TWI597572B - A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same - Google Patents

A colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same Download PDF

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TWI597572B
TWI597572B TW104106838A TW104106838A TWI597572B TW I597572 B TWI597572 B TW I597572B TW 104106838 A TW104106838 A TW 104106838A TW 104106838 A TW104106838 A TW 104106838A TW I597572 B TWI597572 B TW I597572B
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resin composition
photosensitive resin
red
colored photosensitive
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TW201535049A (en
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申泳璨
金秀虎
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東友精細化工有限公司
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Description

濾色器用著色感光性樹脂組合物、濾色器及具備其的液晶顯示裝置 Coloring photosensitive resin composition for color filter, color filter, and liquid crystal display device therewith

本發明涉及著色感光性樹脂組合物，更詳細的，涉及在製造用於彩色液晶顯示器等的紅色濾色器時使用的紅色濾色器用著色感光性樹脂組合物。 The present invention relates to a colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition for a red color filter used in the production of a red color filter for a color liquid crystal display or the like.

近期，隨著對液晶顯示器(LCD)用濾色器的高色彩再現的需求，製造濾色器時所使用的著色感光性樹脂組合物的著色材料的含量持續上升。並且，為了製造可視性優異的高品質濾色器，正持續形成對對比度的改善需求。 Recently, with the demand for high color reproduction of color filters for liquid crystal displays (LCDs), the content of the coloring materials of the colored photosensitive resin compositions used in the production of color filters has continued to increase. Further, in order to manufacture a high-quality color filter excellent in visibility, there is a continuing need to improve the contrast.

但是，在現有的顏料分散體系中，著色感光性樹脂組合物內的顏料含量正達到極限，並且，通過顏料的微粒化所進行的對比度的改善也達到了極限。當前，正在研究將顏料和染料同時用作著色劑的方法。但是，當利用將染料用作著色劑的著色感光性樹脂組合物來製造濾色器的情況下，由於缺乏靈敏度，因而在利用鹼性顯影液進行顯影工序時，產生所形成的圖案剝離的現象。並且，在使用包含染料的著色感光性樹脂組合物製造濾色器時，由於染料在 硬烘烤工序中缺乏相容性，因而染料向表面析出，導致對比度下降，因此難以使用足量的染料。 However, in the conventional pigment dispersion system, the pigment content in the colored photosensitive resin composition is reaching the limit, and the improvement in contrast by the micronization of the pigment also reaches the limit. Currently, methods for simultaneously using pigments and dyes as colorants are being studied. However, when a color filter is manufactured by using the colored photosensitive resin composition using a dye as a coloring agent, since the sensitivity is lacking, the formed pattern peeling phenomenon occurs when the developing process is performed by the alkaline developing solution. . Further, when a color filter is produced using a colored photosensitive resin composition containing a dye, since the dye is The lack of compatibility in the hard baking process causes the dye to precipitate on the surface, resulting in a decrease in contrast, so that it is difficult to use a sufficient amount of dye.

現有技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：韓國公開專利2012-0112121號 Patent Document 1: Korean Patent Publication No. 2012-0112121

本發明的目的在於，使用最少量的染料來實現高透射、高對比，並以靈敏度不因染料而下降的方式，解決在顯影工序中圖案被剝離的問題。 An object of the present invention is to achieve high transmission and high contrast using a minimum amount of dye, and to solve the problem that the pattern is peeled off in the development process in such a manner that the sensitivity is not lowered by the dye.

為了實現上述目的，本發明提供紅色像素用著色感光性樹脂組合物，其特徵在於，是包含著色劑(A)、鹼可溶性樹脂(B)、光聚合性化合物(C)、光聚合引發劑(D)、溶劑(E)的著色感光性樹脂組合物，上述著色劑(A)包含C.I.顏料紅254和C.I.顏料紅177，並包含選自C.I.顏料紅242、由下述化學式1表示的呫噸系染料和金屬配位元化合物結構的偶氮系染料中的2種以上，上述光聚合引發劑(D)包含由下述化學式2表示的含有二苯硫基的肟酯系光引發劑， In order to achieve the above object, the present invention provides a colored photosensitive resin composition for red pixels, which comprises a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), and a photopolymerization initiator ( D) The colored photosensitive resin composition of the solvent (E), wherein the coloring agent (A) contains CI Pigment Red 254 and CI Pigment Red 177, and contains x-tons selected from CI Pigment Red 242 and represented by the following Chemical Formula 1 Two or more of the azo dyes having a dye and a metal complex compound structure, and the photopolymerization initiator (D) contains a diphenylthio group-containing oxime ester photoinitiator represented by the following Chemical Formula 2,

在上述式中，R1、R2、R3、R4、R5和R6各自獨立地為氫或C1~C5的烷基，R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、SO3Na、COOCH3或COOCH2CH3。 In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen or a C1 to C5 alkyl group, and R 7 and R 8 are each independently hydrogen, COOH, COO - , SO 3 - , SO 3 H, SO 3 Na, COOCH 3 or COOCH 2 CH 3 .

在上述式中，R9為下述化學式3，R10為C1~C8的烷基、被取代或未被取代的苯基、或被取代或未被取代的苄基，R11為二苯硫基；[化學式3]-R12-R13 In the above formula, R 9 is a chemical formula 3, R 10 is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R 11 is diphenyl sulfide. Base; [Chemical Formula 3]-R12-R13

在上述式中，R12為C1~C4的亞烷基，R13為C3~C8的烴或C3~C8的環烴。 In the above formula, R12 is a C1 to C4 alkylene group, and R13 is a C3 to C8 hydrocarbon or a C3 to C8 cyclic hydrocarbon.

本發明提供紅色像素用著色感光性樹脂組合物，其特徵在於，相對於上述著色感光性樹脂組合物中的總固體成分，包含5~60重量%的著色劑(A)、10~80重量%的鹼可溶性樹脂(B)和5~45重量%的光聚合性化合物(C)；相對於上述鹼可溶性樹脂(B)和光聚合性化合物(C)的固體成分的重量，包含0.1~40重量%的光聚合引發劑(D)。 The present invention provides a colored photosensitive resin composition for a red pixel, which comprises 5 to 60% by weight of a coloring agent (A) and 10 to 80% by weight based on the total solid content of the colored photosensitive resin composition. The alkali-soluble resin (B) and 5 to 45% by weight of the photopolymerizable compound (C); and 0.1 to 40% by weight based on the weight of the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) Photopolymerization initiator (D).

本發明提供由上述紅色像素用著色感光性樹脂組合物製成的濾色器。 The present invention provides a color filter made of the above-described colored photosensitive resin composition for red pixels.

本發明提供包括上述濾色器的液晶顯示裝置。 The present invention provides a liquid crystal display device including the above color filter.

本發明的著色感光性樹脂組合物具有透射度和對比度優異，且在低曝光量下圖案也不會被剝離的優異的效果。並且，亮度和對比度(contrast)優異。 The colored photosensitive resin composition of the present invention is excellent in transmittance and contrast, and has an excellent effect that the pattern is not peeled off at a low exposure amount. Also, the brightness and contrast are excellent.

本發明提供紅色像素用著色感光性樹脂組合物，其特徵在於，是包含著色劑(A)、鹼可溶性樹脂(B)、光聚合性化合物(C)、光聚合引發劑(D)、溶劑(E)的著色感光性樹脂組合物，上述著色劑(A)包含C.I.顏料紅254和C.I.顏料紅177，並包含選自C.I.顏料紅242、由下述化學式1表示的呫噸系染料和金屬配位元化合物結構的偶氮系染料中的2種以上，上述光聚合引發劑(D)包含由下述化學式2表示的含有二苯硫基的肟酯系光引發劑， The present invention provides a coloring photosensitive resin composition for a red pixel, which comprises a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent ( In the colored photosensitive resin composition of E), the coloring agent (A) contains CI Pigment Red 254 and CI Pigment Red 177, and contains a xanthene-based dye selected from the following Chemical Formula 1 and a metal compound selected from CI Pigment Red 242. The photopolymerization initiator (D) containing the diphenylthio group-containing oxime ester photoinitiator represented by the following Chemical Formula 2, and two or more of the azo dyes of the steric compound structure,

在上述式中，R1、R2、R3、R4、R5和R6各自獨立地為氫或C1~C5的烷基，R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、SO3Na、COOCH3或COOCH2CH3；[化學式2] In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen or a C1 to C5 alkyl group, and R 7 and R 8 are each independently hydrogen, COOH, COO - , SO 3 - , SO 3 H, SO 3 Na, COOCH 3 or COOCH 2 CH 3 ; [Chemical Formula 2]

在上述式中，R9為下述化學式3，R10為C1~C8的烷基、被取代或未被取代的苯基、或被取代或未被取代的苄基，R11為二苯硫基；[化學式3]-R12-R13 In the above formula, R 9 is a chemical formula 3, R 10 is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R 11 is diphenyl sulfide. Base; [Chemical Formula 3]-R12-R13

在所述化學式3中，R12為C1~C4的亞烷基，R13為C3~C8的烴或C3~C8的環烴。 In the chemical formula 3, R12 is a C1 to C4 alkylene group, and R13 is a C3 to C8 hydrocarbon or a C3 to C8 cyclic hydrocarbon.

本發明的紅色像素用著色感光性樹脂組合物通過使用將染料作為著色劑的四元系，從而具有透射度和對比度優異，且在使用染料的情況下圖案也不會被剝離的優異的效果。並且，亮度和對比度(CR)優異。 The colored photosensitive resin composition for red pixels of the present invention is excellent in transmittance and contrast by using a quaternary system using a dye as a coloring agent, and has an excellent effect that the pattern is not peeled off when a dye is used. Also, brightness and contrast (CR) are excellent.

並且，通過包含含有二苯硫基的肟酯系光引發劑，從而防止由染料造成的靈敏度和透射率下降，並使將染料作為著色劑的本發明的著色感光性樹脂組合物能夠表達有效的光聚合特性。 Further, by including an oxime ester-based photoinitiator containing a diphenylthio group, the sensitivity and transmittance of the dye are prevented from being lowered, and the colored photosensitive resin composition of the present invention containing a dye as a colorant can be expressed efficiently. Photopolymerization characteristics.

以下，對構成本發明的紅色像素用著色感光性樹脂組合物的各成分進行說明。 Hereinafter, each component constituting the colored photosensitive resin composition for red pixels of the present invention will be described.

著色劑(A) Colorant (A)

上述著色劑(A)以C.I.顏料紅254、C.I.顏料紅177兩種顏料作為必要成分，並以選自C.I.顏料紅242、由下述化學式1表示的呫噸系染料和金屬配位元化合物結構的 偶氮系染料中的2種以上作為必要成分。 The coloring agent (A) has two pigments, CI Pigment Red 254 and CI Pigment Red 177, as essential components, and a xanthene-based dye and a metal complex compound structure selected from CI Pigment Red 242 and represented by Chemical Formula 1 below. of Two or more kinds of azo dyes are essential components.

