter manufactured in the foregoing process, the line width of the pattern formed on the mask having a line width of 20 μm, after each measurement, the amount of change in line width caused by the standing time (Δ) The CD was measured and the results are shown in Table 8 below.

△CD=以當天所製造的樹脂組成物進行評價的圖型的線寬-以經常溫放置的樹脂組成物進行評價的圖型的線寬 ΔCD = line width of the pattern evaluated by the resin composition manufactured on the day - line width of the pattern evaluated by the resin composition placed at room temperature

○：△CD=0.5μm以下 ○: ΔCD = 0.5 μm or less

△：△CD=0.5~1.0μm △: △ CD = 0.5 ~ 1.0 μm

×：△CD=1.0μm以上 ×: ΔCD = 1.0 μm or more

如前述表8所示，於常溫下，基於組成物的放置時間，實施例的黑色感光性樹脂組成物並無造成圖型線寬的差，但是比較例的組成物則自放置3日後，開始顯示圖型線寬的變化。 As shown in the above Table 8, at the normal temperature, the black photosensitive resin composition of the example did not cause a difference in pattern line width based on the standing time of the composition, but the composition of the comparative example was started after being placed for 3 days. Displays the change in the line width of the pattern.

〔<實驗例3>微細性及感度的評價〕 [<Experimental Example 3> Evaluation of fineness and sensitivity]

將於前述實施例與比較例的組成物，以旋轉塗布法塗布於玻璃基板上後，置於加熱板上於溫度100℃中，維持2分鐘使其形成薄膜。載置具有20μm的圖型的測試光罩，並與測試光罩設定間隔50μm，進行紫外線照射。此時，紫外線光源是使用含有g、h、i線全部的1KW的高壓水銀燈，以50mJ/cm2的照度進行照射，並無使用特別的光學濾光片。將照射過前述紫外線的薄膜沉入pH10.5的KOH水溶液顯影溶液中2分鐘，進行顯影。將貼附有此薄膜的玻璃板使用蒸餾水進行洗滌後，使用光學顯微鏡，觀察幾μm的圖型為止殘存著，並列示於下列表9。 The composition of the above examples and comparative examples was applied onto a glass substrate by a spin coating method, and then placed on a hot plate at a temperature of 100 ° C for 2 minutes to form a film. A test reticle having a pattern of 20 μm was placed and set at a distance of 50 μm from the test reticle to perform ultraviolet ray irradiation. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm 2 using a high-pressure mercury lamp of 1 kW containing all of the g, h, and i lines, and no special optical filter was used. The film irradiated with the above ultraviolet rays was submerged in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to carry out development. The glass plate to which the film was attached was washed with distilled water, and then left to observe a pattern of several μm using an optical microscope, and is shown in Table 9 below.

〔表9〕 [Table 9]

如前述表9所示，可得知實施例的組成物，因8μm的圖型為止仍殘存著，故其感度優異，而比較例的組成物，因8μm的圖型為止亦仍殘存著，故其感度良好。可得知化學式1或化學式2的單體的含量較小的實施例10、11及13的場合，密著性及基於此原因感度多少會減少。此外，可得知化學式1或化學式2的單體的含量較高的實施例12及14的場合，顯示隨密著性的増加，因而微細圖型間產生殘膜的連接，感度進而減少的傾向。 As shown in the above-mentioned Table 9, it can be seen that the composition of the example remains in the pattern of 8 μm, so that the sensitivity is excellent, and the composition of the comparative example still remains due to the pattern of 8 μm. Its sensitivity is good. In the case of Examples 10, 11 and 13 in which the content of the monomer of Chemical Formula 1 or Chemical Formula 2 was small, the adhesion and the degree of sensitivity were somewhat reduced. Further, in the case of Examples 12 and 14 in which the content of the monomer of Chemical Formula 1 or Chemical Formula 2 is high, it is revealed that the adhesion is caused by the adhesion, and the connection of the residual film occurs between the fine patterns, and the sensitivity is further reduced. .

〔<實驗例4>密著性的評價〕 [<Experimental Example 4>Evaluation of Adhesion]

以與前述實驗例1~3相同的方法進行至顯影工程為止後，於超高壓洗滌工程(2MPa)，使用蒸餾水進行30秒鐘洗滌後，使用光學顯微鏡，觀察幾μm的圖型為止有無圖型洗除，並列示於表10。 After the development process was carried out in the same manner as in the above Experimental Examples 1 to 3, the ultrahigh pressure washing process (2 MPa) was carried out by using distilled water for 30 seconds, and then an optical microscope was used to observe the pattern of a few μm. Washed out and listed in Table 10.