顏料(a1) Pigment (a1)

在本發明中，顏料以C.I.顏料紅254(以下，稱為R254)、C.I.顏料紅177(以下，稱為R177)兩種顏料作為必要成分。 In the present invention, the pigment is an essential component of C.I. Pigment Red 254 (hereinafter referred to as R254) and C.I. Pigment Red 177 (hereinafter referred to as R177).

R254雖然具有透射度良好的優點，但對比度不高，並且具有由於莫耳吸光率低，因而需提高著色劑的含量的缺點，因而，在著色劑中優選含30~80重量%以下。若小於30重量%，則亮度的上升幅度不大，若大於80重量%，則對比度低，並且由於著色感光性樹脂組合物中的著色劑的比率上升，因而並不優選。 Although R254 has an advantage of good transmittance, the contrast is not high, and since the molar absorption rate is low, it is required to increase the content of the colorant. Therefore, it is preferable that the coloring agent contains 30 to 80% by weight or less. When the amount is less than 30% by weight, the increase in brightness is not large. When the amount is more than 80% by weight, the contrast is low, and the ratio of the coloring agent in the colored photosensitive resin composition is increased, which is not preferable.

由於C.I.顏料紅177可靠性良好，且容易實現微粒化，因而容易提高對比，但透射度不高。優選地，在總著色劑中，包含10~50重量%。若小於10重量%，則對比度的上升效果不明顯，並且使著色劑中的染料的比率上升，因而導致可靠性變差，若大於50重量%，則會使透射度下降。 Since C.I. Pigment Red 177 has good reliability and is easy to achieve micronization, it is easy to improve the contrast, but the transmittance is not high. Preferably, it comprises 10 to 50% by weight in the total colorant. If it is less than 10% by weight, the effect of increasing the contrast is not remarkable, and the ratio of the dye in the colorant is increased, so that the reliability is deteriorated, and if it is more than 50% by weight, the transmittance is lowered.

本發明除C.I.顏料紅254、C.I.顏料紅177之外，還包含2種以上的顏料/染料，因而與現有的R254/R177色料形成的著色感光性樹脂組合物相比，能夠實現高透射度和高對比。 Since the present invention contains two or more kinds of pigments/dyes in addition to CI Pigment Red 254 and CI Pigment Red 177, it is possible to achieve high transmittance as compared with the conventional coloring photosensitive resin composition formed of the R254/R177 colorant. And high contrast.

由於與R254相比，C.I.顏料紅242(以下稱為R242)的對比度和可靠性優異，但莫耳吸光率低，因而，在總著色劑中優選包含5~20重量%以下的C.I.顏料紅242。若小於5重量%，則亮度和對比度的提高效果不明顯，若大於 20重量%，則由於著色感光性樹脂組合物中的著色劑的比率上升，因而並不優選。 CI Pigment Red 242 (hereinafter referred to as R242) is superior in contrast and reliability to R254, but has a low molar absorbance. Therefore, it is preferable to contain 5 to 20% by weight or less of CI Pigment Red 242 in the total colorant. . If it is less than 5% by weight, the effect of improving brightness and contrast is not significant, if it is greater than When it is 20% by weight, the ratio of the coloring agent in the colored photosensitive resin composition increases, which is not preferable.

上述顏料優選使用其粒徑均勻分散的顏料分散液。作為使顏料的粒徑均勻分散的方法的一例，有包含顏料分散劑(a4)來進行分散處理的方法，借助該方法，可得到顏料均勻分散於溶液中的狀態的顏料分散液。 As the above pigment, it is preferred to use a pigment dispersion liquid whose particle diameter is uniformly dispersed. As an example of a method of uniformly dispersing the particle diameter of the pigment, there is a method in which a pigment dispersant (a4) is used for dispersion treatment, and a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained by this method.

顏料分散劑(a4) Pigment dispersant (a4)

上述颜料分散剂(a4)是为了颜料的抗凝聚()和维持稳定性而添加的，能够以不受限制的方式使用本領域通常使用的颜料分散剂。 The above pigment dispersant (a4) is for the anti-agglomeration of the pigment ( And the addition of the pigment dispersant commonly used in the art can be used in an unrestricted manner.

上述顏料分散劑的具體例有陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系等的表面活性劑等，這些顏料分散劑可分別單獨使用或組合2種以上來使用。 Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric, a polyester-based, and a polyamine-based surfactant. These pigment dispersants may be used alone or in combination of two or more.

上述顏料分散劑包含優選丙烯酸酯系分散劑(以下稱為丙烯酸酯分散劑)，上述丙烯酸酯系分散劑包含BMA(甲基丙烯酸丁酯)或DMAEMA(甲基丙烯酸N,N-二甲氨基乙酯)。此時，如在韓國公開專利2004-0014311號所提示的那樣，優選借助活性控制方法來製造上述丙烯酸分散劑，在市場上銷售的通過上述活性控制方法來製造的丙烯酸酯系分散劑可例舉DISPER BYK-2000、DISPER BYK-2001、DISPER BYK-2070、DISPER BYK-2150等。 The above pigment dispersant comprises an acrylate dispersant (hereinafter referred to as an acrylate dispersant), and the acrylate dispersant comprises BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate) ester). In this case, as described in Korean Laid-Open Patent Publication No. 2004-0014311, it is preferred to produce the above acrylic dispersant by means of an activity control method, and an acrylate-based dispersant which is commercially available and which is produced by the above-described activity control method can be exemplified. DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc.

上述例示的丙烯酸酯分散劑可分別單獨使用或組合2種以上來使用。 The above-exemplified acrylate dispersants may be used alone or in combination of two or more.

除了上述丙烯酸酯分散劑，還可將其它樹脂類型的顏 料分散劑用作上述顏料分散劑(a4)。上述其它樹脂類型的顏料分散劑可使用公知的樹脂類型的顏料分散劑，尤其可舉出以聚氨酯、聚丙烯酸酯為代表的聚羧酸酯，不飽和聚醯胺、聚羧酸、聚羧酸的(部分)胺鹽、聚羧酸的銨鹽、聚羧酸的烷基胺鹽、聚矽氧烷、長鏈聚氨基醯胺磷酸酯鹽、含羥基聚羧酸的酯和它們的改性生成物，或具有自由(free)羧基的聚酯與聚(低級烯化亞胺)的反應來形成的胺、或它們的鹽之類的乳化分散劑；(甲基)丙烯酸苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-馬來酸共聚物、聚乙烯醇或聚乙烯吡咯烷酮之類的水溶性樹脂或水溶性聚合物；聚酯；改性聚丙烯酸酯；環氧乙烷/環氧丙烷的附加生成物和磷酸酯等。 In addition to the above acrylate dispersants, other resin types can be used. A dispersant is used as the above pigment dispersant (a4). As the pigment dispersant of the above other resin type, a pigment dispersant of a known resin type can be used, and in particular, a polycarboxylate represented by polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, or a polycarboxylic acid can be mentioned. (partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polyoxyalkylene oxides, long chain polyaminoguanamine phosphates, esters of hydroxyl-containing polycarboxylic acids and their modification a product, or an emulsified dispersant such as an amine formed by reacting a polyester having a free carboxyl group with a poly(lower alkyleneimine), or a salt thereof; a (meth)acrylic styrene copolymer; Water-soluble resin or water-soluble polymer such as (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylic acid Ester; additional product of ethylene oxide/propylene oxide, phosphate ester, and the like.

作為上述樹脂類型的顏料分散劑的市售品，例如可舉出BYK化工的商品名：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184；巴斯夫(BASF)公司的商品名：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800；Lubirzol公司的商品名：SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；KAWAKEN Fine化學公司的商品名：HINOACT T-6000、HINOACT T-7000、HINOACT T-8000； Ajinomoto公司的商品名：AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823；共榮社化學公司的商品名：FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33、FLORENE DOPA-44等。除了上述丙烯酸酯分散劑之外的其它樹脂類型的顏料分散劑可分別單獨使用或組合2種以上來使用，還可與丙烯酸分散劑並用。 As a commercial item of the above-mentioned resin type pigment dispersing agent, for example, BYK Chemical's trade name: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK -166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050 , EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Lubirzol's trade name: SOLSPERS-24000 , SOLSPERS-32550, NBZ-4204/10; KAWAKEN Fine Chemical Company's trade name: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto's trade names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Kyoritsu Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. . Other resin type pigment dispersing agents other than the above acrylate dispersing agent may be used singly or in combination of two or more kinds, and may be used in combination with an acrylic dispersing agent.

上述顏料分散劑(a4)的使用量相對於顏料(a1)的固體成分100重量份，使用5~60重量份，更優選使用15~50重量份範圍。按上述的基準，若顏料分散劑(a4)的含量超過60重量份，則有可能使黏度變高，若小於5重量份，則有可能使顏料難以微粒化，或有可能引起分散後凝膠化等的問題。 The amount of the pigment dispersant (a4) used is 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). According to the above-mentioned criteria, if the content of the pigment dispersant (a4) exceeds 60 parts by weight, the viscosity may become high, and if it is less than 5 parts by weight, the pigment may be difficult to be microparticulated or may cause a gel after dispersion. Problems such as chemistry.

呫噸系染料(a2) Xanthene dye (a2)

具有上述[化學式1]的結構的呫噸系染料由於透射率和耐熱性良好，因而優選，但由於對溶劑的溶解度和相容性不足，因而難以在著色感光性樹脂組合物中足量使用。因此，在總著色劑中，優選包含5~15重量%以下。若小於5重量%，透射度的上升幅度不明顯，若大於15重量%， 則容易在塗膜內產生染料析出，由此導致對比度下降，並使著色感光性樹脂組合物的儲藏穩定性下降。 The xanthene-based dye having the structure of the above [Chemical Formula 1] is preferable because it has good transmittance and heat resistance. However, since solubility in a solvent and compatibility are insufficient, it is difficult to use it in a sufficient amount in the colored photosensitive resin composition. Therefore, it is preferable to contain 5 to 15% by weight or less of the total colorant. If it is less than 5% by weight, the increase in transmittance is not significant, and if it is more than 15% by weight, In this case, it is easy to cause dye deposition in the coating film, which causes a decrease in contrast and a decrease in storage stability of the colored photosensitive resin composition.

上述染料的具體例有酸性紅52(Acid Red 52)、鹼性紅1(Basic Red 1)、鹼性紫10(Basic Violet 10)、鹼性紫11(Basic Violet 11)、羅丹明B(Rhodamine B)、羅丹明6G(Rhodamine 6G)、羅丹明123(Rhodamine 123)、磺基羅丹明B(Sulforhodamine B)等，但並不限定於此，這些染料可分別單獨使用或組合2種以上來使用。 Specific examples of the above dyes include Acid Red 52, Basic Red 1, Basic Violet 10, Basic Violet 11, and Rhodamine B. B), Rhodamine 6G, Rhodamine 123, Sulforhodamine B, etc., but not limited thereto, these dyes may be used alone or in combination of two or more. .

金屬配位元化合物結構的偶氮系染料(a3) Azo dyes of metal coordination compound structure (a3)

與普通的偶氮系染料相比，本發明的金屬配位元化合物結構的偶氮系染料的耐熱性和溶解度良好，因而對比度優異，並且可提高著色感光性樹脂組合物內的染料的含量，因而能夠實現高亮度。但是，由於與上述的顏料/呫噸系染料相比，可靠性低，因而，在總著色劑中優選包含5~15重量%以下的上述金屬配位元化合物結構的偶氮系染料(a3)。若大於15重量%，則容易產生整個耐熱性/耐溶劑性等可靠性方面的問題，若小於5重量%，則對比度和透射率的上升並不明顯。 The azo dye of the metal complex compound structure of the present invention has good heat resistance and solubility as compared with the conventional azo dye, and thus has excellent contrast and can increase the content of the dye in the colored photosensitive resin composition. Therefore, high brightness can be achieved. However, since the reliability is low as compared with the above-described pigment/xanthene dye, the azo dye (a3) containing the above metal complex compound structure of 5 to 15% by weight or less is preferably contained in the total colorant. . When it is more than 15% by weight, reliability problems such as heat resistance and solvent resistance are likely to occur, and if it is less than 5% by weight, the increase in contrast and transmittance is not remarkable.

上述染料的具體例有C.I.溶劑黃13(C.I.Solvent Yellow 13)、C.I.溶劑黃19(C.I.Solvent Yellow 19)、C.I.溶劑黃21(C.I.Solvent Yellow 21)、C.I.溶劑黃25(C.I.Solvent Yellow 25)、C.I.溶劑黃25：1(C.I.Solvent Yellow 25：1)、C.I.溶劑黃81(C.I.Solvent Yellow 81)、C.I.溶劑黃82(C.I.Solvent Yellow 82)、C.I.溶劑黃88(C.I. Solvent Yellow 88)、C.I.溶劑黃89(C.I.Solvent Yellow 89)、C.I.溶劑黃90(C.I.Solvent Yellow 90)、C.I.溶劑橙5(C.I.Solvent Orange 5)、C.I.溶劑橙20(C.I.Solvent Orange 20)、C.I.溶劑橙40：1(C.I.Solvent Orange 40：1)、C.I.溶劑橙41(C.I.Solvent Orange 41)、C.I.溶劑橙45(C.I.Solvent Orange 45)、C.I.溶劑橙54(C.I.Solvent Orange 54)、C.I.溶劑橙56(C.I.Solvent Orange 56)、C.I.溶劑橙58(C.I.Solvent Orange 58)、C.I.溶劑橙62(C.I.Solvent Orange 62)、C.I.溶劑橙81(C.I.Solvent Orange 81)、C.I.溶劑橙99(C.I.Solvent Orange 99)、C.I.溶劑紅8(C.I.Solvent Red 8)、C.I.溶劑紅83：1(C.I.Solvent Red 83：1)、C.I.溶劑紅84：1(C.I.Solvent Red 84：1)、C.I.溶劑紅90(C.I.Solvent Red 90)、C.I.溶劑紅90：1(C.I.Solvent Red 90：1)、C.I.溶劑紅91(C.I.Solvent Red 91)、C.I.溶劑紅118(C.I.Solvent Red 118)、C.I.溶劑紅119(C.I.Solvent Red 119)、C.I.溶劑紅122(C.I.Solvent Red 122)、C.I.溶劑紅127(C.I.Solvent Red 127)、C.I.溶劑紅130(C.I.Solvent Red 130)、C.I.溶劑紅132(C.I.Solvent Red 132)、C.I.溶劑紅160(C.I.Solvent Red 160)、C.I.溶劑紅234(C.I.Solvent Red 234)、C.I.溶劑紅243(C.I.Solvent Red 243)、C.I.溶劑紫21：1(C.I.Solvent Violet 21：1)、C.I.溶劑紫58(C.I.Solvent Violet 58)、C.I.溶劑藍137(C.I.Solvent Blue 137)等。 Specific examples of the above dyes include CI Solvent Yellow 13 (CI Solvent Yellow 19), CI Solvent Yellow 19, CI Solvent Yellow 21, CI Solvent Yellow 25, CI Solvent Yellow 25, CI Solvent Yellow 25:1 (CI Solvent Yellow 25:1), CI Solvent Yellow 81 (CI Solvent Yellow 81), CI Solvent Yellow 82 (CI Solvent Yellow 82), CI Solvent Yellow 88 (CI Solvent Yellow 88), CI Solvent Yellow 89, CI Solvent Yellow 90, CI Solvent Orange 5, CI Solvent Orange 20, CI Solvent Orange 40:1 (CI Solvent Orange 40:1), CI Solvent Orange 41, CI Solvent Orange 45, CI Solvent Orange 54 (CI Solvent Orange 54), CI Solvent Orange 56 (CI Solvent Orange 56), CI Solvent Orange 58 (CI Solvent Orange 62), CI Solvent Orange 62, CI Solvent Orange 81, CI Solvent Orange 99 (CI Solvent Orange 99) ) CI Solvent Red 8 , CI Solvent Red 83:1 (CI Solvent Red 83:1), CI Solvent Red 84:1 (CI Solvent Red 84:1), CI Solvent Red 90 (CI Solvent) Red 90), CI Solvent Red 90:1 (CI Solvent Red 90:1), CI Solvent Red 91 (CI Solvent Red 91), CI Solvent Red 118 (CI Solvent Red 118), CI Solvent Red 119 (CISolvent Red 119 ) CI Solvent Red 122, CI Solvent Red 127, CI Solvent Red 130 (CISolvent R) Ed 130), CI Solvent Red 132, CI Solvent Red 160, CI Solvent Red 234, CI Solvent Red 243, CI Solvent Red 243, CI Solvent Violet 21:1 (CI Solvent Violet 21:1), CI Solvent Violet 58 (CI Solvent Violet 58), CI Solvent Blue 137 (CI Solvent Blue 137), and the like.

上述著色劑(A)的含量相對於著色感光性樹脂組合 物中的固體成分，包含5~60重量%，優選包含10~45重量%。按上述基準，在上述著色劑(A)包含5~60重量%的情況下，即使形成薄膜，像素的顏色濃度也飽滿，顯影時非像素部分的遺漏性()也不會下降，因而難以產生殘渣，因此優選。 The content of the coloring agent (A) is 5 to 60% by weight, and preferably 10 to 45% by weight, based on the solid content of the colored photosensitive resin composition. According to the above criteria, in the case where the coloring agent (A) contains 5 to 60% by weight, even if a film is formed, the color density of the pixel is full, and the non-pixel portion is missing during development ( It is also preferable because it does not fall and it is difficult to generate a residue.

在本發明中，著色感光性樹脂組合物中的總固體成分的含量意味著在著色感光性樹脂組合物中除溶劑的其餘成分的總含量。 In the present invention, the content of the total solid content in the colored photosensitive resin composition means the total content of the remaining components of the solvent in the colored photosensitive resin composition.

鹼可溶性樹脂(B) Alkali soluble resin (B)

為了對形成圖案時的顯影處理工序中所利用的鹼顯影液具有可溶性，鹼可溶性樹脂(B)以包含羧基的乙烯性不飽和單體(b1)作為必要成分來進行共聚。並且，為了確保與染料(a2)的相容性和確保著色感光性樹脂組合物的儲藏穩定性，鹼可溶性樹脂(B)的酸值優選為30~150mgKOH/g。若鹼可溶性樹脂(B)的酸值小於30mgKOH/g，則著色感光性樹脂組合物難以確保充分的顯影速度，若大於150mgKOH/g，則由於與基板之間的密合性下降，因而容易產生圖案的短路，並且由於與染料之間的相容性產生問題，因而會導致著色感光性樹脂組合物內的染料析出，或由於著色感光性樹脂組合物的儲藏穩定性下降，因而容易使黏度上升。 The alkali-soluble resin (B) is copolymerized with an ethylenically unsaturated monomer (b1) containing a carboxyl group as an essential component in order to be soluble in the alkali developer used in the development treatment step at the time of pattern formation. Further, in order to ensure compatibility with the dye (a2) and to ensure storage stability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin (B) is preferably from 30 to 150 mgKOH/g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH/g, it is difficult to ensure a sufficient development speed in the colored photosensitive resin composition, and if it is more than 150 mgKOH/g, the adhesion to the substrate is lowered, so that it is likely to be generated. The pattern is short-circuited, and the compatibility with the dye causes a problem, so that the dye in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered, so that the viscosity is easily increased. .

上述包含羧基的乙烯性不飽和單體(b1)的具體例可舉出丙烯酸、甲基丙烯酸、巴豆酸等一元羧酸類；富馬酸、中康酸、衣康酸等二元羧酸類和它們的二元羧酸的酐；ω- 羧基-聚己內酯單(甲基)丙烯酸酯等在兩個末端具有羧基和羥基的聚合物的單(甲基)丙烯酸酯類等；其中，優選為丙烯酸、甲基丙烯酸。 Specific examples of the carboxyl group-containing ethylenically unsaturated monomer (b1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and Anhydride of a dicarboxylic acid; ω- A mono(meth)acrylate such as a carboxyl group-polycaprolactone mono(meth)acrylate or the like having a carboxyl group and a hydroxyl group at both terminals; among them, acrylic acid or methacrylic acid is preferable.

為了向鹼可溶性樹脂(B)賦予羥基，可通過使具有羧基的乙烯性不飽和單體(b1)與具有羥基的乙烯性不飽和單體(b2)共聚來製造，並且可通過使具有羧基的乙烯性不飽和單體(b1)與具有縮水甘油基的化合物(b3)進一步反應來製造。並且，還可通過使具有羧基的乙烯性不飽和單體(b1)和具有羥基的乙烯性不飽和單體(b2)的共聚物與具有縮水甘油基的化合物(b3)進一步反應來製造上述鹼可溶性樹脂(B)。 In order to impart a hydroxyl group to the alkali-soluble resin (B), it can be produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group with an ethylenically unsaturated monomer (b2) having a hydroxyl group, and can be obtained by having a carboxyl group. The ethylenically unsaturated monomer (b1) is further reacted with a compound (b3) having a glycidyl group to produce. Further, the above base can also be produced by further reacting a copolymer of a carboxyl group-containing ethylenically unsaturated monomer (b1) and a hydroxyl group-containing ethylenically unsaturated monomer (b2) with a glycidyl group-containing compound (b3). Soluble resin (B).

上述具有羥基的乙烯性不飽和單體(b2)的具體例可舉出(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸-4-羥基丁基酯、(甲基)丙烯酸-2-羥基-3-苯氧基丙酯、N-羥乙基丙烯醯胺等(甲基)丙烯酸羥乙酯類。 Specific examples of the above-mentioned ethylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxyl (meth)acrylate. A hydroxyethyl (meth)acrylate such as butyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate or N-hydroxyethyl acrylamide.