根據前述表10，可得知實施例的組成物的場合，與比較例的組成物相較，至微細圖型為止並無洗除現象與亦無圖型間的連接顯影。 According to the above Table 10, when the composition of the example was known, compared with the composition of the comparative example, there was no washing phenomenon and no connection development between the patterns and the fine pattern.

如前述所示，包含將含有本發明的化學式1的化合物的單 體進行聚合後所製造的鹼可溶性樹脂的黑色感光性樹脂組成物，不僅與基板間的密著性、感度、儲藏安定性優異，因曝後烤處理之際的熱流動性較弱，而可減少圖型的流下現象，故可提供光學密度平均的圖型及黑色矩陣。 As indicated above, a single containing a compound containing the chemical formula 1 of the present invention is contained. The black photosensitive resin composition of the alkali-soluble resin produced by the polymerization is excellent not only in adhesion to the substrate, sensitivity, and storage stability, but also in heat flow during the post-exposure baking treatment. By reducing the downflow of the pattern, an optical density average pattern and a black matrix can be provided.

Claims (8)

一種黑色感光性樹脂組成物，係為包含以含有下列一化學式1中所記載之化合物之一單體進行聚合反應而獲得之一鹼可溶性樹脂(B)之該黑色感光性樹脂組成物， (化學式1中，n表示2~4的常數)，該單體更包含下列一化學式2中所記載之化合物， (化學式2中，m表示0~2的常數)，其中該單體不包含含有氟原子的化合物。 A black photosensitive resin composition comprising the black photosensitive resin composition obtained by polymerizing a monomer containing one of the compounds described in the following Chemical Formula 1 to obtain an alkali-soluble resin (B). (In Chemical Formula 1, n represents a constant of 2 to 4), and the monomer further contains the compound described in the following Chemical Formula 2, (In Chemical Formula 2, m represents a constant of 0 to 2), wherein the monomer does not contain a compound containing a fluorine atom. 如申請專利範圍第1項所述之黑色感光性樹脂組成物，該化學式1中所記載之化合物相對於該單體，係含有10~40重量部。 The black photosensitive resin composition according to the first aspect of the invention, wherein the compound of the chemical formula 1 contains 10 to 40 parts by weight based on the monomer. 如申請專利範圍第1項所述之黑色感光性樹脂組成物，該化學式2中所記載之化合物相對於該單體，係含有10~40重量部。 The black photosensitive resin composition according to the first aspect of the invention, wherein the compound of the chemical formula 2 contains 10 to 40 parts by weight based on the monomer. 如申請專利範圍第1項所述之黑色感光性樹脂組成 物，該鹼可溶性樹脂(B)相對於組成物之固形成分，係含有4~25重量部。 The composition of the black photosensitive resin as described in claim 1 The alkali-soluble resin (B) contains 4 to 25 parts by weight relative to the solid content of the composition. 如申請專利範圍第1項所述之黑色感光性樹脂組成物，該單體係更包含(甲基)丙烯酸酯系化合物、芳香族乙烯基化合物、羧酸乙烯基酯化合物、氰化乙烯基化合物、馬來醯亞胺化合物、乙烯基羧酸酯化合物、不飽和環氧丙烷羧酸酯化合物、單羧酸化合物、二羧酸化合物及二末端具有羧基與羥基的化合物所組成群組所選出之單獨或複數種之混合物。 The black photosensitive resin composition according to claim 1, wherein the single system further comprises a (meth) acrylate compound, an aromatic vinyl compound, a carboxylic acid vinyl ester compound, and a vinyl cyanide compound. Selected from the group consisting of a maleimide compound, a vinyl carboxylate compound, an unsaturated propylene oxide carboxylate compound, a monocarboxylic acid compound, a dicarboxylic acid compound, and a compound having a carboxyl group and a hydroxyl group at both terminals A mixture of singly or plural. 如申請專利範圍第1項所述之黑色感光性樹脂組成物，該黑色感光性樹脂組成物係更包含自著色劑(A)、光聚合性化合物(C)、光聚合開始劑(D)及溶劑(E)所組成群組所選出之單獨或複數種之混合物。 The black photosensitive resin composition according to the first aspect of the invention, wherein the black photosensitive resin composition further comprises a coloring agent (A), a photopolymerizable compound (C), a photopolymerization initiator (D), and A mixture of individual or plural selected from the group consisting of solvents (E). 一種黑色矩陣(Black Matrix)，係將申請專利範圍第1項至第6項中任一項所述之黑色感光性樹脂組成物進行塗布、曝光及顯影而獲得。 A black matrix obtained by coating, exposing, and developing a black photosensitive resin composition according to any one of claims 1 to 6. 一種彩色濾光片(Color Filter)，係具備有申請專利範圍第7項所述之黑色矩陣。 A color filter having a black matrix as described in claim 7 of the patent application.
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