上述具有縮水甘油基的化合物(b3)的具體例有丁基縮水甘油醚、縮水甘油丙基醚、縮水甘油苯醚、2-乙基己基縮水甘油醚、丁酸縮水甘油酯、縮水甘油基甲醚、乙基縮水甘油基醚、縮水甘油異丙基醚、叔丁基縮水甘油基醚、苄基縮水甘油醚、苯甲酸縮水甘油基4-叔丁基酯、硬脂酸縮水甘油基酯、芳基縮水甘油醚、甲基丙烯酸縮水甘油酯等，其中優選為丁基縮水甘油醚、芳基縮水甘油醚、甲基丙烯酸縮水甘油酯，可組合2種以上來使用。 Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, and glycidyl group. Ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl benzoate 4-tert-butyl ester, glycidyl stearate, Among them, aryl glycidyl ether and glycidyl methacrylate are preferable, and among them, butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate are preferable, and two or more types may be used in combination.

在製造上述鹼可溶性樹脂(B)時，上述具有羧基的乙烯性不飽和單體(b1)除了與具有羥基的乙烯性不飽和單體(b2)和具有縮水甘油基的化合物(b3)共聚，還可與能夠實現共聚的不飽和單體(b4)共聚。在下面例示了上述能夠實現共聚的不飽和單體(b4)，但並不限定於此。 In the production of the above alkali-soluble resin (B), the ethylenically unsaturated monomer (b1) having a carboxyl group is copolymerized with an ethylenically unsaturated monomer (b2) having a hydroxyl group and a compound (b3) having a glycidyl group. It is also copolymerizable with the unsaturated monomer (b4) capable of achieving copolymerization. Although the above-mentioned unsaturated monomer (b4) which can be copolymerized is illustrated below, it is not limited to this.

能夠實現共聚的具有不飽和鍵的聚合單體(b4)的具體例有：苯乙烯、乙烯基甲苯、α-甲基苯乙烯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基苄基甲基醚、間乙烯基苄基甲基醚、對乙烯基苄基甲基醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚等芳香族乙烯化合物；N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-鄰羥基苯基馬來醯亞胺、N-間羥基苯基馬來醯亞胺、N-對羥基苯基馬來醯亞胺、N-鄰甲基苯基馬來醯亞胺、N-間甲基苯基馬來醯亞胺、N-對甲基苯基馬來醯亞胺、N-鄰甲氧基苯基馬來醯亞胺、N-間甲氧基苯基馬來醯亞胺、N-對甲氧基苯基馬來醯亞胺等N-取代馬來醯亞胺系化合物；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯等(甲基)丙烯酸烷基酯類；(甲基)丙烯酸環戊基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-甲基環己基酯、三環[5.2.1.02,6]癸-8- 基(甲基)丙烯酸酯、(甲基)丙烯酸2-二環戊基氧基乙酯、(甲基)丙烯酸異冰片酯等脂環族(甲基)丙烯酸類；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄基酯等(甲基)丙烯酸芳基酯類；3-(甲基丙烯醯氧基甲基)氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、2-(甲基丙烯醯氧基甲基)氧雜環丁烷、2-(甲基丙烯醯氧基甲基)-4-三氟甲基氧雜環丁烷等的不飽和氧雜環丁烷化合物等。 Specific examples of the polymerizable monomer (b4) having an unsaturated bond capable of achieving copolymerization are: styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxy group. Styrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinyl benzyl An aromatic vinyl compound such as glycidyl ether or p-vinylbenzyl glycidyl ether; N-cyclohexylmaleimide, N-benzyl maleimide, N-phenyl maleimide, N - o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N- M-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenyl malayan N-substituted maleimide compound such as amine, N-p-methoxyphenylmaleimide; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate Ester, isopropyl (meth)acrylate, (A ) (meth)acrylic acid alkyl esters such as n-butyl acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate; cyclopentane (meth)acrylate Base ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]癸-8- Aliphatic (meth)acrylic acid such as (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate (aryl) (meth) acrylate such as benzyl (meth)acrylate; 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl) 3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2 -phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane An unsaturated oxetane compound such as an alkane.

作為上述(b4)來例示的單體可分別單獨使用或組合2種以上使用。 The monomers exemplified as the above (b4) may be used alone or in combination of two or more.

上述鹼可溶性樹脂(B)的含量相對於感光性樹脂組合物中的固體成分，包含10~80重量%，優選包含10~70重量%。按上述的基準，若上述鹼可溶性樹脂(B)的含量為10~80重量%，則上述鹼可溶性樹脂(B)在顯影液中具有充分的溶解性，因而容易形成圖案，並防止顯影時曝光部的像素部分的膜減少，非像素部分的遺漏性變的良好，因而優選。 The content of the alkali-soluble resin (B) is 10 to 80% by weight, and preferably 10 to 70% by weight, based on the solid content of the photosensitive resin composition. According to the above-mentioned criteria, when the content of the alkali-soluble resin (B) is from 10 to 80% by weight, the alkali-soluble resin (B) has sufficient solubility in the developer, and thus it is easy to form a pattern and prevent exposure during development. The film of the pixel portion of the portion is reduced, and the leakage of the non-pixel portion is improved, which is preferable.

光聚合性化合物(C) Photopolymerizable compound (C)

上述光聚合性化合物(C)是借助下述光聚合引發劑(D)的作用來能夠聚合的化合物，可使用單官能單體、二官能單體或多官能單體，可優選使用二官能以上的多官能單體。 The photopolymerizable compound (C) is a compound which can be polymerized by the action of the photopolymerization initiator (D) described below, and a monofunctional monomer, a difunctional monomer or a polyfunctional monomer can be used, and a difunctional or higher functional group can be preferably used. Polyfunctional monomer.

上述單官能單體的具體例有丙烯酸壬基苯基卡必醇酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸2-乙基己基卡必醇酯、丙烯酸2-羥基乙酯或N-乙烯基吡咯烷酮等，但並不限定於此。 Specific examples of the above monofunctional monomer are nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate or N-vinylpyrrolidone or the like, but is not limited thereto.

上述二官能單體的具體例有1,6-己二醇二(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(丙烯醯氧乙基)醚或3-甲基戊二醇二(甲基)丙烯酸酯等，但並不限定於此。 Specific examples of the above difunctional monomer are 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol. The alcohol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, etc. are not limited to this.

上述多官能單體的具體例有三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基三羥甲基丙烷三(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、乙氧基二季戊四醇六(甲基)丙烯酸酯、丙氧基二季戊四醇六(甲基)丙烯酸酯或二季戊四醇六(甲基)丙烯酸酯等，但並不限定於此。 Specific examples of the above polyfunctional monomer are trimethylolpropane tri(meth)acrylate, ethoxytrimethylolpropane tri(meth)acrylate, and propoxytrimethylolpropane tri(methyl). Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxydipentaerythritol hexa(meth)acrylate, propoxydipentaerythritol (meth) acrylate or dipentaerythritol hexa (meth) acrylate, etc., but is not limited thereto.

上述光聚合性化合物(C)相對於著色感光性樹脂組合物中的固體成分，優選包含5~45重量%，尤其，更優選包含7~45重量%。若按上述基準，上述光聚合性化合物(C)包含5~45重量%的情況下，則像素部的強度或平滑性變的良好，因而優選。 The photopolymerizable compound (C) is preferably contained in an amount of 5 to 45% by weight, particularly preferably 7 to 45% by weight, based on the solid content of the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in an amount of 5 to 45% by weight, the strength or smoothness of the pixel portion is improved, which is preferable.

光聚合引發劑(D) Photopolymerization initiator (D)

上述光聚合引發劑(D)以下述化學式2的光聚合引發劑(d1)為必要成分。 The photopolymerization initiator (D) contains the photopolymerization initiator (d1) of the following Chemical Formula 2 as an essential component.

在上述化學式2中，R9由下述化學式3表示，R10為C1~C8的烷基、被取代或未被取代的苯、或被取代或未被取代的苄基，R11為二苯硫基；[化學式3]-R12-R13 In the above Chemical Formula 2, R 9 is represented by the following Chemical Formula 3, R 10 is a C1 to C8 alkyl group, a substituted or unsubstituted benzene, or a substituted or unsubstituted benzyl group, and R 11 is a diphenyl group. Sulfur; [Chemical Formula 3]-R12-R13

在上述化學式3中，R12為C1~C4的亞烷基，R13為C3~C8的烴或C3~C8環烴。 In the above Chemical Formula 3, R12 is a C1 to C4 alkylene group, and R13 is a C3 to C8 hydrocarbon or a C3 to C8 cyclic hydrocarbon.

上述化學式2的光聚合引發劑(d1)通過防止由於染料引起的靈敏度和透射率的下降，從而可使包含染料作為著色劑的本發明的著色感光性樹脂組合物表達有效的光聚合特性。 The photopolymerization initiator (d1) of the above Chemical Formula 2 can exhibit an effective photopolymerization property by the color-sensitive photosensitive resin composition of the present invention containing a dye as a colorant by preventing a decrease in sensitivity and transmittance due to the dye.

上述化學式2的光聚合引發劑(d1)的例有TR-PBG-305等。 Examples of the photopolymerization initiator (d1) of the above Chemical Formula 2 include TR-PBG-305 and the like.

並且，在不損害本發明的效果的範圍內，還可並用除上述之外的光聚合引發劑(d2)，具有代表性地，優選使用選自苯乙酮系化合物、二苯甲酮系化合物、三嗪系化合物、聯咪唑系化合物和噻噸酮系化合物組成的組中的一種以上的化合物。 In addition, the photopolymerization initiator (d2) other than the above may be used in combination, and it is preferable to use a compound selected from the group consisting of an acetophenone-based compound and a benzophenone-based compound. And one or more compounds selected from the group consisting of a triazine compound, a biimidazole compound, and a thioxanthone compound.

上述苯乙酮系化合物的具體例，可舉出二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苄基二甲基縮酮、2- 羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙烷-1-酮、1-羥基環己基苯基甲酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉代-丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-嗎啉代苯基)丁烷-1-酮、2-羥基-2-甲基-1[4-(1-甲基乙烯基)苯基]丙烷-1-酮、2-(4-甲基苄基)-2-(二甲基氨基)-1-(4-嗎啉代苯基)丁烷-1-酮等。 Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl) Thiophenyl)-2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2- Hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1- (4-morpholinophenyl)butan-1-one and the like.

作為上述二苯甲酮系化合物，例如有二苯甲酮、O-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(叔丁基過氧羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等。 Examples of the benzophenone-based compound include benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thioether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

上述三嗪系化合物的具體例，可舉出2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-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-甲氧基苯乙烯基)-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-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。 Specific examples of the above triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-double. (trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-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)vinyl]-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 and the like.

上述聯咪唑化合物的具體例有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、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(三烷氧基苯基)聯咪唑、2,2'-雙(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、或4,4',5,5'位置的苯基被羰烷基取代的咪唑 化合物等。其中，優選使用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、2,2'-雙(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑。 Specific examples of the above biimidazole compound are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2'-bis (2 , 6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or phenyl group at the 4,4',5,5' position is replaced by a carbonylalkyl group Imidazole Compounds, etc. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) is preferably used. -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole.

作為上述噻噸酮系化合物，例如有2-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 As the above thioxanthone-based compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythiophene Tons of ketone and so on.

並且，為了提高本發明的著色感光性樹脂組合物的靈敏度，上述光聚合引發劑(D)還可包括光聚合引發助劑(d3)。本發明的著色感光性樹脂組合物通過包含光聚合引發助劑(d3)，使得靈敏度更高，從而可提高生產率。 Further, in order to increase the sensitivity of the colored photosensitive resin composition of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation aid (d3). The colored photosensitive resin composition of the present invention contains a photopolymerization initiation aid (d3) to make the sensitivity higher, thereby improving productivity.

上述光聚合引發助劑(d3)可優選使用選自胺化合物、羧酸化合物中的一種以上的化合物。 As the photopolymerization initiation aid (d3), one or more compounds selected from the group consisting of an amine compound and a carboxylic acid compound can be preferably used.

上述胺化合物優選使用芳香族胺化合物，具體可使用三乙醇胺、甲基二乙醇胺、三異丙醇胺等脂肪族胺化合物、4-二甲氨基苯甲酸甲酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸異戊酯、4-二甲氨基苯甲酸2-乙基己基酯、苯甲酸2-二甲基氨基乙酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲氨基)二苯甲酮(統稱：米氏酮)、4,4'-雙(二乙氨基)二苯甲酮等。 The above amine compound is preferably an aromatic amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate or 4-dimethylaminobenzoate B can be used. Ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4 4'-bis(dimethylamino)benzophenone (collectively: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like.

上述羧酸化合物優選為芳香族雜環乙酸類，具體可舉出苯硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯硫基乙酸、二甲基苯硫基乙酸、甲氧基苯硫基乙酸、二甲氧基苯硫基乙酸、氯苯硫基乙酸、二氯苯硫基乙酸、N-苯基甘氨酸、苯氧乙酸、萘硫基乙酸、N-萘基甘 氨酸、萘氧基乙酸等。 The carboxylic acid compound is preferably an aromatic heterocyclic acetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethyl group. Phenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl Amino acid, naphthoxyacetic acid, and the like.

以固體成分為基準，上述光聚合引發劑(D)相對於鹼可溶性樹脂(B)和光聚合性化合物(C)之和100重量份，包含0.1~40重量份，優選包含1~30重量份。若上述光聚合引發劑(D)的含量在0.1~40重量份的範圍內，則著色感光性樹脂組合物被高靈敏度化，由此縮短曝光時間，從而提高了生產率，並可維持高解析度，因而優選。並且，通過使用滿足上述條件的組合物來形成的像素部的強度和上述像素部的表面的平滑性也變得良好。並且，在總光聚合引發劑(D)中，應包含10~100重量%的上述光聚合引發劑(d1)，優選地，應包含20~100重量%。若在總光聚合引發劑中，光聚合引發劑(d1)的比率小於10重量%，則無法抑制由染料引起的靈敏度的下降，並在顯影工序中容易產生圖案短路()。 The photopolymerization initiator (D) is contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the sum of the alkali-soluble resin (B) and the photopolymerizable compound (C), based on the solid content. When the content of the photopolymerization initiator (D) is in the range of 0.1 to 40 parts by weight, the colored photosensitive resin composition is highly sensitive, thereby shortening the exposure time, thereby improving productivity and maintaining high resolution. And thus preferred. Further, the strength of the pixel portion formed by using the composition satisfying the above conditions and the smoothness of the surface of the pixel portion are also improved. Further, the total photopolymerization initiator (D) should contain 10 to 100% by weight of the photopolymerization initiator (d1), and preferably 20 to 100% by weight. When the ratio of the photopolymerization initiator (d1) is less than 10% by weight in the total photopolymerization initiator, the decrease in sensitivity due to the dye cannot be suppressed, and pattern short-circuiting is likely to occur in the development process ( ).

並且，若還使用上述光聚合引發助劑(d3)，則以固體成分為基準，上述光聚合引發助劑(d3)相對於鹼可溶性樹脂(B)和光聚合性化合物(C)之和100重量份，可以包含0.1~40重量份，優選包含1~30重量份。若上述光聚合引發助劑(d3)的使用量在上述的0.1~40重量份的範圍內，則可更加提高著色感光性樹脂組合物的靈敏度，並提供提高通過使用上述組合物來形成的濾色器的生產率的效果。 In addition, when the photopolymerization initiation aid (d3) is used, the photopolymerization initiation aid (d3) is 100 wt% based on the sum of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the solid content. The fraction may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight. When the amount of the photopolymerization initiation aid (d3) used is in the range of 0.1 to 40 parts by weight, the sensitivity of the colored photosensitive resin composition can be further improved, and the filtration formed by using the above composition can be provided. The effect of the productivity of the color.

溶劑(E) Solvent (E)

本發明的溶劑(E)只要是可有效溶解包含於著色感 光性樹脂組合物的其它成分，則能夠使用，從塗敷性和乾燥性方面考慮，優選使用沸點為100℃~200℃的有機溶劑。更優選地，可使用丙二醇單***乙酸酯、環己酮、乳酸乙酯、乳酸丁酯、3-乙氧基丙酸乙酯和3-甲氧基丙酸甲酯等。 The solvent (E) of the present invention is effective as long as it is contained in the coloring Other components of the photo-resin composition can be used, and from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferably used. More preferably, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate or the like can be used.

並且，根據本發明的一實施例，優選使用丙二醇單甲醚乙酸酯(e1)和4-羥基-4-甲基-2-戊酮(e2)的混合溶劑。 Further, according to an embodiment of the present invention, a mixed solvent of propylene glycol monomethyl ether acetate (e1) and 4-hydroxy-4-methyl-2-pentanone (e2) is preferably used.

在使用上述混合溶劑的情況下，優選著色感光性樹脂組合物中的4-羥基-4-甲基-2-戊酮的含量為15~45重量%、丙二醇單甲醚乙酸酯的含量為20~70重量%。 In the case of using the above mixed solvent, it is preferred that the content of 4-hydroxy-4-methyl-2-pentanone in the colored photosensitive resin composition is 15 to 45% by weight, and the content of propylene glycol monomethyl ether acetate is 20 to 70% by weight.

若4-羥基-4-甲基-2-戊酮的含量在上述範圍，則不會產生在著色感光性樹脂組合物中因染料的析出而造成的異物，並且不會減少對比度，並由於著色感光性樹脂組合物將具有適當的分散性，因而可確保黏度的穩定性。並且，若丙二醇單甲醚乙酸酯的含量在上述範圍，則可確保包含染料的著色感光性樹脂組合物的黏度的穩定性。 When the content of 4-hydroxy-4-methyl-2-pentanone is in the above range, foreign matter due to precipitation of the dye in the colored photosensitive resin composition does not occur, and contrast is not reduced, and coloring is caused. The photosensitive resin composition will have appropriate dispersibility, and thus stability of viscosity can be ensured. Further, when the content of the propylene glycol monomethyl ether acetate is in the above range, the stability of the viscosity of the colored photosensitive resin composition containing the dye can be ensured.

作為本發明的溶劑，可與上述混合溶劑一同混合可有效溶解包含於著色感光性樹脂組合物的其它成分並通常用於著色感光性樹脂組合物的溶劑(e3)來使用。尤其，優選為醚類、芳香族烴類、酮類、醇類、酯類或醯胺類等。 The solvent of the present invention can be used by being mixed with the above-mentioned mixed solvent to effectively dissolve the other components contained in the colored photosensitive resin composition and usually used for coloring the photosensitive resin composition (e3). In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, guanamines and the like are preferable.

上述溶劑(e3)具體可舉出乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚等乙二醇單烷基醚類；二乙二醇二甲醚、二乙二醇二***、二乙二醇二丙醚、二乙二醇二丁醚等二乙二醇二烷基醚類；乙二醇甲醚乙酸 酯、乙二醇***乙酸酯等乙二醇烷基醚乙酸酯類；丙二醇單***乙酸酯、丙二醇單丙醚乙二醇、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯等亞烷基二醇烷基醚乙酸酯類；苯、甲苯、二甲苯、均三甲苯等芳香族烴類；甲基乙基酮、丙酮、甲基戊酮、甲基異丁基甲酮、環己酮等酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等的醇類；以及3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯等的酯類；以及γ-丁內酯等的環狀酯類等。 Specific examples of the solvent (e3) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol methyl ether acetate Ethylene glycol alkyl ether acetate such as ester, ethylene glycol ethyl ether acetate; propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether glycol, methoxybutyl acetate, methoxypentyl An alkylene glycol alkyl ether acetate such as an acid ester; an aromatic hydrocarbon such as benzene, toluene, xylene or mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, etc.; and ethyl 3-ethoxypropionate, 3-methoxypropionic acid An ester such as a methyl ester; or a cyclic ester such as γ-butyrolactone.

以本發明的著色感光性樹脂組合物的總重量為基準，本發明的溶劑(E)可包含60~90重量%，優選包含70~85重量%。若上述溶劑(E)的含量在上述的60~90重量%的範圍，則當使用輥塗機、旋轉塗布機、狹縫與旋轉塗布機、狹縫塗布機(還被稱作擠壓式塗布機)、噴墨機等塗敷裝置塗敷時，可提供塗敷性變得良好的效果。 The solvent (E) of the present invention may comprise 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the content of the solvent (E) is in the range of 60 to 90% by weight as described above, a roll coater, a spin coater, a slit and a spin coater, and a slit coater (also referred to as extrusion coating) are used. When the coating device such as an inkjet machine is applied, it is possible to provide an effect that the coating property is good.

抗氧化劑(F) Antioxidant (F)

本發明的著色感光性樹脂組合物還可包含抗氧化劑。 The colored photosensitive resin composition of the present invention may further comprise an antioxidant.

抗氧化劑(F)可包含酚系抗氧化劑的一種以上和磷系抗氧化劑的一種以上，並且，酚系抗氧化劑應在150℃的烘箱中200小時以上不被劣化()。 The antioxidant (F) may contain one or more of a phenolic antioxidant and one or more of a phosphorus-based antioxidant, and the phenolic antioxidant should not be deteriorated in an oven at 150 ° C for more than 200 hours ( ).

本發明的酚系抗氧化劑優選地使用受阻酚系抗氧化劑，並且具體例如下。 The phenolic antioxidant of the present invention preferably uses a hindered phenol-based antioxidant, and is specifically, for example, the following.

3-(3,5-二叔丁基-4-羥基苯基)丙酸十八烷基酯(Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)(264小時)、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羥基 苄基)苯(1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene)(240小時)、四(3,5-二叔丁基-4-羥基氫化肉桂酸)季戊四醇酯(Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))(960小時)。 Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenylproppropate) (264 hours) 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyl Benzyl)benzene (1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene) (240 hours), four (3,5-di-uncle Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (960 hours).

上述磷系抗氧化劑的具體例如下。 Specific examples of the above phosphorus-based antioxidant are as follows.

磷酸三苯酯(Triphenyl phosphate)、磷酸異癸基二苯酯(Isodecyl diphenyl phosphate)、三(2,4-二叔丁基苯基)磷酸酯(Tris(2,4-di-tert-butylphenyl)phosphate)、3,9-雙(十八烷氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷(3,9-Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane)、2,2'-亞甲基雙(4,6-二叔丁基苯基)-2-乙基己基磷酸酯(2,2'-methylenebis(4,6-di-tert-butyl-phenyl)-2-ethylhexyl phosphate)。 Triphenyl phosphate, Isodecyl diphenyl phosphate, Tris(2,4-di-tert-butylphenyl) Phosphate, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (3,9-Bis(octadecyloxy) )-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane), 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl Phosphate (2,2'-methylenebis(4,6-di-tert-butyl-phenyl)-2-ethylhexyl phosphate).

以固體成分為基準，相對於100重量份的光聚合引發劑(D)，上述抗氧化劑(F)包含1~100重量份，優選包含2~50重量份。若上述抗氧化劑(F)的含量在上述的1~100重量份的範圍內，則可期待著色感光性樹脂組合物在靈敏度不下降的情況下提高透射率，因而優選。若上述抗氧化劑(F)的含量小於1重量份，則難以期待提高透射率，若上述抗氧化劑(F)的含量大於100重量份，則難以抑制因染料造成的靈敏度的下降，因而難以實現高靈敏度，並容易在顯影工序中產生圖案短路。 The antioxidant (F) is contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D), based on the solid content. When the content of the antioxidant (F) is in the range of 1 to 100 parts by weight as described above, it is expected that the colored photosensitive resin composition can improve the transmittance without lowering the sensitivity, which is preferable. When the content of the antioxidant (F) is less than 1 part by weight, it is difficult to expect an increase in transmittance. When the content of the antioxidant (F) is more than 100 parts by weight, it is difficult to suppress a decrease in sensitivity due to a dye, and thus it is difficult to achieve high density. Sensitivity and easy pattern short circuit in the development process.

添加劑(G) Additive (G)

本發明的著色感光性樹脂組合物除上述成分外，在不阻礙本發明的目的範圍內，可根據技術人員的需要並用填充劑、其它高分子化合物、固化劑、顏料分散劑、密合促進劑、紫外線吸收劑和抗凝聚劑等添加劑(G)。 The color-sensitive photosensitive resin composition of the present invention can be used in combination with a filler, another polymer compound, a curing agent, a pigment dispersant, and an adhesion promoter in accordance with the needs of the skilled person, in addition to the above-described components, without departing from the object of the present invention. Additives (G) such as UV absorbers and anti-agglomerating agents.

上述填充劑具體可使用玻璃、二氧化矽、氧化鋁等，但並不限定於此。 Specifically, glass, cerium oxide, aluminum oxide, or the like can be used as the above filler, but is not limited thereto.

上述其它高分子化合物具體可使用：環氧樹脂、馬來醯亞胺樹脂等固化性樹脂；聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、多氟烷基丙烯酸酯、聚酯、聚氨酯等熱塑性樹脂等，但並不限定於此。 Specific examples of the above polymer compound include curable resins such as epoxy resins and maleic imine resins; polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and polyester. A thermoplastic resin such as polyurethane is not limited thereto.

上述固化劑用於實現深度固化和提高機械性強度，具體可使用環氧化合物、多官能異氰酸酯化合物、三聚氰胺化合物、氧雜環丁烷化合物等，但並不限定於此。上述環氧化合物具體可使用雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、其它芳香族系環氧樹脂、脂環族系環氧樹脂、縮水甘油酯系樹脂、縮水甘油胺系樹脂、或這些環氧樹脂的溴化衍生物、環氧樹脂及其溴化衍生物之外的脂肪族和脂環族或芳香族環氧化合物、丁二烯(共)聚合物的環氧化物、異戊二烯(共)聚合物的環氧化物、(甲基)丙烯酸縮水甘油酯(共)聚合物、異氰脲酸三縮水甘油酯等，但並不限定於此。上述氧雜環丁烷化合物具體可使用碳酸酯雙氧雜環丁烷、二甲苯雙氧雜環丁烷、己二酸酯雙氧雜環 丁烷、對苯二甲酸酯雙氧雜環丁烷、環己烷二羧酸雙氧雜環丁烷等，但並不限定於此。 The curing agent is used for achieving deep curing and improving mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, or the like can be used, but is not limited thereto. Specifically, the above epoxy compound may be a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol F type epoxy resin, a novolak type epoxy resin, or the like. Family epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or brominated derivatives of these epoxy resins, epoxy resins and fats other than brominated derivatives thereof Family and alicyclic or aromatic epoxy compounds, epoxides of butadiene (co)polymers, epoxides of isoprene (co)polymers, glycidyl (meth)acrylate (total) The polymer, triglycidyl isocyanurate or the like is not limited thereto. Specifically, the above oxetane compound may be a carbonate dioxetane, a xylene dioxetane or an adipate dioxane. Butane, terephthalate dioxetane, cyclohexanedicarboxylic acid dioxetane, etc., but are not limited thereto.

上述固化劑可與固化劑一同並用能夠使環氧化合物的環氧基和氧雜環丁烷化合物的氧雜環丁烷骨架開環聚合的固化輔助化合物。上述固化輔助化合物具體可使用多元羧酸類、多元羧酸酐類、產酸劑等。上述羧酸酐類可利用在市場上銷售的環氧樹脂固化劑。市場上銷售的上述環氧樹脂固化劑例如可舉出ADEKA HARDENER EH-700(商品名)(Adek工業株式會社製造)、RIKACID HH(商品名)(新日本理化株式會社製造)、MH-700(商品名)(新日本理化株式會社製造)等。 The curing agent may be used together with a curing agent to form a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like. As the above carboxylic acid anhydride, an epoxy resin curing agent which is commercially available can be used. For example, ADEKA HARDENER EH-700 (trade name) (manufactured by Adek Industries Co., Ltd.), RIKACID HH (trade name) (manufactured by Shin-Nippon Chemical Co., Ltd.), and MH-700 (for example) Product name) (manufactured by Shin-Nippon Chemical Co., Ltd.).

在上述中例示的固化劑和固化輔助化合物可分別單獨使用或混合2種以上來使用。 The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

上述顏料分散劑可使用市場上銷售的表面活性劑，具體可單獨使用選自矽系、氟系、酯系、陽離子系、陰離子系、非離子系和兩性表面活性劑中的表面活性劑，或可使用它們的混合物。更具體地，可使用聚氧乙烯烷基醚類、聚氧乙烯烷基苯醚類、聚氧乙烯乙二醇酯類、山梨坦脂肪酸酯類、脂肪酸改性聚酯類、叔胺改性聚氨酯類、聚乙烯亞胺類等，此外，以商品名為例，可使用KP(信越化學工業有限公司)、POLYFLOW(共榮社化學有限公司)、EFTOP(Tohkem Products公司)、MEGAFAC(日本油墨化學有限公司)、Flourad(日本住友3M有限公司)、Asahi guard和Surflon(以上為旭硝子玻璃有限公司)、SOLSPERSE (Lubrizol公司)、EFKA(EFKA化工公司)、PB 821(Ajinomoto公司)、Disperbyk-series(BYK-chemi)等。 As the above pigment dispersant, a commercially available surfactant may be used, and specifically, a surfactant selected from the group consisting of a lanthanide, a fluorine-based, an ester-based, a cationic, an anionic, a nonionic, and an amphoteric surfactant may be used alone, or A mixture of them can be used. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene glycol esters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes can be used. For example, KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Toray E-Chemical Co., Ltd.), EFTOP (Tohkem Products), MEGAFAC (Japan Ink Chemistry) can be used as a product name. Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard and Surflon (above: Asahi Glass Co., Ltd.), SOLSPERSE (Lubrizol), EFKA (EFKA Chemical Company), PB 821 (Ajinomoto), Disperbyk-series (BYK-chemi), etc.

上述密合促進劑具體可單獨使用選自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-氨乙基)-3-氨丙基甲基二甲氧基矽烷、N-(2-氨乙基)-3-氨丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-縮水甘油丙基三甲氧基矽烷、3-縮水甘油丙基甲基二甲氧基矽烷、2-(3,4-環氧環己烷)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-甲基丙烯醯氧丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷和3-異氰酸酯基丙基三乙氧基矽烷中的物質或它們的混合物。 The above adhesion promoter may be specifically selected from the group consisting of vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl). -3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidron Trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexane)ethyltrimethoxy decane, 3-chloropropylmethyldimethoxy Baseline, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxydecane, and 3- A substance in isocyanatopropyltriethoxydecane or a mixture thereof.

相對於組合物的總固體成分，上述密合促進劑可包含0.01~10重量%的，可優選包含0.05~2重量%。 The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, and preferably 0.05 to 2% by weight, based on the total solid content of the composition.

上述紫外線吸收劑具體可使用2-(3-叔丁基-2-羥基-5-甲基苯基)-5-氯苯並***、烷氧基苯甲酮等，但並不限定於此。 Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone, but are not limited thereto. .

上述抗凝聚劑具體可使用聚丙烯酸鈉等，但並不限定於此。 Specifically, the above anti-agglomerating agent may be sodium polyacrylate or the like, but is not limited thereto.

可如下舉例說明本發明的著色感光性樹脂組合物的製造方法。 The method for producing the colored photosensitive resin composition of the present invention can be exemplified as follows.

首先，混合上述著色劑(A)中的顏料(a1)與溶劑(E)，並利用珠磨機等進行分散，直到顏料的平均粒徑達到0.2μm以下程度。此時，根據需要可與溶劑(E)一 同混合顏料分散劑(a4)、鹼可溶性樹脂(B)的一部分或全部、或染料(a2)，進行溶解或分散。 First, the pigment (a1) and the solvent (E) in the coloring agent (A) are mixed and dispersed by a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, it can be combined with the solvent (E) as needed. A part or all of the mixed pigment dispersant (a4), the alkali-soluble resin (B), or the dye (a2) is dissolved or dispersed.

向上述混合的分散液中添加染料(a2)、染料(a3)、其餘的鹼可溶性樹脂(B)、光聚合性化合物(C)、光聚合引發劑(D)，必要時還添加抗氧化劑(F)、添加劑(G)、以及溶劑(E)，使其達到預定的濃度，從而可製造本發明的著色感光性樹脂組合物。 To the above-mentioned mixed dispersion, a dye (a2), a dye (a3), the remaining alkali-soluble resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D) are added, and if necessary, an antioxidant is added ( F), the additive (G), and the solvent (E) are brought to a predetermined concentration to produce the colored photosensitive resin composition of the present invention.

以下，以本發明的實施例為基礎進行更加詳細的說明，但下述公開的本發明的實施方式僅僅是例示性的，本發明的範圍並不受這些實施方式的限制。本發明的權利要求書示出本發明的範圍，尤其包含具有與本發明要求保護範圍的記載同等的意義及在與本發明要求保護範圍的記載同等的範圍內的所有變更。並且，若沒有特殊的說明，在以下實施例、比較例中，表示含量的“%”和“份”為重量基準。 In the following, the embodiments of the present invention are described in more detail based on the embodiments of the present invention, but the scope of the present invention is not limited by the embodiments. The scope of the present invention is defined by the scope of the present invention, and is intended to include all modifications within the scope equivalent to the scope of the claims. Further, unless otherwise specified, in the following examples and comparative examples, "%" and "parts" indicating the content are based on the weight.

製造顏料分散組合物 Manufacturing pigment dispersion composition <顏料分散組合物M1> <Pigment Dispersion Composition M1>

借助珠磨機對12.0重量份的作為顏料的C.I.顏料紅254、5.0重量份的作為顏料分散劑的DISPERBYK-2001(BYK公司製造)、13.0重量份的作為溶劑的4-羥基-4-甲基-2-戊酮、70.0重量份的丙二醇甲醚乙酸酯進行12小時的混合/分散，從而製造出顏料分散組合物M1。 12.0 parts by weight of CI Pigment Red 254 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK Corporation) as a pigment dispersant, and 13.0 parts by weight of 4-hydroxy-4-methyl as a solvent by means of a bead mill 2-pentanone, 70.0 parts by weight of propylene glycol methyl ether acetate was mixed/dispersed for 12 hours to produce a pigment dispersion composition M1.

<顏料分散組合物M2> <Pigment Dispersion Composition M2>

借助珠磨機對12.0重量份的作為顏料的C.I.顏料紅 177、5.0重量份的作為顏料分散劑的DISPERBYK-2001(BYK公司製造)、13.0重量份的作為溶劑的4-羥基-4-甲基-2-戊酮、70.0重量份的丙二醇甲醚乙酸酯進行12小時的混合/分散，從而製造出顏料分散組合物M2。 12.0 parts by weight of C.I. Pigment Red as a pigment by means of a bead mill 177, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK Corporation) as a pigment dispersant, 13.0 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 70.0 parts by weight of propylene glycol methyl ether acetate The ester was subjected to mixing/dispersion for 12 hours to produce a pigment dispersion composition M2.

<顏料分散組合物M3> <Pigment Dispersion Composition M3>

借助珠磨機對12.0重量份的作為顏料的C.I.顏料紅242、5.0重量份的作為顏料分散劑的DISPERBYK-2001(BYK公司製造)、13.0重量份的作為溶劑的4-羥基-4-甲基-2-戊酮、70.0重量份的丙二醇甲醚乙酸酯進行12小時的混合/分散，從而製造出顏料分散組合物M3。 12.0 parts by weight of CI Pigment Red 242 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK Corporation) as a pigment dispersant, and 13.0 parts by weight of 4-hydroxy-4-methyl as a solvent by a bead mill 2-pentanone, 70.0 parts by weight of propylene glycol methyl ether acetate was mixed/dispersed for 12 hours to produce a pigment dispersion composition M3.

鹼可溶性樹脂的合成 Synthesis of alkali soluble resin <合成例1> <Synthesis Example 1>

向具備攪拌器、溫度計、回流冷卻管、滴液漏斗和氮導入管的燒瓶投入120重量份的丙二醇單甲醚乙酸酯、80重量份的丙二醇單甲醚、2重量份的偶氮二異丁腈(AIBN)、13.0重量份丙烯酸、10重量份的甲基丙烯酸苄基酯、57.0重量份的4-甲基苯乙烯、20重量份的甲基丙烯酸甲酯、3重量份的正十二烷基硫醇，並進行了氮置換。之後進行攪拌，並將反應液的溫度提升為110℃，進行了6個小時的反應。這樣合成的鹼可溶性樹脂的固體成分的酸值為100.2mgKOH/g，利用凝膠滲透色譜法(GPC)測定的重均分子量Mw約為15110。 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, and 2 parts by weight of azo diisobutyl ether were placed in a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube. Nitrile (AIBN), 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of ortho 12 Alkyl mercaptan and nitrogen substitution. Thereafter, stirring was carried out, and the temperature of the reaction liquid was raised to 110 ° C, and the reaction was carried out for 6 hours. The solid content of the alkali-soluble resin thus synthesized was 100.2 mgKOH/g, and the weight average molecular weight Mw measured by gel permeation chromatography (GPC) was about 15,110.

著色感光性樹脂組合物的製造 Production of coloring photosensitive resin composition <實施例1> <Example 1>

混合29.74重量份的上述<顏料分散組合物M1>、5.66重量份的<顏料分散組合物M2>、0.52重量份的酸性紅52(Acid Red 52，TCI America公司)、0.41重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、9.32重量份的<合成例1>的樹脂、9.32重量份的KAYARAD DPHA(日本化藥公司製造)、0.93重量份的TR-PBG-305(TRONLY公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、31.34重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 29.74 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 5.66 parts by weight of <Pigment Dispersion Composition M2>, 0.52 parts by weight of Acid Red 52 (Acid Red 52, TCI America), and 0.41 parts by weight of Solvent Red 122 were mixed. (CI Solvent Red 122, Basf), 9.32 parts by weight of the resin of <Synthesis Example 1>, 9.32 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.93 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 31.34 parts by weight of propylene glycol monomethyl ether acetate were used to produce a colored photosensitive resin composition.

<實施例2> <Example 2>

混合16.31重量份的上述<顏料分散組合物M1>、21.90重量份的<顏料分散組合物M2>、4.66重量份的<顏料分散組合物M3>、0.45重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、8.42重量份的<合成例1>的樹脂、8.42重量份的KAYARAD DPHA(日本化藥公司製造)、0.84重量份的TR-PBG-305(TRONLY公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、26.27重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 16.31 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 21.90 parts by weight of <Pigment Dispersion Composition M2>, 4.66 parts by weight of <Pigment Dispersion Composition M3>, and 0.45 parts by weight of Solvent Red 122 (CISolvent Red 122) , Basf company, 8.42 parts by weight of the resin of <Synthesis Example 1>, 8.42 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 0.84 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), and 12.75 parts by weight 4-hydroxy-4-methyl-2-pentanone and 26.27 parts by weight of propylene glycol monomethyl ether acetate were used to produce a colored photosensitive resin composition.

<比較例1> <Comparative Example 1>

混合21.20重量份的上述<顏料分散組合物M1>、3.50重量份的<顏料分散組合物M2>、2.55重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、9.55重量份的<合成例1>的樹脂、9.55重量份的KAYARAD DPHA(日本化藥公司製造)、0.95重量份的TR-PBG-305(TRONLY公司 製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、26.27重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 21.20 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 3.50 parts by weight of <Pigment Dispersion Composition M2>, 2.55 parts by weight of Solvent Red 122 (CISolvent Red 122, Basf Corporation), and 9.55 parts by weight of <Synthesis Example 1> resin, 9.55 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.95 parts by weight of TR-PBG-305 (TRONLY Co., Ltd.) (manufactured), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 26.27 parts by weight of propylene glycol monomethyl ether acetate to produce a colored photosensitive resin composition.

<比較例2> <Comparative Example 2>

混合32.88重量份的上述<顏料分散組合物M1>、0.71重量份的酸性紅(Acid Red 52，TCI America公司)、0.40重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、9.61重量份的<合成例1>的樹脂、9.61重量份的KAYARAD DPHA(日本化藥公司製造)、0.95重量份的TR-PBG-305(TRONLY公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、33.08重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 32.88 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 0.71 part by weight of Acid Red (Acid Red 52, TCI America), 0.40 parts by weight of Solvent Red 122 (CISolvent Red 122, Basf), and 9.61 parts by weight. Resin of <Synthesis Example 1>, 9.61 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 0.95 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), and 12.75 parts by weight of 4-hydroxy-4-methyl 2-pentanone and 33.08 parts by weight of propylene glycol monomethyl ether acetate were used to produce a colored photosensitive resin composition.

<比較例3> <Comparative Example 3>

混合25.11重量份的上述<顏料分散組合物M2>、19.93重量份的<顏料分散組合物M3>、0.47重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、7.96重量份的<合成例1>的樹脂、7.96重量份的KAYARAD DPHA(日本化藥公司製造)、0.79重量份的TR-PBG-305(TRONLY公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、25.03重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 25.11 parts by weight of the above-mentioned <Pigment Dispersion Composition M2>, 19.93 parts by weight of <Pigment Dispersion Composition M3>, 0.47 parts by weight of Solvent Red 122 (CISolvent Red 122, Basf Corporation), and 7.96 parts by weight of <Synthesis Example 1> resin, 7.96 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), 0.79 parts by weight of TR-PBG-305 (manufactured by TRONLY Co., Ltd.), and 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentyl A ketone and 25.03 parts by weight of propylene glycol monomethyl ether acetate were used to produce a colored photosensitive resin composition.

<比較例4> <Comparative Example 4>

混合29.74重量份的上述<顏料分散組合物M1>、5.66重量份的<顏料分散組合物M2>、0.52重量份的酸性紅52 (Acid Red 52，TCI America公司)、0.41重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、9.32重量份的<合成例1>的樹脂、9.32重量份的KAYARAD DPHA(日本化藥公司製造)、0.64重量份的2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮(Ciba公司製造)、0.28重量份的2，4-二乙基噻噸酮(Sigma-Aldrich公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、31.34重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 29.74 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 5.66 parts by weight of <Pigment Dispersion Composition M2>, and 0.52 parts by weight of Acid Red 52 were mixed. (Acid Red 52, TCI America), 0.41 part by weight of solvent red 122 (CISolvent Red 122, Basf), 9.32 parts by weight of the resin of <Synthesis Example 1>, and 9.32 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) Manufactured, 0.64 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by Ciba Co., Ltd.), 0.28 parts by weight of 2,4-diethyl A thioxanthone (manufactured by Sigma-Aldrich Co., Ltd.), 12.75 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 31.34 parts by weight of propylene glycol monomethyl ether acetate to produce a colored photosensitive resin composition .

<比較例5> <Comparative Example 5>

混合16.31重量份的上述<顏料分散組合物M1>、21.90重量份的<顏料分散組合物M2>、4.66重量份的<顏料分散組合物M3>、0.45重量份的溶劑紅122(C.I.Solvent Red 122，Basf公司)、8.42重量份的<合成例1>的樹脂、8.42重量份的KAYARAD DPHA(日本化藥公司製造)、0.64重量份的2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮(Ciba公司製造)、0.28重量份的2,4-二乙基噻噸酮(Sigma-Aldrich公司製造)、12.75重量份的4-羥基-4-甲基-2-戊酮、26.27重量份的丙二醇單甲醚乙酸酯來製造出著色感光性樹脂組合物。 16.31 parts by weight of the above-mentioned <Pigment Dispersion Composition M1>, 21.90 parts by weight of <Pigment Dispersion Composition M2>, 4.66 parts by weight of <Pigment Dispersion Composition M3>, and 0.45 parts by weight of Solvent Red 122 (CISolvent Red 122) , Basf company), 8.42 parts by weight of the resin of <Synthesis Example 1>, 8.42 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and 0.64 parts by weight of 2-methyl-1-(4-methylthiophenyl) )-2-morpholinopropan-1-one (manufactured by Ciba Co., Ltd.), 0.28 parts by weight of 2,4-diethylthioxanthone (manufactured by Sigma-Aldrich Co., Ltd.), and 12.75 parts by weight of 4-hydroxy-4- Methyl-2-pentanone and 26.27 parts by weight of propylene glycol monomethyl ether acetate were used to produce a colored photosensitive resin composition.

<實驗例1>測定密合性、透射率和對比度 <Experimental Example 1> Measurement of adhesion, transmittance, and contrast

利用在上述實施例1至2和比較例1至3中製造的著色感光性樹脂組合物來製造出濾色器。 A color filter was produced using the colored photosensitive resin compositions produced in the above Examples 1 to 2 and Comparative Examples 1 to 3.

具體地，利用旋塗法在2英寸見方的玻璃基板(康寧公司製造，“EAGLE XG”)上分別塗敷上述各著色感光 性樹脂組合物，之後放置於加熱板上，並在100℃的溫度下維持3分鐘，從而形成了薄膜。接著，將具有1μm至100μm的線/間隔圖案的試驗光掩膜放置於上述薄膜上，以與試驗光掩膜形成300μm的間隔的方式來照射了紫外線。此時，紫外線光源使用一併包含g、h、i線的1KW的高壓汞燈，並以60mJ/cm2的照度進行了照射，且未使用特殊的光學濾光器。將照射紫外線的上述薄膜浸泡於pH為10.5的KOH水溶液顯影溶液2分鐘，來進行顯影。利用蒸餾水對上述塗敷有薄膜的玻璃板進行洗滌之後，吹送氮氣來進行乾燥，並在230℃的加熱烘箱中加熱25分鐘，從而製造出濾色器。 Specifically, each of the colored photosensitive resin compositions described above was applied to a 2 inch square glass substrate ("EAGLE XG" manufactured by Corning Incorporated) by spin coating, and then placed on a hot plate at a temperature of 100 ° C. It was maintained for 3 minutes to form a film. Next, a test photomask having a line/space pattern of 1 μm to 100 μm was placed on the above film, and ultraviolet rays were irradiated so as to form a space of 300 μm with the test photomask. At this time, the ultraviolet light source was irradiated with a 1 KW high-pressure mercury lamp including g, h, and i lines, and was irradiated with an illuminance of 60 mJ/cm 2 , and a special optical filter was not used. The above-mentioned film irradiated with ultraviolet rays was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to carry out development. The above-mentioned film-coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 25 minutes to produce a color filter.

在上述中製造出的濾色器的膜的厚度為2.4μm。 The film of the color filter manufactured in the above had a thickness of 2.4 μm.

<測定透射率和對比度> <Measure Transmittance and Contrast>

除了未使用試驗光掩膜，以與上述<實驗例1>相同的方式製造出濾色器，並利用色度計(奧林巴斯公司製造，OSP-200)測定了透射率。 A color filter was produced in the same manner as in the above <Experimental Example 1 except that the test photomask was not used, and the transmittance was measured by a colorimeter (Olympus Corporation, OSP-200).

<密合性> <adhesion>

在通過光學顯微鏡評價所生成的圖案時，按如下標準評價圖案上的剝落()現象程度，並顯示在下述<表1>。 When the generated pattern was evaluated by an optical microscope, the peeling on the pattern was evaluated according to the following criteria ( The degree of phenomenon is shown in <Table 1> below.

○：圖案上沒有剝落。 ○: There is no peeling on the pattern.

△：圖案上剝落1~3個。 △: 1 to 3 peeling off the pattern.

×：圖案上剝落4個以上。 ×: Four or more sheets were peeled off from the pattern.

將上述實驗例的結果顯示於<表1>。 The results of the above experimental examples are shown in <Table 1>.

根據上述表1，在實施例1中，由於包含酸性紅52，因而具有對比度略有下降，但亮度高的特徵。即，可知，與表現出相似的對比度的比較例1相比，亮度更加優異。 According to the above Table 1, in the first embodiment, since the acid red 52 is contained, the contrast is slightly lowered, but the luminance is high. That is, it is understood that the brightness is more excellent than that of Comparative Example 1 which exhibits a similar contrast.

在實施例2中，由於包含C.I.顏料紅242，因而具有亮度略低，但對比度非常高的特徵。即，可知，當與比較例1進行比較時，亮度相似，但對比度優異。 In Example 2, since C.I. Pigment Red 242 was contained, it had a characteristic that the brightness was slightly low, but the contrast was very high. That is, it is understood that when compared with Comparative Example 1, the luminance is similar, but the contrast is excellent.

即，雖然亮度和對比度屬於權衡(Trade-Off)關係，但若使用本發明的四元系組合物，則可製造具有適當亮度和對比度的濾色器。 That is, although the brightness and contrast are in a trade-off relationship, if the quaternary composition of the present invention is used, a color filter having appropriate brightness and contrast can be produced.

另一方面，雖然如本發明的組合物那樣包含含有染料作為著色劑的四元系，但使用了不同的光聚合引發劑的比較例4和比較例5中，雖然表現出適當的亮度和對比度，但密合性下降。 On the other hand, although the quaternary system containing a dye as a colorant is contained as in the composition of the present invention, in Comparative Example 4 and Comparative Example 5 using different photopolymerization initiators, although appropriate brightness and contrast are exhibited. , but the adhesion is declining.

即，本發明的組合物具有表現出適當的亮度和對比 度，並且密合性也優異的卓越的效果。 That is, the composition of the present invention has an appropriate brightness and contrast The superior effect of the excellentness is excellent.

Claims (9)

一種紅色像素用著色感光性樹脂組合物，所述著色感光性樹脂組合物包含著色劑A、鹼可溶性樹脂B、光聚合性化合物C、光聚合引發劑D以及溶劑E，其中，所述著色劑A包含C.I.顏料紅254和C.I.顏料紅177，並包含選自C.I.顏料紅242、由下述化學式1表示的呫噸系染料和金屬配位元化合物結構的偶氮系染料中的2種以上，所述光聚合引發劑D包含由下述化學式2表示的含有二苯硫基的肟酯系光引發劑， 在上述式中，R1、R2、R3、R4、R5和R6各自獨立地為氫或C1~C5的烷基，R7和R8各自獨立地為氫、COOH、COO-、SO3 -、SO3H、SO3Na、COOCH3或COOCH2CH3；化學式2： 在上述式中，R9為下述化學式3，R10為C1~C8的烷基、被取代或未被取代的苯基、或被取代或未被取代的苄基，R11為二苯硫基；化學式3：-R12-R13在上述式中，R12為C1~C4的亞烷基，R13為C3~C8的烴或C3~C8的環烴。 A colored photosensitive resin composition for a red pixel, the colored photosensitive resin composition comprising a colorant A, an alkali-soluble resin B, a photopolymerizable compound C, a photopolymerization initiator D, and a solvent E, wherein the colorant A contains CI Pigment Red 254 and CI Pigment Red 177, and contains two or more kinds of azo dyes selected from the group consisting of CI Pigment Red 242, a xanthene-based dye represented by the following Chemical Formula 1, and a metal complex compound structure. The photopolymerization initiator D contains a diphenylthio group-containing oxime ester photoinitiator represented by the following Chemical Formula 2, In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen or a C1 to C5 alkyl group, and R 7 and R 8 are each independently hydrogen, COOH, COO - , SO 3 - , SO 3 H, SO 3 Na, COOCH 3 or COOCH 2 CH 3 ; Chemical Formula 2: In the above formula, R 9 is a chemical formula 3, R 10 is a C1 to C8 alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R 11 is diphenyl sulfide. In the above formula, R12 is a C1 to C4 alkylene group, and R13 is a C3 to C8 hydrocarbon or a C3 to C8 cyclic hydrocarbon. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，在所述著色劑A中包含30~80重量%的C.I.顏料紅254、10~50重量%的C.I.顏料紅177。 The coloring photosensitive resin composition for red pixels according to claim 1, wherein the coloring agent A contains 30 to 80% by weight of C.I. Pigment Red 254 and 10 to 50% by weight of C.I. Pigment Red 177. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，在所述著色劑A中包含5~20重量%的C.I.顏料紅242。 The coloring photosensitive resin composition for red pixels according to claim 1, wherein the coloring agent A contains 5 to 20% by weight of C.I. Pigment Red 242. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，在所述著色劑A中包含5~15重量%的由所述化學式1表示的呫噸系染料。 The colored photosensitive resin composition for red pixels according to claim 1, wherein the colorant A contains 5 to 15% by weight of the xanthene dye represented by the chemical formula 1. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，在所述著色劑A中包含5~15重量%的金屬配位元化合物結構的偶氮系染料。 The colored photosensitive resin composition for red pixels according to claim 1, wherein the colorant A contains an azo dye of 5 to 15% by weight of a metal complex compound structure. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，相對於所述著色感光性樹脂組合物中的總固體成分，包含5~60重量%的著色劑A、10~80重量%的鹼可溶性樹脂B和5~45重量%的光聚合性化合物C；相對於所述鹼可溶性樹脂B和光聚合性化合物C的固體成分的重量，包含0.1~40重量%的光聚合引發劑D。 The colored photosensitive resin composition for red pixels according to claim 1, wherein the coloring agent A is contained in an amount of 5 to 60% by weight, and 10 to 80% by weight based on the total solid content of the colored photosensitive resin composition. The alkali-soluble resin B and the photopolymerizable compound C in an amount of 5 to 45% by weight; the photopolymerization initiator D is contained in an amount of 0.1 to 40% by weight based on the weight of the solid content of the alkali-soluble resin B and the photopolymerizable compound C. 如請求項1之紅色像素用著色感光性樹脂組合物，其中，所述溶劑為丙二醇單甲醚乙酸酯e1和4-羥基-4-甲基-2-戊酮e2的混合溶劑。 The coloring photosensitive resin composition for red pixels according to claim 1, wherein the solvent is a mixed solvent of propylene glycol monomethyl ether acetate e1 and 4-hydroxy-4-methyl-2-pentanone e2. 一種濾色器，其係由如請求項1之紅色像素用著色感光性樹脂組合物製成。 A color filter made of a colored photosensitive resin composition for red pixels as claimed in claim 1. 一種液晶顯示裝置，其包括如請求項8之濾色器。 A liquid crystal display device comprising the color filter of claim 8.
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